An apparatus has been designed and constructed which will rapidly mix two gaseous reactants, isolate them in a reaction cell, and, by means of light absorption, follow the course of the reaction photoelectrically in one‐tenth of a second or less. The output of the photoelectric tube is recorded by a time‐exposure photograph of the screen of an oscilloscope.

The kinetics of the fast reaction between ozone and nitrogen dioxide was studied over a tenfold range of concentration of each reactant. The rate law was found to be
−d(O3)/dt=k(NO2)(O3)
over the entire course of the reaction. From the temperature coefficient of the rate of reaction the energy of activation was found to be 7.0±0.6 kilo‐calories per mole. A mechanism is proposed to account for the observations.
1.
O. R.
Wulf
,
F.
Daniels
, and
S.
Karrer
,
J. Am. Chem. Soc.
44
,
2398
(
1922
).
2.
F. H.
Verhoek
and
F.
Daniels
,
J. Am. Chem. Soc.
53
,
1250
(
1931
).
3.
W. F.
Giauque
and
J. D.
Kemp
,
J. Chem. Phys.
6
,
40
(
1938
).
4.
H.
Hartridge
and
F. J. W.
Roughton
,
Proc. Camb. Phil. Soc.
23
,
450
(
1926
).
5.
P. D.
Brass
and
R. C.
Tolman
,
J. Am. Chem. Soc.
54
,
1003
(
1932
).
6.
F. R. Bichowsky and F. D. Rossini, The Thermochemistry of Chemical Substances (Reinhold Publishing Corporation, New York, 1936).
7.
R. A. Fisher, Statistical Methods for Research Workers (Oliver and Boyd, Edinburgh, 1938), p. 139.
8.
H. J.
Schumacher
and
G.
Sprenger
,
Zeits. f. Physik. Chemie
B2
,
267
(
1929
);
G.
Sprenger
,
Zeits. f. Elektrochem.
37
,
674
(
1931
).
9.
J. H.
Smith
and
F.
Daniels
,
J. Am. Chem. Soc.
69
,
1735
(
1947
).
10.
R. A.
Ogg
, Jr.
,
J. Chem. Phys.
15
,
337
(
1947
).
11.
H. J.
Jones
and
O. R.
Wulf
,
J. Chem. Phys.
5
,
873
(
1937
).
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