Time-resolved infrared study of bimolecular reactions between tert-butyl radicals

The gas phase IR spectrum of t-butyl radicals near ∼3μm has been observed by the time-resolved infrared technique known as TRISP. The transient spectrum is observed to decay with second-order kinetics, and a total rate of decay kc + kd = 1010.26 liter mole-1 sec-1 is measured. From a gas chromatograph/mass spectrometer analysis of the reaction products, it is found that kd/kc = 2.9. Thus kc = 109.6 l and kd = 10 10.13 liter mole-1 sec-1. The t-butyl radicals were created by ruby laser photolysis of monomeric (CH3) 3CNO vapor. © 1981 American Institute of Physics.