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NSRDS-NBS 70

U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards
NATIONAL BUREAU OF STANDARDS

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Rate Constants for Reactions

of Aliphatic Carbon-Centered Radicals

in Aqueous Solution

NBS

RESEARCH

INFORMATION CENTER QC\CO

•U51 3

#70

mz

Alberta B. Ross and Pedatsur Neta

Radiation Chemistry Data Center

Radiation Laboratory

University of Notre Dame

Notre Dame, IN 46556

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

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued October 1982
Library of Congress Cataloging in Publication Data

Ross, Alberta B. Rate constants for reactions of aliphatic carbon-centered radicals in aqueous solution. (NSRDS-NBS ; 70) “Issued October 1982.”

1. Chemcial reaction, Rate of—Tables. 2. Radicals (Chemistry)

Tables. I. Neta, Pedatsur. II. Title. III. Series. QC100.U573 no. 70 [QD502] 602M8s 82-2096

[547. 1 ’394] AACR2

NSRDS-NBS 70

Natl. Stand. Ref. Data Ser., Natl. Bur. Stand. (U.S.), 70, 103 pages (Oct. 1982) CODEN: NSRDAP

© 1982 by the Secretary of Commerce on Behalf of the United States Government

U S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1982

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, DC 20402

Price $5.50

(Add 25 percent for other than U.S. mailing).
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

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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

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

Ernest Ambler, Director

iii
Preface

This report is one of a series of data publications on radiation chemistry; the aim of the series

is to compile, evaluate, and present the numerical results on processes occurring in systems which

have been subjected to ionizing radiation. Various kinds of data are important in radiation chemistry. The quantities which were measured first were the observed radiation yields or G values (molecules formed or destroyed per 100 eV). Various indirect methods based on G values have been used to determine yields of transient species and relative rates of reactions. The spectral properties (optical, electron spin resonance) of transients have provided a direct method for their identification, and rates of the very fast reactions of transients which occur in irradiated systems have been measured directly

by spectroscopic methods. Conductivity and luminescence methods have also provided a means of measuring properties of transients and their kinetics. Some reactions which occur in irradiated systems

have also been studied by other methods, such as photochemistry, electric discharge, ultrasonics, chemical initiation, electron impact, etc. The emphasis in these publications is on the data of radiation

chemistry, but where other pertinent data exist, they are included.

The data of radiation chemistry are voluminous; thousands of systems have been investigated.

As a result there are certain collections, e.g. rate constants of particular types of reactions or certain properties of transients, for which tabulations of the data are considered essential, but for which

critical assessment of each value is impossible. On the other hand, certain systems and properties

have been studied so extensively that critical examination of these data is desirable and timely.

Authors of this series of data publications have been asked to evaluate the extent to which the data can be critically assessed, to describe their criteria for evaluation, and to designate preferred values whenever possible.

IV
Contents

Page

Introduction 1 List of Abbreviations and Symbols 3

List of Aliphatic Radicals 4

Table 1. Rate Constants for Reactions of Aliphatic Radicals with Inorganic Solutes

in Aqueous Solution 7

Table 2. Rate Constants for Reactions of Aliphatic Radicals with Organic Solutes

in Aqueous Solution 33

Table 3. Rate Constants for Acid- and Base-catalyzed Proton Transfer Reactions of

Aliphatic Radicals in Aqueous Solution 73

Table 4. Rate Constants for Second Order Decay of Selected Aliphatic Radicals

in Aqueous Solution 77

Index to Radical Reactions 80

Radical Formula Index 83

Substrate Formula Index 85

References 89

v
e.g. the OH radical abstracts hydrogen from alcohols mostly

from the alpha position and to some extent from other sites. As a result the system contains a mixture of the reducing

a-hydroxyalkyl radicals and the much less feactive /3-hydroxy-and y-hydroxy-, etc. or alkoxyl radicals, b. Both

OH and H may react with the substrate but yield different

radicals, e.g. OH and H adducts, c. The radical produced by

the initial attack may undergo certain processes before

reacting with the substrate, e.g. protonation on carbon, acidbase equilibria, water elimination. Under certain conditions more than one form of the radical may react with the

substrate, d. The aliphatic radical may react with the substrate by more than one mechanism, e.g. electron transfer and

addition, of which only one is spectrophotometrically

monitored, e. The aliphatic radical may react with the

substrate slowly and undergo radical-radical decay as a competing process.

In many of the above cases, the reaction observed

constitutes the main process (>90%) so that the rate constant measured can be taken to represent that reaction. However,

when the observation is made on a less dominant process, the experimental rate constant may not represent the real value for that reaction. In these cases, the experimental values are reported in the tables and marked “uncorrected”. The

corrected value can sometimes be derived after considering the unobserved reactions.

Arrangement of the Tables

A numbered list of the radicals for which reaction rate data have been compiled precedes the tables. Numbers have

been assigned to the radicals for use in numbering the

reactions in subsequent tables, to identify the radical and to provide a means of generating an index. A name and line formula are listed for most of the radicals. Line formulae for radicals containing rings are written with dashes at the left and right to indicate the cycle, as -0CHCH2 0(CH2 ) 2- for the radical from dioxane (2,5-dioxacyclohexyl, 104). When

more than one radical species may be involved the radicals are

identified only by their origin, as “Radicals from glucose +

OH”.

Tables 1-3 contain the rate data for the reactions of the

radicals with various substrates. Inorganic ions and molecules

are grouped in table 1, in alphabetic order by the symbol for the main element. Organic substrates are listed alphabetically

by name in table 2. Table 3 contains proton transfer reactions of radicals with acids, bases and buffer components. Entries

for each substrate are numbered, and each reaction has an

entry number including both the number of the substrate and

the radical number. For example, the reaction of oxygen with

methyl radical is 93.001, while oxygen with carboxymethyl

radical is 93.035. Reactions of substrates with radicals in more than one acid-base form are listed in the tables under

the same entry number.

Table 4 contains a few representative radical-radical

reactions whose rates have been determined in most cases by

measuring the second-order decay rate of the optical

absorption {2k/ e). The molar absorptivity, €, used to calculate the rate constant k is given in the Comments column.

Products are listed only for those reactions for which

evidence has been obtained on the nature of the products. The

error limits given are those reported in the original papers; lacking such a statement the uncertainty in the rate constant should be assumed to be ± 25%. Many of the second order

rate constants are derived from pseudo-first order rates for the decay of the transient radical or the substrate or the build-up

of a product. Rate constants for certain reactions have been

used as reference values to determine values for other

reactions, which are labeled “rel.”; in those cases the reference values are listed in the Comments column. The label “uncor.”

is used for observed values of k measured in systems in which more than one process is occurring.

Temperature is assumed to be ambient unless otherwise

specified. The Method column indicates the method for generation of the transient and in the Comments column the method of measurement is indicated along with the source of the transient and other information such as activation energy, pK, etc. When the symbol R is used in a Comment, such as in £(R) or A;(R + R), it refers to the radical of the same entry. References are indicated by the serial number from the Radiation Chemistry Data Center bibliographic data base, from

which the reference list was generated. The first two digits of the serial number represent the year in which the work was

published.

Indexes have been produced from tables 1-3 for reactions of (1) the radicals in order of their number and for (2) the

radicals and substrates by molecular formula. The indexes

follow the tables.

Acknowledgments

The assistance of Dr. W. Phillip Helman in providing

programs for indexing and text processing is gratefully

acknowledged. We also wish to thank Dr. Norman Lichtin and

Dr. Guillermo Ferraudi for their useful comments on tables 3

and 1, respectively.

The Radiation Laboratory is operated under Contract DEAC02-76ER00038 with the Department of Energy. The

Radiation Chemistry Data Center is supported jointly by the

Office of Standard Reference Data of the National Bureau of Standards and of the Office of Basic Energy Sciences and the

Office of Health and Environmental Research of the Department of Energy. This is Radiation Laboratory Document

No. NDRL-2196.

2
List of Abbreviations and Symbols

A frequency factor G radiation yield (molecules per 100 eV)

Ac acetyl g!y glycine or glycinato

ala alanine AH\ activation enthalpy

abs. absorption I ionic strength

abstr. abstraction irradn. irradiation addn. addition K equilibrium constant

alk. alkaline k rate constant bpy 2,2'-bipyridine k( specific rate of the forward reaction BuOH butanol K specific rate of the reverse reaction

calcd. calculated L ligand

chem. chemical Me methyl

c.k. competition kinetics meas. measured

concn. concentration MeOH methanol

condy. conductivity NaLS sodium dodecylsulfate

contg. containing obs. observed

cor. corrected o.d. optical density

CTAB hexadecyltrimethylammonium bromide p.b.k. product buildup kinetics

detd. determined phot. photolysis

dien diethylenetriamine P^a negative logarithm of the acid dissociation

d.k. decay kinetics (decay of radical absorption constant, e.g., where AH -f H2 0 A" + H30

and bleaching of substrate absorption) PNAP />-nitroacetophenone

e-r. electron radiolysis PNBPA />-nitrobenzoato(pentaammine)cobalt(III) ion

€ extinction coefficient (molar absorptivity) p.r. pulse radiolysis activation energy PrOH propanol en ethylenediamine R radical esr electron spin resonance redn. reduction

estd. estimated rel. relative EtOH ethanol RNO A^7V-dimethyl-/>-nitrosoaniline Et2 0 ethyl ether AS\ activation entropy

f.p. flash photolysis satd. saturated formn. formation soln. solution y-r. gamma radiolysis

3
List of Aliphatic Radicals

Reactions of the following radicals are included in these

tables; comments within the tables identify the compounds

from which the radicals were derived. Only one acid-base

form is listed below but different forms may be used in the

tables, depending on pH. The entry numbers for the reactions

in the tables include the three-digit numbers listed below

following the decimal point. Thus, the first reaction in the

tables is numbered 1.016 and involves the radical from tertbutanol, •CH2 C(CH3)2 OH, which is 016 in the following list. The numbers have been used to create an index to reactions of the various radicals; the index follows the tables. Radicals

herein are restricted to carbon radicals and have been ordered

from the most hydrogen substitution on carbon to the most

oxygen substitution. That is, radicals -CXYZ are ordered as X,

Y, and Z progressively represent H, C, halogens, N, and 0.

001 Methyl •ch3 002 Ethyl •ch2 ch3 002a 1-Methylethyl (CH3) 2 CH

002b 1 , 1 -Dimethylethyl (CH3) 3 C

003 Radicals from pentane •C5 Hu 004 Cyclopentyl c-C5 H9 005 2-Chloroethyl •ch2 ch2 ci 006 2-Carboxy-2,2-dimethylethyl •CH2 C(CH3)2 C02 H

007 Radicals from oleate + OH R

008 Radicals from linoleate + OH R

009 Radicals from linolenate + OH R

010 Radicals from arachidonate -T OH R

Oil 2-Aminoethyl •CH2 CH2NH2 012 2-Amino-2,2-dimethylethyl •CH2 C(CH3) 2 NH2 013 2-Amino-2-carboxy-2-methylethyl •CH2 C(CH3 )(NH2 )C02 H

014 2-Hydroxyethyl •ch2 ch2 oh

015 2-Hydroxypropyl •ch2 chohch3 016 2-Hydroxy-2,2-dimethylethyl •CH2 C(CH3) 2 OH

016a Radicals from cyclopentene + OH R

017 2-Carboxy-2-hydroxy-2-methylethyl •CH2 C(CH3)(0H)C02 H

018 Radicals from allyl alcohol + OH R

019 Radicals from crotyl alcohol + OH R

020 Formylmethyl •ch2 cho

021 1-Formylethyl ch3 chcho

022 2-Hydroxyethenyl •CH = CHOH

023 2-Oxopropyl •CH2 COCH3 024 1-Acetylethyl ch3 cochch3 025 2-Oxocyclohexyl -(CH2 ) 4CHCO026 l-Formyl-2-hydroxyethyl hoch2 chcho

027 4-Hydroxy-2-oxobutyl hoch2 ch2 coch2 028 l-Formyl-4-hydroxybutyl HOCH2 (CH2 ) 2 CHCHO

029 l-Formyl-5-hydroxypentyl HOCH2 (CH2 ) 3 CHCHO

030 Radicals from meso-erythritol R

031 Radicals from xylitol R

032 2-Oxo-3,4,5-trihydroxycyclohexyl -(CHOH)3 CH2 CHCO033 Radicals from sorbitol R

034 Carbamoylmethyl •CH2 CONH2 035 Carboxymethyl •ch2 co2 h

036 Methoxycarbonylmethyl •ch2 co2 ch3 037 1-Carboxyethyl ch3 chco2 h

038 1 -Carboxypropyl ch3 ch2 chco2 h

039 1 -Carboxy-2-hydroxyethyl hoch2 chco2 h

040 l-Carboxy-2-hydroxypropyl ch3 chohchco2 h

040a 1,2-Dicarboxyethyl ho2 cchch2 co2 h

041 l,2-Dicarboxy-2-hydroxyethyl ho2 cchohchco2 h

4
042 Dicarboxymethyl •CH(C02 H)2 043 Chloromethyl •ch2 ci 044 Difluoromethyl •chf2 045 Dichloromethyl •chci2 046 Dichlorofluoromethyl •cfci2 047 Trifluoromethyl •cf3 048 Trichloromethyl •CC13 049 1-Aminoethyl ch3 chnh2 050 1-Amino-l-methylethyl (CH3) 2 CNH2 051 l-(7V,7V-Diethylamino)ethyl CH3 CHN(C2 H5) 2 052 Triethylammonioethyl CH3 CHN+

(C2 H5)3 053 (TV-Acetylamino)methyl ch3 conhch2 054 (N-Formyl-./V-methylamino)methyl HCON(CH3 )CH2 055 (TV-Acetyl-A-methylamino)methyl CH3 CON(CH3)CH2 056 Amino(carboxy)methyl nh2 chco2 h

057 Amino(carbamoyl)methyl nh2 chconh2 058 Radicals from glycylglycinamide OH R

059 Carboxy(./V-methylamino)methyl ch3 nhchco2 h

060 A-Acetylamino(carboxy)methyl ch3 conhchco2 h

061 7V-Acetyl-7V-methylamino(carboxy)methyl CH3 C0N(CH3)CHC02 H

062 Radical from glycine anhydride + OH R

063 Radical from alanine anhydride + OH R

064 Radical from sarcosine anhydride -f OH R

065 Radicals from diglycine OH R

066 Radicals from glycylsarcosine + OH R

067 Radicals from acetyldiglycine + OH R

068 Radicals from triglycine + OH R

069 Radicals from acetyltriglycine + OH R

070 Radicals from acetyltrialanine + OH R

071 Radicals from acetyltrisarcosine + OH R

072 Radicals from acetylserineamide + OH R

073 Radicals from acetylasparagine + OH R

074 Radical from 2-pyrrolidone-5-carboxylic acid R

075 Hydroxymethyl •CH2OH

076 1-Hydroxyethyl ch3 choh

077 1 -Hydroxypropyl ch3 ch2 choh

078 1-Hydroxy-l-methylethyl (CH3)2 COH

079 1-Hydroxybutyl CH3 (CH2)2 CHOH

080 1 -Hydroxy- 1 -methylpropy1 ch3ch2 cohch3 081 l-Hydroxy-2-methylpropyl (CH3) 2 CHCHOH

082 1 -Hydroxypentyl CH3 (CH2)3tHOH

083 (Cyclohexyl)hydroxymethyl c-C6HnCHOH

084 1 -Hydroxycyclobutyl -CH2 COH(CH2)2- 085 1 -Hydroxycyclopentyl -CH2COH(CH2) 3- 086 1 -Hydroxycyclohexy1 -CH2 COH(CH2)4- 087 1-Hydroxycycloheptyl -CH2 COH(CH2)5- 088 1-Hydroxycyclooctyl -CH2COH(CH2) 6- 089 2,2,2-Trifluoro-l-hydroxyethyl •chohcf3 090 Acetoxymethyl CH3 C02 tH2 091 1-Sulfatoethyl CH3 CH0S03

- 092 Radicals from sodium dodecylsulfate R

092a Methoxymethyl •CH2 OCH3 093 1-Ethoxyethyl CH3 CHOC2 Hs 093a 1,1-Dimethylethoxymethyl •CH2 OC(CH3 )3 094 2-Tetrahydrofuryl -OCH(CH2)3- 094a (Methoxymethoxy)methyl •ch2 och2 och3 095 1,4-Dihydroxybutyl •chohch2 ch2 ch2 oh

096 l,3-Dihydroxy-2,2-di(hydroxymethyl)propyl •CHOHC(CH2 OH)3
097

098

099

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

141

142

143

144

146

147

148

2-Carboxy- 1-hydroxy- 1 -methylethyl

2-Amino-l-hydroxyethyl

2-Amino-l-phosphoryloxyethyl

2-Amino-2-carboxy-l-hydroxyethyl

1

.2-

Dihydroxyethyl

1.2-

Dihydroxypropyl

1

.2-

Dihydroxy- 1-methylpropyl

2.5-

Dioxacyclohexyl

Radicals from polyethyleneglycol

1,2,3-Trihydroxypropyl

1 -Hydroxy- 1 -methy1-2-oxopropyl

Radicals from deoxyribose + OH

Radicals from ribose + OH

Radicals from ribose phosphate + OH

Radicals from glucose + OH

Radicals from sucrose + OH

Radical from ascorbate -f OH

(Carbamoyl)hydroxymethyl

(Carboxy)hydroxymethyl

1 -Carbamoyl- 1 -hydroxyethyl

1 -Carboxy-1 -hydroxyethyl

l-Hydroxy-l-(methoxycarbonyl)ethyl

(Dicarboxy)hydroxymethyl

1.2-

Dicarboxy-l-hydroxyethyl

1.2-

Dicarboxy-l,2-dihydroxyethyl

1.3-

Dicarboxy-l-hydroxypropyl

Dihydroxymethyl

Dimethoxymethyl

2.5-

Dioxacyclopentyl

2,2,2-Trichloro- 1 , 1-dihydroxyethyl

Carbamoyl

Electron adduct of acrylamide

Electron adduct of crotonamide

Electron adduct of methacrylamide

Electron adduct of /3,/3-dimethylacrylamide

Electron adduct of AyV-dimethylacrylamide

Electron adduct of Diamide

Electron adduct of acrylate Electron adduct of crotonate Electron adduct of methacrylate

Electron adduct of /3,/3-dimethylacrylate Electron adduct of methyl methacrylate

Electron adduct of sorbate Electron adduct of dimethyl fumarate

Electron adduct of glycine anhydride

Electron adduct of alanine anhydride

Electron adduct of sarcosine anhydride

Electron adduct of acetylglycylglycinamide

Carboxyl

Electron adduct of methyl acetate

CH3 C0HCH2 C02H

NH2 CH2 CHOH

nh2 ch2chopo2 oh

•CH0HCH(NH2)C02 H

•chohch2 oh

•CHOHCHOHCHg

CH3COHCHOHCH3

-0CHCH20(CH2) 2- -OCHCH2 (OCH2 CH2)-

•chohchohch2 oh

( + CH2OHCOHCH2 OH)

CH3 C0C(0-)CH3 R

R

R

R

R

•A- •chohconh2 •chohco2 h

ch3 cohconh2 ch3 cohco2 h

ch3 cohco2 ch3 ho2 ccohco2 h

ho2 ccohch2 co2 h

ho2 ccohchohco2 h

H02 CC0H(CH2)2 C02 H

•CH(OH)2 •CH(OCH3)2 -OCHO(CH2)2 -

CC13 C(0H)2 •conh2 [CH2 CHCONH2].- [CH3 CHCHCONH2]-- [CH2 C(CH3)CONH2

]-- [(CH3 ) 2 CCHCONH2

].- [CH2 CHCON(CH3)2].- R

[CH2CHC02 HK

[CH3 CHCHC02 H]--

[CH2C(CH3)C02H]*-

[(CH3)2 CCHC02 H]-'

[CH2 C(CH3)C02 CH3K

[CH3CHCHCHCHC02H].-

R

R

R

R

R

•C027-C02 H

CH3 C(0-)0CH3

6
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution

No. Reaction k (L mol"'s'

1 ) pH Method Comment Ref.

Ag

1. Silver(I) ion

1.016 •CH2 C(CH3) 2OH + Ag + Ag° nat p.r. No electron transfer to give Ag° in 0.1 mol Lf

1 tert-BuOH. 78A410

1.075 •CH2 OH + Ag + Ag° nat p.r. No electron transfer to give Ag° in 0.1 mol L'

1 MeOH.

78A410

1.078 (CH3)2COH + Ag+ — Ag° nat p.r. No electron transfer to give Ag° in 0.1 mol L"

1 2-PrOH. 78A410

1.128 [CH2CHCONH2

]-- + Ag + — Ag° + H

+ + CH2 =CHCONH2

(1.1 ± 0.4) x 108 ~6 p.r. P.b.k. at 313 nm in soln. contg. acrylamide. 70G052

1.147

2.

•C02

* + Ag + —>• AgC02 (+ Ag+

) — Ag2C02 +

Silver(I) ion, complex with Ag(0)

nat p.r. Ag+ was reduced in 10'2 mol L'

1 formate soln. contg. C02 by a complex mechanism.

78A410

2.016 •CH2C(CH3 )2 OH + Ag2 +

2 Ag + + OH' + CH2 = C(CH3)2

2.0 x 109 nat p.r. Calcd. from best fit for increase

in condy. as function of time in 0.1 mol L"

1 tert-BuOH-5 x 10"4 mol L'

1 AgC104 soln.

78A410

2.075 •CH2 OH + Ag2 + Ag2 CH2OH+ —* CH2 0 + H

+ + Ag2

5.0 x 109 nat p.r. Calcd. from increase in condy. as function of time in 0.1 mol L"

1 MeOH5 x 10

-4 mol L"

1 AgC104 soln. assuming

values for k(R + R), [Ag2 +

], [R], and [H2 02].

78A410

2.076 CH3CHOH + Ag2 + —

CH3 CHO + H

+ + Ag2

1.0 x 109

p.r. Calcd. from increase in condy. as function of time in Et0H-AgC104 soln. assuming values for &(R + R), [Ag2 +

], [R], and [H202 ].

78A410

2.078 (CH3)2£OH + Ag2 + —

(CH3 )2 CO + H

+ + Ag2

2.5 x 109 p.r. Calcd. from increase in condy. as function of time in 0.1 mol LT

1 78A410

2-PrOH-5 x 10-4 mol L'

1 AgC104 soln. assuming values for £(R + R), [Ag2 +

], [R], and [H2 02],

Br

3.3.076 Bromate ion CH3tHOH + Br03

- <5 x 106 6 p.r. D.k.; radical from ethanol. 72A018 CHjCHO' + Br03

- (3.0 ± 0.5) x 107 11.8

4.4.016

Cd

Cadmium(I) ions •CH2 C(CH3) 2 OH + Cd + ~1 x 109 nat p.r. Calcd. from opt. and condy. 75A064

Cd2+ + (CH3)2 C=CH2 + OH-

•CH2C(CH3) 2 OH + Cd22+ — OH- + ~1 x 109 nat p.r.

studies in <er/-BuOH-Cd2+soln. assuming values for competing

reactions. See above. 75A064

4.075 Cd + + (CH3)2C = CH2 + Cd2+ •CH2 OH + Cd + — CdCH2OH+

2 x 108 nat p.r. D.k. at 300 nm (Cd +

) in soln. 75A064

contg. MeOH and Cd2 +

, as well as condy. and p.b.k. at 240 nm

(Cd2 2+

); assumed k(Cd + + H2 02) =

1.5 x 109

, k( R + R) = 1.2 x 109

.
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mop's'

1 ) PH Method Comment Ref.

4.076 CH3tHOH + Cd + — CdCHOHCH3 +

(1.3 ± 0.6) x 109 nat p.r. D.k. at 300 nm (Cd +

) in soln. contg. EtOH and Cd2+

, as well

as condy. and p.b.k. at 240 nm

(Cd2 2+

); assumed £(Cd + + H2 02) =

1.5 x 109

, k( R + R) = 1.15 x 109 and 2/t(Cd + + Cd +

) = 3.0 x 109

.

75A064

4.078 (CH3 ) 2COH + Cd +

(2.4 ± 1.2) x 109 nat p.r. D.k. at 300 nm (Cd +

) in soln. 75A064

CdC(CH3) 2 OH+

contg. 2-PrOH and Cd2 +

, as well

as condy. and p.b.k. at 240 nm

(Cd2 2+

); assumed &(Cd + + H2 02) =

1.5 x 109

, t(R + R) = 7x 108 and 2£(Cd + + Cd +

) = 3.0 x 109

. 4.105 -0CHCH2(0CH2 CH20)n - + Cd + <2 x 108 nat p.r. D.k. of Cd +

in the presence of polyethylene glycol entirely by Cd + + Cd +

(2k = 5 x 109

); 2A(R + R) = 2.2 x 107

.

75A153

5. Cadmium(II) ion

5.016 •CH2C(CH3)2OH + Cd2+ <106 nat p.r. Est. from lack of increase in Cd +

in 0.1 mol L"

1 Cd2+

soln. upon

addn. of 0.1 mol L~* iert-BuOH.

75A027

<2.5 x 105 nat p.r. No reaction. 75A153

5.075 •CH2OH + Cd2+ <102 nat p.r. Est. from lack of increase in Cd +

in 0.1 mol L”

1 Cd2+

soln. upon

addn. of 0.1 mol L'

1 MeOH.

75A027

5.076 CH3tHOH + Cd2+ <2.5 x 10s nat p.r. No reaction. 75A153

5.078 (CH3) 2COH + Cd2+ <106 p.r. Est. from lack of increase in Cd +

in 0.1 mol L'

1 Cd2+

soln. upon

addn. of 0.1 mol L~' 2-PrOH.

75A027

<2.5 x 105 nat p.r. No reaction 75A153

5.101 •CHOHCH2OH -f Cd2+ <2.5 x 105 nat p.r. No reaction. 75A153

5.105 -0CHCH2(0CH2 CH20)n- + Cd2+ <2.5 x 105 nat p.r. No reaction obs. in polyethylene

glycol soln. 75A153

5.106 CHOHCHOHCH2OH + Cd2+ <2.5 x 10s nat p.r. No reaction. 75A153

5.147 •C02- + Cd2+ -V Cd + + co2 ~105 p.r. Est. from increase in Cd +in 0.1 mol L"

1 Cd2+

soln. contg. 0.1 mol L'

1 HC02

‘, C02-satd.

75A027

(5.1 ± 0.3) x 106 nat p.r. No details given. 75A153

Co

6. Cobalt(II) ions 6.016 •CH2C(CH3) 2OH + Co2+ Co+ <106 nat p.r. Est. from lack of increase in Co +

in 0.1 mol L'

1 Co2+

soln. upon

addn. of 0.1 mol L"

1 tert-BuOH.

75A027

6.075 •CH2OH + Co2+ Co+ *0 V nat p.r. Est. from lack of increase in Co +

in 0.1 mol L'

1 Co2+

soln. upon

addn. of 0.1 mol L

_1 MeOH.

75A027

6.078 (CH3)2COH + Co2+ Co + <106 nat p.r. Est. from lack of increase in Co +

in 0.1 mol L"

1 Co2+

soln. upon

addn. of 0.1 mol L'

1 2-PrOH.

75A027

6.147 •C02- + Co2+ C02 + Co + 102 < k < 105 nat p.r. Est. from lack of increase in Co +

in 0.1 mol L'

1 Co2+

soln. upon addn.

of 0.1 mol L'

1 formate, as well

as y-r. expts. (73G039).

75A027

7. Diaqua( 2,3,9, 10-tetramethyl-l ,4,8, 1 1 -tetraazacyclotetradeca- 1 ,3,8, 10--tetraene)cobalt(II) ion

7.078 (CH3) 2COH + CoZ(H2 0)22+ — Co(I) 5.5 x 109 1.25, p.r. P.b.k. in 2 mol L"

1 2-PrOH. 76A001

6.5 7.147 •C02- + CoI(H20)22+ — Co(I) 4.7 x 109 6.5 p.r. P.b.k. in 0.1 mol L"

1 formate. 76A001

8
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

8. Diaqua(5,7,7,12,14,14-hexamethyl-•1,4,8, ll-tetraazacyclotetradeca-4,14-diene)cobalt(II) ion

8.078 (CH3)2 tOH + CoZ(H2 0)22+ — Co(I) «107 6.5 p.r. No reaction in 2 mol L

1 2-PrOH. 76A001

8.147 •CO/ + CoZ(H20)22+ -» Co(I) «107 6.5 p.r. No reaction in 0.1 mol L"

1 formate. 76A001

9. Diaqua(5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll-diene)cobalt(II) ion

9.001 •CH3 + CoZ(OH2)22+ — — 7 x 108 1 f.p. Radical from Co(NH3)502 CCH3 2+

in 74F644 CH3CoinZ(OH2) 22+

(1 to 2) x 108 9.5 p.r. HC104 soln. D.k. at 330 nm (Co

11 ) as well as

p.b.k. at 280 nm in Ar-satd. 1 mol L'

1 rerr-BuOH soln. contg. 5 x 10”3 mol L*

1 CH3

I.

76A203

9.016 •CH2 C(CH3)2OH + CoZ(OH2)22+ <1 x 107 p.r. No reaction obs. 78A200

9.020 •CH2CH0 + CoZ(0H2 )22+ — 8 x 107 1-3, p.r. P.b.k. in N2 0-satd. soln. contg. 78A200

CoinZCH2 CHO 7-10 1 mol L'

1 ethylene glycol. 9.035 •CH2 C0/ 4- CoZ(OH2) 22+ <1 x 107 p.r. No reaction obs. 78A200

9.075 •CH2 OH + CoZ(OH2)22+ — (7 ± 1) x 107 1-6 p.r. P.b.k. in N2 0-satd. soln. contg. 78A200

Co,uZCH2 OH 1 mol L'

1 MeOH.

9.076 CH3 CH0H + CoZ(OH2) 22+

(3.0 ± 0.4) x 107 1-6 p.r. P.b.k. in N2 0-satd. soln. contg. 78A200

CoMIZCH0HCH3 1 mol L'

1 EtOH.

9.078 (CH3)2COH + CoZ(OH2) 22+ <107 6.5 p.r. No reaction obs. in soln. contg. 2 mol L'

1 2-PrOH. 76A001 <107 p.r. No reaction obs. 78A200

9.089 •CHOHCF3 + CoZ(OH2)22+ — (1 ± 0.5) x 107 6 p.r. P.b.k. 78A200

CoIUZCHOHCF3 9.098 NH/ CH2CH0H + CoZ(OH2 )22+ 4.0 x 107 7.0 p.r. P.b.k. in N2 0-satd. soln. contg. 0.1 mol L’

1 2-aminoethanol; rate pH

dependent.

78A200

9.101 •CHOHCH2 OH + CoZ(0H2)22+ -» -1 x 10' 3-7 P-r- P.b.k. in N2 0-satd. soln. contg. 78A200

CoinZCHOHCH2 OH 1 mol L"

1 ethylene glycol. 9.147 •C02* + CoZ(OH2)22+ <107 6.5 p.r. No reaction obs. in soln. contg. 0.1 mol L”

1 formate. 76A001

10. Cobal(II)amin (Vitamin B12r)

10.001 •CH3 + B12r— methvlcobalamin ~1.5 x 109 f.p. D.k. following irrad. -induced Co-CH3 homolysis of methylcobalamin; back reaction.

77F005

10.016 •CH2C(CH3)2OH + B12r —* B12a 2.4 x 108 5 p.r. P.b.k. at 350-60 nm in N2 0-satd. 75A169

(B12a See 54.) soln. contg. 0.1 mol L'

1 terf-BuOH. 10.078 (CK3 ) 2COH + B12r — (4 ± 2) x 109 f.p. D.k. at 474 nm in 90% 2-PrOH 79A158

B12s (Co

1 ) + (CH3)2CO + H

+

soln. of adenosyl cobalamin after homolysis of the adenosyl group. 10.101 •CHOHCH2 OH + B12r —»• B12a 2.4 x 108 p.r. P.b.k. at 525 nm as well as d.k. 75A169

(B12a See 54.) at 400 nm in N20-satd. soln. contg. 0.05 mol L”

1 ethylene glycol. 10.147 •CO/ + B12r — C02 + B12s (Co

1 ) 8.2 x 108 9.2 p.r. D.k. at 311 and 478 nm as well as

p.b.k. at 386 and 280 nm in N2 0-satd. soln. contg. 0.1 mol L"

1

formate.

74A105

10a. 3,10,17,24—Tetra8ulfophthalocyaninecobalt(II) ion dimer

10a. 016 •CH2C(CH3)2 OH + (Co'pts)^ — 2.2 x 108 9 p.r. P.b.k. at 440 nm in N2 0-satd. soln. 80A146

addn. contg. 0. 1-0.2 mol L'

1 tert-BuOH; mechanism suggested to involve addn.

followed by splitting to give (RCo", pts)

5-. 10a.075 •CH2 OH + (Co'^ts)^ —

electron transfer

(CH3)2COH -f- (Co**pts)2^ —

2.2 x 108 9 p.r. D.k. in NjO-satd. soln. contg.

0. 1-0.2 mol l/

1 MeOH; mechanism

suggested to involve ligand-radical formation, followed by metal oxid. and dimer splitting to give (Co'pts)'

-

.

80A146

10a.078 1.5 x 109 9 p.r. D.k. in N20-satd. soln. contg. 80A 146

electron transfer 2-PrOH; see above.

9
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mop's*1 ) PH Method Comment Ref.

11. 11.016

Nitrilotriacetatocobaltate(II) ion •CH2C(CH3)2OH + Co"NTA — (1.1 ± 0.2) x 107 7 p.r. P.b.k. at 330 nm in N2 0-satd. 79A255

11.147 [NTACoCH2 C(CH3)2 OH]-•C02- + Co"NTA ^[NTACo(C02)]2- (7.3 ± 0.7) x 107 7 p.r.

soln. contg. 0.5 mol

P.b.k. at 270 nm in

L*

1 tert-BuOH. Nz O-satd. 79A255

soln. contg. 0.2 mol L*

1 formate.

Cobalt(III) ions

12. Hexaamminecobalt(III) ion

12.035 •CH2C02

- + Co(NH3)63+ <3.2 x 106 7.3 p.r. D.k. in N20-satd. soln. contg. 0.01 mol L*

1 acetate. 72A018

•CH2C02H + Co(NH3)63+ <1.0 x 107 2.5 p.r. D.k. in Ar-satd. soln. contg. 0.01 mol L*

1 acetic acid. 72A018

12.042 •CH(C02H)2 + Co(NH3)63+ <8.0 x 106 2.5 p.r. D.k. in Ar-satd. soln. contg. 0.01 mol L"' malonic acid. 72A018

12.054 HCON(CH3 )CH2 + Co(NH3)63+ < 1.0 x 107 6.0 p.r. D.k. in N20-satd. soln. contg. 0.01 mol L*

1 dimethylformamide.

72A018

12.056 NH3 + £HC02- + Co(NH3)63+ <1.2 x 107 5.7 p.r. D.k. in N20-satd. soln. contg. 0.1 mol L*

1 glycine. 72A018

12.075 •CH20- + Co(NH3)63+ — (9.0 ± 1.4) x 109 12 p.r. D.k. in N20-satd. soln. contg. 72A018

CH20 + Co(NH3)62+ 0.01 mol L*

1 MeOH.

•CH2OH + Co(NH3)63+ — (1.4 ± 0.2) x 10" 5-6 p.r. D.k. in N20-satd. soln. contg. 72A018

CH20 + H

+ + Co(NH3)62+

(1.4 ± 0.2) x 108 6.1 p.r.

0.01 mol L*1 MeOH.

D.k. in N20-satd. soln. contg. 77A100

(1.4 ± 0.2) x 108 5.75 1 mol L*

1 MeOH.

(6 ± 0.9) x 107 4.9

(4.5 ± 0.7) x 107 4.5 <1 x 107 3.5 12.076 CH3 CHO- + Co(NH3)63+

(8.5 ± 1.3) x 109 12 p.r. D.k. in N20-satd. soln. contg. 72A018

CHjCHOH + Co(NH3)63+

(5.2 ± 0.8) x 107 5-6 0.01 mol L*1 EtOH; e-transfer. 12.078 (CH3)2tO- + Co(NH3)63+

(5.0 ± 0.8) x 109 12 p.r. D.k. in N2 0-satd. soln. contg. 72A018

(CH3)2CHOH + Co(NH3)63+

(1.3 ± 0.2) x 107 5-6 0.01 mol L*

1 2-PrOH; e-transfer. 12.093 CH3CHOC2 Hs + Co(NH3 )63+

-0CHCH20(CH2)2- + Co(NH3)63+

<5 x 106 5.5-6 p.r. D.k. in N20-satd. soln. contg.

ethyl ether. 77A100

12.104 <2 x 106 3.5-4 p.r. D.k. in N20-satd. soln. contg. dioxane. 77A100

12.107 CH3C0C(0*)CH3 + Co(NH3 )63+ <1.8 x 10s 5.5 p.r. D.k. in N20-satd. soln. contg. 72A018

CH3COfi(OH)CH3 + Co(NH3)63+ <2.0 x 10s 1.2 0.01 mol L*

1 biacetyl. 12.117 CH3C(0-)C02

- + Co(NH3)63+ 2.4 x

10'° 12.0 p.r. D.k. in N20-satd. soln. contg. 72A018

CH3C(0H)C02

- + Co(NH3)63+ 7.0 x 106 6.0 0.01 mol L'

1 lactate; e-transfer. 12.127 •CONH2

-1- Co(NH3)63+ <3.6 x 107 6.2 p.r. D.k. in N20-satd. soln. contg. 0.01 mol Lf 1 formamide. 72A018

12.147 •C02* + Co(NH3)63+ — 4.0 x 107 4.8 p.r. D.k. in N20-satd. soln. contg. 72A018

C02 + Co(NH3)62+

(1.1 ± 0.3) x 108 6.9 p.r.

0.01 mol L'

1 formate.

C.k. in N20-satd. soln. contg. 73A075

(rel.) 0.1 mol L"

1 formate rel. to A(*C02‘ + PNBPA) = 1.9 x 109 .[26.147]

13. Pentaammineaquacobalt(III) ion

13.075 •CH2OH + Co(NH3)5OH23+ — (1.5 ± 0.5) x 106 3.5-4 y-r. Calcd. from C(Co2+

), dose rate 77A100

Co(II) (rel.) and A(R + R) = 2.4 x 109

. 13.147 •C02

* + Co(NH3)sOH23+ — (1.7 ± 0.3) x 108 5.2 p.r. C.k. in N20-satd. soln. contg. 73A075

Co(II) (rel.) 0.1 mol Lf

1 formate; rel. to A(-C02- + PNBPA) = 1.9 x 109.[26.147]

14. Pentaamminehydroxycobalt( III ) ion

14.147 •C02* + Co(NH3)3OH2+ <(3 ± 1.5) x 107 7.8 p.r. C.k. in N20-satd. soln. contg. 73A075

Co(ll) (rel.) 0.1 mol L*

1 formate; rel. to

k(-C02

- + PNBPA) = 1.9 x 109 .[26.147]

10
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol V1 ) PH Method Comment Ref.

15. Pentaamminebromocobalt(III) ion

15.075 •CH2OH + Co(NH3 ) 5 Br

2+

(9.0 ± 1.4) x 107 6.1 p.r. D.k. in N20-satd. soln. contg. 77A100

(2.5 ± 0.4) x 107 4.9 1 mol L'

1 MeOH.

(2.0 ± 0.3) x 107 4.5

(1.8 ± 0.3) x 107 3.5

(1.8 ± 0.3) x 107 2.0

(1.8 ± 0.3) x 107 1.0 15.076 CHjtHOH + Co(NH3)5 Br2+

(1.5 ± 0.2) x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtOH. 77A100

15.078 (CH3)2COH + Co(NH3) 5Br2+(3.0 ± 0.45) x 108 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. 2-PrOH. 77A100

15.093 CH3 CHOC2 H5 + Co(NH3 ) 5Br

2+

(1.6 ± 0.2) x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg.

ethyl ether. 77A100

15.104 -0£HCH2 0(CH2)2- + Co(NH3 )5 Br2+ <2 x 106 3.5-4 p.r. D.k. in N20-satd. soln. contg. dioxane. 77A 100

16. Pentaamminechlorocobalt(III) ion

16.075 •CH2 OH + Co(NH3 )5C12+

(3 ± 1) x 106 3.5-4 y-r Est. from effect of complex concn. 77A100

(rel.) on C(Co2+

) assuming 2£(R -H R) =

2.4 x 109. 16.076 CH3CH0H + Co(NH3)5C12+

(3.0 ± 0.4) x 106 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. EtOH. 77A100

16.078 (CH3)2tOH + Co(NH3 )5C12+

(4.0 ± 0.6) x 107 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. 2-PrOH. 77A100

16.093 CH3 CHOC2 H5 + Co(NH3) 5C12+

(1.4 ± 0.2) x 107 3.5-4 p.r. D.k. in N2 0-satd. soln. contg.

ethyl ether. 77A100

16.104 -0CHCH2 0(CH2)2- + Co(NH3)5C12+ <2 x 106 3.5-4 p.r. D.k. in N20-satd. soln. contg. dioxane. 77A100

16.147 •C02- + Co(NH3) 5C12+

(1.5 ± 0.3) x 108 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) £(C02- + PNBPA) = 1.9 x 109

in N20-satd. soln. contg. 0.1 mol L*

1 formate. [26.147]

17. Pentaamminefluorocobalt(III) ion

17.075 •CH2 0H + Co(NH3) 5F

2+

(5.5 ± 2) x 105 3.5-4 y-r. Est. from effect of complex concn. 77A100

(rel.) on C(Co2+

) assuming 2Ar(R + R) =

2.4 x 109

.

18. Pentaammine(nitrito-N)cobalt(III) ion

18.147 •C02‘ + Co(NH3)5N02 2+ <(2 ± 1) x 107 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) *(C02

- + PNBPA) = 1.9 x 109

in N2 0-satd. soln. contg. 0.1 mol L*

1

formate. [26.147]

19. Pentaammine(nitrato-0)cobalt(III) ion

19.147 •C02- + Co(NH3)5N032+

(2.1 ± 0.3) x 108 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) /t(C02- + PNBPA) = 1.9 x 109

in N20-satd. soln. contg. 0.1 mol L'

1

formate. [26.147]

20. (Acetato)pentaamminecobalt(III) ion

20.001 •CH3 + Co(NH3) 502 CCH3 2+ — (4 ± 1) x 103 phot. Est. from intensity dependence of 71F579 CH4 + Co2+ + 4NH4 + + NH2 + + (rel.) CH4 and C2 H6 formn. assuming

ch3 co2 h k(R + R) = 2 x 10‘°. 20.147 •C02- + Co(NH3) 502 CCH32+

(1.1 ± 0.3) x 108 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) *(C02

- + PNBPA) = 1.9 x 109

in N2 0-satd. soln. contg. 0.1 mol L'

1

formate. [26.147]

21. Pentaammine(phenylacetato)cobalt(III) ion

21.147 •C02- + Co(NH3 )502CCH2 C6 H.

2+

(7.0 ± 2) x 107 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) *(C02

- + PNBPA) = 1.9 x 109

in N20-satd. soln. contg. 0.1 mol L"

1 formate. [26.147]

11
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol^s l ) PH Method Comment Ref.

22. Pentaammine(4-nitrophenylacetato)cobalt(III) ion

22.147 •C02

- + Co(NH3) 502 CCH2 C6H4 N022+

(1.2 ±0.1) x 109 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) £(C02' + PNBPA) = 1.9 x 109

in N2 0-satd. soln. contg. 0.1 mol L'

1

formate. [26.147]

23. Pentaammine(benzoato)cobalt(III) ion

23.147 •C02

- + Co(NH3 )502 CC6H52+

(4.5 ± 2) X 107 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) £(C02- + PNBPA) = 1.9 x 109

in N20-satd. soln. contg. 0.1 mol L"

1 formate. [26.147]

24. Pentaammine(2-nitrobenzoato)cobalt(III) ion

24.078 (CH3)2 tOH + 1.7 X 109 7.0 p.r. P.b.k. 77A027

Co(NH3)502CC6H4N022+ 24.147 •C02

- + Co(NH3)502 CC6H4N02 2+ 2.0 x 109 7.0 p.r. P.b.k. 77A027

25. Pentaammine(3-nitrobenzoato)cobalt(III) ion

25.078 (CH3)2 COH + 1.5 X 109 7.0 p.r. P.b.k. 77A027

Co(NH3)502CC6H4N02 2+ 25.147 •C02" + Co(NH3)5 02CC6H4N022+ 1.5 x 109 7.0 p.r. P.b.k. 77A027

26. Pentaammine(4-nitrobenzoato)cobalt(III) ion (PNBPA)

26.078 (CH3)2COH + 2.6 X 109 4.5 p.r. Condy. in N20-satd. soln. contg. 74A002

Co(NH3)502 CC6H4N022+ -> 0.2 mol L’

1 2-PrOH. (CH3 )2CO + H

+ + 2.6 X 109 Cohi (NH3)502 CC6H4N02

- 7.0 p.r. P.b.k. 77A027

26.147 •CO-T + Co(NH3)502CC6H4N022+ — 1.9 X 109 7.0 p.r. P.b.k. in N20-satd. soln. contg. 72G340

C02 + Coin(NH3) 5 02 CC6H4N02- 0.1 mol L'

1 formate. 77A027

27. Pentaammine(2,4-dinitrobenzoato)cobalt(III) ion

27.078 (CH3)2tOH + 4.3 X 109 7.0 p.r. P.b.k. 77A027

Co(NH3 )502 CC6H3(N02)22+ 27.147 •C02- + Co(NH3)502CC6H3(N02)22+

7.5 x 109 7.0 p.r. P.b.k. 77A027

28. Pentaammine(3,5-dinitrobenzoato)cobalt(III) ion

28.078 (CH3)2 COH + 2.9 X 109 7.0 p.r. P.b.k. 77A027

Co(NH3) 502 CC6 H3(N02 )22+ 28.147 •C02" + Co(NH3)502 CC6H3(N02)22+

8.1 x 109 7.0 p.r. P.b.k. 77A027

29. Hexaammmebis(ju.-hydroxy)[/u-(4-nitrobeiizoato)]dicobalt(III) ion

29.078 (CH3 )2 COH + ...N02 (2 ± 0.4) X 109 0.7- p.r. P.b.k. in N2 0-satd. soln. contg. 78A108

(CH3)2CO + H

+ + ...N02

- 6.0 1 mol L'

1 2-PrOH.

(1.4 ± 0.4) x 109 p.r. P.b.k. at 370 nm in soln. contg. 1% 2-PrOH; AH\ = 3.1 ± 2.0 kcal mol’’ (13 kj mol"1 ); k decreases with concn.

of 2-PrOH; k = 1.25 x 109 in 99% D2 0-

1% 2-PrOH.

80A066

29.101 •CHOHCH2OH + ...N02 - ...N02 (8 ± 2) x 107 p.r. P.b.k. at 370 nm in soln. of 50% H2 0-50% ethylene glycol; AH\ =

5.4 ± 0.3 kcal mol"1 (21 kj mol"1 )

80A066

30. Pentaammine(4-cyanobenzoato)cobalt(III) ion

30.147 •C02- + Co(NH3)502 CC6H4CN2+

(4.6 ± 2) x 107 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) *(C02" + PNBPA) = 1.9 x 109

in N2 0-satd. soln. contg. 0.1 mol L"

1 formate. [26.147]

31. Pentaammine(pyridine)cobalt(III) ion

31.078 (CH3)2COH + Co(NH3 ) 5C5H5N

3+ — ~109 1-7 y-r. Est. from C(Co2+

) in N2 0-satd. 79A213

Co2+ + 5NH3 + C5H5N soln. contg. 1 mol L"

1 2-PrOH. + (CH3 ) 2CO + H

+

12
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L moT's'

1 ) pH Method Comment Ref.

31.147 •C02

- + Co(NH3 ) 5C5 Hs N

3+

(3.3 ± 0.4) x 108 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) A(C02

- + PNBPA) = 1.9 x 109

in N20-satd. soln. contg. 0.1 mol L~' formate. [26.147]

32. Pentaammine(pyridinecarboxylato)cobalt(III) ion

32.147 •C02

- + Co(NH3 )502 CC5 H4 N

2+

(5.1 ± 2) x 107 6.9 p.r. C.k. with PNBPA assuming 73A075

(rel.) A(C02

- + PNBPA) = 1.9 x 109

in N20-satd. soln. contg. 0.1 mol L"

1 formate. [26.147]

33. Pentaammine(pyrazinecarboxylato)cobalt(III) ion

33.078 (CH3) 2 COH + (4.0 ± 0.6) x 108 0-5 p.r. P.b.k. in N20 or Ar-satd. soln. 78A222

Co(NH3)s02 CC4H3N2 2+ —

(CH3 ) 2CO + ...INJH

contg. 1 mol L"

1 2-PrOH.

34. Tetraammine(pyrazinecarboxylato-0,N)cobalt(III) ion

34.078 (CH3) 2COH + (9 ± 2) x 108 5 p.r. P.b.k. in N20 or Ar-satd. soln. 78A222

Co(NH3)402CC4 H3N22+ (CH3) 2CO + Co"

contg. 1 mol L"

1 2-PrOH.

35. Hexaamminebis(/x-hydroxy)[ni-(pyrazinecarboxylato)](dicobalt(III)1 ion

35.078 (CH3 )2 COH + ...N -> (4.2 ± 0.4) x 108 0-6 p.r. P.b.k. in N20 or Ar-satd. soln. 78A222

(CH3 )2CO + ...5iH contg. 1 mol L"

1 2-PrOH.

