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U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards

U, 2
NATIONAL BUREAU OF STANDARDS

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Table of Recommended Rate Constants

4 1980

for Chemical Reactions gOccurring in Combustion *^

5ZVS

^

£S

Francis Westley

Chemical Kinetics Information Center

National Measurement Laboratory

National Bureau of Standards

Washington, D.C. 20234

Sponsored by the

Department of Energy

Washington, D.C. 20545

and

Office of Standard Reference Data

National Bureau of Standards Washington, D.C 20234

N SRP S

U.S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary

Luther H. Hodges, Jr., Deputy Secretary

Jordan J. Baruch, Assistant Secretary for Productivity, Technology, and Innovation

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued April 1 980
Library of Congress Cataloging in Publication Data

Westley, Francis. Table of recommended rate constants for chemical reactions occurring

in combustion.

(Nat. stand, ref. data ser. ; NSRDS-NBS 67) "National standard reference data system.”

Supt. of Docs, no.: 03.48:67

1. Chemical reaction. Rate of--Tables, etc. 2. Combustion-Tables, etc.

I. Title. II. Series: United States. National Bureau of Standards. National standard reference data series ; NSRDS-NBS 67. QC100.U573 no. 67 [QD502] 602’. Is [541.3’61’0212] 79-607159

NSRDS-NBS 67

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 67, 119 pages (Apr. 1980)

CODEN: NSRDAP

© 1980 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1980 For sale by the superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

Price S4.25
Foreword

The National Standard Reference Data System provides access to the quantitative data of physical science, critically evaluated and compiled for convenience and readily accessible through a

variety of distribution channels. The System was established in 1963 by action of the President’s

Office of Science and Technology and the Federal Council for Science and Technology, and

responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National

Research Council of the National Academy of Sciences-National Academy of Engineering. A number of Advisory Panels, each concerned with a single technical area, meet regularly to examine

major portions of the program, assign relative priorities, and identify specific key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels

which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of advisory services contributes greatly to the guidance of NSRDS activities. The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically

evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computations of useful functions derived from standard reference data. The centers and projects ?lso establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being

planned: nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and surface properties.

Reliable data on the properties of matter and materials are a major foundation of scientific and technical progress. Such important activities as basic scientific research, industrial quality control, development of new materials for building and other technologies, measuring and correcting

environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility

to support American science, industry, and commerce is vitally fulfilled.

Ernest Ambler, Director

III
Contents

Page

Foreword Ill 1. Introduction 1 2. Guidelines for the User 2

Table of Arrhenius parameters for chemical reactions occurring in combustion 8

Reactions of: 0 8

02 14

Oa 16

H 16

H2 22

OH 24

HO2 26

H2 0 28

H2 O2 28

S 28

S2 31

SO 31

SO2 32

SH 32

H2 S 33

N 33

N2 36

NO 37

NO2 39

NO3 40

N2 0 40

N2 O4 41

N2 O5 41

NH 41

NH2 42

NH3 42

NH2 NH2 42

HN3 43

HNO 43

HNO3 43

NS 44

Ci compounds 44

C 2 compounds 72

C 3 compounds 81

C 4 compounds 86

C 5 compounds 96

C 6 compounds 100

C 7 compounds 104

Cg compounds 106

C 9 compounds 109

C 10 compounds 109

3. Sources of Recommended Rate Constants 109

Appendix: Conversion Tables 110

IV
Table of Recommended Rate Constants for Chemical*

Reactions Occurring in Combustion

Francis Westley

National Bureau of Standards, Chemical Kinetics Division, Center for Thermodynamics and Molecular Science, Washington, DC 20234

A table of recommended rate constants for gas phase chemical reactions occurring in combustion is presented.

Specifically, it gives in tabular form the values of the parameters for the modified Arrhenius equation k = AT Bexp

( — E/RT). The table covers reactions occurring in the combustion, oxidation and decomposition of aliphatic saturated or unsaturated Ci to Cio hydrocarbons, alcohols, aldehydes, ketones, thiols, ethers, peroxides, amines, amides and their free radicals, as well as the reactions of 0, O2, H, H2, OH, H2O, H2O2, N, N2, NO, N2O, NO2,

N2O4, N2O5, S, S2, SH, SO, SO2, SOH, NS, with each other. The table includes 169 first order reactions 782

second order reactions and 57 third order reactions. There are 1770 entries covering 1008 distinct chemical

reactions. These recommendations have been taken from eleven evaluations and critical reviews published between 1970 and 1976. The papers examined by the evaluators extend from the nineteen fifties up to and

including 1975.

Keywords: Arrhenius parameters; chemical kinetics; combustion; decomposition; free radicals; gas phase;

hydrocarbons; hydrogen; nitrogen; oxygen; rate of reaction; sulfur.

1. Introduction

This publication consists of a table of recommended

reaction rate constants for the combustion, oxidation, and

decomposition reactions of aliphatic saturated and unsaturated hydrocarbons, their oxygenated sulfur and ami- no derivatives, as well as for the reactions of hydrogen,

nitrogen, oxygen, sulfur and their inorganic derivatives

with each other. The table is a compilation of recom- mended rate constants given in eleven critical reviews on

the kinetics of combustion, oxidation and decomposition

reactions, published between 1970 and 1976. Its purpose

is to provide the kineticists and kinetic modelers with a comprehensive and easy-to-consult reference book on the

kinetic data for combustion and oxidation processes. The

table gives 1008 recommended reaction rate constants from these eleven sources. A summary of the content of

the table is given in the following listing of quotations

from each source.

No. of Recommended

Source Rate Constants

Baulch et al. (1972) 40

Baulch et al. (1973) 64

Baulch et al. (1976) 36

Benson and O’Neal (1970) 167

Benson et al. (1975) 119

‘This work was supported by the Department of Energy and by the Office of Standard

Reference Data of the National Bureau of Standards.

Engleman (1976) 123

Herron and Huie (1973) 46

Kerr and Parsonage (1972) 185

Kerr and Parsonage (1976) 181

Kondratiev (1970) 37

Lloyd (1974) 10

Total 1008

For ease of reference the bimolecular and termolecular

reactions included in the table are listed separately under

each reactant, so that a grouping of the reaction according

to the first reactant is obtained. As a result, the total number of tabulated entries is 1770, although the real number of distinct chemical reactions is 1008.

The presentation of kinetic data is standardized and

simplified as much as possible. Rate constants are ex- pressed in the modified Arrhenius equation & =ATBexp

( — E/RT). In general uncertainties are given only for the

rate constant k itself and not for the individual parameters in this equation. Sometimes an uncertainty is given

for the value of El R. This uncertainty is only of secondary importance and has been included in the uncertainty

stated for the value of the rate constant. Rate constants

are expressed in units of s -1

, cm3mol -1

s -1

, and

cmSiol

- ^

-1

for reactions of first, second, and third

order, respectively.

For the readers who prefer other kinetic units than the

standard ones, two conversion tables for equivalent sec- ond and third order rate constant units are appended at the end of this publication.

1
The arrangement of the tables is described in detail below, in the “Guidelines for the User.”

It is hoped that this table of kinetic data will serve as a handy and easy to use reference book for all the kineticists and kinetic modelers interested in combustion and

oxidation processes. This publication is not the result of the effort of a single person, but of the whole staff of Chemical Kinetics

Information Center. My thanks to all of them.

In particular, I wish to thank Dr. David Garvin, Chief

of the Chemical Thermodynamics Division, and Dr. Robert F. Hampson, Jr., Director of the Chemical Kinetics

Information Center, for their more than helpful suggestions and constant guidance; Dr. Wing Tsang, Chief of

the Chemical Kinetics Division, for his encouragement in having this table published; Mr. James G. Koch, Supervisor, for putting the tables into a printable computer

form; Mrs. Bettijoyce Molino and Mrs. Carla G. Messina

from the Office of Standard Reference Data for applying

the OMNIDATA and GPSDIC programs to the present

tables; Mrs. Geraldine Zumwalt and Mrs. Janice L. Jones

for punching and typing a difficult typescript, full of

digits and numbers, with particular care.

2. Guidelines for the User

General

As pointed out above, the presentation of the kinetic

data in this publication is an attempt to simplify and

standardize them. In that respect, the choice of standard

units for rate constants was easy; it was found that the

most commonly used units for gas phase rate constants

are the cubic centimeter, the mole and the second. The

choice of a standard form for uncertainty limits is some- what more complicated, but when a series of recommended rate constants is to be presented in a tabular form, the

uncertainty limits cannot be omitted, for an uncertainty

assigned to the recommended value of a rate constant is an estimate by the evaluator of the absolute accuracy of

the preferred value. It is to be emphasized that in the

present tables the concern is with the overall uncertainty

of a reaction rate constant and not with the expression of

precision of a set of experimental measurements. Most of

the uncertainty limits included in this table are uniform

within the respective temperature range indicated. However, for a limited number of reactions, the data warrant

or require variable limits. In such cases, a note under the

respective data indicates for which interval of the temperature range there is a change in the uncertainty limits.

It is thought that the uncertainty limits expressed in the form of lower and upper k factors,/ and F, respectively, are the most suitable for tabulation. Thus, if kQ

is the

central value of a rate constant the limits of reliability for the rate constant kQ are defined by the relationship:

fk0 <k<Fk0 (1)

i.e., multiplication of the central value kQ by / and F

gives, respectively, the lower and upper reliability limits of the rate constant. In this standardized formulation of

uncertainty limits, the value of/is less than unity and the

value of F is greater than unity.

However the k factors are not the only way to express

the uncertainty limits of a rate constant and different

authors use different forms to indicate the degree of

reliability of a recommended rate constant. It follows that

certain mathematical relationships are needed to translate the different forms of uncertainty limits into the standard

form used in this table (lower and upper k factors). The

tranformation formulas are given and discussed below.

In general there are two ways to state uncertainty

limits: (1) by factors and by algebraic addends.

Uncertainty Expressed by Factors

Besides the standard form of uncertainty limits ex- pressd by the lower and upper factors/ and F, as defined

by the above given relationship (1), there is another form

which expresses the uncertainty limits by a unique factor. Thus, if kQ

is the central value of a rate constant, the statement that kQ

is uncertain to a factor of F means that the uncertainty limits are defined by the relationship:

k0/F<k<k0F (2)

which shows that division and multiplication of the

central value kQ by F gives, respectively, the lower and

upper reliability limits of the rate constant. By comparing

relationships (1) and (2), it is obvious that in the case of an uncertainty expressed by a unique F the upper factor

is equal to the unique factor itself, while the lower factor

/

is the reciprocal of F: f=l/F (3)

Uncertainty Expressed by Algebraic Addends

There are three types of uncertainty limits for rate constants expressed as algebraic addends which are cur- rently used by kineticists: (a) Uncertainty appended to one of the Arrhenius factors (A , B, or E/R), (b) Uncertainty appended to logioA;0, and (c) Uncertainty expressed

as a percentage of kQ. With respect to the type (a) uncertainties, the B factor uncertainties have been elimi- nated as being unimportant, while the uncertainties for

2
logio£0 /^< logioA < logio-fifc, the E/R factor may be omitted because they are of

secondary importance and are included in the k factors. Therefore, the only uncertainty of type (a) considered

below is the one appended to the coefficient of the A

factor.

(a) Uncertainty appended to the coefficient of A factor. In scientific notation, the A factor is of the form:

A =aX 10" (4)

where a is a numerical coefficient less than 10 and n is the power of 10. If an uncertainty dta' is appended to the

coefficient a, the A factor takes the form:

A=(a±a')X 10 n

(5)

If lower and upper factors if and F) are wanted instead,

the A factor takes the form:

A=faX 10" (6)

or A=FaX 10n

(7)

Comparison of (6) and (7) to (5) leads to the relationships:

fa=a—a and Fa=a+a from which the following for- mulas are obtained:

f=\—a/a (8)

and F= l+a'/a (9)

Formulas (8) and (9) are the relationships needed to transform an uncertainty appended to the coefficient of

the A factor into one using a k factor. A numerical

example follows: A =(2.0±:0.5)X 10 14

, therefore: a =2.0

and a =0.5; a'/a =0.5/2.0 =0.25 and the k factors are: /= 1 - 0.25 = 0.75 and F=l +0.25 = 1.25.

(b) Uncertainty appended to logioA;0

. If kQ

is the central value of a rate constant, C its logarithm to the base 10

and D the uncertainty expressed as an algebraic addend

to C, then the following relationship is true:

logiok = C±D (10)

where C

logioA:0

. If D is put in logarithmic form, say: D= logio/’ (11)

then relationship (10) becomes:

logioA: = logio^o —logio/

1 (12)

which can take the form:

or k0 /F<k<Fk0 (13)

Replacing 1 IF by/, relationship (1) is obvious that the k factors f and F are the

of —and D, respectively:

obtained. It is antilogarithms

/=antilog (—D) = 10-£> (14)

.F= antilog D=10D

(15)

Formulas (14) and (15) are the relationships needed to transform the type b uncertainties into reliability limits expressed by k factors. A numerical example follows: logio£ = 14.23±0.3, therefore: /=10-a3 =0.5 and

/’=10a3=2.0.

(c) Uncertainty expressed in percentage of kQ. Some

kineticists prefer to use percentage for defining the

uncertainty limits of a rate constant. Thus, the statement

that a rate constant is ±: p% uncertain means that the

uncertainty limits of kQ are defined by the relationship:

kQ -ip/ 100)£o <k <£0 +(p / 1 00)kQ

or (l-/>/100)£o <£<(l+/>/100)£o (16)

Replacing the percentage by the rate, defined as r=p/ 100, relationship (16) becomes:

(1

r)kQ <A: <(1 +r)k0 (17)

Comparison of relationships (17) and (1) leads to the

following formulas:

f=l~r (18)

and /’=l+r (19)

which are the relationships needed to transform the type

c uncertainties into reliability limits expressed by

k factors. A numerical example follows: k = 3.7X 10 12it20%, therefore p =20% and r=0.2.

Thus: /= 1-0.2 = 0.8 and ^=1 +0.2 = 1.2. When a percent error has been stated as > 100%, the F

factor is determined first, according to relationship (19)

then, instead of relationship (18), one simply sets: f=l/F. E.g., for a 150% error, r=1.5, /’=l+r=2.5

and /= 1 /F= 0.4.

The above given relationships: (3), (8) and (9), (14) and

(15), (18) and (19) can be used in reverse by the reader

who prefers other types of uncertainty limits than the

3
standard k factors,/ and F. However a word of caution is necessary. In contrast with the standard uncertainty

limits, other types of uncertainties for rate constants using a unique factor or algebraic addend have a constraint imposed upon them. Thus, the uncertainties ex- pressed by a unique algebraic addend are required to be

symmetrical with respect to the central value to which

they are appended, while the uncertainty expressed by a unique factor, F, indicates in fact that the upper factor F

and the lower factor f are required to be inverse to each

other \f=\/F). No such constraints are imposed on the

standard uncertainty limits used here and for that reason

this type of uncertainty has been found most suitable for tabulation purposed. Why some evaluators prefer uncertainty limits with constraints in not clear. It would seem more logical if the lower and upper uncertainty limits were studied independently from each other, without

imposing any constraints on them. Probably it is a matter

of convenience to express an uncertainty in the form, say:

logiok = C±D rather than by the inequality:

fk0 <k<Fk0

. If the transformation of the standard uncertainty limits into uncertainties with constraints is desired, some ad- justments may be necessary according to the case. The

following examples, for transformation of standard uncertainty into a unique factor uncertainty, are an illustration of the necessary adjustments:

(1) Standard factors: /= 0.5 and F= 2.0. It is obvious

that f=\/F and no adjustment is necessary.

(2) Standard factors:/=0.8 and F= 1.2. In this case, f

and F are not inverse to each other. Indeed

/ = 1 /F= 0.83 while F' = 1 //= 1 .25. The two pairs of factors (f = 0.83; F= 1.2, and/=0.8;

F' = 1.25) are quite close. However, it is safer to choose

the pair 0.8 and 1.25, by enlarging slightly the uncertainty range.

(3) Standard factors: /=0.6 and F=1A. In this case, not only are the factors not inverse to each other, but the

difference is significant: f = l//r =0.71 and

F = l//=1.67.

The two pairs of factors (f = 0.71; F= 1.4, and/= 0.6; F'

1.67) are significantly different. Again, it is safer to choose the pair 0.6 and 1.67 by enlarging the uncertainty

range. And, since the concepts of uncertainty and reliability are opposite to each other, enlargement of the uncertainty range will result in a decrease in reliability.

The same adjustments may be necessary for transfor- mation of k factors uncertainties into another type of

uncertainties.

Arrangement of the Table

The table is arranged in six columns including the

chemical reactions, temperature range, the parameters^,

B, and E/R for the modified Arrhenius equation

/r = AT Bexp ( —E/RI), and the uncertainty limits ex- pressed as k factors f and F. Section 3, the bibliography to the table includes the

full references for the 11 critical reviews from which the

present table was compiled. Following the bibliography,

two conversion tables for equivalent second and third

order rat constant units are appended.

Column 1 includes the chemical reactions indicating

both the reactants and the products. In the same column,

under each chemical reaction, the names of the reactants are given. The chemical nomenclature adopted is the one

used in the Chemical Substance Indexes of Chemical

Abstracts. Alternative names are not given. The chemical names of the products are not given. The line with

chemical names is indented with respect to the line above

it. Under the chemical names, the short reference of

reviewer’s book or article is given. It includes the last two

digits of publication’s year, followed by the first three

letters of author’s name. If two authors are given, a slash

separates each author’s three letters. Again, the short

reference line is indented with respect to the line above

it, e.g., 73 HER/HUI indicates the review of rate constants

for the reactions between aliphatic hydrocarbons and

atomic oxygen, published by Herron and Huie in 1973.

In the same line with the short reference, but spaced

out, the order of reaction is indicated by the words

“Reaction order” followed by one of the digits 1, 2, or 3. As pointed out in the introduction, the order of reaction

helps to establish the proper standard units for the

reactions, as follows:

1 for first order reactions s _1

2 for second order reactions cm ^ol ~ h

~ 1

3 for third order reactions cm^ol - ^

-1

Following the reaction order, on the same line, the

presence of an inert reaction partner “third body” is indicated by the letter M, followed by its chemical

formula, e.g., M:Ar or M:C02. No indication is given if M is undefined, or if the reaction does not include M. In

all, there are 112 reactions with M specified.

For 124 reactions, no Arrhenius parameters are indi- cated. Instead, for each of these 124 reactions, the ratio of the rate constant with respect to the rate of a reference

reaction, taken as unity, is given. This information

follows the reaction order information, on the same line,

and is indicated by the symbol k/krei: followed by a number, e.g., k/kTef: 0.59.

4
The last line of column 1, placed under the line including the short reference and reaction order information, begins with the heading Note:. It is given only when

necessary and might include information about the de- pendence of k factors on temperature range, or the

reaction taken as reference when the ratio k/kref is given

in the previous line, or other information pertinent to the

reaction indicated above. The rate constant, kTef, for the

reference reaction indicated in the note (by the same

author) can be found in the table in the proper place. For

a certain number of reactions taken from Baulch et al. (1972, 1973, and 1976) the relationship k\=Kk-\ in- cluded in the note indicates that the respective rate constant was calculated from the equilibrium constant K

and the rate constant k-\ of the reverse reaction. In such

cases, the author usually gives the rate constant of the

reverse reaction immediately after the data for the for- ward reaction. The arrangement of the present table (based on the standard order, as described below in the

following paragraph) does not allow the forward rate constant of a reaction to be followed immediately by its reverse reaction data. The reader will have to locate the

rate constant of a reverse reaction (by the same author) in

its proper place in the table. Column 2, with the heading T/K, indicates in kelvins the temperature range of validity of the recom- mended rate parameters. For some reactions only one

temperature is given, meaning that the reaction was

studied only at one temperature. If no temperature at all

is indicated, it means that the kinetic parameters of the

corresponding reaction are valid throughout the normal

temperature range for combustion. The data estimated by

Benson and Golden in tlieir report “Estimating the

Kinetics of Combustion” are in this category. The temperatures are alined with the short reference and the

reaction order information.

Column 3, with the heading +, gives the value of A for the equation & =ATBexp ( — E/RT) in short scientific notation. In other words, it appears as a number less than

10, followed by a parenthesis including an integer pre- ceded by the sign -f or -. The number less than 10 is the coefficient of the A factor, while the integer inside

the parenthesis is the exponent of 10. Therefore, e.g., 3.5

(+14) should be read as 3.5X10+14

. The coefficient of

the A factor has no more than one digit after the decimal

point. The units of the + factor are the same as for the

rate constant k\ according to the order of the respective

reaction, as shown above. For those cases when the

recommended value is only for one temperature, the entry

under this column is in fact the value of the rate constant

k at this temperature. As for the temperatures, the data

for the + factor are alined with the short reference and

reaction order information. If a dash appears in this

column, it means that no A factor value was reported by

the evaluator for the corresponding reaction.

Column 4, with the heading B, gives the value of B for the equation & =ATBexp ( — E/RT). the value of B is usually low and varies from 0 to about 3 or 4. It may be

negative or positive. The negative values of B are pre- ceded by the sign — , while the positive values are without sign. No more than one digit is given after the

decimal dot. If in this column a dash appears instead of a

figure, it means that no B value was reported by the

evaluator for the corresponding reaction. As for the

temperature and + factor, the data for B are alined with

the short reference and reaction order information.

Column 5, with the heading E/R, indicates the value of

E/R for the equation & =ATB exp ( — E/RT). Since E is the activation energy in cal mol

and R the gas constant with a value of 1.987 cal mol-1K

-1

, it follows that the

units of E/R are kelvins. The values given in column 5

for E/R may vary from 0 to over 100000 kelvins. The

E/R values may be positive or negative. The negative

values are preceded by — , while the positive values are without sign. Some of the E/R values included in the

table are followed by an uncertainty with plus or minus

sign. As pointed out in the introduction, these uncertainties may be ignored, as being included in the lower and

upper k factors indicatd in the right column of the table.

If in this column a dash appears instead of a figure, it means that no E/R value was reported by the evaluator. As for the data from the previous columns, the values for the E/R factor are alined with the short reference and

reaction order information.

Column 6, with the heading “

factors” and two

subheadings, 4 y” and “P’, indicates the two uncertainty k

factors, the lower factor f in the left subcolumn and the

upper factor F in the right subcolumn. To find the

uncertainty limits of a reaction, its rate constant is to be

multiplied by the two factors, as shown above in relation

(1): fk0 <k<Fk0

. The values of both factors are always

positive. If no uncertainty limits are indicated by the

evaluator, both subcolumns of the column 6 are left blank. As for the data from the previous columns, the k

factors are alined with the short reference and reaction

order information.

Ordering of Chemical Reactions

The general rule for ordering the chemical equations of

the reactions listed in column 1 of the table is the

standard order of arrangement as described in NBS

Technical Note 270-3 pp. 5, 6, and 22 *). This rule is applied to the first reactants of the reactions listed in the

table, as well as to the reactants following the first. The

first reactant of a reaction takes precedence over the

5
following ones. The compounds listed as reactants may

include the atoms 0, H, S, N, and C, either each of them

separately, or several, in any possible combination. The

standard order of arangement, when applied to these five atomic species, will result in the sequence 0, H, S, N, C,

each atom in it taking precedence over the following

ones. When applied to the first reactants listed in the

table, the standard order of arrangement will result in a sequence of five chemical systems, whose order of prece- dence is as follows:

( 1 ) 0 system, (2) H-0 system, ( 3) S-O-H system, (4) N- O-H-S system, and ( 5) C-O-H-S-N system.

In each system, the first atom is underlined to show

that the compounds containing this atom only, should be

listed first. It is to be noted that the atomic species

following the underlined atom are in standard order,

while the underlined atom itself should be put at the end

if the standard order were to be followed. As it will be

shown below, this exception to the standard rule, which is apparent only but not real, is due to the fact that all the

compounds containing the atoms of a system with the

exception of the underlined atom, are already listed in the

previous systems. In each of these five chemical systems,

the order of the compounds listed in the table as first reactants is as follows:

(1) 0 system: 0, O2, O3.

(2) H-0 system: H, H2, OH, HO2, H2O, H2O2.

( 3) S-O-H system: S, S2, SO, SO3, SH, SH2, SOH.

( 4) N-O-H-S system: N, N2, NO, NO2, NO3, N2O, N2O4,

N2O5, NH, NH2 , NH3, N2H4, HN3 , HNO, HNO3, NS.

( 5) C-O-H-S-N system: Ci compounds: C, CO, CO2, CH,

CH2 , CH3, CH4, CHO, HCHO, CHaO-, CH3OH, CHaOOH,

CS, CS2, COS, CHaS, CHaSH, CN, C(N02)4 , CHN,

CH3NH2, CH=N=N, CH3NHNH2, CH3NO, CH3NO2,

CH3NO3, CH3ONH2. C2 compounds: C2, GO, CH=CH,

CH2 =CH2 , CHaCH2 -, CH3CH3, CH2=C=0, etc. G

compounds, etc., up to C10 compounds follow, being

ordered according to the same pattern.

It is clear now that, for instance, the compounds

included in the S-O-H system contain at least one sulfur atom, while the compounds containing only H, or 0

atoms, or both, are already listed in the previous two

systems (O-system and H-0 system). It is to be noted that

for the C-O-H-S-N system the standard order is applied in

a slightly different way: the compounds are first grouped

according to the number of C atoms, then the rule for the

standard order of arrangement is applied for each group

apart. This is necessary as a result of the very large

number of organic compounds.

1 Wagman, D. D., Evans, W. H., Parker, V. B., Halow, I., Bailey, S. M., and Schumm, R. H., “Selected Values of Chemical Thermodynamic

Properties,” NBS Tech. Note 270-3 pp. 5, 16, 22 (1968).

The standard order is applied in the same way for the

second, or third reactants of chemical reactions. Since the

reactants of a chemical equation can be switched around,

a number of bimolecular and termolecular reactions are inserted in the table in two and three places, respectively.

E.g., reaction CH4 + O—CH3* + 0H, is inserted in the C- O-H-S-N system. This reaction may also be written as O + CH*—0H-I-CH3* and, as such, is listed in the 0

system. The advantage of such a procedure is obvious:

referring to the example just given the reader will find

the reaction between methane and oxygen listed with CH4

as first reactant if he is interested in the reactions of

methane, or listed with 0 as first reactant, if he is interested in the reactions of oxygen atom. The bimolecular reactions are the largest group of reactions included in the table. There are about 750 reactions listed in the

table, having as reactants two distinct chemical compounds. Since each of these reactions is inserted twice,

the number of entries for them will amount to about

1500. Only a small number of termolecular reactions has

three distinct reactants. As an example, one of them is NO + NO2 + O2—N2O5. This reaction will also be insert- ed under the forms: NO2 + NO +O2—N2O5 and 02-l- NO +N02—*N205. A number of second and third order

reactions includes a second and third body M, respectively. For this group of reactions, M will always be

placed after all the other reactants, which means that the

second order reactions with M as reactant will be inserted

in the table only once, while the third order reactions

with M as reactant will be inserted only twice. E.g.,

reaction O3 + M—O+ O2 + M is inserted in the table only

once, while reaction NO + O + M—>N02 + M is inserted

as such, and also under the form O + NO + M—^-NCfe + M.

Most of the chemical reactions included in the table are balanced. A number of reactions are only apparently

unbalanced. For instance, reaction

CH3CH2CH2CH3 +H—CH3CH2CH2CH2-

CH3CH2CHOCH3 + H2 (20)

has a rate constant which is in fact the sum of the rate constants for the two reactions

CH3CH2CH2CH3 + H^CH3CH2 CH2CH2 +H2 (21)

and CH3CH2CH2CH3 + H^CH3CH2 CH(.)CH3 + H2 (22)

Since the Arrhenius parameters listed in the table refer

to the total rate constant, the reaction is listed in the table under the form (20) rather than in two separate forms. In some instances, a reaction is balanced, but the alkyl

radicals formed as products are not specified, e.g.:

CH3* + (CH3 )2 CHCH(CH3 )CH(CH3 )2 ^CH4 + [GHi7 -] (23)

6
The unspecified octyl radical inserted in square brackets as product in equation (23) represents all primary,

secondary and tertiary octyl radicals that could be formed

by abstraction of a H atom from the reactant 2,3,4-

trimethyl-pentane. There are a number of reactions with

the products totally unspecified. In such a case, the word

“products” appears after the arrow:

Alkyl radicals. The unpaired electron of each alkyl

radical is always indicated, e.g.:

Methyl free radical CHa*

Ethyl, 1 -methyl-, free radical

(Isopropyl) (CHakCH.

Methyl, hydroxy-, free radical *CH20H

(CH3)2 C=CHCH3 -f N—^products (24)

Display of Chemical Reactions and Formulae

A chemical reaction equation should show as clearly as possible the formation of products from the reactants. For

that reason, the reactions listed in the table are written on

the basis of semi-structural formulas.

Straight chain hydrocarbons. All saturated normal

hydrocarbons up to, and including n-pentane, are written

so as to show separately each methyl and methylene

group in the chain: CH4 , CH3 CH3 , CH3 CH2 CH3 , CH3 CH2 CH2 CH3 , CH3 CH2 CH2 CH2 CH3 . The higher hydrocarbons, from rc-hexane to n-decane,

are written in a more condensed form to facilitate the

counting of the number of methylene groups in the chain:

CH3(CH2 )4 CH3, CH3(CH2 )5CH3, CH3(CH2 )6CH3,

CH3(CH2 >7CH3, CH3(CH2 )8CH3.

The unsaturated hydrocarbons are written so as to show the position of each double or triple bond in the

molecule, e.g.:

Ethyne (Acetylene)

1.2-

Propadiene (Allene)

1.3-

Butadiyne

cw-2-Pentene

1-Heptene

CH=CH

CH2=C=CH2 CH=CC=CH

cw-CH3CH2 CH=CHCH3

CH3(CH2 )4CH=CH2

If the unpaired electron of an alkyl radical belongs to a carbon in the middle of the chain, it is indicated inside a parenthesis following the carbon atom, e.g.:

Propyl, 1 -methyl-, free radical

(sec-Butyl) CHaCHaCHOCHa

Butyl, 1,1 -dimethyl-, free radical (2-Methyl-2-pentyl) CHaCH2 CH2 C(-)(CHa )2 Methyl, oxo-, free radical

(Formyl) is written: *CHO

Oxy free radicals. If the oxygen atom of an oxy radical

is attached to the terminal carbon atom, the radical is written in the usual manner: CH3 O. If the oxygen atom of

the oxy radical is attached to a C atom in the middle of

the chain, then the oxygen atom, together with the

unpaired electron, are inside a parenthesis following the

C atom: (CHa^CWCHaCHa.

Peroxo, and other free radicals. The rules for writing peroxo, and other free radicals are the same as for the

oxy free radicals: CHa 02 -, CHaS*.

Atoms, like 0, H, S, N, and simple radicals like OH,

SH, NH, CH, CH2 , are written without dot. Hydroperoxyl

free radical is written H02 * (with dot).

7
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0+0+ M - 02 +M

OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 3. M: Ar NOTE: k FACTORS CHANGING TO: f = 0.4; F = 1.6 AT 4000K.

M: N2

M: 02 NOTE: k, = Kk_, . k FACTORS CHANGING TO: f = 0.5; F = 2.0

0 + 02 - 02 + 0 OXYGEN ATOM + OXYGEN MOLECULE

76 BEN/GOL REACTION ORDER: 2.

0 + 02 + M - 03 + M OXYGEN ATOM + OXYGEN

76 BAU/DRY

NOTE: M eff: 02 (1.5)

NOTE: M eff: Ar(l.O)

NOTE: M eff: N2 (1.4)

0 + 03 - 02 + 02 OXYGEN ATOM + OZONE

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.6; F = 3.0 AT a 1000K

0 + H + M - OH + M OXYGEN + HYDROGEN ATOMS

76 ENG REACTION ORDER: 3.

0 + H2 - OH + H OXYGEN ATOM + HYDROGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2.

0 + D2

-* OD + D OXYGEN ATOM + DEUTERIUM MOLECULE

72 BAU/DRY REACTION ORDER: 2.

0 + OH - 02 + H OXYGEN ATOM + HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 76 ENG

0 + OH - 02 + H OXYGEN ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + OH + M - H02 + M OXYGEN ATOM + HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 3.

0 + OH - OH + 0 OXYGEN ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + H 20 - OH + OH OXYGEN ATOM + WATER

72 BAU/DRY REACTION ORDER: 2.

0 + s2 - SO + s OXYGEN ATOM + SULFUR DIMER

75 BEN/GOL REACTION ORDER: 2.

0 + SO -» 02 + s OXYGEN ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

0 + SO - SO + 0 OXYGEN ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

0 + SO + M - S02 + M OXYGEN ATOM + SULFUR MONOXIDE

76 BAU/DRY REACTION ORDER: 3. M: Ar

MOLECULE

REACTION ORDER: 3. u2

AR

7VK A B E/R

(in K)

k factors

f F

190-4000 1.9(+13) 0 -900+175 0.8 1.2 190-400 1 .0( +14) 0 -720 0.5 1.5 2000-10000 4.7(+23) -2.5 0 0.4 2.5

AT s 8000K.

6 . 3 ( + 1 1

)

0.5 0

300 2 . 2 ( + 14) - - 0.8 1.2

300 1 . 5 ( +14) - - 0.8 1.3

300 2 . 1 ( +14) - - 0.8 1.2

200-500 5 . 2 ( + 12

)

0 2090+260 0.5 1.5

1500-2500 7.9(+15) 0 0 0.1 10.

400-2000 1.8(+10) 1.0 4480+150 0.7 1.3

416-968 2.0(+13) 0 5500 0.5 2.0

300 2.3(+13) 0.6 1.4 1500-2500 2.5(+13) 0 0 0.5 2.0

6 . 3( +11

)

0.5 0

1500-2500 1 . 0( +17

)

0 0 0.01 100.

6 . 3 ( + 1 1

)

0.5 4000

300-2000 6.8(+13) 0 9240+200 0.7 1.5

6 . 3 ( + 1 1

)

0.5 0

2 . 0 ( + 1 1

)

0.5 2770

6 . 3 ( + 1 1

)

0.5 0

298 6.7(+16) - - 0.7 1.3

8
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0 4 S02

-> 02 4 SO OXYGEN ATOM + SULFUR DIOXIDE

76 BAU/DRY REACTION ORDER: 2. NOTE: k x = Kk_!

0 4 SH - H + SO OXYGEN ATOM 4 MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 4 SH - OH + S OXYGEN ATOM 4 MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 4 N 4 M - NO 4 M OXYGEN ATOM 4 NITROGEN ATOM

73 BAU/DRY REACTION ORDER: 3. M:

0 + N2 - NO + N OXYGEN ATOM + NITROGEN MOLECULE

73 BAU/DRY REACTION ORDER: 2. NOTE: k L = Kk_ x 0 + N2 + M - N2 0 + M OXYGEN ATOM 4 NITROGEN MOLECULE

73 BAU/DRY REACTION ORDER: 3. M:

0 4 NO - 02 4 N OXYGEN ATOM 4 NITROGEN OXIDE(NO)

73 BAU/DRY REACTION ORDER: 2. NOTE: k x = Kk_j . k FACTORS CHANGING TO:

f = 0.5; F = 2.0 AT 3000K

0 4 NO - NO 4 0 OXYGEN ATOM 4 NITROGEN OX IDE (NO) 75 BEN/GOL REACTION ORDER: 2.

0 4 NO 4 M - N02 4 M OXYGEN ATOM 4 NITROGEN OXIDE(NO)

73 BAU/DRY REACTION ORDER: 3. NOTE: M eff: 02 (1.0) AT 297K

Ar(O.l) AT 297K

H20(6. 1) AT 297K

D20(5.0) AT 297K

SF6 (2.6) AT 297K

N2(l .4) AT 297K

N20(2. 1) AT 297K

C02 (2.1) AT 297K

CH4 (2 .2) AT 297K

CF4 (2.2) AT 297K

M

M

M

M

M

M

M

M

M

M

0 4 N02 - 02 4 NO OXYGEN ATOM 4 NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 2.

0 4 N02 - 02 4 NO OXYGEN ATOM 4 NITROGEN 0XIDE(N02 ) 76 ENG REACTION ORDER: 2.

0 4 N02 4 M - N03 4 M OXYGEN ATOM 4 NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 3. M (LOW PRESSURE). REACTION ORDER: 2. M NOTE: LIMITING HIGH PRESSURE k.

77 K A B E/R

(in K)

k factors

f F

440-2100 1.3(414) -0.5 9980 0.3 1.7

6.3(411) 0.5 0

6.3(411) 0 4000

n2 200-400 6.4(416) -0.5 0

2000-5000 7.6(413) 0 38000+150 0.5 2.0

Ar 1300-2500 1.4(413) 0 10400+1500 0.7 1.5

1000-3000 1.5(4 9) 1.0 19500+150 0.7 1.3

6.3(411) 0.5 0

02 200-500 1.1(415) 0 -940+50 0.8 1.2

Ar 200-500 1.1(414) 0 -940±50 0.8 1.2

H2 0 200-500 6.7(415) 0 -940±15 0.8 1.2

d2 o 200-500 5.5(415) 0 -940+50 0.8 1.2

SF6 200-500 2.9(415) 0 -940+50 0.8 1.2

n2 200-500 1.5(415) 0 -940+50 0.8 1.2

n2o 200-500 2.3(415) 0 -940150 0.8 1.2

co2 200-500 2.3(415) 0 -940+50 0.8 1.2

ch4 200-500 2.4(415) 0 -940+50 0.8 1.2

CF4 200-500 2.4(415) 0 -940+50 0.8 1.2

300-550 1.0(413) 0 300+100 0.8 1.3

1500-2500 1.0(413) 0 500+250 0.5 2.0

n2 295 2.3(416) - - 0.4 2.5

n2 295 1.1(413) 0.4 2.5

9
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0 + N20 - 02 + N2 OXYGEN ATOM + NITROGEN 0XIDE(N20) 73 BAU/DRY REACTION ORDER: 2.

0 + N20 - NO + NO OXYGEN ATOM + NITROGEN 0XIDE(N2 0) 73 BAU/DRY REACTION ORDER: 2.

0 + NH - OH + N OXYGEN ATOM + IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + NH - NO + H OXYGEN ATOM + IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + NH + M - HNO + M OXYGEN ATOM + IMIDOGEN FREE RADICAL

76 ENG REACTION ORDER: 3.

0 + NH3 - OH + NH2 OXYGEN ATOM + AMMONIA

73 BAU/DRY REACTION ORDER: 2.

0 + HNO - OH + NO OXYGEN ATOM + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2.

0 + HNO - 02 + NH OXYGEN ATOM + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2.

0 + HNO - N02 + H OXYGEN ATOM + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2.

0 + NS - SO + N OXYGEN ATOM + NITROGEN SULFIDE (NS) 75 BEN/GOL REACTION ORDER: 2.

0 + NS - NO + S OXYGEN ATOM + NITROGEN SULFIDE(NS)

75 BEN/GOL REACTION ORDER: 2.

0 + C + M - CO + M OXYGEN ATOM + CARBON ATOM 76 BAU/DRY REACTION ORDER: 3. NOTE: M = Ar, OR CO = Kk_!

0 + CO - 02 + C OXYGEN ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

0 + CO - CO + 0 OXYGEN ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

0 + CO + M -» CO + M OXYGEN ATOM + CARBON MONOXIDE

76 BAU/DRY REACTION ORDER: 3. M: CO

NOTE: k FACTORS CHANGING TO: f = 0.5; F = 1.2 AT 500K.

0 + C02 - 02 + CO OXYGEN ATOM + CARBON DIOXIDE

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.5; F = 1.5 AT 3000K.

k, = Kk_,

0 + CH - OH + C OXYGEN ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

1200-2000 1.0(+14) 0 14100+2000 0.4 2.5

1200-2000 1.0(+14) 0 14100+1500 0.5 2.0

6.3(+ll) 0.5 4000

6 . 3 ( + 1 1

)

0.5 0

1500-2500 1.0(116) -0.5 0+2500 0.3 3.2

300-1000 1 . 5 ( + 12

)

0 3000+300 0.5 1.5

1500-2500 5 . 0 ( + 1 1

)

0.5 • 0+2500 0.3 3.2

1500-2500 1.0(+11) 0.5 3500+2500 0.3 3.2

1500-2500 5.0(110) 0.5 0+2500 0.3 3.2

6.3(+ll) 0.5 4000

6 . 3( +1 1

)

0.5 0

7000-15000 3.3(+26) -3.1 2114 0.3 1.8

1 . 0( +12

)

0.5 69300

6 . 3 ( + 1 1

)

0.5 0

250-500 2.4(+15) 0 2184+280 0.8 1.2

1500-3000 1.7 (+13) 0 26500+2500 0.5 2.0

6.3(+ll) 0.5 4000

10
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0 + CH - CO + H OXYGEN ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + CH + M - CHO + M OXYGEN ATOM + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 3.

0 + :CH2 - H + .CHO OXYGEN ATOM + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2.

0 + :CH2 - OH + CH OXYGEN ATOM + METHYLENE

76 ENG FREE RADICAL

REACTION ORDER: 2 .

0 + CH3

. - H + OXYGEN ATOM + 76 ENG

HCHO METHYL FREE RADICAL

REACTION ORDER: 2 .

0 + CH4 - OH + CH3

. OXYGEN ATOM + METHANE

73 HER/HUI REACTION ORDER: 2. 76 ENG

0 + .CHO - H + C02 OXYGEN ATOM + METHYL, OXO- , FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

0 + .CHO - OH + CO OXYGEN ATOM + METHYL, 0X0- , FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

0 + HCHO -> OH + .CHO OXYGEN ATOM + FORMALDEHYDE

76 ENG REACTION ORDER: 2.

0 + HCHO -* products OXYGEN ATOM + FORMALDEHYDE

73 HER/HUI REACTION ORDER: 2.

0 + HCDO -> products OXYGEN ATOM + FORMALDEHYDE-d

73 HER/HUI REACTION ORDER: 2.

0 + CH3

0. - OH + HCHO OXYGEN ATOM + METHOXY FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED

0 + CS - C + SO OXYGEN ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + CS - CO + S OXYGEN ATOM + CARBON MONOSULFIDE FREE RADICAL

76 BAU/DRY REACTION ORDER: 2. 75 BEN/GOL

0 + cs2 - s + COS OXYGEN ATOM + CARBON DISULFIDE

76 BAU/DRY REACTION ORDER: 2.

0 + CS -» SO + CS OXYGEN ATOM + CARBON DISULFIDE

76 BAU/DRY REACTION ORDER: 2.

0 + COS - SO + CO OXYGEN ATOM + CARBON OXIDE SULFIDE

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.3; F = 3.0 ABOVE 600K.

77 K A B E/R

(in K) k factorsf F

6 . 3 ( + 1 10.5 0

1500-2500 1.0(+16) -0.5 0+2500 0.3 3.2

1500-2500 5 . 0 ( + 1 10.5 2000r2500 0.3 3.2

1500-2500 2 . 0 ( + 1 10.7 13100i2500 0.3 3.2

1500-2500 5.0(+13) 0 0 0.5 2.0

350-1000 2 . 1 ( +13

0 4550 0.7 1.3 1500-2500 2 . 0( +13

0 4530+500 0.6 1.6

1500-2500 3.2(tll) 0 0+1500

1500-2500 3 . 2 ( +1 11.0 250+1500

1500-2500 1.0(+11) 1.0 175011000 0.5 1.2

300 9.0(+10) - - 0.7 1.3

300 4.9(+10) - -

1500-2500 1.0(+14) 0 0+1500

1.6(+12) 0.5 28940

300 1-3 ( +13

0.5 1.5

6 . 3 ( +1 10.5 0

302 2 . 2 ( + 1 1

- - 0.5 1.5

200-1000 2.2(+13) 0 7001150 0.7 1.3

190-1200 1 . 6( +13

0 2250+250 0.5 1.5

11
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0 + CN - C + NO OXYGEN ATOM + CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

0 + CN - CO + N OXYGEN ATOM + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2.

0 + C2 - CO + C OXYGEN ATOM + CARBON DIMER

75 BEN/GOL

0 + CHsCH -» products OXYGEN ATOM + ETHYNE

73 HER/HUI

0 + CH2 =CH2 - cy-CH2CH20 OXYGEN ATOM + ETHENE

73 HER/HUI

0 + CH3CH3 - OH + CH2 CH2. OXYGEN ATOM + ETHANE

73 HER/HUI

0 + CH2 =C=0 -* products

OXYGEN ATOM + ETHENONE

73 HER/HUI

0 + CH3 CHO - products OXYGEN ATOM + ACETALDEHYDE

73 HER/HUI

0 + cy-CH2 CH2 0 -+ products OXYGEN ATOM + OXIRANE

73 HER/HUI

0 + CH3 CH2OH -» products

OXYGEN ATOM + ETHANOL

73 HER/HUI

0 + CH3OCH3 -» products

OXYGEN ATOM + METHANE, OXYBIS73 HER/HUI REACTION ORDER: 2.

0 + CH3CsCH -» products OXYGEN ATOM + PROPYNE

73 HER/HUI REACTION ORDER: 2.

0 + CH3CH=CH2 - cy-(CH3 )CHCH20 OXYGEN ATOM + 1-PROPENE

73 HER/HUI REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

REACTION ORDER: 2.

f ch3ch2ch3 - OXYGEN ATOM + 73 HER/HUI

OH + CH3 CH2 CH2 . \ (CH3 ) 2 CH. PROPANE REACTION ORDER: 2.

0 + (CH3 ) 2CHOH -* products

OXYGEN ATOM + 2-PROPANOL

73 HER/HUI REACTION ORDER: 2.

0 + (CH.} ) 2C=CH2 cy-(CH3 ) 2CCH20 OXYGEN ATOM + 1-PROPENE, 2-METHYL73 HER/HUI REACTION ORDER: 2. 0 + CH=CC=CH -* products

OXYGEN ATOM + 1 ,3-Bl'TADIYNE 73 HER/HUI REACTION ORDER: 2. 0 + CH2 =CHCH=CH 2 -» products

OXYGEN ATOM + 1 , 3-BUTADIENE

73 HER/HUI REACTION ORDER: 2.

77K A B E/R

(in K)

k factors

f F

1 . 3 ( + 12

)

0.5 14545

1500-2500 1.0(112) 0 0+2500 0.3 3.2

6.3(+ll) 0.5 0

200-700 1.4(+13) 0 1500 0.8 1.2

200-500 3.3(+12) 0 565 0.8 1.2

298-650 2 . 5 ( + 13

)

0 3200 0.7 1.3

298 5 . 3 ( + 1 1

)

l - 0.7 1.3

298-500 1 .4(+13) 0 1140 0.5 2.0

298 7.0(+ 8) - - 0.6 1.5

298 8.7(410) - - 0.6 1.5

200-500 5.9(412) 0 1520 0.7 1.3

298 4.0(+ll) - - 0.5 2.0

200-500 2.5(412) 0 38 0.8 1.2

298 9.0(+ 9) - - 0.7 2

298 1.3(411) - - 0.6 1.5

298 1 . 2 ( 413) - - 0.7 1.3

300 9.0(111) - - 0.7 1.4

298-400 3.4(+12) 0 -380 0.7 1.3

12
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0 1 CH3CH2 CH=CH2 - cy-(CH3CH2 )CHCH20 OXYGEN ATOM l 1-BUTENE

73 HER/HUI REACTION ORDER: 2.

0 1 cis-CH3CH=CHCH3 -* products

OXYGEN ATOM 1 cis-2-BUTENE

73 HER/HUI REACTION ORDER: 2.

0 1 trans-CH3CH=CHCH3 -* products

OXYGEN ATOM 1 trans-2-BUTENE

73 HER/HUI REACTION ORDER: 2.

0 + CH3CH2CH2CH3 - OH l CH3CH2CH2CH2

. OXYGEN ATOM 1 BUTANE

73 HER/HUI REACTION ORDER: 2.

0 1 CH3CH2CH2CH3 - OH 1 CH3CH2CH(.)CH3 OXYGEN ATOM l BUTANE

73 HER/HUI REACTION ORDER: 2.

0 l CH3CH2 CH2 CH=CH2 - cy-(CH3 CH2 CH2 )CHCH20 OXYGEN ATOM 1 1-PENTENE

73 HER/HUI REACTION ORDER: 2.

0 1 cis-CH3CH2 CH=CHCH3

-* products

OXYGEN ATOM 1 cis-2-PENTENE

73 HER/HUI REACTION ORDER: 2.

0 1 (CH3 ) 2C=CHCH3 -> products

OXYGEN ATOM l 2-BUTENE, 2-METHYL73 HER/HUI REACTION ORDER: 2.

0 l CH3CH2 CH2 CH2CH3

-* OH l CH3CH2 CH2CH2CH2. OXYGEN ATOM 1 PENTANE

73 HER/HUI REACTION ORDER: 2.

0 1 CH3CH2 CH2CH2CH3 - OH 1 CH3CH2 CH2CH(.)CH3

1 CH3CH2 CH(.)CH2 CH3 OXYGEN ATOM 1 PENTANE

73 HER/HUI REACTION ORDER: 2.

0 1 (CH3 ) 2CHCH2CH3 - OH l (CH3 ) 2C(.)CH2CH3

+ (CH3 ) 2CHCH(.)CH3 l (CH3 ) 2CHCH2 CH2 . 1 CH2CH(CH3 )CH2CH3 OXYGEN ATOM l BUTANE, 2-METHYL73 HER/HUI REACTION ORDER: 2.

0 l (CH3 ) 4C - OH 1 (CH3 ) 3CCH2

. OXYGEN ATOM 1 PROPANE, 2, 2-D I METHYL73 HER/HUI REACTION ORDER: 2.

