Magnetic, thermal and spectral characterization of 2,4-dimethoxybenzoates of Mn(II), Co(II) and Cu(II)

2,4 - Dimethoxybenzoates of Mn(II), Co(II) and Cu(II) have been synthesized as hydrated or anyhydrous polycrystalline solids and characterized by elemental analysis, IR spectroscopy, magnetic studies and X-ray diffraction measurements. They possess the following colours: Mn(II) - white, Co(II) - pink and Cu(II) - blue. The carboxylate groups bind as monodentate, or a symmetrical bidentate bridging ligands and tridentate. The thermal stabilities were determined in air at 293-1173K. When heated the hydrated complexes dehydrate to from anhydous salts which are decomposed to the oxides of respective metals. The magnetic susceptibilites of the 2,4-dimethoxybenzoates were measured over the range 76-303 K and their magnetic moments were calculated. The results reveal the complexes of Mn(II), Co(II) to be high-spin complexes and that of Cu(II) to form dimer.

The physico-chemical properties of 4-chlorophenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 4-chlorophenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: pink for Co(II), green for Ni(II), blue for Cu(II) and a pale pink for Mn(II) compounds. The carboxylate group binds as monodentate and bidentate ligands. On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals. Their magnetic moments were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

Stability constants and thermodynamic parameters of cadmium complexes with sulfonamides and cephapirin

Stability constant (log beta) and thermodynamic parameters of Cd2+ complexes with sulfonamide and cephapirin were determined by Polarographic technique at pH = 7.30 ± 0.01 and µ = 1.0 M KNO3 at 250°C. The sulfonamides were sulfadiazine, sulfisoxazole, sulfamethaxazole, sulfamethazine, sulfathiazole, sulfacetamide and sulfanilamide used as primary ligands and cephapirin as secondary ligand. Cd2+ formed 1:1:1, 1:2:1 and 1:1:2 complexes. The nature of electrode processes were reversible and diffusion controlled. The stability constants and thermodynamic parameters (deltaG, deltaH and deltaS) were determined. The formation of the metal complexes has been found to be spontaneous, exothermic in nature, and entropically unfavourable at higher temperature.

Comparison of some properties of 2,3 - and 3,4 - dimethoxybenzoates of Cu(II), Co(II) and Nd(III)

The physicochemical properties of 2,4-, and 3,4- dimethoxybenzoates of Cu(II), Co(II) and Nd(III) were studied and compared to observe the -OCH3 substituent positions in benzene ring on the character of complexes. The analysed compounds are crystalline hydrated or anhydrous salts with colours depending on the kind of central ions: blue for Cu(II), pink for Co(II) and violet for Nd(III) complexes. The carboxylate groups bind as monodentate, bidentate bridging or chelating and even tridentate ligands. Their thermal stabilities were studied in air at 293-1173K. When heated the hydrated complexes release the water molecules and form anhydrous compounds which are then decomposed to the oxides of respective metals. Their magnetic moment values were determined in the range of 76-303K. The results reveal the compounds of Nd(III) and Co(II) to be the high-spin and that of Cu(II) forms dimer. The various positions of -OCH3 groups in benzene ring influence some of physicochemical properties of analysed compounds.

Polarographic study and electrode kinetics of [Zn(II) - antibiotics - cephaloglycin] system vis a vis kinetics of electrode reactions

Electrode kinetics and complex formation of Zn(II) using doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin, chloramphenicol and cephaloglycin were reported at pH = 7.30 ± 0.01 in = 1.0 molL-1 NaClO4 used as supporting electrolyte at 25.0°C. Kinetic parameters viz. transfer coefficient (α), degree of irreversibility (λ) and rate constant (k) were determined. The study showed that 'Transition state' behaves between reactant (O) and product (R) response to applied potential. The stability constants varied from 2.14 to 10.31 showing that these drugs or their complexes could be used against Zn toxicity.

Synthesis and magnetic studies of copper(II)-lanthanide(III) 5-bromosalicylideneglycylglycine

The physico-chemical properties of the new 3d-4f heteronuclear complexes with general formula LnCu3(C11H8N2 O4Br)3·13H2O (where Ln = Pr, Eu, Gd, Tb, Er, Yb and H3(C11H8N2 O4Br) - 5-bromosalicylideneglycylglycine) were studied. The compounds were characterized by elemental, spectral and thermal analyses and magnetic measurements. The formation of Schiff base is evidenced by a strong band at ca. 1646-1650 cm-1 attributable to C=N stretching mode. The presence of water molecules is confirmed by broad absorptions with maximum at 3360 - 3368 cm-1. The Cu(II)-Ln(III) complexes are stable up to ca. 318 K. During dehydration process the water molecules are lost probably in two stages. The magnetic susceptibility data for these complexes change with temperature according to the Curie-Weiss law.

