• Title/Summary/Keyword: 압력반응

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Nucleophile Effects for the Reactions of Nucleophilic Substitution by Pressure and Temperature (친핵성치환반응에서 압력과 온도변화에 따른 친핵체 효과)

  • Kim, Se-Kyong;Choi, Sung-Yong;Ko, Young-Shin
    • Journal of the Korean Chemical Society
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    • v.48 no.5
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    • pp.461-466
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    • 2004
  • Kinetics for the nucleophiles have been studied under high vacuum and high pressures in various temperatures. Pseudo-first order rate constants, second order rate constants, thermodynamic parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\neq},\;{\Delta}{\beta}^{\neq}\;and\;{\Delta}S^{\neq}$are all negative. The Hammett r-values are negative for the nucleophile (${\rho}$x) over the pressure range studied. The results of kinetic studies for pressure and nucleophilet show that these reactions proceed in typical $S_N2$ reaction mechanism and change of mechanism.

Kinetic Studies for the Reactions of Pyridine with Benzoylchlorides under High Pressure and High Vacuum (고압 및 고진공에서의 피리딘과 벤조일클로라이드류의 반응에 관한 속도론적 연구)

  • Kim, Se-Kyong
    • Journal of the Korean Chemical Society
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    • v.48 no.3
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    • pp.254-260
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    • 2004
  • The reaction rates of para-substituted benzoyl chlorides ($p-CH_3$, p-H, $p-NO_2$) with pyridine have been measured employing the conductometry method in acetonitrile. The pseudo first-order and second-order rate constants were determined at various pressures and temperatures. The activation parameters (${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger},\;{\Delta}H{\ddagger},\;{\Delta}S{\ddagger},\;{\Delta}G{\ddagger}$) and the Hammett ${\rho}$-values are determined from the values of rate constant. The values of ${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger}\;and\;{\Delta}S{\ddagger}$ are all negative. The Hammett ${\rho}$-values are positive for the substrate (${\rho}_Y$) over the given pressure range. The results of kinetic studies, for the pressure and substituent changes, show that these reactions are proceeded by a typical $SN_2$reaction mechanism and its bond formation is favored with elevating pressure.

Kinetic Studies for the Nucleopilic Substitution Reactions under High Pressure (친핵성 치환반응에 관한 고압에서의 속도론적 연구)

  • Kim Young Cheul;Kim Se Kyong
    • Journal of the Korean Chemical Society
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    • v.37 no.6
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    • pp.577-584
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    • 1993
  • The reaction rates of para-substituted benzoyl chlorides with substituted pyridines have been measured employing the conductometry method in acetonitrile, and pseudo-first order and second order rate constants are determined at various pressures and temperatures. The activation parameters (${\Delta}V^\neq, {\Delta}{\beta}^{\neq}, {\Delta}H^{\neq}, {\Delta}S^{\neq} {\Delta}G^{\neq}$) and the Hammett ρ-values are determined from the values of rate constants. The values of △${\Delta}V^\neq, {\Delta}{\beta}^{\neq}and {\Delta}S^{\neq}$ are all negative. The Hammett ρ-values are negative for the nucleophile (ρ$_X$), and positive for the substrate (ρ$_Y$) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S$_N$2 reaction mechanism and in bond formation favored with elevating pressure.

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Analysis of a Hydrogen Generation Membrane Reactor (수소 생산용 막반응기의 해석)

  • Kim Hyung Gyu;Suh Jung Chul;Baek Young Soon
    • Journal of the Korean Institute of Gas
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    • v.8 no.3 s.24
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    • pp.16-23
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    • 2004
  • A membrane reactor concept, which combines the typical characteristics of chemical reaction with separation process, has been analyzed and simulated in this study. The advantages of the use of a membrane reactor include chemical equilibrium shift towards higher reactant conversion and purer product than the traditional reactors. A membrane reactor model which incorporates a catalytic reaction zone and a separation membrane is proposed. The water-gas shift reaction to produce hydrogen was chosen as a model reaction to be investigated. The membrane reactor is divided into smaller parts by number of n and each part (named cell), which contains both reaction and product separation function is modeled. One of the membrane outlet streams is connected to the next cell, which is repeated up to the last cell. The simulation results can be used for various purposes including decision of optimum operating condition and membrane reactor design.

