Rate coefficients for the reactions of OH with butanols from 298 K to temperatures relevant for low‐temperature combustion

• Published in: International journal of chemical kinetics Vol. 52; no. 12; pp. 1046 - 1059
• Main Authors: Sime, Samantha L., Blitz, Mark A., Seakins, Paul W.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc 01.12.2020
• Subjects: Butanol; butanols; Coefficients; curved Arrhenius; Decomposition; low‐temperature combustion; Radicals; Temperature; Temperature dependence
• ISSN: 0538-8066; 1097-4601
• DOI: 10.1002/kin.21422

Rate coefficients for the reactions of OH with n, s, and iso‐butanol have been measured over the temperature range 298 to ∼650 K. The rate coefficients display significant curvature over this temperature range and bridge the gap between previous low‐temperature measurements with a negative temperature dependence and higher temperature shock tube measurements that have a positive temperature dependence. In combination with literature data, the following parameterizations are recommended: k1,OH + n‐butanol(T) = (3.8 ± 10.4) × 10−19T2.48 ± 0.37exp ((840 ± 161)/T) cm3 molecule−1 s−1 k2,OH + s‐butanol(T) = (3.5 ± 3.0) × 10−20T2.76 ± 0.12exp ((1085 ± 55)/T) cm3 molecule−1 s−1 k3,OH + i‐butanol(T) = (5.1 ± 5.3) × 10−20T2.72 ± 0.14exp ((1059 ± 66)/T) cm3 molecule−1 s−1 k4,OH + t‐butanol(T) = (8.8 ± 10.4) × 10−22T3.24 ± 0.15exp ((711 ± 83)/T) cm3 molecule−1 s−1 Comparison of the current data with the higher shock tube measurements suggests that at temperatures of ∼1000 K, the OH yields, primarily from decomposition of β‐hydroxyperoxy radicals, are ∼0.3 (n‐butanol), ∼0.3 (s‐butanol) and ∼0.2 (iso‐butanol) with β‐hydroxyperoxy decompositions generating OH, and a butene as the main products. The data suggest that decomposition of β‐hydroxyperoxy radicals predominantly occurs via OH elimination.