NSRDS—NBS 42

NSRDS

Selected Specific Rates

of Reactions

of the Solvated Electron

in Alcohols

\ sJjfa

.

;

mjf a ;
NATIONAL BUREAU OF STANDARDS

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OGT 1 2 1972

-yuy-^t ~Selected Specific Rates of Reactions

<VS IS

of the Solvated Electron in Alcohols

Edgar Watson, Jr., and Sathyabhama Roy

Radiation Chemistry Data Center,

Radiation Laboratory,

University of Notre Dame,

Notre Dame, Indiana 46556

NSRDS

U.S. DEPARTMENT OF COMMERCE, Peter G. Peterson, Secretary

NATIONAL BUREAU OF STANDARDS, Lawrence M. Kushner, Acting Director, £ f 5 Rrx-J/SS

Issued August 1972
Library of Congress Catalog Card Number: 72-600051

NSRDS-NBS 42

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 42, 22 pages (Aug. 1972)

CODEN: NSRDAP

(C) 1972 by the Secretary of Commerce on Behalf of the United States Government

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

(Order by SD Catalog No. C13. 48:42). Price 30 cents. Stock Number 0303-0985
Foreword

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Lawrence M. Kushner, Acting • Director
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 dis- charge, 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 Foreword III Preface iv

Introduction 1 Table 1. Rate Constants of Reactions of the Solvated Electron in Methanol (1.01a— 1.28). __ 2

Table 2. Rate Constants of Reactions of the Solvated Electron in Ethanol (2.01a—2.30) 5

Table 3. Rate Constants of Reactions of the Solvated Electron in Propanols and Butanol

(3.01a—3.15) 5,1 | 9

Table 4. Arrhenius Parameters for Reactions of the Solvated Electron in Alcohol Solutions 11

Table 5. Index of Entry Numbers (Tables 1, 2, and 3) for the Reaction of Solvated Electrons

in Various Alcohol Solutions 11

References ^ 12

V

Selected Specific Rates of Reactions of the Solvated

Electron in Alcohols

Edgar Watson, Jr., and Sathyabhama Roy

Radiation Chemistry Data Center, Radiation Laboratory,*

University of Notre Dame, Notre Dame, Indiana 46556

Solvated electrons are generated in alcohols by radiolysis, photolysis, reaction with sodium,

etc. Rates of reactions of e~ with solvent and solute molecules, ions, and transients, in alcohol solu- tions, have been compiled. Arrhenius parameters are tabulated for some reactions. Key words: Alcohols; chemical kinetics; data compilation: radiation chemistry; rates: solvated electron.

Introduction

The nature and chemical properties of solvated

electrons in selected solvent media have been the

subject of extensive study. One of the important

characteristics of this species is its reactivity

toward a large number of reagents. The latest rate data compilation for the hydrated electron includes over 700 compounds for which specific rates of

reaction have been measured [71— 0061]. 1 Although

several reviews [65—9018; 68—0520; 69—0334;

69—0451; 71—0062] containing rate data for sol- vated electrons in alcohols have been published,

there has been no comprehensive compilation of

these data. This compilation of rate constants and

Arrhenius parameters has been prepared in order

to consolidate the information available in the

literature. These data are presented as reported

without critical evaluation. Critical assessment

of the kinetic parameters of several of the reactions

will appear in forthcoming critical reviews [71—0062

and 71-0362].

Rate parameters contained in this compilation

include data obtained by pulse radiolysis, flash

photolysis, and y-radiolysis. Competition kinetic

studies in alcohols, unlike water, have yielded a large portion of the rate information available. For

optimum utilization of the relative rates thus

obtained, it is required that the specific rate for one of the competing processes be known. Specific

rates obtained from relative rates are listed only

when the normalizing rate constants used seemed to be reliable and consistent. Generally, the normalization rate constants are from pulse radiolysis

*The Radiation Laboratory is operated under contract with the Atomic Energy

Commission. The work of the Center is supported jointly by the National Bureau of Standards, Office of Standard Reference Data and The AEC. This is AEC Document COO-38-784.

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

studies which offer the most reliable kinetic method

available to obtain rate data involving the solvated

electron. Due to the abundance of relative rates obtained using N2 0 as a competing solute and the

lack of consistent measurements of its specific rate (e.g. in methanol A-fe^ + NoO) values obtained

from the available data vary over an order of

magnitude), the specific rate of reaction of the

hydrated electron with N2 0 in water has been used

to normalize relative rates involving N2 0. Hence,

specific rates thus obtained are presented only

for comparison purposes and should be considered

with caution.

An attempt has been made to include all rate data which have been reported for alcohols. Duplication of references has been avoided in cases where it was apparent that two or more publications report the same experimental results.

Temperature when not specified is to be taken

as ambient, 15 to 25 °C. Rate constants obtained

at other temperatures have the appropriate temperature noted below the constant. No data on glassy

or solid alcohols have been included. No corrections have been made for the effect of ionic strength on the reaction rates of e~, but information pertinent to /x has been reported as given in the

reference.

Table 4 contains Arrhenius parameters obtained

for reactions of e~ in alcohols. Given in this table

are; log A, En , AST, temperature range, and the

reference.

Arrangement of Tables 1,2, and 3

Solute and Reaction. The first “solute” listed

in each table is the solvent (without solute) followed

by solvent mixtures (with no solute), and an alphabetical arrangement of the other solutes. The

products which have been identified are included

1
in the listed reactions. In competition studies the

reaction of e~ with the solute of entry appears as reaction (1) and is followed by the competing reaction (2). Solute concentrations were, in most cases

10

3 mol dm -3 or less. Higher concentrations are noted under Comments.

kdk-i. Relative rate constants listed are unitless

(both second order rates in units of dm3 mol_1

s _1

)- Relative constants are listed once [under solute of

reaction (1)]. Table 5 gives an index to entries for rate constants with the various solutes (relative and

specific) listed in tables 1, 2, and 3. k. Specific rate constants are listed and are in

units of dm3 mol _1 s

_1

. In the case of the reaction

of e~ with the alcohol, conversion of a second

order rate to a first order rate can be made by

multiplying the rate constant by the molarity of

the alcohol. Half-lives are also given under Comments. Specific rates calculated from relative rates are for reaction (1), and the footnote gives

the standard specific rate used for normalization.

Error limits and ionic strength have been given

as reported by authors. Except where otherwise

indicated, all solutions are neutral. Most numerical

values of k have been rounded off to one or two

significant figures.

Method. Abbreviations used under Method are:

y-r. = gamma radiolysis

p.r. = pulse radiolysis

f. phot. = flash photolysis

c.k. = competition kinetics

d.k. = decay kinetics

calc. = calculation.

Additional details of the method used are found

in the Comments column.

Comments. Included under Comments are additional experimental details not included with the

methods: £ 1 / 2 , measured quantities, corrections

applied, etc. For brevity, the following abbreviations and symbols have been utilized:

A = frequency factor

abs. = absorption

anal. = analysis

aq. = aqueous

av. = average

cone. = concentration

const. = constant

corr. = correction

d. = decay

dissocn. = dissociation

Ea = activation energy

elec, condy. = electrical conductivity

eq. = equation

f.o. = first order

G = radiation yield; (molecules or ions

per lOOeV absorbed)

k = specific rate H m ionic strength

Pv = vapor pressure

react. = reaction

S — alcohol (solvent)

S m = mixed solvent

ASt — entropy of activation

s = second

scav. = scavenger

soln. = solution

spec. = spectrophotometrically

£ 1/2 = half-life

Units used in tables 1,2,3, and 4:

k, A dm3 mol_1

s _1

En kj mol -1 ASt J moU'deg-1 T °C

Pv N m~2

.

