• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3293-3297
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• 2012

The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-$NO_2(C_4H_2O)$-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of $1.20{\pm}0.05$ and $0.37{\pm}0.02$ for l and m, respectively. The activation enthalpies (${\Delta}H^{\neq}$) were 5.63 to $13.0kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -25.9 to $-43.4cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.65 was also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism.

• 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 Korean Society of Environmental Engineers
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• v.27 no.11
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• pp.1238-1243
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• 2005

The batch experiments of biosorption were carried out for the removal of lead ion from metal solution using Laminaria japonica and Kjellmaniella crassifolia, two species of marine algaes as biosorbent. We have investigated biosorption kinetics and equilibrium of lead by using marine algaes. We observed that biosorption of lead occurred very rapidly by marine algaes ; the biosorption reached equilibrium less than 2 hr. These experimental data could be accurately described by a pseudo-second-order rate equation, obtaining values between $0.883{\times}10^{-3}$ and $0.628{\times}10^{-3}\;g/mg/min$ for the biosorption rate constant $k_{2,ad}$. It could be described with Langmuir, Redlich-Peterson, and Koble-Corrigan(Langmuir-Freundlich) equation. The biosorption capacity by L. japonica and K. crassifolia were in the sequence of Pb>Cd>Cr>Cu and Pb>Cu>Cd>Cr, respectively. The biosorption capacity of L. japonica were increased with pH increasing.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.11
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• pp.941-946
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• 2009

Two types of synthetic zeolites, commercially used (Z-WK) and synthesized by coal fly ash (Z-C1), and raw coal fly ash(F-C1) were examined for its kinetics and adsorption capacities of cobalt. Experimental data are fitted with kinetic models, Lagergen $1^{st}$ and $2^{nd}$ order models, and four types of adsorption isotherm models, Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan. Synthesized zeolite (Z-C1) which had 1.51 of Si/Al ratio was synthesized by raw coal fly ash from a thermal power plant. Adsorption capacities with three types of adsorbents, Z-WK, Z-C1, and F-C1, were in the order of Z-C1 (94.15 mg/g) > F-C1 (92.94 mg/g) > Z-WK (88.56mg/g). The adsorption kinetics of Z-WK and Z-C1 with cobalt could be accurately described by a pseudo-second-order rate equation. The adsorption isotherms of Z-WK and Z-C1 with cobalt were well fitted by the Langmuir and Redlich-Peterson equation. Z-C1 will be used to remove cobalt in water as a more efficient absorbent.

• Journal of Life Science
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• v.15 no.1 s.68
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• pp.15-20
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• 2005

The unstructured model was tested to describe mycelial growth, exopolysaccharide formation, and substrate consumption in submerged mycelial culture of Paeeiliomyees tenuipes C240. The Logistic equation for mycelial growth, the Luedeking-Piret equation for exopolysaccharide formation, and Luedeking­Piret-like equations for glucose consumptions were successfully incorporated into the model. The value of the key kinetic constants were: maximum specific growth rate ${\mu}m,\;0.7281\;h^{-1};$ growth­associated constant for exopolysaccharide production $(\alpha),\;0.1743g(g\;cells)^{-1}$; non-growth associated constant for exopolysaccharide production $(\beta),\;0.0019g(g\;cells)^{-1}\;;$ maintenance coefficient $(m_s),\;0.0572g\;(g\;cells)^{-1}$. When compared with batch experimental data, the model successfully provided a reasonable description for each parameter during the entire growth phase. The model showed that the production of exopolysaccharide in P. tenuipes C240 was growth-associated. The model tested in the present study can be applied to the design, scale-up, and control of fermentation process for other kinds of basidiomycetes or ascomycetes.

• The Journal of Engineering Research
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• v.3 no.1
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• pp.223-233
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• 1998

The kinetic and mechanism of the hydrothermal reaction between lime and quartz used solid state reaction equations have been investigated. Hydrothermal reaction on the starting materials was carried out in an autoclave that quartz mixed with calcium hydroxide in CaO/$SiO_2$ ratio of 0.8-1.0 for 0.5-8 hour at saturated steam pressure of $180-200^{\circ}C$. The rate of reaction was given from the ratio of uncombined lime and quartz content to the total lime and quartz content. The rate of reaction was obtained the results by the Jander's equation $[1-(1-\alpha)^{1/3}]^N=Kt$. The reaction of lime is controlled mainly by the dissolution such as N=1, and the reaction of quartz is controlled mostly by the diffusion such as $N\risingdotseq2$. The rate of hydrothermal reaction in the calcium silicate hydrates system is suggested to be determined generally by the mass transfer through the product laver formed around the reactant particles. The rate equation for whole hydrothermal reaction is shown that it is converted into the rate determining step by the diffusion from the boundary reaction such as approximately $N=1-2$.

