• Title/Summary/Keyword: activation rate constant

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An Analysis of Characteristics for the Non-catalytic Esterification of Palm Fatty Acid Distillate (PFAD) (팜지방산 디스틸레이트의 무촉매 에스테르화 반응특성 연구)

  • Hong, Seok Won;Cho, Hyun Jun;Yeo, Yeong-Koo
    • Korean Chemical Engineering Research
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    • v.52 no.3
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    • pp.395-401
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    • 2014
  • In this work, the reaction characteristics for the non-catalytic esterification of palm fatty acid distillate were analyzed. The esterification reaction was assumed as the pseudo homogeneous $2^{nd}$ order reversible reaction and 'reaction effectiveness factor (${\eta}$)' was used to take accounts into evaporation and reaction of water and methanol, which take place simultaneously in the liquid phase. The nonlinear programming was used to derive appropriate kinetic parameters, the reaction rate constant and mass transfer coefficient, minimizing the error between experimental data and the numerical values. Based on these parameters, the apparent activation energy was calculated to be 43.98 kJ/mol.

Comparative Study of the Dehydrofluorination of the Structural Isomers of $C_2H_2F_4$ ($C_2H_2F_4$ 이성질체의 탈플루오르화 수소반응에 있어서의 비교연구)

  • Tschuikow-Roux E.;Maltman K. R.;Millward G. M.;Jung K. H.
    • Journal of the Korean Chemical Society
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    • v.23 no.3
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    • pp.132-135
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    • 1979
  • The thermal decomposition of a dilute mixture of 1,1,2,2,-$C_2H_2F_4$ in argon has been investigated in a single-pulse shock tube between 1146 and $1232^{\circ}K$ at total reflected shock pressures of about 3000 torr. Under these conditions the reaction proceeds exclusively by the molecular elimination of hydrogen fluoride. It has been found that the asymmetric isomer with the fully fluorinated ${\alpha}$-carbon requires the higher activation energy which may be attributed to the difference in atomic charge densities between isomers. The rate constant ratio is given by $log(k_1/k_2) = -0.069 {\pm} 0.021 +(1388{\pm}113) / 2.303RT$ in good agreement with previous independent studies.

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Natural Dyeing of Silk Fabrics with the Extract of Leaves of Rose of Sharon [Hibiscus syriacus L.] (무궁화 잎을 이용한 견직물의 천연염색에 관한 연구)

  • Cho, Im Sun;Lee, Jeong Sook
    • Fashion & Textile Research Journal
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    • v.19 no.4
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    • pp.515-522
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    • 2017
  • The natural dyeing industry has been faced with increasing demands of constant needs for environmentally and body friendly clothing products among modern consumers. Natural dyeing has attracted attention as a next-generation technology in green textiles. Dyestuffs need to be diversified for technological development activation in order to meet the increasing demands for natural dyeing. This study extracted dyeing solutions from the leaves of the Rose of Sharon (the national flower of South Korea) and investigated its dyeing properties for the development of various natural dyestuffs. This study investigates the dyeability of silk fabrics with Rose of Sharon leaves extract. Optimal conditions for dyeing of silk fabrics with the extract of Rose of Sharon were $40^{\circ}C/80min$ and $90^{\circ}C/60min$ with 100% concentration. Looking at the results, it showed the best K/S value at pH3, Sn pre-mordanting and Fe post-mordanting. Color fastness to washing, dry cleaning, rubbing and perspiration was good at grade 4-5 or 4. However, light fastness was observed in grade 2. In aspect of functional property, it showed an excellent result of 90% deodorization rate. In addition, its proven functionalities (deodorant properties) will help to produce high value added environment-friendly products. Those findings demonstrate the possibilities of the Rose of Sharon as an environment-friendly dye.

