The roles of added chlorine and sulfur on ash deposition mechanisms during solid fuel combustion

The focus of this paper is on effects of chlorine and sulfur on coal ash deposition rates, under practically relevant but systematically controlled combustion conditions. This problem is important, not so much for coal, but to understand and predict deposition rates for biomass combustion where chlorine contents can be high. To this end, ash deposition rates on a controlled temperature surface were measured for controlled amounts of chlorine and sulfur added to a pulverized coal, doped with potassium and burned in a 100 kW rated combustion rig. Previous work with 35 tests on 11 coal, biomass and petroleum coke fuels burned under a range of operating conditions had strongly suggested that the deposition rate of the tightly bound inside deposits was independent of the ash aerosol composition, and depended only on PM₁ in the flue gas. The loosely bound outside deposition rate was dependent primarily on the total alkali content in the flue gas. The new results using chlorine added to the fuel (in the form of ammonium chloride) required these previous conclusions to be drastically revised. They showed that chlorine, not alkali alone, had large effects on the deposition rate of the inside deposits, which now were orders of magnitude higher than without chlorine addition, and did not fit previous (multi-fuel) correlations with PM₁. Sulfur addition, together with chlorine, did not affect deposition rates much, although it did lower the chlorine content of the deposit. These results are interpreted in terms of the ash aerosol size segregated composition, which was also measured, and potential sulfation reactions within the deposit.     

Editorial

On behalf of your students your colleagues, and your friends     

Chaos synchronization in networks of coupled maps with time-varying topologies

Complexity of dynamical networks can arise not only from the complexity of the topological structure but also from the time evolution of the topology. In this paper, we study the synchronous motion of coupled maps in time-varying complex networks both analytically and numerically. The temporal variation is rather general and formalized as being driven by a metric dynamical system. Four network models are discussed in detail in which the interconnections between vertices vary through time randomly. These models are: 1) i.i.d. sequences of random graphs with fixed wiring probability, 2) groups of graphs with random switches between the individual graphs, 3) graphs with temporary random failures of nodes, and 4) the meet-for-dinner model where the vertices are randomly grouped. We show that the temporal variation and randomness of the connection topology can enhance synchronizability in many cases; however, there are also instances where they reduce synchronizability. In analytical terms, the Hajnal diameter of the coupling matrix sequence is presented as a measure for the synchronizability of the graph topology. In topological terms, the decisive criterion for synchronization of coupled chaotic maps is that the union of the time-varying graphs contains a spanning tree.     

Search for weakly interacting sub-eV particles with the OSQAR laser-based experiment: results and perspectives

Recent Planck measurements show some CMB anomalies on large angular scales, which confirms the early observations by WMAP. We show that an inflationary model, in which before the slow-roll inflation the Universe is in a superinflationary phase, can generate a large-scale cutoff in the primordial power spectrum, which may account for not only the power suppression on large angular scales, but also a large dipole power asymmetry in the CMB. We discuss an implementation of our model in string theory.     

On the regularity of minimal surfaces with free boundaries in Riemannian manifolds

We show c^1,-regularity of minimal surfaces in Riemannian manifolds with a free boundary on C²-hypersurfaces with bounded second fundamental form and a uniform neighborhood on which the nearest point projection is uniquely defined and differentiable. The decisive step is the proof of continuity at the free boundary.partially supported by SFB 72 (Deutsche Forschungsgemeinschaft)     

Modeling of the submicron particles formation and initial layer ash deposition during high temperature oxy-coal combustion

The future use of coal as a fuel for power generation in the US depends on the availability of financially viable technologies for capture and storage of CO₂ emissions from power plants. Key second-generation candidates for CO₂ capture include high temperature and pressurized oxy-firing of coal, which has the potential to increase efficiency, lower capital costs, avoid air ingress and reduce oxygen requirements. However, unquantified challenges, such as flame behavior, heat transfer, ash transformation, ash deposition and char oxidation, still exist for those technologies. This study specifically focuses on the formation of submicron particles and initial layer ash deposition during high temperature oxy-coal combustion. Previous work has shown that the initial layer deposits are mainly formed of submicron size ash aerosols transported by thermophoresis. Unfortunately, the importance of submicron particle deposition has not received much attention, probably due to the insignificant deposit mass and difficulty in prediction of the submicron particles formation. In this work, models including mineral matter vaporization model, scavenging model and deposition model are developed and applied into a three-dimensional CFD framework to predict the submicron particles formation and subsequent initial layer deposits formation. The model results are comparable to experimental data. The merits of this work are that it has led to the development of a novel approach to predict both submicron particle formation and initial layer ash deposition during oxy-coal combustion.     

