NATL INST. OF STAND & TECH R.LC.

a 1 1 1 o s STaaot publications

NBSIR 81-2254

Tables of Experimental Rate

Constants for Chemical Reactions

Occurring in Combustion

(1971 - 1977)

Francis Westley

Chemical Kinetics Division

Center for Chemical Physics

National Measurement Laboratory

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

April 1981

Interim Report

Prepared for

Department of Energy

Washington, DC 20545

and

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81-2254

1981- - c.2

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234
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NBSIR 81-2254

TABLES OF EXPERIMENTAL RATE

CONSTANTS FOR CHEMICAL REACTIONS

OCCURRING IN COMBUSTION

( 1971 - 1977)

Francis Westley

•ATIOMaL *U*4*U

OF OTaKDA&D*

LMMUftT

JUN x o 1981

noVoiCc

QlC^IOC

J

Chemical Kinetics Division

Center for Chemical Physics

National Measurement Laboratory

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

April 1981

Interim Report

Prepared for Department of Energy

Washington, DC 20545

and

Office of Standard Reference Data

National Bureau of Standards

Washington, DC 20234

U.S. DEPARTMENT OF COMMERCE, Malcolm Baidrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
A.*.*-,* **

t *v'>k .••••’« * -s if*****- -
Table of Contents

Abstract

Introduction

Guidelines for the User

Table of Arrhenius parameters for chemical reactions

occurring in combustion

Reactions of: 0

°2 * °3 *

H. .

h

2

. OH . ho

2

.

h

2 o.

h

2 o2 s.

S

2

SO

so

2

SH

h

2

s

N.

N

2

. NO . no

2

. NO..

n

2 o. N.O. 4N 2°5

NH . nh

2

. nh

3

. NHNH

nh

2 nh

1

2

3

20

20

38

47

52

70

73

88

92

93

94

97

97

97

100

100

101

103

104

113

121

122

125

125

125

126

126

127

129

129
NH 2

NH 2 129

HN 3

130

HNO 130

HN0 3 131

HN04

132

C-j compounds 133 C 2 compounds 163 C 3 compounds 18* C 4 compounds 195

Cg compounds 213

Cg compounds 222 C -j compounds 230

Cg compounds 231

Cg compounds 233

C-jq compounds 234

List of References 235

Appendix: Conversion Tables 296
1

TABLE OF EXPERIMENTAL RATE CONSTANTS FOR CHEMICAL

REACTIONS OCCURRING IN COMBUSTION

(1971 - 1977 )*

Francis Westley

National Bureau of Standards

Chemical Kinetics Division

Center for Thermodynamics and Molecular Science

Washinaton, DC 20234

A table of exoerimental rate constants for aas nhase chemical reactions

occurrinq in combustion is oresented. Specifically, it qives in tabular

form the values of the parameters for the modified Arrhenius equation

g

k = AT^exol-E/RT) . The table covers reactions occurrinq in the combustion,

oxidation and decomposition of aliohatic saturated or unsaturated C-j to

C-jg hydrocarbons , alcohols, aldehydes, ketones, thiols, ethers, peroxides,

amines, amides and their free radicals, as well as the reactions of 0, 0^,

H, , OH, H2O, ^ 2^2 5 NO, N2O, NO25 ^2^4* ^

2 ^ 5

5 ^ 5 ^2 5 ^ 5 ^ ’ ^®2 5

SOH, NS, with each other. The table includes 220 monomolecular, 1092 bimolecular,

and 108 termolecular reactions totalling 1420 distinct chemical reactions.

There are 2608 distinct entries, distributed as follows: 308 for first

order reactions, 1984 for second order reactions and 316 for third order

reactions. The kinetic data were comoiled from 843 exoerimental oaoers

published between 1971 and 1977.

