THE RADIOLYSIS OF ETHANOL

111. LIQUID PHASE

J. J. J. MYRONAND G. R. FREEMAN
Chenzistry Department, University of Alberta, Edmonton, Alberta
Received September 11, 1964
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ABSTRACT
T h e G values of the major products of the r-radiolysis of liquid ethanol a t a dose of 2 X 1020
eV/g are: hydrogen, 4.2; acetaldehyde, 1.9; 2,s-butanediol, 2.2; G(-CzHsOH) = 7.5. At pro-
gressively lower doses G(Hz),increases t o a ~naximumof 5.0. The yield of water, G(Hz0) = 0.5,
is equal t o the sum of the y ~ e l d sof the Ce fragments found in the other products.
The approximate yields of three kinetically distinguishable sources of hydrogen were found
t o be G(e& free ion) = 0.9, G(H) = 2.7 and G(unscavengeab1e Hz) = 1.5. The half,life of
solvated electrons with respect t o reactions such a s

is 3 ps.
e,,, + CeH50-+ H
Both l,3-pentadiene and benzene inhibit hydrogen and glycol formation but neither affect
the high dose yield of acetaldehyde. Pentadiene reacts with H atoms and other radicals and
possibly also with eklV. Benzene appears to inhibit hydrogen and glycol formation mainly
by a n unidentified activation transfer process.

INTRODUCTION
Can. J. Chem. 1965.43:381-394.

The yields of products of the 7-radiolysis of liquid ethanol that are reported in the
literature show poor agreement (1-5). Values of G(H2) range from 3.7 to 5.5 and the
yields of acetaldehyde and 2,3-butanediol show a similarly wide variation. The ratios
of the reported yields of the products also vary greatly; for example, the value of the
ratio G(acetaldehyde)/G(2,3-butanediol) has been reported to be 1.8 (3) and 0.7 (5).
The discrepancies between the several sets of results are probably due partly to different
experimental conditions (dose, dose rate, etc.) and partly to the presence of small amounts
of impurities that act as inhibitors.
Three products, hydrogen, acetaldehyde, and 2,3-butanediol, account for 8.5% of the
observed decomposition. Proposed mechanisms have included free radical, molecular, and
ionic reactions (1-8).
The present work was done to obtain further information about the yields of the
products, including water, and about the reaction mechanism.
EXPERIMENTAL
Materials
Benzene-free absolute ethanol from Reliance Chemical Company was used. T h e only impurity detectable
by gas chromatography (g.c.) was water (0.1%). T h e water content was reduced t o ,<0.005% by treatment
with sodium and diethylphthalate follo\ved by distillation (9). T h e purification system was protected from
atmospheric moisture. For low-dose samples ( < 1 X 1020eV/g), the drying was preceded by a modification
of the procedure outlined by Wild (10) for the preparation of 2,4-dinitrophenylhydrazones,t o remove a n y
aldehyde present. T h e purified ethanol was thoroughly degassed and distilled under vacuum into a Pyrex
reservoir.
Phillips Research Grade benzene was distilled, the middle third being retained and stored in the vacuum
system; g.c. analysis showed no detectable hydrocarbon impurities and <0.001% water.
T h e l,3-pentadiene (Columbia Organic Chemicals Company) was purified by vacuum distillation, and
g.c. analysis showed i t t o be 95% pure.
Sample Preparation
T h e sample cells were cleaned with hot sulfonitric acid, rinsed several times with dilute sodium carbonate
solution, then rinsed many times with doubly distilled water.
Most of the samples were 1.0-2.2 ml of liquid contiined in 15 mm O.D. tubes of about 4 ml capacity.
Canadian Journal of Chemistry. Volume 43 (1965)
 382 CANADIAN JOURNAL O F CHEMISTRY. VOL. 43, 1966

