Pressure Stabilization of Criegee Intermediates Formed from Symmetric trans-Alkene Ozonolysis

Hakala, J.P., and N.M. Donahue (2018), Pressure Stabilization of Criegee Intermediates Formed from Symmetric trans-Alkene Ozonolysis, J. Phys. Chem. A, 122, 9426-9434, doi:10.1021/acs.jpca.8b09650.
Abstract

We explore the pressure dependence of a stabilized Criegee Intermediate

Downloaded via CARNEGIE MELLON UNIV on January 3, 2019 at 15:16:48 (UTC). (sCI) formation from a sequence of trans-alkene ozonolysis reactions. To study the effect of carbon chain length on the stabilization, we select five symmetric trans-alkenes ranging from trans-2-butene (C4) through trans-7-tetradecene (C14). We measure the pressure falloff curves for each alkene from 50 to 900 Torr in a flow reactor using conversion of SO2 to H2SO4 with and without an OH scavenger, and subsequent detection of H2SO4 with a nitrate chemical ionization mass spectrometer to constrain sCI yields. As the length of the carbon chain increases, we observe a systematic increase in Criegee Intermediate stabilization at a given pressure, along with a systematic decrease in the low-pressure limit. Our results also suggest that for these symmetrical systems the anticonformer of the Criegee Intermediate stabilizes before (at lower pressure than) the syn conformer.

PDF of Publication
Download from publisher's website
Research Program
Atmospheric Composition
Tropospheric Composition Program (TCP)