• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.362-367
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• 1991

Rates of nucleophilic substitution reaction ([Pd (ONN) Cl] + Y$^-\;{\rightleftharpoons}$ [Pd (ONN)Y] + Cl$^-$ ; Y = SCN$^-$, CN$^-$, N$_3^-$, imidazole, pyridine) have been measured in methanol by spectrophotometric method at various temperatures. A set of nucleophilic reactivity constants, n$_{Pd}^{\circ}$ has been calculated. These values show an order of nucleophilicity CN$^-$ > SCN$^-$ > N$_3^-$ > Imidazole > Pyridine. The enthalpy of activation are small positive values and the entropy of activation are large negative values. From these results, it can be inferred that the nucleophilic substitution reaction proceeds through an associative (A) mechanism.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.327-332
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• 1996

The rates of solvolylsis of methyl chloroformate, phenyl chloroformate and 1-adamantyl derivatives in binary solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters were estimated from the rate constants. The activation volume (${\Delta}V_o^{\neq}$) and the activation entropy (${\Delta}S^{\neq}$) are both negative, but the activation enthalpy (${\Delta}H^{\neq}$) is positive. This behavior is discussed in terms of electrostriction of solvation. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies. From these results, it could be estimated that the solvolyses of 1-adamantyl fluoroformate (in aqueous TFE) and 1-adamantyl tosylate have pathway involving unimolecular reaction, while the reaction of methyl chloroformate, phenyl chloroformate and 1-adamantyl fluoroformate (in aqueous alcohol) proceed through a bimolecular reaction.

• Microbiology and Biotechnology Letters
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• v.20 no.4
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• pp.422-429
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• 1992

The effect of various water-activity depressors, such as pol yo Is, sugars, and polymers, on the conversion yields of the enzymatic synthesis of maltosyl-$\beta$-cyclodextrin from $\beta$-cyc1odextrin and maltose through reverse reaction of pullulanase was investigated. PEG 6000 of concentration of 10% (w/w) was found to be the most acceptable water-activity depressor resulting for increment of conversion yield from 43.0% to 55.9%, corresponding maltosyl-$\beta$-cyc1odextrin concentration of 3.02 g/100 ml H20. Water activity was changed from initial 0.966 to 0.914 upon addition of 20% (w/w) of PEG 6000. The conversion yields were inversely proportional to the water activities, and the increased conversion yield was caused by water activity depression which inhibited the hydrolysis reaction of maltosyl-$\beta$-CD to maltose and $\beta$-cyc1odextrin. The changes of enthalpy ($\Delta$H), entropy ($\Delta$S), and Gibbs free energy ($\Delta$G) were calculated to be 36.788 kJ/mole, 0.067 kJ/mole K. and 14.433 kJ/mole, respectively. The synthesis of maltosyl-$\beta$-CD could be increased substantially by the intermittent feeding of $\beta$-cyclodextrin. PEG 6000 could be separated effectively from reaction mixture using ultrafiltration membrane for reutilization.

• Electrical & Electronic Materials
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• v.10 no.2
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• pp.141-149
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• 1997

L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ powders were prepared by both GNP(Glycine-Nitrate Process) and solid state reaction method in various of calcination temperature(800-1000.deg. C) and time in air. Also, L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ cathode contacts on YSZ(Yttria-Stabilized Zirconia) substrate were prepared by screen printing and sintering method as a function of sintering temperature(1100-1450.deg. C) in air. Sintering behaviors have been investigated by SEM(Scanning Electron Microscope) and porosity measurement. Compositional and structural characterization were carried out by X-ray diffractometer and ICP AES(Inductively Coupled Plasma-Atomic Emission Spectrometry) analysis. Electrical characterization was carried out by the electrical conductivity with linear 4 point probe method. As the calcination period increased in solid state reaction method, L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ phase increased. Although L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ single phase was obtained only for 48hrs at 1000.deg. C, in GNP method it was easy to get single and ultra-fine L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ powders with submicron particle size at 650.deg. C for 30min. The particle size and thickness of L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ cathode contact by solid state reaction method did not change during the heat treatment, while those by GNP method showed good sintering characteristics because initial powder size fabricated from GNP method is smaller than that fabricated from solid state reaction method. Based on enthalpy change from thermodynamic data and ICP-AES analysis, it was suggested to make cathode contact in composition of (L $a_{0.7}$S $r_{0.3}$)$_{0.91}$ Mn $O_{3}$ which have little second phase (L $a_{2}$Z $r_{2}$ $O_{7}$) for high efficient solid oxide fuel cells applications. As (L $a_{0.7}$S $r_{0.3}$)$_{0.91}$Mn $O_{3}$ cathode contact on YSZ substrate was sintering at 1250.deg. C the temperature that liquid phase sintering did not occur. It was possible to obtain proper cathode contacts with electrical conductivity of 150(S/cm) and porosity content of 30-40%.m) and porosity content of 30-40%.

