A 11 10 2 06022b

NATL INST OF STANDARDS & TECH R.I.C.

All 102080226

Baxendale, John H/The radiolysis of math

5 R30.B3 1975 C.1 NSRDS 1975 NSRDS-NBS 54

U.S. DEPARTMENT OF COMMERCE /

National Bureau of Standards

The Radiolysis of Methanol:

Product Yields, Rate Constants,

and Spectroscopic Parameters

of Intermediates

^|£ssj

f

imm
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5RS0 The Radiolysis of Methanol:

.33 Product Yields, Rate Constants,

and Spectroscopic Parameters

of Intermediates

J. H. Baxendale + • Chemistry Department

University of Manchester,

Manchester, U.K.

and

Peter Wardman

Gray Laboratory,

Mount Vernon Hospital,

Northwood, Middlesex, U.K.

N SRD S

U.S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretary

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

Issued April 1975
Library of Congress Cataloging in Publication Data

Baxendale, J. H., 1917 —

The radiolysis of methanol.

(NSRDS-NBS 54)

Supt. of Docs, no.: C 13.48.54

1. Radiation chemistry. 2. Methanol,.

I. Wardman, Peter, joint author. II. Title. III. Series:

United States. National Bureau of Standards. National

standard reference data series, NSRDS-NBS 54. QC100.U573 no. 54 (QD651.M4) 389’.6’08s (547’. 031)

74-19001

NSRDS-NBS 54

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 54, 26 pages (Apr. 1975)

CODEN: NSRDAP

1975 by the Secretary of Commerce on Behalf of the United States Government

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WASHINGTON: 1975 For sale hy the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

(Order by SD Catalog No. C13.48:54). Price 85 cents.
Foreword

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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

1. Gas phase radiolysis of methanol 1 1.1. Final products 1 1.2. Primary products 1 1.3. Dosimetry 2

2. Liquid phase radiolysis of methanol 2

2.1. Final products 2

2.2. Primary products 2

2.3. Reaction of the solvated electron with methanol 3

2.4. Determination of the yields of free and geminate ions 3

3. Radiolysis of solid methanol. 12

4. Reaction rate parameters 15

5. Spectroscopic parameters 20

5.1. Optical absorption of trapped electrons in methanol glass 20

5.2. Optical absorption of solvated electrons in methanol liquid 21

5.3. Optical absorption of CH2OH and CH3CL in methanoL 21

5.4. Electron spin resonance parameters for ej and CH2 OH in irradiated solid methanol... 22

References 22

List of Tables

Page

1. Methanol vapor: Product yields 5

2.1.1. Liquid methanol: Product yields 6

2.1.2. Isotopic composition of hydrogen from methanol deuterated in the methyl or hydroxyl

positions: 9

2.2. Liquid methanol: Primary yields 10

3. Solid methanol: Product yields 13

4.1. Hydrogen atom reaction rates in methanol vapor 15

4.2. Hydrogen atom reaction rates in methanol liquid 15

4.3. Solvated electron reaction rates in methanol: Relative rates 16

4.4. Solvated electron reaction rates in methanol by pulse radiolysis 17

4.5. Solvated electron reaction rates in methanol: Recommended values 18

4.6. Rate of disappearance of solvated and trapped electrons in methanoL 18

4.7. Methyl radical reactions in methanol vapor or solid 19

4.8. Rates of reactions of other transients in methanol liquid 19

5.1. Spectroscopic parameters of e~t in CH3OH glass 20

5.2. Spectroscopic parameters of e~ in liquid methanol 21

v

The Radiolysis of Methanol: Product Yields, Rate Constants, and

Spectroscopic Parameters of Intermediates *

J. H. Baxendale

Chemistry Department, University of Manchester, Manchester, U.K.

Peter Wardman

Gray Laboratory, Mount Vernon Hospital, Northwood, Middlesex, U.K.

Product yields and primary yields in the radiolysis of methanol in the solid, liquid and vapor phase

have been compiled and reviewed. Preferred values for G of the major products in the vapor and liquid

states are listed. Rates of reactions of solvated and trapped electrons and other transient ions and

radicals, and optical absorption and esr parameters for e~, e~, CH2OH and CHsO- are also included. Key words: Chemical kinetics; data compilation; methanol; radiation chemistry; rates; review.

Introduction

The presentation and evaluation of the numerical

data summarized in this review attempts to bring

together much of the published quantitative information concerning the radiation chemistry of

methanol. Discussion of the mechanism of radiolysis

is restricted only to explanation of the data. For

further discussion of mechanistic detail see [690736,

690391 and 700239]. 1 Reference to all the early work on the stable

product yields from irradiated methanol has been

included (even though more recent and more reli- able data are often available), because the early

references may contain qualitative information

concerning the effects of additives which is not

tabulated here but which may be of interest to the

reader. However, some attempt to be critical in

the selection of numerical values has been made.

For example, since the reaction of the solvated

electron with methanol is clearly no faster than

observed in [710101], reference to earlier investiga-

*This is a data review prepared for. and in cooperation with the Radiation Chemistry

Data Center of the Radiation Laboratory. University of Notre Dame. Notre Dame. In- diana 46556. The Laboratory is operated under contract with the Atomic Energy Commission. The work of the Center is supported in part by the National Bureau of Standards, Office of Standard Reference Data. ‘The coding of the Radiation Chemistry Data Center is used for references throughout this survey.

tions (especially indirect estimates from the effects

of nitrous oxide) do nothing but confuse the reader

and are omitted.

The uncertainties listed in the tables of product

yields and most of the rate parameters are those

given in the original work. In many cases they are simply the reproducibility of the experiments and

the true uncertainty may be much larger.

1. Gas Phase Radiolysis of Methanol

1.1. Final Products

At room temperature and low doses of 60 Co y- irradiation, the final products are mainly hydrogen,

formaldehyde, ethylene glycol, carbon monoxide

and methane. G{ H2 ) 2 seems to increase at higher

temperatures but this effect is offset at higher pres- sures, an observation attributed to ion-molecule

clusters [670071].

1.2. Primary Products

At the time of reporting, few values for the unscav- engeable hydrogen and formaldehyde, and for hydrogen atoms and electrons are available. The latter give reasonable values for IF 3 in methanol (see

2 The symbol G denotes yield of product per 100 eV (1.602 X 10 17 J) energy absorbed.

3The symbol Wdenotes the number of ion pairs produced per 100 eV energy absorbed.

1
[720441]), but confirmation and extension of such

observations are required before reliable conclusions concerning the nature and yields of the

primary products can be made.

1.3. Dosimetry

In comparing product yields from different in- vestigations, note should be taken of the assumptions used in dosimetry, e.g. G(N2 ) from irradiated

nitrous oxide.

Table 1. Methanol vapor: Product yields (molec. (100 eV)-1

)

Ref. Product

Preferred

values 610021 630063 640154 650432 670071 670205 701047 k h2 a 11.0±0.5 10.4 11.8±0.3 10 ±2 11 . 2 ± 0.6 10 to 22 10.84 ±0.07 11.1 (CH.OHh 3.4 3.1 ch2 o 5.6 CR 0.38 ±0.05 0.26 0.5 ±0.1 0.35 ±0.05 0.7 to 1.5 0.42 ± 0.01 j 0.42 CO 1.2 ± 0.1 0.84 1 . 0 ± 0.2 1.18±0.06 1.41 ±0.07 j 1.25 G(-CH3OH) b 12.9 - e~ 4.5±0.7 4.1 ± 0.7 h 4.0

[ 8.65 f (with SF6 ) H 5.4±0.2 J 4.9 ± 0.2 h 8.48 ± 5.1 0.15 g> j (with C3 R)

Unscavengeable 2.3 ±0.2 1.75 f 1.9 g 2.1 ± 0 . 1

1 2.36 ± 2.0 h2 0.05 g j (SF«, C3 H6 ) Unscavengeable 2.25 f ch2 o

Radiation c y y y electrons y y y y

(260 keV) Dose d 5 to 50 5 to 50 5 0.4 to 5 3 to 90 350 < 800 30 to 600

( 1018 eV gr

1 ) Dose rate 0.02 to 0.4 0.017 and 0.08 5 X 108 0.4 7 9 2.3 to 3.5

( 1015 eV gr

1 s- 1 ) 0.17 T( K) 295 295 389 314 293 323 to 523 room 290 ±2

Pressure (Torr) e ~ 100 80 300 200 87 1900 80 Dosimetry n2 o N2 0 N,0 n2 o _ N2 0 N2 0 -.M)

G(N2)= 10.6 G(N2) = 9.68 G(N2 ) = 11.0 G(N2 ) = 9.68 G(N2 ) = 9.68 G(N2 ) = 10.6 G(N2 ) = 9.7 Vessel 5 dm3 5 dm3 3 dm3 6.5 dm3 0.13 dm3 0.25 dm3 soft glass soft glass Pyrex Pyrex Pyrex Pyrex

a See table 2.1.2 for isotopic composition of hydrogen from deuterated methanols.

b Calculated as 2G(glycol) + GfCR) + C(CH2 0) + G(CO).

c All -y-irradiations use 60 Co sources.

d Doses are approximate; 1 eV g

-1 = 1.602 X 10-16 J kg-1

; where the yields are dose dependent, extrapolation to zero dose is nor- mally made.

e 1 Torr= 133.3 Pa (N m-2

).

f With benzene.

g With propylene.

h With CRBr or CCL,.

1 With C2 H4.

j Measured yields were per ion pair, and were converted to G values by the authors using W = 27.7 ion pairs (100 eV)-1

; for a recent

value of W see [720441],

k [701014] is a preliminary report.

2
2. Liquid Phase Radiolysis

of Methanol

2.1. Final Products

As in the gas phase, the final products of radiolysis are almost entirely made up of hydrogen, ethyl- ene gylcol, carbon monoxide, formaldehyde, and

methane for irradiation at room temperature with

low doses of 60Co y radiation. The yields in general

decrease at lower temperatures [610015, 650507,

680189, 680397, 680407, 680610]. Small amounts of

other products have also been reported [540005,

610020, 640121, 650507].

Low values of G(H2 ) are generally attributable to the presence of electron scavengers as impurities,

scavenger concentrations as low as a few micromolar 4 being sufficient to reduce G(H2 ) by several

tenths of a C-unit. This effect was originally used

[610015] to demonstrate the reactivity of the elec- tron as a precursor of hydrogen. The removal of car- bon dioxide by the degassing procedure is of prime

importance [700947] because of the high solubility

in methanol; the inadequate removal of C02 from

the sample may cause difficulties even in the solid

phase [690456]. In general, under similar conditions

of dose, temperature and additive, the higher G

values are to be preferred. Variations in other

yields probably arise from errors in the methods of

analysis.

There is little effect of dose or dose rate on the

yields from 60Co y irradiations. Recoil nuclei from

the 10B(n, o:)

7 Li reaction give similar values of

G(H2 ) to y-radiolysis, but give increased CH20 and

CO yields with a much reduced glycol yield. Inter- pretation of data from the recoil nuclei irradiations

is complicated by the need to include ca. 0.1 M4

tri- methyl borate in all the samples, but the gross

effects of the different linear energy transfer of the

radiation are apparent from the tables.

