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  • Author or Editor: K. Hasegawa x
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Abstract  

The rate constants for thallium(I)-thallium(III) exchange with various alcohols in sulfuric acid solution were determined. In all cases involving alcohols, methanol, ethanol, 2-propanol, 2-methyl-2-propanol, the reaction rates were not accelerated. The larger the formation constants of solvato-complexes for 2-propanol and 2-methyl-2-propanol lead to lower reaction rates in the solution. The mechanism of the exchange reaction was also studied.

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Abstract  

To understand the behaviour of Tl/II/ and the bridging group SO 4 2– in radiation induced electron exchange reactions we have investigated the rate constants and mechanisms of reaction of Tl/II/ with Tl/I/ and Tl/III/ in perchloric acid solutions. The results indicated that Tl/II/ is an intermediate in the -ray induced electron exchange process of T1/I/–T1/III/. Sulfate ions at [SO 4 2– ]>-0.02M serve as bridging groups and play an important role in accelerating the T1/II/–T1/I/ reaction. A cooperative effect was found between hydrogen peroxide and sulfate ion at low sulfate ion concentration, [SO 4 2– ]0.02M in perchloric acid solution.

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Abstract  

The cause of the low detection efficiencies of Cherenkov radiation by the liquid scintillation counter was investigated. The detection limit of the liquid scintillation counter was assumed and the increase of counting rates for the increase of refractive index was calculated from Cherenkov photo yields and -distribution.

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Abstract  

The values of Sb(III), Tl(I), Te(IV), and biological substance, DNA determined by sub- and super-equivalence method of isotope dilution analysis (SSE-IDA) and substoichiometric isotope dilution analysis (Subst-IDA) under the same condition were compared. From the results, it was proved that SEE-IDA did not need the strict condition necessary for Subst-IDA and the determination by SEE-IDA was possible within the error of a few percent, and the range of determination was wider than that of Subst-IDA. The various variants of SSE-IDA reported so far were classified into SEE-Reverse-IDA and SEE-Direct-IDA. Finally, the characteristics of SEE-IDA allowing accurate determination were discussed and summarized.

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Abstract  

The counting efficiency of Cherenkov radiation by the liquid scintillation counter is studied in several solvents. The relation between the strength of the pulse height by the Cherenkov radiation and the maximum energy of -rays was fairly proportional. The colour quenching can be corrected by measuring the absorbance of solution.

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Abstract  

The rate constant of radiation induced exchange reaction between thallium(I) and thallium(III) ions has been studied for elucidating the mechanisms which are responsible for (T1(II) intermediates or bridging groups (SO 4 2– ) in sulfuric acid and perchloric acid solutions. It was found that the radiation induced exchange reaction is accelerated by the sulfate ion, and the rate of the thallium(II)-thallium(I) reaction is faster than that of the thallium(II)-thallium(III) process in perchloric acid solution.

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Abstract  

A new sub-superequivalence method of radiometric analysis is proposed, which is derived by combining the sub-superequivalence method of isotope dilution analysis with substoichiometric radiometric analysis. This method using redox reaction is applied for the determination of trace amount of antimony and was proved to be an excellent technique. The fundamental problems of this method are discussed analytically.

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Abstract  

The reduction reaction mechanism of carrier-free125Sb in HCl solution was studied kinetically. Sb(III) and Sb(v) were separated by solvent extraction using n-benzoyl-n-phenylhydroxylamine(BPHA) in chloroform at different constant time in interval and the reaction rate was determined by measuring the radioactivities of125Sb in both organic and aqueous phases. Plot of log[125Sb(V)/ [125Sb(III)+125Sb(V)] against the elasped time do not give straight lines. The curves can be solved to be ABC type reactions by a non-linear squares. On the basis of dependence of the reactions, overall reactions can be expressed as follows;

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Abstract  

In this paper, several small-scale screening test methods were discussed on evaluating the thermal hazard of reactive substances. Generally the sensitivities of DSC and ARC are not high enough to evaluate the thermal hazards for all reactive substance, especially, for those of complex reactions containing a phase and/or chemical reaction mechanism change in the lower temperature range. Using the C80, however, the reaction can easily be detected in the lower temperature range due to its high sensitivity. Therefore, the C80 gives generally more accurate results than DSC and ARC. Data from C80 and Dewar vessel were compared and it indicates that the Dewar vessel has also high enough sensitivity to evaluate the thermal hazard and determine the heat flux in lower temperature range of reactive substances.

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Abstract  

The behavior of uranium under various redox conditions was investigated in the brackish Obuchi lake surrounded by an uranium enrichment plant and facilities currently under construction for reprocessing of spent nuclear fuel in Rokkasho Village in northern Japan. Our investigation showed that uranium in water under oxic conditions can be explained by the simple mixing of freshwater and seawater, and the source of uranium in the lake is mainly seawater. The ratios of 238U/salinity under oxic conditions were approximately 0.09-0.12 g.l-1.psu-1. However, the ratios of 238U/salinity in bottom layer water under anoxic condition in summer were lower (0.07-0.09 g.l-1.psu-1) than those in seawater. 238U concentrations in pore water sampled under anoxic conditions were very low (0.05-0.06 g.l-1.psu-1). Moreover, the relationships between the 238U/Al ratios and the Fe/Al ratios of particle substances were strongly correlated. This suggests that uranium in the bottom-layer water may be precipitated to an insoluble form in the anoxic state, and Fe is the major carrier of insoluble uranium.

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