Perchlorate

Abstract: The linear quadridentate N2S2 donor ligand 1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1 : 1 copper(II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue. The deep green monohydrate of the perchlorate salt crystallises as the mononuclear aqua-complex, [Cu(bmdhp)(OH2)][ClO4]2, in the monoclinic space group P21/n, with Z= 4, a= 18.459(3), b= 10.362(2), c= 16.365(3)A, and β= 117.14(1)°. The structure was solved and refined by standard Patterson, Fourier, and least-squares techniques to R= 0.047 and R′= 0.075 for 3 343 independent reflections with l > 2σ(l). The compound consists of [Cu(bmdhp)(OH2)]2+ ions and ClO4– counter ions. The co-ordination around copper is intermediate between trigonal bipyramidal and square pyramidal, with Cu–N distances of 1.950(4) and 1.997(4)A, Cu–O(water) 2.225(4)A, and Cu–S 2.328(1) and 2.337(1)A. In the solid state, the perchlorate dihydrate's co-ordination sphere may be a topoisomer of the monohydrate's. A new angular structural parameter, τ, is defined and proposed as an index of trigonality, as a general descriptor of five-co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmdhp)(OH2)]2+ in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether)→ Cu charge-transfer bands by comparison with those of the colourless complex Zn(bmdhp)(OH)(ClO4). E.s.r. and ligand-field spectra show that the copper(II) compounds adopt a tetragonal structure in donor solvents.

Abstract: The Wet Chemistry Laboratory on the Phoenix Mars Lander performed aqueous chemical analyses of martian soil from the polygon-patterned northern plains of the Vastitas Borealis. The solutions contained ~10 mM of dissolved salts with 0.4 to 0.6% perchlorate (ClO 4 ) by mass leached from each sample. The remaining anions included small concentrations of chloride, bicarbonate, and possibly sulfate. Cations were dominated by Mg 2+ and Na + , with small contributions from K + and Ca 2+ . A moderately alkaline pH of 7.7 ± 0.5 was measured, consistent with a carbonate-buffered solution. Samples analyzed from the surface and the excavated boundary of the ~5-centimeter-deep ice table showed no significant difference in soluble chemistry.

Abstract: The novel Lewis acids (CH3)3SiOSO2CF3 (3), (CH3)5SiOSO2C4F9 (6), and (CH3)3SiClO4 (4) are highly selective and efficient Friedel-Crafts catalysts for nucleoside formation form silylated heterocycles and peracylated sugars as well as for rearrangements of persilylated protected nucleosides. With basic silylated heterocycles these new catalysts give much higher yields of the natural N-1-nucleosides than with SnCl4.

Abstract: The methods of preparation of ferric hydrous oxide sots consisting of particles, uniform in shape, of narrow size distribution are described in detail. To produce such sots, acidic solutions, containing ferric ions and nitrate, perchlorate, or chloride ions, respectively, were aged at elevated temperatures for times ranging from a few hours to a few weeks. Solids formed from the solutions containing chloride consisted of either β-FeOOH or α-Fe2O3 depending on the concentration of ferric and chloride ions, whereas particles generated in solutions containing nitrate or perchlorate ions consisted of α-Fe2O3. Particle shape varied greatly as the conditions of colloid preparation were altered. It was possible to produce systems consisting of cubic, ellipsoidal, pyramidal, rodlike, and spherical particles. Such dispersions differed greatly in color. Complete domains are given in terms of ferric salt and corresponding acid concentrations which delineate regions of particle formation of given chemical composition and shape. Electrokinetic measurements show relatively small difference in point of zero charge for the various sots studied.

Abstract: Since the discovery of perchlorate in the ground and surface waters of several western states, there has been increasing interest in the health effects resulting from chronic exposure to low (parts per billion [ppb]) levels. With this concern has come a need to investigate technologies that might be used to remediate contaminated sites or to treat contaminated water to make it safe for drinking. Possible technologies include physical separation (precipitation, anion exchange, reverse osmosis, and electrodialysis), chemical and electrochemical reduction, and biological or biochemical reduction. A fairly unique combination of chemical and physical properties of perchlorate poses challenges to its analysis and reduction in the environment or in drinking water. The implications of these properties are discussed in terms of remediative or treatment strategies. Recent developments are also covered.