Abstract. The study of water in minerals with infrared spectroscopy is reviewed with emphasis on natural and synthetic quartz. Water can be recognized in minerals as fluid inclusions and as isolated molecules and can be distinguished from hydroxide ion. The distinction between very small inclusions and aggregates of structurally bound molecules is difficult. New studies of synthetic quartz using near-infrared spectroscopy are reported. These demonstrate that water molecules are the dominant hydrogen containing species in synthetic quartz but that this water is not in aggregates large enough to form ice when cooled.

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A panel of five zinc-chelated aza-macrocycle ligands and their ability to catalyze the hydration of carbon dioxide to bicarbonate, H(2)O + CO(2) → H(+) + HCO(3)(–), was investigated using quantum-mechanical methods and stopped-flow experiments. The key intermediates in the reaction coordinate were optimized using the M06-2X density functional with aug-cc-pVTZ basis set. Activation energies for the first step in the catalytic cycle, nucleophilic CO(2) addition, were calculated from gas-phase optimized transition-state geometries. The computationally derived trend in activation energies was found to not correspond with the experimentally observed rates. However, activation energies for the second, bicarbonate release step, which were estimated using calculated bond dissociation energies, provided good agreement with the observed trend in rate constants. Thus, the joint theoretical and experimental results provide evidence that bicarbonate release, not CO(2) addition, may be the rate-limiting step in CO(2) hydration by zinc complexes of aza-macrocyclic ligands. pH-independent rate constants were found to increase with decreasing Lewis acidity of the ligand-Zn complex, and the trend in rate constants was correlated with molecular properties of the ligands. It is suggested that tuning catalytic efficiency through the first coordination shell of Zn(2+) ligands is predominantly a balance between increasing charge-donating character of the ligand and maintaining the catalytically relevant pK(a) below the operating pH.

Methane (CH 4 ) is an important greenhouse gas, second only to CO 2 , and is emitted into the atmosphere at different concentrations from a variety of sources. However, unlike CO 2 , which has a quadrupole moment and can be captured both physically and chemically in a variety of solvents and porous solids, methane is completely non-polar and interacts very weakly with most materials. Thus, methane capture poses a challenge that can only be addressed through extensive material screening and ingenious molecular-level designs. Here we report systematic in silico studies on the methane capture effectiveness of two different materials systems, that is, liquid solvents (including ionic liquids) and nanoporous zeolites. Although none of the liquid solvents appears effective as methane sorbents, systematic screening of over 87,000 zeolite structures led to the discovery of a handful of candidates that have sufficient methane sorption capacity as well as appropriate CH 4 /CO 2 and/or CH 4 /N 2 selectivity to be technologically promising.

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Attempts to introduce molecular water into dry, natural quartz crystals by diffusive transport and thus weaken them hydrolytically at T = 700°-90(JOC and Pu,o = 400-1550 MPa have failed. Infrared spectroscopy of hydrothermally annealed single crystals of natural quartz reveals the diffusive uptake of interstitial hydrogen (resulting in hydroxyl groups) at rates similar to those previously proposed for intracrystalline water at high water pressures. The solubility of interstitial hydrogen at these conditions is independent of temperature and pressure; instead, it depends upon the initial aluminum concentration by the local charge neutrality condition [H, "] . Deformation experiments following hydrothermal annealing show no mechanical weakening, and the lack of any detectable broadband absorption associated with molecular water shows that the diffusion rates of structural water are much lower than those of hydrogen. These results are consistent with the available oxygen diffusion data for quartz and with the failure to observe weakening in previous studies of quartz deformation at pressures of 300-500 MPa; they call into question the rapid rates of diffusion originally suggested for the hydrolytic weakening defect. It is suggested that the observed weakening in many previous experiments was complicated by microcracking processes in response to nonhydrostatic stresses and low effective confining pressures. Extensive microcracking may prm:ide a mechanism for molecular water to enter quartz and allow local plastic deformation to occur. It does not appear that molecular water can diffuse far enough into uncracked quartz to allow hydrolytic weakening over annealing times that are feasible in the laboratory.

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