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NSRDS-NBS 64

U.S. DEPARTMENT OF COMMERCE j

National Bureau of Standards
NATIONAL BUREAU OF STANDARDS

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neujndi Durcau ui APR i 2 1978

n#T ftc c. ~

Rate Coefficients for Ion-Molecule Reactions

G

. us • * Organic Ions Other than Those Containing Only C and H

L. Wayne Sieck

National Measurement Laboratory

National Bureau of Standards

Washington, DC 20234

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued February 1979
Library af CMgrew Cataloging in Publication Data

Sieck, L Wayne.

Rate coefficients for ion-molecule reactions.

(Nat. stand, ref. data scr.; NSRDS-NBS 64)

“National Standard Reference Data System.”

Supt. of Docs, no.: C 13.48:64

1. Chemical reaction, Rate of. 2. Ions. 3. Molecules.

4. Chemistry, Physical organic. I. Title. II. Series: United States. National Bureau of Standards. National standard reference data series

; NSRDS-NBS 64. QD502.S52 547M39 78-10710

NSRDS-NBS 64

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 64, 27 pages (Feb. 1979)

(£) 1979 by the Secretary of Commerce on Behalf of the United States Government

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Foreword

The National Standard Reference Data System provides access to the quantitative data of physical science, critically evaluated and compiled for convenience and readily accessible through a variety of distribution channels. The System was established in 1963 by action of the President’s

Office of Science and Technology and the Federal Council for Science and Technology, and

responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National

Research Council of the National Academy of Sciences-National Academy of Engineering. A number of Advisory Panels, each concerned with a single technical area, meet regularly to examine

major portions of the program, assign relative priorities, and identify specific key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels

which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of advisory services contributes greatly to the guidance of NSRDS activities. The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically

evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computations of useful functions derived from standard reference data. The centers and projects also establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being

planned : nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and surface properties.

Reliable data on the properties of matter and materials are a major foundation of scientific and technical progress. Such important activities as basic scientific research, industrial quality control, development of new materials for building and other technologies, measuring and correcting

environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility

to support American science, industry, and commerce is vitally fulfilled.

Ernest Ambler, Director
Contents

Pago Foreword Ill

1. Introduction 1

2. Reaction Rate Tables 2

Table 1. Rate Coefficients for Reactions of Organic Cations 4

Table 2. Rate Coefficients for Reactions of Organic Anions 17

Acknowledgements 19

References 19

IV
Rate Coefficients for Ion-Molecule Reactions.

Organic Ions Other Than Those Containing Only C and H

L. Wayne Sieck

National Measurement Laboratory, National Bureau oj\ Standards, Washington, DC 20234

A compilation is presented of all experimentally determined bimolecular and termolecular rate

coefficients for the reactions of organic ions (other than those containing only C and H) with

neutral molecules in the vapor phase. The literature covered is from 1960 to the present, and both

positive and negative ions are considered. Five hundred and seventy-seven separate reaction- partners are tabulated, and experimental conditions are specified wherever possible. Preferred values

are suggested for a number of these processes. Key words: Chemical kinetics; data evaluation; gas phase ion-molecule reactions; mass spectrometry; organic molecules; rate coefficients.

1. Introduction

During the past decade, the detailed investigation of

the dynamics, rates, and mechanisms associated with

the interactions of ions with molecules in the vapor

phase has been characterized by an almost exponential

growth. The current widespread interest in these processes can be attributed to their recognized role in the

upper atmosphere, combustion systems, in materials

exposed to high energy radiation, and to their application in industrial chemical synthesis and trace analysis,

especially in air and water pollution. This is the second

in a series of compilations and evaluations of rate

coefficients for ion-molecule reactions occurring at thermal or near thermal ion kinetic energies. The first segment, which dealt exclusively with the reactions of

organic ions containing only C and H, was published

in 1976 [l] 1

. This portion deals with the reactivities of all other organic ions (other than those containing

C and H only). Ions which constitute “borderline”

organics, such as HCN+

, CS2

+

, CS2

", and C03", C04

_

, and CN”, as well as protonated CO and C02 , will be

considered in a subsequent article. Our goal in preparing these articles is twofold. First, we wish to provide a comprehensive, up-to-date compilation of those bimolecular and termolecular ionmolecule reactions and the associated rate constants

(coefficients) recorded under reasonably well-specified

experimental conditions at ion kinetic energies < 0.5 eV. We have restricted our entries to those data

expressed in units of cm3/molecule-s or cm6/molecule^s, which encompass more than 95 percent of the

figures in brackets indicate literature references at the end of this paper.

recent measurements carried out at thermal or nearly

thermal energies. Second, since rate coefficients have

now been determined under a variety of experimental

conditions it is possible, in individual cases, to subject

the combined literature to critical evaluation and to suggest a preferred value. We feel that this objective

is of prime importance since many investigators use

reference reactions for instrumental calibration purposes. Unfortunately, depending upon the particular

laboratory, different values have been assumed in many cases for the same calibration reaction, and in several instances the value chosen by a given laboratory has changed with time. One would hope that the

assignment of a preferred value with appropriate error

limits would provide a common reference base for use by the various research groups.

The following journals were searched for entries

from 1960 to the cut-off date, approximately 1 January 1978.

Journal of Chemical Physics

Journal of Physical Chemistry

Journal of the American Chemical Society

Journal of Research of the National Bureau of

Standards

The International Journal of Mass Spectrometry

and Ion Physics

International Journal of Chemical Kinetics

Canadian Journal of Chemistry

Chemical Physics Letters Transactions of the Faraday Society

Other pertinent entries were found by scanning Current

Contents, Advances in Mass Spectrometry, and the

published proceedings of various symposia and meet1
ings dealing with this subject. Unpublished results, as

well as any which were not subjected to prior critical review via the normal scientific refereeing channels, are not included. In spite of the fact that every effort has been made to extract all of the relevant kinetic

data from the literature it is possible, in an undertaking of this magnitude, that pertinent references may

have been inadvertently overlooked. Any omissions

which may have accidentally occurred are not intended

to reflect the authors’ judgments concerning the validity of individual rate measurements or the potential

accuracy of the experimental technique used by any

particular laboratory.

1.1.

Evaluation of Data

With respect to error limits and the reliability of

data, it is often difficult to make an objective judgment

concerning the validity of a particlar rate coefficient. However, it is our feeling that greater than 98 percent

of the tabulated values for fast reactions are most

certainly correct to within a factor of 2 of the true value at the stated temperature and/or kinetic energy.

Difficulties often arise in assigning more stringent

limits. For example, one of the perplexing aspects of

the chemistry associated with complex ions is the fact that the reactivity of these species may depend critically

upon the internal energy content of the reactant ion.

Whenever specific reactions have been shown to exhibit

such effects it is so stated in the compilation. Second,

many of the older values reflect the reactivities of ions

which were translationally excited due to the presence

of electric fields within the reaction zone. Although this condition would not necessarily affect the total reactivity of any given ion, it is well established that

resultant product distributions are often seriously af- fected. Moreover, in many cases the original authors

did not properly state their experimental conditions,

particularly with respect to the temperature of the bulk

gas. Even when the temperature was stated it is unlikely that the neutral flow component had achieved

equilibrium, especially in measurements carried out at reduced pressures. Taken together, these complications,

as well as others discussed elsewhere [2,3], introduce

a large and often undefinable uncertainty in a number

of the tabulated values.

When the accuracy limits given by the original

authors seem appropriate within the framework of the

possible sources of error, the original error limits are

cited. Otherwise, either a reasonable estimate is applied

or limits are simply not stated. In general, the most

recent values tend to be the most accurate for any

given reaction-pair.

2. Reaction Rate Tables

Two tables are presented, table 1 covering positive

ion reactions and table 2, negative ion reactions. The

entries in the various columns are described as follows: 2.1.

Reaction

The reactions are listed sequentially according to the following format:

(a) Carbon number of the reactant ion; i.e., all of the Ci’s appear first. (b) Increasing atomic number (Z) of the highest

Z element. A Ci ion containing only H and B (regardless of the number of boron atoms) would therefore

appear before CHNH+

, C2F6

+ would be listed before

C2H4FBU, and so forth.

(c) When the reactivity of any single ion towards

two or more neutrals has been reported, the ordering

sequence reflects the hierarchy of the neutral within

the procedure outlined in (a) and (b).

Only the empirical formula of the reactant ion is given. The neutral from which the ion was derived, or the structure suggested by the original author, is given under the column entitled Comments (see be- low) . The name or the structural formula of the

neutral reactant is always given under the Reaction

column. In order to conserve space, the abbreviations n (normal), i (iso), t (tertiary), and c (cyclo) are

also sometimes used to define structural isomers. Due

to the complexity of the product distributions asso- ciated with many of the reactions which are listed, as well as the fact that the branching ratios are often

sensitive to changes in temperature, pressure, and

internal energy, the reaction products are not specified.

Moreover, in many cases only the total reactivity of a given ion towards a given neutral was reported, with- out specifying reaction products.

2.2.

Rate Coefficient (fc)

Rate coefficients are given in units of cm3 molecule'1

s'

1 for bimolecular reactions and cm6 molecule"2 s'

1

for third order processes. Unless otherwise stated, the error limits given are those imposed by the original

authors (see Introduction for discussion). The most

recent experimental determination is listed first, the

other following in reverse chronological order. When a given laboratory has reported two or more values, or a corrected value, for a given reaction using the same

2
technique, then only the more recent or corrected

value is reported.

2.3.

Temperature (T)

When the system temperature was specified, then

that value is given in degrees K. All ion cyclotron resonance measurements may be assumed to have been

carried out at, or slightly above, ambient laboratory

temperatures (295 -f- 15, —5 K)

.

2.4.

