• Title/Summary/Keyword: Aprotic

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Electrochemical Behaviour of (2,4-difluoro-phenyl)-(2-phenyl-1H-quinolin-4-ylidene)-amine in Aprotic Media (비양자성 매개물에서 (2, 4-difluoro-phenyl)-(2-phenyl-1H-quinolin-4-ylidene)-amine의 전기화학적 반응)

  • Kumari, Mamta;Sharma, D.K.
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.50-56
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    • 2011
  • The electrochemical reduction of (2,4-difluoro-phenyl)-(2-phenyl-1H-quinolin-4-ylidene)-amine was investigated in 0.1 M tetrabutylammoniumbromide in N,N-dimethylformamide at glassy carbon electrode (GCE) using the technique of cyclic voltammetry at the room temperature (290 K). The reduction of imines occurs in two successive steps, involving one electron in each. In this medium the first peak was observed at about -0.793 V (vs Ag/$Ag^+$) at the glassy carbon electrode surface, which is more stable and well defined as compared to the second peak. The diffusion coefficient ($D_0$) of imine in the investigated solvent media has been calculated using the modified Randles-Sevcik equation. The electron transfer coefficient ($\alpha$) of the reactant species has also been calculated.

The Behavior of Electrolytes in Nonaqueous Solutions (IV). Relative Viscosities and Osmotic Coefficients of Alkaline Metal Iodides (물아닌 용액에서의 전해질의 행동에 관한 연구 (제4보). 요오드화알칼리금속의 상대점도와 삼투계수)

  • Si-Joong Kim;Jin-Ho Kim;Kyu-Seong Choi
    • Journal of the Korean Chemical Society
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    • v.28 no.6
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    • pp.349-354
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    • 1984
  • The relative viscosities and the osmotic coefficients of alkaline metal iodides (NaI, KI, RbI, CsI) in methanol, ethanol, dimethylsulfoxide (DMSO), and sulfolane (TMS) have been measured by Ubbelohde viscometer and vapor pressure osmometry at 45 ∼ $120^{\circ}C.$ The order of A and B coefficients in viscosity for alkaline metal iodides are MeOH > EtOH > TMS > DMSO, and TMS > EtOH > DMSO > MeOH. dB/dT values for the alkaline metal iodides are in the order of NaI > KI > RbI > CsI in the protic solvents, while those for the aprotic solvents are in the reverse order. The order of the osmotic coefficients for the alkaline metal iodides is EtOH > DMSO > MeOH > TMS.

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Electrochemical Reduction of Iodine in Non-aqueous Solvents (물아닌 용매속에서의 요오드의 전기화학적 환원)

  • Park Doo Won;Choi Won Hyung
    • Journal of the Korean Chemical Society
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    • v.19 no.2
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    • pp.104-115
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    • 1975
  • The electrochemical reduction of iodine in non-aqueous media have been studied by polarography, chronopotentiometry, cyclic voltammetry and controlled potential coulometry at dropping mercury electrode and platinum, gold and amalgamated platium electrodes. In amphiprotic solvents such as methanol, ethanol, isopropanol and pyridine, iodine were reduced to iodide ions via one step reduction involving 1 electron and in aprotic solvents such as acetonitrile, dimethylformamide and dimethylsulfoxide via two step reduction involving all 3 electrons. The reductions of iodine give well defined polarograms at dropping mercury electrode and irreversible chronopotentiograms at platinum electrode, but less defined irreversible chronopotentiograms at gold and amalgamated platinum electrodes, those are all diffusion controlled. The diffusion coefficients of iodine in various solvents were estimated from the chronopotentiometric data and Sand equation.

