Description of Mg2+ Release from Forsterite Using Ab Initio Methods

作者：Morrow Christin P; Kubicki James D^*; Mueller Karl T; Cole David R

来源：Journal of Physical Chemistry C, 2010, 114(12): 5417-5428.

DOI：10.1021/jp9057719

Molecular clusters representative of protonated, neutral, and deprotonated sites on a forsterite (Mg2SiO4) surface were employed to facilitate examination of Mg-O-hr bond-breaking via density functional theory (DFT) calculations with the B3LYP/6-31+G(d,p) methodology. Hydrolysis reactions of the molecular clusters with a H2O molecule yielded barrier heights of 21, 54, and 39 kJ/mol for protonated, neutral,;and deprotonated sites in the as-phase, respectively, and the rate constants calculated using these barrier heights were 5.7 x 10(8), 2.7 x 10(4), and 2.2 x 10(6) s(-1), respectively. Aqueous-phase calculations on the gas-phase Structures were also performed, and the barrier heights were 33, 40, and 21 kJ/mol for the protonated, neutral, and deprotonated models. Rate constants were 4.3 x 10(6), 6.1 x 10(5), and 6.0 x 10(8) s(-1). For models energy-minimized in the aqueous-phase, the barrier heights were 37, 44, and 40 kJ/mol, and the rate constants were 1.7 x 10(6), 3.0 x 10(4), and 9.9 x 10(5) s(-1), respectively. These differences highlight the importance of modeling Structures with inclusion of solvent effects. Rates of Mg2+ release from the forsterite surface were predicted using these rate constants and models of the reactive site density and the H+ or OH- surface speciation. These calculations are consistent with a more rapid rate of Mg2+ release under acidic conditions even though the activation energy barriers are equivalent within computational uncertainty. A comparison of these results to previous data shows that the predicted rates are much faster than experimentally measured Mg2+ release rates, suggesting that breaking the Mg-O-hr bond is a rapid process which is a component of Mg2+ release from the Surface consistent with previous experimental observation of preferential Mg2+ leaching from forsterite. A dissolution mechanism involving polymerization and hydrolysis of Si-O-br-Si linkages is discussed that is consistent with the discrepancy between Mg2+ release rates and dissolution rates of forsterite.

• 出版日期2010-4-1