• Bulletin of the Korean Chemical Society
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• v.4 no.4
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• pp.180-183
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• 1983

The reaction of $IrClH_2(CO)(Ph_3P)_2$ ($Ph_3P$=triphenylphosphine) with acrylonitrile (AN) produces a stoichiometric amount of propionitrile (PN) at $100^{\circ}C$ under nitrogen, which suggests that the catalytic hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ proceeds through the hydride route where the formation of the dihydrido complex, $IrClH_2(CO)(Ph_3P)_2$ is the initial step. The rate of the hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ is decreased by the presence of excess $Cl^-$ in the reaction system, which suggests that $Cl^-$ is the dissociating ligand in the catalytic cycle. It has been also found that the rate of the hydrogenation increases with inercase both in hydrogen pressure and in concentration of free $Ph_3P$, and with decrease in AN concentration in the reaction system.

• Bulletin of the Korean Chemical Society
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• v.7 no.4
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• pp.279-282
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• 1986

The MNDO calculations were performed in order to investigate the gas-phase reaction mechanism of 2-propene-1-al oxide, as a model compound of dypnone oxide(1,3-diphenyl-2-butene-1-one oxide) with the chloride ion. Optimized geometries and heats of formation for two probable concerted pathways, CHO and H migration, were determined and their activation energies were obtained. MO results show that although the formyl migration is thermodynamically more favorable than the hydride migration, the latter kinetically predominates over the formyl migration, which is contrary to the established migrating preferences. It is concluded that the hydride migratory propensity is catalyzed by the chloride ion by reducing the capability of the carbonyl ${\pi}$ bond to participate in the migration.

• Mass Spectrometry Letters
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• v.7 no.2
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• pp.50-54
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• 2016

Multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) is currently used in our laboratory for isotopic and quantitative analyses of nuclear materials at ultra-trace levels in environmental swipe samples, which is a very useful for monitoring undeclared nuclear activities. In this study, to improve measurement precisions of uranium isotopes at ultratrace levels, we adopted a desolvating nebulizer system (Aridus-II, CETAC., USA), which can improve signal sensitivity and reduce formation of uranium hydride. A peristaltic pump was combined with Aridus-II in the sample introduction system of MC-ICP-MS to reduce long-term signal fluctuations by maintaining a constant flow rate of the sample solution. The signal sensitivity in the presence of Aridus-II was improved more than 10-fold and the formation ratio of UH/U decreased by 16- to 17- fold compared to a normal spray chamber. Long-term signal fluctuations were significantly reduced by using the peristaltic pump. Detailed optimizations and evaluations with uranium standards are also discussed in this paper.

• Resources Recycling
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• v.32 no.2
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• pp.19-32
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• 2023

A novel method for the synthesis of titanium hydride powder from titanium tetrachloride via the magnesiothermic reduction in an hydrogen gas atmosphere was investigated. To examine the influence of temperature on the formation of titanium hydride, the reduction was conducted at 1023~1123 K under 1 atm of hydrogen gas atmosphere for approximately 30 min. Subsequently, the titanium hydride powder was sintered by maintaining the temperature for 0~120 min, and the decrease in the oxygen concentration of the powder was investigated. The experimental results showed that TiH_1.924 was produced at 1023 K, whereas mixtures of TiH_1.924 and TiH_1.5 were produced at 1073 K and 1123 K. In addition, the hydrogen concentration in the powder decreased with increasing temperature. The concentration of oxygen in the powder decreased with increasing temperature and sintering time owing to the decrease in the specific surface area of the powder. The minimum concentration of oxygen was 0.246 mass% when the mixture of TiH_1.924 and TiH_1.5 was obtained at 1073 K and a sintering time of 120 min.

• Journal of Industrial Technology
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• v.3
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• pp.47-51
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• 1983

The fragmentation of Mg and Mg-25(w/o) Al alloy particles in hydriding-dehydriding was studied. The formation of hydride was made in autoclave, and formed hydrides were $MgH_2$ in both pure Mg and Mg-25(w/o) Al alloy particles. Pure Mg was more fractured than Mg-25(w/o) Al alloy in hydriding. The addition of Al exhibited fragmentation in hydriding, but displayed the same fragmentation as Mg in dehydriding.

