Pyrolysis mechanism of R601a/R245fa mixture: A ReaxFF-MD and DFT study

R601a/R245fa mixture is one kind of promising working fluid in ORC. In this study, the thermal decomposition mechanism of R601a/R245fa mixture was studied by reactive molecular dynamic simulation (ReaxFF-MD) and density function theory (DFT). In the R601a/R245fa mixed working fluid system, pyrolysis begins with the C-C bond breaking of R601a, generating a large number of CH3 radicals, which further decompose to produce a certain amount of H radicals. Due to the presence of R245fa, the hydrogen extraction reactions between CH3, H radicals and R601a, which have low energy barriers were inhabited to a certain extent. The addition of R245fa reduces the generation of small molecule flammable gases such as H2 and CH4, however, it increases the risk of HF generation. When the molar ratio of R245fa exceeds 0.5, pyrolysis will cause more serious HF corrosion problems than pure R245fa.