• Korean Chemical Engineering Research
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• v.57 no.2
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• pp.198-204
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• 2019

For the removal of carbon dioxide from the chemical process, a chemical absorption method is typically used industrially. Development of new processes for the removal of carbon dioxide by the chemical absorption method has been developing new absorbents by using various absorbents. Thermodynamic data of the sorbent mixture in the new process design using hybrid absorbent is essential to reduce the equipment cost and operating costs of the process. In this study, densities of water+diisopropanolamine (DIPA), DIPA+MDEA(Methyldiethanolamine) binary systems and Water+DIPA+MDEA ternary system were measured over the full range of composition at temperatures from 303.15 K to 333.15 K by using an Anton Paar digital vibrating tube densimeter (DMA4500). The experimental excess volumes have been obtained from the experimental density results and have been fitted using the Redlich-Kister-Muggianu expression. The parameters obtained from the binary excess volume data were used for the correlation of ternary system with one additional ternary parameter for each isotherm. All investigated binary and ternary systems are completely miscible, because the values of excess volume are negative under the examined conditions.

• Journal of the Korean Chemical Society
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• v.29 no.3
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• pp.239-246
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• 1985

The equilibria of chemical reaction between [Cu(dl-trans-[14]-diene)]$^{2+}$ and L$^{n-}$(S$_2$O$_3^{2-}$, SCN$^-$, I$^-$, NO$_2^-$) ions were studied by the spectrophotometric method in the range of 15 to 35$^{\circ}C$ and 1 to 1500bar. The equilibrium constants(K) for L$^{n-}$ = S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at 25$^{\circ}C$ and 1500bar were 3.0, 1.9, 0.6 and 0.5, respectively. The values of K decreased with increasing pressure and temperature. From the temperature effect on equlibrium constant, the thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$) of reaction were evaluated and the reactions of [Cu(dl-trans-[14]-diene)]2+ ion with S$_2$O$_3^{2-}$, SCN$^-$ and I$^-$ except NO$_2^-$ ion were exothermic. The volume changes of reaction(${\Delta}$V) had positive values for all the used anions. The values of ${\Delta}$V in cm$^3$/mole for S$_2$O$_3^{2-}$ ion at 1,500, 1,000 and 1,500bar were 26, 22, 19 and 16, and those for S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at atmospheric pressure 26, 30, 64 and 45, respectively. Bonding character between Cu(Ⅱ)-complex ion and L$^{n-}$ was discussed by comparing both the equlibrium constants experimentally determined and those calculated according to Fuoss's ion-pair equation in case of S$_2$O$_3^{2-}$ ion.

• Journal of the Korean Electrochemical Society
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• v.5 no.3
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• pp.131-142
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• 2002

The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

• Journal of the Korean Electrochemical Society
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• v.10 no.2
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• pp.132-140
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• 2007

The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

• 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.55 no.5
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• pp.660-667
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• 2017

Equilibrium data of the mixture is essential in the design and operation of separation equipment such as distillation or extraction in chemical processes. These equilibrium data can be obtained through experiments or by calculations using the known binary parameters and the thermodynamic models. Generally, to obtain these parameters, phase equilibrium experimental data such as gas-liquid and liquid-liquid are used. In this study, the excess enthalpy of the mixture was measured using the flow type microcalorimeter which is a simpler method than phase equilibria experiments, and the parameters of various theories were obtained by using this data. In order to investigate the relationship between carbon chain length, enthalpy and binary parameters in the alkane system, excess enthalpies for the n-hexane + alkane (n-pentane, n-heptane, n-octane and n-dodecane) were measured at 298.15 K and the banary interaction parameters of Wilson, NRTL, and UNIQUAC were obtained from the experimental data. In addition, we wanted to obtain basic information on the interaction and association phenomena of the system including electrolyte applicable to various fields by using the excess enthalpy experimental data and the existing theory. First, we investigated the excess enthalpy for the NaOH / Water / Ethanol system as a basic experiment and examined the applicability using the electrolyte-NRTL (eNRTL) theory.

• Applied Chemistry for Engineering
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• v.9 no.6
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• pp.829-834
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• 1998

Concerned with environmental issue, a new decomposition method for CFCs that caused the destruction of ozone layer was proposed. Using thermal plasma process, CFC113 decomposed completely. In order to quantify the tendency in decomposition and recombination of CFC113, thermodynamic equilibrium calculations were performed. The calculation was conducted with CFC113, $H_2$, $O_2$ at 1 atm and 300 K~5000 K. In the experiment, products which are generated after decomposition in the plasma were examined by varying reacting gases($H_2$, $O_2$) flow rates and the changes of inside diameters of quenching tubes. Decomposition products were analyzed using Gas Chromatograph. The results are very promising with a decomposition efficiency greater than 99.99%. As to CFC113/$H_2$=1/3, conversion to CO decreased with increasing $O_2$ ratio. When CFC113/$O_2$=1/1, 1/1.5 and 1/2, conversion to CO increases above $H_2$ ratio of 3. The change of CO conversion is not sensitive to power changes. As total flow rate increased, CO conversion was slightly decreased. When the inside diameter of the quenching tube was changed from 8mm into 4mm, CO conversion was increased due to enhanced quenching rate.

