NBSIR 79-1941

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Table of Recommended Rate

Constants for Chemical Reactions

Occurring in Combustion

Francis Westley

Chemical Kinetics Division

National Measurement Laboratory

National Bureau of Standards

U.S. Department of Commerce

Washington, D.C. 20234

November 1979

Prepared for Department of Energy

Washington, D.C. 20545

and

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C. 20234

NBSIR 79-1941

TABLE OF RECOMMENDED RATE

CONSTANTS FOR CHEMICAL REACTIONS

OCCURRING IN COMBUSTION

Francis Westley

Chemical Kinetics Division

National Measurement Laboratory

National Bureau of Standards

U.S. Department of Commerce

Washington, D.C. 20234

November 1979

Prepared for Department of Energy

Washington, D.C. 20545

and

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C. 20234

U.S. DEPARTMENT OF COMMERCE

Luther H. Hodges, Jr., Under Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
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Table of Recommended Rate Constants for Chemical

Reactions Occurring in Combustion

by

Francis Westley

Chemical Kinetics Information Center

National Measurement Laboratory

National Bureau of Standards

Washington, DC 2023^

Sponsored by the

Department of Energy

Washington, DC 205^5

and

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 2023^
Table of Contents

Abstract

Introduction

Guidelines for the User

Sources of Recommended Rate Constants

Table of Arrhenius parameters for chemical reactions

occurring in combustion

Reactions of; 0

H

OH . H02*

H2O

S

SO . SO2

SH . H2S

N .

NO . . . NO2 . . NO3 . . N2O , .

NH . NH2 . NH3 . NH2NH2

1

2

4

20

22

22

31

33

34

42

44

48

50

,50

50

54

55

55

56

57

57

62

63

65

67

67

68

68

68

70

70

70
HN3

70

HNO 70

HNO372

NS 72

C-| compounds 72 C2 compounds Ill C3 ompounds 124

compounds 131

Cg compounds 144

Cg compounds 150

Cy compounds 156

Cg compounds 158

Cg compounds 162

C-|Q compounds 162

Appendix: Conversion Tables 163
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70

W
TABLE OF RECOMMENDED RATE CONSTANTS FOR CHEMICAL

REACTIONS OCCURRING IN COMBUSTION

Francis West ley

National Bureau of Standards

Chemical Kinetics Division

Center for Thermodynamics and Molecular Science

Washington, DC 2023^

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 exp(-E/RT). The table covers reactions occurring in the combustion,

oxidation and decomposition of aliphatic saturated or unsaturated C^ to C^q

hydrocarbons, alcohols, aldehydes, ketones, thiols, ethers, peroxides, amines

amides and their free radicals, as well as the reactions of 0 , 0^, H, H2, OH,

H^O, H2O2, N, N2, NO, N2O, NO2. N20^, N20g, S, S2, SH, SO, SO2. SOH, NS, with

each other. The table includes I69 first order reactions 782 second

order reactions and 57 third order reactions. There are 1770 entries

covering IOO8 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.

This work was supported by the Department of Energy and by the

Office of Standard Reference Data of the National Bureau of Standards.
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 amino 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 recommended 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-consul t 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.

SOURCE # RECOMMENDED RATE

BAULCH et al (1972) ko

BAULCH et al (1973) 6A

BAULCH et al (1976) 36

BENSON and O'NEAL (1970) 167

BENSON et al (1975) 119

ENGLEMAN (1976) 123

HERRON and HUIE (1973) ^6

KERR and PARSONAGE (1972) 185

KERR and PARSONAGE (1976) 181

KONDRATIEV (1970) 37

LLOYD (197^) 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

2
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 expressed in the modified Arrhenius

g equation k = AT exp(-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 E/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 , cm mol s , and cm mol s 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 second and - respectively - third order

rate constant units are appended at the end of this publication.

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 al 1 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;

3
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.

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 somewhat more complicated, but when a series

of recommended rate constants is to be presented in a tabular form, the

uncertainty limits can not 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 i s 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 lowe

and upper k factors - f and F, respectively - are the most suitable for
tabulation. Thus, if k is the central value of a rate constant the

o limits of reliability for the rate constant k are defined by the

o

rel at ionsh i p:

fk < k < Fk (1) o o

i.e. multiplication of the central value k^ by f and F gives respectively

the lower and upper reliability limits of the rate constant. In this

standardized formulation of uncertainty limits, the value of f 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 transformation 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 .

