Initiation and Carbene Induced Radical Chain Reactions in CH 2 F 2 Pyrolysis

Shaik, Rizwan A.; Jasper, Ahren W.; Lynch, Patrick T.; Sivaramakrishnan, Raghu; Tranter, Robert S.

doi:10.1002/cphc.202400362

Title: Initiation and Carbene Induced Radical Chain Reactions in CH ₂ F ₂ Pyrolysis

Journal Article · 20 June 2024 · ChemPhysChem

DOI: https://doi.org/10.1002/cphc.202400362 · OSTI ID:2375915

Shaik, Rizwan A. ^[1]; Jasper, Ahren W. ^[2];

^[1];

^[2]; Tranter, Robert S. ^[2]

Department of Mechanical &, Industrial Engineering University of Illinois at Chicago 842 W Taylor Street Chicago IL-60607 USA
Chemical Dynamics Group Chemical Sciences &, Engineering Division Argonne National Laboratory 9700 S Cass Avenue Lemont IL-60439 USA

Abstract High temperature dissociations of organic molecules typically involve a competition between radical and molecular processes. In this work, we use a modeling, experiment, theory (MET) framework to characterize the high temperature thermal dissociation of CH ₂ F ₂ , a flammable hydrofluorocarbon (HFC) that finds widespread use as a refrigerant. Initiation in CH ₂ F ₂ proceeds via a molecular elimination channel; CH ₂ F ₂ →CHF+HF. Here we show that the subsequent self‐reactions of the singlet carbene, CHF, are fast multichannel processes and a facile source of radicals that initiate rapid chain propagation reactions. These have a marked influence on the decomposition kinetics of CH ₂ F ₂ . The inclusion of these reactions brings the simulations into better agreement with the present and literature experiments. Additionally, flame simulations indicate that inclusion of the CHF+CHF multichannel reaction leads to a noticeable enhancement in predictions of laminar flame speeds, a key parameter that is used to determine the flammability of a refrigerant.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; AC02-06CH11357

OSTI ID:: 2375915

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem; ISSN 1439-4235

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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