0 l CH3CH2CH2CH2CH=CH2 - cy-(CH3CH2CH2CH2 )CHCH20 OXYGEN ATOM 1 1-HEXENE

73 HER/HUI REACTION ORDER: 2.

0 + (CH3 ) 2 C=C(CH3 ) 2 -* products

OXYGEN ATOM + 2-BUTENE, 2, 3-D I METHYL73 HER/HUI REACTION ORDER: 2.

0 + CH3 (CH2 ) 4CH3

-» OH + CH3 (CH2 ) 4CH2 . OXYGEN ATOM + HEXANE

73 HER/HUI REACTION ORDER: 2.

0 + CH3 (CH2 ) 4CH3 - OH + CH3CH(.)CH2CH2 CH2CH3

+ CH3CH2CH(.)CH2CH2CH3 OXYGEN ATOM + HEXANE

73 HER/HUI REACTION ORDER: 2.

0 + (CH3 ) 2CHCH(CH3 ) 2 - OH + CH2 CH(CH3 )CH(CH3 ) 2 OXYGEN ATOM + BUTANE, 2,3-DIMETHYL3 73 HER/HUI REACTION ORDER: 2.

0 + (CH3 ) 2 CHCH(CH3 ) 2 - OH + (CH3 ) 2 C(.)CH(CH3 ) 2 OXYGEN ATOM + BUTANE, 2, 3-DI METHYL73 HER/HUI REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

298 2.3(+12) - - 0.8 1.2

250-500 5.9(+12) 0 -165 0.8 1.2

298 1.4(+13) - - 0.7 1.3

298-650 3 . 0( +13) 0 2920 0.7 1.3

298-650 4.3(+13) 0 2410 0.7 1.3

298 2.8(+12) - - 0.7 1.3

298 1.1(113) - - 0.7 1.3

298-400 3.9(+12) 0 -680 0.8 1.2

298-650 2.9(113) 0 2920 0.7 1.3

298-650 8.0(+13) 0 2320 0.7 1.3

307 8.0(110) - - 0.7 1.4

298-650 5.9(113) 0 2920 0.7 1.4

298 3.1(112) - - 0.7 1.3

298-400 3.4(112) 0 -790 0.8 1.2

298-650 2.9(113) 0 2920 0.7 1.3

298-650 1.1(114) 0 2250 0.8 1.3

298-650 5.9(113) 0 2920 0.7 1.3

298-650 3.1(113) 0 1650 0.7 1.3

13
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

0 4 CH3 (CH2 ) 5CH 3 - OH + CH3 (CH2 ) 5CH2

. OXYGEN ATOM + HEPTANE

73 HER/HII REACTION ORDER: 2.

0 4 CH3 (CH2 ) 5CH3 - OH 4 CH3 (CH2 ) 4CH(.)CH3

+ CH 3 (CH.,) 3 CH'(.)(CH2).,CH 3 + CH 3 (CH2 ) 2 CH(.)(CH2 ) 2 CH3 OXYGEN ATOM + HEPTANE

73 HER/HII REACTION ORDER: 2.

0 4 (CH 3 ) 3 C(CH2 ) 2 CH 3 - products

OXYGEN' ATOM 4 PENTANE, 2, 2-D I METHYL73 HER/HII REACTION ORDER: 2.

0 4 (CH 3 ) 2 CHCH2 CH(CH 3 ) 2 -> products OXYGEN ATOM + PENTANE, 2, 4-D I METHYL73 HER/HII REACTION ORDER: 2.

0 + CH 3 (CH2 ) f) CH3 - OH 4 CH3 (CH2 ) 6CH2

. OXYGEN ATOM 4 OCTANE

73 HER/HII REACTION ORDER: 2.

0 4 CH3 (CH2 ) 6

CH3 - OH 4 CH3 (CH2 ) 5CH(.)CH3

4 CH 3 (CH2 ) 4CH( . )CH2 CH3 4 CH3 (CH2 ) 3CH(.)(CH2 ) 2CH3 OXYGEN ATOM + OCTANE

73 HER/HU I REACTION ORDER: 2.

0 4 (CH3 ) 3 CCH2 CH(CH3 ) 2 - products

OXYGEN' ATOM 4 PENTANE, 2, 2, 4-TR I METHYL73 HER/HII REACTION ORDER: 2.

0 4 (CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 -* products OXYGEN ATOM 4 PENTANE, 2 , 3 , 4-TR I METHYL73 HER/HII REACTION ORDER: 2.

0 + (CH3 ) 3 CC(CH3 ) 3 -* products

OXYGEN' ATOM 4 BUTANE, 2,2,3, 3-TETRAMETHYL73 HER/HUI REACTION ORDER: 2.

02 4 0 - 0 4 02 OXYGEN MOLECULE 4 OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

02 + 0 + M - 03 4 M OXYGEN MOLECULE 4 OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 3. NOTE: M eff: 02 ( 1 . 5

)

Ar(l.O)

N 2 (1.4)

M:

M:

M:

02 4 H - 0 t OH OXYGEN MOLECULE 4 HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 2. 72 KON

02 4 D - 0 4 OD OXYGEN MOLECULE 4 DEUTERIUM ATOM

72 BAU/DRY REACTION ORDER: 2.

02 4 H 4 M - H02 + M OXYGEN MOLECULE + HYDROGEN ATOM

72 BAU/DRY

M eff: H2 ( 1 .0) REACTION ORDER

02 (0.4)

H 2 0(6.4)

He(0.3)

.

1

II

Ar(0.3) 1

II

N2 (0.4)

M

M

M

M

M

M

T/K A B E/R

(in K)

k factors

f F

298-650 2 . 9 ( + 13

)

0 2920 0.7 1.3

298-650 1.2(4-14) 0 2190 0.7 1.3

307 6.5(410) - - 0.7 1.4

307 1.0(411) - - 0.7 1.4

298-650 2.9(413) 0 2920 0.7 1.3

298-650 9.3(413) 0 2030 0.7 1.3

307 5.5(410) - - 0.6 1.5

307 3.0(410) - - 0.6 1.5

307 8.0(4 9) - - 0.6 1.5

6.3(411) 0.5 0

02 300 2.2(414) - - 0.8 1.2

Ar 300 1.5(414) - - 0.8 1.3

n 2 300 2.1(414) - - 0.8 1.2

700-2500 2.2(414) 0 8450+250 0.7 1.3 310-2060 1.5(414) 0 8420+125 0.9 1.2

800-1000 8.9(413) - 7500

h 2 300-2000 5.0(+ 15) 0 -500+250 0.5 1.5

02 300-2000 2.0( + 15) 0 -500+250 0.5 1.5

h 2o 300-2000 3.2(4-16) 0 -500+250 0.5 1.5

He 300-2000 1.5(4-15) 0 -500+250 0.5 1.5

Ar 300-2000 1.5(4-15) 0 -500+250 0.5 1.5

n2 300-2000 2.0(4-15) 0 -500+250 0.5 1.5

14
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K) k

f factors

F 300-2000 7.5(+15) 0 -500+250 0.5 1.5

1500-2500 2 . 5 ( +12

0 19630+5000 0.1 10.

290-800 5 . 5 ( + 13

0 29100+350 0.4 2.5

250-450 1.4(+12) 0 0+50 0.3 1.7

440-2100 4.5(+ll) 0 3250+590 0.3 1.7

300-3000 6.4(+ 9) 1.0 3150+150 0.7 1.3

1200-2000 6.3(+13) 0 55200+2000 0.4 2.5

300-550 1 . 7 ( +12

0 23400 0.8 1.3

273-660 1.2(+ 9) 0 -530+100 0.5 1.5

ID2 )300-500 2.9(4 7) 0 -400+500 0.4 2.5

6.3(411) 0.5 0

1500-3000 2.5(412) 0 24000+2500 0.5 2.0

1500-2500 5.0(411) 0.5 3000+2500 0.3 3.2

5.0(411) 0.5 3500+2500 0.3 3.2

1500-2500 3.2(412) 0 15100+1500

1500-2500 3.2(413) 0 10000+5000 0.3 3.2

1500-2500 3.2(412) 0 34975+1500

M: CO,

02 + H2 - OH 4 OXYGEN MOLECULE 4 HYDROGEN MOLECULE

76 ENG REACTION ORDER: 2.

C02 (1.5)

OH 4 OH

0* + Hs H02 4 H OXYGEN MOLECULE 4 HYDROGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2.

02 4 S - 0 4 SO OXYGEN MOLECULE 4 SULFUR ATOM

76 BAU/DRY REACTION ORDER: 2.

02 4 SO - 0 + S02 OXYGEN MOLECULE + SULFUR MONOXIDE

76 BAU/DRY REACTION ORDER: 2.

02 4 N - 0 4 NO OXYGEN MOLECULE 4 NITROGEN ATOM

73 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f=0.5; F = 2.0 AT 3000K.

Oo 4 N, 0 4 N~0 OXYGEN MOLECULE 4 NITROGEN MOLECULE

73 BAU/DRY REACTION ORDER: 2. NOTE: kj = Kk_!

02 4 NO - 0 + N02 OXYGEN MOLECULE 4 NITROGEN OXIDE(NO)

73 BAU/DRY REACTION ORDER: 2. NOTE: k x = Kk_ x

02 4 NO 4 NO - N02 4 N02 OXYGEN MOLECULE 4 NITROGEN OXIDE(NO)

73 BAU/DRY REACTION ORDER: 3.

02 4 NO 4 N02 N02 4 NO,

02 4 C

73 BAU/DRY

0 4 CO

REACTION ORDER: 3.

OXYGEN MOLECULE 4 CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

02 4 CO - 0 + C02 OXYGEN MOLECULE + CARBON MONOXIDE

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING T0:f=0.5;F=1.5AT 3000K.

02 + CH - 0 + .CHO OXYGEN MOLECULE + METHYL I DYNE FREE RADICAL

76 ENG REACTION ORDER: 2.

02 + CH2 - 0 + HCHO

OXYGEN MOLECULE + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2.

02 + CH, 0 + CH»0. OXYGEN MOLECULE + METHYL FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

02 + CH3

. - OH + HCHO OXYGEN MOLECULE + METHYL FREE RADICAL

76 ENG REACTION ORDER: 2.

02 + CH3

. - H02 . + :CH2 OXYGEN MOLECULE + METHYL FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED

15
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R

(in K)

k factors

f F

02 + .CHO - H02 + CO OXYGEN MOLECULE + METHYL, OXO- , FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1 .

6

(

12 ) 0 3500+1500

NOTE: k ESTIMATED.

02 + CH30. - H02 + HCHO

OXYGEN MOLECULE + METHOXY FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1 . 0 (+ 12 ) 0 3000+1500

NOTE: k ESTIMATED.

02 + CN - CO + NO OXYGEN MOLECULE + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3 .

2

(

1

1

) 0 0+5000 0.3 3.2

02 + M - 0 + 0 + M OXYGEN MOLECULE

76 BAU/DRY REACTION ORDER: 2. 2500-8000 3 .

5

( +25 ) -2.5 59380 0.5 2.0

H 02 2000-10000 9.8(+24) -2.5 59380 0.4 2.5

NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 AT s 8000K

.

M Ar 3000-18000 1.8(+18) - 1.0 59380+4900 0.5 2.0

o3 + 0 - 02 + 02 OZONE + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 2. 200-500 5.2(+12) 0 2090+260 0.5 1.5

NOTE: k FACTORS CHANGING TO: f = 0.3; F = 3.0 AT LOOOK

03 + H - 02 + OH OZONE + HYDROGEN ATOM

76 BAU/DRY REACTION ORDER: 2. 300 1 . 6 ( +13

)

- - 0.5 2.0

O3 + OH - Oo + H02 OZONE t HYDROXYL FREE RADICAL

76 BAU/DRY REACTION ORDER: 2. 300 3.9(+10) - - 0.5 1.5

O3 + H02 - 02 + 02 + OH OZONE + HYDROPEROXYL FREE RADICAL

76 BAU/DRY REACTION ORDER: 2. 298 9. 1 (+ 8 ) - - 0.5 1.5

03 + H2 S - S02 + H2 0 OZONE + HYDROGEN SULFIDE

76 BAU/DRY REACTION ORDER: 2. 298 4.0(+ 2) - - 0.1 10 .

03 + NO - 02 + N02 OZONE + NITROGEN OXIDE(NO)

73 BAU/DRY REACTION ORDER: 2. 200-350 8 . 9 ( + 1

1

) 0 1330+130 0.5 1.5

03 + N02 - 02 + N03 OZONE r NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 2. 286-302 5 . 9(

12 ) 0 3500 0.5 2.0

03 +M - o+o2 +m

OZONE

76 BAU/DRY REACTION ORDER: 2. M Ar 200-1000 2.48(+14) 0 11430+120 0.8 1.3 H+O+M - OH+M

HYDROGEN ATOM + OXYGEN ATOM

76 ENG REACTION ORDER: 3. 1500-2500 7 . 9 ( + 15

)

0 0 0.1 10 .

H + 02 - OH + 0 HYDROGEN ATOM + OXYGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2. 700-2500 2.2(+14) 0 8450+250 0.7 1.3

D + Oo - OD + 0 DEUTERIUM ATOM - OXYGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2. 800-1000 8 . 9 ( + 13

)

0 7500

H + Oo + M - H02 + M HYDROGEN ATOM + OXYGEN MOLECULE

72 BAU/DRY REACTION ORDER: 3. M h 2 300-2000 5.0( + 15) 0 -500+250 0.5 1.5 NOTE: M eff: H 2 (1.0)

M O2 300-2000 2.0( + 15) 0 -500+250 0.5 1.5

02 (0.4)

M h 2o 300-2000 3.2(+ 16) 0 -500+250 0.5 1.5

H20 (6.4)

16
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77K A B E/R k

: actors

(in K) f F

M: He 300-2000 1.5( + 15) 0 -500+250 0.5 1.5 He(0.3) . ki = Kk_!

M: Ar 300-2000 1.5(4-15) 0 -500+250 0.5 1.5 Ar(0.3) . k x = Kk_!

M: n2 300-2000 2.0(4-15) 0 -500+250 0.5 1.5

N2 (0.4)

M: COo 300-2000 7.5(4-15) 0 -500+250 0.5 1.5 C02 (1.5)

H 4 03 - OH + 02 HYDROGEN ATOM 4 OZONE

76 BAU/DRY REACTION ORDER: 2. 300 1.6(413) - - 0.5 2.0

H 4 H 4 M - H2 + M HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 3. M: H2 300 3.0(415) - - 0.5 1.5

M: h2 2500-5000 2.6(415) -1.0 0 0.4 2.5

NOTE: M eff: H-(l.O)

M: Ar 2500-5000 6.4(417) -1.0 0 0.4 2.5

Ar(0.25) . kj = Kk_ x

H + H2 - H2 + H HYDROGEN ATOM 4 HYDROGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 4000

H + D2 - DH + D HYDROGEN ATOM 4 DEUTERIUM MOLECULE

72 KON REACTION ORDER: 2. 368-1000 3.1(413) 0 4485+250 0.6 1.6

D 4 H2 - DH 4 H DEUTERIUM ATOM 4 HYDROGEN MOLECULE

72 KON REACTION ORDER: 2. 400-1000 5.0(413) 0 3890+40 0.9 1.1

H + OH - H2 + 0 HYDROGEN ATOM 4 HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 400-2000 8.3(4 9) 1.0 3500+150 0.7 1.3

H 4 OH - OH 4 H HYDROGEN ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 0

H 4 OH 4 M - H20 4 M HYDROGEN ATOM + HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 3. M: H„0 1000-3000 1.4(423) -2.0 0 0.7 1.5

NOTE: M eff: H20(1.0). k, = Kk_,

M: Ar 1000-3000 8.4(421) -2.0 0 0.5 2.0

Ar ( 0 . 06

M: n2 1000-3000 2.2(422) -2.0 0 0.5 2.0

N2 (0. 16)

H + H02 - 0 + H20 HYDROGEN ATOM + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. 300-1000 5. (413) 0 500 0.3 3.2

NOTE: E ESTIMATED.

76 ENG 1500-2500 1.0(413) 0 5004500 0.1 1.0

H 4 H02-» H2 4 02 HYDROGEN ATOM 4 HYDROPEROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 290-800 2.5(413) 0 350+350 0.4 2.5

76 ENG 1500-2500 2.5(413) 0 350+350 0.5 2.0

H 4 H02 - OH + OH HYDROGEN ATOM + HYDROPEROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 290-800 2.5(414) 0 950r350 0.5 2.0

76 ENG 1500-2500 2.5(414) 0 950+500 0.5 2.0

H 4 H20 - OH + H2 HYDROGEN ATOM + WATER

72 BAU/DRY REACTION ORDER: 2. 300-2500 9.3(413) 0 10250+100 0.5 1.5

NOTE: ERROR LIMITS ARE 50% FOR UPPER T'S.

H 4 H202 - H2 4 ho2 HYDROGEN ATOM 4 HYDROGEN PEROXIDE

72 BAU/DRY REACTION ORDER: 2. 300-800 1.7(412) 0 1900+250 0.5 2.0

17
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A' B E/R

(in K) kf Factors

F

H + S2 - SH + S HYDROGEN ATOM + SULFUR DIMER

75 BEN/GOL REACTION ORDER: 2. 7.9(+12) 0.5 8355

H + SO - OH + S HYDROGEN ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 4.0(+12) 0.5 11200

H + SO - SH + 0 HYDROGEN ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 19930

H + S02 + M - HS02 + M HYDROGEN ATOM + SULFUR DIOXIDE

76 BAU/DRY REACTION ORDER: 3. 1660-2120 5. 1 (+15) 0.5 1.5

H + SH - H 2 + S HYDROGEN ATOM + MERCAPTO

76 BAU/DRY

FREE RADICAL

REACTION ORDER: 2. 298 1 . 5( +13) 0.5 1.5

H + SH - SH + H HYDROGEN ATOM + MERCAPTO

75 BEN/GOL

FREE RADICAL

REACTION ORDER: 2. 6 . 3 ( + 1 1

)

0.5 0

H + H2S - H 2 + SH HYDROGEN ATOM + HYDROGEN

76 BAU/DRY SULFIDE

REACTION ORDER: 2. 190-470 7 . 8 ( + 12

)

0 860150 0.5 1.5

H + N + M - NH + M HYDROGEN ATOM + NITROGEN

76 ENG ATOMREACTION ORDER: 3. 1500-2500 2 . 5 ( +17

)

-0.5 0+1000 0.1 10.

H + N2 - NH + N HYDROGEN ATOM + NITROGEN

75 BEN/GOL

MOLECULE

REACTION ORDER: 2. 2.0(+13) 0.5 75945

H + NO - OH + N HYDROGEN ATOM + NITROGEN

75 BEN/GOL

OXIDE(NO) REACTION ORDER: 2. 2.5(+12) 0.5 24460

H + NO - NH + 0 HYDROGEN ATOM + NITROGEN

75 BEN/GOL

OXIDE(NO) REACTION ORDER: 2. 5 . 0( +12

)

0.5 38200

H + NO + M - HNO + M HYDROGEN ATOM + NITROGEN

73 BAU/DRY

OXIDE(NO) REACTION ORDER: 3. 230-700 5.4(+15) 0 -3001100 0.5 1.5 H + NO + U - HNO + M HYDROGEN ATOM + NITROGEN

76 ENG OXIDE(NO) REACTION ORDER: 3. V : H2 1500-2500 5 . 0 ( + 15

)

0 -3001 150 0.5 2.0

H + N02 - OH + NO HYDROGEN ATOM + NITROGEN

73 BAU/DRY

NOTE: k FACTORS CHANGING TO

0XIDE(N02 ) REACTION ORDER: 2.

f = 0.5; F = 2.0 AT T = 633K. 298-630 3.5(+14) 0 7401500 0.5 1.5

H + N02 - OH + NO HYDROGEN ATOM + NITROGEN

76 ENG 0XIDE(N02 ) REACTION ORDER: 2. 1500-2500 3.2(+14) 0 7501500 0.5 2.0

H + N 20 - OH + N2 HYDROGEN ATOM + NITROGEN

73 BAU/DRY

0XIDE(N20) REACTION ORDER: 2. 700-2500 7.6(+13) 0 76001500 0.5 1.5

H + N20 - NH + NO HYDROGEN ATOM + NITROGEN

76 ENG 0XIDE(N20) REACTION ORDER: 2. 1500-2500 1.0(+11) 0.5 1510012500 0.3 3.2

H + NH - H2 + N HYDROGEN ATOM + IMIDOGEN

75 BEN/GOL

FREE RADICAL

REACTION ORDER: 2. 6.3(+ll) 0.5 4000

18
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R k factors

(in K) f F

H + NH - NH + H HYDROGEN ATOM + IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( + 1 1

0.5 0

H + NH2 + M - NH3 + M HYDROGEN ATOM + AMIDOGEN FREE RADICAL

73 BAU/DRY REACTION ORDER: 3. M: Ar 2000-3000 4.8(+14) 0 -8300r2500 0.5 2.0

NOTE: k x = Kk_!

H + NHeNHe - He + NHeNH. HYDROGEN ATOM + HYDRAZINE

73 BAU/DRY REACTION ORDER: 2. 250-500 1.3 ( +13) 0 1260rl00 0.5 2.0

H + HNO - H2 + NO HYDROGEN ATOM + NITROSYL HYDRIDE

73 BAU/DRY REACTION ORDER: 2. 2000 4.8(+12) - - 0.5 1.5

H + HNO - OH + NH HYDROGEN ATOM + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2. 1500-2500 2.0(+ll) 0.5 11600±2500 0.3 3.2

H + NS - SH + N HYDROGEN ATOM + NITROGEN SULFIDE(NO)

75 BEN/GOL REACTION ORDER: 2. 2 . 5 ( +12

0.5 15700

H + NS - NH + S HYDROGEN ATOM + NITROGEN SULFIDE (NO) 75 BEN/GOL REACTION ORDER: 2. 2.5(+12) 0.5 20735

H + CO - OH + C HYDROGEN ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 2 . 0 ( +13

0.5 77755

H + CO - CH + 0 HYDROGEN ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 2 . 5 ( +13

0.5 88020

H + CO + M - .CHO + M HYDROGEN ATOM + CARBON MONOXIDE

76 BAU/DRY REACTION ORDER: 3. M: H 2 298-773 6.9(+14) 0 850±500 0.7 1.3

NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 AT 773K. 76 ENG 1500-2500 1.6(+20) -1.5 0 0.3 3.2

H + C02 - OH + CO HYDROGEN ATOM + CARBON DIOXIDE

76 BAU/DRY REACTION ORDER: 2. 1000-3000 1.5(+14) 0 13300±150 0.8 1.2

H + CH - H2 + C HYDROGEN ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 4000

H + CH - CH + H HYDROGEN ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( +1 1

0.5 0

H + CH + M - CH2 + M HYDROGEN ATOM + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 3. 1500-2500 1 . 0( +19) -1.0 0 0.3 3.2

H + CH2 - H2 + CH HYDROGEN ATOM + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3 . 2 ( +11

0.7 250012500 0.3 3.2

H I ch4 - h 2 + ch3 . HYDROGEN ATOM + METHANE

76 ENG REACTION ORDER: 2. 1500-2500 6.3(+13) 0 5990il50 0.5 2.0

D + CH4 - DH + ch3

. DEUTERIUM ATOM + METHANE

72 KON REACTION ORDER: 2. 523-673 8.3(+12) 0 5100

H + .CHO - He + CO HYDROGEN ATOM + METHYL, OXO- , FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1.6(+12) 0.5 0i2500 0.3 3.2

19
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

H 4 HCHO - H 2 4 .CHO HYDROGEN ATOM 4 FORMALDEHYDE

76 ENG REACTION ORDER: 2.

H + CH30. - H2 4 HCHO HYDROGEN ATOM 4 METHOXY FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

H 4 CS - C 4 SH HYDROGEN ATOM 4 CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

H 4 CS - CH 4 S HYDROGEN ATOM 4 CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

H 4 COS - HS 4 CO HYDROGEN ATOM + CARBON OXIDE SULFIDE

76 BAU/DRY REACTION ORDER: 2.

H 4 CN - C 4 NH HYDROGEN ATOM 4 CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

H 4 CN - CH 4 N HYDROGEN ATOM 4 CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

H + CN + M - HCN 4 M HYDROGEN ATOM 4 CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 3.

H 4 C2 - CH 4 C HYDROGEN ATOM 4 CARBON DIMER

75 BEN/GOL REACTION ORDER: 2.

H 4 CH2 =CH2 - CH3CH2

. HYDROGEN ATOM 4 ETHENE

72 KER/PAR REACTION ORDER: 2.

H 4 CH2 =CH2 4 M - CH3CH2

. HYDROGEN ATOM 4 ETHENE

72 KON

4 MREACTION ORDER: 3.

H 4 CH3 CH3 - H2 4 CH3CH2. HYDROGEN ATOM 4 ETHANE

72 KON REACTION ORDER: 2.

H 4 CH3C=CH - CH3CH=CH 4 CH3C(.)=CH2 HYDROGEN ATOM 4 1-PROPYNE

72 KER/PAR REACTION ORDER: 2. NOTE: k TAKEN AS LOWER LIMIT.

H 4 CH3CH=CH2 - CH3CH2 CH2

. HYDROGEN ATOM + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

H + CH3CH=CH2 - CH3CH(.)CH3 HYDROGEN ATOM + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. NOTE: ARRHENIUS PARAMETERS ARE MINIMUM VALUES

OF THEIR HIGH-PRESSURE LIMITS.

H + CH 3CH2CH3 - H2 + (CH3 ) 2CH. + CH3CH2CH2. HYDROGEN ATOM + PROPANE

72 KON REACTION ORDER: 2.

H + (CH3 ) 2CO - H 2 + CH3C(0)CH2. HYDROGEN ATOM + 2-PR0PAN0NE

72 KON REACTION ORDER: 2.

TV K A B E/R

(in K)

k factors

f F

1500-2500 1.3(110) 1.0 1600 0.3 3.2

1500-2500 1.0(+14) 0 0+1500

2.0(113) 0.5 48870

1 . 3 ( +13

)

0.5 50930

298 1.3(+10) - - 0.8 1.3

1.0(+13) 0.5 52745

6.3(+12) 0.5 49775

1500-2500 3.2(416) -0.5 0+2500 0.3 3.2

1.6(413) 0.5 30450

298 9.3(413) 0 1410

298-813 5.6(417) 0.5 495

285-1440 1.0(414) 0 4815+70 0.8 1.2

298 0.5(411) - -

298 7.2(412) 0 1460

298 7.2(412) 0 605

333-933 1.0(413) 0 3130+180 0.7 1.4

298-873 4.6(413) 0 4220+20

20
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

H + CH2 =CHCH=CH2 - CH2 =CHCH(.)CH3 + CH2 =CHCH2CH2

. HYDROGEN ATOM 4 1,3-BUTADIENE

72 KER/PAR REACTION ORDER: 2. NOTE: AVERAGED RATE CONSTANT.

H + CH2 =CHCH=CH2 - CH2 =CHCH(.)CH3 4 CH2 =CHCH2 CH2

. HYDROGEN ATOM 4 1,3-BUTADIENE

72 KER/PAR REACTION ORDER: 2. k/kref : 4.9

NOTE: k ref : H+ CH3 CH=CH2

H 4 CH3CH2CH=CH2 - CH3CH2 CH(.)CH3 4 CH3 CH2 CH2CH2

. HYDROGEN ATOM + 1-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.03

NOTE: k ref : H 4 CH3 CH=CH2

H 4 CH3 CH2CH=CH2 - CH3 CH2CH2 CH2

. HYDROGEN ATOM + 1-BUTENE

72 KER/PAR REACTION ORDER: 2. NOTE: CALCULATED ON THE BASIS OF 5.7% NON-TERMINAL

ADDITION OF H TO 1-BUTENE.

H + CH3CH2 CH=CH2 - CH3 CH2 CH(.)CH3 HYDROGEN ATOM 4 1-BUTENE

72 KER/PAR REACTION ORDER: 2. NOTE: CALCULATED ON THE BASIS OF 5.7% NON-TERMINAL

ADDITION OF H TO 1-BUTENE. •

H + cis-CH3 CH=CHCH3 - CH3CH2 CH( . )CH3 HYDROGEN ATOM 4 cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. NOTE: NO KINETIC DATA ON REVERSE RADICAL DECOMPOSITION.

k/k ref : 0.47

NOTE: k ref : H + CH3 CH=CH2

.

H T trans-CH3CH=CHCH3 - CH3 CH2 CH( . )CH3 HYDROGEN ATOM 4 trans-2-BUTENE

72 KER/P.AR REACTION ORDER: 2. NOTE: AVERAGE k k/k ref : 0.59

NOTE: k ref : H 4 CH3 CH=CH2

.

H 4 (CH3 ) 2 C=CH2 - (CH3 ) 3

C. HYDROGEN ATOM 4 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2.

H 4 (CH3 ) 2C=CH2 - (CH3 ) 2CHCH2

. HYDROGEN ATOM 4 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. NOTE: CALCULATED ON THE BASIS OF 0.5% NON-TERMINAL

ADDITION OF H TO (CH3 ) 2C=CH2

.

H + (CH3 ) 2C=CH2 - (CH3 ) 3

C. + (CH3 ) 2 CHCH2 . HYDROGEN ATOM + 1-PROPENE, 2-METHYL72 KER/P.AR RLACTION ORDER: 2. k/k ref : 2.52

NOTE: k ref : H 4 CH3CH=CH2

H + CH3 CH2CH2 CH3 HYDROGEN ATOM

72 KON

- H2 + CH3 CH2CH(.)CH3 + CH3CH2 CH2 CH2

. + BUTANE

REACTION ORDER: 2.

H + (CH3 ) 3CH -

HYDROGEN ATOM

72 KON

H2 + (CH3 ) 3

C. 4 (CH3 ) 2CHCH2

. + PROPANE, 2-METHYLREACTION ORDER: 2.

H - CH3CH2CH2CH=CH2 - CH3CH2CH2CH(.)CH3

+ CH3CH2 CH2 CH2 CH2

. HYDROGEN ATOM + 1-PENTENE

72 KER/PAR RLACTION ORDER: 2. k/k

NOTE: k ref : H + CH3CH=CH2

. 0.89

T! K A B E/R

(in K)

298 4.10(413) 0 655

300 - - -

300 _ _ _

298 8.7(411) - -

298 5.0(410) - -

298 8.1(411) - -

298 4.6(411)

•

300 - - -

298 5.6(411) _ _

300 - - -

298 3.10(413) 0 755

298 1.3(411) - -

300 - - -

320-930 4.1(412) 0 2637+320

300-800 1.9(413) 0 2680t85

298 8.3(411) 300

21
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77K A B E/R

(in K)

k factors

f F

298 3 . 8 ( + 1 1

)

300

298 4. 1 ( +1 1

)

300

298 9. 1(+11) - -

298 2.0(+12) - -

298 7.4(+ll) - -

298 7 . 6( +1 1

)

- -

298 9. 1(+11)

300

298 7.8(+ll)

300

298 1 .6(+12) - -

400-2000 1.8(410) 1.0 4480+150 0.7 1.3

416-968 2.0(413) 0 5500 0.5 2.0

290-800 5.5(413) 0 29100+350 0.4 2.5

1500-2500 2.5(+12) 0 19630+5000 0.1 10.

6.3(411) 0.5 4000

H + c i s-CH3CH2 CH=CHCH3 - CH3CH2CH( . )CH2 CH3

+ CH3 CH2CH2 CH(.)CH3 HYDROGEN ATOM + cis-2-PENTENE

72 KER/PAR REACTION ORDER: 2. k/k re f

: 0.39

NOTE: k ref : H + CH3CH=CH2

.

H + trans-CH3 CH2CH=CHCH3 - CH3CH2CH(.)CH2CH3

+ CH3CH2 CH2 CH(.)CH3 HYDROGEN ATOM + trans-2-PENTENE

72 KER/PAR REACTION ORDER: 2. k/k re f

NOTE: k. H + CH„CH=CH;CH3CH2 H + CH3CH2C(CH3 )=CH2 C(.)(CH3 ) 2

+ CH3 CH2 CH(CH3 )CH2

. HYDROGEN ATOM + 1 -BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2.

D + CH3CH2C(CH3 )=CH2 - CH3CH2C(.)(CH3 )CH2 D

+ CH 3CH2CD(CH3 )CH2

. DEUTERIUM ATOM + 1-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2.

H + (CH3 ) 2 CHCH=CH2 - (CH3 ) 2 CHCH(.)CH3

+ (CH3 ) 2CHCH2CH2

. HYDROGEN ATOM + 1-BUTENE, 3-METHYL72 KER/PAR REACTION ORDER: 2.

D + (CH3 ) 2CHCH=CH2 - (CH3 ) 2CHCH(.)CH2 D

+ (CH3 ) 2 CHCHDCH2

. DEUTERIUM ATOM + 1-BUTENE, 3-METHYL72 KER/PAR REACTION ORDER: 2.

H + (CH3 ) 2C=CHCH3 - (CH3 ) 2CHCH(.)CH3

+ (CH3 ) 2C(.)CH2CH3 HYDROGEN ATOM + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k, NOTE: k ref : H + CH3CH=CH2

H + (CH3) 2 C=C(CH3) 2 - (CH3) 2CHC(.)(CH3) 2 HYDROGEN ATOM + 2-BUTENE, 2, 3-D I METHYL72 KER/PAR REACTION ORDER: 2. k/k, NOTE: k ref : H + CH3CH=CH2

H + (CH3 ) 3CC(CH3 )=CH2 - (CH3 ) 3CCH(CH3 )CH2

. + (CH3 ) 3CC(.)(CH3 ) 2 HYDROGEN ATOM + 1 -BUTENE, 2, 3,3, -TR I METHYL72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE VALUE BASED ON REACTION:

H + (CH3 ) 2C=CH2

H. + 0 - H + OH HYDROGEN MOLECULE + OXYGEN ATOM

72 BAU/DRY REACTION ORDER: 2.

+ 0 - D + OD DEUTERIUM MOLECULE + OXYGEN ATOM

72 BAU/DRY REACTION ORDER: 2.

+ 02 - H + H02

. HYDROGEN MOLECULE

72 BAU/DRY OXYGEN MOLECULE

REACTION ORDER: 2.

2 + 02 - OH + OH HYDROGEN MOLECULE + OXYGEN MOLECULE

76 ENG REACTION ORDER: 2.

H 2 + H - H + H 2 HYDROGEN MOLECULE + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER:

0.44

1.03

0.84

22
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions 7VK A B E/R

(in K) k factors

f F

H2 + D - H + HD HYDROGEN MOLECULE + DEUTERIUM ATOM

72 KON REACTION ORDER: 2. 400-1000 5.0(+13) 0 3890140 0.9 1.1

D2 + H - D + DH DEUTERIUM MOLECULE HYDROGEN ATOM

72 KON REACTION ORDER: 2. 1000 3 . 1 ( +13

0 4485+250 0.6 1.6

H2 + OH - H + H2 0 HYDROGEN MOLECULE + HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 300-2500 2.2(+13) 0 2590+100 0.8 1.2

NOTE: k FACTORS CHANGING TO: f = a. 5: F = 1.5 FOR T :300K T >300K

D2 + OH - D + DHO DEUTERIUM MOLECULE HYDROXYL FREE RADICAL

72 KON REACTION ORDER: 2. 300-623 1 . 9( +13) 0 2904+280 0.5 2.0

H, + HO, - H + H,0, HYDROGEN MOLECULE + HYDROPEROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 300-800 7.3(111) 0 9400+250 0.5 2.0

H2 + S - H + SH HYDROGEN MOLECULE + SULFUR ATOM

76 BAU/DRY REACTION ORDER: 2. 298 1 - 3

(— 1) - - 0.5 1.5

NOTE: k x = Kk x 75 BEN/GOL 2 . 5 ( +12

0.5 13640

H2 + N - H + NH HYDROGEN MOLECULE + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 2.5(+12) 0.5 18700

H2 + C - H + CH HYDROGEN MOLECULE + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2. 1.6(+12) 0.5 15700

H2 + C02 - H2 0 + CO HYDROGEN MOLECULE + CARBON DIOXIDE

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+ 9) 0.5 7550+2500 0.3 3.2

H2 + CH2 - H + CH3. HYDROGEN MOLECULE + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(+12) 0 3525+1500

NOTE: k ESTIMATED.

H2 + CH3

. - H + CH4 HYDROGEN MOLECULE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 370-700 8.5(+ll) 0 5500±500 0.7 1.3

H2 + CD3

. - H + CD3H HYDROGEN MOLECULE + METHYL-D3-FREE RADICAL

72 KON REACTION ORDER: 2. 400-570 7.4(+ll) 0 5250+235 0.6 1.7

DH + CH3

. - H + CH3 D DEUTERIUM HYDRIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 400-700 2.4(+ll) 0 5635±500 0.5 1.5

DH + CH3

. - D + CH4 DEUTERIUM HYDRIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 400-700 2 . 1 ( + 1 1

0 5300+500 0.5 1.5

D2 + CH3

. - D + CH3D DEUTERIUM MOLECULE f METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 300-700 7.1 ( +11

0 5990+250 0.7 1.3

H2 + CN - H + HCN HYDROGEN MOLECULE + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(+12) 0 2500+1500

NOTE: k ESTIMATED.

h2 + CH3CH2

. - H + CH3 CH3 HYDROGEN MOLECULE + ETHYL FREE RADICAL

72 KON REACTION ORDER: 2. 473-823 3.0(+ll) 0 5435

23
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical react ions 7VK A B E/R

(in K) k factorsf F

H2 + M - H + H + M HYDROGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2. M: Ar 2500-5000 2.2(114) 0 48300+2000 0.5 2.0

NOTE: k, = Kk_!

OH + 0 - 0 + OH HYDROXYL FREE RADICAL + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( + 1 1

)

0.5 4000

OH + 0 - H + 02 HYDROXYL FREE RADICAL + OXYGEN ATOM

72 BAU/DRY REACTION ORDER: 2. 300 2.3(+13) - - 0.6 1.4

NOTE: k, CALCULATED FROM k_|K IS: 1.3 X 10 13 cc.mo le-’s’*

OH + 0 - H + 02 HYDROXYL FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 2.5(113) 0 0 0.5 2.0

OH + 0 + M - H02 + M HYDROXYL FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 3. 1500-2500 1 .0(+17) 0 0 0.01 100.

OH + 03 - H02 . + 02 HYDROXYL FREE RADICAL + OZONE

76 BAU/DRY REACTION ORDER: 2. 300 3.9(+10) - - 0.5 1.5

OH + H - 0 + H2 HYDROXYL FREE RADICAL + HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 2. 400-2000 8.3(+ 9) 1.0 3500+150 0.7 1.3

OH + H - H + OH HYDROXYL FREE RADICAL + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

OH + H + M - H 2 0 + M HYDROXYL FREE RADICAL + HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 3. M: H 20 1000-3000 1.4(+23) -2.0 0 0.7 1.5

NOTE: M eff: H20(1.0). k t = Kk_!

M: Ar 1000-3000 8 . 4( +2 1

)

-2.0 0 0.5 2.0

Ar (0.06)

M: n 2 1000-3000 2.2(122) -2.0 0 0.5 2.0

N2

(0. 16)

OH + H2 - H20 + H HYDROXYL FREE RADICAL + HYDROGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2. 300-2500 2.2(+13) 0 2590+100 0.8 1.2 NOTE: k FACTORS CHANGING TO: f = 0.5; F = 1.5 FOR T >300K

OH + D2 - DHO + D HYDROXYL FREE RADICAL + DEUTERIUM MOLECULE

72 KON REACTION ORDER: 2. 300-623 1.9(413) 0 2904+280 0.5 2.0

OH + OH - H02 + H HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 290-800 1.2(413) 0 20200+350 0.5 2.0

OH + OH - H2 0 + 0 HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. 300-2000 6.3(+12) 0 550+200 0.7 1.5

OH + OH + M - H202 + M HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 3. M: n 2 700-1500 9.1(+14) 0 2550+1000 0.8 1.3 NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 AT 1500K.

OH + H 202 - H 20 + H02 HYDROXYL FREE RADICAL + HYDROGEN PEROXIDE

72 BAU/DRY REACTION ORDER: 2. 300-800 1.0(+13) 0 910+150 0.5 1.5

OH + S - 0 + SH HYDROXYL FREE RADICAL I SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2. 1.3(412) 0.5 12700

24
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77K A B E/R

(in K)

OH + S - H + SO HYDROXYL FREE RADICAL + SULFUR ATOM

75 BEN/G0L REACTION ORDER: 2. 6 . 3 ( +1 1

0.5 0

OH + H2 S - H2 0 + HS HYDROXYL FREE RADICAL + HYDROGEN SULFIDE

76 BAU/DRY REACTION ORDER: 2. 298-900 6 . 3 ( +12

0 200±150

NOTE: k FACTORS INCREASING TO: f = 0.5; F = 1.5 AT 900K.

OH + N - 0 + NH HYDROXYL FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 1 . 3 ( +12

0.5 17765

OH + N - H + NO HYDROXYL FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

OH + N + M - HNO + M HYDROXYL FREE RADICAL + NITROGEN ATOM

76 ENG REACTION ORDER: 3. 1500-2500 1.0(+15) -0.5 0

OH + N02 + M - HNOo + M HYDROXYL FREE RADICAL + NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 3. 300 5.0 ( +17

- -

OH + N2 0 - H02 + N2 HYDROXYL FREE RADICAL + NITROGEN 0XIDE(N20) 76 ENG REACTION ORDER: 2. 1500-2500 3.2(+13) 0 7550

NOTE: k ESTIMATED.

OH + NH - HoO + N HYDROXYL FREE RADICAL AND IMIDOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 5.0(+ll) 0.5 1000+2500

OH + HNO - H20 + NO HYDROXYL FREE RADICAL + NITROSYL HYDRIDE

73 BAU/DRY REACTION ORDER: 2. 2000 3.6(+13) - -

OH + HN03 - H20 + N03 HYDROXYL FREE RADICAL + NITRIC ACID

73 BAU/DRY REACTION ORDER: 2. 300 8 . 0 ( +10

- -

OH + C - 0 + CH HYDROXYL FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2. 7.9(+ll) 0.5 14800

OH + C - H + CO HYDROXYL FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(111) 0.5 0

OH + CO - H + C02 HYDROXYL FREE RADICAL + CYRBON MONOXIDE

76 BAU/DRY REACTION ORDER: 2. 250-2000 1 - 5 ( + 7) 1.3 - 385

NOTE: k FACTORS OVER 1000K: f = 0.5; F = 1.5. RECOMMENDED k FOR 250-2500K:

log(k)ccmol *s

1 = 10.83 + 3 .94~4T

OH + CH - H+ .CHO HYDROXYL FREE RADICAL AND METHYL I DYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 5.0(+ll) 0.5 5000+2500

OH + CH2 - 0 + CH3 . HYDROXYL FREE RADICAL AND METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 5 . 0 ( +1 1

0.5 3000=2500

OH + CH2 - H + HCHO HYDROXYL FREE RADICAL AND METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1 . 0( +13

0 2517

NOTE: k ESTIMATED.

OH + CH2 - H 20 + CH HYDROXYL FREE RADICAL AND METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 5 . 0 ( +1 1

0.5 3000+2500

k factors

f F

0.7 1.3

0.4 1.6

0.3 3.2

0.5 1.5

0.5 2.0

0.8 1.2

0.3 3.2

0.3 3.2

0.3 3.2

25
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R k factors

(in K) f F

OH + CH3. - H + CH30. HYDROXYL FREE RADICAL AND METHYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 6.3(+12) 0 0

OH + CH3. - H 20 + ch2 HYDROXYL FREE RADICAL AND METHYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 6.3(+10) 0.7 1000+2500 0.3 3.2

OH + CH4 - H 20 + ch 3. HYDROXYL FREE RADICAL + METHANE

76 ENG REACTION ORDER: 2. 1500-2500 3 .

2

( + 13

)

0 2500+250 0.5 2.0

OH - .CHO - H 2 0 * CO HYDROXYL FREE RADICAL + METHYL, OXO-, FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(+10) 1.0 0+1500

NOTE: k ESTIMATED.

OH + CH3

0. - H20 + HCHO HYDROXYL FREE RADICAL + METHOXY FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3 .

2

( + 13

)

0 0+1500

NOTE: k ESTIMATED.

OH + HCHO - H 20 + .CHO HYDROXYL FREE RADICAL + FORMALDEHYDE

76 ENG REACTION ORDER: 2. 1500-2500 3 .

2

(

10 ) 1.0 0+1500 0.5 2.0

OH + CN - 0 + HCN HYDROXYL FREE RADICAL + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(+12) 0 1500+1500

OH + HCN - H20 + .CN HYDROXYL FREE RADICAL + HYDROCYANIC ACID

76 ENG REACTION ORDER: 2. 1500-2500 2 . 0 (+ll) 0.6 2500+2500 0.3 3.2

OH + CH=CH - H20 + CH=CH. HYDROXYL FREE RADICAL + ETHYNE

72 KON REACTION ORDER: 2. 300-2000 7.6(+12) 0 2335+400 0.5 2.1

OH + CH2 =CH2 - H 2 0 + CH2 =CH. HYDROXYL FREE RADICAL + EHTENE

72 KON REACTION ORDER: 2. 3500-1400 1.6(+14) 0 2831+445 0.4 2.4

OH + CH2 =CH2 - .CH2 CH2OH HYDROXYL FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER: 2. 300 1 . 1 (+ 12 ) - - 0.8 1.3

OH + CH3CH3 - H20 + CH3CH2. HYDROXYL FREE RADICAL + ETHANE

72 KON REACTION ORDER: 2. 302-793 1.3(+14) 0 1998

OH + CH3CH=CH2 - CH3 CH(.)CH2OH + CH3CH(OH)CH2. HYDROXYL FREE RADICAL + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. 300 6 .

6

(

12 ) _ _

NOTE: ADDITION TO TERMINAL CARBON OF DOUBLE BOND

IS PROBABLY 95%

H02 + 03 - OH + 02 + 02 HYDROPEROXYL FREE RADICAL + OZONE

76 BAU/DRY REACTION ORDER: 2. 298 9. 1(+ 8 ) - - 0.5 1.5

HO, + H - 02 + H 2 HYDROPEROXYL FREE RADICAL + HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 2. 290-800 2.5(+13) 0 350+350 0.4 2.5

76 ENG 1500-2500 2.5(+13) 0 350+500 0.5 2.0

HO, + H - H20 + 0 HYDROPEROXYL FREE RADICAL + HYDROGEN ATOM

74 LLO REACTION ORDER: 2. 300-1000 5. (+13) 0 500 0.3 3.2

NOTE: E ESTIMATED.

HO, + H - OH + OH HYDROPEROXYL FREE RADICAL + HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 2. 290-800 2.5(+14) 0 950+350 0.5 2.0 I 76 ENG 1500-2500 2.5(+14) 0 956+500 0.5 2.0

26
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

H02 + H - H2 0 + 0 HYDROPEROXYL FREE RADICAL + HYDROGEN ATOM

76 ENG REACTION ORDER: 2.

H02 + H2 - H202 + H HYDROPEROXYL FREE RADICAL + HYDROGEN MOLECULE

72 BAU/DRY REACTION ORDER: 2.

H02 + H02 - H2 02 + 02 HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: E ESTIMATED, k FACTORS ARE LARGER AT T>300K.

H02 + H2 0 - H202 + OH HYDROPEROXYL FREE RADICAL + WATER

72 BAU/DRY REACTION ORDER: 2.

H02 + S02

-* OH + S03 HYDROPEROXYL FREE RADICAL + SULFUR DIOXIDE

74 LLO REACTION ORDER: 2.

H02 + N - 02 + NH HYDROPEROXYL FREE RADICAL + NITROGEN ATOM

76 ENG REACTION ORDER: 2.

H02 | CO - OH + C02 HYDROPEROXYL FREE RADICAL + CARBON MONOXIDE

76 BAU/DRY REACTION ORDER: 2.

H02 + CH - 02 + CH2 HYDROPEROXYL FREE RADICAL AND METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2.

H02 + CH - OH + .CHO HYDROPEROXYL FREE RADICAL AND METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2.

H02 + CH3

. - 02 + CH4 HYDROPEROXYL FREE RADICAL AND METHYL FREE RADICAL

76 ENG REACTION ORDER: 2.

H02 + .CHO - 02 + HCHO HYDROPEROXYL FREE RADICAL + METHYL, OXO-, FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

H02 + HCHO - H202 + .CHO HYDROPEROXYL FREE RADICAL + FORMALDEHYDE

74 LLO REACTION ORDER: 2. NOTE: k FACTORS ARE: f = 0.1; F = 10. AT 300 K.

H02 f CH2 =CH2 -> products HYDROPEROXYL FREE RADICAL + ETHENE

74 LLO REACTION ORDER: 2. NOTE: RATIO DATA VERSUS kref FOR H02 + CO -> OH + C02 . k FACTORS MIGHT BE HIGHER.

H02 + CH3 CH3 H2 02 + CH3 CH2

. HYDROPEROXYL RADICAL + ETHANE

74 LLO REACTION ORDER: 2. NOTE: E ESTIMATED. UPPER LIMIT RECOMMENDED.

k ref IS FOR H02 + CO - OH + C02

.

HO, CHoCHoCHc H202 + (CH3 ) 2 CH. HYDROPEROXYL FREE RADICAL

74 LLO

NOTE: UPPER LIMIT RECOMMENDED

FOR H02 + H02 - H202 + 02

+ PROPANE

REACTION ORDER: RATIO DATA VERSUS k.