Beside the standard form of uncertainty 1 imi ts expressed by the lower

and upper factors f and F, as defined by the above given relationship (1),

there is another form which expresses the uncertainty limits by a un i que

factor. Thus, if k^ is the central value of a rate constant, the statement

that k is uncertain to a factor of F means that the uncertainty limits

are defined by the relationship:

k /F < k < k F (2) o o

which shows that division and multiplication of the central value k by F

gives respectively the lower and upper reliability limits of the rate

5
constant. By comparing relationships (1) and (2), it is obvious that in the

case of an uncertainty expressed by an unique F the upper factor is equal to

the unique factor itself, while the lower factor f is the reciprocal of F:

f = 1/F (3)

Uncertainty expressed by algebraic addends .

There are three types of uncertainty limits for rate constants expressed

as algebraic addends, which are currently used by kineticists: a). Uncerta i nty

appended to one of the Arrhenius factors (A, B, or E/R) ; b) . Uncerta i nty

appended to log ^^k^; and c) . Uncertainty expressed as a percentage of k^ With

respect to the type a) uncertainties, the B factor uncertainties have

been eliminated as being unimportant, while the uncertainties for 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 = axlO*^ (A)

where a is a numerical coefficient less than 10 and n is the power of 10.

If an uncertainty jja ' is appended to the coefficient a, the A factor takes

the form:

A = (a + a' ) X 10^ (5)

If lower and upper factors (f and F) are wanted instead, the A factor takes

the form:

A = fa X 10^ (6)

or A = Fa X lo" (7)

6
Comparison of (6) and (7) to (5) leads to the relationships: fa = a - a' and

Fa = a + a ' from which the following formulas are obtained:

f = 1 - a'/a (8)

and F = 1 + 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^^ therefore: a = 2.0 and a' = 0.5

a'/a = 0. 5/2.0 = 0.25 and the k factors are: f = 1 - 0.25 = 0.75

and F = 1 + 0.25 = 1.25

b) . Uncertainty appended to log ^^k^. If k^ 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:

log^^k = C + D

where C = log^^k^. If D is put in logarithmic form, say:

D = 1o9|qF

then relationship (10) becomes:

( 10 )

( 11 )

=

log|o'<o 1 '°9|o''

which can take the form:

( 12 )

log|flk^/F < log,pk < log,gFk_^

or

k /F < k < Fk (13) o o

'

Replacing 1/F by f, relationship (1) is obtained. It is obvious that the

k factors f and F are the ant i logar i thms of -D and D, respectively:

f = ant i log (-D) = 10-“ (H)

F = ant i logD = io“ (15)

7
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:

log^^k = 14.23 ^ 0.3 therefore: f = 10 = 0.5 and F = 10^*^ = 2.0

c) . Uncertainty expressed in percentage of k^ . Some kineticists prefer

to use percentage for defining the uncertainty limits of a rate constant.

Thus, the statement that a rate constant i s ^ p% uncertain means that the

uncertainty limits of k^ are defined by the relationship:

k - (p/100)k < k < k + (p/100)k

o o o o or (1 - p/100)k^ < k < (1 + p/100)k^ (16)

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

(1 - r)k < k < (1 + r)k (17) o o

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

formu 1 as

f = 1 - r (18)

and F = 1 + r (19)

which are the relationships needed to transform the type c uncertainties

into reliability limits expressed by k factors. A numerical example

fol lows

k = 3-7 X lo'^ + 20^ therefore p = 20^ and r = 0.2

Thus : f= 1 -0.2=0.

and F = 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 = 1/F. E.g.: for a 150% error, r = 1.5, F = 1 + r =

2.5 and f = 1/F = 0.4.

8
The above given relationships: (3), (8) and (9) i (1^) and (15). (18)

and (19) can be used in reverse by the reader who prefers other types of

uncertainty limits than the standard k factors, f 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

expressed 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 un i que factor, F, indicates in fact that the upper factor F

and the lower factor f are required to be inverse to each other (f = 1/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 purposes. Why some evaluators prefer uncertainty limits

with constraints is not clear. It would seem more logical if the lower and

upper uncertainty limits were studied each 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 - : log^^k = C D

rather than by the inequality: fk^ < k < Fk^.

If the transformation of the standard uncertainty limits into uncertainties

with constraints is desired, some adjustments 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: f = 0.5 and F = 2.0 It is obvious that f = 1/F

and no adjustment is necessary.

2)

. Standard factors: f = 0.8 and F = 1.2 In this case, f and F are

not inverse to each other. Indeed f = 1/F = 0.83 while F' = 1/f = 1.25.

