• Title/Summary/Keyword: Aprotic

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A thermodynamic analysis on thermochromism of fluoran dyes (Fluoran계 염료의 열변색 현상에 관한 열역학적 분석)

  • Kim, Jae-Uk;Ji, Myoung-Jin;Kim, Jong-Gyu
    • Analytical Science and Technology
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    • v.22 no.2
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    • pp.159-165
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    • 2009
  • The thermochromism of fluoran has been examined. The DCF exists as a colorless lactone in aprotic solvents. However, the DCF exists in the form of an equilibrium mixture of a colored zwitter-ion and a colorless lactone in protic solvents. When an acid is added to the solution, the DCF exists an equilibrium mixture as a colorless lactone and a colored cation even in aprotic solvents. In order to understand the interaction between the DCF and the solvent, absorption spectra of the DCF in various solvents were measured. The thermodynamic parameters of the DCF have also been investigated. From the variation of absorbance with temperature, the standard enthalpy changes ${\Delta}H^0$ of the equilibrium between the lactone and the zwitter-ion in various solvents have been determined. The standard enthalpy change ${\Delta}H^0$ is approximately -2.0 kJ/mol in protic solvents. In acidic solution, the standard enthalpy change is measured to be to zero in protic solvents within the experimental error. When the carboxylic group is protonated in acidic solution, a poor interaction between the dye and the solvent is expected.

Kinetic Studies on Halogen Exchange of 1-Naphthyl Methyl Halides (1-나프틸메틸 할라이드의 할로겐 교환반응)

  • Lee Kae-Soo
    • Journal of the Korean Chemical Society
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    • v.13 no.2
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    • pp.115-120
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    • 1969
  • Kinetics of reactions of halide ions with 1-naphthyl methyl halide have been investigated in anhydrous acetone. Semi-quantitative analysis of the results shows that if the softness of the substrate increases remarkably, the nucleophilicity order of halide ions is $I^- > Br^- > Cl^-$ even in dipolar aprotic solvent. But for 1-naphthyl methyl bromide, though the reaction center which was made soft by symbiosis of bromine atom raises the reactivity of soft nucleophile, nucleophilicity order indicates that soft-soft interaction is interfered by perihydrogen.

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Polarographic Behavior of Azo Series Organic Compounds (III). Reduction of Benzeneazoresorcinol in Acetonitrile (Azo계 유기화합물의 폴라로그래프법적 거동 (제3보). 아세토니트릴중에서 Benzeneazoresorcinol의 환원)

  • Heung Lark Lee;Zun Ung Bae
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.130-134
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    • 1984
  • The polarographic behavior of benzeneazoresorcinol (BAR) in acetonitrile as an aprotic solvent has been investigated by direct current polarography and controlled-potential coulometry. The reduction of BAR in $1.0{\times}10^{-2}$M tetraethylammonium perchrolate solution proceeds along four one-electron steps to give the corresponding amine compounds. Each reduction wave was considerably diffusion-controlled and not completely reversible.

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Explorative and Mechanistic Studies of the Photooxygenation of Sulfides

  • Albini, Angelo;Bonesi, Sergio M.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.1-7
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    • 2003
  • The results of recent work on the dye-sensitized photooxygenation of sulfides is discussed. In the case of dialkyl sulfides, the weakly bonded adduct initially formed with singlet oxygen (the persulfoxide) decays unproductively unless protonation by an acid (an alcohol or a carboxylic acid) facilitates its conversion to the sulfoxide. The effect is proportional to the strength of the acid (eg., less than 0.1 % chloroacetic acid in benzene is sufficient for maximal efficiency) and corresponds to general acid catalysis, suggesting that protonation of the persulfoxide occurs. On the other hand, with sulfides possessing an activated hydrogen in ${\alpha}$ position (eg., benzyl and allyl sulfides), hydrogen transfer becomes an efficient process in aprotic media and yields a S-hydroperoxysulfoniumm ylide, possibly arising from a conformation of the persulfoxide that is different from the one protonated in the presence of acids. Calculations on some substituted sulfides support this hypothesis. This process, which leads to C-S bond fragmentation with formation of an aldehyde, may be viewed as a general method for the preparation of aryl and heteroaryl aldehydes. In this effort, mechanistic studies offered new hints on the structure of the intermediate persulfoxide.

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A study of the High Sensitive Nonsilver Halide Imaging Material( I ) - Purification of CuPc pigment by a train sublimation technique and preparation of CuPc pigment thin films and it's application for electrophotoconductor - (고감도 비은염 화상재료 개발연구( I ) - CuPc안료의 승화정제 및 전해석출법에 의한 CuPc 박막의 제작과 전자사진감광체에의 응용)

  • 이상남
    • Journal of the Korean Graphic Arts Communication Society
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    • v.8 no.1
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    • pp.53-70
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    • 1990
  • It is well known that viologens such as 1.1 - disubstituted 4, 4` - bipyridinium salts and those used as redox indicator, herbicide and electrocheromic display device because those possess the lowest redox potential in any organic system. Viologen salts produced reversible high blue color under the influence of radical cation by photoreduction This study is related to the synthesis of viologen derivatives and the photoreduction property in water solution stats and the polar aprotic polyvinylpyrrolidone(PVP) matrix.

