• Bulletin of the Korean Chemical Society
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• v.7 no.1
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• pp.66-69
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• 1986

The reaction of potassium trialkoxyborohydrides of varying steric requirements with lithium chloride in tetrahydrofuran(THF) was examined in detail to establish the generality of this synthesis of the corresponding lithium trialkoxyborohydrides. The metal ion exchange reaction between potassium triisopropoxyborohydride and lithium chloride in THF proceeded instantly at room temperature and the corresponding lithium salt was very stable toward disproportionation. However, for R = s-Bu, t-Bu and 2-methylcyclohexyl, with increasing steric requirement, the lithium derivatives were unstable and thus dissociated into $(RO)BH_3^-\;and\; (RO)_4B^-$. The stereoselectivity of lithium triisopropoxyborohydride(LIPBH) in the reduction of representative cyclic ketones was examined and compared with that of the potassium derivative.

• Bulletin of the Korean Chemical Society
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• v.9 no.6
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• pp.388-393
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• 1988

The chemisorption of CO molecules on polycrystalline nickel surface has been studied by investigating the resulting chemisorbed species with the X-ray photoelectron spectroscopy at temperatures between 300K through 433K. It is found that the adsorbed CO molecules are dissociated by the simple C-O bond cleavage as well as by the disproportionation reaction at temperatures above 373K. The former type dissociation is more favored at low coverages and at elevated temperatures. The isotherms of CO chemisorption are obtained from the xps intensities of C 1s peaks, and then the activation energy of the dissociative adsorption is estimated as a function of the CO exposure. These activation energies are extrapolated to zero coverage to obtain the activation energy of chemisorption in which thermal C-O bond cleavage takes place. The value obtained is 38.1 kJ/mol.

• Bulletin of the Korean Chemical Society
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• v.10 no.6
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• pp.509-514
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• 1989

Reactions of thianthrene cation radical perchlorate (1) with N-(p-methoxyphenyl)benzenesulphonamide (14) in acetonitrile at room temperature afforded various products : thianthrene (3), N-(p-hydroxyphenyl)benzenesulphonamide (16), benzenesulphonamide (18), hydroquinone (20); 5-(5-benzenesulphonamido-2-methoxyphenyl)-thia nthrenium perchlorate(21), 2-benzenesulphonamido-2'-hydroxy-5,5'-dimethoxy biphenyl(24), 2-benzenesulphonamido-2',5'-dihydroxy-5-methoxy -biphenyl(25), and a traceable amount of p-quinone(23). The formations of part of (3) and (21) can be explained by either disproportionation or half-regeneration mechanism but those of the remainders by diverse reactions of sulphonamidyl radical (27) derived from (14) (through single electron transfer, followed by deprotonation processes). Similar results were observed from the reaction with N-(p-methoxyphenyl)methanesulphonamide (15).

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

• Korean Journal of Mineralogy and Petrology
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• v.34 no.3
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• pp.157-167
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• 2021

Lead (Pb) is one of the key trace elements, exhibiting a peculiar partitioning behavior into silicate melts in contact with minerals. Partitioning behaviors of Pb between silicate mineral and melt have been known to depend on melt composition and thus, the atomic structures of corresponding silicate liquids. Despite the importance, detailed structural studies of Pb-bearing silicate melts are still lacking due to experimental difficulties. Here, we explored the effect of lead content on the atomic structures, particularly the evolution of silicate networks in Pb-bearing sodium metasilicate ([(PbO)_x(Na₂O)_1-x]·SiO₂) glasses as a model system for trace metal bearing natural silicate melts, using ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy. As the PbO content increases, the ²⁹Si peak widths increase, and the maximum peak positions shift from -76.2, -77.8, -80.3, -81.5, -84.6, to -87.7 ppm with increasing PbO contents of 0, 0.25, 0.5, 0.67, 0.86, and 1, respectively. The ²⁹Si MAS NMR spectra for the glasses were simulated with Gaussian functions for Qⁿ species (SiO₄ tetrahedra with n BOs) for providing quantitative resolution. The simulation results reveal the evolution of each Qⁿ species with varying PbO content. Na-endmember Na₂SiO₃ glass consists of predominant Q² species together with equal proportions of Q¹ and Q³. As Pb replaces Na, the fraction of Q² species tends to decrease, while those for Q¹ and Q³ species increase indicating an increase in disproportionation among Qⁿ species. Simulation results on the ²⁹Si NMR spectrum showed increases in structural disorder and chemical disorder as evidenced by an increase in disproportionation factor with an increase in average cation field strengths of the network modifying cations. Changes in the topological and configurational disorder of the model silicate melt by Pb imply an intrinsic origin of macroscopic properties such as element partitioning behavior.

