Premium
Kinetics of Reactions of CHF 2 CF 2 CH 2 OH with Cl Atoms and CHF 2 CF 2 CHO with OH Radicals and Atmospheric Degradation Pathways of CHF 2 CF 2 CH 2 OH: A Theoretical Investigation
Author(s) -
Baidya Bidisha,
Lily Makroni,
Chandra Asit K.
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201901571
Subject(s) - chemistry , chemical kinetics , thermochemistry , transition state theory , reaction rate constant , ab initio , reactivity (psychology) , kinetics , kinetic energy , atmospheric temperature range , ab initio quantum chemistry methods , thermodynamics , computational chemistry , molecule , physics , organic chemistry , medicine , alternative medicine , pathology , quantum mechanics
The H‐abstraction reaction between CHF 2 CF 2 CH 2 OH and Cl atoms has been systematically investigated using ab initio CCSD(T)//MP2/6‐311++G(d,p) method along with kinetic calculations using conventional transition state theory and Eckart's tunelling corrections. The rate coefficients for the titled reaction are reported over a temperature range of 250–500 K and found to agree quite well with the available experimental values. The computed thermochemical data and branching ratios indicate that H‐abstraction from the –CH 2 – site is the most favorable reaction channel. The atmospheric oxidative degradation pathways for CHF 2 CF 2 CH 2 OH has been explored for the first time using (P)MP2/6‐311++G(d,p) method. The reaction of the primary oxidation product CHF 2 CF 2 CHO, generated from the reaction of CHF 2 CF 2 CHOH radical with atmospheric O 2 , with OH radical has also been investigated for the first time using the same techniques. The calculated rate coefficient for CHF 2 CF 2 CHO +OH reaction agrees quite well with the value estimated from the structure‐reactivity relationship. Effective atmospheric lifetime and Global Warming Potential (GWP) of CHF 2 CF 2 CH 2 OH and CHF 2 CF 2 CHO are also reported.