A quantitative understanding of the thermochemistry of silicate solution systems is necessaryfor the design,optimizationand controlof sol-gel,colloid and zeoliteprepara- tions. This review is intended to be a compendium of ready informationfor the growing numberof chemicalengineersactiveinsolution-basedmaterialssynthesis.Experimental measurements of silica solubility, silicate speciation and silanol deprotonation in aque- ous solutions are summarized and critiqued. The thermochemical properties of monomeric and dimeric silicate anions are also assessed, The trends that are then evi- dent are compared with expectationsfrom simplisticgas-phase molecular orbital calcu- lations to illustrate the importance of solvation. Finalb, the equilibrium behavior of simple silicate oligomers is rationalized,and the future direction to quantitative model- ing of the behavior of more complex oligomers is suggested.
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