• 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.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.327-332
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• 1996

The rates of solvolylsis of methyl chloroformate, phenyl chloroformate and 1-adamantyl derivatives in binary solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters were estimated from the rate constants. The activation volume (${\Delta}V_o^{\neq}$) and the activation entropy (${\Delta}S^{\neq}$) are both negative, but the activation enthalpy (${\Delta}H^{\neq}$) is positive. This behavior is discussed in terms of electrostriction of solvation. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies. From these results, it could be estimated that the solvolyses of 1-adamantyl fluoroformate (in aqueous TFE) and 1-adamantyl tosylate have pathway involving unimolecular reaction, while the reaction of methyl chloroformate, phenyl chloroformate and 1-adamantyl fluoroformate (in aqueous alcohol) proceed through a bimolecular reaction.

• Textile Coloration and Finishing
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• v.12 no.6
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• pp.372-379
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• 2000

Four kinds of neutral salts with different cations, LiCl, NaCl, KCl, and CsCl, were added to the dye bath to accurately understand the effect of cations on the reactive dyeing of silk with C. I. Reactive Black 5. The cations of salts added lowered the negative surface potential of the silk, improving equilibrium adsorption and the accessibility of the dyestuff to the fiber greatly and speeding up the dyeing rate in the order of $Li^+>Na^+>K^+>Cs^+$. The activation energy$(E_a)$ for the dyeing was in the order of$Li^+>Na^+>K^+>Cs^+$ but the activation free energy$(\Delta{G}^*)$, or the real energy barrier for the reaction, was in the order of $Li^+>Na^+>K^+>Cs^+$ because the degree of the contribution of E$^{a}$ to the activation entropy$(\Delta{S}^*)$ was $Li^+>Na^+>K^+>Cs^+$. It was found from this result that LiCl had the strongest lowering effect on the negative surface potential of silk. The decrease in $\Delta{S}^*$ should be attributed to the loosely bonded activated complex of dyestufffs, cations and fiber molecules at transition state. It was clarified from the Bronsted equation that salts had the ionic strength effect and the specific salt effect on the reactive dyeing.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.582-587
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• 1989

Rates for aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ ion in aqueous acidic solution have been measured by spectrophotometric method at various temperatures and pressures. The volume of activation for the aquation is small negative and lies in the limited range -2.76 ∼ -3.65 $cm^3mol^{-1}$. The entropy and compressibility coefficient of activation are small negative values. From the results of thermodynamic activation parameters, it can be inferred that the aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ ion proceeds through an associative interchange($I_a$) mechanism.

• 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.42 no.2
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• pp.150-155
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• 1998

Kinetic studies on the reaction of isoquinoline with para-substituted benzylbromides were conducted under various pressures (1 ~1000 bar) in acetonitrile. From the rate constants obtained, the activation parameters such as$\DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq}$ and Ea were evaluated. Reaction rate increasing the pressure and temperature. The activation compressibility coefficient and the activation entropy showed negative values. From the substituent effect and the results, it was found that the reaction proceeds through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

• 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.

• International Journal of Advanced Culture Technology
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• v.5 no.2
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• pp.82-89
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• 2017

The range of problems that can be handled by the activation of big data and the development of hardware has been rapidly expanded and machine learning such as deep learning has become a very versatile technology. In this paper, mnist data set is used as experimental data, and the Cross Entropy function is used as a loss model for evaluating the efficiency of machine learning, and the value of the loss function in the steepest descent method is We applied the GradientDescentOptimize algorithm to minimize and updated weight and bias via backpropagation. In this way we analyze optimal reliability value corresponding to the number of exercises and optimal reliability value without overfitting. And comparing the overfitting time according to the number of data changes based on the number of training times, when the training frequency was 1110 times, we obtained the result of 92%, which is the optimal reliability value without overfitting.

• KSII Transactions on Internet and Information Systems (TIIS)
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• v.14 no.8
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• pp.3519-3533
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• 2020

Tuberculosis is a chronic and delayed infection which is easily experienced by young people. According to the statistics of the World Health Organization (WHO), there are nearly ten million fell ill with tuberculosis and a total of 1.5 million people died from tuberculosis in 2018 (including 251000 people with HIV). Tuberculosis is the largest single infectious pathogen that leads to death. In order to help doctors with tuberculosis diagnosis, we compare the tuberculosis classification abilities of six popular convolutional neural network (CNN) models in the same data set to find the best model. Before training, we optimize three parts of CNN to achieve better results. We employ sigmoid function to replace the step function as the activation function. What's more, we use binary cross entropy function as the cost function to replace traditional quadratic cost function. Finally, we choose stochastic gradient descent (SGD) as gradient descent algorithm. From the results of our experiments, we find that Densenet121 is most suitable for tuberculosis diagnosis and achieve a highest accuracy of 0.835. The optimization and expansion depend on the increase of data set and the improvements of Densenet121.

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.50-57
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• 1989

A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.