2-Mercaptoimidazole covalently bonded to a silica gel surface for the selective separation of mercury(II) from an aqueous solution

Silica gel with a specific surface area of 365 m(2).g(-1) and an average pore diameter of 60 Angstrom was chemically modified with 2-mercaptoimidazole. The degree of functionalization of the covalently attached molecule, (drop SiO)(3)(CH2)(3) - MI, where MI is the 2-mercaptoimidazole bound to the silica surface by a propyl group, was 0.58 mmolg.(-1). In individual metal adsorption experiments from aqueous solutions by the batch procedure, the affinity order was Hg(II)much greater than Cd-II > Cu-II approximate to Zn-II approximate to Pb-II > Mn-II at solution pHs between 4 and 7. Due to the high affinity by the sulfur atom, Hg-II is strongly bound to the functional groups. When solution containing a mixture of Hg-II, Cd-II, Cu-II, Zn-II, Pb-II, and Mn-II ions was passed through a column packed with the adsorbent, Hg-II was the only one whose adsorption and elution was not affected by the presence of other ions.

Synthesis, characterisation and thermal behaviour of solid state compounds of 4-methylbenzylidenepyruvate with some bivalent metal ions

Solid state M-4-Me-BP compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu, Zn, Pb and 4-Me-BP is 4-methylbenzylidenepyruvate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterise and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Exchange narrowing effects in the EPR linewidth of Gd diluted in Ce compounds

Anomalous thermal behavior on the EPR linewidths of Gd impurities diluted in Cc compounds has been observed. In metals, the local magnetic moment EPR linewidth, Delta H, is expected to increase linearly with the temperature. In contrast, in CexLa1-xOs2 the Gd EPR spectra show a nonlinear increase. In this work, the mechanisms that are responsible for the thermal behavior of the EPR lines in CexLa1-xOs2 are examined. We show that the exchange interaction between the local magnetic moments and the conduction electrons are responsible for the narrowing of the spectra at low temperatures. At high temperatures, the contribution to the linewidth of the exchange interaction between the local magnetic moments and the Ce ions has an exponential dependence on the excitation energy of the intermediate valent ions. A complete fitting of the EPR spectra for powdered samples is obtained, (C) 1998 American Institute of Physics. [S0021-8979(98)39911-9].

INPLANE RESISTIVITY IN GRAPHITE-INTERCALATION COMPOUNDS OBTAINED FROM CONDUCTION-ELECTRON-SPIN-RESONANCE MEASUREMENTS

We developed a procedure to take advantage of the magnetic-field-modulation-frequency effect on the line shape of conduction-electron-spin resonance of graphite intercalation compounds (GIC's) to extract the absolute value of the in-plane resistivity. We calculated the power absorbed in each slice of the sample normal to the wave penetration, multiplied by a factor to account for the magnetic-field-modulation-frequency effect. Room-temperature spectra of stage-I AlCl3-intercalated GIC in both H-0 perpendicular-to c and H-0 parallel-to c configurations were fitted to the theoretical line shapes and the value of in-plane resistivity (and also the value of c-axis resistivity) obtained from the fitting parameters are in reasonable agreement with those from the literature.

THERMAL ANALYSES OF COORDINATION-COMPOUNDS .2. THERMAL-DECOMPOSITION OF PALLADIUM COMPLEXES WITH TRIPHENYLPHOSPHINE, TRIPHENYLARSINE AND TRIPHENYLSTIBINE

The compounds [PdCl(2)L(2)] and [PdL(4)] (L=PPh(3), AsPh(3), SbPh(3)) were studied by thermogravimetric and differential thermal analyses in air. The residues of thermal decomposition consist of metallic palladium, except in the case of the complexes containing SbPh(3), when the residues are palladium and antimony mixtures in appropriate proportions with respect to the stoichiometry of the related complexes.

Cyclometallated compounds of intramolecular coordination.

This article supplies a review on the chemistry of cyclometallated compounds. Emphasis is given to those formed by cyclometallation reactions. In this class of complexes, called organometallic intramolecular-coordination compounds, a special attention is given to the reactivity of cyclometallated of palladium(II) due to their use in important chemical processes. Metal-carbon bonds in these palladium(II) complexes can undergo a large variety of insertion reactions and they offer a potentially important sequence in organic synthetic methodology,homogeneous catalysis and liquid crystals manufacturing.

