AD-AO'8 386 SECOND EDITION. REVISION NUMBER 5, JUNE 1975 … · AD-AO'8 386 DEFENSE NUCLEAR AGENCY REACTION RATE HANDBOOK. SECOND EDITION. REVISION NUMBER 5, JUNE 1975 M. H. Bortner,

AD-AO'8 386

DEFENSE NUCLEAR AGENCY REACTION RATE HANDBOOK. SECOND EDITION. REVISION NUMBER 5, JUNE 1975

M. H. Bortner, et al

General Elec ric Company

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Defense Nuclear Agency

June 1975

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Revision No. 5, June 1975 DNA 1948H

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DEFENSE NUCLEAR AGENCY

REACTION RATE HANDBOOK

SECOND EDITION

Editors in Chief:

Dr. M.H. Bortner

Dr. T. Baurer

MARCH 1972

Project Officer Dr C.A Blank

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CHAPTER ISA

18. ION-NEUTRAL REACTIONS A. THERMAL PROCESSES

Eldon E. Ferguson Aeronomy Laboratory

National Oceanic and Atmospheric Administration Research Laboratories

(Latest Revision 25 February i975).

18A.1 INTRODUCTION

Progress in the field of ion-neutral reactions has been very rapid in the few years since the first edition of the Reaction Hate Handbook was prepared. 1 he number of atmospherically relevant rate constants known has multiplied greatly and most of those previously known 'nave been improved so that an almost complete rewriting of this chapter iprepared by Wade I.. Fite in the first edition of the Handbook i was ailed t<>r. I he convenient format of Fite is retained. The emphasis of this « hapter is on data tabulation. The reactions reported are positive- and negative-ion < harge-transfer (electron transfer) with neutrals, ion-atom-interchange reactions (chemical rearrangementl, and three-body association reactions. Associative- detachment reactions of negative ions ar^ covered in Chapter 17. The survey is restricted largely to low (near-thermal) energies.

Some useful general references and review articles are:

• a' Sinnott, (i.A., Bibliography of Ion-Molecule Reaction Kate I>a»a, .MI.A Information (enter Report No. '*, I'niversity of Colorado, Boulder, Colorado i P**-'M.

bi McDaniel, K.W., V. Cermak, A. Palgarno, K. K. Ferguson, and I . Friedman, 1 o n - M o 1 c c u 1 e Reat ti»>ns. John Wiley, New- York i 1'.*?()).

M » Hochstim, A. R. , Kd. , i ibln».; raphy >>f Chemical Kinetics and Collision I roc esses, Plenum Kress, New York (I9t><*),

d. Franklin, J. 1.. , J.Ci. Dillard, U.M. Rosenstock, I.J. Herron, K. Draxl, and 1 •'. li. Field, lonization Potentials, Appearance Potentials, and Heats of Formation of Caseous Ions, NSRDS-NI'.S Z» , INS. (iov't. Printing Office. Wash- ington ( 1 '*»;'•).

(el Schiff, H.i. , Kd. , Proceedings < f the Symposium on Labora- tory Measurements of Aeronomic Interest, Can. J. Chern. 47, No. 10 i IW).

18A-1

DNA 1948H

ifi h'fpjson, i , K. , Ann. (leophys. J.^, M1' il'»*'M.

. L: i Ki'ru'is.iu, !..!•.., Ann. deophys. J' , ' >•'' il'*7U).

ihi I rain-lin, ,:.i .. Ld. , 1 >n- Mole- ule Kcu t l'.n.s, ^ Volumes, I ifMvtiii i i'fftt», New Vort il »7»d).

,11 I- f rc. .-s :., i- . i. • , \cc ts . «. he in. Res., >. 4<)<£ ( lw70i.

i •• v_:>•:; K.h. , I aburatory Measurements <>i D-Region i<>n-M<.lcv ule Reactions, in I ;OIT Atmospheric Mod« Is and ;<f iat <•'! i'.A'n'ri:' «Mit .s, (,. i-joiio, Kd. , Reidel, i )o rdrev ht, i i .! land 1 ' V 1 •.

i *•". I Kerens n, K. [•'.. , Ann. (jeophys. ZH, JhV il *72i.

>'. i rernuson, !•..{•.., Revs. Cjeophys. Space F'hys. \jL, 703

18A.2 TECHNIQUES

I lie experimental : »•. hniu ies in use arc des» ribed in detail in l'hapter 7, in referent e item ibl above, and elsewhere. Only brief referent «• is made here to re« ent advanc es which have led to new rea« tion- rate data.

18A .2.1 Stationary Afterglows

I be I;M- of stationary afterglows for ion-neutral reaction studies

is des« ribed in < haptei 7. important studies i Reference thA-1) in the complex mtri« »xide system have been carried out with and with-

i ;• added water vapor, looking at both positive- and negative-ion •s. t •:.«•!• •.'..:•.- iReferem.es I-A-J, ISA- 31 has concentrated

i .r,n&j>iit*ri' reactions, varying the pas temperature from \Hb i • :. l n home « • » ses .

lÂ.2.2 cloAing Afterglow

'.-..•• t. .•.•.:..- ifter;:low technique, a versatile method for ion- r.f itr.ii reai tn-n stu<lies ir the sen.» e ui bein«.' applicable to a wide .'•!:._•• ',{ ion and neutral reutants, has been extended to cover the »«•riiperat ;r«- rmn1 -«»-•.0U K for some rea«'ions (References IKA-4, l-A-: r. '.' has been applied io metal-ion reactions (Reference I8A-0I iri'i ' »lire««- body ion reactions iReferenies IHA-7 through IKA-'M. 1 he method has been applied to measurements of atmospheric-ion

i harye-t ransfer with sodium (Reference IKA-lOl and ion reactions A.t:. water iReferenies I8A-I1 through IMA- 1 31. I ne NUAA system

13A-? Rrv«i«on No b. Jure 1975

CHAPTER 18A

dis» issed in c hauler i' has t.een *- -. t«-i.«i«-<i m .study C- and C,^ reaction)

•••. ui elo» t rutiu a I is ex» it ed ( , a A . ' H cftTfru e I -A - 1 i i, and lu stud)

r «i :> ' > t .it i- > I • r:: iod : .\ an l «:. - in* ut r.i 1 foai tion .-.;>»•• t r- . s< ..pic a 1 ly in

• :.c i t..i r . i- t r.msiiT • •! lit-' with '. , Kef or en« <• I - A - i

ISA.2.3 Secondary lorn In Moss SDOCnometers

1 he :• ..is .- - s:>e. t r meter i« >n -s mri e to« hniquo, U>n»j the standaid

t> M)j f. ir radiation « hemist ry, has made in. in rtant ront ri hut ions to

i nos;>herit r«•.*» tn-n-rate .ata. 1 he pl.otoi« nization sour« e n eti.od

it '.'. arnt'i r i i<»'formt es 1 - A - 1 • , i - A - 17» t..« s allowed tho n i-as ire-

ment of .t larne numher of ionospheric reactions, _»•:.«• r.i il\ •• urr«.b-

I'.i'ini: earlier afterL'iny. results. I ho isotope studios of 1'aulson

Koto Ten« e i - A - 1 - i ha Vo all Wt-d So me loo» hanisms of lonoS pherit

roa< 'i >r.s tu ;,«• doterminod. In addition i aulson ha.-- obtained data

>:i the finTi'v dopendem »• ••! < ertaii rea« tmns, and Las also oxtondod

the :• a.s.s spe« troinotor to * :.«• si idy of ionospheric negative ions

i !•'floront o 1-A-l •».. i enarle Referent es l.Â-J", lhA-iill has

mad* i:: ;. • r*.11.' u:cas irementft t lw«t- and three-hody reactions in-

v '.vi:._ water, whi* h ar».- diffic ult to dti otherwise. S\eharle and als •

i nway have n eas ;:•••': equilibrium « instants in hi^h-pressure mass-

s io • r. ui .»•• •• r ion sounes, addim. greatly U» mir i nowledfje of the

in : pfitut i inoÄpl.eri -ion . hen :s?ry.

1HA.2.-J Crossed* Beam Experiments

I he nn'iii'.d of lurnor and Rutherford ic f. Chapter /1 i ontinuos tu

:>y .du« •• iit'.''' aiiio ints -t valuable ionospheric information on > harê«

trar.Mer ;>r •< •?•>>•>, hoth for positive and negative ions, at energies

«: ••. n " i l'o'.v elottron volts i !•' efereiu e l.-A-J»i». 1 he relative con-

.-••.:. \ : •. > r. ••-' ran.;sfe r rate constants from thermal levels .o

M'V»T.I! •-.•• 'r :. v>»It:- .til-.ws a reasonable extrapolation of the low-

iT.fr.) r ->••':-••!:: dat.i in many '«ist*«. Important data on the

:•<•: '..-.s I •••-' it t'i\ -stv»t •• ions, v.'.i' :. ire alnmst u lavailable .<\ any

t; »-r '«•• t.t.iq ui-, have »Is-« !.o«n ot,t«nne<i • Heferenev 1-A-.'. S., I he

i r .M-ed- .I«-: • iciies i..«v stiown jreat versatility in the rinds of

r • • • i '. s r. • - : t .': i«•' i.

Y8A.2.5 Df«^-Tuhe Te*Hnique5

A vor;, promising !.»*w develo uieni is tin us«- of drift tunes to

study ionospheric ion-neutral re; »tions o»er a ranpe ui energies,

from thermal !«-vols several electron volts, not otherwise readily

a« < essihle. i he woirs »t luondi iHeferences lSA-^4, IKA-<£3},

18A-3 M... s,.,n tin b Jur..- IV?'..

DNA 1948H

Varney (Reference IHA-2M, Hasted iReferences 18A-J7, iMA-ZMi, McDaniel iReference 18.A-Z"l, and Kaneko iReference IHA-301 ar« especially noteworthy .

18A.3 FXAMPLES OF IMPORTANT IONOSPHERIC REACTIONS

Several >t the more important ionospheric rea« tions are dis< ussed in some detail in this sei tion. A variety <»1 different types of n-ai - tions are discussed in ord« r tu point nit ci i t * * • - * • n! kinds of problems which arise. Reviews are «* ailable by I it«- i Reference IsA-il) for aeronumit positive-ion reactions, and !>•• r ergusuu (Reference IhA- iw> for at-ron<»mit neuative-ion reai tior.i:.

18A.3.1 He • Nj - N' • N • He

- N2 • He

I his is an example of ••nv • •! the simplest ionospheric reactions to he measured, involving an i«>n of a stable neutral reacting with a stable neutral. Consequently a number <>l measurements in a variety uf experimentJ» support a value - •!..'. : <i. 51 •. 1' "'•!;. ' set . "1 he rate constant is insensitive ••> temperature variation and to vibrational ex«, itation oi' the nit i •»•e:i. I he brant hinu ratio, i. »•. , *. *. * product ratio, is less « ertain than the rat»--c onstant measurement, since it involves a knowledge of the sampling eftii ten« y las a function of ma Ms i tor the mass suet trometer, \c t: I v i. i.^ unnet essary for the rate-« on.stant measurement alone in «ertain ?«•• hmques. 1 he !. *. > ratio lies hetween on** and two, <*u<l depends on the nitrogen vibrational temperature. 1 hi.* reaction is near resonant iharjie transfer into the N <-i state, which then radiates the second-negative system to Live urou?d-statc !. < , r predissoc iates» to Live !. iRel- erence 1 ~ ,-\ - 1 - •. i his is ««ne >«! the few reactions for which the produ« t states are well known. I her»* is «-vider.ee that the N , produced is rotatic/nallv ex« ited.

18A.3.2 0 • 02 - Cj • O

'I his reaction has been measured by several Workers; all results are consistent with K <J.ux I""11 i . 3uur '' ^ inr sec for the temperature ranjze HO-»«)«! K i References 18A-3 through lhA-t>). Recent data on the energy dependence are presented by Mi tar land et al Referent e lhA-i 5).

I

18A-4

Hevs.on No 5. June 197b

CHAPTER 18A

ISA.3.3 O -N -NO • N

I his rea«. tion has been studied in ^jreat detail, often with i oiiflit t- iiiL results. 1 he rate t ont-tani is 1 . J. \ I»;" « m set at iUO K, and de< r eases t.> <»: >i>\:f \ 1«• ~ "* LIM set at '.Uli L liefe rente lhA-4).

1 he reat tion-rate « onstant i^ extremely sensitive- tu the nitrogen vil rationell tfi. [HTuuirf, in« reasin^ sharply (or 1 vjt, > I wOt) i ilief-

tTeiii e lÂ-54». At higher energies, wheri' tin- t ' »-inetit energy «••.' «.-«-(Is i. i'V, the rate > »nstanl a'su in« reases sharply, it seems lii fly ti.a'. in 11 **.• important i«>n«i:»pl.eri« temperat ire ratine • IX)- Z' •'•> K Tt.* effe« t «it nitrojjfn vmratioiiai-temperature in« rease will dominate the effe * f Kinetn -energy im rease. hanei-u et al iRef- «•!«!.>«• l*A-3'i' have «>t>tained i r«iss»-sv» ti«>n data for ionrineti« enemies from thermal levels t«i about one electron volt. i. 'MaHey

fsas deveUjped a the - r\ tor this re »• tion whi« i. yields some ext rapo- lation tabled lieferen« e I--A- > i. M« tar land et al have re«.ently

provided expressions f«Jr t:.<- <•:.« r.v dependen«. e lieferen« e l-A-5i>.

18A.3.4 Nj • C2 - C2 • N2

.' ihnsen et a! lieferen« «• l.-A-J find the r.ite i uiistant to be »• ..it ' \ I-'" ' ' i ti s.t'1 at i'J i. «::': to de« rease regularly to about

1 '"'-•»! . r- «•> .it " . > r i:.»-tl« er.erLV equal to Me ele«. t Ton Volt. 1 his

agrees very well •.«. ith •:.«• t. iwir.i: -alters! •••'• data [•'t-tvrei < e lÂ-4i in the region •! »verb:;», \ • • •-• h. A »nor»' « "ii ipr eh ens ive ex- pression for the ••:.•:•_'. fiependen« «• i.dh recently been provided by M« ! arland «•• al ;•'• tereii« « 1 - '•• - •» Ji.

18.3.5 S;0" • 0 - 51' • 02

hi: i"• i. 11 ti, !..t > •;•»•: •. . .:.<: • have a rate • >nj-' ant > t appro\i-

! i. a * e 1 v J. \ 1 ' n. ' ';•«•»»•:«:.'• 1 ••••-•• i. A r e a« 11 o n .*» u«. h a s

*: l *• i^ Vt-r\ fllttl' .:' " i ti ensure, M!s< • trie r« .•. t.»:.* loti ^ !..it ! «-a'ii

•• r .<i' «•••':, a:.(i J>II.>. «• * r.v t.e ;t ra 1 rea ' \.:.' I - •!;>!,!: Ii . *. < e\ • «• r: -

:.»•:. 'si :• e'h <:. «-xi-t i:. 'A hi« :. 'he '« :: :»erat ire 'lependen« e >1 :« «• -

ti >r.^ H'.v ilvii.t ir.s* it* « :.«• »'ral> • it. : «• t1 eaMsre«».

IB.3.6 Mc' • C3 - MgO' • C?

! his !••••«• M !. :. t.- a rate • oüätaitt «C, .al to J.. i >. I')" • v :•, "' se

HefereTi« e l"A-' ', and repiesents .-. r ind of reai tion whi«. h i^ uiiti- < -'.It to me.ts'ire be«.ause of problen ^ in handling both tie i«>n ttnd neutral rea« tants. '1 he measurements are « orrespondingly less a« • curate than for experiment«tliy simpler reactions, and SIK h details as the: energy dependen« «• of the rat«- lonstanl are not available.

18A-5

DNA T948H

18A.3.7 02 • No - No' i 02

Ihis reaction and the analogous N, and NU charge-transfer reactions have been measured in a flowing-afterglow system < Refer ~ erne lHA-iO», the rate constant lor the Oj reaction being t. 7 x 10"*° CO» sec at 3<n) \.. Hea« tions of ions with neutral metals pose problems in measurement because of the difficulty of handling and meas- uring the neutral reactasi. However, such, reactions are oeing treated in t rossed-tjeam experiments, down to a few electron volts of ion energy isee Table lhA-»). Because of the difficulties enu- merated above, c rossed-beam measurements will probably supply the bulk of useful information of this Kind for some years, in the vase of charge-transfrr reactions generally, the rate-constant dependent e on energy is usually relatively slight, so that the long extrapolation from a few electron volts to atmospheric temperatures is not so hazardous as would be the usr for ion-atom interchange. However, for 0 , + Na the extrapolation gives about twice as large a rate constant as the flowing -afterglow measurement, and for \ t

+ Na the discrepancy is a factor of four, the extrapolated beam result again being larger. An important detail about reactions such as this which remains undetermined is the chen.icel state of the products, i. e. , either C , or 0 r C> could be produced in the present instant e.

18A.3.8 Oj • Oj • M - 04 • M

Ihis reaction is particularly important witn respect to the D-region chemistry iReferen« e I-A- i7>. Reactions such as this one are diffi- cult to measure in the laboratory and good rate data are correspond- ingly sparse. I he problem is compounded by the fact that several third bodies IMI are of potential importance in the atmosphere, and by the additional fat t that three-body rate constants are markedly temperature-dependent. Much of the atmospheric interest is in »he D-region where "1 < 500 K, which is not a readily accessible ran\;e in most laboratory experiments. For M (J^ and 1 «2'*H K, Durden et al iReference L8A-20I find k I. H x 10-*° cm* /sec for the above reatti >n. For M He and 1 HO K. Böhme et al (Reference 18A-8) find k 3. 1 x 10-~'* cm'1/ sec. Ihis illustrates the marked increase in rate constant with decreasing temperature, a very general finding. U is unlikely that helium is as effective a third body as molecular oxygen at any temperature. In the analogous N^ reaction at 300 K, molecular nitrogen is /.. 5 times as effective as helium, for example «Reference 1KA-MI. This reaction <N£ • ZN^ - N4 • N^> is about 18 times faster than the corresponding Oj reaction cited above.

18A-6 Revision No 5. June 1975

CHAPTER 13A

whii h 1* attributable to a larger N, dissociation energy« 'Ihree- body-association rate constants are expected to increase markedly, both with the dissociation energy of the complex formed and with the sizes of the mole« ales involved, as well as with a dec rease in 'v.. .:>•• ratu re.

ISA.3.<? c; o f/ - o M

it i.- re>.. „:.:.-..•«: that v . !• rmation may ! •• •! g r« at importance in D-regi : :•. stive-ii n chemistry 'Reference l-A-i.s», -Avinj: to a : .•• er ui r.c.uti c. reactions, e.g. * \'( *<,'<.,. whi« h

•t t lead to stable non-ele«, tron-dtlachingi products. ' v s reaction appears I I «• quite slow; M< Knight and .Sawina (Reier »nee I8A- i *• re:.^rt r J \ I"" ' - r ' >«*• at .< 1" K, from drift-tuie studies. This is an «rder t magnitude slower than the analogous O» positive. ion ass ciation at room temperature, suggesting » definite anonialy masmui h as the C, dissociation energy is thought t«. be greater .:'.-'* eV'l than the C, bond energy |0.4<£ eVl.

18A.3.10 NO^ • N02 - NO3 • NO

I i.i^ reaction is observed to ta*e place with a rat»* constant of approximately 4 % I')-*- < >.i.J *• iKeference l<-A-3-), indicating tha« i.A •:.( , • i.AAt ,1 • . • eV, or that iA«/. v. ^» • 1.1 eV at least, and pr ihably > i. I e\ . Additionally, these data seem tu estaolis! thai the reverse rea- tion "A . * NCI is endothermic

wever, it has also been f • • md Keferen« e l-A-40i that a form of \( * it. : «• -<r >duced which reacts readily with NC in the laboratory, 1'res in.ably this 'A . is a different stable geometrical form of the same empiric*, formula 'A. "A 1'olyatomit ions are known to exist indifferent is merit forms, e.g., U-N-C-C" and l-'.-t. in the

c- presen! instance. ] his suggests .1 potential source of error in cer- tain .•»:• -ratory • hservati« :;.-, as well a.^ •• considerable additional

mpiexit} f •:.«• l>-r«>ion chemistry, where such factors may have an importan« ::.! ien< «• ipon the ion chemistry in particular.

1 he el« itr •. iffmi'y ->f .*.(.,, has» been determined to be 1. 3s : 0.0» eV »Keferen« «• i -A -4 I i and that of NCi has been determined to be

• . • • . d eV iKef« ren< •• 1 .-A -4d».

13A.3.11 The Oj - H?0 Seque., e?

A rea« tion sc heme which pro« eeds sequentially from O , to M X) • !i ,0 and higher hydrated clusters, is known t«» be very

Hrv.i.o»' No !». Jo»* »97b

18A-7

DNA 1948H

significant in the O-region. The three-body association of O^ to O^, discissed in subsection 1 8A. I, 8, is efficient at approximately 200 K in the D-region, Following this initial step, the sequence proceeds via:

0Ä • Ho - u • H,u • •\

M.o . «Mi • o.

I. I « li 1.1 • 11

* • »0*10 1.1 • |6

I.4» • I"

!.0 ' jo -9

».••-,fl .i,o-io-,e ..... l0

» I • »0 ». I • 19 1.4 « 10

HÔ • OH

These are followed in turn by further three-body clustering of water molecules to the hydrated cluster-ions. Reaction (c) (producing 11*0* I is almost certainlv endothermic and presumably occurs as a consequence of vibrational excitation of the reactant 0*"H*,0. This may account for reported variations in the branching ratio represented by reactions (b) and (c), with different experimental conditions. Fehsenfeld (Reference lnA-41) has found that the reaction:

ie» °4 ' ° "C2 ' °3

has a large rate constant, i.e., k = (3 t 2) * 10" cmvsec. This plays an important role in the O", - H>() reaction scheme in the D- region.

In addition to 0**11 >t> production from el, direct C* hydration v an t»t «. ur:

Ifl O ; • M.O • M -O, -I! ,C • M

2 8 f> Howard et al have found the rate constant to be 2. 3 y 10"** en. /sec for M - O» at 2% K (Reference I8A-13», and Ciood et al (Reference I8A-21) and Fehsenfeld et al iReference I8A-9) have obtained simi- lar results.

Rate constants from Kebarle Reference 18A-21). in cm /sec. Rate constants from Fehsenfeld (Reference I8A-9), in cm* sec. Rate constants from Howard «Reference I HA-13). in cm sec.

18A-8 Hevivon Nu S. June 1976

CHAPTER 18A

18A.3. 12 The NO - rLO Sequence

The sequence of events involved in NO* hydration in the D-region has been shown (References 18A-1, 18A-U. 18A-37, 18A-43, 18A- 44» to include:

(*» NO • H ,C • M • NO • H ,0 • M , k • I.» x 10 -28

<ö> NO H,0 • H,0 • M ^ NO |H 01 • M . h = 1.0 h JO

k -- < I x 10

-27

-13

<c> NO IH.O» • H O* M r SO JH.O) • M . * 2. 0 • 10

k 1.1x10

-27

-12

<4' NO IM,0)^-1,0 -HjO (H,0^*HNOr k = 8 I 10 11

H

1.4 x 10 -28

1.2 x 10

i. 7 « 10

-2?

-14

1.4 x 10

1.4 x 10

-27

-12

7 * 10 -11

- 28 ti 1. fc x 10 err /*ec.

1.1 ft lO'Z7cmbt%tc.

1.4 a 10"l4cir>3/«ec.

1.9 * 10" cm /•*€.

1.9» 10*l2cmJ/«ec.

7 x 10 err /sec.

The results presented above agree remarkably well in view of the complexity of the coupled reaction sequence.

-10 18A.3.13 N02 • NO - NC + NOj

This reaction has been found to be very rapid; k = 2. 9 * 10 cm3 sec (Reference 18A-45*. which iJ important insofar as it con- firms that IPQiO?) >IP(NO).

18A.3.14 NO +CO* * M-NO^-C02 + M

The reaction, where M s N,, has been found to have a rate constant of i ' 10--' cm ^/sec at 197 K in the afterglow (Reference 18A-46). Furthermore, the reaction NC^-CCj^ • 11,0 -NO^'IUO + CO, is very fast, i.e. , k — 10" * cm , sec. These combined results are important in that the CO? association with NO , followed by the

Rate constants under "F ' (via flowing afterglow, where M S^ are from Fehsenfeid et al (Reference I8A-43), who also report data for M : He, Ar. Rate constants under ' H (via flowing afterglow, where M N3) are from Howard et al (Reference 18A-12», who also report data for M = He, Ar, O?. Rate constants under

P (via stationary afterglow, where M - NO) are from Puckett and Teague (Reference 18A-44). All data pertain to room-temperature measurements.

18A-9 Rwwon No. 5. Jon« 1975

DNA 1948H

rapid 'switching" of CO, and H2C, appears to be a more rapid means of hydrating NO+ in the D-region than the direct three-body association of NO* and H20.

18A.4 SUMMARY OF REAaiON RATE CONSTANTS

Following are several tables of reaction-rate constants of atmospheric interest: Table 18A-1, positive-ion charge-iransfer reactions Table 18A-2, negative-ion charge-transfer reactions; Table 18A-3, positive-ion atom-interchange reactions: Table 18A-4, negative-ion atom-interchange reactions; Table 18A-5, three-body positive-ion reactions; Table 18A-6, three-body negative-ion reactions; and Table 18A-7, the Gulf General Atomic charge-transfer reactions of positive ions with metallic neutrals. The latter are kept separate because they form a cohesive set of data and because of the special extrapolation methods used to estimate the thermal-energy rate constants. Throughout all tables except the last (18A-7), the rate constants are reported in the form m(-ni, which designates m x 10"n.

Unless otherwise specified, rate constants were obtained at room temperature. For some older measurements, review papers are referenced rather than the original papers.

18A-10 Revision No. 5. June 1975

.

z c

£

Tabl

e 18

A-1

.

Po

siti

ve-'

on c

har

ge-

tran

sfer

.

Rea

ctio

n k

(crr

r/$e

c)

Ref

eren

ces

Com

iTie

nts

I.O

. b.

He* -

» N

2- H

e *

N + N

*

- H

e +

Nj

1.2

(-9)

18A

-31, 4

7 48

Se

e pa

r.

18A

.3.1

.

2.

He* •

02 -

He

+ O + 0

+

1.1

(-9

) 18

A-3

1, 4

7 A

lso

prod

uces

O-

.

3.

He* • N

2 - 2

He

+ N

*.

1.2

(-9)

18A

-48, 4

9 20

0-90

0K

4.

0+ + H

-O «

• H+

6.8

(-10)

18A

-50, 5

1 rt

= 20

-40

A2

5.*

o

* +

o2 -

o • o

2

2.0

(-1

1)

18A

-3,4

, 33

Se

e pa

r.

18A

.3.2

.

6.

O*

• N

O - O

+ N

O*

~8

(-1

3)

18A

-52

300K

; k

incr

ease

s to ~ 1

(-

11)

at 1 e

V r

elai

've

ion

kin

etic e

ner

gy.

7.

O

+ N

Oj

• N

02 +

O

1.6

(-9)

18A

-53

393K

8.

O4

+ N

O -

N?0*

+ O

2.2

(-10)

18A

-54

Cf. T

able 1

8A-3

, R

eact

ion

1 2*

9.

O^

+ H

,0-

H20*

+ 0

2.3

3(-

9)

18A

-11

!<>.•

N

* +

O -

N + 0

2

5.5

(-10)

18A

-4,

25,

33

Cf.

Tabl

e 18

A-3

, R

eact

ion

5 •

Rec

ent

dat

a on

the

ene

rgy

depe

nden

ces

of

thes

e re

actio

ns a

re c

olle

cted

in

Ref

eren

ce 1

8A-3

3.

n x >

3 00

>

^

—

•'•" •

—

'•"•

*

2 ro

Tab

le

18A

-1.

(Co

nt'

d)

Rea

ctio

n

k (c

m3 /

sec)

R

efer

ence

s C

omm

ents

11.

Is

T *

NO

-N + N

O*

8.0

(-10)

18

A-5

5

12.

N

* •

HjO

- H

2C

/ -

N

2.5

7(-

9)

18A

-11

13.

O

j(o

4n

u)^

°2"*

°2 +

02

3(-

10)

18

A-5

6

Qu

ench

ing r

ea

cti

on

.

14.

O

j(o

4n

u)

fN2~

N2

+ °

2

4.0

(-1

0)

18A

-56

15.a

. O

JX

n

) •

NO

- 0

0 + N

O"

4.4

(-10)

18

A-5

7

*

b. 0

2(a

4 n

o)

* N

O -

02 «

• NO

4

1.1

(-9

) 18A

-57

16.

O

j +

N0

2 -

N0

2 + 0

2

6.6

(-10)

18

A-5

9

17.

O

l *

Na -0

2 •*

• No

* 6.7

(-10)

18

A-1

0

See

par.

18A

.3.7

.

Cf.

T

able 1

8A

-3,

Rea

ctio

n

10.

18.

N

0 • O

- N

0 +

O

I.O

(-II)

18A

-60

**

19.

N

2

+ N -

N

j +

N+

<

1.0

(-1

1)

18A

-61

No

t o

bse

rved

.

* k

for

the

gro

un

d-s

tate r

eact

ion (

15

.a.) w

as f

orm

erly

cit

ed a

s 6.3

(-10),

base

d on

th

e in

adve

rten

t e

xp

eri

- m

enta

l ad

mix

ture

of

the

ex

cit

ed

-sta

te r

eact

ion (

15.b

.) (

Ref

eren

ces

18

A-2

5, 1

8A

-58).

30

0K;

alm

ost

ind

epen

den

t o

f te

mp

erat

ure

. B

ran

chin

g r

ati

o f

avor

s b

y 0

.93

/0.0

7.

Rea

ctio

n 1

1,

Tab

le

18

A-3

ove

r th

is

Z

> i C

O

X

m

M

i ..i

ii .

. T

' —

•

Tabl

e I8

A-1

. (C

on

t'd)

?

I

Rea

ctio

n V

(cm

J/$

ec)

Ref

eren

ces

Com

men

ts

20

/ »

VO

2-N

2*O

; 5.0

(-11)

18A

-25, 3

1,

33,

47

See

par.

18A

.3.4

.

21.

N!

+ N

O -

N2 *

NO

+

3.3

(-10)

18A

-58

22

.a.

Nj •

H20

- H

20

+ +

N2

2.1

9(-

9)

18A

-11

b.

- N

2H

+ O

H

23.

N2 +

No -

N2 +

Na4

5.8

(-10)

18A

-10

N m

ay d

isso

ciat

e

24.

N4+

°2**°2

42

N2

4(-

10)

18A

-46

25.

NO

* +

Na -

NO + N

a4

7.0

(-11)

18A

-10

26.

N0

2 * N

O -

N0

2 + N

O4

2.9

(-10)

18A

-45

See

par.

18

A.3

.12

.

27.

H*

+ O

- O

4 •

H

3.8

(-10)

18A

-51

28.

H+ +

NO

- N

O4 +

H

1.9

(-9)

18A

-51

29.

OH

* +

02 - O

H + 0

2

~2.0

(-10)

18A

-62

* R

ecen

t da

ta o

n th

e en

ergy

dep

ende

nce

of t

his

reac

t! o

n ar

e co

dec

red

in R

efer

ence 1

8A-3

3.

n x

> 3 00

>

m

Tab

le

18

A-1

. (C

on

t'd

.)

00

>

I 1

Rea

ctio

n k

(cm

s

ec)

Ref

eren

ces

Com

men

ts

30.

H 20

* • 0

2-H

?0

• 0

2

-2.0

(-10)

18

*-4

7,

62

31.

CO

' •

O

• O

* •

CO

1.4

M0)

18A

-51

32.

CO

* *

NO

- N

O' •

CO

3.3

(-10)

18A

-51

33.

co

2 +

o ^

co2 • O

—

K-1

0)

18A

-58

Cf.

Tabl

e 18

A-3

, R

eact

ion

31.

34.

co

2 * o

2 -

co

2 • o

2

5.0

H1)

18A

-58

35.

C0

2

• N

O-C

02 •

NO

* l.

2(-

10

) 18

A-5

8

36.

C0

2 • H

- H

' -C

02

—

K-1

0)

18A

-63

Cf. T

able 1

8A-3

, R

eact

ion

32.

37,

S*

* N

O -

NO

* *

S 4.2

(-10)

18A

-64

38.

30

2 *

• 02 -

02

• S

02

2.8

(-10)

18A

-64

z > 2 00

1111

,1

•

m.i

i iJ

i IIU

.IIIIU

II

00

>

I

Tab

le 1

8A

-2.

N

eg

ati

ve

-Io

n c

har

ge-

-tra

nsfe

r.

Rea

ctio

n

k

(cm /

jec)

Ref

eren

ces

Com

men

ts

i. o

" ^

o3-o

- O

j 5.3

(-10)

18A

-32

2.

O

" •

NO

j -

O + N

O"

1.2

(-9)

18A

-32

3.*

0

^0

3-0

^0

3

4.0

(-10)

18A

-32

4.*

O

j + N

Oj -

02 * N

O' 7

8.0

(-10)

18A

-32

5.

02 - S

02 - S

O~

- 0

2

4.8

(-10)

18A

-65

6.

0

3 • N

Oj -

Prod

ucts

2.8

(-10)

18A

-41

7.

N

O"

* 0

2 -

O"

* N

O

5.0

(-10)

18A

-66

8.

H

" +•

N0

2 -

H 4

NO

~

2.9

(-9

) 18

A-3

2

9.

O

H"

* N

02 - O

H +

N0

2

1.0

(-9)

18A

-32

10.

o

l* H

jO +

O3

- Pr

oduc

ts

3(-1

0)

18A

-65

11.

0

2(H

20) 2

+ 0

3 -

Pro

du

cts

3.4

(-10)

I8A

-65

' *

-

•

-.,

• -

k fo

r th

ese

reoc

tions

is

litt

le a

ffec

ted b

y on

e or

tw

o w

ater

s of

hyd

ratio

n on

the

O-

ion

(Ref

eren

ce 1

8A-6

5).

o

>

—<

m

XI

00

>

• i"

iM'W

Wi"

"

-—

- -

"

"

i '..

H'U

Miw

ifN

Miia

! -I

U

5 i

Ta

ble

18

A-2

.

