THE t-C_4H_9OCH_2 RADICAL IN THE GAS PHASE: DETECTION BY MULTIPHOTON IONIZATION AND THE REACTIONS WITH O, O_2, O_3, H, AND NO

摘要

The detection of the t-C_4H_9OCH_2 and the CH_3OCH_2 radical by the multiphoton ionization/mass spec-trometry/discharge fast flow reactor technique has been investigated in the wavelength region λ= 420-530 nm. For both radicals, unstructured bands were observed. The rate of the five reactions of the t-C_4H_9OCH_2 radical with O, O_2, O_3, H, and NO have been determined with reference to the corresponding CH_3OCH_2 radical reactions in the temperature range of 249-684 K at low pressure (around 2 mbar) t-C_4H_9OCH_2 + O → products κ_1 = (1.80 +- 0.5) ·10~(14)(T/300 K)~(0.46+-0.15) cm~3 mol~(-1) s~(-1) (253 ≤ T/K ≤ 684) (1) t-C_4H_9OCH_2 + O_2→ products κ_2 = (6.7 +- 0.04)·10~(11)(T/300 K)~(-1.1+-0.2) cm~3 mol~(-1) s~(-1) (2) t-C_4H_9OCH_2 + O_3→ products κ_3 = (6.7 +- 0.1)·10~(12)(T/300 K)~(-0.73+-0.3) cm~3 mol~(-1) s~(-1) (249 ≤ T/K≤363) (3) t-C_4H_9OCH_2 + H products κ_4 = (2.5 +- 0.1) ·10~(13)(T/300 K)~(-0.50+-0.1) cm~3 mol~(-1) s~(-1) (4) t-C_4H_9OCH_2 + NO→ products κ_5 = (2.6 +- 0.1)·10~(10)(T/300 K)~(1.5+-0.6) cm~3 mol~(-1) s~(-1) (5) The formation of the primary products is discussed on the basis of mass spectrometric detection using low-energy electron impact ionization.