• Journal of the Korean Chemical Society
• /
• v.68 no.2
• /
• pp.65-73
• /
• 2024

The halide-acetylene anions, X^--HCCH (X = F, Cl, and Br) have been studied by using several different ab initio and DFT methods to determine structures, hydrogen-bond energies, vibrational frequencies of the anion complexes. Although the halide-acetylene complexes all have linear equilibrium structures, it is found that the fluoride complex is characterized with distinctively different structure and interactions compared to those of the chloride and bromide complexes. The performance of various density functionals on describing ionic hydrogen-bonded complexes is assessed by examining statistical deviations with respect to high level ab initio CCSD(T) results as reference. The density functionals employed in the present work show considerably varying degrees of performance depending on the properties computed. The performances of each density functional on geometrical parameters related with the hydrogen bond, hydrogen-bond energies, and scaled harmonic frequencies of the anion complexes are examined and discussed based on the statistical deviations.

• Journal of the Korean Chemical Society
• /
• v.6 no.2
• /
• pp.122-124
• /
• 1962

The silver halide precipitate tends to separate in curdy form of flocculated colloid when it is precipitated by direct mixing of reactant solutions. This type of precipitate has a great tendency to adsorb or occlude foreign ions in the solution.When silver halide in precipitated from homogeneous solution using the slow hydrolysis of Alkyl halide or Ally halide, the precipitate becomes dense, filterable and uniform in particle size which is very advantageous in gravimetric analysis.We found that silver halide precipitates obtained from homogeneous solution with hydrogen halide formed by the hydrolysis of alkyl halide do not give the color change with fluorescein as adsorption indicater, while silver halide precipitates obtained by direct mixing method give sharply pink color which appear to be uniformly distributed through the solution in silver ion excess.

• Journal of the Korean Chemical Society
• /
• v.29 no.1
• /
• pp.45-51
• /
• 1985

Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

• Transactions of the Korean hydrogen and new energy society
• /
• v.25 no.6
• /
• pp.602-608
• /
• 2014

The sequence of bond overlap population of metal hydrogen binding is in Al-H > Fe-H > Zr-H > V-H. This results shows the binding energy of Al-H is the biggest in this metals (Al, Fe, Zr, and V) and hydrogen interaction. The Vanadium-hydrogen binding shows the weakest binding energy compared to other metals and it causes easy hydrogen desorption from the corresponding metals. The net charge of Al-H show the biggest value of 0.2248 and the severe localizations of electrons around aluminum and imply strongest covalent binding nature in these metals. This study is applicable to the purification of hydrogen in other bulk gas.

• Journal of the Korean Chemical Society
• /
• v.30 no.3
• /
• pp.265-272
• /
• 1986

Kinetic studies for the methanolysis of tert-butyl halides (t-BuCl, t-BuBr, t-BuI) were carried out in MeOH-1,1,2,2-tetrachloroethane mixtures. The solvatochromic comparison method was used with six indicators to analyze solvent effects on the ionizations of tert-butyl halides. It was shown that the cooperative effect of solvent polarity-polarizability was the most important factor influenced on the methanolysis rates of tert-butyl halides, but the electrophilic assistance for halide leaving group and the nucleophilic assistance for tert-butylium ion were considerably influential, too. And it was found that the electrophilic assistance caused by hydrogen bonding and the nucleophilic assistance for carbon center were stronger for more basic leaving group ($I^-) and more polarizable leaving group(t-BuCl

• Journal of the Korean Chemical Society
• /
• v.32 no.2
• /
• pp.85-93
• /
• 1988

Solvolyses of t-butylhalides (X = Cl, Br, I) in quasi isodielectric solvent system, MeOH-nitromethane, MeOH-nitrobenzene and MeOH-ethyleneglycol have been studied kinetically. Methanolyses for t-butylhalides in MeOH-NM and MeOH-NB show rate maxima at 40~100 % (v/v) MeOH. The rate maxima observed have been interpreted as a result of cooperative enhancement of polarity-polarizability and hydrogen bonddonor ability of solvents. The influences of polarity-polarizability and hydrogen bonddonor ability on reactivities of substrates have been discussed in terms of Y value changes. The solvolysis rates for t-butylhalides in E.G. are more than 20 fold faster than those in MeOH and this was attributed to the solvent structure of E.G.

• Prospectives of Industrial Chemistry
• /
• v.24 no.1
• /
• pp.14-24
• /
• 2021

최근 전 세계적으로 이산화탄소를 포함한 대기 오염원의 배출을 줄이고 화석연료를 대체할 수 있는 차세대 청정에너지원으로 '수소'를 주목하고 있다. 하지만 현재까지 사회에 유통되는 대부분의 수소는 화석연료 개질을 기반으로 생산되기 때문에 2차 환경오염의 위험을 가지고 있다. 이에 이산화탄소 배출이 없이 태양에너지로부터 물을 분해해 수소를 생산하는 광전기화학 수소 생산 기술이 주목받고 있다. 단 광전기화학 물분해 수소생산을 실현하기 위해서는 수소를 충분히 생산시킬 수 있는 충분한 전류밀도, 과전압을 최소화하는 높은 개시전위, 및 그 생산비용을 최소화 할 수 있는 저렴한 공정 등을 동시에 만족시킬 수 있는 광전극 소재 개발이 필요하다. 최근 광소자용 소재로 각광을 받는 유기금속 할라이드 페로브스카이트 소재가 상기의 조건들을 상당히 만족할 것으로 기대되고 있어 광전기화학 물분해 셀로 적용되는 연구들이 수행되고 있다. 본 기고문에서는 유기금속 할라이드 페로브스카이트 소재기반 광전기화학 물분해 관련 최신 연구동향과 전망을 다루고자 한다.

• Clean Technology
• /
• v.6 no.1
• /
• pp.71-78
• /
• 2000

Removal rates of hydrogen sulfide were investigated to known effects of several light sources with external and internal irradiation on the desulfurization using C. thiosulfatophilum. In the case of internal illumination system, optical-fiber photobioreactor was applied to increase the light availability. Furthermore, sunlight was used as the main light energy in the daytime and metal-halide lamp was applied as an additional light energy at night. Light energy of 99% was saved by the application of the LED's array in comparison with the incandescent light source. $H_2S$ removal rates at 5,000 lux in a 4-L photobioreactor were shown as 0.040, 0.138, 0.136, and 0.134 (${\mu}mol$ $H_2S/min$)/(mg protein/L), respectively, in the following order of light sources, when several light sources such as fluorescent, energy-saving, incandescent, halogen lamp, and filtered light at 460 nm were applied. Removal rate per unit cell concentration with the internal light diffused optical-fibers increased about 1 six times as much as that with the external light sources. Removal rate per unit cell concentration, using sunlight in the daytime and a metal-halide lamp at night, was 0.41 less than 0.869 (${\mu}mol$ $H_2S/min$)/(mg protein/L) using a 400 W metal-halide lamp day and night, since the automatic sunlight collection system can transmit the light intensity as only 10% of that with a metal-halide lamp.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.3
• /
• pp.803-808
• /
• 2012

We have implemented two-component spin-orbit relativistic effective core potential (SOREP) methods in an all-electron relativistic program DIRAC. This extends the capacity of the two-component SOREP method to many ground and excited state calculations in a single program. As the test cases, geometries and energies of the small halogen molecules were studied. Several two-component methods are compared by using spin-orbit and scalar relativistic effective core potentials. For the $I_2$ molecule, excitation energies of low-lying excited states agree well with those from corresponding all-electron methods. Efficiencies in SOREP calculations enhanced by using symmetries are also discussed briefly.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.4
• /
• pp.1004-1013
• /
• 2010

Three-dimensional superstructures of unique self-assemblies generated by exploring the conformational flexibility of various dipyrromethenes through creation of hydrogen-bonds with metal-halide anions are reported and the conformational diversity is thoroughly described in the solid and solution states by X-ray diffraction analysis and variable temperature NMR spectroscopy. The tetrahedral or octahedral structures of their precursors, various metal-dipyrromethene complexes, are also reported, based on the crystallographic data. STM images of the self-assemblies observed on graphite surfaces present interesting arrangements and appear as tubular bunches.