However, for water analysis, very thin-walled spherical bulbs (capacity = 0.5 ml) were used to contain
0.1 ml samples.
Irradiation
Co60 y-irradiations were done with three different sources; the approxilnate dose rates were 0.9, 5, and
60 X 1018eV/g h. The dosimetry was done with the Fricke dosimeter. Dose rates for ethanol and ethanol-
inhibitor solutions were calculated using the assumption t h a t the dose rate was proportional to the electron
density of the solution. T o obtain the dose rates for the 0.1 ml samples, a plot of sample volume vs. dose
rate was extrapolated from 0.5 ml t o 0.1 ml.
The temperature during irradiation was 25 f 4 "C.
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T h e ethanol-benzene solutiolls were given a dose of 1.5 X loZoeV/g and the ethanol-1,3-pentadiene
solutions were given 3.5 X loz0eV/g.
Product Analysis
Gaseous products were separated into two fractions by successive distillations of the samples through
traps a t different temperatures (-196' and -112"). T h e total amount of each fraction was measured in
a gas burette and each fraction was analyzed by g.c. with either a charcoal or a silica gel column.
T h e glycols, sec-butyl alcohol, and acetal were measured by g.c. using a di-?z-decyl phthalate on Fluoropak
80 column. T h e glycols used were separated from each other in the following order; ethylene glycol, 13-
propanediol, 2,3-butanediol, 1,s-propanediol, 1,s-butanediol, and 1,4-butanediol.
Acetaldehyde was determined polarographically using a 0.1 M aqueous lithium hydroxide supporting
electrolyte solution a t 0 "C. The total acetaldehyde yield was determined by adding the yields of acetalde-
hyde and acetal. 111 some salnples part of the acetaldehyde reacted with ethanol to produce acetal and
water. Although the amounts of acid present in the salnples were less than that required to alfect the
radiolysis mechanism ( l l ) , otlly a small trace of acid is required (12) to catalyze the reaction
Can. J. Chem. 1965.43:381-394.

Forlualdehyde was analyzed by the chrolnotropic acid neth hod (13).

Water analysis was effected by crushing the thin-walled bulbs directly in the carrier gas stream above
the chromatographic colulnn. After water analysis on a Carbowax 1500 on Fluoropak 80 column, the
sample was led from the first detector cell via a heated stainless steel capillary tube to a second column
(di-72-decyl phthalate on Fluoropak) and detector, by which the acetal yield was determined. The value
of G(H20) was obtained by subtracting the amount of acetal fro111 the total amount of water.

RESULTS
Pure Ethanol
Gaseous Products
The yield of hydrogen decreased rapidly with increasing dose a t low doses, then de-
creased more slowly as the dose increased above about 3 X loL9eV/g (Fig. 1). The value
of G(H2)extrapolated to zero dose was GI(H2) = 5.0. The hydrogen yield was independent
of dose rate and was the same for samples that contained 0.005% or 0.2% water.
The yields of methane, carbon monoxide, ethane, ethylene, and propane are shown as
a function of dose in Fig. 2. Only G(ethy1ene) shows an appreciable dependence on dose
and dose rate (Fig. 2D). Variations in the yields of the other products with dose rate were
random and were within experimental error of each other.
The initial G values of these products are given in Table I.
Liquid Prodz~cts
The yields of acetaldehyde (G = 1.9), formaldehyde (G = 0.13), 2,3-butanediol
(G = 2.2), and 1,2-propanediol (G = 0.13) were independent of dose over the ranges
studied (Fig. 3). However, analytical difficulties prevented the measurement of liquid
product yields in the dose region where the hydrogen yield increased rapidly with de-
creasing dose (i.e., < loi9eV/g).
At high doses ( > 5 X loz0eV/g) the 2,3-butanediol g.c. peak was resolved into a
doublet. With the aid of authentic samples of meso- and d,l-2,3-butanedioll it was estab-
lished that the doublet peak was due to approxiinately equal amounts of the two
diasterioisomers.
' W e are grateful to Dr. F. A. L. Anet of the University of Ottawa for a sawaple of d,l-2,s-bz~lanediol.
 MYRON AND FREEMAN: RADIOL\'SIS O F ETIIANOL
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Can. J. Chem. 1965.43:381-394.

