• Title/Summary/Keyword: basicity

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Complex Formation of Substituted Benzo-1,4,7,10,13-pentaoxacyclopentadecane (B15C5) with Nd(Ⅲ) (Nd(Ⅲ)과 치환된 Benzo-1,4,7,10,13-pentaoxacyclopentadecane (B15C5)와의 착물 형성에 관한 연구)

  • Kim, Hae-Joong;Kim, Jeong;Kim, Si-Joong
    • Journal of the Korean Chemical Society
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    • v.39 no.6
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    • pp.440-445
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    • 1995
  • The chemical compositions and stability constants, thermodynamic parameters for the neodymium(Ⅲ) complexes of substituted benzo-1,4,7,10,13-pentaoxacyclopentadecane(B15C5) have been determined by spectrophotometry and conductometry in methanol solution at various temperatures. As substituents, CH3, Br, CHO, NO2, and 3,4-(NO2)2 were used. In methanol solution the ratios of neodymium(Ⅲ) to the ligands in the complexes are 1 : 1. The stability constants were increased in order of B15C5-3,4-(NO2)2 < B15C5-NO2 < B15C5-CHO < B15C5-Br < B15C5 < B15C5-CH3. This observation can be explained in terms of the substituent effect. The order of stability constants was dimethylsulfoxide < acetone < acetonitrile in solution and the magnitudes were found to be inversely proportional to the solvents donicities. These results could be understood in terms of solvent basicity, ligand basicity, solvation of the cation, and entropy changes of complex formation.

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A Study on the Reduction of Electric Arc Furnace Dust with Carbon (탄소에 의한 전기로 분진의 환원반응에 관한 연구)

  • 진영주;김영진;박병구;이광학;김영홍;이재운
    • Resources Recycling
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    • v.7 no.3
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    • pp.27-35
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    • 1998
  • EAF dust generated from electric arc steelmaking process is classified as "hazardous" materials by tbe environmental regulation because of the existence of water leachable heavy metals such as Fe, Zn, Pb, and Cd. However, Fe and Zn among t the elements in the dust can be recovered to high valuable materials by applying a proper process. Therefore, in order to study t the possibility of recovery of iron from EAF dust, the effect oE carbon content and basicity, of synthesized EAF dust on the reduction rate of iron oxide was studied. Experimental results are as follows: TIle softening and melting temperature of the slag w was illcreased with increasing carbon addition amount [or carbon reduction eqUIvalent. At the carbon addition amount of 100% for carbon reduction equivalent and basicity of 1.7, reduction rate of $Fe_2O$ in the slag was the highest. The reaction order fur reduction of $Fe_2O$ by carbon was nearly first order.

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Catalytic Effect of $MO_4^{2-_4}$ (M=Cr, Mo and W) on Hydrolyses of Carbon and Phosphorus Esters

  • An, Byeong Tae;Park, Hui Seon;Lee, Eun Ju;Eom, Ik Hwan
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.905-908
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    • 2000
  • Second-order rate constants have been measured spectrophotometrically for the hydrolysis of p-nitrophenyl ac-etate (PNPA) and p-nitrophenyl diphenylphosphinate (PNPDPP) with MO42- (M = Cr, Mo and W) in phos-phate buffer (pH = 8.00) at 35.0 $^{\circ}C.$ Thes e MO42- species exhibit large catalytic effect in the hydrolysis of PNPA and PNPDPP except WO42- in the reaction with PNPA. The catalytic effect of these MO42- species has been observed to be much more significantin the hydrolysis of PNPDPP than in the hydrolysis of PNPA. Since the smallest CrO42-would be most highly solvated by H2O molecules, CrO42- is expected to exhibit the least catalytic effect, if solvation effect is the most important factor. However, in fact, CrO42- shows the highest cat-alytic effect toward PNPA, indicating that solvation effect is not solely responsible for the catalytic effect. The most basic CrO42- shows the highest catalytic effect, while the least basic WO42- is least reactive toward PNPA, indicating that the basicity of MO4 2- might bean important factor. However, in the hydrolysis of PNPDPP, no correlation is observed between the basicity and catalytic effect, suggesting thatbasicity alone can not be re-sponsible for the catalytic effect shown by the MO42- species. Formation of a chelate is suggested to be respon-sible for the high catalytic effect of MO42- in the hydrolysis reaction of PNPA and PNPDPP. The formation of chelate is considered to be more suitable for the reaction with PNPDPP than with PNPA based on the larger catalytic effect observed in the reaction with PNPDPP than with PNPA.

