Deuterium isotope effect on π-complex formation between a rhodium complex and the unimolecular reaction products of alkyl halides and their deuterated derivatives

Abstract

(Part A) Application of Laser-Induced fluorescence Technique to the Trace Analysis of Uranium, Europium, and Samarium. Detection technique of trace amount of uranium, europium, and samarium was developed utilizing laser-induced fluoresce method with a compact nitrogen laser. The fluorescence emission and excitation spectra were observed by adding fluorescence enhancing reagents. The fluorescence lifetimes of these elements were also measured. The intensities of emission were found to be linear with respect to concentration of the elements over the wide range. The detection limits for U(VI), Eu(III), and Sm(III) were established as 0. 05, 0.1, and 10 ppb, respectively. The study suggested that this is a suitable technique for the quantitative analysis of uranium and rare earth elements.(Part B) Deuterium Isotope Effect on $\pi$ -Complex Formation between a Rhodium Complex and the Unimolecular reaction Products of Alkyl Halides and Their Deuterated Derivatives.. The origen of the inverse secondary equilibrium isotope effects on rhodium-ethylene and rhodium-ethylene-dicomplexes was studied in the condensed phase at 290 K. comparing the inverse secondary equilibrium isotope effects of the internal modes with those of the external modes, zero point energy and vibrational excitation terms contribute to the positive effects, whereas classical vibrational partition function or external terms conbribute to the negative effect. Assuming the complex forming reaction at 298 K as activated complex system, the calculated isotope effect at 298 K, Kd / Kh = 1.0636, found to be in reasonably good agreement with expriment value 1.06. The thermodynamic quantities, i.e., Gd - Gh, Hd - Hh, and Sd - Sh, in this study are -115.17 cal/mole, -75.86 cal/more, and 0.13 cal/mole*degree, respectively. Among the vibrational characteristic modes by the isotope substitution, the contributions to the inverse secondary equilibrium isotope effects are mainly due to negative normal secondary equi...