Journal of Physical Chemistry A, Vol.112, No.29, 6609-6620, 2008
Desorption of nitric acid from boehmite and gibbsite
Solid-state Fourier transform infrared spectroscopy (FTIR), evolved gas analysis-FTIR (EGA-FTIR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSQ have been used to investigate the desorption of nitric acid from boehmite and from gibbsite. Samples containing between 3 and 36% of adsorbed nitric acid by mass were prepared by placing the mineral in a 70% nitric acid solution or by the adsorption of nitric acid vapors in humid air. FTIR established that water-solvated nitrate was the main species adsorbed on the surface of either mineral under these conditions. The water-solvated nitrate vaporized as nitric acid at similar to 400 K with an enthalpy of desorption of similar to 50 kJ/mol for both surfaces. A second nitric acid desorption occur-red at similar to 450 K and had an enthalpy of desorption of 85 kJ/mol (95 kJ/mol) for boehmite (gibbsite). This was assigned as desorption of partially solvated aluminum hydroxylated nitrate. Monodentate and bridging nitrate were also observed on the boehmite. These species desorbed at similar to 725 K as NO2 and O-2 with an enthalpy of reaction of similar to 55 kJ/mol of NO2 desorbed.