• Clean Technology
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• v.27 no.3
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• pp.261-268
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• 2021

Equilibrium, kinetics, and thermodynamics of adsorption of acid black 1 (AB1) by coal-based granular activated carbon (CGAC) were investigated with the adsorption variables of initial concentration of dye, contact time, temperature, and pH. The adsorption reaction of AB1 by activated carbon was caused by electrostatic attraction between the surface (H⁺) of activated carbon and the sulfite ions (SO₃^-) and nitrite ions (NO₂^-) possessed by AB1, and the degree of reaction was highest at pH 3 (97.7%). The isothermal data of AB1 were best fitted with Freundlich isotherm model. From the calculated separation factor (1/n) of Freundlich, it was confirmed that adsorption of AB1 by activated carbon could be very effective. The heat of adsorption in the Temkin model suggested a physical adsorption process (< 20 J mol^-1). The kinetic experiment favored the pseudo second order model, and the equilibrium adsorption amount estimated from the model agreed to that given by the experiments (error < 9.73% ). Intraparticle diffusion was a rate controlling step in this adsorption process. From the activation energy and enthalpy change, it was confirmed that the adsorption reaction is an endothermic reaction proceeding with physical adsorption. The entropy change was positive because of an active reaction at the solid-liquid interface during adsorption of AB1 on the activated carbon surface. The free energy change indicated that the spontaneity of the adsorption reaction increased as the temperature increased.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.201-207
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• 1983

The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

• Journal of Photoscience
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• v.9 no.2
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• pp.130-133
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• 2002

The last step in the photocycle of photoactive yellow protein (PYP) is a spontaneous recovery of the dark state from the active state in which the p-coumaric acid chromophore is thermally isomerized, concomitantly with the deprotona- tion of the chtomophore and the refolding of the protein moicty. For the purpose of understanding the mechanism of the thermal back-isomerization, we have investigated the rate-determining step by analyzing mutant PYPs of Met100, which was previously shown to play a major role in facilitating the reaction (1). The mutation to Lys, Leu, Ala, or Glu decelerated the dark state recovery by 1 to 3 three orders of magnitude. By evaluating temperature-dependence and pH-dependence of the kinetics of the dark state recovery, it was found that the retardation by mutations resulted from elevation of the activation enthalpy ( H$\^$┿/) and that the pKa of the chromophore, which was affected by the mutation, is in a linier correlation with the amplitude of the rate constants. It was, therefore, deduced from the correlation that the free energy for crossing the activated state in the dark recovery process is proportional to the free energy for the deprotonation of the chromophore, identifying the rate-determining step as the deprotonation of the chromophore. (1) Devanathan, S. Genick, U. K. Canestrelli, I. L. Meyer, T. E. Cusanovich, M. A. Getzoff, E. D. Tollin, G., Biochemistry 1998, 37, 11563 - 11568

• Journal of Mechanical Science and Technology
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• v.14 no.8
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• pp.879-890
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• 2000

This study investigates the nonpremixed $H_2/CO$-air turbulent flames numerically. The turbulent combustion process is represented by a reaction progress variable model coupled with the presumed joint probability function. In the present study, the turbulent combustion model is applied to analyze the nonadiabatic flames by introducing additional variable in the transport equation of enthalpy and the radiative heat loss is calculated using a local, geometry independent model. Calculations are compared with experimental data in terms of temperature, and mass fraction of major species, radical, and NO. Numerical results indicate that the lower and higher fuel-jet velocity flames have the distinctly different flame structures and NO formation characteristics in the proximity of the outer core vortex zone. The present model correctly predicts the essential features of flame structure and the characteristics of NO formation in the bluff-body stabilized flames. The effects of nonequilibrium chemistry and radiative heat loss on the thermal NO formation are discussed in detail.

• Transactions of the Korean Society of Mechanical Engineers
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• v.11 no.1
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• pp.177-188
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• 1987

A compute program based on the minimization of total Gibbs' free energy and enthalpy balance was developed to calculate the chemical equilibrium composition and adiabatic flame temperature, especially stressed on NO and CO concentration of Heavy oil. Twenty four components of combustion gases which would be produced from the combustion of Heavy oil were chosen and utilized for the products composition analysis of competing combustion reaction. As the results, following conclusions were turned out; (1) Maximum adiabatic flame temperature was found around to be 2900K, when the stoichiometric air ratio was 0.8. (2) Maximum NO quantity in adiabatic process was occurred when supplied air quantity was around 120% of theoretical air requirement. (3) NO and CO quantities were increased with combustion gas temperature at constant stoichiometric air ratio. (4) At constant temperature of combustion gas, NO quantity was increased and Co quantity was decreased with supplied air quantity.

• Journal of the Korean Society of Clothing and Textiles
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• v.13 no.2 s.30
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• pp.128-136
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• 1989

In order to investigate a practical application of fibrous adsorbents to heavy metal ions, amidoxime fibers, as a particular class of solid chelate agents, were prepared by hydroxylamine treatment for acrylic fibers in a recipe of neutralization. Among the important problems from plant effluents are toxic concentrations of heavy metals such as copper. Accordingly, the properties of Cu (II) adsorption and its chelates were studied. The results obtained are as follows; The fibrous adsorbents have the property of increasing the swelling volumes by amidoximation. The adsorption of Cu (II) ion is characterized by an endothermic reaction, which is estimated as the plus values in the enthalpy change ($\delta$H=1.30 Kcal/mol. and 3.14 Kcal/mol.). The Cu (II) ions are adsorbed in the range of pH $3\~8$ and the maximum adsorptions are occurred about pH 8. Owing to the anions $(NO_3^-,\;Cl^-)$ of copper salts, amidoxime fibers form 1:1 and 2:1 (ligand: metal) chelating complexes with Cu (II). The nitrate anion chelates to amide I (NH) of amidoxime groups and the chlorine anion does to nitrosyl (NO). These effects relate to the crystallization of the complex and the thermal property.