• Title/Summary/Keyword: Reaction Rate Constant

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Innovative Approaches to Increase the Longevity of PRBs Containing Zero-Valent Iron

  • 이태윤;박재우;최은경;허보연
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2002.09a
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    • pp.122-124
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    • 2002
  • The removal capacity of zero-valent iron for Cr(Ⅵ) was evaluated using batch kinetic tests. The rate constants for zero-valent iron dramatically increased as initial Cr(Ⅵ) concentration decreased. Generally, the reaction rates of Cr(Ⅵ) with zero-valent iron were faster than that of a biotic degradation of Cr(Ⅵ), and furthermore the reaction rates were inversely proportional to the initial Cr(Ⅵ) concentrations. After certain reaction time elapsed. no further decrease of Cr(Ⅵ) was observed, indicating a loss of iron reactivity. The loss of iron reactivity was primarily due to the passivation of iron surfaces with iron-Cr precipitates, but the reactivity of iron was recovered by adding iron-reducing bacteria. Even though the addition of bacteria itself removed Cr(Ⅵ), the combination of iron-reducing bactera and oxidized iron significantly enhanced the reaction rate for Cr(Ⅵ) removal. The results from column tests also confirmed that the innoculation of iron-reducing bacteria to the column containing completely oxidized iron partially enhanced the recovery of the iron reactivity.

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망간산화물을 이용한 1-Naphthol의 산화-공유결합 반응 속도 연구

  • Im Dong-Min;Sin Hyeon-Sang;Jeon Byeong-U;Gang Gi-Hun
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2005.04a
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    • pp.49-52
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    • 2005
  • In this study, abiotic transformation of 1-naphthol via oxidative-coupling reaction was evaluated using Mn oxide which is ubiquitous in natural soils. The transformation of 1-naphthol catalyzed by synthetic birnessite $({\delta}-MnO_2)$ followed pseudo-lst order reaction, and the rate constants was in the range of $0.053{\sim}0.13\;min^{-1}$ with birnessite loadings of $12.5{\sim}50\;mg/20\;mL$. Since the oxidation of 1-naphthol was occurred on the reactive surface of the oxide particles, the rate constants with various birnessite loadings were correlated with birnessite surface area concentration. The correlation showed a strong linearity, which confirms the supposition of the surface reaction. From the correlation, therefore, the surface area normalized rate constant, $k_{surf}$, was determined to be 0.032 $L/m^2\;min$.

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Kinetics of the Oxidation of Substituted Benzyl Alcohols with 4-(Dimethylamino)pyridinium Dichromate (4-(Dimethylamino)pyridinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도)

  • Choi, Sun do;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.16 no.1
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    • pp.153-157
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    • 2005
  • 4-(Dimethylamino)pyridinium dichromate was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium(VI)trioxide in $H_2O$, and characterized by IR, EA and ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexen < chloroform < acetone < N,N-dimethylformamide. In the presence of hydrochloric acid(HCl), 4-(dimethylamino)pyridinium dichromate oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) smoothly in N,N-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron-withdrawing groups retarded the reaction. The Hammett reaction constant($\rho$) was -0.70 at 303K. The observed experimental data have been rationalized as follows: the proton transfer occurs after the prior formation of a chromate ester in the rate-determining step.

Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Cr(VI)-4,4'-Bipyridine Complex (크롬(VI)-4,4'-Bipyridine 착물에 의한 치환 벤질 알코올류의 산화반응 속도론과 메카니즘)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.13 no.1
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    • pp.462-469
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    • 2012
  • Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.

Kinetics of the Oxidation of Substituted Benzyl Alcohols using 6-Methylquinolinium Dichromate (6-Methylquinolinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.12 no.12
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    • pp.5990-5996
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    • 2011
  • 6-Methylquinolinium dichromate[$(C_{10}H_9NH)_2Cr_2O_7$] was synthesized by the reaction of 6-methylquinoline with chromium trioxide in $H_2O$, and characterized by IR, ICP. The oxidation of benzyl alcohol using 6-methylquinolinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene < chloroform < acetone < N,N- dimethylformamide. In the presence of hydrochloric acid($H_2SO_4$ solution), 6-methylquinolinium dichromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.67(303K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

Degradation of residual pharmaceuticals in water by UV/H2O2 advanced oxidation process (UV/H2O2 고도산화기술을 이용한 수중 잔류의약물질 제거)

  • Park, Chinyoung;Seo, Sangwon;Cho, Ikhwan;Jun, Yongsung;Ha, Hyunsup;Hwang, Tae-Mun
    • Journal of Korean Society of Water and Wastewater
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    • v.33 no.6
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    • pp.469-480
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    • 2019
  • This study was conducted to evaluate the degradation and mineralization of PPCPs (Pharmaceuticals and Personal Care Products) using a CBD(Collimated Beam Device) of UV/H2O2 advanced oxidation process. The decomposition rate of each substance was regarded as the first reaction rate to the ultraviolet irradiation dose. The decomposition rate constants for PPCPs were determined by the concentration of hydrogen peroxide and ultraviolet irradiation intensity. If the decomposition rate constant is large, the PPCPs concentration decreases rapidly. According to the decomposition rate constant, chlortetracycline and sulfamethoxazole are expected to be sufficiently removed by UV irradiation only without the addition of hydrogen peroxide. In the case of carbamazepine, however, very high UV dose was required in the absence of hydrogen peroxide. Other PPCPs required an appropriate concentration of hydrogen peroxide and ultraviolet irradiation intensity. The UV dose required to remove 90% of each PPCPs using the degradation rate constant can be calculated according to the concentration of hydrogen peroxide in each sample. Using this reaction rate, the optimum UV dose and hydrogen peroxide concentration for achieving the target removal rate can be obtained by the target PPCPs and water properties. It can be a necessary data to establish design and operating conditions such as UV lamp type, quantity and hydrogen peroxide concentration depending on the residence time for the most economical operation.

