Electricity production from lignocellulosic biomass by direct coupling of a gasifier and a nickel/yttria-stabilized zirconia-based solid oxide fuel cell: influence of the H<Subscript>2</Subscript>S content of the syngas onto performances and aging

The aim of this work is to study the reactivity of a Ni-YSZ-based solid oxide fuel cell (SOFC) fueled with gaseous mixtures having the same composition as the syngas issued from a fixed-bed downdraft and staged gasification pilot. The syngas issued from the gasifier contains some ppm(v) of H₂S, and in order to adapt the purification process, the influence of this compound on the Ni-YSZ-based SOFCs is evaluated at 600 and 850 °C. The influence of H₂S depends on fuel composition, temperature but also of current density. In H₂–N₂ mixtures and only at 600 °C, a significant decrease of cell performances is observed for H₂S?>?4.5 ppm(v). For H₂–CO–CO₂–N₂ mixtures, the influence is more important since a small decrease of performance can be observed for 1 ppm(v) of H₂S even at 850 °C. Nevertheless, at 600 °C, it is possible to avoid damage by limiting the current density. Aging experiments, realized at 750 °C, show that the influence of 1 and 2 ppm(v) of H₂S is more important during the first 20 h and is reversible: at this temperature, after poisoning with 1 ppm(v) of H₂S during 72 h, the cell recovers 91% of its initial power density after 100 h in pure hydrogen, and after subsequent poisoning with 2 ppm(v) of H₂S during 77 h, the cell recovers 94% of its initial power density after 168 h in pure hydrogen.     

The elusive atomic rationale for DNA base pair stability

A systematic analysis of the electrostatic interaction between 27 natural DNA base pairs was carried out, based on ab initio correlated wave functions and the topology of the electron density. Using high rank multipole moments we show that the atomic partitioning of the interaction energy contains many substantial contributions between distant atoms. Profiles of cumulative energy versus internuclear distance show large fluctuations and provide an electrostatic fingerprint of the partitioning of interaction energy in a complex. A quantified comparison between each pair of energy profiles, one for each base pair, makes clear that there is no correlation between the total base pair interaction energy and the shape of the profile. In other words, base pairs with similar interaction energy are not stable for the same reasons in terms of atomic partitioning. In summary, simple rules to rationalize the pattern of energetic stability of naturally occurring base pairs in terms of subsets of atoms are elusive. Our work cautions against inappropriate use of Jorgensen's secondary interaction hypothesis.     

Ring dehydration mechanisms and kinetics of polyamic acid models in solution and in the solid state

We have synthesized and studied the ring dehydration mechanisms and kinetics of polyamic acid models in solution and in the solid state using ¹³C-NMR (solid and liquid), HPLC, FTIR, and x-ray diffraction. Results obtained in solution show the role of temperature, catalysts, and the basicity of the amine in ring dehydration mechanisms and kinetics, as well as conformation and intramolecular bonds in the amic acid bond in the solid state. © 1993 John Wiley & Sons, Inc.     

High pressure synthesis and crystal structure of a new series of perovskite-like compounds CMn7O12 (C = Na,Ca, Cd,Sr, La,Nd)

A new series of perovskite-like compounds CMn₇O₁₂ have been synthesized under high pressure and high temperature conditions. C is a large divalent or trivalent cation such as Ca, Cd, Sr, La and Nd. The structures of the quenched materials have been determined from powder X-ray data. They are distortions of the NaMn₇O₁₂ cubic structure. The [C²⁺Mn³⁺₃](Mn³⁺₃Mn⁴⁺)O₁₂ compounds are trigonal ($\text{R}\text{3}$). The C²⁺ and Mn³⁺ as well as the Mn³⁺ and Mn⁴⁺ cations are ordered on the corresponding A and B sites of the perovskite structure, respectively. The [C³⁺Mn³⁺₃] (Mn³⁺₄)O₁₂ compounds are monoclinic ($\text{I}\text{2}\text{m}$). In these compounds the order exists only in the A sites. It is shown that the lower symmetry may be the result of a cooperative Jahn-Teller effect of the Mn³⁺ cations occupying the B sites.     

An alternating direction scheme on a nonuniform mesh for reaction-diffusion parabolic problems

In this paper we develop a numerical method for two-dimensionaltime-dependent reaction-diffusion problems. This method, whichcan immediately be generalized to higher dimensions, is shownto be uniformly convergent with respect to the diffusion problems.This method, which can immediately be generalized to higherdimensions, is shown to be uniformly convergent with respectto the diffusion parameter.