文献类型：期刊文献

英文题名：Thermodynamics and kinetics analysis of thermal dissociation of tri-n-octylamine hydrochloride in open system: A DFT and TGA study

作者：Dong, Chunhua[1,2,3];Song, Xingfu[1];Zhang, Jie[1];Liu, Dongfan[1];Meijer, Evert Jan[2,3];Yu, Jianguo[1]

机构：[1]East China Univ Sci & Technol, Natl Engn Res Ctr Integrated Utilizat Salt Lake R, Meilong Rd 130, Shanghai 200237, Peoples R China;[2]Univ Amsterdam, Vant Hoff Inst Mol Sci, NL-1098 XH Amsterdam, Netherlands;[3]Univ Amsterdam, Amsterdam Ctr Multiscale Modeling, NL-1098 XH Amsterdam, Netherlands

年份：2018

卷号：670

起止页码：35

外文期刊名：THERMOCHIMICA ACTA

收录：;EI(收录号：20184205959652);WOS:【SCI-EXPANDED(收录号:WOS:000452945500006)】；

基金：This study is financially supported by the National High Technology Research and Development Program of China (Grant No. 2011AA06A107). Also we thank China Scholarship Council for the support of this project. Authors thank the SURFsara in the Netherlands for offering computing resources of Gaussian 09.

语种：英文

外文关键词：Thermal dissociation; Thermodynamics; Kinetics; DFT calculation; Isoconversional methods

摘要：The thermal dissociation of tri-n-octylamine hydrochloride (TOAHCl) in open system was investigated by TGA and DFT methods. The dissociation starts at the temperature of about 120 degrees C which was predicted with DFT calculations and verified by isothermal TGA. Then a thermodynamic cycle depicting the dissociation process was built. The thermal dissociation which couples with the evaporation of products tri-n-octylamine (TOA) and HCl undergoes two continuous steps due to the evaporation speed difference between the two compounds. Based on the assumption, kinetics analysis was performed by employing isoconversional methods of Friedman, Kissinger-Akahira-Sunose (KAS) and Starink. The activation energies of the two steps fall in the range of 81.1 +/- 2.6 kJ mol(-1) and 96.8 +/- 13.4 kJ mol(-1), which are comparable with the enthalpy values from 94.7 +/- 5.6 kJ mol(-1) to 100.1 +/- 5.4 kJ mol(-1). The comparability indicates that the dissociation of TOAHCl is a process with no transition state which is in accordance with the DFT prediction. Model-fitting methods were performed by simultaneous treatment of kinetic curves under different temperature programs via reaction-order kinetics mechanism. And the results reveal that the reaction orders are 0.21 and 0.07 respectively for the two steps.