I
0
0 I 2 3 4 5
D O S E ( I OV
~ /~g~)
FIG.1. Hydrogen yield as a function of dose. A: Dose rate = 5 X 1018eV/gh and Hz0 content of
ethanol = 0.005y0; the curve represents equation [iii]. B: Taken from plot A (above), Q dose rate
= 0.9 X 1018eV/g h and Hz0 content = 0.2%; 0 dose rate = 0.9 X 1018eV/g h and H20 content =
0.005y0, dose rate = 5 X 1018eV/g h and Hz0 content = 0.005%, average of four values a t three
different dose rates, 0.9, 5, and 60 X 1018eV/g h, the four values being too close to each other to plot
separately.
TABLE I
Product yields

Lowest dose used Dose rate

Product G (1019 eV/g) (10t8 eV/g h)
Hydrogen
Acetaldehyde
2,3-Butanediol
Water
Methane
Carbon monoxide
Ethane
Ethylene
Acetylene
Propane
Butane
sec-Butanol
Formaldehyde
Ethylene glycol
1,2-Propanediol
1,3-Propanediol
1,3-Butanediol
1.4-Butatlediol
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 43, lOG.5
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Can. J. Chem. 1965.43:381-394.

D O S E ( I O ~e ~V / g )
FIG.2. Various gaseous product yields a s a function of dose. A: Methane. B: Carbon monoxide. C:
Ethane, average of four values a t three different dose rates (0.9, 5, and 60 X 1018eV/g h). D: Ethylene,
0 dose rate = 0.9 X 1018eV/g h, 0dose rate = 5 X 1018eV/g h, dose rate = 60 X 10'8 eV/g h (aver-
age of two values). E : Propane, @ average of two values a t a dose rate of GO X 10'8 eV/g h.

Small yields of 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, ethylene glycol, and

sec-butanol were measured a t doses greater than loz1eV/g (see Table I).
The determination of the value of G(H20) was difficult because of the hygroscopic
nature of pure ethanol and because of the conversion of varying amounts of the acetalde-
hyde into acetal and water. For these reasons, previous values of G(H20) from liquid
phase (8) and vapor phase (13) radiolyses of ethanol were probably too high. Under the
present conditions, the water yield could not be measured accurately a t doses below
6 X log0eV/g ; G(H20) = 0.5 (see Fig. 4 and Table I).
Ethanol-Inhibitor Solutions
The yields of the three major products, hydrogen, acetaldehyde, and 2,3-butanediol,
are plotted a s functions of the electron fraction of inhibitor, E, in Figs. 5 and 6. The
 MYRON A N D F R E E M A N : RADIO1,YSIS O F ETHANOL
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0.0
0 I 2 3 4
DOSE ( lo2' e V / g )
0.3

DOSE (lo2' e V / g )
Can. J. Chem. 1965.43:381-394.

3.0 . I I I I /I 1 I I

0 A 0 0 n

2.0 -
U 0
0 % 0 C

1.0 - C -

0.0 . I I I I / I 1 I
I I I I o/+~I I
0.2 - D
-
0.1
0

0
- I

C
0 0
0.0 I I I / I

0 I 2 3 4 / 9 11 13
DOSE ( lo2' e V / g )
FIG.3. Liquid product yields as a function of dose. A : Acetaldehyde, Q average of two values, 9aver-
age of three values, - - - theoretical yield. B: Formaldehyde. C: 2,3-Butanediol, @ average of two values,
Q average of four values. D: l,ZPropanediol, average of four values.

broken lines in the figures represent values of G(product) that would be expected if the
radiolysis of the inhibitor and of ethanol were unaffected by the presence of each other.
The most remarkable result is t h a t both benzene and 1,3-pentadiene inhibit the formation
of hydrogen and of 2,3-butanediol (Figs. 5, 6B, 6C) but neither additive appreciably
inhibits the formation of acetaldehyde (Fig. 6A). Methane formation is also inhibitable
by both additives (Fig. 7). Where inhibition effects occur, 1,3-pentadiene is a more
efficient inhibitor than is benzene.
Three new products were measured in the pentadiene-ethanol solutions. The g.c. peaks
of these products appeared in the region where Clo hydrocarbon pealts appeared from
 CANADIAN JOURNAL O F CIIEMISTRY. VOL. 43. 1965

