Enthalpies of ordering in the plagioclase feldspar solid solution

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Scientific paper

Enthalpies of solution in lead borate at ~700°C have been measured for 36 natural and heat treated plagioclase feldspars. The samples made up two series, as characterised by TEM and XRD. A "low" series contained the natural ordered material and a "high" series the same samples annealed at high temperatures to induce cation disorder. Enthalpy of solution differences between the two series give the enthalpy changes associated with the disordering reactions: low albite high albite: ~3 kcal/mole "e" structure C high albite structure: ~ 1.4-2.8 kcal/mole I structure - C high albite structure: ~0.7-1.9 kcal/mole I structure equilibrated at low temperature I structure equilibrated at high temperature: ~ 1.8-0.8 kcal/mole. H soln data for the high series overlap with the data of et al. (1980) for synthetic high structural state plagioclases except in the composition range ~An 90 -An 100 . They are consistent with an interpretation of the solid solution as being composed, at high temperatures, of two ideal (zero heat of mixing) segments, one with C symmetry and one with Il symmetry, and having a non-first order (continuous) order/disorder transformation between them. The low series can also be separated into two distinct trends, for I and "e" structures. Values of the enthalpy change due to disordering ( H ord ) also show a number of systematic trends. Firstly, the values for e C are larger than for I C in the composition range where both e and I structures are observed (~An 65 -An 72 ). Secondly, the enthalpy change on disordering the most ordered e structures at An-rich compositions is larger than for Ab-rich e structures. The apparent change in H ord , which occurs at ~An 50 , may be important for the origin of the Bøggild miscibility gap. Thirdly, the large enthalpy change of the e structure, due to ordering, may be sufficient to stabilise it relative even to a mixture of low albite plus anorthite. Values for the enthalpy change on disordering I anorthites and bytownites to a C structure have been estimated by assuming that the C solid solution is ideal (non-enthalpic) and then extrapolating a straight line through the data for Ab-rich compositions to pure anorthite.

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