• Title/Summary/Keyword: alkali metal agent

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The Effect of Alkali Metal Ions on Reactions of 8-(5-Nitroquinolyl) 3-Furoate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Eum, Ik Hwan;Lee, Seong Eun;Min, Ji Suk
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.673-677
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    • 2001
  • Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.

Influence of Alkali Metal Cation Type on Ionization Characteristics of Carbohydrates in ESI-MS

  • Choi, Sung-Seen;Kim, Jong-Chul
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1996-2000
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    • 2009
  • Alkali metal salts were introduced to enhance the ionization efficiency of glucose and maltooligoses in electrospray ionization-mass spectrometry (ESI-MS). A mixture of the same moles of glucose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, and maltoheptaose was used. Salts of lithium, sodium, potassium, and cesium were employed as the cationizing agent. The ionization efficiency varied with the alkali metal cation types as well as the analyte sizes. Ion abundance distribution of the [M+$cation]^+$ ions of the carbohydrates varied with the fragmentor voltage. The maximum ion abundance at low fragmentor voltage was observed at maltose, while the maximum ion abundance at high fragmentor voltage shifted to maltotriose or maltotetraose for Na, K, and Cs. Variation of the ionization efficiency was explained with the hydrated cation size and the binding energy of the analyte and alkali metal cation.

The Catalytic Effect of Alkali Metal Ions on Reactions of 8-(5-Nitroquinolyl) 2-Furoate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Eum, Ik Hwan;Lee, Seong Eun;Min, Ji Suk
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.669-672
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    • 2001
  • Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

Studies on the Stabilities of Insectcides Combined with some Stabilizers (살충제제(殺蟲製劑)의 안정성(安定性)에 관(關)한 연구(硏究))

  • Woo, Chong-Hak;Kim, Jae-Wan
    • Journal of Pharmaceutical Investigation
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    • v.1 no.1
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    • pp.101-108
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    • 1971
  • The stability and toxicity test for p.p'-DDT, DDVP and dipterex that put to used sample in this study effects is follows A. about p.p'-DDT (1) In elevating the stability of p.p'-DDT, best stabilizing solvent was benzene. (2) The stability-agent has no difficulty as long as it not contain metal ion for instance $Z_n^{2+}$,$C_r^{3+}$,$Al^{3+}$,and $Fe^{2+or3+}$ but in case of contain $F_e^{3+}$, the combination of salicylaminoguanidine is best effective. (3) Using this product for water-suspension, We must use span 40 for stability agent and adding it at the same time. (4) We must use container which does not week alkali and metal ion but it is to preserved in tight light-resistant container. (5) The stopper of container is adapted with above-mentioned condition of container, but it is better not to use metal material. (6) This product needs opening ventilation more than 30 minutes after diffusion or spray and in the room we remove cause of remained poison by cleaning the bottom. B. about DDVP and Dipterex (1) Benzene or toluene in best solvent to preserve stability of DDVP and Dipterex. (2) Span 40 is superior for stability agent of this product and second is span 80. (3) The pH of solution is very stable in pH 5-6 and comparative stable in alkali more than p,p'-DDT. (4) Container is to preserved in tight, lightresistant container and especially be careful of outflow and inflow of water. (5) Because this product is centeral stimulant poison, we must pay attention to prevent cause of contact diadermic toxicity after use.

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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.

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.

The Characteristics of Cr-Free Coating Hot Dip Galvanized Sheet Steel

  • Kim, Jong-Gi;Moon, Man-Been;Yun, Jeong-Mo
    • Corrosion Science and Technology
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    • v.10 no.1
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    • pp.24-29
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    • 2011
  • The greatest purpose of chromate treatment is to improve anti-corrosion by stabilizing a metal surface. Because metal surface forms a compound by absorbing oxygen or water in the air by being generally unstable, it is necessary to improve anti-corrosion of the metal by forming the metal surface with a stable film. When considering the economical efficiency and requirements together because the film of the metal surface treated with chromate has good anti-corrosion and the stability also in the air by being compact and strong, Chromate treatment has been used most up to the electronics industry from the auto industry. However, these days, because hexavalent chromium is both a toxic agent to be able to cause cancers and deadly poisonous environmental pollutant, the strong legal controls on its use is being imposed all over the world. Because of this reason, a new anti-corrosion method is being required. Also, by users' various demands, the passivations that have recently been developed require various characteristics such as conductivity, chemical resistance, alkali cleaning resistance as well as anti-corrosion. We could confirm the results such as excellent anti-corrosion compared to chromate, conductivity, chemical resistance and detergent resistance as the result of analysis of various characteristics of the galvannealed sheet steels coated with Cr-Free solution developed in this research.

A Development of High Power Activated Carbon Using the KOH Activation of Soft Carbon Series Cokes

  • Kim, Jung-Ae;Park, In-Soo;Seo, Ji-Hye;Lee, Jung-Joon
    • Transactions on Electrical and Electronic Materials
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    • v.15 no.2
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    • pp.81-86
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    • 2014
  • The process parameter in optimized KOH alkali activation of soft carbon series coke material in high purity was set with DOE experiments design. The activated carbon was produced by performing the activation process based on the set process parameters. The specific surface area was measured and pore size was analyzed by $N_2$ absorption method for the produced activated carbon. The surface functional group was analyzed by Boehm method and metal impurities were analyzed by XRF method. The specific surface area was increased over 2,000 $m^2/g$ as the mixing ratio of activation agent increased. The micro pores in $5{\sim}15{\AA}$ and surface functional group under 0.4 meq/g were obtained. The contents of the metal impurity in activated carbon which is the factor for reducing the electrochemical characteristics was reduced less than 100 ppm through the cleansing process optimization. The electrochemical characteristics of activated carbon in 38.5 F/g and 26.6 F/cc were checked through the impedance measuring with cyclic voltammetry scan rate in 50~300 mV/s and frequency in 10 mHz ~100 kHz. The activated carbon was made in the optimized activation process conditions of activation time in 40 minutes, mixing ratio of activation agent in 4.5 : 1.0 and heat treatment temperature over $650^{\circ}C$.

Study on Solvent Extraction Using Salen(NEt2)2 as a Chelating Agent for Determination of Trace Cu(II), Mn(II), and Zn(II) in Water Samples

  • In, Gyo;Kim, Young-Sang;Choi, Jong-Moon
    • Bulletin of the Korean Chemical Society
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    • v.29 no.5
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    • pp.969-973
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    • 2008
  • Solvent extraction using a Schiff-base, salen$(NEt_2)_2$, as a chelating agent has been conducted on several water samples to study the determination of trace Cu(II), Mn(II) and Zn(II). Experimental conditions for the formation and extraction of metal complexes were optimized with an aqueous solution similar in composition to the samples. The matrix difference between the sample and standard solutions was approximately matched, and the pH of each sample solution was adjusted to 9.5 with $NaHCO_3/NaOH$ buffer. The concentration of salen$(NEt_2)_2$ was $7.3\;{\times}\;10^{-3}$ mol/L, and the complexes were extracted into MIBK solvent followed by the measurement of AAS absorbance. The potential interference of concomitant ions was investigated, but no interference from alkaline and alkali earth ions was shown in this procedure. The given procedure is precise, as judged from the relative standard deviation of less than 5% for five measured data. The recovery of 93-103% shows that this method is quantitative for such trace metal analysis.