(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 contribute 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 equilibrium isotope effect, CD-s-stretching, CHD-scissoring, negative inverse secondary equilibrium isotope effect, CHD-wagging, positive inverse secondary equilibrium isotope effect, CHD-rocking, and CHD-twisting.
로듐-에틸렌 과 로듐-에틸렌-$d_1$ 착화합물에 관한 역 2차 평형 동위 원소 효과들의 근원을 298에서의 응축상에서 연구 하였다.
외부 모드와 함께 내부 모드들, 즉 영점 에너지 그리고 진동 여기 모드들의 역 2차 평형 동위 원소들의 효과 비교는 양의 효과들에 기여 하였고, 반면에 고전 진동 분배 함수 또는 외부 요소들은 음의 효과에 기여하였다.
활성 착화합물 계로서 298K에서 착화합물 형성 반응을 가정 함으로써, 298K에서 계산된 동위 원소 효과들은, 즉, $K_d/K_h=1.0636$은 실험적인 값 1.06과 합리적으로 좋은 일치를 보여 주었다.
이 활성화 착화합물들의 열역학 양들은, 즉, 이 연구에서, 각각
\begin{eqnarray*} \Delta{G_d} - \Delta{G_h} & = & -115.7 \mbox{cal/mole}\\
\Delta{H_d} - \Delta{H_h} & = & -75.86 \mbox{cal/mole}\\
\Delta{S_d} - \Delta{S_h} & = & 0.13 \mbox{cal/mole} \ast \mbox{degree} \end{eqnarray*} 이다.
동위 원소 치환에 의한 진동 속성 모드들 중에서 역 2차 평형 동위 원소 효과들에 대한 기여들은 주로, CD-s-스트레칭, CHD-씨저링은 음의 2차 평형 동위 원소 효과에 의존하였고 (에틸렌), CHD-웨깅은 음의 역 2차 평형 동위 원소 효과에 의존 하였고 (로듐-에틸렌, 로듐-에틸렌-$d_1$ 착화합물) CHD-락킹, 그리고 CHD-트위스팅은 이 연구에서 중요한 양의 역 2차 평형 동위 원소 효과에 의존 하였다. (에틸렌-$d_1$)
