SAFEKINEX SAFe and Efficient hydrocarbon oxidation processes by KINetics and Explosion

eXpertise and development of computational process engineering tools

Project No. EVG1-CT-2002-00072

Work Package 5

Kinetic Reduction Software

Deliverable 38

Reduced Kinetic Models for Different Classes of Problems

University of Leeds Leeds LS2 9JT

UK

. FairweatheM r

M.J. Pilling R. Porter

A. S. Tomlin

J. F. Griffiths K. J. Hughes

Contents

1 Introduction 3

2 Summary of Model Reduction Methods

a) Background 3 b) Sensitivity-based reduction procedures for kinetic models 4 c) Timescale-based reduction procedures for kinetic models 5

3 C1 – C3 Alkanes

a) Reduced models for propane derived in zero-dimensional simulations 7 b) Application to and further development from one-dimensional simulations 11

4 C4 – C10 Alkanes 14

5 Alkenes 17

6 Cyclic Alkanes (Naphthenes) 19

7 Aromatic Compounds 24

8 Prediction of the Minimum Autoignition Temperature (MIT)

a) Background 26 b) Autoignition temperature (AIT) predicted from comprehensive schemes

for a range of alkanes 27

c) Prediction of AIT using reduced kinetic models 32

9 Discussion and Conclusions

a) Relationships between redundant species identified in the comprehensive schemes

33

b) Redundant reactions patterns 36 c) Quasi steady state species 36 d) Summary of the scale of reduction of kinetic mechanisms and the gain in

speed-up of computation 37

e) The status of chemical computation with CFD analyses, with reference to AIT prediction.

38

10 References 39

11 Publications and Conference Presentations 40

12 Appendices

a) Propane oxidation reduced to 42 species in 166 reactions 42 b) N-butane oxidation reduced to 74 species in 300 reactions 45 c) Cyclohexane oxidation reduced to 47-100 species in 157-238 reactions 52 d) Classes of reactions removed from cyclohexane and n-butane schemes 60

2

1. Introduction This report constitutes the background and commentary on Deliverable 38 as a contribution to WP 5 “Reduction Methods and Validation”. The purpose of Deliverable 38 is to provide reduced kinetic models for different classes of hydrocarbons that may be used for the prediction of autoignition hazards. The models have been derived using the methodology discussed in Deliverable 37, “Kinetic reduction software: report on reduction techniques”. The numerical programs can be accessed from the SAFEKINEX website (www.safekinex.org). In this report we describe the models appropriate to each of the classes considered and what is achieved in terms of the extent of reduction that is possible from the comprehensive schemes derived using the automatic generation methods of EXGAS (Deliverables 35 and 36) and the speed-up in computation that can be achieved. Results illustrating the application of the reduced schemes are also presented here and representative reduced schemes are given in Appendices. The classes of compounds that have been considered are C1 – C3 hydrocarbons, alkanes from C4 – C10, cyclic alkanes (naphthenes), alkenes and aromatic compounds. The development and performance of comprehensive kinetic models for these classes of compounds were part of WP3 and are reported in the preliminary Deliverables 26 – 28 and the final Deliverables 34 – 36. In Deliverable 38 we refer to a comprehensive kinetic scheme as one that contains all of the kinetic information that is available to represent the behaviour of a particular substance over specified ranges of conditions. For the present purpose, each of these schemes will have been generated by use of EXGAS. A mechanism that has then undergone some manipulation to reduce its complexity is generally referred to as a reduced scheme. A limiting condition for this reduction procedure, creating a kinetic model that has been reduced only by removal of redundant species and reactions and cannot be reduced further without losing the kinetic form of the mechanism (that is, it is the shortest form of the reaction scheme that can be achieved whilst still retaining the format of the original elementary reactions) is called a “skeleton scheme”. As noted below (Section 2c) and illustrated in Sections 4 and 6, quite considerable further reductions of the skeleton scheme can be achieved, but it is at the expense of the explicit mechanistic structure represented by elementary reactions. We might recognise the anatomical connection of reducing the comprehensive scheme to its “bare bones” to generate the skeleton scheme, but with all of its main connections intact. Unfortunately, there is no analogous anatomical state to correspond to that which constitutes the “lumping” of species and reaction parameters in subsequent stages.

2. Summary of Reduction Methods a) Background Except in the simplest, idealised scenarios, the need for reduction of comprehensive kinetic models that are applied to combustion problems and hazards arises because the detail and complexity of the models (incorporating hundreds of chemical species and thousands of reactions) makes their computational application too inefficient, or even not viable when the complementary physical processes such as heat and mass transfer or gas motion are also embodied in the simulations.

In order to bring about reduction in the numbers of reaction species and reactions, without losing the quantitative capability to predict the required information about the combustion system or chemical process, it is necessary to exploit formal mathematical methods and,

3

where practicable, to incorporate them in automated numerical programs in a format that is widely applicable. The format in which we have set up the programs includes thermodynamic data in the form of 14 NASA polynomial coefficients for each chemical species and a list of reactions and associated Arrhenius parameters. The mechanisms are in a standard CHEMKIN [1] format (see Deliverable 37).

The focus of Work Package 5 is on the behaviour of the chemical models. Consequently, because the starting point for mechanism reduction is kinetically complex, the developments themselves have been made within the idealised context of a spatially uniform chemical reactor. This enables gas motion, either intentionally induced or arising from natural convection in practical circumstances, to be disregarded and for heat transport from the system to be characterised by a Newtonian heat transfer coefficient. The implications of such simplifications (which do not themselves impinge on Work package 5) are discussed in Deliverable 18.

Nevertheless, an example to illustrate the application and use of the reduced model in a more complex physical environment involving heat and mass transport by diffusion, which requires a spatio-temporal computation in at least one dimension, is also included here. This example, pertaining to the spontaneous combustion and ignition of propane [2], highlighted some of the potential limitations in the fundamental data that are incorporated in comprehensive mechanisms themselves (regardless of their scientific origin). Moreover, through this particular example, by application of new methods for “uncertainty analysis” we have been able to inform the combustion community the extent to which discrepancies may exist in the assigned data. One publication [3], in the journal “Physical Chemistry Chemical Physics”, was announced as a “hot topic” in June 2006 by the Royal Society of Chemistry for its timeliness and importance (http://www.rsc.org/Publishing/Journals/CP/Hotindex.asp). Subsequently the same methods were applied by us to another topical area for potential combustion hazards involving carbon monoxide and hydrogen mixtures [4]. b) Sensitivity-based reduction procedures for kinetic models

The foundation for kinetic model reduction used here is “local sensitivity analysis”, which embodies a series of stages. The purpose is to reduce the numbers of species and reactions of the mechanism while retaining the desired quantitative output from the model. In sensitivity analysis, the effect of making small changes in parameters or variables on the magnitude of other variables of the system is investigated, for example as the effect of small changes of concentration of each species on rates of product generation. The effect of perturbations applied to each variable can be quantified and ranked in importance, such that thresholds can then be applied to decide which species (or reactions) can be retained and which can be discarded [5]. The conventional procedure is first to identify redundant species via investigation of the Jacobian matrix. Subsequently, reactions can be removed using either the overall sensitivity of production rates of necessary species to changes in rate parameters using a least squares objective function, or through principal component analysis of the rate sensitivity matrix [6].

There is a range of chemical kinetic based software available to aid the chemist or engineer. The most common of these are based on the CHEMKIN family of numerical codes [1] which are used worldwide in combustion modelling and have had a large impact on the research community by providing a common framework for communicating work via a “CHEMKIN format” [7]. The KINAL [8, 9] or KINALC [6, 10] packages, the latter of which

4

uses the CHEMKIN format, are examples for the application of sensitivity methods and have been used in WP5. Just as the manual construction of comprehensive mechanisms is laborious and prone to error, and has been circumvented by the development and application of EXGAS (WP3, Deliverable 35), so the reduction of schemes in an intensive interactive way is both laborious, prone to potential error and requires a detailed understanding of the principles involved. Thus the reliability of the results, and the scope of application are enhanced, and many man hours saved by the use of automatic reduction software. The codes are based on the use of UNIX shell scripts to completely automate the utilisation of numerical integration and local sensitivity analysis software in a CHEMKIN format as described in Deliverable 37. The main requirement of the user is the definition of sensitivity thresholds which define the eventual size and resulting accuracy of the reduced schemes. The software has been designed to allow the user to specify several thresholds so that schemes of varying size can be easily developed depending on the required accuracy of the final application.

The reduced mechanisms must be validated at the various stages of reduction and this is done through comparison to output predictions obtained from the comprehensive mechanism. With regard to the prediction of autoignition temperature (AIT), as a primary goal of SAFEKINEX, comparisons were made between the predicted temperature - time profiles at specified initial and boundary conditions and also the automatically generated ignition diagram, which shows the conditions within which a range of complex modes of combustion phenomena occur (see Deliverable 37). The precision with which quantitative agreement between the reduced and full models is established becomes a determinant of the extent of the reduction that can be achieved. This is controlled by tests at different thresholds. The overall target becomes a balance between computational efficiency and accuracy of reproduction of the output of the model. Within this environment, models retain mass balance and compatibility with any CHEMKIN based software. The computational time taken to obtain a numerical solution from a mechanism of given size is typically ∝ N2, where N is the number of species, or n, where n is the number of reactions. Therefore large computational savings can be made, especially when the number of species is reduced, as noted later.

∝

c) Timescale-based reduction procedures for kinetic models

Further reduction may be achieved by the exploitation of the range of time scales present

in the system via the application of the Quasi Steady State Approximation (QSSA) combined with reaction lumping [11, 12]. The QSSA method is employed in mechanism reduction to identify species which react on a very short time scale and locally equilibrate with respect to species whose concentrations vary on a slower timescale. These fast reacting species are known as quasi-steady state (QSS) species and their removal can reduce the stiffness of the resulting reduced models. The main assumption of the QSSA is that the equilibration of the QSS species is instantaneous. The concentration of the QSSA species can then be determined (to good approximation) from a local algebraic expression rather than a differential equation. The algebraic expression is derived by setting the QSS species rate of production to zero.

Previous applications of the QSSA to complex kinetic schemes have tended to employ

iterative methods to solve the algebraic expressions for the concentrations of coupled QSS species. Although this results in a reduction in the number of differential equations that need to be solved, additional computational effort is required to solve for the QSS species, which limits the speed-ups that can be achieved. Substantial computational savings can be made

5

when the QSS species is removed via reaction lumping [11, 12]. In its simplest form a reaction scheme or subset consists of a set of reactions from reactants going to intermediates, or a coupled set of intermediates that are QSS species, which then form products. Via reaction lumping, this set of reactions is changed to a single reaction involving only reactants going to products. QSS species intermediates are therefore eliminated. The rate constants of the lumped reactions will be algebraic combinations of the rate parameters of the original reactions and, in many cases, also intermediate species concentrations and are derived subsequent to the application of QSSA. This is illustrated in the following, where B is a QSS species linking the reactant A to the product C.

k1

k-1

k2A B C (1)

When the QSSA is applied,

0][B=

d

that

(2)dt

so

][][21

1 Akk

kB+

=−

(3)

ence H

21

212

][][][kkAkkBkd

dtC

=+

=−

(4)

where

21 kk +−

21' kk= (5)

Therefore the above set of reactions can be replaced by a single reaction of the form

wit

edure, as shown in the examples below. If the concentrations of any of tablished, they can be regenerated using the appropriate

k

A → C

(6)

h the effective rate coefficient, k’, as defined. The quantitative kinetic involvement of the

intermediate species B in the overall reaction is encapsulated in k’.

Although it may then be possible to parameterise the k’ terms with a conventional Arrhenius type expression, this is not generally the case, and therefore the resulting scheme no longer complies with traditional CHEMKIN formulations. However, mass balance is retained in the scheme and simple subroutines describing the chemical rate equations can be automatically developed. The savings, in terms of the number of species eliminated, make this a worthwhile procthe QSS species need to be es

6

alg

dentify those which play the most important part and to rank the order of their significance. This procedure is classified as “uncertainty an nd is illustrated in Section 3b

ith reference to the performance of a reduced model for propane combustion.

1 3

000 K (Deliverable 35). Kinetic parameters were btained from literature values or derived

ebraic expressions, although usually only the major products and temperature are required from the simulation.

The versatility of the automated reduction codes and their application to different

classifications of fuels is illustrated next, and considerably reduced chemical models which can be used in higher dimensional simulations are obtained as output (see Appendices). Application of the QSSA to the reduced mechanisms is also shown, making substantial computational savings whilst incurring very little error in the kinetic model performance. The removal of redundant species and reactions provides the potential for further exploitation of the reduced schemes to investigate the consequences of uncertainty in parameter values. Such tests are important because quantitative discrepancies between model predictions and experimental results may be attributed to incorrectly assigned parameter values. Not all parameters control the response of the system equally, so it is important to i

alysis”, as noted in Section 2a, aw

3. C – C Hydrocarbons

a) Reduced models for propane derived in zero-dimensional simulations

The predicted behaviour of the smallest hydrocarbon molecules is illustrated here with respect to propane. The starting point was the comprehensive model for propane combustion, developed at CNRS-DCPR, Nancy, comprising 122 species in 1137 irreversible reactions and validated elsewhere over the temperature range 600 – 2

ousing additivity rules [13, 14]. The thermochemistry, equilibrium constants and hence the reverse reaction rate coefficients were derived from NASA polynomial functions.

500 520 540 560 580 600 620 6400

20

40

120

60

80

100

Slow reaction

Pre

Ta/K

1 cool flame

Multiplecool flames

2 stage ignitionssur

e/kP

a

4 stage3 stage

5+

igure 1. Full Nancy scheme simulated p-Ta ignition diagram for equimolar C3H8 + O2 in a closed

vessel under spatially uniform conditions. This, and other, C3H8 ignition diagrams were computed at 2K intervals using an automatic generation procedure, giving precision of the boundary to +

F

70 Pa (+ 0.5 torr). Black squares denote the user selected operating conditions for model reduction.

7

The model, in a CHEMKIN format, was tested for its ability to predict cool flame and ignition phenomena under spatially uniform, closed vessel conditions over the vessel temperature range 500 – 650 K at sub atmospheric pressures. All of the qualitative structure of the ignition diagram, including the complex multiple-stage ignition phenomena, was recovered [15], as shown in Fig. 1. As outlined above, the reduction of this comprehensive kinetic model was performed by a combination of local Jacobian analysis for the reduction of species, followed by the use of rate sensitivities for the reduction of reactions as available in KINALC, subject to the improvements made within this project and described in Deliverable 37. The variation in performance of the resulting reduced schemes comprising 63 down to 41 species is shown in Figure 2 as a function of the predicted temperature – time record for two-stage ignition of equimolar propane + oxygen in a closed vessel at 620 K and a total pressure of 85.3 kPa.

1.0 1.2 1.4 1.6

600

800

1000

(a)(b) (c)

1200

1400

T/K

t/s

Figure 2. Illustration of the predicted 2-stage ignition of an equimolar propane +oxygen mixture at 620 K and 85.3 kPa. When the full scheme (solid line) is reduced to a 63 necessary species scheme (circles) the agreement with the full scheme is nearly perfect. The other simulations relate to reduced models, as discussed below.

As can be seen in Figure 2, even reducing the number of species in the kinetic model to 50% maintains an excellent quantitative agreement with the performance of the comprehensive scheme. Further reductions begin to introduce quantitative discrepancies in the time dependence, and in a complex way. Two species removal strategies were tested. In the first, a single set of thresholds were applied with increasing tolerances producing smaller and smaller schemes. In the second approach, a two stage reduction was attempted. The first stage reduction to 63 species was achieved with excellent agreement, as shown in Figure 2. Further species removal at this stage by relaxing the tolerances results in a 62 species scheme (Fig. 2 curve a) whose output has incurred significant error when compared to the full cheme. Alternatively a second stage reduction is performed with the 63 necessary species s

scheme as the starting point, to produce schemes of 42 species (Fig. 2 curve b) and 41 species (Fig. 2 curve c). The agreement of the 42 species scheme is deemed acceptable but in the case of the 41 species scheme it is deemed unacceptable. That the performance of a 62 species model (Fig.2, curve a) appears to be inferior to that of the 42 (Fig. 2, curve b) species model

8

arises because the application of a two stage reduction strategy leads to slightly different couplings of the species at different reduction stages. In the single stage reduction, further species removal at each stage using relaxed tolerances resulted in poorer quality reduced mechanisms, this being reflected in the temperature profiles and also in the ignition diagrams. The need to perform a second stage reduction arises because, during the iterative Jacobian analysis, redundant species can be incorporated into the reduced mechanism before all necessary species have been incorporated. These incorporated redundant species can be more easily removed by performing a second stage reduction due to the altered couplings. The need for a two-stage reduction strategy is not unique to Jacobian analyses. It has also been used by other researchers in the reduction methods of direct relation graphs [16]. Nevertheless some deviation from the prediction of the comprehensive scheme may be acceptable in the interests of more efficient computation without significant loss of precision in the prediction. In the present example (Fig. 2, curve c), the reduction to 41 species in the model has affected the maximum temperature reached in the second stage of

ove

two stage ignition. This would not be of particular concern when the purpose is solely to predict the occurrence of ignition or its time dependence. The abscissa of Figure 2 is scaled to highlight the discrepancy, but the (important) elimination of over 60% of the original species from the comprehensive kinetic scheme has lengthened the predicted

rall ignition delay by only 10%. The time to the occurrence of the first stage of ignition, and the temperature reached in it has not been affected by the model reduction. Consequently, if the interest was solely in a prediction to avoid the possible onset of two-stage ignition (that is, via the cool flame stage) and the time at which this is attained, it might be possible to gain further, significant, kinetic model reductions. As discussed in later Sections, further reductions in the propane model applied to autoignition, could certainly be attained by application of QSSA. The success of the reduced scheme for propane combustion comprising 42 species involved in 545 irreversible reactions, as measured with respect to the predicted p- Ta ignition diagram from the full scheme, is shown in Figure 3.

500 520 540 560 580 600 620 6400

20

40

60

80

100

120

Pres

sure

/k

Ta/K

2 stage ignition

Slow reaction

Multiple stage ignitionsand cool flames

Figure 3. Comparison of the p – Ta ignition diagrams produced by species reduced mechanisms for equimolar propane +oxygen. Solid line: full mechanism, 122 species and irreversible 1137 reactions. Dashed line: reduced mechanism, 42 species and 545 irreversible reactions. Dotted line: further species reduced mechanism, 41 species and 507 reactions.

Pa

9

Having identified the subset of necessary species, principle component analysis (PCA) of the rate sensitivity matrix was then applied to the partially reduced mechanism in order reduce the numbers of reactions in the scheme whilst retaining a good agreement with the output of the full scheme. Smaller subsets of necessary species, specific to each time point, found from local Jacobian analysis were used in the objective function of the sensitivity measure. This method has been found to achieve a better reduction than the conventional alternative of using the combined list of necessary species in the objective function. The combined list is collated from all time points considered for sensitivity analysis and is used to directly construct the reduced mechanism (see deliverable 37 for further details). The investigation of a variety of thresholds yielded a mechanism consisting of 42 species and 166 irreversible reactions which gave the best trade off between minimum number of variables and good agreement with the output from the full mechanism. Altered thresholds for the PCA tolerances resulted in further reaction removal down to 42 species and 145 irreversible reactions. However, the error induced by the removal of these extra 21 reactions (see Figure 4) over the range of operating conditions was deemed to be unacceptable when the limited computational speed-up achieved was taken into account.

500 520 540 560 580 600 620 6400

20

40

60

80

100

120

Pres

sure

/kPa

Ta/K

2 stage ignition

Slow reaction

Multiple stage ignitionsand cool flames

Figure 4. Comparison of the p-Ta ignition diagrams produced by reaction reduced mechanisms equimolar propane +oxygen. Solid line: Species reduced mechanism, 42 species and 545 reactions. Dashed line: PCA reaction reduced mechanism, 42 species and 166 reactions. Dotted line: further PCA reaction reduced mechanism, 41 species and 145 reactions.

The p-Ta diagram of skeleton mechanism consisting of 42 necessary species and 166

irreversible reactions shown in Figure 4 displays all the types of dynamic behaviour exhibited by the full system. Quantitatively, the agreement with the full scheme is excellent over the range of operating conditions, with only very minor differences. The agreement between the

w temperature ignition boundaries produced by the full and final reduced mechanisms is nearly perfect. Good agreement can also be found between the temperature profiles of the full and final reduced schemes. After species reduction to 42 species and 545 reactions, the computational time for a single zero-dimensional calculation is faster and is 37% that of the full scheme. The final reduced scheme has a 15% run time compared to that of the full kinetic model. It is known that the run time of the reduced scheme should be N2, where N is the number of species. So our calculated run time compares well to the estimated run time of 12% of the full mechanism.

lo

∝

10

b) Application to and further development from one-dimensional simulations As part of the present study, relating to a system involving heat and mass diffusion in a one-dimensional calculation, some additional quantitative changes were then made within the comprehensive mechanism in order to incorporate both modified rate parameters and reaction paths for oxidation reactions involving n-C3H7, i-C3H7 and C2H5, calculated using a master equation model by DeSain et al [17], leading to a final model of 122 species and 765 reversible reactions. These data relate to all of the reaction channels in which the respective alkylperoxy and hydroperoxyalkyl radicals are involved, leading to OH, HO2, oxygenated molecular intermediates and alkenes. The kinetic data, as presented by DeSain et al [17], do have a constraint in that the pressure dependence was reported through tabulations restricted to the three pressures of 30 and 760 torr, and 10 atm, the 760 torr data set being implemented here. However, these data are appropriate for application to the simulation of minimum ignition temperature (MIT), as discussed in Section 8. Additionally, slight adjustments to the heats of formation of seven alkylperoxy and alkylhydroperoxy radicals (appropriate to the DeSain et al data [17]) were made to give a consistent set of parameters throughout the entire scheme. The performance of this model was tested when heat and mass transport occur solely by diffusion, involving a one-dimensional simulation [2]. This physical environment is established in microgravity and avoids the uncertainty associated with the need to assume an idealised heat transport process.

