Rúbia R. Viana

Adsorption of thorium cation on modified clays MTTZ derivative.

Diquite (D) and bentonite (B) mineral samples from the Amazon region, Brazil, were modified by MTTZ derivative (5-mercapto-1-methyltetrazole) using heterogeneous route. These materials were characterized by textural and elemental analysis, transmission electron microscopy (TEM), power X-ray diffraction and (13)C NMR spectroscopy. The chemically modified clay (D(MTTZ) and B(MTTZ)) samples showed modification of its physical-chemical properties including: specific area 41.4 (B) to 398.5m(2)g(-1) (B(MTTZ)) and 25.0 (D) to 178.8m(2)g(-1) (D(MTTZ)). The adsorption experiments performed under batch process with Th(IV) concentration, pH and contact time as variables. The ability of these materials to remove thorium from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 2.0, with variable concentration of Th(IV). The maximum number of moles adsorbed was determined to be 10.45 x 10(-2) and 12.76 x 10(-2)mmol g(-1) for D(MTTZ) and B(MTTZ), respectively. The energetic effects (Delta(int)H degrees , Delta(int)G degrees and Delta(int)S degrees ) caused by thorium cation adsorption were determined through calorimetric titrations.

Amazon kaolinite functionalized with diethylenetriamine moieties for U(VI) removal: thermodynamic of cation-basic interactions.

The compound N-[3-(trimethoxysilyl)propyl]diethylenetriamine (MPDET) was anchored onto Amazon kaolinite surface (KLT) by heterogeneous route. The modified and natural kaolinite clay samples were characterized by transmission electron microscopy (TEM), scanning electron microscopic (SEM), N(2) adsorption, powder X-ray diffraction, thermal analysis, ion exchange capacities, and nuclear magnetic nuclei of (29)Si and (13)C. The well-defined peaks obtained in the (13)C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The adsorption of uranyl on natural (KLT) and modified (KLT(MPDET)) kaolinite clays was investigated as a function of the solution pH, metal concentration, temperature, and ionic strength. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 8.37 x 10(-3) and 13.87 x 10(-3) mmol g(-1) for KLT and KLT(MPDET) at 298 K, respectively. The energetic effects (Delta(int)H, Delta(int)G, and Delta(int)S) caused by metal cations adsorption were determined through calorimetric titrations.

Adsorption of arsenic ions on Brazilian sepiolite: Effect of contact time, pH, concentration, and calorimetric investigation

The original sepiolite clay mineral has been collected from Amazon region, Brazil. The compound 2-aminomethylpyridine (AMP) was anchored onto Amazon sepiolite surface by heterogeneous route. The natural (SPT) and modified (SPT(AMP)) sepiolite samples were characterized by elemental analysis, SEM, N(2) adsorption, and nuclear magnetic nuclei of (29)Si and (13)C. The well-defined peaks obtained in the (13)C NMR spectrum in the 0-160 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove As(V) from aqueous solution was followed by a series of adsorption isotherms at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 7.26×10(-2) and 11.70×10(-2) mmol g(-1) for SPT and SPT(AMP), respectively. In order to evaluate the clay samples as adsorbents in dynamic system, a glass column was fulfilled with clay samples (1.0 g) and it was fed with 2.0×10(-2) mmol dm(-3) As(V) at pH 4.0. The energetic effects caused by metal cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such As(V)-nitrogen interactions.

Adsorption of thorium(IV) on chemically modified Amazon clays

Amostras de caulinita e esmectita oriundas da regiao Amazonica, Brasil, foram modificadas com 2-mercaptobenzimidazol (MBI) usando rotas homogenea e heterogenea. As amostras de argilas modificadas (KHOM, SHOM, KHET e SHET) foram caracterizadas por analise textural, MEV e espectroscopia 13C NMR. As argilas modificadas quimicamente apresentaram modificacoes em suas propriedades fisico-quimicas incluindo: area especifica 48,0 (S) para 869,8 m2 g-1 (SHET). A habilidade destes materiais para remover torio(IV) em solucoes aquosas foi investigada por um serie de isotermas de adsorcao ajustadas pela equacao de Sips em temperatura ambiente e pH 2,0. O numero maximo de mols adsorvidos foi determinado em 8,29, 8,86, 9,57 e 9,89 10-1 mmol g-1 para KHOM, KHET, SHOM e SHET, respectivamente. Os efeitos energeticos causados pela adsorcao do cation torio(IV) foram determinados atraves de metodologia calorimetrica.

Adsorption of methylene blue on raw and MTZ/imogolite hybrid surfaces: Effect of concentration and calorimetric investigation

The synthetic imogolite sample was used for organofunctionalization process with 2-mercaptothiazoline (MTZ). The compound 2-mercaptothiazoline was anchored onto imogolite surface by heterogeneous route. Due to the increment of basic centers attached to the pendant chains the dye adsorption capability of the final chelating material, was found to be higher than is precursor. The ability of these materials to remove methylene blue from aqueous solution was followed by a series of adsorption isotherms at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 40.32×10(-2) and 65.13×10(-2) mmol g(-1) for IMO and IMO(MTZ), respectively. The energetic effects caused by dye cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such methylene blue-nitrogen and sulfur interactions.

Kinetic and thermodynamic uranyl (II) adsorption process into modified Na-Magadiite and Na-Kanemite.

