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NATIONAL BUREAU OF STANDARDS REPORT

9884

A COMPENDIUM OF

EVALUATED AND ESTIMATED RATE COEFFICIENTS

July 1968

This project is an activity of the Chemical Kinetics Information

Center, N.B.S. The work was supported by the Naval Ordnance

Systems Command ORD 3311 as part of a program to foster the

production of tables of chemical kinetics.

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

i
THE NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards1 provides measurement and technical information services

essential to the efficiency and effectiveness of the work of the Nation’s scientists and engineers. The

Bureau serves also as a focal point in the Federal Government for assuring maximum application of

the physical and engineering sciences to the advancement of technology in industry and commerce. To

accomplish this mission, the Bureau is organized into three institutes covering broad program areas of

research and services:

THE INSTITUTE FOR BASIC STANDARDS . . . provides the central basis within the United

States for a complete and consistent system of physical measurements, coordinates that system with the

measurement systems of other nations, and furnishes essential services leading to accurate and uniform

physical measurements throughout the Nation’s scientific community, industry, and commerce. This

Institute comprises a series of divisions, each serving a classical subject matter area: —Applied Mathematics—Electricity—Metrology—Mechanics—Heat—Atomic Physics—Physical

Chemistry—Radiation Physics—Laboratory Astrophysics2—Radio Standards Laboratory, 2 which

includes Radio Standards Physics and Radio Standards Engineering—Office of Standard Refer- ence Data. THE INSTITUTE FOR MATERIALS RESEARCH . . . conducts materials research and provides

associated materials services including mainly reference materials and data on the properties of materials. Beyond its direct interest to the Nation’s scientists and engineers, this Institute yields services

which are essential to the advancement of technology in industry and commerce. This Institute is or- ganized primarily by technical fields: —Analytical Chemistry—Metallurgy—Reactor Radiations—Polymers—Inorganic Materials—Cryogenics2—Office of Standard Reference Materials.

THE INSTITUTE FOR APPLIED TECHNOLOGY . . . provides technical services to promote the use of available technology and to facilitate technological innovation in industry and government. The

principal elements of this Institute are: —Building Research—Electronic Instrumentation—Technical Analysis—Center for Computer Sci- ences and Technology—Textile and Apparel Technology Center—Office of Weights and Measures —Office of Engineering Standards Services—Office of Invention and Innovation—Office of Vehicle

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Evaluation Laboratory—NBS/GSA Testing Laboratory.

1 Headquarters and Laboratories at Gaithersburg, Maryland, unless otherwise noted; mailing address Washington, D. C., 20234.

2 Located at Boulder, Colorado, 80302.

3 Located at 5285 Port Royal Road, Springfield, Virginia 22151.
NATIONAL BUREAU OF STANDARDS REPORT

NBS PROJECT NBS REPORT

316.51-11-316.0520 9884

A COMPENDIUM OF

EVALUATED AND ESTIMATED RATE COEFFICIENTS

Edited By

David Garvin

Institute for Materials Research

July 1968

This project is an activity of the Chemical Kinetics Information

Center, N.B.S. The work was supported by the Naval Ordnance

Systems Command ORD 3311 as part of a program to foster the

production of tables of chemical kinetics.

IMPORTANT NOTICE NATIONAL BUREAU OF

for use within the Governmen

and review. For this reason, whole or in part, is not autl Bureau of Standards, Washin

the Report has been specitica

Approved for public release by the

Director of the National Institute of

Standards and Technology (NIST) on October 9, 2015

»ress accounting documents intended

is subjected to additional evaluation

ire listing of this Report, either in the Office of the Director, National

', by the Government agency for which

I copies for its own use.

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS
/
TABLE OF CONTENTS

i CHAPTER 1: INTRODUCTION 1-1

CHAPTER 2: PRESENTATION OF RATE EVALUATIONS 2-1

CHAPTER 3: ORGANIZATION OF THE REPORT , 3-1

A. General Description * 3-1

B. Processing of the Original Data:

Uncertainties and Significant Figures 3-2

CHAPTER 4: TABLE OF RATE COEFFICIENTS 4-1

A. Guide to the Rate Coefficient Table 4-3

B. Conversion Factors, 4-4

C. List of Chemical Formulae 4-5

D. Table of Rate Coefficients 4-7

CHAPTER 5: RATE EVALUATIONS AND REACTION SUMMARIES 5-1

A. Kinetics Tables for the Reactions of Hydroxyl Radicals

by Wm. E, Wilson, Jr 5-2

CO + OH = C0

2

+ H 5-3

H

2 + OH = H + H

2

0 5-14

OH + OH = H

2

0 + 0 5-24

CH. + OH = CH0 + Ho0 5-30

4 3 2

B. Kinetics Tables for the Reactions N + 0 = NO + 0 and

NO + 0 = N + 0

2 by Wm. E. Wilson, Jr. and David Garvin.... 5-38

C. Reaction Summaries for

H + 0

2 = 0 + OH 5-47

H

2

+ M = H + H + M 5-51

H

? + 0 = H + OH . 5-55

0

2 + M = 0 + 0 + M... 5-58

0o +M=0 + 0 o +M and 0 + 0„ = 0 o + 0 o .... 5-62

CHAPTER 6: GENERAL NOTE CODES 6-1

CHAPTER 7: SPECIFIC NUMBERED NOTES FOR THE TABLE OF RATE

COEFFICIENTS 7-1

CHAPTER 8 GENERAL BIBLIOGRAPHY « fc 8-1
I

1

.
1-1

CHAPTER 1: INTRODUCTION

This report is an annotated handbook on rates of elementary gas

phase reactions. It is limited to rate evaluations. No attempt has

been made to record all research papers pertinent to a particular

reaction. There are two principal parts to the report, a compilation

and a set of rate evaluations.

The compilation merges the information presented in several recent

journal articles and reports that are devoted to the evaluation or estimation of rate coefficients for elementary reactions. A single table,

arranged by reaction, lists the various recommended rates in a common

format. Notes to the table show what data sources were used by each

evaluator, and, where possible, how his recommended value was determined.

The person requiring a rate for a specific reaction may compare the

recommendations, compare their data bases and also extract a bibliography

of the pertinent work.

The rate evaluations, which are presented in full, stand independent

of the main table. They are for reactions of some importance to combustion and atmospheric chemistry. They are presented in a form suited to

the reaction-by-reaction evaluation of rate data as opposed to that used

in monographs. It is hoped that they will serve as models, albeit ones

to be improved upon, for future rate data examinations.

It is also hoped that this technique for presenting rate evaluations,

either one or a few reactions at a time, will find favor among kineticists.

The labor involved is modest, particularly for the scientist who needs to

review previous work during the design of his own experiments. Such evaluations would be welcome additions to later editions of this report. It

is only by a cooperative effort that the basic kinetic data used in

applied research and technology can be improved significantly in a reasonable time.

The restriction to evaluated material means that the values listed

here are the results of a process of reexamination of available data. One

may hope that there has been a detailed examination of the data and a comparison with the behavior of similar reactions. That is, that the purview
1-2

of the evaluator may be broader than that of the experimenter. The

results of such reexamination may be a selection, a composite of acceptable data, a calculation, or, in the absence of other guides, a guess.

Evaluation, particularly when the data are few, seems to be a highly

subjective process. The skills developed during the examination of

many reactions are applied * The quality of the work and the reliability

of the results are highly variable.

The reader must be warned that this compilation is incomplete.

Worthy candidates for inclusion, both new and old continue to come to

our attention. It became apparent that no reasonable terminal date

could be set for the preparation of the material from all available

sources. Arbitrarily, it was decided to issue the material prepared by

the end of June 1968 and then continue the collection of data.

This implies that the report may be revised, expanded and reissued.

That is our intention, should the work prove useful. It is also our

hope to provide not only a current table of rate data but to offer an

outlet for the presentation of rate evaluations. To these ends the

principal table and the bibliography have been prepared in machine

readable form and are stored on magnetic tape. Eventually most of the

other material will be transcribed. It will be possible to produce

upon demand a current version of the main table and the bibliography

as computer printout, magnetic tape records or on cards. The numberical

material is arranged in fixed locations so that it may be used directly

for input to computation programs.

Suggestions for improvement and correction and contributions of

evaluated material will be welcome. Without readers and readability a compilation of this type serves no purpose.
1-3

Acknowledgments

The proposal made by Dr. Charles W. Beckett and by the ad_ hoc

committee chaired by Dr. Robert M. Fristrom that kinetics tables

analogous to the JANAF Thermo chemical Tables are needed provided the

initial impetus for this work. Both Drs. Beckett and Fristrom have

offered encouragement and valuable acvice.

The work was made possible through financial support by the Naval

Ordnance Systems Command, ORD 33 11, for this project and by the Office

of Standard Reference Data, NBS and the Advanced Research Projects

Agency for the operation of the Chemical Kinetics Information Center.

Dr. Leroy Schieler gave us a punched card file of the contents

of the extensive Aerospace Corporation compilation. This formed the

starting point for our table of rate coefficients. Correspondence

with Dr. Schieler, Dr. S. S. Cherry and Mr. G. S. Bahn has been of

assistance in interpreting their reports. Dr. Wm. E. Wilson has provided the rate evaluations in Chapter 5. These are based on earlier

reports but have been rewritten extensively for this collection.

The organization and preparation of the report has been the

province of Mrs. M. C. Peter. Preparation of computer-based table

in Chapter IV and of the bibliography was carried out in the Chemical

Kinetics Information Center under the supervision of Mr. James G.

Koch, Sr. The bibliography was typed and cross checked by Mrs.

Robert M. Henderson, Computer programs for calculating and converting

rate coefficients while controlling significant figures were designed

and written by Clayton L. Albright and J. Robert Arms of the Computer

Services Division, NBS.

To all of them go our thanks for able and good natured advice and

aid

2-1

CHAPTER 2: PRESENTATION OF RATE EVALUATIONS

This part records suggestions about the content of a rate evaluation and the form in which it is presented. No new features are suggested, each appears in some report, but all rarely appear in the same.

The remarks are not based upon experience in making rate evaluations

but on that accumulated in using them. As is so often true, it is the

failures that lead the user to suggest.

Potential users have made suggestions. An ad hoc committee on

chemical kinetics data dissemination sponsored by the JANAF Thermochemical Panel made the following suggestions in April 1967.^ The committee

had in mind the production of data sheets, each to be devoted to a single reaction. The model in view at the time was N. H. Pratt's

2 compi lation.

a. That evaluations of both the forward and reverse reactions of

a system be presented together.

b. That the results of each research paper be included in a table

together with their temperature ranges and limits of error when known.

c. That all results be presented in a consistent form and the

same set of units. The recommended form for rate expressions is k = AT

8 exp(-C/T). The values of the rate parameters should be consistent

with time in seconds, temperature in Kelvin, and concentration in molecules (particles) per cubic centimeter. It was recommended that the

activation energy term be reported in the form C = E*/R, where E* is the

activation energy and R the gas constant.

d. That each rate coefficient expression be accompanied by a value

for a common reference temperature.

e. That the tabulated results and the recommended expression be

displayed in graphical form.

f. That equilibrium data be included.

1. ’’Report on the Establishment of Chemical Kinetics Tables”, Chemical

Propulsion Information Agency, unnumbered report, April 1967, p. 16.

2. Pratt, N. H., ’’Some Chemical Reaction Rate Data for Gas Dynamic

Studies”, National Gas Turbine Establishment (Pyestock, Hants,

England), unnumbered report, October 1963.
2-2

}

' These are good guides. They allow the evaluator ample scope. Tha

3 ideas have been used effectively for some years. Kaskan and Browne and

4 Schofield demonstrated the effective use of figures in rate evaluations.

The latter provided easy to use tables. The recent report‘d f rom t he

University, Leeds, ha& an exemplary format. All of these merit study by

the potential evaluator. A few additional suggestions are offered below.

Make an evaluation complete enough so the reader will have little

need to examine the original papers. If this can be done, matters of

form become secondary. Make it unnecessary for the next man to redo

the work. With this in mind:

a. Tabulate data points where ever possible. If necessary, scale

them from figures

b. Base the evaluation on data points if possible. Rate coefficients are usually more reliable than rate parameters.

c. Summarize how the results were obtained in each study and record

an opinion on the work. Comparison of several papers often reveals possible flaws. That not obvious to the casual reader comes to light.

d. Explain how the recommended value was obtained. Give temperature

limits and uncertainties.

e. Graph the material. There is no more useful form of presentation. New data can be easily added and assessed.

f. Cite the sources actually used. Cite B, not A, if B’s summary of

A

1 work was consulted. Explain recalculations and non- trivial conversions.

g. Discuss the reaction at any suitable length. Spend space to save

future effort.

3. Kaskan, W. E. and Browne, W. G., General Electric Company Space Sciences Laboratory Report R64SD37, July 1964.

4. Schofield, K., Planet. Space Sci. 13

643 (1967).

5. Baulch, D. L., Drysdale, D. D., and Lloyd, A. C., "Critical Evaluation of Rate Data for Homogeneous Gas -Phase Reactions of Interest in

High Temperature Systems", Dept, of Physical Chemistry, The University,

Leeds, England, High Temperature Reaction Rate Data Report No. 1, May

1968.
3-1

CHAPTER 3: ORGANIZATION OF THE REPORT

A. General Description

The bulk of the report is a table of rate coefficients (Chapter

*

i 4). This is the main entry point for the reader, A guide to the

arrangement of the table is given at the beginning of Chapter 4, The

table is followed by a group of "Reaction Summaries" (Chapter 5), Five

of these are rate evaluations. The others are collections of notes

about reactions that have received considerable attention. They are not

single summaries, one per reaction, but are separate notes, one per

evaluation. These notes are gathered together for convenience. Each

collection shares a common reference list.

Chapters 6 and 7 contain notes to the main table. These are of

two types: general and specific. The gene ral notes in Chapter 6 are

explanations of abbreviations used throughout the main table. These

categorize the basis used by the evaluator in developing his recommendation. The specific notes , Chapter 7, are arranged in separate sets

for each source quoted in the main table. A complete identification

of the papers is given at the start of the section. The sets of notes

are ordered alphabetically by author. Wherever practical the notes are

those given in the papers, rewritten to meet the needs of this larger

collection. In some cases they are interpretations of extensive material. In any case, the editor of this report, and not the original

author, is responsible for errors of fact and interpretation. Each

note has its own reference list. The citations identify the source,

but are kept brief.

The references cited are those given by the original authors. The

papers have not all been examined. Occasionally an obvious error has

been corrected and occasionally a citation has been expanded to include

companion papers. A few items remain for which the citations are incomplete or ambiguous.

Chapter 8 is a general bibliography, arranged by author. It lists

the articles referred to throughout the report. These citations are

intended to be unambiguous and complete. Most include titles.
3-2

B. Processing of the Original Data:

Uncertainties and Significant Figures

The data tabulated here came from diverse sources. The conventions

used by the authors varied. All data have been reduced to a common form.

These rules have been followed in processing the numbers:

1. A tabulated number should reflect the precision to which

the original number was stated*

2. Explicit uncertainties should be stated only when they

were explicitly stated for the original number.

3. Numbers received without stated uncertainties should be

treated as if they were precise to ±1 in the least

significant figure.

4. Calculations of rate coefficients using the tabulated

numbers should report results consonant with the uncertainties, explicit or implied, in the rate parameters.

5. The propagation of uncertainties, of whatever origin,

through a calculation may be treated by the same rule

as that used for standard errors:

W = f(x,y)

(J^ = (df/dx)^!^ Qf/^y)20

-2 w x y

\ where the sigma’s are the absolute uncertainties.

The use of this last rule does not imply that the stated uncertainties are standard statistical errors. Most of them are personal estimates.

The meaning of an uncertainty varies from source to source.

These rules pose no problems to the compiler who applies them in hand

calculations. However, when computer technology is introduced the rules

must be implemented explicitly case by case. This implementation has been

made and applied in the construction of the table. Hopefully, it may be

of use to others. The programming of this trivial problem revealed a number of machine -calculation pitfalls.
3-3

The rules stated above are an incomplete description of the

process. In some cases the input number was rounded before it was

accepted. These were cases for which the implied precision was

unbelievable. Also, the dividing line for bounding up is .505 not

.5. This assures that activation energy estimates of 5 and 6 kilocalories per mole (for example) will not, when divided by the gas

3

constant, both become 3 x 10 . The problem arises only for numbers

for which uncertainties were not stated.
J.j
4-1

CHAPTER 4: TABLE OF RATE COEFFICIENTS

Part D of this chapter is a table of rate coefficients for elementary gas phase reactions. There are over 1600 entries for about 1450

reactions. Each entry is an evaluation, a calculation, an estimate or

a selection recommended as the best available value.

The structure of the table is explained in Part A. Factors for converting the rate parameters are tabulated in Part B. The formulae for

the molecules that appear in the rate coefficient table are listed in

Part C in the order in which they appear. Chapters 6 and 7 contain supporting notes for the table.

Several points about the rate coefficients merit mention here.

(1) The form used for presenting the rate coefficients is

k = 10

A

T

B

exp (-1000 C/T)

Here the number C is related to the activation energy by

t 1000 C = E/R where 1 is the gas constant. For the kineticist,

who still compares activation energies in kcal mol ^ the conversion E = 1.987 C will serve.

(2) The calculation of a rate coefficient at a particular temperature from the tabulated data is most easily done using

log

10

k = A + B log

1Q

T - 434.3 C/T

(3) The preexponential term in the Arrhenius equation

k = a exp(-E/RT)

here becomes

i^A _B

a = 10 T

This term a is often used for rapid comparison of the kinetic

behavior of reactions. For any set of units a has a typical

range of values. These are shown below for the two common

sets of concentration units used in the original papers.
4-2

molecule cm

^ mol

-3

cm

First order io

10

- 10

16

io

10

- io

16

Second order io~

13

- io"

9

io

10

- 10

14

Third order ;’cf

32

- io’

30

10

15

- io

17

3 The table in Part D lists k’s consistent with molecules/cm . These

characteristic ranges are of help in interpreting a rate expression for

which no units are stated. This situation occasionally arises in the

notes quoted in Chapters 5 and 7. In passing it may he noted that

3 molecule/cm rate expressions have distinct ranges for values of a for

t reactions of different orders. The only other practical set of units

3

for which a has distinguishable ranges is mol/m , which, to date, has

been used very little.
Guide

to

the

Rate

Coefficient

Table

4-3 o

+icj'—oooax i g •

PQ

CO54G

44

cu

5-i

CCS PQ

CD

4-1

CCS pi O o o o O CM CM

-H

r—

• • X

II 00

r- a H • • 50 CO CO O 44 co CO

XI CCS i i © U

+1u

PQ

+1

PQ<

+1 $ 5- ^

in

i-v. ino 3L

CM CNJ

PQ 00 ! •H 54 6

44 o CO CM — rO CCS EH • • • J <3 54 p-4 <3 CCS as d PS co co co • • as 54 • •H i-O

—. 1 i i d 54 o. d d CCS <d as as a. d o d 44 +1 44 O- CCS cr •H as < CCS CCS CO 44 +4 50

54 r4 P4 CO CCS a d O as d d d PS 44 d cs as •H

l—

'TO 54 }4 54 x> I—

d •H *p4 pH d

54 CO CO CO ccS CCS ccS 44 i-4 •H

II O 44 d 44 d •H O s

•p-i a as 44 O 5-i -X as 50 CCS CO d as 54 •H as o as as 44

54 as o ccS 54 54 pH d 54 as O 500 ^ 

O o •H CCS d 44 d o J -A r-- } co i-4 d

CM

CO

as

4-1 O

cnO

II S 0

/^S d i CM d S v-/

CCS n- + <—

as CCS o

54 coo xb >

PQ

PSo A VO 00, CO II vO VO

CSV CT\| di—

Sj i—

u | Vi

•H +1 23

44 EH

CS CM o CO

CCS G

Pi O CO , ! < 4- PQ t o

23 = od

o>

CM

P-i X

r^. vO

CT>

PmOo

J1 do

•H

4-> O

ccS ai

5-4 g

co

5-4 as>

as

5-4

5-i O

<4-4

£]

eg

ps ; co

as,

<d CO • CO as as d d d r4

as •H as PS 44 1-4 PI- G

ccS PS as 44 d o r—

CO o 54 o

50 6

as d

}4 as as d

CCS 44 cs •H d 54 d *p4 PS d d 54 • o o

CCS P-i CO CO *p4 54 44

CO CO CCS as CCS as 44 as • r—|

54 •H o- a. VO 50 44

44d T3

CiccS 54 d

•H das

•rl a as CO o

CCS CO as 44 d • 44 X 44 pi- CCS o Eh

54 PS o ces o

as CO d 6

54 O cs • O d «—

CO <44 CO co 3 • 1 •rl as d • d X3 as CO d

as o o 44 co as o CO

54 •rl 44 a <r

eel 44 || d o as i CCS as • d CO i — PS 1 X3 CO U cr o & 54 pH d £h

as as i—

•H o d •• m X) <3 p-4 d as co g 50

ccS 44 44 54 3 e O

ecs as as d • •p-l t-4

— 54 44 r- 44 PQ

PQ o pi- d d ecs ce} as 54 n + as

4-1 PU

CCS dMd / \ O G

•p4 rH

•H XI

CCS CCS P> 4-1

54 as

as x!

4-1 4-1

1-4 <3

as

as6 C

ccS *H

5-4

CCS P- pH

4-1 as «h

4-1 O

CCS *H

54 i-4a

x: X o as •H

4-1 c • as

4-1 CO

<4-4 as

as 54a.C

as

CO §

4-1 C co

ccS as §

4-1 o

00

54

54 *p4 O 50 44

Pi d • d as d ° •£ o

•rl £ «p4 44 44

TCJ X O

PS pH ccS cr d as PQ o Pi • •

i-l CM

CCS ccS

54O

44

a,

ccS

as

as COd

as

4-1 o

PSa*

aso

542O

CO

co dO

•H

4-1

CCS PS i—

CCS >

0) Xo

CCS asdo

COas

4-1 odo

°r4 44

•i4G

asOCO

54O

44

CO •H

CO

cc) X>

50d

•r4 •H

54G

CO

as d

as

4-1 od

ccS 54

asa

as O

ccS d > -H

as

co

co 5-4 •H CCS d

•rl>

r—

as Xd

•H

as54d

4-1

CCS 54

as04B

as

4-1 s

•rl

ii &o

r—t 50OXOoo

44

CCS

X! as as u d

44 a. 50 G

Pi- d 44 •rl d ces CCS d G o 54 G •rl 44 44

as as CO 44

44 6 54 •H G O <u PS CO O d 44 44 d G

•p-i CCS o d 54 G G

as CO as 44

54 CO PU co CCS as as B 54 54 xi pH as as £ d 44 44 44 3 pj as O d as 3

pH ccS e u 54 UP 54 • x:

•P-i as CCS ceSco 44

<44 •rl xs

44 G

•rl PU § t G G r4 G CCS as 50 PU 44 54 50

PI- o Pu CCS G O

CO 44 <3 Pi PU • • • • VO CO

©

©

©
4-4

B. Conversion Factors

i Conversion of log ink or A to a different concentration ^

A _B basis for the equation: k = 10 x exp(-1000 C/T)

To convert from X to Y add tabulated value.

To convert from Y to X, s ubstract . \^Y - 3

cm liter _ -1 -1

atm s _ -1 -1torr s X l mole second mole second

3

cm

molecule - second

23.780 20.780 21.86 -log T 18.98 -log T

\^Y - 6

cm liter2

. -2 -1

atm s -2 -1

X mole second mole second lorr s

6

cm

molecule

second

47.560 41.560 43.73 -21og T 37.96 -2Iog T

k(cm3 molecule ^s = k(cmPmol 7 = k(atm ^s *RT/N^

vog

k(cm^molecule 2

s = k(cm^mol 2s /^v

= K(atm 2

s ^)*(RT/N^

v )

2

N = 6.02252 x 10

23 molecule mol

Avog

Conversion of ’’energy coefficient", C, in the

A B exponential term of k = 10 T exp (-1000 C/T)

To convert from X to Y multiply by the tabulated

number. To convert from Y to X divide.

N.Y -

X i

*

E

kj mol ^

*

E

T l " 1

J mol

*

E

kcal mol

^

* -• E

cal mol

^

*

E

eV molecule ^

c in Kelvin 8.314 8.314xl03 1.987 1.987xl03 8.617xl0"

2

*

E

-i

kcal mol 4.184 4.184xl03

1 10

3 4.336xl0' 2

1000 C = e'7r, R = 8.3143 J mol'Tt

-1 = 1.9872 cal mol" 1

K

_1 = 8.6170 x 10“ 5

eV K

_1
4-5

C. List of Chemical Formulae

The formulae used for molecules that appear in reactions in Part

D are listed below. Barring error, each molecule is represented only

one way.

The order in which the formulae are listed is related to the reactions

in Part D in the following way:

(a) The sequence of first reactants is the same as in the

list below.

(b) Reactants and products are ordered ( separate*. ly) in the

sequence shown below, with the exceptions

(1) The electron, E[-], the photon, PHOTON, and the

generalized third body, M are always placed last within

a set of reactants or products.

(2) Specific third bodies do not appear in reactions,

they are identified in a following parenthetical

expression.

This ordering scheme is strictly alphabetical, being produced by a character- by- character sort from left to right over the entire reaction.

The sorting order is: blank. numerals, letters . This arrangement is not chemical. The procedure makes no distinction

between upper and lower case letters as in Ba, BC,Be, BO. Here, as in

printing the table^we have surrendered and accepted the available computer

technology.

A1 aif

2

B[ +] BeCIF

Al[+] aif

3

B 2°2 BeF

ai

2o A1H B2°3 BeF

2

ai

2

o[+] A10 Be BeH

A12°2 aio

2

Be [ +] BeH

2

A1C1 aio

2

h Be

2

0

2

BeO

A1C1

2 A10C1 Be3°3 Be0

2

H

A1C1

3 A10F Se4°4 BeOH

A1C1F A10H BeCl BF

AIF B BeCl

2 CM

PQ
4-6

bf3

ch2o

BH ®3

bh 2 CH,4

bh3 GHO

BO CHO[+]

BO[+] Cl

bo 2

Cl[ -]

bo 2h

C12

BOF

C1F

BOH

CIO

Br

CN c

CN[ - ] C2

CO

co 0 C 0Hz Cs C2H2 Cs[+] C2H3

CsCl C2H4

CsOH D C2H5 D2 C2H6 F C2° F[-] S F 2 SH 7 HH [ — ] C3H8 H2 C4H 9 h2o C4H

10 H2°2

CH

h3

o[+]

CH,Z HBr

HC1 Na[+]

HCN NaCl

HD NaF

HF NaH

HI NaH 2

0[+]

HNO NaO

ho 2 Na0 2

HOC1 NaOH I NH K NH

K[+] z NH0

KI-I 3

kh2

o[+] nh3 [+]

KOz NO

KOH

Li

NO[+]

no2

Li[+] no3

LiCl 0

LiH o[ -]

LiH2

0[+]

°2

LiO o 2 [-l

Li0 2 °3

LiOH OH

Mg OH[ - ] MgH p N

PH

N2 S n2o SH N2°4 Si N2°5

Na

SiH
4-7

«_ - - o

<3 O

44X II CO tn & X * 43 OC X 43 K) evj 43 4) 43

fr— • • • • • • • • • • • • • O o <4 C\J CM o <4 o CM H H in 43 <4 O 1— H H H m •4 H H «-» If) 3 < I 1 1 1 1 i 1 |-*v i 1 I 1 1 u — 44 *-

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44

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4-1 K < $ 44

4-4

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a: C4 C4 <4 (4 C4

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CL UJ C4 3 C4 rt X X X 3 >- 3 -J 4 4 < 3 4 X U U

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NOTE:

RATE

COEFFICIENTS

ARE

for

CONCENTRATION

IN

MOLFCULES

PER

CU.CM, *

TIME

IN

SECONDS

AND

TtMPERATURE

IN

KELVIN.

LOG(BASE

10) K=A

4-8

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BOND

ORDER,

CT=

COLLISION

THEORY,

EST=

ESTIMATE

BY

ANAL

OGY,

EVALFULL

SCALE

EVALUATION,

J*P=

JOHNSTON 4

PARR

CALC.,

REV=

FROM

THE

REVERSE

REACTION*

SLL=

SELECTED

DATA,

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTES,

SEE

CHAPTER 7
(ASA*)

(BSB* )

RATE

PARAMETERS

FOR

K:

10T

EXP(-1000(CSC*

)/T)

4-t o < o H ©

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m « 9 cs- 9

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(AtA*)

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PARAMETERS

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4-11 o < o'

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(ASA*)

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RATE

PARAMETERS

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4-12 o

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(ASA*)

(BSB* )

RATE

PARAMETERS

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(-1000

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4-14 o < o M O

II « O' in « 2 a 83 rCM 47 o

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MAYER-1968

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RATE

PARAMETERS

FOR Ks

10T

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(-1000

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NOTE:

RATE

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IN

MOLFCULES

PEE

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TIME

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NOTES!

BERO=

BOND

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NOTES#

SEE

CHAPTER 7
(ASA*)

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3

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4-16

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(ASA*)

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4-18 o 4*0

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(ASA*)

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RATE

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T

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(ASA*)

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NOTE:

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COEFFICIENTS

are

FOR

CONCENTRATION

IN

MOLECULES

PER

CU.CM.,

TIME

IN

SECONDS

AND

TEMPERATURE

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LOG

(BASE

10) K=A4B

LOG T

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SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

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ENERGY-BOND

ORDER,

CT“

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XP=

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ON

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DATA.

FOR

NUMBERED

NOTES,

SEE

CHAPTER 7
4-22 ~ - o o O

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note:

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for

concentration

in

molecules

per

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time

in

seconds

and

TLMPERATURE

IN

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LOG (

BASE

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LOG T

-434.30/%

SUPERSCRIPTS

SHOWN

IN

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notes:

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CT=

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SEE

CHAPTER 7
(

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RATE

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(At

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RATE

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(-1000

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4-26

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© O' go o r- H- • • • • • • •

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o z u X |S- Is I 1 1 1 1 2 *-» H- O < Ul X

CJ 2 2 X Ul Ui X b- X O 1- Ui X X X > 4 2 X UJ UJ X »-« X II X CJ Ui 1- I- UJ UJ 2 CL X X UJ

4-J »-* Ui b- X

UJ

Sr— X o o o o o * 2 - • • • • • a> X > O X H "4 CM O •H K) a as as X UJ

•4 + -I- -JT UJ o U. H- u £L ui o » X X II 2 X X b- > u • 2

Ul Q X jJ X 1“ o X

Ui X -< - UJ Q. cj x X X m *-« O 2

r- X X X X X * ..j _j a • • • • • • UJ 3- -J < 2 e c c o o c _l K C CJ 4 + + <4 •¥ X zt U X

CJ 1 X o u II X lL H- I— <x o U 0. • 2 CS <a c • + b 2 -J X 'X 4- M Ui 2 Q o « CM 4* cd a O o X X X X 2 H- _J 9 9 • • • • O o X <

CM CM H CM CM CM 2 »-

•—

aH h- <c c X 2 1 1 1 1 1 1 < 2 O UJ

as O a 2 H II X s—

a a a a a a Z 8 SI X 2 2 2 2 2 2 Ul if >• X LJ CM CM CM CM CM CM CJ O + X 2 *' X a x O O ui UJ o -4 2 at UJ 2 2

oc Ui O O o x a cm u < 2 b~ a X o < X

Ul ->

x a x X a _i < O < O II < X X CM m a c > u X X O X X UJ II u cj (j O 1- • X X X u CM 2 2 X UJ x

-4 KJ O UJ *—

a X —

+ CJ »-» > < • o I X X CJ J CJ 4C ui a o a O X c u X Ul u -=« u. «• X x + UJ + UJ + Ul 2 O 2 2 u *: x X X X X X X o X o UJ o u. Ui a a A X Ol 2 >- a

ii rA 4-

A I'- a rA I'- c -4 O a c X II X ll X II X ll X A X CJ 2 U. Ul O O' O' O' O' O' II O' UJ bCM ^ m — o - o — u as II O X 1 i i X 1 X 1 X 1 O 1 1- ‘ • a a u as U X U X CJ X u as U X H- X -4 a

UJ UJ Ul UJ Ui UJ as 4 I— > a 4 X 4 a a o - X X X Ui a x 2 z 2 z 2 2 99 'ul X O X O X O X O X O X C X UI x cj » ii Ui H UI ” UJ 4- UJ H* IUK Ul b- 1- 2 < x a X X X X X X o -d X x a 2 1- X o X
(ASA 9)

(BSBM

RATE

PARAMETERS

FOR K=

10T

EXP

(-1000

(CSC

*)

/T)

4-34

000 T

*s* ii a a a v£

m r- o • • • • • • • O CVI eg CM CM in o CVI O h- in H H H »~i -I < i 1 9 1 1 I 1 - •u

44 o o O in in O • • • • • o m m in r- o

4- 4 m

CD

44 in in in in r- in in CD • • • • • • • c c c c c c c I

-4- 4 4 m<

44 O' o*

94 CO CO CC eg cc < • • • • • • • w CVI eg eg eg eg eg

in H H H 94 94 i 1 1 i 1 1 l ac

Ul Q a Q Q a a o Q ac z 2 2 2 2 2

<r

m cvj eg eg eg eg eg o o >- Ul o 2 O O < 2 H < \ II ac i- 2*—Z I u 2 o 1-4 o u u 2 ~ -1 cn i a

Ul I 4 4-

m 4

4- o w O Ul X I X X I 2 X u I u o u c u c a. o u C U z o z Ul z Ul z UJ 4 UJ z UJ z a A O Ul o CD O a o a “5 a o a o 2 II a < r* a r- a r- a r- a r- A I'- Z a A a ii a ii a ii a ii a ll a 2 Ul O' II O' O' O' O' O' O' o o «* O 94 _i — 2 o - i —

•“> ac 1 (V 1 eg i O 1 U 1 2 1 M | H 15 I X I X X X I X I X X X -1 X U O Ul Ul Ul Ul Ul UJ Ul < l/l 4 Q 2 a + a 4- 2 4- a 4 2

UJ 2 2 2 2 2 2 2

ac O 2 O 3 C 2 O 2 O 2 O 2 O 2

Ui»- UJ 4- uj y- UJ4- UJ 4- UJ h- Ul h- a CQ a a a a a a O' o a iJ- o eg O' • • • • • • • •

CM ** eg eg eg o a -4 H H H H ^4 H *4 •4 Is 1 1 1 1 1 1 o O in in in o • • • • • • in in H m eg o o m 4 4 + 4 4 4

in in in in in in

m in • • • • • • • • o c c c o c c e 4 4 4 4 4 4 4 4 a a a a

55 67 H • • • • • • • • eg eg eg eg eg H eg -4 94 H H I I i 1 1 i 1 1 a o 2 2 2 2 2 2 2 2 2 2 2 2 2 2

eg eg eg eg eg eg eg eg o o H 4 eg -J < 2 X X 2 2 — 2 — 4 4 2 a a 4 4 m 4 m X o X 4 —» w eg o 2 X o X X o u u U o u Ui u I U G U O U! u a z 4 Z Ul z a z o z Ul z Ul Z 4 Z o O a o o Ul o a o a o O A UJ A a Ul

ii r- a rA I'- II rA I'-

A I'- a r- a a ll a a a a ll a ll a a X O' A O' O' X O' II O' O' O' A O' o — II -4 X — O -4 ev — m —4 II -4 H | 1 < 1 < 1 X 1 X 1 i i 1 -J X 2 X 2 X 2 X 2 X 2 X 2 X O X

UJ Ul UJ UJ Ul Ul Ul Ul 4 2 4 2 4 2 4 2 4 2 4 2 4 2 4 2 2 2 2 2 2 2 2 2 O 2 O 2 O 2 O 2 O 2 O 2 O 2 O 2

Ul 1— UJ h- UJ H- Ul 1- Ul I- UJ 1- Ul H* UJ h- a a a a a a a a
(ASA' )(

BSR *)

RATE

PARAMETERS

FOR K=

10T

EXP(-1000(CSC*

)/T>

4-35

44 O * II 2 c O « in a* if o o CM - • . • • • • • • • • • • • 49 oa K) CM o ^4 mm CM CM CM ** O R- *4 H H •-» H H H H H H H

-1 < 1 1 1 1 1 I i 1 ^ 1 I 1 1 1 U

44

(J o o ID o in in in in • • * • • • • • «o CM H o o CM CM CM O CM 4 4 4> + 4- 4 4 m

44 in

m in r- in in in in in in in in • . • • • . • . . m . . . c c c c c c c c c C c e c 4 4 4 4- 4 4 4 <

44 n

CC 2 a m 2 2 < • • . • . • CM CM CM CM CM CM mm 2 1 1 1 1 1 I

UJ a a a a a Q a z z z z z Z 2O

CM CM CM CM CM CM

CM 2 .2 mm 2 2 in 2 r- • • . • • . • CM CM CM CM CM CM CM

rt 1 1 1 1 1 1 1 a a a 3 3 3 3 z z z Z Z Z Z

CM CM CM CM CM CM CM o

ui o o a z -

<x "x x ri H < 1 -I Z

UI O * z C CM 4 o 4 z CM -I 4 < O 4 z U — CM z -* CM —* CM

1/) O 4 o Z 2 U. 2 CM CM Z 2 Z X 2 Z 2

UJ z lO I <n Z Z CM 4 m CM o m

m

H» o z 4 4 — CM O mm O w 4 — O UJ o 4 O UJ o UJ 4 z I u. X u UJ Ik C X c u u. X U LL X u u u X u U. c u o z z 2 Z UJ 4 UJ z o z O 4 2 Z z 2 Z z o z UJ z a UI o A O o 2 3 2 O UJ o UJ 3 O A O o A O UJ o 2 O z 2 II A 2 2 A II A II 2

<* r* II R* a r* a r** R- ii r* r- ii r* a r- A 2 i—» ^ 2 II 2 II 2 A 2 A 2 2 Z 2 2 Z 2 A 2 II 2 Z UJ ii o • O Z O' O' O' II O II O' Z O O O' o o o o II O o o o m* Ui ** « Z — -j — mm O - mm u < — < rnm mm z -

*-» 2 Z 1 X 1 1 U 1 O 1 U. 1 Z 1 X 1 -1 1 Z 1 Z 1 O 1 O 1 K 3 o z O X X X 2 2 X X X X X X X O O UJ UJ CM UJ 4- UJ 4 UJ 4- UJ 4 UJ 4 UJ 4 UJ 4 UJ 4 UJ 4 UI 4 UJ < m 3 4- 3 Z 3 3 3 3 3 3 3 3 3 3 3

UI z Z CM Z Z Z Z Z Z Z z z Z Z X Z z z Z Z X Z Z Z 2 O 3 O 3 O 3 O 3 O 3 O 3 O 3 O 3 O 3 O 3 O 3 C 3 O 3

UJ UJ H- UJ H- UJ 1- UJ H- UJ »- UJ H- UJ h- UJ #- UJ UJ H- UJ r- UI t- 2 2 2 2 2 2 2 2 2 2 2 2 2

NOTE :

RATE

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLFCIJ'

ES

PER

CU.CM.#

TIME

IN

SECONDS

AND

TEMPERATURE

IN

KELVIN.

