• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2628-2632
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• 2011

The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

• Journal of Environmental Science International
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• v.9 no.2
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• pp.165-171
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• 2000

A kinetic study for anion exchange was performed for commercially available Cl- type anion exchange resin in use to remove nitrate in water. The obtained results from the batch reactor were applied to the Langmuir and Freundlich models. The constants for Lagmuir model were qmax =29.82 and b=0.202, and for Freundlich model were K=5.509 and n=1.772. Langmuir model showed betterfit than Frendlich model for the experimental results. Ion exchange reaction rate was also calculated and the the approximate first-order reaction, rate constant k1 was 0.16 L/mg.hr. Effective diffusion coefficient was obtained in the range from $9.67$\times$10^{-8} cm^2/sec$ for initial concentration change, and from $6.09$\times$10^{-7} to 3.98$\times$10^{-6} cm^2/sec$ for reaction temperature change. Activation energy during the diffusion was calculated as 26 kcal/mol.

• Journal of the Korean Chemical Society
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• v.34 no.4
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• pp.319-324
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• 1990

Kinetic of substitution of dibenzoylmethanate (dbm) for one acetylacetonate (acac) in VO (acac)$_2$ have been studied in various solvents by spectrophotometry. Under the condition [VO (acac)$_2$] 》[Hdbm], the rate law for the substitution reaction is expressed as, rate = k$_2$K[VO(acac)$_2$] [Hdbm] / (1 ＋ K[VO(acac)$_2$]) where K = [VO (acac)$_2$dbmH] / [VO(acac)$_2$][Hdbm] and the rate constant k$_2$ corresponds to that of proton transfer from coordinated Hdbm to leaving acac- in VO(acac)$_2$dbmH.

• Journal of the Korean Ceramic Society
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• v.35 no.5
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• pp.443-450
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• 1998

Layered double hydroxides(LDHs) [{{{{ {Mg }_{1-x } }}{{{{ {Al }_{x } }}({{{{ {OH}_{2 } }})]ζ+({{{{ {CO }`_{3 } ^{2- } ){ }_{x/2 } }}$.${{{{ { yH}_{2 }O }} wioth variation of layer charge densitywere synthesized by co-precipitation methdo since their charge densities have a very important role to be det-ermined the physicochemical properties of layered materials. The XRD IR and thermal studies of them were discussed and the kinetic study for the decarbonation reaction was also carried out. From the results of XRD analysis we found that the lattice parameter and the unit cell volume were linearly decreased with the amount of Al substituents(x) in the vicinity of x=2∼10${\times}$1/3${\times}$10-1 but they had nearly constant values when the x are far from these vicinit. The activation energies for the decarbonation reaction of x=6.8, 10${\times}$1/3${\times}${{{{ { 10}^{-1 } }} were estimated to be 47.0, 37.6, 39.3 kcal/mol The specific surface areas(90-120 m2/g) of stable hy-drotalcite-type LDHs were dractically decreased with increasing of layer charge density.

• Korean Chemical Engineering Research
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• v.55 no.4
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• pp.574-577
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• 2017

In Indonesia, vetiver oil is one commodity that plays an important role in the country's foreign exchange earnings. Currently, the extraction of essential oil from vetiver still uses conventional methods. Therefore, the aim of this study was to know and verify the kinetics and mechanism of microwave hydrodistillation of vetiver based on two models. In this study, microwave hydrodistillation was used to extract essential oils from vetiver. The extraction was carried out in nine extraction cycles of 20 min to 3 hours. The rate constant, the equilibrium extraction capacity, and the initial extraction rate were calculated using the two models. Kinetics of oil extraction from vetiver by microwave hydrodistillation proved that the extraction process was based on the second-order extraction model. The second-order model was satisfactorily applied, with high coefficients of correlation ($R^2=0.9427$), showing that it well described the process.

• KOREAN JOURNAL OF CROP SCIENCE
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• v.44 no.2
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• pp.102-105
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• 1999

Mineralization of organic N is an important factor in determining the appropriate rate of organic matter application to paddy fields. A kinetic analysis was conducted for nitrogen mineralization of rice, barley, Chinese milk Ovetch (Astragalus sinicus L.; MV) and narrow leaf vetch straw in paddy soil. Nitrogen immobilization occurred rapidly and its rate increased in straw with high C/N ratio. The amount of nitrogen mineralization was rapid in the first year of rice-vetch cropping system. The rate constant (K) depended on the C/N ratio of organic matter. Mineralization of straw increased at high temperature. The amount of available N increment resulted in fast mineralization of straw, especially in rice and barley straw. Chinese milk vetch had the greatest mineralization rate at all temperatures and fertilization levels followed by narrow-leaf vetch. However, rice and barley straws with high C/N ratio immobilized the soil N at the initial incubation duration. Chinese milk vetch or narrow leaf vetch was not effectively mineralized in mixed treatments with rice or barley straw. The mineralization rate of organic matter was mostly affected by the C/N ratio of straw and temperature of incubation. Organic matter with low C/N ratio should be recommended to avoid the immobilization of soil N and the increasing mineralization rate of straw.

