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Correlation between Microscopic Structure and Chemical Reaction in Low-density Supercritical Water

Research Project

Project/Area Number 09440207
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

YAMAGUCHI Toshio  Fukuoka University, Faculty of Science, Prof., 理学部教授 (70158111)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥8,300,000 (Direct Cost: ¥8,300,000)
Fiscal Year 1998: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1997: ¥6,400,000 (Direct Cost: ¥6,400,000)
KeywordsHydrogen-bonded cluster / Supercritical water / Supercritical methanol / Neutron diffraction / XAFS / Hydration structure / X-ray diffraction / EXAFS / 中性子回折 / X線回折 / 超臨界 / 小角散乱 / 臨界点
Research Abstract

(1)High-temperature and high-pressure solution sample cells for XAFS, small-angle X-ray and neutron scattering have been constructed. Maximum pressure and temperature used for the cells are 50 MPa and 400 ゚C.
(2)XAFS measurements on 0.1 M aqueous Co(N03)2 solution were made at 25゚C(0.1 MPa), 250゚C(30 MPa), and 400゚C(35 MPa). It has been found that the hydration number of Co^<2+> decreases from 6 at 25゚C to 4 at 400゚C, the Co-H_2 distance being 2.06-2.08 A.
(3)The structure of methanol at ambient (25゚C), subcritical (202゚C), and supercritical(253゚C)temperatures has been investIgated by neutron diffraction with hydroxyl H/D) substitution and Empiricat Parameter Structure Refinement methods. It has been found that methanol molecules are arranged as chain-like by hydrogen bonding and that clusters of 5-6 methanol molecules are formed at the supercritical temperature and are broken down with decreasing density.
(4)X-ray diffraction measurements on a methanol-water binary solution (methanol mole fraction is 0.3) were made over a temperature range 25-200゚C.It has been found that hydrogen bonds at 2.9 A are largely broken down with increasing non-hydrogen bonds at 3.5 A.
(5)The orientational correlation function on Cl hydration in supercritical water has been derived by neutron diffraction on a 3 m LiCl solution in D_2 with ^<35>C/^<37>C substitution, EPSR, and spherical harmonic expansion methods. It has been found that all water molecules around Cl remain in the first coordination shell, but are randomly oriented toward Cl.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] P.Smirnov: "X-ray Diffraction Study on Aqueous Scandium (III) Perchlorate and Chloride Solutions over a Temperature Range -45 -95 ℃" J.Phys.Chem.102(24). 4801-4808 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi: "Structure of Subcritical and Supercritical Hydrogen-bonded Liquids and Solutions" J.Mol.Liq.78. 43-50 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Takamuku: "Liquid Structure of Acetonitrile-Water Mixtures by X-ray Diffraction and Infrared Spectroscopy" J.Phys.Chem.102(44). 8880-8888 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi: "Observation of Chloride-ion Hydration in High-termperature Liquid and Supercitical Water by Spherical Hrmonic Expansion Analysis" J.Chem.Phys.110(7). 3529-3535 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi: "Development of a Rapid Liquid and Amorphous X-ray Diffractometer Using an Imagin Plate Area Detector." Fukuoka Univ.Sci.Reports. 29(1). 127-136 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi: "The Structure of Liquid Methanol Revisited : A Neutron Diffraction Experiment at -80℃ and +25℃." Mol.Phys.in press. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] P.Smirnov, et al.: "An X-Ray Diffraction Study on Concentrated Aqueous Calcium Nirate Solutions at Subzero Temperatures" J.Mol.Lip.73/74. 305-316 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Ohtaki, et al.: "Structure of Water under the Subcritical and Supercritical Conditions Studied by Means of Solution X-ray Diffraction" Chem.Soc.Rev.41-51 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Nakahara, et al: "The Structure of Water and Aqueous Electrolyte Solutions under Extreme Conditions" in Recent Research Development in Physical Chemistry. 1. 17-49 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Valli, et al: "An in situ X-ray Absorption Fine Structure Study of Different Oxidation States of Oxo-and Hydroxo-bridged Ruthenium Dimers in Acetonitrile Solution" Inorg.Chem.36. 4622-4626 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Takamuku, et al.: "X-ray Diffraction Studies on Supercooled Aqueous Lithium Bromide and Lithium Iodide Solutions" Z.Naturforsch. 