Isomer-selective study of the OH initiated oxidation of isoprene in the presence of O(2) and NO. I. The minor inner OH-addition channel

The Journal of Physical Chemistry. a
Erin E GreenwaldSimon W North

Abstract

We report isomer-selective kinetics and mechanistic details for the hydroxyl radical-initiated oxidation of isoprene, in the presence of O(2) and NO, employing complementary experimental and theoretical techniques. Using a recently demonstrated photolytic route to initiate isomer-selective kinetics in OH-initiated oxidation of unsaturated hydrocarbons via the UV photolysis of iodohydrins, the photolysis of 1-iodo-2-methyl-3-buten-2-ol results in a single isomer of the possible four OH-isoprene adducts, specifically the minor channel associated with OH addition to one of the inner carbon atoms. Employing both the laser-photolysis/laser-induced fluorescence (LP/LIF) technique and time-dependent multiplexed photoionization mass spectrometry, we find clear experimental evidence supporting the prompt rearrangement of the initially formed beta-hydroxyalkyl radicals to alpha-hydroxyalkyl radicals, in agreement with Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation predictions. We have determined a rate constant of (3.3 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) for molecular oxygen to abstract a hydrogen atom from the alpha-hydroxyalkyl radical to form 4-penten-2-one and HO(2). This reaction provides a mechanistic route to C(5) ca...Continue Reading

References

Apr 1, 2004·Chemistry : a European Journal·José BarluengaJosé M González
Dec 27, 2005·The Journal of Chemical Physics·Hahkjoon KimSimon W North
Jul 13, 2006·The Journal of Physical Chemistry. a·Erin E GreenwaldStephen J Klippenstein
Oct 13, 2006·Journal of the American Chemical Society·Giovanni MeloniDavid L Osborn
Jun 2, 2007·The Journal of Physical Chemistry. a·Erin E GreenwaldStephen J Klippenstein
Oct 19, 2007·Journal of the American Chemical Society·Giovanni MeloniCraig A Taatjes
Dec 14, 2007·Physical Chemistry Chemical Physics : PCCP·Craig A TaatjesPhillip R Westmoreland
Jan 5, 2008·Physical Chemistry Chemical Physics : PCCP·N HansenT A Cool
Aug 16, 2008·Journal of the American Chemical Society·Craig A TaatjesDudley E Shallcross
Nov 27, 2008·The Journal of Physical Chemistry. a·Giovanni MeloniCraig A Taatjes
Dec 3, 2008·The Review of Scientific Instruments·David L OsbornStephen R Leone
Mar 7, 2005·Physical Chemistry Chemical Physics : PCCP·Craig A TaatjesPhillip R Westmoreland

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Citations

Oct 1, 2010·Physical Chemistry Chemical Physics : PCCP·Jozef Peeters, Jean-François Müller
Jun 5, 2012·Chemical Society Reviews·Luc Vereecken, Joseph S Francisco
Apr 7, 2010·The Journal of Physical Chemistry. a·Buddhadeb GhoshSimon W North
Mar 10, 2018·Chemical Reviews·Paul O WennbergJohn H Seinfeld

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