Enthalpy effects associated with Al/Si ordering in anhydrous Mg-cordierite

Measurements of the heats of solution (ΔH_soln) in molten Pb₂B₂O₅ at 708°C of anhydrous magnesian cordierites, prepared with a range of structural states, show that the enthalpy effect associated with Al/Si ordering is substantial (≳ 9.76 ± 1.56 kcal mole^-1). Differences in the state of order between synthetic cordierites used in phase equilibrium studies and cordierites in the natural environment could lead to significant errors in the estimation of palaeo-pressures and temperatures. A continuous change of ΔH_soln with annealing time supports the suggestion of putnis (1980) that the hexagonal → orthorhombic transformation in cordierite, which can occur via a modulated structure, is truly continuous under metastable conditions. In addition, a linear relation between ΔH_soln and the logarithm of annealing time has been found, which provides some insight into the nature of the ordering mechanisms at an atomic level. Al and Si exchanges occur continuously between neighbouring tetrahedral sites with a net drift towards increasing order. No kinetic or thermochemical distinction can be made between the development of long range and short range order. The enthalpy of vitrification (~ 12 kcal mole^-1) for a metastable stuffed β-quartz polymorph of cordierite composition is similar to that for pure quartz (on a per two oxygen basis), while the heat of vitrification for even the most disordered cordierite seen in this study is more than a factor of three greater (~40 kcal mole^-1). This is consistent with the view that cordierite glass resembles the quartz structure more closely than the crystalline cordierite structure, and that crystallisation of the glass below ~900°C is controlled by a tetrahedral framework.