Experimental Methods

The nomenclature used to describe the various

measurements techniques is similar to that used by

Ferguson [4]. Method See below for short description

DT Drift Tube

FA Flowing Afterglow

ICR Ion Cyclotron Resonance

MS Mass Spectrometer Ion Source

B Beam Apparatus

TI Ion Trap

a. Drift Tube (DT)

This is a relatively new technique which yields rate

coefficients from thermal to several electron volts kinetic energy. It has been mainly applied to the

reactions of inorganic ions of aeronomic interest.

b. Flowing Afterglow (FA)

This versatile method, which utilizes a buffer gas at relatively high pressures, assures that the reactant ions are essentially always in thermodynamic equilibrium

prior to reaction. The gas temperature is variable over

a considerable range (up to 900 K). FA has been

especially useful for the determination of equilibrium

constants and other thermodynamic quantities perti- nent to ionic association and particle transfer reactions as well as reactions of aeronomic importance.

c. Ion Cyclotron Resonance (ICR)

Ion Cyclotron Resonance mass spectrometry is a low pressure technique (1CT7 to 10'3 Nm'2

) in which

the reaction time is usually the variable experimental

parameter. Most of the rate data have been obtained at nearly thermal kinetic energies and at ambient room

temperature.

d. Mass Spectrometer Ion Source (MS)

This is a catchall category used to denote measure- ments involving a single reaction chamber associated

with a mass analysis system. The application of this technique varies considerably from laboratory to laboratory. Some groups work in the pressure range 10~3

to 10'1 Nm'2

, with or without pulsed chambers, while

others have extended the pressure range up to nearly one atmosphere. Both photoionization and electron

impact have been utilized to produce reactant ions. Many of the earlier low pressure studies involved the

application of a electric field across the reaction zone

for the purposes of ion extraction. In these cases the reactant ions were continuously accelerated, giving an

epithermal kinetic energy distribution.

e. Beam (B)

Beam experiments involve the generation of a mass

and energy selected ion beam which is impacted on a neutral target in a collision chamber coupled with a second mass analyzer. The kinetic energy may be

varied from nearly thermal values up to tens of kilovolts.

f. Ion Trap (TI)

This relatively new technique involves the trapping

of ions for a variable period of time in the negative

space charge of a continuous low energy electron

beam. The reactant ions may have kinetic energies in excess of thermal values, in some cases up to several

tenths of an electron volt. In many cases characterization of an experiment as being of the Beam type, Mass Spectrometer ion source

type, etc., is not sufficient for defining the exact meas- urement technique. The reader should always refer to the specific literature citation associated with the

quoted rate coefficient for details of the variation used

to generate any particular value.

2.5.

Comments

This column is used to provide descriptive information pertinent to the measurement such as “

k

varies

with temperature, photoionization,” etc. When the

quoted value of k for any particular reaction was

determined relative to an assumed value for a calibration reaction, then the assumed value for the calibration reaction is given. For ions containing two or more C atoms, one or more structural isomers may be

present in any given experiment. In every case where

the identity of the reactant ion is not obvious, we have

listed either the neutral from which the ion was derived

or the probable structural formula. The following

abbreviations are also used: KE = ion kinetic energy,

IEE = ion exit energy, and V cm'1 to denote the

magnitude of the imposed potential within the reaction

chamber. Several of the ICR values were determined

by pressure variation. When such measurements are

reported, the entry “Pressure varied” is included.

Comments pertinent to our choice of a preferred value

are also given in this column.

3
Table 1. Rate coefficients* for reactions of organic cations

Reaction T k Method Comments Ref. CH2N* + CHaNHa 370 £> CO MS 13eV e-, 3.4eV IEE 5 370 2.4 ( —9) MS 15eV e", 3.4eV IEE 5 370 1.6 ( —9) MS 50eV e-, 3.4eV IEE 5 9±1(—10) MS 6 + (CHs)aNH -> • 5 ( —10) MS 6

+ c-CsHsNHa 8.0±0.2(—10) ICR 7 + (CH3 ) 3N -» 5 ( —10) MS 6 CHS N* 4- CHaNHa - 370 2.6 ( —9) MS 13eV e“, 3.4eV IEE 5 370 2.6 (—9) MS 15eVe-,3.4eVIEE 5 370 1.9(— 9) MS 50eV e~, 3.4eV IEE 5 9±1 (—10) MS 6

CH4 N* 4- CHaNHa 295 1.1±0.1 (—9) MS Photoionization 8 370 1.8 ( —9) MS 13eV e~, 3.4eV IEE 5

4- CHaNHa 370 1.8 ( —9) MS 15eV e-, 3.4eV IEE 5 370 1.2 (—9) MS 50eV e", 3.4eV IEE 5 7±1(—10) MS 6

4- (CHa)aNH -> 6±2(—10) MS 6

4- CaHaNHo 298 1.97±0.2(—9) MS Photoionization 9

4- n-CaH7 NHa - 298 1.56±0.2(—9) MS Photoionization 9

4- (CHa)aN 4 ( —10) MS 6 CHsN* 4- CHaNHa -* 1.64(—9) ICR Time varied 10

2.06 (-9) ICR Pressure varied 10

295 1.21±0.1 (—9) MS Photoionization 8 370 2.7 (—9) MS 13eV e-, 3.4eV IEE 5 370 2.6 (-9) MS 15eV e-, 3.4eV IEE 5 370 1.9 ( —9) MS 50eV e", 3.4eV IEE 5 9±1(—10) MS 6 CH2DaN* 4- CDaNHa - 1.85 (-9) ICR From CDaNHa 10 CH«N* 4- 2CHaNHa -> 250 3.0( —26) MS CHaNHa+ 11 350 1.6 (-26) MS CHaNHa* 11 CH5 DN* 4- CHaNHa 6.4±0.2(—10) TI CHaNHaD* 12 ch2 d4 n* + CDaNHa 4.8(— 10) ICR CDaNHaD* 10

3.1 (—10) ICR CD3NH2D* 10

CH3N2* 4- CHaNaCH, -> 7.8±1.0(—10) ICR 13

ch2o* 4- CHaO -> 1.3 ( —10) ICR 14

1.77 (-9) ICR 15 373 1.93±0.02(—9) MS 3.4eV IEE 16 373 2.00±0.01 (—9) MS 2.4eV IEE 16

4- CHaOH 373 2.03±0.1(—9) MS Thermal ions 17

373 1.40±0.2(—9) MS 3.4eV IEE 17 CHjO* 4- (CH,)aB -* 2.2±0.4(— 10) ICR 18

4- CHaO -» 6.7 (-11) ICR 14

4- CHaOH -*• 373 2.11±0.3(—9) MS lleV e", Thermal 17 373 1.68±0.2(—9) MS 50eV e". Thermal 17 373 1.58±0.2(-9) MS lleV e“, 3.4eV IEE 17 373 8.0±2.0(—10) MS 50eV e~, 3.4eV IEE 17

0

VO 00 rH TI 19

4- CHaCHO -+ 1.80 ( —9) ICR 15

4- Ethylene oxide -* 1.16±0.15(—9) MS 20

+ HCOaCHa -> 2.0±0.2(—9) MS 21

-f Dimethylsulfoxide -> 408 4.5±0.5(—9) MS 0.71eV IEE 22 408 4.5±0.5(—9) MS 1.07eV IEE 22 CH2 DO* 4” DCOaCHa 1.9±0.2(—9) MS 2.4eV IEE 21 chd3o* 4- CDaOH -> 373 1.44 ( —9) MS From CD3OH, thermal 17 CH4 0* + CHaOH 2.17 ( —9) ICR Pressure varied, CHaOH* 10

2.08 (—9) ICR Time varied, CH30H* 10 1.86(—9) ICR CHaOH* 15

1.90(—9) ICR CH.OH* 23

4
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. ch4 o

+ + CH3OH -> 373 2.53±0.2(—9) MS lleV e

-

, thermal, CH30H+ 17 373 2.47±0.2(—9) MS 50eV e

-

, thermal, CH3 OH+ 17 373 2.56±0.4(—9) MS lleV c-,3.4eV IEE, CH3 OH+ 17 373 2.5±0.2(—9) MS 50eV e", 3.4eV IEE, CH3OH+ 17 450 2.0(— 9) MS 9.1 V cm"1

, CH30H+ 24 420 2.45 (-9) MS 0.86 V cm"1

, CH3 OH+ 19 See footnote c for further comment.

4- HC02CH3 370 2.54±0.1 ( —9) MS 2.4eV IEE, CH30H+ 21 + 2-pentanone -» 7.5 (-10) B 0.3eV KE, CH3OH+ 25 ch3 do+ + CH30H 450 2.0(—9) MS 9.1 V cm’1

, CH30D+ 24 + DCOaCHs 370 2.41±0.1(—9) MS 2.4eV IEE, CH3OD+ 21 chd3o

+ + CD30H 2.56 (—9) ICR CD30H+ 10 373 2.19 (—9) MS Thermal, CD3OH+ 17 450 2.0 (—9) MS 0.9eV IEE, CD3OH+ 24 CHsO* + CH3OH -> 1.1 (-10) ICR Time varied, CH3 OH2+ 10 1.0(-10) ICR Pressure varied, CH3OH2+ 10

8 ( —11) ICR CH3 OH2+ 15 CHsDsO^ + CD30H 1.5(—10) ICR Pressure varied, CD30H2+ 10

1.3 ( —10) ICR Time varied, CD30H2+ 10 chd4o

+ + CDaOH -> 4.4 (-10) ICR Pressure varied, CD3OHD+ 10

4.2 (-10) ICR Time varied, CD30HD+ 10 4.0±0.5(—10) TI CD3 OHD+ 12 cdo2+ + DCOaH -» 370 1.72±0.1(—9) MS 2.4eV IEE 21 CH202+ + H20 -> 174 3 ( —10) MS 26

200 3 ( —10) MS 26 280 3(—10) MS 26 CHDO/ + DC02H -» 370 1.59±0.1(—9) MS 2.4eV IEE 21 CH4N02+ + 2 CHaOH -> 1.9±0.4( —27) MS (CH3OH)NO+ 27 CF+ + CH3F 373 4.7 (-10) MS 0.24eV IEE 28

373 4.8 (—10) MS 0.65eV IEE 28

4- HFCO 5(—11) ICR 29

+ CH2F2 -> 320 1.12 (-9) MS 30 + CF4 320 3.3 (-10) MS 30

4- CHCRF -> 4 (-10) MS 0.2eV KE 31 + CC14 5.9 (—10) MS 0.2eV KE 31 4~ C2H2F2 —

320 1.12 (—9) MS 30

4" C2F6 -295 1.9±0.4(—10) MS Photoionization 32

3.9 (—11) B 0.3eV KE 33

4" C3Fs —

7.1 (-11) B 0.3eV KE 34

4- 1,1,2,2,-c-CJRF

1.78 ( —10) MS Average of two methods 35

4- SiD4 -» 1.1±0.1(-10) B l.OeV KE 36 CHF+ + CHsF -> 373 1.21 (-9) MS 0.24eV KE 28

373 1.10 (—9) MS 0.65eV KE 28

1.6 (-9) MS 0.2eV IEE 37

4" CH2F2 —

320 1.32 (-9) MS 30

317 1.77 (—9) MS 38 + CHCL.F -> 1.53 (—9) MS 0.2eV KE 31

4- CHQF2 3 ( —10) MS 0.2 eV KE 31 + CHF3 -> 1(—10) MS 0.2eV KE 31 CH2F

+ 4- 2 CHsF -* 320 2.8 (-26) MS 200eV e- 30 320 3.45 (-26) MS 14.5eV e“ 30 + CH2F2 1.30 ( —9) ICR 39

2.2 (-10) ICR 40

4“ 2 CHaF2 320 1.1 (—26) MS 30

4- CHaFCl 1.04±0.2(—9) ICR 41 + C2HsF -> 1.9±0.1 (—9) MS 42 + 2 CH2 CF2 317 7.8 (-25) MS 38

5
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. CHsF* + CHsF -> 320 1.86 (—9) MS 14.5eV e" 30

320 2.30 (-9) MS 200eV e' 30

1.73 (—9) ICR 39

1.37 (-9) ICR 43

1.38 (-9) ICR 44

373 1.53 (-9) MS 0.24eV IEE 28

373 2.27 (-9) MS l.leV IEE, Increases with

increasing IEE 28

2.2 (-9) MS 0.2eV KE

See footnote d for further comment.

