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A new, fast, and simple method based on size exclusion chromatography permits determination of the volumes of open and closed pores of rigid solids such as silica or porous glasses, together with the specific surface and the pore‐size distribution for pore diameters ranging from 10 to 4000Å. The results are in good agreement with those obtained by classical methods (capillary condensation, mercury porosimetry).

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Ein neues, einfaches und schnelles Verfahren, das auf der Methode der Ausschlufi-Chromatographie beruht, ermoglicht bei Festkorpern wie Silicagelen die Bestimmung des Porenvolumens, der spezifischen Oberflache, des Volumens der geschlossenen Poren sowie der Porendurchmesser-Verteilung fur Porendurchmesser zwischen lOA und 4000A. Die Ergebnisse stimmen gut rnit denen der klassischen Methoden (Kapillarkondensation, Quecksilber-Porosimetrie) iiberein. 54Angew. Chem. 90, 954-Y61 (1978)

The molecular structures of various silica gels are compared using 29 Si NMR and laser Raman spectroscopy. When gels are deposited onto a porous organic resin from tetra ethyl orthosilicate, TEOS, at acidic or basic conditions, their appearance and physical properties show dramatic differences. It is demonstrated that these differences are associated with distinct Q 3 /Q 4 SiÀOÀSi connectivity ratios in the two materials although both are mainly constructed from 3 and 5 member siloxane rings (3R and 5R). Comparative NMR and Raman spectroscopic experiments on these gels and related model calculations indicate that Raman is disproportionally more sensitive for Q 1 and Q 2 connectivities than for Q 3 and Q 4 . This is an important new aspect to consider in the Raman identification of Q n connectivities in amorphous silicates. It is also shown that the molecular structures of TEOS based gels differ when made in the presence or absence of the porous organic substrate. Hence the substrate seems to exert structure directing effect. Characteristic structural differences have been identified also between the TEOS based silica gels and gels prepared from a commercial 3.22 SiO 2 /Na 2 O ratio aqueous sodium silicate solution. Moreover the structure of an "as synthesized" base set Na-silicate hydrogel is also different from that of its acid set counterpart: the former gel contains mainly 4 and 5 member and larger siloxane rings while the latter one virtually does not show any ring-associated Raman vibration. This result provides direct experimental support for the decades-old theoretical predictions that physical differences of acid and base set gels might be related to their ring and branched linear chain structures, respectively. We also demonstrate that the acid set gel gradually develops siloxane rings during its washing and aging procedures.

To facilitate molecular spectroscopic observation of the mysterious transition of dissolved sodium silicate molecules into nanoparticles of desired silica gel and zeolite structures, the IR and Raman spectra of Na 2 H 2 SiO 4 monomers are studied here in details. It is demonstrated that the 3-0.2 mol/L aqueous solutions of Na 2 SiO 3 and Na 2 SiO 3 Â 9H 2 O contain mostly Na 2 H 2 SiO 4 monomers dissociated about 30%-80%, respectively. In contrast to the common belief the Si-O vibrations of these monomers depend on their dissociation level generating FTIR and Raman bands which are frequently associated with polymer silica structures in the current literature. To stay consistent with the molweight and dissociation measurements, these vibrational assignments are revised in this paper. Some unique and unexpected effects of D 2 O used instead of H 2 O as solvent are also reported.

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