• Korean Journal of Soil Science and Fertilizer
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• v.36 no.4
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• pp.210-217
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• 2003

An alternative method to the empirical approach such as Langmuir and Freundlich model, surface complexation model using thermodynamic database is used to simulate adsorption behavior of cadmium for oxide minerals. Sorption of cadmium onto amorphous silica ($SiO_2$) and synthetic goethite (${\alpha}$-FeOOH) at various conditions of pH, initial cadmium loading, oxide concentration, and ionic strength, were investigated. For both oxide minerals, increasing cadmium concentration resulted in right shifting of the sorption curve of cadmium as the function of pH. The $pH_{50}$, where 50% of cadmium sorbed, of goethite (pH 5.25) was much smaller than that of the silica (pH 7.83). The sorption of cadmium onto both minerals were not affected by the background ion strength from $10^{-1}$ to $10^{-2}$ M of $KNO_3$. It indicated that the binding affinity of goethite surface for cadmium is much stronger than that of silica. The strong affinity of oxide mineral for cadmium can be explained by the existence of coordination or covalent bond between cadmium and surface of it.

• Membrane Journal
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• v.17 no.3
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• pp.219-232
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• 2007

The polyethersulfone(PES)-titanium oxide($TiO_2$) hybrid membranes were prepared by immersion precipitation phase inversion method. The casting solution for the preparation of $PES-TiO_2$ hybrid membrane was provided by adding $TiO_2$ nano particles into the basis polymer solution of 14 wt% and 20 wt% PES/N-methyl-2-pyrrolidone(NMP). The $TiO_2$ loading [wt% ($TiO_2/NMP$)] in eating solution was varied from 0 to 60 wt%. Membrane performance and morphological change of the resulting $PES-TiO_2$ hybrid membranes were discussed in aspect of $TiO_2$ loading, by viscosity, coagulation value and light transmittance of the casting solution, measurement of tensile strength, pore size and contact angle, surface and cross sectional SEM images of the hybrid membrane, and ultrafiltration experiments using the hybrid membrane. According as increase of $TiO_2$ loading in the casting solution, viscosity is increased and coagulation value becomes lower, therefore the thermodynamic instability of the casting solution is increased. It is found that when $TiO_2$ loading is increased, 1) precipitation rate becomes faster while instantaneous demixing is maintained, 2) pure water flux, membrane pore size and compaction stability of the resulting membranes are increased, 3) tensile strength and contact angle are decreased. Dead-end ultrafiltration of bovine serum albumin(BSA) solution using the hybrid membrane shows that membrane performance(flux of BSA solution) enhanced up to 7 times compared with the results obtained using the pure PES membrane(not containing $TiO_2$ particle), due to the increase of hydrophilicity.

• Proceedings of the Korean Society of Applied Pharmacology
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• 1997.04a
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• pp.116-116
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• 1997

Complex formation of practically insoluble dexamethasone dipropionate (DDP) with ${\beta}$-cyclodextrin (${\beta}$-CD), dimethyl-${\beta}$-cyclodextrin (DMCD), trimethyl-${\beta}$-cyclodextrin (TMCD), 2-hydroxypropyl-${\beta}$-cyclodextrin (HPCD) and sulfobutyl ether ${\beta}$-cyclodextrin (SBCD) in water was investigated by solubility method at various temperatures. Water solubility of DDP was found to be 1.78 $\mu\textrm{g}$/$m\ell$ at 37$^{\circ}C$. Propylene glycol (PG)-water cosolvent increased the solubility of DDP, but the solubilization was not sufficient (8.93 $\mu\textrm{g}$/$m\ell$ in 20% PG). The addition of CD markedly increased the solubility of DDP in water, and A$\sub$L/ type phase solubility diagrams were obtained with ${\beta}$-CD, TMCD, HPCD and SBCD, where the apparent stability constants of the soluble complexes at 25$^{\circ}C$ were determined to be 1388, 216, 1054, and 1992 M$\^$-1/, respectively. However, DMCD remarkably increased the solubility of DDP, and showed an A$\sub$P/ type diagram, suggesting that DMCD forms a soluble complex of high order with DDP. The stability constant for the DDP-DMCD complex at 25$^{\circ}C$ was determined to be 19132 M$\^$-1/. The thermodynamic parameters were calculated for the inclusion complex formation in aqueous solution. CD (1${\times}$10$\^$-2/M) remarkably decreased the partition coefficients of DDP between isopropyl myristate/water in the order of TMCD < ${\beta}$-CD < HPCD < SBCD < DMCD, and in squalane/water system in the order of HPCD < TMCD < ${\beta}$-CD < DMCD < DMCD $\leq$ SBCD. This finding represents that, in a o/w type cream, cyclodextrin complexation with DDP may result in high concentration of DDP in aqueous phase. The permeation of DDP through a cellophane membrane was highly suppressed by the addition of CD, and the degree of suppression was different among CDs, indicating that CD may control the skin permeation of DDP. The dissolution rates of solid dispersions with CDs were much faster than those of drugs alone and corresponding physical mixtures. All DDP-CD solid dispersions exceeded the equilibrium solubility. Consequently these results suggest that complex formation of DDP with CDs may provide useful means to markedly enhance the solubility, and CDs are useful in the semi-solid preparations such as creams and gels for topical application.