Key words: 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.
2

INTRODUCTION

This publication consists of a table of experimental reaction rate

constants for the combustion, oxidation and decomposition reactions of

aliphatic saturated and unsaturated hydrocarbons, their ox.yqenated sulfur

and amino derivatives, as well as for the reactions of hydrogen, nitrogen

oxyqen, sulfur and their inorganic derivatives with each other. The table

is a comDilation of exDerimental rate constants given in 843 oapers

published between 1971 and 1977. 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 2608 distinct reaction rate constants from these 843 experimental

papers. A list of references including the 843 papers, arranged alphabetically

by author for each separate year, is appended at the end of the table.

For each of reference the bimolecular and termolecular reactions included

in the table are listed separately under each reactant, so that a grouping

of the reactions according to the first reactant is obtained. As a

result, the total number of tabulated entries is 4425, although the real

number of distinct entries if 2608.

The presentation of kinetic data is standardized and simplified as

much as oossible. Rate constants are expressed in the modified Arrhenius

n 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

Dmol~

_ s~ for reactions

of first, second and third order resDecti vely.
3

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 aopended at the end of this publication.

The arranqement of the tables is described in detail below, in the

"Guidelines for the User".

It is honed 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 Drocesses.

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. Hamoson, Jr., Director of the

Chemical Kinetics Information Center, for their more than helpful suggestions

and constant guidance; Dr. Wing Tsana, 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. 3ettijoyce Molino and Mrs. Carla G. Messina from the Office of Standard

Reference Data for apDlying the OMNIDATA and GPSDIC programs to the present

tables: Mrs. Geraldine Zumwalt, Miss Natalie C. Atkins, and Mrs. Janice L. Jones

for punching and tyoing 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
4

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 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

1 imi ts

.

It is thought that the uncertainty limits expressed in the form of

lower and upper k factors - f and F, respectively - are the most suitable for

tabulation. Thus, if k

Q

is the central value of a rate constant the

limits of reliability for the rate constant k

Q are defined by the

rel ationsni p

fk

Q

< k < Fk

0 (1)

i.e. multiplication of the central value k Q 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
5

the different forms of uncertainty limits into the standard form used in

this table (lower and uooer k factors). The transformation formulas are

given and discussed below.

In general there are two wavs to state uncertainty limits: 1) by factors

and 2) by algebraic addends

Uncertainty expressed by factors .

Beside the standard form of uncertainty limits expressed by the lower

and upoer factors f 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 k

Q

is the central value of a rate constant, the statement

that k

Q

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

are defined by the relationship:

k

0

/F < k < k oF (2)

which shows that division and multiplication of the central value k

Q

by F gives, respectively, the lower and uooer reliability limits of the

rate 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 alaebraic addends, which are currently used by kineticists:

a) . Uncertainty appended to one of the Arrhenius factors (A, B, or E/R)

;

b) . Uncertainty appended to log -|n^ 0

i and c). Uncertainty expressed as a

percentage of k . With respect to the type a) uncertainties, the B factor
b

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 = axl

0

n (4)

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

10. If an uncertainty +a‘ is appended to the coefficient a, the A factor

takes the form:

A = (a + a

1 ) x 10

n (5)

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

takes the form:

A = fa x 10

n (6)

or A = Fa x 10

n (7)

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 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
7

b). Uncertainty appended to 1oq -| Q

k Q

. If k

Q

is the central value of

a rate constant, C its logarithm to the base 10 and D the uncertainty expressed

as an alqebraic addend to C, then the following relationship is true:

log-j gk = C + D (10)

where C = lon-jQk . If D is out in logarithmic form, say:

D = log-, qF 01)

then relationship (10) becomes:

log

10

k = log

10

k

Q + log

1Q

F (12)

which can take the form:

lo9lO

k

O

/F < log 10k < lo 9lOFk

O

° r k./F < k < Fk

O 0 (13)

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

k factors f and F are the antil ocarithms of -D and D, respectively

f = antilog (-D) = 10

_D

(14)

F = antiloaD = 1

O

3

05)

Formulas (14) and (15) are the relationshios needed to transform

the type b uncertainties into reliability limits expressed by k factors.

