2,3-Dimethyl-2-butene (TME) Ozonolysis: Pressure Dependence of Stabilized Criegee Intermediates and Evidence of Stabilized Vinyl Hydroperoxides
The Journal of Physical Chemistry A2010Vol. 115(2), pp. 161–166
Citations Over TimeTop 10% of 2010 papers
Abstract
We present measurements of the pressure dependence of stabilized Criegee intermediate (SCI) formation utilizing a hexafluoroacetone scavenger. SCI yields in the ozonolysis of 2,3-dimethyl-2-butene (TME) were measured in a high pressure flow reactor within a range of 50-710 Torr. Within this pressure range, SCI yields increase linearly with pressure. A zero pressure intercept of about 15% indicates that a significant fraction of CI are formed below the barrier to isomerization. By comparison of our results of the pressure dependence of SCI formation and both prompt and long-time OH yields, our results indicate that OH formation from ozonolysis proceeds via at least two intermediates, the SCI and presumably a vinylhydroperoxide (VHP).
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