H02 + (CH3 ) 2 C=CH2 -> products

HYDROPEROXYL FREE RADICAL + 1-PROPENE, 2-METHYL74 LLO REACTION ORDER: 2. NOTE: SUGGESTED k VALUE.

7VK A B E/R

(in K)

k factors

f F

1500-2500 1 . 0 ( + 13

0 500+500 0.1 10.

300-800 7.3(+ll) 0 9400+250 0.5 2.0

300-1000 1 . 0( +13) 0 500 0.5 2.0

300-800 2 . 8 ( +13

0 16500+500 0.5 1.5

300 5 . 2 ( + 8) - - 0.9 1.2

1500-2500 1.0(+11) 0 0+2500 0.3 3.2

700-1000 1 . 5 ( +14) 0 11900+1000 0.3 3.0

1500-2500 1.0(+10) 0.5 7550+2500 0.3 3.2

1500-2500 5.0(+ll) 0.5 300012500 0.3 3.2

1500-2500 1.0(+11) 0.5 3000+2500 0.3 3.2

1500-2500 1.0(+14) 0 1500+1500

300-800 1 . 0( +12) 0 4000 0.7 1.5

300 1.0(+ 7) - - 0.1 10.

300-1000 1 . 0( +12

0 7000 0.1 10.

300-1000 2 . 0( +11

0 5300 0.1 10.

300 1.0(+ 8) - - 0.1 10.

27
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K)

k factors

f F

300-1000 5.0(+ll

)

0 5285 0.1 10.

300-1000 1.0(111) 0 3500 0.1 10.

300-2000 2. 1 ( + 15

)

0 23000+250 0.5 1.5

300-2000 6.8(113) 0 9240+200 0.7 1.5

300-2500 9.3(113) 0 10250+100 0.5 1.5

300-800 2.8(+13) 0 16500+500 0.5 1.5

1500-2500 1 .0(411) 0.5 1500+2500 0.3 3.2

1273-1773 7.1(412) 0 12900+1000 0.5 2.C

h2 o 2000-6000 2.2(+16) 0 52900+2500 0.7 1.5

Ar 2000-6000 1.3(415) 0 52900+2500 0.5 2.0

N2 2000-6000 3.5(415) 0 52900+2500 0.5 2.0

300-800 1.7(412) 0 1900+250 0.5 2.0

300-800 1.0(+13) 0 910+150 0.5 1.5

n 2 700-1500 1.20(417) 0 22900+1000 0.8 1.3

250-450 1.4(+12) 0 0.0+50 0.5 1.5

298 1 - 3 (— 1) _ - 0.5 1.5

2.5(+12) 0.5 13640

6.3(+ll) 0.5 0

H02 + CH3 CH2CH2 CH3 - H2 02 + CH3 CH2CH(.)CH3 HYDROPEROXYL FREE RADICAL + BUTANE

74 LLO REACTION ORDER: 2. NOTE: UPPER LIMIT RECOMMENDED. RATIO DATA VERSUS kref

FOR HO, + HO, - H,0, + 0,

H02 + (CH0) 3CH - H2 02 + (CH3 ) 3C. HYDROPEROXYL FREE RADICAL + PROPANE, 2-METHYL

74 LLO REACTION ORDER: 2. NOTE: UPPER LIMIT RECOMMENDED. RATIO DATA VERSUS k ref FOR HO, + HO, - H,0, + 0,

H02 + M - H + 02 + M HYDROPEROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2. NOTE: M = AR, OR He. k, = Kk_,

H,0 + 0 OH + OH WATER + OXYGEN ATOM

72 BAU/DRY REACTION ORDER: 2.

H 20 + H - H2 + OH WATER + HYDROGEN ATOM

72 BAU/DRY REACTION ORDER: 2. NOTE: GIVEN k FACTORS ARE FOR HIGH T'S.

H2 0 + H02 - OH + H2 02 WATER + HYDROPEROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2.

H20 + NH - H2 + HNO WATER + IMIDOGEN FREE RADICAL

76 ENG REACTION ORDER: 2.

H20 + CH3. - OH + CH4 WATER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

H20 + M - H + OH + M WATER

72 BAU/DRY

NOTE: M eff: H20(1.0).

Ar(0.06)

N2 (0 . 16)

h2o2 + h - ho2 + h2 HYDROGEN PEROXIDE

72 BAU/DRY

REACTION ORDER: 2. M

kj = Kk_ x M

M

HYDROGEN ATOM REACTION ORDER: 2.

H 2 02 + OH - H02 + H20 HYDROGEN PEROXIDE + HYDROXYL FREE RADICAL

72 BAU/DRY REACTION ORDER: 2.

H 202 + M - OH + OH + M HYDROGEN PEROXIDE

72 BAU/DRY REACTION ORDER: 2. M: NOTE: k FACTORS CHANGING TO: f = 0.5; F 2.0 AT I500K.

S + 02 - SO + 0 SULFUR ATOM + OXYGEN MOLECULE

76 BAU/DRY REACTION ORDER: 2.

S + H2 - SH * H SULFUR ATOM + HYDROGEN MOLECULE

76 BAU/DRY REACTION ORDER: 2. NOTE: k, = Kk_ x 75 BEN/GOL

S - OH - SO - H SULFUR ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

28
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R

(in K)

k factors

f F

S 4 OH - SH 4 0 SULFUR ATOM 4 HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 1.3(112) 0.5 12700

s + s2 - s2 + s SULFUR ATOM 4 SULFUR DIMER

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

s 4 SO - So + 0 SULFUR ATOM 4 SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 11500

s 4 SO - so 4 s SULFUR ATOM 4 SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 6.3(111) 0.5 0

s 4 SH - S2 4 H SULFUR ATOM 4 MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

s 4 SH - SH 4 S SULFUR ATOM + MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(4-11) 0.5 4000

s 4 N2 - NS 4 N SULFUR ATOM 4 NITROGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2. 4.0(+12) 0.5 55200

s 4 NO - SO 4 N SULFUR ATOM 4 NITROGEN OXIDE (NO) 75 BEN/GOL REACTION ORDER: 2. 4.0(411) 0.5 17260

s 4 NO - NS 4 0 SULFUR ATOM 4 NITROGEN OXIDE (NO) 75 BEN/GOL REACTION ORDER: 2. 1.0(412) 0.5 17465

s 4 NH - SH 4 N SULFUR ATOM 4 IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 4000

s 4 NH - NS 4 H SULFUR ATOM 4 IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 0

s 4 NS - S2 + N SULFUR ATOM 4 NITROGEN SULFIDE(NS)

75 BEN/GOL REACTION ORDER: 2. 2.0(411) 0.5 10870

s + NS -* NS 4 S SULFUR ATOM 4 NITROGEN SULFIDE(NS)

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 0

s + CO - SO 4 C SULFUR ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 4.0(412) 0.5 66530

s + CO - CS + 0 SULFUR ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2. 1.3(412) 0.5 37600

s + CH - SH + C SULFUR ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 4000

s + CH - CS + H SULFUR ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 0

s + CS - So f c SULFUR ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 1.6(412) . 0.5 40463

29
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

s + cs - cs + s SULFUR ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

S + CS + M -* CS + M SULFUR ATOM + CARBON MONOSULFIDE FREE RADICAL

76 BAU/DRY REACTION ORDER: 3. NOTE: k, = Kk_!

S + CS2

-• S2 + cs SULFUR ATOM + CARBON DISULFIDE

76 BAU/DRY REACTION ORDER: 2.

S + COS - S + CO SULFUR ATOM + CARBON OXIDE SULFIDE

76 BAU/DRY REACTION ORDER: 2.

S + CN -* NS + C SULFUR ATOM + CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

S + CN - CS + N SULFUR ATOM + CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

S + C2

-* CS + c SULFUR ATOM + CARBON DIMER

75 BEN/GOL REACTION ORDER: 2.

S + CH=CH - cy-CH=CHS SULFUR ATOM + ETHYNE

72 KER/PAR REACTION ORDER: 2.

S + CH2 =CH2 - cy-CH2 CH2 S SULFUR ATOM + ETHENE

72 KER/PAR REACTION ORDER: 2.

S + CH3 CTCH - cy-(CH3 )C=CHS SULFUR ATOM * 1-PROPYNE

72 KER/PAR REACTION ORDER: 2.

S + CH3CH=CH2 - cy-(CH3 )CHCH2 S SULFUR ATOM + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. k/k re f

: NOTE: k ref : S + CH2 =CH2 SVD) + CH3CH=CH2 - cy-(CH3 )CHCH2 S SULFUR ATOM ( l D) + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : S’( X D) + CH2 =CH2

S + CH3CTCCH3 - cy- ( CH3) C=C ( CH3)

S

SULFUR ATOM + 2-BUTYNE

72 KER/PAR REACTION ORDER: 2.

S + CH2 =CHCH=CH2 - cy-(CH2 =CH)CHCH2 S SULFUR ATOM + 1,3-BUTADIENE

72 KER/PAR REACTION ORDER: 2.

S + CH3CH2 CH=CH2 - cy-(CH3 CH2 )CHCH2S SULFUR ATOM - 1-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k re f

NOTE: k ref : S + CH2 =CH2 S + cis-CH3 CH=CHCH3 - cy-(CH3 )CHCH(CH3 )S SULFUR ATOM + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k rc f

NOTE: k ref : S + CH2 =CH2

77 K A B E/R

(in K)

k factors

f F

6.3(+ll) 0.5 0

1800-3700 8.7(113) 0 4370 0.5 1.5

298 3.9(+ll) - - 0.5 1.5

230-2600 1.7(+12) 0 2050+230 0.3 3.0

2.0(+12) 0.5 32010

6.3(111) 0.5 0

6.3(+ll) 0.5 0

298 1 . 7 ( + 1 1

)

- -

298 8. 1 ( + 1 1

)

- -

298 1.1(112) - -

298 5.8(+12)

6.9 298

1.7 300 - - -

298 1 -9( +13) - -

298 6 . 0 ( + 13

)

- -

298 9.3(112)

10.0 298

298 1.4(+13)

16.0 298

30
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

S + trans-CH3 CH=CHCH3 - cy- ( CH3

) CHCH ( CH3

)

SULFUR ATOM + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : S + CH2 =CH2

S + (CH3 ) 2C=CH2 - cy-(CH3 ) 2CCH2S SULFUR ATOM + 1-PROPENE, 2-METHYL

72 KER/PAR REACTION ORDER: 2. k/k re f

NOTE: k ref : S + CH2 =CH2

S*( X D) t (CH3 ) 2C=CH2 - cy-(CH3 ) 2 CCH2 S SULFUR ATOM ( 1 D) t 1-PROPENE, 2 -METHYL72 KER/P.AR REACTION ORDER: 2. k/k ref : NOTE: k ref : S*(M)) + CH2 =CH2

S + CH3 (CH2 ) 2CH=CH2 - cy-CH3 (CH2 )CHCH2 S SULFUR ATOM + 1-PENTENE

72 KER/PAR REACTION ORDER: 2.

S + CH 3 CH2 C(CH3 )=CH2 - cy-CH3 CH2 C(CH3 )CH2 S SULFUR ATOM + 1-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2.

S + (CH3 ) 2 C=CHCH3 - cy-(CH3 ) 2CCH(CH3

)S SULFUR ATOM + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/kre f

: NOTE: k ref : S + CH2 =CH2 S + (CH3 ) 2 C=C(CH3 ) 2 - cy-(CH3 ) 2CC(CH3 ) 2

S SULFUR ATOM + 2-BUTENE, 2, 3-D I METHYL72 KER/PAR

S2 + 0 - S + SO SULFUR DIMER + 75 BEN/GOL

S2 + H - S + SH SULFUR DIMER + 75 BEN/GOL

S2 + S - S + S2 SULFUR DIMER + 75 BEN/GOL

S2 + N - S + NS SULFUR DIMER + 75 BEN/GOL

S2 + C - S + CS SULFUR DIMER + 75 BEN/GOL

SO + 0 - 0 + SO SULFUR MONOXIDE + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

SO + 0 - S + 02 SULFUR MONOXIDE - OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

SO + 0 | M - S02 + M SULFUR MONOXIDE + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 3.

SO + 02 - S02 + 0 SULFUR MONOXIDE + OXYGEN MOLECULE

76 BAU/DRY REACTION ORDER: 2. SO + H - 0 + SH SULFUR MONOXIDE + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

REACTION ORDER: 2.

OXYGEN ATOM REACTION ORDER: 2.

HYDROGEN ATOMREACTION ORDER: 2.

SULFUR ATOM REACTION ORDER: 2.

NITROGEN ATOMREACTION ORDER: 2.

CARBON ATOM REACTION ORDER: 2.

7VK A B E/R

(in K)

298 1.4(+13) 20.0 298

298 4.0(+13)

50.0 298

3.5 300 % - -

298 8.1(rl2) - -

298 7.4(+13) - -

298 6.5(~13)

56. 298

298 8.5(+13) - -

6.3(+ll) 0.5 0

7 .9(412) 0.5 8355

6.3(411) 0.5 0

6.3(411) 0.5 4000

6.3(411) 0.5 0

6.3(+ll) 0.5 0

2.0(+ll) 0.5 2770

298 6.7(413) - -

440-2100 4.5(411) 0 3250±590

6.3(411

0.5 19930

31
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chem ical reactions m A B E/R

(in K)

kf factors

F

SO + H - S + OH SULFUR MONOXIDE + 75 BEN/GOL

HYDROGEN ATOM REACTION ORDER: 2. 4.0(+12) 0.5 11200

SO + S - 0 + S2 SULFUR MONOXIDE + 75 BEN/GOL

SULFUR ATOMREACTION ORDER: 2. 6.3(111) 0.5 11500

SO + S - S + SO SULFUR MONOXIDE + 75 BEN/GOL

SULFUR ATOMREACTION ORDER: 2. 6

.

3( +11

)

0.5 0

SO + N - 0 + NS SULFUR MONOXIDE + 75 BEN/GOL

NITROGEN ATOM REACTION ORDER: 2. 1.6(+12) 0.5 8254

SO + N - S + NO SULFUR MONOXIDE + 75 BEN/GOL

NITROGEN ATOM REACTION ORDER: 2. 6 . 3 (

1

1

) 0.5 4000

SO + C - 0 * CS SULFUR MONOXIDE + 75 BEN/GOL

CARBON ATOMREACTION ORDER: 2. 6.3(111) 0.5 0

SO t C - S + CO SULFUR MONOXIDE + 75 BEN/GOL

CARBON ATOMREACTION ORDER: 2. 6 . 3 (

1

1

) 0.5 0

S02+ 0 - SO + 02 SULFUR DIOXIDE + 76 BAU/DRY

NOTE: k, = Kk.!

OXYGEN ATOM

REACTION ORDER: 2. 440-2100 1.3(+14) -0.5 9980 0.3 1.7

S02 + H + M - HS02 SULFUR DIOXIDE + 76 BAU/DRY

+ M HYDROGEN ATOM REACTION ORDER: 3. 1660-2120 5.1(+15) 0.5 1.5

S02 + H02 - S03 + OH SULFUR DIOXIDE + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: RATIO DATA VERSUS kref FOR REACTION

H02 + H02 - H202 + 02.

300 5.2(1 8) - - 0.9 1.2

SH + 0 - S + OH MERCAPTO FREE RADICAL + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 4000

SH + 0 - SO + H MERCAPTO FREE RADICAL + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( + 1 1

)

0.5 0

SH + H - S + H2 MERCAPTO FREE RADICAL + HYDROGEN ATOM

76 BAU/DRY REACTION ORDER: 2. 298 1.5(113) 0.5 1.5

SH + H - H + SH MERCAPTO FREE RADICAL + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( + 1 1

)

0.5 0

SH + S - H + S2 MERCAPTO FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3( +1 1

)

0.5 0

SH + S - S + SH MERCAPTO FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( PI 1

)

0.5 4000

SH + SH - H2S + S MERCAPTO FREE RADICAL

76 BAU/DRY REACTION ORDER: 2. 295 7.8(+12) 0.5 1.5

SH + N - H + NS MERCAPTO FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( + 1 1

)

0.5 403

32
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

SH + N - S + NH MERCAPTO FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

SH + C - H + CS MERCAPTO FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

SH + C - S + CH MERCAPTO FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

H2

S + 03 - H20 + S02 HYDROGEN SULFIDE + OZONE

76 BAU/DRY REACTION ORDER: 2.

H2S + H - SH + H2 HYDROGEN SULFIDE + HYDROGEN ATOM

76 BAU/DRY REACTION ORDER: 2.

H2S + OH - SH + H2 0 HYDROGEN SULFIDE + HYDROXYL FREE RADICAL

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.5; F = 1.5 AT 900K.

H2S + CH3. - SH + CH4 HYDROGEN SULFIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

N + 0 + M - NO + M NITROGEN ATOM + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 3. M: N2

N + '02 - NO + 0 NITROGEN ATOM + OXYGEN MOLECULE

73 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 AT 3000K.

N + H + M - NH + M NITROGEN ATOM + HYDROGEN ATOM

76 ENG REACTION ORDER: 3.

N + H2 - NH + H NITROGEN ATOM + HYDROGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2.

N + OH - NO + H NITROGEN ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

N + OH - NH + 0 NITROGEN ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

N + OH + M - HNO + M NITROGEN ATOM + HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 3.

N + H02 - NH + 02 NITROGEN ATOM + HYDROPEROXYL FREE RADICAL

76 ENG REACTION ORDER: 2.

N + S2 - NS + S NITROGEN ATOM + SULFUR DIMER

75 BEN/GOL REACTION ORDER: 2.

N + SO - NO + S NITROGEN ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

N + SO - NS + 0 NITROGEN ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

7VK A B E/R

(in K) k factorsf F

6.3(4-11) 0.5 9060

6.3(+ll) 0.5 0

4.0(+ll) 0.5 6090

298 4.0(+ 2) - - 0.1 10.

190-470 7.8(+12) 0 860+50 0.5 1.5

298-900 6.3(+12) 0 200+150 0.7 1.3

300-600 2 .00 (+11) 0 2065+150 0.4 2.5

200-400 6.4(+16) -0.5 0 0.5 1.5

300-3000 6.4(+ 9) 1.0 3150+150 0.7 1.3

1500-2500 2 . 5( +17) -0.5 0+1000

2 . 5 ( +12

0.5 18700

6.3(+ll) 0.5 0

1.3(+12) 0.5 17765

1500-2500 1.00(+15) -0.5 0

1500-2500 1.00(+11) 0 0+2500 0.3 3.2

6.3(+ll) 0.5 4000

6 . 3 ( + 1 10.5 4000

1 . 6( +120.5 8254

33
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

N + SH - NH + S NITROGEN ATOM + MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

N + SH - NS + H NITROGEN ATOM + MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

N + N + M - N2 + M NITROGEN ATOM

73 BAU/DRY REACTION ORDER: 3. M: N 2 NOTE: k FACTORS RANGE: 200-600K, BUT MIGHT INCREASE

AT LOWER T'S.

N + N 2 - N 2 + N NITROGEN ATOM + NITROGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2.

N + NO - N 2 + 0 NITROGEN ATOM + NITROGEN OX IDE (NO) 73 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGE TO: f = 0.5; F = 2.0 ABOVE 2000K.

N + NO - NO + N NITROGEN ATOM + NITROGEN OXIDE(NO)

75 BEN/GOL REACTION ORDER: 2.

N + N02 - N2 + 02 NITROGEN ATOM + NITROGEN 0XIDE(N02 ) 76 ENG REACTION ORDER: 2.

N + N02 - NO + NO NITROGEN ATOM + NITROGEN 0XIDE(N02 ) 76 ENG REACTION ORDER: 2.

N + N02 - N20 + 0 NITROGEN ATOM + NITROGEN 0XIDE(N02 ) 76 ENG REACTION ORDER: 2.

N + N20 - NO + N2 NITROGEN ATOM + NITROGEN 0XIDE(N20) 76 ENG REACTION ORDER: 2.

N + NH - N2 + H NITROGEN ATOM + IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

N + NH - NH + N NITROGEN ATOM + I MIDGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

N + HNO - H + N20 NITROGEN ATOM + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2.

N + HNO - NH + NO NITROGEN ATOM + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2.

N + NS - N2 + S NITROGEN ATOM + NITROGEN SULFIDE(NS)

75 BEN/GOL REACTION ORDER: 2.

N + NS - NS + N NITROGEN ATOM + NITROGEN SULFIDE(NS)

75 BEN/GOL REACTION ORDER: 2.

N + CO - NO + C NITROGEN ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

N + CO - CN + 0 NITROGEN ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

6 . 3 ( + 1 1

)

0.5 9060

6 . 3 ( + 1 1

)

0.5 403

100-600 3.0(+14) 0 - 500+50 0.5 1.5

6.3(+ll) 0.5 4000

300-5000 1 . 6 ( + 13

)

0 0 0.8 1.2

6.3(+ll) 0.5 4000

1500-2500 1.0(+12) 0 0+1500

1500-2500 4.0(+12) 0 0+1500 0.2 5.0

1500-2500 5.0(+12) 0 0+1500 0.5 2.0

1500-2500 5 . 0 ( + 8) 0 5000+2500 0.3 3.2

6.3(111) 0.5 0

6.3(111) 0.5 4000

1500-2500 5.0(110) 0.5 1500+2500

1500-2500 1.0(+11) 0.5 1000+2500

6 . 3 ( + 1 1

)

0.5 0

6 . 3 ( + 1 1

)

0.5 4000

5.0(+12) 0.5 57300

3 . 2 ( + 12

)

0.5 38800

34
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77K A B E/R

(in K)

N + C0„ - NO + CO NITROGEN ATOM + CARBON DIOXIDE

76 ENG REACTION ORDER: 2. 1500-2500 2 . 00 (+11) 0.5 1500+10000

N + CH - NH + C NITROGEN ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 1.0(+12) 0.5 6995

N + CH - CN + H NITROGEN ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 0

N + CHo - NH + CH NITROGEN ATOM + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 6.3(+ll) 0.67 20400=2500

N + .CHO - 0 + HCN NITROGEN ATOM + FORMYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1.0(414) 0 0 NOTE: k ESTIMATED.

N + .CHO - NH + CO NITROGEN ATOM + FORMYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 2.0(411) 0.5 1000+2500

N + CHoO. -> NH + HCHO

NITROGEN ATOM + METHOXY FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1.0(414) 0 0+1500

N + CS - C + NS NITROGEN ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 4.0(+12) 0.5 37200

N + CS - .CN + S NITROGEN ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 1.3(412) 0.5 1160

N + CN - No + C NITROGEN ATOM + CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. 6.3(411) 0.5 0

N | C2 - CN + C NITROGEN ATOM + CARBON DIMER

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

N + CH^CH - C2 H2

N NITROGEN ATOM + ETHYNE

72 KER/PAR REACTION ORDER: 2. 440 2.0(4 9) — _

NOTE: UPPER LIMIT.

N + CH2 =CH2 -» products

NITROGEN ATOM + ETHENE

72 KER/PAR REACTION ORDER: 2. 320-550 2.0(+10) 0 353

N + CH3CsCH -* products

NITROGEN ATOM + 1-PROPYNE

72 KER/PAR REACTION ORDER: 2. 320-550 6.9(110) 0 745 k/k re f

: 6.5 435 _ — _

NOTE: k ref : N + CH=CH

N + CH3CH=CH2 -» products

NITROGEN ATOM + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. 320-550 1.2(411) 0 655

k/k re f: 2.8 435 _ _ _

NOTE: k ref : N + CH2 =CH2

N + CH3 CH2C2CH - products

NITROGEN ATOM + 1-BUTYNE

72 KER/PAR REACTION ORDER: 2. 320-550 3.5(111) 0 1125 k/k re f

: 13.0 435 _ _ _

NOTE: k ref : N + CH^CH

k factors

f F

0.1 10 .

0.3 3.2

35
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

N + CH3C=CCH3 - products NITROGEN ATOM + 2-BUTYNE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k rcf : N + CH=CH.

N + CH2 =CHCH=CH2 - products

NITROGEN ATOM + 1.3-BUTADIENE

72 KER/PAR REACTION ORDER: 2.

N + CH3CH2CH=CH2 - products

NITROGEN ATOM + 1-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k re ,-: NOTE: k ref : N + CH2 =CH2

.

N + cis-CH3 CH=CHCH3

-* products NITROGEN ATOM + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : N + CH2 =CH2

N + trans-CH3CH=CHCH3

-» products NITROGEN ATOM + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k

NOTE: k ref : N + CH2 =CH2

N + (CH3 ) 2C=CH2 -» products NITROGEN ATOM + 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/kref : NOTE: k ref : N + CH2 =CH2

N + CH3 CH2 CH2CsCH - products

NITROGEN ATOM + 1-PENTYNE

72 KER/PAR REACTION ORDER: 2. k/k : NOTE: k ref : N. + CH=CH

N + (CH3 ) 2C=CHCH3 -» products

NITROGEN ATOM + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k rcf : N + CH2 =CH2

N + CH3CH2CH2 CH2 C=CH - products NITROGEN ATOM + 1-HEXYNE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k rcf : N + CH=CH

N + CH3 CH2 CsCCH2CH3 -* products NITROGEN ATOM + 3-HEXYNE

72 KER/PAR REACTION ORDER: 2. k/k re f

NOTE: k ref : N + CH=CH

N + (CH3 ) 2C=C(CH3 ) 2 -* products NITROGEN ATOM' + 2-BUTENE, 2, 3-D I METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k rcf : N + CH2 =CH2

N 2 + 0 - N + NO NITROGEN MOLECULE + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2. NOTE: k, = Kk_ x

N 2 + 0 + M - N20 + M NITROGEN MOLECULE + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 3. M:

7VK A B E/R

(in K)

12.0 320-550435

1 . 9( +1 1

)

0 926

340 3.5(110) - -

3.4

320-550

435

1 . 6( +1 1

)

0 660

2.4

320-550

435

2 . 3 ( + 1 1

)

0 995

3.0 320-550

435

3.4(111) 0 1055

4.1 320-550435 7.8(110) 0 277

14.0 320-550435 3.0(+ll) 0 1047

3.5 320-550435

9.3(110) 0 433

14.0 320-55435 4.6(+ll

)

0 1233

14.0 320-550

435

3.4(+ll) 0 1102

3.5 320-550435

1.7(+11) 0 690

2000-5000 7.6(113) 0 38000+150

Ar 1300-2500 1.4(+13) 0 10400+1500

k factors

f F

0.5 2.0

0.7 1.5

36
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R

(in K) k factors

f F

1200-2000 6.3(+13) 0 55200+2000 0.4 2.5

2.0(+13) 0.5 75945

4.0(+12) 0.5 55200

6.3(+ll) 0.5 4000

1 . 3 ( +120.5 22750

1500-2500 1.0(+11) 0 9560

1500-2500 3 . 2 ( +14) 0 46300+10000

1500-2500 1.0(+14) 0 35230+10000

M: n2 1500-2500 6000-15000

4.0(+21)

3. 7 (+21)

-1.6

-1.6

13240+500

113200+500 0.3 3.0

6.3(+ll) 0.5 0

3000K. 1000-3000 1.5(+ 9) 1.0 19500+150 0.7 1.3

M: O2 200-500 1 . 1 ( +15

0 -940x50 0.8 1.2

M: Ar 200-500 1.1 ( +14) 0 -940+50 0.8 1.2

M: H20 200-500 6 . 7 ( +15

0 -940x50 0.8 1.2

M: d2o 200-500 5.5(+15) 0 -940+50 0.8 1.2

M: sf6 200-500 2.9(+15) 0 -940+50 0.8 1.2

M: n2 200-500 1 . 5 ( +15

0 -940+50 0.8 1.2

M: n2o 200-500 2.3(+15) 0 -940+50 0.8 1.2

M: co2 200-500 2 . 3 ( +15

0 -940+50 0.8 1.2

M: ch4 200-500 2.4(+15) 0 -940+50 0.8 1.2

M: CF4 200-500 2.4(+15) 0 -940x50 0.8 1.2

No + 0, NoO + 0 NITROGEN MOLECULE + OXYGEN MOLECULE

73 BAU/DRY REACTION ORDER: 2. NOTE: kj = Kk^

N, H N + NH NITROGEN MOLECULE + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

N2 + S - N + NS NITROGEN MOLECULE + SULFUR ATOM

75 BEN/GOL REACTION ORDER:

N2 + N - N + N2 NITROGEN MOLECULE + NITROGEN ATOM

75 BEN/GOL REACTION ORDER:

N2 + C - N + CN NITROGEN MOLECULE + CARBON ATOM

75 BEN/GOL REACTION ORDER:

N2 + CH - N + HCN NITROGEN MOLECULE + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: REVISED ESTIMATE.

N2 + CH - NH + CN NITROGEN MOLECULE

76 ENG

NOTE: k ESTIMATED.

METHYLIDYNE FREE RADICAL

REACTION ORDER: 2.

N2 + CH2 - NH + HCN NITROGEN MOLECULE + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

N2 + M - N + N + M NITROGEN MOLECULE

76 ENG

73 BAU/DRY REACTION ORDER: 2.

NO + 0 - 0 + NO NITROGEN OXIDE (NO) + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

NO + 0 - N + 02 NITROGEN OXIDE(NO) + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS INCREASING TO: f = 0.5; F = 2.0

k x = Kk_ x NO + 0 + M - N02 + M NITROGEN OXIDE(NO) + OXYGEN ATOM

73 BAU/DRY REACT!

NOTE: M eff: 02 (1.0) AT 297K

Ar(O.l) AT 297K

H20(6. 1) AT 297K

D20(5.0) AT 297K

SF6 (2.6) AT 297K

N2

(l .4) AT 297K

N2 0(2.1) AT 297K

C02 (2.1) AT 297K

CH4 (2.2) AT 297K

CF4 (2.2) AT 297K

37
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemica 1 reactions 77 K A B E/R k factors

(in K) f F

NO + 02 - N02 + 0 NITROGEN OX IDE (NO) + OXYGEN MOLECULE

73 BAU/DRY REACTION ORDER: 2. 300-550 1.7(112) 0 23400 0.8 1.3

NOTE: k t = Kk_,

NO + o3 - no2 + 02 NITROGEN OXIDE(NO) + OZONE

73 BAU/DRY REACTION ORDER: 2. 200-350 8.9(111) 0 1330+130 0.5 1.5

NO + H - 0 + NH NITROGEN OXIDE(NO) + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 5.0(+12) 0.5 38200

NO + H - N + OH NITROGEN OXIDE(NO) + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 2.5(+12) 0.5 24460

NO + H + M - HNO + M NITROGEN OXIDE(NO) + HYDROGEN ATOM

73 BAU/DRY REACTION ORDER: 3. M: H2 230-700 5.4(+15) 0 -300+100 0.5 1.5 76 ENG M: H2 1500-2500 5 . 0 ( + 15

)

0 -300+150 0.5 2.0

NO + S - 0 + NS NITROGEN OXIDE(NO) + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2. 1 . 0 ( +12

)

0.5 17465

NO + S - N + SO NITROGEN OXIDE(NO) + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2. 4.0(+ll) 0.5 17260

NO + N - 0 + N2 NITROGEN OXIDE(NO) + NITROGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 300-5000 1.6(+13) - - 0.8 1.2

NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 ABOVE 2000K

NO + N - N + NO NITROGEN OXIDE(NO) + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 4000

NO + NO - N2 + 02 NITROGEN 0XIDE(N02 ) OXYGEN MOLECULE

72 KON REACTION ORDER: 2. 1370-4300 1 . 3( +14) 0 38060+720 0.7 1.5

NO + NO - N 20 + 0 NITROGEN OXIDE (NO) 73 BAU/DRY REACTION ORDER: 2. 1200-2000 1 . 3 ( + 12

)

0 32100+1500 0.5 2.0

NO + NO + 02

-» N02 + 1S02 NITROGEN OXIDE(NO) + OXYGEN MOLECULE

73 BAU/DRY REACTION ORDER: 3. 273-660 1.2(1 9) 0 -530+100 0.5 1.5

NO * NO2

“* N2O ^ ^2 NITROGEN OXIDE(NO) + NITROGEN 0XIDE(N02 ) 76 ENG REACTION ORDER: 2. 1500-2500 1.0 (+12) 0 30200 0.01 100.

NO + N02 + 02 - N02 + N03 NITROGEN OX IDE (NO) + NITROGEN 0XIDE(N02 ) + OXYGEN MOLECULE

73 BAU/DRY REACTION ORDER: 3. 300-500 2.9(+ 7) 0 -400+500 0.4 2.5

NO + N03 - N02 + no2 NITROGEN OX IDE (NO) + NITROGEN 0XIDE(N03 ) 72 KON REACTION ORDER: 2. 298-547 1 . 5( +14) 0 1163+115 0.7 1.4

NO * ^2^ N0<2 *f N2 NITROGEN OXIDE(NO) + NITROGEN 0XIDE(N20) 76 ENG REACTION ORDER: 2. 1500-2500 2 . 0 ( + 14) 0 25000 0.1 1.0

NO + HNO - N20 + OH NITROGEN OXIDE(NO) + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2. 1500-2500 2.0(+12) 0 13000+2500 0.5 2.0

38
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77K A B E/R

(in K) k factors

f F

NO + C - 0 + CN NITROGEN OX IDE (NO) + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2. 6 . 3 ( + 1 1

0.5 0

NO + C - N + CO NITROGEN OX IDE (NO) + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 4000

NO + CH - 0 + HCN NITROGEN OX IDE (NO) + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 2.0(+12) 0 0+1000

NOTE: kESTIMATED.

NO + CH - N + .CHO NITROGEN OX IDE (NO) + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1 . 6(+13) 0 5000+3000

NOTE: k ESTIMATED.

NO + CH2 - N + HCHO NITROGEN OX IDE (NO) + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1.6 (+12) 0 3500x2000

NOTE: k ESTIMATED.

NO + .CHO - HNO + CO NITROGEN OX IDE (NO) + FORMYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 2 . 0( +11

0.5 1000+2500 0.3 3.2

NO A CN - N2 + CO NITROGEN OXIDE(NO) + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3 . 2 ( +1 1

0 0x2500 0.3 3.2

NO + M - N + 0 + M NITROGEN OX IDE (NO) 76 ENG REACTION ORDER: 2. 1500-2500 4.0(+20) -1.5 75500x2500 0.3 3.2

NOTE: M = Ar, OR N2 OR 02. GIVEN WITH CAUTION.

72 KON M: Ar 3000-8000 8.00(+ 2) -1.5 75500

N02 + 0 - NO + 02 NITROGEN 0XIDE(N02 ) + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 300-550 1 . 0 ( +13

0 300x100 0.8 1.3 76 ENG 1500-2500 1 . 0 ( +13

0 500±250 0.5 2.0

N02 + 0 + M - N03 + M NITROGEN 0XIDE(N02 ) i OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2. M: N2 295 1 . 1(+13) - 0.4 2.5

NOTE: LIMITING HIGH PRESSURE kREACTION ORDER: 3. 295 2.3(+16) _ — 0.4 2.5

kQ (LOT PRESSURE)

N02 + o3 - no3 + 02 NITROGEN 0XIDE(N02 ) + OZONE

73 BAU/DRY REACTION ORDER: 2. 286-302 5.9(+12) 0 3500 0.5 2.0

N02 + H - NO + OH NITROGEN 0XIDE(N02 ) + HYDROGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 298-630 3.5(+14) 0 740x500 0.5 1.5

NOTE: k FACTORS CHANGING T0:f=0.5;F=2.0AT 633K. 76 ENG 1500-2500 3.2(+14) 0 750+500 0.5 2.0

N02 + OH + M - HN03 + M NITROGEN 0XIDE(N02 ) + HYDROXYL FREE RADICAL

73 BAU/DRY REACTION ORDER: 3. M: He 300 5 . 0(+17) - - 0.4 1.6

N02 + N - 0 + N20 NITROGEN 0XIDE(N02 ) + NITROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 5.0(+12) 0 0+1500 0.5 2.0

N02 + N - 02 + N2 NITROGEN 0XIDE(N02 ) + NITROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 1 . 0 ( +12

0 0+1500 0.5 2.0

N02 + N - NO + NO NITROGEN OXIDE (N02 ) + NITROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 4.0(+12) 0 0x1500 0.2 5.0

39
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical react ions 7VK A B E/R

(in K)

k factors

f F

N02 + NO - 02 + N 20 NITROGEN 0XIDE(N02 ) + NITROGEN OX IDE (NO) 76 ENG REACTION ORDER: 2. 1500-2500 1 . 0 ( +12

)

0 30200 0.01 100.

N02 + NO + 02 - NO, + vo2 NITROGEN 0XIDE(N02 )

4- NITROGEN OXIDE(NO)

+ OXYGEN MOLECULE

73 BAU/DRY REACTION ORDER: 3. 300-500 2.9(+ 7) 0 -400+500 0.4 2.5

N02 + N02 - NO + NO + 02 NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 2. 600-2000 2.0(+12) 0 13500+100 0.7 1.3 NOTE: k FACTORS INCREASING SLIGHTLY ABOVE 1000K.

N02 + N02 + M - N 20a + M NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 3. M: n2 250-350 1.1(113) 0 -1040 0.7 1.3 NOTE: CORRECTED k VALUE (PERSONAL COMMUNICATION

FROM DR. BAULCH TO DR. HAMPSON). k x = Kk_ t N02 + NO, - NO + N02 + 02 NITROGEN 0XIDE(N02 ) + NITROGEN 0XIDE(N03 ) 73 BAU/DRY REACTION ORDER: 2. 300-850 1.4(+11) 0 1610+500 0.4 2.5

no2 + N03 + M - N205

-L M NITROGEN 0XIDE(N02 ) + NITROGEN 0XIDE(N03 ) 73 BAU/DRY REACTION ORDER: 2. 300 2.3(+12) - - 0.4 2.5

NOTE: LIMITING HIGH PRESSURE k M IS A N205 + NO MIXTURE

REACTION ORDER: 3. 300 1.0(118) - - 0.5 2.0

kQ( LOW PRESSURE). M IS A N205 + NO MIXTURE

N02 + NH - NO + HNO NITROGEN 0XIDE(N02 ) + IMIDOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 2.0(+ll) 0.5 2500+2500 0.3 3.2

N02 + CO - NO + C02 NITROGEN 0XIDE(N02 ) + CARBON MONOXIDE

72 KON REACTION ORDER: 2. 500-800 1.9(+12) 0 14726+385 0.5 1.9

76 ENG 1500-2500 2.00(+12) 0 15000+1500 0.5 2.0

N02 + M - NO + 0 + M NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 2. M: Ar 1400-2400 1.1(+16) 0 33000+750 0.8 1.3

N03 + NO - N02 + no2 NITROGEN OXIDE (N03 ) NITROGEN OXIDE(NO)

72 KON REACTION ORDER: 2. 298-547 1 .5(414) 0 1160+120 0.7 1.4

NO, + N02 - N02 + NO + 02 NITROGEN 0XIDE(N03 ) + NITROGEN 0XIDE(N02 ) 73 BAU/DRY REACTION ORDER: 2. 300-850 1.4(411) 0 1600+500 0.4 2.5

no3 + no2 + M - N205M NITROGEN 0XIDE(N03 ) NITROGEN 0XIDE(N02 ) 72 BAU/DRY REACTION ORDER: 2. 300 2.3(412) - - 0.4 2.5

NOTE: LIMITING HIGH-PRESSURE k. M IS A N 20, + NO MIXTURE.

k, = Kk_j REACTION ORDER: 3. 300 1.0(118) - - 0.5 2.0

ko (L0W PRESSURE). M IS A N 205 + NO MIXTURE

NO, + M - NO + 02 + M NITROGEN OXIDE(NO,)

72 KON REACTION ORDER: 2. M: no2 500-1100 1.9(411) 0 1990+110 0.8 1.3

N20 + 0 - N2 + 02 NITROGEN 0XIDE(N20) OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 1200-2000 1.0(+14) 0 14100+2000 0.4 2.5

N20 + 0 - NO + NO NITROGEN 0XIDE(N20) + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 1200-2000 1 .0(414) 0 14000+1500 0.5 2.0

72 KON 900-2300 3.6(413) 0 13700

40
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K)

k

f factors

F

N20 + H - N2 + OH NITROGEN 0XIDE(N2 0) + HYDROGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 700-2500 7.6(113) 0 7600+500 0.5 1.5

N20 + H - NO + NH NITROGEN 0XIDE(N2 0) + HYDROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+11) 0.5 15100+2500 0.3 3.2

N,0 + OH - N, + HO, NITROGEN 0XIDE(N20) + HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(+13) 0 7550

NOTE: k ESTIMATED.

N20 + N -» N2 + NO NITROGEN 0XIDE(N2 0) + NITROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 5 . 0 ( + 8) 0 5000+2500 0.3 3.2

N,0 + NO - N, + NO, NITROGEN 0XIDE(N20) + NITROGEN OXIDE (NO) 76 ENG REACTION ORDER: 2. 1500-2500 2.0(+14) 0 25165 0.1 10.

N,0 + CO - N, + CO, NITROGEN 0XIDE(N2 0) + CARBON MONOXIDE

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+11) 0 10000±1500 0.5 2.0

N20 + M - N2 + 0 + M NITROGEN 0XIDE(N2 0) 73 BAU/DRY REACTION ORDER: 2. 1300-2500 5.0(114) 0 29000+1500 0.7 1.5

N,0a. - NO, + NO, NITROGEN 0XIDE(N2 04 ) 70 BEN/O 'N REACTION ORDER: 1. 253-301 1 . 0( +16) 0 6600

N,0^ + M - NO, + NO, + M NITROGEN 0XIDE(N2 04 ) 73 BAU/DRY REACTION ORDER: 2. M: N2 250-350 2.5(+17) 0 5550+500 0.7 1.3 N,0^ + M -> NO, + NO, + M NITROGEN OXIDE (N205 ) 73 BAU/DRY REACTION ORDER: 1. 300-340 5 . 7 ( + 14) 0 10600 0.4 2.5

NOTE: LIMITING HIGH-PRESSURE k. M IS A N,0 S + NO MIXTURE. REACTION ORDER: 2. 1 . 3 ( + 19

0 9700 0.5 2.0

ko (L0W PRESSURE). M IS A N2

05 + NO MIXTURE.

NH + 0 - H | NO

IMIDOGEN FREE RADICAL + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

NH + 0 - N + OH IMIDOGEN FREE RADICAL + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 4000

NH + 0 + M - HNO + M IMIDOGEN FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+16) -0.5 0+2500 0.3 3.2

NH + H H + NH IMIDOGEN FREE RADICAL + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 0

NH + H - N + H2 IMIDOGEN FREE RADICAL + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. 6.3(+ll) 0.5 4000

NH + OH - N + H20 IMIDOGEN FREE RADICAL + HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 5.0(+ll) 0.5 1000+2500 0.3 3.2

NH + H20 - HNO + H2 IMIDOGEN FREE RADICAL + WATER

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+11) 0.5 1500±2500 0.3 3.2

41
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

NH + S - H + NS IMIDOGEN FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

NH + S - N + SH IMIDOGEN FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

NH + N - H + N2 IMIDOGEN FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

NH + N - N + NH IMIDOGEN FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

NH + N02 - HNO + NO IMIDOGEN FREE RADICAL + NITROGEN 0XIDE(N02 ) 76 ENG REACTION ORDER: 2.

NH + NH - H2 + N2 IMIDOGEN FREE RADICAL

76 ENG REACTION ORDER: 2.

NH + C - H + CN IMIDOGEN FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

NH + C - N + CH IMIDOGEN FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

NH + CN - N + HCN IMIDOGEN FREE RADICAL + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2.

NH2 + H + M - NH3 + M AMIDOGEN FREE RADICAL + HYDROGEN ATOM

73 BAU/DRY REACTION ORDER: 3. M: NOTE: kj = Kk_j

NH3 + 0 •- NH2 + OH AMMONIA + OXYGEN ATOM

73 BAU/DRY REACTION ORDER: 2.

NH3 + CH3

. - NH2 + CH4 AMMONIA + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

ND3 + CH3. - ND2 + CH3 D AMMONIA-D3 + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

NH3 + M - H + NH2 + M AMMONIA

73 BAU/DRY REACTION ORDER: 2. M:

NH2 NH2 + H - NH2 NH. + H 2 HYDRAZINE + HYDROGEN ATOM

73 BAU/DRY REACTION ORDER: 2.

NH2 NH2 + CH3. - NH2 NH. + CH4 HYDRAZINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

ND2ND2 + CH3. - ND2

ND. + CH3

D HYDRAZINE-D4 + METHYL FREE' RADICAL

76 KER/PAR REACTION ORDER: 2.

NH2 NH2 + M - NH2

. + NH2 . + M HYDRAZINE

73 BAU/DRY REACTION ORDER: 2. M: NOTE: LIMITING HIGH PRESSURE k.

77K A B E/R

(in K)

k factors

f F

6 . 3 ( + 1 1

)

0.5 0

6 . 3 ( + 1 1

)

0.5 4000

6 . 3 ( + 1 1

)

0.5 0

6 . 3( +1 1

)

0.5 4000

1500-2500 2.0(111) 0.5 2500+2500 0.3 3.2

1500-2500 1 - 0( +13

)

0 0 0.1 10.

6.3(+ll) 0.5 0

6 . 3 ( +1 1

)

0.5 4000

1500-2500 1.0(+11) 0.5 1000+25000

2000-3000 4.8(+14) 0 -8300+2500 0.5 2.0

300-1000 1 . 5( +12

)

0 3020+300 0.5 1.5

350-650 1.0(111) 0 5100+500 0.3 1.3

350-500 1.0(111) 0 5535+500 0.3 1.3

2000-3000 9.2(+15) 0 42400+2500 0.5 2.0

250-500 1 . 3 ( + 13

)

0 1260+100 0.5 2.0

350-500 1.0(+11) 0 2515+500 0.5 2.0

350-500 7.2(+10) 0 3200+500 0.5 2.0

1250-1400 8.0(113) 0 27700+1000 0.3 3.0

42
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R

(in K) k factorsf F

NH2NH2 + M - NH2 . + NH2 . + M HYDRAZINE

73 BAU/DRY REACTION ORDER: 2. M: Ar 1250-1400 4.0(+15) 0 20600+1000 0.3 3.0

NOTE: ko (L0W PRESSURE).

HN3 + CH3. - N3 . + ch4 HYDRAZOIC ACID + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 300-400 1.0(111) 0 2100+500 0.5 2.0

NOTE: TENTATIVE k VALUE.

HNO + 0 - H + N02 NITROSYL HYDRIDE + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 5.0(+10) 0.5 0+2500 0.3 3.2

HNO + 0 - NO + OH NITROSYL HYDRIDE + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 5 . 0 ( + 1 1

0.5 0+2500 0.3 3.2

HNO + 0 - NH + 02 NITROSYL HYDRIDE + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 1 . 0( +11

0.5 3500+2500 0.3 3.2

HNO + H - NO + H2 NITROSYL HYDRIDE + HYDROGEN ATOM

73 BAU/DRY REACTION ORDER: 2. 2000 4.8(+12) - - 0.5 1.5

HNO + H - NH + OH NITROSYL HYDRIDE + HYDROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 2.0(+ll) 0.5 11600+2500 0.3 3.2

HNO + OH - NO + H20 NITROSYL HYDRIDE + HYDROXYL FREE RADICAL

73 BAU/DRY REACTION ORDER: 2. 2000 3.6(+13) - - 0.5 1.5

HNO + N - NO + NH NITROSYL HYDRIDE + NITROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 1.0(111) 0.5 1000±2500 0.3 3.2

HNO + N - N20 + H NITROSYL HYDRIDE + NITROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 5.0(+10) 0.5 1500+2500 0.3 3.2

HNO + NO - OH + N20 NITROSYL HYDRIDE + NITROGEN OXIDE(NO)

76 ENG REACTION ORDER: 2. 1500-2500 2 . 0( +12) 0 13100+2500 0.5 2.0

HNO + CO - NH + C02 NITROSYL HYDRIDE + CARBON MONOXIDE

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+11) 0.5 3500+2500 0.3 3.2

HNO + CH - NO + CH2 NITROSYL HYDRIDE + METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 6.3(+ll) 0.5 0+2500 0.3 3.2

HNO + CH2 - NO + CH 3 . NITROSYL HYDRIDE + METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 6.3(+ll) 0.5 0±2500 0.3 3.2

HNO + CH,. - NO + CH4 NITROSYL HYDRIDE + METHYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 5.0(+ll) 0.5 0+2500 0.3 3.2

HNO + .CHO - NO + HCHO NITROSYL HYDRIDE + METHYL, OXO-, FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(+ll) 0.5 0+2500 0.3 3.2

HNO + CN - NO + HCN NITROSYL HYDRIDE + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 4. 00 (+11) 0.5 0+2500 0.3 3.2

HN03 + OH - NO, + H 2 o NITRIC ACID + HYDROXYL FREE RADICAL

73 BAU/DRY REACTION ORDER: 2. 300 8.0(+10) 0.5 2.0

43
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

HN03 + M - N02 + OH + M NITRIC ACID

73 BAU/DRY REACTION ORDER: 2. M:

NS +0 - S + NO NITROGEN SULFIDE(NS) + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2

NS - 0 - N * SO NITROGEN SULFIDE (NS) + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2

NS T H - S + NH NITROGEN SULFIDE(NS) + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2

NS - H - N f SH NITROGEN SULFIDE(NS) + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2

NS + S - S + NS NITROGEN SULFIDE(NS) + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2

NS + S -> N + S2 NITROGEN SULFIDE(NS) + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2

NS + N - S + N2 NITROGEN SULFIDE (NS) + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2

NS + N - N + NS NITROGEN SULFIDE (NS) + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2

NS + C - S + CN NITROGEN SULFIDE(NS) + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2

NS + C - N + CS NITROGEN SULFIDE(NS) + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2 C+O+M - CO + M CARBON ATOM + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 3. NOTE: M = Ar, OR CO k x = Kk.j

C + 02

-* CO + 0 CARBON ATOM + OXYGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2.