I I I 1 I

- -
- 0 0 -
o-o-
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0-
- -
L
0
0
- -
I I I I I

DOSE (102'eV/g)
FIG.4. Water yield as,a function of dose.
Can. J. Chem. 1965.43:381-394.

the same column. The areas of the peaks are plotted against the electron fraction of
1,3-pentadiene, E,, in Fig. 8. Using a calibration factor estimated from those of other
compounds that appeared in the same region, 1 area unit corresponds to a G value of
0.12 -1: 0.02. Thus the maximum G value of product A (Fig. 8) was 1.8 i 0.3, of product
I3 was 0.5 i 0.1, and of C was 0.7 4 0.1. The yield of product A increased approximately
linearly with increasing E,, whereas B and C passed through maxima a t E, = 0.04 and
then decreased linearly with increasing E,.

DISCUSSION
-Mass Balance
A mass balance for carbon, hydrogen, and oxygen, using product yields obtained from
the graphs a t a dose of 2 X loz0eV/g, gave an empirical formula of Cz.00H6.1101.01
and
G(-C2H60) = 7.5. There was a slight stoichiometric excess of hydrogen over the carbon
and oxygen in the products. The excess corresponds to G(H2) = 0.4.
Reaction Mechanism
The present results are consistent with many of the features of the mechanism proposed
for the radiolysis of liquid ethanol by Adams and Sedgwick (4). A similar mechanism
had been proposed earlier by Baxendale and iVIellows for the radiolysis of methanol (14).
The main features of the overall radiolysis are: (a) there are three precursors of hydrogen
that are distinguishable by their ease of reaction with inhibitors; (b) most of the butanediol
is scavengeable; (c) the acetaldehyde produced a t high doses is not scavengeable, although
part of the larger yield of acetaldehyde produced a t low doses is probably scavengeable.
Hydrogen
Adams and Sedgwick (4) suggested that solvated electrons and hydrogen atoms were
kinetically distinguishable precursors of hydrogen and that there was also a "molecular
yield" of hydrogen. The following is a refinement of their mechanism that is suggested
by the present results and consideration of the yields of free ions in various kinds of
liquids (15). The square brackets indicate that the entities are within a spur.
 MYRON A N D F R E E M A N : RADIOLYSIS O F ETHANOL
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Can. J. Chem. 1965.43:381-394.

EXI0
FIG.5. Hydrogen yield as a function of additive concentration, where 6 = electron fraction of additive;
0 l,3-pentadiene, benzene.

[e,lv + CZH$OHZ+]+ [nCzHsOH + HI

+ e;lv + C?H50H2+(free ions)
 C A N A D I A N JOURNAL O F CHEMISTRY. VOL. 43. 1965

5
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Can. J. Chem. 1965.43:381-394.

FIG.6. Acetaldehyde and 2,3-butanediol yields as functions of additive concentration, where a = electron
fraction of additive. A: Acetaldehyde yield, 0 1,3-pentadiene solutions, benzene solutions. B: Butallediol
from benzene solutions. C: Butanediol from pentadiene solutions.

At doses > 1018eV/g, reactions [lo] and [ l l ] become important.

The mechanism does not involve excited molecules as such; however, reaction [2] is
simply reaction [l] involving a more energetic precursor. Excited neutral molecule
reactions cannot be excluded, b u t they appear to contribute less than do the ionic reactions
 MYRON AND FREEMAN: RADIOLYSIS O F ETHANOL
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Can. J. Chem. 1965.43:381-394.