The addition of acid increases C(H2 ) and

G(CH20) except at the lower concentrations but

leaves the CO, CH4 and glycol yields unchanged. An

increase in hydrogen yield in the presence of small

amounts of acid is often reported, but this effect

arises from competition between the acid and impurities for the solvated electrons. Hydrogen yields as a

* Concentrations of additives are generally expressed in molar units throughout.

1 M= 1 mol dm -3

; 1 mA/=10- 3 mol dm -3

. Second order rate constants are also expressed in units of M~ l s

_1 = dm3 mol _,

s _1

.

function of pressure (including the effects of acid)

have been reported [730292].

2.2. Primary Products

The term “primary product” is applied to those

species (ions, radicals, or atoms) which are precursors of the final products. The presence of precursors is usually established by the use of scavengers

which affect the yields of the final products. However, conclusions as to their nature frequently

require the assumption of a reaction mechanism

which cannot be proven and only rarely can it be

established that the precursor is truly a “primary

product”.

A demonstration of this uncertainty is provided

by the data in [610015], which were analyzed to show

the presence of two precursors of hydrogen. The

more reactive precursor was correctly identified as the electron, and later direct observations of the

solvated electron permit us to assign the readily

scavengeable hydrogen to those electrons which

escape the Coulombic field of the positive ions and

are “free”. The less reactive precursor of hydrogen was thought to be the hydrogen atom, but the

analysis of the data cannot indicate the source of

these atoms. It is impossible to say what fraction

of these hydrogen atoms arise from the neutralization of electrons which do not diffuse a sufficient

distance to become “free” but rather return to positive ions in the spur, and hydrogen atoms aris- ing from the decomposition of excited molecules.

It is apparent that many atoms or radicals often

described as primary products are in fact secondary

products arising from the true primary ions or electronically excited molecules. Thus, “primary

product” is rather an indefinite term in the present

state of knowledge. The same uncertainty attaches

to the numerical values of “primary” product yields,

which again require the assumption of a reaction

mechanism or model. It is important to realize in

using tables 1 to 3 that a “primary” product may

itself have a precursor.

A further complication arises because in general,

scavenging kinetics depend on the concentration

of scavenger used. At low concentrations, usually

less than about 10-3 M, the kinetics are usually in

accord with the assumption that the species

scavenged are homogeneously distributed throughout the medium. At higher concentrations, the

3
scavenger may react with species in high local

concentrations (“spurs”), i.e. the reacting species

are not homogeneously distributed. Simple kinetic

treatment of the scavenging efficiency is no longer

possible, and models accounting for the non- homogeneous distribution of radicals must contain an element of empiricism to a greater or lesser

extent. It is seldom possible to establish experimentally that the total amount of primary product

has been scavenged and recourse must be made

to a model to calculate such yields. Values for the

yields of primary products which are scavenged in

the spurs are therefore somewhat empirical.

Although CH2 OH has been reported as a scav- engable primary product, it is important to realize

that much of the so-called “primary” yield arises

from secondary abstraction by H atoms or by the

CH3O radical, the latter being expected to be

produced in significant yield in irradiated methanol

[690456] and identified from its oxidizing properties

[690045, 720115, 720122]. 5 These difficulties in assigning the true yields of

the primary species in irradiated methanol un- fortunately result in some confusion in interpreting the tables of primary yields. Because of the lack

of a detailed understanding of many of the processes

involved, a more rigorous nomenclature is not yet

possible.

2.3. Reaction of the Solvated Electron

with Methanol

Electrons which escape the Coulombic field of

positive ions in the spur are observed to decay by

first-order kinetics in either liquid [710101] or solid

[675117] methanol. Although the decay is assumed

to arise from reaction of e~ or e\ with methanol, it is not known whether the reaction is a simple bi- molecular dissociative electron capture such as:

CH3OH + » CH3 0

- + H.

Accordingly in table 4.6 it is listed as a first-order

decomposition. In the literature, several estimates

have been made of the rate constant for this reaction by applying simple competition kinetics to the

effects of scavengers on the hydrogen yield or to the nitrogen yield from solutions of nitrous oxide.

5 Confirmation that the oxidizing radical is indeed CH.,0 has been provided by ESR

using the spin trapping technique [725141],

This indirect method has been superceded by direct

observation of e~ by pulse radiolysis, and the

earlier approaches are now only of interest as a guide to the purity of the alcohol and reference to indirect estimates is omitted.

Experience with the analogous reaction in water

showed that the early estimates of the rate of the

decomposition of the solvated electron in water

proved to be orders of magnitude too high. Further,

it was only because considerable information was

available concerning reactions of e aq with other

radicals that confident estimates of the rate of

decomposition of e

~

q could be made. It is clear that

reliable measurements of the decomposition of e~

in alcohols can only be made by direct observation

by pulse radiolysis, and that the lowest rate measured supercedes all higher values. In the present

state of knowledge, this must only be an upper

limit. Only one study of the decomposition of e~ is listed in table 4.6. Longer lifetimes may be possible

at high concentrations of alkali, but the structure

of the solvent may be sufficiently changed that the

rate constant may not be applicable to the pure

solvent. There seems little doubt that further work

will supercede the values listed in table 4.6, although

the similar activation energies observed in the liquid

and solid phases (the latter for the case with K+ as the counter-ion) is noteworthy.

2.4. Determination of £(e~)fi and G(e~)gi We have already distinguished two kinds of ions:

the “free ions”, (e“)fi which have diffused suffi- ciently from their geminate cations to be regarded

as homogeneous and decaying by first-order kinetics

at low dose rates, and the “geminate ions”, ( e~) gj which, if left, would recombine with their geminate

cations. The yields of these species have been the

subject of several investigations, but it seems premature to recommend values of these important

parameters.

The difficulty of the non-homogeneous distribution

of the geminate ions has already been noted, but even

the application of simple competition kinetics to the scavenging of the free ions is not without objection if only stable products are measured. Further

information concerning the lifetime both of the free

and geminate ions under the conditions used is necessary.

4
Thus if, under the conditions being studied, the

half-life of the free ions is (typically) 2 /u.s, then for

98% scavenging of the free ions a scavenger with

concentration [S] is required such that (/c(e“ + S)

•[S]) — 2 X 107 s -1 and the first-order half-life of e -

fi at this [S] is then — 3 X 10-8

s. Direct observation of

that fraction of the geminate ions which survive

longer than ca. 1 X 10-8

s has established that a yield

of G — 0.4 of e -

gi survive longer than 10-8

s but have

all decayed by 2 X 10-7s. 6 Thus the concentration

region in which a scavenger will react with essentially all the free ions but remove a negligible

fraction of the geminate ions is quite narrow.

Application of empirical models to scavenging of

the geminate ions must consider the often neglected

possibility that at high scavenger concentrations

the electrons may be scavenged prior to the formation of the ionic atmosphere, when the electron

mobility may be orders of magnitude greater than e~. Such scavenging of “dry” electrons has been conclusively demonstrated [730087].

Direct observation of aromatic anions produced

by electron attachment [650499, 700360] in principle provides a satisfactory method of determining

G(e -

) fi . The absence of an increase in G(diphenyl-

) at high concentrations of diphenyl is attributed to spur neutralization of diphenylat times less than

10 -6

s. Measurement of the yield of a scavenger

anion of uncertain extinction coefficient in polar sol- vents, with unknown rate constant for electron capture and at a single concentration of scavenger

[700360] is quite insufficient to estimate G(e -

) fi , and much further work is required.

The products from electron capture by N2 O,

CIUBr, or SF6 appear a simple route to estimating

scavengeable electron yields, but the rate constants

of e - with these solutes have not been measured

directly and are known to no better than ±30% at best. The N2 0 system generally appears to predict

G(e-

) fi — 1.9 7

, e.g. [720197], whereas the ClUBr

or SF6 systems suggest a value of about 1.05

[700064] . The halide systems suffer from the prob6 J. H. Baxendale and P. Wardman. unpublished work, see [710101].

7 A value in accord with conductivity measurements [710064, 730042].

lem of buildup of acid at high doses, but this objection can readily be tested either by calculation or experiment. Unfortunately the doses used were not

reported. The marked increase in G(CH20) at high

concentrations of N2 0 [700947] probably results

from a secondary reaction (possibly the slow reduction of N2 0 by CH2 OH radicals). The rate constant

ratio for electron capture by N2 0 and a second sol- ute is independent of N2 0 concentration even at high concentrations [670065, 670313] so this complication does not appear to interfere. The nitrous

oxide technique seems to be useful as a reasonable

guide to electron rate constants even though in

principle the use of homogeneous kinetics is often

not valid at the concentrations of scavenger used.

G(e -

) fi may in principle be estimated from the

application of simple competition kinetics to the

decrease in G(H 2 ) on addition of electron scav- engers. This approach is no less direct than the

nitrous oxide or alkyl halide methods. The values

obtained depend upon the extrapolation of AG(H2 ) to infinite concentrations of scavenger. The re- liability of the method depends upon the weight

given to the values of AG(H2) corresponding to high

scavenger concentrations, values which for this

purpose may be erroneously high due to spur scav- enging and/or reaction with hydrogen atoms, both

of which may lead to high values of £(e -

) fi . On

the other hand, the low concentration values, which

are free from this objection, are subject to the

greatest experimental uncertainty. Thus workers

reporting the same G(H2) from pure methanol have

estimated G(e -

) fi to be 1.3 [610015] or 1.8 (see

[730292]) using this technique, and we can see no

reason for preferring either value.

The importance of a reliable estimate of C(e -

) fi is that the ratio of free to geminate ions can be measured directly by pulse radiolysis. It has been shown

[710101] that, at least at low temperature, for those

electrons which survive long enough to establish

the equilibrium ion atmosphere, G(e~) n = G(e~)

It is now possible to make similar measurements

at room temperature [730147].

5
i Table 2.1.1. Liquid methanol: Product yields (molec.(100 eV)~ 1 )*

Ref. Preferred 530004 540005 550003 580003 580005 590017 590017

Product values

H,a 5.4 ±0.1 5.0 ±0.3 3.46 ± 0.05 4.0 ±0.3 4.1 5.39 4.57 ± 0.08 (CH 2 OH)2 3.2 ±0.2 1.74 ± 0.04 3.0 ±0.2 3.1 3.63 2.91 ±0.11 2.96 ± 0.09s ch2 o 2.0 ±0.1 1.67 ±0.05 1.3 ±0.1 2.05 1.84 T.91 ± 0.06 1.84 ± 0.128 ch4 0.43 ± 0.03 0.4 0.36 0.24 ±0.06 1.23 0.54

jo. 36 jo.368 CO 0.13 ±0.03 0.23 0.16 ±0.02 0.15 0.11 Others See belowe G( — CH3OH) b 9.0 5.5 7.7 9.6 9.8 8.1 8.1 g

Radiation 0 y P ( 14 C) He + y y y y electrons

( -28 MeV) (2 MeV)

Dose d ~ 4000 See belowf 0.8 to 20 4 to 400 2 to 300 2 to 200

(10 18 eV g" 1 ) Dose rate 5 0.05 to 0.1 2 0.4 40 to 80

(10 15 eV g-'s- 1 ) T(K) 293 to 303 room 289 room room room 293 to 298 room

Notes Very high doses used See below8

Table 2.1.1. Liquid methanol: Product yields ( molec. (100 eV) *)* — Continued

Ref. Product

604001 610014 610015 610015 610020 610020 610027

H2 a 5.14±0.02 4.1 5.40 4.15 5.66 -5.3

(CH2OH)2 1.40±0.10 2.43 3.7 4.0 2.10 -3.4

ch2o 3.45 ±0.10 1.41 2.15 0.65 1.0 -1.8

ch4 0.67 ±0.04 0.39 0.80 0.45 0.57 -0.4

CO 0.92 ±0.06 0.13 0.15 0.13 0.45 Others 0. 14 G(—CH3OH)b 7.8 6.8 10.5 9.2 6.5

Radiation0 recoils y y y y X-rays y

10B(n, a) 7Li (3 MeV pk.) Dosed 30 0.1 to 0.5 0.1 to 0.5 10 -200 600 to 6000

(1018 eV g- 1 ) Dose rate 0.03 0.04 or 0.6 0.04 or 0.6 3.0 40 9

(1015 eV g" 1 s- 1 ) nK)

Notes See belowh 293 292 195 299 room

Very high doses used

* Footnotes follow the table.

