• Title/Summary/Keyword: $S_N1$ mechanism

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The Effects of Solvent Composition and Pressure on the Rate of Solvolysis of trans-$[Co(en)_2Cl_2]^+$, trans-$[Co(N-eten)_2Cl-2]^+$, trans-$[Co(N-meen)_2Cl-2]^+$ and trans-$[Co(tn)_2Cl-2]^+$ in Aceton-Water Mixture. Excess Free Energy & Free Energy Cycle and Reaction Mechanism (아세톤-물 혼합용매에서 trans-$[Co(en)_2Cl-2]^+$, trans-$[Co(N-eten)_2Cl-2]^+$, trans-$[Co(N-meen)_2Cl_2]^+$, trans-$[Co(tn)_2Cl_2]^+$ 착이온의 가용매 분해반응에 대한 압력과 용매조성의 영향. 반응메카니즘과 자유에너지 변화사이클 및 Excess 자유에너지)

  • Yu-Chul Park;Young-Je Cho
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.629-636
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    • 1985
  • The rates of solvolysis of trans-$[Co(AA)_2Cl_2]^+$ in which AA indicates ethylenediamine(en), N-ethylethylenediamine (N-eten), N-methylethylenediamino (N-meen) and trimethylenediamine(tn) respectively have been investigated using conductometric and spectrophotometric methods at various pressure up to 2,000 bar in acetone-water mixture. The activation volumes (${\Delta}V^{\neq}) obtained from the pressure effect on rate constants were -0.2∼0.9 $cm^3mole^{-1}$ for en, -0.2∼0.6 $cm^3mole^{-1}$ for N-eten, -0.8∼6.0 $cm^3mole^{-1}$ for N-meen and 0.7∼7.0$cm^3mole^{-1}$ for tn. The rates of solvolysis of these complexes were analyzed by comparing with the results obtained from excess free energy ($G^E$) and free energy cycle. It was found that $S_N1$ character was increased with decreasing the pressure and increasing the content of acetone in the mixture solvent. In addition to that, the effect of charge separation on the mechanism of solvolysis was discussed.

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(Photosensitive Polymers VII) Mechanism of Photosensitized Curing Reaction of Cinnamoylated Polymers ((感光性 高分子에 關한 硏究 VII) Cinnamoylated Polymers의 光增感 硬化反應機構)

  • Kim, Kwang-Sup;Shim, Jyong-Sup
    • Journal of the Korean Chemical Society
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    • v.10 no.4
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    • pp.166-174
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    • 1966
  • The multistep mechanism of photosensitized curing reaction cinnamoylated photosensitive polymer is proposed from the energy level diagram of cinnamic acid and sensitizer, and from the fact that excess of sensitizer brings the sensitivity to a limiting value etc. Various factors which have effects on the ability of sensitizer are also discussed. The mechanism involves following steps: activation to the first excited singlet states of cinnamoyl group(C) and sensitizer(S) by their absorption of photon, their intersystem crossing to the lowest triplet state, bimolecular internal quenching by formation of excimer of sensitizer, triplet excitation energy transfer and intermolecular addition between cinnamoyl group in ground state and that in triplet state. The rate equation derived from this mechanism is $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ where $I^c_{abs}\;and\;I^s_{abs}$: the rates of absorption of photon by cinnamoyl group and sensitizer $K_n$: Constants. It is proved with the cinnamate of poly(glyceryl phthalate)(PGC) in the absence of sensitizer using the infrared analytical method and successfully applied for the experimental data reported on the effects of the degree of cinnamoyl esterification and the concentration of sensitizer upon the sensitivity.

