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M.J. Mo6na , S.P. Sander , Jet Prqlulslon laboraIory 

O.M.Golden 

SRI International 

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R.F. Hampson , .' 

M.J. KurylO, " 

NaIionaJ BureaJ 01 StandanfS 

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TECHNICAl. REPORT STANDARD TlTLf PAGE 

) -1.--Report-No.- 87-4-1 -2 .--GowI'rllMnt-Ac:ceafon-No.- --3. -"clplent~ .-Catalog-No.· 

4. TItle and Subtitle -5. ~ Date I 

Chemical Kinetics and Photochemical,Data for September 15, 1987 I 

Use in Stratospheric Modeling 6. P.rforming Organization Code I 

Evalu ation Number 8 I 

7. Author,,) W.B. DeMore, M.J. Molina, S.P. Sandel: ,8. Performing Organization Report No./ 

D.M. Golden, R.F. Hampson, M.J. Kurvlo* 

9. Performing ~Izatlon Name and Address 10. Work lkIit No. 

JET PROPL~ION LABORATORY 

California 11. Contract « Grant No. Institute of Technology NAS7-918 I . - - 48QO ,Qak Grove I)rive. ____ ' -- -- .- -.. - Pasadena, California 91109 13. Type of Report and Period Co.,..d I 

External Report, I 

12. Spon5«ing ~y Name and Addrea JPL Publication . NATIONAL AERONAUTICS AND SPACE-ADMINISTRATION 

Washington, 1". Sponsoring ~'!'!cy Code D.C. 20546 RE4 BP-147-5l-02 

15. Supplementary Notes 

. --- --_ . ~. - -~ - '- . -

*Authors, continued: C.J. Howard,. A.R. Ravishankara' - -- - - _. 

16. Alxtract 

This is the eighth in a series of evaluated sets of rate 

constants and photochemical cross sections complied by the 

NASA Panel for Data Evaluation. The primary application of 

the data is in the modeling of stratospheric processes, with 

particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of 

this evaluation are available from the Jet Propulsion Laboratory, Documentation Section, lll-ll6B, California Institute 

of Technology, Pasadena, California, 91109. 

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17. Key Wort. (Selected by Authcr(s» 18. Distribution Statement 

Physical Chemistry; Geosciences Unclassified; unlimited 

and Oceanography (General); Space 

Sciences (General) 

19. Security Clauif. ~f Hlis report) 20. Security Claaif. (of this page) 21. No. 01 Pages 22. Price 

Unclassified Unclassified 

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-Chemical Kinetics-and Photoehemical 

Data for Use in Stratospheric Modeling 

Evaluation- Niimber 8 

NASA Panel foiData Evaluation: 

W.B. DeMore 

M.J. Molina 

S.P. Sander 

Jet Propulsion Laboratory 

D.M. Golden 

SRlintematiOna.l 

September 15, 1987 

I\II\SI\ 

NatIOOIII AeronaIJiCS and 

Space AanlrisIrlIDOIl 

Jet PropuIIiOn l.IbOratory 

CaiIorria InsIiIIAe ~ TechnOlogy 

Pasadena. CaIiIorna 

R.F. Hampson 

M.J. Kurylo 

National Bureau of Standards 

C.J. Howard 

A.A. Ravishankara 

NO,lA Envirorwnental Research Laboratory 

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The research described in this publication was carned out by the Jet Propulsion 

Laboratory. California Institute of Technology, under a contract with the National 

Aeronautics and Space Administration. 

Reference herein to any specific commercial product. process, or service by trade 

name, trademark, manufacturer, or otherwise, does not constitute or Imply Its 

endorsement by the United States Government or the Jet Propulsion LabOratOlY, 

California Institute of .TechnoJogy--· 

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INTRODUCTION . . • . . . . . 

BASIS OF THE RECOMMENDATIONS 

RECENT CHANGES AND CURRENT NEEDS 

OF LABORATORY KINETICS 

- Ox Reactions 

O( 10) React_ions 

- HOx Reactions 

- NOx Reactions 

- Hydrocarbon Oxidation . . 

- Halogen Chemistry 

SOx Reactions . 

- Ketal Chemistry 

CONTENTS 

- Photochemical Cross Sections 

ATMOSPHERIC CHEMISTRY 

- Overview 

·-Heterogeneous Effects 

RATE CONSTANT DATA . 

. Bimolecular Reactions 

. Termo1ecu1ar Reactions 

:-Uric'er~ainty Estimates 

- Units 

-,,-- . --. -.. " -.-

- . 

;-

- TABLE 1. RATE CONSTANTS FOR SECOND-ORDER REACTIONS 

- Notes 

- TABLE 2. RATE CONSTANTS FOR THREE-BODY REACTIONS 

- Notes • . • . • • • . • 

iii 

~-."'~~~' 

1 

3 

4 

6 

6 

7 

_ 7 __ 

8 

9 

10 

12 

13 

13 

13 

16 

18 

18 

21 - -- - _. 

25 

28 

29 

43 

81 

83 

... 

• 

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EQUIUBRImf CONSTANTS 

- Fonaat 

- Table of Data • 

- Notes 

PHOTOCHEKlCAL DATA • • 

- Discussion of Format and E~or Est~te •. -~ - -.~ "~- _ ... 

- Photochemical Reactions of Stratospheric 

Interest •• • • • • • . • • • • • • 

- -eo.bined Uncer~inties for Cross' Sections ancr 

QuantuJII Yields ••.•••..•••....• 

Data Entries 

-°2· 

- °3 

Absorption Cross Sections 

Quantum Yields in Photolysis 

- H02 • 

- H202 

- N02 

- N03 

- H20 

.-.- Absorption C1.0S-s. Sections ciS-FUnction of -Temperature 

Absorption Cr.oss Sections at 298 K 

- N205 

- RONO 

- RN03 

- H02N02 

- C12 

CI0 

iv 

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89 

89 

90 

91 

92 

,_ 92 

93 

94 

95 

96 

98 

99 

99 

101 

102 

104 

108 

-108 

109 

110 

111 

111 

114 

115 

116 

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- ClOO 

- OClO 

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~ C1202 

- IiCl . . . . . . . . . . . . . . . . . . 

- HOCI 

....... - -- - ClNO 

- ClN02 .. ... ... .. ... .. . . . . . . . . . 

ClONO 

- ClON02 - .. ... .. ... .. .. ... ... .. . . . . . .. .. .. .. 

'Halocarbon Absorption Cross Sections and Quantum Yields 

CC14 

- CC1)F 

- CC12F2 

- CHC1F2 

- CH3Cl 

- CC120 

- CC1FO 

- CF20 

- CH)CC13 

CBrC1F2 

- CBrF3 

- BrO • 

- BrON02 

- HF • 

CH20 

- CH)OOH 

------

v 

~ 

116 

117 

119 

119 

120 

121 

- -- 122 --_.- -

124 

, , 

. 125 

126 

.- 128-

129 

130 

131 

133 

134 

135 

135 

135' 

135 

137 

137 

138 

140 

141 

141 

143 

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) 

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------_._-- ---.---~ 

- HeN • 

- CH3CN 

- 502 

- OCS 

- C52 • 

- HaCl 

- HaOH 

APPENDIX: GAS PHASE ENTHALPY DATA • 

REFERENCES -. -; 

FIGURE 

1. Symmetric and Asymmetric Error-Limits 

vi 

_ a _ _ _" 

143 

143 

144 

144 

145 

145 

147 

148 

149 

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ABSTRACT 

This is the eighth in a·series of ~valuated s~t~9f rate c~~t~~~s_~~d 

photochemical cross sections compiled by the NASA Panel for Data Evaluation. 

The primary applicat~on of the data is in the modeling of stratospheric 

processes, with particular emphasis on the ozone layer and its possible 

perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory, Documentation Section,-·-

111-116B, California Institute of Technology, Pasadena, California, 91109. 

vii 

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C. .J. Howard (H~x chemistry, O(lD) reactions, metal chemistry) 

M. J. Kurylo (SOx chemistry) 

M. J. Kolina (photochemical data) 

A. R. Ravishankara (hydrocarbon oxidation) 

S. P. Sander (NOx chemistry) 

As shown above, each Panel member conce~tra~~s his ~ffQrt on a given. 

area or type of data. Nevertheless, the final recommendations of the Panel 

represent a consensus of the entire Panel. Each member reviews the basis 

for all recommendations, and is cognizant of the final decision in every 

case. Communications regarding particular reactions may be addressed to 

thp appropriate panel member: 

Y. B. DeMore 

M. J. Molina 

S. P. Sander 

Jet Propulsion Laboratory 

183-301 

4800 Oak Grove Drive 

Pasadena, CA 91109 

D. M. Golden 

PS-03l 

SRI International 

333 Ravenswood Ave. 

Menlo Park, CA 94025 

R. F. Hampson 

M. J. Kurylo' 

National Bureau of Standards 

Chemical Kinetics Division 

Gaithersburg, KD 20899 

c. J. Howard 

A. R. Ravishankara 

NOAA-ERL, R/E/AL2 

325 Broadway 

Boulder, CO 80303 

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Copies of this evaluation may be obtained by requesting JPL Publication 

87-41 from: 

Documentation Section 

111-1168 

4800 Oak Grove Drive 

Pasadena, CA 91109 

Telephone: (818) 354-5090 

BASIS OF THE RECOMMENDATIONS 

The recommended rate constants and cross sactions are based on laboratory measurements. In order to provide recommendations that are as up-todate as possible, preprints and writte~ private communications are a~c~pte~, 

--out- only when -it is expected that -they will appear as published journal 

articles. In no cases are rate constants adjusted to fit observations of 

stratospheric concentrations. The Panel considers the question of consistency of data with expectations based on the theory of reaction kinetics, 

and when a discrepancy appears to exist this fact is pointed out in the 

accompanying note. -The maJor use of theoret1cal extrapolation of data is 

in connection with three-body reactions, in which the required pressure or 

temperature dependence is sometimes unavailable from laboratory measurements. 

and can be estimated by use of appropriate theoretical treatment. In the 

case--of important rate constants for which no ·experimenta~ :data are available, the panel may provide estimates of rate constant parameters based on 

analogy to similar reactions for which data are available. 

3 

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RECEh"T CHANGES AND CURRENT NEEDS 

OF LABORATORY KINETICS 

Laboratory studies have produced no major changes in the kinetics and 

photochemistry used to model. the normal stratosphere since the publication 

of our previous evaluation, JPL Publication 85-37. There are approximately 

thirty-seven changes in the rate constant recommendacions in the present 

evaluation, but these are for the most part minor. Nonetheless, an 

importanl~ refinement has been made in the rate constant for OH + H02 , and 

some significant changes in NOx chemistry have also been made. Forty-ewo 

new reactions have been added, representing processes which play small but 

possibly significant roles in the stratosphere. Some reactions ~hich are 

.thought_to be unimportant in.the stra~osphere are ineludedfor completeness .. 

and for possible applications to laboratory studies. 

The recent emphasis on Antarctic chemistry, with its unusualcharacteristics of low temperature and the presence of polar stratospheric clouds, 

has focused attention on three areas of stratospher·c chemistry not 

previously. considered very important: .(1) chemistry at temperatures as low 

as 180 K; (2) heterogeneous reactions, especially on ice particles; and 

(3) certain reactions such as C10 + C10, which are normally not competitive 

in the stratosphere because of the low C10 concentration. 

Very few laboratory studies of. stratosp~~r~c ·~hemis~. have- been·'· -----

conducted at temperatures below 220 K, partly because of difficulties with 

enhanced surface reactivity, and because such work has no~ been considered 

relevant to the stratosphere. It is now apparent that increased emphasis 

should be placed on the temperature regime of 180-220 K, especially since 

the simple Arrhenius temperature coefficients of several very important 

reactions,· e.g., Cl + CH4 and H02 + 03 , are not sufficiently reliable 

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) for extrapolation to very low temperatures. Indeed, the Arrhenius equation 

may prove to be unacceptable for wide temperature ranges, because of the 

more complex dependence shown by many reactions. 

An additional aspect of low temperature chemistry is the possibly 

enhanced role of complex formation. Examples are the formation of 02 

complexes with species such as ClO and atomic chlorine. The kinetics and 

. thermochemistry-for-these processes are not well known. In-this connection, 

we have now provided uncertainty esttmates in the tabulation of equilibrium 

constants, Table. 3. The chemistry and .photochemistry of complexes may also 

be significant in certain cases . 

. Heterogeneous chemistry on aerosol pe.rticles has previously been 

considered to be of marginal importance in the stratosphere- (i. e., see'-the 

discussion on heterogeneous chemistry on page 16). It has nevertheless 

long been recognized that certain very slow gas phase processes, such as 

hydrolysis of chlorine nitrate, might be significantly accelerated on 

particle surfaces. It is now thought that such processes on ice particles 

are possibly of major importance in Antarctic ozone chemistry. The effects 

of volcanic emissions, which temporarily increase the stratospheric particle 

loading by large amounts, may also be important in short term (two to three 

year) ozone fluctuations. 

Measurements in Antarctica show that unexpectedly high concentrations' 

of ClO are present in c;ertain regions within the po~ar vortex. As a 

consequence, reactions such as ClO + ClO may play a major role in the 

chlorine chemistry of that region. V~ry little is known about the chemistry // 

of the C1202 dimer, which may exist in more than one isomeric form. In 

the present evaluation, we have not attempted to ~ke recommendations for 

. ~ the high chlorine chemistry because of the lack of information . ',. 

5 

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With regard to changes Dade in the present evaluation, it should also 

be llIentioned that a table ;,f enthalpy data has now been added as an Appendix. 

Qx Reactions 

The kinetics of the 0, 02' and 03 system appear to be well established. 

There remains some concern about the possible roles of excited states of °

2 , 

.- especially 02(1t.)-;- but at" present there is no evidence that -these states 

have any important effects on the overall chemistry of the stratosphere. 

Bair and coworkers (Locker ~Al.,1987) report formation of about 60% 

electronically excited 03(3B2) as an intermediate in the ° + 02 + M reaction. 

Based on their rate constant for quenching to the ground state, the ratio 

of excited 03 to ground state 03 is at;: most a few parts per thousand at 

60 km, and decreases sharply at lower altitudes. Thus, unless the quenching 

process itself results in chemical change, the process may be insignificant. 

OC1D) Reactions 

The data base for 0(10) kinetics is in fairly good condition. There 

is good to excellent agreement among independent measurements of the absolute 

rate constants for 0(10) deactivation by the major atmospheric components, 

N2 and 02' and by the critical radica1-produclngcomponents, H20, CH4' N20. 

and HZ'- - There are fever c:lirect studies of the-products of the deactivation--

processes, but in most cases these details appear to be of minor importance. 

Some processes of interest for product studies include the reactions of 

O(lD) with 014 and ha1ocarbons. Possible kinetic energy effects from 

photolytically generated O(lD) are probably not important in the atmosphere 

but may contribute ca.p1ications in laboratory studies. The rate coefficient 

for the reaction of 0(10) with HCN should be measured since it may playa 

role in the atmospheric oxidation of this trace gas. 

6 

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HQx Reactions 

Our knowledge of the kinetics of HOx radicals has continued to improve. 

The most significant development with this report is on the OH + H02 

reaction. This reaction is a key HOx radical termination step throughout 

much of the atmosphere. New measurements by Keyser (1987) appear to explain 

a discrepancy between previous low pressure and high pressure measurements. 

- ---- - --_ .. - Keyser has found a systematic error due to the presence of atomic Hand ° 

in the low pressure discharge flow experiments. The recommended rate 

'coefficient for the OH + H02 reaction has been increased and the previous 

pressure dependence has been removed. The recommendation for k(H02 + 03) 

has--also-been revised, but the overall situation for this reaction is less 

satisfactory. All of the data for the temperature range 240-400 K cannot 

be fit satisfactorily with a single Arrhenius equation. The recommendation 

is weighted heavily toward the low temperature data for stratospheric 

applications. High quality measurements that avoid the limitations of the 

previous studies are still needed for both reactions. 

NOx Reactions 

The data base for NOx reactions is relatively well established. The 

rate constant for the important ° + N02 reaction has been revised reSUlting 

Trl~l 20% -incr~as~ at 220 K. Our understanding of the impo~tant OH + HN03 

reaction has improved due to confirmation of a small pressure dependence, 

which helps explain some of the earlier divergence between flash and flow 

studies. The equally important OH + H02N02 reaction is not as well 

characterized, particularly with regard to the temperature dependence. 

Additional studies of the H02 + N02 + K recombination are also needed, 

especially on the temperature depeno;!ence of the low pressure limit. 

7 

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) Recently, direct studies of some key N03 reactions have become available, 

greatly improving the reliability of that data base. 

The data for NH2 reactions are sparse. There are a large number of 

studies only for the NH2 + NO reactions and these show a factor of two 

discrepancy between flow and flash systems. 

Hydrocarbon Oxidation 

Our understanding of hydrocarbon. oxidation in the atmosphere has 

improved considerably in the past few years. All hydrocarbons are released 

at the surface of the earth, and their degradation in the troposphere is 

initiated by reaction with OH (and with ozone in the case of olenns). 

Depending-on-their reactivity with OH, only a fraction of the surface·flux 

of hydrocarbons is transported into the stratosphere, where their oxidation 

serves as a source of water vapor. In addition, the reaction of atomic 

chlorine with these hydrocarbons (mainly CH4 ) constitutes one of the major 

sink mechanisms for active chlorine. Even though CH4 is the predominant 

hydrocarbon in the-stratosphere-, we have included in this evaluation .certain 

reactions of a few heavier hydrocarbon species. 

In the stratosphere, CH4 oxidation is initiated by its reaction with 

either OH or Cl (and to a limited extent 0(10», leading to formation of 

--·cH3and- subseque~:;ly_ CH302' Several details-of the-subsequent chemistry 

are unclear, primarily because two key reactions are not well characterized. 

These reactions are: (1) CH302 + H02' which exhibits an unusual temperature 

dependence analogous to that for the H02 + H02 reaction and (2) CH300H + OH, 

which has been recently studied in a competitive system and found to be 

extremely rapid. Discrepancies in the absorption cross sections of CH30 2 

and H02 have added to the uncertainty regarding the rate coefficient for the 

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CH302 + H02 reaction. Even though the rate constants for the two reactions 

mentioned above are not very well known, the effects of these uncertainties 

on stratospheric 03 perturbation calculations are negligible. 

One area of hydrocarbon oxidation which has seen a great deal of 

improvement is that of product analysis. However, some additional work 

may be required to measure branching ratios for reactions such as CH302 + 

CH302 and CH302 + H02' 

The oxidation scheme for higher hydrocarbona has not been fully 

elucidated. However, the rate of transport of these hydrocarbons into the 

stratosphere can be easily calculated since the rates of reactions with OH 

are well known. In most cases iti~ expected that the radicals formed f~o~ 

the initial OH or Cl attack will follow courses analogous to CH3' and 

ultimately lead to co. 

Halogen Chemistry 

The recommendations for the important ClOx reactions have not changed 

significantly since the previous evaluation. This reflects the fact that 

most of the important homogeneous gas phase processes are well understood. 

There is a better upper limit to the rate of reaction of ClON02 with HCl 

and a new entry for the reaction of ClON02 with H20. The data indicate 

that-these homogeneous gas phase reactions are too slow to be important in 

the chemistry of the stratosphere, but it is possib~e that the corresponding 

heterogeneous reactions may be important under certain conditions such as 

those in the atmosphere above Antarctica. There are new entries for the 

reactions of OH with seven potential alternative chlorofluorocarbons. 

There are still a number of questions regarding the important ClO + ClO 

reaction: the absolute rate as a function of T and P; the relative 

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importance of bimolecular and termolecular reactiorrchannels as a function 

of T and P; the dependence of product branching ratios on T and P; importance 

of the dimer and its reactions and photochemistry; possible role of complex 

formation with 02' There are only minor changes in the data base for 

reactions of BrOx and FOx species apart from changes in the recommendations 

for t.1te. _reactions .. of B,r. ~~o~s ~it:1.! H~2 _.a!1d J!202 . There have been several.. 

recent studies of the important BrO + ClO reaction which have improved our 

knowledge of the rate constant at room temperature, but further work is 

required to determine the temperature dependence and product ratios. 

SOx ReactionsThe data base on homogeneous sulfur chemistry continues to change and 

expand as we obtain more detailed laboratory data on a number of oxidative 

processes. In particular, we now have information on the temperaturedependence of several SH reactions important in the atmospheric oxidation 

of H2S and first-time information on several HSO reactions. Nevertheless, 

our understanding of the reactivity of these radicals is still far from 

complete. Similar improvements have been seen in the data for the reactions 

of SO with several atmospheric molecules (notably ClO, BrO, and· N02)' Of 

particular interest are the first direct measurements of HO~02- ~h_ich had 

. been postulated by Stockwell and Calvert (l983)-and Hargitan (1984a) as an 

intermediate in the oxidation of S02 into sulfuric acid via the sequence 

OH + S02 + H ~ HOS02 + H 

HOS02 + 02 ~ H02 + 503 

New data by Gleason~. (1987) and by Gleason and Howard (1987) result 

in a direct determination of the rate constant for the second reaction and 

support a homogeneous gas phase S02 oxidation mechanism involving no net 

10 

~~~,-'-

,~ 

t: 

11 
:-:-

r,>~r.r=t:"'. _. ___ .n. - ... ~ 

) 

. ~. 

;:/ 

1':" . .. :, 

,-I , .) 

.... 

k 

·change in HOx per H2S04 foxmed while negating a reaction sequence 

involving S03 formation via the. OH + HOS02 reaction (a mechanism which 

would have resulted in the loss of two OH radicals per H2S04 formed). 

However, there is a need for still further information on the atmospheric 

reactivity of HOS02 and perhaps even on reactions involving its possible 

c9mp1:~xes with 92 or H20~ Along ~hese_1atter_J.ines, a recent study_by 

Huie and Neta (1984) demonStrates that the formation of the HOS02 ·02 

adduct pre~ominates in solution. While the acidic natures ~~ both __ ~OS02 

and HOS02"02 result in their deprotonation in solution and existence as the 

S03 - and SOS - anions, these results suggest the possible atmospheric 

importance of the· -02 adduct- in its -hydrated form. In this and· mostdiscussions, S03 has been thought of as equivalent to sulfuric acid. This 

is supported by recent experiments by Hofmann-Sievert and Castleman (1984) 

... hich suggest the rapid isomerization of the adduct S03 "H20 to H2S04 

with a barrier to this process of less than 13 kca1/mo1. Further information 

on the reactions of S03 with other atmospheric-species is needed to assess 

the competition of these reactions with s03 hydrolysis. 

Additional progress has been made in developing an understanding of 

the mechanisms of OCS and CS2 oxidation. There are now additional studies 

. providing. rate -constant and primary product informati"on -for the- ·reactionS --

of OH with both species . In the case of CS2. there have been direct 

observations of reversible adduct formation with OH as well as further 

confirmation of its 02-enhanced pressure dependent oxidation by OH. Recent 

data for OH + oes does not reveal a rate constant dependence on total 

pressure or O2 pressure despite the observation of direct formation of SH 

in both the CS2 and OCS reactions and the postulation of similar complex 

(adduct) mechanislllS. New data indicate that the direct bimolecular reactions 

11 

._--_. 

.. r .~~~.~. 

-----.---.--- ---_._---. 

! 

-" 

,. 

r 

:A. 

-'J 
pr. p.: . .i!'~""' _.- -- -.- " _. -. 

'. 

) 

) 

I 

I 

,.~--

have lIarkedly different Arrhenius paraaeters from one another, thereby 

suggesting significant energetic differences in the reaction surfaces 

describing adduct formation. Further information regarding the elementary 

steps in the oxidation of both species should further our understanding of 

complex mechanisms in general. 

- Ketal Chemistry 

Twelve new reactions of sodiUII species have been introduced in this 

evaluation. - Sodium is-deposited in-the upper atDosphere by meteors along 

with larger amounts of silicon, magnesium, and iron; comparable amounts of 

aluminum, nickel,- -and carcfum;-and smal~.~ ~ounts of potassium_, chromium, 

manganese, and other elements. The interest is greatest in the alkali 

metals because they form the least stable oxides and thus free atoms can 

be regenerated through photolysis and reactions with ° and 03. The other 

meteoric elements are expected to form more stable oxides. 

The total flux of alkali metals through the atmosphere is relatively 

small, e.g., one or two orders of magnitude less than CF1ls. Therefore 

extremely efficient catalytic cycles are required in order for Na to have 

a significant effect on stratospheric chemistry. There are no measurements--

of metals or ~eta~5~~~oun~_ in_ the _str~tosphere which ipdicate a ~ignifi:,,_ 

cant role. 

It has been proposed that the highly polar metal compounds may 

polymerize to form clusters and that the stratospheric conc.mtrations of free 

metal compounds are too small to playa significant role in the chemistry. 

Some recent studies have shown that the polar species NaO and NaOH 

associate with abundant gases such as 02 and CO2 with very fast rates in 

the atmosphere. It has been proposed that reactions of this type will lead 

12 

'\1: 

,-

! --

r;, 

l~ 
rll!: 

) 

; 

, 

.' •. 

.. 

.. 

-

:.-

~ 

y~ .~., 

:. 

.. 

f· 

~. 

-)1 Cl 

!\r--~·'l. 

to the production of clusters with many molecules attached to the sodium 

compounds. Photolysis is expected to compete with the association 

reactions and to limit the cluster concentrations in daylight. If 

atmospheric sodium does form large clusters, it is unlikely that Na 

species can have a significant role in stratospheric ozone chemistry. In 

order to assess the importance of these processes, data are needed on the 

association rates and the photolysis rates involving the cluster species. 

Photochemical Cross Seetions 

Tho absorption cross sections of 02 around 200 IUD that is, at the 

onset of the Herzberg continuum -- have been remeasured in the laboratory 

and are now in better agreement -with the values inferred· from solar 

irradiance measurements in the stratosphere. 

The temperature dependence of the absorption cross sections of H02N02 

and H202 in the 300 IUD region might be significant and should be determined. 

The photochemistry of the CIO dimer, Cl202' must be studied in detail. 

ATMOSPHERIC CHEMISTRY 

Overview 

The ozone content of earth's atmosphere can be considered to exist in 

-three distinct_~~gi_ons_, ~he--t~oposphere, stratosphere, and meso·sphere. The 

unpolluted troposphere contains small amounts of ozone, which come from both 

downward transport from the stratosphere and froll in situ photochemical 

production. The chemistry of the global troposphere is complex, with both 

homogeneous and heterogeneous (e.g., raiu-out) processes playing important 

roles. The homogeneous chemistry is governed by coupling between the 

carbon/nitrogen/hydrogen and oxygen systellS and can be considered to be 

13 

r 

! 

~ 

.. 

~ 

I 

- - --- -~!'t 

\: 
r- ..... -~~ 

) 

.. 

.. 

.. 

-<' 

~ 

~ :. 

J 

) f 

4 

III 

,- ., 

more complex than the chemistry of the stratosphere, due to the presence 

of higher hydrocarbons, long photochemical relaxation times, higher total 

pressures, and the high relative humidity which may affect the reactivity 

of certain key species such as H02' Significant progress is being made 

in understanding the coupling between the different chemical systems, 

especially the mechanism of methane oxidation which partially controls 

the 'odd hydrogen -budget.-' 'this is' an' !.Diportant'development,--'asreactions 

of the hydroxyl radical are the primary loss mechanism for compounds 

containing- C-H ,<CH4' -cH3C1,' CHF2Cl, etc.) or c-c (C2C14' C2HC13' C7.H4'; 

etc.), thus limiting the fraction transported into the stratosphere. 

The stratosphere is the' region- of-the atmosphere 'where the bulk of 

the ozone resides, with the concentration reaching a maximum value of 

about 5 x 1012 molecule cm- 3 at an altitude of -25 kII. Ozone in the 

stratosphere is removed predominantly by catalytic (I.e., non-Chapman) 

processes, but the assignment of their relative importance and the 

prediction of their future impact are dependent on a detailed understanding 

of chemical reactions which form, remove and interconvert the catalytic 

species. A model calculation of stratospheric composition may include 

some 150 chemical reactions and photochemical processes, which vary greatly 

in their importance in controlling the density of ozone. Laboretory 

measurements of the rates of these reactions have progressed rapidly in 

recent years, and have given us a basic understanding of the processes 

involved, particularly in the upper stratosphere. Despite the basically 

sound understanding of overall stratospheric cheIlistry which presently 

exists, much remains to be done to quantify errors, to identify reaction 

channels positively, and to measure reaction rates both under conditions 

corresponding to the lower stratosphere (-210 K, -75 torr) as well as the 

14 

''''-d 

-. 

.~" . 

1.-

G • .1: 

.~ 
". J1: . .i':.-~-'~" -" " " " .~ 

---

) 

. " 

;; 

-:.. 

~ . :. 

) j 

, 

.top of the stratosphere· (-270 K, .-1 torr). As previously mentioned, 

Antarctic conditions require the consideration of even lower temperatures. 

The chemistry of the upper stratosphere, i.e. 30-50 km, is thought to 

be reasonably well defined, although there appear to be some significant 

differences between the predicted and observed chemical composition of 

this region of the atmos~h~re whi~h_~y be du~. to ~na~c~rat~ ~~t~~~a. or 

mi~s ing chemis try . In this region the composition of the atmosphere is 

predominantly photochemically controlled and the photolytic lifetimes of 

temporary reservoir species such as HOC1, H02N02' C10N02' N205 and H202 

are short and hence they play a minor role. Thus the important processes 

above 30 km all involve atoms "and small molecules. The maj ority of 

laboratory studies of these reactions has been carried out under the 

conditions of pressure and temperature which are encountered in the upper 

stratosphere, and their overall status appears to be good. No significant 

changes in rate coefficients for the key reactions such as Cl + 03' NO + ClO, 

NO + 03' etc., have occurred in the last few years. Historically, a-major 

area of concr.rn in the chemistry of the upper stratosphere has involved the 

reaction between HO and H02 radicals, which has had considerable uncertainty 

in the rate constant. This HOx termination reaction plays an important role 

in detemitUog die absoluteconcentraetonsorHO and HOi, "and. since HO play5-

a central role in controlling the catalytic efficiencies of both NOx and 

C10x ' it is a reaction of considerable importance. Recently the uncertainty 

in the rate coefficient for the reaction has decreased, now being thought 

to be about a factor of 1. 3 to 1. 8 over the range of atmospheric conditions. 

It should be noted that the HO + H202' HO + RN03 and HO + H02N02 reactions 

have little effect on controlling the HOx concentrations above 30 km. 

For reactions such as ° + HO and ° + H02' which control the HOx radical 

15 

, -

,~ 

r. 

----'--.---~---.-.--------~ 
~..2-~ -'.--,- ... -- - - - .-." --.- -.- ---. ---- -- ~-- - --- -. -_. 

) 

partitioning above 40 lcm,. the data base· can be considered to be quite good. 

One area in which additional studies ruy be needed is that of excited 

state chemistry, Le., studies to determine whether electronic or vibrational 

states of certain atmospheric constituents may be more iIIportant than hitherto 

recognized. Possible examples are 02 '* ' 03 '* ' HO * • or N2 * • 

The chemistry of the lower stratosphere is quite .c_o~~e~, w_it.~ s!~!~~-_ 

cant coupling between the HOx ' NOx and ClOx faJllilies. In this region of 

the atllosphere (15-30 lcm). both dynamics and photochemistry play key roles· 

in controlling the trace gas distributions. It is also within this region 

that the question of the pressure and temperature dependences of the rate 

. coefficients is most critical; due to the low temperatures (210 Kand lower) . 

and the high total pressures (30-200 torr). 

Heterogeneous Effects 

A continuing question in stratospheric modeling is whether or not 

aerosols perturb the homogeneous chemistry to a significant degree. This 

question has assumed much greater importance in connection with the possible 

role of polar stratospheric clouds in Antarctic chemistry. Effects could 

arise through the following processes: 

1_ Surface catalysis of chemical reactions. 

2. Production or removal:of-active species. 

3. Effects of aerosol precursors such as S02. 

In NASA Reference Publications 1010 and 1049, processes 1 and 2 above 

were discussed in general terms. It was shown that, with a few possibly 

significant exceptions, surface catalysis of chemical reactions is not 

expected to compete with the rates of homogeneous gas phase reactions_ 

The essential reason is that the frequency of collision of a gas phase 

16 

J 

'.:!: 

-'~ 

, .--

~ 

~, 
rJl:.·>tl~ 

... 

.\ 

; 

.. I 

- -) 

~ 

:<-

;;. 

.... 

. . 

.. 

1 

: 

, 

)1 

~ 

--. 

--.----- \;! 

molecule. with the aerosol surface is typically of the order of ro-S sec-I, 

whereas most of the key gas phase reactions occur with much greater 

frequency, for example, conversion of atomic chlorine to HCl by the Cl + 

CH4 reaction (10- 2 sec-I). Thus, even in the unlikely case of unit 

reaction efficiency on the aerosol surface the heterogeneous process 

cannot be significant. Possible _ exceptions occur for reactions which are __ 

extremely slow in the gas phase, such as hydrolysis of an anhydride, 

as in the _ re~ctio~ N20S_+ " H20 .. 2HN03~ There remains sOlie ~certainty 

with regard to the role of these latter processes. 

It was also shown in NASA Publications 1010 and 1049 that there is 

-no evidence that aerosols serve as significant" sources - or sinks -of the 

major active species such as chlorine compounds. However, Hunten et aI, 

(1980) have suggested that dust particles of meteoritic origin may scavenge 

metallic atoms and ions, and in particular may remove Na diffusing f=~m the 

mesosphere in the form of absorbed NaOH or Na2S04' 

Althougnit appears that aerosols do not greatly perturb the ambient 

concentrations of active species through direct interaction with the 

surfaces, the aerosol precursors may significantly perturb the stratospheric 

cycles through removal of species such as OH radicals. For example. a-

_" -large injection -o-f S02' 's"uch as that-which--ciccurred -in the -El Chichoneruption, has the potential of significantly depleting HOx radical concentrations, as was discussed in the section on SOx chemistry, It must be 

reiterated, however, that recent studies of the mechanism of 502 oxieation 

have shown that OH plays a catalytic role, and, therefore, the process does 

not result in a net loss of OH froll the system . 

17 

,. 

,.. 

• 

~, 
) The effects of aerosols on the radiation field and on the temperature 

may also need to be considered. These effects are probably scalI, however. 

There are two problems with regard to detecting the effects of aerosol 

injections such as that following the EI Chichon eruption. ~ne is that no 

adequate baseline exists for the unperturbed atmosphere, and therefore a 

given observation cannot unambiguously be assigned to the enhanced presence 

of the aerosol loading. ~. ~ - .. . . - - -- -- A second problem is that, as already discussed, 

the effects are expected to be subtle and probably of small magnitude. 

Thus, in spite or- -large changes that; may -occur -in- th-e aerosol content 

of the lower stratosphere, effects on the chemical balance will be 

difficult to detect~ 

RATE CONSTANT DATA 

In Table 1 (Rate Constants for Second Order Reactions) the reactions 

are grouped into the classes Ox' 0(10), HOx ' NOx ' Hydrocarbon Reactions, 

ClOx ' BrOx ' FOx, and SOx. The data in Table 2 (Rate Constants for ThreeBody Reactions), while not grouped by class, are presented in the same order 

as the bimolecular reactions. Further, the presentation of photochemical 

cross section data follows the same sequence. 

- Bimote-cular Reactions-- -

Some of the reactions in Table 1 are actually more complex than simple 

two-body reactions. To explain the anomalous pressure and te~erature dependences occasionally seen in reactions of this type, it is necessar'J to 

consider the bimolecular class of reactions in terms of two subcategories, 

direct (concerted) and indirect (non-concerted) reactions. 

18 

): 

-); 

.r 

C; 

, 

.. 
· ,.".', --:-~ .. p- -..-

---- ._-- .. ----- ~r .. ~ 

.( 

) A direct or concerted bimolecular reaction is one in which the reactants A and B proceed to products C and D without the intermediate formation 

of an AB adduct which has appreciable bonding, i.e., no stable A-B molecule 

~ 

exists, and there is no reaction intermediate other than the transition 

state of the reaction, (AB)~. 

A + B ~ (AB)~ ~ C + D 

The reaction of OH with CH4 forming H20 +,CH3 is an example of a :eaction 

of this~ class. ~ 

Very useful correlations between the expected structure of the transition state [ABJ~ and the A~.factor of the reaction rate constant can be 

made, especially in reactions which are constrained to follow a well-defined I 

approach of the two reactants in order to minimize energy requirements in 

the making and breaking of bonds. The rate constants for these reactions 

are well represented by the Arrhenius expression k - A exp( -E/RT) in the 

200-300 K temperature range. These rate constants are not pressure dependent. 

The indirect or non-concerted class of bimolecular reactions is characterized by a more complex reaction path involving a potential well between 

reactants and products, leading to a bound adduct (or reaction complex) 

formed between the reactants A and B: 

A + B : [ABJ* ~ C + D 

The intermediate [AB]* is different from the transition state [AB]~, in that 

'-;;1 it is a bound molecule which can, in principle, be isolated. (Of course, 

transition states are involved in all of the above reactions, both fo~ard 

and backward, but are not explicitly shown.) An example of this reaction 

,,.. 

00 ..... 

:. 

19 

::-) 

-- ,... -.....-- --.. --_ .. ----- -_._-_._-- -.... --~---

-_. -_._----
.~-....,..-------- .- "S'~Y'~-.""'''''i'~''.- ~------ --.. _-on 

-:....<-----

) 

,-

". 

., 

~-) 

type is CIO + NO, which normally produces CI + N02 as a bimolecular 

product, but which undoubtedly involves CIONO (chlorine nitrite) as an 

intermediate. This can be viewed as a chemical activation process forming 

(CIaNO) * which decOlllposes to the ultiJaate products, CI + N02' Reactions 

of the non-concerted type can have a more complex temperature dependence, 

can exhibit a pressure dependence if the lifetime of [AB]* is comparable 

- - - * . - - ~o the rate of collisional deactivation of [AS] • This arises because the 

relative rate at which [AS] * goes to products C + D vs. reactants A + B is 

a sensitive function of--its excitation- energy. - Thus, in reactions of this 

type, the distinction between the bimolecular and termolecular classification 

becomes less meaningful, and -it is especially necessary to study such 

reactions under the temperature and pressure conditions in which they are 

to be used in model calculations. 

The rate constant tabulation for second-order reactions (Table 1) is 

given in Arrhenius form: k(T) - A exp «_~)(l» and contains ~he following R T 

information: 

1. Reaction stoichiometry and products (if known). The 

pressure dependences are included, where appropriate. 

2, Arrhenius A-factor. 

3. Temperature dependence and associated uncertainty 

(-activation temperature" EfR±aEfR). 

4. Rate constant at 298 K. 

5. Uncertainty factor at 298 K. 

6. Note giving basis of recommendation and any other 

pertinent information. 

20 

':-Glr 

~ 

-.. 

- ---..• - ------.' ----:.-~ ".-w ~ -.-~ --.- - --.-. - --------
~.~~~~",., ... -:--:,,-------.-.~ . - .. -... --...--.-~ .. --.~~--~----~ ~~ 

) 

:; 

~ 

ri 

i 

" 

$ 

.~ r) 

.. _----

------

Termolecular Reactions 

Rate constants for third order reactions (Table 2) of the type 

A -. * K + B .. [AS) -. AB are given in the form 

ko(T) - ko

300(T/300)-n c.6 molecule-2 s-l, 

(where the value is suitable for air as the third body). together with the 

.- - - - - -

recolIDended value of n. Where pressure fall-off corrections are necessary, 

an additional entry gives the limiting high pressure rate constant in a· 

similar form: 

~(T) - ~OO(T/300)-m cm3 molecule-l s-l. 

To obtain the effective second-order rate constant for a given condition of 

temperature and pressure (altitude), the following formula is used: 

k(Z) - k(K,T) - ( 

1 

ko(T)[K] (l + [loglO(ko(T)[K]~(T»12)-1 .....,,;..--.,;.....:.---) 0.6 

+ (ko(T) [K)Ik=(T» 

The fixed value 0.6 which appears in this formula fits the data for all 

listed reactions adequately, . although in principle this quantity may be 

different for each reaction. 

Thus, a compilation of rate constants of this type requires the stipulation of the four parameters, ko(300), n-, 1c,.,(300) , and m. . These- can 

be found in Table 2. The discussion that follows outlines the general 

methods we have used in establishing this table, and the notes to the table 

discuss specific data sources. 

21 

.-, 

.. -

t: 

t l':: 

tY;:~~ --- ---- .~~ 
~J! ... ~'f' F?t i"\ .---:-----....... --.---.-

" 

. --p-- _. __ .... ~----... ---~-- ---~"'---'."'J. 

.. .. 

~ 

. 

• 

~ 

-:/ 

r. 

. ~ .. :. 

#' 

<-" 

J 

) Low-Pressure LWting Rate Constant [~(T) I 

Troe (1977) has described a simple lIethod for obtaining low-pressure 

limiting rate constants. In essence this Jlethod depends on the definition: 

~(T) • Px~,sc(r) 

Here sc signifies ·strong" collisions, x denotes the bath gas, and Px is 

an efficiency parameter (0 < P < 1), which provides a lIeasure of energy 

transfer. 

The coefficient Px is related to the average energy -transferred in a 

collision with gas x, <l.E>x' via: 

Px 

l-P 1/2 

x 

<AE>x 

FE ItT 

Notice that <AD is quite sensitive to p. FE is the correction factor of the 

energy dependence of the density of states (a quantity of the order of 1.1 for 

most species of stratospheric interest). 

For many of the reactions of possible stratospheric interest revieved 

here, there exist data in the lov-pressure limit (or very close thereto), and 

we have chosen to evaluate and unify this data by calculating ~ sc (T) for , 

the appropriate bath gas ~ and_ c~~~ting the value .of Px corresp0E.dingto ~e 

experimental value [Troe (1977)]. A recent compilation (Patrick and Golden, 

1983) gives details for many of the reactions considered here. 

From the Px values (most of which are for H2' i.e., f1N 2)' we compute 

<AE>x according to the above equation. Values of <A~ 2 of approximately 

0.3-1 kcal lIlOle-l are generally expected. If multiple data exist, we average 

the values of ~ and recolIIJIend a rate constant corresponding to the flN 2 2 

computed in the equation above. 

22 

~~.." .. 

,. 

.. 

, 

-'~ 
fl"0l'.trFh"\ ., 0 --- - --~-

" 

: 

- --

:;.-

-/ 

y' 

~ .. , :. 

I 

r, 

~) 

) Yhere no data exist we have estiaated the lov-pressure rate constant by 

taking PN - 0.3 at T - 300 K, a value based on those eases where data exist. 

2 

Temperature Dependence of Low-Pressure Limiting Rate Constants: n 

The value of n recommended here comes frolll a calculation of ~ from 

the data at 300 K. and a computation of I1N (200 K) assuming that <A~ is 2 2 

,independent_oLtemper_ature in this range •. This ~ (200 K), va].ue is cC?~bine~ 

with the computed value of ko sc (200 K) to give the expected value of the 

actual rate constant at 200 K. This latter in -combination with the value 

at 300 K yields the value of n. 

This procedure can be directly compared with measured values of ko 

-- (200 l{)---when those exist. Unfortunately-;- very few- values at 200 K are 

available. There are often temperature-dependent studies, but some ambiguity 

exists when one attempts to extrapolate these down to 200 K. If data are 

to be extrapolated beyond the measured temperature range. a choice must be 

made as to the functional form of the temperature dependence. There are 

two general-ways-of expressing- the temperature dependence of rate constants. 

Either the Arrhenius expression ko(T) - Aexp(-EjRT) or the form ko(T) - A' 

T-n is employed. Since neither of these extrapolation techniques is soundly 

based, and since they often yield values that differ substantially, we have 

uSed 'the method explained earlier a5the -basis 0 of our recommendations. 

High-Pressure Limit Rate-Constants [~(T)] 

High-pressure rate constants can often be obtained experimenta~ly, but 

those for the relatively small species of atmospheric importance usually 

reach the high-pressure limit at inaccessihly high pressures. This leaves 

two sources of these mzmbers, the first being guesses based upon some model. 

and the second being extrapolation of fall-off data up to higher pressures. 

23 

'-'~ _1J"" ...... - .. 

-~ 

I 

i 

.' 

.-

• 

~ 

-'-:'1 

./ 
,~-.------

· . 

.. 

· · 

) 

.-, 

), 

I 

Stratospheric conditions generally render reactions of interest much closer 

to the low-pressure limit, and thus are fairly insensitive to the highpressure value. This means that while the extrapolation is long, and the 

value of ~(T) not very accurate, a ·reasonable guess· of ~(T) will then 

suffice. In some cases we have declined to guess since the low-pressure 

limit is effective over the entire range of stratospheric conditions. 

Temperature Dependence of High-Pressure LiDit Rate Constants: m 

There are very little data upon which to base a recomm~ndation for 

values of m. Values in Table 2 are estimated, based on models for the transition state of bond association reactions and whatever data are available. 

Isomer Formation 

A particular problem with association reactions arises when there are 

easily accessible isomeric forms of the molecule AB. In this situation, if 

the laboratory measurement of the rate constant is accomplished by following 

the disappearance of reactants, the value ascertained may be the sum of two 

or more processes that should be measured and tabulated independently. A 

specific example of such a case is found in Table 2 for the reactions of 

Cl-atoms with NOZ' These reactants may come together to form either ClN02 

or ClONO. \fuether or not isomer formatio~, _ ~t1ch _ as discussed above, is 

important depends on the relative stability of the possible products. At 

the moment the only case that we are sure about is the above example. In 

the past however, there was some thought that data on the reaction between 

CIa radicals and N02 could be understood only in terms of the formation of 

both chlorine nitrate (CION02) and other isomers (ClOONO, OClONO). Experiments have shown that this is not the case and that chlorine nitrate is the 

24 

--- ../' 

... ~~----., -

----Ii 

J' t ._ 

h 

--~ 
~",.~~"'" -- ;r.,. 

'.':' 

-) 

~ 

: 

::;--

-/ 

r. - ~ .. . :. 

-.. 

~ 

'-, 

~ 

___ 4"'~" ... _, 

sole product. This question is discussed at sOllie length in note 16 of_ 

Table 2. 

There are many other possibilities for isomer formation in the reactions listed in Table 2. In some of the notes we have specifically pointed 

this out, but even for reactions where no mention is made of isomers, because 

we felt that they could not contribute under atmospheric conditions, extrapolation to higher pressures and lower temperatures should be done with the 

possibilities kept in'mind. 

uncertainty Estimates 

,For second-order rate constants in Table 1, an estimate._of the uncertainty at any given temperature may be obtained from the following expression: 

f(T) - f(298) exp I Ai ( 1 _ -1- ) R T 298 

An upper or lower bound (corresponding approximately to one standard deviation) of the rate constant at any temperature T can be obtained by multiplying 

or dividing the value of the rate constant at that temperature by the factor 

f(T). The quantities f(298) and 6EjR are, respectively, the uncertainty in 

the rate constant at 298 K and in the Arrhenius temperature coefficient, as 

listed in Table 1. This approach is based on the fact that rate constants 

are almost always known with minimum uncertainty at room temperature. The 

overall uncertainty normally increases at other temperatures, because there 

are usually fewer data and it is almost always more difficult to make 

measurements at other temperatures. It is important to note that the 

uncertainty at a temperature T cannot be calculated from the expression 

exp(6EjRT) . The above expression for f(T) must be used to obtain the 

correct result. 

25 

,/ 

. - - --------------

'1:1 

~ 
t~~-

.. 

) 

~ 

,-

. 

.. 

, 

--'~ ! 

~,-.~ .. 

The uncertainty represented by f(298) is normally symmetric; i.e., the 

rate constant may be greater than or less than the central value, k(298), 

by the factor f(298). In a few cases in Table 1 asymmetric uncertainties 

are given in the te.perature coefficient. Examples of symmetric and asymmetric error liIlits are shown in Figure 1. 

For three-body reactions (Table 2) a somewhat analogous procedure is 

used. Uncertainties expressed as increments to kc and k.., are given 

for these rate constants at room temperature. The additional uncertainty 

arising from the temperature extrapolation is expressed as an uncertainty 

in the temperature coefficients n and m . 

- -The as Signed- ~~e~inties r~present the subjective ju~gm~n~ -.!>f _ the 

Panel. They are not determined by a rigorous, statistical analysis of the 

data base, which generally is too limited to permit such an analysis. 

Rather, the uncertainties are based on a knowledge of the techniques, the 

difficulties of the experiments, and the potential for systematic errors. 

There is obviously no way to quantify these "unknown" errors. The spread 

in results among differel~t techniques for a given reaction may provide some 

basis for an uncertainty, but the possibility of the same, or compensating, 

systematic errors in all the studies must be recognized. -Furthermore, the 

___ p;~bal?J.lity_ dis_triJ?ution may not follow the normal, __ Gaussian form. For 

measurements subject to large systematic errors, the true rate constant may 

be much further from the recommended value than would be expected based on 

a Gaussian distribution with the stated uncertainty. As an example, the 

recommended rate constants for the reactions H02 + NO and Cl + ClON02 

have changed by factors of 30-50, occurrences which could not have been 

allowed for with any reasonable values of a in a Gaussian distribution. 

26 

--~13 

t~ 

U 

\1 

• 
-----

-y 

I 

;;:. 

I"" 

:. 

I 

.; 

~T'~ 

.. --- ---·-----1 

Th. H+03 Raactlan 

._--- ,...... -10.1 1 -=-. ARRHENIUS UN£! .,.... -1 0.2 f.... ........ UPPER AND LOWER I 

ERROR W.AITS I I 

IIJ 

I 

CD 

:J 

U 

CD 

0 

I ................. -10.3, ............... I 

E 

I") 

-1 0'41~ ________ ~~ - - - - _____ i -10.51-

1 0 6 

j 

__________________ 

.. _ ... ~.......... ___.. _ 

~ 

I 

-1 O. ~ __ ............... E 

u - '7; -. ..... ..... ..... ..... ';1 - . ..... -10.8, ............... 

~ - -10.9, . T--- .:< , , 

- -11.0~ TRIC , " 5.0 

'" I SYMME. , 4.5 o -11.1-l ' , 4.0 

...J. -:"'11.2 ' 3:0 ' 3.5(10_

3 

K1

) 

2.5 1 IT 

Th. H02 +03 Reaction 

-14.2~K:~--------------~-~----------·---------~ 

::' -1 4.3 ~ " " - ARRHENIUS UNE 

I 1 4 4 : " UPPER AND LOWER IIJ - • -:" ERROR W,cITS 

"I -14.5~ "" 

:J. ! -14.6~ ~---

u CD ·-14.7.r--_ : _____ __ -----__ I 

"0 -14.8~ -_ ~-_ i E I......... - ' 

-I") - -...,..14~9--~ _ _ '- ......... _ _ _ __ _ _ ~ -l 

-- E -1 5.0 j - ......... -- I ~ -15.1 ~ .......................... -----i ,...... -15.2i "" 

.::t I ......... 

_ -15.3~ " 

(,!) -15.41 "" - g -15.5 J ASYMMETRIC ......... " I 

-15.6 I '" I' "I"" i 

2.5 3.0 3.5 4:0 ' 4:5 ' 5.0 

1 IT (10-3 K- 1) 

Fig. 1. Symmetric and Asymmetric Error Limits 

27 I' 

~ 

~ 
-~ -

r

pr 

~~~.-.~ -"'''' .... 

'J 

-.-

:/ 

,.. 

. ~. 

:. 

1 

I 

, 

<f 

~ ~ 

""-~-~~, 

. --

-----,----- ----- ---------- \:! 

~ 

The rate constants are given in units of concentration expressed as 

molecules per cubic centimeter and tiDe in seconds. Thus, for first-, 

second-, and third-order reactions the units of k are s-l, cm3 mo1ecu1e-1 

8-1 , and cm6 D01ecu1e-2 s-l, respectively. Cross sections are expressed as 

cm2 mo1ecule-l , base e. 

28 

----

J. 

--

-

~ 

~ 
, r---

:'~ 

~ " 

: -) 

~ 

" 

.,: 

-, 

.'1 

~ 

/' 

~ 

r.; 

~ -, 

6 

~ 

• 

~ 

rT_~_-

Table 1. __ llate_ConatantL-fo~econcLOrder-lleactionaa 

It.utlca _ .l-'.c.tor· III:t(AIII) 11;(211 1:) fUU)b Jrot" 

0+02 .0, " 

0+~·0z+02 

OC,,'- + Ii' • 1 2 + Oz-

·.,+m 

_ • 0('" + HzO ·_011 + (II 

octo) + Cl4 • 011 + CI:J 

• Hz + ClzO 

OC", ~ Hz .. 011 + B 

OC", + 12 " ° + ·z 

K 

OC", + I Z .. 120 

OC,,) + Oz .. 0 + Oz 

OC", + alZ • 0 + CDz 

OC", + 03 .. 02 + Oz 

"°2+ 0 + 0 

• 0 C ,,) + II:l. .. prodacta 

OC", + BF .. 011 + r 

CSM TablA 2) 

•• 0z10-12 

- 4.lb:l0-11-

1.7:.:10-11 

2.2:1:10-10 

1.4:.:10-10 

- __ 1~4zl0-=-1~ 

1.~10-10 

1.1:1:10-11 

(SM TablA 2) 

3.2z10-11 

7.4zl0-11 

1.2z10-1O 

1.2z10·1O 

1 • .5:.:10-10 

1.4zl0-1O 

----- ----,-

10C'" +B!r-. produeta 1 • .5:1:10-10 

I OC", + c~ .. procturt. 2.lzlO-1O 

01 It'ctlN 

20~ S.Oz1O-15 1.15 .l1 

OC ,)) I"ctlon' 

-~OO --4.1b:1O-11- 1.3 .l2,A3 

~OO a.7z1O-11 1.3 .l2,A3 

01:100 2.2z10-1O 1.2_ .l2, A4 

01:100 1.4:1:10-10 1.2 A2,A3 

01:100 1~4:1:10-1_1 1.2 A2,A3 

.. _---- - - 1. 0z10-10- 01:100 1.2 A2 

-C1101:100) 2.1:1:10-11 1.2 A2 

-C70:t100) 4.0:1:10-11 1.2 A2 

-C1201:100) 1.lz1O-1O 1.2 A2 

~OO 1.2z10-1O 1.3 .l2,M 

01:100 1.2z10-1O 1.3 A2,M 

01:100 1 • .5:1:10-10 1.2 A2, A7 

~OO 1.4:1:10-10 2.0 AI 

- 01:100 1 • .5:1:10-10 •• 0 AS 

01:100 2.1:1:10-10 2.0 AlO 

-- -. --

OC", + eel4 .. proclacta 3.3zl0-1O 01:100 3.3:1:10-10 1.Z A2, All 

• Unit. Ir' ca3/_l.ca.Lt-.. c. 

b f(298) 11 th. UDC.rt.t1Dty .t:. ZaaI:. To ctlJ:ulpta the UDC.rt.t1nty .t. oth.r t-.penturll, 

..... the aprlla1oa: fCt) - fCZSI) up ~ C 1 - -1.. ) I. 1I0t. thet the tzpODCt:. 11 

ahaoluta nlu •• Il t %SIS 

• IDdic.t. ... chtDa. !rca the prrn-a Pan.l ....u..atiOD (JPL "-37). s.au. rOUDd-ott chlD&lI 

hlV' bee Md. tor .... nil lIlt.d .. lD the tabl.: th.a. Ir. DOt .arlttcl b7 .. t.ria-. 

I IDdic.t ... n_ ent,q thet ... DOt in the prrrioua ... tluat.loa. 

• Indlc.tII • chtDa. 1:l the IIott. 

29 

--

~ 

,. 

.. 

. 

~ 

--- ~ 
r:~~'!" 

~ 

:.-

, 

-) 

. . 

, " 

), 

~--~'I 

Tablrl~ " (Continued) 

Reac!:l!2D 6-la~~2Ii:a :;lRt'Al&lBl t'Z98 tl ftZ98 ),b 

O(in, + CFC~ .. producta 2.3zl0-1O 0±100 2.3zl0-1O 1.2 

O(in) + r::P2C~ .. producta 1.4zl0-1O 0±100 1.4z10-1O 1.3 

O(in) + CF4 " r::P 4 + ° 1.Sz10-13 0±100 1.lIzlO-13 2.0 

O(in) + CC1z0 .. producta 3.IIZ10-1O 0±100 3.lIzI0-1O 2.0 

" O(in, + CFCW .. prodUct. - 1.9z10-1O 0±100 ~- 1.;;10;-10' 2.0 

O(in) + CF20" producta 7.4zl0-11 0±100 7.4zl0-11 2.0 

O(in) + ~ .. CII-+ IIBz - "" - -"2.~10-10 CH:I00 2.~10-10 1.3 

BO Ra.cUcn. x 

H 

B+02 "802 (Saa tabla 2)" 

B+03 "08+02 1.4zl0-1O 470±200 2.9z10-11 1.25 

• B + 802 .. product. 8.lz10-11 0±200 8.1z10-11 1.3 

0+CII"02 +8 2.2z10-11 -(UO±100) 3.3zl0-11 1.2 

&0+802 -08+0Z 3. Oz10-11 -(ZOO±100) S.9z10-11 1.2 

o + Hz0z .. 011 + 1102 1.4zl0-12 200CH:I000 1.7z10-15 2.0 

.OS+1I02 -8Z0+02 4.6zl0-11 -(230±200) 1.0Z10-1O 1.3 

& 08 + 03 .. IIOZ + 0z 1.6zl0 -12 94CH:300 6.8z10-14 1.3 

08+CII-B2O+O 4.2z10-12 Z40±240 "1.9z10-U 1.4 

H 

.. B20Z (Sa. tabla 2) 

---~- -----

08 + Hz02 - 8Z0 +,802 " 3.3z10-12 200±i00 00 1.7z10-U 1:3 

OB+Hz-BZO+8 5.5z10 -12 200CH:400 6.7z10-15 1.2 

a Unit. are ca3/molacu1.-.ac. 

b !(298) 1. the uncertainty at 29BX. 

us. the azpre •• iOD: !(t) - !(298) 

ab.o1.ut.e valu •• ' 

to calculata the UDcert&1nty at other ~r.turaa, 

up 1 g ( 1 - -L ) I. Jot. that the 1EZpCD~ is 

R t 298 

• IncUcat.a a chana. trOIS the previous I'm.l avaluatica (Jl'L &5-37). s.au round-of! chan&e. 

have beoa SIAd. tor .avaral _tri.a 1D tha tabla: theaa are 1Iat. -"eo! ~ .. tariaka. 

I IndJ.cat.a a n .. entry that ... not 1D the pravioaa ."aluatica. 

" IncUcat.a • chma. 1D tha Jota. 

30 

~, 

~ 

A2, All 

AZ, All 

A2, All 

A2, A12 

A2, Al2 

A2, A12 

A2, Al3 

I~ 

. --

r+ 

1 
) 

~ --- ~------------------- ------- --.-----~--. ----- - ---" 

·i 

, . 

• .. ' 

-) 

~ 

~ 

' . 

.. 

;,.-

~ 

J":-

. ~ ... ;; 

.. : 

, 

~ 

,t 

'* 

~ 

-rable-r. -(Continued) 

Ruction A-l.etor' EIB±(glR) 1«291 Xl t(29llb !fotA. 

&. BOZ T OOz .. 1Iz02 T 0z 

H 

.. lIz0z T 02 

* B02 T 03 .. 08 T 202 

II T 0z .. 110 T ° 

II T 03 "lIOTOZ 

-II T 110 "'lIz + ° 

&.II T IIOZ "IIZ0 T O 

H 

o T 110" 1102 

*OTMOZ "1I0T02 

H ° T MOZ .. 1103 

° T 1103 .. 0z T !IOz 

o T IIZ05 .. products 

° T 1!II03 .. OB T 503 

° T B02110Z .. product. 

°3TIIO"IIOZTOZ 

&. 110 T BOZ .. MOZ T OB 

_* II~~ 1I()3_"_ ~2 

H~ 

OB T 110 .. BOlIO 

H 

OS T IIOZ .. 1!lI03 

• Units sr. cm3,.,leeulr •• c. 

2.3xl0-13 -(500±200) 

1.7Xl0-33 [H) -(100ot400) 

1.1xl0-14 

4.1xl0-12 

3.4il0-11 

(s •• Table 2)-

6.5J:10-1Z 

(s •• Table 2) 

1.0Xl0-11 

7.lxl0-11 

Z.Oxl0-12 

3.7xl0-U 

1.7xl0-11 

(5 •• Table Z) 

(5 .. Table Z) 

500 50ot100 

"x Beacttem. 

3Z00±400 

0±100 

-(120±UO) 

0±1.50 

3400±7.50 

1400±200 

-(Z40±80J 

-(150±100) 

1.7xl0-1Z 1.3 

4.Slzl0-32[H) 1.3 

Z.Oxl0-15 1.3 

a.Slz10- 17 -- 1.Z5 

<1. 0x10-15 

3.4J:10-11 - 1.3 

3. Oxl0-U 3.0 

9.7J:10-1Z 1.1 

1.0xl0-11 1.5 

<3.Orl0-16 

<3.Oxl0-17 

8.6xl0-16 3.0 

1. Sxl0-14 1.Z 

a.3xlo-12 1.Z 

Z.SlzIO-11 1.3 

b t(298) is the unc.rt.inty .t 2981:. To c.lculate the ""c.rt.iDty .t other temper.tur ... 

u .. the .xpre.dOll: t(T) - t(29a) up t g ( 1 - -L ) t. lIota that the 'xpOIleDt. is 

ab.olut.. v.lu •• Il T Z98 

* llIAUc.t. ... chm&. fie.- the previoaa Pan.l eval.uat.ioa (JPL 85-37). s.aU round-ott ch..,. •• 

hav. b .. D ...s. tor .everel IDtri .. 1D the table; th ... are DOt. auk'" by .. terlu •• 

, lDdic.ta •• _ IDtry that. ... DOt. 1D the prenoua waluatiOD. 

&. llIAUc.t. ••• chm&. in the lat. •• 

31 

/'~-

./ 

----------

311 

311 

3U 

Cl 

C2 

C3 

C4 

C5 

C6 

C7 

ca 

C9 

CIO 

Cll 

CU 

" 

.. 

;,. 

j 

- -1t; 
r. 

• 

) 

/ 

.' 

. J .. 

.. 

~ 

Table 1. (Continued) 

Resctlm A-f,ctor ' !lRteAEIB) teZil! Ii) tc29§)b 

&. OR + D)3 .. &,.0 + 1103 (S •• lot. C13 aDd ~ b.1Dw) 1.3 

&. OR + IIlr-02 .. product.. 1.31:10-U _(3S~270) SOo 4.I5Xl0-12 1.S 

H 

i!Oz + 102 .. OOz1D2 (S •• tabla Z) 

03 + 102 .. 1t03 + 02 1.~xl0-13 ZSOCH:140 3.:Xl0-17 1.1S 

03 + 11m2 .. O2 + HB03 

-111 .. <S.Cb:l0· -" 

H 

002 + 103 .. 1IZO, (S .. tabl. Z) 

.. &. .l!zOs + a,.0 .. 2Bl!>3 <2. Cb:l0-:,1 

&. OR + m, .. BZO + IIBZ 3.6xl0-U 1130%200 1.6xl0-13 1.4 

II!Iz + IIlZ .. product. 3.41:10-11 2.0 -------- -

& NBZ + 10 .. prociuct. . 3.~10-U -(450±150) - l.-:7Xlo-11 Z.O 

&. KH2 + !O2 .. product. 2.1xl0-12 -(1550%250) 1.lIxl0-11 3.0 

& NB2 + 0z .. product~ <3.0Xl0-18 

lIH2 • 03 .. product.. ~.ax10-12 ~30:t500 2.1:1:10- 13 3.0 

HYdrocarbon Reactlons 

* OB + CO .. CO2 + B -13 1.5xlO (l+O.6Patm) 0%300 1. 5xlO-13 (1+0. 6P.tm) 1.3 

OB + CR4 .. CB3 + &,.0 Z.3xlO-12 l70~00 7.7x10-1S 1.2 

f oe + 13CR4 .. 13ea, + Bz0 (S •• lIot.) 

OB + CzB6 .. B20 + C2B5 1.1xl0-11 110 0±20 0 2.8Xl0-13 1.Z 

a Units ar.-cm3/lDOlacul.-•• c.' 

b '(298) i. the unc.rt.aint.y .t 29m(. To c~lcul.t. the unc.rtainty .t oLb.r temperatur •• , 

us. the 'xpression: '(t) - '(Z98) .xp I ~ ( 1 - __ 1 __ ) \. 1I0t. that the .xpon.nt is 

absolnta v.1u.. It T Z98 

)!ot •• 

C13 

C1S 

---CllSC17 

C18 

C19 

C20 

C21 

C22 

C23 

01 

oz 

03 

04 

• Indicata. a CI1an&' 'rOlll the pnvious Pan.l waluAt.ion (JPL 85-37). s.rs.ll rouod-o" ch""os 

have b .... _d. 'or • ..,.ra1 antri •• in the t.abl.; th ••• are not ~ad by .. t..rlslt •• 

f Indic.ta. a now ... t.ry th.t ... not in th. prwiou.a ..,.luatlon. 

&. Indic.ta •• cban&' in th. lIot •• 

~ CB + D)3 pr ... ur. and t~ratur. depend ... c. !it by 

( -lS k [HI ) ko - 7.Z x !O arp(785/T) 

kCH. T) - ko + 3 with l kZ - ~.1 x 10-16 arp(1440/t) 

k 3 [HI k3 - 1.9 x 10-33 'xp(7Z5/t) 

1+-

kZ 

32 

~ 

f 

--

-4' 

\! 
,_ ':<i>¥'\:' -~ -- ~ .. " ... .-----.---==~.~~ --_______ . ____ ~~~~-_~~~ 

-) 

. . 

II 

, 

It 

If 

~ 

" ~ 

! 

" 

~ 

~ 

) 

Table 1. (Continued) 

RnctlQII A-'ao:tora _ !.lti.u.!.lRL ___ t12IJa 1:) _ fC29S)b __ IIot •• 

• 011 + SHS .. Hzo + C3B7 1.4Z10-11 7S0±200 1.1z10-12 1.3 

011 + CiJ4 .. producta (Sa. Tabla 2) 

011 + CzHz .. product. (S.a Table 2) 

011 + fL;.al .. fL;.0 + IC) 1. Oxl0-11 0±200 1. Ox10-11 1.25 

, 011 +_ Cll:J(3) .. CB3~ + H20 _ . II.Oxl0-12 -(250±200) 1.4z10-11 1.4 

011 + Cll:JOCB .. product. 1.0z10-11 0±200 1.Oxl0-11 Z.O 

OR + Bel .. product. 1.2z10 -13 400%150 3.1z10-U 3.0 

os + Cll:JCJI .. product. 4.5z10-13 900:400 Z.2z10-U Z.O 

IIOZ + CHzO .. adduct 4.Sz10-14 10.0 

# 0 + IICII .... prociucta-- 1.0zl0-11. 4000%1000 -- -1.Sz10-17 10.0 

o + CzHz .. product. 3.0z10-11 1600%250 1.4z10-13 1.3 

o + BZCO .. producta 3.4Z10-11 1600%250 1.lIzl0-13 1.Z5 

I ° + CH3CBO .. ClI3CO + CD 1.8zl0-11 1100:1:200 4.5z10-13 1.2S 

° + CH3 .. product. 1.1Z10-10 0%250 1.1z10-1O 1.3 

CB3 + 0Z" product. <3.0%10-16 

H ~ + 0z .. CB30Z (s •• Table 2) 

• CBZOD + Oz .. CB20 + IIOZ 9.6z10-12 01:500 9.6z10-12 1.3 

• ~O + 02 .. CB20 + 1102 3.9z10-14 900:t300 1.9z10-lS 1.S 

BOO-'" 0z -.. CO +802 3.~Z10-12 -(140:140) 5. Sz10'';12 1.3 

CB3 + 03 .. producta S.4zl0-12 220tlSO 2.6zl0-12 Z.O 

* CB302 + 03 .. product. <3. Oxl0-17 

a Unit. are cm3/mal.cul.-•• c. 

b !(298) i. the unc.rtainty It Z98E. 

u •• the erpr •• aion: f(T) - f(Z98, 

ab.olute value. 

To calculat. the unclrtainty at othar temperatur.s. 

up I ~ ( 1 - -L ) I. Bot. that the exponent 11 

R T 298 

* Indicatea a chana. frCIIII thl previ ..... Panel evlluat101l (JPL 85-37). Soaall roomd-o!! cbm& .. 

h"". b.ea IIId. for .ev.ral entri •• in the tabla; th ••• are not marltacl by uteri.t •• 

I Indic.te. a n_ eatry that wa. not in the prrrlou. ""aluation. 

& Indicate. a chana. in the Jot •• 

33 

D5 

Dfi 

D7 

DI 

D9 

D10 

Dll 

D12 

D13 

D14 

D1S 

D16 

D17 

D1S 

D19 

D20 

D21 

D22 

r. 

~/ 

;ll~ • .-~-' ----' \ r 
-&~., .--.. --.----.-..... -.----~ r .'1.\""'- ,-," . 

-. "" . . . - -- ._---" ... _------.-

.----.... -.. _--._----.-.... -.. -..... . . --------------.------ -.-- --~-- .-.... 

) 

Table l. (Continued)-

Ruet.ion __ A-"tlQ~ __ ..EJIl±(AEIR) );(2911 1:) t(Z9I1L lIot .. 

.. 

:;.-

;;;-

I" 

:. " 

.r 

. ") _:a 

r-U . ..:1r -

* ~oz + ~oz 4 produc:.a 

CB30Z + 110 .. ~O + 110% 

H 

~02 + 110% 4 ~0"J!'Oz 

~02 + 80% 4 ~008 + O2 

* 003 + co .. product.. 

1103 + CB%O .. procluc:t.. 

, 1103 !. cs,CUO ... products 

& Cl + 03 4 ClO + 0z 

Cl + B2 .. SCl + B 

Cl + CB4 .. SCl + CB3 

Cl + CiJ6 .. DCl + C2BS 

Cl + C3B8 4 BCl + C3B7 

Cl + CiJ% .. product.. 

* Cl + CB30B .. CHzOll + BCl 

Cl + ~Cl .. CHzCl + BCl 

Cl + CB3CH .. product. 

Cl + ~cc~ 4 CHzCC~ + 11:1 

Cl + BZCO 4 DCl + IICO 

Cl + BZO% 4 DCl + 00% 

& Cl + !lXl .. Clz + OIl 

• Unit.s are aa3'8Dl.CII1.-s.e. 

1,azlO-13 -(220±220) 

4.2xl0-12 -(laot180) 

(S_ Tabl. 2) 

-14 500 7,7s10 -(130~1300 

1.4x10-12 190WOO 

ClOs Ruction • 

2.9x10-11 26~100 

3:7rlO-11 2300%200 

1.1xlO-11 1400:1:150 

7.7s10-11 90:1:110 

1.4:1::0'10 -(40%250) 

(Se. Tabl. 2) 

S.7rlO-ll 0%250-

3.3x10-11 1250%200 

8.1xlO-ll 30:1:100· 

1.WO-ll 980:1:500 

3. 0xl0-12 130%250 

4.Oxl0-13 1.5 

7.6xl0-12 1.2 

6.Oxl0-12 3.0 

.<4. Oxl0-111 

II. Oxl0-1S 1.S 

2.4x10-1S 1.3 

1.2xl0-11 1.15 

r.6Z10-14 1.15 

1. Oxl0-13 1.1 

S.7x10-11 1.1 

:..6X10-10 1.5 

S;7x10-11 1.5 

4.9%10- 13 1.2 

<%.OS10-15 

<4.0xl0-14 

7 .3x1o::.~1 -- . 1.15 

4.1xl0-13 1.5 

1.9%10-12 2.0 

b !(21111) 1. th. uac.rt.a1nt,. at. 21111X. To cal.cuut. th. IIDC.rtaiDt.,. .t. other t.aaperat.ur ••• 

.... th. expn.doa: f(T) - f(298) up I g 1 - -L ) I. iotA that. th •• zpoo&Ilt. is 

absolut.. valli •• R T 2118 

D23 

D24 

D15 

D26 

D27 

D28 

El 

-E2 

E3 

E4 

ES 

·E6 

E7 

E8 

E9 

£10 

Ell 

E12 

.. IDd1c.t... • c:hm&. frca tb. prrnoua Pm.l evaluat.ioa (JPL '5-37). s..u rOUDd-off chana •• 

haY. bem aade for ._.ral mtri •• ill th. t.abla: th ••• are DOe aad:ad by .. tArim. 

, Iodie.t. •• a n_ .oUT that ••• _to ill th. previOllS _al ... t.iCID. 

of. Iodicat... a c:hm&. 1D the Iot. •• 

34 

- --------------

.-

• & 

'li 

... 
.. z~·-·'· ---- ..... . ...... -... , ..... _... .. "-y --- •• - •. -~ 

. I 

i ) I 

Table 1. (Continued) 

R.actlon A-Faet.ol'a _____ ~_~~ __ t(298Ib _ l'otes 

, 

Cl ... HII03 4 producta <1.7z10-14 Ell 

" Cl ... 11)2 4 11:1 ... 02 1.8ltl0-11 -(170t200) 3.2zl0-11 1.5 E14 

~ 4.1xlO-11 1I.1z10-12 4 CS + ClO 4S0i:200 2.0 El4 

Cl + C~O - C~ + ClO 1I.8z10-11 0t250 G.blO-11 1.2 E15 

- ~- -.~ - Cl ... OClO - ClO + ClD 5;8x10 -11 __ 0t250 5.adO-1.

1 1.25 .E16 

Cl ... CJ.Ga)2 4 pl'oducta 5.5%10-12 -(1~) 1.2:1:10-11 1.3 E17 

Cl ... 110 " - JIOCl-- (S.a Table Zl 

. " ~ Cl ... IOZ - ClOIIJ (ClJI)Z) (S.a Table Z) 

... • Cl + 103 - ClO + IIOZ .5.2xlO-ll 0±400 5.2:1:10-11 Z.O E18 .' , -r 

• . t"!' 

, Cl ... 820 - ClO + 12 (S •• Jota) nil 

• Cl ... ClIO - JIO + C~ 6.0xlO-11 ~~ 5.Dz10-11 Z.O UO 

Cl + 0z -" ClOD (S •• Tabla 2) 

Cl ... ClOO 4 C1Z ... 0z 1.4x10-1O 0+...230 1.4x10 -10 3.0 EZ1 

- CLO + CLO 8.0z10-12 ot2.5O 5.Dz10-12 3.0 Ul 

• CLO + ° 4 Cl ... 0z 3.0%10-11 -(70t70) 3.8%10-11 1.2 Ell 

CLO ... 110 - IIOZ + C1 6.4%10-12 -(290±l00) 1.7x10-11 1.15 E23 

H 

CLO ... IOZ 4 ClOllOZ _ (S .. Table Z) 

CLO ... 103 4 pl'oducta 4.0z10-13 0±400 4.Dz10-13 Z.O EZ4 

" CLO + IJJZ - HOCl + 0z 4.8xl0-13 -(70~0) 00 5.Dzl0-1Z . - -1~4 EZ5 

:: . ..-' CLO ... BzCO • producta _1.0z10-12 >Z100 <1.Dzl0-15 U6 

• CLO + C8 - producta 1.1x10-U -(~) 1.7zl0-11 1.5 E27 

a Unit_ are ca3/molecula-.ec. 

:/ b t(ZIIS) is the UDcarta1Dty at ~. To cal.culat.e tbe _art.aiDty at other t.e.p&ratura •• 

.... the axpr ••• 1oa: f(T) • f(298) up 1 g ( 1 - -1- ) I. Iota that the apoDeDt 1 • 

abaoluta val.ue. Il T %SIS 

• IDd1cata. a chan&e !rca the pnrlous 1'_1 evalDatloa (JPL 85-37). s.au roaad-oU chGJa .. 

~a bee -.ada for __ ral .aula. 1D tbe table: tbea. are _t ..uecl by utarlaka. 

:'" I Indicates a n_ eDtry that ... not 1D the previous ..,aluatica. 

:. " Indicates. chana. in the 1Iota. 

35 

~.) ... 1 

Q! 
~ ""'-"\ ------- --

Tabre 1. (Contlnued) 

-) ~ioa A-r.ctor· zmcUII> :tUlLE) ___ t(Z8S)b "ote. 

ClO .. CB4 4 producta -1. Oz10-12. >3700 <4.0z10-1S 

ClO .. B:z 4 producta -1. Oz10-12. >4800 <1.0z10-18 

ClO .. (X) 4 product. -1. Oz10-12. >3700 <4. Oz10-lS 

ClO .. -2.° 4 product. -1. Oz10-12. >4300 <s.0z10-18 

~ ClO .. ClO 4 product. S.0z10-1~ 12.~0 .. 1.2%10-14. - 2.0 

~ 

"',7'r -... 

ClO .. 03 4 ClOO .. 02 1. Oz10-12. >4000 

4_OClO " 02 __ _ 1. Oz10-12. >4000 

• 011 .. C~ 4 SX:l .. Cl 1.4Z10-12 800±400 

• 011 .. DCl 4 ~O .. Cl 2.8z10-12. 3'0±100 

-. 011 .. IIOCl" ~O .. ClO :;:02:10-12 - - 'O~OO 

011 .. ~Cl .. CH2Cl .. Hz0 1.7z10-12 1100±200 

011 .. CB2Cl2 .. CBCl2 .. H

2

0 4.7z10-12 10'0±200 

OH + CBCl3 .. CC13 + H20 3.4Z10-12 10S0±200 

011 .. CBFCl2 .. CPClz .. H20 S.8z10-13 1000±200 

011 + CJIP 2C1 .. r:I 2Cl .. H20 S.3z10-13 1"0±200 

011 + CB2ClF .. CBClF .. H

2

0 2.1%10-12 11'0±1'0 

011 + CB3CCl3 .. CH2CCl3 .. H20 S.0z10-12 1800±ZOO 

-12 # 011 + CB3CF2C1 .. CH2

CFzCl + HzO 1 • .5zl0 lSOO±ZOO 

- .- - - - . - -12 , OH + CB3

CJIPZ .. product. 1.9z10 

, 011 + CBClzr:l3 .. CCIzCF3 + H

2

0 1.1%10-12. 