A numerical example follows:

log

lQ

k = 14.23 + 0.3 therefore: f = 10~ 0,3

= 0.5 and F = 1 0°* 3 = 2.0

c). Uncertainty expressed in percentage of k . Some kineti cists

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 k

Q are defined by the relationship:
8

k

Q

- ( p/1 00)

k

Q

< k < k

Q + ( p/1 00)

k

Q or (1 - p/1 00)k

Q

< k < (1 + p/1 00)k

Q (16)

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

(1 - r)k

Q

< k < (1 + r)k

Q (17)

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

formulas:

f = 1 - r 08)

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

follows:

k = 3.7 x 10^ + 20% therefore p = 20% and r = 0.2

Thus: f = 1 - 0.2 = 0.8

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.

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 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
9

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 = 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.

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 = 1/F = 0.83 while F' = 1/f = 1.25.

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

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

f' = 1/F = 0.71 and F' = 1/f = 1.67.

The two pairs of factors, (f 1 = 0.71); F = 1.4 and f = 0.6; F

1 = 1.67)

are significantly different. Again, it is safer to choose the pair 0.6
10

and 1.67, by enlarqinq the uncertainty ranqe. And, since the concepts

of uncertainty and reliability are opposite to each other, enlargement of

the uncertainty ranqe 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, arranqed in six columns including the chemical

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

g Arrhenius equation k = AT exo(-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 843 experimental naoers from which the present table wa s compiled.

Followinq the bibl iograohy, two conversion tables for equivalent second

and - respectively - third order rate constant units are appended. The

contents of part I are described in detail below:

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 qiven. 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 resoect 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 bv 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 resoect to the line above it. E.g. :
11

74 HER/HU I indicates the review of rate constants for the

reactions between aliphatic hydrocarbons and

atomic oxvqen, published by Herron and Huie

in 1974.

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 diqits 1, 2, or 3. As pointed out in the introduction, the order

of reaction indicates the units for the rate constants as follows:

1 for first order reactions s"^

3 -1-1

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 Dartner ("third body") is indicated by the letter M:

followed by its chemical formula. E.g.: M:Ar or f^CC^. No indication

is given if M is undefined, or if the reaction does not include M.

For a number of reactions, no Arrhenius parameters are indicated.

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

resoect to the rate constant of a reference reaction is given. This

information follows the reaction order information, on the same line,

and is indicated by the symbol k/k followed by a number.

E.n.: k/k fef

: 0.59.

The last line of column 1, olaced under the line including the

short reference and reaction order information, begins with the heading

NOTE: It is niven only when necessary and might include information
12

about the dependence of k factors on temperature range, or the reaction

taken as reference when the ratio k/k

re ^ is niven in the previous line, or

other information pertinent to the reaction indicated above. The rate

constant, k .p, 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 the relationship k-j = K k_-j included in the note indicates

that the respective rate constant was calculated from the equilibrium

constant K and the rate constant k_-j 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

next section) 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 dearees Kelvin the

temperature ranae of validity of the corresoondina rate parameters. For

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

was studied only at one temperature. The temperatures are alined with

the short reference and the reaction order information.

Column 3 , with the headinc A, gives the value of A for the equation

g

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

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

inteqer preceded by the siqn +, or -. The number less than 10 is the

coefficient of the A factor, while the inteaer inside the parenthesis is

the exponent of 10. Therefore, e.q., 3.5 (+ 14) should be read as

+ 1

4

3.5 x 10 . The coefficient of the A factor has no more than one digit
13

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. For those cases when the recommended value is only 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 4 , 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 4. 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 point. If in this column

a dash appears instead of a figure, it means that no B value was reported

by the evaluator for the correspond! ng 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 values 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 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 indicated in the right
14

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 subheading, "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

Q

. 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

i nformation.

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 Mote 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

*). Wagman, D. D., Evans, W. H. Parker, V. B. Halow, I., Bailey, S. M.

,

and Schumm, R. H., "Selected Values of Chemical Thermodynamics

Properties," NBS Tech. Note 270-3 pgs. 5, 16, 22 (1968).
15

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). H_-0 system, 3). S-O-H system, 4). N_-0-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, 0 9 , 0^.

2)

. H_-0 system: H, OH, H02> H

2

O, H

2

O

2

.

