• Title/Summary/Keyword: first order kinetics

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Simulation and Measurement of Degradation and Movement of Insecticide Ethoprophos in Soil (토양(土壤)중 살충제(殺蟲劑) ethoprophos의 분해성(分解性) 및 이동성(移動性)의 측정(測定)과 예측(豫測)에 관한 모델 연구(硏究))

  • Moon, Young-Hee;Kim, Yun-Tae;Kim, Young-Seok;Han, Soo-Kon
    • Korean Journal of Environmental Agriculture
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    • v.12 no.3
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    • pp.209-218
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    • 1993
  • The behaviour of insectcide ethoprophos (O-ethyl S,S-propyl phosphorodithioate) in soil was investigated. In a laboratory study, the degradation of ethoprophos in soil followed first-order reaction kinetics. The half-life of the insecticide in the soil incubated with 10, 18 and $25^{\circ}C$ was 12.4, 5.5 and 2.5 days, respectively. Arrhenius activation energy was 73.8 KJ/mole. The half-life was 46.4, 17.6 and 6.9 day in the soil with 7, 14 and 19% of soil water content, respectively. The moisture dependence B value in empirical equation was 1.67. The adsorption isotherm for ethoprophos in the soil agreed with freundlich equation. The adsorption distribution coefficient (Kd) was 0.27. In a field study prepared in autumn with undisturbed soil column in a mini-lysimeter system, ethoprophos residues were largely distributed in the top $0{\sim}2cm$ soil layer and moved down to the top 6cm soil layer. Persistence of ethoprophos in field soil was correlated with variation in weather pattern during the period of experiments. The half-life of ethoprophos treated at March and October was about 17 and 5 days, respectively. The ethoprophos woil was degraded up to 90% at 37day after the both treatment. In persistence and mobility of ethoprophos in field soil, the observed data were reasonably corresponded with predicted data by some computer model of pesticide behaviour.

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Polymer-Supported Crown Ethers (II). Efficiency for Phase Transfer Catalyst (고분자 물질로 지지된 크라운 에테르류(II) 상이동 촉매 효능)

  • Jae Hu Shim;Kwang Bo Chung;Seung Hyun Chang;Dae Kyung Song;Yong Kiel Sung
    • Journal of the Korean Chemical Society
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    • v.32 no.6
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    • pp.593-602
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    • 1988
  • Polymer-supported crown ethers (Ps-CE) which can be used for phase-transfer catalyst (PTC) were synthesized for the purpose of allowing reusable function to ordinary crown ethers, and the kinetics of the liquid-solid-liquid triphase-catalyzed nucleophilic displacement reaction of iodide (aqueous phase) on 1-bromooctane (organic phase) using synthesized Ps-CE (solid) were studied. Ps-CE were obtained by grafting of hydroxymethyl crown ethers to 1~2% cross-linked chloromethylated polystyrene. All reactions followed a pseudo-first order dependency on the 1-bromooctane concentration and the observed rate constants $(k_{obsd})$ were linearly related to the molar equivalents of Ps-CE, and were subjected to the influence of cross-linking density of polymer backbone, solvent and the reaction temperature. The catalytic activity of Ps-CE was also compared with that of structurally similar soluble crown ethers, and used Ps-CE were easily recovered after the reaction by simple filtration and could be reused without loss of catalytic activity in the same anionic displacement reaction. Enthalpies and entropies of activation associated with the displacement were 10~20kcal $mol^{-1}, 20~55eu. respectively, and the free energy of activation was ~30kcal mol^{-1}$.

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Characteristics of Isotherm, Kinetic, and Thermodynamic Parameters for Reactive Blue 4 Dye Adsorption by Activated Carbon (활성탄에 의한 Reactive Blue 4 염료의 흡착에 대한 등온선, 동력학 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.26 no.2
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    • pp.122-130
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    • 2020
  • The isotherm, kinetic, and thermodynamic parameters of reactive blue 4 adsorbed by activated carbon were investigated for activated carbon dose, pH, initial concentration, contact time, and temperature data. The adsorption of the RB 4 dye by activated carbon showed a concave shape in which the percentage of adsorption increased in both directions starting from pH 7. The isothermal adsorption data were applied to Langmuir, Freundlich, and Temkin isotherms. Both Freundlich and Langmuir isothermal adsorption models fit well. From determined Freundlich separation factor (1/n = 0.125 ~ 0.232) and Langmuir separation factor (RL = 1.53 ~ 1.59), adsorption of RB 4 by activated carbon could be employed as an effective treatment method. The constant related to the adsorption heat (BT = 2.147 ~ 2.562 J mol-1) of Temkin showed that this process was physical adsorption. From kinetic experiments, the adsorption process followed the pseudo second order model with good agreement. The results of the intraparticle diffusion model showed that the inclination of the first straight line representing the surface diffusion was smaller than that of the second straight line representing the intraparticle pore diffusion. Therefore, it was confirmed that intraparticle pore diffusion is the rate-controlling step. The negative Gibbs free energy change (ΔG = -3.262 ~ -7.581 kJ mol-1) and the positive enthalpy change (ΔH = 61.08 kJ mol-1) indicated the spontaneous and endothermic nature of the adsorption process, proving this process to be spontaneous and endothermic.

