Physical Chemistry of Surfaces Sixth Edition ARTHUR W. ADAMSON Department of Chemistry, University of Southern California Los Angeles, California and ALICE P. GAST Department of Chemical Engineering, Stanford University Stanford, California ®) [A WILEY-INTERSCIENCE PUBLICATION John Wiley & Sons, Inc. NEW YORK / CHICHESTER / WEINHEIM / BRISBANE / SINGAPORE / TORONTOAbout the Front Cover Design ‘The fer-like shapes are two-dimensional dendritic crystals of the protein streptavidin bound to a lipid monolayer. These dendrites were produced by Andrew Ku with the help of Seth Darst, Roger Kornberg, and Channing Robertson and are described in Chapter XV; note Fig. XV-5. ‘The island pattern is from a marbled paper, for which we thank Mrs. Phoebe Easton. Marbling is an ancient process whereby colored oils with surfactant are spread on the surface of water stiffened by agar-agar and the pattern lifted onto the paper. The pattern could be that of domains ‘of 2 and of CO chemisorbed on PX(100); note Fig. XVILI-28. is book is printed on acid-free paper. © Copyright © 1997 by John Wiley & Sons, In. All rights reserved. Published simultaneously in Canada. [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, scanning or ‘otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright ‘Act, without either the prior written permission of the Publisher, or authorization through ‘payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (508) 750-8400, fax (508) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., (605 Third Avenue, New York. NY 10158-0012, (212) 850-6011, fax (212) 850-6008. E-Mail: PERMREQ @ WILEY.COM. Library of Congress Cataloging in Publication Data: ‘Adamson, Arthur W. Physical chemistry of surfaces / Arthur W. Adamson and Alice P. Gast. —6th ed. P. om, “A Wiley-Interscience Publication.” Includes bibliographical references and index. ISBN 0-471-14873-3 (cloth : alk. paper) 1. Surface chemistry. 2. Chemistry, Physical and theoretical L. Gast, Alice P. (Alice Petry), 1958- Il, Tile. QD506.A3 1997 541.3°3—de21 Printed in the United States of America 10987654321To Virginia, without whose fifty-five years of steady support this book and its previous editions would not have been written, and 10 Bradley, whose devotion and encouragement made this edition possibleIL. Capiltarity .. . The Young-Laplace Equation . The Maximum Bubble Pressure Method . . Detachment Methods... ; . Methods Based on the Shape of Static Drops a ‘or Bubbles. . Dynamic Methods of Measuring Surface Tension. Contents Surface Tension and Surface Free Ener Some Experiments with Soap Films The Treatment of Capillary Rise . A. Introductory Discussion ...... B. Exact Solutions to the Capillary Rise Problem C. Experimental Aspects of the Capillary Rise Method ‘A. The Drop Weight Method... B. The Ring Method . C. Wilhelmy Slide Method - ‘A. Pendant Drop Method ...........+ B, Sessile Drop or Bubble Method C. Sources of Other Deformed Shapes... A. Flow Methods. B. Capillary Waves C. Maximum Bubble Pressure Method. . Surface Tension Values as Obtained ce Different Methods... Problems .. General References . Textual References. viivili a Te cea ae a ee 1 IV. Surface Films on Liquid Substrates. . Structural and Theoretical Treatments of Liquid Interfaces . |. Orientation at Interfaces. |. The Surface Tension of Solutions . CONTENTS One-Component Systems A. Surface Thermodynamic Quantities for a Pure Substance . B. The Total Surface Energy, ES c le ies ot Corea carn sure Tension .... D. The Effect of Pressure on Surface Tension A. Further Development of the Thermodynamic ‘Treatment of the Surface Region B. Calculation of the Surface Interfaces .. A. Binary Solutions B. The Surface Tension of Systems . : ‘Thermodynamics of Binary Systems: The Gibbs Equation ... A. Definition of Surface Excess : B. The Gibbs Equation C. The Dividing Surface