• Transactions of the Korean hydrogen and new energy society
• /
• v.10 no.4
• /
• pp.191-196
• /
• 1999

4-probe resistivity measurement technique was used to study hydrogen A-D(Absorption-Desorption)kinetics on Pd films(18 to 67nm thick) from 25 to $50^{\circ}C$, from 0 to 5 torr hydrogen pressure. Pd films were made on sapphire substrate by thermal evaporation technique under high vacuum at room temperature. Upto about 100 hydrogen A-D cyclings, no pulverization was observed, but film was detached partially from substrate. Forward reaction and backward reaction rate were analyzed separately. The activation energies of hydrogen A-D processes were obtained from the Arrhenius plot of the reaction rates. The activation energies of Pd films are not strongly dependent on the thickness of the film. But the activation energy of very thin film( l8nm thick) was smaller than the others.

• Applied Chemistry for Engineering
• /
• v.10 no.8
• /
• pp.1161-1168
• /
• 1999

The redox property of oxide materials of the 3rd period transition metals(Cr~Zn), V, Mo, and W was studied with temperature-programmed reduction/temperature-programmed oxidation(TPR/TPO) experiment. The peak temperatures of TPO spectra were equal to or lower than those of TPR spectra. And the peak shapes of TPO spectra were broader than those of TPR ones. The activation energies of TPR/TPO for the oxides of the 3rd period transition metals showed in the range of 33~149 kJ/mol, while for the oxides of V, Mo, and W, they showed relatively higher values. The change of activation energies of TPR/TPO with various metal oxides showed a similar trend to the change of their metal-oxygen bond strengths. The change of activation energies of o-xylene oxidation for various metal oxides was proportional to the difference (${\Delta}E_a$) between the activation energy of TPR and that of TPO. From these results, we concluded that the oxidation of o-xylene over various metal oxide catalysts follows the Mars-van Krevelen mechanism including the surface reduction-oxidation of the metal oxide itself.

• Economic and Environmental Geology
• /
• v.29 no.3
• /
• pp.269-279
• /
• 1996

Dehydroxylation and mullitization of primary and secondary kaolins were investigated in order to compare and understand the differences in thermal behaviours by DTA and TG up to $1,100^{\circ}C$. Chemical analyses and EPMA of the samples revealed nearly ideal unit-cell formulae of kaolins. The weight losses of dickite and halloysite are 14% and 12.5% on the average, respectively. The activation energies of dehydroxylation of kaolin minerals were calculated according to Kissinger's approach which uses various heating rates in DTA to estimate the activation energy of thermal reactions. The activation energies of dehydroxylation of halloysites from Daemoung and Buksam mines are about $163kJmor^{-1}$ (white), $168kJmor^{-1}$ (pink), and $176kJmor^{-1}$ respectively. The activation energies of dickites collected from Sungsan and Ogmae mines are about $166kJmor^{-1}$ and $387kJmor^{-1}$. The asymmetric shape of endothermic peak in DTA, the relative intensities of OH-stretching bands in FTIR spectroscopy and the existence of residual XRD peaks of the samples which were heated at $550^{\circ}C$ for 2 hours indicate that Sungsan dickite may be more disordered than Ogmae dickite. The new phase formed in thermally treated samples in the range of $900^{\circ}C$ to $1,100^{\circ}C$ was identified as mullite by XRD on the basis of disappearing of the characteristic peaks of kaolins and increasing of amorphous background upon heat treatment. On further heating, loss of more water from dehydroxylate resulted in the formation of mullite and the characteristic X-ray diffraction patterns of mullite began to appear at about $900{\sim}1,000^{\circ}C$ in kaolins.

• Journal of the Korean Chemical Society
• /
• v.34 no.2
• /
• pp.136-142
• /
• 1990

PMO (Pertubation Molecular Orbital) energies, ${\delta}E$, have been calculated from NBMO (Nonbonding Molecular Orbital) coefficient for some hydrocarbons by PMO method. It was found that the stabilization energies are correlated with activation energies, bond dissociation energies, and G-values observed from vapor phase radiolysis in the free radical reactions.