37

CH.F* + CH*F -» 320 1.36 (—9) MS 200eVe- 30 320 9.5 (—10) MS 14.5eV e~ 30

9.9 (—10) ICR 39

7.1 (-10) ICR 44

9.0 (—10) MS 28

8.0 (-10 ) ICR 43

CHOP + HFCO - 2.5 (—9) ICR HFCO+ 29

CH*FO+ + HFCO -» 1.2 (

10) ICR (HFCO)H+ 29

CFa* + CHFS -> 320 9.3 (-10) MS 30 9.2(—10) MS 0.2eV KE 31 + cf4 -> 320 2.7 ( —10) MS 30

1.7(—10) ICR 39

1.4 ( —10) MS 0.2eV KE 31 + CHQFj -*> 390 4.0 (-10) MS 0.2eV KE 31

-f- CClaFa ~ 390 4.0(—10) MS 0.2eV KE 31

•f CH2 CFa -

317 2.15(—9) MS 38

-f- CoF

e

295 1.45±0.3(—10) MS Photoionization 32

6.7 (-11) B 0.3eV KE 33 + CaFs -> 2. 8 (—10 ) B 0.3eV KE 34 + SiH, -» 1 . 1 ±0. 1 (—9) B l.OeVKE 36 chf2+

-f- 1-C4H10 -

1.24±0.08(-9) ICR 45

+ neo-CjH^ -> 1.22±0.06(—9) ICR 45

+ CHsOH -> 1.41 (-9) ICR 46 + HCOOH -> 1.16 ( —9) ICR 46

4- CHsCHO ^ 9.6 (-10) ICR 46

4- CaHsOH - 1.1K-9) ICR 46

+ CHsOCHs 1.0 (—9) ICR 46

4- CHsCOOH 1.9 ( —9) ICR 46

4- HCOOCHa 1.53 ( —9) ICR 46 + CHaCOCH, -> 1.84(— 9) ICR 46 4 HCOOC2Hfi 1 . 86 (—9) ICR 46 4 CHaCOOCHa 1.51 (-9) ICR 46 4 CHaCOGHs 1.27 ( —9) ICR 46 4 (CHa)aCHCHO 2.05 (-9) ICR 46 4 HCOOC4 H# -> 1.56 ( —9) ICR 46 4 CHaFa -> 320 6.0 (

10 ) MS 30

1.9(—10) ICR 39

2.2 (—10 ) ICR 39

1.4 ( —10) ICR 40

4 CHFa 1.4 ( —10) ICR 39 4 CF2Cla ~ 9.7±1.4(— 10) ICR 41 4 CClaH -> 1.35±0.20(—9) ICR 41 4 CFCla -

1.21±0.18(— 9) ICR 41 4 CCU -> 1.28±0.19(-9) ICR 41 4 NHa 1.0 ( —9) ICR 46

CH2Fa+ 4 CHaFa ~ 320 1.77 ( —9) MS 200eV e" 30 320 1.13 ( —9) MS 14.5eV e- 30

6
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. ch2f2+

-f- CH2F2 -> 1.30 (-9) ICR 39 ch3f2+

-f- CH2F2 —

>

1.40 (-9) ICR 39 cf3+

-f- C2H6 323 3.6±0.4(—10) MS 15 V cm'1 47

-f- i-CiHio -

5.5±0.5(—10) ICR 45

-}- —

7.3±0.5(—10) ICR 45

-|- neo-CsH^ -» 4.9±0.4(—10) ICR 45 + CH3 F 2.7±0.7(—10) ICR 41 + chf3 -> 320 6.4(—10) MS 30

2.1 (-10) ICR 39 5.9(—10) MS 0.2eV KE 31 + CH2FC1 7.3±1.1 (—10) ICR 41

-f- CF2C12 —

5.8±0.9(—10) ICR 41 + CHCls -» 9.1±1.4(—10) ICR 41 + CFC13 -» 7.7±1.2(—10) ICR 41

-j- CC14 —

>

9.1 ±1.4 (—10) ICR 41

-j- C2F6 -> 295 4±1( —11) MS Photoionization 32

3.4 (-11) B 0.3eV KE 33 CsF8 2.9 (-11) B 0.3eV KE 34

-|- SiH4 -

>

6.5±0.7( —10) B l.OeVKE 36 ch2f3+ + CHF3 8.2 (-11) ICR (CHFs)H+ 39 CHSi+ + CH3 SiH3 -> 1.9±0.3(—10) MS 48

CH.SP + CH3SiH3 -» 1.7±0.4(—10) MS 48 CHsSP + CH3 SiH3 -> 1.26±0.33(—9) MS 48 + (CH3 ) 4 Si -> 1.6±0.4(—9) MS 11.7 V cm'1 49 CH4 Si+ + CH3 SiH3 -» 2.45±0.6(—9) MS (CH3SiH) + 48

4- (CH3 ) 2SiH2 —

1.3 ( —9) MS (CHsSiH) + 50 CH5Si+ + CH3 SiH3 3.2±0.8(—10) MS (CH3SiH2 ) + 48 + (CH3 ) 2SiH2 7.5 ( —10) MS (CH3SiH2 ) + 50 CH2SiF2+ 4" CHsSiFs —

6.1 (-11) ICR 51 CH3SiF2+ 4" CHsSiFs —

>

1.3 ( —11) ICR 51

-j- (CH3 ) 2SiF2 —

3.2 (-10) ICR 51 CH3SiF3+ 4" CH3 SiFs —

>

6.7 (—11) ICR 51 CH5 F

+ + CHsPH2 9.5±2.0(—10) ICR CH3PH2+ 52 CS+ + h2 7.3±1.1( —10) ICR 53

4- CH4 -> 9.5±1.4(—10) ICR 53 CHS+ + CH3SH -> 8.0±1.0(-10) MS 10.7 V cm"1 54

7 ( —10) MS 3.4eV IEE 55 + (CH3 ) 2SH 1.0±0.2(—9) MS 10.7 V cm"1 54 CDS+ 4- CD3SH -> 3.5±0.2(—10) TI 0.4eV KE 56 CH2S

+ + CH3 SH -> 8±1(—10) TI 0.4eV KE 56

4- (CH3 ) 2S 2.0±0.3(-9) MS 10 V cm

-1 54

4* dimethylsulfoxide -> 408 3.2±0.3(—9) MS >0.7eV KE 22 CHDS+ 4- CD3SH -» 7.9±1.5(-10) TI 0.4eV KE 56 CD2S

+ -f CD3SH 4.7±0.3(—10) TI 0.4eV KE 56 ch3 s

+ 4- CH3 SH 6.3±1.6(-10) TI 0.4eV KE 56 1.6±0.2(—9) MS 10.7 V cm

-1 54 1.04±0.03(-9) MS 3.4eV IEE 55

4* (CH3 ) 2S —

>

1.5±0.2(-9) MS 10.7 V cm1 54

4- dimethylsulfoxide -» 408 2.7±0.3(—9) MS 0.7eV IEE 22 408 2.6±0.3(-9) MS l.leV IEE 22 chd2s

+ + CD3 SH 6.7±0.2(-10) TI 0.4eV KE 56 8.0±0.6( —10) MS 3.4eV IEE 55 CDsS

+ + CD3 SH 7.2±0.6(—10) TI 0.4eV KE 56 1.00±0.04(-9) MS 3.4eV IEE 55 CH4 S

+ + CH3SH -» 1.41±0.07(—9) MS Photoionization 57 7.7±0.2(—10) TI 0.41V KE 56 1.19±0.06(—10) MS 3.4eV IEE 55

4- CsHsCHO - 1.8±0.1 (—9) MS 58

7
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. chd3s* .+ CH3 CHO + 1.2±0.2(—9) MS (CD3 SH) + 58 + CD3 SH 8.2+0.2(— 10) TI 0.4eV KE, (CD3 SH) + 56 1.21±0.03(— 9) MS (CD3 SH) + 55

4- CH3 OCH3 + 1.51+0.36(— 9) MS (CD3SH) + 58 ch5 s

+ + ch3sh 7.6 (—12) TI 0.4eV KE, CH3SH2+ 56 5.3+0.8(— 10) MS 10 V cm'1

, CH3SH2+ 54 + GHsCHO + 5.6+0.3(—10) MS ch3sh2+ 58 + (CH3 ):>S + 1.74±0.05(—9) MS ch3sh2+ 58

4- CH3COCH3 + 2.30+0.21 (-9) MS ch3 sh2+ 58 CH,DS+ 4- CH,S + 4.4±0.6(— 10) TI ch3 shd+ 12 CH2D3S* + ch3 och3 + 1.24+0.10 (-9) MS cd3sh2+ 58 CHD,S* 4

- chd3 s 1.3+0.2(—10) TI k reflects sources 56

of CD3 SHD+ 2.6+0.3(—10) TI k reflects source cd3shd+ 56

4- CH3 CHO h> 7.3+0.9(—10) MS cd3 shd+ 58 CHs SO* 4- dimethylsulfoxide -» 408 3.4+0.3(—9) MS 1.07eV IEE 22 408 3.4+0.3(—9) MS 0.71 IEE 22 408 3.2+0.3(—9) MS Thermal 22 ccr + CH3C1 + 373 1.2 ( —10) MS 0.21eV IEE 28 373 1.7(—10) MS 0.46eV IEE 28

4- CH3C1 373 2.1 (-10) MS 0.65eV IEE 28 373 1.4 ( —10) MS l.leVIEE 28

4- CHC1F2 + 2.0(—10) MS 0.2eV IEE 31

4- CHFC12 -> 4.0 (—10) MS 0.2eV IEE 31

4- CHCU -> 7.0(—10) MS 0.2eV IEE 31 + CC14 -> 4.0 (—10) MS 0.2eV IEE 31 chcr + CH3C1 -> 373 6.1 (-10) MS 0.2eV IEE 28 373 4.4 ( —10) MS 0.46eV IEE 28 373 3.3 (—10) MS 0.65eV IEE 28 373 3.2 (—10) MS l.leV IEE 28

