title: Kinetics and quantitative structure-activity relationship study on the degradation reaction from perfluorooctanoic acid to trifluoroacetic acid.
abstract: Investigation of the degradation kinetics of perfluorooctanoic acid (PFOA) has been carried out to calculate rate constants of the main elementary reactions using the multichannel Rice-Ramsperger-Kassel-Marcus theory and canonical variational transition state theory with small-curvature tunneling correction over a temperature range of 200~500 K. The Arrhenius equations of rate constants of elementary reactions are fitted. The decarboxylation is role step in the degradation mechanism of PFOA. For the perfluorinated carboxylic acids from perfluorooctanoic acid to trifluoroacetic acid, the quantitative structure-activity relationship of the decarboxylation was analyzed with the genetic function approximation method and the structure-activity model was constructed. The main parameters governing rate constants of the decarboxylation reaction from the eight-carbon chain to the two-carbon chain were obtained. As the structure-activity model shows, the bond length and energy of C1-C2 (RC1-C2 and EC1-C2) are positively correlated to rate constants, while the volume (V), the energy difference between EHOMO and ELUMO (ΔE), and the net atomic charges on atom C2 (QC2) are negatively correlated.
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. gongchen06@lzu.edu.cn.
authors.forename: Chen
authors.initials: C
authors.lastname: Gong
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. sxmwch@sdu.edu.cn.
authors.forename: Xiaomin
authors.initials: X
authors.lastname: Sun
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. sdzhangcx@163.com.
authors.forename: Chenxi
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Environment Research Institute, Shandong University, Jinan 250100, China. zxue_117@126.com.
authors.forename: Xue
authors.initials: X
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875, China. junfengn@bnu.edu.cn.
authors.forename: Junfeng
authors.initials: J
authors.lastname: Niu
mesh_terms: D002210:Caprylates / Q000737:chemistry*; D004563:Electrochemistry; D005466:Fluorocarbons / Q000737:chemistry*; D007700:Kinetics; D021281:Quantitative Structure-Activity Relationship; D014269:Trifluoroacetic Acid / Q000737:chemistry*
chemical_list: D002210:Caprylates; D005466:Fluorocarbons; C023036:perfluorooctanoic acid; D014269:Trifluoroacetic Acid