超臨界水の構造・ダイナミクス・反応  [in Japanese] Structure, Dynamics, and Reaction of Supercritical Water  [in Japanese]

Access this Article

Search this Article

Author(s)

    • 松林 伸幸 MATUBAYASI Nobuyuki
    • 京都大学化学研究所界面物性研究部門 Division of Solution and Interface Chemistry, Institute for Chemical Research, Kyoto University

Abstract

The hydrogen bonding structure and dynamics of supercritical water is studied by means of high-temperature and high-pressure NMR. The proton chemical shift is measured over a wide range of thermodynamic conditions and is related to the number of hydrogen bonds in supercritical water with the help of computer simulations. It is found that the hydrogen bonding persists at supercritical temperatures and that the average number of hydrogen bonds is at least one in the supercritical densities. The spin-lattice relaxation time is further measured to determine the reorientational correlation time. It is shown that while the reorientational relaxation proceeds on the order of picosecond in ambient water, it does on the order of several tens of femtoseconds in supercritical water. The role of water in noncatalytic reactions in hydrothermal conditions is also examined by focusing on the dehydration of 1, 4-butanediol into tetrahydrofuran, which proceeds under the presence of a strong acid at ambient conditions. The water-induced and acid-catalyzed rate constants are separately determined, and water is proven to promote the reaction in its undissociated form.

Journal

  • The Review of High Pressure Science and Technology

    The Review of High Pressure Science and Technology 12(2), 159-166, 2002-05-20

    The Japan Society of High Pressure Science and Technology

References:  32

  • <no title>

    水熱科学ハンドブック編集委員会

    水熱科学ハンドブック, 1997

    Cited by (7)

  • <no title>

    MATUBAYASI N.

    Phys. Rev. Lett. 78, 2573, 4309, 1997

    Cited by (3)

  • <no title>

    松林伸幸

    高圧力の科学と技術 6, 16, 1997

    Cited by (3)

  • <no title>

    松林伸幸

    高圧力の科学と技術 10, 283, 2000

    Cited by (1)

  • <no title>

    SHAW R. W.

    Chem. Eng. News Dec. 23, 26, 1991

    Cited by (3)

  • <no title>

    TOWNSEND S. H.

    Ind. Eng. Chem. Res. 27, 143, 1988

    Cited by (16)

  • <no title>

    KLEIN M. T.

    Ind. Eng. Chem. Res. 31, 182, 1992

    Cited by (3)

  • <no title>

    KATRITZKY A. R.

    Acc.Chem.Res. 29, 399, 1996

    Cited by (9)

  • <no title>

    AN J.

    J.Org.Chem. 62, 2505, 1997

    Cited by (5)

  • <no title>

    JARRELL C. L.

    Advances in Environmental Research 1, 373, 1997

    Cited by (1)

  • <no title>

    SAVAGE P. E.

    Chem.Rev. 99, 603, 1999

    Cited by (12)

  • <no title>

    BROLL D.

    Angew. Chem. Int. Ed. 38, 2998, 1999

    Cited by (5)

  • <no title>

    IKUSHIMA Y.

    Angew. Chem. Int. Ed. 40, 210, 2001

    Cited by (3)

  • <no title>

    日本機械学会

    技術資料 流体の熱物性値表, 1983

    Cited by (2)

  • <no title>

    POSTORINO P.

    Nature 366, 668, 1993

    Cited by (8)

  • <no title>

    MOUNTAIN R. D.

    J. Chem. Phys. 90, 1866, 1989

    Cited by (5)

  • <no title>

    LAMB W. J.

    J. Chem. Phys. 74, 913, 1981

    Cited by (5)

  • <no title>

    LAMB W. J.

    J. Chem. Phys. 74, 6875, 1981

    Cited by (4)

  • <no title>

    OKADA K.

    J.Chem.Phys. 107, 9302, 1997

    Cited by (5)

  • <no title>

    OKADA K.

    J. Chem. Phys. 110, 3026, 1999

    Cited by (4)

  • <no title>

    BALBUENA P. B.

    J. Phys. Chem. B102, 3806, 1998

    Cited by (2)

  • <no title>

    OKAZAKI S.

    J. Chem. Phys. 103, 8594, 1995

    Cited by (4)

  • <no title>

    HERTZ H. G.

    Water, A comprehensive treatize, 1973

    Cited by (1)

  • <no title>

    PITZER K. S.

    Activity coefficients in electrolyte solutions, 1991

    Cited by (2)

  • <no title>

    大野惇吉

    最も単純な有機化学反応, 1997

    Cited by (1)

  • <no title>

    R. T. モリソン

    有機化学, 1994

    Cited by (1)

  • <no title>

    HUDSON B. G.

    J. Org. Chem. 32, 3650, 1967

    Cited by (2)

  • <no title>

    MATUBAYASI N.

    J. Chem. Phys. 107, 9133, 1997

    DOI  Cited by (17)

  • <no title>

    MATUBAYASI N.

    J. Chem. Phys. 110, 8000, 1999

    DOI  Cited by (7)

  • Noncatalytic Cannizzaro - type Reaction of Formaldehyde in Hot Water

    TSUJINO Yasuo , WAKAI Chihiro , MATSUBAYASHI Nobuyuki , NAKAHARA Masaru

    Chem. Lett. 1999(4), 287-288, 1999-04-05

    References (19) Cited by (2)

  • <no title>

    YOSHII N.

    J. Chem. Phys. 109, 4873, 1998

    DOI  Cited by (7)

  • Structural study of supercritical water. III. Rotational dynamics

    Matubayasi N , Nakao N , Nakahara M

    JOURNAL OF CHEMICAL PHYSICS 114(9), 4107-4115, 2001-03-01

    IR  DOI  Cited by (10)

Codes

  • NII Article ID (NAID)
    10008628926
  • NII NACSIS-CAT ID (NCID)
    AN10452913
  • Text Lang
    JPN
  • Article Type
    REV
  • ISSN
    0917639X
  • NDL Article ID
    6183377
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z17-1589
  • Data Source
    CJP  NDL  J-STAGE 
Page Top