4- CHFCla -+ 7.6 (-10) MS 0.2eV KE 31

4- CHCU -» 7 ( —10) MS 0.2eV KE 31 CH2C1+ +CH3 C1 -* 373 4.6(— 10) MS 17

4- CHF2C1 -> 1.5+0.5(—10) ICR 41

4* CH2C12 -<1.0(—11) ICR 41

4- C2H5 C1 -> 320 1.15+0.08(—9) MS 42 ch3ci+ 4- CH3C1 + 1.25 (—9) ICR 44

373 1.54+0.08 (-9) MS Value over range

0.21 to l.leV IEE 28

1.66 (—9) MS 0.2eV KE 59 373 1.70(— 9) MS 17 CHX1+ + CH3C1 + 1.4(— 10) ICR 44 373 1.0(-10) MS 0.45eV IEE 28

CNC1+ + CNC1 + 1.2 (—9) MS 60 cfcr 4- CHC1F2 - 4.2(— 10) MS 0.2eV KE 31

4- CHFC12 + 5.0 ( —10) MS 0.2eV KE 31

4* CFjCIj —* 6.1 (-10) MS 0.2eV KE 31 CHFC1+ + CHFC12 + 3.0+0.5(—11) ICR 41 CFjCR + CHFC12 + 2.2+0.3(— 10) ICR 41

4* CFCla -

4.0+0.6(—10) ICR 41

4~ CC1» -

5.0+0.8(— 10) ICR 41 4 i-C«Hio -

3.3 ( —10) MS 0.2eV KE 31 CC12

+ 4- CHFCU + 2.4+O.K—10) ICR 45

4- CHCls -> 3.6 ( —10) MS 0.2eV KE 31 4- ecu -> 5.9 (—10) MS 0.2eV KE 31 CHC12+ 4- CHaOH -» 7.5 (-11) ICR 46

4- HCOOH - 5.7 (-11) ICR 46

8
Table 1. Rate coefficients* for reactions of organic cations

-Continued

Reaction T k Method Comments Ref. CHC1/ + CH3 CHO + 5.6( —10) ICR 46 + C2H50H + 5.2 (—10) ICR 46 + CHaOCHa -» 4.0 ( —10) ICR 46 + HCOOCHa + 3.9 (—10) ICR 46 + CHaCOCHa + 5.7 ( —10) ICR 46 + HCOOG-Ho + 8.3(—10) ICR 46

4- CHaCOOCHa + 9.8 ( —10) ICR 46 + 1 -C4 H10 + 6.7+0.3(-10) ICR 45 + CHaCOCaHs + 7.2 (-10) ICR 46 + (CHa) 2CHCH0 + 1.33 ( —9) ICR 46 + GH5OGH5 -> 9.0(—10) ICR 46 + i-CsHi2 —

>

8.4+0.3(—10) ICR 45 + neo-CsHia -» 3.5+0.3(—10) ICR 45 + HCOOC4H9 -» 1.01 (-9) ICR 46 + CO* + 8.0+1.2(-ll) ICR 41 CDCl/ + NHa + 7.8(—10) ICR 46 + (CHa)aN + 1.37 (—9) ICR 46 CFO/ + CHCla -> <4 (—12) ICR 41 + CClaF 1.3+0.2(—11) ICR 41 + CCL + <4(—12) ICR 41 + I-C4H1O 7.4+1.0(-ll) ICR 45 + 2, 2-dimethylpentane -> 1.2+0.2(—10) ICR 45 + 3,3-dimethylpentane 1.8±0.1(—10) ICR 45 + 2-methylheptane + 7.3±0.4(—10) ICR 45 + 2,3-dimethylliexane + 5.8+0.3(—10) ICR 45 + 2,4-dimethylhexane -» 3.7±0.3(—SO) ICR 45 + 2,5-dimethylhexane + 4.5+O.K—10) ICR 45 + 2,3,4-trimethylpentane -> 3.4+0.2(-10) ICR 45 CC1/ + 2-methylheptane -» 6.0+0.4(—11) ICR 45 + 3-methylheptane -» 6.8+0.4(—11) ICR 45 + 2,3-dimethylhexane —> 6.2+0.5(—11) ICR 45 + 2,4-dimethylhexane -» 4.6+0.6(—11) ICR 45 + 2,5-dimethylhexane -» 1.1+0.H—10) ICR 45 + 2,3,4-trimethylpentane -» 4.9+0.7(—11) ICR 45 CH3Br+ + CHaBr + 295 5.8±0.4(—11) MS Photoionization at lO.OeV 61 295 3.8+0.3(—11) MS Photoionization at 11.7eV 61

5.5 ( —11) ICR 44 CH3I

+ + CH3I + 220 2.46±0.25 (—11) MS Photoionization 62 295 2.37+0.12 (—11) MS Photoionization 62 320 2.37+0.05(—11) MS Photoionization 62 + CHal + 295 1 .2+0.5 (

11) MS Photoionization 61

5.5 ( —12) ICR 44 + 2CHaI -> 295 3.3+O.K—25) MS Photoionization 62 CD3I

+ + CDal -> 220 2.04+0.12 (-11) MS Photoionization 62 295 2.23+0.05 (—11) MS Photoionization 62 320 2.16+0.12 (-11 ) MS Photoionization 62 + 2CDaI 295 9.4+3.0(—25) MS Photoionization 62 CH3Hg+ + C2H4 + 2.7+0.4(—10) ICR 63 + CaHe -> 2.9+0.3(—10) ICR 63 + Allene -> 1.5+0.5(—10) ICR 63 + 1,3-butadiene -> 3. 9+1.3(—10) ICR 63 + 1 -C4 H8 + 1.6+O.K—10) ICR 63 + iso-CtHg + 3.7+0.9(—10) ICR 63 + trans-2-CiH.a + 5.2(—10) ICR 63 +2-methyl-2-butene -» 5.2 ( —10) ICR 63 C2H6B

+ + (CHa)aB -> 2.6+0.4( —10) ICR (CHa)^ 18 GN+ + ch3cn -» 300 2.6 ( —9) MS Pressure varied 64 + C2HsCN 2.1 (-9) MS Pressure varied 64 2.0(— 9) MS Time varied 64

9
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. G>HN+ + CH3CN 3.54 ( —9) ICR CHCN+ 15 300 3.0 (—9) MS Pressure varied, CHCN+ 64

C2 DN* 4- CD3 CN 300 2.5 ( —9) MS Pressure varied, CDCN+ 64

300 6.7 (-9) MS Time varied, CDCN+ 64 c2h2n

+ + CHsCN 300 1.78 ( —9) MS Pressure varied, CH2CN+ 64

2.09 (—9) ICR CH2CN+ 15

4- C2H5CN 300 9 ( —10) MS Pressure varied, CH2CN+ 64

300 1 (—9) MS Time varied, CH2CN+ 64

CaD2N

+ + CDsCN -» 300 1.15 ( —9) MS Pressure varied, CD2 CN+ 64

300 1.08 ( —9) MS Time varied, CD2CN+ 64

CJW 4~ D2 —

>

1.0(-10) MS 3.4eV IEE, CH3CN+ 65 + CHsCN 2.09 (—9) ICR CH3CN+ 15 373 1.96 (—9) MS Thermal, CH3CN+ 17 300 2.01 (-9) MS Pressure varied, CH3CN+ 64 300 2.38 (—9) MS Time varied, CH3CN+ 64 2.15±0.21 (—9) MS 3.7eV IEE, CH3CN+ See 65

footnote e for further information

C2DsN

+ + CDsCN 300 2.45 (-9) MS Pressure varied, CD3 CN+ 64 300 1.98 (—9) MS Time varied, CD3CN+ 64 c2h4 n

+ + (CH3 ) 2NH 4 ( —10) MS From (CH3 ) 2NH 6 c2h5n* + (CH3 ) 2NH 5 ( —10) MS From (CH3 ) 2NH 6 G>HeN+ + (CHsJaNH -> 1.00±0.13(—9) MS ch3 nhch2+ 8 373 8 ( —10) MS 3.4eV IEE, (CH3 ) 2NH+ 5 4±1(—10) MS ch3 nhch2+ 6 CaH7N

+ + (CH3 )aNH -> 1.28 (—9) ICR Pressure varied, (CH3 ) 2NH+ 10

1.49 (—9) ICR Time varied, (CH3 )aNH+ 10 295 1.16±0.08(—9) MS Photoionization at 8.4eV 8 295 1.02±0.08(-9) MS Photoionization at 10.0, 11.7eV 8

373 1.2 ( —9) MS 3.4 eV IEE, (ChaIJMH* 5 6±1 (—10) MS (CH3 ) 2NH+ 6 + c2h5nh2 -» 298 1.83±0.09(—9) MS Photoionization, C2H6NH2+ 9 c2hd6n

+ + (CD3 ) 2NH 1.4 ( —9) ICR (CD3 ) 2NH+ 10 C2H*N+ + 2(CH3 ) 2NH -» 350 2.6 (-26) MS (CH3 ) 2NH2+ 11 + (CH3 )sN -> 3.5 (-10) MS From (CHsIsN 6 GH7DN+ 4- (CHalsNH -» 3.1±0.2(—10) TI (CH3 ) 2NHD+ 12 c2hd7n* + (CDsJaNH -> 3.4 (-10) ICR Pressure varied, (CD3 ) 2NHD+ 10

00 H o ICR Time varied, (CDs^NHD* 10 c2h3o

+ + CHsCHO -> 373 1.3±1.0(—10) MS 2.4eV IEE, CH3 CO+ 16 + CH3COCH3 -> 2.0(—10) ICR ch3co+ 66

2.33±0.10(— 10) ICR CHsCO+ from acetone 67 2.30±0.10(-10) ICR CH3CO+ from protonated ketene 67 2.2±0.2(—10) TI CH3C0+ 20

295 4.6±0.6(— 10) MS CH3C0+

, Photoionization 68 4.3±0.3(—10) ICR CH3 CO+ 69

473 3.0 ( —10) MS ch3co+ 69

+ CHsCOC2H5 7.0 ( —10) ICR ch3 co+ 66

4- vinyl formate -» 1.4 (—9) MS 2.4eV IEE 16

4- C3Hs COCH3 7.1±2.1(—10) ICR CH3 CO+ 7 + CeHsCHO -> 1.2 ( —10) ICR ch3 co+ 70

4- GHsOCaHs - 2.3(—10) ICR ch3 co+ 70

4- o-methylanisole -> 2 (—10) ICR CH3 CO+ from acetone 71 1.9±0.4(— 9) ICR CH3 CO+ from biacetyl 71 + m-methylanisole -» 1.8±0.4(— 10) ICR CH3C0+ from biacetyl 71

4- p-methylanisole -» 3.5±0.7(-10) ICR CH3C0+ from biacetyl 71

4- o-cresol -> 5.6=t0.6(—10) ICR CH3CO+ from biacetyl 72

10
Table 1. Rate coefficients8 for reactions of organic cations—Continued

Reaction T k Method Comments Ref. GIW -|- CD3 COCD3 -

295 4.6±0.6(—10) MS Photoionization, CD3 CO+ 69 C2H40

+ + ch3 cho 1.99( —9) ICR CH3CHO+ 15 2.49±0.10(—9) TI ch3cho+ 20

373 1.91db0.20( —9) MS Thermal, CH3CHO+ 16

-f- ethylene oxide -» 1.9±0.2(— 10) ICR From ethylene oxide 73 1.5±0.3(—10) TI From ethylene oxide 20

373 2±1 (

10 ) MS 2.4eV IEE 16 (mo* -f- CD3CD0 —

2.46 (-9) TI cd3cdo+ 20

+ ethylene oxide (d4 ) -* 1.9±0.2( —10) TI From deuterated

ethylene oxide 20 GH5CP + 2CH3CHO -> 1.25 (-25) TI CH3CHOH+ 20

+ GHsOH 1 . 12 (—9) ICR From C2H5 OH 10 473 1 . 2 ±0. 6 (—9) MS From C2H5OH 74 + (CH3 ) 20 1.3±0.9(—11) TI ch3coch2+ 20