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Preparation of New Polyenaminonitriles Containing Cyclic and Methylene Units and Their Thermal Properties

  • Cho, Jeong-Hyun;Gong, Myoung-Seon
    • Macromolecular Research
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    • v.8 no.5
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    • pp.209-214
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    • 2000
  • Polyenaminonitriles containing cycloaliphatic and aliphatic units were prepared by interfacial or solution polymerization reaction of p-bis(1-chloro-2,2-dicyanovinyl) benzene (1) with 4-aminobenzyl-amine, 1-(2-aminoethyl)piperazine, 2-(aminomethyl)pyrrolidine and 4-(aminomethyl)piperidine. The chemical structure of the polymers was confirmed through a syntheses of the model compound. The resulting polymers possessed inherent viscosities of 0.29∼0.62 dL/g and they were easily soluble in polar aprotic solvents and common organic solvents. Thermal properties of the polymers such as curability and stability were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and infrared spectroscopy. The polymers exhibited a large exotherm in DSC analyses and underwent a curing reaction around 340-370$\^{C}$ to form insoluble materials. The polymers showed 70-80% residual weight at 600 $\^{C}$ under nitrogen.

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Polarographic Behavior of Azo Series Organic Compounds (II). Reduction of 1-(2-Pyridylazo)-2-naphthol in Acetonitrile (Azo계 유기화합물의 폴라로그래프법적 거동 (제2보). 아세토니트릴 중에서 1-(2-Pyridylazo)-2-naphthol의 환원)

  • Heung Lark Lee;Zun Ung Bae
    • Journal of the Korean Chemical Society
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    • v.27 no.1
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    • pp.24-30
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    • 1983
  • The polarographic behavior of 1-(2-pyridylazo)-2-naphthol (PAN) in acetonitrile as an aprotic solvent has been investigated. The reduction of PAN in $10^{-2}$ molarity of tetraethyl-ammonium perchlorate acetonitrile solution proceeds along two one-electron steps to give the corresponding hydrazo compound. Every reduction wave was diffusion controlled and considerably reversible. The reduction mechanism of PAN in acetonitrile is estimated as follows;

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Redox Reaction of Poly(ethyleneterephthalate) Polymer in Aprotic Solvent

  • Choi, Chil-Nami
    • Environmental Sciences Bulletin of The Korean Environmental Sciences Society
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    • v.10 no.S_1
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    • pp.47-53
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    • 2001
  • We carroed our to measure the variations of potential with current density (polarization curves) for poly(ethyleneterephthalate). The results were particularly examined to identify the influences on corrosion potential and corrosion rate of various factors including temperature, pH, exposure time, salt, and enzyme. The Tafel slope for anodic dissolution was determined by the polarization effect depending on these conditions. The optimum conditions were established for each case. The second anodic current density peak and maximum passive current density were designated as the relative corrosion sensitivity$(I_r/I_f)$. The mass transfer coefficient value$(\alpha)$ was determined with the Tafel slope for anodic dissolution based on the polarization effect with optimum conditions.

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Phenol/formaldehyde-derived macroporous carbon foams prepared with aprotic ionic liquid as liquid template

  • Byun, Hae-Bong;Nam, Gi-Min;Rhym, Young-Mok;Shim, Sang-Eun
    • Carbon letters
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    • v.13 no.2
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    • pp.94-98
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    • 2012
  • Herein, macroporous carbon foams were successfully prepared with phenol and formaldehyde as carbon precursors and an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ($BMIPF_6$), as a pore generator by employing a polymerization-induced phase separation method. During the polycondensation reaction of phenol and formaldehyde, $BMIPF_6$ forms a clustered structure which in turn yields macropores upon carbonization. The morphology, pore structure, electrical conductivity of carbon foams were investigated in terms of the amount of the ionic liquid. The as-prepared macroporous carbon foams had around 100-150 ${\mu}m$-sized pores. More importantly, the electrical conductivity of the carbon foams was linearly improved by the addition of $BMIPF_6$. To the best of the author's knowledge, this is the first result reporting the possibility of the use of an ionic liquid to prepare porous carbon materials.

Nucleophilic Displacement at Sulfur Center (X). Solvolysis of Phenylmethanesulfonyl Chloride (黃의 親核性 置換反應(제10보). 鹽化페닐메탄술포닐의 加溶媒分解反應)

  • Ikchoon Lee;Wang Ki Kim
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.111-116
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    • 1978
  • The kinetics of phenylmethanesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been investigated. The rate was faster in protic solvents than in aprotic solvents while susceptibility of rate to the ionizing power, i. e., m of the Winstein plot and solvation number of the transition state were much smaller in protic solvents. This was considered in the light of initial state stabilization by hydrogen-bonding solvation of the protic solvents. It was concluded that the reaction proceeds by an $S_N2$ mechanism in which bond-formation precedes bond-breaking at the transition state in all solvent systems.

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