• Journal of the Korean Chemical Society
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• v.20 no.6
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• pp.469-478
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• 1976

Clinoptilolite zeolite samples were treated with hydrochloric acid, sulfuric acid and phosphoric acid of different strength and the adsorption characteristics and crystal structures of the original and acid-treated clinoptilolites were studied. By treating with hydrochloric acid, the adsorbed amount increased to 5-fold for nitrogen, to 3-fold for benzene, but for methanol no significant change was observed. As acid strength increased further, there were declines both in adsorption capacity and crystallinity. The results showed that the increase of adsorbed amount was caused by the rearrangement of the pore entrance and cation exchange. A method for determination of clinoptilolite content in natural mineral based on benzene adsorption on acid-treated sample is proposed. By this method, the original sample used in this study was found to contain approximately 40% of clinoptilolite. Using pulse technique in micro-catalytic reactor system, the catalytic activities of hydrochloric acid-treated clinoptilolites in cumene cracking and toluene disproportionation reactions were measured. For cumene cracking reaction, the maximum conversion was observed for the 0.5 N hydrochloric acid-treated sample. It is instructive to note that the maximum benzene adsorption was also observed for the sample treated with 0.5 N HCl. This suggest that the conversion rate was determined mainly by the rate of transport of reactants and the products through the pore structure. In the toluene disproportionation reaction, the same trend was observed. But the rate of deactivation was high for samples with strong acid sites. Since catalyst having higher activity was deactivated more easily, the conversion maximum was shifted to the sample treated with higher concentration of acid, -1N. The catalytic activity of $Ca^{2+} and La^{3+} ion exchanged samples for the toluene disproportion was much lower than that of acid-treated samples. Introduction of Ca^{2+} and La^{3+}$ into the pore structure apparently decreases the effective pore diameter of acid-treated clinoptilolite thus limiting the diffusion of reactants and products.

• Journal of the Korean Chemical Society
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• v.39 no.6
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• pp.446-452
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• 1995

Lithium intercalates, $Li_xFeMoO_4Cl$ ($1{\leq}X{\leq}2$) prepared by electrochemical lithiation of $FeMoO_4Cl$ crystallizes in monoclinic structure for all x values as revealed by x-ray diffraction and galvanostatic discharge experiments. According to the x-ray photoelectron spectroscopic study, Fe(III) is at first reduced to Fe(II) upon lithium intercalation with the x domain of $0{\leq}X{\leq}1$, where the crystal symmetry is changed from tetragonal to monoclinic. On the other hand, Mo(VI) is reduced to lower valent state upon further lithium intercalation ($1{\leq}X{\leq}2$), where no crystal symmetry transformation and reduction of Fe(II) to lower valent state are observed. The Mo 3d spectrum for $Li_2FeMoO_4Cl$ appears as a complex shape, but can be deconvoluted into the three sets of the doublet on the basis of Gaussian function, those which correspond to Mo(VI), Mo(V) and Mo(IV) states, respectively. The mixed valent states of molybdenum after further lithiation may be due to a competitive reaction between the formation of Mo(V) and its disproportionation to Mo(IV) and Mo(VI).

• Journal of the Korean Chemical Society
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• v.28 no.1
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• pp.62-69
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• 1984

The reaction of toluene with ethanol was studied over various cation-exchanged pentasil zeolite catalysts. The toluene disproportionation reaction to produce xylenes increased with increasing reaction temperature and the activity of alkylation of toluene with ethanol showed maximum at around $400^{\circ}C$. Only Cs-ZSM-5 catalyst showed pronounced p-ethyltoluene selectivity increasing to 96% with increasing degree of Cs-exchange. The sorption rate of m-xylene was lower for Cs-exchanged ZSM-5 than H-ZSM-5 catalyst. These phenomena were interpreted in terms of shape selectivity arising from the partial blocking of channel intersections by large cesium ions.

• Journal of Magnetics
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• v.19 no.1
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• pp.49-54
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• 2014

The influence regarding the dehydrogenation speed, at the desorption-recombination state during the hydrogenation-disproportionation-desorption-recombination (HDDR) process, on the microstructure and magnetic properties of Nd-Fe-B magnetic powders has been studied. Strip cast Nd-Fe-B-based alloys were subjected to the HDDR process after the homogenization heat treatment. During the desorption-recombination stage, both the pumping speed and time of hydrogen were systematically changed in order to control the speed of the desorption-recombination reaction. The magnetic properties of HDDR powders were improved as the pumping speed of hydrogen at the desorption-recombination stage was decreased. The lower pumping speed resulted in a smaller grain size and higher DoA. The coercivity and the remanence of the 200-300 ${\mu}m$ sized HDDR powder increased from 12.7 to 14.6 kOe and from 8.9 to 10.0 kG, respectively. In addition, the remanence was further increased to 11.8 kG by milling the powders down to about 25-90 ${\mu}m$, resulting in $(BH)_{max}$ of 28.8 MGOe.

• Textile Coloration and Finishing
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• v.27 no.1
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• pp.1-10
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• 2015

The aim of the current study is to identify the dimerization and decomposition kinetics of the F-$D_M$ type. The regeneration of F-VS from $F_iF_j-D_M$ or the reversibility of the dimerizations were investigated. The order of real rate constants of the dimerization('$K_D{^{ij}}$) would seem to be similar to that of rate constants of a dimerization($K_D{^{ij}}$) for VS dyes at a given pH because of the constancy of the equilibrium constants($K_a{^j}$-value). The reverse reactions of the $D_M$ types are appeared to occur in two steps, the deprotonation of ${\alpha}$-carbon of the $D_M$ types and disproportionation. The ratio of the decomposition of the $D_M$ type to F-Hy and F-VS appears to be related with the ratio of $K_i/K_j$. Similarities were also found among various other reactions, including homo- and mixed dimerization. VS dyes undergoing fast hydrolysis have difficulty in forming a dimer. The higher the reactivity with cellulose or hydroxide ion, the smaller the dimerization. The easiness of the dimerization was thus found to be inversely proportional to the rate of hydrolysis.