The compound 2-mercaptopyrimidine (MPY) was attached onto synthetic Na-Magadiite (M) and Na-Kanemite (K) samples by homogeneous route. The final matrices named M(MPY) and K(MPY) have been characterized through X-ray powder diffraction and scanning electron microscopy (SEM). The resulted materials were submitted to process of adsorption with uranyl solution at pH 2.0 and 298+/-1K. The kinetic parameters were analyzed by the Lagergren and Elovich models of adsorption and demonstrated to be good fit for all experiments. From calorimetric determinations the quantitative thermal effects for uranyl(II)/basic center interactions gave exothermic enthalpy, negative Gibbs free energy, and positive entropy. These thermodynamic data confirmed the energetically favorable condition of such interactions at the solid/liquid interface for all systems.

Aplicação de Zr/Ti-PILC no processo de adsorção de Cu(II), Co(II) e Ni(II) utilizando modelos físico-químicos de adsorção e termodinâmica do processo

The aim of this investigation is to study how Zr/Ti-PILC adsorbs metals. The physico-chemical proprieties of Zr/Ti-PILC have been optimized with pillarization processes and Cu(II), Ni(II) and Co(II) adsorption from aqueous solution has been carried out, with maximum adsorption values of 8.85, 8.30 and 7.78 x10-1 mmol g-1, respectively. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data with a linear regression process. The energetic effect caused by metal interaction was determined through calorimetric titration at the solid-liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.

Designed pendant chain covalently bonded to analogue of heulandite for removal of divalent toxic metals from aqueous solution: thermodynamic and equilibrium study.

An analogue of heulandite was synthesized by using inorganic salts as a source for silicon and aluminum in the hydrothermal synthesis of the material. The resulting solid was modified by organofunctionalization with 1,4-bis(3-aminopropyl)piperazine and subsequent reaction with methylacrylate in a heterogeneous route. The original (HEU) and modified silicate (HEU(APPMA)) samples were characterized by textural analysis, SEM, and nuclear magnetic nuclei of (29)Si and (13)C. The chemically modified silicate sample showed modification of its physical-chemical properties including specific area 459.0-978.8 m(2) g(-1). The ability of this material to remove nickel(II), cobalt(II), and copper(II) from aqueous solutions was followed by a series of adsorption isotherms adjusted to a Sips equation. The quick adsorption process reached the equilibrium before 10, 15, and 20 min for Cu(II), Ni(II), and Co(II), respectively, with maximum adsorptions at pH 4.0. Based on the capacity of adsorption of HEU(APPMA) to interact with metal ions, the following results were obtained 12.9, 9.8, and 7.5 mmol g(-1) for Cu(II), Ni(II), and Co(II), respectively, reflecting a maximum adsorption order of Cu(II)>Ni(II)>Co(II). The energetic effects caused by metal cation adsorption were determined through calorimetric titrations.

USE OF NATURAL AND MODIFIED MAGADIITE AS ADSORBENTS TO REMOVE Th(IV), U(VI), AND Eu(III) FROM AQUEOUS MEDIA – THERMODYNAMIC AND EQUILIBRIUM STUDY

The contamination of aquatic environments by toxic metals such as radionuclides is of great concern because of the tendency of those metals to accumulate in the vital organs of humans and animals, causing severe health problems. The objective of this study was to investigate the use of natural and modified magadiite clay as an adsorbent to remove Th(IV), U(VI), and Eu(III) from aqueous solutions. Magadiite from the Amazon region, Brazil, was modified chemically with 5-mercapto-1-methyltetrazole (MTTZ) using a multi-step or heterogeneous synthesis pathway. The natural and modified materials were characterized using 29Si and 13C nuclear magnetic resonance, scanning electron microscopy, nitrogen gas adsorption, and elemental analysis. The physical-chemical properties of the chemically modified magadiite sample were modified, e.g. the specific surface area changed from 35.0 to 678.9 m2 g−1. The ability of the magadiite to remove Th(IV), U(VI), and Eu(III) from aqueous solution was then tested by a series of adsorption isotherms adjusted to a Sips equation. The effects of properties such as pH, contact time, and metal concentration on the adsorption capacity were studied. The adsorption maxima were determined to be 7.5 × 10−3, 9.8 × 10−3, and 12.9 × 10−3 mmol g−1 for Th(IV), U(VI), and Eu(III), respectively. From calorimetric determinations, the quantitative thermal effects for all these cations/basic center interactions gave exothermic enthalpy, negative Gibbs free energy, and positive entropy, confirming the energetically favorable conditions of such interactions at the solid/liquid interface for all systems.

Layer silicates modified with 1,4-bis(3-aminopropyl)piperazine for the removal of Th(IV), U(VI) and Eu(III) from aqueous media.

Natural montmorillonite (M) and synthetic kanemite (K) have been functionalized with 1,4-bis(3-aminopropyl)piperazine reacted with methylacrylate to yield new inorganic-organic chelating materials. The original and modified materials were characterized by X-ray diffractometry, textural analysis, SEM and nuclear magnetic nuclei of carbon-13 and silicon-29. The chemically modified clay samples (M-APPMA and K-APPMA) showed modification of its physical-chemical properties including: specific area 45.0m(2)g(-1) (M) to 978.8 m(2)g(-1) (M-APPMA) and 23.5m(2)g(-1) (K) to 898.9 m(2)g(-1) (K-APPMA). The ability of these materials to remove thorium(IV), uranyl(VI) and europium(III) from aqueous solution was followed by a series of adsorption isotherms, which were fitted to non-linear Sips adsorption isotherm model. To achieve the best adsorption conditions the influence of pH and variation of metal concentration were investigated. The energetic effects (Delta(int)H degrees , Delta(int)G degrees and Delta(int)S degrees ) caused by metal ions adsorption were determined through calorimetric titrations.