• Bulletin of the Korean Chemical Society
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• v.25 no.8
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• pp.1231-1237
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• 2004

Rate constants for photolytic reactions of p-substituted 2-diazopropiophenones were determined in acetonitrile. The reactions show a comparatively low value of activation energy and activation enthalpy to alkylcarbenes or other arylcarbenes. The transition state corresponds to the step of a new carbonyl bond formation. The high negative ρ -values are shown in Hammett plots. The kinetics results and EPR spectrum are in accord with a phenomenon that occurs in interconversion between singlet and triplet carbenes.

• Bulletin of the Korean Chemical Society
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• v.16 no.1
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• pp.53-58
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• 1995

Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

• Textile Coloration and Finishing
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• v.2 no.3
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• pp.26-35
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• 1990

This study was carried out with the view of fundamental investigating to improve the tactile and the hygroscopicity of Poly(ethylene Terephthalate) (PET)fibers. Mono-sodium ethylene glycolate in ethylene glycol (MSEG-EG) solution was prepared and PET films were treated with it. The following conclusions were obtained. When PET films were decomposed in MSEG-EG solution, decomposition rate constant showed an exponential relationship with treating temperature; activition energy was 23.30 Kcal/mol, activation enthalpy was 22.52~22.60 Kcal/mol and activation entropy was -29.20~ -29.41 e.u. On the basis of the results obtained above and structure identification of decomposition products, it was found that the decomposition reaction proceeded through ester interchange reaction.

• Journal of the Korean Chemical Society
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• v.63 no.4
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• pp.233-236
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• 2019

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Textile Coloration and Finishing
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• v.12 no.1
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• pp.52-60
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• 2000

In the prior studies, we reported that the dye uptakes of C. I. Disperse Violet 1 on polyester fiber in hexane and cyclohexane were higher than those in the other solvents, as the number of carbon atoms of alkanes decreased, the dye uptake increased, and the logarithmic plot of the dye uptakes vs. the solubilities of the dye showed that the dye uptakes are inversely proportional to the solubilities. In this study, for Interpretation of dyeing behavior of C. I. Disperse Violet 1 on polyester in alkanes, the thremodynamic parameters of dyeing, such as standard affnity, heat of dyeing(enthalpy change), entropy change, diffusion coefficient, and activation energy of diffusion, were obtained from isotherms and dyeing rates at different temperature. As the number of carbon atoms of alkanes increased, the standard affinity decreased, but the heat of dyeing(enthalpy change) and the entropy change showed larger negative values. These results mean that as the number of carbon atoms of alkanes increases, the dye uptake decreases, but both the fraction of the dye molecules dyed at relatively highly aligned or compact region of polyester fiber and the regularity of dye aggregates in the fiber become increased. As the number of carbon atoms of alkanes increased, the diffusion coefficient decreased, but the activation energy of diffusion increased. In the alkane of larger number of carbon atoms, because the solubility of the dye is higher, the desorption rate of the dye is faster and the diffusion coefficient is smaller than those in the smaller alkanes. But the energy required to separate the dye molecules from the alkane molecules is much higher because the interaction between the alkane molecule and the dye molecule become strong with the number of carbon atoms.

• 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.

• Bulletin of the Korean Chemical Society
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• v.8 no.1
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• pp.31-39
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• 1987

By using a complete rate constant($k_e$) which treats a solvent (water) as a reactant, and a conventional rate constant($k_c$), which ignores the solvent in describing the rate, the parameters ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were introduced. These quantities represent the volume change, the enthalpy change, and the entropy change accompanying the electrostriction which occurs when solvent molecules condense on the activated complex. The authors measured the rates of the solvolysis of benzoyl chloride in water-acetone mixtures at $15^{\circ}$ to $30^{\circ}C$ and 1 bar to 2500 bars. Applying the authors' theory to the experimental results, the parameters, ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were evaluated, and it was found that they are all negative, indicating that water dipoles condense on the activated complex. They also proposed the following equations: ${\Delta}H^{\neq}_c\;=\;{\Delta}H^{\neq}_e\;+\;{\Delta}H^{\neq}_s\;and\; {\Delta}S^{\neq}_c\;=\;{\Delta}S^{\neq}_e\;+{\Delta}S^{\neq}_s\;,\;where\;{\Delta}H^{\neq}_c\;and\;{\Delta}H^{\neq}_c\;and\;{\Delta}S^{\neq}_s $are the activation enthalpy change and the activation entropy change for the conventional reaction rate, respectively, and ${\Delta}H^{\neq}_e$ and ${\Delta}S^{\neq}_e$ are the corresponding quantities for the complete reaction rate. The authors proposed that for the $SN_1$ type, all the quantities, ${\Delta}V^{\neq}_s,\;{\Delta}S^{\neq}_s\;,{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ are comparatively large, and for the $SN_2$ type, these quantities are smaller than for the $SN_1$ type, and occasionally the case ${\Delta}S^{\neq}_e$ < 0 occurs. Using these criteria, the authors concluded that at high temperature, high pressure and for a high water content solvent, the SN_1$ type mechanism predominates whereas in the reversed case the $SN_2$M type predominates.

• Bulletin of the Korean Chemical Society
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• v.8 no.5
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• pp.408-414
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• 1987

The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

• Journal of the Korean Chemical Society
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• v.14 no.1
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• pp.85-89
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• 1970

The rate of the bromine-exchange reaction between gallium bromide and isopropyl bromide in nitrobenzene was measured at 19$^{\circ},\;25^{\circ}$ and 40$^{\circ}C$., using isopropyl 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 isopropyl bromide. The third-order rate constant determined at 19$^{\circ}C$. was 3.2 ${\times}10^{-2}l^2{\cdot}mole^{-2}sec^{-1}$. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.