Synthesis of Diketo Copper(II) Complex and Its Binding toward Calf Thymus DNA (CTDNA) (이케토 구리(II) 착물의 합성 및 송아지 Thymus DNA(CTDNA)와의 상호작용)

  • Tak, Aijaz Ahmad;Arjmand, Farukh
    • Journal of the Korean Chemical Society
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    • v.55 no.2
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    • pp.177-182
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    • 2011
  • A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.

Purification and Characterization of Chinese Cabbage Pectinesterase (배추 펙틴에스테라제의 정제 및 특성)

  • Ko, Young-Hwan;Park, Kwan-Hwa
    • Korean Journal of Food Science and Technology
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    • v.16 no.2
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    • pp.235-241
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    • 1984
  • Two fractions of pectinesterase from Chinese cabbage were isolated by ammonium sulfate fractionation, ion exchange chromatography on DEAE-cellulose and Sephadex G-150 gel filtration. The fraction F-A and F-B were purified approximately 340- and 10-fold. The similar salt effects and pH optima (pH 7.5-8.0) were obtained for the two pectinesterase fractions. The maximum activity of both two. fractions were obtained at 20-50mM of divalent rations and at 250mM of monovalent rations. The apparent Michaelis constant of the F-A was 0.01% for citrus pectin. The temperature optima for F-A and F-B were $48^{\circ}$ and $55^{\circ}C$, respectively and both fractions were stable in the region of pH 5.0-8.0 at room temperature. The thermal inactivation of the two fractions followed the first order reaction kinetics. From D and Z-values obtained the thermal resistance of the two fractions were characterized.

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Thermal Stability of the Major Color Component, Cyanidin 3-glucoside, from a Korean Pigmented Rice Variety in Aqueous Solution (한국산 유색미의 주요성분인 Cyanidin 3-glucoside의 수용액에서의 열안정성)

  • Jo, Man-Ho;Yoon, Hye-Hyun;Hahn, Tae-Ryong
    • Applied Biological Chemistry
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    • v.39 no.3
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    • pp.245-248
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    • 1996
  • Thermal stability of the major color component, cyanidin 3-glucoside, isolated from Korean pigmented rice (Oryza sativa var. Suwon 415) were investigated to explore possible application of value-added natural colors as food additives. The anthocyanin showed red and blue color with maximum absorption peaks at 511 nm and 572 nm in acidic (pH 2.0) and alkaline (pH 9.0) buffer solutions, respectively, and the thermal degradation reactions were carried out with different temperature ranges at $50{\sim}95^{\circ}C$. Degree of degradation was determined with UV/Vis spectra which indicate characteristic absorption patterns with sharp isosbestic points at 350 nm (pH 2.0), and 275, 310, and 405 nm (pH 9.0). Thus the reaction follows simple first-order kinetics. The anthocyanin was very stable against heat at acidic pH and relatively stable at alkaline pH with half-life values of 50.3 hr and 0.6 hr at $70^{\circ}C$, respectively. The activation energies and Arrhenius frequency factors of the pigment were 26.9 kcal $mol^{-1}\;and\;6.0{\times}10^{11}\;s^{-1}$, at pH 2.0, and 15.2 kcal $mol^{-1}\;and\;1.4{\times}10^{6}\;s^{-1}$, pH 9.0, and respectively.

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Effects of Calcium on TCE Degradation Reaction in Cement/Fe(II) and Hematite/Fe(II) Systems (시멘트/Fe(II) 및 hematite/Fe(II) 시스템의 TCE 분해반응 시 Ca 성분의 영향)

  • Kim, Hong-Seok;Hwang, Kyung-Yup;Ahn, Jun-Young;Yi, Jou-Young;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.16 no.1
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    • pp.82-90
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    • 2011
  • Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons have not been identified. The previous studies showed that a hematite/CaO/Fe(II) system had TCE degradation characteristics similar to those of cement/Fe(II) systems with regard to degradation kinetics and that lime (CaO) plays an important role in enhancing the reactivity for TCE dechlorination. The current study shows identified the formation of gypsum ($CaSO_4$) in the hematite/CaO/$FeSO_4$ system through the XRD analysis. The amounts of the gypsum increased with increment of the initial CaO dose. However, when CaO in the hematite/CaO/$FeSO_4$ system was replaced with gypsum, TCE degradation was not observed. Ca-removed Portland cement extracts (CPCX) in combination with $FeSO_4(CPCX/FeSO_4)$ showed no TCE degradation. On the other hands, the Portland cement extracts (PCX) in the presence of $FeSO_4(PCX/FeSO_4)$ and CPCX/CaO/$FeSO_4$ systems degraded 0.2 mM TCE within 5 days, indicating that CaO also played an important role dechlorination reactions in the systems. The pseudo-first-order rate constants (k) of the CPCX/CaO/$FeSO_4$ systems were 0.20, 0.24, and 0.72 $day^{-1}$, when the CaO dosages were 25, 50 and 75 g/L, respectively. The XRD analyses showed identified the common peaks having the d-values of 3.02, 2.27, and 1.87 in the reaction systems that showed TCE degradation. However, it was not possible to clearly identify the crystalline minerals having the three peaks from the references in JCPDS cards. This study reveals that the reactive agents in the cement/Fe(II) and the hematite/Fe(II) systems are likely to be those containing CaO and Fe(II).