References. The serial number used in Radiation

Chemistry Data Center files has been used for

reference citation. The first two numbers indicate

the year of publication.

Table 1 . Rate constants of reactions of the solvated electron in methanol

No. Solute and reaction kjk. A:(dm 3 mol _1 s

_1

) Method Comments Ref.

1.01a No solute (e~ +S)

e~ + CH.iOH —» CH:i O' + H

1.48 X 10-1 p.r.; d.k. [64-0080],

1.01b same (1.26 ± 0.04) X 10 4 p.r.; d.k. [69-0456].

mol dm -3

; d.f.o. over 3—4

half-lives; beyond 10 ~ 3 mol

dm -3 CH.jO", 1 1/2 in- creases to 3.1 fJLs at 1 mol

dm -3

. d.f.o. over 3-4 half-lives;

little change in k with re- 1.01c same 0.9 x 104 p.r.; d.k. [69-0146],[68-0260],

l.Old same 1.9 x 10 4 p.r.; d.k.

peated pulsing (~ 830

pulses); no ChCOH radical

abs. detected,

d. curves not of simple

order and probably in- [64-0113],

elude reaction with counter

ion. 2
Table 1. Rate constants of reactions of the solvated electron in methanol—Continued

No. Solute and reaction ktlkt /c(dm 3 mol 's

1 ) Method Comments Ref.

l.Ole same 1.7 X 104 (LiCl)

1.9 X 104 (NaBr)

1.5 X 104 (Nal)

( 8 —» 5.4) x 103 (KOH)

p.r.; d.k. C /2 — 1.7 |xs with added LiCl

(cone, independent); C / 2 =

1.5 /zs with added NaBr;

C/ 2 = 1.9 p, s with added

Nal (cone, independent);

cone, of KOH 0.15—» 2.65 mol dm -3

.

[70-0246J.

l.Olf same ~ 3.5 x 103 (T = - 78±2)

p.r.; d.k. d. curves not of simple

order and probably in- clude reaction with counter

ion.

[66-0082],

l.Olg No solute ej + ej * D2 + CH.jO-

(S = CHijOD)

(3.3 ±2)X 109 c.k. Reacted Na with CH:i OD and

measured D2 , HD, and disso- lution rate of Na; k calc, based on diffusion and homogeneous reaction kinetics.

[71-9165]

1.02 H2 0 (30 mol %)

e s +S m * ~ 1 x 104 p.r.; d.k. See l.Olf. [66-0082],

1.03 CH3CHOHCH3 (50 mol %)

«7 + S m

1.9 x 104 2.8 x 103 (T — — 78)

p.r.; d.k. See l.Olf; after —20 pulses

C/2 drops from 1.5 /xs to 0.6

/JiS.

[66-0082],

1.04a acetone

( 1 ) e- + (CH3) 2 CO->

(2) ey + N2 0 —^Na + O^

0.825 7.2 x 109c y-r.; c.k. Measured G(N2 ) : ki/k-z calc, on the basis of two cone, and is an av. value.[67-0313],

1.04b same 0.57 5.0 x 10yc y-r.; c.k. Two solute system (SFs and

(CH 3 LCO) to determine

Q! acet.; ki/ko obtained from

ratio of empirical a values

for acetone and N2 Og.

[70-0064],

1.05a acetophenone

(1) e7 + C 6H5COCH3-*

(2) e 7 + N2 0 ^N2 + 0

-

1.8 1.6 x 10 ,0C y-r.; c.k. Measured G(N2 ). [66-0045],

1.05b same I.85 1.6 x 10 10c y-r.; c.k. Measured G(N2 ); ki/k-> is an

average from two cone. [67-0313].

1.06a benzene

(1) ej + C«Hfi —

( 2 ) e~ + N2 0 —* N2 + O2.3 x lO-3 2.0 x 10 7c y-r.; c.k. Measured G(N2 ). [67-0313].

1.06b same 2.9 x 10-3 2.5 x 10 7c y-r.; c.k. Measured G(N2 ). [66-0045],

1.07a benzonitrile

(1) ej + CsHoCN —>

(2) e 7 + N2 0 ^N2 + 0

-

2.05 1.8 x 10 10c y-r.; c.k. Measured G(N2 ). [67-0313],

1.07b same 2.1 1.8 x 10 10c y-r.; c.k. Measured G(N2 ). [66-0045],

1.08 benzoquinone

e~ + CeH^Oa ~> 3x 10 10 p.r.; d.k. Corr. made for natural d. of

e~. [70-0198],

1.09a benzyl chloride ej + C 6H5CH2 C1 —

c«h5 ch2 + ci-

(5.0 ± 1.2) x 10 9 p.r.; d.k. Corr. for d. of e~ in pure

solvent; benzyl radical

identified spec, from 317.1 and 305.5 nm bands.

[64-0113],

1.09b same (5.7 ±1.2) x 10 9 p.r.; d.k. Benzyl radical observed

spec.; e~ cone, varied

two-fold.

[63-0059],

1.09c benzyl chloride

(1) es7 + CK H5 CH2 C1 —

(2) e~ + N2 0—» N2 + 0-

0.725 6.3 x 10 9c y-r.; c.k. Measured G(N2 ); kjk> an

average for two cone.

[67-0313],

1.09d same 0.36 ±0.04 3.5 x 109c y-r.; c.k. Measured G(N2 ): constant /z maintained using LiCl. [69-0456],

1.10 carbon tetrachloride

(1) e~ + CCI4 —

( 2 ) e'

s: + N2 0^ N2 + 0-

6.3 4.05.5 x 10 lrtc 3.5 x 10 loc y-r.; c.k. Measured G(N2 ); k\/k> given

for two cone, studied. [67-0313].

3
Table 1. Rate constants of reactions of the solvated electron in methanol Continued

No. Solute and reaction k\l k> &(dm3 mol 's

1 ) Method Comments Ref.

1.11 chloroacetate ion

(1) e67 + ClCH2 COO~

(2) es7 + N2 0—> N2 + 0~

« 1 «8.7X 10 !,c y-r.; c.k. Measured G(N2 ); constant ix maintained using LiCl.

[69-0456],

1.12a chlorobenzene

(1) e~+ CfiHoCl—

(2) + N2 0—» N2 + 0~

9.5 x 10-2 8.3 X 108c y-r.; c.k. Measured G(N2 ). [66-0045],

1.12b same 9.5 x 10 -2 8.3 x 10 3C y-r.; c.k. Measured G(N2 ); ki/k-> is average for two cone.

[67-0313],

1.13 cyanogen iodide

(1) e" + ICN —> 1 + CN~

(2) e s7 + N2 0^ N2 + 0-

0.53 4.6 x 10 !,c y-r.; c.k. Measured G(N2 ). [69-0220],

1.14 duroquinone

e~ -f- C id H 1 2 02 * C 1( ,H 12 0.7

~ 10'° p.r.; d.k. Corr. for e~ d. in pure

solvent.

[70-0198],

1.15a fluorobenzene

(1) e~ + CkH.-,F *

(2) es- + N2 0^ N2 + 0-

5.85 x 10-;i 5.1 x 10 7c y-r.; c.k. Measured G(N2 ); kjk> is average for two cone.

[67-0313],

1.15b same 5.9 x 10-3 5.1 x 10 7c y-r.; c.k. Measured G(N2 ). [66-0045], 1.16a H;

e~ + H4 -1* H

<H2 S04 or HC1)

(3.7 ± 1.0) x 10 ,() p.r.; d.k. Corr. for counter ion contribution (~ 3%).[63-0059],

1.16b same (3.9 + 0.9) X 10 10 p.r.; d.k. Corr. for e~ d. in pure

solvent.

