화학공학소재연구정보센터
Journal of Chemical Thermodynamics, Vol.136, 182-189, 2019
Applied predictive thermodynamics (ThermAP). Part 2. Apatites containing Ni-2+, Co2+, Mn2+, or Fe2+ ions
Apatites are minerals encountered in many fields including geochemistry, nuclear and environmental sciences as well as medicine. This ubiquity is likely related to the diversity of ion substitutions that the apatite structure can accommodate, making of it an excellent ion reservoir either in natural settings or for the intentional production of doped systems with tailored properties. Despite this widespread interest for apatite compounds, however, only few studies are dedicated to study their thermodynamic properties. Yet, their knowledge becomes necessary for assessing stability domains and understanding evolutionary trends in solution or upon heating, for example. Recently, the experimental thermodynamics of 33 phosphate apatite compounds (deriving from the composition M-10(PO4)(6)X-2) have been reviewed and their comparison allowed the development of the additive predictive model ThermAP (Applied Predictive Thermodynamics) capable of adequately predicting properties such as standard enthalpies (Delta H-f degrees), Gibbs free energies of formation (Delta G(f)degrees), or entropies (S) at T= 298 K, for any composition involving ions among M2+ = Ca2+, Ba2+, Sr2+, Mg2+, Cd2+, Pb2+, Cu2+, Zn2+ and X = OH, F, Cl or Br. Although experimental data for apatites involving other divalent cations such as Ni2+, Co2+, Mn2+ or Fe2+ do not seem to be available, the exploration of apatites doped with these ions is appealing from a practical and fundamental viewpoint, for example for understanding geochemical events, or when using apatite precipitation for the elimination of metal cations from industrial wastewaters, or else for conferring magnetic properties to apatite systems in medicine. Based on multiple physicochemical correlations, the present contribution extends the additive predictive model ThermAP to Ni, Co, Mn(II) and Fe(II)doped apatites. It provides for the first time estimations of enthalpies, Gibbs free energies of formation and entropies, unveiling the general stability ranking Mn(II)-apatite > Fe(II)apatite > Co-apatite Niapatite. This additive approach also allows one to estimate these properties for any composition in view of enabling thermodynamic calculations for applicative or fundamental purposes. (C) 2015 Elsevier Ltd. All rights reserved.