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Temperature-jump induced cation exchange kinetics in (Co0.1Mg0.9)2SiO4 olivine: an in situ optical spectroscopic study

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Abstract

In the olivine crystal structure, cations are distributed over two inequivalent octahedral sites, M1 and M2. Kinetics of cation exchange between the two octahedral sites in (Co0.1Mg0.9)2SiO4 single crystal have been studied in the temperature range from 600 to 800°C by monitoring the time evolution of the absorbance of Co2+ ions in M1 or M2 sites using optical spectroscopy after rapid temperature jumps. It was found from such temperature-jump induced relaxation experiments that with increasing temperature the absorbance of Co2+ ions in the M1 site decreases while that in the M2 site increases. This indicates a tendency of Co2+ cations to populate the M2 site with increasing temperatures and vice versa. The experimental relaxation data can be modeled using a triple exponential equation based on theoretical analysis. Activation energies of 221 ± 4 and 213 ± 10 kJ/mol were derived from relaxation experiments on the M2 site and M1 site, respectively, for the cation exchange processes in (Co0.1Mg0.9)2SiO4 olivine. Implications for cation diffusion at low temperatures are discussed.

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Acknowledgments

The authors would like to thank Dr. S. Kipp, M. Schrader, S. Dlugocz and A. Tiefnig for their help during this work. Thanks are also due to Prof. P. G. Jones’s group for performing single crystal diffraction experiments and Dr. J. Koepke, University of Hanover, for electron microprobe analysis. Financial support from Deutsche Forschungsgemeinschaft (DFG) is greatly acknowledged.

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Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Braunschweig University of Technology, Hans-Sommer-Strasse 10, 38106, Braunschweig, Germany

    Jianmin Shi & Klaus Dieter Becker

  2. Solid State Chemistry, Institute of Physics, University of Augsburg, Universitätsstrasse 1, 86159, Augsburg, Germany

    Stefan G. Ebbinghaus

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  1. Jianmin Shi
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  2. Stefan G. Ebbinghaus
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  3. Klaus Dieter Becker
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Correspondence to Jianmin Shi.

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Shi, J., Ebbinghaus, S.G. & Becker, K.D. Temperature-jump induced cation exchange kinetics in (Co0.1Mg0.9)2SiO4 olivine: an in situ optical spectroscopic study. Phys Chem Minerals 35, 1–9 (2008). https://doi.org/10.1007/s00269-007-0187-1

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  • DOI: https://doi.org/10.1007/s00269-007-0187-1

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