Table Of ContentSURFACE AND
COLLOID SCIENCE
Volume 13
ADVISORY BOARD
BORIS V. DERJAGUIN, Institute of Physical Chemistry, Academy of Science
of the USSR, Moscow, USSR
TOMLINSON, FORT. Jr., California Polytechnic State University,
San Luis Obispo, California
STIG FRIBERG, Department of Chemistry, University of Missouri-Rolla,
Rolla-Missouri
J. ADIN MANN, Jr., Chemical Engineering Division, Case Western Reserve
University, Cleveland, Ohio
BARRY W. NINHAM, Institute of Advanced Studies, Australian National
University, Canberra, Australia
ROBERT A. PIEROTTI, Department of Chemistry, Georgia Institute of Tech
nology, Atlanta, Georgia
VELIMIR PRAV DIC, Institute "Rudjer Boskovic," Zagreb, Yugoslavia
KOZO SHINODA, Department of Applied Chemistry, Yokohama National
University, Minamiku, Yokohama, Japan
STANISLAS J. TEICHNER, Universite Claude Bernard-Lyon 1, Villeurbanne,
France
CAREL J. VAN OSS, School of Medicine, State University of New York at
Buffalo, Buffalo, New York
AGIENUS VRIJ, Van't Hoff Laboratorium, Rijksuniversiteit, Utrecht, The
Netherlands
ERVIN WOLFRAM, Department of Colloid Science, Lorand Eotvos Universi
ty, Budapest, Hungary
ALBERT C. ZETTLEMOYER, Lehigh University, Bethlehem, Pennsylvania
A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume im
mediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the
publisher.
SURFACE AND
COLLOID SCIENCE
Volume 13
Edited by
EGON MATIJEVIC
Institute of Colloid and Surface Science
Ctarkson University
Potsdam, New York
and
ROBERT 1. GOOD
State University of New York at Buffato
Amherst, New York
Springer Science+Business Media, LLC
The Library of Congress cataloged the first Plenum Press edition of this title as folIows:
Main entry under title:
Surface and colloid science.
Vol. 10- published by Plenum Press, New York.
Includes bibliographies.
1. Surface chemistry-Collected works. 2. Colloids-Collected works. I. Matijevic, Egon,
1922- ed.
QD506.S78 541/.345 67-29459
ISBN 978-1-4615-7974-8 ISBN 978-1-4615-7972-4 (eBook)
DOI 10.1007/978-1-4615-7972-4
© Springer Science+Business Media New York
Originally published by Plenum Press, New York 1984
Softcover reprint of the hardcover 1s t edition 1984
A Division of Plenum Publishing Corporat i on
233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Preface to the Series
A need for a comprehensive treatise on surface and colloid science has been
felt for a long time. Our series endeavors to fill this need. Its format has been
shaped by the features of this widely roaming science. Since the subjects to
be discussed represent such a broad spectrum, no single person could write a
critical review on more than a very limited number of topics. Thus, the
volumes will consist of chapters written by specialists. We expect this series
to represent a treatise by offering texts and critical reviews that will describe
theories, systems, and processes, handle these in a vigorous way, and
indicate solved problems and problems which still require further research.
Purely descriptive colloid chemistry will be limited to a minimum. Qualita
tive observations of poorly defined systems, which in the past have been so
much in evidence, will be avoided. Thus, the chapters are neither supposed
to possess the character of advances. nor to represent reviews of authors'
own work. Instead, it is hoped that each contribution will treat a subject
critically, giving the historic development as well as a digest of the newest
results. Every effort will be made to include chapters on novel systems and
phenomena.
It is impossible to publish a work of this magnitude with all chapters in
a logical order. Rather, the contributions will appear as they arrive, as soon
as the editor receives sufficient material for a volume. A certain amount of
overlap is unavoidable but will be kept to a minimum. Also, uniform
treatment and style cannot be expected in a work that represents the effort
of so many. Notwithstanding these anticipated difficulties, the series
presented here appears to be the only practical way to accomplish the task
of a high-level and modern treatise on surface and colloid science.
Some general remarks may be in order. In modern times, few disci
plines have fluctuated in "popularity" as much as colloid and surface
science. However, it seems that these sporadic declines in interest in the
science of "neglected dimensions" have been only apparent. In reality, there
has been a steady increase in research through the years, especially in
industrial laboratories. The fluctuations have been most noticeable in
academic institutions, especially with regard to teaching of specialized
v
vi
courses. It is thus only natural that university professors with surface and
colloid science as their abiding interest have expressed frequent concern for
and have repeatedly warned of the need for better and more intensive
education, especially on the graduate level.
