• Title/Summary/Keyword: 분해반응속도

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Alkaline Hydrolysis of Esters across the Heterogeneous Liquid-Liquid Interface (불균일계 액-액 접촉 계면을 통한 ester의 알카리 가수분해 반응)

  • Park, Sang-Wook;Moon, Jin-Bok;Ko, Myung-Sook;Kim, Gun-Woo
    • Applied Chemistry for Engineering
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    • v.3 no.1
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    • pp.119-129
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    • 1992
  • The rates of mass transfer with the alkaline hydrolysis of ethyl acetate and n-butyl acetate were measured by using a modified Lewis cell. The rates of mass transfer with chemical reaction were independent of the speed of agitation, and the reaction enhancement factors were independent of the ionic strength. The second order reaction rate constants of ethyl acetate and n-butyl acetate could be obtained from an approximate solution of a diffusion equation by film theory, and their values were $0.041m^3/kg\;mol{\cdot}s$ and $0.338m^3/kgmol{\cdot}s$, respectively.

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Measurement and Acceleration of Biodegradation in Soil. (토양매립에 의한 생분해도 측정 및 가속화)

  • 김은정;박태현;신평균
    • Microbiology and Biotechnology Letters
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    • v.26 no.5
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    • pp.465-469
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    • 1998
  • The quantitative and rapid method for measuring the biodegradation of polymer materials in soil was developed. In this study, cellophane film was used as a model biodegradable polymer and the biodegradation was assayed by measuring the amount of glucose which was produced by a hydrolysis reaction using HCl after collecting the film from soil. Cellophane film was degraded 41.2% in 4 months during winter while it was degraded 76.5% in 2 months during summer. It means that biodegradation in soil is affected by environmental conditions. The biodegradation was also measured in an incubator (30$^{\circ}C$, humidity 50-55%) to exclude the environmental variations. Cellophane film was degraded 94% in that condition in 40 days. The biodegradation showed the first order kinetics and the rate constant was 0.067 (1/day). Acceleration of the biodegradation in soil was also studied. We added cultured soil microorganisms or nutrients such as N, P, and S into the soil. While the addition of microorganisms showed the temporary increase of rate constant, the addition of nutrients not only showed the increase of rate constant from 0.096 (1/day) to 0.21 (1/day) but also maintained the effect continuously.

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Production of Chiral Styrene Oxide by Microbial Enantioselective Hydrolysis Reaction (미생물 입체선택성 가수분해 반응을 이용한 광학활성 Styrene Oxide 생산)

  • 윤성준;이은열
    • KSBB Journal
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    • v.15 no.6
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    • pp.630-634
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    • 2000
  • Chiral epoxides are useful chiral synthons in organic synthesis, and various biological methods have been investigated for their production. In this work, the enantioselective resolution of racemic styrene oxide was investigated using Aspergillus niger sp. for the production of optically pure (S)-styrene oxide. The enantioselectivity and initial hydrolysis rates of the racemic substrate were highly dependent of the pH, temperature, and the volume ratio of cosolvent. Experimental sets of pH, temperature, and the volume ratio of cosolvent were investigated using a central composite experimental design, and reaction conditions were optimized by response surface analysis. The optimal conditions of pH, temperature, and the volume ratio of cosolvent were determined to be 7.78, $28.32^{\circ}C$, and 2.4%(v/v), respectively, and optically pure (S)-styrene oxide (>99% ee) was obtained at 35% yield using this microbial enantioselective hydrolysis reaction.

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The Kinetics and Mechanism of the Hydrolysis of a 1,1-Dicyano-2-p-dimethylaminophenyl-2-chloroethylene (1,1-Dicyano-2-p-dimethylaminophenyl-2-chloroethylene의 가수분해 반응메카니즘과 그의 반응속도론적 연구)

  • Tae Rin Kim;Tae Seong Huh
    • Journal of the Korean Chemical Society
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    • v.18 no.6
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    • pp.430-436
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    • 1974
  • The rate constants of hydrolysis of 1,1-dicyano-2-p-dimethylaminophenyl-2-chloroethylene(DPC) were determined at various pH and the rate equation which can be applied over wide pH range is obtained. From the rate equation the mechanism of the hydrolysis of a DPC over wide pH range is fully explained; below pH 3 and above pH 7.5, the rate constant is proportional to the concentration of hydronium ion and hydroxide ion, respectively. However, in the range of pH 3 to 7.5, water, hydronium ion and hydroxide ion catalyze the hydrolysis of DPC.

