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...
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2025-01-01
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| author | Ramesh Sapkota Trang Nguyen Paul Marshall |
| author_facet | Ramesh Sapkota Trang Nguyen Paul Marshall |
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| description | 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. |
| format | Article |
| id | doaj-art-33a55ec78624479cbcb6c74f5be124f8 |
| institution | DOAJ |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-01-01 |
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| spelling | doaj-art-33a55ec78624479cbcb6c74f5be124f82025-08-20T02:48:09ZengMDPI AGMolecules1420-30492025-01-0130347810.3390/molecules30030478The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl FluorideRamesh Sapkota0Trang Nguyen1Paul Marshall2Department of Chemistry, Rhodes College, 2000 North Parkway, Memphis, TN 38112, USADepartment of Chemistry, University of North Texas, 1155 Union Circle #305070, Denton, TX 76203, USADepartment of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle #305070, Denton, TX 76203, USAFluorinated 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.https://www.mdpi.com/1420-3049/30/3/478kineticsmechanismrelative ratecross-sectionglobal warming potential |
| spellingShingle | Ramesh Sapkota Trang Nguyen Paul Marshall The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride Molecules kinetics mechanism relative rate cross-section global warming potential |
| title | The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride |
| title_full | The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride |
| title_fullStr | The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride |
| title_full_unstemmed | The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride |
| title_short | The Atmospheric Chemistry of Fluoroacetonitrile and the Characterization of the Major Product, Cyanoformyl Fluoride |
| title_sort | atmospheric chemistry of fluoroacetonitrile and the characterization of the major product cyanoformyl fluoride |
| topic | kinetics mechanism relative rate cross-section global warming potential |
| url | https://www.mdpi.com/1420-3049/30/3/478 |
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