There are several reasons for the discrepancy between the need of
industrial and academic research laboratories for well-trained surface and
colloid scientists and the efforts of the academic institutions to provide
specialization in these disciplines. Many instructors believe that a good
background in the basic principles of chemistry, physics, and mathematics
will enable a professional person to engage in research in surface and colloid
science. This may be true, but only after much additional professional
growth. Indeed, many people active in this area are self-educated. Further
more, this science deals with an unusually wide range of systems and
principles. This makes a uniform treatment of problems in surface and
colloid science not only challenging but also a very difficult task. As a
matter of fact, certain branches of colloid science have grown into separate,
independent disciplines which only in a broad sense are now considered a
part of the "parent" science. Finally, there is often a stigma associated with
the name "colloids." To many, the term symbolizes empirically and poorly
described, irreproducible, etc., systems to which exact science cannot as yet
be applied. The latter impression is in part based on the fact that a
considerable number of papers were and are published that leave much to be
desired with regard to the rigorousness of the approach.
Yet, during the first half of this century some of the most acclaimed
scientists have occupied themselves with colloid and surface science prob
lems. One needs to mention only a few such as Einstein, von Smoluchowski,
Oebye, Perrin, Loeb, Freundlich, Zsigmondy, Pauli, Langmuir, McBain,
Harkins, Donnan, Kruyt, Svedberg, Tiselius, Frumkin, Adam, and Rideal,
who have made substantial contributions to the classical foundations of
colloid and surface science. This work has led to many fundamental
theoretical advances and to a tremendous number of practical applications
in a variety of systems such a natural and synthetic polymers, proteins and
nucleic acids, ceramics, textiles, coatings, detergents, lubricants, paints,
catalysts, fuels, foams, emulsions, membranes, pharmaceuticals, ores, com
posites, soils, air and water pollutants, and many others.
It is therefore our hope that this treatise will be of value to scientists of
all descriptions, and that it will provide a stimulating reference work for
those who do not need to be convinced of the importance of colloid and
surface science in nature and in application.
EGON MATIJEVIC
Preface to Volume 13
Dr. Robert Good has been asked by the publisher to edit volumes of Surface
and Colloid Science that deal primarily with experimental methods as a
sequence of an earlier series titled Techniques of Surface and Colloid
Chemistry and Physics. In order to expedite the publication of chapters
received by Dr. Good and by myself, Volume 13 appears as a joint editorial
effort. The variety of topics contained in this book should be of interest to a
broad spectrum of scientists active in interfacial and colloid phenomena.
EGON MATIJEVIC
vii
Contents
1. Electrochemistry of Oil-Water Interfaces
Akira Watanabe
1. Potential Difference at Oil-Water Interfaces 1
1.1. Equilibrium ........ . 1
1.2. Nernst Potential ..... . 5
1.3. Surface and Interfacial Potential 7
1.4. Diffusion Potential ..... 9
2. Electrocapillarity . . . . . . . . . 10
2.1. Thermodynamics of Electrocapillarity 10
2.2. Electrocapillarity at Oil-Water Interfaces 13
2.3. Adsorption at Oil-Water Interfaces 15
2.3.1. Poisson's Equation .. 15
2.3.2. Conservation of Energy 15
2.3.3. Adsorption Isotherm . 18
2.3.4. Calculation of Adsorption 19
2.4. Mechanism of the Decrease in Interfacial Tension by
Applying Potential 22
3. Binding at Oil-Water Interfaces 28
3.1. Counterion Binding . 28
3.2. Hydrogen Ion Binding 32
3.3. Competing Binding 35
3.4. Stern Effect 37
3.5. Mixed Adsorption 39
4. Electrocapillary Emulsification 41
4.1. General Principles 41
4.2. Condition of Emulsification 42
4.3. Stability and Droplet Size Distribution 43
4.4. Mechanism of Electrocapillary Emulsification 45
5. Coalescence of Droplets .......... . 49
5.1. DLV O Theory and Coalescence of Mercury Droplets 49
5.2. Coalescence of Aqueous Drops in Oil Phase 53
