• 제목/요약/키워드: $S_N1$ mechanism

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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 (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)

  • 박유철;조영제
    • 대한화학회지
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    • 제29권6호
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    • pp.629-636
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    • 1985
  • 아세톤-물 혼합용매에서 trans-$[Co(AA)_2Cl_2]^+$ 착이온의 가용매분해반응속도를 전도도법과 분광광도법을 사용하여 1~2000bar의 압력범위ㅣ에서 측정하였다. 여기서 AA는 에틸렌디아민(en), N-에틸에틸렌디아민(N-eten), N-메틸에틸렌디아민(N-meen)과 트리메틸렌디아민(tn)을 각각 의미한다. 속도상수에 대한 압력의 영향으로부터 구한 활성화 체적은 AA가 en, N-eten, N-meen 및 tn 일때 각각 -0.2∼0.9 $cm^3mole^{-1}$, -0.2∼0.6 $cm^3mole^{-1}$, -0.8∼6.0 $cm^3mole^{-1}$, 0.7∼7.0$cm^3mole^{-1}$이었다. 이들 착이온의 가용매분해반응성은 excess 자유에너지와 자유에너지 사이클로부터 얻을 결과를 비교하여 검토하였다. 가용매분해반응성은 압력이 감소할수록, 그리고 아세톤의 함량이 증가할수록 $S_N1$ 경향성이 증가하였다. 또한 가용매 분해반응의 메카니즘에 미치는 하전분리 효과도 고찰하였다.

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

  • 김광섭;심정섭
    • 대한화학회지
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    • 제10권4호
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    • pp.166-174
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    • 1966
  • cinnamoylated photosensitive polymer의 광증감 경화반응기구를 반응속도론적으로 연구했다. Cinnamic acid(C)와 증감제(S)의 first excited singlet and lowest triplet energy level diagram과 증감제의 농도증가에 따른 sensitivity의 포화 등의 사실로부터 이 반응의 주요과정은 C와 S의 광 energy흡수에 의한 $C^{*(1)}$$S^{*(1)}$로의 여기, $S^{*(1)}{\to}S^{*(3)}$ intersystem crossing, S의 excimer 형성, $S^{*(3)}{\to}C^{*(3)}$ energy transfer 그리고 $C^{*(3)}$와 C의 termination 등임을 가정하고 다음 반응속도를 구했다. $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ $I^c_{abs}$$I^s_{abs}$ ;C 및 S의 광흡수율 $K_n$;상수 적외선 흡수스펙트럼 분석의 결과, Cinnamoyl 에스테르화도와 sensitivity의 관계 및 증감제의 농도와 sensitivity의 관계에 대하여 발표된 실험 data는 윗식을 만족시키므로 가정한 반응기구에 대한 뒷받침을 얻었다.

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

  • 이상은;정광용
    • 한국토양비료학회지
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    • 제29권2호
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    • pp.107-112
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    • 1996
  • 토양의 규산 흡착기작을 밝히고자 continuous stirred-flow(연속진탕흘림) 법을 이용하여 시간 경과에 따른 규산 흡착량 변화에 대한 실험을 $25^{\circ}C$, pH 3수준(5, 6.5, 8)에서 실시하였다. 규산 흡착량은 실험기간내 최대 흡착량을 보이지 않고 계속 증가 하였다. 시간에 따른 규산의 흡착과정을 2단계로 구분 하였고, 1단계 반응과정은 아래의 지수함수식에서 고도의 유의성있는 상관관계를 보였다 $$R_{ad}=K_a*(Q_{OH}^S)^n$$ 여기서 $R_{ad}$는 규산흡착속도($Si\;{\mu}mal/min$), $Q_{OH}^S$는 알칼리 투여를 통하여 생성된 토양표면 음전하량, $K_a$와 n 은 상수이다. 1단계 반응과정의 n값은 1.1로 한자리 결합(monolantate ligand bonding)에 의한 흡착과정인 것으로 나타났다. 2단계 과정은 아래 식에서 고도의 유의성있는 상관관계를 보였다. $$R_{ad}=K_b*(pH)$$ 이때 $K_b$ 는 비례상수로, pH 증가에 따른 규산 흡착 속도의 증가 추세가 지수 함수적으로 감소하는 경향을 보였다.

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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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    • 제35권1호
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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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    • 제18권3호
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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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    • 제67권
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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

  • 박유철;조영제
    • Bulletin of the Korean Chemical Society
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    • 제9권1호
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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.

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

  • 김원종;홍진웅
    • 한국전기전자재료학회논문지
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    • 제22권11호
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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
    • 한국펄프종이공학회:학술대회논문집
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    • 한국펄프종이공학회 1999년도 Pre-symposium of the 10th ISWPC Recent Advances in Paper Science and Technology
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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.