Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

Pyrochemical treatment of spent nitride fuels for MA transmutation

Nitride fuels have several advantages including high thermal conductivity and high metal density(like metallic fuels) and high melting point and isotropic crystal structure(like oxide fuels). Since the late 1990 s, the partitioning and transmutation of minor actinides(MA) has been studied to decrease the long-term radio-toxicity of high-level waste and to mitigate the burden of final disposal. Japan Atomic Energy Agency(JAEA) has proposed a dedicated transmutation cycle using an accelerator-driven system(ADS) with nitride fuels containing MA. The nitride fuel cycle we have developed includes a pyrochemical process. Our focus is on the electrolysis of nitride fuels and their refabrication from the recovered actinides; other processes are similar to the technology for metal fuel treatment and have been studied elsewhere. Here, we summarize our activity on the development of the pyrochemical treatment of spent nitride fuels.     

13C-selective IRMPD of CBr2F2/Cl2 and CCl2F2/Br2 systems

The CO₂ TEA laser irradiation of CBr₂F₂ in the presence of Cl₂ yielded ¹³C-enriched CBrClF₂ and ¹³C-enriched CCl₂F₂ under selected experimental conditions. As the photolysis proceeded, the ¹³C concentration of CBrClF₂ decreased gradually and that of CCl₂F₂ increased up to 90% or higher. These results can be explained by the mechanism involving the secondary ¹³C-selective IRMPD of the primary product CBrClF₂. On the other hand, the carbon-containing product for a CCl₂F₂/Br₂ system was only CBrClF₂; the further IRMPD of which probably regenerated CBrClF₂ in the presence of Br₂. The decomposition probabilities of ¹²C- and ¹³C-containing molecules in both systems were measured as functions of laser line, laser fluence, and reactant pressures.     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.     

NUMERICAL SIMULATION OF THE PHENOMENA DUE TO THE PASSING-BY OF TWO BODIES USING THE UNSTEADY BOUNDARY ELEMENT METHOD

In this paper a numerical analysis was made to investigate the aerodynamic forces surrounding two bodies in relative motion in a fluid at rest in three dimensions. The unsteady boundary element method was employed in the numerical calculations. This method is very convenient for obtaining an approximate expression of the velocity potential, especially for practical use. The passing-by of two spheres in an incompressible perfect fluid which extends to infinity is treated by the present method. The resultant pressure coefficients on two spheres passing each other in opposite directions are calculated and discussed numerically. Numerical examples are presented to show the validity of the present method. The method is also applied to the calculation of the passing-by of two trains in an open area in order to investigate its applicability.     

Preparation of water-soluble sodium deoxycellulosesulfonate from homogeneously prepared tosylcellulose

Water-soluble sodium deoxycellulosesulfonate (DCS-Na) was prepared by nucleophilic substitution of the p-toluenesulfonyl (tosyl) groups of cellulose p-toluenesulfonate (tosylcellulose) by a sulfonate group in aqueous Na2SO3 solution. In the substitution, the yield and degree of substitution (DS) by the sulfonate group (DSsul) were found to increase with increasing reaction temperature and with reaction time, and reached up to 80% and 0.28, respectively, at 100 °C for 72 h. Although the DS of the tosyl group (DStosyl) decreased with increasing reaction temperature and with reaction time, a respectable amount of tosyl group still remained even at 100 °C for 72 h. Furthermore, the intrinsic viscosity, [], of the DCS-Na obtained decreased considerably with increasing reaction temperature and with reaction time. The decreases in DStosyl and [] were very similar to each other in that increasing DSsul was independent of the reaction temperature and the reaction time. The similarity of the decreases suggests that the mechanisms of scission of the cellulose backbone and the leaving of the tosyl groups (from tosylcellulose) in the nucleophilic substitution were closely related to each other. The partial conversion of the tosyl group in the tosylcellulose to the sulfonate group, by the nucleophilic substitution, was also confirmed by the change in the IR absorption spectrum. The product could be considered to be a ter-polymer from the point of view of the AGU (anhydro glucose unit). Thus, we have AGU-co-DAGUS-Na-tosyl AGU as possible options