36. Tris(ethylenediamine)cobalt(III) ion

36.075 •CH2 0H + Co(en)33+ no reaction 3.5-4 p.r. D.k. in N20-satd. soln. contg. MeOH. 77A100

36.076 CH3 CHOH + Co(en)33+ no reaction 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. EtOH. 77A100

36.078 (CH3) 2COH + Co(en)33+ no reaction 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. 2-PrOH. 77A100

37. ci«-Amminechlorobis(ethylenediamine)cobalt(in) ion

37.075 •CH2 OH + Co(NH3)Cl(en)22+ <2 x 106 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. MeOH. 77A100

37.076 CH3 CHOH + Co(NH3)Cl(en)22+ 4.2 x 106 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. EtOH. 77A100

37.078 (CH3 )2COH + Co(NH3)Cl(en)22+ 2.2 X 107 3.5-4 p.r. D.k. in N20-satd. soln. contg. 2-PrOH. 77A100

37.093 CH3CHOC2 H5 + Co(NH3)Cl(en)22+ 4.6 x 106 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtjO. 77A100

38. cis-Aquachlorobi8(ethylenediamine)cobalt(III) ion

38.075 •CH2 OH + Co(OH2 )Cl(en)2 (1.8 ± 0.5) x 106 3.5-4 p.r. . D.k. in N20-satd. soln. contg. MeOH. 77A100

38.076 CH3 CH0H + Co(OH2 )Cl(en)22+ 2.0 x 107 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtOH. 77A100

38.078 (CH3 )2COH + Co(OH2)Cl(en)22+ 8.2 x 107 3.5-4 p.r. D.k. in N20-satd. soln. contg. 2-PrOH. 77A100

38.093 CH3CHOC2 H5 + Co(OH2 )Cl(en)22+ 3.5 x 107 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtjO. 77A100

39. trans-Dibromobi8(ethylenediamine)cobalt(III) ion

39.075 •CH2 OH + Co(en)2 Br2 +

2.6 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. MeOH. 77A100

39.076 CH3CHOH + Co(en)2 Br2 +

5.7 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtOH. 77A100

39.078 (CH3)2 COH + Co(en)2Br2 +

6.8 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. 2-PrOH. 77A100

39.093 CH3 CHOC2 Hs + Co(en)2 Br2 +

6.5 x 108 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. Et20. 77A100

39.104 -0CHCH2 0(CH2 )2—f Co(en)2 Br2 + 4.4 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. dioxane. 77A100

40. cis-Bromobis(ethylenediamine)fluorocobalt(III) ion

40.075 •CH2 OH + CoBr(en)2 F

+ <2 x 106 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. MeOH. 77A100

40.076 CH3 CHOH + CoBr(en)2F

+

2.8 x 107 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. EtOH. 77A100

40.078 (CH3)2tOH + CoBr(en)2F

+

1.1 x 108 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. 2-PrOH. 77A100

40.093 CH3tHOC2 H5 + CoBr(en)2 F

+ 4.9 x 107 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. Et20. 77A100

41. cis-Dichlorobi8(ethylenediamine)cobalt(IIl) ion 41.075 •CH2OH + CoCl2 (en)2 + <5 x 106 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. MeOH. 77A100

13
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 's

! ) pH Method Comment Ref.

41.076 CH3 CHOH + CoCl2(en)2 +

3.8 x 107 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtOH. 77A100

41.078 (CH3)2 COH + CoCl2(en)2 +

1.0 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. 2-PrOH. 77A100

42. trans-Dichlorobis(ethylenediamine)cobalt(in) ion

42.075 •CH2OH + CoCl2 (en)2 +

(8 ± 2) x 106 3.5-4 p.r. D.k. in N20-satd. soln. contg. MeOH. 77A100

42.076 CH3 CHOH + CoCl2(en)2 +

1.5 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtOH. 77A100

42.078 (CH3 ) 2COH + CoCl2 (en)2 +

3.8 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. 2-PrOH. 77A100

42.093 CH3 CHOC2 H5 + CoCl2 (en)2 +

1.5 x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. E^O. 77A100

42.104 -0CHCH2 0(CH2) 2- + CoCl2 (en)2 +

3.5 x 107 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. dioxane. 77A100

43. trans-Bis(ethylenediamine)difluorocobalt(III) ion

43.075 •CH2OH + CoF2(en)2 + no reaction 3.5-4 p.r. D.k. in N20-satd. soln. contg. MeOH. 77A100

43.076 CH3CHOH + CoF2(en)2 + no reaction 3.5-4 p.r. D.k. in N20-satd. soln. contg. EtOH. 77A100

43.078 (CH3)2 COH + CoF2 (en)2 +

no reaction 3.5-4 p.r. D.k. in N20-satd. soln. contg. 2-PrOH. 77A100

44. Tris( 2

,2 '-bipyridine)cobalt(III) ion 44.075 •CH2 OH + Co(bpy)33+ - 2 x 108 1,7 p.r. P.b.k. at 326 nm in N2 0-satd. soln. 79A034

Co(bpy)32+

contg. 0.25 mol L

" 1 MeOH.

44.078 (CH3) 2COH + Co(bpy)33+ —* (2.5 ± 0.3) x 109 0.5, p.r. P.b.k. at 330 nm in N2 0-satd. soln. 79A034

Co(bpy) 3

2 +

7.8 contg. 0.1 mol L

' 1 2-PrOH.

44.147 •C02

“ + Co(bpy)33+ —* (7.6 ± 0.2) x 109 6.9 p.r. C.k. with PNBPA assuming 73A075

Co(bpy)32+

(rel.) k(C02

- + PNBPA) = 1.9 X 109

in N20-satd. soln. contg. 0.1 mol L

' 1 formate. [26.147]

(7.8 ± 0.5) x 109 6.9 p.r. P.b.k. at 330 nm in N2 0-satd. soln. contg. 0.1 mol L

" 1 formate. 79A034

45. Tris( 1 , lO-phenanthroline)cobalt(III) ion

45.075 •CH2 OH + Co(phen)33+ -* 8 x 108 1-7 p.r. P.b.k. at 475 nm in N2 0-satd. soln. 80A227

addn. to ligand contg. 2.5 mol L

" 1 MeOH; c.k. with 02 gave (7 ± 1) x 108 assuming

k(R + 02) = 4.2 x 109

. 45.076 CH3 CHOH + Co(phen)3 3+ -> 3.8 x 109 1-7 p.r. P.b.k. at 475 nm in N2 0-satd. soln. 80A227

addn. to ligand contg. 0.25 mol L

' 1 EtOH.

45.078 (CH3)2 COH + Co(phen)33+ —

>

4.6 x 109 7.0 p.r. P.b.k. at 360 nm in N20-satd. soln. 79A034

Co(phen)32+

contg. 0.5 mol L

" 1 2-PrOH.

45a. Tris( 5,6-dimethyl-1 , 1 0-phenant hroline )cobalt( III ) ion

45a. 075 •CH2OH + Co(5,6-Me2phen)33+ —>• 4.9 x 108 — 7 p.r. P.b.k., as well as d.k. at 380 nm 80A227

Co(5,6-Me2phen)3 2+

in N2 0-satd. soln. contg. 2.5 mol L

'1 MeOH.

45a. 076 CH3CHOH + Co(5,6-Me2 phen)33+ -> 3.1 x 109 ~7 p.r. P.b.k., as well as d.k. at 380 nm in 80A227

Co(5,6-Me2 phen) 3

2 + N2 0-satd. coin, contg. 0.25 mol L

" 1 EtOH.

45a.078 (CH3)2 tOH + Co(5,6-Me2 phen)33+ - 3.21 x 109 ~7 p.r. P.b.k., as well as d.k. at 380 nm in 80A227

Co(5,6-Me2 phen)32+ N20-satd. soln. contg. 0.25 mol L

" 1 2-PrOH; same product from eaq

~

reaction.

46. Diaqua(5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll-diene)cobalt(III) ion

46.078 (CH3 )2COH + Co1 " -* Co" 2.0 x 108 2.0 p.r. P.b.k. 76A203

46.147 •CO/ + Co1 " -* Co" 8.1 x 108 2.5 p.r. P.b.k. 76A203

47. Aqua(5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll-diene)hydroxycobalt(III) ion

47.078 (CH3) 2COH + Co" 1 - Co" 1.1 x 108 6.0 p.r. P.b.k. 76A203

48. (5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll-diene)dihydroxycobalt(III) ion

48.078 (CH3 ) 2 COH + Co1 " -* Co" 1.1 x 108 10.0 p.r. P.b.k. 76A203

14
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L moC's ') PH Method Comment Ref.

49. Dichloro(5,7,7,12,14,14-hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,l l-diene)eobalt(III) ion 49.078 (CH3)2 tOH + Co"1 — Co" 7.0 X 108 1.0 p.r. P.b.k. 76A203

49.147 •C02- + Co1 " — Co" 1.1 x 109 2.5 p.r. P.b.k. 76A203

50. Diaqua(2,3,9,10-tetramethyl-l,4,8,ll-tetraazacyclotetradeca-l,3,8,10-tetraene)cobalt(III) ion

50.078 (CH3)2tOH + Co1 " — Co" 1.9 X 109 1.0 p.r. P.b.k. 76A203

50.147 •C02

- + Co"1 — Co" 6.4 x 109 2.5 p.r. P.b.k. 76A203

51. Aquahydroxy(2,3,9,10-tetramethyl-l,4,8,ll-tetraazacyclotetradeca-l,3,8,10-tetraene)cobalt(III) j on

51.078 (CHj)2 COH 4- Co1 " — Co" .5.5 X 108 5.0 p.r. P.b.k. 76A203

52. Dibydroxy(2,3,9,10-tetramethyl-l,4,8,l 1-tetraazacyclotetradeca--l,3,8,10-tetraene)cobalt(III) ion

52.078 (CH3)2COH 4- Co1 " Co" 3.3 X 108 9.0 p.r. P.b.k. 76A203

53. Cyanocobf III )alamin( Vitamin B12)

53.147 •C02‘ + B12 — B12r 1.2 x 109 6.0 p.r. P.b.k. at 530 nm as well as d.k. 73G116

(B12r See 10.) at 390 nm in soln. contg. 0.1 mol L"

1 ferr-BuOH, satd. with C02

. no reaction p.r. No change in o.d. in N20 or C02-satd.

soln. contg. 0.1 mol L"

1 formate, or C02 -satd. soln. contg. 0.1 mol L"

1 te/t-BuOH.

74A105

54. Hydroxocob( III )alamin( Vitamin B 1 2a

)

54.147 •C<V + B12a — B12r 1.45 x 109 9.2 p.r. D.k. at 350 nm as well as p.b.k. at 74A105

(B12r See 10.) 310 nm in C02-satd. soln. contg. tert-BuOH.

55.

Cr

Chromium! II) ion 55.006 •CH2C(CH3)2 C02 H + CRH2 0)62+ (H2 0)5 Cr"

l CH2C(CH3)2C02H

1.1 x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg.

pivalic acid-HC104. 74A146

55.016 •CH2QCH3 ) 2OH + Cr(H2 0)62+ —

(H2 0)5 Cr'"CH2C(CH3)20H

1.0 x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg. tert-Bu0H-HC104

. 74A146

55.020 •CH2CHO 4- Cr(H20)62+ —

(H20)5 Cr

in CH2 CH(0H)2

(3.5 ± 0.5) x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg. ethylene glycol-HC104; -CHOHCH2OH

loses water in acid soln.

74A146

55.035 •CH2 C02 H + CRH20)62+ —

(H20)5 CrmCH2C02 H

2.5 x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg.

acetic acid-HC104. 74A146

55.037 CH3 CHC02 H + CifH2 0)62+ —

(H2 0)5 Cr"'CH(CH3)C02 H

1.1 x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg. propionic acid-HC104

. 74A146

55.042 •CH(C02 H)2 + Cr(H2 0)62+ —

(H20)5Cr"'CH(C02 H)2

6.0 x 107 ~1 p.r. P.b.k. in Ar-satd. soln. contg. malonic acid-HC104

. 74A146

55.054 HCON(CH3)tH2 + CRH20)62+ —

(H20)5 Cr"'CH2 N(CH3 )CH0

(1.1 ± 0.1) x 108 ~5 p.r. P.b.k. in At or N20-satd. soln. contg. dimethylformamide. 74A146

55.075 •CH2OH + Cr(H20)62+ —

(H2 0)5 Cr"'CH2 0H

1.6 x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg. Me0H-HC104

. 74A146

55.076 ch3 Choh + CRH20)62+ —

(H 2 0)5 Cr'"CH0HCH3

7.9 x 107 ~1 p.r. P.b.k. in Ar-satd. soln. contg. Et0H-HC104

. 74A146

55.078 (CH3)2COH + Cr(H2 0)62+ —

(H2 0)5Cr'"C(CH3)20H

5.1 x 107 ~1 p.r. P.b.k. in Ar-satd. soln. contg. 2-Pr0H-HC104

. 74A146

55.093 CHjCHOQHj -(- CRH2 0)62+ —

(HjO^CrH'CHlCHjjOQHj

3.4 x 107 ~1 p.r. P.b.k. in Ar-satd. soln. contg. EtjO-HClO,. 74A146

55.101 •CHOHCH2OH + Cr(H20)62+ —

(H20)5CrmCH2 CH(0H)2

(1.5 ± 0.2) x 108 3.0-

4.5

p.r. P.b.k. in Ar-satd. soln. contg. ethylene glycol-HC104; product same as in 55.020.

74A146

55.104 -0CHCH2 0(CH2 ) 2- -f- Cr(H20)62+ —

(H20)5Cr'"R

1.0 x 108 ~1 p.r. P.b.k. in Ar-satd. soln. contg. dioxane-HC104

. 74A146

55.115 •CHOHCOjH 4- CHH20)62+ —

(H 2 0)5Cr"'CH0HC02 H

X o ~1 p.r. P.b.k. in Ar-satd. soln. contg.

glycolic acid-HC104. 74A146

15
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L moC's'1 ) pH Method Comment Ref.

55.117 CH3C0HC02 H + Cr(H2 0)62+ 9.2 x 107 ~1 p.r. P.b.k. in Ar-satd. soln. contg. 74A146

(H2 0)5Cr

in C0H(CH3)C02 H lactic acid-HC104

. 55.127 •CONH2 + Cr(H20)62+ -+ (6.5 ± 0.6) x 108 ~5 p.r. P.b.k. in Ar- or N20-satd. soln. 74A146

(H2 0)5Cr

|[l C0NH2 contg. formamide. 55.147 •C02-(-C02 H) + Cr" Crin C02

- (1.1 ± 0.1) x 109 1.4 p.r. D.k. in soln. contg. 1 mol L"

1 formic acid; product spectrum similar

to products containing C-Cr bonds

[74A146].

73A057

56. Chromium) III) ion

56.147 •C02-(-C02 H) + Cr

111 no reaction 1.4 p.r. D.k. in soln. contg. 1 mol L'

1 formic acid. 73A057

Cu

57. Copper(I) ions 57.014 •CH2CH2OH + Cu + Cu"CH2 CH2 OH+

(1.9 ± 0.6) x 1010 4.5 p.r. Est. from p.b.k. in N2 0-satd. soln. 78A322

Cu2+ + C2 H4

-(- OH- contg. ethylene and Cu2+

. 57.016 •CH2C(CH3 ) 2OH + Cu + ^ (2.6 ± 0.9) 4.5 p.r. Est. from p.b.k. at 400 nm in 78A322 Cu"CH2C(CH3)2OH+

x 1010 N20-satd. soln. contg. rert-BuOH Cu2+ + OH- + CH2 = C(CH3)2 and Cu2+

. 57.075 •CH2OH + Cu + ^ Cu"CH2OH+ -1010 4.5 p.r. Est. from growth and decay of absorption in soln. contg. MeOH

and Cu2+

; K = 104 dm3 mol" 1

.

78A322

— 6 x 109 4.0 p.r Est. from growth and decay of absorption in soln. contg. MeOH

and Cu2+

; K ss 5 x 103 dm3 mol"1

.

80A278

57.078 (Ch3 )2 (!;oh + Cu + -5 x 109 4.5 p.r. Est. from growth and decay of absorption in soln. contg. 2-PrOH

and Cu2+.

78A322

58. Copper(I) ion, complex with ethylene

58.014 •CH2 CH2OH + CuC2 H4 +

(7.8 ± 2.5) x 107 4.5 p.r. Est. from effect of [C2 H4] on rate 78A322

2C2 H4 + Cu2+ + OH- of formn. and decay of CuC2H4 +

at 227 nm; radical from OH + ethylene. 58.016 •CH2 C(CH3) 2OH + CuC2 H4 +

(5.3 ± 1.6) x 107 4.5 p.r. Est. from effect of [C2 H4] on rate 78A322 C2 H4 + CH2 = C(CH3 )2 + Cu2+

of formn. and decay of CuC2 H4 +at + OH’ 227 nm in soln. contg. ierr-BuOH.

58a. Ethylenediaminetetraacetatocuprate(I) ion

58a.079 CH3CH2CH2 CHOH + CuEDTA3- — (4 to 5) x 109 7.5 p.r. P.b.k. at 440 nm in soln. contg. 80A153

RCuEDTA3- 0.01 mol L"

1 CuEDTA2 * and 0.06 mol L"

1 1-BuOH assuming 2A(R + R) = 109

.

59. Copper(II) ions 59.001 •CH3 + Cuaq2+ CH3Cu2+

(7.4 ± 0.6) x 10s ~2 f.p. P.b.k. in 10~2 mol L"

1 HC104 soln. contg. 0.01-0.2 mol L"

1 Cu2+ and Co(NH3) 502CCH32+

.

78F301

59.014 •CH2CH2 OH + Cua() 2+ — (1.9 ± 0.4) x 107 4.5 p.r. P.b.k. at 270 nm (Cu'C2 H4) in 78A322

Cu'"-CH2 CH2 OH+

(2.2 ± 0.4) x 107 2 N20-contg. ethylene (10"3 mol L"

1 ) Cu + + prod.

(3 ± 1) x 107 6 p.r.

soln.; *C2 H5 is present at pH 4.5 (-10%) and pH 2( — 50%).

P.b.k. in soln. contg. (1-5) x 10~4 mol L"

1 CuS04 satd. with ethylene- N20 (1:1).

80A277

59.016 •CH2 C(CH3 ) 2 OH + Cua2+ Cum

-R (2.7 ± 0.5) x 106 4.5 p.r. P.b.k. at 320 nm (Cu'CH2CHCONH2) in 78A322 —» Cu + + prod. (3.2 ± 0.6) x 106 3 N2 0-satd. soln. contg. rer/-BuOH

and acrylamide.

(5 ± 2) x 106 6 p.r. P.b.k. in N2 0-satd. soln. contg. 80A277

(1-5) x 10 4 mol L'

1 CuS04 and 0.1 mol L'

1 tert-BuOH. 16
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 's'

1 PH Method Comment Ref.

59.035 •CH2C02

- + Cu2+ Cu'"CH2 C02 + —*• Cu + + prod.

(6.4 ± 1.5) x 108 6.0 p.r. D.k. in N20-satd. 10"2 mol L'

1

acetate soln. 77A025

59.037 CH3 CHC02

- + Cu,

q 2+ — Cu'"-R —> Cu~ + prod.

(5 ± 0.5) x 108 6 p.r. P.b.k. in N2 0-satd. soln. contg. (2-10) x 10"5 mol L"

1 CuS04 and 10~2 mol L

-1 propionate.

80A277

59.041 -0

2CCH0HCHC02- + Cu.

q2+ —

Cum-R —*• Cu + + prod.

(8 ± 0.3) x 108 6 p.r. P.b.k. in N2 0-satd. soln. contg. (5-10) x 10’5 mol L'

1 CuS04 and (2.5-10) x 10"4 mol L"

1 fumarate; pH dependent, k = 8.0 x 108

, 1.8 x 108

, 1.2 x 108

, 6.4 x 107, 3.1 x 107, and <2 x 107 at pH 5.0, 3.5, 3.0, 2.6, 2.1, and 1.5, resp.

80A277

59.048 •CC13 (+ -CHC12) + Cu,

q2+ —

Cul[l -CCl3 -> Cu + + prod.

(3 ± 1.5) x 107 6 p.r. P.b.k. in Ar-satd. soln. contg. (2-10) x 10~5 mol L"

1 CuS04 and (1-10) 80A277

x 10'2 mol L1 CHC13; G(-CHC12) =

G(e,

q

~) and C(-CC13) = G(OH). 59.075 •CH2 OH + Cuaq2+ — Cu + + 1+ O X o 5-6 p.r. D.k. in N20-satd. 10 2 mol L

1 72A018 CH20 + H

+

(1.6 ± 0.3) x 108 2-5 p.r. MeOH soln. P.b.k. at 320 nm (Cu'CH2 CHCONH2 ) in soln. contg. MeOH and acrylamide

(10‘2 mol L-').

78A322

(1.9 ± 0.4) x 108 <3 p.r. D.k. 78A322

(1.6 ± 0.2) x 108 6 p.r. D.k. at ~300 nm (radical) in N2 0-satd. soln. contg. 0.1 mol L"

1 MeOH.

80A277

59.076 CH3 CHOH + Cu,

q 2+ -> Cu + + (7.4 ± 1.1) x 107 5-6 p.r. D.k. in N2 0-satd. 10"2 mol L"

1 72A018 CH3CHO + h

+

(9.4 ± 1.9) x 107 2-5 p.r. EtOH soln. P.b.k. at 320 nm (Cu'CH2CHCONH2 ) in soln. contg. EtOH and acrylamide

(10'2 mol L’

1 ).

78A322

(9 ± 2) x 107 6 p.r. D.k. at ~300 nm (radical) in N2 0-satd. soln. contg. 0.1 mol L'

1 EtOH.

80A277

59.078 (CH3)2COH + Cujq 2+ — Cu + + (4.5 ± 0.7) x 107 5-6 p.r. D.k. in N20-satd. 10'2 mol L'

1 72A018

(5.2 ± 1.0) x 107 2-5 p.r. 2-PrOH soln. P.b.k. at 320 nm (Cu'CH2CHCONH2 ) in soln. contg. 2-PrOH and acrylamide

(lO'

2 mol L'1 ).

78A322

(5.0 ± 1.0) x 107 <3 p.r. D.k. 78A322

(5.0 ± 1.5) x 107 6 p.r. D.k. at ~300 nm (radical) in N20-

satd. soln. contg. 0.1 mol L'

1 2-PrOH.

80A277

59.113 •A* + Cu,

q 2+ A o phot. Est. 78A394

(A- = Radical from ascorbate) 59.147 •C02

- + Cuiq 2+ — C02 + Cu +

(1.5 ± 0.3) x 108 6.8 p.r. D.k. at 260 nm in N20-satd. formate (0.1 mol L'

1 ) soln. 78A176

60. (5,7,7,12,14,14-Hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll-diene)copper(II) ion 60.075 •CH2 OH + Cu"Z, — Cu'L <2 x 106 3.5- p.r. P.b.k. in N20-satd. soln. contg. 80A 189

10 0.1 mol L'

1 MeOH; product ident. with that from e,

q

". •CH20- + Cu"L — Cu'Z.

CH,tHOH + Cu"Z, -> Cu'Z.

9.0 x 108 12.0 p.r. P.b.k. at 410 nm; no reduction obs.

in neutral soln.; in methanolic soln. k = 2.2 x 104 was detd. by f.phot.

(p.b.k. at 415 nm)[77F639].

76A039

60.076 <2 x 106 3.5- p.r. P.b.k. in N20-satd. soln. contg. 80A 189

10 0.1 mol L"' EtOH; product ident. with that from e^~. 60.078 (CH3)2tOH + Cu"Z. -> Cu'Z. <2 x 106 3.5- p.r. P.b.k. in N2 0-satd. soln. contg. 80A189

10 0.1 mol L'

1 2-PrOH; product ident. with that from e,

q

~. (CH3)2 CO' + Cu"Z, — Cu'Z. 9.0 x 108 12.5 p.r. P.b.k. at 410 nm; no redn. obs. in 76A039

neutral soln. 17
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L moR's

-1

) pH Method Comment Ref.

60.147 •C02

- + CuUL Cu'L 2.3 x 109 7.0 p.r. P.b.k. at 410 nm. 76A039

61. Glycylglycylglycinatocopper(ll) complex

D.k. at 550 nm (Cu11 ) in N2 61.147 •C02 + Cu (gly3 ) — Cu(I) + C02 (2.8 ± 0.3) x 10 0-satd.

8 9.1 p.r. 76A016

formate (10‘2 mol L"

1 ) soln. contg.

Cu(II) and gly3 in 1:5, 1:3 and

1:2 ratio. 62. (Oxidized glutathione)copper(II) complex

D.k. at 595 nm (Cu11 ) in N2 62.147 •C0 0-satd. 2

* + Cu (GSSG)n (1.0 ± 0.2) x 108 11 p.r. 76A016

Cu(I) + C02 soln. contg. formate ion; 10% of the •C02

~ reacted with the disulfide —* GSSG" (p.b.k. at 410 nm).

63. Histidinecopper(II) complex

(4.1 ± 0.4) x 108 D.k. at 600 nm (Cu11 ) in Nz 63.147 •C0 O-satd. 2- + Cu(II) -> Cu(I) 11.0 p.r. 77A138

soln. contg. formate.

64. Glycylhistidinecopper(II) complex

D.k. at 565 nm (Cu11 ) in N2 64.147 •C0 0-satd. 2- + Cu(I I) (4.5 ± 0.3) x 108 6.6 p.r. 77A138

(1.6 ± 0.2) x 107 11.0 soln. contg. formate.

65. /3-Alanylhistidinecopper(II) complex

D.k. at 600 nm (Cu

11 ) in N2 65.147 •C0 0-satd. 2“ + Cu(II) (3.5 ± 0.4) x 108 7.5-11 p.r. 77A138

soln. contg. formate.

65a. Ethylenediaminetetraacetatocuprate(II) ion

65a.079 CH3CH2CH2CHOH + CuEDTA2 - (0.5 to 1) x 106 7.5 p.r. Calcd. from concn. effect on p.b.k.

for RCuEDTA3-

; see 58a.079. 80A153

Eu

66. Europium(III) ion

Est. from p.b.k. at 250 nm (Eu11 66.147 •C0 ). 2 H(-C02

-) + Eu(III) -> Eu(II) > 7 x 106 1.4 p.r. 73A057

Fe

67. Iron(II) ion

67.078 (CH3) 2COH + Fe(H2 0)62+ 2.9 x 106 ~2 p.r. Est. from change in abs. at 250 nm;

product suggested to be Fe(H20)5R

2+

. 75A166

Deuteroheme See 223.

68. Iron(III) ions 68.075 •CH2 OH + Fe3+ -+ 1 x 108 (rel.) ~1 y-r. C.k. rel. to k( R + QNO^ = 77G411

Fe2+ + CH2 0 + H

+

(8 ± 2) x 107

5 x 109

; obs. C(N03)3' and Fe2+

yields. Unpubl. data, C.N. Barnes and

G.V. Buxton. 78A322

68.076 CH3CHOH + Fe3+ 2.7 x 108 (rel.) ~1 y-T. C.k. rel. to A(R + CINO^J = 77G411

Fe2+ + H

+ + CH3 CHO

(3.8 ± 0.2) x 108

5 x 109

; obs. C(N02)3

~ and Fe2+

yields. Unpubl. data, C.N. Barnes and

G.V. Buxton. 78A322

68.078 (CH3 )2 COH + Fe3+ — (4.5 ± 0.4) x 108 ~1 p.r. D.k. at 270 nm in soln. contg. 1 74A074

Fe2+ + H

+ + (CH3 ) 2 CO

1.8 x 108 (rel.) ~1 y-r.

mol L*

1 2-PrOH, 2 x W* mol L'

1 Fe(C104)3 and 0.5 mol L'

1 HC104; /x = 1 mol L"

1

. C.k. rel. to A(R + C(N02)4) =

5 x 109

; obs. C(N02)3" and Fe2+

yields.

77G411

(5.8 ± 0.3) x 108 Unpubl. data, C.N. Barnes and

G.V. Buxton. 78A322

18
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L moF's" 1 ) PH Method Comment Ref.

69. Ferricyanide ion

69.001 •CH3 + FelCN),

3- (5 ± 1) x 106 6-7 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. dimethyl sulfoxide. 81A003

69.002 •CH2CH3 + FelCNV*- (5.0 ± 0.5) x 107 6-7 p.r. D.k. at 420 nm in N20-satd. soln. contg. diethyl sulfoxide. 81A003

69.002a (CH3)2CH + Fe(CN)6

3- (1.25 ± 0.5) x 109 6-7 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. di-(l-methylethyl) sulfoxide. 81A003

69.002b (CH3)3C + Fe(CN)6*- (3.6 ± 1.5) x 109 6-7 p.r. D.k. at 420 nm in N20-satd. soln. contg. di-(tert-butyl) sulfoxide. 81A003

69.014 •CH2 CH2 OH + FelCN)^ ~107 7 p.r. D.k. in soln. of 10'2 mol L“' ethylene contg. 10*2 mol L'

1 N2 0. 69G522

69.035 •CH2 C02 H + Fe(CN)6

3- 2 x 106 3.3 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. acetic acid. 81A003

69.043 •CH2 C1 + FelCNJg

3* <5 x 105 6-7 p.r. D.k. at 420 nm in N20-satd. soln. contg. methylene chloride. 81A003

69.045 •CHC12 + Fe(CN)6^ <5 x 10° 6-7 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. chloroform. 81A003

69.056 NH2 tHC02

" + FelCN)*,

3- 1 x 109 p.r. D.k. at 420 nm in soln. contg.

glycine. 76A082

69.075 •CH2 OH + FefCN)*

3" — 4.0 x 109 7 p.r. D.k. at 410 nm (ferricyanide) in 68G308

CH2 0 + H

+ + FelCN)^ soln. contg. MeOH. 69G522

(4.2 ± 0.4) x 109 ~6 p.r. Condy. change in N2 0-satd. soln. contg. MeOH.70G254

•CH2 0' -I- Fe(CN)63- 3.1 x 109 13 p.r. D.k. at 410 nm (ferricyanide) in 68G308

CH2 0 + FelCN)^ soln. contg. MeOH.

69.076 CH/HOH + FelCN^3* 5.3 x 109 7 p.r. D.k. at 410 nm in 0.1 mol L'

1 EtOH soln. 69G522

4 x 109 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. EtOH. 79N061

69.077 CH3CH2CHOH + Fe(CN)6

3' 3.7 x 109 7 p.r. D.k. at 410 nm in 0.1 mol L'1 1-PrOH soln. 69G522

69.078 (CH3)2 COH + FelCN)^ 4.7 x 109 7 p.r. D.k. at 410 nm in 0.1 mol L'

1 2-PrOH soln. 69G522

(5.6 ± 0.6) x 109 7.0 p.r. D.k. at 420 nm. 73A104

69.080 CH3COHCH2 CH3 + FefCN)*

3" 4.8 x 109 7 p.r. D.k. at 410 nm in 0.1 mol L

_1 2-BuOH soln. 69G522

69.081 (CH3 )2CHCHOH + FelCN)^

CH3(CH2 )3CHOH + FelCN^3-

3.0 x 109 7 p.r. D.k. at 410 nm in 0.3 mol L'

1 2-methyl-l-propanol soln. 69G522

69.082 (9 ± 2) x 108 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. 1-pentanol. 79N061

-CH2COH(CH2) 2- + FelCN)* 69.084 3- -» 2.6 x 109 7 p.r. D.k. at 410 nm in soln. contg. 76A103 R = 0 + FefCN^4- + H

+ 10"3 mol L'1 cyclobutanone and

0.1 mol L"

1 /er/-BuOH at 2°C;

k = 5.3 x 109 at 64° C; £„= 2.1 kcal mol" 1 (8.8 kj mol'1 )- 69.085 -CH2 tOH(CH2 )3- + FefCN)*3" — 2.3 x 109 7 p.r. D.k. at 410 nm in soln. contg. 10"3 76A103 R = 0 + Fe(CN)6

4_ + H

+ mol L"

1 cyclopentanone and 0.1 mol L’

1 /er<-BuOH at 2°C; k = 5.4

x 109 at 64°C; E, = 2.6 kcal mol"

1 (10.9 kj mol" 1 ). 69.086 -CH2 COH(CH2 )4- + Fe(CN)6

3' -> 1.8 x 109 7 p.r. D.k. at 410 nm in soln. contg. 10"3 76A103 R = 0 + FefCN),

3" + H

+ mol L"1 cyclohexanone and 0.1 mol L"

1 <ert-BuOH at 2°C; k = 5.0 x 109 at 64°C;

E, = 2.9 kcal mol" 1 (12.1 kj mol"1 ). (1.0 ± 0.2) x 109 p.r. D.k. at 420 nm in N20-satd. soln. contg. cyclohexanol. 79N061

69.087 -CH2 tOH(CH2 ) 5- + FefCN^3" — 2.1 x 109 7 p.r. D.k. at 410 nm in soln. contg. 10"3 76A103 R = 0 + FelCN^4- + H

+ mol L"

1 cycloheptanone and 0.1 mol L"

1 tert-BuOH at 2°C; k = 5.4 x 109 at 64°C; Et = 2.8 kcal mol" 1 (11.7 kj mol' 1 ). 69.088 -CH2 £OH(CH2) 6- -(- Fe(CN)6

3' — 2.2 x 109 7 p.r. D.k. at 410 nm in soln. contg. 10"3 76A103

R = 0 + Fe(CN)6

*- + H

+ mol L"

1 cyclooctanone and 0.1 mol L"

1 tert-BuOH at 2°C; k = 5.4 x 109 at 64°C; Et = 2.8 kcal mol' 1 (11.7 kj mol' 1 ).

19
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L moF's ') PH Method Comment Ref.

69.091 CH3 CH0S03

' + Fe(CN)6

3- ~ 2 x 108 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. ethylsulfate ion; values are given also for radicals produced from

reaction of OH with higher alkyl

sulfates.

79N061

69.092a •CH2 OCH3 + Fe(CN)6

3- (4.3 ± 0.23) x 109 6-7 p.r. D.k. at 420 nm in N2 0-satd. soln. contg. dimethyl ether. 81A003

69.097 CH3 (C0')CH2 C02’ + Fe(CN)6

3' (7.3 ± 0.7) x 108 7.0 p.r. D.k. at 420 nm in soln. contg. 73A104

acetoacetate ion (radical by

reaction with e ’). 69.100 •CH0HCH(NH2)C02- + Fe(CN)6

3- 3.2 x 109 7 p.r. D.k. at 410 nm in soln. contg. 0.3 mol L"

1 serine. 69G522

69.101 •CHOHCH2 OH + Fe(CN)6

3' 3.6 x 109 7 p.r. D.k. at 410 nm in soln. contg. 0.3 mol L"

1 ethylene glycol. 69G522

69.105 R + Fe(CN)6

3- 2.1 x 109 7 p.r. D.k. at 410 nm in soln. contg. 69G522

(R = Radicals from

polyethylene oxide) ~2% polyethylene oxide.

69.106 •CHOHCHOHCH2OH + Fe(CN)6

3 ~ 3.3 x 109 7 p.r. D.k. at 410 nm in soln. contg. 69G522

(+ CH2COHCH2 OH) 0.3 mol L’

1 glycerol. 69.108 R + Fe(CN)6

3’ 2.8 x 109 7 p.r. D.k. at 410 nm in soln. contg. 71G618

(R — Radicals from deoxyribose)

1.4 x 109 p.r.

0.3 mol L

_1 deoxyribose

Soln. contains 2-deoxy-D-ribose. 78A175

69.111 R + Fe(CN)6

3- 1.9 x 109 7 p.r. D.k. at 410 nm in soln. contg. 69G522

(R = Radicals from glucose) 0.3 mol L'

1 glucose. 69.115 •CHOHCO-f + Fe(CN)6

3- 5 x 108 7 p.r. D.k. at 410 nm in soln. contg. 0.3 mol L'

1 glycolate ion. 69G522

•CHOHC02H + Fe(CN)6

3- 1.0 x 108 3.4 p.r. D.k. at 420 nm in N20-satd. soln. 81A003

•CH(0)C02

' + Fe(CN)6

3’ 7.5 x 108 11.5 contg. glycolate. 69.117 CH3C0HC02

- + Fe(CN)6

3- 1.5 x 109 7 p.r. D.k. at 410 nm in soln. contg. 0.3 mol L”

1 lactate ion. 69G522

69.147 •C02- + Fe(CN)6

3’ 1.06 x 109 7 p.r. D.k. at 410 nm in soln. contg. 69G522

C02 + Fe(CN)6^ 0.3 mol L”

1 formate ion.

70. Pentacyanonitro8ylferrate(III) ion

70.075 •CH2 OH + Fe(CN)5N02- 6.7 x 108 8.5 p.r. P.b.k. in N2 0-satd. 0.5 mol L'

1 77A120

CH20 + H

+ + Fe(CN)sN03- MeOH soln. 70.078 (CH3 )2COH + Fe(CN)5 N02- 2.9 x 109 7.0 p.r. P.b.k. in N2 0-satd. 0.5 mol L

_1 2-PrOH soln. 77A120

70.147 •C02- + Fe(CN)5N02~ -+ 3.7 x 108 7 p.r. P.b.k. at 450 nm in N2 0-satd. 69G052

C02 + Fe(CN)5N03 -

4.0 x 108 7.0 p.r.

2 x 10”2 mol L

_1 formate soln.; / = 0.02.

P.b.k. in N2 0-satd. 0.1 mol L“’ formate soln. 77A120

71. Pentacyanonitro8ylferrate(III) radical ion (electron adduct)

71.006 •CH2 C(CH3 )2C02- + Fe(CN)5 N03- (2.0 ± 0.3) x 109 6.0- p.r. D.k. at 380 nm (nitrosyl radical, e = 3.5 x 103 L mol'1 cm'

1 ), 79A134

Fe(CN)5N(0)CH2C(CH3 )2C024- 7.5

as well as p.b.k. in soln. contg. 0.3 mol L"

1 pivalate ion and 5 x 10"4 mol L'

1 Fe(CN)5N02'. 71.012 •CH2C(CH3)2 NH3+ + Fe(CN)sN03' (1.2 ± 0.2) x 10 10 6.0- p.r. D.k. at 380 nm (nitrosyl radical, 79A134

Fe(CN)5N(0)CH2C(CH3 ) 2 NH32- 7.5 € = 3.5 x 103 L mol' 1 cm'

1 ). as well as p.b.k. in soln. contg. 0.3 mol L'

1 /err-butylamine and 5 x 10"4 mol L'

1 Fe(CN)s N02'. 71.013 •CH2C(CH3)(NH3 + )C02- + (1.6 ± 0.2) x 109 6.0- p.r. D.k. at 380 nm (nitrosyl radical. 79A134

Fe(CN)5N03’ 7.5 € != 3.5 x 103 L mol’ 1 cm'1 ), Fe(CN)5N(0)CH2C(CH3 )(NH3)C02

3' as well as p.b.k. in soln. contg. 0.3 mol L'

1 2-aminoisobutyrate ion and

5 x 10-4 mol L'

1 Fe(CN)5N02-

20
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L molds'1 ) PH Method Comment Ref.

71.016 •CH2C(CH3 ) 2 OH + Fe(CN)5N03" — (2.5 ± 0.4) x 109 6.0- p.r. D.k. at 380 nm (nitrosyl radical, 79A134

Fe(CN)s N(0)CH2 C(CH3 )2 0H3- 7.5 € = 3.5 x 103 L mol-1 cm"1 ), as well as p.b.k. in soln. contg. 0.3 mol L"

1 <ert-BuOH and 5 x 10"4 mol L"

1 Fe(CN)sN02". 71.017 •CH2 C0H(CH3)C02

" + (6.3 ± 0.9) x 108 6.0- p.r. D.k. at 380 nm (nitrosyl radical, 79A134

Fe(CN)s N03" — 7.5 e = 3.5 x 103 L mol" 1 cm"1 ), Fe(CN)5N(0)CH2 C0H(CH3)C02*- as well as p.b.k. in soln. contg. 0.3 mol L"

1 2-hydroxyisobutyrate

ion and 5 x 10"4 mol L"

1 Fe(CN)s N02". 71.055 CH3CON(CH3)CH2 + Fe(CN5)N03' (3.5 ± 0.5) x 10 10 6.0- p.r. D.k. at 380 nm (nitrosyl radical, € = 3.5 x 103 L mol" 1 cm"1 ), 79A134

-+ Fe(CN)5N(0)CH2 N(CH3)C(0)CH3

3- 7.5

as well as p.b.k. in soln. contg. 0.3 mol L"

1 AyV-dimethylacetamide and

5 x 10"4 mol L"

1 Fe(CN)5N02".

72. 72.016 Tris( 1 , 1 0-phenanthroline )iron( III ) ion •CH2 C(CH3)2OH + Fe(phen)33+ ~107 acid p.r. P.b.k. in 9oln. contg. /e/t-BuOH, 79A174 —*• Fe(phen)32+ H2 S04 and HC104; slower process

follows fa9t H reaction.

Deuterohemin See 222.

Hemin See 224.

Hemin c See 225.

Methemerythrin See 256.

Ga

73. Gallium(II) ions 73.075 •CH2OH + Ga2+ -+ 1.1 x 109 2.3 p.r. D.k. in soln. contg. MeOH; Ga(II) 79A190 CH20 + H

+ + Ga + formed from e

~ + Ga(III); cor. to •CH2OH + Ga(OH) + -* 1.0 x 109 2.9 1= 0. CH2 0 + H2 0 + Ga+ •CH20" + GalOHlg

4- —> prod. 7.8 x 108 12.0 73.076 •CH3CHO- + GalOH^4" - prod.

(CH3)2CO" + Ga(OH)64_ -> prod.

1.2 x 109 12.0 p.r. D.k. in soln. contg. EtOH; Ga(II) from eaq" + Ga(III); cor. to /= 0. 79A190

73.078 1.7 x 109 12.0 p.r. D.k. in soln. contg. 2-PrOH; Ga(II) from eaq" + Ga(IlI); cor. to 1= 0. 79A190

Hg

74. Mercuric bromide

74.078 (CH3)2 tOH 4- HgBr2 — (2.4 ± 0.6) x 109

p.r. P.b.k. in N2 0-satd. 0.1 mol L"

1 76A042

HgBr + Br" + H

+ + (CH3) 2 CO 2-PrOH soln. 74.147 •C02

" + HgBr2 — C02 -I- Hg(I) <9 x 109 p.r. P.b.k. at 360 nm in soln. contg. formate ion; based on max. optical density in various solns.; rel. rates are -C02

" 1.0, (CH3)2£OH 0.89, CH3 CHOH 0.87, and -CH2 OH 0.63.

76A087

75. 75.078 Mercuric chloride (CH3)2 tOH + HgCl2 -

HgCl + Cl" + H

+ + (CH3)2CO

(2.0 ± 0.2) x 109 p.r. P.b.k. in N2 0-satd. 0.1 mol L

1 2-PrOH soln. 73G043

76A042

76. 76.076 Mercuric iodide CH3CHOH + Hgl2 (7 ± 2.5) x 108 p.r. P.b.k. in N20-satd. 9oln. contg. 78A165

EtOH.

21
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol : s

’) pH Method Comment Ref.

76.078 (CH3)2COH + Hgl2 -> (2.0 ± 0.5) x 109 p.r. P.b.k. in N2 0-satd. soln. contg. 76A042

Hgl + r + H

+ + (CH3)2CO

(1.0 ± 0.5) x 109 p.r.

O. 1 mol L'

1 2-PrOH.

P. b.k. in N2 0-satd. soln. contg. 2-PrOH. 78A165

76.147 •C02 + Hgl2 (3.0 ± 1.0) x 109 p.r. P.b.k. in N2 0-satd. soln. contg. formate ion. 78A165

77. Mercurous cyanide

77.016 •CH2 C(CH3)2OH + HgCN 1.6 x 109 p.r. Calcd. from increase in decay rate

at 285 nm in soln. contg. tert-BuOH

and Hg(CN)2 ; 2*(HgCN + HgCN) = 3.4 x 109

.

75A203

77.075 •CH2 OH + HgCN

CH3CHOH + HgCN

4.0 x 109 p.r. Calcd. from increase in decay rate

at 285 nm in soln. contg. MeOH and Hg(CN)2 ; 2£(HgCN + HgCN) = 3.4 x 109

.

75A203

77.076 3.9 x 109 p.r. Calcd. from increase in decay rate

at 285 nm in soln. contg. EtOH and Hg(CN)2; 2&(HgCN + HgCN) = 3.4 x 109

.

75A203

77.078 (CH3) 2£OH + HgCN 2.4 x 109 p.r. Calcd. from increase in decay rate

at 285 nm in soln. contg. 2-PrOH and Hg(CN)2 ; 2&(HgCN + HgCN) = 3.4 x 109

.

75A203

78. Mercuric cyanide

78.147 •C02

- + Hg(CN)2 - C02 + Hg(I) (3.4 ± 0.2) x 109 p.r. P.b.k. at 285 nm in N2 0-satd. soln. contg. formate. 75A203

79. 79.078 Mercuric thiocyanate

(CH3)2tOH + Hg(SCN)2 HgSCN + SCN- + H

+ + (CH3) 2 CO

I

Iodine

(2.2 ± 0.5) x 109 p.r. P.b.k. in N2 0-satd. soln. contg. 0.1 mol L’

1 2-PrOH. 76A042

80. 80.001 •CH3 + I 2 -> .[CH3

I 2] 6.0 x 109 (rel.) p.r. C.k. with 02 ; radical from Mel;

rel. to &(CH3 + 02) = 4.7 x 109. 67G041

81. Iodate ion 81.076 ch3Choh + I03

- <5 x 106 6 p.r. D.k. in N2 0-satd. soln. contg. EtOH. 72A018

CH3tHO' + 103- (7.5 ± 0.2) x 108 11.8

Ir

Iridium(IV) ions

81a. Hexachloroiridate(IV) ion

81a.001 •CH3 + IrCl

2" (1.15 ± 0.5) x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln.; radical from dimethyl sulfoxide. 81A003

81a.002 •CH2 CH3 + IrCl6

2'

(CH3)2 CH + IrCl6

2-

(3.1 ± 0.8) x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln.; radical from diethyl sulfoxide. 81A003

81a.002a (3.6 ± 0.4) x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln.; radical from di-(l-methylethyl)

sulfoxide.

81A003

81a.002b (CH3)3C + IrCl6

2- (3.8 ± 1.1) x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln.; radical from di-(tert-butyl) sulfoxide.

81A003

81a.005 •CH2CH2 C1 + lrCl6

2 - ~1 x 109 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. 1,2-dichloroethane. 81A003

81a.014 •CH2 CH2OH + IrClf) 2- ~ 2 x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln. contg. ethylene. 81A003

81a. 016 •CH2C(CH3)2OH + IrClf)2- (1.2 ± 0.16) x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln. contg. <ert-BuOH. 81A003

81a.020 •CH2 CHO + IrCl6

2' 1.7 x 109 7 p.r. D.k. at 490 nm in soln. contg. 81A003

2-chloroethanol. 22
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol ’s ') pH Method Comment Ref.

81a.035 •CH2 C02- + IrCl6

2- 4.2 x 108 7 p.r. D.k. at 490 nm in N20-satd. soln. 81A003

•CH2C02 H + IrCl6

2' 1.4 x 109 3.3 contg. acetate. 81a. 040a -o2 cChch2 co2

- 4 IrCl6

2- 1.1 x 108 7 p.r. D.k. at 490 nm in N2 0-satd. soln. 81A003 H02CtHCH2 C02H + IrCl6

2- 4.6 x 108 3.3 contg. succinate. 81a.043 •CH2C1 4 irci6

2- ~1 x 109 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. dichloromethane. 81A003

81a. 048 •CC13 + IrCl6

2- 2.8 x 107 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. carbon tetrachloride. 81A003

81a. 075 •CH2OH + IrCl6

2'

CHjtHOH 4 IrCl6

2-

6.0 x 109 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. MeOH.81A003

81a.076 4.5 x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln. contg. EtOH. 81A003

(CH3)2COH 4 IrCl6

2' 81a. 078 4.7 x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln. contg. 2-PrOH. 81A003

81a.092 •CH2OCH3 + IrCl6

2'

CH3tHOC2H5 4 IrCl6

2-

6.5 x 109 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. dimethyl ether. 81A003

81a. 093 5.7 x 109 6-7 p.r. D.k. at 490 nm in N2 0-satd. soln. contg. diethyl ether. 81A003

-CH2CH0CH2CH2 0- 4 IrClg

2' 81a. 104 5.4 x 109 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. dioxane. 81A003

81a. 115 •CHOHC02H + IrCl6

2" 2.3 x 109 3.3 p.r. D.k. at 490 nm in N20-satd. soln. 81A003 •CHOHC02

- + IrClg

2' 2.0 x 109 6.9 contg. glycolate. •CH(0-)C02

- 4 IrCl6

2- 1.8 x 109 10.7

81a. 147 •C02- 4 IrCl6

2' 1.7 x 109 6-7 p.r. D.k. at 490 nm in N20-satd. soln. contg. formate. 81A003

82. 82.147

83. 83.001

Mn

Manganese(II) ions •C02

- + Mn2+ — C02 + Mn +

Permanganate ion •CH3 + Mn04

~

<2 x 10s

1.05 x 109 6-7

p.r.

p.r.

No effect of Mn2+ on d.k. of -CO^

at 280 or 256 nm in N2 0-satd. soln. contg. 10”2 mol L”

1 formate.

D.k. at 545 nm in N20-satd. soln.;

76A109

81A003

83.002 •CH2 CH3 4 Mn04* ~2 x 109 6-7 p.r.

radical from dimethyl sulfoxide. D.k. at 545 nm in N20-satd. soln. 81A003

83.016 •CH2C(CH3)2OH 4 Mn04

- 1.3 x 109 6-7 p.r.

radical from diethyl sulfoxide. D.k. at 545 nm in N2 0-satd. soln. 81A003

83.043 •CH2C1 + Mn04

- ~ 1 x 109 6-7 p.r.

contg. tert-BuOH.

D.k. at 545 nm in N2 0-satd. soln. 81A033

83.045 •CHC12 + Mn04

' ~1 x 109 6-7 p.r.

contg. dichloromethane.

D.k. at 545 nm in N2 0-satd. soln. 81A003

83.048 •CC13 + Mn04

' ~4 x 108 6-7 p.r.

contg. chloroform.

D.k. at 545 nm in N2 0-satd. soln. 81A003

83.078 (CH3)2COH 4 Mn04

- (4.2 ± 0.4) x 109 7.0 p.r.

contg. carbon tetrachloride. D.k. at 545 nm in N2 0-satd. soln. 73A104

83.097 CH3C(0*)CH2 C02

- 4 Mn04

- (4.8 ± 0.5) x 109 9.2 p.r.

contg. 2-PrOH.

D.k. at 545 nm in Ar-satd. soln. 73A104

83.104 -CH2CH0CH2 CH20- 4 Mn04

- (6.5 ± 1.3) x 109 6-7 p.r.

contg. acetoacetate and tert-BuOH.

D.k. at 545 nm in N2 0-satd. soln. 81A003

84. 84.078

Nitrogen compounds

Hydroxylamine

(CHj)2COH 4 NH2 OH — -nh2 <3 x 103 <2 chem.

contg. dioxane.

Est. from esr in Ti(IIl)-NH 2 OH soln. 76D419

contg. 2-PrOH.

23
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

85. Nitrous oxide

85.078 (CH3)2CO- + N20 (3.8 ± 0.4) x 104

(rel.)

13.5 y-r. Est. from G(acetone) based on an assumed mechanism and values for competing reactions.

72G167

86. 86.076Nitrite ion ch3 Choh + N02- <5 x 106 6 p.r. D.k. in N2 0-satd. EtOH soln. 72A018

87. 87.076

87.078

Nitrate ion ch3£hoh + no3

- (CH3)2COH + N03

- <5x 106 28

6 p.r. y-r.D.k. in N2 0-satd. EtOH soln. Calcd. from G for destruction of N03

‘ in soln. of 0. 1-0.2 mol L'

1

72A018

80N062

acetone, 0.2-0.4 mol L'

1 2-PrOH and

2.5 x 10^ mol L"

1 Ag+ and 10~3 mol L'

1 Na dodecylsulfate assuming G(R) = 5.8 and 2£(R + R) =

1.4 x 109.

