Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates
Crystallization of Al-bearing solid phases from highly alkaline Na2O:Al2O3:H2O solutions commonly necessitates an Al3+ coordination change from tetrahedral to octahedral, but intermediate coordination states are often difficult to isolate. Here, a similar Al3+ coordination change process is examined during the solid-state recrystallization of sodium oxohydroxoaluminate hydrate (MSA) to nonasodium bis(hexahydroxy aluminate) trihydroxide hexahydrate (NSA) at ambient temperature. While the MSA structure contains solely polymerized tetrahedral Al3+, the NSA structure is a molecular aluminate salt solely based upon monomeric octahedral Al3+. Spontaneous recrystallization of MSA and excess sodium hydroxide hydrate into NSA over 3 days of reaction time was clearly evident in X-ray diffractograms and in Raman spectra. In situ 27Al multiple quantum MAS NMR spectroscopy showed no evidence of intermediate aluminates, suggesting that intermediates, such as pentacoordinate Al3+, are short-lived and require more highly time resolved spectroscopies to detect. Such research is advancing upon detailed mechanistic understanding of Al3+ coordination change mechanisms in these highly alkaline systems, with relevance to aluminum refining, corrosion sciences, and nuclear waste processing.
Revised: February 15, 2021 |
Published: May 18, 2020