0 4 8 12 16 200

20

40

60

80

100

p/kP

a

t/s

Figure 5. Simulated pressure time records (solid lines) respectively at 20, 25, 30 and 35 kPa initial pressures for an equimolar propane + oxygen mixture under zero gravity, and experimental pressure time records (dashed lines) respectively at pressures of 51.6, 64.2 and 78.6 kPa at 593 K under microgravity [2]. These conditions confer a sound foundation for a quantitative comparison with appropriate experimental measurements, as shown in Figure 5 in terms of pressure – time profiles at different initial pressures. The significance of these results is that, in order to reproduce similar ignition delay and times to the cool flame as those measured experimentally, it was necessary to reduce the initial pressure for the simulations. There

11

is an inescapable conclusion that there is a greater reactivity of predicted behaviour with respect to reactant concentration (or pressure) than that found experimentally, which is reflected in the quantitative comparison of the predicted ignition boundary of Figure 1 with that found experimentally [15], and illustrated in Figure 6. From supplementary tests, the temperature dependence that is built into the parameters of the kinetic model seems to be satisfactory. For this reason it was deemed necessary to explore uncertainties in the magnitudes of assigned parameters, with particular reference to thermochemistry of intermediate species.

70

80

90

520 540 560 580 6000

10

20

30

40

50

60

Pre

ssur

e/kP

a

T/K

Figure 6. Experimental [PCCP 4] and modeled 2-stage ignition and cool flame boundaries for a 1:1 C3H8:O2 mixture in a reaction volume of 300 cm3. The simulated heat loss rate was 2 mW cm-3 K-1, which corresponds to a heat transfer coefficient of 28 W m-2 K-1. _____ Experimental 2-stage ignition boundary. ------- Experimental cool flame boundary. -.-.-.-.- Simulated 2-stage ignition boundary. ……… Simulated cool flame boundary

An example of uncertainty analysis using the Morris one-at-a-time method [18] is illustrated in Figure 7. These results reveal the most important species of the reduced model the thermochemistry of which controls the time to the first stage of two-stage ignition, the

influence and the species can be ranked in terms of their er of importance. The standard deviation expresses the nonlinearity of the output response

r these species is embodied in the results of the Morris analysis as the standard deviation, but the extent to which changes in the parameters will affect the output has to be tested using Monte Carlo methods. The results of these analyses are discussed fully elsewhere [3], but we should note that the changes that are necessary for certain thermochemical parameters in order to improve the quantitative performance of the kinetic models do not fall outside the errors that would be assigned to those parameter values on the basis of current knowledge. In summary, there has to be an on-going investigation and refinement of (potentially quite limited numbers of) parameter values used in comprehensive and reduced models in order to improve the quantitative prediction of combustion behaviour. It is also important to note that

temperature reached in the first stage and the time of evolution from the first to the second stage. Those species with the highest absolute mean perturbations to each output can be interpreted as having the highestordwith respect to perturbations in the parameters. t is conspicuous that the thermochemistry of the same few species predominates in the determination of these three very important

eters. The extent of interactions between the variation of individual heats of formation

I

paramfo

12

the application of the quantitative approaches to uncertainty analysis requires the development and use of reduced schemes in order for the techniques to be computationally viable.

5

10

15

20

25

30

00 2 4 6 8 10 12 14 16

Sta

ndar

d D

evia

tion

τ absolute mean perturbation/s

O2OOH

1

n-C3H7O2

i-C3H7O2

. OOH

Figure 7a. Morris analysis for the species heats of formation with respect to time to the first stage of two

60

stage ignition, τ1. Specified variations are made in the magnitude of ∆Hof for each species.

70

80

90

100

0 5 10 15 200

10

20

30

40

50

n

O2OOH

Stan

iatio

τ2 absolute mean perturbation/s

C2H5O2

n-C3H

7O

2

dard

Dev

i-C3H7O2

Figure 7b. Morris analysis for the species heats of formation with respect to time to the second stage of two-stage ignition, τ2. Specified variations are made in the magnitude of ∆Ho

f for each species. .

13

0 20 40 60 80 100 120 140 1600

5

10

15

20

25

30

35

40

45

50

55

60

Sda

rd D

evia

tion

O2OOH

tan

T1 absolute mean perturbation/K

OOH.

C2H5OOH

n-C3H7O2

C4 – C10 Alkanes

Section 2b and illustrated in Section ensive scheme included 358 species in 2411 irreversible reactions.

he re mprehensive model to its skeleton form comprised 218 necessary

C2H5O2i-C3H7O2

Figure 7c. Morris analysis for the species heats of formation with respect to temperature reached in the first stage of two-stage ignition, T1. Specified variations are made in the magnitude of ∆Ho

f for each species.

4.

Here we show that such methods can be successfully applied to highly complex reaction sequences such as those occurring in alkane combustion. An EXGAS generated n-heptane scheme was simplified by the reduction procedures outlined in

3. The comprehduction of this coT

species in 810 reactions. This scheme gave an excellent quantitative match to that from the comprehensive mechanism, when the overall ignition delay was computed as a function of reaction vessel temperature, for an n-heptane + air mixture at φ = 0.65, as shown in Figure 8.

1200

0 1 4.8 5.0 5.2 5.4 5.6500

600

700

800

900

1000

1100

T/K

t/s

Figure 8. Typical temperature profiles calculated from the comprehensive (358 species in 2411 reactions - solid line) and skeleton (218 necessary species in 810 reactions) - dashed line) n-heptane reaction mechanisms (Ta = 550 K, p = 173.3 kPa (1.711 atm).

14

15

Over 100 QSS species can be identified amongst the 218 necessary species of the skeleton

scheme but many of them are involved in highly coupled reaction sequences. One example is the reaction mechanism of the symmetrical heptylperoxy isomer as illustrated in Figure 9, which proceeds via a set of connected QSS species to 13 different product channels.

ents involving the QSS species in Figure 9.

a e replaced with a direct reaction of C7H15OO to product w

pecies have been removed and replaced by direct reaction of C7H15OO to each of the 13 product channels.

C7H15OOO2

Q1OOH Q2OOH Q3OOHQ4OOH

O2Q1OOH O2Q4OOH O2Q2OOH O2Q3OOH

2 productchannels

2 productchannels

4 productchannels

4 productchannels

OH + C7H14O3

C7H15OOO2O2

Q1OOH Q2OOH Q3OOHQ4OOH

O2Q1OOH O2Q4OOH O2Q2OOH O2Q3OOH

2 productchannels

2 productchannels

4 productchannels

4 productchannels

OH + C7H14O3

Figure 9. Reactions of the symmetrical heptylperoxy isomer via a set of connected QSS species to products.

Here, all of the Q’OOH and O2Q’OOH species are QSSA candidates, but it is not a straightforward matter to remove them via reaction lumping, as the set of simultaneous algebraic equations defining the concentrations of the connected QSS species obtained from such a complex set of interactions are too intractable to easily be solved manually. However, by the use of an algebraic equation manipulation package such as MAPLE to solve the set of simultaneous equations resulting from the application of the QSSA, this problem can be overcome. The solutions produced by MAPLE are of the form:

[Q1OOH] = f1(k) [C7H15OO]

(7)

Similar relationships exist for Q2OOH etc., where f1(k), f2(k) etc. are complicated functions of all of the individual rate coeffici

decompositionproductsdecompositionproducts

Thus, if there is a reaction leading to a product species, such as: Q1OOH → A

(8)

ith a rate coefficient k , then it can bwA ith an effective rate coefficient given by the product ka f1(k). A similar procedure can be performed for all 13 individual product channels in Figure 9 to give a final mechanism in

hich all of the QSS species in Figure 9 along with the individual reactions involving these ws

By systematically applying this procedure to most of the identified QSS species, more than half of the species in the skeleton n-heptane scheme can be removed, with a minimal effect on the temperature profile, as illustrated in Figure 10. Not all QSS species have been removed, the simplest QSS species, principally small radicals such as H, O, OH etc. are involved in so many reactions that even with the use of MAPLE, their removal is not practical. As noted previously, such a scheme is no longer compatible with standard CHEMKIN codes due to the need to compute the complex f(k) expressions that cannot necessarily be parameterised using the standard functional forms available within CHEMKIN.

900

1000

1100

1200

700

800

500

600

0 1 4.8 5.0 5.2 5.4 5.6

T/K

n 2b can be re-applied to identify yet more redundant species and reactions, reducing the scheme to 110

en removed, and hence exist only as reaction products. Nevertheless these species cannot be removed because the reactions that produce them are important with respect to prediction of the temperature and/or other important species. However, a further approximation can be made by amalgamating these product species into a single “dummy” product. We have assigned the thermodynamic properties of carbon dioxide to the dummy product since, amongst these product-only species, CO2 is present in the highest concentration. This produces a scheme of 81 necessary species and 452 reactions which, in addition to the incompatibility with CHEMKIN introduced by the QSSA rate coefficient expressions, strict mass balance and an accurate heat release calculation are no longer preserved. However in practice, this does not prevent the mechanism producing an excellent reproduction of the temperature profile, as illustrated in Figure 11.

t/s

Figure 10. Comparison of the typical temperature profile to that from the full (358 species in 2411 reactions – solid line) and skeleton (218 necessary species in 810 reactions – dashed line) mechanisms calculated from the reduced scheme generated after applying the QSSA (117 species in 571 reactions – dotted line).

Yet further reductions in the mechanism obtained after application of the QSSA are possible. As the structure of the scheme is now radically different from the starting comprehensive scheme and also the skeleton scheme, then the methods of Sectio

species and 452 reactions while still retaining excellent agreement. In addition, the issue of species that are now only present as products can be addressed. This arises because in the residual scheme there are a number of species the consuming reactions of which have be

16

0 1 4.8 5.0 5.2 5.4 5.6500

600

700

800

900

1000

1100

1200

T/K

t/s

Figure 11. Comparison of typical temperature profiles produced by all the n-heptane schemes, full –

The computed ignition diagrams from the comprehensive, skeleton, and minimal scheme of 8

358 species in 2411 reactions (solid line), skeleton – 218 necessary species in 810 reactions (dashed line), QSSA – 117 species in 571 reactions (dotted line), and reduced QSSA scheme – 81 necessary species in 452 reactions (dash-dot line).

1 necessary species in 452 reactions, are shown in Figure 12.

140

160

180

200

220

500 550 600 650 700 750 800 8500

20

40

60

80

100

Ignition

120

Slowreaction

Cool flames

P/k

Pa

T/K

Figure 12. Complete ignition diagram produced by the comprehensive (358 species in 2411 reactions – solid line), skeleton (218 necessary species in 810 reactions – dashed line), and reduced QSSA scheme (81 necessary species in 452 reactions – dash-dot line).

5. Alkenes

reversible and irreversible reactions (6437 reversible reactions). The chiometric 1-hexene/air

mixture is shown in Figure dicted ignition diagram

A comprehensive scheme for 1-hexene was developed by the research group at Nancy,

consisting of 1128 species and 5005 mixed ir ignition diagram generated for a stoi

13 and, with it for comparison, is a pre

17

from a skeleton reduced scheme of 816 species in 2520 irreversible reactions. This shows an excellent agreement between the full and skeleton scheme at this extent of reduction.

120

140

160

180

200

220

500 550 600 650 700 750 800 8500

20

40

60

80

100

P/k

T/K

Cool flames

Slow reaction

Figure 13. Comparison of predicted ignit

P

ion diagrams from comprehensive (solid line), and Skeleton (dashed line) 1-hexene schemes. The square symbols denote the sets of initial conditions of temperature and pressure for which the mechanism reduction procedure was performed.

However, there are still a large number of species and reactions in this skeleton scheme, and very little further progress can be made by the conventional methods of species and reaction removal before the agreement between comprehensive and reduced schemes breaks down.

a

Ignition

20

40

60

500 550 600 650 700 750 800 8500

80

100

120

140

160

180

200

220

P/k

Pa

T/K

Ignition

Cool flames

Slow reaction

Figure 14. Comparison of ignition diagrams from the comprehensive (solid line) and species-reduced skeleton scheme (dashed line) when only conditions close to the low temperature boundary were chosen to perform the reduction. The square symbols denote the initial conditions chosen for the reduction in this instance.

By concentrating solely on reduction conditions near the low temperature ignition boundary, in a similar manner to that discussed in Section 6 with respect to cyclohexane, an improved reduction could be obtained that would still reproduce this low temperature boundary, but deviate in other regions of the ignition diagram. This is illustrated in Figure 14,

18

in which the species and reaction reduction was performed only at the two points indicated close to the low temperature ignition boundary. The resultant skeleton scheme comprised 617 species in 2604 reactions, the higher number of reactions than that involved in Figure 13 arising from the adoption of different reduction thresholds.

QSS candidate species were also identified in the skeleton 1-hexene mechanism, as discussed in previous and subsequent Sections. Although these QSS species have not been removed by analytical methods from the mechanism, it is possible to adjust the numerical integration code to force their time derivative to be zero in order to simulate the effect of actually applying the QSSA to these species. The predicted temperature profiles are shown in Figure 15, obtained from simulations at conditions corresponding to those marked in Figure 14. The temperature profile from the skeleton scheme is compared against profiles obtained with 2 levels of approximation (a 10 or 15% threshold of instantaneous QSSA error) in identifying the QSSA species. These show that, in principle, over 350 of the 617 original species in the skeleton scheme could be removed with negligible consequences on the predicted behaviour. The presence of large numbers of intermediate QSS species is, perhaps, an indication that some lumping of the reaction mechanism at the generation stage might facilitate subsequent mechanism reduction.

0 1 2 3 4 29 30 31 32 33 34 35500

600

700

800

900

1000

1100

T/K

t/s

Figure 15. Comparison of a temperature profile prediction from the skeleton scheme of 617 species (solid line) against the predictions obtained by applying the QSSA to 345 (10% threshold, dashed line) or 376 (15% threshold, dotted line) of these species.

6. Cyclic Alkanes (Naphthenes)

The full cyclohexane mechanism generated by EXGAS comprises 499 species in 1025 reversible reactions and 1298 irreversible reactions (giving 2323 reactions equivalent to 3348 irreversible reactions in total). As in previous examples, the initial mechanism reduction was performed on the simulation of autoignition phenomena in the temperature range 500 – 800 K, with particular reference to the location of the p- Ta ignition boundary. Based on three

ure 17) with ommensurate accuracy in the time dependent response (Figure 18).

conditions in this ignition diagram (Figure 16), three stages of species reduction gave a skeleton scheme comprising 106 necessary species in 541 reversible and irreversible reactions which enabled a very accurate prediction of the ignition diagram (Figc

19

The reduction of the cyclohexane mechanism thus far retains excellent agreement with the low temperature ignition boundary generated with the full mechanism over the temperature range of 500 – 550 K. The comparisons of temperature profiles as output from all of the presented full and reduced mechanisms in this region of operating conditions also show excellent agreement. Therefore, further reductions were carried out in order to assess what is the minimum size of mechanism which will retain these characteristics. The resulting reduced mechanisms enable a quick calculation of AIT and are useful in evaluating the underlying kinetics driving the transition from slow reaction to 2-stage ignition behaviour when initial ambient conditions vary.

500 550 600 650 700 750 800

0

50

100

150

200

250

300

350

Pres

sure

/kPa

Ta/K

Figure 16. Simulated p-T

2 - stage ignition

SlowReaction

Cool flame

SlowReaction2 cf

6 12GAS scheme. The black squares are

e

a ignition diagram for stoichiometric c-C H + air in a closed vessel under patially uniform conditions derived from the comprehensive EXs

th user selected operating conditions for reduction of the scheme.

500 550 600 650 700 750 800

0

50

100

300

350

250

150

200

Pres

sure

/kP

2 - stage ignition

a

Ta/K

SlowReaction

SlowReaction

Cool flames

Figure 17. Comparison of the p-Ta ignition diagrams produced by the full and species reduced mechanisms for stoichiometric cyclohexane in air showing the full mechanism (solid line) and reduced mechanism comprising 106 species and 541 reactions (open circles).

20

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

600

800

1000

1200

1400

T/K

t/s

Figure 18. Comparison of the temperature profiles output from the full and species reduced cyclohexane mechanisms in a stoichiometric c-C6H12 + air mixture at 650 K and 175.4 kPa, symbols

further reductions. Two alternative operating conditions for nsitivity analysis were selected clo perature ignition boundary. The

objective of the reduction was to pro uced scheme which would retain the haracteristics of the low temperature ignition boundary and low temperature time dependent

beh io

ns. The number of reactions was successfully duced and this resulted in a mechanism

ies whose p-Ta ignition diagram gives reasonable agreement with that of the full mechanism, but whose calculated ignition delay times have incurred significant error. Both of these mechanisms are summarised in the Appendix.

as in Figure 17. The reduced mechanism comprising 106 necessary species and 541 reactions was used as

he starting point for thetse se to the low tem

duce a further redc

av ur produced using the full mechanism. The reduction proceeded by performing further multi-stage Jacobian analyses. This resulted in the creation of reduced mechanism comprising 59 necessary species in 290 reactions. Next, PCA methods were employed to remove reactions. Once again small subsets of necessary species were used in the objective function at each time point to which they are specific. The reactions of the 59 necessary species mechanism were converted to irreversible form and this resulted in 493 irreversible reactio

recomprising 59 necessary species and 238 irreversible reactions. This mechanism is shown schematically in Figure 21a, illustrating the major reaction pathways. The reduced mechanism was then validated by the construction of the p-Ta ignition diagram and by making a comparison with the same diagram generated with the full mechanism. The comparison of the p-Ta ignition diagrams produced by the full mechanism and reduced mechanism (Figure 19) shows excellent agreement between their low temperature ignition and cool flame/slow reaction boundaries, however significant error has been incurred above the temperature of 540 K to the ignition/cool flame boundary in the reduction. Further species and reaction removal using the sensitivity techniques alone results in a scheme comprising 48 necessary spec

21

500 520 540 560 580 6000

50

100

150

200

250

300

350

Pres

sure

/kPa

Ta/K

Cool flames

2-stage ignition

SlowReaction

Figure 19. Comparison of the p-Ta ignition diagrams produced by the full and mechanism C for toichiometric cyclohexane in air. Solid line: full mechanism, 499 species and 2323 reactions. Circles:

diction of the ignition iagram based on a mechanism with only 33 necessary species in 323 reactions (Figure 20).

sreduced mechanism comprising 59 species and 238 irreversible reactions, post PCAF.

The QSSA combined with reaction lumping was applied to the 59 necessary species mechanism to further eliminate a number of intermediate species whilst incurring little error to output ignition delay predictions. Thresholds were applied to the calculated instantaneous QSSA error for each species over all considered time points, thus providing an automatic way of identifying QSS species. These procedures gave a successful pred

350

500 520 540 560 580 600 6200

50

100

150

300

250

200

Pres

sure

/

Ta/K

Cool flames

2-stage ignition

SlowReaction

Figure 20. Comparison of the p-T

kPa

a ignition diagrams produced by the full mechanism and reaction lumped 35 species mechanism with product species lumped into 1 dummy species. Conditions are for stoichiometric cyclohexane + air mixture. Solid line; full mechanism. Open circles; QSSA reduced ec

am hanism comprising 33 species and 323 reactions.

This mechanism requires a dedicated integration code in order to solve the resulting new algebraic formulations for the lumped reaction rate parameters. The mechanism and code are

22

available in electronic form from the authors. The reduced QSSA mechanism is shown diagrammatically in two forms in Figure 21.

Ketohydroperoxides

CH2OCO

C2H4

CH2CO

OO

O

HOOHO

HOO HOO HOO

OHOO

OO

HOO

+O2

+O2+O2

O

OO

H

O

HOOH

O

H

OOH

O

H

OO

OOH

O

H

OOH

O

H

OOH

O

H

OOOOH

O

H OO

O

H

O

OOH

O

O

+O2

+O2

+O2

Figure 21a. Major fluxes of carbon atoms during simulated isothermal oxidation of cyclohexane in air using the 59 species 238 reactions mechanism. Conditions relate to the molar proportions 1:2, 470 K and 1 atm. Arrow thickness is scaled to magnitude of element flux.

23

Ketohydroperoxides

CH2OCO

C2H4

CH2CO

OO HOOHO

HOO

OO

HOO OO

O

H

O

OOH

O

O

+O2

+O2

+O2

+O2+O2

Figure 21b. Schematic of major carbon fluxes during isothermal oxidation of the QSSA reduced mechanism comprising 33 species and 323 reactions. Simulated at 470 K, 1 atm and cyclohexane + air in the molar proportions 1:2.

7. Aromatics

Comprehensive schemes for o-xylene (188 species, 1238 reversible and irreversible reactions), m-xylene (186 species, 1238 reversible and irreversible reactions), and p-xylene (190 species, 1236 reversible and irreversible reactions) were provided by Nancy. An ignition diagram generated for a stoichiometric o-xylene + air mixture is shown in Figure 22. The points indicated on the figure represent the initial conditions at which redundant species and reactions were identified in the construction of a reduced mechanism. An interesting,

200

250

820 840 860 880 900 920 940 960 980 10000

50

100

150

1

2

3 4

5

Pres

sure

/kPa

T/K

Figure 22. Predicted ignition diagram for o-xylene from the full mboundary; dashed line, cool flame boundary; dotte multiple cool flame boundar

echanism: solid line, ignition d line, y. Numbers

represent the initial conditions at which redundant species and reaction identification was performed.

24

periodic, non-isothermal phenomenon was predicted in the ignition diagram for o-xylene (Figure 22), which occurred at a high ambient temperature as typified by the temperature/time rofile simulated at point 3, and shown in Figure 23. This periodic behaviour is reminiscent

of th e/air mixtures. In this case, however, it is controlled by distinctly different kinetic processes than those which accounting for the behavio 7.

pe multiple cool flames that occur at much lower ambient temperatures in alkan

ur in alkanes, as discussed in Deliverables 45-4

940

950

960

970

980

0 1 2 3 20 21 22 23 24 25900

910

920

930

T/K

t/s

Figure 23. The predicted periodic behaviour for o-xylene at point 3 in Figure 22. Identification of the redundant species and reactions from investigation of points 1 to 5 (Figure 22) produced a reduced o-xylene mechanism of 129 species and 918 irreversible reactions. The comparison of the ignition diagrams produced from the full and reduced schemes is shown in Figure 24. In general there is excellent quantitative agreement, except for a small region of the ignition boundary around 910K that is not matched exactly. Very similar behaviour and ignition diagrams are predicted from the meta- and para-xylene mechanisms, except for the absence of a region of periodic behaviour.

50

100

150

200

250

820 8400

860 880 900 920 940 960 980 1000

1

25

3 4

Pre

ssur

e/kP

a

T/K

Figure 24. co me and the reduced schem

mparison of ortho-xylene/air ignition boundary calculated from the full schee of 129 species and 918 irreversible reactions.