Ni

88. Nickel(I) ion 88.004 c-C5H9 + Ni + C5 H9Ni +

2.8 x 109 p.r. D.k. at 300 nm (as well as p.b.k.)

in soln. contg. NiS04 and cyclopentane. 74A037

88.016 •CH2C(CH3) 2OH + Ni + —

Ni2+ + CH2 = C(CH3 )2 + OH3 x 109 p.r. D.k. at 300 nm (Ni +

) in soln. contg. NiS04 and Jert-BuOH; assume

G(Ni+

) = G(R) = 2.7.

74A037

88.075 •CH2OH + Ni + -* NiCH2OH+

4.2 x 109 p.r. D.k. at 300 nm (as well as p.b.k.

at 250 nm); assume G(Ni +

) = G(R) = 3.2;

soln. contains NiS04 and MeOH.

74A037

88.076 CH3 CHOH + Ni + — NiCHOHCH3 +

2.3 x 109 p.r. D.k. at 300 nm (as well as p.b.k.)

in soln. cont. NiS04 and EtOH. 74A037

88.078 (CH3)2COH + Ni +— NiC(OH)(CH3)2 +

1.4 x 109 p.r. D.k. at 300 nm (as well as p.b.k.)

in soln. contg. NiS04 and 2-PrOH. 74A037

88.147

89.

•C02- + Ni + -+ NiC02

Nickel(II) ions

6.6 x 109 5.0 p.r. D.k. at 300 nm (as well as p.b.k.)

in soln. contg. NiS04 and formate ion. 74A037

89.016 •CH2C(CH3)2OH + Ni2+ <106 p.r. Est. from lack of increase in Ni +

in 0.1 mol L~' Ni2+ on addn. of 0.1 mol L'

1 teri-BuOH.

75A027

89.075 •CH2OH + Ni2+ <102 p.r. Est. from lack of increase in Ni +

in 0.1 mol L'

1 Ni2+ on addn. of 0.1 mol L"

1 MeOH.

75A027

89.078 (CH3)2 COH + Ni2+ <106 p.r. Est. from lack of increase in Ni +

in 0.1 mol Lf1 Ni2+ on addn. of 0.1 mol L1 2-PrOH.

75A027

89.147

90.

•C02- + Ni2+ C02 + Ni +

Tetracyanonickelate(II) ion

102 <k < 10s p.r. Est. from lack of increase in Ni +

in 0.1 mol L"

1 Ni2+ on addn. of

0.1 mol L*

1 formate ion.

75A027

90.147 •C02

- + Ni(CN)4

2- C02 + Ni(CN)4

3- (1.2 ± 0.1) x 109 p.r. P.b.k. at 240 nm in N20-satd. soln. contg. 0.1 mol L*

1 formate ion. 74A072

91. (5,7,7,12,12,14-Hexamethyl-l,4,8,ll-tetraazacyclotetradecane)nickel(II) ion

91.147 •C02* + Ni I — Ni l + C02 5.7 x 109 7.0 p.r. P.b.k. in Ar-satd. soln. contg. 0.1 mol L'

1 formate; Ni(I) is also formed by reaction of eaq

~.

76A039

92. (5,7,7,12,12,14)Hexamethyl-l,4,8,ll-tetraazacyclotetradeca-4,ll-diene)nickel(II) ion

92.147 •C02

- + Ni Z, — Ni I + C02 6.7 x 109 7.0 p.r. P.b.k. in Ar-satd. 0.1 mol L

1 formate. 76A039

24
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ) pH Method Comment Ref.

93. Oxygen

93.001 •CH, + 02 — CH3 02

- (4.7 ± 0.7) x 109

(3.2 ± 0.4) x 108

93.002 •CH2 CH3 + 02 —

C2 H5 02

- (2.9 ± 0.8) x 109

93.004 c-C5 H9 + 02 — R02

- (4.9 ± 0.6) x 109

93.007 R + 02 —> R02

- (R = Radicals from oleate)

1.0 x 109

93.008 R + 02 —» R02

- (R = Radicals from linoleate)

3 x 108

93.009 R -T 02 — R02

* (R = Radicals from linolenate)

3 x 108

93.010 R + 02 —* R02

- (R = Radicals from arachidonate)

2 x 108

93.014 •CH2CH2 OH + 02 — -o2ch2ch2 oh (6.6 ± 1.3) x 109

93.035 •CH2C02

' + 02 — -0

2CH2C02

‘ (5.0 ± 0.8) x 108

(2.1 ± 0.3) x 109

93.036 •CH2 C02 CH3 -T 02 —> •02CH2C02 CH3 (1.8 ± 0.2) x 109

93.052 CH3CHN +

(C2 H5)3 + 02 -* addn. 93.057 NH2 CHC02

- + o2 ~ 1 x 109

93.062 R -f- 02 — R02

- (1.2 ± 0.1) x 109 (R = Radical from glycine anhydride)

(2.8 ± 0.3) x 108

93.063 R -f- 02 — R02

* (1.0 ± 0.2) x 109 (R = Radical from alanine anhydride)

(1.1 ± 0.2) x 109

93.064 R -f 02 — R02

- (R = Radical from sarcosine anhydride)

(9 ± 2) x 108

93.067 R -f 02 — R02

- (R = Radicals from acetyldiglycine)

(5.5 ± 0.8) x 108

93.075 •CH2OH + o2 — -o2 ch2oh 4.9 x 109 (rel.)

(4.2 ± 0.5) x 109

93.076 ch3 Choh + o2 — -0

2 CH0HCH3 3.6 x 108 (rel.)

4.6 x 109 (rel.)

93.077 ch,ch2Choh + 02 4.7 x 109 (rel.)

nat p.r. P.b.k. at 260 nm in soln. contg. CH3 Br, 02 and N20 or SCN~; Ea = 3.5 ± 0.5 kcal mor'(14.6 kj mol' 1 ).

67G041

5.5 p.r. P.b.k. at 250 nm in soln. contg. CH4 and 02

. 72G445

nat p.r. P.b.k. at 270 nm in soln. contg. 6 x 10"’ mol L'

1 02 and ethane. 75A055

7 p.r. P.b.k. at 270 nm in N20-satd. soln. contg. cyclopentane. 74A051

13 p.r. P.b.k. at 280 nm in 02-N20-contg. ~ 0.4-0.8 x 10'3 mol L'

1 soap soln. 78A365

10.5, 13

p.r. D.k. at 280 nm in 02-N2 0-contg.

soln. of 10"5 mol L'

1 soap and

0.02 mol L'

1 phosphate.

78A365

10.5, 13

p.r. D.k. at 280 nm in 02 -N2 0-contg.

soln. of 0.4-0.8 x 10'3 mol L'

1 soap. 78A365

13 p.r. D.k. at 280 nm in 02 -N20-contg.

soln. of ~ 0.4-0.8 x 10'3 mol L'

1 soap. 78A365

1 p.r. P.b.k. at 240 nm; radical from OH addn. in soln. contg. ethylene-02 (99:1); includes 02 reaction with •C2 H5 from H addn.

67G269

4-9 p.r. D.k. at 350 nm in N2 0-satd. soln. contg. acetate ion. 73A052

8.2 p.r. D.k. at 366 nm in N2 0-satd. 0.01 mol L'

1 acetate soln.; cor. for &(R +

R) = 5.5 x 108.

76A082

4 p.r. D.k. at 340 nm in soln. contg. methyl

chloroacetate and formate ion. 78A402

13 p.r. Est. that k( R + R)/&(R -f- 02) = 10. 78A095

7.9 p.r. D.k. at 307 nm in 02-N20-satd.

0.2 mol L"

1 glycine soln.; c.k. with

ferricyanide also gave ~109 assuming

2&(R + ferricyanide) = 1 x 109.

76A082

5.0 12.0p.r. D.k. at 360 nm in N2 0-satd. soln. contg. glycine anhydride.71G554

5.4 12.0

p.r. D.k. at 360 nm in N20-satd. soln. alanine anhydride. 71G554

5.2 p.r. D.k. at 360 nm in N20-satd. soln. contg. sarcosine anhydride. 71G554

5.5 p.r. D.k. at 330 nm in N2 0-satd. soln. contg. acetyldiglycine. 73A052

7 p.r. C.k. in 0.1 mol L'

1 MeOH soln. contg. ferricyanide; Ar(R + ferri- cyanide) = 4.0 x 109

.

69G522

10.7 p.r. Calcd. from abs. at 248 nm

assuming &[02] = rate of 02

* formn. from peroxy radical.

74A099

7 p.r. C.k. with RNO (Ar(R -f RNO) =

2.4 x 109

]. 69G156

7 p.r. C.k. in 0.1 mol L'

1 EtOH soln. contg. ferricyanide; A:(R + ferri- cyanide) = 5.3 x 109

.

69G522

7 p.r. C.k. in 0.1 mol L'

1 1-PrOH soln. contg. ferricyanide; £(R + ferri- cyanide) = 5.3 x 109

.

69G522

25
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 1 s

-1

) pH Method Comment Ref.

93.078 (CH3)2fiOH + 02 — 6.2 x 108 (rel.) 7 p.r. C.k. with RNO [*(R + RNO) =

3.2 x 109

]. 69G156

(CH3)2C(0H)02

. 4.2 x 109 (rel.) 7 p.r. C.k. in 0.1 mol L"

1 2-PrOH soln. 69G522

contg. ferricyanide; £(R + ferri- cyanide) = 4.7 x 109

. 3.5 x 109

(rel.) 5-6 p.r. C.k. in N2 0-satd. 0.1 mol L'

1 2-PrOH

soln. with />-nitroacetophenone; A(R +

PNAP) = 3.8 x 109.

71G618

(4.5 ± 0.5) x 109 ~1 p.r. D.k. at 290-300 nm in air-satd. soln. 74A074

contg. 1 mol L'

1 2-PrOH and 0.5 mol L’

1 HC104

. 93.080 CH3CH2tOHCH3 + 02

(CH3)2CHCHOH + 02

4.0 x 109(rel.) 7 p.r. C.k. in soln. contg. 0.3 mol L"

1 2-BuOH with ferricyanide; &(R +

ferricyanide) — 4.8 x 109.

69G522

93.081 3.4 x 109

(rel.) 7 p.r. C.k. in soln. contg. 0.3 mol L"

1 2-methyl-l-propanol with ferricyanide; k(R + ferricyanide) = 3.0 x 109

.

69G522

CH3C02CH2

-)- 02 — CH3C02CH202 93.090 - (1.35 ± 0.15) 6.4 p.r. P.b.k. at 260 nm as well as d.k. at 78A402

x 1010 260 nm in soln. contg. methyl

acetate and N20. 93.100 •CH0HCH(NH2)C02

- + 02 2.4 x 109

(rel.) 7 p.r. C.k. in 0.3 mol L"

1 serine soln. 69G522

contg. ferricyanide; &(R -f- ferri- cyanide) = 3.2 x 109

. 93.101 CHOHCHjjOH + 02 3.2 x 109

(rel.) 7 p.r. C.k. in soln. contg. 0.3 mol L"

1 69G522

ethylene glycol with ferricyanide; A(R + ferricyanide) = 3.6 x 109

. 93.105 R + 02 (1.9 - 2.9) x 109 7 p.r. C.k. in soln. contg. ~2% 69G522

(R = Radicals from polyethylene oxide with ferricyanide; polyethylene oxide) k( R + ferricyanide) = 2.1 x 109

. 93.106 •CHOHCHOHCH2OH + 02 3.3 x 109

(rel.) 7 p.r. C.k. in soln. contg. 0.4 mol L"

1 69G522

(+ CH2OHCOHCH2OH) glycerol with ferricyanide; £(R + ferricyanide) = 3.3 x 109

. 93.108 R + 02 2.0 x 109

(rel.) 5-6 p.r. C.k. with ferricyanide in N2 0-satd. 71G618

(R = Radicals from deoxyribose) soln. contg. deoxyribose; rel. to &(R

4- ferricyanide) = 2.8 x 109

. 93.111 R 4- 02 1.6 x 109

(rel.) 7 p.r. C.k. in soln. contg. 0.3 mol L"

1 69G522

(R = Radicals from glucose) glucose and ferricyanide; £(R +

ferricyanide) = 1.9 x 109. 93.113 •A + 02 <5 x 102 8.6 p.r. D.k. at 360 nm in N2 0-satd. soln. 75A240

(A = Radical from ascorbate) ~6 x 102 y-r.

contg. ascorbate ion. Obs. rate of consumption of 02

. 78A417

93.115 •chohco2

- + o2

ch3Cohco2

- + 02

1.8 x 109 (rel.) 7 p.r. C.k. in 0.3 mol L"

1 glycolate soln. contg. ferricyanide; £(R + ferri- cyanide) = 5 x 108

.

69G522

93.117 2.6 x 109

(rel.) 7 p.r. C.k. in 0.3 mol L”

1 lactate soln. 69G522

<IH3C(62)(0H)C02

- contg. ferricyanide; &(R + ferri- cyanide) = 1.5 x 109

. (3.5 ± 0.5) x 108 7.3 p.r. D.k. at 270 nm in N2 0-satd. soln. contg. lactate ion. 73A052

93.123 •CH(OH)2 + 02 .02CH(0H)2 7.7 x 108 5.7 p.r. D.k. at 250 nm in N2 0-satd. soln. 71G424 ^ -02CH(0H)0- + H

+

(4.5 ± 0.7) x 109 3.5- p.r.

contg. formaldehyde, as well as condy. increase. Condy. increase in oxygenated soln. 80A282

CCl3t(OH)2 + 02 -> •0

2 C(0H)2CC13

6.5 contg. 5 x 10"3 mol L"

1 formaldehyde;

products are formate and H2 02

. 93.126 (1.0 ± 0.2) x 108 5.9 p.r. D.k. at 250 nm in N2 0-satd. soln. contg. chloral. 73G062

93.141 R + 02 5.3 x 109 11 p.r. D.k. 67G729

(R = Electron adduct of 2.2 x 109 p.r. D.k. 73G097

dimethyl fumarate)

26
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mop's"

1 ) pH Method Comment Ref.

93.147 •CO2

“|” O2 CO2”|” O2 7.7 x 108 (rel.) 7 p.r. C.k. with RNO in N2 0-std. soln. contg. formate; £(R + RNO) = 1.84

x 109.

69G156

2.4 x 109(rel.) 7 p.r. C.k. with ferricyanide in 0.3 mol L

" 1 formate soln.; £(R + ferricyanide) = 1.06 x 109

.

69G522

(2.0 ± 0.4) x 109 8.0 p.r. P.b.k. at 260 nm in 0.1 mol L

' 1 formate soln. satd. with oxygen. 76A072

(4.2 ± 0.4) x 109 6.8 p.r. D.k. at 270 nm and 300 nm in 0.18 mol L

" 1 formate ion. 76A132

1 x 109 (rel.) 1-4 p.r. Est. from buildup of C(N02)3" in 02-satd. 0.01 mol L

" 1 HC02 H contg. C(N02)4; rel. to k(R + TNM) =

4 x 109.(336.147)

78A177

94. Hydrogen peroxide

94.001 •CH3 + H2 O2 < 106 nat p.r. Addn. of 10

-3 and 10

~2 mol L' 1 H202 had no effect on second order d.k. of -CH3

. Suggested that reaction is slow compared to R + R and may

form H02

.

75A055

94.003 •C5Hn + H202 3.4 x 104

(rel.) y-r. Est. from dose rate effect on 76A254

G(H202), assuming 2A:(R + R) = 2 x 109 in soln. contg. 5 x 10

"3 mol L

" 1 pentane and 10

"2 mol L

”1 N20. 94.004 c-C5H9 + H2 02 4.6 x 104

(rel.) y-r. Est. from dose rate effect on 76A254

G(H202), assuming 2£(R + R) = 1.5 x 109 in soln. contg. 2.5 x 10

'3 mol L

' 1 cyclopentane and 10

"2 mol L

' 1 N20. 94.016a R + H202 3.7 x 104

(rel.) y-r. Est. from dose rate effect on 76A254

(R = Radicals from cyclopentene G(H2 02), assuming 2&(R + R) = 1.5 x + OH, 73% addn.. 109

, in soln. contg. 8.2 x 10

"3 mol L

" 1 23% abstraction) cyclopentene and 10

~2 mol L

' 1 N20. 94.075 •CH2 OH -(- H2 02 -* (4.0 ± 0.4) x 104 y-r. Calcd. from dose rate effect on 70G338

CH20 + H20 + OH (rel.) H202 redn. in 0.99 mol L

" 1 MeOH soln. assuming 2A(R + R) = 2.4 x 109

. (2.3 ± 0.8) x 104 chem. Calcd. from esr of Ti(III)—

H

2 02 74D144

(rel.) soln. contg. MeOH and tert-BuOH; 2A(R + R) = 2 x 109

. 94.076 ch3Choh + H2 02 — 1.5 x 10s (rel.) y-r. Calcd. from dose rate effect on 67G094

CH3 CHO + H2 0 + OH G(H2 02) in soln. contg. EtOH assuming 2k(R + R) = 2.0 x 109

. 94.078 (CH3) 2COH + h2 o2 5 x 10s (rel.) 1,7 phot. Esr; effect of [H202 ] on [R] in 71D227 CH3COCH3 + H2 0 + OH soln. contg. 2-PrOH and acetone; 2*(R + R) = 1-4 x 109

. 94.093 ch3Choc2 h5 + h2o2 (5.5 ± 1.1) x 104 chem. Calcd. from esr in Ti(III)-H2 02 74D144

(rel.) soln. contg. E^O; assumed

2k(R + R) = 3 x 109

. 94.094 -OCH(CH2 ) 3- + h2o2 3.0 x 104

(rel.) chem. Calcd. from esr in Ti(lII)—

H

2 02 soln. contg. tetrahydrofuran; assumed 24(R + R) = 3 x 109

.

74D144

94.104 -0tHCH2 0(CH2)2- + h2o2 (3.0 ± 0.6) x 104 chem. Calcd. from esr in Ti(III)-H2 02 74D144

(rel.) soln. contg. dioxane and tert-BuOH; assumed 2A:(R + R) = 2 x 109

. 94.124 •CH(OCH3) 2 “I- H2 O2 (1.1 ± 0.3) x 106 chem. Calcd. from esr in Ti(III)—

H

2 02 74D144

(rel.) soln. contg. dimethoxymethane; assumed 2£(R + R) = 2 x 109

. 94.125 -OCHOfCHJjj- + H2 02 > 6 x 104 (rel.) chem. Calcd. from esr in Ti(III)-H 2 02 74D144

soln. contg. dioxolane; assumed

2A(R + R) = 3 x 109

. 94.147 •C02 "f* H202 <7 x 10s (rel.) 7 phot. Calcd. from assumed chain mechanism 63F005

in C0-H202 soln.; k < 2.2 x 10° assuming 2A(R + R) < 10

l0

, recalcd.

in 74D144 assuming 2£(R + R) = 3 * 109

27
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ’) pH Method Comment Ref.

Pb

95. Lead(I) ions 95.075 •CH2 OH + Pb + — PbCH2OH +

2.9 x 109

95.076 CH3CHOH + Pb + PbCHOHCH3 +

1.7 x 109

95.078 (CH3)2COH + Pb + ^ 1.1 x 109 PbC(CH3 )2 OH+

95.096 •CHOHC(CH2OH)3 + Pb + -+ 7.0 x 108 PbCHOHC(CH2 OH)3 +

96. Lead(II) ions 96.078 (CH3)2COH + Pb2+ — 3.0 x 104 (CH3)2CO + Pb+ + h

+

p.r. D.k. at 300 nm (Pb +

) in soln. contg. 76A170

Pb2+ and MeOH, knowing initial [R] and [Pb +

]; cor. for R + R.

p.r. D.k. at 300 nm (Pb +

) in soln. contg. 76A170

Pb2+ and EtOH, knowing initial [R] and [Pb +

]; cor. for R + R.

p.r. D.k. at 300 nm (Pb +

) in soln. contg. 76A170

5 x 10"4 mol L’

1 Pb2+ and 5 x 10”2 mol L’

1 2-PrOH knowing initial [R] and

[Pb +

]; cor. for R + R.

p.r. D.k. at 300 nm (Pb +

) in soln. contg. 76A170

Pb2+ and pentaerythritol knowing

initial [R] and [Pb +

]; cor. for R + R.

P.b.k. at 300 nm in 1 mol L'

1 2-PrOH 76A170

and 1 mol L”

1 Pb2+ during 100 pis after pulse; Pb + formed initially by + Pb2+

-

Pt

97. tr<ms-Dichlorobi8(ethylenediamine)platinum(IV) ion

97.075 -CH2 OH + Pt(en)2 Cl2 2+

Pt(III) (6.9 ± 1.0) x 108

97.078 (CH3)2COH + Pt(en)2 Cl22+

(8.1 ± 1.1) x 108

Pt(III)

Rh

98. Tris(2,2'-bipyridine)rhodium(III) ion

98.075 -CH2 OH + Rh(bpy)33+

(2.2 ± 0.2) x 108 98.078 (CH3)2 COH + Rh(bpy)33+

(2.9 ± 0.3) x 109 98.147 -C02- + Rh(bpy)33+

(6.2 ± 0.6) x 109

98a. Tris(l,10-phenanthroline)rhodium(III) ion

98a. 075 -CH2OH + Rh(phen)3 3+ -* 4 x 108 addn. to ligand 98a.076 CH3 CHOH + Rh(phen)33+ 2.5 x 109 addn. to ligand 98a. 078 (CH3) 2COH + Rh(phen)33+ - 3.2 x 109 Rh(phen)3

2 +

Ru

Ruthenium(II) ions

99. Tris( 2,2 '-bipyridine )ru t henium( II

)

ion 99.016 •CH2 C(CH3)2OH + Ru(bpy)32+ <106 99.075 •CH2 0

_ + Ru(bpy)32+ — 2.9 x 10' Ru(bpy), +

•CH2 OH + Ru(bpy)3

2 + <106 99.076 CH3 CHO- + Ru(bpy)3

2 + 7.0 x 10‘ CH3CHOH + Ru(bpy)3 2+ <106

7 p.r. P.b.k. at 240-340 nm in N20-satd.

soln. contg. 1-4 mol L'

1 MeOH.

75A188

7 p.r. P.b.k. at 260-340 nm in 2 mol L'

1 2-PrOH soln.; same product as from e~ reaction. a q

75A188

7 p.r. P.b.k. 74A167

7 p.r. P.b.k.; same product as from eaq~

. 74A167

7 p.r. P.b.k.; same product as from eaq ~

. 74A167

p.r. P.b.k. at 475 nm in N20-satd. soln. contg. 2.5 mol L

_1 MeOH.

80A227

p.r. P.b.k. at 475 nm in N20-satd. soln. contg. 0.25 mol EtOH. 80A227

~7 p.r. P.b.k. at 365 nm in N20-satd. soln. contg. 0.25 mol L"

1 2-PrOH; same

product as with eaq

”.

80A227

7 p.r. P.b.k.; no reduction. 78A068

11-13 p.r. Same product as from eaq

” reaction; suggested to be [Ru(bpy)2(bpy')] + 78A068

[72G381].

7 p.r. No reduction. 78A068

11-13 p.r. Same product as from eaq " reaction. 78A068

7 p.r. No reduction 78A068

28
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mop's'1 ) PH Method Comment Ref.

99.078 (CH3 ) 2CO- + Ru(bpy)32+ -*• 4.9 x 109 11-13 p.r. Same product as from elq

~ reaction. 78A068

Ru(bpy)3 + (CH)3 )2 COH 1- Ru(bpy)32+ <106 7 p.r. No reduction 78A068

~1.5 x 10® 1 p.r. Radical addn. to ligand. 80A227

99.147 •C02

' + Ru(bpy)32+ <106 7 p.r. No reduction. 78A068

99a. Tris(l,10-phenanthroline)ruthenium(II) ion

99a. 075 •CH2 0" + Ru(phen)32+ — 5.2 x 109 11 p.r. P.b.k. in N20-satd. soln. contg. 80A227

Ru(phen)3 +2.5 mol L1 MeOH.

99a. 076 CH3tHO‘ + Ru(phen)32+ —* 5.9 x 109 12 p.r. P.b.k. in N20-satd. soln. contg. 80A227

Ru(phen)3 + 0.25 mol L1 EtOH; k ~ 10® at pH 1. 99a. 078 (CH3 ) 2tO~ + Ru(phen)32+ —

3.7 x 109 13 p.r. P.b.k. in N20-satd. soln. contg. 80A227

Ru(phen)3 + 0.25 mol L'

1 2-PrOH.

(CH3) 2 tOH + Ru(phen)32+ 8 x 10® 1 p.r. P.b.k. in Ar-satd. soln. 80A227

Ruthenium! Ill) ions

100. Hexaammineruthenium(III) ion

100.035 •CH2 C02 H + Ru(NH3)63+ <3.0 x 107 2.5 p.r. D.k. in Ar-satd. 0.01 mol L~' acetic acid soln. 72A018

<5 x 106 3.9 p.r. D.k. in N2 0-satd. 0.5-1 mol L'

1

acetic acid soln. 77A100

•CH2C02- + Ru(NH3)63+ <1 x 107 7.3 p.r. D.k. in N2 0-satd. 0.01 mol L'

1

acetate soln. 72A018

100.042 •CH(C02H)2 + Ru(NH3)63+ <1.1 x 10® 2.5 p.r. D.k. in Ar-satd. 0.01 mol L"

1 malonic acid soln. 72A018

100.054 HCON(CH3)CH2 + Ru(NH3)63+

NH2tHC02 " + Ru(NH3)63+

<3.0 x 107 6.0 p.r. D.k. in N20-satd. 10~2 mol L'

1 dimethylformamide soln.; e-transfer. 72A018

100.056 (4.0 ± 0.6) x 10® 5.7 p.r. D.k. in N20-satd. 0.01 mol L"

1

glycine soln.; e-transfer. 72A018

100.075 •CH2 OH + Ru(NH3)63+ — (4.1 ± 0.6) x 107 5-6 p.r. D.k. in N20-satd 0.01 mol L'

1 MeOH 72A018 CH2 0 + H

+ + Ru(NH3)62+

soln. 100.076 CH3CHOH + Ru(NH3)63+

(5.5 ± 1.6) x 10® 5-6 p.r. D.k. in N20-satd. 0.01 mol L'

1 EtOH

soln.; e-transfer. 72A018

100.078 (CH3) 2 tOH + Ru(NH3) 63+

(9.2 ± 1.4) x 10® 5-6 p.r. D.k. in N2 0-satd. 0.01 mol L'

1 2-PrOH soln.; e-transfer. 72A018

100.093 CH3CHOC2 H5 + Ru(NH3) 63+

-0tHCH2 0(CH2)2- + Ru(NH3)63+

(1.0 ± 0.15) x 10® 3.5-4 p.r. D.k. in N20-satd. 0.5-1 mol L'

1

ethyl ether soln. 77A100

100.104 (5.0 ± 0.75) x 106 3.5-4 p.r. D.k. in N2 0-satd. 0.5-1 mol L"

1 dioxane soln. 77A100

100.107 CH3COt(OH)CH3 + Ru(NH3)63+ <3.8 x 106 1.2 p.r. D.k. in Ar-satd. lO

-3 mol L"

1

biacetyl soln. 72A018

CH3C0HC02

- + Ru(NH3)63+

2.0 x 109 5.5 p.r. D.k. in N2 0-satd. 10"2 mol L"

1

biacetyl soln. 72A018

100.117 (2.5 ± 0.4) x 109 6.0 p.r. D.k. in N2 0-satd. 10"2 mol L'

1

lactate ion; e-transfer. 72A018

100.127 •CONH2 + Ru(NH3)63+ <7.0 x 107 6.2 p.r. D.k. n N20-satd. 10"2 mol L~* formamide soln.; e-transfer. 72A018

100.147 •C02 - + Ru(NH3)63+ — (2.0 ± 0.6) x 109 4.8 p.r. D.k. in N20-satd. 10”2 mol L'

1 72A018 C02 + Ru(NH3)62+ formate soln.; e-transfer. 101. Bromopentaammineruthenium(III) ion

101.035 •CH2 C02 H + Ru(NH3)sBr2+

(4.6 ± 0.7) x 10® 3.9 p.r. D.k. in N20-satd. 0.5-1 mol L"

1

acetic acid. 77A100

101.093 CH^HOQH; -1- Ru(NH3)sBr

2+

-0tHCH20(CH2)2- + Ru(NH3) sBr2+

(5.8 ± 0.9) x 10® 3.5-4 p.r. D.k. in N20-satd. 0.5-1 mol L*

1

ethyl ether soln. 77A100

101.104 (2.7 ± 0.4) x 10® 3.5-4 p.r. D.k. in N20-satd. 0.5-1 mol L'

1 dioxane soln. 77A100

102. Chloropentaammineruthenium(III) ion

102.035 •CH2 C02 H + Ru(NH3) sC12+

(4.0 ± 0.6) x 107 3.9 p.r. D.k. in N20-satd. soln. contg. 0.5-1 mol L'

1 acetic acid. 77A100

102.075 •CH2OH + Ru(NH3)5C12+

(1.2 ± 0.2) x 10® 3.4-5 p.r. D.k. in N20-satd. soln. contg. 77A100

0.5-1 mol L"

1 methanol. 29

i
TABLE 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol *s PH Method Comment Ref.

102.076 CHjCHOH + Ru(NH3)5 C12+(8.0 ± 1.2) x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. 0.5-1 mol L'

1 ethanol. 77A100

102.078 (CH3 ) 2 COH + Ru(NH3) 5C12+

CH3 CHOC2H5 + Ru(NH3)5C12+

(1.3 ± 0.2) x 109 3.5-4 p.r. D.k. in N2 0-satd. soln. contg. 0.5-1 mol L'

1 2-propanol.

77A100

102.093 (2.6 ± 0.4) x 108 3.5-4 p.r. D.k. in N20-satd. soln. contg. 0.5-1 mol L'

1 ethyl ether. 77A100

102.104 -0CHCH20(CH2)2- + Ru(NH3) 5C12+

(8.3 ± 1.2) x 107 3.5-4 p.r. D.k. in N,0-satd. soln. contg. 0.5-1 mol L'

1 dioxane. 77A100

103. Nitrosopentaammineruthenium(III) ion

103.078 (CH3)2 COH + Ru(NH3) 5 N03+ -> 5.5 x 108 5.0 p.r. P.b.k. at 280 nm in N2 0-satd. soln. 75A049

Ru(NH3)5N02+ + (CH3)2CO + h

+

contg. 0.5 mol L"

1 2-PrOH.

103.147 •C02 - + Ru(NH3) 5N03+ 3.1 x 109 6.6 p.r. P.b.k. at 280 nm in N20-satd. soln. 75A049

Ru(NH3)5N02+ + co2 contg. 0.5 mol L'

1 formate ion.

104. Nitrosopentaammineruthenium(III) radical ion (electron adduct)

104.006 •CH2C(CH3)2 C02 + Ru(NH3)5N02+

(2.9 ± 0.4) x 109 6.0- p.r. D.k. at 280 nm (nitrosyl radical, 79A134

[Ru(NH3 )5N(0)CH2C(CH3 ) 2C02] +

7.5 € = 3.8 x 103 L mol'1 cm'

1 ), as well

as p.b.k. in soln. contg. 0.3 mol L'

1

pivalate ion and 5 x lO^1 mol L'

1 Ru(NH3) 5 N03+

. 104.012 •CH2 C(CH3) 2 NH3 + + (2.0 ± 0.3) x 109 6.0- p.r. D.k. at 280 nm (nitrosyl radical, 79A134

Ru(NH3) 5N02+ -+ 7.5 € = 3.8 x 103 L mol'1 cm'

1 ), as well [Ru(NH3)5 N(0)CH2 C(CH3 )2 NH3]3+

as p.b.k. in soln. contg. 0.3 mol L*1 tert-BuNH2 and 5 x 10*4 mol L'

1 Ru(NH3)5N03+

. 104.013 •CH2 C(CH3)(NH3 + )C02

- (3.1 ± 0.5) x lO9 6.0- p.r. D.k. at 280 nm (nitrosyl radical, 79A134 + Ru(NH3)5N02+

7.5 € = 3.8 x 103 L mol'1 cm'1 ), as [Ru(NH3)s N(0)CH2 C(CH3)(NH3)C02] 2+

well as p.b.k. in soln. contg. 0.3 mol L'

1 2-aminoisobutyrate ion and

5 x 10-4 mol L'

1 Ru(NH3)5N03+

. 104.016 •CH2 C(CH3)2OH + Ru(NH3 ) 5 N02+

(3.7 ± 0.6) x 109 6.0- p.r. D.k. at 280 nm (nitrosyl radical, 79A134

[Ru(NH3)5N(0)CH2C(CH3)20H]2+ 7.5 € = 3.8 x 103 L mol'1 cm'1 ), as well

as p.b.k. in soln. contg. 0.3 mol L'

1 tert-BuOH and 5 x 10"4 mol L'

1 Ru(NH3)5N03+

. 104.017 •CH2 C(CH3)(0H)C02- + (3.0 ± 0.4) x 109 6.0- p.r. D.k. at 280 nm (nitrosyl radical, 79A134

Ru(NH3) 5N02+

7.5 e = 3.8 x 103 L mob'cm'1

) as well [Ru(NH3)sN(0)CH2 C(CH3)(0H)C02] +

as p.b.k. in soln. contg. 0.3 mol L'

1 2-hydroxyisobutyrate ion and 4 x 10"4 mol L'

1 Ru(NH3)5N03+

. 104.055 CH3 CON(CH3 )CH2 + (2.9 ± 0.4) x 109 6.0- p.r. D.k. at 280 nm (nitrosyl radical, 79A134

Ru(NH3) 5N02+ -> 7.5 € = 3.8 x 103 L mol'1 cm'

1 ), [Ru(NH3)5 N(0)CH2 N(CH3)C(0)CH3]2+

as well as p.b.k. in soln. contg. 0.3 mol L'

1 7V,jV-dimethylacetamide and 5 x 10-4 mol L'

1 Ru(NH3) 5N03+

.

105. Tris( 2,2 '-bipyridine )ruthenium( III ) ion

105.016 •CH2 C(CH3)2OH + Ru(bpy)33+

1.3 x 108 acid p.r. 72G462

Ru(bpy)3

2 +

(1.9 ± 0.2) x 108 4.6 p.r. P.b.k. in N2 0-satd. soln. contg. iert-BuOH. 78A070

Sulfur compounds

106. Hydrogen sulfide 106.016 •CH2 C(CH3)2 OH + h2 s ^ 6 p.r. Effect of [H2 S] on p.b.k. at 67G262

H2SCH2C(CH3 ) 2OH 380 nm (complex) gave K = 1 x 10'3 (CH3)3 COH + -SH mol L'

1

; ^(complex —> fert-BuOH + -SH) =

1.3 x 105 s'

1

. 106.075 •ch2 oh + h2s — H2 §CH2 OH 6 p.r. Effect of [H2 S] on p.b.k. at 67G262 — CH3 OH + -SH 360 nm (complex) gave K = 5.3 x 10"4 mol L'

1 ; &(complex —> MeOH + -SH) =

2.3 x 105 s'

1

. 30
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol-s" ) PH Method Comment Ref.

106.076 ch3 £hoh + H2 S ^ H2$CHOHCH3 6 p.r. Effect of [H 2 S] on p.b.k. at 67G262 — CH3 CH2OH + -SH 380 nm (complex) gave K = 6.4 x 10"4 mol L"

1 ; ^(complex — EtOH + -SH) =

4.6 x 105 s'

1

. 106.077 ch3 ch2(!:hoh + H2S 6 p.r. Effect of [H 2 S] on p.b.k. at 67G262 H2$CHOHCH2 CH3 380 nm (complex) gave K = 5.7 x 10

-4 — CH3CH2CH2 OH + -SH mol L”

1

; ^(complex —*• 1-PrOH -|- -SH) =

3.8 x 10s s"

1

. 106.078 (CH3) 2 £oh + h2s 6 p.r. Effect of [H2S] on p.b.k. at 67G262

H2 $COH(CH3)2 — 380 nm (complex) gave K = 1.1 x 10‘3 (CH3) 2CHOH + -SH mol L

_1

; ^(complex —> 2-PrOH + -SH) =

8.6 x 105 s'

1 .

107. Sulfur dioxide

107.147 •C02 S02 — S02 -f C02 (7.6 ± 1) x 108 3.1 p.r. P.b.k. at 320 nm in soln. contg.

1 mol L'

1 formate; 2k(R + R) =

7.6 x 108

.

75A118

108. Tetrathionate ion

108.147 •C02 + S406

2 — C02 + S4063 5.8 x 107 p.r. P.b.k. at 370 nm in N2 0-satd. soln. contg. 0.1 mol L'

1 formate, as well as

d.k. at 280 nm.

73A027

Sc

109. Scandium(III) ions 109.147 •C02-(-C02H) + Sc(III) 1.4 p.r. No reaction in 1 mol L"

1 formic acid and 1 x 10“2 mol L"

1 Sc(III). 73A057

Ti

110. Titanium(III) ions 110.035 •CH2C02 H + Ti3+ — Ti3+ -CH2C02 H (4 ± 1) x 106 0.5 p.r. Complex formn. deduced from 79A341 — Ti(IV) transient spectra. 110.042 •CH(C02H)2 + Ti(III) — Ti(IV) 8 x 106 ~0 e-r. Calcd. from effect of [Ti

111 ] on on esr signal intensity; 2£(R + R) ~ 109

.

73G249

110.075 •CH2OH + Ti(lII) p.r. No reaction in soln. contg. 1 mol

L’

1 MeOH and 10’2 mol L'

1 Ti(III). 73A057

110.147 •C02 - + Ti(III) — Ti(Il)

•C02 H(-C02

-) + Ti3+ — Ti3+ -C02 H

~5 x 106 1.4 p.r. D.k. in 1 mol L'

1 formic acid soln.; p£a (-C02H) = 1.4. 73A057

(4 ± 1) x 106 0.5 p.r. Complex formn. deduced from 79A341 - Ti(II) transient spectra.

Tl

111. Thallium(I) ion 111.076 ch3Cho- + Tl + — Tl2 +

1.5 x 109 13 p.r. P.b.k. at 420 nm in soln. contg.

0.1 mol L'

1 EtOH and 2 x lO

-4 mol 80A123

L"

1 Tl +

; no reaction in neutral or

acid soln. 111.078 (CH3)2 CO- + Tl + — Tl2 +

3.0 x 109 13 p.r. P.b.k. at 420 nm in soln. contg.

0.1 mol L1 2-PrOH and 1 x lO"

4 80A123

mol L“' Tl +

; no reaction in neutral or

acid soln. See also 79G191.

111.147 •C02 - + Tl + — Tl2 +

2.3 x 106 13 p.r. P.b.k. at 420 nm in soln. contg.

1 mol L"

1 formate and 1.5 x 10'2 80A123

mol L"

1 Tl

+

; reaction also obs. for neutral and acid soln.

31
Table 1. Rate constants for reactions of aliphatic radicals with inorganic solutes in aqueous solution—Continued

No. Reaction k (L mol V) PH Method Comment Ref.

111a.

111a. 075

Thallium(I) ion, complex with T1(0) •CH2OH + Tl2 + + H

+ -* 4.0 x 109 6 p.r. Calcd. from d.k. at 420 nm. and 80A123

llla.076

CH3OH + 2 Tl +

ch3Choh + Tl2 + + H

+

3.0 x 109 6 p.r.

condy. change in soln. contg. alcohol and Tl + assuming values for 2&(T12 + + Tl2 +

), &OV + H202 ) and 2k(R + R). See above. 80A123

11 la. 078 CH3 CH2OH + 2 Tl + (CH3)2£OH + Tl2 + + H

+ -> 3.0 x 109 6 p.r. See above. 80A123

112. 112.147

(CH3 )2CHOH + 2 Tl +

Yb

Ytterbium(III) ions •C02-(-C02H) + Yb(III) 1.4 p.r. No reaction in soln. contg. 1 mol 73A057

113. 113.016

Zn

Zinc(I) ion •CH2C(CH3)2 OH + Zn + (+ H

+

) (1.0 ± 0.3) x 109 7 p.r.

L'

1 formic acid and 10'2 mol L"1

Yb(III).

Calcd. from d.k. at 310 nm (Zn +

) 77A011

113.075

Zn2+ + (CH3)3COH

•CH2OH + Zn + (+ H

+

) — (2.5 ± 0.3) x 109 7 p.r.

in tert-BuOH-ZnS04 soln. assuming

k(H + H) = 1.3 x 1010

, k(Zn + + Zn +

) =

4 x 108

, k(R + R) = 6.5 x 108 and

k(Zn + + H) = 2.8 x 109. Calcd. from d.k. at 310 nm (Zn +

) 77A011

113.078

Zn2+ + CH3OH

(CH3)2 COH + Zn +

( + H

+ )-> (1.3 ± 0.25) ~3,7 p.r.

in N2 0-Me0H-ZnS04 soln. taking k(Zn + + Zn +

) = 4.5 x 108

, A(Zn + + H2 02) = 2.4 x 109

, k(Zn + + N20) = 1.6 x 107 and k(R + R) = 1.5 x 109

. Calcd. from d.k. at 310 nm (Zn +

) 77A011

113.147

Zn2+ -|- (CH3) 2 CHOH

•CO," + Zn+ ( + H

+

) —

x 109

~4 x 109 p.r.

in 2-Pr0H-ZnS04 soln. taking k( Zn + +

Zn +

) = 4.5 x 108

. Est. from first-order decay at 310 77A011

114. 114.016

Zn2+ + HC02

-

Zinc(II) ion •CH2C(CH3)2 OH + Zn2+ V © p.r.

nm (Zn +

) in formate-ZnS04 soln.

Est. from lack of increase in Zn +in 75A027

114.075 •CH2OH + Zn2+ <102 p.r.

0.1 mol L

_1 Zn2+

soln. upon addn. of

0.1 mol L’

1 tert-BuOH.

Est. from lack of increase in Zn +

in 75A027

114.078 (CH3)2COH + Zn2+ <106 p.r.

0.1 mol l/

1 Zn2+

soln. upon addn. of

0.1 mol L*

1 MeOH.

Est. from lack of increase in Zn +

in 75A027

114.147 •CO," + Zn2+ <102 p.r. 2-PrOH.

Est. from lack of increase in Zn +in 75A027

Zinc hematoporphyrin See 221.

Zinc(II)-Jnsulin See 233a.

<2 x 104 p.r.

0.1 mol L'

1 Zn2+

soln. upon addn. of

0.1 mol LT

1 formate ion. No reaction in 0.5 mol L

_1 ZnS04

. 77A011

32
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution

No. Reaction k (L mol 's ') pH Method Comment Ref.

115. Acetic acid 115.001 •ch3 + ch3 co2 h — 2 x 102 ~1 chem. Radical from dimethyl sulfoxide 75D188 CH4 + -CH2C02 H in Ti ln-H2 02 soln.; est. from

esr meas. and values for competing

reactions.

116. Acetone

116.001 •ch3 + CH3COCH3 -* 0.99[Ar(R + R]05 nat phot. Est. from quantum yields of 60F004 ch4 + -CH2 COCH3 1.00[£(R + R)]os

nat phot. CH4, CO, and C2 H6

. Obs. yields of CH4 and C2 H6; log k (in cm

3 mop's"1 ) =

[(4.47 ± 0.05)-(1335 ± 18)/T] -

0.5 log A(R 4- R).

69F176

117. Acetonitrile

117.001 •CH3 + CH3CN -+ <3 x 102 ~1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 + -ch2cn Ti

MI -H202 soln.; est. from esr.

118. 118.076 Acetophenone

CH3CHO" + C6H5COCH3 CH3 CHO + (C6H5 COCH3

)-"

(CH3) 2C0" + C6H5 COCH3

1.1 x 109 13 p.r. P.b.k. at 440 nm in N20-satd. soln. contg. 1 mol L"

1 EtOH; pH dependent,

k extrapolated to pH 14.

73G122

118.078 7.8 x 108 13 p.r. P.b.k. at 440 nm in acetone soln. 67G729

CH3COCH3 + (C6H5 COCH3K 9 x 108 13 p.r. P.b.k. at 440 nm in N2 0-satd. soln. contg. 1 mol L"

1 2-PrOH; pH dependent,

k extrapolated to pH 14.

73G122

118.142 R + C6H5COCH3 -> (C6H5COCH3

).- (2.3 ± 0.3) x 109 5.2 p.r. P.b.k. at 280 nm (320 at pH 12.3) in 71G554

(R = Electron adduct of

glycine anhydride)

(2.0 ± 0.3) x 109 12.3 soln. contg. 1 mol L'

1 /ert-BuOH.

118.143 R + C6H5COCH3 — (C6H5COCH3

).- (2.0 ± 0.3) x 109 5.2 p.r. P.b.k. at 280 nm (320 at pH 12.2) in 71G554

(R = Electron adduct of alanine anhydride)

(1.5 ± 0.4) x 109 12.2 soln. contg. 1 mol L"

1 ter/-BuOH.

118.144 R + C6H5COCH3 - (C6H5COCH3

).- (2.0 ± 0.2) x 109 5.2 p.r. P.b.k. at 280 nm (320 at pH 12.4) in 71G554

(R = Electron adduct of

sarcosine anhydride)

(2.1 ± 0.2) x 109 12.4 soln. contg. 1 mol L'

1 ter/-BuOH.

118.147 •co2- + c6h5 coch3 1 x 107 12 p.r. P.b.k. at 440 nm. 68G308

C02 + (C6H5COCH3

)-"

119. Acetylene

119.022 •CH = CHOH + CH = CH (8.8 ± 0.9) x 106 4.0, p.r. Radical from OH + C2H2; p.b.k. at 78A007

6.0 290 nm; Ea — 25.1 kj mol" 1

; product thought to be hydroxybutadienyl which

reacts to give hydroxyhexatrienyl

(p.b.k. at 260 nm, k = 5 x 106 L molds'1 ).

120. 3-Acetylpyridine

120.078 (CH3 ) 2COH 4- CH3 COC5 H4NH+ — (8.6 ± 1.7) x 109 0.6 p.r. P.b.k.; no e-transfer in 74A089

e-transfer neutral soln.; pKa = 4.9.

121. 121.075 Acridine

•ch2oh + c13h9 nh+

(CH3)2C0 4 C13 H9N —

5.0 x 108 2.0 p.r. P.b.k. in N20-satd. soln. contg. MeOH; ~30% e-transfer; no reaction

at pH 7.6; pKt = 5.6.

74A127

121.078 3 x 109 13 p.r. P.b.k. in N20-satd. soln. 79A305

(CH3)2CO 4- A" contg. 2-PrOH.

(CH3)2COH 4- c13h9n — 3.0 x 108 7.6 p.r. P.b.k. in N20-satd. soln. contg. 74A127

•AR 4- -A (50% redn.. 2-PrOH; ~40% e-transfer. 50% addn.) ~3 x 108 7-9 p.r. P.b.k. 79A305

(CH3 )2 tOH + CI3 H9 NH+ — 3.7 x 109 2.0 p.r. P.b.k. in N20-satd. soln. contg. 74A127

(CH3)2 CO + H

+ + -AH

3.3 x 109 4 p.r. 2-PrOH; ~90% e-transfer.

P.b.k. 79A305

33
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mop's*1 ) PH Method Comment Ref.

121.147 •C02

- + AH+ — -AH ~3 x 108 7 p.r. P.b.k.; at pH 13 adduct is formed (•CO.f + A —*• "ACC^"). 79A305

122. Acriflavin (3,10-Diamino-10-methylacridinium chloride)

122.147 •CO2 A (3.7 ± 0.4) x 108 p.r. D.k. (dye) in Ar-satd. 0.1 mol Lf1

formate; same product as concurrent

fast reaction with e~.aq

70G241

123. Acrylamide

123.016 •CH2C(CH3 )2OH + ch2 =chconh2 — (4.5 ± 1.4) x 107 4.5 p.r. C.k. in N20-satd. soln. contg. 78A322

hoc(ch3)2ch2ch2Chconh2 (6.8 ± 2) x 107 3 tert-BuOH and Cu2+

; rel. to

(rel.) k( R + Cu2+

) = 2.7 x 106 at pH 4.5 and 3.2 x 106 at pH 3. 123.075 •ch2oh + ch2 =chconh2 — (2.6 ± 0.8) x 107 2-5 p.r. C.k. in N2 0-satd. soln. contg. MeOH 78A322

hoch2ch2Chconh (rel.) and Cu2+

; rel. to A(R + Cu2+

) =

1.6 x 108. 123.076 ch3Choh + ch2 =chconh2 ^ (2.6 ± 0.8) x 107 2-5 p.r. C.k. in N20-satd. soln. contg. EtOH 78A322

ch3chohch2Chconh2 (rel.) and Cu2+

; rel. to Ar(R + Cu2+

) =

9.4 x 107. 123.078 (CH3)2COH + ch2 =chconh2 — (4.1 ± 1.2) x 107 2-5 p.r. C.k. in NzO-satd. soln. contg. 78A322

(CH3)2C(OH)CH2CHCONH2 (rel.) 2-PrOH and Cu2+

; rel. to &(R + Cu2+

) =

5.2 x 107. 123.128 [CH2CHCONH2K + ch2 = chconh2 ^ (2.5 ± 0.4) x 105 ~6 p.r. D.k. at 275 nm. 70G052

H0C(NH2

) =CH(CH2)2 CHCONH2 123.147 •C02

- + CH2 = CHCONH2 —» addn. ~(4 ± 1) x 107 ~5 p.r. Electron transfer not obs. 70G052

124. Adenosine

124.078 (CH3)2COH + A ^ 4.7 x 107 2.2 p.r. P.b.k. 75A060

e-transfer <106 7.0 (CH3)2CO- -1- A <106 13.6

125. Adenosine monophosphate

125.147 •CO2 + A <106 8.3 p.r. P.b.k. at 550 nm (A')

in N20-satd. 0.1 mol L'

1 formate. 68G441

126. 126.147 Alloxan

•C02

- + A( + H

+

) —*• C02 + AH

(3.7 ± 1.1) x 107 4.8 p.r. P.b.k. at 310 nm in N20-satd. soln. contg. 0.1 mol L"

1 formate;

cor. for decay of -CO^.

79A327

80A197

127. 127.078 2-Amino-5-nitrothiazole

(CH3)2COH + NX —

(CH3)2CO + NX- + H

+

2.0 x 109 p.r. P.b.k. 76A075

128. 128.020 4—Aminophenoxide ion •CH2CHO + NH2C6H40- ch3cho + nh2c6h4o2.1 x 109 — 1 1.5 p.r. Soln. contg. N20 and ethylene glycol. 79A051

129. 129.078 4-Aminopyrimidine

(CH3)2COH + A

(CH3)2£o- + A

0.8-

13.0

p.r. No e-transfer. 77A034

130. 130.036 Aniline

•CF3 + C6H5 NH2 — addn. (4.7 ± 0.9) x 106 9-10 p.r. P.b.k. at 330 nm in N20-satd.

soln. contg. CF3C1; c.k. rel. to A(CF3 + HC02

-) = 3.4 x 105 gave k = 5.6 x 106

.