-f- (CD3 ) 20 —

>

1.88±0.05(-9) TI ch3 choh+ 20 + (CH3 ) 2CO ^ 3.3±1.0(—11) TI ch3och2+ 20

2.25 (—9) TI ch3choh+ 20 + i'-CsHtOH -> 295 1 . 1 ±0. 1 (—9) MS Photoionization, CH3CHOH+ 75 1.5±0.3(—9) ICR ch3choh+ 76 c2h2d3o

+

-f- CD3OC2H5 1.75±0.05(— 10) TI cd3 och2+ 20 c2hd4 o

+

-(- C2D5 OH —> 1.04(—9) ICR cd3cdoh+ 10 c2h6o

+

-{- ( CH3 ) 20

+ —

>

1.58±0.15(— 9) TI (CH3 ) 20

+ 20

+ (CH3 ) 20

+ -> 373 1.45±0.1 (—9) MS 2.4eV IEE, (CH3 ) 20+ 16 373 1.93(—9) MS Thermal, (CH3 ) 20

+ 17 + c2h5oh -> 1.78 ( —10) ICR C2H5 OH+ 10

3.03 (-9) MS 10 V cm

-1

, C2H5OIP 77 c2h3d3 o

+ -h CH30CD3 —

>

373 2.09 (-9) MS Thermal, CH3 OCD3+ 17 c2d6 o

+

-f- CD3OCD3 —> 1.58 ( —9) TI (CD3 ) 20

+ 20 c2h7o

+ + C2H5OH 2.2 (—9) ICR Pressure varied, C2H5 0H2+ 10

2.4 (—9) ICR Time varied, C2H5OH2+ 10 + 2(CH3 ) 20 1.0±0.2(—25) TI (CH3 ) 2OH+ 20

~f- (CH3 ) 2CO —

>

1.0±0.1 (—9) TI (CH3 ) 2OH+ 20 c2h2d5o

+ + c2d5 oh -* 1.7 ( —10) ICR Pressure varied, C2D5 OH2+ 10

1.4 ( —10) ICR Time varied, C2D5 0H2+ 10 c2hd6o

+ C2D5OH —

3.7( —10) ICR Pressure varied, C2D5 0HD+ 10

2.8 (-10) ICR Time varied, C2D5OHD+ 10 GJRO/ + HC02CH3 ^ 370 1.57±0.10(—9) MS 2.4eV IEE, HC02CH3+ 21 C2H3 D02

+

-(- dco2ch3 -> 370 1.65±0.10(—9) MS 2.4eV IEE, DC02CH3+ 21 GHsN03+ + 2CH3OH -> 2 (—27) MS (CH3OH) 2NO+ 27 c2f

+

-f- ch2cf2 —

>

317 1.91 (-9) MS 38 GHF* -f- c2h3f —

>

1.93±0.12(—9) MS 78 370 1.95 (-9) MS 79

-(- ch2cf2 —

317 1.84 (—9) MS 38 C2H2F

+ C2H3F —

1.03±0.06(—9) MS 78 370 7.5±1.0(—10) MS 79 + c-HsF -> 1.75±0.19(—9) MS 42 c2h3f

+

-(- c2h4 —

>

5.9±1.8(—10) ICR 80

-{- C2D4 —

>

5.1 (—10) 7CR 81

-f- c2h3f —

>

300 2.9 (—10) CR k varies with internal energy 82 C2HsF+ + c2h3f 2.1 (-10) CR 81 295 3.2±0.2(— 10) MS Photoionization 83

2.1 (-10) ICR 84

1.34 (—10) ICR 85 2.2±0.4(—10) TI 86 370 3.0 (-11) MS 19eV e” 79

370 2.3 (-11) MS lleV e" 79

-|- 2C2H3 F —

>

1.61 (-25) MS 78 + c2h5f ^ 320 5.9 (—10) MS From C2H3F 42

-f- ch2cf2 —

1.02 (-9) ICR 81

11
Table 1 . Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. c2h*f+ + cis-CHFCHF 1.4 ( —9) ICR 81

4- frans-CHFCHF -> 1.3 ( —9) ICR 81 + C2HF3 -> 1.3 ( —9) ICR 81 + C2F4 8.8 ( —10) ICR 81

-|- 2-fluoropropane -* 1.3±0.2(—9) ICR From 2-fluoropropane 87 C*H4F* + CsHsF - 4.2±0.7(— 10) MS 78

4- C2H5F -> 320 ].06±0.10(—9) MS 42

4- 2-fluoropropane -» 1.4±0.2(— 9) ICR From 2-fluoropropane 87 C,H5F

+ 4- C2H3F -> 320 1.53±0.12(—9) MS 200eV e" 42

320 1.18±0.20(— 9) MS 14eV e

_ 42

1.50 ( —9) ICR 44 c2h«f* + 2CH3F -> 320 1.5( —27) MS 200eV e", (CH,)*P 30 320 2.3 (—27) MS 14.5eVe- (CH3 ) 2F

+ 30

-f- 2CH2F2 ~ 320 5.88(—28) MS 30

4- C2H5F -> 320 1.33±0.14(— 9) MS 42

1.4 (—9) ICR 44 CaF2* 4" GFg —> 1.2 ( —10) B 0.3eV KE 34 c2h2f2+ 4- GH* 3.4±0.5(— 10) ICR CHFCHF+ 80 2.5±0.5(—10) ICR CH2CF2+ 80

1.6 ( —10) ICR From cis-CHFCHF 81

8.5 ( —11

)

ICR From frans-CHFCHF 81

1.7 ( —10) ICR CH2CF2+ 81

4" GD4 —i 2.9 ( —10) ICR ch2cf2+ 81 + C2HsF -» 5.1 (-10) ICR ch2cf2+ 81

1.9 ( —10) ICR From frans-CHFCHF 81

4- CH2CF2 3.5 (—10) ICR From cis-CHFCHF 81

2.2 (—10) ICR From frans-CHFCHF 81

4- cis-CHFCHF -> 8.9 ( —10) ICR CH2CF2+ 81

6.3 ( —12

)

ICR From cis-CHFCHF,

Charge transfer only 88

8.3 (—11) ICR From frans-CHFCHF, 88 charge transfer only

6 ( —12) ICR From cis-CHFCHF, 81 condensation only

2.6 ( —10) ICR From frans-CHFCHF 81

4- frans-CHFCHF -> 5.7 (-10) ICR From cis-CHFCHF 81 3(—12) ICR From frans-CHFCHF,

condensation only 81

2.4( —10) ICR From cis-CHFCHF,

charge transfer only 88

3 ( —12) ICR From frans-CHFCHF,

charge transfer only 88

4" 2CH2CF2 320 5.98 (-26) MS CH2CF2+ 38 1.1±0.2(—24) ICR ch2cf2+ 89

+ C2HF3 -* 8.9(—10) ICR ch2cf2+ 81

7.8 (—10) ICR From cis-CHFCHF 81

5.4 ( —10) ICR From frans-CHFCHF 81

4* C2 F4 —

>

6.4 (—10) ICR CH2CF2+ 81

5.7 ( —10) ICR From cis-CHFCHF 81

3.9 (—10) ICR From frans-CHFCHF 81 c2d2f2+ +C2H3F - 3.5(—10) ICR From cis-CDFCDF 81 1.9±0.4(—10) MS 78 c2f/ 4" GF8 —

>

8.3 ( —11 ) B 0.3eV KE 34 ghf3+ 4" C2H4 —

>

1.7 ( —10) ICR 81 6.7±0.7(— 10) ICR 80

4- CH2CF2 -» 1.8 ( —10) ICR CHFCF4 81 + cis-CHFCHF -> 2.7 (—10) ICR chfcf2+ 81

4- frans-CHFCHF -» 2.8(—10) ICR chfcf2+ 81 + GHF3 -> 5 ( —11) ICR Condensation only 81

12
Table 1. Rate coefficients3 for reactions of organic cations—Continued

Reaction T k Method Comments Ref. C2 HF3+ + c2hf3 -> 5.6 (—11) ICR chfcf2+ 90

4.8 (-11) ICR CHFCF/ 85 + c2f4 -» 2.2(—10) ICR chfcf2+ 81

5.7 (—11) ICR chfcf2+ 90 c2df3+ + GHsF 1.4 ( —10) ICR cdfcf2+ 81 cjw»+ + 2CH2F2 5.16(—28) MS 30 cjv + C2H4 1.7(—10) ICR 81 1.07±0.30(— 10) ICR 80 + C2HsF -» 1.6 (-10) ICR 81 + C2F2 l.O(-ll) ICR 90 + ch2cf2 1.5(—10) ICR 81 + cfs-CHFCHF 1.9 ( —10) ICR 81 + frans-CHFCHF -» 2.0 (—10) ICR 81 + C2HF3 2.1 (-10) ICR 81 1.06(—10) ICR 90 + C2F4 1.5 ( —11) ICR Condensation only 81 l.O(-ll) ICR Condensation only 85 c2f5+ + c2f6 7.1 (-11) B 0.3eV KE 34 + CsF8 —> 8.6 (—12) B 0.3eV KE 34 C2H6 Si+ + (CHaJ^iH, —> 7.0(—10) MS (CH3 ) 2Si+ 50 C2H6FSi+ + (CH3 ) 2SiF2 5 (—10) ICR (CH3 ) 2SiF+ 51 + (CH3 ) 3SiF 7.4 (-10) ICR (CH3 ) 2SiF* 51 C2H6F2Si+ + (CH3 ) 2SiF2 -» 2.0(— 10) ICR (CftOsSiF* 51 C2H7P

+ + (CH3 ) 2PH 6.3±1.2(—10) ICR (CH3 ) 2PH+ 52 c2h5s

+ + CH3SH -» 1.5±0.2(—10) MS 10.7 V cm1 54 + (CH3) 2S -» 3.5±0.5(—10) MS 10.7 V cm1 54 CsHeS" + C2H5SH -» 1.25±0.06(—9) MS Photoionization, C2H5 SH" 57 + (CH3 ) 2SH -» 3.2 (—12) MS (CH3 ) 2 S

+ 58 C2HtS

+ + (CH3 ) 2S -> 2.8±0.4(— 10) MS 54 c2h6 os+ + dimethylsulfoxide 408 1.9±0.2(— 9) MS From dimethylsulfoxide 22 c2h3 ci+ + C2H3C1 295 1.78±0.09(—10) MS Photoionization 83

