The photochemistry of nitrosyl halides: The X+NOX→X2+NO(v) reaction (X=Cl, Br)

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Abstract
The primary and secondary photochemistry of NOBr and NOCl has been monitored by detecting infrared fluorescence from vibrationally excited NO following pulsed photolysis of the parent compound with a tunable laser. For wavelengths greater than 480 nm the primary photolysis of NOX to NO+X produces little if any vibrational excitation in the NO product. However, secondary photochemistry produces excited NO through the reaction X+NOX→X2+NO(v). From the dependence of the rise time of NO fluorescence on the pressure of NOBr or NOCl at a constant pressure of added argon, it is found that the rate constants for the Br+NOBr and Cl+NOCl reactions are (5.16±0.28) ×10−12 and (5.40±0.47) ×10−12 cm3 molecule−1 sec−1, respectively. The reaction of Br with NOBr produces more NO in v=3 and/or v=2 than in v=1. At 355 nm roughly half of the NO vibrational fluorescence is due to the primary dissociation NOX→X+NO(v).

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