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플라즈마를 이용한 GaAs 반응성 이온 식각

  • Lee, Seong-Hyeon;No, Ho-Seop;Choe, Gyeong-Hun;Park, Ju-Hong;Jo, Gwan-Sik;Lee, Je-Won
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2009.05a
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    • pp.26.2-26.2
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    • 2009
  • 이 논문은 반응성 $BCl_3$ 플라즈마로 GaAs의 건식 식각을 진행한 후 그 결과에 대하여 연구 분석 한 것이다. 이 때 사용한 식각 공정 변수는 $BCl_3$ 플라즈마에서의 가스유량, 공정 압력과 RIE 척 파워의 변화이다. 먼저 공정 압력을 75 mTorr 고정시킨 후 $BCl_3$ 유량을 변화 (2.5~10 sccm)해서 실험하였다. 또한 BCl3의 유량을 5 sccm으로 고정시킨 후 공정압력을 변화(47~180 mTorr)해서 식각 실험을 실시하였다. 마지막으로 47 mTorr와 100 mTorr 의 각각의 공정압력에서 RF 척 파워를 변화시켜 (50~200 W) 실험하였다. GaAs 플라즈마 식각이 끝난 후 표면단차 측정기 (Surface profiler)를 사용하여 표면의 단차와 거칠기를 분석하였다. 그 후 그 결과를 이용하여 식각율 (Etch rate), 식각 표면 거칠기 (RMS roughness), 식각 선택비 (Selectivity) 등의 식각 특성평가를 하였다. 또한 식각 공정 중에 샘플 척에 발생하는 자기 바이어스와 $BCl_3$ 플라즈마 가스를 광학 발광 분석기 (Optical Emission Spectroscopy)를 이용하여 플라즈마의 상태를 실시간으로 분석하였다. 이 실험 결과에 따르면 공정 압력의 증가는 샘플 척의 자기 바이어스의 값을 감소시켰다. $BCl_3$ 압력 변화에 의한 GaAs의 식각 결과를 정리하면 5 sccm의 $BCl_3$ 가스유량과 RF 척 파워를 100 W로 고정시켰을 때 식각율은 47 mTorr에서 가장 높았으며, 그 값은 $0.42{\mu}m/min$ 이었다. GaAs의 식각 속도는 공정압력이 증가할수록 감소하였으며 180 mTorr에서는 식각율이 $0.03{\mu}m/min$로 거의 식각되지 않았다. 또한 공정압력을 75 mTorr, RF 척 파워를 100 W로 고정시키고, $BCl_3$ 가스유량을 2.5 sccm에서 10 sccm까지 변화시켰을 때, 10 sccm 의 $BCl_3$ 가스유량에서 가장 높은 식각율인 $0.87{\mu}m/min$이 측정되었다. 압력에 따른 GaAs의 식각 후 표면 거칠기는 최대 2 nm 정도로 비교적 매끈하였으며, 거의 식각되지 않은 180mTorr의 조건에서는 약 1 nm로 낮아졌다. 본 실험 조건에서 GaAs의 감광제에 대한 식각 선택비는 최대 약 3:1 이내였다.

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Kinetic Analysis by High Pressure and High Vacuum Apparatus for the Nucleophilic Substitution Reaction (고압 및 고진공장치를 이용한 친핵성치환반응에 대한 속도론적 분석)

  • Kim, Se-Kyong
    • Analytical Science and Technology
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    • v.17 no.5
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    • pp.375-380
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    • 2004
  • Kinetics have been studied by high vacuum and high pressure apparatus under various temperatures and pressures for the nucleophilic substitution reaction. Rate constants, activated parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\ddag}$, ${\Delta}{\beta}^{\ddag}$ and ${\Delta}S^{\ddag}$ are all negative. The Hammett ${\rho}$-values are negative for the nucleophile (${\rho}x$) over the pressure range studied. Consequently the rate constant increases as the pressure increases, and some decrease in vacuum. So these reactions proceed in typical $S_N2$ reaction mechanism.

Experimental Analysis of Small Thruster Chamber Design (소형 추력기 반응기 설계에 대한 실험적 고찰)

  • Lee, Jeong-Sub;Kim, Su-Kyum;Yu, Myoung-Jong;Kwon, Se-Jin
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2011.04a
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    • pp.117-120
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    • 2011
  • The parameters which can affect the performance of small thruster were verified by experiments. The loss of catalyst through the port for pressure sensor was prevented by chamber wall mesh. There was no performance decrease due to chamber wall mesh, and stable supply of propellant is the key of stability of the thruster. However, sudden pressure drop in the chamber can decrease the performance instantly. Therefore, the sudden pressure drop should be eliminated as much as possible. The cross type distributor showed more stable performance than circular type, and structural strength is also stronger.