25

8. Prediction of the Minimum Autoignition Temperature (MIT) a) Background

As has been set out in the discussion of expe easure ts (Deliverable 5, 29 and 31), in the links to the numerical prediction of AIT (Deliverable 18) and as summarised in Deliverable titative con ts on numecomplex flow fields that affect both heat and s transport in the existing standard procedures f um autoignition temperature ). Since open flasks are utilised in the current test procedures (IEC 60079-4, DIN 51794, ASTM 659-78, BS 4056 and EN 14522),

e loss fr ystem of reactant vapour in its partial mixture r is inevitable once elf heating leads to buoyancy and convection of the heated, lower density reactants. eg

ection, the variable rates of heat and mass transport induced by it, and the oupling of complex kinetics to these difficult simulations of the physics (see Deliverable 18).

the

herefore, even without a fully quantitative representation of the physics and fluid motion, it

is important to establish how successful are the kinetic schemes (both in full and reduced form) for the prediction of autoignition temperature, with particular reference to MIT. Since, at present, major approximations have to be incorporated into models to represent the physical process associated with the experimental measurement of MIT, which compromises the scope for a fully quantitative match, the main criterion for measuring the success of the kinetic models must be based on the relative positions and magnitudes of the predicted values for MIT over a range of compounds, rather than on their absolute values. This is the purpose of the present Section.

In order to dissociate the chemistry entirely from the physics of autoignition one might

presume to investigate the behaviour in adiabatic conditions. However, since adiabatic reaction means that ignition of a fuel + air mixture is inevitable, regardless of the reactor temperature, the criterion for the existence of an ignition limit (i.e. to determine an AIT) can be related only to a prescribed maximum ignition delay time. This criterion is used within current experimental procedures (IEC 60079-4 etc.), for which the limit is set at 300 s, and is viable in practice because the effect of heat loss coupled to heat release (as must occur in

) is to impose a parametric sensitivity on the combustion system which delineates nition from non-ignition in finite time. It cannot work satisfactorily for an idealised

adiabatic state.

rimental m men

45-47, there are major quan strain rical predictions set by the mas

or minim (MIT

soms

om the s with ai

R ardless of the degree of simplicity of the chemistry that might be built into numerical simulations, this eventuality is beyond the scope of prediction of MIT using any fluid mechanical models that exist today, at least in an acceptable or meaningful representation.

Even within a closed system, as has been used in SAFEKINEX and advocated for revisions of test procedures (Deliverable 5), difficulties for the quantitative numerical prediction of MIT are connected with the formulation and calculation of the flow field created by natural convcFurthermore, there is a need for predictions to e extended to cover applications at elevated pressures (with evaluation using the new and important data provided in Deliverable 5) which then require the fluid mechanical elements to be able to accommodate to the consequences of

b

variation in pressure and, through it, the Rayleigh number.

The “raison d’être” for setting up reduced models from the comprehensive kinetic schemes is that a viable combination of chemical kinetics with the physics of the processes involved can become computationally possible only when the chemical detail, and in

articular the number of species involved in it, is reduced to an acceptable minimum. pT

realityig

26

The consequence of setting a maximum ignition delay in a numerical simulation is

illustrated in Figure 25 with respect to the predicted AIT of n-heptane under adiabatic on

andc ditions. Ignition is predicted to occur on relatively short timescales in very rich mixtures

the predicted AIT falls as the proportion of fuel is reduced. The minimum in the curve at 17.5 mol% n-heptane, corresponding also to a discontinuity in the gradient as the mixture

6 9 12 15 18 21 24

480

500

520

540

T a / K

mol% n-heptane in air

ature (AIT) predicted from comprehensive schemes for a range of alkanes

As outlined in the Introduction and discussed in detail in Deliverable 18 the prediction of autoignition temperature for alkanes, based on comprehensive or skeleton kinetic schemes, necessitates the assumption of spatial uniformity of premixed fuel + air in a closed system. That is, no temperature or concentration gradients exist at any time throughout reaction and the rate of heat loss from the system is controlled by a surface heat transfer coefficient. This is the procedure that has been applied and reported here in a representative numerical investigation of AIT and MIT for the series of alkanes comprising propane, n-butane, n-pentane, n-hexane, n-heptane, the two isomers, 2,3-dimethylpentane and 2,2,3-trimethylbutane, and also for cyclohexane. The comprehensive kinetic schemes were generated from EXGAS, and reduced using the methods discussed and illustrated in Section 2 onwards and applied subsequently.

First, the dependence of AIT on composition was derived for each of the fuels, based on a criterion of “ignition” being characterised when the reactant temperature exceeded 1000 K at an “ignition delay” of less than 300 s. The temperature threshold may seem low, but in reality

AIT on composition, with the

Figure 25. Predicted AIT as a function of mol% n-heptane in air under adiabatic conditions. becomes less rich in fuel, does not represent the MIT but is a result of the intervention of the (assumed) 300 s ignition delay cut-off. This reductio ad absurdum is avoided when allowance is made for some heat loss using a Newtonian heat transfer coefficient, as discussed in Section 8b. b) Autoignition temper

it is unlikely to rise much higher than that in very rich mixtures. As shown in Figure 26, in each case there is a strong dependence of the predicted

27

minimum autoignition temperature (MIT) being established in very fuel rich mixtures. With the exception of cyclohexane, for which the most reactive mixture appears to be at φ = 4.80, the richest compositions in air at 1 atm falls in the range 7.40 < φ < 8.10 (Table 1). One might expect there to be a very similar sensitivity of isomeric structure to composition, but it appears that the MIT for 2,2,3-trimethylbutane occurs in a slightly richer mixture than that for its other isomeric structures, 2.3-dimethylpentane or n-heptane.

580

0 4 8 12 16 20 24 28 32500

cyclohexane

propane2.2.3-trimethyl butane

540

560

n-butanen-pentane

n-hexanen-heptane

2.3-dimethyl pentane

T a / K

520

mol% fuel in air

Figure 26. Variation of predicted AIT for a range of alkanes, derived from comprehensive kinetic models generated by EXGAS.

Table 1. Reactant compositions in stoichiometric fuel + air mixtures and in the mixtures at which the MIT is predicted. Composition at φ = 1 mol % reactant

(φ = 1) mol% reactant (+ 0.25) at MIT

φ (+ 0.15) at MIT

1.00 C3H8 + 5.00 O2 + 18.75 N2 3.73 27.5 7.40 1.00 C4H10 + 6.50 O2 + 24.45 N2 3.13 20.50 7.85 1.00 C5H12 + 8.00 O2 + 30.09 N2 2.55 17.50 8.10 1.00 C6H14 + 9.50 O2 + 35.73 N2 2.16 14.50 7.65 1.00 C7H16 + 11.00 O2 + 41.38 N2 1.87 13.25 7.90 1.00 C6H12 + 9.00 O2 + 33.84 N2 2.28 11.00 4.80

The origin of the fuel-rich basis for the MIT can be traced back to the temperature and

composition dependence of the rate of heat release in the range 600 – 750 K, as is illustrated for the oxidation of n-butane (Figure 27). The development of the overall negative temperature dependence of heat release rate is clearly evident, the kinetic origins of which are discussed in Deliverables 5 and 18. The heat release rates in this range of temperature are a very small fraction of those associated with “high temperature” flame chemistry. Moreover, the emphasis of higher reactivity in very rich mixtures at low temperatures also contrasts with the behaviour during flame propagation in air, for which the greatest reactivity is associated with compositions close to the stoichiometric mixture (φ = 1). A comparison between the

28

predicted and measured minimum ignition temperatures is given in Table 2 and shown graphically in Figure 28.

600 650 700 750 800 8500

250

500

750R

/ kW

m-3

φ = 9

φ = 6.5

φ = 1

Figure 27. The simulated rate of heat release in three mixtures containing n-butane in air increasing

the stoichiometric mixture at φ = 1 to a mixture in which fuel and oxygen are in equimolar roportion (φ = 6.5) and at φ = 9.

Table 2. Predicted and measured minimum ignition temperatures (MIT).

modification of the ASTM method by Scott et al [20].

fromp

Experimental data are taken from Jackson [19], as determined by a

Reactant Measured

MIT / K

Predicted

MIT / K C3H8 766 550 (728.5) 2,2,3-trimethylbutane (C7H16) 708 550 n-C4H10 705 514 2,3-dimethylpentane (C7H16) 610 532 n-C5H12 557 511.5 c-C6H12 543 511 n-C6H14 533 509.5 n-C7H16 520 507.5

The relationship between the measured values of the MIT for these fuels, as determined by chemical reactivity, is reflected qualitatively in the hierarchy of the predicted behaviour. However, there are quantitative discrepancies insofar that the sensitivity to structure is not captured so strongly by the predictions as is shown experimentally. There are three particularly conspicuous departures, related to propane, n-butane and 2,2,3-trimethylbutane. Each of these compounds exhibits an MIT exceeding 700 K, whereas the predictions fall at or below 550 K.

29

2 3 4 5 6 7 8500

600

700

800

cyclohexane

propane

n-pentan

n-butane

n-hexane heptane

2.2.3-trimethylbutan

2.3- thylpentane

T a / K

Number C atoms

en-

e

dime

of

( ).

Figure 28. Predicted (soli experime ally measured (open symbols) values of the MIT for a range of alkanes. The two values for the MIT that are predicted for propane are discussed below.

Although there is no comprehensive experimental information obtained at atmospheric

ressure to illustrate clearly how such an inconsistency can occur, it can be explained by refe

d symbols) and nt

prence to the p- Ta ignition diagrams obtained in a closed vessel for mixtures of n-hexane

and n-butane premixed with air at φ = 1, as shown in Figure 29 [21]. The broken lines shown in Figure 29, enclosing a region below each ignition boundary, defines the cool flame region.

Figure 29. Experimental ignition boundaries measured for stoichiometric mixtures butane in air, measured by Chamberlain and Townend [21] in a stainless steel cdm3). The ignition boundary is given by the solid line.

Ignition

Slow reaction

Cool flames

a b

c d

30

of n-hexane and n-losed vessel (0.19

Since the measurements shown in Figure 29 were made in compositions that are much leaner than the most reactive mixtures it is necessary to address the behaviour at elevated

ressures in order to interpret the trends in ignition behaviour. Thus, measurements of AIT at

ecause, whereas there is sufficient heat release from the “low temperature” hemistry of n-hexane at this pressu

activit to sustain auto perat tly autoignition can only be brought about as a result of chem iated with the interm mperature regime, and the AIT occurs in that tem . The cool flame behaviour of n-butane that can occur at 0.2 MPa would not be disvisual diagnosis employed in the fo ethods, and so wo recognized as an “igniti One furth al implication o s is that these feature gram wh to this demarcat autoignition at low or interm es cannot be recovered in a numcondit

Th ation is that this explanation for the marked distinction between n-hexane and n-butane reactivity at 0.2 MPa in their respective stoichiometric m es a feature of their combustion at atmospheric p Pa) in the mixtures at the MIT. There appear to tal results irm this interpretation, but it is well supported by the general trend to enha ctivity at lower pressures. This is illustrated in Figure 30 for propane + air, diagram for a p ean mixture at 2.5 m ) is overlaid on ewhat richer, t 7.5 mol% (φ = 2.00).

p0.3 MPa yield the temperatures of 530 (point a) and 590 K (point b) for n-hexane and n-butane respectively, both of which fall on the “low temperature” branch of the ignition boundary. By contrast, measurements of AIT at 0.2 MPa yield the respective temperatures of 550 K (point c) and 725 K (point d) for n-hexane and n-butane. This significantly larger

ifference arises bdc re for the AIT to be controlled by it, there is in

ignition in the low temsufficient

ure regime. Consequenistry assoc

y of n-butane

ediate te perature rangetinguishable using the

uld not be rmal test mon” phenomenon. er fundament f this analysis of the ignition dia

ediate temperaturich give rise ion between

erical analysis if adiabatic ions are assumed.

e implicixtures, becom

ressure (101.325 k very rich fuel + air be no experimen available to conf

nced combustion a where the ignition

remixed l ol% (φ = 0.67 one that is soma

Figure 30. Experimentally determined ignition and cool flame boundaries in a 0.19 dm3 stainless steel, spherical, closed vessel for mixtures of propane in air [22].

ue concerns the failure of the comprehensive models to capture satisfactorily the modes of reactivity in the low and intermediate temperature regimes that leads to the experimental measurements of the MIT for propane, n-butane and

A most important remaining iss

31

2,2

icted AIT of 735 K at φ = 5.1.

,3-trimethylbutane at temperatures that are distinctly higher than those of the other alkanes investigated (see Table 2). As discussed in the Introduction, the MIT is controlled to a significant extent by the physical processes of heat and mass transport occurring within the reaction vessel. These cannot be captured in an adequate way using a zero-dimensional simulation, which must make a significant contribution to the quantitative discrepancies between the numerical simulation and experiment.

Furthermore, as discussed in Section 3 with reference to propane, there is evidence that revisions to some important thermochemical parameters may be appropriate. This hypothesis has been tested with respect to the uncertainties in key thermochemical parameters for intermediate species involved in the low temperature oxidation of propane. The predictions can be are compared with those included in Figure 26. The revisions of the thermochemical parameters yield a pred

725

5 10 15 20 25 30 35700

750

775

T a / K

mol% propane in air

Figure 31. Predicted composition dependence of the AIT for propane when thermochemical parameters are revised according to the predictions from ref [2].

Clearly the revision of data for thermochemical parameters corrects the qualitative failure of the numerical predictions for propane, and is likely to underlie the similar problems associated with the predictions for n-butane and 2,2,3-trimethylbutane. There are two important observations to be made from this analysis. The first is that, as more accurate data becomes available, the models that are already in place in both full and reduced forms can be updated to provide more accurate predictive tools. The second is that when the predicted MIT falls at temperatures above 700 K it is associated with rather less rich compositions than those in the low temperature region, notabl

Revised thermochemical parameters

y at φ = 5.1 at 730 K versus 7.4 at 532 K in the

AIT using reduced kinetic models

predictions for propane.

c) Prediction of

In this subsection, taking n-heptane as an example, we test the applicability of various reduced models to the prediction of AIT and MIT by comparison with the results obtained from the comprehensive kinetic schemes. As can be seen in Figure 32, there is excellent consistency between all of the schemes for mixture compositions that lie on the lean side of the MIT. The prediction of the MIT itself is in satisfactory accord. The behaviour in very

32

rich mixtures shows some inconsistency. Particularly for the “reduced QSSA” scheme, for which there are potential complications arising from inappropriate thermochemistry that is an inevitable consequence of classifying a range of products with a single heat of formation. In this particular case, the assignment of the heat of formation for CO2 tends to exaggerate the exothermicity of the reaction. Independent tests assigning the heat of formation of the single product to that of nitrogen shows that the behaviour can be modified, but this also remains an approximation. In confirmation of the results discussed in Section 4, the quantitative behaviour of the skeleton scheme is rigorously maintained following application of the QSSA if the identities of the product-only species are retained.

530

540

550

4500

6 8 10 12 14 16 18

510

520

Reduced QSS

T

A

QSSA

Comprehensive

Skeleton

a / K

mol% h-heptane in air

Figure 32 ariation of AIT fo ane, derived from the comprehen ineti el

ated an from various uction, as di ed in Se 4. The co QSSA scheme 117 species in 571 reactions and

e reduce QSSA sche poratin uct only species as a single com t) 83 ies 452 reactions.

9. Disc and Conclusi

) Relatio ships betw identified in the comprehensive schemes

It is worthwhile to compare the classes of species and reactions removed at the different tages for different fuels in order to a the nera ds emerge. Such trends, if resent, ay be useful in indica x reduction achievable for higher

. V predicted r n-hept sive kion

c mod skeleton gener

chemby EXGAS

prises 236 species in 810 reactions, the d stages of its red scuss ct e

s mth d me (incor g all prod ponen specin

ussion ons

a n een redundant species

s sting the esess whe r any ge

tent ofl tren

p mhydrocarbons of similar classes as well as for perhaps indicating modifications which may be made at the mechanism generation stage for a given application.

The investigation of the Jacobian matrix led to the removal of 53 species from the

comprehensive (128 species) n-butane mechanism, leaving 75 necessary species in the partially reduced mechanism. Eighty species were removed from the comprehensive (122 species) propane mechanism, generating a partially reduced mechanism comprising 42 species. Of the 53 species removed from the n-butane mechanism 42 of these (79%) were identical to species also removed from the propane mechanism. These common species are shown in Table 4. Certain of these are referred to as “secondary species”. This is a

33

consequence of the procedures built into EXGAS for mechanism generation where, in order to provide a degree of simplification, isomeric species that are considered peripheral to the overall mechanism are represented by one generic species.

ndary species” are underlined. The species are represented by the formulation used in e EXGAS input programs, as is also the case where discussed in the text.

Table 4. Common species removed from the comprehensive n-butane and propane mechanisms. The common “secoth

C0 – C2 C3, C4 C5, C6 C7 + B3C C2H3CHOZ C5H10OOY C7H12Y2B4CH C2H3O#4COOOH C5H10Y C8H14Y2B6CH2 C2H6CO C5H9OHY C2H2T C3H5CHOY C6H10Y2 CH3COOOH C3H5OHY C6H10Z#6 CH4 C3H5OOHZ C6H12Y R12CHCOV C3H6O#3 R6CH2OH C3H6O#4 R9C2HT C3H7CHO C3H7OH C3H8CO C4H6Z2 C4H7OHY C4H7CHOY C4H8OOY R27C4H8OOH R35C4H8OOOOH ZC3H4O#4OOH ZC3H5O#4 ZCOC2H3Z ZCOC3H7 ZCOOOC2H5 ZCOOOC3H7 ZOOC3H4O#4OOH ZOOC3H5O#4

With the exception of the alkene hydroperoxide species (“C3H5OOHY”) in the propane

scheme, all of the species which were classed as secondary molecules in the EXGAS program were identified as redundant for the reduced schemes. These include pentene, hexene, dienes, alkene alcohols and alkene hydroperoxides.

There are also patterns between the removed species with respect to alkanes other than the

primary fuel and their sub-mechanisms, as shown in Table 5. For instance, C3H8 was removed from the n-butane mechanism and C4H10-1 (signifying n-butane) was removed

om the propane mechanism. Many of the species involved in the primary mechanism of C3H

ary reaction chains f the higher hydrocarbons.

fr8 were also removed from the n-butane mechanism during the reduction process, such as

C3H7 (propyl radicals), both isomers of C3H7O2 (propyl peroxy radicals) and of C3H7OOH. (propyl hydroperoxide). The corresponding types of free radicals as derivatives of n-butane were removed during the propane reduction. It may seem surprising that there should be any reference to oxidation chemistry of butane in a propane oxidation scheme. It should be born in mind, however, that in the nature of a comprehensive chemical model, association reactions between radicals (for example C3H7 + CH3 –> C4H10) can promote subsidio

34

Methane was removed in both of the reduction processes, but ethane was removed only

during the propane reduction. However, although it was not identified as redundant in the n-butane reduction, the elimination of the three remaining ethane consuming reactions from the n-butane reduced scheme did not incur a significant error. This constitutes the classification of C2H6 as an unidentified redundant product. The common removal of components of the sub-mechanisms of other intermediate alkanes is limited to C3 and upwards because ethyl and methyl radicals are known to be integral to the reduced propane mechanism. Pentane and higher alkanes were not present in either of the full mechanisms. Four cyclic species classed s primary species, three classed as secondary species, and eight species classed as cyclic free

radicals, were removed from the prop

m th

mechanism

aane mechanism.

Table 5. Classes of chemical species related to the submechanisms of alkanes commonly removed fro e comprehensive n-butane and propane mechanisms. (Note that the prefix R**, to represent

d fromradicals, does not give rise to a unique identifier for a particular species whenever it is generateEXGAS. For example, R33 is assigned to a C3 species in the propane scheme and a C4 species in the n-butane scheme.)

Species type Removed from butane Removed from propane mechanism

Alkane C3H8, CH4 C4H10-1, CH4

Alkyl radical R19C3H7 R20C4H9

Alkylperoxy radical R22C3H7OO R23C4H9OO

Alkyl hydroperoxide C3H7OOH C4H9OOH

Products of intramolecular R25C3H6OOH R27C4H8OOisomerisation of alkyl peroxy R26C3H6OOH R28C4H8OOH

radicals R29C4H8OOH,8OOH R36C4H

H

Dihydro peroxy radicals R33C3H6OOOOH R33C4H8OOOR34C4H8OOOOH R34C3H6OOOOH

R35C4H8OOOOH R38C4H8OOOOH

OH

Peracids CH3COOOH CH3COOOH

The hieved in the pre n further

, 38 of se 38, 31 were removed, the

COC2H3, H4. However, CH4 had all of its consuming reactions removed at the reaction reduction

stage and thus co 5 alkanes were moved, as were the relevan

lkyl hydroperoxides and alkanes higher than ane was not removed in the reduction down to

on of other ydrocarbon mechanisms. C2 – C6 aldehydes were removed from the cyclohexane

re is further common ground with respect to the species reductions accom hensive cyclohexane mechanism, initially as 499 to 100 species, thereductions to 60 and 47 species. Of the 53 species removed in the n-butane mechanismthese also existed in the full cyclohexane mechanism. Of theexceptions being C2H3CHOZ, C4H6Z2, C6H10Z#6, R12CHOV, R6CH2OH, ZC

uld be considered as a redundant product. All of the C3-Ct associated alkyl radicals, alkyl peroxy radicals, re

dihydroperoxides and ketohydroperoxides. Aentane were absent from the full scheme. Ethp

100 species but its consuming reactions were removed in the reaction reduction of the 60 species mechanism. The trend of removal of >C3 alkanes and their associated species also ook place in the cyclohexane reductions and is likely to be a feature in the reductit

h

35

mechanism. In common with propane and n-butane, all 17 secondary molecules of the comprehensive cyclohexane mechanism were removed. One species that was classed as primary cyclic and all 5 secondary cyclic species were removed, as occurred in the propane

duction. With the exception of the unidentified redundant species C6H6# (benzene), all 34

respecies classed as additional allene in the full mechanisms were removed.

b) Redundant reactions patterns

An investigation and comparison of the classes of reactions removed using principal component analysis of the rate sensitivity matrix F~ was made in the cases of n-butane and yclohexane oxidation mechanisms. The comprehensive n-butane mechanismc comprises 314

ery substantial

reactions. Most of these t and were removed, leaving only

ttle error to the output

species to be removed, even those that have relatively large

n lumping, 23 species were removed from the cyclohexane mechanism. Many of these

radicals, ethynyloxy radicals, acetyl radicals and

irreversible and 417 reversible reactions. The reduced mechanism comprises 300 reactions and the classes of reactions removed are shown in the Appendices. The comprehensive cyclohexane mechanism contains 1025 reversible reactions and 1298 irreversible reactions.

he numbers of reactions were reduced to 238 irreversible. This was a vTreduction and the many classes of reactions removed are also cited in the Appendices. The comprehensive cyclohexane mechanism contains a large subsection for benzene formation eactions which has 52 irreversible reactions and 290 reversible r

reactions were identified automatically as being redundanix reactions. The manual removal of this remainder incurred very lis

ignition delay times. Unimolecular initiations were removed in both n-butane and cyclohexane reductions.

