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Studies on Characteristic Properties of Supercritical Fluids from the View Point of Fluctuation

Research Project

Project/Area Number 13440173
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionChiba University

Principal Investigator

NISHIKAWA Keiko  Chiba University, Graduate School of Science and technology, Professor, 大学院・自然科学研究科, 教授 (60080470)

Co-Investigator(Kenkyū-buntansha) MORITA Takeshi  Faculty of Engineering, Tokyo University, Agriculture and Technology, Research Associate, 工学部, 助手 (80332633)
SAITOW Ken-ichi  Chiba University, Graduate School of Science and technology, Research Associate, 大学院・自然科学研究科, 助手 (80302579)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥17,300,000 (Direct Cost: ¥17,300,000)
Fiscal Year 2002: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 2001: ¥14,800,000 (Direct Cost: ¥14,800,000)
Keywordssupercritical fluids / supercritical solutions / fluctuation / small-angle X-ray scattering / Raman scattering / dynamic light scattering / active region / swelling / テラヘルツ電磁波
Research Abstract

Supercritical fluids are characterized by large inhomogeneity of molecular distribution. The density fluctuation is a suitable parameter for quantitative and direct description of the inhomogeneity. We have comprehensively investigated the density fluctuation of several kinds of supercritical fluids by means of small-angle X-ray scattering (SAXS) experiments and have found the following facts. .
(i)The density fluctuation forms a ridge when the contour map of their values is drawn in a phase diagram. (ii)The ridge corresponds to extrema of the various physical quantities of supercritical fluids, which are related to the second derivatives of the Gibbs free energy. (iii)The rate of increase in solubility becomes maximum on the ridge. Namely, the ridge separates the supercritical region into two, regions, in which the solubility is extremely different, (iv) The rate constants or equilibrium constants of various chemical reactions in supercritical fluids show singular behaviors on the ridge. It is concluded that the density fluctuation is one of the most fundamental factors which determine properties of supercritical fluids and its ridge is the boundary which separates, the supercritical region into two.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] K.Nishikawa, et al.: "Inhomogeneity of Mixing in Acetonitrile Aqueous Solution Studied by Small-Angle X-ray Scattering"The Journal of Physical Chemistry B. 106・3. 693-700 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Saitow, H.Ochiai, K.Kato, K.Nishikawa: "Correlation Time of Density Fluctuation for Supercritical Ethylene Studied by Dynamic Light Scattering"The Journal of Chemical Physics. 116・12. 4985-4992 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Koga, K.Nishikawa et al.: "Density-Fluctuation-Induced Swelling of Polymer Thin Films in Carbon Dioxide"Physical Review Letters. 89・12. 125506-1-125506-4 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Tozaki, J.Kudo, Z.Chen, K.Nishikawa: "Development of Apparatus for High-Resolution Measurement of Permittivity of Fluids near Critical Point and Detection of Critical Anomaly for Supercritical Ethylene"Japanese Journal of Applied Physics. 41・11A. 6455-6460 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Nishikawa, H.Ochiai, K.Saitow, T.Morita: "Static Inhomogeneity of Supercritical Ethylene Studied by Small-Angle X-ray Scattering"Chemical Physics. 286・2. 421-430 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Saitow, K.Otake, H.Nakayama, K.Ishii, K.Nishikawa: "Local Density Enhancement in Neat Supercritical Fluids due to Attractive Intermolecular Interaction"Chemical Physics Letters. 368. 209-214 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Nishikawa, K.Kusano, A.A.Arai, T.Morita: "Density Fluctuation of a van der Waals fluid in Supercritical state"The Journal of Chemical Physics. 118・3. 1341-1346 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Ayusawa, T. Morita, K. Nishikawa et al.: "Construction of a Sample Cell of Poisonous Organic Solvents in Supercritical State, for SAXS Measurement Construction of a Sample Cell of Poisonous Organic"Jpn. J. Appl Phys.. 40. 4260-4261 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Saitow, H. Ohtake, N. Sarukura and K. Nishikawa: "Terahertz Absorption Spectra of Supercritical CHF_3 to Investigate Local Structure through Rotational and Hindered Rotational Motions"Chem. Phys. Lett.. 341. 