Colloid Science Volume 3 a review of the literature published 1974-1977

350 Pages·1979·28.722 MB·English

by  D H Everett;

A Specialist Periodical Report
Colloid Science
Volume 3
A Review of the Literature Published 1974-1977
Senior Reporter
D. H. Everett, M.B.E., Department of Physical Chemistry,
University of Bristol
Reporters
G. T. Barnes, University of Queensland, Australia
J. M. Brow.n, University of Oxford
T. Cosgrove, University of Bristol
S. S. Davis, Departmenf of Pharmacy, University of Noftingham
J. F. Goodman, Proctor and Gamble, Cincinnati, Ohio, U.S.A.
D. Nicholson, Brunel Universify, Uxbridge
R. T. Podoll, University of Bristol
K. S. W. Sing, Brunel University, Uxbridge
B. Vincent, Universify of Brisfol
T. Walker, Procfor and Gamble, Cincinnati, Ohio, U.S.A.
The Chemical Society
Burlington House, London, WIV OBN
British Library Cataloguing in Publication Data
Colloid Science. -
(Chemical Society. Specialist periodical reports; 3).
VOl. 3
1. Colloids
I. Everett, Douglas Hugh 11. Series
541'.3451 QD549 72-95096
ISBN 0-851 86-528-3
ISSN 0305-9723
Copyright 0 1979
The Chemical Society
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means graphic, electronic,
-
including photocopying, recording, taping or
inf ormation storage and retrieval systems - without
written permission from The Chemical Society
Printed in Great Britain by Henry Ling Ltd.,
at the Dorset Press, Dorchester, Dorset.
This volume of the Specialist Periodical Reports on Colloid Science continues to
review work on solid/gas interfaces (Chapter l), on solid/liquid interfaces
(Chapter 2), and on emulsions (Chapter 4). In Chapter 3 the earlier report on the
equilibrium aspects of insoluble monolayers is extended to dynamic aspects.
Two aspects of micellization are dealt with in Chapters 5 and 6. The former is
mainly concerned with phase behaviour and thermodynamics, the latter with the
rapidly expanding topic of structure and chemical reactivity in micellar aggregates.
In Chapter 7 recent work on the application of a variety of spectroscopic tech-
niques to the study of the gas/solid interface is reviewed. In general, the present
volume covers the period 1974-77, although in the case of new topics earlier
background work is outlined.
Again the emphasis has been on a critical assessment of recent work and on
the integration and correlation of material from a wide range of sources. Thus
although the literature coverage is not exhaustive, it is hoped that all the more
important recent developments in the areas dealt with have been noted.
Bristol D. H. Everett
September 1978

