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I. 54 54 I. INTRODUCTION The diffusion cloud (flame) technique developed by Hartel and Polanyi’, in the 1930s is one of the early methods of studying rapid bimolecular chemical reactions under pseudo-first-order, steady-state conditions. This method is the source of most measured rates for reactions of alkali metals with halogenated compounds3 and still serves as a basis for experimental4 and theoretical’ studies. In most applications of the technique, sodium metal is heated in an oven, mixed with an inert carrier gas, and allowed to diffuse into a background of a reactant gas.

7. Stern-Volmer plots of NO fluorescence quenching by oxygen and nitromethane. Data are shown for the ground vibrational states of the A 2 Z + , C'lr and D 2 Z + of NO, as indicated in the figure. Square symbols refer to CH,NO,, circles to 0,. were converted to energy transfer cross-sections, u, using kq=U(V) (23) where ( V ) is the average relative velocity given by ( V ) = (8kT/77p)'l2,p being the reduced mass of the collision pair. A case of special interest is that of SO,, whose one-photon absorption is also known to overlap that of NO.

Referen~s. . . . . . . . . . . . . . . . . . . . . . . I. 54 54 I. INTRODUCTION The diffusion cloud (flame) technique developed by Hartel and Polanyi’, in the 1930s is one of the early methods of studying rapid bimolecular chemical reactions under pseudo-first-order, steady-state conditions. This method is the source of most measured rates for reactions of alkali metals with halogenated compounds3 and still serves as a basis for experimental4 and theoretical’ studies. In most applications of the technique, sodium metal is heated in an oven, mixed with an inert carrier gas, and allowed to diffuse into a background of a reactant gas.

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