c

UNCLASSIFIED

REPORT NO. KAPL-1111

Chemistry

^ 438/4

General Electric Company

KNOLLS ATOMIC POWER LABORATORY
Schenectady, New York

THE ION-PAIR YIELD OF THE TRITIUM-OXYGEN REACTION

L. M. Dorfman
B. A. Hemmer

April 14, 1954

Operated for the

United States Atomic Energy Commission
by the
General Electric Company
Contract No. W-31-109 Eng-52

UNCLASSIFIED
 DISCLAIMER

This report was prepared as an account of work sponsored by an

agency of the United States Government. Neither the United States
Government nor any agency thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal liability
or responsibility for the accuracy, completeness, or usefulness of any
information, apparatus, product, or process disclosed, or represents
that its use would not infringe privately owned rights. Reference
herein to any specific commercial product, process, or service by
trade name, trademark, manufacturer, or otherwise does not
necessarily constitute or imply its endorsement, recommendation, or
favoring by the United States Government or any agency thereof. The
views and opinions of authors expressed herein do not necessarily
state or reflect those of the United States Government or any agency
thereof.

D IS C L A IM E R

Portions of this document may be illegible in electronic image

products. Images are produced from the best available
original document.
 I I

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ACKNOWLEDGMENT

The authors are indebted to Miss C. J. Hibbert and personnel of the

Machine Calculations Unit and to Dr. W. S. Horton of the Chemistry and
Chemical Engineering Section for their assistance in the curve-fitting
computations.
 KAPL-1111

COHTEHTS

Page

Abstract......................................................................................................................................................................... 11

Introduction ................................................................................................................................................... 13

Preliminary Experiments...................................................................................................................................13

Experimental Methods . 14

Eesults and Discussion...................................................... 19

LIST OF ILLUSTRATIONS

K-6A5755 Bourdon Gauge ..................................................................................................................... 15

KH-9A3126 Bourdon Gauge Calibration . py

KH-9A3158 Rate Curves for Runs 5 and 8.....................................................................................21

KH-9A3159 Dependence of Yield on Isotopic Composition of Hydrogen . . 25

KH-9A316O Test of Equation 4............................................................................................................27

 ABSTRACT

The rate of reaction of tritium and oxygen, initiated by the tritium

beta-radiation, has been investigated at 25°C in the absence of mercury
vapour, by using a sensitive Bourdon gauge as the manometer. The rate is
not linear with time, but shows a small continual decrease as the reaction
proceeds. The initial reaction rate was found to be directly proportional
to the tritium pressure and hence proportional to the radiation intensity.
It was independent of the oxygen concentration over the range investigated.
The reaction rate shows a slight dependence on the isotopic composition of
the hydrogen reactant, tending to rise with increase in the mole fraction
of protium. The initial reaction rate may be represented by:

R0 = 1.19 X 1CT4 CT2 (1 + 0.3 mH)

where is the tritium concentration in moles/liter or other absolute

concentration units, and mH is the mole fraction of protium in the hydrogen
reactant. On the basis of a requirement of 33 ev Ve:r i°n pair in the
reactant mixture, the initial ion-pair yield for tritium disappearance or
water formation is (M/N)0 = 3*2^ for the reaction of pure tritium with
oxygen. Material balance measurements indicate that little or no peroxide
appears in the product.

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 1
13

THE IOH-PAIE TIEID OF THE TRITIUM-OXYGEN REACTION

L. M. Dorfman and B. A. Hemmer

INTRODUCTION

The combination of hydrogen and oxygen under various types of initiation

and activation to form water and,, under certain conditions^ hydrogen peroxide,
has been the subject of very extensive investigations over a period of years.
The mechanism of the thermal reaction,, which has received the greatest part
of this attention, is reasonably well established.-^^ A considerable amount
of work has been done on the synthesis of water in various types of electric
discharge,and reaction rates have also been determined for the combination
of hydrogen and oxygen induced by alpha particles.5 In an investigation of
this latter effect Lind^ found a water yield of 3*92 molecules per ion pair.
Marshall,^ in his work on the hydrogen-oxygen combination under the effect
of cathode rays, reported yields similar to those of Lind. He found also
that in a flow system substantial amounts of hydrogen peroxide were obtained.
Photochemical investigations^ have been made both by absorption in the
Schumann region and by mercury photosensitization. In the latter type of
studies quantum yields on the order of 2 have been obtained.