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Catalytic Recycling of Waste Polymer II. A Study of the Mechanism on the Catalytic Glycolysis of Flexible Polyurethane Foam (촉매를 이용한 폐고분자 물질의 자원화 II. 연질 폴리우레탄 폼의 글리콜분해반응 메카니즘)

  • Park, Chong-Rae;Kim, Sung-Ick;Kim, Young-Chul;Park, Nam-Cook;Seo, Gon
    • Applied Chemistry for Engineering
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    • v.10 no.3
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    • pp.388-393
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    • 1999
  • Polyurethane foams are polymeric material with repeating groups of urethane and urea. When these are heated with ethylene glycol and K acetate catalyst at $200^{\circ}C$, the transesterification of them leads to soluble products. The mechanisms of the reaction were investigated from the molecular weight and the component distributions of the products by GPC and IR analysis. The degradation of the urethane groups was faster than that of urea groups in transesterification reaction. K acetate catalyst accelerated the rate of the transesterification because it had a high ionization tendency. Each reaction, using K or Sr acetate as a catalyst, progressed in the same reaction path but yielded different compositions in products because of the difference of the reaction rate.

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Effects of Medium on Nucleophilic Substitution Reactions (I). Methanolysis of t-Butylbromide and Benzoylchloride in Methanol-Acetonitrile Mixtures (친핵치환반응에 미치는 용매효과 (제1보) 메탄올-아세토니트릴 혼합용매에서 t-Butylbromide 및 Benzoylchloride 의 가메탄올 분해반응)

  • Hai Whang Lee;Sangmoo La;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.115-120
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    • 1980
  • A kinetic study of the methanolysis of t-butylbromide and benzoylchloride in methanol-acetonitrile mixtures is reported. First order rate constants for the methanolysis of t-butyl bromide show maximum at $X_{MeOH}$=0.75∼0.9 and 25∼$50^{\circ}C$. Apparent second order rate constants for the methanolysis of benzoylchloride also show maximum at $X_{MeOH}$= 0.6∼0.95 and 12∼$26^{\circ}C$. The maximum rate is ascribed to the solvent structure change; the addition of acetonitrile to methanol perturbs the methanol structure increasing the free methanol molecules available to stabilize the transition state for the methanolysis of t-butylbromide and benzoylchloride. It has been shown that methanol acts as nucleophilic and electrophilic catalyst upon methanolysis of t-butylbromide and as electrophilic catalyst upon methanolysis of benzoylchloride.

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A Kinetic Study of Thermal-Oxidative Decomposition of Waste Polyurethane (폐폴리우레탄의 열적 산화분해에 대한 속도론적 연구)

  • Jun, Hyun Chul;Oh, Sea Cheon;Lee, Hae Pyeong;Kim, Hee Taik
    • Applied Chemistry for Engineering
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    • v.17 no.3
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    • pp.296-302
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    • 2006
  • The kinetics of the thermal-oxidative decomposition of waste polyurethane (PU) according to oxygen concentration has been studied using a non-isothermal thermogravimetric technique at several heating rates from 10 to $50^{\circ}C/min$. A kinetic model accounting for the effects of the oxygen concentration by the differential and integral method based on Arrhenius equation was proposed to describe the thermal-oxidative decomposition of waste PU. To obtain the information on the kinetic parameters such as activation energy, reaction order, and pre-exponential factor, the thermogravimetric analysis curves and its derivatives have been analyzed using the kinetic analysis method proposed in this work. From this work, it was found that reaction orders for oxygen concentration had a negative sign, and activation energy decreased as the oxygen concentration increased. It was also found that the kinetic parameters obtained from the integral method using the single heating rate experiments varied with heating rates. Therefore, it is thought that the differential method using the multiple heating rate experiments more effectively represents the thermal-oxidative decomposition of waste polyurethane.

