Silicon-29 NMR Studies of Tetraalkylammonium Silicate Solutions. 2. Polymerization Kinetics.
The kinetics of formation of the silicate cubic octamer, Q(3)(8), in aqueous tetramethylammonium (TMA) silicate solutions was investigated by (29)Si NMR. The rate equation for solutions at pH 13.2-13.6 is d[Q(3)(8)]/dt = k(f) [H(+)](1.6)(+/-)(0.1)[TMA(+)](0.36)(+/-)(0.08)[Si](0.8)(+/-)(0.3) where k(f) = (2.2 +/- 0.8) x 10(16) mol(-)(1.8) kg(1.8) s(-)(1) at 296 K. The findings prove unequivocally that alkylammonium cations participate directly in the formation and subsequent stabilization of cagelike polysilicate anions. This implies a radically different mechanistic role than "templating" for alkylammonium cations in the synthesis of molecular sieves.
Kinrade
Stephen D.
SD
Department of Chemistry, Lakehead University, Thunder Bay, Ontario, P7B 5E1, Canada, and School of Chemical Sciences, University of Illinois at Urbana-Champaign, 505 South Mathews Avenue, Urbana, Illinois 61801.
Knight
Christopher T. G.
CT
Pole
David L.
DL
Syvitski
Raymond T.
RT