[64-0113],

1.16c same (6.81 + 0.63) x

10 10 p.r.; d.k. Measured elec, condy. d.; effect of pH (4-10), N2 0,

and H2 0 observed.

[71-0064].

1.16d H+

(1) e; + HJ -> H

<H 2 S04 ) (2) e~ + N2 0—> N2 4- 0"

10

(n= 0)

8.7 X 10 10C y-r.; c.k. Measured G(N2 ); primary

salt effect evident

(kJk-> = 2. 93-+ 8.00);

/q//r2 at /jl — 0 obtained

from Broensted-Bjerrum

plot.

[67-0313],

1.16e same 3.0 2.6 x 10 10C y-r.; c.k. Measured G(H2 ) and G(N2 ). [66-0094],

[67-0018].

1.17 iodine

(1) ej + 1 2 —> (2) ej + S-*

10 7 y-r.; c.k. Measured G(H2 ); k is deduced from inequality conditions applied to scavenging equation.

[67-0030],

1.18a methyl bromide

(1) e; + CH;i Br^CH:i +

Br-

(2) e; + N2 0->N2 + 0-

1.46 1.3 X 10 100 y-r.; c.k. Measured G( 14 CH4 ) from

14 CH:! Br; aC H.,Br deter- mined from single solute

exp.; kfi.

2

obtained from

ratio of empirical a values

for CH;jBr and N2 08

.

[70-0064].

1.18b methyl bromide

(1) e; + CH:i Br^ CH:i +

Br-

(2) e; + S-»

1.35 x 106 1.2 X 10 ,,,a y-r.; c.k. Measured G( ,4 CH4 ); at low

cone, of CH:i Br empirical a eq. modified to include

c. of e~ d. as in pure

solvent 8.

[70-0064],

1.19 naphthalene

e; + C I0 H„-> ~ 2 x 10” p.r.: d.k. Spectrum shows product is not C.oHs- but probably

C„»H9 radical.

[64-0080],

1.20 nitrate ion

(1) ej + NO*-*

(2) e; + N2 0^N2 + 0-

1 <? 8.7 x 10 !,c y-r.; c.k. Measured G(N2 ); const, /jl maintained.

[69-0456].

1.21 nitrite ion

(1) ej + NO.;-*

(2) e~ + N2 0-* N2 4- O

-

« 1 « 8.7 x 10i,c y-r.; c.k. See 1.20. [69-0456].

1.22a nitrobenzene

(1) e~ + CeH5 N02 —>

(2) e~ + N2 0-» N2 + 0-

4.1 3.6 x 10 1(,c y-r.; c.k. Measured G(N2 ). [66-0045].

1.22b same 4.0 3.5 x 10 10c y-r.; c.k. Measured G(N2 ). [67-0313].

4
Table 1. Rate constants of reactions of the solvated electron in methanol— Continued

No. Solute and reaction kjk2 ^(dm3 mol 4 s

4 ) Method Comments Ref.

1.23a nitrous oxide

(1) es7 + N2 0—» N2 + 0-

(2) ej + S —

2.7 X 105 4.2 X lO5 (T=-97)

1.0 X 105

( T= 150

2.4 X 10Ha

y-r.; c.k. Measured G(N2 ): at T—

150. Pe = 1.32 X 106 Nm"2

; see table 4 for Arrhenius parameters.

[68-0610].

1.23b same > 4.55 x 10 4 >4.1 X 108a

y-r.; c.k. Measured G(N2 )[67-0313],

1.23c nitrous oxide

(1) ej + N2 0—» N2 + 0-

(2) e~ + Hj —» H

0.126

(fi = 0: T=0)

1.95 x 10!ld y-r.; c.k. Measured G(N2 ); kilk2 measured as function of pi. Corr. for counter ion[67-0065],

[63-0059]. 1.24a

1.24b

oxygen

e~ + 02 —

Oy

same

(2.1 ±0.4) x 10'"

(1.9 -‘-0.4) x 10"’

p.r.; d.k.

p.r.; d.k.

contribution (~ 3%).

Corr. for e~ d. in pure

solvent.

[64-0113].

1.24c oxygen

(1) e s: + 02 ^ 0.r

(2) c- + Hs+ ->H

(H2 SO^)

0.36 ±0.11 1.6 x 10 1,lb y-r.: c.k. Measured G (H2 ). [69-0146],

[68-0260],

1.25 silver ion

(1) e~ + Ag+ —> Ag°

(2) e~ + N2 0-^ N2 + 0-

2.4

(/x = 0; T= 0)

4.7 x 109e y-r.; c.k. Measured G(N2 ); ki/k>

measured as a function of

/z.

[67-0065].

1.26 sulfur hexafluoride

(1) e~ + SF« —> SF.-, + F~

(2) e~ + N2 0 —* N2 + O

-

3.2 2.8 x 10"' e y-r.; c.k. Measured G( ,4 CH4 ) from

I4 CH:i Br: two solute system ( ,4 CH;! Br + SF« ) used to determine aSFK ; kjk> from ratio of aSF(; to aN2 o.

B

[70-0064],

1.27a toluene

( 1 ) e~ + CfiH.-X H;i —

(2) e~ + N2 O

2 + 0-

7.2 X 10- 4 6.3 x 10KC y-r.; c.k. Measured G(N2 ). [66-0045],

1.27b same 5.9 x 10- 4 5.1 x 10KC y-r.; c.k. Measured G(N2 ): kJk-> from

single cone. ex|>.

[67-0313],

1.28 ubiquinone (Q)

f e; + Q-> Q

- 1.7X10'°

(± 20%)

p.r.; d.k. Corr. for natural d. of e^; k dependent on cone, of Q;

absorption spectrum of

radical anion observed.

[70-0198],

a k(e~ + S) =9 X 10'! dnr'moF's-1

; cf. 1.01c.

b k(e~ + H+ ) =4 x 10"’ dm:5 mol_, s

_l

; cf. 1.16a. 1.16b.

c k(e~ + N2 0) ~ A(e“

q + N2 0) = 8.7 X 10" dm:i mol _l s

_l (see Introduction).

d k(e~ + H+) = 1.54 X 10 10 dm:i mol~ l s-1 (7’=0) obtained by correcting (b) assuming E„ — 11 kj mol -1 -

e A(c; + N2 0) = 1.95x 10!

' dnUmoU's- 1 (T= 0); cf. 1.23c.

f Ubiquinone is a coenzyme quinone with 6 isoprenoid units in side chain.

* G (product) resulting from the scavenging of e~ by a solute A can be fitted to an empirical equation containing aA (or a A . a B . . . for two or more solutes) as an adjustable parameter. The a’s are characteristic of the solute and are shown [cf. 70—0064] to be related

to the rate constant for scavenging by: aA — k{e~ -F A)/A,

where A is a constant for a given medium. Hence, two a’s measured in the same alcohol have the following relationship: aa/«b = k (e; + A) /k (e; + B )

Table 2. Rate constants of reactions of the solvated electron in ethanol

No. Solute and reaction ki/h A(dm:! mol_, s

_1

) Method Comments Ref.

2.01a No solute (e~ + S)

ej + C2 H.-,OH —» H + C.H-,0-

6.8 X 10:! p.r.; d.k. 1 1 / 2 dose dependent; zero dose £]/•> (6 pis) from

computer anal.

[70-0172].

2.01b same (0. 8-1.0) X 10 4 p.r.; d.k. Sodium ethoxide addition increases 1 1 / 2 from neutral value. 4 pis. to 5.3 Ms.

