• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1981-1985
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• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• Journal of the Korean Applied Science and Technology
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• v.25 no.4
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• pp.418-428
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• 2008

Transesterification of fat of Tra catfish with methanol in the presence of the KOH catalyst yields fatty acid methyl esters (FAME) and glycerol (GL). The effects of the reaction temperature and reaction time on rate constants and kinetic order were investigated. Three regions were observed. In the initial stage, the immiscibility of the Tra fat and methanol limited the reaction rate, hence this region was controlled by the mass transfer. Subsequent to this region, produced FAME like a co-solvent made the reaction mixture homogeneous, therefore the conversion rate increased rapidly so it was controlled by the kinetic parameters of the reaction until the equilibrium was approached in the final slow region. A second-order kinetic mechanism was proposed involving second regions for the forward reaction. The rate determining step for the overall KOH catalyzed-methanolysis of Tra fat was the conversion of triglycerides (TG) to diglycerides (DG). This rate constant was increased from 0.003 to $0.019min^{-1}$ when the reaction temperature was increased from 35 to $60^{\circ}C$. Its calculated activation energy was 14.379 ($kcal.mol^{-1}$).

• 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 applied mathematics & informatics
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• v.29 no.1_2
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• pp.427-442
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• 2011

Calcium is a vital second messenger for signal transduction in neurons. Calcium plays an important role in almost every part of the human body but in neuronal cytosol, it is of utmost importance. In order to understand the calcium signaling mechanism in a better way a finite element model has been developed to study the flow of calcium in two dimensions with time. This model assumes EBA (Excess Buffering Approximation), incorporating all the important parameters like time, association rate, influx, buffer concentration, diffusion constant etc. Finite element method is used to obtain calcium concentration in two dimensions and numerical integration is used to compute effect of time over 2-D Calcium profile. Comparative study of calcium signaling in two dimensions with time is done with other important physiological parameters. A MATLAB program has been developed for the entire problem and simulated on an x64 machine to compute the numerical results.

• YAKHAK HOEJI
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• v.19 no.2
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• pp.101-110
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• 1975

p-Chloronitrobenzene(substrate) and p-nitrophenetole (product) were quantitatively analyzed to know the degree of extent of reaction in the process of time. The calibration curve was prepared by the internal satndard method in gaschromatography. 2,6-Dimethyl-naphthalene was used as internal standard. The rate constant(k), the reaction velocity in various concentrations of NaOH altered, and the formation of byproducts(azo-compound and p-nitrophenol) with the amounts of MnO$_{2}$ and NaOH altered, were studied. From the results of these of MnO$_{2}$ and NaOH altered, were studied. From the results of these experiments, this reaction was second order and the rate constant was k=10.3 $\times$ 10$^{-3}$ mole$^{-21$. When p-chloronitrobenaene 1 pt. NaOH 0.56pts. MnO$_{2}$ 0.5pts. and ethanol 25 pts-were reacted about 10 hours, p-nitrophenetole was nearly quantitatively obtained without byproducts.

• Korean Journal of Food Science and Technology
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• v.29 no.6
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• pp.1094-1100
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• 1997

Effects of sodium hypochlorite (NaOCl) concentration, temperature and pH on oxidation mechanism of corn starch were investigated. The rate of oxidation was dependent on the concentration of hypochlorite, pH and temperature of oxidation. The reaction was either first or second order depending on the concentration of NaOCl. At oxidant concentration of $0.75{\sim}3.0%$ active Cl/g starch, the reaction was first-order and it was second-order at $3.75{\sim}4.5%$ active Cl/g starch. The first-order rate constants were increased with increasing oxidant concentration. The rate of oxidation of starch was highest at pH 7 and decreased with increasing acidity or alkalinity of the medium. As the reaction temperature increased, the rate of oxidation was increased.

• BMB Reports
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• v.32 no.4
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• pp.326-330
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• 1999

An aspartase purified from Hafnia alvei was inactivated by diethylpyrocarbonate (DEP) in a pseudo-first-order inactivation. The first-order plot was biphasic. The inactivation process was not saturable and the second order rate constant was $1.3\;M^{-1}s^{-1}$. The inactivated aspartase was reactivated with NH₂OH. The difference absorption spectrum of DEP-inactivated vs native enzyme preparations revealed a marked peak around 242 nm. The pH dependence of the inactivation rate suggests that an amino acid residue having a pK value of 7.2 was involved in the inactivation. L-aspartate, fumarate (substrates), and chloride ion (inhibitor) protected the enzyme against inactivation, indicating that histidine residues for the enzyme activity are located at the active site of this aspartase. Inspection of the presence and absence of $Cl^-$ ion demonstrated that the number of essential histidine residues is less than two. Thus, one or two histidines are in or near the aspartate binding site and participate in an essential step of the catalytic reaction.

• Bulletin of the Korean Chemical Society
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• v.2 no.4
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• pp.138-141
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• 1981

The rate of the bromine-exchange reaction between gallium bromide and i-butyl bromide in 1,2,4-trichlorobenzene or nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using i-butyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to i-butyl bromide. The third-order rate constant determined at $19{\circ}C$ was $3.28{\times}10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $9.25{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Bulletin of the Korean Chemical Society
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• v.2 no.3
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• pp.86-89
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• 1981

The rate of the bromine-exchange reaction between gallium bromide and n-propyl bromide in 1,2,4-trichlorobenzene and in nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using n-propyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to n-propyl bromide. The third-order rate constant determined at $19^{\circ}C$ is $2.9{\times} 10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $4.5{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$. in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined. Reaction mechanism for the bromine exchange of n-propyl bromide seemed to be similar to those observed in earlier studies with other alkyl bromides.

• Korean Journal of Ecology and Environment
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• v.39 no.4 s.118
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• pp.450-461
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• 2006

In this study, sorption kinetics of lead (Pb) and cadmium (Cd) onto coastal sediments were investigated at pH 5.5 using laboratory batch adsorbers. Four different models: one-site mass transfer model (OSMTM), pseudo-first-order kinetic model (PFOKM) ,pseudo-second-order kinetic model (PSOKM) and two compartment first-order kinetic model (TCFOKM) were used to analyze the sorption kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM, PFOKM and PSOKM in describing sorption kinetics of Pb and Cd onto sediments. Most sorption of Pb and Cd was rapidly completed within the first three hours, followed by slow sorption in the subsequent period of sorption. All models predicted that the sorbed amount at the apparent sorption ($q_{e,s}$) equilibria increased as the CEC and surface area of the sediments increased, regardless of initial spiking concentration ($C_0$) and heavy metal and the sediment type. The sorption rate constant ($k_s,\;hr^{-1}$) in OSMTM also increased as the CEC and BET surface area increased. The rate constant of pseudo-first-order sorption ($k_{p1,s},\;hr^{-1}$) in PFOKM were not correlated with sediment characteristics. The results of PSOKM analysis showed that the rate constant of pseudo-second-order sorption ($k_{p2,s},\;g\;mmol^{-1}\;hr^{-1}$) and the initial sorption rate ($v_{o,s},\;mg\;g^{-1}\;hr^{-1}$) were not correlated with sediment characteristics. The fast sorption fraction ($f_{1,s}$) in TCFOKM increased as CEC and BET surface increased regardless of initial aqueous phase concentrations. The sorption rate constant of fast fraction ($k_{1,s}=10^{0.1}-10^{1.0}\;hr^{-1}$) was much greater than that of slow sorption fraction ($k_{2,s}=10^{-2}-10^{-4}\;hr^{-1}$) respectively.