• Title/Summary/Keyword: chemical composition transition

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Microwave-assisted Synthesis of Mixed Ligand Complexes of Zn(II), Cd(II) and Hg(II) Derived from 4-aminopyridine and Nitrite Ion: Spectral, Thermal and Biological Investigations

  • Dhaveethu, Karuthakannan;Ramachandramoorthy, Thiagarajan;Thirunavukkarasu, Kandasamy
    • Journal of the Korean Chemical Society
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    • v.57 no.3
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    • pp.341-351
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    • 2013
  • Zn(II), Cd(II) and Hg(II) complexes with a general composition[$M(L)_2(X)_2$], where L=4-aminopyridine (4AP) and $X=NO_2{^-}$ were prepared under microwave irradiation. The metal complexes were characterized by elemental analyses, molar conductance, IR, Far-IR, electronic, NMR ($^1H$, $^{13}C$), XPS spectral and thermal studies. The spectroscopic studies reveal the composition, different modes of bonding, electronic transition, different chemical environment of C and H atoms and the electronic state of the metal atoms. On the basis of the characterization data, tetrahedral geometry is suggested for all the complexes. The free ligand (4-aminopyridine) and their metal complexes were screened against phytopathogenic fungi and bacteria in vitro and the activities were compared.

The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)$_2Cl_2]^+$ in Water-t-butyl Alcohol Mixture

  • Park Yu Chul;Cho Young Je
    • Bulletin of the Korean Chemical Society
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    • v.9 no.1
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    • pp.1-4
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    • 1988
  • Rates of solvolysis of trans-[Co$(N-eten)_2Cl_2$]$^+$ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ${\Delta}V^{\neq}$ obtained from pressure effect on the rate constants were 2.55∼ 5.83 $cm^3mol^{-1}$. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant ($Ds^{-1}$). The gradient, m of Grunwald-Winstein plot for the trans-[Co$(N-eten)_2Cl_2$]$^+$ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.

Preparation of High Transparent Olefin Copolymer with Metallocene Catalyst

  • Lee, Dong-Ho;Choi, Yeon-Seok;Ha, Ki-Ryong
    • 한국정보디스플레이학회:학술대회논문집
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    • 2003.07a
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    • pp.1028-1029
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    • 2003
  • The copolymerization of ethylene and norbornene was carried out with ansa-metallocene and modified methylaluminoxane (MMAO) cocatalyst. The copolymerization behavior was changed with the structure of metallocene catalysts. In addition the catalyst activity was dependent on the structure of MMAO, i.e.. MMAO-4 which contains less i-butyl group compared to MMAO-3A exhibited higher catalyst activity than MMAO-3A. The glass transition temperature and the composition of the produced copolymer were not affected by MMAO type.

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Thermodynamic and Electrical Properties of Aminophenol and Anthranilic Acid Complexes with Some Transition Metals

  • M. G. Abd El Wahed;S. M. Metwally;M. M. El Gamel;S. M. Abd El Haleem
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.663-668
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    • 2001
  • Thermodynamic and electrical functions of aminophenol and anthranilic acid complexes with Mn(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) were determined. ΔG°, ΔH° and ΔS° were calculated with the help of stability constant values at different temperatures. It was found that the complexing processes have an exothermic nature. The studied complexes behave like semiconductors. The conduction takes place according to hopping mechanism. To show the composition of complexes conductometric and photometric titrations, IR spectra, thermal analysis and X-ray diffraction techniques were employed.

Petrogenesis of the Skarn at the Dielette, Cotentin, France (디엘레트지역(地域) 스카른의 암석학적(岩石學的) 성인연구(成因硏究))

  • Chang, Ho Wan
    • Economic and Environmental Geology
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    • v.18 no.2
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    • pp.139-150
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    • 1985
  • Skarn at the Dielette formed largely in calc-silicate hornfels at the contact with the Flamanville granite. The skarn consists mainly of garnet and pyroxene, and less frequently vesuvianite. Traversing toward calc-silicate hornfels wall rock from a central zone of the skarn, the general sequence of formation of mineral assemblages is: (1) dark brown garnet (2) pale brown garnet-vesuvianite-pyroxene, and (3) pyroxene-prehnite-scapolite-wollastonite envelopes (designated as transition zone) developed between skarn and calc-silicate hornfels. The central zone of the skarn consists mainly of dark brown garnets (garnet I) that contain little or no pyroxene. The pale brown garnet (garnet II) is associated with pyroxene and vesuvianite. The sequence of these garnets results from the zonal growth outward. There is an abrupt discontinuity in composition between garnet I formed in early stage and garnet II in late stage, while each garnet shows relatively uniform composition. At the zone in contact with the granite, the iron contents of garnets decrease toward the marginal zone of the skarn, from an average value of 36 mole % andradite in garnet I to 18 mole % andradite in garnet II. At the zone distant from the granite, the andradite component decreases from 28 mole % in garnet 1 to 19 mole % in garnet II. The variation of the iron contents of pyroxenes is also similar to that of garnets. The sharp discontinuity in composition of garnets and pyroxenes suggests that the skarn of study area was formed by infiltration metasomatic process. The results of the analyses of mineral assemblages of the transition zone by chemical potential diagrams suggest that the transition zone was made by the diffusion of the elements Ca, K and Fe from the skarn to the calc-silicate hornfels contact zone. The estimated temperatures and $Xco_2$ for the formation of the transition zone show $300^{\circ}C$$440^{\circ}C$ and $0.07{\pm}0.05<Xco_2<0.02{\pm}0.01$ at 1 Kb respectively.