[70-0172],

5
Table 2. Rale constants of reactions of the solvated electron in ethanol — Continued

No. Solute and reaction kfkz £(dm3 mol 's ! ) Method Comments Ref.

2 . 01 c same 1.9 X 103

f. phot.;

d.k.

e~ generated from I -

; abs. [64-7006].' corrected for Ij.

d. curves not of simple

order and probably in- 2 . Old same 1.35 X 10 4 p.r.; d.k. [64-0113],

[63-0059],

elude reaction with counter ion; £i / 2 = 3 /xs;

f 1/2 longer in basic soln. 2 . Ole same 2.3 X 10 4 p.r.; d.k. C/2 = 1.7 |U.s with added

LiCl (cone, independ-

[70-0246].

(LiCl) 2.0 X 10 4 (LiBr)

(9->6) X 103 (KOH or NaOC2 H5 ) 2.0 x 103 2 . 01 f same p.r.; d.k.

ent); C/2 = 2.0 /xs with added LiBr (> 0.1 mol

dm-3

); cone, of KOH and

MOC2 H5 0

- 6 ) x 10 -1 mol dm-3

. C/2 = 20 /xs; d. nearly f.o. but shows deviation at [66-0082],

(T = — 78±2)

early times. 2 . 01 g same ~ 1.8 x 104 calc. G(H2 ) used c.k. eq.; data from [64-0279] and

[67-0030],

( 1 ) ej + s —

( 2 ) e; + A^ [65-0501]; A is ace- tone. acetaldehyde, and

Ni2+

; k\ estimated

using &(eq + A) and is an av. value for three

solutes. 2 . 01 h No solute (5±4)x 109f (7±3)X 10*

c.k. Reacted Na with C>H-,OD [71-9165].

ej T ej > D2 T" C2 H5 O

- and measured D2 , HD,

(S is C2 H5 OD) (5.3±2)X10B and dissolution rate of (T=- 78) Na; k calc, based on dif- fusion and|homogeneous

reaction kinetics. 2.02 glycerol (31 & 12 mol %) 8.2 x 104 p.r.; d.k. C /2 = 0.50 and 0.75 /xs for 31 and 12%, respectively;

[66-0082],

(31 mol %)

5.4 X 10 4 (12 mol %)

1.0 X 10 5 2.03

es S7n ^ H2 0 (10, 20, and 36 mol %) p.r.; d.k.d. nearly f.o. but shows

deviation at early times. C/2 = 0-4, 2.5, 2.2 fxs for 10, 20, and 36 mol %,

[66-0082],

(10 mol %)

es T S m

* 1.6 X 10 4 (20 mol %)

1.8 X 104

respectively; see 2 . 02 .

2.04 NaOH

(36 mol %)

p.r.; d.k. Rapid d. on ns time scale; with added NaOH rapid

[67-0126],

2.05a acetaldehyde (4 + 0.5) X 10 3 p.r.; d.k.

decaying transient reduced; postulated as reaction within spur;

r ~ 80 ns but d. may not be of simple order. [70-0172], + CH.iCHO

2.05b acetaldehyde 1.6 X 10s 1.1 X 10 Ha

y-r.; c.k. Measured G(H2 ). [64-0279],

( 1 ) eg + CHisCHO —:

(2 ) eif + S —

2.06a acetone 7.1 x 105 4.8 X 10!,a •y-r. ; c.k. Measured G(H2 ). [64-0279],

( 1 ) es + (CH^CO -*

(2) e.7 + S —

2.06b same 4 x 105 2.7 X 10!,a y-r.; c.k. Measured G(H2 ). [67-0004], 2.06c acetone 0.52 3.1 X 10!,c y-r.; c.k. Measured G( , 4 CH_t) from [70-0064],

(1) e.7 + (CH.hCO —

two solute system

( 2 ) + N2 0^ N2 + O- ( 14 CH:i Br + (CHiibCO) to determine aacet.' kjk-z

obtained from the ratio of empirical a values for acetone and N2 O

d

.

6
Table 2. Rate constants of reactions of the solvated electron in ethanol — Continued

No. Solute and reaction kfk. Ar(dm3 mol-1 s

-1

) Method Comments Ref.

2.07 anthracene 2.4 x 108 1.6 X i0 ,0a y-r.; c.k. Measured G(H2 ). [64-0279],

(1) eg + Ci-iHio -*

(2) e.7 + S^

2.08

2.09a

benzene

(1) ej + ChHb —

(2) e.7 + S->

benzyl chloride

8.5 x 102 5.8 X 108a

5.1 X 10H

y-r.; c.k.

p.r.; d.k.

Measured G(H2 ): corr. for reaction of ej with

impurities. Corr. for ej d. in pure S.

[69-0651],

[64-0138].

2.09b

ej + ChHsCH^CI —

c6h5ch2 +cTM

same (5.1 ±1.2) x 10H p.r.; d.k. Corr. for ep d. in pure S; [64-0113].

2.09c same (5.3 ±1.3) X 10H p.r.; d.k.

benzyl radical identified spec, from 317.1 and

305.5 nm bands. Benzyl radical absorption observed. [63-0059],

2.10a biphenyl > 2 x 10H p.r.; d.k. Biphenylide ion identified [64-0113].

2.10b

e$ + C 12 H 10 * Ci 2 Hfo

biphenyl

(1) ej + C^Hio -* Ci 2 Hfo

(4.3 ±0.7) x 10H p.r.; c.k.

spec, from 405. 610,

and 635 nm bands. O.D. of biphenylide ion measured at midpoint of [64-0084]

(2) ej + naphthalene —* 0.4 ^s pulse in pres- ence of various amounts

of CioHh; see 2.19 for k{e~ + C I0 Hh) . 2.11a carbon tetrachloride 1.0 X104 6.8 x 107a y-r.; c.k. Measured G( H2 )

[64-0279],

(1) e.7 + CCh —

(2) es- + S->

2.11b

2.11c

carbon tetrachloride

(1) ej + CCh —*

(2) ej + N2 0—

carbon tetrachloride

ej + CCli —

< 1.3 < 1.1 x 10 10C

1.1 x 1010

y-r.; c.k.

p.r.; d.k.

Dose and base affect k; upper limit because no

corr. for acid formed.

Neutral and basic soln.

[71-0009J.

[71-0009],

2.12a chloroacetic acid 1.1 x 105 7.5 x 10 8a y-r.; c.k. Measured G(H2 ). [64-0279]

(1) e* + ClCH2 COOH —

(2) e.7 + S^

2.12b same 1.3 x 105 8.9 x 10 8a y-r.: c.k. Measured dose effect on [65-0045],

G(H2 ) and G(CH3 CHO).

2.12c same 1.0 x 105 5.0 x 104 (T= 0)

7.3 x 103 (T=-20)

4.1 x 103

6.8 X. 10sa y-r.; c.k. Measured G(H2 )

[67-0173],

(r=— 72 ) 2.12d chloroacetic acid 1.0±0.35 2 x 101,,b y-r.; c.k. Measured G(H2 ); utilized [65-0501].

(1) es- + ClCH2 COOH^ G(H2 ) given in [64-

Cl- + CH2 COOH 0279] to obtain ki/k>.

(2) es- + H;^ H

2.13a cvclopentyl bromide 0.48 9.6 x 10Hb y-r.; c.k. Cone, of Cl- and CoH9 Br [70-0248].

(1) ej + C5 H9 Br—> Br~ was 0.1 mol dm-3

; cone.