Adsorption Equilibrium, Kinetic and Thermodynamic Param (활성탄을 이용한 Acid Green 27의 흡착평형, 동역학 및 열역학 파라미터의 연구)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.55 no.4
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    • pp.514-519
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    • 2017
  • Adsorption characteristics of acid green 27 dye using activated carbon were investigated as function of adsorbent dose, pH, initial concentration, contact time and temperature. Freundlich isotherm explained adsorption of acid green 27 dye very well and Freundlich separation factors (1/n=0.293~0.387) were found that this process could be employed as effective treatment method. Kinetic studies showed that the kinetic data were well described by the pseudo second-order kinetic model. Pseudo second rate constant ($k_2$) decreased with the increase in initial acid green 27 concentration. Activation energy (10.457 kJ/mol) and enthalpy (79.946 kJ/mol) indicated that adsorption process was physisorption and endothermic. Since Gibbs free energy decreased with increasing temperature, spontaneity of adsorption reaction increased with increasing temperature in the temperature range of 298 K~318 K.

Evaluation of Methyl Methacrylate-Butyl Methacrylate Copolymer Films and Kinetics of Nitrofurazone Release (메칠메타크릴레이트-부틸메타크릴레이트 공중합체 필름의 평가 및 니트로푸라존 방출의 속도론적 연구)

  • Chun, In-Koo
    • Journal of Pharmaceutical Investigation
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    • v.17 no.3
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    • pp.111-126
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    • 1987
  • Methyl methacrylate-butyl methacrylate copolymer (MMBM)-dibutyl phthalate (DBP) films were investigated as a potential topical drug delivery system for the controlled release of nitrofurazone. The kinetic analysis of release data indicated that drug release followed a diffusion-controlled granular matrix model, where the quantity released per unit area is proportional to the square root of time. DBP of several hydrophobic plasticizers selected was found to give the highest release of nitrofurazone. However, hydrophilic plasticizers such as propylene glycol and polyethylene glycol 400 had no controlled release properties and acceptable film formation. The effects of changes in film composition, drug concentration, film thickness, pH of release medium, and temperature on the in vitro release of nitrofurazone were analyzed both theoretically and experimentally. The release rate constant (k') was found to be proportional to DBP content, pH, and the temperature of release medium, but independent of film thickness, and drug concentration in a range of 0.1-0.4% by weight. The linear relationship was found to exist between the log k' and DBP content. The release of nitrofurazone from MMBM-DBP (8:2) films was found to be an energy-linked process. Two energy terms were calculated ; the activation energy for matrix diffusion was 13.45 kcal/mole, and the heat of drug crystal solvation was 27.26-29.34 kcal/mole. Observation of scanning electron micrographs and microscopic photographs showed that the incorporation of DBP in films increased markedly the particle size of nitrofurazone dispersed in the film matrix, comparing with the fine dispersion of nitrofurazone in pure MMBM film alone.

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Phase Transfer Catalytic Effects for Thiocyanate Displacement on Benzyl Chloride (티오시안산 염에 의한 염화벤질의 치환반응에 미치는 상이동 촉매효과)

  • Seung Hyun Chang;Mu Hong Yoon;Chang Su Kim;Kwang Bo Chung;Jae Hu Shim
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.651-656
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    • 1989
  • The catalytic effects of several phase-transfer catalysts (PTC) on the liquid-liquid heterogeneous nucleophilic displacement reaction of thiocyanate on benzyl chloride have been determined. Reactions followed a pseudo-first order dependency on the benzyl chloride concentration and the observed rate constant $(k_{obsd})$ were linearly related to the concentration of catalyst and varied with variables such as reaction temperature and solvent. The sequences of catalytic activity of the displacement were $NH_4Cl$ < BTMAC < 18-crown-6 < BTEAC < PEG < TBAC < CTMAB. Enthalpies and entropies of activation associated with the displacement were 15∼20 Kcal$mo^{l-1}$, -12∼-29 eu. respectively and the reaction occurs in the interphase comprising of microemulsion.

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An Experimental and Modeling Study on the Oxidation Kinetics of Nitric Oxide over Platinum-based Catalysts (백금계 촉매상에서 산화질소(NO)의 산화반응속도에 관한 실험 및 모델링 연구)

  • Kim, Young-Deuk;Jeong, Soo-Jin;Kim, Woo-Seung
    • Transactions of the Korean Society of Automotive Engineers
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    • v.20 no.5
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    • pp.71-80
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    • 2012
  • To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

Kinetics of the Reaction of Substituted Pyridines with Benzyl Benzenesulfonate (Ⅴ) (Benzyl Benzenesulfonate 와 置換피리딘類의 反應에 關한 反應速度論的 硏究 (第5報).)