EX10
FIG.7. Methane yield as a function of additive concentration, where e = electron fraction of additive;
0 1,s-pentadiene, benzene.

to the present system. The results indicate that reactions [I] and [2] occur to similar
extents if G(tota1 ionization) = 3-4.
In a mass spectrometric study of ion-molecule reactions, Ryan et al. (16) found that
CH3CHOH+ was the important precursor for the formation of CH3CHZOH2+. Reaction
[3] probably involves the shift of a hydrogen atom along a hydrogen bond in the liquid
phase.
Reactions similar to [5], [6], and [7] will be discussed elsewhere (15).
An alternative to reaction [8] as a fate for the solvated electrons, e,,,, that exist as
free ions in the bulk solution might be
[G'l e,,, + C2H60Hz+ -+ nCzH50H + H.
However, Adams and Sedgwick (4) found that reaction [6'] was not important in neutral
~ ethanol. This conclusion is confirmed by kinetic calculations (17) involving the dose rate,
 CANADIAN JOURNAL OF CHEMISTRY. VOL. 43. 1965
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Can. J. Chem. 1965.43:381-394.

EpxlO
FIG.8. Clohydrocarbon products as functions of pentadiene concentration, e,. The ordinate, area units,
refers to the g.c. peak area of the product. Using an estimated calibration factor, 1.0 area unit corresponds
to a G value of 0.12 f 0.02.

G(free e,,) = 1, the value of the autodissociation constant of ethanol (pK = 19.1,
ref. 18), kg' = 2.0 X 101° l/mole s (19a), k10/k6' = 0.080 (4), and. the curves in Fig. 1.
Briefly, the concentration of CzH60H2+fromthe autodissociation of ethanol (3 X 10-lo M )
is more than an order of magnitude greater than that from the "free ions" generated by
radiolysis. The total [C2HjOH2+]is four or five orders of magnitude too small t o explain
the curve in Fig. 1A by a competition between reactions [lo] and [6'].
The decrease in G(H2) from 5.0 to 4.2 with increasing dose can be explained b ~ com-
r
petition between reactions [8] and [lo]. Thus, G(H2) is given by
 MYRON A N D FREEMAY: RADIOLYSIS OF ETHASOL 3!)1

a t a particular value of [CHBCMO].Since the acetaldehyde concentration increases with

increasing dose, the observed hydrogen yield a t dose D is an average value:"

[ii]
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0.8 In (1 + r)
[iii] = 4.2 +- r ,
where

and

The halfway point between G(H2) = 5.0 and 4.2 occurs a t r = 2.6 and D = 1.1 X 10'"
eV/g. Equation [v] was solved graphically by assuming that G(CH3CHO) varied3 from
Can. J. Chem. 1965.43:381-394.

2.8 t o 1.9 as G(H2) varied from 5.0 t o 4.2 (see later discussion). A t 1.1 X l O l g eV/g,
[CH3CHO] = 3.4 X M and

Thus the half-life of the solvated electron in ethanol is 3.3 ps. Taub et al. (19a) measured
the half-life of the solvated electron in neutral ethanol and found it t o be 3 ps. They
supgested that this half-life was partly due to reaction [GI]. An estimate of 4.0 ps for the
half-life of the solvated electron can be obtained by coinbining data of Adams (4) with
Taub's value of k6,(19a). I t therefore appears likely that the contribution of reaction [GI]
to the decay of the solvated electrons was small, even a t the high dose rate in the pulse
used by Taub (2 X loz3eV/g s (19a)).
The value G(e,,,) = 0.8 is obtained from the data in Fig. 1. Adams and Sedg~vick
(4) reported a value of 1.02 which included a contribution of G = 0.07 for the reaction
(transcribed into the present symbolism)
[I21 e&, -+ C'H, + OH-.
Addition of this contribution to the present yield gives G(e,,,) = 0.9. Taub et al. (19b)
reported G ( ~ L ~ ,=
) 1.0 f 0.3. The three values are in reasonably good agreement.
The inhibition studies were done a t high doses (to give measureable concentrations of
liquid products) where reaction [lo] was proceeding to the exclusion of reaction [8].
Pentadiene was a more effective inhibitor of hydrogen forination than was benzene in
the low concentration region (Fig. 5). The shapes of the pentadiene curves in Figs. 5A
and 5B indicate that there are scavengeable (G = 2.7) and unscavengeable (G = 1.5)
precursors of hydrogen in addition t o the solvated electrons discussed above. The results
are consistent with the suggestion of Adams and Sedgwick (4) that the scavengeable
precursor is atomic hydrogen (they reported G(H) = 2.25 and G,(H2) = 1.65). The
'The following is a rejinenzent of the treatnaent originally presented and w a s suggested by one of the referees.
3The variation i n the acetaldehyde yield i s expected to occr~rat such low doses (see Fig. 3) that the present
method of analysis could not measure i t . The good agreement between the two yields measawed at 0.1 and
0.2 X l P Oe V / g i s fortuitous because they were measured near the detection limit of the method.
 3'32 CANADIAN JOURNAL O F CHEMISTRY. VOL. 13. 1965

