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Silicic acid magadiite as a host for n-alkyldiamine guest molecules and features related to the thermodynamics of intercalation

Published online by Cambridge University Press:  01 January 2024

Thaís R. Macedo ,
Giovanni C. Petrucelli  and
Claudio Airoldi
Thaís R. Macedo
Affiliation:
Instituto de Química,, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, São Paulo, Brazil
Giovanni C. Petrucelli
Affiliation:
Instituto de Química,, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, São Paulo, Brazil
Claudio Airoldi*
Affiliation:
Instituto de Química,, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, São Paulo, Brazil
*
*E-mail address of corresponding author: airoldi@iqm.unicamp.br
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Abstract

Somen-alkyldiamines with thegeneral formulae H2N(CH2)nNH2 (n = 2–5) were intercalated into the layered silicic acid magadiite, from aqueous solution, causing an increase in the original interlayer distance of 1172 pm. The synthetic magadiite and all intercalated compounds were characterized by elemental analysis, infrared vibrational spectroscopy, X-ray diffractometry, 29Si nuclear magnetic resonance in the solid state, thermogravimetry, scanning electron microscopy, surface area and porosity. The intercalation was followed through a batch-wise method at 298±1 K and gave the maximum amounts 3.70, 2.80, 1.75 and 1.18 mmol g−1, for n varying from 2 to 5, respectively. The well characterized magadiite was calorimetrically titrated in a heterogeneous medium, to obtain the thermodynamic data of intercalation at the solid/liquid interface. Linear correlations were obtained for the number of moles intercalated (Nf), th einterlamellar distance (d) and the specific enthalpy (Δinth) values of the interactive process as a function of the number of C atoms of the aliphatic organic chains (nC) for n-alkyldiamine: Nf = (5.36±0.25) − (0.86±0.07)nC, d = (1406.6±1.9) + (20.9±0.5)nC and Δinth = (5.96±0.25) + (0.06±0.01)nC. The basic N guest atom/silanol acidic center interactions inside the host nanospace gallery gave exothermic enthalpies, positive entropies and negative Gibbs free energy values. This set of data suggests the spontaneity of these intercalation reactions.

Keywords

CalorimetryIntercalationMagadiiten-alkyldiaminesSilicic Acid

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 55 , Issue 2 , April 2007 , pp. 151 - 159
Copyright
Copyright © 2007, The Clay Minerals Society

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