Small angle X-ray scattering and IR spectroscopy study of metal carbonyl complexes immobilized on a silica gel surface chemically modified with piperazine

The carbonyl complexes [WCl(CO)(3)(bipy) (HgCl)] (1), [Fe(CO)(4)(HgCl)(2)] (2) and W(CO)(6)] (3) were immobilized on a silica gel surface organofunctionalized with piperazine groups. The products obtained were studied by IR spectroscopy and small angle X-ray scattering (SAXS) techniques. The IR data show that the immobilization of heterobimetallic compounds 1 and 2, on the functionalized surface, occurred through the mercury atom, while for 3 the displacement of one CO group by the nitrogen of a piperazine molecule was observed. The data obtained from SAXS indicate that particles have a uniform size and reveal suitable modifications on the functionalized surface after immobilization of metal carbonyl complexes. The average intermolecular distance (l(ij)) for piperazine ligands on support is 8.7 Angstrom, for the metal carbonyl complex 1 it is 18.8 Angstrom, for complex 2 it is 16.2 Angstrom and for complex 3 it is 15.3 Angstrom. Copyright (C) 1996 Elsevier B.V. Ltd

Reduction of mercury(II) by tropical river humic substances (Rio Negro) - Part II. Influence of structural features (molecular size, aromaticity, phenolic groups, organically bound sulfur)

The influence of structural features of tropical river humic substances (HS) on their capability to reduce mercury(II) in aqueous solutions was studied. The HS investigated were conventionally isolated from Rio Negro water-Amazonas State/Brazil by means of the collector XAD 8. In addition, the isolated HS were on-line fractionated by tangential-flow multistage ultrafiltration (nominal molecular-weight cut-offs: 100, 50, 30, 10, 5 kDa) and characterized by potentiometry and UV/VIS spectroscopy. The reduction of Hg(II) ions to elemental Hg by size-fractions of Rio Negro HS was assessed by cold-vapor AAS (CVAAS). UV/VIS spectrometry revealed that the fractions of high molecular-size (F-1 > 100 kDa and F-2: 50-100 kDa) have a higher aromaticity compared to the fractions of small molecular-size (F-5: 5-10 kDa, F-6: < 5 kDa). In contrast, the potentiometric study showed different concentration of functional groups in the studied HS fractions. The reduction of Hg(II) by aquatic HS fractions at pH 5 proceeded in two steps (I, II) of slow first order kinetics (t(1/2) of I: 160 min, t(1/2) of II: 300 min) weakly influenced by the molecular-size, in contrast to the differing degree of Hg(II) reduction (F-5 > F-2 > > F-1 > F-3 > F-4 > > F-6). Accordingly, Hg(II) ions were preferably reduced by HS molecules having a relatively high ratio of phenolic/carboxylic groups and a small concentration of sulfur. From these results a complex 'competition' between reduction and complexation of mercury(II) by aquatic HS occurring in tropical rivers such as the Rio Negro can be suggested. (C) 2003 Elsevier B.V. All rights reserved.

Thermodynamic aspects of ion intercalation in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: Application to the Everit's salt/Prussian Blue transition

The K+ reversible processes for ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K+ ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.

Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion

The low-weight Pd(II) coordination polymers [(N(3))(HL)Pd {Pd(3)(mu-N(3))(mu-L)(5)}10(mu-L)(2)Pd(L)(HL)]{L = Pz(-) (1); mPz(-) (2), IPz(-)(3)} and [(N(3))(HPz)Pd{Pd(6)(mu-N(3))(2)(mu-PZ)(5)(mu-L)(5)}(10)(mu-L)(2)Pd(Pz)(HPz)] {L = mPz(-) (4), dmPz(-) (5); IPz(-) (6)} {L = pyrazolate (Pz(-)), 4-methylpyrazolate(mPz(-)), 4-iodopyrazo late (IPz(-)), 3,5-dimethylpyrazolate (dmPz(-))} have been prepared in this work. IR spectra clearly indicated the exobidentate nature of pyrazolato ligands as well the end-on coordination mode of the azido group. The molecular weight determinations by osmometry indicated that the species have a low degree of polymerization (n = 10). NMR experiments showed two pyrazolate environments in a 2:1 ratio, being assigned to the six-membered ring Pd(mu-L)(2)Pd and the Pd(mu-N(3))(mu-L)Pd metallocycle, respectively. UV-visible spectroscopy gave further evidences for the oligomeric structures of 1-6. Some alternative structures for the isostructural polymers have been suggested. (c) 2005 Elsevier Ltd. All rights reserved.

Compounds of triphenylstibine and platinum: synthesis, properties and reactivity

The reactivity of [Pt(SbPh3)(3)], a compound of zerovalent platinum, exceptionally stable in air, is described. The compounds [{Pt(SbPh3)(3)}(2)N-2], containing bridging dinitrogen, [{Pt(SbPh3)(3)}(2)C-2], with an ethynediyl group also bridging, and [Pt(CO)(2)(SbPh3)(2)], were all obtained under ordinary pressure of nitrogen, acetylene or carbon monoxide, respectively, and are also described. Among the products of the reactions, the dimer [PtBr3(SbPh3)(2)](2) and the mixed complexes [PtL2(SbPh3)(2)] (L = PPh3, AsPh3) were also obtained. Some of these complexes are luminescent when excited by u.v. radiation.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

Thermal behaviour of malonic acid, sodium malonate and its compounds with some bivalent transition metal ions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal behaviour of fumaric acid, sodium fumarate and its compounds with light trivalent lanthanides in air atmosphere

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A Preliminary and Qualitative Metallomics Study of Mercury in the Muscle of Fish from Amazonas, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)