Fast pyrolysis of coals under N2 and CO2 atmospheres

Oxyfuel combustion represents one way for cleaner energy production using coal as combustible. The comparison between the oxycombustion and the conventional air combustion process starts with the investigation of the pyrolysis step. The aim of this contribution is to evaluate the impact of N₂ (for conventional air combustion) and CO₂ (for oxy-fuel combustion) atmospheres during pyrolysis of three different coals. The experiments are conducted in a drop tube furnace over a wide temperature range 800–1400 °C and for residence time ranging between 0.2 and 1.2 s. Coal devolatilized in N₂ and CO₂ atmospheres at low temperatures (?1200 °C) and longer residence times (>?0.5 s), the char-CO₂ reaction is clearly observed, whose intensity depends on the nature of the coal. Furthermore, the volatile yields are simulated using Kobayashi’s scheme and kinetic parameters are predicted for each coal. The char gasification under CO₂ is also accounted for by the model.

     

Structure and spectroscopy of Tb[Au(CN)2]3.3H2O

The compound Tb[Au(CN)2]3.3H(2)O crystallizes in a layered structure in the hexagonal space group P6(3)/mcm with the 9-coordinate environment of Tb3+ comprising six (CN)- and three OH2 in a tricapped trigonal prism. The shortest Au...Au distance is 3.31 angstroms. The vibrational spectra show that the series Ln[Au(CN)2]3.3H2O (Ln = Y, Pr, Sm, Eu, Tb) are isostructural. The electronic spectra of Eu[Au(CN)2]3.3H2O clearly show that Eu3+ occupies one site of spectroscopic site symmetry D3h, in agreement with the crystallographic data. The electronic emission and absorption spectra of Tb[Au(CN)2]3.3H2O have been recorded at temperatures down to 1.5 K, and the f-f pure electronic transitions are interpreted in detail as arising from the lowest electronic states (in D3h symmetry) (7F6)E' in absorption and (5D4)E' in emission. At low energy, further bands are assigned to the vibronic structure of the CN stretching and water stretching modes, with the latter more predominant. Although the CN stretching vibrations show exclusive infrared or Raman activity in Tb[Au(CN)2]3.3H2O, both of these infrared and Raman active modes are observed in the two-center vibronic transitions. The reasons for this are discussed.     

Continuous fractionation of enantiomer pairs in free solution using an electrophoretic analog of simulated moving bed chromatography

Continuous fractionation of the left and right enantiomers of Piperoxan was performed in free solution in a vortex-stabilized electrophoresis apparatus. Sulfated beta-cyclodextrin was used as the chiral selector. A capillary electrophoresis (CE) study of the separation of Piperoxan enantiomers was carried out in order to find the buffer conditions that produce the maximum peak separation time between the two enantiomers and the optimal chiral selector concentration. These peak separation times were then used to calculate the electrophoretic mobilities of the enantiomer-ligand complexes. The difference in electrophoretic mobilities, when used in a preliminary model of the enantiomer separation, indicated that, by imposing a fluid flow opposite the direction of electromigration, it would be possible to force the fast and slow enantiomers to move in opposite directions within the vortex-stabilized apparatus. Using the predictions of the preliminary separation model, the vortex stabilized electrophoresis apparatus was configured with a feed port at the center of the chamber axis and offtake ports near the cathode and anode. This allowed for continuous operation of the apparatus. Continuous fractionations were completed at throughputs of 1.5 and 4.0 mg/h with both offtakes showing greater than 99% enantiomeric purity at 4.0 mg/h using CE. Fractionation was achieved at a throughput of 10 mg/h, but while the slow enantiomer was recovered with greater than 99% purity, only 96% enantiomeric purity of the fast stereoisomer was achieved. The loss of resolution at higher volumetric throughputs supports our hypothesis that a mobility-dependent "window" of operation exists in which two solutes can be completely separated.     

Quasi-free scattering in the 3-N continuum

The interaction of a nucleon with the deuteron leading to break-up at the quasi-free scattering (QFS) condition is studied atE _N ^lab =12.0, 22.7, 68.0, and 140.0 MeV. Results of rigorous Faddeev calculations and of the impulse approximation (IA) are compared at these energies for bothn-p andp-p QFS in order to study the importance of rescattering terms. For the two-nucleon interaction the Paris potential is used. It is restricted to act in two-body states with total angular momentumj2. Also we compare the Faddeev calculations with experimental data for the QFS cross section and analyzing powerA _y and find overall agreement. The behaviour of scattering observables turns out to be different forn-p andp-p QFS. Also the energy dependence of rescattering terms is different in the two cases. For all energies studied the IA is not reliable.     

Electrochemical precipitation of neptunium with a micro electrochemical quartz crystal microbalance

Journal of Radioanalytical and Nuclear Chemistry - Microliter volumes are used in electrochemical detection and preconcentration of radionuclides to reduce the dose received by researchers and...     

The structure of higher-dimensional Iwasawa modules under a far-fetched assumption

From the assumption that Leopoldt’s conjecture fails and some mild extra assumptions, we deduce the existence of multiple $$\mathbb {Z}_p$$-extensions whose Iwasawa modules are “large” in a precise sense. We are not aware of any constructions of such extensions that avoid our preposterously strong hypothesis.     

Simultaneous Determination of Testosterone and Testosterone Enanthate in Equine Plasma by UHPLC-MS-MS

Testosterone and testosterone enanthate are performance-enhancing substances that are banned in racehorses competing in the State of Pennsylvania (PA). A tolerance concentration of 2,000 pg mL^?1 plasma has been established for testosterone in intact colts and stallions at the time they are competing in PA. Testosterone enanthate is a precursor of testosterone and can be used to boost plasma testosterone concentration above natural, age and seasonally variable plasma concentration. To control abuse, a verifiable method for rapid determination of both substances in equine plasma was needed. For this reason, an ultra high performance liquid chromatography-tandem mass spectrometry method for high-throughput analysis of both analytes in equine plasma was developed. Analytes were recovered from plasma by liquid–liquid extraction using mixture of methyl tert-butyl ether and ethyl acetate (50:50, v/v), separated on a C₁₈ sub-2 μm column and detected on a triple quadrupole mass spectrometer using positive electrospray ionization mode with selected reaction monitoring scan. SRM ion transitions of m/z 289 → m/z 97, m/z 289 → m/z 109, m/z 289 → m/z 79 were used for testosterone identification while m/z 401 → m/z 253, m/z 401 → m/z 271, m/z 401 → m/z 97 were employed for testosterone enanthate. Retention time and product ion intensity ratio were used as confirmation criteria to ascertain the presence of both analytes in equine plasma. The limits of detection, quantification and confirmation were 50 pg 0.5 mL^?1, 100 pg 0.5 mL^?1 and 250 pg 0.5 mL^?1, respectively for both analytes. The method was validated for recovery efficiency, sensitivity, matrix effect, linearity, precision and accuracy. This method is routinely used in the PA program for androgenic anabolic steroids doping control in racehorses and in the on-going testosterone enanthate pharmacokinetics study. The method is defensible, fast, selective, specific and reproducibly reliable.