These reactions are only important at high temperature initial conditions. Intermediate lkane reactions were commonly removed in both reductions by virtue of the removal of the a

species, as were the classes of alcohol reactions, peracid radical decompositions and Diels-Alder reactions. There are a number of reaction classes of the C0 – C2 base mechanism which were removed in both of the reductions. They are reactions of H2, B4CH, B6CH, B5CH2, CH4, C2H2T, R9C2HT, R10C2H3V, C2H4Z, R6CH2OH, R12CHCOVD, R14CH3CO, CO2, and R16CH3COOOH. It seems likely that these would be removed from all higher lkane schemes. a

c) Quasi steady state species

Investigation of the various mechanisms to identify species to which the QSSA approximation can be applied show that in principle all radical intermediates can be onsidered as candidate c

instantaneous QSSA errors of up to 10%. One caveat to this is for radicals immediately, or closely connected to the parent molecule, for example heptylperoxy radicals formed from reaction of heptyl + O2, had instantaneous QSSA errors of the order of 5%, which was sufficient to cause a significant change in the computed ignition profile when these species were removed by application of the QSSA. Through the application of the QSSA and

actiorewere large radicals and can be deduced from the comparison of Figures 21a and 21b, with notable absentees from Figure 21 b being the cylohexyl radical, various isomers of the cyclohexyl peroxy radical, the cyclohexyl alcoxy radical, the ring breakage of this molecule and subsequent successive additions of oxygen and isomerizations. A number of other maller radicals were eliminated with vinyl s

allyl radicals falling into this category.

36

d) Summary of the scale of reduction of kinetic mechanisms and the gain in speed-up of computation.

Theoretical predictions of the computational speed-ups resulting from the removal of species (total number = N) from a chemical scheme are usually quoted to scale with N2 since the majority of the computational effort for implicit solvers results from the manipulation of

e N x N Jacobian matrix. Where no species are removed then the speed-ups resulting from

le would therefore be expected to be between a ctor of N and N n. Following the removal of QSS species it is also possible that the

duced. However, for implicit olvers this may not always lead to large gains in computational time. Given these theoretical

some discussion as to the otential for use of the reduced mechanisms in future CFD calculations as discussed in the

l sub-model.

ththe removal of reactions (total number = n) is estimated to scale with n, since the effort required to compute the right hand sides of the rate equations is reduced where reactions are removed. The maximum speed-up achievab

2 2fastiffness of the system (the ratio of fast to slow time-scales) is resestimations it is useful to evaluate how the reductions carried out in this work compare with predicted speed-ups. The calculated speed-ups will also allowpnext section, since the computational effort in reactive flow calculations is often dominated by that required to solve the chemica Table 6. Summary of the numbers of species and reactions contained in each of the reduced mechanisms and corresponding calculated and estimated runtimes. Runtimes are estimated from runtime being proportional to the squared number of species ( ∝ N2) or from runtime being proportional to the number of reactions ( ∝ N). Reaction numbers correspond to equivalent number of rreversible reactions. Spei cies numbers for reduced schemes correspond to the numbers of necessary

species, excluding species with no consuming reactions and thus only present as reaction products, and accounts for any inconsistence in stated species number when compared to deliverable 37.

Runtime % of full scheme Fu Full mechanism

1 Skeleton mechanism Post Jacobian analysis

2nd Skeleton mechanism Post rate sensitivity

Final reduced scheme following QSSA

Calculated run time

Estimate from ∝ 2

Estimate from

el st

N∝ n

analysis Species

(reaction) Species (reactions)

Species (reactions)

Species (reactions)

C3H8 122 (1137) 42 (545) 37% 12% 48% 42(166) 15% 12% 15% nC4H10 128 (1148) 75 (715) 62.3% 34% 62% 74 (300) 18.3% 33% 26% 59 (270) 16.5% 21% 24% cC6H12 499 (3348) 106 (845) 15% 4.5% 25.2% 99 (238) 5% 4% 7.1% 59 (238) 2.1% 1.4% 7.1% 48 (157) 1.04% 0.9% 4.7% 33 (323) 0.5% 0.4% 9.6% nC7H16 358 (2411) 223 (1696) 19% 39% 70% 218 (810) 18% 37% 34% 81 (452) 5% 5.1% 19% The computational speed-ups achieved using the reduced mechanisms at each stage of the reduction when compared to the full schemes are presented in Table 6. In most cases, the

37

speed-ups are at least as good as, o stimated from a scaling of N2. In articular, for cyclohexane the computational effort required to solve the reduced model is

ired for the full scheme, giving the indication that at least for some els, the combination of local sensitivity and QSSA analysis is sufficient to provide schemes

of

ion has been possible for the cyclohexane scheme when compared with the alkane schemes.

) The status of chemical computation with CFD analyses, with reference to AIT ed

T g of chemical kin ex fluid d s ssiblemputational fluid dynamic (C these metho ap of he n tion, pressure fects, with asso abl nns occur in the nally, o nth turbulent flow wever, limitati po h k can be CFD code, rea y c plex pre to comp mately bec ep

The length and time-scale al reaction iffe rgn haracter . T all re e to be u e flow field he ott different me sequently to pr mp te desh . Chemistry can be coupled d d t ftth p er runer istry can nd stored bas with tie FD calculation. In turbulent flows, account of the co ling bu try must e mode oac A nume dologies have b odelling turbu is interth , the stochastic transported probability density function (PDF) methvi s approach finite-rate ch ffe throut the joint sca velocity-sc w e the

re ical species cons n of large, m sio l PDFe gnificant co nd at present p ent a l

to ber of scalar mbers of species) employed in practical li y contrast, the ditional mome (C C) ape endently by Kl r [24], provide co mical n inetic effects h w calculation equence, can m ated with practical geo v ts of specie ditionally av a f ed valse riable, the inates the m e non-l

ate terms wit sport equation n C D codki clusion of k . Typically m est cou orted PDF h e applied with tens of chemical s

ils d can han .

r better than, those epless than 1% of that requfu

use for CFD calculations. In other cases, such as n-heptane, although the degree of reduction is large leading to final run times of only 5% of the full scheme, the remaining number of species may necessitate the use of alternative methods for including the kinetics in CFD computations such as the use of look-up tables. Interestingly, the extent of the final reduced schemes do not appear to depend on the size of the starting mechanism and a much higher degree of reduct

epr iction.

he linkin etics and compl ynamics i ds being

po using co FD) techniques, with c able andling th atural convec and buoyancy ef ciated vari e heat a

igd mass

n of tra port, likely to flows of interest. Additio modelling f the itiobo laminar and s is possible. Ho ons are im sed by t e level of inetic detail that incorporated in any with inc singl omre sentations leading uter run times that ulti ome unacc table.

s involved in chemic s often d r by o ders of ma itude from the

havc istic fluid flow time-scales

thhis gener y requi

stry (es that

diff rent methods sed for computing and the c mi perator spli ing), with the thods coupled sub ovide a co le cription of t e reacting flow and CFD codes irectly, an his is o en used in e case of laminar flows, although this ca

natively, the chemn lead to excessive com

computed a priori aut times.

Alt be in a data e, he data retr ved during the C up etween turb lence and chemis also be made through som lling appr h. ber of diff rent metho een proposed for m lence-chem try actions. At e present time od [23] pro des a rigorou to the inclusion of emistry e cts gh the solu ion of either lar PDF, or a joint alar PDF, her scalars rep sent the chem

iidered. Solutio

aulti-dimen na s does,

how ver, require s mputing resources, this can re res imiting fac r in the num dimensions (i.e. nuapp cations. B deterministic con nt closure M proach, dev loped indep imenko and Bilge s a more e no method of i corporating k wit in turbulent flo s that, as a consbe ore readily integr in computations of metries. By consideration of the arious momen

as concentration, con

imeraged at ix ue of a

con rved scalar v CMC approach el ajor sourc of inearityfrom the reaction r hin the species tran s solved i F es, thus ma ng the direct in inetic effects feasible , and with od mputer reso rces, the transp met od can currently b pecies, wh t the CMC metho dle hundreds of species

38

The reduced kinetic scheme work ar c able ole D codes r the flow r l

ci accoun ry intera he tter caet ensional r pler) representation of the ignition vessel is ui t in m e significant c n es onal els that can be run using more modest an re capvi ons in the time- e l app

F mains, both t th contaim nd reactions e accuracy of their more complex parent em ethods for in fluid flow m ap achesle hat without the reduction work performed i nt dy, thit able to analy t pplication of ch ac CFD d due to siz ensive kinetic s ailablee. The present work has th kinetic repres at be b forts to si e the accuracy licabD g flows o nce to safety issues.

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pre se method used to t for turbulence-chemist t la se, and wh her full three-dim (o some simreq red, this could resul od ls that require omputer ru tim large, par lel computers, or mod resources d a able of pro ding soluti scal s desirable for industria lication.

urther work re in terms of the provision of kine ic schemes at n fewer che ical species a , but which retain thsch es, and on m terfacing kinetic and odelling pro . What is c ar, however, is t n the prese stu e range of s uations amen sis hrough the a emically re ting codeswas severely limite e of the compreh mechanism av at the tim erefore resulted in entations th can used as the asis of further ef

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11. Publica n ference Pres

e

Fa hs, K.J. H e an, “Cool f ac exper n tudies of propan . Comb. Inst

. Hughes a role and yd po ng hydrocarbon ion”, Proc. Comb. Inst. 30, 1083 - 1091 05

B F. Batti e J. Hughe G fiths, “ ai echanisms for the prediction of autoignitions”, rehe 19 , 2 ,

. J. weather and A. S. Tomlin, “Evaluation of models for the low kanes through interpretation of pressure - temperature

iti Ch s ysics, 2006, 3197 - 3210

, M. Fairw h .M. Hug .S lin Significance e elementary reactio O during the co of Hydro arbon

s at high pres b. Inst., 31, 2007, in press.

K. L . Griffiths, A.A. Burluka, “Flames of di-tert-butyl-peroxide urbulen a , 2007, in pre

Poste blished proceedings marked*)

. F hs, K.J. Hughes, R. Porter and A.S. Tomlin, (2005) “Kinetic e toignition of effect of f echanismu t urrent Resea b A

, Loughborough University, UK, 2005.

, F. Buda, M. Fairweather, P.A. Glaude, J.F. Griffiths, K.J. Hughes, R. e lin, “The E c chanism Red im ed P

Quantitativ pact of ntie Pa European Co u g, ECM 2005, a-N

F. Buda, M a Glaude, J.F , K . Huge lin, “A u tudy of the Kinetic Origins of Two-Stage

the Dependen perature on Reactant Pressure in Lean s,” Second o on Meeting, E Louvain-la-Neuve,

.

Fairweather F Hughes, , li “Au ced reaction s for hydrocarbon oxidation with application to

i dary prediction for explosion hazards m th European p puter Aid P ring, Garm any,

tio s and Con entations Pap rs published in peer revie dwe journals R. irlie, J.F. Griffit ugh s and H. Pearlm lames in sp e: imental and umerical s e combustion”, Proc ., 30, 1057, 2005 J.F Griffiths, K.J. nd R. Porter, “The rate of h rogen eroxide dec mposition duri two-stage ignit(20 ) F. uda, P.A. Glaude, n-L clerc, R. Porter, K. s and J.F. rif Use ofdet led kinetic m Journal of Loss P vention in t Process Industries, 006 227-232 K Hughes, J. F. Griffiths, M. Fair

n of altemperature combustiohysical ign on diagrams”, P emi try Chemical Ph

G. Mittal, C.-J. Sung eat er, J.F. Griffiths, K hes and A . Tom , “and rate of th n HO2 + C mbustion gen + CMonoxide mixture sures”, Proc. Com

iu, M. Ormsby,w, T

J.Fdecomposition”, Flo ce nd Combustion ss

r presentations (pu M airweather, J.F. Griffitmod

n alling of two-stage au alkanes and the

ute of Physics Cormal m

rch in Com reduction

ustion:ofor Research Students and Young Researchers

toignition temperatures,” Insti Forum

* F. Battin-LeclercPort r, and A.S. Tom ffe t of Formal Me uction on S ulat ropane Autoignition and a e Assessment of the Im Uncertai s in rameterValues,” Second mb stion Meetin Louvain-l euve, Belgium, Paper 16, 2005. * Battin-Leclerc, . F irweather, P.A. . Griffiths .J hes, R. Port r, and A.S. Tom N merical SAutoignition and ce of Autoignition TemAlkane-Air Mixture Eur pean Combusti CM 200 ,5Belgium, Paper 25, 2005 * R. Porter, M. , J. . Griffiths, K.J. A.S. Tom n, tomaticgeneration of redu mechanismauto gnition boun itigation,” 16Sym osium on Com ed rocess Enginee ish-Partenkirchen, Germ2006.

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M. F F. Griffith es, R. Porter and A.S. Tom , “Aued reaction r hydrocarbon oxidation with application to

y predicti o ards mitiga E search London K

Fairweather, J.F. Gr J. Hughes and A , he aueduced reaction it pplica

uto n,” Thirty-first International Symposium on Combustion, Heidelberg, Germany, 2006.

Fairweather, F . Porter and l “Sysi SA to com s reduction v lu ping,” irty- osium o o erm

her, J.F. Griffiths, K.J. Hughes and A.S. Tom , “Sim lated d Oxidation of Cyclohexane,” Third European Combustion Meeting,

ce, 200 c

f tions (pub arked*)

undamentals o u emistry, One- ng f the i , xford, 2003.

alski, “The SAFEKINEX project,” U on aison g , 2004

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, K.J. Hughes, J M. Fairweather, “The Use of Global Uncertainty h n ition as t

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airweather, J. s, K.J. Hugh lin tomatic generation of reduc mechanisms foauto ignition boundar on f r explosions haz tion,” CAP re poster day, University College , U , 2006. R. Porter, M. iffiths, K. .S. Tomlin “T tomatic generation of r mechanisms for hydrocarbon oxidation w h a tion to a ignition boundary prediction for explosions hazards mitigatio

K.J Hughes, M. J. . Griffiths, R A.S. Tom in, tematic appl cation of the QS bu tion mechanism ia reaction m Thfirst International Symp n C mbustion, Heidelberg, G any, 2006. R. Porter, M. Fairweat lin uAutoignition (AIT) anECM2007, Chania, Gree 7, a cepted. Con erence presenta lished proceedings m J.F. Griffiths, F f a to-ignition ch day meeti o British Sect on of the Combustion Institute University of O J.F. Griffiths and A. Pek K Explosi Li Group, Lou hborough University . * F. Buda, P.A. Glaude, F. ttin Leclerc, R. Porter, K.J. H es and J.F rif “Udeta led kinetic m for the prediction itions,” Sym n and Mitigation of trial Expl on PMIE, Krakow, Poland, 20 * J.F. Griffith ry l cture, “Cool flam co ropean Combustion Meeting, L a-N uve, Belgium, 2005 * A.S. Tomlin .F Griffiths,Met ods in the Evaluation of Ki etic Models using Ign

cal Combustion, GranadDelay Me uremen s,” 11th

International Conferen mer ain, 200

. Porter, “Kinetic Mechanism Reduction for Chemical PrRSPEME research meeting, University of Leeds, UK

41

42

12. Appendices

u s

T llowing c e Arrhenius f nexp(-E/RT) and ecules, v . Electronic f lch ble fro h /reaction luw equire u u es to be sol e ep nd their o codes are a abl c

m . r ion reduced 4 6 reactions

A n E

Red ced kinetic scheme

he units for the fo me hanisms are in th orm k=ATare specified as mol

anisms are availaKel in, cm3 and s-1 copies o the fol owing

me m t e authors. QSSA mped mechanisms are not QSSA/rsho n here as they r niq e integration cod ved. Thes action

lum ed mechanisms ors

a ass ciated integration lso avail e in ele tronic for from the auth

a) P opane oxidat to 2 species in 16 # Reactions 1 C3H8 → R4CH3+R11C2H5 5. 0 4000×1016 3011.33 2 C3H8+O2 → R3OOH+R21C3H7 3. 0 2321×10-11 4157.02 3 C3H8+O2 → R3OOH+R19C3H7 4. 0 2151×10-11 4660.29 4 R19C3H7+O2 → R22C3H7OO 3 - 0.653×10-5 2.5 5 R22C3H7OO → R19C3H7+O2 3. - 1163×1026 3.9311 7104.59 6 R21C3H7+O2 → R24C3H7OO 3 - 0.653×10-5 2.5 7 R24C3H7OO → R21C3H7+O2 2. - 514 1917×1028 4.5 8102.49 8 R25C3H6OOH+O2 H 3. - 0→ R31C3H6OOOO 653×10-5 2.5 9 R31C3H6OOOOH → R25C3H6OOH+O2 1. - 841 1743×1029 4.6 8163.23 10 R26C3H6OOH+O2 → R32C3H6OOOOH 3 - 0.653×10-5 2.5 11 R32C3H6OOOOH → R26C3H6OOH+O2 2. - 884 1272×1027 4.1 7015.41 12 R30C3H6OOH+O2 → R37C3H6OOOOH 3 - 0.653×10-5 2.5 13 R37C3H6OOOOH → R30C3H6OOH+O2 4. - 871 1494×1027 4.1 6662.42 14 R22C3H7OO → R25C3H6OOH 3 1 1.300×109 6356.32 15 R22C3H7OO → R26C3H6OOH 8. 1 1600×108 4343.23 16 R26C3H6OOH → R22C3H7OO 6 1. 01 7.938×106 15 227.68 17 R24C3H7OO → R30C3H6OOH 1. 1 1000×1010 7866.13 18 R31C3H6OOOOH → R2OH+C2H5COOOH 3 1 1.300×109 5349.77 19 R32C3H6OOOOH → R2OH+C2H5COOOH 5. 1 1700×108 1826.88 20 R37C3H6OOOOH → R2OH+C2H5COOOH 1 1 1.700×109 3839.96 21 R37C3H6OOOOH → R2OH+C2H5COOOH 8. 1 1600×108 4343.23 22 R19C3H7 → R4CH3+C2H4Z 2 0 1.000×1013 5601.41 23 R25C3H6OOH → R3OOH+C3H6Y 8. 0 1500×1012 3085.05 24 R30C3H6OOH 8 0 1→ R3OOH+C3H6Y .500×1012 3085.05 25 R25C3H6OOH 3. 0 9→ R2OH+C3H6O#3 000×1011 864.12 26 R26C3H6OOH #4 2. 0 7→ R2OH+C3H6O 500×1010 674.89 27 R30C3H6OOH #3 3. 0 9→ R2OH+C3H6O 000×1011 864.12 28 R19C3H7+O2 → C3H6Y+R3OOH 2 0 2.656×10-12 516.36 29 R21C3H7+O2 → C3H6Y+R3OOH 2. 0 2324×10-12 516.36 30 C3H8+R1H → H2+R21C3H7 1 2 2.494×10-17 516.36 31 C3H8+R1H → H2+R19C3H7 9. 2 3464×10-17 875.19 32 C3H8+R2OH → H2O+R21C3H7 4 2 -.317×10-18 385 33 C3H8+R2OH → H2O+R19C3H7 8. 2 2966×10-18 26.47 34 C3H8+R3OOH → H2O2+R21C3H7 6 0 7.641×10-13 800.7 35 C3H8+R3OOH → H2O2+R19C3H7 1. 0 8992×10-12 555.61 36 C3H8+R4CH3 → CH4+R21C3H7 3 0 4.321×10-13 831.4 37 C3H8+R4CH3 → CH4+R19C3H7 9. 4 4962×10-25 126.82 38 C3H8+R7CH3O 2 0 2→ CH3OH+R21C3H7 .490×10-13 264.72 39 C3H8+R7CH3O 5. 0 3→ CH3OH+R19C3H7 313×10-13 673.88 40 C3H8+R8CH3OO 7 4 0 8→ CH3OOH+R21C3H .981×10-12 807.25 41 C3H8+R8CH3OO 7 1. 0 1→ CH3OOH+R19C3H 992×10-11 0065.43 42 C3H8+R22C3H7OO 7 4. 0 88→ C3H7OOH+R21C3H 981×10-12 07.25

43 C3H8+R22C3H7OO 7 1. 0 1→ C3H7OOH+R19C3H 992×10-11 0065.43 44 C3H8+R24C3H7OO 7 4. 0 8→ C3H7OOH+R21C3H 981×10-12 807.25 45 C3H8+R24C3H7OO 7 1. 0 1→ C3H7OOH+R19C3H 992×10-11 0065.43 46 R3OOH+R21C3H7 6 0 0→ .641×10-12 C3H7OOH 47 R4CH3+R21C3H7 1. 0 0→ C4H10 992×10-11 48 R22C3H7OO+R3OOH 3 0 -→ C3H7OOH+O2 .321×10-13 654.25 49 R24C3H7OO+R3OOH 3. 0 -→ C3H7OOH+O2 321×10-13 654.25 50 → R2OH+HCHO+R11C2H5 1. 0 2500×1016C3H7OOH 1137.39 51 → R2OH+HCHO+R10C2H3V 1. 0 2500×1016C3H5OOHY 1137.39 52 → R2OH+HCHO+B2CO+R4CH3 1. 0 2 9 500×1016C2H5COOOH 1137.353 → C2H4Z+R4CH3 1. 0 1195×10-11C3H6Y+R1H 459.49 54 C3H6Y+R2OH → R4CH3+CH3CHO 2 0 -.324×10-12 452.94 55 C3H6Y+R2OH → HCHO+R11C2H5 2. 0 -324×10-12 452.94 56 C3H6Y+R3OOH → R2OH+C3H6O#3 1. 0 7660×10-12 247.11 57 C3H6Y+R1H → ZC3H5Y+H2 9. 2. 1464×10-20 5 45.95 58 C3H6Y+R2OH → ZC3H5Y+H2O 4 2 -.981×10-18 762.46 59 C3H6Y+R3OOH → ZC3H5Y+H2O2 1. 2. 6046×10-20 6 240.56 60 C3H6Y+R4CH3 → ZC3H5Y+CH4 2 3. 1.158×10-24 5 799.19 61 ZC3H5Y+R3OOH → C3H5OOHY 8. 0 0302×10-12 62 ZC3H5Y+R4CH3 → C4H8Y 1 0 0.660×10-11 63 → C4H8OOY 1. 0 0660×10-11 ZC3H5Y+R8CH3OO 64 2ZC3H5Y → C6H10Y2 1 0 0 .660×10-11

65 2R4CH3(+M) → C2H6(+M) 5 0 0 .994×10-11

O2/0.4/ B2CO/0.75/ CO2/1.5/ / N2/0. 10-6 -7 1389.03 3 1180 /

H2O 6.5/ CH4/3/ C2H6/3/ AR/0.34/ 4/ HE/0.34/ LOW / 1.001× / TROE / 0.62 7

66 R11C2H5+R1H - 903 1→ 2R4CH3 2.188×10-7 0.6 195.51 67 R1H+R4CH3(+M) 0 0→ CH4(+M) 2.773×10-10 O2/0.4/ B2CO/0.75/ CO2/1.5/ / 4/ N2/0.