-13 , 011 + CBClFCF3 .. CClFCF3 + HZO 7.2z10 

a Unit. are cm3/DOl.cul.-•• c. 

lZ00±300 

10'0±300 

12.'0±300 

<1.0z10-lS 

<1.0z10-18 

8.7zl0-14 1.2 

8. Oz10-13 1.3 

,.~10-13 3.0 

4.3zl0-14 1.Z 

1.4zl0-13 1.2 

1.0zl0-13 1.Z 

3.0z10-14 1.3 

4.lIzlO-1S- 1.Z 

4.4zl0-14 1.Z 

1.2%10-14 1.3 

3.8zl0-1

' 1.3 

3. 4zl0;-14 .. 1.3 

3.2%10-14 1.3 

1.1%10-14 1.3 

b C(Z98) i. the uncerteinty .t 2g~. 

ua. the azpr ••• loa: f(T)· C(ZgS) 

To calculate the unc.rtainty .t ath.r tamper.tur •• , 

azp I M ( 1 - -l.. ) I. "ate that the .:rponent is 

ab • .,lute v.lue. Il T 2gS 

• Indicate •• chll!&' frcao the pravioua Pan.l evalu.tiaa (JPL 8'-37). Solan rOllDd-aff chanaes 

hay. bean made Cor .evaral entrie. in the tabla; th ... are not aadtacl by .. tni.k •• 

# Indic.te. a n .. entry that .11 not. in the previous lV.lu.tion. 

• Indic.t.e. • chll!&e in the "at.e. 

36 

us 

us 

us 

us 

U8 

co 

!30 

E31 

ElZ 

El3 

E34 

!34 

E34 

E34 

E34 

E34 

E3' 

E36 

E3i 

El8 

El9 

.~~ 

! 

I , 

!~: 

fL 

~ 
4 ". 

.. 

,,-

; 

j 

i 

<' '. 1 

-; 

y:-

y: 

, .. : . 

. ., 

" ~ 

~-

J 

• 

."...~",,", 

. :,' 

Table-l. -(Continued)-

b "Ictloa A-rlctora IIRtCAElRl k(Z88 Xl _~(Z~81 "ot •• 

I C8 + ~Cux:llz • CB:l.CClJ'z + ~o 3.4z10-12 11S0D±300 1.8z10-14 2.0 

I C8 + ~3 • CI!l'CJ'3 + ~o 1S.8z10-13 130D±300 8.4z10-15 1.5 

I C8 + ~a;t,!. ~a;t,! + H20 3.4z10-12 1IS0~00 a.Osl0-15 3.0 

C8+CZC14 .~ 1I.4z10-12 1200±200 1.7z10-13 1.25 

CiI" C?=~ • products 4.1IZ10-13 -(4~0±200) Z~2z10-12- - 1.25 

C8 + crc~ • ~t.. -1. 0s10-12 >3700 <5. 0s10-1a 

-- C8 + CF zClz • prodacts --_1.0Z10-1Z- >31S00 -<IS.Dz10~la -

C8 + ClCIIOZ • products 1.2z10-12 330±200 3.9z10-13 1.5 

-0 + 1IC1 .. OS + Cl 1. 0s10-11 330D±350 1. 51I:l0-11S 2.0 

o + BXl .. C8 + ClD 1.0dO-11 2200±1000 IS.OsI0-15 10.0 

o + ClCIIOz .. product.s 2.9z10-12 800±200 Z.0s10-13 1.5 

o + ClzO • C10 + C10 Z.9z10-11 1S30±200 3.5zl0-12 1.4 

o + OClD .. ClO + 0z Z.8z10-11 1Z00±300 ~.OzlO-13 Z.O 

I C8 + OClO .. 1IX:1 + 02 4.~zlO-13 -(800±200) 1S.8Z10-12 2.0 

110 + OClD .. IIOZ + ClO Z.5zl0-12 1S00±300 3.4zl0-13 2.0 

* 11:1 + C1OIIOZ .. product. <1. 0s10-Z0 

_11:1 + OOz"OZ .. products <1. 0s10-Z0 

I ~O + ClOlIOZ .. products <Z.0s10-21 

BrOz R •• ctiens 

* !r+03 -BrD + 02 1.7Z10-11 800±200 1.2z10-12 1.2 

* !r + lIz0z .. IIBr + Bl2 1.0zl0-11 >3000 <5.0s10-16 

a lhlits ara cal/lIIOlecule-s ... 

b !(~8) 1s tha UDcart.atnty at ZII8X. to calculat. tha UDcarta1nty at othar temperaturas. 

u .. the azpre .. loa: !(t) - !(29a) asp 1 A1< ( 1 - -1- ) I. lIota that u,. nponmt 1a 

absolute valua. It t 211a 

* IDd1cat.a. a chan&. be. tha prevlous Panal evaluatloa (JPL 85-37). Soaall round-ott cb&n&es 

h.na been JUde tor s."aral entrla. in tha tabla: tha.a ua not lllUkacl by a.tadus. 

I IDd1cat.as a new entry that ... not In tha prevlous evaluatloa. 

to IDd1cat.a. a chan&. in tha lot •• 

37 

140 

141 

142 

143 

144 

145 

145 

146 

147 

148 

E49 

150 

E~l 

152 

153 

154 

1~5 

1~6 

_FL 

F2 

·"1 

.' 

.. 

~ 

-1 

• 
~!\.~....-:" ••• '.' ~ 

' .. 

) 

Table l. (Continued) 

.. 

- R •• ct12!l 6-la~~"a l:LBiUA:an Is'Z9S II mHlb he. 

,. Br + B2

C1J .. BBr + IICO 1.7xl0-11 SOOUOO 1.1xl0-12 1.3 Fl 

.. - 1.'xlO-11 2.0%10-12 • Br + 11)% .. BBr + O2 6OoteOO %.0 n 

# Br + c~o .. BrCl + ClO 3.SxlO-12 %.0 rs 

-- _. --

BrO + 0 .. Br + oz 3. Ox10-11 OU50 3.0%10-11 3.0 n 

" BrC + ClO .. Br + OClO 8.7x10-12 0U50 8.7z10-12 1.5 F7 

.. Br + ClOD 8.7xlO-12 OU50 8.7xlO-12 1.5 F7 

BrC + 110 .. 110% + Br 8.8xlO-1% -(%60%130) %.1xl0-11 1.15 Fa l 

l _H ~ 

Br<) + 110% ~ BrOM02 (s •• Tabla~) 

BrO + BrO .. % Br + 0% 1.4xlO-12 -(150t150) %.3xlO-12 1.~ n 

.. Br% + 0% 8.0xlO-14 -(600%600) 4.4xlO-13 1.~ n 

BrO + 03 .. Br + 20Z -1.0x10-1% >1600 <,.Ox10-1S r" 

BrO + 80% .. product. 5.0%10-12 3.0 F1! 

1.0xlO-11 I 

BrO + DB .. product. 5.0 F12 

• OS + Br% .. BOBr + Br 4.2z10-l1 oteOo 4.2z10-11 1.3 F13 

" OB + BBr .. H%O + Br 1.1x10-11 OUSO 1.1x10-11 1.% F1' 

oa + CB3Br .. CB2

Br + B%O 8.0x10-13 S%OUOO 3.8x10-14 1.~ F15 

0+ BBr" OB_~ Br -1% 8.1%10- . l'SOUOO 3.7z10-14 1.3- FlS' 

FOz Reaction. 

;;" , + 03 .. FO + 02 2.8xlO-11 %lOUOO 1.3z10-11 2.0 G1 

F+B2 "BF+B 1.'xlO-1O '2OUSO Z.7z10-11 1.3 GZ 

, + CB4 .. BF + ~ 3.0xlO-1O 400%300 8.0XI0-11 1.5 G3 

,;;; 

a ODit. are ca3/.alecul.-•• c. 

b t(Z98) i. the unc.rtainty at Z9SE. To calculata the UDcartaiDty at oth.r e-parat.uns. 

us. the azpr ••• ioa: f(T) - f(Za8) up 1 ~ ( 1 - -1..) I. JIote that the azpoaeat is 

ab.olut. valu •• Il T 298 

r. • Indicat •• a chm&. frDIII the pr..,io.g Peal ..,aluat1ca (JPL 85-37). s.aU rouDd-oU d1an& •• 

:0 have b.au ....s. for • ..,er.l mtd •• iD the tabl.: the .. u. ~ aad:ad 117 at.riu •• 

# Indicat •• a D" mt.%)' that ... DOt iD the previo.g rn1uatica. 

" IDdicat.. • chm&. iD the lIot •• ( 

i) 38 G 

.. -~ 

~-
.......... -.'-"\ 

) 

-I 

---t-- .-

! 

, 

-" 

-/ 

Y . . . ~-­ ":. 

'., 

• 

)

r-

~ 

~ 

'~" 

--

Table 1. (Continued) 

R .. ctlon _ ___ A-Factor· r:1R;t(U/R) );(298 lC) !(29J11b 

·r+~o"BF+CII 

H 

r + 0z .. iOZ 

H 

r + \10 .. FJIO 

-' -"- -- _. _ .. r + NOZ .. ~(rato) 

ItO + iO .. IIOz + r 

- FO+iO"Zr+OZ 

FO+03 .. r+zoZ 

.. FOz + °z 

H 

FO + IIOZ .. ftB)Z 

o+ro .. r+oZ 

O+roZ"FO+OZ 

a 3

0Z + NO .. a 3

0 + NOZ 

C7ZC10Z + ItO .. CFZClO + IOZ 

C'C1ZOZ + ItO .. CFClzO + IOZ 

a:~OZ + NO" a:~O .. .,z 

" ce + HZS .. sa + HZO 

* ce + OCS .. ~ct. 

" ce + CS2 .. product. 

H 

ce + S02 .. iIlSOZ 

O+BzS .. ce+SB 

a tIIlita are .. 3'80laeu1_. 

4.8xlO-11 

(s •• Toble Z) 

(S •• Table Z) 

(S •• Tobb Z) 

Z.8x1O-11 

1.5x1O-11 

(S •• lot.) 

(S •• lot.) 

(S .. Tobb Z) 

5.0x1D-ll 

5. 0zl0-11 

3.9%1.0- 1Z 

3.lx10-1Z 

3.5%10-1Z 

5.7x10-1Z 

5.9%1.0-12 

lolx10- i3 

(S •• Jot.) 

(Sa. Tabla 2) 

9.2xl0-12 

400:1:200 1.2x10-11 1.5 

o±250 Z.8X10-11 2.0 

0:1:2.50 1.5x10-11 .3.0 

0%250 5.0x10-11 3.0 

0%250 5.0X10-11 5.0 

-(400:1:200) 1.!%10-11 1.3 

-(500%200) 1.8xlO-11 1.3 

-(430%200) 1.5x10-11 1.3 

-(330%200) 1.7%10-11 1.3 

SOx Reactlona 

70±70 4.7%10- 12 1.Z 

LZOO±500 1.9%10-15 2.0 

1800±550 Z.2x10-H 1.7 

b !(298) 1. the UDcart.a1Dty .t. Z981:. To calculate the UDearta1nty at other t.aparaturas, 

.... the upna.1011: !tT) - f(Z98) up I M ( 1 - J... ) \. lote that tha axponent is 

... olut.a vaLa.. R T 298 

• lAdlcat.a •• chaz>&. fr.- tha F_loaa Pan.l ..,alaaUoa (JPt. 85-37). Small round-ott chana .. 

hav. b._ ~ tor ._al _trl .. in the tabla; th ••• are rIOt ...u.s by aat.adalta. 

I lAdlcat ••• _ 811~ tZlat " .. DOt in the prav1~ ..,alaatloa. 

&. !:Idleate. a chaz>&a 1D eM Iota • 

39 

. ---' ---- --- '--

'\;! 

Notes 

G4 

G5 

G6 

G7 

G7 

G8 

G9 

G10 

G10 

G10 

G10 

81 

HZ 

83 

84 

:-* 

.. 

• 

• L _______ __ 

--
... 

......... -. 

J_ .~.,- -

tI! ,":r. -'-,' ", . __ 1t~_' _ _ ._ 

") 

It 

. 

.. 

' . • 

;;,-

~ 

.r. 

• '!' .. 

:i 

" 

oj 

)

' .r: 

~ 

~ 

-----

Table 1. (Continued) 

Ruo:.tim1A-'lctorl EIlJ:tCAlIlU tCZU .. .Xl_ !.f298)b Rot os 

O+ocs-co+5O Z.1xl0-11 Z20~ 1.3z10-14 1.Z 

O+CSZ-cs+5O 3.ZX10-11 1I~13O 3.lIz10-U 1.Z 

5+0Z -5O+0 Z.3z10-U OiZOO Z.3z10-U 1.Z 

S+03- 5O + 0Z 1.2z10-11 z.O 

S+OS-5O+B 1I.lIzl0-11 3.0 

SO+Oz-SOZ+o Z.lIzl0-13 Z40~O 1.4Z10-17 2.0 

so + 03 - SOz + 0z 3.lIzlO-U 110otzOO 1I.0z10-14 1.Z 

SO+08-SOZ +9 1I.lSdO-ll z.O 

so + IIOZ 0-' SOz + NO 1.4zl0-11• ~O 1.4Z10-llo 1.: 

* so + ClO - SOz + Cl Z.lIzlO-ll ~O 2.8z10-ll 1.3 

so + OClO - SOz + ClO 1.Slzl0-12 3.0 

* so + BrO 4 so:: + Br 5.7dO-ll 1.4 

SOz + 90Z - products <1.0dO-1B 

SOz + CB30Z - product. <5.0dO-17 

S02 + 1I0Z - products <Z.OdO-26 

S03 + 1I0Z .. products 1.0dO-111 10.0 

I SOz + 1103 .. products <7.0dO-2I 

:?Oz ~ 03 - S03 + 0z 3.0z10-1Z >7000 <2.0dO-22 

* Cl + 9ZS .. acl + SH 5.7zl0-11 ~O 5.7dO-ll 1.3 

&. Cl + OCS .. SCl + CO <1.0xl0-16 

C10 + OCS .. product. <2. Oz10-115 

a Units are aD3/molecule-sac. 

b !(29B) h tba uncertainty It Z98lt. 

u •• tb. expr ••• ion: f(T) - f(29I) 

absolute vllu •• 

To calculata tha unc.rtainty It otber temparltures. 

azp I g ( ! - ..L ) I. lIot. tbat tb. exponent is 

II T 298 

* Indicat .. I chan&' frOID tha prari ..... P .... l ..,aluati_ (JPL 15-37). Small round-of! chana .. 

have been _de !or IlVeral mtri .. in tb. tabla; th ... ara not lUrked by nterhka. 

I Indicat .. a new IIItry that was DOt in tb. pr..,i ..... ."Ilultion • 

&. Indicate. a chan&' in tbe lIot •• 

40 

..-

-.. -

95 

HIS 

H7 

H8 

H9 

910 

911 

H1Z 

913 

914 

H1S 

H16 

H17 

91B 

919 

B19 

920 

BZl 

922 

923 

924 

_o\~ 

, . 

--

• 

~, 
y:. ,." .. .,_.- ,. 

) 

,. 

j; 

.-----

;.-:.~ 

:-:-1 

~ 

r: 

, , 

:. 

! 

)! 

~ 

-.. -._- .-.. _-----_ .. _--------

Table 1. (Continued) 

Reaction ____ A--F_G~a tll!:t CAEIR 1 k(2Q& Xl !(298)b 

ClO + S02 .. Cl + S03 

SB + Bz02 .. producta 

SB+O"S+SO 

* SB.+ 02"! 08.+ ~ 

*SB+03 "SSO+02 

• SB + 1102 .. ~ + 110 

H 

SB + 110 .. lIS1IO 

# BSO + NO .. products 

9.7:11:10-U 

2.9:11:10-11 

(S •• Table 2) 

<4. 0s10-18 

<S.0s10-lS 

1.lIslO-10 5.0 

<4.0s10-19 

280%200 3.&slO-U 1.3 

-(240±100) 11.5:11:10-11 1.3 

<1.0s10-1S 

"ota. 

824 

825 

8211 

827 

S28 

829 

B30 

# BSO '+ NOZ .. BS02 + NO 9.IIX1~2 2-;0 --.. '··-830 

# BSO + 02 .. products <2.0:11:10-17 

&SO + 03 .. products 1.0sl0-13 5.0 

, !!S02 + 02 - !!O2 + 502 3.0:11:10-13 3.0 

• B0S02 + 02 - 1Il2 + S03 1.3x10-U 330:1:200 4.4:11:10-13 1.2 

I SZS + N03 .. product. <3.0s10-14 

CS + 02 .. OCS + ° 2.9:11:10-19 2.0 

CS + 03 .. OCS + 02 3.0:10-16 3.0 

CS + N02 .. OCS + NO 7.6x10-17 3.0 

MetaL Reactions 

H 

Ifa + 02 .. N.o2 (S .. Table 2) 

&. !fa + 03 .. N.o + 02 S:II:l0-10 0:1400 S.0s10-10 1.S 

H.o2 + ° <3:11:10- 11 0:1400 <3. 0s10-11 

a Units ar. aa3'lIOlacul.-sac. 

b !(298) is the uncertainty at 298X. To calculate the uncertainty at. other temperaturws, 

use the .:pre.alon: 

absclut. value. 

t(T) - !(298) up 1 g ( 1 - ...L) I. Jot. that. the exponent. is 

Il T 29& 

* IMicah. a chan&e !rom the previous Pmel evaluation (JPL 85-37). Small round-ott ehan&as 

haTe bean made tor several antri.s in the table; the .. are not. marked by asterisks. 

I IMicate. a ~ entry that was not. in the previous eveluat.ion. 

&. IMicate. a chan&a in the 'ote. 

41 

B30 

B31 

832 

B33 

B34 

B35 

B36 

B36 

Jl 

Jl 

~ 

r 

~ )t 

\: 
._ 

~ • .:.X.:... ~ .. 

) 

.. 

.. 

• 

,: 

~ 

:;,-

-:/ 

yo 

, . :. 

-! 

J 

,I 

J -,., 

~ 

.- -

Table 1. (Continued) 

React!S!!] A-F.e~,,· !:a:;'~£Bl !5'Z98 Xl ~'298lb 

1 Ife + 1120 .. lfaO + liz 2.4xl0-1O 1600±400 1.1xl0-12 1.3 

, Ife + Clz .. lfaCl + Cl 7.3dO-1O WOO 7.3xl0-1O 1.3 

l.aO+0"lIe+02 3.7xl0-1O 0:1400 3.7xl0-1O 3.0 

H 

1 .aO + 02 .. ~~3 . _ (Saa tabla 2) 

- ~-.-. --

1 .aO + 03 .. lfa02 + 02 1.6dO-1O 0±400 1.6Xl0-1O 2.0 

.. Ife + 202 

6xl0-11' OiSOO 6.Oxl0-11 3.0 

1 .aa + liz .. lfaOB + B 2.6xl0-11 moo 2.6xl0-11 2.0 

'.'O+B2

O ... 'OB+OB 2.2%10-10 01400 2.2%10-10 2.0 

, llaO + 110 "-lie + N02 

-10 1.5xl0 _ 0:1400 -10 1.5xl0 _ __ 4.0 _ 

H , llaO + CO2 .. lIaC03 (Saa tabla 2) 

• .0 + OCl .. product. 2.8xl0-1O 01.00 2.8Xl0-1O 3.0 

I NaO, +NO" NaO + lIO, <10- U 

I If a02 + OCl .. produc ts 2.3xl0-1O 01.00 2.3xl0-1O 3.0 

lIaOH + OCl .. HaCl + H2O 2.8x10-1O 01.00 2.8X10-1O 3.0 

H 

I llaOH + COz .. RaBC03 (5 .. tabla 2) 

a Unit. ar. cm3/malacula-.ae. 

b ~(298) i. the uncertainty at 298le. to calculata tbe uncartainty at otber temparaturas. 

usa tbe ezpr .. aion: !(T) - !(298) axp 1 g ( 1 - _1_ ) I. lIote tbet tbe axponent is 

---absolute Value.· R _ T _ 298 

• Indicat .. a chan&e !rem the previous Pan.l evaluation (.JPL 85-37). Small round-of! chan&es 

have bean made for sevaral entrias in tba table; tb .. e ara not marked by asterisk •• 

, Indicat •• a new entry that was not in tbe-previou. evaluation. 

& Indicat •• a chan&e in the Kota. 

42 

~ 

Notes 

.12 

.13 

.1. 

.15 

. J5 

J6 

J7 

_J8_ 

J9 

J10 

J11 

JU 

f' 

. 

-

~ 

~ 

, ... 
"'~.--'-' --.-.-, .•. _' .. ,-_ .. _-, .... II! 

): 

.. 

.. 

,... 

~-

~:,' 

/;> 

Yi 

.~ ~ 

:, 

~ 

)i 

~ 

Al. 

NOTES TO TABLE 1 

° + 03' Tha recOlDllellded r.t.a upraaa10n ia from Wine li..!l. (1983) mel is • liDaar 1 ... t. squar .. 

fit. at all dat.. (=-iaht.ad) frca D..,is ~. (1973b), HcCraob mel Eautman (1V72), Wa.t. !i...!!. 

(1978), Arnold and Come. (1979), and Wine at. al. (1983). 

A2. 0(10) Ra.cUons. These racaa.lldat.iona ara buad co avaraa_ ot the ab.oluta r.t.a constant. 

.... ur_t.. raportad by Strait.~. (1975), D8Y1daco et. al. (1977) and Davidaon~. (1978) 

_~or H20, ~O".CU4' ~, .1'2,.°2 , ,03, __ B::l ... _cg4'" CFC!:J, a 2

c lz, ~, mel CO2 : b7' Amimoto at. d. 

(1978), AIIIiIDoto et. al. (1979), and Force and Wh ... t.ld (198la,b) tor "20' ~O, CU,,' " 2 , ~, ° 2 , 

° 3, CO2 , CC14, CFC~, a2clz' and a 4 : by Win. and R.avialumkara (1981, 1982, 1983) tor H20, ~O, 

H2 , ~, ° 3, CO2 , and CF20; by Brock and Wat.aco (private aaamJ.cat.iOD, 1980) tor H2 , 02 and CO2 ; 

by Lae mel Slmaer (1978 and 1979) tor D20 mel 02; and by Gericke and CaDes (1981) tor S2- The 

, -'t..i&lit.-of the 8Y1dence freiD th ••• sb.idie. iiidJ.c.t. •• that. the result.. of S.idner mel S .... in (1973), 

Seidn.r at. al. (1973) and Fletcher and au •• in (1975., 1976h) cant.a1n • ayse-t.1c error. For the 

crit.ic.l atlDe.pberic r .. ct.ant.., such as H20, ~O, and CB", the recOlDllellded absolute r.t.. constant.s 

are in ,oad asr .... nt. with the previous r.l.Un ma •• ur.....,t.. when cClllpll1'ad with H2 •• the reteronc. 

-'re.ct.ant.. --A-.1m1l.Ar' compariSOD with 02 a. the r.tarenc. reactant. ,iv.s .cmawhat. poorer aare8lllont.--

Win.' end Ravhhlnltara (1982) -hav.' 'd.t.e=1ned the' yi.ld of 0(3p ) frOID 0(10) +'2 'is . <4;91.- -

AJ. 0(10) + H20. Th. branch1n& raUo for t.he raacUco at 0(10) with H20 to &ive H2 + 02 or NO + NO 

is an .v.r.,. of the v.lu •• reported by Davidson~. (1979); Volltrauer!i...!!. (1979); Marx 

~. (1979) and L_ at a1. (1981), wUh •• pread in It(m + 1IO)Ilt(TOrAL) - 0.S2 - 0.52. The 

recCXllll8nded brancbins ratio aarNS _11 with ,earlier .. asur ....... t.. of the quanball yield frOID H2

0 

photolysis CCalvert ar.d Pitts lS6Eb). The OC-D) translational enersy and temperature deper.dence 

eUects are not clearly re.olvad. Wine and Ravishmkar. (1982) have d.t.rmined that the yield at 

0(3p ) frOID 0(10) + H

2

0 is <4.0%. Th. unc.rt.a1nty for this r •• ction include. f.ctors for both 

the ov.rall r.t. coefficient. and the wranch1n& ratio. 

A4. 0(10) + S20. Measurement. at the 02 + S2 product yhld _re mad. by Z.llner!i...!!. (1980) (1+O.S 

or -1)% and by Glinski and Birks (198S) (0.005 + 0.007 or -0.006)%. Win. and Ravishmkara (1982) 

have d.temined that the yhld of 0(3p ) from 0(10) + ~O is «4.9.1:3.2)%. 

AS. 0(10) + CB4• Th. branch1n& r.tio tor th. reaction at 0(10) with CB" to ,iva OS + CU3 or ~O + ~ 

is from Lin and DeMore (1973). A IDOlecul.ar b ..... t.udy by Casavacchia et al. (1980) indic.tes that 

an additicaal path fomins CB30 (or CSzClIl + H .... y b. important. thi. pouibiUty requires further 

-l~~';ti,atic;,:- win. and' Ravlshankai. (1982) hav. d.i.-;miDed that. the 'yhld' of 0(3p) from O( 10) . + 

CB" is <4.3%. 

AS. 0(10) + 03' Th. brancbins r.ti" for reactica of 0(10, with 03 to ,iva O2 + 02 or 02 + 0 + 0 is 

from Davenport !L!l,. (1972). This is supportad by .. asurtllMllts at IcWDoto~. (1978) >otIo 

report.ad that co av.ras. on. around st..t. ° is produced par 0(10) raact.ion with 03' It ...... 

unlik.ly th.t this could result frOID 100% quenchins at the 0(10) by 03' 

A7. 0(10) + B:l.. Th. recoamand.ttca is th. averq. of ~t.a by Davidson at al., (1977) and 

Win. ~. (1985). Product. .t.ucU .. by the lat.ter indicata: 0(3p ) + 1I:1(9±S)%; H + CLO(2"±S)%; 

and OB + CIC57±10)%. 

AB. 0(10) + BF. Rat. coeUicient. mel product. yield _uurad by Win. at. al. (1984, ~1vat.. cOlllllZl1c.-

tion). Tha 0(3p ) yi.ld is 1 ... than 41. 

43 

~ 

f 

_. 

,.. 

:.c 

.. -
s 

")" 

L 

. 

~ 

. 

-

;,... 

~ 

y. 

.. . :. 

" 

)~. 

~ 

M. 0(;') + Dr. late c:oefticiet. md pEOduct.a __ ur" 117 WiDe.tl..ll. (ll1S5). ProdIJct. p.1da: 

Dr + O(l!) (ZQt7)%, B + BrC <4.3%, and CB + Br (50±U)%. 

AlO. 0(;') + C~. late coefticiet. cd 0(3p ) product. _ .. azed 117 WiDe.tl..ll. (ll1S'). Pro&lct. pe1da: 

C~ + O(lp) (2.!It10)%. the belmc. 18 prcbeb1:r ClO + Cl. AD euUar iDdirect. .tudy 117 'reude.teiD 

md Biedeokapp (11175) 18 iD reuoaabl. e&n_t. 011 tile 7i.ld of ClO. 

All. 0(;') + ha1ocadloDa. the halocubaa rate ccmat.ant.a an for the tot.a1 cU .. ppeumc. of 0(;') aDd 

probably iDClude pbyaical qumch1D&. Producta of th. nsct.1_ chaaDela ..,. includ. CI.i' + X. 

~o + X:t, md ~ + lID, .... re X • B, F, or Cl iD vaz:ious cCllbiDet.1_. O1l.odue md hJdroIm are 

..:In .ully dJ.aplac" than fluoriDe freD halocubaaa u 1nd1cat.e4 117 appron-te1:r 1001 qu-vbtns 

for CF4 • A UMfI:al. fo~ for •• t.1aat.1D& 0(1,) ~l rat. .. 117 _do ..... md ethce type halocubaDa 

-" .~- &lve 1I7n..r!daoD ~. (11178): k(CnBibclcj. -D.32a + 0.03011 + 0.74c Un uDJ.t.a 10-10 _3- _1ecul.- 1 .-1). thla espr ... iaa do .. DOt. work for _bcub. with atea.i_ fluoriD. aubst.itat.1aa. 

Scaa value. b.-. beaD z:eport.ed for the fract.ioaa of th. t.ot.a1 rate of diaappaumc. of 0(1,) 

procaed1D& t.hroa&h quechiD& md react.in =-ala. 'or CC14: ~. (14:t5)% aDd reecUaa-

(a&t5)%; -(Forca CId Wie.mt.1d, 11151a); for CFC~: qumch1D& • (2SUO)X," ClO fo%lMUoD -

(60±15)% (DcDcInIl, private cQlllll2llJ.cat.ica, 11180); for CF2C~: ~ • (14t7)% md nact.ica 

• (S6U4)1 (lorc. CId Wi •• mt.ld, 1981a) , qu.nchiD& • (10UO)%, C10 fomat.ion • (»tl')1 

(Dc:movan, prbate cQlllll2llJ.cat1aa, 1980); for CF,,: qumchiD&· 100% (Forc. IIld Wi •• ent.1d, 11181.). 

AU. 0(;') + CC~O, CFClO and CF20. Forth. raact.icaa of 0(1,) with CC1:z0 md CFClO t.ba-rec~ 

rate coast.""ta u. darived frCIII dat.a of Flat.ch.r cd lluaain (11178). For coa.1ateney, t.ba recaaIHDdad valu •• for th ... rate constant.s ware deriv" usiD& a .ca1iD& factor (0.') which corract.a for 

the diff.rane. batween rate ccast.lIIlts frail th. au.aiD Laboratory md th. reCCllllllOOdat.icaa for ot.bar 

0(;') rate ccaat.llllts in this t.abla. tha rec.-ndat1on for CFt' 1& freD tile data of WiDe aDd 

Raviah&lll<ua (1983). Their result. 1a preferrad ovar th. valu. of Fletchar aDd Buaain (1978) becaus. 

it appaars to follow the pattern of d.creased reactivit.y with incn .. ad !lucrina substitution 

obauvad for eth.r balocarbons. thea. r ... ctiona bava baen studied only at 298 K. Baaad on 

ccaaidaratioa of .t=ilar O(le) raactioaa, it. i .... umed that. Eta aquala z.ro, ""d th.r.fore the 

value shown for the A-factor baa been .at aqual to k(Z98 K). 

,13. O(le) + 1III:l. SlIIldars li..!!. (1980.) have datectad tha producta JIB(.lA) and CB formaci in the 

reaction. th.,. report the yiald of lIB(a1

A) 1& in tile ran&a 3-1'% of th • .m>UDt of OB detected. 

B1. B + 03 • th. rec.-ndation 1& an avuqa of th. recmt re.ults of La. at al. (1978b) aDd x.,. •• r 

(19711), ..t1ich are iD axcallent &&r.-nt ovar th. 200-400 II: ran&a. An auUer study by Cl,... aDd 

Hockhouaa (19n) ia in vary &oed qre_mt on tha T dap.adanc. in tile ran&. 300-~60 I: but. U .. about. 

60% bal"" th. racOOlllllndad valua.. Althou&h wa bav. no reason not. to baU..,. tha Clyn. and MIx*boua. 

va1l>o., -.. ~pnf • .i: the two -st.udlaa _.tbat are in axcallent qra_t, .. paciall,. ainc.- th.,. war. 

curled out. over tha t ran&a 0' interest. Recant results by Finlayson-Pitt. and Uaindianat (1979) 

qr ... all with th. present recClllDaDdations. Reports of a chcmal foDlina 11)2 + 0 (Finlayaoa-Pitta 

aDd"UaiDdian&t, 1979: -2~%, ""d Forc. IIIld Wh.mfeld, 1981h: -40%) have bean contradict." by oth.r 

.tudias (Bowari aDd Fin1ay.oa-Pitta, 1980: <3%; Wuh1da ~., 198Oa: <6%; Finlayson-Pitta at a1., 

1981: <2%). and Dodonov at. a1., 1985: <0.3%). s.condary cbam1&try ia beUwed to be reapcaaib1e 

'or tha obaarwd Q-atoma iD thia .,.st_. Waabid.~. (1980c) MUUred a law It=it. «O.U) for 

tile production of s1n&1at. 1D01ecular o%y&an iD th. reaction B + 03 • 

82. B + 11)2. thara are flv. racant studi •• of thb raaction: Back at a1. (1978), Back at. al. (1979c), 

thrush aDd Wllkinaon (198lh), Sddhullll~. (1982) IIIld x.,..ar (1986). Ralae.d .arly ...mt aDd 

cCllliluat.ion st.ucl1 .. are referenced in the Sddharan at a1. paper. AU five .tudie. used diacharp flow 

.,..~. It ia difficult. to obteiD a direct. ..... ur .... t 0' tha rat. ccaat.llllt. for this raact.ioa bee ..... 

both reactllllts u. redicala aDd tha products oa CId 0 ara vary raact.i_"towant th. 11:)2 raact.llllt.. 

44 

..--

I 

~: 

,..., 
----------------- - ------------------- ~. -- ._--._._._------_ .. --- '-. -----', .. _._.,--_._-" 

) 

~ 

0# 

4. 

-, 

): 

~ 

lb. nc.-dat.iCD 1a beaed CD" t.be det.a of-Sridbu_·~ • .ad Ee7a.r bee .... t.h.ir ... aur.-nt.a 

"1'. the m.t. direct. IDd required t.be t-t. conecUcau. Th. ot.her ... uur-=->t.a, (5.0±1.3) x 

10-11 _3 1II0111CUl.-l .-1 117 thruah mel IfllJtlnaoD (1l111lh) .ad (4.115 :t 1) x 10-11 117 Rack ~. 

(111711c) are 1D re .. oaaha aar~t. wit.h the nc-W valu.. Thn. of the .toudi •• reported the 

prodDct. chcm.1a: (.) 2C8. (b) ~o + O. aDd (c) II: + OZ' 1IacIt~. (1978) k,llt - 0.611. 

~ S- O.OZ. _ kclk - 0.211: Sridhar_ 5..!l. (lI111Z) k.1k - 0.87tO.04, ~Ik - O.04%O.OZ. 

Itclk - 0.01l:t.045: mel ~r (11188) 1t.1k - 0.SIO:tO.64, ~Ik - 0.02:10.0Z. mel kclk - • 

0.08:tO.04. Bl.lDp mel W.,ue (11177) GId Ee7aer~. (11185) nported on the yield of 0Z(b~) -4 -3 b.bI& formed 1D chazm.l (c) .. (Z.8:±1.3) x 10 mel <8 x 10 of the t.ot.al nect.ioa.. x.y .. r 

fOUDd the nt.. coefficient. -S product. ylelda to b. JJ:depaDd1llt. of t.eparat.w:. for 300 <T <245 X. 

BJ. ° + C:" lb. rat.a coaat. .. t. for 0 + CD 1a a nt.·-to t.hr';' t..-parat.w:. dep«ldanc •• t.udi .. : Weat.enb.ri-

~. (11170a), Lawi ... d Wat.aaa (11180). IIr:Iward mel s.ith (11181). nu. ncca.nd.t.1on i. coaal.t. .. t. 

with euUer ...,0: neu ~ t..-parat.w:. u nvi-.! b,- IAwi. -S Wat.aOD (11180) .. d with the rec .... 

_aaur_t.. of Brun. 5..!l. (11183). The rat.io 1t,0 + II)Z)Ik(O + CB) _aaur..s 117 Xayser (1983) aar-

.with th.-rat.a ccaat. .. t.a-rec-.ded hu.. -

B4. 0+ II)Z' lbe rec...od.t.ion for the ° + Ill: react.1oa rat.a constant. 1a the .... ras. of fiva st.udi •• at 

1'001II t8lllperat.ur. (l:ay •• r, 198Z. Sridb.nn !Ul., 198Z, RaviahCllt81' •• t a1., 19!3b, Brune~., 1983 

aDd IUcovich and Win., 1987)·f1t.t.ed to the t8IIIparat.ur. dependance liven 117 ~ser (1982) and IHcovich 

and Win. (1987). EarUer at.ud1 •• '1I7-BacIt ~.- (1979.) and 5ur:rows 5...!.l.. (1977, 1979) ar.nat 

consid.r.d. because the CB .. B20Z re.ct.ion w.. important. in the.. .t.ud1aa and the value used for 

it.a rat.. ccnstant. 1D their maly ••• h .. baen shown t.o b. in error. Dat.a!rem Ll1~. (1980c) 

is not. considered, bacau •• it. 1a b ••• d on only four ezpariment.a mel involvu a curv. fit.t.inS procedure 

thet. appear. to be in.enait.1ve to the d .. ired nt.. coost.ant.. Oat.a!rom R.avishanlt.r. a .. ,.1. (1983b) 

.t. 298 X show no dependence on pr .. aun bat._en 10 and SOO t.orr "2' n,~ rat.1o k(O + 1I)2)Ik(O + CBl 

measured by Keysor (1983) -sr •• s wlth the rate constants rec~end.d here. Sridharan.to ot. (198!) 

showed that. the react.ion prociuct.a cornspond to abstractiea 0' an oltYsan atom !rom 3:>2 by the 0 

nact.ant.. Key.er~. (1985) reported <1% 0z (b~) yield. 

B5. ° + Hz0z' lbe.e 81'e t...., direct. st.udla. of the-O + 1I:0z-raactlan:- Davis~. '1974c) and Wina 

~. (1983). Th. racOlllll&tlded value 1a a fit to the ccmblned <i2t.a. Wine.!L.!l,. SUSSes .. that. the 

earller meuureanta may ba too hi&h bacaUSIt of sacon.u:ry chllll1stry. The A-'actor for both d.ta 

sat. is quita low cOlllp8red t.o similar at.aD-lllt>lacul. reactions. An indinct measurement 0' the E/ll 

by Rosco. (1982) is can.lstent with the .a<ClllWDdatlon. 

B6. OB + 002 , A new study by ~ser (1987) appaars t.o nsolve a discrepancy bet_en low prusure 

disch81'se flow azparlmanta toblch all sava rate coe'!1ciant.a naar 7 x 10-11 cm? IDOlecula -1 s -1: 

.~ 1I:.,..e-' ,(1981), !hiUsh '.nd'WiliiDsan (198la)", Sridharan~. (1981, 1984), Tamps and Wasner (198Zr. 

and Rozenshtein~. (1984). end atmospheric pressur. studies toblch sava rate coa!!1clents near 

11 x 10-11 : Lll~. (1980a), Bochenedal~. (1980). Defiore (1982), Co% at al. (1981), Burrows 

~. (1981) and- ;UZ:Ylo ~. (1981). Laboratory .... sur....,t. us1ns a disch81'se !low experiment 

and a chemicallllOde1 analysis of the re.ults by lI:ayser (1987) ~trata that the prevl:.u. discbaqe 

flow me .. uramenta were probably .ubject to int.rferenc. f:tall IIIIAl.l IIIIOUnts of 0 mel B. It> the 

pruenc. of exc ... 80Z th .. e at.oms senerat. C8 and re.ult. in a rat.. coe!!1cient. measurement. whlch 

falls b.low the true v.lue. The t8lllperat.ura dependence is !rom lI:ayser (~£'a7) who covered the rlU:&e 

254 to 38Z 11:. An addit.1onal study of thi. r .. ction 1ncludillS the t~rature dependance is needed. 

B7. OR + °

3 , lb. ncca.nd.t.ion !or th. OB + 03 rata constant. is basad on the room t8lllperatura mea.ura1118Dt.a of Xurylo (1973) and Zalmlsez: GId Boward (1980) GId the teparat.w:. dependance studies 0' 

Anderson and ICau!man (1973), I!av1shanltara~. (1979b) and SaIlth at .1. (1984). '=7lo's vaba 

w .. adjusted (-81) to cornct. for an _uor in the ozone coocantrat1oa Masur_nt. (Hampson -S 

45 

t 

~ 
fiI' __ ;'" 

) 

:/' 

r 

:. 

)~ ~ 

BB. 

B9. 

-14 3 Garvin, 1977). The Anderson and Kaufman rate cexatanta .exe ""m.lizeci to k - 6.2 x 10 "" 

1IIC!1ecule-1 .-1 at Z95 K a. sugHted by Chan& and Kw!man (1978). 

09 + 09. The rec...-ndation fox the CD + 09 reaction i. the aver .. e o! siX ...... ux......,ta neu 298 r:: 

We.r.enber, and de 9 ... (1973.), ~ie~. (1973), Clyne and OOlfD (1974), traiDor and 1IOJl 

RosenbeXS (1974), Farquharson and Smith (1980) and Wqner and tellner (1981). The r1te constants -12 3 -1 -1 for '..he.e studi .. ill f.U beboeen (1.4 and 2.3) x 10 em :DOlecule •• The t.amperatare 

dependence i. fraa Wqner and tellner, who rep'rted rata conatant. fox the rmae t - 250-580 11:. 

09 + Hz0z' Thexe are exten.ive data on the 09 + Hz0z re.ctiCill. The recOllllOlDClatica is a fit to 

the tsaperatux. dependance studi .. of: r:ay.er (l98Ob), Sdc:lbarllD~. (1980), Wine et al. (1981c) 

-and Kurylo ~r (198210). The !int. two_re!arenc .. contain ._~.~s1~! some p' •• ible x .... ons 

for the discrepancies with eulier work and an ............ t of: the impact. of the new value on othex 

kiDetic studio.. A .... sux_t. at. 298 r: by Maxin.W and Johnston (1982.) aaxe.: with the r8CQDlIlendation. th.re is SOllIe evidence that. !/R d.cr ..... with tealpexatuxa .. discu."ed by L.IIIlb et al. 

(1983); tha~.fore, __ the recoammdat.ion incorp)uta. a larse erxor liIIlit. on the tamperatare 

dependance. 

Bl0. 09 + Hz. The CD + 9Z reaction has been the subjact of DUlll8rous studies (sa. Ravishankaxa at al. 

(198lb) for a xIIView o! expexilllental and theoxetical work). ~e recClllD8ndation' is fixed to the 

avera,e of nine studies at Z98 K: GreiDer (1969), Stuhl and IUki (1972), Westenbax& and de lIaas 

(1973c), &!dth and tellner (1974).-Atkinson et&l.~- (1975), Overend -et al. (197:1), tully and 

Ravishankara (1980), Zellnex and Steinert (1981), and Ravishankara~. (198lbl. 

Bll. 90Z + 9OZ' two sepaxat. expressions are liven for the rate ccnstant for the 907 + 90Z xeaction. 

The aUective rate constant i: liven by the SlD o! these two equations. This roaction has l;een 

!hown to have a ?reS3UXa independent bioolecular component and a pressure dependent termoloculax 

c:c:mponent.. 3eth c:ca:ponen:.s ::AVe negati·/~ !.~pera:."..l.r& :::ef!:':~an:'3. :he bi::xllecula= exprasslcn 

is obtained fxOlD data of Cox and Buxrows (1979), thrush and -=r..dall (198Za,b). Kircher and Seder 

(1984), Takacs and Bowaxd (1984, 1986), Sande.: (1984) and Kuxylo~. (1986). Data o( Rozensht.ein 

.!l:....!!. (1984) axe consistant. with the low pressure reccxtlDendat!on !)ut they rep'rt no c!lan&e in k 

with pressure up to 1 atlll. Eaxl1er results oC-Thrush and~-WiWnson (1979) are iDconsistant with 

the nCClllDllndation. the termolecular expression is obtained !ran data o( Sander ~. (lS8Z). 

Simcnaitis and aeicklen (198Z) and Kurylo.!l:....!!. (1986) at roan temperatuxa and Kircher and :>andex 

(1984) for the temperatuxe dependence. this equation applies to !1 - aix. On this reaction ","st...." 

there is ,oneral ",reaDent """"" iDvestisat.ors on the foUowins aspects of tha reaction at. hi&h 

pressure (P -1 atlll): (a) the 90Z uv al;sorption cross section: l'auke~ and Johnston (1972), Cox and 

Buxrows (1919), 90chanadel~. (1980), Sander~. (!982), and Kurylo!l-!!. (1987a); (b) the 

rate constant. at 300 1C: Paukort and Johnston (19721, !lamiltcn and L11 (1977), Cox and llurrows 

'(1979),:L11 ~t aL~ -(~~97-9-)~t~:chlya -and Ifak"":";a nS1S), Sande; ot. a1:- -(198Z), Si::Ionattis al:,d-- - - _. - -12 

Beicltlen (1982), and Kuxylo ~. (1986) (all valu .. tall ~" the ran,e (Z.5 to 4.7)- x :0 

cm3 :DOlecuia1 s -1); (c) tha rate const.ant temporat.ure depmdonc" Cox and Bur:""s (1379), 

L11 at a1. (1979), and Kircher and Sander (1984); (d) the rote constant. water vapox dependmce: 

9eJ.lton (1975), IIochanedal~. (1972), 9amilton and Lii (1977), Cox and Burrows (1979), llottlre 

(1979). Lii~. (1981), and Sander~. (198Z); (a) the :!Jtl isotope e!eact: a-ilton and Ui 

(1977) and Sander ~. (l98Z); and (f) the focat:.cn of "2:)Z + O2 as tha lIlajor prodw:u at. 

300 J::: Su ~. (1979b) , 1fik1 ~. (1980), Sander .!U1.. (198Z), and SiIIloneitu and Beicltlorn 

(198Z). s.netchian~. (l98Z, 1987) ,ive evidence !or tl:e !o=ation o! • ......u lIIlOunt of liZ 

(-101) at tCIpButuxa" naU ~OO IC ':out Baldwin ~. (1984) '~'18 evidanca that the yield 1II1lIt. be 

!laJCh leu. Gl.1naIt1 and lIirk. (1985) report an uppex !.iaU t of 11 liZ yield at. a total presS<tre 01: 

about ~O tou and Z98 J:: but theix experu..at. cr. have iDter!.rence !rca .all xeactions. For 

sy.e- conta1n1Il& __ tar vapor, the factors ,ive :,. 1.11 ~. (1981) and XJrthar and Sandex 

-Zl (1984; can be incorpoxated: 1 + 1.4 x 10 [9Z

0) up(2200r.). 

46 

\1 

.-

• 

" 
~ ........... .., 

~ 

... 

4 

~ 

r 

, 

t 

~ ~. 

l~ t... 

t~ 

r 

r 

~ 

r 

i 

~ l 

, 

tt 

.. 

--: 

~: 

/...; 

. ~ 

/" 

) 

') 

:!J:'-

B1Z. BJi-+-03' The-re~tica-ia-baaect-~.t..U • .-uaiJlaofiacisu&~~~: 

Zahniser md Boward (1980) at. 245 to 3115 E. Hma __ Lll. (111811) at. :zga E. aDd Sinha ~. 

(1987) at. 2.4Lto 413-1:. Indirect. st.udi .. by SlaaDaiUa md BeicUc- (!4I73). D-"or. md Ta~ 

Raux (1974). md D-"or. (1979). are ccaubt.lat. with t.ha direct. .aaur_ta •. The .,.t. ~i'" 

teperature dependcce .tudy (Sinha 5....!l .• 11187) inlUcat.ea a curvature in the Arm.u..a plat. 

A similar but le .. obvious curvat.ure is found in the data 0' Zahniser aDd IIowud (1Q80) IIId 

DoHare (11;79). lba rlC......atiOD incorporatea 001,. clJ.ract. ___ to data at. t..peratur .. les. 

t.hmI 300 E and is not. valid 'or t.ealparatur .. areatar the 300 1:. tha vaUdit.,. 0' the rae _ iad 

e:q:re .. iOD is qu •• t.1cmahle at. t.eperatoures la .. t.ban 240 1:. wbara there are DO data. Biah quaUt,. 

low t.epereture _--=-t.a are needed 'or thia react.iCD. 

Cl. 5 ~ O2 , lbe activatlOll en.rc' is baaed CD Becker ti..l1, (1S111I1). The value aDd UDcert.alnt.)' at 

298 E are asailDed !rClll tha .".r&&e 0' Cl7Da and tb=ab (1961). Wllaon (1S1117). Becker ~. 

(1969), Ci.a.::k aDd" W.,na" (1970) md w..t.lllbarS n...Jl. (1117Ob). IDdepandct. confu...at.101l" 0" the 

teperat.ure dependance is naedad. 

C2. 5 + 0 3 , lba rec:or:mmdatiOll is baaad ea resulte 0' SUe' .t. al. (111711). Kot. thet. uu.a ia an 

upper Umlt baaed ea iDat.ruc>antal ..... it.ivit,.. Reault.a 0' Stie' ~. md Garvin and Braida" 

(1963) ca.t doubt. on tha !out. rata reported by l'bll!.1pa aDd SchiU (1Q62). 

C3. 5 + NO. RacClllDCldat.iao is baaed on the reault.. 0' L .. et. al. (1978c). A recent. .t.udy 0' Bassin 

and Slatar (1980) report. a roc:m ~ature rat.a constant. 30 percent. hlsher t.ban the reC'O!!DM!C!ed 

value. 

C4. N + K02 • lb. Panel accapt.. the results 0' Cl7Da and Ck>o (1982) for tha value 0' the rate caoat.lat 

at. 298 E. this is a factor 0' 2 hlshar than that. reported by Cl7D& and HeDermid (11l7S). BCIIMVU, 

Cl7De and Ono consider that. the more recant. .t.udy is probabl,. .. re reUable. Busain and Slatar 

-11 3 -1 -1 (1980) reported a roaD t.amperature rata caoat.ant. 0' 3.8 x 10 em molecule s • which is a 

!act.or a! 12 sreatar than the value reported by Clyne aDd Cbo. lbla hish value rtJ.try indicate the 

presance a! catalytic cycles, as discI:ssed by Clyna and McD.rmid, and Clyne and Ono. There are no 

studi .. a! the t.emperature d.pendenca 0' the rat.a caoataat.. The react.iea products are taken to !:Ie 

N20 + 0 (Clyne end HeOarmid). A recent. stud)' by Iwata at. a1. (1986) sugest.ad en uppu Uait 0' 

3.3 x 1Q-13 ~ .IIIOlecula-1 s-l __ !or. tha correspODclJ.!l&--raact.ion 1DvolviD& 1I(20)-an4 11(_,,) atmIS 

(sum 0' all react.ion channels). 

C5. 0 + N02 • Chanaed 'rom JPL 85-37. k(2.98 1:) is baaed CD tha results 0' Davis~. (1973a) , 

Slan&er It a1. (1973). B--m~. (1974). Oaast.ed cd Birks (lSlaS) md Gnra-tbller and Sblbl. 

(1987). lbe recOlllllOlndation tor !/R is trca Davis et. aL. Clbpt.ad end Birks. and Gnra-tbU.ar and 

Stuhl with the A-tactor adJu.st.ad t.o sive the racOlllllCldad 1t(2.98 1:) value. 

C6. a + N03 . Based on the study at Grab~ __ aci:f Johnston (1978)"at. 298JC and 32.9 E. Whil." Umlt.ed_-iii 

tauparatura ranae, tho data indicat.a no t.~rature d~ence. Further.lllOra, by anale&:>, with the 

reaction ot a with K02 ' it is assumed that. this rata ccaut.mt is independent. ot tllllparatun. 

Clearly, teq>erature depend eat Itudies· are Deeded; 

C7. 0 + 520 5 , Basad CD ICa1su and Japar (1978). 

C8. a + l!lI:J3' lbe upper l.im1t. reported by ~ and WaJDa (1974) is accepted. 

C9. 0 + 1I02K02 • lba rlCaaDa>ded value is buecI CD the study 0' Clm& et. d. (1981). thAI l.aqa 

uncertaint.y b l/R and k at. 298 E an due to tl:8 !act. that. t.h1a is a sin&la stud7 • 

47 

~~ 

I 

I 

, 

; 

,I 

r. 

\ 
t' ...J~-:.~:-

L' .' 

" 

: 

~ 

) 

) 

r.r 

-

---..:....:..--------'---~--~ - ~~-

CW. 03 + 10. th. nc _ rIed Arc-1ua GFeuicID 18 • 1aaa~ -auana n~ to tile cIa~ npozted by 

IIUb A.I1. (1SJ78). LlW--.I1...Il. (1DaO). Ia7 IDd llataas (UIIllt}, ttldled. JL.U. (Ull) cd 

~n -S iuta (1H2) a~ -S belaw ~ u.pentan. with the cIa~ R cloaa17 apec:.cl 

t..peratan& raportecl in L1~~. aDd IIorden -S ISUU IMiDe aZ'OaI*I toaetber 80 that 

the_ ti_ atocU.a an .. 1&hted acpall7. rua apnaaica tita all tile clata wiWD the ~at.ora 

rca. las-304 E rapoztacl iD tll ... five atocU_ to witIaiD 20 percct.. 0bl7 die data b.-.a 111' 

aDd 304 E.ara _ad to clari_ the nc~ad ~ua apreaaiem. dIM to the CIiIaarv.d __ liDear 

.urt-uua bebaYiar (0.,- ~. (11184). Claaah .ad !hruab (11187). 111m. .5.J1 .• tuc:bael~. 

aDd Barden aDOS lIim). Cl.au&h mel ThrIWl. II1rb !L.Il.. Scharath ~. (11181). -S IUcbael 

fi...51. Mn all npart.ad iDdlviclaal. ArrllmJ.ua par-.t.ara tar MCh at the t.J prt.u7 nacUem 

cbcm.a. tha rcaa ~ valu .. !or k at atrat.o.pbertc tallparaturM i. a--.c. laraar thas IIDul.d 

be npec:tad tor ... ch .. any nacUCII to atudJ. tha --=-t.a ot Stect.e ...s .J.kJ. (1~3) md~ 

II-md~'- (11174) R 2118 E ua in ucaUmt aan-t. with tJoJe rac 'acs n1ue at k R 2118 E. 

C!l. 10 + 11)2' tha n~~iCD tor 11)2 + 10 1a baad em the cnnca ot .1% _ .. ur_~ ot tha 

rata ccaatmt Dear ~ taooperablra: Boward IDd !lnuca (1SJ77). Leu (11171b). a-ard (111711). 

Glaach1ck-schJ.mpt-~. (13711). lIack n-u. (11l8O). aod thrab -S Wi1k1mm (111S1a)~- All atthea. ara in quita ~ qra_. AD aarUar atudJ. 1Iurrc.a!L!l. (111711). h .. b_ dropped 

bec ..... of m error in tha "fanaca rat. cCllRmt. k(CB + B.fJ2)' the roc. c..paratur. atudy of 

Rasaoahtain~. (1984) baa alao bem dlanprdacS clue to lID iDaclaquata diac .... iCD of poealbla 

__ sec0adu7 nactioaa. th. t-.pantur .. dapmdaDc. is ~ IIcorud (11180) ... ~ 1& iD rNSODabl. 

_qr~t with that &1v" by Leu (111711». A blab p~ssar. atudJ 18 Deedad m vi_ of ~the -.ny ~ -

unusual. aUec~ s_ in oth.r 1102 reactiana. 

CU, 110 + 1103 , Olmaed fraa JPL 8'-37. the 2118 I: r.c:caomdaUCD 1& baaed 011 the studi.s of torahi 

and Ravbhmltara (1984), S-r~. (1988) -S Smdar and Eircbar (11188), toII1cb an in ac.Umt 

qr.-nt.. th. t dapeclaDc. la baed em an ... arq. of the r .. w.~ fraa SGlder md ICirchar. mel the 

data of B~r ~. ~,l~w 300 K. 

C13. CH + BII03 • th. int .... ive study of thla nactian over the pu~ t_ ,.ars baa &!&nitlclIDtly nduead 

amy at the apparmt dbcnpllZlCi.s .aca (a) tha early studias yi.ldiJIc a law. tallparatur. iJldepaDdmt 

rat. eoaatmt (SaI1th ad Zelln.r. W, and Har&1tm .t al., 11115); (b}80r .. r.ect1OOrk (JIIOatly~n .. h 

photolysh) with a k(298) appra:n-taly 40% luau, and. atrona lMIativ. t clapmdenc. bate. rocm 

t.aperatura (WID. £.....!1.. 1981b; Iaryla ~.. 1982a; Har&itm ... Wahon. 1982; HarinaW IIDd 

Jcbnatcm, 1982a; Raviah.El<ar. ~ .• 1982; Jooudain et .t .• 1882; C. A. Salth~ •• 1984; Jolly 

et at.. 1118' (298 E). Stacbn1lt et a1., 1988); and (e) recent dlacbar,a law stadies yhl.d1n& the 

te.u valae for kC298 1:) but aboor1n& substantial Deptin t dapeclaDc. (Dnal.dar et at .. 11184: 

eoun.ll and Boward. 1985). Major fa.ture. of the do~ are (1) a strena DepUv. T dapcd.Dee 

below ro<III temperatura. (2) • I!l.Icb _alter t.aalperatur. dapandene. above roaa ta.peratura. pouibly 

lavelina oU around ~o 1:.- (3) szull, ..... urable prauura dapaDdanca .mlcb bac::aMS iraatar at ~1Ow 

t.aperaturaa. the preuura d8pend.nc. h .. ~~m d.tam1ned by Har&itm .ad WateoD (1982) ...... r the 

reD, .. 20-100 torr and 225-298 I: cd by Stacbn1k et e1. (1886) .t pnuur .. of lIl, 60 and 730 torr 

at 2118 1:. lb. boo st.diea are 1:2 excallent .~. their -te. pr ... ur. liIII1t- aar __ 11 - -13 3-1 

.ith the ..... r ... k(298 I) - 1.0 x !O CIII s d.rived trem the !oar law prMmr. diacbarp rlaw 

studi... the vatu ... uurad for pra .. ur .. typical of the other f1uh pbatal,.i. studi .. (20-'0 

torr) also eara ••• 11. lb. t100 praaur. d~. studias iDdJ.cata that th.!dab pr.ssure limit 

is approximataly SOX ar,ar..ar than ~ low pressar. llm1t st 298 E. and about a !actor of 2 araat.r 

at 240 1:. thus, ov.r the Darrow preuur. rea .. s explored in _t flaah pbatalys1a studies, the 

P depaDdmc. OIO\Ild escape notice. For taooparatur.s bate. 300 I:, the prasao:e and t.a.puatura 

dapeadeac. CID be rapresmt.ed by cClllbinina a 1_ pr .. aur. (bt.olecw.u) limit. ko' with a 

L1Dd.aaml-B1Dahallooad apression for tha P dapoar:Imc.: 

48 

.~l~ 

J-

. , 

~ 

-'3 
-----" .. -. - . --

r ~ 

j 

.. 

,: 

~. 

r 

. " "_"f 

) 

~.) 

!T 

1t3 [HI 

It(H, T> - Ito + 1t

3

[HI 

1 + ItZ 

with 

Ito - 7.Z Z 10-1'-Czp(78'1t) 

ItZ - 4.1 Z 10-15 ap(14401t) 

~ - 1.11 Z 10-33 ap(7~1t) 

l'be coefnciC1ta ~ ROd ItZ are the te~lecu1.ar AD4 hlab F- Ualt.a for the • ... oclation· 

cbaa:1.1. The valu. of It at hlab F-aun. i. the ... Ito +~. the weak preaaur. dapeadenc. 

aDd wak T depeadeDc. eav. 300 I: apla1D MIZJ' of the ~ d1.cr~in for aU the data 

(1nClud1D& the 1117' .tudi •• >, .xcept for a f_ mz.or f .. turn tIblch are probably due to the 

noza.Uy 1IIC000t.nd azped-..tal acatter. the 3a1th ...s ZellDa: n .. b pboto17.1a valuea an 

law cClllp&Ad to oth ... flaah ay.t_ (cloeu to the flow .bodin>, althaaab the differ_. 1a 

Dot. _ual. (-30%). OlaY.n.l7,- the .:Ioouda1D ~. flow atudy la h1&b "latin to the other 

ODea. the eo-.ll ...s IIowud T dapeDd_. (bel.cM 300 1:) 1& .~ficmtlT ...ur thaD the other 

.t:ucU ... th. failur. of SIalth~. to cb ....... F"av.n eUKt be~ '0 _ 760 ton, ev.n 

at 240 1:, i. in &hArp caaf1ict with the ."act _ by StacbDJ.It Jl..l1. _u the ._ r .... in 

e_8UCb aInII deta1~ ~tudy. _~oUy 5...!l., &lao could DOt. det.ect a pr .. ..r. depend_ce bebl.an 

1 torr (H - Jm:)3) _ 600 torr (H - SFI\) .t 2118 1:. B.uon ~.- (1l1e1), .Jourda1D ~. and 

tt.n.hclltua ~. have all ahOllD that within aperlMDtal. error the yhld of 11)3 (per OB 

r~ed> la urolty at. 2981:, with .imilar r .. u1ts at Z50 I: (ltaviah...tua ~.:. 

C14. CB_ +_IIO~~ __ Th. __ ~acaDendat.1OD f~r both It at 29S I: _ the .AnbeDiua apr .. den 1& baaed upon 

the elata of Trevor at d. (lSSZ) , iame. -.t a1:(1981>, C. A. Salth .t &. (1984) az:d l!am .. 

• t .1. (1986b). T~""'~~, .t.ud1ed thi. ~eect.iClD over the r..penture RIll. 246-324 I: and 

-12 3 -1 -1 repotted a taeperat~. invariant value of 4.0 Z 10 em _lead. a ,althoush a .. t&!1t.ed 

t-.t squar.a fit to their d.ta yi.lds an Anhml_ uprna1ca with an E/Jl valu. of (193±l93) K. 

In cenUaat, SIIIlth .t .1. .tudied the reaction over the temperataA rmae Z40-300 I: IIDd cbaerved 

• n.s .... h. t*"Per.t~e d.pendanc •• lth an t/R value of -(6!'O±30) 1:. Th •• arly Barn •• ~. 

study (loa1) ••• carried out. only .t. rocm t.".,.rst.ura and 1 ton total pressure whi1. thoi: IDOst 

recent. at.bdy _a perfo.-d 1D the pr ••• ~. rmae 1-300 torr -z aDd taq>er.tara r&l1&e 26<1-295 K 

with DO rat.e coaataot variation beina ot...rved. In addit1C11l, Itzss dedved in Barn •• ~. 

-12 -U 

(1981) was ~_1&ed .... ard 1D the later at.bdy fraa 4.1 Z 10 to '.0 Z 10 due to 3 cbazla. in 

the rate conatant for the r.ference reaction. -n.e "nw.. of It at 298-1:: -fraor the fow.- studi.s 

are 1D ac.llent. esr_nt. Ion lmM.i&!1tad l ... t squar •• fit to the data fiClll the abov.-

.-Jtiooed studi •• yi.lds the recDlllHOded Armenia. uprns1oo. the le •• preda. value for k at 

298 x: reported by Littlejohn and JohDsten (lSSO) 1& in falr a&J: .... t. with tha reccmnended value. 

The error 11m1t.. en the racClllllanded till are .ufficient encomp ... the re.u1ts of both Trevor .t .1. 

-aDd SIIIlth .t. d. It ahould be notad that. the valu •• of It at 220 I: deduced !raa the t_ studies 

diff.r by • f.ctor of Z. Claarly additional .tudi •• "'! It as a f'uDctioo of ~rature _ the 

__ id.ntification of the react.ion produc~ are n.eded. 

C

•• -. 03 + 11)2' Ba.ed en l •• at. '-<jUar •• fit to elata in studi .. of Davi •• t 81. (1914b), Gra!laal and 

JobnatoD (1914) _ 1Iui. and Benen (1974). 

ca. 03 + 1DIOz. Baaed on J:01&ar ad .:Iapar (lSln) and Streit~. (1117S1). 

C:'1. SZ0!; + !.z0. Upper llmlt heaed on Tuuoa!L!1. (1983) C1d Bjorth .t. d. (lSS1) , tobo suu.st 

that th1& Uait ...,. be clo .. to the true boaIosaneoua rata canatllDt. 

Cl!. CB +~. The rec~ed vatu. at 298 r: 1& the averq. of the nlu •• reported by St.uhl. (1913b), 

s.1th _ Zellner (11175), P.rry~. (l976b), Silver _ Xolh (11180), ...s StapIwna (1984). Th • 

.... al .... uported by Paaabus .t .1. (1979) _ Cox et .1. (1975) wn not ccaaldered bec_ th •• e 

.t.ud1 •• 1nY01vad the lDalyai. of a CCIIIplez ...,bIIDl_ and the ~t. are _U outside the error 

49 

.-
•• (o\ .~"'"- . ,. 'f ••• 

I 

• 

If 

• 

~;' 

--

~ 

y 

/. t :. 

I 

) 

~J 

limits implied by the above fiv. direct. .tudi... Th. relUlta of Iurylo (1973) md Back .t al. (1974) 

.are not. COII8idered b.c ..... of their lar,. di.crepanci .. with the other direct. .tudia. "actors of 

3.9 and 1.6 at. room t.mperatura, re.pectively). The taaoperatura dapandaDca i. hued on the reaults 

reported by SaI1th aDd Zallner, l'ury at. al., Silvar md rolb, md Stephaoa, md the pra-aponmt.ial 

factor has bean aalocted to fit. the rac~ed 1'001II t.aaoperat.ura value. 

C19. IIIIz + 1102 , Thare is a fairly load asra.-nt. 00 the val ... of It at. 298 ~ batwam the dir.ct. at.udy 0' ~as .. a and L .. claux (198Ob) , md the ralat.1va .tud1 .. of Olaslt1. md Sarltbov (1979) md 

l'assber, at al. (11179). Tha rac~ed valua h tha __ rqa of the valuea raported in tha .. 

thr ... t.udi... Tha idantit.y of the producte h not. 1aIoooD; hoomrar, J:uraa_ aDd Laacl.aJx .\l&Ia.t. 

that. tha ... t. prob.ble react.ioo charm.La aiva aither JlB3 + 02 or BIll + B2.0 as product.a. 

C20. IIIIz + 110. the rac.-nded value for It .t. 298 ~ h the warqa of the valo .. reported by Gordon 

~. (1971), Gebr1n&~. (1973), La.cLaux~. (1117S), Bmcoclt at. d. (1117:1), Sarkbov at. a1. 

(1978), Back~. (111711), SUaf.t. d. (1982), Silver aDd roll> (1982), ...s Wbyt.a md Phillip. 

(1983). the valua. raPort.ad in the.e at.udi .. for It at. 2.98 ~ r&ll&a f~ 8.3 to 27.0 (x 10-12) cm3 

IIIOl~cula-l .-1, which is -n.it.part.ic:uiarly aat.hfactory. Th. n.ult.s t.aDd to .aparate into t.wo 

-11 3 -1 -1 &r0upa. Th. flash pboto:'y.is ra.ulte ... arasa 1.9 x 10 em IIIOlacula ., while t.hosa obt.a1nad 

-11 3 -1 -1 uaina tha dischars. flow t.achniqua ... arasa 0.9 x 10 em IIIOlacula s. Tha apparent. discrepancy caanot. aimply ba dua to a pra •• ura aUact. •• the pra.aura ranaa. of the flaah photolysis 

and diachAraa flOw .tudi •• overlapped, and nona of the .tudias ob .. rved a pra •• ura dapcdance for 

k:" Thaia hiva -tialn . fOUr .t.udiaa of thi tamparatura -aapecdanca of It. Each.t.uay reported It· t.o 

-1 25 -1 85 dacreasa with increasina t.emparatura, i... T' (Lasclaux.t. a1. frcm 300-S00 1:), T • 

(Back at d. !rOIl 210-503 ~), T-1 •

67 (St.1.f ~. !rail 216-4801:) and T-2•

3 .xp(-684fT) (Silver 

and ~ll> !rail 294-1215 1:). The reCOllllleDded t..mperature dapandanca is takan to b. a _i&bted averqa 

of tha data balow 500 I: !rOIl all tour studi... Th. cxpr .. a1oo is: It - 1.6 x 10-11 (T/298) -1.5 

for the temperat.ur. ransa 210-500 1:. 

Thara ara many poslible product. channals !or this raaction. Strcns aVidenca qainat. the !oDnation 

o! B atQIIS arists. Both Silver md ~lb (1982) and Andrasan~. (1982.) report aubstantial yields 

of OB of 401 and ~651, rupect.1va1y, in dhqr"lIIant with Stia!~. (1982), Ball!l...!l. (1986) 

and DoLaoo (1986) who ob •• rv.d 1'001II tamparatura-CII yhlds o!-<22%, 13:t21 md-<15%. respactivaly. 

In addit.1oo. Andralan~. aat. a lower Umit. of ~91 tor tha channal "2 + SzO. 

C21. KH2 + !Il2' Thera have baan tour .tudias of this reaction (Baclt et a1. (l979b). turasawa and 

Lasc1aux ClIl7I1). loIlyt.a and l'bilUpa (11183) md XiC1l et. al. (11185». Thare i. vary poor qre_ant 

8IIIOna tha .. atudios both tor It at. 298 ~ (factor of 2..3) md tor tha t.emperatura dapendance of It 

(T-3 •0 and T- 1•3 ). Tha racOlllHDdad valu .. of It at. 298 ~ and the temperatura dependanca of It are 

averases o! t.ha ruults raport..d in thasa tour st.udie.. Back~. have s~ that. tha pradQllinant. 

-r;a~t.1o~ -ch.m;al (>951) produces '520 + Szo. -Just. as !o~ th • .lIB;:" NO react.1~. u.. ~u tor this 

raact.ion sa_ to indicat. a fact.or of two diacrepancy betwaan !Low and flaah teclmiquas, althoush 

tha data basa is auch II1II&11.1'. 

-18 CU. KHz + 02' Tha racClllllHnd.atioo is based on tha reported upper Umit.a o! 3 x 10 (La.cleux md 

0 .... 1&.,.. 11177), 8 x 10-1S (Pqsbar, ~.. 1979). 1.S x 10-17 (Claaltb and Sultbov, 1979). 

3 x 10-18 (Lozovalty .!.L!l. .• 19M), 1 x 10-17 (l'atrick aDd Goldm. 1984b) md 7.7 x 10-18 

(Hichaal et. ai., 1985b) all axpre •• ed .. b1alDlacular rata cooatct.a with 1Zlit.a of CtJI,3 .-1. The 

t.erD)lecular rate con.tmt. upper Umit. ...w.d be 2 X· 10- 315 CtJI,5 a -1. Tha Yalues reported by Baclt 

et. a1. (l9!2) , It - 3.6 x 10-33 (T/2.9S)-2. .. 5 .-1 and Jayanty et. d. (1976). It - 4 x 10- 1S CfA3 

• -1 ara DOt. used in arriv1n& at. the rac.-.adat.1oo. BacJt and LlrxJta (l98S) have obaarved a 

react.ion bebrMD l1li2 and 02.(lb ). cbta1n1n& a rata cooat.aat. of (1 ~ 0.3) x 10-14 ca3 1I01ecul.a-1 

• -l bat._m 2.115 aDd 353 1:. 

50 

~ 

, 

, -" 

~ 

~ 
t 

• 

) 

4 

.. 

r 

p. 

-;/ 

-1'"< 

:. 

J 

---_._-------, 

C23. HB2--+· 03 ,- Chan&ed-traa-.1PL-83-62~ -Ther.--i.-poor-qr~t.-bebNea the ree .. t. studi .. oC-Pat.rick 

and Golden (1984b). k(298) - 3.25 x 10-13 em3 .-1. and t.l» earUer .tudie. by !lack ll...!l.. (981). 

1.84 x 10-13 em3 .-1; .Bulat.av~. (1980). -1.2 x 10-13 t:ta3 .-1, and rnr..- 'A Lesclaux-

(1980a). 0.63 x 10-13 em3 .-1. The very law value oL ~_ .ad Laacl .. ~ may be due to 

resenaration ot: ~ !real .econdary reaction. (._ Pat.rick and GoldeD). end it. is cU.resardecl here. 

The discharse t:law valua ot: Back~. i. nearly e factor ot: t..., le •• thm the recent. Patrick md 

Golden nasb phot.olyd. value. The lars. discrepancy be~ Bulatov et 81. cd Pstrick md Golden 

elude. explanation. The recOllllllCldation is the k(298) --ras. of these thr ... t.udJ. ••• cd E/R is 

m averase ot: Pat.rick and Gold.n (1151 X) with Beck~. (710 ~). 

D1. OB + CO. The recOlllll8Ddation allows t:or an increas. in It with pre •• ure. n.. zero pressure vatu. 

was d.rived by avuasins all direct. low pr ••• ur. detaJ:lll1nat.lona (those llst.ed 111 Baulch et. al. 

(1980) md the valu .. report..d by Dreier md Wolt:rua (11J8O). &Min at. al. (1981). b'ri.banltara 

and Thaapaca (1983)-;- ParukevopoUlo-.- md IrWin (1984). sOtzlOUbaus .ad Std>l -(984). md Frit.z 

and Zellner (priv.te ccamunication. 1987». AD increas. 111 k with pr_sura bas been ob .. rved by a 

lar,e nuailer ot: 1nvastisator. (OIr.rend and Paraakevopoulo. U977a). P.rxy .t. al. (1977). ChG1 at. al. 

(1977). B1e=m at. al. (1978). Cox~. (1976b). But.ler et al. (1978). Paraltevopoulo. and Irwin 

(1982h. 1984). DeHore (1984). Bof%Ullllhau. and St.ubl (1984). Fritz IIId Zellner (privata c_ication. 

1987). llyn .. at. al. (1986). Stachn1lt and MoUna (privata c~lcat.1on. 1987) mel Walmar cd Zet.zacb 

(privat.e cClllllUnicaUca. 1987). In addition. Iflki ~. (1984) haw __ ured k relative to CS + Cz!14 

ln one atmosphere of air by t:allowin& CO2 product.ica uslna FTIR. The rec~ded 298 r; value was 

obt.ained by usln& a _l&bt.ed nca-linear least. squar .. anal.yds ot: aU. pressare depeodeot. dat.a in 

1f2-(Paraskavopoulos-and~Irw1ll.(1984). DeMore (1984), Bofz..ah .... -cd Stubl (1384) aDd llyus ~. 

(1986» as _11 as tho.. in air (Fri t% and Zellner (privat.. COIIIIIUnJ.cat.l=. lSS7). Hill ~. 

(1984), Bynes ~. (1988). St.acbnlk and Molina (privata coam.m1cat.loa. 1987). Walmer IIId Zet.zach 

(privat.e ccamunicaUon. 1987) t.o the faJ:III k - (A+BP)/(C+DP) wbare P la pressure in .talspher ... 

The dat.a _re best. !it. with D - 0 and t.herefore a linear ~= is nc~ded. 

Previous controversy re,ardln, tha ef!ect. o( small amounts o( 02 (Bierman et 01.) has be", resolved 

and is at.tribut.ed to secoodary reactions (DeMore (1984). BoLzIaIIabaa and St.uhl (1984». n.. re .. ults 

o( But.ler~. (1978) have to be re-evaluat.ed in the lisht of n!1n-..t.. in the rat.e coet:ficient. 

for the OB + ~02 nactica. The correct.ed rat.e coeUlchat. is 1D approximate a&r_nt with tho 

recClDllloded value. Current.ly. there are no .indications to sU&& .. t that. the pr .. ence-o( O2 bas my 

eft:ect. on the rat.e coefficient. other than as a third body. The EIR value in the pressure raDIe 

SO-760 torr has b.en shown t.o be essent.ially %aro b.tw .... 220 IIId 298 X by Byn_ ~. (1986). 

and Stachnik and H:lUns (privat. coamunicat.ions. 1987). Further Sl>bst.antiatlan oL the taIlperat.ure 

iodependence of k at 1 atlll. may be worthwhile. The uncertainty factor is !or 1 atlll. of air. In 

the pre .. nc. ot: O2 , the BXO intaJ:llledlat.e ia converted to B02 + CO2 (D.t1on. 1984). 1IIDo~. 

(198S) observe lin .ahanc_nt. of k with w.t.er vapor which Is in canfUct. with the Lusb p,otolysls 

studio •• e.s •• Ravbbanlt.ra and Thompson (1983). Paraakavcpouloa mel Irwin (1984). DaHere (1984). 

and lfYne. ll...!!.. - (1986) •. 

D2. CB + CB4 • Thi. 1& m utr __ ly well cbaract.erized nact.ion. All t.llllp8rat.are dependenc •• t.udies 

are in Scod asreamcnt. (Grainer (1970b). Davis ~. (1974a). Har&it8ll~. (1974). Zellner md 

Stain.rt. (1976). Tully md ltavishanltara (1980). Jeon& mel ~!man (1982». Dee to this ,cod qr.e1IIClt.. and the curved nst.ure ot: the Arrheniu. plot. at. h1&ber tamparatures. the Tal_ ot: Dni. ~. 

obt.ained in the t.empent.ure int..rval 240 <T <373 Ii: is nCClDlllnded. 

D3. CB + 13Cf4 (k13 ). ru. react.ion bas bem st.udied relat,ive to t.ba 011 + Cf4 01:12) reacUca. sinc. 

the ratio ot: the nta coeUlcienta k131lt12 is the quantit.y needed for 1dent.ifr1n& _u.- sourc ... 

Rust. and St..., ... (1980) obtained a vatue ot: 1.003 for kU/U at. 298 r; wbile t.ba rae_to _urlDlClt. 

ot: Davidson!L!J.. (1987) yields 1.010±0.007 at. tha s_ t..operat,ure. 110 data on tha t.8perature 

dapandence ot: k131lt12 i. available. We have rec~ed the value ... urad by Cavidson!L!l,. since 

51 

f 

r 

04 

T. _-!L: ___________________ _ 

.NIl 

1L- - ------____ .... _-_._---31 
r~'·~ 

) 

• 

II 

,; 

r. 

