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四氟乙烷中的电子驱动反应:正负离子的形成

Electron Driven Reactions in Tetrafluoroethane: Positive and Negative Ion Formation.

作者信息

Pereira-da-Silva João, Rodrigues Rodrigo, Ramos João, Brígido Carlos, Botnari Alexandru, Silvestre Miguel, Ameixa João, Mendes Mónica, Zappa Fábio, Mullock Stephen J, Araújo João M M, Varella Márcio T do N, Cornetta Lucas M, da Silva Filipe Ferreira

机构信息

CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal.

Departamento de Física-ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36036-900 Juiz de Fora, MG, Brazil.

出版信息

J Am Soc Mass Spectrom. 2021 Jun 2;32(6):1459-1468. doi: 10.1021/jasms.1c00057. Epub 2021 May 17.

Abstract

In the search for alternatives to chlorine-containing gases, tetrafluoroethane, CFCHF (R134a), a widely used refrigerant gas, has been recognized as a promising substitute for dichlorodifluoromethane, CClF (R12). When R12 is replaced by R134a, the global warming potential drops from 8100 to 1430, the ozone depletion potential changes from 1 to 0, and the atmospheric lifetime decreases from 100 to 14 years. Electron interactions in the gas phase play a fundamental role in the atmospheric sciences. Here, we present a detailed study on electron-driven fragmentation pathways of CFCHF, in which we have investigated processes induced by both electron ionization and electron attachment. The measurements allow us to report the ion efficiency curves for ion formation in the energy range of 0 up to 25 eV. For positive ion formation, R134a dissociates into a wide assortment of ions, in which CF is observed as the most abundant out of seven ions with a relative intensity above 2%. The results are supported by quantum chemical calculations based on bound state techniques, electron-impact ionization models, and electron-molecule scattering simulations, showing a good agreement. Moreover, the experimental first ionization potential was found at 13.10 ± 0.17 eV and the second at around 14.25 eV. For negative ion formation, CF was detected as the only anion formed, above 8.3 eV. This study demonstrates the role of electrons in the dissociation of R134a, which is relevant for an improvement of the refrigeration processes as well as in atmospheric chemistry and plasma sciences.

摘要

在寻找含氯气体的替代品时,四氟乙烷CF₂CHF₂(R134a),一种广泛使用的制冷剂气体,已被认为是二氯二氟甲烷CCl₂F₂(R12)的有前途的替代品。当R12被R134a取代时,全球变暖潜能值从8100降至1430,臭氧消耗潜能值从1变为0,大气寿命从100年减少到14年。气相中的电子相互作用在大气科学中起着基础性作用。在此,我们对CF₂CHF₂的电子驱动碎片化途径进行了详细研究,其中我们研究了由电子电离和电子附着诱导的过程。这些测量使我们能够报告在0至25 eV能量范围内离子形成的离子效率曲线。对于正离子形成,R134a分解成各种各样的离子,其中CF⁺被观察到是七种相对强度高于2%的离子中最丰富的。结果得到了基于束缚态技术、电子碰撞电离模型和电子 - 分子散射模拟的量子化学计算的支持,显示出良好的一致性。此外,实验测得的第一电离能为13.10±0.17 eV,第二电离能约为14.25 eV。对于负离子形成,在高于8.3 eV时检测到CF⁻是唯一形成的阴离子。这项研究证明了电子在R134a解离中的作用,这对于改进制冷过程以及大气化学和等离子体科学是相关的。

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