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  • Author or Editor: S. Lin x
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Abstract  

The highly reactive and unstable exothermal features of methyl ethyl ketone peroxide (MEKPO) have led to a large number of thermal explosions and runaway reaction accidents in the manufacturing process. To evaluate the self-accelerating decomposition temperature (SADT) of MEKPO in various storage vessels, we used differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). The thermokinetic parameters were, in turn, used to calculate the SADT from theoretical equations based on the Semenov model. This study aimed at the SADT prediction value of various storage vessels in Taiwan compared with the UN 25 kg package and UN 0.51 L Dewar vessel. An important index, such as SADT, temperature of no return (T NR) and adiabatic time maximum rate (TMRad), was necessary and useful to ensure safe storage or transportation for self-reactive substances in the process industries.

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Abstract  

Tert-butyl peroxybenzoate (TBPB) is one of the sensitive and hazardous chemicals which have been popularly employed in petrifaction industries in the past. This study attempted to elucidate its unsafe characteristics and thermally sensitive structure so as to help prevent runaway reactions, fires or explosions in the process environment. We employed differential scanning calorimetry (DSC) to assess the kinetic parameters (such as exothermic onset temperature (T 0), heat of reaction (ΔH), frequency factor (A)), and the other safety parameters using four different scanning rates (1, 2, 4 and 10°C min−1) combined with curve-fitting method. The results indicated that TBPB becomes very dangerous during decomposition reactions; the onset temperature and reaction heat were about 100°C and 1300 J g−1, respectively. Through this study, TBPB accidents could be reduced to an accepted level with safety parameters under control. According to the findings in the study and the concept of inherent safety, TBPB runaway reactions could be thoroughly prevented in the relevant plants.

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The exothermic decomposition of cumene hydroperoxide (CHP) in cumene liquid was characterized by isothermal microcalorimetry, involving the thermal activity monitor (TAM). Unlike the exothermic behaviors previously determined from an adiabatic calorimeter, such as the vent sizing package 2 (VSP2), or differential scanning calorimetry (DSC), thermal curves revealed that CHP undergoes an autocatalytic decomposition detectable between 75 and 90°C. Previous studies have shown that the CHP in a temperature range higher than 100°C conformed to an n th order reaction rate model. CHP heat of decomposition and autocatalytic kinetics behavior were measured and compared with previous reports, and the methodology and the advantages of using the TAM to obtain an autocatalytic model by curve fitting are reported. With various autocatalytic models, such as the Prout-Tompkins equation and the Avrami-Erofeev rate law, the best curve fit among models was also investigated and proposed.

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Hair samples from junior high school students in metropolitan areas of Taichung, Taiwan were tested for a total of 13 elements, Al, Ag, Br, Cl, Cr, Fe, K, La, Mn, Na, Sc, Se, and Zn by instrumental neutron activation analysis (INAA) to establish seasonal variations, gender and environmental exposures. The seasonal variations of hairs in 39 healthy students (18 males and 21 females; age 13.3 ± 0.4 years; height, 158.0 ± 4.1 cm; weight, 53.4 ± 5.7 kg) were collected at 1.5-month intervals for 1 year starting from late August, 2008. The concentrations of the above elements varied from 103 to 10−2 μg g−1 at different sampling times. A quantified index of agreement (AT) was introduced to help classify the elements. A smaller AT indicated highly consistent quantities of specific metals in the hair while a larger AT indicated increased fluctuation, i.e., less agreement. The different ATs in various hair samples were discussed. The concentrations of these elements are compared with the data in the literature.