~ 

) 

at 

"!J 

- .~-----.. -------- - --- ------.- ------ -------_.-

th"7 pr .. ct. &cae nuooa .. to tIby .... t. ad S~' nlue cOlll4 be low. the uro~ bu 18 

1.01O±O.007 ....t it. anrtap. with the_uured value of~""t. aDdSt.evma. 

04. OIl + r;!1a. Thera 1a aaod -are-to ~ nine at.adiea of thia raacUOD at. 2114 X, i.e., Graina~ 

(11170a), BcMud aDd EwcaCil (11171511), On~ead~. (11175), Lee ad tma (11142), LaII (1117S1b), Tully 

~. (1883), Jaca& 5..!l. (111&4), Tully~. (111411), -S .hum n...sJ.. (11188). All Uleae 

.t.ud1 .. wan DOt. carried _to at. euct.ly 2118 X. therefon," hava racalculat.ad the 2114 X value, 

by .. a..iII& lID E/ll of 1100 X, !or thoae .t.wU.. _ua the _ t.e.puat.un ... 1lOt. 2118 X. tha 

ava~ .. e of th .. a nine ...-r-m.. 1& k(2114 X). n.. t...-paratun dapcdaalce ... CCIIplt.ed by "ina 

the dat.a of Grainer (1II70a), Tully~. (11153), aDd Jaaaa~. (11144). Bl&bar ~nt.ura 

ra.ult.a of Baulcb.6-l1. (11143), met Tull,.~. (11188) ue ill ~ __ t. .ith the nCO"'"DCled 

vall». Jlec~t. ~~ by 1lu.uD&~ n...s1. ~~1_~8?b) ~~ th~ t.e.puat.ure rmae ~4-438 X ue_ 

in aaocI ~-r. with the ~e~ed valu ... 

~. OIl + SBa. the~e an IUDY _uw:~t.a of the rat.e coeWc1mt. at. za8 X. In W. waluat.lco •• 

h ..... ccaaide~ed onl,. the direct. ... ur_t.a that. ue report.ed in the llt.erature. The •• u. 

_asur_t.a byGnlDar (1970a), Tully n...sl. (11153), Droa,e met Tully (111411), ScbIII1dt. at el. 

(1985), Baulch .t al. (1985), aDd Bradley!l...!l. (1973). the za8 X value 18 tha avera,e of tha •• 

• ix .t.ud1a.. are1Dar (197Ca), Tully at. al. (1983), met Droa,e ad Tully (1986) have _aaured tha 

t.emperatura dapG)dmca of thi. rucUca, ad the rac:~ed E/ll ... obtained frca a linau laut. 

.quara. aaa1.y.1a of the dat.e~ traa th .... t.wUa. at. T balow "'0 X. The A-fact.or ... acljuat.ed to 

~aproduce k(298- X);- thi.~ ~eactico baa t.wo po .. ible~ch.aaau, i.a. ;-ab.tract.icm of the P~1JDarT or 

the .ac:ond&ry B-atool. th.~.fora, DOD-Ar~han1ua beh."ior 18 ashlhited oyar a .ida t.ampara~a rmaa, 

a •• hoooD by Tull,. .t. al., Imd Drca,a met Tull,.. Th. hranch1n& rat.io •• ara a.timated from the latter: 

k pr1Jlary - 6.3 x 10-12 axp(-1050/T) ca3 ..,lacula-1 .-1 

ksecondary - 6.3 x 10-12 np(-5601T) =3 molecu1a-1 .-1 

These nlDban are in rauCll.ble &&ra_t .ith tha oldar dat.a of Grainar. 

D6. OS + B.z.OJ. Tha value for k(298~1:) 18 the avuqa of thoaa-det.amlned by Atkinson ad Pitt.a- (1978} 

....t SUef ll....!I.. (1980), both usln& the flash photoly.i.-ra.onance nuorucenca t.acbDiqua. tha 

value reported by Horri. and lI1ki (1971) &&r". withill the .t.ated uncartainty. there ua bOO 

relative valua. which are not in qra_t with the ~acCllllllaDdatlODS. The valua of Hilti !1..!,l. 

(1978h) nlat.iv. to C8 + C2B4 1a M&har tohila the value of SaUth (1978) nlatl".. to CD + C8 is 

lower. the lat.t.er dat.a ue alao at varhnca .ith the nealislhla t.IIperatur. dapaadenc. ob.uvad 

in the two nub photol,..is .tudi... Althou&h Atkinson aDd Pitt.a a .. lan a small activat.ion .... r'y 

(EtR - 901150), th.ir data .,t. 3!6 K and 426 K and that. of Stief li..!1. at. 228 1:, 257 I: and ~62 x: 

are aU w[thin~ 10% of" the ~ k(293 !c:) valua. Thus, th":-c:od>iIlad data •• ~ __ .Uis~ •• t.a EIR - O~. ~th • 

.bst.ractlca re.ctico shown in th. tAbla is probabl,. the lIISjor channal; other chann.la 111&1' cCXltributa 

(Horowitz !L!1., 1978). 

D7. OH + ~CD. Th.n ara six lDeasurem ... t. of this rata coeffic1ent. at. 298 X, Horri.li..!1. (1)>11), 

Hilti ~. (1978h), AtltiDson aDd Pitt.a (1978), Xarr cd Sheppard (1981), s-.~. (11i85) , 

and Micha.l!1-!.l.. (1985a). Tha recoamendad velu. of It(m X) 1& the averqa of the ........ ur_ts. 

Atkinacm aDd Pit.ts, s-.. ~ .. and Michaal ~ ....... ured the tempara~a depaadance of thi. 

rat.e coaffic1 .. t. and !ound it. to axhlbit a ,..,ative taparature d-s>eadenc.. Tha ncoamandad 'ftlue 

of EIR is the ."arasa EIR of thasa .t.udie.. Tha A-factor has baan adjuat.ad to ,.lald tha raccaomended valu. of 1t(298 X). 

52 

--l 

I 

-

~ 
-.r: .:0;. 

" 

.. ' 

) 

.. 

'" 

,: 

;.-

-:/ 

. Y 

,/. .... :, 

.~ 

~ 

08. CB + Cll:!CXlB. lb. ree~ed vahI. ia that. of .iki J1..1).. Cll183). t1w7...aured tha ute eoeUicict. 

relati". to that. of CB with CiJ4 by amitodna Cll:!CXlB diaappeu_ce valDa m "Ill .yat.. rua 

... asured value ia _ry f .. t. md heea ia DOt. .zpec:tecI to ahaw .w..t.antial ~atun dependmc:e • 

lIiki ~. have detemiDed that the rate coeUiciwt. fo~ B-atea abat.ract1ea ~_ the CB;, I%OIIP 

h appnmimately 0.7 tiMa that. fo~ B-atea abstraction ~_ the CB &rOUP. IndapDdct., direct. 

_~ts of thia rate coeUic:iwt. are nHded. 

09. OS + l1:li. thb react.iea ia pr ... u. depcdant.. The ~ac:~ value 18 the hiab presaua u.1t. 

..... ured by Frits~. (11184) uaiDa a lasax pbotol.ysia-~ .. _a fiuoreacwc:a apparat.ua. PlUlUpa 

(111711) .tudied thia ~.ac:t.iea uaiDa a di.ehaqa f~ ~atua at. ~ puuur .. and found the ~_ 

co.ffic:iwt. to have ~.ac:had the hi&h pr ... u~. liIIit. at. -10 t= at. 2118 1:. F~it.&!L.!l. 'a ~.au1ta 

ceatradict this findina. they &&r" with PhilUp'. -.urad nl._, within a fact-= of tMo, at 7 

to~~ but th.,. fiJld k-to incre ... fut.ha~ with p~ .. sure. tha pcodgcte of the ~.ac:t.iea u. ~. 

Th • .....ued A-facto~ a~an to be ~. 

010. OS + Cll:!a. rua ~ata co.ffic:ict haa bem ~uued .. a fllDCt.i= of t..parat.ura, by ~ia !L.!l. 

(1981) betw.en 29,8 md 424.1:, J:u1")'lo mel w:nabla. (111114) betarMn 230 and 363 1:. and Rhua and ZallDe~ 

(private c.-.zUcation, 1987) b.t_w 295 and 520 1:. In additica, tha 2911 I: value has b.m _aaued 

by Zatzach (private cOlllllUllication, 1987) and Paul.t~. (19114a). lb. 2911 J: rasulta of Burl. 

~. are in di.&&r._t with all other _ .. u_ta and tlIerafo~. have not. bem inCluded. Iha 

~ac.-xlad 298 I: value ia tha av.~q •. .!If aU other studi... The t.Ipa~atu. d.paDdwc .... CCIIIpUteci 

usin& the results of ¥Urylo .md.~la..!.~0-3.~~!C) aDd the lowaJ:.t-.pa~atu. ~alu!!_(i ••• , 295-3911:) 

of Rhaaa md Z.Uner. TM> pointa ara worth notin&: (a) Rhua aDd ZaUner ob .. rve a curved Armwi"s 

plot. ..,e in the ~~at.u. ran&a of 295-520 I: and th.refore azt.~apolat1an of the recOllllleOded 

."Pression could l.ad to lui •• rron. and (b) Zau.ch oburnd a pr ... u. d.pendaat. incr .... at. 

k (298 1:) tohich levela off at. about. 1 atmosphar... rua ob •• rvation ia contradictory to the result. 

of other inv •• Us.t.iona. A cOlllpl.x resct.ion a:otcban1 .. camot. be Nl.d out.. Th. producta of the 

reaction are unknown. 

011. H02 + ClzO. It. i. b.Uaved that thi. reaction procHds throush addition of 002 to 'CHzO (Su !La., 

1979b,c, Veyrot. ~ •• 1982). Th. value of the rat. co.fficient d.duced by Su.!l...!1. (1979c), 

b .. ad CD IDOd.Una a ccmplex .ysta 1nvolvins the oxid.tion of CHz0' ia approximat.ly aave tt-s 

lower thm that. obtained by Veyr.t .t al. (1982), .me also mod.led a ccmplax .yat.aD. Ih. racOlllMDdad 

value is m averas. of tha two _ .. UlIMDt. and 18 vary UDcart.a1n. Su~. (1979c) have daduced 

t.hat the lifltime of the adduct towards d.cOIIIpOaition to ClzO and 802 is -1 sac at. 298 1:. 

D12. 0 + IDI. Thi. reaction h .. be ... studi.d at hiab tllllpOlratu •• , i ••• , T >1000 1:, bacaus. of its 

import.mco in ccmbustion sy.t._, Roth~. (1980), Szek.ly It. at. (1984), and Lous. and Bmson 

(1984). Cavils md Thrush (1968) studied this react.ion between 469 mel 574 I: whil. l'arry aid 

M.lius (1984) studied it..b.t. .... n 540 and 900 K. R.uults of l'arr)' .. and M.lius are in asr._nt with 

tbos. of Davils and Thrush. Ou~ recarmandation ia basad an th ••• two studios. Thia-react.ion has two 

reactiCD pathway.: 0 + ~ ~ B + 11M, t.B - -6 kcd/lDOl (ka); mel 0 + o::lI ~ CO + HH (Itb), t.B - -36 

kcal/1D01. Th. brancbins ration kan" for ~.s. t...., charm.la has b.m lDIasured to_b~_-2 at. T .. 860 1:. 

Th. brmchin& rat.io at. lowa~ tllllp.rat.u •• is unknown. 

013. 0 + Crrz. Thl value at. 298 I: 18 m .varq. of taD ..... UllMDta; Arrin&t.on It al. (1965), SulUnn 

and Warnick (1965), Brown and thrush (19'j7). HOYlmann.!S:...!l. (1967. 1969). w.atanbers and da!i&as 

(1969b), J ..... md Glasa (1970), Stuhl md lIiki (1971), W.atwbars and daB ... (1977), mel Aleksandrov 

ll...!!. (1981). Th.ra 18 raasonably ,oad &&r._t aDOD& the .. studi.s. Arrinston~. (l965) 

did not. obs.rv. a t.lIIIpOIrat.ur. d.pendaac., an obslrvatioa which ... lat..r .oooon to be .rran""" by 

W.stacMr, and daHua (19691». w.staabar, aDd daB ... (l96Slb) , Boylrmcm .t. d. (1969), mel 

AlokslCdrov~. (1981) are the only authors who have _ .. urad the t..paratura depend.nc. below 

500 !C. Wastleb.r, and dlBs .. obs.rrad a curved Arrbanius plot at hi&har tllllperature. In the rlll:& • 

53 

---- ----I 

"' 
-'-'!T ....... 

') 

r 

~. 

--...... -

.r 

J~ ~. 

~ 

D14. 

............ 

~5-450 1:. Auhei ... behaY10r provid .... ad.qu.te d •• cription md the E/R obtained by • !it 0' the 

~ trom theae thr •• ,rogp. in thi. tamperatur. rUII. is rec.-nded. Th. A-!actor .... calculated 

!.o r.produc. k(298 1:), rue re.ctica can have t..., aeta 0' producta. i •••• C200 + B or ~ + CD. 

tlD:Ier molecular be. coMJ.Uons C-PJ has bae ahooa to b. the aoajor product. Th. atudy by 

A1aItsandrov rt. al. ua1n& • di.char,. !low-reaonanc. !luore.c ... c. _thad (under und.!ined pr ... w:. 

ccadit!cas) indicates that the C2,OO + B chu!n.l ccotrihut •• no IIIOr. than 7% to the net. react.ion at. 

238 X • .,U. a aimilar atudy by Vinickhr.!Ul.. (1985) auu .. t. that. both CBz md CDzO .re tozmed. 

o + B2CO. !h. r.c~nded valu .. 'or A. E/R and k(298 1:) are the avarqe. a! tho .. detez:a1ned by 

n- (1979) ua1n& !laah pbotolya1&-reacamc. !luareaceoc. (250 to 498 1:). by n_ .t d. (1960) 

cs1n& d1achaq. !Low-resca.nc. fiuar .. cenc. (2,98 to 748 1:) and Chan& and Barker (1979) ua1D& 

dischars. tl.c=-mass spact.rCIMtry (296 _ to 436 1:). ~All thr.. at.udi.. are in ,oad qre ...... t.. 'th. 

k(298 X) valua 1& .lao Cell. is tent. with tha reaulta a! 111ki ~. (1969). Barron and Penzhorn 

(1969). and Hack and Thruah (1973). AlthOUlh the maehanl_ tor 0 + B2,CO has bam ccaaidered to b. 

the ab.traction r •• ction y1eld1n& OS + IDJ. Chea md Barker .\lIIe.t. that. ... ddition channel 

yi.ld1n& B + 11:02 ....,. b. occur~1n& to the enet. o,~ 30% 0' the total re.ctico. rue coac1uaica 1. 

based on an cbaervat.ion 0' CO2 ... product. a! the reaction under conditions where reactions .uch 

as 0 + BCO - 1I + CO2 and 0 + IDJ .. OB + CO apparently do not. occur. This int..restins sugest.len 

:aada indopmdent. contirmation. 

015. ° + ~CBO. Th. recoamend.d k(298 1:) is the averq. o! thr.e me .. ur_nts by Cadle md Powers 

(:.967). Hack and Thrush (1974".~ .nd'lfin,I.tOn at a1. (1977). which are in sood.irii ..... nt.. C.dl. 

cd Powers acd Sin'let.on.!S:....!l. st.udied this r.action .. • !unct.ion a! t.emperature bet_en 298 I: 

cd 475 X and obt.ained v.ry s1m1lar Arrhenius paramet..rs. n,e r.cClllllended E/R value was obt.ained 

l:y considoriq both seta o! data. ru. reaction is known to proceed vi. B-atom ab.t.raction (Hack 

cd Thrush. 1374; Avery and evet.anov1c. 1965; and Sin&lot.on ~ •• 1977). 

016, :? CH3. ~~. recommend.d k(298 Xl is the w.i&htod avarase o! throe moasurements by Washida and 

;.yes (1976), Washiaa (1980), and PllmIb and Ryan (1982b)' Th. E/R value 1& based on the result.s 

;f Wash1da acd Bayes (1976), who found k to be ind.pmdet. a! t.omper.t.ure betw.en 259 and 341 II:. 

D17. ~ + 02' :bis bimolecular react.ion is not. expect..d to be important., based on the result.s of 

-17 3 -1 -1 !aldwin and :.olden (1978.), who found k < 5 x 10 em IIIOlecule s tor temperatur.s up t.o 

:.2ll0 X. !Chis!.!<....!.!. (1979) tailed to d.tect OB (via ~ + 02 - CB2

0 + OB) at. 368 X and placed an 

-16 3 -1 -1 

;;per limit. of 3 x 10 em IIIOlecule • tor this rat.. cO.!!icient.. Bh .. karan.!1....!!. (1919) 

-11 3 -1 -1 ... und k - 1 x 10 ap(-12,9001T) em molecul. • tor 1800 ~ <2200 !C. Th. latter two 

studies thu. support. the re.ult.. 0' B.ldwin and Gold.... R.ec ... t. .tudi •• by Selzer and Bay .. (1983) 

cd U\mb and Ryan (198211) confirm the low value tor this rate co.!ticient. Puvioua studi •• of 

-ashida and ::.yes (1976) are superseded by tho •• a! S.lzer and Bay... Pluai> and Ryan have placed - . - --16 3 . -1 -1 ,- ,--. c upper ll::it. o! 3 x 10 em molecule • b ... d on their inability to tind BCBO in thelr 

rr;>.r iments • 

018. ~C8 + 02' :be rat.e co.Wcient. .. as tint. m ••• ur.d directly by Radford (1980) bi det..'ct1D& the B'J2 

r=o<iuct. in a laser _",.Uc resonance spectrometer. The .. all 10 .. 0' CB2,0B could have int.roduced 

a lars. error in thi. _uur~t.. Radtord also showed that. the prwioua lDI .. ur~t a! Avr_nko 

-12 3 cd Kolunik--.a (1961) .... in error. WUII!L!1. (1984) .... ured a v.lu. of 1.4 x 10 em 

.. lecule-1 .-l by d.t.ect.1D& th. 802 product.. Rac ... t.l,., Dabe!l...!l. 098S). Grothaer ~. (1985). 

KId Payn.~. (1987) hwe _ .. ured 1t(298 1:) to be clos. to 1.0 x 10-11 ca3 IIOlacule-1 .-1 under 

:=cdit.1aa wilere ... U 10_ are smaU. The recoameadod value i. the averqe 0' th •• e thr ... t.ud1_. 

Since this nact.iOl1 i. qdt.e , .. t. the E/ll is .xpac:t.ad to b. clo •• to zero, Very rec ... t.ly. St.ia, 

(;:riv.t. c.-micat.ions) baa obtained. poeit.iv. act.ivat.ion -raY tor this reaction, 

54 

\:l 

; , 

-" 

.. 

• 

• 
T-~""-

... "I 

J 

)" 

.. 

.. 

II'" 

.: 

;; 

.. 

~ 

., 

,..; 

J ~ 

------ _ .. - -- - .. -.----- ______ .-S 

019. ~O .. OZ' th. recCllllllmded v.lu. for k(Z1I8 It) 1& the av.r ... of tho .. reported bT Lorenz 

~. (1985) CId· Wantuclt~. (1987). th. reCOlllller1ded A-f.ctor and E/R are those obtained 

ua1n& the results o! GutlllaD~. (198Z), Lorma~. (11185), and Wmtuclt !1....!1. (1987) in the 

t~rature ranee Z98 to 500 IC. Thaae inveatileton have llMlaaured k directly under pseudo-first 

ordar conditiema bT !ollOlfiDa ClI:30 vi. laser iMuced fluorescece. the t&IIIparature intuvala 

ware 413 to 608 IC (bT GutIIIaD .!L!l. ), Z98 to 450 It CbT Lorenz !L!1.), and 298 to 973 IC (bT Wmtuclt 

.!.L!l.). COlI:.!.L!1. (1980) uaed m CId product. _lya1& technique to llMlaaure k clown to 298 It. the 

previous hiah tamperature _aaur_ts (Buker~. (11177) and Batt CId Robinson (19711», ue in 

reaaoaabl.. acra-nt. with the derived ezpreaaioa. k(298 IC) is calcu .. ated from the rec~ 

azpraaaion. Ibis val.ue is conaistent with the :zaa IC reaulta of COx!1....!1. (1980) GId with the 

upper l.imJ.t. llMlaaured bT Smden~. (1980b). the A-factor appeua to b. too 1Dw for a b)-drolm 

aU. trmafer reaction. the Arrhmiua pl.ot. is curnd at. hiaher t.aparature· (Wantuclt ~.). the 

reaction -.y be IIIOr. ~licated th .. a aimpl.. ailat.ract.ion. th. products of this reactioo are 

!IOZ and CHz0' .. ahOWD by Hilti~. (1981), llbich is cooabtet. .ith a reported r:s,.0 yield of 

0.8.5±O.lS (Z.llner, private communication, 11187). 

OZO. 11:0" 02' tha value of k(298-1C) is th. aver .. e of the detemiDat.ions by Washida!1....!1. (1974), 

Shibura ~. (1977), Veyrat. and Lescl.aux (1981), md l.an&ford GId Moore (1984). there u. thrae 

maaaur-..t.s of k lOb.r. IICO ... monit.ored via the intracavity dye l.aser absorption technique (Reilly 

~. (1978), lIadtochenko~. (1979), GId GiU~. (1981». Evan thouah there ia azceU ... t. 

acr_t. b.t ..... thes. thre. studi .. , they yield ccaSiatantly_ lDwar valuea t~ tho .. obtein.cCby. 

othar tsc:bniqu.a. There are several. po.aibl. -re_ for thia diacrepmcy: (a) Tba relat.ionship 

bet ..... fICO concantration and laser attenuation a1&ht. not b. lineu, (b) th.re couLd have baen 

daplatioo of 02 in the atatic ayst_ that. .er. used (aa auuaatad by Veyret. GId L .. cl.aux), md 

(c) tbaae ezperlmants •• ra d"i&neci IIIOra for the atudy of pbotochamistry thm kinetics. Therefore, 

tha.. val.ues are not. included in obtslnin& the r&cOlllDaDded value. the recOlllll ... ded tamperatura 

dapacdmce is ... antially identical to that measur.d by Veyret and Lesclaux. We have ezprlssed 

the ':.Emp8raturo ~ependence i:l an A:::'mius foCI even tho~ the authors preferred a :f' form 

(It - S.S x 10-11 r-(O.4%O.3) cm3 molacule-l a-l ). 

OZl. C!f3 + °

3 , The recoamanded A-factor and E/R u. thoae obtained frail the reaults of O&rYzl.o .!U!. 

(1.981). Th. r.aults··o! SiJDonaitla and-Bdcltl.an (11175), basad 011 an malyals o! a cOlllplex syat_, 

are not used. Waahida~. (1980b) used ° .. CzH. aa the aource of C!f:J. Recent. reaults (Bu .. 

at -1. (1981), neinermanna and Lunt: (1981), Bunzlkar.!L!l. (1981), and Inou. IIDd AIt1moto (1981» 

hava shown the ° .. CzH" reaction to ba s poor source of C!f3' Therefore, the reaults of Washid • 

.!L!l. are also not used. 

022. ClI:302" 03' Ibere ue no direct. at.udi.a of this reaction. the quoted uppar limit. is ba.ed on 

indirect evidllllca obtained by SJ.mana~ti~ ~_d Baic_klaa (1975). 

023. ClI:302 + ClI:30Z' The racccmanded val.ue for k(298 Itl _s derived !rail the stucUes bT Bochanadel 

~. (1977), Park .. (!977) , Anaatui ll...!!. (19781, !Can~. (1979), Sanhu .. a ~ •. (1979),_._ 

Sander CId Wataen (1981e), HcM_ ~. (1987), and ICuryl.o md WaUinat.OD (1987). All. the above 

deta%2lnatioos used ult.raviolet abaorpUoo taclm1quas to IDC1litor C!f302 md hane •• aured "ItT, 

wh.re tT is the absorptiOD cro .. a.ctioa for C!f302 at the monitored .avalllll&th. tharefore, tha 

derivad val.u. of It critically depends on the valua of tT uaed. Currantl.y, th.re are lu,e 

dUcrapccia. (apprazilllat.al,. a factor of 2) b.t_aa tba value. of tT _uured by Bochanadal. et. a1., 

Pubs. Sander and W.tSOD, Machi at d. (1980), HeM...!L!l. (11187), CId 1Cury1.o.!U!. (11187e). 

To obtain the val.ua at. 298 It, lID aver",e vah. of tT u. 2.50 ZIII .a obt.ained. Uain& thU val.ue of tT 

and the .. i&btad aver ... value of ItlfT at 2.50 _ th. ftlu. o! 1t(2IIS IC) ... darivad. Iha rec~ 

t.aparatur. d.pendanc. 1& that .aaurad bT Sander IDd Watson (1981c) and 1Cury1.o GId Wal.llnat.OD 

(1987) uain& • value o! tT indapendent of T. It is not clau lOb.thar the above procedure of 

55 

.' 

I J _ 

~ 

~ 

"~ 

~, 
P-~~'!;'.: 

) 

---'-

~ 

l 

~ 

01 

rltCalcu1at.~ k uu. m _ ... ..w. of' 11..ud. bnfon. the error Ualt.a II-. ~ 

1Dcnaeed to IIICCIIIIpMI the val.uee of k ca1=1at.ecl byvut_ ctlIorl. nu.. rHlCt.iClll baa 

t.hrM poel1hlA .. U of prodoxU, 1 •••• 

~O+~ ka 

~OZ + CB;,Oz .. CB.z.O + ~a! + Oz ~ 

CB;,ooc:a, + Oz ko 

__ ~Ill_at.ad1.1 117~ J1-U. (1a80) aad 11kl JLIl. (lSI1) arl lD r..-.hl. ecn-t. _ b~ 

rat.loa at. ZIII )';; kalk ~.3'. ~/lt ~.10. - ~. of th. CIItla~I~f .aUple- p.u-7a, Uut 

t..-parlt.ura c\epIDd_ of k ..,. be caapla:. hrthar· work 1& raqulncl OIl beth the ~. 

dapeDdaac • ...s thl varl.t.iea of brlllChUl& r.t.lo1 with t. .... r.tura. 

D:z4. ·~Oz +-m. the value of k(2111 )';) 18 tJW avuq.-of tho .. dataDdDad 117 Selder-.... W.t._ (1110), 

RrI1ahckara.!1..!1. (1lI81.). Caz IIDd Tyndall (11180). PlI.B~. (lasl). S1aKma1t.1a cd BaictlAD 

(l911) mil ZellDer JS:....5l.. (198a). Valua. loorar 117 _n t.hm • factor of two haw bam report.a4 by 

AdachJ. mil Baaco (1979) aid S~it.lI aid Be1cklaD (19711). The fomar dir.ct. atad7 ... prcblbly 

. iD arror bac.a of lDt.arlarcca 117 CII:lCllO fomaUOIl. l'bI rMulta of SlmonaiUa cd Baictl.aa 

(l1l711) mil Pl_~. (11179) are .. -.I to be-aapanadad 117 tha1r _n recct. valDaa. Rariahdua -- ---

~. (l981a) md S1IDorIaiti. mil Bucklan (las1) bava ...... urad tha t.emparatun dapaDdcca of k 

owr Uait.ecl t.IIIpIr.t.ura rmsa.. l'bI rec~ad A-factor IIDd E/Jl_n obt.ainad bJ • l ... t. aqaara. 

IDIlpla of the data frtID thl t._ .t.ud1I1. lba value of k(218 11:) obt.aiDad by oiillloDa1U. cd BaictlAD 

(11181) 11 Dot. includad; howevar. the larsa arror booa:Ida allow t.ba cal.cul.t.ad VIla of k .t. ns 11: 

t.o O'Iarlap that. _.aurad !l7 S1mcrIaiti. and Be1ckle. Ravlahcltara ll..!!. (19811) flDd that. the 

ruct.ion chamal laad1n& ~o N02 account. for at. la .. t. 80% o! tha ruction. Zel!.:.ar at. al. (1986) 

have ...... urad thl ,,1ald of ~O to be 1.0%0.2. lba.a re.ulta. in conjunction W1th tha 1Dd.1.ract. 

mdaDc:e obt.a1nad by P.ta.!U.l. (1974). conUra th.t. 1t02 fozmat.ica 11 tha major. if DOt. tha ooly, 

reaction path. 

D~. ~02 + 802 • lba rOCCl t.8IOp4Irat.ura valua 11 that. of Caz IIDd 1'7ndall (1979. 1980). Cox aDd Tyrdall 

.110 raport. • larse na,.tiva E/lI. valua ovar a t..Iperat.ura rlDSa 274-338 11:. which is .imilar to 

that. fo1md !or thl 802 + 002 r.action by IIIIDY &rOUP. (a.a DOt.e on 002 + 1102 ). there ara larae 

di.crapclc1 .. in the value of IT ~02 ( ... 024). Tharlfora. t.ba UIIcert.aint.y baa bee lDcrMaed. 

lban an varioua othar rlCllftt. _uur ... ta by t.uylo ~. (198711). Dqaut. ~ (1I1S7), HcAd-. 

at. a1. (1987). Cox (privata camam1catiOll) that. ,,1ald cootra4ictory re.ulta. :barafora. it. 1. 

cautiooad that. tha recam.odad valua may ba incorrect.. In t.ba Ibullca of cCll1lllt.ent. data. _ 

have dacided not. to cMnle th. - prwicUa iacCaii.zxl.t.ion. l'bI rat.a coef!1cill1t. DMda indepoox!ct. 

varific.t.ion at on •• tmQ~ara. IIDd furthar _uur_t.a of pre •• ura ••• t.ar vapor. cd tAalparature 

dapecdanc... It. i, ·.lao nec ... ary to _aaura the "illd. of prnduct.a in t.h1. raac+.J.on to aback for 

the preaenca 0.( IIIUl.Upla .,.thwaya. 

D25. \103 + CO. '%ha upper llmit. 11 b .. ad 00 the reaul.t.a of Rldl.a7 md McFarland (privata c~caUOIl. 

1984) aDd BJorth at. d. (1988). Ridley and HcFarlmd e.t.1Mt.ad an upper llmit. of 1 x 10-%1 _3 

-1 -1 _lac:ull • baaed on their _~t. of ~ 10.. 111 Gca •• co. BJort.b~. obta1l:iod an -111 3 -1 -1 

upper Uait. 0' 4 x 10 CIII _lac:ula • baaed OIl an TrIll 4IZIalyai. of bou.p1cally l.abal.ed 

CO 10 .. in the prllec. of \103. !arroora~. (1118~) obtained 111 uppar l.JJa1t. of 4 x 10-15 _3 

..,lac:ula -1 .-1. which b conai.tact. with the other two awcu.M. Product.. ara ezpect.ad to be 

\102 + CO2 • 

56 

.~-\; 

--

~­

~ 

• 
--

~:'J"" 

) 

t ---

~ 

i 

~ 

-.~ 

~l 

-' 

/.; 

Yo 

f.~ •• 

• )-

" ~ 

---------- -----~- ~----~----~--~. ~---------."- .~ 

D27. 11)3. + CILJl. there are taoa ___ ta of th1a ratA -'Uc1 .. t. at. 2a8 1:, At.kUIaaa~. (laB4) 

aDd Cct.Hll~. (ua5). th. wl.ue nport.s b7 ~.ILI1. CIa' \), k - (3.23:t0.U) z 10-111 

ca3 _J.ec:ua -1 .-1, ia correctacl too 5.' z 10-111 ca3 .,UeulA -1 .-1 to 8CCOUDt. for th. 

di~ nl_ of the eqa1um:t. _t.ct. for the 11)3 + .02 : 12°

5 r • .ct.1aa that. ... ....ured 

aubaeqalllt. to th18 atacf7' b7 the ._ aroap aU. the ._ appuatu8. th18 cornctlon ia in 

accordmc. with their auca.at.lal (ra.- A.IJ" lDS4). the TAlue reported b)' emuaU ~., 

k - 11.3 z 10-15 ca3 .,lecul.-1 a-1 1a in aood aar~ with th. conected Yalu. of AtkiDaoD 

5..11. the HC_ rIM .alii. ia tM .vance of th ... t;., .tadi... CaDtnU!L.!l. haw ,ood 

wi.s-c. to .UU .. t. that. 8103 lad ClIO are th. producta of thi. nactioa. th. t.ealparatun 

d~. of w. rata c_Ulclat. i • ..w-. 

D2II. - ." + CB:sCllO ... -... eDtz7 •. " ~re .. t-.r _IF a~ of thb nt. caaatmt, Houia &ad II1k! (11174). 

Atk1DaOD~. (laB4), CaaU.UJS...I1. (1I11III), Dl,.altccky cd IIowarcI (privat. coaamicatioa, laB7). 

the -we rapartad b)' Atlt1n_~. (1*), k - (1.34to.2II) z 10-15 ca3 IIIOlacul.-1 .1, ia 

corneted to 2.4 x 10-15 _3 ~-1 .-1 .. dlac:aa.ed for tM IIO:s + ~CO n8Ct.iaa abono aDd .. 

• usa .. ted b)' tuuaa!1..5l. (11114). the rae ded value i. the -aa. of the ~u .. obt.aJned by 

Atk1DaOD n..sl,. (2.4 x 10-15 ca' _i.~1~-1 .-1,-: -CaDtnU ~. (2.1 x 10-15 "a.' _lKUi.-1 

.-1), aDd DluackanckJ and Boord (2.74 x 10-15 _, IIIOlacula-1 .-1). th. n.ulta of Houl. aad 

lUU ear .. with th. nc.-aded Yalua .me thelr od&iDal data 18 re-analyzad usiD& th. CU%rct.ly 

rec~ed ~ value f_= th._ aqullJ])d.. coastaDt fIn: the nect.1oa \1)2 + 1103 : 12°

5 .. shoim by 

Dl.u&ak&DCk7 aDd Boorud. Dluacbacky md ~ ~. .tudled the t-p.r~.tun d8J*ld.nc. of thia 

reacti';"~- th~lr _uarad ";aiua of E/ll-b ~~. th-."A-fact.or h .. ~-ti'-.n "calculated to yl.ld"-

k(2911) r8C~ad han. Mania aDd lI1ltl, aDd C .. ueU~. ob.arved the fomatlon of l1li:)3 mel 

PAll in tba1r atudie., ooh1cl> .trexllly .uu •• ta that 8103 cd c:B:lCO an the producta of thia nact.1oa. 

n. Cl + 0,. the re.ulta raportAd !m: k(2lI8 1:) b)' Wataon~. (111111), Z&lmbar!!...!l.. (19111), lUrylo 

ancl Braun (1916) and Clyne and J1p (1916a) an In looci aln_t, mel have been used to eletermine 

the preforred value at. this taperatu%e. n:.. valu •• repcrtad by Leu and DeMore (1976) (due to the 

wiele .rror l1m1ta) c-.cl Clyne &ad Vataoa (19"a) (tM valua b in.xpUcably hlah) ara not. considered. 

the tow: Arzbclua apre .. lema are In fair aar_t witbiD tll. teperatura r..... 205-300 X. In 

thi. ~ature ranp, ~ rata conatant. at. cry partlcular t.emparatur. aar" to within 30-40%. 

Althou&h th. valu •• of the Ilcti"ftt1oo -al:l7 obtained by Vataon et al. mel lUrylo ancl Braun are in 

exc.u.- qra_t, the value of k in the .tudy of 1Wzy1o and Braun b cons latently (-11%) lower 

thaD that of Wataon et a1. thia..,. .uaa-t. a ayat_tlc unel.r •• tilllat. of th. ,rate constmt, a. 

:.he valuas frCIII the other thr .. e&ree so ... U at 2911 X. A IIOra elbturb1n& difference 1. the Icatter 

In ~ value. reported for the activatlan onartD' (338-831 call_l). However, thare b DO reason 

to pr.fer u:ry on ••• of data to cry other; thanfoni~ tha pre fen&<! Arrhenius exprasslon shown 

shove w_ obta1nad b)' computbla the _an of the fOU% noulta between 205 mel 298 X. Inclusion 

_of lUahar t.llllplretun (s 466 1:) uperimental data would ylelel the foUowlna Arrhanlua expreuloa: 

k - ~3.W.0) X 10-11-exp(-3~0±151T). -" --" " 

C. 

Vanelenmclm ancl Buta (1982) brra interpret.ecf tMlr observatlon of OX}'IID atoma ln thb ayar..a as 

wiclenc. for ICQa production -(a~l-O.S%) of Oz (1:;) in thb reaction. Tha pcSSlbl. production 

of a1qlat. 1I01ecuiar 0%)"&- in W. r.acUoa baa at.o b_ dbcuaaed b)' DeMore (1981), in coanecUon 

wlth the ~ pboto .... ltiXed cSa<:c.poaltiOD of 0_. lIoorever 0100 mel Leu (1985) _n unabl. to 

detect Oz(li) or 02(1~) In the Cl + 03 .,-st- and lit upper Utita to the branchina ratio. for 

-4 -2 their production of S x 10 lid 2.S x 10 ,napac:t.1Y1iy. n... tha _chanl_ for productioa of 

oX7l- _ in thiS syat_ b _l.ar. 

Cl + liz. Thia Arz!I&Dlua apraaica b l:aacl CD the data below 300 I: reportad b)' Wataon ~. 

(1975), lae~. (Un), Hilla sad Gordea (111111), aDd nta mel Stacban (1982). Th. reaulta of 

th.ae .taUe. are in uceU_t. ~t belDw 300 1:; the data at. blaher t.ll!lplratur .. are in aCllllOlbat 

poonr e&rI_t. ~ resulta of Wataon et .1., Hillar and Gordoa, ancl nta oncl Stecmm aare. 

57 

--- -------

t-

. 

~ 

~ 
---

.... _; • .1" .. 

III! 

) 

.. 

.. 

'" 

.: 

.::; 

.I 

J~ 

..:...I 

_11 (att.r ut.rapolat,1cm) with the r.ul.ta d a-c.~. (taU) ...t Stein.r GId 1Ud •• l (1939) 

.t, hi&her taperatur... For. di.cuaaica ot t.be larp.-b0d7 otrata data. "-hi&h t.eperatur ...... 

the nvi .. b7 Baulch~. (1980). HiUar GId Gordea mcS Xita ...s St;.eciua wo _uured the rat • 

ot the revers. ruction, and fOUDd the ratio to be in &OOd ecr_ wUb eq:&iUbri_ c .... t.ant. dAta. 

D. Cl + ca4• Th. val .... reported tra. the thirt.eeD u.olut.e rate _~ieat. atudi .. for It at. 298 !C 

fall in the rana. (0.99 to 1.48) x 10-13, rith a _ Yal. ... of 1.1.5 s 10-13 • Bowever, ba.ed 

upon the .t.at.ed confid.nc. Uaita reported 1D each .bod)', the nIlI. ~ valaa. far exceed. th.t. to -13 b. upected. A pr.f.rred aver ... val ... of 1.0 s 10 ~ be clet.ez:.ined frOID the ahao1ut. rat. 

coetticient. .tudi.. for It at. 298 ~ by ~viDa equal .. ~ to U. Yalu_ reported in Lin .t. .L. 

(1978.), Wataoa .t 81. (1976), HamUl2a ...s J:oJr.rlo (1877), Wbrt.ocIt at d. (11177), Zahni.er .t. d. 

(1978), Hicha.l md L •• (1977), ~r (1878), ~ Ilavi.abaz*er. _ Wu.- (1Il10). %be Valu •• derived 

for It-a~298-!C f= tJi.-cciiPeUt.ive chlorinatJ.ca .t.odi .. o~1'riUhard.n...!l. (1954),- raOs--(19"), 

Pritchard at a1. (19~~), ~ and hlaca (19'11), and LiD ~. (197Se) raa&. !raD (0.9S-1.13) X 

10-13, with ... aver ... value of 1.02 s 10-13• the prec.x:red ftlu. ot 1.0 s 10-13 ... obt.eined 

by talt1n& a ...... value frca the _.t. rali~ abeolute CId ra1.at.i.... rate coa~ciant. .tudi ••• 

Ther. have haan Din. absolute .tudi_ ot lb. teqI.rat.or. deopeDdance o~ It. In ,.n.ral tha qr .... ant. 

b.t. .... o mo.t of lb ••• • t.udJ. .. em be coaalderad to b. quite aoocl. 1Iooravwr,!Dr. "'-iD&ful maly.is 

ot the rapart.ed .tudi .. it. is b •• t. to diacu •• th_ in e.u.a of be) cH.at.1Dct. t.emperatur. ra,iona, 

(.) b.low 300 IC, and (b) above 300 !C. Thr .. r.&OIIIIDC. fiDor.ac:aaca .t.udiea·have haan performed 

_.over the teq>eratur. rana. -200-S00 !C (~ ~. (1S17)..--Zabniser ~ .1, -(1978) and lC.,.aer . 

(1978» and in .ach cua a atrona noalinaar Arrhaniaa behavior ... cb •• rnd. Raviahmkara md 

Win. (1980) alao noted nonlin.ar Arshaniaa ~or onr • mon limited taoperat.ur. rma.. Thi. 

behavior t.end. to .xplain partJ.aUy t.ba lara. varianc. in the valuea ~ E/1 reported hatwHn tho •• 

oth.r inv.at.i,ator. who pradaaiDmt.ly .t.odiad this raact.icID below 300 ~ (Wataon at al. (1976) and 

Hannina and lCurylo (1977» ...s tho •• tlbo oo1y .tudied it. abcrra 300 !C (Cl.yn. _ Wallter (1973), Poulet. 

~. (974). and Lin~. (1978a». :h. a&r.ament. bet_.n all .tudias bolow 300 K 11 &ood, with 

valuea of (a) EIR ran&in& from 1229-1320 IC, and (b) It(Z30 IC) rmain& !r:a (2.64-3.32) x 10-14 • 

Th .... an of the t .... discbar,. flow value. (ZabJlJ.aar!i...!l. (1978) ODd ~.r (1:178» i. 2.67 X 10-14, 

whi1. tha ....... of lb. four flash pwtolyaia vah»a (Wataoa~. (1976), HIaUn& GId IWr7lo (1977), 

Wbyt.oclt.ot. a1. (1917), md Raviahankara ...s WiDe ClG80» 1a 3.22 s 10-~4 at. 230 L Ther. have not. 

b.an artT absoluta st.udies at. atratospheric t..aparatur .. other the tho .. .mtch ut.ilized lb. naonanc. 

fluore.cmc. techDiqu.. Raviahmltara...s WiDe (1980) hawa &aU_ted that. the r •• ulta obt.ained 

uaina lb. diachar,. flow md caapet.itJ.... chloriDatica techniquaa m6T b. in .rror at. the lower 

tamparaturos «240 IC) due to • DOD-aquil1hraUOD of the Zp,1.I2 ...s 2p31% .tate. ot at.allic chlorin •• 

Ravishmkara and Wina obaarvad .. that. at. teperatur .. below .240 !C tba appuent. bimolecular rata 

coa.t. ... t. ... d.pmdmt. upCID the ch..tcal caopoalt.ion of the react.ioa .t%tun; 1. •• , it lb. lllisture 

did not CCX1tain an .Uicimt. .pin equilibrator, •• ,. Ar or c:t:l.., the bia:llecular rate coast.mt 

- d.creued ·.t _hi&h CR. ccncmtraUoaa;·· :h. ch8Dical compoaitioa·in each of the nash photoly.is 

atudi.a contain.d an ."iciant. spin. aquilibr.t.or,- tlbarau this .... noe tha cu. in tha diachar,. 

flow .tudi... However, the raactor walla in the diacllarp flow at.ud1as COIll.d have hac .xpected 

to have acted as an .'ficiant·.pin·equilibrator. Conaaqoant.1y, CDtU tba hypoth.ai. ot Ravishmltara 

and WiD. 1& prove it. i ... ...ad that. tha diaebar,. n- ...t a.pat.1tiv. chlorinat.ion.raault.a are 

nliable. 

Above 300 IC the thrH re.oalDC. fluor .. cane •• tudia. nported (a) -averaaed- valu .. of !/R rana1D& 

fro. ~30-1623 IC, md (b) "slue. ~ 1t(~0 !C) rlll&blc ~ (7.74-8.76) s 10-13• thr ...... 

.pect.roIIIIItric .t.udi .. have ham ~JlIIed ahc-ra 300 !C with EJ1...u... rllllin& !raD 1409-1790 !C. 

The dAt.a of Poulat.!!<....!l. (1974) ara apuH -S .c:attarad, that. of Cl.7JlS ODd Walker (1973) .bow 

too .t.roaa a tamparatur. depaDdaDca (c:aapuad to aU otber abaolute .ad a.patiU.". stadia.) and 

1t(298 !C) 1s -20% h1&har thaD lb. p~t.n:ed vahM at. 2Il8~, while that. of L!D~. (1i78a) i. in 

fair qr._t. with the r •• cnmce fl.aoraacanca ~ault.a • 

58 

-~ 

.I' 

f ._. 

~ 
, 

) 

III 

• 

i 

J 

..:...I 

In cCillclusion, it should b. stated that the best Yel. .... of It trc. the .. solute studi .. , both abow 

and below 300 1:, are obtained traa th. resonanc. flaox.acenc. stDdi .. _ n.. CCIIIp8titiv. chlorination 

reaulta diUer trca thos. obtained fro. the shsolute .tudi .. in thet linear Armeniu. behavior is 

obsarnd. 'Ibis dUferenc. ia the =-.ior diacr.pIDC7 bet_en the t_ t7PH of ezper1ments. The 

valu.s of E/R rllJl&. from 1503 to lSl0 1:, and 1t(230 1:) from (2.11-2.'4) :It 10-14 with a .... an value 

of 2.27 :It 10-14• It can b. SND fro. the abov. discussion that the aver ... valu.s at 230 K are: 

3.19 :It 10-14 (nub pbotolyaia), 2.67 :It 10-14 (di.chars. a-) end 2.27 :It 10-14 (comp.titive 

chlorination). Th.s. diUerenc •• increu. et lower t.eaperatur.a. IlI1til the bypoth.a1s of 

RaviabSllkara WId Win. (1980) ia z:.-.x-1ned, the praf.rred Arm..uua expression attllllpts to belt 

fit tha re.ulta cbtaiDed betaoaeD 200 end 300 r: trc. all aourcaa. the averq. valu. of It at 298 x: 

ia 1.04 :It 10-13, IIId at 230 r: ia 2.71 :It 10-14 (thia 1& a aimpla _ of tha thr .. averq. valu .. ). 

the prefarred Arrhanius apraaaiOD ,.1alda valu.. ai.Uar to thos. obtained in th. discbar,. flowraaClll&c. nuoreacenc.-at.udias;-- IC·-CIIllj -nub-pbotol:rs1&-reSCIIUIDC. n .... nac.aca resulta .~. used 

then an altarnate apressiCill of 6.4 x 10-U (up(-UOOIT» can be obtainad C1t(298 1:) - 1.07 x 102-13 

and 1t(230 1:) - 3.19 x 10-14 ) • 

. ~.tudy (BlOle&han et al. (1981» us1n& very low pre .. ur. reactor tacbniqu .. reporta results !rOlll 

233 to 338 K in exc.Uent qr .. lII.nt with the other recent .uur_ta. thay account for the 

curvature 1D the Arrhenius plot at h1&har t-.paratur.a by transition state theory. H.asured 

equillbrilD cClllStmta are used to derive a value of the heat of formatiCill of the .... thyl radical at 

298 ~o..f_3'.1±0.1 kcalllllOl. 

E4. Cl + CzB6' The absolute rata coefficients reported in all !our .tudies (Davi. at a1. (1970). 

HamUn& and Kurylo (1977), Lewis et al. (1980), end It.,- et at. (1980» are iD ,ood qreaDant at 

298 K. Th. value reported by D.,,1& et at. was prob .. l,. ovareatiaatad by -10% (th. authors assumed 

that If wu proportional to [ClI O•

9 , wIlerea. a linear relatlClllahip betwaao If end [Cl] probably 

held Ullder their experiaaota! ccaditiClllS). Th. preferred valoe at 298 r: was taken to b. a staple _1' ",ean of the four values (the value reported by Davis ~. "as reduced by 10%), 1. e .• S. 7 x 10 ••. 

The tl'O values reported for EIR are in &ood· qre.....,t; E/R - 61 K (MaJm1n& and Kurylo) and E/R • 

130 K (Lewi. ~.). A aimple l.ut square. fit to all the data would unfairl,. _i&!>t the data 

of Lewis ~. due to the lar&er tamparatur. rene. covered. Th.r.fore, th. pr.ferred value of 

7.7 x 10-11 u:p(-90/T) is an apr.Sa1C11l which be.t !Us the data of Lewia ~. and Hanning and 

Kurylo between 220 &.nd 3S0 !C. 

£5. Cl + C3Ba. 'Ibis recClllD&Ddation is baaed on resulta ov.r the taeparature rane. 220-607 !C reported 

in the recent diachar,. tlow-resonance fluorucence study of :..ria ~. (198·0). These results 

are conaistent with those obtained iD the ccmpatitiva chlor~tion studie._ of Pritchard ~. 

(1955) and Knox and 1f.1aon (1959). 

_!S •.. Cl...Y_~OII. This reccmmendation is baaed on the 20o-~0 !C reaultaof MiChael. et -a1; (1979b) by the 

flash pbotol,..ia-resonance tAcbn1qu. and the 298 I: raauUs of P.,.ua ~. (1987) by the disct.ar&e 

now-maaa .pectr .... try tecbnique. Product anal,.si. and isotopic auhatitutiCill have estabUshed that 

the ruction .... cbmi .. consista of abstraction- of a bydro,an .tea-from the _thyl group rather than 

trOlD tha bydroxyl &roup. Se. Rad!ord (1980), Radford .!L!l. (1981), Heier ~. (1984), and 

Payne at al. (1987). this ruction haa been used u a .ource of ~CB and as a source of B02 by 

t.h4 raaction of CBzOll with 02' 

E7. Cl + ~Cl. Th. resulta reported by Cl,... and Walker (1973) and KaoniD& and J:urylo (1977) are in 

good acr_t et 2118 1:. Bowver, the"al..- of the activatiClll -ru _aaured by Hlmn1n& and 

Kurylo ia s1&D1ficantl,. l.<Mar thaD that .uurad by Clyn. and WalItar. !loth groups of workers 

.... urad the rate c:onatant !.or the Cl + CB4 .ad, s1ailarly, the activetica -ru ... ured by 

Hmn1n& and Kurylo was si9l1fic .. U,. l.<Mar the that _uurad by Cl)'Da sad Walker. It ia suueated 

that tha di.charae no .. "." apec:tr~c tacbniqaa ... in this cu. aubJect to • systematic 

59 

-, 

..J 

~ .- )f 

-- .. --- .-. -- ,. 
• .. .:=:- • 

) 

.. •

tt 

. .. 

) 

Ea. 

.uor, m4 1~ 1. rec~ that. the flub pbotol7ah naal.t.a be uecI for .uatoapber1c calculaticma 

ill the 200-300" tallpUat.ar. r ... (ae. cl1acuadaa of the Cl + CB. atudl .. ). In the di • .::ua.iaa of 

the Cl + CB4 nacUaa 1~ .......... tact that. _ of the apparaa~ diacrapaDC7 bet.oaD the n&Ult. 

of Clyne aDd w.lltu aDd the fl.uh pboWl7ala .tuIU •• CC1 be aplaiDad by ~au ArmaaJ.ua 1:IaMv10r. 

If-.r, i~ 18 la .. llk.17 that. thb CaD be 1mrcItad for W. r~1oD .. the pra-azpxMnt1al Afactor ( .. __ ad ill the fl.&aA pbotol.7ala .tuIU •• ) I .• alraadT -3.5 :It 10-11 aDd the dlDif1caD~ 

curvatur. tCich woul.ci be nqW.:r:ad iD the ~UII plot to -.It. the data cc.s-t1hl. 1IOUld r ... ult 

-10 ill ID UDl:NaClDlbl,. M&b valua for A (>2 :It 10 ) • 

Cl + CB3a. the n~Uaa accapU the uppal: lia1~ at roc. t.puatun npoRad by I:ur)olo and 

!:Dabl. (1118') "'111& flub pbotol.7a18-n.--. ~n.cec.. Paulat 4...11. (1II84a) uaad cUachars. 

fJ.ow-.u. apac~tJ:7 IDd r~ the azpr.daa It - 3.5:1t 10-11 ap(-2785n) ovar the tallpUatur. 

-15 nasa 478-723 1: •. nwy. alae npo~ a-_ ta.puatur. val.ua of 8 z 10 ,tCich 1. a factor of 

3 anatar the that ca1cu1.at.ad fro. their aprHaiaa. It. -wean Ukel,. t.ba~ their _ ~ntun 

obauvatiaaa wen .troaal,. 1afiuaacad by baWJ:OlaDaOUa proc •• a.. It ahoul.cI be DOtad t.bat. th.ir 

azu.polatAd _ ~a.paraton valu. is appra1Jaatal,. equal to Xazylo m4 IDabla'. uppal: Uait. 

Olllnit •• t ale (19M) reportad value •. .Mar 400 11: that aar •• , with. raulta of .Poul.t li...!!. 

D. Cl + ~CC~. th.ra baa bean 0111,. 011 •• tudy of t.h.i. rat., that by WiDe~. (1982), ualas a 

l .. u flub pbotol,.d.7r .. cmaac. fluore.caac. tacIm1qu.. It ... caacludad that the pr •• ec. of a 

r.activ. impurity accouatad for a .1IDificm~ fracUoa of the Cl ~l, aDd therefore oal,. uppar 

-'-limit. to-the i-ata- _r'- r.'rt.ad for tb. taall)u~tura rma. 259-3.58 1:., Thia re .. ctioa ,1&_ tGo_.l<>w _" __ _ 

to'be of .n,. '1iiPortaac. 1n at.ilD.J;b.i-lc cb..tatry. 

El0. Cl + ~CO. the re.ult. fraa five of the dx pubUabad studi •• C1Ucba.l~. (1979a), Anduson 

aDd Xurylo (1979), IUki~. U978a). F .. aao and Kosar (1981) and Poul.t~. (1981)) ar. in 

Soad &lre_t at -298 11:, !Nt -.501 ar.atar the the value reported by FOOD .t ale (lSl78). tho 

pref.rred valu. at 298 11: was obtaiaed by ccmbinias tho absolute velu •• reported by Micha.l !U1 .. 

And.rson and Kurylo. and 'uana and Kosar. with the valu.s obtatnad by caobinias the ratio of 

k(Cl + ~CO)Ilt(Cl + C-;!l6) reported by 1I1k1 et al. (1.3±O.1) and by Poul.t 5....!l. (1.16±0.12) 

-11 .ith the pref.rred value of .5.7 x 10 for k(Cl + C-;!l5) at 298 1:. the pref.rnd valu. of E/R • .,. 

obtaiDed frail a laut square. fit to all the data reported in Micha.l at ale and ill Anderson and 

lCurylo. Th. A-factor ... adjusted to ,.i.ld the pnferred value at 298 IC. 

Ell. Cl + ~02' Th. absolute rata co.fficiaata d.ta"",iDed at -Z98 11: by Wataoa~. (1976). Leu and 

DoHore (1976), Micha.l ~. (1977). Poulat.~. (1978a) and lC.,.ser (1980e) rana. in value frem 

-13 (3.6-6.2) z 10 • Th. studi .. of Michael ~ .• 1C.,. •• r. and Poulat~. ara pr ... a~l,. ccmaldared 

to be the molt reUable. the pnf.rred value for tho Arrhm1us uprHa10n is' takm to ba that 

reported by 1I:.,. •• r. Th. A-factor reportAd by Micha.l ~. is coaaiderabl,. lower than that .zpactad 

__ f~ _ ~oont!c.l ~onaid!raU~ and . ...,. po .. ibl,. be attributed to docaapos1ticm..o!. Bz02 at. tomporatuns above 300 IC. the data of· Micha.l~. at and b.low 300 I: are in &ood aar • ..u~ .ith the 

Arrhoaius .zpr .. aioa reported by lC.,.ser. Han data are required b.for. the Arrhenius par_ters 

cm b. conaidtred to b. _11 a.tablished. Se.shan and Saaacn (1983), uaias ..... SpactrClllatry. 

confirmed that W. naction procaeda onl,. by tb. abltracUon ... chani ... S1v1n& 1IC1 and 1102 as 

product •• 

E12. Cl + BJCl. This rocOCllD8lldation 1& bued on nsults over tb. t.aarsrator. rana. 2'3-36.5 IC us1a& tho 

dlacbarsa fl.ooMMa •• pactraDotdc taclmiqu. ill tb. 0111,. reportAd study of thla raw, Cook !.L!1. 

(198la). EmU. and Biro (1985) have _ .. ured tho product cUstribution ill a dlacbu,. f1oor-1u.as 

spactrcDatric ayat.a aDd fo<a:Id that the -.Jor r.acUoa chcm.l la ~ to &1- tba product. C~ + OS 

.ith e ,.1ald of 111±61. 

60 

~ 

j 

....; 

, --

t(i 

"' 
"±'- ,W" 

') 

~'-) 

E13. Cl + l1li:)3. Th.n-ar. wo .tudi .. of thi. rate in OIhich the decq of Cl-__ in -=_ ~ w .. 

lIICCitoreel 117 naoaanc. fluor .. ccc. (~lo ~;-.t;IS3b'-or by r_c:ellbaorpti __ (~., 

1982) • Both report. val .... hiah.r thaD tboa. cbt.aiD*l in eerller dUchar:ae n-. apect:rcaet.ric 

st.udi •• 117 Leu ....s o.Hon (11l11S) -S by PcodAt.~. (187~a) tobich .mJ.toud the decq of-~in 

axc... Cl. Xuz71o~. nport. • value fox !/Jl of 1700 X for the ~nt .. re r.>&a :'3-~ 1:. 

Poulet. ~. report. a value for E/ll of 43110 I: for tha t.lperatun rllD&. ..38-633 X. 'lb. ~r 

t~ret.ur. date of Poalet. ~. are DOt. direeUy .ppUcabla to at.xatospheric coadiUona, and 

axtrapoLat.ioa to roaa t.-.pant.uxa ..,. DOt. be "ftlJ.d. Tha pnfuxeel ftlue 1& b .. ad CID ....u.a that. 

t.ha I:OC8 tAllparet.ur. data of J:urylo~. repr .. -.t.. m upper U&Ilt.. Th. b1&bar valDa nport.eeI 

by Clark~. i. baaed on dAt.a tobich lIXhibit. alanific_ acat.ter ..t 1.& DOt. COD&ldered 1D daxlvin& 

t.ha pref.rrad value. 

E14. Cl + 11)2. 'lba recOlllMCdatioaa tor the t.o reactioa chaDDala are baMcI apoa t.ha r...ute lIT r.... ....s 

_ Boward (1~2) udna a d1achaxs •. tlow qat..a with laa.r MID.t.ic r_ d.teetiCD ot 11)2' 011 ....s 

Cl.O. The t.otal rat.. conat.a:Dt. ia t.opar.t.ur. ~ with .. ~ ot (4.2±0.1) x 10-11 -cA3 

.... leeul. -1 .-1 over the t.aperatun x .... ~0-420 X. ru. value for t.ha t.otal rat. cooatalt. 18 

In ...,._t. with th. rssult.a ot indirect. stud1 .. nlaUva to Cl + Bil2 (Leu aDd o.Hon (1916), 

Poul.t. ~. (1~;8a), Burrows et al. (1918» or to Cl + Hz (Cox (USO». Th. cODtrlbuUoa of tha 

re.ction channal producins CIB + Cl.O (21% at. roca t.lp&ratur.) i.-wach Maher tbau-th.-appar Um1t. 

reported by Burrows et d. (11 ot t.otal nacUoa). Cat.t.aU aDd Cox (1986) ualns a ... l.cular ......h.Lat.iOD-UV absorpt.ion teclm1que over th. pr ... ur. r~. 50-760 t.orr nport. usult.a in Sood asxa_t. 

with t.ho •• ot L •• and Boward both for th. ovuall r.te COIl.t.ant ..t for the relaU". CCIluihut.1OD 

ot th. t.o reaction charmaLa. Tha rat.. c .... t.ant. for tha ch..u.l pn:oduc1%l& C10 + CIB can be ccalbined 

-With t.bAt. tor-th.-reacUon Cl.O + 08 > Cl + 11)2 to &1va m aqu1Ubz±a CODat.ant trc. .c1ch • valua 

ot th. heat of tozmation of 502 at. 298 II: ot 3.0 kcalllllOl can be dttivad. 

E15. Cl + CLz0. Th. pre tarred value _. dateClllDed froaa t.o indapaDlfant. absolute r.t.a coafficlent 

swd1 •• reported by Ray.!!<.....!!. (1980), us1D& t.ha dbcbAqa tlow-re-.ux:. tluoraac....:. cddi.c:harsa 

!low-ma .. I!p&Ctrcmet.ric t.achniqu... '!'ab valua haa be .. conflrmed by lIurrows CId Cox (1981) tobo 

determined the rat.ia !t(Cl + C120l!1t(Cl + H2' - 6900 !.:l lDOdulated photolysis exper!.:>ent.s. Th. 

aarU.r valua raportad by Basco and Dosr. (1971a) haa ba .. rej.cted, Th. Arrh .. 1us par_ters have 

not. bean axparu-ntally det.ermined; how_ar, the hiah value of k at. 298 ~ preclude. a sui>st.ant.1al 

po.it.iv. act.lvat.lon &Darsy. 

E16. Cl + CX:1.O. Dat.. reported by ~, Clyn. CId w.t.aoa (1913). 

E17. Cl + ClalO2• Flash pIIot.olysis/resonanc. fiuor •• canca at.udia. by l!ar&it.an (1983.) cd by Xurylo 

et al. (1983al, which are In Sood sar._t., .how that. th. rate const.ant. !ar this :aacUoa is 

.t....st. tMo ordars of ma&nit.ud. tastar thaD that. ludicatad lIT th. prmous work ot lWrylo and Hmm1D& 

(1971) and Raviahankara!.L!l. (1977b). It is probable that. th. slower raaction obs.rvwd by Xurylo 

and Harm1D&.as acwally ° ... ClOO3, not. Cl ... Cl.II:)3. 'lbe pretarred valua aver,,!_ t.boo rasult.s o! 

tha _ t.wo n ... studi.s. 

Ela. Cl + 1103 • Th. racamomded rOaD tamper.t.un value is U.a evarsaa at tha re.ult.a repc~ed by Cox 

!.L!.!. (1984a)~-Burrows et. at. (198~), and Cox~. (1987). In all studia. the kinetic behavior 

ot 1103 in tha lIIOdulated }'hotelysis ot CLz - Cl.aI02 lII1xt.ora. wa. _itorad in absorpt.!.cQ. In tha 

lat •• t. .tudy Cox at. al •• lao IIICI11t.ored Cl.O in ab.orpt1oa. the lack of tomparatur. d.pendanc. ls 

troD thl. lat •• t. study. 

E19. Cl'" '1/2°. I ... Entry. Thl. rata caatticlIDt. has been dat.am1nad in a at..ady ot the balosm-c.t.al.yzad 

decClllPOs1t.ioo ot niu ..... oxlda at. about. 10001: lIT Kaufman t'f. 01. (1956). the lar&aat. Yalua :apc>rtad __ 

10-17 CfI? .... leeul.-1 .-1, wlth lID activat.ioo mara ot 34 !tc.U .... L !:%trapolat.ion ot ~s. results 

t.o 1Dw t.cIperat.ur. &bars th.t. W. react.1oo cannot. b. ot IrD7 .1snUlcanc. in abzloapbart<: ch..t.t.ry. 

61 

--- :...-- - ~.-' .--:--

- -- ~:.-~=-" ";.";.--:-

-.'-- ~~- - ,. ---- --.:~~..- '- - -- ~- - ._.-- . -.. - .;--~-

.... ., .... ~----.--. 

---~ 

\ 

.....I 

,. 

J( 

I 1--

.---

, 
,-,r_.-· 

-

t· 

... 

....... 

y 

r 

• 

... 

) 

~) 

r.T 

E20. Cl ... CllIO. ~ported valu •• of thi. rate ccmataDt differ by IIIOre thm an order of ma&nitude. n.. 

~_t.-rec:ent.-st.ucU"rOlbic:b-ar. by-lC.sbi tt·~.- (1987)-ua1n&-dlac:bar&.-floormu .... pec:trcmetrT,-0DdItta and Stedman (1982) usina di.c:har,. fl.ow-nacmanc:. fluar .. c:eac:., report valDe. substantially 

Mah.r thm valuas reported .arlier. Th •• arUer resulta _re obtained by .alson and -JoImatcG 

(1981) us1na laser flub pbotolya1s-ruonanc:. fluoresc:enc.,· Grt.aly aDd Bouaton (1980) by pulsed 

laser photolysi. in a static: .,.sta with c:baillA1n.sc:mc:. d.tactico, and Clyne and Cruse (1972) 

by disc:bar&. flow-rescoanc:. fluoruc:enc.. In aU but the study by •• sbitt et at., C1IlO .... t.ba 

axc:a •• sped •• ; thus, Imowlq. of ita absolute conc:mtrat1OD ... required. It is po.sible that 

the low valu. of Grimely and Houston ...,. be chM to edaorpt.1on and decClllpOa1t1co of CllIJ co t.ba 

walla of their static: s,..ta. ~sults frae t.ba studlas of •• sbitt pt. al., lUta and StacbIa, ODd 

Clyne lind Crus. form the b .. la for the n_ recClllllllndation. Th.r. are no raliabl. data ca U.e 

taperatur. d.pandmc:e. 

-10 -11 -10 E21. Cl'" ClOO. Values ')f 1.S5 x 10 ,11.8 x 10 ,and 1.117 x 10 b.-n bean reported for ka(Cl ... 

- -ClOO "-C~ ""°

2 ) by -Johnston et li1. (1969), Cox!1...!1. (11179), aDd Aahford et ·al. (1978), r"~­

tivaly. Valu •• ot: 108, 20.9, 17, aDd 15 have bem reported for ka(Cl ... ClOO" Clz ... 02)/k(C1 ... -

ClOO .. 2 ClO) by Jobnaton ~., Cox ~., Ashford et al., and .ic:bol .. aDd I/orrhb (iSIIIa). 

Obviously the value of 108 by Jobnaton at al. is not c:onalatant .ith th. oth.rs, md the pr.t:arred 

value of 17.6 .a. obtained by aver&&ina the other thr •• valu •• (thla i. in-aar-..t-.ith • nl.ae 

that CIIn be derived !rem a study by Port.er and Wriaht (19S3». The abaoluta valu •• ot k &lid ~ 

o 0 a are dependmt upon tb. choic:. of 6lIf (C1OO) (th. values at: AlIf (ClOO) reported by Cox ~. 

and Asbford~. are in .xc:.llent eare_t, i .•• 22.7 md 22.S kc:aUlDOl, resp.ctively). lbe 

pret.rred valu. at: k (Cl ... ClOO .. C12 ... 02) ia takan to b. tha avaraa. of tb. thr .. reported value., 

-10 f -1 -1 i .•. 1.4 " 10._ aD. molecule • • eonsaquctly, th.- preferred -valu. of~(Cl ... C100 .. 2 ClC) 

is k /17.6, i ••• 8.0 x 10-12 =3 molecule -1 .-1. Th. EIR valu •• are uti_t.d to b. zero, lIbic:h a i& consistent with ather e"P.r1mentally d.ta=ined !ilt valu.. for atem-radicaL reections. 

E22. 0'" CLO. Ilac:antly there bav. be.n five studias of thh rat. c:onstant av.r an aztanded t.emparatur. 

r .. ,a usina a variety of techniqua.: Lau (1984b); Hu,it .. (1984b); Scbwab at al. (1984); Q>ptad 

and Birks (1986); and IHcavicb.!!:....!l. (1987). The raecmnended val"e is based en a but '"ares 

fit. to tha data reported in the." studies and in the aarliar studia. at: Zahnisar and Kaufman (lSI77) 

and anastad and Birks (1984). Values reported in tha early studies of B ...... oi at a1. (1973) aDd 

Clyne and lip C1976b) ara aian1ficanUy hiaher and _re not usad in darivina tha nCOIIIIMIDded val .... 

E23. CLO ... I/O. The aboolute rata coefficients datermined in the four dischar,. n.,.......... spectr.-tric 

studies (Clyne lind Watson (1974a), Lau and DeHara (1978), Ray and Watson (1981&) and Clyne aDd 

HacRobert (1980» and the discher,e flow la.ar l14&natic rescallnc. study L •• ~. (198Z) ara in 

altCallent eare_nt. at 298 K, and are averaaed to yhld the preferred valu.. The value reported by 

~ser aDd Xaufman (1977) from. cOlllpetit1v. study is not used in the der1v.tica of u.. prat:erred 

valu. as it 1a about 33% biaher. The maanituda. of the taqJarat.ure dapaadenc:_ reported by Leu 

and DeHore (1918) and L .. ~. era in ezceUent aareaant. Althauab the EIll value reported by 

Zahniser and Kau~ (l977)-ls in t:air qreaent." with the ather valua., it- is_nat considerad as it 

is dependct upon the EIll value .. s\lHd t:or the Cl ... 03 reaction. Th. Arrhanica expression was· 

derived frem a lea.t sCiU&ru fit to the data reported by Clyn. and Wauao, Leu &lid DeHore, Ray aDd 

Watson, Clyne and Hac:Robert--and·1a.~. 

E24. ClO ... !I03' Th. reeClllllllnded valu. h based on results reported by Cox et d. (1984a) and by Cos 

~. (1987) in the only reported studies of this reac:tiOD. Both st.ucUe. uaecl ~e IIIOdulated 

pbotolysis af C~ ... Cl.OlIl2 III1zturas. In the n_ study a .....u. taq>eratur. depeadcc. 1. reported. 

but bac ...... of uncertainties in the data a t.eslparaturr1ndependant nlua is ra<:QlllDaCded in this 

evaluation. 

----. :.---~ ---~----

-..... -.. --. -.-::---- ----

62 

- ~ - -=-=. 

-1 

--

,. . 

-' 

't 

--.~ .--

:"-:. 

~'-
!T. 

.. ) 

... 

~. 

-, 

~I 

:y_ .... 

. -

~) 

-:7--

E25. C"..o + 11)2' Thera haw 11'* bee Un at.ud1_ of thia ut.a coaatult.. thr .. wera low pr .. aan 

dischar,a flow at.udiaa, aech uailll a diUanat. ~rt.mt.al dat.ac:t.iCla t.aclDiqua ~1IIIIIDD and 

~, 1978: st.1IlIpna ~.. li79: Lack~., 1980), ~ bIG .. ra _lacular .adulat.iCla 

at.udJ. .. : at. 0Da af.D)8pbara (lIur~ aDd CaIt, 1981), and owr tha pr .. aura r8Zlla 50-760 t.ou 

(Cat.t.all me! Cox, 1986). the 298 X value. nportad, in CI1it.a of 10-12 r:a3 _lacula -1 a -1, era: 

3.8±0.5 (Ralmum and lCaufmIID), 6.hl.3 (St.~la ~.), 4.S:tO.1I (Lack ll...!1.), 5.4 (llurrowa 

and Cox), and 6.2%1.5 (Cat.teU and Caz). DIe rec-.ded valIla is t.ba _an of tha.a val ..... 

The at.ud7 of Cat.t.all and Caz over an a:xt.andad pr.aaura razIIa wbaa cClllbinad with r .. ulta of the 

10w pre .. ura dhchaqa n- at.ud1.. a_ to 1Dd1cat.a that. t.h1a nact.ioa uhihit.a DO pre .. ura 

d.paodanca at. rOOlll t..aparat.un. The CI1l.,. f.aIIIIICatura dapDdaace at.udJ (St.1mpfle ti..!!.) reaultad 

in a non-Unaar Arrhmiua behavior. The clat.a wr. beat. dHcr1hed I:rJ a four par_tar &quat.ieo of 

the fOml It - M -lilT + r::t', poaa1h~ auap.t.ilII that. e- diUareet. MchmJ._ 11&7 be occurriDI. the 

apraaalOD forwarded I:rJ St.t.pfla ~ .... 3.3 z 10-U axp(-S50n) + 4.' x 10-12 (T/300)-3.7. 

r.o poaa1ble prafarred va1.uea cm ba aug_tad ~r tha t.a.paret.ura dapao:l.,ca of It: (a) a 

apreaalon of t.ha. Lom auu .. ted I:rJ St.t.pfla ~., but. llbare t.ha val .... of A and C ara adJuatad 

-12 - to yield a valua of 5.0 x 10 at. 2lI8 ]C, or (1) a a1lllple Auhan1ua apr .. a1oa which Uta t.ha data 

-12 obt.ainad at. and below 300 IC (nomalized to 5.0 x 10 at. 298 ]C). Tha lat.t.er fOml is prefarred. 

The t.wo _at. probable paln of raacUca proctuct.a ara, (1) IIlCl + 02 and (2) 11:1 + 03' Lau (198Ob) 

_aM.Lad: at. al. uaed .... apector...uic dat.act.1C1a of ozcaa to placa uppar.l1III1t.~ of 1.5~(2~ 1:). 

and 3.0% (248 IC): and 2.0% (298 X), raapecUYa1,., CD Itz'lt. Burrowa me! Coz raport an upper Umit. 

of 0.3% for 1t2/1t at. 300 1:. 

-15 3 -1 -1 E2S. CLO + S£1J. Poulat. et d. (1980) haw raported eo upper llmit. of 10 CID _lacula a for k 

. at.. 298_ IC uailll tha .diac~,a n.,.,..tm t.echniqga:. 

E27. CLO + OS. Tha rac~ val.ua ia baaed on a Ut. t.o t.ha 219-373 IC data of Billa and Boward (1984), 

tha 243-298 IC data of l!urrowa ~. (19I14a), and tha 298 IC data of Poulet. et. al. (1986a). Data 

reported in tha atudi .. of Rav1&he1<ara at al. (laa3a), cd Leu cd Lin (1979) .. n not. uaad in 

der1viDI the recCllllMDdad value becawe in the .. atudiaa the ceocantoraUCia of CIO ... not. detarmined 

directly. Tha results of Burrows~. are tallperatura-l.:ldapendant while those of Sills and Boward 

sbow a ali&ht ne,ative tamparatura dependenca. Tha fraction of total r .. ction yieldin, B02 + Cl u 

producta h .. baen datamJ.nad by :.- and Lin (>0.6'): lIurrowa et. al. (0.8S±0.2): Billa and lIoward 

(0.86%0.14): and Poulat~. (0.98±O.12). lb. lataat atudy aivaa an upper limit of 0.14 !or 

tha branchinl ratio to alva 11:1 + Oz .. producU. Tha .-artalnti .. in all atudiaa allow for the 

poaalbillt,. that th. 11:1 yield la indeed zero. 

E28. C,LO RaacUona. Tha .. upper l1III1ta are b .. ed CIa tha data of Walker (reported in Clyna and Wataon, 

1974a). Tha upper Umita abown for k(zg8) vera actually datermined frCID data coUect.ac! at aither 

587 or 670 IC. The Arrh.,iua axpr .. aicaa _re .. tlmated basad on thia -600 IC data. 

E29. CLO + CLO. there ara thraa po.albla bimolecular chaanala for thia reaction: CLO + ClO ~ OCLO + Cl 

(1t1 ): CLO.+ CIO ~ Cl t ClOO (Itz): me! ClD + CLO.~ C~ ,. O2 (k3 ). the reCOlllllandad valuea ,iven ban. 

an for tha total rate coefficient. at low prnaur... Tbey are baaed laraaly CIa reaulta obtained 

in tha diachar,. now atudi .. of Cl1ua and co-..orkara aa diacuaaacf in the revi ... by WataOD (19n, 

1980). Bota that tha rata coaatant ia here daUnad .. -d(ClOlIdt - 2 It (CLO)2. Holacular lDOdulat1on 

_t.udJ..a auch .. thoaa of Cox md ccrworkara ( ... s.,.an .t al., 1986) haw liven a aiJllilar temperature depeadanc:a but .....cat lowr rata conatIDt. "aluaa. Tha procllct brmchilll ratioa and thair 

dapaadanc:e CIa temperatura aDd prauura ara not. .. U .. tabliahad. the 10w praaaura resulta indicate' 

that k2 and k3 ara both 1oIportant, "'ila kl repr .. eota caly about 10 parcent of the total reaction. 

The reaction exhibita bot.h b1,a)l" ..l.ar aDd tamolacal.ar nactiCD =-la (a .. .,try for thla reaction in Table 2). Tha tazmolecul.ar r .. ctioa, pn.-bly to ,iva t.ba diaar, doalnat .. at pr.aaurn 

hiahar thea about 10 torr: howavar, the role of the .u-r in the overall react.iOD la unclaar -

wbathar it la _rel,. in equilibria with CLO or daccaIpoa_ to liva the __ producta ,ivee in the 

63 

, . 

----- .~""';"'-....--- ---.-- - ---.- -, ... ~ 

~ 

/' 

/.c_ ' . 

. --~- . 

------ --

_ --W· 
) 

J 

.:.r. 

ElO. 

Ell. 

blal1.ecul.az ~MCt.laI~. S-_pRCIact. b~ zat.io dat.a haft bMa dartwcl tzc. .t.udJ. .. 

-of-tbe--cbloriDe-pb0t.0HD81t.iucl-cIecQIIIIOa1t.i ___ of-oaca.. ~.--~-thue In 1mCutault.1 .. 

ccace=1Jla the DHCl fDr _ r-U- of the ClzOz cc:.p1a 1D cmIft to &CCOUDt. for t.be .t.Ra& 

~ratun d~. of the 0_ qIIIIIIt.Ia ,.leU mil alia -U1WIc- tM ~.JlIl.e mla- of ClO 

cc.pl.eK flmlat.10D with 02 mil labuquct. nect.iema of the C~2 cc.pla. DIe eqIl111bd_ 

caaat..lt. !Dr tomct.1C111 of the ClzOz di8u 1a &1- 1D Tabla 3. 

ClO + 03. DIe brlllCbJDa r.t.io beblNa the t.o p' .. 1I:Ila chaaDela 1a DOt.~, but, tor the ~HCt. 

dUc:uaa1C111, 1a .. .....s to be_it,.. Then le DO w1d_ that. e1~ nact.iCIII 1Ctu&ll.,. OCCUH. 

tile Aa:hc1... pu~. vue e.t1aat.ed, mil the upper llalt. nt.e _toaDt.a In beaed CIII dat.a 

Hported 1:17 o.ttare, LJD mil Jaffe Cla711) cd b7 Ifoa&dcmui-St.uper JL.Il. (11178). 

CB + Clz. DIe nc~ =- ~.t.un ya1ue 1. the ... ~ ... of the n.al.t.e "P'RacI b7 

BoocIaab1- JL.Il. (1l1li7), ~1D IDd ADden«a (1l1li4), briahalltua~. (11183.), -S Leu 

IZid LiD -UIl711).-tJie -tAlllpenwH cS.peDdiDc:e 1. tzc. -BoocIa&h1ma JL.Il. x-&taiD aa4 AzldUIOD 

det.e~ that. the uc1ua1 .... prodIacta ue C1 + IIOCl. 

El2. CB + B:l. DIe ~e-,*, value 11 b .. ed 011 a la .. t. aquana fit. to the dat.. HpoRacl 1D the ncmt. 

.tudt_ b7""llDa~. Cl1184), ~u Cl11I14), mil bvbbClltua~. (1SII3b). III the .. at.udr.s 

put,icu1u .t.t.ct.i_ ... p&1d t.o the dat.azmlnat.iOD of the ablOlut.a CCIIIceDt.ntiCIII of 11:1 b7 UV md 

III .J»Ct.~tr7. EuUer .t.ud1e'"b7 TMIC. mil Glu. Cl1173c), Zahntau.!1-!l. Cl1174), SIalth 

cad z.1lJM~ (1974), briIhClkua~. (11177a) , Back n....!J.. (11177), 1Iua&1D n....!J.. Cll1l11), CcmoD 

~. (1&84), ....... iD J1....!1. (1l1li4), cd SIalth cd WiUi_ (111811) had rlP'rtecl • .....tllt. lower 

__ roca. t..oper.t.ure valueI. 

E33. CB + 1IX1. In the CIll,. ~apo~t...: .t.uc!y of thi • .,..t._ Emlls IDd BUb (111117) np'RacI the YIl ... of 

thi. rate CCIIIItmt. at. roaD t.aooperatare to Ue in the ranee Cl.7 - 11.5) z 10-13 .. 3.,lecula-l .-1. 

A t.8IDperatare dlpllldct. aprHaiCIII baa bND e.ttmat.ed 1:17 ctaoo.iII& a pre-ezpClllct1al factor b7 

malos:r with the 011 + Hz02 react.iCIII cd .. lect.in& the IllidpoiDt. of the lZpI~imlDtal rlD&e fDr the 

room t.emperature rat.e constant. the larae uncertaint,. !actor 11 nHd.d t.o mcaopa.. the entir. 

r"", •• 

E34. CB + Sub.tituted Hethm... Tbere h."e been • ."ual .tud1.s of .aell of the CB + CB.~';C4-Z-Y) 

ex - C1 o~ Br) reactiODa, i.e., CB + Cll;,Cl, Cl2Clz, C3:t,~ CBFC1z~CllFzCl~arr:u-r end ~Br. 

In .ach c ... there baa been quit.a &OOd eare_t het"l11 the reported rault.a Cucept for Clyne 

cad Bolt., C1979b», both .t -2911 J.: cd .. a function of t-.peratur.. I!ow.".r, in certain e .... ~t 

em he noted that the E/R val .... obt&1ned f~ .tudi •• pedon.d pndoaWlantl,. above 298 J.: were 

sreater the the E/R nIu.. obt.eiDed ~CID .tud1l. per!o~ 0'V'1r • t-er tAqIIratare rmsa. For 

.x..ople, the E/R valu. tor CB + ~Cl reported 1:17 Perry n....!J.. (1117I1a) 11 aia:nificIIIU,. hlsber than 

that repoRacl b7 Davi. J1....!1. (111711). Th ... -tol hut 'ilDificmt. diUer .. c •• could be sttributed 

to lither experiJlllntal .rror or noa-Unear Anhllllua heb..,ior. The reault.e of Jecma end taufmIn 

(1982) haw aboooD a DCIIIliD.ar Arrhea1us beh"'lo~ for •• ch reaction .t.ud1ed. They!ound that their--

date could best be nPrHIllt.ed b7 -a ~;e par_ter equaUoa ~f tha fona Ar~e-BIT). Th~ 

experimcltal ArezpC-IIIT) fit is ateted 1:17 the autbora to be in eare ... t. with that. IZpIcted from 

_transit.iOD .t.te theory. 

The pref.rred val .... ahoooo in thia rev1_ .. re obt&1ned 1:17 fiut fittins aU of the ablOlute rate 

data for .ecb reaction Cucept Clyne cd Bolt (1979h» to the thr •• par_tar equatlC11 ArezpC-B/T), 

cad thea a1lllpUty1n& th .. e equati<llll to • a.t of Arrhenius apr •• alema Clllt.ared .t 265 lC, a 

tAlplratur. repr .. ctetive of the atd-tropoapbere. The ArezpC-IIIT) ezprHa10na are &1- tor 

.ach reactiCIII in the iDdiv1Qul notea, ..taUe the Arrbc1ua aprHeiCIIII are .. t.ared in the tabU; of 

pref.rred YI1ues. ClIYioual,.. Arrheniua ezpr •• alona cm be cilltered at. IftT t..aperature frta the 

64 

" 

-'-

~ .-

~ 

" 

-, 
~ f1TdC... ___ _ 

... 

-l 

') 

.. 

~ , 

, 

.: 

~ 

/~' 

, 

) 

thr_ pu-.t.u etpat.i_ (then 8baul.tLbe.-Dat.rictecl-to-.. UJWt-the-t .. u.biL~1III8 atalUed) ~ 

T~!.om1D& It - ~ap(-Bn) to the !.om It - A'ap(-E/T): E' - II + 2T ... A' - A:II: aZ :II: yZ. 

t8 -+ ~Cl. the pnferncl vaI..a _e obtalDed uailla ClD1:1 IIb801aata rate =-tUci .... Uta. the 

data ot IIoorerd -S ZnDa«l (lin.,.), Davia J1...Il. (lInS) , hnJ' &...Il. (mSa) , Parutnapouloa 

.!LSl: (lasl) aDd .1 __ aDd ~ (11182) an ill aood qr...c. IDd wen uecI to det.eTWf_ tha 

preterred .. ~. rittiJla the Uta to liD npnaa1cD ot the !.om ~ap(-I/T) r-uta ill tha 

equat.iaa 3.411 :II: 10-18 yZezp(-~) _ tha tallpantuH rep (Z47-4I3)L nu. naul.ta ill a 

-14 3 -1 -1 

pre tarred yat- ot 4.3 :II: 10 ~ _1acu1a • tor It .t zu It. the deriYed .um.aJ.aa apnaaiCID 

cmtered at. 2M X ia 1.7 :II: 10-U ap(-UOO/T). 

t8 -+ CB.£1z. !be pnferncl YU- _e obta1Ded uailla GDl:T abaolllta rate =-tUcimt Uta. tha 

accurac}' oC the ar + CB4/011 -+ car~ atudy (CaE 1L.i1., lin.,.) __ probIiIly DO batter thaD a , 

!actor oC 2.,-!be 4ata ot,1Ioward mil Z-- (1117k), DaYia n..sl. (1117S), Parry~. (1Ia78a), 

aDd Jacaa mil Xautmm (1I1SZ) an m aood aar~ mil ware uaed to data-m. the praCarrad _lua 

(tha val ... ot Davia tLIl. ara ~t ~ (201) th8D tM .. a nportad lD the other atudl_ but 

an lDc1.Ddad lD tha ..,.luatiCID). FU.tillll tha data to au apnuicm ot the !.om Ai'ap(-Jl/T) 

reaulta 1D the aquat1cD 8.~ :II: 10-18 yZap(-502/T) onr the teoIparatun rllll8 245-455 It.' -"1'h1a 

raaulta 1D a - pnta~ed ~e ot 1.4 :II: 10-13 _3 .,lacu1a-l a-l tor It at 2118 X. the derived - -lZ 

AahaDiua apraaaiOll _tared at 2115 X 1. 4.7 :II: 10 ap(-1050/T). 

011 -+~. Ibe praCerred valuaa _e obta1Ded ua1llll ClD1:1 abaohlta r.te =-tUcimt data. - the 

acruac}' of the t8 + CB4/0B.! ca::t, atud:r_.L~ &..11., 1117I1a) .... ~y 110 battar th_ a !actor 

ot 2: - lhe--data of Iboud cd Z-_ (1~7ISa), Davia n...u. (111711) aDd Jecma aDd Xaut.a (1982) 

are in &oed aar- mil _re ... ed to datemlDe tha pratarred Yalu... rittina the dat.a to an 

axpra •• iOll ot the fom ,uZezp(-IIT) ruulta lD the aquatiCID 11.3 :II: 10-111 yZap(-3D4/T) ovar tha 

t.aparature ranae 245-487 X. th1a r .. ulta in a praCerred value ot 1.0 :II: 10-13 _3 .,lacul.a-l 

• -1 Cor It at 2118 It. the derived Anhmiua axpraaaica Cll1terad at Z85 It 18 3.4:11: 10-U axp(-1050/T). 

ell + orn:~. The prohrrad valu •• ware derived ua1n& tha abaoluta rate coaWcimt data reportad 

by Boward mil EveoaOll (l1l7k), Parry ~. (1117I1a), Watscm~. (11177), a.aaa md ~ 

C1977a), Parultavopouloa ~. (l1l81) cui Jacma cd EalfIDIIn (lgaz). l'ba data ot Cl}Da aDd Bolt 

(l979b) ... not. ccaai&ored a. it. 18 lD rather poor aar..-nt with the other data within the t..pera.,. 

ture ranaa .tudied, a.I. thare i. a dit~ar8DCa ot -e51 at 400 It. FlttlDa tha dat.a to an apr ... ion 

at the fo .. .uZupC-IIT) rasult. m the equatica 1.71 :II: 10-18 yZaxp(-483/T) ..... ~ the taa!parat.ure 

rllD&e 241-483 It. Thi. raautt. m a prafarred value ot 3.0 :II: 10-14 _3 IDOlacula-l .-1 Cor It at 

298 1:. lba dedvad ArrhaDiua axpra.a1on cantered at 285 I: 18 O.ISS :II: 10-12axpC-l000/T). 

C8 + CHl'2Cl. The praferred val .... _re derived uain& the absoluta rata coamelmt. data reported 

loy Boward ODd Evaaaca C1976a), AtIt1naCXl at al. (11175), Wataca et al. (11177), a.aaa mot ltautaan 

(1977a), l!mdwarlt_ and Zellnar (l978), Paraaltavopouloa~. (198U cui Jeocs and ltauCmm (1982); - -

which are 1D aood ear_to The data of Cl}De-iiDd Holt. (111711» ... not coaaiderad .. it is in 

=ather poor a&:-.>t with the otbar data withm tha t~ratuH ranaa .tudied, except at 298 x: 

-11 3 -1 -1 (the reported A-tactor ot -1 X 10 em ~la~. ,is 1DcoDaistent with that expected 

:haoret1cal17). FittiD& tha data to ~ ~zpr·a.a1on ot tha fom AyZap(-I/T) raaulta in tha equat.ion 

l.5l :II: 10-18 yZcqlC-l000/T) ovar the taq>eratura rllD&a 250-482 L Ibis raaulta in a preCarred 

-IS 3 -1 -1 Talue ot 4.5 :II: 10 c:a IDOlacula • tor It at 2118 It. tha dariv.d Arrhenius axpra.a1ca clI1tered 

-lZ It. 26S IC is 0.83 :II: 10 upC-1550IT). 

=a + CHzFCl. The praCerred valoa. ware dar!vad uain& tha abaoluta rata coeffielmt. data raport.ad 

~ Howard ODd £vw<gca C1II78a), WatacD at. at. (11177). IImdIfark IIId ZeUner (l1n8), Paraalte'l'ClpOlll.o • 

.r. a1. Cl981) aDd JeCDI aDd JCaur.c (1982) which ara m tair~. rit.tiJI& the data to an - ,-.2 . -18 -.2 apre.don of the fom .u-axp(-IIT) raaulta in the equation 3.77 :II: 10 rap(-6D4IT) ewar the 

65 

~ 

. 

• j 

i 

~ 

" 
p 

) 

.. 

.. 

". 

p. 

,-

r/ 

_r . .. .... :. 

, 

4 

J 

.,,' 

~5. 

06. 

-14 3 -1 -1 t.e.perabar. ral&. 245-486 JC. thia r.au1ta 1D • pr.ferred valu. of 4 •• :II: 10 ca IIOlecul. • 

for It at. 298 E. the der1ved Ar1:hc1ua apr .. dOD cmtared .t 285 1 1. 2.1 :II: 10-1Zap~115O/Il.._ 

CE + c:a,CC~. thia rlaluatiCD h baaed CD the ata of Jaoa& IIDd Eautam nIl711) ODd Xur7lo !1.!l . 

(19711). III.1r re.uJ.ta are 1n acaU8Ut a&r"lIImt over the tamperatura ral&a 250-460 JC. Tba 'aarlhr 

r •• ulta of IkMud IDd Ev_on (11176b), Wataon~. (11177), CbazI& ODd Iau~ (11177a) a:.>d C1)'D. 

CId Bolt (11179&) .. n d1.counted 1D fcvor of the _r re.ult.. the aarUar re.ult. ab-.d bJ.&ber 

valu •• of the rate CCDSt.ant, IDd lower EIll valu... th1 • .,. 1Dd1cata that the CBfC~ uaed lA the 

.arly atadi ..... cOllr.-inated with _U -.unta of • reactlve olefinic u.pu1ty. 

08 + r::a.p2Cl. If .. !I1u,.. th.ra hev. bac thra. t~rature dapmdaDt .tudi •• of th1a rate conat.IDt: 

W.t.soD!L!l. UIl77) over the c..perat .. re rma. 273-375 E; IIaDdIruIt ODd Zellner (11178) at. 293 &d 

373 JC: IDd C1YD. mid Bolt. (11179b) frcIII 2113 to 417 E. AU .t.udi .. are 1D -ar._t. OD the 1IIqII.1tud. 

of the tamperatur. ~. (!IIl- 1800 E). III. reta coast.ct. ... alao Muw:ad at. rooaI taaIper.tur. 

by Bowud md·!vanaoa UII76b) IIDd by Pa.rukavopoulo.~. (11181). III. value re_dad .t. room -

t.aparatara 1& the .. & of aU the reported v.l .... uc.pt. that. of Clyn. IIDd Bolt., tlbich 1& al&n1!lcmt.l.y 

hJ.&har. the prraponentl.1 factor ... fit.t.ed to the rac.-nded valu. at. room t..apar.t:ora. 

El7. CE + c:a,C1IY 2' II~ !I1try. Thara baa been only on. .t.udy of thi. rata con.teat. .. • functiCll of _ 

t..aparablra, that. by Clyn. aDd Bolt (111711b) over the t.-.paratura r&ll&a 293-417 JC. In additioo tl:<or. 

haY. hac room t.aa>perat.ur. _ .. arllllClta by Boward mid Evanson (l976b), IlaDdwarit lind ZaUn.r (1918), 

CId lIip~. (1919). th ••• thra. let.t.er _ .. uramant.. are lA ,ood -ara_t., ..tUl. the valaa of 

Clyne IDd Bolt. 11 .. 50% Msher. the value rac...-uded .t rOClll t..aperat.ura 1. the _an of aU the 

~al.... ~~pt. __ ~t. of Clyruo ~_ Bolt.. the .~llt.ur. dap.adanc. h t.~m froaa Clyn. aDd Bolt.,. 

b .. t .ith mcr .... d arror lJ.m,I.ta. Th. pr.-upon.nti.l f.ctor ... f1t.t.ed to the racOllllD&1>C!ed ...w. 

at roaa tClpar.t.ura. 

El8. OB + ~CF3' N ... Entry. Th. racClllDllnded val ... at. rOCIII t.-.par.t.ur. 1. the evarq. of the valoa. 

reported by Wat.aon!L!l. (1979b) and by Boward and Ev ... on (l976b). the t.eIIIparatur. dap....-..:. 

is !rca !ha 245-375 1: d.t.a of Watson~. Tha 293-~29 K data of Clyna and Bolt (1979b) .aro not 

used i!l dlr1vins the recoamendad val .... 

El9. OB + CJ:U'CF3 • II ... Entry. the racOlllDanded val ... at. rooaa tl!Dp&ratur. is the evarq. of the vat:.es 

reported by Watsoc~. (197911) and by Boward and Ev ... on (l976b). the t.eIIIparat.ur. dependo<l<:. 

1& fraa the 250-375 E of Wataon ~. 

E40. Oft + CBflCClF2 • Jf ... Entry. the rac~ed upra .. ion is derived frail a leut squares fit. to 

the correct.d 250-350 II: dat.a reported by Wat..on at a1. (1979b). Th. measured rata const.ants lOU. 

corr.cted for the pr .... c. of alken. impUr1ti... III. 249-473 II: au of Jaoat .• t. al. (1964) ara a 

factor of t.wo Msh.r at the l ...... t. t.eIIIparat.ur • .ad .. re not. used 1n d.riv!n& the raccamendad vat:.e. 

_EH. 

E42. 

E43. 

Of! + CSr-a3 • _ II .. Ent.ry. the racoamended a"Preaalon is d.rived fica a -laast.- squar •• fit. to !h. 

249-473 1: data reported by Jaocs .t.al. (1984)' and-tha 298 E data of Hartin' and Paraaltavopoa!.os 

(1983). the 294-429 r: data of Clyn. aDd Bolt. (l979b) .. r. not ... ad in dariv1n& the recClllll>OCd.ad 

val .... 

CII + ~r::::!i" New Ent.ry. Than are no reported data on the rata of th1a reactioa. III. re~ 

val ... i ... tilllatad by analoG' with aimilar react.loas. 

OB + C2Cl4• lb. preferred valAa at. 298 II: is • _ao of the value. raport.ad by Boward (1976) ODd 

Chana and J:aufIaan (19na). the nlua raport.ecS by WlAar ~. (1978), 1Ih1ch 1& more thao a fac-..or 

of 10 sroat.r, 1& rejected. the pref.rred Arrheaius par_tara are t!M». of C>-. and ~. 

66 

--~ 

, --- , 

~ 

~ 
;.,.r. 

) 

~ 

.. 

~ 

•• 

p 

/,> 

y 

:. 

.a_ 

~ -~ 

!""'" 

EH. CB + CzBC~. the preferred value at. 298 1: h a III .. D a! the valu .. report.ed by Boward (1976) and 

ChuI& and tautblm (1977a). the val ... derived from e relat.ive rata coe!!iciant. .t.udy by Winer li..!! . 

(1976) i. a !act.or a! -2 &raat.er than tha other valua. and i. not. coaaidarad in dariviD& the 

preferred value at. 298 IC. tha Arrhani... par_tara are b .. ed on tho.e report.ed by Quma and 

JCautblm (tha A-!act.or h reducad t.o yield tha preferred value at. 298 IC) • 

E45. 08 + CFC~ and CII + CF2

Clz. tha A-!act.or _. a.t.ilDat.ad, and a tc.ar liIDit. ... darived tor E/R by 

u.iD& tha uwar limit.. report.ad tor the rat.e ccaat.anta by Olana and J:au!man (1977b) at. about. -480 IC. 

the .. upre .. ioas ara quit.e ccmpat.1bla .ith tha upper Um1ta raportad !or th .. e ret.a coaat.ant.a by 

Atkinson!Ul.. (1975), Soward and Evanaon (11176&), Cos at d. (11176&) and Clyne and Bolt. (1979h). 

None a! the iuve.t.i&at.ors reported arrt evidance tor r .. ction bet_an CJI and the.e chlorofiuoraoethma •• 

E46. 08 + Clat02 • the reault. reported by Zalmhar ~. (1917) and Ilavhbanltara~. C1977b) ara 

in sood &&re_t at. -245 IC ( .. ithin 25%), coaaiderin& the d1!ficultia. a .. ociat.ad .. ith bandlinS 

Cl.OH02 • tha preferred value i. that. a! Zahn1 .. r et al. Naither .tudy raportad aD)' data on the 

reaction_product. •• 

E47. 0 + Bel. Fair ",reGant exists bat_an the rasulta a! Brown and Salith (1975), Won& and Ballas 

(1971), R.av1shanltara~. (1977a), Back~. (1977) .and Sinsletoa and Cvat.anovic (1981) at. 

300 IC (SOIDa a! the_ values tor k(300 IC) .ere obtainad by axtrapolation a! the experimentaUy 

detarmined Arrhaniu. arpre.s1ons), but the.e are a factor a! -7 lower than that. o!·Ba1akhnin .t Ill • 

. (1971)." iin(~rt.;;at-;iy, th~- valu .. report..d-(or E/R are- in ~~lat.a disqreoaiant, rllll&ina~ 

2260-3755 IC. Tha praferrod value .... ba.ed on tha result. report.ad by Brown and . Smith, Wons and 

Bellas, lUvisbankara ~., Hack~. and Sin&leton and evet.movic but. not. tho •• reported by 

Balakbnin !Lll . 

.046. 0 + HO:l. Thero are no expere>ental data; this is lID est1mated value based on rat. .. o( O-ateal 

reactions with similar coa:pounds. 

E49. 0 + ClD1IJ2 • the results reported by Molina~. (1977b) and Xluylo (1971) are in Soad &&re_nt., 

and this data h .. bean used to darive the preferred Arrhani ... arpra .. ion. the value raport.ed by 

Ravisbankara~. (1977b) at. 245 IC is a !act.or o( 2 &reater than those !rCIII the othar studies, 

and this ID&7 poslibly be attributed to (a) secondary kinet.ic compUcat.ions, (b) presenca a! N02 as 

a reactiva impurity in the CLOIIJ2, or (c) (ozmation o( reactive Plot.olytic products. !Jone o( tha 

studies reported identification o( tha raact.ion products. The room temperat.ura result. o( AdlarGolden and Wie.an!ald (1981) J.a in lOod &&ra_nt. .ith the recClDCldad valua. 

E50. 0 + ClzO. The nCamlandation averasaa the resulta a! H1z101alt and Molina (1978) (or 236-295 IC 

- .. ith- the approximately 30 percent. lower values_of Wacker .!!:....!l •. (19.8.2) over the s_&me t.empeJ:atura 

rmse. EarUar results by B .. co end Desra (1971c) and Fre_-and Phillips (1968) have not. baan 

included in the darivation o( tha pre(erredvalua dua to data analy.is di!(icult.ias in bo~ studies. 

E51. 0 + OClD. Tha Arrbeoius axprelSiCXI .... e.t1lDated based on 298 1: data report.ed by BCI&ZId, Clyne and 

Watson (1973). 

£52. OS + 0:10. New Entry. The rocClllllClded value 18 that report.ed by PouLat !.L!1 .. (1986b), the only 

reported Itudy oC this rata coaatmt., uUn& a diachuse Clow .,..r..a in ..t1ich CII decay .as _aaured 

by LIF or Em over the tlllli'lrature raD&e 293-473 IC. Product. IIOCl ... dat.ected by IIIOdulat.ad 

IDOlecular be. IDSsa lpact.raz>et.ry. the branchin& ratio (or tha channel t.o produce BCX:l + O2 .... 

datermined t.o be c~e t.o unity, but ezperilDeDtal uncertainty would au.- it. t.o be .. l.Gw .. O.SO. 

E53. !IO + 0:10. Tha Arrheoi ... axpr .. sion ... a.tilDated b .. ed CIl 298 1: data raported by s-nd, Clyna 

and W~t.son (1973). 

67 

_ .. _'-, 
.. 

• 

) 

~ 

-

". 

.: 

'/ 

:' 

j 

,.". 

-

E54. 11:1 + ClCIIOZ• beetl,.. r .. ·uta of four stadi .. of the kinatic. of thb 87St- hn'e be_ p>b~. 

in tCJ.ch th. folloorm._upper l.1IIIita to t.be~ ~, __ b~18CllUr--z.tA-COJI8t.aDt.-.. :cLZeport.acl:-

1 :K 10-111 =3 IDOlecul.-l .-1 by •• tatic ..a-l ... l.caI-path OV abaozptica tAchniqu. and • steadystatA flDw nIll tAcbDiqua U:allne ~ •• 11185); ,~ 10-18 uam. • f1Dw re.ctor with rrm ana1yai. 

(Friedl. fi....!l.. 111815); and 8.4 :K 10-21 uaiDa • static pbotolyai. .,.st_ with nm ana1yai. 

-111 (Batak.,._ aDd Leu. 111815). aDd 1.5 :K 10 by nIll enalyais of th. dec.,. of ClCIIOZ in th. preaenc. 

of 11:1 in lUI ....... l .... (2500 and 5800 Utara) taflca or t.floD-co.ted chaaban (Atkin_ et al. 

11187). Earller. BiB. at al. ClIl77) bed reported. hiaMr upper l.1IIIit. All studie. fOUDd tbi. 

re.ctiOD to ba catalyzed by surface.. The dlUercce. in tha reported upper liait. CGID be acCO<Zltad 

for in tame of the _ry diUer_t reactor cbaractAd.tic. aDd detectiea .caitivit1a. of th. 

varioua .tudi ... The bomoawaou. r •• ction 1. too alow to hn'e my .i&Dificant. eUect ea .tmo.pbuie 

ch •• try. 

E55. 1IC1 + 1IOz1C2. ru. upper 11m1t 18 bued ca raaulta DC .tatie pbotoly.la-nm expart.aDt.a CH. t. 

L .... priv.t. c~c.tion. 11185)~ 

ES6. H20 + Cl.OIK)2. • .. Entry. Thla reccmMOdatica i. baed on the upper l.1IIIita to th. bomoSanaou. 

b1lDOlecular rate conat.aDt reportad by A~ ~. (19815). mid by Batak.,._ and L ... (11186). 

~Atk1DaOD at d. obnrv.d by nm malyzia th. dec.,. of ClCII02 in the pre .. nce of Hz0 in Wlevol ... (2500 md 5800 litera) taflea or taflca-co.ted chad>ara. Thair ob •• rvad dr..,. r.ta Ii-. an upper Um1t to th. homoa,",aoua I" ph ... rat. coaat .. t. and th.,. ceaclud. that th. d.c.y ob •• rvad 

18 due to h.t.UOlcaoua proc...... H.tale.,. ... end Leu. u.ins •• tatic pbotolyzi. ayat.a w1th nm 

analya1 •• d.rt," •• 1mi.lar upper limit. ~l.aDd~. (111815) cCllcluded that th. dec.,. th.,. oburvad 

re.ul~!rem ~api,! h.taEoalD~ua proe...... _Th. hcoIosan~ .!-•• ction i. too alow to_ have any 

siSDificant affect. on .tmospharic chami.try. 

Fl. Br + 03. Th. ruulta reportad for 1I;(2118~) by Clyne end W.taon (11175). Lau aDd DeHore (1977). 

Mich .. l at a1. (1978). Michaal and Payne (19711). md toob.,.~. (1118711) are in exc.llent. .sre-nt. 

The prefarred value at 298 K is derived by takiD& s simpl. _lID of the •• fi_ v.lu ... Th. taq>arature 

dapondencea reportad for k by Leu and DeItlr. end by Toohey ~. are in sood q:allDent. but they 

can only be considered to be in fair qrt_ent with those reported by Micha.l~. and Michael 

and Payn.. Th. preferred value .... aynt.buized to but fit .11 the data reported !rem thes. fiv • 

• tudie •• 

F2. Br + Hz02. Th. recOlllHDdad upp.r 11m1t. to th. v.Lu. of th. rata CODataDt .t roaII tClplutur. 1& 

based on relult. reported in th. recant. .tady by toohay.t d. (1987.) uaiDS • dbchul. flow-1aaer 

lDa&DetiC relODaDc. techniqu.. Thair upper 11m1t detamined ov.r thL teoaparatur. ransa 298-378 1C 

is coasiatent .. ith Less .ensitiv. upper llalt. detatml".d by Leu (1980.) aDd Po • .,.!L!l. (1981) 

usill& th. discbar,. flow-lDa .. spectrometric t.dmiqu.. The...eh M&har value reported by Haneshan 

and Banson (1983) DJrY result !rem th. proSCIC. of excited Br .t.cma in th. very low preuur. reactor. 

The pr.-a:zpo"entlal factor was chosen to be consi.tant with that for the Cl + 1Iz02 rat. COIISt.ant. 

and ~th. fIR value was fitted to tb.~ upper limit st~ 298 X •. 

F3. Br + IIzCO. Th.re bav. been two studi •• of thla rata conatant ... functiea of t.8IIIp8ratur.; !lav. 

~. (1981). uaiDS th.~ !lash photolysis-re.onanc. fluore.can,,-.~ tacbDlqu •• and PouLet ~. 

(1981). u.in& the dis chars. !low-IDa ••• pectrometric techniqu.. Th ••• r •• ult. are in r.asonably 

soo<1 All:.-.t. Th. Arrhenius expressiea ... derived frail • Lea.t. squar •• fit. to th. d.t. reportad 

in th ... tMO studi... Th. M&her roem tAalperature v.l.ua of LaBr .. et el. (11180) uaiDS th. dlachu,. 

flow-EPR tecbDiqua has been sboMl to be in .rror chM to secondary chem1.try (PouLet ~.). 

F4. Br + 002 • Thla recOllllMlDdatioa is ba.ed 011 r •• ulta obtained over the 260-3110 X e-peratur. rans. 

in the recmt .tudy by Tooh.,.!!<..ll. (1987a). uam. • dlachu,. !low .y.~ with LKl d.tectloa of 

802 dec.,. in exc ... Br. Th. roaD tamparar.ur. v.lu. reported in thla .tudy is a !actor of thr •• 

68 

------ -

Ii 

I 

-~ 
) 

/~ 

, 

-J 

FS. 

F6. 

hi&her the that. reported by Poul.t.._~ __ (1D14b)ua1n& LI7 mil HI t.echD1que. IDd 1& m order at 

- mq:ni t.ude--l.uC.r-thm-th.-value--ot-Po.~~. --(11111) .--'%he--1IDcut.alDt.)'-1D-EJ]l-b-.et.--to-_COIIIPu.-

th. valu. !/ll - O. aa tor oth.r radical-redical raact.ic:a.. th. rNct.1caa ot I!J: a~ with ~O~. 

-IICDJ. md IIJ~ u. aU aloore~ t.hm th. corn.poQdJ.a& nact.icaa ot Cl-a~ by oae to t.o orden at 

mq:ni tude. 

Br + C~O. 11_ Entr7. Th. nccm.rx!ed value 1& a pnlJ.aiDc7 _lu. by SOlIder ...s Friedl (privat.. 

cClllllLllllcat.1ea. 1987). It. wu d.dved by oba.J:V1n& th. foDiRi_ ot ClD ua1D& 1ca& path uv 

abaorpt,iea toUow1D& th. fluh photolya1& ot a BrZ - ClzO a1%t.unI. 

BrO + O. Th. preflrred value la baaed on tha valu. reported by Clyne~. (11118). thi. valu. 

appeu. to be quite reasonable 1D 11&ht. ot the kz>oom r .. ct.ivUy ot ClD redic.La with at.aD!c axnen. 

Th. t.&q)U.t.ur. depenclenc. It laexpect.ed to be ~l tor III at.ooo-%edical proe •••• a.c •• 0 + ClO. 

n. BrO + ClO. Th. reCOll:OlCld.d room t.oiiDpereturit valil.-i. bued 'cD th. DFJtB riault.a ot Cl,ue mel Wat.aon 

(1917). the r.cent. :IF/llF/UiR re.ult.. at Toohey~. (privete c-=1cat.1ea. 1981). &Del the recent. 

FP/UV ABS and OF1t5 re.ulta ot Fdedl ...s SIIDd.r (privat.. c.-mJ.cat.1oa. 1987). aU at Mlich are 

in &aod &&r~t. CD th. value at th. tot.al rate co.tUcilDt.. Th. lower value reported by HUla 

at al. (lDl1).-alt.bou&h nat. u.ed in th. derivat.ion ot tha recOlllll&llded value. i. encaapaaaed wiWn 

th. at.at.ed unc.rtunt.y 11mJ.t.a. th .... ch lower valu. ot Buco mel Doera (1971b). derived .... 1n& a 

ditt.r.nt. int..rpr.t.at.1ca ot th. r.act.ion _cllanblD. ia not. used h.r.. It. baa baen ahalon by Clyna 

and Wat.son. Toohey at at .• md Il1Ua ~. that. tha naction procaede approxllDot.aly equally by 

t.he two channels indicated. In the at.ma.pban th. Cl.OO PU0X7 redical tozmed 1D the .eccad 

r.act.1on chmnal will--rapldly dlasociat. 1Dto Cl + -OZ' -_Tha laclt oCt.-.peratura dependence 

report.ed by Hllla~. la conslat.ent. with th. pre.ant. .. t.1IDat.1_ ot !/R - 0; bawevar. turt..her 

worlt in oth.r laboratorl.s current.ly ln proar •• a aucc.ate an .ppr.ciable na&aUve t.emperat.ur. 

d.pendanc •• 

F8. BrO + 110. Tha r.sult.. ot th. thr .. low pres.ur ..... aa .pect..roeetric .tudi .. (Clyna md Wat.son. 1915; 

Ray and ;;&taon. 1"a~.; Leu. 1979a) and the hl&h pr ... ur. UV absorptlon study (Watsan~ .• 1919.). 

which a1: uaed par.ldo !lrst-ordor ccadltlons. are ln &7c.Uont. qr • .....,t. at. 298 )C. and ue thou&bt. 

to b. aa.ch more reUabl. than t.h •• arlier low pre.sure uv .·baorptl_ .tudy (Clyne and Crus.. 1910b). 

The r.sult. 0' tho two temperatura d.pendenc •• tudle. ua !'l &ood qre_t. md bath .how a ..... 11 

nesatlv. t.emperat.ura d.pendance. Tha pr.terred Arrhanlus apra •• iea ... darlved frem a least. 

squar •• fit. to all the data report.ad In th. 'our recent. .tudi... By COIObininS tha data r.ported 

by Watsea et al. with that 'rem th. thr.e ..... s .pect.r~trlc .tudi ••• It. cm be ahown that. W. 

r.act.lon do •• not. uhlblt any observabla pr ... ure depedanc. b.t._en 1 and 100 t.orr tot.al pressure. 

Th. t.emperat.ur. dependences 0' It for th. analo&ous ClD and 1IJ:z r:act.ioas ara also n.,ativ •• and are 

s1mllar 1D .... snlt.ud •• 

F9. BrC +- BrO. Th.re sre two posslbl. b1m:>lacular clumn.ts tor t.hia react.lea: BrO + BrO ~ 2l!r + O2 (1t1) 

and BrO -+- BrC ~ B~ +- O2 (It,," - Th. total rat. cOllstmt. tor disappearance 0' BrC (It -- k1 + 1t2 ) has 

been stoudlod by a vari!lty 0' techniques. lnclud1n& di'.char&. tlow-ultravlol..t. abSorption (Clyn. 

and Crus •• 1:110a). l1schar&a now-m.ass spectrematry (Clyn. ODd Wat.aca. 1915) and nash pbotol,.sisultraviolet abp.ol"pt.lon (Baaco and Dcsra~ 1911b; Sand.r and Wataea. 1981b). Since ,t.h1. raaction- la 

second ordn in [BrO). those st.udl .. monltorina [BrO) by ult..r..,lolet. abaorpt.i_ requ1red tha valu. 

ot t.h. :rass sectien ~ t.o det.rmin. It. Ther. 1_ .ub.t.mtial diaaar.-at. in the reported value. 

of ~. Althou&h the lII&&Dit.ud. ot iT is depe"dont upon the part.lcular .pectral transit.1on select.ed 

and l.nst::-.:CI8nt.al "arltll>llters such as spectral bandwidth. th. ma.t liltll,. explanation for th. lu&. 

d1t!erOt>CH in tho reported valu .. ot iT ;.s th .. t th. t.echnlque. (bued 011 r.act.iea .t.alchlOllMlt.ri •• ) 

us.d to det.rmine ~ In th. early studi •• _r. used 1DconecU,. ( ••• dlscua.lon by Cl,ue md Wat.son). 

Th. study 0' Sander and Watson used totaUy lndependent. _thoda to determin. tha valuaa ot iT and 

(iT/i:). :!I. recCIIIDC1datlons 'or 1t1 &Del kZ are consl.tent. wlth a raca.oadaticn of It - 1.14 X 10-U 

69 

1 .... 

I 

.. -~ 
~ 

) 

.. 

04 

~ 

.: 

r 

';:--

// 

y 

,,:. ~. 

~ 

;; 

~ 

~ 

"p(+ZSS/T) c;m3 IIIOlec:uI..-l .-1. this tempuature d~e is the co=ected value fn>e SlIDI:5er 

-l2 cd--Watson.-md-the-pr ... upoo_thl tact.or...has bMn_chose to fit. the Yalue of k(29IIC) - 2.7" 10 

3 -1 -1 c:a IIIOlecua • • MUch i. the aver .. e of the valu .. reported II,- C1JD8 &ad Watson (tho IQaSS 

r,>ect:rcmetrlc study .mare tnowled&e of iT is aot required) 8Dd by Sander &ad Wataoa (the lat.est 

.::sorption study). Thore was no observable pr.ssure dopeodence fra. SO to 47S torr in the lattoer 

s~dy. en,,~. (1982) used the IDOleculor illDdulation techniquo llith ultraviolot absoq:(.ion :.0 

derive a tAmperature indepeodent value of tz which 1& SO percent &ruter than the 298 't val!:>e 

nc __ nded horo • 

~ partitlonin& of tho total ratA constant. into its t.., ccmpcmonta. kl M>d tz. has been ... sured 

!:f Sander aDd Watson at 298 1:. by JaUe and Mainquist (1980) frcaa 2S8 to 333 't. and by Colt It. aJ.. 

(1982) frOlll 278 to 348 IC. AU. are in aa,re-.t that k l/k - 0.84±0.03 at 298 IC. In the t.q>eratGre 

d.epend.nt st.udie. th •. quant..e yield (or the bro.1ne pboto.-iti:tod decaaposit.ion of ozcn. vas 

DUsur.d. JaUe and Hainqulst. observed a stron&. un'''Plained d.poDdece of the qu.ant.\III yield at. 

298 X on (8r21. and -their resulta -.. ore obta1necl" at· mob hi&her [!r21 valu .. than wore those -of 

~~. Tbls malte. a comparisc:a o( rnub diUicult.. Fr_ an cal.ysls o( both set.s o( tempc:::-

ature dependent data. the fol1.owill& .xpressic:as (or k l/k _re d.rived: 0.98 ezp(-44/T) (J&((o ..,d 

~nquist.); 1.4Z e"P(-l63fT) (Cox ~.); md 1.18 '''P(-104fT) ( .. ID val_). this mean value ~s 

c..n canbinod with t.h. ~_sic:a (or kl sbooa in the table. Th. "pressica (or ltz resulta .~ 

~e nUllerical values of k2 at ZOO IC and 300 't derived (rail the avalDat.ion o( these expressic:as ~r 

"1 and for k-(1"1 +" kZ)· 

FlO. 3.0 + 03. Based on a st.udy nport.ed by Sander and Watson (198ll1). Clyn. and Crus. <1970&) 

-14 3 -1 -1 :.ported an upper limit-of .8 ,,10_ _cm __ lDDl.ecule s (or th_ia ru~tion. _ ~~.studies repo,..-...ed 

~t thero is no avid ... c. (or this react.ion. The analDaoua CI0 ruction h .. a rate ccnrt.ant. o( 

-18 3 -1 -1 <10 c;m ..,l.cule s • 

F11. ~ + BOZ' The preferred value is based on the valu. of k(CLO + !Il2). eo" &ad Sheppard (1se2) 

!:.ave st.udied the rat.e of this reaction in ... imrestisat.ioo of the pbotolysis of 03 in th. prese::aee 

:! Br2 • HZ' and 02 USlr-& the ItOlocular moe:ol.tion-ultnviolet absorption t.ec!::lique. Al:!:cugh ~e 

:.ported value is not very precise. it. does snow that. tl1is reactien occurs and at. a rate c:x:.,arable 

:0 that for ClO + 002 • By analac' with the ClO + 002 sysr.... the product. ~ b •• xpect.ed to be 

3JIIr + 0Z" 

F12. :to + OB. Value chosen to be cc:asistent with k(CLO + Clil. due to the absence 0' any .xperi.mea::.al 

uta. 

F13. OB + BrZ' Th. recCllllleUded roaD temperatnr. value is the avena. of the values report.ed by 

;ood&&hians at. al. (1987). Lo_nstein cd Anderson (1984). IICd Poul.et~. (1983l. ::h. 

~rature independanc:. is frca Booda&hics.!!:...!1. !.a_t.in and Andersen d.t.rmi:ed tbat. 

~. exclusive product.s are Br + Dr. 

Fl4" OR + BBr. The preferred value at room ':.aperature is the IlVUq. of the varue. reported by 

iavishankara .!!:...!1. (1979a) usill& FP-RF. !:f Jourdain!L!l. (1981) usin& CF-EPR. and II,- Cac::>On 

!E....!!.!. (1984) uSin& FP-UF. and by Ravishmaar.~. (198Sa) us1q LFP-RF and_Li!'.:LIF t.ec!:nicpes. 

:n this latest study the IIBr ccmcentrat.ion ns direct.ly :DIIasured !n-aita in tho slow (low sys~ 

"::y UV abSOrptiDD. the rate ccast.mt d.t.r:sined in this re1mrest.!&at.iou is idooatical to the val.u. 

:ecazmended h.re. the date 0' ILavishankara!!<....!.1. (1979.) sbow tID depeDdenc:. c:a t.emperatAre .,.".r 

~. ranae 249-416 IC. Values reported by !lkacs IIUd Glass (1973.) ODd by Busain .t &1. (1341) are 

a !actor of bOO ID-er .ad .. re not i:lCluded in the derivat.ion of the preferred v~. 

70 

---=-... -

• 

4 .-~ 

" 
) 

/--' 

) 

on 

Fl5. aI + CB;,Br. The" absolute ratA coeWc1_ta deteraiDed b7-8oward~md-tv.naen (1976.) and Davi. et a1.-

(19711) are 111 a:cellet. ear--t. at. --298~--n.e 11_ approech-has heen used-t,o-deteDlline-tbe--

preferred Anheniu. par.et.er. •• __ ed fDr the 08 + CSJ~yC14-X7 r .. ctioo:. Fit.tiq the data 

to an aspn.sionof U. fDlD ,.rap (-BIT) reault. 111 the- equation 1.17 z 10:1 -r2.zp(-295/T) over 

the tAlllptlrature rlll\&. 24"-350 1:. Thi. r •• ults 111 a pretarred value of 3.8 z 10.14 cm3 DOl.cule-1 

.-1 for It at. 298 IC. the der1v.d Ar%h.u.u. apres.ien cetared at. 265 1: is 6.0 z 10-13ezp(-820/T). 

F111. ° + BBr. Ileaulta of the fl.uh pbotolyai.·resenance nooreaCeDc •• t.udy of Bava!3:...!!. (1983) for 

221-455 1: provide th. caly data at. str.toaph.ric tAlllptlrat.ur... R •• ulta have also h.m report.ed by 

Sin&let.ca cd Cftt.movic (1978) for 2911-554 1: b7 e pha •• ·.hift. tacbniqu., and di.chara. flaw results 

of Broooa cd Smith (197.5) tor 267-"30 1: and of Tak.ca and Glasa (1973b) at 298 1:. the preferred 

value is baaed on the reaul.t. of ...... et &1. and tho.e of Sinabtcn and Cvetanovic over the SaH 

tcparature rana., .iZlCe th ••• re...u. are l.a •• subject to cClllplicationa clue to .econdary chadstry 

_~ _ar.~. r •• ult. aeina diachaqe _on".. t.aclmique_~._ the uncertainty at 298 1: has ball1 aet to 

ancaDpA •• the •• l.attar reaul.ta. 

Gl. F + 03' the only a:parlment.al. data i. that. reported by Waaner.!Ul.. (1972). the value appears 

to h. quita re .. onabl.a iD view of the _11 Jtno.l reactivit.y of ataaic chl.orine with 03' 

G2. F + B

2 • the value of It at. 298 l' ._ to he _ll established with the result. report.ed by Zhitneva 

and Pshezhetslti1 (1978), Beidner~. (1979, 1980), Wunbua and Bousten (19110), Dadcnov !!.....!!!. 

(1971), Clyn.~. (1973), Bozzalli (1973), and Iaoshin et at. (197"), heiDI in ezcellent. aareement ~ -11 3 -1 -1 (ranse of It beiDa 2.3-3.0 z 10 (Ill molecule • ).-- the preferred value at 298 l' is taken to 

be the _an-of the value. raport.Gd in the-sa reference •• -Val.uu-of!/R ranse fram 433-.595 ~ (Beidner--- -

et al.: Wurzhera and IIoaston: IaoabiD~.). th. preferred value of EIP. is taken to ba the ",ean 

of the result. frem all of the atudiea. the A·factor was choam to fit the r.c..-nded roaa 

temperature value. 

G3. F + CH.. Tile three absolut.. rate coefficienta determined by Wsaner ~. (1971), Clyne ~. 

(1973) and lCDmpa and Wanner (1972) at. 298 IC are in aocd saraement; however, this II>I1Y be sanewha~ 

fortuitous as the ratios of It(F + ~)/It(F + CH,,) determined by thase s ... aroups can only be 

considered to he in fair a&r8elll8Zlt, 0.23, 0.42 and 0.88. the value. determined for It (298) from 

the rel.ativ. rate coeWcieet. atudies are also in aoad eareament. wit.h those detezm1nad in the 

-ab.olut;e rata coef!icimt. studies, and the value of 0.42 repor. I for It(F + Hz)IIt(F +-CS,,) by -Focn 

and Raid (1971) is 111 aoad sare......,t with that. reported by Clyne~. Faaano and lIo&ar (1982) 

det.ermined the absolute rOCllll tlllllpSrature rata coefflci.nt, and the rat.e coefficient. nlatlva to 

that. of the reacUon F + D2 • tba pzeferred value for It (298) is e waiahted _an of all the 

ruulta. the JDa&Ilitude of the t.aq>arature dapcdance is aClHOlhat unc.rtain. the preferred Arrhenius 

par_tera are h .. ed C1D th. data reported b7 w.aner et al., and Foon and Reid, and the preferred 

Arrhenius par ..... t.rs of the F + Hz reacUm. thia reaction has been reviewed by both Foan and 

lCatlfman (1975) lind Jonas and SkolJillt (1976). the A·factor .... y b. too hiah. 

G4. F + B20. the- recam>andad ezpress10a is based on th. 2"3-369 l' results of Walthe:: and Wsaner (1983) 

and the racmt. 298 l' result. of Frost.~. (1986). the pre·exponential factor bas hem adjusted 

to aive the recCJlllMlnded roaa t.aq>arature velue, which 1. the _an of the enly two reported v.lu .... ---

GS. 110 + ro. Thi. is the .,.!ue reported by Ray cd Wat..m (l98h) for It at. 298 1: usin& the discharae 

f~a. apect.~tric t.echnlque. Tbe taparat-ure dependence of It is npacted to ba small for 

auch a radical.-radical. react.ion. lb. t.cparature depalldenc .. of It for the anal.oac:u5 Cl.O and BrC 

react.ions (Tabla 1) are small aid D8&at.ive. 

71 

-------~ -,-------. ..~. ~~ .... ". 

~ 

~­

~ .-

-.Jf 
) 

~ 

4 

.. 

.. 

.-

-'" 

.,y' 

y< 

/. ~ :. 

1 

" "l 

t 

i ); 

~. 

" 

Ga. 1'0 + FO. lb.~valu.-of It(FO+ PO) nported b7 Cl)'De-...s~W~(1Q74b) ... obteiJ*l 1A. _re 

eUrect ___ rthaD-thet.-oC"WepMr ~.---(1g72), md .. auch 1. le ...... c.pt1hl. to enac clue to 

the pr .. me. of CCIIIPllceUn& .~ react.l=-. The valu. rec~ed 1A thl ...... _ 18 • 

.. laht.ed -anrqe- of th. t.» .tudi... Frca th. d.ta of Wqner ~. lt cm -be aac-th.t. the cIaa1naDt 

n.ct.lon ebmll.l 18 that. produc1n& 'Zl + Oz. a-er, th.lr data b ... 1. not adequ.te to CC8lCl,ud. 

that th18 is the cml.7 proc.a •• 

G7. PO + 03' lhe FO + "J react.lca baa t..) poN1hle patbwa7a oGicb an uothem1c, n.ult.1Jl& 1A the 

production of P + 2 0z OJ: FOZ + 02' Althouah thi. r .. ct.1o b .. not. bee atudied in a .imple, 

dlrect .-r, boO .tucU .. of COllPla c~cal .,..t.aaaa b.... reported _ kinetic 1nfeDIat.1on 

about. 1t.. StL~lco~. (lS1eZ) llMaared qumba yl.lds for 0_ d •• t.J:uctlon in 'Z/03 .ut.ur •• , 

and att.r1hut.ad the blah value., -4500, to be due to the rapld rel_ntion of at.aDlc fluatin. via 

tha FO + 03 ~ P + 20Z reaction. B_, th.lr n.ult.an probably al.ao COD81atant with the chain 

propq.tica proc... b.iDa FO + FO ~_ 'Zl + ~Z (th. l_.ttar r ... cti~ _.b" bee _ .!-udied t.w1c., (Wq:nar 

et- ';i.,1972; Clyn. and Wataca, 1974b) , aa4 alt.bou&h the valu. of [PJproduced"FOJeon • .-d 

18 ItnowD to b. clo .. to \alt,., lt, baa not. been accuratel,. dataa:uned. Con.equentl,. It. b 1Apoa.lble 

to .. c.rtain !%aD the uparlmaotal naalt. of St.anico at, a1. wh.ther or not the blah 'l\UDba ,.1.ld. 

tor ozona daat.ructica .hould b •• ttributed to the PO + 03 ra.ct.1on produclna eith.r F + 2 0z or 

1'02 + 0z (thi. proe ••• 1& .lao .-cha1A propq.tion .tap if the ruult1n& FOZ neUc.l pnf.rmtially 

r .. ct. with ozona r.ther, thm wlth .1th.r FO or lta.lf). Wqn.r.t al. utiUzed a' low pre.sur. 

dbchara. flow-ma.. .paet~t.r1e .,..tAdI to .tueIT th. , + 03 lind 1'0 + 1'0 reaction. b7 cUzect,ly 

IIIODltor1n& the time hiatory of th. cODCantratl=- of'. 1'0 mel 03. lb.,. concludad that. the 1'0 + 03 

reactlon .... UdimpOrtmt. lD their .,..tAdI. ao...v.r. thair papar do .. not pr .. ent enouah in!o ...... tion 

to w.rrant this ccaclualon. Ind.ed, thetr valu. of-It(FO + 1'0) 'of 3 x 10-11 is about a ta=-0C"4-

,raaUr than th.t. reported by Clyn. and Wat.aon, which ..... ,. po .. lbl,. be att.ributed to either ~ ... ctlve 

impurltl •• be1n& pr ... nt ln their ayat_, •• a •• 0(3p ). or th. 1'0 + 03 re.ctlone heine DOt ot 

n.,llaibl. lJIportance In -... " , '_ ,.,. Consaqumtl,.. it is not po .. 1hla to d.t.~m1ne a value for the 

1'0 + 03 n.ctien rate coaat_ LrOlD aist.1Da .xperimental dat.a. It is worth notlDa the a:a1oaDUs 

-18 3 -1 -1 CLO + 03 naetlona are artr .... l,. .1Dw «10 CIII molecule .) (DOlMan !.L.!1.. 1!176). and 

-14 -lS 3 -1 -' uppar lim! ts of 8 x 10 (Clyne and Cruse. 1970a) and 5 x 10 em "",locula s' (Sander 

and Watson. 1981b) bave baen ,reported for BrC + 03• 

G8. 0+1'0. Thi. '5t1lllllte 1& probabl,. accurat. to within a factor of 3. and is b .. ed upon the aas::mption 

__ that th.-reactivity of 1'0 ls 5111111ar to- that ot: C10 and-ErC. lb. temperatur. dependence of-the 

rat.e comtant is arpected to b ....... 11. as for the analo&o ... ClO re .. ction. 

G9, ° + FOZ• 110 .xper1JDeDtal data. Th. rat. constant t:or such a raeUcal-at.aa proclSs ls expected to 

approech th. ,n colllsien frequenC'f. cd ls not .xpect.ad to .xhibit a strona t~rature dapo:ldance. 

Gl0. ~OZ + 110. the •• reCOlDlleDdad value. tor the reactions of III with th. perhelo, .. atad _tllrlperoxy 

radlcals are based on the results reported b,. Dosnon !..!:....!!. (198S) for th. tea:parature rq. 230-

430 -K. The., are in aoad 'aar ...... nt -With -th. rciOm temperatura values reported !or-the rea:-..J.ori: ot: __ 

CF3

0Z (PlI.IDI> mel Ryan. 198Za), CFC1i'z (Leaclaux and Caralp. 1984), and CC13

0Z (Ryan ~ P11:I%b. 

1984) • Dosnon ~. h..,e shown that .,Z 1. the major product lD the.. reactions. 

H1. CB + SZS. the value of 1t(298) 1& an ..... ra&. at: th. rat. constanta reported by P.rry et. al. (197€b). 

Cox and Sheppard (1980). Wine ~. (1981a), Leu and Smith (1982a), Mich .. l.!L!..\.. (19.2). Lin 

(198Z). Lln!.L.!1. (1985'. and Earn .. ~. (1986a). Th. value of E/R is talc.n frOCl a C2:p0site 

unwllahtad !lUt squar •• !it to th. lDeUvidual dat.a polDta t:rom the first sav.n studles. Tha 

studie. of Leu and Smith (1982a), L1A~. (198S). and to a l .. ser extent. Lin (l98Z) show a 

sU&ht paraboUc temperat.ur. d.pendaoc. of It with e mlnilluD oc=1D& n.ar rOOlD tcrparatUJ:e. 

!!owcver. withlD the error lll11its stated in this evaluation. all data are !it r.uenabl,. _u by an 

72 

J 

.. 

i4 
, 

) 

.. 

• 

If 

l! 

, 

i, - -- Po!-

!, 

.. 

it 

~ 

i~--

. 

! 

f 

i 

i 

, 

'. 

~ 

r 

~ 

1 

) f 

82. 

83. 

Anheaiua apra .. lcm. lb ... 1Pt of wid_ ~ tha .. ncct. ~t.a ..... ata that. tha 

eullu .t.ooq by .... t.chua mel daIlua (1873b) ... in .COI: (qIl1t.a po •• 1h17 due to MCODdazy ~aecticma). 1be roca t.a.pentun valDa of St.uhl (1874) 11 .. Jut. outalda tlIe 26 .no~ llIII1t. .. t. !D~ 

It(Z") • 

CII + OCS. 1be value of 1t(2" 1:) 1a ID _&I. of the det.ualDat.1oaa by WahDu eod Jl.wiabankar. 

(~1I7) IDd CI&& IDd Lea (1"5). 1be valuea detamlDed by th ... authan Ua a fact.o~ of tlIna 

hJ.&he~ t.hID the .uUu _ ~.t.IA"a ___ ta of Lea GIll a.ith (11181). Aa d18cuaaed 1D 

u.. rec_t. atadl.a. W. diUu_ ..,. ba due to ID _conacUcm of the dat.a by !Au ..... SIIt1th 

to accoomt. = CII raact1ClD with HiS ~1t.l.a IDd a1ao to po .. 1h1e rqlll8r.t.1oa of CII. If."utha1.... the ~ty factor at:. 281 I: ha.- bela a.t. to lD~a tha .arllar .t:.udr wit.h1D 26. %be 

worlt by WaIDu IDd JlnUbaDtar. (W7) aupera.a the .tudT of Jl.w1ahaDbra !!<...!1. (18I1Ob) wbicb 

_lRiDiai.~ ~llcat.l~_ due to MCCDClar7 mdlor _uclt.ed .t:.at:.e .-rMct.1oa8 _ lnt..rt:.m.a witll u.. upu~ta of AtklDacm.!L!1. (18711) mel r.&rylo (11178). 1be upper liait. tor 1t(2" J:) reportad by 

Cas IIIld Sbeppcd (1"0) ia t.oo ma-1t.i_ to pam1t. ~1aca with tha 80ra racmt. .t.Uln.a. n.. 

rocaa t.eIIIpanbIl'a _t.a W~ ,- 4 JlavialllDbra .s-t:.rat.. tha l&cIt of aD aUact. of total 

pn.aur. (or ~ partial pnaaura) OIl tha rat.a CODatIDt. IIIld ara aupportad by the _ra l1a1t.ad pre •• ara 

and 02 at.ud1aa ot Ch.,. mel La.-: -nia E/R valUa ~ac...;.m.sad 18 that. ot 01..& an4 IA~~ ..bich 1& 

ccma1d.rably lower thlD nported by !Au IIIld Sa1th. althou&h th18 du:terlOllCa _y be due in part. to 

u.. aarll~tiCDad Oftrcorrect.ion at tha d.ta by the.a latt:.er authors. 

- Product. obaarnt.1cma by !Au IIIld Sa1th indicat. t:.hat. SB 18 • pJi1iaari-product. of thb ~ .. cticm ODd 

tll1t:.atl_1y ccmt1l2 t:.ha .,,"a.tlon ot r.&rylo lad LaufH (187S1f that tha -~ .. ctlcm pJioduc •• p~­

nmtly SB + Cl)Z thrOU&h a cClllpla: (edduct.) IHChmi_ (.iailar to tha .dduct tomatlcm •• m in tha 

CII + COz raactiona). Boweva~. tha ab.mc. ot all 0z/pre •• ura attact. to~ OB + cx::s i. markedly 

dlfferent. fDa ob •• rv.t1oa8 in tha C8 + csz raact:.ion .,..t. (.a. tollow1n& !lOt:.e). 

OB + cs2 • Dlera 1. a cona .... u. ot .xpe~1m ... tal evidenca Indlc.tlns that this ~ .. ctlon p~oc.od, 

'/ery ,lowly as a direct. bimolecular proc.... Wina~. (1980) sat. an '"Wer limIt. on k(298 Kl c! 

-15 3 -1 -1 1.~ x 10 COl IDOhcule • • A conaiatmt. upp4r llalt. 1. alao reported by Iy.~ and RowlODd 

(1980) !o~ the rata ot dlnct production ot OCS ill thi. reactiOll .,..t_. aQ&&a:t.1n& that OCS and sa 

ara pJi~ pzoducta ot a b~l.cular p~ca... nu. IMChmiatic int:.erpretation is turt.ha~ aupported 

by-th.-.tucU..--ot Lao md Smith (1S1l12bt IIIld Ble=-m at at. (1982) • .tllch a.t ..-..bat. Mlhar upper 

llalt. oa 1t(298 11:). The 8O~a rapld r .. ction rat .. cb.arved by Atltillacm~. (1878). l:urylo (1978). 

and Cox an4 Slappard (1980) 'IIIIq b. attributed to .. vera cCSlpllcationa arlallla t%OIII ucitad .t.ata 

md .. COlDdar)' ch-s..t~ in th.ir pboto1yt:.ic .,..t.e.. Th. Cas and Shappard atudy in partlcular f21 

lava bHD aUected by tlIe nacticm ot alact:.ron1cally aclt:.ad CSz (pJioducad vIa the 3~ !a pbotolya1a) 

with 02 (ill the 1 ata>ap,er. aynt.heUc ur adx) e ... U as by the acc.larat1n& a!tect of 02 on u.. 

C8 + CSz reecUon wl!lch baa ba_ ob.ervad by otha~ _nara and 1a suamarizod below. n.. impo~t.IIDC. 

ot tha alactrODically ~it.ed CSz ~ .. ctlon in_ tha_ t~_apb.r1_c oltidaUoo o! CSz_to OCS has bem 

ellacussed by Il1na ~. (1981d). 

M1 acceleratiq at!ect ot 02 on the CII + CS2 ~ .. ct.1on rat:.e bea bHn ob .. rwd by Jona • .e at. (1982). 

Barna. ~_ (1983). md Jtavtahankar. et at. (1986). elon& with. naar unity product.yhld for sl2 

and OCS. ID tha let.tu ttoO atudt ... tha effactiv. b~lecular rata constAnt. _. too.nd to be a 

fUl1ct100 o! total prenara (OZ + -Z) as _U. and abib1t:.ad all apprecilbla Mpt.iw t.q>aratun 

dependenca. the.. cb •• rvat.lona en con.1stmt with th. !D~tion ot e lona-llwct .dduct. u 

postulated br ~lo (W8) an4 l:urylo and Laufar (1978). tollowed by lta ~aact.1ClD with Oz: 

73 

1 I 

I 

.i 

I 

{ 

~ 
) 

-, 

r 

) + ... 

k. 

OB + CSz + H ~ SOCSz + H 

~ 

kc 

lIOCSZ + 0z .. Producta 

Ravisballltar.~. (1986) have. 1n !act.. direct.1y ab •• ned the approacb to .qullibd_ ~n this 

revera1b~ ... dduct formatim. In their .tudy. the aquJ.libri_ ccnatant ... _ .. urad ... function 

of t.emper.tur. and the h •• t. of format.1e11 of BOCSZ c.lculated (-12.4 kcal/mole). A rearrenaaDent. 

of th1. adduct followed by di •• oci.tim 1nto a:s md sa corr •• pondl to the low k (b1:D01ecular) 

cham.l referred to •• rll.r. Raviabmkar •• t. d. (1986) -.ur •• rate ccmat.aDt. for thia process 

in u.. abaenc. of o~ (at. approximat..ly 00 •• t.moapher.··of 'Z) equal to S :It 10~16·CIII3 molecule-·1 . 

a -1 lb. .f!act1ve ucac4-ord.r r.te c .... t.mt tor CSz or 011 r....,..,.l 1n th. abov. naction 

ach... CaD be .xpnlled .a 

11k." -(~/ltakc)(llP02) + (11k.H1IPH) 

wh.re P02 11 t.h. parti.l prellur. 0' 0z and PH equala POZ + P1I2• Tne .... lldity 0' this .xpression 

require. that. ka and ~ are invar1ant. With ~. P02/PIQ r.tio. A 11k va 1/POZ plot. of th. data of 

JOIl .. .!Ul. (taken· at .blr:lapber1c preuur.) ah!b1ta ....ned curv.tur ••. IU&&eltina • mor. complex 

IIIecban1atic ·1Dvolv .. ant. of.02• tober •• 1 the data of Barn. ___ et at. _and_a.v1s~.ar_. et. al. are mor.'!.. 

s.tisfact.orily repnaented by thb lII1al1S1a. Heverth.l .... toblle the qual1t.at.1v. feat.ures of the 

dat.a frCIII all thre. laboratorial sar ••• there are 1<1118 qu~~·.tiv. inCQ'lI1.t.anc!.ea. FirSt.. under 

similar cond1t.ions of 02 cd HZ pr ••• ures. th. Barn ••• t. al. rat.. constant. u. approxilUt.ely 601 

hi&her than tho •• of Jon .. ~. and up to a f.ctor of Z b1Pr than t.he .... ur~ta by Ravisbanlcara 

!l...!.l.. S.condly. t.wo !it. eacb of both the Barn .. and Ravilbenkar. data can be .... d.: one at fixed 

P!i and var'/in& ?:z. and t:'. other at. find P02 and v.ry1n& ?M (i .•.• vL"'7ina addud lIZl. Wit:.in each 

dat.a ".t.. rat.. ccxu.!.ant.s ~alculat.ed fr:m both !ita a&re. reasona.bly ",,11 for .... .;.. !ract.iC!a a! Cz near 0.2 (.quivalent. to airl. but. d1s8&r •• by mor. than • factor of 2 for _asurellleDt.s in • pure 0z 

.1St.... Finall,.. the t.emperature d~. (frail 264-293 1:) 0' the )t." values frOCll Barxwos ~. 

vari .. -.ay.r.-t.1caUy. frOlll aD E/R 0' -1300 X for runs in pur. °

2 (at 700 torr t.otal pr.ssur.) t.o 

-2900 Ie in a SO torr 02 plns 650 torr .2 lIl1xt.ure. An Arrbwu. fit. of the Ravbhankar. at. al. dat.a 

(!rail 251-348 Ie) recorded ill synthet.lc air .t. 690 torr y1elda an Eta - -3250 Ie. Thes. observations 

I\l&&e.t. that. ka and ~ an DOt. ind.!*ldent. 0' the 1dentity of H. For tbia reason. ". limit. our 

recClllllendat.ion to air mixtures (1 •••• P02/Pza - 0.2S). 

The pr .. ent. recClllllend.t.1on accepta the _aaur_t.. of Rarliballltar.~. (1986) tobicb appear t.o 

be tbe "",.t. sensitiv. of tbe thre. iuvest.i,.t.iClCS. Thus. k(298 Ie) is ba.ed on lID avera,. o( the 

-t...o··(~v.-ment.ioned) Cit.so( the Ravish4Dlcar. dlta·7ieldin& (in unlte.· of =3 1II01ecule-1 ,,-11 __ 

k(298 1:) - (1.8 x 10-15) P 

when P (th. total pre.surel 1& expr .. sed in torr. lb. """,ertaint.,. fa""..ol: ('298 - 1.5) .,cocopasses 

t.be r.sult. of Barn .. ~. (1983) "ithin 26. To caaput.e valu •• of k b.low 298 11: ... have t.aken 

t.be E/R value Crall tb. Ravisbankar. data aDd adJust.ed t.be pn-upoceot.lal factor to ,iv •• xaet. 

8&r.-nt. "itb k(Z98 Ie). ~. reault.iD& ezprua10n 1& 

k(T) - {(3.3 z lO-20)-xp(32S0 + 500)IT)} P 

14 

:.--...... 

,.. 

;; 

~ 

-~ 
~ ' ... ~-----.--- ----------- -... - -- -- _ .. _. -.. 

-. 

• 

~-f , 

~ 

i ;-. 

, 

< 

r -.- , 

i 

--.. 

f " 

,. 

If. 

-. 

- ... ": 

" ... ~. 

., 

! 

:(' 

'""" 

...-...... 

.... . , 

;' 

'-

-~ 

) 

~-.--

4aln. t.bb recClllllcdat.iClQ is vaUd ClQly for O%YIIm-tdtroalft a1xt.urea at. • tot.al pru.ure P Un 

torr) hav10a an OXJIC 1II01e fr.ct.iClQ orO~Z;--the-anrh .. been .. t-to mcompa .. -(.it.hiu~:z.r)~th.­

aver ... Ellt value frCIII th •• tudy ot lIam .. !.L!!. It. is int.are.t.J.oa to nota that. meuur_ta by 

Ilavtshaclta.n~. (1986) at. ~pproldmately ZSO 11: result. in !teft vawes·wbich are independlftt. of 

the pr.sence (or 1IIIQWIt.) ot OZ. This sUSlaaes that. th • ..tduct. is quita st.able with :aapect. to 

dinod.t.ion into th. reactanta (al + CSZ) .t t.hia low temperatura cut the .ttectiv. rate ccnst.ant 

(or re.ctant. remov.l is equal to the el.-ntary rat. CClQstlftt for the adduct tormatioa. Clearly 

additional work IfMiY be needed bet:ore th. tull details ot this complez re.ct.ion an _derstood. 

H". O. HZS. This reccamcdation is derived frCIII an unwaiahted laut. .quarea fit ot th. data ot: 

Sinalaton et. a1. (1919) and Wby~.oclt et. a1. (1916). Th. results ot Slslla et. a1. (1978) show very 

load aare_t tor E/R L. th. temperatura reaion of. overlap (300-S00 11:) but lie systematically 

hiaher at. avery t.mperatur.. The uncertainty tactor at. Z98 11: h .. been chosen to aocClllp&&a the 

valu~s of. !t(Z98 11:) dot.ulIlined by S1&al.~. (1978) and HoWndc at d. (1970). Other than th. 

Z63 J: data point ot WbJt.oclt ~. (i976) and the Z81 11: point. of.-Staal. et al. (1978) th. main 

body of. rat. ccnstant data below Z98 J: CCIIIBS trCIII th •• tudy of. HoWndc et. a1. (1970). which 

indic.t.. a dr_tic cbans. in Ellt in this temperatura relion. th .... 6EJR ... set to account tor 

tha •• observations. Such a non-linearity in th. Arrhmiua plot miaht indicate • cban,. 1n -th. 

reaction mecbanl_ t:rCIII abstractien (Iii Wr1ttm) to adilitlem. An ._dditionar channel' (resu1t1na in 

B-ataal dbpac_nt) has b.c proposed tor thia reaction by Sa,le et. at. (1978). Sinal.t.on at. a1.. 

(1919). and Sinalaton et. a1. (1982). In th. two Sinaleton .t.udi •• 1ft uppar limit. ot ZO% l.a placed 

em th. diaplac_nt channel. Direct observation ot product BSO ... mad. in the recent re.ctlve 

sc.t.t.erin& experiment.. of ClaDO ~.- (1981) and D.vidaClQ.!L!!. (l98Z). A threshold eneray- ot 

3.3 !tc.l/1D01 •••• observed (similar to th •• ctiv.tion eneray .... sured in earlier st.udi .. ,· sussest.inathe importance ot this direct displ.caunt channel. Add1tion products trOlD this reaction have been 

SHU in e .. tdx by SoDardz .... !ti and Lin (1977). Fu~ther kinetics studies in the 200 to 300 X 

rm& ... _U as quantitative direct. _chanistic in!omatiOll could clarity these issues. This 

re.ctlon is tbouaht t.o be of limited st.retospheric 1IIIportanca. bowawr. 

H5. 0'" oXS. !he va:ue for k(298 K) is the averqe of five ditferent studies of this reaction: 

Westellber5 and d. Haas (1969a). KlI!I!III and St.ief (197"). Wei and TimDons (1975). ManniIl& ~. 

(1976) and Bnckenridae ane: Miller (1972). The recoamended v.lu. tor Ellt is the .verase ot thos .. 

determined in the temperat.ure studies r .. p~rted in the first thre. references. Bsu.t a1. (1919) 

report (.h.t this reactlon proceeds-exclusively-by- .. strippina mechanism. 

H6. 0 + CSZ• the value ot k(Z98 X) is the aver .. e of. seven dataIlllin.tions: Wei and TiI!IDons (197S). 

Westellbera and da B •• s (1969.). Slaale ~. (197'.). C.Uear end Smith (1967). CaUaar and 

Hedse. (1910). I!oawm .t a1. (1968). and Grahlllll and Gutman (1917). The!IR value is .... varaae of 

those determined by Wei and TimDons (1975) cut GrahO!ll and Gutman (1971). 6EIR bu bellO set to 

encompass the llallt.ed tempece~ure dat.a of. We.tanbers and de 1Lt .. (1969a). The principal reaction 

products are thouaht to be CS ... SO. Bow&ver. Bsu~. (1979) report thet 1.n ot the reaction 

at. 298 X Pro~'aeds -t.hrouall th .. ch4!l11el ihidlna dl-+ S2 &lid c&lcui.i.e ~ rat._constant:!Ortn.ov.~alI 

process in qr .. lllent .ith that recClllDended. Grabam and GutIUD (1977) luv. focnd that 9.6% of the 

r •• ct10n proceeds to yield OCS ... 3 at room temper.ture. 

H7. S + OZ. This recOlllllend.tion is bued primarily on the study ot Devis ~. (1972). Modest 

aare_nt at Z98 J: is provided by the studies of Fair and Thrush (1969). Fair at al. (1971). Dooovan 

and Little (l91Z) and Clyne and Townund (1915). The study by Clyne and Whitefield (1979). Nbich 

indicates a sliaht.ly nea.tiv. Ellt bet_en 300 and 400 X. is eocompas .. dby th. present reCOlllMlldatiOD • 

75 

---

-~ 

, 

, 
CT._ 

) 

) 

BS. S + 0,. thi_ ftC dat1ca accepta tbe CII1l,. ...table ~tal. data: t.hG trc.-CI7D. aDd 

-TOIIUaad---(11175). ID-th-___ tucfT-tbeH-autbon-repaR--.--...1a.-taJ:-S-+--o:i La J:---.hle 

a&J:_t. with that. "~. 'lb. enol: U81t. citAd I:.tlecta both the a&J:_t. .ad t.be need 

fOJ: iDd~t. ccatimet.1ca. 

B9. S + 011. 'lbia J:.~t.1CIQ 1_ baaed CIQ t.be .iJI&le .tudy by Jouzda1D.u....s1. (111711). th.1J: IMUUJ:ed 

wbeD CD. ccma1du. 

the .U&bU,. II:Ht.U aotbemiclt.,. of the pr • .-t. 1:HCt.1ca. 

Bl0. SO + 02. thi_ ~t.1ca 18 baaed ca t.be tc. t..pentun ~ of B1.edi:.I1.J1. (11182&. 

11182b). 'lb. _ t..-penb.lre value accepta t.be let.tu J:.8UlU ... J:.~ed by the aut.bon. 

'%be UDcut.aLat.1._ cUed nfiect. tbe JINd taJ: fw:tbu cClll!lmat.lca ..s the feet. t.het. th ... J: .. ulta 

U. 81pIU1c&llt.l7 h!&beJ: thm &II at.J:~lat.lca of the hi&heJ: ~at.un data of IIaaIID .IL.!l. 

(1968). A roc. t..-ptJ:at.ur. uppaJ: limt. CIQ k .at. by ·kackllDrtda. IIDd Klllu (1Sl72) 18 La &ood 

a&J:-t. with the Black~. data. 

Bll. SO + 03. '%be value of k(2118 X) 18 &II ftuq. of the dataD\Laat.1caa by llalatud IIDd thJ:uah (11168). 

RcbeJ:tabw .ad Saltth (11180). and Black sL.!.l. (11182&. 11l82b) ."Laa w1d.l,. diU.dlll tac!mlqu ... 

t.be value of E/It ia III avuq. of t.be ~ .. J:apoJ:ted by-Balataed-.scl 'fbJ:uah (.1*) cd'lIlack.lL.!l.· _.-

(1982b). with the A-factoJ: calculated to tit the value I:.~ fOJ: k(298 X). 

BU. SO + 011. '%be value J:ec-med fOJ: k(211S X) ia &II -q. of the datemLaat1caa by Fail: and Thrush 

. (11l69) and Jourdain~. (1979). loth .. t_ of dat.a· hav. baeD cou.ctacl ualna the pn.ct 

. __ .l:ec-mat.loD taJ: the. ° + CS nactioD. 

B13. SO + 11)2. th. value of 1t(2IIS X) 1& an .vuq. of the .... UJ:_ta b,. Cl7D. ODd Hacllcbut (11l80)' 

Black .t .1. (1982&). aDd lI=lna and Sti.f (11186&). which qna quite _U with the I:.ta can.tllnt 

calculated !J:CIII the nlativ. J:.t. _ta of Cl~ ~. (11166). '%be ArJ:b&llias pu_tus 

u. take from Bruzmi". aDd Sthf (11l86.). 

H14. SO .. CW. th. value of It(Z98 X) i_ an avarq. of the .. a.ur-.nt.. by CI7DII and ~2.0bart. (1981) 

and by Brurm1n& aDd SU.f (1986.). "be t_pn.tun lMapendene. ia takm fn. BruDIIina and Still!. 

with the A-f.ctoJ: calculated to fit. t.be value of 1t(2118 X). 

B1S. SO + 0::10. thia l:.c~daUon 1& ba.ad on t.bAo 81".la I:OCIII t. ... pu&t.UJ: •• tudy by CI7D. aDd HacRobert 

(1981). th. uncnta1nt,. nfiacta the ab .. llc. of 1107 conf11:lD1". Lav •• tl,.tleD. 

H16. SO + BJ:O. this l:ac~at.1on 1& b .. ad on the IMasur_t. of 1Ir=nU1& aDd Stlef (1986h) pufo~ 

Ulldu both uc ••• BJ:O aDd .xc ••• SIJ cCDditions. th. uta constant. ia .uppoJ:ted by the 10 .. 111: Uml.t 

a .. l&n.d by Clyn. and HacRobeJ:t (1981) !J:aa -=_ta of S02 productloa. 

B17·. SOz .... 002 • thh UJIlMJ: UaUt.- 1& baaad ca the atmosJ:b.d,?-pua.ur1i .tudy ·of Grlll;l~.t.l. (1979): .-----

A iow pnuun la.n _~tiC J: .. onw. _tudy by II!Juows .t d. (19711) plac .. · a • .....nat. MIh.r 

-17 

upper UaUt 011 k(Z98 r;) of 4 x 10 (dataadnad nat.iv. to 011" Bz02). '%belJ: llm1t 1& buad on 

. ___ the ..••• Ullpt.lon that the product. u. CS" S03. l'ba ... i&ht. of both fob •••• tudi •• auu .. ta an uror 

ill the .uU.r dat.adnat.1011 by P.,u.~. (1973). 

B18. SOz + ClI:J02. this racc:am.sdat.lon acc.pta n.ulta !%aa the _body of Smdu and WIItaOD (198111). 

which 1& b.U."ocl to be fob. DO.r. appropriate at.ud7 !oJ: atJ:Stoapbarie IIIOd.U". purpo ... ~ tho •• 

which baY. beea coaduct.ad. '%bell: axpad .. ota _r. c:ondu.cted ..aLaS .. ch tow.r ~Oz J:Sdical 

ccacantratiClllS thaD 111 the .arUn .t.ud1 .. of SanblJeza .t d. (19711) and Xc~. (11l79). both 

of ..tIich nsultad 111 1t(298 r;) values approximllt.l,. laO u ... laqu. A utu npoJ:t by )';an !.S:...!!. 