6
Table 2.1.1. Liquid methanol: Product yields ( molec. (100 eP)-1)* — Continued

^''''''-^Ref.

Product^"''---^^ 610029 610029 630056 630056 630056 630060 640121 640121 H2 a 4.79 9.68 4.60 ± 0.17 4.99 ± 0.36 4.81 ± 0.14 4.99 4.98 ± 0.08 5.53 ±0.16

(CH2 OH) 2 2.54 0.77 2.92 ± 0.4 0.60 ± 0.09 1.95 ± 0.26 2.99 3.23 ±0.10 0.87 ± 0.07 ch2 o 2.28 3.6 ±0.4 2.41 ±0.28 3.15 ±0.38 2.00 ± 0.17 1.96 2.2 3.04 ±0.02

ch4 0.52 0.88 0.31 ± 0.05 0.57 ±0.14 0.32 ± 0.04 0.41 0.43 ± 0.09 0.66 CO 0.30 2.98 0.15 ±0.05 1.00 ± 0.13 0.15 ±0.02 0.10 0.06 1.0 Others See below1 See below1 See below1 C2 H4 0.035 G( — CH3 OH) b 8.2 9.0 8.7 5.9 6.4 8.5 9.2 6.4

Radiation0 n, y (pile) fissionJ y recoils y y y recoils fragments 10 B(n, a) 7 Li 10 B(n, a) 7 Li Dosed 600 to 800 500 to 1000 8 to 30 6 to 140 8 to 30 40 2 to 16

(10 18 eV g" 1 ) Dose rate ~ 50 4 0.01 to 0.5 4 2.5 to 13 4 0.1 to 0.5 (10 15 eV g- 1 s- 1 ) T (K) 373 373 ~ 293 ambient ~ 293 room 293 ambient

Notes

' See belowk See belowk See belowk

Table 2.1.1. Liquid methanol: Product yields (molec. (100 eV) 1 )* — Continued

'""'\Ref.

Product''^.

640166 650230 650501 650507 650507 650773 660013 660259

H2a 5.1 to 5.6 4.24 ±0.30 5.26 ±0.1 4.6 ±0.2 3.4 to 6.5 4.92 ±0.03 5.3 4.32 (CH2 OH)2 0.6 to 0.8 2.72 ±0.19 5.7 ±0.3 3.2 to 8.4 2.95 3.24 ch2 o 3.0 to 3.6 1.34±0.07 0.57 ±0.06 1.0 to 0.33" 2.2 CR, 0.58 to 0.64 0.24 ±0.03 1.5 ±0.1 0.9 to 2.2 ~0.6

CO 1.0 to 1.1 0.20±0.06 0.09 ±0.01 0.08 to 0.11 Others CH3OCH3 CROCR

0.074 0.10 to 0.055 G(-CH30H) b ~ 6.4 7.2 13.6

Radiation0 recoils y y y y y y y

10 B(n, a) 7 Li Dosed 10 to 20 <60 0.7 15 to 200 15 to 200 600 10 to 300

(1018 eV g

-1

) Dose rate 0.01 to 0.5 1.5 0.4 3 3 3 0.35 0.8

(1015 eV g

-1 s_1

) T( K)

- 293 room . 295 213 to 398° room 293 ±5

Notes See belowk See below"1 See below1"

‘Footnotes follow the table.

7
Table 2.1.1. Liquid methanol: Product yields ( molec. (100 eV)* 1 )* — Continued

8
Table 2.1.1. Liquid methanol: Product yields ( molec

.

( 100 eV) 7 ) — Continued

a See table 2.1.2 for isotopic composition of hydrogen from deuterated methanols.

b Calculated as 2G(glycol) + G(CH4 ) + G(CH2 0) + G(CO).

c All y irradiations use 60 Co source.

d Doses are approximate; 1 eVg-1 = 1.602 X 10-16 J kg-1

; where the yields are dose dependent, extrapolation to zero dose is normally

made.

e G(H2 0) = 0.93 ± 0.03; G(C2 Hg) =0.014 ±0.001. Note 2 to 3% decomposition of methanol.

f Dose ~ (4.5 to 18) X 1018 eV g

-1 to measure gaseous products. Dose ~ (0.4 to 2) X 1021 eV g

-1 to measure liquid products (very high).

g All product yields are normalized assuming G(H2 ) =4.57 under these conditions.

b All solutions contained 0.2 M BIOCH^.

1 Data for higher hydrocarbons.

3 84 MeV recoils. Data for 4 different types of 235 U source.

k All radiolysis samples for recoil nuclei irradiations contain —0.1 M B(OCH3 ) 3 . The data in column 2 [630056] are for -y-radiolysis of a similar sample. 'C2 H4, 0.004; C2 He, 0.006. m Glycol and CH2 0 yields clearly in error.

n CH2 0 found as CH2 (OCH3 ) 2 at 398 K.

0 Data for several temperatures over this range.

p [650187] is a preliminary report of these data.

q Samples contained 0.24 to 0.27 M BIOCH^.

r Independent of pressure in the range 1 to 5400 bar (105 to 5.4 X 108 Pa). Independent of HCIO4 up to 0.5 mM.

Table 2.1.2. Isotopic composition of hydrogen from methanola deuterated in the methyl or hydroxyl positions

Reference Phase Alcohol T (K) % h2 % HD % d2 Notes

610021 vapor ch3 od 295 56 44 0.2 701047 vapor cd3 oh 290 31 38 30 Also data with added SF6 and C3 H6 . 570027 liquid ch3 od room 36 60 4 630060 liquid cd3 oh room 11 78 11 See belowb 650507 liquid ch3 od 195 29 68 3 650507 liquid ch3 od 295 34 63 3 650507 liquid ch3 od 398 33 66 2 650507 liquid cd3 oh 295 15 73 12 650507 liquid cd3 oh 398 13 75 12 680167 liquid ch3 od room 38 59 3 See belowc

a All samples irradiated with 60 Co-y-rays.

b Also data with added LaCl3 , KI; also CD4 /CD3 H = 2.4.

c Also data with added FeCl3 , N2 0. Also data for samples after recoil nuclei irradiations ( 10 B(n,a) 7 Li).

9
Table 2.2. Liquid methanol: Primary yields ((100 eV) *)*

Product

580003 580005 580026 590029 600011 610015

Total

13v Scavengeable 6.55 a 6.3 6.6 6.8 6.3 c -o

cd Total e~

Im ) V (e* )ti 1 3.8 b 1.3

Xi

cd

0) («s )wi j

} 2.5

WDC H- J «

> CH2 OH 2.7

cn ch3 o- ch3 1.0

JV3 h2 1.7 2.0 1.6 to 1.7 d

1) « 2 "3 u (CH2 OHh 0.2 0.1 O 3

S> 4) "O ch2 o 2.05 8 0.36 0.65 e « o £ « S a ch4 0.2 0.2 0.22 f c ^

3

CO 0.15 ~0.1 0.12

Radiation h 7\K) Notes

y

room y

room

With I2 (0.04 M)

y

room

With FeCh

y

room

With 0.01 M

C(N02 ) 4

y

room

2 X G(I2 ) with ICN

yroom

Table 2.2. Liquid methanol: Primary yields ((100 eV) *)* — Continued

10
Table 2.2. Liquid methanol: Primary yields ((100 eV) 1 )* — Continued

Ref. Product 660259 670018 670030 670313 680594 680610

Scavengeable

radicals

Total Scavengeable

Total e -

(e s )fi

(e s )gi HCH2 OH

ch3 o- ch3

J

2.0r

5

1.05

2.8

l.l 1 4.6

2.0 ±0.2

Unscavengeable

(‘molecular’)

products h2 (CH2 OH)2 ch2 o

ch4 CO

1.7 1.4 to 1.9 1.7

^

0.3

Radiation 71 y y y y y y T(K) room room room room room 176 to 423 Notes With See also See belows With FeCl3 See belowu

pyridine 650187

TABLE 2.2. Liquid methanol: Primary yields ((100 eV) 1 )* — Continued

Ref. Product

690146 700064 700360 700947 710064 720115 aa 730042 730292

Scavengeable

radicals

Total Scavengeable

Total e~

(es )n

( es )gi

H-CH2 OH

ch3 o

ch3

\

3.96

^ ±0.27

2.02 ±0.18

4

4.15

1.05 1.10 x 4.9 ~1.3 2.0±0.2 Z

2.5 bb

J 1.8±0.2 CC 1.7 ±0.1 dd

Unscavengeable

(‘molecular’)

products h2 (CH2 OH)2 ch2 o

ch4 CO

1.81±0.27

Radiation h T(K)

Notes

y

296 See below v

7 room

See below w

electrons room

Pulse

radiolysis

7

room

See below y

electrons 298

Pulse

radiolysis

electrons room

Pulse

radiolysis

electrons room

Pulse

radiolysis

7

296

‘Footnotes follow the table.

11
Table 2.2. Liquid methanol: Primary yields {(100 eV) ') — Continued

Footnotes for table 2.2.

a With 1 mM FeCl3 in neutral CH3 OH. C(Fe(II)) increased to 7.6 at 0.1 M FeCl3 . b In presence of acid to convert all e$ to H.

c With FeCl3 , benzoquinone, duroquinone (see also 590020).

d With FeCl3 . benzoquinone, duroquinone, benzene, aromatic polycyclic hydrocarbons.

e With anthracene, benzene, and naphthalene at 195 K.

f With FeCl3 . 8 With benzene.

h All y-irradiations use 60 Co source.

1 Read from graph.

j With 0.1 M KI.

k With 0.5 M LaCl3 .

1 AD radiolysis samples for recoil nuclei irradiations contain ~ 0.1 M B(OCH3 ) 3 . m

l,l-diphenyl-2-picrylhydrazyl.

n G(diphenyl _

) from solutions of diphenyl. Assumed G(diphenyl_

) = 1.0 in ethanol( e diphenyi-) = 5.8 X 104 M~l cm-1 at 405 nm).

Uncertainty ± 30%. See discussion.

