• Title/Summary/Keyword: Alkali-metal effect

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Effect of the Addition of Si and Alkali Metal on the Viscosity and Molecular Behavior of Water Glass (Si와 알칼리 금속의 첨가에 따른 물유리의 점도 및 분자결합구조 특성변화)

  • Ryu, Young Bok;Lee, Man Sig
    • Applied Chemistry for Engineering
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    • v.29 no.1
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    • pp.112-116
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    • 2018
  • In this study, the mixing characteristics of water glass and additives (Si, alkali metal), which are one of the main raw materials of silicate based binder used in the production of molds during casting process, were examined. Molecular structures of water glass, additives and mixtures were analyzed FT-IR and viscosity measurements and their correlation were compared. The addition of Si source to the water glass accelerated the Si networking in the material and increased the viscosity. When the alkali metal was added, the viscosity of the water glass decreased by suppressing the Si networking of the water glass. Viscosities of the water glass and lithium silicate (LS) mixtures increased when the content of LS was less than 20 wt% and gradually decreased when the content was more than 20 wt%. By adding KOH to the water glass, the viscosity could be lowered and it could be used effectively to mix with colloidal silica (CS) or potassium methyl siliconate (PMS).

Effect of Alkali Metal Nitrates on the Ru/C-catalyzed Ring Hydrogenation of m-Xylylenediamine to 1,3-Cyclohexanebis(methylamine)

  • Kim, Young Jin;Lee, Jae Hyeok;Widyaya, Vania Tanda;Kim, Hoon Sik;Lee, Hyunjoo
    • Bulletin of the Korean Chemical Society
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    • v.35 no.4
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    • pp.1117-1120
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    • 2014
  • Ru/C-catalyzed hydrogenation of m-xylylene diamine into 1,3-cyclohexanebis(methylamine) was greatly accelerated by the presence of $LiNO_3$, $NaNO_2$, or $NaNO_3$. It was found that the effect of the nitrate salt was significantly affected by the size of cation. The promoting effect of the nitrate salt increased with the decrease of the cation size: $LiNO_3$ ~ $NaNO_2$ > $KNO_3$ > $CsNO_3$ >> [1-butyl-3-methylimidazolium]$NO_3$. XRD analysis of the recovered catalysts after the hydrogenation reactions showed that $LiNO_3$ and $NaNO_2$ were completely transformed into LiOH and NaOH, respectively, along with the evolution of $NH_3$, while $KNO_3$ and $CsNO_3$ remained unchanged.

Influence of Inorganic Salts on Aqueous Solubilities of Polycyclic Aromatic Hydrocarbons

  • Yim, Soobin
    • Journal of Soil and Groundwater Environment
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    • v.8 no.3
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    • pp.23-29
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    • 2003
  • Setschenow constants of six alkali and alkaline earth metal-based electrolytes (i.e., NaCl, KCl, CaCl$_2$, K$_2$SO$_4$, Na$_2$SO$_4$, NaClO$_4$) for three polycyclic aromatic hydrocarbons (PAHs) (i.e., naphthalene, pyrene, and perylene) were investigated to evaluate the influence of a variety of inorganic salts on the aqueous solubility of PAHs. Inorganic salts showed a wide range of K$\_$s/ values (L/mol), ranging from 0.1108 (NaClO$_4$) to 0.6680 (Na$_2$SO$_4$) for naphthalene, 0.1071 (NaClO$_4$) to 0.7355 (Na$_2$SO$_4$) for pyrene, and 0.1526 (NaClO$_4$) to 0.8136 (Na$_2$SO$_4$) for perylene. In general, the salting out effect of metal cations decreased in the order of Ca$\^$2+/>Na$\^$+/>K$\^$+/. The effect of SO$_4$$\^$2-/>Cl$\^$-/>ClO4$\^$-/ was observed for anions of inorganic salts. The K$\_$s/ values decreased in the order of perylene>pyrene>naphthalene for K$_2$SO$_4$. However, the order of decreasing salting out effect for NaCl, KCl, CaCl$_2$, and NaClO$_4$ was perylene>naphthalene>pyrene. Hydration free energy of the 1:1 and 2:1 alkali and alkaline earth metal-based inorganic salts solution was observed to have a meaningful correlation with Setschenow constants. Thermodynamic interactions between PAH molecules and salt solution can be of importance in determining the magnitude of salting out effect for PAHs at a given salt solution.