2.13b

+ C5 Hh (2) es- + Hs--^H

cyclopentyl bromide 2.3x10" p.r.; d.k.

of H+ 0.2—» 1 mol dm-3

; 95% ethanol. [71-0475].

ej + CsHaBr—

2.14 ethyl acetate 1.1 X 104 7.5 x 107a y-r.; c.k. Measured G(H2 ). [64-0279].

(1) ej + CH3 COOC9 H5 —

( 2) es- + S^

2.15a H;

es- + H;-> H

(2. 1 + 0.4) x 10 10 (HC1)

p.r.; d.k. Cone. Hf calc, assuming [63-0059],

complete dissocn. of HC1

(2.2 ± 0.3) x 10 1 " and first dissocn. of (H2 S04 ) h2 so4 .

7
Table 2. Rate constants of reactions of the solvated electron in ethanol — Continued

No. Solute and reaction

2.15b same

kdk.

2.15c same

2.15d same

2.15e

2.15f

H;

( 1 ) ei + Hi H

(2) e,- + S-»

H/

(1) ef + H/ —> H

(2) e.r + N2 0—» N2 + 0~

2.0 x 10s

4.1 >2.9

2.16a

2.16b

2.17

2.18

2.19

2.20

2. 21 a

2 . 21 b

2 . 21 c

2 . 22 a

2 . 22 b

2.23

2.24

methyl bromide

(1) ej + CH.iBr —

CH3 + Br~

(2) ej + N2 0 -> N2 + Omethyl bromide

(1) ef + CHsBr —» CH:s + Br-

( 2 ) ei + S

methyl chloride

( 1 ) ej+CHaCl-^CH.., + ci-

( 2) e- + N2 0 -» N2 + Onaphthacene

ej + C1 sHi > —

naphthalene

ej + C 1 <)Hk —* nitrate ion

( 1 ) ei + NO3

" —* no2 +oh-+c2 h5 o-

(2) ei + Ri^H

nitrous oxide

(1) c7 + N2 0->N2 +0-

( 2) ej + S —>

same

nitrous oxide

(1) ei + N2 0 —:

N2 + O

-

(2) er + CH3CHO—

oxygen

ei + 02 —* Oi

same

perfluorocyclohexane

ei + CbF) 2 ->

phenol

ei + CeHsOH -»«

1.52

1.0 X 106

0.38

( 1 .45 zt 0.45) X 10

7.1 x 105 6.8 x 105 (r=-112)

5.8 x 105 (r= 90)

1.1 x 10K (7’= 145)

1.0 x 10H 5.0 x 10> (r= 90)

5.4 x 105 (T

145)

5.4 x 105 (T =1-112)

1.75

&(dm3 mol-1s *) Method Comments Ref.

(2.0 ±0.4) X 1010 p.r.; d.k. Corr. applied for es7 d. in [64-0113],

(HC1 and pure solvent; see [63-

H2 S04 ) 0059] for Hy. cone.

(4.49 ± 0.1 7)X 1010 p.r.; d.k. Measured elec, condv.d.; [71-0064],

effect of pH(4-10). N2 0. and H2 0 observed: see

table 4 for Arrhenius

parameters.

1.1 x 10 10 (HC1) p.r.; d.k. Assumed only single ioniza- [71-0475J.

1.4X1010 (H2 S04 ) tion of H2 S04 . 1.4 x 10 1,)a y-r.; c.k. Measured G(H2 ). [64-0279],

3.6x 1010c y-r.; c.k. Measured G(N2 ); k — 3.6X [71-0009J. > 2.5x 10,oc 101H based on kdiss (H2 S04 )= 1.7 X 10~:i and

k > 2.5 X 101(l is for complete dissocn. of H2 S04 . 9.1 x 10!,c y-r.; c.k. Measured G( , 4 CH4 ) from [70-0064],

, 4 CH3 Br; kfk-> ob- tained from ratio of empirical a values. d 6.8 x 109a y-r.; c.k. See 2.16a. [70-0064],

2.3 x 109c y-r.: c.k. See 2.06c: two solute sys- [70-0064],

tern CH3 CI and l 4 CH3 Br.

( 1.02 0.08) X 1010 p.r.; d.k.

p.r.; d.k.

[64-0084]

(5.4 + 0.5)X 10 [64-0084] 9

3 x 109b y-r.; c.k. See 2.12d. [65-0501].

4.8 x 109a y-r.: c.k. Data from [68-0047]: at [69-8025],

T=90. P, = 1.62 X 105 Nm'2

; at 7’= 145, Pv =

8.5 X 105 Nm-2

; see table 4 for Arrhenius parameters.

6.8 x 10Ha y-r.; c.k. Measured G(H2 ). [67-0012],

[68-0047].

7x 109e y-r.; c.k. Measured G(N2 ). [71-0009],

. (1.9±0.3)x 10 10 p.r.; d.k. Corr. applied for ei d. in [64-0113]

. (2.0±0.3) x 10'° p.r.: d.k. pure S. [63-0059],

(2.5 + 0.5) x 109 p.r.; d.k.

p.r.; d.k.

[70-0172],

4.5 X107 [71-0475],

8
Table 2. Rate constants of reactions of the solvated electron in ethanol— Continued

No. Solute and reaction ki/k-2 « A:(dm3 mol_1 s

_1

) Method Comments Ref.

2.25a propyl bromide 3.0X109 p.r.; d.k. Neutral and basic soln. [71-0009],

ey + C3 H7 Br > C3 H7 + Br~

2.25b propyl bromide 0.19 s= 1.7X 109c y-r.; c.k. Dose effect on A; upper [71-0009].

( 1 ) ey + C3 H7 Br—

limit for k because no

(2) ey + N2 0 —> N2 + 0- corr. for acid formed.

2.26 propvl chloride 2.4 X HP2 4.8X 10sn y-r.; c.k. Cone, of CP and C:)H 7 C1 [70-0248]

( 1 ) ey + C3 H7 CI—> C.5 H7 was 1 and 0.1 mol dm-3

; + CP cone, of FP 0.05—>1.0

( 2 ) ey + H+ ^H mol dm-3

; 95% ethanol.

2.27 sulfur hexafluoride 1.5 1.3 X 1010C y-r.; c.k. Measured G( , 4 CH4 ) from [70-0064].

(1) ey + SFe—> SF.5 +F-

( 14 CH3 Br+SFK ) soln.

(2) ey -+- N2 0—

N2-bO_

to obtain aSP6 ; see 2.06c. 2.28 p-terphenyl (7.2 ±0.6) X 109 p.r.; d.k. C1 k

14 identified spec. [64-0084],

ey + CihHi 4 > CisHfj from 435.8 nm band.

2.29a 3.5X1010 p.r.; d.k. [71-0009],

ey + C(N02 )4 —

2.29b tetranitromethane 2.7 2.4X 1010C y-r.; c.k. Measured G(N2 ). [71-0009],

(1) ey + C(N02 )4 —

( 2) ey + N2 0 —> N2 +

2.30 triphenylmethanol (2.0±0.4)X 108 p.r.; d.k. Corr. applied for ey d. in [64-0113],

ey + (CnHshCOH—

S; triphenylmethyl

(C«H-,bC + OH- radical identified spec.

a A(ey + S) = 6.8 X 103 dm:i mol-1

s

-1

; cf. 2.01a.

h k(es“ + Hs+ )=2X 10‘° dnPmoP's-1

; cf. 2.15.

c k(ey + N2 0) ~ k(e~

q+ N2 0) = 8.7X 109 dnPmoP's-1

. d See footnote (g). table 1.

e k(ej + CH.iCHO) = 4 X 109 dnPmoP's-1

: cf. 2.05a.

f A(ey + ey) = (5± 4) X 109 calc, based on A(ey + S) = 5.4 X 103 dm3mol-1

s-1

, and k(ej + ey)= (7± 3) X 109 based on A(ey + S) =

6.8 X 103 dm3 mol_1s_1

.