C + H2 - CH + H CARBON ATOM + HYDROGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2.

C + OH - CO + H CARBON ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2. C + OH - CH * 0 CARBON ATOM + HYDROXYL FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + S2 - CS + S CARBON ATOM + SULFUR DIMER

75 BEN/GOL REACTION ORDER: 2.

C + SO - CO + S CARBON ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

Ar

7VK A B E/R

(in K)

800-1200 1 . 6( + 15

)

0 15400+1500

6 . 3 ( + 1 1

)

0.5 0

6.3(+ll) 0.5 4000

2.5(+12) 0.5 20735

2.5(+12) 0.5 15700

6 . 3 ( + 1 1

)

0.5 0

2.0(+ll) 0.5 10870

6 . 3 ( +1 1

)

0.5 0

6.3(+ll) 0.5 4000

6.3(+ll) 0.5 0

6 . 3 ( + 1 1

)

0.5 4000

7000-14000 3.3(+26) -3.1 -2114

6.3(+ll) 0.5 0

1.6(+12) 0.5 15700

6.3(111) 0.5 0

7 . 9 ( + 1 1

)

0.5 14800

6 . 3 ( + 1 1

)

0.5 0

6 . 3 ( + 1 1

)

0.5 0

k factors

f F

0.4 2.5

0.3 1.8

44
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

c + SO - CS + 0 CARBON ATOM + SULFUR MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

C + SH -» CH + S CARBON ATOM + MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C I SH - CS + H CARBON ATOM + MERCAPTO FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C f N2 - CN + N CARBON ATOM + NITROGEN MOLECULE

75 BEN/GOL REACTION ORDER: 2.

C + NO - CO + N CARBON ATOM + NITROGEN OXIDE(NO)

75 BEN/GOL REACTION ORDER: 2.

C + NO - CN + 0 CARBON ATOM + NITROGEN OXIDE(NO)

75 BEN/GOL REACTION ORDER: 2.

C + NH - CH + N CARBON ATOM + IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + NH - CN + H CARBON ATOM + IMIDOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + NS - CS + N CARBON ATOM ATOM + NITRIC SULFIDE

75 BEN/GOL REACTION ORDER: 2.

C + NS -» CN + S CARBON ATOM + NITRIC SULFIDE

75 BEN/GOL REACTION ORDER: 2.

C + CO -> C2 + 0 CARBON ATOM + CARBON MONOXIDE

75 BEN/GOL REACTION ORDER: 2.

C + CH -» CH + C CARBON ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + CH - C2 + H CARBON ATOM + METHYLIDYNE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C | CS -» CS + c CARBON ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C | CS -> c + s CARBON ATOM + CARBON MONOSULFIDE FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + CN - CN + C CARBON ATOM + CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + CN C2 + N CARBON ATOM + CYANOGEN FREE RADICAL

75 BEN/GOL REACTION ORDER: 2.

C + C2 - C2 + C CARBON ATOM + CARBON DIMER

75 BEN/GOL REACTION ORDER: 2.

7VK B E/R

(in K)

6.3(+ll) 0.5 0

4.0(+ll) 0.5 6090

6.3(111) 0.5 0

1 . 3 ( +12

0.5 22750

6.3(+ll) 0.5 4000

6 . 3 ( +1 1

0.5 0

6 . 3 ( +11

0.5 4000

6 . 3 ( +1 1

0.5 0

6.3(111) 0.5 4000

6.3(+ll) 0.5 0

1 . 0( +120.5 58025

6 . 3 ( + 1 1

0.5 4000

6.3(+ll) 0.5 0

6.3(+ll) 0.5 0

5 . 0 ( +1 10.5 20435

6.3(111) 0.5 0

2 . 5( +110.5 19300

6 . 3 ( +1 10.5 0

k factors

f F

45
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CO + 0 - 0 4 CO CARBON MONOXIDE 4 OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2. CO 4 0 4 M - C02 4 M CARBON MONOXIDE 4 OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 3. M: CO

NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 AT 500K.

CO 4 0 - C 4 02 CARBON MONOXIDE 4 OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CO 4 02 - C02 + 0 CARBON MONOXIDE 4 OXYGEN MOLECULE

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.5; F = 1.5 AT 3000K.

CO * H - 0 + CH CARBON MONOXIDE 4 HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CO 4 H - C + OH CARBON MONOXIDE + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CO 4 H 4 M - .CHO 4 M CARBON MONOXIDE 4 HYDROGEN ATOM 76 BAU/DRY REACTION ORDER: 3. M: H2 NOTE: k FACTORS CHANGING TO: f = 0.5; F = 2.0 AT 773K.

CO 4 H 4 M - .CHO + M CARBON MONOXIDE 4 HYDROGEN ATOM

76 ENG REACTION ORDER: 3.

CO 4 OH - C02 4 H CARBON MONOXIDE 4 HYDROXYL FREE RADICAL

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS OVER 1000K: f = 0.5; F = 1.5. RECOMMENDED k FOR 250-2500K:

log k(cm3mole-1

s-1

) = 10.83 4 3.94 x 10_4T

CO - H02 - C02 4 OH CARBON MONOXIDE 4 HYDROPEROXYL FREE RADICAL

76 BAU/DRY REACTION ORDER: 2.

CO 4 S - 0 4 CS CARBON MONOXIDE 4 SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

CO - S - C + SO CARBON MONOXIDE 4 SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

CO 4 N - 0 4 CN CARBON MONOXIDE 4 NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CO + N - C 4 NO CARBON MONOXIDE 4 NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2. CO 4 N02 - C02 4 NO CARBON MONOXIDE 4 NITROGEN 0XIDE(N02 ) 72 KON REACTION ORDER: 2. 76 ENG

CO 4 N20 - C02 4 N2 CARBON MONOXIDE 4 NITROGEN 0XIDE(N2 0) 76 ENG REACTION ORDER: 2. CO 4 HNO - C02 + NH CARBON MONOXIDE + NITROSYL HYDRIDE

76 ENG REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

6 . 3 ( + 1 1

)

0.5 0

250-500 2.4(+15) 0 2180+280 0.8 1.2

1.0(412) 0.5 69300

1500-3000 2.5(+12) 0 24000+2500 0.5 2.0

2.5(+13) 0.5 88020

2.0(+13) 0.5 77755

298-773 7.2(114) 0 850+500 0.7 1.3

1500-2500 1.6(420) -1.5 0 0.3 3.2

250-2000 1-5(4 7) 1.3 -385 0.8 1.2

700-1000 1.5(414) 0 11900+1000 0.3 3.0

1.3(412) 0.5 37600

4.0(412) 0.5 66530

3.2(412) 0.5 38800

5.0(412) 0.5 57300

500-800 1.9(412) 0 14726+385 0.5 1.9 1500-2500 2.0(412) 0 15000+1500 0.5 2.0

1500-2500 1.0(411) 0 10000+1500 0.5 2.0

1500-2500 1.0(411) 0.5 3500+2500 0.3 3.2

46
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7V K A B E/R

(in K) k

f factorsF

CO + C - 0 + C2 CARBON MONOXIDE + CARBON

75 BEN/GOL

ATOMREACTION ORDER: 2. 1.0(412) 0.5 58025

CO + CH3

. - CH3 C(0). CARBON MONOXIDE + METHYL

72 KON

FREE RADICAL

REACTION ORDER: 2. 273-400 3.8(4 8) 0 1965

CO + M - C + 0 + M CARBON MONOXIDE

76 BAU/DRY

NOTE: k FACTORS CHANGING TO: OVER 10000K. M = Ar OR

REACTION ORDER: 2.

f = 0.5; F = 1.5 CO

7000-15000 8. 8 (+29) -3.5 128700rl800 0.3 1.8

C02 + 0 - CO + 02 CARBON DIOXIDE + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING T0:f=0.5;F=1.5AT 3000K.

k, = Kk j

1500-3000 1.7(413) 0 26500±2500 0.5 2.0

C02 + H - CO + OH CARBON DIOXIDE + HYDROGEN

76 BAU/DRY

ATOM

REACTION ORDER: 2. 1000-3000 1-5(414) 0 13300±150 0.8 1.2

C02 + H2 - CO + H20 CARBON DIOXIDE + HYDROGEN

76 ENG MOLECULEREACTION ORDER: 2. 1500-2500 1-0(4 9) 0.5 755012500 0.3 3.2

C02 + N - CO + NO CARBON DIOXIDE + NITROGEN

76 ENG ATOM

REACTION ORDER: 2. 1500-2500 2.0(411) 0.5 15000+10000 0.1 1.0

C02 + CH - CO + .CHO CARBON DIOXIDE + METHYL I DYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+10) 0.5 3000i2500 0.3 3.2

C02 + M - CO + 0 + M CARBON DIOXIDE

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+15) 0 50000r2500 0.5 2.0

CH + 0 - H + CO METHYLIDYNE FREE RADICAL

75 BEN/GOL

+ OXYGEN ATOM REACTION ORDER: 2. 6.3(411) 0.5 0

CH + 0 - C + OH METHYLIDYNE FREE RADICAL

75 BEN/GOL

+ OXYGEN ATOM REACTION ORDER: 2. 6.3(411) 0.5 4000

CH + 0 + M - .CHO + M METHYLIDYNE FREE RADICAL

76 ENG

+ OXYGEN ATOM REACTION ORDER: 3. 1500-2500 1.0(+16) -0.5 012500 0.3 3.2

CH + 02 - .CHO + 0 METHYLIDYNE FREE RADICAL

76 ENG

+ OXYGEN MOLECULE

REACTION ORDER: 2. 1500-2500 5.0(+ll) 0.5 300012500 0.3 3.2

CH + H - H + CH METHYLIDYNE FREE RADICAL

75 BEN/GOL

+ HYDROGEN ATOM

REACTION ORDER: 2. 6.3(+ll) 0.5 0

CH + H - C + H2 METHYLIDYNE FREE RADICAL

75 BEN/GOL

+ HYDROGEN ATOM REACTION ORDER: 2. 6 . 3 ( + 1 1

0.5 4000

CH + H + M - CH2 + M METHYLIDYNE FREE RADICAL

76 ENG

+ HYDROGEN ATOM REACTION ORDER: 3. 1500-2500 1.00(419) -1.0 0 0.3 3.2

CH + OH - .CHO + H METHYLIDYNE FREE RADICAL

76 ENG

+ HYDROPEROXYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 5.0(411) 0.5 500012500 0.3 3.2

47
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH + H02 _ ch2 + 02 METHYLIDYNE FREE RADICAL + HYDROPEROXYL FREE RADICAL

76 ENG REACTION ORDER: 2.

CH + HOo - .CHO + OH METHYLIDYNE FREE RADICAL + HYDROPEROXYL FREE RADICAL

76 ENG REACTION ORDER: 2.

CH + S - H + CS METHYLIDYNE FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

CH + S - C + SH METHYLIDYNE FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

CH + N - H + CN METHYLIDYNE FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CH + N - C + NH METHYLIDYNE FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CH + N2 - CN | NH METHYLIDYNE FREE RADICAL + NITROGEN MOLECULE

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH + N2 - HCN + N METHYLIDYNE FREE RADICAL + NITROGEN MOLECULE

76 ENG REACTION ORDER: 2. NOTE: REVISED ESTIMATE.

CH + NO - .CHO + N METHYLIDYNE FREE RADICAL + NITROGEN OX IDE (NO) 76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH + NO - HCN + 0 METHYLIDYNE FREE RADICAL + NITROGEN OXIDE(NO)

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH + HNO - CH2 + NO METHYLIDYNE FREE RADICAL

76 ENG NITROSYL HYDRIDEREACTION ORDER: 2.

CH + C - H + C2 METHYLIDYNE FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

CH + C - C + CH METHYLIDYNE FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

CH + C02 - .CHO + CO METHYLIDYNE FREE RADICAL + CARBON DIOXIDE

76 ENG REACTION ORDER: 2.

CH + CH4 - CH2 + CH3

. METHYLIDYNE FREE RADICAL

76 ENG METHANE REACTION ORDER: 2.

CH + .CHO - CH2 + CO METHYLIDYNE FREE RADICAL

76 ENG

METHYL, OXO-, FREE RADICAL

REACTION ORDER: 2.

CH + HCHO - CH2 + .CHO METHYLIDYNE FREE RADICAL

76 ENG FORMALDEHYDEREACTION ORDER: 2.

7VK A B E/R

(in K) k factors

f F

1500-2500 1.0(+10) 0.5 7550+2500 0.3 3.2

1500-2500 5 . 0 ( + 1 1

)

0.5 3000+2500 0.3 3.2

6 . 3 ( + 1 1

)

0.5 0 \

6 . 3 ( + 1 1

)

0.5 4000

6.3(111) 0.5 0

1.0(112) 0.5 6995

1500-2500 3 . 2 ( +14) 0 46300+10000

1500-2500 1.0(+11) 0 9560

1500-2500 1.6(113) 0 5000+3000

1500-2500 2.0(+12) 0 0+1000

1500-2500 6.3(111) 0.5 0+2500 0.3 3.2

6 . 3( +1 1

)

0.5 0

6 . 3 ( + 1 1

)

0.5 4000

1500-2500 1.0(110) 0.5 3000+2500 0.3 3.2

1500-2500 2.5(111) 0.7 3000+2500 0.3 3.2

1500-2500 3 . 2 ( + 10

)

0.7 500+2500 0.3 3.2

1500-2500 l.O(lll) 0.7 2000+2500 0.3 3.2

48
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH2 + 0 - CH + OH METHYLENE FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 2.

CH2 + 0 - .CHO + H METHYLENE FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 2.

CH2 + 02 - HCHO + 0 METHYLENE FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 2.

CH2 + H - CH f H2 METHYLENE FREE RADICAL + HYDROGEN ATOM

76 ENG REACTION ORDER: 2.

CH2 + H2 - CH3

. + H METHYLENE FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CH2 + OH - CH + H20 METHYLENE FREE RADICAL + 76 ENG

CH2 + OH - CH3

. + 0 METHYLENE FREE RADICAL + 76 ENG

CH2 + OH -> HCHO + H METHYLENE FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CH2 + N - CH + NH METHYLENE FREE RADICAL + 76 ENG

CH2 + N2 - HCN + NH METHYLENE FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CH2 + NO - HCHO + N METHYLENE FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CH2 + HNO - CH3 . + NO METHYLENE FREE RADICAL + 76 ENG

CH2 + CH2 - CH + CH3

. METHYLENE FREE RADICAL

76 ENG

HYDROGEN MOLECULE

REACTION ORDER: 2.

HYDROXYL FREE RADICAL

REACTION ORDER: 2.

HYDROXYL FREE RADICAL

REACTION ORDER: 2.

HYDROXYL FREE RADICAL

REACTION ORDER: 2.

NITROGEN ATOM REACTION ORDER: 2.

NITROGEN MOLECULE

REACTION ORDER: 2.

NITROGEN OXIDE(NO) REACTION ORDER: 2.

NITROSYL HYDRIDE

REACTION ORDER: 2.

REACTION ORDER: 2.

CH2 + CH4 - CH3 . + CH3

. METHYLENE FREE RADICAL + METHANE

76 ENG REACTION ORDER: 2.

CH2 + .CHO - CH3 . + CO METHYLENE FREE RADICAL + METHYL, OXO-, FREE RADICAL

76 ENG REACTION ORDER: 2.

CH2 + HCHO - CH3

. + CHO METHYLENE FREE RADICAL + FORMALDEHYDE

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH2 + CN - CH + HCN METHYLENE FREE RADICAL + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

77K A B E/R

(in K) k factors

f F

1500-2500 2 . 0( +110.7 13000+2500 0.3 3.2

1500-2500 5.0(+ll) 0.5 2000±2500 0.3 3.2

1500-2500 5.0(+ll) 0.5 3500+2500 0.3 3.2

1500-2500 3.2 ( +110.7 2500+2500 0.3 3.2

1500-2500 3 . 2 ( +120 3525+1500

1500-2500 5 . 0(+ll0.5 3000+2500 0.3 3.2

1500-2500 5 . 0( +110.5 3000+2500 0.3 3.2

1500-2500 1.0(+13) 0 2500

1500-2500 6.3(+ll) 0.67 20400+2500 0.3 3.2

1500-2500 1.0(+14) 0 35230+10000

1500-2500 1.6(+12) 0 3500+2000

1500-2500 6.3 ( +110.5 0+2500 0.3 3.2

1500-2500 5 . 0 ( +1 1

0.5 3000+2500 0.3 3.2

1500-2500 1.3(+12) 0.7 10000+2500 0.3 3.2

1500-2500 3.2(+10) 0.7 500+2500 0.3 3.2

1500-2500 2.0(+ll) 0 3270+1500

1500-2500 3 . 2 ( +12

0 2500+1500

49
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

1 CH2 + CH3CH=CH2 - products METHYLENE FREE RADICAL + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : *CH2 + CH2 =CH2

3 CH2 + CH3 CH=CH2 -• products METHYLENE FREE RADICAL + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3CH2 + CH2 =CH2

1 CH2 + CH3CH2 CH=CH2 - products METHYLENE FREE RADICAL + 1-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : l CW2 + CH2 =CH2 3CH2 + CH3 CH2 CH=CH2 - products METHYLENE FREE RADICAL + 1 -BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3CH2 + CH2 =CH2

1 CH2 + cis-CH3CH=CHCH3 -* products METHYLENE FREE RADICAL + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : *CH2 + CH2 =CH2 3 CH2

: + cis-CH3CH=CHCH3 -* products METHYLENE FREE RADICAL + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3CH2 + CH2 =CH2

1 CH2 + t rans-CH 3 CH=CHCH3 -* products METHYLENE FREE RADICAL + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : X CH2 + CH2 =CH2

3 CH2 + trans-CH3CH=CHCH3 -* products METHYLENE FREE RADICAL + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3CH2 + CH2 =CH2

1 CH2 + (CH3 ) 2C=CH2 - products METHYLENE FREE RADICAL + 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 1 CH2 + CH2 =CH2

3 CH2 + (CH3 ) 2C=CH2 - products METHYLENE FREE RADICAL + 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3CH2 + CH2 =CH2

*CH2 + (CH3 ) 2C=CHCH3 -• products METHYLENE FREE RADICAL + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : X CW2 + CH2 =CH2

3 CH2 + (CH3 ) 2 C=CHCH3 -* products METHYLENE FREE RADICAL + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3CH2 + CH2 =CH2

'CH2 + ( CH3 ) 2C=C( CH3 ) 2 -» products METHYLENE FREE RADICAL + 2-BUTENE, 2,3-DIMETHYU

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 'C\\2 + CH2 =CH2

3 CH2 + ( CH3 ) 2 C=C( CH3 ) 2 -* products METHYLENE FREE RADICAL + 2-BUTENE, 2, 3-D I METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : 3 CH2 + CH2 =CH2 CH3

. + 0 - HCHO + H METHYL FREE RADICAL + OXYGEN ATOM

76 ENG REACTION ORDER: 2.

1.27

1.0

1.63

1.6

1.37

0.94

1.39

0.89

1.96

2.86

2.12

1.83

2.16

2.74

7VK A B E/R

(in K)

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

297 - - -

1500-2500 5.0(113) 0 0

k factors

f F

0.5 2.0

50
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K) kf factors

F

CH3

. + 02 - CH2 + ho2 METHYL FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

OXYGEN MOLECULE

REACTION ORDER: 2. 1500-2500 3 . 2 ( +12

0 34975+1500

CH3

. + 02 - HCHO + OH METHYL FREE RADICAL + 76 ENG OXYGEN MOLECULE

REACTION ORDER: 2. 1500-2500 3.2(113) 0 10000+5000 0.3 3.2

CH3

. + 02 - CH3

0. + 0 METHYL FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

OXYGEN MOLECULE

REACTION ORDER: 2. 1500-2500 3.2(+12) 0 15100+1500

CH3. + H2 - CH4 + H. METHYL FREE RADICAL + 72 KER/PAR HYDROGEN MOLECULE

REACTION ORDER: 2. 370-700 8.5(+ll) 0 5500+500 0.7 1.3

CH3 . + HD -* CH3

D + H. METHYL FREE RADICAL + 76 KER/PAR DEUTERIUM HYDRIDE

REACTION ORDER: 2. 400-700 2.4(+ll) 0 5635+500 0.5 1.5

CH3 . + HD -> CH4 | D. METHYL FREE RADICAL + 76 KER/PAR DEUTERIUM HYDRIDE

REACTION ORDER: 2. 400-700 2 . 1 ( +11

0 5300+500 0.5 1.5

CH3 . + D2 - CH3D + D. METHYL FREE RADICAL + 76 KER/PAR DEUTERIUM MOLECULE

REACTION ORDER: 2. 300-700 7 . 1 ( +110 5990+250 0.7 1.3

CD3 . + H2 - CD3

H + H. METHYL-D3 FREE RADICAL + HYDROGEN MOLECULE

72 KON REACTION ORDER: 2. 400-570 7.4(+ll) 0 5250+235 0.6 1.7

CH3 . + OH - CH2 + H20 METHYL FREE RADICAL + 76 ENG HYDROXYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 6 . 3 ( +10) 0.7 1000+2500 0.3 3.2

CH3 . + OH CH30. + H METHYL FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

HYDROXYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 6.3(+12) 0 0

CH3 . + H02 - CH4 + 02 METHYL FREE RADICAL + 76 ENG HYDROPEROXYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 1.0(111) 0.5 3000+2500 0.3 3.2

CH3 . + H20 - CH4 + .OH METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

WATERREACTION ORDER: 2. 1273-1773 7 . 1 ( +12) 0 12900+1000 0.5 2.0

CH3 . + H2 S CH4 + SH METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

HYDROGEN SULFIDE

REACTION ORDER: 2. 300-600 2.0(+ll) 0 2065+750 0.4 2.5

ch3 . + nh3 - ch4 + nh2 METHYL FREE RADICAL + 76 KER/PAR AMMONIA

REACTION ORDER: 2. 350-650 1.0(+11) 0 5100+500 0.3 1.8

CH3 . + ND3 - CH3D + nd2 METHYL FREE RADICAL + AMMONIA-d3 76 KER/PAR REACTION ORDER: 2. 350-500 1.0(+11) 0 5535+500 0.3 1.8

CH3 . + NH2NH2 - CH4 + NH2NH. METHYL FREE RADICAL + HYDRAZINE

76 KER/PAR REACTION ORDER: 2. 350-500 1.0(+11) 0 2500+500 0.5 2.0

CH3 . + ND2ND2 - CH3D + METHYL FREE RADICAL + 76 KER/PAR

ND2 ND. HYDRAZINE-d4 REACTION ORDER: 2. 350-500 7.2(+10) 0 3200+500 0.5 2.0

51
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3

. + HN3 - CH4 + N 3 METHYL FREE RADICAL + HYDRAZOIC ACID

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + HNO - CH4 + NO METHYL FREE RADICAL + NITROSYL HYDRIDE

76 KER/PAR REACTION ORDER: 2.

CH3

. + CO - CH3C(0). METHYL FREE RADICAL + CARBON MONOXIDE

72 KON REACTION ORDER: 2.

CH3 . + CH4 - CH4 + CH3. METHYL FREE RADICAL + METHANE

76 KER/PAR REACTION ORDER: 2.

CH3

. + CHD3 - CH4 + CD3

. METHYL FREE RADICAL + METHANE-d3 76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CD4 - CH3 D + CD3

. METHYL FREE RADICAL + METHANE-d4

76 KER/PAR REACTION ORDER: 2.

CD3

. + CH3

D - CD4 + CH3. METHYL-d3-FREE RADICAL + METHANE-d

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CD3

. + CD4 - CD4 + CD3

.

‘ METHYL-d3-FREE RADICAL + METHANE-d4

72 KON REACTION ORDER: 2.

CH3

. + .CHO - CH4 + CO METHYL FREE RADICAL + METHYL, 0X0- , FREE RADICAL

76 ENG REACTION ORDER: 2.

CH3

. + HCHO - CH4 + .CHO METHYL FREE RADICAL + FORMALDEHYDE

76 KER/PAR REACTION ORDER: 2.

CH3 . + HCHO - CH4 + .CHO METHYL FREE RADICAL + FORMALDEHYDE

76 ENG REACTION ORDER: 2.

CH3

. + DCDO - CH3 D + .CDO METHYL FREE RADICAL + FORMALDEHYDE-d2 76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3OH - CH4 + CH30. METHYL FREE RADICAL + METHANOL

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3OH - CH4 + .CH2OH METHYL FREE RADICAL + METHANOL

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3OH - CH4 + CH30. + .CH2OH METHYL FREE RADICAL + METHANOL

76 KER/PAR REACTION ORDER: 2.

CH3

. + CD3OH - CH3 D + .CD2OH METHYL FREE RADICAL + METHAN-d3-OL

76 KER/PAR REACTION ORDR: 2.

CH3. + CD3OH - CH4 + CD3

0.

' METHYL FREE RADICAL + METHAN-d3-OL

76 KER/PAR REACTION ORDER: 2. CD3

. + CH3OD - CD3

H + .CH2OD METHYL-d3 FREE RADICAL + METHANOL-d

76 KER/PAR REACTION ORDER: 2.

77 K A B E/R

(in K)

k factors

f F

300-400 1.0(+11) 0 2100+500 0.5 2.0

1500-2500 5.0(+ll) 0.5 0+2500 0.3 3.2

273-400 3.8(+8) 0 1968

450-800 4.0(+ll) 0 7045+250 0.7 1.3

400-650 l.K+ll) 0 6995+250 0.7 1.3

400-650 2.5(+ll) 0 7700+500 0.5 1.5

400-650 5.0(+10) 0 7200+500 0.5 1.5

473-623 4.1(112) 0 8960+250

1500-2500 3 . 2 ( + 1 1

)

0.5 0+2500 0.3 3.2

300-500 l.K+ll) 0 3070+500 0.5 1.5

1500-2500 1.0(110) 0.5 3000+2500 0.3 3.2

300-500 1 . 4( + 1 1

)

0 3975+500 0.5 1.5

350-550 6.2(+10) 0 4900+500 0.6 1.4

350-500 1.9(111) 0 5035+500 0.6 1.4

350-550 2.3(+ll) 0 4900+500 0.6 1.4

370-550 2.0(+ll) 0 5940+500 0.6 1.4

370-550 6.2(+10) 0 4900+500 0.6 1.4

400-500 1 .9(411) 0 5000+500 0.5 2.0

52
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CD3. + CH30D - CD4 + CH3

0. METHYL-d3 FREE RADICAL + METHANOL-d

76 KER/PAR REACTION ORDER: 2. NOTE: GIVEN WITH CAUTION

CH3

. + CH3 SH - ch4 + ch3

s. + .ch2 sh METHYL FREE RADICAL + METHANETHIOL

76 KER/PAR REACTION ORDER: 2.

CH3. + CD3SH - CH4 + CD3

S. METHYL FREE RADICAL + METHANE-d3-TH I OL

76 KF.R/PAR REACTION ORDER: 2.

CH3

. + CD3SH - CH3 D + ,CD2SH METHYL FREE RADICAL + METHANE-d3-TH I OL

76 KER/PAR REACTION ORDER: 2.

CH3 . + CN - CH2 + HCN METHYL FREE RADICAL + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2.

CH3

. + CH3 NH2 - CH4 + .CH2 NH2 METHYL FREE RADICAL + METHANAMINE

72 KON REACTION ORDER: 2.

CH3. + CH3NH2 - CH4 + CH3NH . + ,CH2 NH2 METHYL FREE RADICAL + METHANAMINE

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3 ND2 - CH4 + .CH2 ND2 METHYL FREE RADICAL + METHANAMINE-d2 76 KER/PAR REACTION ORDER 2.

CH3

. + CH3ND2 - CH3D + CH3 ND METHYL FREE RADICAL + METHANAMINE-d2 76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + CD3 NH2 - CH4 + CD3 NH

METHYL FREE RADICAL + METHAN-d3-AMI NE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + CD3NH2 - CH3 D t .CD2NH2 METHYL FREE RADICAL + METHAN-d3-AMINE

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3 NHNH2 - CH4 + CH3N(.)NH2 + CH3NHNH.

+ .CH2 NHNH2 METHYL FREE RADICAL + HYDRAZINE, METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + HCONH2 - CH4 + HCONH. + ,CONH2 METHYL FREE RADICAL + FORMAM IDE 76 KER/PAR REACTION ORDER: 2.

CH3 . 1 HCOND2 - CH4 + ,COND2 METHYL FREE RADICAL + FORMAM I DE-N , N-d2 76 KER/PAR REACTION ORDER: 2.

CH3 . + HCOND2 - CH3 D + HCOND

METHYL FREE RADICAL + FORMAM I DE-N, N-d2 76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + ch3 no2 - ch4 + ,CH2N02 METHYL FREE RADICAL + METHANE, NITRO76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + CH3ONH2 - CH4 + CH3ONH

METHYL FREE RADICAL + HYDROXYLAMINE, O-METHYL76 KER/PAR REACTION ORDER: 2.

77K A B E/R

(in K) k factorsf F

400-500 3.2(+10) 0 5700±1000 0.5 2.0

303 1 . 2 ( + 8 ) - - 0.5 2.0

400-500 l.l(+ll) 0 2050±500 0.5 2.0

400-500 7

6 (10 ) 0 4200+250 0.5 2.0

1500-2500 1 . 0 (+ 11 ) 0.7 1500+2500 0.3 3.2

388-617 5.4(+ll) 0 5020+500 0.3 3.0

350-650 2 . 1 ( + 11 ) 0 4330+500 0.7 1.3

350-450 1 . 4(

11 ) 0 4530+500 0.7 1.3

350-450 2 . 0 (

1

) 0 5135+1000 0.5 1.5

400-500 2 . 0( +11 ) 0 4530+750 0.5 2.0

400-500 7.2(+10) 0 5100+500 0.5 1.5

420 6.3(+ 8 ) - -

350-500 3.6(+10) 0 3300+500 0.5 1.5

350-500 5 . 5 (

10 ) 0 3575+500 0.5 2.0

350-500 2 . 0( +1

) 0 4900+500 0.5 2.0

300-500 1 . 0 (+ 11 ) 0 5100+750 0.5 2.5

300-500 5.0(110) 0 2265+500 0.5 1.5

53
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH 3 . + CH 30ND2 - CH 3 D + CH3OND. METHYL FREE RADICAL + HYDROXYLAM I NE-N , N-d2 , 0-METHYL76 KER/PAR REACTION ORDER: 2.

CH3

. + CH^CH - CH4 + CHsC. METHYL FREE RADICAL + ETHYNE

76 KER/PAR REACTION ORDER: 2. NOTE: GIVEN WITH CAUTION.

CH3 . + CHsCH - CH3CH=CH.

' METHYL FREE RADICAL + ETHYNE

72 KER/PAR REACTION ORDER: 2.

CH3

. + CH2 =CH2 - CH4 + CH2 =CH. METHYL FREE RADICAL + ETHENE

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH2 =CH2 - CH3CH2 CH2

. METHYL FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER: 2.

CH3

. + CH2 =CH2 - CH3CH2 CH2. + (CH3 ) 2 CH. METHYL FREE RADICAL + ETHENE

72 KON REACTION ORDER: 2.

CH3

. + CH3 CH3 - CH4 + CH3 CH2

. METHYL FREE RADICAL + ETHANE

76 KER/PAR REACTION ORDER: 2.

CH3

. + CD3CD3 - CH3 D + CD3CD2

. METHYL FREE RADICAL + ETHANE-d6 76 KER/PAR REACTION ORDER: 2.

CD3

. + CH3CH3 - CD3

H + CH3CH2

. METHYL-d3 FREE RADICAL + ETHANE

72 KON REACTION ORDER: 2.

CD3

. + CH3CD3

-» CD3

H + CD3CH2. METHYL-d3 FREE RADICAL + ETHANE-1 , 1 , l-d3 76 KER/PAR REACTION ORDER: 2.

CD3

. + CH3CD3 - CD4 + CH3CD2 METHYL-d3 FREE RADICAL + ETHANE-1 , 1 , l-d3 76 KER/PAR REACTION ORDER: 2.

CD3

. + CD3CD3 - CD4 + CD3 CD2

. METHYL-d3 FREE RADICAL + ETHANE-d6 72 KON REACTION ORDER: 2.

CH3

. + CH3CHO - CH4 + CH3 C(0). METHYL FREE RADICAL + ACETALDEHYDE

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3 CDO - CH3 D + CH3 C(0). METHYL FREE RADICAL + ACETALDEHYDE-l-d

76 KER/PAR REACTION ORDER: 2.

CH3 . + cy-CH2 CH20 - CH4 + cy-CH2CH(.)0

METHYL FREE RADICAL + OXIRANE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + HCOOCH3 - CH4 METHYL FREE RADICAL

76 KER/PAR

.COOCH3 FORMIC ACID METHYL ESTER REACTION ORDER: 2.

CH3

. + HCOOCH3 - CH4 METHYL FREE RADICAL

76 KER/PAR

hcooch2. FORMIC ACID METHYL ESTER REACTION ORDER: 2.

CH3 . + HCOOCH3 - CH4 METHYL FREE RADICAL

76 KER/PAR

.cooch3 + HCOOCH2 FORMIC ACID METHYL ESTER REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

300-500 3.5(+10) 0 2970+500 0.5 1.5

473-773 - - 7100

371-479 2 . 5

(

+1

1

) 0 3900

350-650 4

.

2 (

1

1

) 0 5600+500 0.5 1.5

353-453 3 . 3 (

1

1

) 0 3900

350-705 2 . 0 ( 111 ) 0 3575+105 0.8 1.3

400-800 5

.

6 (1

1

) 0 5840+250 0.7 1.3

500-900 5

.

6( +1

1

) 0 6600+250 0.7 1.3

390-800 1 . 0 (+ 12 ) 0 6085+165 0.7 1.4

500-750 3

.

0 (1

1

) 0 5900+250 0.7 1.3

500-750 4 . 3 (

1

1

) 0 6845+250 0.7 1.3

550-760 4

.

6( +1

1

) 0 6405

300-525 8.5(+10) 0 3000+250 0.4 1.6

300-500 1 . 0 (+ 11 ) 0 3975+500 0.5 1.5

350-500 2.5(+ll) 0 5435+750 0.5 2.0

350-550 2 . 0 (

1

1

) 0 4900+500 0.5 1.5

350-550 1 . 6 (

1

1

) 0 5635+500 0.5 1.5

350-550 3.0(+ll) 0 4980+500 0.5 1.5

54
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3. + DCOOCHg - CH3 D + .C00CH3 METHYL FREE RADICAL + FORMIC-d ACID METHYL ESTER

76 KER/PAR REACTION ORDER: 2.

CH3. + DC00CH3 - CH4 + DC00CH2

. METHYL FREE RADICAL + FORMIC-d ACID METHYL ESTER

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3. + CH3C00D - CH4 + .CH2 C00D METHYL FREE RADICAL + ACETIC ACID-d

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3 CH2 0H - CH4 + CH3CH2

0. METHYL FREE RADICAL + ETHANOL

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3 CH2 0H - CH4 + CH3CH(.)0H METHYL FREE RADICAL + ETHANOL

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3CH20H - CH4 + CH3 CH2

0. + CH3 CH(.)0H

+ .CH2CH2 0H METHYL FREE RADICAL + ETHANOL

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3CD20H - CH4 + CH3CD2

0. + .CH2 CD2 0H METHYL FREE RADICAL + ETHAN-1 , l-d2-0L

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3CD20H - CH3D + CH3 CD(.)OH

METHYL FREE RADICAL + ETHAN-1 , l-d2 -0L

76 KER/PAR REACTION ORDER: 2.

CD3 . + CH3 CH2 0D - CD3H + CH3CH(.)0D + ,CH2 CH20D METHYL-d3 FREE RADICAL + ETHANOL-d

76 KER/PAR REACTION ORDER: 2.

CD3

. + CH3CH2OD - CD4 + CH3CH2

0. METHYL-d3 FREE RADICAL + ETHANOL-d

76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3OCH3 - CH4 + CH3OCH2. METHYL FREE RADICAL + METHANE, OXYBIS76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3OOCH3 - CH4 + CH3OOCH2

. METHYL FREE RADICAL + PEROXIDE, DIMETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CD3 . + cy-CH2 CH2 S - CD3

H + cy-CH2CH(.)S

METHYL-d3 FREE RADICAL + THIIRANE

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3CH2SH - CH4 + CH3CH2

S. + CH3CH(.)SH

+ .CH 2 CH2SH METHYL FREE RADICAL + ETHANETHIOL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + CH3CN - CH4 + .CH2CN METHYL FREE RADICAL + ACETONITRILE

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3CH2NH2 - CH4 + CH3 CH2 NH. + CH3CH(.)NH2

+ .CH2 CH2NH2 METHYL FREE RADICAL + ETHANAMINE

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3CH2NH2 - ch4 + ch3ch2 nh. METHYL FREE RADICAL + ETHANAMINE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

7VK A B E/R

(in K) k factorsf F

350-550 2.5(111) 0 5900+500 0.5 1.5

350-550 1.6(+11) 0 5635+500 0.5 1.5

300-600 1.6(+11) 0 5135+500 0.6 1.4

400-625 7 . 9( +10) 0 4730+500 0.6 1.4

400-625 4.00(+ll) 0 4900+500 0.6 1.4

400-625 5.1(111) 0 4900+500 0.6 1.4

400-550 7 . 1 ( +10) 0 4530+500 0.6 1.4

400-550 4.1(+11) 0 5735+500 0.6 1.4

400-525 4.4(+ll) 0 4900+500 0.6 1.4

400-525 6.2(+10) 0 5135+500 0.5 2.0

300-550 4.2(+ll) 0 5035+500 0.5 1.5

350-500 4 . 2 ( + 1 1

0 5000+1000 0.3 3.0

300-500 2.2(+ll) 0 4800+500 0.5 2.0

303 3.5(+ 7) - ' - 0.5 2.0

350-600 5.4(111) 0 5100+500 0.5 1.5

350-500 2.9(111) 0 4200+500 0.5 2.0

350-500 2 . 0 ( + 1 1

0 4600+500 0.5 2.0

55
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3 . + CD3CH2 NH2 - CH4 + CH3 D + CD3CH(.)NH2 + .CD2CH2NH2 METHYL FREE RADICAL + ETHAN-2, 2, 2-d3 -AM I NE 76 KER/PAR REACTION ORDER: 2.

CH3

. + CD3CH2 NH2 - CH4 + CD3CH2 NH. METHYL FREE RADICAL + ETHAN-2, 2, 2-d3-AM I NE 76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 ) 2 NH - CH4 + (CH3 ) 2

N. + .CH2NHCH3 METHYL FREE RADICAL + M ETHANAMINE, N-METHYL76 KER/PAR REACTION ORDER: 2.

CH3

. + (CH3 ) 2NH - CH4 + (CH3 ) 2

N. METHYL FREE RADICAL + METHANAMINE, N-METHYL76 KER/PAR REACTION ORDER: 2.

CH3. + (CH3 ) 2ND - CH4 + .CH2 NDCH3 METHYL FREE RADICAL + METHANAMINE-d, N-METHYL76 KER/PAR REACTION ORDER: 2.

CH3. + (CH3 ) 2 ND - CH3 D + (CH3 ) 2

N. METHYL FREE RADICAL + METHANAMINE-d, N-METHYL76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3 N=NCH3 - CH4 + ,CH2 N=NCH3 METHYL FREE RADICAL + DIAZENE, DIMETHYL76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3 N=NCH3 - (CH3 ) 2NN(.)CH3 METHYL FREE RADICAL + DIAZENE, DIMETHYL72 KON REACTION ORDER: 2.

CD3

. + CD3 N=NCD3 - CD4 + CD2N=NCD3 METHYL-d3 FREE RADICAL + DIAZENE, DI (METHYL-d3 )- 76 KER/PAR REACTION ORDER: 2.

CH3 . + NH2 CH2 CH2 NH2 - CH4 + .NHCH2CH2 NH2

+ NH2CH(.)CH2 NH2 METHYL FREE RADICAL + 1 ,2-ETHANEDIAMINE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + NH2CH2CH2 NH2 - CH4 + .NHCH2 CH2 NH2 METHYL FREE RADICAL + 1 ,2-ETHANEDIAMINE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + ND2 CH2 CH2 ND2 - CH4 + ND2 CH(.)CH2ND2 METHYL FREE RADICAL + 1 , 2-ETHANEDI (AMINE-d2 ) 76 KER/PAR REACTION ORDER: 2.

CH3

. + ND2 CH2CH2 ND2 - CH3 D + .NDCH2CH2 ND2 METHYL FREE RADICAL + 1 , 2-ETHANEDI (AMI NE-d2 ) 76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 ) 2 NNH2 - CH4 + (CH3 ) 2 NNH METHYL FREE RADICAL + HYDRAZINE, 1 , 1 -DIMETHYL76 KER/PAR REACTION ORDER: 2.

CH3. + (CH3 ) 2NNH2 - CH4 + (CH3 ) 2 NNH. + .CH2 N(CH3 )NH2 METHYL FREE RADICAL + HYDRAZINE, 1,1-DIMETHYL76 KER/PAR REACTION ORDER: 2.

CH3

. + (CH3 ) 2 NND2 - CH4 + .CH2 N(CH3

)ND. METHYL FREE RADICAL + HYDRAZINE-d2 , 1 , 1 -DIMETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 ) 2NND2 - CH3D + (CH3 ) 2NND. METHYL FREE RADICAL + HYDRAZINE-d2 , 1 , 1-DI METHYL76 KER/PAR REACTION ORDER: 2.

77K A B E/R

(in K) k factorsf F

350-500 2 . 9 ( + 1 1

)

0 4200+500 0.5 2.0

423 4 . 0 ( + 5) -• -

350-650 1 . 6( +1 1

)

0 3500+500 0.5 2.0

350-650 6.5(+10) 0 3200+500 0.5 2.0

350-500 2.9(+ll) 0 4400+500 0.5 1.5

350-500 1.0(+11) 0 4300+500 0.5 1.5

300-500 1.1(111) 0 3975+250 0.7 1.3

300-450 5.0(110) 0 3040+355 0.4 2.6

300-500 6.6(+10) 0 4125+500 0.5 1.5

350-500 3 . 8 ( + 1 1

)

0 4200+500 0.5 2.0

350-500 2.0(+ll) 0 4430+500 0.5 2.0

350-500 2 . 0 ( + 1 1

)

0 4000+500 0.5 2.0

350-500 3.2(+ll) 0 5100+500 0.5 2.0

350-500 1.7(+11) 0 2870+500 0.5 1.5

350-500 2.4(+ll) 0 2970+500 0.5 1.5

350-500 3.2(+ll) 0 4125+750 0.5 2.0

350-500 2.1(+11) 0 3400+500 0.5 1.5

56
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K)

k factors

f F

350-500 2 . 5 (

1

) 0 2400+250 0.5 2.0

350-500 2 . 0 ( 111 ) 0 2700±500 0.5 2.0

400-600 7 . 9 (

10 ) 0 3800+500 0.5 1.5

350-600 2 . 1 ( 111 ) 0 5235±500 0.5 1.5

350-600 1 . 0 (+ 11 ) 0 5200+500 0.5 1.5

350-600 l.l(+ll) 0 5235+500 0.5 1.5

350-600 1.4(+11) 0 5800+500 0.5 1.5

379-465 5

0 (1

) 0 4400

373-483 2 . 0 (+ll) 0 4100

350-600 1.4(+11) 0 4430+500 0.6 1.4

350-580 3.2(110) 0 3775±300 0.5 2.0

353-453 1.7(+11) 0 3700

453

550-750 2 . 0 (+ll) 0 4830+250 0.7 1.3

550-750 4.4(411) 0 5735+250 0.7 1.3

550-750 2.5(411) 0 5735+250 0.7 1.3

350-500 1.0(411) 0 2970+500 0.4 1.6

CH3. 4 CH3 NHNHCH3 - CH4 4 CH3N(.)NHCH3 4 .CH2 NHNHCH3 METHYL FREE RADICAL 4 HYDRAZINE, 1 ,2-D I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3. 4 CH3 NDNDCH3 - CH3

D 4 CH3N(.)NDCH3 METHYL FREE RADICAL 4 HYDRAZINE-1 ,2-d2 , 1,2-D I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3. + HCONHCH3 - CH4

+ HC0NHCH2

. METHYL FREE RADICAL

76 KER/PAR

- . CONHCH3 4 HC0N(.)CH3 FORMAMIDE, N-METHYLREACTION ORDER: 2.

CH,. 4 CHoCONH, CH. METHYL FREE RADICAL

76 KER/PAR

4 CH3CONH . 4 .CH2C0NH.

4 ACETAMIDE

REACTION ORDER: 2 .

CH,. 4 CH,C0NH, CH. METHYL FREE RADICAL

76 KER/PAR

- ,CH2 C0NH2 ACETAMIDE

REACTION ORDER: 2.

CD3

. 4 CD3 C0NH2 - CD3H 4 CD3CONH

METHYL FREE RADICAL 4 ACETAMIDE-2, 2, 2-d3 76 KER/PAR REACTION ORDER: 2.

CD3

. 4 CD3 C0NH2

-* CD4 METHYL FREE RADICAL

76 KER/PAR

+ .CD2C0NH2

- ACETAMIDE-2, 2, 2-d3 REACTION ORDER: 2.

CH, CHoC^CH (CH3 ) 2C=CH. 4 CH3C(.)=CHOL

METHYL FREE RADICAL 4 1-PROPYNE

72 KER/PAR REACTION ORDER:

NOTE: TENTATIVE k VALUE. CH3 ADDITION OCCURS

AT TERMINAL C ATOM.

CH3 . 4 CH2 =C=CH2 - CH3 CH2C(.)=CH2 METHYL FREE RADICAL 4 1,2-PROPADIENE

72 KER/PAR REACTION ORDER: 2 .

CH3

. 4 CH3CH=CH2 - CH4 METHYL FREE RADICAL - 76 KER/PAR

4 CH3C(.)=CH2 1-PROPENE REACTION ORDER:

CH3 . 4 CH3CH=CH2 - CH4 4 [C3H5 .] METHYL FREE RADICAL 4 1-PROPENE

72 KON REACTION ORDER: 2. QL . 4 CH3CH=CH2 - CH3CH2CH(.)CH3 4 (CH3 ) 2CHCH2

. METHYL FREE RADICAL + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. k/k ref : ref CH3 . + CH2 =CH2 0.72

NOTE: k

CH3 . + CH3 CH2 CH3 - CH4 + (CH3 ) 2CH. METHYL FREE RADICAL + PROPANE

76 KER/PAR REACTION ORDER: 2.

CD3 . + ch3cd2 ch3 - cd3h METHYL-dg FREE RADICAL

76 KER/PAR

CH3CD2CH2

. PROPANE-2, 2-d2 REACTION ORDER:

CD.

CH

+ CH3CD2CH3

-> CD4 + METHYL-d3 FREE RADICAL

76 KER/PAR

(CH3 ) 2CD.

+ PROPANE-2, 2-d2 REACTION ORDER:

CH3CH2 CH0 - CH4 + CH3CH2C(0). METHYL FREE RADICAL + PROPANAL

76 KER/PAR REACTION ORDER:

NOTE: TENTATIVE k VALUE.

57
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions T!K A B E/R

(in K)

k factors

f F

CH3. + (CH3 ) 2C0 - CH4 + CH3C(0)CH2

. METHYL FREE RADICAL + 2-PR0PAN0NE

76 KER/PAR REACTION ORDER: 2. 350-700 3

.

5( +1 1

)

0 4900+250 0.8 1.3

CD3. + (CD3 ) 2C0 - CD4 + CD3C(0)CD2

. METHYL-d3 FREE RADICAL + 2-PR0PAN0NE-1 , I , 1 , 3 , 3 , 3-d6 76 KER/PAR REACTION ORDER: 2. 350-800 4.8(+ll) 0 5735+250 0.8 1.3

CH3. + HC00CH2CH3 - CH4 + .C00CH2 CH3 + HC00CH(.)CH3 METHYL FREE RADICAL + FORMIC ACID ETHYL ESTER

76 KER/PAR REACTION ORDER: 2. 350-500 2 . 5 ( + 1

1

) 0 5100+500 0.5 2.0

NOTE: TENTATIVE k VALUE.

CH3. + CH3 C00CH3 - CH4 + .CH2C00CH3 + CH3C00CH2

. METHYL FREE RADICAL - ACETIC ACID METHYL ESTER

76 KER/PAR REACTION ORDER: 2. 350-600 2.1(+11) 0 5035+500 0.5 1.5

CH3 . + CH3C00CD3 - CH4 + ,CH2C00CD3 METHYL' FREE RADICAL + ACETIC ACID METHYL-d3 ESTER

76 KER/PAR REACTION ORDER: 2. 350-650 1.9(111) 0 5035+500 0.4 1.6

CH3 . + CD3C00CH3 - CH4 + CD3C00CH2

. METHYL' FREE RADICAL + ACETIC-d3 ACID METHYL ESTER

76 KER/PAR REACTION ORDER: 2. 400-600 1 .

7

( +1

1

) 0 5990+500 0.5 1.5

CH 3 . + CH3OCOOCH3 - CH4 + ,CH2OCOOCH 3

' METHYL FREE RADICAL + CARBONIC ACID DIMETHYL ESTER

76 KER/PAR REACTION ORDER: 2. 350-500 3.2(+ll) 0 5800+750 0.5 2.0

NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 2CDOH - CH3 D + (CH3 ) 2C(.)OH METHYL FREE RADICAL + 2-PR0PAN-2-d-0L

76 KER/PAR REACTION ORDER: 2. 400-525 1.9(4-11) 0 4900+500 0.6 1.4

CD3

. + (CH3 ) 2 CHOD - CD3

H + (CH3 ) 2 C(.)OD + ,CH2 CH(CH3 )0D

METHYL-d 3 FREE RADICAL + 2-PROP ANOL-d

76 KER/PAR REACTION ORDER: 2. 400-525 1 . 5 ( + 1 1

)

0 3975+500 0.6 1.4

CH3

. + cy-CH2CH2 CH2 S - CH4 + cy-CH2CH( . )CH2S METHYL FREE RADICAL + THIETANE

76 KER/PAR REACTION ORDER: 2. 300-450 3 . 2( +11

)

0 4630+750 0.5 2.0

NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 ) 2 CHSH - CH4 + (CH3 ) 2CHS. + (CH3 ) 2C(.)SH

+ .CH2 CH(CH3 )SH METHYL FREE RADICAL + 2-PR0PANETHI0L

76 KER/PAR REACTION ORDER: 2. 303 4. 1(+ 7) 0.5 2.0

NOTE: TENTATIVE k VALUE.

