Linear‐Reactor‐IR.‐Matrix and Microwave Spectroscopy of the System O3/NO2/(Z)‐2‐Butene

Helvetica Chimica Acta - Tập 65 Số 2 - Trang 504-520 - 1982
J. Dommen1, Martin Förster1, Heidi Ruprecht1, A. Bauder1, Hans‐Heinrich Günthard1
1Laboratorium für Physikalische Chemie, Eidgenössische Technische Hochschule, CH‐8092 Zürich

Tóm tắt

AbstractInvestigation 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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Helvetica Chimica Acta

Tập 65 Số 2

504-520

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