(Co

nt'

d.)

Re

actio

n

k 'c

m*5

sec)

R

efe

ren

ces

C

om

men

ts

12. c

o;.o

3-o

; co

2-o

2

13.

S

O^

• N

02 -

N0

2

• 0

2

• S

02

I.3

M0

)

2.5

(-1

0)

18A

-65

ISA

-65

Als

o g

ive

s N

O-.

Z

>

CO

Ta

ble

18A

-3.

Po

sit

ive

-io

n a

tom

-in

terc

ha

ng

e<

k

Reachon

!

(cm

3

sec)

R

efe

rence

s |

C

om

me

nts

1.*

O

*

Mv

l 2 -

N

• N

O *

1.2(

-12)

18

A-3

1,

33

47

See

par.

18A

.3.3

.

2.

O*

•» N

LO

- N

O' • N

O

\ 2

.3 (

-10)

18

A-5

4 C

f.

Ta

ble

18A

-1, R

eacti

on

8

.

3.

o*

•*• H2-H

+

OH

* 2

.0(-

9)

18A

-62

4.

o'

+co

2-c

o • o

2

1.1

(-9

) 18

A-2

5, 3

1 47

C

f.

Ref.

18

A-2

5 f

or

en

erg

y

dep

en

den

ce.

5.*

N

>

02-0

;N

O

5.5

(-10)

18A

-4,

25,

33

| C

f.

Tab

le

18A

-1, R

eacti

on

6.

N

+

H2 -

H

+ N

H

5.6

(-10)

18A

-62

7.

Oj

+ N

-O

•

NO

* 1.8

(-10)

18A

-31, 4

7 *

Re

ce

nt

da

ta o

n

the

en

erg

y d

ep

en

de

nc

es o

f th

ese

reacti

on

s a

re c

ollecte

d in R

efe

ren

ce

18A

-33.

... 4

Mb

'-"-•'".'

wn

i.n

.JM

'11

•

"il

.fP

ILpül

*

00

>

Tobl«

18A

-3.

(C

on

t'd.)

React

ion

k 3

(cm

see)

R

efer

ence

s C

omm

ents

8.

0

2 -

N

-N

O

- N

O'

<1

.0f-

15

) 18A

-31,

47

N

ot

obse

rve

d;

rate c

on

sta

nt

limita

tio

n s

ho

vn h

ere I

s ap-

plic

able

at

300 a

nd 6

00K

.

9.

0

? - h

' -

Pro

du

ct

<1.0

(-M

) 18A

-62

10.

O

j *

Na -

O

* N

aO

* 7

.7(-

ll)

18A

-67

C

f.

Table

18A

-1,

Re

act

ion

17

.

11.

N

' •

O- N

•

NO

' 1

.4(-

10

) 1

8A

-58

, 60

+

12.

N

2

• H

? -H

•

N?

H

1.7

(-9)

18A

-62

13.

N

3

• 0

2-

Pro

du

cts

1.0

t0.3

(-10)

18A

-46

2

00

K

14.

0

4*0

- 0

20

3

~3(-

10)

18

A-6

8

is.

o4 - H

2O

- o

? * c

yH

2o

1.5

(-9)

18A

-13

S

ee p

ar.

18A

.3.

11.

16.

N

4 + 0

2 -

02

» N

?

• N

2

4±1(

-!0)

1

18A

-46

200K

17.

N

O*

' 0

3-

NO

* *

02

<

1(-1

4)

L

13A

-59

'Energ

y d

ep

en

de

nce i

s g

ive

n i

n R

e T

eren

ce 18A

-60.

I8A

-»

by

0.9

3

0.0

7.

Bra

nch

ing r

atio f

avo

rs t

his

ove

r R

eact

ion

18 o

f T

able

n >

-a

oo

>

>

i So

Tabl

e 18

A-3

.

(Co

nt'd

.)

Rea

ctio

n |

k

(cm

J

sec)

R

efer

ence

s C

omm

ents

!

18.

H'

• C

02-H

CO

' •

O

S 3

(-9)

18

A-6

3

19.

s'

• c

2-so

' •

O

1.6

M1

) 18

A-6

4

20.

°?'N

2 *0

.N

•

O*

l:0

.5r-

9)

Aut

hor's

21.

£

*

-

£

«-

•

°2*

N2

* H2° "

°2

* H2°

* N

2 4t2

(-9)

est.

18A

-13

22. o

.O^'^

O f

H20 -

02

*- O

H

- H

O*"

2(

-10)

18

A-1

3 Se

e pa

r.

18A

.3.

11.

b.

-

02

» H3

O^.

OH

1.0

(-9)

18A

-13

23.

NO

^N

O *

H20

- N

O'-H

?0 *

NO

1.4

(-9)

18A

-44

24.

NC

'«H

20

«• N

O -

NO

'-N

O J

HO

9

(-1

4)

18A

-44

296K

25.

NO

^-H

20 •

• H -

H 30*

" *

NO

*7

(-12)

18A

-69

26.

NO

*-H

20 *

• OH -

H3Of «

• N0

2

<6

(-ll

) 18

A-6

9

1 2

7.

NO

*(H

20) 3 • H

20

- H

30

*(H

20) 2

• H

N0

2

7(-

ll)

18A

-12, 4

3,

44

See

par

. 18A

.3.1

2

Z

>

u

. -

•-•D

JU

!• „

.Ma

-

—""

'

I

Tabl

e 18

A-3

.

(Co

nt'

d.)

Rea

ctio

n k

(cm

s

ec)

1 R

efer

ence

s C

omm

ents

28.

NO

*'C

02

* H ?

0 -

NO

*-H

O «

- C

O?

~

l(-9

) 18

A-4

6 Se

e p

ar.

18

A.3

.14

.

29.

H2°

4 * H

20"*

H3°

*

OH

1.8

(-9)

18A

-21, 3

1

30.

H 30

+-O

H f H

20-H

3o

'-H

20 *

OH

1.4

(-9)

! 1

8A-1

3

31

. C

O*

• O

-CO • O

j ~

1.6

(-10)

18A

-58

Cf.

Tabl

e 18

A-1

, R

eact

ion

33.

32.

C0

2 * H

- H

CO

* O

6(

-10)

18

A-6

3 C

f.

Tabl

e 18

A-1

, R

eact

ion

36.

33.

No

f

03 - 0

2 + N

aO

<

1.0

(-11)

18A

-6

No

t ob

serv

ed.

34.

K*

+ 0

3- 0

2 i K

O*

<1.0

(-11)

18A

-6

No

t ob

serv

ed*

35.

Mg"

• 0

3-0

2 + M

gO

+

2.3

(-10)

18A

-6

36.

Co*

• O

, -

02 * C

oO

* l.

6(-

10

) 18

A-6

37.

Fe* *0

3-0

2

* F

eO*

1.5

(-1

0)

18A

-6

38.

u* * o

2- u

o4 * O

8.5

^(-

10)

18A

-70

n

x >

3

CO

>

""""

"

—

»«"•

'••«

•"*"

* •*-"

•

5 i »o

o

Tab

le

18A

-3.

(Co

nt'

d.)

Rea

ctio

n

k (c

m*5

sec)

R

efer

ence

s C

omm

ents

39

.

U

• N

j-U

N'

•

N

<1

(-tt

) 1

1

8A

-70

40

.

Mg

O*

• O - 0

2

i M

g'

- 1

.0M

1)

18

A-6

41

.

S

iO*

• O

- 0

2

* S

i*

-2.0

M0

) 1

8A

-36

S

ee p

ar. 1

8A

.3.5

.

o

Z

>

ô

•u

oo

X

Tab

le

18A

-4.

N

eg

ati

ve-i

on a

tom

-in

terc

han

ge.

Rea

ctio

n

k (c

m3

sec)

R

efer

ence

s j

Com

men

ts

1.

o"

• NjO

- N

O

• N

O"

2.3

r0.5

(-1

0)

18A

-71

2.

D

J- N

2-0

2-

N20"

<

1.0

(-1

5)

18

A-3

2

No

t o

bse

rved

.

3.

O

"-

NO

- 0

2

* N

02

I.O

MU

18A

-32

P

rodu

ct i

de

nti

fic

ati

on

(N

O3

• O

) g

iven

in

Ref

. 1

8A

-32 I

s p

rob

ably

in

corr

ect

4.

O

-. H

-OH

" • o

2

8.4

(-10)

18

A-7

2

5.

O

"'

C0

2 -

02

• C

O"

4.0

(-10)

18

A-3

2

•

* k

for

this

{R

efer

ence

«»ac

tion

is s

lig

htl

y d

ecre

ased

fo

r on

e w

ate

r o

f h

ydra

t.o

n a

nd d

rast

ical

l>

I8A

-65).

d

ecre

ased

fo

r tw

o

_

——

—

•"—

' w

tm

CO

>

I

Tab

le

ISA

-4.

(C

ont'd

.)

Re

act

ion

lc

'cm

3

sec)

R

efer

ence

s C

omm

ents

|

6.

o;-

o-o

2.o

- 4

.0M

0)

18A

-38

2 0o

'

O

may

be

a m

inor

pro

duct c

ha

nn

el.

7.

O"

•

NO -

O

• N

O"

4

2

J

i

2

.5(-

10

)

! 18

A-3

8

8.

°4

• H?0-0' 2-H

20

0

2

1.4

(-9)

18A

-73

9.

°4

• C

°2

- °

2

• C°4

4.

3<-1

0>

18A

-38

10.

NO

l •

O -

Pro

duct

s *I

.OM

I)

18A

-74

No

t o

bse

rve

d.

11.

NO

l •

N -

Pro

du

cts

<1.

0M1)

I8

A-7

4

Not

ob

serv

ed

.

12.a

b

. N

O"

• H

-OH

" •

NO |

-HN

Oj

e

1

4(-

10

) 18

A-7

2 k 1

2o *

0.5

k12j

°4k

12

b *v

\2

13.

N°2

' °

3"*

°2 '

N°3

1.8

M1)

18A

-32

14.

NO

j •

NO

j -N

O

• N

O*

-4.0

(-12t

18A

-38

See

par.

18A

.3.1

0.

15.

NO

l •

O -

Pro

duct

s <

1.0

(-1

1)

18A

-38

Not

obse

rved

.

WP

P!"

"'""'

*~_

5 i 8

Tabl

e 18

A-4

.

(Co

nt'

d.)

Rea

ctio

n It

(cm

s

ec)

Ref

eren

ces

Com

men

ts

16.

N

O3 >

- N - P

rodu

cts

«1

.0H

D

18A

-38

No

t ob

serv

ed.

17.

N

O3

• N

O-N

Oj

N

Oj

«1.0

MU

18

A-3

8 Se

e pa

r.

18

A.3

.10

.

18.

O

ON

O"

• N

O - N

O,

N

Oj

- I.

5(-

1I)

18

A-4

0

19.

C

O3

• O

- C

02

• 0

2

8.0

M1

) 18

A-3

2

20.

C

O3

• N

O -

CO

j •

N0

2

9.0

(-1

2)

18A

-32

*

21.

C

O"

* N

02-

C

02 •

NO

3 2(

-10)

18

A-7

2 #

22.

C

O"

• 0-0

2 • C

O3

1.5

(-1

0)

18A

-38

CO

j •

O3

may

be

a m

inor

pr

oduc

t ch

ann

el.

1

23.

C

O*

• N

O -

C0

0

• N

O~

•»

2

3

4.8

(-11)

18A

-38

24.

O

j H

20 * N

O -

H20 * N

O~

3

.K-1

0)

18A

-40

25.

0

2-H

20

• C

02 -

H20

* C

O^

5.8

(-10)

18A

-40

26.

O

-'H

-O

• C

O- -

Ptod

uets

3(

-10)

18

A-6

5

* k

for

thes

e re

actio

ns i

s lit

tle

affe

cted

by

one

wat

er o

f hy

drat

ion

(Ref

eren

ce

ISA

- •65

).

I

' -"*

-*-•

IIM

M

—«'•

•'

Tobl

e 18

A-4

. (

Co

nt'

d.)

Rea

ctio

n k

(cm

s

ec)

Ref

eren

ces

Com

men

ts

1 27

# O

l(H

jO>

2 • C

02 -

Pro

duct

s 2(

-10)

16

A-6

5

28.

NO

j • H

?0

• S

02 - N

O"

• SO

? * H

20

1.5

(-9)

18A

-65

29.

C0

3*H

2°

' N

O"

Pro

dü

Cts

l.

8(-

11

) 18

A-6

3

!

30.

CC

j- H

O • N

O? -

Pro

duct

s i.5

(-;o

) 18

A-6

5

n x

>

a>

>

^3

co

>

mm

P

*H

ll .

11

.llllj

l I»

ww

»«5W

Pt«

*».l.

lll ,«

l|.

HIP

P.1 I,

I

II

I1-I

.1J.

II.II

I

.l,|

i|.P

i,|H

UI'.

).u

:yw

CO

>

I

f o a 5 en

Tab

le

18

A-5

.

Th

ree-

bo

dy

po

sit

ive-i

on r

eact

ion

s.

Rea

ctio

n

k 1 (

cm6's

ec)

Ref

eren

ces

Com

men

ts

1.

0

*+ N

2 + H

e-N

O''+ N

+

He

5.4

(-2

9)

18A

-8

82K

; N

-O a

pp

ears

to f

orm

a

t fi

rst

and

then

pre

dis

soci

- ate

.

|

2.

0

2+

20

2-0

^ + 0

2

2.8

(-3

0)

1S

A-2

0

307K

; se

e p

ar. 1

8A

.3.8

.

!

3.

O

j •

N2 i N

2-0

2-N

2

'- N

2

8*4

(-3

1)

18

A-1

3

200K

4.

0

2 +

N20 + H

e - 0

2 •

NjO

+ H

e 5.2

(-29)

18A

40

200K

5.

0

2 + H

20 +

02 -

02 •

H20 - 0

2

2.3

(-2

8)

18

A-1

3

296K

; se

e p

ar.

18A

.3.1

1.

6.

0

2 +

C0

2^ H

e-0

2-C

02 + H

e 2.3

(-29)

18A

-40

200 K

7.

N2 + N

2 +

He - N

* +

He

tl.2

(-28)

|1.9

(-29)

18A

-8

18A

-8

82K

28

0K

8.

N

j+2N

2-N

^N

2

5.0

(-2

9)

18A

-29

30

0K

1

9.

NO

+ +

02 +

He-N

O+»

02 + H

e <

6(-

34)

18

A-4

6

200K

10.

N

O+ + N

2 + H

e -

NO

+-N

2 -

f H

e 4(-

30)

18

A-7

4

90K *

* B

ecau

se o

f th

e se

riou

s b

reak

up p

rob

lem

, th

e eq

uilib

riu

m c

on

stan

t is m

ore

rele

va

nt

than

th

e ra

te c

on

stan

t 1

a

lon

e; K

is

rep

ort

ed a

s <

1(-

19

) a

t 20

0 an

d 22

5K (

Ref

eren

ces

18A

-46,

18

A-7

5)

and a

s > 1

(-2

0)

at 2

98K

(R

efer

ence

18

A-7

6).

o

Z

>

CO

X

• -

- -

—

' "

'•••—

• •

- --

-

?

Tab

le 1

8A

-5.

(C

on

t'd

.^

Rea

ctio

n

k (c

m6

sec)

;

R

efer

ence

s C

omni

ents

11.

N

O'

4 N

2

* N

O-

No

"'N

„

*• N

O

2(-

31)

! 1

8A

-77

30

0K *

!

12.

N

O*

*•

2 N

O r

NO

*"-

NO * N

O

5.0

(-30)

18A

-1

300K

; re

vers

e ra

te c

on

stan

t =

9(-

16)c

m3/s

ec.

13.

N

O'

* H

jO

+• N

2- N

O*"

-H20

«• N

?

1.5

(-2

8)

18

A-1

2,

43

300K

; se

e p

ar.

18A

.3.1

2.

14.

N

O'

* C

Oj

+ H

e - N

O*-

C0

2 *

He

1.0

(-29)

18

A-4

6

200K

15.

N

O'

• C

Oj

* N

2 -

NO

+*C

02 * N

2

3(-

29)

18

A-4

6

200K

16.

NO

* +

C0

2 < C

02 - N

O**

C0

2 +

C0

2

2(-

29)

18

A-7

8

300K

17.

H

30

+

• H

jO

- 0

2

• H30'

• H20 J

02

3

.7(-

27

) 18

A-2

1 30

7K

Rev

erse

rat

e co

nst

ant

18.

H

30* +

HjO

«

N2-H

30

+-H

20 A N

2

3.4

(-2

7)

18A

-21

300K

=

7(-

26

)cm

3/s

ec.

19.

H30

^-H

20 +

H20 f

02 z

H30

+(H

20) 2

+ 0

2

2.0

(-27)

18A

-21

307K

] R

ever

se r

ate

con

stan

t =

7(-

18

)cm

3/s

ec.

20

.

H

30

*-

H20 4

- H20 + N

2 r

H30

+(H

20) 2

+ N

2

2.3

(-27)

18A

-21

30

0K

i *

Bec

ause

of

the

seri

ous

bre

aku

p p

rob

lem

, th

e eq

uilib

riu

m c

on

stan

t is m

ore

rele

van

t th

an t

he

rate c

on

stan

t \

alo

ne;

K is r

epo

rted

s <

1(-

19

) at

200

and

225

K

(Ref

eren

ces

18

/ ̂-4

6,

18

A-7

5)

and

as >

l(-

20)

at

298K

!

|

(R

efer

ence 1

8A

-76

).

o

X

>

co

>

'

-••'«

—'--•

00

>

I Ox

Tab

le 1

8A

-5.

