title: Theoretical studies on the unimolecular decomposition of propanediols and glycerol.
abstract: Polyols, a typical type of alcohol containing multiple hydroxyl groups, are being regarded as a new generation of a green energy platform. In this paper, the decomposition mechanisms for three polyol molecules, i.e., 1,2-propanediol, 1,3-propanediol, and glycerol, have been investigated by quantum chemistry calculations. The potential energy surfaces of propanediols and glycerol have been built by the QCISD(T) and CBS-QB3 methods, respectively. For the three molecules studied, the H(2)O-elimination and C-C bond dissociation reactions show great importance among all of the unimolecular decomposition channels. Rate constant calculations further demonstrate that the H(2)O-elimination reactions are predominant at low temperature and pressure, whereas the direct C-C bond dissociation reactions prevail at high temperature and pressure. The temperature and pressure dependence of calculated rate constants was demonstrated by the fitted Arrhenius equations. This work aims to better understand the thermal decomposition process of polyols and provide useful thermochemical and kinetic data for kinetic modeling of polyols-derived fuel combustion.
authors.affiliation: National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, P. R. China.
authors.forename: Lili
authors.initials: L
authors.lastname: Ye
authors.forename: Feng
authors.initials: F
authors.lastname: Zhang
authors.forename: Lidong
authors.initials: L
authors.lastname: Zhang
authors.forename: Fei
authors.initials: F
authors.lastname: Qi
mesh_terms: D056804:Biofuels; D005990:Glycerol / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D011312:Pressure; D019946:Propylene Glycol / Q000737:chemistry*; D011409:Propylene Glycols / Q000737:chemistry*; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D056804:Biofuels; D011409:Propylene Glycols; D014867:Water; C041787:1,3-propanediol; D019946:Propylene Glycol; D005990:Glycerol