Table 3. Rate constants of reactions of the solvated electron in 1-propanol (1-PrOH), 2-propanol (2-PrOH), and 1 -butanol (1-BuOH)

No. Solute and reaction ki/ki A(dm3 moP1 s

_1

) Method Comments Ref.

3.01a No solute; S— 1 -PrOH

ey + C3 H7 OH —* H

+ C3 H7 O-

- 2 . 6 X 104 p.r.; d.k. d. not of simple order; probably includes reaction with counter ion; 1 1/ 2 ~ 2 /xs.

[64-0113].

3.01b No solute; S=2-PrOH

ey + CHsCHOHCH:,-* H + (CH3 ) 2 CHO-

~ 1.1 X104 p.r.; d.k. tn2 ~ 5/zs; see 3.01a. [64-0113].

3.02a acetone; S — 2 -PrOH

(1) ey + (CH3 )2 CO—

(2) ey + CH;i CH2 CH2 OH —

7.7 x 104 y-r; c.k. Measured G(H2 ). [67-0004].

[67-0174],

[ 66 - 0221 ], 3.02b acetone; S = 2-PrOH

( 1 ) ey + (CH;s)2 CO—

(2) ey + N2 + O'

0.59 5.1 x 10 9a y-r; c.k. Measured G(N2 ); single cone, determination.

[66-0027],

3.02c acetone; S=l-BuOH

(1) ey + (CH3 ) 2 CO >

(2)

ey + CH3 (CH2 ) 3 OH^

1.4 x 102 y-r.; c.k. Measured G(H2 ). [67-0004],

3.03 acetophenone; S=2-PrOH

(1) ey 4- CbHsCOCHs —

(2) ey + N2 0 —> N2 + 0“

1.7 1.5 X 10 ,oa y-r.; c.k. Measured G(N2 ). [67-0045].

3.04a benzene; S= 2-PrOH

(1) ey 4- CsH« —

( 2 ) ey + N2 O —> N2 + 0~

2.1 x 10-2 1.8 x 103ay-r.; c.k. Measured G(N2 ). [66-0045],

3.04b same 2. Ox BP2 1.7 x 10Ha y-r.; c.k. Measured G(N2 ). [66-0027],

3.05 benzonitrile; S= 2-PrOH

( 1 ) ey + Ch H.-, C N —

( 2 ) ey + N2 O —> N2 + CP

1.9 1.7 x 10 1,,a y-r.; c.k. Measured G(N2 ). [66-0045],

3.06 benzophenone: S=2-PrOH

( 1 ) ey -+- (ChHs ) 2 CO—

(2) ey + N2 0 —> N2 + 0~

1.30 1.1 x 10 ,na y-r.; c.k. Measured G(N2 ); single cone, determination.[66-0027],

9
Table 3. Rate constants of reactions of the solvated electron in 1-propanol (1-PrOH), 2-propanol (2-PrOH), and 1-butanol (1-BuOH) — Con.

No. Solute and reaction kfk-> A(dm:! mol_l s _1

) Method Comments Ref.

3.07 carbon tetrachloride; S= 2-PrOH

( 1 ) c.7 + C C 1-1 *

(2) 67 + N2 0 —» N. + O2.26 2.0 X 10 ,,,a y-r.; c.k. Measured G(N2 ); single cone, determination.

[66-0027].

3.08 chlorobenzene; S= 2-PrOH

( 1 ) 67 Ch H.-> C 1 * (2) e7 + N2 0-» N2 + O0.54 4.7 X 10 9a y-r.; c.k. Measured G (

N

2 )

.

[66-0045],

3.09 ferric ion: S= 1-PrOH

(1) e.7 + Fe T-i —> F e

+ -

(2) ej-F CH:i CH2 CH2 OH—

5.6 x 104 y-r.; c.k. Measured G (

H

2 )

.

[67-0174],

3.10 fluorobenzene: S= 2-PrOH

(1) e.7 + Ch H.->F —

(2) e7+N2 0-> N2 + O5.0 X 10" 2 4.4 X 10xa

y-r.; c.k. Measured G (

N

2 )

.

[66-0045].

3.11a Hs: ; S= 1-PrOH

'(1 )c7 + H;-> H(H,SCG)

(2) e.7 + N2 0—> N2 + 0-

5.0(pH = 2.4) 5.6(pH = 2.7) 4.4 X 10 ,lla 4.9 X 10 loa y-r.; c.k. Measured G(N2 ); ki/k> used

in calc, of G(N2 ) to good

fit with exp.; taken from

CH3 OH data [67-0065]

and adjusted for p..

[69-0387].

3.11b Hs: ; S= 1-PrOH

e.7 + H+ —> H

(2.55 ±0.19) x 10 10 p.r.; d.k. Measured elec, condy. d.; effect of pH(4-10), N2 0,

and H2 0 observed; see

table 4 for Arrhenius

parameters.

[71-0064].

3.11c Hs~

; S— 2-PrOH

(1) e.7 + Hs+ —> H(HC1)

(2)

e7 + N2 0-* N2 + 0-

0.5 4.4 x 10 9a y-r.; c.k. Measured G( N2 ) ; k\/k> is av. for pH= 1.3—» 2.3. [66-0027],

3. lid H;; S= 2-PrOH

V+ H; -> H

(1.67 + 0.14) x 10 10 p.r.; d.k. Measured elec, condy. d.; effect of pH (4 — 10), N2 0,

and H20 observed: see

table 4 for Arrhenius

parameters.

[71-0064].

3.12a nitrobenzene: S= 2-PrOH

(1) e~ CfiH.->N02 *

(2) e~ + N2 0 —> N2 + O

-

2.3 2.0 x I01,,a y-r.; c.k. Measured G(N2 ). [66-0045],

3.12b same 2.3 2.0 x 10")a y-r.; c.k. Measured G(N2 ). 1 66—0027].

3.13a nitrous oxide: S= 1-PrOH

(1) e~ + N2 0 —» N2 + 0

~

(2) e x + CH;i CH2 CH2OH —

1.5 x 10’ 6.4 X 104 (T=- 120)

1.2 x 10' (7’= 140)

y-r.; c.k. Measured G(N2 ): at 7=140,

P, =3.8X 10’ Nrn --; see

table 4 for Arrhenius

parameters.

[69-0387],

3.13b nitrous oxide: S=2-PrOH

(1) e~ + N2 0 —* N2 + 0~

(2) e~ + CH.jCHOHCH.j —

5.9 x 10:i y-r.; c.k. Measured G(H2 ). [66-0027 ).

3.13c same 2.2 x 10’ 8.4 x 10’ (7=-85)

2.1 x 105 (T — 140)

y-r.; c.k. G(N2) from [68-0042]; at 7=140, P, = 6.6 X 105 NmA see table 4 for Arrhenius parameters.

[69-8025],

3.14 propionaldehyde: S= 1-PrOH

(1) e~ + CH.iCH2 CHO —

(2) e~ + CH:! CH2 CH2 OH —

1 x 10> y-r.; c.k. Measured G(H2 ). [67-0174],

3.15 toluene: S=2-PrOH

(1) c- + C«H5CH3 ->

(2) e; + N2 0-^N2 + 0-

1.4 X 10-2 1.2 x 10 8a

y-r.; c.k. Measured G(N2). [66-0045],

a

/. (ej + NjO) ~/. (e

aq +N^O) =8.7X 10 9 dm3 mol_1 s

_I (see Introduction).