70G407

131. 131.078 9,10-Anthraquinone

(CH3)2tOH + A -*

semiquinone

(1.6 ± 0.1) x 109 7.0 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. 2-PrOH. 73A104

34
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mor’s'1 ) PH Method Comment Ref.

131.097 CH3C(0-)CH2 C02

- + A — (6.7 ± 0.7) x 108 9.2 p.r. P.b.k. at 400 nm in Ar-satd. soln. 73A104

semiquinone contg. acetoacetate and 1 mol L"

1 tert-BuOH.

132. 9, 10-Anthraquinone-l -sulfonate ion

132.147 •C02

" + A —»• semiquinone 1.0 x 109 3 p.r. P.b.k. 72G391

3.3 x 109 7

133. 9,10-Anthraquinone-2-sulfonate ion 133.056 NH2 CHC02 + A —* semiquinone (2.2 ± 0.2) x 109 8.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. glycine. 73A 104

133.068 R + A —*• semiquinone (1.4 ± 0.1) x 109 10 p.r. P.b.k. at 400 nm in N20-satd. soln. 73A104

(R = Radicals from triglycine) contg. triglycine. 133.078 (CH3)2tOH + A —>• semiquinone (3.0 ± 0.3) x 109 7.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. 2-PrOH.

73A 104

(5.6 ± 0.6) x 109 p.r. P.b.k. in N20-satd. soln. contg. 0.1 mol L"

1 2-PrOH. 76A070

133.097 CH3 £(0-)CH2 C02

- + A — (2.1 ± 0.2) x 109 9.2 p.r. P.b.k. at 400 nm. in Ar-satd. soln. 73A104

semiquinone

(7.1 ± 0.7) x 108 contg. acetoacetate and /err-BuOH. 133.115 •CH0HC02

' + A —* semiquinone 7.0 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. glycolate. 73A104

133.147 •C02

" + A —»• semiquinone 2.8 x 109 3 p.r. P.b.k. in soln. contg. formate. 72G391

3.1 x 109 7

(1.6 ± 0.2) x 109 7 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. formate. 73A104

134. 9,10-Anthraquinone-2,6-disulfonate ion

134.056 NH2 CHC02 + A —» semiquinone (2.6 ± 0.3) x 109 8.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. glycine. 73A104

134.068 R + A —* semiquinone (1.8 ± 0.2) x 109 10 p.r. P.b.k. at 400 nm in N20-satd. soln. 73A104

(R = Radicals from triglycine) contg. triglycine. 134.078 (CH3) 2tOH + A —*• semiquinone

CH3 C(0')CH2C02- + A -

(4.6 ± 0.5) x 109 7.0 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. 2-PrOH. 73A104

134.097 (7.2 ± 0.7) x 108 9.2 p.r. P.b.k. at 400 nm. in Ar-satd. soln. 73A104

semiquinone contg. acetoacetate and tert-BuOH. 134.117 ch3Cohco2h + A 3.0 x 109 7.0 p.r. P.b.k. in N2 0-satd. soln. contg. 5 x 10"3 mol L"

1 lactate; 58% e- 75A051

transfer. 134.147 •C02“ + A —* semiquinone (2.4 ± 0.2) x 109 7.0 p.r. P.b.k. in N2 0-satd. soln. contg. formate. 73A104

135. Ascorbate ion 135.020 •CH2 CHO -1- A* (+ H2 0) — 8.8 x 107 7 p.r. Radical from C1CH2 CH2 0H by reaction 79A051 CH3CHO -1- -A' + OH" with OH and HC1 elimination. 135.042 •CH(C02

-)2 + AH' — (1.3 ± 0.1) x 107 7.5 p.r. P.b.k. in N2 0-satd. soln. 73R006 CH2 (C02 )2 “f

- -A contg. 0.8 mol L"

1 malonate. 135.075 •CH2 OH + AH- <106 p.r. 77A036

135.078 (CH3 )2tOH + AH' — (1.2 ± 0.1) x 106 6.1 p.r. P.b.k. in soln. contg. 1 mol L"

1 73R006

(CH3)2CHOH + -A' acetone and 2 mol L"

1 2-PrOH.

136. Azobenzene

136.075 •CH2 0- + QHsN = NC5H5 — 1 x 109 14 p.r. P.b.k. at 380 nm in soln. contg. 77A169 ch2 o + [C6H5N=NQH5

].- MeOH; k same for syn- and antiisomers. 136.078 (CH3 )2tOH + c6 h5 n=nc6 h5 — 4 x 108 ~7 p.r. P.b.k. at 380 nm in soln. contg. 77A169

(CH3)2 CO + H

+ + -[C6 H5N = NC6H5

]- 2-PrOH; anti- isomer. <ch3 )2<!:o- + c6h5 n=nqhs — 2 x 109 14 p.r. P.b.k. at 380 nm in soln. contg. 77A169

(CH3)2 CO + .[C6 H5 N = NC6H5r 2-PrOH; an/i-isomer.

137. Benzophenone

137.075 •CH2 0- + (C6Hs)2CO — 1.2 x 108 13 p.r. P.b.k. at 610 nm in N20-satd. soln. 75A125 CH2 0 + (C6Hs)2Co- 1 mol L1 MeOH.

35
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol *s ; pH Method Comment Ref.

137.076 CHjCHO- + (C6H5)2CO - 1 X 109 13 p.r. P.b.k. at 610 nm in N2 0-satd. soln. 74A010

CH3 CHO + (C6H5)2CO"

2.6 X 108 13 p.r.

contg. EtOH; Ea ~ 3.1 kcal mol

" 1

(13 kj mol"1 ). P.b.k. at 610 nm in N2 0-satd. soln. 75A125

137.078 (CH3)2 CO- + (C6H5) 2CO — 1.2 X 109 12 p.r. P.b.k. 68G308

(CH3)2CO + (C6H5)2CO * (1.6 ± 0.2) X 109 13.1 p.r. P.b.k. at 605 nm in N20-satd. soln. contg. 2 mol L

" 1 2-PrOH. 72G359

R + (C6H5) 2 CO -> (C6H5)2CO7.0 x 108 13 p.r. P.b.k. at 610 nm in N20-satd. soln. contg. 2-PrOH. 75A125137.142 (2.2 ± 0.3) x 109 5.5 p.r P.b.k. at 330 nm (320 at pH 12.3) 71G554

(R = Electron adduct of

glycine anhydride)

(2.5 ± 0.4) x 109 12.3 in soln. contg. 1 mol L

" 1 fe/t-BuOH.

137.143 R + (C6H5)2CO (C6H5) 2 CO- ( 1.6 ± 0. 2) x 109 5.2 p.r. P.b.k. at 330 nm (320 at pH 12.2) in 71G554

(R = Electron adduct of alanine anhydride)

(1.9 ± 0.3) x 109 12.2 soln. contg. 1 mol L

" 1 (ert-BuOH.

137.144 R + (C6H5)2CO (C6H5)2CO- (2.3 ± 0.2) x 109 5.2 p.r. P.b.k. at 330 nm (320 at pH 12.2) in 71G554

(R = Electron adduct of

sarcosine anhydride)

(2.4 ± 0.2) x 109 12.2 soln. contg. 1 mol L

" 1 tert-BuOH.

138. Benzoquinone

138.056 NH2 CHC02~ + Q —> semiquinone (3.9 ± 0.4) x 109 8.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. glycine. 73A104

138.062 R + Q —> semiquinone 2.2 x 109 10.5 p.r. P.b.k. in N2 0-satd. soln. contg. 73A052

(R = Radical from glycine anhydride)glycine anhydride; 87% e-transfer.

138.068 R -f- Q —* semiquinone (2.5 ± 0.2) x 109 10 p.r. P.b.k. at 400 nm in N2 0-satd. soln. 73A104

(R = Radicals from triglycine) contg. triglycine 138.075 •CH2 OH + Q — CH2 0 + H

+ + -Q" 6.1 x 109 nat p.r. P.b.k. at 430nm in N2 0-satd. soln. contg. 1 mol L

" 1 MeOH.

71G619

4.8 x 109 6.2 p.r. P.b.k. at 430 nm in N2 0-satd. soln. contg. 1 mol L

"1 MeOH.

73G049

138.076 CH3CHOH + Q 4.5 x 109 nat p.r. P.b.k. at 430 nm in N20-satd. soln. 71G619

CHjCHO + H

+ + -Q" contg. 1 mol L

"1 EtOH.

138.078 (CH3)2fiOH + Q 5.0 x 109 nat p.r. P.b.k. at 430 nm in N20-satd. soln. 71G619

(CH3)2 CO + H

+ + -Q-

(5.4 ± 0.5) x 109 7.0 p.r.

contg. 1 mol L

' 1 2-PrOH.

P.b.k. at 400 nm in N2 0-satd. soln. contg. 2-PrOH. 73A104

5 x 109 6.9 p.r. P.b.k. at 430 nm in N2 0-satd. soln. contg. 0.2 mol L

" 1 2-PrOH. 73G049

5.0 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L

" 1 acetone and 1 mol L

" 1 2-PrOH. 73G125

138.092 R + Q - -Q' 1.2 x 109 p.r. P.b.k. at 430 nm in soln. contg. 78A261

(R = Radicals from sodium 0.1 mol L

" 1 sodium dodecylsulfate

dodecylsulfate) A(R + micelle) = 9.9 x 108

. 138.108 R + Q

—* semiquinone 2.7 x 109 5.6 p.r. P.b.k. at 430 nm in N20-satd. soln. 73G049

(R = Radicals from deoxyribose) contg. deoxyribose. 138.115 •chohco2- + Q — -Q" 2.2 x 109 7.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. 73A052

contg. glycolate 72% e-transfer. 73A104

138.116 CH3COHCONH2 + Q

.Q- 2.0 x 109 5.0 p.r. P.b.k. in N20-satd. soln. 73A052

3.6 x 109 7.3 contg. lactamide. 138.117 CH3C0HC02

- + Q — -Q- 6.5 x 109 7.3 p.r. P.b.k. in N2 0-satd. soln. 73A052

~7.0 x 109 10.8 contg. lactate; 97% e-transfer. 138.147 •C02

- + Q C02 + -Q- 6.6 x 109 ~7 p.r. P.b.k. in N20-satd. soln. contg. 0.2 mol L

" 1 formate. 71G619

7 x 109 6.9 p.r. P.b.k. at 430 nm in N2 0-satd. soln. contg. 0.1 mol L

" 1 formate. 73G049

(6.6 ± 0.7) x 109 7.0 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. formate. 73A104

139. 3-Benzoyl-l-methylpyridinium ion

139.078 (CH3)2 COH + C6HsCOC5H4N

+ CH3 (2.3 ± 0.3) x 109 5.0, p.r. P.b.k. at 530 nm in N20-satd. 72G359

(CH3 )2 CO + (C6H5COHC5 H4NCH3

)- +

1.0 soln. contg. 2 mol L

" 1 2-PrOH.

36
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L moP's'1 ) pH Method Comment Ref.

140. 2-Benzoylpyridine

140.078 (CH3)2tOH + c5h5coc5 h4nh+ —

(CH3)2CO + (C5H5 COHC5 H4NH)- +

(3.0 ± 0.3) x 109 1.0 p.r. P.b.k. at 500 nm, as well as at 330 nm, in N2 0-satd. soln. contg. 2 mol L'

1 2-PrOH.

72G359

(CH3)2COH + c6h5coc5 h4n —

(CH3)2 CO + (C6 H5COC5 H4NH)-

(1.5 ± 0.2) x 108 5.9 p.r. P.b.k. at 500 nm, as well as at 330 nm, in N2 0-satd. soln. contg. 2 mol L1 2-PrOH.72G359

141.

(CH3 ) 2Co- + C6 H5 COCs H4N —

(CH3)2 CO + (C6H5COC5H4N).-

3-Benzoylpyridine

(2.3 ± 0.2) x 109 13.2 p.r. P.b.k. at 550 nm, as well as at 330 nm, in N2 0-satd. soln. contg. 2 mol L"

1 2-PrOH.

72G359

141.078 (CH3 ) 2tOH + C6 H5COC5H4NH+ (CH3)2 CO + (C6H5COHC5 H4NH). +(1.7 ± 0.2) x 109 0.9 p.r. P.b.k. at 500 nm, as well as at 330 nm (at pH 0.5 giving k = 2.3 x 109

) in N20-satd. soln. contg. 2 mol L*

1 2-PrOH.

72G359

(CH3)2 £OH + C6H5COC5 H4N -»

(CH3 )2 CO + (C6H5 COC5H4NH).

(1.0 ± 0.2) x 108 5.1 p.r. P.b.k. at 530 nm, as well as at 330 nm in N20-satd. soln. contg. 2 mol IT

1 2-PrOH.

72G359

142.

(ch3 ) 2 Cct + c6h5coc5 h4n —

(CH3)2CO + (C6H5 COC5H4N)-“

4-Benzoylpyridine

(2.0 ± 0.2) x 109 13.0 p.r. P.b.k. at 605 nm, as well as at 341 nm, in N2 0-satd. soln. contg. 2 mol L*

1 2-PrOH.

72G359

142.078 (CH3 ) 2tOH + C6H5 COC5 H4NH+ (CH3) 2CO + (C6H5 COHC5 H4NH). +

(2.5 ± 0.2) x 109 0.7 p.r. P.b.k. at 510 nm in N2 0-satd. soln. contg. 2 mol L'

1 2-PrOH. 72G359

(CH3) 2 COH + c6h5cocs h4n —

(CH3)2CO + (C6H5COC5 H4NH)-

(2.4 ± 0.4) x 108 7.7 p.r. P.b.k. at 500 nm in N2 0-satd. soln. contg. 2 mol L'

1 2-PrOH. 72G359

143.

(CH2) 2CCT + C6H5 COC5 H4N — (2.5 ± 0.2) x 109 (CH3)2CO + (C6H5COC5 H4N).-

Benzyl viologen See 1,1'-Dibenzyl-4, 4'-bipyridinium ion 171.

Biacetyl See 2,3-Butanedione 148.

2,2'-Bipyridine

13.2 p.r. P.b.k. at 575 nm in N20-satd. soln. contg. 2 mol L'

1 2-PrOH. 72G359

143.075 •CH2 OH + bpy <106 7 p.r. P.b.k. 79A148

•CH2 0" + bpy <106 alk. p.r. P.b.k. 79A148

143.078 (CH3) 2tOH + bpy <106 7 p.r. P.b.k. 79A148

(CH3) 2tOH + bpyH + ->

(CH3)2CO + bpyH2

- +

3.5 x 108 1.4, 3.7

p.r. P.b.k. at 375 nm in N2 0-satd. soln. contg. 0.2 mol L‘* 2-PrOH. 79A148

(CH3)2tO- + bpy —*• (CH3)2CO + bpy-”

1.3 x 108 13.0 p.r. P.b.k. at 365 nm in soln. contg. 0.1 mol L'

1 2-PrOH and 0.1 mol L'1

acetone.

79A148

143.147 C02

* + bpy <106 7 p.r. P.b.k. 79A148

144.

•C02

' + bpyH + 5.0 x 108

1 , 1 '-Bisf 2-hydroxyethyl)-4,4'-bipyridinium ion

4.4 p.r. P.b.k. at 375 nm in N20-satd. soln. contg. 0.2 mol L"

1 formate. 79A148

144.147

145.

•C02

- + BP2+ C02 + -BP +

2-Bromo-5-nitrothiazole

1.9 x 10 10 6.8 p.r. P.b.k. in N2 0-satd. soln. contg. 0.1 mol L'

1 formate. 78A321

145.078

146.

(CH3) 2tOH + NX —

(CH3)2CO + H

+ + -NX5-Bromouracil

3.0 x 109 p.r. P.b.k. 76A075

146.078 (CH3) 2 COH + BrU 2 x 107 (rel.) p.r. C.k. rel. to A:(R + PNAP) =

3.8 x 109. 73A140

146.147 •C02

- + BrU —

CO2 Br -f U* >1.0 x 108 p.r. P.b.k. at 440 nm (BrUC02”) in N20-satd. soln. contg. formate. 69G826

37
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol ’s ') pH Method Comment Ref.

147. Butadiene

147.001 •CH3 + C4H6 -» addn. 1.25 x 106 (rel.) y-r. C.k. with MeOH in soln. contg. Mel; obs. G(CH4); rel. to A(CH3 + 02) = 4.7 x 109

.

67G041

147.047 •CF3 4- C4H6 —* addn. (5.8 ± 1.0) x 108 9-10 y-r. C.k. with 2-PrOH in soln. contg. 70G407

(rel.) CF3 C1; rel. to k{CF3 + HC02

") =

3.4 x 105.

148. 2,3-Butanedione

148.075 •CH2OH + CH3 COCOCH3 (B) 1.1 x 108 p.r. P.b.k. at 300 nm in N2 0-satd. soln. 68G249

CH20 + H+ + -B- (6.5 ± 1) x 107 5-6 p.r.contg. 10'2 mol L"

1 MeOH.

D.k. in N2 0-satd. soln. contg. lO'2 mol L1 MeOH.

72A018

148.076 ch3Choh + B 5.6 x 108 p.r. P.b.k. at 300 nm in N2 0-satd. soln. 68G249

ch3cho + h

+ + -B- contg. 10"2 mol L"

1 EtOH.

148.077 ch3ch2Choh + b -* 6.8 x 108 p.r. P.b.k. at 300 nm in N2 0-satd. soln. 68G249

CH3CH2 CHO + H

+ + -B" contg. 1-PrOH.

148.078 (CH3)2tOH + B -+ 8.6 x 108 p.r. P.b.k. at 300 nm in N20-satd. soln. 68G249

(CH3)2 CO + h

+ + -B- 6.0 x 108 5-6 p.r.

contg. 10"2 mol L"

1 2-PrOH.

D.k. in N20-satd. soln. contg. lO’

2 mol L1 2-PrOH. 72A018

148.080 ch3ch2 cohch3 + B ^ 7.2 x 108 p.r. P.b.k. at 300 nm in N2 0-satd. soln. 68G249

CH3COCH2 CH3 + h

+ + -B- contg. 2-BuOH.

148.083 c-C6Hh CHOH + B 2.6 x 108 p.r. P.b.k. at 300 nm in N20-satd. soln. 68G249

C6Hn CHO + H

+ + -B- contg. cyclohexanemethanol. 148.117 ch3 Cohco2

- + B 2.8 x 107 6.0 p.r. D.k. in N2 0-satd. soln. contg. 10~2 mol L"

1 lactate. 72A018

149. 1 -Butene

149.001 •CH3 + C4H8 —> addn. 3.0 x 104(rel.) y-r. C.k. with MeOH in soln. contg. Mel;

obs. ^(CH^; rel. to £(CH3 +

02) = 4.7 x 109.

67G041

149.047 •CF3 + C4H8 —> addn. (5.3 ± 0.7) x 107 9-10 y-r. C.k. with 2-PrOH; rel. to 70G407

(rel.) A(CF3 + HC02

-) = 3.4 x 10s

.

1,1'-Butylene-2,2'-bipyridinium ion See Tetramethylene-2,2'-bipyridinium ion 341.

150. Camphor

150.147 •C02 RC=0 <106 13 p.r. D.k. of -C02

- at 260 nm. in N20-satd. soln. contg. 0.1 mol L"

1 formate and 0.1 mol L"

1 NaOH same in the presence and absence of 10"3 mol I/

1 camphor.

79A191

151. 3-Carbamoyl-l-methylpyridinium ion

151.078 (CH3)2COH + CH3N

+ C5 H4CONH2 (3.6 ± 0.7) x 108 9.5 p.r. P.b.k. (pyridinyl radical) in N20-

satd. soln. contg. 1-2 mol L"

1 2-PrOH. 74A089

151.147 •C02- + CH3N

+ C5H4CONH2 4.6 x 109 8.5 p.r. P.b.k. at 420 nm in N2 0-satd. soln. contg. 0.1 mol Lr

1 formate. 68G441

152. Carbon tetrachloride 152.075 •CH2 OH + CC14 — <106 p.r. Condy.; G(Cr) ~ 0.3G(-CH2 OH). 71G778

•CC13 + Cl- + ch2 o + h

+ 152.078 (CH3) 2 £OH + CC14 -»• 1.0 x 108 p.r. Condy.; build-up of HC1 in N2 0-satd. 71G778

•CC13 + Cl- + (CH3) 2 CO + h

+

7 x 108 (rel.) p.r.

soln. contg. 0.1 mol L"

1 2-PrOH.

C.k. with /)-nitroacetophenone 73A140

in soln. contg. 2-PrOH and acetone;

rel. to A(R + PNAP) = 3.8 x 109. 73A150

152.093 ch3 Choc2 h5 + CC14 Cl- 2.5 x 107 p.r. Condy.; buildup of HC1 in N20-satd.

soln. contg. Et20. 71G778

38
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mop's'

1 ) PH Method Comment Ref.

152.094 -OCH(CH2)s- + CC14 — Cl* 2.0 x 107 p.r. Condy.; buildup of HC1 in N20-satd.

soln. contg. tetrahydrofuran. 71G778

152.147 •CO2 + CCl^ no reaction p.r. Condy. 71G778

153. 3-Carboxy-l-methylpyridinium ion

153.078 (CH3 ) 2tOH 4 CH3 N

+ C5H4C02' 1.0 x 108 9.2 p.r. P.b.k. (pyridinyl radical) at 400 nm in N2 0-satd. soln. contg. 0.5 mol L'

1 2-PrOH.

74A106

154. 4—Carboxy-l-methylpyridinium ion

154.075 •CH2 0- 4 CH3N

+ C5H4C02

- 3.8 x 109 12.7 p.r. P.b.k. at 395 nm in N20-satd.

soln. contg. 0.1 mol L'

1 MeOH.

79A051

154.076 ch3£ho- 4 CH3N

+ C5 H4C02- 3.8 x 109 12.7 p.r. P.b.k. at 395 nm in N20-satd.

soln. contg. 0.1 mol L'

1 EtOH. 79A051

154.078 (Ch3)2(!:oh 4 ch3 n

+ c5 h4co2

- 1.5 x 109 8.6 p.r. P.b.k. at 400 nm in soln contg. 0.5 mol L'

1 2-PrOH. 79A106

Catechol See 1,2-Dihydroxybenzene 1 76.

155. Chloral hydrate

155.078 (CH3)2tOH + Cl3 CH(OH)2 1 x 106 (rel.) p.r. C.k. with />-nitroacetophenone in 73A140

soln. contg. 2-PrOH and acetone;

rel. to k(R 4 PNAP) = 3.8 x 109

. 73A150

Chloranil See Tetrachlorobenzoquinone 338.

156. Chloroacetic acid 156.001 •ch3 4 C1CH2C02 H — 3.0 x 103 ~1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 4 ci£hco2 h Tiln-H202 soln.; est. from esr meas. and values for competing reactions.

156a. m-Chlorobenzonitrile

156a.078 (CH3)2 tO' + C1C6H4CN (2 ± 0.5) x 10® 13 p.r. P.b.k. at 310 nm (radical anion); 81A001

(CH3)2 CO 4 (C1C6H4CN).- k < 107 at pH 7.

157. Chloroform

157.078 (CH3)2 tOH 4 chci3 <1 x 10' (rel.) p.r. C.k. with />-nitroacetophenone 73A140

in soln. contg. 2-PrOH and acetone;

rel. to k(R 4 PNAP) = 3.8 x 109.

158. /j-Chloronitrobenzene

158.111 R 4 C1C5H4N02 4.0 x 108 p.r. 77R167

(R = Radicals from glucose) 158.147 •C02- 4 C1C5H4N02 3 x 108 p.r. 77R167

159. 159.056

Crystal Violet NH2CHC02- 4 dye

(CH3) 2tOH 4 dye

1.2 x 109 7 p.r. D.k. at 525 nm in N2 0-satd. soln. contg. glycine; 56% e-transfer. 73A078

159.078 2.3 x 109 7 p.r. D.k. at 525 nm in NzO-satd. soln. contg. 2-PrOH; 84% e-transfer. 73A078

159.147 •C02' 4 dye —

C02 4 dye' 1.5 x 109 7 p.r. D.k. at 520 nm as well as p.b.k.

at ~ 400 nm. 73A078

160. Cyanoacetic acid 160.001 •ch3 4 cnch2 co2 h — >6.6 x 103 ~1 chem. Radical from dimethyl sulfoxide 75D188 ch4 4 cnChco2 h in Ti m-H202 soln.; est. from esr and values for competing reactions.

2-Cyanoethanol See 3-Hydroxypropionitrile 230.

39
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mop's'

1 ) pH Method Comment Ref.

160a. Cystamine

(1.2 ± 0.3) x 108 160a. 142 R + Cys —* e-transfer 5.7, p.r. D.k. at 265 nm (R) in soln. contg. 71G554

(R = Electron adduct of

glycine anhydride)

(1.1 ± 0.2) x 108

11.0 1 mol L"

1 rert-BuOH.

160a. 143 R + Cys —> e-transfer 5.1, p.r. D.k. at 265 nm (R) in soln. contg. 71G554

(R = Electron adduct of alanine anhydride)

11.4 1 mol L'

1 rert-BuOH.

161. Cysteamine

161.016 -CH2 C(CH3)2OH + RSH - 1.8 x 107 p.r. P.b.k. at 410 nm (RSSR') in N20- 68G132

(CH3)3COH + RS- satd. soln. contg. tert-BuOH. 161.018 R' + RSH <1 x 107 p.r. P.b.k. at 410 nm (RSSR') in N20- 68G132

(R' = Radicals from

allyl alcohol)

satd. soln. contg. allyl alcohol.

161.033 •CH2 COCH3 + RSH ~4 x 108 p.r. P.b.k. at 410 nm (RSSR*) in N2 0- 68G132

CH3COCH3 + RS- satd. soln. contg. acetone. 161.075 •CH2 OH + RSH 6.8 x 107 7.6 p.r. P.b.k. at 410 nm (RSSR*) in N2 0- 68G132

CH3OH + RS2.9 x 107 7 p.r.

satd. soln. contg. MeOH; ialx 107

at pH 12. D.k. in N20-satd. soln. contg. MeOH. 72R003

161.076 CH3CHOH + RSH -* 1.4 x 108 p.r. P.b.k. at 410 nm (RSSR") in N20- 68G132

CH3CH2 OH + RS- satd. soln. contg. EtOH.

161.078 (CH3)2£OH + RSH 4.2 x 108 p.r. P.b.k. at 410 nm (RSSR") in N20- 68G132

(CH3)2 CHOH + RS2.0 x 108 7 p.r.

satd. soln. contg. 2-PrOH.

D.k. in N2 0-satd. soln. contg. 2-PrOH. 72R003

161.079 CH3CH2CH2CHOH + RSH 8.2 x 107 p.r. P.b.k. at 410 nm (RSSR*) in N2 0- 68G132

CH3CH2 CH2CH2OH + RS- satd. soln. contg. 1-BuOH.

161.081 (CH3)2CHCHOH + RSH — 1.4 x 108 p.r. P.b.k. at 410 nm (RSSR') in N20- 68G132

(CH3)2CHCH2OH + RS- satd. soln. contg. 2-methyl-l-propanol. 161.095 •CHOHCH2 CH2CH2 OH + RSH — 1.1 x 108 p.r. P.b.k. at 410 nm (RSSR") in N2 0- 68G132

(CH2CH2OH)2 + RS- satd. soln. contg. 1,4-butanediol. 161.111 R' + RSH R'H + RS- 3.2 x 107 p.r. P.b.k. at 410 nm (RSSR*) in N2 0- 68A132

(R' = Radicals from glucose) satd. soln. contg. glucose.

162. Cysteine

162.075 •CH2OH + RSH -* CH3 OH + RS. 0.5[A(CH2OH + 02)] y-r. C.k. with 02; obs. CH20 and

glycol yields. 69G524

4.2 x 107 7 p.r. D.k. in N2 0-satd. soln. contg. MeOH. 72R003

162.062 R + Cys —* no e-transfer <107 6,10, p.r. No change in d.k. at 265 nm on 71G554

(R = Radicals from

glycine anhydride + OH)

12 addn. of cysteine in N2 0-satd. soln.

162.142 R + Cys —e-transfer (2.1 ± 0.4) x 108 6.4 p.r. D.k. at 265 nm in soln. contg. 71G554

(R = Electron adduct of glycine anhydride)1 mol L'

1 fert-BuOH.

162.143 R + Cys —* e-transfer (1.4 ± 0.3) x 108 7.4 p.r. D.k. at 265 nm in soln. contg. 71G554

(R = Electron adduct of

alanine anhydride)

1 mol L"

1 rert-BuOH.

162.144 R Cys —* e-transfer (1.5 ± 0.3) x 108 7.0 p.r. D.k. at 265 nm in soln. contg. 71G554

(R = Electron adduct of

sarcosine anhydride)

1 mol L"

1 tert-BuOH.

163. Cytochrome c 163.016 •CH2 C(CH3)2 OH + Fe3+

cyt c p.r. No reaction; p.b.k. at 550 nm in N2 0-satd. soln. contg. 10"2 mol L"

1 78A288

tert-BuOH. 163.062 R + Fe ,+

cyt c <107 6.8 p.r. P.b.k. at 550 nm in N20-satd. soln. 78A288

(R = Radical from glycine anhydride)

contg. glycine anhydride.

163.075 •CH2OH + Fe ,+ cyt c — (3.0 ± 0.5) x 107 7 p.r. Abs. change at 550 and 435 nm in 79A153

Fe

2+

cyt c N20-satd. soln. contg. MeOH; 100% redn.

40
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

163.076 CH3 CHOH + Fe3+cyt c -* 2.4 x 108 2.0 p.r. 77A128

Fe2+cyt c (1.4 ± 0.2) x 108 7 p.r. Abs. change at 550 and 435 nm in N20-satd. soln. contg. EtOH; 100% redn. 79A153

1.8 x 108 ~7 p.r. Abs. change at 550 and 450 nm in N2 0-satd. soln. contg. 0.1 mol L

" 1 EtOH; see also 74A007 and 77A128.

79A312

163.078 (CH3)2COH + Fe3+

cyt c —* 3.8 x 108 7 p.r. P.b.k. at 550 nm; radical from 75A012

Fe2+cyt c 1.6 x 108 9.3 2-PrOH.

163.096 •CHOHC(CH2 OH) 3 + Fe3+cyt c - < 106 5.6 p.r. P.b.k. at 550 nm; radical from 75A012

Fe2+

cyt c 1.4 x 108 9.1 pentaerythritol. 1.6 x 108 9.8 163.106 •CHOHCHOHCH2 OH + Fe3+

cyt c 2.5 x 106 7 p.r. P.b.k. at 550 nm; radicals from 75A012

( + CH2OHCOHCH2OH) glycerol. 163.113 •A' + Fe3+

cyt c —* 6.6 x 103 7.4 p.r. D.k. at 360 nm in N2 0-satd. 75A240 A + Fe

2+

cyt c (•A" = radical from ascorbate ion)soln. contg. ascorbate

163.117 CH3 C0HC02

- + Fe3+

cyt c — (2.4 ± 0.2) x 108 p.r. P.b.k. at 550 nm in soln. contg. 74A007

Fe2+

cyt c 2.3 x 108 7 p.r.

lactate. P.b.k. at 550 nm in N2 0-satd. soln. 75A012

2.5 x 108 11 contg. 0.2 mol L

' 1 lactate. 163.120 "0

2CC0HCH2 C02" + Fe3+

cyt c - (8.5 ± 0.8) x 107 6.4 p.r. P.b.k. at 550 nm in malate soln.; 74A007

Fe2+cyt c Ea — 3 kcal mol

* 1 (12 kj mol"1 ). 163.121 "0

2CC0HCH0HC02

" + Fe3+

cyt c 1.7 x 108 7 p.r. P.b.k. at 550 nm in tartrate soln. 75A012

163.142 R + Fe3+

cyt c 8 x 108 6.8 p.r. P.b.k. at 500 nm in soln. contg. 78A288

(R = Electron adduct of

glycine anhydride)

glycine anhydride.

163.147 •C02 ~ + Fe3+

cyt c —

>

~5 x 108 >4 p.r. P.b.k. at 550 nm in soln. contg. 71G327 C02 + Fe

2+

cyt c ~3 x 109 <4 0.03-1 mol L

" 1 formate; concn. effect. 6.9 x 108 7 p.r. P.b.k. at 550 nm in N2 0-satd. soln. 75A012

2.5 x 108 10.8 contg. formate. O X O

O 6.2 p.r. Abs. change at 450 and 550 nm 76A127

6.3 x 108 8.7 in 0.1 mol L

* 1 formate soln.; at pH

6.2 Ea = 2.7 kcal mol

" 1 and A = 1.0 x 10"; at pH 8.7 £a =

3.0 and A = 1.0 x 10 11. (7 ± 0.5) x 108 7.4 p.r. P.b.k. in N20-satd. 0.1 mol L

” 1

formate; k = (5.0 ± 0.6) x 108 in 77A096

basic soln. 7.4 x 108 6.7 p.r. 77A128

9.4 x 108 2.0

1.3 x 109 7.0 p.r. P.b.k. at 550 nm in 1 atm N20, and 0.01 mol L

" 1 formate. 78A288

1.0 x 108 ~7 p.r. D.k. in formate soln.; / =0.1. 79A312

164. Cytochrome c, acetylated 164.076 CHjtHOH + Ac-cyt c 2.5 x 108 ~7 p.r. Abs. change at 550 and 450 nm

in N20-satd. 0.1 mol L

" 1 EtOH soln.; / - 0.005.

79A312

164.147 •C02

" + Ac-cyt c 1.5 x 109 — 7 p.r. D.k. at 550 nm in formate soln.; I = 0. 1 . 79A312

165. Cytochrome c, carboxymethyiated

165.076 CH3CHOH + Cxm-cyt c 3.5 x 108 ~7 p.r. Abs. change at 550 nm and 450 nm

in N20-satd. 0.1 mol L

" 1 EtOH soln. 79A312

165.121 "0

2 Ct0HCH0HC02

" + Cxm-cyt c 2.8 x 107 7 p.r. Radical from tartrate ion 78A288

165.147 •C02

~ + Cxm-cyt c 1.4 x 108 7 p.r. Radical from formate ion. 78A288

1.3 x 108 ~7 p.r. D.k. at 550 nm in formate soln.;

/ = 0 . 1 . 79A312

167. Cytochrome c, succinylated 167.076 CH jCHOH 4- Suc-cyt c 1.8 x 109 ~7 p.r. Abs. change at 550 and 450 nm

in N20-satd. 0.1 mol L

" 1 EtOH soln. 79A312

41
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mop's

-1

) PH Method Comment Ref.

167.147 •C02

’ + Suc-cyt c 4.0 x 109 ~7 p.r. D.k. at 550 nm in formate soln.; 1= 0.1. 79A312

168. Cytochrome c3 2.1 x 108 168.147 •C02* + cyt c3 8.1 p.r. D.k. in N20-satd. formate soln. 78A232

169. Cytochrome P450

169.147 •C02

" + cyt P450 No redn. obs. in N20-satd. soln. contg. formate. 79A036

Deuteroheme See 223.

Deuterohemin See 222.

Deuteroporphyrin dimethyl ester See 221a.

170. Diamide (Tetramethyldiazenedicarboxamide)

170.078 (CH3)2COH + D -+ ~2.5 x 109 p.r. P.b.k. at 400 nm. 75A194

D- + H

+ + (CH3)2CO

170.147 •C02

' + D — D~ + C02 ~2.5 x 109 p.r. P.b.k. at 400 nm. 75A194 D = (CH3)2 NCON = NCON(CH3)2

171. 1,1 '-Dibenzyl-4,4'-bipyridinium ion (Benzyl viologen)

171.078 (CH3)2COH + bv2+ -* (3.0 ± 0.1) 109 p.r. P.b.k. at 400 or 600 nm in N2 0- 76A070

(CH3)2CO + h

+ + bv- +

satd. soln. contg. 0.2 mol L"

1 2-PrOH.

171.147 •C02- + BV2+ — C02 + BV- +6.7 x 109 7.0 p.r. P.b.k. at 680 nm in N20-satd.

soln. contg. 0.2 mol L"

1 formate. 76A169

1.7 x

10'° 6.8 p.r. P.b.k. in N20-satd. soln. contg. 0.1 mol L"

1 formate. 78A321

172. l,l'-Di(carboxyethyl)-4,4'-bipyridinium ion

172.147 •C02- + BP2+ -> C02 + BP- +

2.0 x 109 7.0 p.r. P.b.k. at 680 nm in N2 0-satd.

soln. contg. 0.2 mol L"

1 formate. 76A169

173. Dichloroindophenol

173.056 NH2CHC02

- + dye 3.6 x 109 7 p.r. D.k. at 600 nm in N20-satd.

soln. contg. glycine; 87% e-transfer. 73A078

173.075 •CH2 0H + dye 3.2 x 109 7 p.r. D.k. at 600 nm in N20-satd.

soln. contg. MeOH; 99% e-transfer. 73A078

173.078 (CH3) 2COH + dye 4.4 x 109 7 p.r. D.k. at 600 nm in NzO-satd.

soln. contg. 2-PrOH; 88% e-transfer. 73A078

173.147 •C02" + dye 3.5 x 109 7 p.r. D.k. at 600 nm in NzO-satd.

soln. contg. formate, as well as

p.b.k. at ~400 nm; 100% e-transfer.

73A078

174. Dichloromethane

174.078 (CH3)2C0H + CH2C12 y-r. No redn. in soln. contg. 79G191

•CH2C1 + (CH3)2CO + H

+ + Cl- 1.5 x 10"3 mol Lf1 Na dodecyl sulfate, 0.2 mol L

_1 2-PrOH and 0.1 mol L"

1

acetone. =106 p.r. 80AQ11

175. l,l'-Di(4-cyanophenyl)-4,4'-bipyridinium ion

175.147 •C02

- + BP2+ -* C02 + BP-+ 1.4 x

10'° 6.8 p.r. P.b.k. in N2 0-satd. soln. contg. 0.1 mol Lf

1 formate. 78A321

Diethyl ketone See 3-Pentanone 305.

176. 1,2-Dihydroxybenzene (Catechol)

176.020 •CH2CH0 + H0C6H40- 7.4 x 108 — 11.5 p.r. Soln. contg. N20 and ethylene 79A051 ch3cho + oc6h4o- glycol.

177. 1,3-Dihydroxybenzene (Resorcinol)

42
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') PH Method Comment Ref.

177.020 •CH2 CH0 -1- H0C6 H40' — 1.6 x 109 -11.5 p.r. Soln. contg. N20 and ethylene 79A051 ch3 cho + 'C6H40- glycol.

1 ,4-Dihydroxybenzene See Hydroquinone 227.

178. l,3-Dihydroxy-2-nitrobenzene

178.078 (CH3) 2 tOH + (0H)2C6H3 N02 — 6.8 x 108 7 p.r. P.b.k. in N20-satd. soln. contg. 76A020

(CH3)2CO + H

+ + (0H)2C6H3N02- 0.1 mol L'

1 2-PrOH.

179. 2-(3,4-Dihydroxyphenyl)ethylamine (Dopamine

)

179.113 •A' + (OH)2C6H3 CH2 CH2NH2 (3.6 ± 0.4) x 102 8.4 p.r. D.k. at 360 nm in N20-satd. 75A240

(•A’ = Radical from

ascorbate)

soln. contg. ascorbate.

180. 2,3-Dimethylbenzoquinone

180.078 (CH3)2C0H + Q — 3.5 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L"

1 73G125

(CH3 ) 2 CO + H

+ + Q* 2-PrOH and 1 mol L"1 acetone.

181. 2.5-Dimethylbenzoquinone

181.078 (CH3) 2tOH + q — 3.9 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L"

1 73G125

(CH3)2 CO + H

+ + Q-- 2-PrOH and 1 mol L'

1 acetone. 181.097 CH3C(0-)CH2C02

- + Q — Q-- 3.3 x 109 9.2 p.r. P.b.k. at 400 nm in Ar-satd. soln. contg. rert-BuOH + acetoacetate ion. 73A104

182. 2,6-Dimethylbenzoquinone

182.078 (CH3 ) 2tOH + q ^ 4.2 x 109 p.r. P.b.k. in soln. contg. 1 mol L"

1 73G125

(CH3)2C0H + H

+ + Q-- 2-PrOH and 1 mol L"

1 acetone.

183. 1 , 1 '-Dimethyl-4,4'-bipyridinium ion1 (Methyl viologen) 183.075 •CH2OH + MV2+ — 3 x 108 p.r. N2 0-satd. 3% MeOH soln. 77A177 CH20 + H

+ + MV- + 183.147 •C02

- + MV2+ — 1.5 x 10‘° p.r. P.b.k. in N20-satd. soln. contg. 73A074 C02 + MV- +

0.1 mol L"

1 formate.

184. Dimethyl fumarate

184.078 (CH3 ) 2 COH + ch3o2cch = chco2 ch3 4.0 x 109 (uncor.) 7.0 p.r. 12% e-transfer. 73G097

184.147 •C02

- + ch3o2cch = chco2 ch3 9 x 108 (uncor.) 7.0 p.r. > 80% e-transfer. 73G097

185. 2,3-Dimethylnaphthoquinone

185.078 (CH3 ) 2tOH + Q — 3.9 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L"

1 73G125

(CH3 )2CO + H

+ + Q-- 2-PrOH and 1 mol L"

1 acetone.

185a. N,N-Dimethyl-4-nitro8oaniline (RNO)

185a. 075 •CH2 OH + RNO

CH3CH0H + RNO

(7.9 ± 0.3) x 108 7 p.r. D.k. at 440 nm in N20-satd. soln.. contg. MeOH.69G156

185a.076 (2.4 ± 0.04) x 109 7 p.r. D.k. at 440 nm in N2 0-satd. soln. contg. 0.5 mol L'

1 EtOH. 69G156

185a.078 (CH3) 2 tOH + RNO (3.2 ± 0.05) x 109 7 p.r. D.k. at 440 nm in N2 0-satd. soln. contg. 0.5 mol L"

1 2-PrOH. 69G156

185a. 147 •C02

* + RNO (1.8 ± 0.01) x 109 7 p.r. D.k. at 440 nm in N2 0-satd. soln. contg. 0.25 mol L"

1 formate. 69G156

186. 3,5-Dinitroanisole

186.078 (CH3)2 tOH + dNA — 2.5 x 109 7 p.r. P.b.k. at 310 nm in soln. contg. 79A176

(CH3) 2 CO + H

+ + dNA-' 0.1 mol L

_l 2-PrOH; reaction observed

as a slower process following

fast e

* reaction.

187. 1,2-Dinitrobenzene

187.078 (CH3

) 2tOH + C6H4(N02 ) 2 — 2.9 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111

(CH3) 2 CO + H

+ + [C6H4(N02)2

].- 2-PrOH; k at pH 0.8 within 20-30%.

43
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

188. 1 ,3-Dinitrobenzene

188.078 (CH3) 2COH + C6 H4(N02)2 -* 3.6 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111

(CH3) 2CO + H

+ +[C6H+(N02 ) 2

]-- 2-PrOH; k at pH 0.8 within 20-30%.

189. 1 ,4-Dinitrobenzene

189.078 (CH3 ) 2 COH + C6H4(N02) 2 3.2 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111

(CH3)2CO + H

+ + [C6H4(N02)2

].- 2-PrOH; k at pH 0.8 within 20-30%.

190. 2,4-Dinitrobenzoate ion

190.078 (CH3)2 COH +

-0

2 CC6H3(N02)2 -> 2.9 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111

(CH3)2CO + H

+ +

[-0

2CC6H3(N02)2

]-- 2-PrOH; k at pH 0.8 within 20-30%.

190.147 •C02

- +

-0

2CC6H3(N02 )2 — 1.8 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111 co2 + [-0

2CC6H3(N02)2

].- formate.

191. 2,5-Dinitrobenzoate ion

191.078 (CH3)2 COH +

-0

2 CC6H3(N02)2 — 3.3 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111

(CH3) 2CO + H

+ +

[-0

2 CC6H3 (N02 )2

].- 2-PrOH; k at pH 0.8 within 20-30%.

191.147 •C02~ +

"0

2 CC6 H3(N02 ) 2 - 1.9 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111 C02 + [-0

2 CC6H3(N02 )2 ].- formate.

192. 3,4-Dinitrobenzoate ion

192.078 (CH3 ) 2COH +

-0

2CC6H3(N02 )2 — 3.2 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111

(CH3) 2CO + H

+ +

[ 02 CC6H3 (N02)2

]- 2-PrOH; k at pH 0.8 within 20-30%.

192.147 •C02

- +

-0

2 CC6H3 (N02) 2 1.8 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111 C02 + [-0

2 CC6 H3(N02 )2].- formate.

193. 3,5-Dinitrobenzoate ion

193.078 (CH3 ) 2COH +

-0

2 CC6H3(N02 ) 2 — 3.1 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111

(CH3)2CO + H

+ +

[ 02CC6H3 (N02) 2

]- 2-PrOH; k at pH 0.8 within 20-30%.

193.147 •C02“ +

"0

2 CC6H3(N02) 2 —

>

2.5 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111 C02 + [ 02CC6H3(N02) 2

]. formate.

194. 3,5-Dinitrobenzonitrile

194.111 R + (N02)2C6H3CN -* 1.0 x 109 p.r. 77R167

[<N02 )2C6H3CN].- (R = Radicals from glucose)

195. l-(2,4-Dinitrophenyl)pyridinium ion

195.100 R + (N02) 2 C6H4N

+ C5H5 1.0 X 109 p.r. 77R167

[(N02) 2C6H4N

+ CsH5].- (R = Radicals from glucose) 195.147 •C02

- + (N02)2C6H4N

+ C5H5 -> 4 x 108 p.r. 77R167

[(N02) 2C6H4N

+ Cs H5].-

196. 1 , 1 '-Diphenyl-4,4'-bipyridinium ion

196.147 •C02

- + BP2+ —»• C02 + BP-+ 1.3 x

10'° 6.8 p.r. P.b.k. in N20-satd. soln. contg. 0.1 mol L'

1 formate ion. 78A321

197. Dithiothreitol 197.016 •CH2 C(CH3)2 OH + (6.8 ± 0.6) x 107 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A020

HSCH2 CHOHCHOHCH2 SH ->

(CH3 )3COH + RS- (-+ RSSR )

contg. 1 mol L'

1 tert-BuOH.

197.075 •CH20H + RSH (6.8 ± 0.6) x 107 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A020

CH30H + RS- contg. 1 mol L'

1 MeOH.

197.078 (CH3 ) 2 COH + RSH -» (2.1 ± 0.2) x 108 7 p.r. P.b.k. at 390 nm in soln. of 73A020

(CH3)2CHOH + RS- 2 mol L’

1 2-PrOH and 1 mol L’1 acetone.

Dopamine See 2-(3,4-Dihydroxyphenyl)ethylamine 179.

44
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mop's

-1

) PH Method Comment Ref.

198. Duroquinone

198.078 (CH3 ) 2£OH + Q — 4.0 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L

-1 73G125

(CH3)2CO + H

+ + -Q- 2-PrOH and 1 mol L

-1 acetone.

199. Eosin

199.076 ch3 Choh + s — (1.1 ± 0.2) x 109 8.5- p.r. P.b.k. at 405 nm in soln. 67G038

CH3 CHO + -S' + H

+

9.0 contg. 10

-2 mol L-1 EtOH and

10

-3 mol L-1 H202

. 199.147 •C02 - + S — C02 + -S' + H

+

(2.5 ± 0.5) x 108 8.5- p.r. P.b.k. at 405 nm in soln. contg. 67G038

9.0 10-2 mol L

-1 HC02

- and 10

-3 mol L-1 H2 02

.

200. Ethanol

200.001 •ch3 + CH3CH2OH — 5.9 x 102 (rel.) y-r. C.k. with 02; radical from Mel; 67G041 ch4 + ch3 £hoh rel. to £(CH3 + 02 ) = 4.7 x 109

. 200.014 •ch2 ch2 oh + C2 H5 OH — 16 ± 3 y-r. Calcd. from obs. yields and assumed 70G338

c2 hsoh + ch3Choh mechanism in oxid. of EtOH by H2 02

. 200.047 •cf3 + C2H5 OH — (4.6 ± 0.5) x 104 9-10 y-r. C.k. with -CF3 addn. to propylene; 70G407 cf3 h + c2h4oh (rel.) obs. CF3 H yield; rel. to k(CF3 +

HC02-

) = 3.4 x 105

.

201. Ethyl acetate 201.001 •CH3 -F CH3 C02Et -> <1.7 x 103 -1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 + ch3co2 <!:hch3 Ti

ni-H2 02 soln.; est. from esr meas. and values for competing reactions.

202. Ethylene

202.001 •ch3 + ch2 =ch2 -* -ch2 ch2 ch3 4.9 x 103 (rel.) y-r. C.k. with 2-PrOH in soln. contg. Mel; obs. G(CH4); rel. to A(-CH3 + 02) = 4.7 x 109

.

67G041

202.014 •ch2ch2 oh + ch2 =ch2 — (1.6 ± 0.5) x 106 4.5 p.r. Radical from OH + ethylene; contains 78A322

•ch2ch2 ch2ch2 oh (rel.) -10% (pH 4.5) and -50% (pH 2)

(4.1 ± 1.2) x 106 2 obs. rate of addn. of Cu +to ethylene

(rel.) (Cu +from OH + Cu2+

in N2 0-satd. soln.);

rel. to k( R + Cu2+

) = 1.9 x 107 (pH 4.5) and 2.2 x 107 (pH 2). (3 ± 2) x 104 y-r. Calcd. from dose rate effect on 80A054

(rel.) yields of a,oo-diols in N20-satd.

soln. contg. ethylene assuming

termination rate constant of chain

reaction is 5 x 108. 202.046 •cfci2 + ch2 =ch2 — cfci2 ch2 Ch2 — 4 x 107 5.9 p.r. Est. from condy meas. in soln. contg. CFC13

. 71G026

202.047 •cf3 + ch2 =ch2 — .ch2ch2cf3 (4.0 ± 0.6) x 107 9-10 y-r. C.k. with 2-PrOH (H abstr. by CF3); 70G407

(rel.) obs. CF3 H yield; rel. to A(-CF3 + HC02

-

) = 3.4 x 105

. -7 x 108 5.9 p.r. Est. from condy. meas. in soln. contg. CF3C1. 71G026

203. 1,1 '-Ethylene-2,2'-bipyridinium ion 203.147 •C02

- + BP2+ — C02 + BP+

4.0 x 109 7.0 p.r. P.b.k. in N2 0-satd. soln. contg. 0.2 mol L

-1 formate ion. 76A169

1.2 x

10'° 6.8 p.r. P.b.k. in N20-satd. soln. contg.

0.1 mol L

-1 formate ion. 78A321

204. Ethylene glycol 204.075 •CH2 OH + HOCH2CH2 OH — - 103-104 y-r. Est. from dose effect on yields 71G929

ch3 oh + hoChch2 oh in MeOH soln.

45
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ’) PH Method Comment Ref.

205. Ethyl ether

205.048 •CC13 + CH3CH2 OEt 35 y-r. Calcd. from dependence of C(C1") 71G778

CHC13 + CH3CHOEt on dose rate in soln. contg. 2 x 10

" 3 mol L"1 CC14 and 0.5 mol L

" 1

ethyl ether; assume 2&(R + R) = 109.

206. /V-Ethylmaleimide (NEM)

206.016 •CH2 C(CH3)2 OH + NEM -NEM-R p.r. No e-transfer; very low addn. rate; radical from tert-BuOH. 72G144

206.053 CH3CONHCH2 + NEM -NEM-R ~ 108 6-7 p.r. 100% addn. based on abs. spectra; radical from TV-methylacetamide.72G144

206.075 •CH20H + NEM

•NEM' + -NEM-CH2 0H

(CH3)2fiOH + NEM

2.4 x 109 (uncor.) 6-7 p.r. P.b.k. in N20-satd. soln. contg. MeOH; 15% e-transfer, 85% addn. based on abs. spectra.

72G144

206.078 5.0 x 109 (uncor.) 6-7 p.r. 47% e-transfer, 50% addn. based on 72G144

•NEM' + -NEM-R abs. spectra; radical from 2-PrOH.

206.109 R + NEM 2.1 x 109 (uncor.) 6-7 p.r. 30% e-transfer, 20% addn. based on 72G144

(R = Radicals from ribose) abs. spectra. 206.141 R + NEM - -NEM' 2.2 x 109 p.r. D.k. 73G097

(R = Electron adduct of dimethyl fumarate) 206.147 •C02

- + NEM C02 + -NEM" 5.4 x 109 6-7 p.r. P.b.k. in N2 0-satd. soln. contg. formate; 100% e-transfer based on abs. spectra.

72G144

207. 4-Ethylphenoxide ion 207.020 •CH2 CH0 + C2 H5C6H40- 7.0 x 107 -11.5 p.r. Soln. contg. N20 and ethylene 79A051 (+ H2 0) -*• CH3 CH0 -f OH- +

c2 h5 c6h4oglycol.

208. Ferredoxin

208.147 •C02

- + ferredoxin (8.0 ± 0.7) x 107 7.5 p.r. D.k. at 420 nm in N20-satd.

soln. contg. 0.1 mol L

" 1 formate. 73A064

Flagyl See Metronidazole 271.

Flavin mononucleotide (FMN) See Riboflavin 5'-phosphate 334.

209. Fluorescein

209.076 CH3 CHOH + Dye —> semiquinone 4.5 x 108 10.8 p.r. D.k. at 500 nm in N2 0-satd. soln. contg. EtOH. 73A078

209.147 •C02

- + Dye —* semiquinone (2.6 ± 0.9) x 107 10.4 p.r. P.b.k. in N20-satd. soln. contg. 10 2 mol L

" 1 formate. 68G172

210. Folic acid 210.078 (CH3)2 COH + FH2 +

1.1 x 109 -0.5 p.r. P.b.k.; structure and abs. spectra 76A060

(CH3) 2 COH + FH — 4.0 x 108 6.0 of reduced species dependent on pH. (CH3)2 CO + H

+ + -FH211 . Formaldehyde

211.075 •CH2OH + CH2(OH) 2 -* ~ 104-105 y-r. Est. from dose effects on yields in 71G929

CH3 OH + -CH(OH) 2 soln. contg. MeOH.

212 . Formate ion 212.047 •cf3 + HC02 - - CF3 H + -C02- (3.4 ± 0.7) x 105 9-10 p.r. P.b.k. at 270 nm (C02

~); radical from CF3 C1 -f eaq

". 70G407

213. 7V-Formylkynurenine

213.147 •C02

- + FK (+ H

+

) — >3 x 107 7.6 p.r. P.b.k. (semiquinone) in N20-satd. 75F361 C02 + -FKH soln. contg. 0.1 mol L

" 1 formate.

46
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

214. Fumarate ion 214.047 •CF3 +

-0

2 CCH = CHC02-^ -108 e-r. Est. from esr. 71G284

-0

2 CtHCH(CF3)C02- 214.075 •CH2OH +

-0

2 CCH = CHC02-^ -107 e-r. Est. by esr from dose rate effect 71G284

-0

2 C£HCH(CH20H)C02

- on -CH2 OH and adduct radical (in 1 mol L'

1 MeOH and 0.01 mol L"1 fumarate) assuming 2&(R + R) = 2.4 x 109

; other

radicals adding to fumarate ion were •CH3, -CHOHCH3, (CH3 ) 2tOH, -chohch2 oh,

•ch2nh2 , -ch2 ci, -chcico2-,-co2

-, -cf3, and •CH(C02 ")CH2 C02

-. 214.113 •A- +

'0

2 CCH = CHC02

- <10 8.7 p.r. D.k. at 360 nm in N2 0-satd. soln. 75A240

(•A* = ascorbate radical) contg. ascorbate ion. 214.147 •C02

- +

-0

2CCH = CHC02 H 2.0 x 107 (uncor.) 4.0 p.r. > 30% e-transfer; no e-transfer at pH 10.0. 73G097

215. Fumaric acid 215.078 (CH3 ) 2 tOH + ho2 cch = chco2h 9.0 x 108 (uncor.) 0.5 p.r. 14% e-transfer. 73G097

215a. Glutathione

215a. 142 R + GSH —* e-transfer (1.8 ± 0.3) x 108 6.4, p.r. D.k. at 265 nm in soln. contg. 71G554

(R = Electron adduct of

glycine anhydride)

7.4 1 mol L*

1 <erf-BuOH.

216. Glutathione disulfide 216.078 (CH3)2COH + GSSG <107 7 p.r. No 420 nm abs. (RSSR") obs. in N20-satd. soln. contg. 0.1 mol L"

1 2-PrOH.

72G388

216.142 R + GSSG - (GSSG)- (4.0 ± 0.4) x 107 6.2 p.r. D.k. at 265 nm in soln. contg. 71G554

(R = Electron adduct of glycine anhydride)

1 mol L'

1 tert-BuOH.

216.147 •CO2 + GSSG A 0 p.r. No 420 nm abs. (RSSR") obs. in N20-satd. soln. contg. 0.1 mol L"

1

formate.

72G388

217. Glycine

217.001 •ch3 + H2NCH2 C02- — ~1.2 x 102 (rel.) -10 phot. •CH3 from cumene hydroperoxide; obs. 70F280 ch4 + H2NCHC02

- formn. of CH4 and C2 H6; assume 2&(R •ch3 + H3N

+ CH2C02

- — 4 (rel.) + R) = 2 x 109

; kH /kD = 10.5 at pH 11.5 [74F528],

218. Glycine anhydride

218.147 •C02 - + -NHCH2 C0NHCH2 C(0)- A o

j 6.2 p.r. No e-transfer obs. in N2 0-

satd. soln. contg. 0.2 mol L"

1 formate.

71G554

219. Glycolic acid 219.001 •ch3 + hoch2co2 h — 3.6 X 103 -1 chem. Radical from dimethylsulfoxide in 75D188 ch4 + ho£hco2 h Ti IM -H2 02 soln.; est. from esr meas. and values for competing reactions.

220. Hematoporphyrin

220.075 •ch2 oh + ph2 — -PH2- <1 x 107 7.0 p.r. P.b.k. at 600-650 nm in N20-satd. 74A040

•ch2o- + ph2 — -PH2

- (3.3 ± 0.5) x 108 13.0 soln. contg. 0.1 mol L"

1 MeOH.

220.076 ch3Cho- + PH2 -» PH2- (7.0 ± 1.0) x 108 13 p.r. P.b.k. at 600-650 nm in N2 0-satd.

soln. contg. 0.1 mol L'

1 EtOH. 74A040

220.078 (CH3 ) 2tOH + PH2 — -PH2

- (2.4 ± 0.4) x 108 7.0 p.r. P.b.k. at 600-650 nm in N2 0-satd. 74A040

(CH3)2Co- + ph2 — -PH2 - (1.1 ± 0.2) x 109 13.0 soln. contg. 0.1 mol L"

1 2-PrOH.

220.147 •C02

- + ph2 — -PH2

- (4 ± 1) x 107 13.0 p.r. P.b.k. at 600-650 nm in N20-satd.

soln. contg. 0.1 mol L"

1 formate. 74A040

47
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's'

1 ) pH Method Comment Ref.

221. Zinc hematoporphyrin

221.078 (CH3)2 tO~ + ZnP -> (1.0 ± 0.1) x 109 13.0 p.r. P.b.k. at 600-650 nm in N20-satd. 74A040

(CH3)2 CO + ZnP-' soln. contg. 1 mol L'

1 2-PrOH.

221a. Deuteroporphyrin dimethyl ester 221a.001 •CH3 + DP (1 to 2) x 107 -13 p.r. Est. from abs. change in soln. contg. 6.5 mol L"

1 2-PrOH, 0.7 mol L'1 acetone and 2.3 x 10'2 mol L"

1 CH3

I; cor. for -CH3 + -CH3

.

81A002

221a.078 (CH3 )2Co- + DP -> DP' (6 ± 1) x 108 -13 p.r. Abs. change in soln. contg. 6.5 mol L'

1 2-PrOH and 0.7 mol L'

1 81A002

acetone.

Deuteroporphyrin (ferri) See Deuterohemin 222.

Deuteroporphyrin (ferro) See Deuteroheme 223.

222. Deuterohemin

222.001 •CH3 + DH«(Fem

) - addn. (2.3 ± 0.5) x 109 -13 p.r. Abs. change in soln. contg. 6.5 81A002

~1.3 x 109 7 mol L'

1 2-PrOH and 4.1 x 10'3 mol L"

1 methyl iodide. 222.050 •CC13 + DH(Feni

) <106 7.2 p.r. No spectral change in soln. contg. 6.5 mol L'

1 2-PrOH, 5 x 10'3 mol L'1 80A011

CC14 and lO^1 mol L'

1 deuterohemin. 222.078 (CH3)2 £OH + DH(FeIM

) 3.7 x 108 7.2 p.r. D.k. in Ar-satd. soln. contg. 6.5 80A011

DH(Fe") mol L"

1 2-PrOH and 3.4 x 10*2 mol L"

1

acetone. (CH3)2CO' + DH(Feni

) -> (9 ± 1) x 108 -13 p.r. D.k. in soln. contg. 6.5 mol L'

1 81A002

DH(Fe") 2-PrOH.

223. Deuteroheme

223.001 •CH3 + DH(Fe") -> addn. (3.9 ± 0.5) x 109 7 p.r. Abs. change in 6.5 mol L"

1 2-PrOH

soln. of deuterohemin chemically reduced by dithionite to which methyl

chloride was added.

81A002

223.043 •CH2C1 + DH(Fe") 2 x 109 7.2 p.r. Abs. change in soln. of deuterohemin 80A011

chemically reduced by dithionite to which 4 x 10'2 mol L'

1 CH2C12 was

added. 223.048 •CC13 + DH(Fe“) (2 ± 1) x 109 7.2 p.r. Abs. change in soln. contg. 6.5 mol L'

1 2-PrOH, 3.2 x 10'2 mol L'1

acetone, CC14, and deuterohemin, the

latter reduced by (CH3) 2tOH.

80AO11

223.078 (CH3)2COH + DH(Fe") (6.3 ± 0.5) x 108 7 p.r. Abs. change in 6.5 mol L'

1 2-PrOH

soln. of deuterohemin chemically reduced by dithionite to which 0.7 mol L"

1 acetone was added.

81A002

224. Hemin (Protoferriheme IX)

224.076 CH3CHO- + H(FeIn

) -* H(Fen

) (9.0 ± 1.0) x 108 13 p.r. Soln. 30% EtOH, N2 0-satd. 74A040

CH3CHOH + H(Fein

) H(Fe") 7.7 x 108 7 p.r. Redn. obs. at 560 nm in N20-satd.

soln. contg. 0.1 mol L*

1 EtOH. 77A128

(5.6 ± 0.6) x 108 9.2 p.r. D.k. at 490 nm in N20-satd. soln. 78A033

(1.6 ± 0.6) x 109 4.0 contg. 1 mol L"

1 EtOH and 0.2 mol L'

1 Na dodecylsulfate (micelles).

225. Hemin c 225.078 (CH3 ) 2COH + H(Fe'") H(Fe") (2.8 ± 0.6) x 109 7.0 p.r. P.b.k. at 413 nm in N20-satd. soln. contg. 0.04 mol L"

1 2-PrOH. 75A241

225.096 •CHOHC(CH2 OH)3 + H(Fe'") -> (3.0 ± 0.6) x 108 7.0 p.r. P.b.k. at 413 nm in N2 0-satd. soln. 75A241

H(Fe") (2.8 ± 0.6) x 108 11.8 contg. 0.25 mol L'

1 pentaerythritol.

48
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

225.106 CH2 OHCOHCH2OH + H(Fe'") — (1.3 ± 0.3) x 109 7.0 p.r. P.b.k. in N20-satd. soln. contg. 75A241

225.117

H(Fe")

( + CH2 OHCHOHtHOH)

CH3t0HC02

- + H(Fem

) — (5.6 ± 1.1) x 108 7.0 p.r.

10~2 mol L"

1 glycerol.

P.b.k. in N20-satd. soln. contg. 75A241

225.121

H(Fe") 02 CCH0HC0HC02

- + H(Fe"‘) (8.1 ± 1.6) x 107 7.0 p.r.

O. 025 mol L~’ lactate. P. b.k. in N20-satd. soln. contg. 75A241

225.147

H(Fe") •C02

- + H(Fem

) — H(Fe") (1.3 ± 0.3) x 109 7.0 p.r.

O. 02 mol L“' tartrate. P. b.k. in N2 0-satd. soln. contg. 75A241

226. 226.075 Hemoglobin

•CH2 OH + H(Felu

) — H(Fe") (9.5 ± 1.5) x 106 7 p.r.

0.02 mol L"

1 formate.

Abs. change at 550 and 435 79A153

226.076 CHjtHOH + H(Fem

) — H(Fe") (4.0 ± 0.4) x 107 7 p.r.

nm in N2 0-satd. soln. contg. MeOH; 100% redn. Abs. change at 550 and 435 79A153

227. 227.016 Hydroquinone

•CH2C(CH3)2OH + H0C6H40H <2 x 106 11.5 p.r.

nm in N2 0-satd. soln. contg. EtOH; 100% redn.

Semiquinone not formed in 79A051

227.020 (CH3)3COH + 0C6H40- •ch2 cho + HOC6H40- (2.2 ± 0.1) x 109 — 11.5 p.r.

tert- BuOH soln. Soln. contg. N20 and ethylene 79A051

227.021

CH3 CHO + -0C6 H40-

•ch2cho + H0C6H40H

ch3Chcho + H0C6H40- <2 x 106

(1.2 ± 0.1) x 109 7.2 -11.5

p.r.

p.r.

glycol or 2-methoxy- or 2-ethoxyethanol. Radical from 2-chloroethanol.

P.b.k. at 430 nm (semiquinone) in 79A051 79A051

227.023

227.024

ch3coCh2 + H0C6 H40-

ch3coch2ch3 + H0C6H40- (5.6 ± 0.5) x 108 -11.5 p.r.

N2 0-satd. soln. contg. 1,2-propanediol; radical mixture.

P.b.k. at 430 nm in N20-satd. 79A051

227.025 -(CH2)4CHCO- + H0C6H40- (5.5 ± 1.9) x 108 -11.5 p.r.

soln. contg. 2,3-butanediol.

P.b.k. at 430 nm in N20-satd. 79A051

227.026 hoch2 chcho + H0C6H40- (1.3 ± 0.1) x 109 -11.5 p.r.

soln. contg. 1,2-cyclohexanediol.

P.b.k. at 430 nm in N20-satd. 79A051

227.027

(and HOCH2 COCH2)

hoch2 ch2 co£h2 + HOC6H4CT (6.2 ± 0.8) x 108 -11.5 p.r.

soln. contg. 2,3-epoxypropanol;

radical also obtained from

glycerol, k = (1.5 ± 0.1) x 109 and glycerol 2-phosphate, k =

(1.7 ± 0.2) x 109

. P.b.k. at 430 nm in N20-satd. 79A051

227.028 HO(CH2 ) 3CHCHO + H0C6H40- (8.6 ± 1.2) x 108 -11.5 p.r.

soln. contg. 2-hydroxyfuran.

P.b.k. at 430 nm in N2 0-satd. 79A051

227.029 HO(CH2 ) 4£HCHO + H0C6H40- (5.2 ± 0.9) x 108 -11.5 p.r.

soln. contg. 2-(hydroxymethyl)furan.

P.b.k. at 430 nm in N2 0-satd. 79A051

227.030 R + H0C6H40- (1.3 ± 0.3) x 109 -11.5 p.r.

soln. contg. 2-(hydroxymethyl)pyrani

P.b.k. at 430 nm in N20-satd. 79A051

227.031

(R = Radicals from

erythritol) R + HOC6H40- (1.2 ± 0.1) x 109 -11.5 p.r.

soln. contg. /rce-so-erythritol.

P.b.k. at 430 nm in N2 0-satd. 79A051

227.032

(R = Radicals from

xylitol) -<CHOH)3CH2tHCO- + hoc6h4o- (6.4 ± 1.1) x 108 -11.5 p.r.

soln. contg. xylitol.

P.b.k. at 430 nm in N2 0-satd. 79A051

227.033 R + H0C6H40- (9.8 ± 1.3) x 108 -11.5 p.r.

soln. contg. meio-inositol.

P.b.k. at 430 nm in N20-satd. 79A051

227.109

(R = Radicals from

sorbitol) R + hoc6h4ct (9.6 ± 1) x 108 -11.5 p.r.

soln. contg. sorbitol.

P.b.k. at 430 nm in N20-satd. 79A051

227.111

(R = Radicals from ribose) R + H0C6 H4Q- (7.1 ± 0.9) x 108 -11.5 p.r.

soln. contg. ribose. P.b.k. at 430 nm in N20-satd. 79A051

(R = Radicals from glucose) soln. contg. glucose.

l-(2-Hydroxyethyl)-2-methyl-5~nitroimidazole See Metronidazole 271.

l-(2-Hydroxy-3-methoxvpropyl)-2-nitroimidazole See Misonidazole 272. 49
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L moP's"1 ) PH Method Comment Ref.

228. 2-Hydroxy-1,4-naphthoquisione

228.042 R + Q

-> -Q- 1.9 x 109 10 p.r. P.b.k. at 400 nm in N2 0-satd. 73A104

(R = Radicals from

triglycine) (3.1 ± 0.3) x 109

soln. contg. triglycine.

228.056 NH2 tHC02

- + Q

-Q-

(CH3)2 COH + Q

-> -Q8.0 p.r. P.b.k. at 400 nm in N20-satd.

soln. contg. glycine. 73A104

228.078 (3.4 ± 0.3) x 109 7.0 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. 2-PrOH. 73A104

CH36(0')CH2 C02 228.097 ' + <?-*•<?' (1.5 ± 0.2) x 109 9.2 p.r. P.b.k. at 400 nm in Ar-satd. soln. contg. acetoacetate ion and

tert- BuOH.

73A104

228.115 •CHOHCO,- + Q

-> -Q- (9.1 ± 0.9) x 108 7.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. glycolate. 73A104

228.147 •C02 + Q —* 'Q (1.95 ± 0.2) x 109 7.0 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. formate. 73A104

229. 3-Hydroxy-2-nitrobenzoate ion

229.078 (CH3 )2COH 4- -0

2CC6H3(0H)N02 -+ 3.3 x 108 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A020

(CH3)2 CO + H

+ +

-0

2 CC6H3 (0H)N02 0.1 mol L'

1 2-PrOH.

230. 3-Hydroxypropionitrile

230.001 •CH3 + CNCH2 CH2OH -V <1.6 x 103 ~1 chem. Radical from dimethyl sulfoxide in 75D188

ch4 + cnch2 Choh TiIU-H202 soln.; est from esr meas. and values for competing reactions.

4-Hydroxy-2,2, 6, 6-tetramethyl-l-piperidinyloxy See Tetramethylhydroxypiperidinyloxy(TMPN) 343.

231. Indigo disulfonate 231.056 NH2£HC02- + Dye 2.8 x 109 9 p.r. D.k. at 610 nm in N20-satd. soln. contg. glycine; 71% e-transfer. 73A078

231.075 •CH2 OH + Dye 2.0 x 109 7 p.r. D.k. at 610 nm in N2 0-satd. 73A078

(CH3) 2COH + Dye

1.9 x 109 9 soln. contg. MeOH; e-transfer 75%

at pH 7 and 62% at pH 9. 231.078 4.0 x 109 7,9 p.r. D.k. at 610 nm in N2 0-satd. soln. contg. 2-PrOH; 88% e-transfer. 73A078

231.147 •C02~ + Dye —» 2.0 x 109 7.0 p.r. D.k. at 610 nm in N20-satd. soln. 73A078

C02 + Dye'

2.1 x 109 7.0 p.r.

contg. formate.

P.b.k. at 400 nm. 73A078

232. Indigo tetrasulfonate 232.056 NH2CHC02

- + Dye 2.6 x 109 7.0 p.r. D.k. at 610 nm in N2 0-satd. soln. contg. glycine; 78% e-transfer. 73A078

232.075 •CH2 OH + Dye 3.0 x 109 7 p.r. D.k. at 610 nm in N20-satd. ssoln. contg. MeOH; 80% e-transfer. 73A078

232.078 (CH3) 2 tOH + Dye 4.2 x 109 7 p.r. D.k. at 610 nm in N20-satd. soln. contg. 2-PrOH; 89% e-transfer. 73A078

233. Indophenol

233.075 •CH2 OH + Dye 3.1 x 109 9 p.r. D.k. at 610 nm in N2 0-satd. soln. contg. MeOH; 92% e-transfer. 73A078

233.078 (CH3)2tOH + Dye 4.0 x 109 9 p.r. D.k. at 610 nm in N20-satd. soln. contg. 2-PrOH; 86% e-transfer. 73A078

233.147 •C02

" + Dye —

>

2.8 x 109 9.0 p.r. D.k. at 610 nm in N20-satd. soln. 73A078

C02 + Dye'

2.7 x 109 9.0 p.r.

contg. formate.

P.b.k. at ~400 nm. 73A078

233a. Zinc(II) Insulin

233a. 147 •C02 ' + Zn(II)Insulin 6 x 108 9.0 p.r. P.b.k. at 420 nm in N2 0-satd. soln. 80A204

contg. 10~2 mol L"

1 formate; based on monomer concn.

50
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

234. Iodoacetamide

234.078 (CH3 ) 2 tOH + ICH2 CONH2 4 x 108 (rel.) p.r. C.k. with /?-nitroacetophenone in soln. contg. 2-PrOH and acetone;

rel. to *(R + PNAP) = 3.8 x 109

.

73A140

235. Iodoacetate ion 235.078 (CH3 ) 2 tOH + ICH2 C02- 7 x 107 (rel.) p.r. C.k. with /?-nitroacetophenone in soln. contg. 2-PrOH and acetone;

rel. to k(R + PNAP) = 3.8 x 109

.

73A 140

236. Iodoacetic acid 236.016 •CH2 C(CH3 ) 2 OH + ich2 co2 h — (1.3 ± 0.3) x 107 1 chem. Est. from esr meas. in TiIM -H2 02 74D286

ICH2 C(CH3) 2OH + -ch2 co2 h (rel.) soln. contg. fert-BuOH; rel. to 2*(-CH2C02 H + -CH2 C02 H) = 1.8 x 109

. 236.075 •ch2oh + ich2co2 h — (2.1 ± 0.7) x 108 1 chem. Est. from esr meas. in Tim-H2 02 74D286

•CH2C02 H + prod. (rel.) soln. contg. MeOH; rel. to 2A(-CH2 C02 H + -CH2 C02 H) = 1.8 x 109

. <3.5 x 108 p.r. P.b.k. at 330 nm. 74D286

237. Iodoacetonitrile 237.016 •CH2 C(CH3 )2OH + ich2cn 2.0 x 107 (rel.) 1 chem. Est. from esr meas. in TiUI -H202 74D286

ICH2C(CH3)2OH + -ch2 cn soln. contg. tert-BuOH; rel. to 2A(-CH2CN + -CH2CN) = 2 x 109

.

238. Iodoethanol

238.016 •CH2 C(CH3 ) 2OH + ICH2 CH2OH 1.5 x 10s (rel.) 1 chem. Est. from esr meas in Tim

-H2 02 74D286

ICH2C(CH3 ) 2 OH + -CH2CH2OH soln. contg. tert-BuOH; rel. to 2£(-CH2CH2 OH + -CH2CH2 OH) = 1.9 x 109

.

238a. Iodomethane

238a.078 (CH3 ) 2 CO- + CH3I -> -CH3 (1.1 ± 0.1) x 108 ~ 13 p.r. C.k. with PNAP in soln. contg. 6.5 81A002

(CH3)2 COH + ch3

i <10s 7 mol L"

1 2-PrOH and 0.68 mol L"1 acetone assuming k = 2.2 x 109 (279.078).

239. 3-Iodopropionic acid 239.016 •CH2 C(CH3 )2OH + ich2ch2 co2 h -> 1.8 x 10s (rel.) 1 chem. Est. from esr meas. in Tiln -H2 02 74D286

ICH2C(CH3 ) 2OH + -ch2 ch2co2 h soln. contg. <ert-BuOH; rel. to 2A(-CH2 CH2 C02 H + -CH2 CH2C02 H) = 2.4 x 109

. 239.075 •ch2oh + ICH2CH2C02 H — 1.0 x 10s (rel.) 1 chem. Est. from esr meas. in Ti m-H2 02 74D286

•CH2 CH2C02 H + prod. soln. contg. MeOH; rel. to 2A(-CH2CH2 C02 H + -CH2 CH2C02 H) = 2.4 x 109

.

240. 3-Iodotyrosine

240.147 •C02 + (1.3 ± 0.1) x 10s 3.0 X-r. Est. from dependence of tyrosine 72G610

IC6 H3(0H)CH2 CH( + NH3)C02 H yields on irrad. time in soln. contg. —*• C02 + 1' + -Ar 10’2mol L'

1 formate assuming 2A(R + R) = 5.0 x 108

.

241. Isobutylene

241.001 •CH3 + (CH3) 2C = CH2 —* addn. 3.9 x 104

(rel.) y-r. C.k. with MeOH in soln. contg. Mel

obs. G(CHJ; rel. to &(-CH3 + 02 ) = 4.7 x 109

.

67G041

242. Isobutyric acid 242.001 •CH, + (CH3)2 CHC02 H — 9.0 x 103 (rel.) ~1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 + (CH3 ) 2tC02 H Ti m

-H2 02 -soln.; est. from esr meas. and values for competing reactions.

51
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol V) pH Method Comment Ref.

243. Isobutyronitrile 243.001 •CH3 + (CH3)2CHCN — 4.5 x 103 (rel.) ~1 chem. Radical from dimethyl sulfoxide in 75D188

CH4 + (CH3 )2CCN Ti

IM -H202-soln.; est. from esr meas. and values for competing reactions.

244. Isonicotinamide

244.078 (CH3 ) 2COH + NH+ — (3.1 ± 0.6) x 109 0.7 p.r. P.b.k. (pyridinyl radical) in 74A089

(CH3)2 CO + H

+ + -NH N20-satd. soln. contg. 2-PrOH.

245. Isonicotinic acid 245.078 (CH3 )2COH + h

+ nc5h4co2 h 2.0 x 109 0.4 p.r. P.b.k. at ~400 nm (pyridinyl 74A106

(CH3) 2COH + H

+ NCs H4C02- 8.5 x 108 3.2 radical) in N20-satd. soln. contg. (CH3) 2COH + NC5 H4C02

- < 1 x 106 9.0 0.5 mol L1 2-PrOH.

(CH3)2Ccr + nc5h4co2- 2 x 108 13.3

Isopropanol See 2-Propanol 314.

246. a-Ketoglutarate ion 246.113 •a- + -o2cch2 ch2coco2

- <10 9.7 p.r. D.k. at 360 nm in N20-satd. soln. 75A240

(•A' = ascorbate radical) contg. ascorbate ion.

247. Lactate ion 247.113 •A' + CH3 CH0HC02

- <10 8.6 p.r. D.k. at 360 nm in N2 0-satd. soln. 75A240

(•A' = ascorbate radical) contg. ascorbate ion

248. Lactic acid 248.001 •ch3 + CH3CH0HC02 H — 1.2 x 104 ~1 chem. Radical from dimethyl sulfoxide in 75D188

ch4 + ch3 Cohco2 h Tinl -H2 02 soln.; est. from esr meas. and values for competing reactions.

249. Lipoate ion 249.076 CH3CHOH + RSSR -> 1.0 x 108 7 p.r. P.b.k. at 410 nm in N2 0-satd. 70G560

(RSSR)- + CH3 CHO + H

+

soln. contg. 0.1 mol L

_1 EtOH.

249.078 (CH3)2tOH + RSSR — 1.8 x 108 7 p.r. P.b.k. at 410 nm in soln. contg. 70G560

(RSSRT + (CH3)2 CO + H

+

1 mol L"

1 acetone and 2-PrOH.

249.147 •C02 ‘ + RSSR — 5.5 x 108 7 p.r. P.b.k. at 410 nm in N20-satd. 70G560

(RSSR)' + C02 5.6 x 108 6.1- p.r.

soln. contg. 0.1 mol L'

1 formate ion. P.b.k. at 410 nm; k — 9 x 108 75A195

9.2 at pH 3. RSSR = -SCH2 CH2CH[(CH2) 4C02 ]S250. Lumazine

250.078 (CH3)2COH + LH2 -> (1.3 ± 0.1) x 109 0.8, p.r. P.b.k. in N20-satd. solns. of 1-2 75A056

(CH3)2CO + lh3

- 5.1 mol L'

1 2-PrOH; 100%, 70% and 85%

(CH3 )2COH + LH- -> (1.7 ± 0.2) x 108 9.5 e-transfer at acid pH and pH 9.5 (CH3)2 CO + LH2

-- (uncor.) and 14.0, resp. (CH3)2 CO- + L

2- (1.0 ± 0.2) x 109 14.0 (CH3)2CO + LH-2- (uncor.)

251. Lysozyme

251.147 •C02

" + lys —* ~5 x 108 ~6 p.r. P.b.k. at 420 nm in N20-satd. 75A080 co2 + (-ss-r soln. contg. 0.1 mol L-' formate and

2 x lO"4 mol L"

1 lysozyme; value from

graph; k pH-dependent.

252. Maleic acid 252.078 (CH3)2tOH + H02CCH = CHC02 H 2.2 x 108 (uncor.) 0.5 p.r. 18% e-transfer; no e-transfer at pH 10.0 (dianion). 73G097

252.147 •C02 - + H02CCH = CHC02- 1.1 x 108 (uncor.) 5.2 p.r. > 65% e-transfer; no e-transfer at 73G097

at pH 10.5 (dianion).

Menaquinone See 2-Methylnaphthoquinone 262.

52
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 1 s

_l

) pH Method Comment Ref.

253. 2-Mercaptoethanol

253.014 •CH2 CH2 OH + HO(CH2 ) 2SH (4.7 ± 0.7) x 107 10 p.r. P.b.k. (RSSR‘) in Ar-satd. soln.; 69G553 CH3 CH2OH + HO(CH2) 2 -S radical from eaq ~ + HO(CH2)2SH.

253.016 •CH2C(CH3)2 OH + HO(CH2 ) 2 SH — (8.2 ± 1.2) x 107 10 p.r. P.b.k. at 420 nm (RSSR~) in N2 0-satd. 69G553

(CH3 )3COH 4- HO(CH2)2 S- soln. contg. 0.1 mol L'

1 tert-BuOH. 253.075 •CH2 OH + HO(CH2 )2 SH — (1.3 ± 0.2) x 108 10 p.r. P.b.k. (RSSR“) in N2 0-satd. soln. 69G553

CH3 OH + HO(CH2)2 S- contg. 0.1 mol L"

1 MeOH.

253.076 CHjCHOH + HO(CH2 ) 2 SH — (2.3 ± 0.3) x 108 10 p.r. P.b.k. (RSSR~) in N2 0-satd. soln. 69G553

CH3CH2 OH + HO(CH2)2 S- contg. 0.1 mol L'

1 EtOH.

253.078 (CH3)2 COH + HO(CH2 )2 SH — (5.1 ± 0.8) x 108 10 p.r. P.b.k. (RSSR~) in N2 0-satd. soln. 69G553

(CH3 )2 CHOH + HO(CH2 )2 S- contg. 0.1 mol L"

1 2-PrOH.

253a. 3-Mercaptopropionate ion

253a.l42 R 4- HSCH2 CH2 C02

" —* e-transfer (3.0 ± 0.3) x 108 5.3, p.r. D.k. at 265 nm in soln. contg. 71G554

(R = Electron adduct of

glycine anhydride)

1 mol L'

1 rert-BuOH.

254. Methanethiol

254.001 •ch3 + ch3 sh — ch4 + ch3 s- (7.4 ± 1) x 107 11 p.r. P.b.k. (RSSR') in Ar-satd. soln.; radical from e

* reaction with CH3SH. 69G553

255. Methanol

255.001 •ch3 + ch3 oh — ch4 + -ch2oh 2.2 x 102 (rel.) y-r. C.k. with 02; radical from Mel;

rel. to A(CH3 4 02) = 4.7 x 109

. 67G041

>1 x 102 1 phot. Radical from Co(NH3)502CCH32+

; est. from effect of addn. of MeOH on CH4 and C2 H6 yields.

71F579

255.047 •cf3 + ch3 oh -* cf3 h + -ch2 oh (8.1 ± 1.2) x 103 9-10 y-r. C.k. with addn. of -CF3 to propylene; 70G407

(rel.) obs. G(CF3H); rel. to A(CF3

-I- HC02

‘) = 3.4 x 105

. 255.113 •A' 4 CH3OH <0.1 8.8 p.r. D.k. at 360 nm in N2 0-satd. soln. 75A240

(•A” = ascorbate radical) contg. ascorbate ion.

256. Methemerythrin

256.147 •C02

- + MFe3+

6.8 x 107 8.2 p.r. D.k. at 360 nm in N2 0-satd. soln. contg. 10'2 mol L

_1 formate; / = 0.03. 79A204

257. 3-Methoxy-2-nitrotoluene

257.078 (CH3 ) 2 tOH 4- ArN02 -> 2.3 x 108 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A020

(CH3 )2CO 4- ArN02

‘ 0.1 mol I/1 2-PrOH.

258. 4—Methoxyphenoxide ion 258.020 •CH2 CHO + CH30C6 H40- (+ H2 0) — On CO X o -11.5 p.r. Soln. contg. N20 and ethylene glycol. 79A051 CH3 CHO + CH3C6H40- 4- OH259. 2-Methylbenzoquinone

259.078 (CH3 ) 2tOH + Q — 3.5 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L~' 73G125

<ch3)2 co + h

+ + -q- 2-PrOH and 1 mol L’

1 acetone.

260. Methylene blue

260.056 NH2 CHC02- + MB+

3.7 x 109 7 p.r. D.k. at 580 nm in N20-satd. soln. contg. glycine; 86% e-transfer. 73A078

260.075 •CH2 OH + MB+

3.4 x 109 7 p.r. D.k. at 580 nm in N2 0-satd. soln. contg. MeOH; 91% e-transfer. 73A078

260.078 (CH3 )2COH + MB+

(4 ± 2) x 109

p.r. 73A150

4.4 x 109 7 p.r. D.k. at 580 nm in N2 0-satd. soln. 73A078

contg. 2-PrOH; 91% e-transfer.

53
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L moR's"

1 ) pH Method Comment Ref.

260.147 •C02- 4- MB+ —> 5.6 x 109 ~9 p.r. D.k. at 580 nm in soln. contg. 65G396

C02 + MB- 0.1 mol L"

1 formate. •C02 H + MB+ -* ~2 x 109 1.75 p.r. D.k. at 580 nm. 65G396

C02 + H

+

4- MB-

•C02 H + MBH2+ -> ~109 H0 = p.r. D.k. at 660 nm. 65G396

C02 + -MBH2 + + H

+

-0.8 •C02H 4- MBH23+ -+ — 7 x 108 H0 = p.r. D.k. at 420 nm. 65G396

C02 4- -MBH22+ + H

+ -5.7

261. 1 -Methylguanosine

261.078 (CH3 )2tOH 4- MG+ —* 8.0 x 107 0.5 p.r. P.b.k. 75A060

(CH3)2CO + mg- + h

+

Methyl iodide See Iodomethane 238a.

1-Methylisonicotinic acid See 4-Carboxy--1-methylpyridinium ion 154.

Methyl mercaptan See Methanethiol 254.

262. 2-Methyl-1 ,4-naphthoquinone

262.011 -CH2CH2 NH2 4- Q 7.5 p.r. P.b.k. in soln. contg. ethylamine; 73A047

10% e-transfer; see 262.049. 262.016 •CH2C(CH3) 2 OH 4- Q 7.0, p.r. P.b.k. in soln. contg. 0.05 mol L'

1 73A047

12.4 tert- BuOH; <5% e-transfer. 262.034 •CH2 CONH2 (or CH3 CONH) (1.1 ± 0.1) x 109 6.0, p.r. P.b.k. at 395 nm in soln. contg. 73A047 + Q--Q- (uncor.) 10.9 acetamide; ~ 17% e-transfer. 262.049 CH3CHNH2 + Q — -Q- (3.3 ± 0.3) x 109 11.6 p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) ethylamine; 34% e-transfer. 262.050 (CH3)2CNH2 + Q — -Q- (3.6 ± 0.4) x 109 11.4 p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) isopropylamine; 41% e-transfer; 14% e-transfer at pH 9.0. 262.051 CH3 CHN(C2H5 )2 + Q

-> .Q- (4.6 ± 0.5) x 109 11.6 p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) triethylamine; 37% e-transfer; — 10% e-transfer at pH 6. 262.053 ch3conhCh2 + Q^-Q- (2.0 ± 0.2) x 109 6.0, p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) 10.9 7V-methylacetamide; 19% e-transfer. 262.055 CH3CON(CH3)CH2 4- Q 6.0, p.r 11% e-transfer in soln. contg. 73A047

10.9 AyV-dimethylacetamide. 262.056 NH2 CHC02- + Q

-* .Q- 3.8 x 109 6.2 p.r. P.b.k. at 400 nm in N20-satd. soln. 72R057

(uncor.) contg. glycine; 78% e-transfer.

(5.5 ± 0.6) x 109 5.4 p.r. P.b.k. at 395 nm in N20-satd. soln. 73A047

(uncor.) contg. glycine; 71% e-transfer. (4.0 ± 0.4) x 109 8.0 p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) glycine; 79% e-transfer. 73A104

262.057 NH3 + CHC0NH2 4- Q

-* .q- (3.6 ± 0.4) x 109 3.2 p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) glycinamide; 24% e-transfer. nh2Chconh2 4- Q 5 x 109 8.0 p.r. P.b.k. at 400 nm in N20-satd. soln. 72R057

(uncor.) contg. glycinamide; 38% e-transfer. (5.4 ± 0.5) x 109 10.4 p.r. P.b.k. at 395 nm in soln. contg. 73A047

(uncor.) glycinamide; 41% e-transfer. 262.058 R 4- Q-»-Q' (8.5 ± 0.9) x 108 6.8 p.r. P.b.k. at 395 nm in N20-satd. soln. 73A047

(R = Radicals from glycyl (8.5 ± 0.9) x 108 11.0 contg. glycylglycinamide; 25% e-transglycinamide) (uncor.) fer at pH 6.8 (16% e-transfer at pH

5.5 and 45% at pH 11.0). 262.059 CH3NHCHC02

- + Q

-+ -Q- (1.1 ± 0.1) x 109 6.0 p.r. P.b.k. at 395 nm in N2 0-satd. soln. 73A047

(uncor.) contg. sarcosine; 33% e-transfer.

(1.7 ± 0.2) x 109 12.5 p.r. P.b.k. at 395 nm in N20-satd. soln. 73A047

(uncor.) contg. sarcosine; 64% e-transfer. 262.061 CH3 C0N(CH3)CHC02

- + Q - -Q- (1.3 ± 0.1) x 109 7.0 p.r. P.b.k. at 395 nm in N2 0-satd. soln. 73A047

(1.0 ± 0.1) x 109 12.5 contg. acetylsarcosine; 39% e-trans-

(uncor.) fer at pH 7, 38% at pH 12.5.

54
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ')

262.062 R + Q - -Q- (4.0 ± 0.4) x 109 (R = Radical from (uncor.) glycine anhydride)

5.0 x 109

(uncor.)

262.063 R + Q—Q- (3.1 ± 0.3) x 109 (R = Radical from

alanine anhydride

(uncor.)

262.065 R + Q —• -Q' (R = Radicals from ( 1.2 ± 0. 1 ) x 109

diglycine) (uncor.) 262.066 R + Q - Q' ( 1.0 ± 0. 1 ) x 109 (R = Radicals from

glycylsarcosine)

(uncor.)

262.067 R + Q - Q- (3.8 ± 0.4) x 109 (R = Radicals from

acetyldiglycine)

(uncor.)

262.068 R + Q

-Q-

( 1.8 ± 0. 2) x 109 (R = Radicals from (uncor.)

triglycine) (1.9 ± 0.2) x 109

(uncor.)

( 1.8 ± 0. 2) x 109

(uncor.) 262.069 R + Q--Q- (3.7 ± 0.4) x 109 (R = Radicals from

acetyltriglycine)

(uncor.)

262.070 R + Q--Q- (2.1 ± 0. 2) x 109 (R = Radicals from (uncor.)

acetyltrialanine) (2.6 ± 0.3) x 109

(uncor.) 262.071 R + Q—Q" (1.3 ± 0.1) x 109 (R = Radicals from

acetyltrisarcosine)

(uncor.)

262.072 R + Q - -Q' (1.5 ± 0.2) x 109 (R — Radicals from (1.9 ± 0.2) x 109 acetylserineamide) (uncor.)

262.073 R + Q - -Q- (1.5 ± 0.2) x 109 (R = Radicals from

acetylasparagine)

(uncor.)

262.075 •CH2 OH + Q — -Q- (3.7 ± 0.4) x 109

•CH2 0- + Q — .Q- (4.4 ± 0.4) x 109

262.076 CH3 CHOH + Q — -Q- (3.8 ± 0.4) x 109

CH3CHO- + Q — Q- (4.2 ± 0.4) x 109

262.078 (CH3) 2(!:OH + Q — Q- 6.2 x 109

(4.2 ± 0.4) x 109

(4.1 ± 0.4) x 109

(4.8 ± 0.5) x 109

(CH3) 2CO- + Q — Q- (4.2 ± 0.4) x 109

pH Method Comment Ref.

10.9 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. glycine anhydride; 88%

e-transfer; no e-transfer at pH 6.7.

73A047

10.9 p.r. P.b.k. at 400 nm in N20-satd. soln. contg. glycine anhydride; 85% etransfer; no e-transfer at pH 7.0.

72R057

10.9 p.r. P.b.k. at 395 nm in soln. contg. alanine anhydride, 75%

e-transfer.

73A047

6.6 11.0p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. diglycine; 19% e-transfer

at pH 6.6 and 47% at pH 11.

73A047

10.9 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. glycylsarcosine; 46% etransfer (20% at pH 6 . 8).

73A047

12.3 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. acetyldiglycine; 55% e-transfer. 73A047

7.0 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. triglycine; 1

% e-transfer. 73A047

10 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. triglycine. 73A104

12.0 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. triglycine; 77% e-transfer. 73A047

12.5 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. acetyltriglycine; 50% etransfer.

73A047

6.9 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. acetyltrialanine; 18% etransfer.

73A047

12.3 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. acetyltrialanine; 47% e-transfer. 73A047

12.5 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. acetyltrisarcosine; 39%

e-transfer at pH 12.5 and 7.0.

73A047

6, 9, 11.0p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. acetylserineamide; 52%,

57%, and 68% e-transfer, resp., at pH

6, 9, and 11.

73A047

12.5 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. acetylasparagine; 39% etransfer; ~ 12 % e-transfer at pH

3.2 and 6.0.

73A047

7.0 p.r. P.b.k. at 395 nm in 0.5 mol L

' 1 MeOH; 88% e-transfer. 73A047

12.4 p.r. P.b.k. at 395 nm in soln. contg. 0.5 mol L

' 1 MeOH; 92% e-transfer. 73A047

7.0 p.r. P.b.k. at 395 nm in soln. contg. 0.5 mol L

' 1 EtOH; 90% e-transfer. 73A047

12.5 p.r. P.b.k. at 395 nm in soln. contg. 0.5 mol L

' 1 EtOH; 92% e-transfer. 73A047

6.9 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. 2-PrOH; 80% e-transfer. 72R057

7 p.r. P.b.k. in soln. cont. 1 mol L

' 1 acetone and 1 mol L

" 1 2-PrOH. 73G125

7.0 p.r. P.b.k. in soln. contg. 0.5 mol L

' 1 2-PrOH; 91% e-transfer. 73A047

7.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. 2-PrOH. 73A104

12.4 p.r. P.b.k. in soln. contg. 0.5 mol L" 73A047

EtOH; 91% e-transfer.

55
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L molds' 1 )

262.079 CH;j CH2 CH2CHOH + Q — -Q~ (4.1 ± 0.4) x 109

(4.2 ± 0.4) x 109

(uncor.) 262.097 CH3C(0-)CH2C02

- + Q -> Q- (3.7 ± 0.4) x 109

262.108 R + Q—Q-

(R = Radicals from deoxyribose) 4 x 109 (uncor.)

(2.1 ± 0.2) x 109

(uncor.) 262.109 R + Q--Q- 2.6 x 109 (R = Radicals from ribose) (uncor.) (1.4 ± 0.1) x 109

(uncor.) 262.110 R 4- Q-Q"

(R = Radicals from

ribose phosphate)

4.0 x 109 (uncor.)

262.113 •A“ + Q

—*• -Q ~ 1.3 x 109

(•A' = Radical from ascorbate) (3.8 ± 0.4) x 109

(uncor.) 262.114 CHO-CONH2 + Q

-+ -Q- (2.3 ± 0.2) x 109

(uncor.) 262.115 CHOHC02 H + Q

-Q- (9.2 ± 0.9) x 108

(uncor.) CHOHC02

- + Q - -Q- (1.5 ± 0.2) x 109

(uncor.) CHO-C02

- + Q -> -Q- (1.6 ± 0.2) x 109

(uncor.) 262.117 CH3C0HC02- + Q

-Q- (1.4 ± 0.1) x 109

(uncor.) CH3C(0-)C02

- + Q

-» -Q‘ (1.9 ± 0.2) x 109

(uncor.)

262.118 CH3 6(0-)C02CH3 + Q — -Q- (2.3 ± 0.2) x 109

(uncor.)

262.119 60-(C02

-)2 + Q

-Q- (2.5 ± 0.3) x 109

262.120 o2 C(!:(OH)CH2co2

- + q ^ .q- (1.1 ± 0.1) x 109

(uncor.)

(3.1 ± 0.3) x 109

262.121 H02CCH0HC(0H)C02H + Q

-Q- (7.0 ± 0.7) x 108

(uncor.) 02CCH0HC(0H)C02- + Q

.Q- (7.0 ± 0.7) x 108

(uncor.) 262.122 -0

2 C(CH2 )2 C(0-)C02

- + Q

-> .Q- (3.8 ± 0.4) x 109

262.142 R + Q -> .Q- (R = Electron adduct of

glycine anhydride)

(4.9 ± 0.5) x 109

262.143 R + Q - -Q- (R = Electron adduct of

alanine anhydride)

(4.8 ± 0.5) x 109

262.144 R + Q

-* -Q- (R = Electron adduct of sarcosine anhydride)

(4.6 ± 0.5) x 109

262.146 R + Q - -Q- (R = Electron adduct of acetylglycylglycinamide)

(2.7 ± 0.3) x 109

PH Method Comment Ref.

7.0 12.7

p.r. P.b.k. in soln. contg. 0.05 mol L'

1 1-BuOH; 32.3% (pH 7) and 40%

(pH 12.7) e-transfer.

73A047

9.2 p.r. P.b.k. at 395 nm in soln. contg. acetoacetate and 1 mol L'

1 tert-BuOH; 95% e-transfer.

73A047

73A104

6.8 p.r. P.b.k. at 400 nm in soln. contg. deoxyribose; 74% e-transfer. 72R057

6.8 p.r. P.b.k. in soln. contg. 0.05 mol L'

1 deoxyribose; 81% e-transfer. 73A047

6.9 p.r. P.b.k. in N20-satd. soln. contg.

ribose; 44% e-transfer. 72R057

6.9 p.r. P.b.k. in N20-satd. soln. contg. 0.5 mol L'

1 ribose; 60% e-transfer. 73A047

6.8 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. ribose-5-phosphate;

25% e-transfer.

72R057

3.3 9.0p.r. P.b.k. in N20-satd. soln. contg. 0.05 mol L"

1 ascorbic acid; 43 and 38%

e-transfer, resp., at pH 3.3 and 9.0.

73A047

7.1 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. glycolamide; 48% e-transfer. 73A047

3.2 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. glycolic acid; 13% e-transfer. 73A047

6.5 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. glycolate ion; 69% e-transfer 73A047

73A104

10.6 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. glycolate ion; 77% e-transfer. 73A047

6.5 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. lactate ion; 55% e-transfer. 73A047

10.6 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. lactate ion; 72% e-transfer (15% at pH 3.2).

73A047

10.4 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. methyl lactate; 74% e-transfer (20% at pH 3.2).

73A047

9.2 p.r. P.b.k. at 395 nm in soln. contg. ketomalonate and 1 mol L'

1 tert- BuOH; 94% e-transfer.

73A047

7.0 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. malate; 47% e-transfer. 73A047

6.2 p.r. P.b.k. at 395 nm in soln. contg. oxaloacetate and 1 mol L'

1 tert- BuOH; 92% e-transfer.

73A047

3.2 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. tartaric acid; 14% e-transfer. 73A047

11.0 p.r. P.b.k. at 395 nm in N , O-satd. soln. contg. tartrate ion; 69% e-transfer. 73A047

10.2 p.r. P.b.k. at 395 nm in soln. contg. a-ketoglutarate and 1 mol L'

1 tert- BuOH; 94% e-transfer.

73A047

6.9 p.r. P.b.k. at 395 nm in soln. contg. glycine anhydride; 98% e-transfer. 73A047

6.0 p.r. P.b.k. at 395 nm in soln. contg. alanine anhydride; 92% etransfer.

73A047

6.0 p.r. P.b.k. at 395 nm in soln. contg. sarcosine anhydride; 91% etransfer.

73A047

7.0 p.r. P.b.k. at 395 nm; 99% e-transfer. 73A047

56
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's ') PH Method Comment Ref.