(1981) po.tulataa that. th ... cUff.nne •• are due to the I:.actlv. raIIO'Y.1 of the ~0z!Dz adduct. at 

76 

,.". 

..../' 

~ -_. 

: J(4 

_ 
." --,---_. .- ------------_._----------_._---- --------- ---------' 

) 

--

p. 

// 

r 

€. 

~. 

) .. _-. 

819. 

Mah-CIIJOz r..u.cal CCIICctz.tJ.oaa, prior to ita rwu.u.le decc:.poaitiCID lDto ~Z- + SOZ. th.,. 

.,,"ut that aacb b.tlwior of a,.oz~z or ita equillbrated addoact with 0z (r:al7.~fJZ) -.ld be 

.zpecte4 lD t.be .t.udJ. .. yhl.d1D& Mah t value., _11 .. dacc.poaitic:a of a.pi!'? lDto reactant. 

tftIUl.d cIoainata in the SmMr md-Watac:a apad_ta. It cIoa. DOt. appau llk.el)' that Ncb .......tuy 

nact.icma lDvolv1D& CB:,0z' .c, or otbar r..tical apech., if th.,. occur, -td be rapid'oaouah 

UDder '_ma1 .t.rato.pbar. CODditicma to ~lete with the addoact daccapo.itiCll. ru. iDtapntation, IIDforbmately, do •• aot ezplain the h1&h rate CODatant dUived by Cock.~. (111815) under 

coad1ticaa of to. [~OZJ. 

S02 + IIOZ: SO;, + IIOZ• tbe re~tiCll. for both of UlNa nscticaa are basad CIl u.. .tDdy of 

Pmzbom .ad c.ao •• (1883) ua1D& •• CODd duiv.tin UV' .pectro.copJ'. th. uppar llIII1t. &1- for 

t(298 ~) in t.be SOz n.ctiOD i •• ctually th.ir __ ured value. a-.r, thair obaarvat1coa 0: 

.tzcoa h.terol~ aDd _ter vapor c.taly&ad .ftacta praapt. us to .cc. th.ir _"ur_t .. an 

~ppu 11III1t. ru. value ia approxiaatel)' t.o orden of -..p1tudelowr thaD that. for • .dad: raactiOD 

ohauved by 3.ft. md nain (111615) in IOZ + SOZ.ut.un. C-h of which IY7' have beau eke to 

h.tuoacaoua ~ ••••• ). Paozhom and CaDG •• auu .. t. t.be product. of u.. SOz r .. ct.loa to be 

110 + S03. th.,. ob •• rv •• mit. uroeol produc..t in the resctiCll of IOZ with SO;, and 1Dta~ it 

to ba the adduct JSCI5,. ru. claiJD ia .upported by ~_.pactr • .:... 

820. S02 + 1103 • rue ncoamended uppar limit CIl t(Z98~) ia tha r.au1t of D.ubmdiak cd Calvert (11175). 

CODaidarably IlIOn CCllAUV.t.iV. uppar 11III1ta hw. bam d.rived by,Bunoora~. (18~) and Wallblaton 

.!S:....!l. (19815). 

821. S02+"3: thia nClllllHllclatioii i. ba.ad on -the Ua1tad d.ta of-D.via .t d; (1874b) .t 300 ~ and 

360 ~ in • .t.oppacI-ficw iIzv •• ti8.tiCll uaina .... apactrClMtrlc .ad \IV .pactroacopic d.t.act.1on. 

822. Cl + HzS. th. val ... of t(298 ~) ia tin war ... of the .... w:_t. by K •• bitt cd Laona (1880), 

which refin •• t.be d.t. of Braithwait. and Leon. (1878), Cl)'Da and OlIO (1983), C1JDS!Ul. (1984), 

and K.". at d. (1985). the zero activatiCll .nuO' b dorived !rem the d.ta o! Kava ~. md 

t.ho A-bctor 1& calculat.ld to &&r". with k(Z98 X). Lu~. (1986) alao measur. a temperature 

indopendent rate constant, and th.ir laraor value 0' t(Z98 ~) - 10.5 z 10-11 JDa)' ba 1ncI1c.ti ... of • 

sll&ht pr ... ura depandmca !or the ra.ction, dna. th.ir .rpar1meDta ... r. par!:).-cI .t 4000 torr. 

-823. Cl+-CX:S. th1a-up;:or llIII1t'ia b •• ad on the 1II1n1Dua'd.teetabla deere ... in .tomic chloriD. measured 

by !ibl1na and ~u!maD (1983). B .. ed on th. ob.arvation of product SCl, th ..... thon sat a lower 

-18 limit on t(298 Ji:) o! 10 for tha re.ction .. -rUt... CODaidarably _r. cCl1Sorv.t1v. appar 

limits on t(Z98 1:, _r. d.teIlllinad in th •• t.ucI.l .. o! Cl7D.~. (1984) and lava '.t al. (1885). 

824. ClO + cx:s: CLO + SOZ. tha .. ree.,....,.ationa are b .. ed c:a th. diachu,. now ..... pec~dc 

data of Eibllna e:1d ~ufman (1983). th. uppar Ua1t on t(Z98 X) for ClO + OCS ...... t fna the 

miniIIuD d.teetabl. d.cr .... o! CLO in thi. re.ctica .".taG~ JIo product. _r. obs.rved. 'PI. ~r 

limit.: 0Ilk(28'S lc) for C10 ; sOz ia i.~ed on the ~thora' - aot.~t~- ~, U..-i; d~t~illty ~or S03. 

th.ir •• tilllat .. o! t(Z98 ~) b .. ed on th. 1111n1Dua detectable deere ... in CLO hna nOt -b ...... ;..ed 

bec..... o! the potlDtial probl_ of CLO refomatiDD !rae tha Cl + 03 .ourc. raaction. 

B2S. S8 + HzOz. rue recOlllll8Dclacl uppar Ua1t 'or t(298 ~) i. baaed CIl the .1Dala study of Friadl 

.!S:....!l. (1985). their val ... 1a c.lculated !raa the lack of sa decay ( ... ured b7 la •• r-!:dac.d 

!luorHconc.) IZ>d the lack of 08 production ( ..... urad b7 raaonanc. !luor •• cmea). lb. thr •• 

possible product chcmala er.: 8z'5 + II)Z' BSC8 + CII, and BSO + H20. 

77 

- -----::;::: -:-

... ' 

-;~.{i~i~·};i;"<l.;,: ::"O~~~.);;L;l'::~;:<':~"'.: ~-~~~~"" ..... _ .... ~i;:.:..,~""*~~li.<"j,~~~,-5i'~w,i;~;:J'iii';:;ii,it,?:;fr7",i.l",~~i::· _" i:.: 
.;.F.-. ,. 

) 

'. 

: 

-. 

// 

. r" 

.. 

:. 

.oj 

) 

1U6. sa + 0. -Th1~ nCClllMDdaUCIIl accepts the reaults of Cupit.t. cd G1au (11175). %be lara. _.re.aiDty 

raflAct..-th.-f.a~t--th_la-onl,..-.-.t.~f-t.he-r"ct.1oD. 

B27. sa + Oz. Thb-n_ upper Uait..for k(2118 1:) b b ..... on the recent. .t.udy by Stachnik IIDd HolJ.ne 

(l9t7) in .xper.tmenb .ensitiv. to the product.iClll ot 08. Hore CCIIlServat.iv. upper lilIIl.t.a on k(298 

1:) of 1.0 x lD-17 &Dei 1.5 x 10-17 war ... dlllad by Fri.dl~. (11185) ...s w.na~. (1987) 

re.pectively !nm det.actiClll .aaait.iv1t.1a. for 011 production sud sa dacay, respect.ively. AD awn 

h1&ber upper Uait. by B1ac:k (11184), b ..... CD the lKk of sa dacay, IU7 haw be.s COSIpUcat..ed by 

sa reaenerat.ion. H..tcb lA ••• ensitive upper lilIIl.ts bad bean calculat. ... by T1_ ~. (1981), 

H1alAen (1979), sud Cup1t.t. and Glas. (11175). StsclmU: sud HollDa (11187) ~ report. a mor. 

-18 cQll!:ervat.iv. upper l..1.IIIit. «1.0 x lD ) for the rate conatant. for the ... ot: the tM) sa + 02 

nact.ion ch __ ls (produc1D& aI + SO IIIId a + SOz). 

1U8. sa + 03' The value for k(ZII8 1:) i. aD averq. of the d.temiDat.iOl1S by Fd."'l at. a1. (1985) 

(laser induce.t fluoruc.oc. detect.ion· of SB), ScbCIIlle .t. a&". (1987)' c-s. spect..rc:aet.r1c det..ction 

of reactant. sa and product. BSO), end Wc!& &Dei Boward (11187) (lsHr -anet.ic r .. cxulDc. dat.ecUCD of 

SB). The t.~nt.ur. d.pmdence b tn. Wana sud Boward, with the A-factor calculated to qre • 

.,ith the rec~'" value of k(ZII8 J:) •. t.(E/Il) renact.s the fact. tbat. the t.perat.ur. depeDdenc:. 

c.,.... frail ... ur ...... b above rOClD t..aparat.ur. cd thus .xt.repolat..1CXl to -t-_ t.ecoparat.u.r_ uy 

h .... addit.ional uncertaiDU ••• 

1U9. sa + liOZ' nus nc~tiOD accape. the recent. _ .. ur~. by Wana et. a1. (1987). lhase 

authors SUU .. t. that. th. lower valua. of k(Z98 J:) ... urad by Blaclt (1984), Fri ... l!l..!!. (1985), 

-and Bulat.oY-.t. a!. (1985) are du. to sa r.a_raUon fraII_th. ~S source.ca.poaDd. In the racent. 

study by St.achnik and HoliDa (11187), at.tAalpts "an mad. at. IIl1D1miziDS .uch resen.raUon. lhas. 

authors obt.a1Dad a k(Z98 1:) value .i&Dificmt.ly. Mahar than did th. .arller inv.sU&ators, but. 

st.ill 30% l.,...r than that. _ .. urad by Wang at. a1., wbo usad boo indapendent. sa sourca reactions. 

A st.ill h1&ber rat.. constmt. value ... ur'" by SchOnl.~. (1987) h .. DOt. bean raCX8leDded dua 

to the .ClIIIMOhat. limit.ed dat.a bas. for th.ir dat.arminat.iCXl. Th. r.act.ion as writt. ... repraseut.. tha 

""'st. exot.har.:lic channel. The absonc. of a primary isotope .ffact.. as obsarved by Wang ~. 

(1987), coupled .,ith the lars a maaniwd. of tha rat.a ccnst.&t., su&aest.s thAt. t.ha (!our-cen~er 

int..= .. diat.a) charmaLa produc1n& SO + 1Il1O &Dei OS + SIlO ara of minor import.cx:.. No rodanc. for a 

thr .. -body caobinat.ion react.ion .... found by either Black (1984) or Friedl~. (19IS). B .... d 

on a pr ... ur .... indapend .. ca o!....t;h • .rat.. CCD.t.mt. babfeell 30 and 300 torr, BlAck •• t. m upper l1m1t. 

-31 o! 7.0 x 10 for the third body rat.. constant.. SiID1larly, Seacbn1k and HoUna (1987) saw no 

chm&a in decay rat.a baboftD 100 md 730 torr .,ith Oz (altbouab tha.a 0z aparu.nt.s IOU. desiplad 

priud1y to llD11 t. sa reaenerat.ion). 

830_ BSO + NO, BSO + NOZ' BSO + OZ' These rac~iona for all thraa react.ioas are Us ... en tha 

...... ur..nt.. of Lov.joy .t. at. (1987), who used lasar f1JJI,pletic rHClDaDce dat.actico to IICDltor BSO 

in a diach&r&a flow reactor. lbeir upper li1D1t. for t.ba ., react.ico i. a !actor of 2S lower t.hao 

the rat.. c~~t. -maasured byllulat.ov lot: d. (1985) usina iDtncavit.y l .. er -absorpUca at. pr_5ur ... 

b.t. ..... 10 mel 100 torr. Sinc. it.i. unlik.ly that. t.bh ruct.ion-rat.'-",,"rsoa. a·!ac_tor:o! .. 25 

increasa bator.an 1 torr (th. pressure of the Lov-ajoy ~. work) sud 10 torr, t.ha bi&har rat.a 

coost.ant.- IU7 be due to secondary ch-utry .. sociat'" with the BSO producUoo. 

The reCCllllMDdaUCD for the IIOZ react.1oD 18 a factor of boo bJ.abar thaD the rata coast.aat. raported 

by Bulat.ov at. at. (11184). Lov.joy~. have at.tribut.ad this dUfaraace to BSO raa_at.1on 

under the upuilMntal CCDditiona used by Bulat.ov at. al. (1984). lb. pro:lact .. a1~t. ~r tha 

1IJ2 react.ion 1& di.cus.ad in DOta 83Z • 

78 

~1""'-~~:~;'~':"':-""'.f'!":~:'i.~,;,,;:;;C"~' :~J.~~_,-,-",",-,,--c .. :....~~;:..:_.. .,_ 

,. 

; 

.. 

• 
) 

.. 

Ii 

• 

f 

.. 

.; 

., 

f 

-r·-

~ 

..... 

/ ..... 

. r. 

" .. 

-

j 

831. 

83Z . 

!ISO ... O:s. nus ~tJ.ea is baMcl ea the .In&l. detemil:lat.1ClD by Fdedl.!L!l. (1Q8,) in 

their .t.udy of the sa ... 03 x_ct.lca. At. bi&hex 03 _1Dt.nUODII, a: .. tex qulDtJ.t.1e. of !ISO 

_n pxoduced in the !low t.ube md sa appxoached a .teady .tate due to 1ta nl_nt.ica via 

SSO ... °

3 • n.. xatoe cCll1Stmt. ~x thi. lat.tex nactJ.ea w.. thus· detamlDed xelatJ.ve to sa ... 03 

tzt. -.-r-U of the .~ .tata sa ceacmt.ntJ.ca .. a fuactJ.ea of the init.ial sa CClDceUatioo. n.. l.a:k of an iSOtope effect. _m SO was aalplD7ed .aue.ta thet. the Producta of the 

SSO ... 03 xeactJ.ca UtI sa ... 20Z (anal01OUS to tho.e fox 11)2 ... ~). 

IISJz ... ~. nu. xac~UOD ia bued ea the nte of II)Z fomat.1ca MUUXad by LDveja,' at al. 

(1917) upca ..sd1Uea of 0z to the SSO ... 80Z xeecUon .,..~. While BSOZ IIU not. cbauvad dixect.l,., 

a ccaaidexatica of the MChmi.t.1c po .. 1biUt.1a. fox !ISO + "Z' coupled with _uax_ta of the 

II)Z prodac:tJ.ca r.te at. vuioua 0z pn.auxe., led the.e authoR to au&le.t. that. IISOZ is both a 

majox pzoduct of the BSO + ':)Z raact.iea md a pxecuraox fox II)Z via nactJ.CD with OZ. 

833. 1ICSOz'" OZ. nus xacCllDeDdatiOD i. bued CD the neet. .t.udi .. o£Glauca!Ul.. (1987) &lid G1euon 

ad Boward (1l1li7), 1D MUch the BOSOZ nactaDt. w .. dinet.l,. .... 1toxad uain& a ch.-J.cal iOD1zatiOD 

__ apectxcaat.dc toecImJ.que. Glaaaon md Bowaxd CCDductad tneix _uux_ta OVOIX the 2i7-423 X 

.t..perat.are xqe, c:onaUtutiD& the 001,. teoapautun dapaadlDce inIrUtis-t1CD. TInaa 6E/lt_haa. bean 

iDC--auad !rca theix quoted limit.. to account. fox the potct1al uncext.aint.1a. in utrapolatin& 

their data to aublDlbict tampaxatux... the value of Jt(29~IC) deriv.. fuxthex aupport. !rca the 

atuar of Bmdo md Bowud (1987), who employad laau IIIqllaUc naoaance detaction of p1"Oduct. BOZ' 

ad rrc. the at.udie. 0' Hu&1taD (1984a) aDd Hartin~. (19811), both oftobaal usad 1IIOdalin& nt. 

o! CB ~ed1eal. da.c~_ ~~e OS .... SOz + H nact..ion .,.a~ in. tha pre.c.ce of OZ. aDd RO. In thi. 

!at.tar .. alyaia, the 8:lSOZ (p1"Odu,ad by OB .... SOz + H) xeacta with 0z y1aldin& II)Z' tohich aub .. -

quct.ly xe,euate. OS tbrou&b it.. xeacUCD with Ill. 

B34. 

B35. 

B36. 

8i' ... 1103 • nu. x.CCIDIICIdatiCD ia hued eo the ..... ux_t. of WalUnat.on et. al. (1986), parfomed 

ua1.ll& fl..a.ab pbotol,.a1. klDatic absoxpUca .pactxcacopy. 

c:; .. OZ. Iha recoamend&Uon ,ivan for k(Z98 K) is basad on tha work 0' Black~. (1983) usm, 

LIF to .:mitor CS dec.,... this value &&r". with the ~t. le .. pnciae datarlllinatieo by 

RiCludsoD (197') usina cx:s !ozmaUca nt •• , .""aat.1n& the vaUdit,. of the n.ct1ca producta as 

writ.tan. the latt.er autbox F •• eata ."idmce that. thi. xeactleo chamwl daaJ.n.t. •• the one pxoduc1n& 

SO ... CO by IlIOn th.n a factox of 10. Heaaux_ta by R1chardaeo at. 293 IC &lid 495 IC ,.ield an E/R 

val» of 1860 IC. Bowver, use of thi. activation meqy with tha xeCOllllMlDded vatu. of k(298 IC) 

-15 renlta 1D .. ...,...ua11y low Aubenius A-factox of 1.' x 10 • In vi .. of thia, no rac~tion 

is .,re ... tl,. &1"" ~r the tamparature depandmce. 

c:s ... 03; c:s ... .,Z. Iha k(298 IC) rac.-ndat.iona fox both nactiona accept the x .. u1ta of Black 

~. (1983), Mlo wed LIF real-time detect.ieo of c:s 1n a laau pbotolyais experiment. at. rOOCII 

t.ea:pera=-re. Ihe =caxt.aint,.. fact.or x.nact.a the. allamce of anr con!1.tm1n&_ ... asurDll!lt.a •. 

Jl. Ifa ~ 03. The reccmmend&t1cn ia the avaraae of ..... ux~ta of Sl1vu cd IColb (1986a) and Alu 

!l...!l. (1986). Tbaa._ ~e. ue DCt. in &ODd aa:eaaot, diU.dna by about a tactox of two. 

Heuur_t • .-:Ie by llusa1n ~. (198') at '00 IC ue ccaai.t .. t. with the xac.-ndat1cn but 

an not. includad because they d1d not. xacoa;n1za that. aacoodary dwaiatry, • .0 + 03 - Ifa ... 2OZ' 

interferes with the rata coef!1cieat MUUX_t. Aler at al •. (1986) e.tiaat.e that. the If.oZ ... ° p~ct cba=al S 5% • 

79 

,. 

./ 

-

~ 

, .. ~ --- ,,; 

~- : ~~~:-.. -: --.--~-"-"--..:.. .... :-~-.~.-~:-.-~ :·~-:~:-~~"i.tif:~4.'f! ,. ~i'~:'''1.t 
~", 

) 

.. 

~ 

p 

.. 

../ 

// 

r 

I ~ ... 

;. 

-. ~ 

y 

J2. lIa + l.p. n. rec~atiCD 1Dc:oqlOr_ tha data of &aaiJl mot HanhaU (1118.5), Aa- 5..!l. 

(11188), and Silvu cd Xalh (1I1SSa). BuaaiD cd HuahaU aDd jan.lUJ,. -.d tha ~.t.IIn 

d~e ovu tha rcaa. 3411 to 1117 lC and 240 to 428 lC, r .. pacU".ly, aDd u. 1D IDOcI ~. 

Silver aDd Xalh .uw:ed a rate coaUic:J.eot at 2115 lC tClch i • .tIout. 351 1oooa~ thaD the other toG • 

EuUu la •• d1ract. .WdJ.a. ua d1ac:ua .... by Aaar~. (11188). n. 1.0 ~t doe. _to ra.a 

alp1ficmt17 with 120 at. roc. t.IIIpe1:at.ure (k (for la + 12 + 0 producta) S 10-16 ee3 _1.ecula-l 

.-1 aDd It (tor lla02 + 12) S 2 x 10-15 jan .IUJ,). 

J3. lIa + C~. ~ _ .. w:_ta of the rate coaUiciant. for W. nect.1CD an 1D _cau..t -ara-: 

Silver (111M) mel talcott. ~. (11188). tha rec-m.d value i. the _qa ot u..... ~ 

t-.parature raaulta. 

-J4. llaO + 0.' The re~t1CD i. baaed OIl a .asur_t. at. 573 lC by Plme aDd lluaa1n (11186) •. n.,.-

reported that S 11 ot the lIa product i. in the 32r axcited atate. 

J,. llaO + 03 , Thia reaction .... tudied by Silver cd 1Colh (lIISSa) and Aaar!L51. (11115), IIb:J qne 

on,.the rata cooUicioat mel branch!Jla rat.io. Thi. ".ar..-ot aq ba tortul_tous ~_SU..:!"'r __ 

JColh u.ed an 1Ddirect. _tbod aDd an mal,..ia baaed CD their rat.e coatfic1_t tor the .. + ~ 

reaction 1Ibich ia about. 1/2 that nported by Aau.n...Y:. jan~. epl.D7ed a .-....bat IICn 

direct. _UW:&llllGt but. tha study ia cCIIIPllcatad by a c:ba1n raactiCD _ban1a 1D the 1a'03, ays~. 

J6. 11.0, + ,1I:z' tho rac~tiCID i. bued CD ... ~_t b7 Aau and JlcMud (1987a). n..y also 

reported a a1p1Uicmt Ita + ~O product. ch_l and that a _u t::action of th.' I. f:rca. tl:I.s 

chumal 1. in the 32r a"cited stata. 

J7. 11.0 + H2

0. tha recaDMnd.t1on i. b .. ad on a _ .. w:-.t by Aller md IIoooard (1987.). 

J8. NIIO + NO. !hI rec~ndation is based on an indirect .... urlllMlnt reported by AIIer~. (19861. 

J9. 11.0 + SC1. !hore ia only one indirect. _ .. w:_t ot the rate coetficioat to~ thls r .. ctioo, tl:at. 

trom the .tudy ot Silver at &1. (11184.). tbay indicate that the products ue lI.el and CO, althoo:lP 

.cme 1I.aI aDd C1 productiCD ia act ruled out. 

Ji0. NII02 + 110. !his reaction is cdotharm1c. The upper lJJa1t reCOllllll&ndad is %roaI an exper1men:.a1. 

study by Aaer It a1. (1986). 

Jll. N.o2 + 11:1. !he rec:camendatiCD is based CD • _uu.r-r. nported b7 Silvu aDd Iolh (198Ei!1). 

The)' indicated th.t the product. ue KaCl + B02 ' but. llaOOR + Cl -r b. pos.ible produc:s. 

J12. 11.00 + OCt. !he rec:CI!ID8l>dati<>D-is based on the ,study, ot Silver~. (19~4a),_ tobi~ is, t,b~ cel,. 

puhUahad study of this'reaction • 

80 

~I:,,'":':ii~":;~;4~;L'_::~:i~~~,:: ... jf'> ""-~''-;;;-''-''-'d';''-'~';i--''''"':'-:;;;;;;:'>- '_' . '''' 

~ 
..., 

.... . ! 

.. • ,

) 

.. 

., 

.-

r 

~ 

.. 

~ - , -

L_ 

: 

. , 

L 

[ 

[, 

~ 

..;:' 

. 

//. 

r 

/":.'!'" 

, 

-. ~ 

Table 2. Rate Constants for Three-Body Reactions 

b.ctiCla 

&.0+02 .0" 3 

H 

::I ( 1n) + 'Z • I'}.O 

-* B_+ OZ· " IIOZ ' . 

011 + CB " • HZOZ 

0_ + Ill· " ~Z. 

° + IIlZ • " 1103 

011 + III • " IKlltO 

&. - os + IOZ " • !!N03 

H 

* 80Z + IOZ • BlZliOZ 

H 

&. IIOZ + 103 • 11205 

11 

Cl ? !!O ~ CllIO 

H 

Cl. + IOZ • ClOIIO 

H 

• COOZ 

Cl. + 0z " ~ Cl.OO 

H 

I Cl. + Cz!!z • C1CZBZ 

H 

, Cl.O + ClO • Cl.zOz 

H 

&. Cl.O + IOZ • ClOIIOZ -- . 

H 

BrO + IOZ • BrOMOZ 

Low Pra •• ur. L1a1t.·· 

k (I) _ k 300(I/300)-D o 0 

k300 

o 

(1I.~.5)(-34) 

(3.~.0)(-37) 

(5.7:l0.5)(-3Z) 

(IS.W.O)(-311 

(1I.0±2.0) (-3Z) 

(1I.~1.0)(-3Z) 

(7.0±2.0)(-311 

(Z:5±O";""3 H-30) 

(1.8:10.3)(-31) 

(Z.2±O.5)(-30) 

(9.0:12.0)(-3Z) 

(1.3:1O.Z)(-30) 

(tUO.3)(-3l") 

(Z.~1.0)("33) 

(1.~.Z)(-Z9) 

(4.0±2.0)(-3Z) 

(1.8:10.3)( .. 31) 

(S.0±2.0)(-31) 

n 

2.UO.5 

O.U;:: 

1.UO.5 

o U Z•O • a.1I 

1.~.3 

Z.~1.0 

z.lSu.a 

3.ZiO.7 

3.2±0.4 

4.Ul.3 

1.StO.S 

Z.0~1.0 

Z.~l;O1.4U.4 

3.~.S 

Z.~1.0 

3.4U.0 

Z.0%2.0 

Biib Pr ... ura Lia1tb 

k.(I) - k!OO(I/300)--

k300 

• 

(7 .~4.0)(-11) 

(1.~.5)(-11) 

(3.~1.0)(-11) 

(Z.2±O.3)(-11) 

(1.~1.0) (-11) 

(Z.4U.Z)(;'11) 

(4.7U.0)(-12) 

(1.~.II)(-1Z) 

(1.~.5) (-10) 

(1.~.5)(-la) 

(S.~l.5) (-11) 

(1.0)(-11±1) 

• 

OU 

1U 

~1 

OU 

0.5:1O.S 

1.3U.3 

1.U1.4 

O.S:1O.S 

1±1 

1±1 

Z.S~O.S 

2:t2 

(1.~0.7)(-11) .1.IIU.9 

(1.~.5)(-11) 1±1 

ko<t)[H) (1 + 11.o110(ko (I)(H)Ik.(I»)Z}-1 

Mota: k(Z) - k(H,I) - ( ) 0.15 

1 + ko(t)[H)Ik.(I) 

:ha valu •• quotacl ara .uitable tor air a. tha thircl body, H • 

• Units are caS/_beulaZ-•• c 

b Units are ca3/CIOlacula-aac 

* IDclicaU. a chana. fro. the pnviou. Pm.l .... luatiOD (JPL 85-37). 

&. Irullc.tes a chana. 1D tha DOte tr_ tha pr ... ioua ... a1uatiOD. 

, Inclic.te. a n .. entry that ... DOt. in the previoua .... lu.t.ion. 

81 

Iota. 

1 

Z 

3 

4 

5 

IS 

7 

'S 

II 

10 

11 

1Z 

12 

13 

14 

lS 

115. 

17 

>;":'"""~~';;'¥' . .';':;';".~.;: :~-'" .,0>.';,:'."; ":-';:'-'=":::'\::,~cj:::;:....o.o~" ... ~'-_:;' ... , '.c., :;".~"., .•. ". . •... ~',H::._;, ~~.;;;'"'.:.:(~ '" 
~ 

]4 .. 

". 

.: 

r 

f 

.... ' 

/; 

J 

) a.. 

Table 2. (Continued) 

Low Pr ... ur. L1Ia1ta 

It (T) - lt300 (T'300,-n o 0 

1l1&h Pr ... =. L1lI.1t.b 

It.(T) - k;OO (T/301l)--

Raactica 

It 

F + 0z - YOz 

It 

F+NO-FIIl 

H 

F + N02 - ~cts 

- H 

YO + IIOZ - FCIIlZ 

H 

&.~+OZ"~OZ 

- !l 

~OZ + IIOZ .. ~0211OZ 

H 

&. CB + 502 .. lI::SOZ 

H 

__ CS +.~zll4 .. BXBZCBZ _ 

H 

c:a + Czllz .. 3XHCB 

H 

• Ci'3 + 02 - Ci'fJz 

H 

crt:1Z + 0z .. ::rc1Z0 Z 

!I 

c:'''"3 + Oz .. =1:30 z 

H 

lt300 

o 

(1.6±0.1)(-3Z) 

(S.9%3.0)(-3Z) 

(1. HO.IS)(-30) 

(Z.6±Z.0)(-31) 

(4 .5:l:l.S)(-31) 

(1.5:1:0.1)(-30 ) 

(3.0±1.0)(-31) 

(1. S:10. 6)( -Z8) 

(S.S±Z.0)(-30) 

(1.S:10.3)(-Z9) 

(S.0:10.8)(-30) 

(1.0±0.7)(-30) 

crt:1ZOZ + II)Z .. CYC1Z0!"Z (3.5:10.5)( -Z9) 

H 

I!S + NO - I!SJIJ (Z.4:10.4)(-31) 

H 

'a + 0z .. 1l00Z (1.9:11)(-30) 

H 

, !l00 + 02 .. '1-, (3.5±O.7)(-30) 

H 

# ,.0 + C:::::z .. !L0C03 (8.7±Z.6)(-.Z8) 

H , llaaJ + CO2 .. laI!COJ (1.3:10.3)(-Z8) 

D 

1.4:i:1.0 

1. 7:i:1. 7 

Z.D±2.0 

1.311.3 

2.011.0 

4.0t2.C 

3.311.S 

0.8±Z.0 

0.0:10.Z 

4t2 

liZ 

Zt2 

4t2 

3:i:1 

1.UO.S 

Zt2 

Zt2 

Zt2 

lt300 

• 

(3.0±2.0)(-11) 

(Z.0±1.0) (-11) 

(1.8:tO.Z.(-lZ) 

(1I.5:I:3.Z)(-lZ) 

(1.5:l:0.5)(-lZ) 

(8.II±O.II)(-lZ) 

(8.311.0)(-13) 

(8.5±1.0)(-lZ) 

(6.0:11.0)(-1Z) 

(Z.5±Z)(-lZ) 

(6.0±1.0)(-lZ) 

(Z.7:10.5)(-11) 

(Z.0:11.8)(-10) 

(S.7:13)(-10) 

-'II. S:I:3) (-10) 

(1I.8±4)(-10) 

• 

Ul 

1.5%1.S 

1.711.7 

2±Z 

~ .. 

~ 

-~ 

1±1 

li1 

1±1 

2±Z 

~ 

0:11 

0:t1 

0:11 

0:11 

JcUo: Itt::) - k(H. T) - ( 

ltoCY)(H) 

) 0.11 

(1 + [lol10CltoCYHH)Ilt.(T»)Z}-1 

1 + lto(Y)[KlIlt.(Y) 

~ valu •• qucted u •• uitabl. for air .. the third bodT. H. 

a :.uta u. ca5'801.cu.l.aZ

-.. e 

b ~t. ue ca1'801.cutr .. e 

• ::.dieata. a chCl&e fr_ the ~rari ..... Pan.l ... aluatioa (Jl'L 85-37). 

&. ::.dieata •• cluma. in the DGt.a !rca the prm-a avalaaUoa. 

, ::.dieat •• a=- antz7 that. was not. in the prari __ rralaatlOD. 

82 

-- ---------- -- - - -... ~ - ~~--=- ;-;-- ---- - -~. -_.- -. 

lIotas 

11 

1i 

2!1 

21 

22 

23 

24 

25 

Z5 

Z7 

23 

22 

30 

31 

3Z 

33 

34 _ 

35 

{. 

--k 
) 

) 

NOTES TO TABLE 2 

1. 0'" OZ' t-,>r •• sur. limit. and T-d.pendmc. are an averq. of lClaia, Anderson, and Iu.%71o (lP80a). 

and Lin md L.u (1982). Th. r.sult. ia in a&r._t. with most. prIVious ..ark (u. r.f.renc.s th.rein). 

ICaY. (1986) has calculated isot.ope effect.s for thi. react.ion, utins met.hoda .illlJ.lar to those di.cussed 

in the InUoduct.ion; Troe (1977). Pat.rick and Gold .. (1983). 

2. 0(10) ... liz. Low-prusur. limit. !rom lCajilllOt.o and Cvetanovic (14176). The T-depandance it obt.ained 

by .... \AUIa a constant. /J. 

electronic curve crossinl. 

The rat.e conat.mt. it ext.r_ly low in this special systllll due t.o 

3. a ... Oz. J:arylo (1972). Won& and Davis (1974) and Bsu ll..!l. (1987) are averased t.o obtain the low 

pr .. -.r. llait.in& value at. 300 te. Th. first. t..a st.udies includ. T-d.pendmc., .s does a roc.nt. .t.udy 

by Btu .t al. (1987b). Th. racarlMDded value it chasm with conat.mt. <t.E>H -.05 kcal _1.-1• 

This v.ry low nomiler nfl.ct.. rotational .!facta. Th. hiah prouur. limit. is Z fiOlll Cobo. et. d. 

(l98S). n:. tAmp.ntur. dependence is ut.1mat.ed. Cobos~ •• stimat ... - -0.6. which i. wit.hin 

our UDC.rt.aint.y. 

4. 08'" OB. z.olln.r :I':ivate carmmication, 1982) report. preuur. and T-dopmdtnc. in "Z tor 2S3 < T 

< 3S3. Thair valu •• art in rcuah asre .... mt. with thos. of ICij .... ky and Iroe (197Z), who r.port lowpressure valu.s in Ar for 9S0 < T < 1450. Trainor and von RostDbers (1974) also roport a value. 

S. 0 ... JK)~; LDw-pressur. limit. and n from direct. ... asurlllllClta of Schi.f.rst.ein et. a1. (1983) and their 

r~.~""'lyS1iOi:- Uie- data of Whyt.ock~-et 81.- (1976;:- E~ror limit.. mcOlllpass -ot.her studies: Biahpressure liIIIJ.t. and .. from Baulch ~. (1980) and Baulch~. (1982). sUahtly modified. 

6. 0 ... II)Z' Valu.s of rate con.tanta and tllllperst.w:. dependmce. frOID t.h. IValuations of Baulch ~. 

(1980). They us. Fc - 0.8 to fit. th ....... ured dat.a at 298 te. but our value of Fc - 0.6 live" a 

similar result. In a supplementary r.vi .... Baulch~. (1982) IU&&est a sU,ht. temperature dependance for Fe' whi.c!l would causa their SU&luted value to risa to F c 0.8S at. 200 K. 

7. OB'" 110. Tha low-prtssur. limit rat. const.ant. has b.m nported by Anderson and 1Cau!man (1972). 

Stubl. and liki (1972). Horley and Smith (1972), West..nlIers and de Baas (1972). Anderson ~. 

(1974). &-ard and Evmson (1974). Barris and Wayne (1975), Atkinson at al. (1975), Ovel'lnd~. 

(1976), Anastasi and Smith (1978). and Burrows ~. (1983). The sen.ral a&reement is Soad. and 

th. r.c~ed value it a ... iaht.ed av.ras •• with h.avy -iaht.in& t.o th • ..ark of Anastasi and Smith. 

Th. r.ported hiah pressure limit. rate conat.ant is smerally obtained from oxt.repolation. Th. recCl!lCIetIded valzoe is • wo1&hted averase of tbe reports in AnastaSi and Smith (1978) and Anderson ~. 

(1974). [!atb ~ and ~--1J:l1D are expacted t.o b. foDllod.l 

_8. __ 08 +_1102, Th. low-pressure limit is_frail M<!erson ~. __ (l974). who report n -_Z.5 (240 < T/K 

< 4!O); Boooard and Evanson (1974): Anastasi and-Smlt.h- (1976). who report n - 2.6 (llO~ < T/te 

< 550) and lIin.~. (1979) who support. the .. value. over the ranse (Z47 < T/IC < 3S2). The recOlll-

-1 _nded valzoe o~ n - 3.2 com .. frOlll <AD" 2 - D.55_.k_cal mole • (This value i. consistent with 

th. expsr~ta.) Burrows~. (1983) confirm th. value of k at. 295 te. Th. hiah-pr .. sure 

limit. and T-dapondmc. come frca RlUCH model of Smith mel Golden (1978). althoush the error limits 

have beaa upanded t.o aacompas ... - O. Robert.m.r and Smith (1982) have _ •• ured k up t.o 8.6 

atIDOspheros of cr 4' Their work suge.ts that. k. maht. be hiaher than suge.t.ed hare (-501). 

:his maht alao be due t.o othar caus •• (i •••• isomer formation or iDYolv_t of escited elect.ronic 

states). lIomthalder~. (1987) bav. abooon that. 8:X)Z is the only is .... r fo~ (yi.ld -

.7~:i~). Th. re~tion her. flta all data eNor the rca. of at.moapbaric interest.. 

83 

..J 

t ." 

:J( 

• 
) 

I::""""" 

) 

4 

.. 

.".. 

.-

r 

, 

, 

ItI 

r 

i 

i 

.. 

~ 

r·-

// 

r .. 

..a_ 

,-.... 

~ 

II. 11)2 + 11)2. Quaaed ~ Jl'I. 1,..31. hcet1y ~lo _ o...11ette (111M) b&ft x-.w:" Che :WO Ie 

xUl&. _t.alt.a. -~~ cd OIMllAt.ta (1Q11) ~ ~ t.be ~nt.ur. cl~a. th. 

xa_dKvalue.-ar.-tU--:~th1.-lat.terr.fft'_ toIwz.iA-tlIelr1lata-wre--eCllbf.Ded--ttb-that. 

of Saldu IIId PetanOil (11184). the rec-.fed ko (300 t) ia _tat.eDt. with Ibrazd (un). Othel: 

.t.udb. b7 S~t.i. m4-Beickl.e -(1;74) mc1 Cos -.zId.-Pat.z1.dt (111711)_ &1:. 1Dn .. cxubla I&I:.-t. 

with t.be nc~at1cna • 

10. 1t02 + 1t03• n.ta em the x..,u .. nact.iem u. frca C:-U --S JcbDatoQ (111111) m4 Viat- ~. 

(11111). (th ... clat.a an uaed 1D thla ~1a 1'7 mlt.lpl)'iJ:I& by Che eqod1.1brila _tat ,ivaD in 

table 3.) A VeE)' thorouah lID&l.7ai. of thi. data cd a .,xe co.pUcat.acl fit. em be fOUIId 1D Halko 

m4 txa. (11182). bCIlllt. .t.ud1 •• b7 U%char~. (1"), Croce de Coboe.lLll. (11184), a.uh »...!l. 

UGI,) , lIoux-. !L!l. (1111'a), cd WalUll&ton .tL.Jl. (1G17a) CCIlfim the current. ~U_. 

the valu .. in table 2 )'ield a curve th.t. _tell .. aU the dat.a up to 5 at.. ru. ~ludaa the boO 

~.t. pr .. auz. po1Dt.a of Cxoc. d. Cabo.~. 111. ftlu_ ~ t.h18 lat.t.ax ""dt abow 1D .bII &1:. 

30% hilbel: t.hci -th.-Cun.. tb. -valu. of n -. 4.3 1. tx_ ~ ~. (11114). the -tu. 0' 

... 0.5tO.' 1a txClll Uxchu~. 111 •• t.udJ of Foww~. (UI2) 18 not.a4 but. DOt. 'IIMd 1n the 

mal,..I.. JoImat.oll at. d. (1I1M) ha'wo xw18WCl tloh XMCt.1ce. 

11;- Cl + Ill. Low-pi: ••• ux. UJdt. fxCIIl L .. s1..!l.. (lll7k), ClazIt~. (11M5S), AaID=. _ SJ*lcer 

(111'"), md Jlavl~hanltara~. (1978) •• 'flqlexat.un ~a fna Lee.!L!l. (11171.' md C1axlt 

5...!l. (19M). 

12. Cl + 1102 ;- Low-px ... ux. Ua1t. IIId t-daJ*ldmc. 'rca Lau (1G14a). (A .. 1al1ll .1Ja1laz t-upendanc. 

-LD-lIZ IIIId-S •• ) --Leu conna. th. oburvatlan of-If Uti.- et .1. (l1l78c) that both ClCIIO mcl-ClB:IZ ax. _ 

'omaed, with t.ha 'ormel: dominat.iIII. thh baa beaD uplaLDed 1'7 a.ca .t. at. (1979a), witll dat.ailed 

calculat.iona 1n rat.zick Cld Goldm (1983). tha t.opar.t.ux. d~. 1& .. pxacl1ct.ed m rat.xick 

md Golden (1983). the lat.t.al: woxlc azt.mcIa to 200 ton mel tha hi&h px ... ux. limit. ... cho.en to 

tit. the ....... ur_ta. l'b-_ tAalpaxat.un dep_d.ac. of the hiah pz ... un l1Ja1t. ia nt.ilDat.ed. 

13. Cl + °2 . St...m.an~. (1958 I and IHc!:clas and Ncrrbh (1968) .... surad thls proc ... !.:1 Ar. The 

recOCllDCd.d value 1a b •• ed on kCNZllltCArI - 1.8 •• IIIId th. T-dep8lclenc. 1a !>ued on t.h. lSsunpt.lon 

of cOll.t.et. c:6E>. 

14. Cl + Clfrfaken from Bruanilll and St.hf (198". tiIo _-=ed It tx_ 210 to 361 J: 1D Al: betwaaD 

epprOXilDat.al)' 10 t.orr and 300 ton. Exparwmt.a 1n '2 at. 296 Ie toen .... d to ':~la the 1<w-pre.suxa 

llIII1t.ll11 r.t.. conatant.. Ezxox l1m1t.. _ra Ulcra .. ed to accocmt. fox the f.ct. that. _ly _ t.aa:paratuz.-<lepandlltlt. study axiat.s • 

M point.ed out. 1n Brunninc and St.i.' (193'), th ... valli" ua nuoaab1,. CCIIIpat.t.-bla W1:h eax11aa: 

.t.udie. ot: Poulet. .t. at. (1973), AU1nsOll md AacbMaD (191'), Laa and RowLmd (1977). Cld Iyaa: 

~. (1983). 

lS. CW + CW. For t.h. t.aDllOleculu r .. ct.lea (with 1f2 md 0z .. third bodies). II~ ~. (1986) 

raport. 

It • (S.CiO.4) x 10-32 x (t/300)-Z.1%O.7 ca6/a 

'fbi. r .. ult. La 1n &ood &&1:- with tha euller .. leculaz ~.t.iOft ruult. of Jom.ton at. _1. 

-32 6 -- (1969), >!blcb &ava It - , x 10 em Is with 02 .s thizel bod)". ethel: pxevioua _ .. ux~ts. such 

as Cox and D.~t. (1979). lIu= and Bunt. (1919), .... Walk.x (11172). ,." • .-bat. u.u re.ult.. 

(approxJ.8etal,. a factor of t._) fDl: sia1lu third bodi... lbe r. .. oaa fOI: the •• dlffancce. ara 

not. Imowa. the rec~t.1CQ _ompa .... the •• valuaa. 

134 

-~. __ ~~:2......::..~_: ___ ~~ . .:.~ 
q 

, 

I 

)4: pI 

--

--

• 

r 

-l.-

t 

~ " t lr~ 

f 

i 

,. 

: 

~ i 

~ ,-

l 

" 

;,;.- --

~ 

:.-

/,.>' 

'r 

"":,--:" 

6. _)8 ... 

11. 

~ 

ClO + ~ DIe anllIbla k1DeUca da~'~ w. na~ Un fallaD blto bIo leta, IIb1ch are 111 

cU--" t. Sennl ~dnC ~_IUH cleteDliDat.~-(z.baJ. .. rA::l1i,--la77. 

BJ.J:ka .Il.I.l., 1877; X- .I:L.Il., 11177; Lae JLI1., 11112) of the nt.. of ClO dlPJIIIeU_. ri. the 

Cl.O + ~ + H ~ an in ... !Jem; aar-t. -S·p".·m· ... na. k o (300) DIU 1.1 s.lO-31 -.S 

.-1. • podIa"- 1dctUleac.1aD _ cacled OIIt., -S It WI .. .-Ii t.bet. the ~NCt.1as ..... ~1111 

Dit.nlt.l;~. III _c.r.at., oUnct. _u_t.I of the ~eta of themal ~1t.1OD of cumZ 

au-tb, 11171; ~ n....s.l •• wa). ealiblDed with the ItflllJhd __ t.mt., 11.,. ko (300) - 4.' s 

10-32 _1.-1 ~ tM cm..-badJ rMct.1= tamiDa c:u.oz. 11Dc. the _aIlU'ed nt.e of Cl.O cUaappeu-

_ • __ U _t.oblhbM 117 !au ~, the I":uuth n-lt.l em be ~Ued with the b1&be~ 

m-.- !IF thHe .uuaz.a" ~~: (1) the -..uncI themal decalpae1t.!«a n~ i. 1Dcon.ct.: 

(Z) th • .oplUIIC1_ COIIIc..tt. 11 111 IZro~ 117 I flCt.a~ of ~.. (~eqoU~1Jla that. the 6IIf u. aU 117 

-1~, *ida. ollila -U. i. -"ida the .t.at.ad anar lJa1t.a); (3) aU the dec.. u. conact., 

-S the ~aun Cl.O cUaaw-u- .t.ud1_ -..uncI 1IOt. 0Dl7 • r .. ct.1OD fOm1D& cumZ' but. 

-.bar m-d fODIda& __ 1~. aud:l u CCllI02' Cl.lXm, or ocum .(CbaDa JLI1., la7k; Hal1u 

~ •• 11801). 

Ilaceat. -" ~ IIIrptm (UJI3b). ~~. (1884b). cd Iou:b>WI ti..I1. (1Q1,-) 1D41clt.e that. thin 

u~~ S-~_ of ~ ~~ Ibaa. altMr.a:plcaUGD (1) mdlo~ (Z) aba9a _to b. 1IIwIted. 

Wal.ll.a&t.:a mel Coz (1886) eoatim -cv:rreut. - Yal.ue., but In UIIoIh1. to upldD t.be .Uact. of 0C10 

abaarvad 117 bath HDUu n-sl.. (1lI801) aDd u...1".. •• 

th. hialrpr ... _. Uatt. rate CClDStct.a aDd tMlr t..-pera~. dep«lilDc:. u. ~ca t.ha .ad.1 of SlUth 

mel Galdoa (lan). ::!I.- ~a:" cccstct.e above fit. _aaw:ed ret.l dat.a fOr t.be d1.~umc. of ~.act.mt. 

(eai cd l.Mrla; 1117;; Daa~ -~.:; 1911). Dlt.a~ .. Bmo:\wIIdt ali-Z.Uuu (lQl4) 1D41c.t.e a .Uaht.ly 

~k ... 

17. &0 + 102 • Dec.. ~ 3pO X an ~CD Suxlu 1L.!.l. (1Q11). th.,- .UU .. t. k - l'.0±1.0)(-31) k. - 0' 01 a (2.01:1:.)(-11) aDd Fe - O.4:tO:OS. Th. t.--s-ret.ure depeadenc •• u •• !mpla •• t.1mat. ••• 

Evan ~ iSCllllr ~=r.III\t.lon .. ..,. to have l:een ruled out for th. ClO + /D2 reaction (1 ••• the isaDllr 

.UiI>Il.aJ 11 ~ looo too make a &1&n1!leClt cCllt.ribut.lon too th. _uw:ad ret.a eonat.ant.). this do.s not 

.u.inate t.be pa .. 1l:ilit.y that. !rO + 1t02 laada t.o IlIOn thaD CIDI .t.abla co.pauDd. In fact. if the 

...-ur .. val ... of k 1s _capt«!. it. cm eal.y ta. th.oret1cally ~acoac1lad with a aill&l. la ... r. o. -1 ~2' ICtch -..J.4!lav •• 6·7 !tca1 _la 1U!!!&.!.I band-thaD ClQC)2" ·This -U fiX.th. beat. 0' fo~t.1.cIa of ~Z ~ b. u.. __ a. CltIIOz. m unl1ltely p"asibllit.y. 

lS. F + °

2, Law-pH..".,. Uait. 1:...". I!oulch li..!l.. (l98Z). "'0 .".rqed th. raau1t.a of Z.t.zach (1973), 

~yumw-~. (lVS). O>an et. d. (1977). and Sb-.xWDa and Xat.ov (111711). Teooparet.w:. dependenc. 

1a ealcalat.ad (l'at.ridt and Golde (1983». 

Ca1.cula:ad v~s c:! the st.rccrcoll1aion rat.a coast.mt yi.ld a mor. pb"Jaical1y IDIIm1n&!u1 value 

of -IJ .... t:h. JAW value 0' :.be h.';t. 0' .fo=at.ion a' 102 la ai!cp~. --Se. DOt..S too "Tabla 3 md 

Pat.dck md Gold .. (:3113). 

111. F + 1IJ. Pu_tan .at.!aat.ed !:ala strona coWaioa calculaUGDI with· <4E> .. t.-at. .42 kcal/lDOla -1. 

ylel.d1q 6 - 0.30 at. 300 X and 6 - 0.311 .t ZOO 1:. 

20. F + IIJZ' Ezpar~ dat.a af Yuma ali IIo&u (1983) _n used t.o dat.amiD. bath t.be blah and low 

pr_SU1:8 Uait.a at. 300 X. :hay fit their data too .. ."Pu .. 1on .uch as ra~ ber •• 

85 

.. _~. :..k~~-,,:-: .... __ ? . .... "'~ 
q 

). .. 

,., 

.: 

r 

~ 

. ~ -

/....--

r-'. :. 

.. -

)3 

21. 

Treatment. of th. dat.. for tllla ayat.a requir .. Imowlq. of the r.laUve atAhiUt.in of ~ aM raIO. 

-Pat.riclt-md-GoldeD-~II83.>-a&a1-.d~ tllat. t.he diUercc. be~ the •• oooul.d b. tlle ._ aa bet>oe ... 

o ~r a th. C1lI02- ilaMr.. thu., u..y CQ:lcluded that. kJOO(1'1I)1) - 1.11 :It 10 GId kJOO(n.D) - '"30 1.4 :It 10 ,UId thet. fORO would be fo....s -3 t.J.mea .,r. t.vorabll" tllm FlI)1' lie ha". faux! an a -29- error of a fact.or of four in t.bair calculaUcaa, which -rd predict. 1t300(fOII) .. 1.06 :It 10 , -30 end thus an avutob.lIII1na ~t. of JatO. th •• uurad value la It -1.05 "! l:; ,OIIUch is ClIIe-tanth 

of tlla predict.ad value • 

A calcul.Uon .t. th. HP-3/6-3~ lw.l bT Evlath (privat.e cxaamic.t.ion, 11114) 1D:Uc.t... that. th. 

-1 

fOIl) i. much IIIOre tllm 10 Itcal. _1 In •• tAhle than 1'11)1 aDd tbat. it.a rat.. of format.leo caD b. 

-30 ianored. thua, _ b.v. It(axp) - k(1'1I)1) - 1.05 :It 10 • 

th. value of Ii - 1 is froaa P.t.rlclt lind Golden, lind tll. v.lua of .. is • rOU&h .. Uat.e from .1.ailar 

re.ct.icoa • 

FO + R01 • Law-pra .. ure Uml.t. frca .t.rona colUaioa c.1culat.iOll UId ~ - 0.33. T-dapand.nee frail 

-1 result.llnt. ~ - .~ kc.l IIIOla • !U&h-pr .. aur. limit. and T-d~c. e.t.lmat.ad. Cbc. &&&ill (5 •• I 

1Iot.. 16) mulUpla chcmala could be iIIIport.ct. bare, tGlcb -rd _lin th.t. tll. re.ct.ion bet.waen ro cui 

1101 could be mucb -fa.t.er, .iDe. tllne vatu .. caoaid.r aaly FaI02 fOmlAt.iOD. 

21. CH3 + 01' Law-pre •• ure Uml.t. frca Selt.zer IIId Bey •• (11113). (The .. "Ode.n detemined the rat. 

conatant.. u • funcUeo of pr ... ur. in 112 , Ar, °

1 , aDd B.. Ol1ly tll. 111 point.a vare used direct.ly 

in th. _.lu.t.ion, but. theothan .re canal.tent..) Pl\lllb end R)'an (11112b) report. a value in B. 

>ohicb is caoalatent. .. it.b1n _error __ Uml.t.a .. itll th ..... _rk of _S.lt.zer and Bey... PiUiD& UId Smith 

(198S) have ...... ur..J tllb proc ••• in Ar (31-490 t.o"). their low presaur. Uml.tia& rar.. coait.ant. 

is ccad.tent. with this evaluation, but. their hi&h presaw:e v.lu. is • Uttle low. Cobo.~. 

(11115) bave made ..... ur_nu in Ar and 112 frail 0.25 t.o 150 atmolphere.. Tbey report. par_t.er. 

SQIIftIb.t. different. than recO'lJDM'ld-.! ber., but. their dat.a are reproduced _U bT the rec.-.nded 

value.. Th. work of L&&""a cui Bau&hC\D (1981) .e_ t.o be in tll. fal.l-off u,ion. Results of 

Pratt. and Wood (1984) in Ar are consist.ant. with t.his r .. cOQllandation. althou&h t.he .... sureor.:r.s ar. 

indirect.. Their T-depandence is within our enimat.e. As can b .... n frem Pat.rick and Golden (1983). 

tll. abov. v.lu. lead. t.o • very .... U ~, -.01, aDd thu. t.eq>erat.ur. dependanc. is bard to cal.=l.ar... 

th •• UU.lted v.tu. i. an e.tlmat.e. Ryan and Pll.IIIb (1984) SUU .. t. that. th •• _ type of c.lculation 

as amployad bT P.t.rick and Golden yielde a r.UODabla value of~. W. bave not. bem u,1. to AfrOduc. 

their results. Th. M&h pressure rat.e constant. fita th. dat.a of Cobo.~. (1985). Th. t.cparat.un d.paadenc. is an .st.imat. •• (~t.II of va:> dm Bar&h and <:&Uear (1971), Bacban.del~. (977), 

Basco~. (1971), Wasbida and Baye. (1976), Laufer and Bas. (1975), IIZId Wasbide (1980) ue also 

conaldarad.) 

23. ~01 + 1101 , Par_t.era fraa • n.sonable fit. t.o tlle tamparatur. and pra •• urrd.pendent. elat.. in 

SUlder UId Wat.son (1980) UId a..tislwlltar.~. (1980.). l'ba formar referenc. report.. tlleir rOClll-

- t.eIIlper-.tun - data in- the ..... tom as berein, but. they allow _ F c to __ vary. They _ :a.p>rt: 

k - 2 33 x 10-30 k - 10-11 o· (T/300)-3.5 F - 0 4 • • • c •. 

The •• par_t.era are a bet.t.er fit. .t. all tamper.t.ure. tllm tho .. raCOlllDaDdad bere. W. do net. .dopt 

the .inc. tllay ara not auch bett.ar in .t.r.t.oapharlc rm&., end they would uqui:. both a c!:.m&. in 

our Fc - 0.5 fOnDIt., and t.ha adoptiOll of a quit.e lu'. nq.tiv. activ.tica ..... rIY !or k •• 

86 

_ .. ~-..... -..:..~~:.:~.:......-~ .. :. ---

'" 

~-'" 

-------
·) 

~ 

b -f 

i 

.~ 

.. 

.' 

!' 

-: 

·,--Jf 

-30 -4 -u n. CCDAtA ~ec ".U- (~ldI!LU., 111&1) are: ko - Z.3 s 10 (T/300) ,k. - 8 s 10 

-mcLl'c - .-T/3Z0 + .-UIOIT;_"i.l41na.J·C - .41 .t. 300 11: aDd .'4 at. ZOO 11:. Th ••• val .... do 

DOt. fit. the clau .. _U .. the c:w:nDt. rec-.dat.i_. It. is iDtu .. t.l.D& t.o DOt. that. the daU 

reqg1r. a nepti_ t-cMpcdeac. for k., .1ailar t.o our n_ IIJZ + .,Z r.~t.ica, aDd th.t 

the value of ~ at 300 11: i. -.Z. 

24. (II + SOZ. Val .... of the raU -at.ant. ... fl.1Dct.iOD of pr ... ure at. 2118 11: fn. Leu (1982), 

Parukwopoulo.~. (11183), md WiD. ~. (11184). The val ... of the ~ pr ... ure l1a1t. i. 

~ L_ (111&1), corrected for fall-off. Th. hiab pre •• ure lUIit. i. froa a fit. t.o all the claU. 

Th. valu. of n c __ • ~ the ebow. claU ccailiDed with calculations such .. tho .. of Patrick aDd 

-1 Goldm (11183), escept. that. the heat. of fozmatiOD of BOSOZ ia rabed by 4 kcal.,l ," .uuuted 

by the .ark of Har&1t.aD (11184). lb. value of • is ut1aat.ed. This 18 DOt. a radical-radical 

raactica aDd 1& UDllk.l" t.o bcv •• posit.iva val ... of III. Th. limlt. of III - -Z corr .. pc.Dda t.o a real 

-activatica mUI)" of -1 keal _1-1• EarUer clau U.ted iD Bau1ch.JL!.1. (11180) aDd Baulch.t. d. 

(1982) are noted. beet. .ark of Hart.1n~. (11186) aDd Barna • .n...!l. (1"6&) ccafima the 

currmt. avaluetica. 

25. (II + Cz!14.- hpadaent.al clat.a of __ Tully (11183), D"'i~ et. al. (11175), Boward (11178), Grainer (11170a), 

Horda et. at. (11171), and Ov.rend ... Paraakevopoloua (1977h) in hall .. , Atkinaca et at. (11177) in 

araon, and Ll.o7d ~. (1976) aDd Cos (11175) and U.iD~. (1984) in Dit.ro,en/ox",an l111stura., 

have bHD coaddued iD the ..,aluatioa. ru. waU-.tudied react.iea 1& conaiduably .,n campus 

than _at. othen in th1& t.abl.. The par_~u. rac-.ded h.r. fit. aactly the ._ curv. proposed 

by 1I:1eiD~. (11184) at 2118 11:. D1&cnpanch. r~n IIDd the .ffact. ot ault.ipl. product. ch8JID.1s 

i. not. _U uadentood. Th. ~.d~~~f the ~pr ••• ~. lUIit. haa tiot.liHD ·dat.=tned 

apar1llleDt.aUy. CalCUlatiODS of the type iD Patrick aDd Golden (1983) yhld the rec~ed value. 

Th. !U&h-pr .. aure limlt t..per.t.un clapendmc. has baeD "atum1ned by .everal work.n. AJ.Ist. all 

obt.aiD n.,ativ. act.1vatiea -ra", the Zellner mel Lorenz (1984) valu. bel.D& equivalmt. t.o III - +0.8 

avu the rena. (296 < T/lr: < 524) at. .a.out. 1 at.mo.pber.. Alt.bou&h thi. could theoretically ui.e at 

a result of reven!billty, t.h • ...,ul1brium const.ant is too hi&h for this possibility. U t.here is 

26. 

a product chamal that proc.eds with a low barrier via • ti&ht t.ransition .tat.e, a COIIIplex :at.e 

conat.ant. ..,. yi.ld the ob •• rved bahavior. Th. actual sddit.ica proc ••• ((II + CzB4) may evan h .... 

a ...u. posit.iva bardu. the r~ed liait.a mcamp ... the reported valu ••• 

(II + CzBz. 1ha rat.e cauotent. for this caoplaproc ... b .. recent.ly bam rr~ed by G. P. Smith 

_t al. (1984) iD the t...-paratun r .... fn. 228 t.o 140011:, aDd in the pressure rena. 1 t.o 760 t.on. 

n.ir malyab, 1IbJ.ch ia c .. t. 1n .biler t.erms t.o tho.e .... ed here, i. the sourc. of the rate conat.anta 

aad t..aperatun dapendcc... at. hotIa U .. .t.t... Th. nesat1v. value of III reflect. the fact that. thdr 

analysis include. a 1.i'kc~~1. burier for the eddlt1ea of (II t.o C2.Bz • 

Th_ clat.a analJ:&ed iDclucl. tho .. of P .. t.r ..... IIDd Carr (1974), P.rry~. (11177), Micba.l _t al • 

. - (1980), IIDd Parry· lind Willi_ca (19&1). Other clat.a of Wilson and.~W .. tanbar, (1967), B~!eD md 

Glu. (1971), s.dth mel Zellner (1173), mel Devis~. (1975) wan not.·1ncluded. _ .. --

Ca1culat.iona of ko via the _thoda of Patrick. and Golden (1983) yiald val .... COIIIpatible with those 

of Smith et d. 

27. CF3 + 02.. Caalaed ~ JPL 85-37. C:Ualp~. (19811) b..-.... ured the rat.e CClUt.ant. in I Z 

babtMD 1 aad 10 t.orr. lh1& .upp1.mt.. the valu. fr<a Carslp aDd Le.claux (11183). they raCCllllMlld 

differmt. par..e.era, bat. the clau ua _11 repre.ent.a.! by the currmUy A-.oded valli... Data 

of Rym aDd Plmb (11142.) an in ~t.. 

87 

~~-;.~ -. ---" - ...... -=---..--_.- -_. ~--.--.--. -- --.. -----,: ... ~ ~---.:.. :-;; •• -.~......-..;.;.;.._...:._..z.. 

.:-" ------

--

-:- ---" ~ ~~.~."'--.-. ~-/ .. 

........ -.. ... ~ ·1 . --.' , ..... ,. f, . ~~. 

.-. ...... ~ -

.... 0--;.--: ..... -:,...--. .--.. ::.~"...,. 

/~ 

·-\~7~~·· 

I 

~. r. ----~ 
) 

-) 

'l 

r. 

.. 

-~ 

... 

28. Cl'C~ + OZ' - Valla .. ~-boClI low- and 1:.1&b-pr ..... n 11a1t.a at. lQl JC an frca C:U.lp mel LHclAux 

(la1l). t.mpentun d~ .. an %'OIIIIr •• t.1aat. .. -blLM4-CIIl-a1a1l.az=..rucUllDS. 

211. CCl:, + O2 , Valu .. for bot.h lw- aDd hiab-F"aur. Uait.a are trt.lt7c ell n,_ (11184). Th." .... 

the ._ for.t. .. :ec~ hue aDd HpOrt., 

k~OO(II.) _ (5.1.t 0.11) Z lO-n, k;OO - 2.5 Z .. :;-12 with P - 0.25. 

w. f1D<l • ,oad ti t. to th.t: d.ta .. dna P - 0.11 to "leU 

k~OO(B.) _ 4 s 10-31, k.ap1D& k!C~ - 2.5 s 10-12. 

Th. nc-.ted val ... 0' k~00(J2) 18 2.5 t.1aa. the val ... in B •• 

T~:.t.w:. clapCldmce. an rou&h •• tlaat. •• bua4 ·_-.IIIUa: :.act1oaa.- A val ... 0' k;OO 

5 s 10-12 baa bam :aport.ad ~ Coope: JL£l. (11180). 

30. CfC~02 + BOZ' V.w .. to: both law- .. 4 hI&b-pn .. ure .UmU •• t. 300 X tum t. ... cla.m .ad Car.lp 

(19S4). Thet:- b-.th , ...... "2 toblch'1a ... .-d to ba equal. to 1f2 in euuv tor_tar chu.c:t..d.t.ic •• 

Tacop.nt.w:. dlpendmc •• are rou&h •• tlaat.a. b ... d on .imUar :lIct.1cmS. 

31. lIS + 110. Dat.a and anal.7aI. a:. t:c:a t.Iw :acmt. .aD: at Sladt .!S...!l. (19S4). lb. t.ampent .. n 

. d.pandmc. at k. b •• baan •• tlrlat.ad. 

32. Ifa + O2 , lb. low-p.: ... w:. l1a1t. and t..apa:at. .. n dapmdanc. u. t.aba. f:naI th. rae_t papar at 

SUva: .t &1. (19841». lha a::o: Ualt.a are brocmad aaDMIb.t.. Patack.ad Golder. (1I1S4.) have 

partoruwd c.lcul..t.i..... 1.Il the mamer at Pat.rick md Gol-ian (1983) wb.lch yhld Pioa - 0.3. 

lb. hiah-pna.w:. Uait.Ins :.t.. conat.ant 11 an ut.imat. by 5U .... : ~. (1984b).2 lb •• uo: Uait.. 

and t.emper.t.ur. d.pu.--.ClC. are •• timat.ed. 

33. lIaO + 02' II .. Ent.ry. Aler and Bowa:4 (1966) have "' ..... :od th. low-pr-saur. l1a1t at. roCID t_rat. .. n in .. ""ra1 bath ,..... ThaI: val... in H2 1a .... d in the :.c_dat.ico. lbey part:ormad • 

Tree calculat.ico •• par Patrick .n4 Goldm (11183) t.o obt.ain collialeD .Uil:ill>C)l' and temp.rat.w:. 

d.pendanc.. Th.... obt.ai1>ad • h1&h-pn.sw:. liait. :.t.. COl:-ltant. ~ ".. of • simple mod.l. Th. 

tllllpar.t.u:. d.p' oo .. c. is .st.imat.ad. 

34. llaO + CO2 , 11_ EDt.r-y. Ala: and lIowud (1986) h."," 1IM .... nd the uta coaat.ant. to: this 9rocess 

1n the -faU-o'f- r.,J.me. Thei: lowst. p: •• aur.a are .... :,. clos. t.o the low-pr ..... :. limit. Th. 

tacop.:.t.W:I d.peOOaac. 11 all .• st.1mat.a. A3u and Boward calcul.at.a t.bI hia,h-prusw:. :.t.. canst.ant 

trail • simple mod.l. Th. t.ampar.t.u:. dependanc. 1a IIll .at.iaat •• 

3!i. N..aJ + CO2 , II .. E::iui. -Ale-r mcfBowerd-(1987b1 hav. _lIurad the low-pnuun UlDit1:l& ;.t. cO"'!~t.. 

Thl t.emp.ratur. d.pan<tmc. i .... st.lIDat... Alar and Boward have c:&1e:aUtAd the hi&!l-p:assur. Hmit. 

uain! • atlDpL. mod.l.. Tba t.mpa:.tur. dapecd.nc. is an •• tiaat. •• 

88 

._- _ ... - -.--".;1""'--- __ -___ ~ 

-... 

, 

.. 

~ ._"..... 
) 

~ 

) 

EQUILIBRIUM CONSTANTS 

Format 

/' 

/// 

-------- .---- ... -

Some of the three-body reactions in Table 2 form products which are 

thermally unstable at atmospheric temperatures. In such cases the thermal 

decomposition reaction may compete with other loss processes, such as photo-

__ dissociation or radical attack. Table -3 lists the - equilibrium constant-s, 

K(T), for six reactions which may fall into this category. The table has 

three column entrl~s, the _first two being the parameters -A and B which can 

be used to express K(T): 

K(T)/cm3 molecule-l - A exp(B/T)-(200 < T < 300 K) 

The third - column entry in Table 3 is the calculated value of K at 298 K. 

The data sources for K(T) are described in the individual notes to 

Table 3. Yhen values of the heats of formation and entropies of all species 

are known at the temperature T. we note that: 

ASo AHo 

log[K(T)/cm3 molecule-I] - T - T + log T - 21.87 

2.303R 2. 30JRT 

where the superscript ·0" refers to a standard state of one atmosphere. 

In some cases K values were calculated from this equation, using thermochemical data. In other cases the K values were calculated directly from 

kinetic data-for the forward and reverse reactions. WhE!n available, JANAF 

values were used for the equilibrium constants. The following equations 

were then used to calculate the parameters A and B: 

B/oK - 2.303 [log K200] (300 x 200 ) 

K300 300 - 200 

- 1382 10g(K200/K300) 

log A - log K(T) - B/2.303 T 

89 

-,- 2--

'-..-, ... ----~ 

. 

-J 

iJr .--

i(+) 
) 

) 

,,''t"' '.I!I- . 

) 

~ - -. -. 

Table 3. Equilibrium Consc&ncs 

React.ion 3 -1 Alea _1.c .. 1. BU!/~ !Ceq(211B !C) !(211a !Cl a 

1102 + *'2 - 1102*'2 2.1 x 10-27 10,IIOOtl,OOO 1.Sxl0-11 

- --_. - -- -.- - , 110 + 1102 - '2°3 3.0 x 10-27 4,700tlOO 2.1xlci-2O-

* 1102 + *'3 - '2°5 1.1 x 10-27 11,200:t500 2.3x10-11 

C1 + 02 - C100 2.3 x 10-25 _.- 3,OOO±750 5.4x10-U . 

C10 + 02 - ClO'02 <2.11 :I< 10-26 <5, OOO:tl, 500 <5.6:10-19 

_.,.C10.+ ClO - C12

02 7.9 : 10-27 B,1500:t2,500 -- 2.7:10-14 

-_ ... _---

&.F+02 -FOO 5.3 : 10-25 7,600 15.3:10-14 

1.1 : 10-25 3,600 1.lIxl0-20 

CH30Z + NOZ - CH3OzNOZ 1. 3 : 10-2a 11,200%1,000 2.7x10-12 

3 -1 lCIem mol.c .. l. - A .:p(B/T) [200 < TIK < 300) 

a !(29a !C) i. th. unc.rt.aint.y at. 2SB!C. To calculat.. th. unc.rt.aint.y at. oth.~ 

t.emperat.ur •• , .... th •• xpr ••• ion: !(Tl - !(2SB !C) .xp(~ I 1 - -1- I ). T 29a 

* Indicat. •• a chana. trOD t.h. pr.vio ... Pan.1 .valuat.ion (JPL 85-37), 

&. Indicat. •• a chana. in th. not.. !rOD th. pr.viou •• valuat.ion. 

, Indicat. •• a n ... ~t.ry. t.hat. was not. in t.he previous eval ... t.ion. 

90 

5 

2 

2 

20 

500 

100 

10 

~ 

Mote 

1 

2 

3 

.. 

5 

6 

7. 

7b 

a 

-~ 
) 

) 

NOTES TO TABLE 3 

1. 1IJ2 + 1102 , the vallie ... cbtained b7 c.-in1n& th. data ot SaDdar aDd '.terSOll (1;8~) tor t.ha 

r.te cooat.mt. ot t.he nacUoo u wr1t.t.eD aDd t.bat. ot Gr~~. (1a77) tor tha unra. react.1on. 

From tha equiUbri_ CODatmt.. it. uy b. inf.rred that. th. themal d.c:o.pI<.loa of 1IJ~2 1& 

un1mponant. in th •• trato.phere. but. 1& iqIorta:lt. in th. t.ropoapb.re. 

2. _~! _1102 , ~._d~t.._~_~ JAM7. thh proe ... i. lDC~ bee ..... .-!ecct. ~aaur.!'MDt. of t.h~ __ 

rate CODat.aDt. b7 SIa1t.h aDd T~ (1;86) .~ t.bat. It. h t.oo .t- to be &II iaport.mt. rata proc •••• 

but. th.n will be .mae equiUbrl_ coacctr.t.ion pr .. ct.. 

3. 1102 + 1103 , Mot.. cbaaaed fro. JPL 65-37. ltecent. _ta cd • n-evalllet.loa of t.ba ant.roPJ of 

1103 leed to •• Uabt,ly--alt.ared valu •• lluir_-~; (1;85«:). tUina t.he1r data mot tbOs". ot GrAhM. 

aDd .JcbDat.on (1a71) .ad th. r_ t.eooperat.ure data of Pamer lLJl. (11115). h..,. putomed • -3rd 1_-

tit.Una th.t. y18lda the rec-..ded par_tara. the •• vala .. are _11 wlt.h1n th. raoa. ot _._t.s 

ot Eircber ll..!l. (1a84). 1u.azon .t d. (1913) and Saa1th.!L!l. (1815). 

-~.-Cl + "2' -Cox.!L!l. (1878) .uured I:.t. 2911:. Their reponed val ... of""I:.-(5:~":1:"2.6 x 10-21 CfA3--

lII01ecu.1.-1 • ..tlm cod>ined wlth .JAlIAF valu.s for th. ant.ropy cbma •• ,iv.s ABt (2a8HCI02 ) - 22.5 

kc.l/1II01-1• thla la in excellent. a&r ..... t. wlth Ashford n...u. (1a71). wbo s""est. ABf (298) (CW2 ) -

22.5:1: .5 kc.l/1II01-1• the .xpre.slon ot Cox~. h: 

-21 I: - 3.71 x 10 T exp(3217/T). 

-1 5. ClO + 02' ZeUner (prlvat. cCllllllUllic.t.1co. 1982) s,,"uta I: < 12.tIII UIdt.II ~ -11 kcal/lIIOl. Th. o -1 -1 correlpcod1na value ot A l .. da to S 300(CW'08

) -73 cal Il101 J:. A M&her :--la~ ot I: bas been 

proposed b7 rraaed (1910). but. it. requ.lr .. S (ClO'02 ) to b. about. 13 cal _1 1 I: 1 • ..tllcb "_ 

unreasonably-Mab. Cart.r- md-ADdr ... (1911) found DO axper1meDt.al evldmc."·tor CW'02 in utrlx 

exper~t.a. 

6. CW + CW. thi. equ1l1brbD const.ant. 1. not. _11 .. tabU.hed. the quot.ed value 1a based primarily 

on the _rk of Cox cd co __ rker. (Cox and DeJ:'lNllt.. la7a and B.,..aD et al •• 1;81). The corre.poodin& 

-1 -1 -1 ant.roPJ of the cI1Der 1& 71 c.l.,l I: md AB 1. -17.1 kcal _1 • 

7. F + 02' (a) Frca.JUAF t.he1:lllOChem1c.l v.w... (thl. valu. favored by ko calculation ••• e lIote 11, 

Tabl-. 2.'- (b) Frca Banson,. (1976) themoch-.1c.i vaw;'. - w&iUi.atmi -.t. .i. fa"lOr th. B~aoD value 

tor F02• based on th. iDd.pendmc.- of 1103 oa diluent. ,U U.e. 112 , 02) when m.kina 1103 b7 F + BlI03 • 

the ccoclua1on 1. that. F + 02 - F02 ls • f .. t. equ.il1briID; t.bey cooclude t.bat. th. Benson value 1& 

correct.. However. the value of the -low-pr .. sure rata conat.aDt. tavon the .JAlIAF vaw. ('atrlck and 

Golden. 1913). 

8. CB;s02 + 1102 , Thermochllllic.l values .t. 300 J: for CB30z!'02 and CB;s02 are trom Baldwin (1912). 

In the ab.ence ot data. ufl IIId !>SO war ... .....s to be 1ndependeat. of t.-peratun. Baht.a!!...!.l.. 

(1982) have ......nd k(dlssocl.Uoo) at. 2153 1:. lIa1n& t.he valu .. of k(raccdliDat1oa) au.&& .. ted in 

t.h1s evaluaUon. t.baoy c:oeputa 1:(253) - (2.58:1: 0.26) x 10-10 .. 3. Our values predict. 3.94 x 10-10 

ca3 • in ,oad aare_t.. 

91 

~ 

~.J-

~ 
,-!' 

) 

) 

) 

PHOTOCHEKICAL DATA 

Discussion of Fowt and Euor Estiutes 

In Table 4 we present a list of photochUllcal reactions considered to 

be of stratospheric int:erest. The absorption cross sections of 02 and 03 

largely determine the extent of penetration of solar radiation into the 

stra:tosPhere and-troposphere. SOM cOlIIHnts and refex:ences _ ~o_ these cross 

sections are presented in the text, but only a sample of the data are listed 

here. - (See,for example, WO Report Ill, _1982; ~-NASA, 1985.) The photodissociation of NO in the 02 SchUIIAnn-Runge band spectral range is another 

-- -important process - requiring special treatment and is not discussed in 

this evaluation (see. for example, FrederiCK arid -Hudson-; --1979; Allen and 

Frederick, 1982; and WO Report #11, 1982). 

For sowe other spedes having highly structured spectra, such as CS2 

and S02' some comments are given in the text, but the photochemical data 

are not presented. The species CH20, N02' N03 and OC10 also have comp1icated spectra, but in view of their importance for atmospheric chemistry a __ 

sample of the data is presented in the evaluation; for more detailed information on their- bigh- resolution spectra and temperature dependence, the reader 

is referred to the original literature. 

