The chemistry of concentrated sodium aluminate solutions stored in many of the large, underground storage tanks containing high-level waste (HLW) at the Hanford and Savannah River Nuclear Reservations is an area of recent research interest. Not only is the presence of aluminate in solution important for continued safe storage of these wastes, the nature of both solid and solution aluminum oxyhydroxides is important for waste pretreatment. Moreover, for many tanks that have leaked high aluminum waste in the past, little is known about the speciation of Al in the soil. In this study, Raman spectroscopy has been used to investigate the speciation of the aqueous species in the Al2O3-Na2O-H2O system over a wide range of solution compositions and hydration. A ternary phase diagram has been used to correlate the observed changes in the spectra with the composition of the solution and with dimerization of aluminate that occurs at elevated aluminate concentrations (>1.5 M). Dimerization is evidenced by growth of new Al-O stretching bands at 535 and 695 cm(-1) at the expense of the aluminate monomer band at 620 cm(-1). The spectrum of water was strongly influenced by the high concentrations of Na+ and OH- (>17 M). Upon increasing the concentration of NaOH in solution, the delta-(H-O-H) bending band of water (v2 mode) increased in frequency to 1663 cm(-1), indicating that the water contained in the concentrated caustic solution was more strongly hydrogen bonded at the higher base content. In addition, the sharp, well-resolved band at 3610 cm(-1), assigned to the v(O-H) of free OH-, increased in intensity with increasing NaOH. Analysis of the v(O-H) bands in the 3800-2600 cm(-1) region supported the overall increase in hydrogen bonding as evidenced by the increase in relative intensity of a strongly hydrated water band at 3118 cm(-1). Taking into consideration the activity of water, the molar concentrations of the monomeric and dimeric aluminate species were estimated using the relative intensities of the Al-O stretching bands from the Raman spectra. A constant apparent log Kdimer value was obtained at aluminate concentrations >1.5 M with a value of 0.97+/-0.04 at approximately 25 degrees C. This study represents the first spectral-based estimation of a thermodynamic equilibrium constant for the Al2O3-Na2O-H2O system.
The bent d(0) titanium metallocene (Cp)(2)Ti(NCS)(2) exhibits an intense phosphorescence from a ligand-to-metal charge transfer triplet excited state at 77 K in an organic glass substrate and a poly(methyl methacrylate) plastic substrate. Quantum chemical calculations and spectroscopic studies show that the orbital parentage of this triplet state arises from the promotion of an electron from an essentially nonbonding symmetry adapted pi molecular orbital located on the NCS(-) ligands to a d(z)2-(y)2 orbital located on the Ti metal. Standard infrared spectroscopy of (Cp)(2)Ti(NCS)(2) in its ground electronic state at 77 K reveals a pair of closely spaced absorptions at (2072 cm(-1), 2038 cm(-1))(glass) and (2055 cm(-1), 2015 cm(-1))(plastic) that are assigned, respectively, to the symmetric and antisymmetric CN stretching modes of the two coordinated NCS(-) ligands. Low-temperature (77 K) time-resolved infrared spectroscopy that accesses the phosphorescing triplet excited state on the ns time scale shows an IR bleach that is coincident with the two ground state CN stretching bands and an associated grow-in of a pair of new IR bands at slightly lower energies (2059 cm(-1), 2013 cm(-1))(glass) and (2049 cm(-1), 1996 cm(-1))(plastic) that are assigned, respectively, to the symmetric and antisymmetric CN stretches in the emitting triplet state. These transient IR bands decay with virtually identical lifetimes to those observed for the phosphorescence decays when measured under identical experimental conditions. Singular value decomposition analysis of the time-resolved infrared data shows that the observed transient IR features arise from the same electronic manifold as measured through luminescence studies. The close similarity between the ground state and excited-state CN stretching bands in (Cp)(2)Ti(NCS)(2) indicates that symmetry breaking does not occur in forming the charge-transfer triplet excited-state manifold; i.e., electron density is withdrawn from a delocalized pi MO spread across both NCS(-) ligands. Calculations at several levels of theory reveal a delocalized ligand-to-metal charge transfer excited triplet manifold. These calculations closely reproduce the relative intensity ratios and frequencies of the symmetric and antisymmetric transient infrared vibrations in the CN region. This study is the first time-resolved infrared investigation of a ligand-to-metal charge-transfer excited state and the first to be performed at cryogenic temperatures in thin-film organic glass and plastic substrates.
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