Promising Isotope Effect in Pd77Ag23 for Hydrogen Separation

Pd–Ag alloys are largely used as hydrogen separation membranes and, as a consequence, the Pd–Ag–H system has been intensively studied. On the contrary, fewer information is available for the Pd–Ag–D system; thus, the aim of this work is to improve the knowledge of the isotope effect on the commercial Pd77Ag23 alloy, especially for temperature above 200 °C. In particular, deuterium absorption measurements are carried out in the Pd77Ag23 alloy in the temperature range between 79 and 400 °C and in the pressure range between 10−2 and 16 bar. In this exploited pressure (p) and composition (c) range, above 300 °C the pc isotherms display the typical shape of materials where only a solid solution of deuterium is present while at lower temperatures these curves seem to be better described by the coexistence of a solid solution and a deuteride in a large composition range. The obtained results are compared and discussed with the ones previously measured with the lightest hydrogen isotope. Such a comparison shows that the Pd77Ag23 alloy exhibits a clear inverse isotope effect, as the equilibrium pressure of the Pd–Ag–D system is higher than in Pd–Ag–H by a factor of ≈2 and the solubility of deuterium is about one half of that of hydrogen. In addition, the absorption measurements were used to assess the deuteration enthalpy that below 300 °C is ΔHdeut = 31.9 ± 0.3 kJ/mol, while for temperatures higher than 300 °C, ΔHdeut increases to 43 ± 1 kJ/mol. Additionally, in this case a comparison with the lighter isotope is given and both deuteration enthalpy values result lower than those reported for hydrogenation. The results described in this paper are of practical interest for applications operating above 200 °C, such as membranes or packing column, in which Pd77Ag23 has to interact with a gas stream containing both hydrogen isotopes.

Nitrogen isotope effects can be used to diagnose N transformations in wastewater anammox systems

Anaerobic ammonium oxidation (anammox) plays an important role in aquatic systems as a sink of bioavailable nitrogen (N), and in engineered processes by removing ammonium from wastewater. The isotope effects anammox imparts in the N isotope signatures (15N/14N) of ammonium, nitrite, and nitrate can be used to estimate its role in environmental settings, to describe physiological and ecological variations in the anammox process, and possibly to optimize anammox-based wastewater treatment. We measured the stable N-isotope composition of ammonium, nitrite, and nitrate in wastewater cultivations of anammox bacteria. We find that the N isotope enrichment factor 15ε for the reduction of nitrite to N2 is consistent across all experimental conditions (13.5‰ ± 3.7‰), suggesting it reflects the composition of the anammox bacteria community. Values of 15ε for the oxidation of nitrite to nitrate (inverse isotope effect, − 16 to − 43‰) and for the reduction of ammonium to N2 (normal isotope effect, 19–32‰) are more variable, and likely controlled by experimental conditions. We argue that the variations in the isotope effects can be tied to the metabolism and physiology of anammox bacteria, and that the broad range of isotope effects observed for anammox introduces complications for analyzing N-isotope mass balances in natural systems.

Theory of Isotope Effect in YBaCuO

This paper is the first to demonstrate that a pure nonphonon mechanism can quantitatively explain all isotope effect experiments in YBaCuO (YBCO) and to conclude that the influence of zero-point oscillation on the two local spin-mediated interaction (TLSMI) causes the isotope effects in YBCO. This paper is the first to calculate the doping dependence of exponents of oxygen isotope effect for all quantities of YBCO, such as , T, pseudogap at , gap at 0 K, and number density of supercurrent carriers at 0 K. This paper points out that the observed inverse isotope effect of comes also from zero-point oscillation.