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Studies on reactive ion etching of GaN using BCl$_{3}$ (BCl$_{3}$를 이용한 GaN계 질화합물 반도체의 RIE에 관한연구)

  • 윤관기;최용석;이일형;유순재;이진구;김송강
    • Proceedings of the IEEK Conference
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    • 1998.06a
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    • pp.409-412
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    • 1998
  • BCl/sub 3/ 및 Cl/sub 2/ 반응가스를 사용하여 RIE 장치로 GaN의 건식식각을 연구하였다. RF 전력, 반응가스의 유량 및 반응가스의 혼합비 등의 변화에 따른 최적의 식각공정 조건 및 결합특성을 연구하였다. RF 전력에 따른 GaN의 식각율은 챔버압력 25mTorr, BCl/sub 3/ 유량 40 sccm의 조건에서 RF 전력이 100W일때 17nm/min을 얻었다. BCl/sub 3/의 유량에 따른 식각율은 RF 전력 100W 챔버압력 20mTorr, Cl/sub 2/ 유량 5sccm의 조건에서 BCl/sub 3/ 유량이 40 sccm일때 65nm/min을 얻었다. Cl/sub 2//BCl/sub 3/ 혼합가스 비율에 따른 식각율은 Cl/sub 2/ 유량을 5sccm으로 고정하고 BCl/sub 3/ 유량을 변화시켰을때 RF 전력 100W 및 챔버압력 20mTorr의 조건에서 혼합비가 0.25일때 50nm/min을 얻었다. RF 전력에 따른 PR의 식각율은 챔버압력 25mTorr, Cl/sub 2/ 유량 0 sccm 및 BCl/sub 3/ 유량 40 sccm의 조건에서 RF 전려이 100W일때 15nm/min을 얻었다. 또한, 챔버압력 20mTorr, Cl/sub 2/ 유량 5 sccm 및 BCl/sub 3/ 유량 20sccm의 조건에서 RF 전력이 100W 일때 82nm/min을 얻었다.

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A Study on the Reaction between Carbon Monoxide and Nitric Oxide on Platinum Catalyst (백금촉매상에서 일산화탄소와 일산화질소의 반응에 관한 연구)

  • Park, Youn-Seok;Kim, Young-Ho;Lee, Ho-In
    • Applied Chemistry for Engineering
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    • v.1 no.2
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    • pp.207-214
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    • 1990
  • The catalytic reaction between CO and NO on polycrystalline Pt surface, which is very important in the development of catalyst for automobile exhaust gas control, has been studied using thermal desorption spectrometry(TDS) and steady-state experiment under ultra-high vacuum(UHV) conditions. With the pressures of CO and NO of each $1{\times}10^{-7}Torr$, the $CO_2$ formation rate showed a maximum at 560K. At the reaction temperature of 560K and the NO pressure of $1{\times}10^{-7}Torr$, the production of $CO_2$ was first order in $CO_2$ was first order in CO pressure below $1.35{\times}10^{-7}Torr$ of CO pressure whereas at higher CO pressures the rate became minus 0.3 order in CO. But the efforts of reactant pressure on the reaction was understood in consideration of the surface concentrations of adsorbates. With the results, we proposed a new reaction mechanism for this reaction.

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The Effect of Pressure on the Solvolysis of Benzylchlorides (II). p-Chlorobenzyl Chloride in Ethanol-Water Mixtures (염화벤질류의 가용매분해반응에 대한 압력의 영향 (제 2 보). 에탄올-물 혼합용매내에서 p-클로로 염화벤질의 분해반응)

  • Oh Cheun Kwun;Jin Burm Kyong
    • Journal of the Korean Chemical Society
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    • v.30 no.2
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    • pp.188-194
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    • 1986
  • The rate constants for the solvolysis reactions of p-chlorobenzyl chloride in ethanol-water mixtures were determinded at 30${\circ}\;and\;40{\circ}$C up to 1,600bar. Rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. The plots of ln k against pressure are fitted to a second-order function in P, and values of ${\Delta}V^{\neq}\;and\;${\Delta}{\beta}^{\neq}$ are obtained. The values of ${\Delta}V^{\neq}\;and\;${\Delta}{\beta}^{\neq}$ extremum behavior at about 0.20 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation. From the relation between the plots of ln k versus the solvent parameter, q ≡ (D-1)/(2D+1), or the logarithmic molar water concentration, In $C_w$, it could be estimated that the reaction proceeds through $S_N1(2)$ mechanism.

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