• Title/Summary/Keyword: Ion formation mechanism

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Solvolyses of t-Butyl Halides in Binary Mixtures of Methanol with 1,2-Dimethoxyethane, 1,2-Dichloroethane and Pyridine

  • Yeol Sakong;Shi Choon Kim;Jin Sung Kim;Ikchoon Lee
    • Bulletin of the Korean Chemical Society
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    • v.11 no.2
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    • pp.99-105
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    • 1990
  • The Gutmann acceptor number(AN), solvatochromic parameters $({\alpha},{\beta}\;and\;{\pi}^{\ast})$ and hydrogen bonding equilibrium constants (KHB) were determined for three binary systems of methanol with 1,2-dimethoxyethane(DME), 1,2-dichloroethane(DCE) and pyridine (PYD). The solvolysis rate constants of t-butyl chloride, bromide and iodide were also determined in the three binary systems. Solvent properties and solvolysis rates have been discussed in the light of various solvent parameters. Solvolysis of t-butyl halides are most conveniently explained by the two-stage mechanism involving ion-pair intermediate with the ion-pair formation for chloride and ion pair dissociation for iodide as rate limiting.

MO Studies on the Gas-Phase Reaction of Dypnone Oxide with Chloride Ion$^\dag$

  • Kim, Wang-Ki;Sohn, Chang-Kook;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.7 no.4
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    • pp.279-282
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    • 1986
  • The MNDO calculations were performed in order to investigate the gas-phase reaction mechanism of 2-propene-1-al oxide, as a model compound of dypnone oxide(1,3-diphenyl-2-butene-1-one oxide) with the chloride ion. Optimized geometries and heats of formation for two probable concerted pathways, CHO and H migration, were determined and their activation energies were obtained. MO results show that although the formyl migration is thermodynamically more favorable than the hydride migration, the latter kinetically predominates over the formyl migration, which is contrary to the established migrating preferences. It is concluded that the hydride migratory propensity is catalyzed by the chloride ion by reducing the capability of the carbonyl ${\pi}$ bond to participate in the migration.

Mechanism on the Formation of Bis-9,9'-thioxanthenylmethane from the Reaction of Thioxanthylium Ion With Dimethylmercury(I)

  • Kim, Sung-Hoon;Kim, Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.157-162
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    • 1982
  • 9-Methylenethioxanthene(6) was synthesized and for the first time good mp and spectral data were taken. Reaction of (6) with thioxanthylium ion (1) in acetonitrile led to a carbenium addition adduct (8) which then was either attacked by a variety of nucleophiles subsequently added or underwent deprotonation reaction to give an olefin (13). From these reactions, was obtained bis-9,9'-thioxanthenylmethane (2). These results indicate clearly that (2) can be formed via (8) by accepting hydride. Isolation of (2) and (6) from the reaction of (1) with 9-methylthioxanthylium ion (18) also supports the involvement of (8) in the reaction of (1) with dimethylmercury. However, addition of thioxanthene radical (4) to (6) has not been ruled out.

Corrosion Mechanism and Bond-Strength Study on Galvanized Steel in Concrete Environment

  • Kouril, M.;Pokorny, P.;Stoulil, J.
    • Corrosion Science and Technology
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    • v.16 no.2
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    • pp.69-75
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    • 2017
  • Zinc coating on carbon steels give the higher corrosion resistance in chloride containing environments and in carbonated concrete. However, hydrogen evolution accompanies the corrosion of zinc in the initial activity in fresh concrete, which can lead to the formation of a porous structure at the reinforcement -concrete interface, which can potentially reduce the bond-strength of the reinforcement with concrete. The present study examines the mechanism of the corrosion of hot-dip galvanized steel in detail, as in the model pore solutions and real concrete. Calcium ion plays an important role in the corrosion mechanism, as it prevents the formation of passive layers on zinc at an elevated alkalinity. The corrosion rate of galvanized steel decreases in accordance with the exposure time; however, the reason for this is not the zinc transition into passivity, but the consumption of the less corrosion-resistant phases of hot-dip galvanizing in the concrete environment. The results on the electrochemical tests have been confirmed by the bond-strength test for the reinforcement of concrete and by evaluating the porosity of the cement adjacent to the reinforcement.

Reversed-Phase Ion-Pair High Performance Liquid Chromatographic Elution Behavior of Noble Metal-Thiacrown Ether Complexes (귀금속-티아크라운에테르 착물들의 역상 이온쌍 고성능 액체크로마토그래피 용리거동)

  • Chung, Yong Soon;Kim, Dong Won;Lee, Kang Woo;Kim, Chang Seok
    • Journal of the Korean Chemical Society
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    • v.42 no.4
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    • pp.416-421
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    • 1998
  • In the reversed-phase ion-pair high performance liquid chromatographic (RPIP-HPLC) elution behavior of noble metal-thiacrown ether complexes, the effects of the concentration of ion-pairing reagent and kind of ligands were studied. It was found that the less the number of atoms in the ring of the thiacrown ether molecule was, the larger the selectivity was, and the elution mechanism of the complexes was explained due to the formation of ion-pair when the concentration of sodium dodecyl sulfate (SDS) in mobile phase was lower than 10 mM and due to the formation of micelle when the SDS concentration was higher than 10 mM. As a conclusion, separations of the noble metal-thiacrown ether complexes in an optimum separation condition were accomplished successfully and the method was proved to be an useful one for the separation and determination of Ag (Ⅰ) ion in a black-white photographic fixing solution.