86-92 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Morita, K. Kusano, K. Nishikawa et al.: "Titanium Sample Holder for SAXS Measurements of Supercritical Aqueous Solutions"Rev. Sci. Instrm. 72. 3013-3018 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Saitow, H. Ochiai, T. Kato and K. Nishikawa: "Correlation Time of Density Fluctuation for Supercritical Ethylene Studied by Dynamic, Light Scattering"J. Chem. Phys. 116. 4985-4992 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Koga and K. Nishikawa. Et. Al.: "Density-Fluctuation-Induced Swelling of Polymer Thin Films in Carbon Dioxide"Phys. Rev. Lett. 89. 125506.1-4 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Tozaki, J. Kudo, Z. Chen and K. Nishikawa: "Development of an Apparatus for High-Resolution Measurement of Permittivity for Fluids near the Critical Point arid Detection of the Critical Anomaly on Supercritical Ethylene"Jpn J. Appl Phys. 41. 6455-6460 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Nishikawa, H. Ochiai, K. Saitow and T. Morita: "Static Inhomogeneity of Supercritical Ethylene Studied by Small-Angle X-ray Scattering"Chem. Phys. 286. 421-430 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Nishikawa, K. Kusano, A.A. Arai and T. Morita: "Density Fluctuation of a van der Waals Fluid at Supercritical State"J. Chem. Phys. 118. 1341-1346 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Saitow, K. Otake, and K. Nishikawa, et al.: "Local Density Enhancement in neat Supercritical Fluid due to Attractive Intermolecular Interactions"Chem. Phys. Lett. 368. 209-214 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Nishikawa et al.: "Inhomogeneity of Mixing in Acetonitrile Aqueous Solution Studied by Small-Angle X-ray Scattering"The Journal of Physical Chemistry B. 106.3. 693-700 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Saitow, H.Ochiai, K.Kato, K.Nishikawa: "Correlation Time of Density Fluctuation for Supercritical Ethylene Studied by Dynamic Light Scattering"The Journal of Chemical Physics. 116.12. 4985-4992 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Koga, K.Nishikawa, et al.: "Density-Fluctuation-Induced Swelling of Polumer Thin Films in Carbon Dioxide"Physical Review Letters. 89.12. 125506-1-125506-4 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Tozaki, J.Kudo, Z.Chen, K.Nishikawa: "Development of Apparatus for High-Resolution Measurement of Permittivity of Fluids near Critical Point and Detection of Critical Anomaly for Supercritical Ethylene"Japanese Journal of Applied Physics. 41.11A. 6455-6460 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Nishikawa, H.Ochiai, K.Saitow, T.Morita: "Static Inhomogeneity of Supercritical Ethylene Studied by Small-Angle X-ray Scattering"Chemical Physics. 286.2. 421-430 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Saitow, K.Otake, H.Nakayama, K.Ishii, K.Nishikawa: "Local Density Enhancement in Neat Supercritical Fluids due to Attractive Intermolecular Interaction"Chemical Physics Letters. 368. 209-214 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Nishikawa, K.Kusano, A.A.Arai, T.Morita: "Density Fluctuation of a van der Waals fluid in Supercritical state"The Journal of Chemical Physics. 118.3. 1341-1346 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Ayusawa, K.Nishikawa, T.Morita et al.: "Construction of Sample Cell of Poisonous Organic Solvents in Supercritical State for Small-Angle X-ray Measurements"Japanese J.Appl.Phys.. 40. 4260-4261 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Saitow, K.Nishikawa et al.: "Tershertz Absorptins Spectra of Sapercritical CHF_3 to Investigate Local Structure through Rotatinul and Hindered Rotational Motions"Chem.Phys.Lett.. 341. 86-92 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Morita, K.Nishikawa: "Titanium Sample Holder for Small-Angle X-ray Scattering Measurenents of Supercritical Aqueous Solutions"Rev.Sci.Instrm. 72. 3013-3018 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Nishikawa et al.: "Inhomogeneity of Mixing in Acetonitrile Aqueous Solutions Studied by Small-Angle X-ray Scattering"J.Phys.Chem.. 106. 693-700 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Saitow, K.Nishikawa et al.: "Correlation Time of Density Fluctuation for Supercritical Ethylene Studied by Dynamic Light Scattering"J.Chem.Phys.. 116. 4085-4992 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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