CD3. + CH 3CH2CN - CD3 H + CH 3CH(.)CN + .CH2CH2CN METHYL-d 3 FREE RADICAL + PROPANENITRILE

76 KER/PAR REACTION ORDER: 2. 400-600 3.6(+ll) 0 4330+500 0.5 1.5

CH3

. + (CH3 ) 3 N - CH4 + .CH2 N(CH3 ) 2 METHYL FREE RADICAL + METHANAM I NE,N,N-D I METHYL76 KER/PAR REACTION ORDER: 2. 350-600 4.7 (+11) 0 4600+500 0.7 1.3

CH3. + HCON(CH3 ) 2 - CH4 + .CON(CH3 ) 2 + HCO-(CH3 )NCH2

. METHYL FREE RADICAL + FORMAMIDE, N,N-D I METHYL76 KER/PAR REACTION ORDER: 2. 400-600 6 . 3 ( + 10

)

0 3600+500 0.5 1.5

NOTE: TENTATIVE k VALUE.

CH3. + CH3CH2C=CH - CH4 + CH 3CH(.)CaCH

+ .CH2CH2 CsCH + CH 3CH2CsC. METHYL FREE RADICAL + 1-BUTYNE

76 KER/PAR REACTION ORDER: 2. 456-620 1 . 9 ( + 12

)

0 5135+500 0.6 1.4

NOTE: TENTATIVE k VALUE.

CH 3

. + CH3CTCCH3 - CH4 + CH 3 C=CCH2

.

' METHYL FREE RADICAL * 2-BUTYNE

76 KER/PAR REACTION ORDER: 2. 486-619 l.K+12) 0 4900+500 0.6 1.4

NOTE: TENTATIVE k VALUE.
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3. + CH3 =CHCH=CH2 - CH3CH2 CH(.)CH=CH2 METHYL FREE RADICAL + 1,3-BUTADIENE

72 KER/PAR REACTION ORDER: 2.

CHo. + CH2 =CHCH=CH2 - CH3 CH2CH(.)CH=CH2

? . CH2 CH ( CH3

) CH=CH2 METHYL FREE RADICAL + 1,3-BUTADIENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 12.0

NOTE: k ref : CH3 + CH2 =CH2

CH3. + CH3CH2CH=CH2 - CH4 + CH3CH(.)CH=CH2 METHYL FREE RADICAL + 1-BUTENE

76 KER/PAR REACTION ORDER: 2.

CH 3 . + CH3 CH2 CH=CH2 - CH3 CH2 CH(.)CHCH3

* CH3CH2 CH(CH3 )CH2

. METHYL FREE RADICAL + 1-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.7

NOTE: k ref : CH3 + CH2 =CH2

CH3

. + cis-CH3 CH=CHCH3 - CH4 + CH3 CH=CHCH2

. METHYL FREE RADICAL + cis-2-BUTENE

76 KER/PAR REACTION ORDER: 2.

CH3. + cis-CH3 CH=CHCH3 - (CH3 ) 2 CHCH( . )CH3 METHYL FREE RADICAL + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/kre f

: 0.2

NOTE: k ref : CH3 . + CH2=CH2

CH3

. + t r ans-CH3CH=CHCH3 - CH4 + CH3 CH=CHCH2. METHYL FREE RADICAL + trans-2-BUTENE

76 KER/PAR REACTION ORDER: 2.

CH3 . + trans-CH3 CH=CHCH3 - (CH3 ) 2CHCH( . )CH3 METHYL FREE RADICAL + t rans-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.4

NOTE: k ref : CH3

. + CH2 =CH2

CH3

. + (CH3 ) 2C=CH2 - CH4 + .CH2C(CH3 )=CH2 METHYL FREE RADICAL + 1-PROPENE, 2-METHYL76 KER/PAR REACTION ORDER: 2.

CH3 . + (CH3 ) 2C=CH2 - (CH3 ) 3 CCH2 . + (CH3 ) 2 C(.)CH2 CH3 METHYL FREE RADICAL + 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/kref : 1.1

NOTE: k ref : CH3 + CH2 =CH2

CH3 + CH3CH2CH2CH3

-* CH4 + CH3 CH2 CH(.)CH3 METHYL FREE RADICAL + BUTANE

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3 CH2 CH2 CH3 - CH4 + CH3CH2 CH(.)CH3

+ CH3CH2 CH2CH2. METHYL FREE RADICAL + BUTANE

72 KON REACTION ORDER: 2.

CD3 . + CH3 CD2CD2 CH3 - CD3

H + CH3CD2 CD2 CH2

. METHYL-d3 FREE RADICAL + BUTANE-2, 2, 3, 3-d4 76 KER/PAR REACTION ORDER: 2.

CD3 . + CH3CD2CD2 CH3 - CD4 + CH3CD2 CD(.)CH3 METHYL-d3 FREE RADICAL + BUTANE-2, 2, 3, 3-d4

76 KER/PAR REACTION ORDER: 2.

CH3 . + (CH3 ) 3CH - CH4 + METHYL FREE RADICAL + 76 KER/PAR

(CH3 ) 3

C. + (CH3 ) 2CHCH2 . PROPANE, 2-METHYLREACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

353-453 8 . 1 ( +10) 0 2065

453 - - -

350-650 2 . 5( +1 1

0 4200±500 0.6 1.4

353-453

453 1.0(+11) 0 3600

350-650 1 . 8 ( +1 1

0 4100+500 0.6 1.4

353-453

453 4.5(+10) 0 3675

350-500 1 . 0( +12

0 4830+500 0.6 1.4

353-453

453

1.4(+11) 0 4075

350-600 3.0(+ll) 0 4500±500 0.6 1.4

353-453

453

1.4(4-11) 0 3475

350-750 4.0(+ll) 0 4830x250 0.7 1.3

350-500 1.6(411) 0 4540±150 0.7 1.4

600-750 4.8+11) 0 57351250 0.7 1.3

600-750 4.5(411) 0 5735+250 0.7 1.3

300-500 8.3(410) 0 4000+500 0.5 2.0

59
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3 . + (CH3 ) 3CH - CH4 + (CH3 ) 3C. METHYL FREE RADICAL + PROPANE, 2-METHYL76 KER/PAR REACTION ORDER: 2.

CD3. + (CH3 ) 3CD - CD3H + (CH3 ) 2 CDCH2. METHYL-d3 FREE RADICAL + PR0PANE-2-d, 2-METHYL76 KER/PAR REACTION ORDER: 2.

CD3

. + (CH3 ) 3CD - CD4 + (CH3 ) 3

C.

' METHYL-d3 FREE RADICAL + PR0PANE-2-d, 2-METHYL76 KER/PAR REACTION ORDER: 2.

CH3

. + CH3 CH=CHCHO - CH4 + CH3 CH=CHC(0). METHYL FREE RADICAL + 2-BUTENAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CH3 C0C0CH3 - CH4 + CH3C0C0CH2

. METHYL FREE RADICAL + 2,3-BUTANEDIONE

76 KER/PAR REACTION ORDER: 2.

CH3

. + (CH3C0) 2 0 - CH4 + CH3 C000CCH2

. METHYL FREE RADICAL + ACETIC ACID ANHYDRIDE

76 KER/PAR REACTION ORDER: 2.

CH3 . + CH3 CH2CH2 CHO - CH4 + CH3 CH2 CH2C(0). METHYL FREE RADICAL + BUTANAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3. + (CH3 ) 2 CHCHO - CH4 + (CH3 ) 2CHC(0). METHYL FREE RADICAL + PROPANAL, 2-METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CH3CH2 COCH3 - CH4 + CH3CH(.)C0CH3 + .CH2CH2 COCH3

+ CH3CH2COCH2

. METHYL FREE RADICAL + 2-BUTANONE

76 KER/PAR REACTION ORDER: 2.

CH3

. + HCOOCH2 CH2 CH3 - CH4 + .COOCH2CH2CH3 METHYL FREE RADICAL + FORMIC ACID PROPYL ESTER

72 KON REACTION ORDER: 2.

CH3

. + HCOOCH2 CH2CH3 - CH4 + .COOCH2 CH2 CH3

+ HCOOCH(.)CH2 CH3 + HCOOCH2 CH(.)CH3

- hcooch 2 ch 2 ch2

. METHYL FREE RADICAL + FORMIC ACID PROPYL ESTER

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + HCOOCH(CH3 ) 2 - CH4 + ,COOCH(CH3 ) 2

+ HCOOC(.)(CH3 ) 2 + HCOOCH(CH3 )CH2. METHYL FREE RADICAL + FORMIC ACID 1-METHYLETHYL ESTER

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CH 3CH2 OCH2 CH3 - CH4 + CH3CH2 OCH(.)CH3

+ ch3 ch2 och2 ch2

. METHYL FREE RADICAL + ETHANE, l,l'-OXYBIS76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 3CSH - CH4 + (CH3 ) 3CS. + .CH2C(CH3 ) 2SH METHYL FREE RADICAL + 2-PR0PANETHI0L, 2-METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CH3CH=NN=CHCH 3 - CH4 + CH3C(.)=NN=CHCH3

+ .CH2 CH=NN=CHCH3 METHYL FREE RADICAL + ACETALDEHYDE ETHYLI DENEHYDRAZONE

76 KER/PAR REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

550-750 9.6(+10) 0 3975+250 0.7 1.3

550-750 6.0(111) 0 5735+250 0.7 1.3

550-750 1 . 2 ( + 1 1

)

0 4800+250 0.7 1.3

350-500 1.0(+11) 0 3400+500 0.4 2.5

300-800 2.2(+ll) 0 4300+500 0.5 1.5

300-500 1 . 8 ( + 1 1

)

0 4830+500 0.6 1.4

350-500 1.0(+11) 0 2970+500 0.4 1.6

350-500 1.0(+11) 0 2970+500 0.4 1.6

300-500 8.2(+10) 0 3700+500 0.5 1.5

347-455 1 . 3 ( + 10

)

0 3675

350-500 2 . 5 ( + 1 1

)

0 5000+500 0.5 2.0

350-500 2.5(111) 0 4980+500 0.5 2.0

400-500 2 . 5 ( + 1 1

)

0 4200+750 0.5 2.0

303 5.9(+ 7) - - 0.5 2.0

350-600 2 .5(411

)

0 3975+500 0.5 2.0

60
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3

. 4 CH3CH2CH2CH2NH2 - CH4 + CH3 CH2 CH2 CH2 NH.

4 CH3CH2 CH2 CH(.)NH2 a .ch2 ch2 ch2 ch2 nh2 METHYL FREE RADICAL + 1-BUTANAMINE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH 3

. A (CH3CH2 ) 2NH - CH4 a (CH3 CH2 ) 2

N.

4 CH3CH(.)NHCH2CH3 + .CH2CH2NHCH2CH3 METHYL FREE RADICAL 4 ETHANAMINE, N-ETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE K VALUE.

CH3

. 4 CH3CH2N(CH3 ) 2 - CH4 a CH3 CH(.)N(CH3 ) 2

A CH2CH2N(CH3 ) 2 + CH3CH2N(CH3 )CH2

. METHYL FREE RADICAL 4 ETHANAMINE, N,N-D I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 4 CH3 C0N(CH3 ) 2 - CH4 a .CH2 C0N(CH3 ) 2

+ CH3 CON(CH3 )CH2

. METHYL FREE RADICAL 4 ACETAMIDE, N,N-D I METHYL76 KER/PAR REACTION ORDER: 2.

CH3

. A CH3C0N(CH3 ) 2 - CH4 + CH3CON(CH 3 )CH2

. METHYL FREE RADICAL A ACETAMIDE, N,N-D I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. a CH3 (CH2 ) 2CH=CH2 - CH4 a CH 3 CH2 CH(.)CH=CH2 METHYL FREE RADICAL A 1-PENTENE

76 KER/PAR REACTION ORDER: 2.

CH3

. A c i s-CH 3CH2 CH=CHCH3 - CH3CH2 CH( . )CH(CH3 ) 2 METHYL FREE RADICAL A cis-2-PENTENE

72 KER/PAR REACTION ORDER: 2.

CH3

. A cis-CH 3CH2 CH=CHCH3 - CH3 CH2 CH(CH 3 )CH( . )CH 3 METHYL FREE RADICAL a' cis-2-PENTENE

72 KER/PAR REACTION ORDER: 2.

CH3 . A (CH3 ) 2CHCH=CH2 - (CH3 ) 2 CHCH(.)CH2 CH3 METHYL FREE RADICAL A 1-BUTENE, 3-METHYL72 KER/PAR REACTION ORDER: 2.

CH3

. a (CH3 ) 2CHCH=CH2 - CH4 A (CH3 ) 2 C(.)CH=CH2 METHYL FREE RADICAL A 1-BUTENE, 3-METHYL76 KER/PAR REACTION ORDER: 2.

CH3 . A (CH3 ) 2C=CHCH3 - CH4 A (CH 3 ) 2 C=CH2 CH2

. * .CH2 C(CH3 )=CHCH3 METHYL FREE RADICAL A 2-BUTENE, 2-METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. a (CH3 ) 2 C=CHCH3 (CH3 ) 3 CCH(.)CH3

+ (CH3 ) 2 C( . )CH(CH3 ) 2 METHYL FREE RADICAL + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : 0.4

NOTE: k ref : CH3 . A CH2 =CH2 TENTATIVE k VALUE.

CH3 . a ch 3ch2 ch2ch2ch3 - CH4 A ch 3ch2 ch2 ch2 ch2 . METHYL FREE RADICAL A PENTANE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CHa. + CH3 CH2 CH2 CH2 CH3 -» CR, + CH3CH2 CH(.)CH2 CH3 + CH3CH2 CH2CH2 (.)CH3 METHYL FREE RADICAL - PENTANE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

7VK A B E/R

(in K)

k factors

f F

426 3 . 2

( - 7) - - 0.5 2.0

350-500 2.2(411) 0 3550-500 0.5 2.0

420 2-6(4 7) - - 0.5 2.0

350-600 2.0(All) 0 4200=500 0.5 1.5

350-600 1.6(411) 0 4125±500 0.5 1.5

450-650 4.5(411) 0 4500=500 0.6 1.4

298 - - 4060

298 - - 4125

298 H - 3500

450-600 4.4(411) 0 4225=7500 0.5 1.5

400-500 4.9(411) 0 4300=500 0.5 1.5

453 403-455 1.4(410) 0 3070

350-800 4.8(4- 1 1) 0 5800=250 0.7 1.3

350-800 6.0(411)

i 0 4830=250 0.7 1.3

61
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical react ions 7VK A B E/R

(in K)

kf Factors

F

CH3

. + (CH3 ) 2 CHCH2 CH 3 -

METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + (CH3 ) 2 C(.)CH2 CH 3 BUTANE, 2-METHYLREACTION ORDER: 2. 350-750 9.6(+10) 0 3975+250 0.7 1.3

CH 3 . + (CH 3 ) 2 CHCH2 CH 3 -

METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + (CH3 ) 2 CHCH(.)CH3 BUTANE, 2-METHYLREACTION ORDER: 2. 350-750 2.0(+ll) 0 4830+250 0.7 1.3

CH3

. + (CH3 ) 2CHCH 2 CH 3 -

+ .CH2 CH(CH 3 )CH2 CH 3 METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + (CH3 ) 2CHCH2 CH2

.

BUTANE, 2-METHYLREACTION ORDER: 2. 350-750 7.1(+11) 0 5800+250 0.7 1.3

CH3

. + (CH3 ) 4C - CH4 + METHYL FREE RADICAL + 76 KER/PAR

(CH 3 ) 3CCH2. PROPANE, 2,2-DIMETHYLREACTION ORDER: 2. 400-600 8.3(+ll) 0 5940+350 0.6 1.4

CH3

. + CH3 CH2 CH2 CH2 CHO - METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + CH3 CH2 CH2CH2 C(0). PFMTANAI REACTION ORDER: 2. 350-500 1-0(111) 0 3000+500 0.4 1.6

CH3

. + CH3 CH2 CH(CH3 )CHO

methyl' FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

- CH4 + CH3 CH2 CH(CH3 )C(0).

BUTANAL, 2-METHYLREACTION ORDER: 2. 350-500 1.0(111) 0 3200+500 0.5 2.0

CH3

. + (CH3 ) 2CHCH2CH3 -

METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + (CH3 ) 2 CHCH2 C(0).

BUTANAL, 3-METHYLREACTION ORDER: 2. 350-500 1.0(+11) 0 3070+500 0.4 1.6

CH3

. + (CH3 ) 3CCH0 - ch4 METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

+ (CH3 ) 3CC(0)

.

PROPANOL, 2,2-DIMETHYLREACTION ORDER: 2. 350-500 1.0(+11) 0 3170+500 0.5 2.0

CH 3

. + (CH3 CH2 ) 2 C0 - Cl

+ .CH2CH2CONH2 CH3 METHYL FREE RADICAL + 76 KER/PAR

4 + CH3 CH(.)COCH3CH3 3-PENTANONE

REACTION ORDER: 2. 300-450 1.9(411) 0 3675+500 0.5 1.5

CH3 . + (CH3CD2 ) 2C0 - CH4 + CH3CD2COCD2CH2. METHYL FREE RADICAL + 3-PENTANONE-2,2,4,4-d4 76 KER/PAR REACTION ORDER: 2. 500-600 2.0(+ll) 0 5535+500 0.5 2.0

CH3 . + (CH3CD2 ) 2C0 - CH 3 D + CH 3 CD2 COCD(.)CH3 METHYL FREE RADICAL + 3-PENTANONE-2,2,4,4-d4

76 KER/PAR REACTION ORDER: 2. 500-600 1.3(411) 0 42001500 0.5 2.0

CH3

. + HCOO(CH2 ) 3CH3 -

+ HCOOCH(.)(CH2 ) 2 CH3 +

+ HCOOCH2 CH2 CH(.)CH3 + METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + ,COO(CH2 ) 3 CH3 HCOOCH2CH(.)CH2 CH3 HCOO(CH2 ) 3CH2 FORMIC ACID BUTYL ESTER REACTION ORDER: 2. 350-500 2.5(411 ) 0 4980+500 0.5 2.0

CH 3

. + CH 3CH2COOCH2 CH 3 - CH4 + CH3 CH(.)COOCH2CH 3

+ CH3CH2 COOCH(.)CH3 + .ch2 ch2 cooch2 ch 3

+ ch 3 ch2 cooch2ch2

. METHYL FREE RADICAL + PROPANOIC ACID ETHYL ESTER

76 KER/PAR REACTION ORDER: 2. 300-650 2.5(111) 0 4125+500 0.5 1.5

CH 3

. + (CH 3 CH2 ) 2 NCH3 -

+ .CH2 CH2 N(CH2 CH 3 )CH3 METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + CH 3 CH(.)N(CH2CH 3 )CH 3 (CH 3 CH2 ) 2NCH2

. ETHANAMINE, N-ETHYL-N-METHYLREACTION ORDER: 2. 420 3.0(+ 7) - - 0.5 2.0

62
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3. + (CH3 ) 2 NC0N(CH3 ) 2 - ch4 + . CH2

N ( CH3) CON ( CH3 ) 2 METHYL FREE RADICAL + UREA TETRAMETHYL76 KER/PAR REACTION ORDER: 2.

CH3. + c

s-CH3CH2 CH2 CH=CHCH3 - CH3 CH2 CH2 CH( . )CH(CH3 ) 2 METHYL FREE RADICAL + cis-2-HEXENE

72 KER/PAR REACTION ORDER: 2.

CH3. + cis-CH3CH2CH2CH=CHCH3 - CH3CH2CH2CH(CH3 )CH( . )CH3 METHYL FREE RADICAL + cis-2-HEXENE

72 KER/PAR REACTION ORDER: 2.

CHo. + CH 3CH2 CH2 C(CH3 )=CH2 - CH3CH2CH2C(.)(CH3 )CH2CH3 METHYL FREE RADICAL + 1-PENTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2.

CH3

. + c i s- ( CH3 ) 2CHCH =CHCH3 - (CH3 ) 2CHCH( . )CH(CH3 ) 2 METHYL FREE RADICAL + cis-2-PENTENE, 4-METHYL72 KER/PAR REACTION ORDER: 2.

CH3 . + (CH3 ) 2C=C(CH3 ) 2 - CH4 + (CH3 ) 2C=(CH3 )CCH2

. METHYL FREE RADICAL + 2-BUTENE, 2-3-D I METHYL76 KER/PAR REACTION ORDER: 2.

CH3 . + (CH3 ) 2 C=C(CH3 ) 2 - (CH3 ) 3CC(.)(CH3 ) 2 METHYL FREE RADICAL + 2-BUTENE, 2-3-DIMETHYL72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. k/k ref : 0.2

NOTE: k ref : CH3 . + CH2 =CH2 CHo. + CH3 (CH2 ) 4CH3 - CH4 + CH3 (CH2 ) 4CH2

.

' METHYL FREE RADICAL + HEXANE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CH3 (CH2 ) 4CH3 - CH4 f CH3CH2CH(.)CH2 CH2 CH3

+ CH3CH2CH2CH2CH(.)CH3 METHYL FREE RADICAL + HEXANE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 ) 2 CHCH(CH3 ) 2 - CH4 + .CH2 CH(CH3 )CH(CH3 ) 2 METHYL FREE RADICAL + BUTANE, 2, 3-D I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 2 CHCH(CH3 ) 2 - CH4 + (CH3 ) 2 C(.)CH(CH3 ) 2 METHYL FREE RADICAL + BUTANE, 2, 3-D I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 2 CHCH(CH3 ) 2 - CH4 + (CH3 ) 2 CHC(.)(CH3 ) 2

+ .CH3CH(CH3 )CH(CH3 ) 2 METHYL FREE RADICAL + BUTANE, 2, 3-D I METHYL72 KON REACTION ORDER: 2.

CD3 . + (CH3 ) 2 CHCH(CH3 ) 2 CD3 H f (CH3 ) 2 C(.)CH(CH3 ) 2

+ .CH2CH(CH3 )CH(CH3 ) 2 METHYL-d3 FREE RADICAL + BUTANE, 2, 3-DI METHYL72 KON REACTION ORDER: 2.

CH3

. + (CH3 ) 2 CHOCH(CH3 ) 2 CH4 + (CH3 ) 2C(.)OCH(CH3 ) 2

+ .CH2CH(CH3 )OCH(CH3 ) 2 METHYL FREE RADICAL + PROPANE, 2,2'-0XYBIS76 KER/PAR REACTION ORDER: 2.

CH3

. + (CH3 ) 2CHOOCH(CH3 ) 2 - CH4 + (CH3 ) 2 C(.)OOCH(CH3 ) 2

+ .CH 2CH(CH3 )OOCH(CH3 ) METHYL FREE RADICAL + PEROXIDE, B I S ( 1-METHYLETHYL )

76 KER/PAR REACTION ORDER: 2.

77 K A B E/fi (in K) k factors

f F

350-550 2.0(+ll) 0 3975+500 0.5 1.5

298 - - 4060

298 - - 4150

298 - - 3450

298 - - 4390

403-614 7.8(+ll) 0 4400+500 0.6 1.4

403-453 1.0(410) 0 3400

453 1 - -

350-800 4.8(+ll) 0 5800+250 0.7 1.3

350-800 7.9(411) 0 4830+250 0.7 1.3

350-750 9.5(411) 0 5800+250 0.7 1.3

350-750 1.9(411) 0 3975+250 0.7 1.3

300-500 5.0(110) 0 3445

439-566 4.7(+ll) 0 4525

400-600 2.1(411) 0 4100+500 0.5 2.0

300-450 2.3(111) 0 4100+500 0.5 1.5

63
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R

(in K) k factors

f F

350-500 8.9(+10) 0 3925+500 0.5 1.5

350-500 2 . 0 ( + 1 1

)

0 3370+750 0.5 2.0

350-600 5.0(+ll) 0 4000+500 0.5 2.0

350-750 9 . 5( +10) 0 3975+250 0.7 1.3

350-750 6.0(+ll) 0 4830+250 0.7 1.3

350-750 7 . 1 ( + 11

)

0 5800+250 0.7 1.3

350-800 4 . 8 ( + 1 1

)

0 58001250 0.7 1.3

350-800 1 . 2 ( + 12

)

0 4830+250 0.7 1.3

350-750 2.0(111) 0 4830+250 0.7 1.3

350-750 9.5(+10) 0 3975+250 0.7 1.3

350-750 1.2(+12) 0 5800+250 0.7 1.3

350-750 1.2(+12) 0 5800+250 0.7 1.3

350-750 2.9(411) 0 3975+250 0.7 1.3

CHo. + CH3CH=NC(CH3/3) CH4 + CH3C(.)=NC(CH3 ), + ,CH2 CH=NC(CH3 ) 3 + CH3CH=NC(CH3 ) 2 CH2

. METHYL FREE RADICAL + PROPAN I MINE, N-ETHYLIDENE-2-METHYL76 KER/PAR REACTION ORDER: 2 .

CH3 . + (CH3 ) 2 CHNHCH(CH3 ) 2 - CH4 + (CH3 ) 2 CHN(.)CH(CH3 ) 2

+ (CH3 ) 2 C(.)NHCH(CH3 ) 2 METHYL FREE RADICAL + 2-PROPANAMINE, N-( 1-METHYLETHYL)-

76 KER/PAR

NOTE: TENTATIVE k VALUE. REACTION ORDER: 2.

CH3

. + (CH3 CH2 ) 3

N

+ .CH2 CH2 N(CH2 CH3 ) 2 METHYL FREE RADICAL + 76 KER/PAR

NOTE: TENTATIVE k VALUE.

CH4 + CH3 CH(.)N(CH2 CH3 ). ETHANAMINE, N,N-D I ETHYLREACTION ORDER: 2.

CH3

. + (CH3CH2 ) 3CH -» CH4 + (CH3CH2 ) 3

C.

' METHYL FREE RADICAL + PENTANE, 3-ETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 CH2 ) 3 CH CH4 + (CH3 CH2 ) 2 CHCH(.)CH3 METHYL FREE RADICAL + PENTANE, 3-ETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH . + (CH3CH2 ) 3CH -» CH4 + (CH3CH2 ) 2 CHCH2 CH2 . METHYL FREE RADICAL + PENTANE, 3-ETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + CH3 (CH2 ) 6CH3 - CH4 + CH3 (CH2 ) 6CH2

. METHYL FREE RADICAL + OCTANE

76 KER/PAR REACTION ORDER:

NOTE: TENTATIVE k VALUE.

2 .

CH3 . + CH3 (CH2 ) 6CH3

-4 CH4 + CH3 (CH2 ) 3 CH(.)CH2 CH2 CH3

+ CH3 (CH2 ) 4CH(.)CH2CH3 + CH3 (CH2 ) 5CH(.)CH3 METHYL FREE RADICAL + OCTANE

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 3 CCH2 CH(CH3 ) 2 - CH4 + (CH3 ) 3CCH(.)CH(CH3 ) METHYL FREE RADICAL + PENTANE, 2, 2, 4-TR I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3

. + (CH3 ) 3CCH2 CH(CH3 ) 2 - CH4 + (CH3 ) 3CCH2C(.)(CH3 ), METHYL FREE RADICAL + PENTANE, 2, 2, 4-TR I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH4 + (CH3 ) 3CCH2CH(CH3 )CHS CH3 . + (CH 3 ) 3CCH2 CH(CH3 ) 2

+ .CH2C(CH 3 ) 2 CH2 CH(CH3 ) 2 METHYL FREE RADICAL + PENTANE, 2, 2, 4-TR I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 2 CHCH(CHO)CH(CH3 ) 2 CH4

+ .CH2 CH(CH3 )CH(CHO)CH(CH3 ) 2 METHYL FREE RADICAL + PENTANE, 2 , 3 , 4-TR I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 . + (CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 CH4

+ (CH3 ) 2 CHC(.)(CH3 )CH(CH3 ) 2 + (CH3 )C(.)CH(CH3 )CH(CH3 ) 2 METHYL FREE RADICAL + PENTANE, 2, 3, 4-TR I METHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

64
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77 K A B E/R

(in K) kf factors

F

CH3

. 1 (CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 - CH4 1 [C8

H 17 .

METHYL FREE RADICAL 1 PENTANE, 2, 3, 4-TR I METHYL72 KON REACTION ORDER: 2. 414-605 4.7(+ll) 0 4575

CH3 1 (CH3 ) 3CC(CH3 ) 3 - CH4 l .CH2C(CH3 ) 2 C(CH3 ) 3 METHYL FREE RADICAL l BUTANE, 2,2,3, 3-TETRAMETHYL76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. 350-800 1.4(+12) 0 5800+250 0.7 1.3

CH3

. 1 (CH3 ) 3 C00C(CH3 ) 3 - CH4 l ,CH2C(CH3 ) 2C00C(CH 3 ) 3 METHYL FREE RADICAL l PEROXIDE, BIS(1, 1-DIMETHYLETHYL)-

76 KER/PAR REACTION ORDER: 2. 350-500 1.8(112) 0 5900+750 0.3 3.0

CH4 - CH3. 1 H METHANE

70 BEN/O'N REACTION ORDER: 1. 1200-1800 2.0(+15) 0 52340

CH4 l 0 - CH3

. l OH METHANE 1 OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2. 350-1000 2.1(113) 0 4550 0.7 1.3

CH4 l 0 - CH3 . l OH METHANE + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 2.0(113) 0 4530+500 0.6 1.6

CH4 1 H - CH3 . + H2 METHANE 1 HYDROGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 6.3(113) 0 5990+150 0.5 2.0

CH4 1 D - CH3 . 1 HD METHANE + DEUTERIUM ATOM

72 KON REACTION ORDER: 2. 523-673 8.3(112) 0 5100

CH4 1 OH - CH3

. 1 H2 0 METHANE l HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 3.2(113) 0 2500+250 0.5 2.0

CH4 1 CH - CH3 . 1 :CH2 METHANE l METHYLIDYNE FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 2.5(111) 0.7 3000+2500 0.3 3.2

CH4 1 CH2 - CH3 . + CH3

. METHANE l METHYLENE FREE

76 ENG RADICAL

REACTION ORDER: 2. 1500-2500 1.3(112) 0.7 10000+2500 0.3 3.2

ch4 + ch3

. - CH3 . + ch4 METHANE l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 450-800 4.0(111) 0 7045+250 0.7 1.3

ch3 d i cd3

. - CH3 . 1 cd4 METHANE-d 1 METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. 400-650 5.0(110) 0 7200+500 0.5 1.5

chd3 + ch3

. - CD3

. + ch4 METHANE-d3 l METHYL FREE

76 KER/PAR

NOTE: TENTATIVE k VALUE.

RADICAL

REACTION ORDER: 2. 400-650 1.1(111) 0 6995+250 0.7 1.3

CD4 + CH3

. - CD3

. l cdh3 METHANE-d4 l METHYL FREE

76 KER/PAR RADICAL

REACTION ORDER: 2. 370-550 2.5(111) 0 7700+500 0.5 1.5

cd4 . + cd3

. - CD3 . l cd4 METHANE-d4 + METHYL-d3 FREE RADICAL

72 KON REACTION ORDER: 2. 473-623 4.1(112) 0 8960+250

CH4 1 CN - HCN l CH3

. METHANE + CYANOGEN FREE

76 ENG RADICAL

REACTION ORDER: 2. 1500-2500 3.2(111) 0.7 2500+2500 0.3 3.2

CH4 + M - CH3

. + H + M METHANE

76 ENG REACTION ORDER: 2. 1500-2500 2.0(117) 0 44035+1000 0.5 2.0

65
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K)

kf factors

F

.CHO - CO + H METHYL, 0X0-, FREE RADICAL

70 BE\/0'

\

REACTION ORDER: 1. 298 5.0(+13) 0 9560

.CHO +0 - C02 + H METHYL, 0X0- , FREE RADICAL

76 ENG NOTE: k ESTIMATED.

+ OXYGEN ATOM REACTION ORDER: 2. 1500-2500 3 . 2 ( + 1

1

) 0 0+1500

.CHO + 0 - CO + OH METHYL, 0X0-, FREE RADICAL

76 ENG

NOTE: k ESTIMATED.

+ OXYGEN ATOM REACTION ORDER: 2. 1500-2500 3 . 2 (

1 1

)

1.0 250+1500

.CHO + 02 - CO + H02 METHYL, 0X0- , FREE RADICAL

76 ENG

NOTE: k ESTIMATED.

+ OXYGEN MOLECULE

REACTION ORDER: 2. 1500-2500 1.6(+12) 0 3500+1500

.CHO - H - CO - H 2 METHYL, 0X0- , FREE RADICAL

76 ENG

+ HYDROGEN ATOM REACTION ORDER: 2. 1500-2500 1.6(+12) 0.5 0+2500 0.3 3.2

.CHO + OH - CO + H20 METHYL, 0X0- , FREE RADICAL

76 ENG

NOTE: k ESTIMATED.

+ HYDROXYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 3.2(+10) 1.0 0+1500

.CHO + H02 - HCHO + 02 METHYL, 0X0-, FREE RADICAL

76 ENG

NOTE: k ESTIMATED.

+ HYDROPEROXYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 1.0(+14) 0 1500+1500

.CHO + N - HCN + 0 METHYL, 0X0-, FREE RADICAL

76 ENG

NOTE: k ESTIMATED.

+ NITROGEN ATOM REACTION ORDER: 2. 1500-2500 1.0(+14) 0 0+1000

.CHO + N - CO + NH METHYL, 0X0-, FREE RADICAL

76 ENG

+ NITROGEN ATOM REACTION ORDER: 2. 1500-2500 2.0(111) 0.5 1000+2500 0.3 3.2

.CHO + NO - CO + HNO

METHYL, 0X0-, FREE RADICAL

76 ENG

+ NITROGEN OX IDE (NO) REACTION ORDER: 2. 1500-2500 2 . 0 ( + 1 1

)

0.5 1000+2500 0.3 3.2

.CHO - HNO - HCHO + NO METHYL, 0X0- , FREE RADICAL

76 ENG

+ NITROSYL HYDRIDE

REACTION ORDER: 2. 1500-2500 3 . 2 (

1

1

) 0.5 0+2500 0.3 3.2

.CHO + CH - CO + CH0 METHYL, 0X0-, FREE RADICAL

76 ENG

+ METHYLIDYNE FREE RADICAL

REACTION ORDER: 2. 1500-2500 3.2(110) 0.7 500+2500 0.3 3.2

.CHO + CH2 - CO + CH3

. METHYL, 0X0- , FREE RADICAL

76 ENG

+ METHYLENE FREE RADICAL

REACTION ORDER: 2. 1500-2500 3 .

2

(

10 ) 0.7 500+2500 0.3 3.2

.CHO + CH3

. -> CO + CH4

METHYL, 0X0-, FREE RADICAL

76 ENG

+ METHYL FREE RADICAL

REACTION ORDER: 2. 1500-2500 3 . 2 (

1

1

) 0.5 0+2500 0.3 3.2

.CHO + .CHO - HCHO + CO

METHYL, 0X0-, FREE RADICAL

76 ENG REACTION ORDER: 2. 1500-2500 1 . 6 (

1

1

) 0.5 0+2500 0.3 3.2

.CHO - CN - HCN - CO

METHYL, 0X0-, FREE RADICAL

76 ENG

+ CYANOGEN FREE RADICAL

REACTION ORDER: 2. 1500-2500 2 . 0 ( + 1 1

)

0.5 0+2500 0.3 3.2

HCHO + 0 - .CHO + OH FORMALDEHYDE + OXYGEN ATOM

76 ENG REACTION ORDER: 2. 1500-2500 1.0(+11) 1.0 1750+1000 0.5 2.0

66
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

HCHO + 0 -* products FORMALDEHYDE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

HCDO 1 0 -> products

FORMALDEHYDE-d 1 OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

HCHO 1 H - .CHO 1 H2 FORMALDEHYDE 1 HYDROGEN ATOM

76 ENG REACTION ORDER: 2.

HCHO 1 OH - .CHO 1 H2 0 FORMALDEHYDE 1 HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 2.

HCHO 1 H02 - .CHO l H2 02 FORMALDEHYDE l HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: k FACTORS ARE: f - 0.1; F = 10. AT 300K.

HCHO 1 CH - .CHO 1 CH2 FORMALDEHYDE 1 METHYL I DYNE FREE RADICAL

76 ENG REACTION ORDER: 2.

HCHO 1 CH2 - .CHO 1 CH3

. FORMALDEHYDE 1 METHYLENE FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

HCHO + CH3. - .CHO 1 CH4 FORMALDEHYDE l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 76 ENG

DCDO + CH3

. - .CDO l CH3 D FORMALDEHYDE-d l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

HCHO 1 CN - .CHO 1 HCN FORMALDEHYDE + CYANOGEN FREE RADICAL

76 ENG REACTION ORDER: 2.

HCHO 1 M -* .CHO l H l M FORMALDEHYDE

76 ENG REACTION ORDER: 2.

CH2 OH - HCHO + H METHYL, HYDROXY-, FREE RADICAL

70 BEN/O' N REACTION ORDER: 2.

CH3

0. 1 0 - HCHO l OH METHOXY FREE RADICAL 1 OXYGEN ATOM

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH3

0. + 02 - HCHO + H02 METHOXY FREE RADICAL l OXYGEN MOLECULE

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH30. 1 H - HCHO l H2 METHOXY FREE RADICAL 1 HYDROGEN ATOM

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH30. + OH - HCHO + H20 METHOXY FREE RADICAL 1 HYDROXY FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH3

0. 1 N - HCHO 1 NH METHOXY FREE RADICAL l NITROGEN ATOM

76 ENG REACTION ORDER: 2.

7VK A B E/R

(in K) k factorsf F

300 9.0(110) - - 0.7 1.3

300 4.9(+10) - - 0.7 1.3

1500-2500 1 . 3 ( + 10

1.0 1600 0.3 3.2

1500-2500 3.2(110) 1.0 0+1500 0.5 2.0

300-800 1.0(112) 0 4000 0.7 1.5

1500-2500 l.O(lll) 0.7 2000+2500 0.3 3.2

1500-2500 2.0(111) 0 3270+1500 - -

300-500 l.K+ll) 0 3070+500 0.5 1.5 1500-2500 1.0(110) 0.5 300012500 0.3 3.2

300-500 1.4(+11) 0 3975+500 0.5 1.5

1500-2500 1.3(111) 0.7 1500+2500 0.3 3.2

1500-2500 3.2(117) 0 4380012500 0.3 3.2

673-773 1.1(113) 0 14600

1500-2500 1.0(114) 0 0il500

1500-2500 1.0(112) 0 3000+1500

1500-2500 1.0(114) 0 011500

1500-2500 3.2(113) 0 0+1500

1500-2500 1.0(114) 0 011500

67
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH.jO. + M - HCHO + H + M

' M ETHOXY FREE RADICAL

76 ENG REACTION ORDER: 2. NOTE: k ESTIMATED.

CH-jOH + CH 3. - .CH.,0H + CH4 METHANOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CHvjOH + CH.}. - CH.} 0. + CH4 METHANOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH 30H l CH 3. - CH 30. + .CH20H + CH4 METHANOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH 3OD + CD3

. - ,CH20D + CD3

H METHANOL-d + METHYL-d 3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH 3OD + CD3 . - CH 30. + CD4 METHANOL-d + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: GIVEN WITH CAUTION.

CD3OH + CH 3. - ,CD2 0H + CH3

D. METHAN-dj-OL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER 2.

CD3OH + CH3. - CD3

0. + CH4 METHAN-d3-OL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3OOH - CH30. + OH HYDROPEROXIDE, METHYL

70 BEN/O' N REACTION ORDER: 1. NOTE: RATE CONSTANTS MAY BE SLIGHTLY LOW.

CS + 0 - S + CO CARBON MONOSULFIDE FREE RADICAL + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 2.

CS + 0 - S + CO CARBON MONOSULFIDE FREE RADICAL + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CS - 0 - SO + C CARBON MONOSULFIDE FREE RADICAL + OXYGEN

75 BEN/GOL REACTION ORDER: 2.

CS + H - S + CH CARBON MONOSULFIDE FREE RADICAL + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + H - SH + C CARBON MONOSULFIDE FREE RADICAL + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + S - S + CS CARBON MONOSULFIDE FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + S - C + S2 CARBON MONOSULFIDE FREE RADICAL + SULFUR ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + S + M - CS j-M CARBON MONOSULFIDE FREE RADICAL + SULFUR ATOM

76 BAU/DRY REACTION ORDER: 3. NOTE: k, = Kk_,

77 K A B E/R

(in K) k factorsf F

1500-2500 4 . 0 ( +40

)

-7.5 11375+1500

350-500 1 . 9( + 1 1

)

0 5035+500 0.6 1.4

6.2(110) 0 4900+500 0.6 1.4

350-550 2 . 3 ( + 1 1

)

0 4930+500 0.6 1.4

400-500 1.9(+11) 0 5000+500 0.5 2.0

400-500 3.2(+10) 0 5700+1000 0.5 2.0

370-550 2.0(+ll) 0 5940+500

370-550 6.2(+10) 0 4900+500 0.6 1.4

565-651 7.9(+14) 0 21640

300 1 . 3 ( +13

)

- - 0.5 1.5

6.3(+ll) 0.5 0

1.6(+12) 0.5 28940

1 . 3 ( + 13

)

0.5 50930

2.0(113) 0.5 48870

6.3(411) 0.5 0

1 .6(412) 0.5 40463

1800-3700 8.7(413) 0 4370 0.5 1.5

68
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CS + N -> S + CN CARBON MONOSULFIDE FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + N -* C + NS CARBON MONOSULFIDE FREE RADICAL + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + C -* S + C2 CARBON MONOSULFIDE FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

CS + c -> C + CS CARBON MONOSULFIDE FREE RADICAL + CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

CS2 + 0 - CS + SO CARBON DISULFIDE + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 2.

CS2 + 0 -» cos + s CARBON DISULFIDE + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 2.

CS2 + S - CS + S2 CARBON DISULFIDE

76 BAU/DRY

SULFUR ATOM REACTION ORDER: 2.

CS2 + M - CS + S + M CARBON DISULFIDE

76 BAU/DRY REACTION ORDER: 2. M: AR

COS + 0 - CO + SO CARBON OXIDE SULFIDE + OXYGEN ATOM

76 BAU/DRY REACTION ORDER: 2. NOTE: k FACTORS CHANGING TO: f = 0.3; F = 3.0 ABOVE 300K.

COS + H - CO + HS CARBON OXIDE SULFIDE

76 BAU/DRY REACTION ORDER: 2.

COS I S -> CO | S2 CARBON OXIDE SULFIDE + SULFUR ATOM

76 BAU/DRY REACTION ORDER: 2.

CH3S. + CH^CH - CH3SCH=CH. METHYLTHIO FREE RADICAL + ETHYNE

72 KER/PAR REACTION ORDER: 2.

CH3S. + CH2 =CH2 - CH3SCH2CH2

. METHYLTHIO FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER: 2.

CH3

S. + CH3 CH=CHCH3 - CH3CH(SCH3 )CH(.)CH3 METHYLTHIO FREE RADICAL + 2-BUTENE

72 KER/PAR REACTION ORDER: 2. NOTE: cis-trans EQUILIBRIUM - WEIGHTED k.

CH3SH - CH3 . + SH METHANETHIOL

70 BEN/O 'N REACTION ORDER: 1.

CH3SH + CH3 - CH3

S. + .CH2SH + CH4 METHANETHIOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3SH + CH3

. - CD3

S. + CH4 METHANE-d3-TH I OL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3SH + CH3

. - .CD2SH + CH3D METHANE-d3-THIOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

77 K A B E/R

(in K)

k factors

f F

1.3(112) 0.5 1160

4.0(+12) 0.5 37200

5 . 0 ( + 1 1

0.5 20435

6.3(+ll) 0.5 0

200-1000 2.2(+13) 0 700 0.7 1.3

302 2.2(+ll) - - 0.5 1.5

298 3.9(111) - - 0.5 1.5

1800-3700 2.6(+15) 0 38960+9000 0.5 1.5

190-1200 1 . 6( +13

0 2250+250 0.5 1.5

298 1.3(110) - - 0.8 1.3

230-2600 1 .'7 (+12) 0 2050+230 0.3 3.0

298-333 7.9(1 7) - -

298 4.8(+ 8) - -

298-333 1 - 6( + 9) - -

1005-1102 3.2(+15) 0 38550

303 1 - 2 ( + 8) - - 0.5 2.0

400-500 l-K+ll) 0 2065+500 0.5 2.0

400-500 7.6(110) 0 4200+250 0.5 2.0

69
Jable of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CN + 0 - N + CO CYANOGEN FREE RADICAL + 76 ENG

CN + 0 - NO + C CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + 02 - NO + CO CYANOGEN FREE RADICAL + 76 ENG

CN + H -» N + CH CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + H - NH + C CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + H + M - HCN + M CYANOGEN FREE RADICAL + 76 ENG

CN + H2 - HCN t H CYANOGEN FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CN + OH - HCN + 0 CYANOGEN FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CN + S - N + CS CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + S - C + NS CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + N - C + N2 CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + NO - CO t N2 CYANOGEN FREE RADICAL + 76 ENG

CN + NH - HCN + N CYANOGEN FREE RADICAL + 76 ENG

CN + HNO - HCN + NO CYANOGEN FREE RADICAL + 76 ENG

CN + C - N + C2 CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + C - C - CN CYANOGEN FREE RADICAL + 75 BEN/GOL

CN + CH2 - HCN + CH CYANOGEN FREE RADICAL + 76 ENG

NOTE: k ESTIMATED.

CN + CH3

. - HCN + CH2 CYANOGEN FREE RADICAL + 76 ENG

OXYGEN ATOM REACTION ORDER: 2.

OXYGEN ATOM REACTION ORDER: 2.

OXYGEN MOLECULE

REACTION ORDER: 2.

HYDROGEN ATOM REACTION ORDER: 2.

HYDROGEN ATOM REACTION ORDER: 2.

HYDROGEN ATOM REACTION ORDER: 3.

HYDROGEN MOLECULE

REACTION ORDER: 2.

HYDROXYL FREE RADICAL

REACTION ORDER: 2.

SULFUR ATOM REACTION ORDER: 2.

SULFUR ATOM REACTION ORDER: 2.

NITROGEN ATOM REACTION ORDER: 2.

NITROGEN OXIDE(NO) REACTION ORDER: 2.

IMIDOGEN FREE RADICAL

REACTION ORDER: 2.

NITROSYL HYDRIDE

REACTION ORDER: 2.

CARBON ATOM REACTION ORDER: 2.

CARBON ATOM REACTION ORDER: 2.

METHYLENE FREE RADICAL

REACTION ORDER: 2.

METHYL FREE RADICAL

REACTION ORDER: 2.

77 K A B E/R

(in K)

k factors

f F

1500-2500 1.0(+12) 0 0+2500 0.3 3.2

1.3 ( +12

)

0.5 14545

1500-2500 3.2(+ll) 0 0+5000 0.3 3.2

6 . 3 ( + 12

)

0.5 49775

1.0(113) 0.5 52745

1500-2500 3 . 2 ( + 16

)

-0.5 0+2500 0.3 3.2

1500-2500 3.2(+12) 0 2500+1500

1500-2500 3.2(+12) 0 1500+1500

6 . 3 ( + 1 1

)

0.5 0

2.0(+12) 0.5 32010

6.3(+ll) 0.5 0

1500-2500 3.2(+ll) 0 0+2500 0.3 3.2

1500-2500 1.0(111) 0.5 1000+2500 0.3 3.2

1500-2500 4 . 0 ( + 1 1

)

0.5 0+2500 0.3 3.2

2 . 5 ( + 1 1

)

0.5 19300

6 . 3 ( + 1 1

)

0.5 0

1500-2500 3.2(112) 0 2500+1500

1500-2500 1.0(111) 0.7 1500+2500

70
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CN 1 CH4 - HCN | CH3 CYANOGEN FREE RADICAL l 76 ENG

CN 1 .CHO -> CO 1 HCN CYANOGEN FREE RADICAL 1 76 ENG

CN l HCHO - HCN 1 CHO CYANOGEN FREE RADICAL 1 76 ENG

C(N02 ) 4 - .C(N02 ) 3 1 N02 METHANE, TETRANITRO70 BEN/0 'N

HCN 1 OH - CN 1 H20 HYDROCYANIC ACID 1 HYDROXYL FREE RADICAL

76 ENG REACTION ORDER: 2.

CH3 NH2 1 CH3. - CH3 NH. + .CH2 NH2 l CH4 METHANAMINE l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3NH2 1 CH3. - .CH2 NH2 1 CH4 METHANAMINE 1 METHYL FREE RADICAL

72 KON REACTION ORDER: 2.

CH3ND2 1 CH3. - CH3 ND. 1 CH3D METHANAMINE-d2 l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3ND2 1 CH3

. - ,CH2ND2 1 CH4 METHANAMINE-d2 l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3NH2 1 CH3. - ,CD2NH2 1 CH3 D METHAN-d3-AMINE l METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CD3 NH2 + CH3. - CD3 NH. l CH4 METHAN-d3-AMINE 1 METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH2 =NsN - ch2 + n2 METHANE, DIAZO70 BEN/O'N REACTION ORDER: 1.

ch3nhnh2 - ch3nh. i nh2 HYDRAZINE, METHYL70 BEN/O'N REACTION ORDER: 1. NOTE: SUSPECT ARRHENIUS FACTORS.