9
The two pairs of factors, (f = 0.83; F = 1.2 and f = 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: f = 0.6 and F = 1.4 In this case, not only the

factors are not inverse to each other, but the difference is significant:

f

' = 1/F = 0.71 and F' = 1/f = 1.6?.

The two pairs of factors, (f = 0.71; F = 1.4 and f = 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 transformation of k factors

uncertainties into another type of uncertainties.

Arrangement of the table

This publication is in two parts:

Part I . The table, arranged in six columns including the chemical

reactions, temperature range, the parameters A, B and E/R for the modified

Arrhenius equation k = AT exp(-E/RT) and the uncertainty limits expressed

as k factors f and F.

Part II . The bibliography of part I, including 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 - respectively - third order rate 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.

10
Alternative neames 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/HU I 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 fol lows

1 for first order reactions s

^

2 for second order reactions cm^mol ^s

^

6 ”2 ” 1 3 for third order reactions cm mol s

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 12A reactions, no Arrhenius parameters are indicated. Instead,

for each of these Mk reactions, the ratio of the rate constant with

11
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 followed by a number.

E.g.: 0.59.

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

dependence of k factors on temperature range, or the reaction taken as

reference when the ratio k/k^^^ is given in the previous line, or other

information pertinent to the reaction indicated above. The rate constant,

k^^^, 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| = K k_^ included 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 forward 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 degrees Kelvin the

temperature range of validity of the recommended rate parameters. For

some reactions only one temperature is given, meaning that the reaction was

12
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 their 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 A, gives the value of A for the equation

g k = AT exp(-E/RT) in short scientific notation . In other words, it appears

as a number less than 10, followed by a parenthesis including an integer

preceded by the sign +, or The number iess than 10 is the coefficient

of the A' factor, while the integer inside the parenthesis is the exponent

+ 1

of 10. Therefore, e.g., 3*5 (+ 1^) should be read as 3*5 x 10 . The

coefficient of the A factor has no more than one digit after the decimal point.

The units of the A factor are the same as for the rate constant k|

according to the order of the respective reaction, as shown above on

page 11 of this introduction. 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 A 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 A , with the heading B, gives the value of B for the equation

g k = AT exp(-E/RT). The value of B is usually low and varies from 0 to

about 3 or A. It may be negative, or positive. The negative values of

B are preceded 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

13
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 A 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 k = AT 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 ^ K \ it follows

that the units of E/R are degrees K. The values given in column 5 for

E/R may vary from 0 to over 100000 degrees K. 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 indicated 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 "k factors" and two subheadings, "f" and

"F", 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): fk^ < k < Fk

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 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 arrangement, 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 precedence is as follows:

1). 0_ system, 2). JH-0 system, 3)- ^“0-H system, h)

system, and

5). £-0-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

*) . 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 pgs. 5, 16, 22 (1968).

15
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, O

2

,

2). H-0 system: H, H^, OH, HO^, H^O, H^O^.

3). S-O-H system: S , $2, SO, SO

2

, SO^, SH, SH

2

, SOH.

N-O-H-S system: N, N

2

, NO, NO

2

. NO^, N

2 O, N20^, N20^, NH, NH

2

,

NH^, N2H^, HN^, HNO, HNO^, NS.

5). C-O-H-S-N system : compounds: C, CO, CO

2

, CH, CH

2

, CH^, CH^, CHO,

HCHO, CH^O., CH^OH, CH^OOH, CS, CS

2

,

COS, CH^S, CH^SH, CN, CCNO^)^, CHN,

CH^NH^, CH=NEN, CH^NHNH^, CH^NO,

CH^NO^, CH^NO^, CH^ONH^.

compounds : C^, C 2

O, CHECH, CH

2

=CH

2

, CH^CH^**

CH^CH^, CH

2

=C=0 , etc.

C^ compounds , etc., up to C^^ compounds follow, being

ordered according to the same pattern.

It is clear now that, for instance, the compounds included in the ^-0-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 (^-system

and ^-0 system). It is to be noted that for the ^-0-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.

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

16
can be switched around, a number of bimolecular and termolecular reactions

are inserted in the table in two - and respectively - three places. E.g.:

Reaction + 0 -> CH^» + OH, is inserted in the £-0-H-S-N system. This

reaction may also be written as 0 + CH^ -> OH + CH^* and, as such, is listed

in the £ 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 CH2

^ 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 i s NO + NO

2

"* ^

N^O^. This reaction will also be inserted under the forms: NO

2 + NO + O

2

N20^ and O

2 + NO + NO2 ^20^. A number of second and third order reactions

includes a second and - respectively - third body M. 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 0^ + M -> 0 + O

2 + M is inserted in the

table only once, while reaction NO + 0 + M -> NO

2 + M is inserted as such,

and also under the form 0 + NO + M NO

2 + M.

