• Title/Summary/Keyword: Cyanide(CN)

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Synthesis of the Tetrazolium Derivatives for Ionic Liquid Rocket Fuel and a Study of Their Ignition Delay Time and Viscosity (이온성 액체로켓 연료용 테트라졸리윰 유도체의 합성 및 점화지연시간 및 점도에 대한 연구)

  • Lee, Hyun-Woong;Choi, Seong-Ho
    • Journal of the Korea Institute of Military Science and Technology
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    • v.25 no.3
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    • pp.285-291
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    • 2022
  • In order to use the liquid rocket fuel, 1,5-diamino-4-methyltetrazolium azide, [DMT]+[N3]- and 1,5-diamino-4-methyltetrazolium cyanide, [DMT]+[CN]- were synthesized and prepared the ionic liquid rocket fuel after dissolving the synthesized solid-type energetic chemicals in hydrazine, respectively. The thermal decomposition temperatures(Td) and densities(d) of the prepared ionic liquid rocket fuels were about 200 ℃ and above 1.0 g/cm3 respectively. The ignition delay times(Idt) of the ionic liqud rock fuels with [DMT]+[N3]- and [DMT]+[CN]- were in a range of 26.6 - 82.5 ms and the 44.0 - 98.5 ms, respectively. These results mean that the synthesized tetrazolium salts could be used as an ionic liquid rocket fuels. The viscosities of the ionic liqud rock fuels with [DMT]+[N3]- and [DMT]+[CN]-, which were dissolved in mixture solution of hydrazine/2-hydroxyethylhydrazine were to be 1.34 - 101 cP, and 1.29 - 80.5 cP, respectively. The synthesized ionic liquid rocket fuels in this study could be used as rocket fuel because the [Idt(100 ms or less), Td(150 ℃ or more), d(1.00 g/cm3 or more), and η(40.0~ 100 cP)] were achieved to satisfy the range of the used liquid rocket fuels.

A New Combined Source of "CN" from N,N-Dimethylformamide and Ammonia in the Palladium-Catalyzed Cyanation of Aryl C-H Bonds

  • Choi, Ji-Ho;Kim, Jin-Ho;Chang, Suk-Bok
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.207-207
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    • 2011
  • Aromatic nitriles possess versatile utilities and are indispensible not only in organic synthesis but also in chemical industry. In fact, the nitrile group is an important precursor for various functional groups such as aldehydes, amines, amidines, tetrazoles, amides, and their carboxyl derivatives. Representative methods for the preparation of organonitriles with cyanide-containing reagents are the Sandmeyer and Rosenmund-von Braun reactions. Recently, a catalytic route to aryl nitriles has been reported on the basis of the chelation-assisted C-H bond activation or metal-catalyzed cyanation of haloarenes. In those cyanation protocols, the "CN" unit is provided from metal-bound precursors of MCN (M=Cu, K, Na, Zn), TMSCN, or K3Fe(CN)6. Additionally, it can be generated in situ from nitromethane or acetone cyanohydrin. Herein, we report the first example of generating "CN" from two different, readily available precursors, ammonia and N,N-dimethylformamide (DMF). In addition, its synthetic utility is demonstrated through the Pd-catalyzed cyanation of arene C-H bonds.

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The Treatment of Heavy Metal-cyanide Complexes Wastewater by Zn$^{+2}$/Fe$^{+2}$ Ion and Coprecipitation in Practical Plant (II) (아연백법 및 공침공정을 이용한 복합 중금속-시안착염 폐수의 현장처리(II))

