Studies in Surface Science and Catalysis 62 CHARACTERIZATION OF POROUS SOLIDS II This Page Intentionally Left Blank Studies in Surface Science and Catalysis Advisory Editors: B. Delmon and J.T. Yates Vol. 62 CHARACTERIZATION OF POROUS SOLIDS II Proceedingso f the IUPAC Symposium (COPS 11). Alicante, Spain, May 6- 9,1990 Editors F. Rodriguez-Reinoso Departamento de Quimica lnorgdnica e Ingenieria Quimica, Universidad de Alicante, Apartado 99, Alicante, Spain J. Rouquerol Centre de Thermodynamiquee t de Microcalorimetrie, CNRS, 7 3003 Marseille, France K.S.W. Sing Department of Chemistry, Brunel University, Uxbridge, Middlesex UB8 3PH, U.K . and K.K. Unger lnstitut fur Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universitat,0 -6500M ainz, F. R. G. - - - ELSEVIER Amsterdam Oxford New York Tokyo 1991 ELSEVIER SCIENCE PUBLISHERS B.V. Sara Burgerhahstraat 25 P.O. Box 2 1 1, 1000 AE Amsterdam, The Netherlands Distributors for the United States and Canada: ELSEVIER SCIENCE PUBLISHING COMPANY INC. 655,A venue of the Americas New York, NY 10010.U SA. Library of Congress Cataloging-in-Publication Data IUPAC Symposium. COPS (2nd : 1990 : Alicante. Spain) Characterization of porous solids I1 : proceedings of the IUPAC Symposium, COPS 11. Alicante. Spain. May 6-9. 1990 I editors, F. Rodriguez-Reinoso ... [et al.1. p. cm. -- (Studies in surface science and catalysis ; 62) Includes bibliographical references and indexes. ISBN 0-444-88569-2 1. Porous materials--Congresses. I. Rodrjguez-Reinoso. F., 1941- 11. International Union of PGre and Applied Chemistry. 111. Title. IV. Title. Characterization of porous solids 2. V. Title: Characterization of porous solids two. VI. Series. TA418.9.P6196 1990 620.1'16--d~20 91 - 10354 C1P ISBN 0-444-88569-2 0 Elsevier Science Publishers B.V., 199 1 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science Publishers B.V./ Physical Sciences & EngineeringD ivision, P.O. Box 330, lo00 AH Amsterdam, The Netherlands. Special regulationsf or readers in the USA -This publication has been registered with the Copyright Clearance Center Inc. (CCC), Salem, Massachusetts. Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the USA. All other copyright questions, including photocopying outside of the USA, should be referred to the publisher. No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any meth- ods, products, instructions or ideas contained in the material herein. Although all advertising material is expected to conform to ethical (medical) standards, inclusion in this publication does not constitute a guarantee or endorsement of the quality or value of such product or of the claims made of it by its manufacturer. This book is printed on acid-free paper. Printed in The Netherlands V CONTENTS Preface XI11 Characterization of porous solids: an introductory survey K.S.W. Sing 1 Simulation of adsorption in model microporous graphite D. Nicholson 11 Theory of adsorption in micropores Z. Tan and K.E. Gubbins 21 Sorption of gases on microporous solids: pore size characterization by gas sorption S.W. Webb and W.C.Conner 31 Analysis of the percolation properties of a real porous material G. Mason and D.W. Mellor 41 The five types of porous structures and their hysteresis loops V. Mayagoitia 51 Model study of the combined effect of heteroporosity of macroscopic heterogeneity gas relative permeability of porous solids N.K. Kanellopoulos, J.K. Petrou and J.H. Petropoulos 61 Percolation theory of capillary hysteresis phenomena and its application for characterization of porous solids A.V. Neimark 67 Modelling of mercury intrusion and extrusion