(Co

nt'

d.)

Rea

ctio

n

k (c

m6's

ec)

Ref

eren

ces

<**c

»mm

ents

I

21

.

! 2

2.

H30

+(H

20) 2

+

H 20 f O

^H

30

+(H

20) 3

^ O

j

H30^

(H20) 2

+ H

20 t N

2* H

30

^(M

20) 3

+N

2

2.0

(-2

7)

2.4

(-27)

18A

-21

1

!8A

-21

307K

j

|

( R

ever

se r

ate

con

stan

t

300K

l"0(-,

4)em

3/s

ee-

23.

H3o

"(H

20) 3

* H

20 +

02r H

30

4(H

20) 40

. 9.0

(-28)

18A

-21

307K

; re

vers

e ra

te c

on

stan

t =

6.0

(-12)c

m3/s

ec

.

24.

NO

+-H

20 * H

20 * N

j-N

0'(

H20) 2

+ N

?

j 1.

1 (-

27)

18A

-12, 4

3 30

0K;

see

par

. 18A

.3.1

2.

25.

NO

^(H

20) 2

+ H

jO

i N

2-

NO

+(H

20) 3

+ N

2

1.6

(-27)

18A

-12, 4

3 30

0K;

see

par

. 18A

.3.1

2.

26.

Mg+

+ 0

2 +

Ar - M

gO

* +

Ar

-2.5

(-30)

18A

-6

300K

27.

Ca+

*

O2 + A

r -

Ca

Ol

+ A

r -6

.6(-

30)

18A

-6

300K

28.

Fe

+ 0

2 +

Ar -

Fe0

2 +

Ar

-1.0

(-30)

18A

-6

300K

29.

i

30.

K*

^C

02 +

C0

2=

?K+.C

0? +

C0

2

Na+

+ C

02 +

C0

2 r

N

a^

-r.C

2 +

CO

?

4^

(-30)

2(-

29

±0

.5)

18A

-79

18A

-80

Rev

erse r

ate

con

stan

t =

+2

5

3

) 2.5

jj3

(-1

3)c

rn

/se

c.

Rev

erse r

ate

con

stan

t *

l(-1

4±0.5

)cm

3/s

ec.

i

31.

Na

*-C

02 +

C0

2 +

C0

2r N

a+(C

02) 2K

02

2(-

29±0.5

) 18

A-8

0 R

ever

se r

ate

con

stan

t •

5(-

13i0

.5)c

m3/s

ec.

Z

>

oo

X

• II

> i

i i

••!•

-in

.

i'

"

•• '

*>>

imm

jmi

• —

•

tmm

*

Table

18A

-6.

Thre

e-b

ody

ne

ga

tive

-io

n r

eact

ions

CO

>

i fSJ

Rea

ctio

n k

(cm

° se

c)

Ref

eren

ces

Com

men

ts

1.

0%

20

2-0

-.0

2

ll.2(-

30)

|1.0

5(-

30

) 18

A-7

3 18

A-8

1 30

0K

298K

!

2.

O"

» N

2

*• H

e - N

jO"

« H

e 1

1.3

(-30)

(~4

.0{-

31

) 18

A-3

2 18

A-4

0 80

K

|

200K

3.

O"

« H20 + 0

2-0

"-H

20 f

O

1.0

(-2

8)

18A

-73

300K

4.

o"

* co

2

• co

2 -

CO

3 • co

2

8.0

(-29)

18A

-82

300K

5.

) 4.0

(-31)

( 3.0

(-31)

18A

-39

310K

; se

e pa

r.

18

A.3

.9.

c;*

o2*

or

-o4%

o 2

18A

-73

18A

-81

300K

; re

vers

e ra

te c

onst

ant

= 2.7

(-14)c

m3/s

ec.

29

8K

i 6#

0

2 <

N

2 • H

e-C

"-N

2 +

He

~

~4.

0(-3

2)

18

A-0

20

0K

7.

02 * H

20 * 0

2 -

0~

- H

?0 +

02

3(-

28)

18A

-73

300K

8.

°2 + C

°2 '

<V

C°4

*°2

4.7

(-29)

18A

-65

300K

9.

o"

• co

2 -

co

2 -

co

~ 4 c

o2

9.0

(-30)

18A

-82

300K

% 1

10.

03^H

20^0

2-°

3-H

20 +

02

2.1

(-2

8)

18A

-73

300K

m

00

>

wm

a^m

wm

CO

>

I CD

Table

18A

-6.

(C

ont'd

. )

Re

act

ion

| k

(cm

° s

ec)

Ref

eren

ces

Com

men

ts

11.

NO

~

• H

20

• N

O-N

O'-

IÔ

* N

O

12.

0~

-H20

*• H

20

* 0

2 -

02(H

20

) 2

•• 0

2

1.3

(-28)

4(-

28)

18

A-1

18

A-7

3

1 3

00K

300K

•

o

Z

>

>o

CO

X

CHAPTER 18A

•%> * Table 18A-7. Charge transfer to neutral metals. *

Measured cross-section Extrapolated value of Reaction i for ions of 1 eV (at the thermal-energy rate

center of mass) constant 1

(cm2) (cm3/sec)**

N* ' No - N * Na+ small ';

O 4 Na - O + No small

N2 i Na - N. + Na^ | 3.0v 10"15 1.9 xlO"9

02 + No-Oj 4 Na' 5.5-,0-15 1.4 K 10"9

NO* 4 No- NO * Na+ 1.2* ?0'15

H.O^ * Na-H.O + Na*

H30" + Na - H30 » Na* j

2.8 • 10"14 2.7 * 10*"9 j

2.4 v 10"14

NJD* + Na- NJD • No* 2.7* 10~14 2.0 *10"9

Na + Na - Na + Na 2.3 * 10"14 2.8 * 10"9

N* * Mg- N * Mg* 1.1 v lo"14 1.2 HO"9

0* • Mg- O » Mg* j small

N*+Mg- N2< Mg' 1.8 *10"14

02 • A^g-02 • Mg* 7.6 *1(f15 ! 1.2'10'9

NO* - Mg- NO + Mg' 1.4 *10**14 1.0 *io~9

HO* * Mg-H O + Mg' 1.8 * 10"U 2.2 v 10"9

H30* * Mg-H30 • Mg 8.8 ' 10"15

N20* • Mg-NjO • Mg* 2.6 vIO"14 2.1 *10"9

Mg * Mg - Mg * Mg -14

3.8 • 10 4.7 * 10"9

N* ^Ca-N J Ca* 5.3 • 10"15 1.1 HO"9

RcvttHHi No 5. Jufw 1975

18A-29

DNA 1948H

Table 18A-7. (Cont'd)

Measured cross-section Extrapolated value of Reaction for ions of 1 eV (at the thermal-energy rate j

center of mass) | constant

(cm?) (cm3/sec)**

0 i Ca - O ; Ca 1.1 v 10"14 7.5 vlO-10

N^ • Ca-N2 • Ca' -14

3.0 10 -9

1.7 v 10

0'7 • Ca-02 • Ca' 1.5 v,<f14 4.1 vio"9

NO' * Ca- NO • Ca' -14

2.2 v 10 4.0 vlO"9

H20' • Ca - H20 * Ca' 5.5 v,o-14 4.0 xlO"9

HO+i Ca- HO 4 Ca' -14

3.4 v 10 ' j 4.4 x 10"9

NO' * Ca- NO • Ca" 4.5 v 10"14 -9

3.7 v 10

Ca *• Ca - Ca • Ca -14

6.0 x 10 1

Measured cross-section for ions of 3 eV (at the

center of mass)

H* • Fe - H • Fe*

(cm2)

9.5 x 10"16

N" • Fe - N • Fe' 1.6- IQ'16 1.5 x 10'9

0 • Fe - O • Fe 1.3 x 10"15 2.9 xlO"9

N2 • Fe - N? • Fe ' 2.9 x 10"15 4.3 xlO"10

NO • Fe - NO • f e' 2.4 *10"15 9.1 xlO"10

02 ' Fe - 02 • Fe' -15

2.0 v 10 1.2 xTO"9

HO' • Fe-H O • Fe' 3.3 x 10"15 1.5v 10"9

* Table kindly supplied by J.A. Rutherford 'Referenc e 18A-83). Cf. also References 18A-84 through 18A-88.

** Extrapolation scheme described in Reference 18A-8 9.

18A-30 Rtrv.vo«» No b. June 197b

CHAPTER 18A

REFERENCES

18A-1.

L8A-2.

18A-3.

18A-4.

18A-5.

18A-6.

18A-7.

Lineberger, W. C., and L. J. Puckett, Phys. Rev. 186, lib (196V); Ibid. 187, 286 (1969); Ibid. AJ_, 1635 (1970).

Copsey, M. J. , D. Smith, and J. Sayers, Planet. Space Sei. J4, 1047 (1966).

Smith, D. , and R.A. Fouracre, Planet. Space Sei. ^6, 24 3 (1968).

Dunkin, D.H., F.C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. 49, 1365 ,1968).

Ferguson, E. E. , U.K. Böhme, F.C. Fehsei.fe'd, and D.B. Dunkin, J. Chem. Phys. 50, 5039(1969).

Ferguson, E. E. , and F.C. Fehsenfeld, J. Geophys. Res. 73, 6215 (1968).

Böhme, D.K., D.H. Dunkin, F.C. Fehsenfeld, and E.E. Ferguson, J. Chem. Phys. 49, 5201 (1968).

18A-8. Böhme, D.K., D. B. Dunkin, F.C. Fehsenfeld, and E.E. Ferguson, J. Chem. Phys. 5^, 863(1969).

18A-9. Fehsenfeld, F.C, M. Mosesman, and E. E. Ferguson, J. Chem. Phys. _55, 2115 (1971).

18A-10. Farragher, A. L. , J.A. Peden, and W. L. Fite, J. Chem. Phys. 50, 287 (1969).

18A-11. Howard, C.J., H.W. Rundle, and F. Kaufman, J. Chem. Phys. 53, 3745 (1970).

18A-12. Howard, C. J. , H.W. Rundle, and F. Kaufman, J. Chem. Phys. 5£, 4772 (1971).

18A-13. Howard, C.J., V.M. Bierbaum, H.W. Rundle, and F. Kaufman, J. Chem. Phys. 57, 3491 (1972).

18A-14. Fehsenfeld, F.C, D. L. Albritton, J.A. Burt, and H.I, Schiff, Can. J. Chem. 47, 1793 (1969).

18A-15. Albritton, D. L. , A. L. Schmeltekopf, and E. E. Ferguson, Bull. Am. Phys. Soc. J_3, 212(1968).

18A-16. Warneck, P., J. Chem. Phys. 47, 4279(1967).

18A-17. Warneck, P., Planet. Space Sei. J^, 1349(1967).

18A-18. Paulson, J. F. , K.P. Mosher, and F. Dale, J. Chem. Phys. 44, 3025 (196o).

18A-31 Revision No 5. June 1975

. .'— - ...'•:*

. •

DNA 1948H

l.vA-11'. Paulson, J . I- . , Adv. Chem. 58, 28(P't,b).

18A-20. Durden, [). A. , 1'. Kebarle, and A. Good, J. ehem. Phys, •'ü, 805 i l'" M.

18A-21. C'iood, A. , i). A. Durden, and P. Kebarle, J. Chern. Phys, 52, 212, 111 • P>70).

18A-22, Turner, B. R., and J.A. Rutherford, J. (ieophys. Res, 73, 6751 119o8».

18A-2S. Turner, :.!•'.. J.A. Rutherford, and I). M..I. Compton, .!. Chem. Phys. A ~, !' ''.. « 1 '•* • i.

i8A-24, Helmer 1, J. , R. Johnsen, and M.A. l>i<>ndi, .. < hem. Phys, 51., 504 ! i 1" ...

!• '.-1-, Johnsen, R., li.l . i r.»v.n, and M.A. hiondi, J. ( hem. Phys. 52, •'<'-'• i I '7III.

L8A-2t>, Golden, D.E., Ci. Siniii.tt, and I'. .. Varney, Phys. Rev. Letts. 20, IS** \ •• - .

< -.\-l~. Böhme, I). I.. . 1'. P, <.,:.. . . . i . i lasted, and !.. R. Meîli, I 'lanet. Spat e Si i. ! , I V 77 I •• A.

1 SA-28'. Ong. P. P. . al\Ü . . : . I:a: led, . . i :.\ .-. [_J. 'I l'""l.

i-A-.i-. Miller, I.M., .'.1. M..seiey, D.VV. Martin, and K.W.

Mt I) a n i e 1, i '••';• . i' < v. ! i • 11 s. 1 I , A > ! • • •*' i.

- A - .'• •. »neko, V. , .. : '*•'••• :-i. uui A l'.anomata, Mass

.s;Je *. t r« Js*. . I -, •!•• 1*7

."•.-•» I . ! .'• . .'• . : . . '• •:. .A i • <•!!•. 17, I 7 '7 ' I ••• '.«».

: <' . - ( ,, • ' •

M i •-.:::'., '.!.,'.:. •i'iM .!., 1 . < . 1 ehsenfeld,

:.. :.. i • r. !!• in, i:.'i A. '.. >, i nur It «•:••.. >t, .:. ( lu'ni.

; •

1 -. \ -

Si i.iin'l'r: .•,;, A. I.. , i.. I.. i- «rsjuson, and i- . (..

I «• i; s<• n!«• • t i. . ( :. < • r i:. i ' i. \ s . t*, 1 '• • I • • - .

( Malley, '..':.. ', < Lern. Phy». ; 1. '!< ' I '7'ii.

:••:-<•::•]';,;.'..<. at.. . ( :.»•;: . 17, I -''•- • I " • .

• »-j..-•••:.:• • l'i. i . « . , i:.»: !... I.. I < r_ • is<>n, J. (ieuphy s. R es,

7-;, 11 17 I •• •!.

5 ehsenield, I . ( . , !..:.. i erûs'iU, and \). K. r.onn.o,

; ; i:.»•' . > , •• • « ~ • l. I i , 1 i • t.

I8A-32 H. v.s..,' "... 'j • .. • 19/')

CHAPTER 18A

C L8A-39. McKnight, L.G., and J.M. Sawina, DASA Symposium on Physics and Chemistry of the I'ppcr Atmosphere, Stan- ford Research Institute (1969).

18A-40. Adams, N.G., D.K. Böhme, D.H. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys. 52, 3133 (1(>70).

18A-41. Dunkin, D.B., F. C. Fehsenteld, and E. E. Ferguson, Chem. Phys. Letts. _L5, 257 (1972).

18A-42. Ferguson, E. E. , D. B. Dunkin, and F. C. Fehsenfeld, J. Chem. Phys. 5]_t 1459(1772).

18A-43. Fehsenfeld, F.C., M. Mosesman, and E. E. Ferguson, J. Chem. Phys. 55_, 2120 (1971).

LsA-44. Puckett, L. J. , andM.W. 'league, J. Chem. Phys. 54, 25<>4 (1971).

18A-45. Fehsenfeld, F.C., E. E. Ferguson, and M. Mosesman, Chem. Phys. Letts. 4, 73 U%9).

18A-46. Dunkin, D. !'.. , F.C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. 54_, 3817 (1971),

1&A-47. Ferguson, E. E. , Revs, Geophys. 2» 505 (19C7).

I8A-48, Lindinger, W,, F.C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, .1. Geophys« Res. 79, 4753 (1974).

18A-49. Böhme, D.E., \.G. Adams, M. Mosesman, D. B. Dunkin, and E. E. Ferguson, J. Chem. Phys. 52, 5094 (1970).

18A-30. Stebbings, R.F., and .i.A. Rutherford, J. Geophys. Res. 73, 1035 1 L" M.

18A-31. Fehsenfeld, I.e., and E. E. Ferguson, J. Chem. Phys. ^>>, So»,». 1 1972).

l-A-52. NKFarland, M. . D. L. Albritton, F.C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Geophys. Res. 79, 2005 t 1974».

18A-33. Dunkin. D. B. , M. Mc Far land, F.C. Fehsenfeld, and E. E. Ferguson, J. Geophys. Res. In*, 3820(1971).

I8A-54. Ryan, K. R. , J. Chem. Phys. 37, 271 »1*71».

I8A-55. Ferguson, E. E. , F.C. Fehsenfeld, P.D. Col dan, and A. L. Schmeltekopf, J. Geophys. Res. To, 4323il9o3).

18A-33 «••v. •...)•• No *>. June 197b

'-- —" — •- •••"•-'

DNA 1948H

lHA-5t'. Lindinge r, W., M. Mi. Far land, F.C Fehsenfeld, A. I.. Schmeltekopf, and E. E. Ferguson, .i. Chem. Phys. in press (1975).

18A-57. Lindiager, W., D.I.. Albritton, F.C. Fehsenfeid, and E. E. Ferguson* J. Geophys. Res., in press (IV75).

18A-58. Fehsenfeld, F.C, D.B. Danhin, and E. E. Ferguson, Planet. Space Sei. J_^. I267<197ü).

