CALORIMETRIC AND SPECTROSCOPIC INVESTIGATION OF THE ACIDITY OF HZSM-5

The cal-ad analysis of HZSM-5 provides a novel characterization of the donor-acceptor properties of this solid acid showing 0.0415 mmol per g of a strong Bronsted site and 0.53 mmol per g of a weaker site. Of a ll studies to date, only cal-ad provides a measure of the extent, K-i; strength, -Delta H-i; and quantity of sites. The relative K values sh ow why gas phase calorimetry, TPD, TGA, DSC, and isopropylamine decomp osition do not resolve the two sites found by cal-ad and incorrectly s uggest 0.6 mmol.g(-1) of strong acid sites. Reaction with pyridine giv es an enthalpy of 42.1 and 8.6 kcal mol(-1), respectively, for the two sites suggesting the latter is a hydrogen bonding site. Other acidity measures average these sites, and their enthalpies contain dispersion as well as donor-acceptor components. Comparison of these results wit h other cal-ad results suggests HZSM-5 is a strong solid acid but not a super acid. Titrations with 2,6-lutidine and 2,6-di-tert-butylpyridi ne indicate that the strong Bronsted sites are located in the 5.5 a ch annels with no detectable amounts on the exterior surface.