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1996 Fiscal Year Final Research Report Summary

Free Radical Processes in the Atmosphere

Research Project

Project/Area Number 05237106
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionNational Institute for Environmental Studies

Principal Investigator

WASHIDA Nobuaki  National Institute for environmental studies, Division Director, 大気圏環境部, 部長 (70101045)

Co-Investigator(Kenkyū-buntansha) MATUMI Yutaka  Hokkaido University, Associate Professor, 電子科学研究所, 助教授 (30209605)
AKIMOTO Hajime  The University of Tokyo, Professor, 先端科学技術センター, 教授 (50101043)
YAMASAKI Katsuyoshi  Niigata University, Associate Professor, 理学部, 助教授 (90210385)
KODA Seiichiro  Dept.of Chemical System engineering, The University of Tokyo, Professor, 工学部, 教授 (10011107)
SHIBUYA Kazuhiko  Tokyo Institute of Technology, Associate Professor, 理学部, 助教授 (30126320)
Project Period (FY) 1993 – 1995
KeywordsRO2 Radical / Ozone / Isoprene / Halocarbon / OH Radical / Laser-Induced-Fluoresence / Impinging-Flow-Method / Uptake Coefficient
Research Abstract

The following studies were carried out during the 1993-1995 fiscal years.
1] Free radical kinetirs related to atmospheric chemistry
1. Rate constants for reactions of RO_2 + NO,CH_2X + O_2, HS+O,NH_2+O,NHO+O,and CH_3 + N have been measured by a combination of pulsed laser photolysis and photoionization mass spectrometry.
2. Rate constants for reactions of the vibrationally excited free radicals, such as CF_2^<**> (v2) + O,NH_2^<**> (v2) + NO,HCO^<**> (v_1, v_2, v_3) + O_2 were determined by using laser induced fluorescence technique.
3. Photodissociation of O_3 at Huggins band (308-326nm) has been studied. The partial cross sections for the O (^1D) production in the photoobsorption of O_3 were determined.
2] Model experiments related to atmospheric chemistry.
1. The OH radical-initiated photooxidation of isoprene has been investigated experimentally by a 6-m^3 photochemical reaction chamber equipped with a long path length Fourier transform infrared spectrometer. The CO yield in the real atm … More osphere was evaluated as 30% on the carbon number basis, and global annual CO production from isoprene was estimated to be 105 TgCyr^<-1>.
2. Ozone destruction by CFC's (CFCl_3 and CF_2Cl_2), BFC's (CF_3Br and C2H_4Br_2), HCFC's (CH_3CCl_2F,CF_3CHCl_2, and CF_3CHCl) and CH3Br was demonstrated using a 6-m^3 evacuable photochemical chamber equipped with UV-enhanced Xe arc lamps. The decay of ozone by a catalytic cycle involving CI of Br atoms released from the photolysis of halocarbons by UV light was evident, although the chain length was far less than in the real stratosphere : It was about 8 for CFCI_3 and 40 for CF_3Br.
3] Development of a monitoring method of OH and HO_2
Detection of OH radicals in low concentration was carried out using an infrared-ultraviolet double resonance (IR-DR) LIF method. The detection limit was determined to be 1.3 * 10^9 radical cm^<-3>.
4] Heterogeneous reactions in the atmosphere.
In order to analyze the transport processes of active species from the bulk atmosphere across the aqueous surfaces, a novel method, named as "impinging flow method" was developed. The uptake of SO^2 by the water was studied and the uptake coefficient was strongly dependent on the pH value of the water and showed a slightly negative temperature dependence. The uptake of OH radicals was also studied and the typical value was 0.006 in the neutral region. Less

