• Title/Summary/Keyword: Alkali ion

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Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 4-Nitrophenyl Nicotinate and Isonicotinate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Choi, Seo-Young;Hong, Yeon-Ju;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1951-1956
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    • 2011
  • A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. 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 shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

A hydrogen ion-selective membrane electrode based on N,N,N,N-Tetrabenzylethylenediamine as neutral carrier (N,N,N,N-Tetrabenzylethylenediamine 중성운반체를 이용한 수소 이온 선택성 막전극)

  • Jeong, Seong-Suk;Park, Myon-Yong;Chung, Koo-Chun;Cho, Dong-Hoe;Lee, Kyeong-Jae;Kim, Jae-Woo
    • Analytical Science and Technology
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    • v.8 no.2
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    • pp.187-193
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    • 1995
  • A PVC membrane ion-selective electrodes based on N,N,N,N-tetrabenzylethylenediamine as neutral carrier has been prepared by addition of plasticizers such as phthalates and sebacate and liphophillic additives such as NaTPB. The membrane electrodes were investigated to the electric resistance, response range to hydrogen ion and the interfering effect of alkali and alkline earth metals. A electric resistance hardly had on effect of plasticizers. In case of 0.7% NaTPB added to membrane, response of the electrodes were shown the values near to theoretical Nernstian slope and interferences by alkali and alkaline earth metal were few influenced. The performances of pH-selective electrodes were shown linerality to hydrogen ion between pH 2 and 10 in the presense of alkali and alkaline earth ions. Reproducibility and stability tests were shown good results in the same pH range.

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Effect of ITO thin films characterization by barrier layers$(SiO_2\;and\;Al_2O_3)$ on soda lime glass substrate (Soda lime glass기판위의 barrier층$(SiO_2,\;Al_2O_3)$이 ITO박막특성에 미치는 영향)

  • Lee, Jung-Min;Choi, Byung-Hyun;Ji, Mi-Jung;An, Yong-Tae;Ju, Byeong-Kwon
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.11a
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    • pp.292-292
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    • 2007
  • To apply PDP panel, Soda lime glass(SLG) is cheeper than Non-alkali glass and PD-200 glass but has problems such as low strain temperature and ion diffusion by alkali metal oxide. In this paper suggest the methode that prohibits ion diffusion by deposing barrier layer on SLG. Indium thin oxide(ITO) thin films and barrier layers were prepared on SLG substrate by Rf-magnetron sputtering. These films show a high electrical resistivity and rough uniformity as compared with PD-200 glass due to the alkali ion from the SLG on diffuse to the ITO film by the heat treatment. However these properties can be improved by introducing a barrier layer of $SiO_2\;or\;Al_2O_3$ between ITO film and SLG substrate. The characteristics of films were examined by the 4-point probe, SEM, UV-VIS spectrometer, and X-ray diffraction. GDS analysis confirmed that barrier layer inhibited Na and Ka ion diffusion from SLG. Especially ITO films deposited on the $Al_2O_3$ barrier layer had higher properties than those deposited on the $SiO_2$ barrier layer.

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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.

Removal of Pb2+ ion from aqueous solution Using crab shell treated by acid and alkali (산-염기 처리한 게 껍질에 의한 수풍의 납 이온 제거)

  • 김동석
    • Journal of Environmental Science International
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    • v.12 no.4
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    • pp.469-476
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    • 2003
  • In order to examine the pre-treatment effect of crab shell en Pb$^{2+}$ removal by crab shell in aqueous solution, acid and alkali pre-treated crab shell were used. Electron microscopy techniques such as TEM (transmission electron microscopy) and SEM (scanning electron microscopy), and EDX (energy dispersive X-ray) and FTIR (Fourier transform infrared) spectrometry techniques were used to investigate the process of Pb$^{2+}$ removal by acid and alkali pre-treated crab shell. The Pb$^{2+}$ removal by acid pre-treated crab shell was much lower than that by untreated crab shell because of the decrease of CaCO$_3$ from the crab shell. However, the Pb$^{2+}$removal by alkali pre-treated crab shell increased compared to that by untreated crab shell. The results were confirmed by TEM, SEM, EDX and FTIR.nd FTIR.