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Two Stage Process Mechanism of Silica Adsorption by Soil in Adsoption Kinetics (토양의 규산 흡착 카이네틱에서 2단계 흡착 기작)

  • Lee, Sang-Eun;Jung, Kwang-Yong
    • Korean Journal of Soil Science and Fertilizer
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    • v.29 no.2
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    • pp.107-112
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    • 1996
  • To clarify the mechanism of silica adsorption to soil, kinetic study using continuous stirred-flow method was conducted with the Luisiana soil at three pH levels (pH 5.0, 6.5, and 8.0). Silica adsorption increased continuously without showing the maximum adsorption for long enough experimental time. Kinetic curve of silica adsorption could be divided into two stage processes. The first stage process was fitted well to the following equation with highly significant correlation coefficient : $$R_{ad}=K_a*(Q_{OH}^S)^n$$ where, $R_{ad}$ is silica adsorption rate($Si\;{\mu}mal/min$). $Q_{OH}^S$ is the negative charge sites on the soil surface created by alkali titration, and $K_a$ and n are constants. The "n" value of the first stage process was 1.1. This value indicates that the silica adsorption is accomplished by the monodendate ligand bonding. The second stage process was fitted well to the following equation : $$R_{ad}=K_b*(pH)$$ where, $K_b$ is a constant. The equation indicates that the silica adsorption is not proportional to the $OH^-$ ion concentration. Rather, the increasing pattern of silica adsorption rate with the increase of $OH^-$ ion concentration would decrease exponentially.

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N III Bowen Lines and Fluorescence Mechanism in the Symbiotic Star AG Peg

  • Hyung, Siek;Lee, Seong-Jae;Lee, Kang Hwan
    • Journal of Astronomy and Space Sciences
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    • v.35 no.1
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    • pp.7-18
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    • 2018
  • We have investigated the intensities and full width at half maximum (FWHM) of the high dispersion spectroscopic N III emission lines of AG Peg, observed with the Hamilton Echelle Spectrograph (HES) in three different epochs at Mt. Hamilton's Lick Observatory. The earlier theoretical Bowen line study assumed the continuum fluorescence effect, presenting a large discrepancy with the present data. Hence, we analyzed the observed N III lines assuming line fluorescence as the only suitable source: (1) The O III and N III resonance line profiles near ${\lambda}$ 374 were decomposed, using the Gaussian function, and the contributions from various O III line components were determined. (2) Based on the theoretical resonant N III intensities, the expected N III Bowen intensities were obtained to fit the observed values. Our study shows that the incoming line photon number ratio must be considered to balance at each N III Bowen line level in the ultraviolet radiation according to the observed lines in the optical zone. We also found that the average FWHM of the N III Bowen lines was about $5km{\cdot}s^{-1}$ greater than that of the O III Bowen lines, perhaps due to the inherently different kinematic characteristics of their emission zones.

The Origin of Coercivity Enhancement of Sintered NdFeB Magnets Prepared by Dy Addition

  • Yu, N.J.;Pan, M.X.;Zhang, P.Y.;Ge, H.L.
    • Journal of Magnetics
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    • v.18 no.3
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    • pp.235-239
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    • 2013
  • The effect of Dy addition on the microstructure and magnetic properties of the sintered NdFeB magnets was investigated. The results of the microstructure analysis showed that Dy-free and Dy-doped samples are composed of $Nd_2Fe_{14}B$ (P42/mnm) and a trace of Nd-rich phase. Dy addition reduces significantly the pole density factor of (004), (006) and (008) crystal faces as estimated by the Horta formula. Accordingly, the coercivity of the Dy-doped sample increases from 2038 $kA{\cdot}m^{-1}$ up to 2288 $kA{\cdot}m^{-1}$. The $H_{cj}(T)/M_s(T)$ versus $H^{min}_N/M_s(T)$ (Kronm$\ddot{u}$ller-plot) behavior shows that the nucleation is the dominating mechanism for the magnetization reversal in these two kinds of magnets, and two microstructural parameters of ${\alpha}_k$ and $N_{eff}$ are obtained. The Kronm$\ddot{u}$ller-Plot gives evidence for an increase of the ${\alpha}_k$ responsible for an increase of the coercivity as the result of the increase of the magnetic field as the magnetic domain reversed.

