• Title/Summary/Keyword: 반응속도식

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A Study on the Kinetics and Mechanism of the Hydrolysis of 5,6-Dihydro-1,4-thiazine Derivatives (5,6-Dihydro-1,4-thiazine 유도체의 가수분해 메카니즘과 반응속도론적 연구)

  • Lee, Gwang Il;Lee, Seok U;Gwak, Cheon Geun;Jang, Byeong Man;Kim, Yeong Ju;Lee, Gi Chang
    • Journal of the Korean Chemical Society
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    • v.38 no.5
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    • pp.366-371
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    • 1994
  • The kinetics of the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives was investigated by ultraviolet spectrophotometry in $H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron donating groups. Final product of the hydrolysis was 2-(N-acetylaminoethylthio)-acetoacetanilide enol from Judging from the results of the rate equation, general base effect, activation parameters and final products, the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives seemed to be initiated by the neutral $H_2O$ molecule which does not dissociate at pH below 10.0, but proceeded by the hydroxide ion at pH above 11.0, and those two reactions occurred competively at pH 10.0∼11.0 range. On the basis of these findings a plausible mechanism for the hydrolysis of 5,6-dihydro-1,4-thiazine derivative was proposed.

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Kinetic Studies on the Nucleophilic Addition of Cysteine to 3,4-Methylenedioxyphenylmethylene Malononitrile (3,4-Methylenedioxyphenylmethylene Malononitrile에 대한 Cysteine의 친핵성 첨가반응에 관한 반응속도론적 연구)

  • Tae-Rin Kim;Dong-Suk Rho;Young-Haeng Lee
    • Journal of the Korean Chemical Society
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    • v.26 no.6
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    • pp.407-413
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    • 1982
  • The rate constants of the nucleophilic addition of cysteine to 3,4-methylenedioxyphenylmethylene malononitrile were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. On the basis of rate equation, it may be concluded that the rate constants were dependent upon only the concentration of hydroxide ion above pH 9.0, however, below pH 6.0, the reaction were initiated by the addition of neutral cysteine molecule to carbon-carbon double bond and at pH 7.0~9.0, the addition of a neutral cysteine molecule and it's anion occurred competitively.

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A Study on the Kinetics and Mechanism of the Hydrolysis of N-Benzylidenebenzenesulfonamide Derivatives (BBSA 유도체의 가수분해메카니즘과 반응속도론적 연구)

  • Suck-Woo Lee;Byung-Man Jang;Gwang Il Lee;Gi Chang Lee
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.919-924
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    • 1992
  • The kinetics of the hydrolysis of N-benzylidenebenzenesulfonamide derivatives have been investigated by ultraviolet spectrophotometry in $H_2O$ at $25^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effect on the hydrolysis of N-benzylidenebenzenesulfonamide derivatives were studied and rate of hydrolysis is known to be accelerated by electron withdrowing group. Final product of the hydrolysis was benzenesulfonamide and benzaldehyde. Base on the rate equation, substituent effect, general base effect and final products, hydrolysis of N-benzylidenebenzenesulfonamide derivatives seemed to be initiated by the hydronium ion at the pH 0.2${\sim}$2.5 and proceeded by the neutral $H_2O$ molecule at pH 3.0${\sim}$8.0 but proceeded by the hydroxide ion at above pH 8.5.

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ETABr 용액내에서 p-Nitrophenyldiphenylphosphinate의 탈인산화반응에 미치는 Benzimidazole의 촉매효과

  • Kim, Jeong-Bae
    • Proceedings of the Korean Environmental Sciences Society Conference
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    • 2006.11a
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    • pp.469-472
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    • 2006
  • BI 및 ETABr의 농도변화에 따른 속도상수의 변화는 이 반응이 단순한 1차 및 2차 반응 속도식에 맞지 않는다. 이와 같은 현상은 용액 속에서 두 반응 시약인 p-NPDPIN 및 BI와 상전이촉매인 ETABr 사이에 많은 수의 작은 응집된 입자(aggregates)을 형성함을 의미한다. 수용액 속에서는 불용성인 p-NPDPIN과 수용성인 BI가 충돌하여 반응할 기회가 적은데 반하여 ETABr은 이 두 시약을 함께 수용하여 세 분자 사이에 응집현상이 일어남으로 p-NPDPIN과 BI가 반응하기에 충분한 거리 내에 있게 된다. 바꾸어 말하면, 이 두 반응물질이 1:1 adducts로 반응하기보다는 여러 ETABr과 함께 많은 수의 반응분자들이 회합(응집) 되어 있음을 뜻한다.