18A-59. Fehsenfeid, F.C, K. E. Ferguson, and C. J. Howard, J. Geophys. Res* 78, 5^7 (1973),

I8A-60. Mc Far land, M. . D.I.. Albritton, F.C. Fehsenfeid, K.M. Ferguson, and A. 1.. Scbmeltekopf, J. Goophys. Res. 79, 2925 1974).

18A-61. Ferguson, E. E., F.C. Fehsenfeid, P.D. Go Ida n, A. I.. Schmeltekopf, and ii.i. Schiff, Planet. Space Sei. 13, 823 | I9t>5).

18A-62. Fehsenfeid, r.C, A. !.. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. 4t>, 2802 1 ••. ,\.

18A-63. Fehsenfeid, F.C, and E. E. Ferguson, J. Geophys. Res. 7b, 845 5 i 197 11.

18A-64. Fehsenfeid, F.C, and E. E. Ferguson, J. Geophys. Res. 78, I» 99 19731.

18A-65. Fehsenfeid, F.C, and E. E. Ferguson, J, ( hem. Phys. M, JIM i 1974).

!-A-»'. McFarland, M., D.i.. Dunkln, F.C Fehsenfeld, A. L. Schmeltekopf, and ii.i".. Ferguson, 3. Chem. Phys. 50, 2358 il'*72>.

I8A-67. Rol, P.K., and i..A. Entemann, J. Chem. Phys. 49, \4i'i i 19**81.

18A»68. Fehsenfeld, F.C, and E. E. Ferguson, Radio Sei. jj\ 113« 1972).

l8A-»'9. Fehsenfeld, F.C. C .'. Howard, VV. liarrop, und iJ. E. Ferguson, .'. Geophys. Res., in press il'*75».

18A-70. Johnsen, R., andM.A. hiondi, J. Chem. Phys. 57, 1975 11972).

18A-7S. Marx, R., G. Mauclaire, F.C. Fehsenfeld, D.B. Dunkin, and E. E. Ferguson, J. Chem. Phys. 58, J2t>7fl973|.

18A-34 Revision Nu 5. June 1975

-. . . : . . . - •— • • - •- • _— - - -1.. _!•*!

CHAPTER 18A

• IBA-72. Fehsenteld, F.C, C.J. Howard, and E. K. Kerûsun, ,1. Chem. Phys. 5jJ, 5841 11973).

18A-73. Pack, J.L., and A. V. Phelps. Bali. Am. Phys. Soc. lb, 214 i 1971).

18A-74. Fehsenteld, F.C. , unpublished results.

18A-75. Blonds, M.A., DASIAC Reaction Kate Data, No. 44, [>. 4 (1974).

18A-76. lieimerl, J.M.. and J.A. Vanderhoff, .1. Chem. Phys. MJ, 4?62 i 1974).

l-A-77. lieimerl, J.M., and J.A. Vanderhoff, American Geophys- ical I'nion Meeting, San I ramisio, California (1^71».

18A-78. Keimerl, J.M.. and 1...I. Puckett, Irans. Am. Ceophys. I'nion 52, ^>3 |P*711.

18A-79. Keller, C.h., and R. A. Beyer, Bull. Am. Phys. Soc. P_. .114 1 -7h.

IHA-80. Keller, G. E. , and I.A. Heyer, J. Geophys. kes. 7»-, 2*^ i 1 *71».

1 A-- Parkes, U.A., Irans. Faraday Soc. t>7, 711 11971),

I8A-82. Moruzzi, .'. i . . and A. V. Phelps, .'. Chem. Phys. 43, 4- 1 7 I 1 •• » >.

l8A-<*o. "lurner, U.K., and .!. \. Kutherford, Gulf General Atomic, Report GA- 'H27 i 1 »70».

18A-H4. Kutherf->rd, J.A», K.P. Mathis, i..K. lurner, and D. A. Vruuin, .i. Chem. Phys. 55, $785 »P*7li.

1-A-"-. Rutherford, J.A., and U.A. Vroom, J. Chem. Phys. 53, • 22 I 1 *T1>.

IHA-Ht.. Kutherford, .I.A., R. F. Mathis, B.R. lurner. and D. A. Vroom, J. Chem. Phys, ^j_» 4»-4 rp.*72i.

I-A--7. Kutherford, .I.A., »-'.!•. Mathis, B.R. 'lurner, and I>. A. Vroom, I. C!hc»>». Phys. 57, J0H7 i l *72».

IriA-Hh, Kutherford, .I.A., and I). A. Vroom, J. Chem. Phys. 57, 30'*! 1972».

l&A-h'*. LVolf, F.A., and U.K. lurner, J. (hem. Phys. 4H, 422» • I "Ml.

18A-35 R»Wf>r No 5. Jwfw 19 ?S

DNA 1948H

THIS PAGE IS INTENTIONALLY LEFT BLANK.

18A-36 ***,*,on N©. S. Ju,«. 1975

CHAPTER 18B

18. ION-NEUTRAL REACTIONS B. NON-THERMAL PROCESSES

David A. Vroom, John A. Rutherford, and Richard L. Voigt IRT Corporation

(Latest Revision 9 October 1974)

18B. 1 INTRODUCTION

D D C

DEC 8 SB

EISEUTTE1 D

Hie principal purpose of this chapter is to supply a compilation of data on ion-molecule and i harge-transfer reactions which are of interest in atmospheric chemistry and physics, 1 he constraint imposed by considering only reactions involving atmospheric species has led to the exclusion of a great deal of interesting information on other, non-atmospheric, ion-neutral processes.

'I he ion-energy rangt? covered by tiu- data in this chapter has been set arbitrarily at approximately l-^öü eV. The lower limit of this range was determined by the earlier lack of data for most reactions ir. the region between thermal energies and approximately one electron volt. [Thermal energy data are presented in Chapter I-A. , More recently, however, considerable data obtained by the use of flowing-aft erg low drift-tab»- methods have become available, and these data do cover the energy regime from near-thermal to several electron volts. The latter information, together with results from drift-tube experiments, have been included wherever available. 1 he upper limit >f uti eV was set arbitrarily such as to be greater th*n the energies <-t most experiments which measure in the low ion-energy region. ( hapter 1 includes data at still higher energies.

13B.2 TfCHNlOUFS

11.e various techniques employed arc for the most part described in t hapter 7. I he ex« eptioti is that <! the flowing »afterglow drift ••;•.(•, which has only re« entl) been developed. A complete descrip- tion of this method is t:iven in lieferen«, e 1 >! • - I.

I be ma or portion • •! ion-neutral data obtained in the energy range .«hove »ne «•!••> *r>:. volt has * une from experiments employ- ing i'.n !>eaii s. The i>eam-gas te« hnicjue, ts employed by diese and Maier Referen» es I.->».-»J through IM -•»». and the «. rossed- beam tet hnique of Stebnings, Rutherford, <t x:ci lurner i eferen«.es

DISTRIBUTION STATEMEKT A Appr'.v'd fci public release;

n- • ' " : Unlimited

18B-1

H.* i> J iy/t>

.•

.

•-

DNA 1948H

18B-5, 18B-6), are typical of experiments of this nature. Both of these employ double-mass-spectrometer systems; in each instance the first mass spectrometer is used to select the primary ion to be studied, and the second to analyze the products of collisions between the primary ions and neutral species« In order to obtain more information on the energetics of ion-neutral reactions, Paulson, Dale, and Studniarz (Reference 18B-7) have used the double-mass- spectrometer concept in conjunction with time-of-flight techniques. This incorporation of time-of-flight allows the translational energy of the product species to be measured.

Another beam technique, merging beams, has been described in two review articles (References 18B-8, 18B-V). This method has the advantage of facilitating the study of reactions in the energy range from near-thermal to several hundreds of electron volts; it can also give information on the kinetic energy of the products of reaction.

Still other methods which have been employed are the mass- spectrometer ion-source experiment (Reference 18B-10) and various drift-tube techniques (References 18B-11 through 18B-13). Both these and the flowing-afterglow drift-tube experiment (Ref- erence l'-'B-l) give data in the energy range from near-thermal to several electron volts. 'I he two drift techniques show promise of being extremely useful for obtaining cross-section data in the near-thermal-energy region.

18B.3 PRESENTATION OF DATA

Most of the data given here cover a considerable energy range and as a consequ nee are presented in the form of graphs. In order to simplify use of the graphical material, ali the information per- taining to a given reaction is provided in the figure caption refer- ring to that reaction. These figure captions include references to the workers who obtained the data, together with the technique* s) employed, any data available about the effects of excited states of the primary ions, any data available about the states of the product species, and other relevant information which may be helpful.

Rate coefficients i-.r a number of reactions which have been measured c* only out ion energy in the non-thermal region are presented in tabular form.

18B-2 Revision No S. June 1975

CHAPTER 18B

18B.3.1 Graphical Data

I wo typ<-*« of graph are included:

(A) 'J he first type (in Subsections 1KB. 3. 1 . 1 through 18B. i. 1. 1^1 is used for data obtained at higher energies r~ 1-500 eV). In these graphs, the ordinate gives the cross section for the reaction and the abscissa, the ion velocity related to that cross- section. I his velocity is obtained directly from the ion energy. 1 he use of velocity on the abscissa conforms with the format used in Chapter IT. It should ' «. noted, however, that the ion velocity does not account for any motion of the neutral primary species. In most cases the neutral primary is at room temperature (300 Kl and its motion is not of importance. For some atomic species which are formed by thermal dissociation the motion of the neutral can, however, become appreciable. The ion velocity will then be found to differ from the velocity in the center-of-mass system at low collision energies. The motion of both species is accounted for when the barycentric or collision energy is considered. This parameter is given across the top axis of each figure.

Data obtained using merging beams are plotted in the same format as is used for other beam data. Here, the collision energy is the energy at the center-of-mass of these experiments. The ion velocity giver, on the abscissa is obtained by taking a reasonable value for the neutral velocity and computing the corresponding ion velocity. I he neutral velocity chosen is that which would be expected in a beam-gas or c rossed-beam experiment involving the same species.

The higher ion-energy '~I-500 eV) data graphs are organized as follows;

1) Data for each neutral reactant are grouped together in a given subsection. These subsections are arranged in the following order; I he atomic neutral species come first 'Subsections 1KB. i. 1. 1 through 1KB. 3. I. 7» in order of increasing atomic weight followed by diatomic (Subsections 1KB. 3. 1.8 through 1KB. 3. 1. 10) and then triatomic (Subsections 1KB. 3. 1. 11 through 1KB. 3. 1. 15) molecular species, -*ac h in order of increasing moitc ular weight.

iii Within each neutral reactant subsection, the data for positive-ion reac tions precede those for negative-ion processes within this grouping the data for the atomic reactant ions precede those for molecular ions. I he atomic and molecular ions are arranged in order of increasing atomic or molecular weight.

18B-3 Revision No. 5. June 1975

DNA :948H

3) For a given set of reactants, if data on formation of more than one set of products are available, the following procedure is followed: If only one or two determinations of each cross-section are used, the data are combined on one plot. If considerable data are available for the different reaction channels, the data are given in different plots which are then ordered as follows:

a) Charge transfer; b) Dissociative charge transfer; cl Ion-molecule processes, in order of

increasing ./eight of the product neutral species.

B) The second type of graph 'in Subsection 18B. 3. 1. 16) is used to present data obtained using drift tubes or flowing-afterglow drift tubes. In these figures the rate constant is plotted on the Or- dinate. For drift-tube data, the electric field strength per unit pressure (E/P) is used on the abscissa and the average ion energy is placed at the top of the figure. For the flowing-afterglow drift- tube studies the energy at the center-of-mass is given on the abscissa and values of electric field strength per unit number density iE/N> are given at the top of the figure. These formats conform with those commonly used by workers in the field.

The reactions are ordered in the same fashion as for the higher- energy data. That is, the information on atomic neutral species precedes that for molecular species and each group is arranged in ord';r of increasing atomic or molecular weight.

18B-4 M.-yiSUiii No 5. Ju»R' 19/5

... - _

188.3.1.1 O-Afom Reactions

(«1IVIW IM»0» 'c«l

1— 1— 1—r T— —T- -T- T

- „• o ... '-' "

*^»°A«P 00 o A4 2".

A «A

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CHAPTER 180

luii I'.imt (««•• IM:

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At

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A o

A A fcAi

a—I—i—L J—»—J—«—l—t-

Figufe 18B4. Cross section for th« reaction H + 0 - H + 0 Orclvi are the data of Rutherford and Vroom (Reference 18B-14) obtained using crossed beam techniques and O atoms produced by thermal dissociation. Triangles are the data of Stabbing». Smith, and Ehrhardt (Reference 18B 15) obtained using crossed beam techniques and O atoms produced in an RF discharge.

Figure IBB 2. Cross-section for th« reaction O • 0 "• 0 • 0+ Circles ar« th« data of Rutherford and Vroom (Reference 18B 14) obtained using crossed beam techniques and O atoms produced by thermal dissociation. Triangles are the data of Stebbings. Smith, and Ehrhardt (Reference 18B 15) obtained using crossed beam techniques and O atoms produced in an RF discharge.

:c ( Mi :•,: * (•*«•,• »•

* <: M tti hC «r, i(K) IM "i—i—r i—t—t—i i i i

o o °o ° O 0 0«

0 o o I

•J—J—I—I—I—I—I—k—i J i I 4

r» »uarc» i >* • tn

COKIMtM (*«,» IM] 0< 0 * 0 » 0 » 0* II I) IS T f i'" T r • T i i t r r T •

J 1 1 t i. II.

Figure 18B 3 Cross section foi the reaction N2 • O • Nj * O Circles are the data of Rutherford and Vroom (Reference 18B 14) obtained using crossed beam techniques and O atoms produced by thermal dissociation

Figure 18B 4 Cross section for the reaction Nj • O * NO • N Circles ar« th« data of Rutherford and Vroom (Reference 188 14) obtained using crossed beam techniques and O atoms produced by thermal dissociation

Revision No. S. June 1975

18B-5

DNA 1948H

'...:•: Ji titm.' Iff

m mm . i v HH y •* • y » T » T '

i I I i l__J t 1

'l :• I i». !•»!•.< . ,

1 1 1—i—i—i—r

°o°oooOoo °

J . 1 i— X 1 1 1 1 L

I» ft. I IT. . 18* •••,».

Figur» 188 5 Cross section for the reaction 0" • 0 *0 • 0" Or cies are the data of Rutherford end Vroom (Refer- ence 188 14) obtained using crossed beam tech-

niques and O atoms produced by thermal dissociation

F igure 18B 6 Cross section for the reaction 02 • 0 -* O2 • 0 Circles are the data of Rutherford and Vroom (Reference 188 14) obtained using crossed beam techniques and O atoms produced by thermal dissociation.

18B.3.1.2 No-Atom Reactions

, lii» 111».' »• (•») 10

< •

< *

I E 0 •

•;•)».

H 1 HHMhfn

*>•*»'*>

. * . ••• . 00 °«o 0 O

• • ' I L_l l__J l_—1

....:-. • ' .,„ «I.'J ;•• :^!* <«

Figure 18d 7 Cross section for the reaction N2 • Na -»N2 • Na Circles are the data of Rutherford et at <Refer enca 188 16) obtained using crossed beam tech

niquw

Figure 188 8 Cross section for the reaction NO • Na ~* NO • Na Circles are the riete of Rutherford tt at (Refer ence 186 16) obtained using crossed beam tech-

niques


CHAPTER 18B

.,*.:••• im*.' •>»

10/0 «U ¥) HO IUD 140

• it, • '(I 11.. .». I« .

Figure 18B 9 Cross sections for the reaction O2 • *» ~*C»2 • Na Diamonds ere the data for ground-state C^. circles are the data for metastable On. and triangles are the data for a composite beam of O9 "> which 32% of the Oo 1» excited All data are from Rüther ford et al (Reference 18B lb) obtained using crossed beam techniques

Figure 18B 10 Crow section for the reaction H20* • Na -• HjO • Na*. Circles art the date of Rutherford et al (Refer- ence 18B 16) obtained using crossed beam tech niques

«ilMOi 1«*

• « « t 1 r— T—1—r t T T

oo

0°

* ,

i—1—I 1—i—1—i 1—

Hl IM« I««.' ..

» . - . * '« 20c MC MC w T 1 1 1—I "» T f T t T I t Ttr

W>

o0 -

-I 1 L 1 J 1 l_

Figure 18B 11 Cross section for the reaction NvO* • H; *N?0 • Ne* Figure 188 12 C'oss section for the reaction H,0* • N* -• HjO « Cycles are the da»» of Rutherford et a> (Reference H • Ne* Circles are the data of Rutherford et al 18B 161 obtained using crossed beam techniques (Reference 188 16) obtained using crowed beam

techniques

Revision No 5. June 1976

18B-7

.

DNA 1948H

18B.3.1.3 Mg-Atom Reactions

i • .

•» -

n tO M 10 140 >M '•• ..'•> t t T ' t I 1 T T 1 t t I

» • •, . ». K|

°0fcO

J u J i i I

» it. «;•• ••%»

». iun ill«.' IM

(0 f* iu; la I4ii

i

S 0 i>

T—i 1—i—r-r-T Tl t T T

o o o o o

J 1 1 1 1 L I i I i

IU« HI OUT» 10*

Figure 18B 13 Cross section for the reaction N* • Mg - N • Mg*

Circles ere the data of Rutherford at al (Reference 188 6) obtained using crossed-baam techniques

Figure 18B-14. Cross section for the reaction N2 • Mg -• N2 • Mg Circles are the data of Rutherford at al (Reference 188-6) obtained using crossad-baam techniques.

