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The structure and thermochemistry of K2CO3–MgCO3 glass

Published online by Cambridge University Press:  16 September 2019

Martin C. Wilding ,
Brian L. Phillips ,
Mark Wilson ,
Geetu Sharma ,
Alexandra Navrotsky ,
Paul A. Bingham ,
Richard Brooker  and
John B. Parise
Martin C. Wilding*
Affiliation:
Materials and Engineering Research Institute, Sheffield Hallam University, Sheffield S1 1WB, U.K.; and Department of Geosciences, Stony Brook University, Stony Brook, New York 11794, USA
Brian L. Phillips
Affiliation:
Department of Geosciences, Stony Brook University, Stony Brook, New York 11794, USA
Mark Wilson
Affiliation:
Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford OX1 3QZ, U.K.
Geetu Sharma
Affiliation:
Peter A. Rock Thermochemistry Laboratory, University of California, Davis, California 95616, USA
Alexandra Navrotsky
Affiliation:
Peter A. Rock Thermochemistry Laboratory, University of California, Davis, California 95616, USA
Paul A. Bingham
Affiliation:
Materials and Engineering Research Institute, Sheffield Hallam University, Sheffield S1 1WB, U.K.
Richard Brooker
Affiliation:
School of Earth Sciences, University of Bristol, Bristol BS8 1RJ, U.K.
John B. Parise
Affiliation:
Department of Geosciences, Stony Brook University, Stony Brook, New York 11794, USA
*
a)Address all correspondence to this author. e-mail: martin.wilding@manchester.ac.uk
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Abstract

Carbonate glasses can be formed routinely in the system K2CO3–MgCO3. The enthalpy of formation for one such 0.55K2CO3–0.45MgCO3 glass was determined at 298 K to be 115.00 ± 1.21 kJ/mol by drop solution calorimetry in molten sodium molybdate (3Na2O·MoO3) at 975 K. The corresponding heat of formation from oxides at 298 K was −261.12 ± 3.02 kJ/mol. This ternary glass is shown to be slightly metastable with respect to binary crystalline components (K2CO3 and MgCO3) and may be further stabilized by entropy terms arising from cation disorder and carbonate group distortions. This high degree of disorder is confirmed by 13C MAS NMR measurement of the average chemical shift tensor values, which show asymmetry of the carbonate anion to be significantly larger than previously reported values. Molecular dynamics simulations show that the structure of this carbonate glass reflects the strong interaction between the oxygen atoms in distorted carbonate anions and potassium cations.

Type
Invited Paper
Information
Journal of Materials Research , Volume 34 , Issue 19: Focus Issue: Thermodynamics of Complex Solids , 14 October 2019 , pp. 3377 - 3388
Copyright
Copyright © Materials Research Society 2019 

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Footnotes

b)

Present Address: University of Manchester at Harwell, Diamond Light Source, Harwell Campus, Didcot, Oxfordshire, OX11 0DE, U.K.

c)

This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/editor-manuscripts/.

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