jp509279d_si_004.txt (142.84 kB)

Effects of New Ab Initio Rate Coefficients on Predictions of Species Formed during n‑Butanol Ignition and Pyrolysis

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posted on 2015-01-29, 00:00 authored by Darshan M. A. Karwat, Margaret S. Wooldridge, Stephen J. Klippenstein, Michael J. Davis
Experimental, time-resolved species profiles provide critical tests in developing accurate combustion models for biofuels such as n-butanol. A number of such species profiles measured by Karwat et al. [Karwat, D. M. A.; et al. J. Phys. Chem. A 2011, 115, 4909] were discordant with predictions from a well-tested chemical kinetic mechanism developed by Black et al. [Black, G.; et al. Combust. Flame 2010, 157, 363]. Since then, significant theoretical and experimental efforts have focused on determining the rate coefficients of primary n-butanol consumption pathways in combustion environments, including H atom abstraction reactions from n-butanol by key radicals such as HO2 and OH, as well as the decomposition of the radicals formed by these H atom abstractions. These reactions not only determine the overall reactivity of n-butanol, but also significantly affect the concentrations of intermediate species formed during n-butanol ignition. In this paper we explore the effect of incorporating new ab initio predictions into the Black et al. mechanism on predictions of ignition delay time and species time histories for the experimental conditions studied by Karwat et al. The revised predictions for the intermediate species time histories are in much improved agreement with the measurements, but some discrepancies persist. A rate of production analysis comparing the effects of various modifications to the Black et al. mechanism shows significant changes in the predicted consumption pathways of n-butanol, and of the hydroxybutyl and butoxy radicals formed by H atom abstraction from n-butanol. The predictions from the newly revised mechanism are in very good agreement with the low-pressure n-butanol pyrolysis product species measurements of Stranic et al. [Stranic, I.; et al. Combust. Flame 2012, 159, 3242] for all but one species. Importantly, the changes to the Black et al. mechanism show that concentrations of small products from n-butanol pyrolysis are sensitive to different reactions than those presented by Stranic et al.