• Journal of the Korean Chemical Society
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• v.53 no.5
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• pp.499-504
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• 2009

Metals have often played important roles to some enzymatic reactions that are essential to biological processes. Therefore many scientists have studied the reaction mechanisms of catalytic reactions in metaloenzymes for many years. Methane MonoOxygenase (MMO) is an enzyme that oxidize methane to methyl alcohol. Recently Tolman et al. studied a model reaction for MMO, which is a hydroxide transfer reaction in Bis-($\mu$-oxo)-dicopper complex, and suggested several possible mechanisms. Later a two-step mechanism, which is hydrogen transfer followed by hydroxide rebound, was proposed from theoretical studies. In this study we calculated the reactant, product, and the transition state structures, and energetics of the first hydrogen transfer reaction using various DFT methods including recently developed the MO6 family of DFT, namely, MO6, MO6L, and MO6-2X. We found that the M06/6-31G(d,p)/LANL2DZ method reproduce the experimental XRD structure of reactants very well. The TS structures, barrier heights, and reaction energies depend very much on the size of the basis sets.

• Resources Recycling
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• v.17 no.3
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• pp.48-55
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• 2008

Leaching of copper and silver from mobile phone PCBs(printed circuit boards) with nitric acid was performed to investigate the effects of nitric acid concentrations, leaching temperatures, agitation speeds, and pulp densities on the leaching behaviors of Cu and Ag. The leaching rate considerably increased with increasing acid concentration and temperature. The leaching ratios of Cu and Ag were found to be 96.4% and 96.5%, respectively, under the optimum condition; at $80^{\circ}C$ with 2mol/L $HNO_3$ and 120g/L in pulp density within 39minutes. The kinetic parameters were determined based on the shrinking core model with reaction control corresponding to small particles. The activation energies for the leaching of copper and silver were found to be 45.5kJ/mol and 60.5kJ/mol at $35{\sim}80^{\circ}C$ with 2mol/L $HNO_3$, respectively.

• Journal of the Korean Chemical Society
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• v.40 no.12
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• pp.748-755
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• 1996

The effects of temperature on the conformational properties of poly(ethylene oxide) (PEO) in aqueous and aqueous urea solutions are reported. The values of intrinsic viscosity and Huggins coefficients for the PEO dissolved in water and urea/water mixtures (urea concentration 0.2, 1, and 2 M) were obtained using a viscometry method and discussed with respect to the change of water structure. At low temperatures (below 22 $^{\circ}C)$, the PEO-water interaction is favorable and the chain can be extended, whereas at higher temperatures (above 24 $^{\circ}C)$, it is less favorable and the chain can be contracted by a hydrophobic hydration, i.e., the PEO-water interaction becomes to be unfavorable with the increase in temperature. As the urea is added to the system, the PEO chain can be more extended and huged by the perturbation of the structured water originating from the unfavorable PEO-water interaction. The effect of temperature on the intrinsic viscosity values shows an Arrhenius behavior. The activation energies of the viscous flow were obtained and discussed.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.953-958
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• 2010

A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within $Ti^+(CH_3COCH_3)_n$ heterocluster ions. The reactions of $Ti^+$ with $CH_3COCH_3$ clusters were found to be dominated exclusively by an oxidation reaction, which produced $TiO^+(CH_3COCH_3)_n$ clusters. These ions were attributed to the insertion of a $Ti^+$ ion into the C=O bond of the acetone molecule within the heteroclusters, followed by $C_3H_6$ elimination. The mass spectra also indicated the formation of minor sequences of heterocluster ions with the formulas $Ti^+(C_3H_4O)(CH_3COCH_3)_n$ and $TiO^+(OH)(CH_3COCH_3)_n$, which could be attributed to C-H bond insertion followed by $H_2$ elimination and to the sequential OH abstraction by the $TiO^+$ ion, respectively. Density functional theory calculations were carried out to model the structures and binding energies of both the association complexes and the relevant reaction products. The reaction pathways and energetics of the $TiO^+\;+\;CH_2CHCH_3$ product channel are presented.

• Elastomers and Composites
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• v.44 no.3
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• pp.269-273
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• 2009

A study on the life-time expectation of a CR-modified NR rubber composite through the change of thermal degradation characteristics was performed using both isothermal thermogravimetric analysis (TGA) and thermomechanical analysis (TMA). Master curves at reference temperature of $90^{\circ}C$ could be obtained with shift factor $a_T$, which was determined empirically using Time-Temperature Superposition Principle (TTSP). Activation energies could be calculated from the slope of Arrhenius plot of shift factor and showed similar values of $E_{a,TGA}$= 41.2 and $E_{a,TMA}$= 54.5 kJ/mol, respectively. It was considered from the results that chemical degradation resulting weight loss of the sample might be closely related to a physical degradation such as the dimensional change of the sample.

