title: Theoretical studies on the unimolecular decomposition of ethylene glycol.
abstract: The unimolecular decomposition processes of ethylene glycol have been investigated with the QCISD(T) method with geometries optimized at the B3LYP/6-311++G(d,p) level. Among the decomposition channels identified, the H(2)O-elimination channels have the lowest barriers, and the C-C bond dissociation is the lowest-energy dissociation channel among the barrierless reactions (the direct bond cleavage reactions). The temperature and pressure dependent rate constant calculations show that the H(2)O-elimination reactions are predominant at low temperature, whereas at high temperature, the direct C-C bond dissociation reaction is dominant. At 1 atm, in the temperature range 500-2000 K, the calculated rate constant is expressed to be 7.63 × 10(47)T(-10.38) exp(-42262/T) for the channel CH(2)OHCH(2)OH → CH(2)CHOH + H(2)O, and 2.48 × 10(51)T(-11.58) exp(-43593/T) for the channel CH(2)OHCH(2)OH → CH(3)CHO + H(2)O, whereas for the direct bond dissociation reaction CH(2)OHCH(2)OH → CH(2)OH + CH(2)OH the rate constant expression is 1.04 × 10(71)T(-16.16) exp(-52414/T).
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: Long
authors.initials: L
authors.lastname: Zhao
authors.forename: Lidong
authors.initials: L
authors.lastname: Zhang
authors.forename: Fei
authors.initials: F
authors.lastname: Qi
mesh_terms: D019855:Ethylene Glycol / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D019855:Ethylene Glycol