• Journal of the Korean Ceramic Society
• /
• v.52 no.5
• /
• pp.331-337
• /
• 2015

$LaBO_3$ (B = Cr, Mn, Fe, Co, and Ni) perovskites, the most common perovskite-type mixed ionic-electronic conductors (MIECs), are promising candidates for intermediate-temperature solid oxide fuel cell (IT-SOFC) cathodes. The catalytic activity on MIEC-based cathodes is closely related to the bulk ionic conductivity. Doping B-site cations with other metals may be one way to enhance the ionic conductivity, which would also be sensitively influenced by the chemical composition of the dopants. Here, using density functional theory (DFT) calculations, we quantitatively assess the activation energies of bulk oxide ion diffusion in $LaBO_3$ perovskites with a wide range of combinations of B-site cations by calculating the oxygen vacancy formation and migration energies. Our results show that bulk oxide ion diffusion dominantly depends on oxygen vacancy formation energy rather than on the migration energy. As a result, we suggest that the late transition metal-based perovskites have relatively low oxygen vacancy formation energies, and thereby exhibit low activation energy barriers. Our results will provide useful insight into the design of new cathode materials with better performance.

• Environmental Engineering Research
• /
• v.22 no.3
• /
• pp.320-328
• /
• 2017

This paper describes the non-isothermal pyrolysis of wood pellet and saw dust, and their blends with bituminous coal. The blends showed the distinct, two peaks in thermogravimetric curves, and the first peak came from the biomass pyrolysis and the second one came from the coal pyrolysis. The interaction in the blend was evaluated in terms of the maximum rate of weight loss, characteristic temperatures, char yields, and the calculated and experimental thermogravimetric curves. The activation energies and frequency factors for the blends were obtained with the multi-stage, Coats and Redfern method. The respective activation energies of 73 and 67 kJ/mol and the frequency factors of 725,100 and $65,262min^{-1}$ were obtained for the present wood pellet and saw dust samples. The thermogravimetric study shows that there is no significant interaction between the present biomass and coal in the blends, and the pyrolysis behavior can be described with the additive rule.

• Carbon letters
• /
• v.9 no.2
• /
• pp.121-126
• /
• 2008

High modulus pitch based carbon fibers (HM) were exposed to isothermal oxidation using tube furnace in carbon dioxide gas to study the oxidation kinetics under the temperature of $800-1100^{\circ}C$. The kinetic equation $f=1-{\exp}(-at^b)$ was introduced and the constant b was obtained in the range of 1.02~1.42. The oxidation kinetics were evaluated by the reaction-controlling regime (RCR) depending upon the apparent activation energies with the conversion increasing from 0.2 to 0.8. The activation energies decrease from 24.7 to 21.0 kcal/mole with the conversion increasing from 0.2 to 0.8, respectively. According to the RCR, the reaction was limited by more diffusion controlling regime for the HM fibers with the conversion increasing. Therefore, it seems that the oxidation which is under the diffusion controlling regime takes place continuously from the skin to the core of the fiber.

• Preventive Nutrition and Food Science
• /
• v.12 no.2
• /
• pp.115-118
• /
• 2007

Tocopherols are important lipid-phase antioxidants that are subject to heat degradation. Therefore, kinetic analyses for oxidative degradation of tocopherols as a function of temperatures and times were performed. Alpha-, gamma- and delta-tocopherols dissolved in glycerol were heated at 100${\sim}$250$^{\circ}C$ for 5～60 min. Oxidized tocopherols were analyzed by HPLC using a reversed phase ${\mu}$-Bondapak C$_{18}$-column with two kinds of elution solvent systems in a gradient mode. The degradation kinetics for tocopherols followed a first-order kinetic model. The rate of tocopherol degradation was dependent on heating temperatures. The degradation rate constants for ${\gamma}$- and ${\delta}$-tocopherols were higher than those for ${\alpha}$-tocopherol. The experimental activation energies of ${\alpha}$-, ${\gamma}$- and ${\delta}$- tocopherols were 2.51, 6.05 and 5.34 kcal/mole, respectively. The experimental activation energies for the oxidative degradation of ${\gamma}$- and ${\delta}$-tocopherols were higher than that of ${\alpha}$-tocopherol.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.5
• /
• pp.391-395
• /
• 1986

MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

• Journal of the Korean Physical Society
• /
• v.73 no.12
• /
• pp.1873-1878
• /
• 2018

We have investigated the ionic conductivity and dielectric relaxation in $Li_2B_4O_7$ (LBO) and $Li_2O-B_2O_3-Ta_2O_5$ (LBTO) glasses. The sample was synthesized by using the melt quenching method. The frequency dependence of the electrical data from the LBO and LBTO glasses has been analyzed in the frameworks of the impedance Cole-Cole formalism and the universal power-law representation driven by the modified fractional Rayleigh equation. The potential barriers in the LBO and the LBTO glasses turn out to be the same. Comparing with the dc and ac activation energies of the LBO glass, these energies of the LBTO glass decrease due to the increasing Coulomb interaction of inter-cationic interaction.