Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Effect of Loading, Voltage Difference and Phase Angle on the Synchronisation of a Small Alternator

Synchronisation of small distributed generation, 30 kVA–2 MVA, employing salient-pole synchronous machines is normally performed within a narrow range of tolerances for voltage, frequency and phase angle. However, there are situations when the ability to synchronise with non-ideal conditions would be beneficial. Such applications include power system islanding and rapid generator start-up. The physical process and effect of out-of-phase synchronisation is investigated both through simulation and experimental tests on a salient-pole alternator. There are many factors that affect synchronisation, but particular attention is given to synchronisation angle, voltage difference and, as generators will be loaded during islanding, the load angle. The results suggest that it would be acceptable for the maximum synchronisation angle of distributed generation to exceed that of current practice. Interesting observations on the nature of out-of-phase synchronisation are made, including some specific to small salient-pole synchronous machines. Furthermore, recommendations are made for synchronisation under different system conditions.