• Journal of Environmental Science International
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• v.29 no.1
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• pp.69-77
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• 2020

Oxidative degradation of phenol, three monochlorophenols (2-chlorophenol, 2-CP; 3-chlorophenol, 3-CP; 4-chlorophenol, 4-CP), four dichlorophenols (2,3-dichlorophenol, 2,3-DCP; 2,4-dichlorophenol, 2,4-DCP; 2,5-dichlorophenol, 2,5-DCP; 2,6-dichlorophenol, 2,6-DCP), and two trichlorophenols (2,4,5-trichlorophenol, 2,4,5-TCP; 2,4,6-trichlorophenol, 2,4,6-TCP) was conducted with heat activated persulfate. As the number of chlorinations increased, the reaction rate also increased. The reaction rate was relatively well fitted to the zero-order kinetic model, rather than the pseudo-first order kinetic model for the reactions at 60 ℃, which can be explained by insufficient activation of the persulfate at 60 ℃, and the oxidation reaction of 2,4,6-TCP at 70 ℃ was relatively well fitted to the pseudo-first order kinetic model. The oxidation reaction rate generally increased with increase of persulfate concentration in the solution. 2,6-dichloro-2,5-cyclohexadiene-1,4-dione was found as a degradation product in a GC/MS analysis. This compound is a non-aromatic compound, and one chlorine was removed. This result is similar to the result of previous studies. The current study proved that heat activated persulfate activation could be an alternative remediation technology for phenol and chlorophenols in soil and groundwater.

• BMB Reports
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• v.33 no.3
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• pp.228-233
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• 2000

The steady-state investigation of the mechanism of Dhydroxyisovalerate dehydrogenase was performed in order to understand this type of kinetic patterns. The initial velocity was measured with various amounts of both substrates, NADPH and 2-ketoisovalerate. Double reciprocal plots gave patterns that conversed on or near the abscissa. Binding studies indicated that NADPH bound first to the enzyme. The product $NADP^+$ was found to be a competitive inhibitor with respect to NADPH at a constant concentration of 2-ketoisovalerate. However, it showed noncompetitive inhibition against 2-ketoisovalerate at a fixed amount of NADPH. Another product, D-hydroxyisovalerate, was a non-competitive inhibitor versus NADPH and 2-ketoisovalerate at constant levels of 2-ketoisovalerate and NADPH, respectively. These results were comparable with an ordered bi-bi mechanism, in which NADPH bound first to the enzyme, followed by the binding of 2- ketoisovalerate. $NADP^+$ is the last product to be released. The ordered reaction manner of D-hydroxyisovalerate dehydrogenase from 2-ketoisovalerate to D-hydroxyisovalerate allows the accurate regulation of valine metabolism and it may lead to the regulation of total biosynthesis of enniatins in the Fusarium species.

• Bulletin of the Korean Chemical Society
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• v.17 no.3
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• pp.269-273
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• 1996

Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

• Preventive Nutrition and Food Science
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• v.4 no.4
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• pp.246-250
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• 1999

This study was conducted to develop the fermentation kinetic modeling for the prediction of pH and acidity changes in kimchi at isothermal and nonisothermal fermentation temperatures(0~15$^{\circ}C$) and salt concentrations(1.5~4.0%) using the traditional two-step method and alternative one-step method. The calculations of the two-step method of pH and acidity change during fermentation followed the pattern of the first order and zero order, respectively. The reaction rate constant of pH by the first order was increased from 0.008 {TEX}$day^{-1}${/TEX} to 0.017 {TEX}$day^{-1}${/TEX} by increasing the temperature from $0^{\circ}C$ to 15$^{\circ}C$ at 2.75% of salt concentration, and was decreased from 0.013 {TEX}$day^{-1}${/TEX} to 0.010 {TEX}$day^{-1}${/TEX} by increasing the salt concentration from 1.5% to 4.0% at 5$^{\circ}C$. For the pH and acidity of Kimchi, the zero order had a higher correlation than the first order to the estimate of the kinetics parameters by the one-step method. The {TEX}$E_{a}${/TEX} ranges of pH and acidity were 61.057~66.086 and 62.417~68.772 kJ/mole with different temperatures and salt concentrations. This one-step method had smaller and more realistic estimates of error(p〈0.05). The effective temperatures, {TEX}$T_{eff}${/TEX}, with 0~15$^{\circ}C$ of square function type of 12 hr intervals were 12.85, 11.48 and 12.46$^{\circ}C$ as increasing the salt concentration, 1.50, 2.75 and 4.00%, respectively. The {TEX}$T_{eff}${/TEX} were higher values than the mean temperature(7.5$^{\circ}C$).

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.137-140
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• 2011

The aminolysis reactions of phenyl N-benzyl thiocarbamate with benzylamines in acetonitrile at $50.0^{\circ}C$ are investigated. The reactions are first order in both the amine and the substrate. Under amine excess, pseudo-first coefficient ($k_{obs}$) are obtained, plot of $k_{obs}$ vs free amine concentration are linear. The signs of ${\rho}_{XZ}$ (< 0) are consistent with concerted mechanism. Moreover, the variations of $\rho_X$ and $\rho_Z$ with respect to the sustituent in the substrate and large ${\rho}_{XZ}$ value indicate that the reactions proceed concerted mechanism. The normal kinetic isotope effects ($k_H/k_D$ = 1.3 ~ 1.5) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-centered-type transition state. The activation parameters, ${\Delta}H^\ddagger$ and ${\Delta}S^\ddagger$, are consistent with this transition state structure.

