A method of obtaining measurable concentrations of 02(1Ag) and Oz(lXC,+) for kinetic studies has been developed, and a number of reactions of these excited molecules are described. Evidence is presented for simultaneous electronic transitions in a weakly bound complex between two 02(1Ag) molecules resulting in emission bands at 6340 and 7030A. The phenomenon is discussed in terms of the " association theory " of gases.The (0,l) 1 -58 , u band of the (1 A, -3 Z ; ) system is one of the more intense features of the atmospheric " day glow " (the (0,O) 1.27 p band is re-absorbed by the lower atmosphere).l A number of excitation mechanisms have been suggested by Vallance Jones ; 2 however, all of them depend on assumptions about the deactivation crosssections for O@A,) which have not yet been determined. A prominent feature of the " night air glow " is the (0,l
A spectroscopic study of an orange-red glow from the products of electrical discharge in chlorine has resulted in an identification of the emitter as Cl2(A3II0u+). A kinetic study has provided evidence for the formation of excited molecules in this state by the preassociation of 2P3/2 chlorine atoms. Several detailed mechanisms for the reaction are discussed.
The adsorption and recombination of H atoms at temperatures between 77 and 110 "K have been studied on various silicate glass surfaces consisting of fused silica, porous Vycor with surface adsorbed water, and porous Vycor with chemically altered surfaces achieved by replacement of the surface functional hydroxyl group by chlorine, fluorine, and methoxy substituents.The concentration of adsorbed H atoms was determined by a measurement of the e.s.r. signal and the kinetics of the disappearance of the hydrogen atoms were observed to be second order in mobile atoms, consistent with a diffusion controlled recombination process.The results require that there be at least two types of surface adsorbed atoms, namely, weakly physically adsorbed atoms that are mobile and immobile. Identification of these adsorbed atom types with a particular surface functional feature leading to the adsorption is proposed.The activation energy for the second order decay of hydrogen atoms at the surface was found to vary from 1.0 to 2.3 kcal/mol, depending upon the chemical nature of the surface. A correlation between this activation energy and an electronegativity function of the surface group is presented.
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