*> '*

«. ' e

S 4

'.», IMS !«•«.« •»

.- w w n iv i«e IM tie 1—i 1—r-r-rrrrrrn

« • »j • « • »j

•••-- e e

J 1 i 1—I 1 i__L

• e .

J—I 10 )0 » 0 4•

I4B «ten" no1«»!

(ttiisioa i«a>* <»»i

I 10 K «0 40 40 100 140 140 I II I I I I I I I f

5

1 M

i r e • o

A

oÄo

o o

o o e

N.^""- A © 4>

i_L. I I I

lamietin (••'<•/«•<) tf4MU

Figure 188 1b Cross section for the reaction NO* • Mg •• NO • Mg* Figure 188 16 Cross sections for the reaction 0*> • Mg -*02 • Mg*. Circles ere the deta of Rutherford et al (Reference Diamonds are the r'.at» for ground-state O*,, circles 18B 6) obteined using crossed baam techniques are the data for metastabla O*,, and triangles are the

data for a composite baam of O*, m which 32% of the 0*, is excited All data are from Rutherford tt al I Heference 188 6) obtained using crossed haam tachmqwat.


_

CHAPTER 18B

KkiiMua tMfti If«I

10 to *o u< m wo ;«. IM> :n T—t 1—r

«J • «•

T T t t t

e oe 'oo o

u u I -

a / .

J L

<IJUI',J0» INK« IM)

1 1 10 M «0 H W 1» IM

T~" "7 T 1 1 r T F T F

.•• \.o' . n, . ,.?u • V

,J" \ l 0

1 t

;\ *••-

1

7 1 } 0

j 0 H - • 1

0 • '

1 ..i. i .i..... J—> i i i i; 10 4 C

I« iiiOCi'» to* (ca/Mc)

10 10 10 I» ttlOClTt (I0*c«/m)

«* oan?

Figure 188 17. Crou »action for the reaction H20* • Mg -»HjO • Mg* Figure 18B-18. Cross-saction for the reaction N20* + Mg •* Circlet are the data of Rutherford et at (Reference N20 • Mg* Circles are the data of Rutherford 188-6) obtained using crossed beam techniques. et al (Reference 18B-6) obtained using crossed-

beam techniques.

CSUIllflMMK« •»

jt__fl « a a '• i» iit m T T I I T T T r

9 a e

<. v ••» ••#•••••»•

1 * I L. MBiueiin nt'i^Mi)

*-i-H-

18B.3.1.4 K-Atom Reactions

[OtllMOD I*«.' '• III) ."» V 4 •

I 1 1 1—I—1—r—T

J_X 1 I I It 0 » 0« II ' 1 is

IS« Ml«IT* lit' CtWMMl

Figur« 188 19 Cross section for the reaction H-jO* • Mg * HjO * H • Mg * Circles are the data of Rutherford et al (Reference 188 6) Obtained using crossed beem techniques

Figure 188 20 Cross section for the reaction Ht* • K - He • K*. Circles are the data of Peterson end Lorants (Reference 188 17) obtained using crossed beam techniques

Revision No. 8. June 1976

18B-9

----- MB • • • —

DNA 1948H

III1 <* !*!«.• -.

T 1 T 1 1—I—r~1—» T T f

0

-Oo°

t. . I l. . ,

J 1 i 1 i 1

18B.3.1.5 Ca-Atorn Reactions

,. ) 0

uumoMaue •• K <ac ia ix

1 1 T t 1—I—r—T

Oo oo

= h*8 ri i't ft ^ i'g rt i^

F.gure 188-21 Cross section for the reaction Ar* • K -»Ar • K*.

Circles are the data of Peterson and Lorents

• Reference 186 17i obtained using crossed beam

techn .jues

Figure 188 22 Cross section for the reaction N* « Cd * N * Ca*

Circles are the data of Rutherford et al (Refer-

ence 188 18) obtained using crossed beam tech-

niques

v T r

fV. M T r—7—I—r—f|

k o o o

- 1 i L—i, -J—i—1—L_J—I—I—L_i- »: « ' • :

« . •. «...

'• i

:%iis!0»i««s« •• •: K 4C K K -K i«G •• I» MS T—T 1 T—t T T T T T » T T T T

i 1 4 1 i 4 1 1 J 1 X—I

Figure 188 23 Cross section tor the reaction O* • Ca • O • Ce'

Circles are the dete of Rutherford et a< (Refer

erne 186 18) obtained using crossed beam tech

niyues

Figure 188 24 Cross section for the reaction N*, • Ca * N2 • Ca*

Circle« ere the data of Rutherford et al (Reference

188 18) obtemed usmg crossed beam techniques

18B-10 Revision No 5. June 1975

z.—'- .-'•- —--

CHAPTER 18B

""»

i« csu «a» mm <w> m mm m mm m

1 • •

•

<• •* • u • m . u* "

'•* t •

1 * V. -

• 0

11

: t

; 4

v. °o

•

0 1 - c L_l_ -X 1 » 1 1 III!

»••

MU

ML

m • • m i I I I I I I I

•J • a * e, • •/

K •••• o«

a o

A 1

* • . I I I I

A 4

; to io «o :o» »t.oc" co* «,»•<

t I JO «.0

»•»mocm no* <»/Mii «•

r mn

F tggrt 188 25 CroM wctton for the reaction NO* • Ca -* NO • Ce*. Figure 188 26 Cross-sections for the reaction oj * Ce -* 02 # Ce* Circles are th» data of Rutherford et al (Reference Square» are the data for ground state 0*>. circles are 188-18) obtained using crossed beam techniques. the data tor metattabteO*,, and triangles are the data

for a composite beam of O*, in «which 32% of the o\ i$ incited. All dauere from Rutherford et all Refer- ence 188-18) obtained using croesed-beam techniques.

• c 2 to <• mm

K

i >

r——T i 1—r—T—r

o»o. »•oca

--U • L« • • .. • ..

A 1 I 1 1 I 1 I 1 1 I I

COUIMO» rast» w

" n * i y f iif ,"f,

V

w

i ° I 0

V • a

•a

< J* • U • SjB • U*

u i. 4 • : »: :•» »f.x •• ie* - «

I I I 0 10 IC

io» »IIK:'» 'ie* v, »I

ar-anaj

Figure 188 27 Cross section for the reaction M^* • Ca-»MjO • Figure 188-28. Cross section for the reaction NjO* • Ce •* NjO • Ce* Ce* Circlet art the data of Rutherford et el Circles are the data of Rutherford et al (Reference

188-181 obtained wing unwedbiaii ejejtejeajej (Reference 188 18) obtained using crossed beam

technique«


•

i • ii i • •

DNA 1948H

• •

J:

matmmm i«) • w m m H m m m m mm r T T T IIITTTTTTTT

e o o • *

_i—»—I—t—l—I—l—i—•—l—i- ) : 4

»• MM*

18B.3.1.6 Fe-Atom Reactions

;*.:i:*n(H' ••

. r. sc .;. • - 1

1 •- -

^ o

oo O 0

•

• 1 0 i

' : » - r 1 t •• •'. • . • : • H

-1 L —1— i ,_i —J J. -i. .

Figu»e 188 29 Crou section tor the reaction MjO* • Ca * MjO • Figure 188 30 Cross section tor the reaction N* • Fe — H * Fe* H • Ca Cycles are the data of Rutherford et «I Circles are the data of Rutherford end Vroom 'Reference 18B 18) obtained using crossed beam (Reference 18B 19) obtained using crossed-beam techniques techniques

-T T T r

' • °°oo~v c 0 o 0 . ;

• •

.4— i -*—i—i—* i—i—i—11—i t—i-

• 1 • .

«e > 'a g * a a« i« ia«mc>! En—»—i i i m iiiinun

> • • e o o

> -

- «—*—* i I ' ' • ' • I : : »: « • : *••••• s* •* s»

Figure IBB 31 Crou section for the reaction O * Fe *0 ' Fe Circles art the data of Rutherford and Vroon. 'Reference 18B 191 obtained using crossed beam techniques

F igur« 188 32 Crou section tor the reaction N2 • Fe • N? • Fa Circles are the data of Rutherford and Vroom ' Reference 188 19> obtained using crossed beam techniques

18B-12 Revision No S. June 197ft

couiuet MUM (••) » 13 ic « M •* -K <m im m

c I I I I I t T t MM

*> '8

(j

7 ' *

S :.

' ***°©V%° • • •

«• • ', . m • ••*

i 1—I—I—I—I 1—-L J 1 ;: > e *: 11

CHAPTER 18B

I e

i t

II

>"

cami«if«a» i#») 1 m m m m m m m m 1 1 T I—I'TlTTimm

V V

o! • H • 0, • »t*

• •• I

a 1 • r-

i "0»

• •

C 2

I 1 1 I L. 1, i U -1—1- (3 JC «J tO

Figure 18B 32. Crou section for the reaction NO* • Fe •* NO • ft Circles are the data of Rutherford and Vroom (Reference 188-191 obtained us ing crossed beam techniques.

Figure 186 34. Cross section for the reaction O*, • Fe — 02 • Fe . Circles are the data of Rutherford and Vroom (Reference 186 19) obtained using crossed beam

techniques. No effects were teen due to rneta- stable Oj m the primary ion beam.

ic • •* .--•• 1

h

1

4 .,

1 r—1—1—r—r—r

• e

1 I I I i i I i 1 .L «—i 1 1 . • : » : t : t»«t. .•• :* v'»

Figure 188 35 Cross sect»o« for me reaction MjO* * Fa * MÔ • Fe* Fifure 188 36 Crow «actions for the reactions M3O* • Fe - HjO • C.rcies are the data of Rutherford and Vroom (Refer h • Fa* and H,0* • Fe •* rfjO • FaH* Triangh*

ere the data for formation of tha Fa* product and ence 188 19> obtamed using cro«ao beam technique« product < circies are the data for formation of FeH* AN data art from Rutherford and Vroom (Reference 188 19> obtained using cd

18B-13 Waemow No. 8. June 197S

- . - --

NA I W8H

- >•. • . . ftc-Alorr tions

T T r

v -

-i 4 1 i.__i L o o

3—»_d L, i: •: * : • c

Ba *Bdf. » N

jl (Reference

jmj technique»

••rgy electron

Figure 18B 38 Composite cross section for the reactions NO • Ba

BaN • 0 and NO* • Ba * BaO* * N Circles are

the data of Neynaber et ai I Reference 18B 20) ob

tamed using merging beams techniques The NO

Aas produced using !ovv energy electron impact

18B.3.1.8 N -Molecule Reactions

M *m A a

%~%

Ba •BaO* • O Figure IBB 40 C-osssection to« the reaction Me* • N? *Me • N*>

at i Reference Circles art the. data of Wer i Reference 18B 21

«ms techniques obtained using beam gat ce*i techniques triangles

ergv e«ei.t»on «re the data of Stebbmgs. Ruthe«tore:, enj Twiner

• Reference IBB 22) obtained usmg crossed beam

technique* and squares ere the data of Gustafsson

and Lmdhotm I Reference IBB 231 obtained uvng

beam gas eel technique*

«3-14

Revision No 5. June 197%

•til 1

CHAPTER !8B i »«•*.-••

6 *

touisiaa mv ,MI

0 %

N* -1H_ :: «9 4 c toi« i» »• l«

•' MM'

ret «

?M

aOQl» o o o or- - c

ii ii 1.1 ic"'« i« * itLOtlTl 'i«« AU.

F ly-re IBB 41 Cross wet •on «or the reaction He • Nj -* He • N •

N Triangles (ape* up) «re :rte Jaw of Mtitf (He

ference IBB 21) obtained using beam gas cJl tec».

mques circles are the data of Stabbing*. Rutherforl.

and Twiner Reference 18B 22) obtained usingcrossed

oeani techniques, triangles <ape* down) «re the data

of Gustafsson end Lmdholm (Reference 188 23)

obtained us ng beam tas ceil techniques, and squares

are the data of Voran and Friedman (Reference 18B

24' obia"»ed u*mg ion source techniques

Figure 188 42. Cross section for tne reacboi \ • Nn -*N • \.

Triangles are the date of Meiei and Mured : Refer

I • 08 25 Obtained using beam gas sei! tec'

mques j..«jre> are th« ?at<» of \ey:iat.'>j< hurtet

for.: tttiO v room 'Reference 18B 26 obtained

using crossed beam techniques ana circles a'i

tne data of Steob ng*, 'urner and j«;' in -e

L-t-.: 18B L'7 jotemed JS HJ - : aa • pa« cc-

te-,' ju* " --.• i • ii :•.»-,.•. . , format! a't

c •.•.••.; -..

_ • o e Oo O

•. . 3 • •,

• • •» ?'i H h h rt *

?«**:

%

1 y 1. «*•

c :

V

Figure 1HB43 Doss section 'or !*« r*.jct,oi O • N2 "* 0 * *5

Note that the O* must be m a rnetestebie state to

••4*1 th« reaction proceed at low energies Circles

Mt the data of Rutherford and Vroom (Reference

IBB 28) obtained using crossed beam techniques

T*>e data «re corrected for t*e amount of metastable

O in tne beam Triangles ere the data of T tarnen

' Refvence 18B 29) obtained using beam gas cell

techniques The data »19 corrected for tha amount

of metastable O* m the beam Squares are the data

of Stabbing*. Turner, end Srr th (Reference ?8B 271

obtained using a beam gas te" technique in which

ail slow ions ere collected No correction for

me composition of the beam is made

Figure IBB 44 - • . .:•.-.: • \ • \

' • >•••, ••. • p r • '. . • .1, . • •-. enc*

1-.' .• J-:.I eo w> j) be«."> uas .e > . ies

c '. - ••• •••! •« . ew • .'•• >»*iv ••:•

• • - : i o .-• " ... "engte

I-:» • i, .-. . • • • -.,•. •'• • • ;i V'CH.

•<e'v •• . - . : :B • *. State C

11 J -.••«•'• e •• !i-.:< .:. .1 , v-- *.»#• u

1 • '' jj: • T f •«.'• -ii»i«'»' ., 1 • . .- it

•> n«0 .••• _. j- »• . !jt* :• j' joj

e j;>i j- « na -iun'fi e-c :in .;

•>• .• t -• >i :- •.<• - • •. ne:rfs. 1:

. aurci ^ - - »( .'

Revision No. S. June 197S

133-15

mmm

DNA 1948H

st

Figure 18B-45.

T—r

uuism «*•*« icvi K «C «t K 'DC !«

T I I I I ? IT I T T •«c no "I I T~T

« i » IC If M

\ • .

\'\ • V V

J 1—1 1 1 t i 1 I J L

—1—T -r-l T ri TT7 rTTI rr T

- -

A -

o o

a - o

4 JL

:

r : ) c •: «. : • 4

Crosj-section ?or the reaction N2 • N2 "* N2 * N2 Fi.it rectangles are the data of Moren and Roberts (Reference 188-32) obtained using a modified ion- source technique, circles are the data of Neff (Refer- ence 188-33) obtained using a beam gas cell system in iwhich all slow ions are collected, squares are the data of Levemhal. Moren. and Friedman (Reference 188-34) obtained using a beem-ges cell technique, triangles (apt* up) are the data of Amme and Ut terbec* (Reference 188-35) obtained using a beam gas ceil technique in which slow ions are collected, and triangles (apex down) «re the data of Steb- bings. Turner, and Smith (Reference 188-27) obtained using a beam-gas cell technique in which

•• ions are collected.

': -4 'i •• K

: * c t .§ • c l i

r smi!

~T T—T—I T T I T r

Figure 180-46. Cross-aaction for the reaction N2 • N2 -* N, •• N • N

Circles are the data for N2 formed by 19.3 eV electrons, squares are the data for N2 formed by 25.5 eV electrons, and triangles are the data for N2 formed by 57.0 eV electrons. The data are from Meier (Reference 18B-3C) obtained using beam-gas cell techniques.

touts ten Mas» ••

' » C « «C i; K X K -K IK

t I

I I I I I ! 1 Ml 1 I I I T 1 I

o eo

: 1— i 11 J c *:

• » A.XT' 'C* CWtfl

J 1 II I

Figure 18847. Cross section for the reaction N2 • N2 • N3 « N Circles are the data for N2 formed by 19 eV electrons, squares are the data for N2 formed by 25.5 eV electrons, and triangles are the data for N2

formsd by 57 eV electron The data are from Maier (Reference 188 36» obtained usicg beam gas cell techniques

Figure 18848. Cross section for the reaction NO* * N2 - NO • NJ.

