• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.79-85
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• 1984

The ionic association constant(K) of 2,4,6, N-tetramethyl pyridinium iodide (TeMPI) in 95 volume percentage ethanol-water mixture were determined by a modified UV and conductance method at $25^{\circ}C$ to $50^{\circ}C$ under 1 to 2,000 bars. The K values increase with increasing pressure and have maximum value at $40^{\circ}C$. The partial molar volume hange (${\Delta}V$) has relatively small negative value and the absolute values of ${\Delta}$ are minimum at $40^{\circ}C$. The ion size parameter(a) of TeMPI have maximum value at $40^{\circ}C$. {\Delta}H^{\circ}$ values are zero, positive and negative at 40^{\circ}C$, $25^{\circ}C$ and $50^{\circ}C$ respectively. Other thermodynamic parameters such as the changes of standard entropy ({\Delta}S^{\circ}$) and free energy {\Delta}G^{\circ}$ were evaluated. From these experimental results, we came to conclusion that TeMPI is stabilized by the elevation of pressure and that of temperature below $40^{\circ}C$ but weakly dimerized at $40^{\circ}C$ because of the intermolecular hydrophobic interaction of eight methyl groups of two molecules. And it thermally decomposed above $50^{\circ}C$.

• Korean Chemical Engineering Research
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• v.49 no.3
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• pp.367-371
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• 2011

TBAB (tetra-n-butyl ammonium bromide) forms a semi-clathrate with water under atmospheric pressure conditions and recently has attracted great attention due to its usage as a thermodynamic promoter in gas storage and separation process using gas hydrate formation. In this study, we measured the three-phase (hydrate (H) - liquid water ($L_{w}$)-vapor (V)) equilibria of the ternary $CH_{4}$+TBAB+water and $CO_{2}$+TBAB+water mixtures at the TBAB concentrations of 5 and 32 wt% to investigate promoting characteristics of TBAB. The greater promotion effect of TBAB was observed at 32 wt% than at 5 wt%. This result was in good agreement with that from pure TBAB semi-clathrate phase diagram under atmospheric pressure conditions. Through $^{13}C$ NMR analysis of the $CH_{4}$+TBAB semi-clathrate, it was found that $CH_{4}$ molecules are enclathrated in the cages of the double semi-clathrate and the position of resonance peak from encaged $CH_{4}$ molocules in the double semi-clathrate is the same as that from encaged $CH_{4}$ molocules in the pure $CH_{4}$ hydrate of structure I.

• Applied Chemistry for Engineering
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• v.8 no.5
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• pp.777-783
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• 1997

$TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.

• Applied Chemistry for Engineering
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• v.8 no.5
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• pp.796-803
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• 1997

The PVT and $^2H$-NMR characteristic of main-chain dimer liquid crystals having structures such as ${\alpha}$, ${\omega}$-bis[4,4'-cyanobiphenyl) oxy] alkane(CBA-10) were studied. In this work, V-T curves obtained from isobaris measurements on various pressures, volume changes were observed at the nematic-isotropic and nematic-crystal phase transition. The volume changes at the transition exhibit slight odd-even effect with respect to the number of methylene unit n. The values of the$({\Delta}S_{tr})_V$ obtained at the NI transition for CBA-10 was $12.6J/mol{\cdot}K$. The values of $({\Delta}S_{CN})_V$ for the CN transition was estimated on the basis of DSC data : $65.3J/mol{\cdot}K$. For both transition, it was found that the correction about the volume change is significant, ranging from 40 to 60% of the total transition entropy observed under constant pressure. The RIS analysis of the spectra was performed so as to elucidate the conformational characteristics of the spacer in the nematic phase. The conformational entropy changes at both CN and NI interphases were estimated on the basis of the nematic conformations taken from the conformation map as well as those derived from the simulation. The estimated conformational entropy change values were then compared with the corresponding constant-volume entropies obtained from PVT measurements. The correspondence between both entropy values was found to be quite good in consideration of the uncertainties involved in both experiment and calculations.

