Observation on Symmetry Properties of Sodium Zinc(II)-2,9,16,23-phthalocyanine Tetracarboxylate in Water:NaOH Solution

The shift of the Q-band of sodium zinc(II)-2,9,16,23-phthalocyanine tetracarboxylate (ZnPc(COONa)₄) to about 800 nm is attributed to the influence of the electron-donating property of the carboxylate groups substituted in the β–position. ZnPc(COONa)₄ which was found to have a symmetry of D _2h characterized by a splitting of the Q transition. This splitting was interpreted by the formation of dianionic symmetric ZnPc(COONa)₄ resulting from the dissociation of the pyrrole protons as well as the possibility of Na⁺ dissolution of ZnPc(COONa)₄ in the aqueous solution of NaOH.     

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra

The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.     

Magnetic resonance studies of jets in a gas–solid fluidised bed

Magnetic resonance imaging (MRI) has been used to study the behaviour of jets at the distributor of a 50 mm diameter fluidised bed of 0.5 mm diameter poppy seeds. Two perforated-plate distributors were examined, containing either 10 or 14 holes, each 1 mm diameter. Ultra-fast MR imaging was able to show the transient nature of the upper parts of the jets, where discrete bubbles are formed. Imaging in 3D showed that the central jets were the longest for flow rates below minimum fluidisation. Above minimum fluidisation, the outer jets, nearest the wall of the fluidised bed, arched inward towards the central axis. In this latter case, interpretation of the time-averaged 3D image required the use of ultra-fast MR imaging to identify the approximate height above the distributor at which discrete bubbles were formed. The apparently continuous void extending along the central axis above this height in the time-averaged 3D image was thus identified, using ultra-fast MR imaging, as representing the averaged paths of released bubbles. Time-averaged MR velocity mapping was also used to identify dead zones of stationary particles resting on the distributor between the jets. The dead zones could be observed when the superficial velocity of the gas approached minimum fluidisation, but they were smaller than those observed at lower gas superficial velocity. Comparable images of a single jet through 1.2 mm diameter poppy seeds from MRI and electrical capacitance volume tomography (ECVT) are also demonstrated.