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Thermodynamic Investigation of the Hydrolysis Behavior of Fluorozirconate Complexes at 423.15–773.15 K and 100 MPa

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Abstract

Metal complexes are thermally unstable in hydrothermal solutions, which may cause metal cation inertness or precipitation. We investigated, for the first time, the hydrolysis behavior of ammonium fluorozirconate ((NH4)2ZrF6) at 423.15–773.15 K and 100 MPa. Kinetic equilibration experiments of the fluorozirconate solution demonstrated that the hydrolysis of the complex reached equilibrium within 4 h. Variable-temperature experiments showed that the complex’s hydrolysis was dependent on the temperature and initial concentration in the hydrothermal solutions, with enhanced hydrolysis at elevated temperature and decreased initial concentrations. Based on our experimental data, we established a linear relationship between the cumulative hydrolysis constants (K) of (NH4)2ZrF6 and absolute temperature T: \(\ln K = \left( {36.06 \pm 3.46} \right) - \left( {29747 \pm 1967} \right)/T,\) from which \(\Delta_{{\text{r}}} H_{{\text{m}}}^{\Theta }\), \(\Delta_{{\text{r}}} S_{{\text{m}}}^{\Theta }\) and \(\Delta_{{\text{r}}} G_{{\text{m}}}^{\Theta }\) values for the hydrolysis reaction were also calculated. This study suggests that fluorine may play an important role in Zr mobility and provide a route to quantitatively characterize the thermodynamic features of metal complexes in hydrothermal solutions.

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Acknowledgements

This study was supported by the National Key R&D Program of China (2016YFC0600204; 2016YFC0600408), the National Natural Science Foundation of China (41773054) and the CAS Science Innovation Project for College Students. This is contribution No. IS-2874 from GIGCAS. We thank LetPub (www.letpub.com) for its linguistic assistance during the preparation of this manuscript.

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Authors and Affiliations

  1. CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China

    Haibo Yan & Junjie He

  2. University of the Chinese Academy of Sciences, Beijing, 100049, China

    Haibo Yan & Junjie He

  3. School of Earth Science and Resources, Chang’an University, Xi’an 710054, China

    Xiaowen Liu, Hongbo Wang & Junfeng Liu

  4. State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China

    Xing Ding

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  1. Haibo Yan
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Yan, H., He, J., Liu, X. et al. Thermodynamic Investigation of the Hydrolysis Behavior of Fluorozirconate Complexes at 423.15–773.15 K and 100 MPa. J Solution Chem 49, 836–848 (2020). https://doi.org/10.1007/s10953-020-00993-1

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  • DOI: https://doi.org/10.1007/s10953-020-00993-1

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