• Clean Technology
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• v.18 no.4
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• pp.360-365
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• 2012

With rapid increase in municipal solid waste (MSW) due to the rising economy, solid waste gasification emerges as one of the promising technologies. Separation of the carbon monoxide (CO) and hydrogen ($H_2$) from syngas obtained by gasification of MSW was studied using the polyamide composite membrane. The separation characteristics of the CO and $H_2$ were studied at different gas flow rates and stage cuts. The permeability of CO and $H_2$ along with the selectivity of $H_2$ with respect to CO was obtained. Furthermore, the Arrhenius plots were obtained to estimate the activation energies of CO and $H_2$ permeabilites.

• Polymer(Korea)
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• v.33 no.4
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• pp.364-370
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• 2009

The curing kinetics and mechanical properties of siloxane-diaminodiphenylmethane (ETSO-DDM) on the two kinds of bisphenol (BPH) system which are DGEBA and DGEBF were investigated with the different contents of ETSO. To investigate the curing kinetics of the ETSO-DDM/BPH systems, differential scanning calorimeter (DSC) was used. The mechanical properties of ETSO-DDM/BPH systems were also examined by universal testing machine (UTM), tensile test and flexural test. From experimental results, the activation energies and mechanical properties of ETSO-DDM/BPH were improved with the decrease contents of ETSO. This was due to the high cross-linking density made from short length of ETSO-DDM, resulting in improving the mechanical inter-locking between ETSO-DDM and BPH in these systems.

• Journal of the Korean Society of Food Science and Nutrition
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• v.22 no.6
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• pp.785-791
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• 1993

Kinetic studies were performed to investigate free-fructose content change in rice during storage. The rice was stored at various water activities(0.44, 0.52, 0.65 and 0.75) and at fluctuating temperature($30/50^{\circ}C$) over period of 22 weeks. At early stage of storage free-furctose content increased by zero-order reaction, whereas at later stage, it decreased by first-order reaction. The reaction rates were positively related to water activity and/or temperature during storage. Activation energies calculated at range of aw 0.44~0.75 were found to be 10.76~19.56kcal/mole and 4.53~8.40kcal/mole, for the period of increase and decrease in the free-fructose contents, respectively. The shelf-life assessed at $25^{\circ}C$ was found to be 252(aw 0.44), 212 (aw 0.52), 193(aw 0.65) and 162(aw 0.75) days.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.28 no.10
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• pp.642-647
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• 2015

The perovskite solid solutions of the $Sr_{1-x}Mg_xFe{^{3+}}_{1-{\tau}}Fe{^{4+}}_{\tau}O_{3-y}$ system (x=0.0, 0.1, 0.2, and 0.3) were synthesized in $N_2$ at $1,150^{\circ}C$. X-ray powder diffraction study assured that all the four samples had cubic symmetries(SM-0: $3.865{\AA}$, SM-1: $3.849{\AA}$, SM-2: $3.833{\AA}$, and SM-3: $3.820{\AA}$) and that the lattice volumes decreased steadily from $57.7{\AA}^3$ to $55.7{\AA}^3$ with x values. The nonstoichiometric chemical formulas were determined by Mohr salt analysis and with the increase of x values the amounts of $Fe^{4+}$ ion and oxygen were decreased simultaneously. Thermal analysis showed that SM-0 started to lose its oxygen at $450^{\circ}C$ and SM-1, Sm-2, and SM-3 began to lose their oxygen at around $350{\sim}400^{\circ}C$. SM-0 showed almost reversible weight change in the cooling process. All the samples exhibited semiconducting behaviors in the temperature range of $10{\sim}400^{\circ}C$. Conductivities of the 4 samples were decreased in the order of SM-0, SM-1, SM-2, and SM-3 at constant temperature. The activation energies of the conductions were in the range of 0.176 eV~0.244 eV.

• Journal of Sensor Science and Technology
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• v.8 no.5
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• pp.388-393
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• 1999

In this study, the $CaSO_4:Eu$ TLDs are fabricated and their trap parameters are determined. The optimum concentration of Eu for fabrication of the $CaSO_4:Eu$ TLD is 0.5 mol% and optimum temperature is $600^{\circ}C$ for 2 hours sintering in air. The glow curve of $CaSO_4:Eu$ consists of two glow peaks and these peaks are isolated by thermal bleaching method. Trap parameters of two glow peaks are measured using the initial rise, the peak shape, the heating rate and the least square curve fitting methods. The activation energies of the glow peak I and II are 1.00 eV and 1.09 eV, and the frequency factors are $7.04{\times}10^{11}\;s^{-1}$ and $5.12{\times}10^{11}\;s^{-1}$ and the kinetic orders are 1.11 and 1.33, respectively.