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

• Applied Chemistry for Engineering
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• v.26 no.2
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• pp.145-153
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• 2015

$Cr_2O_3/AP$ (ammonium perchlorate) energetic composites were prepared by a method of solvent/anti-solvent. XRD analysis revealed that the crystalline structure of AP in $Cr_2O_3/AP$ composites is the same as that of pure AP. SEM photomicrograph shows that an average size of cuboid $Cr_2O_3/AP$ composites is approximately $2.5{\mu}m$. TGA analysis shows that the addition of submicron $Cr_2O_3$ particles into AP lowers the HTD (high-temperature decomposition) compared to that of neat AP and the activation energy of the $Cr_2O_3/AP$ composites was calculated by the isoconversional Starlink method. Considering changes in the activation energy, the decomposition reaction mechanism of AP was suggested as follows; the decomposition with the formation of nucleation sites renders formation of porous structure in the composites up to conversion of about 0.25 and after further conversion of over 0.3, it seems that decomposition reaction vigorously takes place rather than sublimation of AP.

• Korean Journal of Food Science and Technology
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• v.13 no.3
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• pp.188-193
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• 1981

Thermal degradation of pantothenic acid in potassium biphthalate buffer and in food samples such as rice, mushroom and beef was studied as functions of temperature and pH. Thermal degradation of pantothenic acid in buffer and food systems followed first order reaction at temperature between $60{\sim}104^{\circ}C$. Activation energy calculated from the Arrhenius equation ranged from 15,700 cal/mole 17,300 cal/mole for both systems. D values at $120^{\circ}C$ were approximately 18 hours for food samples and 15.4 hours at pH 5.65 for buffer sample. Z values of food samples were about $37^{\circ}C$, which were similar to those of buffer sample. The decomposition rate constant of pantothenic acid in buffer sample decreased when the pH increased from 4.0 to 6.46, but activation energy increased. In the range of $pH\;6.46{\sim}8.0$, decomposition rate constant increased but activation energy decreased as pH increased. The kinetic model of pantothenic acid decomposition in buffer system was proposed on the basis of empirical relationship.

• Journal of the Korean Chemical Society
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• v.54 no.2
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• pp.192-197
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• 2010

The spinel compound was obtained by the thermal decomposition of Zn-Co and Zn-Ni gel prepared by sol-gel method using oxalic acid as a chelating agent. The formation of spinel compound has been comfirmed by thermogravimetric analysis (TGA), x-ray powder diffraction (XRD) and infrared spectroscopy (IR). The particle size of 13 nm~16 nm was calculated by Scherrer's equation. The sol-gel method provides a practicable and effective route for the synthesis of the spinel compound at low temperature ($350^{\circ}C$). The kinetic parameters such as activation energy (Ea) and pre-exponential factor (A) for each compound were found by means of the Kissinger method and Arrhenius equation. The decomposition of spinel compound has an activation energy about 155 kJ/mol. Finally, the thermodynamic parameters (${\Delta}G^{\varphi}$, ${\Delta}H^{\varphi}$, ${\Delta}S^{\varphi}$) for decomposition of spinel compound was determined.

• Journal of Korean Society on Water Environment
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• v.32 no.1
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• pp.23-29
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• 2016

Ozonation was investigated for its ability to remove pyruvic acid in a laboratory-scale batch reactor under various experimental conditions, including UV irradiation, TiO₂ addition, and variations in temperature. An ozone flow rate of 1.0 L min^-1 and a concentration of 75±5 mg L^-1 were maintained throughout the experiment, and pH, COD, and TOC were measured at 10 min intervals during a 60 min reaction. Our results confirmed that the combination of UV irradiation and photocatalytic TiO₂ in the ozonation reaction improved the removal efficiency of both COD and TOC in aqueous solution at 20℃. Pseudo first-order rate constants and activation energies were quantified based on the COD and TOC measurements. We observed that the O₃/UV, O₃/UV/TiO₂ system increased mineralization and reduced the activation energy (E_a) necessary for pyruvic acid decomposition.

