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Type: Artigo de evento
Title: Thermochemical Data For N-alkylmonoamine Intercalation Into Crystalline Lamellar Zirconium Phenylphosphonate
Author: Ruiz V.S.O.
Airoldi C.
Abstract: Layered crystalline zirconium phenylphosphonate, Zr(O3PC 6H5)2, changed its interlamellar distance of 1481 pm after intercalation of n-alkylmonoamines, CH3-(CH 2)n-NH2 (n=0-6). The infrared spectra of the precursor host and the corresponding intercalated compounds presented vibrations associated with PO3 groups in the 1163-1039 cm-1 range and additional bands related to C-H stretching bands in the 2950-2850 cm -1 interval were observed after amine insertion. The thermogravimetric curves showed a mass loss assigned to the phenyl group; however, the amine intercalated fraction was not quantitatively determined. A peak in the 31P NMR spectrum centered at -6 ppm for the host was observed. The surface area was 42.0±0.2 m2 g-1 and the scanning electron micrograph gave images consistent with lamellar structural features. The layered compound was calorimetrically titrated with amine in ethanol, requiring three independent operations: (i) titration of matrix with amine, (ii) matrix salvation, and (iii) dilution of the amine solution. From those thermal effects the variation in enthalpy was calculated as: -41±1.00,-33.28±0.50,-34.40±0.80,-10.40±0.40,-12. 40±0.42,-16.10±0.08 and -7.0±0.04 kJ mol-1, for n=0-6, respectively. The exothermic enthalpic values reflected a favorable energetic process of amine-host intercalation in ethanol. The negative Gibbs free energy results supported the spontaneity of all these intercalation reactions. The positive favorable entropic values, as carbon chain size increased, are in agreement with the free solvent molecules in the medium, as the amines are progressively bonded to the crystalline lamellar inorganic matrix at the solid/liquid interface. © 2004 Elsevier B.V. All rights reserved.
Rights: fechado
Identifier DOI: 10.1016/j.tca.2003.10.029
Date Issue: 2004
Appears in Collections:Unicamp - Artigos e Outros Documentos

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