• Bulletin of the Korean Chemical Society
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• 제20권12호
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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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• 제13권6호
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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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• 제4권5호
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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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• 제12권3호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 1995년도 춘계학술대회 논문집
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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 $(Pb_{1-x}Ca_x)(Zr_{1-y}Sn_y)O_3$.

• 한국자기학회지
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• 제16권1호
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• pp.23-27
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• 2006

역스피넬 산화물 $CoFe_2O_4$에서 Co를 Mn 또는 Cr클 치환하여 얻어지는 $Mn_xCo_{1-x}Fe_2O_4$ 및 $Cr_xCo_{1-x}Fe_2P_4$ 박막시료 들을 졸-겔 방법을 이용하여 제작하고 그 구조적, 자기적 특성들을 비교분석 하였다. X-ray diffraction 측정 결과, Mn 치환의 경우는 치환량의 증가에 따라 격자상수가 증가하였지만 Cr치환의 경우는 격자상수가 거의 변화하지 않음이 관측되었다. 이와 같은 결과는 Mn 치환의 경우 팔면체 자리의 Co이온과 같은 원자가 +2를 가지게 되는 것으로 설명 가능하며 Cr치환의 경우는 +3을 가지게 되어 같은 양의 $Fe^{3+}$이온들의 $Fe^{2+}$로의 환원이 발생하는 것으로 설명되어질 수 있다. $Cr_Co_{1-x}Fe_2O_4$박막들에 대한 Mossbauer 스펙트럼 측정 결과 사면체 자리에 $Fe^{2+}$이온의 존재가 관측되었으며 이는 $Cr^{3+}$이온의 팔면체 자리 치환에 의하여 야기되는 사면체 자리의 $Fe^{3+}{\rightarrow}Fe^{2+}$ 환원에 의한 것으로 해석된다. 반면에 $Mn_xCo_{1-x}Fe_2O_4$ 박막들에 대한 Mossbauer스펙트럼 측정 결과, $Fe^{2+}$ 이온의 존재는 관측되지 않았으며 Mn 치환량이 큰 경우 (>0.47)팔면체 자리의 $Fe^{3+}$이온들의 사면체 자리로의 이동이 관측되었다. 박막들에 대한 진동시료자화(vibrating sample magnetometry)측정 결과, Mn, Cr 치환의 경우 모두 $CoFe_2O_4$와 비교하여 포화자화량이 증가함이 나타났으며 치환에 관여한 이온들 간의 스핀 자기 능률 크기의 비교를 통하여 그 정성적인 설명이 가능하다.

• 한국분말재료학회지
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• 제19권2호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 하계학술대회 논문집
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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.

• 폴리머
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• 제25권6호
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• pp.796-802
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• 2001

나프탈렌을 측쇄로 갖는 새로운 폴리벤즈이미다졸 단량체을 합성하고, 이 단량체를 친핵치환반응에 의해 중합하였다. 4-Methoxy-N-naphthyl-1,2-phenylenediamine과 4-fluoro-benzoyl chloride의 반응으로 N-(4-fluorobenzoyl)-4-methoxy-N'-naphthyl-1,2-phenyl-enediamine이 합성되었고 이로부터 고리화반응 및 demethylation에 의해 단량체인 2-(4-fluoro-benzoyl)-5-hydroxy-1-naphthylbenzimidazole이 얻어졌다. 중합반응은 potassium carbonate를 함유하는 N-cyclohexyl-2-pyrrolidinone (CHP)에서 행해졌다. 생성된 폴리벤즈이미다졸은 N-methyl-2-pyrrolidinone (NMP)에 용해되었고 0.38 dL/g (NMP at $30^{\circ}C$)의 대수 점도를 가졌다. 유리전이온도($T_g$)는 $270^{\circ}C$였고 열중량분석에서 5% 중량감소를 보이는 온도는 질소분위기에서는 $550^{\circ}C$, 공기중에서는 $540^{\circ}C$였다.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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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.