Thiadiazole-thione surfactants: Preparation, flotation performance and adsorption mechanism to malachite

  • Huang, Yaoguo;Liu, Guangyi;Liu, Jun;Yang, Xianglin;Zhang, Zhiyong
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.99-108
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    • 2018
  • In this paper, novel thiadiazole-thione surfactants including 5-heptyl-1,3,4-thiadiazole-2-thione (HpSDT), 5-phenyl-1,3,4-thiadiazole-2-thione (PSDT) and 5-(2-hydroxyphenyl)-1,3,4-thiadiazole-2-thione (HPhSDT) were synthesized and originally introduced as collectors in froth flotation. Microflotation tests showed that HpSDT exhibited better flotation response to malachite than PSDT and HPhSDT, as well as excellent flotation selectivity against quartz. The contact angle results inferred that the hydrophobization intensity of these collectors toward malachite was in the order as HpSDT> PSDT> HPhSDT. ${\zeta}$-potential recommended a chemisorption of HpSDT on malachite surfaces. FTIR deduced that cupric or cuprous atoms might bond with the S and N atoms of HpSDT to form a conjugated ring. XPS further gave an additional evidence that HpSDT-Cu(I) complexes were produced on malachite surfaces via combining surface Cu atoms with HpSDT's N and S atoms, with reducing surface Cu(II) to Cu (I). The tighter orientation arrangement on malachite and stronger hydrophobicity rendered HpSDT to possess better flotation affinity toward malachite than PSDT and HPhSDT.

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.

Influence of the Optical Characteristics and Conductive Mechanism depending on the Deposition Condition of BCP (BCP의 증착 조건에 따른 광학적 특성 및 전도 기구에 미치는 영향)

  • Kim, Weon-Jong;Hong, Jin-Woong
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.22 no.11
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    • pp.980-986
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    • 2009
  • In a triple-layered structure of ITO/N,N'-diph enyl-N,N'bis(3-methylphenyl)-1,1' - biphenyl-4,4'-diamine(TPD)/tris(8-hydroxyquinoline)aluminum($Alq_3$)/(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline(BCP)/Al device, we have studied the electrical and optical characteristics of organic light-emitting diodes(OLEDs) depending on the deposition condition of BCP layer. Several different sizes of holes on boat and several different deposition rates were employed in evaporating the organic materials. And then, electrical properties of the organic light-emitting diodes were measured and the performance of the devices was analyzed. It was found that the hole-size of crucible boat and the evaporation rate affect on the surface roughness of BCP layer as well as the performance of the device. When the hole-size of crucible boat and the deposition rate of BCP are 1.2 mm and $1.0\;{\AA}/s$, respectively, average surface roughness of BCP layer is lower and the efficiency of the device is higher than the ones made with other conditions. From the analysis of current density-luminance-voltage characteristics of a triple layered device, we divided the conductive mechanism by four region according to applied voltage. So we have obtained a coefficient of ${\beta}_{ST}$ in schottky region is $3.85{\times}10^{-24}$, a coefficient of ${\beta}_{PF}$ in Poole-Frenkel region is $7.35{\times}10^{-24}$, and a potential barrier of ${\phi}_{FN}$ in Fower-Nordheim region is 0.39 eV.

Surface Analysis of Papers Treated with N-chloro-polyacrylamide Using X-ray Photoelectron Spectroscopy: Mechanism of Wet Strength Development

  • Chen Shaoping;Wu Zonghua;Tanaka Hiroo
    • Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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    • 1999.04b
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    • pp.276-281
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    • 1999
  • The surfaces of sheets added with N-chloro-polyacrylamide (N-Cl-PAM) are analyzed using X-ray photoelectron spectroscopy (XPS) to clarify the chemical bonding involved in the paper strength development induced by N-Cl-PAM. The comparison of the observed N1s chemical shift of the sheet with those of the paper strength additives and the model compound, 1-butyryl-3-propyl urea, illustrated the presence of covalent bonds of alkyl acyl urea and urethane on the fiber surfaces. Thus the formation of the covalent bonds by N-Cl-PAM themselves and by N-Cl-PAM with cellulose and hemicellulose may be an explanation for much higher effectiveness of N-Cl-PAM on the improvement of wet strength of paper than A-PAM.