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A study on the SEI film formation as organic solvent decomposition of lithium ion batteries and its electrochemical behavior (리튬이온전지의 유기용매분해에 따른 SEI film형성과 전기화학적 거동에 관한 연구)

  • 김민성;구할본
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2001.11a
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    • pp.545-549
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    • 2001
  • We have produced electrolyte solution out of 1.15M LiPF$\sub$6/ EC/EMC/DEC/PC(30/55/10/5 by vol%) as a reference, and at the same time, performed basic physical property test using a single solvent of 1.15M LiPF$\sub$6/DEC, DMC, EMC and a 2 component electrolyte solution of 1.15M LiPF$\sub$6/ EC/DEC(1/2 by vo%%) and PC/DEC(1/2 by vol%). Cyclic Voltammetry Analysis showed that, compared to existing carbonate organic solvent, the addition of DEC, DMC and EMC brought the de-decomposition peak of salt anion of PF$\sub$6/$\^$-/ and the solvent at lower oxidization potential of 2.3V, 0.7V and 2.1V(vs. Li/Li$\^$+/\`). In addition, a kinetics current peak, in which intercalation of Li$\^$+/ is proceeded at 750mv, 450mv(vs. Li/Li$\^$+/), was confirmed. These findings suggest that the DEC solvent decomposition occurred at an electric potential lower than that of oxidization of existing carbonate organic solvent. Through the impedance analysis, we checked electric charge transfer resistance(R$\sub$ct/) according to the electric potential of Li$\^$+/ intercalation at 750mv(vs. Li/Li$\^$+/), which was the same as the resistance (R$\sub$f/) and cyclic voltammetry of SEI film that was formed at Reference. By doing so, we found that the significant decrease of polarization resistance(R$\sub$p/) when Reference was played a part in the formation of compact SEI layer at the initial decomposition reaction.

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Synthesis of Pentadentate Schiff Base Molybdenum(Ⅴ) Complexes and Their Electrochemical Properties in Aprotic Solvents (다섯자리 Schiff Base Molybdenum(Ⅴ) 착물들의 합성과 비수용매에서의 전기화학적 성질)

  • Kim, Seon Suk;Choe, Ju Hyeong;Choe, Yong Guk;Jeong, Byeong Gu
    • Journal of the Korean Chemical Society
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    • v.38 no.2
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    • pp.160-168
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    • 1994
  • Pentadentate Schiff base molybdenum(Ⅴ) complexes such as [Mo(Ⅴ)O(Sal-DET)(NCS)] and [Mo(Ⅴ)O(Sal-DPT)(NCS)] were synthesized by Sabat method. The structure of these complexes were identified by elemental analysis, spectroscopy, and thermogravimetric analysis(T.G.A.). It was found that the mole ratio of Schiff base ligand to the complexes was found to be 1 : 1. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic technique in nonaqueous solvent containing 0. 1 M tetraethyl ammonium perchlorate(TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes of four steps with one electron were 2Mo(Ⅴ)$\rightleftarrow^{e-}$ Mo(Ⅴ)Mo(Ⅳ) $\longrightarrow^{e-}$ 2Mo(Ⅳ), Mo(Ⅳ) $\longrightarrow^{e-}$ Mo(Ⅲ) $\longrightarrow^{e-}$ Mo(Ⅱ)

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Studies on the Electrochemical Properties of Oxygen Adducts Tetradentate Schiff Base Cobalt (Ⅱ) Complexes in Aprotic Solvents (Ⅱ) (비수용매에서 네자리 Schiff Base Cobalt (II) 착물들의 산소첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 2 보))

  • Ki-Hyung Chjo;Jin-Soon Chung;Heui-Suk Ham;Seoing-Seob Seo
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.192-202
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    • 1989
  • Tetradentate schiff bases cabalt (II) complexes; Co(SED) and Co(ο-BSDT) were synthesized and these complexes allowed to reaction with dry oxygen to form oxygen adduct cobalt(III) complexes such as $[Co(o-BSDT)(DMSO)]_2O_2,\;[Co(SED)(Py)]_2O_2\;and\;[Co(o-BSDT)(Py)]_2O_2$ in DMSO and pyridine solutions. It has been found that the oxygen adduct cobalt(III) complexes have hexacoordinated octahedral configuration with tetradentate schiff base cobalt(II), DMSO or pyridine and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1:2. The redox processes, were investigated for Co(SEDT) and Co(ο-BSD) complexes in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine by cyclic voltammetry with glassy carbon electrode. As a result the redox processes of Co(II)/Co(III) and Co(II)/Co(I) found to be reversible or quasi-reversible for non uptake oxygen complexes but oxygen adduct complexes found to be irreversible processes and reaction processes of oxygen for oxygen adduct complexes are quasi-reversible process, the potential range was $E_{pc}=-0.85{\sim}-1.19V\;and\;E_{pa}=-0.74{\sim}-0.89V$.