D. Other Surface Thermodynamic Re Determination of Surface Excess Quantities . A. Experimental Methods... B. Historical Footnote and Commentary - C. Theoretical Calculation of Surface Excess Quantities Gibbs Monolayers .. A. The Two-Dimensional Ideal-Gas Law. B. Nonideal Two-Dimensional Gases C. The Osmotic Pressure Point of View D. Surface Elasticity E. Traube’s Rule... F. Some Further Comments on Gibbs Monolayers. Problems .. General References . ‘Textual References. crria for Spreading .. B. Empirical and Theoretical Treatments. C. Kinetics of Spreading Processes D. The Marangoni Effect E. Lenses-Line Tension . : Experimental Techniques forthe Swdy ‘of Monomolecular Films... : A. Measurement of 7. B. Surface Potentials . 101 101 104 104 107 110 mt 42 43. 44 116era V. Electrical Aspects of Surface Chemistry .... aueene |. States of Monomolecular Films . Mixed Films, . Dissolution of Monolayers . |. The Electrified Solid—Liquid Interface .. CONTENTS C. Measurement of Surface Viscosity D. Optical Properties of Monolayers . E. Microscopic Evaluation of Monainyers, F. Diffraction Studies .. . Gaseous Films . Gas-Liquid Transitions . Condensed Phases . The Solid State.. Monolayer Collapse... 2. Domain Shapes and Interactions Sm MOOD > Evaporation Rates through Monomolecular Films Reactions in Monomolecular Films A. Kinetics of Reactions in Films. B. Kinetics of Formation and Hydrolysis of Esters . C. Other Chemical Reactions . Problems .... General References . Textual References. Introduction ...... : The Electrical Double Layer .. The Stem Layer... The Free Energy of a Diffuse Double Layer. Repulsion between Two Planar Double Layers... The Zeta Potential A. Electrophoresis B. Electroosmosis ... C. Streaming Potential...... D. Sedimentation Potential. E, Interrelationships in Electrokinetic Phenomena F. Potential, Surface Charge, and Colloidal Stability Electrocapillarity.. A. Thermodynamics of the Electrocapillary Effect. B. Experimental Methods C. Results for the Mercury-/ lution Interface . D. Effect of Uncharged Solutes and Changes of Solvent. E. Other Electrocapillary Systems . : A. Electrode-Solution Interface . B. Electrochemistry in Dispersed Phases . C. Photoelectrochemistry; Solar Energy Conversion 1. Types of Potentials and the Meaning of Potential Difference When Two Phases Are Involved. A. The Various Types of Potentials us. 126 128 130 131 BL 132 133 135 136 136 140 146 148 15 151 152 155 156 158 158 169VI. Long-Range Forces .. VIL. Surfaces of Solids . CONTENTS B. Volta Potentials, Surface Potential Differences, and the Thermionic Work Function C. Electrode Potentials .. D. Irreversible Electrode Phenomena. 10, Problems . . General References . Textual References. 1, Introduction .. 2. Forces between Atoms and Molecule: 3. Long-Range Forces .. ‘A. The Microscopic Approach B. The Retarded Dispersion Interaction . C. Experimental Measurements . 4, Long-Range Forces in Solution. A. Dispersion Forces in Condensed Media B. Electric Double-Layer Repulsion. C. Forces Due to Solvent Structure D. Thin-Film Viscosity .... Forces in Biological Systems. ‘The Disjoining Pressure. Anomalous Water.. Dipole-Induced Dipole Propagation... Problems . General References ... ‘Textual References pena 1. Introduction .. ‘A. The Surface Mobility of Solids : B. Effect of Processing on the Condition of Solid Surfaces 2. Thermodynamics of Crystals... AA Surface Tension and Surface Free Energy B. The Equilibrium Shape of a Crystal..... C. The Kelvin Equation .. 3. Theoretical Estimates of Surface Energies and Free Bnecgies- ‘A. Covalently Bonded Crystals ......--. : B. Rare-Gas Crystals C. Tonic Crystals... D. Molecular Crystals E. Metals 4, Factors Affecting the Surface ‘Actual Crystals A. State of Subdivision B. Deviations from Ideality C. Fractal Surfaces......... D. Dislocations... and Surface Tensions of