title: Linear free energy relationships between dissolution rates and molecular modeling energies of rhombohedral carbonates.
abstract: Bulk and surface energies are calculated for endmembers of the isostructural rhombohedral carbonate mineral family, including Ca, Cd, Co, Fe, Mg, Mn, Ni, and Zn compositions. The calculations for the bulk agree with the densities, bond distances, bond angles, and lattice enthalpies reported in the literature. The calculated energies also correlate with measured dissolution rates: the lattice energies show a log-linear relationship to the macroscopic dissolution rates at circumneutral pH. Moreover, the energies of ion pairs translated along surface steps are calculated and found to predict experimentally observed microscopic step retreat velocities. Finally, pit formation excess energies decrease with increasing pit size, which is consistent with the nonlinear dissolution kinetics hypothesized for the initial stages of pit formation.
authors.affiliation: Division of Engineering and Applied Sciences, Pierce Hall, 29 Oxford Street, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Owen W
authors.initials: OW
authors.lastname: Duckworth
authors.forename: Randall T
authors.initials: RT
authors.lastname: Cygan
authors.forename: Scot T
authors.initials: ST
authors.lastname: Martin
mesh_terms: D002254:Carbonates / Q000737:chemistry*; D003198:Computer Simulation; D016014:Linear Models; D008956:Models, Chemical; D008958:Models, Molecular; D012996:Solutions / Q000737:chemistry; D013499:Surface Properties; D013816:Thermodynamics
chemical_list: D002254:Carbonates; D012996:Solutions