Kinetics and Thermodynamics of Mg-Al Disorder in MgAl2O4-Spinel: A Review

The MgAl2O4-spinel has wide applications in various industries and in geosciences. It shows a significant inter-site Mg-Al cation exchange (denoted by the inversion parameter x), which modifies structural features, such as the unit-cell parameters and the sizes of the component polyhedra, and influences the physical and chemical properties. Previous studies mainly focused on the kinetics and thermodynamics of the Mg-Al exchange reaction, with the aim to ascertain the correlation between the inversion parameter and temperature; these studies, however, reached conflicting results. Here, we first reviewed the kinetics studies on the Mg-Al cation exchange reaction, and then reviewed all thermodynamic experiments, with special attention paid to the Mg-Al cation exchange equilibrium and the quench process, which might have modified the cation distributions once attained at high temperatures. We also assessed the accuracies in the temperature measurements and in the quantifications of the x by different analytical methods. With some necessary temperature correction and data removal, we have landed with a generally reliable x-T dataset covering the T-x space of 873 < T < 1887 K and 0.18(1) < x < 0.357(60) (71 data pairs in total). Fitting these x-T data to three most commonly used thermodynamic models, we have obtained more accurate model parameters. Further, we also evaluated the constituent items of the Gibbs free energy for the Mg-Al cation exchange reaction with experimental results from different research fields and reached the conclusion that highly possibly the T Δ S D should not be neglected. Based on this review, we suggest that: (1) Further kinetics study on the Mg-Al exchange reaction should be performed at both low T (<~973 K) and high T (>~1173 K); (2) further Mg-Al exchange equilibrium studies should be carried out at relatively low T and ambient P, as well as in vast ranges of simultaneous high P and high T; and (3) direct experimental measures about the entropies or the enthalpies of the MgAl2O4-spinels disordered to different extents should be conducted with full characterization of the starting materials and detailed description of the experimental procedures.