• Title/Summary/Keyword: activation rate constant

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Growth of Interfacial Reaction Layer by the Isothermal Heat Treatment of Cast-Bonded Fe-C-(Si)/Nb/Fe-C-(Si) (Nb/Fe-C-(Si) 주조접합재에서 등온열처리시 계면반응층의 성장에 관한 연구)

  • Jung, B.H.;Kim, M.G.;Jeong, S.H.;Park, H.I.;Ahn, Y.S.;Lee, S.Y.
    • Journal of the Korean Society for Heat Treatment
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    • v.16 no.5
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    • pp.260-266
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    • 2003
  • In order to study the interfacial reaction between Nb thin sheet and Fe-C-(Si) alloy with different Chemical compositions, they were cast-bonded. The growth of carbide layer formed at the interface after isothermal heat treatment at 1173K, 1223K, 1273K and 1323K for various times was investigated. The carbide formed at the interface was NbC and the thickness of NbC layer was increased linearly in proportional to the heat treating time. Therefore, It was found that the growth of NbC layer was controlled by the interfacial reaction. The growth rate constant of NbC layer was slightly increased with increase of carbon content when the silicon content is similar in the cast irons. However, as silicon content increases with no great difference in carbon content, the growth of NbC layer was greatly retarded. The calculated activation energy for the growth of NbC layer was varied in the range of 447.4~549.3 kJ/moI with the compositions of cast irons.

Kinetic Study on the Polycondensation Reaction of Bis-hydroxyethyl Naphthalate (Bis-hydroxyethyl Naphthalate의 축중합 반응에 관한 속도론적 연구)

  • 이성진;정성일
    • Polymer(Korea)
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    • v.26 no.4
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    • pp.422-430
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    • 2002
  • The kinetics of polycondensation of bishydroxyethyl naphthalate has been studied in the range of 241 -$260^{\circ}C$ using antimony trioxide catalyst. The reaction was performed in a batch reactor and the concentration of reaction mixture was measured with HPLC. The activation energy values of forward and reverse reaction determined from molecular species model were found to be 19.7 and 31.4 kcal/mole, respectively, and the equilibrium constants were in the range of 1.4-2.0, which were larger than that of polycondensation of PET and varied to some degree with temperature. It was confirmed by applying the Flory's distribution function that the reaction rate of the hyroxyethyl group does not depend on the molecular size. By applying functional group model, we observed that there was few difference between the activation energy of the forward reaction and that of reverse reaction, therefore the equilibrium constant has almost constant value of 1.4. The rate constants obtained from functional group model was about 3-4 times larger than that from molecular species model, which showed that both model explains the reaction system well. Although the molecular species model should predict the concentration of as many as ten molecules, it fits for the experimental results well.

Kinetics on the Reaction of 1-Adamantyl Fluoroformate with Substituted Pyridines (치환 피리딘류와 1-Adamantyl Fluoroformate의 반응에 대한 속도론적 연구)

  • Park, Byoung Chun;Park, Soo Hyun;Kyong, Jin Burm;Kim, Chang Bae
    • Journal of the Korean Chemical Society
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    • v.43 no.4
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    • pp.456-460
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    • 1999
  • Rates of 1-adamantyl fluoroformate with substituted pyridines ($3-CH_3,\;4-CH_3,\;H,\;3-Cl,\;3,4-(CH_3)_2,\;3,5-(CH_3)_2$) in methanol have been measured by conductometric method at various temperatures and concentrations. The activation parameters (${\Delta}H^{\neq},\;{\Delta}S^{\neq}$) and Hammett reaction constant (${\rho}$) or Bronsted coefficient (${\beta}$) were evaluated from rate constants. The activation entropies are large and negative, and the activation enthalpies are small and positive. The Hammett reaction constant (${\rho}$) and Bronsted coefficient (${\beta}$) values were -4.15 and 0.63, respectively. From the above results, it may be concluded that this reaction proceeds to a concerted displacement mechanism in methanol.

