Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

Structural study of a series of synthetic goethites obtained in aqueous solutions containing cadmium(II) ions

The capacity of goethite for Cd-II substitution has been explored in a series of synthetic samples prepared from Fe-III and Cd-II nitrate solutions aged 21 days in alkaline media. The total metal content ([ Fe] + [ Cd]) was 0.071 M in all preparations. The samples have been characterized by chemical and X-ray diffraction analysis; the morphology of the solids is described. The cell parameters for all samples were obtained by the Rietveld fits to the X-ray diffraction data. Refined structures show that for samples prepared at the final molar ratio mu(Cd)less than or equal to5.50 (expressed as mu(Cd) = 100X[Cd]/[Cd] + [Fe]), a (Cd, Fe)-goethite is the only crystalline product. In these samples, the unit cell parameters increased as a function of Cd concentration, indicating Cd incorporation in the structural frame. At the preparative ratio, mu(Cd)=7.03, the incorporation of Cd in the goethite structure is drastically reduced and a probable Cd-substituted hematite is formed together with the Fe,Cd-goethite. (C) 2003 International Centre for Diffraction Data.

Temperature and concentration dependence of heat capacity of model aqueous solutions

Heat capacities of binary aqueous solutions of different concentrations of sucrose, glucose, fructose, citric acid, malic acid, and inorganic salts were measured with a differential scanning calorimeter in the temperature range from 5degreesC to 65degreesC. Heat capacity increased with increasing water content and increasing temperature. At low concentrations, heat capacity approached that of pure water, with a less pronounced effect of temperature, and similar abnormal behavior of pure water with a minimum around 30degreesC-40degreesC. Literature data, when available agreed relatively well with experimental values. A correction factor, based on the assumption of chemical equilibrium between liquid and gas phase in the Differential Scanning Calorimeter, was proposed to correct for the water evaporation due to temperature rise. Experimental data were fitted to predictive models. Excess molar heat capacity was calculated using the Redlich-Kister equation to represent the deviation from the additive ideal model.

Influence of pH and precipitation temperature on the structural characteristics of aluminium hydroxides prepared form nitrate aqueous solutions

Aluminium Hydroxides were precipitated from Aluminium Nitrate and Ammonium Hydroxide, at the temperatures 64 degrees C (hot) and 25 degrees C (cold), under the pH conditions 5, 7 and 9. The samples were characterized by X-Ray Diffraction (XRD) and Differential Thermal Analysis (DTA). The hydroxide precipitated at pH 9 and 64 degrees C is built up by pseudoboehmite and a minor share of others apparently amorphous hydroxides. The crystallinity of the hot yielded pseudoboehmite diminishes with the pH. The crystallite size was evaluated as about 40 Angstrom for the best crystallized sample. The cold precipitated product is apparently composed by amorphous or very poorly crystallized hydroxides. Upon heating, the cold precipitated hydroxides, and the low pH and hot precipitated hydroxide, release their structural water before the occurrence, about 430 degrees C, of the transition of the pseudoboehmite to gamma-alumina, and exhibit a shifting (towards low temperature side) and a broadening in the peak of the transition to alpha-alumina, which occurs at 1200 degrees C in the pseudoboehmite pattern. The yielded pseudo-boehmite peptized by HNO3, addition and gelified by evaporation in a critical concentration approximately 0.17 gcm(-3).

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.

Adsorption of Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II) from aqueous solutions on a 2-mercaptobenzimidazole-modified silica gel

The chemically modified silica, obtained by reacting 2-mercaptobenz-imidazole with 3-chloropropyl silica gel, was used to adsorb Cu(II), Zn(II), Cd(II) and Pb(II) from aqueous solutions at various pH. Between pH 3-5, the order of selectivity was Hg(II) > Cd(II) ≫ Cu(II) ∼ Zn(II) ∼ Pb(II). Under batch conditions retentions of 100% were achieved for all metals except for Pb(II) where 93% was attained. Under column conditions recoveries of 100% were obtained for all metals. © 1990 Springer-Verlag.

