• Analytical Science and Technology
• /
• v.25 no.6
• /
• pp.339-344
• /
• 2012

In this research, hydride generation in HPLC-ICPMS for the selenium speciation was investigated. Chemical and photochemical vapor generation techniques were compared for the effective generation of selenium vapour. $HBr/KBrO_3$ was used for the chemical reduction and a UV lamp was used for the photochemical reduction. It was found out that the photochemical reduction was more effective than the chemical reduction in all of selenium species studied. The optimum conditions for the generation of vapour are 0.4% KI, 2.5% $NaBH_4$, and 1.0 M HCl. The enhancement factor using a photochemical hydride generation was from 6.3 to 16.7 times for inorganic and organic selenium species.

• Bulletin of the Korean Chemical Society
• /
• v.12 no.6
• /
• pp.662-665
• /
• 1991

In order to prepare new chiral borohydrides (4) possessing chirality on dialkyl moieties, a series of B-alkoxydiisopinocampheylborinates (3) were synthesized by treatment of diisopinocampheylborane ($Ipc_2BH$) with alcohols (R in ROH: Me, Et, i-Pr, t-Bu) and reacted with excess of potassium hydride. Of these chiral borinic esters, only B-methoxydiisopinocampheyl borinate (3a) was converted into the corresponding dialkylmonoalkoxyborohydride (4a). For the other borinic esters, hydride uptake reactions were very slow at room temperature, accompanying disproportionation products at $65^{\circ}C$. The hydride (4a) formed is stable at $0^{\circ}C$ and can be stored over potassium hydride for few months. In the asymmetric reduction of the selected ketones, 4a provided the corresponding alcohols, such as 21% ee for 3-methyl-2-butanone, 11% ee for 2,2-dimethylcyclopentanone, 24% ee for acetophenone, 32% ee for 3-acetylpyridine, 30% for methyl benzoylformate, 31% ee for 4-phenyl-3-butyn-2-one, 39% ee for 3-butyn-2-one, and 34% ee for 3-hexyn-2-one.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.6
• /
• pp.670-676
• /
• 1992

A systematic study of the partial reduction of carboxylic acids and their derivatives to the corresponding aldehydes with lithium tris(dialkylamino)aluminum hydrides under practical conditions has been carried out. The diethylaminosubstituted derivative of lithium aluminum hydride, lithium tris(diethylamino)aluminum hydride (LTDEA), shows quite general applicability in the conversion of carboxylic acids, carboxylic esters, and primary carboxamides to the corresponding aldehydes. Lithium tripiperidinoaluminum hydride (LTPDA) also appears to be a reagent of choice for such partial transformation of primary carboxamides. In additioin, both LTDEA and LTPDA reduce tertiary carboxyamides to aldehydes in high yields. Finally, lithium tris(dihexylamino)aluminum hydride (LTDHA) is capable of achieving the chemoselective reduction of aromatic nitriles to aldehydes in the presence of aliphatic nitriles under practical conditions.

• Transactions of the Korean hydrogen and new energy society
• /
• v.31 no.6
• /
• pp.564-570
• /
• 2020

Metal hydride is suitable for safe storage of hydrogen. The hydrogen storage kinetics of the metal hydride are highly dependent on its heat transfer characteristics. This study presents a metal hydride-expended graphite composite with improved thermal conductivity and its hydrogen storage kinetics. To improve the heat transfer characteristics, a metal hydride was mixed and compacted with a high thermal conductivity additive. As the hydrogen storage material, AB5 type metal hydride La0.9Ce0.1Ni5 was used. As an additive, flakes-type expended graphite was used. With improved heat transfer characteristics, the metal hydride-expended graphite composite stores hydrogen four times faster than metal hydride powder.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.5
• /
• pp.531-537
• /
• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• Resources Recycling
• /
• v.27 no.5
• /
• pp.30-37
• /
• 2018