LOG

(BASE

10) K=A

4- B

LOG T

-454.3C/T

S’n

FRSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BONO

ENERGY-BONU

ORDER,

CT=

COLLISK

THEORY#

ESTr

ESTIMATE

BY

ANAL

OoY,

EVAL =

FULL

SCALE

EVALUATION,

J+P=

JOHNSTON

4-

PARR

CALC.#

REV=

FROM

THE

REVERSE

REACTION#

SEL=

SELFCTED

DATA,

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOT,

SEE

CHAPTER 7
(A*A

•)

(B*BM

RATE

PARAMETERS

FOR Ks

10T

EXP

(-1000

<C*C

*)

/T)

4-36 o in O CO O o O < a’ • • • • • • • • M o •4 CM <4 fO <4 to CM •* X II W a* •4 IO r- CO «4 cc ^ X * «4 in

x K • • • • • • • • • • • • • • • •

<9 •4 •4 CM cr H CM * *4 O CM CM O' CM CM O K- •4 •4 •4 fO •4 •4 <4 to H •4 H H *4 CM •4 *4

-1 < 1 1 1 i 1 1 1 1 i 1 1 9 1 1 1 1 uH

<0

rO in4

CO O in

m co o • • • • • IO CM CT\ CM IO

4-m4

4*

asM

in in in in

mm in in in in

m in in in in in • • • • • • • • • • o • • • • • c a a c c o c e c o O C c c c c + I 1 4* 4 4* 4- 4- 4- 4- a

uj a O a z< N x iCM IO

r-IO o

IO Z<

>-z< o

CM

CO <o <t> M3 (0 CO 44 M3 CO CO O' CO COm CC co < • • • • • • • • • • • • • • • • CM CM CM CM CM CM CM CM CM CM ~4 CM CM m CM CM 4 •4 .4 KJ 44 H 44 m 44 44 44 44 44 H 44 44

CC 1 1 1 1 1 1 1 i 1 1 1 1 1 i 1 1

UJ o a a a o a a a a a a a a Q O Q Q z z z at z z z cc z z z z z Z Z Z

CCo

CM CM CM

m CM CM CM

m CM CM CM CM CM CM CM CM X — t—

X — 1 1—1 0 4* in u. X UJ X u UJ X

UJ CM Ll 0 4 CM 4 CM Ll 4 CM

»- Z 00 >4 4 U.

w 4 0 Ll

— z o CM- 4 CM Ll 4 ll X z O U. U. 4> UJ Ll uj cv u. 4 U. Ll UJ O Ll! UJ Ll UJ 4 X UJ c u: Ll 4 UJ UJ UJX m x x 33 X Ll X X X X X O X O X CM X X X 4 X X X a 330 0 0 0 O 03 O CM O 4- O O CDO DO Ll — 0 0 O Ll O O z CQ 33 A Ll A O A O 0 4 A I’- r- r- 11 a r- cc r* 0 r» 11 r- a r- a r» x r- 11 r- X 1^ n rll M3 A M3 A X M3 II X X 33 X 0 II 0 II X X M3 X X X X z UJ O' II O' II O' X O’ O' A O' O' X O' O' O' A O' O' n g\ A O' A O' O' o o Z •* 4» 44 44 n 44 II ^ A 44 i-i 44 n *4 II — 1 ^ II 44 || 44 4 a O 1 CM 1 CM 1 4- 1 1 1 1 II 1 4 1 1 1 1 1 1 1 u 1 1 1 H 3 a U. >- O >- >- ui ac CM >- >- >* |_J X i_t X CM >- X CM X X >- I >- X O O 4* UJ X 33 cr U. C£ lL UJ Ll. cr O X 0 X O UJ O UJ O X UJ O UJ 0 X O X UJ < in a 4 X x X a z X X 0 a X a 3 X X 3

UJ z z UJ 4- UJ 4- UJ z 4- UJ 4 UJ 4 UJ 4 Z 4 z 4 UJ z 4 Z 4 UJ 4 UJ Z x O 3 CM z z Z 3 Z z z 3 z 3 3 X I 3

UJ H- (£« 0 u. 0 u. 0 Ll - u. 0 Ll O Ll c_> ll h- Ll - Ll

U Ll 1- Ll u L.U K

33 CQ 33 33 33 JO X X X X X X X X
(ASA*)

(BSR<)

RATE

PARAMETERS

FOR Ks

10T

EXP(-1000(C»C*

)/T)

4-37 o it o o o o < ® • • • • • • o CM CM CM CM * It « « X CC PO « vC O' >C a: vC - • • • • • • • • • • • . • • . o lO CM OJ CM r- CM CM CM CM CM CM CM o - H H H H CM H lO •H H H H •4 H

-J 1 I 1 1 1 1 1 1 1 I*- 1 1 1 1 1 t

r* o * O in o co O O ^ O • • • • • • • • • . . • 4 in lO lO X O O O in m lO lO n lO lO 4 4 4 lO 4 4 4 4 4 4 4 4

CD «f m in

m

m in

m

CD . • • • • • c a o c o c c 4 4 4 4 4 4 1 • * a it < . . • H o

CM

W

O' <XJ CC « in CO < . . . • • • • f CM CM CM IQ CM CM

•4 .4 ^4 *4

m 1 1 1 1 1 1 i a:Ui a a 3 a a o o a z z z z z z CC

(X CM CM CM CM CM CM (O O

in in

m in in

m in n • • • . . . • • c c c c c e c c + 4 4 4 4 4 4 4 O O a . • . CM CM CM

<C CC « <£ <S CC « • . . • • . . . CM CM CM CM CM CM CM CM

^4 «* ^4 *-4 1 1 1 1 1 1 1 1 a a o a a o a o z z z z z z z z

CM CM CM CM CM CM CM CM o

Ui C3 O O Z -* < >x a — z<

ii i U. X u o Ui <

in u. IX X 4 X LX z

Ui X O CM 4 IX < - X 4 m «-> u. Z 4 u. o - 4 — ix m X 4 z vC u: 4 uj UJ U lx ix X u. lx lx lx lx lx 4 lx! C lx 4 Lx UJ

lx CM X X X O X X X X X 4 X X •n

x X U. X X X a co — o ix o o X o (O o A O o O o U. O 1x0 X o LL 3 z X X II A IX X X O

<c a r- r- r* a X R* r* ii r- X 1^ r* a r*

x r* r*

II X X A X X II X X X X r X X A X A X II X X X Z UI O' O' II O' O' O' A O' O' n A O' O' II O' II O' O' A O' O' o o CM — CM — II 4 — 1 — II — 4“ u. — II — •— M a: U. 1 I C 1 1 O 1 1 1 u 1 1 1 lx 1 < 1 < i 1 i K 3 X >» X X >- X X >- lx X lx >- lx X X >- X X >- Z X z x 3 > X U O X Ui X UJ X UJ X Ui X UJ X UJ UJ X UJ < Si 4 X 3 4 X 3 4 X 4 3 4 X 4 3 4 X 3 4 X 4 3 4 3 4 X 3

Ui UJ Z UJ z UJ z UJ Z UJ Z X Z Z UJ Z x CM X 3 CM I 3 CM I CM 3 CM X CM 3 CM I 3 CM X CM 3 CM 3 CM X 3

lx o 1— U.U - lxU lx lx O IX H- lx (_> H- lx

U lx H- u. *- U. o i- X X X X X X X X X X X

NOTE:

RATF

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLFCULES

PER

CU.CM. .

TIME

In

SECONDS

AND

TtMPEH

ATIJRE

IN

KFLVIN.

LOG(BASE

10) K=A4B

LOG T

-434.3C/T

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES!

BEBO=

BOND

ENERGY-BOND

ORDER.

CT=

COLLISION

THEOR

EST=

ESTIMATE

BY

ANAL

OGY»

EVAL =

FULL

SCALE

EVALUATION.

J+P=

JOHNSTON 4

PARR

CALC.' )

cV=

FROM

THE

REVERSE

REACTION 

SEL=

SELECTED

DATA.

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMB- J

NOTES t

SEE

CHAPTER 7
(ASA*)

(B*B* )

RATE

PARAMETERS

FOR Ks

10T

EXP

(-1000

(CSC

•)

/T)

4-38 o o

**o • • « O IO 1 s II CU CM CM 04 CM O' O' O' o CM 36 02 X to 1- • • • • • • • • • • • • • • •

(0 in to CM CM •4 O o O' H CM H CM o o 1- CM •4 H «-• «4 H 1 H •H to H

-1 < i 1 1 1 1 1 1 Is ( 1 1 1 1 1 oM •—

CO CM X

in * O o •4 to in

U • • • • • • • o CM & to •4 •o to 4 4 4 4* 4 _ 4 m

asH

in M3

m in in CM O r» M3 a • • • • • • • o o c •H o o

4* 4* 4- 4- 4- a < • •

«ft to •4

O' cf in to in ffl CO CM CO r- Is* < • • • • • • • to CM CM O CM *4 *4 *4 •4 »4 ^4 «4 •4 ^4 1 1 1 1 1 1 1 x

Ui a a a a a a a a z z z z z z z

<E CM CM CM CM CM CM CM O a

RANGE T/X00 o 4^ u. CM X

I/I u. M3 o X X u

Ul X CM X X u h» X 4 O - 4 •4 X 4 z Ui Ui u i a I X a CM Q. U. X CM X CM X 4* u 4 CM 4 X 4 o o o U O X o “3 “3 I “3 X 3 z X X X 4 X

<* f* r>* r* X h- a r* A X A X A X X X X A X II X Z Ul II O' II O' II O' A X X II O' O' o u 4« II O' A O' O *4 •4 ac X 1 O 1 to 1 II -4 CM 1 CM 1 K 3 o >* X >* X X X l 1 X X I X o o X x X Ul X X U X CJ UJ CJ Ui < in 4 X 4 X X Ui Ui a 3

Ui Ul Ui 4 Z 4- >- 4 >- 4 Z 4 Z x CM X to I 3 <* < 3 W

U.O u. u X t- X X X X X »- X h- X X X X X X X O r- *4 -4 X o in o to CM O' • • • • • • CM 4 O to H CM O + 4 4 4 4 * r* •-4 r- X in X Is* X • • • • • • • • e a c a o c c c 4 4 4 4 4 4 1 4 X X X CM X O' o H * O O' X H «*4 Is* • • • • • • • • CM CM CM CM CM •4 •4 H H •4 H •4 to •4 1 i 1 1 1 1 1 1 a Q a a o a a Q z Z z z z z cr z

CM CM CM CM CM CM to CM

>-z<

II X

CM to X X X O X z u u CJ to 4 CJ w 3 4 4 4 CJ CM 4 a CL Ul I X u a cm a I Ui a. CM 4 CM 4 CM X 4 X 4 X 4 X X CM 4 X 3 X 3 X o 4 3 3 3 o X 3 X X X 4 4 A X Is* r* X II Is* A X A X A X . X X cc X X X A -0

II O' II O' II O'

A X X X X O' II O H <4 ii a A O' A O' to 1 ^ 1 O 1 II -4 II -4 4 1 Z 1 X X X X I X 3 » 1 1 X CJ X

CJ Ui CJ Ul CJ Ui CJ X u. cr X X X Ul X Ui 3 3 a Ui Ul Ul 3 a 4 Z 4 Z 4 Z 4 >- 4 >- 4 >- 4 Z 4 Z 3 3 3 < < < 3 3 X >- X H* X t- X X X X X X X I- X — X X X X X X X X
<A±A»)

(B*R«)

RATE

PARAMETERS

FOR K=

10T

EXP <

-1000

<C*C •)

/T

4-39 O < O « © * II r* it (O X CO X tO CM « CM O' co a- CM x O ct o CM If) 1- • • • • . • • • • • • • • o O to co in X a o CM o f- O H «-4 H «-4 H H H •H H

_l < 1 t I 1 i I 1 i 1 1 I t I uH a <o X H If) to in CM r~ a- © if CO X o o If) CM to • • • • • • • • • • • • r- cr * X vO tO CM 4- if 4 CO H H 4 4 4 H + 4 4 m«

CM a* *4 r> •H •-t in a (0 o in cr- O' X X X CO in « • • • • • • • • • • • . c c c c e o c a e c o o + 4 4 4- 4 4- 4 4- <

«4 if a O' X O' in CO O' 3- CO H r- < • • • • • • CM CM CM CM •4 *4 «-t H

CL 1 1 1 1 1 I

UJ a a a Q Q a a 2 2 2 2 2 2

CLO

CM CM CM CM CM CM O

UJ o

(D O 2 -t < N X

<o vO to X CM in o O' CM in O • • • • • • •

CM CM H CM CM CM •H H •”4 ^4 1 i 1 1 9 1 1 Q a o a a a Q 2 2 2 2 2 2

CM CM CM CM CM CM CM

CM

V) O vO X X

Id 2 tO z 2 - — X X X X O 4- • H CD O < 4 4 1~* o 2 Ul x a -1 X X X i a 2 X X X X X I X I X O) X

CM X X 4 * 4 4 UJ 2 4 4 CM 4 CM 4 O 4 X 4 1/) 4 UJ Q XO ~y “3 4 -5 4 X “3 4 “3 X “3 X -3 ~3 ~3 ~3 4 X 2 X 4 4 4 X X 4 4 4 < r* X X X r~ X A X X X X X X X X X X A X a r X X X X X X O 2 UJ II O' X X A X A X X A X II O' II O' X X X A X O U «•* A O' A O' II O' II O' A O' II O' mM A O' A O' A O' II O' a O 1 II ~ II -4 II — «>» CM 1 to 1 II *4 II -4 II ^4 »- D 2 X 1 1 -4 | CD I 1 < 1 X X X X 1 1 1 ~t 1 o o X UJ X * X _J X X X 2 X 2 X 2 UJ 2 Ul O X X X in X in x < U) a X UJ Ul Ul Ul UJ X a UJ Ul UJ UJ Ul 4- 2 4- >- 4 >- 4 >- 4 >- 4 >- 4 >- 4 2 4 2 4 >- 4 >- 4 >- 4 >- X «* < < « < < 3 D < <t «t <

XI- X X X X X X X X X X X X X #— X t— X X X X X X X X X X X X X X X X X X X X X

note:

rate

coefficients

are

for

concentration

in

molecules

per

cu.cm.#

time

IN

SECONDS

AND

TtMPERATURE

IN

KELVIN.

LOG (

BASE

10) K=A+B

LOG T

-434.3C/T*

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BOND

ORDER »

CT=

COLLISION

THi

0PY#

EST=

ESTIMATE

BY

ANAL

OGY.

EVAL=

FULL

SCALE

EVALUATION#

J+P=

JOHNSTON 4

PARR

CAL C»

TEVFROM

THE

REVERSE

REACTION#

SLL=

SELECTED

DATA.

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTTS.

SEE

CHAPTER 7
(ASA* )

<B*B»)

RATE

PARAMETERS

FOR Ks

10T

EXP <

-1000

(C*C •

)/T)

4-40 o (X) < '© • • « o <-4 H wt * II X m X p- in r*- X IT io H h* IO IO - • • • • • • • • • • • • • • • o CM H CM o o o H o IO * H H O 4- H H •-4 H H H H IO H

-1 < 1 • 1 1 1 1 1 l*v 1 i 1 1 1 1 1 •© . M o o CO O CO in U • • • • • • • IO O IO o o o 4- IO 4- O in O o H ©

4- 4 4- 4 x

in in in

m inm X X M3 in in in in

m in

CD • • • • • • • • • • • • • • • © o c © o © c © © o o o o o ©

4* 4- 4- 4- 4- 4- 4- 4- 4- 1 4 4* 4- • * P- 4 •

44 «-4 p- « © IO © © © CM © O O' r- X © X ©

©

© < • • • • • • • • • • • • • • • CM CM CM CM CM CM CM —* CM CM CM CM CM CM W H H *4 H lO *•4 •H 4-4 1 1 1 1 1 1 1 i i 1 1 1 1 1 1 cr

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4- 3 U. X X 1 O X X 1 *4 X O 3 X O X X UL X I 1 O X O X < 4-m <X 3 o O 4 UJ »-• a: M Ui CD X Ui CM3 UI CM Ui < UI < UJ < X <UI < 3 X < 4- > 3 < in 3 3 3 UI 3 a Z UI z a Zu 3 Z 3 Z 3 Z 3 Z 3 Z 3 z 3 X 3 3 in UI z >- z >- z o Z Z z z >- Z Z • • 3

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(ASA ')

(B*B *)

RATE

PARAMETERS

FOR Ks

10T

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4-74 o < o

44 O

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4-75

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m in X in o ffl ® lO IO CM CM CM CM CM < O' H O • • • • • *4 m * II O' O' m o o X o in x X in ITlTOO^ o o (VI in (V «\J O' z m O' O' h- • • • • • • • • • • • • • • • • • • • 0 CM CM lO lO io m m io •H CM CM ~4 CM CM H O h- H H H H H H H IO io IO ro m m IO m IO »-i H

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note:

ratf

coefficients

are

for

concentration

in

molfcules

per

cu.cm.#

time

in

seconds

and

TEMPERATURE

IN

KELVIN.

LOG (

BASE

10) K=A4B

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BOND

ORDER,

CT=

COLLISION

THEORY,

EST=

ESTIMATE

BY

ANAL

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FULL

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BASED

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FOR

NUMBERED

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CHAPTER 7
4-76

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RATE

PARAMETERS

FOR K=

1Q

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4-78 & IO IO it

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cr CM it X CM CC ao in r- r- X O CM ac ^ X r* X • • • • • • • • • • • • • • • • • • © CM IO o CM x O' o O' «-• O' 0^0 o o o o o - CM H CM «-l H CM IO CM IO CM IO IO IO CM IO CM IO IO

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CO o o CM CM CM Is* flO in in o o X in co X X

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4- 1 1 8 1 1 1 1 1 1

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44 44 *4 •4 8 8 8 8 i 1 i i i 1 1 1 1 1 8 8 1 cr

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UJ o • • CO o IO X x

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II 91 II IS II II II x- X X X X X X X -4 4«5> — >- — >- *4 V 4 >- 4 A o« cr *«> cr —> 4* X — X •—. 01 I o I o #— < — in in 4 — in in < — X X < X

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N*

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UJ >- z 4- >- 4- Z 4- Z 4- X 4- X 4- Ul X 03 03 + Ul X 03 03 4- UJ X X X 4- Ul X 4- X

CC < UJ <* UJ «* 4 03 4 4 4 Ol 4 4 4 4 4 4 X 4 4

CM X CM CM X CM t— CM CM CO CM 03 CM CO CO *C CM CD GO X CM CD X CM X CM X X X X X X X X X X X X X
4-79

moo o 60 < o • • • • M o *» *» x II o cc o O' eg eg to -4 vO *4 o o X tv o r- eg « O' d r* <? O O' - • • • • • • • • • • • • • • • • • o eg * eg C\i fO to eg eg eg o eg eg •4 d O' 2 o 4- eg eg •4 H H *4 *4 rO H eg -4 eg

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cv z CV Z eg Z eg k CV 3 eg 2 2 3 Z Z 2 h- CV 1- eg t- CV 2 2 t— CV 2 O z X X X X X X X X X

NOTE:

RATF

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLECULES

PER

CU.CM. »

TIME

IN

SECONDS

AND

TEMPERATURE

IN

KFLV/IN.

LOG (

BASE

10) K=A+B

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BONn

ORDER.

CT=

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EST=

ESTIMATE

BY

ANAL

OGY,

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FULL

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DATA.

FOR

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SEE

CHAPTER 7
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m cm

m cm n cm in

ac o < o <r O UI 3 O 3 o in «t < < u 3 o < «x o <* o < o <x o <

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NOTE:

RATE

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLECULES

PER

CU.CM.#

TIME

IN

SECONDS

AND

TEMPERATURE

IN

KELVIN.

LOG (

BASE

10) K=A4B

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

HEROBOND

ENERGY-BOND

ORDER.

CT=

COLLISION

THEORY#

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ESTIMATE

BY

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FULL

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XP=

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FOR

NUMBERED

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SEE

CHAPTER 7
(ASA*)

(8*0* )

RATE

PARAMETERS

FOR KS

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(C1C •

)/T)

4-82

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NOTE:

RATE

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLECULES

PER

CU.CM.#

TIME

IN

SECONDS

AND

TEMPERATURE

IN

KELVIN.

LOG (

BASE

10) K=AB

LOG T

-434.

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SUPERSCRIPTS

SHOWN

IN

SQUARE

brackets,

notes:

bebo=

bond

energy-bond

order,

ct=

collision

theory,

est=

estimate

by

anal

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FULL

SCALE

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J+P=

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THE

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XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTES,

SEE

CHAPTER 7
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AtA)•

(B*B •)

RATE

PARAMETERS

FOR Ks

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4-84 o

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MAYER-1968

BErO

2ND

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(ASA*)

(BSR«)

RATE

PARAMETERS

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4-85

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w* * It 49 5fl in K) in

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QO u. o X X 4 X 4 X 3 4 4 4 4 a r«* u 1-4 U. X II <0 U. X U. X X X X 44 30 X o X S3 A X S3 X A O' l-l —< A O A O II o A O A O'

II

— 1 1 II II »4 II -4 II -4 1 LJ Z 1 1 -4 1 1 1 o z O UI a. z to z in z 44 a: * z

UJ a UJ ul UI UJ UI 4 >- 4 2 4 >- 4 >- 4 >- 4 >- 4 >- < < « < « <t U. X U. P U. X U. X U. X 4 X 44 X X X X X X X X

note:

ratf

coefficients

are

for

concentration

in

molfcules

per

cu.cm.#

time

in

seconds

and

TtMPERATURE

IN

KFLVIN.

L0G(BASE

10) K=A4B

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BERO=

BONO

ENERGY-BOND

ORDER.

CT=

COLLISION

THEORY#

EST=

ESTIMATE

BY

ANAL

OGY.

EVALr

FULL

SCALE

EVALUATION#

J4P=

JOHNSTON

4-

PARR

CALC.#

REV=

FROM

THE

REVERSE

REACTION#

SLL=

SELECTED

DATA.

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTES.

SEE

CHAPTER 7
4-86 < o H O

*4 X II vOCM IT o 4

O' o

*44 o 00

m

© it IT in cc 4 • • • • • • • • • • • • • • • O ID in o © o o o in tM o H H CM CM O 4 *4 •4 H 4 H H H 4 H H 4 4 H •4 H

-1 < 1 1 1 1 1 1 1 I'' 1 1 1 1 9 1 • uH m O' O O in M3 in O' 4 © CM in o O © m in O o in in • u • • • • • • • • • • • • • u CM m in 4 4 •4 4 o H o m M 4 <4 *4 <*«$ 4* 4- + 4 U 4 ©M

0.

© 4 4 X CM in in 4 m M3 in in in in in in in in in UI CO • • • • • • • • • • • • • • • c a o o o © c o o © a a o ©

4* 4 4 4- 4- 4- 4 4- 4* 4 4 4 4 ©M

<S• ©

© CM in it M3 M3 in 4 O' « 4 4 •t in it CM o 4 © -4 in O' «4

© H < • • • • • • • • • • • • • • • < m •4 •4 CM •4 CM <4 •4 m CM CM CM CM m CM 4 4 4 *4 4 H 4 4 *4 «4 4 •4 H •4 4

10

cc 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

Ui a a Q Q Q a a a a a a a a a a

II a z z Z Z Z z z z z z z z z z z *

oco

u.

I/I x

RANGE

OR

T/1Q0Q

CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM

UI

Uix oz —

— o < in © o «n z —

a. Ui 4 in Z 4 © 4 z X X X o o w —* 4 m CM CM UI o • *4 M> O o <x o o 4 O CM z X 4 • O O 4 z _i a z z 1 1 Z X X X x a I X in x z u u O Ui 4 m m Z UJ Ui < 4 Ui Z Ui 4 O Ui X 4 mui Ui z 4 Z < z cm in X 4 z 4 Z

cr a 4 “3 4 ©

© 4 X © “3© 4 © 4 O o z o X Ui z~ 4 O o z 4 4 4 4 X z X < 4* 44 4 4 i 4 z 4 A I'- 4 A 4 X 4 Z 4 © © •4 © © 4 © 4 © 4 © © © © ll © A © II © © © z Ui A © A © © A © © © © A © A O' A O' O' II O' O' A O' A O' o a II O' II O' A O' II O' A O' A O' A O' II O' II 4 II 4 O 4 CM 4 II 4 II 4

4*

x 4 II 4 II 4 II 4 II 4 t 1 < 1 X 1 X 1 1 1 4 3 4 | O 1 1 < 1 1 1 H | Z X Z X Z X Z X Z X O X O X O O _i a X cc z cr z cr O X X X in cr in © Ui Ui Ui UI Ui Ui Ui < in Ui Ui UI UI ui Ui UI Ui 4 a 4 a 4 a 4 a 4 a 4 a 4 a

Ui 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 z z Z z z z z X «* «t < < < < < < O X O X! O X O X O X O X O X

<4 3E 4 S <-• X •4 Z Hi 4 I 4 I 4 X Z 4 Z 4 Z 4 Z 4 Z 4 Z 4 Z 4 I z z I I X X X X X X X X X X
(ASA*)

(B*R*>

RATE

PARAMETERS

FOR KZ

10T

EXPI-1000

(C*C •

>/T)

4-87 o o o o <' o • • • •

44 O CM H CM CM X tl K) 03 03 vO IT O (M o r- o IT K3 h- • • • • • • • • • • • • • O a 44 eo o o K) CM CM O -4 —

44 -4 H w H 44 «-4 H H

-I < 1 1 1 l l 1 1 i 1 1 i 1 •u

41 a O' O' 03 CM o CM -4 o in rO 03 U • • • • • • . a o m m o o o o yO in H K) CM CM 4- •f 4> •m

44 H a- vO O' m in O CM r** in vO £ • • • • • . . • c c o CM C a a o c c o c 1 + 4- 4- • a o O 4 . . . . 44 CM H CM CM

CO a in 44 to 44 03 o in in O 03 O r** o 44 03 O r- < • • • • • . • . . . . m . CM CM H *•4 r*. o o 44 m m CM CM .4 —4 I i 44 •4 H •4 44 44 44 9*4 1 1 1 1 1 1 1 1 1 1 1 crUi a O a a o a Q o o 3 a o Q a z z z z z z Z z z Z z z Z

a: CM CM CM CM CM CM CM CM CM CM CM CM CM o a in in in in

Ui a • • . • o a >- m K) K> m z *4 Z i 1 1 i 4 N. 4 H •4 •4 44 a HII 2w

CM o 4. O — 2 — 4» 44 CM

—

m 0) O m sO

— CM *4 XN z r* ui m z — + *4 *4 O' in o in in IT 4— I — K) w w ^ z ~ w 4- — 44 O < O • o — CM CM o 4- -1 2 O Z z UI C _i a -i > H K 1- O H * a. a. X 0. z O 0L CM UI UI UJ in o in oin —i in 4- 4- UI 9 o CM X z in in a UI CM Ui -JUJ out 4- -) "3 £ *> z o £ CM z u 4 44 44 4 z r* r- A IT z j* o r* a r*» 4 z z z

vCA 4 II vO sO £ A vO

A £ II £ z « CO £ £ z Ui A O' II O' O' a in o' A O' II O' II O' O' i£ A «£ A £ A £ o o II — m* CM — II 'C —4 II -« 4* *4 z - A O' II O' II O II O' 44 ac 1 £ 1 O 1 O' 1 1 Z 1 O 1 O 1 II -4 44 K D O X X £ CO 2 *4 Z o z o z z z 1 z » Z 1 Z 1 U o Ui Ui X 1 4 Ui Ui 4> UJ 4- Ui z cr 4 X u> cr < cr 4 o 4- a <J 4- Z * 4- n 4- in n m SCC UJ J UI 2 UJ z uj Ui z z n i in z z £ z -J z >* >- > >

cr o O £ CM 4 CM 4 4 CM UJ CM UI (j UJ O UI 4- « 4> < 4- « < z — Z t- O £ O £ X O "V O £ 03 O “3 2 2 2 2 £ £ £ £ £ £ £ £ -4 44 H NOTE!

RATE

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLFCULES

PER

CU.CM. »

TIME

IN

SECONDS

AND

TtMPER

ATliRE

IN

KELVIN.

LOG

(BASE

10J K=A

4- B

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BONn

ORDER,

CT=

COLLISION

THEORY,

EST=

ESTIMATE

BY

ANAL

OGY,

EVALz

FULL

SCALE

EVALUATION,

J4-p=

JOHNSTON +

PARR

CALC.,

REV=

FROM

THE

REVERSE

REACTION'

SLL=

SELECTED

DATA,

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTES,

SEE

CHAPTER 7
4-88 O 40

44 O

*4 ^ II CM CM 36 H* • • • O lO H O H- •4 H

-J « 1 1 i

r- CM

CO O' CM CM • • • • K> o CM If) H —1 H H i 1 1 i

IO 4” &

IO CM O' h* • • • •

CM CM O' o

«-4 H H

Is 1 i l o If) • •

CO

x o ID X CM • • • • • m m O CM CO m CM in m —i l 1 I i 1 oH

O’ o -4 in in c*

m cf 4- O M3 CM

in \0 r** r* c* CM o M3 CM H O' M3 • o • • • • • • • • • *... • • • u M3 in H |S- M3 in in M3 m O O ~4 O O CO M H 4- 4 >4 4 CM m u . 4 Ooo

COH

CL fs- CM CO O O' in r^ ct X in in M3 m m m m CM CO in O CO o in 03 Ui CD • • • • • • • • • • • • • • • • c o o c o a c ^4 c *- c o 4 4 4 4 4 4 4 4* 4 1 •4 3 1 4 0BH

CO

m a m

h- <t • •

44 <f4 o M3 m s**> in CM O CO O M3 CM O < O' M3 O' CM in H 3- CM o in in -4 r- N < • • • • • • • • • • • « • • • • < •4 CM -4 CM m m m m CM CM o CM «h CM «4 H H •4 «4 «•« «-« H •H 4 m ^4 cm m H O 1 § 1 1 9 i 9 i i 1 1 i 8 i i i •4 Z

Ui Q Q o a a Q a Q Q a Q a O O Q a

II Q Z Z z z z Z z Z Z z Z cc z Z CC z Z CM CM CM CM CM CM CM CM CM CM CM m CM m m CM X O Z o m in O UI O • • IL o o > m >- m Z -4 Z 1 Z 1 cn < s < -4 <

oc CX 1- UiUJz

ii z

in oz

a. Ui 4 4 ^ 4 in 4- 4 H CD < CM UJ O o O o in o -1 Z z n CM X ~

H* z Z X O X o. a m

x X x a a 0. CL z a 4 UJ O H- o a. o Ul o. a < UI UI 4 Ui 4 UI * 4 4 4 4 4 4 4 4 i_i Z ^c n 4 U X z 4 a a 4* CD 4 CD 4 "3 4 00 CO “3 “3 “3 “3 4 “3 * O Ul 4 “3 X o 4 “3 z 1-4 4 X X X A A

«*

M •— *—i 4 X 3C 5C 5C I a ii r- I ii r- X X X I 03 X 03 X X X < X X X X * X II X X * X X X 2C X Z Ui M3 M3 M3 M3 A X X A X A X A X X O' Z O' X Z O' O' X o u A O A O' A U A O' II O' a a II O II O' II O' A O' r-i *=. *4 A O' A O' ** (X II — II — II -• II *4 II -4 II -4 4 1 4 1 11 4 1 1 II -4

4- 3 1 | 1 1 X 1 1 X 1 X I I 1 1 t_t Z

~y 1 z z 1 o o X Z x cr X z X z *-» z X z *-4 ac CD Z < z X z O Ul CM ui X z X Ul Ul X z < l/l Z UI o UI a ui l/) UJ n ui sC ui _l UI Z UJ Z UJ Z UI Z Q o n Ul o n o a uj UI >~ >- > >- >- >- >- >* >- >- z z >- z z >- z 4 <* 4 < 4 < 4 < 4 < 4 < 4 < 4 <X 4 < 4 < 4 X 4 UJ 4 < 4 UJ 4 < Z Z Z z Z Z Z Z z z »- “3 z ~3 h- Z

t-e *4 H4 >-4 * * JC * * a£ jC *
(ASA')

(BSR* )

RATE

PARAMETERS

FOR Ks

10T

EXP

(-1000

(CSC •

)/T!

4-89

CM o in o

<'o • • M O CM * II K> o o C\J O r» 43 CO r* CM 3- IT in sr * sO CM vO • • • • • • • • • • • • • O cm vO CC CO CM H H CM CM O t- CM <4 <\J CM 1 fO H H H •4 H H

-i < l 1 1 1 1 1 1 •‘•I i 1 1 | w •u . H

CM K) * n r» CO r- CO CO 'O r** CO rO O' H vO o U • • • • • • • • •

M3 d- o o o o in S3 CM •O CM c*

m

CM 4 4 4 4 4 4

COM

K3 <D r- 43 CO #o in Kl

CO CM tn n in tn H CM r^ CM r- r* r*

CO • • • • • • • • • • • • • c c e c o o o 1 1 I 1 4 4 4 4 4 4 m m o < • . H CM r* o in o CM o O 4*

43 r* O' o a CM rO r- in r* r- 43 < • • • . . • • • • • . • . CM •h rO r* o K> fO CM m CM CM CM

»4 CM CM i K) H —4 1 1 1 1 1 1 I 1 1 1 1 1 CC

U1 a a a o a — a Q Q a a Q Q o Q z z cr cc z >- X Z Z z z Z Z z

CC CM CM

m rO CM z m CM CM CM CM CM CM CM o —

<

>- a z in in ii

UJ a < • • X o a IO #o «« Z II 1 1 < \ X -4 .4

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w X X X I o <»* o -» z

in sc: cr cf UI CM 4 fO

A

#-M

A

w II I X X o in II Z l—! < z in a. Ql > UJ K X u. _i a x a i a z a i a X CL

x a. 4 4- 4 x ui x a in X 4- 4 Z 4 4 O 4 0L 4 n 4 a 4 ~i x o II Ui 4 o 4- 4 “3 “3 4 ~> “3 3 “3 z X •4 4 4 4 4 X sc r- r* ri r- St St St St (O CC ^ o o 1 43 1 o « cC st « 33 St « St 33 z <o z Ui 43 A 43 1 O' O' l_l O i_j o A vO A vO -O A vC vO NO 43 o u A O' II O' ^ X I — II O II O A O II O' A O A O A O

cr II •4 UJ 1 1 O 1 O 1 II -4 II -4 II -4 II *4 #- 3 | X 1 Z X z X -• 1 1 1 4 1 1 1 1 u O x cr »-• a: UJ UJ 4- UJ 4- UJ JK X X z a Z X O X a x in x < in in ui in uj in a in a Ui UJ UJ UJ UJ UJ UJ Ui >- >- r"> z z r"* z n ^ 4- >- 4 >- 4 >- 4 > 4 >- 4 >- 4 >-

CC 4 < 4 < 4- UJ 3 4 UJ 4 3 <X < <« <t < < < X X uTh t_i “3 i_J H- X X X X X X X X X X X X X X z z Z Z Z z St z z St z z

NOTE:

RATE

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLFCULES

PER

CU.CM. »

TIME

IN

SECONDS

AND

TEMPERATURE

IN

KELVIN.

LOG

(BASE

10) K=A+B

LOG T

-434.3C/T.

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BOND

ORDER,

CT=

COLLISION

THEORY,

EST=

ESTIMATE

BY

ANAL

OGY,

EVALr

FULL

SCALE

EVALUATION,

J+P=

JOHNSTON 4

PARR

CALC.#

REV=

FROM

THE

REVERSE

REACTION#

SEL=

SELECTED

DATA.

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTES,

SEE

CHAPTER 7
(ASA*)

«B*BM

RATE

PARAMETERS

FOR Kz

10T

EXP(-1000(C*C*

)/T)

4-90 & ID vO o r^

© ID < o s • • • 9 •

44 O *1 CM rl -*

$2 II *d ID O o r*- ID « O fO o ID O' «1 it r- M3 © M3 ID vC SO 4- • • • • • • • • • • • • • • • • © •4 fO r- o it CM CO o Csl K) O O CM in O H- W l H 1 •1 H •4 —• !D ID CM ID ID H J < 1 9 6 8 1

8- ** 1 1 1 i 1 1 1 1 oM

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© H © «*4 ID ID o f- © ID

S3 e • • • • ® • • • • • • a a s © ^4 —4 © © ^4 3 «i e <*=4 4 4 4 f i 4 1 1 4

«* SD ID

© r» o ID < 9 9 9 9 9 •

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•1 —4 CM

ID & © ID H

O' O

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© CM CM tn CM o CM ID —4

«* » s • • a « 9 9 9 • • 9 9 9 9 9 ID r* © a ID ID »D ID CM —4 © CM ID

si 8 S 1

5*4 s>«S 5-4 5-4 5-4 ID ID -i CM ID *i 1 8 8 8 8 1 1 1 8 S 1 1 8 s >»

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©

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II O' 4 «* II O' •» ae •=4 1 1 1 X 1 X -4 X -4 X -4 u 1 4 1 1 1 1 1= <-» l ^ z •"» Z ^ 2 o z 9^ | © i M 1 X 8 O X X CM Z X 1 X Z X X 1 o © id oe 4* Ul 4 UJ UJ UJ a k X QC Z (X z ce Z UJ O UJ O UJ O X O UJ UJ X X < ID ui u* M3 tj »D uj vD + ID UJ ul UJ UJ o Q cD ul id a UJ Ul + >- O Z Q Z o z z 4 >- 4 A 4 > 4 >- 4 Z 4 Z 4 Z 4 >- 4 Z Z 4 >- \ «s CM Ui CM U! CM Ui CM Ui «* <1 »t < X X UJ < U 3 «* X I X “3 X © © a -» X 1-1 X »-4 x t"-s 4- 91 » *i © *4X •i ~i 4- -4 £

a£ 32 jC a a a a -J a a a a
(ASA* )

(B*R» )

RATE

PARAMETERS

FOR K=

10T

EXP(-1000(C1C*

)/T)

4-91 o in o <o • • O CM w* * II CM o o o fO cc CM *-< m r* in in X o O' H

H- • • • • » • • • • • • • • O X m cc «-» o CC H CSi CM K> * O “ H CM CM rO H i K) H H H —< *4

-1 < 1 1 1 1 1 1 1 1 1 i 1 moM

r** o X O' CM H in o If) O' K) CM O • . • • • • • • CO CO o o o CM O o lO H O' X O 4 4- 4 4 4 •

CO

m

CO 96 o m in in in n in in 00 00 inH

CD • • . a • • . • • • • • • c c CM 4* o c o c c o 4 1 1 1 4- l l 4 4 4 4- 4- • in a < . . 44 co X

CM « X 4

r» o' O H o o CO X in lO H < • • . • • • • . • . • . . CM K) O' (O o H o CM CM CM m H f-4 -4 CM m H i K) •4 *4 -4 ^4 1 1 1 1 i i 1 1 1 1 1 1 X >-

Ul a a Q 3 -» 3 a a z o a o a a o Q z z — X X >- X z z < X z z z z z X CM CM >- rO rO z m CM CM in CM CM CM CM CM o z < it < X o in it in w

UJ o II • X • o o x m w K> z i 1 X < \ •4 X H- X X 4 O 4 I M 4 O X O _l O o UJ H 4 4 -J 4 X

-1 -1 4 o

in

M O cl"

A r-i 4 X X

UJ in

A CM

A 4 4 KJ II 1 3 o <t »- in II w II -1 -I-' UJ X X z o 4 X -1 4 z z 4- a a X > u. X UJ A Uj A »- UJ a u Ui 4 X X 4 0.

•4 X 4 UJ X X II X ii in 4 X X *4 Z 4 4 4 4 a X 3 -• 3 4 X o 4 O o UJ o AO -JO U4 "J 3 U4 “3 z *-« J n n n II -J -1 < -1 fi h* fl |U i i r* i A -1

CO a a 1 X c 1 X uj X uj X uj X r-i II X A X X A X z UJ A vO II X L_l O' O' uj O' CM O' X O' X O' 1 O' o II X A X II X o u II O O' UJ O - O — O *« o — UJ O -4 o II O o

44 X •-4 X ^ 1 1 1 1 1 1 O 1 4 | O 44 < 44 K 3 X 1 H | 4 Z X 4 X 4 X 4 Z 4 X X -1 X X 1 Z 1 Z 1 o o in x in x UJ UJ UJ UJ UJ UJ 4 UJ UJ X X X < in UJ UJ r-i in a n a r-i q r-i v/) I-I o a 4 a 4 UJ 4 UJ 4 UJ UJ 4 >- 4 >- 4 z z 4 Z 4 Z 4 Z 4 Z -1 z z >- >- > X < < UJ UJ 3 uj 3 uj 3 u. UJ uj 3 U 3 I 3 X < I «* X < H X 4 3 — 4 h- 4 H- *-•3 4 K 4 K U4 »- U4 Z >4 X 4 X

-1 -J -1 -I -I -J -1 3 -J -1 -1 -I

NOTE:

RATE

COEFFICIENTS

ARE

FOR

CONCENTRATION

IN

MOLFCULES

per

CU.CM. *

TIME

IN

SECONDS

AND

TtMPER

ATURE

IN

KELVIN.

LOG(BASE

10)K=A48

LOG T

-434.3C/T,

SUPERSCRIPTS

SHOWN

IN

SQUARE

BRACKETS.

NOTES:

BEBO=

BOND

ENERGY-BOND

ORDER.

CT=

COLLISION

THEORY.

EST=

ESTIMATE

BY

ANAL

OGY.

EVaL=

FULL

SCALE

EVALUATION.

J+P=

JOHNSTON 4

PARR

CALC..

REV=

FROM

THE

REVERSE

REACTION#

SEL=

SELECTED

DATA.

XP=

BASED

ON

EXPERIMENTAL

DATA.

FOR

NUMBERED

NOTES.

SEE

CHAPTER 7
(ASA* )

RATE

PARAMETERS

FOR K3

10T

EXP(-1000(C*C»

>/TI

4-92 O

«'o

44 a ©

© o • • • •"»•*« C\J * II 04 P“ o GO O O fO a X o O o 00 o r- o it r-- 4- • • • • • • • • • • • • • • • O 04 04 •H 04 OJ 04 © O r- 04 04 04 *« O 4- H H H H l I H *-* X < 1 1 1 1 1 1 i • s i 1 1 1 1 I u

44 04 o in in in of in O o in in in in in • • • • • • • • • • • • •

<-4 04 H in in

©

m O 04 04 04 04 4 4 4 > 4 4 04 4 4 4 * •a

41 in in r-

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80

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04 04 04

rl «-4 i 1 1 asUl a Q a Q z Z z

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(At o o o z< N

at 4- Xo

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-1 X H © H

in ** r-- o • • • • G c a

4- 4 4

in o © © in • • • • 04 KJ 04 04 H •*« 1 1 1 1 Q a Q a Z z Z z

04 04 04 04

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a.