source of the unscavengeable hydrogen is possibly a combination of direct decomposition

of ethanol to form i~lolecularproducts,
(13~1 CHsCHzOH* + CHICHO HZ +
[13b] + CH-=CHOH Hz, +
and reaction of hot hydrogen atoms generated by reactions [2] and [GI.
Low concentrations of 1,3-pentadiene are roughly 20 times a s efficient as benzene in
inhibiting hydrogen forillation and about 30 times as efficient a s benzene in inhibiting
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methane formation. The value of the ratio of the methyl affinity of 1,3-pentadiene to
that of benzene in alkane solutions is about 3 000 (20, 21) and it seems unlikely that this
value would be reduced 100-fold by changing the solvent from alltane to ethanol. I t
therefore appears that benzene affects the product yields mainly by an activation transfer
process. The activated species with which benzene interacts has several possible identities
(C2HjOI-I+, e-, [e,,,]) anlong which it is not yet possible to choose. The gas phase
proton affinity of benzene (6.26 eV) is much smaller than that of ethanol (8.4 eV) (22)
so the species is probably not C?HSOH2+.
Kinetic analysis of the data according to the general mechanism4
1141 k + hydrogen
[I31 h + C6Ha + no hydrogen
Can. J. Chem. 1965.43:381-394.

gave kl:/k14 = 0.54 l/mole. Other values obtained for this rate constant ratio are 0.58
for methylcyclohexane-benzene solutions (23), 0.78 for cyclohexane-benzene (24), 0.54
for cyclohexane-cyclohexene (25), 0.2 for cyclol~exanone-benzene (26), and 0.2 for
cyclohexene-benzene (27).
Acetaldehyde and 2,s-Butanediol
Acetaldehyde is formed by reactions [4] and [13], and both acetaldehyde and butanediol
are products of reactions such as [16]-[18].
1161 2CHaCHOH + (CHICHOH),
[17a] CHJCHOH + CI33CH20 + CHICHO + CH3CH20H
[17b] -, CH3CH(OH)OCHzCHs (hemiacetal)
[la BCHICH?O + CH3CHO + CHaCHsOH
The hemiacetal from reaction [17b] is equivalent to acetaldehyde in the present
analytical system.
Pentadiene inhibited the formation of butanediol but not the net rate of formation of
acetaldehyde a t the high dose used. Hayon and Weiss (3) found G(acetalde11yde) = 3.1
a t a low dose (1 X lo1' eV/g), which is higher than the value found a t doses in the
vicinity of 1020eV/g. Although reported product yields vary too much to confidently
draw conclusions from differences between them, the present work indicates that a high
acetaldehyde yield (G = 2.8) would be found in neutral ethanol a t low doses. At high
doses, solvated electrons destroy 0.9 units of the aldehyde. Since the high dose yield of
aldehyde is not inhibited by pentadiene, either (i) the diene reacts both with free radicals
that generate aldehyde in the bulk solution and with the solvated electrons t h a t exist a s
free ions, or (ii) if the diene does not react with solvated electrons, reactions [17] and [18]
occur mainly in the spurs. I t appears that (i) is more likely because reaction [16] occurs
mainly in the bulk medium and is readily inhibitable by the diene. I t is improbable that
reaction [16] would occur mainly in the bulk solution if reactions [17] and [18] occurred
mainly in the spurs.
4U~1knownhydrogen preczrrsors are synzbolized by h.
 MYRON ASD FREEMAN: RADIOLYSIS OF ETI-IANOL 393

Methane
The results from the pentadiene solutions (Fig. 7) show that about 70% of the methane
is scavengeable. Methyl radicals are probably the precursors of the scavengeable methane.
Ethane, Et17,ylene, and Water
Ethane is probably formed by the reaction
[I91 C2H5 + C2HjOH + CzHa + CHaCHOH.
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Ethyl radicals have been detected in photolyzed solid ethanol by electron spin resonance
spectroscopy (28). Possible sources of ethyl radicals in the radiolysis are reactions [12] and
1201 CrH50H* C2H.s + OH
-t

PI1 e,~,. + C2HbOH2+ + CeHj + H20.