10
Table 4. Arrhenius parameters for reactions of the solvated electron in alcohol solutions

Reaction Alcohol log A

(dm:! mol-1s

-1

) Ea (kj mol-1

) AS'*

(J mol-1 deg-1

) T

(°C)

Ref.

e- + S —

methanol 6.47a 15.5 -88 -97 to 150 [68-0610],

ethanol 7.16a 19.2 -88 -112 to 145 [69-8025]

[68-0047],

1-propanol 18.8 -80 -120 to 140 [69-0387].

2-propanol 26.4 -59 — 85 to 140 [69-8025],

[68-0042],

e 7 + Hs ethanol 11.00 (19.7 ± 1.3) — 33 1 ' 26 to 50 [71-0064],

1-propanol 10.80 (24.3 ±2.1) -21" 24 to 50 [71-0064],

er + er

2-propanol

ethanol-c?i

10.79 (30.5 ±2.1)

<32 ±8)

-21" 25 to 46 -78 to 25 [71-0064],

[71-9165],

d Log A calculated using experimental E„ and rate constants given in 1.01c and 2.01a.

b AS* calculated using experimental log A and the preexponential relationship of the transition — state theory.

Table 5. Index of entry numbers (tables 1, 2, and 3) for the reaction of solvated electrons in various alcohol solutions

Solute added Methanol Ethanol 1-Propanol 2-Propanol 1-Butanol

None ( e

j

-T S ) 1.01a, 1.01b,

1.01c, l.Old,

l.Ole, l.Olf, 1.17, 1.18b,

1.23a, 1.23b

l.Olg

2.01a. 2.01b. 3.01a. 3.02a, 3.01b. 3.02a, 3.02c.

None (ei + e<r) acetaldehyde

2.01c, 2. Old,

2. Ole, 2.01f, 2.01g, 2.05b,

2.06a, 2.06b. 2.07,2.08.2.11a,

2.12a. 2.12b.

2.12c, 2.14, 2.15e, 2.16b,

2.21a, 2.21b 2.01A

2.05a. 2.05b

3.09, 3.13a, 3.14

3.13b, 3.13c

acetone 1.04a, 1.04b

1.05a, 1.05b

1.06a, 1.06b

2.06a, 2.06b, 2.21b, 2.06c 3.02a 3.02b 3.02c.

acetophenone 3.03 anthracene benzene

2.07

2.08a, 2.08b 3.04a, 3.04b

3.05 3.06

benzonitrile benzophenone

benzoquinone

benzyl chloride

1.08

1.09a, 1.09b,

1.09c, 1.09d

2.09a, 2.09b, 2.09c

2.10a, 2.10b

2.11a, 2.11b, 2.11c

2.12a, 2.12b,

2.12c, 2.12d

2.13a, 2.13b

biphenyl

carbon tetrachloride chloroacetic acid1.10 3.07

chloroacetate ion chlorobenzene cyanogen iodide cyclopentyl bromide

duroquinone

1.11 1.12a, 1.12b

1.13

1.14

3.08

ethyl acetate 2.14

ferric ion 3.09 H 1.16a, 1.16b, 3.11a, 3.11b

1.16c, 1.16d,

1.16e, 1.23c, 1.24c

1.17

1.18a, 1.18b

2.12d, 2.13a,

2.15a, 2.15b,

2.15c, 2.15d,

2.15f, 2.20, 2.24

2.16a, 2.16b

2 17

3.11c, 3. lid

iodine methyl bromide

methyl chloride naphthacene 2.18 3.03

11
Table 5. Index of entry numbers ( tables 1 , 2, and 3) for the reaction of solvated electrons in various alcohol solutions — Continued

Solute added Methanol Ethanol 1 -Propanol 2-Propanol 1-Butanol

1.19 2.10b, 2.19

1.20 2.20

1.21 1.22a, 1.22b 3.12a. 3.12b

1.04a, 1.04b. 2.06c, 2.11b, 2. 15 f. 3.13a 3.04a, 3.04b,

oxygen

1.05a, 1.05b,

1.06a, 1.06b,

1.09c, 1.09d,

1.10, 1.11, 1.12a, 1.12b,

1.13, 1.15a, 1.16d, 1.16e,

1.18a, 1.20,

1.21, 1.22a, 1.22b, 1.23a, 1.23b, 1.23c,

1.25, 1.26, 1.27a, 1.27b

1.24a, 1.24b, 1.24c

2.16a,2.17, 2.21a,

2.21b, 2.21c, 2.25b

2.27, 2.29b

2.22a, 2.22b

2.23

3.05, 3.06, 3.07, 3.08,3.10,3.11a,

3.11c, 3.12a,

3.12b, 3.13b,

3.13c, 3.15

perfluorocyclohexane

propionaldehyde 3.14 propyl bromide 2.25a, 2.25b

propyl chloride 2.26

1.25 sulfur hexafluoride 1.26 2 27

p-terphenyl 2.28

2.29a, 2.29b

toluene 1.27a, 1.27b 3.15

triphenyl methanol 2.30 ubiquinone 1.28

References

[63-0059] Pulse radiolysis studies of the reactivity of the solvated

electron in ethanol and methanol. Taub, I. A., Sauer,

M. C., Jr., Dorfman, L. M., Discussions Faraday Soc. 36,206-13(1963).

[64-0080] 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, .)., Proc. Chem. Soc. 265-6 (1964). [64-0084] 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). [64-0113] Pulse radiolysis studies. IV, The solvated electron in the aliphatic alcohols. Taub. I. A.. Harter, D. A.. Sauer, M. C.. Jr., Dorfman, L. M., J. Chem. Phys. 41(4),

979-85(1964).

[64-0138] The reactivity of aromatic compounds toward hydrated

electrons. Anbar, M.. Hart. E. J., J. Am. Chem. Soc. 86,5633-7(1964).

[64-0279] Mechanism of hydrogen formation in the radiolysis of

liquid ethanol. Adams, C. E., Sedgwick, R. D.. Trans. Faraday Soc. 60, 865-72 (1964). [64-7006] Primary processes in the photo-oxidation of iodide ion

in ethanol. Dobson, G., Grossweiner, L. I.. Radiation

Res. 23,290-9(1964).

[65-0045] The radiolysis of ethanol. III. Liquid phase. Myron,

J- J- J., Freeman. G. R., Can. J. Chem. 43, 381-94

(1965). [65-0501] Electron capture by solutes in the radiolysis of methanol and ethanol. Havon, E.. Moreau, M., J. Phys.

Chem. 69, 4053-7 (1965). [65-9018] The solvated electron in organic liquids. Dorfman.

L. M., Advan. Chem. Ser. 50, 36-44 (1965).

[66-0027] The y-radiolysis of liquid 2-propanol. Effect of nitrous oxide and sulfuric acid. Sherman. W. V., J. Phys.

Chem. 70(3), 667-72 (1966). [66-0045] The reactivity of electrons produced in the y-radiolysis of aliphatic alcohols. Sherman. W. V.. J. Am. Chem.

Soc. 88(7), 1567-8(1966).

[66-0082] 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). [66-0094] Linear energy transfer effect in the radiation chemistry

of liquid methanol. Imamura, M., U.S. -Japan Seminar

on Radiation Chemistry of Organic Compounds.

Honolulu, Hawaii, May 2-6, 1966. [66-0221] Yields and rate constants of the precursors of hydrogen

in the radiolysis of n-propanol. Basson. R. A., van der Linde, H. J.. Nature (London) 210, 943-4 (1966). [67-0004] Polarity effects in the radiolysis of n-alcohols, Basson,

R. A., van der Linde, H. J., J. Chem. Soc. Pt. A. (1), 28-32(1967).

[67-0012] The radiolysis of ethanol. V. Reactions of the primary

reducing species in the liquid phase. Russell, J. C., Freeman, G. R.. J. Phys. Chem. 71, 755-62 (1967). [67-0018] Radiolysis yields from y-irradiated liquid methanol

containing nitrous oxide and the effect of acid. Seki,

H.: Imamura, M., J. Phys. Chem. 71(4), 870-5 (1967). [67-0030] Hydrogen formation in the radiolysis of liquid methanol

and ethanol. Teply, J., Habersbergerova, A., Collection Czech. Chem. Commun. 32, 1350—8 ( 1 967). [67-0065] Kinetic salt effects on reactions of the solvated electron

in methanol. Buxton, G. V., Dainton, F. S., Hammerli,

M., Trans. Faraday Soc. 63(533), 1191-7 (1967). [67-0126] Direct observation of regions of high ion and radical concentration in the radiolysis of water and ethanol.

12
Thomas, J. K., Bensasson, R. V., J. Chem. Phys. 46,

4147-8(1967).

[67-0173] Effect of temperature on the yields of the precursors of hydrogen in the radiolysis of ethanol. Basson, R. A.,

J. Chem. Soc. Pt. A. (7), 1179-82 (1967). [67-0174] The radiation chemistry of rc-propanol. Part I. Formation of the major products. Basson, R. A., van der Linde, H. J., J. Chem. Soc. Pt. A. 1182-6 (1967). [67-0313] 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). [68-0042] Reactions of the primary reducing species in the radi- olysis of liquid 2-propanol. Russell. J. C., Freeman.

G.' R., J. Phys. Chem. 72(3), 808-15 (1968). [68-0047] The yields of the primary reducing species in the

radiolysis of liquid ethanol. Hussell. J. C., Freeman,

G. R., J. Phys. Chem. 72(3), 816-21 (1968). [68-0260] Radiolysis of methanol, pulse studies and competition

kinetics with oxygen and acid. Suryanarayanan, K., Lichtin. N. N., 156th Am. Chem. Soc. Meeting. Div. Phys. Chem., Atlantic City, New Jersey, Abstract No.

22, 8-13 Sept., 1968. [68-0520] Methods of production of solvated electrons and their chemical and physical properties. Thomas, J. K., Radiation Res. Rev. 1 , 183-208 (1968). [68-0610] 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). [69-0146] The radiolysis of methanol and methanolic solutions. V. The acid effect. Suryanarayanan. K., Lichtin. N. N., J. Phys. Chem. 73(5), 1384-9i (1969). [69-0220] Radiolysis of methanol containing cyanogen iodide,

Ogura, H., Miyagawa, T., Kondo, M., Bull. Chem. Soc. Japan 42, 1763-5 (1969). [69-0334] Technique of pulse-irradiation. Arai, S.. Radiation

Chemistry 4(8), 2-13 (1969). [69-0387] Effect of temperature on the reactions of electrons during the y-radiolysis of liquid n-propanol. Jha,

K. N.. Freeman, G. R., J. Chem. Phys. 51(7), 2839-46

(1969). [69-0451] Pulse radiolysis, Matheson, M. S., Dorfman. L. M., (The M. I. T. Press, Cambridge, Mass., 1969), 202 pp. [69-0456] The radiation chemistry of liquid and glassy methanol.

Dainton, F. S., Salmon, G. A.. Wardman, P., Proc. Roy. Soc. (London) Ser. A3 13, 1-30 (1969). [69-0651] Radiolysis of liquid ethanol-benzene mixtures in the

presence of electron scavengers. Holcman, ,).. Karol- czak, S., Kroh, J., Mayer, J., Mienska, M., Intern. J. Radiation Phys. Chem. 1(4), 457-64 (1969). [69-8025] Application of the refined model of nonhomogeneous

kinetics to the reactions of electrons during the y-radiolysis of ethanol and 2-propanol. Energies and entropies

of activation of the reactions of solvated electrons with

alcohols and with water. Jha, K. N., Freeman, G. R.,

J. Chem. Phys. 51(7), 2846-50 (1969). [70-0064] Electron scavenging in y-irradiated liquid methanol

and ethanol. Rzad. S. J., Fendler, J. H., J. Chem.

Anbar, M., Bambenek, M., Ross, A. B., to be published.

[70-0172] Pulse radiolysis of ethanol. Fletcher,.!. W., Richards,

P. J., Seddon, W. A.. Can. J. Chem. 48(11). 1645-50

(1970). [70-0198] One-electron reactions in biochemical systems as studied by pulse radiolysis. III. Ubiquinone. Land, E.

.)., Swallow, A. J., J. Biol. Chem. 245(8), 1890-4

(1970). [70-0246] Pulse radiolysis studies of deaerated alcoholic solu- tions of alkali halides and potassium hydroxide,

Arai, S.. Kira, A., Imamura, M., J. Phys. Chem.

74(10), 2102-7 (1970). [70-0248] Evidence for very early ionic events in the radiolysis of ethanol. Khorana, S., Hamill, W. H.. J. Phys.

Chem. 74(15),2885-8(1970).

[71-0061] Selected specific rates of reaction of transients from water in aqueous solution. I. Hydrated electron. Anbar, M., Bambenek, M., Ross, A. B., to be published.

[71-0009] y-Radiolysis of liquid ethanol. Yields of hydrogen and

free ions. Solvated electron rate constants. Akhtar,

S. M. S., Freeman, G. R., J. Phys. Chem. 75(18),

2756-62 (1971). [71-0062] Radiolysis of ethanol. Freeman. G. R.. to be published.

[71-0064] Pulse radiolytic induced transient electrical con- ductance 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). [71-0362] Radiolysis of methanol. Baxendale. J. H.. to be

published.

[71-0475] Rate constants and relative yields of solvated elec- trons in concentrated solutions. Rabani, J., Steen,

H. B., Bugge, H., Brustad, T., Chem. Commun. (21), 1353-4(1971).

[71-9165] 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).

13
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FORM NBS-114A (i-7i) U.s. DEPT, of COMM. 1. PUBLICATION OR REPORT NO. 2. Gov t Accession

BIBLI0G

SHEET

C DATA NSRDS-NBS 42 No‘ 3. Recipient s Accession No.

4. TITLE AND SUBTITLE

Selected Specific Rates of Reactions of the Solvated

Electron in Alcohols

5. Publication Date August 1972

6. Performing Organization Code

7. AUTHOR(S)

Edgar Watson, Jr. and Sathyabhama Roy

8. Performing Organization

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NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Address

Atomic Energy Commission and National Bureau of

Standards

13. Type of Report & Period

Covered

NA

14. Sponsoring Agency Code

vmimimm. —

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or less factual summary of most significant information,

bibliography or literature survey, mention it here.)

If document includes a significant

Solvated electrons are generated in alcohols by radiolvsis,

photolysis, reaction with sodium, etc. Rates of reactions

of e“ with solvent and solute molecules, ions, and transients,

in afcohol solutions, have been compiled. Arrhenius parameters

are tabulated for some reactions.

17. KEY WORDS (Alphabetical order, separated by semicolons)

Alcohols* chemical Nineties: data compilation; radiation chemistry; rates;

solvated electron.

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(THIS REPORT)

21. NO. OF PAGES

Ixx] UNLIMITED.

UNCLASSIFIED

22

1 1 FOR OFFICIAL DISTRIBUTION. DO NOT RELEASE

TO NTIS.

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22. Price

30 cents UNCLASSIFIED

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