Note that the NO* must be m a metastabie state to make the reaction proceed at low energies. Circles are the data of Neynaber. Rutherford, and Vroom (Reference 188 26) obtained using crossed-beam techniques. The cross-sections are corrected for the fraction of metastabie ions present in the beem


L

:*.:*:» I««S" t>

8

i . K «C fc- K X tie is tn 11 ! » t 1 T T » I! 1 T T T T n

**

-

ot • », • 9 • »I -

o o

• 0 '

0

. f i 1 i » --1 i...I —I -,..

v^rw^ncr* IOD

10 10 IB «0

I

t

* i-

S "" 9 - '

I :* . 2

T——t r—i—i—r—r

- o o

I I ' I I 1 1 1 L ; o 4 : t : c i *

:» IUOC:*« '3* - *»

•' ;»M4

Ftgure 188-49- Cross section for the reaction 02 • N2 "* 02 • N2

Note that the 02 must be in a metestebie state to make the reaction proceec at low energies Triangles are the data of Rutherford (Reference 188 37) ob tamed using crossed beam techniques These data .re corrected for the fraction of metastebie ions present in the beam Of ,les are the data of Amme and Utteroeck (Referer ie 188 35). and squares are the data of ^tebbmgs. Turner, and Smith (Reference 188 27) Bovh of the latter sets of data «were obtained with beam gas cell techniques using slow-ion collection, and nvither is corrected for the excited states m the beam.

^.:#:D» !««• ••

to l' «: i :

~r T r—T—r—T—t—i—i

Figure 188 50. C .sectionfor the reaction 02 • N2 •*NO • NO- Ou a are the data of Rutherford (Reference 188-37) obtained using crossed beam techniques

18B.3.1.9 NO-Atolecule Reactions

..:•. .* «M»t- ti

J J 4—J L- J 1 L

-T 7 » T 1 1—I t I T T

L_ •» • *c . •» • \

J 1 L.

o o

J—I—I—1. «c i c * :

• rtiocr*» eJ .»

Figure 188 61 Cross section for the raactior N20" • N2 -*0 • N2 • Figure 18B 62 Cross section for the reaction He *NO-*Me*N • N2 Circles are the data of Tu man and Clow (Refer O Circles are the data of Moran and Friedman (Refer- ence 188 38) obtained using bevm gat cell techniques ence 188 241 obtained using ion source techniques

18B-17 Revision Mo. 5. June 1975

DNA 1948H

1 r

i>u ;•>'*> !««•-• IM)

1—I ! I I IIHUI

i • * • « » ac

J 1 l__i 1 1 L u_J

««ti'.K» rn.ni ft)

10 fo t0 • 100 l«0 IM) MO NO 100 n—i—i—i—i i ? i i ii iTi

AA

HA AA** A* A

lOOO o oo o oo o o o < T J L, i 1 1 L

!'* XiW It»

Fi9ure Ibii 53 Cross section lor t * reaction N* • NO - N * NO* Figure 18B-54. Cross iect.ons for the reaction O • NO "*O • NO Circle* »re the date of Türner. Rutherford, and Triangle« are the data for metastable O* ions and Stebbmgs I Reference 18B 39) obtained using crossed- cycles are the data for ground-state ions All

beam techniques. daU "• from n"*n«,*0,d (Reference 186 37) and «were obtained using crossed beam techniques.

• •%-,' .. DII'. J» i«tt»'.

i—T-T—i—-r—T—rrrTTTTTT

_i I I i 1 L-_l 1 l—L

l r 1—i—i—i—rr

« . r . •/. . *

o o <

i I i I i i i I 1 1 I i I t I I .•» > » 4 •• •- SI '•

Figure 18B 55 Cross section for the reaction N2 • NO -»Nj • NO* Figure 18B 56 Cross section for the reaction NO »NO • NO* NO* Circles are the data of Paulson (Reference 18B-30» Circles tn the data of Ghosh and Sheridan (Refer- obtamed using beam-gas cell techniques, and triangles «nee 180 40) obtained using beam-gas cell techniques are the data of Neyneber. Rutherford, and Vroom (Reference IBB 26) obtained using crossed beam techniques The encess energy in this reaction is such that either the NO* or the Nj product may be left m an excited state

18B-18 Revision No. S. June 1975

CHAPTER 18B

•IH. 1' 1 * (*«(.• »t

- •• * It - r "i" T~

0

, - *' IJ •»••,'•

- o

'

o •

- 0

0

'

• 0

•

o •

-

°1 JJ i I i -i 4

I'NI !',li» I »mi,« ,#•

i. I« I» T—I 1—I—I—I—I—r~1—ITT

« • •* • M » •

A_t_J—I—I I 1 i 1- i. i L ! .' II • » I '

:r* If ia If» HO* • •<«•

»l mid

Figure 18B 57 Cross section lor the reaction NO* * NO * NO • N* • Figure IBB 58 Cross section for the reaction NO* • NO •*NO • N • 0 Circles are the data of Moran and Roberts (Refer 0 Circles are the data of Mot an and Roberts

ence 186 321 obtained using a modified ion source (Reference 188 32) obtained using a modified ion- technique source technique

3—n—i r—?—i T r T r T r r l

Lt

K c

% 0 nD O "• Q

4. i... i J i-.i I J J L

(01. I', I» ••*».>

4 •» »

i—n—i—i—i—m -T -r rr T T

ft

I- \

-,' • « • -i.C • «K

o o o o

o o

L. J 1 I 1 1—J » 1 1 L :

F.gurei8B59 Cross sections tor the reaction 0*. • NO »02 • NO* Figure18B60 Cross section for the reaction MjO • NO-HjO* Crcies are the data of Paulson (Reference 188 30) NO Circles ere the data of Turner and Rüther obtain«! using beam gas techniques with a mined »ord (Reference 188-41) Obtained usmg crossed

beat" Squares are the data for metastabie Oj. tn beam techniques

angles (ape« down) are the data for a ground state be*m. and triangles (ape« ue) ere the data for a composite beam, ail three sets of data coming from Rutherford (Reference 188 37) ltd ob tamed using crossed beam techniques

18B-19


DNA 1948H

i»! i'.:i» !••<•• '•

r 4 so so ton

•» 1 1 T—T I T I I I ! I I

... • « . n • nj) • as

J 1 * 1 1 I • 1 — I

,(.»:•• '*.-- <•»

18B.3.1.10 Oj-Molecule Reactions

a

lOll IM« IWKi» 'MT)

•v. !•» AK. Hl tltl Mi i—i—»—r T T » ? n t

i -i I 1 1 1 L L. 0 .' 04 '* ü H 1 j I .' ' • : *

IM «liKtTt (!u (• •..

Figure t8B 61 Cross section for the reaction H_0* • NO — H •

H^ü • NO * Circles are the data of Turner and Rutherford (reference 18B-41I obtained using crossed beam techniques

Figure 18B-62. Cross-section for the reaction He* • 02 ~* He • 0 • O . Triangles (ape* up) are the data of Meier (Reference 18B-21) obtained using beam-gas call techniques, circles are the data of Fite et al (Refer- ence 188 42) obtained using crossed beam techniques with slow ion measurements, squares ere the data of Stebbings. Rutherford, and Turner (Reference 18B-22) obuined using crossed beam techniques, and triangles (apex down) are the data of Utterback and Arnim (Reference 186 43) obtained using a beam gas cell technique with slow- ion collection

T—i 1 T 1— 1—1—r—n

»00 A °°oo ° o o o a) o

A -

f

A i. J L

»(IM.« !«•.• .,

T 1—T—r

o _ O o »°0

-I—i I 1 1 1 1 X -1—1

Figure 18B 63 Cross section for the reaction N * • 0^ *N • O^

Circles are the data of Neynaber. Rutherford, and Vroom (Reference 188-44) obtained using crossed beam techniques, and triangles are the data of Stebbings. Turner, and Smith (Reference 188 27) obtained using beam gas cell techniques with total slow ion collection

Figure 18B 64 Cross section for the reaction N**02*N*0* O* Circles are the data of Neynaber. Rutherford. and Vroom (Reference 18B44) obtained using crossed beam techniques


CHAPTER 18B

I . 1:1 WKil •( « ,' ' * I «I kl.' »•

10 •'<> «ii * mo wo i*i .'.•'. /«.< tec

•'' ' T r r r T nnnn

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e°?d%«>

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•

• o

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rr T- T T T r t n T TTT TTTT

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qmhptvf**!** A A 1— 1 '

Figure 18B 66 Cross section for the reaction N* • 02 * NO* • O Figur« 18B 66 Circles «re the data of Neyruuer, Hutherford, and Vroom (Reference IBB 44) obtained using crossed b«am techniques

• o2 *0 • O 2 ons and in

Cross sections for the reaction O Circles are the data for metastable O angles (apex up) are the data for ground state ions Both sets of data are from Hutherford (Reference 18B 37) obtained using crossed beam techniques. Triangles (apex down) are the data of Stabbing».

Turner, and Smith (Reference 18B 27) obtained using crossed beam techniques and »low-ion col lection No state selection of the primary beam was used

T -7 • 1 r

L i X 1 C

F.gure 18B67 Ooss section for the reaction N*> • Oo ' N2 * °2 / f'*wr* '8B 68 Cross section for the re?ction 02 • 02 * 02 • ->2

Circle» are the date for both reattants having a mini rriuiri of internal energy, squares are the data tor N-, having minimum internal energy and O-, heated to 1600 K. and tnangles (ape« up) am the data for N2

formed by 40 eV electrons and U-, hawing minimum internal energy All three- sett of data are from Neynaber. Rutherford, and Vroom (Reference 18B 44) obtained using crossed beam techniques Tn angles (apex down) are the data of Stebbings Turner, and Smith (Reference 18B 27) obtained using crossed beam techniques with vow ion collection

Tnangles *i% the data of A mm* and Utterbeck (Reference 18B 35) obtained using beam gat cell techniques with total slow IOI< collection, and circle. ere the data of Stabbing». Turrvw. and Smith (Re ference 188 27) obtained using crossed beam tech mques with slow »on collect*»-.


18B-21

.

DNA 1948H

1—i—i—i—i—i—i—n

-S 1 i 1 i » 1-

4 'C K

Cd

4C

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K tC /C «C K W.

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1 .

I T I » 1 T T T T r

ä*

Figur« 186 69 Cross section for the reacton <J2 • ü2 •• On • O • Figur* 18B 70 Cross section for the reaction HjO* • 02 "• H20 •

O Circles «re the data of Moron and Huberts <Ft«f«r«nce 18B 32» obtained using a modified •on source experiment

02 Circles are the data of Turner and Rutherford (Reference 186 41) obtained using crossed beam

techniques

.<x.:v» t«K- •>

" 0 • C- • ' • .,

« 1 » 6 * o

-1 o o

f. »! .- "o. 7

i -%• 40« ft « i 4 *

LY°'+* ' * * —rX _» SLL 19 1_ X 1. ...

-T—r

00 o • o

O O

Po i—i—i—»—r o

0»

OO

oo

8

. • 1 -i A A- A_i 1—L—1 I t- i- J i i TTTTTIMTII

Figure 186 71 Cross sections for the reaction 0" • 02 ' O • 0;

Fiat rectangles n* the date of Paulson (Reference 186 4b/ obtained uung beam gas ce'l techniques, circles ere the data of Badey and Mahadevan (Re ference 186 46) obtained using a beam get cell tech nique *ith slow ion collection, squares are the data of Snow. Hundei. and Gebellt (Reference 186 47» obtained using crossed beam techniques, triangles (ape* up) «r« the data for a ground state 02 tar git and tnangies (ape« down» »it the date for a mttMtable 02 target from Mathis (Reference 186 48) obtained using crossed beam techniques, end

diamonds are the data of Rutherford and Turner (Reference IBB 491 obtained using crossed beam

technique«

Figure 186 7? Cross section for the reaction NO' • 02 * NO • 02 Circles are the data of Paulsen (Reference 188 30» obtained using beam-gas cell techniques

18B-22 Revision No. S. June 1975

—— —_

CHAPTER 18B

» l«K< ••

:c* «.«:*• ':* » *t

18B.3.1.11 H20-Molecule Reactions

ca.:vi» «««• it»; , , t >C K « K K :jc i« iK ;.'i

« ' «

^ i e 6

c »

-r~1—I 1 »—rTTTTTTT

A o oo

I i t I I I I i 1 I -i j 1. f S i c «o to ic

!0» KlKfl '3* ca/Mt

Figure 188 73 Cross section for tht reaction Oj > 02 ~* Oj • Oj Figure 188 74 Cross section for tht reaction N • HjO -* N • Triangles art tht data of Rutherford and Turntr HÔ Circles art tht data of Turner and Ruther- (Rtftrtnct 188 49) obtained using crossed beam ford (Reference 188-41) obtained using crossed techniques, and circles are the data of Bailey and beam techniques Mahadevan (Reference 188 46) obtained using a beam gas cell technique *ith slow ion collection

;&

x m tt * •* « • i—i r——t—r—r—T ~T n r

i : •

• • -

o < O »0 o o

-i 1—J ~J—1—A—4—t-

« «C Kl 'XIR'« r—r—i 1 1 1—i—i 1 f"

o e

J—i—i—i—i—o 1 i i <

figure 188 76 Cross section f'« the reaction 0* • HjO * O • Figure 188 76 Cross section for tht reaction Nj • H20 •* N2 • M2ü* Circle are the data of Turner and Rüther MjO* Circles are the data u» Turner and Rüther ford (Reference 188 41) obtained using crossed ford (Reference 188 41) obtained using crossed beam techniques beam techniques

18B-23 Revision No S. June 1975

DNA 1948H

K K *• K. X K >«

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Figure 18a 77 Cross section for the reaction NO* • H,0 * NO • Figure 188 78 Cross section for the reaction OX • H20 "• Oj

h-.ü Note that the NO mutt buna metastable state tor the reaction to proceed at low energies Circles are the data of Turner and Rutherford (Re ference 188 41) obtained using crossed beam tech nigues The data are corrected for the fraction of metastable ions in the beam

H-,0 Note that the 02 must be in a metastable state for the reaction to proceed at lei* energies Circles v* the data of Turner and Rutherford (Reference 18B41) obtained using crossed beam techniques The data «re corrected for the free tion of metastable ions in the beam

j». i » may •• ; t • « » »

~r—f—i—i—T—r -T~r

i—i_-l—1—J—1—i—I—i-

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• » • • ; « i

Figure 188 79 Cross sett^n for the reaction MjO* • MÔ • Figure 18B 80 Cross section for the faction O • MjO • OM • M30* • QH Circles are the data of Turner and OH Orel« are the date ol Paulson (Reference Rutherford (Reference 186 411 obtained using 188 30) obtained using beam gas cell technmues

crossed beam techniques

188-24 Revision No 5, June 1976

- ... — .

CHAPTER 18B

18B.3.1.12 N20-iMolecule Reactions

COUUiO» (««• («)

1 0

V« 9

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Figura 188 81. Cross $act»ons for the ructions S* • N20 - N • Fifurt 188-82. Cross sections for the roKtiora Nj * hUO * N2 • N20* (circle). N* * N20 -* NO* *N*N (tri NjO* (triangles) and NJ • HjO •* NO* N2 • N angles). sndN** N,0 - N, • NO (square*). All (circles) All data arv from Murad (Rtfaranot angles), and N • N20 - N2 • NO (squares, dato art from Murad (Rafaranca 188-50) obtained using Liimgii call technique«

188 SO) obtained using bump call techniques

i. »••.».• t,

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g »: .

• i"T4 •• •• ia it >« i« • a is*

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Figure 188 83 Cross section for the njaction O • NjO "• NO' •

NO Circles arc tha data of Tiarnan and CNNM

(Rafaranca 188 38) obtained uwi| beam gas catl techniques, triangles am tha data of Paulson (Ra- faranca 189 61) obtained using beam gai call tach mouat. and m# square it she datum of Stocfcdaie. Compton. and Hamnardt (Rafaranca its« 52) obtained uwng ton« produced by Ü—tOMbU attachment

Figure 188 84 Croat-aaction for dta raaction O" * N20 -»0~ • N2

Circles ara tha data of Paulson (Rafaranca 188-61) obtained using baam gat call techniques-


DNA 1948M

-IX. '.i» !•*•«.•

So«

-| r r—r

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Figure 18B db Crou section for the reaction NO' * NÔ • NO • Vu Triangles are the date of Paulson lH«t«?r ence 186 51) and circles «re the data «f Tiernan 4«'"J COA 'Reference 18B 38) both obtained using beam gas ceil technique»

Figure 186 8b Crou «action for the reaction N-,0 • No0 • 0" No * N-)Q Circles are the data of Tiernan and do* (Reference 186 36) obtained using beam gas cell tech iciues

18B.3.1.13 CO^-Molecule Reocticru

.±

». • i«t«i> •. 4 «. « ' # |

f—T . . T -t—r—T

A o00 0

& A ° ° "•

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[ 4

F<g-r« 186 87 Cryss sections tor the rtact.un O • C02 »O • CU^. Ffjure 186 88 Cwtiatj ere the <U'a tor ground »tat« O and tr>*ng<es are th« oat* for e«c<ted state 0 A 'tata •'•• from T.ernen 'Reference 186 ifl*i obt* ••<,0 jung oeem

gas ceil technique*

Crou sections for the reaction 0 • C00 * 0? • CO Triangle« are the data of Pau'son 8Rafaranca 188 JO) obtained »sing beam gat c«<' techniques, bewares and circles are the data of T««rnan (Re ference »8B 2*J> for ground state and em. .ted 0* •uns «espec lively obtained usmg beam gas ceM techniques

188-26 Rryisio« No b. Juru- 1975

CHAPTER 18B

saun« I««I MM * 'C It IC

—? ", 1 1—I—r

i* .0.