• Journal of the Korean Society of Industry Convergence
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• v.8 no.3
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• pp.155-160
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• 2005

Kinetic studies were carried out for aquation of carbonatobis(ethylenediamine)cobalt(III) complexes in [H+] aqueous solution by UV/VIS-spectrophotometry. The rate law that in deduced from rate data is $rate=k_H{^+}[H^+]^{1.4}$ {$[Co(en)_2(CO_3)]^+$}1.0 where $k_H{^+}$ is the rate constant considering acidic catalyst, $H^+$ ion whose value is $0.241l{\cdot}mol^{-1}{\cdot}sec^{-1}$. The values of activation parameters Ea, ${\Delta}H^{\ast}$ and ${\Delta}S^{\ast}$ were $15.33Kcal{\cdot}mol^{-1}$, $14.52Kcal{\cdot}mol^{-1}$ and -57.49 e.u. respectively. On the basis of kinetic data and the observed activation parameters, we have proposed the mechanism that proceeds with two step protonations. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation. It has been seen that our modified mechanism for Harris's proton freequilibrium one prefer to the his concerted mechanism, and more the last product substitute $H_2O$ for $OH^-$ the Harris's mechanism in the acidity range 2 < pH < 5.

• Journal of the Korean Chemical Society
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• v.6 no.1
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• pp.14-18
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• 1962

Solution to the diffusion layer for the first order reaction at a droping mercury electrode (D.M.E.) is presented. Equations are derived for polarographic currents for the reactions at the D.M.E. A factor which is applicable to the D.M.E. is derived, when we use the equations of the polarographic currents for the reactions at a plane electrode(P.E.), and the rate constants of the backward reactions are negligibly small. Polarographic currents from a combination of diffusions and reactions are obtained at the D.M.E. with special approximation. Rate constant for the reaction of ferrous ion with hydrogen-peroxide is determined at the D.M.E.,using the data of Kolthoff and Perry. The agreement of the equation with the data of Kolthoff and Perry for the kinetic current of ferric ion in the presence of hydrogen-peroxide is good. Ratios of diffusion layer at the D.M.E. to the diffusion layer at the P.E. are discussed and show that, when the rate constants of the backward reactions for the first order reactions are larger than 1/0.05 sec-1. and drop-time about 3 sec., these ratioes are about one.

• Journal of Forest and Environmental Science
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• v.32 no.3
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• pp.253-261
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• 2016

Xanthoceras sorbifolia seed coat (XSSC) is a processing residue of the bioenergy crop. This work aimed to evaluate the applicability of using the steam explosion to modify the residue for dye biosorption from aqueous solutions by using methylene blue as a model cationic dye. Equilibrium, kinetic and thermodynamic parameters for the biosorption of methylene blue on the steam-exploded XSSC (SE-XSSC) were evaluated. The kinetic data followed the pseudo-second-order model, and the rate-limiting step was the chemical adsorption. Intraparticle diffusion was one of the rate-controlling factors. The equilibrium data agreed well with the Langmuir isotherm, and the biosorption was favorable. The steam-explosion pretreatment strongly affected the biosorption in some respects. It reduced the adsorption rate constant and the initial sorption rate of the pseudo-second-order model. It enhanced the adsorption capacity of methylene blue at higher temperatures while reduced the capacity at lower ones. It changed the biosorption from an exothermic process driven by both the enthalpy and the entropy to an endothermic one driven by entropy only. It increased the surface area and decreased the pH point of zero charge of the biomass. Compared with the native XSSC, SE-XSSC is preferable to MB biosorption from warmer dye effluents.

• Journal of Microbiology and Biotechnology
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• v.21 no.7
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• pp.753-756
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• 2011

A methane-oxidizing bacterium was isolated from the enriched culture of a landfill cover soil. The closest relative of the isolate, designated M6, is Methylocystis sp. Based on a kinetic analysis, the maximum specific methane oxidation rate and saturation constant were 4.93 mmol gdry cell $weight^{-1}{\cdot}h^{-1}$ and 23${\mu}M$, respectively. This was the first time a kinetic analysis was performed using pure methanotrophic culture. The methane oxidation by M6 was investigated in the presence of aromatic (m- and pxylene and ethylbenzene) or sulfur (hydrogen sulfide, dimethyl sulfide, methanthiol) compounds. The methane oxidation was inhibited by the presence of aromatic or sulfur compounds.