262.147 •C02 + Q —* -Q 5.4 x 109 6.9 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. formate; 100% e-transfer. 72R057

(4.8 ± 0.5) x 109 7 p.r. P.b.k. at 400 nm in N2 0-satd. soln. 73A047

contg. formate. 73A104

1 -Methy[nicotinamide See 3-Carbamoyl-l--methylpyridinium ion 151.

1-Methylnicotinate ion See 3-Carboxy-l-methylpyridinium ion 153.

3-Methyl-2-nitroanisole See 3-Methoxy-2-nitrotoluene 25 7.

263. 3-Methyl-2-nitrobenzoate ion 263.078 (CH3 ) 2 COH + N02B- - 1.9 x 108 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A020

(CH3)2CO + H

+ + -N02 B

2- 0.1 mol L’

1 2-PrOH.

264. 2-Methyl-5-nitroimidazole

264.078 (CH2 ) 2 COH + NX —*> 2.5 x 109 p.r. P.b.k. 76A075

(CH3) 2CO + H

+ + NX'

265. 3-Methyl-2-nitrophenol

265.078 (CH3) 2 C0H + CH3(0H)C6 H3 N02 — 2.9 x 108 p.r. P.b.k. in N2 0-satd. soln. contg. 76A020

(CH3)2CO + H

+ + CH3(0H)C6H3 N02- 0.1 mol L1 2-PrOH.

266. 4-Methylphenoxide ion

266.020 •CH2 CH0 + CH3C6H+0- (+ H2 0) 9.0 x 10' -11.5 p.r. Soln. contg. N2 0 and ethylene 79A051 CH3 CH0 + CH3 C6H40- + OH- glycol.

267. Methyl propionate

267.001 •ch3 + c2 h5 co2 ch3 -> 2.9 x 103 (rel.) -1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 + ch3 chco2 ch3 Ti MI-H2 02-soln.; est. from esr meas. and values of competing reactions.

268. 3-Methylpterin

268.075 •CH20H + PtH + 6 x 107 (uncor.) 0.8 p.r. P.b.k. in N2 0-satd. soln. contg. MeOH; —45% e-transfer. 76A060

268.076 CH3CH0H + Pt 3.2 x 10' (uncor.) 6.3 p.r. P.b.k. in N20-satd. soln. contg. EtOH; 55% e-transfer. 76A060

268.078 (CH3 ) 2COH + PtH +

1.9 x 109 0.8 p.r. P.b.k. in N2 0-satd. soln. contg. 76A060

(CH3)2 COH + Pt 2.9 x 108 7.0 2-PrOH; 100% e-transfer.

269. 9-Methylpurine

269.076 CH3 CHOH + MP — MPH- <2 x 107 8.2 p.r. P.b.k.; N20-satd. soln. contg. EtOH. 76A060 CH3CHO- + MP -* MP' 5.1 x 108 13.6 269.078 (CH3 ) 2 COH + MPH+ — MPH3

. 2+

1.9 x 109 -0 p.r. P.b.k. in N20-satd. soln. contg. 76A060

(CH3 ) 2 COH + MP — MPH- 1.7 x 108 8.6 2-PrOH.

(CH3 ) 2 CO- + MP —* MP' 8.7 x 108 13.6

J-Methyl~3-pyridinecarboxylate ion See 3-Carboxy-l-methylpyridinium ion 153.

l-Methyl-4-pyridinecarboxylate ion See 4-Carboxy-l-methylpyridinium ion 154.

Methylviologen See 1,1'-Dimethyl-4,4'-bipyridinium ion 183.

270. Metmyoglobin

270.075 •CH2 OH + M(Fe‘") -H- CH2 0 + H

+ + M(Fe")

(2.4 ± 0.5) x 107 7 p.r. 95% redn. of hemoprotein in N2 0-satd.

soln. contg. MeOH; obs. abs. change

at 550 and 435 nm.

79A153

270.076 CH3 CHOH + M(Feni

) (5.5 ± 0.5) x 107 7 p.r. 95% redn. of hemoprotein in N2 0-satd.

soln. contg. EtOH. 79A153

270.078 (CH3 ) 2 tOH -f M(Fem

) ^ M(Fe") - 1 x 108 7.5 p.r. G = 2.2. 79A371

270.121 -0

2 CCH0Ht0HC02

- + M(Fe"') (3.5 ± 0.7) x 107 7 p.r. Redn. in soln. contg. 10"2 mol L"

1

tartrate. 78A288

D /
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mor's'1 ) pH Method Comment Ref.

270.147 •C02

- + M(Fein

) (2.0 ± 0.4) X 109 7 p.r. Redn. in soln. contg. 10“2 mol L"

1

formate. 78A288

2.9 X 109 8.2 p.r. D.k. at 360 nm in N2 0-satd. soln. contg. 10'2 mol L"

1 formate; / = 0.03. 79A204

271. Metronidazole [l-(2-Hydroxyethyl)-2-methyl-5-nitroimidazole]

271.075 •ch2 oh + rno2 108 p.r. D.k. at 320 nm in N2 0-satd. soln. contg. 0.1 mol L'

1 MeOH.

74A135

271.076 ch3Choh + rno2

(CH3 )2tOH + rno2

2 x 108 p.r. D.k. at 320 nm in N2 0-satd. soln. contg. EtOH. 74A135

271.078 7 x 108 p.r. D.k. at 320 nm in N2 0-satd. soln. contg. 2-PrOH. 74A135

271.147 •C02 + RN02 8 x 108 p.r. D.k. at 320 nm in N2 0-satd. soln. contg. 0.1 mol L”

1 formate ion; also

c.k. gave 8 x 108 rel. to &(-C02~ +

TAN) = 6 x 108 [342.147],

74A135

272. Misonidazole [l-(2-Hydroxy-3--methoxypropyl)-2-nitroimidazole]

272.078 (CH3)2COH + rno2 — (2.8 ± 0.4) x 109 p.r. P.b.k. in N2 0-satd. soln. contg. 76A070

(CH3)2CO + H

+ + RN02

- 0.1 mol IT

1 2-PrOH.

273. 1 ,4-Naphthoquinone

273.078 (CH3)2tOH + q ^ -Q- 3.6 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L"

1 2-PrOH and 1 mol L'

1 acetone. 73G125

274. 1 ,4-Naphthoquinone-2-sulfonate ion 274.056 NH2CHC02

- + Q

Q- (3.3 ± 0.3) x 109 8.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. glycine. 73A104

274.068 R + Q--Q- (2.0 ± 0.2) x 109 10 p.r. P.b.k. at 400 nm in N20-satd. soln. 73A104

(R = Radicals from contg. triglycine.

triglycine) 274.115 •CHOHCCy + Q

-Q- (1.7 ± 0.2) x 109 7.0 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. glycolate ion. 73A104

275. Nicotinamide

275.078 (CH3)2tOH -1- NH + —*• (2.1 ± 0.4) x 108 0.9 p.r. P.b.k.; no e-transfer in 74A089

(CH3)2CO + NH + H

+

neutral soln.

(CH3)2COH + N

4.0 x 108 1.9 p.r. P.b.k. at ~400 nm in N2 0-satd.

soln. contg. 0.5 mol L"

1 2-PrOH. 74A106 < 1 x 106 9.2 p.r. P.b.k. at ~400 nm in N2 0-satd.

soln. contg. 0.5 mol L

_1 2-PrOH. 74A106

276. Nicotinamide-adenine dinucleotide 276.056 NH2tHC02

- + NAD+

1.5 x 109 6.0 p.r. 73A104

276.075 •CH2OH + NAD+

1.0 x 109 6.0 p.r. 73A104

276.078 (CH3)2COH + nad+

1.0 x 109 p.r. Est. from buildup and decay of -NAD 70R013

(CH3)2CO + H

+ + -NAD

1.0 x 109 6.0 p.r.

at 400 nm in soln. contg. 1 mol L"

1

acetone, 1 mol L"

1 2-PrOH, 2 x 10"4 mol L'

1 02 and 2 x 10"s mol L

_1 benzoquinone.

73A104

276.147 •C02

- + NAD+ — C02 4- NAD 1.6 x 109 6.4 p.r. P.b.k. at 400 nm in N2 0-satd. soln. contg. 0.1 mol L"

1 formate. 68G441

277. Nicotinic acid 277.078 (CH3)2COH + h

+ nc5 h4co2 h 3.5 x 108 0.0 p.r. P.b.k. at ~400 nm (pyridinyl 74A106

(CH,)2COH + H

+ NCsH4C02

- 1.8 x 108 3.4 radical) in N2 0-satd. soln. (CH3) 26oh + nc5 h4co2

- < 1 x 106 8.2 contg. 0.5 mol L'

1 2-PrOH.

(CH3)2tO- + NC-H4C02

- >1 x 108 13.1

58
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mop's"1 ) PH Method Comment Ref.

278. Nifuroxime [anti-5-Nitro-2-furaldoxime

278.018 R + NF 5.1 x 109 (uncor.) 7 p.r. P.b.k. at 395 nm (NF*) in 73A062

(R = Radicals from N2 0-satd. soln. contg. allyl 73A099

allyl alcohol) alcohol; 3% e-transfer. 278.019 R + NF 5.6 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm (NP) in N2 0-satd. 73A099

(R = Radicals from soln. contg. crotyl alcohol;

crotyl alcohol) 2.4 x 109 (uncor.) 7 p.r. 24% e-transfer.

P.b.k. at 395 nm in N20-satd.

soln. contg. crotyl alcohol; 10% e-transfer.

73A052

278.037 CH3CHC02

- + NF

CH3 CH2 CHC02- + NF

4.0 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm (NP) in N20-satd. soln. contg. 0.2 mol L'

1 propionate ion; 2% e-transfer based on abs. spectra.

73A099

278.038 4.9 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm (NP) in N20-satd. soln. contg. 0.2 mol L'

1 butyrate ion; 2% e-transfer.

73A099

278.039 H0CH2CHC02- + NF 6 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in soln. contg. 4 x 10*4 mol L'

1 acrylate ion; 73A099

65% e-transfer. 278.040 ch3 choh<!:hco2- + nf 5.5 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in soln. contg. crotonate ion; 25% e-transfer. 73A099

278.041 -0

2CCHCH0HC02

- + NF 2.4 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in soln. contg. maleate ion; 3% e-transfer. 73A099

278.042 •CH(C02

-)

2 + NF 1.3 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 0.2 mol L"

1 malonate ion; 3% e-transfer.

73A099

278.075 •ch2oh + nf ^ np 8 x 108 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 0.2 mol L'

1 MeOH; 90% etransfer.

73A099

278.076 CHjtHOH + NF —*• NP > 1.5 x 109 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A099

(uncor.) contg. 0.2 mol L'

1 EtOH; > 75% etransfer. 278.077 ch3 ch2 6hoh + NF — Nr 3.2 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 1-PrOH; 52% e-transfer. 73A062

3.2 x 109 7 p.r. P.b.k. at 395 nm in N2 0-satd. soln. contg. 1-PrOH; 95% e-transfer. 73A099

278.078 (CH3)2COH + NF Nr 3.3 x 109 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 0.2 mol L'

1 2-PrOH; 100% etransfer.

73A099

3.5 x 109 p.r. P.b.k. 76A075

278.079 CH3 CH2 CH2tHOH + NF — Nr 5.1 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 1-BuOH; 75% e-transfer. 73A099

3.4 x 109 (uncor.) 7 p.r. P.b.k. at 395 nm in N20-satd. soln. contg. 1-BuOH; 32% e-transfer. 73A062

278.099 NH3 + CH2tH0P032' + NF 3.0 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N20-satd. soln. contg. 10'2 mol L"

1 o-phosphorylethanolamine; 1% e-transfer.

73A099

278.106 CH2 OHCHOHtHOH + NF 1.3 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A099

( + CH2 OHtOHCH2OH) contg. 0.2 mol L'

1 glycerol; 20% etransfer. 278.108 R + NF — Nr 1.4 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A099

(R 4- Radicals from contg. 10'2 mol L'

1 deoxyribose; 70%

deoxyribose) e-transfer. 278.109 R + nf — Nr 1.5 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A099

(R = Radicals from contg. 10"2 mol L'

1 ribose; 50% eribose) transfer. 278.110 R + NF 1.7 x 109 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. 73A099

(R = Radicals from contg. 10

-3 mol L"

1 ribose phosphate;

ribose phosphate) 10% e-transfer.

59
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L moP’s"1 ) pH Method Comment Ref.

278.117 CH3C0HC02 - + NF - NF" 1.5 x 109 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 0.2 mol L

" 1 lactate ion; 100%

e-transfer.

73A099

278.120 02CCH2C0HC02- + NF 1.2 x 108 (uncor.) 7 p.r. P.b.k. at 390 nm in N2 0-satd. soln. contg. 0.2 mol L

" 1 malate ion; 30% etransfer.

73A099

278.147 •C02- + NF -* NF- 2.7 x 109 p.r. P.b.k. at 390 nm in C02-satd. soln. contg. tert-BuOH or 0.2 mol L

" 1 formate; 100% e-transfer.

73A099

279. />-Nitroacetophenone

279.018 R + PNAP 2.7 x 109 (uncor.) 7 p.r. P.b.k. at 360 and 550 nm (PNAP") 73A062

(R = Radicals from in N20-satd. soln. contg. allyl

allyl alcohol) alcohol; 3% e-transfer. 279.019 R + PNAP 2.0 x 109 (uncor.) 7 p.r. P.b.k. at 360 and 550 nm (PNAP") 73A062

(R = Radicals from in N20-satd. soln. contg. crotyl

crotyl alcohol) alcohol; 9% e-transfer. 279.075 •CH2 OH + PNAP addn. 1 x 108 7 p.r. P.b.k. at 330 nm in N2 0-satd. soln. contg. MeOH.

73G122

•CH2OH + PNAP — PNAP" 1 x 107 7 p.r. P.b.k. at 550 nm in N20-satd. soln. contg. MeOH.

73G122

•CH2 0- + PNAP PNAP- CH3CHOH + PNAP PNAP'

(4.7 ± 0.5) x 109 13 p.r. P.b.k. at 550 nm in N20-satd. soln. contg. MeOH.73G122

279.076 (8 ± 2) x 108 11 p.r. P.b.k. at 550 nm in N20-satd. soln. contg. EtOH. 73G122

279.077 CH3CH2 CHOH + PNAP 2.4 x 109 (uncor.) 7 p.r. P.b.k. at 360 and 550 nm in N2 0-satd. soln. contg. 1-PrOH; 45% e-transfer.

73A062

279.078 (CH3)2COH + PNAP -> PNAP" (3.8 ± 0.4) x 109 11 p.r. P.b.k. at 550 nm in N2 0-satd. soln. contg. 2-PrOH. 73G122

2.2 x 109 ~ 13 p.r. P.b.k. at 355 nm in soln. contg. 6.5 mol L

" 1 2-PrOH and 0.68 mol L

" 1 81A002

acetone. 279.079 CH3CH2 CH2CHOH + PNAP 2.2 x 109 (uncor.) 7 p.r. P.b.k. at 360 and 550 nm in N2 0-satd. soln. contg. 1-BuOH; 24% e-transfer.

73A062

279.108 R + PNAP -> PNAP" (1.0 ± 0.3) x 109 p.r. P.b.k.; 47% e-transfer. 75A207

(R — Radicals from deoxyribose) 279.111 R + PNAP PNAP" 9 x 108 p.r. 77R167

(R = Radicals from glucose) 279.147 •C02- + PNAP - PNAP" (1.0 ± 0.1) x 109 10 p.r. P.b.k. at 550 nm in N2 0-satd. soln. contg. formate ion. 73G122

7 x 108 p.r. Radical from formate. 77R167

280. o-Nit roaniline 280.078 (CH3)2 COH + nh2 c6h4no2 — 9.2 x 108 7 p.r. P.b.k. in NzO-satd. soln. contg. 76A020

(CH302 C0 + H

+ + NH2C6H4ft02' 0.1 mol L

- 1 2-PrOH.

281. m-Nitroaniline

281.078 (CH3)2 COH + nh2 c6h4no2 - 1.5 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A020

(CH3)2CO + H

+ + NH2 C6H4fi02' 0.1 mol L

- 1 2-PrOH.

282. p-Nitroaniline 282.078 (CH3)2 COH + nh2 c6h4no2 7.2 x 108 7 p.r. P.b.k. in N20-satd. soln. contg. 76A020

(CH3)2CO + H

+ + NH2 C6H4N02-

(1.9 ± 0.2) x 109 10.7 p.r.

O. 1 mol L

" 1 2-PrOH.

P. b.k. at 380 nm in N20-satd. soln.

soln. contg. 0.1 mol L

" 1 2-PrOH. 77A118

283. Nitrobenzene

283.018 R + C6H5 N02 ~ 1.5 x 109 7 p.r. P.b.k. at 400 nm in N2 0-satd. soln. 73A062

(R = Radicals from

allyl alcohol)

(uncor.) contg. allyl alcohol; 5% e-transfer.

60
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's'

1 ) PH Method Comment Ref.

283.019 R + C6H5 N02 — 1 x 109 (uncor.) 7 p.r. P.b.k. at 400 nm in N20-satd. soln. 73A062

(R = Radicals from

crotyl alcohol)

contg. crotyl alcohol; 8% e-transfer.

283.075 •CH2 OH + C6 H5 N02 <107 7 p.r. P.b.k. at 285 nm in N20-satd. soln. 66G432

ch2 o + c6h5 no2

-

(6.0 ± 0.9) X 107 5-6 p.r.

contg. 0.1 mol L"

1 MeOH. N2 0-satd. soln. contg.

0.1 mol L'

1 MeOH.

72A018

•CH2 0' + C6H5N02 — 2.7 X 109 13 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

CH2 0 + C6H5 N02

' contg. 0.1 mol L'

1 MeOH.

283.076 ch3 Choh + c6h5 no2 — 3.3 X 108 7 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

CHjCHO + H

+ + C6 H5 N02

'

(2.4 ± 0.7) X 108 5-6 p.r.

contg. 0.1 mol L’

1 EtOH. N2 0-satd. soln. contg.

0.1 mol L'

1 EtOH. 72A018 CH3 CH0' + QHjNO;, 3.1 X 109 13 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

CHjCHO + C6 HsN02 '

3 X 109 13 p.r.

contg. 0.1 mol L'

1 EtOH.

P.b.k. at 285 nm in N2 0-satd. soln. contg. EtOH; Ea = 3.3 kcal mol' 1 (14 kj mol' 1 ).

74A010

283.077 ch3ch2 £hoh + c6h5 no2 — 3.5 x 108 7 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

CH3 CH2 CHO + H

+ + C6HsN02-

1.0 x 109 (uncor.) 7 p.r.

contg. 0.1 mol L'

1 1-PrOH; 68% etransfer. P.b.k. at 400 nm in N2 0-satd. soln. contg. 1-PrOH; 60% e-transfer. 73A062

CH3CH2 CHO' + c6h5 no2 — 3.1 x 109 13 p.r. P.b.k. at 285 nm in N20-satd. soln. 66G432

CH3 CH2 CHO -)- C6H5 N02- contg. 0.1 mol L'

1 1-PrOH.

283.078 (CH3)2 COH + c6h5 no2 -* 1.6 x 109 7 p.r. P.b.k. at 285 nm in N20-satd. soln. 66G432

(CH3)2CO + H

+ + C6H5 N02

' contg. 0.1 mol L'

1 2-PrOH.

(CH3 ) 2 6o- + c6 h5 no2 -+ 3.0 x 109 13 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

(CH3)2CO + C6 H5 N02 - contg. 0.1 mol L'

1 2-PrOH.

283.079 ch3ch2 ch2 choh + c6 h5no2 -> 4.0 x 108 7 p.r. P.b.k. at 285 nm in N20-satd. soln. 66G432

CH3 CH2 CH2 CHO + H

+ + C6 H5N02

'

1.1 x 109 (uncor.) 7 p.r.

contg. 0.1 mol L'

1 1-BuOH; 35% etransfer. P.b.k. at 400 nm in N2 0-satd. soln. contg. 1-BuOH; 31% e-transfer; 73A062 ch3ch2 ch2 Cho- + c6 h5 no2 — 3.1 x 109 13 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

CH3 CH2 CH2 CHO + C6 H5N02- contg. 0.1 mol L'

1 1-BuOH.

283.081 (CH3) 2CHCHOH + c6h5 no2 — 3.9 x 108 7 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

(CH3)2CHCHO + H

+

4- C6H5N02- contg. 0.1 mol L'

1 2-methyl-l-propanol;

39% e-transfer. (CH3 ) 2CHtHO- + C6 H5 NO 2.9 x 109 13 p.r. P.b.k. at 285 nm in N2 0-satd. soln. 66G432

(CH3)2CHCHO + C6H5 N02- contg. 2-methyl-l-propanol. 283.084 -CH2 60H(CH2)2- + c6h5 no2 — 1.5 x 109

p.r. P.b.k. at 280 nm in soln. contg. 76A103

R = 0 + H

+ + C6H5N02

- 10'3 mol L'

1 cyclobutanone and 0.1 mol L'

1 tert-BuOH at 2°C; k =

3.2 x 109 at 64° C; E, = 2.3 kcal mol' 1

(9.6 kj mol'1 ). 283.085 -CH2 £OH(CH2 ) 3- + c6h5 no2 — 1.4 x 109 p.r. P.b.k. at 280 nm in soln. contg. 76A103 R = 0 + C6 H5 N02- 10'3 mol L'

1 cyclopentanone and 0.1 mol L'

1 tert-BuOH at 2°C; k =

5.2 x 10

9 at 64°C; Et = 4.0 kcal mol' 1

(17 kj mol' 1 ). 283.086 -CH2 tOH(CH2 ) 4- + c6 h5 no2 — X O p.r. P.b.k. at 280 nm in soln. contg. 76A103

R = 0 + C6Hs N02

- 10'3 mol L'

1 cyclohexanone and 0.1 mol L"

1 ter/-BuOH at 2°C;

k = 2.0 x 109 at 64°C Et = 3.1 kcal mol' 1 (13 kj mol' 1 ). 283.087 -CH2 £OH(CH2 ) 5- + c6h5 no2 — 1.4 x 109 p.r. P.b.k. at 280 nm in soln. contg. 76A103

R = 0 + c6 h5 5jo2- 10

-3 mol L'

1 cycloheptanone and 0.1 mol L'

1 /ert-BuOH at 2°C;

k = 4.9 x 109 at 64° C; E, = 3.8 kcal mol' 1 (16 kj mol' 1 ).

61
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mor's"1 ) PH Method Comment Ref.

283.088 -CH2 COH(CH2)6- + c6h5no2 — 1.6 x 109 p.r. P.b.k. at 280 nm in soln. contg. 76A103 R = 0 + QH5N02

- 10"3 mol L"

1 cyclooctanone and 0.1 mol L"

1 <ert-BuOH at 2°C;

k = 5.2 x 109 at 64° C; Et = 3.7 kcal mol' 1 (15.5 kj mol* 1 ). 283.093 ch3£hoc2 h5 + c6h5no2 2.5 x 108 p.r. D.k.; radical from ethyl ether. 77A100

283.104 -0CHCH20(CH2) 2- + c6h5no2 2.5 x 107 p.r. D.k.; radical from dioxane. 77A100

283.117 ch3Cohco2

- + c6h5 no2 (6.5 ± 2) x 107 6.0 p.r. N20-satd. soln. contg. 0.1 mol L"

1 lactate ion. 72A018

283.123 •CH(OH)2 + c6h5 no2 -* 1.9 x 109 5.8 p.r. P.b.k. at 290 nm in N2 0-satd. soln. 71G424

HC02

- + 2 H

+ + C6H5IV02

- contg. 10"2 mol L"

1 formaldehyde;

•CH(0H)0- + C6H5 N02 — 4.5 x 109 12 also condy. HC02

- + h

+ + c6H5fto2

- 283.147 •C02

‘ + c6h5no2 -> (1.0 ± 0.2) x 109 6-7 p.r. P.b.k. at 295 nm in N2 0-satd. 70G303 co2 + c6h55jo2- (5.6 ± 1) x 108 ~3 soln. contg. 10"3 mol L"

1 formate.

(5.8 ± 0.6) x 108 9.4 p.r. P.b.k. 73G085

(7.5 ± 0.7) x 108 2.5

(4.6 ± 0.5) x 108 0

284. o-Nitrobenzoate ion

284.078 (CH3)2COH + N02 C6H4C02

- - 5.4 x 108 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111

(CH3)2CO + H

+ + N02-C6H4C02

- 2-PrOH; at pH 0.8 k was the same ± 20-30%.

284.147 •CO2 N02C6H4C02 — 2.4 x 108 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111 C02 + N02 c6h4co2 formate; at pH 0.8 k was the same ± 20-30%.

285. m—Nitrobenzoate ion

285.078 (CH3)2 COH + N02C6H4C02- 9.0 x 108 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111

(CH3 )2CO + H

+ + 1V02-C6H4C02

- 2-PrOH; at pH 0.8 k was the same ± 20-30%.

285.147 •C02 + N02C6H4C02 — 6.3 x 108 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111 C02 + N02-C6H4C02

- formate; at pH 0.8 k was the same ± 20-30%.

286. />-Nitrobenzoate ion 286.078 (CH3)2COH + N02C6H4C02

- — 2.1 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111

(CH3)2CO + H

+ + N02-C6H4C02

- 2-PrOH; at pH 0.8 k was the same ± 20-30%.

286.147 •C02 + N02C6H4C02 — 8.0 x 108 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A111 C02 + N02'C6H4C02- formate; at pH 0.8 k was the same ± 20-30%.

287. p-Ni t robenzonitrile 287.111 R + N02C6H4CN 1.0 x 109 p.r. 77R167

(R = Radicals from glucose)

287a. Nitro blue tetrazolium

287a. 147 •C02

- + NBT2+ -> C02 + NBT-+ (6.4 ± 0.2) x 109 10 p.r. P.b.k. at 405 nm in N2 0-satd.

soln. contg. 0.1 mol L"

1 formate. 80A085

anti-5-Nilro-2-furaldoxime see Nifuroxime 278.

288. 5-Nitrofuroate ion 288.078 (CH3)2COH + ...N02 - 1.5 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 73G114

(CH3)2CO + H

+ + N02

- 0.1 mol L1 2-PrOH.

289. 2-Nit roimidazole

289.078 (CH3)2COH -f NX —* 3.5 x 109

p.r. P.b.k. 76A075

(CH3)2CO + H

+ + NX290. 4—Nitroimidazole 290.078 (CH3)2tOH + NX — 3.5 x 109 p.r. P.b.k. 76A075

(CH3)2CO + H

+ + NX- 62
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol-'s"

1 )

291. 2-Nitroisophthalate ion 291.078 (CH3 ) 2 tOH + r02C)2 C5H3 N02 —

(CH3)2 CO + H

+ + ('OjQjQHaNCV

1.5 x 108

292. Nitromethane

292.047 •cf3 + CH2 N02 - —

CF3CH2 fi02

- 5 x 108

(rel.)

293. />-Nitroperoxybenzoic acid 293.075 •ch2oh + no2c6h4co2 oh —

CH2 0 + H

+ + ft02-C6H4C02 0H

(+ adduct formn.)

2 x 108

293.078 <ch3)2 (!:oh + no2c6h4co2 oh —

(CH3) 2 CO + h

+ + no2-c6h4co2oh

3.3 x 109

294. o-Nitrophenol

294.078 (CH3)2COH + hoc6h4no2 —

(CH3)2CO + H

+ + H0C6 H4N02- 2.6 x 109

(CH3 ) 2CO- + -0C6H4N02 — 1.4 x 109

295. 2-Nitropyrrole

295.078 (CH3)2 tOH + NX -

(CH^CO + H

+ + NX"

2.0 x 109

296. 3-Nitropyrrole 296.078 (CH3)2COH + NX —* (CH3)2CO + H

+ + NX2.0 x 109

2-NitroresoTcinol See l,3-Dihydroxy-2-nitrobenzene 178.

297. Nitrosobenzene

297.075 •ch2 oh + C6H5 NO -> ch2 o + C6H5 NOH

3.2 x 109

•ch2 o- + C6H5NO —

ch2 o + C6H5 NO6.8 x 109

297.076 ch3 Choh + C6H5NO —

CHjCHO + C6H5 NOH

3.9 x 109

ch3 Cho- + c6h5no —

CH3CH0 + C6H5 ftO6.4 x 109

297.077 CH3 CH2 tHOH + QH5 NO —

CH3CH2 CHO + C6H5ftOH

4.0 x 109

297.078 (CH3)2 COH + C6H5NO —

(CH3 )2CO + C6H5NOH

5.0 x 109

(CH3) 2CO- + c6h5 no —

(CH3 )2CO + QHsftcr

7.0 x 109

297.079 ch3 ch2 ch2 Choh + C6H5NO —

CH3CH2 CH2 CHO + C6H5I^OH

4.0 x 109

297.081 (CH3 ) 2CHCHOH + C6 Hs N0 —

(CH3 ) 2 CHCHO + c6h5 ivoh

4.0 x 109

297.147 •C02

- + c6 h5no —

C02 + QHsNO4.0 x 109

p-Nitroso-N,N-dimethylaniline See N, N-Dimethyl-4-nitrosoaniline,

298. 2-Nitrothiophene

298.078 (CH3)2tOH + NX —

(CH3)2CO + H

+ + NX3.0 x 109

pH Method Comment Ref.

7 p.r. P.b.k. at 310 nm in N2 0-satd. soln. contg. 0.1 mol L"

1 2-PrOH. 76A020

y-r. C.k. in soln. contg. 1 mol L"

1 2-PrOH and CF3C1; rel. to A(CF3 +

2-PrOH) = 10s

; product radical

identified by esr.

72G244

p.r. P.b.k. at 330 nm in N2 0-satd. soln. contg. MeOH; 20% e-transfer based on

condy. change.

74A078

5.0 p.r. P.b.k. at 330 nm in N2 0-satd. soln. contg. 2-PrOH. 74A078

1 p.r. P.b.k. in soln. contg. 2-PrOH. 69G270

13 p.r. P.b.k. in soln. contg. 2-PrOH. 69G270

p.r. P.b.k. 76A075

p.r. P.b.k. 76A075

7.0 p.r. P.b.k. at 450 nm in N2 0-satd. soln. contg. 0.05 mol L"

1 MeOH.

66G433

13.0 p.r. P.b.k. at 450 nm in N2 0-satd. soln. contg. 0.05 mol L"

1 MeOH.

66G433

7.0 p.r. P.b.k. at 450 nm in N20-satd. soln. contg. 0.05 mol L"

1 EtOH. 66G433

13.0 p.r. P.b.k. at 450 nm in N20-satd. soln. contg. 0.05 mol L"

1 EtOH. 66G433

7.0 p.r. P.b.k. at 450 nm in N20-satd. soln. contg. 0.05 mol L"

1 1-PrOH; includes

i3-alcohol radical reaction.

66G433

7.0 p.r. P.b.k. at 450 nm in N20-satd. soln. contg. 0.05 mol L"

1 2-PrOH. 66G433

13.0 p.r. P.b.k. at 450 nm in N2 0-satd. soln. contg. 0.05 mol L"

1 2-PrOH. 66G433

7.0 p.r. P.b.k. at 450 nm in N2 0-satd. soln. contg. 0.05 mol L"

1 1-BuOH; includes

/3- and y-alcohol radical reaction.

66G433

7.0 p.r. P.b.k. at 450 nm in N2 0-satd. soln. contg. 0.05 mol L"

1 2-methyl-l-propanol;

includes /3-alcohol radical reaction.

66G433

p.r. P.b.k. at 450 nm in soln. contg. formate ion. 66G433

186a.

p.r. P.b.k. 76A075

63
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's'

1 ) pH Method Comment Ref.

299. 3-Nitrothiophene

299.078 (CH3)2 COH + NX — 2.0 x 109 p.r. P.b.k. 76A075

(CH3 )2 CO + H

+ + NX'

300. o-Nitrotoluene

300.078 (CH3) 2COH + ch3c6h4no2 — 4.8 x 108 7 p.r. P.b.k. in N2 0-satd. soln. contg. 76A020

(CH3)2 CO + H

+ + CH3 C6H4N02

- 0.1 mol L1 2-PrOH.

301. 5-Nitrouracil

301.078 (CH3) 2COH + NX (7 ± 3.5) x 108 p.r. 73A150

302. Norpseudopelletierine-N-oxyl

302.016 •CH2C(CH3)2OH + NPPN (5.1 ± 0.5) x 108 p.r. 71G061

302.078 (CH3)2 tOH + NPPN (8.1 ± 0.8) x 108 p.r. 71G061

303. Orotate ion 303.078 (CH3 )2 COH + orotate (1 ± 0.5) x 108 p.r. 73A150

Paraquat See 1,1' -Dimethyl-4, 4' -bipyridinium ion 183.

304. Penicillamine

304.075 •CH2 OH + RSH (1.1 ± 0.1) x 108 p.r. P.b.k. at 450 nm in soln. 73A073

CH3OH + RS- RSSR-) contg. 0.5 or 1 mol L"

1 MeOH.

305. 3-Pentanone

305.001 •ch3 + C2 HsCOC2 H5 1.4 x 104 chem. Radical from dimethyl sulfoxide in 75D188

ch4 + CH3 CHCOC2 Hs Ti

ni -H2 02 soln.; est. from esr meas. and values for competing

reactions.

306. 1 , 10-Phenanthroline

306.075 •CH2 OH + phen <10fc 7 p.r. P.b.k. in soln. contg. 0.2 mol L"

1 79A148

•CH2 0" + phen <106 13 MeOH.

CH3 CHO' + phen —* -phenH

<1 x 107 ~ 13 p.r. P.b.k. at 490 nm in N2 0-satd. soln. contg. 1 mol L"

1 MeOH.

80A115

306.076 (8 ± 2) x 108 ~ 13 p.r. P.b.k. at 490 nm in N2 0-satd. soln. contg. 1 mol L"

1 EtOH. 80A115

306.078 (CH3) 2 COH + phen —>• -phenH (3.2 ± 0.2) x 109 1 p.r. P.b.k. at 520 nm in soln. contg.

1 mol L'

1 2-PrOH. 80A115

1.9 x 109 3.0 p.r. P.b.k. in Ar-satd. soln. contg. 0.1 mol L"

1 2-PrOH. 79A148

1 x 108 5.5 p.r. P.b.k. in N2 0-satd. soln. 80A115

A X O 8 contg. 2-PrOH.

1.2 x 107 7 P.b.k. in soln. contg. 2-PrOH and 79A148

acetone. (CH3 ) 2 tO- + phen —* -phenH 6.0 x 108 13 P.b.k. in Ar-satd. soln. contg. 0.1 mol L1 2-PrOH.

79A 148

5.7 x 108 13 p.r. P.b.k. 79A305

(3.0 ± 0.5) x 109 ~ 13 p.r. P.b.k. at 490 nm in N2 0-satd. soln. contg. 1 mol L"

1 2-PrOH. 80A115

307. Phenazine

307.078 (CH3 ) 2CO-+ Pz - (CH3 ) 2CO + -PzH 3 x 109 13 p.r. p.b.k. 79A305

308. Phenosafranine

308.056 NH2 CHC02

- + dye 1.9 x 109 (uncor.) 7 p.r. D.k. at 520 nm in N2 0-satd. soln. contg. glycine; 66% e-transfer. 73A078

308.075 •CH2 OH + dye

(CH3 ) 2tOH + dye

1.2 x 109 (uncor.) 7 p.r. D.k at 520 nm in N2 0-satd. soln. contg. MeOH; 22% e-transfer. 73A078

308.078 3.2 x 109 7 p.r. D.k. at 520 nm in N2 0-satd. soln. 73A078

contg. 2-PrOH; 82% e-transfer.

64
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution —Continued

No. Reaction k (L mol 's ’) pH Method Comment Ref.

309. Phenoxide ion 309.020 •CH2 CHO + C6H5 0-(+ H2 0) — 4.3 x 106 -11.5 p.r. Soln. contg. N20 and ethylene glycol. 79A051 CH3 CHO + C6 H50- 4- OH310. o-Phenylenediamine

310.020 •ch2 cho + h2 nc6h4nh2 — 7.3 x 107 -11.5 p.r. Soln. contg. N2 0 and ethylene glycol. 79A051 CH3CHO 4- H2NC6H4NH

311. />-Phenylenediamine

4.0 x 108 311.020 •CH2CHO 4- H2 NC6H4NH2 -* -11.5 p.r. Soln. contg. N20 and ethylene glycol. 79A051 CH3CHO 4- h2nc6h4nh

312. Promethazine

312.048 •CC13 4- PZ slow 12 p.r Suggested that fast reaction is with 78B128

CC13 62 and not -CC13

. 80A053

313. 1-Propanol

313.047 •cf3 4- CH3CH2CH2 OH (4.4 ± 0.7) x 104 9-10 y-r. C.k. with addn. of CF3 to propylene 70G407

(rel.) obs. G(CF3 H); rel. to Ar(CF3 4- HC02

~) = 3.4 x 105

.

314. 2-Propanol

314.001 •CH3 4- (CH3)2CHOH 3.4 x 103 (rel.) y-r. C.k. with 02; radical from Mel; 67G041 CH4 4- (CH3 )2 COH

>(1.6 ± 0.3) x 1 phot.

rel. to A(CH3 4- 02) = 4.7 x 109. Est. from effect of addn. of 2-PrOH 71F579

103 (rel.) on CH4 and C2H6 yields in photolysis

of Co(NH3) s02 CCH32+. 314.015 •CH2CHOHCH3 + (CH3 ) 2 CHOH -+ >53 ± 10 y-r. Est. from rel. rates and G(-H2 02) 70G104

(CH3)2CH0H 4- (CH3) 2COH in soln. contg. H2 02 and 2-PrOH.

314.047 •CF3 4- (CH3)2CHOH - (9.2 ± 0.9) x 104 9-10 y-r. C.k. with addn. of -CF3 to propylene; 70G407 CHF3 4- (CH3 )2COH (rel.) obs. G(CHF3); rel. to A(-CF3 4- HC02

") = 3.4 x 105

. 314.048 CC13 4- (CH3)2CHOH -104 p.r. Reaction proposed to explain initial 73A 140

CCI3- + H

+

4- (CH3)2COH increase of abs. of PNAP" in soln. contg. CCl4-PNAP-2-PrOH-acetone.

•CC13 4- (CH3) 2CHOH — 79 y-r. Calcd. from dependence of G(Cr) on 71G778

CHClj + (CH3)2C0H dose rate in soln. contg. CC14 and 2-PrOH assuming 2A(-CC13 4- -CC13) =

109.

315. Propionic acid 315.001 •CH3 4- CH3 CH2 C02 H -* 3.0 x 103 -1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 4- ch3Chco2 h Ti'"-H202 soln.; est. from esr meas. and values for competing reactions.

316. Propionitrile 316.001 •CH3 4- CH3 CH2CN — 1.2 x 103 -1 chem. Radical from dimethyl sulfoxide in 75D188 ch4 4- ch3 Chcn Ti

MI -H2 02 soln.; est. from esr meas. and values for competing reactions.

317. Propylene

317.001 •CH3 4- CH3 CH = CH2 — addn. 5.3 x 103 (rel.) y-r. C.k. with 2-PrOH in soln. contg. Mel

obs. GfCHj; rel. to A(CH3 4- =

4.7 x 109

.

67G041

317.047 •CF, 4- CH3 CH = CH2 — addn. (7.2 ± 0.4) x 107 9-10 y-r - C.k. with 2-PrOH; radical from CF3 C1; 70G407

(rel.) obs. G(CF3 H) by H abstr. from formate

rel. to A(CF3 4- HC02

') = 3.4 x 10\

1 , T-Propylene-2,2'-bipyridinium ion See Trimethylene-2,2'-bipyridinium ion 354.

318. Pteridine

318.075 •CH2 OH 4- P 3.6 x 108 6.0 p.r. P.b.k. in N20-satd. soln. contg. MeOH.

76A060

65
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mor's"1 ) PH Method Comment Ref.

319. Pterin 319.075 •CH2OH -(- PtH2 +

9.0 x 107 (uncor.) 0.8 p.r. P.b.k. in N20-satd. soln. 76A060

•CH2OH + PtH <107 7.0 contg. MeOH; ~40% e-transfer •ch2o- + Pt* 6.0 x 108 13.0 at pH 0.8, ~ 100% at pH 13. 319.076 ch3Choh + PtH 3.7 x 107 (uncor.) 7.0 p.r. P.b.k. in N20-satd. soln. 76A060

ch3Cho- + pr

(CH3)2 COH + PtH2 +

1.2 x 109 13.0 contg. EtOH; ~40% e-transfer at pH 7, -100% at pH 13. 319.078 2.0 x 109 0.8 p.r. P.b.k. in N20-satd. soln. 76A060

(CH3)2COH + PtH 4.5 x 108 7.0 contg. 2-PrOH; — 100% e-transfer. (ch3)2Coh + pr <107 9.4 (CH3 )2Co- + Pt- 1.5 x 109 13.0 319.147 •C02

- + PtH 4.6 x 108 7.0 p.r. P.b.k. in N20-satd. soln. 76A060

•C02 “f" Pt <107 9.5- contg. formate ion; 100% e-transfer 13.0 at pH 7.

320. Purine

320.078 (CH3)2COH + ph2 +2.7 x 109 ~0 p.r. P.b.k. in N20-satd. soln. contg. 75A060

(CH3)2 COH + PH <107 6.0 1-2 mol L'

1 2-PrOH.

(CH3)2Co- +

p- <107 13.3 320.147 •C02

- + PH <107 6.0 p.r. P.b.k. in N20-satd. soln. 75A060

321. Pyrazine

321.078 (CH3)2COH + PzH +2.8 x 109 -0 p.r. P.b.k. in N20-satd. soln. contg. 74A127

(CH3)2COH + Pz <107 5.0, 2-PrOH; k * 5 x 109 in 70% HC104 soln. 11.0 (CH3)2 Co- + Pz 1.7 x 109 13.6 321.147 •C02" + Pz <107 5.0, p.r. P.b.k. in N20-satd. soln. 74A127

11.0 contg. formate ion.

322. Pyrazinecarboxylic acid 322.078 (CH3) 2tOH + PzC02 H - ~8.5 x 108 p.r. P.b.k. 78A222

(CH3)2CO + -Pz(H)C02 H

323. Pyrene

323.075 •CH20- + Py no reaction 13 p.r. Buildup of Py" in micellar soln. contg. 0.2 mol L"

1 MeOH after 76A062

phot, attributed to triplet pyrene; A(-CH20' +

3Py) = 1.8 x 1010

. 323.076 CH3CHO- + Py - 1.7 x 108 13 p.r. P.b.k. at 495 nm in soln. 76A062

CH3CHO + Py' contg. 0.2 mol L"

1 EtOH and 10"3 mol LTl pyrene solubilized by 5 x 10"3 mol Lf1

(CH3)2tO- + Py —

hexadecyl trimethylammonium bromide;

after photolysis k{R +

3Py) = 8 x 109

. 323.078 2.3 x 109 13 p.r. P.b.k. at 495 nm in soln. contg. 76A062

(CH3)2CO + Py- 2 x 10^ mol L"

1 pyrene, 0.2 mol L"

1 2-PrOH, 0.1 mol L"

1 acetone and 5 x 10"3 mol L'

1 hexadecyl trimethyl-ammonium

bromide; after photolysis k(R -)- 3Py) =

2.3 x 109. 323.147 •C02" + Py no reaction 13 p.r. Buildup of 495 nm abs. in micellar

soln. (C02-satd.) only after photolysis; A(-C02" +

3Py) = 5 x 109

; calcd. A(-C02

" + Py") = 1.8 x 1010 from

76A062

d.k. at 495 nm in micellar C02-free

soln. contg. formate ion.

324. Pyridazine

324.078 (CH3)2COH + PdH + — 2.6 x 109 ~0 p.r. P.b.k. in N20-satd. soln. 74A127

(CH3)2CO + -PdH2 + (CH3)2tOH + Pd <107 5.0,

contg. 2-PrOH. 74A127

11.0 (Ch3)2Co- + Pd — 2.1 x 109 13.6 74A127

(CH3)2CO + -PdH + OH- 66
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L moP's ') pH Method Comment Ref.

324.147 •co2

- + Pd <107 5.0, p.r. < 10% e-transfer. 74A127

11.0

325. 4-Pvridinecarboxaldoxime

325.078 (CH3) 2£OH + HN+ Cs H4CH = NOH 1.7 x 109 acid p.r. P.b.k. (pyridinyl radical) 76A182 <107 7 in N20-satd. soln. contg. 2-PrOH;

(CH3) 2CO- + NC5 H4CH = NO- 1.7 x 108 13.3 e-transfer in strong acid or base.

326. 2-Pyridinecarboxaldoxime methochloride

326.078 (CH3)2COH + CH3 N

+ C5 H4CH = NOH 6 x 108 3,7, p.r. P.b.k.; e-transfer. 76A182

11

3-Pyridinecarboxamide See Nicotinamide 275.

4-Pyridinecarboxamide See Isonicotinamide 244.

3-Pyridinecarboxylic acid See Nicotinic acid 277.

4-Pyridinecarboxylic acid See Isonicotinic acid 245.

327. Pyridoxal-5-phosphate

327.078 (CH3)2Coh + p — -p 5.8 x 108 1.0 p.r. P.b.k. in N20-satd. soln. 75A024

(CH3 )2Coh + p — -p 1.3 x 108 5.6 contg. 1 mol L"

1 2-PrOH.

(ch3) 2Co- + p -p 2.9 x 108 10.0, 13.3

328. Pyridoxine

328.078 (CH3 )2 COH + PH <107 1,7, p.r. P.b.k. in N2 0-satd. soln. 75A024

13.5 contg. 1 mol L'

1 2-PrOH.

329. Pyrimidine

329.078 (CH3) 2 (!:OH + PmH +

2.2 x 109 ~0 p.r. P.b.k. in N20-satd. soln. contg. 74A127

(CH3)2 CO + •PmH2 + 2-PrOH.

(CH3 )2 COH + Pm <107 5.0, p.r. P.b.k. in N2 0-satd.soln. contg. 74A127

11.0 2-PrOH.

(CH3 )2 CO- + Pm ^io17 13.6 p.r. P.b.k. in N20-satd. soln. contg. 2-PrOH. 74A127

329.147 •C02

" + Pm <107 5.0, p.r. P.b.k. in N20-satd. soln. contg. 74A127

11.0 formate ion; < 10% e-transfer.

330. Pyruvate ion 330.113 •A" + CH3C0C02

- <10 8.6 p.r. D.k. at 360 nm in N2 0-satd. soln. 75A240

(•A‘ = ascorbate radical) contg. ascorbate ion.

331. Quinoxaline

331.076 CH3CHOH + Qx ^ 6.5 x 107 (uncor.) 6.5 p.r. P.b.k. in N20-satd. soln. contg. 74A127 CH3 CH0 + QxH EtOH; 70% e-transfer. 331.078 (CH3 )2COH + QxH + —

(CH3 )2 CO + -QxH2 +

(CH3) 2 COH + Qx—

3.7 x 109 ~0 p.r. P.b.k. in N20-satd. soln. contg. 2 mol Lf

1 HC104 and 2 mol L'1 2-PrOH; k =* 7.0 x 108 at 70% HC104

.

74A127

1.6 x 108 6.5 p.r. P.b.k. in N20-satd. 9oln. contg. 74A127

(CH3 )2 CO + -QxH 2-PrOH.

Resorcinol See 1,3-Dihydroxybenzene 1 77.

332. Rhodamine B

332.147 C02

- + RhB -* C02 + RhBrcd (1.8 ±0.5) x 108 p.r. D.k. at 510 nm as well as p.b.k.

at 410 nm in soln. contg. 0.1 mol L'

1 formate ion.

67E053

333. Riboflavin 333.056 NH2 CHC02

- + RF (2.7 ± 0.3) x 109 8.0 p.r. P.b.k. at 560 nm in N2 0-satd. soln. contg. glycine; e-transfer. 73A104

67
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution —Continued

No. Reaction k (L mol ’s’

1 ) pH Method Comment Ref.

333.078 (CH3)2 COH + RF (2.3 ± 0.2) x 109 7.0 p.r. P.b.k. at 560 nm in N2 0-satd. soln. contg. 2-PrOH; e-transfer. 73A104

333.115 CHOHCCV + RF (9.3 ± 0.9) x 108 7.0 p.r. P.b.k. at 560 nm in N2 0-satd. soln. contg. glycolate ion; e-transfer. 73A104

333.147 •C02‘ + RF 1.4 x 109 alk p.r. D.k. at 460 nm as well as p.b.k. 69G238

3.6 x 109 5.9 at 560 nm (semiquinone) in N2 0-satd.

soln. contg. formate ion. 3.6 x 109 3 p.r. D.k. at 420 nm in N20-satd. soln. 69G238

3.0 x 109 H0 =-2 contg. formate ion. (1.7 ± 0.2) x 109 7.0 p.r. P.b.k. at 560 nm in N2 0-satd. soln. contg. formate ion; e-transfer. 73A104

334. Riboflavine 5'-pho8phate (Flavine mononucleotide)

334.078 (CH3 ) 2 COH + FMN (1 ± 0.5) x 109 p.r. 73A150

335. Ribonuclease

335.045 •CHC12 + RNase 6 x 108 11 p.r. P.b.k. in soln. contg. CHC13 and tert-BuOH. 73A140

336. 336.056 Safranine T

NH2 CHC02

- + Dye

(CH3)2 60H + Dye

1.6 x 109 (uncor.) 7 p.r. D.k. at 520 nm in N2 0-satd. soln. contg. glycine; 60% e-transfer. 73A078

336.078 2.8 x 109 7 p.r. D.k. at 520 nm in N2 0-satd. soln. contg. 2-PrOH; 86% e-transfer. 73A078

337. meso-Tetra(4-carboxyphenyl)porphyrin

337.078 (CH3 ) 2COH + H2TCPP -* H2 TCPP-- (9 ± 1) x 108 7-11 p.r. P.b.k. at 460 and 700 nm

in N20-satd. soln. contg. 0.2 mol L’

1 2-PrOH.

79A143

338. Tetrachlorobenzoquinone (Chloranil)

338.076 ch3 choh + 0 =C6C14 =0-* (2.9 to 3.4) x 109 p.r. P.b.k. in CTAB or NaLS micelles; 76A104

e-transfer soln. contains 0.1 mol L"

1 EtOH; cor. for e

’ reaction. aq

339. 1 ,2,4,5-Tetracyanobenzene

339.076 CH3 CHOH + C6H2(CN)4 -> (3.3 to 4.1) x 109 p.r. P.b.k. in CTAB or NaLS micelles; 76A104

e-transfer soln. contains 0.1 mol L’

1 EtOH; cor. for e

" reaction. aq

340. Tetrahydrofuran

340.048 •CC13 + c4h8o 57 Calcd. from dependence of G(Cl’) on dose rate in soln. contg. CC14 and

tetrahydrofuran.

71G778

Tetramethyl-p-benzoquinone See Duroquinone 198.

