• Title/Summary/Keyword: $S_N2$ mechanism

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Effect of an temperatures of post-spray heat treatment on wear behavior of $8%Y_2O_3-ZrO_2$ coating

  • Chae, Y.H.;Kim, S.S.
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 2002.10b
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    • pp.181-182
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    • 2002
  • Most recent, Plasma ceramic spray is used on parts of tribosystem, has been investigated on the tribological performance. The application of ceramic coatings by plasma spray has become essential in tribosystems to produce better wear resistance and longer life in various conditions. The purpose of this work was to investigate the wear behavior of $8%Y_2O_3-ZrO_2$ coating due to temperatures of post-spay heat treatment. The plasma-sprayed $8%Y_2O_3--Zirconia$ coating was idiscussed to know the relationship between phase transformations and temperatures of post- spray heat treatment. Wear tests was carried out with ball on disk type on normal load of 50N, 70N and 90N under room temperature. The transformation of phase and the value of residual stress were measured by X-ray diffraction method(XRD). Tribological characteristics and wear mechanisms of coatings was observed by SEM. The tribologieal wear performance was discussed a point of view for residual stress. Consequently. post-spray heat treatment plays an important role in decreasing residual stress. Residual stress in coating system has a significant influence on the wear mechanism of coating.

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Nucleophilic Displacement at Sulfur Center (XI). Reaction of Naphthalenesulfonyl Chlorides with Anilines (황의 친핵성 치환반응 (제11보). 염화나프탈렌술포닐과 아닐린과의 반응)

  • Lee Ik Chon;Uhm Tae Seop;Lee Euk Suk
    • Journal of the Korean Chemical Society
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    • v.22 no.5
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    • pp.281-288
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    • 1978
  • Pseudo-first order rate constants $k_{obs}$ were determined for the reactions of naphthalenesulfonyl chlorides (1-NSC and 2-NSC) and anilines. The second order rate constant $k_2$ and third order catalytic $k_3$ were then determined from $k_{obs}$. For 1-NSC peri-hydrogen effect was observed. The large Brønsted ${\beta}$ and large negative slopes ${\rho}$ for the Hammett plots were obtained. These results with the unsually low values of activation parameters were consistent with the $S_AN$-elimination mechanism, but these can be equally well interpreted with the associative $S_N2$mechanism.

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Anomaly Detection Mechanism against DDoS on BcN (BcN 상에서의 DDoS에 대한 Anomaly Detection 연구)

  • Song, Byung-Hak;Lee, Seung-Yeon;Hong, Choong-Seon;Huh, Eui-Nam;Sohn, Seong-Won
    • Journal of Internet Computing and Services
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    • v.8 no.2
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    • pp.55-65
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    • 2007
  • BcN is a high-quality broadband network for multimedia services integrating telecommunication, broadcasting, and Internet seamlessly at anywhere, anytime, and using any device. BcN is Particularly vulnerable to intrusion because it merges various traditional networks, wired, wireless and data networks. Because of this, one of the most important aspects in BcN is security in terms of reliability. So, in this paper, we suggest the sharing mechanism of security data among various service networks on the BcN. This distributed, hierarchical architecture enables BcN to be robust of attacks and failures, controls data traffic going in and out the backbone core through IP edge routers integrated with IDRS. Our proposed anomaly detection scheme on IDRS for BcN service also improves detection rate compared to the previous conventional approaches.

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Application of the Extended Grunwald-Winstein Equation to the Solvolyses of Phenyl Methanesulfonyl Chloride in Aqueous Binary Mixtures

  • Koh, Han-Joong;Kang, Suk-Jin
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1897-1901
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    • 2011
  • This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

Correlation of the Rates of Solvolysis of 4-Morpholinecarbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Kim, Ran;Ali, Dildar;Lee, Jong-Pal;Yang, Ki-Yull;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.31 no.7
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    • pp.1963-1967
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    • 2010
  • The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

Kinetics and Mechanism for Reactions of Substituted Phenacyl Bromides with Quinoline (치환 브롬화페나실과 퀴놀린과의 반응에 관한 반응속도론적 연구)

  • Kim, Chang-Suk;Hong, Soon-Yung
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.265-268
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    • 1984
  • Rates of reactions of nine m-or p-substituted phenacyl bromides with quinoline in methanol were measured by an electric conductivity method. These reactions were found to proceed through an $S_N2$ path and were accelerated by both electron-donating and electron-withdrawing substituents. A plausible reaction mechanism for this observation was proposed. Some activation parameters for these reactions were also calculated.

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Studies on the Reaction of 2-Phenylethyl Arenesulfonates with Pyridine under High Pressure (2-Phenylethyl Arenesulfonates와 피리딘과의 고압반응에 관한 연구)

  • Yoh Soo Dong;Park, Jong Hwan
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.383-388
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    • 1986
  • Kinetics of the reaction of 2-phenylethylarenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40∼60${\circ}C$. The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reactions of benzyl benzenesulfonate with pyridine in acetoneitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40~60${\circ}C$ .The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reaction of benzyl benzenesulfonate with pyridine in acetone. The activation volumes and activation entropies of 2-phenylethyl m-nosylate were more negatively large than those of benzyl benzenesulfonate. From these phenomena it can be deduced that 2-phenylethyl system has more firmly $S_N2$ character in tranistion state. The Hammett reaction constants are also estimated from the second-order reaction constants. With increasing pressures the reaction parameters $({\rho})$ were decreased, but the $S_N2$ characters were increased. From these results, the reaction mechanism can be adequately described as typical $S_N2$ process under high pressure.

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Nucleophilic Substitutions at a Carbonyl Carbon Atom (ⅩⅡ). Solvolysis of Methylchloroformate and Its Thioanalogues in $CH_3CN-H_2O$ and $CH_3COCH_3-H_2$ Mixtures (카르보닐탄소원자의 친핵성 치환반응 (제 12 보).아세토니트릴-물 및 아세톤-물 혼합용 매속에서 메틸클로로훠메이트와 그 티오유도체들의 가용매분해반응에 관한 연구)

  • Sangmoo La;Kyeong Shin Koh;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.8-14
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    • 1980
  • Solvolysis rate constants for methylchloroformate, $CH_3O$(CO)Cl, methylthiono-chloroformate, $CH_3O$(CS)Cl, and methylthiolchloroformate, $CH_3S$(CO)Cl, have been determined conductometrically in acetone-water and acetonitrile-water mixtures, and activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, have been derived. Results show that in water-rich regions the order of rate increases as $$CH_3O(CO)Cl while in dipolar aprotic solvent-rich region this order reverses. The plots of log k vs. solvent parameters, Y, $\frac{D-1}{2D+1}$ and log($H_2$) show that the order of rate increase in water-rich region is the results of increase in $S_N1$ character. It is concluded that $CH_3S$(CO)Cl solvolyzes via $S_N1$ mechanism whereas $CH_3O$(CO)Cl reacts via $S_N2$ and $CH_3O$(CS)Cl via intermediate mechanism in water-rich region.

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Kinetics Studies on the Mechanism of Hydrolysis of S-Phenyl-S-vinyl-N-p-tosylsulfilimine Derivatives

  • Pyun, Sang-Yong;Kim, Tae-Rin;Lee, Chong-Ryoul;Kim, Whan-Gi
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.306-310
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    • 2003
  • Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

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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