Journal of Physical Chemistry p. 2268 - 2274 (1985)
Update date:2022-08-17
Topics:
Macpherson, Martyn T.
Pilling, Michael J.
Smith, Martin J. C.
The absorption cross section, ?, for the CH3 transition at 216.36 nm has been measured for a 0.60-nm band-pass.At 298 K, the cross section was determined by comparing the ethane yield, as measured by gas chromatography, with zero-time CH3 absorbance following laser flash photolysis of azomethane at 193 nm. ? was also measured over the temperature range 298-537 K by a repetitive photolysis method in which a known initial pressure of azomethane was repeatedly photolyzed with an ArF laser and the zero-time absorbance determined following each laser pulse.The two room-temperature determinations gave cross sections in good agreement < 4.12+/- 0,24)E-17 cm2 (end product analysis) and (4.01+/-0,26)E-17 cm2 (repeated photolysis)>.Combining these cross sections with our recent determination of k/q, where k is the recombination rate constant, gives a limiting high-pressure rate constant (k infinite) at 296 K of (6.47+/-0.20)E-11 cm3/molecule*sec which is significantly higher than the currently recommended value. k infinite decreases slightly with temperature, and it may be expressed in the form k infinite = (4.09+/-0.36)E-11 exp((137+/-33)/(T/K)) cm3/molecule*sec over the temperature range 296-577 K.The quoted errors represent 95percent confidence limits.
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