Direct and simultaneous spectrophotometric determination of Ni (II) and Co (II) using diethanoldithiocarbamate as complexing agent

A direct spectrophotometric method for simultaneous determination of Co(II) and Ni(II), with diethanoldithiocarbamate (DEDC) as complexing agent, is proposed using the maximum absorption at 360 and 638 nm (Co(II)/DEDC) and 390 nm (Ni/DEDC). Adjusting the best metal/ligand ratio, supporting eletrolite, pH, and time of analysis, linear analytical curves from 1.0 10-6-4.0 10-4 for Co(II) in the presence of Ni 1.0 10-6-1.0 10-4 mol L-1 were observed. No further treatment or calculation processes have been necessary. Recoveries in different mixing ratios were of 99%. Interference of Fe(III), Cu(II), Zn(II) and Cd(II), and anions as NO3-, Cl-, ClO4-, citrate and phosphate has been evaluated. The method was applied to natural waters spiked with the cations.

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Divalent metal complexes of ligand 2-methoxybenzylidenepyruvate with Fe, Co, Ni, Cu and Zn as well as sodium salt were synthesized and investigated in the solid state. TG curves of these compounds were obtained with masses sample of 1 and 5mg under nitrogen atmosphere. Different heating rates were used to characterize and study these compounds from the kinetic point of view. The activation energy and pre-exponential factor were obtained applying the Wall-Flynn-Ozawa method to the TG curves. The obtained data were evaluated and the values of activation energy (Ea / kJ mol-1) was plotted in function of the conversion degree (α). The results show that due to mass sample, different activation energies were obtained. The results are discussed mainly taking into account the linear dependence between the activation energy and the pre exponential factor, where was verified the effect of kinetic compensation (KCE) and possible linear relations between the dehydrations steps of these compounds.

The physico-chemical properties of 2-methoxyphenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 2-methoxyhenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)with the general formula: M(C9H9O4)3·4H2O, where M(II) = Mn, Co, Ni and Cu have been synthesized and characterized by elemental analysis, IR spectroscopy, magnetic and thermogravimetric studies and also X-ray diffraction measurements. The complexes have colours typical for M(II) ions (Mn(II) - a pale pink, Co(II) - pink, Ni(II) - green, and Cu(II) - blue). The carboxylate group binds as monodentate and bidentate ligands. On heating to 1273K in air the complexes decompose in the same way. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals with the intermediate formation of the oxycarbonates. Their solubility in water at 293K is of the order of 10-5 mol·dm-3. The magnetic moments of analysed complexes were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

Thermal behaviour of succinic acid, sodium succinate and its compounds with some bivalent transitions metal ions in dynamic N2 and CO2 atmospheres

Thermal stability and thermal decomposition of succinic acid, sodium succinate and its compounds with Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA) in nitrogen and carbon dioxide atmospheres and TG-FTIR in nitrogen atmosphere. On heating, in both atmospheres the succinic acid melt and evaporate, while for the sodium succinate the thermal decomposition occurs with the formation of sodium carbonate. For the transition metal succinates the final residue up to 1180 ºC in N2 atmosphere was a mixture of metal and metal oxide in no simple stoichiometric relation, except for Zn compound, where the residue was a small quantity of carbonaceous residue. For the CO2 atmosphere the final residue up to 980 ºC was: MnO, Fe3O4, CoO, ZnO and mixtures of Ni, NiO and Cu, Cu2O.

Uso de sílica e sílica-titânia organofuncionalizadas para a remoção de Cu(II) em aguardentes

Devido a necessidade da presença de cobre nos alambiques e as exigências cada vez mais acirradas com relação ao seu teor no destilado, é de interesse o desenvolvimento de metodologias para o controle deste metal nos destilados e/ou a sua remoção até níveis aceitáveis, em conformidade com as legislações nacional e internacional. Este trabalho investigou a potencialidade de dois sólidos: sílica modificada com trimetóxisili(propil)etilenodiamina (Si-Dia), e sílica-titânia, também modificada com trimetóxisili(propil)etilenodiamina (Si-Ti-Dia), como agentes removedores de íons Cu2+. Foram empregadas tanto soluções padrão de Cu2+, com teor alcoólico que simulavam aguardentes, como amostras reais de destilados. Os resultados indicam que um grama das matrizes Si-Dia e Si-Ti-Dia adsorvem 1,39 e 73,5mmol de Cu2+, respectivamente, a partir das soluções padrão, nas seguintes condições: tempo de contato 22h, pH 4,0; temperatura 25 ± 1,0°C e agitação constante. Para amostras reais, sob as mesmas condições de análises, o sólido Si-Dia reduziu as concentrações dos íons divalentes Cu, Zn e Fe em, respectivamente, 82, 83 e 64%, enquanto o Si-Ti-Dia, reduziu os mesmos íons em 88, 31 e 22%, respectivamente.