N,N,JY,IV-Tetramethyldiazenedicarboxamide See Diamide 1 70.

341. l,l'-Tetramethylene-2,2'-bipyridinium ion

341.147 •C02- + BP2+ - C02 + -BP’ 9.0 x 109 7.0 p.r. P.b.k. at 680 nm in N20-satd. soln. contg. 0.2 mol L"

1 formate. 76A169

7 x 109 6.8 p.r. P.b.k. in N2 0-satd. soln. contg. 0.1 mol L’

1 formate ion. 78A321

342. 2,2,6,6-Tetramethyl-4-oxo-l-piperidinyloxy (TAN)

342.004 c-C5 H9 + TAN (4.0 ± 0.4) x 108 acid p.r. Condy. changes in N20-satd. soln. contg. 10’2 mol L"

1 cyclopentane; addn. 76A067

reaction. 342.016 •CH2 C(CH3 ) 2 OH + TAN (2.8 ± 0.3) x 108 2.4 p.r. Condy. changes in N2 0-satd. soln. contg. 0.1 mol L’

1 tert-BuOH; addn.

reaction.

76A067

68
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L moR's'

1 ) PH Method Comment Ref.

342.075 •CH2 OH + TAN 7.2 x 108 5-6 p.r. C.k. in N2 0-satd. soln. contg. 71G618

(rel.) 1 mol L'

1 MeOH; *(-CH2OH +

ferricyanide) = 4.0 x 109. (7.2 ± 0.7) x 108 acid p.r. Condy. changes in N2 0-satd. soln. contg. 0.1 mol L'

1 MeOH; addn.

reaction.

76A067

342.076 CHjCHOH + TAN 6.4 x 108 5-6 p.r. C.k. in N2 0-satd. soln. contg. 71G618

(rel.) EtOH assuming &(R + ferricyanide) =

5.3 x 109.

. (4.0 ± 0.4) x 108 acid p.r. Condy. changes in N2 0-satd. soln. contg. 0.1 mol I/

1 EtOH; e-transfer. 76A067

342.078 (CH3 )2 tOH + TAN 3.9 x 108 5-6 p.r. C.k. in N2 0-satd. soln. contg. 71G618

(rel.) 2-PrOH, rel. to A(R + ferricyanide) =

4.7 x 109

; k = 4.7 x 108 rel. to

k( R + PNAP) = 3.8 x 109

. (4.3 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L'

1 2-PrOH; addn.

reaction.

76A067

342.105 R + TAN 1.9 x 108 5-6 p.r. C.k. in N2 0-satd. soln. contg. 71G618

(R = Radicals from (rel.) PEO(20000), rel. to k( R + ferri- polyethylene oxide) cyanide) = 2.1 x 109

; similar values were obtained for PEO(600) and PEO(200). 342.108 R + TAN 3.9 x 108 5-6 p.r. C.k. in N20-satd. soln. contg. 71G618

(R = Radicals from deoxy- (rel.) deoxyribose, rel. to &(R + ferri- ribose) cyanide) = 2.8 x 109

. 342.111 R + TAN <1 x 108 5-6 p.r. C.k. in N20-satd. soln. contg. 71G618

(R = Radicals from (rel.) glucose, rel. to £(R + ferricyanide) glucose)

(5.9 ± 0.6) x 107 acid p.r. = 1.9 x 109

. Condy. change in N20-satd. soln. contg. 0.1 mol L"

1 glucose. 76A067

342.147 •co2

- + tan 7.0 x 108 7-8 p.r. P.b.k. at 310 nm in N2 0-satd. soln. contg. formate. 71G618

5.4 x 108 7-8 p.r. C.k. in N2 0-satd. soln. contg. 71G618

(rel.) formate, rel. to k(-C02~ + ferri- cyanide) = 1.06 x 109

.

343. 2,2,6,6-Tetramethyl-4-hydroxy-l-piperidinyloxy (TMPN)

343.004 c-C5 H9 + TMPN (4.3 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 10~2 mol L'

1 cyclopentane; addn. 76A067

reaction. 343.016 •CH2 C(CH3 )2 OH + TMPN (1.5 ± 0.2) x 108 2.6 p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L"

1 tert-BuOH; addn.

reaction.

76A067

343.075 •CH2 OH + TMPN (4.4 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L"

1 MeOH; addn. reaction. 76A067

343.076 CH3 CHOH + TMPN (4.9 ± 0.5) x 108 acid p.r. Condy change in N2 0-satd. soln. contg. 0.1 mol L"

1 EtOH; e-transfer. 76A067

343.078 (CH3 )2 £OH + TMPN (3.6 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L"

1 2-PrOH; e-transfer. 76A067

343.111 R + TMPN (4.9 ± 0.5) x 107 acid p.r. Condy. change in N2 0-satd. soln. 76A067

(R = Radicals from glucose) contg. 0.1 mol L"

1 glucose; addn.

reaction.

344. A^WjTV'jTV-Tetramethyl-p-phienylenediamine

344.020 •CH2 CHO + TMPD (+ H2 0) — 2.0 x 109 — 1 1.5 p.r. Soln. contg. N2 0 and ethylene glycol; 70A051 CH3CHO + TMPD- + OH' radical cation ident. by abs. spectra.

345. 2,2,5,5-Tetramethyl-l-pyrrolidinyloxy-3-carboxamide (NX-s)

345.001 •CH3 + NX-s (7.5 ± 0.8) x 108 3.0 p.r. Condy. change in N2 0-satd. soln. 76A152

contg. 10 2-10_1 mol L"

1 dimethyl

sulfoxide; addn. reaction.

69
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mor's'1 ) pH Method Comment Ref.

345.004 c-C5 H9 + NX-s (3.5 ± 0.4) X 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 10'2-10'’ mol Lf

1 cyclopentane; addn. reaction.

76A152

345.014 •CH2 CH2 OH + NX-s (4.7 ± 0.5) X 108 acid p.r. Condy. change in N20-satd. soln. contg. 10

-2— 10_1 mol L"

1 ethylene; addn. reaction.

76A152

345.016 •CH2 C(CH3) 2OH + NX-s (1.8 ± 0.2) X 108 acid p.r. Condy. change in N20-satd. soln. contg. lO^-lO" 1 mol L'

1 tert-BuOH;

addn. reaction.

76A152

345.075 •CH2OH + NX-s (4.6 ± 0.5) X 108 acid p.r. Condy. change in N20-satd. soln. contg. 0.1 mol L'

1 MeOH; addn. reaction. 76A152

345.076 CH3CHOH + NX-s (4.3 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L'

1 EtOH; e-transfer. 76A152

345.078 (CH3)2 tOH + NX-s (3.3 ± 0.3) x 108 acid p.r. Condy. change in N20-satd. soln. contg. 0.1 mol L'

1 2-PrOH; e-transfer. 76A152

345.111

346.

R + NX-s

(R = Radicals from glucose)

2,2,5,5-Tetramethyl-3-pyrrolin-l-

(5.1 ± 0.5) x 107 acid

-yloxy-3-carboxamide (NX-u)

p.r. Condy. change in N20-satd. soln. contg. 0.1 mol L'

1 glucose; e-transfer. 76A152

346.001 •CH3 + NX-u (7.8 ± 0.8) x 108 acid. p.r. Condy. change in N2 0-satd. soln. contg. 10

-2— 10_1 mol L*

1 dimethyl

sulfoxide; addn. reaction.

76A152

346.004 c-C5H9 + NX-u (3.6 ± 0.4) x 108 acid p.r. Condy. change in N20-satd. soln. contg. 10'2-10'' mol L'

1 cyclopentane; addn. reaction.

76A152

346.014 •CH2CH2 OH + NX-u (4.8 ± 0.5) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 10

-2— 10_1 mol L'

1 ethylene; addn. reaction.

76A152

346.016 •CH2C(CH3)2 OH + NX-u (2.0 ± 0.2) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. lO^-lO'1 mol L'

1 tert-BuOH;

addn. reaction.

76A152

346.075 •CH2 OH + NX-u (3.5 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L'

1 MeOH; addn. reaction. 76A152

346.076 CH3CHOH + NX-u (6.2 ± 0.6) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L"

1 EtOH; e-transfer. 76A152

346.078 (CH3) 2 tOH + NX-U (3.6 ± 0.4) x 108 acid p.r. Condy. change in N2 0-satd. soln. contg. 0.1 mol L

_1 2-PrOH; e-transfer. 76A152

346.111

347.

R + NX-u

(R = Radicals from glucose) Tetranitromethane

(4.3 ± 0.4) x 107 acid p.r. Condy. chnge in N2 0-satd. soln. contg. 0.1 mol L"

1 glucose; e-transfer. 76A152

347.075 •CH2 0H 4- C(N02 )4 -* CH20 + N02 + H

+ + C(N02)3

- (5.0 ± 1) x 109 p.r. P.b.k. at 350 nm in N20-satd. soln. contg. 0.1 mol L'

1 MeOH.

64G133

347.076 CH3CHOH + C(N02 ) 4 CH3CHO + N02 + H

+ + C(N02) 3- 5.6 x 109

~3.5 x 109

~1 p.r.

p.r.

P.b.k. at 366 nm in soln. contg.

O. 5 mol L'

1 EtOH.

P. b.k. in solns. contg. 0.1 mol L'

1 EtOH and either 0.1 mol L'

1 Na dodecyl

sulfate or 0.02 mol L"

1 dodecyltri- methylammonium chloride.

65G183

76A104

347.077 CH3 CH2 CHOH + C(N02)4 -

CH3CH2 CHO + N02 + H

+

-)- C(N02 ) 3

(4.7 ± 1) x 109 p.r. P.b.k. at 350 nm in N2 0-satd. soln. contg. 0.1 mol L*

1 1-PrOH. 64G133

347.078 (CH3)2 COH + C(N02)4 (CH3)2 CO + H

+ + N02 + C(N02)3

- (5.0 ± 1) x 109 p.r. P.b.k. at 350 nm in N20-satd. soln. contg. 0.1 mol Lf

1 2-PrOH. 64G133

347.092a •CH2OCH3 + C(N02) 4 —

CH30CH20N + (0')C(N02)3 * CH3 0CH2 0N(6)C(N02)3

ON X o p.r. P.b.k. at 300 nm in N20-satd.

soln. contg. 0.05 mol L'

1 methyl ether; adduct decomposes to nitroform anion, k = 1.1 x 104 s'

1

.

80A071

347.093 CH3CH2 OCHCH3 + C(N02 ) 4 —

C(N02 ) 3

- ~4 x 109 p.r. P.b.k. at 350 nm in N20-satd.

soln. contg. ethyl ether. 80A071

347.093a •CH2 OC(CH:j ) 3 + C(N02)4 — — 3 x 109 p.r. P.b.k. at 350 nm in N20-satd. 80A071 C(N02)3 soln. contg. methyl ierf-butyl ether.

70
Table 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol ’s'

1 ) PH Method Comment Ref.

347.094a •CH2 OCH2 OCH3 + C(N02 )4 — 5 x 109 4-13 p.r. P.b.k. at 300 nm in N2 0-satd. 80A071 CH3 0CH2 0CH2 0N(6)C(N02)3 soln. contg. 0.1 mol I/

1 dimethoxymethane;

adduct decomposes to nitroform anion

(A 350 nm), k = 8.2 x 102 s'

1

. 347.101 CH2OHCHOH + C(N02) 4 CH3 CHOHCHOH + C(N02 ) 4

1.7 x 109 p.r. P.b.k. in soln. contg. 0.2 mol L"

1 ethylene glycol. 73G126

347.102 3.2 x 109 p.r. P.b.k. in soln. contg. 0.2 mol L'

1 1,2-propanediol. 73G126

347.103 CH3 CHOHCOHCH3 + C(N02 ) 4 3.3 x 109 p.r. P.b.k. in soln. contg. 0.2 mol L'

1 2,3-butanediol. 73G126

347.106 CH2 0HCH0H6H0H + C(N02 ) 4 (2.4 ± 0.3) x 109p.r. P.b.k. at 350 nm in N2 0-satd. soln. 64G133

(+ CH2 OHCOHCH2 OH) contg. 0.1 mol L~’ glycerol. 347.111 R + C(N02 )4 2.6 x 109 p.r. P.b.k. at 366 nm in N2 0-satd. soln. 65G183

(R = Radicals from glucose) 0.25 mol L'

1 glucose. 347.112 R + C(N02 ) 4 (7.0 ± 1) x 10s p.r. P.b.k. at 350 nm in N2 0-satd. soln. 64G133

(R = Radicals from sucrose)

(8.5 ± 1) x 108 p.r.

contg. 0.1 mol L"

1 sucrose.

P.b.k. in soln. contg. 0.1 or 0.01 mol L"

1 sucrose. 65G183

347.147 •CO2 + C(N02)4 (4 ± 1) x 109 p.r. P.b.k.; independent of pH between

3 and 7. 70G303

348. Thiamine

348.078 (CH3 ) 2 COH + TmH+ — 2.2 x 108 0.5 p.r. P.b.k. in soln. contg. 2-PrOH. 77A034

(CH3)2CO + •TmH2 + (CH2) 2 COH + Tm — 1.9 x 108 6.6 p.r. P.b.k. in soln. contg. 2-PrOH. 77A034

(CH3)2CO + •TmH +

349. Thiazole

349.078 (CH3)2 tOH + c3h3 snh+

6.2 x 108 0.8 p.r. P.b.k. in soln. contg. 2-PrOH. 77A034

(CH3)2CO + -c3h3 snh2 + (CH3)2 £o- + c3 h3sn 13.3 p.r. No electron transfer. 77A034

350. Thionine

350.056 NH2CHC02

- + Dye 3.2 x 109 8 p.r. D.k. at 600 nm in N20-satd. soln. contg. glycine; 85% e-transfer. 73A078

350.075 •CH2OH + Dye 2.6 x 109 8 p.r. D.k. at 600 nm in N2 0-satd. soln. contg. MeOH; 86% e-transfer. 73A078

350.078 (CH3 ) 2tOH + Dye 4.2 x 109 8 p.r. D.k. at 600 nm in N2 0-satd. soln. contg. 2-PrOH; 88% e-transfer. 73A078

351. Trichloroacetate ion 351.078 (CH3)2(:oh + cci3co2- 5 x 106 (rel.) p.r. C.k. in soln. contg. 2-PrOH and

acetone; rel. to &(R + PNAP) =

3.8 x 109

.

73A140

(CH3)2tO- + cci3 co2

- 3 x 108 (rel.) 13 p.r. C.k. in soln. contg. 2-PrOH and

acetone; rel. to A:(R + PNAP) =

3.8 x 109.

73A140

352. Trifluoroacetate ion

352.078 (CH3)2tOH + CF3C02

- < 1 x 10s (rel.) p.r. C.k. in soln. contg. 2-PrOH and

acetone; rel. to k( R + PNAP) =

3.8 x 109

.

73A140

353. 2,3,5-Trimet hylbenzoquinone

353.078 (CH3)2tOH + Q — 3.6 x 109 7 p.r. P.b.k. in soln. contg. 1 mol L'

1 73G125

(CH3)2CO + H

+ + Q

+ 2-PrOH and 1 mol L'

1 acetone. 354. l,l'-Trimethylene-2,2'-bipyridinium ion 354.147 •C02

- + BP^ — C02 + -BP +

7.5 x 109 7.0 p.r. P.b.k. at 680 nm in N20-satd. soln. contg. 0.2 mol L'

1 formate ion. 76A169

1.1 x 10'° 6.8 p.r. P.b.k. in N2 0-satd. soln. contg. 78A321

0.1 mol L'

1 formate. 4

71
TABLE 2. Rate constants for reactions of aliphatic radicals with organic solutes in aqueous solution—Continued

No. Reaction k (L mol 's"

1 ) pH Method Comment Ref.

355. Trinitrobenzenesulfonate ion

355.111 R + (N02) 3C6H2S03

- 1.1 x 109 p.r. 77R167

(R = Radicals from glucose)

356. 2,4,6-Trinitrobenzoate ion 356.078 (CH3)2COH + (N02 ) 3C6H2C02

- — 3.9 x 109 7 p.r. P.b.k. in N20-satd. soln. contg. 76A111

(CH3)2 CO + H

+ +

(N02-)(N02) 2 C6H2C02- 2-PrOH; k at pH 0.8 within 20-30%.

356.147 •co2 + (N02 )3 C6H2C02 3.4 x 109 7 p.r. P.b.k. in N2 0-satd. soln. contg. formate; k at pH 0.8 within 20-30%. 76A111

357. Trypan blue

357.078 (CH3)2COH + Dye (3 ± 1.5) x 109 p.r. 73A150

358. Tyrosine

358.048 •CC13 + ArO~ slow 12 p.r. Suggested that fast reaction is 78B128

CC1362 + ArCT -+ ArO- (k = 1.6 x 108

) and -CC^ is less reactive. 80A053

359. Ubiquinone

359.078 (CH3)2 COH + Q — 1.9 x 109 7 p.r. P.b.k. in soln. contg. 7 mol L"

1 73G125

(CH3)2CO + -Q- + H

+ 2-PrOH and 1 mol L"

1 acetone.

Vitamin Bs See Nicotinamide 275.

Vitamin BI2 See Cyanocobalamin (under Cobalt(III) ions) 53.

Vitamin BI2a See Hydroxocobalamin (under Cobalt(III) ions) 54.

Vitamin BI2r See Cobalamin (under Cobalt(II) ions) 10.

360. 360.078 Vitamin

(CH3) 2 COH + Q

-> 1.7 x 109 7 p.r. P.b.k. in soln. contg. 5 mol 73G125

(CH3)2CO + -Q' + h

+

L”

1 2-PrOH and 2 mol L'

1 acetone.

Vitamin K3 See 2-Methyl-1,4-naphthoquinone 262.

72
Tabi.F. 3. Rate constants for acid- and base-catalyzed proton transfer reactions of aliphatic radicals in aqueous solution

No. Reaction k (L mol 's ') pH Method Comment Ref.

361. Hydronium ion 361.075 •ch2 oh + h3 o

+ — k{ = 1.76 x 108 chem. Esr; radicals from Ti(III)-H 2 02 -Me0H. 65D040

•ch2 oh2 + + h2 o k< = 3.6 x 107 phot. Esr; soln. contg. 10% acetone and 5% MeOH.

66D162

k, -- (3.19 ± 0.04) chem. Esr; radicals from Ti(III)-H 2 02-Me0H 68M058

x 107 at 30.4°C; Ea = 2.8 ± 5 kcal mol

-1

(11.7 kj moE1 ) at 5.7-41°C; A = 9.5 s’

1

. 361.078 (CH3 ) 2 £OH + h3 o

+

k, = 7.2 x 107 phot. Esr; soln. contg. 10% acetone and 66D162

(CH3) 2 COH2 + + h2o

k, = (6.44 ± 0.30) chem. 5% 2-PrOH.

Esr; radicals from Ti(III)-H 2 02 - 68M058

x 107 2-PrOH.

361.148 CH3C(0-)0CH3 + h3 o

+ — 1.4 x 1010 p.r. D.k. at 360 nm in soln. contg. 78A402 CH3 C(OH)OCH3

-(- h2 o methyl acetate and HC104 (1-5 x

10-5 mol L’

1 ).

362. Hydroxide ion 362.022 •CH=CHOH + OH — kf = (1.5 ± 0.3) 9.4-10 p.r. D.k. at 260 nm in 10"3 mol L'

1 78A007

[•CH = CHO*] + H2 0 x 1010 acetylene soln.; hydrolysis product

is formylmethyl radical. 362.060 CHjCONHCHCOO' -(- OH' — k( = (8 ± 2) x 108 >13 e-r. Est. by esr from pH dependence of 76D198 ch3 con-£hcoo- + H2 0 line width in N2 0-satd. soln. contg.

acetylglycine; kr — 1.6 x 10 ‘; (p^a = 14.0). 362.062 R(NH) + OH' R(N") + H2 0 ~(8 ± 2) x 109 ~9.2- p.r. P.b.k. at 300 nm in N2 0-satd. soln. 71G554

(R = Radicals from 10.5 contg. 4 x 10~3 mol L'

1 glycine

glycine anhydride) anhydride. 362.063 R(NH) + OH" — R(N1 + H2 0 ~(1.1 ± 0.2) x ~9.2- p.r. P.b.k. at 300 nm in N2 0-satd. soln. 71G554

(R = Radicals from 10'° 10.5 contg. 4 x 10"3 mol L"

1 alanine

alanine anhydride) anhydride. 362.074 -(CH2)2 CONHC(COO> + OH' —

-(CH2) 2CON-C(COO> + H20

ch3Choh + oh- —

kf = 1 x 109 e-r. Est. by esr from pH depencence of

line width in N2 0-satd. soln. contg. 2-pyrrolidone-5-carboxylic acid; (p/Ca = 12.7).

77D087

362.076 k( =7x 109 11-12 e-r. Esr line broadening in N2 0-satd.

soln. contg. 0.1 mol L"

1 EtOH;

kr = 4.1 x 10s

( P

A:a = 11.51).

73D065 ch3Cho- + h2 o

(CH 362.078 3) 2 COH + OH- — kt = 9 x 109 11-12 e-r. Esr line broadening in N20-satd. 73D065

(CH3)2tO- + h2 o

kf = 7.5 x 109 10.4- p.r.

soln. contg. 0.1 mol L"

1 2-PrOH;

kT = 1.8 x 106

( P

A:a = 12.03). Condy. in soln. contg. 1 mol L1 80A323

11.0 acetone gave kT = (1.4 ± 0.1) x 106

; kf calcd. from pKa = 12.00. 362.101 •CHOHCH2 OH + OH- — ~ 10 10 10 p.r. Absorption spectrum immediately after 73G004

[•CHO-CH2 OH] 4- H2 0 pulse in N20-satd. soln. contg. -CH2 CHO + OH- ethylene glycol decays in < 10 pis to formylmethyl spectrum. 362.114 •CHOHCONH2 + OH" — kf = 1.1 x 10 10 8.3- p.r. Calcd. from effect of [OH'] in 75A053 •CHO-CONH2 + h2 o 9.9 buffer soln. on d.k. at 290 nm in N2 0-satd. soln. contg. glycolamide;

cor. to / = 0. 362.115 •CHOHC02- + OH- k, = 3.9 x 109 9.5- p.r. Calcd. from effect of [OH"] in 75A053 •CH0C02- + h2 o 10.5 buffer soln. on d.k. at 270 nm in N2 0-satd. glycolate soln.; cor. to 1=0, k = (3.1 ± 0.4) x 109 in unbuffered soln. 362.116 •COH(CH3 )CONH2 + OH- — k, = 1.1 x 10'° 8.0- p.r. Calcd. from effect of [OH-

] in 75A053

•CO-(CH3 )CONH2 + h2 o 10.2 buffer soln. on d.k. at 300 nm in N2 0-satd. lactamide soln.; cor. to 1=0.

73
Table 3. Rate constants for acid- and base-catalyzed proton transfer reactions of aliphatic radicals in aqueous solution-—Continued

No. Reaction k (L mol 's"

1 ) PH Method Comment Ref.

362.134 [CH2CHC02HK + OH' 7.7 x 108 >7 p.r. Calcd. from effect of [OH"] on

d.k. in acrylate soln.; cor. to / = 0; for mechanism and evidence for protonation at the /3 position see 74G033.

76A113

362.135 [CH3CHCHC02H]-- + OH' ~1.2 x 108 >7.5 p.r. Calcd. from effect of [OH"] on 76A113

ch3 ch2 <!:hco2

- + oh- d.k. in tra/w-crotonate soln.;

cor. to / = 0. 362.136 [CH2 C(CH3)C02 HK + OH- - 8 x 108 >5.3 p.r. Calcd. from effect of [OH"] on 76A113

(CH3)2tC02- + OH- d.k. in soln. contg. methacrylate;

cor to / = 0. 362.137 [(CH3)2 CCHC02 H].- + OH- - 3 x 106 >8.0 p.r. Calcd. from effect of [OH"] on 76A113

(CH3)2 ch<!:co2- + oh- d.k. in /3,/3-dimethylacrylate soln.; cor. to 1 = 0. 362.139 [CH3 CHCHCHCHC02 H]-- + OH- -2 x 107 >6.4 p.r. Calcd. from effect of [OH"] on

d.k. in soln. contg. sorbate;

cor. to / = 0.

76A113

363. Water

363.128 [CH2CHCONH2

].- + h2o - 1.4 x 105 s'

1 9.3- p.r. D.k. in acrylamide soln contg. 75A052

ch3Chconh2 + OH- 13 10"3 mol L"

1 borate buffer; general

acid catalysis by buffer components,

e.g. B(OH)3 , NH4 +

, (CH3 )3NH +, HC03

‘, HP04

2

-, etc. 363.129 [CH3CHCHCONH2

].- + h2 o 2 x 104 s'

1 10.2 p.r. D.k. in traras-crotonamide soln. 75A052

ch3 ch2 Chconh2 + OH- contg. borate buffer, as above. 363.130 [CH2C(CH3)CONH2

]-- + h2o 1.3 x 106 s'

1 10-13 p.r. D.k. in methacrylamide soln. contg. 75A052

CH3 t(CH3)CONH2 + OH- borate buffer, as above. 363.131 [(CH3)2 CCHCONH2K + h2o — 2 x 104

s'

1 10.2 p.r. D.k. in /3,/3-dimethylacrylamide soln. 75A052

(CH3)2 CHCHCONH2 + OH- cor. to / = 0. 363.132 [CH2CHCON(CH3)2

]-- + h2o 3.7 x 105 s'

1 10 p.r. D.k. in ./V,/V-dimethylacrylamide soln. 75A052

CH3CHCON(CH3)2 + OH- contg. borate buffer, as above. 363.134 [CH2CHC02H]-- + h2 o 4.0 x 104 s'

1 6.0 p.r. D.k. in acrylate soln.; extrapolated 76A113

3.0 x 104 s’

1 9.5 to zero concn. of buffer. 363.135 [CH3CHCHC02H]-- + h2 o - 1.0 x 104 s'

1 10.4 p.r. D.k. in crotonate soln.; extrapolated 76A113

ch3 ch2 Chco2- + h2o to zero concn. of buffer. 363.136 [CH2C(CH3)C02 H]-- + h2o -> 2.0 x 105 s'

1 9.0 p.r. D.k. in methacrylate soln.; extrapo- 76A113

CH3 C(CH3)C02- + h2o lated to zero concn. of buffer. 363.137 [(CH3)2CCHC02H]-- + h2 o -> 9 x 103 s'

1 11.0 p.r. D.k. in /3,/3-dimethylacrylate 76A113

(CH3)2 CHCHC02

- + h2 o soln.; extrapolated to zero concn.

of buffer. 363.138 [CH2 C(CH3)C02CH3K + h2 o — 4.5 x 10s s'

1 9.8- p.r. D.k. in methyl methacrylate soln. 75A052

CH3C(CH3)C02 CH3 + OH- 12.8 contg. borate buffer; see 363.128. 363.139 [CH3CHCHCHCHC02 HK + h2o 5.0 x 104 s'

1 11.1 p.r. D.k. in sorbate soln.; extrapolated

to zero concn. of buffer. 76A113

364. Ammonium ion 364.128 [CH2 CHCONH2].- + nh4 + — 9.5 x 106 p.r. D.k. in soln. contg. acrylamide; 75A052

ch3Chconh2 + nh3 cor. to / = 0. 74A182

364.134 [CH2 CHC02 H].- + nh4 + -> 1.8 x 106 >7 p.r. Calcd. from effect of [NH4 +

] on 76A113

ch36hco2

- + nh4 +

d.k. in acrylate soln.; cor. to / = 0.

365. Ammonia

365.114 •chohconh2 + nh3 kf = 1.2 x 109 8.05, p.r. Calcd. from effect of [NH3] in 75A053

•CHO-CONH2 + nh4 +

8.25 buffer soln. on d.k. at 290 nm in N2 0-satd. glycolamide soln.; cor. to 7=0.

365.115 •chohco2

- + nh3 k, = 7.5 x 108 9.26, p.r. Calcd. from effect of [NH3 ] in 75A053

•CH0-C02

- + nh4 + 9.75 buffer soln. on d.k. at 270 nm in N20-satd. glycolate soln.; cor. to 7=0.

74
TABLE 3. Rate constants for acid- and base-catalyzed proton transfer reactions of aliphatic radicals in aqueous solution—Continued

No. Reaction k (L mop's"

1 ) pH Method Comment Ref.

365.116 •COH(CH3 )CONH2 + NH3 k( = 9.7 x 10® 8.05 p.r. Calcd. from effect of [NH3 ] in 75A053

•CO-(CH3 )CONH2 + nh4 +

buffer soln. on d.k. at 300 nm in N2 0-satd. lactamide soln.; cor. to 7=0.

365.134 [CH2 CHC02 HK + NH3 — (2.8 ± 1.0) x 106 >7 p.r. Calcd. from effect of [NH3 ] on 76A113 CH3CHC02

- + nh3 d.k. in acrylate soln.; cor. to 7 = 0.

366. Tetrahydroborate ion 366.114 •CHOHCONH2 + B(0H)4

- 9.1 x 10® 8.25 p.r. Calcd. from effect of borate on 75A053 •CHO-CONH2 + B(OH)3 + h2 o d.k. at 290 nm in N2 0-satd. soln. contg. glycolamide; cor. to / = 0. 366.115 •CHOHCOO' + B(0H)4

- 1.4 x 107 9.16, p.r. Calcd. from effect of borate on 75A053

•CHO-COO- + B(OH)3 + h2o 9.75 d.k. at 270 nm in N2 0-satd. soln. contg. glycolate; cor. to / = 0. 366.116 •COH(CH3 )CONH2 + B(0H)4

- — 3.1 x 10® 8.30 p.r. Calcd. from effect of borate on 75A053

•CO-(CH3)CONH2 + B(OH)3 + h2 o d.k. at 300 nm in N2 0-satd. soln. contg. lactamide; cor. to 7 = 0. 366.134 [CH2 CHC02 H]-- + B(OH)4

- -*• 2.3 x 10s >7 p.r. Calcd. from effect of borate on 76A113 CH3CHC02- + B(0H)4

- d.k. in acrylate soln.; cor. to 7 = 0.

367. Boric acid 367.128 [CH2 CHCONH2

].- + B(OH)3 + h2o -> 1.6 x 106 9.8 p.r. D.k. in soln. contg. acrylamide; 75A052 CH3 CHCONH2 + B(0H)4

- cor. to 7 = 0. 74A182

367.134 [CH2 CHC02 H] - + B(OH)3 -> 2.8 x 10s >7 p.r. Calcd. from effect of borate on 76A113 CH3 CHC02

- + B(OH)3 d.k. in acrylate soln.

368. Phosphate ion 368.114 •CHOHCONH2 + HPO/- k, = 1.8 x 109 8.3 p.r. Calcd. from effects of [HPO/"] 75A053 •choconh2 + h2 po4 on d.k. at 290 nm in N2 0-satd. glycolamide soln.; cor. to 7 = 0. 368.116 •COH(CH3 )CONH2 + HP04

2- — k, = 8.5 x 10® 6.2 p.r. Calcd. from effect of [HPO/"] 75A053

•CO-(CH3)CONH2 + H2 P04

- on d.k. at 300 nm in N20-satd.

lactamide soln.; cor. to 7 = 0. 368.128 [CH2 CHCONH2 ].- + H2 P04

- -> 3.8 x 106 p.r. D.k. in soln. contg. acrylamide; 75A052 CH3CHCONH2 + HPO/- cor. to 7 = 0. 74A182

[CH2 CHCONH2 ].- + HP04

2- -+ 8.6 x 104 p.r. D.k. in soln. contg. acrylamide; 75A052 CH3 CHCONH2 + P04

3- cor. to 7 = 0. 74A182

368.133 [(CH3)2NCONNCON(CH3)2K + (7 ± 1) x 107 6-9 p.r. Effect of [H2 P04

"] on 75A194 H2 P04

2- ^(CH3 ) 2 NCONHNCON(CH3)2 d.k. at 300 nm in soln. contg. + HPO/- 10"4 mol L"

1 Diamide and 0.2 mol L"1 tert-BuOH. 368.134 [CH2 CHCOOH].- + HPO/- — 7 x 103 >7 p.r. Calcd. from effect of [HPO/"] 76A113 CH3£HC02

-

-(- HPO/- on d.k. in acrylate soln.; cor.

to 7 = 0. [CH2 CHCOOH].- + H2 P04

- — 5.7 x 106 >7 p.r. Calcd. from effect of [H2 P04

"] 76A113 ch3Chco2 - + H2 P04

- on d.k. in acrylate soln.; cor.

to 7 = 0.

369. Pyrophosphate ion 369.114 •chohconh2 + HP2 07 3- -> 1.1 x 109 6.10, p.r. Calcd. from effect of [HP2 07 3

"] 75A053

•CHO CONH2 + H2 P20/- 6.40 on d.k. at 290 nm in N20-satd. glycolamide soln.; cor. to 7 = 0. 369.115 •CHOHCOO- + P2 07 4- — 5.8 x 106 9.26, p.r. Calcd. from effect of [P2 07 4-

] on 75A053

•CHO-COO- + HP2 07 3- 9.75 d.k. at 270 nm in N2 0-satd. glycolate

soln.; cor. to 7 = 0. 369.116 COH(CH3 )CONH2 + HP207

3- — 3.7 x 10® 8.1, p.r. Calcd. from effect of [HP207 3

‘] 75A053

•CO-(CH3)CONH2 + H2 P2 0/- 9.3 on d.k. at 300 nm in N2 0-satd.

soln. contg. lactamide; k =

8.5 x 10® for P20/-. 369.134 [CH2 CHCOOH].- + HP2073- — 9.1 x 104 >7 p.r. Calcd. from effect of [HP2 07

3

"] 76A113 CH3tHC02

- + HP207

3- on d.k. in acrylate soln.; cor.

to / = 0.

75
TABLE 3. Rate constants for acid- and base-catalyzed proton transfer reactions of aliphatic radicals in aqueous solution —Continued

No. Reaction k (L mol 's ') pH Method Comment Ref.

370. 370.128 Bicarbonate ion [CH2 CHCONH2K + HC03- CH3CHCONH2 + C032- 8.6 x 10s p.r. D.k. in soln. contg.

cor. to / = 0.

acrylamide; 75A052

74A182

371. 371.128 Trimethylammonium ion [CH2 CHCONH2 ].- + (CH3 )3 NH + CH3CHCONH2 + (CH3) 3 N

2.1 x 109 p.r. D.k. in soln. contg.

cor. to I — 0.

acrylamide; 75A052

74A182

372. 372.128 Ethylammonium ion [CH2 CHCONH2K + c2 h5 nh3 + ch3chconh2 + c2h5nh2

1.5 x 107 p.r. D.k. in soln. contg. acrylamide. 75A052

74A182

373. 373.128 Diethylammonium ion [CH2 CHCONH2 ]-- + (C2 H5 )2 NH2 + —

CH3 CHCONH2 + (C2 H5) 2 NH

7.2 x 107 p.r. D.k. in soln. contg. acrylamide. 75A052

74A182

374. 374.128 Triethylammonium ion [CH2CHCONH2 ]-- + (C2 H5)3 NH + -> CH3CHCONH2 + (C2 H5)3 N

1.3 x 108 10.3- p.r. 11.8

D.k. in soln. contg.

cor. to / = 0.

acrylamide; 75A052 74A182

375. 375.128 Cyclohexylammonium ion [CH2CHCONH2

]-- + c-C5 H n NH3 + CH3CHCONH2 + c-C6H n NH2

1.4 x 107 p.r. D.k. in soln. contg. acrylamide. 75A052

74A182

376. 376.128 Pyrrolidinium ion [CH2CHCONH2 ]-- + c-C4H8NH2 + CH3 CHCONH2 + c-C4H8 NH

2.0 x 108 p.r. D.k. in soln. contg. acrylamide. 75A052

74A182

377. 377.128 Piperidinium ion [CH2 CHCONH2K + c-C5H 10NH2 + -> CH3CHCONH2 + c-C5 H 10NH

6.3 x 107 p.r. D.k. in soln. contg. acrylamide. 75A052

74A182

378. 378.128 Glycine

[CH2 CHCONH2K + H3 N

+ CH2 C02 --> ch,chconh2 + H2NCH2 C02

- 2.5 x 107 p.r. D.k. in soln. contg. acrylamide. 75A052

74A182

76
TABLE 4. Rate constants for second order decay of selected aliphatic radicals in aqueous solution—Continued

No. Reaction k‘ (L moD's"1 ) pH Method Comment

.001 Methyl

•CH3 + -CH3 - C,H6 (1.24 ± 0.2) x 109 5.5 p.r. D.k. in soln. contg. 10"2 mol L'

1 CH4 and 0.25 mol L'

1 N2 0; € = 850 L mor'cm' 1 at 220 nm.

(1.6 ± 0.2) x 109 4.4 p.r. D.k. in soln. contg. 0.4 mol L"

1 CH4 (30 atm) and 2.5 x 10

-3 mol L"

1 N20;

€ = 1600 and 975 L mor’cm'1 at 213 and 220 nm., resp.; E, = 3.9 ± 0.4 kcal mol' 1 (16 kj mol'1 ).

.002 Ethyl

•ch2 ch3 + ch2ch3 (9.6 ± 2) x 108 5.5 p.r. D.k. in soln. contg. 10'2 mol L'

1 ethane and 0.25 mol L"

1 N20; e =

520 and 330 L moC'cm"1 at 220 and 250 nm, resp. (1.2 ± 0.2) x 109 4.4 p.r. D.k. in soln. contg. 5 x 10"2 mol

L'

1 ethane (30 atm) and 2.5 x 10'3 mol L'

1 N2 0; e = 790, 750, 700, 545

and 375 L mol'W1 at 210, 215, 220, 230

and 250 nm, resp.; E, = 3.9 ± 0.4

kcal mol' 1 (16 kj mol' 1 ).

.004 Cyclopentyl

c-tjH, + c-C5 H9 —

(1.0 ± 0.2) x 109 7 p.r. D.k. in soln. contg. N2 0 and 1.3 x

18 an^ 10"5 mol L'

1 cyclopentane; € = 480

^5^10 C5 H8 L mor'cm"1 at 248 nm.

.016 2-Hydroxy-2,2-dimethylethyl

•CH2 C(CH3)2 OH + -CH2C(CH3)2OH 7 x 108 6 p.r. D.k. in N2 0-satd. soln. contg. 6 x 108 13.5 tert-BuOH; € = 900, 200 and 30 L mol"1 cm"1 at 225, 250 and 280 nm, resp. 2k/e = 1.3 x 107 and 1.1 x 107 at pH 6 and 13.5, resp.

.020 Formylmethyl

•ch2 cho + -ch2cho 4.5 x 108 10 p.r. D.k. in N2 0-satd. soln. contg. 0.1 mol L'

1 ethylene glycol; € = 260

L mor’cm"1 at 300 nm.

4.5 x 108 9.8 p.r. D.k. in N2 0-satd. soln. contg. 10

-3 mol L"

1 acetylene; 2k/e = 3.4 x 106 cm s'*.

.021 2-Hydroxyethenyl

•CH = CHOH + •CH = CHOH — 3.2 x 109 <7 p.r. P.b.k. in N2 0-satd. soln. contg. HOCH = CHCH = CHOH 10"3 mol L'

1 acetylene at 240 nm

(e = 8.1 x 103 L moC'cm" 1 ); 2k/e =

2.0 x 10s cm s'

1

; prod, rearranges to succinaldehyde.

.035 Carboxymethyl

•ch2 co2

- + ch2 co2 - (5.5 ± 1) x 108 6.5 p.r. D.k. at 366 nm in N2 0-satd. soln. contg. Na acetate; € = 780 L mol' 1 cm'1

. 5 x 108 10 p.r. D.k. in N2 0-satd. soln. contg.

acetate ion; € = 800 L mol" 1 cm'1

at 350 nm. •ch2 co2 h + ch2 co2 h 9 x 108 3 p.r. D.k. in N2 0-satd. soln. contg.

acetic acid; € = 650 L mol" 1 cm' 1

at 320 nm; pK, = 4.5.

.048 Trichlorome thy 1 •CC13 + CC13 -* CjClf, (3.7 ± 0.9) x 108 5.5- p.r. D.k. at 230 nm in 10*4 mol L"

1 CC14 12.4 soln.; € = 2300 ± 450 L mol' 1 cm" 1 .

Ref.

72G445

75A055

72G445

75A055

74A051

69G419

73G004

78A007

78A007

76A082

69G446

69G446

74A043

77
Table 4. Rate constants for second order decay of selected aliphatic radicals in aqueous solution—Continued

No. Reaction k‘ (L molds'1 ) pH Method Comment Ref.

.075 Hydroxymethyl

•ch2 oh + -ch2 oh 1.2 x 109 6 p.r. D.k. at 280 and 350 nm, resp., at pH 69G419

•CH2 0- 4

- -CH2 0- 4.5 x 108 12 6 and 12 in N2 0-satd. soln. contg. MeOH; 2k/e = 6.2 x 106 and 1.5 x 106

at pH 6 and 12, resp. (e = 390 and 600); pKa = 10.7 [66G074], •ch2oh + -ch2 oh (1.5 ± 1) x 109 p.r. D.k. in N20-satd. soln. contg. MeOH; e — 270 ± 15 L mol

" 1 cm" 1 77A011

at 310 nm.

.076 1-Hydroxyethyl

CH3 CHOH + CH3 CHOH (5.5 ± 1.5) x 108 ~7 p.r. D.k. at 289.4 nm in deaerated soln. 62G140

-> CH3 CHOHCHOHCH3 (I) kx = (4.4 ± 1) contg. EtOH; e = 260 ± 65 L mol

" 1 x 108 cm"1

; relative disproportionation and CH3CHO + CH3CH2OH (II) kn = (1.1 ± 0.3) combination est. from product yields. x 108

(7 ± 2) x 108 ~1 p.r. D.k. at 296.7 nm in deaerated

soln. contg. EtOH and 0.8 N H2S04; € = 240 ± 45 L mol

" 1 cm"1

.

63G045

(1.2 ± 0.3) x 109 6 p.r. D.k. at 280 and 300 nm, resp., at pH

6 and 13 in N20-satd. soln. contg. 69G419

CH3 CHO- + CH3 CHCT (2.5 ± 0.5) x 108 13 EtOH; p

A

a - 11.6 [66G074]; 2k/

e

= 4.7 X 106 and 5.7 x 106

resp., at pH 6 and 13.

.078 1-Hydroxy-l-methylethyl

(CH3)2COH + (CH3)2tOH (7 ± 1.5) x 108 6 p.r. D.k. at 280 and 300 nm, resp. at pH 69G419

(CH3)2CO- + (CH3 )2CO- (2 ± 0.4) x 108 13.3 6 and 13.3 in N2 0-satd. soln. contg. 2-PrOH; 2k/e = 2.1 x 106 and 2.7 x 10s

at pH 6 and 13.3, resp.; pKt — 12.2 [66G074].

(6.5 ± 0.5) x 108 p.r. D.k. at 310 nm in N2 0-satd. soln. contg. 0.02 mol L

" 1 2-PrOH; € = 353 ±

15 L mol

" 1 cm"

1

.

77A011

.101 1 ,2-Dihydroxyethyl

•chohch2 oh + -chohch2 oh 3.4 x 108 6.0 p.r. D.k. at 250 nm in N20-satd. soln. contg. ethylene glycol; 2k/e = 1.1 x 106 (e = 610 L mol

’ 1 cm'1 ).

73G004

.113 Ascorbate radical

•A' + -A' (+ H

+

) — (1.9 ± 0.2) x 10s 8.7 p.r. D.k. at 360 nm in N20-satd. soln. 75A240 A + HA' contg. ascorbate; € = 3300 L mol

" 1 cm

' 1 [77A036]; PAa = -0.45 [72D181],

.115 (Carboxy)hydroxymethyl

•chohco2h + -chohco2 h (6.5 ± 1) x 108 1 p.r. D.k. in N2 0-satd. soln. contg. 69G447

•chohco2- + -CH0HC02- (4.3 ± 0.7) x 108 7.2 0.05 mol L

" 1 glycolic acid (e 6000 L mol-'cm-1 •CH0-C02 ); pAa = 4.6, 8. 8. - + -CH0-C02

- (7.5 ± 1) x 106 12

.123 Dihydroxymethyl

•CH(OH) 2 + -CH(OH) 2 3.6 x 108 6.3 p.r. D.k. at 250 nm, as well as condy. 71G424

CH2(OH) 2 + HC02- + H

+

2.3 x 108 12 change, in N2 0-satd. soln. contg. formaldehyde, as well as in soln. contg. rert-BuOH and CO; € s 850 and 1500 L mol

" 1 cm

" 1 at pH 6 and 11.8,

resp.; pKa = 9.5.

78
Table 4. Rate constants for second order decay of selected aliphatic radicals in aqueous solution—Continued

No. Reaction k‘ (L mol 's ') pH Method Comment Ref.

.147 Carboxyl

•CO2 “I- -C02 — C20^ 5 x 108 5 p.r. D.k. at 250 nm in C02 -satd. soln. contg. 10~2 mol L"

1 formate; e = 2250

L mol” 1 cm

-1

; k cor. to / = 0.

65G384

7.5 x 108 3.1,9 p.r. D.k. at 255 nm in N20-satd. 69G446

8.5 x 108 13 soln. contg. formate, as well as in C02 -satd. soln. contg. formate;

€max = 3000 L mol

-1 cm" 1 at 235 nm.

(4.5 ± 0.15) x 108 2.8-7 p.r. D.k. in CO-satd. soln. at 260 nm

(€ = 2200 L mol" 1 cm'1 ) as well as condy. change; same result in N2 0-satd. formate soln.

70G303

(3.8 ± 0.35) x 108 2.7- p.r. D.k. at 250 nm in N2 0-satd. 0.1 mol 73G085

13 L"

1 formate soln.; € = 2050 L mol" 1

(8.5 ± 1) x 108 0 cm"1 (1100 at pH 0); k cor.

to / = 0; p/Ta(.C02 H) = 1.4.

* k is defined by the expression -d[R]/dt = 2£[R]2

.

79
Index to Radical Reactions

Radicals are listed in number order. Following the name of

the radical are the entry numbers for the substrates for which reactions of that radical are included in tables 1-3. For example, the first reaction in the tables for methyl

radical is under entry 9 and the reaction is numbered

9.001.

001 Methyl 9, 10, 20, 59, 69, 80, 81a, 83, 93, 94, 115, 116, 117, 147,

149, 156, 160, 200, 201, 202, 217, 219, 221a, 222, 223,

230, 241, 242, 243, 248, 254, 255, 267, 305, 314, 315,

316, 317, 345, 346.

002 Ethyl 69, 81a, 83, 93.

002a 1-Methylethyl 69, 81a.

002b 1,1-Dimethylethyl 69, 81a.

003 Radicals from pentane 94.

004 Cyclopentyl 88, 93, 94, 342, 343, 345, 346.

005 2-Chloroethyl 81a.

006 2-Carboxy-2,2-dimethylethyl 55, 71, 104.

007 Radicals from oleate + OH 93.

008 Radicals from linoleate + OH 93.

009 Radicals from linolenate + OH 93.

010 Radicals from arachidonate + OH 93.

011 2-Aminoethyl 262.

012 2-Amino-2,2-dimethylethyl 71, 104.

013 2-Amino-2-carboxy-2-methylethyl 71, 104.

014 2-Hydroxyethyl 57, 58, 59, 69, 81a, 93, 200, 202, 253, 345, 346.

015 2-Hydroxypropyl 314.

016 2-Hydroxy-2,2-dimethylethyl 1, 2, 4, 5, 6, 9, 10, 10a, 11, 55, 57,

58, 59, 71, 72, 77, 81a, 83, 88, 89, 99, 104, 105, 106, 113,

114, 123, 161, 163, 197, 206, 227, 236, 237, 238, 239,

253, 262, 302, 342, 343, 345, 346.

016a Radicals from cyclopentene + OH 94.

017 2-Carboxy-2-hydroxy-2-methylethyl 71, 104.

018 Radicals from allyl alcohol + OH 161, 278, 279, 283.

019 Radicals from crotyl alcohol + OH 278, 279, 283.

020 Formylmethyl 9, 55, 81a, 128, 135, 176, 177, 207, 227, 258, 266,

309, 310, 311, 344.

021 1-Formylethyl 227.

022 2-Hydroxyethenyl 119, 362.

023 2-Oxopropyl 227.

024 1-Acetylethyl 227.

025 2-Oxocyclohexyl 227.

026 l-Formyl-2-hydroxyethyl 227.

027 4-Hydroxy-2-oxobutyl 227,

028 l-Formyl-4-hydroxybutyl 227.

029 l-Formyl-5-hydroxypentyl 227.

030 Radicals from meso-erythritol 227.

031 Radicals from xylitol 227.

032 2-Oxo-3,4,5-trihydroxycyclohexyl 227.

033 Radicals from sorbitol 161, 227.

034 Carbamoylmethyl 262.

035 Carboxymethyl 9, 12, 55, 59, 81a, 93, 100, 101, 102, 110.

036 Methoxycarbonylmethyl 93.

037 1-Carboxyethyl 55, 59, 278.

038 1-Carboxypropyl 278.

039 l-Carboxy-2-hydroxyethyl 278.

040 l-Carboxy-2-hydroxypropyl 278.

040a 1,2-Dicarboxyethyl 81a.

041 l,2-Dicarboxy-2-hydroxyethyl 59, 278.

042 Dicarboxymethyl 12, 55, 100, 110, 135, 228, 278.

043 Chloromethyl 69, 81a, 83, 223.

044 Difluoromethyl

045 Dichloromethyl 69, 83, 335.

046 Dichlorofluoromethyl 202.

047 Trifluoromethyl 130, 147, 149, 200, 202, 212, 214, 255, 292, 313,

314, 317.

048 Trichloromethyl 59, 81a, 83, 205, 223, 312, 314, 340, 358.

049 1-Aminoethyl 262.

050 1-Amino-l-methylethyl 222, 262.

051 l-(jV,./V-Diethylamino)ethyl 262.

052 Triethylammonioethyl 93.

053 (TV-Acetylamino)methyl 206, 262.

054 (yV-Formyl-yV-methylamino)methyl 12, 55, 100.

055 (TV-Acetyl-A-methylaminoimethyl 71, 104, 262.

80
056 Amino(carboxv)methyl 12, 69, 100, 133, 134, 138, 159, 1<3, 228,

231, 232, 260. 262, 274, 276, 308, 333, 336, 350.

057 Amino(carbamoyl)methyl 93, 262.

058 Radicals from glycylglycinamide 4- OH 262.

059 CarboxylA^-methylaminolmethyl 262.

060 7V-Acetylamino(carboxy)methyl 362.

061 A^-AcetylWV-methylaminolcarboxylmethyl 262.

062 Radical from glycine anhydride + OH 93, 138, 162, 163, 262,

273, 362.