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Degraded Paddy Soils. I. Theoretical Analysis on the Sultide Formation and the Effect of Iron Hydroxide Upon Removal of Sulfide from Solution

  • Cho, Chai-Moo
    • Applied Biological Chemistry
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    • v.2
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    • pp.9-14
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    • 1961
  • The formation of sulfide from sulfate has been discussed from the thermodynamic principles. No mechanism of the reaction has been presented. From the stoichiometric and Nernst equations for the conversion of sulfate into sulfide, it was concluded that the formation of sulfide from sulfate can take place more readily if pH of a medium is low. The difficulty of this conversion increases with increasing pH. As pH of a medium increases, the degree of dissociation of H₂S into S= increases and this, in turn, renders the chance of precipitation of sulfide as FeS easier. Higher the pH of a soil or medium, greater is the S= concentration. The concentration of ferrous ion required to remove dissolved sulfide in a medium by forming insoluble FeS decreases with increasing pH. From the theory it was pointed out that an application of lime and iron rich foreign substances to a soil may be effective in causing the removal of dissolved sulfide from solution.

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Effect of Carboxylic Acid on the Hydration of Plaster of Paris under Alkalinity (알카리성 분위기에서 소석고의 수화에 미치는 카르복실산의 영향)

  • 이승헌
    • Journal of the Korean Ceramic Society
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    • v.31 no.10
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    • pp.1107-1114
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    • 1994
  • Although various theories have been presented on the mechanism of setting retardation of plaster in addition to organic admixtures. The purpose of this paper is that Hydration studies of plaster of paris in the presence of carboxylic acids under alkalinity are examined in the coordination chemistry. Setting of plaster of paris is retarded by the addition of carboxylic acids except oxalic acid. And setting of plaster of paris contained 5 wt% of Ca(OH)2 is also retarded by the addition of above-mentioned carboxylic acids. The degree of retarding effect under alkalinity is found to be a function of the number of the functional group and the length of carbon chain of carboxyl acids. These reasons are attributed to the soluble complex formation, that is calcium complex formation between calcium ion and carboxylic acids. The author's proposal was confirmed by the results of electrical conductivity measurement. The formation of calcium complex was surpported by IR spectra.

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Mechanistic Studies on the Formation of Soluble Intermediate during the Electrochemical Nucleation of Lead Dioxide

  • Hwang Euijin;Cho Keunchang;Kim Ho Il;Kim Hasuck
    • Bulletin of the Korean Chemical Society
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    • v.15 no.12
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    • pp.1054-1058
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    • 1994
  • Different behavior on the formation of soluble intermediate was observed depending on the substrate employed during the nucleation of lead dioxide from plumbous ion using a rotating ring-disk electrode. It was found that no soluble intermediate was formed at glassy carbon electrode, while the presence of soluble intermediate could be detected at platinum substrate. From the different anodic behavior of two substrates, the formation of a probable Pb(Ⅲ) soluble intermediate was suggested. A most probable nucleation mechanism at the platinum substrate involving a second order chemical reaction was derived on the basis of rotating disk electrode experiments.

Metal Ion Dissolution in Nitric Acid with Lead-Borosilicate Glass for Barrier Ribs in PDP

  • Kim, Jae-Myung;Lee, Chong-Mu;Kim, Hyung-Sun
    • 한국정보디스플레이학회:학술대회논문집
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    • 2005.07b
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    • pp.1252-1254
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    • 2005
  • Recently, PDP barrier ribs require the formation of complex structure so that they are usually formed by etching method. For producing the fine ribs structure, during the etching process the metal ions of matrix (glass) of barrier materials should be understood on the etching mechanism with etching condition. We analyzed the quantity of Pb, Si, and B ions from the etch solution as a function of etching time.

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Interaction of pharmaceuticals with betacyclodextrin III Influence of Betacyclodextrin on Phenobarbital Hydrolysis

  • Min, Shin-Hong
    • YAKHAK HOEJI
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    • v.16 no.4
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    • pp.155-161
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    • 1972
  • The hydrolysis of phenobarbital is decelerated in alkaline solution by betacyclodextrin. The betacyclodextrin inhibits the degradation of phenobarbital up to 1.5 fold in the system containing 1% betacyclodextrin. The degradation mechanism in systems containing betacyclodextrin is the same that in system without complexing agent, although the rate constants are different. The pH dependence of the hydrolysis rate deceleration is compared with the ionization percent of betacyclodextrin. The results indicate that a direct relationship does not exist between the ionization of betacyclodextrin. It seems reasonable therefore that the phenobarbital undergoes a stable complex with betacyclodextrin and complex formation would provide a better shield for the phenobarbital from hydroxyl ion attack.

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