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to

m to to H H H- < c X Z o i i t 1 1 1 1 1 1 1 1 i 1 < z O 3

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z & o UJ a cm CM CM CM II 3 Z Z

ll o a i to X fO Z to O (O X X UJ o o z i 1 1 1 w o UJ a >—

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5-1

CHAPTER 5 : RATE EVALUATIONS AND REACTION SUMMARIES

? Two types of material are included in this chapter. The first is

a set of rate coefficient evaluations for the reactions

CO + OH = C0

2

+ H

H

2

+ OH = H

2

0 + H

OH + OH = H

2

0 + 0

CH. + OH = C0 o + H

4 2

N + 0

2 = NO + 0

presented in that order.

The remainder of the chapter is a series of reaction summaries for

reactions that have been studied widely and are reported on by several

evaluators. These are for the reactions

H + 0

2 = 0 + OH

h

2

+ m= h + h + m

H

2

+ 0 = H + OH

o

2

+ m= o + o + m

o

3

+m=o + o

2

+m

0 + 0

3 = 02 + 02

Each summary is a collection of notes, one per evaluation, instead of a single descriptive statement. However, each summary has a common reference list covering all its notes. Usually the notes follow those given by

/ the authors of the papers, but they have occasionally been rewritten. The

sources, here identified by one author and a year, are identified in more

detail in Chapter 7, Specific Notes.
5-2

KINETICS TABLES FOR THE REACTIONS OF HYDROXYL RADICALS

*

f

Wm. E. Wilson, Jr.

Applied Physics Laboratory

The Johns Hopkins University, Silver Spring, Maryland

la Introduction

Rate data for four gas phase reactions of hydroxyl radicals are

reviewed. Recommendations, values for the rate constants, the applicable temperatures and uncertainties are:

CO 4- OH - CO + H

-IS 4-0 7

k = 5.0 x 10 exp(-300/T), 300-2000 K, log kTM

3

H + OH - H + H O

^ ^-11 4-0 3

k = 3.8 x 10 exp(-2600/T), 300-1500 K, log k

TM

“U & / OH 4- OH -» HO 4- 0

k = (2.57 ± 0.50) x 10" 12

, 300 K

CH. 4- OH -* CH 4- H O

4 3 2

k = 4.7 x 10” liexp(-2.5 x 10^/T), 300-2000 K, log k±0.7

The concentration units for which these rates apply are molecules per

3

cm . The hydroxyl disproportionation rate is one -half the rate for OH

disappearance. Rates for the reverse reactions, calculated using equilibrium data are also given.

Work performed at The Applied Physics Laboratory under Contract

N0w62-0604-c with the Bureau of Naval Weapons. An earlier version of

this material was presented at the 1967 Spring Meeting of the Western

States Section, The Combustion Institute, La Jolla, California 24-25

April 1967, Paper WSCI-67-16. Part of the material appeared in "Report

on the Establishment of Chemical Kinetics Tables", Chemical Propulsion

Information Agency, unnumbered report, April 1967, p. 20 and CPIA Publication No. 146, Vol. 1, p. 147 (May 1967).

' ) Present address: Battelle Memorial Institute, 505 King Avenue, Columbus,

Ohio.
5-3

These rates are based upon an evaluation of the absolute rate for

CO + OH and rate ratio data for the others. They are the same as those

1 2* previously reported. 9 The introduction of new data does not cause

sufficient changes to warrant revisions at this time.

Each evaluation is presented in a separate section. The available data are tabulated and graphed. References and comments on them

i are given in each section.

2. Rate Constant for the Reaction CO 4- OH * CO^ + H

The reaction of CO with OH is an important one for several reasons.

This is the primary means of converting CO to CO

2

. Much of the information of OH kinetics exists as ratios of the rate of CO + OH to that

of other reactions. In particular the rates of H^ 4- OH and CH^ 4- OH

are best determined from a value of the rate of CO 4- OH and measurements

of the rate ratio. This reaction also provides a test for theoretical

rate calculations.

This argument could, of course, be inverted and some other reaction

chosen as the base for interpretation of rate ratio data. The only

other choice at present is H^ + OH = H^O 4- H. Two reasons for rejecting

this choice are advanced. (1) The available data on H^ + OH suitable

for setting an absolute value for the rate constant, including its temperature dependence, are less reliable than those for CO 4- OH. This is

discussed below and elaborated in the comments on the H^ 4- OH evaluation.

(2) The activation energy of the CO 4- OH reaction is lower. Errors in

its determination will have little effect on the rates of the other

reactions

There are only four experimental data points for H^ + OH. Three

different measurements at room temperature establish that point (and

24 29 disprove Avramenko's measurements). Kaufman estimated an activation

energy and frequency factor by using his room temperature point and an

27

rate equation given by Fenimore and Jones. Investigation of their

equation indicates that it can give no better than order of magnitude

28 estimates. Kaufman's expression was later used by Ripley and Gardiner

See reference list in Section 2 for CO 4- OH = CO

2

+ H.
5-4

to fit OH concentration data measured in a shock tube to a kinetic

scheme. Although valuable data, this is not considered adequate to

establish a rate equation because other mechanisms, or combinations of

rate expressions might fit the data. Iri addition the calculated fit

seemed to be less sensitive to k(H 4- OH) than other parameters. A

^ 13

more reliable point is due to Dixon-Lewis but he suggests that it may

be only an upper limit. The conclusion then is that the rate of

H^ + OH is so poorly established that it can not be used with rate

ratios to determine another rate. Because there is much more data on

the CO + OH reaction it seems more logical to take it as a standard and

use it with ratios to determine other rate constants.

The pertinent experimental data are presented in Table I and

Figure 1. The suggested value was obtained by assuming the room temperature point of reference 1 to be correct and subjective weighing of

the various high temperature points. The line was then adjusted to

give only one significant figure in the activation energy. The quality

and quantity of the data is not sufficient to justify more sophisticated fitting techniques. This 300 K point was chosen instead of

the point due to Greiner because of the large scatter in Greiner’s

measurements.

The scatter of the points obtained in flames (over an order of

magnitude) is perhaps not so bad as it looks at first glance. Some of

the scatter can be explained. The analysis is complex. Figure 2 shows

the data chain required for the reevaluation of the work of Fenimore

5 8 and Jones. 9 The conclusion reached here is that their reported values

are low because an incorrect value was used for the rate coefficient of

H + D D 4- HD. The high flame points, from the work of Westenberg and

^

£ Fristrom on hydrocarbon oxygen flames may be high because [OH], assumed

to have its equilibrium value, may well exceed this in these flames.

17 18 Relation of this work to other evaluations .Bahn, Cherry, et al,

19 20 Tunder, et al, and Jensen and Kurzius all select the rate expression

of Dixon-Lewis, Wilson, and Westenberg'*' which is that suggested here.

21 22 Fristrom and Westenberg and also Kaskan and Browne included the low
5-5

24

temperature results of Avramenko in their evaluations. These results

are incorrect. They account for the higher activation energies in the

two evaluations.

23 -12

Schofield gives k = 1.1 x 10 exp(-515/T) as a least-square fit

to the results of references 1, 4-6, 8, 13-16. His value falls within

the error limits suggested here. Both analyses use the same low temperature tie point^ and share the flame derived results of references 4, 6

and 8. Schofield includes explosion limit

^

and photolysis results^

not used here. However, the two analyses differ in an important respect.

The flame, photolysis and explosion limit work all determined rate ratios

involving the two systems CO d- OH = CO^ + H and H^ + OH = H + H^O.

Schofield established the rates for the latter system first and then used

them to calculate the CO 4- OH rate. His rate for H^ + OH is 50 percent

higher at 1000 K than that presented in our evaluation of that reaction.

This lead to higher values for the CO 4- OH high temperature data points,

as recalculated by him, and to a higher recommended rate coefficient.

3 1 -13

Baulch et al recommend k = (7.0 ±13.3) x 10 exp(-545 ± 250/T) . Their analysis uses the low temperature results of references 1 and 2,

14 15 those of Ung and Back and Baldwin and Cowe in the middle region and

the higher temperature results from references 3-7, 10-12. They note but

30

do not use the recent report by Wong et al . Their rate parallels

Schofield’s and uses a preassigned value for the rate of H^ + OH

H^O + 0 to interpret rate ratios.

The differences among these last two rate expressions and that given

here are small, particularly when the scatter of the high temperature

points is considered. More and better high temperature results are needed.

-13

A dashed line, k = 8 x 10 exp ( -450 /T), is included in Figure 1 to show

our estimate of the likely maximum temperature dependence of the reaction.

31 22 Both Baulch et al and Kaskan and Browne give rate constants for

the reverse reaction. They are calculated from CO + OH and the equilibrium

32

constant. Baulch also lists the single available value for the reaction

CO + 0D - C0

2

4- D.
5-6

TABLE I: CO + OH - CO„ + H £H* /R = *12.5

Z ZyO

Equilibrium Constant, = 2.34 x 10

3 exp(12,400/T) 300-1000 K

K

p = 8.26 x 10~ 3

exp(ll, 135/T) 1000-2500 K

Rate Constant

in 13r 3i t - 1 - 1

10 k? cm molecule s

-emp • K Ref. Coiranent

1.91 ± .08 300 1 EST

1.48 ± .15 300 2 KS

3.67 1400 3 Well-stirred reactor

3.8 1072 4 Flame, reverse

1.66 1200" 5 Flame, reverse

2.09 1350^

15 1950 6a Flame

3-10 1850 6b Flame

8-16 1650 6c Flame

3.0 1380 7 CO reactor

4.2 1720

2.5 ± 3 1200 9 Flame, reverse

11.5 ± 1.5 2000' 9 CH, flame

4

8.3 ± .2 2150 9 +CH

3

Br

15 ± .2 2000 9 +HC1

12.5 ± .5 2150 9 +CH0 C1

3

.85 ± .3 300 10 Mass spec ., production

1.73 ± .02 300 11 of C0

2

3.2 1600 12 Flame

Suggested Value 300-2000 K k at 1000 K Error Limits

k = 5.0 x 10" 13 exp(-300/T)

3 -1-1

cm molecule s

-13

3.7 x 10 log

10

k

-0 .3

For the reverse reaction,7 calculate k - k/K using K appropriate to

r eq eq

the temperature range of interest.
CO

+

OH

-CO,

+

H

5-7

D9S

4

lo

CNJ

r—H

i

sapjjjBd

e iuD ')) 6o|

LA

CNJ

r-H

i o

OA

i I

roO

CNJ

,_D9S • ,_S9|01U plUO *>| 60|

Figure

1:

Rate

data

for

CO+

OH

=

CO^

+

H.

Recommended

value

.

Line

with

likely

maximum

slope

—

(k

=8

x

10

^exp(

-450/T)

.
DATA

CHAIN

FOR kR

DETERMINED

FROM

FLAME

STRUCTURE

5-8

x • O

44 -d

0) Pi cud

II o

PQ d 1 •H

S3 d • • o ! •

CO •rl o u 44 44

cu trt CU p- p cO •N P-i o X

r—

'a o

-Cl cO •rl 44 u C 4-1 <U CU CO -d e rd 4-1 •H 4J o C d

0) CU co cu 4-1 X CO d

CU O •r4 •rl 44 -d 'd O d (U

•rl CO

co d

5-i CO O CO -C O cO

4-1 5-< d 5-4 c0 CO 4-1 CO to CU •5

5-4 54

0> 0) 44 • -9

CU LO 6

5-4 d • d

CO 44

<U (U cO CO

CU CU -d II 4-1 44 CO d *d 54

CU P-4 CU )4 d

CO cu Cu co 60

T—

C5 O

•H • 44 44

co cu •d

t-—

Pi cu c« co

•rl II d

44 •H CO d i co M O £

CM

CUud

60

•rl Pu
5-9

References and Comments: CO + OH = CO^ 4- H

1.

Dixon-Lewis, G., Wilson, W. E., and Westenberg, A. A., "Studies of

Hydroxyl Radical Kinetics by Quantitative ESR", J. Chem. Phys . 44

,

2877 (1966).

The OH was generated by H 4- NO^ - NO + OH. Quantitative

electron spin resonance was used to determine the initial

concentration and to follow the hydroxyl radical decay in

a fast flow system at ~ 1mm pressure.

2.

Greiner, N. R., "Hydroxyl Radical Kinetics hy Kinetic Spectroscopy.

I. Reactions with H2 , CO and CH4 at 300°K", J. Chem. Phys. 46,

2795 (1967).

The OH was generated by flash photolysis of H2O and the

decay followed by kinetic spectroscopy (absorption,

static system, pressure 20-200 mm.) Because of the

short time of reaction (< 200 x 10 “^ s ) and the large

ratio of reactant to OH the reaction could be treated

as second order and wall and three -body reactions were

not significant.

3.

Hottel, H. C., Williams, G. C., Nerheim, N. M., and Schneider, G. R.,

"Kinetic Studies in Stirred Reactors: Combustion of Carbon Monoxide

and Propane", Symp. Combust. 10th (The Combustion Institute, 1965)

p. 111 .k was calculated from a study of CO combustion rates

in a well stirred reactor.

Dixon-Lewis, G., Sutton, M. M., and Williams, A., "Reactions Contributing to the Establishment of the Water Gas Equilibrium When Carbon

Dioxide is Added to a Hydrogen-Oxygen Flame", Trans. Faraday Soc. 61

,

255 (1965).

The ratio k (H 4- D

2 0 -» HD + 0D)/k(H + C0 2 - CO + OH) = 4.3 was determined at 1072 K by the addition of small

amounts of D 20 and CO to a previously studied H 2

- 0 2

flame, k was calculated from the equilibrium constant

and k(H 4* D 20 ) = 1.56 x 10”^-^exp( -11, 000/T) cm^ molecule

-1

-1 given in Dixon-Lewis, G., Sutton, M. M„, and Williams, A.

"The Reactions of Hydrogen Atoms with Nitrous Oxide."

J. Chem. Soc. 5724 (1965). This value depends ultimately

on k(H + D

2

”* HD 4* D) . The value used was probably high

by a factor of 1 . 8 ; the resulting k may therefore be low

by as much as a factor of 1 . 8 .

5. Fenimore, C. P. and Jones, G. W., "The Reaction of Hydrogen Atoms with

Carbon Dioxide at 1200-1350°K", J. Phys. Chem. 62. 1578 (1958).

The ratio k(H 4* D20)/k(ft 4

s C0 2 )was determined in the post

flame gases of several flames» The value 3 exp(-3900/T) for

this work was reported in ref. 8 . k may be slightly low

because no corrections were made for diffusion. Comments

under 4 apply here also.
5-10

6 a. Westenberg, A. A. and Fristrom, D. M., " Me than^ -Oxygen Flame

Structure. IV. Chemical Kinetics Considerations”, J. Phys. Chem.

65, 591 (1961).

6b, c. Westenberg, A. A. and Fristrom, R. M., ”H and 0 Atom Profiles

Measured by ESR in C

2 Hydrocarbon Flames", Symp. Combust. 10th

(The Combustion Institute, 1965) p. 473.

k was determined in low pressure ( 1/10 atm) flames

[( 6a):CH4 + 0 2 , ( 6b): C2H6 + 0 2 , ( 6 c): C2H4 + 02

] from the measured [CO], [d CO/dt] chem, and assuming

[OH] at hot boundary is given by chemical equilibrium

conditions. Since [OH] may well exceed equilibrium

values these rates may be too high.

7. Jost, W., Schecker, H. Gg., and Wagner, H. Gg., Z. Physik. Chem.

(Frankfurt) 45, 47 (1965). , OH was generated in a flame and the combustion gases

allowed to come to equilibrium; additional CO was

added and reaction rate measured.

8 . Fenimore, C. P. and Jones, G. W., "Rate of Reaction in Hydrogen,

Nitrous Oxide and in Some Other Flames", J. Phys. Chem. 63, 1154

(1959).

The ratio k(C02 + H)/k(D

2 + OH) was found to be 7-9

in the 1000-1200 K region of a flame. Diffusion

corrections were made. See comments under 4.

9. Wilson, Wm. E., Jr., O'Donovan, J. T., and Fristrom, R. M., "Flame

Inhibition by Halogen Compounds", Symp. Combust. 12th (Poitiers,

France, 1968)

(a): CH4 + 02 uninhibited, (b) : inhibited with C^Br,

(c) : inhibited with HC1, (d) : inhibited with CH3 CI.

CH^Br is the most effective inhibitor and Br is probably a good catalyst for recombination so 9a should

have [OH] nearest the equilibrium value and does have

the lowest rate. See comments under 8 .

10.

Herron, John T., "Mass -Spectrome trie Study of the Rate of the Reaction

cf CO + OH", J. Chem. Phys. 45, 1854 (1966).

The OH was generated by H + N02

-* NO + OH, with excess

NO2 , the H generated by CO + OH -* CO2 + H regenerates

a OH so that d(0H)/dt is not effected by the CO reaction.

From a measurement of the initial [OH], the C02 formed as

a function of [CO], and k for the OH decay it is possible

to calculate k(C0 + OH) . Herron used k(0H + OH) = 0.75 x lO-^ dUe to Kaufman, Xf k(0H + OH) = 1.55 x 10 -^ due to Dixon-Lewis, Wilson, Westenberg is used Herron's

results give k(C0 + OH) = .45 - .92 x 10^ (all in mole

units) . The low value and large scatter are the result

of reaction of OH with N0 2 which was not recognized by

Herron. This value was ignored in determining the suggested values.
5-11

I 11. Wilson, Wm. E., Jr. an<l 0 Donovan, J. T., Mass -Spectrometric Study

of the Reaction Rate of OH with Itself and With CO", J. Chem. Phys

47, 5455 (1967).

See 10 above. When Herron’s experiment was repeated

it was discovered that the value of k(C0 + OH) obtained

was a function of the The reaction was studied

as a function of [ NO 2 ] and [NO2 ] extrapolated to 0 to

obtain the value shown.

12. Porter, R. P., Clark, A. H., Kaskan, W. E., and Browne, W. E., "A

Study of Hydrocarbon Flames", Symp. Combust. 11th (1967), p. 907.

The burnt gas region of a low pressure (18 Torr)

acetylene -oxygen-nitrogen flame was analyzed. CO

and CO

2

determined by gas chromatography. OH determined spectrophotometrically . The CO + OH reaction

assumed (quite properly) to be the main producer of

CO

2

. This is a "preliminary analysis" of one flame.

13. Dixon-Lewis, G., Sutton, M. M., and Williams, A., Symp. Combust. 10th,

(1965), p. 495.

14. Ung, A. Y-M. and Back, R. A., Can. J. Chem. 42. 753 (1964).

15. Baldwin, R. R., Jackson, D., Walker, R. W., and Webster, S. J.,

Symp. Combust. 10th (1965), p. 423.

16. Baldwin, R. R. and Cowe, D. W., Trans. Faraday Soc. 58, 1768 (1962).

17. Bahn, G. S., Pyrodynamics 6, 101 (1968).

18. Cherry, S. S., Gold, P. I., and Van Nice, L. J., TRW Systems, Redondo

Beach, California, Report 08832-6001-T0000

19. Tunder, R., Mayer, S., Cook, E., and Schieler, L., Aerospace Corp.,

Thermochemistry Research Dept., Report No. TR-1001(9210-02) -1 (1967).

20. Jensen, D. E. and Kurzius, S. C., Aerochem Research Laboratories,

Princeton, N. J., March 1967. Report TP-149.

21. Fristrom, R. M. and Westenberg, A. A., "Flame Structure" (McGrawHill Book Co., New York, p. 367 (1965)).

22. Kaskan, W. E. and Browne, W. G., General Electric Co. Space Sciences

Laboratory Report R64SD37, July 1964.

23. Schofield, K., Planet. Space Sci. 15, 643 (1967).

Reaction 4, Table 1; Table 5; Figure 2c, Figure 5.
5-12

24. Avramenko, L. I. and Lorentso, R. V., Z. Fiz. Khim. 24, 207 (1950).

The objection to the use of results from this paper

rests on an examination of the products of a discharge through water vapor. Hydroxyl concentrations

are low and relatively constant. Rates based on

measurement df [OH] will then be low and invalid.

See references 25, 26.

25a. Kaufman, F. and Del Greco, F. P., "Formation, Lifetime and Decay of

OH Radicals in Discharge -Flow Systems", J. Chem. Phys . 35. 1895

(1961).

25b. Del Greco, F. P. and Kaufman, F., "Lifetime and Reactions of OH

Radicals in Discharge Flow Systems", Dis. Faraday Soc. 33

,

128 (1962).

Measurements of the concentration of OH downstream of

an electric discharge through water vapor (optical

absorption) showed that the discharge is an inefficient source of OH (but is efficient in producing H)

and that the concentration of OH exhibited an abnormal

variation, often S -shaped, instead of the expected

monotonic decrease with distance. O

2

increases the

[OH] slightly. It is suggested that reactions of H

with O 2 regenerate OH and that OH is readily dissociated

by the discharge. The chemical production of OH by

H + NO2 = NO + OH does not exhibit this behavior. A

graph comparing the two OH sources is included in the

second paper.

26. Westenberg, A. A. and De Haas, N., "Quantitative ESR Measurements

of Gas Phase H and OH Concentrations in the H-N0« Reaction",

J. Chem. Phys. 43, 1550 (1965).

A study of the H and OH concentrations from H + NO2 - NO + OH showed that this method is a reliable producer

of OH and that the [OH] is directly related to the N0£

flow at low [OH], At higher levels, the concentration

reaches a plateau due to the reactions OH 4- OH = H2O + 0,

0 + OH = H 4- O

2 competing with OH production. See ref. 11.

27. Fenimore, C. P. and Jones, G. W., J. Phys. Chem. 65, 993 (1961).

• / 28. Ripley, D. L. and Gardiner, Wm. C., Jr., J. Chem. Phys. 44, 2285

(1966).

29. Kaufman, F. and Del Greco, F. P., Symp. Combust. 9th, p. 659 (1963).

30. Wong, E. L ., Potter, A. E,, and Belles, F. E., NASA TN D-4162 (1967).

31. Baulch, D. L., Drysdale, D. D., and Lloyd, A 0 C., High Temperature

Reaction Rate Data, Report No. 1, May 1968, Dept, of Physical Chemistry, The University, Leeds, England.
5-13

The value cited here is taken from page 4 of the report.

That on page 1 appears to be a misprint. The estimated

precision on page 1 has been interpreted as logk ± 0.3.

32. Westenberg, A. A. and Wilson, Wm. E., Jr., J. Chem. Phys . 45. 338

(1966).
5-14

3, Rate Constant for the Reaction + OH = H + H^O

This reaction has received much attention since it figures jlarge

in the interpretation of the hydrogen-oxygen system. It has been

studied directly at room temperature using three analytical techniques,

estimated from competitive experiments in studies on water photolysis,

explosion limits in vairious flames, and determined in shock wave

studies of the reaction.

This reaction is the alternative to CO + OH = CO^ + H as the basic

reaction against which rates of other OH reactions are to be scaled.

There are direct measures of the rate of the H^ + OH reaction. They are

not considered to be sufficiently accurate to be used to establish a value for the rate. Consequently, rate ratio data are relied upon here.

The choice of the base reaction is discussed in the introductory material for this set of evaluations. The limitations of the individual

numbers are discussed in the notes following each reference.

Analytical problems concerning the determination of [OH] are discussed in the evaluation of OH + OH = ^0 + H. They are not so important here because this reaction has been studied in the presence of a high concentration of H^, that is, under pseudo-first order conditions.

In contrast to the OH disproportionation the room temperature rates

for this reaction are in good agreement.

The data are listed in Table II. The rate ratio kCl^ + OH = H^O + H) /

k(C0 + OH = C0^ + H) is shown in Figure 5 (from reference 2). This is

used to determine the temperature coefficient, the rate constant for

CO + OH being taken from a separate evaluation. The ratios at 300 K

are not from competitive studies, but were calculated from direct

measurements on the two reactions. The lower 300 K ratio is used as a tie -point on the graph. Adjustment to include the work of Greiner

would raise the pre-exponential factor to 0.038 but would not affect

the activation energy. In view of the spread of the high temperature

values, introduction of this small change is not warranted at present.

Figure 4 shows the recommended rate constant as a function of temperature.
5-1'*

Relation to Other Evaluations

14

For the reaction H + OH = H 4- H O both Tunder, et al and Cherry,

15

1 1

2

et al adopt the rate of Dixon-Lewis, Wilson, and Westenberg. By

considering the range of other reported data (mostly higher) the latter

assigns an uncertainty factor of 10 to cover the probable value. Tunder,

+0 5

et al recast the rate to include a T

* term. They also give a rate for

H + H^O = + OH calculated by a modified Johnston and Parr technique.

The ratio of this rate and that, in reference 1 do not yield the equilibrium constant.

16 17 Bahn and also Kaskan and Browne chose rates recommended by

31) Kaufman and Del Greco.

18 3a Bascombe used the data of Del Greco and Kaufman and Dixon-Lewis,

Sutton and Williams^* to construct the rate for H^ + OH = H + H^O and

then used equilibrium data to get that for the reverse.

< 19 Schofield bases his value on the measurements of reference 2

(300 K) and the shock tube study (1500-2500 K) of Ripley and Gardiner."*

His rate and that given here agree at 300 K. His is 40% higher at 1000 K.

20 Fristrom and Westenberg developed a rate constant for H + H

9 0 =

11 / ^ H^ + OH, k = 8.3 x 10 exp(-1.0 x 10 /T) from the results of references

3b, 6a, 7a.

Jensen and Kurzius^ suggest that the higher temperature work indicates higher activation energies for both the forward and reverse reaction

than by Fristrom and Westenberg. Their rate is 40% lower at 300 K than

that given here and agrees with it around 1000 K.

21
5-16

TABLE II : H

2

+ OH - H O + H AH°

293 /r = -7.56

Equilibrium Constant, K = 0.211 exp(7640/T)

Rate Constant

, 3 i

. — 1 — 1

kj cm molecule s Temp • K Ref. Comment

3.65 x

10' 13

T°*

56exp(-2200/T) 1-4 x 10

3

1 Calc.

6.5 ± 0.3 x 10‘ 15 300 2 ESR

-15

7 ±2 x 10 300 3 Abs. Spec.

6.6 + 0.3 x 10' 15 301 4 Yq.AU

6.5 x 10

_11exp( -2850/T) 1.4-2. 5 x 10

3

5 Shock wave

Computer fit

-12

2.9 x 10 1072 6 Flame

4.2 x 10' 13 exp(-5000/T) 1285-1700 7 Flame

Rate ratio: k(H

2

+

0.034 ± .003

0.045 ± 0.006

0.429

0.615

0.875

1.221

4.5 ± 0.5

8.4

22.3

H

2

0 + H)/k(C0 + OH

300

301

473~

523

573

623

773

1072 K

1275

C0

2

+ H)

9

10

11

Direct studies

both k’s

H

2

0 photolysis

Explosion limits

Flame

F lame

Suggested Values 300-1500 K k at 1000 K Error Limits

R = kjj /k

CQ = 0.034 ± 0.003

exp{ [ 2300 ± 150 ] / [ 1/300 -1/T]}

Using k (CO + OH) =

5.0 x 10" 13 exp(-300/T)

k(H

2

+ OH) = 3.8 x 10' Uexp(-2600/T)

For the reverse reaction

k(H + Ho0) =

^ in 4. 1.8 x 10 iUexp( -1.0 x 10 /T)

7.3

- +0 . 3

log R

-0 . 17

log R -0.17

2.8 x 10

-12

log k+0.3

-0.7

8.2 x 10

-15
5-17

l/T ( K-' x 10 3

)

Figure 3: Rate ratio data (H^ + OH)/k^(CO + OH). ® Fenimore

and Jones, ref. 11, + Dixon-Lewis et al, ref. 10,

A Baldwin, ref. 9, O Ung and Back, ref. 8, O Dixon-Lewis

et al, ref. 2, V Greiner, ref. 4. Figure reproduced from

J. Chem. Phys. 44, 2883 (1966) with the permission of the

American Institute of Physics. Point from ref. 4 added.
5-18

Figure 4: Rate data for H

2 + OH -^O-f- H —recommended

-11 value, k = 3 8 x 10 exp( 2600/TV refs 2, 3,4. 0— ref. 6, a-ref. 1, b-ref. 1, c-ref. 5
5-19

References and Comments: + OH = H^O + H

1. Mayer, S. W., Schieler, L., and Johnston, H. S., "Computation of

High -Temperature Rate Constants for Bimolecular Reactions of

Combustion Products", Symp. Combust. 11th, p. 837 (1967).

Equation fits calculated rates from 1000-4000 K.

This equation agrees well, within a factor of 2,

with the suggested value from 300-2500 K.

2. Dixon-Lewis, G., Wilson, W. E., and Westenberg, A. A., "Studies of

Hydroxyl Radical Kinetics by Quantitative ESR", J. Chem. Phys. 44,

2877 (1966).

The OH was generated by H + NO 2 = NO + OH. Quantitative

electron spin resonance was used to determine the initial

concentration and to follow the hydroxyl radical decay in

a fast flow system at ~ 1 mm pressure.

3a. Del Greco, F. P. and Kaufman, F., "Lifetime and Reactions of OH

Radicals in Discharge Flow Systems", Dis. Faraday Soc. 33

,

128

(1962).

b. Kaufman, F. and Del Greco, F. P., "Fast Reactions of OH Radicals",

Symp. Combust. 9th, p. 659 (1963).

c. Kaufman, F., Ann. Geophys. 20, 106 (1964).

The OH was generated by H + NO2 = NO + OH. Adsorption spectrometry was used to determine the initial

concentration and to follow the OH decay in a fast

flow los pressure system. ’ In the experiments H

2 + OH

and OH + OH are competitive, the former being the

faster. The first two papers describe the experimental

work. The value is quoted from the last.

4. Greiner, N. R., "Hydroxyl Radical Kinetics by Kinetic Spectroscopy.

I. Reactions with H^, CO and CH at 300°K", J. Chem. Phys. 46,

2795 (1967).

4

The OH was generated by flash photolysis of H2 O and the

decay followed by kinetic spectroscopy (absorption).

(static system, pressure 20-200 mm.) Because of the

short time of reaction (< 200 x 10“^ s ) and the large

ratio of reactant to OH the reaction could be treated

as second order and wall and three-body reactions were

not significant.

5. Ripley, D. L. and Gardiner, W. C., Jr,, "Shock -Tube Study of the

Hydrogen-Oxygen Reaction. II. Role of Exchange Initiation", J. Chem.

Phys. 44, 2285 (1966).

Induction time measurements on the H2 -O 2 reaction

(~ 1400-2500 K) were interpreted in terms of hydrogen
5-20

and oxygen dissociation, H + 0£ = OH + 0, 0 + H

2 = OH + H and OH + H2 = H2O + H* The analytical solution for this set of reactions yielded the best fit

rate parameters. The results suggest that the

behavior of the system is not very sensitive to the

rate of OH + H2

. Because of this and because some

modified mechanism might fit the data equally well

this rate constant is not considered adequate for

use in establishing a recommended rate.

6a. Dixon-Lewis, G. and Williams, A.), "Some Observations on the Structure

of a Slow Burning Flame Supported by the Reaction between Hydrogen

and Oxygen at Atmospheric Pressure", Symp. Combust 9th, p. 576 (1963).

6b. Dixon-Lewis, G., Sutton, M. M., and Williams, A., "Some Reactions of

Hydrogen Atoms and Simple Radicals at High Temperatures", Symp. Combust,

10th, p. 495 (1965).

Potentially, this work provides a rate estimate

independent of rate ratios involving other hydroxyl

reactions. The first paper reported k(H + D^O = HD + OH) = 5.0 x 10 9 cm

3 mol" 1

’

1 s" 1 at 1072 K from

(d[D20]/dt) c|iem and [H], [H ] established by D

2

tracer technique II + D2 = HD + D in early part of

flame, chemiluminescence in central portion, and

D2O tracer in burned gas portion of flame, The D2

tracer gives absolute [H], the others relative. D2

trace results are then used to scale [H] in other

regions. The k then depends on a number of assumptions. The authors state "this may be an upper limit".

The k also depends on the value of k(H + D

2

) used.

Recent studies of H + D

2 indicates a rate of k(H + D

2

)

only about one -half of that used. 19 This value is

therefore, not considered reliable enough to use in

establishing a value of k 0 The second paper includes a value for k(H + D9 0

HD + OH = 3.6 x 109 cm3 mol -1 s" 1 at 1072 K based

on new experiments on H2 -O 2 flames and a revised

estimate for k(H + H2 O

-* H2 + OH) = 6.7 x 109 based on

references 6a, 3b. The value in the table was calculated

from the latter and the equilibrium constant.

7a. Fenimore C. P. and Jones, G. W., "Determination of Hydrogen Atoms in

Rich, Flat, Premixed Flames by Reaction with Heavy Water", J. Phys.

Chem. 62, 693 (1958).

7b. Fenimore, C. P. and Jones, G. W., "Rate of Reaction, 0 + H

2

“* OH + H,

in Flames", J. Phys. Chem. 65, 993 (1961).

Potentially this work would provide a measurement of

the rate that is independent of rates of other hydroxyl

radical reactions.
5-21

D 2O was added to a rich H2 and H2 + CO Flames and

(d HD/dt) chem from H + D 2O -* HD + OD determined.

The temperature range was 1285-1500 K in H

2

flames

and 1345-1700 K in hydrocarbon flames. The Avramenko

and Lorentso^ value for k(0H + H^) and the equilibrium

constant were used to obtain k(H + H2O) . This value

was then increased by a factor of two in the flame

temperature range. This value of k(H + H2O) was then

used to determine [H], (All isotopic rates were assumed

to be the same.) The [H] found was said to be consistent with that of Bulewicz, James and Sugden measured by a different method at a higher temperature.

The consistency was based on log [H]/[H]

e(^. being linear

with 1/T for both sets of flames. Considering the number and extent of assumptions made and that Avramenko

and Lorentso’s rate value is low by 100 to 1000 in the

temperature in which they measured it, the agreement

between the [H] of Bulewicz, et al and that reported

here is more accidental than meaningful.

The rate (d[D20 ] /dt) chein was also measured in rich

hydrocarbon flames. The k(H + D2O) used earlier gave

[H] equal to the equilibrium concentration. This is

better evidence for k(H2 + OH) but still can hardly

be considered to be of better than order of magnitude

accuracy

In the second paper, the rate equation k(H2 + OH) =

2.5 x 10^1 exp(-5 x 10^ /T) cm^mol"ls“l was stated for

these experiments. This retains the Avramenko and

Lorentso temperature dependence. Kaufman^b used his

room temperature value and a value for 1500 K calculated from this equation to give k = 10 ^- 0 • 8 ± .7

exp(-2.95 ± X.0/T). This value has been widely quoted

in the literature, usually without the large uncertainty

given by Kaufman. Considering how the high temperature

point was obtained an uncertainty of only 1 kcal was

decidedly optimistic. In all fairness it should be

pointed out that in 1960 order of magnitude values of

reaction rates in flame were of interest. To attempt

to use them today to provide rate constants reliable

to a factor of two or better is not justified.

8 . Ung, A. Y. M. and Back, R. A., "The Photolysis of Water Vapor and

Reactions of Hydroxyl Radicals", Can. J. Chem. 42, 753 (1964).

The OH was generated by photolysis of water, CO 2 was

formed when CO was present. The rate ratio was determined from the decrease in CO 2 formed when H2 was added.

Evidently the three body recombination to form H2O2 was

sufficiently fast to interfere at lower temperatures.
5-22

The H present would react with to give HC>2 which

might react with CO. If this reaction sequence contributed aboVe 473 K it would cause the measured k's

to be low.

9.

Baldwin, R. R., private communication. A revision of the value,

3, reported earlier by Baldwin, R. R. and Cowe, D. W., "The

Inhibition of the Hydrogen and Oxygen Reaction by Formaldehyde",

Trans. Faraday Soc. 58, 1768 (1962). Quoted from reference 2.

10. Dixon-Lewis, G., Sutton, M. M., and Williams, A., "Reactions Contributing to the Establishment of the Water Gas Equilibrium When Carbon

Dioxide is Added to a Hydrogen-Oxygen Flame", Trans. Faraday Soc. 61,

235 (1965).

The ratio of k(H + C02 ) to k(H + D20) = 4.3 ± 0.5

was measured in a H2 -02flame. Assuming k(H + H20)

to be larger than k(H + D

20) by a factor determined

by the zero-point energy difference between single

0-H and 0-D bonds ( 5*4 kJ mol"^ ) f k(H + H20) /

k(H + C02

) = 7.9 ± 1.0, k is then obtained via the

water-gas reaction, C02 + H2 = CO + H20, equilibrium

constant. Their article, Symp. Combust. 10th, p. 495

(1965) also reports on this work.

11. Fenimore, C. P. and Jones, G. W., "The Reaction of Hydrogen Atoms

with Carbon Dioxide at 1200-1350 K", J. Phys. Chem. 62, 1578 (1958),

Idem, Ibid 63, 1154 (1959).

Measured k(H + D20)/k(H + C0 2 ) = 7.0. The second

paper states the ratio as 3 exp(-3925/T) . The

value in the table calculated from this. For conversion method see comment on reference 10.

12. Avramenko, L. I. and Lorentso, R. V., Z. Fiz. Khim. 24, 207 (1950).

Discharge through water vapor used as OH source. Rejected.

13. Bulewicz, E. M., James, C. G., and Sugden, T. M., Proc. Roy. Soc.

A235, 89 (1956).

14. Tunder, R., Mayer, S., Cook, E., and Schieler, L., Aerospace Corp„,

Thermochemistry Research Dept., Report No. TR-1001(9210-02) -1 (1967).

15. Cherry, S. S., Gold, P. I., and Van Nice, L. J., TRW Systems, Redondo

Beach, California, Report 08832-6001-T0000

16. Bahn, G. S., Pyrodynamics 3., 245 (1965).

17. Kaskan, W. E. and Browne, W. G., General Electric Co. Space Sciences

Laboratory Report R64SD37, July 1964.

18. Bascombe, K. N., "Reaction Rate Data: The Hydrogen/Oxygen System",

Ministry of Aviation, Explosives Research and Development Establishment, Waltham Abbey, Essex, England, E.R.D.E. l/S/65
5-23

19. Schofield, K., Planet. Space Sci. 15. 643 (1967).

20. Fristrom, R. M. and Westenberg, A. A., "Flame Structure" (McGraw

Hill Book Co., New York, p. 367 (1965)).

21. Jensen, D. E. and Kurzius, S. C., Aerochem Research Laboratories

Princeton, N. J., March 1967. Repoft TP-149.
5-24

4 r Rate Constant for the Reaction OH + OH = H^O + 0

i

1 Studies on the disproportionation of hydroxyl radicals at 300 K

have been made using several techniques. Higher temperature values

8

are not available. There is one estimate for the activation energy

— 1 of the reverse reaction, E“ = 19 kcal mol , slightly greater than

the endo the rmi city of the reaction. Kaufman has suggested, on the

basis of the magnitude of the rate constant that the forward reaction

cannot have an activation energy of more than i.5 kcal mol This

is reasonable but as yet not supported by measurements.

Here the procedure is to establish only a value at 300 K. That

chosen is the higher value. This is consistent with modem work on

the CO + OH reaction. The rate constant for the latter is developed

in a separate evaluation.

An accurate estimate of the absolute concentration of OH is needed

for rate measurements on this reaction. The need is acute, the reaction

being second order on OH and a value for the concentration appearing in

the rate expression. This is in contrast to the other OH reactions

which can be run in the presence of an excess of the other reagent,

that is, under pseudo-first order conditions. Most of the discrepancy

between the two measurements on this reaction is undoubtedly due to

uncertainty in the analytical calibrations.

Relation to Other Evaluations

2 The work of Kaufman and Del Greco is the basis for several evaluations. They used their 300 K measurements and an assumed 1000 kcal

""1 mole activation energy. The alternative energy item, E = 18 kcal /mole

g for the reverse reaction is also used. These are equivalent. Kaskan

9 10 11 12 and Browne, Bascombe, Bahn, and Tunder, et al all report numbers

13 traceable to Kaufman. Cherry, et al selected a value calculated by

14 Bahn based on Langen and Creswell’s equivalent expression for the

reverse reaction. Schofield‘S adopts the 1000 cal mol ^ activation
5-25

energy and the room temperature value from reference 1. For his

definition of k, this value should be doubled. His rate for the

reverse reaction uses equilibrium data and the 18 kcal mol ^ va lue
5-26

TABLE III

OH + OH = H„0 + 0 £H° 0 /R = 8.49 x 10

3

2 Zyo

-0

Equilibrium Constant, K = 5.88 x 10 exp(8580/T)

Rate Constant i

cm^ molecule ^s Temp. K Ref

Comment

2.57 + 0.25 x 10" 12

300 1 ESR

1.4 ± 0.25 300 2 Abs. Spec.

2.2 ± 0.6 x 10' 12 300 3 ESR

-13

>, 1.7 x 10 300 4 Surface combination

of H atoms

Several mass-spectrometric studies 5

support the higher value of k if 6

k(C0 + OH - CO + H) =

-13 3 -1

1.9 ± 0.4 x 10 cm molecule

7

s” 1 is accepted

Definition of k: d[OH]/dt =~2k[OH]^

Suggested Values k at 300 K

OH + OH = H

2

0 + 0 2.57 ± 0.50 x 10~ 12

3 , , -1 -1

cm molecule s H

2

0 + 0 = OH + OH 3.4 x 10

-24
5-27

References aid Comments: OH + OH - H^O + 0

1. Dixon-Lewis, G., Wilson, W. E., and Westenberg; A. A., "Studies of

Hydroxyl Radical Kinetics by Quantitative ESR", J. Chem. Phys. 44,

2877 (1966).