3)

. S_-0-H system: S, $

2

, SO, SO

2

^ S0

3

, SH, SH

2

> SOH.

4)

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

2

, NO, N0

2

, NO-, N

2 0, N 2

0

4

, N

2 0

5

, NH, NH

2

,

nh

3

, n

2 h4

, nh

3

, HNO , hno

3

, NS.

5)

. C_-0-H-S-N system: C-| compounds: C, CO, CH, CH

2

, CH

3

, CH

4

, CHO,

HCHO , CH

3 0, CH

3

0H, CH

3

00H, CS , CS

2

,

cos, ch

3

s, ch

3

sh, cn, c(no

2

) 4

, CHN,

CH

3

NH

2

, CH=N=N, CH

3

NHNH

2

, CH

3

NO s

CH

3

N0

2

, ch

3 no

3

, ch

3

onh 9

.
16

C£ compounds: ^2^’ CH=CH, CH

2

=CH

2

, CH

3

CH

2 *,

CH^CH^j CH

2

= C= 0 , etc.

compounds, etc., up to compounds follow,

being ordered according to the same

pattern.

It is clear now that, for instance, the compounds included in the S_-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

system (0-system and H_-0 system). It is to be noted that for the C_-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 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 CH^ + 0 CH^ + OH, is inserted in the C_-0-H-S-N system.

This reaction may also be written as 0 + CH^ -* OH + CH^ 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 CH^ 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 1092 reactions listed in the table, having as reactants two distinct

chemical compounds. Since each of these reactions is inserted twice,
17

the number of entries for them will amount to about 2000. Only a small

number of termolecular reactions has three distinct reactants. As an

example, one of them is NO + N0

2 + 02 ^0^. This reaction will also

be inserted under the forms: NO

2 + NO + O

2

+ N

2 03

and O

2 + NO + NO2 -

N^Og - 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

3 + M - 0 + 0

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

3

CH

2

CH

2

CH

3 + H + CH

3

CH

2 CH2 CH2* + CH

3

CH

2

CH( • )CH

3 + H

2 (20)

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

the two reactions

CH

3

CH

2 CH

2 CH3 + H + CH

3

CH

2 CH2

CH

2

* + H

2

_( 21 )

and CH

3

CH

2

CH

2

CH

3 + H -> CH3

CH

2 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.

CH

3 + (CH

3

) 2 CHCH(CH

3

)CH(CH

3

) 2 - CH

4 + [CqH-j

7

• ] (23)
18

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:

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^j CH^CI^CH^ CH^CF^CF^CHo ,

The unsaturated hydrocarbons are written so as to show the position

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

(CF^^C = CFICFI^ + N products (24)

Display of Chemical Reactions and Formulae .

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

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

Ethyne (Acetylene)

1 ,2-Propadiene (All ene

)

1 ,3-Butadiyne CFl=CC=CFi

ch 2 =c=ch

2

CH=CH

ci s-2-Pentene cis-CH

3

CH

2 CH=CHCFi

1 -Heptene ch

3

(ch

2

) 4

ch=ch

2
19

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

indicated, with the exception of Methyl free radical. E.g.:

Methyl free radical CH

3 (no dot)

Ethyl, 1 -methyl-, free radical

(Isopropyl) (CH^^CH*

Methyl, hydroxy-, free radical *CH

2 0H

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 ) CH

3 CH

2 CH( • )CH

3 Butyl, 1 ,1 -dimethyl - , free radical

(2 -Methyl - 2-pentyl ) CH ? CH

2 CH2 C( *

) (CH

3

) 2 Methyl, oxo-, free radical (Formyl)

(i s 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:

CH

3 0. 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

3

) 2 C(0* )CH

? CH 0

.

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

and other free radicals are the same as for the oxy free radicals: CPUCL*,

CH,S-

.

Atoms, like 0, H, S, N, and simple radicals like OH, H0 ?

, SH , NH,

CH, CH

2

, CHo, CN are written without dot.
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Ualokhnln,

V.

P.,

and

Egorov,

V.

