• Title/Summary/Keyword: 반응 속도론

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Determination of Kinetic Parameters for Texture Changes of Sweet Potatoes during Heating (고구마 조직의 가열변화에 대한 반응속도론적 상수 결정)

  • Lee, Jung-Ju;Rhim, Jong-Whan
    • Korean Journal of Food Science and Technology
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    • v.33 no.1
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    • pp.66-71
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    • 2001
  • Kinetic parameters for the texture degradation of three varieties of sweet potato during heating were determined using two alternative methods, the biphasic model and the fractional conversion method. The texture degradation of sweet potatoes during heating could be expressed by two simultaneous first order reactions using the biphasic method, whose activation energies were ranged $71.0{\sim}75.1\;kJ/mol\;and\;48.4{\sim}59.6\;kJ/mol$ for the initial fast texture degradation reaction and the slow texture degradation reaction at a prolonged heating period, respectively. However, the whole texture degradation phenomena of sweet potatoes during heating could also be explained by a single first order reaction using the fractional conversion method. The activation energies were $67.5{\sim}75.3\;kJ/mol$, which were comparable with those of the first phase reaction for the texture degradation determined by the biphasic model. A kinetic compensation effect shown between the kinetic parameters determined by both methods indicates that both methods can be conveniently used to determine kinetic parameters for the texture degradation of sweet potatoes by heating.

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Cure Kinetcs of DGEBA/MDA/GN/HQ System by DSC Analysis (DSC 분석에 의한 DGEBA/MDA/GN/HQ계의 경화반응 속도론)

  • Lee, J.Y.;Shim, M.J.;Kim, S.W.
    • Applied Chemistry for Engineering
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    • v.5 no.5
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    • pp.904-909
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    • 1994
  • Cure kinetics of DGEBA(diglycidyl ether of bisphenol A)/MDA(4,4'-methylene dianiline)/GN(glutaronitrile) system with and without HQ(hydroquinone) as a catalyst was studied by Kissinger equation and Fractional life method. The activation energy of the system with HQ was somewhat lower and the pre-exponential factor of that was higher by about 30% than those of the system without HQ. As 1.25phr of HQ was added, reaction rates increased about 1.8 times.

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Kinetic Study on the Reaction of para-substitued Benzylbromide with Isoquinoline under High Pressure (고압하에서의 이소퀴놀린과 브롬화 벤질류의 반응에 관한 속도론적인 연구)

  • Kim, Young Cheul;Lim, Jong Wan;Choi, Sung Yong
    • Journal of the Korean Chemical Society
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    • v.42 no.2
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    • pp.150-155
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    • 1998
  • Kinetic studies on the reaction of isoquinoline with para-substituted benzylbromides were conducted under various pressures (1 ~1000 bar) in acetonitrile. From the rate constants obtained, the activation parameters such as$\DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq}$ and Ea were evaluated. Reaction rate increasing the pressure and temperature. The activation compressibility coefficient and the activation entropy showed negative values. From the substituent effect and the results, it was found that the reaction proceeds through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

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Dissolution Kinetics of Thiourea in Triglycol Solution (트리글리콜용액에서 싸이오우레아 용해 반응속도론)

  • Li, Hua;Guo, Feng;Hu, Guoqin;Zhao, Lei;Zhang, Yadong
    • Journal of the Korean Chemical Society
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    • v.54 no.1
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    • pp.88-92
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    • 2010
  • Isopropyl mercaptan is an important pharmaceutical intermediate and chemical material. And thiourea and triglycol are the main materials for the synthesis of isopropyl mercaptan. Therefore the dissolution of thiourea in triglycol solution is very important for the production of isopropyl mercaptan. The aims of this study are to examine the dissolution kinetics of thiourea in triglycol solution, and to present an alternative process for producing isopropyl mercaptan. In order to investigate the dissolution kinetics of thiourea in triglycol solution, the concentrations of solution and reaction temperature were selected as experimental parameters. It was determined that the dissolution rate of thiourea increased with the increase in solution concentration and temperature. An empirical equation was used in fitting the data. Statistical analysis indicated small errors and the results should be reliable.

Cure Konetics and Mechanism of DGEBA-MDA-Malononitrile System (Malononitrile로 개질된 DGEBA-MDA계의 경화반응 속도론 및 반응 메카니즘)

  • Im, Seong-Su;Jo, Seong-U;Yu, Hui-Yeol;Sim, Mi-Ja;Kim, Sang-Uk
    • Korean Journal of Materials Research
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    • v.3 no.3
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    • pp.215-222
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    • 1993
  • Malononitrile(MN) as a reactive additive was added to Diglycidyl ether of bisphenol A (DGEBA)/Methylene dianiline (MDA) system in order to modify a thermosetting epoxy resin. Cure ki. netics and cure mechanism of this modified system were investigated by using DSC(differential scanning calorimetry) and FT-IR(fourier transform infrared spectrometry). Cure kinetics gave an information that the DGEBA/MDA system modified with MN should cure at over $110^{\circ}C$ after curing at about $80^{\circ}C$ for the complete curing. The activation energy of the first cure was nearly constant and that of the second cure was increased as the MN content was increased. Cure mechanism for the system was investigated with the samples cured every $30^{\circ}C$, from $80^{\circ}C$ to $170^{\circ}C$, for Ihr. It was known that the cure reactions of the epoxy-diamine system were composed of PA -E, SA - E and E-OH reactions. Beside these three reactions, in the DGEBA/MDA/MN system PA-CN and CN-OH reaction was found.

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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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Kinetic Study on the Alkaline Hydrolysis of the 4-Substituted Phenyl Ethyl Benzylphosphonates (4-치환 Phenyl Ethyl Benzylphosphonate의 알칼리 가수분해 반응에 대한 속도론적 연구)

  • Shon, Kyoung Hwa;Park, Kyung Kone;Lee, Bu Young;Shin, Bu Young
    • Journal of the Korean Chemical Society
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    • v.41 no.6
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    • pp.299-303
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    • 1997
  • The rate constants($k_{OH}$) for the alkaline hydrolysis of the 4-substituted phenyl ethyl benzylphosphonates were determined in various buffer solutions by UV(Vis spectrophotometer. The activation entropies of the title reactions show negative values and this result is not consistent with a dissociative mechanism (EA) for which a positive or slightly negative value of the entropy of activation should be expected. An associative mechanism(AE) is favorable because the negligible negative charge is generated on the leaving group in the rate determining step from a good Hammett relationship(ρ=1.89). By the results of a kinetic study, we conclude that a dissociative mechanism is not proceeded in the title reactions.

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Nucleophilic Substitution at a Carbonyl Carbon Atom (V). Kinetic Studies on Halogen Exchange Reactions of N,N-Dialkylcarbamoyl Chlorides in Dry Acetone (카르보닐 탄소원자의 친핵치환 반응 (제5보). 아세톤 용매속에서의 Dialkylcarbamoyl Chloride의 할로겐 교환반응에 관한 속도론적 연구)

  • Kim Shi Choon;Lee, Ik Choon
    • Journal of the Korean Chemical Society
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    • v.19 no.1
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    • pp.11-15
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    • 1975
  • Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

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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.