Division of Atmospheric Chemistry, Max-Planck-Institut für Chemie, 55020 Mainz, Germany.
J Phys Chem A. 2012 Jun 21;116(24):6051-8. doi: 10.1021/jp211241x. Epub 2012 Feb 10.
Absolute (pulsed laser photolysis, 4-639 Torr N(2) or air, 240-357 K) and relative rate methods (50 and 760 Torr air, 296 K) were used to measure rate coefficients k(1) for the title reaction, OH + C(4)H(5)N → products (R1). Although the pressure and temperature dependent rate coefficient is adequately represented by a falloff parametrization, calculations of the potential energy surface indicate a complex reaction system with multiple reaction paths (addition only) in the falloff regime. At 298 K and 760 Torr (1 Torr = 1.33 mbar) the rate coefficient obtained from the parametrization is k(1) = (1.28 ± 0.1) × 10(-10) cm(3) molecule(-1) s(-1), in good agreement with the value of (1.10 ± 0.27) × 10(-10) cm(3) molecule(-1) s(-1) obtained in the relative rate study (relative to C(5)H(8), isoprene) at this temperature and pressure. The accuracy of the absolute rate coefficient determination was enhanced by online optical absorption measurements of the C(4)H(5)N concentration at 184.95 nm using a value σ(184.95nm) = (1.26 ± 0.02) × 10(-17) cm(2) molecule(-1), which was determined in this work.
绝对（脉冲激光光解，4-639 托 N2 或空气，240-357 K）和相对速率方法（50 和 760 托空气，296 K）用于测量标题反应的速率系数 k(1)，OH + C(4)H(5)N → 产物 (R1)。尽管压力和温度相关的速率系数可以通过下降参数化来很好地表示，但势能面的计算表明在下降区存在一个具有多个反应路径（仅加成）的复杂反应体系。在 298 K 和 760 Torr（1 Torr = 1.33 mbar）下，从参数化中获得的速率系数为 k(1) = (1.28 ± 0.1) × 10(-10) cm(3) molecule(-1) s(-1)，与相对速率研究（相对于 C(5)H(8)，异戊二烯）在该温度和压力下获得的 (1.10 ± 0.27) × 10(-10) cm(3) molecule(-1) s(-1) 值吻合较好。通过使用在 184.95nm 处的 C(4)H(5)N 浓度的在线光学吸收测量来增强绝对速率系数的确定的准确性，该吸收测量使用的值 σ(184.95nm) = (1.26 ± 0.02) × 10(-17) cm(2) molecule(-1)，该值是在本工作中确定的。