I,,

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investigation

of

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72

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Cox,

K*

A.,

and

Penkett,

S*

A.,

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from

Sulphur

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in

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72

P^IR/SNE

Fortin,

C.

J.

Snell

Ing,

D.

R.»

and

Iardlf,

A.,

"The

Ultraviolet

Flash

Photolysis

of

Ozone

and

the

Reaction

of

Ol

*UI

with

ll^O."

Can.

J.

Chem.

2747 (

1972)
243

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and

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N.,

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nnd

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with

N(^*i),"

Client,

Phys,

Lett,

12.

607 (1

973 )
73

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Castellano,

E.,

und

Schumacher,

II.

J.,

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unil

dtr

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dea

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Ollft/ELI

Ghormley,

J.

A..

Ellswortli,

R«

E.,

end

Hochanadel,

C.

J.,

"Reaction

of

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with

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Hate

Const

for

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of

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with

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Oxide

and

with

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Dioxide

J.

Phys.

Cl

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22.

1341 <1

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69

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2124

(1973)

73

JON/HAlfl

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!.

T.

N..

and

Hayes,

K.

D.,

“Free-Radical

Formation

In

the

O

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Synip,

Combust.

jLi

•

(Combustion

Institute

Pittsburgh,

p

a.,

1973)

277

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I,

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Am.

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Soc

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97

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4504

(

1975)

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J

• F

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Helcklen,

J.

,

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the

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of

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J.

Photochem

455

(

1975

)
75

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Mendenhall,

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D.,

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D.

M.,

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Benson,

W

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J.

Chen,

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I,

725

11975)

275

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APPENDIX.;

CONVERSION

TABLES

296

System,

But

te

rwor

ths,

London,

1972.
EQUIVALENT

THIRD

ORDER

RATE

CONSTANTS

297

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NBS-114A irev. 2 -eci U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO. NBSIR 81-2254

2. Performing Organ. Report No . 3. Pub! i cation Data

4. TITLE AND SUBTITLE ^ , , * • , Table of Experimental Rate Constants for Chemical Reactions Occurring in Combust >r (1971 -1977)

5. AUTHOR(S)

Francis Westley

6. PERFORMING ORGANIZATION (If joint or other than N BS,

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

see in struction s) 7. Contract/Gram No.

8. Type of Report 3. Period Cove r ed

1 9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. Stale. ZIP, Department of Energy, Washington, DC and

Office of Standard Reference Data, National Bureau of Standards, Washington, DC

10. SUPPLEMENTARY NOTES

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

11. ABSTRACT (

A

200- word or less factual summary of most si gn i fi cant in formation . If rlocumen t includes a significant

bi bl iography or literature survey, mention it here) A table of experimental rate constants for gas phase chemica'' reactions

occurrina in combustion is nresented. Specifically, it gives in tabular

form the values of the parameters for the modified Arrhenius equation

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

oxidation and decomposition of aliphatic saturated or unsaturated C-j to

u, n hydrocarbons, alcohols, aldehydes, ketones, thiols, ethers, r

_. amines, amides and their free radicals, as well as the reactions of 0, J-’

H, HL, OH, H~0, HpOp, N, N~> NO, N

2 O, NOoj N^O. , ‘^2^5’ ^2’ ’ ^2’

SOH, NS, witn eacn other. The table includes 220 monomol ecul ar , 1092 bi~c

and 108 termolecular reactions totalling 1420 distinct chemical reactions.

There are 2608 distinct entries, distributed as follows: 308 for first

order reactions, 1984 for second order reactions and 316 for third order

reactions. The kinetic data were compiled from 843 experimental papers

published between 1971 and 1977.

12. KEY WORDS (Six to twelve entries; alphabeti cal order; capitalize only proper names; and separate key words by : e— co o^s

Arrhenius Darameters, chemical kinetics, combustion, decomposition, ^ree rad' cals,

gas ohase, hydrocarbons, hydrogen, nitrogen, oxygen, rate of reaction, su."ur

13. AVAILABILITY 14. NO. OF

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C /\J ~! Order From Superintendent of Documents, U.S. Government Printing Off; 20402.

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