Accession Number : AD0830238
Title : ION CHEMISTRY.
Descriptive Note : Final technical rept. 1 Nov 65-31 Oct 67,
Corporate Author : KANSAS UNIV LAWRENCE DEPT OF CHEMISTRY
Personal Author(s) : Kevan, Larry ; Zimbrick, John ; Viswanathan, N. S.
Report Date : DEC 1967
Pagination or Media Count : 233
Abstract : The paramagnetic relaxation characteristics of trapped electrons and hydrogen atoms in gamma-irradiated alkaline, acid and oxyanion ices and of trapped radicals in methacrylate polymers were studied by power saturation methods. The relaxation times were measured as a function of radiation dose, deuteration, phase and temperature. Linewidths were measured under various conditions. The trapped electron EPR line is inhomogeneously broadened by nuclear hyperfine interactions; the spin-lattice relaxation mechanism is a cross relaxation process with O(-). The electrons are trapped with a nonuniform spatial distribution in vacancy sites in radiation-produced spurs of 30A radius. The H atoms are trapped with spatial uniformity at interstitial sites near oxyanions. The formation of dielectrons in irradiated alkaline ices is demonstrated by high radiation doses and by optical bleaching. Dielectrons are diamagnetic and have a broad optical band with a maximum near 900 nm. The relative reaction rates of mobile electrons in ice are given and compared with solvated electron rates in water. Mobile and solvated electrons appear to be structurally similar and to react by an electron transfer tunneling mechanism. t-C4H9(+) reactions in liquid isobutene were also studied. An experimental technique for generating ions in the vapor by photoionization and then injecting them into a liquid with an electric field is described. A study of the C8 products showed that olefins predominate. Proton transfer is the important termination step for the t-C4H9(+) reactions but hydride transfer also occurs. Evidence for vibrationally excited t-C4H9(+) is given. (Author)
Descriptors : *IONS), (*RADIATION CHEMISTRY, ELECTRONS, ATOMS, FREE RADICALS, SOLID SOLUTIONS, PARAMAGNETIC RESONANCE, DEUTERIUM COMPOUNDS, HYPERFINE STRUCTURE, LINE SPECTRA, CRYSTAL LATTICES, ICE, ACRYLIC RESINS, REACTION KINETICS, PHOTOLYSIS, ALKENES.
Subject Categories : Radiation and Nuclear Chemistry
Distribution Statement : APPROVED FOR PUBLIC RELEASE