• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2034-2040
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• 2007

Efficient catalytic systems, where Ni or Pd is introduced in a supporting material of nanoporous carbon, have been developed for a liquid-phase hydrogenation of carboxylic acids and ketones at room temperature. It has been found that the catalysts reliably show high activities and selectivities for the hydrogenation to alcohols even in acidic conditions, and the catalytic activities depend on the preparative method of catalysts, the hydrogen pressure, the agitation rate, and the catalytic species. The hydrogenation of carboxylic acids and ketones clearly shows that the reaction rate is affected by the electronic and the steric effects, and a plausible reaction mechanism using metal hydrides as catalytic species is proposed.

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.743-749
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• 1993

The approximate rates and stoichiometry of the reaction of excess lithium tris(dihexylamino)aluminum hydride(LTDHA) with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 0$^{\circ}$C) were studied in order to define the reducing characteristics of the reagent for selective reductions. The reducing ability of LTDHA was also compared with those of the parent lithium aluminum hydride(LAH), lithium tris(diethylamino)aluminum hydride(LTDEA), and lithium tris(dibutylamino)aluminum hydride(LTDBA). In general, the reactivity toward organic functionalities is in order of $LAH{\gg}LTDEA{\geq}LTDBA>LTDHA$. LTDHA shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, epoxides, and tertiary amides readily. Anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol without hydrogen evolution, whereas p-benzoquinone in inert to LTDHA. In addition to that, disulfides are also readily reduced to thiols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly. Especially, this reagent reduces aromatic nitriles to the corresponding aldehydes in good yields.

• Bulletin of the Korean Chemical Society
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• 제9권6호
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• pp.384-388
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• 1988

New methods of the reduction of carboxylic acid salts to aldehydes with 2 equiv of thexylbromoborane-dimethyl sulfide (ThxBHBr${\cdot}SMe_2$) or 9-borabicyclo[3.3.1]nonane (9-BBN) are described. Both these reagents provide the corresponding aldehydes from various as sodium and lithium salts of carboxylic acids in high yields both at room temperature. Such facile reductions are explained as the simple substitution for the bromo group of ThxBHBr by a carboxylate to form thexyl(acyloxty)borane followed by reduction with excess reagent and the formation of an ate complex followed by reduction with excess 9-BBN.

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.436-442
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• 1994

Heterobimetallic complexes have a donor-accepter metal-metal bond in which two electrons from the electron-rich metal moiety are donated to the other electron-deficient one. Based on the competition reactions, Cotton-Kraihanzel force constants, ν(CO)IR band resolution and the relative nucleophilicity comparison of the donor ligands, the following relative ligating ability of the donor ligands toward $M(CO)_5$ (M=Cr, W) is assessed: cis-HW$(CO)_4P(OMe)_3^-$, $HW(CO)_5^-$ > $HCr(CO)_5^-$-$Br^-$ > trans-HFe$(CO)_3P(OMe)_3^-$ > $Mn(CO)_5^-$ > $HFe(CO)_4^-$ > PP$h_3$

• Bulletin of the Korean Chemical Society
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• 제12권6호
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• pp.644-649
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• 1991

The approximate rates and stoichiometry of the reaction of excess lithium tris(dibutylamino)aluminum hydride (LT-DBA) with selected organic compounds containing representative functional groups under standardized conditions (tetrahydrofuran, $0^{\circ}C$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of LTDBA was also compared with those of the parent lithium aluminum hydride and the alkoxy derivatives. The reagent appears to be much milder than the parent reagent, but stronger than lithium tri-t-butoxyaluminohydride in reducing strength. LTDBA shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, acid chlorides, epoxides, and amides readily. In addition to that, ${\alpha},{\beta}$-unsaturated aldehyde is reduced to ${\alpha},{\beta}$-unsaturated alcohol. Quinones are reduced to the corresponding diols without evolution of hydrogen. Tertiary amides and aromatic nitriles are converted to aldehydes with a limiting amount of LTDBA. Finally, disulfides and sulfoxides are readily reduced to thiols and sulfides, respectively, without hydrogen evolution.