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Reevaluation of. the effect of Triton X-100 on the assay of superoxide radical by the nitrobluetetrazolium reduction method (NBT 환원방법에 의한 superoxide 라디칼의 검량에 미치는 Triton X-100 효과에 대한 재평가)

  • Kim, Hong-Suk;Chung, Soon-Kyu;Jung, Jin
    • Applied Biological Chemistry
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    • v.36 no.5
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    • pp.364-369
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    • 1993
  • Triton X-100 enhances to a marked extent the analytical sensitivity of the nitrobluetetrazolium (NBT) reduction method for the assay of superoxide$(O^-_{\.{^.2}})$ production. In the present work, it was attempted to elucidate the physicochemical nature of this Triton X-100 effect, focusing on not only the surfactant-caused stabilization of the water-insoluble formazan colloid but also the kinetic competition between the $NBT-O^-_{\.{^.2}}$ reaction and the autodisproportionation of concommitantly occuring in aqueous media. The measurements of formazan and $H_2O_2$ formed in a number of reaction systems, as prepared by vortex-mixing potassium superoxide dissolved in an aprotic solvent with aqueous solutions of NBT, revealed that Triton X-100 exerts its effect both through preventing formazan colloid from aggregation and thereby increasing the formazan absorbance and through suppressing the autodisproportionation reaction of $O^-_{\.{^.2}}$. It also turned out that the relative shares of the colloid stabilization effect and the kinetic effect in the contribution to the sensitivity amplification of the NBT method are dependent upon the reaction conditions, particulary the molar concentration ratio of NBT to $O^-_{\.{^.2}}$ in the reaction systems.

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Formation of New Thorium (IV) Complexes with Crown Ethers (새로운 Thorium (IV)-Crown Ether 착물형성)

  • Jung, Hak-Jin;Jung, Oh-Jin;Suh, Hyouck-Choon
    • Journal of the Korean Chemical Society
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    • v.31 no.3
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    • pp.258-270
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    • 1987
  • A series of new thorium nitrate complexes with crown ethers have been synthesized from the reaction of the hydrated thorium nitrate, with the appropriate crown ethers of different cavity sizes in various solvents such as methanol, ethanol, butanol, methylacetate, acetone, tetrahydrofuran and acetylacetone. CHN elemental analysis, ICPAS, thermal analysis and Karl-Fischer method have been used to characterize their compositions, and the spectroscopic methods of IR, UV, $^1H-NMR$, and X-ray diffraction have been employed to determine the structures and solvolysis phenomena of these complexes. and the electrical conductances were measured in DMSO, and water solvent. The solvolysis have been observed only in the complexes synthesized in acetylacetone solvent. In the solvated complexes of 15-crown-5 and 18-crown-6, the mole ratio of $Th^{4+}$: ligand : acetylacetone is found to be 1:1:1, but in the non-solvated complexes of 12-crown-4 and 15-crown-5, the mole ratios of Th:L are 1:2 and 2:3, respectively, and that in the complexes of both 18-crown-6 and dicyclohexano-18-crown-6 is 1:1. All complexes which were not solvated have shown $n{\to}{\sigma}^{\ast}$ electronic transitions of crown ether whereas complexes solvated have exhibited both $n{\to}{\sigma}^{\ast}$ of crown ether and $n{\to}{\pi}^{\ast}$ transitions of acac. The dissociation mole ratio of $Th^{4+}$ and nitrate ion is found to be 1:1 in aprotic solvent, and 1:4 in protic solvent like water.