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

number of reactions are only apparently unbalanced . For instance, reaction

CH^CH2CH2CH^ + H ^ CH^CH2CH2CH2* + CH^CH2CH(*) CH^ + H

2 (20)

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

reactions

17
( 21 )

( 22 )

CH^CH2CH2CH^ + H CH^CH2CH2CH2‘ + H 2

and CH^CH

2

CH

2

CH^ + H ^ CH^CH

2

CH (

• ) CH^ + H 2

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.:

CH^- + (CH^)2CHCH(CH^)CH(CH^)2 CH^ + [CgHj^-] (23)

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, ^"Trimethyl -pentane. There are a number of reactions with the products totally

unspecified. In such a case, the word "products" appears after the arrow:

(CH^)

2

C = CHCH^ + N -> products (2^)

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: CH^^, CH^CH^, CH^CH

2

CH^, CH^CH

2

CH

2

CH^

CH^CH2CH2CH2CH^.

The higher hydrocarbons, from n-hexane to n-decane, are written in

a more condensed form to facilitate the counting of the number of methylene

groups in the chain: CH^ (CH

2

)

2^CH^ , CH^ (CH

2

) , CH^ (CH

2 )gCH^, CH^ (CH

2

) , CH^(CH2)gCH^.

18
The unsaturated hydrocarbons are written so as to show the position of

each double or triple bond in the molecule. E.g.:

Ethyne (Acetylene) CHECH

1 ,2-Propad iene (Allene) CH2=C=CH2

1 ,3"Butad i yne CHeCCeCH

c i s-2-Pentene cis-CH^CH2CH=CHCH^

1 -Heptene CH^(CH2)2^CH=CH2

Alkyl radicals . The unpaired electron of each alkyl radical is always

indicated. E.g.

Methyl free radical CH^*

Ethyl, 1-methyl-, free radical

( 1 sopropy 1

(CH^)2CH*

Methyl, hydroxy-, free radical •CH

2

OH

If the unpaired electron of an alkyl radical belongs to a carbon in the

middle of the chain, it Is indicated insi

carbon atom. E.g.

ide a parenthesis following the

Propyl, 1-methyl-, free radical

(sec-Buty 1

CH^CH2CH(*)CH^

Butyl, 1 ,

1 -d imethy 1 - , free radical

(2 -Methyl -2-pentyl

CH^CH2CH2C(-) (CH^)2

Methyl, 0x0 -, free radical (Formyl)

i s wr i tten

•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: CH^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: (CH

2

) 2

C (0* )CH

2

CH^.

19
Peroxo, and other free radicals . The rules for writing peroxo, and

other free radicals are the same as for the oxy free radicals: CH^02», CH^S**

Atoms, like 0 , H, S, N, and simple radicals like OH, SH, NH, CH,

CH2, are written without dot. Hydroperoxyl free radical is written

HO^* (wi th dot)

20
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 ^ 2~^2 (Butterworths , London, 1972).

Baulch, D. L. , Drysdale, D. D. , and Horne, D. G., "Evaluated Kinetic Data for

high Temperature Reactions, Vol. 2: Homogeneous Gas Phase Reactions

of the ^VStem," (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 02*^3 System, the C0-02"H2 System, and

of Sulphur-Containing Species (Butterworths , London, 197^).

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. 20^02).

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'^P) with Organic Compounds in the Gas Phase," J. Phys. Chem.

Ref. Data ^67-518 (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," (Butterworths, London

1976).

Kondratiev, V. N. , "Konstanty Skorosti Gazofaznykh Reaktsij Spravochn i k,"

(Izdatelstvo "Nauka", Moskva, 1970); also issued as "Rate Constants of

Gas Phase Reactions, Reference Book," R. M. Fristrom, Ed., Translated

by L. J. Holtschlag COM-72-1001^, 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).