Simple Route to High-performance and Solution-processed ZnO Thin Film Transistors Using Alkali Metal Doping

  • Kim, Yeon-Sang;Park, Si-Yun;Kim, Gyeong-Jun;Im, Geon-Hui
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.187-187
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    • 2012
  • Solution-processed metal-alloy oxides such as indium zinc oxide (IZO), indium gallium zinc oxide (IGZO) has been extensively researched due to their high electron mobility, environmental stability, optical transparency, and solution-processibility. In spite of their excellent material properties, however, there remains a challenging problem for utilizing IZO or IGZO in electronic devices: the supply shortage of indium (In). The cost of indium is high, what is more, indium is becoming more expensive and scarce and thus strategically important. Therefore, developing an alternative route to improve carrier mobility of solution-processable ZnO is critical and essential. Here, we introduce a simple route to achieve high-performance and low-temperature solution-processed ZnO thin film transistors (TFTs) by employing alkali-metal doping such as Li, Na, K or Rb. Li-doped ZnO TFTs exhibited excellent device performance with a field-effect mobility of $7.3cm^2{\cdot}V-1{\cdot}s-1$ and an on/off current ratio of more than 107. Also, in case of higher drain voltage operation (VD=60V), the field effect mobility increased up to $11.45cm^2{\cdot}V-1{\cdot}s-1$. These all alkali metal doped ZnO TFTs were fabricated at maximum process temperature as low as $300^{\circ}C$. Moreover, low-voltage operating ZnO TFTs was fabricated with the ion gel gate dielectrics. The ultra high capacitance of the ion gel gate dielectrics allowed high on-current operation at low voltage. These devices also showed excellent operational stability.

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Alkali Recovery by Electrodialysis Process: A Review (전기투석 공정에 의한 알칼리 회수: 총설)

  • Sarsenbek Assel;Rajkumar Patel
    • Membrane Journal
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    • v.33 no.3
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    • pp.87-93
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    • 2023
  • Electrodialysis (ED) is essential in separating ions through an ion exchange membrane. The disposal of brine generated from seawater desalination is a primary environmental concern, and its recycling through membrane separation technology is highly efficient. Alkali is produced by several chemical industries such as leather, electroplating, dyeing, and smelting, etc. A high concentration of alkali in the waste needs treatment before releasing into the environment as it is highly corrosive and has a chemical oxygen demand (COD) value. The concentration of calcium and magnesium is almost double in brine and is the perfect candidate for carbon dioxide adsorption, a major environmental pollutant. Sodium hydroxide is essential for the metal carbonation process which, is easily produced by the bipolar membrane electrodialysis process. Various strategies are available for its recovery, like reverse osmosis (RO), nanofiltration (NF), ultrafiltration (UF), and ED. This review discusses the ED process by ion exchange membrane for alkali recovery are discussed.

Sodium Ion-Selective Membrane Electrode Based on Dibenzopyridino-18-Crown-6

  • Tavakkoli, Nahid
    • Bulletin of the Korean Chemical Society
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    • v.25 no.10
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    • pp.1474-1476
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    • 2004
  • A sodium ion- selective electrode based on dibenzopyridino-18-crown-6 as membrane carrier was successfully prepared. The electrode exhibits a Nernstian response for $Na^+$ ions within the concentration range of $1.0\;{\times}\;10^{-4}-1.0\;{\times}\;10^{-1}$ M. The response time of the sensor is 20 s. The sodium ion-selective electrode exhibited comparatively good selectivities with respect to alkali, alkaline earth and some transition metal ions.

A Study on the Synthesis of Carboxymethyl Chitin and Separation of Alkali-Earth Metal ions by Adsorption (Carboxymethyl Chitin의 합성 및 알칼리 토금속 이온의 흡착분리에 관한 연구)

  • Choi, Kyu-Suk;Chang, Byung-Kwon;Kim, Chong-Hee;Kim, Yong-Moon
    • Applied Chemistry for Engineering
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    • v.2 no.3
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    • pp.270-278
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    • 1991
  • Carboxymethyl chitin(CM-chitin) was prepared by the reaction of alkali chitin with monochloroacetic acid in isopropyl alcohol. According to the pH variation, the adsorptivity of this chelating polymer to the alkali-earth metal ions such as $Ca^{2+},\;Mg^{2+}$, $Sr^{2+}$, $Ba^{2+}$ ions was determined by batch method. The adsorption tendency of this chelating polymer to most metal ions was increased with the increase of pH. The highest degree of adsorption was observed toward $Ca^{2+}$ ion among the alkali-earth metal ions. The selectivity adsorption property toward $Ca^{2+}$ ion was examined in the solution of $Ca^{2+}$ and $Mg^{2+}$ ions, and it was observed that CM-chitin showed excellent selectivity to $Ca^{2+}$ ion than $Mg^{2+}$ ion. $Mg^{2+}$ ion bound to CM-chitin molecule in the presence of $Ca^{2+}$ ion owing to low equilibrium constant. In the adsorption experiment of $Ca^{2+}$ and $Mg^{2+}$ ions to the CM-chitin under coexistence of $Na^+$ and $K^+$ ions, it observed that adsorptivity of only $Ca^{2+}$ ions was not affected by these monovalent cations.

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