Origins of Deviations from Transition-State Theory: Formulating a New Kinetic Rate Law for Dissolution of Silicates

Icenhower, Jonathan ; McGrail, B. P. ; Luttge, A. ; London, D.

Pacific Northwest National Lab., Richland, WA

关键词: Origin;    Saturation;    Forecasting;    Computerized Simulation;    Dissolution;   

DOI  :  10.2172/834824
RP-ID  :  EMSP-81908-2002
RP-ID  :  FG07-01ER63287
RP-ID  :  834824

美国|英语

来源: UNT Digital Library

【 摘 要 】

Present models for dissolution of silicate minerals and glasses, based on transition-state theory (TST), overestimate the reaction rate as solution compositions approach saturation with respect to the rate-governing solid. Therefore, the reactivity of key materials in the environment, such as feldspar, mica, and borosilicate glass, is uncertain, and any prediction of future aqueous durability is suspect. The core objective of this investigation is to determine the origin of these discrepancies and to fashion a quantitative model that reliably predicts the reactivity of silicate materials in realistic environmental conditions. This is being accomplished using newly developed experimental techniques checked against computer simulations based upon first principle theory.