The Effects of Reaction Conditions and NOM on Persulfate Oxidation of RDX (Persulfate에 의한 RDX 산화시 반응조건과 NOM의 영향)

  • Wu, Dabo;Bae, Bum-Han
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.10
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    • pp.723-730
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    • 2011
  • In this experiment, persulfate, a strong oxidant for ISCO (In-Situ Chemical Oxidation) was used to degraded RDX in artificial ground water at ambient temperature. Results of RDX degradation by persulfate in a batch reactor showed that the oxidation reaction was pseudo first order with estimated Ea (activation energy) of $1.14{\times}10^2kJ/mol$ and the rate was increased with the increase of reaction temperature. The oxidation of RDX by persulfate increased slightly with the increase of initial solution pH from 4 to 8. The RDX oxidation rate increased 13 times at pH 10 compared with that at pH 4, however, alkaline hydrolysis was found to be the main reaction of RDX degradation rather than oxidation. The study also showed that the oxidation rate of RDX by persulfate was linearly dependent upon the molar ratios of persulfate to RDX from 5 : 1 up to 100 : 1, with a proportion constant of $4{\times}10^{-4}$ ($min^{-1}$/molar ratio) at $70^{\circ}C$. While NOM (Natural Organic Matter) exerted negative effects on the oxidation rate of RDX by persulfate, with a proportion constant of $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$) at $70^{\circ}C$ and persulfate/NOM molar ratio of 10/1. The decrease in RDX oxidation rate was linearly dependent upon the added NOM concentration. However, the estimated activation energy in the presence of 20 mg-NOM/L was within 3.3% error compared to that without NOM, which implies the addition of NOM does not alter intrinsic oxidation reaction.

1H NMR Kinetic Studies for Degradation of Nitramine Explosives Using PdO Nanoparticle (PdO 나노입자를 이용한 니트라민 폭발물 분해반응에 대한 1H NMR 반응속도연구)

  • Kye, Young-Sik;Kumbier, Mathew;Kim, Dongwook;Harbison, Gerard S.;Langell, Marjorie A.
    • Applied Chemistry for Engineering
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    • v.33 no.3
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    • pp.302-308
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    • 2022
  • The PdO nanoparticle with large surface area was selected to solve the environmental pollution problem at fire range caused by high energy explosives research department explosive (RDX) and high melting explosive (HMX). By simulating water pollution, RDX and HMX nitramine explosives were dissolved in water, followed by the degradation reaction at 313 K by adding PdO. In order to measure the degradation reaction rate of explosives, 1H NMR was used, which can monitor the reaction rate without losing sample during reaction, and observe the progress of the reaction through the spectrum. The results showed that the degradation of RDX and HMX by PdO nanoparticles are pseudo-first order reaction. The degradation of explosives compounds were observed via the chemical shift and peak intensity analysis of NMR peaks. The measured rate constants for these reactions of RDX and HMX were 2.10 × 10-2 and 6.35 × 10-4 h-1, respectively. This study showed that the application of PdO nanoparticles for explosives degradation is a feasible option.

Effect of Operation Conditions on Pyrolysis of Larch Sawdust in a Bubbling Fluidized Bed (기포유동층 반응기를 이용한 낙엽송 톱밥의 열분해 특성)

  • Yoo, Kyung-Seun;Eom, Min-Seop;Lee, See Hoon
    • Applied Chemistry for Engineering
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    • v.27 no.5
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    • pp.478-482
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    • 2016
  • In this study, a bubbling fluidized bed pyrolyzer (0.076 m I.D. and 0.8 m high) was employed to investigate the fast pyrolysis characteristics of larch sawdust which is abundant in Korea. The effects of operation conditions, such as bed temperature ($350-550^{\circ}C$), fluidization velocity ratio ($U_o/U_{mf} $: 2.0-6.0) and feeding rate (2.2-7.0 g/min) on product yields and their chemical components were studied. The number of chemical compounds in the bio-oil decreased with the increasing bed temperature because of secondary pyrolysis. The effects of the Uo/Umf ratio and feeding rate on bio-oil compositions were relatively lower than those of the bed temperature.