• Journal of the Korean Applied Science and Technology
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• v.22 no.1
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• pp.50-55
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• 2005

A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of $Na^+$ and $Ca^{2+}$ appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{3}$. As the result, $Na^+$ and $Ca^{2+}$ are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{4}$was found to be somewhat selective for $Na^+$ over $Li^+$ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid $\underline{4}$, $Ca^{2+}$ and $Sr^{2+}$ are the appropriate sizes, but lager $Ba^{2+}$ may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.

• Journal of the Korean Applied Science and Technology
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• v.22 no.3
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• pp.219-227
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• 2005

Competitive solvent extraction of the mixure of alkali metal and alkaline earth cation from water into organic solvent containing the crown ether carboxylic acid and anlogous crown ether phosphonic acid was investigated as follows. The lipophilic group is found to strongly influence to the selective extraction in the mixed systems from only alkali metal cation for sym-(n-decyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ to mostly alkaline earth metal cation for sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxyacetic acid $\underline{3}$. Monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{2}$. and monoethyl-sym- bis]4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{4}$ showed good selectivity for $Na^+$ over $Mg^{2+}$, the second extracted ion. Structural variation in the crown ether phosphonic acid somewhat was influenced to the extraction selectivity in the mixed systems. when variation of the ionized group is influenced in the mixed systems, the selectivity of $Na^+$ as the second extracted ion was much better crown ether carboxylic acid $\underline{1}$ than crown ether phosphonic acid $\underline{2}$, while the efficiency of $Na^+$ extraction was better $\underline{2}$ (83% total loading) than $\underline{1}$ (32%).

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2669-2674
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• 2012

Crown ether is one of well-known host molecules and able to selectively sequester metal cation. We employed M06-2X density functional theory with IEFPCM and SMD continuum solvation models to study selectivity of dibenzo-18-crown-6-ether (DB18C6) for alkaline earth dications, $Ba^{2+}$, $Sr^{2+}$, $Ca^{2+}$, and $Mg^{2+}$ in the gas phase and in aqueous solution. $Mg^{2+}$ showed predominantly strong binding affinity in the gas phase because of strong polarization of CO bonds by cation. In aqueous solution, binding free energy differences became smaller among these dications. However, $Mg^{2+}$ had the best binding, being incompatible with experimental observations in aqueous solution. The enthalpies of the dication exchange reaction between DB18C6 and water cluster molecules were computed as another estimation of selectivity in aqueous solution. These results also demonstrated that $Mg^{2+}$ bound to DB18C6 better than $Ba^{2+}$. We speculated that the species determining selectivity in water could be 2:1 complexes of two DB18C6s and one dication.

• Bulletin of the Korean Chemical Society
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• v.16 no.8
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• pp.716-720
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• 1995

• Applied Chemistry for Engineering
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• v.16 no.6
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• pp.857-864
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• 2005

Dealuminated and alkali/alkaline-earth metal exchanged Y-type and ZSM-5 zeolites were prepared as catalytic materials. Comparing with the composition of starting material, the magnitude of Si/Al ratio was increased after dealumination and cation exchange process. The ratio of Si/Al on surface was appeared to be larger than that in bulk. The destruction of basic frame in catalysts observed was understood to be due to a detachment of aluminum, which results in reducing framework while increasing non-framework. This phenomenon becomes more serious with increasing time of steam treatment and even more significant for the cation exchanged catalysts. The desorption peaks of the NO-TPD profiles taken after dealumination and cation exchanged Y-type and ZSM-5 zeolites shifted to the low temperature region. It was also found that the longer the steam treatment time, the degree of shift toward low temperature region was increased. The catalytic activities are dependent on the nature of cation exchanged, the ratio of Si/Al and the ratio of framework/non-framework by a change in basic frame.

• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.351-359
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• 1992

Interaction of xenon with alkaline-earth cations in Y zeolite supercage was studied by xenon adsorption and $^{129}Xe$ NMR experiments. The CaY and the BaY samples were prepared by exchanging $Ca^{2+}$ and $Ba^{2+}$ into a high-purity NaY zeolite. Xenon adsorption isotherms of these samples were obtained by using a conventional volummetric gas adsorption apparatus in the range of 260 to 320 K and the chemical shift in the $^{129}Xe$ NMR spectrum of the adsorbed xenon was measured at 296 K. The chemical shift against pressure was quantitatively explained assuming that the xenon gas exchanged very rapidly between various adsorption sites consisting of zeolite-framework surface and alkaline-earth ion. From this analysis, it was found that the alkaline-earth ion adsorbed xenon more strongly than $Na^+$ ion and zeolite-framework surface. Baring on the difference of the adsorption strength, the number of the alkaline-earth cations present in the zeolite supercage could be estimated by analyzing the adsorption isotherm.

• Journal of the Korean Chemical Society
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• v.17 no.6
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• pp.416-423
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• 1973

Formation of the complexes of alkaline earth metal ions with malonate and o-phthalate ions in aqueous, ethanol-water and acetone-water solutions (20% by volume) was studied at room temperature by the equilibrium ion exchange technique. This technique involved the measurements of distribution of radioactivity between cation exchange resin(Ion Exchange Resin CGC 241) and solution phases after the radioactive metal ions were equilibriated with the cation exchange resin in the presence of malonate or o-phthalate ions of varying concentrations. The pH of the solutions was controlled to 7.2~7.5, and the ionic strength of the solutions was kept at 0.10~0.11. The results of the present study indicated that the alkaline earth metal ions formed one-to-one complexes with the dibasic organic acids in all solvent systems examined. The present study showed that the relative stabilities of the complexes increased in the order: $Ba^{++}\;<\;Sr^{++}\;<\;Ca^{++}$ complexes. It was also observed that the relative tendency of the o-phthalate ion for the complex formation was somewhat greater than that of malonate ion in each solvent system. Furthermore, it was noted that the complexes were formed more readily in the mixed solvent than in the aqueous solution.

• Journal of the Korean Chemical Society
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• v.15 no.2
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• pp.45-48
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• 1971

The various eluents have been used for the separations of alkaline earth metals by elutions through cation exchange resin column by many investigators. We find, the mixed solution of 1M HAc and 1M NaAc (pH 4.75) is the best eluent for this purpose, becouse the one step elution through 7cm Dowex 50w${\times}$8(100~200mesh) resin column with this eluent, gives the quantitative separation. When 2M NaAc is used as a eluent Sr(II) and Ba(II) is separated easily without any contamination of Mg(II) andCa(II). The Ca-Pb alloy which is composed of Cu, Ca, Sr, Ba and abundance of Pb metal is separated quantitatively into its components by the two step elution with 0.3M HAc + 0.3M NaAc(PH 4.75) and 0.5M HAc + 0.5M NaAc(PH 4.75) as eluents through 10cm resin column.

• Journal of the Korean Chemical Society
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• v.38 no.2
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• pp.129-135
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• 1994

Acyclic polyether dicarboxylic acid have been studied as metal cation carriers in a bulk liquid membrane system. The proton-ionizable ligands feature allows the coupling of a cation transport to reverse proton transport. This feature offers promise for the effective separation and concentration of metal cations with the metal cation transport being driven by a pH gradient. Metal cation transport increased regularly with increasing hydroxide($H^-$) concentration of source phase and with proton($H^+$) concentration of receiving phase. Competitive transport by the acyclic polyether dicarboxylic acids is selective for calcium ion over other alkaline-earth cations.

• Journal of the Korean Chemical Society
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• v.27 no.2
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• pp.127-132
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• 1983

The catalytic activity of ZSM-5 catalyst for the disproportionation of toluene is dependent on the type of cation exchanged, the degree of ion-exchange and the reaction temperature. The activity increases in the order of alkaline-, alkali earth-, hydrogen, and rare-earth-exchanged ZSM-5 and decreases with increasing degree of cation exchange. Among the ion-exchanged ZSM-5 catalyst, only Cs-ZSM-5 shows predominant selectivity for p-xylene. The selectivity increases with increasing degree of $Cs^+$-exchange and decreasing reaction temperature. This phenomenon is interpreted in terms of shape selectivity arising from the partial blocking of channel intersections by large cesium ions.