The OH was generated by H + NO 2 NO + OH. Quantitative electron spin resonance was used to determine

the initial concentration and to follow the second

order OH decay in a fast flow system at ~ 1mm

pressure

2. Del Greco, F. P. and Kaufman, F., "Lifetime and Reactions of OH

Radicals in Discharge Flow Systems", Disc. Faraday Soc. 33. 128

(1962); Kaufman, F. and Del Greco, F. P # , "Fast Reactions of OH

Radicals", Symp. Combust. 9th, p. 659 (1963); Kaufman, F.,

"Aeronomic Reactions Involving Hydrogen. A Review of Recent Laboratory Studies", Ann. Geophys. 20. 106 (1964).

The OH was generated by H + NO2 ^ NO + OH and the

second order decay measured by absorption spectroscopy near 3000 A. The initial OH concentration

[OH] was determined by assuming 1) that there was a region where H + NO 2

”* NO + OH had gone to completion and OH + OH H 2O 4- 0 had not yet begun and 2)

that [OH] in this region was given by the NO2 flow

rate. The light absorption path integrated 1/3 msec

of reaction time and mixing required 1 msec. It

appears that the initial OH concentration was overestimated because both the finite mixing time and

the overlapping of the formation and decay reactions

would lead to a lower actual [OH] than given by the

NO2 flow rate. If the actual [OH] were % of the

anticipated [OH] the derived k would agree with that

from Ref. 1. The calibration, [OH] vs absorption,

may also require revision. This depends upon the f

number for OH. A recent study (reference 16) reports

an f number higher by a factor of 2 than that used by

Kaufman .

U

Use of a higher f number would reduce [OH]

and increase the rate.

Experimental procedures and results are described in

the first two papers. The value quoted here is based

on the last. (The definition of k in these papers is

d[0H]/dt = -k[0H]2. That used here is d[0H]/dt =

-2k[0H] 2

.)
5-28

3. Westenberg, A. A. and De Haas, N 0 , "Quantitative ESR Measurements

of Gas Phase H and OH Concentrations in the H-NO2 Reaction", J. Chem.

Phys. 43, 1550 (1965).

A study of H and OH concentrations as a function of

H and NO flow rates showed the occurance of OH + OH -* H2O + 0 and 0 + OH ^ H + 02* The value quoted in the

table is the revised one given in reference 1. Considered by the authors to be an estimate, and to be

superseded by the later study (reference 1) . -

4. Wise, H., Ablow, C. M., and Sancier, K. M., "Diffusion and Heterogeneous Reaction. VI. Surface Recombination in ,the Presence of

Distributed Atom Sources", J. Chem. Phys. 41, 3569 (1964).

Only a lower limit for the rate coefficient was

obtained

5. Reference 1 also reports a mass-spectrometric study of the CO-OH

reaction in which the ratio O 2 /CO 2 (O 2 formed via OH + OH = H2O + 0,

0 + OH = O 2 + H and CO2 formed via CO + OH - CO2 + H) supports the

higher value of k.

6. Herron, J. T., "Mass Spectrometric Study of the Rate of Reaction of

CO with OH", J. Chem. Phys. 45, 1845 (1966).

If the rate of CO + OH is assumed to have the value

indicated in the table, Herron's measurements,

corrected for the effect of NO2 on the rate, support

the suggested value. See reference 7.

7. Wilson, Wm. E., Jr. and O'Donovah, J. T., "Mass Spectrometric Study

of the Reaction Rate of OH with Itself and with CO", J. Chem. Phys.

47, 5455 (1967).

A repetition of the experiments of reference 6 showing that the CO + OH rate depends upon the NO2 concentration. (The reaction NO 2 + H = NO + OH used to

produce hydroxyl.) The suggested value for OH + OH

given in the table is shown to be consistent with the

recommended CO + OH rate.

8. Voevodsky, V. V. and Kondratiev, V. N., Progr. Reaction Kinetics 1,

41 (1961).

Citing preliminary work of Azatyan.

9. Kaskan, W. E. and Browne, W. G., General Electric Co. Space Sciences

Laboratory Report R64SD37, July 1964.

10.

Bascombe, K. H., "Reaction Rate Data: The Hydrogen/Oxygen System",

Ministry of Aviation, Explosives Research and Development Establishment, Waltham Abbey, Essex, England, E.R.D.E. l/S/65
5-29

11. Bahn, G. S., "Chemical Kinetics. Reactions Among H2O, HO2 , H2O2 , and O3 , also Involving H2 , O 2 , OH, H and 0", Pyrodynamics 2,

245 (1965).

12. Tunder, R., Mayer, S., Cook, E., and Schieler, L., Aerospace Corp.,

Thermochemistry Research Dept., Report No. TR-1001(9210-02) -1 (1967).

Quoting from Fristrom, R. M. and Westenberg, A. A.,

"Flame Structure" (McGraw-Hill Book Co., New York,

p. 367 (1965))

13. Cherry, S. S., Gold, F. I., and Van Nice, L. J., TRW Systems,

Redondo Beach, California, Report 08832-6001-T0000

14. Langen, W. T., Creswell, J. D., and Browne, W. G., "Effects of

Ablation Products on Ionization in Hypersonic Wakes", J. Am. Inst.

Aeron. Astronaut. 3_, 2211 (1965).

A secondary source for rate data. The report of

these authors. General Electric Technical Information Series 65SD208 (January 1965), same title, is

stated to contain the detailed analysis. (Not

examined)

15. Schofield, K., Planet. Space Sci. 15. 643 (1967).

16. Anketell, J. and Pery-Thorne, A., "Oscillator Strength in the Band

System of OH by the Hook Method", Proc. Roy. Soc. A301. 343 (1967).

The value, fQO = 14.8 x 10"^ is the highest of

those that need to be considered. Based on assumed

equilibrium [OH] produced from an 0? + H2O mixture

in a flow system 1550-1675° C. The product [OH] x f

is always measured. In f number determination,

understatement of [OH] produces a high f. At comparable temperatures in flames, [OH] can exceed the

equilibrium value. In analysis, a low f causes

overstatement of [OH], Other recent f number

determinations reviewed.

17. Golden, D. M., Del Greco, F. P., and Kaufman, F., "Experimental

Oscillator Strength of OH, -» 2[], by a Chemical Method", J. Chem.

Phys. 39, 3034 (1963).

Hydroxyl production and initial concentrations

based on H + NO 2 = NO + OH in a flow system.

The value, f = 7.1 x 10“^, is considered by the

authors to be more likely low than high.
5-30

5. Rate Constant for the Reaction CH, + OH = CH0 + Ho0

4 3 2

The reaction of methane with hydroxyl radical las been studied

directly over the temperature range 300-1200 K using three different

methods of analysis, in the "slow combustion" of CH^ by 0^ (700-900 K)

and in flames. In the last two, rate ratios are determined, the rates

of CH^ and CO with OH usually being compared.

The data are presented in Table IV. Remarks on individual papers

are included in the reference list. Most of the intermediate temperature range data must be discarded because of the likely importance of

other reactions, notably that of HO^ with CH^, which may compete that

of hydroxyl. These studies, which are marked in the table, give lower

rates than those accepted.

The rate constant for the CH^ + OH reaction has been set here by

first establishing the temperature variation of the ratio k(CH^ + OH)/

k(C0 + OH) and then using the value of the rate for the latter,

k = 5.0 x 10

-13

exp(-300/T) cm

3-1-1

molecule s

,

. discussed in a separate

evaluation and based on reference 16. The ratio data are plotted in

Figure $. The 300 K points are combinations of direct measurements.

That based on references 5 and 16 is used as a pivot on the plot.

The recommended value is shown in Figure 6 together with several

data items not used in determining the rate ratio and two high temperature rate expressions. The 300 K fit is, of course, not independent

of Figure 5. If the pre-exponential factor were lowered by only 207>

the line would run through the points of Greiner and Dixon-Lewis and

Williams. When the spread of the high temperature data is considered,

it is not appropriate to introduce this change at present.

The suggested rate for CH^ + H^O was obtained using the equilibrium constant.

Schofield has also presented an analysis of this reaction. His

value k = 1.2 x 10

^

exp(-2980/T) , is a least squares fit to the data

of references 2,5,6,9-12,14. The data of the last two have been rejected

here. Apart from the influence of these points, his rate has a stronger

temperature dependence because of the stronger dependence adopted by him

for the CO + OH rate coefficient, k = 1.1 x 10

^

exp(-519/T).
5-31

TABLE IV: CH

4 + OH - CH

3 + ^298 /R = ' 8 * 1

Equilibrium Constant, K = 5.87 exp(8600/T), 300-2500 K

Rate Constant, k = kT5, exp(C/T) Temp . K Ref. Comment

3

i i -1 -1

cm molecule s A

-13

1.83 x 10

B C

0.675 1100 1000-5000 1 Calc

1.8 x 10' 10

0 3270 1350-1850 2 Flame

4 x 10' 10

0 4250 300-600 3 NG*

1 3 n -1 -1 1 k, cm molecule s 8.8 ± 0. 3 x 10" 15 301 4 KS

10.8 ± 2. 5 x 10“ 15 300 5 ESR

5 ± 2 x 10" 12

1285 6 Flame

Rate ratio: k(CH

4 + OH - CH3

+ H

2

0)/k(C0 + OH - C0

2 + H)

0.056 ± 0.013 at 300 K 5, 16

0.060 ± 0.006 at 301 K 4

3.2 - 6.0 at 773 K 7 Exp lim

20 - 25 at 1750-3000 K 8 Flame

17 at 1748, 24 at 1789 K 9 Flame

38 at 1709, 27 at 1743, 33 at 1797 K 10 Flame

15.2 exp (650/T) at 1200-1800 K 11 Flame

1.8 ± 0.9 at 773 K 12 NG* Slow

1.0 at 673 K, 1.5 at 773 K 13 NG* _Comb

0.83 at 673 K, 1.10 at 723 K, 2.1 at 798 K 14 NG*, H2°2

3-5 at 1200 K 15 NG* *

NG: Not considered reliable. Not used in determining the suggested value.
5-32

j TABLE IV (Cont'd),

Suggested Values 300-2000 K k at 1000 K Error Limits

R = k^ /k

CQ = (5.6 ± 1.3) x 10

2 x

4-

1 9.5

log R ± 0.3

exp{[ 2200 ± 150] /[ 1/300 - 1/T ]

k

(CH + OH) = 4.7 x 10‘ 11exp(-2.5 x 10

3

/T)

using k(C0 + OH) = 5.0 x 10"exp(-300/T)

-12

3.86 x 10 i

t +0* 7

108 k

-0.3

^(CH + H 0) ~ X ^0 exp(-ll.l x 10 /T) 1.2 x 10" 16
5-33

k 6 (CH 4 + OH)

log VS

k„ (CO + OH)

0

WILSON AND WESTENBERG

HOARE, 1962

BLUNDELL

BALDWIN a WALKER

<> PRATT

GREINER

FLAMES

1/20 ATM I WESTENBERG

1/ 10 ATM ( a FRISTROM

INHIBITED, WILSON

FENIMORE a JONES

V DIXON- LEWIS

k *

= 5.15 X IO"

l3 EXP (-600/RT)

k 6= 4.7 XIO"11 EXP (- 5000/RT)

I03/T K

3

Figure 5: Rate ratio data for k(CH^ + OH)/k(CO + OH) . A-ref. 5^ 16^

® -ref . 14, #-ref. 12, -ref. 7, O -ref. 15,

V-ref . 4, 0-ref. 9, -ref. 10, — ref. 8, ref, 11,

V-ref. 6. Reproduced from Symp. Combust. 11th, p. 1148

(1967) by permission of the Combustion Institute. Point

from reference 4 added.
5-34

CH 4 + OH —CHg-h H 2 0

oCD

CO

CO

CDo

E

o

8*

Sco

CO

CD

COQ_

E

o

cr> o

io

3

/t k

Figure 6: Rate constants determined directly^ calculations and

recommended values for CH, + OH = CH0 + HO.

4 3 2
5-35

References and Comments: CH. + OH = CH 0 + Ho 0

4 3 2

1. Mayer, S. W. and Schieler, L., "Computed High -Temperature Rate

Constants for Polyatomic Combustion Products", to be published.

2. Fristrom, R. M., "Radical Concentrations and Reactions in a MethaneOxygen Flame", Symp. Combust. 9th, p. 560 (1963).

A compilation of results from several flame studies.

Actually, based on the experimental determination of

k(CH^ + 0H)/k(C0 + OH) and the use of a value of k,

now known to be incorrect, for k(C0 + OH). However,

the value of [OH] does not change much in the temperature range covered so an experimental value of

[OH] determined in a flame similar to the one studied

here was used to correct this value, i.e. the rate

constant in the reference was multiplied by 0.8 to

account for the difference between the experimental

value of [OH] and that calculated using k(C0 + OH).

3. Avramenko, L. I. and Kolensnikova, R. V., "Mechanisms and Rate Constants of Elementary Gas Phase Reactions Involving Hydroxyl Radicals

and Oxygen Atoms", Advances in Photochemistry, Vol. 2, Interscience,

N. Y., 1964, p. 25.

Citing Avramenko, L. I., Ph.D. Thesis Moscow 1952.

This article reviews the Russian work. In the cited

study OH was generated by an electric discharge in

water, the decay in a flow tube was measured by

absorption spectroscopy. Since this is not a satisfactory source of OH for kinetic studies this value

is ignored. This was for many years the only value

at lower than flame temperatures and is responsible

for many erroneous rate equations with activation

energies of ~ 10 kcal which are still found in the

literature. This value should be ignored. The production of OH in electric discharges is discussed

in the CO + OH rate evaluation, Section 2.

4. Greiner, N. R., "Hydroxyl Radical Kinetics by Kinetic Spectroscopy.

I. Reactions with H2 , CO, and CH4. at 300 K", J. Chem. Phys. 46, 2795

(1967).

The OH was generated by flash photolysis of H2O and

the decay was followed by kinetic spectroscopy.

(static system, pressure range 20-200 mm) Because

of the short time of reaction (< 200 x 10 "° s ) and

the large ratio of reactant to OH the reaction could

be treated as first order in OH and wall reactions

could not be significant.
5-36

5. Wilson, W. E. and Westenberg, A. A., "Study of the Reaction of

Hydroxyl Radical with Methane", Symp. Combust. 11th, p. 1143 (1967).

The OH was generated by H f NO2

”* NO + OH.

Quantitative electron spin resonance was used

to determine the initial concentration and to

follow the hydroxyl decay in a fast flow system

at ~ 1 mm pressure. The large error limits give

the limits set by several possible reaction

mechanisms involving OH reactions subsequent to

the initial reaction.

6. Dixon-Lewis, G. and Williams, A., "Some Observations on the Combustion of Methane in Premixed Flames", Symp. Combust. 11th, p. 951

(1967).

[CH^] and d[ CH^ ] /dt

c^em

were measured in a flame by flame structure techniques; [OH] was

determined by absorption spectroscopy and

k(CH^ + OH) calculated at the point of maximum

rate of disappearance of CH4

.

7. Baldwin, R. R., Norris, A. C., and Walker, R. W., "Reactions of Methane

in Slowly Reacting Hydrogen-Oxygen Mixtures", Symp. Combust. 11th,

p. 889 (1967).

Computer treatment of explosion limits of

H2 -O 2 with small additions of methane to give

k(CH4 + OH)/k(H2 + OH) and CO to give

k(CO 4- 0H)/k(H2 + OH); these ratios then give

k(CH4 + OH)/k(CO + OH).

8. Wilson, Wm. E. Jr., O'Donovan, J. T., and Fristrom, R. M., "Flame

Inhibition by Halogen Compounds", Symp. Combust. 12th, Potiers, France,

July 1968, paper 93.

9,10. Westenberg, A. A. and Fristrom, R. M;, "Me thane -Oxygen Flame Structure.

IV. Chemical Kinetic Considerations", J. Phys. Chem. 65, 591 (1961).

Flame structure studies of (9) 1/10 and (10)

1/20 atm CH^ - 0

2

flames.

11. Fenimore, C. P. and Jones, G. W # , "Rate of Reaction of Methane with H

Atoms and OH Radicals", J. Chem. Phys. 65, 2200 (1961).

Flame structure studies of several flames.

Ratio quoted in Table IV calculated (Reference 5) from the rate constants given by

Fenimore and Jones. Note that the activation

energy has the opposite sign from the suggested equation, but that absolute values agree

within the range of experimental measurements.
5-37

12. Blundell, R. V., Cook, W. G. A., Hoare, D. E., and Milne, G. S.,

"Rates of Radical Reactions in Methane Oxidation", Symp. Combust.

10 th, p. 445 (1965).

Slow combustion of CH^ with analysis of CO,

CO2 and H2 CO at times up to 750 sec., pressure

60-450 mm, temp. 773-998 K. Catalytic oxidation of CO on the surface and reaction with HO2

probably cause this value to be low. Because

of expected errors this number is ignored.

13. Slow combustion studies by a variety of workers. Discussion and

references given in Ref. 12 above. These numbers are ignored because

of the reasons given under Ref. 12.

14. Hoare, D. E., "Reactions of Gaseous Hydroxyl Radicals", Nature 194

,

283 (1962). Hoare, D. E., "Studies of the Reactions of Hydroxyl

Radicals. I", Proc. Roy. Soc. A291, 73 (1966). Hoare, D. E. and

Peacock, G. B., "Studies of the Reactions of Hydroxyl Radicals. II",

Proc. Roy. Soc. A29l, 85 (1966).

The thermal decomposition of H2 O2 was used as

a source of OH. The OH formed reacts rapidly

with H2O 2 to form HO 2 which complicates the

reaction mechanism. Because of the presence

of HO2 which also reacts with CO and possibly

with CH4 these numbers are ignored.

15. Pratt, N. H., Symp. Combust. 11th, p. 1150 (1967) and Ph.D. Thesis,

University of London, 1962.

A thermal flow reactor was used. This number

is considered to be in error because of wall

and HO 9 reactions and is ignored.

16. Dixon-Lewis, G., Wilson, Wm. E., Jr., and Westenberg, A. A., "Studies

of Hydroxyl Radical Kinetics by Quantitative ESR", J. Chem. P'nys . 44,

2877 (1966).

17. Schofield, K., Planet. Space Sci. 15, 643 (1967).
5-38

KINETICS TABLES FOR THE REACTIONS

N + 0 = NO + 0 (k,

)

A T

NO + 0 = N -b 0

2

(k_)

-k Wm. E. Wilson, Jr.

Applied Physics Laboratory

The Johns Hopkins University, Silver Spring, Maryland

and

David Garvin

National Bureau of Standards, Washington, D. C Q

The rates of both reactions in this system have been studied, the

forward rate in the temperature range 300-900 K and the reverse rate

in the ranges 1500-1900 and near 5000 K. Data points (which usually

are averages) and rate expressions are listed in Tables I and II.

Remarks on the papers are included in the reference list.

The 0 + NO reaction catalyzes the homogeneous decomposition of NO,

the oxygen atoms being formed by dissociation of 0^ or possibly by

NO + NO N^O + 0. Oxygen molecules also promote the recombination of

N atoms, the simplest sequence being N + 0^ = NO + 0, N + NO = N^ + 0.

The second reaction is much faster, having a rate near the collision

frequency. The net effect is the replacement of N atoms by 0 atoms

with the release of 445 kJ/mol of 0^ consumed.

Work performed at The Applied Physics Laboratory under Contract

N0w62-0604-c with the Bureau of Naval Weapons. An earlier version

(by W.E.W.) appeared in "Report on the Establishment of Chemical

Kinetics Tables", Chemical Propulsion Information Agency, unnumbered

report, April 1967, p. 20 and CPIA Publication No. 146, Vol. 1,

p. 147 (May 1967).

Present address: Battelle Memorial Institute, 505 King Avenue, Columbus,

Ohio.
5-39

The preferred rate coefficient given in Table III cannot be obtained

by averaging the rate parameters. Nor is it easy to visualize from them

the relationship between the various expressions or their agreement or

disagreement. A plot of the points is necessary (Figure 1). Here, the

data for k has been converted to k using the equilibrium constant

• l" values listed in Table I (which have been calculated from the JANAF

Tables)."* All of the measurements agree well in the temperature range

9 in which they overlap except for that of Kretschmer and Petersen.

The range of log k at any temperature is only 0.3. It is reasonable to

treat all of the data as samples drawn from the same set. The suggested

rate expression is a least squares fit to log k - log T = A + C/T. Only

the N + C>2 data have been used. The 0 + NO data has been used only to

dictate the inclusion of a log T term. The listed rate for 0 + NO

has been calculated from that for N + 0^ and the equilibrium constant

(300-900 K).

The kinetic data for this reaction are extensive and good. It is

unusual to find agreement of better than a factor of two over a temperature range as large as 300-5000 K. When there is such good agreement

among a variety of different types of studies the rate equation may be

considered reliable.

Relation to other evaluations. Wray and Teare combined their

5000 K value for the rate of 0 + NO 55 N + 0« with ’mid-range’ values

1

13 taken from references 4,6,8 and 10b. Tunder, et al estimated k from

12 Wray and Teare. Schofield also lists Wray’sk value and remarks that

it fits well, as indeed it does. He presents two least squares fits for

N + 0

2 = NO + 0

k = 2.46 x lCf

16

T

1-5

exp(-2860/T) 400-5000 K

k = 2.52 x 10

-11

exp(-3922/T) 400-1700 K

The former uses data from references 4,6,8,10b and 17. The latter

excludes the 5000 K point. A figure is given which shows points representing the ends of the experimental temperature ranges for each study.
5-40

The fits are good. The present evaluation extends the coverage to

include references 10a and 15, which were not available to Schofield.

3 2

Cherry quotes the valu6 of Bortner and assigns an uncertainty factor

(maximum range?) of log k ± 0.7. Bortner cites references 4, 6-8, 10b, 11,

14, 16. Bahn, in 1964^ recommended k_ calculated from the work of

8 18 4 Kistiakowsky and Volpi. Kaufman adopts the value of Clyne and Thrush

for N + 0^ (see Table I) and then calculates a value for 0 + NO,

k = (3.1 ± 0.6 x 10

^

exp[-(19.8 ± 0.2) x 10^/T], using equilibrium data

for the 1000-5000 K range.
5-41

f TABLE I

(k+

) N + 0

2 = NO + 0 AB®

98

/r = -16,03,

Rate Constant

3 i i - 1 -1

cm molecule s

~ Temp K Ref. Comment

k = 3 x 10" 12 exp(-3100/T)

10

14

k 0.13

0.33

0.45

0.89

394-517

394

437

471 1 517

Mass spec,

analysis

k =

10

14

2 ) X 10

'-12

ex

‘ 0 ..25 + 0. 02

0 ,.42 + 0. 02

0 ,.83 + 0. 03

1 ,.5 + 0. 1 4 ,.2 + 0. 3

6,.6 + 0. 8

15 + 0. 5

412-755

412

435

476

538

610

665

775

NO titration

of N

k = 6.3 x 10

_12 exp( -3500/T)

14

10 k = 0.18

0.93

2.1

453-603

453

538

603

10a NO titration

of N.

N0„ reaction

for 0

k = (2.34 ± 0.12) x 10" 11

eXp(-3975 ± 100/T)

5.0 x

10" 13

T

0 * 5 exp(-3590/T)

300-910 15

1.44 x 10

io

14

-14

T exp(-3390/T)

10

14

0.008 + 0.001 300

0.0360 + 0.0008 353

0.050 + 0.003 360

0.14 + 0.02 408

0.48 + 0.02 470

2.71 + 0.08 586

29.4 + 1.3 910

0.008 350

ESR

Emission from

N + 0 + M -

NO 4- M
5-42

TABLE II

(k_) 0 + NO = N + 0

2

AH°

298

/R = +16,03

2

Rate Constant

3

1 ! -! - 1

cm molecule s

Temp . K RefComment

k = 6.0 x 10' 12

exp(-19.8 x 10

3

/T)

log k = -16.72

-16.59

-16.52

-16.42

1575-1663

1575

1606

1637

1663

6 NO decomp,

in presence of

O^ .Optical

absorption

k = 2.3 x 10" 11

exp(-21.

0 x 10

3

/T)

log k = -16.57 ± 0.01

-15.99 ± 0.06

-15.61 ± 0.04

-15.38 ± 0.05

1525-1912

1525

1690

1840

1912

14,7,6 NO decomp,

in presence of

0

2

. Chemical analysis

k - 5.3 x 10 ^T exp(-19.6,_ x 10

3

/T)

log k = -12.30

400-5000

5000

17 Evaluation

Shock heating

NO + 0

Optical absorption of NO

Equilibrium Constant, K = k /k T ~ log K = 2.03 5000 5 Calculated, ideal

log K = 0.678 + 7003 /T 1500-1900 gas functions

log K = 0.673 + 6963 /T 300-900

TABLE III

Suggested Values 300-5000 K

Rate Constant k at 1000 K Error Limits

3 -1 -1

cm molecule s

k(N + 0 ) = 1.00 x 10" 14

T exp (-3 .2 x 10

3

/T)

k(0 + NO) = 2.2 x 10" 15

T exp(-19.2 x 10

3

/T)

-13

25 x 10

-20

1.0 x 10

iog

10

k ± o.:
5-43

log ,o( k

/

t ) for k in cm3 molecule -1

sec

- '

oo <J> cn 4^

Figure 1: Rate data for N-hC^-* NO + O. Points above 1000 K and

that from ref. 9 not used in setting the recommended value.

0—Wilson (15), O -Kretchmer and Petersen (9), —Kistiakowsky

and Volpi (8),A-Clyne and Thrush (4), V-Vlastaras and

Winkler ( 10a), -Kaufman and Decker (6), • -Vetter

( 14,7,6), —Wray and Teare (17).
5-44

References and Comments

1. Bahn, G. S., "Chemical Kinetics u Reactions Involving N , 0 , NO,

N and 0", Pyrodynamics 1 , 147 (1964),

2. Bortner, M. H., "Chemical Kinetics in a Reentry Flow Field",

General Electric Missile and Space Division Report No. R63SD63

(1963).

3. Cherry, S. S., Gold, P. I., and Van Nice, L. J., Phase I Final

Report, "Screening of Reaction Rates", 22 May 1967. TRW Systems,

Redondo Beach, California, Report 08832-6001-T0000

4. Clyne, M.A.A. and Thrush, B. A., "Kinetics of the Reactions of

Active Nitrogen with Oxygen and with Nitric Oxide’1 , Proc. Roy.

Soc. A261 , 259 (1961).

Fast flow (~ 1 mm), N determined by NO titration.

5. JANAF Thermochemical Tables, PB 168-370, PB 168-370-1, PB 168-370-2,

The Dow Chemical Co., Midland, Michigan.

6. Kaufman, F. and Decker, L. J., "Effect of Oxygen on Thermal Decomposition of Nitric Oxide at High Temperatures", Symp. Combust. 7th

p. 57 (1959).

Effect of oxygen on thermal decomposition of NO in

furnace. Interpretation requires a value of the

rate coefficient for NO decomposition and assumption

of 0-atoms in equilibrium with O 2

. Both of these

have stronger temperature dependences than does the

0 + NO reaction. Points scaled from figure showing

k as a function of temperature.

7. Kaufman, F. and Kelso, J. R., "Thermal Decomposition of Nitric

Oxide", J. Chem. Phys . 23, 1702 (1955).

8. Kistiakowsky, G. B. and Volpi, G. G., "Reactions of Nitrogen Atoms.

I. Oxygen and Oxides of Nitrogen", J. Chem. Phys. 27, 1141 (1957).

Low pressure (~ 1 mm) stirred reactor, N determined

by mass spectroscopy. Points scaled from figure

showing k as a function of temperature.

9. Kretschmer, C. B. and Petersen, H. L., "Kinetics of Three-Body

Atom Recombination", J. Chem. Phys. 39, 1772 (1963).

N + N, N 4- 0 and H + H combination studied. The

N + O

2 = NO + 0 rate determined in the N + 0 study.

A mixture of N2 and O 2 passed through a microwave

discharge. The intensity of NO emission (blue afterglow) studied. The rate quoted in Table I is lower

than others by a factor of 5. The N atom recombination rate in this paper is also low. The reason for

the discrepancy is unknown to us. Point is not used

in developing the suggested rate.
5-45

10a. Vlastaras, A. S. and Winkler, C. A., "Reaction of Active Nitrogen

with Oxygen", Can. J. Chem. 45, 2837 (1967).

10b. Mavroyannis, C. and Winkler, C. A., "The Reaction of Active Nitrogen

with Molecular Oxygen", in Chemical Reactions in the Lower and

Upper Atmosphere (Interscience, 1961) p. 287.

10a supersedes results reported in 10b where a faulty analytical method was used. In the later

study N and O 2 at roughly equal concentrations but

in a vast excess of N

2

were reacted in a flow

reactor at 3 torr. N-atoms analyzed by NO titration and 0-atoms from NO production in the 0 + NO

2

reaction (chemical analysis). The 0 formed is less

than the N reacted, contrary to the mechanism used.

This would have only a slight effect on the reported

rates. Atom combination and wall losses (not considered in the analysis) would reduce the rates.

Reported rates are lower by a factor of two than

others in the same temperature range. Overstatement

of the pressure could cause this.

11. Sulzmann, K.P. G. and Ludwig, C. B., "Duration of the Slow NO Decomposition Regime Behind Shock Waves Around 3000 K and Its Relation

to the Rate Coefficient of the Exchange Path, NO + 0 N +

Convair, San Diego, California, Report ZPh-087, March 1961.

(Not examined)

12. Schofield, K., "An Evaluation of Kinetic Rate Data for Reactions of

Neutrals of Atmospheric Interest", Planet. Space Sic. 15, 643 (1967).

13. Tunder, R., Mayer, S., Cook, E., and Schieler, L., "Compilation of

Reaction Rate Data for Nonequilibrium Performance and Reentry Calculation Programs", Aerospace Corp., Thermochemistry Research Dept.,

Aerospace Report No. TR-1001(9210-02) -1 (1967).

14. Vetter, K., "Kinetik der thermischen Zersetzung und Bildung von

Stickoxyd. I and II", Z. Elektrochem. 53

,

369, 376 (1949).

Study of thermal decomposition of NO from 1500-1900 K

including work with added oxygen. NO 2 used as source

of NO. Values given in Table I are from the reinterpretation by Kaufman and Kelso? who used their NO

decomposition rate in the fit of Vetter's data. The

expression is quoted from Kaufman and Decker.

15. Wilson, W. E., "Rate Constant for the Reaction N + 0^ NO + 0”,

J. Chem. Phys. 46, 2017 (1967).

Fast flow (~ 1 mm), N determined by quantitative

electron spin resonance.
I 5-46

16. Wray, K. L., "Chemical Kinetics of High Temperature Air",

AVCO-Everett Report 104, June 1961. (Not examined)

i 17. Wray, K. L. and Teare, J. D., "Shock Tube Study of the Kinetics

of Nitric Oxide at High Temperatures", J. Chem. Phys. 36, 2582

(1962).

Thermal decomposition of NO in the presence of O

2

. Optical absorption of NO used for analysis. Several reactions occur, the 0 + NO = N + O2 being

relatively minor. A value for the rate was developed

from studies of a 0.57o NO, 0.257> O

2 , 99.25% Ar mixture in the 3900-600 K range. The expression is

based on a fit to this work and references 4,6,8,10b.

The 5000 K value in Table I was calculated from the

expression. Since this work provides the high

temperature tie point, more information on the spread

of the experimental values is desirable.

18. Kaufman, F., "Nautral Reactions" in "DASA Reaction Rate Handbook"

(DASA Information and Analysis Center, Santa Barbara, Calif. 1967)

Chapter 14. DASA-1948.
5-47

H + 0

2 = 0 + OH

REACTION SUMMARY f

H + 0

2 = 0 + OH

CHERRY-1967

Bahn^ has calculated the rate reported here for the reverse reaction on the basis of that for the forward (endothermic) reaction

estimated by Langen et al?® The rate is in good agreement with those

determined from experimental data. An uncertainty factor of 5 was

assessed

JENSEN-1967

This reaction has been studied over a very wide range of temperatures. Fristrom and WestenbergIS recommend a rate constant of 3.7 x

10 " -^e

“ 16500 /RT. Kurzius^ finds k = 2.8 x iO“10e"-^200/RT. it £ s difficult to see how this rate constant can be greatly in error in the

temperature range of interest.

SCHOFIELD -19 6

Least squares fit for the forward reaction combining room temperature flow system, 13"-14, 25 f lame,

^

explosion limit^* 5, 7, 22, 27 and

high temperature shock tube29,30 data. Rate for the reverse reaction

calculated using equilibrium data. Data and recommended value presented

in both graphical and tabular forms.

TUNDER-1967

23*

Rate quoted from Kaskan and Browne.

BAHN-1965

The preferred expressions for the forward reaction are from Kaufman

and Del Greco. ^5 Two values are provided for different temperature ranges

k = 1.2 x 10

15 exp(-17,800/RT) cn3 /mol-s 300-600 K

k = 7.2 x 10 14 exp(-16,900/RT) cnf7mol-s 1500-1700 K

For general utility the latter expression is preferred. Equilibrium constant expression also given.

•kListed separately in this reaction summary.

^Quoted activation energies are in cal mol R = 1.987 cal mol K
5-48

H + 0

2 - 0 + OH

BAS COMBE -1965

8* The value of the forward reaction is that suggested by Baldwin.

The rate for the reverse reaction was develbped using equilibrium data.

This rate coefficient is cited as being consistent with other contemporary evaluations . 10a, 13, 14, 34

The available data are abundant. Sources recorded are references

2,7,9.10, 12,15-17,19-22,24,30-33. Tl'e rate parameters of Karmilova,

et al^2,32 and of Azatyan, et al^ were considered to be low and those

of Fenimore and Jones^-' to be high. Schott and Kinsey's results^

were recalculated.

KASKAN-1964

The reaction has previously been reviewed by Kaufman and Del Greco

and by Voevodskii and Kondratiev. ^3 The estimates for the rate coefficients listed combine data on the forward reaction from references 4,7,

11,17,22,30,33 and from references 12,25 for the reverse reaction.

Strehlow and Cohen 's32a activation energy for the forward reaction is

consistent with the other data.

The experimental data and recommended values are graphed.

BALDWIN-1963

Selected data for H + O 2 = 0 + OH were used to determine the rate

coefficient applicable to the temperature range 293-1500 K. These data

are taken from references 10,12,17,25,30,31, the studies of Kaufman and

Del Greco^S and Clynel2 being on the reverse reaction. Reference 10

summarizes earlier work.

1

Listed separately in this reaction summary.
5-49

H + 0

2 = 0 4 OH

REFERENCES

1. Aganesyan and Nalbandyan, Proc. Acad. Sci. USSR Phys. Chem. Sec.

160, 18 (1965).

2. Azatyan, Nalbandyan, and Meng-Yuan, Dokl. Akad. Nauk SSSR 147.

361 (1962).

3. Azatyan, Nalbandyan, and Meng -Yuan, Proc. Acad. Sci. USSR Chem.

Sec. 147, 973 (1962).

4. Azatayan, Voevodskii, and Nalbanciyan, Dokl. Akad. Nauk SSSR 132,

864 (1960).

5. Azatyan, Voevodskii, and Nalbandyan, Kinetics Catalysis (USSR) 2,

315 (1961).

6. Bahn, private communication to Cherry, Gold and Van Nice for

'Phase I Final Report. Screening of Reaction Rates', TRW Systems,

Redondo Beach, Calif., Report No. 08832-6001T0000 (1967).

7. Baldwin, Trans. Faraday Soc. 52^ 1344 (1956).

8. Baldwin, Symp. Combust. 9th, p. 667 (1963).

9. Baldwin, Corney, and Simmons, Symp. Combust. 5th, p. 502 (1955).

10. Baldwin and Cowe, Trans. Faraday Soc. 58, 1768 (1962).

10a. Baldwin and Melvin, J. Chem. Soc. 1785 (1964).

11. Baldwin and Walsh, Disc. Faraday Soc. 17, 96 (1954).

12. Clyne, Symp. Combust. 9th, p. 211 (1963).

13. Clyne and Thrush, Proc. Roy. Soc. A275, 544 (1963).

14. Clyne and Thrush, Proc. Roy. Soc. A275, 559 (1963).

15. Del Greco and Kaufman, Disc. Faraday Soc. 33

,

128 (1962).

16. Dixon-Lewis, Sutton, and Williams, Symp. Combust. 10th, p. 495 (1965).

17. Fenimore and Jones, J. Phys. Chem. 63

,

1154 (1959).

18. Fristrom and Westenberg, 'Flame Structure' (McGraw-Hill Book Co.,

New York, 1965)
5-50

H + 0

2 * 0 + OH

19. Hoare and Walsh, Chem. Soc. (London) Spec. Publ. 9_, 21 (1957).

20. Just, Luig, and Wagner, Z. Elektrochem. 65. 403 (1961).

21. Just and Wagner, Z. Elektrochem. 64_, 501 (1960).

22. Karmilova, Nalbandyan, and Semenov, Zh. Fiz. Khim. 32. 1193 (1958).

23. Kaskan and Browne, G.E. Missile and Space Division Report R64SD-37

(1964).

24. Kaufman and Del Greco, J. Chem. Fhys. 35. 1895 (1961).

25. Kaufman and Del Greco, Symp. Combust. 9th, p. 659 (1963).

26. Kurzius, 'Kinetics of the Branching Step in the Reaction of Hydrogen

with Oxygen', Ph.D. Dissertation ASTIA AD 635 159, Princeton Univ.

(1964).

27. Kurzius, Symp. Combust. 10th, p. 385 (1965).

28. Langen, et al, AIAA J. 3j 2211 (1965).

29. Ripley and Gardiner, J. Chem. Phys Q 44, 2285 (1966).

30. Schott and Kinsey, J. Chem. Phys. 29, 1177 (1958).

31. Semenov, Acta Physicochimica URSS 20, 291 (1945).

32. Semenov, 'Some Problems in Chemical Kinetics and Reactivity',

Pergamon Press, Vol. II, Chapter X, p. 47 (1959).

32a. Strehlow and Cohen, Phys. Fluids _5, 97 (1962).

33. Voevodskii and Kondratiev, Progr. Reaction Kinetics 1, 43 (1961).

34. Westenberg and Fri strom, Symp. Combust. 10th, p. 473 (1965).
5-51

h

2

+m = h + h + m

REACTION SUMMARY

h

2

+m = h + h + m

CHERRY-1967

Hydrogen atom recombination is perhaps more thoroughly studied than

any other. The identity of the third body, however, materially affects

the rate constant. The rate (based on references 3,4,18,28) chosen was

selected to provide an effective check on the upper limit with an uncertainty of a factor of 10.

JENSEN-1967

Values given only for the combination reaction. Work reported by

Fristrom and We stenberg H suggests, for various third bodies,

-29 -1

k = 3 x 10 J

k = 1 x 10"29!' 1

k = 4 x lO'

30!" 1

-29 -1

k ~ 4 x 10 T

(M = H)

(M = H

2

)

(M = rare gas atom)

(Mf H

20)

The direct measurements of H atom combination, however, are in consider

able disagreement, and shock tube measurements on the dissociation are

also difficult to interpret. ^ The value given is in reasonable agreement

with the most convincing experiments . 1°, 22 it implies a pre -exponential

factor in the rate constant for the dissociation of several hundred times

the collision frequency. Our practice of listing rate constants for

"average” third bodies is open to considerable doubt in this case; H

2

G

appears to be very much more efficient than H

2

, for example.

SCHOFIELD -196

Values for the combination rate coefficient are tabulated from

references 5a, 8, 12, 12a, 15-17, 17a, 17b, 18, 18a, 19“ 20, 22 and 26. No synthesis

is made nor rate coefficient recommended

TUNDER-1967

Values given only for the combination rate. For M = H

2

, H,

the general case these are the rates given by Kaskan and Browne,

value for M = OH is from Wilde , ^8

H_0 and

14 2 The
5-52

h

2

+ m«h + h + m

BAHN-1965

Values given for the dissociation rate. An equilibrium constant

expression is included for use in calculating the combination rate.

For the generalized third body, the preferred expression is that of

Duff, 9 which has been cited in many collections. The rates for M * Xe,

H2 and H are from Gardiner and Kistiakowsky • 12 Those for M = Ar and

H

2

0 are from Skinner, et al.^3

BAS COMBE -1965

^

I g Recombination data from studies near room temperature ’ and

shock wave dissociation data (2800 K and above) 12, 18, 19, 26 were used

to set the recombination rates for M H and M - H2

. Interpolation

to 1400 K and comparison with flame data^j 13,20 Was used to set rates

for M * H and M = H2O. These results lead to small negative activation energies for recombination. They are reflected in the reported

activation energies for dissociation. Other references cited: 1,2,10,5,

21,24,25,27,29.

KASKAN-1964

h + h + m»h

2

+m

Evaluation of this rate is made in connection with that for

H + OH + M - H2O + M, since they occur together in flames where H and

OH appear to be present in their equilibrium ratio.

The rates for H2 dissociation and H atom combination are based

on room temperature combination data 17 and high temperature shock

tube^j 18, 18, 26 and flamed 7, 13 studies of the dissociation.

