Chhantyal-Pun, Rabi, McGillen, Max R., Beames, Joseph  ORCID: https://orcid.org/0000-0002-5508-8236, Khan, M. Anwar H., Percival, Carl J., Shallcross, Dudley E. and Orr-Ewing, Andrew J.
2017.
Temperature-dependence of the rates of reaction of trifluoroacetic acid with criegee intermediates.
Angewandte Chemie - International Edition
56
(31)
, pp. 9044-9047.
10.1002/anie.201703700
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Abstract
The rate coefficients for gas-phase reaction of trifluoroacetic acid (TFA) with two Criegee intermediates, formaldehyde oxide and acetone oxide, decrease with increasing temperature in the range 240–340 K. The rate coefficients k(CH2OO + CF3COOH)=(3.4±0.3)×10−10 cm3 s−1 and k((CH3)2COO + CF3COOH)=(6.1±0.2)×10−10 cm3 s−1 at 294 K exceed estimates for collision-limited values, suggesting rate enhancement by capture mechanisms because of the large permanent dipole moments of the two reactants. The observed temperature dependence is attributed to competitive stabilization of a pre-reactive complex. Fits to a model incorporating this complex formation give k [cm3 s−1]=(3.8±2.6)×10−18 T2 exp((1620±180)/T) + 2.5×10−10 and k [cm3 s−1]=(4.9±4.1)×10−18 T2 exp((1620±230)/T) + 5.2×10−10 for the CH2OO + CF3COOH and (CH3)2COO + CF3COOH reactions, respectively. The consequences are explored for removal of TFA from the atmosphere by reaction with biogenic Criegee intermediates.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Uncontrolled Keywords: | atmospheric chemistry; Criegee biradical; kinetics; reactive intermediates; trifluoroacetic acid; zwitterions |
| Publisher: | Wiley-Blackwell |
| ISSN: | 1433-7851 |
| Funders: | Natural Environment Research Council and Marie Sk�odowska-Curie Individual Fellowships |
| Date of First Compliant Deposit: | 30 June 2017 |
| Date of Acceptance: | 14 June 2017 |
| Last Modified: | 04 May 2023 23:55 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/101960 |
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