The isotopic hydrogen-oxygen system consisting of tritium and oxygen

presents a rather interesting study since it has a self-contained source
of ionizing radiation, the nuclear beta-particles from the tritium decay,
and will therefore undergo reaction at room temperature in the absence of
any external excitation energy. The intensity of ionizing radiation is
readily determinable from the tritium concentration since the radioactive
half life and the average energy of the beta-spectrum are accurately known.
In order to determine reaction yields, therefore, the rate of the beta-
particle induced reactions

T2 * jp2 ~ T2° (1)

has been investigated at 25°C in the absence of mercury vapour, by using a

sensitive glass Bourdon gauge as the manometric device.

PRELIMINARY EXPERIMENTS

Complete details of four preliminary runs will not be given. These

experiments are being mentioned here only insofar as they demonstrate the
need for a mercury-free reaction cell in the investigation which followed.
These preliminary runs were carried out in a cylindrical quartz cell
connected to a mercury manometer. The reaction rate was determined by
following the pressure drop. At the end of each run the condensable
product was frozen out and its pressure subsequently measured to determine
the material balance. If tritiated water is the only reaction product,
complete material balance would be represented by P^/bAP = 1, where is
the pressure of the water product and AP the pressure drop. Substantial

KAPL-1111
deficienciss were always foundj the values for this ratio ranged from 0.70 to
0.87. During the runs a thin yellowish deposit accumulated on the walls of
the cell and the mercury in the manometer 'became discolored, probably because
of oxidation.

After these runs the occasion arose to store some tritium in this same
cell, which had previously been degassed. At the end of a week the yellowish
deposit on the walls of the cell had disappeared and the mercury appeared
quite clean. Tritiated water had been formed from the reduction of the
mercury oxide, probably through the action of the tritium atoms present.

Hg° + T s H + OT (2)

The-water was frozen out and measured. The amount present was sufficient to
bring the cumulative material balance for the four run,3 up to 0.9^• It was
clear, then, that oxidation of the mercury was the major reason for the
material balance deficiency, Subsequent runs were therefore carried out in
a mercury-free reaction cell.

EXESRIMEKTA1, METHODS

Pure reactants were obtained in the following manner. Oxygen was prepared
by thermally decomposing potassium permanganate which had previously been warmed
and degassed repeatedly in the vacuum system. The oxygen liberated was passed
through a coil immersed in liquid nitrogen and then into a storage bulb closed
off by a Fugassi valve. Hydrogen was purified by sorption, pumping, and sub­
sequent desorption os a uranium bed. The hydrogen was stored in a Pyrex bulb
connected to a Fugassi valve. The tritium was stored on a uranium bed and
desorbed as required for each run. Krypton gas, used in one run, was degassed
for a short time at -195°C and then pumped into the reaction cell through a
trap immersed in a dry ice - acetone bath.

The H2“^2 mi-xtures use3 in the runs were analyzed on the General Electric
analytical mass spectrometer in use here. Previous calibrations^ had shown
that the two isotopes have equal mass speetrometrie sensitivities.

A modified glass Bourdon gauge with a tilting mirror attachment was used
to follow the pressure drop during the run. The arrangement employed a lamp
and translucent scale at a distance of 50 inches from the tilting mirror. The
Bourdon gauge with reaction vessel attached .is shown in Figure K-6A5755• The
tilting mirror M is suspended in a glass stirrup T and has a connection to
the tip of the spoon gauge S, by means of the glass hook H. W is a plane
window and J a ground glass joint. In the event of breakage of the spoon a
relacement could be made without removing the whole assembly from the hot
laboratory.

Beproducible calibrations showed a gauge sensitivity of 27-9 scale

deflection per mm, pressure differential. The calibration curves are shown
in Figure KH-9A3126. The response was linear over a pressure difference of
at least 10 mm, and the gauge could therefore be used either as a direct

KAPL-1111
 GENERAL electric CO.
KNOLLS ATOMIC POWER LAB.

BOURDON GAUGE

L.M. DORFMAN MAY 12, 1954

ISSUED! /^r /4,/9jT'f
 GENERAL ELECTRIC CO.
KNOLLS ATOMIC POWER LAB.