-1.8 0 / 61 /

H2O 6.5/ CH4/3/ C2H6/3/ AR/0.3 4/ HE/0.34/ LOW / 3.881×10-24

TROE / 0.37 331568 → CH4+R1H 3 3. 24 3.007×10-22 11R4CH3+H2 722.09 69 R10C2H3V(+M) → C2H2T+R1H(+M) 2.000×1014 0 2 0030.2 O2/0.4/ B2CO/0.75/

18 CO2/1.5/ / 4/ N2/0.4/ HE/0.3.5 22924.

8 /

H2O 6.5/ CH4/3/ AR/0.3 4/ LOW / 1.976×10 -7

1 1×1001 /

TROE / 0.3570 C2H4Z+R1H 8 1. 6→ R10C2H3V+H2 .302×10-17 93 542.53 71 R11C2H5(+M) → C2H4Z+R1H(+M) 8 0 2.200×1013 0130.85 O2/0.4/ B2CO/0.75/ CO2/1.5/ / 6/3/ AR/0.34/ N2/0.

0 16809.26 379 /

H2O 6.5/ CH4/3/ C2H 4/ HE/0.34/LOW / 5.645×10-7 / TROE / 0.75 97 1

72 C2H4Z+R1H(+M) 2 - 932 2→ R11C2H5(+M) .653×10-10 0.0 046.07 O2/0.4/ B2CO/0.75/ CO2/1.5/ / 3/ AR/0.34/ N2/0.

-0.09 -1275 /

H2O 6.5/ CH4/3/ C2H6/ 4/ HE/0.34/ LOW / 1.827×10-30 .53 / TROE / 0.75 97 1379

73 R2OH+H2 → R1H+H2O 1 1. 1.660×10-16 6 660.8 74 R2OH+C2H4Z → R10C2H3V+H2O 3 0 2 9.3 .321×10-11 9675 R2OH+C2H4Z → R4CH3+HCHO 3 0 4 .94 .321×10-12 5276 R14CH3CO(+M) B2CO+R4CH3(+M) 7 - 3 8→ .552×1014 0.494 654.1 LOW / 2.759×10-7 -0.49 7093.96 /

TROE / 0.5 1 1×108 / 77 B2CO+R2OH → CO2+R1H 1 1. -.046×10-17 5 251.64 78 R5CHO+M → R1H+B2CO+M 3 - 8.155×10-7 1 555.61 H2/2/ B2CO/1.5/ CO2/2/ H2O/6/ 79 R5CHO+R4CH3 1 0 0→ CH4+B2CO .992×10-10 80 R4CH3+HCHO → R5CHO+CH4 1 6. 9.278×10-31 1 91.44 81 R11C2H5+HCHO 9 2. 2→ R5CHO+C2H6 .248×10-21 81 949.17 82 HCHO+R1H → R5CHO+H2 2 1. 1.158×10-16 62 056.87

43

83 HCHO+R2OH → R5CHO+H2O 5 1. -.645×10-15 18 201.31 84 R7CH3O+M → HCHO+R1H+M 2 0 6.573×10-10 794.16 O2/0.4/ B2CO/0.75/ CO2/1.5/ / 4/ N2/0.H2O 6.5/ CH4/3/ C2H6/3/ AR/0.3 4/ HE/0.34/ 85 R7CH3O+R4CH3 → HCHO+CH4 3 0 0.985×10-11 86 R7CH3O+R11C2H5 0 0 → HCHO+C2H6 3.985×10-11

87 R7CH3O+HCHO O 1 0 1→ CH3OH+R5CH .660×10-13 509.81 88 2R7CH3O → CH3OH+HCHO 9. 0 0 962×10-11

89 CH3OH+R1H → R4CH3+H2O 3 0 2.321×10-10 667.34 90 R7CH3O+H2 → CH3OH+R1H 1 2. 1 2.178×10-19 59 096.73 91 CH3OH+R2OH → R6CH2OH+H2O 5 2 -.147×10-18 171.11 92 CH3CHO+R1H → H2+R14CH3CO 6 0 2.641×10-11 113.74 93 CH3CHO+R4CH3 → R14CH3CO+CH4 3 5. 1.321×10-30 6 258.18 94 CH3CHO+R2OH → R14CH3CO+H2O 6.973×10-12 0 2 51.64 95 CH3CHO+R7CH3O → R14CH3CO+CH3OH 3. 0 9985×10-13 05.89 96 R15C2H5O → HCHO+R4CH3 8 0 1.000×1013 0820.33 97 R15C2H5O → CH3CHO+R1H 2.000×1014 0 1 1726.22 98 R11C2H5+R2OH(+M) 3. - 7 .05 881×10-8 C2H5OH(+M) 0.327 70 CO2/3/ H2O/5/ B2CO/2/ H2/2

7.6 10281 5000 /

/ LOW / 1.718×1031 -1 .88 / TROE / 0.5 300 900

99 C2H5OH+R2OH → H2O+R15C2H5O 1. 0. 8 .23 245×10-12 3 05100 C2H5OH+R2OH → H2O+R2OH+C2H4Z 2. 0. 3 .96 823×10-13 27 01101 C2H5OH+R2OH → H2O+CH3CHO+R1H 7. 0. 0637×10-13 15 102 O2+R1H → R2OH+B1O 1. 0 7 8.41 627×10-10 44103 O2+R1H(+M) → R3OOH(+M) 7. 0 0 505×10-11

O2/0.4/ B2CLOW / 4.96

O/0.75/ CO2/1.5/ / 2H6/3/ AR/0.28/ HE/0.34 -30 -0.8 0 /

8

/ N2/0.67/ H2O 0/ CH4/3/ C 2×10

TROE / 0.5 1 1×10 / 104 0 0 O2+R1H(+H2O) → R3OOH(+H2O) 7.505×10-11

LOW / 1.902×10-32 0 -1046.8 / TROE / 0.45 1 1×108 /

105 O2+R4CH3(+M) O(+M) 1. 0→ R8CH3O 295×10-15 1.2 LOW / 1.544×10-22 -3.3 0 /

TROE / 0.36 1 1×108 / 106 → O2+R4CH3(+M) 1.928×10 .474 15055.04 R8CH3OO(+M) 16 -0 15055.04 /

×10 / LOW / 2.298×109 -4.97

8TROE / 0.36 1 1107 .69 18419.73 O2+R4CH3 → HCHO+R2OH 4.981×106 -4108 O2+CH4 5.286×10 .4975 514.26 R4CH3+R3OOH → -11 -0109 → C2H2T+R3OOH 2.225×10-18 1.61 -201.31 O2+R10C2H3V 110 O2+R10C2H3V → HCHO+R5CHO 7. 5471×10-8 -1.39 03.27 111 0.77 -301.96 O2+R11C2H5 → R17C2H5OO 3.653×10-14

112 O2+R11C2H5 3.910×10 -1.0132 15798.82 R17C2H5OO → 18

113 → C2H4Z+R3OOH 1.395×10-12 0 1962.76 O2+R11C2H5 114 C2H4Z+R3OOH → O2+R11C2H5 3. 358 8 0.68 224×10-11 -0.3 23115 O2+R11C2H5 3→ CH3CHO+R2OH 9.962×10-14 0 472.57 116 R11C2H5+R3OOH 7 -→ O2+C2H6 .150×10-13 0.0624 320.33 117 O2+R5CHO → B2CO+R3OOH 1. 2262×10-11 0 06.34 118 O2+R7CH3O → HCHO+R3OOH 3 8.653×10-14 0 55.56 119 HCHO+R3OOH 7 1→ O2+R6CH2OH .500×10-11 -0.321 1177.93 120 R14CH3CO+R3OOH 2 -→ O2+CH3CHO .963×10-12 0.0659 2270.31 121 O2+R15C2H5O 9 8→ CH3CHO+R3OOH .962×10-14 0 55.56 122 R3OOH+R1H → H2+O2 7 7.139×10-11 0 04.58 123 R3OOH+R1H 2 4→ 2R2OH .823×10-10 0 52.94 124 R3OOH+R1H 4 8→ H2O+B1O .981×10-11 0 55.56 125 R3OOH+R4CH3 → R7CH3O+R2OH 2.989×10-11 0 0 126 → R2OH+R4CH3+B2CO 4.981×10 0 0 R3OOH+R10C2H3V -11

127 → R4CH3+HCHO+R2OH 3.985×10-11 0 0 R3OOH+R11C2H5

44

128 R3OOH+R2OH → H2O+O2 4 -.815×10-11 0 251.64 129 R3OOH+B2CO → CO2+R2OH 2 1.490×10-10 0 1877.2 130 R3OOH+R5CHO → R2OH+R1H+CO2 4.981×10-11 0 0 131 R3OOH+HCHO → R5CHO+H2O2 4. 6 2.53 981×10-12 0 54132 R3OOH+CH3CHO 1 5 2.71 → R14CH3CO+H2O2 .660×10-12 0 03133 2R3OOH → H2O2+O2 2 -.158×10-13 0 820.33 134 2R3OOH → H2O2+O2 6 6.973×10-10 0 029.19 135 H2O2(+M) → 2R2OH(+M) 3. 2000×1014 0 4408.66 O2/0.4/ B2CO/0.75/ CO2/1.5/ / 3/ C2H6/3/ AR/0.34/ N2/0.

22898.84 H2O 6.5/ CH4/ 4/ HE/0.34/

LOW / 4.981×10-7 0 / TROE / 0.5 1 1×108 /

136 → H2O+R2OH 1.660×10-11 0 1811.78 H2O2+R1H 137 H2O2+R2OH → H2O+R3OOH 1. 6295×10-11 0 54.25 138 0 R8CH3OO+R1H → R7CH3O+R2OH 1.594×10-10 0 139 R8CH3OO+R4CH3 8 -→ 2R7CH3O .302×10-12 0 704.58 140 R8CH3OO+C2H4Z O#3 1. 1→ R7CH3O+C2H4 826×10-9 0 0065.43 141 R8CH3OO+R11C2H5 → 2H5O 3. 0 0 R7CH3O+R15C 985×10-11

142 R8CH3OO+R2OH → CH3OH+O2 9. -11962×10 0 0 143 R8CH3OO+HCHO → CH3OOH+R5CHO 1. 6660×10-12 0 089.58 144 R8CH3OO+R3OOH → O2 4.151×10-13 0 -8 5.23 CH3OOH+ 0145 R8CH3OO+R3OOH +H2O 8.→ O2+HCHO 302×10-14 0 0 146 R8CH3OO+H2O2 → CH3OOH+R3OOH 3. 4985×10-12 0 982.39 147 2R8CH3OO → CH3OH+HCHO+O2 4. - .62 151×10-14 0 402148 2R8CH3OO → 2R7CH3O+O2 4. - .62 151×10-14 0 402149 CH3OOH → R7CH3O+R2OH 6. 2 88.38 000×1014 0 12150 CH3OOH+R2OH OO 2. -→ H2O+R8CH3 989×10-12 0 186.21 151 R17C2H5OO+R4CH3 H3O 3. -→ R15C2H5O+R7C 321×10-12 0 603.93 152 R17C2H5OO+C2H4Z 4O#3 3. 1→ R15C2H5O+C2H 819×10-8 0 1021.64 153 R17C2H5OO+HCHO HO 7. 7→ C2H5OOH+R5C 471×10-12 0 247.11 154 R17C2H5OO+R3OOH 6→ O2+C2H5OOH .475×10-13 0 -654.25 155 R17C2H5OO+R8CH3OO → R15C2H5O+R7CH3O+O2 3.321×10-13 0 0 156 2R17C2H5OO → 2R15C2H5O+O2 6. 1 .65 807×10-14 0 00157 2R17C2H5OO → C2H5OH+CH3CHO+O2 2 1 .65 .989×10-14 0 00158 R16C2H4OOH → R6CH2OH+HCHO 2. 1 39.96 500×1013 0 38159 R16C2H4OOH → C2H4Z+R3OOH 2.000×1013 0 11826.88 160 C2H4Z+R3OOH → R16C2H4OOH 5 987 8.273×10-16 1.2 404.06 161 C2H5OOH → R15C2H5O+R2OH 4. 2 90.34 000×1015 0 15162 C2H5OOH+R2OH H2O 9. 4→ CH3CHO+R2OH+ 796×10-12 0 52.94 163 C2H4Z+R4CH3 3 3→ R19C3H7 .487×10-13 0 699.04 164 2R11C2H5 → C4H10 1 0.826×10-11 0 165 B2CO+R10C2H3V+R3OOH 2 1. -→ C2H3CHOZ+O 177×10-53 5.0715 17114.76 166 ZC3H5Y+R3OOH 2OH 1. 0→ C2H3CHOZ+R1H+R 162×10-5 -2 b) n- n reduce 300 reactions

s discussed

butane oxidatio d to 74 species in This mechanism wa in Deliverable 37. # Reactions A E n 1 C4H10-1+O2 → R3OOH+R20C4H9 6.973×10-10 0 26716.41 2 C4H10-1+O2 → R3OOH+R21C4H9 6 4.649×10-10 0 25432.23 R20C4H9+O2 → R23C4H9OO 1.494×10-5 -2.5 0 4 R23C4H9OO O2 .903 → R20C4H9+ 9.853×1025 -3 16764.69 5 R21C4H9+O2 .5 → R24C4H9OO 2.823×10-5 -2 0 6 R24C4H9OO → R21C4H9+O2 3.090×1028 -4.5621 18764.997 R28C4H8OOH+O2 H .5 → R36C4H8OOOO 2.823×10-5 -2 0 8 R36C4H8OOOOH 2 .6819 → R28C4H8OOH+O 6.417×1028 -4 18872.23

45

9 R29C4H8OOH+O2 → R37C4H8OOOOH 1.494×10-5 -2.5 0 10 R29C4H8OOH+O2 1.371×1027 -4.1844 17315.82 R37C4H8OOOOH →11 39C4H8OOOOH 2.490×10-6 -2.5 0 R30C4H8OOH+O2 → R12 R39C4H8OOOOH → R30C4H8OOH+O2 2.290×1026 8 1-4.184 6692.11 13 R31C4H8OOH+O2 → R40C4H8OOOOH 1.577×10-5 -2.5 0 14 R40C4H8OOOOH 97 → R31C4H8OOH+O2 7.059×1028 -4.67 18871.3815 R32C4H8OOH+O2 → R41C4H8OOOOH 1.494×10-5 -2.5 0 16 R41C4H8OOOOH → R32C4H8OOH+O2 6.867×1026 -4.1847 17316.0517 R38C4H8OOH+O2 OOH → R42C4H8OO 1.660×10-5 -2.5 0 18 R42C4H8OOOOH +O2 → R38C4H8OOH 1.021×1028 -4.1173 18592.99 19 R23C4H9OO → R28C4H8OOH 5.700×108 1 12581.78 20 3832 6498.76 R28C4H8OOH → R23C4H9OO 8.758×105 1.21 → R29C4H8OOH 1.500×108 1 12581.78 R23C4H9OO 22 R29C4H8OOH → R23C4H9OO 1.211×106 1498 5466.53 1.23 R24C4H9OO → R30C4H8OOH 5.000×109 1 17866.13 24 R24C4H9OO 4.079×107 1.1486 11103.38 R30C4H8OOH →25 R24C4H9OO → R31C4H8OOH 3.300×109 11 6356.32 26 R24C4H9OO → R32C4H8OOH 8.600×108 1 14091.6 27 R32C4H8OOH 1482 → R24C4H9OO 7.038×106 1. 6976.75 28 R29C4H8OOH → R38C4H8OOH 5.700×108 1 7700.05 29 R30C4H8OOH → R32C4H8OOH 8.600×108 1 9964.77 30 → R30C4H8OOH 8.627×108 0.9995 9612.67 R32C4H8OOH 31 R36C4H8OOOOH → R2OH+C3H7COOOH 3.300×109 1 16356.32 32 R36C4H8OOOOH → R2OH+C3H7COOOH 5.700×108 1 11575.24 33 H+C3H7COOOH 5.700×108 1 12581.78 R37C4H8OOOOH → R2O34 R37C4H8OOOOH OOH → R2OH+C3H7CO 9.900×107 1 10065.43 35 R39C4H8OOOOH OH → R2OH+C3H7COO 1.700×109 1 13839.96 36 R39C4H8OOOOH OH 8 → R2OH+C3H7COO 5.700×108 1 12581.737 R39C4H8OOOOH → R2OH+C3H7COOOH 1.500×108 1 12581.78 38 R40C4H8OOOOH OOOH → R2OH+C3H7C 1.700×109 1 13839.9639 R40C4H8OOOOH OOOH → R2OH+C3H7C 8.600×108 1 14091.6 40 R41C4H8OOOOH OH → R2OH+C3H7COO 3.300×109 1 16356.3241 R41C4H8OOOOH OOOH → R2OH+C3H7C 2.900×108 1 10065.4342 R41C4H8OOOOH OH → R2OH+C3H7COO 1.500×108 1 12581.7843 R42C4H8OOOOH → R2OH+C3H7COOOH 8 5.700×108 1 12581.744 R20C4H9 → R11C2H5+C2H4Z 9 2.000×1013 0 14443.845 R21C4H9 → R4CH3+C3H6Y 2.000×1013 0 15601.41 46 R21C4H9 → R1H+C4H8Y 3.000×1013 0 19124.31 47 R21C4H9 → R1H+C4H8Y 3.000×1013 0 19627.58 48 R30C4H8OOH → R3OOH+C4H8Y 8.500×1012 0 13085.05 49 R31C4H8OOH → R3OOH+C4H8Y 8.500×1012 0 13085.05 50 R31C4H8OOH → R4CH3+C3H5OOHZ 2.000×1013 0 15601.4151 R38C4H8OOH → R2OH+C3H7CHO 1.000×109 0 3774.53 52 R28C4H8OOH → R2OH+HCHO+C3H6Y 2.000×1013 0 14443.89 53 R32C4H8OOH → R2OH+CH3CHO+C2H4Z 1 2.000×1013 0 13940.654 R30C4H8OOH → R2OH+R13CH2CHO+R11C2H5 9 2.000×1013 0 14443.855 R38C4H8OOH → R2OH+R13CH2CHO+R11C2H5 9 2.000×1013 0 14443.856 R28C4H8OOH → R2OH+C4H8O#4 9.200×1010 0 8354.3 57 R29C4H8OOH → R2OH+C4H8O#5 3.600×109 0 3522.9 58 R30C4H8OOH → R2OH+C4H8O#3 6.100×1011 0 9033.72 59 R31C4H8OOH → R2OH+C4H8O#3 6.100×1011 0 9033.72 60 R32C4H8OOH → R2OH+C4H8O#4 9.200×1010 0 8354.3

46

61 R20C4H9+O2 → C4H8Y+R3OOH 2.109×10-12 0 2516.36 62 R21C4H9+O2 → C4H8Y+R3OOH 2.109×10-12 0 2516.36 63 R21C4H9+O2 → C4H8Y+R3OOH 8.966×10-13 0 2516.36 64 B1O+C4H10-1 → R2OH+R20C4H9 1.660×10-10 0 3950.68 65 B1O+C4H10-1 → R2OH+R21C4H9 8.634×10-11 0 2617.01 66 C4H10-1+R1H → H2+R20C4H9 9.464×10-17 2 3875.19 67 C4H10-1+R1H → H2+R21C4H9 2.989×10-17 2 2516.36 68 C4H10-1+R2OH → H2O+R20C4H9 8.966×10-18 2 226.47 69 C4H10-1+R2OH → H2O+R21C4H9 8.634×10-18 2 -385 70 C4H10-1+R3OOH C4H9 → H2O2+R20 1.992×10-12 0 8555.61 71 C4H10-1+R3OOH C4H9 → H2O2+R21 1.328×10-12 0 7800.7 72 C4H10-1+R4CH3 9 26.82 → CH4+R20C4H 9.962×10-25 4 4173 0 4831.4 C4H10-1+R4CH3 → CH4+R21C4H9 6.641×10-13

74 → CH3OH+R20C4H9 5.313×10-13 0 3673.88 C4H10-1+R7CH3O 75 C4H10-1+R7CH3O → CH3OH+R21C4H9 -134.815×10 0 2264.72 76 C4H10-1+R8CH3OO 1C4H9 9.962×10→ CH3OOH+R2 -12 0 8807.25 77 0 8807.25 C4H10-1+R23C4H9OO → C4H9OOH+R21C4H9 9.962×10-12

