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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
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥75,500,000 (Direct Cost: ¥75,500,000)
Fiscal Year 1995: ¥21,400,000 (Direct Cost: ¥21,400,000)
Fiscal Year 1994: ¥26,100,000 (Direct Cost: ¥26,100,000)
Fiscal Year 1993: ¥28,000,000 (Direct Cost: ¥28,000,000)
KeywordsRO2 Radical / Ozone / Isoprene / Halocarbon / OH Radical / Laser-Induced-Fluoresence / Impinging-Flow-Method / Uptake Coefficient / NH_2ラジカル / 反応速度 / 置換メチルラジカル / 光イオン化質量分析法 / 赤外-紫外二重共鳴 / CF_2ラジカル / 適応係数 / CH_3O_2ラジカル / HO_2ラジカル / 反応機構
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

Report

(4 results)
  • 1996 Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (35 results)

All Other

All Publications (35 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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [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
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T. Imamura, N. Washida: "Measurements of Rate Constants for HO_2+NO and NH_2+NO Reactions by Time-Resolved Photoionization Mass Spectrometry." Laser Chem.16. 43-51 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A. Masaki, S. Tsunashima and N. Washida: "Rate Constants for Reactions 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)

    • Related Report
      1995 Annual Research Report
  • [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)

    • Related Report
      1995 Annual Research Report
  • [Publications] A. Watanabe, K. Yamasaki, and I. Tokue: "Collision Energy Dependence of the Overall Rate Constant for the Reactions." Laser. Chem.15. 183 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Yamasaki, A. Tanaka, K. Yokoyama, A. Watanase and Ikuo Tokue: "Rate Constant for the Reaction of CF_2(X^1A_<1, v2>=0 and 1)+O Determined by a Photodissociation/Laser-Induced Fluorescence Technique" J. Phys. Chem.99. 15086 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Matsumi, S. M. Shamsuddm: "Vibrational and Rotational Energy Distribution of ClO produced in Reactions of O(^1D)atoms with HCl CCl_4 and Chlorofluoromethans." J Chem Phys. 103. 4490 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A.Watanabe,I.Tokue and K.Yamasaki: "Collision Energy Dependence of the Overall Rate Constant for the Reactions NH(a^1Δ)+NH_3" Laser Chem.(in press).

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Shibuya,T.Kusumoto and H.Nagai: "Optical-optical double resonance spectroscopy of NO2 in the 590.1 min region" Laser Chem.14. 119 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Tsuji,K.Shibuya,and K.Obi: "Intermolecular vibrations of the complex of NO in the nδRydberg states and Ar" Laser Chem.15. 000 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] A.Miyoshi,H.Matsui,and N.Washida: "Detection and Reactions of HOCO Radical in Gas Phase." J.Chem.Phys.100. 3532 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] A.Masaki,S.Tsunashima,and N.Washida: "Rate Constant for the Reaction of CH_3O_2 with NO." J.Chem.Phys.Lett.,. 218. 523 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] A.Miyoshi,S.Hatakeyama,and N.Washida: "OH Radical-Inititated Photooxidation of Isoprene:An Estimate of Global CO production" J.Geophys.Res.99. 18779-18787 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] A.Miyoshi,H.Matsui,N.Washida: "Detection and reactions of the HOCO radical in gas phase" J.Chem.Phys. 100. 3532-3539 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] A.Masaki,S.Tsunashima N.Washida: "Rate constant for the reaction of CH_3O_2with NO." Chem Phys Lett. (印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Tanaka,Y.Kajii K.Shibuya,M.Nakata: "Visible-light-induced reactions of NO_2 with conjugated dienes in a low-temperature Ar matrix." J.Phys.Chem. 97. 7048-7053 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Aoki,H.Nagai K.Hoshina,K.Shibuya: "Rotational quantum number and vibronic symmetry of NO excited with visible light in the region of 563-566nm." J.Phys.Chem.97. 8889-8894 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Tsuji,K.Shibuya,K.Obi: "Bound-bound A^2SIGMA^+-X^2〓transition of NO-Ar van der waals complexes." J.Chem.Phys.(印刷中)100. (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Yamasaki,A.Tanaka,I.Tokue,Y.Ito: "Spin-forbidden excitation of CF_2(a^3B_1X^1A_1)by collision with N_2(A^3SIGMAu^+)." Chem.Phys.Lett.215. 483-487 (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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