Abstract
A perfected kinetic intracavity laser spectroscopy method based on a ring travelling wave dye laser with a highly linear algorithm for absorption spectra processing has been developed. Rate constants for the reactions (i) HNO+O 2→ k 1 products, (ii) HNO+HNO→ k 2products have been measured over a temperature range 296-421 K using the developed method. Least-squares fits to Arrhenius expressions yield k 1( T)=2.2×10 10exp[-(4600±200)/ T] cm 3 mol −1 s −1, and k 2( T=3.7 ×10 11×exp[-(1790±80)/ T]cm 3 mol ±1 s ±1. Heterogenous HNO decay has been explored on a quartz surface. The fraction γ of wall collisions that remove HNO obeys the relation 6.6×10 −4exp[-(1530±90)/ T] over a temperature range 296-421 K at initial concentrations [HNO] 0≲3.2×10 −12mol/cm 3.
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