• Bulletin of the Korean Chemical Society
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• v.2 no.4
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• pp.138-141
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• 1981

The rate of the bromine-exchange reaction between gallium bromide and i-butyl bromide in 1,2,4-trichlorobenzene or nitrobenzene was measured at 19, 25 and $40^{\circ}C$, using i-butyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to i-butyl bromide. The third-order rate constant determined at $19{\circ}C$ was $3.28{\times}10^{-2}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in 1,2,4-trichlorobenzene and $9.25{\times}10^{-3}l^2{\cdot}mole^{-2}{\cdot}sec^{-1}$ in nitrobenzene. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

• Bulletin of the Korean Chemical Society
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• v.25 no.11
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• pp.1645-1647
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• 2004

Potential energy surfaces for the reaction Al + $O_2{\to}$AlO + O have been calculated with the multireference configuration interaction (MRCI) method using molecular orbitals derived from the complete active space selfconsistent field (CASSCF) calculations. The end-on geometry is the most favourable for the reaction to take place. The small reaction barrier in the present calculation (0.11 eV) is probably an artefact related to the ionicneutral avoided crossing. The charge analysis implies that the title oxidation reaction occurs through a harpooning mechanism. Along the potential energy surface of the reaction, there are two stable intermediates of $AlO_2(C_{{\infty}v}$ and $C_{2v}$) at least 2.74 eV below the energy of reactants. The calculated enthalpy of the reaction (-0.07 eV) is in excellent agreement with the experimental value (-0.155 eV) in part due to the fortuitous cancellation of errors in AlO and $O_2$ calculations.

• Transactions of the Korean hydrogen and new energy society
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• v.9 no.1
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• pp.25-30
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• 1998

4-probe resistivity measurement technique was used to study kinetics of hydrogen absorption on Pd film ($180{\AA}$ thick) in the ${\alpha}$ phase. Hydrogen gas was introduced to the activated Pd film. For very low hydrogen concentration the following rate law is valid in ${\alpha}$ phase very thin Pd film $$v=k\frac{1}{1+KX{_H}}PH{_2}-k^{\prime}\frac{KX{_H}{^2}}{1+KX{_H}}$$ which is similar to that of bulk. The activation energy of the forward reaction is 4.6kcal/mol H and of the backward reaction 8.4kcal/mol H, which yields the reaction enthalpy -3.8kcal/mol H in the temperature range between 25 and $40^{\circ}C$. The values of activation and enthalpy of thin film are rather smaller than that of bulk sample. This may be due to surface area difference between bulk and film.

• Journal of the Korean Chemical Society
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• v.57 no.6
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• pp.684-690
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• 2013

Since a glycerol molecule has three active sites, two ${\alpha}$ and one ${\beta}$ hydroxyl groups; it undergoes condensation by releasing water molecules to produce linear, nonlinear and heterocyclic oligomers. The Gibbs free energy (G), enthalpy (H) and internal energy (E) of 7 diglycerol, 15 triglycerol and 23 tetraglycerol isomers were calculated at B3LYP level of theory using 6-311++G(d, p) basis set, in both gas and aqueous phases. Linear oligomers, ${\alpha}{\alpha}$-diglycerol, ${\alpha}{\alpha}$, ${\alpha}{\alpha}$-triglycerol and ${\alpha}{\alpha}$, ${\alpha}{\alpha}$, ${\alpha}{\alpha}$-tetraglycerol, were found to be the most stable oligomers in aqueous phase. It was found that the stability of cyclic oligomers decreases as the size of their rings increases. Cyclic oligomers are produced by dehydration of the acyclic ones which is an endothermic reaction while its ${\Delta}G$ is negative. The dehydration reaction is less endothermic in aqueous phase.

• Textile Coloration and Finishing
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• v.19 no.4
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• pp.18-25
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• 2007

Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Green 9(G-9) of dinitrothiophene disperse dye were investigated. As soon as G-9 contacted with alkali, instant and continuous decreases of color strength of G-9 followed with increasing time. The hydrolysis rate of G-9 increased with increasing alkali, and it was found that alkali appeared first order dependence. The observed rate constants obtained from hydrolysis of various amount of dye were similar values, and calculation of initial rates showed that G-9 hydrolyzed by first order reaction for dye. Therefore it was confirmed that the overall reaction was second order, $SN_2$ of nucleophilic substitution reaction. Increasing temperature enhanced the hydrolysis of G-9. From the results of hydrolysis performed at various temperatures, it was obtained that activation energy(Ea) was 12.6 kcal/mole, enthalpy of reaction(${\triangle}H$) was 12.0 kcal/mole, and entropy of reaction(${\triangle}S$) was $29.8J/mol{\cdot}K$.