9.6 (-11) ICR 84

5.2 ( —11) ICR 85 370 1.81 ±0.06 (—11) MS 20eV e" 91 370 1.35(— 11) MS 15eV e“ 91 370 1.03(—11) MS 10.5eV e" 91 c2H5a+ + C2H5C1 -» 320 1.78±0.09(—9) MS 42 GH5C1+ + C2H5 C1 -» 1.50 ( —9) ICR 44 c2h6 ci+ + C2H5 C1 -> 320 1.36 ( —9) MS C2H5 C1H+ 42 5.5(—10) ICR C2H5 C1H+ 44 C2H3Br+ + C2H3Br 295 1.25(—10) MS Photoionization 83 370 6.5±0.2(— 12) MS 2.4eV IEE 91 + 2C2H3Br -» 370 5.5±0.2(—26) MS 91 C2HsBr+ + C2H5Br -» 295 6.7±0.5(—11) MS Photoionization 61

5.6 ( —11) ICR 44 C2H6Br+ + CoHsBr -» 5(—11) ICR C2H3 BrH+ 44 c2h5i+ + C2H5I 295 2.0±0.1(—11) MS Photoionization 62 1.6(—11) ICR 44 + 2C2HsI 295 4.1 (-24) MS Photoionization 62 c2h3 d2i

+ + CHaCDJ 295 2.0±0.1 ( —11) MS Photoionization, CH3 CD2I

+ 62 c2h3d2i

+ + 2CH.CDJ -> 295 5.3 (-24) MS Photoionization, CH3 CD2I

+ 62 c2h2d3i

+ + CDsCHJ -a. 295 2.0±0.1 ( —11) MS Photoionization, CD3 CH2I+ 62 + 2CD3 CHJ 295 7.4 (-24) MS Photoionization, CD3 CH2I

+ 62 c2d5i

+ + C2DsI -» 295 2.0±0.1(—11) MS Photoionization 62 + 2C0D5I -» 295 1.01 (-23) MS Photoionization 62 c3hn+ + CJisCN 300 3.7 (-9) MS From C2H3 CN 64 CsH2N

+ + C2HsCN -a- 300 1.9 ( —9) MS From C2H3 CN 64 c3h4 n

+ + C2H5CN 300 1.2 ( —9) MS Pressure varied, C2H4 CN+ 64

13
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. GH4 N* + CaH.CN 0.6 (-9) MS Time varied, GH4 CN* 64 GD.N* + CaDsCN -* 300 1.7 (—9) MS Pressure varied, GD4 CN* 64

300 0.5- (9) MS Time varied, C»D4CN* 64 gh9n* 4- cyc/o-GH.NHa -» 1.3±0.4(-10) ICR From cyc/o-GHsNHa 7 gh7n* 4- cyc/o-GH.NHa -» 1.9 ( —10) ICR From cyc/o-GHsNHa 7 + (CHa)aN -> 1 . 0 (- 10 ) MS From (CHs)aN 6 CaHaN* 4- diethylamine -» 298 1.36±0.14(—9) MS From diethylamine 9

4- pyridine -> 5.3 ( —10) ICR (CHa)aNHa* 92 GH*N* + n-GH7NHa 298 1.56±0.08(-9) MS From n-GH7 NH2 9 + (CHa)aN 295 8.2±0.3(— 10) MS Photoionization at 8.4eV, 8 (CHa)aN*

+ (CHa)aN 295 5.5±0.5(—10) MS Photoionization at lO.OeV,

(CHa)aN+ 8 295 4.9±0.3(— 10) MS Photoionization at 11.7eV,

(CHa)aN+ 8

3.3 ( —10) MS (CHa)aN* 6 CsHioN+ + 4-methylpyridine -> 2.6 (—10) ICR (CH3 )aNH+ 92 GHuBsNs* + (CH«)aBaNsHs -> 7.0±0.4(— 10) MS (CHa) 3 BaNaHa+ 93 GHs O* 4- cyc/o-GH5OH -> 2. 0±0. 6 (—10 ) ICR From cyc/o-CaHsOH 7 4* 2-butanone -> 6. 0 (—11 ) ICR GH.CO* 66 GH6 0* + Cyc/o-GHsOH -> 1.5±0.5(—10) ICR From cyc/o-GHsOH 7

+ CHaCOCHa -» 6.0 (

10 ) ICR CHaCOCHa* 66

2.0 (—10) ICR Condensation only 72 6.5±0.3(—10) TI CHaCOCHa* 20 5.4±0.4(— 10) ICR CHaCOCHa* 69

+ CHaCOCHa - 473 5.1 (—10) MS CHaCOCHa* 69 300 8.5±0.3(— 10) MS Photoionization at lO.OeV,

CHaCOCHa* 68

300 7.6±0.3(—10) MS Photoionization at 11.7eV,

CHaCOCHa* 68 GD9 0* -)- CD3 COCD3 300 7.0±0.3(— 10) MS Photoionization at lO.OeV,

CD3 COCD3* 68

300 6.8±0.3(—10) MS Photoionization at 11.7eV,

CDaCOCDa* 68 gh7 o* + CHaCO - 2.98±0.10(— 10) ICR (CHa)aCOH* 67 + CHaCOCHa -* 4.0 (—11) ICR (CHa)aCOH* 66 473 4.3 (-10) MS 12 V cm1

, (CHa)aCOH* 69

+ 2CHaCOCHa - 6.5±0.5(—25) TI (CHa)aCOH* 20

+ iso-GHs -> 7.1 (-11) ICR (CHa)aCOH* 92

-f- tGH»OH 1.1 (-9) ICR (CHa)aCOH* 94 3.7±0.5(— 10) ICR (CHa)aCOH* 95 gh8 d3 o* f CDaOCaH. -> 1.43±0.05(—9) TI CD30 C2H5 * 20 GHiOa+ 4- vinyl formate -* 373 1.4 ( —9) MS From vinyl formate 16 CaHaOa* 4~ t-GHoOH -> 6.8(— 10) ICR (CHahCOHOHa* 94 GH4 F* + CaHaF - 2.2±0.7(-10) MS 78

4- CHaCFa -* 320 3.49 (-10) MS 38 C3H6 F* 4- 2-fluoropropane -> 4.4±0.6(— 10) ICR (CHa)aCF* 87 GHaFa* 4- CaHaF 5(—11) MS 78

4- CHaCFa 320 1.24 ( —10) MS 38 ghjv 4” CHaCFa 320 6.6 (

11 ) MS 38

4- CaHFa -> 3.0 (11) ICR 90 GHioSi* 4- (CHa)aSiH 7 (

11) MS (CHa)aSiH* 50 GHoFSi* 4- (CHa)aSiF 6.5 (

10) ICR (CHa)aSiF* 51 GH*P* 4- (CHa)aP -* 5.9±1.2(—10) ICR (CHa)aP* 52 GHsS* 4- C,H7SH - 1.13±0.56(—9) MS Photoionization, CaH7SH* 57 GH.Sa* 4“ (CHa)aS —

>

1.6±0.2(-11) MS 10.7 V cm"1 54 GH8 N* 4- CaH.CN - 1.78±0.54(— 9) ICR CaH.CN* 7 GHuN* 4- diethylamine -» 298 1.25±0.06(—9) MS From diethylamine 9

14
Table 1. Rate coefficients8 for reactions of organic cations—Continued

Reaction T

C4H4 0

+ + toluene -» C4H70

+ + diisopropyl ketone -» C4H80

+ + 2-butanone -» C4 H90

+

-f- 2-butanone C4HnO+ + t-butanol -» C4H602+

-f- biacetyl -> + pyrolle -> C4Hi202+ + t-butanol -» C4Hi0 S

+ + (CH3 )sCSH

CsHeN+ + (CHsJsNH

C5Hi2N+ + triethylamine -» 298 CsH80

+ + cyc/o-CsHsCOCHs ->

CoffioO"*" -f- 3-pentanone

C5HiiO+ + 3-pentanone -* C5H9 02+ + CH3COCH3 473 + CeHsNHa -> + c6h5no2 + anisole (H-substituted) -» + anisole (o-methyl substituted) ->

4- anisole (m-methyl substituted) 4- anisole (p-methyl substituted) -»

4- anisole (p-ethyl substituted) ->

4- o-cresol -»

4- m-cresol -»

-f- p-cresol

+ CeHsOH

+ CeHoCHO

4- C6H3OCH3 4~ C6H5OCD3 4- c6h5coch3 -> 4- GH5OGH5 -» GHsFe+ + FeCCsHa).

CsH5Ni+ 4- CH3CHOh>

C6HsN+ 4- (CH3 ) 3N ^

CJR5N+ + (C2H5 )sN -» 298 C6 Hi6N

+ 4- quinuclidine -» C6Hn02+ + 2-butanone -» GHb03+ 4- CeHsNHa

4- o-cresol -> G>H903+ 4* m-cresol

4- p-cresol 4- anisole (H-substituted) -»

4- anisole (o-methyl substituted) -»

4- anisole (m-methyl substituted)

4- anisole (p-methyl substituted) -»

4* anisole (p-ethyl substituted)

4- pyrrole ->

4- CeHaOH -»

4- CeH5N02 4- CeHsCN

4- CeHsCHO

4- C6H5OCH3 4- C6H5OCD3 —

>

4- CeHsCOCHs

4- C6 H5OC2H5

k Method Comments Ref. 1.28±0.19(— 9) ICR From furan 96

1.1 (-10) ICR (CH3 ) 2CHCO+ 66

9( —11) ICR ch3 coc2h5+ 66

9.0 (-11) ICR (CH3 COC2Hs)H+ 66

7.2( —10) ICR (CH3 ) 3COH2+ 94 7.5±1.0(—10) ICR (CH3 CO) 2+ 97

4.3 (-10) ICR (CHsCO)/ 97

2.3 ( —10) ICR (CH3 ) 3 COH2OH2+ 94

5.7 (—10) MS (CHa)sCSH+ 57

3.3 (-10) ICR Protonated pyridine 92 1.28±0.13(— 10) MS (C2H5 ) 2NCH/ 9 2.0±0.6(—10) ICR From cycZo-C3HoCOCH3 7 8(—11) ICR From 3-pentanone 66

5( —11) ICR Protonated 3-pentanone 66

8 ( —11) ICR (CH3 COCH3 )CH3 CO+ 66 5.4±0.4(—10) ICR (CH3COCH3 )CH3CO+ 69

5.1 (-10) MS (CH3COCH3 ) ch3 co+ 69

1.5 ( —10) ICR CHsCO (COCHs) CH3+ 98 4( —11) ICR CH3CO(COCH3 )CH3+ 71 2.9±0.6(—10) ICR CH3 CO(COCH3 )CH3+ 71 4.0±0.8(—10) ICR CH3 CO(COCH3 )CH3+ 71 5.4±1.1(—10) ICR CH3CO(COCH3 )CH3+ 71 3.0±0.6(—10) ICR CH3 CO(COCH3 )CH3+ 71 3.7±0.7(—10) ICR CH3 CO(COCH3 )CH3+ 71 5.8±0.6(—10) ICR CHsCO (COCHs) CHs+ 72 6.1±0.6(— 10) ICR CHsCO (COCHs) CHs+ 72 4.6±0.5(—10) ICR CH3 C0(C0CH3 )CH3+ 72