  • Lee, Jong-Cheul;Lee, Young-Man;Kang, Ik-Joong
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.5
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    • pp.524-533
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    • 2008
  • Industrial wastewater generated in the electroplating and metal finishing industries typically contain toxic free and complex metal cyanide with various heavy metals. Alkaline chlorination, the normal treatment method destroys only free cyanide, not complex metal cyanide. A novel treatment method has been developed which destroys both free and complex metal cyanide as compared with Practical Plant(I). Prior to the removal of complex metal cyanide by Fe/Zn coprecipitation and removal of others(Cu, Ni), Chromium is reduced from the hexavalent to the trivalent form by Sodium bisulfite(NaHSO$_3$), followed by alkaline-chlorination for the cyanide destruction. The maximum removal efficiency of chromium by reduction was found to be 99.92% under pH 2.0, ORP 250 mV for 0.5 hours. The removal efficiency of complex metal cyanide was max. 98.24%(residual CN: 4.50 mg/L) in pH 9.5, 240 rpm with 3.0 $\times$ 10$^{-4}$ mol of FeSO$_4$/ZnCl$_2$ for 0.5 hours. The removal efficiency of Cu, Ni using both hydroxide and sulfide precipitation was found to be max. 99.9% as Cu in 3.0 mol of Na$_2$S and 93.86% as Ni in 4.0 mol of Na$_2$S under pH 9.0$\sim$10.0, 240 rpm for 0.5 hours. The concentration of residual CN by alkaline-chlorination was 0.21 mg/L(removal efficiencies: 95.33%) under the following conditions; 1st Oxidation : pH 10.0, ORP 350 mV, reaction time 0.5 hours, 2nd Oxidation : pH 8.0, ORP 650 mV, reaction time 0.5 hours. It is important to note that the removal of free and complex metal cyanide from the electroplating wastewater should be employed by chromium reduction, Fe/Zn coprecipitation and, sulfide precipitation, followed by alkaline-chlorination for the Korean permissible limit of wastewater discharge, where the better results could be found as compared to the preceding paper as indicated in practical treatment(I).

Studies on the Anodic Oxidation Behavior of Methanol and L-Ascorbic Acid by Using Glassy Carbon Electrodes Modified with Inorganic-Metal Polymeric Films (무기 금속 고분자 막을 도포시킨 유리질 탄소전극을 이용한 메탄올과 L-ascorbic acid의 양극 산화 거동에 관한 연구)

  • Yoo, Kwang-Sik;Woo, Sang-Beom
    • Analytical Science and Technology
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    • v.11 no.5
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    • pp.347-352
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    • 1998
  • A study was carried out on the elelctrochemical characteristics of chemically modified electrodes (CMEs) by cyclic voltammetry. Fabrication of CMEs was made by coating with mixed valence (mv) inorganic-metal polymeric films on the glassy carbon electrode surface by potential cycling. Anodic oxidation behavior of methanol and L-ascorbic acid was studied by using CMEs working electrode. Deposition of films such as mv ruthenium oxo/ruthenium cyanide film (mv Ru-O/CN-Ru), mv ruthenium oxo/ferrocyanide film (mv Ru-O/$Fe(CN)_6$), and mv ruthenium oxo/ruthenium cyanide/Rhodium film (mv Ru-O/CN-Ru/Rh) was obtained to coat by scan rate of 50 mV/sec within the specified potential range (-0.5V ~ +1.2V). Film thickness was controlled by the repeat of the potential cycling. Anodic oxidation behavior of methanol was as follow. Calibration graph by using mv Ru-O/CN-Ru film showed linearly from 10 mM to 80 mM MeOH with slope factor of $-7.552{\mu}A/cm^2$. Although slope factor by using mv Ru-O/$Fe(CN)_6$ film was $-5.13{\mu}A/cm^2$, yet linear range of calibration graph could be extended from 10 mM to 100 mM MeOH. Anodic oxidation behavior of L-ascorbic acid was studied by mv Ru-O/CN-Ru film on the glassy carbon electrode and the glassy carbon electrode with Rh film, Glassy carbon electrode modified with Ru polymeric film was showed better sensitivity than the Rh-glassy carbon modified electrode (mv Ru-O/CN-Ru/Rh). Calibration graph was linear from 0.1 mM to 5 mM L-ascorbic acid by using glassy carbon electrode modified with Ru polymeric film. Solpe factor and relative coefficient are $-84.78{\mu}A/mM$ and 0.998, respectively.

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Electrochemical Reduction for trans-Complexes of Cobalt (III) with Bis(ethylenediamine) and Monodendate Ligands (한자리 리간드를 포함하는 트란스비스 (에틸렌디아민) 코발트 (III) 이온의 전극 환원반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Jae-Duck Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.215-224
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    • 1989
  • Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

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Protective Effects of Ginsenosides on Cyanide-induced Neurotoxicity in Cultured Rat Cerebellar Granule Cells