0 This conclusion not apparent from results.

p AG(H2 ) with 0.1 to 0.5 mM NiCl2 . q With 1.0 M LiN03 . r Total electrons scavenged with ~ 5 mM N2 0 (see discussion). '’From theoretical treatment of G(H2 ) in presence of N20, 02 , I2 or FeCl3 . Low G(H2 ) in absence of solute. 'From AG(H2) with 1 to 10 mM N20. Low G(H2) in absence, of solute.

u From theoretical treatment of G(H2 ) and G(N2 ) in presence of N2 0.

' From theoretical treatment of G(H2 ) in presence of 02 and H2 S04 . w From theoretical treatment of G(product) in presence of CH3 Br or SFe.

x G(pyrene~) in presence of 10 mM pyrene using e max=4.95 X 104 M 1 cm-1

. See discussion.

y From theoretical treatment of G(N2 ) in presence of N2 0.

z Total negative free ion yield as measured by conductivity.

aa [690045] is a preliminary report of these data.

bb Of which G = 2.0 escapes spurs.

cc Negative ion yield with 1 to 10 mM benzyl chloride, measured by conductivity. G(CH3 0~)= 0.35 ±0.15.

dd From effect of nitrobenzene or acetone on G(H2 ). G(e^)fi = 1.9±0.1 at 5.4 kbar (5.4 XJO8 Pa).

3. Radiolysis of solid methanol

Methanol frozen to 77 K may be either polycrystalline (when anhydrous) or glassy (e.g. with

2 to 3% v/v water or propanol as an additive which

can be considered inert for most purposes). Depending on the degree of crystallinity, major dif- ferences are found in the nature and yields of the

species trapped at 77 K or measured after melting.

Electrons are trapped only in glassy methanol and

the red-purple color of e~ can be removed by

illumination with visible light (photobleaching),

changing the yield of the radicals trapped in the

glass or measured after melting.

Differences in yields in the solid (anhydrous)

methanol probably reflect differences in macroscopic structure, since regions where the alcohol

is glassy may be produced by rapid freezing even of

anhydrous methanol. This will be especially true

of small diameter sample tubes where more rapid

cooling is obtained.

In glassy methanol G(e~[) — 2.5 and an increased

yield of H2 and glycol is observed if the trapped

electrons are photobleached prior to melting, when

the net decomposition G( — CH3OH) is similar to that observed in the liquid. Much lower yields of

formaldehyde are observed after irradiation of

solid methanol than in the liquid or vapor phase

radiolysis.

12
Table 3. Solid methanol: Product yields (molec. ( 100 eV) *)*

Reference 610014 610020 610020 625003 630220 645001

Polycrystalline or cryst. cryst. cryst. cryst. cryst. glass

glassy? Additive none none none none none h2 o

(‘inert’) h2 3.84 3.60 5% (v/v ?)

(CH2 OH)2 3.31 1.77 ch2 o 0 0.8 CR, 0.51 1.56 CO 0.25 0.33 Others c2 r H2 0

0.10 2.5

G(- CROH) a 7.4 6.4

e r

2.2 e ch2 oh 4.5 e Total radicals 5.5 e 5.0 ± 0.8 e 6.7 e

Radiation b X rays y X rays y or X rays electrons y

200 keV 3 MeV pk. 1.6 MeV

Dose c 10 ~ 200 0.1 to 10 ~ 50 to 300 20 to 150

(1018 eV g

-1

) Dose rate 0.24 3.0 40 0.3 to 0.5 19

(10 15 eV g-1 s"1 ) r(K) q 77 77 77 77 87 to 93 77 Notes See below d See below d

Table 3. Solid methanol: Product yields {molec. (100 eV)-1 )* — Continued

Reference 650204 650218 650230 660609 670110 670110

Polycrystalline or glass cryst. cryst. glass glass cryst. glassy? Additive H2 0 none none h2 o h2 o none

(‘inert’) 5% (v/v?) 2.4% v/v 5 mol %

h2 3.2 f 2.41 ±0.05 3.2±0.1 3.4 2.8

(4.4 ±0.1) g (CH2 OH)2 2. 12 ±0.17 2.9±0.2

(4.1 ±0.2) 8 ch2 o 0.47 ±0.05 0.1 (0. 1 ) 8 ch4 0.15 f 0.34 0.50 1.60

(0.41) 8 CO 0.22 f 0.08 (0.15) 8 0.06 0.08 Others HCO 0.15 e G(-CH3OH) a 6.3 (8.9) 8 «f . 3

e 2.9 ± 0.3 h ch2oh 2

e Total radicals 5

e ’ f 3.8 a

Radiation b y y y y X rays X rays

3 MeV pk. 3 MeV pk. Dose c - 60 to 120 ~~ 300 <50 0.07 to 5 10 to 100 10 to 100

( 1018 eV g

-1

) Dose rate 30 0.7 or 1.2 ~ 8

(10 15 eV g

- 1 s -1

) T (K) q 77 77 77 77 77 77 Notes See below 1

‘Footnotes follow the table.

13
Table 3. Solid methanol: Product yields (molec

.

(100 eV) D - Continued*

Reference 680407 685054 685054 685146 690089 690089 690456 n

Polycrystalline or cryst. glass glass glass cryst. glass

glassy? Additive none H2 0 H2 0 H2 0 H20

(‘inert’) 5.8 mol % 5.8 mol % 5.8 mol % 5.3 mol %

h 2 2.30 2.9 k 2.9 3.2 ±0.1 0

(4.2) 8 (4.4 ±0.1) 8 (CH 2 OH)2 2.84 2.8 2.7 2.9±0.2

(3.9) 8 (4.1 ±0.2) 8 ch2 o 1.48 0.2 0.7 0.1

(0.3) 8 (0.1)

8 ch 4 0.60 0.4

(0.4)

8 CO 0.1

(0.1)

8 Others See below p C(— CH3OH) a 6.4

(8.8)

8 ei

2.61 e 2.22 e 2.3 1 2.7 ± 0.3 r ±0.12 ±0.05

CH2 OH

Total radicals

(6.12 ±0.31

)

(5.14 ±0. 16) e - 8 7.5 e

Radiation b y y (8 y y y y

(3 H/HTO) j Dose c 600 0.8 to 5 0.8 to 5 0.007 to 5

(1018 eV g

-1

) Dose rate 5 0.0043 0.0042 60 3 3 10

(1015 eV g~* s

_1

) T (K) q 77 77 77 77 77 77 77 Notes See below m See below 0

a Calculated as 2 G(glycol) + G(CH4 ) + G(CH2 0) + G(CO).

b All y irradiations use 60 Co source.

c Doses are approximate; 1 eV g

-1 = 1.602 X 10 -16 J kg-1

; where the yields are dose dependent, extrapolation to zero dose is normally

made.

d UV illumination at 77 K after irradiation increased yields of all products.

e By electron spin resonance (ESR).

f Read from figure.

g Yields in parentheses are after photobleaching ef with visible light at 77 K prior to melting.

h Estimated from G(C (NO 2)3") with 0.1 M C(N02 )4 measured at 80 K.

1 Stable products after rapidly melting the sample.

j [680599] also gives the total radical yields (ESR) after 3 H-/3 irradiation (also y and 210 Po-a) but all the samples contained 4 vol %

1 M HNO,. See also [700418] for 210 Po-a

k G(H2 ) increased by ~0.8 if ef thermally bleached at 102 to 104 K prior to melting. ‘From G(H2 ) with I2 or C(N02 )4- G(H)scavengeable 0.5 ( ally1 alcohol); G(H)unscavengeabi e 1.1; G(H2 ) unscavengeab| e 0.3.

n [680370] is a preliminary report of these data.

0 Yields from rapidly melted samples. G(H2 ) increased by 0.2 to 0.6 if slowly warmed without photobleaching.

p Very low G values (~ 0.001 to 0.01) of C2 , C3 and C4 hydrocarbons.

q Temperatures given are those of irradiation; irradiated solids are melted to room temperature to measure the stable products.

r From G(C(N02 )3") measured at ~ 80 K in samples containing C(N02 )4; see also [660609].

14
4. Reaction Rate Parameters

See tables 4.1 to 4.8.

Table 4.1. Hydrogen atom reaction rates in methanol vapor

Reaction(s) H + CH3OH -> H2 + CH2OH

-> H2 + CH3O

H + S —» products

(la) I (lb) J

Method: Application of simple competition kinetics to the decrease in hydrogen yield caused by various concentrations of additive S. Assumes reaction (2) does not produce hydrogen.

Reference S T (K) k2 jk\ Notes

610021 benzene 295 100 ± 20 610021 benzene 295 100 ±20

( k2 lkia

)

With CH3OD (HD yield)

610021 benzene 295 65 ±20

(k2 /k lb ) With CH3OD (HD yield)

650432 ethylene 293 1300 ±200

650432 propylene 293 3000 ±700

670205 propylene room 2700 ± 100 701047 propylene 290 ±2 4300

Table 4.2. Hydrogen atom reaction rates in methanol liquid

Reaction(s) H+CH3OH

H+S

H2 + CH2 OH. . . • - (la)l

• (1) H2 + CH30. . . . products

. . (lb)J

• (2)

Method: As for table 4.1.

Reference S T (K) k2 l k 1 Notes

580003 benzoquinone 292 1730 a 610015 benzoquinone 292 1700 a 580003 FeCla 292 3170 a 610015 FeCla 292 3600 a 610015 diphenyl 292 600

610015 naphthalene 292 940

610015 anthracene 292 4000

610015 benzene 292 140 610015 benzene 195 330 See below b 620067 n-hexane 296 5.6± 1.0 In n-hexane solvent 670030 pyridine room 1900 Data from 660259 c 670030 I2 room 21000

690146 02 296 5800 ±700

a Estimated from graph.

b Estimated that E2 — Ex = 4 kj.

c Also values of k2\k\ for other H atom scavengers, recalculations of data from [610015] using same method as [610015], not original data.

15
Table 4.3. Solvated electron reaction rates in methanol: relative rates

Reaction(s) es + N2 O —* N2 + O ... (3)

e,r + S —» products ... (4)

Method: Application of simple competition kinetics to yield of products from (3) or (4) (generally N2 from (3)) caused by presence of second scavenger S in addition to N2 O. If N2 measured, the product of (4) must not react with N2 O to produce N2 .

4 Reference

fm s T (K) A' 4/^3 Ionic strength

[N2 0](mM) Notes

670018 H

+ room 3.0 a (0.4 to 3) 4 to 6

1 CO X O 670018 H

+ room ~ 4.5 a ’ b 0 4 to 6 670065 H

+ 273 7.9 o

c — 9 or 90 670313 H+ room ~ 11.7 a 0 1 and 50 Read from graph

700947 H

+ room 4.5 0.013 7 to 70 700947 H

+ room -10.1 b 0 7 to 70 Recommended value H+ room 9 ±2 0 670065 Ag + 273 2.4 0

C — 9 or 90 670313 toluene room 5.9 x 10—1 0 0.5 670313 benzene room 2.3X10-3 0 0.5 to 5 670313 fluorobenzene room 5.8x10-3 0 1.0 670313 chlorobenzene room 0.093 a 0 10 670313 acetophenone room 1.9 a 0 1.0 670313 benzonitrile room 2.1 a 0 1.0 670313 benzyl chloride room 0.75 a .0 1.0 670313 acetone room 0.83 a 0 1.0 670313 CC14 room 6.3 a 0 1.0 690456 benzyl chloride 298 0.36 ±0.04 0 10 700064 CH3 Br room 1.5 a 0 0.1 to 2.5 CH4 yield measured d 700064 SFe room 3.2 a 0 2.7 to 181 F“ yield measured d 700064 acetone room 0.57 a 0 See below d ’ e 670313 nitrobenzene room 4.0 a 0 1.0

a N2 0 concentration may have been ~ 18% higher than authors assumed (see [690456] and discussion). This possibility taken into account in recommending values, but not in tabulating authors’ original data or for simple ionic strength corrections to the original data, as on this sheet. This would increase &4 /A3 by ~ 18%.

b Estimated by Reviewer assuming effect of ionic strength on reaction (4) given by the Brpnsted-Bjerrum/extended Debye-Hiickel

treatments (see [670065]).

c Data over full range of ionic strengths.

d Data fitted to Schuler-Asmus-Warman scavenging curve to account for geminate ion scavenging as well as free ions.

e Indirectly compared via SFe (F“ yield).