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.

Alkali-Metal Ion Catalysis in Alkaline Ethanolysis of 2-Pyridyl Benzoate and Benzyl 2-Pyridyl Carbonate: Effect of Modification of Nonleaving Group from Benzoyl to Benzyloxycarbonyl

  • Um, Ik-Hwan;Kang, Ji-Sun;Kim, Chae-Won;Lee, Jae-In
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.519-523
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    • 2012
  • A kinetic study is reported on nucleophilic displacement reactions of benzyl 2-pyridyl carbonate 6 with alkalimetal ethoxides, EtOM (M = Li, Na, and K), in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of pseudo-firstorder rate constant $k_{obsd}$ vs. [EtOM] curve upward, a typical phenomenon reported previously for alkaline ethanolysis of esters in which alkali-metal ions behave as a Lewis-acid catalyst. The kobsd value for the reaction of 6 with a fixed EtOK concentration decreases rapidly upon addition of 18-crown-6-ether (18C6), a complexing agent for $K^+$ ion up to [18C6]/[EtOK] = 1.0 and then remains constant thereafter, indicating that the catalytic effect exerted by K+ ion disappears in the presence of excess 18C6. The reactivity of EtOM towards 6 increases in the order $EtO^-$ < EtOLi < EtONa < EtOK, which is contrasting to the reactivity order reported for the corresponding reactions of 2-pyridyl benzoate 4, i.e., $EtO^-$ < EtOK < EtONa < EtOLi. Besides, 6 is 1.7 and 3.5 times more reactive than 4 towards dissociated $EtO^-$ and ion-paired EtOK, respectively. The reactivity difference and the contrasting metal-ion selectivity are discussed in terms of electronic effects and transition-state structures.

Joining and Performance of Alkali Metal Thermal-to-electric Converter (AMTEC) (알칼리금속 열전기변환장치의 접합과 출력성능)

  • Suh, Min-Soo;Lee, Wook-Hyun;Woo, Sang-Kuk
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.41 no.7
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    • pp.665-671
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    • 2017
  • The alkali-Metal Thermal-to-electric Converter (AMTEC) is one of the promising static energy conversion technologies for the direct conversion of thermal energy to electrical energy. The advantages over a conventional energy converter are its high theoretical conversion efficiency of 40% and power density of 500 W/kg. The working principle of an AMTEC battery is the electrochemical reaction of the sodium through an ion conducting electrolyte. Sodium ion pass through the hot side of the beta"-alumina solid electrolyte (BASE) primarily as a result of the pressure difference. This pressure difference across the BASE has a significant effect on the overall performance of the AMTEC system. In order to build the high pressure difference across the BASE, hermeticity is required for each joined components for high temperature range of $900^{\circ}C$. The AMTEC battery was manufactured by utilizing robust joining technology of BASE/insulator/metal flange interfaces of the system for both structural and electrical stability. The electrical potential difference between the anode and cathode sides, where the electrons emitted from sodium ionization and recombined into sodium, was characterized as the open-circuit voltage. The efforts of technological improvement were concentrated on a high-power output and conversion efficiency. This paper discusses about the joining and performance of the AMTEC systems.

The Effects of the Heavy Metal Ions on the Hydration and Microstructure of the Cement Paste (중금속이온이 시멘트의 수화 및 미세구조에 미치는 영향)

  • 김창은;이승규
    • Journal of the Korean Ceramic Society
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    • v.30 no.11
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    • pp.967-973
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    • 1993
  • The effect on the hydration of cement was that Cu and Pb reacted with alkali to form soluble hydrates at theinitial stage and then there followed a slow reaction forming insoluble metal hydroxides. These hydroxides were deposited on the surface of cement particles providing a barrier against further hydration. But as a slow reaction continued, the insoluble layers were eventually destroyed and the hydration reaction resumed. Thereafter, another retardation occured by restricting the polymerization of silicates, shown by FT-IR spectroscopy analysis. In the case of Cr, as its reaction with cement caused H2O, the coordinator of Cr complex, to replace or polymerize with OH-, the formation of Cr complex promoted the leakage of OH- and increased the heat of dissolution. So the total heat evolution during hydration was larger than that in the case of Pb or Cu. The retarding effect of heavy metal ions was in the order Pb>Cu>Cr.