  • Seong, yeon-Hee;Koh, Sang-Bum;Jo, Soon-Ok
    • Journal of Ginseng Research
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    • v.24 no.4
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    • pp.196-201
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    • 2000
  • Effects of ginsenosides on NaCN-induced neuronal cell death were studied in cultured rat cerebellar granule cells. NaCN produced a concentration-dependent (1-10 mM) reduction of cell viability (measured by frypan blue exclusion test), that was blocked by N-methyl-D-aspartate receptor antagonist (MK-801) and L-type Ca$\^$2+/ channel blocker (verapamil). Pretreatment with ginsenosides (Rb$_1$, Rc, Re, Rf and Rg$_1$) significantly decreased the neuronal cell death in a concentration range of 0.5∼5$\mu\textrm{g}$/ml. Ginsenosides Rb$_1$ and Rc (5 $\mu\textrm{g}$/ml) inhibited glutamate release into medium induced by NaCN (5 mM). NaCN (1 mM)-induced increase of [Ca$\^$2+/], was significantly inhibited by the pretreatment of Rb$_1$ and Rc (5 $\mu\textrm{g}$/ml). Other ginsenosides caused relatively little inhibition on the elevation of glutamate release and of (Ca$\^$2+/). These results suggest that the NaCN-induced neurotoxicity was related to a series of cell responses consisting of glutamate release and [Ca$\^$2+/]i elevation via glutamate (NMDA and kainate) receptors and resultant cell death, and that ginsenosides, especially Rb$_1$ and Rc, prevented the neuronal cell death by the blockade of the NaCN-induced Ca$\^$2+/influx.

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Homolytic Reactions of Isonitriles (이소니트릴의 자유라디칼반응)

  • Sung Soo Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.3
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    • pp.250-258
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    • 1980
  • Various radicals may add to isonitriles to give imidoyl radcals RN=CR'. This may be also generated via abstraction of imidoyl hydrogen from imine in the following manner: RN=CR' + R"${\cdot}{\rightarrow}$ RN=CR' + R"-H Imidoyl radicals would be stabilized via two pathways, ${\beta}$-cleavage and atom transfer reactions. ${\beta}$-Cleavage may occur in two directions depending upon structure of the radicals. Cyanide transfer and the "so-called" normal ${\beta}$-cleavage are the two modes of ${\beta}$-cleavage. Addition of t-butoxy radical to t-butyl isocyanide 7 generates an imidoyl radical t-Bu-N=C-O-Bu-t, which undergoes ${\beta}$-cleavage to give t-butyl isocyanate and t-butyl radical. Addition of phenyl radical to 7 forms the intermediate radical t-Bu-N=$C-C_6H_5$, which decomposes to give benzonitrile and t-butyl radical. The t-butyl radical generated from the ${\beta}$-cleavage adds to 7 giving the radical t-Bu-N=C-Bu-t, which cleaves only to pivalonitrile and t-butyl radical, inducing radical chain isomerization. Trimethylsilyl radical adds to 7 to give the intermediate t-Bu-N=$C-Si(CH_3)_3$, which collapses to $(CH_3)_3$SiCN and a t-butyl radical.

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Matrix Infrared Spectra and DFT Computations of CH2CNH and CH2NCH Produced from CH3CN by Laser-Ablation Plume Radiation

  • Cho, Han-Gook
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1361-1365
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    • 2013
  • The smallest ketenimine and hydrogen cyanide N-methylide ($CH_2CNH$ and $CH_2NCH$) are provided from the argon/acetonitrile matrix samples exposed to radiation from laser ablation of transition-metals. New infrared bands are observed in addition to better determination of the vibrational characteristics for the previously reported bands, and the $^{13}C$ substituted isotopomers ($^{13}{CH_2}^{13}CNH$ and $^{13}CH_2N^{13}CH$) are also generated. Density functional frequency calculations and the D and $^{13}C$ isotopic shifts substantiate the vibrational assignments. $CH_2CNH$ is probably produced through single-step conversion of $CH_3CN$, whereas $CH_2NCH$ through two-step conversion via 2H-azirine. Inter-conversions between these two products evidently do not occur during photolysis and annealing.

Quantitative Analysis of Prussic Acid by "Micro-Diffusion Analsis." II Determination of Prussic Acid in Human Blood (미량확산분석법에 의한 청산의 정량법 (제2보) 혈액중(CN-Met Hb)청산의 정량)

  • 심상혁;서정현
    • YAKHAK HOEJI
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    • v.4 no.1
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    • pp.47-49
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    • 1959
  • Another application of the new quantitative analytical method of prussic acid by "Microdiffusion analysis" for the determination of prussic acid in human blood was studied. The blood containing potassium cyanide was dropped in outer room of unit, and then N-sulfuric acid was added. The liberated HCN gas was absorbed into nickel sulfate solution of inner room, afterward, absorbed prussic acid was determined with EDTA by residual titration. The result was coincided with the result of Liebig Denigs' method at ordinary temperature.

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