• Bulletin of the Korean Chemical Society
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• 제8권4호
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• pp.276-280
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• 1987

Several chiral potassium B-alkyl-9-boratabicyclo[3.3.1]nonanes $(K\; B-R^*-9-BBNH)$ and potassium B-alkoxy-9-boratabicyclo[3.3.1]nonanes $(K \;B-OR^*-9-BBNH)$ were synthesized by treatment of the corresponding trialkylboranes and dialkylmonoalkoxyboranes with a small excess of potassium hydride. The chiral B-alkoxy derivatives generally reduce representative ketones, such as acetophenone and 3-methyl-2-butanone, with greater optical induction than the corresponding B-alkyl derivatives, suggesting the involvement of the oxygen atom in the control process for asymmetric synthesis.

• 한국표면공학회지
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• 제29권5호
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• pp.494-497
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• 1996

The effect of implanted nitrogen and carbon ion into SUS 304 on the absorption of hydrogen by cathodic chaging were studied. Implantations of $N^+$, $C^+$ were performed with doses of $3\times10^{17}$ ions $\textrm{cm}^2$ and $5\times10^{17}N^+cm^2$, and $5\times10^{17}C^+cm^2$, at an energy of 90 keV. Nitrides and carbide were investigatedby X-ray diffraction, Auger electron spectroscopy (AES) and scanning electron microscope (SEM). Formation of hydrides during cathodic charging were depressed by a modified surface layer. It is concluded that the both nitrides and carbides act as the barrier of hydrogen migration and the catalyst of desorption of cathodically charged hydrogen.

• Nuclear Engineering and Technology
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• 제56권2호
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• pp.728-744
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• 2024

The presence of hydrogen absorbed by zirconium-based cladding materials during reactor operation can trigger degradation mechanisms and endanger the rod integrity. Ensuring the durability of the rods in extended time-frames like dry storage requires anticipating hydrogen behavior using numerical modeling. In this context, the present paper describes a hydrogen post-processing tool for Falcon - HYPE, a PSI's in-house tool able to calculate hydrogen uptake, transport, thermochemistry, reorientation of hydrides and hydrogen-related failure criteria. The tool extracts all necessary data from a Falcon output file; therefore, it can be considered loosely coupled to Falcon. HYPE has been successfully validated against experimental data and applied to reactor operation and interim storage scenarios to present its capabilities.

• Nuclear Engineering and Technology
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• 제56권3호
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• pp.824-831
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• 2024

In order to investigate the occurring processes during long-term dry storage of spent fuel assemblies, a joined project called SPIZWURZ, between the Karlsruhe Institute of Technology and the Gesellschaft für Anlagen-und Reaktorsicherheit (GRS), was started. Aim of the SPIZWURZ project is the determination and quantification of the influence of texture and elastic strain on diffusion and solubility of hydrogen in three different zirconium alloys used in western Europe during a long-term cooling transient (1 K/d) starting at 400 ℃. The strain in the cladding of an irradiated spent fuel rod shall be measured. Models predicting the formation of radial oriented hydrides will be validated, improved, and implemented in the GRS fuel rod performance code TESPA-ROD. This paper describes the SPIZWURZ project and already obtained first results.

• 공업화학
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• 제9권2호
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• pp.255-260
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• 1998

금속수소화물 $LaNi_5$와 $LaNi_{4.5}Al_{0.5}$을 화학적 합성법으로 제조하여, 합성된 금속수소화물의 물성을 다양한 방법으로 확인하였다. $LaNi_5$와 $LaNi_{4.5}Al_{0.5}$은 2회 정도 수소화/탈수소화 반응을 시키면 활성화되었으며, 압력-농도-온도 곡선을 측정한 결과 각각 6개와 5.5개의 수소원자가 저장되었다. $LaNi_{4.5}Al_{0.5}$의 경우 수소화 반응속도를 초기속도법으로 구한 결과 비반응 수축핵모델이 잘 적용되었으며, 수소화반응의 율속단계는 $LaNi_{4.5}Al_{0.5}$의 표면에서 수소분자의 해리화학흡착임을 알 수 있었다. $LaNi_{4.5}Al_{0.5}$의 수소화반응 활성화에너지는 $9.506kcal/mol-H_2$이었으며, 반응속도식은 273~343K와 $P_o-P_{eq}=0.25{\sim}0.66atm$의 범위에서 아래와 같이 표시되었다. $\frac{dX}{dt}=4.636(P_o-P_{eq})$ exp$\frac{-9506}{RT}$).