• Journal of the Korea Organic Resources Recycling Association
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• v.9 no.3
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• pp.70-76
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• 2001

Proper design and improvement of the biofiltration process depend upon quantitative understanding of the kinetic behavior in the biofilter. This study was conducted to evaluate kinetics of biofiltration of gasoline vapor. Filling material of the biofilter was compost. Gas inlet concentration ranged from about $300mg/m^3$ to $7,000mg/m^3$. Gas velocities were 6m/hr and 15m/hr, respectively. At 6m/hr gas velocity, about 60% of gasoline TPH below $3,000mg/m^3$ was removed in the lower quarter part of the biofilter. First order kinetics described well the degradation rate of gasoline TPH with high correlation. First order kinetic removal constant at the gas velocity of 6m/hr was higher than that of 15m/hr from about $300mg/m^3$ to $7,000mg/m^3$. When the inlet concentration was over $3,000mg/m^3$, first order kinetic removal constant at the gas velocity of 6m/hr was over twice that at 15m/hr. In order to obtain over 80% of removal efficiency, gasoline vapor should be injected into the biofilter at concentration below about $2,000mg/m^3$, 100cm filling height and the gas velocity of 6m/hr.

• Journal of Korean Society of Water and Wastewater
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• v.29 no.6
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• pp.609-615
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• 2015

This study was carried out for characterization of MIO synthesized in our laboratory by co-precipitation method and applied isotherm and kinetic models for adsorption properties. XRD analysis were conducted to find crystal structure of synthesized MIO. Further SEM and XPS analysis was performed before and after phosphate adsorption, and BET analysis for surface characterization. Phosphate stock solution was prepared by KH2PO4 for characterization of phosphate adsorption, and batch experiment was conducted using 50 ml conical tube. Langmuir and Freundlich models were applied based on adsorption equilibrium test of MIO by initial phosphate solution. Pseudo first order and pseudo second order models were applied for interpretation of kinetic model by temperature. Surface area and pore size of MIO were found $89.6m^2/g$ and 16 nm respectively. And, the determination coefficient ($R^2$) value of Langmuir model was 0.9779, which was comparatively higher than that of Freundlich isotherm model 0.9340.

• Journal of Environmental Science International
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• v.27 no.3
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• pp.167-177
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• 2018

The removal characteristics of As and Se ions from aqueous solution by hexadecyl trimethyl ammonium bromide (HTMAB) modified anthracite (HTMAB-AT) were investigated under various conditions of contact time, pH and temperature. When the pH is 6, the zeta potential value of anthracite (AT) is -24 mV and on the other hand, the zeta potential value of the HTMAB-AT is +44 mV. It can be seen that the overall increase of about 60 mV. Increasing the (+) potential value indicates that the surface of the adsorbent had a stronger positive charge, so adsorption for the anion metal was increased. The isotherm data was well described by Langmuir and Temkin isotherm model. The maximum adsorption capacity was found to be 7.81 and 6.89 mg/g for As and Se ions from the Langmuir isotherm model at 298 K, respectively. The kinetic data was tested using pseudo first and pseudo second order models. The results indicated that adsorption fitted well with the pseudo second order kinetic model. The mechanism of the adsorption process showed that adsorption was dependent on intra particle diffusion model according to two step diffusion. The thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, and ${\Delta}S^{\circ}$) were also determined using the equilibrium constant value obtained at different temperatures. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process.

• Journal of the Korean Chemical Society
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• v.58 no.4
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• pp.351-358
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• 2014

Anionic (sodium lauryl sulphate, NaLS) cationic (cetyl ammonium bromide, CTAB) and non-ionic (Tween-80) surfactants have been found to inhibit the rate of oxiadation L-proline and L-methionine by alkaline $KMnO_4$. A first order dependence of rate of oxidation was observed with respect to $MnO_4{^-}$. The order of reaction in substrate and alkali was found to be fractional nearby 0.65 and 0.55 in Aminoacid and $OH^-$, respectively. An aggregation/association between $MnO_4{^-}$ and surfactant has been confirmed spectrophotometrically. A mechanism, involving kinetically inactive [$MnO_4{^-}$ surfactant] aggregate and consistent with kinetic data, has been proposed. The effect of surfactants has been discussed in terms of hydrophobic and electrostatic interactions.

• Journal of the Korean Chemical Society
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• v.57 no.2
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• pp.210-215
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• 2013

Kinetics of oxidation of indole by peroxomonosulphate (PMS) in aqueous acetonitrile medium has been investigated. The reaction follows a total second order, first order each with respect to [Indole] and [PMS]. The rate of the reaction was not affected by added [$H^+$]. Variation of ionic strength (${\mu}$) had no influence on the rate. Increase of percentage of acetonitrile decreased the rate. Absen ce of any polymerization indicated a nonradical pathway. Activation and thermodynamic parameters have bee n computed. A suitable kinetic scheme based on these observations is proposed. The reactivity of PMS towards Indole was found to be higher than that with peroxodisulphate.