16
Table 4.4. Solvated electron reaction rates in methanol by pulse radiolysis

Reaction(s) e s +S —> products .... (5)

Method: Direct observation of e$ or product of (5) by pulse radiolysis, usually using optical detection. Kinetic analysis of increased

rate of decay of e$ in presence of S and/or rate of appearance of product. Effects of ionic strength very small.

Reference S T(K) 10- 10 • kstM- 1 s- 1 )

630059 H+ 296 3.9±0.9

630059 o2 296 1.9 ± 0.4 630059 benzyl chloride 296 0.50^=0.12 640080 naphthalene 293 0.2 710064 H+ 298 6.81 ±0.63 b 710644 no3- a room 0.13 710644 no2- a room 0.05±0.01

710644 cich2 co2- a room 0.035 ±0.004

710644 diphenyl room 0.13 -710644 naphthalene room 0.27 710644 acetone room 0.25 717394 N20 room 1.3 c 720062 H+ 293 ±2 5.2 ±0.2

720194 H+ 293 6.5 730292 nitrobenzene 295 2.0 730292 acetone 295 0.42 730292 hexene1

295 1 X 10-5 730292 benzene 295 1 x 10- 4 730292 phenol 295 7x 10-4 730292 c-hexene 295 < 10-6

a Ionic strength effects may have been substantial because of the relatively high concentration of scavenger required. True rate constant may be at least 30% smaller than reported, when extrapolated to zero ionic strength.

b Conductivity method.

c See note a, table 4.3. This value not consistent with A:(e^ + H+

), now known to 20% or better, and the measured ratio

A:(er + H +)/A:(e^ + N20) (see table 4.5).

17
Table 4.5. Solvated electron reaction rates in methanol: Recommended values

Reaction(s) Recommended values for reaction (5): ej + S—» products at room temperature in liquid methanol.

s io- 10

•

k

(M-‘ s- 1 ) b References S 10 10

•

k

{M~ l s" 1 ) References

H+a 5.6±0.8 710064, 720062, C6 H5 COCH3 1.4±0.4 670313

N2 0 0.62±0.16

720194 See table 4.3 c6 h5 no2 2.0 670313, 730292

Ag+ a 1.5±0.5

(cf. to H+

) 670065 (CeHsh -0.13 710644

o2 1.9 ±0.4 630059, 690146 naphthalene 0.2 to 0.3 640080, 710644

sf6 2.3 ±0.8 700064 C6 HsF -0.004 670313

N(V a -0.10 710644 c6 h6 io- 4 ‘ 730292

N(V a -0.03 710644 (690456) CeHsCH, - 0.0004 670313

C1CH2 C02 - a -0.02 710644 (690456) CeHsOH 7X 10- 4 730292

CCb

CH3 Br (CH3 ) 2 CO

c6 h5 ch2 ci C6 H5 CN

C6 H5 C1

4.6± 1.5 0.9±0.3

-0.42

-0.5

1.5 ±0.5

0.07 ±0.02

670313

700064

670313, 700064,

710644, 730292

630059, 670313 c 670313

670313

3 At zero ionic strength. Corrections for ionic strength effects made by reviewer (see [670065]) to data reported in [710644].

b The uncertainties are provided by the reviewer; experience will prove some of them to be optimistic.

c Data in [690456] suggest a lower value.

Table 4.6. Rate of disappearance of solvated and trapped electrons in methanol

Reaction(s) (es )n ~* products (liquid) 1 e~—

products (glass) J

• • ( 6 )

Method: In the liquid, direct observation of e s by pulse radiolysis. In the solid, by observation of the decay of ef by ESR or optical spectroscopy.

Reference Phase T( K) h (s- 1 ) logio A E (kj) Notes

710101 liquid 298 =£ 1.0 X 105 710101 liquid 195 ^ 1.9 X 103 710101 liquid 179 to 333 8.70 ±0.11 20.2 ± 0.5 Max. value of ks (s' 1 ) 650460 glass (5.3 mol % 101 to 105 13.9 ± 1.5 32 ±3

water) (s- 1 ) 675117 solid 3 88 to 98 7.0 (s- 1 ) 20 ±2

a Preparation of e~ by reaction of K with CH3 OH on rotating cryostat. The counter ion is therefore K+ rather than the proton as in radiolysis experiments.

18
Table 4.7. Methyl radical reactions in methanol vapor or solid

Reaction(s) CH3 + CH3OH —* CH4 + CH2OH (7a)l -* CH4 + CH3 0 (7b)J

" ’

Method: Vapor phase: photolysis of acetone or acetone-c?6 - Solid phase: ESR measurement of rate of decay of CH3 and/or rate of growth of CH2 OH.

Reference Reaction and phase T(K) k(M 1 s

1

) logio^ £(kJ) Notes

687279 (7) vapor 413 to 523 8.26 0/- 1 S" 1 )

41 See below3

687279 (7a) vapor (with 413 to 523 8.29 42 CH3 OD) (M~ l s- 1 ) 687279 (7a) vapor (CD3 OH) 408 to 523 8.34 (M- 1 s" 1 )

50

687279 (7b) vapor (CD3 OH) 408 to 523 7.5 (M- 1 s- 1 )

40

637003 (7) solid 77 - 2.2 x 10- 5 670110 (7) solid 77 ~ 3.7X10 - 5 697036 (7) solid 77 ~ 8 x 10- 6 Complex kineticsb 725012 (7) solid (CH3OH/H2O, 1:1)

77 ~ 7 x 10 - 8

725140 (7) solid 77 - 9 x 10 - 5 725140 (7) solid (CH3 OD) 77 ~ 1.1 x 10- 4

J — 3.46 - 3.6 725140 (7) solid (CH3 OD) 67 - 4.5 x 10

- 5

a See references in this paper for further work on vapor phase reactions.

b Data for full range of methanol-water mixtures. Considerable effect of matrix.

Table 4.8. Rates of reactions of other transients in methanol liquid

Reaction(s) Other reactions in methanol

Method: Pulse radiolysis. Usually, direct observation of optical absorption of reactant or product.

Reaction Kinetic parameters Reference

Ar- + CH3 OH -*• ArH + CH3 OAr = diphenyl

.... ( 8 ) k8 = (6.9 ± 1.2) X 104 Tkf- 1 s - 1 at 298 K. 640084 Ar = anthracene *8 = (8.1 ± 2.0) X 104 M- 1 s “ 1 at 298 K. 640084 Ar — p-terphenyl k8 = (4 ± 1) X 102 A/ _ 1 s _1

at 298 K. 640084 Ar = anthracene k8 = 3.7 X W-expiS.SkJIRT^M-'s- 1 670188 Ar = diphenyl k8 — 6.2 X 106 • exp(— 1

1

.3k]/RDM “ 1 s _ 1 670188

CH3 O- + CH3 OH2 + -»> 2 CH3 OH ... (9) k9 = (7.1 ± 0.3) X 1010 A/ _ 1 s _1

at 298 K. 7100643

2 ej —> products .... ( 10 )

Eg = 12.6 ± 0.6 kj

kio = (3.3 ± 2) X 109 M- 1 s _1 in CH3 OD at 298 K

7100643 719165b ch3 o + s-> ch3 o- + s

+ • • (ID knlk 12 = (1.4 ± 0.1) X 104 at ~ 293 K 720115 CH3 O + CH3 OH ->'CH3 OH + CH2 OH ... ( 12 ) S=I-orTMPD c CH3 O + TMPDC -»> CH3 O- + TMPD + (13) k 13 = (6.10 ± 0.05) X lOW-^- 1 at ~ 293 K 720122

k n — 3.7 X 109M- 1 s- 1 (S= I') at- 293 K

k 12 = ( 2.63 ± 0.1) X 105 M_ 1 s _1 720122

a By conductivity measurements.

b Theoretical treatment of evolution of hydrogen from the dissolution of sodium in methanol.

c N, A

T,V,W,'-tetramethyl-p-phenylene diamine.

19
5. Spectroscopic Parameters

5.1. Optical Absorption of Trapped Electrons in Methanol Glass

See table 5.1

Table 5.1. Spectroscopic parameters of et in CH3OH glass

Reference T (K) additive ^max(nm) a W1/2 (+) b W1/2 (-) c (eV) (eV)

10-4 Ge d Notes

620028 77 2 M CH3 ONa 540

650298 77 496 0.68 0.35 650460 80 H2 0 533 3.46

5.3 mol %

660188 77 n- propanol 520

4 vol. %

660609 80-85 h2 o 526 0.64 0.36 3.0 See also [690456]

5.3 mol % ±Jh04^±J103 ^ ±0.3

670230 77 h2 o 514 0.83 Also data for 30 to 70 mol %

10 mol % water

670651 77 513 ^TSToT^T Data for CH3 OD in parentheses

(518) (0.99) 685130 77 isopropanol 521

1 mol %

700096 80 h2 o 528 0.74 0.36 3.17

5.8 mol % ± 0.01 ± 0.01 ±0.07

700096 80 NaOCH3 541 0.74 0.38 . 3.65

(1 M)

710091 e 4.2 H2 0 605 1.5 Also data for 4-80 K.

5 mol %

720145 77 h2 o 520 Also data for 25 and 60% water. 5 mol %

720428 77 none 519

3 Wavelength of maximum absorption.

b Energy separation between A. max and half-height on high energy side of A max . c Energy separation between A. max and half-height on low energy side of A max . d Units are M-1 cm -1 (100 eV) _1

. Product of G and € at absorption maximum.

e For data for methanol/ethanol mixtures at 4 K see [710526].

20
5.2. Optical Absorption of Solvated Electrons in Methanol Liquid

See table 5.2.

