Kaline S. Sousa

Ethylenesulfide as a useful agent for incorporation into the biopolymer chitosan in a solvent-free reaction for use in cation removal.

Chitosan (Ch) was chemically modified with ethylenesulfide (Es) under solvent-free conditions to give (ChEs), displaying a high content of thiol groups due to opening of the three member cyclic reagent. Elemental analysis showed a decrease in nitrogen content. This result indicated the incorporation of two ethylenesulfide molecules for each unit of the polymeric structure of the precursor biopolymer. Infrared spectroscopy, thermogravimetry, and (13)C NMR in the solid state demonstrated the effectiveness of the reaction, with signals at 30 ppm for ChEs due to the change in the methylene group environment. Divalent metal uptake by chemically modified biopolymer gave the order Cu>Ni>Co>Zn, reflecting the corresponding acidity of these cations in bonding to the sulfur and the basic nitrogen atoms available on the pendant chains. The equilibrium data were fitted to Freundlich, Temkin, and Langmuir models. The maximum monolayer adsorption capacity for the cations was found to be 1.54+/-0.02, 1.25+/-0.03, 1.13+/-0.01, and 0.83+/-0.03 mmol g(-1), respectively. The Langmuir model best explained the cation-sulfur bond interactions at the solid-liquid interface. The thermodynamics for these interactions gave exothermic enthalpic values of -43.02+/-0.03, -28.72+/-0.02, -26.27+/-0.04, and -17.32+/-0.02 kJ mol(-1), respectively. The spontaneity of the systems is given by negative Gibbs free energies of -31.2+/-0.1, -32.7+/-0.1, -31.7+/-0.1, and -32.2+/-0.1 kJ mol(-1), respectively, in spite of the unfavorable negative entropic values of -39+/-1, -13+/-1, -18+/-1, and -49+/-1 J K(-1)mol(-1) due to solvent ordering in the course of complexation. This newly synthesized biopolymer is presented as a chemically useful material for cation removal from aqueous solution.

Immobilization of ethylene sulfide in aminated cellulose for removal of the divalent cations

Cellulose (Cel) was first chemically modified with thionyl chloride to increase its reactivity. In the next step CelCl was reacted with ethylenediamine (CelEn) and subsequently reacted with ethylene sulfide to obtain a solid substance, CelEnEs. The modification reactions were confirmed by elemental analysis, TG, XRD, (13)C NMR and FTIR. The chemically modified biopolymer CelEnEs had an order of divalent metal sorption of Pb(2+)>Cd(2+)>Ni(2+)>Co(2+)>Cu(2+)>Zn(2+), and the maximum adsorption capacities were found to be 6.282±0.023, 5.783±0.015, 5.561±0.017, 4.694±0.013, 1.944±0.062 and 1.733±0.020 mmol g(-1), respectively. The equilibrium data were fitted to Langmuir, Freundlich and Temkin models, and in general, the experimental data best fit the Freundlich model. This newly synthesized biopolymer proved to be a chemically useful material for cations removal from aqueous solution.

Brazilian Palygorskite as Adsorbent for Metal Ions from Aqueous Solution—Kinetic and Equilibrium Studies

Natural palygorskite was used as an adsorbent for the removal of copper, cobalt and nickel from an aqueous solution. All assays were performed under controlled conditions to establish the adsorption capacity of the solid. Initially, the clay was characterized by chemical analysis, XRD, infrared spectroscopy and thermogravimetry. Adsorption experiments for the ions in aqueous solution were carried out by a batch method through which the reaction time, initial concentration of cations, temperature and pH of the aqueous solution were systematically varied. First-order, pseudo-second-order and intraparticle diffusion models were used to describe the kinetic data. The results show that the processes were fitted well by the pseudo-second-order model. Moreover, the equilibrium solid–cation systems followed the Langmuir isotherm model. The results indicate that raw palygorskite could be employed as a low-cost material for the removal of heavy metals from aqueous solution.

Quimissorção de cátions divalentes em sílica gel modificada com ácido tioglicólico: a influência do pH e força iônica

A novel type of heavy metal adsorbent was prepared by the covalent grafting of thioglycolic acid molecules on a silica gel surface previsiouly modified with 3-aminopropyltrimethoxysilane. The amount of thioglycolic acid immobilized was 1.03 mmol per gram of silica. This material displayed a chelating moiety containing nitrogen, sulfur, and oxygen basic centers which are potentially capable of extracting from aqueous solutions cations such as Cu(II), Ni(II), Co(II), influenced by pH and ionic strength. This process of extraction was carried out by the batch method when similar chemisorption isotherms were observed for all cations. A modified Langmuir equation describes the experimental data.

Chemical Modification of Chitosan in the Absence of Solvent for Diclofenac Sodium Removal: pH and Kinetics Studies

Chitosan was modified with acetylacetone and ethylenediamine in the absence of solvent. The new biopolymer obtained from the modification was characterized by elemental analysis and NMR 13C and applied in the removal of diclofenac sodium aqueous solution varying the pH and time. Through elemental analysis was possible to verify a decreasing in C/N relation after reaction with acetylacetone and an increasing after modification with ethylenediamine. From NMR analysis was verified the appearance of peaks around 160-210 ppm in both materials due to free carbonyl groups in the first step of the modification, besides the formation of imine bonds. The adsorption tests showed that the highest value occurred at pH 4 and from the results of the kinetic study was found that maximum adsorption occurred within 45 minutes and experimental data adjusted better to linear adjustment, following pseudo second-order model. The results show a material efficient in the removal of emerging pollutants.

Synthesis and characterization of a silylated Brazilian clay mineral surface

Clay mineral containing kaolinite, illite and montmorillonite was organofunctionalized with silylating agents: (3-aminopropyl)triethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane and (3-mercaptopropyl)trimethoxy-silane, to yield three hybrids labelled Clay1, Clay2 and Clay3, respectively. These solids were characterized using elemental analysis, thermogravimetry, X-ray diffractometry, infrared spectroscopy, scanning electron micrograph, and 29Si and 27Al solid state NMR. Immobilized quantities of the organic groups were 0.66 mmol g−1, 0.48 mmol g−1 and 0.88 mmol g−1 for Clayx (x = 1–3), respectively. X-ray diffraction patterns confirmed the immobilization of silanes onto the surface without changes in the textural properties of the clay mineral as noted from the SEM images. Spectroscopic measurements were in agreement with the covalent bonding between the silanes and the hydroxyl groups deposited on the surface. The new hybrids were utilized as adsorbents of cobalt in aqueous solution, with retention values of 0.78 mmol g−1, 1.1 mmol g−1 and 0.70 mmol g−1 for Clayx (x = 1–3), respectively.