M. Day, I.B. Parker, J. Bell, M. Thomas, R. Fletcher and J. Duffie 75 Wetting phenomena in porous solids: Mechanisms and models A. Winter 85 The contact angle of liquids in porous media U. Demlehner 97 The main principles of modelling of porous solids. Models of systems with needle-like particles A.P. Karnaukhov 105 Adsorption-desorption hysteresis in porous networks D.K. Efremov and V.B. Fenelonov 115 VI The determination of the pore size distribution of porous solids using a molecular model to interpret nitrogen adsorption measurements C.A. Jessop, S.M. Riddiford, N.A. Seaton, J.P.R.B. Walton and N. Quirke 123 Standardisation, reference materials and comparative measurements for surface area and pore characterisation E. Robens and K.-F. Krebs 133 Fractal characterization of the porosity of organic tissue by interferometry M. Sernetz, H.R. Bittner, P. Bach and B. Glittenberg 141 Determination of surface properties of porous solids K.S. Birdi, D.T. Vu, S.I. Andersen, A. Winter, H. Topsrae and S.V. Christensen 151 A new apparatus for continuous adsorption. Application to the characterization of microporous solids H. Ajot, J.F. Joly, F. Raatz and C. Russmann 161 A new mercury intrusion-retraction simulator used as a means for the characterization of porous materials C.D. Tsakiroglou and A.C. Payatakes 169 Film surface area measurements for microporosity and surface roughness analysis G.P. Johnston, D.M. Smith, A.J. Hurd and P. Pfeifer 179 Some problems about gas adsorption isotherm measurements by automated procedures in manometric devices J.L. Ginoux and L. Bonnetain 189 Morphological influences on unsteady gas diffusivities in porous solids W. C. Conner, S.W. Webb, P. Buckley, S.V. Christiansen, G. Parthun, J.A. Hansen and H. Topsrae 199 Textural characterization of ultrafiltration membranes by thermoporometry and liquid flow measurement J.F. Quinson, N. Nameri and B. Bariou 209 Characterization of the surface fractal dimension of evaporated silver and gold films through adsorption isotherm measurements J. Krim and V. Panella 217 Influence of pore structure parameters on the intraparticle pressure change during adsorption S.E. Scholl and A.B. Mersmann 225 VII Neutron scattering investigation of adsorption processes in model porous systems J.D.F. Ramsay and R.G. Avery 235 Small angle and ultra-small angle scattering techniques for characterization of porous materials J.C. Dore and A.N. North 245 Gel-precipitated oxide gels with controlled porosity-determination of structure by small angle neutron scattering and adsorption isotherm measurements J.D.F. Ramsay, P.J. Russell and S.W. Swanton 257 Small-angle neutron scattering study of fumed silica powder compaction A.J. Hurd, G.P. Johnston and D.M. Smith 267 The determination of permeability and binary gas diffusion coefficients in novel forms of porous carbons S.B. Bhowmik, S.P. Waldram, R. McMurray and S.R. Tennison 273 Pore-size analysis for permeability estimation in porous material T. Sat0 283 The effects of pore and particle geometry on NMR diffusion measurements in adsorbed liquids S. Bahceli, A.R.S. Al-Kaisi, K. Krynicki and J.H. Strange 293 Pore size analysis of wet materials via low-field NMR D.M. Smith and P.J. Davis 30 1 Characterization of microporosity and surface homogeneity by the study of argon and nitrogen isotherm crossing and measurement of differential enthalpies of adsorption J.M. Martin-Martinez, F. Rodriguez-Reinoso, Y. Grillet, F. Rouquerol and J. Rouquerol 311 Adsorptive properties of activated carbons prepared from kevlar J.J. Freeman, F.G.R. Gimblett, R.A. Hayes, Z. Mohd. Amin and K.S.W. Sing 319 Modification in porous texture and oxygen