• Applied Chemistry for Engineering
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• v.31 no.4
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• pp.443-451
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• 2020

In this study, the physico-chemical properties and pyrolysis kinetics of livestock mature solid fuel were investigated to know its feasibility as a fuel. Ultimate and proximate analysis results showed that livestock mature solid fuel has high contents of volatile matter (64.94%), carbon (44.35%), and hydrogen (5.54%). The low heating value of livestock mature solid fuel (3880 kcal/kg) was also higher than the standard requirement of solid fuel (3000 kcal/kg). Thermogravimetic analysis results indicated that livestock mature solid fuel has three decomposition temperature regions. The first temperature zone (130~330 ℃) was consisted with the vaporization of extracts and the decomposition of hemicellulose and cellulose. The second (330~480 ℃) and third (550~800 ℃) temperature regions were derived from the decomposition of lignin and additional decomposition of carbonaceous materials, respectively. The activation energy derived from model free kinetic analysis results including Friedman, Flynn-Wall-Ozawa (FWO), and Kissinger-Akahira-Sunose (KAS) methods for the pyrolysis of livestock mature solid fuel was in the range of 173.98 to 525.79 kJ/mol with a conversion rate of 0.1 to 0.9. In particular, the activation energy increased largely at the higher conversion than 0.6. The kinetic analysis using a curve-fitting method suggested that livestock mature solid fuel was decomposed via a multi-step reaction which can be divided into five decomposition steps.

• Environmental Engineering Research
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• v.11 no.5
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• pp.250-256
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• 2006

The combustion kinetics of poly(ethylene terephthalate) (PET) was studied by the dynamic model which accounts for the thermal decomposition of polymer at any time. The kinetic analysis was performed by a conventional nonisothermal thermogravimetric (TG) technique at several heating rates between 10 and 40 K/min in air atmosphere. The thermal decomposition of PET in air atmosphere was found to be a complex process composed of at least two stages for which kinetic values can be calculated. The combustion kinetic analysis of PET gave apparent activation energy for the first stage of $257.3{\sim}269.9\;kJ/mol$, with a value of $140.5{\sim}213.8\;kJ/mol$ for the second stage. To verify the effectiveness of the kinetic analysis method used in this work, the kinetic analysis results were compared with those of various analytical methods. The kinetic parameters were also compared with values of the pyrolysis of PET in nitrogen atmosphere.

• Journal of the Korean Chemical Society
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• v.57 no.1
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• pp.109-114
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• 2013

The effects of aluminum nanoparticles (AlNs) on the thermal decomposition of ammonia perchlorate (AP) were investigated by DSC, TG-DSC and DSC-TG-MS-FTIR. Addition of AlNs resulted in an increase in the temperature of the first exothermic peak of AP and a decrease in the second. The processing of non-isothermal data at various heating rates with and without AlNs was performed using Netzsch Thermokinetics. The dependence of the activation energy calculated by Friedman's isoconversional method on the conversion degree indicated the decomposition process can be divided into three steps. They were C1/D1/D1 for neat AP, determined by Multivariate Non-linear Regression, and changed to C1/D1/F2 after addition of AlNs into AP. The isothermal curves showed that the thermal stability of AP in the low temperature stage was improved in the presence of AlNs.

• Journal of the Korean Society of Safety
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• v.20 no.3 s.71
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• pp.84-90
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• 2005

Thermal decomposition of the copolymer of ${\alpha}$-Methylstyrene(AMS) with Acrylonitrile(AN) was investigated. The copolymer was synthesized in a continuous stirred tank reactor(CSTR) at $80^{\circ}C$ using toluene and benzoyl peroxide(BPO) as solvent and initiator, respectively. The reactor volume was 0.3 liters and residence time was 3 hours. The activation energy of thermal decomposition was in the ranges of $34{\sim}54$ kcal/mol for AMS with AN copolymer. The thermogravimetric trace curves were well agreed with the theoretical calculation.

• Transactions of the Korean Society of Pressure Vessels and Piping
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• v.20 no.1
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• pp.56-65
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• 2024

Cast austenitic stainless steels (CASS) and austenitic stainless steel weldments with a ferrite-austenite duplex structure are widely used in nuclear power plants, incorporating ferrite phase to enhance strength, stress relief, and corrosion resistance. Thermal aging at 290-325℃ can induce embrittlement, primarily due to spinodal decomposition and G-phase precipitation in the ferrite phase. This study evaluates the effects of thermal aging by collecting and analyzing various mechanical properties, such as Charpy impact energy, ferrite microhardness, and tensile strength, from various literature sources. Different model expressions, including hyperbolic tangent and phase transformation equations, are applied to calculate activation energy (Q) of room-temperature impact energies, and the results are compared. Additionally, predictive models for Q based on material composition are evaluated, and the potential of machine learning techniques for improving prediction accuracy is explored. The study also examines the use of ferrite microhardness and tensile strength in calculating Q and assessing thermal embrittlement. The findings provide insights for developing advanced prediction models for the thermal embrittlement behavior of CASS and the weldments of austenitic steels, contributing to the safety and reliability of nuclear power plant components.