Adsorption, Surface Area and Porosity SECOND EDITION S. J. Gregg K. S. W. Sing Formerly of the Department Department of Applied Chemistry, of Chemistry, University of Exeter, Brunel University, Uxbridge, Exeter, U.K. Middlesex, U.K. 1982 @) ACADEMIC PRESS A Subsidiary of Harcourt Brace Jovanovich, Publishers LONDON - NEW YORK PARIS « SAN DIEGO - SAN FRANCISCO SAO PAULO - SYDNEY - TOKYO - TORONTOACADEMIC PRESS ING. (LONDON) LTD 24/28 Oval Road, London NW1 7DX United Statas Edition published by ACADEMIC PRESS INC. 111 Fifth Avenue, New York, Naw York 10003 Copyright © 1982 by ACADEMIC PRESS INC. (LONDON) LTD All Rights Resewed No part of this book may be reproduced in any form by photostat, microfilm, or any other means without written permission from the publishers British Library Cataloguing in Publication Date Gregg. S. J. Adsorption, surface area and porosity.—2nd ed. 1. Surface chemistry 2. Surfaces (Physical) |. Title Il Sing, KS. W. 541.3453 QD506 — LCCCN 66-29432 ISBN 0-12-300956-1 ‘Monophoto’ Times New Roman ices (Typesetters) Ltd, Beccles, Sutfotk Printed in Great Britain by ‘St Edmundsbury Press, Bury St Edmunds, SutfolkPreface The principal aim of the second edition of this book remains the same as that of the first edition: to give a critical exposition of the use of the adsorption methods for the assessment of the surface area and pore size distribution of finely divided and porous solids. A vast amount of research has been undertaken on adsorption pheno- mena and the nature of solid surfaces over the fifteen years since the first edition was published, but for the most part this work has resulted in the refinement of existing theoretical principles and experimental procedures rather than in the formulation of entirely new concepts. In spite of the acknowledged weakness of its theoretical foundations, the Brunauer— Emmett-Teller (BET) method still remains the most widely used procedure for the determination of surface area; similarly, methods based on the Kelvin equation are still generally applied for the computation of mesopore size distribution from gas adsorption data. However, the more recent studies, especially those carried out on well defined surfaces, have led to a clearer understanding of the scope and limitations of these methods; furthermore, the growing awareness of the importance of molecular sieve carbons and zeolites has generated considerable interest in the properties of microporous solids and the mechanism of micropore filling. The incorporation of the new material without any increase in the overall length of the book has been achieved in part by extensive re-writing, with the compression of earlier material, and in part by restricting the scope to the physical adsorption of gases (apart from a section on mercury porosimetry). The topics of chemisorption and adsorption from solution, both of which were dealt with in some detail in the first edition, have been omitted: chemisorption processes are obviously dependent on the chemical nature of the surface and therefore cannot be relied upon. for the determination of the foal surface area; and methods based on adsorption from solution have not been developed, as was once hoped, into routine procedures for surface area determination. Likewise omitted. on grounds of v