Thermochemistry of glasses along joins of pyroxene stoichiometry in the system Ca 2 Si 2 O 6 -Mg 2 Si 2 O 6 -Al 4 O 6

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Enthalpies of solution in 2PbO · B 2 O 3 at 974 K have been measured for glasses along the joins Ca 2 Si 2 O 6 (Wo)-Mg 2 Si 2 O 6 (En) and Mg 2 Si 2 O 6 -MgAl 2 SiO 6 (MgTs). Heats of mixing are symmetric and negative for Wo-En with W H = -31.0 ± 3.6 kJ mol - . Negative heats of mixing were also found for the En-MgTs glasses ( W H = -33.4 ± 3.7 kJ mol - ). Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation. Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al / Si 1 is suggested.

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