Sensing the physicochemical nature of he and ne in micropores by adsorption measurements

He and Ne in contact with molecular sieves in the form of crystalline A zeolites and amorphous carbon molecular sieves fibers (CMSF) were studied by adsorption measurements. Classification of the effective enclosure of zeolitic apertures and of graphitic constrictions, as determined by recent temperature-programmed desorption mass spectrometry (TPD-MS) studies of adsorption of He and Ne onto these materials, was utilized in making a prudent choice of samples and experimental conditions. In view of the former TPD information, the behaviors of adsorption and volumetric measurements reported herein are straightforwardly interpreted. The combined TPD, adsorption isotherms, and dead volume data deepen the understanding of the physicochemical nature of adsorbed gas, where gas adsorption in the vicinity of pore constrictions and/or apertures as well as on the inner surface areas of pores and/or cages could be resolved. Previous conclusions that the huge activation energies measured for Ne/CMSF at high temperatures are unlikely to characterize chemical desorption but reflect those required for overcoming the barrier of effectively constricted apertures were confirmed by the volumetric data presented here. At 77 K, considerable He adsorption was observed in the porous solids and found to be responsible for abnormal deduced values of dead volumes. The occurrence of significant adsorption of He onto A zeolites and CMSF at 77 K warrants the realization that in cases concerning porous materials, volumetrically deduced quantities should not be taken for granted, but should be carefully considered and uniquely interpreted in relation to the specific experimental conditions under which they are taken.     

A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O

Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.     

The role of the cation in the oxygen isotopic exchange in crystalline sulfate salt hydrates

The oxygen isotopic exchange during dehydration and decomposition of five sulfate salt hydrates (CoSO₄·6H₂O, NiSO₄·7H₂O, ZnSO₄·7H₂O, CaSO₄·2H₂O, Li₂SO₄·H₂O) was studied in detail by temperature programmed desorption mass spectrometry (TPD-MS) in a supersonic molecular beam (SMB) inlet mode. Crystals of the ¹⁸O-enriched salts were grown and the detailed desorption steps of the various gaseous products released during dehydration and decomposition of these compounds were recorded. The desorption patterns confirmed the known characteristic stepwise dehydration of these salts, where regardless of the crystalline structure and composition, in all the salts (excluding the Li and Ca sulfates) a major group of n ? 1 loosely bounded water of crystallization molecules (out of total of n molecules in the fully hydrated form) are released at adjacent temperatures in a typical low temperature range (<200 °C), while the last, most strongly bounded water molecule, consistently desorbs at relatively higher temperatures (240 < T < 440 °C). Interestingly, it is established that the oxygen isotopic exchange occurs exclusively between that latter, most strongly bound water molecule, and the salt anion. Remarkably, the results point out that the exchange process is mostly of solid-solid nature. Finally, the results point out that the probability of the isotopic exchange increases with the increment in the desorption temperature of the last dehydration step, i.e. with the bond strength in the monohydrate, between the last water molecule of crystallization and the cation.