21
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X u NW « a a Z B a B m a tk w z u y 4 Nl y X M w Q • n P (M 0 1 B u a 1 m 0 B 1 y 4 z «4 B U)P B o y H z u Z n Ft p4 Z H fc •4 Z y h p4 Z ^ a4 Z CM 44 at Z y Z B M Z z

y \ ^ • % y f « B r)4* \ CM^ % m % B lOZ \ BX % (MP \ V w iJ V w B y n m a y n Q V B a V z B Z 44 a y X Z B P

n N Nl o V N ^ -Q M X » y V m N 'O M N y X N zw M N y B N X y z X X

y u z n V M z D a y z • CM a y z B a y Z w y Z Z w P z y z Z B w 4 z z

CMH n u P u n 0 ^ w m 0 w « 0 a B B B n u y < B u B B Z H z 4

PQ V n »H NH n y B y B u B y B Z 1 X a zz B B u Z B B

y z M m z w • y W 4 y w 4 y i-j y y By z X P CM W y

o U y 4 o B 1 H o o n 1 o n M o B H O • B y o y B O B 44 B o B y H N M NH • R K in y c H N y a H N y H K y y X w 1 X 0) y X z

1 z B f- C *1 w y -H B y B y B CMw « B x4 •4 n u • t y w O V u •* y u u y 0 y y y • 4 U 4 •a 0 4 •• y 0. n y < B y < y 4 y •< 10 >« p4 m«4 B fO ^ B

H B n* H n* !»> P> B 0 B X B X

n o U B y n B B y y y y y

u z >4 y z y y y 44 W z w z
appendix::

conversion

tables

EQUIVALENT

SECOND

ORDER

RATE

CONSTANTS

163

«lBOOVOc9U r-l

CO

u o o

<4-1 uo

4Jo ; cd I- <4-1 ( •I G 4 O F 2 ' O <-( > I C ( O 1-1 U I

0) o

•c

B

4J CO 6

*oc o

•H 4J iM

1-^ «Q| I

0) I <0 0) ^ GO C 0)

«d o 2"b:

os

M

4J 0) ^ > B B 9 OU

M-1O

O

00

0)

M Ps ,D C

(d 4J

COGOo

Cd P>

4J%GOo i

'Oc

cd

o> 4=u

4-1OO

cd (S

0)

CO

Cd S

Cd Oo

0)G

0)50O6oX

0)6PO>

COGo

•H

4JO

cd

0) od

0)D

JJ

cd

d)CLB

<u H

.c:50

-r4 Xuo

4-1

cd • 4J CN

Cd r- Q ON

1-^

O

-r-l •v U c

0) 0 G •dG

d) •s 4J CO

cd pC 9 iJu

cd o > h a

d>

4-) o 4J u d

4-1 PQ T3

d)

a

U

d

a, 4J

Cd CO •o Ps

cd CO

d)

t»4

O1 cd CN H X
EQUIVALENT

THIRD

ORDER

RATE

CONSTANTS

164

See

note

to

Table

for

Second

Order

Rate

Constants
MBS-114A '^cv. ••7ti

U.S. DE.PT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NBSIR 79-1941

Z.Gov’L Accession Nc. 1. R-»ciCipnt’$ Aeceroion No.

j

4, TITLE AND SUBTITLE S. Publication Date Table of recommended rate constants for chemical reactions

occurring in combustion

Nov. 1979

i. Performing O'ganiution Co<ie

7. AUTHOR(S)

Francis Westley

8. Performing Organ. Report No. EA-77-A-01-0610

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

10. Projecl/Task/Work Unit No.

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS rSfre.r, Citr. Sisia. 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

Final

1950-1975

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

] Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or loam factual aummary of moat aighificant information. If document ineludea a aignificant bibliography or

literature aurvey, 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 = AT°exp(-E/RT) . The table covers reactions occurring in the combustion,

oxidation and decomposition of aliphatic saturated or unsaturated C, to C^q

hydrocarbons, alcohols, aldehydes, ketones, thiols, ethers, peroxides, amines.

amides and their free radicals, as well as HpO, HpOp, N, N«. NO, NnO, NOo, N^O., N^O

each other. Th

the reactions of 0, O

2

, H, OH,

NO, NpO, NO., N.0,, N.O., S, S., SH, SO, SO., SOH, NS, with

table Includes approximately 170 first order reactions

760 second order reactions and 50 third order reactions. There are 1805

entries covering about 1100 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 (aix to twelae antriea; alphabetical order; capitalize only the firat letter of the lirat key word unleaa a proper name;

aeparaied by aemicolona)

Arrhenius parameters; combustion; decomposition; free radicals; hydrocarbons;

hydrogen; nitrogen; oxidation; oxygen; oxygenated; organic compounds; rate

constant; sulfur

18. AVAILABILITY XX) Unlimited

I

I For Official Distribution. Do Mot Release to NTIS

I Order From Sup. of Doc., U.S. Government Printing Office, Washington, DC

20402, SD Stock No. SN003-003-

^ Order From National Technical Information Service (NTIS), Springfield,

VA. 22161

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF

PRINTED PAGES

169

22. Price

USCOMM-DC
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