• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Journal of the Mineralogical Society of Korea
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• v.21 no.4
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• pp.415-423
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• 2008

Earth outer core is composed of iron mainly with some diluent elements, which account for the observed ca. 10% density deficit compared to the pure iron. Among candidates as the light diluents, hydrogen and oxygen were selected, and the thermodynamic stability of the following reaction was calculated; hematite + hydrogen $\to$ goethite + iron. At ambient conditions, Gibb's free energy of this reaction is 12.62 kJ/mol. On increasing pressure at room temperature, it decreases to zero at 0.068 GPa. This energy decreases at constant rate down to 200 GPa, which shows -208.26 kJ/mol at that pressure. From these results, this chemical reaction prefers the reduction environment forming the iron element and iron oxyhydroxide, so possible presence of iron oxyhydroxide with iron at proto-core can not be ruled out.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2325-2329
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• 2013

Second-order rate constants $k_N$ have been measured for reactions of benzyl 2-pyridyl thionocarbonate (4b) and t-butyl 2-pyridyl thionocarbonate (5b) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 4b and 5b have been compared with those reported previously for the corresponding reactions of benzyl 2-pyridyl carbonate (4a) and t-butyl 2-pyridyl carbonate (5a) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and reaction mechanism. The thiono compound 4b is more reactive than its oxygen analogue 4a. The Br${\o}$nsted-type plots for the reactions of 4a and 4b are linear with ${\beta}_{nuc}=0.57$ and 0.37, respectively. The reactions of 4a were previously reported to proceed through a concerted mechanism, while those of 4b in this study have been concluded to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step on the basis of the ${\beta}_{nuc}$ value of 0.37. Enhanced polarizability upon changing the C=O in 4a by C=S has been suggested to be responsible for the reactivity order and the contrasting reaction mechanisms. In contrast, the reactivity of 5a and 5b is similar, but they are much less reactive than 4a and 4b. Furthermore, the reactions of 5a and 5b have been concluded to proceed through the same mechanism (i.e., a concerted mechanism) on the basis of linear Bronsted-type plots with ${\beta}_{nuc}=0.45$ or 0.47. It has been concluded that the strong steric hindrance exerted by the t-Bu in 5a and 5b causes a decrease in their reactivity and forces the reactions to proceed through a concerted mechanism.

• Journal of the Korean Chemical Society
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• v.30 no.4
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• pp.345-351
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• 1986

Monoxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_3\;(bipy)_2\;(NCS)_4]$ in aqueous acetone mixture produces the corresponding dioxo-bridged binuclear molybdenum(V) complex, $MoO_4(bipy)_2(NCS)_2$. The rate of conversion of $[Mo_2O_3(bipy)_2(NCS)_4]$ to $MoO_4(bipy)_2(NCS)_2$ has been measured by spectrophotometric method. The rate of formation of dioxo-bridged binuclear molybdenum(V) complexes with solvent water follows the rate law, rate = k$[Mo_2O_3(bipy)_2(NCS)_4]\;[H_2O]$. The reaction mechanism for the formation of dioxo-bridged complex is discussed. The observed negative volume of activation shows that the complex is strongly attracted to the solvent molecules at transition state.

• Journal of Physiology & Pathology in Korean Medicine
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• v.23 no.6
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• pp.1305-1313
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• 2009

Saengjihwangeum-ja (SJHEJ) was recorded in DongEuiBoGam as being able to be used for treatment of Sogal whose concept had been applied to Diabetes Mellitus (DM). Modification of proteins by long term circulation of glucose leads to the formation of advanced glycation end product(AGE). Recent immunological studies demonstrated that ligation of AGE play an important role in the development of diabetic complications including atherosclerosis, which includes activation, adhesion, and migration of monocytes. Also, AGE and Maillard reaction product(MRP) could augment monocyte inflammatory responses via ligation of AGE receptor. In this study, the effects of SJHEJ extracts on the expression of inflammatory response-related genes such as tumor necrosis factor-$\alpha$, monocyte chemoattractant protein-1, interferon-g-inducible protein-10, and cyclooxygenase-2 in the human monocyte cell line, THP-1 cells. Reverse transcriptase-polymerase chain reaction revealed that SJHEJ had inhibitory effects on the expression of the TNF-a, MCP-1, IP-10, COX2, IL-1b genes in MRP-induced THP-1 cells. Treatment with SJHEJ had reduced reactive oxygen production in THP-1 cells stimulated by MRP. These inhibitory effects might be exerted via prevention of oxidative stress in activated monocytes. In addition, radical scavenging activity of SJHEJ was increased. These results suggest that SJHEJ has a beneficial effects for improve diabetic vascular complication.