Ethylene inay be formed by
[221 CI-13CH20HS + C?H, + H?O.
Some ethane and ethylene might also be formed by the disproportionation of ethyl
radicals with other radicals.
The decrease in G(ethy1ene) with increasing dose can be ascribed to the reaction
[231 R + C2H4 -+ RCzH,..
The average lifetime of the radicals with respect to radical-radical reactions decreases
Can. J. Chem. 1965.43:381-394.

with increasing dose rate, so the dose dependence of the ethylene yield decreases with
increasing dose rate.
Water can be forilled by reactions [21] and [22] and by
[241 OH + CrHjOH H?O + CH3CHOH
+

1251 OH- + C2I-I,OH?+ H?O + CrHjOH.

+

The water yield (G = 0.5) equals the sum of the Cz hydrocarbon fragments found in the
other products:

Clo Hydrocarbons from the Pentadiene Solutions

The maximum yield of two of the Clo products occurs a t e, = 0.04 (Figs. 8B and 8C).
The hydrogen atoms are essentially coinpletely scavenged a t the same diene concentration
(Fig. 5A). I t appears that these Clo compounds are formed by the reactions
[261 H + CHz=CH-CH=CH-CH3 CHa-CH--CH--CH-CH3
+

I
~ 7 1 21 + Clo isomers

G(H) 2G(Cio) 2.4 f 0.4,-

There is evidence that allylic radicals do not disproportionate to an appreciable extent
(26). Thus,

where G(Cl0) refers to the n~axiinumyield of the compounds represented in Figs. 8B and
8C. This value is in good agreement with the estimates of G(H) mentioned earlier.
The Clo hydrocarbon represented in Fig. 8A is apparently a product of the direct
radiolysis of pentadiene.
The products of reactions such as
[281 CHKHOH + CjHs + .ClHuOH
[29I 2 .C.IHI~OH+ (CiHlrOH)2
would not have been observed with the present analytical system.
 394 CANADIAN JOURNAL O F CHEMISTRY. VOL. 43, 1965

Free Radicals and Glycol Formation

The ratio of CH3CHOH:CH2CH20Hradicals contained in the glycols is 69:l. These
figures roughly reflect the relative ease of abstraction of hydrogen from the a- and
P-carbons in ethanol. If this difference is attributed to the difference in the activation
energies of the two abstraction reactions, then A E = 2.7 kcal/mole. This is siinilar to the
value (E31 - E30) = 2.0 kcal/mole (29) found for the reactions
1301 CH3 + CaHs -+ CH4 + CH~CHCHI
Downloaded from www.nrcresearchpress.com by 114.125.173.39 on 11/07/19. For personal use only.

(311 --+ CH1 + CH2CH2CH3.

ACKNOWLEDGMENTS
This work received financial assistance from the National Research Council.

NOTEADDEDIN PROOF:
G. Dobson and L. I. Grossweiner (Radiation Res. 23, 290 (1964)) have recently
photolyzed potassium iodide in ethanol solution, and their results indicate that the
solvated electrons so produced have a half-life of 21 ps. The difference between this half-
life and those reported in the present paper might be due to the difference in reaction
conditions, although the size of the difference is surprising.
Can. J. Chem. 1965.43:381-394.

F. S. Dainton, J. P. Keene, T. J . Kemp, G. A. Salmon and J. Teply (Proc. Chem. Soc.

265 (1964) found a half-life of 1.9 ps for solvated electrons in methanol a t 20°. This is in
general agreement with the present results.

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Can. J. Chem. 1965.43:381-394.