  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] A.Miyoshi,S.Hatakeyama.And N.Washida: "OH Radical-Initiated Photooxidation of Isoprene:An estimate of Global CO Production" J.Geophys.Res.99. 18779-18787 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Masaki S.Tsunashima,And N.Washida: "Rate Constant for Substitutes Methyl Radicals(CH_2OCH_3,CH_2NH_2,CH_2I,and CH_2CN)with O_2" J.Phys.Chem.99. 13126-13131 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Washida,T.Imamura,and H.Bandow.: "Experimental studied of Ozone Depletion by Chlorofluorocarbons(CFC's),Bromofluorocarbons(BFC's)Hydrochlorofluorocarbons(HCFC's),and CH3Br Using a 6-m^3 Photochemical Chamber" Bull.Chem.Soc.Jpn.69. 535-541 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.shimono and S.Koda: "Laser-spectroscopic measurement of uptake coefficients of trace gaseous species on aqueous surfaces" J.Chem.Eng.Japan.28. 779-785 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Akiike,K.Tsuji,K.Shibuya and K.Obi: "van der Waals vibrations of NO-methane complexes in the A^2 Σ^+state" Chem.Phys.Letters. 243. 89-93 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Yamasaki,A.Tanaka,A.Watanabe,K.Yokoyama and I.Tokue: "Rate Constants for the Reactions CF_2(X^1A_1,ν_2-0 Determined by a Photodissociation/Laser-Induced Fluorescence Technique" J.Phys.Chem.99. 15086-15092 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Matumi and S.M.Shamsuddin: "Vibrational and Rotational Encrgy Distribution of CIO Produced in Reactions of O(^1D)Atoms withe HCI,CCI_4 and Chlorofluoromethanes" J.Chem.Phys.103. 4490-4495 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inagaki,M.Abe,Y.Matsumi and M.Kawasaki and H.Tachikawa: "Collisional Excitation of CO by S(^1D)/S(^3P)Atoms" J.Phys.Chem.99. 12822-12828 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Miyoshi, S.Hatakeyama, and N.Washida: "OH Radical-Initiated Photooxidation of Isprene : An estimate of Global CO Production." J.Geophys.Res.99 (D9). 18779-18787 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Masaki, S.Tsunashima, and N.Washida: "Rate Constant for Reaction of Substituted Methyl Radicals (CH_2OCH_3, CH_2NH_2, CH_2I,and CH_2CN) with O_2." J.Phys.Chem.99. 13126-13131 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Washida, T.Imamura, and H.Bandow: "Experimental Studies of Ozone Depletion by Chlorofluorocarbons (CFC's), Bromofluorocarbons (BFC's), Hydrochlorofluorocarbons (HCFC's), and CH_3Br Using a 6-m^3 Photochemical Chamber." Bull.Chem.Soc.Jpn.69. 535-541 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Shimono and S.Koda: "Laser-Spectroscopic Measurement of Uptake Coefficients of Trace Gaseous Species on Aqueous Surfaces." J.Chem.Eng.Japan.28. 779-785 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Watanabe, K.Yamasaki, and I.Tokue: "Collision Energy Dependence of the Overall Rate Constant for the Reactions NH (a^1DELTA) +HN_3." Laser Chem.15. 183 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Yamasaki, A.Tanaka, A.Watanabe, K.Yokoyama, and I.Tokue: "Rate Constants for the Reactions CF_2 (X^1A_1, v_2=0 and 1) + O Determined by a Photodissociation/Laser-Induced Fluorescence Technique." J.Phys.Chem.99. 15086-15092 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Matsumi and S.M.Shamsuddin: "Vibrational and Rotational Energy Distribution of ClO Produced in Reactions of O (^1D) atoms with HCI,CCl_4 and Chlorofluoromethanes." J.Chem.Phys.103. 4490-4508 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Inagaki, M.Abe, Y.Matsumi, M.Kawasaki and H.Tachikawa: "Collisional Excitation of CO by S (^1D)/S (^3P) Atoms." J.Phys.Chem.99. 12822-12828 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Sato, Y.Matsumi, M.Kawasaki, K.Tsukiyama and R.Bersohn: "Ion Imaging of the Photodissociation of OCS near 217 and 230 nm." J.Phys.Chem.99. 16307-16314 (1995)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-09  

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