CH3NHNH2 1 CH3. - CH3N(.)NH2 l CH3 NHNH.

i .ch2 nhnh2 i ch4 HYDRAZINE, METHYL-, l METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3NO - CH2 =NOH

METHANE, NITROSO70 BEN/O'N REACTION ORDER: 1. HCONH2 1 CH3

. - HCONH. + .CONH2 + CH4 FORMAMIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. HCOND2 + CH3

. - HCOND. + CH3

D FORMAM I DE-N , N-d2 + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

METHANE

REACTION ORDER: 2.

METHYL, 0X0- , FREE RADICAL

REACTION ORDER: 2.

FORMALDEHYDE

REACTION ORDER: 2.

REACTION ORDER: 1.

77K A B E/R

(in K)

k factors

f F

1500-2500 3.2(+ll) 0.7 2500+2500 0.3 3.2

1500-2500 2.0(+ll) 0.5 0+2500 0.3 3.2

1500-2500 1 . 3 ( + 1 10.7 1500+2500 0.3 3.2

443-506 3.4(117) 0 20575

1500-2500 2.0(+ll) 0.6 2500+2500 0.3 3.2

350-650 2.1(+11) 0 4330+500 0.7 1.3

388-617 5.4(+ll) 0 5020+500 0.3 3.0

350-450 2.0(+ll) 0 5135+1000 0.5 1.5

350-450 1.4(411) 0 4530+500 0.7 1.3

400-500 7.2(+10) 0 5100+500 0.5 1.5

400-500 2.0(+ll) 0 4530+750 0.5 2.0

498-723 1.0(113) 0 17600

746-862 5.0(116) - 32600

420 6.3(1 8) - -

633-698 7.9(112) 0 19800

350-500 3.6(110) 0 3300+5000 0.5 1.5

350-500 2.0(111) 0 4900+500 0.5 2.0

71
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

HC0ND2 + CH3

. - .C0ND2 + CH4 FORMAM I DE-N , N-d2 + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3ONO - CH3

0. + NO NITROUS ACID METHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3N02 - CH3

. + N02 METHANE, NITRO70 BEN/O'N REACTION ORDER: 1.

CH3N02 + CH3. - .CH2 N02 + CH4 METHANE, NITRO- + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH30N02 - CH3

0. + N02 NITRIC ACID METHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH30NH2 + CH3. - CH3ONH. + CH4 HYDROXYLAMINE, 0-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3OND2 + CH3

. - CHO3ND. + CH3 D HYDROXYLAM I NE-N , N-d2 , O-METHYL, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

C2 + 0 - C + CO CARBON DIMER + OXYGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

C2 + H - C + CH CARBON DIMER + HYDROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

C2 + s -* c + cs CARBON DIMER + SULFUR ATOM

75 BEN/GOL REACTION ODER: 2.

C2 + N - C + CN CARBON DIMER + NITROGEN ATOM

75 BEN/GOL REACTION ORDER: 2.

Cz CARBON DIMER

C

+ CARBON ATOM

75 BEN/GOL REACTION ORDER: 2.

CCO + CH=CH -* products

CARBON 0XIDE(C2 0) + ETHYNE

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.3

NOTE: k ref : CCO + CH2 =CH2 CCO + CH3CH=CH2 - CO + CH3CH=C=CH2 CARBON 0XIDE(C20) + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 5.7

NOTE: k ref : CCO + CH2 =CH2 CCO + CH3 CsCCH3 -• products CARBON 0XIDE(C20) + 2-BUTYNE

72 KER/PAR REACTION ORDER: 2. k/k ref : 8.5

NOTE: k ref : CCO + CH2 =CH2 CCO + CH2 =CHCH=CH2 - CO + CH2 =C=CHCH=CH2 CARBON 0XIDE(C2 0) + 1,3-BUTADIENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 210. NOTE: k ref : CCO + CH2 =CH2 CCO + CH3 CH2CH=CH2 - CH3CH2CH=C=CH2 + CO CARBON 0XIDE(C20) + 1-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 7.0

NOTE: k ref : CCO + CH2 =CH2

T/ K A B E/fi (in K) k factors

f F

350-500 5.5(+10) 0 3575+500 0.5 2.0

453-513 4.0(+15) 0 20700

660 4.0(+15) 0 29700

300-500 1.0(+11) 0 5100+750 0.4 2.5

483-513 3 . 2 ( + 15

)

0 20030

300-500 5.0(+10) 0 2265+500 0.5 1.5

300-500 3.5(+10) 0 2970+500 0.5 1.5

6 . 3 ( + 1 1

)

0.5 0

1.6(113) 0.5 30450

6.3(+ll) 0.5 0

6.3(+ll) 0.5 0

6 . 3 ( + 1 1

)

0.5 0

304 - - -

297 - - -

304 - - -

298 - - -

298 - - -

72
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CCO + cis-CH3CH=CHCH3 - CO + cis-CH3CH=C=CHCH3 CARBON 0XIDE(C20) + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 9.1

NOTE: k ref : CCO + CH2 =CH2 CCO + trans-CH3CH=CHCH3

-* CO + trans-CH3CH=C=CHCH3 CARBON 0XIDE(C20) + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2. k/k ref : 10.6

NOTE: k ref : CCO + CH2 =CH2 CCO + (CH3 ) 2C=CH2

-* CO + (CH3 ) 2C=C=CH2 CARBON 0XIDE(C20) + 1-PROPENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : 50.0

NOTE: k ref : CCO + CH2 =CH2 CCO + (CH3 ) 2C=CHCH3

-> CO + (CH3 ) 2C=C=CHCH3 CARBON 0XIDE(C20) + 2-BUTENE, 2-METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : 100. NOTE: k ref : CCO + CH2 =CH2 CCO + (CH3 ) 2 C=C(CH3 ) 2 - CO + (CH3 ) 2C=C=C(CH3 ) 2 CARBON 0XIDE(C20) + 2-BUTENE, 2, 3-D I METHYL72 KER/PAR REACTION ORDER: 2. k/k ref : 250. NOTE: k ref : CCO + CH2=CH2 CCO + (CH3 ) 2 C=C=C(CH3 ) 2

-> CO + (CH3 ) 2C=C=C(CH3 ) 2 CARBON 0XIDE(C20) + 2, 3-PENTAD I ENE, 2, 4-D I METHYL72 KER/PAR REACTION ORDER: 2. k/kref : 113. NOTE: k ref : CCO + CH2 =CH2 CH^CH + 0 -* products ETHYNE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2. CHhCH + OH - CHsC. + H2 0 ETHYNE + HYDROXYL FREE RADICAL

72 KON REACTION ORDER: 2. OM + S - cy-CH=CHS ETHYNE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. CHsCH + N - C2H2N ETHYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: UPPER LIMIT. CHsCH + CH3

. - CH=C. + CH4 ETHYNE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: GIVEN WITH CAUTION.

CH=CH + CH3. - CH3CH=CH. ETHYNE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2 OM + CH3

S. - CH3SCH=CH. ETHYNE + METHYLTHIO FREE RADICAL

72 KER/PAR REACTION ORDER: 2. CH=CH + CCO -» products ETHYNE + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k ref : 0.3

NOTE: k ref : CH2 =CH2 + CCO

CHsCH + CH3CH2

. - CH3 CH2CH=CH. ETHYNE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. CHsCH + (CH3 ) 2CH. - (CH3 ) 2CHCH=CH. ETHYNE + ETHYL, 1-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

77K A B E/R

(in K)

297 - - -

297 - - -

297 - - -

298 - - -

298 - - -

304 - - -

200-700 1.4(+13) 0 1500

300-2000 7.6(tl2) 0 2335+400

298 1 . 7 ( +1 1

- -

440 2.0(+ 9) - -

473-773 - - 7100

371-479 2 . 5 ( +1 1

0 3900

298-333 7.9(+ 7) - -

304 - - -

373-473 5.0(+10) 0 3500

5.0(+10) 0 3475

k factors

f F

0.8 1.2

0.5 2.1

73
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH=CH * (CH3 ) 3

C. - (CH3 ) 3 CCH=CH. ETHYNE + ETHYL, 1,1-DIMETHYL-, FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. cis-CDH=CDH - trans-CDH=CHD

c i s-ETHENE-1 , 2-d2 70 BEN/0'N REACTION ORDER: 1.

CH2 =CH2 + 0 - cy-CH2CH20 ETHENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH2 =CH2 + H - CH3CH2

. ETHENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

CH2 =CH2 + H + M - CH3CH2

. + M ETHENE + HYDROGEN ATOM

72 KON REACTION ORDER: 3. M: H2 CH2 =CH2 + OH - CH2 =CH. + H20 ETHENE + HYDROXYL FREE RADICAL

72 KON REACTION ORDER: 2.

CH2 =CH2 + OH - .CH2CH2OH ETHENE + HYDROXYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =CH2 + H02 -» products

ETHENE + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: RATIO DATA VERSUS kref. FOR H02 + CO - C02 + OH

k FACTORS MIGHT BE HIGH.

CH2 =CH2 + S - cy--CH 2 CH2 S ETHENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2

CH2 =CH2 + N -* products

ETHENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2

ch2 =ch2 + ch3. - CH2 =CH. + CH4 ETHENE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2

CH2 =CH2 + ch3. - CH,CH0 CH0 . ETHENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2 CH,=CH, + CH,. - CH,CH,CH,. + (CH,),CH. ETHENE + METHYL FREE RADICAL

72 KON REACTION ORDER: 2 CH,=CH, + CH„S. - CH,SCH,CH,. ETHENE + METHYLTHIO FREE RADICAL

72 KER/PAR REACTION ORDER: 2 CH,=CH, + OUCH*. - CH„CH,CH,CH.,. ETHENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2

CH2 =CH2 + CH3 CH2CH2

. - CH3CH2CH2 CH2CH2. ETHENE - PROPYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH2 =CH2 + (CH3 ) 2CH. - (CH3 ) 2CHCH2CH2. ETHENE + ETHYL, 1-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

363-577 1.0(111) 0 3875

723-823 1.0(+13) 0 32700

200-500 3.3(+12) 0 565 0.8 1.2

298 9.3(+13) 0 1410

298-813 5 . 6( +17

)

0.5 495

3500-1400 1 . 6( +14) 0 2831+445 0.4 2.4

1.1(112) - - 0.8 1.3

300 1.0(+ 7) - - 0.1 10.

298 8. 1 ( + 1 1

)

- -

320-550 2.0(+10) 0 353

350-650 4.2(+ll) 0 5600+500 0.5 1.5

353-453 3 . 3 ( + 1 1

)

0 3900

350-705 2.0(111) 0 3575+105 0.8 1.3

298 4.8(+ 8) - -

348-482 1.6(4-11) 0 3675

375-503 1.9(+10) 0 3070

340-457 6.9(+10) 0 3475

74
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH2 =CH2 + CH3CH2 CH2

. - CH3 (CH2 ) 4CH2

. ETHENE + BUTYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH2 =CH2 + (CH3 ) 3

C. (CH3 ) 3CCH2 CH. ETHENE + ETHYL, 1,1-DIMETHYL-, FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =CH2 + (CH3 ) 2 CHCH2 CH2 (CH3 ) 2CH(CH2 ) 3CH2

. ETHENE + BUTYL, 3-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH2 . - CH2 =CH2 + H ETHYL FREE RADICAL

72 KON REACTION ORDER: 1.

CH3CH2 . + H2 - CH3 CH3 + H ETHYL FREE RADICAL + HYDROGEN MOLECULE

72 KON REACTION ORDER:

CHoCH*. + CHsCH CHoCH0 CH=CH. ETHYL FREE RADICAL

72 KER/PAR

ETHYNEREACTION ORDER: 2.

CH3CH2 . + CH2 =CH2 - CH3 CH2 CH2CH ETHYL FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER:

CH3CH2 . + CH2 =CTCH2 - CH3 CH2 CH2C(.)=CH2 ETHYL FREE RADICAL + 1, 2-PROPAD I ENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + CH2 =CHCH2 0H - CH3 CH2CH(.)CH2OH

+ ,CH2CH(CH2CH3 )CH2OH ETHYL FREE RAD I CL + 2-PR0PEN-1-0L

72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + CH2 =CHCN - CH3 CH2 CH2CH(.)CN + .CH2CH(CH2CH3 )CN ETHYL FREE RADICAL + 2-PROPENEN ITR I LE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + CH3CH2 CH=CH2 - CH3 CH2 CH2CH(.)CH2 CH3 ETHYL FREE RADICAL + 1-BUTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + cis-CH3 CH=CHCH2 - CH3 CH(CH2 CH3 )CH( . )CH3 ETHYL FREE RADICAL + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + t rans-CH3CH=CHCH3 - CH3CH(CH2 CH3 )CH( . )CH3 ETHYL FREE RADICAL + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + CH3C00CH=CH2 - CH3C00CH(.)CH2 CH2 CH3

+ CH3COOCH(CH2 CH3 )CH2

. ETHYL FREE RADICAL + ACETIC ACID ETHENYL ESTER

72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + cis-CH3CH=CHCN - CH3CH(CH2CH3 )CH( . )CN

+ CH3 CH(.)CH(CH2 CH3 )CN ETHYL FREE RADICAL + c i s-2-BUTENEN ITR I LE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + t rans-CH3CH=CHCN - CH3CH(CH2 CH 3 )CH( . )CN

+ CH3CH(.)CH(CH2CH3 )CN ETHYL FREE RADICAL + trans-2-BUTENENITRILE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + CH2 =C(CH3 )CN - CH3 CH2 CH2C(.)(CH3 )CN

+ CH2C(CH3 )(CH2CH3 )CN ETHYL FREE RADICAL + 2-PROPENEN ITR I LE, 2-METHYL72 KER/PAR REACTION ORDER: 2.

77K A B E/R

(in K)

352-405 2.3(+10) 0 3370

300-650 2.8(+10) 0 3575

340-413 1.2(+10) 0 3235

673-893 2.3(+14) 0 19990+355

473-823 3.0(+ll) 0 5435

373-473 5.0(+10) 0 3500

348-482 1 . 6 ( + 1 1

0 3675

379-465 3.2(+ll) 0 4630

323-415 1 . 9 ( + 1 1

0 3901

323-454 6.2(+10) 0 1700

298 - - 3675

298 - - 4265

298 - - 4350

303-417 7 . 8 ( +10

0 3475

323-454 1 . 5( +10) 0 2500

323754 3.1 ( +10) 0 2600

312-400 2.5(+ll) 0 2300

k factors

f F

0.6 1.6

75
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 7VK A B E/R

(in K)

298 - - 4300

298 - - 3620

308-448 2.5(+ll) 0 3900

300-520 2.8(+ll) 0 3986+100

318-414 1 . 6( +11

)

0 2265

338-435

i

3.9(+10) 0 3400

352-435 2.5(111) 0 3875

303-435 2.5(+10) 0 3070

300-455 3 . 9( +11

)

0 4430

359-439 6.2(+10) 0 3500

322-364 7.8(+ 9) 0 2800

328-420 6.2(fl0) 0 3300

339-425 1 . 2 ( + 1 1

)

0 3825

309-364 1 - 9( + 10) 0 2870

k factors

f F CH3CH2 . + cis-CH3CH2CH=CHCH3 - CH3CH2CH(CH2CH 3 )CH( . )CH3 ETHYL FREE RADICAL + cis-2-PENTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + (CH 3 ) 2 CHCH=CH2 - (CH3 ) 2 CHCH(.)CH2 CH2 CH 3

' ETHYL FREE RADICAL + 1-BUTENE, 3-METHYL72 KER/PAR REACTION ORDER: 2.

CH 3 CH2 . + CH.,C00CH2 CH=CH2 - CH3COOCH2CH(.)CH2CH2CH3

+ CH3 C00CH2 CH ( CH2 CH3

) ch2. ETHYL FREE RADICAL + ACETIC ACID 2-PROPENYL ESTER

72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + CH3 CH2COCH2 CH3 ETHYL FREE RADICAL

72 KON

CH3CH3 + ,CH2 CH2COCH2 CHc 3-PENTANONE

REACTION ORDER: 2.

CH3 CH2 CH2 =C(CH3 )C(CH3 )=CHs CH3 CH2 CH„C( . )

( CH3) C( CH3) =CH2

+ .CH2C(CH2 )(CH2 CH3 )C(CH3 )=CH2 ETHYL FREE RADICAL + 1,3-BUTADIENE, 2,3-DIMETHYL72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + CH3 (CH2 ) 3CH=CH2 - CH3 (CH2 ) 3 CH(.)CH2 CH2 CH3

+ CH3 (CH2 ) 3 CH(CH2 CH3 )CH2

. ETHVl FREE RADICAL + 1-HEXENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + CH3CH2C00CH2CH=CH3 - CH3CH2 COOCH2 CH(.)CH2 CH2CH

+ CH3 CH2 C00CH2 CH ( CH2 CH3 ) CH2

. ETHYL FREE RADICAL + PROPANOIC ACID 2-PROPENYL ESTER

72 KER/PAR REACTION ORDER: 2.

CH3CH2 . + CH 2 =CHO(CH2 ) 3 CH3 - CH3CH2CH2 CH(.)0(CH2 ) 3CH3

+ .CH2CH(CH2 CH3 )0(CH2 ) 3CH3 ETHYL FREE RADICAL + BUTANE, 1-ETHENYLOXY72 KER/PAR REACTION ORDER: 2.

CH3 CH2 CH3 ((CH2 ) 4C(.)=CHCH2 CHS

. + CH3 (CH2 ) 4CTCH -

+ CH3 (CH2 ) 4C(CH2CH3 )=CH. ETHYL FREE RADICAL + 1-HEPTYNE

72 KER/PAR REACTION ORDER: 2 .

CH3 CH2 . + CH3 (CH2 ) 4CH=CH2 - CH3 (CH2 ) 4CH(.)CH2CH2 CH,

+ CH3 (CH2 ) 4CH(CH2CH3 )CH2

. ETHYL FREE RADICAL + 1-HEPTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + (CH3 ) 3CC(CH3 )=CH2 -

CH3 C(CH3 ) 2 C( . ) (CH3 )CH2CH2CH3

+ CH3C(CH3 ) 2C(CH3 )(CH2CH3 )CH2 . ETHYL FREE RADICAL + 1-BUTENE, 2, 3, 3-TR I METHYL72 KER/PAR REACTION ORDER: 2.

CH3 CH2 . + (CH3 ) 2C=CHCH=C(CH3 ) 2 -

(CH3 ) 2C(CH2CH3 )CH( . )CH=C(CH3 ) 2

+ (CH3 ) 2C( . )CH(CH2CH3 )CH=C(CH3 ) 2 ETHYL FREE RADICAL + 2,4-HEXADIENE, 2, 5-DI METHYL72 KER/PAR REACTION ORDER: 2.

CH3CH2

. + CH3 (CH2 ) 5 CH=CH2 - CH3 (CH2 ) 5CH(.)CH2 CH2CH3

+ CH3 (CH2 ) 5CH(CH2CH3 )CH2

. ETHVl FREE RADICAL + 1-OCTENE

72 KER/PAR REACTION ORDER: 2.

CHoCH 3v... 2

. + (CH3 ) 3CCH2C(CH3 )=CH2 -

(CH3 ) 3CCH2 C( . ) (CH3 )CH2 CH2 CH3

+ ( CH3 ) 3CCH2C ( CH3 ) ( CH2CH3

) ch2

. ETHYL FREE RADICAL + 1-PENTENE, 2, 4, 4-TR I METHYL72 KER/PAR REACTION ORDER: 2.

0.4 2.2

76
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3CH3 - CH3

. + CH3

. ETHANE

70 BEN/0'N REACTION ORDER: 1.

CH3CH3 + 0 - CH3CH2

. + OH ETHANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 CH3 + H -* CH3CH2 . + H2 ETHANE + HYDROGEN ATOM

72 KON REACTION ORDER: 2.

CH3CH3 + OH -> CH3CH2 . + H2 0 ETHANE + HYDROXYL FREE RADICAL

72 KON REACTION ORDER: 2.

CH3CH3 + H02 - CH3CH2 . + H2 02 ETHANE + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: UPPER LIMIT RECOMMENDED. RATIO DATA VERSUS k ref FOR H02 + CO - HO + C02 CH3CH3 + ch3

. - ch3 ch2 . + ch4 ETHANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH3 + cd3. - ch3ch2 . + cd3 h ETHANE + METHYL-dg FREE RADICAL

72 KON REACTION ORDER: 2.

CH3CD3 -f- CDg . —> CH3CD2.

-)- CD4

ETHANE-1, l,l-d3 + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3CH3 + cd3. - cd3ch2 . + cd3 h ETHANE-1 , 1 , l-d3 + METHYL-dg FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3CD3 + ch3

. - cd3cd2 . + ch3d ETHANE-d6 + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3CD3 + cd3. - cd3cd2 . + cd4 ETHANE-d^, + METHYL-d3 FREE RADICAL

72 KON REACTION ORDER: 2.

CH2 =C=0 + 0 -* products ETHENONE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2. HOOC-COOH - HCOOH + C02 ETHANEDIOIC ACID

70 BEN/O'N REACTION ORDER: 1.

CH3 C(0). - CH3

. ETHYL, 1-0X0-

72 KON

+ CO FREE RADIOL

REACTION ORDER: 1.

CH3C(0). - CH3

. ETHYL, 1-0X0-

70 BEN/O'N

+ CO FREE RADICAL

REACTION ORDER: 1.

CH3CHO + 0 -* products ACETALDEHYDE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3CHO + CH3

. - CHgC(O). + CH4 ACETALDEHYDE + METHYL FREE RADIOL

76 KER/PAR REACTION ORDER: 2.

CH3CDO + CH3 . - CH3C(0). + ch3d ACETALDEHYDE- 1 -d + METHYL FREE RADIOL

76 KER/PAR REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

298-858 5.6(+16) 0 45045

2 . 5 ( +130 3200 0.7 1.3

285-1440 1.0(+14) 0 4815170 0.8 1.2

1.3(+14) 0 1998

300-1000 1 . 0 ( 112 ) 0 7000 0.1 10 .

5.6(111) 0 5840r250 0.7 1.3

390-800 1 . 0 ( 112 ) 0 6085=165 0.7 1.4

500-750 4.3(111) 0 6845+250 0.7 1.3

3.0(111) 0 59001250 0.7 1.3

500-900 5.6(111) 0 66001250 0.7 1.3

4.6(111) 0 6405

298 5.3(111) - - 0.7 1.3

390-420 7.9(111) 0 15100

273-413 1.5(110) 0 67901115 0.7 1.4

2 . 0 ( 110 ) 0 7550

298-500 1.4(113) 0 1140 0.5 2.0

300-525 8.5(110) 0 30001250 0.4 1.6

3C0-500 1 . 0 ( 111 ) 0 39751500 0.5 1.5

77
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions T! K A B E/R

(in K)

k factors

f F

298 7.0(+ 8 ) - - 0.6 1.5

350-500 2.5(411) 0 5435+750 0.5 2.0

350-550 2 . 0 ( 111 ) 0 4900+500 0.5 1.5

350-550 1.6(411) 0 5635+500 0.5 1.5

350-550 3.0(411) 0 4980+500 0.5 1.5

350-550 2.5(411) 0 5900+500 0.5 1.5

1.6(411) 0 5635+500 0.5 1.5

773-973 8.9(412) 0 33970

300-600 1.6(411) 0 5135+500 0.6 1.4

488-468 2.5(413) 0 8805

298 8.7(+10) - - 0.6 1.5

400-625 7.9(410) 0 4730+500 0.6 1.4

400-625

*

4.0(+ll

)

0 4900+500 0.6 1.4

400-625 5.1(411) 0 4900+500 0.6 1.4

400-550 4.1(411) 0 5735+500 0.6 1.4

400-550 7.1(410) 0 4530+500 0.6 1.4

400-525 6 . 2 (+ 10 ) 0 5135+500 0.5 2.0

400-525 4.4(+ll) 0 4900+500 0.6 1.4

cy-CH2 CH2 0 + 0 - products OXIRANE + OXYGEN ATOM

73 HER /HLI REACTION ORDER: 2. cy-CH2 CH20 + CH3

. - cy-CH2 CH(.)0 + CH4 OXIRANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. hcooch3 + ch3

. - ,cooch3 + FORMIC ACID METHYL ESTER - 76 KER/PARCH4METHYL FREE RADICAL

REACTION ORDER: 2. HCOOCH, + CH, HCOOCH, FORMIC ACID METHYL ESTER

76 KER/PAR

CH4 METHYL FREE RADICAL

REACTION ORDER: 2. HCOOCH* - CH 3

. - .C00CH3 + HC00CH3

. + CH4 FORMIC ACID METHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. DC00CH3 + CH3

. - .C00CH3 + CH3

D FORMIC-d ACID METHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. DCOOCH3 + ch3

. - dcooch2

. + ch4 FORMIC-d ACID METHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 C00H - CH2 =C=0 + H 2 0

‘ ACETIC ACID

70 BEN/O'N

NOTE: SUSPECT VALUE. REACTION ORDER: 1.

CH3COOD + CH3. - ACETIC ACT D-d

76 KER/PAR

.CH2 COOD + CH4 METHYL FREE RADICAL

REACTION ORDER:

CH3CH2

0. - CH3

. + HCHO ETHOXY FREE RADICAL

70 BEN/O'N

CH3 CH2OH + 0 - products

‘ ETHANOL + OXYGEN ATOM

73 HER/HUI

REACTION ORDER: 1.

REACTION ORDER: 2.

CH3CH2 OH + CH3. - CH3 CH2

0. + CH4 ETHANOL 4 METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH2OH + CH3. - CH3CH(.)OH + CH4 ETHANOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER:

CH3 CH2 OH + CH3. - CH3CH2 0 . + CH3CH(.)OH + .CH2CH2 OH 4 ETHANOL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CD2OH + CH3. -

ETHAN-1, l-d2-OL

76 KER/PAR

CH3CD2OH + CH3. -

ETHAN-1 , l-d2 -OL

76 KER/PAR

CH 0 CH 0 OD + CD,. -

CH3CD(.)0H + CH3 D

I- METHYL FREE RADICAL

REACTION ORDER: 2 .

ch3cd2o. + ,ch2cd2oh + ch4

h METHYL FREE RADICAL

REACTION ORDER: 2.

CH,CHoO. + CD. ETHANOL-d + METHYL-d

76 KER/PAR

3 FREE RADICAL

REACTION ORDER: 2.

CH3CH20D + CD3. - CH3CH(.)0D + .CH2CH20D + ETHANOUd + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2

CD,H

78
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

- =

Chemical reactions 77 K A B E/R

(in K) kf factors

F

CH3OCH3 - CH3

0. + ch3

. METHANE, OXYBIS70 BEN/O'N REACTION ORDER: 1. 750-820 1.0(+16) 0 40765

CH3OCH3 + 0 -* products

METHANE, 0XYBIS-, + OXYGEN

73 HER/HUI ATOM REACTION ORDER: 2. 200-500 5.9(+12) 0 1520 0.7 1.3

CH3OCH3 + ch3. - ch3och2

. METHANE, 0XYBIS-, + METHYL

76 KER/PAR

+CH4 FREE RADICAL

REACTION ORDER: 2. 300-550 4.2(+ll) 0 5035+500 0.5 1.5

CH3OOCH3 - CH30. + CH30. PEROXIDE, DIMETHYL70 BEN/O'N REACTION ORDER: 1. 393-452 4.0(+15) 0 18570

CH3OOCH3 + CH3

. - CH3 00CH2 . + ch4 PEROXIDE, DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. 350-500 4.2(411) 0 5000+1000 0.3 3.0

CH3CH200H - CH3CH20. + OH HYDROPEROXYDE, ETHYL70 BEN/O'N

NOTE: k PROBABLY RELIABLE. REACTION ORDER: 1. 553-653 2.2(+15) 0 21640

cy-CH2 CH2S + CD3. - cy-CH3 CH(.)S + CD3

H THYIRANE + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 300-500 2 . 2 (+ll) 0 4800+500 0.5 2.0

CH3CH2 SH - CH2 =CH2 + H2 S ETHANETHIOL

70 BEN/O'N REACTION ORDER: 1. 785-938 1.0(+13) 0 25900

CH3CH2 SH - CH3CH2 . + .SH ETHANETHIOL

70 BEN/O'N REACTION ORDER: 1. 785-938 6.31+15) 0 36336

CH3CH2SH + ch3. - CH3CH2S.

+ .CH2CH2SH + ch4 ETHANETHIOL + METHYL FREE

76 KER/PAR

NOTE: TENTATIVE k VALUE.

+ CH3CH(.)SH RADICAL

REACTION ORDER: 2. 303 3.5(4 7) - - 0.5 2.0

ch3so2ch3 - CH3S02 . + CH3 METHANE, SULFONYLBIS70 BEN/O'N REACTION ORDER: 1. 783-913 2.0(+14) 0 30500

CH3NC - CH3CN METHANE, ISOCYANO70 BEN/O'N REACTION ORDER: 1. 472-533 4.0(413) 0 19325

CH3CN + ch3

. - .ch2ch + ch4 ACETONITRILE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 350-600 5.4(411) 0 5100+500 0.7 1.5

CH3CH2 NH2 + CH3

. - CH3CH2NH. + CH3CH(.)NH2

+ .CH2 CH2 NH2 + CH4 ETHANAMINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 350-500 2.9(411) 0 4200+500 0.5 2.0

CH3CH2 NH2 + ch3

. - CH3 CH2NH. + ch4 ETHANAMINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. 350-500 2 . 0 (+ll) 0 4600+500 0.5 2.0

CD3CH2NH2 + CH3

. - CH4 + CH3 D + CD3CH(.)NH2 + .CD2CH2 NH2 ETHAN-2, 2, 2-d3-AM I NE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 350-500 2.9(411) 0 4200+500 0.5 2.0

CD3CH2 NH2 + CH3

-» CD3CH2NH. + ch4

ETHAN-2, 2, 2-dg-AMINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. 423 4.0(+ 5) - -

79
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

(CH3 ),NH + CH, METHAN AMINE, N-METHYL-, 76 KER/PAR

(CH3 ) 2N. + .CH2 NH(CH3 ) + CH, METHYL FREE RADICAL

REACTION ORDER: 2.

(CH 3 ) 2 NH + CH3. METHANAMINE, N-METHYL-, 76 KER/PAR(CH CH, 3 ) 2N. + METHYL FREE RADICAL

REACTION ORDER: 2.

(CH3 ) 2 ND + CH3. - CH2 NDCH3 METHANAMINE-d, N-METHYL-,

76 KER/PAR

+ CH4

+ METHYL FREE RADICAL

REACTION ORDER: 2.

(CH3 ) 2 ND + CH3. METHANAMINE-d, N-METHYL-, 76 KER/PAR

(CH3 ) 2N. + CH3 D

+ METHYL FREE RADICAL

REACTION ORDER: 2.

CH„N=NCH, .311 — nv..i CH, 3 - v,*. 3 . + CH3N = N. DIAZENE, DIMETHYL70 BEN/0 'N REACTION ORDER: 1.

CH3 N=NCH3 + CH3. - CH2 N=NCH3 + CH4

DIAZENE, DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3 N=NCH3 + CH3

. - (CH3 ) 2NN(.)CH3 DIAZENE, DIMETHYL-, + METHYL FREE RADICAL

72 KON REACTION ORDER: 2.

CD3 N=NCD3 + CD3

. - .CD2 N=NCD3 + CD4 DIAZENE, DI(METHYL-d3 )-, + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

NH2 CH2CH2 NH2 + CH3. - .NHCH2 CH2 NH2

+ NH2 CH(.)CH2 NH2 + CH4 ETHANEDIAMINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

NH2CH2 CH2 NH2 + CH3

. ,NHCH2 CH2 NH2 + CH4 ETHANEDIAMINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

ND2 CH2 CH2 ND2 + CH3. - .NDCH2CH2 ND2 + CH3D ETHANDI (AMINE-d2 ) + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

ND2CH2CH2 ND2 + CH3. - ND2CH(.)CH2 ND2 + CH4 ETHANEDI ( AM I NE-d2 ) + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 NNH2 + CH3

. - (CH3 ) 2 NNH. + CH4 HYDRAZINE, 1,1-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 NNH2 + CH3

. - (CH3 ) 2 NNH. + .CH2 N(CH3 )NH2 + CH4 HYDRAZINE, 1 , 1-DIMETHYL^, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 NND2 + CH3

. - (CH3 ) 2 NND. + CH3 D HYDRAZINE-d2 , 1,1-DIMETHYU, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 NND2 + CH3. - CH2N(CH3 )ND2 + CH4 HYDRAZINE-d2 , 1,1-DIMETHYU, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 NHNHCH3 + CH3

. - CH3 N(.)NHCH3 + .CH2 NHNHCH3 + CH4 HYDRAZINE, 1 , 2-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

77 K A B E/R

(in K)

k factors

f F

350-650 1 . 6( +1 1

)

0 3500+500 0.5 2.0

350-650 6.5(110) 0 3200+500 0.5 2.0

350-500 2 . 9 ( + 1 1

)

0 4400+500 0.5 1.5

350-500 1.0(+11) 0 4300+500 0.5 1.5

552-600 3.2(+16) 0 26400

300-500 1 . 1 (+11

)

0 3975+250

300-450 5.0(110) 0 3040+355

300-500 6.6(+10) 0 4125+500

350-500 3.8(+ll) 0 4200+500

350-500 2 . 0 ( + 1 1

)

0 4430+500

350-500 3.2(+ll) 0 5100+500

350-500 2.0(+ll) 0 4025+500

350-500 1 . 7 ( + 1 1

)

0 2870+500

350-500 2.4(+ll) 0 2970+500

350-500 2 . 1 ( + 1 1

)

0 3400+500

350-500 3 . 2 ( + 1 1

)

0 4125+750

350-500

l

2 . 5(+ll

)

0 2400+250

80
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

1 = =^=

Chemical reactions

CH3 NDNDCH3 + CH3

. - CH3 N(.)NDCH3 + CH3 D HYDRAZINE-d2 , 1 , 2-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH=N0H - CH3CH=N. + OH ACETALDEHYDE, OXIME

70 BEN/0 'N REACTION ORDER: 1.

HCONHCH3 + CH3

. - . CONHCHg + HC0N(.)CH3

+ hconhch2

. + ch4

FORMAMIDE, N-METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3C0NH2 + CH3

. - CH3CONH . + .CH2 C0NH2 + CH4 ACETAMIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3C0NH2 + CH3. - .CH2C0NH2 + CH4 ACETAMIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3C0NH2 + CD3

. - ,CD2C0NH2 + CD4 ACETAMIDE-2, 2, 2-d3 + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3C0NH2 + CD3 - CD3CONH. + CD3 H ACETAMIDE-2, 2, 2-d3 + METHYL~d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH2 N02 - CH2 =CH2 + HONO

ETHANE, NITRO70 BEN/O 'N REACTION ORDER: 1.

CH3CH2ONO - CH3 CH2

0. + NO NITROUS ACID ETHYL ESTER

70 BEN/O 'N REACTION ORDER: 1.

CH3CH20N02 - CH3 CH20. + N02 NITRIC ACID ETHYL ESTER

70 BEN/O 'N REACTION ORDER: 1.

02NOCH2 CH2ONO2 -* products

1,2-ETHANEDIOL, DINITRATE

70 BEN/O 'N REACTION ORDER: 1.

CH3N(0)N(0)CH3 - CH3NO + CH3 NO DIAZENE, DIMETHYL-1, 2-DIOXIDE70 BEN/O' N REACTION ORDER: 1.

CH3CTCH + 0 -* products

1-PROPYNE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3CTCH + H -> CH3 CH=CH. + CH3C(.)=CH2 1-PROPYNE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: k TAKEN AS LOWER LIMIT. CH3CTCH +S- cy-CH3C=CHS

1-PROPYNE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

CH3CTCH + N -* products 1-PROPYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

CH 3CTCH + N - products 1-PROPYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: k ref : CHCH + N

77 K A B E/R

(in K)

350-500 2 . 0 (+ll) 0 2700+500

603-713 6 . 8 (+ 12 ) 0 23655

400-600 7.9(+10) 0 3800+500

350-600 2 . 1 (+ 11 ) 0 5235+500

350-600 1 . 0 (+ 11 ) 0 5200+500

350-600 1.4(+11) 0 5800+500

350-600 l.K+ll) 0 5235+500

583-715 2.5(412) 0 22645

484-505 1.2(+16) 0 20400

434-474 3.2(+16) 0 19830

358-378 7 . 9 ( +15

0 19630

374-404 2 . 5 ( +13

0 11600

298 4.0(+ll) - -

298 2.5(+ll) - -

298 1 - 1 (

12 ) - -

320-550 6.9(+10) 0 745

435 - - -

k factors

f F

0.5 2.0

81
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3C=CH + CH3. - (CH3 ) 2C=CH. + CH3C(.)=CHCH3 1-PROPYNE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. CH3 ADDITION OCCURS PREDOMINANTLY AT TERMINAL C ATOM.

CH3ChCH + (CH3 ) 2CH. - (CH3 ) 2 CHCH=C(.)CH3 1-PROPYNE + ETHYL, 1 -METHYL-, FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: SUSPECT k VALUE.

CH3GeCH + (CH3 ) 3C. - (CH3 ) 3 CC(CH3 )=CH.

+ (CH3 ) 3CCH=C(.)CH3 1-PROPYNE + ETHYL-, 1,1-DIMETHYL-, FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: SUSPECT k VALUE.

CH2 =C=CH2 + CH3

. - CH3 CH2 C(.)=CH2

1 ,2-PROPADIENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3 =C=CH2 + CH3CH2. - CH3 CH2 CH2 C(.)CH2 1,2-PROPAD I ENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =C=CH2 + (CH3 ) 2CH. - (CH3 ) 2CHCH2C(.)=CH2

1 ,2-PROPADIENE + ETHYL, 1-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH=CH2 - CH2 =CHCH2

. + H 1-PROPENE

70 BEN/O'N REACTION ORDER: 1.

CH3CH=CH2 + 0 - cy-(CH3 )CHCH2 0 1-PROPENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3CH=CH2 + H - CH3CH2 CH2. 1-PROPENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 CH=CH2 + H - CH3 CH(.)CH3 1-PROPENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: ARRHENIUS PARAMETERS ARE MINIMUM VALUES

OF THEIR HIGH PRESSURE LIMITS.

CH3CH=CH2 + OH - CH3 CH(.)CH2OH + CH3CH(OH)CH2

. 1-PROPENE + HYDROXYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: ADDITION TO TERMINAL CARBON OF DOUBLE BOND

IS PROBABLY 95%.

CH3CH=CH2 + S - cy-(CH3 )CHCH2 S 1-PROPENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

CH3CH=CH2 + S - cy-(CH3 )CHCH2 S 1-PROPENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 6.9

NOTE: k ref : CH2 =CH2 + S

CH3CH=CH2 + S’(*D) - cy-(CH3 )CHCH2 S 1-PROPENE + SULFUR ATOM^D)

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.7 NOTE: k ref : CH2 =CH2 + S*(*D)

CH3CH=CH2 + N -• products

1-PROPENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

7VK A B E/R

(in K)

379-465 5.0(+ll) 0 4400

360-439 1.9(+ 9) 0 2870

360-439 5.0(+ 8) 0 2770

373-483 2.0(+ll) 0 4100

379-465 3.2(111) 0 4630

366-473 3.6(+10) 0 3660

953-1143 2 . 0( + 15

)

0 44900

200-500 2 . 5 ( + 12

)

0 38

298 11.2(+12) 0 1460

298 7.2(+12) 0 600

300 6.6(+12) - -

298 5 . 8 ( + 12

)

- -

298 - - -

300 - - -

320-550 1.2(+11) 0 655

k factors

f F

0.8 1.2

82
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3CH=CH2 + N - products

1-PROPENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 2.8

NOTE: k ref : CH2 =CH2 + N

CH3CH=CH2 +

1 CH2 -* products

1-PROPENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.27

NOTE: k ref : CH2 =CH2 +

1 CH2 CH3 CH=CH2 + 3 CH2 - products

1-PROPENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.0

NOTE: k ref : CH2 =CH2 + 3 CH2 CH3CH=CH2 + CH3

. - CH3C(.)=CH2 + CH4 1-PROPENE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH=CH2 + CH3

. - [C3H5 .] + CH4 1-PROPENE + METHYL FREE RADICAL

72 KON REACTION ORDER: 2.

CH3CH=CH2 + CH3

. - CH3CH2 CH(.)CH3 + (CH3 ) 2CHCH2

. 1-PROPENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3CH=CH2 + CH3. - CH3 CH2CH(.)CH3 + (CH3 ) 2 CHCH2 . 1-PROPENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.72

NOTE: k ref : CH2 =CH2 + CH3 CH3CH=CH2 + CCO - CH3 CH=C=CH2 + CO 1-PROPENE + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/kref : 5.7

NOTE: k ref : CH2 =CH2 + CCO

CH3CH=CH2 + CH3 CH2 CH(.)CH3 - CH3CH2CH(CH3 )CH(CH3 )CH2 . + CH3 CH2 CH ( CH3

) CH2CH ( . ) ch3 1-PROPENE + PROPYL, 1-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH2 CH2

. - CH3

. + CH2 =CH2 1-PROPYL FREE RADICAL

72 KON REACTION ORDER: 1.

CH3 CH2CH2

. - CH3

. + CH2 =CH2 1-PROPYL FREE RADICYL

70 BEN/ O' N REACTION ORDER: 1.

CH3CH2 CH2

. - CH3CH=CH2 + H 1-PROPYL FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

CH3 CH2CH2 . + CH2 =CH2 - CH3 CH2CH2CH2 CH2

. 1-PROPYL FREE RADICAL + ETHENE

72 KON REACTION ORDER: 2. NOTE: TENTATIVE k VALUE

CH3CH2 CH2 . + CH3CH2 CH=CH2 - CH3CH2 CH(.)CH2CH2 CH2CH3 1-PROPYL FREE RADICYL + 1-BUTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 CH2 . + cis-CH3CH=CHCH3 - CH3 CH(CH2 CH2 CH3 )CH( . )CH3 1-PROPYL FREE RADICAL + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2CH2

. + t rans-CH3CH=CHCH3 -

CH3 CH(CH2 CH2 CH3 )CH( . )CH3 1-PROPYL FREE RADICYL + trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2.

7VK A B E/R

(in K)

435 - - -

297 - - -

297 - - -

350-600 1 . 4( +11) 0 4430r500

350-580 3.2(410) 0 3775*300

353-453 1-7 (+11

0 3770

453 - - -

297 - - -

381-412 6.3(410) 0 3725

300-750 5.8(414) 0 16880±350

297-564 4.0(il3) 0 16660

298-723 6.3(413) 0 1 9100

375-503 1.9(+10) 0 3070

298 - - 3630

298 . - - 4370

298 - - 4515

k factors

f F

83
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3 CH2CH2. + CH3 CH2 CH2 CH=CH2 -

CH3 CH2CH2 CH( . )CH2 CH2CH2 CH3 1-PROPYL FREE RADICAL + 1-PENTENE

72

KER/PAR REACTION ORDER: 2.

(CH3 ) 2CH. - CH3 + CH2 =CH2 ETHYL, 1-METHYL- , FREE RADICAL

72 KON REACTION ORDER: Y.

(CH3 ) 2 CD. - CH3 CD=CH2 + H. ETHYL-l-d, 1 -METHYL- , FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 CH. + CH=CH - (CH3 ) 2 CHCH=CH.

ETHYL, 1-METHYL, FREE RADICAL + ETHYNE

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2CH. + CH2 =CH2 - (CH3 ) 2 CHCH2CH2

. ETHYL, 1-METHYL- , FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CH. + CH3C=CH - (CH3 ) 2CHCH=C(.)CH3 ETHYL, 1 -METHYL-, FREE RADICAL + 1-PROPYNE

72 KER/PAR REACTION ORDER: 2. NOTE: SUSPECT k VALUE.

(CH3 ) 2CH. + CH2 =C=CH2 - (CH3 ) 2CHCH2C(.)=CH2 ETHYL, 1 -METHYL-, FREE RADICAL + 1,2-PROPADIENE

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CH. + CH3 CH2 CH=CH2 - (CH3 ) 2CHCH2 CH(.)CH2CH3 ETHYL, 1-METHYL-, FREE RADICAL + 1-BUTENE

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2CH. + cis-CH3CH=CHCH3 - CH3 CH[CH(CH3 ) 2 ]CH( . )CH3 ETHYL, 1-METHYL- , FREE RADICAL + cis-2-BUTENE

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CH. + t rans-CH3CH=CHCH - CH3CH[CH(CH3 ) 2 ]CH( . )CH3 ETHYL, 1 -METHYL-, FREE RADICAL I trans-2-BUTENE

72 KER/PAR REACTION ORDER: 2.

CH3CH2 CH3 + 0 -* products

' PROPANE + OXYGEN ATOM

73

HER/HUI REACTION ORDER: 2.

CH3CH2CH3 + H - (CH3 ) 2CH. + CH3CH2CH2 . + H2 PROPANE + HYDROGEN ATOM

72 KON REACTION ORDER: 2.

CH3CH2 CH3 + H02 - (CH3 ) 2 CH. + H 202 PROPANE + HYDROPEROXYL FREE RADICAL

74

LLO REACTION ORDER: 2. NOTE: UPPER LIMIT RECOMMENDED. RATIO DATA VERSUS k ref FOR H02 + H02 - H2

02 + 02 CH3CH2CH3 + CH3

. - (CH3 ) 2CH. + CH4 PROPANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CD2CH3 + CD3. - (CH3 ) 2CD. + CD4 PROPANE-2, 2-d2 + METHYUd3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CD2 CH3 + CD3. - CH3CD2 CH2

. + CD3

H

‘ PROPANE-2, 2-d2 + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

77 K A B E/R

(in K)

298 - - 3410

690-814 1 .9(411

)

0 16045+1150

673-777 2.00(+14) 0 20800

363-577 5.0(+10) 0 3475

340-457 6.9(+10) 0 3475

360-439 1 . 90 ( + 9) 0 2870

366-473 3 . 6 ( + 10

)

0 3600

298 - - 3480

298 - - 3950

298 - - 4065

298 9.0(+ 9) - -

333-933 1.0(+13) 0 3130+180

300-1000 2.0(+ll) 0 5300

550-750 2.0(+ll) 0 4820+250

550-750 2.5(411) 0 5735+250

550-750 4.4(+ll) 0 5735+250

k factors

f F

0.7 2.0

84
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3C0CH2

. - CH3

. + CH2 =C=0

PROPYL, 2-0X0- , FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

CH3CH2 CH0 + CH3

. - CH3CH2 C(0). + CH4 PROPANOL + METHYL FREE RAD I CL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 C0 - CH3C(0). + CH3

. I-PROPANONE

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2C0 + H - CH3C0CH2 . f H2 2-PR0PAN0NE + HYDROGEN ATOM

72 KON REACTION ORDER: 2.

(CH3 ) 2C0 + CH3 - CH3C0CH2 . + CH4 2-PR0PAN0NE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CD3 ) 2C0 + CD3

. - CD3C0CD2

. + CD4 2-PR0PAN0NE-1 , 1 , 1 , 3 , 3 , 3-d6 + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH2 =CHCH2OH + CH3 CH2

. - CH3 CH2 CH2 CH(.)CH2OH

+ ,CH2 CH(CH2 CH3 )CH2 OH 2-PR0PEN-1-0L + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

HCOOCH2 CH3 - HCOOH + CH2 =CH2 FORMIC ACID ETHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

HCOOCH2CH3 + CH3. - ,COOCH2 CH2 + HCOOCH(.)CH3 + CH4 FORMIC ACID ETHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 COOCH3 + CH3. - ,CH2 COOCH3 + CH3COOCH2 . + CH4 ACETIC ACID METHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3COOCD3 + CH3. - ,CH2COOCD3 + CH4 ACETIC ACID METHYL-d3 ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CD3COOCH3 + CH3. - CD3COOCH2 + CH4 ACETIC-d3 ACID METHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3OCOOCH3 + CH3. - ,CH2 OCOOCH3 + CH4 CARBONIC ACID DIMETHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CHOH + 0 -» products

2-PROPANOL + OXYGEN ATOM

73 HER /HU I REACTION ORDER: 2.

(CH3 ) 2CDOH + CH3

. - (CH3 ) 2C(.)OH + CH3

D 2-PR0PAN-2-d-0L + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CHOD + CD3

. - (CH3 ) 2 C(.)OD + .CH2CH(CH3 )OD + CD3H 2-PR0PAN0L-d + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CHOOH - (CH3 ) 2CHO. + OH HYDROPEROXIDE, 1-METHYLETHYL

70 BEN/O'N REACTION ORDER: 1.

77K A B E/R

(in K)

365-435 3 . 2 ( +12

0 20130

350-500 1.0(+11) 0 2970+500

990-1101 1 . 8( +16) 0 40765

298-873 4.6(+13) 0 4220+20

350-700 3.5(+ll) 0 4900±250

350-800 4 . 8 ( +1 1

0 5735+250

323-415 1 . 9 ( +1 1

0 3901

648-920 2.5(+12) 0 24300

350-500 2.5(411) 0 5100+500

350-600 2.1(+11) 0 5035+500

350-650 1.9(+11) 0 5035±500

400-600 1.7(411) 0 5990+500

350-500 3.2(411) 0 5800i750

298 1.3(411) - -

400-525 1.9(411) 0 49901500

400-525 1.5(411) 0 3975+500

553-653 3.2(+15) 0 21640

k factors

f F

0.6 1.5

85
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

cy-CH2CH2 CH2 S + CH3 - cy-CH2 CH( . )CH2S + CH4 THIETANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2CHSH + CH3. - (CH3 ) 2 CHS. + (CH3 ) 2 C(.)SH

+ ,CH2CH(CH3 )SH + ch4 2-PROPANETH I OL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH2 =CHCN + CH3CH2. - CH3CH2 CH2 CH(.)CN + .CH2 CH(CH2 CH3 )CN

2-PROPENEN ITR I LE + ETHVL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3CH2 CN - CH3

. + .CH2 CN PROPANENITRILE

70 BEN/O'N REACTION ORDER: 1.

CH3CH2CN + CD3

. - CH3CH(.)CN + .CH2 CH2 CN + CD3

H PROPANENITRILE + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 3

N + CH3

. - .CH2 N(CH3 ) 2 + ch4 METHANAMINE, N,N-D I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

02N0CH2CH(0N02 )CH2 0N02 -* products

1 ,2,3-PROPANETRIOL, TRINITRATE

70 BEN/O'N REACTION ORDER: 1.

02 N0CH2 CH(0N02 )CH3

-* products

1,2-PROPANEDIOL, DINITRATE

70 BEN/O'N REACTION ORDER: 1.

02 N0CH2 CH2 CH20N02 -» products

1,3-PROPANEDIOL, DINITRATE

70 BEN/O'N REACTION ORDER: 1. HCON(CH3 ) 2 + CH3

. - CON(CH3 ) 2 + HCO-(CH3 )NCH2 . + CH4 FORMAMIDE, N,N-D I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH2CH2N02 - CH 3CH=CH2 + HONO

PROPANE, 1-NITRO70 BEN/O'N REACTION ORDER: 1.