78 C4H9OOH+R20C4H9 1.992×10-11 0 10065.43 C4H10-1+R24C4H9OO →79 C4H10-1+R24C4H9OO → C4H9OOH+R21C4H9 -129.962×10 0 8807.25 80 R23C4H9OO+R3OOH 2 → C4H9OOH+O 3.321×10-13 0 -654.25 81 R24C4H9OO+R3OOH → C4H9OOH+O2 3.321×10-13 0 -654.25 82 C4H9OOH → R2OH+CH3CHO+R11C2H5 9 1.500×1016 0 21137.383 C4H7OOHY → R2OH+CH3CHO+R10C2H3V 1.500×1016 0 21137.39 84 C3H5OOHY → R2OH+HCHO+R10C2H3V 1.500×1016 0 21137.39 85 C3H7COOOH → R2OH+HCHO+B2CO+R11C2H5 1.500×1016 0 21137.39 86 C4H8O#3+R1H → H2+CH2COZ+R11C2H5 16.36 4.483×10-17 2 2587 C4H8O#3+R2OH → H2O+CH2COZ+R11C2H5 5 1.295×10-17 2 -3888 C4H8O#3+B1O → R2OH+R13CH2CHO+C2H4Z 17.01 1.295×10-10 0 2689 C4H8O#4+R1H → H2+ZC4H7O#4 4.483×10-17 2 2516.36 90 C4H8O#4+R2OH → H2O+ZC4H7O#4 1.295×10-17 2 -385 91 C4H8O#5+R1H → H2+ZC4H7O#5 4.483×10-17 2 2516.36 92 C4H8O#5+R2OH → H2O+ZC4H7O#5 1.295×10-17 2 -385 93 ZC4H7O#4 → R13CH2CHO+C2H4Z 5.000×1013 0 14494.21 94 ZC4H7O#5 → R13CH2CHO+C2H4Z 5.000×1013 0 14494.2195 ZC4H7O#4+O2 → ZOOC4H7O#4 4.981×10-5 -2.5 0 96 ZC4H7O#5+O2 → ZOOC4H7O#5 4.981×10-5 -2.5 0 97 ZOOC4H7O#4 → ZC4H7O#4+O2 5.000×1022 -2.5 20130.85 98 ZOOC4H7O#4 → ZC4H6O#4OOH 8.000×1013 0 12833.4299 ZOOC4H7O#5 → ZC4H6O#5OOH 8.000×1013 0 12833.42 100 ZC4H6O#4OOH → ZOOC4H7O#4 4.800×1012 0 9562.15 101 ZC4H6O#5OOH → ZOOC4H7O#5 4.800×1012 0 9562.15 102 ZC4H6O#4OOH+O2 H → ZOOC4H6O#4OO 4.981×10-5 -2.5 0 103 ZC4H6O#5OOH+O2 → ZOOC4H6O#5OOH 4.981×10-5 -2.5 0 104 ZOOC4H6O#4OOH → ZC4H6O#4OOH+O2 5.000×1022 -2.5 20130.85 105 ZOOC4H6O#4OOH → R2OH+C3H5O#4COOOH 1.000×109 0 3774.53 106 ZOOC4H6O#5OOH → R2OH+C3H5O#5COOOH 1.000×109 0 3774.53 107 C3H5O#4COOOH → R2OH+CO2+R5CHO+C2H4Z 1.500×1016 0 21137.39108 C3H5O#5COOOH → R2OH+CO2+R5CHO+C2H4Z 1.500×1016 0 21137.39109 C4H8Y+R1H → C2H4Z+R11C2H5 1.195×10-11 0 1459.49 110 C3H6Y+R2OH → R4CH3+CH3CHO 2.324×10-12 0 -452.94 111 C4H8Y+R2OH → R4CH3+C2H5CHO 2.324×10-12 0 -452.94 112 C3H6Y+R2OH → HCHO+R11C2H5 2.324×10-12 0 -452.94

47

113 C4H8Y+R2OH → HCHO+R4CH3+C2H4Z 2.324×10-12 0 -452.94 114 C3H6Y+B1O → CH2COZ+R4CH3+R1H 5.645×10-17 1.83 276.8 115 C4H8Y+B1O → CH2COZ+R11C2H5+R1H 5.645×10-17 1.83 276.8 116 C4H8Y+R3OOH → R2OH+C4H8O#3 1.660×10-12 0 7247.11 117 C3H6Y+R1H → ZC3H5Y+H2 9.464×10-20 2.5 145.95 118 C3H6Y+R2OH → ZC3H5Y+H2O 4.981×10-20 2 -762.46 119 C4H8Y+R1H → ZC4H7Y+H2 9.464×10-20 2.5 145.95 120 C4H8Y+R2OH → ZC4H7Y+H2O 4.981×10-18 2 -762.46 121 C4H8Y+R3OOH → ZC4H7Y+H2O2 1.046×10-20 2.6 6240.56 122 C2H5CHO+R1H → H2+ZCOC2H5 6.641×10-11 0 2113.74 123 C2H5CHO+R2OH → H2O+ZCOC2H5 6.973×10-12 0 251.64 124 C2H5CHO+R3OOH → H2O2+ZCOC2H5 1.660×10-12 0 5032.71 125 C2H5CHO+R4CH3 → CH4+ZCOC2H5 3.321×10-30 5.6 1258.18 126 ZCOC2H5 → B2CO+R11C2H5 2.000×1013 0 14443.89 127 ZCOC2H5+O2 → ZCOOOC2H5 4.981×10-5 -2.5 0 128 ZC3H5Y+R3OOH → C3H5OOHY 8.302×10-12 0 0 129 ZC3H5Y+R4CH3 → C4H8Y 1.660×10-11 0 0 130 ZC4H7Y+R3OOH → C4H7OOHY 8.302×10-12 0 0 131 ZC4H7Y+R4CH3 → C5H10Y 1.660×10-11 0 0 132 ZC4H7Y+R8CH3OO → C5H10OOY 1.660×10-11 0 0 133 ZC4H7Y+R11C2H5 → C6H12Y 1.660×10-11 0 0 134 2ZC3H5Y → C6H10Y2 1.660×10-11 0 0 135 ZC3H5Y+ZC4H7Y → C7H12Y2 1.660×10-11 0 0 136 2ZC4H7Y → C8H14Y2 1.660×10-11 0 0 137 2R4CH3(+M) → C2H6(+M) 5.994×10-11 0 0 O2/ / B2 5/ 4 /0.4/ HE/0

/ 1.0TR / 0.6

0.4 CO/0.75/ CO2/1.5/ H2O/6. CH /3/ C2H6/3/ AR/0.34/ N2 .34/ LOW 00×10-6 -7 1389.03 /

OE 2 73 1180 / 138 R11C2H5+R1H → 2R4CH3 2.188×10-7 -0.6903 1195.51 139 R1H+R4CH3(+M) → CH4(+M) 2.773×10-10 0 0 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 3.881×10-24 -1.8 0 / TROE / 0.37 3315 61 /

140 R11C2H5(+M) → C2H4Z+R1H(+M) 8.200×1013 0 20130.85 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 5.645×10-7 0 16809.26 / TROE / 0.75 97 1379 /

141 C2H4Z+R1H(+M) → R11C2H5(+M) 2.654×10-10 -0.0932 2046.06 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 1.827×10-30 -0.09 -1275.53 / TROE / 0.75 97 1379 /

142 R11C2H5+R1H → C2H6 5.977×10-11 0 0 143 C2H6+R1H → R11C2H5+H2 2.324×10-15 1.5 3724.21 144 B1O+H2 → R2OH+R1H 8.468×10-20 2.67 3120.28 145 B1O+R4CH3 → HCHO+R1H 1.395×10-10 0 0 146 B1O+C2H4Z → R4CH3+R5CHO 1.345×10-17 1.88 100.65 147 B1O+C2H4Z → R13CH2CHO+R1H 7.803×10-18 1.88 100.65 148 B1O+C2H4Z → R2OH+R10C2H3V 2.490×10-17 1.91 1862.1 149 B1O+C2H6 → R11C2H5+R2OH 1.660×10-15 1.5 2918.97 150 R2OH+H2 → R1H+H2O 1.660×10-16 1.6 1660.8 151 R1H+H2O → R2OH+H2 1.434×10-15 1.5259 9400.56 152 R2OH+R4CH3(+M) → CH3OH(+M) 9.962×10-11 0 0 LOW / 3.859×10-4 -8.2 0 /

TROE / 0.82 200 1438 /

48

153 R7CH3O+R1H → R2OH+R4CH3 1.023×10-8 -0.5465 929.91 154 R2OH+C2H4Z → R10C2H3V+H2O 3.321×10-11 0 2969.3 155 R2OH+C2H4Z → R4CH3+HCHO 3.321×10-12 0 452.94 156 R2OH+R11C2H5 → C2H4Z+H2O 3.985×10-11 0 0 157 R2OH+R11C2H5 → R4CH3+R1H+HCHO 3.985×10-11 0 0 158 R2OH+C2H6 → R11C2H5+H2O 1.195×10-17 2 452.94 159 2R2OH → H2O+B1O 2.490×10-15 1.14 50.33 160 H2O+B1O → 2R2OH 3.194×10-14 1.1275 8741.48 161 R14CH3CO(+M) → B2CO+R4CH3(+M) 7.551×1014 -0.4943 8654.1 LOW / 2.758×10-7 -0.49 7093.96 /

TROE / 0.5 1 1.000×108 / 162 B2CO+B1O+M → CO2+M 4.245×10-33 0 1509.81 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ 163 B2CO+R2OH → CO2+R1H 1.046×10-17 1.5 -251.64 164 R5CHO+M → R1H+B2CO+M 3.155×10-7 -1 8555.61 H2/2/ B2CO/1.5/ CO2/2/ H2O/6/ 165 R1H+B2CO+M → R5CHO+M 4.245×10-31 -0.9364 280.34 H2/2/ B2CO/1.5/ CO2/2/ H2O/6/ 166 R5CHO+R1H → H2+B2CO 1.494×10-10 0 0 167 R11C2H5+HCHO → R5CHO+C2H6 9.248×1 2949.17 0-21 2.81168 R5CHO+B1O → R1H+CO2 4.981×10-11 0 0 169 R5CHO+B1O → R2OH+B2CO 4.981×10-11 0 0 170 R5CHO+R2OH → H2O+B2CO 1.826×10-10 0 0 171 HCHO+R1H → R5CHO+H2 2.158×10-16 1.62 1056.87 172 HCHO+B1O → R5CHO+R2OH 6.807×10-13 0.57 1358.83 173 HCHO+R2OH → R5CHO+H2O 5.645×10-15 1.18 -201.31 174 R7CH3O+M → HCHO+R1H+M 2.573×10-10 0 6794.16 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ 175 R7CH3O+R1H → HCHO+H2 2.989×10-11 0 0 176 R7CH3O+R11C2H5 → HCHO+C2H6 3.985×10-11 0 0 177 R7CH3O+R2OH → HCHO+H2O 2.989×10-11 0 0 178 R7CH3O+B2CO → R4CH3+CO2 2.656×10-11 0 5888.27 179 R7CH3O+HCHO → CH3OH+R5CHO 1.660×10-13 0 1509.81 180 2R7CH3O → CH3OH+HCHO 9.962×10-11 0 0 181 CH3OH+R1H → R4CH3+H2O 3.321×10-10 0 2667.34 182 CH3OH+R1H → R7CH3O+H2 6.973×10-18 2.1 2466.03 183 R7CH3O+H2 → CH3OH+R1H 7.033×10-20 2.6598 2057.33 184 CH3OH+R2OH → R7CH3O+H2O 8.966×10-19 2 -171.11 185 CH2COZ+R1H → R4CH3+B2CO 2.989×10-11 0 1711.12 186 CH2COZ+B1O → B5CH2+CO2 2.989×10-12 0 654.25 187 CH2COZ+R2OH → R4CH3+CO2 4.184×10-12 0 0 188 R13CH2CHO → R1H+CH2COZ 1.600×1013 0 17614.49 189 R1H+CH2COZ → R13CH2CHO 8.042×10-18 1.8894 -539.03 190 CH3CHO+R1H → H2+R14CH3CO 6.641×10-11 0 2113.74 191 CH3CHO+B1O → R14CH3CO+R2OH 2.324×10-11 0 1157.52 192 CH3CHO+R2OH → R14CH3CO+H2O 6.973×10-12 0 251.64 193 CH3CHO+R7CH3O → R14CH3CO+CH3OH 3.985×10-13 0 905.89 194 C2H4O#3 → CH3CHO 7.300×1013 0 28787.12 195 C2H4O#3 → R4CH3+R5CHO 3.600×1013 0 28787.12 196 C2H4O#3+R2OH → H2O+R13CH2CHO 2.989×10-11 0 1811.78 197 R15C2H5O → HCHO+R4CH3 8.000×1013 0 10820.33 198 R15C2H5O → CH3CHO+R1H 2.000×1014 0 11726.22 199 CH3CHO+R1H → R15C2H5O 3.705×10-14 0.8797 3126.09

49

200 R11C2H5+R2OH(+M) → C2H5OH(+M) 3.882×10-8 -0.327 770.05 CO2/3/ H2O/5/ B2CO/2/ H2/2/

LOW / 1.719×1031 -17.6 10281.88 / TROE / 0.5 300 900 5000 /

201 C2H5OH+R2OH → H2O+R15C2H5O 1.245×10-12 0.3 805.23 202 C2H5OH+R1H → H2+CH3CHO+R1H 4.317×10-17 1.65 1409.16 203 C2H5OH+R2OH → H2O+CH3CHO+R1H 7.637×10-13 0.15 0 204 C2H5OH+R3OOH → H2O2+CH3CHO+R1H 1.361×10-20 2.55 5385 205 O2+R1H → R2OH+B1O 1.627×10-10 0 7448.41 206 R2OH+B1O → O2+R1H 4.180×10-13 0.4032 -1248.65 207 O2+R1H(+M) → R3OOH(+M) 7.505×10-11 0 0 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/0/ CH4/3/ C2H6/3/ AR/0.28/ HE/0.34/ N2/0.67/

LOW / 4.962×10-30 -0.8 0 / TROE / 0.5 1 1.000×108 /

208 O2+R1H(+H2O) → R3OOH(+H2O) 7.505×10-11 0 0 LOW / 1.902×10-32 0 -1046.8 /

TROE / 0.45 1 1.000×108 / 209 O2+B5CH2 → R5CHO+R2OH 7.139×10-14 0 -251.64 210 O2+B5CH2 → CO2+2R1H 2.656×10-12 0 503.27 211 O2+B5CH2 → HCHO+B1O 1.660×10-10 0 2264.72 212 O2+R4CH3(+M) → R8CH3OO(+M) 1.295×10-15 1.2 0 LOW / 1.544×10-22 -3.3 0 /

TROE / 0.36 1 1.000×108 / 213 R8CH3OO(+M) → O2+R4CH3(+M) 7.060×1015 -0.3397 15482.06 LOW / 8.418×108 -4.84 15482.06 /

TROE / 0.36 1 1.000×108 / 214 O2+R4CH3 → R7CH3O+B1O 2.158×10-10 0 15752.39 215 O2+R4CH3 → HCHO+R2OH 4.981×106 -4.69 18419.73 216 O2+R10C2H3V → HCHO+R5CHO 7.471×10-8 -1.39 503.27 217 O2+R10C2H3V → B1O+R13CH2CHO 5.479×10-13 -0.29 5.03 218 O2+R11C2H5 → R17C2H5OO 3.653×10-14 0.77 -301.96 219 R17C2H5OO → O2+R11C2H5 1.296×1018 -0.8654 16369.22 220 O2+R11C2H5 → C2H4Z+R3OOH 1.395×10-12 0 1962.76 221 C2H4Z+R3OOH → O2+R11C2H5 4.833×10-11 -0.3898 8714.45 222 O2+R11C2H5 → CH3CHO+R2OH 9.962×10-14 0 3472.57 223 R11C2H5+R3OOH → O2+C2H6 1.071×10-12 0.0084 163.44 224 R3OOH+B1O → O2+R2OH 4.644×10-5 -0.6024 139.75 225 O2+R5CHO → B2CO+R3OOH 1.262×10-11 0 206.34 226 O2+R7CH3O → HCHO+R3OOH 3.653×10-14 0 855.56 227 O2+R14CH3CO → R18CH3COOO 3.985×10-12 0 0 228 R18CH3COOO → O2+R14CH3CO 1.612×1023 -2.3641 21764.8 229 O2+R13CH2CHO → HCHO+R2OH+B2CO 9.796×10-15 0 -704.58 230 O2+R13CH2CHO → CH2COZ+R3OOH 1.660×10-14 0 -704.58 231 O2+CH3CHO → R14CH3CO+R3OOH 8.302×10-11 0 18319.07 232 R14CH3CO+R3OOH → O2+CH3CHO 4.441×10-12 0.0119 -1786.55 233 R13CH2CHO+R3OOH → O2+CH3CHO 9.500×10-4 -2.2051 -98.75 234 O2+R15C2H5O → CH3CHO+R3OOH 9.962×10-14 0 855.56 235 R3OOH+R1H → H2+O2 7.139×10-11 0 704.58 236 R3OOH+R1H → 2R2OH 2.823×10-10 0 452.94 237 R3OOH+R1H → H2O+B1O 4.981×10-11 0 855.56 238 R3OOH+R4CH3 → R7CH3O+R2OH 2.989×10-11 0 0 239 R3OOH+R10C2H3V → R2OH+R4CH3+B2CO 4.981×10-11 0 0 240 R3OOH+C2H4Z → CH3CHO+R2OH 9.962×10-15 0 3975.84

50

241 R3OOH+C2H4Z → C2H4O#3+R2OH 3.653×10-12 0 8656.27 242 R3OOH+R11C2H5 → R4CH3+HCHO+R2OH 3.985×10-11 0 0 243 R3OOH+R2OH → H2O+O2 4.815×10-11 0 -251.64 244 R3OOH+B2CO → CO2+R2OH 2.490×10-10 0 11877.2 245 R3OOH+R5CHO → R2OH+R1H+CO2 4.981×10-11 0 0 246 R3OOH+HCHO → R5CHO+H2O2 4.981×10-12 0 6542.53 247 R3OOH+R7CH3O → HCHO+H2O2 4.981×10-13 0 0 248 R3OOH+R14CH3CO → R4CH3+CO2+R2OH 4.981×10-11 0 0 249 R3OOH+CH3CHO → R14CH3CO+H2O2 1.660×10-12 0 5032.71 250 2R3OOH → H2O2+O2 2.158×10-13 0 -820.33 251 2R3OOH → H2O2+O2 6.973×10-10 0 6029.19 252 2R2OH(+M) → H2O2(+M) 1.200×10-10 -0.37 0 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 1.524×10-28 -0.76 0 / TROE / 0.5 1 1.000×108 /

253 H2O2(+M) → 2R2OH(+M) 3.000×1014 0 24408.66 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 4.981×108 0 22898.84 / TROE / 0.5 1 1.000×108 /

254 H2O2+R1H → H2+R3OOH 2.823×10-12 0 1862.1 255 H2O2+R1H → H2O+R2OH 1.660×10-11 0 1811.78 256 H2O2+R2OH → H2O+R3OOH 1.295×10-11 0 654.25 257 R8CH3OO+R1H → R7CH3O+R2OH 1.594×10-10 0 0 258 R8CH3OO+R4CH3 → 2R7CH3O 8.302×10-12 0 -704.58 259 R8CH3OO+C2H4Z → R7CH3O+C2H4O#3 1.826E-09 0 10065.43 260 R8CH3OO+R11C2H5 → R7CH3O+R15C2H5O 3.985×10-11 0 0 261 R8CH3OO+R2OH → CH3OH+O2 9.962×10-11 0 0 262 R8CH3OO+R2OH → R7CH3O+R3OOH 4.981×10-12 0 0 263 R8CH3OO+R5CHO → R7CH3O+R1H+CO2 4.981×10-11 0 0 264 R8CH3OO+HCHO → CH3OOH+R5CHO 1.660×10-12 0 6089.58 265 R8CH3OO+R7CH3O → HCHO+CH3OOH 4.981×10-13 0 0 266 R8CH3OO+R14CH3CO → R4CH3+CO2+R7CH3O 3.985×10-11 0 0 267 R8CH3OO+CH3CHO → CH3OOH+R14CH3CO 1.660×10-12 0 6089.58 268 R8CH3OO+R3OOH → CH3OOH+O2 4.151×10-13 0 -805.23 269 R8CH3OO+R3OOH → O2+HCHO+H2O 8.302×10-14 0 0 270 R8CH3OO+H2O2 → CH3OOH+R3OOH 3.985×10-12 0 4982.39 271 CH3OOH+R3OOH → R8CH3OO+H2O2 7.326×10-12 -0.2231 5308.69 272 2R8CH3OO → CH3OH+HCHO+O2 4.151×10-14 0 -402.62 273 2R8CH3OO → 2R7CH3O+O2 4.151×10-14 0 -402.62 274 CH3OOH → R7CH3O+R2OH 6.000×1014 0 21288.38 275 R7CH3O+R2OH → CH3OOH 3.586×10-18 2.1584 -1872.68 276 CH3OOH+R2OH → H2O+R8CH3OO 2.989×10-12 0 -186.21 277 C2H5OOH+R1H → R17C2H5OO+H2 4.378×10-10 -0.5218 2040.25 278 R17C2H5OO+R4CH3 → R15C2H5O+R7CH3O 3.321×10-12 0 -603.93 279 R17C2H5OO+C2H4Z → R15C2H5O+C2H4O#3 3.819×10-8 0 11021.64 280 C2H5OOH+R2OH → R17C2H5OO+H2O 3.592×10-11 -0.4477 -868.11 281 R17C2H5OO+HCHO → C2H5OOH+R5CHO 7.471×10-12 0 7247.11 282 C2H5OOH+R7CH3O → R17C2H5OO+CH3OH 1.565×10-13 0.038 323.04 283 R17C2H5OO+CH3CHO → C2H5OOH+R14CH3CO 6.475×10-12 0 7247.11 284 R17C2H5OO+R3OOH → O2+C2H5OOH 6.475×10-13 0 -654.25 285 R17C2H5OO+R8CH3OO → R15C2H5O+R7CH3O+O2 3.321×10-13 0 0 286 2R17C2H5OO → 2R15C2H5O+O2 6.807×10-14 0 100.65 287 2R17C2H5OO → C2H5OH+CH3CHO+O2 2.989×10-14 0 100.65