• Journal of the Korean Geotechnical Society
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• v.30 no.9
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• pp.67-75
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• 2014

Methane gas hydrate which is considered energy source for the next generation has an urgent need to develop reliable numerical simulator for coupled THM phenomena in the porous media, to minimize problems arising during the production and optimize production procedures. International collaborations to improve previous numerical codes are in progress, but they still have mismatch in the predicted value and unstable convergence. In this paper, FEM code for fully coupled THM phenomena is developed to analyze methane hydrate dissociation in the porous media. Coupled partial differential equations are derived from four mass balance equations (methane hydrate, soil, water, and hydrate gas), energy balance equation, and force equilibrium equation. Five main variables (displacement, gas saturation, fluid pressure, temperature, and hydrate saturation) are chosen to give higher numerical convergence through trial combinations of variables, and they can analyze the whole region of a phase change in hydrate bearing porous media. The kinetic model is used to predict dissociation of methane hydrate. Developed THM FEM code is applied to the comparative study on a Masuda's laboratory experiment for the hydrate production, and verified for the stability and convergence.

• Environmental Engineering Research
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• v.25 no.4
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• pp.479-487
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• 2020

Current assumptions are used in the formulation of pseudo-first (PFO) and second-order (PSO) models to describe the kinetic data of filtration based on ideal operating conditions. This paper presents a new model developed with pseudo n^th order and based on real assumption. A comparison was performed between PFO, PSO and the new model to highlight their performance and the optimisation of the pseudo-order equation, using MATLAB software. Adsorption characteristic of bovine serum albumin adsorption on the track-etched membrane are used as a medium based on protein filtration data were extracted from the literature for different concentrations to demonstrate the comparison between PFO/PSO and the new model. The pseudo first and second-order kinetic models were applied to test the experimental data and they did not provide reasonable values. The results show that the predicted values are consistent with experimental values giving a good correlation coefficient R² = 0.997 and a minimum root mean squared error RMSE = 0.0171. Indeed, the experimental results follow the new model and the optimal pseudo equation order n = 1.115, the most suitable curves for the new model. As a result, we used different experimental adsorption data from the literature to examine and check the applicability and validity of the model.

• Journal of the Korean institute of surface engineering
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• v.44 no.4
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• pp.131-136
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• 2011

A kinetic study has been made for the growth of nanocrystalline diamond (NCD) particles to a continuous thin film on silicon substrate in a microwave plasma chemical vapor deposition reactor. Parameters of deposition have been microwave power of 1.2 kW, the chamber pressure of 110 Torr, and the Ar/$CH_4$ ratio of 200/2 sccm. The deposition has been carried out at temperatures in the range of $400\sim700^{\circ}C$ for the times of 0.5~16 h. It has been revealed that a continuous diamond film evolves from the growth and coalescence of diamond crystallites (or particles), which have been heterogeneously nucleated at the previously scratched sites. The diamond particles grow following an $h^2$ = k't relationship, where h is the height of particles, k' is the particle growth rate constant, and t is the deposition time. The k' values at the different deposition temperatures satisfy an Arrhenius equation with the apparent activation energy of 4.37 kcal/mol or 0.19 eV/ atom. The rate limiting step should be the diffusion of carbon species over the Si substrate surface. The growth of diamond film thickness (H) shows an H = kt relationship with deposition time, t. The film growth rate constant, k, values at the different deposition temperatures show another Arrhenius-type expression with the apparent activation energy of 3.89 kcal/mol or 0.17 eV/atom. In this case, the rate limiting step might be the incorporation reaction of carbon species from the plasma on the film surface.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.309-314
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• 1989

A kinetic study was carried out for the redox reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in acidic solution by spectrophotometric methods. This redox reaction system have been found to show a third order for overall reaction as the respective first order with respect to reactant cis-$[Co(en)_2(N_3)_2]^+$, Fe(II), and $H^+$ catalyst. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were obtained as 14.2Kcal/mol and -16.7 e.u., respectively. On the basis of the kinetic data, we suggest that the redox reaction system proceeds via inner sphere mechanism. The rate equation derived from the proposed mechanism is in agreement with the observed rate equation.