Thermal equations of state for B1 and B2 KCl

Publication Type  Journal Article
Year of Publication  2002
Authors  Walker, D.; Cranswick, L. M. D.; Verma, P. K.; Clark, S. M.; Buhre, S.
Journal Title  American Mineralogist
Volume  87
Issue  7
Pages  805-812
Journal Date  Jul
ISBN Number  0003-004X
Accession Number  ISI:000176670000001
Key Words  high-pressures; alkali-halides
Abstract  

Compressibility of solids generally drops as compression proceeds. Bonds shorten and stiffen with density increase in the same structure. However for the B1-B2 phase transition in many measured alkali halides, bond lengths increase in going to the denser phase. And IR mode frequencies decrease (Hofmeister 1997), leading to the counter-intuitive expectation that compressibility should increase in going to the denser B2 phase. Past volume measurements have been equivocal at best in recognizing any such compressibility increase. New thermal equations of state for B1 and B2 KCl from in-situ X-ray diffraction measurements of phase volumes on Station 16.4 of the CLRC Daresbury Laboratory are no less equivocal about the issue of whether compressibility increases or decreases across the transition. In contrast, the new volume measurements show an easily resolved thermal expansion increase in going from B1 to B2 KCl. The product alpha.K, which is better known than either alpha or K, increases from 0.0195+/-0.0005 kbar/degreesC in B1 to 0.0275+/-0.0009 kbar/degreesC in B2 KCl. Yagi (1978) demonstrated a similar increase for KF, also supported mainly by increases in alpha. This increase can also be seen in RbCl (Walker er al. 2001). Bond weakening indicated by the thermal expansion increase is consistent with the elusive compressibility increase that is expected across the B1-B2 transition but which is not resolved from volume measurements. The thermal effects are more visible than the compressional effects on alpha.K across the transition. Bond tightening upon decompression reduces alpha, increases solid viscosity, and hence decreases the Rayleigh number. An upwelling of material undergoing a decompression phase change with decrease of coordination number may have its convective friskiness damped at such a transition.

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570QWTimes Cited:6Cited References Count:21

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