A simulation model of a high-capacity methane adsorptive storage system

A two-dimensional model is developed to describe the hydrodynamics, heat transfer and adsorption phenomena associated with the adsorptive storage of natural gas (NG) in cylindrical reservoirs. Intraparticle and film resistances to both heat and mass transfer are neglected. In the momentum equation, Ergun's law is considered locally valid and is extended to two dimensions. These assumptions are fully justified in the paper. Numerical results are presented concerning the pressurization and blowdown of an ultra-lightweight 50 litre cylinder, commercially available for the storage of compressed NG, if it were filled with an activated carbon having a good adsorptive storage capacity. A simple formula is also proposed to predict the filling times for fast charges. The predicted temperature changes in the packed-bed are in good agreement with those reported in the literature for an experimental charge/discharge.     

Two nickel complexes stabilized by nitrate counter‐ions

Two new nickel nitrates, di­aqua­bis(3,4,7,8‐tetra­methyl‐1,10‐phenanthroline‐κ²N,N′)­nickel(II) dinitrate methanol solvate, [Ni(C₁₆H₁₆N₂)₂(H₂O)₂](NO₃)₂·CH₄O, (I), and tri­aqua­[2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine‐κ³N¹,N²,N⁶]nickel(II) di­ni­trate trihydrate, [Ni(C₁₈H₁₂N₆)(H₂O)₃](NO₃)₂·3H₂O, (II), are reported. In both structures, the cation is octahedrally coordinated, to two bidentate 3,4,7,8‐tetra­methyl‐1,10‐phenanthroline (tmp) and two water mol­ecules in (I), and to one tridentate 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tpt) and three water mol­ecules in (II). Both structures are stabilized by extensive hydrogen‐bonding interactions.     

Reaction of N‐Heterocyclic Silylenes with Thioketone: Formation of Silicon–Sulfur Three (Si‐C‐S)‐ and Five (Si‐C‐C‐C‐S)‐Membered Ring Systems

Three‐ and five‐membered rings that bear the (Si‐C‐S ) and (Si‐C‐C‐C‐S ) unit have been synthesized by the reactions of L SiCl ( 1 ; L =PhC(NtBu)₂) and L′ Si ( 2 ; L′ =CH{(C?CH₂)(CMe)(2,6‐iPr₂C₆H₃N)₂}) with the thioketone 4,4′‐bis(dimethylamino)thiobenzophenone. Treatment of 4,4′‐bis(dimethylamino)thiobenzophenone with L SiCl at room temperature furnished the [1+2]‐cycloaddition product silathiacyclopropane 3 . However, reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si at low temperature afforded a [1+4]‐cycloaddition to yield the five‐membered ring product 4 . Compounds 3 and 4 were characterized by NMR spectroscopy, EIMS, and elemental analysis. The molecular structures of 3 and 4 were unambiguously established by single‐crystal X‐ray structural analysis. The room‐temperature reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si resulted in products 4 and 5 , in which 4 is the dearomatized product and 5 is formed under the 1,3‐migration of a hydrogen atom from the aromatic phenyl ring to the carbon atom of the C? S unit. Furthermore, the optimized structures of probable products were investigated by using DFT calculations.     

Raman and Infrared Spectroscopic Characterization of the Phosphate Mineral Lithiophilite—LiMnPO4

Abstract

The metal lithium is very important in industry, including lithium batteries. An important source of lithium besides continental brines is granitic pegmatites as in Australia. Lithiophilite is a lithium and manganese phosphate with chemical formula LiMnPO₄ and forms a solid solution with triphylite, its Fe analog, and belongs to the triphylite group that includes karenwebberite, natrophilite, and sicklerite. The mineral lithiophilite was characterized by chemical analysis and spectroscopic techniques. The chemical is: Li_1.01(Mn_0.60, Fe_0.41, Mg_0.01, Ca_0.01)(PO₄)_0.99 and corresponds to an intermediate member of the triphylite-lithiophilite series, with predominance of the lithiophilite member. The mineral lithiophilite is readily characterized by Raman and infrared spectroscopy.     

Copper corrosion in buffered and non-buffered synthetic seawater: a comparative study

The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s^–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater.     

The Keto–Enol Tautomerism of Biliverdin in Bacteriophytochrome: Could it Explain the Bathochromic Shift in the Pfr Form?†

Phytochromes are ubiquitous photoreceptors found in plants, eukaryotic algae, bacteria and fungi. Particularly, when bacteriophytochrome is irradiated with light, a Z‐to‐E (photo)isomerization takes place in the biliverdin chromophore as part of the Pr‐to‐Pfr conversion. This photoisomerization is concomitant with a bathochromic shift in the Q‐band. Based on experimental evidence, we studied a possible keto–enol tautomerization of BV, as an alternative reaction channel after its photoisomerization. In this contribution, the noncatalyzed and water‐assisted reaction pathways for the lactam–lactim interconversion through consecutive keto–enol tautomerization of a model BV species were studied deeply. It was found that in the absence of water molecules, the proton transfer reaction is unable to take place at normal conditions, due to large activation energies, and the endothermic formation of lactim derivatives prevents its occurrence. However, when a water molecule assists the process by catalyzing the proton transfer reaction, the activation free energy lowers considerably. The drastic lowering in the activation energy for the keto–enol tautomerism is due to the stabilization of the water moiety through hydrogen bonds along the reaction coordinate. The absorption spectra were computed for all tautomers. It was found that the UV–visible absorption bands are in reasonable agreement with the experimental data. Our results suggest that although the keto–enol equilibrium is likely favoring the lactam tautomer, the equilibrium could eventually be shifted in favor of the lactim, as it has been reported to occur in the dark reversion mechanism of bathy phytochromes.     

Photophysics of aromatic molecules with low-lying pi sigma* states: excitation-energy dependence of fluorescence in jet-cooled aromatic nitriles

Excitation-energy dependence of fluorescence intensity and fluorescence lifetime has been measured for 4-dimethylaminobenzonitrile (DMABN), 4-aminobenzonitrile (ABN), 4-diisopropylaminobenzonitrile (DIABN), and 1-naphthonitrile (NN) in a supersonic free jet. In all cases, the fluorescence yield decreases rather dramatically, whereas the fluorescence lifetime decreases only moderately for S1 (pi pi*, L(b)) excess vibrational energy exceeding about 1000 cm(-1). This is confirmed by comparison of the normalized fluorescence excitation spectrum with the absorption spectrum of the compound in the vapor phase. The result indicates that the strong decrease in the relative fluorescence yield at higher energies is due mostly to a decrease in the radiative decay rate of the emitting state. Comparison of the experimental results with the TDDFT potential energy curves for excited states strongly suggests that the decrease in the radiative decay rate of the aminobenzonitriles at higher energies is due to the crossing of the pi pi* singlet state by the lower-lying pi sigma*(C[triple bond]N) singlet state of very small radiative decay rate. The threshold energy for the fluorescence "break-off" is in good agreement with the computed energy barrier for the pi pi*/pi sigma* crossing. For NN, on the other hand, the observed decrease is in fluorescence yield at higher excitation energies can best be attributed to the crossing of the pi pi* singlet state by the pi sigma* triplet state.