Thermochemistry of stuffed quartz-derivative phases along the join LiAlSiO4-SiO2

Hongwu Xu, Peter J. Heaney, Alexandra Navrotsky, Letitia Topor, Jun Liu

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Abstract

Enthalpies of drop-solution (ΔH(drop-soln)) of a suite of stuffed quartz-derivative phases with the composition Li(1-x)Al(1-x)Si(1+x)O4 (0 ≤ x ≤ 1) have been measured in molten 2PbO·B2O3 at 974 K. Substitution of Si4+ for Li+ + Al3+ results in more exothermic enthalpies of drop-solution, which is consistent with behavior seen in other crystalline and glassy aluminosilicates. Al/Si ordering serves to stabilize these phases, and long-range ordering for compositions with x approximately <0.3 can be discerned in both calorimetric data and in structural data obtained by electron and synchrotron X-ray diffraction (XRD). In contrast, a structural but not an energetic discontinuity is apparent at x κ 0.65, which corresponds to a compositionally induced α-β quartz transition with a small enthalpy of transformation. An enthalpy for the Al/Si order-disorder reaction in β-eucryptite was measured as 25.9 ± 2.6 kJ/mol. Standard molar enthalpies of formation of the stuffed quartz-derivative phases from constituent oxides (ΔH(f,ox)0) and elements (ΔH(f,el)0) at 298 K also are presented. ΔH(f,ox)0 = -69.78 ± 1.38 kJ/mol and ΔH(f,el)0 = -2117.84 ± 2.50 kJ/mol for β-eucryptite, which are in good agreement with results previously determined by HF solution calorimetry at 346.7 K (Barany and Adami 1966). The enthalpies of formation of other compositions are reported for the first time.

Original languageEnglish (US)
Pages (from-to)1360-1369
Number of pages10
JournalAmerican Mineralogist
Volume84
Issue number9
DOIs
StatePublished - Sep 1999

All Science Journal Classification (ASJC) codes

  • Geophysics
  • Geochemistry and Petrology

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