12 100 mm

11 SENSITIVITY ____ _______ ________

27.9 mm. SCALE / mm. PRESSURE

300 mm.
10

8 200 mm.

BOURDON GUAGE
CALIBRATION
2

SCALE READING (mm.)

0,
190 230 270 310 350 390 430 470
L.M. DORFMAN APRIL 16, 1954 KH-9A3I26
 19
II
reading or a null instrument. The outside envelope of the Bourdon gauge was
connected to a mercury bulb for sensitive pressure adjustment^ and to a
mercury manometer on which the pressure was read with a cathetometer. The
inside of the gauge was connected to the reaction cell C.

The reaction vessel was a spherical Pyrex bulb to which was connected
a very small U-tube for freezing out the water product at the end of the
run. The actual bulb volume was 212 cc_, the total reaction volume 248 cc.
The reaction cell was closed by a 2 mm vacuum stopcock. V, lubricated with
Apiezon-N grease. The outlet arm of this stopcock was connected to a
U-tube and hence to the vacuum system. This outside U-tube was kept in
a dry ice - acetone bath to remove mercury vapour from the cell during
degassing and to prevent its re-entry during filling of the cell. At no
time during the series of 11 runs was there any discoloration or deposit
on the walls of the cell,, which would have resulted from oxidation of the
mercury.

The reactants were mixed in a separate bulb, transferred to the

reaction cell by means of a Tospler pump, and the pressure readings were
started. The reaction cell was immersed in a water bath, which, although
not thermostated, maintained a temperature of 25-0 * 2.0°C. Precise
temperature readings, using a thermometer with 0.02°C graduations, were
taken at the time of each pressure reading. The pressure was read inter­
mittently for a period of 20 to 40 hours over a total pressure change of
at least 3 ™n and in no case more than 8 mm. The pressure of the water
product was thus always below its equilibrium vapour pressure to ensure
that the tritium would remain in the gas phase.

If, at the end of a run, material balance measurements were desired,

the condensable product was frozen inside the cell using liquid nitrogen
and the remaining tritium-oxygen mixture removed. The pressure of the
condensable product- could then be read. The tritium-oxygen mixture, and
later the water product, was processed over a magnesium bed at 600°C to
remove the oxygen and to permit the tritium to be taken up again on a
uranium bed.

In the single run which contained krypton, the krypton was frozen in
the cell at -195°C and the reactant gases were then added in the normal
manner to start the run.

EESULTS AND DISCUSSION

A series of 11 runs was carried out involving varying amounts of the

two hydrogen isotopes and oxygen. To avoid any confusion in nomenclature
the normal stable isotope will be referred to as protium, and a mixture of
the two isotopes, protium and tritium, will be referred to as hydrogen.

The tritium pressure covered a range of 30 to 104 mm, the oxygen

pressure ranged from 69 to 218 mm. The mole fraction of protium in the
hydrogen reactant ranged from 0.055; the purest tritium used, to O.83I.
The details of these experimental conditions are listed in Table I. The

KAPL-1111
20

results of marierial balance measurements for six of the runs are listed in
column 5. They show that the over-all reaction may5 indeed,, he almost
completely represented by Equation 1. If water is the only condensable
product^ PW/2AP - 1. This ratio attains values as high as 0.97 and O.98,
indicating that if any hydrogen peroxide is formed it must., in the static
system involved here,, have only a transitory existence, ultimately
amounting to less than 2 to 3^ of the condensable product.

TABLE I

RESULTS OF TR IT HIM-OXYGEN BURS

Material SS) t - 0 . ^0.

Run, Pressure of Reac■tants, mm Balance • dt‘ - ^ (1/0.3 TO)
Bo. Tritium Prot,iuTn Oxygen Pw/2AP mm/min x 103 mxn ■L x 10*

7 104.4 7-4 69.4 0.94 6.16 1.16

1 95»8 16.9 115.5 0.97 6.57 1.31

? 92.6 10.5 218.3 0.97 5.03 1.06

8 73-8 4.4 138.0 O.96 4.53 1.21

10* 56.9 3-3 93-7 - 2.90 1.00

9 45.2 127.3 99.9 - 3.26 1.18

4 42.2 16.4 106.8 0.98 2.62 l.l4

ll 39.8 195.9 68.9 - 2.80 1.13

6 37-5 72.2 90.2 - 2.94 1.31

5 32.4 82.1 103.0 2.12 1.08

3 30.2 18.5 184.0 0.96 2.24 1.30

♦Mean = 1.19

*Run 10 contains , in addition to the reactants shown. krypton at a

pressure of 85.6 mm. It has teen omitted in averaging the values for k.

