0000000000222361
AUTHOR
Jean Rouquerol
Confinement in micropores and enthalpies of physisorption
Abstract The use of quasi-equilibrium volumetry associated with isothermal microcalorimetry at 77 K allows direct measurement of the interactions on adsorption of simple probe molecules within well crystallised aluminophosphate and zeolite molecular sieves. Four particular cases are presented which show: the effect of varying micropore diameter, the effect of adsorbing molecules with a favourable geometric compatibility with a given micropore system, the effect of varying the field potential within a given micropore system and finally, the effect of variable selective blocking of the micropore system.
A microcalorimetric study of the different states of argon and nitrogen adsorbed AT 77 K on silicalite-I and ZSM-5
The adsorption of argon and nitrogen on a series of MFI-type zeolites (silicalite-I (Si/Al>1000) and HZSM-5 (16<Si/Al<120)) was studied by isothermal microcalorimetry, volumetry and neutron diffraction.
Investigation on the Adsorption of N2 Ar, CO and CH4 on Aluminophosphates
Abstract Adsorption isotherms at different temperatures and isothermal micro-calorimetric curves were measured for N2 Ar, CO, and CH4 on various molecular sieves as VPI-5, MCM-9, AlPO4-8, AlPO4-H, AlPO4-5, SAPO-5, AlPO4-39, AlPO4-C. It was shown that the isosteric heats of adsorption correlated with the pore-sizes of the studied molecular sieves.
High Resolution Sorption Studies of Argon and Nitrogen on Large Crystals of Aluminophosphate AlPO4-5 AND ZEOLITE ZSM-5
High resolution adsorption (HRADS) with argon and nitrogen at 77 K in the pressure range of 10−6 < p/p° < 0.5 were performed on large crystals of zeolite ZSM-5 (180 μm) and aluminophosphate AlPO4-5 (150 μm) using a novel volumetric device. Multi-step isotherms of both adsorptives on ZSM-5 could be observed for the first time. The adsorption followed by low temperature microcalorimetry resulted in distinct exothermic signals at the steps in the adsorption isotherms. Based on the results of atom-atom potential energy calculations (AAP) as well as independent model building it was shown that 24 ‘kinetic’ adsorbate molecules can be filled into a ZSM-5 unit cell. Experimental results are reasona…
Interactions of lysozyme with hydrophilic and hydrophobic polymethacrylate stationary phases in reversed phase chromatography (RPC)
Two silicas, one with a mean pore diameter of 30 nm and the other non-porous, were coated with polymethacrylates of increasing hydrophobicity in the sequence: poly-2-hydroxyethylmethacrylate (P2HEMA)1 polyethylmethacrylate (PEMA) and poly-n-octylmethacrylate (POMA). Association constants, Kass, between lysozyme and the coated silicas were determined by means of frontal analysis, and the apparent heats of adsorption, delta Happ, by means of microcalorimetry. Using Kass and delta Happ the changes in the apparent free energy, delta Gapp, and in the apparent entropy, delta Sapp, were calculated at a concentration of lysozyme < 10 mumol/l. The association between the lysozyme and the coated sili…
Water Sorption on Mesoporous Aluminosilicate MCM-41
Characterization of the interaction of water with the highly ordered mesoporous solid MCM-41 (pore diameter ∼2.5 nm) is undertaken with the aid of several techniques (adsorption gravimetry, X-ray diffraction, Fourier transform infrared spectroscopy, and controlled rate-evolved gas analysis). The relatively complex water-MCM-41 interactions are characterized by a type V isotherm indicating an initial repulsive character followed by a capillary condensation step of the adsorbate. This highlights both hydrophobic and hydrophilic properties of this potential model mesoporous adsorbent.
Liquid intrusion and alternative methods for the characterization of macroporous materials (IUPAC Technical Report)
This document deals with the characterization of porous materials having pore widths in the macropore range of 50 nm to 500 μm. In recent years, the development of advanced adsorbents and catalysts (e.g., monoliths having hierarchical pore networks) has brought about a renewed interest in macropore structures. Mercury intrusion–extrusion porosimetry is a well-established method, which is at present the most widely used for determining the macropore size distribution. However, because of the reservations raised by the use of mercury, it is now evident that the principles involved in the application of mercury porosimetry require reappraisal and that alternative methods are worth being listed…
A microcalorimetric comparison of the effect ofn-alkane preadsorption on the adsorption of argon and nitrogen on Silicalite-I
Then-alkanes of different lengths were preadsorbed to selectively block part of the micropores of a MFI-type zeolite, Silicalite-I. The porosity available to argon and nitrogen was then studied by quasi-equilibrium adsorption microcalorimetry and volumetry at 77K and compared to what was found for the bare zeolite. Indeed, although partial adsorption ofn-alkanes does not alter the value of the differential enthalpies of adsorption for both argon and nitrogen, then-butane preadsorption diminishes the adsorption capacity by inducing inaccessible volumes in the micropore network. Moreover, the microcalorimetric experiments clearly show thatn-butane is not evenly distributed in the zeolite chan…
Sorption of argon and nitrogen on network types of zeolites and aluminophosphates
Abstract Synthetic zeolites and aluminophosphates comprising 10- and 12- membered ring openings, unidimensional and network type of pore systems (MFI, MEL, ERI, LTA, AEL, AFI and FAU) were used as model adsorbents to examine the impact of micropore structure on the sorption properties. Argon and nitrogen were employed as adsorptives. Adsorption measurements were carried out on gravimetric and volumetric sorption devices and also monitored by microcalorimetry. From the low coverage regime of the isotherm Henry's constants and isosteric heats of adsorption were derived. Both quantities allowed the discrimination between 10- and 12- membered ring systems. Unidimensional 10- and 12- membered ri…