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MAS-NMR Studies in Mixed Alkali Silicate Glasses with low Fe2O3 Content (미소량의 Fe2O3를 첨가시킨 혼합 알칼리 Silicate 유리들의 MAS-NMR 연구)

  • Kang, Myoung-Jin;Shim, Moon-Sik
    • Journal of Korean Ophthalmic Optics Society
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    • v.1 no.1
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    • pp.1-14
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    • 1996
  • The mixed alkali silicate glasses doped 0.1 mol% $Fe_2O_3$ are fabricated for studying the effect of transition metal oxides, which is related to the $Li^-$ ion movement in Magic-Angle-Spinning NMR. We have investigated the spin-lattice relaxation times in the room temperature and measured the $^7Li$ MAS-NMR spectrum with temperature. When the $Fe_2O_3$ oxides are added in alkali silicate glasses, the width of spectrum is changed a little but the line shape is hardly varied. For this reason, we can think that the mixed alkali effects are shown sufficiently in the spin-spin relaxation processes. However, it is not mixed alkali effects in this case. The activation energy of $Li^-$ ions are diminished in mixed alkali glasses. From the analysis of $Li^-$ diffusion environment, spin-lattice relaxation time and the nuclear magnetization, it is confirmed that the alkali mixed effects are not shown in $^7Li$ spin-lattice relaxation processes.

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Neutralization and removal of heavy metal ions in Plating wastewater utilizing Oyster Shells (굴껍질을 이용한 도금폐수의 중화 및 중금속 이온 제거)

  • 성낙창;김은호;김정권;김형석
    • Journal of Environmental Health Sciences
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    • v.22 no.3
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    • pp.81-87
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    • 1996
  • The purpose of this research is to examine the utilization of oyster shells for neutralization and removal of heavy metal ions in plating wastewater, because oyster shells have been known to be very porous, to have high specific surface area and to have alkaline minerals such as calcium and magnesium. The results obtianed from this research showed that oyster shells had a buffer capacity to neutralize an acidic.alkali system in plating wastewater. Generally, it could be showed that the removal efficiencies of heavy metal ions were very influenced by reaction times and oyster shell dosages. In point of ocean waste, if oyster shells substituted for a valuable adsorbent such as actviated carbon, they could look forward to an expected economical effect.

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Synthesis of Diazacrown Ethers Containing Phenolic Side Arms and Their Complex with Divalent Metal Ions

  • Chi, Ki-Whan;Ahn, Yoon-Soo;Shim, Kwang-Taeg;Huh, Hwang;Ahn, Jeong-Soo
    • Bulletin of the Korean Chemical Society
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    • v.23 no.5
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    • pp.688-692
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    • 2002
  • The aminomethylation of phenols with para-substituents by the Mannich reaction has successfully been accomplished to produce the Mannich bases 2-6. The compounds 7-8 have also been synthesized in order to identify the effect of the side arms and t he macrocycle in the complex formation. Protonation constants and stability constants of the double armed diaza-18-crown-6 ethers 2-7 with metal ions have been determined by potentiometric method at 25 $^{\circ}C$ in 95 % methanol solution. Under a basic condition (pH > 8.0), the double-armed crown ethers 2-6 revealed stronger interaction with divalent metal ions than the simple diazacrown ether 1. The stability constants with these metal ions were Co 2+ < Ni2+ < Cu2+ > Zn 2+ in increasing order, which are in accordance with the order of the Williams-Irving series. The stability constants with alkali earth metal ions were Ca 2+ < Sr 2+ < Ba 2+ in increasing order, which may be explained by the concept of size effect. It is noteworthy that the hosts 2-6, which have phenolic side arms and a macrocycle, bind stronger with metal ions than the hosts 1 and 7. On the other hand, the host 8, which has phenolic side arms with a pyperazine ring,provided comparable stability constants to those with the host 3. These facts demonstrate that phenolic side arms play a more important role than the azacrown ether ring in the process of making a complex with metal ions especially in a basic condition. In particular, the log KML values for complexation of divalent metal ions with the hosts 2-6 had the sequence, i.e., 2 (R=OCH3) < 3 (R=CH3) < 4 (R=H) < 5 (R=Cl) < 6 (R=CF3). The stability constants of the hosts 5 and 6 containing an electron-withdrawing group are larger than those of the hosts 2 and 3 containing an electron-donating group. This substituent effect is attributed to the solvent effect in which the aryl oxide with an electron-donating group has a tendency to be tied strongly with protic solvents.