Preconcentration of heavy metals ions from aqueous solutions by means of cellulose phosphate: An application in water analysis

Cellulose phosphate (CELLPHOS) was studied as a collector for analytical preconcentration of traces of Cd(II), Cr(III), Cu(II) and Ni(II) from aqueous sample solution. It has been proved that using chromatographic columns packed with CELLPHOS for preconcentration and 1.0 mol 1 -1 HCl for elution the adsorbed analytes are quantitatively enriched. An enrichment factor of 20 (100 ml sample, 5 ml concentrate) was achieved by this separation procedure, which was applied to a series of water analyses (river, sea, bog water).

Rheological behavior of binary aqueous solutions of poly(ethylene glycol) of 1500 g·mol-1 as affected by temperature and polymer concentration

The rheological behavior of poly(ethylene glycol) of 1500 g·mol -1(PEG1500) aqueous solutions with various polymer concentrations (w = 0.05, 0.10, 0.15, 0.20 and 0.25) was studied at different temperatures (T = 283.15, 288.15, 293.15, 298.15 and 303.15) K. The analyses were carried out considering shear rates ranging from (20 to 350) s-1, using a cone-and-plate rheometer under controlled stress and temperature. Classical rheological models (Newton, Bingham, Power Law, Casson, and Herschel-Bulkley) were tested. The Power Law model was shown suitable to mathematically represent the rheological behavior of these solutions. Well-adjusted empirical models were derived for consistency index variations in function of temperature (Arrhenius-type model; R2 > 0.96), polymer concentration (exponential model; R2 > 0.99) or the combination of both (R 2 > 0.99). Additionally, linear models were used to represent the variations of behavior index in the functions of temperature (R2 > 0.83) and concentration (R2 > 0.87). © 2013 American Chemical Society.

Application of carbon composite adsorbents prepared from coffee waste and clay for the removal of reactive dyes from aqueous solutions

A novel carbon composite was prepared from a mixture of coffee waste and clay with inorganic:organic ratio of 1.3 (CC-1.3). The mixture was pyrolysed at 700 °C. Considering the application of this adsorbent for removal of anionic dyes, the CC-1.3 was treated with a 6 mol L^-1 HCl for 24 h to obtain ACC-1.3. Fourier transform infrared (FTIR), N₂ adsorption/desorption curves, scanning electron microscope (SEM) and powder X-ray diffractometry (XRD) were used for characterisation of CC-1.3 and ACC-1.3 carbon adsorbents. The adsorbents were effectively utilised for removal of reactive blue 19 (RB-19) and reactive violet 5 (RV-5) textile dyes from aqueous solutions. The maximum amounts of RB-19 dye adsorbed at 25 °C are 63.59 (CC-1.3) and 110.6 mg g^-1 (ACC-1.3), and 54.34 (CC-1.3) and 94.32 mg g^-1 (ACC-1.3) for RV-5 dye. Four simulated dye-house effluents were used to test the application of the adsorbents for treatment of effluents.

Density, Refractive Index, Apparent Specific Volume, and Electrical Conductivity of Aqueous Solutions of Poly(ethylene glycol) 1500 at Different Temperatures

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Water activity of aqueous solutions of ethylene oxide-propylene oxide block copolymers and maltodextrins

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

The effect of power-ultrasound on the pretreatment of acidified aqueous solutions of banana flower-stalk: Structural, chemical and statistical analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Association and Structure of Thermosensitive Comblike Block Copolymers in Aqueous Solutions

The structures and association properties of thermosensitive block copolymers of poly(methoxyoligo( ethylene glycol) norbornenyl esters) in D2O were investigated by small angle neutron scattering (SANS). Each block is a comblike polymer with a polynorbornene (PNB) backbone and oligo ethylene glycol (OEG) side chains (one side chain per NB repeat unit). The chemical formula of the block copolymer is (OEG3NB) 79- (OEG6.6NB) 67, where subscripts represent the degree of polymerization (DP) of OEG and NB in each block. The polymer concentration was fixed at 2.0 wt % and the structural changes were investigated over a temperature range between 25 and 68°C. It was found that at room temperature polymers associate to form micelles with a spherical core formed by the block (OEG3NB) 79 and corona formed by the block (OEG6.6NB) 67 and that the shape of the polymer in the corona could be described by the form factor of rigid cylinders. At elevated temperatures, the aggregation number increased and the micelles became more compact. At temperatures around the cloud point temperature (CPT) T ) 60 °C a correlation peak started to appear and became pronounced at 68 °C due to the formation of a partially ordered structure with a correlation length ∼349 Å.