• Title/Summary/Keyword: kinetic equation

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Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride

  • Kim, Soo Ryeon;Choi, Hojune;Park, Jong Keun;Koo, In Sun;Koh, Han Joong
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.51-56
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    • 2014
  • The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $0.93{\pm}0.14$ and $0.65{\pm}0.06$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.4 to $14.6kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -15.5 to -$32.3kcal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, $k_{ww}$ and $k_{aa}$, were calculated from the rate constants ($k_{obs}$), together with $k_{aw}$ and $k_{wa}$ calculated from the intercept and slope of the plot of 1/S vs. [water]/[alcohol]. The calculated rate constants, $k_{calc}$ ($k_{ww}$, $k_{aw}$, $k_{wa}$ and $k_{aa}$), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

Kinetic Investigation of Olefin Oxidation by Al(III)-Porphyrin Complexes (Al(lll)-Porphyrin착물에 의한 올레핀 산화반응 메카니즘 연구)

  • Na, Hun-Gil;Han, Man-So
    • Journal of the Korean Chemical Society
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    • v.50 no.1
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    • pp.46-52
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    • 2006
  • studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p-X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and (p-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin.

Distribution Behavior of Solute Element in Al-Mg-Zn Alloy Continuous Cast Billet During Homogenization Treatment (Al-Mg-Zn계 알루미늄 합금 연주 빌렛 균질화처리과정 중 용질원소 거동변화)

  • Myoung-Gyun Kim
    • Journal of Korea Foundry Society
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    • v.43 no.6
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    • pp.286-293
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    • 2023
  • In this study, we investigated the microstructural evolution of Al-Mg-Zn aluminum alloy billet during homogenization treatment using OM, SEM, EDS and DSC. There were numerous phases found, such as; AlMgZn, AlMgFe, and AlMgZnSi phases, in the grain of the cast billet. After 6 hours homogenization treatment, Zn was mostly dissolved, whereas, Mg and Si were only partly dissolved. Accordingly, only AlMgFe and AlMgSi remained. After 18 hours, all of the leftover Mg and Si were dissolved, leaving only AlMgFe, which was also found after 24 hours. The results of the alloy design program, JMatPro showed that Mg dissloved more rapidly than Zn. According to the homogenization kinetic equation, Mg and Zn are completely dissolved within 1.9 and 3.5 hours, respectively.

A Study on the Vibration Analysis of Linear Stepping Motor using FEM and ACSL (유한요소법과 ACSL을 이용한 Linear Stepping Motor의 진동해석에 관한 연구)

  • 이상호;정도영
    • Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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    • v.18 no.1
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    • pp.122-128
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    • 2004
  • In this paper, the vibration characteristics of a linear stepping motor(LSM) are analyzed using the ACSL. A magnetic equivalent circuit is based on the structure of the LSM, and then the electric equivalent circuit of the LSM is derived by solving equations for the magnetic equivalent circuit. A normal force is calculated using finite element method(FEM). And the vibration characteristics(continuous vibration) of the LSM are simulated by the ACSL(Advanced Continuous Simulation language) with the voltage equations, the thrust equation, the normal force equation and the kinetic equation.

Calculation of Two-Phase Turbulent Jet with a Two-Equation Model (2-方程式 모델 에 의한 二相亂流 제트流動 의 數値解析)

  • 양선규;최영돈
    • Transactions of the Korean Society of Mechanical Engineers
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    • v.9 no.6
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    • pp.714-724
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    • 1985
  • Two-phase(air-solid, air-liquid droplet) turbulent round jet has been analyzed numerically using two equation turbulence model. The mean motion of suspending particles in air has been treated as the secondary fluid with virtual density and eddy viscosity. In this paper, the local mean velocity of secondary fluid is not assumed to be the same as that of the primary one. Dissipation rate of turbulent kinetic energy which arises because the particles can not catch up with the turbulent fluctuations of the primary fluid has been modelled by using the concept of Kolmogorov's spectral energy transfer. Numerical computations were performed for flows with different volume fraction of the dispersed phase and the diameter of particle. Results show that the total rate of turbulent energy dissipation, turbulent intensities and spreading rate of jets are reduced by the increase of volume fraction of dispersed phase. However it does not show consistent tendency with increasing the particle diameter. This investigation also shows that presence of particles in the fluid modifies the structure of the primary fluid flow significantly. Predicted velocity profiles and turbulence properties qualitatively agree with available data.

A study on the vibration of 2-phase HB type Linear Stepping Motor (2상 HB형 선형 STEPPING 전동기의 진동해석에 관한 연구)

  • Oh, H.S.;Jung, E.N.;Sim, S.H.;Lim, Y.H.;Lee, S.K.;Shim, J.S.;Shim, N.S.;Lee, S.H.
    • Proceedings of the KIEE Conference
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    • 2001.07b
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    • pp.852-854
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    • 2001
  • In this paper, the vibration characteristics of a 2-phase Hybrid type Linear Stepping Motor(HLSM) are analyzed using the ACSL. A magnetic equivalent circuit is based on the structure of the HLSM, and then the electric equivalent circuit of the HLSM is derived by solving equations for the magnetic equivalent circuit. A normal force is calculated using FEM(Flux2D). And the vibration characteristics(Continuous vibration) of the HLSM are simulated by the ACSL with the voltage equations, the thrust equation, the normal force equation and the kinetic equation.

