Poutsma John C, Midey Anthony J, Viggiano Albert A
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Massachusetts 01731, USA.
J Chem Phys. 2006 Feb 21;124(7):74301. doi: 10.1063/1.2168152.
The absolute rate coefficients at 298 K for the reactions of O(2) (-) + N((4)S(3/2)) and O(2) (-) + O((3)P) have been determined in a selected-ion flow tube instrument. O atoms are generated by the quantitative titration of N atoms with NO, where the N atoms are produced by microwave discharge on N(2). The experimental procedure allows for the determination of rate constants for the reaction of the reactant ion with N((4)S(3/2)) and O((3)P). The rate coefficient for O(2) (-) + N is found to be 2.3x10(-10)+/-40% cm(3) molecule(-1) s(-1), a factor of 2 slower than previously determined. In addition, it was found that the reaction proceeds by two different reaction channels to give (1) NO(2)+e(-) and (2) O(-)+NO. The second channel was not reported in the previous study and accounts for ca. 35% of the reaction. An overall rate coefficient of 3.9 x 10(-10) cm(3) molecule(-1) s(-1) was determined for O(2) (-) + O, which is slightly faster than previously reported. Branching ratios for this reaction were determined to be <55%O(3) + e(-) and >45%O(-) + O(2).
在选定离子流动管仪器中测定了298 K时O₂⁻ + N(⁴S₃/₂)和O₂⁻ + O(³P)反应的绝对速率系数。O原子通过用NO对N原子进行定量滴定产生,其中N原子由N₂上的微波放电产生。该实验程序允许测定反应物离子与N(⁴S₃/₂)和O(³P)反应的速率常数。发现O₂⁻ + N的速率系数为2.3×10⁻¹⁰±40% cm³·分子⁻¹·s⁻¹,比先前测定的慢2倍。此外,发现该反应通过两个不同的反应通道进行,生成(1) NO₂ + e⁻和(2) O⁻ + NO。第二个通道在先前的研究中未被报道,约占反应的35%。测定O₂⁻ + O的总速率系数为3.9×10⁻¹⁰ cm³·分子⁻¹·s⁻¹,略快于先前报道的值。该反应的分支比确定为<55% O₃ + e⁻和>45% O⁻ + O₂。