The reactions of O(³P) with ozone and carbonyl sulfide

Abstract

The competitive reactions between 2-trifluoromethylpropene (TMP) and OCS for O( atoms were studied between 300" and 523"K, using the mercury-senstitized photolysis of N20 as a source of O ( 3 P ) . From the known value for the rate constant of the O ( 3 P ) 4-TMP reaction, k3 was found to be 1.6X10-l1 exp (-4500/RT) cm3/particle-sec, where reaction (3) is (3) O~P )+ ocs co + soMixtures of p3 and OCS were photolyzed at 197", 228", 273", and 299°K with radiation above 4300 A to produce O ( 3 P ) from the photolysis of 03, and thus study the competition between reaction (3) and (1) o ( 3~) + 0 3 -zo2

Gas Phase Reaction Kinetics

“…Another reaction of importance in the atmosphere is 0 + 03 -+ 202• A new flow study (44) of this reaction using 0 generated by thermal decomposition of 03 (thus avoiding excited species from a discharge) and 0 + NO chemi luminescent detection over the range 269-409°K has given the result k = 6.3 X 101 2 exp (-4310/RT), which is in excellent agreement with a slightly earlier study (45) over the overlapping range 197-299°K. The latter was a competitive rate study relying on a series of two other relative rates, however, and the error possibilities are obvious.…”

Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide

“…An examination of the previous studies of reaction (1) shows primarily two values for k 1 with a rather large discrepancy between them. 9 The values are (l-2)xlO exp(-5800/RT)cm molec sec reported by Wagner 2 ' 3 and (1.6-3.2)xl0 -1 1 exp(-4500/RT)cm 3 molec -sec-1 reported by Heicklen 6 and Westenberg. 4 The most obvious disagreement lies in the factor of -6 in the A-factor.…”

Global ozone balance in the natural stratosphere

“…Rate constants, k, including values from 1906 to 1972, for e reaction e are given in Figure 16 [ Davis et al, 1973a;McCrumb and Kaufman, 1972;Krezenski et al, 1971;Jones and Davidson, 1962;Garvin, 1954;Jahn, 1906;Glissmen and Schumacher, 1933]. The line through the points was used in these calculations, except when ke was varied as a sensitivity test.…”