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Cyano-modified pre-coated plates — a medium polar modification for high performance thin-layer chromatography

Summary The introduction of a cyano-modified, pre-coated layer substantially widens the selectivity of stationary phases in thin-layer chromatography. This is a moderately polar sorbent based on silica gel 60, which can be used both in adsorption chromatography and in reversed-phase chromatography. This new pre-coated layer is particularly suitable for separation of steroids, alkaloids and derivatized amino acids. The possibility of separating habitforming drugs and preservatives in the presence of ionpair reagents is also discussed.     

Disproportionation of Bromous Acid HOBrO by Direct O-Transfer and via Anhydrides O(BrO)(2) and BrO-BrO(2). An Ab Initio Study of the Mechanism of a Key Step of the Belousov-Zhabotinsky Oscillating Reaction

The results are reported of an ab initio study of the thermochemistry and of the kinetics of the HOBrO disproportionation reaction 2HOBrO (2) ? HOBr (1) + HBrO(3) (3), reaction ( R4' ), in gas phase (MP2(full)/6-311G*) and aqueous solution (SMD(MP2(full)/6-311G*)). The reaction energy of bromous acid disproportionation is discussed in the context of the coupled reaction system R2-R4 of the FKN mechanism of the Belousov-Zhabotinsky reaction and considering the acidities of HBr and HOBrO(2). The structures were determined of ten dimeric aggregates 4 of bromous acid, (HOBrO)(2), of eight mixed aggregates 5 formed between the products of disproportionation, (HOBr)(HOBrO(2)), and of four transition states structures 6 for disproportionation by direct O-transfer. It was found that the condensation of two HOBrO molecules provides facile access to bromous acid anhydride 7, O(BrO)(2). A discussion of the potential energy surface of Br(2)O(3) shows that O(BrO)(2) is prone to isomerization to the mixed anhydride 8, BrO-BrO(2), and to dissociation to 9, BrO, and 10, BrO(2), and their radical pair 11. Hence, three possible paths from O(BrO)(2) to the products of disproportionation, HOBr and HOBrO(2), are discussed: (1) hydrolysis of O(BrO)(2) along a path that differs from its formation, (2) isomerization of O(BrO)(2) to BrO-BrO(2) followed by hydrolysis, and (3) O(BrO)(2) dissociation to BrO and BrO(2) and their reactions with water. The results of the potential energy surface analysis show that the rate-limiting step in the disproportionation of HOBrO consists of the formation of the hydrate 12a of bromous acid anhydride 7 via transition state structure 14a. The computed activation free enthalpy ΔG(act)(SMD) = 13.6 kcal/mol for the process 2·2a → [14a](?) → 12a corresponds to the reaction rate constant k(4) = 667.5 M(-1) s(-1) and is in very good agreement with experimental measurements. The potential energy surface analysis further shows that anhydride 7 is kinetically and thermodynamically unstable with regard to hydrolysis to HOBr and HOBrO(2) via transition state structure 14b. The transition state structure 14b is much more stable than 14a, and, hence, the formation of the "symmetrical anhydride" from bromous acid becomes an irreversible reaction for all practical purposes because 7 will instead be hydrolyzed as a "mixed anhydride" to afford HOBr and HOBrO(2). The mixed anhydride 8, BrO-BrO(2), does not play a significant role in bromous acid disproportionation.     

Acetamidiniumhexafluorometallate von Aluminium,Gallium, Indium,Vanadium, Chrom,Mangan, Eisen und Cobalt

Acetamidiniumhexafluorometallates of Aluminium, Gallium, Indium, Vanadium, Chromium, Manganese, Iron and Cobalt The title compounds were crystallized from F-containing aqueous solutions of their hexafluoro-metallate acids by adding acetamidine. Their unit cells were determined and the thermal decomposition was investigated thermoanalytically. The crystal structure of [CH₃C(NH₂)₂]₃AlF₆ was determined: Space group P4₁2₁2/P4₃2₁2, a = 8,987(1), c = 17,894(3) Å, R = 0,054. The unit cell parameters: .