The Catalytic Effects of o-Iodosobenzoate Ion on Hydrolysis of p-Nitrophenylvalate in ETAMs Solution (ETAMs 용액내에서 p-Nitrophenylvalate의 가수분해반응에 미치는 o-Iodosobenzoate Ion의 촉매효과)

  • Kim, Jeung-Bea
    • Journal of Environmental Science International
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    • v.20 no.1
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    • pp.119-126
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    • 2011
  • In this study, reaction model and reactions rate accelerated by o-iodosobenzoate ion(IB$^{\ominus}$) on hydrolysis reaction of p-nitrophenyl valate(NPV) using ethyl tri-octyl ammonium mesylate(ETAMs) for quaternary ammonium salts, the phase transfer catalysis(PTC) reagent, were investigated. The effect of IB$^{\ominus}$ on hydrolysis reaction rate constant of NPV was weak without ETAMs solutions. Otherwise, in ETAMs solutions, the hydrolysis reactions exhibit higher first order kinetics with respect to the nucleophile, IB$^{\ominus}$, and ETAMs, suggesting that reactions are occurring in small aggregates of the three species including the substrate(NPV), whereas the reaction of NPV with OH$^{\ominus}$ is not catalyzed by ETAMs. Different concentrations of NPV were tested to measure the change of rate constants to investigate the effect of NPV as substrate and the results showed that the effect was weak. This means the reaction would be the first order kinetics with respect to the nucleophile. This behavior for the drastic rate-enhancement of the hydrolysis is referred as 'Aggregation complex model' for reaction of hydrophobic organic ester with o-iodosobenzoate ion(IB$^{\ominus}$) in hydrophobic quarternary ammonium salt(ETAMs) solutions.

The Study of the Hydrogen Absorption and Desorption Reactions of Mg under Near Constant Pressure Using the Sievert's Type Automatic Apparatus (부피법 자동장치를 이용한 유사 일정 압력에서 Mg의 수소 흡수 및 방출 반응에 대한 연구)

  • HAN, JEONG-SEB;KIM, SUNJUNG
    • Journal of Hydrogen and New Energy
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    • v.30 no.1
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    • pp.8-13
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    • 2019
  • In order to apply the Sievert's type automatic apparatus to thermal analysis of hydrogen absorbing materials, the Sievert's type automatic apparatus was modified in my laboratory. In this study, an experiment was conducted to see if hydrogen absorption and desorption reactions are possible under near constant pressure (${\pm}0.05atm$) using this device. The hydrogenation and dehydrogenation of the Mg-H system was investigated. And the program was also modified for the kinetics. It was found that it is possible to measure the hydrogen absorption rate under near constant pressure of Mg by using the modified Sievert's type automatic apparatus at 573 K and 598 K. And using this system, the hydrogen desorption rate of Mg hydride under near constant pressure at 623 K was also measurable. However, since the hydrogen desorption rate of Mg hydride is fast at 648 K, the hydrogen desorption reaction did not proceed within a constant pressure range of $0.15{\pm}0.05atm$.

Delignification Kinetics of Trema orientalis (Nalita) in Kraft Pulping

  • Jahan, M. Sarwar;Rubaiyat, A.;Sabina, R.
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.39 no.5
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    • pp.7-11
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    • 2007
  • Kraft pulping of Trema orientalis (Nalita) was studied in order to find kinetic data for delignification. Pulping runs were carried out in the temperature range of $160-180\;^{\circ}C$ under constant and well-defined conditions. The delignification was found to be first order with respect to residual lignin and was chemically controlled. The rate of delignification reaction was increased 1.11-1.23 for $10\;^{\circ}C$ temperature increase in the range of $160-180\;^{\circ}C$ range. A mean value of 93% of lignin was removed at the transition between bulk and residual delignification. The influence of cooking temperature on the rate constant was expressed by an Arrhenius-type equation. The obtained activation energy of the delignification reaction was 6,164 cal/mol. The transition point between bulk and residual phase was shifted to lower lignin and carbohydrate yield with the increase of temperature.

Loss of HCN from the Pyrimidine Molecular Ion: A Computational Study

  • Yim, Min Kyoung;Jung, Sun Hwa;Kim, Myung Soo;Choe, Joong Chul
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4098-4102
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    • 2012
  • The potential energy surface (PES) for the loss of HCN from the pyrimidine molecular ion has been explored using quantum chemical calculations. Possible reaction pathways to form five $C_3H_3N^{+{\bullet}}$ isomers have been obtained with Gaussian 4 model calculations. The rate constant for the HCN loss and the product branching ratio have been calculated using the Rice-Ramsperger-Kassel-Marcus theory on the basis of the obtained PES. The resultant rate constant agrees with the previous experimental result. By a kinetic analysis, it is proposed that the formation of $CH=CHC{\equiv}NH^{+{\bullet}}$ is favored near the dissociation threshold, while the formation of $CH=CHN{\equiv}CH^{+{\bullet}}$ is favored at high energies.