Abstract
Experimental work on the OH-initiated oxidation reactionsof fluorotelomer aldehydes (FTALs) strongly suggests thatthe respective rate coefficients do not depend on the sizeof the CxF2x+1 fluoroalkyl chain. FTALs hence representa challenging test to our multiconformer transition statetheory (MC-TST) protocol based on constrained transition state randomization (CTSR), since the calculated ratecoefficients should not show significant variations with increasing values of x. In this work we apply the MC-TST/CTSR protocol to the x = 2, 3 cases and calculate both rate coefficients at 298.15 K with a value ofk = (2.4±1.4)×10-12 cm3 molecule-1 s-1 , practicallycoincident with the recommended experimental value ofkexp = (2.8±1.4)×10-12 cm3 molecule-1 s-1. We alsoshow that the use of tunneling corrections based on improved semiclassical TST is critical in obtaining Arrhenius-Kooij curves with a correct behavior at lower temperatures.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