The rate curves for two of the runs !are shown in Figure KH-9A3158 in
which the pre ssure, on a greatly expanded scale, is plotted against the
time in minutes„ It may be seen that the rate is not independent of time
hut shows a slight continual decrease as the reaction proceeds. The most
definitive rate to be: used in a correlation of the data is the initial rate.
obtained from the slope of the z•ate curves at the ordinate axis. These
initial slopes have been calculated for each run by fitting the third degree
polynomial: ^
y ™ a + bx + ex^ + dx' (3)

KAPL-1111
 GENERAL ELECTRIC CO.
KNOLLS ATOMIC POWER LAB.
»

2000
l

1600
1200
J3

400
L.M. DORFMAN MAY 12, 1954 K H -9 A ^ 5 8
 lyL 23

to each set of points. The limiting slope ¥83 obtained as the coefficient
of the first degree term. These calculations were carried out by the machine
calculations group. The results are listed in column 6 of Table which
shows the initial rate of pressure decrease in mm/min. The initial reaction
rate^ in terms of hydrogen disappearance or water formation^ will be twice
the rate of pressure decrease.

The intensity of beta-radiation may be calculated directly from the

tritium concentration. The tritium beta-spectrum has an end-point energy
of 18 kev°>9 aE(j aE average energy of 5>69 kev.-*-® The range11 for these
nuclear beta-particles is 0.7 mg/crn^. From the results of a recent deter-
mination1^ of the absorption curves for tritium beta-particles in hydrogen
and oxygen^ it can be shown that in the present investigation, with a
reaction cell 73 ™n in diameter, the gas density is sufficiently high in
all runs so that practically all the beta-particle energy is absorbed in
the gas phase. For the series of runs shown in Table I, therefore, the
absorbed beta-intensity is proportional to the tritium pressure.

It may be seen from the data that, the reaction rate increases with
increasing tritium pressure, or, in other words, with increasing intensity
of the initiating beta-radiation. It can be shown that the initial rate
is directly proportional to the tritium pressure. There is, however, a
small secondary effect which must be taken into account in this correlation.
The reaction rate shows a slight dependence on the isotopic composition of
the hydrogen reactant, tending to rise with increase in the mole fraction
of protium. This may be seen from Figure KH-9A3159 is which the initial
rate divided by the tritium pressure is plotted against the mole fraction
of protium in the hydrogen. The ratio on the ordinate is proportional to
the initial ion-pair yield. As an approximation this isotope effect has
been represented as a linear trend. Evidence of such an effect was obtained
in the preliminary experiments in which mass speetrometrie analyses showed
an isotopic fractionation in the reaction, with protium concentrating in
the water product.

The initial reaction rate, for the conditions of this investigation,

may be represented by the equation:

Eq - (1 + hmg) (4)

where R0 is the initial reaction rate, with units determined by the units
in which is expressed. Crpp is the tritium concentration in moles/liter
or other absolute concentration unitsj k is the rate constant in min_15 b,
the isotope effect correction, has the value 0.3! a:E^ mH ls m°le
fraction of protium in the hydrogen reactant.

The validity of Equation 4 may be seen from Figure KH-9A3160, in which

R0/(l + 0.3 mjj) is plotted against the tritium, pressure. A straight line
through the origin fits the data reasonably well over a 3 l/2-fold variation
in tritium pressure. The values of k for each run are listed in column 7 of
Table I. k has a mean value of 1.19 x 10“^ min"1, with an average deviation
from the mean of 0.076 or 6.4$.

KAPL-1111
2k
>3
Since the initial rate is directly proportional to the tritium pressure,
and hence to the absorbed beta-energy, the initial ion-pair yield (M/N)0 for
hydrogen disappearance will be independent of the tritium pressure. On the
basis of an energy requirement's of 33 ev Per iOE pair in the reactant mixture
Equation 4 gives an initial yield of (m/n)-^ = molecules/ion pair for the
reaction of pure tritium with oxygen. On ?he basis of the observed isotope
effect the initial yield for the beta-particle induced reaction of pure
protium with oxygen is (m/n)^ =4.2 molecules/ion pair. This latter value
compares very closely with tSe value 3-92 obtained by Lind^ for the alpha-
particle induced reaction. Lind's value is obtained directly from the
measurement of a finite pressure change, and may be expected to be somewhat
lower than the initial yield. The experimental yield values above correspond
to G values of 9-8 and 12.7 molecules/lOO ev, respectively.

