Synthesis, characterization and thermal behaviour of solid 2-methoxycinnamylidenepyruvate of some bivalent metal ions in CO2 and N2 atmospheres

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

Sorption and preconcentration of metal ions on silica gel modified with 2,5-dimercapto-1,3,4-thiadiazole

Silica gel, chemically modified with 2,5-dimercapto-1,3,4-thiadiazole [=Si(CH2)(3)-NC2HNS3], abbreviated as SiB, was used to adsorb metal ions from ethanol by both batch and column techniques. Elution of Cu(II) was done with a solvent mixture of acetone and hydrochloric acid (9:1 v/v). Zn(II), Cd(II), Ni(II), Pb(II), Co(II) and Fe(III) were eluted with 0.5 mol l(-1) HC1 in ethanol solution. The modified silica was applied in the preconcentration of metal ions from commercial ethanol, normally used as engine fuel. The method is suitable for quantifying these metals at low mu g l(-1) levels.

The use of silica-immobilized brown alga (Pilayella littoralis) for metal preconcentration and determination by inductively coupled plasma optical emission spectrometry

The brown alga Pilayella littoralis was used as a new biosorbent in an on-line metal preconcentration procedure in a flow-injection system. Al, Co, Cu and Fe were determined in lake water samples by inductively coupled plasma optical emission spectrometry (ICP-OES) after preconcentration in a silica-immobilized alga column. Like other algae, P. littoralis exhibited strong affinity for these metals proving to be an effective accumulation medium. Metals were bound at pH 5.5 and were displaced at pH < 2 with diluted HCl. The enrichment factors for Cu-II, Fe-III, Al-III and Co-II were 13, 7, 16 and 11, respectively. Metal sorption efficiency ranged from 86 to 90%. The method accuracy was assessed by using drinking water certified reference material and graphite furnace atomic absorption spectrometry (GFAAS) as a comparison technique. The column procedure allowed a less time consuming, easy regeneration of the biomaterial and rigidity of the alga provided by its immobilization on silica gel. (C) 2003 Elsevier B.V. All rights reserved.

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 and spectroscopic data to investigate the oxamic acid, sodium oxamate and its compounds with some bivalent transition metal ions

Synthesis, characterization, and thermal behavior of transition metal oxamates, M(NH(2)C(2)O(3))(2)center dot nH(2)O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as the thermal behavior of oxamic acid and its sodium salt (NaNH(2)C(2)O(3)) were investigated employing simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), experimental and theoretical infrared spectroscopy, TG-DSC coupled to FTIR, elemental analysis and complexometry. The results led to information about the composition, dehydration, thermal stability, thermal decomposition, as well as of the gaseous products evolved during the thermal decomposition of these compounds in dynamic air and N(2) atmospheres.

Thermal behaviour of succinic acid, sodium succinate and its compounds with some bivalent transition metal ions

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

Thermal behaviour of mandelic acid, sodium mandelate and its compounds with some bivalent transition metal ions

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

Spectrophotometric study of binary and ternary systems involving metal ions and benzylidenepyruvates: Equilibria in aqueous solutions

The protonation of 4-dimethylaminobenzylidenepyruvate (DMBP) and 2-chloro-4-dimethylaminobenzylidenepyruvate (2-CI-DMBP) and their complex formation with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II) and Al(III) have been studied by potentiometric and spectrophotometric methods at 25 °C and ionic strength 0.500 M, held with sodium perchlorate. The stability order found for 1 :1 complexes of both ligands is Al(III) > Cu(II) > Pb(II) > Ni(II) > Zn(II) > Co(II) > Cd(II) > Mn(II). The stability changes move in the same direction as the pKa of the ligands. The results are compared with literature values reported for metal ion pyruvate systems. Thermodynamic stabilities of ternary complexes formed in Cu(II)-B-L- systems, where B = 2,2′-bipyridyl (bipy), ethylenediamine or glycinate and L = DMBP or 2-CI-DMBP, were also determined. The Cu(bipy)L+ species are more stable than would be expected on purely statistical grounds. The importance of the :t system associated with bipy on the enhanced stability of its mixed ligand complexes is stressed. Analytical applications of the investigated ligands are outlined.

