Micellization, Solubilization, and Microemulsions: Volume 2

459 Pages·1977·1.89 MB·English

by  K. Martinek, A. K. Yatsimirski, A. V. Levashov, I. V. Berezin (auth.), K. L. Mittal (eds.)

Micellization,
Solubilization, and
Microemulsions
Volume 2
Micellization,
Solubilization, and
Microemulsions
Volume 2
Edited by
K.L. Mittal
IBM Corporation
East Fishkill Facility
Hopewell Junction, New York
Plenum Press· New York and London
Library of Congress Cataloging in Publication Data
Symposium on Micellization, Solubilization, and Microemulsions, Albany, 1976.
Micellization, solubilization, and microemulsions.
Symposium held at the Seventh Northeast regional meeting of the American Chemical
Society.
Includes indexes.
1. Micelles-Congresses. 2. Solubilization-Congresses. 3. Emulsions-Congresses. I. Mittal,
K. L., 1945- II. Title. III. Title: Microemulsions.
00549.8976 1976 541'.3451 77-1126
ISBN-13: 978-1-4613-4159-8 e-ISBN-13: 978-1-4613-4157-4
001: 10.1007/978-1-4613-4157-4
Proceedings of the second half of the International Symposium on Micellization,
Solubilization, and Microemulsions held at the Seventh Northeast Regional Meeting of the
American Chemical Society in Albany, New York, August 8-11, 1976
© 1977 Plenum Press, New York
Softcover reprint of the hardcover 15t edition 1977
A Division of Plenum Publishing Corporation
227 West 17th Street, New York, N.Y. 10011
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
This volume and its companion Volume 1 chronicle the proceed-
ings of the International Symposium on Micellization, Solubiliza-
tion, and tficroemulsions held under the auspices of the Northeast
Regional Meeting of the American Chemical Society in Albany, New
York, August 8-11, 1976. The technical program consisted of 48
papers by 91 authors from twelve countries. The program was divided
into six sessions, and Dr. Hartley delivered the Concluding Remarks.
Subsequently, six more papers were contributed for the proceedings
volumes with the result that these volumes contain Sl papers (three
papers are not included for certain reasons) and are divided into
seven parts. The first three parts are embodied in Volume I and
the remaining four parts constitute Volume 2; each part is followed
by a Discussion Section. Dr. Hartley's Concluding Remarks are in-
cluded in both volumes.
When the idea of arranging a symposium on micelles was broached
to me, I accepted it without an iota of hesitation. I had two op-
tions: either to make it a one- or two-sessions symposium, or
bring together the global community actively carrying out research
in this area. I opted for the latter as the subject was very
timely and I knew that it would elicit very enthusiastic response.
In order to broaden the scope of the symposium, I suggested that
the theme of the symposium should be Micellizationy Solubilization
and Microemulsions.
Two salient features of this symposium should be mentioned:
(i) a truly international symposium of this magnitude rarely occurs
at a Regional Meeting, and (ii) I do not know whether there was
ever a symposium of this quality, magnitude, and breadth of coverage
on this topic.
Micelles are colloidal species in solution that are produced
by aggregation of a relatively large number (from 20 up to thousands)
of small amphiphilic molecules or ions. Micellar systems are
v
PREFACE
usually described as association colloids. The fundamental char-
acteristics of micelle-forming monomers is their amphiphilicity -
the presence of both polar and nonpolar portions in the same
molecule. The great variety of possible monomers produces micelles
of widely differing surface composition and interior. The applica-
tions of amphiphilic substances ranges from A to Z (anesthesiology
to zoology) and their micelle formation has important ramifications.
Micelle formation occurs by cooperative association of monomers
over a narrow concentration range known as the critical micelliza-
tion concentration (c.m.c.).
Their special structural characteristics and their ability to
solubilize otherwise insoluble substances render micelles both
important and useful. Among other things, micelles act as good
model systems and are excellent catalysts for a host of reactions.
The many and varied applications of micelles and microemulsions
are summarized in the opening chapter of these proceedings volumes.
The earlier research activity in the area of micelles was
primarily carried out by colloid chemists but a glance at the
literature on this topic attests that presently researchers from
many disciplines are actively pursuing research in this area. The
energy crisis has given an impetus for increased work on applica-
tion of microemulsions and micellar solutions for tertiary oil
recovery. Also, permanent storage of energy through light-driven
redox reactions is shown to be feasible using micellar surfactant
systems. It should be added that the availability of sophisticated
instrumentation has been a boon in micellar research.
These proceedings volumes contain a comprehensive coverage of
both theoretical and practical aspects of micellization, solubiliza-
tion, and microemulsions. These volumes bring together the latest
theoretical and experimental research activities being carried out
by scientists from various disciplines, bring out clearly the inter-