Table 5.2. Spectroscopic parameters of e$ in liquid methanol

Reference T (K) additive ^max (nm) W1/2 (+) a W1/2 (-) a (eV) (eV)

10 -4Ge

(fi) 10 -4Ge(gi) Notes a,b

640113 -295 none 1.1 ±0.1

(546 nm)

640080 -295 none 650 0.93 d 0.33 d 1.39 650499 -295 none 630 0.78 d 0.48 d 1.9 650397 -295 none 630 d P.88_? 04I

d See below e 660082 195 none 580 d 25^

700246 -295 -0.1 M Nal 730 d 0.2 d 0.2 d 710101 293 none 1.79 ±

0.11

0.43

710101 187 none 1.83 ± 1.94 ±

0.11 0.2 710727 -295 none 640

720197 183 none 557 0.69 d 0.43 d 1.9 (176 K)

720197 294 none 635 0.87 d 0.43 d 1.9 720197 358 none 710

720197 423 none 1.9 720293 303 none 640

720437 -295 none 640 L23~± 0.04

a See footnotes on table 5.1 for definition of symbols.

b

fi = free ions; gi= geminate ions (see discussion). Ge product at A max unless stated.

c Also data for solutions containing CH3 0

- or OHd Estimated from figure.

e Also data for mixtures of methanol with tetrahydrofuran or cyclohexane.

5.3. Optical Absorption of CH2OH and

CH30 in Methanol

Few quantitative studies have been reported;

there are some difficulties in interpretation and

recommended data cannot be given. In irradiated glassy methanol, an absorption in

the ultra-violet remains after photobleaching the

trapped electrons, but the absorption at ca. 200 nm

does not change significantly during photobleaching ([690456]; an earlier report to the contrary

[640080] has' not been substantiated [700096]).

Since the ESR signal of CH2 OH increases considerably during photobleaching, positive assignment of this UV absorption wholly to CH2 OH

cannot be made [690456].

A similar UV absorption has been reported in

liquid methanol after pulse radiolysis [690456,

690419], and at times longer than ca. 1 /as (when

CH3O has completely decayed [720122]) this can

confidently be ascribed to CH2 OH. The early spectrum reported with Xmax = 290 nm appears to be

erroneous [640080]. Data for the Ge product and decay constant k/e have been reported [690456,

690418] for CH2 OH in liquid methanol and aqueous

methanol solutions. The latter studies permit

estimation of the extinction coefficient. With

0.5 M methanol in water saturated with N2 O,

Ge(CH2 OH) = (1.8 ± 0.2) X 103 M'cm"1 (100

eV) _1at 300 nm [690456], giving e = 250 ± 40 M~ l cm-1

at 300 nm if G(OH) = 7.3 in this solution.

The data read from the graph in [690418] appear

not inconsistent with this estimate, but the as- sumed G(0H) was not reported.

The possibility of an absorption ascribable to CH3O at times shorter than 1 /as in pulse-irradiated

liquid methanol has been explored [720122] but

it was concluded that the absorption spectra of

CH2 OH and CH3O may be similar.

21
5.4. Electron Spin Resonance Parameters

for e~ and CH2OH in Irradiated Solid

Methanol

In irradiated solid (glassy) methanol the ESR

absorption of e t~ is difficult to establish precisely

because of the underlying signal from CH2 OH. The

line shape may be characterized by the parameter

AHms , the line width between points of maximum

slope on the absorption curve. Values of AHms for

ef range from 1.1 mT (11 gauss) 8 to 2.0 mT [625001,

645001, 685088, 685130, 695078]. Electrons trapped

in solid methanol on the rotating cryostat by reaction

of K atoms with methanol (there being no CH2 OH to obscure the spectra) have AHms = 1.12 ±0.1 mT and

2.0018 at 77 K [675117].

The CH2 OH radical is observed in irradiated polycrystalline or glassy methanol, with line shape characteristic of a CH2 X species with restricted rotation

and anisotropic proton hyperfine coupling. In solids

the average splitting is often reported, presumably

(Ah + 2A ±)/3. An average coupling A ch2 = 1-8 mT is observed [585000, 625001, 640080, 650230] with

g= 2.001 [585000]. In solution the CH2OH radical is well characterized, e.g. from the photolysis of hydrogen peroxide in liquid methanol, Aqh2 ~ 1.784 to 1.726 mT, 4qH = 0.175 to 0.100 mT, and g= 2.00333

in methanol at 223 to 314 K [660840].

The radical CH2 0~ has been reported in solid

alkoxides [645013] with /1 ch2 =

\

^ mT- In sulfuric acid glass theCIkOtk radical has been

identified, with AqH2 = 2.22 mT and AqH2 = 0.5 ± 0.1

mT [695130].

Acknowledgement

Dr. Alberta B. Ross of the Radiation Chemistry

Data Center made the compiling of this review much

less of a chore than such things usually are by maintaining a continuous supply of relevant data and

references. For this and the other ways in which she

has been helpful, we are extremely grateful.

References

[530004] The decomposition of methanol-C 14 under the in- fluence of its own radiation. Skraba, W. J.; Burr,

J. G. Jr.; Hess, D. N. J. Chem. Phys. 21: 1296 (1953).

1 gauss corresponds to 10 4 tesla.

[540005] The radiation chemistry of the aliphatic alcohols. McDonell, W. R.; Newton, A. S. J. Amer. Chem.

Soc. 76: 4651-8(1954).

[550003] Decomposition of methyl alcohol by Co60 gamma radiation. McDonell, W. R.; Gordon, S. J. Chem. Phys. 23:

208 (1955). [570027] Decomposition of methyl alcohol by Co60 gamma rays. Yizuka, Y.; Ouchi, Y.; Hirota, K.; Kusumoto, G. Nippon

Kagaku Zasshi 78: 129-31 (1957). [580003] Radical and molecular yields in the y-irradiation of

liquid methanol. Adams, G. E.; Baxendale, J. H. J. Amer. Chem. Soc. 80 : 4215-19 (1958). [580005] Radiolysis of liquid methanol by Co60 gamma-radiation.

Meshitsuka, G.; Burton, M. Radiat. Res. 8(4): 285-97

(1958). [580026] Ferric chloride as a radical scavenger in the radiolysis of organic compounds. Cherniak, E. A.; Collinson, E.; Dainton, F. S.; Meaburn, G. M. Proc. Chem. Soc.: 54

(1958). [585000] Electron resonance studies of the change in free radical spectra of solid alcohols with variation of temperature

and time of U.-V. irradiation. Fujimoto, M.; Ingram,

D. J. E. Trans. Faraday Soc. 54: 1304—15 (1958). [590017] Radiolysis of methanol and methanolic solutions by

Co60 y-rays and 1.95 X 106 volt Van de Graaff electrons. Lichtin, N. N. J. Phys. Chem. 63: 1449—54 (1959). [590020] Some radical and molecular yields in the y-irradiation of some organic liquids. Adams, G. E.; Baxendale,

J. H.; Sedgwick, R. D. J. Phys. Chem. 63: 854-58

(1959). [590029] Tetranitromethane as a radical scavenger in radiation chemical studies. Henglein, A.; Langhoff, J.; Schmidt,

G. J. Phys. Chem. 63: 980 (1959). [600011] Radiolysis of organic liquids containing dissolved ICN.

Hughes, G.; Garrison, W. M. J. Phys. Chem. 64: 695-6

(1960).

[604001] Radiolysis of methanol by recoils from the B

10 (n, a) Li7 reaction. Choi, S. U.; Lichtin, N. N.; Rush, J. L. J. Amer. Chem. Soc. 82: 3225 (1960).

[610014] The chemical action of ionising radiations on simple ali- phatic alcohols. Part II. Irradiation of methanol in the absence and in the presence of oxygen in the solid and

in the liquid state. Hayon, E.; Weiss, J. J. J. Chem. Soc.: 3970-3 (1961).

[610015] The y-radiolysis of methanol and methanol solutions. Baxendale, J. H.; Mellows, F. W. J. Amer. Chem. Soc. 83: 4720-26 (1961).

[610020] The photolysis of trapped free radicals produced by

ionizing radiation. Johnsen, R. H. J. Phys. Chem. 65:

2144-7 (1961).

[610021] Radiolysis of methanol vapour. Baxendale, J. H.; Sedgwick, R. D. Trans. Faraday Soc. 57(12): 2157-66

(1961).

[610027] Radiolysis of liquid methanol — Inhibitory effects of

additives. Brown, W. G.; Eberhardt, M. K. ARL 90, Nov., 1961, 17p. (Aeronautical Res. Lab., Univ. of Chicago).

[610029] The production of chemicals from reactors. Part. V. Ethylene glycol from the pile (n + y) and fission fragment

irradiation of liquid methanol. Landsman, D. A.; Butterfield, J. E. AERE-R 3625, Apr. 1961, 25p. (Atomic

Energy Res. Establ., Harwell).

22
[620028] Solvated electrons in frozen solutions. Schulte- Frohlinde, D.; Eiben, K. Z. Naturforsch. Pt. A 17: 445-6

(1962).

[620067] The reactivity of hydrogen atoms in the liquid phase. II. The reaction with some organic solutes. Hardwick, T. J.

J. Phys. Chem. 66: 117-25 (1962).

[625001] On the radiation stability of solid organic compounds.

Voevodskii, V. V.; Molin, Yu. N. Radiat. Res. 17:

366-78 (1962).

[625003] Electron paramagnetic resonance study of radiation- induced-oxidation-reduction mechanisms. Larin, V. A.; Grishina, A. D.; Bakh, N. A. Proc. Acad. Sci. USSR,

Phys. Chem. Sect. 42(4): 113-6 (1962); translated from

Dokl. Akad. Nauk SSSR 142(4): 847-50 (1962).

[630056] The radiolysis of methanol and methanolic solutions.

II. Comparison of radiolysis by Co60 y-rays and by

B

10 (n,a) Li7 recoils. Imamura, M.; Choi, S. U.; Lichtin, N. N. J. Amer. Chem. Soc. 85: 3565-70 (1963). [630059] Pulse radiolysis studies of the reactivity of the solvated

electron in ethanol and methanol. Taub, I. A.; Sauer, M. C. Jr.; Dorfman, L. M. Discuss. Faraday Soc. 36:

206-13 (1963). [630060] Radiolysis of liquid methanol and some methanolic

salt solutions. Theard, L. M.; Burton, M. J. Phys.

Chem. 67 : 59-64(1963).

[630063] The y-radiolysis of water vapour. Baxendale, J. H.;

Gilbert, G. P. Discuss. Faraday Soc. 36: 186-92 (1963). [630220] Sil, K. K.; Zimin, A. V.; Sharpatyi, V. I.; Khimicheskaya

Promyshlennost 7 : 492—5 (1963) [637003] The photochemical decomposition of alcohols at low

temperatures: The kinetics of the decomposition of methyl alcohol. Shelimov, B. N.; Fok, N. V.; Voevodskii,

V. V. Kinetics Catalysis (USSR) 4(4): 473-80 (1963); translated from Kinet. Katal. 4(4): 539-48 (1963). [640080] Pulse radiolysis and matrix isolation data for methanol

and 2-methyltetrahydrofuran (MTHF). Dainton, F.S.; Keene, J. P.; Kemp, T. J.; Salmon, G. A.; Teply, J. Proc. Chem. Soc.: 265-6 (1964). [640084] Pulse radiolysis studies. VI. The lifetimes of aromatic

anions in the aliphatic alcohols. Arai, S.; Dorfman, L. M.

J. Chem. Phys. 41(7): 2190-4 (1964). [640113] Pulse radiolysis studies. IV. The solvated electron in the ahphatic alcohols. Taub, I. A.; Harter, D. A.; Sauer, M. C. Jr.; Dorfman, L. M. J. Chem. Phys. 41(7): 2190-4

(1964). [640121] The radiolysis of methanol and methanohc solutions.

