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Reactions of peroxyacetyl radicals with reduced sulfur compounds

Reaktionen von Peroxyacetylradikalen mit reduzierten Schwefelverbindungen

  • Anorganische Und Physikalische Chemie
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Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Summary

The reaction of peroxyacetyl radicals with reduced sulfur compounds was studied at 55°C in N2 at 1 000 mbar total pressure. The radicals were generated in equilibrium with peroxyacetyl nitrate and NO2 in large excess. The pseudo first order decay ofPAN was measured in the absence and presence of several 100 ppm CH3SH, C2H5SH,n-C4H9SH, (CH3)2S, and (CH3S)2. Computer simulations yielded the following rate constants of peroxyacetyl radicals with the above mentioned sulfur compounds: 3.7, 2.8, 13.0, 0.9, and 1.8·10−16 cm3/s, respectively. An electron capturing compound of the thiols with NO2 was observed.

Zusammenfassung

Die Reaktionen von Peroxyacetylradikalen mit reduzierten Schwefelverbindungen wurden bei 55°C in NO2 bei einem Totaldruck von 1 000 mbar untersucht. Die Radikale wurden im Gleichgewicht mit Peroxyacetylnitrat und NO2 in großem Überschuß generiert. Der nach erster Ordnung verlaufende Zerfall vonPAN wurde in Abwesenheit und Anwesenheit und von einigen ppm CH3SH, C2H5SH,n-C4H9SH, (CH3)2S und (CH3S)2 gemessen. Computersimulierung der Geschwindigkeitskonstanten für die Peroxyacetylradikale ergab mit den genannten Schwefelverbindungen 3.7, 2.8, 13.0, 0.9 und 1.8·10−16 ch3/s. Eine elektronenfangende Verbindung der Thiole mit NO2 wurde beobachtet.

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References

  1. Pate C. T., Atkinson R., Pitts J. N. (1976). J. Environ. Sci. Health, Environ. Sci. Eng.A II (1): 19

    Google Scholar 

  2. Cox R. A., Roffey M. J. (1977) Environ. Sci. Technol.11: 900

    Google Scholar 

  3. Schurath U., Vipprecht V. (1980) In: Versino B., Ott H. (eds.) Physico-Chemical Behaviour of Atmospheric Pollutants. Reidel D., Dordrecht, p. 157

    Google Scholar 

  4. Erickson D. J., Ghan S. J., Penner J. E. (1990) J. Geophys. Res.95: 7543

    Google Scholar 

  5. Gaffney J. S., Fajer R., Senum G. I. (1984) Atmos. Environ.18: 215

    Google Scholar 

  6. Roumelis N., Glavas S. (1992) Monatsh. Chem.123: 63

    Google Scholar 

  7. Atkinson R., Baulch D. L., Cox R. A., Hampson R. F. Jr., Kerr J. A., Troe J. (1989) J. Phys. Chem. Ref. Data18: 881

    Google Scholar 

  8. Moortgat G., Veyret B., Lesclaux R. (1989) J. Phys. Chem.93: 2362

    Google Scholar 

  9. Moortgat G. K., Veyret B., Lesclaux R. (1987) Cost 611, WP 2 Meeting Riso National Laboratory, Denmark, p. 24

  10. Batt L., Rattray G. N. (1979) Int. J. Chem. Kinet.11: 1183

    Google Scholar 

  11. Yamada F., Slangle I., Gutman D. (1981) Chem. Phys. Letts.83: 409

    Google Scholar 

  12. Atkinson R., Lloyd A. C. (1984) J. Phys. Chem. Ref. Data13: 315

    Google Scholar 

  13. DeMore W. B., Sander S. P., Golden D. M., Molina M. J., Hampson R. F., Kurylo M. J., Howard C. J., Ravishankara A. R. (1990) Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling9

  14. Balla R. J., Heicklen J. (1985) J. Phys. Chem.89: 4596

    Google Scholar 

  15. Balla R. J., Nelson H. H., McDonald J. R. (1986) Chem. Phys.109: 101

    Google Scholar 

  16. Black G., Jusinski L. E., Patrick R. (1988) J. Phys. Chem.92: 5972

    Google Scholar 

  17. McLeod H., Aschmann S. M., Atkinson R., Tuazon E. C., Winer A. M., Pitts J. N. Jr. (1986) J. Geophys. Res.91: 5338

    Google Scholar 

  18. Atkinson R. (1985) Chem. Rev.85: 69

    Google Scholar 

  19. Balla R. J., Heicklen J. (1984) J. Phys. Chem.88: 6314

    Google Scholar 

  20. Andreae M. O., Ferek R. J., Bermond F., Byrd K. P., Engstrom R. T., Hardin S., Houmere P. D., LeMarrec F. and Raemdonck H. (1985) J. Geophys. Res.90: 12891

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, University of Patras, GR-26110, Patras, Greece

    Gerassimos Mineshos & Sotirios Glavas

  2. Institut für Physikalische Chemie, Universität Bonn, D-W-5300, Bonn, Federal Republic of Germany

    Ulrich Schurath

Authors
  1. Gerassimos Mineshos
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  2. Sotirios Glavas
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  3. Ulrich Schurath
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Mineshos, G., Glavas, S. & Schurath, U. Reactions of peroxyacetyl radicals with reduced sulfur compounds. Monatsh Chem 123, 501–508 (1992). https://doi.org/10.1007/BF00816843

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  • DOI: https://doi.org/10.1007/BF00816843

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