An analytical protocol involving gas chromatography (GC), gas chromatography-mass spectrometry (GCMS), and /sup 29/Si//sup 1/H/ NMR spectroscopy, was developed to determine the structures of the polysilicate intermediates formed during silica sol-gel polymerization. This protocol allowed the structural identification of mono- through hexasilicate species (1less than or equal to /times/ less than or equal to6 in (Si/sub x/O/sub y/) (OCH/sub 3/)/sub a/) formed during partial hydrolysis and condensation of tetramethylorthosilicate. The analytical protocol employing capillary gas chromatography was applied to monitor the stoichiometry, structures, and abundances of low molecular weight polysilcates (1less than or equal to /times/ less than or equal to6 in (Si/sub x/O/sub y/)(OCH/sub 3/)/sub a/) formed during partial hydrolysis of methanolic tetramethylorthosilicate under acidic (HCl) and basic (KOH) conditions. The same procedure was applied to study the redistributions of methanolic hexamethyldisilicate and octamethyltrisilicate under similar reaction conditions. The polysilicate molecular weight distributions (expressed in terms of mole percent of total silicon present) were determined as a function of the degree of polymerization. 69 refs., 33 figs., 16 tabs.