• Journal of the Korean Society of Safety
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• v.28 no.3
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• pp.39-43
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• 2013

The present study has been conducted to investigate the fire combustion properties and fire behavior of an IEEE-383 qualified flame retardant cable. The reference reaction rate and reference temperature which are commonly used in pyrolysis model of fire propagation process was obtained by the thermo-gravimetric analysis of the cable component materials. The mass fraction of FR-PVC sheath abruptly decreased near temperature range of $250{\sim}260^{\circ}C$ and its maximum reaction rate was about $2.58{\times}10^{-3}$[1/s]. For the XLPE insulation of the cable, the temperature causing maximum mass fraction change was ranged about $380{\sim}390^{\circ}C$ and it has reached to the maximum reaction rate of $5.10{\times}10^{-3}$[1/s]. The flame retardant cable was burned by a pilot flame meker buner and the burning behavior of the cable was observed during the fire test. Heat release rate of the flame retardant cable was measured by a laboratory scale oxygen consumption calorimeter and the mass loss rate of the cable was calculated by the measured cable mass during the burning test. The representative value of the effective heat of combustion was evaluated by the total released energy integrated by the measured heat release rate and burned mass. This study can contribute to study the electric cable fire and provide the pyrolysis properties for the computational modeling.

• Resources Recycling
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• v.21 no.6
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• pp.32-38
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• 2012

In this study, direct reduction of $ZrO_2$ using liquid calcium was investigated. The influence of molar ratio of Ca and $ZrO_2$, reaction time and temperature on the reduction behavior of $ZrO_2$ was studied. Experiments were conducted in a closed stainless steel chamber under Ar atmosphere during 5 to 60 minutes. Most of the $ZrO_2$ was reduced to Zr in 5 minutes at 1223 K and 3 Ca/$ZrO_2$ molar ratio. The minimum oxygen content in reduced metal Zr was obtained about 0.66 wt% at 1373 K after 30 minutes and 4 Ca/$ZrO_2$ molar ratio. The morphology of zirconium powder obtained was highly affected by the reaction temperature and reaction time.

• Applied Chemistry for Engineering
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• v.29 no.6
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• pp.657-662
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• 2018

In this study, the effect of $Pt/TiO_2$ catalysts on the CO oxidation reaction at room temperature was investigated using various $TiO_2$ supports with different physical properties to compare and evaluate $Pt/TiO_2$ catalysts. Physicochemical properties of the catalyst were alanyzed using XPS, CO-chemisorption, BET, and CO-TPD. As a result, when the active particle diameter was smaller, while the metal dispersion and surface area were larger, the CO room temperature oxidation reaction was better. These physical properties increased the number of active sites, causing the target material to increase the adsorption amount of CO. In addition, when the $O_2$-consumption increased, the CO-room temperature oxidation reaction activity increased due to the excellent oxygen-transferring ability.

• Journal of Korean Society of Water and Wastewater
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• v.33 no.4
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• pp.243-250
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• 2019

This objective of this study was to investigate the degradation characteristics of phenol, a refractory substance, by using a submerged dielectric barrier discharge (DBD) plasma reactor. To indirectly determine the concentration of active species produced in the DBD plasma, the dissolved ozone was measured. To investigate the phenol degradation characteristics, the phenol and chemical oxygen demand (COD) concentrations were evaluated based on pH and the discharge power. The dissolved ozone was measured based on the air flow rate and power discharged. The highest dissolved ozone concentration was recorded when the injected air flow rate was 5 L/min. At a discharge power of 40W as compared to 70W, the dissolved ozone was approximately 2.7 - 6.5 times higher. In regards to phenol degradation, the final degradation rate was highest at about 74.06%, when the initial pH was 10. At a discharged power of 40W, the rate of phenol decomposition was observed to be approximately 1.25 times higher compared to when the discharged power was 70W. It was established that the phenol degradation reaction was a primary reaction, and when the discharge power was 40W as opposed to 70W, the reaction rate constant(k) was approximately 1.72 times higher.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.31 no.2
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• pp.96-101
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• 2021

Developing effective and earth-abundant electrocatalyst for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is critical for the commercialization of a water splitting system. In particular, the overpotential of the OER is relatively higher than the HER, and thus, it is considered that one of the important methods to enhance the performance of the electrocatalyst is to reduce the overpotential of the OER. We report effects of incorporation of metalloid into Ni(OH)2 microcrystal on electrocatalytic activities. In this study, Te incorporated Ni(OH)2 (��Te-Ni(OH)2) were grown on three-dimensional porous NF by a facile solvothermal method with �� = 1, 3 and 5. Homogeneous microplate structure on the NF was clearly observed for the Ni(OH)2/NF and ��Te-Ni(OH)2/NF samples. However, irregular and collapsed nanostructures were found on the surface of nickel foam when Te precursor ratio is (��) over 3. Electrocatalytic OER properties were analysed by Linear sweep voltammetry (LSV) and Electrochemical impedance spectroscopy (EIS). The amount of Te incorporation used in the electrocatalytic reaction was found to play a crucial role in improving catalytic activity. The optimum Te amount (��) introduced into the Ni(OH)2/NF was discussed with respect to their OER performance.