REFERENCES

1. Amdur, J. Am. Chem. Soc. 60, 2347 (1938).

2. Amdur and Robinson, J. Am. Chem. Soc. 55. 1395 (1933).

3. Bahn, private communication to Cherry, Gold, and Van Nice for

’Phase I Final Report. Screening of Reaction Rates', TRW Systems,

Redondo Beach, Calif., Report No. 08832-6001-T-0000 (1967).

4. Bittker, NASA TN D03607 (1966).
5-53

h

2

+ m*h+h + m

5. Bulewicz and Sugden, Trans. Faraday Soc. 54, 1855 (1958).

i 5a. Carabetta and Kaskan, Symp. Combust. 11th, p. 321 (1967).

6. Chesick and Kistiakowsky, J. Chem. Phys . 28, 956 (1958).

7. Dixon-Lewis, et al. Disc. Faraday Soc. 33. 205 (1962).

8. Dixon-Lewis, et al, Symp. Combust. 10th, p. 495 (1965).

9. Duff, J. Chem. Phys. 2$, 1193 (1958).

10. Farkas and Sachsse, Z. Physik. Chem. B27

,

111 (1934).

11. Fristrom and Westenberg, 'Flame Structure' (McGraw-Hill Book Co.,

New York, 1965)

12. Gardiner and Kistiakowsky, J. Chem. Phys. 35. 1765 (1961).

12a. Hurle, Symp. Combust. 11th, p. 827 (1967).

13. Kaskan, Combust. Flame 2, 229 (1958).

14. Kaskan and Browne, G.E. Missile and Space Division Report R64-SD-37

(1964).

15. Kretschmer and Petersen, J. Chem. Phys. 39. 1772 (1963).

16. Larkin and Thursh, Symp. Combust. 10th, p. 397 (1965).

17. Marshall, Phys. Fluids _5, 743 (1962).

17a. Myerson, et al, J. Chem. Phys. 42. 3331 (1965).

17b. Padley and Sugden, Proc. Roy. Soc. A248, 248 (1958).

18. Patch, J. Chem. Phys. 36, 1919 (1962).

18a. Phillips and Sugden, Trans. Faraday Soc. 57, 2188 (1961).

19. Rink, J. Chem. Phys. 36. 262 (1962).

19a. Rink, J. Chem. Phys. 36

,

1398 (1962).

20. Rosenfeld and Sugden, Combust. Flame 8, 44 (1964).

21. Schott, J. Chem. Phys. 32, 710 (1960).

22. Schott and Bird, J, Chem. Phys. 41. 2869 (1964).
5-54

H

2

+M = H+ H + M

23. Skinner, et al, U.S.A.F. Systems Command Report ASD-TDR-62-1042

(December 1962).

24. Smallwood, J. Am. Chem. Soc. 56. 1542 (1934).

25. Steiner, Trans. Faraday Soc. 31^ 623 (1935).

26. Sutton, J. Chem. Phys. 36. 2923 (1962).

27. Widawsky, et al, J. Am. Rocket Soc. 32. 1927 (1962).

28. Wilde, AIAA J. Z, 374 (1964).

29. Wise and Ablow, J. Chem. Phys. 35. 10 (1961).
5-55

H

2 + 0 - H + OH

REACTION SUMMARY f

H

2

+ 0 = H + OH

MAYER- 1968

Rate coefficients for both directions calculated by a modified

Johnston and Parr technique. (See J+P in General Notes).

CHERRY-1967

The rate reported for the reverse reaction has been calculated

by Balm"* on the basis of estimates^ for the forward (endothermic)

reaction. This rate is in good agreement with those determined from

experimental data.16 An uncertainty factor of 5 was assessed.

JENSEN-1967

14 Fristrom and Westenberg suggest k “ 2 x in -ll -9400/RT K . 10 e , but

their estimate is perhaps rather too heavily weighted in favor of the

results of Clyne and Thrush, and the results in Fig. XIV-20 of Ref.

14 themselves suggest a somewhat lower activation energy. The rate

constant given above is in fair agreement with the results of Wong

and Potter^ and of Kurzius^ and seems a fair compromise.

SCHOFIELD-1967

g |Q Data from low temperature flow experiments y and high temperature shock tube work^ were combined to give the recommended value for

the forward reaction. These and other data^j 13> 24, 25 are presented in

tabular and graphical form. The rate coefficient for the reverse

reaction was calculated using equilibrium data. Other references noted

Nos. 1,3, but not used on the basis of Baldwin* s^ discussion.

TUNDER-1967

Value cited by A. A. Westenberg in ’Report on the Establishment of

Chemical Kinetics Tables', CPIA unnumbered report April 1967, p. 48.

BAHN-1965

The preferred rate coefficient is that of Kaufman and Del Greco^'

who have examined this and related reactions in detail.

t

~ TjT li ~

Quoted activation energies are in cal mol . R = 1.987 cal mol K
5-56

H

2 + 0 = H + OH

BAS COMBE -1965

i ) 8 Q

The value selected for the forward reaction is that of Clyne ’

and Clyne and Thrush .1^,11 The rate coefficient of the reverse reaction was derived using equilibrium data. Other work discussed:

references 4,6,13,15,18,21,23,24. Of these, the early work of Harteck

and Kopsch-*-^ was rejected. Azatyan’ s^ value was rejected on the basis

of Baldwin’s discussion. ^ [He states that he could not find evidence

in their papers for a surface reaction destroying 0 atoms (as assumed)

and that the comparison with CO + 0 « CO2 required in interpreting

their data may not be valid, since this combination is likely to be

termolecular . ] Baldwin’s experimental value^ for the activation energy

was accepted, but his preexponential factor rejected. The value finally

selected is representative of the modern work.

KASKAN-1964

8 , 12

Data from the work of Clyne, Fe’nimore and Jones, and Azatyan,

et al^ (cited in reference 16) were combined in this estimate. Reference 12 includes Baldwin's estimate ^ which was previously considered

as the coefficient for H2 + OH = H + H2O. The data and recommended

value for the rate of the forward reaction are graphed. The reverse

rate was calculated using equilibrium data.

REFERENCES

1. Azatyan, et al, Proc. Acad. Sci. USSR Phys. Chem. Sec. 132, 453 (1960).

2. Azatyan, et al, Dokl. Akad. Nauk SSSR 132, 864 (1960) <,

3. Azatyan, et al, Kinetics and Catalysis (USSR) 2, 315 (1961) [English];

Kinetika i Kataliz (USSR) 2^ 340 (1961) [Russian]

5. Bahn, private communication to Cherry, Gold and Van Nice for 'Phase

I Final Report. Screening of Reaction Rates’, TRW Systems, Redondo

Beach, Calif., P^eport No. 08832-6001-T0000 (1967).

6. Baldwin, Trans. Faraday Soc. 52, 1344 (1956).

7. Baldwin, Symp. Combust. 9th, p. 668 (1963).

8. Clyne, Symp. Combust. 9th, p. 211 (1963).

9. Clyne, Nature 189, 135 (1961).
5-57

H

2

+ 0 * H + OH

10. Clyne and Thrush, Proc. Roy. Soc. A275, 544 (1963).

11. Clyne and Thrush, Proc. Roy. Soc. A275, 559 (1963).

12. Fenimore and Jones, J. Phys. Chem. 62, 693 (1958).

13. Fenimore and Jones, J. Phys. Chem. 65. 993 (1961).

14. Fristrom and Westenberg, ’Flame Structure’ (McGraw-Hill Book Co.,

New York, 1965)

15. Harteck and Kopsch, Z. Physik. Chem. B12, 327 (1931).

16. Kaskan and Browne, G.E. Missile and Space Division Report R64SD-37

(1964).

17. Kaufman and Del Greco, Symp. Cot'ibust. 9th, p. 659 (1963).

18. Kondratiev, Symp. Combust. 7th, p. 41 (1959).

19. Kurzius, 'Kinetics of the Branching Step in the Reaction of Hydrogen

with Oxygen', Ph.D. Dissertation ASTIA AD 635 159, Princeton Univ.

(1964).

20. Langen, et al, AIAA J. 3, 2211 (1965).

21. Nalbandyan and Voevodskii, "Mechanism of Oxidation and Combustion

of Hydrogen’, Moscow (1949).

22. Ripley and Gardiner, J. Chem. Phys. 44, 2285 (1966).

23. Semenov, 'Some Problems of Chemical Kinetics and Reactivity’,

Pergamon Press, Vol. II, Chapter X, p. 47 (1959).

24. Wong and Potter, J. Chem. Phys. 39, 2211 (1963).

25. Wong and Potter, J. Chem. Phys. 43. 3371 (1965).
5-58

0

2

+M=0 + 0 + M

0 + 0 + M=0

2 + M

REACTION SUMMARY

o

2

+m*o + o + m

0 + O + M = 0

2 + M

JOHNSTON- 1968

Data points for the dissociation of 02^ ^ and for recombination

of 0 in Ar and 0^ were analyzed separately then combined (using

equilibrium data) to permit calculation of the rate of dissociation

over a wide range of temperature. From this analysis, the individual

recommended rate coefficients kp(Ar), kp(02)* kj^(Ar), and k^(02) were

developed, assuming the same tempera ture dependence for O2 and Ar as

third bodies. Rate coefficients for Ar as the third body are for the

temperature range 300-15,000 K. Those for O2 as the third body are

for 1000-8000 K.

Reports considered but not used in the analysis (usually because

data points were not available: references 14-17.

BAS COMBE -1965

Combination of 0 atoms has been studied below 700 9,11,12,18

and in shocks above 1500 K.5 j 9, 13 Dissociation experiments (3000 K

and above) 2, 5, 14, 16, 17 a i so lead to combination rates, via the

equilibrium constant. The temperature dependence derived from the

dissociation experiments scatter (and are at times assumed) . The rates

do not extrapolate to the room temperature values. There are earlier

reviews by Kaufman-*-8 and Wray.^

The recommended rates are based on the choice of a value (for

combination) at 3500 K, the lower end of the temperature range for

the shock tube work, of (1.4 ± 0.3) x 10"^ cm6 molecule"2 s”-*-, and a value at room temperature of (3.0 ± 0.5) x 10”33 # Nitrogen is taken

as equally efficient as O2 and 0 atoms as 2.5 times more efficient.

The dissociation rate was recalculated from the combination results.

Other references cited: Nos. 3, 19-22.

JENSEN-1967

23 Fristrom and Westenberg recommend the results of Morgan and

Schiff^ as the only unambiguous ones for direct recombination. For
5-59

o

2

+m = o + o + m

o + o+ m=o

2

+m

M = N

2 they give k s 3 x 10 cm molecule s at room temperature,

which suggests k - Shock tube studies^*on dissociation would imply that k should be much larger, and suggest that the T~1

temperature dependence is reasonable in the range 1500-3500 K range.

Note that dissociation rate constants^* 16, 1 7 agree quite well with each

other and have pre -exponential factors some 100 times larger than the

collision frequency. The recombination rate coefficient selected implies

pre -exponential factor in the dissociation rate coefficient of only 10

times the collision frequency. Discrepancies could perhaps be explained

in terms of deviations from the macroscopic rate quotient law. The

value of k given seems a reasonable compromise for an 'average' third

body.

KASKAN-1964

The recommended values for M = O 2 ate based on Wray's results’*^

for the dissociation reaction. The available information on this system

both at low and high temperatures is graphed (as combination rates).

The data scatter badly. [Wray's rate coefficients are the lowest of

those reported for the combination reaction.]

Critical reviews of the dissociation and combination reactions have

been made by Harteck and Reeves, 24 Kaufman and Kelso^ and Kaufman.

3

The low temperature work surveyed?* 9, 11, 12, 19, 25-28 is all for the combination reaction. Kaufman and Kelso suggest a combination rate of

about (1 ± 0.3) x lO^ 3 cnA molecule “2 g"i for low temperatures and

M= 02- High temperature data are available both for the dissociation

(2500-18,000 K) 2, 5, 6, 14, 16, 17 and combination (1300-3000 K) 5> 6 * 30 in

shock tubes. The third body efficiencies measured in the various experiments conflict. Those recommended reflect the general trend of the

high temperature data.

CHERRY-1967

The value selected for the combination reaction was determined for

the third bodies O 2

9 ^31,32,39 arid H2O

. 27, 3 1, 32, 39 An assigned

uncertainty of a factor of 10 ensures coverage of the full range of

probable values reported. 3 1> 33

TUNPER-1967

The values reported for the dissociation rates (M = 0, 02* and in

general) are those selected by Bortner3 ^ and reported by Wray.®
5-60

Q

2

+M=0 + 0+ M

0 + 0+ M~0

2

+M

BAHN-1964

Dissociation rates are given, and an equilibrium expression for

use in calculating the combination rate. Where the third body is

identified, the values are those of Wray. 39 The generalized third body

rate coefficient is based oti the data of Matthews^® for which M + 0

2

*

REFERENCES

1. Anderson, United Aircraft Corp. Res. Lab. Report R-1828-1 (1961).

2. Camac and Vaughan, J. Chem. Phys. 34, 460 (1961).

3. Schexnayder and Evans, NASA TR R-108 (1961).

4. Wray, Symp. Combust. 10th, p. 523 (1964).

5. Wray, J. Chem. Phys. 37, 1254 (1962).

6. Wray, J. Chem. Phys. 38, 1518 (1963).

7. Golden and Myerson, J. Chem. Phys. 28, 978 (1958).

8. Golden and Myerson, Planet. Space Sci. 3_, 175 (1961).

9. Kaufman and Kelso, 'Chemical Reactions in the Lower and Upper

Atmosphere, p. 255 (Interscience, 1961).

10. Kiefer and Lutz, J. Chem. Phys. 42, 1709 (1965).

11. Morgan and Schiff, J. Chem. Phys. 38, 1495 (1963).

12. Reeves, et al, J. Chem. Phys. 32, 632 (1960).

13. Wilson, PL.D. Thesis, Cornell University (1962). University

Microfilms 63-714, ASTIA No. 276 626.

14. Byron, J. Chem. Phys. 30, 1380 (1959).

15. Generalov and Losev, J. Quant. Spectry Radiative Transfer 6, 101

(1966).

16. Matthews, Phys. Fluids 2, 170 (1959).
5-61

0 () +M®0+0+M

0 + 0 + M=0

2

+M

17. Rink, et al, J. Chem. Phys . 34, 1942 (1961).

18. Kaufman 'Progress in Reaction Kinetics', Vol. I, p. 3 (Pergamon

Press, 1961)

19. Elias, et al, Can. J. Chem. 3J7> 1680 (1959).

20. Barth, Jet Propulsion Lab., Calif. Insti. Tech. Research Summary

No. 36-9, Vol. 1, p. 64 (1961).

21. Losev, Doklady Akad. Nauk SSSR 120. 1291 (1958}.

22. Chesick and Kistiakowsky, J. Chem. Phys. 28, 956 (1958).

23. Fristrom and Westenberg, "Flame Structure' (McGraw-Hill Book

Company, New York, 1965)

24. Harteck and Reeves, "Chemical Reactions in the Lower and Upper

Atmosphere', p. 219 (1961).

25. Kretschmer and Petersen, J. Chem. Phys. 33, 948 (1960).

26. Morgan, et al, J. Chem. Phys. 331, 930 (1960).

27. Krongelb and Strandberg, J. Chem. Phys. 37, 1196 (1959).

28. Marshall, Phys. Fluids 5, 743 (1962).

29. E ekenaan, Fh.D. Thesis, Catholic University (195o).

30. Wilson, Ph.D. Thesis, Cornell (1962).

31. Bortner, GE Missile and Space Division Report R63SB63 (1963),

32. Langen, et al, ATAA J. 3, 2211 (1965).

33. Lezherg, et al, NASA TN D-2883 (1965).

34. Kaskan and Browne, G.E. Report R64SD3 7 (1964).

35. Sarii, et al, NASA CR-54221 (1964).

36. Mayer, et al, Aerospace Corp. Report TDR-269(4210-10) -6 (1964).

37. Migdal, Grumman Airera4 ' f- Eng. Corp. Report ADR 01-10-64,1 (1964).

38. Montchilof£, et al, Symp. Combus t * 9th, p. 220 (1963).

39. Wray, 'Hypersonic Flow Research', Riddell, ed., p. 181 (Academic

Press, N. Y., 1962).
5-62

0

3

+ M = 0 + 0

2 + M (1,2) ° + °

3 = °

2 + °

2 0, 4 )

REACTION SUMMARY

0

3 + M « 0 + 0

2 + M (1,2) ° + °

3 - °2 + °

2 (3,4)

JOHNSTON-1968

The evaluation of rate coefficients for these four reactions was

combined. They are interrelated, 1, 2 and 3 being steps in the thermal

decomposition of ozone. Only two values may be extracted from the ozone

decomposition rate. The ratio is also available from photolyses

of ozone. Reactions 2 and 3 have been studied directly. Reaction 4 has

not been studied. Its rate is deduced from 3 and equilibrium data.

Recommended rate coefficients for reactions 1, 2 and 3 were developed

from photolysis^ and thermal decomposition data . 1* ^2, 15, 17, 22, 26-8, 31, 32

Other earlier work (reviewed in reference 1) that shows large scatter

of points was rejected. The recommended third body efficiencies of O3 , O2 , He, Ar, N2 , and CO2 were estimated from the papers cited above and

reference 2 . The values for the rate coefficients for reactions 1 and 2 (developed

solely from kinetic data) were shown to be consistent with the equilibrium

constant. Then the equilibrium data was used to extend the range of

applicability of measurements on reactions 1, 2 and 3 in developing the

reported recommended values.

The rate coefficients are applicable from 200 to 1000 K. The data

used are tabulated and graphed.

SCHOFIELD -19 6

Least squares fit for 0 + O2 + M « O3 + M. Ozone decomposition

rates^^ 17,^2 and fiow reactor studies of the 0 + O2 reaction?* 21, 22

used. Results of reference 32 recalculated. Results presented in tabular and graphical form. The data fit the Arrhenius form k * A exp(-E/RT)

well, but fit the form k - AT“n poorly. [Not listed as a recommended

value .

]

TUNDER-1967

The value for the rate coefficient for decomposition of ozone

(reaction 1

Axworthy

^ is based on those recommended by Bortner^ and by Benson and
5-63

( 1 , 2 )

(3,4)

0

3

+M=0 + 0

2

+M

0 + o

3 - o2 + o

2

BAS COMBS - 1965

A value was set for the rate coefficient 0 + O2 + M = O3 + M at

room temperature; k = (2,5 ± 0.8) x 10” cm^ molecule’- s"^, M " O2

and E taken as -1000 calories. Both the rate and E emphasize Benson

and Axworthy's^ 1957 reinterpretation of most of the earlier ozone

pyrolysis work, particularly that of Glissman and Schumacher • ^

A

later revision of the O2 dissociation energy^ was used in setting E.

Other work is included in the analysis, both ozone pyrolysis^*

and direct combination studies . 18-21, 25 Rates for M “ O3 and

M = N2 are scaled approximately as set by Benson and Axworthy.^ The

pyrolysis rate (reaction 1) was reevaluated using equilibrium data

after establishment of the values for the combination.

2 The value for reaction 3 is that of Benson and Axworthy with a revised activation energy, E = 5600 cal/mol (because of the revision

of the dissociation energy of oxygen). 5 This leads to a rate coefficient at room temperature of (8.3 ± 0.6) x 10”^-’ cm^molecule”lsec"l.

Shock wave ozone pyrolysis data^ are in good agreement. However,

other ozone pyrolysesTM and direct studies of reaction 3 (mass spec,

analysis and 0 formed by an electric discharge)^ give room temperature values of 3.5 x 10"^ and 2.5 x 10“^, respectively. The activation energy is considered to be uncertain. The rate for reaction 4

was calculated using the equilibrium constant.

KAS KAN-1964

The recommended expression for reaction 2 is that of Benson and

Axworthy, and that for reaction 1 is consistent with it and equilibrium data. Results from references 2,9,10, 14, 17,18,23,24,29,32 are

considered. With the exception of a shock wave decomposition study Lt

the experiments are for low temperatures. Certain results from references 9,10,14 were rejected because of likely wall effects, impurities

and incorrect assumptions. See reference 23 for discussion. Earlier

reviews are to be found in references 14,20, and 23.

BAHN-1964

On an "engineering selection1

' basis the preferred expressions are

those of Davidson.^ Rate coefficients are stated for reactions 1 and 4

Equilibrium constant equations are provided for calculation of the other

rates

6-1

CHAPTER 6: GENERAL NOTE CODES

BEBO Bond energy-bond order calculation of activation energy.

See description in this chapter.

CT Collision theory estimate.

EST The rate has been estimated by analogy to similar specific

reactions. Usually no experimental data are available.

EVAL A detailed analysis of the available data is presented. The

basis for (or method used in deriving) the recommended rate

is made evident.

J+P Johnston and Parr linear transition state calculation of rate

coefficient, including BEBO determined activation energy.

See description in this chapter.

OME Order of Magnitude Estimate used for reactions of similar

formal type (bimolecular, termolecular, ion -molecule, etc.)

See description in this chapter.

REV From data (usually experimental) on the reverse reaction,

SEL The rate reported is a value selected from the available data.

It may be the only available datum.

XP Rate developed from available experimental data. May include

acceptance of an earlier evaluation .
6-2

BEBO Bond -energy -bond order calculation of activation energies

This technique is a component of the Johnston and Parr method

described in a separate general note. References are given there.

The notation BEBO in the table means that the activation energy was

calculated by this technique, but that collision theory was used for

the pre -exponential term (because of the appearance of unreasonable

geometric factors in the transition state calculation)

The bond energy-bond order technique calculates an activation

energy from a potential energy surface that represents the interaction

of the (linear) reacting system. The problem solved is how to calculate

the surface, or at least the energies along the reaction coordinate.

An empirical surface is used that is based on atom-pair interactions

and includes repulsive interaction of the type introduced by Sato.

The atom-pair interactions are needed at distances other than equilibrium (where they are given by molecular constants). These interactions

are set by correlating equilibrium bond-energies of similar bonds with

inter-atom distances and then using the functional relationship to

establish energies at other distances. This permits calculation of

the surface

The reaction coordinate is specified by another postulate: that

the total bond order remains constant along the reaction coordinate.

That is, as one bond is formed, its order increases while the order of

the bond being broken decreases a corresponding amount. A definition

of bond order as a function of distance is needed. This is established

by correlating equilibrium bond orders with distance for related bonds,

as for example, the carbon-carbon triple, double and single bonds, using

inert gas interaction distances for zero bond order. In effect, the

technique applies the chemist’s concept of bond order, as developed by

Pauling, to the calculation of activation energies.

This method has been applied extensively in the computation of

reaction rates by Tunder, Mayer, Cook and Schieler and by Mayer and

Schieler that are included in this compendium.
6-3

J+P Johnston and Parr technique for the calculation of rate coefficients

This is an empirical (or semiempirical) method for calculating

3 7

rate of reaction. 9 It is a development that uses the formalism of

absolute rate theory and a special approximation (bond energy-bond

1 2

order) for estimating the activation energy. 9 The application of the technique to elementary reactions in this

A- 6 9 table is primarily to hydrogen atom transfers: 9 9

A + BH - AH + B

(although some application has been made to other transfers^) and is

limited to the estimation of their rates at high temperatures. This

last restriction deemphasizes any errors in the activation energy calculation.

In the Johnston and Parr technique for hydrogen transfer reactions,

a linear transition state is assumed. The partition function ratio

between this state and the reagents is calculated from molecular parameters for the reagents and the structure of the transition state as determined by the bond energy-bond order approximation to the potential

surface. The BEBO also gives the activation energy. In effect there

are no parameters derived from kinetics introduced into the calculation.

In recent work certain atom transfer reactions have been excluded

from the Johnston and Parr treatments. The exclusion is based on the

appearance in the partition function of unreasonable geometric factors

L\. b

for the angle of approach of the atom to the diatomic molecule. 9 The technique has been used extensively in the compilations of

8 6

Tunder, Mayer, Cook and Schieler and of Mayer and Schieler included

here

References

1. Johnston, H. S., Adv. Chem. Phys. .3, 131 (1960).

2. Johnston, H. S. and Goldfinger, P., J. Chem. Phys. 37,

700 (1962).

3. Johnston, H. S. and Parr, C., J. Am. Chem. Soc. 85,

2544 (1963).
6-4

4. Mayer, S. W., Schieler, L., and Johnston, H. S., J. Chem.

Phys. 45, 385 (1966).

5. Mayer, S. W., Schieler, L., and Johnston, H. S., Symp.

Combust. 11th, p. 837 (1967). Considers transfers other

than H-atom. Discussion by W. E. Wilson and G. S. Bahn

follow this paper* Mayer and Schieleri, CPIA Pub. 106,

p. 106 (1966) is an earlier version superseded by the

present reference.

6. Mayer, S. W., and Schieler, L., J. Phys. Chem. 72. 236 (1968)

Also appeared in CPIA Pub. 146, Vol. 1, p. 121 (1967).

7. Johnston, H. S., "Gas Phase Reaction Rate Theory", Roland

Press (1966), Chap. 11 and Appendix E.

8. Tunder, R., Mayer, S., Cook, E., and Schieler, L t , Aerospace

Corp., Thermochemistry Research Dept., Aerospace Report

No. TR-1001(9210-02) -1 (1967).

9. Mayer, S. W. and Schieler, L., J. Phys. Chem. 72. 2628 (1968)
6-5

ORDER OF '.MAGNITUDE ESTIMATES FOR RATE COEFFICIENTS

When no experimental data nor theoretical calculations are available for a reaction, estimates are often made. These usually fall into

two categories: argument by analogy to specific reactions similar to

the one in question, and forms 1 estimates based on reaction types.

It is the latter class that is described here. For these formal

estimates one does not enquire about what atoms or molecules react,

but merely is the reaction one between two atoms, between an atom and

a molecule, how many atoms there are in the molecule, whether the

mechanism is an atom (or group) transfer or a four center exchange.

At times the size of the molecule is considered. A ntmber of these

estimates are tabulated at the end of this section.

All order of magnitude estimates should be taken with a grain of

salt. They may be good or very bad. Chemistry is not that simple.

Also, estimates do not always match the tabulated rules. The evaluator

tends to shift the value to fit the specific case. It is common to

find lower estimates as the molecular complexity increases.

These estimates are invariably estimates of the rate parameters : pre -exponential factor, coefficient of a temperature term and activation energy as opposed to a direct estimate of the rate coefficient.

They are not precise. They are intended to serve either until more

specific information becomes available on the reaction or to set a limit on the likely value of the rate.

Collision theory provides an upper limit for bimolecular reaction

rate pre -exponential factors although a rough one. The term 1Q^T® may

be estimated from

where |JL is the reduced mass in g/raole, d, the collision diameter in A,

ct the symmetry number (1 for unlike reactants, 2 for like), P, the

steric factor and a is a count of equivalent reaction paths.

DISCUSSION

o

3 The path count as used by Tunder, et a! for hydrogen atom transfers in the reaction AH 4- B - A + BH is

a = r

s (g

where r is the number of equivalent hydrogens and the g's are electronic

multiplicities.
6-6

The estimation of actLvation energies is an art. The simple

rules are empirical or semi -empirical. Hirschfelder ' s two rules,

for atom transfer and exchange reactions are listed in the tables.

The Johnston and Parr Technique calculations (which also rest on

linear transition state theory) do not give results that agree

with these rules.

Another widely cited rule for atom transfer reactions is based

on the suggestion of Evans and Polanyi.8 This calls for a proportionality between the heat of an exothermic reaction and the

activation energies in a set of homologous reactions. As developed

and displayed by SemenOv^

E* = 11.5 + 0.25 AH kcal mol ^

where AH has its normal sign (- for exothermic reactions). Benson

and DeMore^ have discussed this and other rules. They point out

exceptions and suggest that the rules have limited use since 90% of

measured exothermic radical abstraction reactions have activation

energies of 8 ± 3 kcal mol

- ^ and the rules rarely predict this well.

The same article summarizes the work on the development of a model for estimating activation energies of four center moleculemolecule reactions H This model assumes polarization of the

bonds involved (

M semi-ion pair"). Activation energies for a^number

of exothermic reactions have been calculated to ±1 kcal mol with a maximum deviation of ±3 kcal mol"^-.

One may hope that the simple order of magnitude estimates will

fade away, will be replaced by more powerful calculation techniques.

But the history of kinetics suggests that the refinement of theories

does not often lead to improved precision. Empirical correlations

will continue to be useful. It appears desirable to develop more of

these and to develop ones that are restricted to sets of closely

similar reactions.
6-7 oooo

co3uoX

<yo•ooo

V-/ o

PL <0 /"V X ,3 /—

mm

a) cO d 4J

m • • PQ <d • o o

4* 00o 3o o

+i +i o pH *H +i rH CO oo cn i—l vO r-i H 00 00 • • 00

it • • • • • rH • o CM • rH r-i rH CM CM rH CT\ rH rH cn

ro cn i i rH rH r-i o VH V-/ rH 1 1 1 o * 1 1 1

co l l ? l ? * 2 l 2 3

•MI

•Hu

CO w3d3

4J •Ha

oo

cd X

<4-i o

Pt

(0 dMo

PQ

cwqT 00

-»\ 3

'-M3 m 00 00 00 o o m m• • o oI I

CO rH2&CO m¥

pci

NJI

PS “N

NJI r*

m¥ m in • • ¥ ¥ do

(0 Bou3

CL) pi m cn cn /-v o o o NJ rH rH rH X X X

NJ

m• m• in• +

rH rH r-H /H1^ i +1 +1 +i wa O O o w • • • <] CM <r VH rQ m O 3 o o X o 4-1 0) 4-1 a) <0 cd rH o

rH H 3 *H O <u u 0

to 0 u <D 3 o

rH o rH o 4J 3 o a o 3 3

Pi •H B r—

X 4J | Pi o rH rH 3 u O o o S O 3

0) •H 4J Ou O 3 0 cd Pi P u

fi »H 3 o •H 0 d MH a) d o 4J § o cd o rC 4H ; 3 o Pi Pi

4-1 d X 4J •4-4 •s o 3 r— 

w rH 3 O CM /*v

pi s X cd u CM o «H Pi *H d Pi o a) a) X NJ Jh d a, d 3 0 3 NS

4* p »H a> 5^ MH O 4" 4H {H

+J r» o X C0 rH 4* 4* 8 in B rH !h 10 4J 3 3 X rH u 3 a. 4- o o 3 3 3 X 3 4”

pi X 3 cd 4* cd g X rH u 4*

m O 4- 3 X rH

©

•H JHM O X N d MH MH •H Pi rH d p£ rO It 4-i X U O 3 3 d d X u o Pi X B 3 u X ts U X Pi 3 3 Cu it 3 o X 3 3 r-s 3 tl It Q) 3 Pi /H O It o pi IH SI 3- O CM 4H ii 14H ii PU O CM IH

4* CO 3 *H CM bn d CO CO O 3 4-1 d VH CM u 3 M O CO rH X 3 SH 3 *H tH O X 3: 3 >« JH cd X Pi H X 4- 3 S 3 0 X P< 3 3

r—

3 P« 00 rH 4- Pi Pi O 60 i-< 4“ 00 4- 3 4- rH 4J 4" 'H H 4- £3 4J 4* 4-4 4-4 4- W rj 3 o 3 O CM rH 3 O rH 3

a) X o 0 X El O 3 3 «PC* B X 0 X pcS 0 3 d r3 X H 3 o o o o rH © rH o o vH 4J u 3 u u O *J Q X g g < *H C Or <U B W

(0 H W
Order

of

Magnitude

Estimates

(Cont'd)

6-8

CO

a)o

55 00 bO bO OU•ooo o1-4 COo X 1—

/V X m

CM

—v a • m o • X-\

r4 x_

+1

+1 PS'

m v— o W • . <j o A

Pi iA

rO

tt O O O o om. m o r-l +i CO 00 CO O . • . 4J m o O CM o 1-4 H r4 St CO 1 1 1 r—

r—

2 2 ? l l d

a) o H d) d r-l 00 d o O d

0) a •r4

U r-l O d O d d o 0 <u d o 4-1 o d td CO <u >4

a) V4 r—i r-4 a. O jj d cd d

•H td 4-J u o a> a a td u a) r-4 u o d to d r-4 d

<u •r-t 4J a <D o o »4 •s

4J td d a a <u (0

td CO r-4 4-> o d § o 4-4 a O d X *H y

4J

V o o a a>

<U 6 o u o 0 o i r-4 i CO 44 a>

•\ o •u e

td pi d r-l >4

1—4 o CNl a o o o a d

td Pi

A i4A *r4 o td o u r—( r-l o d 4-4 4-1 X 4-1 44

4-» td PS 4J II td II o td CO N_/ 3 o td V4 td +

<U i4 II

V

y a> 4-1 44 d d d <4-4 o 4-1 o u o r—4 o o

td CM o 6 O J! j Pd •r4

es

M (35 o u d d 4-1 »4 l a A d A td o II o td td r-4 + o o r-4 i-4 •rl U

r—

«d •H 4* l4 + d CO X CD d d o H 4J 4J o r-4 r-4 i—4 4J o *H C*5 t4 X *r4 pi 4) d PS d td

<u d d d i—

d. a CO

1-4 td d d Q X X d o £ <H a w w d a

ft

SO ts=> +z&

II

t3eA

Decomposition

with

internal

ring

formation ~

11.5 ±

0.5 0>

AE/R
Order

of

Magnitud

e

Estimates

(Cont'd)

6-9

co

<u

4-1 o

55 0 0

<4-1 0

<4-4 0

•s 4^ 0

44 0

•V M-l

O

O

o

o

PQ m in

i o• >—

i m

oi mo

m

d

<

r\i CT> VO CM CM H • • • • • • CM cn r>» Ov ON CM

*—l

1 CM

1 CM

1 CM

1 CM

1 T-l1

l l l l l ?

V5 0) r-4o

•rl 4Ju

d

04

03

d

o

•H

4—1 03N

0) o r-f s 0 X W S3 X d c 4J

J-i 4J 3-4 4

* •H 4

* d

03 eg + + 4-1 4J <u .C / * \ 0 4-1 0 JH d f 0 1 O + 1 T-i X d 1 <D X d >4 ,d 0) >* >+ JQ Si X 0 “H X o

fif B If 0 1

11 ,Q d 4“ d u + + o -d II d 0 II 4J

<u o X o o s o <U m >C X 03 X i-4 c S3 03 X rH CO 0 4" 4-1 4-1 4

* o a II 13 o 4-1 + d r-4 4

* a) II > 03 u 1 Cd a d >

0 S-i >-( >-l 4-1 Q) 1 •H >4 i >4 •H H o 0 d -O 4-1 4-J + + a> 4- o 4- d d 4

- CO a) u 4

- <u + •H 0 CuO + • S3 4- 4-1 o -f d O i O X X l X O X X X O X

03 d <11 d d CO

4-1 6

o r-4 o o 0) o M W M M
6-10

NOTES

a. Units: time in seconds, temperature in Kelvin, concentration in

molecules /cnP . The order of the reaction is equal to the number

o:: reactants shown*

b. Coefficients of the temperature term are invariably based on

theory, when they are non zero.

c. 1000 *C is the activation energy, E*, divided by the gas constant,

R. The factor of 1000 is introduced to maintain consistency with

the main table where C is scaled,, To convert C to kilojoules /mole,

multiply by 8.315.

An activation energy for an exothermic reaction represents the

dynamic energy barrier. That for the reverse, endothermic reaction

should be the endothermicity plus the same barrier. However, for

highly endothermic decompositions the experimental activation

energy is often very close to the energy of the reaction.

d. These estimates are, essentially, for reaction on every triple

collision. Schofield^- tabulates measured combination rates for

atoms and atoms plus diatomic molecules. These k's show small negative temperature coefficients and fall in the range 10”34 £0

10 "29 cm^molecule"2s"^.

e. Reference 2.

f. Reference 3.

g. Benson's estimates for bimolecular reactions based on examination

of rates of reaction of organic molecules.^ The decomposition rates

apply in the high pressure region.

h. Collision theory value for unlike reactants (cr = 1), collision

diameter, d ® 0.2 ran, reduced mass 4 g/mol"l(M = 8) and one reaction

path (a = 1) ,see discussion. P is the steric factor < 1.

i. Activation energy set according to Hirschfelder ' s rule.-* Cherry,

et al use a = 0.055. Tunder, et al use a = 0.06. AE is the energy

of the dissociation reaction: YZ-J-M^Y + Z + M AE = AH - RT

Also see discussion.

3

j. A modified collision theory equation is used by Tunder, et al for

hydrogen transfer reactions in which there is more than one equivalent hydrogen, e.g. for NH^ + F = NH2 + HF. The modification consists of counting the reaction paths in terms of the number of

equivalent hydrogens and the electronic multiplicities. P (steric

factor) = 0.1. This method gives slightly higher value than do

other formal estimates.
6-11

k. Activation energy set according to Hirschfelder 1 s rule for exchange,

reactions.^ Cherry, et al use b = 0.2. Also see discussion.

l. Estimated by Benson and DeMore.^ A comprehensive review of unimolecular reactions by S . W. Benson and H. O'Neil that provides

evaluated rates for several hundred reactions is in press (NSRDS

Series)

3 m. Estimates developed by Tunder, et al based on rates compiled by

Bortner .

REFERENCES

1. Schofield, K., Planet. Space Sci. 15. 643 (1967).

2. Cherry, S. S., Gold, P. I., and Van Nice, L. J. TRW Systems,

Redondo Beach, California, Report 08832-6001-T0000

3. Tunder, R., Mayer, S., Cook, E., and Schieler, L., Aerospace

Corp., Thermochemistry Research Dept., Report No. TR-1001

(9210-02) -1 (1967).

4. Benson, S. W., Ind. Eng. Chem. 56. 18 (1964).

5. Hirschfelder, J. 0., J. Chem. Phys. 9, 645 (1941).

6. Benson, S. W. and DeMore, W. B., Ann. Rev. Phys. Chem. 16 9 397 (1965).

7. Bortner, M., General Electric Missile and Space Division,

Report No. R63SD34 (1964).

8. Evans, M. G. and Polanyi, M., Trans. Faraday Soc. 34, 11 (1938).

9. Semenov, N. N., "Some Problems in Chemical Reactivity", trans.

by M. M. Boudart (Princeton 1958), Vol. 1, Ch. 1, p. 29.

10. Benson, S. W. and Bose, A. N., J. Chem. Phys. 39. 3463 (1963).

11. Benson, S. W. , Bose, A. N., and Nangia, P., J. Am. Chem. Soc. 85,

1388 (1963).

7-1

CHAPTER 7: SPECIFIC NUMBERED NOTES FOR THE TABLE OF RATE COEFFICIENTS

A set of notes for each evaluation source cited in the table is

included here. These refer to the numbers in parentheses after the

source identification. Each source has a separate set. These sets

are arranged alphabetically by author.

If the paper or report was written as a table with notes, those

given here follow the original material. However, they have been rewritten to make them fit into this larger collection. Internal cross references have been spelled out and references included. Occasionally an

obvious error has been rectified or an ambiguity noted. If the paper was

in the form of an extended discussion, only the briefest summary has been

extracted. This shows the data considered and, occasionally, the basis

of the evaluation.

The sources for which notes are provided here follow.

BAHN-1964, 1965, 1968

Bahn, G. S., Pyrodynamics 1, 147, 271, 335 (1964); 2^ 91, 197, 315 (1965);

3, 245 (1965); 6, 101 (1968).

BALDWN - 1963

Baldwin, R. R., Ninth Symposium (International) on Combustion, p. 667

(1963), Academic Press, N. Y.

BASCMB -1965

Bascombe, K. N., "Reaction Rate Data" The Hydrogen/Oxygen System", . Ministry of Aviation, Explosives Research and Development

Establishment, Waltham Abbey, Essex, England, E.R.D.E. l/S/65

BAULCH .1968

Baulch, D. L., Drysdale, D. D., and Lloyd, A. C., "Critical Evaluation

of Rate Data for Homogeneous, Gas -Phase Reactions of Interest in

High -Temperature Systems", Dept, of Physical Chemistry, The University,

Leeds, England, High Temperature Reaction Rate Data, Report No. 1,

May 1968.

CHERRY -1967

Cherry, S. S., Gold, P. I., and Van Nice, L. J., Phase I Final Report,

"Screening of Reaction Rates" 22 May 1967. TRW Systems, Redondo

Beach, California, Report 08832-6001-T0000
7-2

JENSEN-1967

Jensen, D. E. and Kurzius, S. C., "Rate Constants for Calculations

on Nozzle and Rocket Exhaust Flow Fields", AeroChem Research

Laboratories, Princeton, New Jersey, March 1967. Report TP-149.

JONSTN -1968

Johnston, H. S., "Gas Phase Reaction Kih.etics of Neutral Oxygen

Species", NSRDS-NBS Monograph Series (in press, 1968).

KASKAN -1964

Kaskan, W. E. and Browne, W. G., "Kinetics of the H

2 /CO/O2 System",

General Electric Company Space Sciences Laboratory Report R64SD37,

July 1964.

MAYER-1968

Mayer, S. W. and Schieler, L., "Computed Activation Energies and Rate

Constants for Forward and Reverse Transfers of Hydrogen Atoms",

J. Phys. Chem. 72, 236 (1968). Also appeared in Chemical Propulsion

Information Agency publication No. 146, Vol. I, p. 121, (1967).

SCOFLD -1967

Schofield, K., "An Evaluation of Kinetic Rate Data for Reactions of

Neutrals of Atmospheric Interest”, Planet. Space Sci. 15

,

643 (1967).

TUNDER -1967

Tunder, R., Mayer, S., Cook, E., and Schieler, L., "Compilation of

Reaction Rate Data for Nonequilibrium Performance and Reentry

Calculation Programs", Aerospace Corp., Thermochemistry Research

Dept., Aerospace Report No. TR-lC01(9210-02) -1 (1967).

WILSON-1968

Wilson, Wm. E., Jr., "Kinetics Tables for the Reactions of Hydroxyl

Radicals", see Chapter V of this report.

Wilson, Wm. E., Jr. and Garvin, David, "Kinetics Tables for the

Reactions N + O

2 = NO + 0 (k_^), NO + 0 = N + O

2

(k )", see Chapter

V of this report.
7-3

BAHN, G. S., Pyrodynamics 1^ (1964); (1965); 3_ (1965); 6^ (1968)

CHEMICAL KINETICS

Introduction

The Chemical Kinetics Section of Pyrodynamics has featured compilations of rate data and lists of selected, ’’preferred" values for rate

coefficients.

Selected values for the 0, N, H, 0-N, and H-0 are presented in

Vols. 1, 2 and 3. Two reactions, CO + OH =» CO 2 + H and CO + 0 + M «

CO2 + M are covered in the first issue of Vol. 6. It is these sections

that are summarized in this compendium. The other Chemical Kinetics

Sections are compilations without selection. Of particular interest is

the extensive compilation (with rate expressions and bibliographic

family trees for them) that has also appeared in Pyrodynamics. This

bibliography is very good in its coverage of the report literature (as

well as published material) . It cites secondary as well as primary

sources and thus carries a heavy burden of simple quotations.

The selection of rati bed as having an

selection" is examination of the available material of the most representative (or widely accepted) value. Simple tests are made for reasonableness, i.e. bimolecular rates not exceeding the collision number.

"Scientific" selection, on the other hand, includes examination of the

method and possible errors.

This compendium includes most of the reactions listed in Vol. 1

(1964) and Vols. 2 and 3 (1965). Some of the HO 2 radical and some for

which temperature dependences are not available have been omitted.

Items that may have been outdated by later work have not been removed.

Rates are tabulated by Bahn for one direction and, in most cases,

equilibrium data are provided for use in calculating the rate in the

other. The equilibrium data are not listed here (nor indicated repeatedly in the notes). Only reactions explicitly tabulated in the original

appear in this compendium.

1. Pyrodynamics 5_, 49, 75, 221, 375 (1967).

2. Bahn, Western States Section, The Combustion Institute, Paper 67-11,

April 1967.

3. Ellis and Bahn, Western States Section, The Combustion Institute,

Paper 62-27, November 1962, Part 1.

4. Bahn, Western States Section, The Combustion Institute, Paper 62-27,

November 1962, Part 2.

n engineering" as opposed it-Engineering
7-4

BAHN-1964

Pyr©dynamics 1_, 147 (1964),

"Chemical Kinetics, Reactions Involving N

2

, 0

2

, NO. N and 0"

Pyrodynanri.cs 1, 271 (1964).

"Chemical Kinetics. Reactions Involving N2O, NO2 and O3 , but

Only One of these Species, with N2 , O 2 , NO, N and 0"

Pyrodynamics l_, 335 (1964).

"Chemical Kinetics. Reactions Among N2O, NO2 , ar.d 0^, Also

Involving N2 , 02 , NO, N and 0"

1. 0

2

+ M = O' + O' + M

See Reaction Summary.

2. N

2

+M=N + N + M

For the generalized third body, the value is that of Eschenroeder,

Boyer and Hall for which M = N2

. The preferred rates when M is to be

identified are those of Wray.

Eschenroeder, et al, Cornell Aeron. Lab. Report AF-1413-A-1 (May 1961).

Wray, "Hypersonic Flow Research" p. 181 (1962), Academic Press, N.Y.

3. N

2

+ 0

2 = NO + NO

Freedman and Daiber, J. Chem. Phys . 34^ 1271 (1961).

4. N0+M=N + 0+ M

The rate expression for the generalized third body is that of

Eschenroeder. That for identified third bodies is from Wray's summary.

Eschenroeder, et al, Cornell Aeron. Lab. Report AF-1413-A-1 (May 1961).

Eschenroeder, et al, Phys. Fluids _5 , 615 (1962).

Wray, "Hypersonic Flow Research" p. 181 (1962), Academic Press, N.Y.
7-5

BAHN-1964

5. N

2

+ 0 = NO + 0

Marrone, Anti-Missile Res. Advisory Council Proc. 4_, 353 (1961).

6. NO + 0 = N + 0

2

Kistiakowsky and Volpi, J. Chem. Phys. 27, 1141 (1957).

Also see Reaction Summary for N + 0

2 = N + NO.

i •

7. 0 + N

2

0 = NO + NO

Fenimore and jones, Symp. Combust. 8th, p. 127 (1962).

8. N

2 + 02

*‘N 0 + 0

9. NO + 0

2 = N0

2

+ 0

Davidson, AVCO Mfg. Corp. Research Report 32 (June 1958).

10. no

2

+ M=N0 + 0 + M

Expression from Levitt, based on data of Huffman and Davidson.

Levitt, Trans. Faraday Soc. 59, 59 (1963).

Huffman and Davidson, J. Am. Chem. Soc. 81, 2311 (1959).

11. N

2

0 + 0 = N + N0

2

N

2

+ °

2 = N + N0

2

Nawrocki and Papa, "Atmospheric Processes" (1963), Prentice -Hall, N.J.

12. Estimate (no data ) made by Ludwig and Sulzmann. No other expression

is available.

Ludwig and Sulzmann, Convair Division, General Dynamics Corp. Report

ZPh-082 (February 1961)
7-6

BAHN-1964

13 . 0

2

+ 0

2 * 0 + 0

3

o

3

+m=o + o

2

+ m

- — - - — — i See Reaction Summary for C> 3

+ M = 0 + ^

2

4- M.

14. N0o + M = NO + 0 + M

j l

Schott and Davidson, J. Am. Chem. Soc. 80. 1841 (195$).

15. N0

9 + 0 * N + 0

3

This expression, fabricated by Ludwig and Sulzmann is the only

one available for the forward reaction that incorporates a temperature dependence.

Ludwig and Sulzmann, General Dynamics Corp. Report ZPh-082 (Feb. 1961).

16. N0

2

+ 0

2 = NO + 0

3

The preferred expression is that of Davidson, which was derived

from the data of Johnston and Crosby [on the reverse reaction],

Davidson, AVCO Mfg. Corp. Research Report 32 (June 1958).

Johnston and Crosby, J. Chem. Phys. 22. 689 (1954).

17. N

2

+ N0

2 - NO + N

2

0

From the compilation of Davidson derived from data of Kaufman

and Kelso.

Davidson, AVCO Mfg. Corp. Research Report 32 (June 1958).

Kaufman and Kelso, J. Chem. Phys. 23. 1702 (1955).

18. N0

2 + N0

2 = NO + NO + 0

2

Huffman and Davidson, J. Am. Chem. Soc. 81. 2311 (1959).
7-7

BAHN-1964, 1965

19. N + N0

2 = N

2

+ 0 + 0

Harteck and Dondea, J. Phys. Chem. 63., 956 (1959).

20. N

2

0 + N0

2 - N

2

+ NO + 0

2

Bortner, GE Missile & Space Vehicle Dept. Rept. R61SD122 (June 1961).

Only available rate constant - determined at 199°K.

BAHN-1965

Pyrodynamics 2_, 91 (1965).

"Chemical Kinetics. Reactions Involving N0^ with N^O, NO

2

, O

3

, ^2*

NO, N and 0. Reactions Involving N

20^ an<* ^2^5 anc* *^

3 "

Pyrodynamics 2j 197 (1965).

"Chemical Kinetics. Reactions Involving H

2

, 0

2

, OH, H and 0"

Pyrodynamics 2, 315 (1965).

"Chemical Kinetics. Reactions Involving H2O, HO2 , and O3 but Only

One of these Species with H

2

, 0

2

, OH, H and 0"

Pyrodynamics !3, 245 (1965).

"Chemical Kinetics. Reactions Among HO, H0„, H«0

2 , and 0~ T also

Involving H

2

, 0

2

, OH, H and 0"

1. Ludwig and Sulzmann, General Dynamics Corp. Rept. ZPh-082 (Feb. 1961).

Only expression available. Estimated. No data.

2. N0

3

+ M * N0

2 + 0 + M

The preferred expression is that documented by Huffman and

Davidson. It is the only one available containing a T” s term.

Huffman and Davidson, J. Am. Chem. Soc. 81, 2311 (1959).
7-8

BAHN-1965 3.

NO + N0

3 = N02

+ N0

2

The preferred expression is that of Davidson and Schott,

indicating that the rate is essentially independent of temperature.

Davidson and Schott, J. Chem. Phys. 27, 317 (1957).

4. no

2 + 0

3 = no3

+ o

2

The preferred expression, given by Ford, is the only one available containing a temperature dependence.

Ford, Symp. Combust. 8 th, p 119 (1962).

5. N0

3

+ N0

3 = N02 + N0

2

+ 0

2

This preferred expression is that documented by Schott and

Davidson, including a stated tolerance on the activation energy.

Schott and Davidson, J. Am. Chem. Soc. 80, 1841 (1958).

6 . N

2

0

4 + M = N0

2

+ N0

2 + M

N2°4

= N°2 + N°2

The preferred expressions for N2O4 decomposition are the only

ones available containing temperature dependencies. The bimolecular

reaction applies at low pressure, and the monomolecular at high

pressure

Carrington and Davidson, J. Phys. Chem. 57, 418 (1953).

7. N

2

0

5

+ M = N0

3 + N02 + M

The preferred expression, given by Schott and Davidson is the

only one available for the forward direction. It applies at high

pressure

Schott and Davidson, J. Am. Chem. Soc. 80, 1841 (1958).
7-9

BAHN-1965

8. N

2

0

5 = N0

2 + N0

3

These expressions are the only ones available for N2O

5 decomposition that contain temperature dependencies.

Histasune, et al, J. Am. Chem. Soc. 7£, 4648 (1957).

9. H

2 + M = H + H + M

See Reaction Summary.

10. Tfye preferred expression is that reported by Skinner, et al based on

their research.

Skinner, et al, U.S.A.F. Systems Command Report ASD-TDR-62-1042 (Dec. 1962)

11. 0H + M~0+H+M

The preferred expression is that of Duff, because of its general

citation and use. Other expressions are not markedly different.

Duff, J. Chem. Phys. 28, 1193 (1958).

12. H + H

2

0 = H

2 + OH

H

2

0 + 0 - OH + OH

H

2 + 0 - H + OH

In each case the preferred expression is that of Kaufman and

Del Greco. These authors examined these reactions in very careful

detail. Also see Reaction Summaries.

Kaufman and Del Greco, Symp. Combust. 9th, p 659 (1963).

13 . H + 0

2 = 0 + OH

See Reaction Summary
7-10

BAHN-1965

14 . H

2

0 + M=*H + OH + M

The four available expressions are from Duff for M * Xe, He,

and from Skinner, et al. for M = Ar, ^0. If the third body is

not to be identified, the value for M = Xe is preferred as more

widely known.

Duff, J. Chem. Phys . 28, 1193 (1958).

Skinner, et al, U.S.A.F. Systems Command Report ASD-TDR-62-1042 (Dec, 1962)

15. H

2

0

2

+ M = OH + OH + M

The only available expressions for peroxide decomposition are

those of Baldwin and Brattan. These authors report an activation

energy of 46.3 kcal mol"-*-. They demonstrate that this value is consistent with the heat of reaction (50.3 kcal by their citation,

51.19 kcal by the JANAF Thermo chemical Tables) if the Rice-Ramsperger

Theory is applied with S = 4 in the equation

k= Z exp(-E/RT)« (E/RT) S " 1 /(S-1)I

This implies zero activation energy for the recombination reaction

and leads to the alternative expression

k = 7.5 x 10

26

T“

3

exp (-50, 100 /RT) cm

3

mol" 1 s. which is also listed.

Baldwin and Brattan, Symp. Combust. 8th, p 110 (1962).

16. H0

2

+ M = H + 0

2

+M

The only available expression.

Skinner, et al, U.S.A.F. Systems Command Report ASD-TDR-62-1042 (Dec. 1962)

17. H0

2

+ H

2

0 « H

2

0

2 + OH

Voevodsky, Symp. Combust. 7th, p 34 (1959).
7-11

BAHN-1968

Pyrodynamics 6, 101 (1968).

"Chemical Kinetics. The Reactions H + (X>2 = OH + CO and

C0

2 + M - 0 + CO + M"

1 . CO + OH = C0

2

-f H

See Reaction Summary.

2. C0

2

+M = CO+O+M

The value cited is an empirical curve fit to the data of

Olschewski, et al (1967) making the activation energy equal to

the dissociation energy and the rate coefficient for the reverse

reaction not exceed the collision frequency at low temperature.

"The expression reproduces the experimental work in the 2000-

5000°K range and precludes ridiculous recombination rates around

500-1000°K. Clearly, however, this reaction urgently needs a detailed scientific review and evaluation of available data, and

probably needs extensive additional experimentation after that."

Data compiled from the following references.

Brabbs, et al, J. Chem. Phys. 38, 1939 (1963).

Michel, et al, Z. Phys. Chem. 39, 129 (1963).

Michel, et al, Z. Phys. Chem. Neue Folge 44, 160 (1965).

Olschewski, et al, Symp. Combust. 11th, p 155 (1967).

Howe, et al, Nat. Aeron. Space Admin. Tech. Note D-1885 (June 1963).

Howe and Sheaffer, Nat. Aeron. Space Admin. Tech. Note D-2131 (Feb. 1964).

Davies, J. Chem. Phys. 41, 1846 (1964).

Davies, Ibid 43, 2809 (1965).

Steinberg, Nat. Aeron Space Admin. Contractor Rept. CR-166 (Feb, 1965).

Fishburne, et al, J. Chem. Phys. 45, 160 (1966).

Myers and Sulzmann, General Dynamics /Astro. Rept. GDA-DBE -64 -001 (June 1964),

Heicklen, AIAA J. 5, 4 (1967).

s
7-12

BALDWIN- 1963

BALDWIN, R. R., Ninth Symposium (International) on Combustion, p. 667

(1963), Academic Press, N. Y.

1. H + 0

2 = 0 + OH

Selected data for H + O

2 = OH + 0 are used to determine the rate

coefficient for the range 293-1500 K. Data used are from

Schott and Kinsey, J. Chem. Phys. 29

,

1177 (1958)

Fenimore and Jones, J. Phys. Chem. 63

,

1154 (1959)

Baldwin and Cowe, Trans. Faraday Soc. 58, 1768 (1962)

f who summarize earlier work

Semenov, Acta Physicochim. URSS 20, 291 (1945)

Clyne, Symp. Combust. 9th, p. 211 (1962)

Kaufman and Del Greco, Symp. Combust. 9th, p. 659 (1962)

the last- two being studies of the reverse reaction

Also see Reaction Summary.
7-13

BAS COMBE -1965

BASCOMBE, K. N., "Reaction Rate Data: The Hydrogen/Oxygen System",

Ministry of Aviation, Explosives Research and

Development Establishment, Waltham Abbey, Essex,

England, E.R.D.E. l/S/65

Introduction

This report summarizes and evaluates the experimental rate data

available for twenty reactions (counting forward and reverse as one)

in the hydrogen-oxygen system. "Best values" are given for most of

these. One hundred thirty -seven references are cited.

The species in the reactions are H, H 2 > H20, H

202, HO?* 0, 0 2 j

O3 and OH. Rate coefficients are stated in the Arrhenius form:

k A exp (-E/RT), no use being made of a T® term. Where possible

uncertainty limits are given for the rate parameters, these being

assessments of reliability of the numbers, not all-inclusive ranges.

Each reaction system (forward and reverse) is discussed separately. The available data are summarized, commented upon and selected

for use in establishing the best value. Data for both the forward and

reverse reaction are employed (using equilibrium data) to set the rate

in one direction. The other rate is then recalculated.

The "best values" are included in this compendium. The other

reactions discussed in the report are:

H0

2

+ M » H + 0

2

+ M h

2 + H°2 - H + H

2

0

2

H + 0o = OH + 0- H0_ + H0„ = H_0n + 0 o 3 2 2 2 2 2 2

OH + 0

3 * H09 + 0

2

H0

2

4- H

2

0 - H

2

0

2

+ OH

H + H0

2 = OH + OH H + H

2

0

2 = H2

0 + OH

H + H0

2 - H2 + 02

h

2°2 + 0 - H0

2 + OH

H + H0

2 = H

2

0 + 0

H0

2 + 0 » OH + 02

h

2

o

2 + ho2 = h

2

o + OH + 0

2

The applicable temperature range for the best values is stated as follows: "The [derived rates] should be applicable not only to hydrogen/

oxygen at all temperatures but also to hydrogen/air systems at temperatures up to 3000°K". Arbitrarily, for this compendium the range is stated

as 300°K to 3000°K except where the reported experimental data include

higher temperatures*

The notes given here are drastic abridgments of Bascombe’s discussions.
7-14

1.

H

2 + OH - H + H

2

0

See Reaction Summary for H + H

2

0 = H

2

4- OH

MSCOMBE -1965

2. H + 0

2 = 0 + OH

See Reaction Summary,

3. H

2 + 0 * H + OH

See Reaction Summary

4.

H + 0

2 + M = H0

2 + M

Only the forward reaction has been studied. Evaluation consisted of setting the rate for one third body (H2O) and then scaling

the rates for others ,0^2, and N2 ) on the basis of relative

efficiency data.

For the rate in the presence of water, high temperature data

from several sources-*-”? were combined with the room temperature

results of Clyne and Thrush, 9 Relative efficiencies of H2 and

H2O are derived from the comparison of H2 and Ar by Lewis and

Von Elbe.-*^ The efficiency of O 2 relative to H2 was set using

data from references 5, 12, and that for N

2

on the basis of references 6, 11,

The sources combined in the evaluation and others discussed

cover work on flames, flow studies of the H2 /O 2 reaction and the

combination reaction and the mercury photosensitized oxidation of

hydrogen.

1. Baldwin and Brooks, Trans. Faraday Soc. 58

,

1782 (1962).

2. Baldwin and Precious, Nature 169

,

290 (1952); and unpublished work.

3. Nalbandyan, Zhur. fiz. Khim. 19, 210 (1945).

4. Broida and Oldenberg, J. Chem. Phys. 19, 196 (1951).

5. Ashmore and Tyler, Trans. Faraday Soc. 58, 1108 (1962).

6. Willbourn and Hinshelwood, Proc. Roy. Soc. A185, 353 (1946).

7. Voevodskii and Tal'rose, Zhur. fiz. Khim. 22, 1192 (1948).

8. Clyne and Thrush, Proc. Roy. Soc. A275, 544 (1963).
7-15

9. BAS COMBE -1965

Clyne and Thrush, Proc. Roy. Soc. A275, 559 (1963).

10. Von Elbe and Lewis. J. Chem. Phys . 10, 366 (1942).

11. Lewis and Von Elbe, "Combustion, Flames and Explosions in Gases"

Chapter II (1961).

12. Voevodsky and Kondratiev, "Progress in Reaction Kinetics",

Vol . 1 (1961), p. 43.

13. Hoare and Walsh, Chem. Soc. Spec. Pub. No. 9, p. 17 (1957).

14. Baldwin and Walsh, Disc. Faraday Soc. 17, 96 (1954).

15. Robertson, Disc. Faraday Soc, 17

,

98, 99 (1954).

16. Patrick and Robb, Disc. Faraday Soc. 17, 98 (1954).

17. Warren, Proc. Roy. Soc. A211, 96 (1952).

18. Avramenko and Kolesnikova, Izvest. Akad. Nauk SSSR, Otdel Khim.

Nauk, 1971 (1961).

19. Callear and Pereira, Trans. Faraday Soc. 59, 2774 (1963), Quoting

Clyne and Thrush for H + 0^ + ”* HO^ + H^, k = 2.0 x 10^-°

cnPmol'^s”^ at 293 K.

20. Baldwin and Doran, Trans. Faraday Soc. 57, 1578 (1961).

5. H

2 + M= H + H+ M

See Reaction Summary.

6. H + OH + M = H

2

0 + M

-31 6 -1

The combination rate was set at k = (4 ± 1) x 10 cm s at 2000°K for M * H2O, based on the flame studies of Padley and

Sugden-^- and McAndrew and Wheeler. ^ A negative activation energy

E = -1850 cal/mol was selected by analogy to the combination of

H atoms. The relative efficiencies of third bodies was set at

H20:N2 = 5:1 based on the work of Rosenfeld and Sugden. 3 Room

temperature data combination studies involving water photolysis,^

and discharge production of radicals^ give much lower rates than

the extrapolation from higher temperatures (and were not used).

Other references cited: 6,7.

1. Padley and Sugden, Proc. Roy. Soc. A248, 248 (1958).

2. McAndrew and Wheeler, J. Phys. Chem. 66, 229 (1962).

3. Rosenfeld and Sugden, Combustion and Flame 8, 44 (1964).
7-16

BAS COMBE -1965

4. Black and Porter, Proc. Roy. Soc. A266, 185 (1962).

5. Oldenberg and Rieke, J. Chem. Phys. 485 (1939).

6. Bulewicz and Sugden, Trans. Faraday Soc. 54. 185! (1958).

7. Dixon-Levis, et al, Symp. Combust. 10th. p 495 (1965).

7. o + o

2

+m«o

3

+m

See Reaction Summary for 0

3 + M * C + 0

2

+ M.

8. 0 + 0

3 = 02 + 02

See Reaction Summary for 0

3 + M « 0 + 0

2

.

9. o

2 + m= o + o + m

See Reaction Summary.

10. OH + OH * H

2

0 + 0

See Reaction Summary.

11. H

?

+ °

2 = °H + OH

’’Semenov, quoted by Singer and Williams [Ann. Rept. Chem. Soc.

45. 77 (1958)] gives A = 2.46 x 1 10~^ T®*5, E = 45,0)0 cal/mol for

the forward reaction.” Using these data the Arrhenius equation preexponential factor was set at 7 x 10“H. This gives k = 2 x 10"-^

exp(-26,330/RT) cnP molecule -

^- sec“^ for OH + OH * H,^ + 0^.

12. H

2

0

2 + M = OH + OH + M

The rate for peroxide dissociation (M = H2O2) in that of Baldwin

and Brattan. Rates with other partners are averages that include

the relative efficiencies reported by Forst^ and Hoare, Protheroe

and Walsh. Both references 2 and 3 provide evaluations of this

system and discuss earlier work.^'^ Direct studies of the OH combination (flash photolysis of water vapor^) are discounted. The

rates are high. The combination rate is calculated using equilibrium data.
7-17 I

BAS COMBE -1965

1. Baldwin and Brattan, Symp. Combust, 8th, p 110 (1962),

2. Forst, Can, J. Chem, 36, 1308 (1958).

3. Hoare, et al, Trans. Faraday Soc. 55, 548 (1959).

4. McLane, J. Chem. Phys. 17, 379 (1949).

5. Giguere and Liu, Can. J. Chem, 35, 283 (1957).

6. Satterfield and Stein, J. Phys. Chem. 61, 53 1 (1957).

7. Black and Porter, Proc. Roy. Soc. A266, 185 (1962).

13. H0

2

+ H0

2 = H

2

0

2

+ 0

2

Dixon-Lewis and Williams room temperature value used to set

the pre -exponential factor. Activation energy taken as zero.

Burgess and Robb's value, 30 times greater is close to the collision frequency and is considered surprising.

Dixon-Lewis and Williams, Nature 196, 1309 (1962).

Burgess and Robb, Chem. Soc. Spec. Pub. No. 9, p. 167 (1957).
7-18

BAULCH-1968

BAULCH, D. L., DRYSDALE, D. D., and LLOYD, A. C., "Critical Evaluation

of Rate Data for Homogeneous, Gas-Phase Reactions of Interest

in High -Temperature Systems", Dept, of Physical Chemistry. The

University, Leeds, England, iHigh Temperature Reaction Rate

Data, Report No. 1, May 1968.

Data sheets on each reaction include thermodynamic data, a table

and a figure showing the available experimental results, a discussion

and a bibliography. The authors do not hesitate to state that no

reliable estimate can be made for a reaction. The general format is

exce llent

1(a). CO + OH = C0

2

+ H

(b) . CO + OD = C0

2

+ D

See reaction summary for CO + OH = C0

2

+ H„

2(a) . CO + 0 = C0

2

+ hv

(b) . CO + 0 = C0

2

(c) . CO + 0 + M = C0

2

+ M

These three reactions are discussed in the same report. A

recommended rate is given for (a), a value stated for the 400-550 K

range for (b), and only an activation energy estimate, 2.5 kcal

mole"! given for (c). This reflects the limited pool of conflicting data.

The mechanism for CO combination with 0 can be written as a combination of steps (a), (b) and (c) . In all three steps, reaction

of ground state CO and 0 must lead to an electronically excited C0

2

* The recommended rate for (a) is based on analysis of chemiluminescence. It combines the data of Clyne and Thrush, Hartunian

et al^ Myers and Bartle^ and Kaskan. 0 The work of Mahan and

Solo which leads to a high activation energy is rejected. The

authors accompany their rate estimate with a warning that the

reaction may not be a simple bimolecular process.

The tentative recommendation for (b) is based on the results

in the 400-500 K regional! and shock wave dissociation studies. 16

Both stirred flow reactor studies are re jec ted . 1^, 15 Their rate

coefficients are lower by one or two orders of magnitude. The

authors note that (b) is unlikely to yield a product stable for

any length of time without participation of a third body.
7-19

BAULCH-1968

No rate is given for either the forward or reverse reactions of

(c) because of the great scatter of the data. Recent studies by Wong

et al^° that show a strong impurity effect are cited to explain this.

Data tabulated from references la, 2-6, 8, 10a, 13, 17, 19 and graphed.

1. Avramenko and Kolesnikova, Izvest, Akad. Nauk. S.S.S.R., Otdel,

Khim. Nauk (1959), 1562. (Same as la)

la. Idem, Bull. Acad. Sci. USSF 9_, 1506 (1959). Quoted in ref. 4.

2. Brabbs and Belles, Symp. Ccmbust. 11th, p. 125 (1967).

3. Brabbs, et al, J. Chem. Phys . 38, 1939 (1963).

4. Clyne and Thrush, Proc. Roy. Soc. A269

,

404 (1962).

5. Davies, J. Chem. Phys. 41, 1846 (1964); 43

2809 (1965).

6. Fishburne, et al, J. Chem. Phys. 45

,

160 (1966).

7. Generalov and Losev, J. Quant. Spectry. Radiative Transfer

6, 101 (1966).

8. Harteck and Dondes, J. Chem. Phys. 23 , 902 (1955).

9. Hartunian,, et al, J. Chem. Phys. 44

,

1765 (1966).

10. Kaskan, Ccmbust. Flame 3^ 39 (1959).

10a. Kaufman, Proc. Roy. Soc. A247

,

123 (1958).

11. Kondratiev and Ptichkin, Kinetika i Kataliz 2k 492 (1961).

12. Mahan and Solo, J. Chem. Phys. 3

, 2669 (1962).

13. Michel, et al, Z. Phys. Chem. Neue Folge 39

,

129 (1963).

14. Myers and Bartle, J. Chem. Phys. 4_7, 1783 (1967).

15. Mulcahy and Williams, Trans. Faraday Soc. 64

,

59 (1958).

16. Olschewski, et al, Symp. Combust. 11th, p. 155 (1967).

17. Steinberg, NASA, CR 68229, February 1965.

18. Wong, et al. NASA, TN D-4162 (1967); CA 68, 72748b (1968).

19. Zeegers, Ph.D. Thesis, University of Utrecht, Holland (1966).

3. C0

2

+ 0 = CO 4- 0

2

The value for the forward reaction cited is an average of the rate

calculated by Schofield from the data of Sulzmann et al on the reverse

and the rate developed by Brokaw reinterpreting the same data. Authors

recommend use of this value with caution. Data tabulated and graphed.

1. Schofield, Planet. Space Sci. 15, 643 (1967).

2. Sulzmann, et al, J. Chem. Phys. 42

,

3969 (1965).

3. Brokaw, Symp. Combust. 11th, p. 1063 (1967).
7-20

CHERRY-1967

CHERRY, S. S., GOLD, P. I., and VAN NICE, L. J., Phase I Final Report,

’’Screening of Reaction Rates" 22 May 1967. TRW Systems,

Redondo Beach, California, Report 08832-6001-T0000.

I ntroduction

This report is part of a study performed by TRW Systems for the

Theoretical Methods Committee of the Interagency Chemical Rocket

Propulsion Group. Phase I of the study was concerned with identifying the chemical reactions that significantly affect performance

calculations for important liquid propellant systems. One objective

of developing such a list was the establishment of criteria for the

minimum set of reactions with which future non-equilibrium performance

calculations should be made. This was the concern of Phase II of the

project.^- Another objective was to indicate to reaction kineticists

those reactions for which precisely determined rate constants are

needed.

Both the Phase I and Phase II reports list the reactions cited

here as CHERRY-1967. Only the Phase I report lists the notes and references pertinent to specific reactions.

A prime objective of the Phase I study was the establishment of

uncertainties for the rate coefficients. These are given for each

reaction. They are not measures of the precision of the data so much

as they are ranges within which the rate coefficients must lie. Thus

they are pertinent to the boundary conditions for the design of propulsion systems. The authors state:

"Selected rates were divided into two categories: those

obtained from the literature which are based on experimental evidence, and those which were analytically determined on the basis of theoretical treatments or otherwise

estimated. The limits of reliability of those based on

experiment were assigned on a somewhat qualitative evaluation of the experimental techniques utilized in their

determination as well as their reported accuracy. Theoretically determined or estimated rate constants were in

most cases assigned uncertainty limits based on collision

frequency considerations.

"In several instances, a choice was made from widely

differing rates. In these cases, rates and uncertainty

limits were selected to insure coverage of the range of

probable values [when the rates were used in] the perturbation study."
7-21

CHERRY-1967

The uncertainties given are multiplicative: 1/a < k/k

Q < a. These convert, in the notation used in the present compilation, to

uncertainties in A: A ± log a.

The authors have made use of other evaluations and compilations

in developing their list. Over 150 references are cited. There are

quotations from compilations that are also included in this compendium. Usually these are not repeated. Instead, a notation appears

in the descriptive material provided for the quoted source.

A substantial number of the reactions also carry notes indicating the participation of G. S. Bahn in the development of the recommended rates and the uncertainties. These are all summarized in the

notes here as ’’private communications”. (The notes that appear in the

Phase I report are reproduced below. 2) The details of these evaluations and calculations are not available. However, Bahn has also

published evaluations and selections of preferred rates (see BAHN1964, 1965, 1968 in this compendium and reference 3) . There is some

overlap. Bahn has indicated that the. published values adequately

reflect his approach to the problem of selecting and calculating

rate coefficients.

Some rate parameters in CHERRY-1967 are stated to a number of

significant figures exceeding the assigned uncertainties. Usually

these numbers were the results of curve fitting procedures or

theoretical calculations. Most of them were rounded prior to being

processed for this compendium. The notes provided here follow those

in CHERRY-1967 closely. The units used in the report and for quotations in these notes are: time in seconds, temperature in Kelvin,

concentration in moles/cm^ and activation energies in cal/mole. The

reactions in the report run from right to left . For some reactions

the activation energy, E*, is given, and for some E*/R.

1. Cherry, S. S. and Van Nice, L. J., "Screening of Fraction Rates,”

Phase II Final Report, Vol. I Technical Analysis, TRW Systems

Group, Redondo Beach, California, 6 December 1967, No. 08832-

6O02-T0O00.

2. "Private Communi cation from Bahn (Marquardt Corp.) to L. J. Van Nice

and RFP SN-82-102 (ICRPG)."

"Unpublished Report on Reactions in the F-C1-H-0 -N System by

G. S. Bahn, Marquardt Corporation, February 1967."

"Private Communication with G. S. Bahn, April 27, 1967"

3. Bahn, G. S., Pyrodynamics 1, 147, 271, 335 (1964); Ibid 2, 91,

197, 315 (1965); Ibid 3 245 (1965); Ibid 4, 63, 211, 305, 371

(1966); Ibid 5, 49, 75, 221, 375 (1967); Ibid 6, 101 (1968).
7-22

CHERRY -196

1.

F

2

+ H = F + HF

Collision theory value, i.e. A set at the collision frequency

recommended by various authors. This is a factor of 10 higher

than the formal order of magnitude estimate for this type of reaction. The value given is probably somewhat high. Uncertainty

assessed at collision frequency , limit

Bahn, Private communication.

Tunder, et al, Aerospace Corp., Thermochemistry Research Dept.,

Report No. TR- 1001(9210-02) -1, January 1967.

Sarli, et al, United Aircraft Res. Lab. Report UAR-E72, May 1966.

Burwell, et al, United Aircraft Corp. preprint for Third Conference on Performance of High Temperature Systems (December 1964)

Klein and Wolfsberg, J. Chem. Phys. 34, 1494 (1961). [Not

directly applicable to H + Paper deals with H -r Cl^ . ]

2.

F + H

2 = H + HF

Determined by analogy to OH + H = H

2 + 0 for which consult

references 1-6. The value given here agrees to within a factor

of 10 with rates derived from experimental data^>3,7,8

k * 1 x 10l2eXp(-E/RT), E = 5000 or 7000 cal /mol . Compared to

the rate estimated by the Johnston and Parr method^* 3, 9, 10 there

is a discrepancy of a factor of 70. The uncertainty was assessed

at a factor of 50.

1. Patch, J. Chem. Phys. 36, 1919 (1962).

2. Bahn, Private communication.

3. Bittker, NASA TN D-3607, August 1966.

4. Mayer, et al, Aerospace Corp. Report No. TDR-269(421Q-10) -6,

18 September 1964.

5. Gold and Weekley, TRW Systems, Redondo Beach, California,

Report 02874 -6001-R000, 6 December 1966.

6. Cook and Schieler, Aerospace Corp. Report TDR-269(9210-02) -1,

October 1964.

7. Jacobs, et al, J. Chem. Phys. 43, 3688 (1965).

8. Levy and Copeland, J. Phys. Chem. 69, 408 (1965).

9. Tunder, et al, Aerospace Corp., Thermochemistry Research Dept.,

Report No. TR-1001(9210-02) -1, January 1967.

10.

Mayer, et al, J. Chem. Phys. 4_5, 385 (1966).
7-23

CHERRY- 1967 3.

H + Cl

2 - Cl + HC1

A number of estimated rates are available.^ ^ These values

agree to within ail order of magnitude. In view of the lack of

experimental data, the selected valued ^-7 wag assessecj a j- an

uncertainty equal to the collision frequency limit.

1. Bahn, Private communication.

2. Mayer, et al, Aerospace Corp. Report TDR-269 (4210-10) -6,

18 September 1964.

3. Mayer and Schieler, Aerospace Corp. Report TDR-669 (9210-02) -2,

May 1966.

4. Schieler and Mayer, CPIA Publication 108, p. 131 (June 1966).

5. Ashmore and Chanmugam, Trans. Faraday Soc. 49, 254 (1953).

6. Thrush, "Progress in Reaction Kinetics", Vol. 3, p. 63

(Pergamon Press, Oxford, 1965)

7. Klein and Wolfsberg, J. Chem. Phys. 34, 1494 (1961).

4.

H + HC1 * Cl + H,

A number of experimentally based rate constants are available. Although these are based on low temperature data, they

agree with each other to within a factor of 4. Furthermore, when

compared to several well based estimated rates, the agreement is

still better than a factor of 5. The value selected, 6.2 x IqIIt0 * 5 exp( -3100/RT) was assessed with an uncertainty of one

order of magnitude.

1. Bahn, Private communication.

2. Clyne and Stedman, Trans. Faraday Soc. 62, 2164 (1966).

3. Fettis and Knox, "Progress in Reaction Kinetics", Vol. 2,

p. 1 (Pergamon Press, New York, 1964)

4. Fishburne, J. Chem. Phys. 45, 4053 (1966).

5. Steiner and Rideal, Proc. Roy. Soc. A173, 503 (1939).
7-24

CHERRY-1967

5 . C1F + H = Cl + HF

C1F + H = F + HC1

Several estimates are available for rates of these reactions. The spread is over one order of magnitude. That from the

Johnston and Parr technique was selected [see General Notes].

There are no experimental data. The uncertainty was assessed

at the collision limit.

1. Bahn, Private communication.

2. Tunder, et al, Aerospace Corp., Thermochemistry Research Dept.,

Report No. TR-1001(9210-02) -1, January 1967. [Order of magnitude estimate]

3. Mayer, et al, J. Chem. Phys. 45, 385 (1966).

4. Mayer and Schieler, Aerospace Corp. Report TDR-669(9210-02) -2

May 1966.

5. Schieler and Mayer, CPIA Publication 108, p. 131 (June 1966).

6. CO + 0

2 = C0

2 + 0

This is the only literature value found. The rate compares

rather poorly [is higher] with formal order of magnitude estimates.

Tunder, et al, Aerospace Corp., Thermochemistry Research Dept.,

Report No. TR-1001(9210-02) -1, January 1967. [quoting Sulzmann,

et al, below]

Sulzmann, et al, J. Chem. Phys. 42, 3969 (1965).

7.

N + NO = N

2 + 0

Bortner'*’ reviews a considerable body of experimental data

regarding this reaction^‘9 and concludes that the rate chosen

should have an uncertainty of about a factor of 2. This might be

somewhat optimistic. A factor of 5 was chosen.

1. Bortner, GE Missile and Space Division Report No. R63SD63,

Augus t 1963

2. Wray and Teare, J. Chem. Phys. 36. 2582 (1962).

t 3. Kaufman and Decker, Symp. Combust. 7th, p. 57 (1959).

4. Glick, et al, J. Chem. Phys. 27, 850 (1957).
7-25

CHERRY-1967

5. Kistiakowsky and Volpi, J. Chem. Phys. 27, 1141 (1957).

6. Verkeke and Winkler, J. Phys. Chem. 64, 319 (I960).

7. Herron, J. Chem. Phys. 35. 1138 (1961).

8i. Clyne and Thrush, Proc. Roy. Soc. A261. 259 (1961).

9.

Duff and Davidson, J. Chem. Phys. 31, 1018 (1959).

8. NO + NO - N

2

4

- C

2

Bortner-^ reviews a considerable body of experimental data

regarding this reaction. ^ “4 Because of uncertainties in the

mechanism, it was concluded that the rate has a factor of 10

uncertainty.

1. Bortner, GE Missile and Space Division Report No. R63SD63,

August 1963.

2. Freedman and Daiber, J. Chem. Phys. 34, 1271 (1961).

3. Kistiakowsky and Volpi, J. Chem. Phys. 27. 1141 (1957).

4. Wise and Freeh, J. Chem. Phys. 20. 22 (1952).

9. N + 0

2

NO + 0

See Reaction Summary.

10. H

2

-f OH * H + H

2

0

See Reaction Summary for H + H

2

0 * H

2

4- OH.

11. 0 + OH * H + 0

2

H + OH * H

2 + 0

See Reaction Summaries for each of the reverse reactions.

12. OH + OH = H

2Q + 0

See Reaction Summary
7-26

CHERRY -19 6

13. OH + OH = H

2 + 02~ 1 2

The selected value was calculated based on data for the

reverse (endothermic) reaction. It is agreed^j^ that this reaction must be very slow with respect to other possible mechanism.

The collision frequency limit was assigned as the uncertainty.

1. Balm, Private communication.

2. Langen, et al, AIAA J. 3_, 2211 (1965).

3. Kaskan and Browne, General Electric Report No. R64SD37,

February 1964.

14 . CO + 0 + M = C0

2 + M

Kaskan and Browne evaluate the available data and recommend

this value as do Gurney, et al. Some uncertainty must, however,

be attached to this value. In fact, in the presence of hydrogen,

H-0 recombination dominates and this reaction may well be ignored.

Because of uncertainties regarding third body efficiency, a factor of 10^*5 Was assigned.

Kaskan and Browne, General Electric Report No. R64SD27, February

1964 , Gurney, et al, in "Aerospace Chemical Engineering", (Chem. Eng.

Progr. Symp. Series, No. 61, Vol. 62, 1966), p. 142.

15 . N + N + M=N

2

+M

N + 0 + M=N0+M

Bortner has made a relatively thorough study of the available

experimentally based rates. Because of uncertainties in the

arbitrary third body assumption, a factor of 10 was assigned.

Bortner, GE Missile and Space Division Report No. R63SD63,

August 1963.

16 • H + Cl + M = HC1 + M

No experimental data are available. The selected rate, an

order of magnitude estimate, agrees to within a factor of two

with that calculated by cascade deactivation theory.^ Other

estimated rates^j^ differ by as much as 10^ *5. Thus, the uncertainty was assessed at the collision frequency limit.
7-27

CHERRY-1967

I 1. Crowe, et al, United Technology Center Report UTC 2128 -FR

(15 June 1966).

i 2. Jensen and Kurzius, Aerochem Research Laboratories, Princeton,

N. J., March 1967. Report TP-149.

3. Cook and Schieler, Aerospace Corp. Report TDR-269(9210-02) -1,

October 1964.