51

288 C2H5OOH → R15C2H5O+R2OH 4.000×1015 0 21590.34 289 R15C2H5O+R2OH → C2H5OOH 2.084×10-15 1.441 -1013.41 290 C2H5OOH+R1H → CH3CHO+R2OH+H2 5.313×10-11 0 3875.19 291 C2H5OOH+R4CH3 → CH3CHO+R2OH+CH4 9.464×10-13 0 4378.46 292 C2H5OOH+R2OH → CH3CHO+R2OH+H2O 9.796×10-12 0 452.94 293 C2H5OOH+R7CH3O → CH3CHO+R2OH+CH3OH 1.046×10-12 0 2767.99 294 C2H5OOH+R17C2H5OO → CH3CHO+R2OH+C2H5OOH 1.826×10-12 0 8404.63 295 R18CH3COOO+C2H5OOH → CH3CHO+R2OH+CH3COOOH 8.302×10-13 0 4630.1 296 2R18CH3COOO → 2R4CH3+O2+2CO2 2.823×10-12 0 -503.27 297 C2H4Z+R4CH3 → R19C3H7 3.487×10-13 0 3699.04 298 R11C2H5+C2H4Z → R20C4H9 1.826×10-13 0 3673.88 299 R11C2H5+R10C2H3V → C4H8Y 2.490×10-11 0 0 300 R5CHO+R10C2H3V → C2H3CHOZ 2.989×10-11 0 0 c) Cyclohexane oxidation reduced to 48-99 species in 157-238 reactions Reactions labeled ● are present in the 99 species 238 reactions mechanism. Reactions labeled † are present in the 59 species 238 reactions mechanism. Reactions labeled * are present in the 48 species 157 reactions mechanism. # Reactions A E n ● † * 1 C6H12#6+O2 → RC1ZC6H11#6+R3OOH 1.378×10-10 0 25598.75 ● † * 2 RC1ZC6H11#6+O2 → RC2ZOOC6H11#6 9.963×10-6 -2.5 0 ● † * 3 RC2ZOOC6H11#6 → RC1ZC6H11#6+O2 1.826×1029 -4.9958 19307.39 ● † 4 RC3ZC5H9#6OOH+O2 → RC7OOC6H10#6OOH 9.963×10-6 -2.5 0 ● † 5 RC7OOC6H10#6OOH → RC3ZC5H9#6OOH+O2 2.518×1029 -4.4523 18604.44 ● † 6 RC4ZC5H9#6OOH+O2 → RC8OOC6H10#6OOH 5.812×10-6 -2.5 0 ● 7 RC8OOC6H10#6OOH → RC4ZC5H9#6OOH+O2 2.386×1027 -4.4164 18886.49 ● † 8 RC5ZC5H9#6OOH+O2 → RC9OOC6H10#6OOH 9.963×10-6 -2.5 0 ● † 9 RC9OOC6H10#6OOH → RC5ZC5H9#6OOH+O2 4.091×1027 -4.4164 18886.49 ● † * 10 RC6ZC5H9#6OOH+O2 → RCDOOC6H10#6OOH 9.963×10-6 -2.5 0 ● † 11 RCDOOC6H10#6OOH → RC6ZC5H9#6OOH+O2 4.091×1027 -4.4164 18886.49 ● 12 R21C6H11Z+O2 → R29C6H11OOZ 1.494×10-5 -2.5 0 ● 13 R29C6H11OOZ → R21C6H11Z+O2 8.551×1026 -4.2071 17381.19 ● 14 R22C6H11X+O2 → R45C6H11OOZ 1.993×10-14 0 -1157.4 ● 15 R45C6H11OOZ → R22C6H11X+O2 1.853×1019 -2.3401 9231.73 ● 16 R22C6H11X+O2 → R46C6H11OOZ 1.993×10-14 0 -1157.4 ● 17 R46C6H11OOZ → R22C6H11X+O2 1.145×1018 -1.8147 8233.35 ● † * 18 R106C5H10CHO+O2 → R107C5H10CHOOO 1.494×10-5 -2.5 0 ● † * 19 R107C5H10CHOOO → R106C5H10CHO+O2 4.424×1026 -4.0817 16518.31 ● † * 20 R37C3H5Y+O2 → R132C3H5OOZ 1.993×10-14 0 -1157.4 ● † * 21 R132C3H5OOZ → R37C3H5Y+O2 8.497×1016 -1.5671 8924.44 ● 22 R43C6H10OOHX+O2 → R118C6H10OOOOHZ 1.993×10-14 0 -1157.4 ● 23 R118C6H10OOOOHZ → R43C6H10OOHX+O2 1.881×1019 -2.3384 9231 ● 24 R43C6H10OOHX+O2 → R119C6H10OOOOHZ 1.993×10-14 0 -1157.4 ● 25 R119C6H10OOOOHZ → R43C6H10OOHX+O2 2.275×1018 -1.81 8230.44 ● 26 R120C6H10OOHZ+O2 → R233C6H10OOOOHZ 1.661×10-5 -2.5 0 ● 27 R233C6H10OOOOHZ → R120C6H10OOHZ+O2 7.324×1027 -4.157 17500.18 ● 28 R133C6H10OOHZ+O2 → R247C6H10OOOOHZ 1.494×10-5 -2.5 0 ● 29 R247C6H10OOOOHZ → R133C6H10OOHZ+O2 7.700×1028 -4.6512 13922.99 ● † 30 R116C5H9CHOOOH+

O2 → R121C5H9CHO3HOO

1.744×10-5-2.5 0

52

● † 31 R121C5H9CHO3HOO → R116C5H9CHOOOH+O2 5.144×1026 -4.3515 14798.17 ● † * 32 R117C5H9CHOOOH+

O2 → R133C5H9CHO3HOO

1.494×10-5-2.5 0

● † * 33 R133C5H9CHO3HOO → R117C5H9CHOOOH+O2 4.319×1028 -4.3526 18246.92 ● † 34 RC2ZOOC6H11#6 → RC3ZC5H9#6OOH 9.700×109 1 17612.66 ● † 35 RC2ZOOC6H11#6 → RC4ZC5H9#6OOH 3.900×1010 1 17756.08 ● † 36 RC2ZOOC6H11#6 → RC5ZC5H9#6OOH 3.900×1010 1 16505.58 ● † * 37 RC2ZOOC6H11#6 → RC6ZC5H9#6OOH 9.700×107 1 12860.26 ● 38 R21C6H11Z → R22C6H11X 5.700×108 1 7196.03 ● 39 R22C6H11X → R21C6H11Z 1.542×109 1.1397 15958.08 ● 40 R29C6H11OOZ → R43C6H10OOHX 9.900×107 1 9812.77 ● 41 R38C6H10OOHZ → R43C6H10OOHX 5.700×108 1 9460.52 ● 42 R39C6H10OOHZ → R69C6H10OOHX 5.700×108 1 6441.2 ● 43 R43C6H10OOHX → R78C6H10OOHX 3.300×109 1 10768.89 ● 44 R78C6H10OOHX → R43C6H10OOHX 7.010×108 1.3133 12539.98 ● 45 R43C6H10OOHX → R121C6H10OOHX 3.300×109 1 10768.89 ● 46 R121C6H10OOHX → R43C6H10OOHX 7.010×108 1.3133 12541.4 ● 47 R46C6H11OOZ → R85C6H10OOHX 5.700×108 1 9309.55 ● 48 R46C6H11OOZ → R86C6H10OOHZ 9.900×107 1 8554.72 ● 49 R59C6H10OOHX → R110C6H11OOZ 2.900×108 1 16807.51 ● 50 R110C6H11OOZ → R59C6H10OOHX 1.109×1012 0.3131 12745.65 ● 51 R59C6H10OOHX → R111C6H10OOHX 3.300×109 1 10768.89 ● 52 R111C6H10OOHX → R59C6H10OOHX 9.387×1010 0.7006 7530.2 ● 53 R59C6H10OOHX → R112C6H10OOHZ 5.700×108 1 11272.1 ● 54 R112C6H10OOHZ → R59C6H10OOHX 4.917×109 0.637 1100.54 ● 55 R59C6H10OOHX → R85C6H10OOHX 3.300×109 1 13788.2 ● 56 R85C6H10OOHX → R59C6H10OOHX 4.020×109 1.1362 10927.62 ● 57 R86C6H10OOHZ → R59C6H10OOHX 3.846×107 1.2362 3189.98 ● 58 R69C6H10OOHX → R119C6H10OOHX 1.700×109 1 8756.01 ● 59 R119C6H10OOHX → R69C6H10OOHX 1.636×108 1.4582 11844.19 ● 60 R69C6H10OOHX → R120C6H10OOHZ 5.700×108 1 11272.1 ● 61 R120C6H10OOHZ → R69C6H10OOHX 7.586×107 1.115 4295.12 ● 62 R78C6H10OOHX → R85C6H10OOHX 3.300×109 1 10768.89 ● 63 R85C6H10OOHX → R78C6H10OOHX 3.783×1010 0.762 10251.18 ● 64 R78C6H10OOHX → R133C6H10OOHZ 5.700×108 1 10265.67 ● 65 R133C6H10OOHZ → R78C6H10OOHX 5.942×107 1.0279 3959.43 ● 66 R85C6H10OOHX → R121C6H10OOHX 3.300×109 1 10768.89 ● 67 R121C6H10OOHX → R85C6H10OOHX 2.879×108 1.238 11288.01 ● 68 R111C6H10OOHX → R119C6H10OOHX 3.300×109 1 10768.89 ● 69 R121C6H10OOHX → R133C6H10OOHZ 5.700×108 1 10265.67 ● 70 R133C6H10OOHZ → R121C6H10OOHX 5.942×107 1.0279 3958.01 ● † * 71 R107C5H10CHOOO → R108C5H9CHOOOH 3.300×109 1 16354.62 ● † * 72 R107C5H10CHOOO → R109C5H9CHOOOH 5.700×108 1 12580.47 ● † * 73 R109C5H9CHOOOH → R107C5H10CHOOO 1.071×106 1.3391 5978.24 ● † * 74 R107C5H10CHOOO → R110C5H9CHOOOH 9.900×107 1 11070.82 ● † * 75 R110C5H9CHOOOH → R107C5H10CHOOO 1.861×105 1.3391 4468.59 ● † * 76 R107C5H10CHOOO → R116C5H9CHOOOH 1.700×107 1 10567.6 ● † * 77 R116C5H9CHOOOH → R107C5H10CHOOO 8.182×106 0.8679 7631.81 ● † * 78 R108C5H9CHOOOH → R116C5H9CHOOOH 5.700×108 1 8705.69 ● † * 79 R116C5H9CHOOOH → R108C5H9CHOOOH 1.459×1011 0.5288 12372.13 ● † * 80 R116C5H9CHOOOH → R117C5H9CHOOOH 9.900×107 1 5535.41 ● † * 81 R117C5H9CHOOOH → R116C5H9CHOOOH 3.470×105 1.488 5034.91 ● † * 82 R117C5H9CHOOOH → R110C5H9CHOOOH 5.700×108 1 8705.69 ● † * 83 R110C5H9CHOOOH → R117C5H9CHOOOH 6.351×108 0.9832 5539.76

53

● 84 R233C6H10OOOOHZ → R2OH+C5H9COOOHZ 9.900×107 1 9812.77 ● † * 85 R133C5H9CHO3HOO → R2OH+CHOC4H8COOOH 5.700×108 1 12580.47 ● † * 86 R133C5H9CHO3HOO → R2OH+CHOC4H8COOOH 9.900×107 1 11070.82 ● † * 87 R133C5H9CHO3HOO → R2OH+CHOC4H8COOOH 1.700×107 1 10567.6 ● 88 RC8OOC6H10#6OOH → R2OH+C5H9CO#6OOH 9.700×109 1 15239.99 ● 89 RC8OOC6H10#6OOH → R2OH+C5H9CO#6OOH 3.900×1010 1 16505.58 ● 90 RC8OOC6H10#6OOH → R2OH+C5H9CO#6OOH 9.700×107 1 12860.26 ● † 91 RC9OOC6H10#6OOH → R2OH+C5H9CO#6OOH 9.700×109 1 13989.49 ● † 92 RCDOOC6H10#6OOH → R2OH+C5H9CO#6OOH 3.900×1010 1 16505.58 ● † * 93 RCDOOC6H10#6OOH → R2OH+C5H9CO#6OOH 4.900×107 1 10344.17 ● 94 RC1ZC6H11#6 → R21C6H11Z 4.000×1013 0 14442.38 ● 95 R21C6H11Z → RC1ZC6H11#6 1.939×105 1.1988 2644.85 ● † * 96 R1H+C6H10Z#6 → RC1ZC6H11#6 4.317×10-11 0 785.02 ● † 97 RC1ZC6H11#6 → R1H+C6H10Z#6 2.273×1016 -0.561 17715.83 ● † 98 RC3ZC5H9#6OOH → R2OH+C5H10#6CO 1.000×1019 0 3774.14 ● 99 RC5ZC5H9#6OOH → R38C6H10OOHZ 2.000×1013 0 14442.38 ● 100 RC5ZC5H9#6OOH → R39C6H10OOHZ 2.000×1013 0 14442.38 ● † * 101 RC11OC6H11#6 → R106C5H10CHO 2.000×1013 0 7548.28 ● 102 R22C6H11X → R11C2H5+C4H6Z2 6.500×1012 0 18065.56 ● 103 R38C6H10OOHZ → R2OH+C5H9CHOZ 1.000×109 0 3774.14 ● 104 R119C6H10OOHX → R2OH+C5H10COZ 5.000×108 0 7397.32 ● † 105 RC4ZC5H9#6OOH → R2OH+C6H10#6O#3 2.060×1013 0 4871.16 ● † 106 RC5ZC5H9#6OOH → R2OH+C5H9CHOZ 2.060×1013 0 9858.06 ● † * 107 RC6ZC5H9#6OOH → R2OH+C6H10#6O#5 2.060×1013 0 8605.04 ● 108 R43C6H10OOHX → R2OH+C6H10O#5Z 1.800×109 0 3522.53 ● 109 R59C6H10OOHX → R2OH+C6H10OZ#4 7.000×1010 0 9485.68 ● 110 R69C6H10OOHX → R2OH+C6H10O#3Z 3.100×1011 0 9032.78 ● 111 R78C6H10OOHX → R2OH+C6H10O#4Z 4.600×1010 0 8353.43 ● 112 R85C6H10OOHX → R2OH+C6H10OZ#5 6.000×109 0 3069.64 ● 113 R121C6H10OOHX → R2OH+C6H10O#4Z 4.600×1010 0 8353.43 ● † * 114 RC1ZC6H11#6+O2 → C6H10Z#6+R3OOH 6.443×10-12 0 2516.09 ● 115 R22C6H11X+O2 → C6H10Z2+R3OOH 2.657×10-12 0 4991.93 ● † * 116 C6H12#6+R1H → RC1ZC6H11#6+H2 4.450×10-16 2 2516.09 ● † * 117 C6H12#6+R2OH → RC1ZC6H11#6+H2O 1.279×10-16 2 -387.48 ● † * 118 C6H12#6+R3OOH → RC1ZC6H11#6+H2O2 1.993×10-11 0 7799.89 ● † * 119 C6H12#6+

RC2ZOOC6H11#6 → RC1ZC6H11#6+C6H11#6OOH

2.989×10-110 8806.33

● † * 120 RC2ZOOC6H11#6+ R3OOH

→ C6H11#6OOH+O2 3.321×10-13

0 -654.18

● † * 121 2RC2ZOOC6H11#6 → C5H10#6CO+C6H11#6OH+O2 2.325×10-14 0 -364.83 ● † * 122 2RC2ZOOC6H11#6 → 2RC11OC6H11#6+O2 1.046×10-13 0 -364.83 ● † * 123 R37C3H5Y+R3OOH → C3H5OOHY 1.661×10-9 -0.8 0 ● † * 124 C3H5OOHY → R2OH+HCHO+R10C2H3V 1.500×1016 0 21135.2 ● † 125 C5H9CO#6OOH → R2OH+C2H4Z+CH2COZ+R13

CH2CHO 1.500×10160 21135.2

● † * 126 CHOC4H8COOOH → R2OH+3R13CH2CHO 1.500×1016 0 21135.2 ● † * 127 C6H11#6OOH → R2OH+RC11OC6H11#6 1.500×1016 0 21135.2 ● † * 128 C6H11#6OH+R1H → H2+R13CH2CHO+2C2H4Z 4.483×10-17 2 2516.09 ● † * 129 C6H11#6OH+R2OH → H2O+R13CH2CHO+2C2H4Z 1.295×10-17 2 -384.96 ● 130 C6H10#6O#5+R1H → H2+C6H9#6O#5 2.756×10-17 2 1207.73 ● 131 C6H10#6O#5+R2OH → H2O+C6H9#6O#5 7.638×10-18 2 -941.02 ● 132 C6H9#6O#5 → C5H9CO#6 2.000×1013 0 7548.28 ● 133 C5H9CO#6 → CH2COZ+C2H4Z+R10C2H3V 4.000×1013 0 14442.38 ● 134 C5H9CO#6+O2 → C5H8CO#6+R3OOH 4.151×10-11 0 2516.09

54

● † * 135 C2H3CHOZ+R1H → H2+ZCOC2H3Z 6.642×10-11 0 2113.52 ● † * 136 C2H3CHOZ+R2OH → H2O+ZCOC2H3Z 6.974×10-12 0 251.61 ● † * 137 C2H3CHOZ+R3OOH → H2O2+ZCOC2H3Z 1.661×10-12 0 5032.19 ● † * 138 C2H3CHOZ+R4CH3 → CH4+ZCOC2H3Z 3.321×10-30 5.6 1258.05 ● 139 C5H9CHOZ+R1H → H2+ZCOC5H9Z 6.642×10-11 0 2113.52 ● 140 C5H9CHOZ+R2OH → H2O+ZCOC5H9Z 6.974×10-12 0 251.61 ● 141 C5H9CHOZ+R3OOH → H2O2+ZCOC5H9Z 1.661×10-12 0 5032.19 ● 142 C5H9CHOZ+R4CH3 → CH4+ZCOC5H9Z 3.321×10-30 5.6 1258.05 ● † * 143 ZCOC2H3Z → B2CO+R10C2H3V 2.000×1013 0 8637.75 ● 144 ZCOC5H9Z → B2CO+C2H4Z+R37C3H5Y 2.000×1013 0 8637.75 ● 145 C5H8CO#6+R1H → H2+C2H2T+CH2COZ+

R10C2H3V 4.483×10-172 2516.09

● 146 C5H8CO#6+R2OH → H2O+C2H2T+CH2COZ+ R10C2H3V 1.295×10-17

2 -384.96

● 147 C6H10Z#6 → C2H4Z+C4H6Z2 1.500×1015 0 33665.35 ● † 148 C6H10Z#6+O2 → RC2C6H9#6Y+R3OOH 1.196×10-10 0 17512.02 ● † * 149 RC2C6H9#6Y+R3OOH → C6H10Z#6+O2 1.744×10-11 -0.2635 230.08 ● † * 150 C6H10Z#6+B1O → C2H3CHOZ+R1H+R37C3H5Y 1.993×10-19 2.56 -568.64 ● 151 RC1C6H9#6Z+O2 → R3OOH+C6H8#6 1.594×10-11 0 1258.05 ● 152 RC2C6H9#6Y+O2 → R3OOH+C6H8#6 1.594×10-11 0 7628.8 ● † * 153 C6H10Z#6+R1H → RC2C6H9#6Y+H2 1.827×10-19 2.5 -956.12 ● † * 154 C6H10Z#6+R2OH → RC1C6H9#6Z+H2O 8.635×10-18 2 -387.48 ● † * 155 C6H10Z#6+R2OH → RC2C6H9#6Y+H2O 9.963×10-18 2 -764.89 ● † * 156 RC2C6H9#6Y+R3OOH → R2OH+C2H4Z+B2CO+

R37C3H5Y 1.661×10-9-0.8 0

● 157 R28C6H9Y2+R3OOH → R2OH+SC3H5+C2H3CHOZ 1.661×10-9 -0.8 0 ● 158 C6H6#+R1H → C6H7#6 6.642×10-11 0 2163.84 ● 159 C6H7#6 → C6H6#+R1H 4.723×1017 -1.737 12891.43 ● 160 C6H8#6+O2 → C6H7#6+R3OOH 2.325×10-11 0 14049.87 ● 161 C6H8#6+R1H → H2+C6H7#6 1.827×10-19 2.5 -956.12 ● 162 C6H8#6+R2OH → H2O+C6H7#6 9.963×10-18 2 -764.89 ● 163 C6H8#6-14 → C6H6#+H2 2.300×1012 0 22040.99 ● 164 C6H7#6+O2 → C6H6#+R3OOH 2.657×10-12 0 1258.05 ● † * 165 2R4CH3(+M) → C2H6(+M) 5.995×10-11 0 0 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 1.000×10-6 -7 1388.88 / TROE / 0.62 73 1180 /

● 166 C2H4Z+R1H(+M) → R11C2H5(+M) 9.748×10-10 -0.274 2096.43 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 6.712×10-30 -0.27 -1224.82 / TROE / 0.75 97 1379 /

● † * 167 B1O+C2H4Z → R4CH3+R5CHO 1.345×10-17 1.88 100.64 ● † 168 R2OH+H2 → R1H+H2O 1.661×10-16 1.6 1660.62 ● † 169 R2OH+R4CH3(+M) → CH3OH(+M) 9.963×10-11 0 0 LOW / 3.860×10-4 -8.2 0 /

TROE / 0.82 200 1438 / ● † * 170 R2OH+C2H4Z → R10C2H3V+H2O 3.321×10-11 0 2968.99 ● † * 171 R2OH+C2H4Z → R4CH3+HCHO 3.321×10-12 0 452.9 ● 172 R2OH+C2H6 → R11C2H5+H2O 1.196×10-17 2 452.9 ● † * 173 R14CH3CO(+M) → B2CO+R4CH3(+M) 1.128×1016 -0.843 8949.13 LOW / 4.122×10-6 -0.84 7389.15 /

TROE / 0.5 1 1.000×108 / ● † * 174 B2CO+R2OH → CO2+R1H 1.046×10-17 1.5 -251.61 ● † * 175 R5CHO+M → R1H+B2CO+M 3.155×10-7 -1 8554.72

55

H2/2/ B2CO/1.5/ CO2/2/ H2O/6/ ● 176 R4CH3+HCHO → R5CHO+CH4 1.279×10-31 6.1 991.34 ● † 177 HCHO+R1H → R5CHO+H2 2.159×10-16 1.62 1056.76 ● † * 178 HCHO+B1O → R5CHO+R2OH 6.808×10-13 0.57 1358.69 ● † * 179 HCHO+R2OH → R5CHO+H2O 5.646×10-15 1.18 -201.29 ● † * 180 R7CH3O+M → HCHO+R1H+M 2.574×10-10 0 6793.46 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ ● † 181 CH3OH+R1H → R4CH3+H2O 3.321×10-10 0 2667.06 ● † 182 CH3OH+R2OH → R6CH2OH+H2O 5.148×10-18 2 -171.09 ● † 183 R12CHCOV+R1H+M → CH2COZ+M 1.526×10-32 -0.1442 -9485.87 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ ● † * 184 CH2COZ+R1H → R4CH3+B2CO 2.989×10-11 0 1710.94 ● † 185 CH2COZ+R2OH → R12CHCOV+H2O 1.245×10-11 0 1006.44 ● † * 186 CH2COZ+R2OH → R4CH3+CO2 4.185×10-12 0 0 ● † * 187 CH2COZ+R2OH → R6CH2OH+B2CO 7.771×10-12 0 0 ● † 188 R13CH2CHO → R1H+CH2COZ 1.600×1013 0 17612.66 ● † * 189 R1H+CH2COZ → R13CH2CHO 1.210×10-13 0.5745 -5.62 ● † 190 CH3CHO+R1H → H2+R14CH3CO 6.642×10-11 0 2113.52 ● 191 CH3CHO+R4CH3 → R14CH3CO+CH4 3.321×10-30 5.6 1258.05 ● † * 192 CH3CHO+B1O → R14CH3CO+R2OH 2.325×10-11 0 1157.4 ● † * 193 CH3CHO+R2OH → R14CH3CO+H2O 6.974×10-12 0 251.61 ● † 194 CH3CHO+R7CH3O → R14CH3CO+CH3OH 3.985×10-13 0 905.79 ● † * 195 O2+R1H → R2OH+B1O 1.627×10-10 0 7447.64 ● † * 196 O2+R1H(+M) → R3OOH(+M) 7.506×10-11 0 0 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/0/ CH4/3/ C2H6/3/ AR/0.28/ HE/0.34/ N2/0.67/

