• Title/Summary/Keyword: Alkali metal ion

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Synthesis and Binding Properties of a Calix[4]crown-6-functionalized Polymeric Ion Acceptor

  • Seol, Wan-Ho;Yang, Yu-Sun;Lee, Chil-Won;Gong, Myoung-Seon
    • Macromolecular Research
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    • v.12 no.4
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    • pp.427-430
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    • 2004
  • Calix[4]crown-6-2,4-bis(2-hydroxyethyl ether) (2), which has crown-6 moieties at the 1- and 3-positions and hydroxyethyl functions at the 2- and 4-positions, was prepared for the syntheses of polyester 3 and polyurethane 4 by reactions with adipoyl chloride and hexamethylene diisocyanate, respectively. The ion binding characteristics of monomer 2 and polymers 3 and 4 toward alkali and alkali earth metal ions were measured by liquid-liquid extraction from the aqueous phase into the organic phase. We observed that the polyurethane 4 has a higher binding affinity toward various metal cations when compared to polyester 3, which exhibits cesium ion selectivity.

Metal Ion Catalysis in Nucleophilic Substitution Reaction of 4-Nitrophenyl Picolinate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Hong, Yeon-Ju;Kim, Song-I;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2483-2487
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    • 2010
  • Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

Effects of Alkali and Chloride ions on the Electric Conduction of ZrF4-Based Heavy Metal Fluoride Glasses (알칼리 및 염소 이온이 지르코늄 플루오르화물 유리의 전기전도에 미치는 영향)

  • 한택상;박순자;조운조;정기호;최상삼
    • Journal of the Korean Ceramic Society
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    • v.26 no.5
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    • pp.601-608
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    • 1989
  • Electrical properties of ZrF4-based heavy metla fluoride glasses were measured by the ac complex impedance method. The effects of alkali and chloride ions addition into fluoro zirconate glasses on the electrical conductivity were examined. The electrical conductivities of fluoride glasses show Arrhenian behavior in the temperature range of the experiment and were decreased by the addition of sodium fluoride up to 15mol%. Mixed alkali substitution resulted in conductivity minimum at intermediate composition which is commonly observed as mixed alkali effect' in alkali oxide glasses. Chloride ion substituted for fluoride ion was found to lower the conductivity.

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Alkali-Metal Ion Catalysis in Nucleophilic Substitution Reactions of 5-Nitro-8-quinolyl Picolinate with Alkali Metal Ethoxides: Effect of Modification of Nonleaving Group from Benzoyl to Picolinyl on Reactivity and Transition State Structure

  • Jeon, Seong Hoon;Yoon, Jung Hwan;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1506-1510
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    • 2014
  • A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

Competitive Solvent Extraction of the Mixture of Alkali Metal and Alkaline Earth Metal Cation containing Crown Ether Carboxylic Acid and Crown Ether Phosphonic Acid (크라운에테르 카르복시산과 크라운에테르 포스포닉산을 포함한 알칼리 금속과 알칼리 토금속 양이온 혼합물의 경쟁적 용매추출)

  • Chung, Yeong-Jin
    • 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%).

Hydration Mechanism of Alkali Activated Slag Cement

  • Jong Cheol Kim;Keun Ho Auh;Sung Yun Hong
    • The Korean Journal of Ceramics
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    • v.5 no.1
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    • pp.35-39
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    • 1999
  • For many years, alkali activated blast furnace slag cement containing no ordinary portland cement has received much attention in the view of energy saving and its many excellent properties. We examined the structural change of slag glass which was activated by alkali metal compounds using IR spectroscopy. The properties of hydrated products and unhydrated slag grains was characterized by XRD and micro-conduction calorimeter. Ion concentration change in the liquid during the hydration of blast furnace slag was also studied to investigated the hydration mechanism.

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Removal of Alkali Metal Ion and Chlorine Ion Using the Ion Exchange Resin (이온교환수지를 이용한 알칼리 금속 이온 및 염소 이온의 제거)

  • Lee, Kyung-Han;Kil, Bo-Min;Ryu, Cheol-Hwi;Hwang, Gab-Jin
    • Membrane Journal
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    • v.30 no.4
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    • pp.276-281
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    • 2020
  • A research was conducted on the removal of ion from the solution involving the alkali metal ion and chlorine ion using ion exchange resin. The cation exchange resin and anion exchange resin was used for the remove of metal ion (Na+ and K+) and chlorine ion (Cl-), respectively. In the case of solution A (involving 36,633 ppm of Na+ and 57,921 ppm of Cl-), the Na+ ion and Cl- ion were removed over 99% within 20 min. In the case of solution B (involving 1,638 ppm of K+), the K+ ion was removed over 99% within 3 min.

Alkali Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 3,4-Dinitrophenyl Diphenylphosphinothioate with Alkali Metal Ethoxides in Anhydrous Ethanol: Effect of Changing Electrophilic Center from P=O to P=S

  • An, Jun-Sung;NamKoong, Gil;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2423-2427
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    • 2011
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-}$ ${\approx}$ $k_{EtOK}$ < $k_{EtOK/18C6}$, indicating that the reaction is inhibited by $Li^+$ and $Na^+$ ions but is catalyzed by 18C6-crowned $K^+$ ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., $k_{EtOLi}$ > $k_{EtONa}$ > $E_{EtOK}$ > $k_{EtO^-}$ ${\approx}$ $k_{EtOK/18C6}$, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of $M^+$ ions is significant. A four-membered cyclic transition-state has been proposed to account for the $M^+$ ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned $K^+$ ion while it interacts weakly with the hard $Li^+$ and $Na^+$ ions.

Synthesis of New Triazacrown Ion Exchanger and Its Ion Exchange Characteristics (새로운 트리아자크라운 이온교환체의 합성과 그의 이온교환 특성)

  • Kim, Dong Won;Chung, Yong Soon;Kim, Chang Suk;Choi, Ki Young;Lee, Yong Ill;Hong, Choon Pyo
    • Journal of the Korean Chemical Society
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    • v.39 no.5
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    • pp.371-378
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    • 1995
  • The triazacrown compound, 1,7-dioxa-4,10,13-triazacyclopentadecane trihydrobromide salt (Na3O2-3HBr) was synthesized. And this compound was used to synthesize the new ion exchanger, which combined with Merrifield peptide resin. This new ion exchanger had a capacity of 3.2 meq/g dry resin. And the distribution coefficients of alkali and alkaline earth metal ions on this ion exchanger in the various concentrations of hydrochloric acid were determined. The ion exchange behaviors of alkali and alkaline earth metal ions in the various hydrochloric acid concentrations are, also, discussed.

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