A thermal analysis study of some transition-metal dithizonates

Solid dithizonates of Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II), have been prepared. Thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and elemental analysis have been used to characterize and study the thermal stability and thermal decomposition of these compounds.

Determination of metal ions in fuel ethanol after preconcentration on 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel

This work describes the synthesis and characterization of 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel (SiATT), and the results of a study of the adsorption and preconcentration (in batch, and in flow using a column technique) of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) in ethanol medium. The adsorption capacities for each metal ion were (in mmol g -1): Cd(II) = 0.11, Co(II) = 0.10, Cu(II) = 0.20, Fe(III) = 0.20, Ni(II) = 0.16, Pb(II) = 0.08 and Zn(II) = 0.12. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of SiATT, using 5 mL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a preconcentration method and quantification by Flame AAS of metal ions at trace level in fuel ethanol.

Exploratory study on sequestration of some essential metals by indigo carmine food dye

Indigo carmine forms a stable complex with different ions, and the stability constant of the complexes were evaluated as log K equal to 5.75; 5.00; 4.89 and 3.89 for complexes with Cu(II), Ni(II), Co(II) and Zn(II) ions, respectively, in 0.1 mol L -1 carbonate buffer solution at pH 10. The interaction between Cu(II) ions and indigo carmine (IC) in alkaline medium resulted in the formation of the Cu 2(IC) complex, measured by the spectrophotometric method, with a stoichiometric ratio between indigo carmine and metal ions of 2:1 (metal-ligand). The reported method has also been successfully tested for determination of copper in pharmaceutical compounds based on copper-gluconate without pre-treatment.

Synthesis, characterization and thermal study of solid mandelate of some bivalent transition metal ions in CO2 and N2 atmospheres

Solid state M-L, where M stands for bivalent transition metals (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) and L is mandelate, were synthesized. Simultaneous thermogravimetry and differential scanning calorimetry, elemental analysis and complexometry were used to establish the stoichiometry and to study the thermal behaviour of these compounds in CO2 and N2 atmospheres. The results show that all the compounds were obtained in the anhydrous state and in agreement with the general formula ML2. The thermal decomposition of the compounds occurs in a single (Cu(II)), two (Ni(II)) three (Fe(II), Co(II)), four (Mn(II)) and five (Zn(II)) steps. The results also provided information concerning the ligand's denticity, thermal behaviour, final residues and identification of gaseous products evolved during the thermal decomposition of these compounds. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and 13C and 29Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmolg -1) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. © 2012 Elsevier Inc.

Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution, and none dealt with ATD and Mo (II) complexes. The new Mo-silsesquioxane organometallic nanomaterial was tested as precursor in the epoxidation of cyclooctene and styrene. © 2012 Elsevier B.V.

Thermal behaviour of α-hydroxyisobutyric acid, sodium α-hydroxyisobutyrate and its compounds with some bivalent transition metal ions

Synthesis, characterization and thermal decomposition of bivalent transition metal α-hydroxyisobutyrates, M(C4H7O 3)2·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as the thermal behaviour of α-hydroxyisobutyric acid and its sodium salt were investigated employing simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), infrared spectroscopy (FTIR), TG-DSC coupled to FTIR, elemental analysis and complexometry. All the compounds were obtained as dihydrated, except the copper one which was obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occurs in a single or two steps and the final residue up to 235 C (Mn), 300 C (Fe), 305 C (Co), 490 C (Ni), 260 C (Cu) and 430 C (Zn) is Mn2O3, Fe2O3, Co3O 4, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity and identification of the gaseous products evolved during the thermal decomposition of these compounds. Copyright © 2013 Published by Elsevier B.V. All rights reserved.