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A Study on the Transesterification of Dimethylphthalate by 1,4-butanediol (Dimethylphthalates와 1,4-butanediol의 에스테르 교환반응에 관한 연구)

  • Jeong, Soon-Wook;Sohn, Byoung-Chung
    • Journal of the Korean Applied Science and Technology
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    • v.9 no.1
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    • pp.41-46
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    • 1992
  • The transesterification of dimethylphthalate by 1,4-butanediol was kinetically investigated In the presence of various metal acetate catalysts at 180$^{\circ}C$. The quantity of dimethylphthalate reacted in the reaction flask was measured by gas chromatography. The transesterification was assumed to obey first-order kinetics with respect to dimethylphthalate and 1,4-butanediol, and a rate equation was derived. The linear relationship was shown between apparent rate constant and reciprocal absolute temperature, the activation energy has been calculated as 7.4kcal with lead acetate. The maximum reaction rate was appeared at the range of 1.5${\sim}$1.6 of electronegativity of metal ions.

Rehydration Characteristic of Dried Root Vegetables (근조 근채류의 복원 특성)

  • Jo, Deok-Je;Lee, Seong-Ho;Im, Hyo-Jin
    • The Korean Journal of Food And Nutrition
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    • v.4 no.1
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    • pp.1-8
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    • 1991
  • This study was attempted to establish the basic data for effective utilization of the dried radish and sweet potato. The rehydration characteristic was carried out from these dried root vegetables in various conditions. The following results were obtained. The rehydration value was increased in glycine solution, whereas It decreased in lactic acid solution. Also the vacuum freezing was higher than that in hot air drying, and it was higher the slow freezing than in the quick freezing. The rehydration rate and the rehydration surface area curve were composed of three stages, and these stages were corresponded to each other. At the range of initial immersion to 2min., the largest rehydration rate was showed. The activation energy obtained from the Arrhenius plot of the rehydration rate constant(K) were 3. Bx103ca11g mol and 3.7$\times$103cal/g mol for dried radish and sweet potato, respectively.

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The Effect of Pressure on the Solvolysis of Benzylchlorides(Ⅰ). p-Methylbenzyl Chloride in Ethanol-Water Mixtures

  • Kwun, Oh-Cheun;Kyong, Jin-Burm
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.259-263
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    • 1985
  • Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and $40^{\circ}C$ under various pressures up to 1600 bar. The rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${\Delta}V^{\neq},{\Delta}{\beta}^{\neq},{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${\Delta}V^{\neq}\;and\;{\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation (electrostriction). From the relation between the reaction rate and the dielectric constant of solvent or the number of water molecule participated in the transition state, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

Biopharmaceutical Studies on the Coprecipitate of Metoclopramide-Polyvinylpyrrolidone (Metoclopramide-Polyvinylpyrrolidone 공침물(共沈物)에 관(關)한 생물약제학적(生物藥劑學的) 연구(硏究))

