Studies on the mechanism of hydrolysis and polymerization of aluminum salts in aqueous solution:: correlations between the "Core-links" model and "Cage-like" Keggin-Al13 model

Two conflicting models describe the mechanism of aluminum (Al) hydrolysis and polymerization in aqueous solution, namely, the "Core-links" model and the "Cage-like" Keggin-Al-13 model. For the sake of simplicity, the expressions of Al-13 in the "Core-links" model and the "Cage-like" model are termed as C-Al-13 and K-Al-13, respectively. The two models have co-existed for almost 50 years, but describe differences in the transformation of polymeric Al speciation in aqueous solution, such as, hydrolysis, polymerization, flocculation, precipitation and crystallization. Many of the polynuclear Al species presented in the literature cannot be adequately described with either the "Core-links" model or the "Cage-like" Keggin-Al-13 model. This paper introduces new considerations for the mechanism of Al hydrolysis and polymerization in aqueous solution, a "Continuous" model representing a unification of the "Core-links" model and "Cage-like" model, based on the systematic summary and analysis of numerous published experimental results. The general viewpoints are: (1) The "Core-links" model can only describe the transient state process for speciation changes of Al in hydrolysis and polymerization. Under a moderate titration rate of Al solution using alkaline solution, the transformation of polynuclear Al species in forced hydrolyzed Al solutions has gone through the continuous speciation change process: from small polymer (linear shape) --> middle polymer (plane shape) --> large polymer (stereoscopic conformation). This is a continuous transient course and can be described by the "Core-links" model. (2) The "Cage-like" Keggin-Al-13 model may only depict the metastable (sub-steady State) speciation of polynuclear Al, which is formed through the structural re-organization (self-assembly) during the aging of transient species. Aging is the prerequisite condition for the formation of K-Al-13. After aging the transient species of polymeric Al produced in titration, the concentration of polymeric Al determined by Ferron timed-spectrometry is equal to that of Al-13 concentration measured by Al-27-NMR, namely Al-b(photometry) approximate to K-Al-13 (OH-/Al = 1.0-2.8). So that the existence of K-Al-13 is universally approved. However, the "Cage-like" K-Al-13 structural model cannot explain the whole transformation process of polynuclear Al in aqueous solution, since many polymeric Al species produced in titration processes (transient state) cannot be detected by Al-27-NMR. In addition, the slow base-neutralization and the moderate reaction atmosphere favors the polymeric Al, facilitating the formation of K-Al-13 by self-assembly. (3) The two models can be unified. They actually reflect the different stages of the Al speciation in hydrolysis and polymerization: Al3+ --> "Core-links" species (transient state) --> K-Al-13 (metastable state) --> Al(OH)(3)(s, steady state) --> Al(OH)(4)(-). There is an inevitable intrinsic connection between the interesting polymeric Al-13 species C-Al-13 and K-Al-13. This connection can be summarized as C-Al-13(9+) --> K-Al-13(7+), which is an irreversible self-assembly course. (4) The reason for the many seemingly inconsistent and even paradoxical literature reports is due to assessment at the different stages of the Al species chain in addition to differences in experimental conditions. Therefore, a combined "Continuous" model is presented to describe the linkage of "Core-links" model and "Cage-like" model. It is based on our newly introduced concept of experimental condition comprehensive parameter-"the flux of alkali neutralization phi". (C) 2004 Elsevier B.V. All rights reserved.