L i tt

A

AA A Al

-l_J 1 1 t 1 1 L

• » =

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*

CO- • 0, • CO

t A A

A A

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* • ' 0 * «

is* .«. . •• «e* v»

F «flure 18B 89 Crou-saction for th« reaction O" • C02 - 0 • CO] Figvrt 188-90 CroM-aaction for tht roKtion O" • CO] ** O] • CO. Cifci« «rt tha date of Tiarnan and Clow (Rafaranct Trianglti art the data of Tioman and Ctovi (Refer 18P 38) and trianote are tne data of Pauiton |Rr one* 138 38) and ctrda« art the data of »tvlaan ftranca 188 51). both obtainad using beam g« catl (Refaranca 188 51». both obtaimd uti.« techniques oat.' tacnmquov

, .'. • « ; • '• .-.- n K I T T T ' 'el I MIHIMrTTI

8

kwil -I i L__l L__j£,

• . •

» tt.X

• • •

F *ure 188 91 Crota-aaction for tha raaction NO' * CO] • NO • F «uit 188 92 CrOMrtastion for ! CO] Circle» art the data of »awHon iRtftrtnoa CO] Cade* art 188 53) obttHiad using baanvoj» ct»» technique» 188 53)

rate two Oj • 00] -» O ] • i date of Paul«» if

18*27 «www No 5. Jona 1978

DNA 1948H

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T 1—»—r TTin

oo •r-o

_k—i—i—1—i_ o o o J 1 4- X—L—i—I—J—i—1—i—i—1—1—1—i

Fujure 18B 99 Cross section tgr the weMn Q2 • CQ2 * £03 • O Fujure 188 94 Cross section tor the reaction O3 • C02 "* CO-j • C.rd«i ere th« data ot Paulson (Reference 188 53t 02 Circles ere the data of Neyneber. Rutherford obtained us.na beam 9« cvtl techniques »"d Vryorn «Reference 188 541 obtained us«ng

crossed beam techniques

180.3.1.14 NOj-Molecüle Reoctimis

e 1

*

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r„* T

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- T -T T-

V

ca. '.-mmm? - um mm

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—••••• a

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F-gure 188 95 Cross Mutton •©» the rafHOn C»2 • %C2 • 02 • N02 Cirwies are tne uata o» f'eu'su" I Reference 18B 30' ubUi"ed «sing be«• gas ,«• '^»•'^-•".

F.gure 188 So Cross section to* the ruction 0 • HOj ' 0 • NO-. Circles are the data of Rutherford IRa «ererKC 188 37) end tr*r«aies are the data of

5now Runde« and Gqfceir« iHercence 188 4 71 both of »ained «.sing crossed Seem tech i.ryuri bttueres are the date ot Stocfcdele Com» to» and Re>nh*<n "Reference 188 52* obtained using ion« produced b» drssoc>etive attachment

18B-28 He»i».on Ht, b Ju»vr 19J5

CHAPTER 18B

I •

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I e

%

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Figurt 188 97 Cross section for the tact*.. Oj • N02 - 02 • NC2 C'fcit» art tht data of Ruthtrford (Refer ence 18B 37) obtained ui.nfl crowd bum tech

Figure 18B 98 Cross «action for tht reaction O3 • N02 •* O3 • N02 Circles are tht data of Rutherford, Turner, and Vroom (Reference 18B 55) obtained using crossed beam techniques.

18B.3.1.15 03-Molecule Reactions

T—T o •I

. 4

:-..•'. • <*.%. t.

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Fûrt 188 99 Crosssect« n for the reaction N* • O3 »NO* • 02 Figure 18B 100 Cross section for tht region O • O3 -O • 0 • C2. Circles er« the data of Nevnaber. Rutherford, and Circles are the data of Neynaber. Rutherford, and Vroom (Reference 188 541 obtained using crossed Vroom (Reference 188 54) obtained using crossed

beam techriKjues beam techniques

18B-29

Revision No. 5. June 1975

DNA 1948H

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Figure 188 101 Crosssection for the reaction N^ * ü3 "* N2 * O • Figure 188 102. Cross section for the reaction 02 + 03 •* 02 • O3.

ot Circles are the data of Neynaber, Rutherford, Circles are the data of Neynaber, Rutherford, and and Vroom (Reference 188-54) obtained using Vroom (Reference 188 54) obtained using crossed

crossed beam techniques, beam techniques

CGU:MM i«tat« „ 1 to a « at a 'x 1« « 2K

;ou;s:o» naw •« i; v. oc ;x JOC

* • 1 1 1 1 1—1—1—1—r

o ,

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J 1 1 1 I L i '. i: 4; I e i :

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ross-section for the reaction NjO* • O3 - N20 • Figure 188 104 Cross section for the reaction O" • O3 - O • O3 3 Circles are the data of Neynaber. Rutherford. Circles ero the data o« Rutherford. Turner, and

Figure 188-103 Cross sect O and Vroom (Reference 186 54) obtained using crossed beam techniques

Vroom (Reference 188 55) obtained uwng crossed beam techniques.

186-30 Revision No 5. June 19/5

CHAPTER 18B

üJUIüJ» t»I«6» ••

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Figure 188-105 Cross section for the reaction OH' • O3 -» OH • Figure 18B 106 Cross section for the reaction 02 • O3-* 02 • O3. OÖ Circles ere the data of Rutherford Turner, Circles ere the.data of Rutherford, Turner, and and Vroom (Reference 18B-55) obtained using Vroom (Reference 18B-55) obtained using crossed crossed beam techniques beam techniques.

18B.3.1.16 Drift-Tube and Flowing-Afterglow Drift-Tube Measurements

cruui» cent I«N 1 10 • • H I « K « IN

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Bo

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a

i 1 tu

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Figure 18B 107 Cross section for the reaction N02 • O-j • N02

0 . Circles ar? the Jeta of Rutherford, Turner, and Vroon-i 'Reference 18B 55) obtained using

crossed üeai" techniques

Figure 18B 108 Rate coefficients as a function of collision energy •n the center of mass for the combined reactions N2 • O - O* • N2 and Nj • O - NO* • N Squares are the data of McFariand et ai (Reference 18B 561 obtained using flowing afterglow drift tachn«4Ut«. and the tr,angle is the thermal energy datum of FehsenfekJ. Dunkin. and Ferguson (Re ference 18B 57) obtained using afterglow techniques Circles are the low energy beam data of Hutherford and Vroom (Reference 188 141 shown et higher energies for comparison


DNA 1948H

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Hill I I I I Hill "T I I » PfU

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Figure IBB 109 Rate coefficients as a function of E/P and of mean ion energy for th« combined reaction* He • Nj "* N* • N » Ht (branching fraction 0 55) and He • N2 ~* N2 * H> (t,,*nchm8 fraction 0 45) Circles are the data of Keimeri, Johnsen, and Biondi (Re- ference IBB 12) obtained using drift-tub* mass spectrometer techniques

Figure 18B 110 Rate coefficients as a function of the collision energy in the center-of-mass for the reaction O • N2 -* NO* • N Squares are the data of McFerlano et al (Reference 18BS8) obtained using flowing- afterglom drift techniques and triangles are the data of Johnsen and Biondi (Reference 186-59) obtained using drift tube mass-spectrometer techniques Circles are the beam dau of Rutherford and Vroom (Reference 18B-28) shown at higher energies for comparison.

,. -o o ti»

;j « « * 'i '* t TT I T 1 1

' • » •

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o ;

.

. •

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Figure IBB 111 Rate coefficients as a function of E/P and of mean •on energy for the reaction O*» * NO "• 02 • NO* Circle* are the data of Johnsen. Brown, and Biondi (Reference 186 60) obtained using drift tube mass spectrometer techniques

Figure 18B 112 Rate coefficients as a function of E/P and of mean ion energy for th« combined reactions He • On ~* O* - Ü • He (branching fraction 08) and He* • Oj * O*, * He (branching fraction 0 2) Circles ere the data of Hetmerl. Johnsen, and Biondi !Re- ference 186 121 obtained using drift tube mass spectrometer techniques


* '

CHAPTER 18B

« x t * 'a I 1 t i 1 t I i i I Hi Figure 188 113

Rate coefficients as a function of the collision energy in the center-of mass for the combined

reactions N* • Oj ~* NO* • O and N* • 02 "* U^ • N Squares are the data of McFarland et al (Reference 186 68) obtained using flowing afterglow drift techniques, and triangles (apex up) are the data of Johnsen, Brown, and Biondi (Reference 188 60) obtained using drift tube mass spectrometer techniques The triangle (ape* down) is the thermal energy datum of üunkin et al (Reference 188 61) obtained using flowing afterglow techniques, and circles are the beam data of Neynaber, Rutherford, and Vroom

(Reference 188 441 shown at higher energies

for comparison

j * i i.i.i-i

V

«+. eqgi o

Figure 18b 114

Rate coefficients as a function of the collision energy m the center of mass for the reaction

O* • 02 • O < O*, Squares are the data of McFarland et al (Reference 188 58) obtained using flowing afterglow drift techniques, and triangles tape« upl are the data of Johnsen and Biondi (Reference 188 69) obtained using drift tube mass spectrometer techniques The tnbngfe lap«» down) is the thermal energy datum of Üuntiin et a< (Reference 188 61)

obtained using flowing afterglow techniques, and the circle >S a beam datum of Stebbmgv Turner, and Rutherford (Reference 188 6) *o*n her« at higher energies tor companion

18B-33

Revision No 6. June 18/6

DNA 1948H

« loo (•»:*«.

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Figur« 18B 115 Hate coaffisivnts as a function of E/P and of mean ion energy for the reaction U • On ~* (JO4 * O Circle» ve the data of Johnsan and Biondi (Re'«rence 188 62» obtained using drift tuba mass spectrometer techniques

Figure 188 116- Rate coefficients as • function of the collision energy in the center of mass for the reaction N2 * °2 ~* N2 * °2 Squares art the data of Mc Far land at al (Reference 188-68) obtained using flowing afterglow drift techniques, and triangles (apex up) are the data of Johnsan, Brown, and Biondi (Reference 188-60) obtained using drift tuba mats-tpactromatar tachniquas. The triangle (ape* down) is the thermal «nergy datum of Dunk in at al (Reference 188-61) obtained using flowing-afterglow techniques Cir- cles ara the beam data of Neynaber. Rutherford. and Vroom (Reference 188-44) shown at higher

energies for comparison

on« prr-T

I/» •!/»•'•»» i

10 '» u

<oo **«%

co. • t: • a.

f 4 8 oo o

i i—i—i-

F igure IBB 111 Rat« coetf««nts as a function of E/P and o* maan ion energy for th« react-on O* • COj "• CO • O*,

Circles «re th« data of Johnsen. Brown, and Biond«

'Relevance 18B601 obtained using drift tub« spectrometer techniques

18B-34 Rev.s.on No 5. Jun« 1975

CHAPTER 13B

18B.3.2 Tabular Data

Hate roeffi« tents which have been measured .it only ane energy in the non-thern .il energy regime are presented in Tables IM'-l i DOS it ive - ion reactions i and |.KB-~ i nejiative-ion reactions!. It should he noted that .t!l rates listed in these t.ti>l«-s were determined using beam techniques. The ion energy employed was "i. •> eV, Fhese « ompilations were urejjareH and kindly supplied to the < hapter authors by Y, t). i iernan >f U right-1'atterson Air lor« «• Base, Ohio.

18B-3.' M. .. ,.- ".

DNA 1948H

Table 18B-1. Rate coefficients for positive-ion reactions.

Rate Coefficient** Reaction k (lO^cmêc'1) Reference

N* • * NL - N * neutral(s) j 0.21 18B-29

^15 15 • NL * N--N. • ISL 2 2 2 2

0.67 18B-29

f* +

°2 >V°2 + N2 0.28 18B-29

1 ; 15 15 N • JNO-N • ^NO j 0.093 18B-29

0* • NO-0 • NO* 0.011 18B-63

18 18 0 * N O- O • neutral(s) 0.091 18B-63 j

0V2D) • NO-O • NO* 0.49 18B-29

N2 * NO-N2 • NO* 0.39 18B-29

02 • N0-02 • NO' 0.72 18B-29

N* * 02-N • 02 0.32 18B-64

j N • 02-N0' • O 0.035 18B-64

o' <o2-o < o2 0.0057 18B-29

0*f2D) • 02-0 • 02 0.59 18B-29

V W°2 0.043 18B-64

o^Vv'S 0.60 18B-29

•Excited state.

**AII rate coefficients are based upon i normalization to 1.2 > -9 1 10 crrTsec"1

forCH4 • CH4-CH5 • CH3.

(continued) 18B-36

Nevition Mo b. June 1976

CHAPTER 18B

Table 18B-1 (Cont'd.)

Reaction Rate Coefficient** I k (10"" crrrsec"'; Reference

N * H20 - N « H20

N * H„0 - OH 4 neutial(s)

N* » HjO'-HNO • H

O' • H2180-OH* I OH*

O* • H- 80-0'* • neutral(s)

O' • H2180-0- H2

180'

N2 * H20 - N2 • H20

N2 • H?0 - N?H • OH

02 • H20 - 02 • H20

02 • H?0 - H02 • OH

02 • H?0 - H?02 • O

Oj • HO -OH • neutral 10

O • N?0 - N?0 • O

O ( 0) • N?0 - N?0 • C

O ( D) • NjO-NO NO

0.65 18B-65

0.32 18B-65

0.038 18B-65

0.027 18B-65

0.151 18B-65

1.13 18B-65

0.61 18B-65

0.55 18B-65

0.36 | 18B-65

0.14 1 18B-65

0.043 18B-65

0.037 1 18B-65

0.44

0.26

0.16

18B-29

18B-29

1CB-2°

•Excited state.

"All rate coefficients are based upon normalization to 1.2 > 10*° cm^sec"' for CH4 • CH4-CH5 • CH3.

M.-.,%M,I. No *» Jv» 19«» 18B-37

DNA 1948H

Toble 18B-2. Rate coefficients for negative-ion reactions.

Reaction Rate Coefficient** | k (HT'cm^sec"1) Reference

CO- • N- - no reaction «0.01 18B-29

O- • NO * no reaction -0.01 18B-29

CO., NO * no reaction <0.01 18B-29

NO" • 02 * NO • O" 0.35 18B-66

O- • 0« • no reaction •'0.05 I 18B-29

CO^ • C- * no reaction 0.01 18B-29

JO 10

C" HO -OH" • OH 0.05 18B-66

JO 12

O" HO • OH" • CH 0.05 18B-66

NO- • H.O *no reaction 0.005 18B-29

i - 18 ' O" • N? O • NO" neutral^ 0.065 18B-29

13 13 O" • N. 0 »N O" • neutrals 0.060 18B-38 '

NO« • N.O • no reaction 0.005 18B-29

0- cc2-ro: o2 0.03 18B-29

,30" • NOj • ,80 NOj 1.03 1 18B-29

• 'All rate coefficients ore bosed uoon normalization to 1.0 . lertiAec"1

1 for O NO. • O NO*.

^continued)

188-38 »'. . •. • ' ! • Vt»

CHAPTER 18B

S Table 18B-2. (Cont'd.)

Rate Coefficient** Reaction k (l<r9cm3iec-1) Reference ,

O" • N02-0" i NO • O 0.09 1 18B-66

NO" • NO?-NO • NOj 0.23 18B-66 |

0^ • N02 - 02 • N0~ 0.76 | 18B-66 |

°3 ' N°2 - °3 ' N02 0.22 18B-29 j

CO- • NO« - no reaction <0.01 18B-29

o" • o3 - 0 • C^ 1 ^0.15 18B-29

V<W°3~ «0.19 19B-29

•'All rate coefficients are based upon normalization to 1.0 > KrtfAec-1

! for 0 • N02-0 • NO .

I8B-39 "••' •" '... *, »„... t9;(j

DNA 1948H

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18B-4!

,/•».

•.-..• • . .

lr-Vn[

• '• " ' "

.* - ;- ;

: • : • .; : * - •: ' . •• . • *

* .: • i :.•..*• • t • :• i

• - •: -1

i t • : - i

• • - •:- i

\ - \<\

• ' - •: - •

• • * :.•; i •<"•:•.>.< ' ; • | ••;,::., • : • \ "\ • • • • • *...;;

' i • 1 • • : :

* -• ••: :••;'..» K * [ • .; pui #:»j ;.;> :,: ,-f *\ ' * '.' ' • ' •'< ' '••'•' '.

• • 7 • ' • ': • \

"' t.'.• 1 !>uri "T,'i 'v "-'** ; * "•*•.:»• ; ' *r>» | * -j-'."-'' i :

.»•»!!.>: ^ p.>::.... ••!)'! *IP-»M ' •! "• ' Ti i.»ui«j i >.><?<

,i ;• :j T «.» Mir\\p\ M\ ' w >| 1 V { * >} pu' •••>*] •;':.:.>:[ •..-.. ;

• i .' :» !•.»?: <!]>;! rititi * ' Y • *:>.;• ;.:-»•;.: ;: • • <. - .; - j

•i I »,. I i . . .,- • "«AIM '!,I-,'i ) *i" '" i ' w •.;»t'i\' * •'t - I -I

'it"*' *'; !'t "I !UPpj.^l«Ul\ • • * -•;•;-;!; I

H8r6i vNa

CHAPTER 18B

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18B-44 a»»*t»w» f« 1 Juw 1975

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