  • Yong, Jae-Ick;Yu, Bong-Shin
    • Journal of Pharmaceutical Investigation
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    • v.10 no.3
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    • pp.33-45
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    • 1980
  • In order to increase the solubility of metoclopramide, various ratio coprecipitates with polyvinylpyrrolidone (M.W. 40,000) were prepared. The experiments of the solubility, physicochemical characteristics were quantitatively developed. The solubility increased as the ratio of rnetoclopramide to polyvinylpyrrolidone in metoclopramide-polyvinylpyrrolindone coprecipitate increased. In powder state, the dissolution rate of metoclopramide-polyvinylpyrrolidone coprecipitate was greater than that of metoclopramide and metoclopramide-polyvinylpyrrolidone physical mixture. Dissolution characteristics of non-disintegrating disk with constant surfacearea was in accord with Noyes-Nernst equation. The intrinsic dissolution rate, G, at $37^{\circ}C$ was $3.98{\times}10^{-7}M/cm^2{\cdot}min$ for metoclopramide, $2.26{\times}10^{-6}\;M/cm^2{\cdot}min$ for 1 : 5 metoclopramide-polyvinylpyrrolidone coprecipitate, respectively. Accordingly, activation energy of metoclopramide was 15,061cal/M, 9,178cal/M for 1 : 5 metoclopramide-polyvinylpyrrolidone coprecipitate and the activation energy decreased as the coprecipitate was formed. X-ray diffraction study revealed the fact that metoclopramide was crystalline, in contrast, there was no crystallinity evident in the 1 : 5 metoclopramide-polyvinylpyrrolidone coprecipitate. There was no difference between physical mixture and coprecipitate in TLC, UV and NMR studies. From the comparision between physical mixture and coprecipitate in IR spectrum, the interaction such as association between metoclopramide and polyvinylpyrrolidone was considered. But the association was easily dissociated in methanol solution.

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A Studyon Synthesis of High Purity $\beta$-SiC Fine Particles from Ethyl Silicate(II) (Powder Properties, Reaction Type and Activation Energy) (Ethyl Silicate를 이용한 고순도 $\beta$-SiC미분말 합성에 관한 연구(II) (분말의 특성, 반응형식 및 활성화에너지))

  • 최용식;박금철
    • Journal of the Korean Ceramic Society
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    • v.26 no.2
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    • pp.195-200
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    • 1989
  • The Silica-Carbon mixture was made with addition of carbon black in the composition which monodispersed spherical fine silica was formed by the hydrolysis of ethylsilicate, mole ratio of Carbon/Alkoxide was 3.1 and $\beta$-SiC powder was synthesized by reacting this mixture at 1,350~1,50$0^{\circ}C$ in Ar atmosphere. The results of this study are as follow : (1) The purity of synthesized $\beta$-SiC powder was above 99.98% and it was in cubic modification with lattice constant of 4.3476$\AA$. (2) The rate-controlling steps varied with the reaction temperature for the syntehsis of $\beta$-SiC in this study ; nucleation and growth of $\beta$-SiC at 1,350~1,40$0^{\circ}C$, interfacial reaction at 1,45$0^{\circ}C$ and diffusion described by Jander Equation at 1,50$0^{\circ}C$. (3) When the rate-determining step was nucleation and growth, the activation energy was about 87.8kcal/mol.

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Characterization of the fracture toughness and fatigue crack propagation of reduced activation ferritic steel(RAFs) (저방사화 페라이트강(RAFs)의 파괴인성 및 피로균열진전 특성)

  • Kim, Dong-Hyun;Yoon, Han-Ki;Kim, Sa-Wong;Kohyama, A.
    • Proceedings of the KSME Conference
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    • 2004.04a
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    • pp.13-18
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    • 2004
  • The objective of this study is to investigate fracture toughness and fatigue crack propagation behavior in the Reduced Activation Ferritic Steel (RAFs) JLF-I. The fracture toughness tests were performed with various size(plane size and thickness) and various side groove of specimens. The fatigue crack propagation behavior of the JLF-I steel was investigated by the constant-amplitude loading test for the stress ratios R=O.I, 0.3 and 0.5 respectively. The effects of stress ratios and specimen size on the fatigue crack growth behaviors for JLF-I steel were discussed within the Paris law. The test results showed the standard CT specimen with the side groove of 40 % represented a valid fracture toughness. The fracture resistance curve increased with increasing plane size and decreased with increasing thickness. However, the fracture resistance curve of half size specimen was similar to that of the standard specimen. The fatigue crack propagation rate of a half size specimen was similar to that of a full size specimen at the stress ratios of 0.1, 0.3 and 0.5 respectively. The fatigue crack propagation behavior of this material were evaluated by using a half size specimen.

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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.