52a. 521-527 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Takamuku, et al.: "Thermal Property, Structure, and Dynamics of Supercooled Water in Porous Silica by Calorimetry, Neutron Scattering, and NMR Relaxation" J.Phys.Chem.B. 101. 5730-5739 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi, et al.: "Scandium(III)Hydration in Aqueous Solution from X-ray Diffraction and X-ray Absorption Fine Structure Measurements" Chem.Phys.Lett.274. 485-490 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] P.Smirnov, et al.: "X-ray Diffraction Study on Aqueous Scandium(III)Perchlorate and Chloride Solutions over a Temperature Range -45-95゚C" J.Phys.Chem.102(24). 4801-4808 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi: "Structure of Subcritical and Supercritical Hydrogen-bonded Liquids and Solutions" J.Mol.Liq.78. 43-50 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Takamuku, et al.: "Liquid Structure of Acetonitrile-Water Mixtures by X-ray Diffraction and Infrared Spectroscopy" J.Phys.Chem.102(44). 8880-8888 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi, et al.: "Observation of Chloride-ion Hydration in High-temperature Liquid and Supercritical Water by Spherical Harmonic Expansion Analysis" J.Chem.Phys.110(7). 3529-3535 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi, et al.: "Development of a Rapid Liquid and Amorphous X-ray Diffractometer Using an Imaging Plate Area Detector" Fukuoka Univ.Sci.Reports. 29(1). 127-136 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Yamaguchi: "The Structure of Liquid Methanol Revisited : A Neutron Diffraction Experiment at -80゚C and +25゚C" Mol.Phys.(in press). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Takamuku, et al.: "Structure and Dynamics of 1,4-Dioxane-Water Binary Solutions Studied by X-ray Diffraction, Mass Spectroscopy, and NMR Relaxation" J.Mol.Liq.(in press). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] P. Smirnov: "X-ray Diffraction Study on Aqueous Scandium(III) Prechlorate and Chloride Solutions over a Temperature Range-45-95℃" J. Phys. Chem.102(24). 4801-4808 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Yamaguchi: "Structure of Subcritical and Supercritical Hydrogen-bonded Liquids and Solutions" J. Mol. Liq.78. 43-50 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Takamuku: "Liquid Structure of Acetonitrile-Water Mixtures by X-ray Diffraction and Infrared Spectroscopy" J. Phys. Chem.102(44). 8880-8888 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Yamaguchi: "Observation of Chlorede-ion Hydration in High-temperature Liquid and Supercritical Water by Spherical Harmonic Expansion Analysis" J. Chem. Phys.110(7). 3529-3535 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Yamaguchi: "Development of a Rapid Liquid and Amorphous X-ray Diffractometer Using an Imaging Area Detector" Fukuoka Univ. Sci. Reports. 29(1). 127-136 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T. Yamaguchi: "The Structure of Liquid Methanol Revisited: A Neutron Diffraction Experiment at -80℃and +25℃" Mol. Phys.(in press.). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Ohtaki: "Structure of water under subcritical and supercritical conditions studied by solution X-ray diffraction" Chem.Soc.Rev.41-51 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] M.Nakahara: "The structure of water and aqueous electrolyte solutions under extreme coditions" Recent Res.Devel.in Phys.Chem.1. 17-49 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Takamuku: "Thermal property,structure,and dynamics of supercooled water in porous silica by calorimetry,neutron scattering,and NMR relaxation" J.Phys.Chem.B.101:29. 5730-5739 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Yamaguchi: "Scandium(III)hydration in aqueous solution from X-ray diffraction and X-ray absorption fine structure measurements" Chem.Phys.Lett.274. 485-490 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Takamuku: "X-ray diffraction studies on supercooled aqueous lithium bromide and lithium iodide solutions" Z.Naturforsch.52a. 521-527 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Yamaguchi: "Structure of subcritical and supercritical hydrogen-bonded liquids and solutions" J.Mol.Liquids. (in press). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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