• Journal of the Korean Ceramic Society
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• v.31 no.6
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• pp.637-642
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• 1994

Using SHS(Self-propagating High-temperature Synthesis) method, the optimum synthetic condition of titanium carbonitride was established by controlling the parameters such as relative density of mixture (Ti+C), nitrogen pressure, additive amounts of titanium hydride(TiH1.924) and protecting heat loss. Under 1 atm nitrogen pressure, nitridation ratio with changing relative density of the sample compacts has a maximum (87.2%) at about 55%, and in the case of enveloping the pellet with a quartz tube, the highest nitridation ratio of 90% was obtained at about 68%. At relative density of 55%, nitridation ratio with the nitrogen pressure has a miximum (87.3%) at 7 atm. As the amounts of additive titanium hydride increased, nitridation ratio decreased at below 7 atm nitrogen pressure and, increased at above this pressure until percent of addition percent reached 15 wt% and decreased abruptly upon futher increases in titanium hydride. In the synthesis of TiCxNy by combustion reaction, heat transfer from combustion zone to preheating zone and nitrogen gas penetration into the compact were found to be important factors affecting the TiCxNy formation. It was difficult to obtain high nitridation ratio when the conbustion temperature was either too high or too low, and it seems that the retention of high temperature after a combustion wave sweeped through the reactant mixture pellet is critical to obtain a satisfactory nitridation ratio.

• Journal of Integrative Natural Science
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• v.6 no.1
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• pp.34-38
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• 2013

Tributyltin hydride ($n-Bu_3SnH$), an endocrine disruptor, was slowly polymerized by the group 4 ${Cp^{\prime}}_2TiCl_2/N$-selectride (Cp' = $C_5H_5$, Cp; $Me-C_5H_4$, Me-Cp; $Me_5C_5$, $Cp^*$) catalyst combination to give two phases of products: one is an insoluble cross-linked solid, polystannane in 3-25% yield as minor product via disproportionation/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 65-90% yield as major product via simple dehydrocoupling process. Disproportionation/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane. The disproportionation/dehydrocoupling of a tertiary hydrostannane mediated by early transition metallocene/inorganic hydride is quite unusual and applicable.

• Journal of the Korean Society of Propulsion Engineers
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• v.23 no.1
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• pp.79-92
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• 2019

Titanium hydride potassium perchlorate (THPP) is one of the commonly utilized pyrotechnic materials in aerospace industries. The current study elucidates the effects of hygrothermal aging on the combustion of THPP experimentally. First, applying the Differential Scanning Calorimetry (DSC) and isocoversional method, both the delay of reaction start and decrease in maximum reaction rate were observed. The kinetics parameters tended to fluctuate depending the thermal reaction or intermediate product formation of THPP. Also, the oxidants decomposition and fuel oxidation phenomenon were discovered by X-ray photoelectron spectroscopy (XPS). The experimental heat from DSC data were verified as reasonable by comparing with the theoretical heat obtained utilizing both THPP formulation from XPS and NASA Chemical Equilibrium with Applications (CEA). Both data had identical variation trend, which expecially had the highest heat value at 10 weeks aged sample.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.2
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• pp.125-132
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• 2006

The alloys which compositions were represented by the formula, $Ti_{(0.22+X)}Cr_{(0.28+1.5X)}V_{(0.5-2.5X)}$ ($0{\leq}X{\leq}0.12$), had the total hydrogen storage capacity higher than 3 wt% and the effective hydrogen storage capacity higher than 1.4 wt%. Particularly, among all the tested alloys, the $Ti_{0.32}Cr_{0.43}V_{0.25}$ alloy exhibited the best effective hydrogen storage capacity of 1.65 wt%. Furthermore, the reversible bcc${\leftrightarrow}$fcc structural transition was observed with hydrogenation and dehydrogenation, which predicted the possibility of pressure cycling. EDS analysis revealed micro-segregation, which suggested the necessity of microstructure homogenization by heat treatment. The $Ti_{0.32}Cr_{0.43}V_{0.25}$ alloy was selected for heat treatment and for other related studies. The results showed that the total and the effective hydrogen storage capacity increased to 3.7 wt% and 2.3 wt%, respectively. The flatness of the plateau region was also greatly improved and heat of hydride formation was determined to be approximately -36 kJ/mol $H_2$.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.546-550
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• 2014

Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.