LOW / 4.963×10-30 -0.8 0 / TROE / 0.5 1 1.000×108 /

● † * 197 O2+R4CH3(+M) → R8CH3OO(+M) 1.295×10-15 1.2 0 LOW / 1.544×10-22 -3.3 0 /

TROE / 0.36 1 1.00×108 / ● † * 198 R8CH3OO(+M) → O2+R4CH3(+M) 2.919×1016 -0.5201 15655.14 LOW / 3.480×109 -5.02 15655.14 /

TROE / 0.36 1 1.000×108 / ● † * 199 O2+R10C2H3V → HCHO+R5CHO 7.472×10-8 -1.39 503.22 ● † * 200 O2+R10C2H3V → B1O+R13CH2CHO 5.480×10-13 -0.29 5.03 ● 201 O2+R11C2H5 → R17C2H5OO 3.653×10-14 0.77 -301.93 ● 202 R17C2H5OO → O2+R11C2H5 1.365×1019 -1.1776 16567.07 ● 203 O2+R11C2H5 → C2H4Z+R3OOH 1.395×10-12 0 1962.55 ● † * 204 O2+R5CHO → B2CO+R3OOH 1.262×10-11 0 206.32 ● † * 205 O2+R6CH2OH → HCHO+R3OOH 1.993×10-12 0 0 ● † 206 O2+R12CHCOV → 2B2CO+R2OH 2.491×10-12 0 1258.05 ● † * 207 O2+R14CH3CO → R18CH3COOO 3.985×10-12 0 0 ● † * 208 R18CH3COOO → O2+R14CH3CO 9.749×1020 -1.672 21437.71 ● † * 209 O2+R13CH2CHO → HCHO+R2OH+B2CO 9.797×10-15 0 -704.51 ● † * 210 O2+R13CH2CHO → CH2COZ+R3OOH 1.661×10-14 0 -704.51 ● † * 211 R13CH2CHO+R3OOH → O2+CH3CHO 3.433×10-10 -0.2263 -1266.23 ● † * 212 R3OOH+R1H → 2R2OH 2.823×10-10 0 452.9 ● † * 213 R3OOH+R1H → H2O+B1O 4.982×10-11 0 855.47 ● † * 214 R3OOH+R4CH3 → R7CH3O+R2OH 2.989×10-11 0 0 ● 215 R3OOH+R11C2H5 → R4CH3+HCHO+R2OH 3.985×10-11 0 0 ● † * 216 R3OOH+R2OH → H2O+O2 4.816×10-11 0 -251.61 ● † * 217 R3OOH+HCHO → R5CHO+H2O2 4.982×10-12 0 6541.85 ● † * 218 R3OOH+CH3CHO → R14CH3CO+H2O2 1.661×10-12 0 5032.19

56

57

● † * 219 2R3OOH → H2O2+O2 2.159×10P

-13P

0 -820.25 ● † * 220 2R3OOH → H2O2+O2 6.974×10P

-10P

0 6028.56 ● † * 221 H2O2(+M) → 2R2OH(+M) 3.000×10P

14P

0 24406.12 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/

LOW / 4.982×10P

-7P 0 22896.46 /

TROE / 0.5 1 1.000×10P

8P /

● † * 222 H2O2+R2OH → H2O+R3OOH 1.295×10P

-11P

0 654.18 ● † * 223 R8CH3OO+R4CH3 → 2R7CH3O 8.303×10P

-12P

0 -704.51 ● † 224 R8CH3OO+R2OH → CH3OH+O2 9.963×10P

-11P

0 0 ● 225 CH3OOH → R7CH3O+R2OH 6.000×10P

14P

0 21286.16 ● † * 226 C2H3CHOZ+R2OH → B2CO+R10C2H3V+H2O 1.661×10P

-11P

0 0 ● † * 227 C2H3CHOZ+B1O → CH2COZ+R5CHO+R1H 8.303×10P

-17P

1.76 40.26 ● † 228 C2H3CHOZ+R1H → B2CO+R10C2H3V+H2 6.642×10P

-11P

0 2113.52 ● † * 229 C2H3CHOZ+R1H → C2H4Z+R5CHO 3.321×10P

-11P

0 1761.27 ● † * 230 R37C3H5Y+R3OOH → C2H3CHOZ+R1H+R2OH 1.162×10P

-5P

-2 0 ● 231 R37C3H5Y+B1O → C2H3CHOZ+R1H 2.989×10P

-10P

0 0 ● † * 232 R37C3H5Y+R2OH → HCHO+C2H4Z 2.491×10P

-11P

0 0 ● 233 C4H6Z2+R2OH → R37C3H5Y+HCHO 4.650×10P

-12P

0 -452.9 ● 234 R37C3H5Y+HCHO → C4H6Z2+R2OH 5.683×10P

-16P

1.1634 10814.87 ● 235 C4H6Z2+R2OH → CH3CHO+R10C2H3V 9.299×10P

-12P

0 -452.9 ● 236 C6H8#6+R1H → R10C2H3V+C4H6Z2 6.887×10P

-21P

3.4832 12065.88 ● 237 R10C2H3V+C4H6Z2 → RC1C6H9#6Z 1.172×10P

-10P

-1.35 2012.88 ● 238 RC1C6H9#6Z → R10C2H3V+C4H6Z2 6.562×10P

26P

-3.7726 29026.15 † 239 RC5ZC5H9#6OOH → RC2ZOOC6H11#6 7.756×10P

8P 0.9998 10172.46

† * 240 R108C5H9CHOOOH → R107C5H10CHOOO 6.203×10P

6P 1.3391 9752.39

† * 241 R133C5H9CHO3HOO → R2OH+CHOC4H8COOOH 3.300×10 P

9P 1 16354.62

† 242 R121C5H9CHO3HOO → R2OH+CHOC4H8COOOH 3.300×10 P

9P 1 16354.62

† 243 R121C5H9CHO3HOO → R2OH+CHOC4H8COOOH 5.700×10 P

8P 1 12580.47

† 244 R121C5H9CHO3HOO → R2OH+CHOC4H8COOOH 9.900×10 P

7P 1 11070.82

† 245 R121C5H9CHO3HOO → R2OH+CHOC4H8COOOH 1.700×10 P

7P 1 10567.6

† 246 RC9OOC6H10#6OOH → R2OH+C5H9CO#6OOH 9.700×10P

9P 1 17612.66

† 247 RC9OOC6H10#6OOH → R2OH+C5H9CO#6OOH 3.900×10P

10P 1 17756.08

† 248 RC9OOC6H10#6OOH → R2OH+C5H9CO#6OOH 9.700×10P

7P 1 12860.26

† 249 RC9OOC6H10#6OOH → R2OH+C5H9CO#6OOH 1.900×10P

10P 1 16505.58

† 250 RCDOOC6H10#6OOH → R2OH+C5H9CO#6OOH 3.900×10P

10P 1 17756.08

† * 251 C6H12#6+R7CH3O → RC1ZC6H11#6+CH3OH 1.443×10 P

-12P 0 2264.49

† * 252 RC2ZOOC6H11#6+ R8CH3OO

→ C5H10#6CO+CH3OH+O2 2.325×10P

-14P 0 -364.83

† * 253 RC2ZOOC6H11#6+ R8CH3OO

→ C6H11#6OH+HCHO+O2 2.325×10P

-14P 0 -364.83

† 254 RC1ZC6H11#6+R1H → C6H12#6 1.661×10P

-10P 0 0

† 255 C6H11#6OH+R3OOH → H2O2+R13CH2CHO+2C2H4Z 1.993×10P

-12P 0 7799.89

† * 256 C6H11#6OH+R4CH3 → CH4+R13CH2CHO+2C2H4Z 9.963×10P

-13P 0 4830.9

† * 257 C6H11#6OH+B1O → R2OH+R13CH2CHO+2C2H4Z 1.295×10P

-10P 0 2616.74

† 258 RC2C6H9#6Y+R1H → C6H10Z#6 2.248×10P

-11P -0.0133 -252.69

† 259 C6H10Z#6+R2OH → RC6C6H10OH#6 4.650×10P

-12P 0 -523.35

† 260 RC6C6H10OH#6 → C6H10Z#6+R2OH 4.999×10P

22P -2.1943 16035.6

† 261 RC6C6H10OH#6 → 2C2H4Z+R13CH2CHO 2.000×10P

13P 0 13435.95

† 262 RC6C6H10OH#6 → R10C2H3V+C2H4Z+CH3CHO 2.000×10P

13P 0 14442.38

† 263 C6H10Z#6+R1H → RC1C6H9#6Z+H2 2.989×10P

-17P 2 2516.09

† * 264 C6H10Z#6+R2OH → RC3C6H9#6V+H2O 3.653×10P

-18P 2 729.67

† 265 C6H10Z#6+R4CH3 → RC2C6H9#6Y+CH4 3.321×10P

-13P 0 3673.5

† * 266 R1H+R4CH3(+M) → CH4(+M) 2.773×10P

-10P 0 0

58

O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ LOW / 3.882×10P

-24P -1.8 0 /

TROE / 0.37 3315 61 / † 267 C2H4Z+R1H → R10C2H3V+H2 8.303×10P

-17P 1.93 6541.85

† * 268 B1O+R4CH3 → HCHO+R1H 1.395×10P

-10P 0 0

† 269 B1O+C2H4Z → CH2COZ+H2 1.096×10P

-18P 1.88 100.64

† * 270 B1O+C2H4Z → R13CH2CHO+R1H 7.805×10P

-18P 1.88 100.64

† * 271 B1O+C2H4Z → R2OH+R10C2H3V 2.491×10P

-17P 1.91 1861.91

† * 272 R7CH3O+R1H → R2OH+R4CH3 2.834×10P

-8P -0.672 1081.96

† * 273 R4CH3+HCHO → R2OH+C2H4Z 4.401×10P

-14P 0.4731 8021.72

† 274 2R2OH → H2O+B1O 2.491×10P

-15P 1.14 50.32

† * 275 B2CO+R4CH3(+M) → R14CH3CO(+M) 8.303×10P

-13P 0 3472.21

LOW / 3.033×10P

-34P 0 1912.23 /

TROE / 0.5 1 1.000×10P

8P /

† 276 B2CO+B1O+M → CO2+M 4.246×10P

-33P 0 1509.66

O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ † * 277 R1H+B2CO+M → R5CHO+M 1.157×10P

-30P -1.0923 323.25

H2/2/ B2CO/1.5/ CO2/2/ H2O/6/ † 278 R5CHO+R1H → H2+B2CO 1.494×10P

-10P 0 0

† 279 R5CHO+R4CH3 → CH3CHO 2.989×10P

-11P 0 0

† 280 R5CHO+R2OH → H2O+B2CO 1.827×10P

-10P 0 0

† * 281 HCHO+R1H+M → R7CH3O+M 6.712×10P

-35P -0.0582 -3297.4

O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ † 282 R7CH3O+R1H → HCHO+H2 2.989×10P

-11P 0 0

† * 283 R7CH3O+R2OH → HCHO+H2O 2.989×10P

-11P 0 0

† * 284 R7CH3O+B2CO → R4CH3+CO2 2.657×10P

-11P 0 5887.66

† 285 R7CH3O+R5CHO → CH3OH+B2CO 1.511×10P

-10P 0 0

† 286 R7CH3O+HCHO → CH3OH+R5CHO 1.661×10P

-13P 0 1509.66

† 287 2R7CH3O → CH3OH+HCHO 9.963×10P

-11P 0 0

† * 288 R6CH2OH+M → HCHO+R1H+M 2.092×10P

-8P 0 15096.57

O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ † * 289 HCHO+R1H+M → R6CH2OH+M 1.447E-31 -0.1175 1923.78 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ † 290 R6CH2OH+R1H → R4CH3+R2OH 1.594×10P

-10P 0 0

† 291 R4CH3+R2OH → R6CH2OH+R1H 1.412×10P

-12P 0.3827 2830.85

† 292 CH3OH+R1H → R6CH2OH+H2 4.434×10P

-16P 1.6376 3955.73

† 293 R6CH2OH+R2OH → H2O+HCHO 3.985×10P

-11P 0 0

† 294 R6CH2OH+R5CHO → CH3OH+B2CO 1.993×10P

-10P 0 0

† 295 R6CH2OH+R5CHO → 2HCHO 2.989×10P

-10P 0 0

† 296 R6CH2OH+HCHO → CH3OH+R5CHO 9.133×10P

-21P 2.8 2968.99

† 297 R6CH2OH+R7CH3O → CH3OH+HCHO 3.985×10P

-11P 0 0

† 298 CH3OH+R1H → R7CH3O+H2 6.974×10P

-18P 2.1 2465.77

† 299 R7CH3O+H2 → CH3OH+R1H 4.644×10P

-19P 2.4031 2171.24

† 300 CH3OH+B1O → R6CH2OH+R2OH 5.646×10P

-11P 0 2767.7

† 301 CH3OH+B1O → R7CH3O+R2OH 1.661×10P

-11P 0 2365.13

† 302 CH3OH+R2OH → R7CH3O+H2O 8.967×10P

-19P 2 -171.09

† 303 R12CHCOV+R2OH → R5CHO+B2CO+R1H 1.661×10P

-11P 0 0

† 304 CH2COZ+R1H → R12CHCOV+H2 8.303×10P

-11P 0 4025.75

† 305 CH2COZ+B1O → R12CHCOV+R2OH 1.661×10P

-11P 0 4025.75

† 306 R14CH3CO+R1H → R4CH3+R5CHO 1.594×10P

-10P 0 0

† 307 CH3CHO+R6CH2OH → R14CH3CO+CH3OH 3.313×10P

-18P 2.0916 2368.41

† * 308 O2+R1H(+H2O) → R3OOH(+H2O) 7.506×10P

-11P 0 0

LOW / 1.903×10P

-32P 0 -1046.7 /

TROE / 0.45 1 1.000×10P

8P /

59

† * 309 O2+R4CH3 → R7CH3O+B1O 2.159×10P

-10P 0 15750.75

† * 310 O2+R4CH3 → HCHO+R2OH 4.982×10P

6P -4.69 18417.81

† * 311 R3OOH+B1O → O2+R2OH 7.688×10P

-9P -0.6669 195.65

† * 312 O2+HCHO → R5CHO+R3OOH 3.321×10P

-11P 0 19524.9

† * 313 O2+R7CH3O → HCHO+R3OOH 3.653×10P

-14P 0 855.47

† 314 R6CH2OH+R3OOH → O2+CH3OH 1.031×10P

-11P -0.348 -1804.64

† * 315 O2+CH3CHO → R14CH3CO+R3OOH 8.303×10P

-11P 0 18317.17

† * 316 R14CH3CO+R3OOH → O2+CH3CHO 6.265×10P

-14P 0.5604 -2260.83

† * 317 O2+CH3CHO → R13CH2CHO+R3OOH 1.661×10P

-11P 0.5 23148.07

† 318 R3OOH+R1H → H2+O2 7.140×10P

-11P 0 704.51

† * 319 R3OOH+C2H4Z → CH3CHO+R2OH 9.963×10P

-15P 0 3975.43

† * 320 R3OOH+B2CO → CO2+R2OH 2.491×10P

-10P 0 11875.97

† * 321 R3OOH+R5CHO → R2OH+R1H+CO2 4.982×10P

-11P 0 0

† * 322 R3OOH+R7CH3O → HCHO+H2O2 4.982×10P

-13P 0 0

† * 323 R3OOH+R6CH2OH → HCHO+H2O2 1.993×10P

-11P 0 0

† 324 R3OOH+CH3OH → R6CH2OH+H2O2 1.594×10P

-13P 0 6340.56

† 325 2R2OH(+M) → H2O2(+M) 1.201×10P

-10P -0.37 0

O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ LOW / 1.525×10P

-28P -0.76 0 /

TROE / 0.5 1 1.000×10P

8P/

† 326 H2O2+R1H → H2+R3OOH 2.823×10P

-12P 0 1861.91

† * 327 H2O2+R1H → H2O+R2OH 1.661×10P

-11P 0 1811.59

† * 328 R8CH3OO → HCHO+R2OH 1.500×10P

13P 0 23651.29

† * 329 R8CH3OO+R1H → R7CH3O+R2OH 1.594×10P

-10P 0 0

† * 330 R8CH3OO+R10C2H3V → R7CH3O+R13CH2CHO 3.985×10P

-11P 0 0

† * 331 R8CH3OO+R2OH → R7CH3O+R3OOH 4.982×10P

-12P 0 0

† * 332 R8CH3OO+B2CO → R7CH3O+CO2 1.661×10P

-10P 0 12077.25

† * 333 R8CH3OO+R5CHO → R7CH3O+R1H+CO2 4.982×10P

-11P 0 0

† * 334 R8CH3OO+R6CH2OH → R7CH3O+R2OH+HCHO 1.993×10P

-11P 0 0

† * 335 R8CH3OO+R14CH3CO → R4CH3+CO2+R7CH3O 3.985×10P

-11P 0 0

† * 336 R8CH3OO+R3OOH → O2+HCHO+H2O 8.303×10P

-14P 0 0

† 337 2R8CH3OO → CH3OH+HCHO+O2 4.151×10P

-14P 0 -402.58

† * 338 2R8CH3OO → 2R7CH3O+O2 4.151×10P

-14P 0 -402.58

† * 339 2R18CH3COOO → 2R4CH3+O2+2CO2 2.823×10P

-12P 0 -503.22

† 340 R14CH3CO+R4CH3 → C2H6CO 6.642×10P

-9P -0.8 0

† * 341 B2CO+R10C2H3V+ R3OOH

→ C2H3CHOZ+O2 1.080×10P

-52P 4.7408 -16732.6

† 342 R37C3H5Y+B1O → R10C2H3V+HCHO 2.989×10P

-10P 0 0

† 343 R10C2H3V+HCHO → R37C3H5Y+B1O 3.371×10P

-17P 1.7125 27923.18

* 344 C6H10Z#6+B1O → RC1C6H9#6Z+R2OH 8.635×10P

-11P 0 2616.74

* 345 C6H10Z#6+B1O → RC2C6H9#6Y+R2OH 2.989×10P

-13P 0.7 1635.46

* 346 R10C2H3V+R1H+M → C2H4Z+M 4.485×10P

-33P 0.1312 -7168.09

* 347 O2/0.4/ B2CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3/ C2H6/3/ AR/0.34/ N2/0.4/ HE/0.34/ * 348 R10C2H3V+R3OOH → O2+C2H4Z 1.981×10P

-12P -0.119 -2106.02

* 349 R3OOH+R10C2H3V → R2OH+R4CH3+B2CO 4.982×10P

-11P 0 0

* 350 R8CH3OO+B1O → R7CH3O+O2 5.978×10P

-11P 0 0

* 351 C2H3CHOZ+R1H+ R2OH → R37C3H5Y+R3OOH 3.257×10P

-22P -4.8301 1156.43

* 352 R37C3H5Y+O2 → C2H3CHOZ+R2OH 2.989×10P

-11P -0.41 11523.71

60

d) Classes of reactions removed from cyclohexane and n-butane schemes cyclohexane mechanism Molecular elimination reactions Retro-ene reaction Unimolecular initiations Alkane reactions Addition of oxygen on cyclo-ether radicals Isomerization of peroxy radicals Addition of oxygen on cyclo-peroxy radicals Formation of cyclo–ether ketohydroperoxides Decomposition of cyclo-ether ketohydroperoxides Alkene reactions Addition of OH on alkenes Addition of O on alkenes

Addition of OOH on alkene Alkene to dienes Metathesis with (YH) (alkenes) Addition of .Y on (YH) (alkenes) Alchohol reactions Ketoradicals addition to O2 Peracid radical decomposition Diels alder .Y termination (Alkene) Unimolecular initiations of C6H10Z#6 Beta scissions (cyclohexene submechanism only) Cyclization of molecule C6H8Z3-135

The C0 – C2 lumped reactions of: H2, B4CH, B6CH, B5CH2, CH4, C2H2T, R9C2HT, R10C2H3V, C2H4Z, C2H6, R6CH2OH, R12CHCOVD, R14CH3CO, C2H4O#, R15C2H5O, C2H5OH. CO2, R17C2H5OO, R16C2H4OOH, R18CH3COOO, CH3COOOH Reactions producing C2+ radicals and C2+ molecules Reactions of C2H2T, C2H3, C2H4, C2H5, HCO, CH3O, CH2OH, CH3CO Benzene formation reactions of; C3H2, C3H3, C3H4T, C3H4T, C3H4Z2, cC3H4 (cyclopropene), sC3H5 (2-methyl vinyl), tC3H7 (1-methyl vinyl), C3H6Y (propene), cC3H6, C3H7. Non oxygen C4 reactions C2H4, nC4H3, iC4H3, C4H4, tC4H4, iC4H5, C4H5-1s, C4H5-1p, C4H5-2 Reactions deducted from those of C3H3 Reactions of C4H6(12) (1,2 butadiene), c-C4H6 (methyl cyclopropane), C4H6-1 (1 Butyne), C4H6-2 (2-butyne), iC4H8Y n-butane mechanism Unimolecular initiations removed. Alkane reactions. Addition of of .Y on YH (Alkenes) Alcohol reactions

Peracid radical decompositions Ketone reactions Diels Alder

The lumped base C0-C2 reactions of: Reactions of the matrix O(0)C(y)H(z) H2, B4CH, B6CH, B5CH2, CH4, C2H2T, R9C2HT, R10C2H3V, C2H4Z Reactions of the matrix O(x)C(y)H(z) H2O, R6CH2OH, R12CHCOVD, R14CH3CO, CO2, R16CH3COOOH Reactions of: C2H2T, C2H3, C2H4, CH3O, CH2OH, CH3CO Reactions added to hold count of propenal