| Project/Area Number |
02640349
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
物理化学一般
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| Research Institution | Hiroshima University |
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Principal Investigator |
SAITO Ko Hiroshima Uni., Fac. Sci., Professor, 理学部, 教授 (00033853)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥100,000 (Direct Cost: ¥100,000)
Fiscal Year 1990: ¥1,900,000 (Direct Cost: ¥1,900,000)
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| Keywords | Chemical Kinetics / Unimolecular reaction / Shock Tube method / IR Laser absorption / Uibrational modo exitation / 衝撃浸管法 / 赤外線レ-ザ-吸収 |
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| Research Abstract |
It is very important in the field of chemical kinetics to investigate that local-vibration-excited molecules behave different mannor from the usual molecules. Theortically, this is discussed on the basis of the coupling of the vibrational modes between the IRC and others. On the other hand, there are few report on the experimental study because of the difficulty of the obserbation. In this project, we tried to observe the reaction behavior by connecting the shock heating method and CO_2 infra-red laser shot. With this method it was found that acrylonitrile was decomposed after laser shot in the shock heated region. Since the laser power was less than 10mJ, laser shot merely perturbed the thermal disrtribution of the vibrational states.
The other method to produce local-vibration-excited molecules was the thermal decompositon of relatively large molecules. If ethyl vinyl ether is decomposed unimolecularly, acetaldehyde and ethylene are produced. The transition state of this reaction have a 6-centered structure and this structure suggests that the methyl group of the product aldehyde is strongly excited in the rotation or H-C-H bending mode. Therefore, it is expected that the acetaldehyde produced in this monnor behaves unusual kinetics. In fact, we found that this aldehyde decomposed with very large rate constants compared with the usual value.
Thus, we ascertained that the local excitation of vibrations affected sensitively the unimolecular decomposition rate.
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