For recylcing of high purity tantalum (Ta) scrap, We investigated manufacture of tantalum powder using hydride-dehydride (HDH) process. Tantalum had excellent properties such as ductile, hardness and high melting point. Usually these properties made difficult to make a powder. In this study, Tantalum powder was manufactured using Tantalum hydride via hydridation. Tantalum hydride was formed at $500^{\circ}C$, 5 hr/$700^{\circ}C$, 3 hr and it is easy to make a tantalum hydride powder because hydrogen in the tantalum act as a defect dislocation and lattice expansion. The powder was pulverized to a size of less than $10{\mu}m$ under a condition of 1300 rpm, 30 min using a ring mill, and tantalum powder with less than 50 ppm hydrogen was prepared through dehydridation in an Ar and low vacuum atmosphere.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.1
• /
• pp.9-10
• /
• 2003

• Journal of Industrial Technology
• /
• v.41 no.1
• /
• pp.25-30
• /
• 2021

Hydride-dehydride process for efficient recycling of tantalum (Ta) is used for manufacturer of Ta powder. In case of metal powder, Impurities as like nitride, oxygen, hydrogen is decreased of physical properties. For manufacture of Ta powder, control of theses impurities is important. In this study, to decreased of impurities on Ta powder using HDH process optimize dehydride condition. Dehydration behavior of Ta is depended on temperature, time, and atmosphere. Phase transition of Ta hydride is analyzed by X-ray diffraction (XRD). Concentration of hydrogen is decreased with temperature increased. At high temperature, concentration of hydrogen in Ta is similar according to time increased. Size and morphology of powder is not observed after dehydride. Ta powder, which is less than 20 um, concentration of hydrogen under 800 ppm is obtain.

• 한국신재생에너지학회:학술대회논문집
• /
• 2009.06a
• /
• pp.781-781
• /
• 2009

We demonstrate that trasition metal catalyst nanoparticle (NP) attached to carbon nitride nanotubes (CNNTs) show selective catalytic activities on hydrogen generation from the water solution including chemical hydride negative ions. The natural bonding orbitals (NBO) obtained from the first-principle calculations shows that the catalysts attached on CNNTs are quite differently polarized when they play for hydrogen generation from chemical hydride ions and hydrogen of water. For Co and Ni nanoparticles attached on CNNTs, their charges are more positively polarized when they interact with $BH_4^-Na^+$ and $H_2O$ while Pt atoms are less positively charged. In this matter, the increased positive charges on catlyst nanoparticles are proven to be more efficient in attracting hydride negative ions, thus improving hydrogen generate rates. Consequently, this result implies that these different charge polarization leads to selective catalytic activities of NPs-CNNTs. In the hydrogen generation experiments, Co-CNNTs shows the highest hydrogen generation rate when the similar amounts of catalyst nanoparticles (Co, Ni, and Pt) are dispersed on the sidewalls of CNNTs.

• Journal of the Korea Institute of Military Science and Technology
• /
• v.15 no.4
• /
• pp.519-526
• /
• 2012

Recently fuel cell is considered to be a new technology that can substitute the ICE(Internal Combustion Engine) as well as overcome environmental issues. In military applications, fuel cell has an unique advantages, which are quietness, namely, stealth. The environmental requirement such as shock and vibration in military application, however, is very severe comparing to civilian demand. Especially, the safety concerning hydrogen storage is the most important problem. Among the candidate methods to store hydrogen, the metal hydride storage is promising method owing to the storage mechanism of chemical absorption of hydrogen to metal hydrides. In this study, the new composition of Ti-Zr type metal hydride(A composition) was suggested and investigated to increase the hydrogen storage capacity. For comparison, the hydrogen charge-discharge properties were investigated with the commercialized Ti-Zr type metal hydride(B composition) using PCT(Pressure-Composition-Temperature) measurement. Also two hydrogen storage cylinders were loaded with each metal hydride and their hydrogen charging and discharging characteristics were investigated. As a result, it was found that the new Ti-Zr type metal hydride has a slightly higher hydrogen storage capacity compared to commercial Ti-Zr type metal hydride.