4.3 (-10) ICR CH3 CO(COCH3 )CH3+ 70

8.5 ( —10) ICR CH3 CO(COCH3 )CH3+ 70 2.9(—10) ICR CHsCO (COCHs) CH3+ 70 2.9(—10) ICR CH3 CO(COCH3 )CH3+ 70

6.3 ( —10) ICR CHsCO (COCHs) CH3+ 70 4.8(—10) ICR CH3CO(COCH3 )CH3

+ 70 2.4±0.5(— 9) MS From cyclopentyl iron 99 7.9±0.7(—10) ICR From cyclopentyl iron 100 8.0±1.6(—10) ICR from cyclopentyl nickel 101

6.5 (—10) ICR Protonated 4-methyl

pyridine 92 7.05±0.35(-10) MS (CJD.N+ 9

5.6 (—10) ICR (C2H5 ) 3NH+ 92

9.0 (—11) ICR (CH3COC2H5 )CH3 CO+ 66

1.8 (—9) ICR CHsCO (COCHs) COCH3+ 98 4.8±0.5(—10) ICR CHsCOCO (COCH3 ) ch3+ 72 4.9±0.5(—10) ICR CH3COCO(COCH3 )CH3+ 72 4.9±0.5(—10) ICR CHsCOCO (COCHs) CH3+ 72 1.4±0.2(—9) ICR CHsCOCO (COCH3 )CH3+ 71 9.5±1.9(-10) ICR CHsCOCO (COCHs) CHs+ 71 1.6±0.3(—9) ICR CHsCOCO ( COCHs) CH3+ 71 1.6±0.3(—9) ICR CHsCOCO (COCHs) CH3+ 71 2.5±0.5(—9) ICR CHsCOCO (COCHs) CHs+ 71

1.1 (—9) ICR (CHsCO) 3+ 97

4.2 (-9) ICR (CHsCO) 3+ 70

1.7 (—9) ICR CHsCO (COCHs) COCHs+ 98

3.0 (-9) ICR CHsCO (COCHs) COCHs+ 98

1.5 (—9 ICR ( CHsCO ) 3+ 70

1.4 (—9) ICR (CHsCO) 3+ 70

1.4 (-9) ICR ( CHsCO ) 3+ 70

6.8 (—9) ICR (CHsCO) 3+ 70

1.2 (-9) ICR ( CHsCO ) 3+ 70

15
Table 1. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. GH903+ 4* o-methyl nitrobenzene -» 9.0 (—10 ) ICR CH3CO(COCH3 )COCH3+ 98

-f- m-methyl nitrobenzene -» <3.0 (

11 ) ICR CKUCO (COCH3 ) COCH3+ 98 CHsF* + p-difluorobenzene -> 1 . 02 ±0. 15 (—9) ICR From fluorobenzene 96

-f- 2-CeHsF —> 295 4±1 (—26 ) MS From fluorobenzene 102 CJRF«* + CcHsF -> 2. 4±0. 4 (—10 ) ICR From p-difluorobenzene 96 CcHsCR + 2GHsCl -» 295 5. 3 ±1 . 0 (—26 ) MS From chlorobenzene 102

4~ C6H5Br 530 1.1 (-9) MS From chlorobenzene 103 570 1-4 (

9 ) MS From chlorobenzene 103 CtHsN* 4” GH6 500 1.3 (

9 ) MS C6H5CN+ 103 CtHhN+ + (CoHs)aN 3.3 ( —10 ) ICR Protonated quinulidine 92 CrHuO* 4- (i-C3H7 ) 2CO 2 ( —11 ) ICR (i-CsHt) 2CO+ 66

CTGO* 4- (i-C3H7 ) 2CO -> 2 ( —11 ) ICR (i-C3H7 ) 2COH+ 66 CtH7 F

+ 4- toluene -* 2. 8 ±0. 4 (—10 ) ICR From p-fluoro toluene 96 C,HsF3

* 4~ GFsH —

>

1 . 16±0. 17 (—9 ) ICR C6H5CF3+ 96 CsHisO/ 4- (C2H5 ) 2CO 3 (

11 ) ICR (C2H5 ) 2COC2HsCO+ 66 CoHu(V 4- CH3COOC7H7 -> 360 2.8 (—9) MS (CH3COOC7H7 )H+ 104 CuHaOa* + (i-C3H7 ) 2CO 2( —11) ICR (i-C3H7 ) 2COC3H7 CO+ 66

•Rate coefficients are in units of cm* molecule"1 s'

1 for bimolecular reactions and cm6 molecule-2 s

-] for termolecular reactions. ‘The numbers in parenthesis should be read as the power 10 of the number. Thus ( —9) is 10"9

. 'The reaction CH30H+

-(- CH3 0H products has been investigated in five different laboratories. The most recent determinations

(refs. 10, 15, and 23) of the overall conversion coefficient were obtained by the ICR technique, and suggest an average value of 2.00 ± 0.17 ( —9) for this process. All earlier values were obtained by single source mass spectrometry (refs. il7, 19, and 24). In each of those studies the rate coefficient for the reaction CH4 -f- CtR products was independently determined and reported.

Taking the reference value which we suggested earlier [1.14 (—9), ref. 1] for the methane reaction together with the methanol

values given in refs. 17, 19, and 24, and appropriately correcting the individual values given for methanol, an average value of 2.47 ± 0.16 ( —9) is obtained for the MS studies. Although one is tempted to suggest that the recent ICR values are more accurate,

it is disconcerting to note that ref. 10 (the most recent ICR study) also reports a value of 2.56 ± 0.17 (—9) for the reaction CD30H+ + CD3 OH -> products, which is essentially equivalent to the MS value for the unlabeled analogue. Taking all factors into consideration, and recognizing that the methanol reaction will exhibit a negative temperature and ion kinetic dependence due to ion-dipole interactions (ref. 23), it would seem that the actual value of the thermal rate coefficient (300 K) for the reaction CH.3 OH+

-f- CH.jOH -* products other than CH3OH+ (resonance electron or hydrogen exchange also gives CH3 OH+

, and would be

undetected) should fall within the limits 2.2 ± 0.3 ( —9). Additional careful measurements involving this reaction pair are encouraged since it appears to represent a model highly reactive oxygenated organic system.

d Taking the most recent value from Beauchamp’s laboratory (ref. 39), the lowest kinetic energy value from ref. 28, the lowest

electron impact energy value of ref. 30, and the earlier ICR value of ref. 43, the current thermal value for this fast reaction falls within the limits 1.64 ± 0.22 ( —9), which is essentially equivalent to a collision efficiency of unity for conversion to products. Contributions from resonant electron or atom exchange cannot be evaluated. 'The rate coefficients reported for this very fast reaction have remained remarkably consistent over the years, and a value of 2.12 ± 0.20 (—9) is suggested at moderate temperatures (~300 K) for thermal ions.

16
Table 2. Rate coefficients* for reactions of organic anions

Reaction T k Method: Comments Ref. CH4N- + CH3F 297 5(—ll) b FA CHsNH- 105 + CH3CI 297 1.7±0.1(—9) FA CHsNH" 105 + C2H2 —

>

297 1.33±0.33(—9) FA CHsNH- 106 CH3O- + CHsOH 1.2±0.3(—9) ICR 107 + CH3F -> 297 1.4±0.2(—11) FA 105 + CH3CI 297 1.3±0.1(—9) FA 105 + C2H2 —

297 1.64±0.41(— 9) FA 106 300 1.3 ( —9) FA 108 + CHsCN -» 297 3.5±0.3(—9) FA 109 + C2H5OH -> 300 >5(—11) FA 110 + allene -> 300 ~5(-12) FA 110 + propylene 300 <5 ( —12) FA 110 + f-C^OH -> 300 >5(—11) FA 110 + CeHsCHs -» 2.0±0.2(—10) ICR 107 300 >5(—12) FA 110 + C6HsCH(CH3)2 300 <5(—12) FA 110 CDsO- + CH3CH2F -» 1.3 ( —10) ICR 111 + CH3CHF2 1.26 (—9) ICR 111 + ch2fchf2 -> 1.68 (—9) ICR 111 + CH3CF3 -> 1.55 ( —10) ICR 111 + CHF2CHF2 -> 1.69 ( —9) ICR 111 + ch2fcf3

CO bo Ti—* 0 ICR 111 + chf2cf3 -» 1.9(=—9) ICR 111 + (CH3 ) 3 B -> 3.85±0.77(—10) ICR 18 ch2no2- + CHCls 300 <5(—12) FA 110 + n GHoSH 300 >1.6 (

10) FA 110 + CsH9 -> 300 <1(—11) FA 110 CHF- + CH3F 297 >4.1 (—10) FA 105 cf3- + N02 3.7 (-10) B 0.3 eV KE 112 + Xe -> 3 ( —12) B 0.3 eV KE 113 ch3s- + ch3f -> 297 <1 (—12) FA 105 + CH3C1 -» 297 l.lztO.l ( —10) FA 105 7.8±1.2(—11) ICR 114

4- CH3Br 1.4±0.2(—10) ICR 114 chci2- + CHsCl + 297 5.1±0.4(—10) FA 105 + GH2 -> 300 —3(—11) FA 110

+ CHsCN -» 300 >2(—10) FA 110 + C2H5 0H 300 <1(-11) FA 110 + CH3SOCH3 -* 300 >1(—11) FA 110 ca3- + ch3no2 -» 300 >1 (—10) FA 110 + CHsCN -> 300 <5 ( —12) FA 110 + CH3COCH3 -» 300 <1 (—12) FA 110 + CsHe 300 ~2(—11) FA 110 c2h2n- + CHCls -> 300 >1(—10) FA ch2cn- 110 + CH3SOCH3 300 <1(—11) FA CHsCN" 110 + CH3COCH3 -> 300 >1 (—10) FA CHsCN- 110 c2h6n- + C2H2 —

297 1.04±0.26(—9) FA (CHshN- 106 297 1.18±0.30(—9) FA c2h5nh- 106 c2h7 n- + H20 2.4 (-9) FA C2Hs NH2- 115 CsHsO" + CHsOH 300 >5(—11) FA no

+ CH2C12 -» 300 >5(—11) FA 110 c2H5o- + C2H2 297 1.41+0.35 (-9) FA 106 300 1.1 (-9) FA 108 + (CHs)sB 4.6±0.9(—10) ICR 18 + i-CsH7 OH -» 300 >5(—11) FA 110 + t-C4H9OH 300 >5(—11) FA no

+ GH5CH3 300 <5 ( —11) FA no

+ C6H5CH(CH3 ) 2 -» 300 <1(-11) FA 110

17
Table 2. Rate coefficients* for reactions of organic cations—Continued

Reaction T k Method Comments Ref. CaHaFr 4- CHsCHFa 1.5±0.4(— 10) ICR CHF2CH0- Ill CaHaFr + CHFaCHaF -> 1.5±0.2(—10) ICR CHFaCHF" 111 + CHsCFs - 7.9±0.9( —10) ICR CFaCHa- 111 CaHFr 4- CHF2CHFa - 1.07±0.10(—9) ICR CHF2CF2' 111 4- CH2FCF3 -> 1.5±0.3( —10) ICR CFaCFH- 111 GFr 4- NOa 3.2 (-10) B 0.3 eV KE 112 + Xe -> 8( —12) B 0.3 eV KE 113 CaHsOS- + CHaCla 300 >2(—10) FA CHaSOCHa" 110