• Journal of the Mineralogical Society of Korea
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• v.12 no.1
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• pp.43-53
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• 1999

The medical mineral menas a single mineral or a complex of minerals. It is natural material. using the medical action of he major or the minor elements, and traditional medicine stuff which has been used since long time ago. Jusa, cinnabar as the mineral name, is the product of the hydrothermal process. It is used to relax the body and cure high blood pressure, apoplexy and cardiopathy. Jusais the major component of "An shin hwan" and "Woo hwang chung shim hwan" nowadays because it has such an excellent calm effect. In addition, it is used to cure cancers such as esophageal cancer and gastric cancer. Jusa composed of mercuric sulfide causes mercury poisoning such as Minamata disease. It is dealt with mineralogical property and chemical composition medical stuff in Korea and China, as well asmercury poisoning and medical action of Jusa in this study. In order to predct accumulation of the interior of the body of the major and minor elements in Jusa, leaching experiment of Jusa by artificial gastric juice was done as well as thermodynamic reaction modelling to know concentration of each species of body fluid. The minor elements of 24 species such as As, Pb, Cd, a and Fe by leaching reaction of Jusa and artificial gastric juice were leached. We can know the fact that as is less than 1 ppm, Hg is less than 25 ppm and Cd and m are not detected. In addition, mercury exists as species of Hg2+, HgCl+, HgCl2, HgCl3-, HgCl42-, HgClOH, HgS(H2S)2, Hg(HS)3-, HgS22-, HgOH and Hg(OH)2 by reaction modelling between Jusa and artificial gastric juice. The concentration of sulfide complexes is 24.2 ppm and that of others is less than 10 ppm. According to increasing pH, the concentration of HgS(H2S)2, Hg(HS)3+, HgS22- and Hg(OH)2 increases, whereas the concentration of HgCl+, HgCl2, HgCl3- and HgCl42- decreases. Therefore, Jusa is very useful for the development of new medicine because it is possible to predict formation of the body species and species accumulation on mercury known as a toxic element and concentration changes of toxicity and efficiency.city and efficiency.

• Resources Recycling
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• v.15 no.3 s.71
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• pp.58-65
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• 2006

The applicability of the waste pulp which produced in the paper recycling process as an adsorbent for the treatment of $Ni^{2+}$ ion in wastewater has been investigated taking the initial concentration of adsorbate, temperature, the amount of adsorbent, and solution pH as the experimental variables. In addition, the effect of the concentration of coexisting solute and pre-treatment of adsorbent on the adsorbability of $Ni^{2+}$ ion were also examined. The electrokinetic potential of waste pulp was observed to be positive below pH 7.8 and negative above this pH. The adsorption reaction of $Ni^{2+}$ ion reached its equilibrium within 4 hours after the reaction was initiated and the adsorbed amount of adsorbate was found to increase with its initial concentration. The adsorbability of $Ni^{2+}$ was raised with temperature so that its adsorption reaction was considered to be exothermic, which was substantiated by thermodynamic calculation. Also, the adsorbed amount of $Ni^{2+}$ was raised with the amount of waste pulp and with pH in the range of pH $3{\sim}6$. This behavior of the adsorption of $Ni^{2+}$ according to the solution pH was well agreed with the electrokinetic characteristics of waste pulp in solution. The amount of coexisting solute was observed to reversely affect on the $Ni^{2+}$ adsorption onto waste pulp under the experimental conditions. With regard to the pre-treatment of adsorbent with NaOH, the adsorbability of $Ni^{2+}$ was increased with the concentration of NaOH to a certain extent. However, it was found to decrease contrarily when the concentration of NaOH became too high.

• Analytical Science and Technology
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• v.27 no.2
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• pp.79-91
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• 2014

Solubility data of carbon dioxide ($CO_2$) in 1-butyl-3-methylpiperidinium bis(trifluoromethylsulfonyl)imide ($[bmpip][Tf_2N]$) ionic liquid are presented at pressures up to about 30 MPa and at temperatures between 303 K and 343 K. As far as we know, the data on the $CO_2$ solubility in the $[bmpip][Tf_2N]$ ionic liquid have never been reported in the literature by other investigators. The solubilities of $CO_2$ were determined by measuring the bubble point or cloud point pressures of the $CO_2+[bmpip][Tf_2N]$ mixtures with various compositions using a high-pressure equilibrium apparatus equipped with a variable-volume view cell. To observe the effect of the cation composing the ionic liquid on the $CO_2$ solubility, the $CO_2$ solubilities in $[bmpip][Tf_2N]$ used in this study were compared with those in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide ($[bmim]Tf_2N]$). As the equilibrium pressure increased, the $CO_2$ solubility in $[bmpip][Tf_2N]$ increased sharply. On the other hand, the $CO_2$ solubility decreased with increasing temperature. The mole fraction-based $CO_2$ solubilities were almost the same for both $[bmpip][Tf_2N]$ and $[bmim][Tf_2N]$, regardless of temperature and pressure. The phase equilibrium data for the $CO_2+[bmpip][Tf_2N]$ systems have been correlated using the Peng-Robinson equation of state.