Stability Constants of Nitrogen-Oxygen Donor Macrocyclic Ligand-Metal Ion Complexes in Aqueous Solutions (질소-산소 주개 거대고리 화합물-금속착물의 수용액에서의 안정도상수)

  • Jeong Kim;Chang-Ju Yoon;Hyu-Bum Park;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.35 no.2
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    • pp.119-127
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    • 1991
  • The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

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Interface Reaction of Molten Converter Slag and Sintered CaO Pellet (용융 전로슬래그와 소결 CaO 펠렛 사이의 계면반응)

  • Kim Yaung-Hwan;Ko In-Yang
    • Resources Recycling
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    • v.13 no.1
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    • pp.47-53
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    • 2004
  • As a basic study of the re-using molten converter slag as an ordinary portland cement by conversion process, molten slag and sintered CaO pellet was reacted each other. The dissolution rate of the sintered CaO pellet into the molten slag was measured and the changes of the reaction layer was also investigated. The converter slag reagent-grade $SiO_2$ added was melted and hold for 30 minutes in MgO crucible between $1350∼1500 ^{\circ}C$. Then sintered CaO pellet heated at the same temperature was dipped into the molten slag and hold for 10∼30 min. After the reaction, the crucible was cooled in air and the specimen was cut off to the horizontal direction of the crucible. The dissolution rate of CaO pellet was measured by the change of the radius of sintered CaO pellet and the interface layer was observed by SEM/EDX and XRD. The dissolution rate of sintered CaO pellet contacted with the slag of basicity 1 was 9.8 $\mu\textrm{m}$/min at $1350^{\circ}C$ and increased to 18.0 $\mu\textrm{m}$/min at $1500^{\circ}C$. The rate was slightly decreased to 7.6 $\mu\textrm{m}$/min at $1350^{\circ}C$ and 15.0 $\mu\textrm{m}$/min at $V^{\circ}C$ in the slag of basicity 2. The dissolution rate of CaO in converter slag was followed to the rule of Arrhenius' temperature dependency, and the apparent activation energy of the dissolution of CaO was 36 kcal/mole. In case of the slag basicity of 1, the thickness of $C_2$S layer was 64-118 $\mu\textrm{m}$ and the thickness of $C_3$S was 28∼90 $\mu\textrm{m}$ for 10∼30 minutes at $1500^{\circ}C$. And the thickness of the $C_3$S layer was 90∼120 $\mu\textrm{m}$ at the same conditions in the slag basicity of 2.

A Preliminary Study on Stratigraphy and Petrochemistry of the Okcheon Group, Southwestern Okcheon Metamorphic Belt (서남 옥천변성대 옥천층군의 층서 및 암석화학에 대한 예비연구)

  • 유인창;김성원;오창환;이덕수
    • Economic and Environmental Geology
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    • v.36 no.6
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    • pp.511-525
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    • 2003
  • The Okcheon Group in the southwestern part of the Okcheon Metamorphic Belt is subdivided into two distinct tectonostratigraphic units: the Boeun unit in the south and the Pibanryeong unit in the north. The Boeun unit consists of petites, psammites, carbonaceous petites, limestones and pebble-bearing quartzites. The Pibanryeong unit is composed of petites, well-sorted fine-grained psammites, carbonaceous psammites and quartzites. In order to outlining stratigraphy and depositional environments of the Okcheon Group, detailed stratigraphic sections were measured in three locations; one section(Gosan section) of the Boeun unit and two sections(Sorungjae and Hwangryeongzae sections) of the Pibanryeong unit. The Gosan section of the Boeun unit is interpreted to be deposited in the shallow marine environments, whereas the Sorungjae and Hwangryeonaiae sections of the Pibanryeong unit appear to be deposited in slope and deep basin environments. This result indicates rapid subsidence between deposition of the Boeun and Pibanryeong units in sedimentary environment. The trace of sedimentological environments in the Hwasan area was investigated by geochemical analysis of 109 metapelitic and psammitic rock samples. Distinct chemical variations of politic and psammitic rocks from the Boeun and Pibanryeong units in the study area are evident from plots of major elements and $A1_2O_3$/$SiO_2$ versus Basicity Index($Fe_2O_3{+}MgO$)/($SiO_2{+}K_2O{+}Na_2O$). The rocks show a progressive chemical trend from the Boeun unit to the Pibanryeong unit on these diagrams. They in the southern sector of the Boeun unit display lower values and a comparatively wide range of $A1_2O_3$/$SiO_2$ and Basicity Index, as compared with those from the northern sector of the Boeun and Pibanryeong units. The southern sector of the Pibanryeong unit including narrow staurolite-bearing zone is characterized by values that are transitional between the Boeun and Pibanryeong units. These data, combined with depositional environment progressively deepened towards the northwest, support a half-graben model for the Okcheon basin, as proposed by Cluzel et al.(1990)

Structure and Intramolecular Proton Transfer of Alanine Radical Cations

  • Lee, Gab-Yong
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1561-1565
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    • 2012
  • The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the $NH_2$ group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [$NH_3{^+}-CHCH_3-COO{\bullet}$], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol.

Novel organic catalysts for nucleophilic fluorination including F-18 radiofluorination

  • Na, Hyeon Su;Kim, Dong Wook
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.3 no.2
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    • pp.116-121
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    • 2017
  • To overcome the low reactivity and solubility of alkali metal fluorides (MFs), various types of phase transfer catalysts (PTCs) have been developed over the last decades. However, since the fluoride activated by such PTC sometimes has a strong basicity, it may cause various side reactions such as elimination reaction or hydroxylation reaction in the nucleophilic fluorination reaction. Also, they may cause separation problems in the compound purification process. In recent advanced study, various PTCs have been developed to solve these problem of conventional catalyst. In this review, we would like to introduce three kinds of novel multifunctional organic catalysts such as bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA), easy separable pyrene-tagged ionic liquid (PIL) by reduced graphene oxide (rGO), and tri-tert-butanolamine organic catalyst.

The Change of Adsorption Characteristics for VOCs by HNO3 Activation of Adsorbent Prepared from MSWI Fly Ash (질산을 이용한 Fly Ash 흡착제의 표면 활성화에 따른 VOCs 흡착 특성의 변화)

  • Shim Choon-Hee;Lee Woo-Keun
    • Journal of Korean Society for Atmospheric Environment
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    • v.21 no.4
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    • pp.471-478
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    • 2005
  • The objective of this research is to improve adsorption efficiency of adsorbent made from MSWI (Municipal Solid Waste Incinerator) ny ash by $HNO_3$ activation. The acidity and the basicity were determined by Boehm's method and the surface structure was studied by BET method with N2 adsorption. The adsorption properties were investigated with benzene and MEK (Methylethylketone). $HNO_3$ activation can modify the surface property of an adsorbent such as specific surface area, pore volume, and functional group. According to the results, the specific surface area of the adsorbent was increased from $309.2m^2/g\;to\;553.2 m^2/g$ by activation. Also oxygen-containing functional groups were formed on it.

The Effect of Anion Catalysts in Transesterification Reaction (에스테르 교환반응(交渙反應)에서 음(陰)이온 촉매(觸媒)의 영향(影響))

  • Park, Keun-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.9 no.2
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    • pp.141-148
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    • 1992
  • Transesterification reactions (methyl methacrylate with diethanolamine, ethylene glycol with dimethylphthalate) were kinetically investigated in the presence of zinc compound catalysts at $120{\sim}170^{\circ}C$ The amount of reactants was measured by gas chromatography. and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively, The overall reaction order was 2nd. The apparent rate constant (k') was found to obey first kinetics with respect to the concentration of catalyst. It shows that according to an increase in basicity of anionic species the rate constant increase, and that a linear relationship exists between ln k and pKa in transesterification reaction of methyl methacrylate with diethanolamine.