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Abstract  

Styrene is an important chemical in the petrochemical industry. In recent years, there have been sporadic releases, runaway reactions, fires, and thermal explosion accidents incurred by styrene and its derivatives worldwide. The purpose of this study was to estimate the impact of styrene and its derivatives of α-methylstyrene (AMS) and trans-β-methylstyrene (TBMS) contacting with benzaldehyde. Experiments were carried out to evaluate the thermokinetic parameters estimated by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III). TAM III was used to determine the fundamental thermokinetics under various isothermal temperatures, 80, 90 and 100°C. This autocatalytic reaction was demonstrated in thermal curves. After styrene was contacted with benzaldehyde, the exothermic onset temperature (T 0) and the total heat of reaction (Q total) were altered by DSC tests. When benzaldehyde is mixed with AMS and TBMS, the reaction time will be shorter but the enthalpy reduced, as revealed by TAM III tests. As AMS and TBMS, respectively, were contacted with benzaldehyde, both exothermic phenomena were changed during the reaction excursion. According to the results of this research, an operator should dictate the oxygen concentration in order to avoid any potential hazards during handling and transportation.

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Abstract  

Spinel (MgAl2O4) was synthesized mechanochemically (MC) by grinding MgO with γ-Al2O3 up to 10 hours. Examination of the MC product by neutron diffraction and infrared spectroscopy showed that it has a higher degree of inversion than its thermally produced counterpart—47% as against 10% respectively. X-ray studies showed that MgAl2O4 crystallites grow equidimensionally at a much higher rate than in the case of α-Al2O3. The higher degree of inversion and higher formation rate when γ-Al2O3 is used, is attributed to similarities in oxygen framework of MgO, Al2O3 and spinel and to the higher retention of the cations coordination number. The equidimensional growth is attributed to the presence of multiple soft modes, the {111} planes.

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Five kinds of urinary stones from 42 patients have been determined for a total of 19 elements by instrumental neutron activation analysis. Of these elements, Ca, Mg, Sr, Na, and Cl are found to be present in the core of all kinds of stones. The differences in elemental composition among the different kinds of stones as well as across the layers of stone are statistically evaluated.

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An attempt was made to establish a reliable method using chemical neutron activation analysis for surveillance of pollutants in waste waters released by plants manufacturing various kinds of products. Since preconcentration process played important role in the entire course of the analysis work, special precaution was taken to re-confirm that the recovery efficiencies for pollutant ions were satisfactory during the preconcentration. It was also re-examined that the Langmuir's adsorption isotherm pattern well obeyed by all ions under investigation. In recent years, significant amounts of rare earth compounds and other raw materials containing representative elements have been imported and consumed to meet the demand due to the rapid progress in new manufacturing technology. Samples were collected from ten various production lines in plants and potential pollutants were determined using the Tsing Hua Open-pool Reactor. It would be noteworthy that the specimens obtained by this preconcentration process also would be usable for Induced Coupled Plasma-Mass Spectrometry analysis for supplementary and/or comparison purposes.

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This work reports the radioiodination of human thyrotropin (hTSH) in our laboratory (IPEN) and evaluates its quality in comparison with a commercial product. The radioiodination yield obtained in 20 experiments ranged from 18.5 to 56.3%, while the purification recovery ranged from 75.5 to 124.0% and the specific activity ranged from 1.01 to 3.10 MBq g–1. The values for the distribution coefficient revealed in the purification of radioiodinated hTSH ranged from 0.232 to 0.371. When tested concomitantly in the same radioimmunoassay system, the IPEN and the commercial tracer presented parallel standard curves. A highly significant correlation ion was observed between the quality control samples estimated through both curves (p<0.001). These results confirm the quality of the hTSH radioiodinated at IPEN and suggest the acquirement of self-sufficiency in this in vitro nuclear technology.

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This work describes an in vivo neutron activation analysis facility for small samples, such as rats or human hand, using two 100 g252Cf neutron sources. The irradiation area is a cylindrical space, of 12 cm diameter and about 15 cm length, with fairly uniform neutron flux distribution. Experimental data on the reproducibility, effects of volume and other conditions for in vivo measurements are given. Comparative atomic absorption data on calcium measurements on rats are reported. The facility is now used for animal experiments as well as human hand irradiations in clinical investigations involving calcium metabolism and bone diseases.

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