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Nucleophilic Fluorination Reactions in Novel Reaction Media for $^{18}F$-Fluorine Labeling Method ($^{18}F$-플루오린 표지를 위한 신개념 반응용매에서 친핵성 불소화 반응)

  • Kim, Dong-Wook;Jeong, Hwan-Jeong;Lim, Seok-Tae;Sohn, Myung-Hee
    • Nuclear Medicine and Molecular Imaging
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    • v.43 no.2
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    • pp.91-99
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    • 2009
  • Noninvasive imaging of molecular and biological processes in living subjects with positron emission tomography(PET) provides exciting opportunities to monitor metabolism and detect diseases in humans. Measuring these processes with PET requires the preparation of specific molecular imaging probes labeled with $^{18}F$-fluorine. In this review we describe recent methods and novel trends for the introduction of $^{18}F$-fluorine into molecules which in turn are intended to serve as imaging agents for PET study. Nucleophilic $^{18}F$-fluorination of some halo- and mesyloxyalkanes to the corresponding $^{18}F$-fluoroalkanes with $^{18}F$-fluoride obtained from an $^{18}O(p,n)^{18}F$ reaction, using novel reaction media system such as an ionic liquidor tert-alcohol, has been studied as a new method for $^{18}F$-fluorine labeling. Ionic liquid method is rapid and particularly convenient because $^{18}F$-fluoride in $H_2O$ can be added directly to the reaction media, obviating the careful drying that is typically required for currently used radiofluorination methods. The nonpolar protic tert-alcohol enhances the nucleophilicity of the fluoride ion dramatically in the absence of any kind of catalyst, greatly increasing the rate of the nucleophilic fluorination and reducing formation of byproducts compared with conventional methods using dipolar aprotic solvents. The great efficacy of this method is a particular advantage in labeling radiopharmaceuticals with $^{18}F$-fluorine for PETimaging, and it is illustrated by the synthesis of $^{18}F$-fluoride radiolabeled molecular imaging probes, such as $^{18}F$-FDG, $^{18}F$-FLT, $^{18}F$-FP-CIT, and $^{18}F$-FMISO, in high yield and purity and in shorter times compared to conventional syntheses.

Selective Oxidation of 2,6-di-tert-butylphenol by Oxygen Adducted Pentadentate Schiff Base Cobalt (Ⅱ) Activated Catalysts and Electrochemical Properties of Cobalt (Ⅱ) Catalysts in Aprotic Solvents (비수용매에서 산소첨가된 다섯자리 Schiff Base Cobalt (Ⅱ) 활성촉매들에 의한 2,6-di-tert-butylphenol의 선택산화와 전기화학적 성질)

  • Chjo, Ki-Hyung;Choi, Yong-Kook;Kim, Sang-Bock;Lee, Song-Ju;Kim, Jong-Soon
    • Journal of the Korean Chemical Society
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    • v.35 no.6
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    • pp.689-698
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    • 1991
  • Activated oxidation catalysts are generated by the treatment of pentadentate Schiff base cobalt(Ⅱ) complexes with the oxygen saturated DMF solution. Oxidation of 2,6-di-tert-butylphenol by homogeneous oxidation catalysts of superoxo type pentadentate schiff base cobalt(Ⅲ) complexes yields 2,6-di-tert-butylbenzoquinone(BQ) as a major product. And $O_2$/Co mole ratio of homogeneous oxidative catalysts such as [Co(Ⅲ)(sal-DET)]$O_2$ and [Co(Ⅲ)(sal-DPT)]$O_2$by PVT method of the oxygen absorption in DMSO and pyridine solution was 1:1, 1:1.52 in DMF solution and ${\mu}$-peroxo type cobalt(Ⅲ) complexes formed at solid state. The redox reaction processes of superoxo type cobalt(Ⅲ) complexes as homogeneous oxidation catalysts were investigated by cyclic voltammetry and DPP method at a glassy carbon electrode. As a result of electrochemical measurements the reduction processes of oxygen adducted superoxo type cobalt(Ⅲ) complexes occurred to four steps including prewave of $O_2$-in 0.1M TEAP-DMSO and 0.1 M TEAP-Pyridine as supporting electrolyte solution.

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