Extraction-chromatographic method for the determination of plutonium-239,240 and plutonium-238 in soils with high natural radioactivity

A highly selective method is described for the determination of ^239,240Pu and ²³⁸Pu in soils by extraction chromatography with Microthene-710/tri-n-octylamine. The method is especially suitable for volcanic soils containing high concentrations of natural alpha radionuclides (Th, Po, U, etc.). The detection limit by α-spectrometry is 2.2 mBq kg^?1 for 50-g soil samples. The average chemical yield, obtained by adding ²⁴²Pu as the internal standard, is 69.5 ± 17.1%. An IAEA reference soil was analyzed, with a relative error of 6.7% for ²³⁹Pu. The concentration of ^2239,240Pu in thirteen analyzed soils and sediments ranged from 26.6 to 429 mBq kg^?1.     

Heptacoordination in MnII,NiII, and CuII complexes of 2,6-diacetylpyridine bis (acetylhydrazone)

Manganese(II), nickel(II), and copper(II) complexes of 2,6-diacetylpyridine bis (acetylhydrazone) (H₂dapac) have been synthesized and structurally characterized by X-ray diffraction methods. [Mn(H₂dapac) (OH₂)₂](NO₃)₂ crystallizes in the monoclinic space groupP2₁/c witha=11.145(3),b=10.723(4),c=17.189(2) Å, =92.81(2)° andZ=4; [Ni(H₂dapac)(OH₂)₂] (NO₃)₂·H₂O crystallizes in the monoclinic space groupP2₁ witha=9.994(3),b=14.423(4),c=7.697(2)Å, =100.37(2)°, andZ=2; [Cu(H₂dapac)(OH₂)₂](NO₃)₂·H₂O crystallizes in the orthorhombic space groupPbcn witha=20.986(5),b=14.552(3),c=6.905(1)Å andZ=4. In each case the metal atom has a slightly distorted pentagonal bipyramidal environment, the equatorial positions being occupied by three nitrogen and two oxygen atoms from the hydrazone ligand and the apices by two water molecules. The crystalline cohesion in ensured by a three-dimensional network of hydrogen bonds involving the complex cations, the nitrate anions, and, where present, the uncoordinate water molecules.     

Shock Layers Interactions for a Relaxation Approximation to Conservation Laws

We consider the interaction between shock waves in a semilinear relaxation approximation to N×N systems of conservation laws. This interaction is described by proving the existence of a particular solution to the relaxing system, with a certain asymptotic as Received July 1998     

Preconcentration and separation of haloacetic acids by ion chromatography

A comparative study was made of the chromatographic behaviour of five haloacetic acids (mono-, dibromoacetic and mono-, di-, trichloroacetic acids). The techniques investigated included reversed-phase ion interaction chromatography with UV detection, suppressed and non-suppressed anion-exchange chromatography. The systems are discussed studying the retention as a function of the mobile phase parameters and the stationary phases used (LiChrospher 100 RP-18, IonPac AS9, AS10 and AS11). A preconcentration step, performed on different substrates, namely LiChrolut-EN and activated vegetal carbon, has been optimized in order to reduce the method detection limits. Results obtained for drinking water samples are shown.     

Orthopalladation of phosphorus ylides in endo position with bidentate ligands

The ortho-metallated complexes [Pd₂{κ²(C,C)-C₆H₄(PPh₂CHC(O)C₆H₅R}₂(μ-Cl)₂] (R = Ph (1a), NO₂ (1b), Br (1c)) were prepared by refluxing equimolar mixtures of Ph₃PCHC(O)C₆H₅R, (R = Ph, NO₂, Br) and Pd(OAc)₂ in MeOH, followed by an excess of NaCl. The dinuclear complexes (1a-1c) react with silver trifluoromethylsulfonate and bidentate ligands [L = bipy (2,2′-bipyridine), phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), dppp (bis(diphenylphosphino)propane)] giving the mononuclear stabilized orthopalladated complexes in endo position [Pd{κ²(C,C)-C₆H₄(PPh₂CHC(O)R}L](OTf) [R = Ph, L = phen (2a), bipy (3a), dppe (4a), dppp (5a); R = NO₂, L = phen (2b), bipy (3b), dppe (4b), dppp (5b); R = Br, L = phen (2c), bipy (3c), dppe (4c), dppp (5c); OTf = trifluoromethylsulfonate anion]. Orthometalation and ylidic C-coordination are demonstrated by an X-ray diffraction study of 2c and 3c. In the structures, the palladium atom shows a slightly distorted square-planar coordination geometry.     

Partial Molar Volumes and Refractions of Cobalt(III) Complexes, Part 2: Homologous Series of Nitrilopentaamminecobalt(III) Complexes

Both the partial molar volumes (V° _2m refractions (R° _2m ) of the solutes at infinite dilution have been determined at 20 °C for a series of six octahedral N₆-coordinated cobalt(III) species featuring five coordinated ammonia ligands along with a sixth N-coordinated organonitrile of increasing ligand size (from acetonitrile to sebaconitrile). The experimental values for V° _2m are consistent with the relative sizes of the ligands but show larger values than those generated by computer modeling as the size of the cation increases, presumably due to the void space of the cation which increases with the size of the nitrile ligand.