The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride

Fluorinated nitriles have been proposed as low-global-warming-potential substitutes for industrial applications such as plasma etching and as dielectric materials in high-voltage equipment. FT-IR spectroscopy was used to measure the radiative efficiency of CH<sub>2</sub>FCN and its react...

Full description

Saved in:
Bibliographic Details
Main Authors: Ramesh Sapkota, Trang Nguyen, Paul Marshall
Format: Article
Language:English
Published: MDPI AG 2025-01-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/30/3/478
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Fluorinated nitriles have been proposed as low-global-warming-potential substitutes for industrial applications such as plasma etching and as dielectric materials in high-voltage equipment. FT-IR spectroscopy was used to measure the radiative efficiency of CH<sub>2</sub>FCN and its reactivity towards Cl and OH radicals, and to determine products from the Cl reaction. Relative rate experiments yielded rate constants for Cl and OH reactions of (2.1 ± 0.3) × 10<sup>−14</sup> and (7.0 ± 1.0) × 10<sup>−14</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>, respectively. The estimated atmospheric lifetime of CH<sub>2</sub>FCN with respect to radical attack was estimated to be 0.45 years, which, combined with the radiative efficiency of 0.042 W m<sup>−2</sup> ppb<sup>−1</sup>, implies a 100-year global warming potential of 20. FCOCN was observed as the only organic product of the Cl-atom reaction in air, consistent with a dominant role for H-abstraction. Absolute infrared cross-sections for FCOCN were determined, to assist future experiments where this molecule may be formed. Quantum calculations at the CBS-APNO//B2PLYP-D3/cc-pVTZ level indicate similar energy barriers to addition and abstraction for OH radical attack, but the looser transition state and greater opportunity for tunneling also favor abstraction in this case.
ISSN:1420-3049