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Evidence of residual entropy in the cubic spinel Zn2TiO4

Jacob, KT and Alcock, CB (1975) Evidence of residual entropy in the cubic spinel Zn2TiO4. In: High Temperatures -High Pressures, 7 . pp. 433-439.

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The standard free energies of formation of Zn2Ti04 and ZnTi03 have been determined in the temperature range 930° to i ioo'x from electromotive force measurements on reversible solid oxide galvanic cells;Ag-5at%znll I Pt, + CaO-Zr02 ZnO I II Ag-5at%Zn Y20r Th02 CaO-Zr02 + ,Pt Zn2Ti04+ ZnTi03 and II Ag-5at%Zn CaO-Zr02 + ,Pt ZnTi03+ Ti02 The values may be expressed by the equations,2ZnO (wurtz) + Ti02(rut) -> Zn2Ti04(sp), f:!:.Go = -750-2-46T (±75)cal;ZnO(wurtz) +Ti02(rut) -> ZnTi03(ilmen) ,f:!:.Co = -]600-0·]99T(±50)cal.Combination of the free energy values with the calorimetric heat of formation, and low-temperature and high-temperature heat capacity of Zn2Ti04 reported in literature, suggests a residual entropy of ],9 (±0·6) cal K-1 mol ? for the cubic spinel. Ideal mixing of Zn2+ and Ti4+ ions on the octahedral sites would result in a configurational contribution to the entropy of 2· 75 cal K-1 rnol ".The difference is indicative of short-range ordering of cations on octahedral sites.

Item Type: Journal Article
Publication: High Temperatures -High Pressures
Department/Centre: Division of Mechanical Sciences > Materials Engineering (formerly Metallurgy)
Date Deposited: 05 Dec 2011 06:50
Last Modified: 05 Dec 2011 06:50
URI: http://eprints.iisc.ac.in/id/eprint/42478

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