Disproportionation to Combination Ratios of Alkoxy Radicals with Nitric Oxide

Article abstract of DOI:10.1021/j100259a041

The disproportionation to combination ratios were measured at 175 deg C for the reactions RO + 15NO -> RO15NO (2a) and RO + 15NO -> RCHO + H15NO (2b), with the following alkoxy radicals: C2H5O, n-C3H7O, n-C4H9O, and i-C4H9O.The alkoxy radical was generated by the termal decomposition of the corresponding alkyl nitrite in the presence of 15NO.The rate of the corresponding isotopically enriched alkyl nitrite was measured by mass spectrometry while the aldehyde rate was determined by gas chromatography.The results obtained for k_2b/k₂ were 0.22 +/= 0.02, 0.26 +/= 0.03, 0.29 +/= 005, and 033 +/= 0.03, respectively, for C2H5O, n-C3H7O, n-C4H9O, and i-C4H9O.With these values of k_2b/k₂ we were able to determine the primary quantum yield of the photolysis of the corresponding alkyl nitrites at 366 nm to be, respectively, 0.32 +/= 0.04, 0.44 +/= 0.06, 0.19 +/= 0.04, and 0.19 +/= 0.02.