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氩气、氧气和一氧化氮与异戊二烯(2-甲基-1,3-丁二烯)反应的动力学随温度(300 - 500K)的变化

Kinetics for the Reactions of Ar, O, and NO with Isoprene (2-Methyl-1,3-butadiene) as a Function of Temperature (300-500 K).

作者信息

Lewis Tucker W R, Long Bryan A, Eyet Nicole, Shuman Nicholas S, Ard Shaun G, Viggiano Albert A

机构信息

Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, United States.

Chemistry Department, Saint Anselm College, Manchester, New Hampshire 03102, United States.

出版信息

J Phys Chem A. 2023 Aug 31;127(34):7221-7227. doi: 10.1021/acs.jpca.3c03914. Epub 2023 Aug 16.

Abstract

Rate constants and product branching fractions were measured for reactions of Ar, O, and NO with isoprene (2-methyl-1,3-butadiene CH) as a function of temperature. The rate constants are large (∼2 × 10 cm s) and increase with temperature, exceeding the ion-dipole/induced dipole capture rate. Adding a hard sphere term to the collision rate provides a more useful upper limit and predicts the positive temperature dependences. Previous kinetic energy-dependent rate constants show a similar trend. NO reacts only by non-dissociative charge transfer. The more energetic O reaction has products formed through both non-dissociative and dissociative charge transfer, or possibly through an H atom transfer. The very energetic Ar has essentially only dissociative products; assumption of statistical behavior in the dissociation reasonably reproduces the product branching fractions.

摘要

测量了氩气(Ar)、氧原子(O)和一氧化氮(NO)与异戊二烯(2-甲基-1,3-丁二烯,CH)反应的速率常数和产物分支比随温度的变化情况。速率常数很大(约2×10 cm³·s⁻¹)且随温度升高而增大,超过了离子 - 偶极/诱导偶极捕获速率。在碰撞速率中加入硬球项可提供更有用的上限,并预测了正温度依赖性。先前与动能相关的速率常数也显示出类似趋势。NO仅通过非解离电荷转移进行反应。能量较高的O反应通过非解离和解离电荷转移形成产物,或者可能通过氢原子转移形成产物。能量非常高的Ar基本上只有解离产物;假设解离过程中的统计行为能够合理再现产物分支比。

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