• Title/Summary/Keyword: cryptand

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Interaction of the Post-transition Metal Ions and New Macrocycles in Solution

  • Jung, Oh-Jin
    • Bulletin of the Korean Chemical Society
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    • v.14 no.6
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    • pp.687-691
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    • 1993
  • Complexation of $Cd^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions with four cryptands were studied by potentiometry and solution calorimetry in various weight percent methanol-aqueous solvent at 25${\circ}$C under $CO_2$free nitrogen atmosphere. The stabilities of the complexes were dependent on the cavity size of macrocycles. The $Hg^{2+}$ ion stability constants are higher than those of $Cd^{2+}\;and\;Pb^{2+}$ ion. All the cryptands formed complexes having 1 : 1 (metal to ligand) mole-ratio except for $Hg^{2+}-L_1$ (cryptand 1,2b: 3,5-benzo-9,14,17-trioxa-1,7-diazabicyclo-(8,5,5) heptadecane) and $Cd^{2+}-L_2$ (cryptand 2,2b: 3,5-benzo-10,13,18,21-tetraoxa-1,7-diazabicyclo (8,5,5) eicosane) complexes. $Hg^{2+}-L_1$ complex was a sandwitch type, and the $Cd^{2+}-L_2$ complex showed two stepwise reactions. Thermodynamic parameters of the $Cd^{2+}-L_2$ complex were $6.08(log\;K_1)$, -7.28 Kcal/mol $({\Delta}H_1)$, and $4.78\;(log\;K_2)$, -4.62 Kcal/mol $({\Delta}H_2)$, respectively, for 1 : 1 and 2: 1 mole-ratio. The sequences of the selectivity were increased in the order of $Hg^{2+}\;>Pb^{2+}\;>Cd^{2+}$ ion for $L_3\;and\;L_4$ macrocycles, and the $L_2$-macrocycle has a selectivity for $Cd^{2+}$ ion relative to $Zn^{2+},\;Ni^{2+},\;Pb^{2+}\;and\;Hg^{2+}$ ions. Thus, it is expected that the $L_2$ can be used as carrier for seperation of the post transition metals by macrocycles-mediated liquid membrane because $L_2$ is not soluble in water, and the difference of stability constants of the metal complexes with $L_2$ are large as compared with the other transition metal complexes. The $^1H\;and\;^{13}C-NMR studies indicated that the nitrogen atoms of cryptands have greater affinity to the post transition metal ions than the oxygen atoms, and that the planarities of the macrocycles were lost by complexation with the metal ions because of the perturbation of ring current of benzene molecule attached to macrocycles and counter-anions.

Adsorption of Metal Ions on Synthetic Resin with Styrene Hazardous Materials in Water Fire Extinguishing Agent (물 소화약제에서 스타이렌 위험물을 포함한 합성수지에 의한 금속 이온들의 흡착)

  • Lee, Chi-Young;Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.21 no.2
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    • pp.142-147
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    • 2010
  • Cryptand resins have been synthesized from 1-aza-18-crown-6 macrocyclic ligand attached to styrene (2th petroleum in 4th class hazardous materials) divinylbenzene copolymer with crosslinkage of 1%, 2%, 10%, and 18% by substitution reaction. The synthesis of these resins was confirmed by the content of chlorine, element analysis, surface area (BET), and IR-spectroscopy. The effects of pH, time and crosslinkage on adsorption of metal ion from water fire extinguishing agentby synthetic resin adsorbent were investigated. Metal ions showed a great adsorption over pH 3 and adsorption equilibriumof metal ions was about two hours. The adsorption selectivity determined in water was in the increasing order of sodium ($Na^{1+}$) > zinc ($Zn^{2+}$) > chromium ($Cr^{3+}$) ion. The adsorption was in the order of 1%, 2%, 10%, and 18% crosslinkage resin.