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Sorption Equilibria and Transport of Gaseous Chlorinated Organic Solvent in Wet Solid Waste Layer (도시고형폐기물(都市固形廢棄物) 및 토양층(土壤層)에 있어서 비(非)이온성(性) 유해유기화학물질(有害有機化學物質)의 거동(擧動)에 관한 연구(硏究) (습윤고형물폐기물층(濕潤固形物廢棄物層)에 있어서 기체상(氣體相) 유해유기염소화물질(有害有機鹽素化物質)을 주대상(主對象)으로))

  • Lee, Donghoon;Tanaka, Nobutoshi
    • Journal of Korean Society of Water and Wastewater
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    • v.7 no.2
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    • pp.9-23
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    • 1993
  • Emission of hazardous and volatile organic chemicals from solid waste landfill site was become to important issue because of environmental pollution and health risk by such chemicals. Laboratory batch and continuous experiments were conducted respectively to elucidate isothermal sorption behaviors and transport phenomena(by gas through unsaturated solid waste layer) in wet solid waste-gas system. Source separated and size reduced refuse(bulky waste) and incinerated ash were used after controlling water content, and trichloroethylene(TCE) was chosen among many such chemicals because of it's generality among those man-created pollutants. Isothermal TCE sorption equilibria wet solid waste-gas system can be described in linear equation and partition coefficient in this system can be estimated approximately by the simple equation derived from schematic structure of the system. Transport equation modified by instantaneous equilibrium sorption fraction and kinetic sorption rate(overall mass transfer capacity coefficient) simulated well the column experiment results.

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Adsorption Characteristics of Reactive Red 120 by Coal-based Granular Activated Carbon : Isotherm, Kinetic and Thermodynamic Parameters (석탄계 입상활성탄에 의한 Reactive Red 120의 흡착 특성 : 등온선, 동력학 및 열역학 파라미터)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.31 no.2
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    • pp.164-171
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    • 2020
  • Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich's equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (RL = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (RL = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich's equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△Hx = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△Hx < 80 kJ/mol).

Biosorption of uranium by Bacillus sp.FB12 isolated from the vicinity of a power plant

  • Xu, Xiaoping;He, Shengbin;Wang, Zhenshou;Zhou, Yang;Lan, Jing
    • Advances in environmental research
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    • v.2 no.3
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    • pp.245-260
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    • 2013
  • Biosorption represents a technological innovation as well as a cost effective excellent remediation technology for cleaning up radionuclides from aqueous environment. In the present study, a bacteria strain FB12 with high adsorption rate of uranium ion was isolated from the vicinity of the nuclear power plant. It was tentatively identified as Bacillus sp.FB12 according to the 16S rDNA sequencing. Efforts were made to further improve the adsorption rate and genetic stability by UV irradiation and UV-LiCl cooperative mutagenesis. The improved strain named Bacillus sp.UV32 obtains excellent genetic stability and a high adsorption rate of 95.9%. The adsorption of uranium U (VI) by Bacillus sp.UV32 from aqueous solution was examined as a function of metal ion concentration, cell concentration, adsorption time, pH, temperature, and the presence of some foreign ions. The adsorption process of U (VI) was found to follow the pseudo-second-order kinetic equation. The adsorption isotherm study indicated that it preferably followed the Langmuir adsorption isotherm. The thermodynamic parameters values calculated clearly indicated that the adsorption process was feasible, spontaneous and endothermic in nature. These properties show that Bacillus sp.UV32 has potential application in the removal of uranium (VI) from the radioactive wastewater.

Experimental and Kinetic Studies of Esterification of Glycerol Using Combustion Synthesized SO42-/CeO2-Al2O3

  • Veluturla, Sravanthi;Narula, Archna;Rao, D. Subba;Indraja., S;Kulkarni, Rajeswari. M.
    • Korean Chemical Engineering Research
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    • v.56 no.4
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    • pp.592-599
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    • 2018
  • An increase in the global production of biodiesel has resulted in the newfound significance of its byproduct, glycerol. The synthesis of acetins is an economical avenue to enhance the value of glycerol derived from biodiesel. WE developed an eco-friendly process for the synthesis of fuel additives from glycerol using a mixed oxide $SO{_4}^{2-}/CeO_2-Al_2O_3$ as catalyst. The $CeO_2-Al_2O_3$ mixed oxide was synthesized by the combustion method and then sulfated. The characterization of the catalyst was by means of XRD, BET, FTIR, and SEM. The influence of temperature, mole ratio and catalyst loading on yield and selectivity of the acetins was studied for the esterification of glycerol. The reaction rate constants ($k_1$, $k_2$ and $k_3$) were estimated using optimization method in MAT lab, and the activation energies ($E_1$, $E_2$ and $E_3$) were determined by the Arrhenius equation. Furthermore, a kinetic model was developed.