An extensive discussion of the reaction mechanism does not seem to be

warranted, since it must be stated that examination of a number of mechanisms
fails to meet the test of uniqueness. Several different reaction schemes
lead to a rate equation of the form E = f (intensity), with E independent of
the reactant pressures as long as the total pressure is high enough for
complete absorption of the beta-radiation. Several significant factors
pertaining to mechanism may, however, be pointed out.

It is clear from the values for the ion-pair yield that the reaction
involves very short chains, but that branched chains do not occur. This
is probably due, as in the case of the thermal reaction, to the fact that
the reaction:

T + 02 = OT + 0 (5)

does not occur at room temperature, having an activation energy^ of 17 kcal

in the case of protium. The fate of the hydrogen atoms is then:

T + 02 = T02 (6)

Although little or no hydrogen peroxide appears in the product, it must be

formed in the reaction, subsequently disappearing by reaction with atoms
and radicals. This conclusion is a necessary consequence of the requirement
for a chain terminating step of the type:

to2 + to2 = t2o2 + o2 (7)

Chain breaking steps which re-form reactants, for example:

T + T = T? (8)
i
lead to a rate equation of the form E = f{lo)d + f'(l0) where I0 is the beta-
intensity, and are therefore excluded.

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 I I I

/4

20
L.M. DORFMAN

KNOLLS ATOMIC POWER LAB.

GENERAL ELECTRIC CO.
MAY

12
12, 1954

DEPENDENCE OF YIELD ON
ISOTOPIC COMPOSITION OF HYDROGEN

8
K H -9 A 3 I5 9

MOLE FRACTION OF PROTIUM

0 0.2 0.4 0.6 0.8 1.0

 GENERAL ELECTRIC CO.
KNOLLS ATOMIC POWER LAB.

120
100

L.M. DORFMAN MAY 12, 1954 KH-9A3I 60

 29

A kinetic analysis of the data will not differentiate between the role
of oxygen atoms or ozone in the reaction with hydrogen molecules. The
possible role of excited ozone molecules is suggested in view of the high
energy of the initiating radiation. And finally, the occurrence of an
efficient energy transfer process is suggested by the fact that the presence
of krypton seems to have little or no effect on the yield. The krypton
would, however, markedly affect the primary absorption process.

KAPL-1111
 31

REFERENCES

1. von Elbe, G. and Lewis, B., J. Chem. Phys. 10, 366 (1942).

2. Lewis, B. and von Elbe, G. Third Symposium on Combustion, Flame and

Explosion Phenomena. Baltimore: Williams and Wilkins Co., 1949>
p. 484.

3. Kirkby, P. J., Proc. Roy. Soc. London A 85, 151 (19H) •

4. Marshall, A. L., J. Am. Chem. Soc. 50, 3197 (1928).

5- Lind, S. C., J. Am. Chem. Soc. 4l, 531 (1919).

6. Noyes, W. A. Jr. and Leighton, P. A. The Photochemistry of Gases.

New York: Reinhold Publishing Corp., 1941, p. 236 f and 250 f.

7. Mattraw, H. C., Pachucki, C. F., and Dorfman, L. M., J. Chem. Phys.

20, 926 (1952).

8. Curran, S. C., Angus, J., and Cockroft, A. L., Phil. Mag. 40, 53
(1949).

9. Hanna, G. C. and Pontecorvo, B., Phys. Rev. 75* 983 (1949)-

10. Jenks, G. H., Ghormley, J. A., and Sweeton, F. H., Phys. Rev. 75>
701 (1949).

11. Glendenin, L. E., Nucleonics 2 No. 1, 12 (1948).

12. Dorfman, L. M., Phys. Rev. in press.

13. Valentine, J. M. and Curran, S. C., Phil. Mag. 4^, 964 (1952).

14. Lewis, B., and von Elbe, G. Combustion, Flames and Explosions of Gases.
New York: Academic Press, 1951> P- 28.

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