A Study on Resin Synthesis and Adsorption Characteristics for Separation and Recovery of U(VI) (우라늄(VI)의 분리회수를 위한 수지합성과 흡착특성에 관한 연구)

  • 강영식;노기환
    • Journal of environmental and Sanitary engineering
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    • v.14 no.1
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    • pp.31-41
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    • 1999
  • Several new ion exchange resins have been synthesized from chloromethyl styrene-1, 4-di-vinylbenzene with 1%, 2%, 5% and 10%-crosslinking and macrocyclic ligands of cryptand type by interpolymerization method. The adsorption characteristics and the pH, time, solvents and concentration dependence of the adsorption of metal ions by this resin were studied. The correlation between the separation characteristics of uranium and transition metal on the resins and the stability constants of complexes with macrocyclic ligands have been examined. The resins were very stable in both acidic and basic media and had good resistance to heat at $280^{\circ}C$. The $UO_2^{2+}$ aqueous solution was not adsorbed on the resins below pH 3.0, but the power of adsorption of $UO_2^{2+}$ increased rapidly above pH 4.0. The optimum equilibrium time for adsorption of metallic ions was twenty minutes and adsorptive power decreased in proportion to crosslinking size of the resins and order of dielectric constants of solvents used and the selective sequence for metal cations is in the order of $UO_2^{2+}$, $Cu^{2+}$ and $Ce^{3+}$ .

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A Study on the Adsorption of U(VI), NiI(II), Nd(III) Metal Ions Using Synthetic Resin (합성수지를 이용한 U(VI), NiI(II), Nd(III) 금속이온들의 흡착에 관한 연구)

  • 박성규;김준태;노기환
    • Journal of environmental and Sanitary engineering
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    • v.15 no.1
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    • pp.77-87
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    • 2000
  • Several new ion exchange resins have been synthesized from chloromethyl styrene-l,4-divinylbenzine with 1%, 2%, 10% and 20%-crosslink and macrocyclic ligands of cryptand type by interpolymerization method. The adsorption characteristics and the pH, time, solvents and concentration dependence of the adsorption of metal ions by this resin were studied. The correlation between the separation characteristics of uranium and transition metal on the resins and the stability constants of complexes with macrocyclic ligands have been examined. The resins were very stable in both acidic and basic media and have good resistance to heat. The $UO_2^{2+}$ was not adsorbed on the resins below pH 3.0, but the power of adsorption of $UO_2^{2+}$ increased rapidly above pH 4.0. The optimum equilibrium time for adsorption of metallic ions was two hours and adsorptive power decreased in proportion to crosslink size of the resins and order of dielectric constants of solvents used and the selective sequence for metal cations was in the order of $UO_2^{2+}$, $Ni{2+}$ and $Nd{3+}$.

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Studies on the New Analytical Methods for Separation and Recovery of Rare Earth Metals (I) : Adsorption Characteristics of U(VI) Ion by New Synthetic Resins with Macrocyclic Compounds (희토류금속 분리 및 회수를 위한 분석화학적 연구 (제1보) : 우라늄(VI)의 분리회수를 위한 선택이온교환수지 합성과 우라늄(VI) 금속이온의 흡착특성)

  • Jung Oh Jin;Hak Jin Jung;Joon Tea Kim
    • Journal of the Korean Chemical Society
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    • v.32 no.4
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    • pp.358-370
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    • 1988
  • Several new ion exchange resins have been synthesized from chloromethyl styrene-1,4-divinylbenzene(DVB) with 1%, 2%, 4%, and 10%-crosslinking and macrocyclic ligands of cryptand type by interpolymerization method. The adsorption characteristics and the pH, time, solvents and concentration dependence of the adsorption of metal ions by this resin were studied. The correlation between the separation characteristics of uranium, rare earths and transition metal on the resins and the stability constants of complexes with macrocyclic ligands have been examined. The resins were very stable in both acidic and basic media and have good resistance to heat at $280^{\circ}C$. The $UO_2^{+2}$ aqueous solution are not adsorbed on the resins below pH 3.0, but the power of adsorption of $UO_2^{2+}$ increased rapidly above pH 4.0. The optimum equilibrium time for adsorption of metallic ions was twenty minutes and adsorptive power decreased in proportion to crosslinking size of the resins and order of dielectric constants of solvents used and the selective sequence for metal cations is in the order of $UO_2^{2+},\;Cu^{2+}\;and\;Nd^{3+}$.

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