III. The effect of oxygen on the radiolysis of hquid

methanol by 60 Co y-rays and by 10 B(n,a)7 Li recoils. Choi, S. U.; Lichtin, N. N. J. Amer. Chem. Soc. 86:

3948-53 (1964). [640154] Production of hydrogen in the radiolysis of methanol

vapour. Meaburn, G. M.; Mellows, F. W.; Reiffsteck,

A. Nature (London) 204: 1301-2 (1964). [640155] Free-radical yields in n-alcohols resulting from yirradiation. Zwiebel, I.; Bretton, R. H. A.I.CH.E. (Am. Inst. Chem. Eng.) J. 10(3): 339—44 (1964). [640166] Radiolysis of methanol by 10 B(n,a) 7 Li recoils. Effect of linear energy transfer on the radiolysis of methanol. Imamura, M. NP-tr-1577, Nov. 17, 1967, 28p.; trans- lated from Rika Gaku Kenkyusho Hokohu 40: 176-84

(1964).

[645001] Etude par resonance parmagnetique electronique des

electrons et des radicaux pieges dans les alcools irradies par les rayons y a 77 °K. Chachaty, C.; Hayon, E. J. Chim. Phys. 61: 1115-28 (1964).

[645013] Electron spin resonance spectra of y-irradiated alkoxides. Bennett, J. E. Nature 203: 514-5 (1964).

[650187] The effect of nitrous oxide on the y-radiolysis of hquid

methanol. Seki, H.; Imamura, M. Bull. Chem. Soc. Japan 38: 1229 (1965).

[650204] The mechanism of the nonadditive formation of radicals

in the radiolysis of frozen solutions of CCI4 + CH3OH.

Roginskii, V. A.; Kotov, A. G.; Pshezhetskii, S. Ya.

Dokl. Phys. Chem., Proc. Acad. Sci. USSR 163 : 625-8

(1965); translated from Dokl. Adad. Nauk SSSR 163:

1433-6 (1965).

[650218] Formation of free radicals under the action of y-radiation

in frozen methanol-carbon tetrachloride mixtures.

Roginskii, V. A.; Kotov, A. G.; Pshezhetskii, S. Ya. Russ. J. Phys. Chem. 39: 1544-7 (1965); translated from Zh. Fiz. Khim. 39: 2892-5 (1965).

[650230] Radiolysis of pure methanol. Teply, J.; Habersbergerova. A.; Vacek, K. Collect. Czech. Chem. Commun.

30: 793-801 (1965).

[650298] Unstable intermediates. Part XXX. Solvated electrons: Line shapes of electronic absorption bands. Blandamer, M. J.; Shields, L.; Symons, M. C. R. J. Chem. Soc.: 3759-62 (1965).

[650397] Some aspects of the quenching of excited states formed

in pulse radiolysis. Kemp, T. J.; Salmon, G. A.; Wardman, P. Pulse Radiolysis, Ebert, M.; Keene, J. P.; Swallow, A. J.; Baxendale, J. H. (eds.). Academic Press, New York, 1965, p.247-57.

[650432] Effect of hydrogen atom and electron scavengers on the

radiolysis of methanol vapour. Meaburn, M.; Mellows,

F. W. Trans, Faraday Soc. 61: 1701-8 (1965).

[650460] The radiation chemistry of low temperature methanohc

glasses. Dainton, F. S.; Salmon, G. A.; Teply, J. Proc. Roy. Soc. (London) Ser. A 2 86 : 27-44 (1965). [650499] Pulse radiolysis studies. VII. The absorption spectra

and radiation chemical yields of the solvated electron

in the aliphatic alcohols. Sauer, M. C. Jr.; Arai, S.; Dorfman, L. M. J. Chem. Phys. 42(2): 708-12 (1965). [650501] Electron capture by solutes in the radiolysis of methanol

and ethanol. Hayon, E.; Moreau, M. J. Phys. Chem.

69 : 4053-7 (1965).

[650507] Gamma radiolysis of methanol. Ladygin, B. Ya.; Saraeva, V. V. Kinetics Catalysis (USSR) 6: 189-95 (1965);

translated from Kinet. Katal. 6(2): 221-8 (1965). [650773] y-ray-induced oxidation of Hquid methanol. Imamura,

M.; Seki, H. Sci. Papers Inst. Phys. Chem. Res. (Tokyo) 59(3): 146—51 (1965). [660013] Radiolysis of binary mixtures. I. Liquid phase studies with benzene-methanol. Ekstrom, A.; Garnett, J. L.

J. Phys. Chem. 70(2): 324-30 (1966). [660082] Absorption spectra of the solvated electron in polar

liquids: Dependence on temperature and composition

of mixtures. Arai, S.; Sauer, M. C. Jr. J. Chem. Phys.

44(6): 2297-305 (1966). [660188] Molecular ions in radiation chemistry. V. Intermediates

in y-irradiated glassy solutions of methanol. Shida, T.; Hamill, W. H. J. Amer. Chem. Soc. 88(16): 3689-94

(1966).

23
[660259] Localization of energy in radiolysis of solutions. IV. Hydrogen yields in binary mixtures of methanol, water, and pyridine. Schweiner, Z.; Janovsky, I.; Bednar, J. Collect. Czech. Chem. Commun. 31: 43-50 (1966). [660260] Mechanism of the hydrogen formation in the radiolysis of low temperature methanolic glasses. Teply, J.; Janovsky, I. UJV-1739, 1967, 31p. (Czechoslovakia

Acad. Sci.) [660609] Radiolysis of glassy methanol and n-propanol at 77 °K. Dainton, F. S.; Salmon, G. A.; Wardman, P.; Zucker, U.

Proc. of the Second Tihany Symposium on Radiation

Chemistry, Dobo, J.; Hedvig, P. (eds.), Publishing House

of the Hungarian Acad, of Sci., Budapest, 1967, p.247-

56. [660840] Paramagnetic resonance study of liquids during photolysis: Hydrogen peroxide and alcohols. Livingston, R.; Zeldes, H. J. Chem. Phys. 44(3): 1245-59 (1966).

[670018] Radiolysis yields from y-irradiated liquid methanol containing nitrous oxide and the effect of acid. Seki, H.; Imamura, M. J. Phys. Chem. 71(4): 870-75 (1967).

[670030] Hydrogen formation in the radiolysis of liquid methanol

and ethanol. Teply, J.; Habersbergerova, A. Collect. Czech. Chem. Commun. 32: 1350-8 (1967).

[670044] Radiolysis of methanolic solutions of nitrous oxide. Teply, J.; Habersbergerova, A. Collect. Czech. Chem.

Commun. 32: 1608-10 (1967).

[670065] Kinetic salt effects on reactions of the solvated electron

in methanol. Buxton, G. V.; Dainton, F. S.; Hammerli, M. Trans. Faraday Soc. 63(533): 1191-1197 (1967).

[670071] Effect of temperature on the y-radiolysis of methanol

vapour. Anderson, A. R.; Lea, C. W. PR/CHEM 12, 1967, p.2-3. (Progress report, AERE, Harwell)

[670110] Ultraviolet photolysis of X-irradiated methanol at 77 °K.

Milliken, S. B.; Johnsen, R. H. J. Phys. Chem. 71(7):

2116-23 (1967).

[670188] Pulse radiolysis studies XI. Protonation reactions of aromatic anions in some aliphatic alcohols. Arai, S.; Tremba, E. L.; Brandon, J. R.; Dorfman, L. M. Can. J. Chem. 45: 1119-23 (1967).

[670205] Effect of electric fields on gamma radiolysis of methanol

vapor. Ohmae, T.; Sakurai, H. Bull. Chem. Soc. Japan

40(6): 1368-72 (1967).

[670230] Nature of electron capture in the radiolysis of polar sys- tems. Ershov, B. G.; Makarov, I. E.; Pikaev, A. K. High

Energy Chem. 1(5): 414-20 (1967); translated from

Khim. Vys. Energ. 1(5): 472-9 (1967).

[670313] Light-induced and radiation-induced reactions in methanol. I. y-Radiolysis of solutions containing nitrous

oxide. Sherman, W. V. J. Phys. Chem. 71(13): 4245-55

(1967). [670651] Radiolysis of methanol in the glassy state. Kosa- Somogyi, I.; Balog, J.; Vertessy, Z. Magy. Kem. Foly.

73(12): 554-61 (1967). [674005] Effect of nitrous oxide on the radiolysis of liquid

methanol with the recoils from the 10 B(n,a) 7 Li reaction. Imamura, M.; Seki, H. Bull. Chem. Soc. Japan 40:

1116-8(1967).

[675117] Trapped electrons produced by the deposition of alkali- metal atoms on ice and solid alcohols at 77 °K. Part II. Chemical reactions during thermal and photolytic

bleaching. Bennett, J. E.; Mile, B.; Thomas, A. J. Chem. Soc. Pt. A (9): 1399-403 (1967).

[680140] Irradiation of methanol with 60 Co y-rays and 4 He ions. Burns, W. G.; Reed, C. R. V. PR/CHEM 14., p. 3-4.,

1 Nov. 1967-30 Apr. 1968. (Progress report, AERE,

Harwell)

[680167] Isotopic compositions of the hydrogen produced from

liquid methanol-di by irradiation of 60 Co y rays and of the 10 B(n,a)7 Li recoil particles. Seki, H.; Imamura, M.

J. Chem. Phys. 48(4): f&66-7 (1968). [680370] Processes in y-irradiated methanol glass. Dainton, F. S.; Salmon, G. A.; Wardman, P. Chem. Commun. (19): 1174-6(1968).

[680397] Irradiation of liquid methanol in the presence of anthra- cene and with radiation-of varying L.E.T. Burns, W. G.; Reed, C. R. V. PR/CHEM 15, p.2-3, 1968. (Progress

report, AERE, Harwell).

[680407] Radiolysis of binary mixtures. Part II. The effect of

irradiation temperature on the radiolysis yields of methanol in benzene. Ekstrom, A ; Garnett, J. L.

J. Chem. Soc. Pt. A: 2408-12 (1968). [680594] y-Radiolysis of a binary mixture of methanol and water. The formation of formaldehyde in the radiolysis of

liquid methanol. Seki, H.; Nagai, R.; Imamura, M.

Bull. Chem. Soc. Japan 41(12): 2877-82 (1968). [680599] The influence of linear energy transfer (LET) on the radi- cal yields in frozen organic systems. Czerwik, Z.; Kroh,

J.; Piekarska, A.; Wypych, M. Bull. Acad. Pol. Sci. Ser.

Sci. Chim. 16(10): 527-30 (1968).

[680610] I. Kinetics of reactions of electrons during radiolysis of liquid methanol. II. Reaction of electrons with liquid alcohols and with water. Jha, K. N.; Freeman, G. R. J. Chem. Phys. 48(12): 5480-90 (1968).

[685054] Comparison of the yields of paramagnetic species in radiolysis of glassy methanol by /3 and y radiation. Habersbergerova, A. Collect. Czech. Chem. Commun.

33: 1925-29 (1968).