CH3CH(N02 )CH3 - CH 3CH=CH2 + HONO

PROPANE, 2-NITRO70 BEN/O'N REACTION ORDER: 1.

CH3 CH2 CH2 ONO - CH3CH2CH20. + NO NITROUS ACID PROPYL ESTER

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2CHONO - (CH3 ) 2 CHO. + NO NITROUS ACID 1-METHYL ETHYL ESTER

70 BEN/O'N REACTION ORDER: 1. CHsCCsCH + 0 -* products

1 ,3-BUTADIYNE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3CH2 C=CH + N -» products

‘ 1-BUTYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 13.0

NOTE: k rcf : CH^CH + N

77K A B E/R

(in K)

300-450 3.2(111) 0 4630+750

303 4. 1( + 7) - -

323-454 6.2(+10) 0 1700

958-1038 1.3(+14) 0 36600

400-600 3 . 6( +11 )

0 4330+500

350-600 4.7(111) 0 4600+500

348-378 1 . 3 ( +17

)

0 20300

353-373 1 . 6(+15) 0 18800

358-383 1.6(115) 0 19175

400-600 6 . 3 ( + 10

)

0 3600+500

687-733 2 . 50 ( + 13

)

0 24005

800-1000 2 . 0 ( + 1 1

)

0 20130

443-483 1.6(+16) 0 20230

443-483 3.2(+16) 0 18600

300 9.0(111) - -

320-550 3 . 5 ( + 1 1

)

0 1125 435

k factors

f F

0.7 1.4

86
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3CH2C=CH + CH3

. - CH3CH(.)(=CH + ,CH2CH2C=CH

+ CH3 CH2 C=C. + CH4 1-BUTYNE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3C=CCH3 + S - cy- ( CH3

) C=C ( CH3)

2-BUTYNE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

CH3C=CCH3 + N -» products

2-BUTYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k re f

: 12.0

NOTE: k ref : OM + N

CH3CsCCH3 + CH3. - CH3C=CH2 . + CH4 2-BUTYNE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3C=CCH3 + CCO -> products

2-BUTYNE + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k ref : 8.5

NOTE: k ref : CH2 =CH2 + CCO

CH2 =CHCH=CH2 + 0 -> products

1,3-BUTADIENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH2 =CHCH=CH2 + H - CH2 =CHCH(.)CH3 + CH2 =CHCH2CH2

. 1,3-BUTADIENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: AVERAGED k. k/kre f

: 4.9

NOTE: k ref : CH3CH=CH2 + H

CH2 =CHCH=CH2 IS- cy- ( CH2 =CH ) CHCH2S 1,3-BUTADIENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

CH2 =CHCH=CH2 + N - products

1,3-BUTADIENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

CH2 =CHCH=CH2 +

1 CH2 - products

1,3-BUTADIENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/kref : 3.2

NOTE: k ref : CH2 =CH2 + ^H., ASSUMING 10% 3CH2 CH2 =CHCH=CH2 + CH3

. - CH3CH2 CH(.)CH=CH2. 1,3-BUTADIENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =CHCH=CH2 + CH3

. - CH3CH2 CH(.)CH=CH2

+ . CH2CH ( CH3

) CH=CH2 1,3-BUTADIENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 12.0

NOTE: k ref : CH2 =CH2 + CH3

.

CH2 =CHCH=CH2 + CCO - CH2 =C=CHCH=CH2 + CO 1,3-BUTADIENE + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k ref : 210. NOTE: k ref : CH2 -CH2 + CCO

CH3CH2CH=CH2 + 0 - cy-(CH3CH2 )CHCH2 0 1-BUTENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3CH2CH=CH2 + H - CH3 CH2CH(.)CH3 + CH3CH2CH2 CH2

. 1-BUTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.03

NOTE: k ref : CH3CH=CH2 + H

7VK A B E/R

(in K)

456-620 1 . 9 ( +12

0 5135+500

298 1 . 9 ( +13

- -

320-550 1.9(111) 0 926

435

486-619 1.1 (+12) 0 4900+500

304 - - -

298-400 3.4(+12) 0 - 380

298 4. 10(+13) 0 655

300 - - -

298 6 . 0( +13

- -

340 3.5(+10) - -

297 - - -

353-453 8.1 ( +10) 0 2065

435 - - -

298 - - -

298 2.3(112) - -

298 8.7(+ll)

300

k factors

f F

0.7 1.3

0.8 1.2

87
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3CH2CH=CH2 + H - CH3CH2CH2 CH2. 1 -BUTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: CALCULATED ON THE BASIS OF 5.7% NON-TERMINAL

ADDITION OF H TO 1-BUTENE.

CH3CH2CH=CH2 + H - CH3 CH2 CH(.)CH3 1-BUTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: CALCULATED ON THE BASIS OF 5.7% NON-TERMINAL

ADDITION OF H TO 1-BUTENE.

CH3CH2 CH=CH2 + S - cy-(CH3CH2 )CHCH2S 1-BUTENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 10.0

NOTE: k ref : CH2 =CH2 + S

CH3CH2 CH=CH2 + N -* products

1-BUTENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k : 3.4

NOTE: k ref : CH2 =CH2 + N

CH3 CH2CH=CH2 + ‘CH-j: - products

1-BUTENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/kref : 1.63

NOTE: k ref : CH2 =CH2 +

1 CH2 CH3CH2 CH=CH2 + 3 CH2 -» products

1-BUTENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.6

NOTE: k ref : CH2 =CH2 + 3CH2 CH3CH2 CH=CH2 + CH3

. - CH3CH(.)CH=CH2 + CH4

‘ 1-BUTENE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH2CH=CH2 + CH3. - CH3CH2 CH(.)CH2 CH3

+ CH3CH2CH(CH3 )CH2

. 1-BUTENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 12.0

NOTE: k ref : CH2 =CH2 + CH3

. ch3ch2ch=ch2 + cco - CH3CH2CH=C=CH2 + CO 1-BUTENE + CARBON 0XIDE(C2 0) 72 KER/PAR REACTION ORDER: 2. k/k ref : 7.0

NOTE: k ref : CH2 =CH2 + CCO

CH3CH2 CH=CH2 + CH3CH2. - CH 3 CH2 CH2 CH(.)CH2 CH3 1-BUTENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3CH2 CH=CH2 + CH3 CH2 CH2

. - CH3 CH2 CH(.)CH2 CH2 CH2 CH3 1-BUTENE + PROPYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3CH2CH=CH2 + (CH3 ) 2 CH. - (CH 3 ) 2CHCH2CH(.)CH2 CH3 1-BUTENE + ETHYL, 1-METHYL-, FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =CHCH2 CH3(+M) - CH2 =CHCH2 . + CH3 .(+M)

1-BUTENE

70 BEN/O'N REACTION ORDER: 1. NOTE: k ESTIMATED.

CH3 CH=CHCH3 + CH3S. - CH3CH(SCH3 )CH(.)CH3 2-BUTENE + METHYLTHIO FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: cis-trans EQUILIBRIUM - WEIGHTED k.

77 K A B E/R

(in K)

298 5 . 0 ( + 10

)

- -

298 8 . 1 ( + 1 1

)

- -

298 9.3(112)

298

320-550 1.6(111) 0 660

435

297 - - -

297 - - -

350-650 2.5(111) 0 4200+500

353-453 1.0(411) 0 3600

453

298 - - -

298 - - 3675

298 - - 3630

298 - - 3480

900-1051 1.00(+16) 0 36900

298-333 1.6(1 9) - -

k factors

f F

0.6 1.4

88
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

cis-CH 3CH=CHCH3 - trans-CH3CH=CHCH3 cis-2-BUTENE

70 BEN/0 'N REACTION ORDER: 1.

cis-CH3CH=CHCH3 + 0 -> products

cis-2-BUTENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

cis-CH3CH=CHCH3 + H -* CH3CH2 CH( . )CH3 cis-2-BUTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: NO KINETIC DATA ON REVERSE RADICAL DECOMPOSITION.

k/k ref : 0.47

NOTE: k ref : CH3CH=CH2 + H

cis-CH3CH=CHCH3 + S - cy-(CH3CH)CH(CH3

)S cis-2-BUTENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k rof : 16.0

NOTE: k ref : CH2 =CH2 + S

cis-CH3CH=CHCH3 + N -> products

cis-2-BUTENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 2.4

NOTE: k ref : CH2 =CH2 + N

cis-CH3CH=CHCH3 +

1 CH2

: -> products

cis-2-BUTENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.37

NOTE: kref : CH2 =CH2 +

1 CH2 cis-CH3 CH=CHCH3 + 3CH2 -> products

cis-2-BUTENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.94

NOTE: k ref : CH2 =CH2 + 3CH2 cis-CH3CH=CHCH3 + CH3

. - CH3CH=CHCH2 . + CH4 cis-2-BUTENE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

cis-CH3CH=CHCH3 + CH3. - (CH3 ) 2CHCH( . )CH3 cis-2-BUTENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.2

NOTE: k ref : CH2 =CH2 + CH3

.

cis-CH3CH=CHCH3 + CCO - cis-CH3CH=C=CHCH3 + CO cis-2-BUTENE + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k ref : 9.1

NOTE: k ref : CH2 =CH2 + CCO

cis-CH3CH=CHCH3 + CH3CH2

. - CH3 CH(CH2CH3 )CH( . )CH3 cis-2-BUTENE + ETHYL FREE RAdIcAL

72 KER/PAR REACTION ORDER: 2.

cis-CH3CH=CHCH3 + CH3CH2CH2

. - CH3CH(CH2 CH2CH3 )CH( . )CH 3 cis-2-BUTENE + PROPYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. cis-CH3CH=CHCH3 + (CH3 ) 2 CH. - CH3CH[CH(CH3 ) 2 ]CH( . )CH3 cis-2-BUTENE + ETHYL, 1-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2. trans-CH3CH=CHCH3 + 0 -* products

trans-2-BUTENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

77K A B E/R

(in K)

686-742 6 . 00 ( + 13

0 31600

250-500 5.9(+12) 0 - 165

208 4 . 6( +1 1

- -

300 - - -

298 1.4(+13) 298

320-550 2.3(111) 0 995

435

297 - - -

297 - - -

350-650 1.8(+11) 0 4100+500

353-453 4.5(+10) 0 3675

453

297 - - -

298 - - 4265

298 - - 4370

298 - - 3950

298 1 . 4( +13)

k factors

f F

0.8 1.2

0.7 1.3

89
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

t rans-CH3CH=CHCH3 + H - CH3CH2CH( . )CH3 trans-2-BUTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: AVERAGE k. k/k ro f

: 0.59

NOTE: k ref : CH3 CH=CH2 + H

t rans-CH3CH=CHCH3 + S - cy-(CH3CH)CH(CH3)S trans-2-BUTENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 20.0

NOTE: k ref : CH2 =CH2 + S

t rans-CH3CH=CHCH3 + N - products

trans-2-BUTENE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 3.0

NOTE: k ref : CH2 =CH2 + N

t rans-CH3CH=CHCH3 +

1 CH2

-* products

trans-2-BUTENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.39

NOTE: k ref : CH2 =CH2 +

X C&2 trans-CH3CH=CHCH3 + 3CH2 -» products

trans-2-BUTENE + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.89

NOTE: k ref : CH2=CH2 + 3CH2

t rans-CH3 CH=CHCH3 trans-2-BUTENE

76 KER/PAR

CH3. - CH3CH=CHCH2

. + CH4 METHYL FREE RADICAL

REACTION ORDER: 2.

t rans-CH3CH=CHCH3

t rans-2-BUTENE

72 KER/PAR

CH3. - (CH3 ) 2CHCH(.)CH3 METHYL FREE RADICAL

REACTION ORDER: 2.

t rans-CH3CH=CHCH3 + CH3. - (CH3 ) 2 CHCH( . )CH3 trans-2-BUTENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.4

NOTE: k ref : CH2 =CH2 + CH3

t rans-CH3CH=CHCH3 + CCO - CH3CH=C=CHCH3 + CO trans-2-BUTENE + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k ref : 10.6

NOTE: k ref : CH2 =CH2 + CCO

t rans-CH3 CH=CHCH3 + CH3CH2. - CH3CH(CH2 CH3 )CH( . )CH3 trans-2-BUTENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

t rans-CH3 CH=CHCH3 + CH3CH2 CH2. -

CH3 CH(CH2 CH2 CH 3 )CH(.)CH3 trans-2-BUTENE + PROPYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

t rans-CH3CH=CHCH3 + (CH3 ) 2CH. - CH3CH[CH(CH3 ) 2 ]CH( . )CH3 trans-2-BUTENE + ETHYL, 1-METHYL- , FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2C=CH2 - .CH2C(CH3 )=CH2 + H 1-PROPENE, 2-METHYL70 BEN/O 'N REACTION ORDER: 1.

(CH3 ) 2C=CH2 + 0 - cy-[ (CH3 ) 2 ]CCH20 1-PROPENE, 2-METHYL- , + OXYGEN ATOM

73 HER/HU I REACTION ORDER: 2.

(CH3 ) 2C=CH2 + H - (CH3 ) 3

C. 1-PROPENE, 2-METHYL- , + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

77K A B E/R

(in K)

298 5 . 6( + 1 1

)

.

300 - - -

298 1 . 4( +13

)

298

320-550 3.4(+ll) 0 1055 435

297 - - -

297 - - -

350-500 1.0(+12) 0 4830+500

353-453 1 . 4( +11

)

0 4075

453 - - -

297 - - -

298 - - 4350

298 - - 4515

298 - - 4065

930-1082 1 . 0( +17

)

0 44400

298 1.2(tl3) - -

298 3 . 1 ( + 13

)

0 755

k factors

f F

0.7 1.3

90
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions 77K A B E/R

(in K)

298

)V 1.3(+11) - -

300 - - -

300 1.0(+ 8) - -

298 4.0(+13)

298

300 - - -

320-550 7.8(+10) 0 277

435 - - -

297 - - -

297 - - -

350-600 3 . 0( +11

0 4500+500

353-453 1.4(+11) 0 3475

453

297 - - -

334-689 4.0(+13) 0 14600

352-405 2.3(+10) 0 3370

523-622 1.4(+14) 0 17060

k factors

f F

(CH3 ) 2C=CH2 + H - (CH3 ) 2CHCH2

. 1-PROPENE, 2-METHYL- , + HYDROGEN ATOM

72 KER/PAR REACTION ORDER:

NOTE: CALCULATED ON THE BASIS OF 0.5% NON-TEF OF H TO (CH3 ) 2C=CH2

.

(CH3 ) 2C=CH2 + H - (CH3 ) 3C. + (CH3 ) 2 CHCH2

. 1-PROPENE, 2-METHYL- , + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: V f : CH 3CH=CH2 + H k/k. 2.52

(CH3 ) 2C=CH2 + H02 -> products

1-PROPENE, 2-METHYL- , + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: SUGGESTED k VALUE.

(CH3 ) 2C=CH2 + S - cy-[ (CH3 ) 2 ]CCH2 S 1-PROPENE, 2-METHYL- , + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k re f

NOTE: k ref : CH2 =CH2 + S

(CH3 ) 2C=CH2 + SVD) - cy-[(CH3 ) 2 ]CCH2

S 1-PROPENE, 2-METHYL- , + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref :

50.0

3.5

NOTE: k. CH2 =CH2 + S’( X D)

(CH3 ) 2C=CH2 + N -» products

1-PROPENE, 2-METHYL- , + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 C=CH2 + N -» products

1-PROPENE, 2-METHYL- , + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k__ f : CH2 =CH2 + N

(CH3 ) 2C=CH2 +

1 CH2 -» products

1-PROPENE, 2-METHYL- , + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k re NOTE: k ref : CH2 =CH2 +

1 CH2 (CH3 ) 2 C=CH2 + 3 CH2 -> products

1-PROPENE, 2-METHYL- , + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/kre NOTE: k CH,=CH, + 3CH,

4.1

1.96

2.86

(CH3 ) 2C=CH2 + CH3. - .CH2 C(CH3 )=CH2 + CH4

1-PROPENE, 2-METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2C=CH2 + CH3. - (CH3 ) 3CCH2

. + (CH3 ) 2C(.)CH2CH3 1-PROPENE, 2-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref ; 1.1 NOTE: k. CH2 =CH2 + CHa

(CH3 ) 2 C=CH2 + CCO - (CH3 ) 2C=C=CH2 + CO 1-PROPENE, 2-METHYL- , + CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k f NOTE: k ref : CH2 =CH2 + CCO

50.0

CH3CH2 CH2 CH2

. - CH3CH2 BUTYL FREE RADICAL

70 BEN/O 'N

+ CH2 =CH2 REACTION ORDER: 1 .

CH3CH2CH2CH2 . + CH2 =CH2 - CH3 (CH2 ) 4CH2 . BUTYL FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER:

NOTE: TENTATIVE k VALUE.

CH3CH2CH(.)CH3 - CH3CH=CH2 + CH3 PROPYL, 1 -METHYL-, FREE RADICAL

70 BEN/O 'N REACTION ORDER: 1.

0.1 10 .

0.6 1.4

91
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

77 K A B E/R

(in K) k factors

f F

381-412 6.3(+10) 0 3725

299-691 1.6(+14) 0 16455

299-691 5.0(113) 0 18420

300-897 4.0(+14) 0 21700 0.2 5.0

363-577 1.0(+11) 0 3875

300-650 2.8(+10) 0 3575

360-439 5 . 0 ( + 8) 0 2770

693-803 4 . 0( +17

)

0 43230

693-803 1.9(+17) 0 41170

298-650 3.0(+13) 0 2920 0.7 1.3

298-650 4 . 6( +13

)

0 2410 0.7 1.3

320-930 4.1 (+12

)

0 2637+320 0.5 2.0

300-1000 5.0(+ll) 0 5285 0.1 10.

350-00 1 .6(+ll) 0 4540+150 0.7 1.4

350-750 4.0(+ll) 0 4830+250 0.7 1.3

600-750 4.5(+ll) 0 5735+250 0.7 1.3

Chemical reactions

CH3 CH2CH(.)CH3 + CH3 CH=CH2 - CH3CH2 CH(CH3 )CH(CH3 )CH,

+ CH3CH2 CH ( CH3

) CH2 CH ( . ) ch3 PROPYL, 1-METHYL- , FREE RADICAL + 1-PROPENE

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2CHCH, CHo . + CHoCH=CH,

PROPYL, 2-METHYL- , FREE RADICAL

70 BEN/O'N REACTION ORDER: 1

(CH3 ) 2CHCH2. - (CH3 ) 3C=CH2 + H PROPYL, 2-METHYL- , FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3

C. (CH3 ) 2C=CH2 + H ETHYL, 1,1-DIMETHYL-, FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3

C. + CH=CH (CH3 ) 3CCH=CH.

ETHYL, 1,1-DIMETHYL-, FREE RADICAL + ETHYNE

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 3C. + CH2 =CH2 - (CH3 ) 3CCH2 CH2. ETHYL, 1,1-DIMETHYL-, FREE RADICAL + ETHENE

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 3C. + CH3C=CH (Ch3 ) 3cc(CH3 )=ch. + (ch3 ) 3 cch=c(.;

ETHYL, 1,1-DIMETHYL-, FREE RADICAL + 1-PROPYNE

72 KER/PAR REACTION ORDER: 2. NOTE: SUSPECT k VALUE.

CH3 CH2 CH2 CH3 BUTANE

70 BEN/O'N

NOTE: k ESTIMATED

CH3CH2CH2 CH3 -

BUTANE

70 BEN/O'N

CH, CH3CH2 CH2

. REACTION ORDER:

CH,CH0 . + CHoCHc REACTION ORDER: 1.

CH3 CH2 CH2CH3 + 0 - CH3CH2 CH2OL

BUTANE OXYGEN ATOM

+ OH

73 HER/HUI REACTION ORDER: 2.

CH 3CH2 CH2 CH 3 + 0 - CH 3CH2 CH(.)CH 3 + OH BUTANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2 .

CH3CH2 CH2 CH3 t H - CH3CH2CH(.)CH3 + CH3CH2CH2 CH2

. BUTANE + HYDROGEN ATOM

72 KON REACTION ORDER: 2.

+ H,

CH3CH2 CH2CH3 + H02 - CH3CH2 CH(.)CH3 + h2o2 BUTANE + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: UPPER LIMIT RECOMMENDED. RATIO DATA VERSUS k ref

HO, HO, H„0„ + 0,

CH3CH2 CH2CH3 + CH3. - CH3CH2CH(.)CH3

+ CH3 CH2 CH2 CH2 . + CH4

BUTANE + METHYL FREE RADICAL

72 KON REACTION ORDER: 2.

CH3CH2 CH2CH3 + CH 3

. - CH 3CH2CH(.)CH3 + CH4 BUTANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH 3 CD2CD2CH3 + CD 3

. BufANE-2^2,3,3^

76 KER/PAR

CH3 CD2CD(.)CH3 + CD4 METHYL-d3 FREE RADICAL

REACTION ORDER: 2.

92
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3CD2CD2 CH3 + CD3

. - CH3CD2 CD2CH2 . + CD3H BUTANE-2, 2, 3, 3-d4 + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH 3 ) 3CH + H - (CH3 ) 3C. + (CH3 ) 2CHCH2 . + H2 PROPANE, 2-METHYL- , + HYDROGEN ATOM

72 KON REACTION ORDER: 2.

(CH3 ) 3CH + H02 - (CH3 ) 3C. + H2

02 PROPANE, 2-METHYL- , + HYDROPEROXYL FREE RADICAL

74 LLO REACTION ORDER: 2. NOTE: UPPER LIMIT RECOMMENDED. RATIO DATA VERSUS k ref H02 + H02 - H202 + 02 (CH3 ) 3CH + ch3

. - (CH3 ) 3

C. + ch4 PROPANE, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 3 CH + CH3

. - (CH3 ) 3

C. + (CH3 ) 2CHCH2 . + CH4 PROPANE, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 3CD + CD3. -• (CH3 ) 3C. + CD4 PR0PANE-2-d , 2-METHYL, + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 3CD + CD3. - (CH3 ) 2CDCH2 . + CD3

H PR0PANE-2-d, 2-METHYL- , + METHYL-d3 FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH=CHCHO f CH3

. - CH3CH=CHC(0). + CH4 2-BUTENAL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH2 =CHCH2 COOH - CH3 CH=CH2 + C02 3-BUTENOIC ACID

70 BEN/O 'N REACTION ORDER: 1.

CH3 COOCH=CH2 + CH3CH2. - CH3COOCH(.)CH2CH2CH3

+ CH3COOCH(CH2CH3 )CH2

. ACETIC ACID ETHENYL ESTER + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3COCOCH3 + CH3

. - CH3COCOCH2 . + CH4 2,3-BUTANEDIONE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3COCOCH3 - CH3C(0). + CH3 C(0).

2,3-BUTANEDIONE

70 BEN/O 'N REACTION ORDER: 1.

(CH3C0) 20 - CH3COOH + CH2 =C=0 ACETIC ACID ANHYDRIDE

70 BEN/O 'N REACTION ORDER: 1.

(CH3C0) 20 + CH3. - CH3COOCOCH2 . + CH4 ACETIC ACID ANHYDRIDE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3C(O)0OC(O)CH3 - CH3C(0)0 + CH3C(0)0.

PEROXIDE, DIACETYL

70 BEN/O 'N REACTION ORDER: 1.

CH3CH2COCH3 + CH3

. - CH3CH(.)COCH3 + .CH2 CH2COCH3

+ ch3ch2 coch2 . + ch4 2-BUTANONE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. HCOOCH2 CH2 CH3 - HCOOH + CH3CH=CH2 FORMIC ACID PROPYL ESTER

70 BEN/O 'N REACTION ORDER: 1.

7VK A B E/R

(in K) k factorsf F

600-750 4.8(+ll) 0 5735+250 0.7 1.3

300-800 1 . 9 ( +13

0 2680+85 0.8 1.2

300-1000 1.0(+11) 0 3500 0.1 10.

550-750 9.6(+10) 0 3975+250 0.7 1.3

300-500 8.3(+10) 0 4000+500 0.5 2.0

550-750 1.2(111) 0 4800+250 0.7 1.3

550-750 6.0(+ll) 0 5735+250 0.7 1.3

350-500 l.O(fll) 0 3400+500 0.4 2.5

587-651 2.2(+ll) 0 20435

303-417 7.8(+10) 0 3475

300-800 2 . 2 (+11

0 4300+500 0.5 1.5

626-698 1 . 6( +16) 0 33970

553-646 1.0(112) 0 17365

300-500 1.8(111) 0 4830+500 0.6 1.4

363-463 1.8(+14) 0 14845

300-500 8.2(+10) 0 3700+500 0.5 1.5

613-673 1.3(112) 0 24006

93
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

HC00CH2CH2CH3 + CH3

. - .C00CH2CH2 CH3 + CH4 FORMIC ACID PROPYL ESTER + METHYL FREE RADICAL

72 KON REACTION ORDER: 2. HCOOCH2 CH2CH3 + CH3

. - .C00CH2CH2CH3 + HC00CH(.)CH2CH3

+ HCOOCH2 CH(.)CH3 + hcooch2 ch2ch2. + ch4 FORMIC ACID PROPYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. HCOOCH(CH3 ) 2 - HCOOH + CH3 CH=CH2 FORMIC ACID 1-METHYLETHYL ESTER

70 BEN/O' N REACTION ORDER: 1. HCOOCH(CH3 ) 2 + CH3

. - .COOCH(CH3 ) 2 + HCOOC(.)(CH3 ) 2

+ HCOOCH(CH3 )CH2 . + CH4 FORMIC ACID 1-METHYLETHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 COOCH2CH3 - CH3COOH + CH2 =CH2 ACETIC ACID ETHYL ESTER

70 BEN/O' N REACTION ORDER: 1.

CH3OCOOCH2CH3 - CH3OH + C02 + CH2 =CH2 CARBONIC ACID ETHYL METHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3CH(.)OCH2 CH3 - CH3CHO + CH3CH2. ETHYL, 1 -ETHOXY-, FREE RADICAL

70 BEN/O'N REACTION ORDER: 1. NOTE: logA PROBABLY LOW.

CH3CH(0.)CH2CH3 - CH3 CHO + CH3 CH2

. ETHOXY, 1 -ETHYL-, FREE RADICAL

70 BEN/O'N REACTION ORDER: 1. NOTE: ESTIMATED ARRHENIUS PARAMETERS

(VERY LIKELY LOWER LIMITS).

(CH3 ) 3CO. - (CH3 ) 2 CO + CH3. ETHOXY, 1,1 -DIMETHYL-, FREE RADICAL

70 BEN/O'N REACTION ORDER: 1. NOTE: TENTATIVE k.

(CH3 ) 3 COH - (CH3 ) 2C=CH2 + H20 2-PROPANOL, 2-METHYL70 BEN/O'N REACTION ORDER: 1.

CH3CH2 OCH2 CH3 - CH3CH2

. + CH3CH20. ETHANE, 1 , 1 '-OXYBIS70 BEN/O'N REACTION ORDER: 1. NOTE: k PROBABLY RELIABLE.

CH3CH2 OCH2 CH3 + CH3

. - CH3CH2OCH(.)CH3

+ CH3CH2 OCH2 CH2 . + CH4

ETHANE, 1 , 1 '-OXYBIS-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH2 OOCH2CH3 - CH3CH2 0. + CH3 CH2 0. PEROXIDE, DIETHYL

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3COOH - (CH3 ) 3CO. + OH HYDROPEROXIDE, 1 , 1-DIMETHYLETHYL

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3CSH - (CH3 ) 2C=CH2 + H2S 2-PROPANETH I OL , 2-METHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3CSH + CH3. - (CH3 ) 3CS. + .CH2C(CH3 ) 2SH + CH4 2-PR0PANETHI0L, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

7VK A B E/R

(in K)

k factors

f F

347-455 1.3(+10) 0 3675

350-500 2 . 5 ( + 1 1

)

0 5000+500 0.5 2.0

721-811 4 . 0 ( + 12

)

0 22145

350-500 2.5(111) 0 4980+500 0.5 2.0

725-883 3 . 9 ( + 12

)

0 24155

573-648 4.0(+12) 0 21640

418-453 8.1(+10) 0 11825

423-463 1.0(+14) 0 8800

393-453 3.2(+13) 0 8300

1050-1300 2.5(+13) 0 31001

833-913 1 . 0 ( + 18

)

0 42275

400-500 2.5(+ll) 0 4200+750 0.5 2.0

413-518 4.0(+15) 0 18770

553-653 4.0(+15) 0 21640

950-1230 2 . 5 ( +13

)

0 27830

303 5 . 9 ( + 7) - -

94
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

CH2 =CHCH2 S02 CH3 - CH2 =CHCH2

. + CH3S02

. 1-PROPENE, 3-METHYLSULFONYL70 BEN/O'N REACTION ORDER: 1.

cis-CH3CH=CHCN - trans-CH3CH=CHCN

c i s-2-BUTENEN ITR I LE

70 BEN/O'N REACTION ORDER: 1.

cis-CH3CH=CHCN + CH3CH2 . - CH3CH(CH2CH3 )CH( . )CN

+ CH3CH(.)CH(CH2CH3 )CN

c i s-2-BUTENEN I TR I LE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

trans-CH3CH=CHCN + CH3CH2

. - CH3CH(CH2 CH3 )CH( . )CN

+ CH3CH(.)CH(CH2CH3 )CN

t rans-2-BUTENEN ITR I LE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =C(CH3 )CN + CH3 CH2

. - CH3CH2 CH2C(.)(CH3 )CN

+ ,CH2C(CH3 )(CH2CH3 )CN 2-PROPENEN I TR I LE , 2-METHYL- , + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3CH=NN=CHCH3 + CH3

. - CH3C(.)=NN=CHCH3

+ .ch2ch=nn=chch3 + ch4 ACETALDEHYDE ETHYLI DENEHYDRAZONE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH2N=NCH2CH3 - CH3CH2 N=N. + CH3CH2. DIAZENE, DIETHYL70 BEN/O'N REACTION ORDER 1.

CH3 N=NCH(CH3 ) 2 - CH3N=N. + (CH3 ) 2CH. DIAZENE, METHYL ( 1-METHYLETHYL )

70 BEN/O'N REACTION ORDER 1.

CH3CH2CH2CH2 NH2 + CH3. - CH3 CH2CH2CH2NH.

+ CH3CH2CH2CH(.)NH2 + .ch2ch2 ch2 ch2nh2 1-BUTANAMINE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 CH2 ) 2 NH + CH3

. - (CH3CH2 ) 2N. + CH3CH(.)NHCH2CH3

+ .CH2CH2NHCH2CH3 + CH4

ETHANAMINE, N-ETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH2N(CH3 ) 2 + CH3

. - CH3 CH(.)N(CH3 ) 2 + .CH2CH2 N(CH3 ) 2

+ CH3CH2N(CH3 )CH2 . + ch4 ETHANAMINE, N,N-D I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 NN=NN(CH3 ) 2 - (CH3 ) 2NN=N. + (CH3 ) 2

N. 2-TETRAZENE , 1,1,4, 4-TETRAMETHYL70 BEN/O'N REACTION ORDER: 1.

CH3CH2OCH=CH2 - CH3CHO + CH2 -CH2 ETHENE, ETHOXY70 BEN/O'N REACTION ORDER: 1.

CH2 =CHCH2CH2OH - CH3CH=CH2 + HCHO 3-BUTEN-l-OL

70 BEN/O'N REACTION ORDER: 1.

CH3CH2 CH2 CHO + CH3

. - CH3CH2CH2 C(0) . + CH4 BUTANAL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

77 K A B E/R

(in K) k factors

f F

633-733 1.3(+14) 0 24006

573-633 5.0(+12) 0 28030

323-454 1.5(+10) 0 2500

323-754 3. 1(+10) 0 2600

312-400 2.5(111) 0 2300

350-600 2.5(111) 0 3975+500 0.5 2.0

2.0(+16) 0 25165

543-605 2.5(+16) 0 23900

426 3 . 2 ( + 7) - - 0.5 2.0

350-500 2.2(+ll) 0 3550+500 0.5 2.0

420 2 . 6( + 7) - - 0.5 2.0

466-539 2.5(+14) 0 18170

640-859 4.0(+ll) 0 22345

643-685 4 . 5 ( +1 1

0 20635

350-500 1.0(111) 0 2970+500 0.4 1.6

95
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

(CH3 ) 2 CHCH0 + CH3. - (CH3 ) 2 CHC(0). + CH4 PROPANAL, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3C0N(CH3 ) 2 + CH3 - CH3CON(CH3 )CH2

. + CH4 ACETAMIDE, N.N-D I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3C0N(CH 3 ) 2 + CH3. - .CH2 C0N(CH3 ) 2

+ CH3CON(CH3 )CH2

. + CH4 ACETAMIDE, N,N-D I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH2 CH2 CH2 ONO - CH3 CH2CH2 CH2

0. + NO NITROUS ACID BUTYL ESTER

70 BEN/0 'N REACTION ORDER: 1.

CH3 CH2CH2C=CH + N -* products

1-PENTYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 14.0

NOTE: k ref : CHCH + N

CH3 (CH2 ) 2 CH=CH2 + 0 - cy-(CH3 CH2 CH2 )CHCH2 0 1-PENTENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 (CH2 ) 2 CH=CH2 + H - CH3 (CH2 ) 2CH(.)CH3 + CH3 (CH2 ) 3CH2. 1-PENTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k re f

: 0.89

NOTE: k ref : CH3 CH=CH2 + H

CH3 (CH2 ) 2CH=CH2 + S - cy-[CH3 (CH2 ) 2 ]CHCH2 S 1-PENTENE + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

CH3 (CH2 ) 2 CH=CH2 + CH3

. - CH3CH2 CH(.)CH=CH2 + CH4 1-PENTENE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3 (CH2 ) 2CH=CH2 + CHCH2 CH2. - CH3 (CH2 ) 2CH(.)CH2 (CH2 ) 2 CH3 1-PENTENE - PROPYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

ci s-CH3CH2 CH=CHCH3 + 0 -* products

c i s-2-PENTENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

c

i

s-CH 3CH2 CH=CHCH 3 + H - CH3 CH2 CH( . )CH2CH3

+ CH3 CH2 CH2CH(.)CH3

c i s-2-PENTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k re f

: 0.39

NOTE: k rcf : CH3CH=CH2 + H

c

i

s-CH3CH2CH=CHCH3 + CH3. - CH3CH2 CH( . )CH(CH3 ) 2 cis-2-PENTENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

c

i

s-CH3 CH2CH=CHCH3 + CH3. - CH3 CH2CH(CH3 )CH( . )CH3 cis-2-PENTENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

c i s-CH3CH2CH=CHCH3 + CH3CH2. - CH3CH2CH(CH2 CH3 )CH( . )CH3 cis-2-PENTENE - ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

7VK A B E/R

(in K)

k factors

f F

350-500 1.0(111) 0 2970+500 0.4 1.6

350-600 1.6(111) 0 4125+500 0.5 1.5

350-600 2.0(111) 0 4200+500 0.5 1.5

443-485 2.0(+16) 0 20400

320-550 3.0(+ll) 0 1047 435

298 2.8(+12) - - 0.7 1.3

298 8 . 3( +11

)

300

298 8.1(112) - -

450-650 4 . 5 ( + 1 1

)

0 4500+500 0.6 1.4

298 - - 3410

298 1 . 1 ( + 13

)

- - 0.7 1.3

298 3 . 8( +1 1

)

300

298 - - 4060

298 - - 4125

298 4300

96
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

t rans-CHoCH2CH=CHCH3 + H -* CH3CH2CH( . )CH2CH3

+ CH3CH2 CH2CH(.)CH3 trans-2-PENTENE + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 0.44

NOTE: k ref : CH3CH=CH2 + H

CH3CH2C(CH3 )=CH2 + H - CH3 CH2C(.)(CH3 ) 2

+ CH3CH2CH(CH3 )CH2

. 1-BUTENE, 2-METHYL- , + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

CH3CH2 C(CH3 )=CH2 + D - CH3CH2 C(.)(CH3 )CH2 D

+ CH3CH2 CD(CH3 )CH2

. 1-BUTENE, 2-METHYL- , + DEUTERIUM ATOM

72 KER/PAR REACTION ORDER: 2.

CH3CH2C(CH3 )=CH2 + S - cy-(CH3CH2 )C(CH3 )CH2 S 1-luTENE, 2-IeTHYL-, + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CHCH=CH2 + H - (CH3 ) 2 CHCH(.)CH3 + (CH3 ) 2 CHCH2 CH2

. 1-BUTENE, 3-METHYL- , + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2CHCH=CH2 + D - (CH3 ) 2 CHCH(.)CH2D + (CH3 ) 2 CHCHDCH2 1-BUTENE, 3-METHYL- , + DEUTERIUM ATOM

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CHCH=CH2 + CH3

. - (CH3 ) 2CHCH(.)CH2CH3 1-BUTENE, 3-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2CHCH=CH2 + CH3. - (CH3 ) 2C(.)CH=CH2 + CH4 1-BUTENE, 3-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 CHCH=CH2 | CH3CH2. - (CH3 ) 2 CHCH(.)CH2CH2CH3 1-BUTENE, 3-METHYL- , + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 C=CHCH3 + 0 -» products

2-BUTENE, 2-METHYL- , + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2 C=CHCH3 + H - (CH3 ) 2 CHC(.)CH3 + (CH3 ) 2C(.)CH2 CH3 2-BUTENE, 2-METHYL- , + HYDROGEN ATOM

73 HER/HUI REACTION ORDER: 2. k/k re f

: 1.03

NOTE: k ref : CH3CH=CH2 + H

(CH3 ) 2C=CHCH3 + S - cy-[(CH3 ) 2 ]CCH(CH3 )S 2-luTENE, 2-METHYL-, + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2. k/k re f

: 56.0

NOTE: k ref : CH2 =CH2 + S

(CH3 ) 2 C=CHCH3 + N -» products

2-BUTENE, 2-METHYL- , + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 3.5

NOTE: k ref : CH2 =CH2 + N

(CH3 )2C=CHCH3 +

1CH2 products

2-BUTENE, 2-METHYL- , + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 2.12

NOTE: k ref : CH2 =CH2 +

1 CH2

(CH3 ) 2C=CHCH3 + 3CH2 -> products

2-BUTENE, 2-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 1.83

NOTE: k ref : CH2 =CH2 + 3CH2

7VK A B E/R

(in K)

300

298 4.1(+11) - -

298 9.1(+11) - -

298 2.0(412) - -

298 7.4(+13) - -

298 7.4(+ll) - -

298 7.6(+ll) - -

298 - - 3500

450-600 4.4(+ll) 0 4225+750

298 - - 3620

298-400 3.9(412) 0 - 680

298 9.1(111) 300

298 6.5(413) 298

320-550 9.3(110) 0 433 435

297 - -

- - -

k factors

f F

0.5 1.5

0.8 1.2

97
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

(CH3 ) 2 C=CHCH3 + CH3

. - (CH3 ),C=CHCH2. + .CH2 C(CH3 )=CHCH3 + CH4 2-BUTENE, 2-METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 C=CHCH3 + CH3. - (CH3 ) 3CCH(.)CH3

+ (CH3 ) 2 C(.)CH(CH3 ) 2 2-BUTENE, 2-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. k/k re f

NOTE: k ref : CH2 =CH2 + CH3 (CH3 ) 2C=CHCH3 + CCO - (CH3 ) 2C=C=CHCH3 + CO

2-BUTENE, 2-METHYL- , + CARBON 0XIDE(C2 0) 72 KER/PAR REACTION ORDER: 2. k/k ref : NOTE: k ref : CH2 =CH2 + CCO

(CH3 ) 3CCH2. - (CH3 ) 2 C=CH2 + CH3

. PROPYL, 2,2-DIMETHYL-, FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 CHCH2CH2 . + CH2 =CH2 - (CH3 ) 2 CH(CH2 ) 3 CH2

. IuTYL, 3-METHYL-, FREE RADICAL +ETHENE

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH2 CH2 CH2 CH3 + 0 - CH3 CH2 CH2 CH2CH2

. + OH PENTANE + OXYGEN ATOM

73 HER/HU I REACTION ORDER: 2.

CH3 CH2 CH2 CH2 CH3 + 0 - CH3 CH2 CH2CH(.)CH3

+ CH3 CH2 CH(.)CH2CH3 + OH PENTANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3CH2 CH2CH2 CH3 + CH3 . - CH3CH2CH2 CH2 CH2 . + CH4 PENTANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 CH2CH2CH2 CH3 + CH3 . - CH3CH2CH(.)CH2CH 3

+ CH3 CH2CH2 CH(.)CH3 + CH4 PENTANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2CHCH2CH3 + 0 - [C5

H X ! . ] + OH BUTANE, 2-METHYL- , + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2 CHCH2CH3 + CH3. - (CH3 ) 2C(.)CH2CH3 + CH4 IuTANE, 2-METHYU, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CHCH2 CH3 + CH3

. - (CH3 ) 2 CHCH(.)CH3 + CH4

BUTANE, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2CHCH2CH3 + CH3

. - (CH3 ) 2CHCH2 CH2. + .CH2CH(CH3 )CH2 CH3 + CH4

BUTANE, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 4C - (CH3 ) 3

C. + CH3 PROPANE, 2,2-DIMEHYL70 BEN/O'N REACTION ORDER: 1.

7VK A B E/R

(in K) k factorsf F

400-500 4.9(+ll) 0 4300+500 0.5 1.5

403-455 1.4(+10) 0 3070

453 - - -

298 - - -

762 1 .0(+14) 0 18875

340-413 1.2(110) 0 3235

298-650 2 .9(+13) 0 2920 0.7 1.3

298-650 8.0(413) 0 2320 0.7 1.3

350-800 4.8(411) 0 5800+250 0.7 1.3

350-800 6.0(+ll) 0 4830+250 0.7 1.3

307 8.0(+10) - - 0.7 1.4

350-750 9.6(+10) 0 3975+250 0.7 1.3

350-750 2.0(411) 0 4830+250 0.7 1.3

350-750 7.1(411) 0 5800+250 0.7 1.3

803-1200 5.0(+16) 0 40465

98
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

(CH3 ) 4C + 0 - (CH3 ) 3CCH2 . + OH PROPANE, 2,2-DIMEHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 4C + CH3. - (CH3 ) 3 CCH2 . + CH4

PROPANE, 2,2-DIMEHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH2 =CHOCH2 CH=CH2 - CH2 =CHCH2 CH2 CHO

1-PROPENE, 3-ETHENYLOXY70 BEN/O'N REACTION ORDER: 1.

cis-CH3CH=CHCOOCH3 - trans-CH3 CH=CHCOOCH3 cis-2-BUTEN0IC ACID METHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

t ran s-CH3CH=CHC00CH3 - cis-CH3CH=CHCOOCH3

t ran s-2-BUTENO I C ACID METHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH 3C00CH2CH=CH2 + CH3 CH2. - CH3 COOCH2 CH(.)CH2CH2 CH3

+ CH3COOCH2 CH(CH2 CH3 )CH2

. ACETIC ACID 2-PROPENYL ESTER + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 C00) 2 CH2 - (CH3 C0) 20 + HCHO

METHANEDIOL, DIACETATE

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 CHOCH=CH2 - CH3CH=CH2 + CH3CHO

PROPANE, 2-(ETHENYL0XY)-

70 BEN/O'N REACTION ORDER: 1.

CH2 =CHCH2 CH(OH)CH3 - CH3CH=CH2 + CH3 CHO 4-PENTEN-2-0L

70 BEN/O'N REACTION ORDER: 1.

CH3 CH2 CH2 CH2CHO + CH3

. - CH3CH2CH2 CH2C(0). + CH4 PENTANAL + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3CH2 CH(CH3 )CHO + CH3. - CH3CH2CH(CH3 )C(0). + CH4

BUTANAL, 2-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2CHCH2 CHO + CH3

. - (CH3 ) 2 CHCH2 C(0). + CH4

BUTANAL, 3-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 3CCHO + CH3. - (CH3 ) 3C(0). + CH4 PROPANAL, 2,2-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3CH2 ) 2 CO + CH3 . - CH3CH(.)COCH2CH3

I ,CH2CH2COCH2CH3 + CH4 3-PENTANONE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3CD2 ) 2 CO + CH3

. - CH3CD2 COCD2 CH2 . + CH4 3-PENTAN0NE-2 ,2,4, 4—

4 + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 CD2 ) 2 CO + CH3 - CH3CD2COCD(.)CH3 + CH4 3-PENTAN0NE-2 ,2,4, 4-d4 + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3CH2 ) 2 CO + CH3CH2

. - ,CH23H2 C0CH2 CH3 + CH 3CH 3 I-PENTANONE + ETHYL FREE RADICAL

72 KON REACTION ORDER: 2.

T! K A B E/R

(in K) k factorsf F

298-650 5 . 9( +13

0 2920 0.7 1.4

400-600 8 . 3 ( + 1 1

0 5940+350 0.6 1.4

440-473 5.0(+ll) 0 15400

673-833 1 .6(+ll) 0 29090

673-833 4.0(+12) 0 29190

308-448 2.5(111) 0 3900

493-578 5.0(110) 0 18300

720-794 3.8(112) 0 21920

625-663 8 . 5 ( + 1 1

0 20600

350-500 1.0(+11) 0 3000+500 0.4 1.6

350-500 1.0(111) 0 3200+500 0 2 .0

350-500 1.0(411) 0 3070+500 0.4 1.6

350-500 1.0(111) 0 3170+500 0.5 2.0

300-450 1.9(411) 0 3675+500 0.5 1.5

500-600 2.0(+ll) 0 5535+500 0.5 2.0

500-600 1.3(411) 0 4200+500 0.5 2.0

300-520 2.8(111) 0 3986+100 0.4 2.2

99
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions T/K A B E/R

(in K)

k factors

f F HC00(CH2 ) 3 CH 3 + CH 3

. - .C00(CH2 ) 3CH3 + HC00CH(.)(CH2 ) 2 CH

+ HC00CH2 C'H(.)CH2 CH3 + HC00CH2 CH2CH(.)CH3

+ HC00(CH2 ) 3 CH2 . + ch4 FORMIC ACID BUTYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

i

350-500 2.5(111) 0 4980+500 0.5 2.0

HC00C(CH 3 ) 3 - (CH3 ) 2 C=CH2 + HCOOH FORMIC ACID 1 , 1-DIMETHYLETHYL ESTER

70 BEN/O'N REACTION ORDER: 1. 503-573 7.9(+12) 0 19730

CH 3 C00CH2 CH2CH3 - CH3CH=CH2 + CH3C00H ACETIC ACID PROPYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: RELIABILITY NO BETTER THAN AN ORDER OF MAGNITUDE. 725-810 2.5(+12) 0 24006

CH3COOCH(CH 3 ) 2 - CH3 CH=CH2 + CH3 COOH ACETIC ACID 1-METHYLETHYL ESTER

70 BEN/O'N REACTION ORDER: I. 586-801 1.0(113) 0 22645

CH3CH2 COOCH2 CH3 - CH3 CH2COOH + ch2 =ch2 PROPANOIC ACID ETHYL ESTER

70 BEN/O'N REACTION ORDER: 1. 778-875 5 . 6 ( + 12

)

0 24400

CH3CH2COOCH2CH3 + CH3

. - CH3CH(.)COOCH2CH3

+ CH3CH2 COOCH(.)CH3 + .CH2 CH2 COOCH2 CH3

+ ch3 ch2 cooch2 ch2 . + ch4 PROPANOIC ACID ETHYL ESTER + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 300-650 2 . 5( +11

)

0 4125+500 0.5 1.5

CH3COOCH2 CH2OCH3 - CH2 =CHOCH3 + CH3 COOH ACETIC ACID (2-METHOXY ETHYL) ESTER

70 BEN/O'N REACTION ORDER: 1. 725-810 1.6(+12) 0 24460

CH3CH2OCOOCH2CH3 - CH3CH2OH + C02 + ch2 =ch2 CARBONIC ACID DIETHYL ESTER

70 BEN/O'N REACTION ORDER: 1. 573-648 7.9(+12) 0 21800

(CH3 CH2 )C(CH3 ) 2 OH - CH 3CH2C(CH3 )=CH2

+ CH3CH=C(CH3 ) 2 + H2 0 2-BUTANOL, 2-METHYL70 BEN/O'N REACTION ORDER: 1. 757-799 3.2(+13) 0 30200

(CH3 ) 3CCN - (CH3 ) 2C(.)CN + CH3. PROPANENITRILE, 2, 2-D I METHYL70 BEN/O'N REACTION ORDER: 1. 875-925 1 . 4( + 15

)

0 35330

(CH 3CH2 ) 2 NCH 3 + CH 3

. - CH3 CH(.)N(CH2CH3CH3

+ .CH2 CH2 N(CH2 CH3 )CH3 + (CH3 CH2 ) 2 NCH2

. + ch4

ETHAN AMINE, N-ETHYL-N-METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. 420 3 . 0 ( + 7) - - 0.5 2.0

(CH3 ) 2 NCON(CH3 ) 2 + CH3. - .CH2 (CH3 )NCON(CH3 ) 2 + ch4 UREA, TETRAMETHYL-', + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. 350-550 2 . 0 ( + 1 1

)

0 3975+500 0.5 1.5

CH2 =CHCH=CHCH=CH2 - cy-CH2CH=CHCH=CHCH2 cis-1 ,3,5-HEXATRIENE

70 BEN/O'N REACTION ORDER: 1. 390-463 7 . 1 ( + 1 1

)

0 15050

CH 3CH2 CH2 CH2CTCH + N - products

‘ 1-HEXYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 14.0

NOTE: k ref : CHCH + N.

