• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1451-1456
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• 1999

Solvolyses of α-methoxy-α-(trifluoromethyl)phenylacetyl chloride in H₂O, D₂O, CH₃OD, 50% D₂O-CH₃OD, and in aqueous binary mixtures of acetone, dioxane, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of first-order rate constants for α-methoxy- α-(trifluoromethyl)phenylacetyl chloride with $Y_{Cl}$ show a dispersion phenomenon. Solvent nucleophilicity N has been shown to give considerable im-provement when it is added as an 1N term to the original Grunwald-Winstein for the solvolyses of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by solvent nucleophilicity. The magnitude of l and m values associated with a change of solvent composition predicts the associative $S_N2$ transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed associative $S_N2$ or $S_AN$ mechanism for the of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.642-647
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• 1992

Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

• Bulletin of the Korean Chemical Society
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• v.4 no.5
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• pp.208-211
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• 1983

Kinetic studies of nucleophilic substitution reactions of para-substituted benzylchlorides with anilines were conducted in a range of MeOH-MeCN mixtures at $55.1^{\circ}C$. Hammett ${\rho}_C$, ${\rho}_N$ values and Bronsted ${\beta}$ values were determined, in other to examine the transition state variations caused by changes in nucleophiles, substituents and solvents properties (${\pi}^{\ast}$ and ${\alpha}$). Applications of potential energy surface (PES) and quantum mechanical (QM) models of transitheion state characterization lead us to conclude that the reaction proceeds via the dissociative $S_N2$ mechanism.

• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.282-286
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• 1991

Kinetic studies of the reactions of benzyl benzenesulfonates with benzylamines in methanol and acetonitrile have been carried out. The reaction was found to proceed by a dissociative $S_N2$ in MeCN but by an associative $S_N2$ mechanism in MeOH. The transition state was rather loose in MeCN whereas it was tight in MeOH, in contrast to a tighter TS in MeCN for the corresponding reactions with aniline. The reaction of benzylamine in MeOH was characteristic of the highly solvated nucleophile, benzylamine, compared to the normal reaction in MeCN.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1995.05a
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• pp.5-8
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• 1995

The crystal structure and dielectric propoerties of $(Pb_{1-x}Ca_x)(Zr_{1-y}Sn_y)O_3$ Ceramics were investigated. Sn substitution reduced the volitility of PbO due to the decrease of the unit cell. The crystal structure of $(Pb_{1-x}Ca_x)(Zr_{1-y}Sn_y)O_3$ Ceramics was refined based on Orthorhombic Cmmm space group, More than two types of phase transition were observed, These phase transitons make the posicitve and negative temperature coefficient of dielectric constant of $(Pb_{1-x}Ca_x)(Zr_{1-y}Sn_y)O_3$.

• Journal of the Korean Magnetics Society
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• v.16 no.1
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• pp.23-27
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• 2006

By substituting Mn or Cr for Co in inverse spinel $CoFe_2O_4,\;Mn_xCo_{1-x}Fe_2O_4\;and\;Cr_xCo_{1-x}Fe_2O_4$ and thin films were prepared by sol-gel method and their structural and magnetic properties were investigated. X-ray diffraction indicates that the cubic lattice constant increase for the Mn substitution while it hardly changes for the Cr substitution. Substitution of $Mn^{2+}$ for octahedral $Co^{2+}$ sites can explain the increase of lattice constant in $Mn_xCo_{1-x}Fe_2O_4$. On the other hand, Substitution of $Cr^{3+}$ for octahedral $Co^{2+}$ and subsequent reduction of $Fe^{3+}$ ion into $Fe^{2+}$ are expected to happen. Mossbauer spectroscopy measurements on $Cr_xCo_{1-x}Fe_2P_4$ indicate the existence of tetrahedral $Fe^{2+}$ ions that are created through reduction of tetrahedral $Fe^{3+}$ ions in order to compensate charge imbalance happened by $Cr^{3+}$ substitution for octahedral $Co^{2+}$ sites. On the other hand, no $Fe^{2+}$ ions were detected by Mossbauer spectroscopy for $Mn_xCo_{1-x}Fe_2O_4$. A migration of $Fe^{3+}$ ions from octahedral to tetrahedral sites In $Mn_xCo_{1-x}Fe_2O_4$ was detected by Mossbauer spectroscopy for x>0.47. Vibrating sample magnetometry measurements on the samples at room temperature revealed that the saturation magnetization increases by Mn and Cr substitution for certain range of x, qualitatively explainable in terms of the comparison of spin magnetic moment among the related transition-metal ions.

