文献类型：期刊文献

英文题名：Mechanism studies on thermal dissociation of tri-n-octylamine hydrochloride with FTIR, TG, DSC and quantum chemical methods

作者：Dong, Chunhua[1,2,3];Song, Xingfu[1];Meijer, Evert Jan[2,3];Chen, Guilan[1];Xu, Yanxia[1];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：2017

卷号：129

期号：9

起止页码：1431

外文期刊名：JOURNAL OF CHEMICAL SCIENCES

收录：;EI(收录号：20173904207130);WOS:【SCI-EXPANDED(收录号:WOS:000410906300011)】；

基金：The authors are greatly thankful to the National High Technology Research and Development Program of China (No. 2011AA06A107) for financial support. Also, authors thank China Scholarship Council (CSC) for backing the project. Authors thank the University of Amsterdam and SURFsara in The Netherlands for offering the resources for calculation on CP2K and Gaussian 09, respectively.

语种：英文

外文关键词：Tri-n-octylamine hydrochloride; TG-FTIR; DSC; thermal dissociation mechanisms; intrinsic reaction coordinate

摘要：The thermal dissociation of tri-n-octylamine hydrochloride (TOAHCl) was investigated using both the quantum chemical simulation and experimental methods. The pathway through which a mixture of tri-n-octylamine (TOA) and hydrogen chloride (HCl), rather than di-n-octylamine (DOA) and 1-chlorooctane, are produced has been determined through transition state (TS) search with Intrinsic Reaction Coordinate (IRC) calculations. Particularly, strong agreement between the experimental FTIR spectra and that of TOA demonstrates the same result for the first time. Moreover, the thermal dissociation of TOAHCl proceeds in two continuous steps, which is different from the low molecular mass amine hydrochlorides. The experimental enthalpy of the dissociation was 70.793 with DSC measurement which is very close to the density functional theory (DFT) calculation result 69.395 . Furthermore, with the aid of DFT calculations, some other important thermochemical characteristics such as crystal lattice energy with the value of 510.597 were evaluated by means of Born-Fajans-Haber cycle. The thermal dissociation of tri-n-octylamine hydrochloride was investigated with both the quantum chemical simulation and experimental methods. Intrinsic reaction coordinate (IRC) calculations suggest that the products are tri-n-octylamine and HCl rather than di-n-octylamine and 1-chlorooctane. Furthermore, the dissociation is a two-stage process as determined by experimental analysis.