19. H + F + M^HF+M

1-3

As has been done by others the rate for this reaction is

Assumed to be equdl to that for H+H + M=H2 +M. Other theoretical estimates are given in references 4-7. The only data,

measured are for M “ Ar with assumed third body efficiencies

The value given here lies in about the middle of the range of

reported values. Assignment of an uncertainty factor of 10l*5

assures that the maximum reported rate will be included.

1. Bahn, Private communication.

2. Bittker, NASA TN D-3607, August 1966.

3. Wilde, AIAA J. 2, 374 (1964).

4. Burwell, et al, United Aircraft Corp. preprint for Third

Conference on Performance of High Temperature Systems

(December 1964)

5. Cole and Roquemore, Boeing Co. Document D5-12210 (29 March

1965)

6. Jacobs, et al, Aerospace Corp. Report TR-669(6240-201) -11

(June 1966)

7. Crowe, et al. United Technology Center Report UTC 2128-FR

(15 June 1966).

8. Weber, Rocketdyne Memo No. RM 12/4-358 (March 1, 1966).

9. Jacobs, et al, Aerospace Corp. Report No. TDR-469(5240-20) -10

(June 1965). Published as J. Chem. Phys . 43 , 3688 (1965).

20. H + OH + M « H

? 0 + M

The value given here is based on evaluation of a series of

rate estimates cited below. There is considerable uncertainty

regarding the effects of third bodies. A factor of 10-* uncertainty

must be assessed to assure coverage of the upper limit of the

probable range in the case of arbitrary third bodies.
7-28

CHERRY-1967

Lezberg, et al, NASA TN D-2883, June 1965.

Bahn, Private communication.

Weber, Rocketdyne Memo No. RM 12/4-358, March 1, 1966.

Mayer, et al, Aerospace Corp. Report No. TDR-269(4210-10) -6,

18 September 1964.

Lezberg and Franciscus, AIAA J. 1^ 2071 (1963).

Langen, et al, AIAA J. 3j 2211 (1965).

Rosenfeld and Sugden, Combust. Flame 8^ 44 (1964).

Dixon-Lewis, et al, Symp. Combust. 10th, p. 495 (1965).

Bulewicz and Sugden, Trans. Faraday Soc. 54. 1855 (1958).

Westenberg and Favin, Symp. Combust. 9th, p. 785 (1963).

21. H + H + M = H

2 + M

See Reaction Summary for H

2

+M = H+ H + M.

22. H + 0 + M = OH + M

1 2

The value selected ’ [is an estimate that equates this

reaction to H + H + M * H2 + M] . It adequately covers the data

found-^^ to within an uncertainty factor of five.

1. Tunder, et al. Aerospace Corp., Thermochemistry Research

Dept., Report No. TR-1001(9210-02) -1, January 1967.

2. Westenberg and Favin, Symp. Combust. 9th, p. 785 (1963).

3. Bahn, Private communication.

4. Langen, et al, AIAA J. 3, 2211 (1965).

23. 0+0+M=0

2

+M

See Reaction Summary for 0

2

+M*=0 + 0 + M.

24 . CO + OH = C0

2 + H

See Reaction Summary.
7-29

CHERRY-1967

25. C0

2

+ N * CO -f NO

This reaction is a so-called "spin-forbidden" reaction and

cannot occur with all species in their ground states. The reaction can, however, occur with atomic nitrogen in its first

excited electronic state, that is.

An "effective" rate constant for C0

2 + N = CO + NO can be

obtained as follows: Suppose the populations of N atoms in the

various electronic states are related by a Boltzmann distribution

where AE = 55000 cal is the energy difference between the ground

and first excited state of N. Then,

C0

2 + N CO + NO k1

-AE/RT

e

r = -k

x (C0

?

)(N*) = -k

x e -AE/RT

(co

2

)(n)

or.

The constant is an order of magnitude estimate. The uncertainty was assessed at the collision frequency limit.

26. Bahn, Private communication.
7-30

JENSEN-1967

JENSEN, D. E. and KURZIUS, S. C., ’’Rate Constants for Calculations

on Nozzle and Rocket Exhaust Flow Fields,” AeroChem

Research Laboratories, Princeton, New Jersey, Kerch 1967.

Report TP- 149.

Int roduction

This report is an annotated tabulation of rate coefficients for

111 reactions (single direction - forward and reverse rates for the

same system are given rarely.) The H-0 system, reactions of halogens

and halogen oxides, reactions of alkali metals, CO, CHO and CE^O are

considered. Some ionization reactions are included. The coefficients

are intended for use in calculations for systems at temperatures

between 1000 and 3500 K.

The rate coefficients are the result of an evaluation of experimental data (where they exist) and estimates based on analogy to

similar reactions. The basis for the value reported is explained.

Uncertainty ranges are given for each case. They are presented as

multiplicative factors: k x 1/a, k x a which, in the notation used in

this compilation, convert to A ± log a (or log k ± log a). These

uncertainties are explained by the authors as follows.

’’The upper possible error factor is defined as the ratio

of our estimate of the probable upper limit of the rate

constant to our estimated rate constant k itself at the

temperature at which the rate constant is least accurately

known. The lower possible error factor is the ratio of k . to our estimate of the probable lower limiting value of

the rate constant at this temperature. These error factors

are the result of reasonable semi -quantitative appraisal

rather than detailed statistical analysis of the available

data and are intended principally to give the engineer a feeling for the uncertainty in each rate constant. The

factors are usually considerably larger than the uncertainties attached to their results by the original experimenters; this is almost always because we have had to

extrapolate available results into temperature ranges

considerably different from those of the experiments

themselves

Where Jensen and Kurzius give unequal upper and lower uncertainty

limits, the larger has been used for the uncertainty in A. Each of

these cases is identified in the notes.
7-31

JENSEN-1967

Combination and dissociation reactions involving a "third body"

energy transfer agent are assigned rates applicable to a generalized

third body. This is a molecule as opposed to an atom. These rates,

as are all the others, are thermal rates. The authors find it impractical at present to take into account excited states in an

explicit manner.

The rate quotient law, K

reactions

eq

k_/k is assumed to hold for all

f r

The values given are "considered to be the best that can be

gleaned from the literature published up to December 1966." Sixtynine references are cited.

The notes in this compendium are based on those of the authors

and are often abbreviated quotations. Some have been rewritten to

make them more understandable in the context and format of the present compilation.

1. 0 + 0 + M~0„+M

See Reaction Summary for 0^+M E 0 + 0-fM,

2 • Q 4- H + M =* OH + M

It appears that no experimental work has been done on this

reaction, [The rate constant was set equal to that for

0 + 0 + M*0

2

+M and H4-H4-M=H„4-M.]

3 . H+H + M*H

2

+M

See Reaction Summary for +

4 . H 4- OH 4* M * H?0 4- M

Little reliable data are available for this reaction. The

agreement between independent values of k obtained by Bulewicz and

Sugden and by McAndrew and Wheeler, for example, is fortuitous in

view of the lack of distinction between contributions from

H 4* H 4- H O * H-0 4- Hn l 2 l

and

H + OH + H„ * H«0 +

Z Z L *

The limits used in the report and in the quoted values in these notes are

time in seconds, temperature in Kelvin, concentration in molecules/cm^,

and activation energy in ca lories /mo le
7-32

JiNSEN-1967

in the former work. Schott and Bird appear to have ol twined a

reasonably reliable value, however, and the wide error limits

suggested here reflect uncertainties in third-body eff Lcicnci^^

The rate constant given corresponds to a very large (~ 3 x 10"^)

pre -exponential factor for the dissociation reaction.

Bulewicz and Sugaen, Trans. Faraday Soc. 54, 1855 (1952)

IdcAuidrew and Wheeler, J. Fhys. Chem. 66, 229 (1962).

Schott and Bird, J. Chem. Phys. 41, 2669 (1964).

5. CO + 0 4- M = C0

2

4- M

The surprising exponential term is suggested by the work of

Clyne and Thrush at temperatures lower than those encountered in

racket exhausts. At 2000 K, the exponential term does not carry

a great deal of weight by comparison with the uncertainties in

the rate constant as a whole. Zeegers’ work suggests that O

2 has

a very high third -body efficiency in this reaction (k 2.4 x 10”^3

fer M = 0 ? at 2350 K) but that 2O

2 is inefficient (k ~ 2.4 x 10”33

for M - CO2 at 2350 K) . The value of k listed is probably an upperlimit value. Unequal error limits given: 0.033 < k/k

Q <3.

Clyne and Thrush, Symp. Combust. 9th, p. 57 (1963).

Zeegers, Ph.D* Thesis, University of Utrecht, Holland (1966).

6. OH + OH « H ?0 + 0

See Reaction Summary.

7

H

2 + OH - H + H

2

0

See Reaction Summary for H + H

2

0 H

2 + OH.

8.

H0 + 0 » H + OH

See Reaction Summary.

9.

H + 0

2 = 0 + OH

See Reaction Summary.
I 7-33

JENSEN-1967

io. co + oh = a>

2 + H

11. See Reaction Summary.

H + Cl0 * Cl + HC1

, The rate constant given was estimated by Fristroxn and

Westenberg on the basis of results obtained by Klein and

Wolfsberg

Fristrom and Westenberg. ’’Flame Structure” (McGraw-Hill Book Co.,

New York, 1965)

Klein and Wolfsberg, J. Chem. Phys . 34, 1494 (1961).

12.

H

2

+ Cl = H + HCl

The estimates of this rate constant given by Fristrom and

Westenberg and by Fettis and Knox are in good agreement with

one another. The rate constant given here is based on these two

estimates

Fristrom and Westenberg, ’’Flame Structure” (McGraw-Hill Book Co.,

New York, 1965)

Fettis and Knox, ’’Progress in Reaction Kinetics”, Vol. 2, p. 1

(Pergamon Press, New York, 1964)

13

Cl + H

2

0 * HCl + OH

Estimated by comparison with Cl + HCl - Cl

2

+ H, due allowance being made for a steric hindrance factor and for an activation energy 4000 cals/mole greater than the endo thermic! ty

14 • Cl + OH = HCl + OH

Estimated by eomnarison with that for OK 4* H * H + 0

(k = 1.3 x lO” 1 ^- e”63uO/RT) # Each of these reaetions Z is spin

allowed and approximately thermoneutral
7-34

JENSEN-1967

15. H + HF =* F + H

2

This rate constant is the result of an experimental study of

the kinetics of decomposition of HF by Jacobs, Giedt, and Cohen.

Note that the pre -exponential factor in the rate constant for

similar reaction H 4- ilCl - H

2

4- Cl, given by Fristrom and Westenberg,

1.0 x 10 ”^, i s 5 times larger.

Jacobs, et al, AIAA Second Propulsion Joint Specialist Conference,

Colorado Springs, June 1966, Paper 66-637.

Fristrom and Westenberg, "Flame Structure" (McGraw-Hill Book Co.,

New York, 1965)

16. F

2

+ H * F + HF

This rate constant is set equal to that for H 4- Cl£ * HC1 4* Cl.

The pre -exponential factor is approximately equal to the collision

frequency. Both reactions are strongly exothermic.

17. HC1 4 Li - H 4 LiCl

HC1 4- Cs = CsCl + H

Estimated by comparison with those for Na 4- HC1 ~ NaCl 4* H

and K 4- HCl = KC1 4- H, the bond energy of the metal halide used

being that listed by Gaydon. [Unequal error limits given:

0.033 < k/k <10.]

o Gaydon, "Dissociation Energies" (Chapman and Hall, London, 1953).

18. HCl 4- Na = H 4- NaCl

This estimate is based on measurements made by M. Polanyi in

1932; no recent measurements appear to be available. However,

Kondratiev reports results of Taylor and Datz which suggest that

the rate constant of the reaction

K 4* HBr = KBr + H; AH = -4000 cals/mol

is given by

k = 3.0 x 10' 12

T°‘

5

e'

3400/,RT

, 500 < T < 800 K

or, at 1600 K, by

k 1 . 2 x 10

- 10

e340°/RT
7-35

JENSEN-1967

These results and others cited hy Kondratiev suggest that the preexponential factors of rate constants of reactions like this one

are close to the collision frequencies* The rate constant given

here stems from adoption of this suggestion. Taylor and Datz used

a molecular beam technique; Polanyi* s early work suffers from uncertainties concetning the possible effects of solid particles.

[Unequal error limits given: 0.033 < k/k^ < 10.]

Polanyi, "Atomic Reactions" (Williams and Norgate, London, 1932).

Kondratiev, "Chemical Kinetics of Gas Reactions "(Pergamon Press,

New York, 1964) p. 90.

Taylor and Datz, J. Chem. Phys. 23, 1711 (1955).

19. HCl + K « H + KC1

This rate constant is based on the work of Polanyi and the

discussion given by Kondratiev. [Unequal error limits given:

0,033 < k/k < 10.]

o Polanyi, "Atomic Reactions" (Williams and Norgate, London, 1932),

Kondratiev, "Chemical Kinetics of Gas Reactions" (Pergamon Press,

New York, 1964) p. 90.

20. Me 4* H^O * MeQH + H (Me * Li, Na, K, Cs)

The rate constant for Li + H„,0 ~ LiOH + H was estimated on

2

the basis of arguments given by Sugden-'- and experimental evidence

obtained by Jensen^ and Jensen and Padley.-^ Hie activation energy

is estimated through reference to the work of Jensen and Padley

p

3000 cals/mol are arbitrarily added to the known e ndo the nsdL city.

The reactions of Na, K and Cs with H^O were estimated in a similar

manner,

1. Sugden, Trans, Faraday Soc. 52, 1465 (1956).

2. Jensen, Ph.D. Dissertation, University of Cambridge, 1965,

3. Jensen and Padley, Trans, Faraday Soc. 62, 2140 (1966),

4. Jensen and Padley, Trans, Faraday Soc, 62, 2132 (1966).
7-36

JENSEN-1967

21. H + Cl + M - HC1 + M

No experimental data appear to be available for this reaction.

The value given is estimated through comparison with rate constants

for other ternary reactions, including H + F + M*HF+M, [Unequal

error limits given: 0.033 < k/kQ < io.]

22. Cl + Cl + M * Cl

2 + M

The work of Jacobs and Giedt^ suggests a rate constant smaller

by a factor of 10. Hiraoka and Hardwick, 2 on the other hand, find

that k « 7 x 10"33 at 1600 K for argon as a third body. This would

correspond to our value for molecular third bodies, assumed to be

three times as efficient as Ar. [The reported pre -exponential is

derived from 3 x 7 x 10”33 *s a x (1600)“ .] Fristrom and Westenberg^

suggest [that] the results of Hiraoka and Hardwick are to be preferred to those of Jacobs and Giedt [because the former check

results on Br atom combination

1

].

1. Jacobs and Giedt, J. Chem. Phys. 39, 749 (1963).

2. Hiraoka and Hardwick, J. Chem. Phys. 36, 1715 (1962).

3. Fristrom and Westenberg, ’’Flame Structure” (McGraw-Hill Book

Co., New York, 1965).

4. Palmer and Homig, J. Chem. Phys. 26, 98 (1957).

23. F + H + M- HF+M

This rate constant has been measured^ with Ar as third body in

the temperature range 4000 < T < 5300 K. The results obtained could

be described in terms of k. * 5 x 10"29t“ 1, but the scatter of

results was rather large. Multiplication of k^r by 5 to allow for

greater efficiency of molecular third bodies would give k 2.5 x

10“28T-1. This seems rather high. The value stated is preferred as

a compromise until further work is done. Note that the experimental

rate constant^ is of the same order of magnitude as that predicted

by Benson and Fueno.

1. Jacobs, et al, AIAA Second Propulsion Joint Specialist Confer

ence, Colorado Springs, June 1966, Paper 66-637.

2. Benson and Fueno, J. Chem. Phys. 3(3, 1597 (1962).
7-37

JENSEN-1967

24. F + F + M=F

2

+M

The rate constant for this reaction is based on the work of

Johnson and Britton^- and Diesen, 2 who studied the dissociation of

F

2 by Ar in shock tubes. The temperature -dependence given corresponds approximately to that found for the reserve reaction by

Johnson and Britton; that suggested by Diesen 1 s work appears

improbably high. Allowance is made for molecules in rocket

exhausts being more efficient in producing dissociation than Ar

atoms. Note that the pre -exponential factor in the rate constant

for the reverse reaction is considerably smaller than those for

the corresponding reactions for the other halogens. ^ [This value

and its uncertainty also cited by Cherry.

1. Johnson and Britton, J. Fhys. Chem. 68. 3032 (1964).

2. Diesen, J. Chem. Phys. 44. 3662 (1966).

3. Cherry, et al, TRW Systems, Redondo Beach, Calif., Report

0883 2 -600 1 -T0000 (1967).

25. Me + OH + M = MeOH + M (Me =* Li« Na. K. Cs)

The value for Li + OH + M = LiOH + M is a very high rate

constant, although certainly not the highest ever suggested for

a ternary recombination reaction - see, for example, McAndrew and

Wheeler. Combination of theoretical arguments of Sugden and

experimental results of Jensen and Padley and Bulewicz and Sugden

shows that the rate constant for the reverse reaction cannot be

much smaller than 6 x 10 ”^T”^e”^-® 1000 /RT, an(j that k therefore cannot be much smaller than 10“27t“ 1

# (The equilibrium constant for

formation of LiOH is approximately 1.6 x 10"24 e lQ100/RT # ) The

value of k recommended above seems a reasonable compromise: it is

not much smaller than 10”27t“ 1 and not much greater than the rather

high rate constant for the formally similar reaction H + OH + M

H2O + M. The ternary combinations of Na, K and Cs with OH were

estimated on the same basis. [Unequal error limits given: 0.033 <

k/k

Q

< 10.]

McAndrew and Wheeler, J. Phys. Chem. 66^ 229 (1962).

Sugden, Trans „ Faraday Soc. 52 1465 (1956).

Jensen and Padley, Trans. Faraday Soc. 6^2, 2140 (1966); Ibid

62, 2132 (1966).

Bulewicz and Sugden, Trans. Faraday Soc. 52. 1481 (1956).
7-38

JENSEN- 1967

26. Me + Cl + M = MeCl + M (M = Li. Na. K. Cs)

No experimental data are available for these reactions. The

rate constant k is perhaps likely to be somewhat smaller than that

for reaction Li + OH + M * LiOH + M (the collision is less " sticky"

note that the rate coefficient of H + Cl + M * HC1 + M is less than

that of H + OH + M = H£0 + M.) The value given for Li + OH is (for

no particularly good reason) the geometric mean of those for

Cl + Cl + M = Cl2 + M and Li + OH + M * LiOH + M. The rates for Na,

K and Cs combining with Cl in a ternary collision were estimated in

a similar manner. [Unequal error limits given: 0.01 < k/k

Q < 30.]

27. Li

+ +e~+M«Li+M

This rate constant was calculated from measurements on the

reverse reaction by Jtensen and Padley at 2475 K. The temperature

dependence is assumed to be the same as that of Na* + e" + M * Na + M,

All molecular third bodies are assumed to have equal third-body

efficiencies. Hollander indicates that atomic third bodies are less

efficient.

Jensen and Padley, Trans. Faraday Soc. 62, 2140 (1966).

Jensen and Padley, Symp. Combust. 11th, p. 351 (1967).

Hollander, Ph.D. Thesis, University of Utrecht, Holland (1964).

28. + e + M * Na + M

Jensen and Padley measured the rate constant of the reverse

reaction at 2020 to 2450 K at atmospheric pressure in H2 /N2 /O 2

flames and calculated k « 1.4 x 10"20t~2 # Hollander, Alkemade,

and Kalff, using CO/N2 /O2 flames in a similar (but narrower) range

of temperature, find k = 1.6 x 10“?®T“2 # Molecular third bodies

tend to have approximately equal efficiencies in this reaction, but

atomic third bodies are much less efficient (Hollander).

Jensen and

Jensen and

Hollander,

Hollander,

Padley, Trans. Faraday Soc. 62, 2140 (1966).

Padley, Symp. Combust. 11th, p. 351 (1967).

et al, J. Chem. Phys. 39. 2558 (1963).

Ph.D. Thesis, University of Utrecht, Holland (1964).
7-39

JENSEN-1967

29. K

+ +e~+M=K + M

This rate constant was calculated from measurements on the

reverse reaction by Jensen and Padley. The corresponding value

for atmospheric-pressure CO/N^/O^ flames is 1.5 x 10"22y-1.5 # Jensen and Padley, Trans. Faraday Soc. 62, 2140 (1966).

Jensen and Padley, Symp. Combust. 11th, p* 351 (1967).

30. Cs* + e~ + M = Cs + M

Calculated from measurements on the reverse reaction by

Jensen and Padley. ^->2 Hollander, Alkemade and Kalff^ find a much

smaller rate constant (2 x 10 - 23 t- 1.5) in CO/N2 /O2 flames.

Jensen and Padley ’s results are preferred (a) because two independent analytical techniques (optical emission spectroscopy and

microwave cavity resonance) gave the same rate constant- -within

the limits of experimental error--in their work, and (b) because

the order of magnitude of their results is consistent with equilibrium ionization of cesium being closely approached under conditions employed by other workers,^ whereas that of Hollander,

Alkemade, and Kalff's results is not.

1. Jensen and Padley, Trans. Faraday Soc. 62, 2140 (1966).

2. Jensen and Padley, Symp. Combust. 11th, p. 351 (1967).

3. Hollander, et al, J. Chem. Phys . 39. 2558 (1963).

4. Knewstubb, Ph.D. Dissertation, University of Cambridge (1956).

5. Hayhurst, Ph.D. Dissertation, University of Cambridge (1964).

6. Padley and Sugden, Symp. Combust. 8th, p. 164 (1962).

31. Li

+

+ Cl' = Li + Cl

Cs

+

+ Cl~ = Cs + Cl

Estimated by comparison with the rates for Na 4- Cl Na + Cl

and K+ + Cl » K + Cl. It may be noted that the value of k for

Li-

*- + Cl“ * Li + Cl corresponds to a rate constant for the reverse

reaction of 4 x 10~10e"^0u0/RT at 2000 K: the pre -exponential factor

of the reverse reaction rate constant is thus close to the collision

frequency. It should also be borne in mind that uncertainties in

crossings of potential energy curves cause one to doubt the validity

of this simplified approach to the determination of mutual neutralization rate constants. It is implicitly assumed, for example, that

for this reaction the potential energy curves involved are favorably

placed with respect to one another. [Unequal error limits given for

Li+ + Cl: 0.01 < k/k

Q < 10.]
t 7-40

JENSEN- 1967

32. Na

+

+ Cl* - Na + Cl

An approximate value for this rate constant was measured by

Hayhurst and is discussed by Hayhurst and Sugden. Baulknight

and Bortner estimate the following theoretical rate constants:

0

+

+ o" - 0 + 0 k - 5.5 x 10-V0 - 5

N

+

+ O' = N + 0 k - 8.4 x 10'7t'°'

5

Comparison with these estimates is the basis for the T

°* 5

temperature dependence in k; Sugden reports that the measured temperature dependence is slight.

Hayhurst, Ph.D. Dissertation, University of Cambridge, 1964.

Hayhurst and Sugden, "The Ionization Processes Associated with

Metallic Additives in Flame Gases,' 1 presented at IUPAC Meeting

on Plasmas, Moscow, 1965 (to be published).

Hayhurst and Sugden, Proc. Roy. Soc. A293. 36 (1966).

Baulknight and Bortner, General Electric Corp. Report R64SD12 (1964).

Sugden, AGARD Combustion and Propulsion Panel Meeting, Pisa, Italy,

September 1965 (to be published)

33. K~*~ -f Cl~ = K + Cl

Measured by Hayhurst and reported by Hayhurst and Sugden.

The temperature dependence of k is based on the theoretical

estimate for O'** + 0"=* 0 + 0 and N+ + 0“ * N + 0 made by

Baulknight and Bortner. [Unequal error limits given: 0.01 <

k/k < 10.]

o Hayhurst, Ph.D. Dissertation, University of Cambridge, 1964.

Hayhurst and Sugden, "The Ionization Processes Associated with

Metallic Additives in Flame Gases," presented at IUPAC Meeting

on Plasmas, Moscow, 1965 (to be published)

Baulknight and Bortner, General Electric Corp. Report R64SD12 (1964).

34. Me

+

+ 0H~ - Me + OH (Me « Li. Na. Kt Cs)

This rate constant is estimated by comparison with Li+ + Cl ** Li + Cl and the rate constants^- suggested for the reactions

0

+

+ 0~ = 0 + 0 k * 5.5 x lO’V0 - 5

N

+

+ 0“ * N + 0 k * 8.4 x 10-V0 * 5
7-41

JENSEN- 1967

The estimate implies that the pre -exponential factor of the

reverse reaction rate constant is close to the collision frequency. [Unequal error limits given: 0.01 < k/k

Q

< 10.]

1. Baulknight and Bortner, General Electric Corp. Report

R64SD12 (1964).

35. 0 + e'+M=0“+M

OH + e“ + M = OH" + M

Cl + e~ + M = Cl" + M

This rate constant for each of these reactions is taken to

be the same as that for ©2 + e" + M - O 2

” + M. It is difficult

to justify this assumption, but equally difficult to suggest a better means of estimating k on the basis of present knowledge.

36. 0

2 + e + M = 0

2

+ M

The value of k given is based on measurements made at about

500 K by Pack and Phelps. These authors found that k increased

slightly with increasing temperature, which is perhaps contrary

to what one might expect. A temperature independent value has

been adopted for 1000 < T < 3500 K. The data on third-body relative efficiencies are meager; Pack and Phelps find that H 2O is

about four times as efficient as O 2 in this reaction. For a review

of attachment of electrons to O2 see McDaniel's book.

Pack and Phelps, Symp. Combust. 10th, p. 569 (1965).

Pack and Phelps, J. Chem. Phys. 44, 1870 (1966).

McDaniel, "Collision Phenomena in Ionized Gases" (Wiley and Sons

Inc., New York, 1964).

37. HCl + e = II 4- Cl

This rate constant was estimated by Calcote and Jensen on

the basis of collision cross-section data obtained by Buchel ’nikova.

Note, however, that recent results of Fehsenfeld, Ferguson, and

Schmeltekopf suggest that the reaction may be considerably faster.

[Unequal error limits given: 0.1 < k/k^ < 300.]

Calcote and Jensen, Advances in Chemistry Series 58, p. 291 (1966).

Buchel f nikova, J. Exp. Theoret. Phys. (USSR) 35, 1119 (1958).

Fehsenfeld, et al, J. Chem. Phys. 45, 1844 (1966).
I 7-42

JENSEN- 196

38. LiH

2

0

+

+ M - U

+

+ H

2

0 + M

This rate constant was estimated by Calcote and Jensen on

the basis of results obtained by Hayhurst and Hayhurst and

Sugden.

Calcote and JensAn, Advances in Chemistry Series 58, p. 291 (1966).

Hayhurst, Ph.D. Dissertation, University of Cambridge, 1964.

Hayhurst, Symp. Combust. 10th, p. 602 (1965) in general discussion of Schofield and Sugden, Symp. Combust. 10th, p. 589 (1965).

Hayhurst and Sugden, Proc. Roy. Soc. A293 t 36 (1966).

39. NaH

2

0

+

+ M * Na

+

+ H

2

0 + M

kh

2

o

+

+ m * k+

+ h

2

o + M

Estimated in a manner similar to that used by Calcote and

Jensen for LiH

2

0+ + M - Li+ + H

2

0 + M.

Calcote and Jensen, Advances in Chemistry Series 58, p. 291 (1966).

40. MeH

2

0

+

+ e" * Me + H

2

0 (Me = Li, Na, K)

This rate constant is estimated by comparison with the known

rate constant of H^O* +e"*H+H+0H. [Unequal error limits

given: 0.033 < k/k^ < 10.]

Calcote, et al, Symp. Combust. 10th, p. 605 (1965).

41. MeH

2

0

+

+ Cl" * Me + Cl + H

2

0 (Me * Li, Na, K)

MeH

2

0

+

+ OH" * Me + OH + H

2

0

Estimated by comparison with preliminary values for the rate

constants of the reactions

H^O"*” + OH = neutral products,

•I- - H^O + Cl * neutral products

measured by Kurzius and Calcote. [Unequal error limits given:

0.01 < k/k < 10.]

o Kurzius and Calcote, AeroChem Research Lab., Princeton, N. J.,

TP-92, DDC AD 351 824, July 1964. (Confidential)
7-43

JENSEN-1967

42. Cl + 0 + M " CIO 4 M

This rate constant is estimated by comparison with the

values for 0 + 0 + M * 0

2

+ M and Cl + Cl + M = Cl

2

+ M.[q.v.]

43. Me 4 CIO = Me Cl +0 (Me = Li. Na. K)

The pre -exponential factor is thought likely to be close

to the collision frequency. An arbitrary activation energy of

3000 cals/mol has been inserted as a result of comparison with

other bimolecular reactions. (Li + CIO = LiCl 4* 0 is 52 kcal/mol

exothermic) [Unequal error limits given: 0.01 < k/k

Q

< 10.]

44. CIO 4- H « HC1 4 0

Estimated by comparison with 0 4 H

? * OH 4- H and OH + Cl = HCl 4 0. [q.v.]

45. CIO 4 0 = Cl 4 0

2

This reaction is thought by Kaufman to be rapid at room

temperature, which would imply that the activation energy is

small. Arbitrarily, the activation energy has been set equal

to 3000 cals/mol . Comparison of this reaction with

OH + 0 =* 0 o 4 H would suggest a pre -exponential factor of about

2 x 10-U. 2

Kaufman, Progress in Reaction Kinetics, Vol. 1, p. 1 (1961).

46. CIO 4 OH « Cl 4- H0

2

The rate constant for the reverse reaction is estimated by

comparison with the rate constant of H + H0„ » OH 4* OK; both

these reactions proceed with essentially zero activation energy.

Note that the ratio of the mte constant for Cl 4- HO. = CIO 4* OH

to that for Cl 4- HO^ * HCl 4- 0

2

has been set equal to 3:1, which

is also the ratio or the rate constants of F 4- HO2

53 OH 4- OH or

H2O 4- 0 and H 4- HO2 = K2 4 O 2 according to Clyne and Thrush.

[Unequal error limits given: 0.01 < k/k^ < 2.]

Clyne and Thrush, Proc. Roy. Soc. A275. 559 (1963).
7-44

JENSEN-1967

47.

Li + 0

2 + M = Li0

2

+ M

K + 0

2 + M = K0

2

4' M

Set equal to the rate of Na + 0

2 + M = Na0

2

48.

Na + 0

2 + M = Na0

2 + M

This rate constant is estimated from the work of Kaskan and

Carabetta. who found values of k ranging from 6.0 x 10“3^ to

8.2 x 10 over the temperature range 1540 < T < 1730. This

work was done on clean H

2

/C0/air flames at 100 Torr.

Kaskan and Carabetta, "Kinetic Studies of Sodium in Flames" in

"Effect of Contaminants on Observables in Re-Entry", (General

Electric Corp., Final Report, Sept. 1965, AD 470984) p. 9.

49. Cl + Me0

2 = MeCl + 02

(Me = Li, Na, K)

Estimated by comparison with H + H0« = H_ + 0«. [Unequal

error limits given: 0.033 < k/k

Q

< 50.]

50. H

2

+ Me0

2 = MeOH + OH (Me = Li, Na, K)

Estimated by comparison with H

2 + H0

2 = H

2

0 + OH.

51. H0

2 + OH = H

2

0 + 0

2

OH + Me0

2 = MeOH + 0

2

(Me = Li, Na, K)

Cl + H0

2 = HC1 + 0

2

H0

2 + 0 = 0

2

+ OH

Estimated by comparison with H + HO2 = H2 + 0 . [Unequal

error limits given: 0.033 </kQ < 50 for the first three and

0.1 < k/k

Q

< 100 for H0

2 + 0 = 0

2 + OH.]

52. H + 0

2

+ M = H0

2 + M

This reaction has been quite widely studied. Getzinger and

Schott found k = 3.9 x 10” for M = Ar at 1500 K in a shock tube.

Clyne and Thrush, using a fast flow discharge system, found

k = 35 x 10~33 at 225 K, k = 30 x 10"33 at 244 K and k = 22 x 10'33

at 293 K for M = Ar. Baldwin gives values obtained from second

explosion limit studies; for M = Ar, k = 4.7 x 10“33 at 813 K, and
7-45

JENSEN-1967

for M = HU, k - 23 x 10 at 813 K. Kurzius found k = 30 x 10

^ at 800 K for M ~ H in his first explosion limit studies. The

value given for a ^general" third body thus seems fairly reliable.

Getzinger and Schott, J. Chem. Fftys. 43, 3237 (1965).

Clyne and Thrush, Proc. Roy. Soc. A275 , 559 (1963).

Baldwin, Symp. Combust. 9th, p. 218 (1963).

Kurzius, Ph.D. Dissertation, Princeton University, 1964. AD 635 159.

53 . H + H0

2 = OH -f OH

This rate constant was estimated by Dixon-Lewis and Williams

to be 1.1 x 10" 10 at 500 K, on the basis of data from several

sources. One might note that the species H and HO^ are thought to

produce H^O and 0 at a small proportion of collisions.

Dixon-Lewis and Williams, Nature 196, 1309 (1962).

54. H + H0

2 * H

2

+ C

; This rate constant is estimated by comparison with H + HO = OH + OH; Clyne and Thrush obtained a value of 3 ± 1 for the ratio

of the rate of chain propagation to the rate of chain breaking in

the reaction between H and HO,.

Clyne and Thrush, Proc. Roy. Soc, A275, 559 (1963).

55. H

2

+ H0

2 * H

2Q + OH (overall)

The rate constant of the reaction between H2 and HO2 was

estimated by Dixon-Lewis and Williams*- to be 2.2 x 10“*-® at 500 K.

These authors made use of data from several sources. This esti- ) mate is some 50 times greater than that made earlier by Voevodsky

and Tal'rose,^ who suggested k - 2 x 10 ~*-®e“ 24000 /RT # ft

important to note that the reaction is thought"' to lead to

H2Q2 + H rather than to H2O + OH, as written above. We have

elected to eliminate from our programs as a result of its

relative unimportance as a reaction intermediate in hightemperature environments. The overall reaction, as written here,

is satisfactory for the purposes of our programs.

1. Dixon-Lewis and Williams, Nature 196, 1309 (1962).

2. Voevodsky and Tal rose, Zh. Fiz. Khim. 22 , 1192 (1948).
7-46

JENSEN-1967

56. CO + H0

2 - C02

+ OH

Estimated by comparison with CO + OH = C02 + H and

H2 + HO2

** H2O + OH. Reaction of CO With HO2 is thought by

Baldwin, Jackson, Walker and Webster to be important at temperatures as low as 500°C, which in itself argues against an

activation energy much higher than 10,000 cals/mol • Baldwin, et al, Symp. Combust. 10th, p. 423 (1965).

57. CHO + 0 « CO + OH C10H + H = CIO + H

f ^ CHO + OH * CO + H

2

0 C10H + OH * CIO + H

2

6

CHO + H * CO + H

2

ClOH + 0 * CIO + OH

No quantitative data are available for these reactions.

The rate constant given for CHO + OH * 00 + H

20 was estimated by

comparison with CO + OH - CO^ + H, OH + H0

2 * H20 + 0 [which was

estimated by comparison with H + H02 02

] and the rate constant

for the reaction CHO + H20 =* CH20 + OH. r Avramenko and Lorentso^-

cited here and by Fristrom and Westenberg^ for the reverse reaction.

Probably reference 3 is intended. Trotman-Dickenson and Milne^

give 1 x 10^exp(-900/RT) from reference 3 and 5 x 10^exp(-13000/RT)

from reference 5, both for the reverse reaction.]

The others were estimated in a similar manner. [Unequal

error limits given for CHO + OH and CHO + H, 0.01 < k/k

Q

< 30.]

1. Avramenko and Lorentso, Doklady Akad. Nauk SSSR 67. 867 (1949).

2. Fristrom and Westenberg, "Flame Structure" (McGraw-Hill Book

Co., New York, 1965).

3. Ayramenko and Lorentso, Doklady Akad. Nauk SSSR 6£, 205 (1949).

4. Trotman-Dickenson and Milne, NSRDS-NBS 9, U.S. Dept. Commerce,

Natl. Bur. Stands • (1967)

,5. Westenberg and Fristrom, Symp. Combust. 10th, p. 473 (1965).
7-47

JENSEN-1967

5 8 . CO + H + M « CEO 4 M

No quantitative data are available for this reaction. The

rate constant given is estimated by comparison with H + OR + M s

H2O + M and CO + 0 + M * CO 2 + M. [Unequal error limits given:

0.033 < k/k <10.]

o

59. CH

4 + OH - CO 4 H

2

0 (overall)

This "rate constant” is based upon the recommendation of

Wilson and Westenberg for the rate constant of the reaction

between CH^ and OH and on the arguments presented by Pergaiient

and Calcote for the use of an artificial overall reaction for

the oxidation of methane.

Wilson and Westenberg, Symp. Combust. 11th, p. 1143 (1967).

Pergament and Calcote, Symp. Combust, 11th, p. 597 (1967).

60. CH, + OH = H-O^ + e" + C0 o (overall)

4 3 2

The artificial overall "rate constant" was estimated by

Pergament and Calcote.

Pergament and Calcote, Symp. Combust. 11th, p. 597 (1967).

6

• CH + 0 « CHO* * e The value given for k is a compromise between theoretical

values of 3 x 10"^' and 1 x 10“H reported by Green and Sugden

and by Calcote, respectively.

Green and Sugden, Symp. Combust. 9th, p. 607 (1963).

Calcote, AeroChem Research Lab., Princeton, N. J., TP-119 (1965).

62. CHO"

1 + H.O * CO + H,0

+

l

'Ihis rate constant is based on arguments put forward by

Calcote

Calcote, AeroChem Research Lab., Princeton, N.J,, TP-119 (1965).
1 7-48

JENSEN-1967

63. H

3

0

+

+ Me = H + H

2

0 + Me

+

(Me - Li, K, Cs)

These rate constants estimated by comparison with + Na *

Na+ + H

2

0 + H.

64. H

3

0

+

+ Na = H + H

2

0 + Na

+

Hayhurst and Telford measured this rate constant in the range

1800 < T < 2500 K. They observed little significant dependence of

k on temperature.

Hayhurst and Telford, Nature 212. 813 (1966).

65. H

3

0

+

+ e" * H + H + OH

This rate constant has been measured by several workers; the

most up-to-date value is given by Calcote, Kurzius and Miller.

Calcote, et al, Symp. Combust. 10th, p. 605 (1965).

66. Cl" + H

3

0

+

* H + HC1 + OH

H

3

0

+

+ OH' = H + H

2

0 + OH

These preliminary values were measured by Kurzius and

Calcote.

Kurzius and Calcote, AeroChem Research Lab., Princeton, N. J.,

TP-92, DDC AD 351 824, July 1964. (Confidential)

Cl + OH + M C10H + M

Estimated by comparison with 0 + Cl + M =* CIO + M [which

was estimated by comparison with 0 + 0 + M a 0«+M and

Cl + Cl + M - Cl

2 + M.] 2

67 .
7-49

JOHNSTON-1968

JOHNSTON, H. S., "Gas Phase Reaction Kinetics of Neutral Oxygen Species",

NSRDS-NBS Monograph Series (in press, 1968).

This review examines the available experimental data on reactions

among 0, 0£ and O3

: atom transfer (including exchange), combination

and dissociation. For the latter two types the effect of various third

bodies is considered. Recommended values of rate coefficients are given.

These are based on a reanalysi.s of the individual data points reported

in the papers considered. Reports giving only rate coefficient expressions are excluded from the analysis. The data used are tabulated, and

displayed in extenso in figures.

The notes are limited to simple descriptions of the approach and

citation of references. They do not adequately display the scope of

the monograph.

1

.

o

2

+m*o + o+ m

See Reaction Summary.

2. 0

3 + M * 0 + 0

2 + M

° + °

3 « °

2 + °2

See Reaction Summary for 0^ + M » 0 + 0^ + M.

3. 0 4* Og “ 0 + 0^ (Exchange)

18 Oxygen atom exchange, using 0 as a tracer, has been studied

only near room temperature. The recommended value is for 273°K. Data

used were taken from the following sources.

1. Brennen and Niki, J. Chem, Phys. 42, 3725 (1965).

2. Herron and Klein, J. Chem. Phys. 40, 2731 (1964).

3. Jaffa and Klein, Trans. Faraday Soc. j|2, 3135 (1966).

4. Ogg and Sutphen, J. Chem. Phys. 21, 2078 (1953).

5. Ogg and Sutphen, Disc. Faraday Soc. 17, 47 (1954).
7-50

I KASKAN-1964

KASKAN, W. E. and BROWNE, W. G., "Kinetics of the H

2 /C0/02 System",

General Electric Company Space Sciences Laboratory Report

R64SD37, July 1964.

Introduction

This report is an evaluation of rates of elementary reactions of

importance in the H-4), C-0 and H-C-0 combustion systems. It is widely

quoted. It is an example of well organized treatment of rate data on

a reaction by reaction basis.