063 Radical from alanine anhydride + OH 93, 262, 362.

064 Radical from sarcosine anhydride + OH 93.

065 Radicals from diglycine + OH 262.

066 Radicals from glycylsarcosine + OH 262.

067 Radicals from acetyldiglycine + OH 93, 262.

068 Radicals from triglycine 4- OH 133, 134, 138, 262, 274.

069 Radicals from acetyltriglvcine + OH 262.

070 Radicals from acetyltrialanine + OH 262.

071 Radicals from acetyltrisarcosine + OH 262.

072 Radicals from acetylserineamide 4- OH 262.

073 Radicals from acetylasparagine + OH 262.

074 Radical from 2-pvrrolidone-5-carboxylic acid 362.

075 Hydroxymethyl 1, 2, 4, 5, 6, 9, 10a, 12, 13, 15, 16, 17, 36, 37, 38,

39, 40, 41, 42, 43, 44, 45, 45a, 55, 57, 59, 60, 68, 69, 70,

73, 77, 81a, 88, 89, 92, 94, 95, 97, 98, 98a, 99, 99a, 100,

102, 106, 110, 111a, 113, 114, 121, 123, 135, 136, 137,

138, 143, 148, 152, 154, 161, 162, 163, 173, 183, 185a,

197, 204, 206, 211, 214, 220, 226, 231, 232, 233, 236,

239, 253, 260, 262, 268, 270, 271, 276, 278, 279, 283,

293, 297, 304, 306, 308, 318, 319, 323, 342, 343, 345,

346, 347, 350, 361.

076 1-Hydroxyethyl 2, 3, 4, 5, 9, 12, 15, 16, 36, 37, 38, 39, 40, 41,

42, 43, 45, 45a, 55, 59, 60, 68, 69, 73, 76, 77, 81, 81a, 86,

87, 88, 93, 94, 95, 98a, 99, 99a, 100, 102, 106, 111, 111a,

118, 123, 137, 138, 148, 154, 161, 163, 164, 165, 185a,

199, 209, 220, 224, 226, 249, 253, 262, 268, 269, 270,

271, 278, 279, 283, 297, 306, 319, 323, 331, 338, 339,

342, 343, 345, 346, 347, 362.

077 1-Hydroxypropyl 69, 93, 106, 148, 278, 279, 283, 297, 347.

078 1-Hydroxy-l-methylethyl 1, 2, 4, 5, 6, 7, 8, 9, 10, 10a, 12, 15,

16, 24, 25, 26, 27, 28, 29, 31, 33, 34, 35, 36, 37, 38, 39,

40, 41, 42, 43, 44. 45, 45a, 46, 47. 48, 49, 50, 51, 52, 55, 57, 59, 60, 67, 68, 69, 70, 73, 74, 75, 76, 77, 79, 81a, 83,

84, 85, 87, 88, 89, 93, 94, 95, 96, 97, 98, 98a, 99, 99a,

100, 102, 103, 106, 111, 111a, 113, 114, 118, 120, 121, 123, 124, 127, 129, 131, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 145, 146, 148, 151, 152, 153,

154, 155, 156a, 157, 159, 161, 163, 170, 171, 173, 174,

178, 180, 181, 182, 184, 185, 185a, 186, 187, 188, 189,

190, 191, 192, 193, 197, 198, 206, 210, 215, 216, 220,

221, 221a, 222, 223, 225, 228, 229, 231, 232, 233, 234,

235, 238a, 244, 245, 249, 250, 252, 253, 257, 259, 260,

261, 262, 263, 264, 265, 268, 269, 270, 271, 272, 273,

275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285,

286, 288, 289, 290, 291, 293, 294, 295, 296, 297, 298, 299, 300, 301, 302, 303, 306, 307, 308, 319, 320, 321,

322, 323, 324, 325, 326, 327, 329, 329, 331, 333, 334,

336, 337, 342, 343, 345, 346, 347, 348, 349, 350, 351,

352, 353, 356, 357, 359, 360, 361, 362.

079 1-Hydroxybutyl 58a, 65a, 161, 262, 278, 279, 283, 297.

080 1-Hydroxy-l-methylpropyl 60, 93, 148.

081 l-Hydroxy-2-methylpropyl 69, 93, 161, 283, 297.

082 1-Hydroxypentyl 69.

083 (Cyclohexyl)hydroxymethyl 148.

084 1-Hydroxycyclobutyl 69, 283.

085 1-Hydroxycyclopentyl 69, 283.

086 1-Hydroxycyclohexyl 69, 283.

087 1-Hydroxycycloheptyl 69, 283.

088 1-Hydroxycyclooctyl 69, 283.

089 2,2,2-Trifluoro-l-hydroxyethyl 9.

090 Acetoxymethyl 93.

091 1-SuIfatoethyl 69.

092 Radicals from sodium dodecylsulfate 138.

092a Methoxymethyl 69, 81a, 347.

093 1-Ethoxyethyl 12, 15, 16, 37, 38, 39, 39, 40, 42, 55, 81a, 94, 100,

101, 102, 152, 283, 347.

093a 1,1-Dimethylethoxymethyl 347.

094 2-Tetrahydrofuryl 94, 152.

094a (Methoxymethoxy)methyl 347.

095 1,4— Dihydroxybutyl 161.

096 l,3-Dihydroxy-2,2-di(hydroxymethyl)propyl 95, 163, 225.

097 2-Carboxy-l-hydroxy-l-methylethyl 69, 83, 131, 133, 134, 181, 228, 262.

098 2-Amino-l-hydroxyethyl 9.

099 2-Amino-l-phosphoryloxyethyl 278.

100 2-Amino-2-carboxy-l-hydroxyethyl 60, 93.

101 1 ,2-Dihydroxyethyl 5, 9, 10, 29, 55, 69, 93, 347, 362.

102 1,2-Dihydroxypropyl 347.

103 1,2-Dihydroxy-l-methylpropyl 347.

81
104 2,5-Dioxacyclohexyl 12, 15, 16, 42, 55, 81a, 83, 94, 100, 101,

102, 283.

105 Radicals from polyethyleneglycol 4, 5, 69, 93.

106 1,2,3-Trihydroxypropyl 5, 69, 93, 163, 225, 278, 347.

107 l-Hydroxy-l-methyl-2-oxopropyl 12, 100.

108 Radicals from deoxyribose + OH 69, 93, 138, 262, 278, 279, 342.

109 Radicals from ribose + OH 206, 227, 262, 278.

110 Radicals from ribose phosphate + OH 262, 278.

111 Radicals from glucose + OH 69, 93, 158, 161, 194, 195, 227,

279, 287, 342, 343, 345, 346, 347, 355.

112 Radicals from sucrose + OH 347.

113 Radical from ascorbate + OH 59, 93, 163, 179, 214, 246, 247,

255, 262, 330.

1 14 (Carbamoyl)hydroxymethyl 262, 362, 365, 366, 368, 369.

115 (Carboxy)hydroxymethyl 55, 69, 81a, 93, 133, 138, 228, 262, 274,

333, 362, 365, 366, 368, 369.

116 1 -Carbamoyl- 1-hydroxyethyl 138, 362, 365, 366, 368, 369.

117 1-Carboxy-l-hydroxyethyl 12, 55, 69, 93, 100, 134, 138, 148,

163, 225, 262, 278, 283.

118 l-Hydroxy-l-(methoxycarbonyl)ethyl 262.

119 (Dicarboxy)hydroxymethyl 262.

120 1,2-Dicarboxy- 1-hydroxyethyl 163, 262, 278.

121 l,2-Dicarboxy-l,2-dihydroxyethyl 163, 165, 225, 262, 270.

122 1,3-Dicarboxy-l-hydroxypropyl 262.

123 Dihydroxymethyl 93, 283.

124 Dimethoxymethyl 94, 347.

125 2,5-Dioxacyclopentyl 94.

126 2,2,2-Trichloro-l,l-dihydroxyethyl 93.

127 Carbamoyl 12, 55, 100.

128 Electron adduct of acrylamide 1, 123, 363, 364, 367, 368, 370, 371, 373, 374, 375, 376, 377, 378.

129 Electron adduct of crotonamide 363.

130 Electron adduct of methacrylamide 363.

131 Electron adduct of /3,/3-dimethylacrylamide 363.

132 Electron adduct of iV,/V-dimethylacrylamide 363.

133 Electron adduct of Diamide 368.

134 Electron adduct of acrylate 362, 364, 365, 366, 367, 368, 369.

135 Electron adduct of crotonate 362, 363.

136 Electron adduct of methacrylate 362, 363.

137 Electron adduct of /3,/3-dimethylacrylate 362, 363.

138 Electron adduct of methyl methacrylate 363.

139 Electron adduct of sorbate 362, 363.

141 Electron adduct of dimethyl fumarate 93, 206.

142 Electron adduct of glycine anhydride 118, 137, 160a, 162, 163, 215a, 216, 253a, 262.

143 Electron adduct of alanine anhydride 118, 137, 160a, 162, 262.

144 Electron adduct of sarcosine anhydride 118, 137, 162, 262.

146 Electron adduct of acetylglycylglycinamide 262.

147 Carboxyl 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 31, 32, 44, 46, 49, 50, 53, 54,

55, 56, 59, 60, 61, 62, 63, 64, 65, 66, 69, 70, 74, 76, 78, 81a, 82, 88, 89, 90, 91, 92, 93, 94, 98, 99, 100, 103, 107, 108, 109, 110, 111, 112, 113, 114, 118, 121, 122, 123,

125, 126, 132, 133, 134, 138, 143, 144, 146, 150, 151,

152, 158, 159, 163, 164, 165, 167, 168, 169, 170, 171, 172, 173, 175, 183, 184, 185a, 190, 191, 192, 193, 195, 196, 199, 203, 206, 208, 209, 213, 214, 216, 218, 220,

225, 228, 231, 233, 233a, 240, 249, 251, 252, 256, 260,

262, 270, 271, 276, 278, 279, 283, 284, 285, 286, 287a, 297, 319, 320, 321, 323, 324, 329, 332, 333, 341, 342, 347, 354, 356.

148 Electron adduct of methyl acetate 361.

82
Radical Formula Index

The radical numbers following the name are contained in the List of Aliphatic Radicals preceding table 1 and in the Index to Radicals just preceding this index.

CC12 F

CC13 CF3 chci2 chf2 ch2 ci ch2no

ch3 ch3 o ch3 o2 C02

- C2H2 C13 02 C,H2F3 0

CAO

c,h3o2 c2h3o3 CAC1 CANO

C2H4N02 c2 h4o4s- ca

C2H5n2o

CjHjO

QHjO,

C2H6N CANO

C2 H: N04P c3 h3 o4 c3 h3 o3 c3 h402- c3 h5 no- c3 h5 0

c3 h5o2

C3H 3 o3

C3H.N0

C3 H.N0, QH.NO,

CjH.O,' c3 h7 C3 Ht 0

c3 h7 o2

c3 h7 o2 c( h7 o,

Dichlorofluoromethyl, 046

Trichloromethyl, 048

Trifluoromethyl, 047

Dichloromethyl, 045

Difluoromethyl, 044

Chloromethyl, 043

Carbamoyl, 127

Methyl, 001

Hydroxymethyl, 075

Dihydroxymethyl, 123

Carboxyl, 147

2.2.2-

Trichloro-l,l-dihydroxyethyl, 126

2.2.2-

Trifluoro-l-hydroxyethyl, 089

Formylmethyl, 020

2-Hydroxyethenyl, 022

Carboxymethyl, 035

(Carboxy)hydroxymethyl, 115

2-Chloroethyl, 005

Carbamoylmethyl, 034

Amino(carboxy)methyl, 056

(Carbamoyl)hydroxymethyl, 114

1-Sulfatoethvl, 091

Ethyl, 002

Amino(carbamoyl)methyl, 057

1-

Hydroxyethyl, 076

2-

Hydroxyethyl, 014

Methoxvmethyl, 092a

1.2-

Dihydroxvethyl, 101

1-

Aminoethyl, 049

2-

Aminoethyl, 011

2-Amino-l-hydroxyethyl, 098

2-Amino-l-phosphoryloxyethyl, 099

Dicarboxymethyl, 042

(Dicarboxy)hydroxymethyl, 119

Electron adduct of acrylate, 134

Electron adduct of acrylamide, 128

1-

Formylethyl, 021

2-

Oxopropyl, 023

Radicals from allvl alcohol + OH, 018

Acetoxymethyl, 090

1-Carboxyethyl, 037

2,5-Dioxacyclopentyl, 125

l-Formyl-2-hydroxyethyl, 026

Methoxycarbonylmethyl, 036

1-Carboxy- 1-hydroxyethyl, 117

l-Carboxy-2-hydroxyethyl, 039

(jV-Acetylamino)methyl, 053

(jV-Formyl-./V-methylamino)methyl, 054

1-

Carbamoyl-l-hydroxyethyl, 116

Carboxy(jV-methylamino)methyl, 059

2-

Amino-2-carboxy- 1-hydroxyethyl, 100

Electron adduct of methyl acetate, 148

1-Methylethyl, 002a

1-Hydroxy-l-methylethyl, 078

1-

Hydroxypropyl, 077

2-

Hydroxypropyl, 015

1.2-

Dihydroxypropyl, 102

Dimethoxymethyl, 124

(Methoxymethoxy)methyl. 094a

Radicals from allyl alcohol + OH. 018

1,2,3-Trihydroxypropyl, 106

C,H8 N

c4h4o4

- c4hs n2 o2 C4Hs04 c4 h5o3 c4h50. c4h.no3 c4h.02

-

c4h: noc4h7 n2 o2

-

c4h7 n2 o3 c4h7o

c4h7 o2

c4h7 o3

c4h8 no

c4h8no2 c4h9 c4h9o

C4H902

C4H902 c4h10n

c3 h7 no3 QH7 o4 csh7 o5 C5 HbN03 CsH802

CsH, CANO'

CjH^jOj c5 h9o

C3 H902

cao4 QH9o8 p Cs H m C5 H,|N2 03 CsH.,0

QH,,o4 QH.O.-

c.h8o2

-

1-Amino-l-methylethyl, 050

Electron adduct of maleate, 140

Radical from glycine anhydride + OH, 062

1.2-

Dicarboxyethyl, 040a

1.2-

Dicarboxy-l-hydroxyethyl,120

1.2-

Dicarboxy-2-hydroxyethyl, 041

1.2-

Dicarboxy-l,2-dihydroxyethyl, 121

jV-Acetylaminolcarboxylmethyl, 060

Electron adduct of crotonate, 135

Electron adduct of methacrylate, 136

Electron adduct of crotonamide, 129

Electron adduct of methacrylamide, 130

Electron adduct of glycine anhydride, 142

Radicals from glycylglycinamide + OH, 058

Radicals from diglycine + OH, 065

1-Acetylethyl, 024

1-

Hydroxycyclobutyl, 084

Radicals from crotyl alcohol + OH, 019

2-

Tetrahydrofuryl, 094

1-Carboxypropyl, 038

2,5-Dioxacyclohexyl, 104

1-

Hydroxy-l-methyl-2-oxopropyl, 107 4—Hydroxy-2-oxobutyl, 027

2-

Carboxy-l-hydroxy-l-methylethyl, 097

2-Carboxy-2-hydroxy-2-methylethyl, 017

l-Carboxy-2-hydroxypropyl, 040

1-

Hydroxy-l-(methoxycarbonyl)ethyl, 1 18

Radicals from meso-erythritoL, 030

(Ar-Acetyl-Ar-methylamino)methyl, 055

2-

Amino-2-carboxy-2-methylethyl, 013

1.1-

Dimethylethyl, 002b

1-Ethoxyethyl, 093

1-

Hydroxybutyl, 079

2-

Hydroxy-2,2-dimethylethyl, 016

1-Hydroxy-l-methylpropyl, 080

1-

Hydroxy-2-methylpropyl, 081

1,4-Dihydroxybutyl, 095

1.2-

Dihydroxy-l-methylpropyl, 103

Radicals from crotyl alcohol + OH, 019

2-

Amino-2,2-dimethylethyl, 012

Radical from 2-pyrrolidone-5-

carboxylic acid, 074

2-Oxocyclopentyl, 032

1.3-

Dicarboxy-l-hydroxypropyl, 122

A^-Acetyl-jV-methylaminofcarboxylmethyl, 061

Electron adduct of /3,/J-dimethylacrylate, 137

Electron adduct of methyl methacrylate, 138

Cyclopentyl, 004

Electron adduct of A^-dimethylacrylamide, 132

Electron adduct of /3,^3-dimethylacrylamide, 131

Radicals from acetylserineamide, 072

1-

Hydroxycyclopentyl, 085

Radicals from cyclopentene + OH, 016a

2-

Carboxy-2,2-dimethylethyl, 006

1 -Formyl-4—hydroxybutyl, 028

Radicals from ribose + OH, 109

Radicals from deoxyribose + OH, 108

Radicals from xylitol, 031

Radicals from ribose phosphate 4- OH, 110

Radicals from pentane, 003

Radicals from glycylsarcosine + OH, 066

1,1-Dimethylethoxymethyl, 093a

1-Hydroxypentyl, 082

1

.3-

Dihydroxy-2,2-di(hydroxy methyljpropy 1, 096

Radical from ascorbate + OH, 113

Electron adduct of sorbate, 139

83
c6h8 o4

- Electron adduct of dimethyl fumarate, 141 C6HI4N l-lA^^-Diethylaminolethyl, 051 C6H9N2 02 Radical from alanine anhydride + OH, 063 c7 h13o (Cyclohexyl)hydroxymethyl, 083

Radical from sarcosine anhydride + OH, 064 1 -Hydroxycycloheptyl, 087 c6h9n2o4 Radicals from acetyldiglycine + OH, 067 C8 H12N305 Radicals from acetyltriglycine + OH, 069 Q,h9o 2-Oxocyclohexyl, 025 Electron adduct of acetyltriglycine, 145

Q>Hi0N2O4 Radicals from acetylasparagine + OH, 073 c8h15o 1 -Hydroxycyclooctyl, 088 QHi0N3O4 Radicals from triglycine -)- OH, 068 c8h19n

+ Triethylammonioethyl, 052 c6hu n202 Electron adduct of alanine anhydride, 143 QiHi8N305 Radicals from acetyltrialanine + OH, 070

Electron adduct of sarcosine anhydride, 144 Radicals from acetyltrisarcosine + OH, 071 C6Hh O 1-Hydroxycyclohexyl, 086 Ci 2 H2 i0 12 Radicals from sucrose + OH, 112 QH1

1

^2 l-Formyl-5-hydroxypentyl, 029 c12 h2404s- Radicals from sodium dodecylsulfate, 092 QHU 05 Radicals from sorbitol, 033 ^18H2802 Radicals from linolenate + OH, 009 c6Hu o6 Radicals from glucose + OH, 111 ^18^3o02 Radicals from linoleate + OH, 008 c6h12 n2 03

- Electron adduct of acetylglycylglycinamide, 146 ^18^32^2 Radicals from oleate + OH, 007

^y^l2N402 Electron adduct of Diamide, 133 ^20^30^2 Radicals from arachidonate + OH, 010

84
Substrate Formula Index

Substrates for radical reactions are indexed by molecular C( Ht N02 S Cysteine, 162 formula. Entry numbers for the reactions in tables 1-3 are c,h8o 1-Propanol, 313

listed following the name.

c3 h I 0n

+ c4h2 n2 o4 C4H3 BrN202

2-Propanol, 314

Trimethylammonium ion, 371

Alloxan, 126

5-Bromouracil, 146 Ag +

Silver(I) ion, 1 c4h3 no2s 2-Nitrothiophene, 298 Ag2 +

Silver(I) ion, complex with Ag(0), 2

3-Nitrothiophene, 299 BH3 O3 Boric acid, 367 c4h3 n3 o4 5-Nitrouracil, 301 BH404

- Tetrahydroborate ion, 366 c4h3o4

- Fumarate ion, 214 BrCoH 15 N52+ Pentaamminebromocobalt(III) ion, 15 c4h4n2 Pyrazine, 321 BrH 15 N5 Ru2+ Bromopentaammineruthenium(III) ion, 101 Pyridazine, 324 Br03‘ Bromate ion, 3 Pyrimidine, 329

Br2 Hg Mercuric bromide, 74 c4h4n2 o2 2-Nitropyrrole, 295

CC14 Carbon tetrachloride, 152 3-Nitropyrrole, 296

CHClj Chloroform, 157 c4h4o4 Fumaric acid, 215 CH02

- Formate ion, 212 Maleic acid, 252 cho3

- Bicarbonate ion, 370 c4h5 n3 4-Aminopyrimidine, 129 CH2 C12 Dichloromethane, 174 c4h5 n3 o2 2-Methyl-5-nitroimidazole, 264 ch2 o Formaldehyde, 211 c4h6 Butadiene, 147 ch3no2 Nitromethane, 292 c4h6n2 o2 Glycine anhydride, 218 ch4o Methanol, 255 c4h6o2 2,3-Butanedione, 148 ch4s Methanethiol, 254 c4h7 n Isobutyronitrile, 243 CHgN Mercurous cyanide, 77 c4h8 1-Butene, 149 cn4o8 Tetranitromethane, 347 Isobutylene, 241 C2 C13 02

~ Trichloroacetate ion, 351 c4h8o Tetrahydrofuran, 340 c2 f3 02 Trifluoroacetate ion, 352 c4h8 02 Ethyl acetate, 201 c2 h2 Acetylene, 119 Isobutyric acid, 242 QH.IN Iodoacetonitrile, 237 Methyl propionate, 267 C2 H2 I02

" Iodoacetate ion, 235 c4h10 n

+

Pyrrolidinium ion, 376 C2 H3 C102 Chloroacetic acid, 156 c4h10o Ethyl ether, 205

C2H3C1302 Chloral hydrate, 155 c4h 10o2 s2 Dithiothreitol, 197 C2 H3 I02 Iodoacetic acid, 236 c4h 12 n

+ Diethylammonium ion, 373 c2 h3 n Acetonitrile, 117 C4Hi 2 N2S2 Cystamine, 160a C2 H4 Ethylene, 202 C4H16BrCoFN4 +

cis-Bromobis(ethylenediamine)

C^Cu* Copper(I) ion, complex with ethylene, 58 fluorocobalt(III) ion, 40 c2h4ino Iodoacetamide, 234 C4H16Br2 CoN4 +

tranj-Dibromobis(ethylenediamine) c2 h4o2 Acetic acid, 115 cobalt(III) ion, 39 c2 h4o3 Glycolic acid, 219 C4H16C12 CoN4 +

ct5-Dichlorobis(ethylenediamine) c2 h5 io Iodoethanol, 238 cobalt(III) ion, 41 c2 h5 no2 Glycine, 217, 378 <ra/w-Dichlorobis(ethylenediamine) QH.O Ethanol, 200 cobalt(III) ion, 42 QHeOS 2-Mercaptoethanol, 253 C4H16Cl2N4Pt2+ trares-Dichlorobis(ethylenediamine)- c2 h602 Ethylene glycol, 204 platinum(IV) ion, 97 c2 h7 ns Cysteamine, 161 C4H16CoF2 N4 +

rra/w-Bis(ethylenediamine) c2 h8n

+ Ethylammonium ion, 372 difluorocobalt(III) ion, 43 C2 H 19 CoN5 02 +

(Acetato)pentaamminecobalt(III) ion, 20 C4H18C1CoN40

2+ cw-Aquachlorobis(ethylene- C2 HgN2 Mercuric cyanide, 78 diamine)cobalt(III) ion, 38 C2 HgN2S2 Mercuric thiocyanate, 79 C4H 19C1CoN52+ cw-Amminechlorobis(ethylene- C3 HBrN02 S 2-Bromo-5-nitrothiazole, 145 diamine)cobalt(III) ion, 37 c3 h3 no2 Cyanoacetic acid, 160 C4N4Ni2' Tetracyanonickelate(II) ion, 90 C3 H3NS Thiazole, 349 C5 FeN60

3- Pentacyanonitrosylferrate(III) ion, 70 c3 h3n302 2-Nitroimidazole, 289

4—Nitroimidazole, 290 QFeNeO4- Pentacyanonitrosylferrate(III) radical ion

(electron adduct), 71 c3 h3 n3o2 s 2-Amino-5-nitrothiazole, 127 cs h2 no5

- 5-Nitrofuroate ion, 288 C3 H303

- Pyruvate ion, 330 c5 h3 n2o4

- Orotate ion, 303 c3 h5 io2 3-lodopropionic acid, 239 c5 h4n2 o2 Pyrazinecarboxylic acid, 322 c3 h5 n Propionitrile, 316 c5h4n2o4 Nifuroxime , 278 c3 h5no Acrylamide, 123 c5 h4n4 Purine, 320

3-Hydroxypropionitrile, 230 cs h4os

2- a-Ketoglutarate ion, 246 C3 H-,02S- 3-Mercapt6propionate ion, 253a c5 h I0o 3-Pentanone, 305 C3 H303

- Lactate ion, 247 c5 h,,no2s Penicillamine, 304 C3 H6 Propylene, 317 Cs H I2 N

+ Piperidinium ion, 377 c3 h60 Acetone, 116 C5 H 15CoN6022+ Tetraammine(pyrazinecarboxy 1810- 0^

C3H602 Propionic acid, 315 cobalt(III) ion, 34 C3 Hh03 Lactic acid, 248 C5 H 18CoN7 022+ Pentaammine(pyrazinecarboxylato)-

85
C5H20CoN63+

cobalt(III) ion, 33 C7 H8 NO+ 3-Carboxy-l-methylpyridinium ion, 153

Pentaammine(pyridine)cobalt(III) ion, 31 4-Carboxy-l-methylpyridinium ion, 154 C5 H23Co2 N8043+ Hexaamminebis(jU,-hydroxy)[jU,-(pyrazine- c7 h9cin2o 2-Pyridinecarboxaldoxime methochloride, 326

carboxylato)]dicobalt(III) ion, 35 c7 h9n2o

+ 3-Carbamoyl-l-methylpyridinium ion, 151 C6C1402 Tetrachlorobenzoquinone, 338 C7 H n N3 03 Misonidazole , 272

Cf,FeN6

3“ Ferricyanide ion, 69 C7 H, 8CoN7 062+ Pentaammine(2,4-dinitrobenzoato)cobalt q,h2 n3o9s- Trinitrobenzenesulfonate ion, 355 (III) ion, 27 c() h4cino2 y?-Chloronitrobenzene, 158 Pentaammine(3,5-dinitrobenzoato)cobalt c6h4n2o4 1,2-Dinitrobenzene, 187 (III) ion, 28

1.3-

Dinitrobenzene, 188

1.4-

Dinitrobenzene, 189 C7 H 19CoN6042+ Pentaammine(4-nitrobenzoato)cobalt

(III) ion, 26 c6h4n4 Pteridine, 318 Pentaammine(2-nitrobenzoato)cobalt c6h4n402 Lumazine, 250 (III) ion, 24 c6h4o2 Benzoquinone, 138 Pentaammine(3-nitrobenzoato)cobalt c6h5 no Nitrosobenzene, 297 (III) ion, 25 c6h5 no2 Isonicotinic acid, 245 C7 H20CoN5O22+ Pentaammine(benzoato)cobalt(III) ion, 23

Nicotinic acid, 277

Nitrobenzene, 283 C7 H24Co2 N7 063+ Hexaamminebis(jLt-hydroxy)[jLt-(4-nitrobenzoato)]dicobalt(III) ion, 29 c6h5 no3 o-Nitrophenol, 294 c8h3N05

2 - 2-Nitroisophthalate ion, 291 c6h5 no4 l,3-Dihydroxy-2-nitrobenzene, 178 c8h6no4

- 3-Methyl-2-nitrobenzoate ion, 263 c6h5n50 Pterin, 319 QH6N2 Quinoxaline, 331 c6h5o- Phenoxide ion, 309 c8h7 no3 />-Nitroacetophenone, 279 C6H6CoN306

- Nitrilotriacetatocobalt(II) ion, 11 c8h8 o Acetophenone, 118 c6h6no- 4-Aminophenoxide ion, 128 QH8o2 2,3-Dimethylbenzoquinone, 180 c6h6n2o Isonicotinamide, 244

Nicotinamide, 275

2.5-

Dimethylbenzoquinone, 181

2.6-

Dimethylbenzoquinone, 182

4-Pyridinecarboxaldoxime, 325 c8 h9no3 3-Methoxy-2-nitrotoluene, 257 c6h6n2o2 o-Nitroaniline, 280 c8h9o- 4-Ethylphenoxide ion, 207

m-Nitroaniline, 281 c8h10no6p Pyridoxal-5-phosphate, 327

jP-Nitroaniline, 282 Qh10n2o iV,A-Dimethyl-4-nitrosoaniline, 185a C6H6N4 9-Methylpurine, 269 c8huno2 2-(3,4-Dihydroxyphenyl)ethylamine, 179 c6h6o2 1,2-Dihydroxybenzene, 176 c8hu no3 Pyridoxine, 328

1,3-Dihydroxybenzene, 177 C8H12 CuN403 Glycylhistidinecopper(II) complex, 64

Hydroquinone, 227 c8h12 no2 Norpseudopelletierine-7V-oxyl, 302 c6h7 n Aniline, 130 QH13 o2s2 Lipoate ion, 249 c6h7 no2 A-Ethylmaleimide, 206 C8H19N602 2+ Pentaammine(4-cyanobenzoato)cobalt(III) ion, 30 c6h7 o6

- Ascorbate ion, 135 C8H21 CoN6042+ Pentaammine(4-nitrophenylacetato) c6h8n2 o-Phenylenediamine, 310 cobalt(III) ion, 22

/>-Phenylenediamine, 311 C8H22CoN5022+ Pentaammine(phenylacetato)cobalt(III) ion, 21 c6h804 Dimethyl fumarate, 184 c9h10 ino3 3-Iodotyrosine, 240 c6h9n303 Metronidazole, 271 c9h10o2 2,3,5-Trimethylbenzoquinone, 353 C6HuCuN3042+ Glycylglycylglycinatocopper(II) c9hu no3 Tyrosine, 358

complex, 61 Cc^NA 2,2,5,5-Tetramethyl-3-pyrrolin-l-yloxyQH12 N402 Diamide, 170 3-carboxamide, 346 C6H14N

+ Cyclohexylammonium ion, 375 CgH^NO, 2,2,6,6-Tetramethyl-4-oxo-l-piperidinyl- c6h16n

+ Triethylammonium ion, 374 oxy, 342 C6H19CoN6022+ Pentaammine(pyridinecarboxylato)

cobalt(III) ion, 32 C9H 17 N2 02 2,2,5,5-Tetramethyl-l-pyrrolidinyloxy3-carboxamide, 345 C6H24CoN63+ Tris(ethylenediamine)cobalt(III) ion, 36 C9Hi8N02 2,2,6,6-Tetramethyl-4-hydroxy-l-piperi- C7 H2 N308 2,4,6-Trinitrobenzoate ion, 356 dinyloxy, 343 c7 h3 n206

- 2,4-Dinitrobenzoate ion, 190 c10h2 n4 1,2,4,5-Tetracyanobenzene, 339

2,5-Dinitrobenzoate ion, 191 ^io^s^sS l,4-Naphthoquinone-2-sulfonate ion, 274

3,4-Dinitrobenzoate ion, 192 6ioH602 1,4-Naphthoquinone, 273

3,5-Dinitrobenzoate ion, 193 c10h6o3 2-Hydroxy-l,4-naphthoquinone, 228 c7 h3 n3o4 3,5-Dinitrobenzonitrile, 194 CioH8 N2 2,2'-Bipyridine, 143 c7 h4cin m-Chlorobenzonitrile, 156a CI0HI2 CuN2O8 Ethylenediaminetetraacetatocuprate(I) ion, 58a c7 h4no4

- o-Nitrobenzoate ion, 284 C10H12 CuN2O8

2- Ethylenediaminetetraacetatocuprate(II) ion, 65a

m-Nitrobenzoate ion, 285 Ci 0Hi 2 O2 Duroquinone, 198

/>-Nitrobenzoate ion, 286 CioH 13 N504 Adenosine, 124 c7 h4no5

- 3-Hydroxy-2-nitrobenzoate ion, 229 CioHhCuNA /3-Alanylhistidinecopper(II) complex, 65 c7 h4n2o2 /?-Nitrobenzonitrile, 287 C10H14N507 P Adenosine monophosphate, 125 c7 h5 no5 /?-Nitroperoxybenzoic acid, 293 CioH 16N2 Arv/V,AA’-Tetramethyl-/>-phenylenedi- c7 h6n2o5 3,5-Dinitroanisole, 186 amine, 344 c7 h6o2 2-Methylbenzoquinone, 259 6h)H ]60 Camphor, 150 c7h7no 3-Acetylpyridine, 120 6ioH 17 N306S Glutathione, 215a c7 h7 no2 o-Nitrotoluene, 300 c„h8n3o4 +

l-(2,4-Dinitrophenyl)pyridinium ion, 195 c7 h7 no3 3-Methyl-2-nitrophenol, 265 Cn H802 2-Methyl-l,4-naphthoquinone, 262 c7h7n5o 3-Methylpterin, 268 ChH|2 N204 A-Formylkynurenine, 213 c7 h7 o- 4-Methylphenoxide ion, 266 CnH,sN505 1-Methylguanosine, 261 c7 h7 o2 - 4-Methoxyphenoxide ion, 258 C I2 H7C1N0 Dichloroindophenol, 173 86
C| 2H8N2 1,10-Phenanthroline, 306 C| 9 H]9N7 06 Folic acid, 210

Phenazine, 307 Eosin, 199 c12 h9no 3-Benzovlpyridine, 141 Qn^ioOs Fluorescein, 209

4—Benzoylpyridine, 142 c20 h 19n4 +

Safranine T, 336

Indophenol, 233 C2 ,H28N7 01 oP2 Nicotinamide-adenine dinucleotide, 276 c12 h9n3 s Thionine, 350 c22hI8n22+ l,l'-Diphenyl-4,4'-bipyridinium ion, 196 C12 H)0N2 Azobenzene, 136 C24h 16n42+

1 , 1 '-Di(4—cyanophenyl)-4,4'-bipyridinC] 2 Hi 0O2 2,3-Dimethylnaphthoquinone, 185 ium ion, 175 c12 h 12 n22+ l,r-Ethylene-2,2'-bipyridinium ion, 203 c24h22 n22+ l,l'-Dibenzyl-4,4'-bipyridinium ion, 171 c I2 h 14n22+ l,l'-Dimethyl-4,4'-bipyridinium ion, 183 F-2sH30C1N3 Crystal Violet, 159 C 12 Hi7C1N40S Thiamine, 348 0:8^3 )N2 03 Rhodamine B, 332 C12Hi8CuN604 Histidinecopper(II) complex, 63 C30H24CoN63+ Tris(2,2'-bipyridine)cobalt(III) ion, 44 c12 n9no 2-Benzoylpyridine, 140 C30H24N6Rh3+ Tris(2,2'-bipyridine)rhodium(III) ion, 98 c13 h9n Acridine, 121 C30H24N6Ru2+ Tris(2,2'-bipyridine)ruthenium(II) ion, 99 C13H10O Benzophenone, 137 C30H24N6Ru3+ Tris(2,2'-bipyridine)ruthenium(III) ion, 105 c13 h12no+ 3-Benzoyl- 1-methylpyridinium ion, 139 F-3oH28FeN406 Deuteroheme, 223 c13 h14n22+ l,l-Trimethylene-2,2'-bipyridinium ion, 354 C30H28 FeN4O6 Deuterohemin, 222 cI4h607 s2

2- 9, 10-Anthraquinone-2,6-disulfonate ion, 134 ^31^46^2 Vitamin Kj, 360 CuH7 05S' 9,10-Anthraquinone-l-sulfonate ion, 132 Q2^34N406 Deuteroporphyrin dimethyl ester, 221a

9,10-Anthraquinone-2-sulfonate ion, 133 ^-'34^24^6^a4^ 14^4 Trypan blue, 357

Ci4H802 9,10-Anthraquinone, 131 C^H^ClFeN^.j Hemin, 224 c14h 14cin3 Acriflavin, 122 ^34^38^4^6 Hematoporphyrin, 220 c14h16n22+ l,l'-Tetramethylene-2,2'-bipyridinium ion, 341 C36H24CoN63+ Tris( 1 , 1 0-phenanthroline)cobalt c14h18n2o22+

1 , 1 '-Bis(2-hydroxyethyl)-4,4'-bipyridin- (III) ion, 45

ium ion, 144 C36H24FeN63+ Tris(l,10-phenanthroline)iron(III) ion, 72 C14H26CoN402 + Dihydroxy(2,3,9,10-tetramethyl-l,4,8,ll- C36H24N6Rh3+ Tris(l,10-phenanthroline)rhodium(III) ion, 98a

tetraazacyclotetradeca-1 ,3,8, 1 0- C36H24N6Ru2+ Tris(l,10-phenanthroline)ruthenium(II) ion, 99a

tetraene)cobalt(III) ion, 52 C4oH3oN10062+ Nitro blue tetrazolium, 287a CI4H27CoN4022+ Aquahydroxy(2,3,9,10-tetramethyl- C40H46ClFeN608S2 Hemin c, 225

1 ,4,8, 1 1-tetraazacyclotetradeca- C42 H58CoN63+ Tris(5,6-dimethyl- 1 , 1 0-phenanthro1,3,8, lO-tetraene)cobalt(III) ion, 51 line)cobalt(III) ion, 45a C14H28CoN4022+ Diaqua(2,3,9, 10-tetramethyl-l,4,8,1 1- ^48^30^4^8 m«50-5-Tetra(4—carboxyphenyl)porphyrin, 337

tetraazacyclotetradeca-1,3,8,10—tetra- C62H9oCoNi3Oi4P Cobal(II)amin, 10

ene)cobalt(II) ion, 7 ^62^91 ^*oNj30j3 P Hydroxocob(III)alamin(Vitamin B12a), 54 C14 H28CoN4023+ Diaqua(2,3,9, 10-tetramethyl-l,4,8,1 1- ^“63^90^°^ 14®14P Cyanocob(III)alamin(Vitamin B12), 53

tetraazacyclotetradeca-l,3,8,10-tetra- C^CoN16024S8 3,10,17,24—Tetrasulfophthalocyaninecoene)cobalt(III) ion, 50 balt(II) ion dimer, 10a C16H6N2 014S4

‘t_ Indigo tetrasulfonate, 232 Cd + Cadmium(I) ions, 4

c,6h8 n2 08s2 Indigo disulfonate, 231 Cd2+ Cadmium(II) ion, 5

^16^10 Pyrene, 323 C1CoH15N52+ Pentaamminechlorocobalt(III) ion, 16

^•16^16N204 l,l'-Dicarboxyethyl-4,4'-bipyridinium, 172 C1H15N5Ru2+ Chloropentaammineruthenium(III) ion, 102

Ci6H18 N3S Methylene blue, 260 Cl2 Hg Mercuric chloride, 75

C,6H32C12CoN4 Dichloro(5,7,7, 12,14, 14—hexamethyl- Cl6 Ir

2- Hexachloroiridate(II) ion, 81a

1 ,4,8, 1 1 -tetraazacyclotetradeca-4, 11- Co2+ Cobalt(II) ions, 6

diene)cobalt(III) ion, 49 CoFH15 N52+ Pentaamminefluorocobalt(III) ion, 17 C16 H32 CuN42+

(5,7,7,12, 14, 14—Hexamethyl-1,4,8, 11- CoH15 N6022+ Pentaammine(nitrito-7V)cobalt(III) ion, 18

tetraazacyclotetradeca-4,1 1- CoH1sN6032+ Pentaammine(nitrato-0)cobalt(III) ion, 19

diene)cobalt(II) ion, 60 CoH 16 N50

2+ Pentaamminehydroxycobalt(III) ion, 14 C15H32N4Ni2+

(5,7,7, 12,12, 14-Hexamethyl-1,4,8,11- CoH17 Ns0

3+ Pentaammineaquacobalt(III) ion, 13

tetraazacyclotetradeca-4, 11- CoH18 N63+ Hexaamminecobalt(III) ion, 12

diene)nickel(II) ion, 92 Cr2+ Chromium(II) ion, 55

C, 6H34CoN402 +

(5,7,7,12,14,14—Hexamethyl-1,4,8, 11- Cr3+ Chromium(III) ion, 56

tetraazacyclotetradeca-4, 11- Cu +Coppeifl) ions, 57

diene)dihydroxycobalt(III) ion, 48 Cu2+ Copper(II) ions, 59

C,6H35CoN4022+ Aqua(5,7,7,12,14,14—hexamethyl- Eu3+ Europium(III) ion, 66

1,4,8, 1 1 -tetraazacyclotetradeca- Fe2+ Iron(II) ion, 67

4,ll-diene)hydroxvcobalt(III) ion, 47 Fe3+

Iron(III) ions, 68 C16 H36CoN4022+ Diaqua(5,7,7,12,14,14-hexamethyl- Ga2+ Gallium(II) ions, 73

1 ,4,8, 1 1 -tetraazacyclotetradeca- HO- Hydroxide ion, 362

4,ll-diene)cobalt(II) ion, 9 H02P23- Pyrophosphate ion, 369 C16H36CoN4023+ Diaqua(5,7,7,12,14,14—hexamethyl- H2 0 Water, 363

1,4,8, 1 1 -tetraazacyclotetradeca- h2 o2 Hydrogen peroxide, 94

4,ll-diene)cobalt(III) ion, 46 H2 04P- Phosphate ion, 368 C16H36N4Ni2+ (5,7,7,12,12,14—Hexamethyl-1,4,8, 11- H2 S Hydrogen sulfide, 106

tetraazacyclotetradecane)nickel(Il) ion, 91 h3 n Ammonia, 365 c17 h20n2s Promethazine, 312 h3 no Hydroxylamine, 84

^“*17^20^4^6 Riboflavine, 333 h3 0

+ Hydronium ion, 361

Riboflavine 5'-phosphate , 334 h4n

+ Ammonium ion, 364 C18 H 1S N4 +

Phenosafranine, 308 H i5N6ORu3+ Nitrosopentaammineruthenium(III) ion, 103

87
HI5

N6ORu2+ Nitrosopentaammineruthenium(III) 02 Oxygen, 93

radical ion (electron adduct), 104 02S Sulfur dioxide, 107 H18N6Ru3+ Hexaammineruthenium(III) ion, 100 o6s42- Tetrathionate ion, 108 Hgl2 Mercuric iodide, 76 Pb+

Lead(I) ions, 95

I03- Iodate ion, 81 Pb2+

Lead(II) ions, 96

h

Iodine, 80 Sc2+ Scandium(II) ions, 109 Mn2+ Manganese(II) ions, 82 Ti3+

Titanium(III) ions, 110 Mn04- Permanganate ion, 83 T,+ Thallium(I) ion, 111 no2- Nitrite ion, 86 Tl2 +

Thallium(I) ion, complex with T1(0), 111a N03- Nitrate ion, 87 Yb3+ Ytterbium(III) ions, 112 N20 Nitrous oxide, 85 Zn +

Zinc(I) ion, 113

Ni + Nickel(I) ion, 88 Zn2+ Zinc(II) ion, 114

Ni2+ Nickel(II) ions, 89
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study of the reaction of Ni +

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73G125 Patel, K.B., Willson, R.L., Semiquinone free radicals and oxygen.

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79(11): 1059-62 (1975). 75A060 Moorthy, P.N., Hayon, E., Free radical intermediates produced from

the one-electron reduction of purine, adenine, and guanine

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mechanism of reduction of cytochrome c as studied by pulse

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Soc., Faraday Trans. 1 72(6): 1377-90 (1976). 76A072 Buxton, G.V., Sellers, R.M., McCracken, D.R., Pulse radiolysis study

of monovalent cadmium, cobalt, nickel and zinc in aqueous

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radiosensitizers, Radiat. Res. 66(3): 472-84 (1976). 76A082 Abramovitch, S., Rabani, J., Pulse radiolytic investigations of peroxy

radicals in aqueous solutions of acetate and glycine, J. Phys. Chem. 8(5): 609-11 (1976). 76A087 Fujita, S., Horii, H., Mori, T., Taniguchi, S., Pulse radiolysis of HgBr2 in aqueous solutions, Bull. Chem. Soc. Jpn. 49(5): 1250-3

(1976). 76A103 Toffel, P., Henglein, A., The temperature dependence of the

electrolytic dissociation of some 1-hydroxy-alkyl radicals in aqueous solution (a pulse radiolysis study), Ber. Bunsenges. Phys. Chem. 80(6): 525-8 (1976). 76A104 Frank, A.J., Graetzel, M., Henglein, A., Janata, E., The influence of

the interface potential on the reactions of hydrated electrons and

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93
76A111 Neta, P., Simic, M.G., Hoffman, M.Z., Pulse radiolysis and electron spin resonance studies of nitroaromatic radical anions. Optical absorption spectra, kinetics, and one-electron redox potentials, J. Phys. Chem. 80(18): 2018-23 (1976). 76A113 Madhavan, V., Lichtin, N.N., Hayon, E., Electron adducts of acrylic acid and homologues. Spectra, kinetics, and protonation reactions. A pulse radiolysis study, J. Org. Chem. 41(13): 2320-6 (1976). 76A127 Seki, H., Ilan, Y.A., Ilan, Y., Stein, G., Reactions of the ferri- ferrocytochrome-c system with superoxide/oxygen and C02~/C02 studied by fast pulse radiolysis, Biochim. Biophys. Acta 440(3): 573-86 (1976). _ 76A132 Ilan, Y., Rabani, J., On some fundamental reactions in radiation chemistry: Nanosecond pulse radiolysis, Int. J. Radiat. Phys. Chem. 8(5): 609-11 (1976). 76A137 Ilan, Y.A., Rabani, J., Czapski, G., One electron reduction of metmyoglobin and methemoglobin and the reaction of the reduced

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94
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/3-hydroxyalkvl radicals with Cu'* and Cu^ ions in aqueous

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in aqueous solution. II. A pulse radiolysis study, Ber. Bunsenges.

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tetrachloride-related peroxy free radical (CC13 02

-) with amino

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complexes. Oxidation-reduction of methyl radicals by copper

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-' and 02-' to bacterial cytochrome P450, Biochem. Biophys. Res. Commun.

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2-alkanonyl radicals produced from 1,2-dihydroxy and

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(1979). 79.4134 Cheney, R.P., Pell, S.D., Hoffman, M.Z., Radiation synthesis of

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M.Z., Simic, M.G., One-electron reduction of aromatic nitrogen

heterocycles in aqueous solution. 2,2'-Bipyridine and 1,10-

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radical cation and OH adduct(s) of 3,5-dinitroanisole studied by

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by e

' and C02

' from pulse radiolysis studies, J. Biol. Chem.

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transfer in the reaction of hydroxyl radicals with (pyridine)pentaamminecobalt(III) ion in aqueous solution, Inorg. Chem. 18(9): 2479-85 (1979). 79.4255 Bhattacharyya, S.N., Srisankar, E.V., Radiation chemistry of

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95
79A312 Ilan, Y., Shafferman, A., Feinberg, B.A., Lau, Y.-K., Partitioning of

electrostatic and conformational contributions in the redox

reactions of modified cytochromes c, Biochim. Biophys. Acta

548(3): 565-78 (1979). 79A327 Houee-Levin, C., Gardes-Albert, M., Ferradini, C., Pucheault, J., Pulse radiolytic investigatins of the redox system alloxan-dialuric

acid: Evidence for a radical intermediate, Biochem. Biophys. Res. Commun. 91(3): 1196-200 (1979). 79A341 Micic, O.I., Nenadovic, M.T., Pulse-radiolytic investigation of the reduction of titanium(III) ions in aqueous solutions, J. Chem. Soc., Dalton Trans. (12): 2011-4 (1979). 79A371 Shieh, J.J,, Sellers, R.M., Hoffman, M.Z., Taub, I. A., Radiation

chemistry of myoglobin, its derivatives, and model compounds in aqueous solution, Radiation Biology and Chemistry. Research

Developments, H.E. Edwards, S. Navaratnam, BJ. Parsons and

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dihydropsoralen: Reaction with nucleic acid bases and amino

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colloidal silver in aqueous solution, J. Phys. Chem. 83(22): 2858-

62 (1979). 79N061 Almgren, M., Grieser, F., Thomas, J.K., Rate of exchange of

surfactant monomer radicals and long chain alcohols between

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R., Swallow, A.J., One-electron reduction of ferrideuteroporphyrin IX and reaction of the oxidized and reduced forms with

chlorinated methyl radicals, J. Am. Chem. Soc. 102(3): 1015-20

(1980). 80A053 Packer, J.E., Willson, R.L., Bahnemann, D., Asmus, K.-D., Electron

transfer reactions of halogenated aliphatic peroxyl radicals: measurement of absolute rate constants by pulse radiolysis, J. Chem. Soc., Perkin Trans. 2 (2): 296-9 (1980). 80A054 Soylemez, T., von Sonntag, C., Hydroxyl radical-induced

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reaction, Inorg. Chem. 19(4): 966-8 (1980). 80A071 Eibenberger, J., Schulte-Frohlinde, D., Steenken, S, One-electron

oxidation of a-monoalkoxyalkyl radicals by tetranitromethane via an intermediate adduct. Influence of radical structure on rate of decomposition of the adduct, J. Phys. Chem. 84(7):704-10 (1980). 80A085 Bielski, B.H.J., Shiue, G.G., Bajuk, S., Reduction of nitro blue

tetrazolium by C02‘ and 02~ radicals, J. Phys. Chem. 84(8): 830-

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I rCl &

2 ~

, Fe(CN) b 3- and Mn04 _

in aqueous solution. Electron

transfer versus chlorine transfer from IrCl b 2_

* J- Am. Chem.

Soc. 104(5): 1244-8 (1982).

96
U.S. DEPT. OF COMM. 1. PUBLICATION OR 2. Performing Organ. Report No. 3. Publication Data BIBLIOGRAPHIC DATA

SHEET (See instructions)

REPORT NO.

NSRDS-NBS 70 October 1982

4. TITLE AND SUBTITLE

Rate Constants for Reactions of Aliphatic Carbon-Centered

Radicals in Aqueous Solution

5. AUTHOR(S)

Alberta B. Ross and Pedatsur Neta

S. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions)

Radiation Chemistry Data Center

7. Contract/Grant No.

Radiation Laboratory 8. Type of Report & Period Covered

University of Notre Dame

Notre Dame, Indiana 46556

N/A

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

National Bureau of Standards

Department of Commerce

Washington, D. C. 20234

10. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 82-2096

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

11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bi bl iography or literature survey, mention it here)

Rate constants have been compiled for reactions of various transient aliphatic

radicals produced mostly by radiolysis in aqueous solutions. In certain cases the

radicals have been produced by photolysis or by a thermal chemical reaction. Data

are included for aliphatic carbon-centered radicals only, i.e., substituted alkyl

radicals in the broad sense, but not for oxyl or aminyl radicals. Reactions of the

aliphatic radicals with inorganic and organic compounds are included.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolon s) alkyl radicals; aminoalkyl radicals; aqueous solution; carboxyalkyl radicals;

chemical kinetics; electron transfer; haloalkyl radicals; hydroxyalkyl radicals;

photolysis; radical anions; radiolysis; rates.

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