Abstract
The rates of reaction of
3
P
oxygen atoms with hydroxyl and hydrogen have been measured in a flow system at pressures around 2 mmHg. The former reaction, O + OH -> H + O
2
, ( — 4) occurred in the products of the rapid reaction between H and NO
2
, and was followed by measurements of atomic oxygen concentrations.
k
-4
was found to be 5±2 x 10
-11
cm
3
molecule
-1
s
-1
at 265 and 293 °K. This result, when combined with data on the reverse reaction at elevated temperatures, gives a value of
k
-4
which is virtually independent of temperature and equal to about 1/20 of the bimolecular collision frequency. The reaction O + H
2
-> OH + H (3) was studied in the absence of molecular oxygen and found to have a rate constant of 6 x 10
-13
exp (-8900/
RT
) cm
3
molecule
-1
s
-1
in the range 409 to 733 °K. This is in good agreement with values obtained at higher temperatures. The rate constant for O + D
2
was significantly less than that for O + H
2
at temperatures between 491 and 671 °K.
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