320-550

435

4.6(111) 0 1233

CH3CH2C2CCH2CH3 + N - products

' 3-HEXYNE + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k ref : 14.0

NOTE: k ref : CH^CH + N

320-550

435 3.4(+ll) 0 1102

100
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

cis-CH2 =CHCH=CHCH2 CH3 - CH3CH=CHCH=CHCH3 cis-1 ,3-HEXADIENE

70 BEN/O'N REACTION ORDER: 1.

CD2 =CHCH2 CH2 CH=CD2 - CH2 =CHCD2 CD2 2 CH=CH2

\ , 5-HEXADIENE-l , 1 , 6, 6-D4 70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2C=CHCH=CH2 - CH2 =C(CH3 )CH=CHCH3 1,1-PENTADIENE, 4-METHYL70 BEN/O'N REACTION ORDER: 1.

CH2 =C(CH3 )C(CH3 )=CH2 + CH3 CH2

. -

+ CH3 CH2 CH2 C(.)(CH3 )C(CH3 )=CH2

+ ,CH2C(CH3 )(CH2 CH3 )C(CH3 )=CH2 1,3-BUTADIENE, 2,3-DIMETHYL-, + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

c i s-CH2 =C ( CH3) CH=CHCH3 - (CH3 ) 2C=CHCH=CH2 cis-1, 3-PENTAD I ENE, 2-METHYL70 BEN/O'N REACTION ORDER: 1.

CH3 (CH2 ) 3CH=CH2 + 0 - cy-[CH3 (CH2 ) 3 ]CHCH20 1-HEXENE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 (CH2 ) 3CH=CH2 + CH3CH2 . - CH3 (CH3 ) 3CH(.)CH2 CH2CH3

+ CH3 (CH2 ) 3 CH(CH2CH3 )CH2

. 1-HEXENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

cs-CH3 CH2 CH2 CH=CHCH3 + CH3

. - CH3CH2CH2CH( . )CH(CH3 ) 2 cis-2-HEXENE + METHYL FREE RADICAL

?

72 KER/PAR REACTION ORDER: 2.

cis-CH3 CH2 CH2 CH=CHCH3 + CH3. - CH3 CH2 CH2CH(CH3 )CH( . )CH3 cis-2-HEXENE + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3 CH2CH2C(CH3 )=CH2 + CH3. - CH3 CH2 CH2 C(.)(CH3 )CH2CH3 1-PENTENE, 2-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

c i s- ( CH3 ) 2 CHCH=CHCH3 + CH3. - (CH3 ) 2CHCH( . )CH(CH3 ) 2 cis-2-PENTENE, 4-METHYL- , + METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2C=C(CH3 ) 2 + 0 -* products

2-BUTENE, 2,3-DIMETHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2 C=C(CH3 ) 2 + H - (CH3 ) 2C(.)CH(CH3 ) 2 2-BUTENE, 2,3-DIMETHYL-, + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/kref : 0.84

NOTE: k ref : CH3 CH=CH2 + H

(CH3 ) 2C=C(CH3 ) 2 + S - cy-[ (CH3 ) 2 ]CC(CH3 ) 2S 2-BUTENE, 2?3-DIMETHYL-, + SULFUR ATOM

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 2C=C(CH3 ) 2 + N -* products

2-BUTENE, 2,3-DIMETHYL-, + NITROGEN ATOM

72 KER/PAR REACTION ORDER: 2. k/k

NOTE: k ref : CH2 =CH2 + N 3.5

(CH3 ) 2 C=C(CH3 ) 2 +

1 CH2 -> products

2-BUTENE, 2,3-DIMETHYL-, + METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 2.16

NOTE: k ref : CH2 =CH2 +

1 CH2

Tl K A B E/R

( in

474-518 6.3(+10) 0 16355

530 1 . 3 ( +1 10 17865

473-510 5 . 2 ( +1 1

0 18199

318-414 1 . 6( +1 1

0 2265

473 1 . 7 ( +1 1

0 16485

298 3 . 1 ( +12

- -

338-435 3.9(+10) 0 3400

298 - - 4060

298 - - 4150

298 - - 3450

298 - - 4390

298-400 3 . 4( +12

0 -790

298 7.8(111)

300

298 8.5(113) - -

320-550 1.7(+11) 0 690

435

297 - - -

k factors

f F

0.7 1.3

0.8 1.2

101
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued Chemical reactions

(CH3 ) 2C=C(CH3 ) 2 4 3 CH2 -* products

2-BUTENE, 2,3-DIMETHYL-, 4 METHYLENE FREE RADICAL

72 KER/PAR REACTION ORDER: 2. k/k ref : 2.74

NOTE: k ref : CH2 =CH2 4 3CH2 (CH3 ) 2 C=C(CH3 ) 2 4 CH3

. - (CH3 ) 2C=(CH3 )CCH2 . 4 CH4 2-BUTENE, 2,3-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2 C=C(CH3 ) 2 4 CH3

. - (CH3 ) 3 CC(.)(CH3 ) 2 2-BUTENE, 2,3-DIMETHYL-, 4 METHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE. k/k re f

: 0.2

NOTE: k ref : CH2 =CH2 4 CH3 (CH3 ) 2C=C(CH3 ) 2 4 CCO - ( CH3 ) 2C=C=C ( CH3 ) 2 4 CO 2-BUTENE, 2,3-DIMETHYL-, 4 CARBON 0XIDE(C20) 72 KER/PAR REACTION ORDER: 2. k/k ref : 250. NOTE: k ref : CH2 =CH2 4 CCO

CH3CH(.)CH2 CH2CH2 CH3 - CH3CH=CH2 4 CH3CH2 CH2

. PENTYL, 1-METHYU, FREE RADICAL

70 BEN/O'N REACTION ORDER: 1.

CH3 (CH2 ) 4CH3 + 0 - CH3 (CH2 ) 4CH2 . 4 OH HEXANE 4 OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 (CH2 ) 4CH3 4 0- CH3 CH(.)CH2 CH2CH2 CH3

4 CH3 CH2 CH(.)CH2 CH2CH3 4 OH HEXANE 4 OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 (CH2 ) 4CH3 4 CH3

. - CH3 (CH2 ) 4CH2 . 4 CH4 HEXANE 4 METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 (CH2 ) 4CH3 4 CH3. - CH3 CH2CH(.)CH2CH2 CH3

4 CH3CH2 CH2 CH2CH(.)CH3 + ch4 HEXANE 4 METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CHCH(CH3 ) 2 - (CH3 ) 2 CH. 4 (CH3 ) 2CH. BUTANE, 2, 3-D I METHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2CHCH(CH3 ) 2 - (CH3 ) 2CH(.)CH(CH3 ) 2 4 CH3. BUTANE, 2, 3-D I METHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 CHCH(CH3 ) 2 4 0- .CH2 CH(CH3 )CH(CH 3 ) 2 4 OH luTANE, 2,3-DIMETHYL-, 4 OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2 CHCH(CH3 ) 2 4 0 - (CH3 ) 2C(.)CH(CH3 ) 2 + OH BUTANE, 2,3-DIMETHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2CHCH(CH3 ) 2 + CH3. - .CH2CH(CH3 )CH(CH3 ) 2 + CH4

BUTANE, 2,3-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CHCH(CH3 ) 2 + CH3

. - (CH3 ) 2 C(.)CH(CH3 ) 2 + CH4

BUTANE, 2,3-DIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

7VK A B E/R

(in K) k factorsf F

297 - - -

403-614 7 . 8 ( + 1 1

)

0 4400+500 0.6 1.4

403-453 1.0(+10) 0 3400

453 - - -

298 - - -

822 2.0(+14) 0 13800

298-650 2.9(+13) 0 2920 0.7 1.3

298-650 1 . 1 (+14) 0 2250 0.7 1.3

350-800 4.8(+ll) 0 5800+250 0.7 1.3

350-800 7.9(+ll) 0 4830+250 0.7 1.3

1000-1200 3.2(4-16) 0 39250

1000-1200 1.0(417) 0 41800

298-650 5.9(413) 0 2920 0.7 1.3

298-650 3.1(413) 0 1650 0.7 1.3

350-750 9.5(411) 0 5800+250 0.7 1.3

350-750 1.9(411) 0 3975+250 0.7 1.3

102
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

(CH3 ) 2CHCH(CH3 ) 2 + CH3

. - (CH3 ) 2 CHC(.)(CH3 ) 2

+ ,CH2 CH(CH3 )CH(CH3 ) 2 + ch4

BUTANE, 2,3-DIMETHYL-, + METHYL FREE RADICAL

72 KON REACTION ORDER: 2.

(CH3 ) 2 CHCH(CH3 ) 2 + CD3

. - (CH3 ) 2C(.)CH(CH3 ) 2

+ .CH2 CH(CH3 )CH(CH3 ) 2 + cd3

h BUTANE, 2,3-DIMETHYL-, + METHYL-d3 FREE RADICAL

72 KON REACTION ORDER: 2.

CH2 =C(CH3 )OCH2CH=CH2 - CH3 C(0)CH2 CH2 CH=CH2 1-PROPENE, 3-( 1-METHYLETHENYLOXY)-

70 BEN/O'N REACTION ORDER: 1.

CH2 =C(CH3 )CH2OCH=CH2 - CH2 =C(CH3 )CH2 CH2 CHO 1-PROPENE , 2-METHYL-3 ( ETHENYLOXY )

70 BEN/O'N REACTION ORDER: 1.

CH2 =CHCH(CH3 )OCH=CH2 - CH3 CH=CHCH2CH2CHO

1-PROPENE , 3-METHYL-3 ( ETHENYLOXY )

70 BEN/O'N REACTION ORDER: 1.

CH2 =CHC(CH3 ) 2C00H - CH3CH=C(CH3 ) 2 + C02 3-BUTENOIC ACID, 2, 2-D I METHYL70 BEN/O'N REACTION ORDER: 1.

CH3CH2C00CH2 CH=CH2 + CH3CH2

. -

CH3CH2 COOCH2 CH(.)CH2 CH2 CH3 + CH3 CH2 COOCH2 CH(CH2 CH3 )CH2 PROPANOIC ACID 2-PROPENYL ESTER + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3COO) 2CHCH3 - CH3 COOCOCH3 + CH3 CHO 1,1-ETHANEDIOL, DIACETATE

70 BEN/O'N REACTION ORDER: 1.

CH3CH2C(0)00C(0)CH2 CH3 - CH3CH2 C(0)0. + CH3 CH2 C(0)0.

PEROXIDE, B IS ( 1-OXOPROPYL)

70 BEN/O'N REACTION ORDER: 1.

CH2 =CHCH2C(OH)(CH3 ) 2 - CH3CH=CH2 + (CH3 ) 2CO 4-PENTEN-2-0L, 2-METHYL70 BEN/O'N REACTION ORDER: 1.

CH2 =CHO(CH2 ) 3 CH3 - CH3CH2CH=CH2 + CH3 CHO

BUTANE, l-( ETHENYLOXY )- 70 BEN/O'N REACTION ORDER: 1.

CH2 =CHO(CH2 ) 3CH3 + CH3 CH2

. - CH3CH2 CH2 CH(.)0(CH3 ) 3CH3

+ .CH2 CH(CH2 CH3 )0(CH2 ) 3 CH3 BUTANE, 1 -ETHENYLOXY-, + ETHYL FREE RADICAL

70 BEN/O'N REACTION ORDER: 2.

CH3COO(CH2 ) 3 CH3 - CH 3 CH2CH=CH2 + CH3 COOH

ACETIC ACID BUTYL ESTER

72 KER/PAR REACTION ORDER: 1.

CH3COOCH(CH3 )CH2CH3 - CH3 COOH l cis-CH3 CH=CHCH3

r t rans-CH3 CH=CHCH3 + CH3 CH2 CH=CH2 ACETIC ACID 1-METHYLPEROPYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 57% 1-BUTENE: trans/c is-2-BUTENE = 0.64.

CH3COOCH2 CH(CH3 ) 2 - (CH3 ) 2C=CH2 + CH3 COOH

ACETIC ACID 2-METHYLPROPYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3COOC(CH3 ) 3 - (CH3 ) 2C=CH3 + CH3 COOH

ACETIC ACID 1 , 1-DIMETHYLETHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2C(OH)CH2COCH3 - (CH3 ) 2CO + (CH3 ) 2CO 2-PENTANONE , 4-HYDR0XY-4-METHYL70 BEN/O'N REACTION ORDER: 1.

7VK A B E/R

(in K)

300-500 5 . 0 ( +10

0 3445

439-566 4.7(+ll) 0 4525

416-467 5 . 4( +1 1

0 14745

423-461 1 . 4( +11

0 14645

423-461 2 . 1 ( +1 1

0 14025

511-548 1 . 4 ( + 1 1

0 18400

352-453 2 . 5 ( +1 1

0 3875

493-541 1 . 9( +10) 0 16560

373-464 2 . 5( +14) 0 15100

607-643 1 . 4( +12

0 20500

590-650 1.4(+11) 0 21330

303-435 2 . 5( +10) 0 3070

725-810 1 . 6( +12

0 23150

576-710 2.0(+13) 0 23450

725-810 7.9(111) 0 23800

514-564 1.4(+13) 0 20130

495-528 4.3(+ll) 0 16255

k factors

f F

103
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

TV K A B E/R

(in K) k factors

f F

650-710 1 . 1 (+13) 0 23450

725-810 1.2(+12) 0 24100

696-760 4.2(+14) 0 31960

400-600 2.1(+11) 0 4100+500 0.5 2.0

420-428 4.0(+15) 0 18700

300-450 2 . 3 ( + 1 1

)

0 4100+500 0.5 1.5

350-500 8.9(+10) 0 3925+500 0.5 1.5

523-563 2 . 5 ( + 16

)

0 23900

IL 350-500 2.0(111) 0 3370+750

350-600 5.0(111) 0 4000+500 0 2.0

445-491 9.3(+ 9) 0 14330

3.9(111) 0 4430

451-523 1.3(+11) 0 16355

451-523 7.1(110) 0 17590

304 - - -

Chemical reactions

CH3 C00CH(CH3 )CH20CH3 - CH3C00H + CH2 =CHCH2OCH3

+ cis- and t rans-CH3CH=CHOCH3 2-PROPANOL, 1-M ETHOXY-, ACETATE

70 BEN/O'N REACTION ORDER: 1. NOTE: 58% PROPENE, 3-METHOXYCHoCOOCH^CHoOCHoCH, ch2 =choch2 ch 3 + ch 3cooh

ETHANOL, 2-ETHOXY- , ACETATE

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 CH0CH(CH3 ) 2 - CH3CH=CH2 + (CH3 ) 2CH0H

PROPANE, 2,2'-0XYBIS70 BEN/O'N REACTION ORDER: 1. NOTE: SUSPECT RATE CONSTANT.

(CH3 ) 2CH0CH(CH3 ) 2 + CH3. - (CH3 ) 2C(.)0CH(CH3 ) 2

+ .CH2 CH(CH3 )0CH(CH3 ) 2 + CH4

PROPANE, 2,2' -0XYBIS-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3 CH2 CH2 OOCH2CH2CH3 ^PEROXIDE, D I PROPYL

70 BEN/O'N

CH3CH2CH2

0. + CH3 CH2 CH2

0. REACTION ORDER: 1.

(CH3 ) 2 CH00CH(CH3 ) 2 + CH3. - (CH3 ) 2C(.)00CH(CH3 ) 2

+ .CH2 CH(CH3 )00CH(CH3 ) 2 + ch2 . + ch4 PEROXIDE, B I S ( 1-METHYLETHYL ) - , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

CH3CH=NC(CH3 ) 3 + CH3

. - CH3C(.)=NC(CH3 ) 3

+ .CH2CH=NC(CH3 ) 3 + CH3CH=NC(CH3 ) 2 CH2 . + CH4 2-PROPANI MINE, N-ETHYLIDENE-2-METHYL-,

+ METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2.

(CH3 ) 2CHN=NCH(CH3 ) 2 - (CH 3 ) 2 CHN=N. + (CH3 ) 2CH. DIAZENE, BIS( 1-METHYLETHYL)-

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2CHNHCH(CH3 ) 2 + CH3. - (CH3 ) 2CHN(.)CH(CH3 ) 2

- (CH3 ) 2C(.)NHCH(CH3 ) 2 + CH2 CH(CH3 )NHCH(CH3 ) 2 + ch,

76 KER/PAR

NOTE: TENTATIVE k VALUE. REACTION ORDER: 2.

(CH3 CH2 ) 3N + CH, CH3CH(.)N(CH2 CH3 ) 2 .CH2 CH2 N(CH2 CH3 ) 2 + CH, ETHANAMINE, N,N-DIETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH2 =C=CHCH2CH2 CH=CH2 1,2, 6-HEPTATRI ENE

70 BEN/O'N

CH2 =CHC(=CH2 )CH2CH=CH2 REACTION ORDER: 1.

CH3 (CH2 ) 4CCH + CH3 CH2

. - CH3 (CH2 ) 4C(.)=CHCH2CH3

- CH3 (CH2 ) 4C(CH2CH 3 )=CH. 1-HEPTYNE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH2 =CHCH2 CH2CH=CHCH,

1 ,5-HEPTADIENE

70 BEN/O'N

CH2 CH=CH2 CH(CH3 )CH=CH2 REACTION ORDER: 1.

CH2 =CHCH(CH 3 )CH2CH=CH3 - CH2 =CHCH2CH2 CH=CHCH 3

1 ,5-HEXADIENE, 3-METHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2C=C=C(CH3 ) 2 + CCO - (CH3 ) 2C=C=C=C(CH3 ) 2 + CO 2,3-PENTADIENE, 2,4-DIMETHYU, + CARBON 0XIDE(C2 0) 70 BEN/O'N REACTION ORDER: 2. k/k. 113. NOTE: k. CH 2 =CH, CCO

104
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3 (CH2 ) 4CH=CH2 + CH3CH2

. - CH3 (CH2 ) 4CH(.)CH2 CH2 CH3

+ CH3 (CH2 ) 4CH(CH2CH,)CH2

. 1-HEPTENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 3 CC(CH3 )=CH2 + H - (CH3 ) 3CCH(CH3 )CH2 . + (CH3 ) 3CC(.)(CH3 ) 2 1-BUTENE, 2,3,3-TRIMETHYL-, + HYDROGEN ATOM

72 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE BASED ON REACTION (CH3 ) 2C=CH2 CH3C(CH3 ) 2C(CH3 )=CH2 + CH3CH2

. -

CH3C(CH3 ) 2C( . ) (CH3 )CH2CH2 CH3

+ CH3C(CH3 ) 2 C(CH3 )(CH2CH3 )CH2

. 1-BUTENE, 2,3,3-TRIMETHYL-, + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3 (CH2 ) 5CH3 + 0 - CH3 (CH2 ) 5CH2 . + OH HEPTANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 (CH2 ) 5CH3 + 0 - CH3 (CH2 ) 4CH(.)CH3

+ CH3 (CH2 ) 3CH(.)((CH2 ) 2 CH3

+ CH3 (CH2 ) 2 CH(.)(CH2 ) 2 CH3 + OH HEPTANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 3C(CH2 ) 2 CH3 + 0 -* products

PENTANE, 2,2-DIMETHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2 CHCH2CH(CH3 ) 2 + 0 - products

PENTANE, 2,4-DIMETHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3CH2 ) 3CH+ CH3 . (CH3CH2 ) 3

C. + CH4

PENTANE, 3-ETHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3CH2 ) 3CH+ CH3

. - (CH3CH2 ) 2CHCH(.)CH3 + CH4

PENTANE, 3-ETHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3CH2 ) 3 CH+ CH3. - (CH3CH2 ) 2CHCH2CH2 . + CH4 PENTANE, 3-ETHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 3CCH(CH3 ) 2 - (CH3 ) 3

C. + (CH3 ) 2 CH. BUTANE, 2, 2, 3-TR I METHYL70 BEN/O'N REACTION ORDER: 1.

CH2 =C(CH3 )C(CH3 ) 2COOH - (CH3 ) 2C=C(CH3 ) 2 + C02 3-BUTENOIC ACID 2, 2, 3-TR I METHYL70 BEN/O'N REACTION ORDER: 1. trans-CH3CH=CHC(CH3 ) 2COOH - CH3CH2CH=C(CH3 ) 2 + C02

t r an s-3-PENTENO I C ACID, 2,2-DIMETHYL70 BEN/O'N REACTION ORDER: 1.

CH3COOCH(CH3 )CH2CH=CH2 - CH3 COOH + CH2 =CHCH2CH=CH2

+ cis-, and trans CH3CH=CHCH=CH2 ACETIC ACID 1-METHYL-3-BUTENYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: trans/cis-l,3-PENTADIENE - 7/3;

1,4-PENTAD I ENE/ 1,3-PENTAD I ENE =1/2.

CH3COOCH(CH3 )CH2COCH3 - CH3 CH=CHCOCH3 + CH3COOH 2-2-PENTANONE, 4-ACETYLOXY70 BEN/O'N REACTION ORDER: 1.

77K A B E/R

(in K)

k factors

f F

359-439 6.2(110) 0 3500

298 1 . 6( +12) - -

322-364 7.8(+ 9) 0 2800

298-650 2.9(+13) 0 2920 0.7 1.3

298-650 1.2(+14) 0 2190 0.7 1.3

307 6. 5( +10) - - 0.7 1.4

307 1.0(+11) - - 0.7 1.4

350-750 9.5(+10) 0 3975+250 0.7 1.3

350-750 6.0(+ll) 0 4830+250 0.7 1.3

350-750 7.1(+11) 0 5800+250 0.7 1.3

1069-1197 1 . 1(+16) 0 36335

447-488 7. 1(+10) 0 16560

526-564 5 . 5 ( + 1 1

0 20300

564-628 2.0(+13) 0 22345

529-570 7 . 9 ( + 1 1

0 18800

105
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

(CH3 CH2C00) 2 CH2 - (CH3CH2 C0) 20 + HCHO

METHANEDIOL, DIPROPANOATE

70 BEN/O'N REACTION ORDER: 1.

CH3 C00(CH2 ) 4CH3 - CH3 CH2 CH2 CH=CH2 + CH3 C00H ACETIC ACID PENTYL IsTER

70 BEN/O'N REACTION ORDER: 1.

CH3COOCH(CH3 )CH2 CH2 CH3

-4 c is-, and trans-CH3 CH=CHCH2 CH3

+ CH3 CH2 CH2 CH=CH2 + CH3C00H ACETIC ACID 1-METHYLBUTYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 55% 1-PENTENE.

CH3 C00CH(CH2 CH3 ) 2 - cis-, and trans-CH3CH=CHCH2 CH3

+ CH3C00H ACETIC ACID 1-ETHYLPR0PYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3COOCH2 CH(CH3 )CH2 CH3 - CH3CH2C(CH3 )=CH2 + CH3C00H ACETIC ACID 2-METHYLBUTYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3C00C[(CH3 ) 2 ]CH2CH3 - CH3 CH2 C(CH3 )=CH2

+ (CH3 ) 2C=CHCH3 + CH3C00H ACETIC ACID 1, 1-DIMETHYLPR0PYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 75% 1 -BUTENE, 2-METHYL-

.

CH3 COOCH2 CH2 CH(CH3 ) 2 - (CH3 ) 2 CHCH=CH2 + CH3COOH ACETIC ACID 3-METHYL BUTYL ESTER

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3CCOOCH2 CH3

-* (CH3 ) 3 CCOOH + CH2 =CH2 PROPANOIC ACID, 2,2-DIMETHYL-, ETHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3 CH2 COOC(CH3 ) 3 - (CH3 ) 2 C=CH2 + CH3CH2 COOH PROPANOIC ACID, 1 , 1-DIMETHYLETHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3 COOCH(CH3 )CH2 N(CH3 ) 2 - CH2 =CHCH2 N(CHO) 2

+ cis-, and trans-CH3 CH=CHN(CH3 ) 2 + CH3 COOH ACETIC ACID 1-METHYL-2-D I METHYLAM I NOETHYL ESTER

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 C=CHCH=C(CH3 ) 2 + 3CH3 CH2 -

(CH3 ) 2 C(CH2 CH3 )CH( . )=C(CH3 ) 2

+ (CH3 ) 2C(.)CH(CH2 CH3 )CH=C(CH3 ) 2 2,4—HEXADIENE, 2,5-DIMETHYL-, + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3 (CH2 ) 5CH=CH2 + CH3 CH2. -» CH3 (CH2 ) 5CH(.)CH2 CH2CH3

+ CH3 (CH2 ) 5 CH(CH2CH3 )CH2

. 1-OCTENE + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

(CH3 ) 3CCH2C(CH3 )=CH2 + CH3 CH2

. -

(CH3 ) 3 CCH2C( . ) (CH3 )CH2 CH2CH3

+ (CH3 ) 3 CCH2C(CH3 )(CH2 CH3 )CH2

. 1-PENTENE, 2,4,4-TRIMETHYL-, + ETHYL FREE RADICAL

72 KER/PAR REACTION ORDER: 2.

CH3 (CH2 ) 6CH3 + 0 - CH3 (CH2 ) 6CH2 . + OH OCTANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

CH3 (CH2 ) 6CH3 + 0 - CH3 (CH2 ) 5CH(.)CH3

+ CH3 (CH2 ) 4CH(.)CH2 CH3 + CH3 (CH2 ) 3 CH(.)(CH2 ) 2CH3 + OH OCTANE + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

7VK A B E/R

(in K)

493-578 5.0(+10) 0 18300

725-810 1.6(412) 0 23350

650-710 5.0(+12) 0 21995

650-710 1.2(413) 0 22500

725-810 7.9(111) 0 23500

501-562 2.5(+13) 0 20300

725-810 1.6(+12) 0 23350

635-694 4.0(+12) 0 24200

513-569 6.3(+12) 0 19730

650-710 6.3(+12) 0 22245

328-420 6.2(410) 0 3300

339-425 1.2(411) 0 3825

309-364 1.9(410) 0 2870

298-650 2.9(413) 0 2920

298-650 9.3(413) 0 2030

k factors

f F

0.7 1.3

0.7 1.3

106
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3 (CH2 ) 6CH3 + CH3

. - CH3 (CH2 ) 6CH2 . + CH4 OCTANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

CH3 (CH2 ) 6CH3 + CH3

. - CH3 (CH2 ) 3CH(.)CH2CH2CH3

+ CH3 (CH2 ) 4CH(.)CH2 CH3 + CH3 (CH2 ) 5CH(.)CH3 + ch4 OCTANE + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 3CCH2 CH(CH3 ) 2 + 0 -» products

PENTANE, 2,2,4-TRIMETHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 3CCH2CH(CH3 ) 2 + CH3. - (CH3 ) 3CCH(.)CH(CH3 ) 2 + CH4

PENTANE, 2 , 2^4CTR I METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 3CCH2 CH(CH3 ) 2 + CH3. - (CH3 ) 3CCH2C(.)(CH3 ) 2 + CH4

PENTANE, 2,2,4-TRIMETHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 3CCH2CH(CH3 ) 2 + CH3. - (CH3 ) 3CCH2CH(CH3 )CH2

. + CH2C(CH3 ) 2CH2CH(CH3 ) 2 + CH4 PENTANE, 2,2, 4-TR I METHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 + 0 -» products

PENTANE, 2, 3, 4-TR I METHYL-, + OXYGEN ATOM

73 HER/HUI REACTION ORDER: 2.

(CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 + CH3. -

.CH2CH(CH3 )CH(CH3 )CH(CH3 ) 2 + CH4

PENTANE, 2, 3, 4-TR I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 + CH3. -

(CH3 ) 2CHC(.)(CH3 )CH(CH3 ) 2 + (CH3 ) 2C(.)CH(CH3 ) 2 + CH4

PENTANE, 2, 3, 4-TR I METHYL-, + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3 ) 2 CHCH(CH3 )CH(CH3 ) 2 + CH3

. - [C8

H 17 .] + CH4 PENTANE, 2, 3, 4-TR I METHYL-, + METHYL FREE RADICAL

72 KON REACTION ORDER: 2.

(CH3 ) 3CC(CH3 ) 3 - (CH3 ) 3

C. + (CH3 ) 3C. BUTANE, 2,2,3, 3-TETRAMETHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3 CC(CH3 ) 3 + 0 -* products

BUTANE, 2,2,3, 3-TETRAMETHYL73 HER/HUI REACTION ORDER: 2.

(CH3 ) 3CC(CH3 ) 3 + CH3

. - .CH2 C(CH3 ) 2CC(CH3 ) 2 + CH4

BUTANE, 2,2,3, 3-TETRAMETHYL- , + METHYL FREE RADICAL

76 KER/PAR REACTION ORDER: 2. NOTE: TENTATIVE k VALUE.

(CH3COO) 2CHCH=CHCH3 - (CH3C0) 20 + c

s-CH3CH=CHCHO

2-BUTENE-l , 1-DIOL, DIACETATE

70 BEN/O'N REACTION ORDER: 1. NOTE: PROBABLY RELIABLE k.

(CH3COO) 2CHCH2 CH2CH3 - (CH3C0) 20 + CH3CH2CH2 CHO

1 , 1-BUTANEDIOL, DIACETATE

70 BEN/O'N REACTION ORDER: 1. NOTE: PROBABLY RELIABLE k.

77K A B E/R

(in K) k factorsf F

350-800 4.8(+ll) 0 5800+250 0.7 1.3

350-800 1.2(+12) 0 4830+250 0.7 1.3

307 5.5(+10) - - 0.6 1.5

350-750 2.0(411) 0 4830+250 0.7 1.3

350-750 9.5(+10) 0 3975+250 0.7 1.3

350-750 1 . 2 ( +12

0 5800+250 0.7 1.3

307 3.0(+10) - - 0.6 1.5

350-750 1 . 2 ( +12

0 5800+250 0.7 1.3

350-750 2.9(111) 0 3975+250 0.7 1.3

414-605 4.7(+ll) 0 4575

985-1119 5 . 0( +16) 0 33800

307 8.0(+ 9) - - 0.6 1.5

350-800 1 . 4( +12

0 5800+250 0.7 1.3

492-533 1 . 3 ( +1 1

0 16600

484-538 3.0(+10) 0 16560

107
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions T/K A B E/R

(in K)

484-538 2.5(+10) 0 16560

370-452 2.0(+14) 0 14900

560-610 1.4(113) 0 19400

725-810 7 . 9 ( + 1 1

)

0 23050

650-710 4.0(+12) 0 21740

560-610 1.5(+13) 0 19525

560-610 1.3(+13) 0 19075

403-443 4.0(+15) 0 18800

L 350-500 1.8(+12) 0 5900+150

473-673 3.2(+16) 0 25165

539-618 4.0(+16) 0 23500

473-673 1.7(+16) 0 24660

473-673 1 . 4( +17

)

0 21900

471-508 2.5(+14) 0 17365

374-402 2.5(+14) 0 12900

k factors

f F

(CH3CH2 C00) 2 CHCH3 - (CH 3CH2C0) 20 + CH3CH0

1 , 1-ETHANEDIOL, DIPROPANOATE

70 BEN/O'N REACTION ORDER: 1.

CH3CH2CH2 C(0)00C(0)CH2 CH2 CH3 -

+ CH3CH2 CH2C(0)0.

PEROXIDE, BIS( l-OXOBITYL)

CH3 CH2CH2 C(0)0.

70 BEN/O'N REACTION ORDER: 1

CH3C00C(CH2 CH3 ) 2 CH3 - cis-, and trans-CH3CH=C(CH3 )CH2 CH 3 + CH2 =C(CH2CH3 ) 2 + CH3C00H ACETIC ACID 1 -ETHYL- 1-METHYLPROPYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 659c 1-BUTENE, 2-ETHYL-

.

CH3C00CH2 CH(CH2 CH3 ) 2 - (CH3CH2 ) 2 C=CH2 + CH3C00H

' ACETIC ACID 2-ETHYLBUTYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3 COOCH(CH3 )CH(CH3 )CH2 CH3 - CH2 =CHCH(CH3 )CH2CH3

+ cis-, and trans-CH3CH=C(CH3 )CH2 CH3 + CH3 C00H ACETIC ACID 1 , 2-D I METHYLBUTYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 16% 1-PENTENE, 3-METHYL-

.

CH3COOC(CH3 ) 2CH2 CH2 CH3 - CH2 =C(CH3 )CH2 CH2 CH3

+ (CH3 ) 2C=CHCH2 CH3 + CH3 C00H ACETIC ACID 1 , 1-DIMETHYLBUTYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 72% 1-PENTENE, 2-METHYL-

.

CH3 C00C ( CH3 ) 2 CH ( CH3 ) 2 - (CH3 ) 2C=C(CH3 ) 2

+ CH2 =C(CH3 )CH(CH3 ) 2 + CH3C00H ACETIC ACID 1,1, 2-TR I METHYLPROPYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 909c 1 -BUTENE, 2,3-DIMETHYL-.

(CH3 ) 3COOC(CH3 ) 3 - (CH3 ) 3CHO. + (CH3 ) 3 CO. PEROXIDE, BIS( 1 , 1-DIMETHYLETHYL)

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3COOC(CH3 ) 3 + CH3. - ,CH2C(CH3 ) 2OOC(CH3 ) 3 + CH< PEROXIDE, BIS(1, 1-DIMETHYLETHYL)-, + METHYL FREE R l 76 KER/PAR REACTION ORDER: 2.

CH3 CH2 CH 2CH2 N=NCH,CH2 CH2CH3

+ CH3CH2CH2CH2

. DIAZENE, DIBUTYL70 BEN/O'N

- CH3 CH2 CH2 CH2 N=N.

REACTION ORDER: 1.

CH3CH2CH(CH3 )N=NCH(CH3 )CH2 CH3 -

+ CH3CH2 CH(.)CH3 DIAZENE, BIS( 1-METHYLPROPYL)-

CH3 CH2 CH(CH3 )N=N.

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 CHCH2 N=NCH2 CH(CH3 ) 2 - (CH3 ) 2CHCH2 N=N.

+ (CH3 ) 2 CHCH2

. DIAZENE, BIS(2-METHYLPR0PYL)-

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 3CN=NC(CH3 ) 3 - (CH3 ) 3CN=N . + (CH3 ) 3

C. DIAZENE, BIS(1, 1-DIMETHYLETHYL)-

70 BEN/O'N REACTION ORDER: 1.

(CH 3CH2 ) 2NN=NN(CH2 CH3 ) 2 - (CH3CH2 ) 2 NN=N. + (CH3CH2 ) 2N. 2-TETRAZENE, 1,1,4, 4-TETRAETHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2CHCH2 N(0)N(0)CH2CH(CH3 ) 2 - (CH3 ) 2 CHCH2 NO

+ (CH3 ) 2 CHCH2 NO PROPANE, 1-NITR0S0-2-METHYL-, DIMERIC

70 BEN/O'N REACTION ORDER: 1.

0.3 3

108
Table of Arrhenius parameters for chemical reactions occurring in combustion—Continued

Chemical reactions

CH3CH=C(CH2 CH3 )C(CH3 ) 2 C00H - (CH3CH2 ) 2 C=C(CH3 ) 2 + C02 PENTANOK ACID, 2 ,2-D I METHYL-3-ETHYLI DENE70 BEN/0 'N REACTION ORDER: 1. NOTE: RELIABLE k.

(CH3CH2 CH2 C00) 2 CH2 - (CH3CH2 CH2 C0) 20 + HCHO

METHANEDIOL, DIBUTANOATE

70 BEN/O'N REACTION ORDER: 1.

CH3C00CH(CH3 )(CH2 ) 4CH3 - CH3 (CH2 ) 4CH=CH2

+ cis-, and trans-CH3 CH=CH(CH2 ) 3CH3 ACETIC ACID 1-METHYLHEXYL ESTER

70 BEN/O'N REACTION ORDER: 1. NOTE: 58% 1-HEPTENE.

CH3COOCH(CH2 CH3 )CH2CH2CH2 CH3 - CH3CH=CH(CH2 ) 3 CH3

+ cis-, and trans-CH3CH2 CH=CHCH2 CH2CH3 + CH3C00H ACETIC ACID 1-ETHYLPENTYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3 C00CH(CH2 CH2 CH3 ) 2 -

+ cis-, and t rans-CH3 CH2 CH=CHCH2 CH2 CH3 + CH3 C00H ACETIC ACID 1-PROPYLBUTYL ESTER

70 BEN/O'N REACTION ORDER: 1.

CH3 C00CH[CH(CH3 ) 2 ] 2 - (CH3 ) 2 CHCH=C(CH3 ) 2 + CH3C00H ACETIC ACID 1- ( 1

' -METHYLETHYL) -2-METHYLPROPYL ESTER

70 BEN/O'N REACTION ORDER: 1.

(CH3 ) 2 C=CHCH2CH2 CH(CH3 )CH=CH2 -

cy- [ CH2 =C ( CH3 )

] CHCH ( CH3) CH ( CH3) CH2 CH2 1,6-OCTADIENE, 3, 7-D I METHYL70 BEN/O'N REACTION ORDER: 1.

(CH3 CH2CH2 C00) 2 CHCH3 - (CH3 CH2CH2C0) 20 + CH3 CH0 1,1-ETHANEDIOL, DIBUTANOATE

70 BEN/O'N REACTION ORDER: 1. NOTE: PROBABLY RELIABLE k.

(CH3 COO) 2CH(CH2 ) 5CH3 - CH3 (CH2 ) 5CHO + (CH3

C0) 20 1,1-HEPTANEDIOL, DIACETATE

70 BEN/O'N REACTION ORDER: 1. NOTE: PROBABLY RELIABLE k.

7VK A B E/R

(in K)

468-502 4.8(+ll) 0 18100

493-578 5.0(+10) 0 18300

650-710 5.4(+12) 0 21995

650-710 5

6 (

12 ) 0 21740

50-710 4.0(112) 0 21500

650-710 6.9(+12) 0 22500

656-682 1 - 2 ( + 9) 0 17700

473-573 1 . 8 (+ 10 ) 0 16600

473-573 3.0(+10) 0 16600

k factors

f F

3. Sources of Recommended Rate

Constants

Baulch, D. L., Drysdale, D. D., Horne, D. G., and Lloyd, A. C., “Evaluated Kinetics Data for High Temperature Reactions, Vol. 1 : Homogeneous Gas Phase Reactions of the H2 -O2 System,” (Butter- worths, London, 1972). Baulch, D. L., Drysdale, D. D., Horne, D. G., “Evaluated Kinetic Data

for High Temperature Reactions, Vol. 2: Homogeneous Gas Phase

Reactions of the H2 -N2 -O2 System,” (Butterworths, London, 1973). Baulch, D. L., Drysdale, D. D., Duxbury, J., and Grant, S. J., “Evaluated Kinetic Data for High Temperature Reactions, Vol. 3: Homogeneous Gas Phase Reactions of the O2 -O3 System, the CO-O2 -H2 System, and of Sulphur-Containing Species,” (Butterworths, London, 1976). Benson, S. W., Golden, D. M., Lawrence, R. W., Shaw, R., and

Woolfolk, R. W., “Estimating the Kinetics of Combustion Including Reactions Involving Oxides of Nitrogen and Sulfur,” Environmental

Protection Agency Report No. EPA-600/2-75-019, August 1975.

Benson, S. W., and O’Neal, H. E., “Kinetic Data on Gas Phase

Unimolecular Reactions,” NBS-NSRDS-21 (1970). (Supt. Doc., U.S.

Govt. Printing Office, Washington, D.C. 20402).

Engleman, V. S., “Survey and Evaluation of Kinetic Data on Reactions

in Methane/Air Combustion,” Environmental Protection Agency

Report No. EPA-600/2-76-003, January 1976.

Herron, J. T., and Huie, R. E., “Rate Constants for the Reactions of Atomic Oxygen (O 3 P) with Organic Compounds in the Gas Phase,” J. Phys. Chem. Ref. Data 2, 467-518 (1973). Kerr, J. A., and Parsonage, M. J., “Evaluated Kinetic Data on Gas

Phase Addition Reactions: Reactions of Atoms and Radicals with Alkenes, Alkynes and Aromatic Compounds,” (Butterworths, London, 1972).

Kerr, J. A., and Parsonage, M. J., “Evaluated Kinetic Data on Gas

Phase Hydrogen Transfer Reactions of Methyl Radicals,” (Butter- worths, London 1976). Kondratiev, V. N., “Konstanty Skorosti Gazofaznykh Reaktsij Spra- vochnik,” (Izdatelstvo “Nauka,” Moskva, 1970); also isued as “Rate

Constants of Gas Phase Reactions, Reference Book,” R. M. Fristrom,

Ed., Translated by L. J. Holtschlag COM-72-10014, Office of Standard Reference Data, NBS (1972) (Distributed by National Technical Information Service, Springfield, Virginia 22151).

Lloyd, A. C., “Evaluated and Estimated Kinetic Data for Gas Phase

Reactions of the Hydroperoxyl Radical,” Int. J. Chem. Kinet. 6, 169-228 (1974).

109
Appendix: Conversion Tables

Equivalent second order rate constants

A B cm ’mol -’s -1 dm ’mol

-

*s -

1

m ’moP's -1 cm ’molecule

-

's

' (mm Hg) *s -

1

atm 's

1 ppm 'min ' m \N 's'

1 cm ’mol “*s ” 1 1 10

- ’ 10 -6 1.66 X10 -24 1.604 X 10

— ’ T

-1 1.219 X10 -2 T~ l 2.453 X10 -9

1.203 XIO -4 T~'

1 dm ’mol

—

*s — *= 10’ 1 10

- ’ 1.66 X10 -2' 1.604 X10 -2 T~'

12.19 T~ l 2.453 X10 -6 1.203 XIO -

' T’ - '

1 m ’moP's -1 10 s 10’ 1 1.66 XlO - ' 8 16.04 T~ l 1.219 XlO 4 T

-1 2.453 xio -3 120.3 T~ l

1 cm ’molecule “

*s - '= 6.023 XlO 23 6.023 X10 20 6.023 X10 17

1 9.658 X 10 18 T

~ 1 7.34 X10 2 ' 7”'

1.478 X10 15 7.244 XIO 19

T" - '

1 (mm Hg)

-

‘s - '= 6.236 X10 4 T62.36 T 6.236 XlO -2 T

1.035 X10 - ' 9 T1 760 4.56 XIO -2 7.500

1 atm

~

*s - '= 82.06 T 8.206 XlO -2 T

8.206 X10 -S T1.362 X10 -22 T1.316 X10 - ’1 6X 10 -s 9.969 XIO -3

1 ppm

-1min -I =

at 298 K, 1 atm

total pressure

4.077 XlO 8 4.077 XlO 5 407.7 6.76 X10 - ' 6 21.93 1.667 X10 4 1 164.5

1 m \N “

's - *= 8.314 T 8.314 T 8.314 X10 -

’ T

1.38 X 10 - 20 7" 0.1333 101.325 6.079 xio -3

1

To convert a rate constant from one set of units A to a new set B find the conversion factor for the row A under column B and multiply the old value by it, e.g., to convert cm Molecule

-

's -

' to m ’mol

-

's ” 1 multiply by 6.023 X 10 ,7

. Table adapted from Evaluated Kinetic Data for High Temperature Reactions, Volume 1: Homogeneous Gas Phase Reactions of the H2-O2 System, Butterworths, London, 1972.

Equivalent third order rate constants

A B cm ®mol

- %- ' dm ^ol - %

-

1

m ^nol 1 cm Siolecule %

1 (mm Hg) %

1 atm

~ 2s~ 1 ppm

- ^nin -1 m

4kN -2

s -1

1 cm *tnol - '= 1 10 -6 10 - 12 2.76 XIO -48 2.57 Xio - » 0 r

-2

1.48 XIO -4 T~ 2 1.003 XIO -19 1.447 X 10 -8 T~ 2

1 dm Siol

- ^-

' = 10-8

1 10-8 2.76 XIO -42 2.57 XIO -4 T~ 2 1.48 T~ 2 1.003 XIO -1’ 1.447 X 10 -2 T~ 2

1 m SnoP% -1 10 12 10 s

1 2.76 XIO -38 257 T

~ 2 1.48 XIO 8 7’ -2

1.003 XIO -7

1.447 XIO4 T~ 2

1 cm *tnolecule ^

l= 3.628 XIO 47 3.628 XIO 41 3.628 XIO’5

1 9.328 XIO’7 T~ 2 5.388 XIO 4 ’ T~ 2 3.64 XIO 28 5.248 X 10 39 T~ 2

1 (mm Hg)

- %

- '= 3-89 XIO 9 7' 2 3-89 T XIO’ T

1 3.89 XIO - ’?" 2 1.07 X 10 -39 T2 1 5.776 XIO 5 3.46 xio -5 56.25

1 atm ~h~ l = 6.733 X10’ T

2 6.733 XIO -

’ T

2 6.733 XIO -9 T

2 1.86 XIO -44 T2 1.73 XIO -8

1 6X10 - " 9.74 xio -5

1 ppm

- ’min -1=

at 298 K, 1 atm

total pressure

9.97 XIO 18 9.97 xio 12 9.97 XIO 8 2.75 XIO -29 2.89 XIO 4 1.667 XIO 10 1 1.623 xio 8

1 m VN -

’s - '= 6.91 T xio 7 r*

69.1 T

2 6.91 xio -5

/

12 1.904 XIO -40 T

2 0.0178 1.027 XIO 4 6.16 XIO -7

1

See note to Table for second order rate constants.

110
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BIBLIOGRAPHIC DATA

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1. PUBLICATION OR REPORT NO. NSRDS-NBS 673. Reclptenf & Accession Wo,

4. TITLE AND SUBTITLE

Table of Recommended Rate Constants for Chemical Reactions

Occurring in Combustion

5. Publication Date April 1980

7. AUTHOR(S)

Francis Westley

8. Performing Organ. Report No

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

M. P»|ect/Taslt/Work iMfNo.

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City, State, ZIP)

Department of Energy, Washington, DC 20545 and

Office of Standard Reference Data, National Bureau of

Standards, Washington, DC 20234

13. Type of Report & Period Covered N/A

14. Sponsoring Agency Code P, 15. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 79-607 159

| | Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or leas factual summary of moat significant information. If document includes a significant bibliography or

literature survey, mention it here.) A table of recommended rate constants for gas: phase chemical reactions occurring

in combustion is presented. Specifically, it gives in tabular form the values of the

parameters for the modified Arrhenius equation k = ATBexp (-E/RT) . The table covers

reactions occurring in the combustion, oxidation, and decomposition of aliphatic

saturated or unsaturated to hydrocarbons, alcohols, aldehydes, ketones, thiols,

ethers, peroxides, amines, amides and their free radicals, as well as the reactions of

o, o

2

, h, h

2

, oh, h

2 o, h2o

2

, n, n

2

, no, n

2 o, no

2

, n

2 o

4

, n

2 o

5

, s, s

2

, SH, so, so

2

, SOH,

NS, with each other. The table includes 169 first order reactions, 782 second order

reactions, and 57 third order reactions. There are 1770 entries covering 1008 distinct

chemical reactions. These recommendations have been taken from eleven evaluations and

critical reviews published between 1970 and 1976. The papers examined by the

evaluators extend from the nineteen fifties up to - and including - 1975.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the firat letter of the first key word unless a proper name;

separated by aemicolona)

Arrhenius parameters; chemical kinetics; combustion ^ decomposition; free radicals;

gas phase; hydrocarbons; hydrogen; nitrogen; oxygen; rate of reaction; sulfur.

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119

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