• Journal of Powder Materials
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• v.19 no.2
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• pp.146-150
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• 2012

The effects of nano $Fe_xC$ addition to superconducting properties of $in$ $situ$ processed $MgB_2$ superconductors was examined. 0.1 wt.% and 1 wt.% nano $Fe_xC$ powders were mixed with boron and magnesium powders by ball milling. The powder mixtures were made into pellets by uniaxial pressing. The pellets were heat-treated at $700^{\circ}C-900^{\circ}C$ in argon atmosphere for $MgB_2$ formation. It was found by powder X-ray diffraction that the raw powders were completely converted into $MgB_2$ after the heat treatment. The superconducting transition temperature ($T_c$) and critical current density ($J_c$), estimated from susceptibility-temperature and $M-H$ curves, were decreased by nano $Fe_xC$ addition. The $T_c$ and $J_c$ decrease by nano $Fe_xC$ addition are attributed to the incorporation of iron and carbon with $MgB_2$ lattices (Fe substitution for Mg and C substitution for B) due to the high reactivity of the nano $Fe_xC$ powder.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.07a
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• pp.624-627
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• 2001

Two kinds of Nd$_{1+x}$Ba$_{2-x}$Cu$_3$O$_{7-{\delta}}$, the sintering samples and zone melting samples, were heat treated under pure Ar at 95$0^{\circ}C$. The substitution of Nd ion for Ba ion in the Nd$_{1+x}$Ba$_{2-x}$Cu$_3$O$_{7-{\delta}}$ before and after the heat treatment were investigated by XRD. In order to know the effects of the heat treatment, the T$_{c}$ and J$_{c}$ of samples with the heat treatment and those without the heat treatment by Ar were comparatively studied. The results show that the substitution of Nd for Ba decreased, T$_{c}$, and J$_{c}$ increased after the treatment under Ar at 95$0^{\circ}C$. The Nd$_{1+x}$Ba$_{2-x}$Cu$_3$O$_{7-{\delta}}$ samples were oxygenated under pure oxygen at 30$0^{\circ}C$. From the XRD pattern it was found that the sample with x< 0.4 could transfer from tetragonal phase to orthorhombic phase after the oxygenation, but the sample with x>0.4 could not make the phase transition even after a long time oxygenation.ion even after a long time oxygenation.ation.n.ation.ation.

• Polymer(Korea)
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• v.25 no.6
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• pp.796-802
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• 2001

Novel monomer for polybenzimidazole was prepared and polymerized via aromatic nucleophilic substitution reaction. Thus, N-(4-fluorobenzoyl)-4-methoxy-N'-naphthyl-1,2-phenylenediamine was synthesized from the reaction of 4-methoxy-N-naphthyl-1,2-phenylenediamine and 4-fluorobenzoyl chloride. N-(4-fluorobenzoyl)-4-methoxy-N'-naphthyl-1,2-phenylenediamine was converted to 2-(4-fluorobenzoyl)-5-hydroxy-1-naphthylbenzimidazole by ring closure and demethylation reaction. Polymerization was done in N-cyclohexyl-2-pyrrolidinone (CHP) containing potassium car bonate. The resulting polymer was soluble in N-methyl-2-pyrrolidinone (NMP) and had inherent viscosity of 0.38 dL/g (NMP at $30^{\circ}C$). The glass transition temperature ($T_g$ ) of the polybenzimidazole was $270^{\circ}C$. The thermogravimetric analysis (TGA) thermograms of this polymer showed 5% weight losses at $550^{\circ}C$ in nitrogen and at $540^{\circ}C$ in air.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.117-121
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• 2008

Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 5-nitro-8-quinolyl benzoate (5) with alkali metal ethoxides, EtO?M+ (M+ = Li+, Na+ and K+) in anhydrous ethanol (EtOH) at 25.0 0.1 C. The plots of kobsd vs. [EtO?M+] exhibit upward curvatures, while the corresponding plots for the reactions of 5 with EtO?Na+ and EtO?K+ in the presence of complexing agents, 15-crown-5-ether and 18-crown-6-ether are linear with rate retardation. The reactions of 5 with EtO?Na+ and EtO?Li+ result in significant rate enhancements on additions of Na+ClO4, indicating that the M+ ions behave as a catalyst. The dissociated EtO and ion-paired EtOM+ have been proposed to react with 5. The second-order rate constants for the reactions with EtO (kEtO) and EtOM+ (kEtOM+) have been calculated from ion-pairing treatments. The kEtO and kEtOM+ values decrease in the order kEtONa+ > kEtOK+ > kEtOLi+ > kEtO, indicating that ion-paired EtOM+ species are more reactive than the dissociated EtO ion, and Na+ ion exhibits the largest catalytic effect. The M+ ions in this study form stronger complex with the transition state than with the ground state. Coordination of the M+ ions with the O and N atoms in the leaving group of 5 has been suggested to be responsible for the catalytic effect shown by the alkali metal ions in this study.