4- GHa 300 <1(-11) FA CH3SOCH2- 110

4- CHsCN 300 >2(—10) FA CHaSOCHa- 110

4- GH5CH3 -> 300 <1 (—12) FA CHaSOCHa- 110 C3H5O" + CHCls 300 >2 (—10) FA CH3COCH2- 110

4- CHsCN 300 <3(—11) FA CH3COCH2- 110

+ CD3COCD3 3.2±1.9(—12) ICR CH3COCH2- 116 + ( C2H5) 2CO 8±4(—12) ICR CHaCOCHa- 116 + CH3COCDCODCH3 -> 3.6±0.3(— 10) ICR CH3COCH2- 116 GIXO 4- CH3COGH5 6.4±4.0(—12) ICR CDaCOCDa- 116 gh7 o- + GHa -

>

297 >8.9±2.3(—10) FA (CHa)aCHCr 106

300 5.2 (-10) FA i-CaH7 0

- 108 + GHsOH h> 300 >5(—11) FA i-C3 H7 0

- 110 + *-GH9 OH 300 >5(—11) FA i-CaH7 0

- 110 GHeDO- + CH3COCD2CH3 -» 1.8±1.5(—12) ICR CHaCOCDCHa- 116 GHsDaO" + CHaCOCDaCHs -> 2.7±2.2(—12) ICR CH2COCD2CH3- 116 gh9 o- + CH30H - 300 >5(—11) FA f-CiHoO" 110 + CHaCla -> 300 >1(-10) FA f-GH0 C>- 110

+ C2H2 300 1.6 ( —10) FA t-C^HsO 108 + GHsOH 300 >5(—11) FA t-CiHoO" 110

+ i-GH-OH 300 >5(—11) FA f-CHnO" 110 gf8- + NOa 1.0(-10) B 0.3 eV KE 117 + SFs 300 <1(—10) FA 118 gh9 s- + CH3NO2 -> 300 <2.6 (—11) FA n-CiHoS" 110 gh9o- + CH3 CD2COCD2 CH3 3.8±3.0(— 12) ICR CH3CH2C0CHCH3- 116 C5 H-Oa- + CeHsSH 3.0±0.3(—10) ICR From CH3COCHCOHCH3 116

4- parachlorophenol -> 1.5±0.4(—10) ICR From CH3COCHCOHCH3 116 G-HsDOa" + CD3COCDCODCD3 -» 1.2±0.3(—11) ICR CH3COCDCOCH3- 116 C5H5D2O2 + CH3 COCDCODCH3 3.0±0.5(— 11) ICR CHaC0CDC0DCH3- 116 GHsO- + parahydroxytoluene -* 6.2±2.0(— 11) ICR Phenoxy anion 116 CeHaNOa" + NOa -> 3.6(— 10) B 0.3 eV KE 117 GFr 4- NOa 2.0 (—10) B 0.3 eV KE 117 GF10 + NOa -* 1.3( —11) B 0.3 eV KE 117 CtH7 0- 4- phenol -> 1.8±0.3(— 10) ICR From parahydroxytoluene 116 c7f8- 4- NOa -*> 7.0 (

11 ) B 0.3 eV KE 117

‘Rate coefficients are in units of cm8 molecule 1 s'

1 for bimolecular reactions and cm8 molecule 2 s'

1 for termolecular reactions. The numbers in parenthesis should be read as the power 10 of the number. This (—9) is 10'9

.

18
Acknowledgements

The author would like to express his sincere gratitude to Dr. Sharon Lias for her assistance in the

literature search and indexing, to Dr. Pierre Ausloos

for his valuable critique and encouragement, and to Ms. Jeanne Miller, of Yale University, for her help

in structuring the tabular material. This work was

supported by the Office of Standard Reference Data,

National Bureau of Standards.

References

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5, 1123 (1976).

[2] Meisels, G. G., ‘Determination of Rate Coefficients of Ion-Molecule Reactions,” in NATO Advanced Study

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2752 (1970).

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S. L., J. Am. Chem. Soc. 94, 2798 (1972).

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[47] Heckel, E., and Hanrahan, F. J., J. Chem. Phys. 62,

1027 (1975).

[48] Mayer, T. M., and Lampe, F. W., J. Phys. Chem. 78, 2424 (1974).

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Ion Phys. 13, 261 (1974).

[50] Potzinger, P., and Lampe, F. W., J. Phys. Chem. 75, 13

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[51] Murphy, M. K., and Beauchamp, J. L., J. Am. Chem.

Soc. 98, 5781 (1976).

[52] Staley, R. H., and Beauchamp, J. L., J. Am. Chem. Soc. 96, 6252 (1974).

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(1974).

[54] Ruska, W. E. W., and Franklin, J. L., Int. J. Mass Spectrom. Ion Phys. 3, 221 (1969).

[55] Nagy, G. P., Thynne, J. C. J., and Harrison, A. G., Can.

J. Chem. 46, 3609 (1968).

19
[56] Solka, B. H., and Harrison, A. G., Int. J. Mass Spectrom.

Ion Phys. 14, 295 (1974).

[57] Brupbacher, J. M., Eagle, C. J., Koprio, J. A., and

Tschuikow-Roux, E., J. Phys. Chem. 81, 1125 (1977).

[58] Solka, B. H., and Harrison, A. G., Int. J. Mass Spectrom. Ion Phys. 17, 379 (1975).

[59] McAskill, N. A., Aust J. Chem. 22, 2275 (1969).

[60] Yergey, A. J., and Franklin, J. L., Int. J. Mass Spectrom.

Ion Phys. 9, 354 (1972).

[61] Sieck, L. W., and Gorden, R., Int. J. Chem. Kinet. 5, 445 (1973).

[62] Sieck, L. W., J. Res. Nat. Bur. Stand. 81A. 267 (1977).

[63] Bach, R. D., Weibel, A. T., Patane, J., and Kevan, L., J. Am. Chem. Soc. 98, 6237 (1976).

[64] Franklin, J. L., Wada, Y., Natalis, P., and Hierl, P. M.,

J. Phys. Chem. 70, 2353 (1966).

[65] Shannon, T. W., and Harrison, A. G., J. Chem. Phys.

43, 4206 (1965).

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Chem. Soc. 99, 32 (1977).

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(1977).

[68] Sieck, L W., and Ausloos, P., Rad. Res. 52, 47 (1972).

[69] MacNeil, K. A. G., and Futrell, J. H., J. Phys. Chem.

76, 409 (1972).

[70] Chatfield, D. A., and Bursey, M. M., Int. J. Mass Spectrom. Ion Phys. 18, 239 (1975).

[71] Chatfield, D. A., and Bursey, M. M., J. Am. Chem. Soc. 98, 6492 (1976).

[72] Chatfield, D. A., and Bursey, M. M., J. Am. Chem. Soc. 97, 3600 (1975).

[73] Corderman, R. R., LeBreton, P. R., Buttrill, S. E., Williamson, A. D., and Beauchamp, J. L., J. Chem. Phys.

65, 4929 (1976).

[74] Sieck, L. W., Abramson, F. P., and Futrell, J. H., J. Chem. Phys. 45, 2859 (1966).

[75] Gorden, R., and Sieck, L. W., J. Res. Nat. Bur. Stand. 76A, 655 (1972).

[76] Beauchamp, J. L., and Dunbar, R. C., J. Am. Chem. Soc. 92, 1477 (1970).

[77] Ryan, K. R., and Futrell, J. H., J. Chem. Phys. 42, 824

(1965).

[78] Tan, H. S., Pabst, M. J. K., and Franklin, J. L., Int. J. Mass Spectrom. Ion Phys. 19, 163 (1976).

[79] Herman, J. A., and Harrison, A. G., Can. J. Chem. 47,

957 (1969).

[80] Ferrer-Correia, A. J., and Jennings, K. R., Int. J. Mass

Spectrom. Ion Phys. 11, 111 (1973).

[81] Anicich, V. G., and Bowers, M. T., Int. J. Mass Spectrom. Ion Phys. 13, 359 (1974).

[82] Williamson, A. D., and Beauchamp, J. L., J. Chem. Phys.

65, 3196 (1976).

[83] Sieck, L. W., Gorden, R., Lias, S. G., and Ausloos, P., Int J. Mass Spectrom. Ion Phys. 15, 181 (1974).

[84] Anicich, V. G., and Bowers, M. T., Int. J. Mass Spectrom. Ion Phys. 12, 231 (1973).

[85] Anicich, V. G., and Bowers, M. T., Int. J. Mass Spectrom. Ion Phys. 11, 329 (1973).

[86] McAskill, N. A., and Harrison, A. G., Int. J. Mass Spectrom. Ion Phys. 5, 193 (1970).

[87] Beauchamp, J. L., and Park, J. Y., J. Phys. Chem. 80,

575 (1976).

[88] Anicich, V. G., and Bowers, M. T., Int. J. Mass Spectrom. Ion Phys. 13, 351 (1974).

[89] O’Malley, R. M., Jennings, K. R., Bowers, M. T., and

Anicich, V. G., Int. J. Mass Spectrom. Ion Phys. 11, 89 (1973).

[90] Anicich, V. G., Bowers, M. T., O’Malley, R. M., and

Jennings, K. R., Int. J. Mass Spectrom. Ion Phys. 11,

99 (1973).

[91] Herman, J. A., Myher, J. J., and Harrison, A. G., Can.

J. Chem. 47, 647 (1969).

[92] Davidson, W. R., Bowers, M. T., Su, T., and Aue, D. H.

Int. J. Mass Spectrom. Ion Phys. 24, 83 (1977).

[93] DeStefano, A. J., and Porter, R. F., J. Phys. Chem. 80,

2918 (1976).

[94] Beauchamp, J. L., Caserio, M. C., and McMahon, T. B.,

J. Am. Chem. Soc. 96, 6243 (1974).

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4831 (1977).

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J. Mass Spectrom. Ion Phys. 13, 195 (1974).

[98] Chatfield, D. A., and Bursey, M. M., Int. J. Mass Spectrom. Ion Phys. 20, 101 (1976).

[99] Schildcrout, S. M., J. Am. Chem. Soc. 95, 3846 (1973).

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[101] Corderman, R. R., and Beauchamp, J. L., J. Am. Chem.

Soc. 98, 5700 (1976).

[102] Sieck, L. W., and Gorden, R., Int. J. Mass Spectrom.

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20

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Rate Coefficients for Ion-Molecule Reactions,

Organic Ions Other Than Those Containing Only C and H

5. Publication Date February 1979

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Chemical kinetics; data evaluation; gas phase ion-molecule reactions;

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