  • Woo Bung Lee;Soo Dong Yoh;Soon Yung Hong
    • Journal of the Korean Chemical Society
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    • v.21 no.1
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    • pp.38-43
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    • 1977
  • The rate constant of the reaction of 3-or 4-substituted pyridines with benzyl benzenesulfonate in acetone at $35^{\circ}C$ were determined by an electric conductivity method. According to the Hammett plot, the rates were increased the electron donating ability at the $S_N2$ reaction of benzyl benzenesulfonate with pyridine and 4-$NH_2$ pyridine was correlated with ${\sigma}^+$ than Hammett ${\sigma}$ value. This result was explained that $NH_2$ group and N atom in pyridine are largely contribute by resonance. In Br$\"{o}$nsted plot, 4-amino and electron attracting group were deviated from the increasing part at linearity. It was considered to solvent effects on substituents. A mechanistic possibility was proposed to account for the results. Some activation parameters were also calculated.

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Rates and Mechanism of the Reaction of Aquaoxomolybdenum(IV) Trimer with Thiocyanate (아쿠아옥소몰리브덴(IV) 삼합체 착물과 티오시안산이온과의 반응에 대한 속도와 메카니즘)

  • Chang-Su Kim;Joong-Ho Lee
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.527-533
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    • 1987
  • Kinetic studies on the complexing of aquamolybdenum(Ⅳ) trimer with thiocyanate have been carried out using the spectrophotometric method. The observed rate constant, $k_{obsd}$ is given by $k_{obsd}\;=\;{k_O + k_H[H^+]^2}(SCN^-) + k_r$. At 25$^{\circ}$C and ionic strength of 2.30 the values of $k_f$ and $k_r$ are $(3.78 {\pm} 0.61) {\times} 10^{-4}M^{-1}s^{-1}$ and $(6.93 {\pm} 2.39) {\times} 10^{-4}s^{-1}$, respectively. Activation parameters are ${\Delta}H^* = 50.71{\pm}6.91 kJmol^{-1}$ and ${\Delta}S^* = -121.65JK^{-1}mol^{-1}$. The mechanism is proposed and discussed.

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Effect of Arginine or Sodium Phosphate Dibasic on the Stability of Omeprazole in Aqueous Solution (아르기닌 또는 인산일수소나트륨이 수용액중에서 오메프라졸의 안정성에 미치는 영향 비교)

  • Shim, Chang-Koo;Han, Yong-Hae;Woo, Jong-Soo;Lee, Chang-Hyun
    • Journal of Pharmaceutical Investigation
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    • v.23 no.4
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    • pp.225-229
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    • 1993
  • The stability of omeprazole in the aqueous solutions containing arginine or sodium phosphate dibasic(SPD) was examined at 30, 40 and $50^{\circ}C$. Arginine or anhydrous SPD was added to omeprazoie solution ($200{\mu}g/\;ml$ in distilled water) to yield $100{\mu}g/\;ml$ concentration of each. Then, the solution was kept at 30, 40 or $50^{\circ}C$ for 90 hrs. Aliquots of the solution were withdrawn at specified time intervals and assayed by HPLC for intact omeprazole. The remaining percentage-time curves revealed that omeprazole was degraded rapidly as funtions of time and temperature following pseudo first-order kinetics. The rate constant in the SPD solution was much higher than in the arginine solution. In other words. the degradation half-lives of omeprazole at $30^{\circ}C$, for example, was 148 and 76 hr in arginine and SPD solutions respectively. The initial pH of the solution containing $100{\mu}g/\;ml$ of arginine or SPD was 9.7 or 8.7, respectively. Since omeprazole is more stable as the pH of its solution becomes more alkaline, the longer half-life of omeprazole in arginine solution could be explained by the more alkaline characteristics of arginine than SPD in the solution. The activation energy necessary for the degradation reaction was almost identical in both solutions, indicating similar degradation mechanisms of omeprazole in the solutions. In conclusion, omprazole was more stable in the presence of arginine than of SPD.

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