RESUMO
Thioglycolic acid was immobilized onto silica gel surface using 3-aminopropyltrimethoxysilane as precursor silylating agent to yield silica. The amount of thioglycolic acid immobilized was 1.03 mmol per gram of silica. This new surface displayed a chelating moiety containing nitrogen, sulfur, and oxygen basic centers which are potentially capable of extracting cations from ethanolic solution, such as MCl3 ( M=Fe, Cr, and Mo). This process of extraction was carried out by the batch method when similar chemisorption isotherms were observed for all cations. The data were adjusted to a modified Langmuir equation. The sequence of the maximum retention capacity was Cr(III) > Mo(III) > Fe(III). The same adsorption was determined by calorimetric titration and the enthalpic values of -35.75 +/- 0.02, 32.90 +/- 0.15, and -84.08 +/- 0.12 kJmol(-1) for chromium, molybdenum, and iron, respectively, were obtained. From the calculated Gibbs free energy -23.4 +/- 0.2, -27.2 +/- 0.2, and -32.7 +/- 0.3 kJmol(-1), the variations in entropy obtained were 42 +/- 1, 201 +/- 1, 172 +/- 1 JK(-1)mol(-1) for the same sequence. All thermodynamic values are in agreement with the spontaneity of the proposed cation-basic center interactions for these chelating processes.
Assuntos
Etanol/química , Dióxido de Silício/química , Tioglicolatos/química , Adsorção , Calorimetria , Quelantes/farmacologia , Cromo/química , Entropia , Géis , Ferro/química , Espectroscopia de Ressonância Magnética , Modelos Químicos , Molibdênio/química , Temperatura , TermodinâmicaRESUMO
Silica gel surface has been modified in two reaction steps: (i) the silylating agent 3-mercaptopropyltrimetoxysilane was firstly immobilized to give a surface Sil-SH and (ii) this precursor incorporated an ethylene sulfide molecule to obtain the surface denoted Sil-SSH. This material was characterized by elemental analysis, IR spectroscopy, thermogravimetry, solid state 13C and 29Si NMR, and surface area measurement. These materials were employed as adsorbents for divalent heavy cations from aqueous solutions at room temperature and the isotherms were adjusted to a modified Langmuir equation. The maxima number of moles adsorbed were 1.0, 1.5, 1.6, 2.2, 2.4 and 3.3 mmol g(-1) for Co, Cu, Ni, Cd, Pb, and Hg, respectively.