Table 5 gives recoCllllended reliability factors -for some -of~he more 

impo rtant pho tochelllical _ reac cions . These factors represent the combined 

uncertainty in cross sections and quantum yields, taking into consideration 

the acospherically illportant wavelength regions. and they refer to the 

total dissociation rat~ regardless of product identity (except in the case 

of O(lD) production froll photolysis of 03)' 

92 

~ 

.. " 

-----A} - .. 
) 

) 

.- .- -- -... -- --

Table 4. Photochemical Reaction. of Stratospheric Interest 

& 02 + hal ~ ° + ° 

* 03 + hal ~ 02 + 0 

03 + hal ~ 02 + 0(1D) 

* H02 + hv ~ products 

.. H20 +-lui-~ Hi-Ole -- -. (1) 

H202 + lui ~ OH + OH 

NO+haI~N+O 

*N02+hv~NO+0 

* N03 + hv ~ products 

_~2<:> + hv_ ~. N2 + O(l~) 

N205 + lui ~-products 

NH3 + hv ~ NH2 + H 

HN02 + lui .. OH + NO 

HN03 + lui .. OH + N02 

HN04 + lui .. products 

C12 + hv ~ C1 + C1 

C10 + hv ~ Cl + 0 

ClOD + lui .. products 

* OC10 + lui .. ° + C10 

C103 + lui .. products 

H C1202 + hv .. products 

HCl + hv .. H + Cl 

--.-- ----- HOC1 "-OH-+ C1 

* ClNO + lui .. C1 + NO 

C1N02 + hv .. products 

C10NO + hv .. products 

C10N02 + lui .. products 

(1) Hudson and Kieffer (1975) 

(2) Turco (1975) 

/J New entry 

(1) 

CC14 + hv ~ products 

CC13F + hv .. products 

CC12F2 + hv ~ products 

CHC1F2 + hv ~~rod~~s --' 

CH3C1 + hv .. products 

CC120 + hv .. products 

CC1FO +_~ - products 

CF20 + hv ~ products 

CH3CC13 + hv ~ products 

I CBrC1F2 + hv~ products 

I CBrFfi; hal -.. product:sBrO + hv .. Br + 0 

BrON02 + hv .. produc ts 

HF+hv"H+F 

CO + hv .. C + 0 

C02 + hv .. CO + 0 

CH4 + hv .. products 

CH20 ~ products 

CH30DH + hv ~ products 

HCN + hv .. products 

CH3CN + hv.- products 

S02 + hv .. SO + 0 

oCS-+ -hi,; .. CO + S 

H2S + hv .. HS + H 

CS2 + hv .. productsI HaCl + hv .. Ha + Cl 

HaOH + hv .. Ha + OH 

* Indicates a change in the recommendation from the previous evaluation. 

& Indicates a change in the note. 

93 

(1) 

(1) 

(2) 

(2) 

.---~ 

r'_~ 

i(;J 
.,. ..:':!."~ - - ---

) 

, 

) 

Table 5. Combined Uncertainties for Cross Sections and 

Quantwl Yields 

Species Uncertainty 

02 (Schumann-Runge bands) 

. - 02' (Continua)- -- _.- -

°3 

03--+ O(ID) 

N02 

N03 -

H20 

N20S 

H202 

HN03 

H02H02 

CH20 

HC1 

HOC1 

C10N02 

CC14 

CC13F 

CC12F2 

CHlCl 

CF20 

CHlOOH 

BrON02 

94 

1.4 

l.l 

1.1 

1.4 

1.l 

2.0 

1-:2 

2.0 

1.4 

1.3 

2.0 

1.4 

1.1 

1.4 

1.3 

1.1 

1.1 

1.1 

1.1 

2.0 

1.4 

1.4 

---- -- ~ 

~ 
) 

) 

. --- .... _--- --.. ------.-----------~----

The absorption cross sections are defined by the following expression 

of Beer's Law: 

I - Ioexp(-cml), 

where 10 an.! I are the incident and transmitted light intensity, respectively; 

a is the absorption cross section in cm2 molecule-I; n is the concentration .-

in molecule ClI-3 , and 1 is the pathlength in cm. The cross sections are 

room ~erature values at the specific wavelengths listed in the tables, 

and the expected photodissociation quantum yields are unity, unless otherwise 

stated. 

02 + hv -+ 0 + ° 

The phoUXtlssociation of molecular oxygen in the stratosphere is due 

primarily to absorption of solar radiation in the 200-220 nm wavelength 

region, i. e., within the Herzberg continuum. The 185 - 200 om region- - the 

02 Schumann-Runge band spectral range--is also very important, since solar 

radiation penetrates efficiently into the stratosphere at those wavelengths. 

Frederick and Mentall (1982) and Herman and Mentall (1982) have estimated 

02 absorption cross sections from balloon measurements of solar irradiance 

in the stratosphere. The latter authors find the cross sections in the 

290-210 nm range to be -35% smaller than the smallest of the older laboratory 

results, which are those of Shardanand and Prasad Rao (1977). There arethree recent laboratory studies (Johnston ~., 1984; Chueng ~., 

1984; Jenouvrier ~., 1986) which confirm the lower values obtained from 

solar irradiance measurements. There is also, however, a study of the 

penetration of stellar UV radiation into the stratosphere which agrees 

better with the higher 02 crOSF- section 1T".lue.3 (Pirre ~., 1984). 

95 

~ ~ 

1-

'.--

(i; 
) 

/ 

J 

·rd~­

".~ 

/. 

., 

:.." 

t 

~ 

~. 

ro ' 

k:. 

) 

.-

.. "_" . __ ." -_. \:I:

The attenuation of solar radiation in the Schuaann-Runge wavelengeh 

region is a problem requiring special treatllent due to the rotational 

structure of the bands; see, for eUllple, Nicolet and Peetenaans (1980); 

Frederick and Hudson (1980); and Allen and Frederick (1982). The effective 

02 cross sections obtained from solar irradiance aeasure.nts in the 

stratosphere -by'-Henian -and Kentall--(1982) ---are in good agreement between 187 

and 195 tua with the values reported by Allen and Frederick (1982), which 

-were-obtained by an empirical fit to the effective-cross sec"tions appropriace 

for stratospheric conditions. Between 195 and 200 lUll the fit yielded values 

which-are" somewhat-- larger than those estimated by Herman and Kentall-: 

. The studies of the penet~ation of solar radiation in the atmosphere in 

the Schumann-Runge wavelength region have been based so far on laboratory 

measurements of cross sections which were affected by instrumental parameters 

due to insufficient spectral resolution. Yoshino et al. (1983) have reported 

high resolution 02 cross section measurements at 300 K, between 179 and 

202 nm, obtaining presumably the first set of results which is independent 

of the instrumental width. The Schumann-Runge cross sections are temperature-dependent, so that additional studies will be required-_in" order to 

carry out detailed atmospheric modeling calculations. Furthermore, for 

. estimates of the solar irradiance in the stratosphere the cross section 

values- which need to be accurately known are those at the wings of the -

rotational lines and in the underlying continuum, and these are several 

orders of magnitude smaller than the peak values. 

03 + hv .... ° + 02 

The 03 absorption cross sections and their temperature dependence have 

been remeasured recently by several groups. For a review see WHO-NASA, 

96 
) 

) 

-------------------

1985; -Table 6 lists a sample of the data taken froll this review, namely 

the 273 K cross section values averaged over the wavelength intervals 

cOmllonly employed in IIOdeling calculations, except for the wavelength range 

185 to 225 nil, where the present recommendation incorporates the averaged 

values froll the recent work of Kolina and Kolina (1986); the older values 

were based on _the_work of Inn and Tanaka -(1953).. -- The-temperature effect is 

negligible for wavelengths shorter than -260 tuI. Recent work by Kauersberger 

~. (198~, 1~8!) y!~Jds a value ~f 1137 x 10-20 cm2 for the cross section 

at 253.7 tuI, the mercury line wavelength; it is about 1% smaller than the 

commonly accept~~_val~e _o_f_ 1~4? x 1~-20 cm2 rel!0rte_d by Hearn (1961) t and 

about 2% smaller than the value obtaine-d-by Kolina and Kolina- (1986) ,1157-

x 10-20 cm2 . The reason for the small discrepancy, which appears to be 

beyond experimental precision, is unclear. 

The quantum yields for 0(1D) production, ~(OlD), for wavelengths 

near 310 nm--Le., the energetic threshold or fall-off region--have been 

measured mostly relative to quantum yields for wavelengths shorter than 

300 nm, which were assumed to be unity. There are several studies which 

indicate that this assumption is not correct: Fairchild~. (1978) 

observed approximately 10% of the primary photolysis products in the 

ground- -state cha~el~;t is, ~(03'p) - "'0.1, .- - ---- at 274 nm; Sparks et a1. 

(1980) also report ~(03p) -0.1, at 266 nm; according to Brock and Watson 

(1980b) ~(OlD) - 0.88 at 266 nm; Amimoto~. (1980) report ~(OlD) - 0.85 

at 248 nil, and Wine and Ravishankara (1982) measured directly ~(OlD) - 0.9 

at 248 nm. There are also some indications that ~(OlD) decreases slightly 

between 304 and 275 nm (see Brock and Watson, 1980a,b). 

97 

~. 

-'~ 

~ .-- jr:; 
• J1' ....:.-. 

) Table 6. Absorption Cross Sections of 03 at 273 K 

). 102Oa(cm2) ). 102Oa(cm2) 

(nm) average (nm) average 

175.439-176.991 81.1 238.095-240.964 797 

176.991-178.571 79.9 240.964-243.902 900 

178.571-180.180 78.6 - .. .. . 243.902 . .,,246.-9.14 1000 

180.180-181.818 76.3 246.914-250.000 1080 

181. 818-183 .486 72.9 250.000-253.165 1130 

183.486:..185.185 68.8 253.165-256.410 - -ll50 

185.185-186.916 62.2 256.410-259.740 ll20 

186.916-188.679 57.6 259.740-265.158 1060 

188.679-190.476 ---52.6 - 263.158·- 266 ~ 667 965 . ~---- -

190:476-192.308 47.6 266.667-270.270 834 

192.308-194.175 42.8 270.270-273.973 092 

194.175-196.078 38.3 273.973-277.778 542 

196.078-198.020 34.7 277.778-281.690 402 

198.020-200.000 32.3 281. 690-285.714 277 

200.000-202.020 31.4 285.714-289.855 179 

202.020-204.082 32.6 289.855-294.118 109 

204.082-206.186 36.4 294.ll8-298.507 62.4 

206.186-208.333 43.4 298.507-303.030 34.3 

208.333-210.526 54.2 303.030-307.692 18.5 

210.526-212.766 69.9 307.692-312.5 9.80 

212.766-215.054 92.1 312.5-317.5 .5.01 

-_._- ----- - 215.054-217.391 119 ·317 .5-322.5 2.49 

217.391-219.780 155 322.5-327.5 1.20 

219.780-222.222 199 327.5-331.5 0.617 

222.222-224.719 256 332.5-337.5 0.274 

224.719-227.273 323 337.5-342.5 .0.117 

227.273-229.885 400 342.5-347.5 0.0588 

229.885-232.558 483 347.5-352.5 0.0266 

232.558-235.294 579 352.5-357.5 0.0109 

235.294-238.095 686 357.5-362.5 0.00549 

98 

) 

-

\.t 

-- - .- ---

I_~ 

li 
fr_ ..... ~- . -'. 

r---

• j 

) 

) :. 

, 

. ---- --.-- - --------.----

The recommendation for the quantum yields in the fall-off region is 

given in Table 7, and is taken from the mathematical expression given by 

Moortgat and KudZus (1978), scaled down by a factor of 0.9 to account for 

the absolute magnitude of ~(OlD) at short wavelengths. The relative values 

are in good agreement with those reported by Brock and Yatson (1980a). 

Table 7. Mathematical Expression for O(lD) Quantum Yields, ~, 

in the Photolysis of 03 

~(~,T) - A(r) arctan[B(r)(~-~o(r»] + C(r) 

where r - T - 230 is-a--temperature-function, with T given in Kelvin; 

-~ is the wavelength in nm, and arctan is expressed in radians. 

The coefficients A(r), B(r), ~o(r) and C(r) are expressed as 

interpolation polynomials of the third order: 

A(r) - 0.332 + 2.S6SxlO-4r + 1.1S2xlO- Sr 2 + 2.313xlO- 8r 3 

B(r) - -0.575 + S.59x10- 3r -1.439x10-Sr 2 - 3.27x10-8r 3 

~o(r) - 308.20 + 4.4871xlO- 2r + 6.9380xlO-Sr 2 - 2-34S2x~0-6r3 

C(r) - 0.466 + 8.883x10-4r - 3.S46xlO-Sr 2 + 3.S19xlO- 7r 3 • 

In the limit where ~(~,T) > 0.9, the quantum yield is set ~ - 0.9. and 

similarly for ~(~.T) < 0, the quantum yield is set ~ - O. 

H02 + hv .... OH + 0 

The absorption cross sections of the hydroperoxy1 radical. H02, in the 

200-2S0 lUll region have been measured at room temperature by Paukert and 

Johnston (1972), Hochanade1 ~. (1972; 1980), Cox and Burrows (1979). 

McAdam~. (1987), and Kury1o~. (1987a); and by Sander~. (1982) 

at 227. S IlII. 

99 

'\.,k, 

:-

~ 
) 

J 

-J1.. ... ~"4_ • 04. 

-_ ... -- -

There are significant discrepancies in. the shape of the spectrum as 

well as in the absolute cross section values; at 227.5 nm, the value ranges 

from 250 to 309 x 10-20 cm2/molecu1e, the average of all measurements 

being 269 x 10-20 cm2/mo1ecu1e. 

Table 8 lists the recommended cross sections, which are computed from 

the mean of the· five sets of reportedva1ues~ -This recommendation-is given 

here merely to indicate that photolysis of H02 in the stratosphere and 

_ . t:ro2.0sphe~e is not an important process and can be neglected.. However, forchemical kinetics studies the simple average presented here need not be the 

best choice and the most suita1,lle cros.s_section values to be used should be 

constdered on a case-by-case basis. 

Lee (1982) has detected O(lD) as a primary photodissociation product 

at 193 and at 248 nm, with a quantum yield which is about 15 times larger 

at the longer wavelength. The abso1~te quantum yield for O(lD) production 

has not been reported yet. 

Table 8. Absorption Cross Sections of H02 

A(nm) 1020u(cm2) 

----... ---- 200 430 

210 430 

220 360 

230 240 

240 120 

250 50 

100 

--. 

._-----_._. ------

~ 

(-~ 

~ 

I':~IP ,~~ . ~-

) 

~ 

J. 

• 

iI 

-- .. - - --_. - - - ---_._._---------- --"-- - --- ._- - - - -

N02 + hv ... NO + 0 

Table 10 lists a sample of the the recommended absorption cross sections of nitrogen dioxide, taken from the work of Bass et a1. (1976). who 

report extinction coefficients every 1/8 nm between 185 and 410 nm at 298 

K, and between 290 and 400 nm at 235 K. For atmospheric photodissociation 

calculations which require cross section values averaged over appropriate 

wavelength intervals the original literature report should be consulted; 

Table lO--Usts the values only at the indicated wavelerigths. 

Recent cross section measurements by Schneider ~. (1987) give 

results which are 2·3% smaller than those of Bass et a1. around 375-395 nm, 

which is the most important wavelength regioa for atmospheric photodissociation, but which are larger by as much as 20-25% around 270 nm and around 

200 nm where the experimental measurements are more difficult. Furthermore, 

measurements by Calvert et al. (private communication) indicate that the 

temperature effect on the cross sections is significantly smaller than 

reported by Bass et al. (1978). The discrepancies are probably due to 

inaccuracies in the correction required to account fer the presence of 

N204 in the absorption cells. 

Harker et a1. (1977) have rc.~orted me~surements of a~sc:'rpt~c:m cross 

sections and quantum yields in the 375-420 nm region. Their cross sections 

are 4-10% larger than the values reported by-Bass et a1. (1976), and their 

quantum yields are, on the average, about 15% smaller than those measured 

by Jones and Bayes (1973). The measurements of the quantum yields by Davenport (1978) at six different wavelengths agree w:!11 with those of Harker 

et a1., and they indicate that the quantum yields themselves are temperature 

dependent. Direct measurements of the solar photodissociation rate of N02 

in the troposphere by Parrish et a1. (1983) agree better witb theoretical 

102 

:l~ ~ 

r 

~ 
- .. _ .. _.- .. 

) 

. -- -.. -

. 

)~ 

-------

Table 10. N02 Absorption Cross Sections at 235 and 298 K 

l 102Oa(cm2) l 102Oa(cm2) 

(nUl) 235 K 298 K (nm) 235 K 298 K 

185 26.0 300 10.9 11.7 

190 - -- 2~.3 -- 305 16.7 16.6 

195 24.2 310 18.3 17.6 

200 25.0 315 21.9 22.5 

205- 37.5 320 23.5 25.4 

210 38.5 325 25.4 27.9 

215 40.2 330 29.1 29.9 

220 39.6 335 31.4 34.5 - --- _. ------- 225 32.4 340 32.3 38.8 

230 24.3 345 34.3 40.7 

235 14.8 350 31.1 41.0 

240 6.70 355 43.7 51. 3 

245 4.35 360 39.0 45.1 

250 2.83 365 53.7 57.8 

255 1.45 370 48.7 54.2 

260 1.90 375 50.0 53.5 

265 2.05 380 59.3 59.9 

270 3.13 385 57.9 59.4 

275 4.02 390 54.9 60.0 

280 5.54 395 56.2 58.9 - -

285 6.99 400- - 66-.6 67.6 

290 6.77 8.18 405 59.6 63.2 

295 8.52 9.67 410 53.2 57.7 

103 

~ 

-- --

., 

. 

. 

~ 
I! .·tt·\ "''T.'~'-'~' 

-.~ -

) 

,. ,. 

)-; 

.; 

i 

.. _._---_ .. _---------- ._-_.-.-- -.-:.~ 

calculations that incorporate the quantum yield values of Jones and Bayes 

(1973) rather than those of Harker~. (1977). 

The previous recoDlJllendation for quantUII yields was based on the work 

of Harker §.L.Al. (1971) and of Davenport (1978) for the atmospherie&llyimportant 375-470 nm region. Recent work by Gardner ~. (1987) yields 

values which are in much better agreement with the values reported-earlier 

by Jone.s and Sayes (1973). The recommended quantum yield values, listed in 

Table 11. are in agreement with the- recoaDendation of Gardner ~. - (1987); 

they are based on a smooth fit to the data of Gardner~. (1987) for the 

wavelength range-.%rC?In _ 3~to_ 4~~ nm; Harker~. (1971) for 397-420 IlD 

(corrected for cross sections); Davenport (1978) for 400-420 nm; and Jones 

and Sayes (1973) for 297-412 nm. 

N03 + hv ~ NO + 02 (~1) 

~ N02 + ° (~2) 

The absorption cross sections of the nitrate·- free radical, N03'· havebeen studied by (1) Johnston and Graham (1974); (2) Graham and Johnston 

(1978); (3) Mitchell ~. (1980); (4) Marinel.'.i~. (1982); (S) RavLshankara and Yine (1983); (6) Burrows ~. (198Sb); (7) Ravishankara and 

Mauldin (1986); (8) Sander (1986); and (9) Cantrell et al __ (1987). The 1st. 

and 4th studies required calculation of the N03 concentration by modeling 

a complex kinetic system. The other studies are more direct and the resulcs 

in terms of integrated absorption coefficients are in good agreement. The 

recommended values at 298 K are the averages of the results of Ravishankara 

and Yine (1983) and Sander (1986). Table 12 lists a sample of these values; 

the original literature should be consulted for a more extended wavelength 

range, and for values at other temperatures. The effects of secondary 

104 

,. 

:-

~ 
., ....... ~-., 

. '\ ,- •. -p .. ----_.-. __ ._-----------

) 

.' 'l+ -.- ---------- ~ 

Table 11. Quantum Yields for N02 Photolysis 

l,nm ~ l,nm ~ 

< 285 1.00 393 0.953 

290 0.999 394 0.950 

295 0.998 395 0.942 .. --- -- -- --.. - 300 0.997 396 0.-922 

305 0.996 397 0.870 

310 0.995 398 0.820 

315 0.994 399 0.760 

320 0.993 400 0.695 

325 0.992 401 0.635 

330 -0.991 402 . - 0.560 -.-

335 0.990 403 0.485 

340 0.989 404 0.425 

345 0.988 405 0.350 

350 0.987 406 0.290 

355 0.986 407 0.225 

360 0.984 408 0.185 

365 0.983 409 0.153 

370 0.981 410 0.130 

375 0.979 411 0.110 

380 0.975 412 0.094 

381 0.974 413 0.083 

382 0·.973· 414 0.070: 

383 0.972 415 0.059 

384 0.971 416 ·0.048-· 

385 0.969 417 0.039 

386 0.967 418 0.030 

387 0.966 419 0.023 

388 0.964 420 0.018 

389 0.962 421 0.012 

390 0.960 422 0.008 

391 0.959 423 0.004 

392 0.957 424 0.000 

) 105 

(-~ 

/G:' 
" .r-'- W

. ' . :., 

J 

". - - - - --

! 

)f 

c. 

... 

1 

- --

- ------- -- _.- - - .. - - .-- -. - -. - -.- -- -- .. _ .. --------_. ---- - _. _.-- It 

Table 12. Absorption Cross Sections of N03 at 298 K 

~ 10200 ~ 1020(7 ~ 1020(7 

(nm) (cm2) (nm) (cm2) (nm) (cm2) 

600 261 625 804 648 61 

-- -- --- - 601 266 626 - -710- - 649 - 52 

602 305 627 722 650 50 

603 354 628 709 651 53 

604 - - - 417- --629 679" - 652 56 

605 419 630 644 653 62 

606 325 631 475 654 77 

607 227 632 ~~8 655 94 

608 172 633 196 656 133 

609 155 634 144 657 17lf 

610 194 635 129 658 221. 

611 173 636 161 659 360 

612 204 637 193 660 665 

613 244 638 195 661 1320 

614 245 639 164 662 2020-

615 212 640 122 663 1760 

616 192 641 100 664 1120 

617 191 642 92 665 760 

618 210 643 94 666 468 

- 619 -- 231 644 93 667--- 25.7 

-620 295 645 86 668 165 

621 455 646 73 669 114 .. ----

622 950 647 70 670 85 

623 1420 

624 1150 

106 

~ 
) 