[685088] Spatial distribution of trapped electrons in gammairradiated organic glasses. Kevan, L.; Chen, D. H. J. Chem. Phys. 49: 1970-1 (1968)

[685130] Effects of matrix polarity on the optical and electron

spin resonance spectra of trapped electrons in organic

glasses. Ekstrom, A.; Willard, J. E. J. Phys. Chem.

72(13): 4599-4603 (1968).

[685146] EPR spin-echo investigation of free radical distribution

in irradiated organic matrices. Tsvetkov, Yu. D.; Rait- simring, A. M.; Zhidomirov, G. M.; Salikhov, K. M.; Voevodsky, V. V. Khim. Vys. Energ. 2(6): 529-35

(1968); translation in High Energ. Chem

[687279] Methyl radical reactions with isopropanol and methanol,

their ethers and their deurated derivatives. Gary, P.; Herod, A. A. Trans. Faraday Soc. 64(10): 2723-34

(1968).

[690045] Evidence for the production ot an oxidising radical on

pulse-radiolysis of methanol. Dainton, F. S.; Janovsky,

I. V.; Salmon, G. A. Chem. Commun. (7): 335-6 (1969).

[690089] The radiolysis of alcohols at low temperatures — I. The

precursors of hydrogen in glassy methanol. Teply, J.; Janovsky, I. Int. J. Radiat. Phys. Chem. 1: 119-31

(1969).

[690146] The radiolysis of methanol and methanolic solutions. V. The acid effect. Suryanarayanan, K.; Lichtin, N. N. J. Phys. Chem. 73(5): 1384-91 (1969).

24
[690391] Radiation chemistry of alcohols, ethers and ketones in condensed states. Teply, J. Radiat. Res. Rev. 1(4): 361-410 (1969). [690419] Pulse radiolysis of alcohols in aqueous solution. Simic, M.; Neta, P.; Hayon, E. J. Phys. Chem. 73(11): 3794-

800 (1969). [690456] The radiation chemistry of liquid and glassy methanol.

Dainton, F. S.; Salmon, G. A.; Wardman, P. Proc. Roy. Soc. Ser. A 313: 1-30 (1969). [690736] Radiation chemistry of frozen polar systems. Kevan,

L. Actions Chim. Biol. Radiat. 13: 57-117 (1969). [695078] Paramagnetic relaxation of trapped electrons in gammairradiated organic glasses. Chen, D. H.; Kevan, L. Mol.

Cryst. 6 : 183-96 (1969). [695130] Unstable intermediates. Part LXV. Electron spin resonance studies of radicals derived from protonated

alcohols by y-irradiation: The radicals R2 COH^.

Brimage, D. R. G.; Cassell, J. D. P.; Sharp, J. H.; Symons, M. C. R. J. Chem. Soc. Pt. A (17): 2619-21

(1969). [697036] Decay kinetics of the methyl radical produced by ultra- violet irradiation of methanol-water matrices at 77 °K. Morgan, C. U. J. Amer. Chem. Soc. 91(7): 1599-1602

(1969). [700064] Electron scavenging in y-irradiated liquid methanol and

ethanol. Rzad, S. J.; Fendler, J. H. J. Chem. Phys.

52(10): 5395-403 (1970). [700096] Radiolysis of alcohols at low temperatures. Part 3. Spectrophotometric investigation of trapped electrons and other species formed by gamma-irradiation in glassy methanol. Habersbergerova, A.; Josimovic,

Lj.; Teply, J. Trans. Faraday Soc. 66 : 656—68 (1970). [700239] The radiolysis of alcohols. Freeman, G. R. Actions

Chim. Biol. Radiat. 14: 73-134 (1970). [700246] Pulse radiolysis studies of deaerated alcoholic solutions

of alkali halides and potassium hydroxide. Arai, S.; Kira, A.; Imamura, M. J. Phys. Chem. 74(10): 2102-7

(1970). [700360] Yield of ions and excited states produced in the radiolysis of polar organic liquids. Hayon, E. J. Chem. Phys.

53(6): 2353-8 (1970).

[700418] Study of the steric distribution of radicals in the a- and

y-radiolysis of methanol and an aqueous solution of H2 SO4 at 77 °K by the electronic spin echo method.

Raitsimring, A. M.; Moralev, V. M.; Tsvetkov, Yu. D. High Energy Chem. 4(2): 157-8 (1970); translated from

Khim. Vys. Energ. 4(2): 180-2 (1970).

[700947] The gamma-radiolysis of methanol. Pinkerton, D. M. AERE-R 6541, 1970, 36p. (Atomic Energy Res. Establ., Harwell).

[701014] The comparison of the radiolysis mechanism in gaseous and liquid methanol. Teply, J. Progress and Problems in Contemporary Radiation Chemistry, Teply, J., Fojtik, A.. Habersbergerova, A., Janovsky, I., Prasil, Z., Santar, I., Spurny, F. (eds.), Vol. III. Prague, 1971, p.505-8. (Proc.

of the 10th Czechoslovak Ann. Meeting on Radiation

Chemistry, June 22-25, 1970).

[701047] Mechanisms of hydrogen formation in the radiolysis of gaseous CH3OH and CD3 OH. Klosova, E.; Teply, J.; Prasil, Z. Int. J. Radiat. Phys. Chem. 2(4): 177-86

(1970).

[710064] Pulse radiolytic induced transient electrical conduct- ance in liquid solutions. Part 4. The radiolysis of methanol, ethanol, 1-propanol and 2-propanol. Fowles, P. Trans. Faraday Soc. 67(2): 428-39 (1971).

[710091] Electronic spectra of trapped electrons in organic

glasses at 4 °K. Hase, H.; Noda, M.; Higashimura, T. J. Chem. Phys. 54(7): 2975-8 (1971).

[710101] Yields and decay processes of the solvated electron in liquid alcohols at low temperature observed by nano- second pulse radiolysis. Baxendale, J. H.: Wardman, P. Chem. Commun. (9): 429-30 (1971).

[710458] Pressure shifts in properties of solvated electrons in alcohols and water. Robinson, M. G.: Jha, K. N.; Free- man. G. R. J. Chem. Phys. 55(10): 4933-5 (1971).

[710526] Electronic spectra of trapped electrons in organic

glasses at 4°K. II. Ethanol-methanol mixtures. Hase. H.; Noda, M.; Higashimura, T. J. Chem. Phys. 55(11):

5411-2 (1971).

[710644] Reactive capacity of the solvated electron in irradiated methyl alcohol. Pikaev, A. K.; Sibirskaya, G. K.; Kabakchi, S. A., Dokl. Phys. Chem., Proc. Acad. Sci. USSR 198(4-6): 554-7 (1971): translated from Dokl. Akad. Nauk SSSR 198(6): 1374-7 (1971). [710727] Effect of KOH on the kinetics of the disappearance of solvated electrons in irradiated methyl alcohol. Pikaev.

A. K.; Sibirskaya, G. K.; Kabakchi. S. A. High Energy

Chem. 5(5): 422-3 (1971); translated from Khim. Vys.

Energ. 5(5): 470-2 (1971) [717394] The reactions of photogenerated solvated electrons in methanolic solutions of potassium iodide. Seki, H.; Imamura, M. Bull. Chem. Soc. Japan 44(6): 1538-43

(1971). [719165] Production of electrons by reaction of sodium with methanol and ethanol: Kinetics of their formation and

subsequent reactions. Fletcher, J. W.; Richards, P. J. Can. J. Chem. 49(13): 2275-82 (1971). [720062] Rate of reaction of solvated electrons with hydrogen

ions in methanol. Baxendale, J. H. Int. J. Radiat. Phys.

Chem 4(1): 113-5(1972).

[720115] The radiation chemistry of liquid methanol. I. The

oxidizing radical. Dainton, F.; Janovsky, I.; Salmon,

G. A. Proc. Roy Soc. (London) Ser. A 3 2 7 : 305-16

(1972). [720122] Nanosecond pulse radiolysis of methanolic and aqueous

solutions of readily oxidizable solutes. Ellison. D. H.; Salmon, G. A.; Wilkinson, F. Proc. Roy. Soc. (London)

Ser. A 328: 23-36(1972).

[720145] The trapping efficiency for electrons in polar glasses

at 77 °K. Sawai, T.; Shinozaki, Y.; Meshitsuka, G.

Bull. Chem. Soc. Japan 45(4): 984-7 (1972). [720194] Solvent structure effects and diffusion control in the

reaction between solvated electrons and solvated pro- tons in alcohols and water. Jha, K. N.; Bolton, G. L.; Freeman, G. R. Can. J. Chem. 50(18): 3073-5 (1972). [720197] Temperature shifts in the optical spectra of solvated

electrons in methanol and ethanol. Jha, K. N.; Bolton, G. L.; Freeman, G. R. J. Phys. Chem. 76(25): 3876-83

(1972). [720293] Optical absorption of solvated electrons in alcohols and their mixtures with alkanes. Hentz, R. R.; KenneyWallace, G. J. Phys. Chem. 76(20): 2931-3 (1972).

25
[720428] Electron absorption spectra of excess electrons in molecular aggregates. I. Trapped electrons in y-irradi- ated amorphous solids at 77 °K. Shida, T.; Iwata, S.; Watanabe, T. J. Phys. Chem. 76(25): 3683-91 (1972).

[720437] Solvated electrons in irradiated concentrated alkaline methanol and water-methanol mixtures. Pikaev, A. K.; Zhestkova, T. P.; Sibirskaya, G. K. J. Phys. Chem.

76(25): 3765-71 (1972).

[720441] Precise measurements of W, the average energy

required for ion pair formation. II. Alcohols and water. Meisels, G. G.; Ethridge, D. R. J. Phys. Chem. 76(25):

3842-6 (1972).

[725012] The thermal growth of the formyl radical at 87 °K in a 50% methanol-water matrix. Morgan, C. U. J. Phys.

Chem. 76(4): 494-6 (1972).

[725140] Hydrogen atom abstraction by methyl radicals in methanol glasses at 67-77 °K. Campion, A.; Williams, F.

J. Amer. Chem. Soc. 94(22): 7633-7 (1972).

[725141] Electron spin resonance studies of radical trapping in the radiolysis of organic liquids. I. Evidence for the pri- mary formation of the methoxy radical in methanol. Wargon, J. A.; Williams, F. J. Amer. Chem. Soc. 94(22):

7917-8 (1972).

[730042] Ionic yields in methanol measured by conductometric

pulse radiolysis. Lilie, J.; Chaudhri, S. A.; Mamou, A.; Graetzel, M.; Rabani, J. J. Phys. Chem. 77(5): 597-600

(1973).

[730087] Electrons in liquid alcohols at low temperatures. Baxendale, J. H.; Wardman, P. J. Chem. Soc. Faraday Trans. I 69(3): 584-94 (1973).

[730147] Picosecond pulse radiolysis. IV. Yield of the solvated

electrons at 30 picoseconds. Wolff, R. K.; Bronskill, M. J.; Aldrich, J. E.; Hunt, J. W. J. Phys. Chem. 77(11):

1350-5 (1973).

[730292] Effect of pressure on the rates of reaction of solvated

electrons and hydrogen atoms in liquid methanol.

Jha, K. N.; Freeman, G. R. J. Am. Chem. Soc. 95(18):

5891-6 (1973).

26
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The Radiolysis of Methanol: Product Yields, Rate Constants

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