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Stoeckli, Fritz
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Stoeckli, Fritz
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Professeur.e émérite
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fritz.stoeckli@unine.ch
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- PublicationAccès libreOn the determination of surface areas in activated carbons(2005)
; Centeno, Teresa A.The paper examines the validity of two approaches frequently used to determine surface areas in activated carbons, namely the BET method and the use of immersion calorimetry. The study is based on 21 well characterized carbons, whose external and microporous surface areas, Se and Smi, have been determined by a variety of independent techniques. It appears clearly that SBET and the real surface area Smi + Se are in agreement only for carbons with average pore widths Lo around 0.8–1.1 nm. Beyond, SBET increases rapidly and SBET− Se is practically the monolayer equivalent of the micropore volume Wo. This confirms that a characterization of surface properties based on SBET is, a priori, not reliable. The study of the enthalpy of immersion of the carbons into benzene at 293 K, based on Dubinin’s theory, shows that ΔiH consists of three contributions, namely from the interactions with the micropore walls (−0.136 J m−2), the external surface (−0.114 J m−2), and from the volume W*o of liquid found between the surface layers in the micropores (−141 J cm−3). It appears that for carbons where Lo> 1 nm, the real surface area cannot be determined in a reliable way from the enthalpy of immersion and a specific heat of wetting alone. - PublicationMétadonnées seulementModelling of water adsorption by activated carbons: effects of microporous structure and oxygen content(2004)
; Seaton, N AThe present paper examines the adsorption of water by microporous carbons containing various amounts of surface oxygen and a smaller proportion of basic centres. The modelling of water adsorption for 293 and 310 K, using variable pore size distributions (PSD), confirms that the overall type IV isotherm is the sum of a type I isotherm associated with the specific interactions, and a type V isotherm reflecting the non-specific interactions. The principle of temperature invariance is followed by these isotherms, which indicates that modelling leads to the Dubinin-Astakhov equation. The present approach allows the prediction of water adsorption near room temperature, on the basis of the PSD and the density of oxygen present on the surface area of the micropores. It is assumed, to a first and good approximation, that the pores are slit-shaped and the oxygen distribution is random. (C) 2004 Elsevier Ltd. All rights reserved. - PublicationMétadonnées seulementDubinin's theory and its contribution to adsorption science(2001)Dubinin's theory for the volume filling of micropores (TVFM), originally developed for the adsorption of single vapours by microporous solids such as activated carbons and Zeolites, has gradually been extended to other areas. They include immersion calorimetry, the adsorption of water vapour and of mixtures, as well as adsorption front aqueous solutions. Recent studies in the field of adsorption from aqueous solutions, by activated carbons, suggest that the principle of temperature invariance is fulfilled and in the case of phenolic compounds a modified DRK equation can be used to predict the adsorption equilibrium over a certain range of temperatures. Computer modelling of CO2 adsorption by carbons at 273 K leads to micropore distributions, which are in good agreement with those derived from other techniques. It also appears that the model isotherm, in single slit-shaped micropores can be fitted to the Hill-de Boer isotherm, in agreement with mathematical studies of the origin of the Dubinin-Astakhov equation.
- PublicationAccès libreOn the mechanisms of phenol adsorption by carbons(2001)
; Hugi-Cleary, D.The removal of phenol and related compounds from dilute aqueous solutions by activated carbons corresponds to the coating of the micropore walls and of the external surface by a monolayer. This process is described by an analog of the Dubinin—Radushkevich—Kaganer equation. On the other hand, as suggested by immersion calorimetry at 293 K, in the case of concentrated solutions, the mechanism corresponds to the volume filling of the micropores, as observed for the adsorption of phenol from the vapor phase. The equilibrium is described by the Dubinin—Astakhov equation. It follows that the removal of phenol from mixtures with water depends on the relative concentrations, and the limiting factor for adsorption is either the effective surface area of the carbon, or the micropore volume. - PublicationAccès libreEvolution of microporosity during activation of carbon(1991)
; Ballerini, LucaVarious adsorption and immersion techniques and a recent model for micropore distributions have been used to assess quantitatively the evolution of the main properties of active carbon. The precursors used in this study were of vegetable and polymeric origin. One activation series based on natural coal was also included. - PublicationAccès libreThe physical and chemical characterization of a sulphur-impregnated active carbon, by combined adsorption and immersion techniques(1991)