Linear-Reactor-IR.-Matrix and Microwave Spectroscopy of the System O3/NO2/(Z)-2-Butene |
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Authors: | Joseph Dommen Martin Forster Heidi Ruprecht Alfred Bauder Hans-Heinrich Günthard |
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Affiliation: | Laboratorium für Physikalische Chemie, Eidgenössische Technische Hochschule, CH-8092 Zürich |
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Abstract: | Investigation of the formation of complex reaction products in the gas-phase system O3/NO2/(Z)-2-butene by combination of linear reactors with IR. matrix and microwave Stark Spectroscopy is reported. Besides the polyatomic products observed earlier in the gas-phase ozonolysis of (Z)-2-butene, the following products were identified; N2O5, HNO3, HNO4, CH3NO2, CH3ONO, CH3COONO2 and CH3COO2NO2 (peroxyacetyl nitrate, PAN). Matrix IR. spectra of N2O5, HNO3. CH3COONO, CH3COONO2 required for reference purposes are presented. It is shown that PAN-formation occurs already in the absence of light. A reaction scheme is proposed for explanation of the observed complex NOx-containing products, which assumes methyldioxirane as a central intermediate. Particular reaction steps of the scheme will be discussed, including thermochemical estimates of reaction enthalpies. |
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