• Applied Chemistry for Engineering
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• v.5 no.3
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• pp.406-412
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• 1994

The ion-exchange properties of $Ca^{2+}$ and $Mg^{2+}$ ions have been studied in ${\delta}-Na_2Si_2O_5$ synthesized from water glass. Results show that optimum temperature for synthesis of ${\delta}-Na_2Si_2O_5$ was $725^{\circ}C$. Ion-exchange isotherms for $Ca^{2+}$ and $Mg^{2+}$ exchange for $Na^+$ in the synthetic ${\delta}-Na_2Si_2O_5$ show that the ion-exchange capacity of magnesium is better than that of calcium, and the ion-exchange of magnesium is less sensitive for temperature than that of calcium. When initial pH of solution is increased between 2 and 6, the ion-exchange capacities of magnesium and calcium decrease a little. However, they are almost constant above pH 6 because of alkali buffer effect of ${\delta}-Na_2Si_2O_5$. In the thermodynamic studies, it was found that Gibbs free energies of reaction of calcium ion-exchange are larger than those of magnesium ion-exchange with inverse order of selectivity. The standard enthalpy and entropy of reaction of calcium ion-exchange are larger than those of magnesium ion-exchange.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2004.09a
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• pp.121-121
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• 2004

The groundwater in the Pocheon area occurs from both a fractured bedrock aquifer in igneous and metamorphic rocks and an alluvial aquifer with a thickness of <50 m, and forms a major source of domestic and agricultural water supply. In this study, we performed a hydrogeochemical study in order to identify the control of geochemical processes on groundwater quality. For this study, groundwater level and physicochemical parameters (EC, Eh, pH, alkalinity) were monitored once a month from a total of 150 groundwater wells between June 2003 to August 2004. A total of 153 water samples (13 surface water, 66 alluvial groundwater, 74 bedrock groundwater) were also collected and analyzed in February 2004. Groundwater chemistry in the study area is very complex, depending on a number of major factors such as geology, degree of chemical weathering, and quality of recharge water. Hydrochemical reactions such as the leaching of surficial and near-solace soil salts, dissolution of calcite, cation exchange, and weathering of silicate minerals are proposed to explain the chemistry of natural groundwater. Alluvial groundwaters locally have very high TDS concentrations, which are characterized by their chloride(nitrate)-sulfate-bicabonate facies and low Na/Cl ratio. Their grondwater levels are highly fluctuated according to rainfall event. We suggest that high nitrate content and salinity in such alluvial groundwaters originates from the local recharge of sewage effluents and/or fertilizers. Likewise, high concentrations of nitrate were also locally observed in some bedrock groundwaters, suggesting their effect of anthropogenic contamination. This is possibly due to the bypass flow taking place through macropores. Tile degree of the weathering of silicate minerals seems to be a major control of the distribution of major cations (sodium, calcium, magnesium, potassium) in bedrock groundwaters, which show a general increase with increasing depth of wells. Thermodynamic interpretation of groundwater chemistry shows that the groundwater in the study area is in chemical equilibrium with kaolinite and Na-montmorillonite, which indicates that weathering of plagioclase to those minerals is a major control of hydrochemistry of bedrock groundwater. The interpretation of the molar ratios among major ions, as well as the mass balance calculation, also indicates the role of both dissolution/precipitation of calcite and Ca-Na cationic exchange as bedrock groundwaters evolves progressively.

• Korean Chemical Engineering Research
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• v.48 no.6
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• pp.776-783
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• 2010

Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. The activities of these catalysts for the partial oxidation of methane was investigated at 1 atm and $CH_4/O_2=2.0$ in the temperature range of $450{\sim}650^{\circ}C$. The reaction activity of $Ni/Al_2O_3$ and $Co/Al_2O_3$ catalysts with different loading was investigated. And the beneficial effects of Ni addition to $Co/Al_2O_3$ and the promotional effects of Ce and La addition to $Ni/Al_2O_3$ and $Co/Al_2O_3$ were investigated. These catalysts were characterized by XRD and SEM/EDX. Comparing catalyst loadings, 10 wt% Co and 10 wt% Ni were found to be optimal at the experimental conditions. The 10 wt% $Ni/Al_2O_3$ and 10 wt% $Co/Al_2O_3$ catalysts in partial oxidation of methane showed $CH_4$ conversions and CO selectivity close to the thermodynamic equilibrium levels, but showed lower $H_2$ selectivity than equilibrium level. The addition of Ni to $Co/Al_2O_3$ exhibited higher $H_2$ selectivity but beneficial effect was not observed in the $CH_4$ conversion. Addition of Ce to $Co/Al_2O_3$ and addition of La to $Ni/Al_2O_3$ a improved the $CH_4$ conversion level and $H_2$ selectivity.