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Liquid Phase Deposition of Transition Metal Ferrite Thin Films: Synthesis and Magnetic Properties

  • Caruntu Gabriel;O'Connor Charles J.
    • Journal of the Korean Ceramic Society
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    • v.43 no.11 s.294
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    • pp.703-709
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    • 2006
  • We report on the synthesis of highly uniform, single phase zinc and cobalt thin films prepared by the Liquid Phase Deposition (LPD) method. X-Ray diffraction, TGA and EDX measurements support the assumption that the as deposited films are constituted by a mixture of crystallized FeOOH and amorphous M(OH)$_2$ (M=Co, Zn) which is converted upon heat treatment in air at 600?C into the corresponding zinc ferrites. The films with adjustable chemical compositions are identified with a crystal structure as spinel-type and present a spherical or rod-like microstructure, depending on the both the nature and concentration of the divalent transition metal ions. Zinc ferrite thin films present a superparamagnetic behavior above blocking temperatures which decrease with increasing the Zn content and are ferromagnetic at 5 K with coercivities ranging between 797.8 and 948.5 Oe, whereas the cobalt ferrite films are ferromagnetic at room temperature with magnetic characteristics strongly dependent on the chemical composition.

Solvolyses of N-Methyl-N-phenylcarbamoyl Chlorides with Electron Acceptor Substituents in A Queous Binary Mixtures

  • Gu, In Seon;An, Seon Gyeong;Yang, Yeol;Go, Han Jung;Choe, Mun Ho;Lee, Ik Chun
    • Bulletin of the Korean Chemical Society
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    • v.22 no.8
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    • pp.842-846
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    • 2001
  • Solvolyses of N-methyl-N-phenylcarbamoyl chlorides in aqueous binary mixtures of acetone, ethanol, methanol and in water, D2O, and 50% D2O-CH3OD are investigated at 25.0 $^{\circ}C.$ The Grunwald-Winstein plots of first-ord er rate constants for N-methyl-N-phenylcarbamoyl chlorides with YCl (based on 2-adamantyl chloride) show a dispersion phenomenon. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original Grunwald-Winstein and extended Grunwald-Winstein correlations for the solvolyses of N-methyl-N-phenylcarbamoyl chlorides. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the dissociative SN2 transition state. The kinetic solvent isotope effects determined in deuterated water are consistent with the proposed mechanism of the general base catalyzed and/or a dissociative SN2 mechanism channel for N-methyl-N-phenylcarbamoyl chlorides solvolyses.

Structural Analysis of Simulated Fission-Produced Noble Metal Alloys and Their Superconductivities

  • Park, Yong Jun;Lee, Gwang Yong;Lee, Jong Gyu;Heo, Yong Deuk;Kim, Won Ho
    • Bulletin of the Korean Chemical Society
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    • v.21 no.12
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    • pp.1187-1192
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    • 2000
  • Ternary (Mo-Ru-Pd) and binary (Mo-Ru, Mo-Pd) alloys have been prepared using an Ar arc melting furnace. Mo and the noble metals, Ru and Pd, are the constituents of metallic insoluble residues, which were found in the early days of post-irradiation studies on uranium oxide fuels. In the present study, the structure of the alloys was evaluated using a powder X-ray diffractometer. Unit cell parameters were determined by least squares refinements of powder X-ray diffraction data. Scanning electron microscopic analyses of the surface of the alloys indicated that surface morphology was dependent on the crystallographic structure as well as its composition. Measurements of the magnetic susceptibility of the alloys showed evidence of superconducting transition from 3 to 9.2 K. Among the ternary and binary alloys, the ${\sigma}-phase$ showed the highest superconducting transition temperature,~9.2 K.

Transition-State Variation in the Solvolyses of Phenyl Chlorothionoformate in Alcohol-Water Mixtures

  • 구인선;양기열;강대호;박혜진;강금덕;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.20 no.5
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    • pp.577-580
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    • 1999
  • Solvolyses of phenyl chlorothionoformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of firstorder rate constants for phenyl chlorothionoformate with Ycl (based on 2-adamantyl chloride) show a dispersion phenomenon, and also the extended Grunwald-Winstein plots show a poor correlation for the solvolyses of phenyl chlorothionoformate. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original and extended Grunwald-Winstein correlations. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by the conjugation between the reaction center and the aromatic ring in the vicinity of the reaction center. This study has shown that the magnitude of l and m values associated with a change of solvent composition leads to predict the SN2 transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed SN2 mechanism.

Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism

  • Park, Yu-Chul;Cho, Young-Je
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.309-313
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    • 1990
  • The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.