Adsorption Characteristics of Reactive Red 120 by Coal-based Granular Activated Carbon : Isotherm, Kinetic and Thermodynamic Parameters (석탄계 입상활성탄에 의한 Reactive Red 120의 흡착 특성 : 등온선, 동력학 및 열역학 파라미터)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.31 no.2
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    • pp.164-171
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    • 2020
  • Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich's equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (RL = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (RL = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich's equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△Hx = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△Hx < 80 kJ/mol).

Microbial Changes of Salted and Fermented Shrimp by High Hydrostatic Pressure Treatment (초고압처리에 의한 새우젓의 미생물변화)

  • Mok, Chul-Kyoon;Song, Ki-Tae;Lee, Sang-Ki;Park, Jong-Hyun;Woo, Gun-Jo;Lim, Sang-Bin
    • Korean Journal of Food Science and Technology
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    • v.32 no.2
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    • pp.349-355
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    • 2000
  • This study was conducted to enhance the storage stability of fermented shrimp with different salt contents using a high hydrostatic pressure. The effects of the magnitude of pressure and treatment time on the microorganisms of the fermented shrimp were investigated. The highest microbial counts with respect to the salt levels were observed at 18% salt, showing $3.4{\times}10^5\;CFU/g$ for general bacteria, $6.4{\times}10^4\;CFU/g$ for halophilic bacteria, $4.2{\times}10^5\;CFU/g$ for yeast and $3.0{\times}10^4\;CFU/g$ for halophilic yeast. The degree of sterilization increased with the magnitude of pressure and treatment time, and the sterilization could be analyzed by the first order reaction kinetics. The sterilization rate constants $(k_p)$ of the halophilic bacteria was lower than that of general bacteria. The $log(k_p)$ increased linearly with pressure and the slope of the regression line of the halophilic bacteria was greater than that of general bacteria, indicating that the sterilization of the halophilic bacteria was more dependent on the pressure. High hydrostatic pressure treatment was an effective non-thermal sterilization method for the salted and fermented shrimp, and the optimum treatment condition was for 10 min at 6,500 atm.

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Determining Kinetic Parameters and Stabilization Efficiency of Heavy Metals with Various Chemical Amendment (중금속 안정화제의 반응 매개변수 결정 및 중금속 안정화 효율성 평가)

  • Oh, Se-Jin;Kim, Sung-Chul;Kim, Tae-Hee;Yeon, Kyu-Hun;Lee, Jin-Soo;Yang, Jae-E.
    • Korean Journal of Soil Science and Fertilizer
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    • v.44 no.6
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    • pp.1063-1070
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    • 2011
  • In this study, total of 5 different chemical amendments were evaluated for determining kinetic parameters and stabilization efficiency of heavy metals in aqueous phase. Standard solution of Cd and Pb ($100mg\;L^{-1}$) was mixed with various ratio of amendments (1, 3, 5, 10%) and heavy metal stabilization efficiency was monitored for 24hrs. All examined amendments showed over 90% of removal efficiency for both Cd and Pb except zerovalent iron (ZVI) for Cd (43-63%). Based on result of heavy metal stabilization efficiency, it was ordered as $CaCO_3$ > Dolomite > Zeolite > Steel slag > ZVI for both Cd and Pb in aqueous phase. For kinetic study, first order kinetic model was adapted to calculate kinetic parameters. In terms of reaction rate constants (k), zeolite showed the fastest reaction rate (k value from 0.4882 for 1% to 2.0105 for 10%) for Cd and ZVI (k value from 0.2304 for 1% to 0.5575 for 10%) for Pb. Considering reaction rate constant and half life for heavy metal stabilization, it was ordered as Zeolite > $CaCO_3$ > Dolomite > Steel slag > ZVI for Cd and $CaCO_3$ > Dolomite > Steel slag > Zeolite > ZVI for Pb. Overall result in this study can be interpreted that lime containing materials are more beneficial to remove heavy metals with high efficiency and less time consuming than absorbent materials.