[en] In this volume, the results of studies of uranium sorption (adsorption and desorption) to both single, well-defined mineral phases, and to selected natural (Koongarra) substrates are reported. The single phases included the amorphous iron oxide ferrihydrite, crystalline silica and two naturally occurring kaolinites, KGa-1 and Nichika. The surface properties of these materials were rigorously defined, and adsorption studies were conducted over a range of solution pH, ionic strength, carbonate content, adsorbent and adsorbate concentrations, and in the presence of uranium complexants and (potentially) competing adsorbates (such as phosphate and fluoride). The results of these studies were modelled using the 'surface complexation' approach, with a diffuse layer description of the electrical double layer. The impacts of mineral phase transformations (specifically the aging of amorphous ferrihydrite to more crystalline forms) on the uptake and desorption of uranium are also reported. The amount of data obtained in this study, with a number of experimental parameters being varied over a wide range, has enabled more confidence to be placed in the modelling results. The derived model for ferrihydrite adequately accounts for the effect on U sorption of a number of parameters, most notably pH, pCO₂ and total U present. Few (if any) of the models previously proposed are adequate in this respect. While the modelling of the data for the natural substrates is not as advanced, the U sorption data on the natural substrates show similar features to the U sorption on the model substrates. This suggests that the insights obtained in the modelling of the data for ferrihydrite will be valuable in deriving a model for the more complex natural substrates

[en] Formation constants for NpO₂(CO₃)_i^l2i (i = 1, 2 and 3), NaNpO₂CO_3(s) and Na₃NpO₂(CO₃)_2(s) are deduced from Simakin's et al. (1977), Maya's (1983), and Vitorge's et al. data, who also found evidence for a mixed Np(V)-OH-CO₃ soluble complex. Simakin (1977) found NpO₂(CO₃)₃^-4, it was confirmed by Riglet (1989), and by Offerle, Capdevilla and Vittorge (1995). Temperature influence was studied by Ullman and Schreiner (1988), and by Offerle, Capdevila and Vittorge (1995). Grenthe, Riglet and Vitorge (1986 and 1989) proved the existence of the trinuclear species (NpO₂)₃(CO₃)₆^-6. Maya (1984) mis-interpreted his data; nevertheless they show evidence of a new polynuclear mixed species, certainly (NpO₂)₂(OH)₃CO₃^-1, as initially proposed by Maya. No other Np(V) or Np(VI) soluble complex could be detected, the proposed ones quantitatively account for all published works. Unpublished data allowed to estimate the stability of intermediary mononuclear complexes and NpO₂CO_3(s) solubility product. M₄NpO₂(CO₃)_3(s) (M⁺ = K⁺ or NH₄⁺) ones are deduced from Gorbenko-Germanov and Klimov (1966), and Moskvin (1975) data as respectively interpreted and reinterpreted by this review. Thermodynamic data determined in this report are under discussion within OECD-NEA-TDB. (author)

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[en] Complexes of S-benzyldithiocarbazate (SBDTC) with lighter and heavier metals, viz., Cr(III), Fe(III), Sb(III), Zr(IV), Th(IV), and U(VI) have been prepared and characterized by elemental analyses, conductivity measurements, and spectral studies. The complexes were all prepared in alkaline media with the compositions of [Cr(SBDTCA)₃], [Fe(SBDTCA)₃], [Sb(SBDTCA)₃], [Sb(SBDTCA)₂CI.H₂O], [Zr(O)(SBDTCA)₂.H₂O], [Th(SBDTCA)(NO₃)₃.H₂O)], and [U(O)₂(SBDTCA)₂]. The complexes were all hexa-coordinated with bidentate, uninegative chelation of the ligand. [Fe(SBDTCA)₃], [Sb(SBDTCA)₃] and [Sb(SBDTCA)₂CI.H₂O] were strongly effective against bacteria, Pseudomonas aeruginosa and Bacillus cereus giving clear inhibition zones. The compounds were poor antifungal. (author)

[en] A new route has been developed, leading to the production of phosphorus (III) oxycyanide, OPCN and phosphorus (III) oxycyanate, OPOCN by an on-line process using phosphoryl chloride, POCL sub 3 as a starting material passed over heated silver at 870 Centigrade and then reacted with AgCN and KOCN heated at 270 Centigrade and 590 Centigrade to produce OPCN and OPOCN respectively. The gas phase fourier transform infrared spectra reported for the first time show the two characterized bonds of OPCN and OPOCN at 2165 cm sup - sup 1 and 2130 cm sup - sup 1 , assigned to the C ident to N stretching fundamentals of OPCN and OPOCN respectively. (Author)

[en] The goal of this research is the understanding of elementary chemical and physical processes important in the combustion of fossil fuels. Interest centers on reactions involving short-lived chemical intermediates and their properties. High-resolution high-sensitivity laser absorption methods are augmented by high temperature flow-tube reaction kinetics studies with mass spectrometric sampling. These experiments provide information on the energy levels, structures and reactivity of molecular flee radical species and, in turn, provide new tools for the study of energy flow and chemical bond cleavage in the radicals in chemical systems. The experimental work is supported by theoretical and computational work using time-dependent quantum wave packet calculations that provide insights into energy flow between the vibrational modes of the molecule

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