Gas-phase rate coefficients for the OH + n-, i-, s-, and t-butanol reactions measured between 220 and 380 K: non-Arrhenius behavior and site-specific reactivity
Mcgillen, MR; Baasandorj, M; Burkholder, JB
| HERO ID | 2325040 |
|---|---|
| In Press | No |
| Year | 2013 |
| Title | Gas-phase rate coefficients for the OH + n-, i-, s-, and t-butanol reactions measured between 220 and 380 K: non-Arrhenius behavior and site-specific reactivity |
| Authors | Mcgillen, MR; Baasandorj, M; Burkholder, JB |
| Journal | Journal of Physical Chemistry A |
| Volume | 117 |
| Issue | 22 |
| Page Numbers | 4636-4656 |
| Abstract | Butanol (C4H9OH) is a potential biofuel alternative in fossil fuel gasoline and diesel formulations. The usage of butanol would necessarily lead to direct emissions into the atmosphere; thus, an understanding of its atmospheric processing and environmental impact is desired. Reaction with the OH radical is expected to be the predominant atmospheric removal process for the four aliphatic isomers of butanol. In this work, rate coefficients, k, for the gas-phase reaction of the n-, i-, s-, and t-butanol isomers with the OH radical were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to monitor its temporal profile. Rate coefficients were measured over the temperature range 221-381 K at total pressures between 50 and 200 Torr (He). The reactions exhibited non-Arrhenius behavior over this temperature range and no dependence on total pressure with k(296 K) values of (9.68 ± 0.75), (9.72 ± 0.72), (8.88 ± 0.69), and (1.04 ± 0.08) (in units of 10(-12) cm(3) molecule(-1) s(-1)) for n-, i-, s-, and t-butanol, respectively. The quoted uncertainties are at the 2σ level and include estimated systematic errors. The observed non-Arrhenius behavior is interpreted here to result from a competition between the available H-atom abstraction reactive sites, which have different activation energies and pre-exponential factors. The present results are compared with results from previous kinetic studies, structure-activity relationships (SARs), and theoretical calculations and the discrepancies are discussed. Results from this work were combined with available high temperature (1200-1800 K) rate coefficient data and room temperature reaction end-product yields, where available, to derive a self-consistent site-specific set of reaction rate coefficients of the form AT(n) exp(-E/RT) for use in atmospheric and combustion chemistry modeling. |
| Doi | 10.1021/jp402702u |
| Pmid | 23627621 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |