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

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Abstract

Abstract 

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 \(\hbox {kJ mol}^{-1}\) with DSC measurement which is very close to the density functional theory (DFT) calculation result 69.395 \(\hbox {kJ mol}^{-1}\). Furthermore, with the aid of DFT calculations, some other important thermochemical characteristics such as crystal lattice energy with the value of 510.597 \(\hbox {kJ mol}^{-1}\) were evaluated by means of Born–Fajans–Haber cycle.

Graphical Abstract 

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.

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Acknowledgements

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.

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Authors and Affiliations

  1. National Engineering Research Center for Integrated Utilization of Salt Lake Resource, East China University of Science and Technology, Meilong Road 130, Shanghai, 200237, China

    CHUNHUA DONG, XINGFU SONG, GUILAN CHEN, YANXIA XU & JIANGUO YU

  2. Van ’t Hoff Institute for Molecular Sciences & Amsterdam Center for Multiscale Modeling, University of Amsterdam, 1098 XH, Amsterdam, The Netherlands

    CHUNHUA DONG & EVERT JAN MEIJER

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  1. CHUNHUA DONG
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Correspondence to XINGFU SONG or JIANGUO YU.

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DONG, C., SONG, X., MEIJER, E.J. et al. Mechanism studies on thermal dissociation of tri-n-octylamine hydrochloride with FTIR, TG, DSC and quantum chemical methods. J Chem Sci 129, 1431–1440 (2017). https://doi.org/10.1007/s12039-017-1357-4

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