surface groups of activated carbons by oxidation M. Molina-Sabio, M.A. Muiiecas-Vidal and F. Rodriguez-Reinoso 329 Adsorption of methanol and water by charcoal cloth A.M. Gonplves da Silva, M.M.L. Ribeiro Carrott, P.J.M. Carrott and M.M. Brotas de Carvalho 341 VIII Influence of coal preoxidation and reactive gas flow rate on textural properties of active carbons J.A. Pajares, J.J. Pis, A.B. Fuertes, A.J. PCrez, M. Mahamud and J.B. Parra 347 Evaluation of microporosity in steam activated brown coal humic acids chars T. Siemieniewska, K. Tomkow, J. Kaczmarczyk, A. Albiniak, Y. Grillet and M. FranGois 357 Induced porosity in activated carbons by catalytic activation A. Linares-Solano, M. Almela-Alardn, C. Salinas-Martinez de Lecea, M.J. Muii6z-Guillena and M.J. IllPn-G6mez 367 Characterization of activated carbon: an approach to the activation process by SAXS and optical microscopy J.M. Guet, Q. Lin, A. Linares-Solano and C. Salinas- Martinez de Lecea 379 Dynamic micropore structures of micrographitic carbons during adsorption K. Kaneko, T. Suzuki, Y. Fujiwara and K. Nishikawa 389 Characterization of the porosity of activated charcoals by adsorption from solution J. FernPndez-Colinas, R. Denoyel and J. Rouquerol 399 The porosity of textile fibre surfaces A. McInally, R.R. Mather and K.S.W.Sing 409 Further comments on low pressure hysteresis in activated carbons: effect of preparation method F. Rodriguez-Reinoso, J.M. Martin-Martinez, A. Linares-Solano and R. Torregrosa 419 Multi-stage micropore filling of N, and Ar by microporous carbon fibers K. Kakei, S. Ozeki, T. Suzuki and K. Kaneko 429 Porous structure of synthetic active carbons N.T. Kartel, A.M. Puzy and V.V. Strelko 439 Evaluation of microporosity in activated carbons with high ash (Cr20,) content M.A. Martinez-Shchez, J.M. Martin-Martinez, A.C. OrgilCs- Barcel6, F. Rodriguez-Reinoso and M.J. SellCs-PCrez 449 Influence of coal oxidation on coke porosity J.J. Pis, R. MenCndez, J.J. Lorenzana, A.J. PCrez, H. Marsh and E. Romero 459 IX Comparative studies of the microporous structure parameters evaluated from the adsorption isotherms of various adsorbates on activated carbons M. Jaroniec, J. Choma, F. Rodriguez-Reinoso and J.M. Mart in-Mart inez 469 Estimating micropore sizes in activated carbons from adsorption isotherms B. McEnaney and T.J. Mays 477 A comparative study of the porous structure of active carbons using benzene and water adsorption, inmersion calorimetry and liquid chromatography K.H. Radeke and P. Briickner 49 1 Mercury porosimetry of porous glass and active carbon preloaded with n-decane or water H. Lentz and Y. Zhou 499 Sorption of hydrocarbons in silicalite-1 and Nay zeolites J.A. Hampson, R.V. Jasra and L.V.C Rees 509 How can an adsorption system show phase transition. A case study on the adsorption of p-xylene in ZSM-5 D. Pan and A.B. Mersmann 5 19 Crystallochemical structure of zeolite micropores and adsorption- energetic characteristics G.U. Rakhmatkariev, A.A. Isirikjan 525 Sorption of argon and nitrogen on network types of zeolites and aluminophosphates H. Reichert, U. Muller, K.K. Unger, Y. Grillet, F. Rouquerol, J. Rouquerol and J.P. Coulomb 535 Porosity of silicas: comparison of nitrogen adsorption and mercury penetration D.R. Milburn, B.D. Adkins and B.H. Davis 543 Characterization and stability of porous structure of titanium-silicalite by sorption methods G. Lmfanti, F. Genoni, M. Padovan, G. Petrini, G. Trezza and A. Zecchina 553 Study of the pore network of dealuminated faujasites by water vapor adsorption M.H. Simonot-Grange, A. Elm’Chaouri, M. Nafis, G. Weber, P. Dufresne, F. Raatz and J.F. Joly 5 65