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Hydrogen-Bonding and Phase Transitions in Proton-Conducting Solid Acids

Published online by Cambridge University Press:  16 February 2011

Sossina M. Haile
Sossina M. Haile*
Affiliation:
Materials Science, 138-78, California Institute of Technology, Pasadena, CA 91125 smhaile@hyperfine.caltech.edu
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Abstract

From an investigation of the structures and electrical properties of compounds in the CsHSO4 - CsH2PO4 system, a simple model is presented for predicting whether or not a solid acid will undergo a structural transition to a disordered, superprotonic phase. Such a transition was measured in ß-Cs3(HSO4)2(H2-x(SxP1-x)O4), α-Cs3(HSO4)2(H2PO4) and Cs2(HSO4)(H2PO4), but not CsH2PO4. It is proposed that entropy drives any solid acid to a high-temperature structure in which the oxygen atoms participate equally in forming hydrogen bonds. If the H:XO4 ratio is not precisely 2:1, such chemical equivalence of oxygen atoms can only be achieved if the structure transforms to a state in which proton occupancies at hydrogen bonds are less than one and/or oxygen site occupancies are less than one. This disorder simultaneously leads to fast proton transport in the high-temperature phase, and thus superprotonic conductivity.

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