Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

Rotavera, Brandon; Zádor, Judit; Welz, Oliver; Sheps, Leonid; Scheer, Adam M.; Savee, John D.; Akbar Ali, Mohamad; Lee, Taek Soon; Simmons, Blake A.; Osborn, David L.; Violi, Angela; Taatjes, Craig A.

doi:10.1021/jp507811d

Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

Journal Article · Fri Sep 19 00:00:00 EDT 2014 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/jp507811d· OSTI ID:1236002

Rotavera, Brandon ^[1]; Zádor, Judit ^[1]; Welz, Oliver ^[1]; Sheps, Leonid ^[1]; Scheer, Adam M. ^[1]; Savee, John D. ^[1]; Akbar Ali, Mohamad ^[2]; Lee, Taek Soon ^[3]; Simmons, Blake A. ^[4]; Osborn, David L. ^[1]; Violi, Angela ^[2]; Taatjes, Craig A. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Univ. of Michigan, Ann Arbor, MI (United States). Applied Physics Program
Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States)
Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)

The product formation from R + O₂ reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO₂ + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O₂ to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O₂-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1236002

Report Number(s):: SAND2014--16997J; 536947

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 44 Vol. 118; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

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