Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF3SO3 Media to 250 °C

Autor:	Michael L. Machesky, Moira K. Ridley, David J. Wesolowski, Milan Předota
Rok vydání:	2015
Předmět:	Denticity Chemistry Analytical chemistry Electrolyte Capacitance Surfaces Coatings and Films Electronic Optical and Magnetic Materials Molecular dynamics General Energy Rutile Titration Physical and Theoretical Chemistry Hydration energy Trifluoromethanesulfonate
Zdroj:	The Journal of Physical Chemistry C. 119:15204-15215
ISSN:	1932-7455 1932-7447
Popis:	A comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3–) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (−0.1 and −0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched wel...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::3e5ffe7e08c8a88910e8a219f37eec81 https://doi.org/10.1021/acs.jpcc.5b02841 Zobrazit plný text záznamu