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Title: Rate constants for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The present work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants. The experimental results can be expressed in Arrhenius form in units of cm{sup 3} molecule{sup -1} s{sup -1} as follows: K{sub OH+n-heptane} = (2.48 {+-} 0.17) x 10{sup -10} exp[(-1927 {+-} 69 K)/T] (838-1287 K); k{sub OH+2,2,3,3-TMB} = (8.26 {+-} 0.89) x 10{sup -11} exp[(-1337 {+-} 94 K)/T] (789-1061 K); K{sub OH+n-pentane} = (1.60 {+-} 0.25) x 10{sup -10} exp[(-1903 {+-} 146 K)/T] (823-1308more » K); K{sub OH+n-hexane} = (2.79 {+-} 0.39) x 10{sup -10} exp[(-2301 {+-} 134 K)/T] (798-1299 K); and k{sub OH+2,3-DMB} = (1.27 {+-} 0.16) x 10{sup -10} exp[(-1617 {+-} 118 K)/T] (843-1292 K). The available experimental data, along with lower-T determinations, were used to obtain evaluations of the experimental rate constants over the temperature range from {approx}230 to 1300 K for most of the title reactions. These extended-temperature-range evaluations, given as three-parameter fits, are as follows: k{sub OH+n-heptane} = 2.059 x 10{sup -5}T{sup 1.401} exp(33 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (241-1287 K); k{sub OH+2,2,3,3-TMB} = 6.835 x 10{sup -17}T{sup 1.886} exp(-365 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (290-1180 K); k{sub OH+n-pentane} = 2.495 x 10{sup -16}T{sup 1.649} exp(80 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (224-1308 K); k{sub OH+n-hexane} = 3.959 x 10{sup -18}T{sup 2.218} exp(443 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (292-1299 K); and k{sub OH+2,3-DMB} = 2.287 x 10{sup -17}T{sup 1.958} exp(365 K/T) cm{sup 3} molecule{sup -1} s{sup -1} (220-1292 K). The experimental data and the evaluations obtained for these five larger alkanes in the present work were used along with prior data/evaluations obtained in this laboratory for H abstractions by OH from a series of smaller alkanes (C{sub 3}?C{sub 5}) to devise rate rules for abstractions from various types of primary, secondary, and tertiary H atoms. Specifically, the current scheme was applied with good success to H abstractions by OH from a series of n-alkanes (n-octane through n-hexadecane). The total rate constants using this group scheme for reactions of OH with selected large alkanes are given as three-parameter fits in this article. The rate constants for the various abstraction channels in any large n-alkane can also be obtained using the groups listed in this article. The present group scheme serves to reduce the uncertainties in rate constants for OH + alkane reactions.« less
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TRN: US200914%%79
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Journal Name: J. Phys. Chem. A; Journal Volume: 113; Journal Issue: 17 ; Apr. 30, 2009; Conference: 6th U.S. National Combustion Meeting; May 17, 2009 - May 20, 2009; Ann Arbor, MI
Research Org:
Argonne National Laboratory (ANL)
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Country of Publication:
United States