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Numerical Analysis of Enzyme Kinetics for Undergraduate Education in Engineering (공학분야 학부교육용 효소반응속도식의 수치해석)

  • Kim, Jae-Seok;Kim, Jae-Yoon;Lee, Jae-Heung
    • The Journal of Korean Institute for Practical Engineering Education
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    • v.2 no.1
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    • pp.35-41
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    • 2010
  • An enzyme-catalized reaction is usually characterized by a very large increase in the rate and high specificity. Kinetics of simple enzyme-catalized reactions are often referred to as Michelis-Menten kinetics. A chemical that interferes with an enzyme's activity is called inhibitor. There are two types of enzyme inhibitions (viz. reversible and irreversible). If an inhibitor attaches to the enzyme with weak bonds, such as hydrogen bonds, the inhibition is usually reversible. Many enzyme reactions are also inhibited reversibly by their corresponding products. The rate of substrate disappearance together with the rate of product formation may be written by nonlinear differential equations. In the present study, numerical analyses of simple enzyme kinetics and inhibited enzyme kinetics are reported for the purpose of undergraduate education in engineering.

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Hydrolysis Mechanism of N-(2,4-dinitrophenyl)benzhydrazonyl Bromide Derivatives (N-(2,4-dinitrophenyl)benzhydrazonyl Bromide 유도체의 가수분해 반응메카니즘)

  • Park, Chan Il;Cha, Ki Won;Lee, Ik Choon;Chang, Byung Du
    • Journal of the Korean Chemical Society
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    • v.41 no.4
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    • pp.198-204
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    • 1997
  • The rate constants for the hydrolysis of N-(2,4-dinitrophenyl)benzhydrazonyl bromide and its derivatives were determined by ultraviolet visible spectrophotometry at 20$^{\circ}C$ and a rate equation which could be applied over a wide pH range was obtained. On the basis of rate equations derived and judging from the solvent effect, substituent effect, salt effect, thermodynamic parameter, plausible mechanisms of hydrolysis have been proposed. It may be concluded that the hydrolysis through SN1 mechanism via carbonium ion intermdiate to pH 3.0, and pH 10.0, the hydrolysis proceeds through 1,3-dipolar or SN2 mechanism.

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Kinetics of Lipase Reactions in Two Phase System (이상계내에서 리파제의 반응동력학)

  • Kwon, Dae Y.;Rhee, Joon S.
    • Microbiology and Biotechnology Letters
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    • v.15 no.2
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    • pp.98-103
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    • 1987
  • Two phase reaction system was used to hydrolyze the olive oil for fat splitting. Kinetics of lipases in two phase system were investigated by determining the hydrolysis rate of triglycerides at various olive oil concentrations in isooctane using the microbial lipases from Candida rugosa and Rhizopus arrhizus. The rate equation in lipid hydrolysis for various olive oil concentrations in two phase system was deviated from the Michaelis-Menten kinetics. The results suggested that the olive oil concentration in isooctane affects the interfacial area. The dependency of the interfacial area on olive oil concentration is greater at the lower olive oil concentration than at the higher substrate concentration. We modified the rate equation by considering the interfacial area between two phases depending on the olive oil concentration in solvent phase.

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Kinetics and Mechanism of the Hydrolysis of an Arylmethylenemalononitrile (Arylmethylenemalononitrile의 가수분해반응메카니즘과 그의 반응속도론적 연구)

  • Tae-Rin Kim;Mu-Ill Lim
    • Journal of the Korean Chemical Society
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    • v.17 no.2
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    • pp.130-135
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    • 1973
  • The rate-constants of hydrolysis of 3, 4-methylenedioxyphenylmethylenemalononitrile are determined by ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range is obtained. The rate equation reveals that below pH 5.0 and above pH 9.0, the hydrolysis is initiated by the addition of water and hydroxide ion respectively. However, at pH 6.0-8.0 the competitive addition of water and hydroxide ion occurs. The catalytic contribution of hydroxide ion and water can be fully explained by the rate equation obtained.

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Kinetics and Mechanism of Nucleophilic Addition of Sodium Thiophenoxide to $\alpha$-(n-Butyl)-N-Phenylnitrone Derivatives ($\alpha$-(n-Butyl)-N-Phenylnitrone 유도체에 대한 Sodium Thiophenoxide의 친핵성 첨가반응 메카니즘과 그의 반응 속도론적 연구)

  • Lee, Gwang Il;Lee, Seok U;Gwak, Cheon Geun;Kim, Yeong Ju;No, Seung Il;Lee, Gi Chang
    • Journal of the Korean Chemical Society
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    • v.38 no.6
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    • pp.442-448
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    • 1994
  • The rate constants of the nucleophilic reaction of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by ultraviolet spectrophotometry at $25^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. Final product of the addition reaction was $\alpha$-phenylthiobutylidene-aniline. Base on the rate equation, genernal base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0 the reaction was inititated by the addition of thiophenol, and in the range of pH 3.0∼10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

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