The experimental results are listed in each discussion and the

data are graphed for most reactions. The forward and reverse reactions

are considered together. The estimate for one direction is made then

equilibrium data are used to set the rate for the reverse.

Twenty -one reactions (counting forward and reverse as one) are

considered. Recommended values are given for eleven of these. The

others discussed are:

OH + 0E « H

2 + 0

2

0 + OH + M * H0

2

4- M

OH + OH + M - H

2

0

2 + M

CO + 0 * co

2

CO + 0 + M * C0„

h

2 + 0

2 - h2

0 + 0

OH + OH * products

H + °

3 * °2 + °H

0 + 0

3 = 0

2 + 02

CO + 0 = C0

2 + hv

The discussion of reactions involving the H0

2

radical and that for CO + 0

combination are especially extensive and informative.

1.

H

2 + OH « H + H

2

0

See Reaction Summary.

2.

H + 0

2 » 0 + OH

See Reaction Summary.

3.

H

2

+ 0 =» H + OH

See Reaction Summary
7-51

KAS KAN- 1964

4. H

2

0 + 0 * OH + OH

See Reaction Summary for OH + OH = H^O + 0.

5.

H+H + M=H

2

+M

H + OH + M * H

2

0 + M

The analyses of these two reactions are interrelated. While

the combination of H atoms has been studied separately, the combination of H and OH has been studied only under conditions where

H-H combination occurs.

The rates for the combination of H atoms and dissociation of

H2 are based on room temperature combination data, ^ high temperature shock tube studies of the dissociation, 2*5 and flame studies. ^-8

See also Reaction Summary for H

2 + M = H + H + M.

The rate for the H + OH combination (water dissociation rates

have not been studied) is based on flame studies. Early direct

studies using radicals produced- from discharged water vapor^ have

been criticized^-*- and are not used. The interpretation of flame

data is discussed in detail. The temperature dependence adopted

is from Ref. 7. The value for M = H

2

0 is recommended only for

mixtures containing about 20% H

2

0.

Data and recommendations for both systems are graphed.

1. Marshall, Phys . Fluids _5, 743 (1962).

2. Chesick and Kistiakowsky, J. Chem. Phys. 23, 956 (1958).

3. Rink, J. Chem. Phys. 36, 262 (1962).

4. Patch, J. Chem. Phys. 36, 1919 (1962).

5. Sutton, J. Chem. Phys. 36, 2923 (1962).

6. Kaskan, Combustion and Flame 2^ 229 (1958).

7. Bulewicz and Sugden, Trans. Faraday Soc. 54, 1855 (1958).

8. Dixon-Lewis, et al. Disc. Faraday Soc. 33, 205 (1962).

9. Bulewicz, et al, Proc. Roy. Soc. A235, 89 (1956).

10. Oldenberg and Rieke, J. Chem. Phys. 7_, 485 (1939).

11. Kaufman and Del Greco, Symp. Combust. 9th, p. 659 (1963).
7-52

KASKAN-1964

6.

H + 0 + M=0H+M

No data found, forward reaction rate estimated as an average

of the rates for H + H + M=H2 +M and 0 + 0 + M=02+M. Reverse

reaction rate calculated using equilibrium data.

7. 0

2

+ M= 0 + 0 + M

See Reaction Summary.

8. 0 + 0

2

+ M * 0

3 + M

See Reaction Summary for 0^ 4- M - 0 + 0

^ + M.

9. H + 0

2 + M * H02 + M

This reaction is discussed in extenso along with 0 + OH + M - H0« + M,

OH + OH * products, and OH + OH + M = H^ + M all of which are

interrelated in flames.

1 2

Apart from flame data, 9 the results considered for H + 0

2 combination are from direct studies at room temperature and

explosion limit experiments. ”” The value given for the combination is an estimate, and may be a weighted average of H + 0„ + M =

H0

2 + M and 0 + OH + M H0

2 + M. Recent data are graphed.

1. Kaskan, Combustion and Flame 2_, 286 (1958).

2. Dixon-Lewis and Williams, Symp. Combust. 9th, p. 576 (1963).

3. Baldwin and Walsh, Disc. Faraday Soc. 17. 96 (1954).

4. Hoare and Walsh, Trans. Faraday Soc. 53, 1102 (1957).

5. Clyne, Symp. Combust. 9th, p. 211 (1963).

6. Voevodsky and Kondratiev, ’’Progress in Reaction Kinetics”,

Vol . 1 (1961), p. 41.

10. CO + OH = C0

2 + H

See Reaction Summary
7-53

MAYER- 1968

MAYER, S. W. and SCHIELER, L., "Computed Activation Energies and

Rate Constants for Forward and Reverse Transfers of

Hydrogen Atoms", J. Phys • Chem. 72. 236 (1968). Also

appeared in Chemical Propulsion Information Agency

publication No. 146, Vol. I, p. 121, (1967).

Activation energies were computed for 324 gas phase hydrogen-atom

transfers

X + YH - XH + Y

where X and Y each run through all members of the set: Al, B, Be, Br,

C, Cl, F, H, I, K, Li, Mg, N, Na, 0, P, S, and Si.

The 324 reactions include the 18 exchange reactions (X = Y) and

both the exothermic and endothermic reactions for X 4 Y.

A modification of the Johnston and Parr method that considers the

temperature region in which the activated complex can be expected to

obey small vibration theory was used to calculate rate constants for

234 reactions at temperatures from 298 to 2500°K. The criterion used

for applicability of this method is that the average vibrational amplitude of the activated complex be less than (2tt) 0*® a t 1000°K. Rate

parameters for these reactions were calculated by fitting the rate

constants to k = AT® exp(-E/RT). These values are marked J + P in this

compendium. See general notes under this heading.

Rate parameters for the other 9P reactions were calculated using

a collision theory treatment for A, B = 0.5 and the bond energy -bond

order method for E. These are marked BEBO in this compendium. See

general notes.

For H^, + 0 = H 4* OH also see the Reaction Summary.

Comparisons with experimental data are presented for five cases.

Some values in this paper apply to reactions for which the authors

have previously reported similar calculations . 1* ® Those reported here

supersede the earlier ones.®

1. Mayer, et al, J. Chem. Phys. 45. 385 (1966).

2. Tunder, et al. Aerospace Corp. Rpt. No. TR-1001(9210-02) -1 (1967).

3. Private communication, L« Schieler (March 26, 1968).
7-54

SCHOFIELD -19 6 7

SCHOFIELD, K., "An Evaluation of Kinetic Rate Data for Reactions of

Neutrals of Atmospheric Interest", Planet# Space

Sci. 15, 643 (1967). +

Introduction

This is a tabulation and analysis of bimblecular and termolecular

rate coefficients for reactions involving H2 ,

C> 2 , N , H2O, H, 0, N, OH,

HO , 0 , the oxides of nitrogen, CO, CO2 , SO2 low molecular weight

hydrocarbons, aldehydes, alkyl and hlkoxy radicals.

It is an important paper for modern rate coefficient evaluation.

Approximately 100 reaction systems are included, with rates given for

both directions (where data are available). Rate coefficient expressions are tabulated for each source, data are recalculated when necessary to allow for revisions in thermodynamic and rate data. The tables

indicate the possible presence of excited products, the temperature

range for each expression, an identification of method and Schofield’s

remarks on the results.

Plots of the rate data for eleven reactions are included. These

show the analyses to be based on data points, as opposed to rate

expressions. Least squares fits are used to develop best values based

on selected data.

The paper covers the published literature up to October 1966 and

lists 280 references.

This compendium lists only a fraction of the material in the paper.

All those rates designated as "recommended values" are included here.

In addition there are listed those cases where a data fit is reported,

the available data are shown in a graph, or a reverse rate is calculated

from a recommended value although not marked recommended. These items

are identified in the notes.

The notes written for this compendium record references, experimental methods, some of the author's remarks and the method used for

setting the recommended value of the rate coefficient.

1. H + H^ - H + H^ (exchange) and the Deuterium Reactions

Experimental data (low temperature) ^-8 are combined with

potential energy surface calculations^* 5 in least squares fits.

The apparently reliable experimental values reported^* 6, 8 recently

Activation energies quoted from this paper are in cal mol

R = 1.987 cal mol“^K“^
7-55

SCHOFIELD -1967

cover only a small temperature range. Consequently an uncertainty

of the order of a factor of two still exists for these rates. The

data and recommended values are presented both in tabular and

graphical form.

Recommended values for more limited temperature ranges are:

H + p-H

2 = o-H

2 + H

log

10

k = -8.326 - 3490/T + 3.836 x 10

5

/T

2

for 300 <T< 444 K (Ref. 1)

D + H

? = H + OH

log.

[()k = -7.539 - 3753/T + 4.154 x 10

5

/T

2

for 274 <T< 468 K (Ref. 6)

H + D

2 = D + HD

k = 7.2 x

10~ 12 exp(-7300/RT) for 368 <T< 468 K (Ref. 8)

1. Schulz and LeRoy, J. Chem. Phys . 42, 3869 (1965).

2. Weston, J. Chem. Phys. 31, 892 (1959).

3. Rapp and Weston, J. Chem. Phys. 36, 2807 (1962).

4. Karplus, et al, J. Chem. Phys. 40, 2033 (1964); 43

,

3259 (1965).

5. Shavitt, J. Chem. Phys. 31, 1359 (1959).

6. Ridley, et al, J. Chem. Phys. 44, 3344 (1966).

7a. Boato, et al, J. Chem. Phys. 24, 783 (1956).

7b. Cimino, et al, J. Chem. Phys. 33

,

616 (1960).

8. Schulz and LeRoy, Can. J. Chem. 42, 2480 (1964).

2. H + 0

2 = 0 + OH

See Reaction Summary.

3. H

2

+ 0 = H + OH

See Reaction Summary.

4. H

2 + OH = H + H

2

0

See Reaction Summary for H + H

2

0 = H0

4- OH.

5. OH + OH = H.

? 0 + 0

See Reaction Summary
7-56

SCHOFIELD-1967 6.

H + N

2

0 = N

2 + OH

Mean value of rates reported in atmospheric pressure flame

studies^ ^ an<i (recalculated) low pressure flame data.^ The

recommended rate, based on 900-1780 K measurements has a value six

times that measured in flow experiments^ when extrapolated down

to their temperature (423 K)

1. Dixon-Lewis, et al, Symp. Combust. 10th, p. 495 (1965).

2. Dixon-Lewis, et al, J. Chem. Soc. 5724 (1965).

3. Fenimore and Jories, J. Phys . Chem. 63. 1154 (1959).

4. Schiavello and Volpi, J. Chem. Phys. 37j 1510 (1962).

7. N

90 + 0 * NO + NO

h — —

1 2 This is the best fit to low pressure flame data, > shock

tube luminescence studies^ and equilibrium measurements on NO

decomposition.4, 5 [Not listed as a recommended value by the

author.] Other data tabulated: references 6,7.

1. Fenimore and Jones, J. Phys. Chem. 62, 178 (1958).

2. Fenimore and Jones, Symp. Combust. 8th, p. 127 (1962).

3. Fishbume and Edse, J.Chem. Phys. 44, 515 (1966).

4. Kaufman and Kelso, J. Chem. Phys. 23. 1702 (1955).

5. Kaufman and Decker, Symp. Combust. 7th, p. 57 (1959).

6. Kaufman, et al, J. Chem. Phys. 25. 106 (1956).

7. Bradley and Kistiakowsky, J. Chem. Phys. 35, 256 (1961).

8. H + N0

2 = NO + OH j Based on flow reactor-*- (mass spectrometry analysis) and

static^ (pressure analysis) studies, the rate for the latter being

recalculated. Another static measurement^ is listed, but the rate

(10 times the collision frequency) is rejected.

1. Phillips and Schiff, J. Chem. Phys. 37, 1233 (1962).

2. Ashmore and Tyler, Trans. Faraday Soc. 58, 1108 (1962).

3. Rosser and Wise, J. Phys. Chem. 65, 532 (1961).
7 ^7 / J /

SCHOFIELD -1967

9. N0

2

+ 0 = NO + 0

9 Rate determined in a flow reactor study" (mass spectrometric

analysis) adopted. Other results tabulated: references 2,3 the

former being recalculated.

1. Klein and Herron, J. Chem. Phys • 41, 1285 (1964); 44, 3645 (1966).

2. Ford and Endow, J. Chem. Phys. 27, 1156 (1957).

3. Phillips and Schiff, J. Chem. Phys. 36, 1509 (1962] .

10. NO + 0 = N + 0

2

See Reaction Summary for N + 0^ = NO + 0.

12. H + HNO = H

? + NO

Atmospheric pressure flame (1600-2000 K) ^ and flow reactor

(226 K)^ data, both using spectrometric analysis were combined in

this estimate.

1. Bulewicz and Sugden, Proc. Roy. Soc. A277 , 143 (1964).

2. Clyne and Thrush, Disc. Faraday Soc. 33139 (1962).

13. N0

2

+ N0

2 = NO + NO + 0

2

Least squares fit to rates determined from thermal (static)

measurements, ^ - shock tube studies (1400-2300 K)^>4 an(j from NO

oxidation rates'^ plus the equilibrium constant. Scatter of

points is small. Activation energy, 28,630 cal/mol ,

?i a little

too large", i.e. 500 to 1000 cal/mol more than the endc the rmi city

of the reaction. [Not listed as a recommended value.]

1. Rosser and Wise, J. Chem. Phys. 24

,

493 (1956).

2. Ashmore and Burnett, Trans. Faraday Soc. 58, 253 (1962).

3. Huffman and Davidson, J. Am. Chem. Soc. 81, 2311 (1959),

4. Fishbume, et al, J. Chem. Phys. 43 1847 (1965).

5. Glasson and Tuesday, J. Am. Chem. Soc. 85 2901 (1963).

6. Bufalini and Stephens, Intern, J. Air Water Pollution 9, 123 (1965).

7. Greig and Hall, Trans. Faraday Soc. 62

652 (1966).

8. Hall and Greig, Chem. Coram. 326 (1966),

9. Ashmore, et al, Trans. Faraday Soc. 58, 685 (1962).
7-58

SCHOFIELD-1967

14, H + °

3 " °

2

+ OH

Flow reactor (titration and mass spectrometric analysis)

value ^ was selected. Data from ref. 2 also listed.

1. Phillips and Schiff, J. Chem. Phys. 37, 1233 (1962).

2. Garvin and McKinley, J. Chem. Phys. 24, 1256 (1956).

15. N + 0

3 - NO + 0

2

Flow reactor (mass spectrometric analysis) value^ selected.

Data from ref. 2 listed, but considered questionable.

1. Phillips and Schiff, J. Chem. Phys. 36, 1509 (1962).

2, Chen and Taylor, J. Chem. Phys. 34, 1344 (1961).

16. NO + 0

3 = N02 (

2

A) + 0

2

1-3

Two values, developed from experiments using flow reactors

’’stopped flow”, photolysis^ and supersonic nozzles.**

-12

The value k * 2.8 x 10 exp(-2820/RT) is a least squares fit

to all these data. The value k * 1.7 x 10“12eXp(_2620/RT) excludes

ref. 5.

1. Phillips and Schiff, J. Chem. Phys. 36, 1509 (1962).

2. Clyne, et al, Trans. Faraday Soc. 60, 359 (1964).

3 . Clough and Thrush, Chem. Comm. 783 (1966)

4. Johnston and Crosby, J. Chem. Phys. 19, 799 (1951); 22, 689 (1954).

5. Ford, et al, Adv. Chem. Series 21, 410 (1959); J. Chem. Phys.

26, 1337 (1957).

6. Marte, et al, J. Chem. Phys. 39, 3277 (1963).

< f

17. CH

4 + H = CH3 + H2

= j. 2 3 4 5

Least squares fit to flame, 9 photolysis, 9 flow reactor

and explosion limit data. 6; ? Results from references 1 and 4

recalculated. Data presented both in tabular and graphical form.
7-59

SCHOFIELD -196

1. Fenimore and Jones, J. Pbys . Chem. 65, 2200 (1961),

2. Dixon-Lewis and Williams, Symp. Combust. 11th, p. 951 (1966),

3. Majury and Steacie, Disc. Faraday Soc. 14, 45 (1953).

4. Klein , et al, J. Chem. Phys . 30, 58 (1959).

5. Jamieson and Brown, Can. J. Chem. 42

,

1638 (1964).

6. Gorban and Nalbandyan, Russ. J. Phys. Chem. 36, 946 (1962).

7. Azatyan, et al. Kinetics and Catalysis USSR 5, 177 (1964).

18. C

?H

6 + H = C

2

H

5 + H2

^ 2

Least squares fit to flame, photolysis and explosion limit

data.^^,7,8 Results of references 2 and 3 recalculated. Flow

reactor (probe detection) results^ rejected per discussions in

references 6 and 8. ’’Quite well defined fit.’’

1. Fenimore and Jones, Symp. Combust. 9th, p. 597 (1963).

2. Darwent and Roberts, Disc. Faraday Soc. 14

,

55 (1953).

3. Baldwin, et al, Symp. Combust. 10th, p. 423 (1965).

4. Gorban and Nalbandyan, Russ. J. Phys. Chem. 36, 946 (1962).

5. Berlie and LeRoy, Disc. Faraday See, 14

,

50 (1953).

6. Schulz and LeRoy, Can. J. Chem. 40, 2413 (1962).

7. Baldwin, Symp. Combust. 9th, p. 604 (1963).

8. Voevodskii and Kondrat’ev, Progress in Reaction Kinetics,

Vol . 1, p. 41 (1961).

19. C

3

H

g

+ H = C

3

H

? + H 0 18 2

Least squares fit to flame, , photolysis" (recalculated),

flow (probe detection)^ and explosion limit data.

1

^’ 7 "Well defined

fit."

1. Fri strom, et al. Rev. Inst. Fr. Petrole L3, 544 (1958).

2. Darwent and Roberts, Disc. Faraday Soc. 14, 55 (1953).

3. Kazmi, et al. Can. J. Chem. 41. 690 (1963),

4. Gorban and Nalbandyan, Russ. J. Phys. Chem. 36, 946 (1962).

5. Voevodskii and Kondrat’ev, Progress in Reaction Kinetics,

Vol. 1, p. 41 (1961).
7

- 6 )

SCHOFIELD-1967

6. Baldwin, et al, Symp. Combust, 10th, p. 423 (1964).

7. Baldwin, Trans. Faraday Soc. 60, 527 (1964).

8. Fristrom and We stenberg," Flame Structure,” p. 366 j 1965.

20. n-C. H- _ + H - n-C. H + H.

4 10 4 9 2

Least squares fit to photolysis^- (recalculated), explosion

limit^J^ and flow (probe detection plus gas chromatography)^

results. "Confirmatory data required."

1. Darwent and Roberts, Disc. Fataday S6c. 14. 55 (1953).

2. Baldwin, et al, Symp. Combust. 10th, p. 423 (1965).

3. Baldwin and Walker, Trans. Faraday Soc. 60. 1236 (1964).

4. Kazmi and LeRoy, Can. J. Chem. 42. 1145 (1964).

21. iso-C. H_ 0 + H = iso-C, HQ + H0 4 10 4 9 2

Least squares fit to photolysis^- (recalculated), and explosion limit data?**^ "More data required outside 600-900 K range."

1. Darwent and Roberts, Disc. Faraday Soc. 14. 55 (1953).

2. Baldwin, et al, Symp. Combust. 10th, p. 423 (1965).

3. Gorban and Nalbandyan, Russ. J. Phys . Chem. 36. 946 (1962).

4. Voevodskii and Kondrat'ev, Progress in Reaction Kinetics,

Vol. 1, p. 41 (1961).

5. Baldwin and Walker, Trans. Faraday Soc. 60. 1236 (1954).

22. C

2

H

4 + H » C2

H

3 + H2

Based on explosion limit data^

- taking E = 6900. (Reasonable

agreement with data of references 2,3.)

1. Baldwin, et al, Trans. Faraday Soc. 62, 2476, 2486 (1966).

2. Voevodskii and Kondrat'ev, Progress in Reaction Kinetics, Vol.

1, p. 41 (1961).

3. Azatyan, et al, Proc. Acad. Sci. USSR Phys. Chem. Sec. 149.

312 (1963).
7-61

SCHOFIELD -196

23 . C

2

H

4 + H = C

2

H

5

*

Least squares fit to photolysis,"’ radiolysis (recalculated)

explosion limit and flow reactor experiments.- Photolysis results

(reference 6) not used. "Reasonable agreement between data.”

1. Allen, et al, Proc. Roy. Soc. A218, 311 (1953).

2. Jennings and Cvetanovic, J. Chem. Phys . 35, 1233 (1961).

3. Yang, J. Am. Chem. Soc. 84

,

719 (1962).

4. Baldwin, et al, Trans. Faraday Soc. 62, 2476, 2486 (1966).

5. Brown, et al, Chem. Comm. 843 (1966).

6. Darwent and Roberts, Disc. Faraday Soc. 14

,

55 (1953).

24. CH. + OH = CH + HO

4 3 2

Flow^, thermal^j^ and flame-* data combined in a least square

fit. Data from reference 2 recalculated. Results presented in

tabular and graphical form. Flow experiments in which water was

passed through an electric discharge to form OH, ^ were rejected.

1. Wilson and Westenberg, Symp. Combust. 11th, p. 1143 (1966).

2. Blundell, et al, Symp. Combust. 10th, p. 445 (1965).

3. Hoare, Nature 194, 293 (1962); Proc. Roy. Soc. A291, 73 (1966).

4. Hoare and Peacock, Proc. Roy. Soc. A291 , 85 (1966).

5. Fenimore and Jones, J. Phys. Chem. 65 , 2200 (1961).

6. Westenberg and Fristrom, J. Phys. Chem. 65

591 (1961).

7. Fristrom, Symp. Combust. 9th, p. 560 (1963).

8. Dixon-Lewis and Williams, Symp. Combust. 11th, p. 951 (1966).

9. Avramenko and Kolesnikova, Advances in Photochemistry, Vol. 2

p. 25 (1964).
7-62

SCHOFIELD-1967

25. CH. + 0 = CH. + OH

4 3 too, / Stirred reactor 1 flow, low pressure flame4 and explosion

limit data^ combined in a least squares fit. Results given in

tabular and graphical form.

1. Wong and Potter, J. Chem. Phys. 39. 2211 (1963); 43, 3371 (1965).

2. Avramenko, et al. Bull. Acad. Sci. USSR Div. Chem. Sci. 557 (1963).

3. Cadle and Allen, J. Phys. Chem. 69. 1611 (1965).

4. Fenimore and Jones, J. Phys. Chem. 65, 2200 (1961).

5. Azatyan, et al. Kinetics and Catalysis 5, 177 (1964) .

26. C«H^ + 0 * C0H_ + OH

2 b 2 5

1 2

Least squares fit to explosion limit, flow reactor and

photolysis data.^ "Reasonable agreement between data but more

needed."

1. Azatyan, et al, Proc. Acad. Sci. USSR Chem. Sect. 147. 973 (1962).

2. Avramenko, et al, Bull. Acad. Sci. USSR Div. Chem. Sci. 557 (1963).

3. Saunders and Heicklen, J. Phys. Chem. 70, 1950 (1966).

27. CH

3

CH0 + 0 = CH

3

C0 + OH

Value selected is that of R. D. Cadle and J. W. Powers

(private communication). Method used: flow reactor with oxygen

atoms produced in an electric discharge and gas chromatographic

analysis of trapped products.

28. CO + OH = C0

2 + H

See Reaction Summary.

o + o

2 + m=o3

+m

See Reaction Summary for 0

3 + M 3 0 + 0^ + M.

29 .
7-63

SCHOFIELD-1967

30. H + 0

2

+ M * HO

? + M

1 2 3-7

Least squares fit to flow reactor, ’ explosion limit

and shock tube data.^ Data from references 4 and 5 recalculated. Flame data of reference 9 not used. Results presented graphically and in tabular form. Both the Arrhenius

equation and the k = AT~en f crm are presented (and are included

in this compendium). [Not listed as recommended values.]

1. Clyne and Thrush, Proc. Roy. Soc. A275, 359 (1963).

2. Larkin and Thrush, Disc. Faraday Soc. 37. 112 (1964).

3. Ashmore and Tyler, Trans. Faraday Soc. 58, 1108 (1962).

4. Webster and Walsh, Symp. Combust. 10th, p. 463 (1965).

5. Baldwin, et al, Trans. Faraday Soc. 56

,

93 (1960).

6. Baldwin and Brooks, Trans . Faraday Soc. 58, 1782 (1962).

7. Lewis and Von Elbe, Combustion, Flames and Explosions of

Gases, p. 29 (Academic Press, N» Y., 1961).

8. Getzinger and Schott, J. Chem. Phys . 43, 3237 (1965).

9. Fenimore and Jones, Symp. Combust. 10th, p. 489 (1965).

31. N + N + M~N

2

+M

This is a mean value for 300 K based on flow and static

experiments in which the nitrogen afterglow-^-"' was monitored,

atom concentrations were measured by ti tration-^ 3 -8 eSR^ , probes and Wrede gauges .

When combined with shock tube

measurements at 6400 K, this room temperature value suggests

a T~^*

7

dependence.

1. Harteck, et al, J. Chem. Phys. 29, 608 (1958).

2. Wentink, et al, J. Chem. Phys. 29, 231 (1958).

3. Kretschmer and Petersen, J. Chem. Phys. 39, 1772 (1963).

4. Barth, Ann. Geophys. 20, 182 (1964).

5. Campbell and Thrush, Chem. Comnu 250 (1965).

6. Herron, et al, J. Chem. Phys, 3jQ , 879 (1959).

7. Mavroyannis and Winkler, Can. J. Chem, 39. 1601 (1961).

8. Avramenko and Krasenen ’ kov. Bull. Acad. Sci. USSR Div. Chem.

Sci • 1095 (1963).
7-64

SCHOFIELD-1967

9.

Evenson and Burch, *1’. Chem. Phys. 45, 2450 (1966).

10. Allen, et al, Phys. Fluids 5^ 284 (1962).

11. Byron, J. Chem. Phys. 44, 1378 (1966).

32. NO + 0 + M - N0

2

+ M (M -

This value, with an apparent negative activation energy

(-1930 cal/mol ) is that determined by Klein and Herron^- in a

flow system, using discharge production of atoms and mass

spectrometric analysis. Other data tabulated: references 2-8.

1. Klein and Herron, J. Chem. Phys. 41, 1285 (1964); 44, 3645

(1966).

2. Ford and Endow, J. Chem. Phys. 27, 1156 (1957).

3. Clyne and Thrush, Proc. Roy. Soc. A269, 404 (1962).

4. Clyne, et al, Trans. Faraday Soc. 61, 2701 (1965).

5. Ogryzlo and Schiff, Can. J. Chem. 37^ 1690 (1959).

6 0 Westenberg and De Haas, J. Chem. Phys. 40, 3087 (1964).

7. Harteck, et al, J. Chem. Phys. 29, 1333 (1958).

8. Kaufman and Kelso, Symp. Chemiluminescence, p. 65 (1965).
7-65

TUNDER-1967

TUNDER, R., MAYER, S., COOK, E., and SCHIELEk, L., "Compilation of

Reaction Rate Data for Nonequi librium Performance and Reentry

Calculation Programs", Aerospace Corp., Thermochemistry Research Dept., Aerospace Report No. TR-1001(9210-02) -1 (1967).^

Introduction

This report lists rate parameters for over 1000 reactions of atoms

and small molecules. The molecules are compounds (or ions) of the following elements: Al, Ee, B, C, Li, N, K, Na, Cl, F, 0 and H. The report

is arranged in 13 tables, the first containing reactions of Al and its

compounds with all others, the second is for Be and its compounds and

all other species except those of Al. Succeeding tables follow this rule,

the last containing only reactions of H, H+, H", with each other.

Many of the reactions listed have never been studied experimentally.

Order of magnitude estimates are given for many of these. Such estimates

are keyed to the "General Notes" section by the code OME, and are not

keyed to a specific note in the list below. The next largest class of

rates in this report are those calculated by the Johnston and Parr linear

transition state, bond energy --bond order method. These are keyed to the

"General Notes" section by J+I or BEBO depending upon whether the full

method was used or only the activation energy was estimated by this

technique

In the text of the report those items now identified by OME were

identified by notes 2, 21 and 36 and were explained in its introduction.

The items keyed J+P or BEBO were keyed to their note 22.

Schieler has indicated'*' that the group at Aerospace consider that

the "order of magnitude estimate" represents a particularly antiquated

state-of-the-art. This type of estimate was made by them before they

decided to explore the possibilities for computing rate constants. Their

later work emphasizes the calculational approach, the details of which

continue to be developed. 3,4^ tes reported in the later papers are to

be preferred, calculated rates are to replace estimates ones. At least

in principle large parts of the compilation (TR-1001(9210-02) -1) have

been superseded.

In keeping with this view we have deleted estimated rates that have

also been calculated by them. The newer values are listed in the main

table and are taken from reference 2.

1. Letter to D. Garvin, 28 March 1968.

2. Mayer, S. W. and Schieler, L., T. Phys . Chem. 72, 236 (1968)

(which is quoted in the table as MAYER-1968).

3. Mayer, S. W., J. Phys. Chem. TL, 4159 (1967).

4. Mayer, S. W. and Schieler, L., J. Phys. Chem. 72

,

2628 (1968).

t A _1 Activation energies quoted from this report are in cal mol

R = 1.987 cal mol"^K“ .
7-66

TUNDER-1967

1. Estimated by A. Q. Eschenroeder and J. A. Lordi, Symp , Combus

.

,

9th, Cornell Univ., Ithaca, N. Y., 1962 , 241 (1963). [Order of

magnitude estimates, rates by analogy with similar reactions and

averages of experimental data.]

3. Selected as in [A. Q. Eschenroeder and J. A. Lordi, Symp . Combus

.

,

9th, Cornell Univ., Ithaca, N, Y., 1962, 241 (1963)] as a weighted

average of experimental data.

4. Selected by N. Cohen as a weighted average of data reported by

A. A. Westenberg and S. Favin, Symp. Combust., 9th, Cornell

Univ,, Ithaca, N. Y., 1962, 785 (1963). (Applicable from 400°

to 1800°K.) [Westenberg and Favin set tbe rate of H + 0 + M

OH + M equal to that for H 4- K 4- M + M. ]

5. Selected by M. H. Bortner, Chemical Kinetics in a Reentry Flow

Field, R 63SD63, General Electric Space Sciences Laboratory,

(1962).

6. K. H. Anderson and S. W. Benson, J. Chem. Phys . 39 , 1677 (1963).

[The rate for CH~0 4- H CHO 4- H„ is quoted in this reference

from J. R. McNesby, R. Klein, and M. Scheer, JCPSA-1960-32-1814,

whose measurement depends upon the rate of D 4- H HO 4- H (R. Klein,

J. R. McNesby, M. Scheer, and L. J. Schoen, JCPSA-1959-30-58) ]

7. S. W. Benson, Ind, Eng. Chem . 56 , 18 (1964). [Rules for making

order of magnitude estimates for abstraction, addition and combination reactions of organic compounds are given here. These

are summarized in the 'General Notes' section.]

9. R. E. Duff. J. Chem, Phys . 28, 1193 (1958); also, C. P. Fenimore

and G. W. Jones, J. Phys. Chem . 65, 993 (1961).

11. Estimated by S . W. Mayer by analogy with the values for H~ 4- CTL = H 4- CH, and H«C0 4- H [given by K. H. Anderson and S. W. Benson,

JCPSA-1963 -39-1677. ] 2

,

13. Estimated by S. W. Mayer based on [R. W. Diesen, JCPSA-1963 -39-

2121]. The A and n values also agree with those of [A. Q. Eschenroder

and J. A. Lordi, SYMCA-1963 -9-241 ] . The E values for atom transfers

involving the N—H bond are about 2 kcal lower than those involving

the C—H bond, but from 2000 to 4000°K this difference has a relatively small effect on the rate constant.

JCPSA = J . Chem. Phys.

SYMCA = Symp. (Inteimational) on Combustion
7-67

TUNDER-1967

14. R. W. Diesen, J. Chem. Phys . 39

,

2121 (1963).

15. Simonaitis, J. Rhys. Chem . 67 , 2227 (1963); also, M. A. A. Clyne,

B. A. Thrush, Trans. Faraday Soc . 57, 1305 (1961). A is the mean

of the results in these two papers; E is given in the latter paper.

16. C. P. Fenimore and G. W. Jones, J. Phys. Chem . 65 . 1532 (1961).

17. J. A. Green and T. M. Sugden, Symp. Combust., 9th. Cornell Univ .

,

Ithaca, N. Y., 1962, 607 (1963). [E values are order of magnitude

estimates by Tunder, et al.]

18. V. N. Kondratiev, Symp. Combust., 7th, London and Oxford 1958

,

31 (1959); B. H. Mahan and R. B. Solo, J. Chem. Phys . 37, 2669

(1962) .

19. K. A. Wilde, AIAA J . 2, 3 74 (1964). [Wilde quotes H + H + M

-» H + M from Patch [ JCPSA-1962-36-1919) , sets H + H + HF - H + HF

equal to the rate for H + H + H

2 + and sets F + H

2 ^ H + HF

equal to the rate of H. + 0 0 + OH reported by F. Kaufman and

F. P. Del Greco, SYMCA- 1963 -9-659 .

]

21. M. H. Bortner, Chemical Kinetics of Atmospheric De -ionization,

R 63 SD 34, General Electric Missile and Space Division (1963).

[This reference is also the basis of order of magnitude estimates,

see 'General Notes'.]

23. R. Dunlap and R. Hermsen, Nonequilibrium Flow in Nozzles, UTC

2032-FR, United Technology Corporation (February 1963).

25. Estimated by N. Cohen from K. L. Wray and J. D. Teare, J. Chem.

Phys . 36, 2582 (1962).

26. W. E. Kaskan and W. G. Browne, Kinetics of the H^ /C0/0 o Systems,

R 64 SD 37, General Electric Missile and Space Division (1964).

See also Reaction Summary for H 2 +M=H+H+M.

28. T. Jacobs, N. Cohen, and R. Giedt, J. Chem. Phys . 43 , 3688 (1965).

29. Estimated by N. Cohen on basis of F. Kaufman and J. Kelso,

Symp. Combust ., 7th, London and Oxford, 1958, 53 (1959).

30. Estimated by N. Cohen from B. Cary, Phys, Fluids 8_, 26 (1965).

31. G. C. Fettis and J. H. Knox, Progress in R~ac i Kinetics , (MacMillan, N. Y., 1964), Vol. 2, p. 22.
7-68

TUNDER-1967

32. F. S. Klein and J. t. Herron, J. Chem. Phys. 41, 1285 (1964).

33. K. L. Wray, J. Chem. Phys. 38, 1518 (1963). (For 1000°K and above).

[Wray combines his data on recombination of 0 with earlier results

to yield k * 2.5 x 10l6T°- 5 exp(-D/RT) or k = 2.4 x 10l8T“lexp( -D/RT)

cm^/mol"^s”^ for 0

2 + Ar -* 0 + 0 + Ar.]

34. S. W. Benson and A. E. Axworthy, J. Chem. Phys. 42, 2614 (1965).

[id, JCPSA-1957-26-1718] See Reaction Summary for 0^ + M * 0 + 0

2 + M.

35. C. D. Johnson and D. Britton, J. Phys. Chem. 68, 3032 (1964).

[Johnson and Britton report their measurement as log-j^k * 9.85 - 6520/T l mole-isec” 1 for F

2

+ Ar - F + F + Ar (5% F

2

in Ar)

]

37. A. A. Westenberg, Letter, in "Report on the Establishment of Chemical Kinetics Tables", Central Propulsion Information Agency

(unnumbered publication) April 1967, p. 48.

38. G. Dixon-Lewis, W. E. Wilson, and A. A. Westenberg, J. Chem. Phys.

44, 2877 (1966). See Reaction Summary for CO + OH * C0

2 + H.

39. K. G. P. Sulzmann, B. F. Myers, and G. R. Bartle, J. Chem. Phys.

42, 3969 (1965).

40. C. P. Fenimore, Chemistry in Premixed Flames, (Pergamon Press,

N. Y., 1964).

41. R. M. Fristrom and A. A. Westenberg, Flame Structure, (McGrawHill Book Company, Inc., N. Y., 1965).

42. M. H. Bortner and R. H.'Kummler, DASA Reaction Rate Handbook,

DASA- 1948, Chapt. 19-

43.

A. V. Phelps, DASA Reaction Rate Handbook, DASA-1948, Chapt. 12.

44.

M. A. Biondi, DASA Reaction Rate Handbook, DASA-1948, Chapt. 11.
7-69

WILSON-1968

WILSON, WM. E., JR., "Kinetics Tables for the Reactions of Hydroxyl

Radicals"

See "Reaction Summaries", Chapter V of this report for evaluations on:

CH. + OH = CH_ + HO

4 3 2

CO + OH = C0

2

+ H

OH + OH *= H

2

0 + 0

H

2

+ OH = H

2

0 + H

WILSON, WM. E., JR. and GARVIN, DAVID, "Kinetics Tables for the

Reactions N + 0

2 = NO + 0 (k

+

), NO + 0 = N + 0

2

(k_)"

See "Reaction Summaries", Chapter V of this report for evaluation on:

N + 0

2 = NO + 0

8-1

CHAPTER 8. General Bibliography

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8-2

Ashmore , P • G .

,

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Burnett, M. G., and Tyler, B. J.

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Avramenko, L. I., and Kolesnikova, R. V., "Mechanisms

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8-3

Avramenko, L. I., and Krasnen’kov, V. M., "The

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with Various Gases. II. Reaction with H

p

and CO,’’

Zh. Piz. Khim. 24_, 207 (1950)

Avramenko, L. I., and Lorentso, R. V., ’’Reaction of

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Free Hydroxyl with Aldehydes,’’ Doklady Akad. Mauk

S.S.S.R. 69, 205 (1949)

Axworthy, A. E., Jr., ’’Collisional Processes in

Gas-Phase Kinetics,” Ph. D. Thesis-University of

Southern California, (Univ. Microfilms, Ann Arbor,

Mich. 1959) L. C. Card No. Mic. 59-1837

Azatyan, V. V., Nalbandyan, A. B., and Meng-Yuan, T.,

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of Atomic Oxygen with Ethane,” Doklady Akad. Nauk S.S.S.R.

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Sect. 147, 973 (1962) English

Azatyan, V. V., Nalbandyan, A. B., and Meng-Yuan, T .

,

’’Determination of the Rate Constants of the Elementary

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8-4

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( 1961 ) Bahn, G. S., "Engineering Selection of Reaction Rate

Constants for Gaseous Chemical Species at High

Temperature. Part 2. Generalizations , " Western

States Section, The Combustion Institute Paper 62-27,

November 1962

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Np, Op, NO, N and 0," Pyrodynamics 1_, 147 (1964)

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NpO, NOp and 0^, but Only One of These Species,

with Np, Op, NO, N and 0," Pyrodynamics 1^, 271 (1964)

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NOp, and 0^, Also Involving Np, Op, NO, N and 0,"

Pyrodynamics 1^, 335 (1964)

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NO^ with N

2 0, N0

2

, 0

3

, N

2

, 0

2

, NO, N and 0."

Pyrodynamics 2_, 91 (1965)

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H

2

, 0

2

, OH, H and 0," Pyrodynamics 2_, 197 (1965)

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H

2 0, H02

, and 0 o but Only One of These Species with

H

2

, 0

2

, OH, H and 0," Pyrodynamics 2, 315 (1965)

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2 0,

H0

2

, HpOp, and 0^ Also Involving Hp, Op, OH, H and

0," Pyrodynamics 3_, 245 (1965)
8-5

Bahn, G. S., "Chemical Kinetics. Detailed Compilation of

Reaction Rate Information for the H-O-N System,"

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N and 0," Pyrodynamics 5> 79 (1967)* Idem, "Reactions

Involving 0 and H," Pyrodynamics 5_, 291 (1967).

Idem, "Reactions Involving N, 0, and H," Pyrodynamics

5, 375 (1967)

Bahn, G. S., "Chemical Kinetics. The Reactions H + C0~ = OH + CO and CO^ + M = 0 + CO + M," Pyrodynamics 6_,

101 (1968). Same data as Western States Sect . /Combust

Institute Paper 67-11

i Bahn, G. S., "Status Report of Effort in Engineering

Selection of Reaction Rate Constants for Gaseous

Chemical Species at High Temperatures, With a

Review of H + C0

? = OH + CO and C0? + M = 0 + CO + M"

Western States Section, The Combustion Institute

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6 , 101 ( 1968 ) Baldwin, R. R., "The First Limit of the Hydrogen+Oxygen

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1963 ), p. 218

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,

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,

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,

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,

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,

Baldwin, R. R., Symp.

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,

9th (Academic Press

,

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!
8-6

Baldwin, R. R.,.and Brattan, D., "Homogeneous Gas-Phase

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8th (Williams and Wilkins, 1962) p, 110

Baldwin, R. R., and Brooks, C. T., "Efficiency of Water

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8-7

Baldwin, R. R., Simmons, R. F., and Walker, R. W.,

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,

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8-8

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8-9

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2

," J. Chen. Phys. £2, 37?5 (196s)
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