) 

~~~~-~. 

chemistry were minimized in these two studies by working with short time 

scales and direct titration of the radicals, but some unexplained discrepancy 

of up to 20% remains. The recommended peak cross section value around 662 

nm is 2.1 x 10.17 cm2 at 298 K, and 2.7 x 10-17 at 220 K, as computed 

from the average of the studies by Ravishankara and Mauldin (1986) and 

Sander (1986); within experimental error, the variation is linear with 

temperature. Note, however, that Cantrell~. (1987) find no measurable 

temperature effect on-- the peaK- -cross --section; the reason is not clear. 

The quantum yields ~l and ~2 have been measured by Graham and Johnston 

- (1978), -and under higher resolution by _M~gn~tt~ _a~d_ Johnston (~980), who 

report the product of the cross section times the quantum yield in the 400 

to 630 nm range. The total quantum yield value ~l + ~2 computed from 

the results of this latter study and the cross sections of Graham and Johnston 

(1978) are above unity for ~ <610 nm, which is, of course, impossible; 

hence, there is some systematic error and it is most likely in the primary 

quantum yield measurements. Magnotta and Johnston (1980) and Marinelli 

et a1. (1982) have discussed the probable sources of this error, but the 

question remains to be resolved and further studies are in order. At 

present, the reco!JUller.dation _rema~ns_ u~changed, namely, to use the following_ 

photodissociation rates estimated by Magnotta and Johnston (1980) for averhead sun at the earth's surface: 

Jl(NO + 02) - 0.022 s-l 

J2(N02 + 0) - 0.18 sol. 

107 

~~ 

l 

1 

t~ ~ 
, 

J!·d~~ - . " 

~-

) 

--- 1-

;--

r 

): 

.>~ 

--, -----

N20 + hv ~ N2 + O(lD) 

The recommended values are taken from the work of Se1wyn~. (1977), 

who measured the temperature dependence of the absorption cross sections in 

the atmospherically relevant wavelength region. They have fitted their 

data with the expression shown in Table 13; Tab1e_14_ presents_ the roo.m 

temperature data. Hubrich and Stub1 (1980) remeasured the N20 cross sections 

at 298 K and 208 K, and their results are in very good agreement with those 

of Selwyn ~. 

Table 13. Mathematical Expression for Absorption Cross 

Sections of N20 as a Function of Temperature 

In a(~.T) - Al + A2~ + A3~2 + A4~3 + A5~4 

+ (T-300)exp(Bl + B2~ + B3~2 + B4~3) 

where T: temperature, Kelvin; 

Al - 68.21023 

A2 - -4.071805 

A3 - 4.301146 x 10-2 

A4 - -1.777846 x 10-4 

AS - 2.520672 x 10- 7 

~ nm 

B1 - 123.4014 

B2 - -2.116255 

B3 - 1.111572 x 10- 2 

B3 -1.881058 x-1O- 5 

Range: 173 to 240 nm; 194 to 320 K 

108 

.:~ 

~-

~ 
J!'~ --- --_.-.,. - -.- .~ - .,- • . ,,". .!'.. .' 

. 

. -----~(£ .... 

~ .- -. ------.-----_ .. - .---.-----. -- --------.--.-. -- ---- - ----.-

j ) 

Table 14. Absorption Cross Sections of N20 at 298 K 

l 1020(7 ~ 1020(7 ~ 102~(7 (nm) (cm2) (nm) (cm2) (nm) (cm ) 

173 11.3 196 6.82 219 0.115 . . ~ - _. - --' - -- _ .. - .- -. -- .- -. ". 

174 11.9 197 6.10 220 0.0922 

175 12.6 198 5.35 221 0.0739 

176 .. 13.4 19_9 _ _.4.70 222 0.0588 

177 14.0 200 4.09 223 0.0474 

178 13.9 201 3.58 224 0.0375 

----". ".- - 179 - -14.4 202 3.09 225·- 0.0303 -- - --- - "--- ".-. -- - 22-6 -_. -0.0239 ----. , 180 14.6 203 2.67 1 

" 181 14.6 204 2.30 227 0.0190 

182 14.7 205 1.95 228 0.0151 

183 14.6 206 1.65 229 0.0120 

184 14.4 207 1.38 230 0.00955 

185 14.3 208 1.16 231 0.00760 

186 13.6 209 0.980 232 0.00605 

187 13.1 210 0.755 233 0.00478 

188 12.5 211 0.619 234 0.00360 

189 11.7 212 0.518 235 0.00301 

190 11.1 213 0.421 236 0.00240 

191 10.4 214 0.342 237 0.00191 -_ .. ----- - - - - .- - -- - 192 9.75 215 0.276 238 0.00152-

193 8.95 216 0.223 239 0.00123 

194 8.11 217 0.179 240 0.00101 

195 7.57 218 0.142 

) 109 

\ 
) 

)--

:w:~~ ,..--------.-... J'.~.: .. ---~---------... _" ~ - --- - ---.-- -----

N20S + hv ~ products 

The absorption cross sections of dinitrogen pentoxide, N20S' have 

been measured at room temperature by Jones and Yulf (1937) between 285 and 

380 nm, by Johnston and Graham (1974) between 210 and 290 nm, by Graham 

(1975) between 205 and 380 nm; and for temperatures in the 223 to 300 K 

range by Yao et al. (1982), between 200 and 380 nm.The agreement is good, 

particularly considering the difficulties in handling N20S. The recolIImended cross section values, listed in Table 15, are taken from Yao ~. 

(1982); for wavelengths shorter than 280 nm there is little or no temperature_dependence._and between-28S and 380 the temperature effect- is best -

computed with the expression listed at the bottom of Table 15. 

There are now several studies on the primary photolysis products of 

N20S: Swanson et a1. (1984) have measured the quantum yield for !;03 

production at 249 and at 350 nm obtaining a value close to unity, a result 

consistent with the observations of. Burrows et a1. -(l984b) for photolysis at 

254 nm. Barker et al. (1985) report a quantum yield for O(3P) production 

at 290 nm of less than 0.1, and near unity for N03. For O-atom production 

Margitan (private communication, 1985) measures a quantum yield value of 

--------0--.35 at 266 nm, and Ravishankara et a1. (1986)-reportvalues of 0.72,0.38, 

0.21 and 0.15 at 248, 266, 287 and 289 nm, respectively, with a quantum yield 

near unity for N03 production at all these wavelengths. It appears, then, 

that N03 is produced with unit quantum yield while the O-atom and hence the 

NO yield increases at shorter wavelengths with a consequent decrease in ~~e 

N02 yield. 

110 

----~, 

f 

C 

r 
) 

-------

) 

,.,--~-,..,....~~--""''''-- .-.... -~.-.- .-. -... - ~~j.~r--·' .. ~- ~\.. ---... ~---.----.-- 

Table 15. Absorption Cross Sections of N205 

l(run) 102Oa(cm2) l(run) 1020a (cm2) 

200 920 245 52 

205 820 250 40 

210 _ SEiO __ _ __ 255 32 

215 370 260 26 

220 220 265 20 

225 - 144 270-- - - ·16.1 

230 99 275 13.0 

235 77 280 11.7 

-240 ·62 .. '-- -- - -.--

For 285 run < 1 < 380 run; 300 K > T > 225 K: 

10200 - exp[2.735 + «4728.5 - 17.127 l)/T)] 

where a is in cm2/mo1ecule; 1 in run; and T in Kelvin. 

HONO + hv ~ HO+ NO 

-- .- -- .. 

_. -- .---

The ultraviolet spectrum of HONO between 300 and 400 run has been 

studied by Stockwell and Calvert (1978) by examination of its equilibrium 

mixtures with NO, N02' H20, N203 and N204 ; the possible interferences by 

_~h~~~_~~~ou~ds w~re taken into_acco~t •. The reco~ended cross sections, 

taken from this work, are listed in Table 16. 

HN03 + hv ~ OH + N02 

The recommended absorption cross sections, listed in Table 17, are 

taken from the work of Molina and Molina (1981). These data are in good 

agreement throughout the 190-330 run range with the values reported by Biaume 

(1973). They are also in very good agreement with the data of Johnston and 

III 

-
~'fF:n. -y; .. $ ....... -" -- •• ,".' , , • , "'.~ •• tlt .~ ._ _ ______________ ._ ::"1" 

) 

Table 16. HONO Absorption Cross Sections 

~ 1020(7 .l. 1020(7 ~ 1020(7 

(nm) (cm2) (m) (cm2) (um) (cm2) 

310 0.0 339 16.3 368 45.0 

311 0.0 340 10.5 369_ 29.3_ -- --- -- -- . - . -- -- -- -- -- - 312 0.2 341 8.70 370 11.9 

313 0.42 342 33.5 371 9.46 

314 0.46 343 20.1 __ 372 8.85 

315 0.42 344 10.2 373 7.44 

316 0.3 345 8.54 374 4.77 

317- 0.46 - 346- 8.32 375 2~7 

- 318- 3-~-6 ---- 347 8.20 376 1.9 

319 6.10 348 7.49 377 1.5 

320 2.1 349 7.13 378 1.9 

321 4.27 350 6.83 379 5.8 

322 4.01 351 17.4 380 7.78 

323 3.93 352 11.4 381 11.4 

324 4.01 353 37.1 382 14.0 

-- 325 4.04 354 49.6 383 17.2 

326 3.13 355 24.6 384 19.9 

327 4.12 356 11.9 385 19.0 

328 7.55 357 9.35 386 -- . 11.9 

329 6.64 358 7.78 387 5.65 - .. . - -- -. -- -- -_._------ 330 7.29 359 7.29 388 3.2 

331 8.70 360 6.83 389 1.9 

332 13.8 361 6.90 390 1.2 

333 5.91 362 7.32 391 0.5 

334 5.91 363 9.00 392 0.0 

335 6.45 364 12.1 393 0.0 

;. 336 5.91 365 13.3 394 0.0 

337 4.58 366 21.3 395 0.0 

338 19.1 367 35.2 395 0.0 

~ 

-:..,.,-

.~ .. 112 ) "..~r 

~~-

i;.. 

, 
UAF\ _. _" __ \ -(£ .w.. <* •. - : + ,ot~· 

~~., . - - - -_ .. -- -.-------- -_. - - ------------------.. -.---- -. --- - -' 

) 

Graham (1973) except towards both ends of the wavelength range. Okabe 

(1980) bas measured the cross sections in the 110-190 nm range; his results 

are 20-30% lower than those of Biaume and of Johnston and Graham around 

185-190 nm. 

Johnston~. (1974) measur,~d_ a_~q~!l~yie1d value of -Lfor the - -- --' - - ... - -" - _. 

OH + N02 channel in the 200-315 nm range, using end product analysis. The 

quantum yield for. O-atom production at 266 nm has been measured to be 0.03, .. ." - - -- - .-

and that for H-atom production less than 0.002, by Kargitan and Yatson (1982), 

who looked directly for these products using atomic resonance fluorescence. 

Jolly et a1. (1986) measured a quantum yield forOH production of 0.S9 ""£" 0-. OS --._.--

at 222 llID. 

Table 17. Absorption Cross Sections of HN03 Vapor 

~ 10200' .\ 10200' 

(nm) (cm2 ) (nm) (cm2 ) 

190 1560 260 1.88 

195 1150 265 1.71 

200 661 270 1.59 

205 293 275 1.35 

- .- - -- - --- ---210- - - - 105 2S0 - 1.10 

215 35.6 2SS 0.848 

220 15.1 290 - 0.607 

225 8.62 295 0.409 

230 5.65 300 0.241 

235 3.72 305 0.146 

240 2.57 310 0.071 

245 2.10 315 0.032 

250 1.91 320 0.012 

255 1.90 325 0.005 

330 0.002 

) 

113 ;--'.-

y!' --- j _/": 

. ----r, 
) 

7~~~~~' """., " .... '-·w:;:-~-~ ... ---..,.-~--- _~·_T ' .. (i 

H02N02 + hv ~ products 

There are four studies of the UV spectrum of H02N02 vapor: Cox and 

Patrick (1979), Morel et a1. (19S0), Graham et a1. (197Sb) and Molina and 

Molina (1981). The latter two studies are the only ones covering the gas 

phase spectrum in the critical wavelength range for atmospheric photodissociation, that is, wavelengths .. longer than .290_nm. The recommended 

values, listed in Table lS are taken from the work of Molina and Molina 

(19Sl), wQich _i~ the more direct .study. The~emperature dependence of the 

cross sections at these longer wavelengths remains to be determined. 

MacLeod ~. __ (..19S~) .E~p0I:~.~hat photolysis at 2~S nm yields one third OH 

and N03 and two thirds Hoi ~+N02. 

Table lS. Absorption Cross Sections of H02N02 Vapor 

A 10200' A 10200' 

(run) (cm2 ) (nm) (cm2) 

190 1010 260· 27.S 

195 816 265 22.4 

200 563 270 17 .S 

205 367 275 13.4 

210 241 2S0 9.3 

-~ .. - 215-- -164 - 285 6-; 3· - -- -.--

220 120 290 4.0 

225 95.2 295 2.6. 

230 SO.S 300 1.6 

235 69.S 305 1.1 

240 59.1 310 0.7 

245 49.7 315 0.4 

250 41.S 320 0.3 

255 35.1 325 0.2 

330 0.1 

114 

) I" 

.' 

r 

~~r 
.,-:;;!'<_ 

~~ .. -•.... _-> ~'.' ",. -_.--.:..... . -.--~- -'._- - -~-~.~(£ 

) 

C12 + hv ~ Cl + C1 

The absorption cross sections of C12, listed in Table 19, are taken 

from the work of Seery and Britton (1964). These results are in good agreement with those reported by Gibson and Bayliss (1933), Fergusson~. 

(1936), and Burkholder and Bair (1983). 

Table 19. Absorption Cross Sections of C12 

~ 10200 ~ 10200 

(run) (cm2) (run) (cm2) 

-- - ---

240 0.08 350 18.9 

250 0.12 360 13.1 

260 0.23 370 8.3 

270 0.88 380 4.9 

280 2.7 390 3.3 

290 6.5 400 1.9 

300 12.0 410 1.3 

310 18.5 420 0.99 

320 23.6 430 0.73 

330 25.6 440 0.53 

340 23.6 450 0.34 

-_ .. ------

115 

) f 

c 

------.. -r! 
,. r 01'-'0~ -,.\ .... 0. 

0) 

- .- - --

;. 

• 

)1 

; 

0\1: 

ClO + rJl .... Cl + 0 

The absorption c"Coss sections of chlorine monoxide. ClO, have been 

reviewed by Watson (1977). There are lIore recent measurements yielding 

results in reasonable agreement with the earlier ones, by Handelman and 

Nicholls (1977) in the 250-310 nil region; by Wine ~. (1977) around 

283 nil; and- by Rigaud~. (1977) and Jourdain~. (1978) in the 

270-310 pq region. 

_The calculations of Coxon KJil. (1976) and Langhoff -~ (1977)-

indicate that photodecomposition of ClO accounts for at most 2 to 3 percent 

of the total destruction rate of ClO in the stratosphere, 'which occurs 

predominantly by reaction with oxygen atoms and nitric oxide. 

ClOO + hv .... ClO + 0 

Johnston et a1. (1969) measured the absorption cross sections of the 

ClOO radical using a molecular modulation technique which required interpre tat ion of a comp.1ex kinetic scheme. The _values listed in Table 20- are 

taken from their work. 

Table 20. Absorption Cross Sections of ClOO 

10200- 102047 -A A 

(nil) (cm2) (nil) (cm2) 

225 260 255 1240 

230 490 260 1000 

235 780 265 730 

240 1050 270 510 

245 1270 275 340 

250 1230 280 230 

116 ,-

f; 

~ 
IIE.-.!.:. .. 

) 

::. 

)~ 

J 

OC10 + hv ~ a + CIO 

The spectrum of OClO is characterized by a series of well developed 

progressions of bands extending from -280 to 480 nm. The spectroscopy of 

this molecule has been studied extensively, and the quantum yield for 

photodissociation appears to be unity throughout the above wavelength 

range- -see, for.example •.. the revie~ by Yatson (19.11). 

Birks ~. (1917) have estimated a half-life against atmospheric 

p~otodissociati~~ of~~l~ of a few seconds. 

The recommended absorption cross section values are those reported by 

Yahner et al. (1981), who measured the spectra with a resolution of 0.25 nm 

at 204-, -296-and 318 ·K; in the wavelength range 240 to 480 nID.· Table. 21 

lists the cross section values at the peak of the bands [a(O) to a(26)]. 

111 

\"!J 

• I 

~ 
r----------- . ------------

) 

Table 21. Absorption Cross Sections 

of OCIO at the Band Peaks 

10200 (cm2) 

.\(nm) 204 K 296 K 378 K 

475.53 13 

461.15 17 17 16 

446.41 94 69 57 

432.81-- 220 166 134 

420.58 393 304 250 

408.83 578 479 378 

397.76 821 ~----

670 .547 

387.37 1046 844 698 

377.44 1212 992 808 

368.30 1365 1136 920 

359.73 1454 1219 984 

351.30 1531 1275 989 

343.44 1507 1230 938 

336.08· -1441 -1139 -864 

329.22 1243 974 746 

322.78 1009 791 628 

317.21 771 618 516 

311.53 542 435 390 

305.99 393 312 - 29l --

300.87 256 219 216 

296.42 190 160 167 

391.77 138 114 130 

287.80 105 86 105 

283.51 089 72 90 

279.64 073 60 79 

275.74 059 46 

272.93 053 33 

118 

) 

--

.... - - -- , 

. 

. 

j-~ ~ 
.r .\T.--.'-" 

. " 

) 

) -; 

" .; 

'\+- -------------- ~ 

Cl03 + hv ~ products 

Table 22 lists absorption cross sections of chlorine trioxide, Cl03' 

for the 200 to 350 nm rang~ obtained by graphical interpolation between the 

data points of Goodeve and Richardson (1937), Although the quantum yield 

for decomposition has not been measured, the continuous nature of the 

spectrum indicates that it is likely to be unity. 

Table 22, Cl03 Absorption Cross Sections 

-l 10200' l 10200' 

- _. - ___ (rua) .. _ (cm2 ) _ - (nm)--- (cm2) 

200 530 280 460 

210 500 290 430 

220 480 300 400 

230 430 310 320 

240 350 320 250 

250 370 330 180 

260 430 340 110 

270 450 350 76 

C1202 + hv 

The UV spect~ of C120 2 has been st_~di!~._ by Basco and Hunt (1979), 

who report cross sections at six wavelengths between 277 and 232 nm, with 

increasing values towards the shorter wavelengths; by Molina and Molina 

(1987), who observed a maximum at about 270 nm; and by Cox and Hayman (1987), 

who report the maximum around 245 IUD. Using IR spectroscopy, Molina and 

Molina (1987) showed that several isomers of C1202 exist, so that the 

discrepancies in the UV spectra might be due at least in part to the presence 

119 

~ -

, • 

~ 
) 

" 

-- ,-

---

) 

·.".#,:~_.,w, - '-~. T~· ..• 

of different isomers. On the other hand. for the atmospherically-important 

wavelength region around 310 lUll the agreement between the last two sets of 

data is good. Clearly, additional studies are needed. Molina and Molina 

(1987) suggest a quantum yield of unity for the production of Cl-atoms, but 

direct studies of the identity of the photodlssociatlon products also need 

to be carried out. 

HCI + hv .. H + CI 

The absorp_t~on_ cro~s __ ~ections of_Hel •. lls~ed_Jn Table 23, are taken 

from the work of Inn (1975). 

Table 23. Absorption Cross Sections of HCl Vapor 

~ 1020(7 ~ 1020u 

(nm) (cm2) (nm) (cm2) 

140 211 185 31.3 

145 281 190 14.5 

150 345 195 6.18 

-155 - 382 - 200 2:56 

160 332 205 0.983 

165 248 210 0.395-

170 163 215 0.137 

175 109 220 0.048 

180 58.8 

120 

• 

.~ 

Jt~~ li:; 

\: 
) 

..' 

.... 

) 

III!I • .,..--,. .. .., 

HOCl + lui .. OH + Cl 

Knauth~. (1979) have measured absorption cross sections of HOCI 

using essentially the same technique as Kolina and Kolina (1978) except for 

a higher temperaeure, which allowed them to obtain a more accurate value 

for the equilibrium constant Keq for the H20-C120-HOCl system. The crosssection values from Kolina and Kolina·s measurements recalculated using the 

new Keq are in excellent agreement with the results of Knauth~. The 

recolamended values, taken from this later-work, are presented in Table 24. 

Kolina et a1. (1980b), by monitoring directly OH radicals produced 

by laser photolysis of HOCl, __ obtain an absorption cross section value of 

-6 x 10-20 cm2 ·around 310 ~, ~g~i~ in exc·elie~t ag~e~me·nt -;lth the data of 

Knauth et al. (1979). 

In contrast, the theoretical predictions of Jaffe and Langhoff (1978) 

indicate negligible absorption at those wavelengths. The reason is not 

known, although it should be pointed out that no precedent exists to validate 

the theoretical approach for this particular type of problem. 

Recently, Kishalanie ~. (1986) reported measurements of the UV 

spectrum of HOC1, using a dynamic source to generate this species, instead 

of equilibrium mixtures with C120 and H20. Overall, their results are in 

reasonable agreement with the recommended cross section values, and lead to 

.slightly smaller atmospheric photodissociation rates _ belClW- -30._kn, but 

yield, at higher altitudes, rates which are larger by a factor of up to 

-1.7. The reason for the discrepancy is not known . 

Butler and Phillips (1983) found no evidence for a-atom production at 

308 nm, and placed an upper limit of -0.02 for the primary.quantum yield 

for the HCI + 0 channel. 

121 

....--. 

...-::;'" ,. 

.~ 

~-I 

;...-

~ 
'-- . .,-. _. -'. . ' -.....:... .. 

) 

- --_. -- -- -.- -

--~- ---

) 

Table 24. Absorption Cross Sections of HOCI 

l. 1020C7 l. lO20C7 

(nm) (cm2) (nm) (cm2) 

200 5.2 310 6.2 

210 6.1 320 _____ - 5~0 

220 11.0 330 3.7 

230 18.6 340 2.4 

___ 240 22.3 350 - 1.4 

250 18.0 360 0.8 

260 10.8 370 0.45 

270 6-.2 380 0.24 - "-- -- 280 4.8 390 0.15 

290 5.3 400 0.05 

300 6.1 420 0.04 

ClNO + hv ~ Cl + NO 

Nitrosyl chlorid~ has a continuous absorption extending beyond 650 nm. 

There is good agreement between the work of Hartin and Gareis (1956) for the 

240 to 420 nm wavelength region, of Ballash and Armstrong (1974) for the 185 to 

540 nm regi~n, and of lIlies and Takacs (1976) for -the 190 to 400 nm region, 

and: of Tyndall et al. (1987) for the 190 to 350 region except- around 230 nm, 

where the values of Ballash and P_rmstrong are larger by almost a factor of two. 

The recommended absorption cross sections, listed in Table 25, are taken froe 

the recent work of Tyndall et ale (1987). 

The quantum yield for the primary photolytic process has been reviewed 

by Calvert and Pitts (1966a); it is unity over the entire visible and nearultraviolet bands. 

122 

.\;t 

J. 

r_--

~ 
.p. ,.~~~.~~- .-- ~. ----------_. '~L+-

"" I 

, 

) 

Table 25. C1NO Absorption Cross Sections 

). lO20a ). lQ20a ). lQ20a ). lQ20a 

(nm) (cm2) (nm) (cm2) (nm) (cm2) (run) (cm2 ) 

190 4320 230 266 270 12.9 310 11.5 

. - - - _ . - -_. -- -_. -'192- . 5340- 2.'2- 212- 272 .- -- ... 12.3 -- - 312 11.9 

194 6150 234 164 274 11.8 314 12.2 

196 6480 236 120 276 11.3 316 12.5 

198 6310 -238 -- 101 278 10~ 7 318 13.0 

200 5860 240 82.5 280 10.6 320 13.4 

202 5250 242 67.2 282 10.2 322 13.6 

204 4540 244 _ _ 55.1 __ 284_. 9.99 _ 324 .. __ -14.0 :i' 

; 

1 • 

206 3840 246 45.2 286 9.84 326 14.3 

208 3210 248 37.7 288 9.71 328 14.6 

210 2630 250 31. 7 290 9.64 330 14.7 

212 2180 252 27.4 292 9.63 332 14.9 

-",_ ... 214 1760 254 23.7 294 9.69 334 15.1 

-,,' 216 1400 256 21.3 296 9.71 336 15.3 

218- 1110 258 19.0 298 9:89 338- 15.3-

220 896 260 17 .5 300 10.0 340 15.2 

.' .. 222 707 262 16.5 302 10.3 342 15.3 

224 552 264 15.3 304 10.5 344 15.1 

226 436 266 14.4 306 10.8 346 15.1 

228- 339 -- -268- - -- 13.6- 308 - 11.1 -- 348 - 14.9---

350 14.5 

,./"''' 

;. 

i 

-

123 

~ 

) ~ 

" 
'-. 

............. 

) 

) 

-............. 

,-~ "'!'......-"",- -

ClN02 + hv ~ products 

The absorption cross sections of nitryl chloride, ClN02' have been 

measured between 230 and 330 nm by Martin and Gareis (1956), between 185 

and 400 nm by 1111es and Takacs (1976), and between 270 and 370 nm by 

Nelson and Johnston (1981). The results are in good agreement below 300 nm. 

Table _26.- lists the recommended .. va1ues which are taken from· ll11es - and 

Takacs (1976) between 190 and 270 nm, and from Nelson and Johnston (1981) 

between 270 and 370.tlJ!l. The~e latter authors showed that an approximate 

6% C12 impurity in the samples used by 111ies and Takacs could explain 

the disc_repa~cy in the results above 300 nm •. _ Nelson and Johnston (1981) 

report a value of one (within' experimental error) for the quantum yield 

for production at Cl-atoms; they also report a negligible quantum yield 

for the production of oxygen atoms. 

Table 26. Absorption Cross Sections of ClN02 

l 102017 l 10200 

(nm) (cm2) (nm) (cm2) 

190 2690 -. 290 18.1 

200 455 300 15.5 

. 

210 339 310 12.5 . 

220 342 320 8.70 

. 230 236 330 5.58 

240 140 340 3.33 

250 98.5 350 1. 78 

260 63.7 360 1.14 

270 37.2 370 0.72 

280 22.3 

124 

-:(± 

.J. 

i 1! _-- : ,~ 
~d.~_-:" ------··I*" 

, .. _------ ... 

) 

CIONO- + hv ... products 

Measurements in the near-ultraviolet of the cross sections of chlorine 

nitrite (C10NO) have been made by Molina and Molina (1977). Their results 

are listed in Table 27. The characteristics of the spectrum and the instability of ClONO strongly suggest that the quantum yield for decomposition 

.is unity __ .The -CI-O bond strength is only about 20- kilocalories. so that' 

chlorine atoms are likely photolysis products. 

Table 27. CIaNO Absorption Cross Sections at 231 K 

~ 10200 ~ 10200 .-----.. (cm2) . - - -' - - -... _. 2 . - - .. -- -(nm) (run) (em) 

235 215.0 320 80.3 

240 176.0 325 75.4 

245 137.0 330 58.7 

250 106.0 335 57.7 

255 65.0 340 43.7 

260 64.6 345 35.7 

265 69.3 350 26.9 

270 90.3 355 22.9 

275 110.0 360 16.1 

280 132.0 365 11.3 - - - --. ----- - 285 144.0 370 9.0 

290 144.0 375 6.9 

295 142.0 380 4.1 

300 129.0 385 3.3 

~ -

305 114.0 390 2.2 

310 105.0 395 1.5 

315 98.1 400 0.6 

125 

) ,-

- --

~ 

.----

.. 
) 

.---

.. /--

J 

Jl-~-.~.:'"--.--'.- ... -~ .. --....... -., ,I\.'l" ." , . ~~: .... -- -..-:-----------_._--.. _-

----.... {.t --_ .. P __ __ _ __ .... _~.-.-- - •• 

.. _-----

C10N02 + hv ~ products 

The recommended cross section values, listed in Table 28, are taken 

from the work of Molina and Koli'Qa (1979), which supersedes the earlier 

work of Rowland, Spencer and Molina (1976). 

The identity of the primary photolytic fragments has been investigated 

by .severaL groups.,_Smith~. (1977) =eport 0 + C10NO as _the.. most likely 

products, using end product analysis and steady-state photolysis. The 

resul:.ts of Chang.et al. (1979~),. ,who el!lployed ,~he "Very Low Pressure Photolysis" (VLPPh) technique, indicate that the products are Cl + N03. 

Adler-Golden and Wiesenfeld (1981), using a flash photo~ysis atomic absorpHon tecnn[que, find O-'atoms to be the predominant pliotol}isis product',ilnd 

report a qualttum yield for Cl-atom production of less than 4X. Marinelli 

and Johnston (1982b) report a quantum yield for N03 production at 249 n2 

between 0.45 and 0.85 ~ith a most likely value of 0.55; they monitored NO; 

by tunable dye-laser absorption at 662 nm. Hargitan (1983a) used atomic 

resonance fluorescence aetection of 0- and Cl-atoms and-fOund the quantu:::a 

yield at 266 and at 355 nm to be 0.9 ± 0.1 for Cl-atom production, and -0.1 

for O-atom production, with no discernible difference at the two wavelengths_ 

The preferred quantum yield values are 0.9 for the Cl + N03 channel, 

and a complementary value of 0.1 for the 0 + CIONO channel. The recommenda- ". 

tion is based on Margitan ~1983a), whose direct study is the only one wi~~ 

results at a wavelength longer than 290 nm, which is where atmospheric 

photodissociation will predominantly occur. The reason for the discrepancy 

with the studies by Adler-Golden and Weisenfeld (1981) and by Marinelli a~d 

Johnston (1982b) is almost surely that the rate consrant for Cl + ClN03 is 

much faster (two orders of magnitude) than previously thought (Margitan, 

1983a; Kurylo ~., 1983a). 

126 

.-J r -- v. 

r· 
.... -:,,~-~.-- •• ~ •••• M -.~ ------- -.. -_ .... _. -~- -.--- --. ._---_ .. _--- ------~------

) Table 28. Absorption Cross Sections ofC10NOZ 

~ 1020o {cm2l ~ 102Ou{cm2l 

(run) 227K 243K 296K (run) 227K 243K 296K 

190 555 589 325 0.463 0.502 0.655 

195 358 381 330 0.353 0.381 0.514 

200 - - -293 --- -- -.- - 307 335 -0.283 ().307 0.397 

205 293 299 340 0.246 0.255 0.323 

210 330 329 345 0.214 0.223 0.285 -_. - --- -- 215 362 360 350 0.198 0.205 0.246 

220 348 344 355 0.182 0.183 0.218 

____ 22;>_ 282 - 286 360 0.170 0 .. J73 0.208 - ... 

-230-- 206 -- - . 210 365 0~155 - --0.-1-59-·-- 0.178 

235 141 149 370 0.142 0.140 0.162 

240 98.5 106 375 0.128 0.130 0.139 

245 70.6 77.0 380 0.113 0.114 0.122 

250 52.6 50.9 57.7 385 0.098 0.100 0.108 

255 39.8 39.1 44.7 390 0.090 0.083 0.090 

260 30.7 30.1 34.6 395 0.069 0.070 0.077 

265 23.3 23.1 26.9 400 0.056 0.058 0.064 

270 18.3 18.0 21.5 405 0.055 

275 13.9 13.5 16.1 410 0.044 

280 10.4 9.98 11.9 415 0.035 

285 7.50 7.33 8.80 420 0.027 

--·-----.--290 5.45 5.3"6· .- ·6.36 -425 - -- - -- 0-;020 

295 3.74 3.83 4.56 430 0.016 

300 2.51 2.61 ·3.30 435 0.013 

305 1.80 1.89 2.38 440 0.009 

310 1.28 1. 35 1.69 445 0.007 

315 0.892 0.954 1.23 450 0.005 

320 0.630 0.681 0.895 

127 

.) 

·ft 

_ . 

. --~--

t_ 

~ 

---r;-
) 

) 

Jr~"¥'~~--'" .•.. , -_-0_-- to • .J.~ ," • 

,r- - o __ ._'.~ " __ .h. ___ H'

Halocarbon Absotption Cross Sections and Quantug Yields 

The primary process in the photodissociation of chlorinated hydrocarbons is well established: absorption of uitraviolet radiation in the 

lowest frequency band is interpreted as an n-a* transition involving 

excitation to a repulsive electronic state (antibonding in C-CI) , which 

dissociates by breaking the carbon chlorine bond (Majer and simons, i964). 

As expected, the chlorofluoromethanes--which are just a particular type of 

chlorinated hydrocarbons--behave in this iash10n-(sandorfy, .1976)~ Hence, .---

the quantum yield for photodissociation is expected to be unity for these 

cOIl!E.0~~ds • There are_several studies which show specifically that this-is 

the case for CF 2Cl2' CFC13 anet CC14. These studies - -which have been reviewed 

in CODATA (1982) - -also indicate that at shorter wavelengths two halogen 

atoms can be released simultaneously in the primary process. 

Several authors have reinvestigated the absorption cross sections for 

CC14 , CCI~F, CC12F2' CHC1F2' and CH3Cl--e.g., Hubrich et ale (1977); Hubrich 

and Stuhl (1980); Vanlaethem-Heuree et ale (1978a,b); Green and Wayne (1976-

1977)--and their results are in general in very good agreement with our 

earlier reco~mendations. Tables 29, 30 and 31 list the present recommendations for._the cross_ sections of CC14 , cg13~ a~«! CC~2F2 respectively; these . -- ----- -----

data are given by the mean of the values reported by various groups--those 

cited above as well as those referred to in earlier evaluations--as reviewed 

by CODATA (1982). For atmospheric photodissociation calculations the change 

in the cross section values with teD!Perature is negligible for CCl4 and 

CFC13; for CF2Cl2 the temperature dependence is given by the expression 

at the bottom of Table 31. The species CHClF2' CH3Cl, CH3CC13' CBrF3 and 

CBrClF2 are discussed individually; their absorption cross sections are 

listed in Tables 32, 33, 35 and 36, respectively. 

. --......... , .. """'-

128 

------. . --

i· 

t ~. 

. ------r, 
W=;¥,~l:~~~_ r~:-._ .• ·~· .------.-;-- .-.------ ~(£ 

._-_._ ... ---- --

) 

Table 29. 

A 

(nm) 

174 

176 

178 

180 

182 

184 

186 

188 -_. --.----- - - ----. 

190 

192 

194 

196 

198 

200 

-202 

204 

206 

208 

210 

214_ 

214 

216 

) 

_ -"V-' ..... 

Absorption Cross Sections of CC14 

1020a A 1020a 

(cm2) (till) (CDl2) 

995 218 21.8 

1007 . 220 - 17.0 

976 222 13.0 

772 224 9.61 

589 226- 7.19 

450 228 5.49 

318 230 4.07 

218 232 3~OL 

144 234 2.16 

98.9 236 1.51 

74.4 238 1.13 

68.2 240 0.784 

66.0 242 0.579 

64.8 244 0.414 

-62.2 246 0.314 

60.4 248 0.240 

56.5 250 0.183 

52.0 255 0.0661 

46.6 260 0.0253 

_39.7 __ 265 -- - -0.0126 - -

33.3 270 0.0061 

27.2 275 0.0024 

129 

-- --- - - -- . 

- ---. ------

., -' -_ . .. /: 

--~--T-
~~.-

) 

. ~ ~ - _. 

---~ .-- --

----- ----- -

) 

.. 

Table 30. Absorption Cross Sections of CC13F 

~ 10200 ~ 1020(7 

(nm) (cm2) (nm) (cm2) 

170 316 208 21.2 

.17L _____ 319 210 .- 15.4-

174 315 212 10.9 

176 311 214 7.52 

178 304 216- 5.28 

180 308 218 3.56 

182 285 220 2.42 

184 260 222 1.60 -- - _. 

186 233 224 1.10 

188 208 226 0.80 

190 178 228 0.55 

192 149 230 0.35 

194 123 235 0.126 

196 99 240 0.0464 

198 80.1 245 0.0173 

200 64.7 250 0.00661 

202 50.8 255 0.00337 

204 38.8 260 0.00147 

206 29.3 

- .- - --

130 

------- .--- ------':t 

-----. 

(-~ 

(.t 
~'-'P-- \."t"J 1""" 

) 

Table 31. Absorption Cross Sections of CC12F2 

.\ 10200 .\ 10200 

(nm) (cm2) (nm) (cm2) 

170 124 200 8.84 

172 -- 151 202 5.60 -- -- -- .. 

174 171 204 3.47 

176 183 206 2.16 

--_. - ---- -178 -189 208 1.52 

180 173 210 0.80 

182 157 212 0.48 --_._- -_.-

184_ . 137 214 0.29- -- -- ----- - 186 104 216 0.18 

188 84.1 218 0.12 

190 62.8 220 0.068 

192 44.5 225 .0.022 

194 30.6 230 0.0055 

196 20.8 235 0.0016 

198- 13.2 240 0.00029 

a T - 0298exp[4.1 x 10-4 (.\-184.9)(T-298)] 

Where: 0298 cross section at 298 K 

.\ run 

T temperature, Kelvin 

131 

) ;. 

~ 
) 

) 

__________ .___ ph_ ._____ ~ 

The absorption cross sections for various other halocarbons not listed 

in this evaluation have also been investigated: for CC1F3' CC12FCC1F2' 

CC1F2CC1F2 and CC1F2CF3 the values given by Hubrich and Stubl (1980) at 

298 K are in very good agreement with the earlier results of Chou ~. 

(1978) and of Robbins (1977); Huhrich and Stubl also report values of 208 K 

-- -for these'- species ~ -- Other absoiptron cross section measurement -inclwie 

the following: CHC12F by Hubrich tt...Al. (1977) ; CHC13' CH2C12' CH2C1F • 

. _CF3CH2Cl. CH3CC1F2-and CH3CH2Cl by Hubrich and Stuhl-(1980) ;--CHC13 • CH3Br. - -

CHFC12' C2F4Br2' C2HC13 and C2H3C13 by Robbins (1917); CH2C12 and CHC13 

_by Vanlaethe~Keuree_~. (1978a); CHC12F. CC1F2CH2Cl. CF3CH2Cl. - CF3ChC12 

and CH3CF2Cl by Green and \layne (1976-1977); and CH3Br. CH2Br2' CBr2F2' 

CBrF2CBrF2 and CBrF2CF3 by Kolina~. (1982). 

As before. the recommendation for the photodissociation quantum yield 

value is unity for all these species. 

132 

-:~!. 

b 
) 

) 

·r.;;;'" 

~--

CHC1F2 + hv ~ products 

The preferred absorption cross sections, listed in Table 32, are the 

mean of the values reported by Robbins and Stolarski (1976) and Chou ~. 

(1976), which are in excellent agreement with each other. Hubrich~. 

(1977) .. h_a'ye report!d c:r.o~~. s~ct~o~ for ._C!!~lF2 at 298 K and 208 K. Their 

results indicate a significant temperature dependence for .\ > 200 nm, and 

their room temperature values are somewhat higher than those of the former 

two groups. 

Photolysis of CHC1F2 is rather unimportant throughout the atmosphere: 

reaction with OH radical is the-dominant destruction process. 

Table 32. Absorption Cross Sections of CHC1F2 

.\(nm) 1020a ( cm2) 

174 5 •. 94 

176 4.06 

178 2.85 

180 1.99 

182 1.30 

--.-.. _--- - 18~ 0.~25 - .- -.--

186 0.476 

190 0.235 

192 0.157 

194 0.100 

196 0.070 

198 0.039 

200 0.026 

202 0.022 

204 0.013 

133 

~ 

,-

~ 
.., .19"'-.:.:' 

) . CH3C1 + bv ... products 

The preferred absorption cross sections, listed in Table 33, are those 

given by Van1aethem-Meuree~. (1978b). These values are in very good 

agreement with those reported by Robbins (1976) at 298 K, as well as with 

those given by Hubrich~. (1977) at 298 K and 208 K, if the temperature 

. _trend is _taken into c~msidera,ti~n. 

Table 33. Absorption Cross Sections of CH3Cl - --- - - .. -

A 

1020u (cm2) 

{nin)---. -- -296K- 279 K 255 K ----.. _. ---

186 24.7 24.7 24.7 

188 17.5 17 .5 17.5 

190 12.7 12.7 12.7 

192 8.86 8.86 8.86 

194 6.03 6.03 6.03 

196 4.01 4.01 4.01 

198 2.66 2.66 2.66 

200 1. 76 1. 76 1. 76 

202 1.09 1.09 1.09 

204 0.691 0.691 0.691 

206 0.483 0.475 0.469 ---.- .---- - - .. . - -- - --

208 0.321 - . 0.301 0.286 

210 0.206 0.189 0.172 

212 0.132 0.121 0.102 

214 0.088 0.074 0.059 

216 0.060 0.048 0.033 

134 

) 

t

-" ------

~ ..... 

~ 

:;. 

~ :..Ail 

if 
) 

) 

~~ 

,/ 

~ !\~.'-'" "~\ ..... 

CC120 + hv ... products, CC1FO + hv ... products, and CF20 + hv .... products 

Table 34 shows the absorption cross sections of CC120 (phosgene) and 

CFClO given by Chou~. (1977), and of CF20 taken from the work of Molina 

and Molina (1982). The spectrum of CF20 shows considerable structure; 

the va1u~~ listectin.Tab1e 34 ~re .ay~r~g~s oyeLea.~h_.5Q wavenumber interval. 

The spectrum of CFClO shows less structure, and the CC120 spectrum is a 

continuum; its photodissociation quantum yield is unity (Calvert and Pitts, 

1966a), 

The quantum yield for the photodissociation of CF20 at 206 nm appears 

to be -0.25 (Molina and Molina-; -1982); additional studies of the quantum 

yield in the 200 nm region are required in order to establish the atmospheric 

photodissociation rate, 

CH3CC13 + hv ~ products 

The absorption cross sections have-been measured bY'Robbins (1977), by 

Vanlaethem-Meuree ~, (1979) and by Hubrich and Stuhl (1980). These 

latter authors corrected the results to account for the presence of a UVabsorbing stabilizer in their samples, a correction which might account for 

"the rather" "iarge dfs·crepancy with the other measurements: "The results ofRobbins (1977) and of Vanlaethem-Meuree~. (1979) are in good agreement. 

The recommended values are taken from this latter work (which reports values 

at 210 1<, 230 K, 250 K, 270 K and 295 K, every 2 nm, and in a separate 

table at wavelengths corresponding to the wavenumber intervals generally 

used in stratospheric photodissociation calculations). Table 35 lists the 

values at 210 K, 250 K and 295 K, every 5 lUll; the odd wavelength values 

were computed by linear interpolation. 

135 

"\

~--

, --' 

~. 

'" 
) 

) 

'J 

! 

-'.-

~-~~~ .. ~~~---

/' - /// 

Table 34. Absorption Cross Sections of CC120, CC1FO, andCF20 

.\ 

102Oa(cm2) 

(nut) CC120 CC1FO CF20 

184.9 204.0 

186.0 189.0 15.-6 -5-.5--- -

187.8 137.0 14.0 4.8 

189.6 117.0 13.4 4.2 - --- - 191.4 93.7 12.9 3.7 

193.2 69.7 12.7 3.1 

195.1 ___ _52._.5 _____ 12.5 2.6 

197.0 -- 41,0 - - -- 12.4--- 2.1 

199.0 31.8 12.3 1.6 

201.0 25.0 12.0 1.3 

103.0 20.4 11. 7 0.95 

205.1 16.9 11.2 0.69 

207.3 15.1 10.5 0.50 

209.4 13.4 9.7 0.34 

211.6 12.2 9.0 0-;-23 

213.9 11.7 7.9 0.15 

216.2 11.6 6.9 0.10 

::18.6 11.9 5.8- 0.06 

221.0 12.3 4.8 0.04 

_--=-223-.5 ----- ---:T2-:-1f - - 4.0 0.03 

226.0 13.2 3.1 

136 

--------- -------"----
~~.-...... ---\t 

-) 

Table 35. Absorption Cross Sections of CH3CC13 

~ 

102Oa(cm2) 

(nm) 295 K 250 K 210 K 

185 _ . 265 -- 265 . - - - - 265 . __ - - -. -- -

190 192 192 129 

200 81.0 81.0 81.0 

205 - 46.;-0- 44.0 - 42.3·-

.~.- 210 24.0 21.6 19.8 

215 10.3 8.67 7.47 

220 4:15 3.42 - 2.90 

------ . - 225 1. 76 1.28 0.97 

230 0.700 0.470 0.330 

235 0.282 0.152 0.088 

240 0.102 0.048 0.024 

·CBrCIF2 + hv ~ products 

The absorption cross sections of CBrC1F2 (Halon 1211, or fluorocarbon 

l2Bl) have been measured by Gio1ando et a1. (1980), and by Molina ~. 

(1982), both at room temperature. Th~ recommend~d cross sections, listed 

-_ ... --.--- .... .- in Table- 36, are -taken-from this latter work. These-cross section values 

are about 20% lower than those reported by Giolando et a1. in the atmospherically important 285-305 nm wavelength region. 

CBrF3 + hv ~ products 

Table 36 shows the absorption cross sections of CF3Br (Halon DOl, 

or fluorocarbon 13B), taken from the work of Molina et al. (1982} who report 

measurements at 298 K. 

137 

) r-~ ~ 

--/" 

---
) 

----

/ 

) 

.• .2:.'-' \~.~ .~ .. - .- - - ...•. _.- ---- .. ---- .-.. -- ---.----.-... - ._- ... 

Table 36. Absorption Cross Sections of CBrF3 and of CBrC1F2 

.l 

10200- (cm2) l 

10200- (cm2) 

(nm) CBrF3 CBrC1F2 (nm) CBrF3 CBrC1F2 

190 G.7f - 42".4-- 265 - - -0:00-905 0.721 

195 9.61 71.1 270 0.00348 0.392 

200 11.8 96.2 275 0.00138 0.190 

205 12.9- 109 280 0.00055 0.0883 

210 12.3 105 285 0.00022 0.0398 

215 10.3 89.6 2~Q _____ 0.00008 0.0182 

220 - 7.50 - 70.0 - - - 295 - -- 0.003---- 0.00821 

225 4.83 51.3 300 0.001 0.00361 

230 2.70 34.2 305 0.00165 

235 1.48 23.3 310 0.00066 

240 0.695 14.4 315 0.00026 

245 0.325 8.87 320 0.000098 

250 0.139 5.29 325 0.000037 

255 0.0589 2.97 330 0.000025 

260 0.0234 1.56 

BrO + hll ... Br + 0 

'IlieBrO radica1.-nas-a bandeaspectrum in-the 290:'380 nm range; -the 

strongest absorption feature lying around 338 nm. The photodissociation 

quantum yield in this wavelength range is expected to be unity due to 

extensive predissociation. 

The recommended absorption cross sections averaged over 5 nm wavelength 

intervals are taken from the work of Cox et ale (1982), and are listed in 

Table 37. These authors estimate a BrO lifetime against atmospheric photo138 

--- -- -.61. 

#-

.-

.... 

.. 
) 

'. 

:. 

) 

oJ' ... r~o--­

I 

-

.. 

L-

"'-

dissociation of -20 seconds at the earth's surface. for a solar zenith 

angle of 30·. 

The earlier BrO cross secticn measurements were carried out mostly 

around 338 nm, and have been reviewed by CODATA (1980; 1982). 

Table 37. Absorption Cross Sections of BrO 

l 

(nm) 

300 - 305 

305 - 310 

310 - 315 

315 - 320 

320 - 325 

325 330 

330 - 335 

335 - 340 

340 - 345 

345 - 350 

350 - 355 

355 - 360 

-360 -~ -365 

365 - 370 

370 - 375 

1020q(cm2) 

average 

200 

259 

454 

391 

600 

753 

628 

589 

515 

399 

228 

172 - -.-- ------ -

139 

161 

92 

51 

-------~ 
---- -_ . 

..... ~~ 

'~ .. ' . 

-.. 

- .--..:=-=

) 

BrON02 + hu ~ products 

The bromine nitrate cross sections have been measured at room temperature by Spencer and Rowland (1978) in the wavelength region 186-390 IUD; 

their results are given in Table 38. The photolysis products arc not known. 

- --. - --'-"-

.--- ./ 

Table 38. Absorption Cross Sections of BrON02 

~ 1020a 1 1020a 

(1lII) (cm2) (nm) (cm2) 

----- "--

186 1500 280" 29 - --"-.. 

190 1300 285 27 

195 1000 290 24 

200 720 295 22 

205 430 300 19 

210 320 305 18 

215 270 310 15 

220 240 315 14 

225 210 320 12 

230 190 325 11 

235 170 330 10 

......-" 240 130 335 9.5 --.-- ----- ·'245 100··- 340 8.7 

250 78 345 8.5 

255 61 350 7.7 

260 48 360 6.2 

265 39 370 4.9 

270 34 380 4.0 

275 31 390 2.9 

) 140 
) 

/' 

.~-.--

// 

) 

-'-,~ ."......_. -'-."~ .. -~ ...• -.-.- -----.. -- ~-=~=~ .. -- :It 

HF+h.v"H+F 

The ultraviolet absorption spectrua of HF has been studied by Safary 

~, (1951). The onset of absorption occurs at l < 170 nm, so that photodissociation of HF should be unimportant in the stratosphere. 

H2CO + hv .. H + HCO (~l)' 

.. H2 + CO (~2) 

Bass et a1. --(1980) have.., measured the- absorption- cross sections of " 

formaldehyde with a resolution of 0.05 nm at 296 K and 223 K. The cross 

sections have also been measured by Koortgat tt.Al. .. (1980;,1983) .with a. 

resolution of 0.5 nm in the 210-360 K temperature range; their values are 

-30% larger than those of Bass et ale for wavelengths longer than 300 run. 

The recommended cross section values, listed in Table 39, are the mean of 

the two sets of data (as computed in CODATA, 1982). 

The quantum yields have been reported with good agreement by Horowitz 

and Calvert (1978), Clark et a1. (1978a), Tang et ale (1979), Moortgat and 

Yarneck (1979), and Moortgat~. (1980; 1983). The recommended values 

listed in Table 39 are based on the results of all of these investigators. 

The quantum yield ~2 is pressure dependent for wavelengths longer than 

329 DIll, and is given by 'the' expression. ';it-' the .bottom of Table 37, which Is 

based on the values reported by Moortgat et a1. (1980; 1983) for 300 K. 

Additional work is needed to determine ~l and the cross sections around 

330 DIll, which i:o the important wa',elength region for atmospheric photodissociation of CH20 to yield H + HCO; only a few scattered measurements of ~l have 

been carried out around this wavelength. At present the recommendation for 

the 320-340 nm wavelength intertal is to calculate ~1 by linear interpolation 

assuming a value of ~l - 0.62 at 320 nm and ~1 - 0 at 340 DIll. 

141 

.-----

; 

~ 
) 

) 

~\~ 'V.~.--.~--. :-". -----_.- --~ 

... - ... ----_ .. _-'-

Table 39. Absorption Cross Sections and Quantum Yields 

for Photolysis of CH20. 

~ 

102Oa(cm2) ~l ~2 

(nm) 290 K 220 K (H + HCO) (H2 + CO) 

140 0.03 . 0.08 0.21 -- 0.42 -

250 0.13 0.08 0.24 0.46 

260 0.47 0.47 0.30 0.48 

270 . - 0:-86 (J.85- 0:40 - -o-~46 

280 1.86 1.93 0.59 0.35 

290 2.51 2.47 0.71 0.26 

- ----. 

300 2_.62 2.58 0.78 0.22 

310 2.45 2.40 0.77 0.23 

320 1.85 1.71 0.62 0.38 

330 1. 76 1.54 0.31 0.69 

340 1.18 1.10 0 0.69* 

350 0.42 0.39 0 0.40* 

360 0.06 0.02 0 0.12* 

Note: The values are averaged for 10 om intervals centered on 

the indicated wavelength. 

* : at P - 760 torr 

For A·> 329-nm,- ~2-at a-given wavelength (not. averaged 

over 10 om intervals) is given by the following 

expression: 

~2 - 1 - exp(112.8-0,347~) 

1 + f (!.:lll) 760 364-~ 

l nm 

P torr 

142 

. - - _. --

------1 
E-~.\~1i,~"W":--- -",.~- :.-., _r-_ -------.---------.. ------- -..-, -~--~ 

) 

CH300H + hv - products 

Molina and Arguello (1979) have measured the absorption cross sections 

of CH300H vapor. Their results are listed in Table 40. 

Table 40. Absorption Cross Sections of CH300H 

. - - -- -- - --- -

~ 10200 l 102°0 

(nm) (cm2) (nm) (cm2) 

210 37.5 290 0.90 

220 22.0 300 0.58 

230 '13.9 . -310 0.34 - ---------

-. - ---

240 8.8 320 0.19 

250 5.8 330 0.11 

260 3.8 340 0.06 

270 2.5 350 0.04 

280 1.5 

HCN + hv ~ products and CH3CN + hv ~ products 

Herzberg and Innes (1957) have studied the spectroscopy of hydrogen 

__ ~yanide, HCN, which starts absorbing weakly at l < 190 om. McElcheran et a1. 

(1958) have reported the spectrum of -methyl -cyanIde, __ -CH3CN; the first 

absorption band appears at A < 216 nm. 

The solar photodissociation rates for these molecules should be rather 

small, even in the upper stratosphere; estimates of these rates would 

require additional studies of the absorption cross sections and q\.lantum 

yields in the 200 nm region. 

143 

) 

,. 

r 
) 

) 

) 

r -, ". <-

S02 + hv ~ products 

The UV absorption spectrum of S02 is highly .tl:UC tured , with a very 

weak absorption in the 340-390 ma region, a veak absorption in the 260-340 

IUD, and a strong absorption extending from 180 to 235 nil; the threshold 

wavelength for photodissociation is -220 tuIl. the atmospheric photocheaistry 

~ - . 

of S02 has been reviewed by Heicklen~. (1980) and by Calvert and 

Stockwell (1983). Direct photo-oxidation at wavelengths longer than -300 nm 

by way of the electronically excited states of ·SOi appears to be relatively 

unimportant. 

The absorption cross se~ti~ns have been measured recently by McGee and ---'-- -- _. --. - - ---. 

Burris (1987) at 295 and 210 'K, between 300 and 324 IUII, which is the wavelength region commonly used for atmospheric monitoring of S~. 

oes + hv ~ CO + S 

The absorption cross sections of OCS have been measured by Breckenridge 

and Taube (1970), who presented their 298 K results in graphical form, 

between 200 and 260 IUD; by Rudolph and Inn (1981) between 200 and -300 run 

(see also Turco et al~, 1981), at 297 and 195 K; by Leroy et al. (1981) at 

294 K, between 210 and 260 l'Ul, using photographic p.!ates; by_Mo1i~.et aI. 

(1981) between 180 and 300 run, at 295 and 225 K, and by Locker et a1. (1983) 

between 195 and 260 IUD, in the 195 K to 40J K temperature range:---The results 

are in good agreement in the regions of overlap, except for ~ > 280 nm, 

where the cross section values reported by Rudolph and Inn (1981) are 

significantly larger than those reported by Molina et a1. (1981). The 

latter authors concluded that solar photodissociation of OCS in the troposphere occurs only to a negligible extent. 

144 

// 

." -
) 

r ' • .... 

.',\ _. - . - --

) 

The recollll8ndad cross seceiona, given in Table 41, are eaken from 

Kolina~. (1981). (The original publication also lists a eable wieh 

cross sections values averaged over 1 om intervals, between 185 and 300 nm.) 

The recollllllended quantum yield for photodissociation is 0.72. This 

value is taken from the work of Rudolph and Inn (1981), who measured ebe 

quantum yield for CO produceion in the 220-254 nm range. 

CSi + lui .. CS + S 

The CS2 absorption spectrum is rather complex. Its photochemistry has 

been reviewed by Okabe (1978). There are two diseinct regions in the riear 

UV spectrum: a serong absorption extending from 185 to 230 nID, and a weaker 

one in the 290-380 nm range. The threshold wavelengeh for photodissociation 

is -280 nm. 

The photo-oxidation of CS2 in the atmosphere has been discussed by 

Wine ~. (198ld), who repore thae electronically excited CS2 may react 

with 02 to yield eventually OCS. 

NaCl + h:I ... Na + Cl 

Ptere ar_e sever~l st~d~~s_!'J th!!UV absorpti~nspec tra_ of NaCl ~apor . __ _ 

For a review of the earlier work, which was carried out at high temperatures, 

see Rowland and Rogers (1982). The recolDlllended cross sections, listed--in 4 ._ ... _._ _ ____ _ 

Table 42, are taken from the work of Silver tt...Al. (1986), who measured 

spectra of gas phase NaCl ae room temperature in the range from -190 to 360 

nID, by directly monitoring the produce Na atoms. 

145 

=--_~\10', 

\ -I 

j. 

1 

i 

.:. 

~ 

~ 
) 

- ~ - - --

------ _. - -

--- ----

----- -

) 

Table 41. Absorption Cross Sections of OCS 

~ 

102Oa(cm2) ~ 

102Oa(cm2) 

(nm) 295 K 225 K (nm) 295 K 225 K 

186.1 18.9 13.0 228.6 26.8 23.7 

187.8 8.33 5.63 231.2 22.1 18.8 

L89~6- 3.75 2.50 233.9- --17~r . 14.0 

191.4 2.21 1.61 236.7 12.5 9.72 

193.2 1. 79 _ 1.53 239.5 8.54 6.24 - 195.1 1.94 1.84 242.5 5.61 3.89 

197.0 2.48 2.44 245.4 3.51 2.29 

199.0 3.30 3.30 248.5 2.11 1 29 

201.0 4.48 4.50 -251.6 -------1.21 -0.679 

203.1 6.12 6.17 254.6 0.674 0.353 

205.1 8.19 8.27 258.1 0.361 0.178 

207.3 10.8 10.9 261.4 0.193 0.0900 

209.4 14.1 14.2 264.9 0.0941 0.0419 

211.6 17.6 17.6 268.5 0.0486 0.0199 

213.9 21.8 21.8 272.1 0.0248 0.0101 

216.2 25 ;5 25.3 275.9 0.0119 0.0048 

218.6 28.2 27.7 279.7 0.0584 0.0021 

221.5 30.5 29.4 283.7 0.0264 0.0009 

223.5 31.9 29.5 287.8 0.0012 0.0005 

226.0 30.2 27.4 292.0 0.0005 0.0002 

- -- --- 296.3- 0.0002 ----

Photodissociation quantum yie1d-~ - 0.72 

146 

'.:. 

-----. 

ill 

.-

-; 

1- ___ ~~ I" J 
---------------------------- -----~ 

) 

Table 42. Absorption Cross Sections of NaCl Vapor at 300 K 

.\ 1020a 

(run) (cm2) 

189.7 612 

193.4 556 --- -- -.. -

203.1 148 

205.3 90.6 

-205.9 89.6 

210.3 73.6 

216.3 151 

218.7 46.3- .. - --- .. --._. 225.2 140- -----

230.4 512 

231.2 947 

234.0 1300 

237.6 638 

241.4 674 

248.4 129 

251.6 251 

254.8 424 

260.2 433 

268.3 174 

277.0 40 --.-. ----- - - -- - -- 291.8 0.8 

NaOH + hv .. Na + OH 

The spectrum of NaOH vapor is poorly characterized. Rowlar~ and Makide 

(1982) inferred the absorption cross section values and the ~/erage solar 

photodissociation rate from the flame measurements of DaiCoji (1979). 

Additional measurements are required. 

147 

) ~ 

': 

~ 
IJ 

/J 

APPENDIX. 

GAS PHASE ENTHALPY DATA 

th. foUow1n& data are adapted _1nly fr_ CCOATA (l1l84), althouah • f .. anU1 .. bav. b.an updatw. 

- ---- - ------- ----- ---------- - - ----- ---- ------ --- - -

KlLECUt.! AB!(ZII8) KlL!CtJl.E AB!(ZII8) tt:UX:UL! AB!(ZII8) KlLlCUL! AB!(Z981 

(~.1I1101) (Eeall.,U (Eeal/IIO!) (ICc al./IDC 11 

-------- -------.-- -------. -------._- -------- --------.- -------- --------.- B 5Z.1 __ C1!30 3.5 BSO -w ~lL __ . 19t! 

BZ 

0.00·· ~OZ 3.8±2 &S03 -1I2U CC14 -Z2.a 

° 511.57 Cllzal -6.: CS 65 ~~ -24.5 

0(1)) 104.11 CB3011 -48.0 CS: Z8.0 CBzCl 2UI 

0: 0.00 CB3Ot8 -31.3 c:s,S 33t2 CB:Clz -22.S 

- --_. -_ .. °Z(1_0ELTA) - 22.5 CB3<*O -15.6 . c:s,sc:s, -8.11 CB Cl- .- -19.6 ,3 

°z(l_SICHA) 37.5 _ CB3OBOz -Z8.6 CB3SSCB~ -5.8 C1CO -4.1 

°3 34.1 CB3OzlfO: -10.1I:U ~ -34 cecl: -S2.6 

HO 11.3 CzB 135 , 18.118 aCl 7:6 

- ------802 3:1:1 - CzBz · 54.35 ': 0.00 CBz' -812 

.- - -BzO -57.81 CzB3 • 118.1 SF . -65.34- - -.-CBCl: Z3.S11 -----

HZOZ -3Z.6 CzB4 12.45 IIOF -Z3.4:1:1 CFCl: -2Z.9 

H 113.00 CzB5 Z8.4 FO ZII:U CFC13 -68.1 

H: 0.00 CzB6 -ZO.O FO: 12:1:3 CFzCl -64.3 

MH 8Z.0 CBZCII 511.11 FOItO -15.: CFZC1Z -117.9 

MHZ 45.3 CB3C11 111.1 FIIOz -Z5.4 CF3Cl -169.Z 

NB3 -10.98 CBZCO -14 .Z3 FOIiOz 2.4 CarC1Z -E3.~ 

110 Z1.S7 CB3CO -5.11 el: -44±2 Car:Cl -l1S.5 

HOZ 7.9 CB3CBO -39." CF3 -112:1:1 COFCl -10Z!8 

H03 17U CZBSO -4.1 CF4 -223.0 Cz

C14 -3.0 

HZO ___ 19.61 CBzCllz°H -13..2 FCC -41:1:14 C2

BC13 -1..; 

If:03 19.8 CzBSOB -S6.Z cor: -151.7 CBzCC:' 11:7 

Hz04 :.Z CB3COZ -411.6 Cl Z8.11 CB3CC13 -34.0 

IfzOs Z.7 C2BS

Oz -1.8 CIz 0.00 Br 26.7 

HMO Z3.8 CB3

OOCB3 -30.0 1IC1 -22.07 Brz 7.J(' 

HMOz -19.0 C3B5 39.4 ClO Z4.4 BBr -8.70 

HM03 -3Z.3 C3B6 4.8 ClOO ZZ.5U BOBr -19+,.2 

HOzIiOz -11:1:2 n-C3

B7 22.6:1:2 OClO 23±2 BrC J~ 

----- ----- CB 14Z.0 1-C3

B7 - 18.2:1:2 . ClOOi >13.4 BrNO 19.,·-

CBz 9Z.3 C3B8 -24.84 C103 37 BrOlfOZ ~!7 

CB3 35.1 C2BS

CBO -404.8 CLz° 111.5 BrCl 3.! 

CB4 -17 .88 CB3COCB3 -Sl.9 CLz°z 31:1:5 - CBzBrz -Z.6:2 

CN 104.0 CB3CBCBzOH -18.0 DOCl -18.6±3 CBzBr 41:2 

BCN 3Z.3 S 66.22 ClIfO 12.4 CB3Br -9.3 

NCO 38 Sz 30.72 CllfOZ 3.0 CBBrz 4!:::.J 

CO -Z6.42 as 34:1:1 ClOtfO 111.8 I ZS.!Z 

COz -94.07 HzS -4.93 C~Z 11.3 I z 14.:12 

BCO 9.0 SO 1.Z FCl -12.1 HI 6.JO 

CBzO -26.0 SOz -70.96 CCl lZ0:I:5 10 4l! 

BCOOB -90.5 S03 -94.6 CC1z 56.11:1:5 lIfO 29a~ 

IlfOi 14.4 

148 ~ 

) If 

~ 
) 

) 

-; 

REFERENCES 

Adachi, H., and N. Basco, 1979, Chem. Phys. Lett. il, p. 490. 

Adachi, H., N. Basco, and D. G. L. James, 1980, Int. J. Chem. Kinet. 11, 

p. 949. 

Adler-Golden, S. H., and J. R. Yiesenfe1d, 1981, Chem. Phys. Lett. li, p. 281. 

Agcr, III, J. Y., 

pp. 1395 -1398. --

and C. J. Howard, 1986, Geophys. Res. Lett. , li, 

Ager, III, J. Y., and C. J. Howard, 1987a, J. Chem. Phys. 11, pp. 921-925. 

--Ager, III, J.-Y., and C. J. Howard, 1987h,-J. Geophys. Res • .2.2., pp. 6675-6678.--

Ager, III, J. Y., C. L. Talcott, and C. J. Howard, 1986, J. Chem. Phys. 85, 

pp. 5584-5592. 

Aleksandrov, E.N._, __ V. S. Arutyunov, and S. N. Koz1ov. __ 198~ Kinetics andCatalysis 21, pp. 391-394. 

Allen, H., and J. E. Frederick, 1982, J. Atmos. Sci. 39, pp. 2066-2075. 

Amimoto, S. T., A. P. Force, and J. R. Wiesenfe1d, 1978, Chem. Phys. Lett. 60, 

pp. 40-43. 

Amimoto, S. T., A. P. Force, R. G. Gu1otty, Jr., and J. R. Wiesenfe1d, 1979, 

J. Chem. Phys. 11, pp. 3640-3647. 

Amimoto, S. T., A. P. Force, J. R. Wiesenfe1d, and R. H. Young, 1980, J. Chem. 

Phys. 11, pp. 1244-1247. 

Anastasi, C., and 1. W. H. Smith, 1976, J. Chem. Soc., Faraday Trans. II 72, 

pp. 1459-1468. 

Anastasi, C., and I. W. H. Smith, 1978, J. Chem. Soc., Faraday Trans. II 74, - _0- ---p-;--1056;- - -- - --

Anastasi, C., 1. W. H. Smith, andD. A. Parkes, 1978, J. Chem. Soc., Farada:: 

Trans. I 74, pp. 1693-1701. 

Anderson, J. G., and F. Kaufman, 1972, Chem. Phys. Lett. 16, pp. 375-379. 

Anderson, J. G., and F. Kaufman, 1973, Chem. Phys. Lett. 19, pp. 4a3-486. 

Anderson, J. G., J. J. Hargitan, and F. Kaufman, 1974, J. Chem. Pbys. 60, 

p. 3310. 

Anderson, P. C., and H. J. Kurylo, 1979, J. Phys. Chem. 83, p. 2055. 

Andresen, P., A. Jacobs, C. K1einermanns, and J. Wolfrum, 1982, 19th Symp. 

(Int1.) Combustion, p. 11. 

149 

------, 

.. 

• 
) 

) 

-- ---- ------- ------ ------

Arnold,!., and -F. J. Comes, 1979, Chem. Phys. !t2., p. 231. 

Arrington, C. A., V. Brennen, G. P. Glass, J. V. Michael, and H. Niki. 1965, 

J. Chem. Phys. ~, p. 525. 

Aru~ov, V. S., L. S. Popov, and A. M. Chaikin, 1976, Kinet. Kata1. 17, 

p. 286. 

Ashford, R. D., N. Basco, and J. E. Hunt, 1978, Int. J. Chem. Kinet. 12, 

pp. 1233-1244. 

.. -- -- -- -- - .- - - .- -- .. 

Ashmore, P. G., and M. S. Spencer, 1959, Trans. Faraday Soc. 55, p. 1868. 

Atkinson, R., and J. N. Pitts, Jr., 1978, J. Chem. Phys. 68, p. 3581. 

--Atkiilson, R., and-So M. Aschmann, 1985, Int:- J.- Chem:-Xineti-cs li, pp. 33·41: 

Atkinson, R., D. A. Hansen, and J. N. Pitts, Jr., 1975, J. Chem. Phys. 63, 

pp. 1703·1706. ---_. --- -

Atkinson, -~ ,-R. A.Perry; and J. N; Pitts; Jr., 1977 , -;1. -Chem: Phys .---66, 

p. 1197. 

Atkinson, R., R. A. Perry, and J. N. Pitts, Jr., 1978. Chem. Phys. Lett. 54, 

p. 14. 

Atkinson, R., C. N. Plum, V. P. L. Cart~r, A. M. Viner, and J. N. Pitts, Jr., 

1984, J. Phys. Chem. 88, pp. 1210-15. 

Atkinson, R., E. C. Tuazon, H. Macleod, S. M. Aschmann, and A. M. Viner, 

1986, Geophys. Res. Lett. 11.-pP~ 117-120. 

Atkinson, R., S. M. Aschmann, E. C. Tuazon, M. A. Goodman. and A. M. Viner, 

1987, J. Atmos. Chem. 2, pp. 83-90. 

Avery, H. E., and R. J. Cvetanovic, 1965, J. Chem. Phys. ~,-pp. 3727·3733. 

Avramenko, L. 1., and R. V. Ko1esnikova, 1961, Bull. Acad. Sci. USSR Div. 

-Chem:-:-ScC, p. 545.- - - --- - -- - - -- - --

Bahta, A .• R. Simonaitis, and J. Heick1en, 1982, J. Phys. Chem. 86, p. 1849. 

Ba1akhnin. V. P., V. 1. Egorov, and E. I. Intezarova, 1971, Kinetics and 

Catalysis 11, p. 299. 

Baldwin, A. C., 

Functional Groups 

1982, "Thermochemistry of Peroxides," in Chemistry of 

(ed. S. Patai) , John \l11ey and Sons, Inc., New York. 

Baldwin, A. C., and D. M. Golden, 1978a, Chem. Phys. v-tt. 22, p. 350. 

Baldwin, A. C., and D. M. Golden, 1978b, J. Phys. Chem. .li. p. 644. 

150 

~ 

• 

• 
) 

---- / 

----I!t:...;.; ..:.,"':""_" _~ ____ _ .-----------.-----------.-~

) 

Baldwin, R. R., and C. E. Dean, M. R. Honeyman, and R. 1I. Ya1ker, 1984, 

J.C.S. Faraday I, ~, pp. 3187-3194. 

Ballash, N. H., and D. A. Armstrong, 1974, Speetrochim. Acta lQA, pp. 941-944. 

Bando, H., and C. J. Howard, 1987, J. Atmos. Chelll. (to be submitted). 

Barker, J. R., S. Y. Benson, and D. H. Golden, 1977, Int. J. Chem. Kinec. ~, 

p. 31. 

Barker, J. R., L. Brouwer, R. Patrick, H. J. Rossi, P. L~ Trevor, -and 

D. H. Golden, 1985, Int. J. Chem. Kinet. 11, pp. 991-1006. 

Sames,- L , __ Yo Bastian, K. H. Becker, E. H. Fink, and F. Zabel, 1981, Chem. 

Phys. Lett. lU, pp. 459-464. " 

Barnes, I., K. H. Becker, E. H. Fink, A. Reimer, F. Zabel, and H. Niki, 1983, 

Int . .J~_ Che_m. __ ~_n~~. _li, P? 631-645. 

Barnes, I. " V.' Bastlan, K.··· H. Becker, E;' H. Fink,- "and Y. Nelson, - 1986a,-

J. Atmos. Chem. ~, pp. 445-466. 

Barnes,!., V. Bastian, K. H. Becker, E. H. Fink, and F. Zabel, 1986b, 

Chelll. Phys. Lett. 121, pp. 28-32. 

Basco, N., and s. K. Dogra, 1971a, Proc. Roy. Soc. A. 323, p. 40l. 

Basco, N., and S. K. Dogra, 1971b, Proe. Roy. Soc. A. ill, p. 417. 

Basco, N., and S. K. 'Dogra, 1971c-, Proe. Roy. Soc. A. 323, p. 29. 

Basco, N, and J. E. Hunt, 1979, ht. J. Chem. Kinet. 11, p. 649. 

Basco, N., D. G. L. James, and F. C. James, 1972, Int. J. Chem. Kinet. !i, 

p. 129. 

Bass ... A •. H~o-and A ... E. J.edJord, 1978, pp. 282-284 in 12th Informal Conference 

_. ~ :---~ on Photochemistry, H. J. Kurylo and Y. Braun, Eds., -NBS ,- Spec: - Publ. 526, 

National Bureau of Standards, Gaithersburg, MD. 

Bass, A. H., A. E. Ledford and A. H. Laufer, 1976, J. Res. NBS ~, 

pp. 145-166. 

Bass, A. H., L. C. Glasgow, C. Miller, J. P. Jesson, and D. L. Filken, 1980. 

Planet. Space Sci. ~, p. 675. 

Batt, L., and G. N. Robinson, 1979, Int. J. Chelll. Kinet. li, p. 1045. 

Baulch, D. L., R. A. Cox, R. F. Hampson, Jr., J. A. Kerr, J. Troe. and 

R. T. Yatson, 1980, J. Pbys. Chelll. Ref. Data i, p. 295. 

Baulch, D. L., R. A. Cox, R. F. Hampson, Jr., J. A. Kerr, J. Troe, and 

R. T. Yatson, 1982, J. Pbys. Chem. Ref. Data 11, pp. 327-496. 

151 
) 

) 

r-------------

Bauleh, D. L., R.. J. B. Craven, K. Din, D. D. Drysdale, S. Grane, D. J_ 

Riehardson, A. Walker, and G. Watling, 1983, J. Chem. Soc., Faraday Trans. 1. 

li, pp. 689-698. 

Baulch, D. L., R. A. Cox, R. F. Hampson, Jr., J. A. Kerr, J. Troe, and 

R. T. Watson, 1984, J. Phys. Chem. Ref. Data 11, pp. 1259-1380. 

Baulch, D. L., I. M. Campbell, and S. K. Saunders, 1985, J. ~em. Soc •• 

Faraday Trans. 1, !l, p. 259. 

Beeker, -K. H., \I. _Groth,- and-D.-Z.-K1ey,--1969, Z. Naturforseh ill, p. 128(}._ 

Bemand, P. P., K. A. A. Clyne, and R. T. Watson, 1973, J. Chem. Soc. Faraday. 

Trans. I. ~, p. 1356. 

Bemand, P. P., K. A. A. Clyne, and R. T. \latson, 1974, J. Chem. Soe. Faraday. 

Trans. II 12, p. 564. 

Beno, M. F., C. D. Jonah, and \I. A. Ku1ac, 1985, Int. J. Chem. Kinet. 11-

pp. l091':ll~~:_ ----_ ~- ~ - - ~ ___ - - ______ _ 

Benson, S. 11., 1976, Thermochemical Kinetics, John llney and Sons, Inc .• 

New York, p. 292. 

Benson, S. Y., F. R. Cruickshank, and R. Shaw, 1969, Int. J. Chem. Kinet. 1. 

p. 29. 

Bhaskaran, K. A., P. Frank, and Th. Just, 1979, paper presented at 12th 

International Shock Tube Symposium, Jerusalem. 

Biaume, F., 1973, J. Photochem.-Z, p.n9. 

Biermann, H. Y., C. Zetzsch, and F. Stubl, 1978, Ber. Bunsenges. Phys. Chem_ 

~, p. 633. 

Biermann, H. 11., G. 11. Harris, and J. N. Pitts, Jr., 1982, J. Phys. Chem. 86. 

pp. 2958-2964. 

----- ----- - - . -- - - --- - Birks, J. W., B. Shoemaker, T. J. Leek, and D. M. Hinton, 1976, J. Chem. Phys_ -ll; p; 5181. 

Birks, J. Y., B. Shoemaker, T. J. Leck, R. A. Borders, and L. J. Hart, 1977. 

J. Chems. Phys. 66, p. 4591. 

Black, G., 1984, J. Chem. Phys. 80, pp. 1103-1107. 

Black, G., R. L. Sharpless, and T. G. Slanger, 1982a, Chem. Phys. Lett. 90. 

pp. 55-58. 

Black, G., R. L. Sharpless, and T. G. Slanger, 1982b, Chem. Phys. Lett. 93. 

pp. 598-602. 

152 

-
) 

; 

~"''; 

"~-\r -' -'-J."~ 

-) 

..... -- ...... -------_. -- .~ 

.:. 

~ 

Black, G., L. E. Jusinski, and T. G. Slanger, 1983, Chem. Phys. LeCC. lQl. 

pp. 64-68. 

Black, G., R. Pacrick, L. E. Jusinski, and T. G. Slanger, 1984, J. Chem. Phys. 

M, p. 4065. 

Boodaghians, R. B., 1. V. Hall, and R. P. Vayne, 1987, J. Chem. Soc., Faraday 

Trans. II ~, pp. 529-538. 

Borders, R. A.. and J. \l. Birks, 1982, J. Phys. Chem. M, pp. 3295-3302. - --- -- -- - .. 

Bozze11i, J. V., 1973, Ph.D. Thesis, Depc. of Chemiscry, Princeton University. 

(Diss. Abstr. InC. B, 34(2), p. 608). 

Bradley, J-. N. ,- V. Hack, K. Hoyermann, and H. Gg. Vagner, 1973-, -J. Chem. Soc.,-

Faraday Trans. 1. ~, p. 1889. 

Braithwaite, H., and S. R. Leone. 1978, J. Chem. Phys. .22, pp. 839-845. 

Braun, H., A. Hofzumahaus,-and-F. Stuh1,--1982, Ber. Bunsenges~ Phys. Chem. ~.-- -

pp. 597-602. 

Breckenridge, V. H., and H. Taube, 1970. J. Chem. Phys. 52. pp. 1713-1715. 

Breckenridge, Y. H., and T. A. Killer, 1972, J. Chem. Phys. 56, p. 465. 

Breen, J. E., and G. P. Glass. 1971, Int. J. Chem. Kinet. 1. p. 145. 

Brock, J. C., and R. T. \latson, 1980a, Chem. Phys. !&. pp. 477-484. 

Brock. J. C., and R. T. \latson, 1980b, Chem. Phys. Lett. 11. pp. 371-375. 

Brown. J. H •• and B. A. Thrush. 1967. Trans. Faraday Soc. 63. p. 630. 

Brown, R. D .• and 1. V. H4 Smith, 1975. Int. J. _Chem. Kinet. 1. p. 301. 

Brune, V. H., J. J. Schwab. and J. G. AnCerson. 1983, J. Phys. Chem. ~. 

4503-4514. - ---.- -----

Brunning, J .• and L. J. Stief. 1985. J. Chem. Phys. 83, pp. 1005-1009. 

Brunning. J.. and L. J. Stief. 1986a, J. Chem. Phys. 84, pp. 4371-4377. 

Brunning. J .• and L. J. Stief. 1986b. J. Chem. Phys. ~. p. 2591. 

Bulatov. V. P .• A. A. Buloyan. S. G. Cheskis. H. Z. Koz1iner. O. H. Sarkisov. 

and A. I. Trosti~. 1980. Chem. Phys. Lett. ~. p. 288. 

Bulatov, V. P., H. Z. Koz1iner, and O. H. Sarkisov, 1984, Khimi. Fiz. 1. 

pp. 1300-1305. 

Bulatov, V. P., H. Z. Kozliner. and O. H. Sarkisov, 1985, KhimL Fiz. ~. 

p. 1353. 

153 
) 

. / 

) 

'" ~~-: ---~ '-

Burkholder, J. B., and E. J. Bair, -1983, J. Phys. Chem. n. pp. 1859-1863. 

Burkholder, J. B., P. D. Hammer, and C. J. Howard. 1987. J. Phys. Chem. 91. 

pp. 2136-2144. 

Burrows, J. P., and R. A. Cox, 1981, J. Chem. S·,Jc., Faraday Trans. I 12. 

p. 2465. 

Burrows, J. P •• G. Y. Harris, and B. A. Thrush, 1977. Nature 267. pp. 233-234. 

Burrows. -J • P. ,.. D ~ I. Cliff, G •• y. .Harris., B •. A..Thrush. and J. P. T. 

Yi1kinson. 1979, Proc. Roy. Soc. (London) A368, p. 463-481. 

Burrows. J. P., 

_pp. 147-168. _ R. A. Cox, and R. G. Derwent, 1981, J. Photochem. 16. 

Burrows. J. P.. T. J. Ya11ington, and R. P. Yayne. 1983. J. Chem. Soc •• 

Faraday Trans. II ~. pp. 111-122. 

Burrows, J. P., T. J.yifHngton, and R. P. Yaine.1984a. J. Chem. Soc .• 

Faraday Trans. 2, M •. pp. 957:'971~-···--· 

Burrows. J. P .• G. S. Tyndall. and G. K. Hoortgat, 1984b. paper presented at 

the 16th Informal Conf. on Photochemistry. Boston, August 1984. 

Burrows. J. P .• D. W. T. Griffith. G. K. Hoortgat, and G. S. Tyndall. 1985a, 

J. Phys. Chem. 89. pp. 266-271. 

Burrows, J. P., G. S. Tyndall. and G. K. Hoortgat. 1985b, J. Phys. Chem. ~. 

pp. 4848-4856. 

Burrows, J. P., G. S. Tyndall, and G. K. Hoortgat. 1985c. Chem. Phys. Lett. 

~. pp. 193-198. 

Buss, R. J., R. J. Baseman, G. He, and Y. T. Lee. 1981, J. Photochem. 17. 

p. 389 • 

.. _Butler, P_.J._D.,_and_.L~F~_Phillip-s •. J.983, J. Phys. Ch!!m. li. pp:.183:1!!.4: __ 

Butler. R •• I. J. Solomon, and A. Snelson, 1978, Chem. Phys. Lett. 54, p. 19. 

Cadle. R. D., and J. y. Powers, 1967, J. Phys. Chem. 11. pp. 1702-1706. 

Callear. A. B., and I. y. K. Smith, 1967, Nature 213. p. 382. 

Callear, A. B., and R. E. K. Hedges. 1970, Trans. Faraday Soc. 66. p. 605 . 

Calvert, J. G., and J. N. Pitts, 1966a, Photochemistry. John ~i1ey & Sons. 

Inc., New York, pp. 230-231. 

Calvert, J. G., and J. N. Pitts, 1966b, op. cit., p. 783. 

154 

-----

--
) 

) 

--- ~ ".,---. ------ -_. _' -. -____ ______ (otCalvert, .J. G., and Y. R. Stockwell, 1983, in Acid Precipitation: S02' NO 

and tlO2 Oxidation Mechanisms; Atmospheric Considerations, Ann Arbor Sci. 

Publishers, Ann Arbor, Michigan. 

Cannon, B. D., .J. S. Robertshaw, I. Y. M. Smith, and K. D. Yilliams, 1984, 

Chem. Phys. Lett. 122, pp. 380-385. 

Cantrell, C. A., Y. R. Stockwell, L. G. Anderson, K. L. Busarow, D. Perner, 

A. Schme1tekopf, J. G. Calvert, and H. S. Johnston, 1985, J. Phys. Chem. 89, 

pp. 139-146. 

Cantrell, C. A., J. A. Davidson, K. L. Busarow, and J. G. Calvert, 1986, J. 

Geophys. Res. 21, pp. 5347-5353. 

CilntreU,.C. A., J. A. Davidson ... R. E. Shetter, B. A. Anderson and-J;G. 

Calvert, 1987, J Phys. Chem. 91, pp. 5858-5863. 

Car alp , F. and R. Lesc1aux, 1983, Chem. Phys. Lett. 102, pp. 54-58. 

C~;-a1p, F., R. Lesc1aux, and.A. M. Dognon, 1986_Chem. Phys •. Lett., 129, 

pp. 433-438. 

Carter, R. 0., and L. Andrews, 1981, .J. Phys. Chem. 85, p. 2351. 

Casavecchia, P., R. J. Buss, S. J. Sibener, and Y. T. Lee, 1980, .J. Chem. 

Phys. 73, pp. 6351-6352. 

Cattell, F. C., and R. A. Cox, 1986, J. Chem. Soc., Faraday Trans. 2, 82, 

pp. 1413-1426. 

Chan, Y. H., Y. H. Uselman, J. G. Calvert, and J. H. Shaw, 1977, Chem. Phys. 

Lett. 45, p. 240. 

Chang, J. S., and F. Kaufman, 1977a, .J. Chem. Phys. 66, p. 4989. 

Chang, J. S., and F. Kaufman, 1977b, Geophys. Res. Lett. !i, p. 192. 

_ Chang,. J_ S .• -and.. F.-Kaufman,--1978-, -J. Phys~ 9tem. 82, pp.-1683-1686:-

Chang, J. S., and J. R. Barker, 1979, .J. Phys. Chem. 83, p. 3059. 

Chang, J. S., A. C. Baldwin, and D. H. Golden, 1979a, J. Chem. Phys. 71, 

p. 2021. 

Chang, J. S., J. R. Barker, .J. E. Davenport, and D. H. Golden, 1979b, Chem. 

Phys. Lett. 60, pp. 385-390. 

Chang, J. S., P. L. Trevor, and J. R. Barker, 1981, Int. J. Chem. Kinet. 13, 

pp. 1151-1161. 

Chapman, C. J., and R. P. Yayne, 1974, Int • .J. Chem. Kinet. 2. pp. 617-630. 

155 

.. 

( 

U 
.F ,.~V'--'!"I. , --

) 

) 

\ 

___ '. ____ , __ ~~~_~IJ, 

Chen, H. L., D. V. Trainor, R. E. Center, and V. T. Fyfe, 1977, J. Chem. Phys. 

~, p. 5513. 

Cheng, B.-K., and Y.-P. Lee, 1986, Int. J. Chem. Kinet. la, pp. 1303-1314. 

Cheung, A. S. C., K. Yoshino, V. H. Parkinson, and D. E. Freeman, 1984, 

Geophys. Res. Lett. 11, p. 580. 

Cheskis, S. G., and O. K. Sarkisov, 1979, Chem. Phys. Lett • .22., p. 72. 

- Choo~ 'K. Y:, and- K. T. 'l.eu-; 1985~ J. Phys.- 'Cheli.-'l2.;- pp--;' ~832-4837. 

Chou, C. C., H. Vera-Rub;, K. Koe, and F.S. Rowland, 1976, unpublished 

results, University of California, Irvine. 

Chou, C. C., G. Crescentini, H. Vera-Ruiz, V. S. Smith, and F. S. Rowland, 

1977, "Stratospheric Photochemistry of CF20, CC1FO, and CCL20, " l73rd 

American Chemical Society Keeting, New Orleans, LA. 

Chou,-C.-C.,.R. J. Kilstein, V.,S. Smith,H. Vera-Ruiz,K. J. Kolina, and 

F. S. Rowland, 1978, J. Phys.·Chem. ~, p. 1. 

Clark, 1. D., and R. P. Vayne, 1970, Proc. Roy. Soc. ~, p. 539. 

Clark, J. H., C. B. Koore, and N. S. No gar , 1978a, J. Chem. Phys. 68, p. 1264. 

Clark, J. H., C. B. Moore, and J. B. Reilly, 1978b, Ine. J. Chem. Kinee. lQ, 

p. 427. 

Clark, R. H., D. Husain, and J. Y. Jezeque1, 1982,. J._.Ehotochem.....ll~ pp. 39-46. 

Clark, T. C., K. A. A. Clyne, and D. H. Stedman, 1966, Trans. Faraday Soc., 

.22" p. 3354. 

Clemo, A. R., F. E. Davidson, G. L. Duncan, and R. Grice, 1981, Chem. Phys. 

Lett. 84, pp. 509-511. 

-Clou~, ,P'-,-N., 'and _~:.'_A-;- Thrush-;--1967-, TranS'.· Far~day Soc.- ,§1,t>.-9l5. 

Clyne, M. A. A., and B. A. Thrush, 1961, Proc. Roy. Soc. A261, p. 259. 

Clyne, K. A. A., and H. V. Cruse, 1970a, Trans. Faraday Soc. ~, p. 2214. 

Clyne, M. A. A., and H. V. Cruse, 1970b, Trans. Faraday Soc. 66, p. 2227. 

Clyne, K. A. A., and H. V. Cruse, 1972, J. Chem. Soc., Faraday Trans. II ,§1!, 

p. 1281. 

Clyne, K. A. A., and R. F. Valker, 1973, J. Chem. Soc., Faraday Trans. I ~, 

p. 1547. 

Clyne, M. A. A., and S. Down, 1974, J. Chem. Soc., Faraday Trans. II 70, 

pp. 253-266. 

156 
) 

) 

" 

.. -_v,y~,-:', .......... --------

Clyne, H. A. A., and R. T. Vatson, 1974a, J. Chem. Soc., Faraday Trans. 1.22, 

p. 2250. 

Clyne, H. A. A., and R. T. Vat~on, 1974b, J. Chem. Soc., Faraday Trans. I 70, 

p. 1109. 

Clyne, H. A. A., and 1. S. KcDermid, 1975, J. Chem. Soc., Faraday Trans. I 11, 

p. 2189. 

Clyne, K. A. A., and L. V. Townsend, 1975, Int. J. Chem. Kinet. Symp. I, 

pp. 73-84. - - - - - - -- -- - --- - --.---

Clyne, H. A. A., and R. T. Vatson, 1975, J. Chem. Soc., Faraday Trans. 111, 

p. 336. 

- - --- - . 

Clyne, K. A. A., and V. S. -Nip, 1976a, J. Chem. Soc., Faraday Trans. II 72, 

p. 838. 

Clyne, K. A. A., and V. S. Nip, 1976~,_J. ~~!I.!._S()~._, Far!ld.ay Trans._ I 72, 

p. 2211.--

Clyne, K. A. A., and P. Honkhouse, 1977, J. Chrm. Soc., Faraday Trans. II 73, 

pp. 298-309. 

Clyne, K. A. A., and R. T. Vatson, 1977, J. Chem. Soc., Faraday Tran~. I 73, 

p. 1169. 

Clyne, M. A. A., and P. H. Holt, 1979a, J. Chem. Soc., Faraday Trans. II 75, 

pp. 569-581. 

Clyne, K. A. A., and P. H. Holt, 1979b, J. Chem. Soc., Faraday Trans. II 75, 

pp. 582-591. 

Clyne, K. A. A., and P. D. Yhitefield, 1979, J. Chem. Soc., Faraday Trans. II 

n, p. 1327. 

Clyne, M. A. A., and A. J. KacRobert, 1980, Int. J. Chem. Kinet. 12, pp. 79-96. 

-. - - --- Clyne, K. A. A., and-A. J~KacRobert, 1981, Int. J. Chem. Kinee-; l3; .pp. 187-

197. - - - --

Clyne, M. A. A., and Y. Ono, 1982, Chem. Phys. 69, pp. 381-388. 

Clyne, H. A. A., and Y. Ono, 1983, Chem. Phys. Lett. 94, pp. 597-602. 

Clyne, M. A. A., B. A. Thrush, and R. P. Vayne, 1964, Trans. Faraday Soc. 60, 

p. 359. 

Clyne, H. A. A., C. J. Halstead, and B. A. Thrush, 1966, Proc. Soc. London, 

Ser. A. 222, p. 355. 

Clyne, M. A. A., D. J. McKenney, and R. F. Valker, 1973, Can. J. Chem. 51, 

p. 3596. 

157 

---:=--~ 

-"I 

~ 

, .. 
, ." 

>'" 

) 

--

-. 

--'-_.-

'-.. " 

.. ~;.---

-. 

-:---........-:-

) 

.-----

-~ .. :.- -.---.. 

" ... -.. :""- ,...---

Clyne, K. A. A., P. B. Konkhouse, and L. V. Townsend. 1976. Int. J. Ch~m. 

Kinet. ~. p. 425. 

Clyne. K. A. A., A. J. KacRobert. T. P. Murrells. and L. J. Stief. 1984, J. 

Chem. Soc. Faraday Trans. 2. 80, pp. 877-886. 

Cobos. C. J., H. Hippler, and J. Troe, 1985, J. Phys. Chem. 89, 342-9. 

Cobos, C. J .. H. Hippler. K. Luther, A. R. Ravishankara, andJ. Troe. 1985. 

J. Phys. Chem., 89, pp. 4332-4338. 

Cocks, A. T., R. P. Fernanado, and 1. S. Fletcher. 1986. Amos. Environ. lQ. 

pp. 2359-2366. 

CODATA, __ 1980, Evaluated Kinetic and Photochemical Data for AtlIOspheric Chem--· -- -

istry, J. Phys. Chem. Ref. Data i, pp. 295-471. 

CODATA, 1982, Evaluated Kinetic and Photochemical Data for AtlIOspheric Chemistry, Suppleme~t I. J.Phys. Chem. Ref. Data 11. pp. 327-496. 

CODATA, 1984, Evaluated Kinetic and Photochemical Data for Aaospheric Chemistry, Supplement II. J. Phys. Chem. Ref. Data 13, pp. 1259-1380. 

Connell, P. S .• and H. S. Johnston, 1979, Geophys. Rev. Lett. 2. p. 553. 

Connell. P. S .• and C. J. Howard. 1985, Int. J. Chem. Kinet. 17. p. 17. 

Cook, J. L., C. A. Ennis, T. J. Leck, and J. W. Birks, 1981a. J. Chem. Phys. 

E. p. 545. 

Cook, J. L .• C. A. Emlis. T. J. Leck, and J. W. Birks. 1981b. J. Chem. Phys. 

75. p. 497. 

Cooper, R., J. B. Cumming, S. Gordon, and V. A. Kulac. 1980. Radiat. Phys. 

Chem. 16, 169. 

Cox, R. A., 1975. Int. J. Chem. Kinet., Symp. 1. p. 379. 

Cox. R. A., 1980. Int. J. Chem. Kinet; 12. p; -649. 

Cox. R. A., and .J. P. Burrows, 1979, J. _Phys. -Chem. 83, p. 2560-2568 • 

Cox, R. A .• and R. Lewis, 1979. J. Chem. Soc •• Faraday Trans. I 75, p. 2649. 

Cox. R. A., and R. Patrick. 1979, Int. J. .Chem. Kinet. 11. p. 635. 

Cox, R. A .• and R. G. Derwent, 1979, J. Chem. Soc. Far. Trans. 1 75. pp. 1635-1647. 

Cox. R. A •• and G. Tyndall. 1979. Chem. Phys. Lett. ~. p. 357. 

Cox. R. A .• and D. Sheppard. 1980. Nature 284. pp. 330-331. 

158 

. --- ... -~:-,,-- -----. -- --.- ---- ''7_~ ="""'""""- _ .. --" - --~ =-~ - =:;---:;: -- .", .. ' 

'-iii. 

i_~ 

i£-
) 

1..-

-.:,. .: 

;..-.. " 

---

-- ) 

Cox, R. A., and G. S. Tyndall, 1980, J. Chem. Soc., Faraday Trans. II ~, 

p. 153. 

Cox, R. A., and D. W. Sheppard, 1982, J. Chem. Soc., Faraday Trans. II 78, 

pp. 1383-1389. 

Cox, R. A., and G. D. Hayman, 1987, manuscript in preparation. 

Cox, R. A., R. G. Derwent, and P. H. Holt, 1975, Chemosphere ~, p. 201. 

Cox, R. A., R. G. Derwent, A. E. J. Eggleton, and J. E. Lovelock, 1976a, 

Amos. Environ. lQ,-p. 30S. 

Cox, R. A., R. G. ~erwent, and P. H. Holt, 1976b, J. Chem. Soc., Faraday 

Trans. I 11, p. 2031. 

Cox, R. A., R. G. Derwent, A. E. J. Eggleton and H. J. Read, 1979, J. Chern. 

Soc., Faraday Trans. I 75, pp. 1648-1666. 

Cox, R. A., R. G. Derwent, S. V. Kearsey, L. Batt, and K. G. Patrick. 1980, 

J. Photochem. il, -po i49. . _ . ___ _ .' . - -- - _. ------

Cox, R. A., J. P. Burrows, and T. J. Wallington, 1981, Chem. Phys. Lett. 84, 

p. 217-221. 

Cox, R. A., D. W. Sheppard, and H. P. Stevens, 1982, J. PhotocheCi. 19. 

pp. 189-207. 

Cox, R. A., R. A. Barton, E. Ljungstrom. and D. W. Stocker, 1984a, Chem. Phys. 

Lett. 108, pp. 228-232. 

~OX, R. A., J. P. Burrows, and G. B. Coker, 1984b, Int. J. Chern. Kinet. 16. 

pp. 445-67. 

Cox, R. A., H. Fowles, D. Houlton, and R. P. Wayne, 1987, J. Phys. Chem. 91. 

pp. 3361-3365. 

Coxon, J. A., W. E. Jones and D. A. Ramsey, 1976, 12th International Symposium 

on. Free. Radicals, _l.a5.ma Beach,. Cal ifornia. 

Croce de Cobos, A. E., H. Hippler. and J. Troe, 1984. J. Phys. CheCi. 88. 

pp. 5083 - 5086. 

Cupitt, L. T., and G. P. Glass. 1975, Int. J. Chem. Kinet., Symp. 1. pp. 39-50, 

Dagaut, P., T. J. Wallington, and H. J. Kurylo, 1987, submitted to J, 

Phys. Chem. 

Daidoji, H., 1979, Bunseki Kagaku lR, p. 77. 

Dasch, W., K.-H. Steinberg, and R. N. Schindler, 1981, Ber. Bunsenges. Phys. 

Chem. ~, p. 611. 

159 

--~ --- --.. -- . .-:.. -~ -- -.-::-"--",..;"" -.-

-'~'.-- . . ~-.. 

.... --~ 

• 

~ 

· 

• 

, 

.:. 

i 

.. 

;t 
) 

) 

Daubend1ek,_ R. L., and J. G. Calvert, 1975. Environ.Lett~ ,!t, p.l03. 

Davenport, J. E., 1978, 

Stratospheric Modeling,-

-Detemination of N02 Photo1yab Parameters for 

Report No. FM-EQ-78-14, FAA, Washington, D.C. 

Davenport, J. E., B. Ridley, H. 1. Schiff, and K. H. Welge, 1972, J. Chem. 

Soc., Faraday Discussion, ~, pp. 230-231. 

Davidson, F. E., A. R. Clemo, G. L. Duncan. R. J. Brovett, J. H. Hobson. and 

R. Grice, 1982, Mo1ec. Phys. ~, pp. 33-40. 