• Resources Recycling
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• v.11 no.6
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• pp.38-46
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• 2002

Fundamental investigations were conducted far the recovery process of waste organic solvent by fractional distillation in the aspects of equilibrium and kinetics. Mixture of toluene and xylene, which were both being used in the largest amount as industrial organic solvent, was taken as the artificial waste organic solvent and their distillation behaviors were studied. The purity of recovered solvent was investigated by Cir Chromatography and shown to be in the range of 94～98%. Based upon equilibrium calculations, the changes in the Gibbs free energy, standard enthalpy, and standard entropy for distillation reaction have been estimated. The standard enthalpy changes for toluene and xylene were shown to be 44.833 and 47.044 kJ $mol^{-1}$ respectively, which were similar to their molar heats of evaporation. The activation energies of distillation fur toluene and xylene obtained from kinetic studies were 3.281 and 2.699 kJ $mol^{-1}$ and they were about one tenths of the standard enthalpy changes of distillation reaction. The highness of the purity of recovered organic solvents suggested the possibility that the recovered waste organic sol-vent could partly replace the original solvent.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.24 no.5
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• pp.340-344
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• 1991

On heating and fleering food-stuffs, it is very important to obtain informations about thermophysical properties of fishes for designing of freezing and heating equipment and analyzing of physico-chemical reaction during storage. It is particularly necessary to measure denaturation enthalpy, temperature, latent heat of freezing, activation energy, enthalpy, entropy and free energy on freezing and heating rate. In this study, DSC was used to study effects of freezing and heating rate on thermophysical properties and denaturation temperature on scanning rate $2.5-10.0^{\circ}C/min$. On increasing scanning rate, denaturation temperature of protein and lipid incresed and freezing point, activation energy, enthalpy, entropy were decreased. In freezing process free energy of fishes were found to be $14.2-18.9 kcal/mol$.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1037-1041
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• 2012

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (${\Delta}S^\neq=-2cal\;mol^{-1}\;K^{-1}$) over considerably unfavorable enthalpy of activation (${\Delta}H^\neq=18.0\;kcal\;mol^{-1}$). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted $S_N2$ mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, $k_H/k_D$ < 1.

• Elastomers and Composites
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• v.18 no.4
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• pp.140-147
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• 1983

The purpose of this dissertation is to increase oxidation resistance for Polybutadiene & Polyisoprene, and to investigate the energetics of inhibited oxidation of Polybutadiene & Polyisoprene stabilized with various types of antioxidants using DSC. The results of the study are as fellows: 1. In the DSC SCREEN for the onset temperature of oxidation, Polybutadiene was faster than Polyisoprene for the samples containing no antioxidant in air. 2. In the DSC evaluation for Polybutadiene, Recipe BG-4 with 2.0phr compounds of antioxidant was the best effective, and Recipe BS-4 with 2.0phr compounds of antioxidant was the worst effective, and the degrees of effect of antioxidant were exhibited in the ranking of G-1, D, BHT, and SP, roughly. 3. In the DSC evaluation for the Polyisoprene, Recipe IG-4 with 2.0phr compounds of antioxidant was the best effective, and Recipe ID-4 with 2.0phr compounds of antioxidant was the worst effective, and the degrees of effect of antioxidant were exhibited in the ranking of G-1, SP, BHT, and D roughly. 4. In the study on enthalpy which depends on exothermal reaction, the enthalpy of Polyisoprene was gloater than that of Polybutadiene. However, the problem was not solved completely, and it needs further studies.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4347-4351
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (2) with X-pyridines are investigated kinetically in acetonitrile at $-20.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. Unusual positive ${\rho}_X$ (= +2.49) and negative ${\beta}_X$ (= -0.41) values are obtained with the weakly basic pyridines, and rationalized by the isokinetic relationship with isokinetic temperature at $t_{ISOKINETIC}=6.6^{\circ}C$. The pyridinolysis rate of 2 with a cyclic five-membered ring is forty thousand times faster than its acyclic counterpart (3: diethyl chlorophosphate) because of great positive value of the entropy of activation of 2 (${\Delta}S^{\neq}$ = +49.2 eu) compared to negative value of 3 (${\Delta}S^{\neq}$ = -44.1 eu) over considerably unfavorable enthalpy of activation of 2 (${\Delta}H^{\neq}=28.4\;kcal\;mol^{-1}$) compared to 3 (${\Delta}H^{\neq}=6.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed.