• 제목/요약/키워드: Reaction rate constant

검색결과 722건 처리시간 0.024초

Acid-Catalyzed Hydrolysis Reaction of Poly(vinyl acetate) (폴리(비닐 아세테이트)의 산촉매 가수분해 반응)

  • Park, Sang-Soo;Yoon, Hi-Sook
    • Polymer(Korea)
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    • 제29권3호
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    • pp.304-307
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    • 2005
  • The acid-catalyzed hydrolysis reaction of poly(vinyl acetate) (PVAc) in water/acetic acid solution at $35^{circ}C$ was studied at two different solvent compositions. The mole fractions of vinyl acetate (Vac) and vinyl alcohol (VA) during the course of the reaction were determined by NMR, and the equilibrium constant $K_{eq}$ of the reaction was determined using the molar ratio of VAc to VA at the chemical equilibrium. $K_{eq}$ was 0.75 (${\pm}0.01$) when the VAc mole faction at the equilibrium was 0.78 (${\pm}0.01$) and it was 0.69 (${\pm}0.01$) when the VAc mole fraction was 0.57 (${\pm}$0.02). The reaction was found to be a pseudo 1-st order reaction with the rate coefficient at $3.4{\times}10^{-6}/sec$.

A Study for Mechanism and Oxidation Reaction of Substituted Benzyl Alcohols using Cr(VI)-Heterocyclic Complex[Cr(VI)-2-methylpyrazine] (Cr(VI)-헤테로고리 착물[Cr(VI)-2-methylpyrazine]를 이용한 치환 벤질 알코올류의 산화반응과 메카니즘에 관한 연구)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • 제14권11호
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    • pp.6039-6046
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    • 2013
  • Cr(VI)-heterocyclic complex[Cr(VI)-2-methylpyrazine] was synthesized by the reaction between of heterocyclic compound(2-methylpyrazine) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-2-methylpyrazine in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene${\rho}$) was Cr(VI)-2-methylpyrazine= -0.65(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

Kinetic Study on the Oxidation Reaction of Substituted Benzyl Alcohols by Cr(VI)-Heterocyclic Complex (2,2'-Bipyridinium Dichromate) (크롬(VI)-헤테로고리 착물(2,2'-Bipyridinium Dichromate)에 의한 치환 벤질 알코올류의 산화반응에 대한 속도론적 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • 제23권2호
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    • pp.241-246
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    • 2012
  • Cr(VI)-heterocyclic complex (2,2'-bipyridinium dichromate) was synthesized by the reaction between of 2,2'-bipyridine and chromium trioxide in $H_2O$, and characterized by IR and ICP. The oxidation of benzyl alcohol using 2,2'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexene < chloroform < acetone < N,N-dimethylformamide. In the presence of DMF solvent with acidic catalyst such as $H_2SO_4$ solution, 2,2'-bipyridinium dichromate oxidized the benzyl alcohol and its derivatives (p-$p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant was -0.66 (303 K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using 2,4'-Bipyridinium Dichromate (2,4'-Bipyridinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • 제22권6호
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    • pp.718-722
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    • 2011
  • 2,4'-Bipyridinium dichromate [$(C_{10}H_8N_2H)_2Cr_2O_7$] was synthesized by the reaction of 2,4'-bipyridinie with chromium trioxide in $H_2O$. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant (${\varepsilon}$), in the order : cyclohexene < chloroform < acetone < N,N'-dimethylformamide. In the presence of hydrochloric acid, 2,4'-bipyridinium dichromate effectively oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant (${\rho}$) was -0.65 at 303 K. The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

과망간산을 이용한 지하수내 TCE 제거효과 평가

  • Yang Seung-Gwan;Go Seok-O
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 한국지하수토양환경학회 2005년도 총회 및 춘계학술발표회
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    • pp.53-56
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    • 2005
  • A Laboratory study was conducted to evaluate the kinetics of oxidation of trichloroethylene (TCE) in groundwater by potassium permanganate $(KMnO_4)$, Consumption of permanganate by TCE and aquifer materials was also evaluated to obtain an appropriate injection rate of $KMnO_4$. TCE degradation by $KMnO_4$ in the absence of aquifer material showed effective with pseudo-first order rate constant, $k_{obs}=1.8110^{-3}\;s^{-1}\;at\;KMnO_4=500mg/L$. TCE oxidation by $KMnO_4$ was found to be second order reaction and the rate constant, $k=0.65{\pm}0.08\;M^{-1}s^{-1}$, was independent of pH changes. $KMnO_4$ consumption rate by groundwater sampled from field site was not significant, indicating that groundwater containing negligible amount of dissolved organic matter does not have any influence on the $KMnO_4$ degradation. Meanwhile, aquifer materials from field site were actively reacted with permanganate, resulting in the significant consumption of $KMnO_4$. It might be attributed to the existence of metal oxides in aquifer materials, Based on the rate constants obtained from this study, appropriate injection rate of permanganate and TCE removal rate in groundwater could be estimated.

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A Study on the Comparison of Advanced Oxidation Reactions Including UV, $Fe^{2+}$, and $H_2O_2$ for the Degradation of Pentachlorophenol (UV와 $Fe^{2+}$, 그리고 $H_2O_2$를 조합한 고급산화 공정에서의 Pentachlorophenol의 분해 속도 연구)

  • Son, Hyun-Seok;Kim, Moon-Kyung;Zoh, Kyung-Duk
    • Journal of Korean Society of Environmental Engineers
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    • 제29권7호
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    • pp.846-851
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    • 2007
  • This study was performed to compare and to examine the degradation efficiencies and degradation mechanism of pentachlorophenol(PCP) by UV, $UV/H_2O_2$, $Fe^{2+}$, $Fe^{2+}/H_2O_2$, and $UV/Fe^{2+}/H_2O_2$ processes. The pseudo-first order rate constant was compared in each process. The addition of $H_2O_2$ increased the rate constant by 13 times compared to the reaction with UV alone. The reaction rate in $Fe^{2+}$ reaction with PCP increased 4 times and 7.25 times by adding 180 mM $H_2O_2$ and 16 mM $H_2O_2$, respectively. Compared to that with $Fe^{2+}/H_2O_2$, the rate constant of the reaction with UV alone reaction increased 3.1 times. These results indicates the enhancement of reaction rate is closely related to the generation of OH radical. The degree of the iron sludge production observed in $Fe^{2+}/H_2O_2$ reaction was significantly reduced by irradiating UV in this process.

Phosphate removal efficiency and the removal rate constant by particle sizes of converter slag and conditions of the wastewater (전로슬래그의 입도 크기 및 폐수의 조건 변화에 따른 인산염 제거효율과 제거 속도상수에 관한 연구)

  • Lee, Sang Ho;Hwang, Jeong Jae
    • Journal of Korean Society of Water and Wastewater
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    • 제26권6호
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    • pp.841-849
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    • 2012
  • The effluent quality of phosphorus is strengthened by the national standard to conserve water resources to lessen the eutrophication threat. The soluble phosphate in the wastewater effluent can be removed using the converter slag as solid waste produced through the steel making process. The experiments for removal efficiencies and removal constants were performed for this research with the artificial wastewater following several different conditions, particle size, phosphate concentration and initial pH. The correlation coefficients of Freundlich adsorption isothem were 0.9505 for $PS_A$, 0.9183 for $PS_B$, respectively. The removal efficiency was 87-94 % for $PS_A$ and 90-96 % for $PS_B$ respectively. The pH of the wastewater was elevated to pH 11.8 for the initial pH 8.5, phosphate removal efficiency was the highest as 84 % ~ 98 %. In case of 10 mg/L of the intial phosphate, the removal efficiency was 96 ~ 98 %. The more initial pH increases, the higher the reaction rate constant is.

Study of Hydrazine-Bromine Reaction in Sulfuric Acid Media (히드라진과 브롬의 반응의 메카니즘에 관한연구)

  • Q. Won Choi;Byoung Bin Park
    • Journal of the Korean Chemical Society
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    • 제19권6호
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    • pp.403-407
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    • 1975
  • The rate constant for the $N_2H_4-Br_2$ reaction has been measured in sulfuric acid media by direct mixing method and chronopotentiometric method. The former gave 105 mole-1 l sec-1 whereas the latter 103 mole-1 l sec-1. It has been inferred that the former represents the rate constant for $N_2H_4-Br_2$ {\rightarrow} $N_2H_2$ and the latter for $N_2H_2+Br_2$ {\rightarrow} X. When the concentrations of KBr and $H_2SO_4$ are both high, drastic reduction of rate constant has been observed.

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Preliminary Study on Chlorination Reaction of Lithium Carbonate for Carbon-Anode-Based Oxide Reduction Applications

  • Jeon, Min Ku;Kim, Sung-Wook;Choi, Eun-Young
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • 제19권2호
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    • pp.225-231
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    • 2021
  • The reaction between Li2CO3 and Cl2 was investigated to verify its occurrence during a carbon-anode-based oxide reduction (OR) process. The reaction temperature was identified as a key factor that determines the reaction rate and maximum conversion ratio. It was found that the reaction should be conducted at or above 500℃ to convert more than 90% of the Li2CO3 to LiCl. Experiments conducted at various total flow rate (Q) / initial sample weight (Wi) ratios revealed that the reaction rate was controlled by the Cl2 mass transfer under the experimental conditions adopted in this work. A linear increase in the progress of reaction with an increase in Cl2 partial pressure (pCl2) was observed in the pCl2 region of 2.03-10.1 kPa for a constant Q of 100 mL·min-1 and Wi of 1.00 g. The results of this study indicate that the reaction between Li2CO3 and Cl2 is fast at 650℃ and the reaction is feasible during the OR process.

Effect of Alcohols Toward the Transphosphatidylation Activity in Phospholipase D Catalyzed Reaction (포스포리파제 D 촉매반응에서 포스파티딜 전달반응 활성에 미치는 알코올의 영향)

  • Koh, Eun-Hie
    • Journal of the Korean Chemical Society
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    • 제54권2호
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    • pp.208-214
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    • 2010
  • In the presence of alcohol, phospholipase D (PLD) is known to perform transphosphatidylation activity, during which the overall reaction rate of PLD increased. To elucidate the reaction mechanism of transphosphatidylation further, we investigated rate constants of transphosphatidylation reaction of the purified ${\alpha}$-type PLD from cabbage in the presence of various alcohols. The second-oder rate constants of PLD transphosphatidylation showed a large increase with the primary alcohols examined as expected. In the case of butanol we observed the second-oder rate constant of $33.33{\pm}1.33M^{-1}sec^{-1}$. This second-order rate constant of transphosphatidylation was as 400 times greater as the second-order hydrolysis rate constant of $0.078M^{-1}sec^{-1}$ which was adjusted for the water concentration. A linear free energy relationship between the $pK_a$ of alcohol and transphosphatidylation rate gives a Br${\o}$nsted slope of ${\beta}_{nu}$ = 0.12 ${\pm}$ 0.03. This small ${\beta}_{nu}$ value implicates that the transition state of break down of phosphatidyl-enzyme intermediate (E-P) is likely dissociative. Finally, a reaction mechanism of cabbage PLD is suggested on the basis of our results presented here and the histidine residue known to be located in the active site of cabbage PLD.