Contents
Chapter 1 Adsorption at the GaslSolid Interface 1
By D. Nicholson and K. S. W. Sing
1 General Aspects of Physisorption
The Potential Energy of Adsorption
Structure oi” Adsorbed Monolayers
Specific Adsorbate-Adsorbent Interactions
Determination of Surface Area
2 Adsorption in Micropores 10
Concept of Microporosity and Interpretation of
Type I Isotherms 10
The Dubinin Theory of Micropore Filling 16
Potential Energy for Adsorption in Micropores 21
Statistical Mechanical Treatments for Adsorption in
Micropores 26
Conclusions 30
3 Adsorption and Surface Effects in Flow and Diffusion 31
Introduction 31
Regimes of Flow 39
Influence of Pore Structure 40
Surface Flow 46
Intra-crystalline Diffusion in Zeolites 57
Chapter 2 Adsorption at the Solid/Liquid Interface:
Non-electrolyte Systems 63
By 0.H . Evereft and R. T, Podoll
1 Introduction 63
2 Thermodynamic Considerations 63
3 Determination of Surface Areas by Adsorption from
Solution 73
4 Relationship between Gas Adsorption and Adsorption
from Solution 78
5 Adsorption from Dilute Solutions 93
vi Colloid Science
6 Adsorption from Multicomponent Solutions 103
7 Liquid Chromatography 115
8 Spectroscopic Methods 118
9 Studies of Specific Systems 126
Silica 126
Carbons 133
No n-porou s Carbons 133
Activated Carbons 138
Miscellaneous Adsorbents 143
Oxide Adsorbents 143
Clay Minerals 147
Chapter 3 Insoluble Monolayers - Dynamic Aspects 150
By G. T. Barnes
1 Introduction 150
2 Rheological Properties 150
Surface Shear Viscosity 150
Dilational Visco-elasticity 155
Relaxation Processes 162
Summary 166
3 Movement across the Interface 166
Spread in g Solvents 166
Spreading from Crystals 167
Spreading Across a Liquid Surface 168
Surface Diffusion 169
4 Mass Transport through Monolayers 170
General Principles 170
Evaporation through Monolayers 17 1
Evaporation of Water Droplets 177
Transport of Gases 177
Transport through Liq uid /Liquid Interfaces 180
5 Penetration of Monolayers 181
Kinetics of Penetration 182
Equilibrium Penetration 183
Theoretical Treatment of Penetration 185
Summary 188
6 Reactions in Monolayers 188
7 Concluding Remarks 192
Cont ents vii
Chapter 4 Emulsions 193
By B. Vincent and S. S. Davis
1 Introduction 193
2 Nun-spontaneous Emulsitication 194
3 Spontaneous Emulsification 197
4 Emulsion Stability 210
5 Emulsion Properties 222
Chapter 5 Micellization in Aqueous Solution 230
By J. F. Goodman and T. Walker
1 Introduction 230
2 Phase Behaviour of Surface Active Agents in Water 233
3 Properties of Micellar Solutions 238
Molecular Motion 238
Micellar Shape 240
4 Thermodynamics of Micellization 243
Thermodynamic Model 243
Monomeric Surfactant Concentration 245
Aggregation Numbers 246
Free Energy and Enthalpy of Micellization 247
5 Theories of Micelle Formation 250
6 General Conclusions 252
Chapter 6 Structure and Reactivity in Micellar Aggregates 253
By J. M, Brown
1 Introduction 253
2 The Structure of Micelles 255
Inverse Micelles 259
3 Dynamic Aspects of Micelle Formation and Break-
down 260
viii Colloid Science
4 Ground- and Excited-state Reactions and Equilibria in
Micelles 264
Transient Intermediates 265
5 Micellar Catalysis 270
Hydrolysis of Acyl Derivatives 270
Ester Hydrolysis by Functional and Mixed Micelles 272
Hydrolysis of Phosphate Esters 277
Carbonium Ion Reactions in Micelles 277
Aromatic Nucleophilic Substitution 280
Proton Transfer in Micelles 28 1
Other Micelle-p r omot ed Reacti ons 282
Catalysis by Inverse Micelles 283
Catalysis of Inorganic Reactions 284
6 Other Aspects of Hydrophobic Catalysis 285
Catalysis in Association Complexes 285
Catalysis by Functional Polymers 290
Chapter 7 Spectroscopic Measurements at the Gas/Solid
Interface 29 3
By T. Cosgrove
1 Introduction 293
2 Infrared Studies 293
Infrared Spectra 293
Zeolite Surfaces 294
Silica Surfaces 295
Alumina Surfaces 295
Other Oxide Surfaces 296
Halide Surfaces 296
Metal Surfaces 296
Supported Metal Surfaces 297
New Techniques 298
3 Nuclear Magnetic Resonance 299
Zeolites 300
Silicas and Aluminas 305
Other Oxides 308
Carbon Surfaces 309
Metal Surfaces 309
Glass Surfaces 310
4 Electron Spin Resonance 3 10
Oxygen Radical Anions 311
Sulphur Anions 313
Small Molecules 313
Paramagnetic Probes 314
New Technique: Adiabatic Rapid Passage 315