Davidson, J. A.--; H. 1. Schiff. G; E: Stre1t~-J. R~ McAfee. A. L. Scluie1tekopf. 

and C. J. Howard. 1977, J. Chem. Phys. ~, pp. 5021-5025. 

Davidson. J. A., H. 1. Schiff, T. J. Brown. and C. J. Howard. 1978. J. Chem. 

Phys. ~. pp.- 4277-4279. 

Davidson, J. A., C. J. Howard, H. 1. Schiff. and F. C. Fehsenfeld. 1979. J. 

Chem. Phys. 12, pp. 1697-1704. 

Davidson, J. _A., ~. Ao- Cantrel1.-_S. C. Tyler. R. -E. Shetter, R. J. Cicerone,-

and J. G. Calvert, 1987, J. Geophys. Res. 21, pp. 2195-2199. 

Davies, P. B., and B. A. Thrush, 1968, Trans. Far. Soc. 64. p. 1836. 

Davis, D. D., W. Braun, and A. M. Bass, 1970, Int. J. Chem. Kinet. 1, p. 101. 

Davis, D. D., R. B. Klemm, and M. Pilling, 1972, Int. J. Chem. Kinet. 4, 

367-382. - -

Davis, D. D., J. T. Herron, anc R. E. Huie, 1973a, J. Chem ._Phys. 58, p----530~ 

Davis, D. D., W. Wong, and J. Lephardt, 1973b, Chem. Phys. Lett. 22, pp. 273· 

278. 

Davis, D. D., S. Fischer, and R. Schiff, 1974a, J. Chem. Phys. ~, pp. 2213-

2219. 

Davis, D. D.-, J-. ·Prusazcyk, H. Dwyer, and P. Kim., 1974b, -J .-Phys. Chem-. -78, - - pp. 1775_-1779. -- - . --

_ Davis, D. D., Y. Yong, and R .. Schiff, 1974c, J. Phys. Chem. 78, pp. 463-464. 

Davis. D. D., S. Fischer, R. Schiff, R. T. Yatson, andW. Bo11ing~r, 1975. J. 

Chem. Phys. 63, p. 1707. 

Davis. D. D., G. Machado, B. Conaway, Y. Oh, and R. T. Yatson, 1976, J. Chem. 

Phys. 22, p. 1268. 

DeMore, Y. B., 1979, J. Phys. Chem. 83, pp. 1113-1118. 

DeMore, Y. B., 1981, results presented at 182nd National Keeting, American 

Chemical Society, New York, August, 1981. 

160 

-------=----..._---=.:.. . ---- -.- ..... ...-: 

~ 

• 

~-J.--

~ 
) 

/. 

-_'._._ 5 

, 

, 

I 

r 

t 

DeMOre. V. B •• 1982. J. Phy •• Chem. 12. pp. 12r-126. 

DeMore. V. B •• 1984. Int. J. Chem. Kinet. 12. pp. 1187-1200. 

DeMore. V. B •• and E. Tschuikow-Roux. 1974. J. Phys. Chem. H. pp. 1447-1451. 

DeMore. V. B •• C. L. Lin. and S. Jaffe. 1976. -12th Inforaal Conference on 

Photochemistry-. K. J. Kurylo and V. Braun. Eels •• NBS Spec. Publ. 526 (1978), 

pp. 287-289. 

_D.eMore. V. B •• L. J._ Stief. F_ Kaufman,.. .D. K. -Golden. Rr F. Hampson. K. J. 

Kurylo. J. J. l-largitan. K. J. Kolina. and R. T. Vatson. 1979. JPL Publication 79-27. Jet Propulsion LaboratorY. California Institute of Technology, 

Pasadena. CA. 

DeMore. -V~-B •• D-:-K. Golden. R. F. Hampson.·-K~ J. Kurylo. J. J. Margitan. 

K. J. Kolina. L. J. Stief. and R. T. Vatson. 1981, JPL Publication 81-3. 

Jet Propulsion Laboratory, Ca1ifomia Institute of Technolo&y. Pasadena. CA. 

DeKore. V. B •• D. K. Golden. R. F-. Hampson. C. J. Howard. K. J •. Kurylo. K. J. 

Kolina, A.R. Ravisharucara.- and-a:- -T:-- Vatson, . 1982. JPL PiiDn:cation 82-57, 

Jet Propulsion Laboratory. Califomia Institute of Technolo&y, Pasadena, CA. 

DeKore, W. B., D. K. Golden, R. F. Hampson, C. J. Howard. K. J. Kurylo, K. J. 

Kolina. A. R. Ravishanka~a. and R. T. Vatson. 1983. JPL Publication 83-62, 

Jet Propulsion Laboratory, Califomia Institute of Technology, Pasadena. CA. 

DeKore, V. B .• D. K. Golden, R. F. Hampson, C. J. Howard, K. J. Kurylo, 

J. J. Hargitan. K. J~ Kolina, A. R. Ravlshankara, and R. T. Watson, 1985, 

JPL Publication 85-37, Jet Propulsion Laboratory, California Institute of 

Technology, Pasadena, CA. 

Devolder. P., M. Carlier, J. F. Pauwels and L. R. Sochet, 1984. Chem. Phys. 

Lett. lll. pp. 94-9. 

Dobe, S .• F. Temps. T. Bohland. and H. Gg. Wagner, 1985, Z. Saturforsch. 40a, 

pp. 1289-1298. 

Dodonov, A. F;. G-. K. -Lavrovskaya, I~ 1. -Korozov, and V. L.·TaP-rose, 1971, 

Dok1. Adak. Nault USSR. 198, 662: Dokl. Phys. Chem. (Engl. Trans). 198, p. 440. 

Dodonov, A. F .• V. V. Zelenov; A. S. Kukui, E. A. Ponomarev. a::dV-.-L. Tal'Rose, 

1985, Khim. Fiz. ~. pp. 1335-1343. 

Dognon. A. M., F. Caralp, and R. Lesclawc, 1985, J. Chim. ?hys. Phys. -Chim. 

BioI. ~. pp.349-352. 

Dolson, D. A., 1986, J. Phys. Chem. 2Q, pp. 6714-6718. 

Donovan, R. J., and D. J. Little, 1972, Chem. Phys. Lett. li, -po 488. 

Dreier, T., and J. Wolfrum, 1980, 18th International Sympos~ on Combustion, 

pp. 801-809. 

161 

1 , 

I 

I 

~ 
,--~ 

) 

-, 

) 

--... ----.~ 

Droege, A. T., andF"". P. Tully, 1986, J. Phys. Chem. 22, pp. 1949-1954. 

Eibling, R. E., and H. Kaufman, 1983, Atmos. Environ. 17, pp. 429·431. 

Ennis, C. A., and J. W. Birks, 1985, J. Phys. Chem. 89, pp. 186-191. 

Ennis, C. A., and J. W. Birks, 1987, manuscript submitted to J. Phys. Chem. 

Fair, R. W., and B. A. Thrush, 1969, Trans. Faraday Soc. 65, p. 1557 . 

. ~air., ~W., A. van Roodae1aar, and-O. P.-Strausz, 1971, Can.-J. Chem.!d, 

p. 1659. 

Fairchild, C. E., E. J. Stone, and G. H. Lawrence, 1978, J. Chem. Phys. £2, 

pp. 3632-3638. 

Farquharson, G. K., and R. H. Smith, 1980, Aust. J. Chem. 33, pp. 1425-1435. 

Fasano, D. H., and N. S. Nogar, 198!_, Int. J. Chem. Kinet. 13, p. 325. 

Fasano, - D. H. ,and N. S. Nogar; -1982-:-Chem~ Phy~·. Lett. 92, pp. 411·414. 

Fa3ano, D. H., and N. S. Nogar, 1983, J. Chem. Phys. 78, pp. 6688-6694. 

Fergusson, W. C., L. Slotin, and W. G. Style, 1936, Trans. Far. Soc. 32, 

p. 956. 

Finlayson-Pitts, B. J., and T. E. Kleindienst, 1979, J. Chem. Phys. 70, 

pp. 4804-4806. 

-F-in1ayson--Pitts, B. J., T. E. Kleindienst, J. J. Ezell, andD. W. Toohey. 1981, 

J. Chem. Phys. 74, pp. 4533-4543. 

Fletcher, I. S. , and D. Husain, 1976a, Can. J. Chem. 54, pp. 1765-1770. 

Fletcher, I. S. , and D. Husain, 1976b, J. Phys. Chem. 80, pp. 1837-1840. 

Fletcher,!. 5., ~md p._liusain,-1978, J. Photochem.--~, pp. -355·361. 

Foon, R., and G. P. Reid, 1971, Trans. Faraday Soc. 67, p. 3513. 

Foon, R.,· and H. Kaufman, 1975, Progress Reaction Kinetics ~, p. 81. 

Foon, R., G. LeBras, and J. Combourieu, 1979, C.R. Acad. Sci. Paris, Series C, 

288, p. 241. 

Force, A. P., and J. R. Wiesenfe1d, 1981a, J. Phys. Chem. 85, pp. 782-785. 

Force, A. P., and J. R. Wiesenfe1d, 1981b, J. Chem. Phys. 74, pp. 1718-1723. 

Fowles, H., D. N. Hitche11, J. W. L. Horgan, and R. P. Wayne, 1982, J. Chern. 

Soc., Faraday Trans. II ~, p. 1239. 

162 

{~ 

~ 
) 

)-

Frederick, J. ~., and R. D. Hudson, 1979, J. Atmos. Sci. 36, pp. 737-745. 

Frederick, J. E., and R. D. Hudson, 1980, J. Atmos. Sci. 11, pp. 1099-1106. 

Frederick, J. E., and J. E. Menta11, 1982, Geophys. Res. Lett. ~, pp. 461-464. 

Freeman, C. G., and L. F. Phillips, 1968, J. Phys. Chem.· 11, p. 3025. 

Freudenstein, K., and D. Biedenkapp, 1976, Ber. Bunsenges. Phys. Chem. 80, 

pp_ 42-48. 

Friedl, R. R., W. H. Brune, and J. G. Anderson, 1985, J. Phys. Chem. ~, 

pp. 5505-5510. 

Friedl, R. R., J. H. Goble, anctS. P. _Sander, 1986, Geophys. Res. Lett_ 13, 

pp_ 1351-1354. 

Fritz, B., K. Lorenz, W. Steinert and R. Zellner, 1984, Oxidation Communications, Vol. 6, pp. 363-370. 

Frost; . R. J., D. S. Green, M. K. Osborn, and 1. W. M. Smith, 1986, Int:. J. 

Chem. Kinet:. 18, pp. 885-898. . 

Gardner, E. P., P. D. Sperry, and J. G. Calvert, 1987, J. Geophys. Res. 92, 

pp. 6642-6652. 

Garvin, D., and H. P. Broida, 1963, 9th Symposium on Combustion, p. 678. 

Geers-Muller, R., and F. Stub1, 1987, Chem. Phys. Lett. 135, pp. 263-268. 

Gehring, M~, x. Hoyermann, H. Sahaeke, and J. Wolfrum, 1973, 14th Int. 

Symposium on Combustion, p. 99. 

Gericke, K.-H., and F. J. Comes, 1981, Chem. Phys. Lett. 81, pp. 218-222. 

Gibson, G. E., and N. S. Bayliss, 1933, Phys. Rev. 44, p. 188. 

qi11, R. J.,.W. 0 ... Johnson, _and G ... 1LAtkinson, 1981, Chem. Phys.·Sa, p. 29; 

Gio1ando, D. M., G. B. Fazekas, Y. D. Taylor, and G. A. Takacs, 1980, J. 

Phot:ochem. 14, p. 335. ___ _ 

Glaschick-Schimpf, I., A. Leiss, P. B. Monkhouse, U. Schurath, K. H. Becker, 

and E. H. Fink, 1979, Chem. Phys. Lett. 67, pp. 318-323. 

Gleason, J. F., and C. J. Howard, 1987, J. Phys. Chem., in press. 

Gleason, J. F., A. Sinha, and C. J. Howard, 1987, J. Phys. Chem. 91, 

pp. 719-724. 

Glinski, R. J., and J. W. Birks, 1985, J. Phys. Chem. 89, pp. 3449-3453 and 

Erratum: 1986, J. Phys. Chem. 90, p. 342. 

16.) 

-.---~ 

, . 

. . ~ 

~ 
r_ '. 

) 

---

/)' 

C-oodeve, C. F., and F. D. Richardson, 1937, Trans. Faraday. Soc. n, 

pp. 453-457. 

Gordon,S., W. Ku1ac, and P. Nangia, 1971, J •. Phys. Chem. 12, p. 2087. 

Graham, R. A., 1975, "Photochemistry of N03 and the Kinetics of the N205-03 

System,· Ph.d. Thesis, University of California, Berkeley. 

Graham, R. A., and H. S. Johnston, 1974, J. Chem. Phys. 22, p. 4628 . 

. . Graham, __ R __ A.,. -and D. J. Gutman,. 1977, J.- Phys-.· Chem. n,·· p .. 201. 

Graham, R. A., and H. S. Johnston, 1978, J. Phys. ~em. n, pp. 254-268. 

Graham, R. A., A. K. Winer, _and J. _N .• Pitts., Jr., 1977, Chem. Phys. Lett. 21. 

-p. 215.· 

Graham, R. A., A. K. Winer, and J. N. Pitts. Jr •• 1978a. J. Chem. Phys. ~, 

PI? 4505-4510_. 

Graham,R. A., A."Ii. Winer~ andJ. N. Pitts·, -Jr~,-i978b;" Geophys. Res. Lett. 

2" p. 909. 

Graham, R. A., A. K. Winer, R. Atkinson, and J. N. Pitts, Jr., 1979, J. Phys. 

Chem. 83, p. 1563. 

Green, R. G., and R. P. Wayne, 1976/77, J. Photochem . .2" pp. 375-377. 

Greiner, N. R., 1969, J. Chem. Phys. 2.1, pp. 5049-5051. 

Greiner, -w. ·R., 1970a, J. Chem. Phys. il, p. 1284. 

Greiner, N. R., 1970b, J. Chem. Phys. 53, pp. 1070-1076. 

Grimley, A. J., and P. L. Houston, 1980, J. Chem. Phys. 11, pp. 1471-1475. 

Grotheer, H. H., R. Gottfried, V. Keier, and T. Just, 1985, Ber. Bunsenges . 

. Phy's. Chem. 89, pp. _18'Z~191. . __ ._ 

Gutman, D., N. Sanders, and J. E. Butler, 1982, J. Phys. Chem. 86, p. 66. 

Hack, Y., and H. Kurzke, 1985, Ber. Bunsenges. Phys. Chem. ~, pp. 86-93~ 

Hack, W., K. Hoyermann, and H. Gg. Wagner, 1974, Ber. Bunsenges. Phys. Chem. 

78, p. 386. 

Hack, Y., G. Kex, and H. Gg. Wagner, 1977, Ber. Bunsenges. Phys. Chern. 81, 

pp. 677-684. 

Hack, W., H. Gg. Wagner, and K. Hoyermann, 1978, Ber. Bunsenges. Phys. Chern. 

~, pp. 713-719. 

164 

~ 

.t' 

~ 
r .. i 

) 

) 

) 

Hack, Y., A. Y. Preuss, F. Temps and H. Gg. Vagner, 1979a, Ber. Bunsenges. 

Phys. Chem. ~, pp. 1275-1279. 

Hack, Y., H. Scbacka, K. Schroter, and H. Gg. Vagner, 1979b, 17th Int. Symp_ 

on Combustion, p. 505. 

Hack, Y., A. V. Preuss, H. Gg. Vagner, and K. Hoyermann, 1979c, Ber. Bunsenges. 

Phys. Chem. ~, pp. 212-217. 

Hack, Y., A. V. Preuss, F. Temps, H. Gg. Vagner, and K. Hoyermann, 1980, Int_ 

-,J. Chem. Kinet.-l:2.,--pp-;-851-860. - - - --

Hack, Y., o. Horie, and H. Gg. Yagner, 1981, Ber. Bunsenges. Phys. Chem. ll .. p. 72. 

Hack, V., o. Horie, and H. Gg. Yagner, 1982, J. Phys. Chem. 86, p. 765_ 

Hall, J. L., D. Zeitz, J. V. Stephens, J. V. V. Kasper, G. P. Glass, R. F _ __ _ Curl, _and F. K. ~it:te1, 1986, J. Phys. Chem. 90, pp. 2501-2505. 

--Halstead, C. J. and B. A. Thrush, 1966, Proc. Roy. Soc. London, Ser. A, 295" 

p. 380. 

Hamilton, E. J., Jr., 1975, J. Chem. Phys. ~, pp. 3682-3683. 

Hamilton, E. J., Jr., and R. -R. Lii, 1917, Int. J. Chern. Kinet. 2., pp. 875-885_ 

Hammer, P. D., E. J. D1ugokencky, and C. J. Howard, 1986, J. Phys. Chem. 90 .. 

pp. 2491-2496. 

Hampson, R. F., Jr., and D. Garvin, Eds., 1977, Reaction Rate and Photochemical 

Data for Atmospheric Chemistry, National Bureau of Standards Special Pub. 513. 

p. 33, Yashington. D.C. 

Hancock, G., V. Lange, K. Lenzi, and K. H. Ve1ge, 1975, Chem. Phys. Lett. 33. 

p. 168. . 

_Handwerk, V. , 

pp. 1161-1166. 

and . R. -Zellner, -1978,- Ber.- - Bunsenges. Phys-. Chem. -ll. 

Handwerk, V., and R. Zellner, 1984, Ber. Bunsenges. Phys~ Chem. 88, p. 405. 

Harker, A. B., Y. Ho, and J. J. Ratto, 1977, Chem. Phys. Lett. 2Q, 394-397. 

Harris, G. Y., and R. P. Yayne, 1975, J. Chem. Soc., Faraday Trans. I 11, 

p. 610. 

Harris, G. Y., T. E. Kleindienst, and J. N. Pitts, Jr., 1981, Chem. Phys. 

Lett. ~, pp. 479-483. 

Hatakeyama, S., and K. T. Leu, 1986, Geophys. Res. Lett. 11, pp. 1343-1346. 

165 

~ 
J 

) 

~-\' 

Hayman, G. D., J. K. Davies, and R. A. Cox, 1986, Geophys. Res. Lett. 13, 

pp. 1347-1350. 

Hearn, A. G., 1961, Proc. Phys. Soc. London, Ia, pp. 932-940. 

Heick1en, J., N. Kelly, and K. Partymi11er, 1980, Rev. Chem. Intermediates 2, 

pp. 315-404. 

Heidner, R. F., III, and D. Husain, 1973, Int. J. Chem. Kinet. 2, pp. 819-831. 

Heidner, -R.-- F. -, --Ill r D-. --Husain, and J. R. Veisenfe1d, 19-73, J; - Chem. Soc.-, -

Faraday Trans. 11 69, pp. 927-938. 

Heidner, R. F., J. F. Bott, C. E. Gardner, and J. E. Helzer, 1979" J. CheCII. 

Phys. 70,_p. 4509. 

Heidner, R. F., J. F. Bott, C. E. Gardner, and J. E. Helzer, 1980, J. Checa. 

Phys. 11, p. 4815. 

H~~eg!!an, S.~.-,--~nd S. V. Be?Son, 1983, Int. J_. Chem. ~i!le~~ 15!. pp_~ 1311-1319. 

Heneghan, S. P., P. A. Knoot, and S. \l. Benson, 1981, Int. J. Chem. Kinet. 12, 

p. 677. 

Herman, J. R., and J. E. Henta11, 1982, J. Geophys. Res. ~, pp. 8967·8975. 

Herron, J. T., and R. D. Penzhorn, 1969, J. Phys. Chem. n, p. 191. 

Herzberg, G., and K. K. Innes, 1957, Canad. J. Phys. 35, p. 842. 

Hills, A. J., and C. J. Howard, 1984, .T. Chem. Phys. 81, pp. 4458·65. 

Hills, A. J., R. J. Cicerone, J. G. Calvert, and J. V. Birks, 1987, Nature 

328, pp. 405-408. 

Hislop, J. R., and R. P. \layne, 1977, J.C.S. -Faraday II n, pp. 506-516. 

________ Jijort:h, J.,.G. Ottobrini, and G. Reste11i,_19_86, __ Int .. J. Chem. Kinet.. 1~, 

pp. 819-828 

Hjorth, J., G. Ottobrini, F. Cappe1lani, and G. Reste11i, 1987._J. Phys. Che~. 

21, pp. 1565-1568. 

Ho chanade 1 , C. J., J. A. Ghormley, and P. J. Ogren, 1972. J. Chem. Phys. S? 

pp. 4426-4432. 

Hochanadel. C. J., J. A. Ghormley. J. Y. Boyle. and P. J. Ogren. 1977. J. 

Phys. Chem. ~, p. 3. 

Hochanadel. C. J., T. J. Sworski and P. J. Ogren, 1980. J. Phys. Chem. 84, 

Pl>. 3274-3277. 

166 

~ 
) 

) ..-;. 

':} 

./ 

Hofmann-Sievert, R., and A. W. Cast1eman~ 1384, J. Phys. Chem. ~. pp. 3329-

3333. 

Hofzumabaus, A., and F. Stuh1, 1984, Ber. Bunsenges, Phys. Chem. 88, pp. 557-

561. 

Ho11inden, G. A., K. J. Kurylo, and R. B. Timmons, 1970, J. Phys. Chem. 74. 

pp. 988-99l. 

Homann, K. H., G. Krome, and H. Gg. Wagner, 1968, Ber. Bunsenges. Phys. Chem_ 

11, p. 9.~8. _____ _ 

Horowitz, A., and J. G. Calvert, 1978, Int. J. Chem. Kinet. 10, p. 805_ 

Horowitz, A., F. Su, and J. G. Calvert, 1978, Int. J. Chem. Kinet. 10, p. 1099_ 

Howard, C. J., 1976, J. Chem. Phys. 65, p. 4771. 

Howard, C. J., 1977, J. Chem. Phys. 67, p. 5258. 

Howard; C~ J-., 1979,-J-. -Chem. Phys. 71, pp. 2352- 2359. -- - - --~.--

Howard, C. J., 1980, J. Am. Chem. Soc. 102, pp. 6937-6941. 

Howard, C. J. , and K. M. Evenson, 1974, J. Chem. Phys. 61, p. 1943._ 

Howard, C. J. , and K. M. Evenson, 1976a, J. Chem. Phys. 64, p. 197. 

Howard, C. J. , and K. M. Evenson, 1976b, J. Chem. Phys. .2!t., p. 4303._ 

Howard, C. J., and-K. -K. Evenson, 1977, Geophys. Res. Lett. !, pp. 437-440_ 

Howard, C. J. , and B. J. Finlayson-Pitts, 1980, J. Chem. Phys. n, pp3842-3843. 

Howard, K. J., and 1. Y. K. Smith, 1981, J. Chem. Soc., Faraday Trans. II 77, 

pp. 997-1008. 

--·--Hoyermann,-K., -H. -G._Yagner, and J:- Wolfrum, -1967; Z-; -Phys.-Chem. -55,-p_ 72. 

Hoyermann, K., H. G. Yagner, and J. Wolfrum, 1969, Z. Phys. Chem. 21, p. 193. 

Hsu, D. S. Y., Y. K. Shaub, T. L. Burks, and K. C. Lin, 1979, Chem. Phys. 4~, 

pp. 143-150. 

Hsu, K. J., J. L. Durant, and F. Kaufman, 1987a, J. Phys. Chem. 21, pp. 1895-

1899. 

Hsu, K. J., S. M. Anderson, J. L. Durant, and F. Kaufman, 1987b, J. Phys. Chem_, 

accepted for publication. 

Hubrich, C., and F. Stuh1, 1980, J. Photochem. 11, pp. 93-107. 

167 
F.. .... \. 

) 

- ,..,-

) ) 

Hubrich, C., C. Zetzsch, and F. Stubl, 1977 ... Ber. Bunsenges. ·Phys. Chem. n, 

p. 437. 

Hudson, R. D., and L. 3. Kieffer, 1975, -Absorption Cross Sections of stratospheric Molecules,· The Natural Stratosphere of 1974, ClAP Monograph I, 

pp. (5-156)-(5-194). 

Huie, R. E., and J. T. Herron, 1974, Chem. Phys. Lett. ll, p. 411. 

Huie, R. E., and P. Neta, 1984, 3. Phys. Chem. ~, pp. 5665-5669. 

Hunten, D. M:; R: 'p'. 'Turco ,- and (f. -B:"Toon, 1980, J. Atmos. nScL li, p. 1342-.. 

Hunziker, H. E., H. Kneppe, and H. R. Wendt, 1981, J. Photochem. 11, p. 377. 

Hus·ain-,-D., and N. K: H; Slater,"1980, J. Chem.- Soc., Faraday.Trans. II 1..&., 

pp. 606-619. '. 

Husain, D., and P. Marshall, 1985, Combust. and Flame 60, pp. 81-87. 

Husain, D.,3-.-M~-C. Plane-,-andN. K. H_.S1ater, 1981, J. Chem. Soc., Faraday Trans. II n, p. 1949. - '. - ---- '--. 

Husain, D., 3. H. C. Plane, and C. C. Xiang, 1984, J. Chem. Soc. Faraday Trans, 

2, 80, pp. 713-728. 

Husain, D., P. Marshall, and J. M. C. Plane, 1985, J. Chern. Soc. Chern. Co~~. 

1985, pp. 1216-1218. 

Hynes, A. J., P. H. Wine, and A. R. Ravishankara, 1986, J. Geophys. Res. 91, 

pp. 11,815-11,820. 

Igoshin, V. I., L. V. Ku1akov, and A. 1. Nik1tin, 1974, Sov. J. Quant. Electron. 1, p. 306. 

Hlies, A. 3., and G. A. Takacs, 1976, J. Photochem. 2., pp. 35-42. 

Inn, E. C. Y., 1975, Atmospheric Sciences 32, p. 2375. --.-~----- - -

Inn, E. C. Y., and Y. Tanaka, 1953, J. Opt. Soc. Am. 43, pp. 870-873. 

Inoue, G. and H. Akimoto, 1981, J. Chem. Phys. 84, pp. 425-433. 

Iwata, R. , R. A. Ferrieri, and A. P. Wolf, 1986, J. Phys. Chern. 90, 

pp. 6722-6726. 

Iyer, R. S., and F. S. Rowland, 1980, Geophys. Res. Lett. 2, pp. 797-800. 

Iyer, R. 5., P. J. Rogers, and F. S. Rowland, 1983, J. Phys. Chem. [I, p. 3799. 

Jaffe, R. L., and S. R. Langhoff, 1978, J. Chem. Phys. 68, p. 1638. 

Jaffe,S., and F. S. Klein, 1966. Trans. Faraday Soc. 62. pp. 2150-2157. 

168 
) 

) 

) 

., .•. ~ 

~-'}'\ 

... --- ····_

Jaffe,S., and V~ K. Hainquist, 1980, J. Phys. Chem. ~, p. 3277. 

James, G. 5., and G. P. Glass, 1970, J. Chem. Phys. 12, p. 2268. 

Jayanty, R. K. M., R. Simonaitis, and J. Heick1en, 1976, J. Phys. Chem. 80, 

p. 443. 

Jenouvrier, A., B. Coquart, and M. F. Merienne, 1986, J. Quant. Spectrosc. 

Radiat. Transfer ~, pp. 349-354. 

- .Jeong, -K~_M., and~. KaufmaI!, 1.97..9_, .£el)_PEY~ Res. Lett.§', pp. 757-759. 

Jeong, K. M., and F. Kaufman, 1982, J. Phys. Chem. M, pp. 1808-1815. 

Jeong, K •. M., K. J. Hsu, J. B. Jeffries, andF. Kaufman, 1984, J. Phys. Chem. 

~, pp. 1222-1226~ 

Johnston, H. 5., and R. Graham, 1973, J. Chem. Phys. II, p. 62. 

Johnston~-H. S. ~-and- R. Graham,' 1974,- Can. J. Chem . .21, pp. 115-1423. 

Johnston, H. 5., E. D. Morris, Jr., and J. Van den Bogaerde, 1969, J. Am. 

Chem. Soc. 21, p. 7712. 

Johnston, H. 5., S. Chang, ~ (. Whitten, 1974, J. Phys. Chem. 78, pp. 1-7. 

Johnston, H. S., M. Paige, and F. Yao, 1984, J. Geophys. Res. 89, p. II, 661. 

Johnston, H. 5., C. A. Cantrell, andJ. G. Calvert, 1986, J. Geophys. Res. 91, 

pp. 5159-5172. 

Jolly, G. 5., G. Paraskevopou10s, and D. L. Singleton, 1985, Chem. Phys. Lett_ 

11l, pp. 132-137. 

Jolly, G. 5., D. L .. Sing1eton, D. J. McKen~ey, and G. Paraskevopoulos, 1986. 

J. Chem. Phys. ~, pp. 6662-6667. 

Jones, B. M. R., J. P. Burrows, R. A. Cox, and S. A. Penkett, 1982, Chem. -·Phys~ Lett~--88, pp:- 372-376~ - _ - -._-

Jones, E. L., and O. R. Wulf, 1937, J. Chem. Phys. 1, p. 873. 

Jones, 1. T. N., and K. Bayes, 1973, J. Chem. Phys. 59, pp. 4836-4844. 

Jones, W. E., and E. G. Skolnik, 1976, Chemical Reviews 76, p. 563. 

Jourdain, J. L., G. Le Bras, G. Poulet, J. Combourieu, P. Rigaud, and B. LeRoy. 

1978, Chem. Phys. Lett. 12, p. 109. 

Jourdain, J. L., G. Le Bras, and J. Combourieu, 1979, Int. J. Chem. Kinet. 11, 

pp. 569-577. 

169 
) 

) ~ 

Jourdain, J. L., G. Le Bras, and J. Combourieu, 1981, Chem. Phys. Lett. 78, 

p. 483. 

Jourdain, J. L., G. Pou1et, and G. Le Bras, 1982, J. Chem. Phys. 76, 

pp. 5827-5833. 

Kaiser, E. W., and S. M. Japar, 1977, Chem. Phys. Lett. 22, p. 121. 

Kaiser, E. W., and S. M. Japar, 1978, Chem. Phys. Lett. 54, p. 265. 

Kaj imoto , 0., and R. J. Cvetanovic, 1976, J. Chem. Phys. 64, p. 1005. 

- Kan, C. S-., -R. D. McQuigg, -M.- R.-- Whitbeck; and J--;- G. Calvert, 1979,-Int. J. 

Chem. Kinet. II, p. 921. 

Kan, C. S., J. G. Calvert, a~~ J. H. Shaw, 1980, J. Phys. Chem. 84, p. 3411. 

Kan, C. S., J. G. Calvert, and J. H. Shaw, 1981, J. Phys. Chem. 85, 

pp. 1126-1132. 

Kaufman, 

32-34. 

F.L_~. J. J,;~rri,_ .and_D_. _A. Pascale, 1956, J. Chem. Phys. 24, pp.--

Kaye, J. A., 1986, J. Geophys. Res. 91, pp. 7865-7874. 

Kerr, J. A., and D. W. Sheppard, 1981, Environ. Sci. Technol. 15, p. 960. 

Keyser, L. F., 1978, J. Chem. Phys. 69, p. 214. 

Keyser, L. F., 1979, J. Phys. Chem. 83, pp. 645-648. 

Keyser, L. F., 1980a. J. Phys. Chem. 84,pp. 11-14. 

Keyser, L. F .. 1980b, J. Phys. Chem. 84, pp. 1659-1663. 

Keyser, L. F., 1981, J. Phys. Chem. 85, pp. 3667-3673. 

Keyser, L. F., 1982, J. Phys. Chem. 86, pp. 3439-3446. 

_ Keyser, L. F_, __ 1983--,--.L_Phys. Chem. 87, pp. 837-841;-- - -- -. --

Keyser. L. F., 1984, J. Phys. Chem. 88, pp. 4750-4758. 

Keyser, L. F., 1986, J. Phys. Chem. 90, pp. 2994-3003. 

Keyser, L. F., 1907, J. Phys. Chem. (in press). 

Keyser, L. F., K. Y. Choo, and M. T. Leu, 1985, Int. J. Chem. Kinet. 17, 

pp. 1169-1185. 

Kijewski, H., and J. Troe, 1972, He1v. Chim. Acta 55, p. 205. 

Kircher, C. C., and S. P. Sander, 1984, J. Phys. Chem. 88, pp. 2082-91. 

170 
) 

) 

Kircher, C. C., J. J. Margitan, and S. P. Sander, 1984, J. Phys. Chern. ~, 

pp. 4370-4375. 

Kita, D., and D. H. Stedman, 1982, J. Chern. Soc. Faraday Trans. II 78, 

pp. 1249 -1259. 

K1ais, 0., P. C. Anderson, A. H. Laufer and M. J. Kurylo, 1979, Chern. Phys. 

Lett. 66, p. 598. 

K1ais, 0., P. C. Anderson, and M. J. Kurylo, 1980a, Int. J. Chern. Kinet. 12, 

p. 469. 

... .. ------ ----_ .. - K1ais, 0., A. H. Laufer, and M. J. Kurylo, 1980b, J. Chern. Phys. 73, pp. 2696-

2699. 

Klein, Th., 1. Barnes, K. H. Becker, E. H. Fink, and F. Zabel; 1984, J. Ph]:;. Chem. S8 ,. pp. 5020-5025. - ---- - -- - - - -

K1einerrnanns. K. , and A. C. Luntz, 1981, J. Phys. Chern. 85, p. 1966. 

Klemm, R. B., 1979, -;-:·-Chein.--Pllys-.-71, p:1987. - - - .- -- ----_. 

Klemm, R. B. , and . .... J. Stief, 1974, J. Chern. Phys. 61, p . 4900. 

Klemm, R. B., E. G. Skolnik, and J. V. Michael, 1980, J. Chern. Phys. 72, 

p. 1256. 

Kn3uth, H. D., 1978, Ber. Bunsenges. Phys. Chern. §l, p. 212. 

Knauth, H. D., H. Alberti, and H. Clausen, 1979, J. Phys. Chern. 83, pp. 1604-

1612. 

Knox, J. H., 1955, Chemistry and Industry, p. 1631. See also Lin et al., 

1978a. 

Knox, J. H., and R. L. Nelson, 1959. Trans. Far. Soc. }2, p. 937. 

Kornp~, K. L .• and J. Wanner. 1972, Chern. Phys. Lett. 12, p. 560. 

----- ----- --Kurasawa, --H.-.- and R. Lesc1aux, 1979. Chern. Phys. Lett. 66, p. 602. 

Kurasawa, H., and R. Lesc1aux, 19ROa, Chern. Phys. Lett. 72, p. 437. 

Kurasawa, H., and R. Lesc1aux. 1980b, 14th Informal P~otochernistry Conference, 

Newport Beach, CA, April 1980. 

Kurylo, M. J., 1972, J. Phys. Chern. 76, p. 3513. 

Kurylo, M. J., 1973. Chern. Phys. Lett. 23, pp. 467-471. 

Kurylo, M. J., 1977, Chern. Phys. Lett. ~, p. 467. 

Kur;10, M. J., 1978, Chern. Phys. Lett. 58, pp. 238-242. 

171 

." 

-

. ---.+ 

.. 

:-

. -- -
--- ~.-' -- -- j:~':~ <.:. ..... -~ r_~' 

-- ' .. 

'. ) 

_.---": - _/ 

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'-

-=-~.-

... --. 

~.~-

-..:..~ :-~-

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-..• ". 

'. 

-/ 

./ 

~-=:;"'-.~~ 

,.:.-

................ 

~ 

---.)~: 

. -' 

~ 

_., . 

_ .. -----;:- ... -1- 0 ; 

.-.~-

Kurylo, K. J., and W. Braun, 1976, Chem. Phys. Lett. 11, p. 232~ 

Kurylo, K. J. and R. Kanning, 1977, Chell. Phys. Lett. ~. p. 279. 

Kurylo, K. J., and A. H. Laufer, 1979, J. Chem. Phys. 12, pp. 2032-2033. 

Kurylo, K. J., and C. L. Knable, 1984, J. Pbys. Chell. .n, pp. 3305-3308. 

Kurylo, K. J., and P. A. Ouellette, 1986, J. Phys. Chelll. 22, pp. 441-444. 

Kurylo, K. J., and P. A. Ouellette, 1987, J. Pbys. Chell. ~, pp. 3365-3368. 

Kurylo, K. J., and T. J. Wallington, 1987, Chell. Phys. Lett. ill, pp. 543-547 . 

Kurylo, K. J., P. C. Anderson, and O. Klais, 1979, Geophys. Res. Lett. ~, 

pp. 760-762. - ---

Kurylo, K. J., O. Klais, and A. H. Laufer, 1981, J. Phys. Chem. ~. pp. 3674-

3678. 

Kurylo, K. J., K. D. Cornett; and J. L. Kurphy._ 1982a, J. Ce_ophys. _ Res. Eo-

--pp;--3081-3085. --- -

----

Kurylo, K. J., J. L. Kurphy, G. S. Haller, and K. D. Cornett, 1982b, Int. J. 

Chem. Kinet. 14, pp. 1149-1161. 

Kurylo, K. J., G. L. Knable, and J. L. Ku=phy, 1983a, Chem. Phys. Lett. 95, 

pp. 9-12. 

Kurylo, K. J., J. L. Kurphy, and G. L. Knable, 1983b, Chem. Phys. Lett. ~, 

pp. 281-284. 

Kurylo, K. J., P. A. Ouellette, and A. H. Laufer, 1986, J. Phys. Chem. ~, 

pp. 437-440. 

Kurylo, K. J .• T. J. Wallington, and P. A. Ouellette. 1987a. J. Photochem. ~. 

Fp. 201-215. 

Kurylo. K. J.. P ~ Dagau:: ._T. J ._JJa11ingtoJl,. and _D. K. Neuman.--1987b, Che:zn. 

Phys. Lett. 139. pp.-513-518.--

Laguna. G. A. and S. L. Baughcum, 1982, Chem. Phys. Lett. 88. 568-7L 

Lam, L., D. R. Hastie. B. A. Ridley, and H. I. Schiff. 1981. J. Photochem. ~. 

pp. 119-130. 

Lamb, J. J. o L. T. Kolina. C. A. Smith, andK. J. Kolina, 1983. J. Phys. Cheor. 

87, pp.4467-4470. 

Langford. A. 0 .• and C. B. Koore, 1984. J. Chem. Phys. 80. pp. 4211·422L 

Langhoff. S. R., L. Jaffe. and J. O. Arnold. 1977, J. Quant. Spectrosc. Raaiat. 

Transfer 18. p. 227. 

172 

"'_.---

lilt 

~ 

l~ 

............ 

~ ' . 
... -: 

-- ) 

- ---~., 

~. ;.,. -

.---

---' 

) 

------------------------------

Laufer, A. H., and A. M. BassI- 1975, Int. J. Chem. Kinet. I, p. 639. 

Le Bras, G., R. Foon, and J. Combourieu, 1980, Chem. Phys. Lett. 11, p. 357. 

Leck, T. J., J. E. Cook, and J. W. Birks, 1980, J. Chem. Phys. ll, pp. 2364-

2373. 

Lee, F. S. C., and F. S. Rowland, 1917, J. Phys. Chem. li, p. 684. 

Lee, J. H., and I. N. TE.llg, 1982, J. Chem. Phys. II, pp. 4459-63. 

Lee;-J. H:, I.V. Michae1,-W. A. Payne, Jr., and L. J. Stief, 1977, J-. Chem.-

Soc. Faraday Trans. I 11, pp. 1530-1536. 

Lee, J. H., J. V. Hlchae1, W. A. Payne, Jr., and L. J. Stief, 1978a, J. Chem. 

Phys. 68, pp. 5410-5413. 

Lee, J. H., J. V. Michael, W. A. Payne, Jr., and L. J. Stief, 1978b, J. Chem. 

Phys. ~, pp. 350-353. 

Lee, .L.-_H_._J. V. Michael, W. A. __ Fayne, Jr., and L. }. Stief, _1978c, J. Chem. 

Phys. 69, pp. 3069-3076. 

Lee, L. C., 1982, J. Chem. Phys. 76, pp. 4909-4915. 

Lee, L. C., and T. G. Slanger, 1978, J. Chem. Phys. 69, pp. 4053-4060 . 

Lee, L. C., and T. G. S1anger, 1979, Geopbys. Res. Lett. ~, pp. 165-166. 

Lee, Y.-P., and C. J. Howard, 1982, J. Chem. Phys. 11, pp. 756-763. 

Lee, Y.-P., R. M. Stimpf1e, R. A. Perry, J. A. Mucha, K. M. Evenson, D. A. 

Jennings, and C. J. Howard, 1982, Int. J. Chem. Kinet. 14, pp. 711-732. 

Leroy, B., G. LeBras, and P. Rigaud, 1981, Ann. Geopbys. 37, pp. 297-302. 

Lesc1awc, R., and K. Demissy, 1977, Nouv. J. Chim. 1, p. 443. 

Lesclaux, R., -and F. Cara1p, 1984, Int..- J. Chem. Kinet. 16, pp. 1111-1128._ 

Lesc1aux, R., P. V. Khe, P. Dezauzier, and J. C. Sou1ignac, 1975, Chem. Phys. 

Lett. 12, p. 493. 

Leu, M. T., 1979a, Chem. Phys. Lett. 61, pp. 275-279. 

Leu, K. T., 1979b, J. Chem. Phys. 22, pp. 1662-1666. 

Leu, M. T., 1980a, Chem. Phys. Lett. ~, pp. 37-39. 

Leu, M. T., 1980b, Geophys. Res. Lett. I, pp. 173-175. 

Leu, K. T., 1982, J. Phys. Chem. 86, p. 4558. 

173 

...., 

,-

~ 

. 

!. 

• I 

~ 
) 

..:-.... 

) 

.--:-.~ 

Leu, M. T., 1984a, Int. J. Chem. Kinetics li, pp. 1311-1320. 

Leu, M. T., 1984b, J. Phys. Chem. ~, pp. 1394-1398. 

Leu, M. T., and W. B. DeMore, 1976, Chem. Phys. Lett. M., pp. 121-124. 

Leu, M. T., and W. B. DeMore, 1977, Chem. Phys. Lett. 48, p. 317. 

Leu, M. T., and W. B. DeMore,' 1978, J. Phys. Chem. ~, p. 2049. 

Leu, M. T., and C. L. Lin, 1979, Geophys. Res. Lett. i, pp. 425-428. 

Leu, M. T., and R. H. Smith, 1981, J. Phys. Chem. ll, pp. 2570-2575. 

Leu, M. T., . and R. H. Smith, 1982a, J. Phys. Chem. 86, pp. 73-81. 

Leu, M. T., and R. H. Smith, 1982b, J. Phys. Chem. 86, pp. 958-961. 

Leu, M. T., C. L. Lin, and W. B. DeMore, 1977, J. Phys. Chem. 81, p. 190. 

_Le~J.~, _R._~~., ___ and R~ T. __ Wats~n, ~98..Q.!.J. Phys. _Che~. M:, p._ 3495-3~03. 

Lewis, R. S., S. P. Sander, S. Wagner, and R. T. Watson, 1980, J. Phys. Chem. 

84, pp. 2009-2015. 

Lii, R. -R., R. A. Gorse, Jr., M. C. Sauer, Jr., and S. Gordon, 1979. J. Phys. 

Chem. 83, pp. 1803-1804. 

Lii, R. -R., R. A. Gorse, Jr., M. C. Sauer, Jr., and S. Gordon, 1980a, J. Phys. 

Chem. 84, pp. 819-821. 

Lii, R. -R., R. A. Gorse, Jr., M. C. Sauer, Jr., and S. Gordon, 1980b, J. Phys. 

Chem. 84, pp. 813-317. 

Lii, R.-R., M. C. Sauer, Jr., and S. Gordon, 1980c, J. Phys. Chem. 84, 

pp. 817 -819. 

Lii, R.-R., M. C Sauer, Jr., and S. Gordon, 1981, J. Phys. Chem. 85, pp. 

_ 2833,.2834. _ 

Lin, C. L., 1982, Int. J. Chem. Kinet. ~, pp. 593-598. 

Lin, C. L. , and W. B. DeMore, 197j~- J. Phys. Chem. 12, pp. 863-869. 

Lin, C. L. , and M. T. Leu, 1982, Int. J. Chell. Kinet. 14, p. 417. 

Lin, C. L., M. T. Leu, and W. B. DeMore, 1978a, J. Phys. Chem. 82, p. 1772. 

Lin, C. L., N. K. Rohatgi, and W. B. DeMore, 1978b, Geophys. Res. Lett. 2, 

pp. 113-115. 

Lin, Y.-L., N-S. Wang, and Y-P. Lee, 1985, Int. J. Chem. Ki.Dec. 12, 

pp. 1201-1214. 

174 

. -::=:- .~-

~ 

. ; 

~ 

~~ 

~ ..... ... 

1 

1 

-j 

~ 

~j 

:.. 

! 
-

) 

) 

Lippmann, H. H., B. Jesser, and U~ Schurath, 1980, Int. J. Chem. Kinet. li, 

pp. 547-554. 

Littlejohn, D., and H. S. Johnston, 1980, EOS ~, p. 966. 

Lloyd, A. C., K. R. Darnall, A. K. Winer, and J. N. Pitts, Jr., 1976, J. Phys. 

Chem. 80, p. 789. 

Locker, J. R., J. B. Burkholder, and E. J. Bair, 1983, J. Phys. Chem. 87, 

pp. 1864-1868. 

Locker, J. R., J. A. Joens, and E. J. Bair, 1987, J. Photochem. 12, pp. 235-245. 

Loewenstein, L. K., and J. G. Anderson, 1984, J. Phys. Chem. M, pp. 6277-6286. 

LOrenz, -K., D. Rhasa, Ie Zelfner, and B. Fritz, 1985, -Ber. Bunsenges. Phys. 

Chem. 89, pp. 341-342. 

Louge, K. and R. K. Hanson,· 1984, Twentieth Symposium (International) on Combustion, pp. 665-~672. 

Lovejoy, E. R., N. S. Wang, and C. J. Howard, 1987, J. Phys. Chem . .2l, 

pp. 5749-5755. 

Lozovslcy, V. A., K. A. Ioffe, and O. K. Sarkisov, 1984, Chem. Phys. Lett. 110, 

pp. 651-4. 

Lu, E. C. C., R. S. Iyer, and F. S. Rowland, 1986, J. Phys. Chem. 90, pp. 1988-

1990. 

Kack, G. P. P •• , and B. Thrush, 1913-; J. -Chem. -Soc., Faraday-Trans. 1 69, 

p. 208. 

Kack, G. P. R., and B. Thrush, 1974, J. Chem. Soc., Faraday Trans. 1, 70, 

pp. 173-186. 

KacLeod, H., G. P. Smith, and D. K. Golden, J. Geophys. Res. (sublritted). 

- -- - - - -. - Kagnotta, F., and H. S. Johnston, 1980, Geophys. Res. Lett. I, pp. 769-772.-

Kajer, J. R., and J. P. Simons, 1964, ·Photochemica1 Processes in Ha10genaced 

Compounds,· J. Pitts, G. Hammond, and W~ A.-Noyes. ed., Advances in Photochemistry, Z, Interscience, New York, pp. 137-181. 

Kalko, K. W., and J. Troe, 1982, Int. J. Chem. Kinet. 14, p. 399. 

Kandelman, K., and R. W. Nicholls, 1977, J. Quant. Spectrosc. Radiat. Trans. 

11, p. 483. 

Manning, R., and K. J. Kurylo, 1977, J. Phys. Chem. ~, p. 291. 

Manning, R. G., W. Braun, and K. J. Kurylo, 1976, J. Chem. Phys. ~, p. 2609. 

175 

---~ 

;-

. 

~ 
) 

) 

Manzan'.lres, E. R., K. Suto, L. C. Lee, and D. Coffey, 1986. J. Chell. Phys. ll, 

pp. 5027-5034. 

Margitan, J. J., 1983a, J. Phys. Chell. 87, pp. 674-679. 

Margitan, J. J., 1983b, J. Geophys. Res. 1a, pp. 5416-5420. 

Hargitan, J. J., 1984a, J. Phys. Chell. 1a, pp. 3314-3318. 

Hargitan, J. J., 1984b, J. Phys. Chell. ~, pp. 3638-3643. 

Hargita~, J. J.,_and R!_T~Jlatson,_1982, J. Phys. Chera. H, pp. 3819-3824. 

Margitan. J. J., F. Kaufman, and J. G. Anderson. 1974, Geophys. Res. Lett. 1, 

pp. 80-81. 

Margitan, J;: J., F. Kaufman, -and- J. G. Anderson, 1975, Int. J. Chem. Kinet. 

Symp. No. i, p. 281. -

Marinelli, Y. J., and H. S. Johnston, 1982a, J. Chem. Phys. li, pp. 1225-1234. 

Marine11i,Y;-J-. ,-and-H~---S. Johnston;-1982b, -Chem:-Phys. Lett. 93, pp. 127-132. 

Marinelli, Y. J., D. M. Swanson, and H. S. Johnston, 1982, J. Chem. Phys. 76, 

pp. 2864-2870. 

Martin, D., J. L. Jourdain, and G. LeBras, 1986,J. Phys. Chem. 90, pp 4143-

4147. 

Martin, H., and R. Gareis, 1956, Z. E1ektrochemie 60, pp. 959-964. 

Hartin, J. -P., and G.Paraskevopou1os, -198-3, -Can. --J. Chem. fl. -pp. 861-865. 

Marx, Y .• F. Bahe. and U. Schurath, 1979, Ber. Bunsenges. Phys. Chem. 83, 

pp. 225-230. 

Mauersberger, _K., J. Barnes, D. Hanson, and J _ Korton, 1986, Geophys. Res. 

Lett. 11, pp. 671-673-

Mauersber-ger, K:.- D.Hanson, -J. Barnes;- and J. Morton:-1987, J. -Geophys. Res. 

92, pp. 8480-8482. 

McAdam, K., B. Veyret, -and R. Lesclaux, 1987, -Chem~-Phys. Lett. 133, pp. 39-44. 

McCrumb, J. L., and F. Kaufman, 1972, J. Chem. Phys. 57, pp. 1270-1276. 

McElcheran, D. E., M. H. J. Yijnen, and E. Y. R. Steacie, 1958, Can. J. Chell. 

36, p. 321. 

McGee, T. J., and J. Burris, 1987, J. QUant. Spectrosc. Radiat. Transfer 37, 

pp. 165-182. 

176 

.. ~~ -- -. - -'. - - - - ----.. 

.,. 

, 

~ -.. 
) 

) 

I 

McKenzie. A .• M. F. R. Mulcahy. and J. R. Steven. 1973. J. Chem. Phys. ~. 

pp. 3244-3254. 

Meier. U •• H. H. Grotheer. and T. Just. 1984. Chem. Phys. Lett. ill. pp. 97-101. 

Michael. J. V •• and J. H. Lee. 1977. Chem. Phys. Lett • .a. p. 303. 

Kichael. J. V •• and W. A. Payne. 1979. Int. J. Chem. Kinet. li. p_ 799. 

Michael. J. V •• D. A. Whytock. J. H. Lee. W. A. Payne. and L. J. Stief. 1977. 

J. Chem. Phys: 22. p. 3533. 

Michael. J. V •• J. H. Lee. Y. A. Payne. and L. J. Stief. 1978. J. Chem. Phys . 

.2!l. p. 4093. 

Michael. J-.- V •• D~-F. Nava. Y. A.-Payne. and L. J. Stief. 1979a. J. Chem_ "Phys. 

N. p. 1147. - -

Michael. J. V •• D. F. Nava. Y. A. Payne. and L. J. Stief. 1979b. J. Chem_ Phys. 

N. p. 3652. 

Kichael. J. V •• D. F. Nava. R. P. Borkowski. W.~A~-pa:yne, and L." J. Stief, 

1980. J. Chem. Phys. 11. p. 6108. 

Michael. J. V •• J. E. Allen. Jr.. and W. D. Br.,bst. 1981. J. Phys. Chem. ~. 

p. 4109. 

Michael, J. V., D. F. Nava, W. Brobst, R. P. Borkowski, and L. J. Stief, 1982, 

J. Phys. Chem. ~, pp. 81-84. 

Michael, J. V., D. G. Keil, and R. B. Klemm, 1985a, J. Chem. Phys. 83, 

pp. 1630-1636. 

Kichael, J. V., P.. B. Klemm, W. D. Brobst, S. R. Bosco, and D. F. Nava. 1985b, 

J. Phys. Chem. 89, pp. 3335-3337. 

Killer, J. C., and R. J. Gordon, 1981. J. Chem. Phys. 12. p_ 5305. 

Misha.lanre;- E"~--A. ,- -C;J.- Rutkowski. R. S.--Hutte, and J. __ ~. Birks,: 1.986, J. 

Phys. Chem. 90. pp. 5578-5584. - -

Kitchell, D. N .• R. P. Yayne. P.J. Allen. R. P. Harrison. and R. J. Twin, 

1980, J. Chem. Soc. Faraday Trans. II 22. p. 785. 

Kiziolek, A. W., and K. J. Molina. 1978. J. Phys. Chem. 82. p. 1769. 

Kolina. L. T., and M. J. Molina. 1977, Geophys. Res. Lett. ~, pp. 83·86. 

Kolina. L. T .• and M. J. Molina, 1978. J. Phys. Chem . .n. pp. 2410-2414. 

Molina, L. T., and K. J. Molina. 1979, J. Photochem. li. pp. 139-144. 

Molina, L. T., andM. J. Kolina. 1981. J. Photochem. 11. p. 97. 

177 

- -------~ 
) 

- --

_._-

J 

Molina, L. T., and M. J. Molina, 1982, "Chemistry of Fluorine in .the stratophere,· l82nd American Chemical Society National Meeting~ New York. August. 

1982. 

Molina, L. T., and M. J. Molina, 1986, J. Geophys. Res • .2]., pp. 14,501-14,508_ 

Molina, L. T., and M. J. Molina, 1987, J. Phys. Chem. 91, pp. 433-436_ 

Molina, L. T., S. D. Schinke, and M. J. Molina, 1977a, Geophys. Res. Lett. ~. 

pp. 580-582. 

Molina, L. T., J. E. Spencer, and M. J. Molina, 1977b, Chern. Phys. Lett. 45. 

- -- -.. - pp. 158-162. 

Molina, L. T., J. J. Lamb, .. nd M. J. Molina • 1981, Geophys. Res. Lett. ~. 

p. 1008. 

Molina, L. T., M. J. Molina, and F. S. Rowland, 1982, J. Phys. Chern. 86, pp_ 

2672-2676. 

Molina, L. T., M. J. Molina,-.R'- A. Stachnik, and R. D. Tom, 1985, J. Phys_ 

Chem. 89, pp. 3779-3781. ___ _ 

Molina, M. J., and G. Arguello, 1979, Geophys. Res. Lett • .2, pp. 953·955_ 

Molina, M. J., L. T. Molina andT.Ishiwata, 1980a, J. Phys. Chem. 84, p. 3100_ 

Molina, M. J., T. Ishiwata, and L. T. Molina, 1980b, J. PhJs. Chern. 24., pp. 

821-826. 

Molina, M. J., L. T. Molina, and C. A. Smith, 1984, Int. J. Chem. Kinet. 16. 

pp. 1151-1160. 

Moortgat, G. K., and E. Kudzus, 1978, Geophys. Res. Lett. ,2, p. 191. 

Moortgat, G. K., and P. {Jarneck, 1979, J. Chem. Phys. 70, pp. 3639-3651-

Moortgat, G. K., {J. Klippel, K. H. Mobius, {J. Seiler, and P. {Jarneck, 1980. 

"Laboratory Measurements of Photolytic Parameters for Formaldehyde,· Report: 

.. _No. FAA·EK-.80-47,-{Jashington, D.C. 

Moor~gat, G. K., W. Seiler, and P. {Jarneck, 1983, J. Chem. Phys. 78, pp. 1185-

1190. __ . __ _ 

Morel, 0., R. Simonaitis, and J. Heicklen, 1980, Chem. Phys. Lett. 73. p. 38. 

Morley, C., and 1. {J. M. Smith, 1972, J. Chem. Soc. Faraday Trans., 68, 

p. 1016. 

Morris, E. D., and H. Niki, 1971, J. Chem. Phys. 55, p. 1991. 

Morris, E. D., and H. Niki, 1974, J. Phys. Chem. 78, pp. 1337-1338. 

178 

, 

~ .. 

:~7 ... -;- ----_ ~ .... "C_':O_ 
) 

) 

Morris, E. D., D. H. Stedman, and H. -Niki, 1971, J. Am. Chem. Soc. 93, p. 3570. 

Nadtochenko, V. A., O. M. Sarkisov, and V. I. Vedeneev, 1979, Doklady Akademii 

Nauk SSSR, 244, p. 152. 

NASA Reference Publication 1010, 1977, Chlorofluorornethanes and the Stratosphere, Hudson, R. D., Editor, NASA, Yashington, D.C. 

NASA Reference Publication 1049, 1979, The Stratosphere: Present and Future, 

Hudson, R. D., and E. I. Reed, Editors, NASA, Washington, D.C. 

Nava, D. F., J. V. Michael, andL-!J. S~ie{,_1981,..J. Phys. Chern.ll, p. 1896. 

Nava, D. F., S. R. Bosco, and L. J. Stief, 1983, J. Chem. Phys. 78, pp. 

2443·2448. 

Nava, D. F. ,-W. D; Brobst, -and L. J. Stief~ -1985~- J-. Phy.:>. Chern. 89, pp. -4703-

4707. 

Nelson, H. H., and H. S. Johnston, 1981, J. l'hys. Chem. 85, p. 3891. 

Nelson, H. H., J. Marinel-1i;-and-H;-S-. --Johnston, 1981, Chern. -Phys-.- Lett. 78, 

pp. 495-499. 

Nesbitt, D. J., and S. R. Leone, 1980, J. Chem. Phys. 72, pp. 1722-1732. 

Nesbitt, F. L., D. F. Nava, W. A. Payne, and L. J. Stief, 1987, J. Phys. 

Chem. 21, pp. 5337-5340. 

Nicholas, J. E., and R. G. W. Norrish, 1968, Proc. Roy. Soc. A 307, p. 391. 

Nicolet, M . .- and W. Peetermans, 1980, Planet. Space Sci. 21), pp. 85-103. 

Nicovich, J. M., and P. H. Wine, 1987, J. Phys. Chem. 91, pp. 5118·5123. 

Nicovich, J. M., P. H. Wine, and A. R. Ravishankara, 1987, manuscript in 

preparation. 

Nielsen, O. J., 1979, "Chemical Kinetics in the Gas Ph~~e Pulse Radio1ysis of 

Hydrogen Su1fide-Systems,-n-Riso-National Labor~tory Pub1ication,-Riso-M·2216, 

Roskilde, Denmark. 

Nielsen, O. J., J. Munk, P. Pagsberg, and A. Sillesen. 1986; Chein'-Phys. Le:::. 

128, pp. 168-171. 

Niki, H., E. E. Oaby and B. Weinstock, 1969, Data reported at Twelfth Syrnposi~~ 

(International) on Combustion, The Combustion Institute, p. 277. 

Niki, H., P. D. Maker, L. P. Breitenbach, and C. M. Savage, 1978a, Chem. Phys. 

Lett. 57, p. 596. 

Niki, H., P. D. Maker, C. M. Savage, and L. P. Breitenbach, 1978b, J. Phys. 

Chem. 82, p. 132. 

179 

----. 

• 

. 

;. 

II 
) 

- - -- --

J 

)' 

Niki, H., P. D. Maker, C. K. Savage, and L. P. Breitenbach, 1978c, Chem. Pbys. 

Lett. 2i, p. 78. 

Niki, H., P. D. Maker, C. K. Savage, and L. P. Breitenbach, 1980, Chem. Phys. 

Lett. 11, pp. 43-46. 

Niki, H., P. D. Maker, C. K. Savage, and L. P. Breitenbach, 1981, J. Pbys. 

Chem. ~, p. 877. 

Niki, H., P. D. Maker, C. K. Savage, and L. P. Breitenbach, 1983, J. Phys. 

Chem. ~, pp. 2190-2193. --- -- _. -

Niki, H., ~. C. Kaker, C. K. Savage, and L. P. Breitenbach, 1984, J. Phys. 

Chem. ~, pp. 2116-2119. 

Nip, Y. ,S., D.,_ L. Singleton, R. OVerend, and_ G. Paraskevopou1os, 1979, .J. __ 

Phys. Chem. !l, pp. 2440-2443. 

Ogryz10, E. A., R. Pa1tenghi, and K. D. Bayes, 1981, Int. J. Chem.'Kinet. ll. 

pp, 667,-675. 

- ___ - ____ .0___". _ 

Okabe, H., 1978, Photochemistry of Small Kolecules, John Yi1ey and Sons, Inc_ , 

New York, p. 217. 

Okabe, H., 1980, J. Chem. Phys. 11, p. 6642. 

01bregts, J., C. Brasseur, and E. J. Arijs, 1984, J. Photochem. ~, pp. 315-

322. 

Ongstad, A. P., and J. Y. Birks, 1984. J. Chem. Phys • .lil, pp. 3922-3930. 

Ongstad, A. P., and J. Y. Birks, 1986, J. Chem. Phys. n, pp. 3359-3368. 

OVerend, R. P., andG. Paraskevopoulos, 1977a, Chem. Phys. Lett. ~, p. 109. 

Overend, R. P., and G. Paraskevopou1os, 1977b, J. Chem. Pbys. fl, p. 674. 

Overend, R. P., C. Paraskevopou1os, and R. J. Cvetanovic, 1975, Can. J. Chea . 

.2.1, p. 3374-3382. -- ---

Overend, R. P., G. Paraskevopou1os, and C. Black, 1976, J. Chem~ Phys. 64, 

p. 4149. 

Pagsberg, P. B., J. Erikson, and H. C. Christensen, 1979, J. Phys. Chem. li, 

p. 582. 

Paraskevopoulos, G., and R. S. Irwin, 1982a, Chem. Phys. Lett. li, pp. 138-143. 

Paraskevopou1os, G., and R. S. Irwin, 1982b, XV Informal Conference on Photochemistry, Stanford, CA June 27-Ju1y 1. 

Paraskovopou10s, G., and R. S. Irwin, 1984, J. Chem. Phys. l!.Q, pp. 259-266. 

180 

Wi! :n::::::::~;; 5 ... ·:G jj __ t:A'..8;~.,. 15· b?£!fF5 .. :::B:l!!i 
) 

~ ) 

rJ 

" 

.:. 

~ 

Paraskevopou1os. G .• D. L. Singleton. and R. S. Irwin, 1981,. J. Phys. Chem. 

~. p. 561. 

Paraskevopou1os, G., D. L. Singleton. and R. S. Irwin, 1983, Chem. Phys. Lect . 

.lQ.Q. pp. 83-87. 

Parkes, D. A., 1977, Int. J. Chem. Kinet. i, p. 451. 

Parrish, D. D., P. C. Murphy, D. L. Albritton, and F. C. Fehsenfe1d, 1963, 

Atmos. Environ. 12. p. 1365. 

-Pastrana-,--A..-v., and R. W. Carr', Jr •• 1974, Int~-J-;Chem. Kinet. §.. --po 587. 

Pate. C. T .• B. J. Finlayson. and J. N. Pitts, Jr., 1974, J. Am. Chem. Soc. 

96,p.6554. 

Patrick, R., and D. M. Golden, 1983, Int. J. Chem. Kinet. 12, pp. 1189-1227. 

Patrick, R .• and D. M. Golden, 1984a, Int. J. Chem. Kinet. 16, pp. 1567-14. 

. - ._..!a~~ick, R.,. and D, M. Go1denL-1984b,_.-l.._Phys. Chem. 88, pp .. 49.k5. 

Paukert,' T. T., and H. S. Johnston, 1972, J. Chem. Phys. 56, pp. 2824-28~B. 

Payne. W. A., L. J. Stief, and D. D. Davis, 1973, J. Am. Chem. Soc. ~, 

p. 7614. 

Payne. '.1. A., D. F. Nava, J. Brunning, and L. J. Stief, 1986, J. Geophys. Res. 

21, pp. 4097-4101. 

Payne, W. A., J. Brunning, M. B. Mitchell, and L. J. Stief, 1987, manuscri~t 

submitted to J. Chem. Kinet. 

Penzhorn, R. D., and C. E. Canosa, 1983, 'Ber. Bunsenges. Pl-,ys. Chem. li, 

pp. 648 - 654 . 

Perner, D., A. Schme1tekopf, R. -H. Winkler, H. S. Johnston, J. G. Ca1verz, 

C. A. Cantrell, and W. R. Stockwell, 1985, J. Geophys. Res. 90, 3807-38L2. 

-Perry, R. A., and D. Williamson, 1982, Chem. Phys. Lett. 93,pp. 331-33~ 

Perry. R. A., and C. F. Melius. 1984,. Twentie~Symposium (Internationa1L?n 

Combustion, pp. 639-646. 

Perry, R. A., R. Atkinson, and J. N. Pitts, Jr., 1976a, J. Chem. Phys. 6~, 

p. 1618. 

Perry, R. A., R. Atkinson, and J. N. Pitts, Jr. 1976b, J. Chem. Phys. 64, 

p. 3237. 

Perry, R. A., R. Atkinson, and J. N. Pitts, Jr., 1977. J. Chem. Phys. fl. 

p. 5577. 

181 

.-------------...... -..,""'-""'=e..= .... "==""~._~._~_~.'!:_~=~.~ .... o;.:O"·-~_~.·~~cx=_~~i5:'~~~~~ 

-
·~ ) 

) 

,.": . 

• 

:; 

, "" 

Phillips, L. F., 1978, _Chem. Phys. Lett. n, pp. 538-539. 

Phillips. L. F. and H. 1. Schiff, 1962,J. Chem. Phys. 36, p. 1509. 

Pilling, M. J. and J. J. C. Smith, 1985, J. Phys. Chem. 89, pp. 4332-4338. 

Pirre, H., P. Rigaud, and D. Huguenin, 1984, Geophys. Res. Lett. 11, p. 1199. 

Plane, J. M. C., and D. Husain, 1986, J. Chem. Soc. Faraday 2, ~, pp. 2047-

2052. 

PlUmb: i: t-. ~- -iinaK. R. Ryan, 1982a-; Chem. Phys. Lett.---ll, pp.- 236-238.. 

Plumb, I. C., and K. R. Ryan, 1982b, Int. J. Chem. Kinet. ~, p. 861-874. 

-Plumb, 1. C.;- K. R. Ryan, J.-R. Steven, and-M. F. R. Mulcahy, 197.9_: .chem. Phys. 

Lett. 63, p. 255. 

Plumb, I. C., K. R. Ryan, J. R. Steven, and M. F. R.Mu1cahy, 1981, J. Phys. 

Chem. ~, p. -3136, 

Porter, G., and F. G. Yright, 1953, Disc. Faraday Soc. ~, p. 23:----

Posey, J., J. Sherwell, and M. Kaufman, 1981, Chem. Phys. Lett. 71, p. 476. 

Poulet, G., J. Barassin, G. Le Bras, and J. Combourieu, 1973, Bull. Soc. 

Chirn. Fr. 1, p. 1.-

Poulet, G., G. Le Bras, and J. Combourieu, 1974, J. Chim. Physique 11, p. 101. 

Poulet, G.,-G. Le Bras, and J. Combourieu, 1977, J. Phys. Chem. il, p. 2303. 

Poulet, G., G. Le Bras, and J. Combourieu, 1978a, J. Chern. Phys. 69, p. 767. 

Pou1et, G., G. Le Bras, and J. Combourieu, 1978b, Proceedings of the Yor1d 

Meteorological Organization Symposium on the Geophysical Aspects and consequences of Changes In the Composition of the Stratosphere. Toronto, 26-30 

June 1918. YMO-y511, p. 289. 

Pou1et, G., G. Le Bras, and- J. Combourieu, 1980, Geophys. Res. Lett:. 2. 

pp. 413-414. 

Pou1et, G., G. Laverdet, and G. Le Bras, 1981, J. Fhys. Chem. 85, p. 1892:-

Fou1et. G., G. Laverdet, and G. Le Bras, 1983, Chem. Phys. Lett. ~, pp. 129-

132. 

Poulet, G., G. Laverdet, J. L. Jourdain, and G. Le Bras, 1984a, J. Phys. Chem. 

88, pp. 6259-6263. 

Poulet, G., G. Laverdet, and G. Le Bras. 1984b, J. Chem. Phys. ~, pp. 1922-

1928. 

182 

_":::::i - •. w::aliVZ2L!!:az2!&3f.£3~!JItJitti!W&Qjb&F~.?ilJh4f'd¥E.!!'¥§!§~ 
) 

_. ~ 

_.- ) 

, 

... F 

--- ----- ---------W0

Pou1ett, G., G. Laverdet, and G. Le Bras, 1986a, J. Phys. Chem. 90, pp. 159-165. 

Pou1ett, G., H. Zagogianni, and G. Le Bras, 1986b, Int. J. Chem~ Kinet. 18, 

pp. 847-859 

Prasad, S. S., 1980, Nature~, p. 152. 

Pratt, G. L., and S. W. Wood, 1984. J. Chem. Soc. Faraday Trans. I, 80, 

pp. 3419-27. 

Pritchard. H. 0., J. B. Pyke, and A. F. Trotman-Dickenson. 1954, J. Amer. Chem. 

Soc. li. p. 1201. _ __ ___ .. - - -- -- -- -- -

Pritchard, H. 0 .• J. B. Pyke. and A. F. Trotman-Dickenson. 1955. J. Amer. Chem. 

Soc. 22. p. 2629. 

Radf?rd. H. E .• 1980. Chem. Phys.-Lett. 11. p. 195. 

Radford. H. E., K. M. Evenson. and D. A. Jennings. 1981, Chem. Phys. Lett . .TIL 

p. 589. 

___ Ravishankara._A. R., and P. H.-Wine, 1980, -.1. -Chem-;- Phys:--ll, pp.25-':-30. 

Ravishankara, A. R., and R. L. Thompson. 1983. Chem. Phys. Lett., 2.2., p. 377. 

Ravishankara. A. R .• and P. H. Wine. 1983, Chem. Phys. Lett. 101. p. 73. 

Ravishankara, A. R., and R. L. Mauldin. 1986. J. Geophys. Res. 21. pp. 8709-

8712. 

Ravishankara, A. R., G. Smith, R. T. Watson, and D. D. Davis. l~l7a. J. Phys. 

Chem. li. _po 2220. 

Ravishankara, A. R., D. D. Davis, G. Smith, G. Tesi. and J. Spencer. 1977b, 

Geophys. Res. Lett. ~. p. 7. 

Ravishankara, A. R., G. Smith, and D. D. Davis. 1978. 13th Informal Photochemistry Conference, Clearwater Beach. Florida, January 1978. 

Ravishankara, A. R., P. H:-\line, and A. 0.- Langford:-1979a-, Chem. Phys. Lett. -- 63, p. 479. - -

Ravishankara, A. R., P. H.- \line, and A. O. Langford, 1979b. J. Chem. Phys. 

70, pp. 984-989. 

Ravishankara, A. R .. F. L. Eisele, and P. H. \line, 1980a, J. Chem .. Phys. 73, 

p. 3743. 

Ravishankara. A. R .• N. M. Kreutter. R. C. Shah, and P. H. \line, 1980b. 

Geophys. Res. Lett. 2. pp. 861-86~. 

Ravishankara, A. R .• F. L. Eisele, N. M. Kreutter. and P. H. \line, 1981a, J_ 

Chem. Phys. ~, p. 2267. 

183 

~ 

=.~tY4!Ji::z&&Aigz:;UQii;i ~ tJIiii!liUkt::a::&i!i . ~ "'i\!il!ili!&4~~ . "<;:::~~~~~_~~~~-:"I; 
) 

~) ;..-

... ---::.~~ 

--~~-

, ..... , .~- ._---_ ..• _-- - .. _---

Rav1shankara, A. R., J. K. Nlcovich, R. L. Thompson. and F. P. Tully, 1981b, 

J. Phys. Chem. ~, pp. 2498-2503. 

Ravishankara, A. R •• F. L. Eisele, and P. H. Wine. 1982, J. Phys. Chem. ~, 

pp. 1854-1958. 

Ravishankara, A. R., F. L. Eisele, and P. H. Wine, 1983a, J. Chem. Phys. ~, 

pp. 1140 -1144. 

Rav1shankara, A. R., P. H. Wine, and J. K. Nicovich. 1983b, J. Chem. Phys. ~, 

pp. _6629:€_6~9._. _______ . _ 

Ravishankara, A. R., P. H. Wine, and J. R. Wells, . 1985a, J. Chem. Phys. fl, 

pp. 447-448. 

---RavishanlCara-, A. R., P. H. Wine, J. R.-Wells, and R. L;-Thompson, 1985b·, Int •. 

J. Chem. Kinet. lI, pp. 1281-1297. 

Ravishankara, A. R., P. H. Wine, C. A. Smith, P. E. Barbone, and A. Torabi, 

- 1986; -J ~- Geophys. Res. fro pp; 5355 - 5360. 

Ravishankara, A. R., E. R. Lovejoy; N. S. Wang, C. J. Howard, P. H. Wina, 

J. M. Nicovich, and A. J. Hynes, 1986, paper presented at the 9th International Symposium on Gas Kinetics,. Bordeaux, France'. 

Ray, G. W., and R. T. Watson, 1981a, J. Phys. Chem. ~, pp. 2955-2960. 

Ray, G. W., and R. T. ,Watson, 1981b, J. Phys. Chem. ~, pp. 1673-1676. 

Ray, G. W., L. F. Keyser, and R. T. Watson, 1980, J. Phys. Chem.~, pp. 1674-

1681. 

Reilly, J. D., J. H. Clark, C. B. Moore, ~nd G. C. Pimentel, 1978, J. Chem. 

Phys. 69, p. 4381. 

Reimann, B., and F. Kaufman, 1978, J. Chem. Phys. ,.22., p. 2925. 

Richardson, R. J., 1975, J. Phys. Chem. 22, pp. 1153-1158. - --- - ----.- -

Rigaud, P., B. Leroy, G. Le Bras, ·G. Poulet, J. L. Jourdain, and J. Combourieu, 

1977, Chem. Phys. Lett. ~, p. 161. 

Robbins, D. E., 1976, Geophys. Res. Lett. 1, p. 213; Erratum, Opt cit. 1, 

p. 757. 

Robbins, D. E., 1977, -International Conference on Problems 2.elated to the 

Stratosphere,- W. Huntress, Jr., and D. Maple, Eds., JPL PublIcation 77-12, 

Jet Propulsion Laboratory, California Institute of Technology, Pasadena. 

California. 

Robbins, D. E., and R. S. Stolarski, 1976, Geophys. Rev. Lett. 1, pp. 603·606. 

Robertshaw, J. S., and I. W. M. Smith, 1980, Int. J. Chem. Kinet. Il, p. 729. 

"'~:-:-..... 

'. 

/ -~>' 

.. ~. /i 

-;.~~-!:". -'.-

.-. ..:~:. !.-;--

184 

._~..r _.:.. -:--'>---

" .' ' .'.---.....: ':~- ..-' .. -::1 .... .:.c:~ -:-:-.-:-'.-~' .. : . '-;.~ :.:_~_ 
.;-

~ ) 

it) 

) 

- -_._-.-. ----" - _____ :...e...- -------

Robertshaw, J. S., and I. V. K. Smith, 1982, J .. Phys. Chem. H, p. 785. 

Roscoe, J. K., 1982, Int. J. Chem. Kinet.l!!., pp. 471':478. 

Roth, P., R. Lohr, and H. D. Hermam 1980, !er. Bunsenges. Phys. Chem. ~, 

pp. 835-840. 

Rowland, F. S •• and Y. Hakide, 1982, GeophY~. Res. Lett. i. p. 473. 

Rowland, F. S., and P. J. Rogers, 1982, Proc. Natl. Acad. Sci. USA 12., p. 2737. 

__ Rowland, ¥. S ._' _ ~d _J. _E._§pen~~t:. and M. J. Kolina, 1976, J. Phys. Chem. M2, 

pp. 2711-2713. .- - - - - -- '.' 

Rowland, F. S., H. Sato, H. lChwaja, and S. K. Elliott, 1986, J. Phy.3. Chem. i2, 

pp. 1985-1988. ' 

Rozenshtein, V. B., Yu. K. Gershenzon, S. O. 11'in, andO. P. Kishkovitch,.1984, 

Chem. Phys. Lett. ~, pp. 473-478. 

---Rudo1ph-;--R';- N., -and- E.' C.- Y. Inn, 1981, J. GeophYs. Res.- M, -po 9891.· 

Rust, F., and C. K. Stevens, 1980, Int. J. Chem. Kinet. li, pp. 371-377. 

Ryan, K. R., and 1. c. Plumb, 1982, J. Phys. Chem., 86, pp. 4678-4683., 

Ryan, K. R., and I. C. Plumb, 1984~ Int. J. Chem. Kinet. ~, pp. 591-602. 

Safary, E., J. Romand, and B. V'odar, 1951,-J. Chem. Phys. 12., p. 379. 

Sahetchian, K. A., A. Heiss, and R. Rigny, 1982, Can. J. Chem. ~, pp. 2896-

2902. 

Sahetchian, K. A., A. Heiss, and R. Rigny, 1987, J. Phys. Chem . .21, pp. 2382-

2386. 

Sander, S. P., 1984, J. Phys. Chem. ~, pp. 6018-6021. 

Sander, S. P., 1986, J. Phys. Chem. 2Q, 1'p. 4135-4142. 

Sander, S. P., and R. T. \latson,' 1980, J.- Phys. Chem. ~, 1'. 1664. 

Sander, S. P., and R. T. Yatson, 1981a, Chem. Phys. Lett.ll.,- pp. 4-73-475_ 

Sander, S. P. , and R. T. \latson, 1981b, J. Phys. C~·.~m. n, p. 4000. 

Sa~"\der , s. P. , and R. T. \latson, 1981c, J. Phys. Chem. 85, p. 2960. 

Sander, S. P., and C. C. Kircher, 1986, Chem. Phys.·Lett. ill, pp. 149-152. 

Sander, s. P. ,and K. Peterson, 1984, J. Phys •. Chem. 88, pp. 1566-71. 

, . 

Sander, S. P., G. Y. Ray, and R. T. Yatson, 1981, J. Pbys. Chell. 85, p. 199. 

185 

-.. 

.. 

.. 

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F..j~ _. -----_. 

) 

; 

~ , 

! 

• r) 

_Sander..--S.-P •• H. Peterson.--R; -T~--tlatson.-ancrR~Patrick;-lg8Z;--J ;-Phys. Chelll. 

~. pp. 1236-1240. 

Sanders. N. D •• J. E. Butler. and J. R. McDonald. 1980a. J. Chelll. Phys. 11. 

pp. 5381-5383. 

Sanders. N. D .• J. E. Butler. L. R. Pasternack. and J. R. HcDona1d. 1980b. 

Chelll. Phys. ~. p. 203. 

Sandorfy. C .• 1976. AtIIlos. Environ. 12. pp. 343-351. 

Sanhueza. E .• R. Su.onaitis. and J. Heicklen. 1979. Int. J. Chelll. Kinet. 11. 

p. 907. 

Sarkisov. O. H .• S. G. Cheskis. and E. A. Sviridenkov. 1978. Bull. Acad. Sci. 

USSR Chelll. Sere 21. p. 2336. 

Schieferstein.- K •• K.- Kohse-Hoinghaus. F. Stub1. 1983; Ber. Bunsenges. Phys. 

Chem. II. pp. 361-366. 

Schmidt. V .• G. Y.' Zhu. K. H. Becker. and E. H. Fink. 1985. Ber. Bunsenges. 

Phys._Chem. ~. p. 321. 

Schneider. \l., G. K. Hoortgat, J. P. Burrows. and G. S. Tyndall. 1987. 

J. Photochem. 40. pp. 195-217. 

Schon1e. G •• H. D. Knauth, and R. N. Schindler. 1979. J. Phys. Chem. 83. 

p. 3297. 

Schonle. G., M. M. Rahman, and R. N. Schindler, 1987, Ber. Bunsenges. Phys. 

Chem. 21. pp. 66-75. 

Schurath. U., H. H. Lippmann. and B. Jesser. 1981, Ber. Bunsenges. -Phys. Chem. 

ll, pp. 807-813. 

Schwab. J. J.. D. tl. Toohey, tl. H. Brune, and J. G. Anderson, 1984. J. Geophys. 

Res. 89, pp. 9581·9587. 

Seery. D. J .• and D. Britton. 1964, J. Phys. Chelll. ~. p. 2263. 

Se1wyn,G .• -J. Podolske,-H;- S.-Johnston,1917, Geophys. Res: Lett.!!.; pp_427-

430. 

Se1zer.~ E. A.. and K. D. Bayes, 1983,- J. Phys. Chell. li.· p.-392':394. 

Semmes. D. H., A. R. Ravishankara, ~. A. Gump-Perkins. and P. H. \line. 1985. 

Int. J. Chelll. Kinet. lIt pp. 303-313. 

Shamonima. N. F.. and A. G. Ketov. 1979. Kinet. Rata1. 22. p. 233. 

Shardanand. and A. D. Prasad Rao. 1977. J. Quant. Spectrosc. Radiat. Transfer 

lIt pp.433-439. 

186 

c-~ ,-

~­

~ 

• 
~ 

.... -'-

~. 

~ 

~. ",.-

.,,-

~. 

~ 

• ) 

Shibuya, IC., T. EbAtu, K. Obi, aMI. Tanaka, 1977, J. Phy •• Chea. n. p. 2292. 

~ Silver, J. A •• 1986, J. enea. Phya. Ii. pp. 4718-4720. 

Silver, J. A.. and C. E. Kolb. 1980. Chea. Phys. Lett. .ll. p. 191. 

Silver, J. A., IlIUi C. E. Kolb. 1982, J. Phys. Chea. U. pp. 3240-3246. 

Silver, J. A •• and C. E. Ko1b, 1986a. J. Phys. Chem. 22. pp. 3263-3266. 

Silver, J. A., and C. E. Ko1b, 1986b, J. Phys. Chea. 22. pp. 3267-3269. 

Silver, J. A., A. D. Stanton. K. S. Zahniser. and C. E. Kolb. 1984&. J. Phys. 

_~8!'._~, __ p~_._._3l23-3l29 • 

Silver, J. A •• K. S. Zahniser. A. C. Stanton. and C. E. Kolb. 1984b, 20th 

International Sywposium on Coabustion, Pittsburgh, PA, pp. 605-612. 

- Silver, J.A., D. ll. Vor.nap, A. Freedman. and C. E. Ko1b,.1986, J. aselll. Phy •• 

~, pp. 4378-4384. 

SiJIonait1s, ll., and J. He1cklen, 1973, J. Phys. Chem. ll, pp. 193~-1935. 

-- -SiJIonaitis, ll., and J. Heicklen, 1975_J •.. Phys .• $.:ll~m._.1.2, p •. 29.8._ 

I 

SiJIonaitis, ll., and J. Heicklen, 1978, Int. J. Chem. Kinet. 12, pp. 67-87. 

Sillonaitis, ll., and J. He ick1en , 1979, Chem. Phys. Lett. ll. p. 361. 

Simonaitis, ll., and J. Heick1en, 1981, J. Phys. Chem. 85, p. 2946. 

Simonaitis, ll., and J. Heicklen. 1982. J. Phys. Chem . .n, pp. 3416-3418. 

Single.ton,_D4 L •. , and R. J. Cvetanovic. 1978, Can. J. Chem. ~. p. 2934. 

Singleton, D. L., and R. J. Cvetanovic, 1981 •. Int. J. Chell. Kinet. U. p. 945. 

Singleton, D. L., ll. S. Irwin, and ll. J. Cvetanovic. 1977, Can. J. Chem. 2i, 

pp. 3321-3327. 

Singleton, D. L., ll. S. Irwin. V. S. Nip. and R. J. Cvetanovic, 1979. J. Phys. 

·Ch~m. n, pp. 2195 - 2200. - .- - --

Singleton, D. L., G. Paraskevopoulos, and R. S. Irwin, 1982, J. Phys. Chea. 

H, pp. 2605-2609. 

Sinha, A .• E. ll. Lovejoy, and C. J. Hovard, 1987, J. Chem. Phys. n. 

pp. 2122-2128. 

Slagle. I. R •• J. ll. Gilbert, and D. Gutan. 1974&. J. Cbea. Phy •• il, 9. 704. 

Slagle, I. R., J. F. Pruss. Jr., and D. CublaD. 1974b. Int. J. Chea. Kinet. i. 

p. 111. 

187 

r 

! , 

• i 

, 

~', .' 

..c.", ····'~"'""''''~~,;;+tic ... , •. , ~;~:'c':",.''':'''~.-''.'.,Y1~ '~:".' ..•.• 
,-I 

".j 

S1qle. I. a. •• F. -Ba1occh1. aDd D. Gut:un._1911.-.l~-Pby8-.-Cbea;--n.p;-l333-.-

) Simser. T. G •• I • .1. tlood. ad G. llack. 1973. Int • .1. Cb ... Unet. ~. p.615. 

Surdz ... ld. a.. a. •• aDd II. C. Lin. 1977 • .1. Cb.. Pby8. ii. pp. 3197-3204. 

Saltb. C. A •• L. T. Molina • .1 • .1. Lab. aDd II • .1. Ko1ina. 1984. Int • .1. Cbea. 

Kinet. li. p. 41-45. 

Saleh. C. A •• A. It. lavbhanhra. aDd P. B. Vine. 1985 • .1. Pby •• Cha. H. 

pp. 1423-1427. 

Saleh. G. P •• and D. II. Golden. 1978. Int • .1. a.... KiDet. l!l. Jl. ~9 • 

. - - - - Salth.--G.-P:-.-·-P~v. Fairchild. aDd D. It. Crosley. 1984 • .1. CheJa. Phy. n. 

p. 2667. 

. ---_. -- - .-

Salth. I. V. K •• and It. Zellner. __ 1973 • .J.. a.ea. Soc •• Faraday-TraNI. II H. 

-po 1617. 

Suth. I. V. K •• and It. Zellder. 1974 • .1. at ... Soc •• Faraday Trans. II 12. 

pp. 1045-1056 • 

Suth.· I. V. K •• and R. Zellner. 1975. Int • .1. Cbe •• JC1net •• SYIIP. 1. p. 341. 

Suth. I. V. K •• and K. D. Vil11 .... 1986 • .1. Chea. Soc. Faraday TraM. 2. n. 

pp. 1043-1055. 

S.lth. I. V. K. and G. Yarwood. 1986. Chem. Phys. Lett. llQ. pp. 24-28. 

Smith. R. H •• 1978. Int. J. Cha.. Kinet. 12. p. 519. 

S.lth. tI. S •• c. C. Chou. and F. S. Rowland. 1977. Geophys. Res. Lett. !. 

pp. 517-.5.19-.-

Sparks. It. K •• L. R. Carlson. IC. Shobatake. K. L. Kowalczyk. and Y. T. Lee. 

1980. J. Che •• Phys. 11. pp. 1401-1402. 

Spencer • .1. E •• and F. S. Rowland. -1978 • .1. Phys. Cbe •• n. pp. 7-10. 

Srldharan. U. C.. B. Reimann L anel r. _Kaufaan •. 1980. J. -Che •• Pbys._ll. 

-pp.- 1~86-1293. -

·LI 

Srldharan. U. C •• L. X. Qlu. and F. KaufJaan. 1981~ _.1. Phys. Chell. n. pp.-' ----

3361-3363. 

Sridharan. U. C .• L. X. Qiu. and F. lCaufJaan. 1982 • .1. Pbys. Cha.. fit pp. 

4569-4574. 

Srldharan. U. C.. L. X. Qiu. arid F. lCaufiun. 1984 • .1. PIty •• Cbea • .n. pp. 

1281-1282. 

188 

) 

-"-, ... -"0:""'''',"1'' ... ~~~~#1O¢;'"?j,~""~~~:;i~~~;~i~J'''~'-jir''~~~~,",;,,.~:,,·,,:.,;",· .-,<, ; ... 

.-

! 

• i 

I 
' ".,pew.(*, ._'8 .. ---.,..---:--,.----_._- I' ,,' .' ., ' •• : 5~ 

\ 

j 

) Sridbaran. U. C .• F. S. Klein. and P. ~·"fwm. 1985. J. Ch ... Pby •• n. 

pp. 592-593. 

Stachnik. 1l. A •• aDd K. J. Kol1na. 1987. J. PhY •• Chell • .2l. p. 4603. 

Staclmik. 1l. A.. K. J. Kol1na. and L. T. Kalina. 1986. J. Phya. Chell. .22. 

pp. 2777-2780. 

Starieeo. E. B •• S. E. Siere. aDd H. J. Se~eber. 1962. Z. Phy •• Chell. R.F. 

ll. p. 385. 

St8dllanr D.- H~. _ .. ncLH~_RiJd ... 1973. J. Pby •• Ch ... 11.. p.~604. _. ___ ._ 

Stedaan. D. H •• K. A. A. Clyne. and J. A. Coxon. 1968. quoted in Clyne and 

Coxon (1968). 

Steiner. -H •• and E. --It. Ridea1. 1939. Proc~--lloy. Soc. (Londen) Sec. A;-lll. 

p. 503. 

____ ~~~p~ens. ~._ D •• 1984. J. Phys. Chea. n. pp. 3308-13. 

Stief. L. J.~-V~-A. Payne. -J. H. Lee, and J. V. Kiehael,-1979,-J-" Chem. Phys. 

~. pp. 5241-5243. 

Stief. L. J., D. P. Nava. V. A. Payne. andJ. V. Kiehael, 1980. J. Chem. Phys. 

11. p. 2254-2253. 

Stief, L. J., V. D. Brobst, D. F. Nava, R. P. Borkowski, and J. V. Michael, 

1982, J. Chea. Soc. Faraday Trans. II la, pp. 1391-1401. 

Stillpf1e, R., R. Perry, and C. J. Howard, 1979, J. Chell. Phys. 11. pp. 5183-

5190. 

Stockwell, V. R., and J. G. Calvert, 1978, J. Photochell. ~, pp. 193-203. 

Stockwell, V. R., and J. G. Calvert, 1983. Atmospheric Environment 11, pp. 

2231-2235. 

_. ________ Stx:,eit._ G. E., C. J. Howard. A. L. Schme1tekopf, J. A. Davidson. and H. 1. 

-' Schiff. 1976.- J. Chem:Phys::- .22. pp. 4761-4764. ---

:.:--" 

.-

y: 

!"~ ":. ;: 

1 

r-")-

Streit. G. E., J. S. Vel1s, F. C. Fehsenfe1d, and C. J. Howard. 1979, J. Chem. 

Phys. 12. pp. 3439-3443. 

Stub1, F., 1973a. Ber. Bunsenges. Phys. Chell. 11. p. 674 • 

Stub1, F., 1973b, J. Chell. Phys. ~. p. 635. 

Stub1, F., 1974. Ber. Bunsenges. Phys. Chea. 11. p. 230. 

Stuhl, P., and H. HUd. 1971, J. Chell. Phys. », p. 3954. 

Stub1, F., and H. Hiki, 1972, J. Chell. Phys. 21, pp. 3671-3677. 

189 

liij~q~~M~-ii~ii······~'il.i.··~'·;:;:!.i·-Ol-Ii'~·~~~~~~~~:.;;.!;c".,"'_>C,. '_' 

t 

t 

I 

i 

I • 

1 

• 
~ .A"'*"C, _~- ... ----....-.. ---:--

) -Su;-F;-,-.L -cr.-C&lvert:. -~-R~ -Undley, V. K. U.elJaan. and .1. H. Shaw, 1979a, .1. PbY •• Chea. il. pp. 912-920. 

) 

-

SUI F., .1. G. Calvert:, .1. H. Shaw, H. Niki, P. D. Kaker, C. K. Savage, and 

L. D. Breitenbach. 1979b, Chem. Phy •. Lett. 22, pp. 221-225. 

SUI F .• .1. G. Calvert. and J. H. Shaw, 1979c, J. Phy •• Chem. 11, pp. 3185-91. 

Sullivan • .1. 0 •• and P. V&meck. 1965, .1. Phy •• Chem. ii, p. 1749. 

Swanson. D., B. Xan. aDd H. S . .1ohnston, 1984, J. Phys. Chem. ~, p. 3115. 

Sze1te1y_. _~ •• _It. _IC~_ ~~n.and C. BovIun, 1984, _ Twentleth_SY1IlP0slwL(Inter- __ 

-national) on eo.bustlon. pp. 647-654. . 

Talcott. C. L., .1. V. Ager.III, and C • .1. Howard. 1986, .1. Chem. Phys. 84, 

pp. 6161-6169. 

Takacs. G. A. , and G. P. Glass. 1973a, J. Phys. Chem. ll, p. 1060. 

Takacs, G. A. , and G. P. Glass, 1973b, J. Phys. Chem. ll, p. 1182. ---_ .. - --- -

Takacs-, G. -A;-,- and G. P. - Glass, -1973c, .1. Pnys-.- -Chem:--z.Z-;- p. 1948. 

Takacs, G. A. , and C • .1. Howard, 1984, J. Phys. Chem. ~, p. 2110. 

Takacs, G. A. , and C. .1. Howard, 1986, .1. Phys. Chell. ~, pp. 687·690. 

Tang, K. Y., P. W. Fairchild, and E. K. C. Lee, 1979, J. Phys. Chem. 83. 

p. 569. 

Temps, F •• and H. Gg. Vagner, 1982, Ber. Bunsenges. Phys. Chell. 86, p. 119. 

Tb%ush, B. A., and .1. P. T. Vi1kinson, 1979, Chem. Phys. Lett. 66, pp. 441· 

443. 

Tb%ush, B. A., and .1. P. T. Vi1kinson, 1981a, Chem. Phys. Lett. 11, pp. 1-3. 

Thrush, B. A., and.1. P. T. Wilkinson, 1981b, Chell. Phys. Lett.~, pp. 17-19. 

----. ---t1iiush, B.- A:, and G. S: Tyndall, 1982a~ J •. Ch-e"~--Soc-: Faraday-II 78. pp. 

1469-1475. 

Thrush, B. A., and G. S. Tyndall, 1982b. Chell. Phys. Lett. 22,.- pp. 232-235. 

Tie8, .1 • .1., F. B. Vapter, R. C. 01denborg, and V. V. Rice, 1981. Chem, Phys. 

Lett. JZ, pp. 80-84. 

Toohey, D. V., V. H. Brune, and .1. G. Anderson. 1987a, .1. Pby •• Chell. n. 

pp. 1215-1222. 

Toohey, D. lI., V. H. Brune, and .1. G. Anderson, 1987b, to be published. 

190 

-

--~ 

J 

---.-

• 

· j, · ;. 

.. 

.~ 

1 

i 

j 

10-

.& 

.. ;"'~;-.'.. ~-;' ,..:.-,.- --:--"":1" --" --~: ""C,· -.:_~.b;' ·f~~.$.~:--.;;;~~~~.fjt::':':::_~""c ... _,"e ... _i 
i --,....-= ---------- • ______ n ---------. ------,-~---=_r, 

I , 

, 

• 

• 

· • 

i • 

-: 

of 

::--" 

;-

A .. 

.. 

-) 

P. 

--1; ~ 

• 

t 

f 

• 

) 

-Torabi,-----A. ,-and-A-.-R..-Ravbbankara-,-1984i-·paper-preaented-ae-the-16th-InfonaalConference on Pbotocbeaf.stry , Harvard Univ.rsity, c.a.hr1.d&e. MA. August 1984. 

Trainor, D. V •• and C. V. von Ros.nberg. Jr •• 1974, J. Cbea. Phys. ll. pp. 

1010-1015. 

Travor. P. L •• G. Black. and J. It. Barker. 1982. J. Phys. Ole •. Ii. p. 1661. 

Troe. J., 1977. J. Cbea. Pbys. H. p. 4745. 

Tsuchiya. S •• and T. Nah.ura. 1979. Bull. O1ea. Soc. Japan 12.. pp. 1527-1528. 

Tuazon. E. C •• R. Atkinson. C. N. PIU11. A. K. Viner and J. H. Pitts. 1983. 

Geophy •• -ae.: lAtt:- lQ. -pp. -953:6.- - -- .- -- --

Tuazon. E. C •• E. Sanhueza. R. Atkinson. V. P. L. Carter. A. K. Viner. and J. H. 

Pitt •• Jr •• 1984. J. PbY •• Cbea. 11. pp. 3095-98. 

Tully. F. P •• 1983, Cbea. Phys. Lett. ~. pp. 148-153. 

Tully. F. P •• and A. R. Ravisbankara. 1980. J. Pbys. Cbe •• .§!t. pp. 3126-3130. 

Tully.F-.-P;-. A. ll.-Ravisbankara. -and Ie. Carr. 1983. Inter.- J.-Ch ... ·Kin.t. 

12. pp. 1111-1118. 

Tully. F. P •• A. T. Droege. K. L. Koszykowski. and C. F. Kallus. 1986. J. Phys. 

Cbea. 22. pp. 691-698. 

Turco. R. P .• 1975. Geophys. Surveys 1. pp. 153-192. 

Turco. R. P .• R. J. Cicerone. E. C. Y. Inn. and L. A. Capone. 1981. J. Geophys. 

Res. ~. p. 5373. 

Tyndall. G. S .• Ie. K. Stedman. V. Schneider. J. P. Burrows. and G. K. Hoortgat. 

1987. J. Pbotochea. ~. pp. 133-139. 

van den Bergh, H. E •• and A. B. Callear, 1971. Trans. Faraday Soc. li. p. 2017. 

Vanderzanden. J. ll •• and J. V. Birks. 1982. Cbe •• Pbys. Lett. n. pp. 109-114. 

--·V&:DIaetnea-Keuree. H .• J. Viseaberg.-and P. C. -Simoti.1978a. BulL Acad; Roy. 

Belgique. Cl. Sci. ~. p. 31. 

Vanlaethea-Keuree, H .• J. Vi seaberg , and P. C. Simon. 1978b. Bull. Acad. Roy. 

Belgique. C1. Sci. ~. p. 42. 

Vanlaethell-Keuree, H •• J. Viseaberg, and P. C. Siaon. 1979. Geophys. Res. Lett. 

i. pp. 451-454 • 

Veyret. B •• and R. Lesc1aux. 1981. J. !hys. Cba.. n. p. 1918. 

Veyret. B •• J. C. Rayez. andll. Lesc1aux. 1982, J. Phys. Olea. Ii. pp. 3424-

3430. 

191 

'-

I , 

, 

i 

.-

~ 

, 

i 

! 

1 

I 

J 

I 

:,.:.~~.;;-:';"''.'-'.:: ':', '" <~'i.i·-·-·i -t,~_: •• ";",!.~" .- ~r~'tG:~#.i..~11f:::~.j,;":~" '.~~..;:;;.~ ,'_.~)I..~ .... , 
,--------------

.viIS! ana .-A_A.-,-l_A.-Davldson,.--F.-C _lebanfalcl,.--and L-&.J.arpa0ll.-1981,-

) l. CMa. fbya. li. p. 6113. 

,; 

0-

:;; 

r. 

:t 

• ) 

V1n1ckier. C •• K. Scbaebra, and l. Peetera. 1985. J. Phys. Cbea. n. pp. 508-

512. -

Volltrauer. B. R •• V. Felder. I.. J. Pirkle. aDd A. Fontijn. 1979 • .J. PbotoCbeli. 

11, ~. 173-181. 

VaJD8r, G., and R. Zellner, 1981. Bar. Bunaeages. Pbys. Ch ... n. pp. 1122-

1128. 

Vqner, B. GS., J. V.matz, and C. Zetzsch, 1971, Anales Aasoc. Quia. Argendna ~, pp. 169-177; - -- - - ~- -- -- - -

Vqner, B. GS., C. Zetzsch, and J. Varnatz, 1972, Bar. Bunseagea. Phys. Chela. 

li, p. 526. 

Vahner, A., G. S. Tyndall, and A. R.. R.avlshankar., 1987, J. PIty •• Chell. n, 

pp. 2734-2738. 

_Vahner • .A •• anetA. R._ R.avlshankara, 1987, J. Geophys. Res. 22, pp.2189-2194. 

Va1br, R. V., 1972, Ph.D. Thesis, Queen Mary College, University of London. 

Vall ington , T. J. and R. A. Cox, 1986, J. Chell. Soc., Faraday Trans., 2.(82), 

pp. 275-289. 

Ya11ington, T. J., R. Atkinson, A. M. Yiner, and J. N. Pitts, Jr., 1986, J. 

Phys. Chell. ~, pp. 5393-5396. 

Val1ington, T. J., R. Atkinson, A. K. Viner, and J. N. Pitts, Jr., 1987a, 

Int. J. Chell. Kinet. U, pp. 243-249. 

Vallington, T. J., D. K. NeUllan, and K. J. Kurylo, 1987b, Int. J. Chem. 

Kinet. 12, pp. 725-739. 

Va1ther, C.-D., and H. Gg. Vagner, 1983, Bar. Bunsenges. l'hys. Chem • .li, 

pp. 403-409. 

-Vang,-N.-- 5, -and -C .. J. Howard, 1987-, J. Phys •. Chem.-, . to be submitted. -

Vang, V. C., K. Suto, and L. C. Lee, 1984, J. Chem. Phys. ~, pp. 3122-3126. 

Vang, N. 5., E. R.. Lovejoy, and C. J. Howard, 1987, J. Thys. Chem. 21, 

pp. 5743-5749. 

Vantuck, P. J., R.. C. 01denberg, S. L. Baugheum, and K. R.. Vinn, 1987, 

J. Phys. Chell. 21, p. 4653. 

Vashida, R., 1980, J. Chell. Phys. :U, p. 1665. 

Vashida, R.. and K. D. P,,!:'es, 1976, Int. T Chell. Kinet. 1, p. 177. 

192 

~it~ '~~~~~~:f .... , :;"" ...... :., <,.~~~~, '," 

.,L' 

-I 

, 
r'" -vr=""" 

, 

-' ~--······;Il 

1 

) 

• • 

• 

I 

~ 

~ 

.. 

, 

t 

~ 

• 

;:"~ 

.- 'l' 

. 

.t: 

..... 

'.!a 

_ ... . 

., 

-~ 

) 

Vuhiela, II., R. J. 1far1:1nez. and )t. D. lay... 1974. Z. Raturforach. lli. 

p. 251. 

Vuhiela. R •• H. AkiJIoto, and II. Okuda. 1980 •• J. Chea. Phys. 11. pp. 5781-5783. 

Vuhiela. R., H. AkbIoto, and II. Okuda. 198Ob, J. CheJa. Pbys. li. p. 1673. 

Wuhiela. R.. H. AlWIoto, and II. Okuda. 1980c. Bull. Cha. Soc. Japan ,ll, 

pp. 3496-3503. 

Watson. I.. T •• 1977. J. Ph,. •. Che •• Reference Data i, pp. 871-917. 

___ Vatson, _I.. T •• ,1980. ,Proceed1ngs~.of-the-RATO Advanced Study Institute on 

Amospberlc Ozone. Report IFAA-EE:80:20. pp. 429-466, Dept. of Transportation, 

Wuhiqton. D.C. 

Vatson, I.. T •• E. S. lIach.do. I.. L. Schiff, S. Fischer. and D. D. Davis, 1975, 

ProceedlDP 'of-the 4th cuP cOnference~ DOT-TSC-OST-75-38. --Cambridge, KA, 

February 1975. Dept. of Transportation, Washington, D.C. 

Watson. I.. T., G. Kachado. S. Fischer, and D. D. Davis, 1976, J. Chea. Phys. n. p. 2126. - ,- - - - - ' -, - - -

Vatson. I.. T •• G. Machado, B. C. Conaway, S. Vagner, and D. D. Davis, 1977, 

J. Phys. Chea. 11, p. 256. 

Vatson, I.. T., S. P. Sander, and Y. L. Yung, 1979a, J. Phys. Chem. n, p. 2936. 

Vatson, R. T., A. R. Ravishankara, G. Machado, S. Vagner, and D. D. Davis, 

1979b, Int. J. Chem. Kinet. 11, pp. 187 -197. 

Vecker. D., I.. Johanssen, and I.. R. Schindler, 1982. Ber. Bunsenges. Phys. 

Chem. 12. pp. 532-538. 

Vei, C. N.. and I.. B. TiJaons. 1975, J. Chem. Phys. ll. p. 3240. 

Vest. G. A., R. E. Veston, Jr .• and G. V. Flynn, 1978. Chem. Phys. Lett. 22, 

p. 429. 

~est~nbe!,g., __ ~._A..~ ape! ~. ~ Haas, 19,69a, _J. Chem. _Phys. ,2.2.. __ p. ,707. 

- -Westenberg. A. A. , and N. de Haas. 1969b, J. Phys. Chem. n. p. 118l. 

Vestenberg. A. A. , and N. de Hau. 1972, J. Chem. Phys. 21., p. 5375. 

Vestenberg, A. A., and N. de Haas. 1973&, J. Chem. Phys. 58. pp. 4066-4071. 

Vestenberg. A. A •• and N. de Haas. 1973b, J. Chem. Phys. 22., p. 6685 . 

We stenberg , A. A., and N. de Haas. 1973c, J. Chem. Phys. ~. pp. 4061-4065. 

Vestenberg. A. A.. and N. de Haas. 1977, J. Chem. Phy.. H. p. 4900 . 

193 

1ti.'#~;-ik;;;.:~.~'~"';~~' ~~~~~~;;.;~~r.,,,~~ '";~"'~~~.¥~~~""-li.;1!'t;j,~,~:", ·::;;"':"~ou'~s.i.s..~.,""-' .' 

I 

! 

-. i 

, 

! 

I 

i 
lL. .,..r--~. ------ ---'-'" -;----- -- ---~=- --. --" .. -_. -- --,--. - ,'~ 

) 

) 

Vestenberg. A. A •• H. de Haas. and J. K. Roscoe. 1970 •• J. Phys. Chelll. 1!!, 

p. 3431. 

Vestenberg, A. A., J. K. Roscoe. and N. de Haas, 1970b, Chem. Phys. Lett. 2. 

pp. 597-599. 

Whyte, A. R., and L. F. Phillips, 1983. Chem. Phys. Lett. lQl. pp. 451-4. 

Whytock. D. A •• R. B. TiIImons, J. H. Lee, J. V. !Uchae1, v. A. Payne, and L. J. 

Stief. 1976, J. Chem. Phys. ~. pp. 2052-2055. 

Whytock. D. A •• J. H. Lee. J. V. Michael. v. A. Payne, and L. J. Stief, 1977. - J.- Chem. Phys:- fi, p~ 2690: - - -' -- -- -- - ---

Vilson, v. E., Jr., 1967. J. Chem. Phys. !2, p. 2017. 

- Vilson, -v. E.,- and-A. A. Vestenberg, 1967 • 11th Symposium on Combustion ('Th~ 

Combustion Institute. Pittsburgh), p. 1143. 

Vine. P. H •• and A. R. Ravlshankara, 1981. Chem. Phys. Lett. 12, pp. 103-109. 

Vine, P. H., and A. R. -Ravishankara, - 1982, Chelll. Phys. ~. pp.- 365-373.-

Vine, P. H., and A. R. Ravishankara, 1983. Chem. Phys. Lett. ~, pp. 129-132. 

Vine, P. H., A. R. Ravishankara. D. L. Phi1en, D. D. Davis, and R. T. Vatson, 

1977. Chelll. Phys. Lett. 22. p. 101. 

Vine, P. H., N. K. Kreutter, and A. R. Ravishankara. 1979. J. Phys. Chem. ~. 

p. 3191. 

Vine. P. H •• R. C. Shah, and A. ll.~Ravishanlcara, 1980. J. Phys. Chelll. 1!!. 

pp. 2499-2503. 

Vine. P. H •• N. K. Kreutter, C. A. Gump, and A. R. Ravishankara, 1981a, J. 

Phys. Chelll. ~, pp. 2660-2665. 

Vine. P. H •• A. R. Ravishankara. N. K. Kreutter. R. C. Shah. J. K. Nicovich. 

R. L. Thompson. and D. J. Vuebb1es, 1981b. J. Geophys. Res. 86, pp. 1105-1112. 

Vine-.:-P~ H •• D. H.Sellllll8s. and A. R. Ravishanlcara. 19S1c. J. Chem. Phys. n. 

pp. 4390-4395. 

Vine. P. H •• V. L. Chameides. and A. R. Ravishankara. 1981d. Geophys. Res. 

Lett. 1. pp. 543-546. 

Vine. P. H •• D. H. SeDDes. and A. R. Ravisha.9)}cara. 1982. Chem. Phys. Lett • .2Q. 

pp. 128-132. 

Vine. P. H •• J. K. Nicovich. R. J. Thompson. and A. R. Ravishankara. 1983. J. 

Phys. Cbea. !I. pp. 3948-54. 

19'. 

~~.~~~j;~<![;.~~~~~L7;;,-".;.~:%t~:,;··~~i~~~~~~J::':~!:''';~.t,~"?~~.~~"""/~.:""'~~~~:';'~:'~~~~Cf.;';~;:~~.!:;":"'~~~" .~ .. ~¥t-H~'~Jr~:\~_i. ~-. :., _ :,,"- .. " 

~ 

i 

i 

i 

t ~ 
r, ===-te-* • - ,=' - .. ,,~ 

") 

I 

~ 

... 

... 

--

? 

~ ~ 

'-) 

... 

': 

I 

Vine. P. H •• It_ J. 'lhcapson. A. It. Ravisbankara. D. H. SeDDes. C. A. Guzap. A. 

Torabi. and J. II. Ricovicb. 1984. J. Pbys. Olea. n.. p. 2095. 

Vine. P. H.. .J. ll. VeIls. and A. R. R.avishaDkara. 1985. J. Pbys. Chelll.a2.. 

pp. 3914-3918. 

Vine. P. H •• .J. ll. VeIls. and A. R. R.avishankara. 1986. J. Chelll. Pbys. M!.. 

pp. 1349-1354. 

Viner. A. H •• A. C. Lloyd. It. R. Darnell. and J. N. Pitts. Jr .• 1976. 

J. !'!tys. Chea. 12. p. 1635. 

\lIfO. Global -Ozone Researcb and.. Konitoring Project. __ 1982 .. Report No. 11. 

The Stratospbere 1981: Tbeory and Keasureaents. 

lmO Gl.oba1 Ozone Researcb and Konitoring Project. 1985. Report No. 16. 

A~spheric ~ 198,. V~rJ.d lIeteorologica1 Organb;ation. Genev~. _ . 

Vong. E. L .• and F. R. Belles. 1971. NASA Tech. Note, NASA TN D-6495. NASA. 

Vasbington. D. C. 

_Vong.V .• _and D. D. _~&yis-;-1974. Itit~ J. Chem. Kinet. 2, p. 401. 

llongdontri-Stuper. V •• R. K. H. Jayanty. R. Simonaitis, and J. Heick1en. 1979. 

J. Pbotocbem. 12. p. 163. 

llurzburg. E.. and P. L. Houston. 1980. J. Chem. Pbys. 12.. p. 4811. 

Xiang. T .• L. K. Torres. and ll. A. Guillory. 1985. J. Chem. Phys. 83, 

pp. 1623-1629. 

Yao. F.. I. Vilson. and H. Johnston. 1982. J. Phys. Chem. 86. p. 3611. 

Yosbino, K •• D. F. Freeman. J. R. Eslllond. and V. H. Parkinson. 1983. Planet. 

Space Sci. 11. pp. 339-353. 

Zahniser. K S. • and F. Kaufman. 1971 • J. Chem. Pbys. 66. p. 3673. 

Zahniser. K. S.. and C. J. Howard. 1980. J. Chem. Pbys. n. pp. 1620-1626. 

----- ----- . -- "Zahniser; K~ ·-S •• F. lCaufllan. and J. G. Anderson. 1974. Chem. Phys. Lett. 

1.1.. p.- 507 ~ - - -

Zahniser. K. S .• F. lCaufllan. and J. G. Anderson. 1976. Chem. Phys. Lett. 

1I. p. 226. 

Zahniser. K. S.. J. Chang. and F. Kaufman. 1977. J. Chem. Pbys. 21.. p. 997. 

Zahniser. K. S •• B. II. Berquist. and F. Kaufman. 1978. Int. J. Chelll. Kinet. 

l2. p. 15. 

Zellner, R •• and V. Steinert. 1976. Int. J. Chem. Kinet. 1. pp. 397-409. 

195 

~~~~~~~'¥'~~.'!.' "!·~'ik.~;.':¥:;,"~;~.z~;~~~;4~~;;ii';':4-,¥,;,,~,,;;'~~;;oi-~.4;';(~;;.i.','~~~~~;';"" ·F,.';, ,;:t;.,§,+,~ 

, -

... .:~ 

I 

l 
(~ , , 

L • 

· 

. 

· 

, 

, 

, 

: 

"! 

'"I 

r-i' .. 

-ZeLlner. R.. and 11. Steinert. 1981. Chea. PIty •• Lett. n. pp. 568-572. 

Zellner. R-.. and K. Lorenz. 1984. J. Phys. -Chea. .9.. pp. 984-989. 

Zellner. R •• G. llagner. and B. Ht... 1980. J. Phys. <21e •• ~. pp. 3196-3198. 

Zellner. R •• B. Fritz. and K. Lorenz. 1986. J. Atmos. Chea. !o. pp. 241-251. 

Zetzsch. C.. 1973. First European Sya. on Coabust. (ed. lleinberg. F. S .• 

Acadeaic Press. London) p. 35. 

Zhitneva. G. P •• and S. Ya. Pshezhetskii, 1978, Kinetika 1 Katsllz 12.. p. 296. 

196 

~-

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