Kinetics of Reactions of CHF₂CF₂CH₂OH with Cl Atoms and CHF₂CF₂CHO with OH Radicals and Atmospheric Degradation Pathways of CHF₂CF₂CH₂OH: A Theoretical Investigation

Abstract

The H‐abstraction reaction between CHF2CF2CH2OH 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 –CH2– site is the most favorable reaction channel. The atmospheric oxidative degradation pathways for CHF2CF2CH2OH has been explored for the first time using (P)MP2/6‐311++G(d,p) method. The reaction of the primary oxidation product CHF2CF2CHO, generated from the reaction of CHF2CF2CHOH radical with atmospheric O2, with OH radical has also been investigated for the first time using the same techniques. The calculated rate coefficient for CHF2CF2CHO +OH reaction agrees quite well with the value estimated from the structure‐reactivity relationship. Effective atmospheric lifetime and Global Warming Potential (GWP) of CHF2CF2CH2OH and CHF2CF2CHO are also reported.