• 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.25 no.4
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• pp.283-290
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• 1981

The reaction rates for the transesterification reaction were measured on the excess sucrose with the five fatty acid methyl ester systems such as methyl laurate, methyl myristate, methyl palmitate, methyl stearate and methyl oleate at temperature range of $50^{\circ}C$ to $90^{\circ}C$ in N,N-dimethylformamide solvent and potassium carbonate as a catalyst. Their activation parameters as well as rate constants were calculated from these measurements. And these reactions were found to be pseudo-first order and depended mainly on the structural changes in fatty acid residue of methyl esters. Also their reactions were found to be of enthalpy-controlled, which were disfavored in the order of methyl laurate, methyl myristate, methyl palmitate, methyl oleate and methyl stearate. Correspondingly their activation energies were 9.3, 9.9, 10.3, 10.9 and 11.1 kcal/mole, respectively.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.150-154
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• 1980

Kinetic studies of the reaction of benzyl benzenesulfonate with pyridine in acetone were carried out by the electric conductivity method under 1 to 2000 bars and at 20 to $40^{\circ}C$. The rate increases with increasing pressure and temperature. The activation enthalpy $({\Delta}H^{\neq}),\;entropy\;({\Delta}S^{\neq})$ and activation volume $({\Delta}V^{\neq})$ of the reaction are obtained by the above experiment. The isokinetic relationship between $({\Delta}H^{\neq})\;and\;({\Delta}S^{\neq})$ for pressure change in the reaction was shown, and its isokinetic temperature was $342^{\circ}K$. From all of the above results it was found that this reaction precedes on the $S_N2$ reaction mechanism in which the rate of the reaction was determined by $C{\cdots}N$ bond formation at transition state.

• Composites Research
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• v.21 no.1
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• pp.16-21
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• 2008

The cure behavior of epoxy resin with a conventional amide-type hardener(HD) was investigated in the presence of castor oil(CO), cashew nut shell liquid(CNSL) and CNSL-formaldehyde resin(CFR) by using a dynamic differential scanning calorimetry(DSC). The activation energy of curing reaction was also calculated based on the non-isothermal DSC thermograms at various heating rates. An one-stage curing was noted in the case of epoxy resin filled with CO, while the epoxy resin with CNSL and CFR showed a two-stage curing process. A competitive cure reaction was noted for the epoxy resin/CNSL(or CFR)/HD blends. In the absence of HD, the CFR showed lower values of curing enthalpy than that of CNSL. The activation energy of epoxy resin curing increased with increasing the CNSL and CFR loading.

• 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 Korean Society on Water Environment
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• v.21 no.1
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• pp.14-20
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• 2005

A feasibility study has been conducted regarding the application of waste coffee grounds as an adsorbent for the treatment of nickel ion containing wastewater. The major variables which considered to influence the adsorbability of nickel ion were its initial concentration, reaction temperature, pH, and coexisting ion. The specific surface area of coffee grounds used in the experiment was found to be ca. $39.67m^2/g$, which suggesting its potential applicability as an adsorbent due to its relatively high surface area. In the experimental conditions, more than 90% of the initial amount of nickel ion was shown to adsorb within 15 minutes and equilibrium in adsorption was attained after 3 hours. The adsorption behavior of nickel ion was well explained by Freundlich model and kinetics study showed that the adsorption reaction was second-order. Adsorption was reduced with temperature and its change of enthalpy in standard state was estimated to be -807.05 kJ/mol. Arrhenius equation was employed for the calculation of the activation energy of adsorption and nickel ion was observed to adsorb on coffee grounds exoentropically based on thermodynamic estimations. As pH rose, the adsorption of nickel ion was diminished presumably due to the formation of cuboidal complex with hydroxide ion and the coexistence of cadmium ion was found to decrease the amount of nickel ion adsorption, which was proportional to the concentration of cadmium ion.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.309-313
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• 1990

The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3657-3664
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• 2012

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.

• Journal of Korean Society on Water Environment
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• v.20 no.5
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• pp.520-524
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• 2004

As a feasibility study for the application of carbon nanotubes to the treatment of environmental pollutants, the adsorption characteristics of humic acid on carbon nanotubes has been investigated. The dispersion features of carbon nanotubes in aquatic environment were investigated by measuring the variation of their electrokinetic potentials with pH, and the effects of some dispersants on their dispersion features were also examined. Under the experimental conditions, humic acid was observed to mostly adsorb on nanotubes within a few minutes and reach the equilibrium state within about one hour. The adsorption features of humic acid on nanotubes were found to follow the Freundlich model better than the Langmuir Model. Humic acid adsorbed on carbon nanotubes endothermically and the change of enthalpy in adsorption reaction was estimated to be ca. 18.37kJ/mol at standard state. The entropic change in adsorption reaction for humic acid was ca. 0.0503kJ/mol at standard state and the activation energy for adsorption was also estimated based on the change of rate constants with temperature. FT-IR investigations showed that the functional groups such as alcohol, ester, and aromatics existing in the chemical structure of humic acid might work as the bridge in its adsorption on nanotubes.

• Journal of the Korean Society for Heat Treatment
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• v.6 no.3
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• pp.138-143
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• 1993

Effects of aging treatment on the microstructural evolution of a rapidly solidified Al-Li-Cu alloy were investigated by differential scanning calorimetry (DSC) and transmission electron microscopy(TEM). It was found that the precipitation sequence was: supersaturated solid solution ${\alpha}^{\prime}$ ${\rightarrow}$ metastable ${\delta}^{\prime}$ + stable precipitate $T_1$ ${\rightarrow}$ stable precipitates ${\delta}+T_1$. Two exothermic and two endothermic peaks are detected by DSC analysis. The two exothermic and endothermic peaks corresponded to ${\delta}^{\prime}$ and ${\delta}+T_1$ precipitation and dissolution reactions respectively. The enthalpy of ${\delta}^{\prime}$ precipitation decreased with increasing of aging temperature and time until the finishing point of precipitation. The activation energy for precipitation of ${\delta}^{\prime}$ was measured as 80KJ/mol and the energy for dissolution was 93KJ/mol. These values arc higher than those of AI-Li binary alloy. Peak hardness value (Hv 170) was obtamed at $210^{\circ}C$ for 1hr aging treatment which coincided with finishing point of ${\delta}^{\prime}$ precipitation.