5.3. Bridge Formation between Water Droplets 53
5.4. Protection by Organic Materials ..... 55
ix
x Contents
6. Potential Distribution of Membrane Systems 57
6.1. Donnan Membrane Potential . 57
6.2. Bi-Ionic Potential . . . . . . 60
6.3. Membrane Potential Difference 61
Abbreviations 64
Notation 65
References 69
2. Kinetic Theory of Flotation of Small Particles
B. V. Derjaguin, S. S. Dukhin, and N N Rulyov
1. Specific Features of the Mechanism Involving Fixation of Small Particles
on the Surface of a Bubble . . . . . . . . . . . . . . . . . .. 71
2. Specific Features of the Mechanism of Transfer of Small Particles to the
Bubble Surface . . . . . . . . . . . . . . . . . . . . . . .. 77
3. Quantitative Theory of Flotation of Small and Medium-Sized Spherical
Particles . . . . . . . . . . . . . . . . . . . . . . . . . .. 80
4. Quantitative Experimental Research into Flotation of Small Particles 89
5. Detachment of Small Particles in Contactless Flotation and the Dynamic
Adsorption Layer of a Bubble ..... 91
6. Nonequilibrium Surface Forces in Flotation .......... 98
7. Collision Efficiency and Flotation Kinetics .......... 102
8. Influence of Aggregation of the Particles on the Elementary Act of
Inertia-free Flotation 102
9. Flotation of Submicron Particles 104
10. Conclusions 105
Notation 109
References 110
3. Specifically Impermeable Precipitate Membranes
Carel 1. van Oss
1. Introduction 115
2. The Hirsch Effect 116
2.1. Membrane Potential 116
2.2. Conditions for Specific Impermeability 117
2.3. "Conditioning" of BaS04 Membranes 117
2.4. Generation of Galvanic Currents and Other Electrical Properties 118
2.5. Precipitate Membranes as Electrodes 118
2.6. "Deconditioning" of BaS04 Membranes 119
2.7. Other Ionic Precipitate Membranes 120
2.8. Mechanism of Specific Impermeability 120
3. Precipitate Formation by Double Diffusion in Gels 121
3.1. Antigens and Antibodies 121
3.2. Antigen-Antibody Precipitates Formed by Double Diffusion
in Gels 122
3.3. Other Double-Diffusion Precipitate Systems 125
Contents xi
4. Place of First Formation of Precipitate Lines in Double Diffusion in Gels 126
4.1. Complex-forming and Non-Complex-forming Substances 126
4.2. Place of First Precipitation of Complex-forming Systems . . 127
4.3. Determination of Diffusion Coefficients of Complex-forming
Biopolymers by Double Diffusion at Right Angles in Gels 129
4.4. Shape of the Precipitate Lines of First Formation of Complex-
forming Systems ................... 130
4.5. Place of First Precipitation of Non-Complex-forming Systems 130
5. Evolution of Precipitate Lines in Double Diffusion as a Function of
Reagent Concentration and Time .............. 131
5.1. Decay of Precipitate Lines of Complex-forming Systems at Excess
of One of the Reagents ........... 131
5.2. Titration by Double-Diffusion Precipitation ....... 132
6. Nondiffusion Methods for Generating Precipitate Lines . . . . . 133
6.1. Other Methods for Inducing Reagents to Meet and Interact 133
6.2. Counterelectrophoresis 134
6.3. Rheophoresis .............. 134
7. Single-Diffusion Precipitation .......... 134
7.1. Monodimensional Single-Diffusion Precipitation 134
7.2. Bidimensional Single-Diffusion Precipitation 135
7.3. Precipitation Induced by Electrophoresis of One Reagent into a
Gel Imbibed with the Other Reagent 136
8. Liesegang Phenomenon . . . . . . . . . . . . . . . . 137
8.1. Earlier Theories ................ 137
8.2. Implications of Specific Impermeability of Precipitates 138
9. Biological Precipitate Membranes ........... 139
9.1. Membranes Specifically Impermeable to Given Ions . 139
9.2. Other Properties of Precipitates of Biological Materials 140
References ........................ 141
4. Dynamic Surface Tension and Capillary Waves
1. Adin Mann, Jr.
1. Introduction: Surface Constitutive Equations ........... 145
2. General Theoretical Discussion ..... ........... 150
3. General Remarks on Ripple Methods for the Study of Dynamic Surface
Tension . . . . . . . . . 167
4. Interfacial Wave Methods . 169
4.1. Theory of the Method 169
4.2. Working Equations 173
4.3. Numerical Analysis of the Working Equations 180
4.4. Instrumentation and Procedures 184
4.5. Analysis of the Ripple Motion 188
4.6. Modes of Data Collection 192
