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INVESTIGATION OF ELEMENTARY REACTION PATHS BY EXPERIMENTS AND THEORETICAL CALCULATIONS

Research Project

Project/Area Number 62470011
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionHiroshima University

Principal Investigator

SAITO Ko  HIROSHIMA UNIV., DEPT. CHEM., ASSOCIATE PROF., 理学部, 助教授 (00033853)

Co-Investigator(Kenkyū-buntansha) KAKUMOTO Terumitsu  HIROSHIMA UNIV., DEPT. CHEM., ASSISTANT, 理学部, 助手 (50185724)
YABUSHITA Satoshi  HIROSHIMA UNIV., DEPT. CHEM., ASSISTANT, 理学部, 助手 (50210315)
KANDA Katsuya  HIROSHIMA UNIV., DEPT. CHEM., ASSISTANT, 理学部, 助手 (10169790)
Project Period (FY) 1987 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1989: ¥100,000 (Direct Cost: ¥100,000)
Fiscal Year 1988: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1987: ¥5,200,000 (Direct Cost: ¥5,200,000)
KeywordsREACTION PATH / TRANSITION STATE / REACTION RATE CONSTANT / UNIMOLECULAR REACTION / SHOCK-TUBE METHOD / AB INITIO CALCULATION / 素反応速定数 / 赤外線レーザー加熱 / 素反応速度定数 / 衝撃波管
Research Abstract

1. We determined the rate constants of elementary steps of several species at high temperatures. In most cases, the rate constants were in good agreement with the theoretically calculated values. In the case of propynal, however, the experimental decomposition rate was found very high in comparison with the calculation. From the calculated transition-state structure, the high experimental rate constant was explained by the fact that at the saddle point there are excited vibrational modes which give a higher number of state than the equilibrium value.
2. It was found that in the consecutive reaction the secondary step was governed by the structure and the energy of the first transition state. This is one of the methods of chemical activation. The activation by this method gives rise to a special molecular structure depending on the parent molecule. In fact, the carboxylic acids produced from the pyrolysis of esters decomposed via competing paths whose branching ratio was not the same as the values of the thermally equilibrated acids. These phenomena were well explained by ab initio calculations.
3. In the cause of this investigation it was confirmed that the theoretical calculation based on the molecular orbital method well corresponded to the experimental results. This fact is thought to contribute to the field of the chemical kinetics where even now many experimentalists do not believe, the results of the theoretical calculation.

Report

(4 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • 1987 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] K.Saito: "Unimolecular Thermal Decomposition of Formaldoxime at High Temperatures:Experiments and Calculations" J.Phys.Chem.,. 92. 4371-4374 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Saito: "The Thermal Unimolecular Decomposition of 3,4-dihydro-2H-pyran behind Refelected Shock Waves" Chem.Phys.Lett.,. 165. 383-385 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Saito: "On the Thermal Unimolecular Decomposition of Propynal" Chem.Phys.Lett.,印刷中.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Saito: "Thermal Decomposition of Ethyl Acetate.Branching Ratio of the Competing paths in the pyrolysis of the Produced Acetic Acid" Chem.Phys.Lett.,印刷中.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Saito: "Investigations of the Unimolecular Behavior of Relatively Large Molecules:Shock Tube Experiments and Molecular Orbital Calculations" Proceedings of the National Symposium on Shock Wave Phenomena,Sagamihara,印刷中.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Shimofuji: "Unimolecular Theraml Decomposition of Ethyl Vinyl Ether and the Consecutive Thermal Reaction of the Intermadiary Product Acetaldehyde:Experiments and Calculations" J.Phys.Chem.,投稿中.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Saito, K. Makishita, T. Sasaki, T. Kakumoto, and A. Imamura: "Unimolecular Thermal Decomposition of Formaldoxime at High Temperatures: Experiments and Calculations." J. Phys. Chem., 92, 4371-4374 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Saito, K. Adachi, M. Watanabe, K. Shimofuji, and A. Imamura: "The Thermal Unimolecular Decomposition of 3,4-dihydro-2H-pyran behind Reflected Shock Waves." Chem. Phys. Lett., 165, 383-385 (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Saito, Y. Mochizuki, I. Yoshinobu, and A. Imamura: "On the Thermal Unimolecular Decomposition of Propynal." Chem. Phys. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Saito, T. Sasaki, I. Yoshinobu, and A. Imamura: "Theramal Decomposition of Ethyl Acetate. Branching Ratio of the Competing Paths in the Pyrolysis of the Produced Acetic Acid." Chem. Phys. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Saito, K. Shimofuji, K. Adachi, M. Watanabe, and A. Imamura: "Investigations of the Unimolecular Behavior of Relatively Large Molecules: Shock Tube experiments and Molecular Orbital Calculations." Proc. National Sympo. on Shock Wave Phenomena.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Shimofuji, K. Saito, and A. Imamura: "Unimolecular Thermal Decomposition of Ethyl Vinyl Ether and the Consecutive Thermal Reaction of the Intermediary Product Acetaldehyde: Experiments and Calculations." J. Phys. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Saito: "Unimolecular Thermal Decomposition of Formaldoxime at High Temperatures:Experiments and Calculations" J.Phys.Chem.92. 4371-4374 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Saito: "The Theraml Unimolecular Decomposition of 3,4-dihydro-2H-pyran behind Reflected Shock Waves" Chem.Phys.Lett.165. 383-385 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Saito: "On the Thermal Unimolecular Decomposition of Propynal" Chem.Phys.Lett.

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Saito: "Thermal Decomposition of Ethyl Acetate.Branching Ratio of the Competing Paths in the Pyrolysis of the Produced Acetic Acid" Chem.Phys.Lett.

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Saito: "Investigations of the Unimolecular Behavior of Relatively Large Molecules:Shock Tube Experiments and Molecular Orbital Calculations" Proceedings of the National Symposium on Shock Wave Phenomena,Sagamihara.

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Shimofuji: "Unimolecular Thermal Decomposition of Ethyl Vinyl Ether and the Consecutive Thermal Reaction of the Intermadiary Product Acetaldehyde:Experiments and Calculations" J.Phys.Chem.

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Saito: J.Phys.Chem.92. 4371-4374 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Saito: Chem.Phys.Lett.

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Saito: J.Amer.Chem.Soc.

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Shimofuji: J.Phys.Chem.

    • Related Report
      1988 Annual Research Report
  • [Publications] I.Yoshinobu: J.Phys.Chem.

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Saito: Chem.Phys.Lett.

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Saito: J.Physical Chamistry. (1988)

    • Related Report
      1987 Annual Research Report
  • [Publications] K.Saito: Chemical Physics Letters.

    • Related Report
      1987 Annual Research Report
  • [Publications] K.Saito: J.American Chemical Society.

    • Related Report
      1987 Annual Research Report

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Published: 1987-04-01   Modified: 2016-04-21  

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