disciplinary and multidisciplinary aspects and importance of the
subject symposium. The topics covered include: history, applica-
tions, and prospects of micelles; thermodynamics and kinetics
of micellization, application of fast reaction kinetics; theo-
retical developments in understanding monomer-micelle equilibria
and stepwise aggregation; stepwise aggregation and the concept of
c.m.c.; micelles of ionic and nonionic surfactants in aqueous and
nonaqueous media; micelles as model systems; micelles and oil
recovery; mixed micelles; application of spectroscopic techniques
to understand mechanisms of reactions and interactions in micellar
media; micellar catalysis of a variety of reactions; solubiliza-
tion of polar and nonpolar substances; formation and structure of
microemulsions and reactions in microemulsion media.
PREFACE vii
These volumes - a product of the efforts of more than one
hundred scientists representing many countries - attest to the brisk
research activity taking place in the realm of micelles and micro-
emulsions, and all signals indicate that this tempo will be con-
tinued. As we probe more into this fascinating area of micelles
and microemu1sions, more new vistas will emerge.
Acknowledgments. First of all I am thankful to Dr. G. S.
Hartley for his presence at the Symposium. His presentation,
"Micelles: Retrospect and Prospect" was the highlight of the pro-
gram. Thanks are due to the officials of the Northeast Regional
Meeting for sponsoring the event, to IBM Corporation for permitting
me to organize the symposium and to edit these volumes. Thanks are
due to our secretary, Us. Julie Hrib, for helping with the correspon-
dence typing. I am thankful to my wife, Usha, for sacrificing many
hours which rightfully belonged to her, and to my daughter, Anita,
and son, Rajesh, for being very nice kids and letting their Daddy
work at home. The reviewers should be thanked for their many valu-
able comments on the manuscripts. The enthusiasm and cooperation
of the contributors, particularly those from overseas, is sincerely
acknowledged. The Petroleum Research Fund of the American Chemical
Society should be thanked for partial travel assistance to three
speakers.
K. 1. Mitta1
IBM Corporation
East Fishkill Facility
Hopewell Junction, New York 12533
CONTENTS OF VOLUME 2
PART IV: REACTIONS IN HICELLES AND HI CELLAR CATALYSIS
IN AQUEOUS HEDIA
The Kinetic Theory and the Hechanisms of Micellar Effects
on Chemical Reactions
K. Hartinek, A. K. Yatsimirski, A. V. Levashov
and I. V. Berezin . . . . . . ... 489
A General Kinetic Theory of Rate Enhancements for
Reactions between Organic Substrates and Hydro-
philic Ions in Micellar Systems
L. S. Romsted ........ . 509
Laser Photolysis Studies of Photo Redox Processes in
Micellar Solutions
H. Gratzel. . . . . . . . . . . . . . . . . . . 531
Radiation-Induced Redox Reactions in Hicellar Solutions
A.J. Frank. . . . . . . . . ..•...... 549
Radiation-Induced Processes in Nonionic Hicelles
K. Kalyanasundaram and J. K. Thomas .. 569
Radiation-Induced Peroxidation in Fatty Acid Soap Micelles
L. K. Patterson and J. L. Redpath . . . . . . . 589
Bifunctional Hicellar Catalysis
R. A. Hoss, R. C. Nahas, and S. Ramaswami .... 603
The Use of Phase Trallsfer Catalysts with Emulsion and
Hicelle Systems in Electro-Organic Synthesis
T. C. Franklin and T. Honda ......... . 617
The Catalytic Role of llicelle-Bisulfite Complexation
in Vinyl Polymerization
O.-K. Kim 627
Discussion 645
ix
x CONTENTS OF VOLUME 2
PART V: REACTIONS IN MICELLES AND MICELLAR CATALYSIS
IN NONAQUEOUS MEDIA
Some Kinetic Studies in the Reversed ~1icellar System-
Aerosol OT (Diisooctyl Sulfosuccinate)/H20/
Heptane Solution
M. Wong and J. K. Thomas ............ . 647
Catalysis by Cations in Cores of Non-Aqueous Micelles
F. M. Fowkes, D. Z. Becher, M. ~rmo, C. Silebi
and C. C. Chao. . . .. ....... . 665
Solubilization and Catalysis of Polar Substances in
Nonaqueous Surfactant Solutions
A. Kitahara and K. Kon-no . . 675
Ligand Exchange Reactions of Hemin and Vitamin B12a in
the Presence of Surfactants in Water and in
Nonpolar Solvents
J. H. Fendler 695
Discussion 711
PART VI: MICROE~LSIONS
Theory for the Phase Behavior of Microemulsions
M. L. Robbins . . . .. ..... . 713
Stability, Phase Equilibria, and Interfacial Free
Energy in Microemulsions
E. Ruckenstein. . . . . 755
Light Scattering of a Concentrated W/O Hicro Emulsion;
Application of Hodern Fluid Theories
A. J. Calj~, W. G. M. Agterof and A. Vrij .... 779
Hicroemulsions Containing Ionic Surfactants
S. Friberg and I. Buraczewska ..... 791
Interactions and Reactions in Hicroemulsions
R. A. Hackay, K. Letts, and C. Jones. 807
Discussion 817
CONTENTS OF VOLUME 2
PART VII. GENERAL PAPERS
Mixed Micelles of Methyl Orange Dye and Cationic Surfactants
R. L. Reeves and S. A. Harkaway. . . ...• 819
Anionic Surfactant Complexes with Charged and Uncharged
Cellulose Ethers
E. D. Goddard and R. B. Hannan ... 835
Proposal for a New Theory of Molecular Transport across
Membranes: Implications for Lung Gas Transference
B. Ecanow, B. H. Gold, R. Balagot, and R. S. Levinson. 847
Interfacial Tension Minima in Two-Phase liicellar Systems
E. Franses, M. S. Bidner and L. E. Scriven .••.. 855
Equilibrium Bicontinuous Structures
L. E. Scriven. . . • . . 877
Intramacromolecular Micelles
U. P. Strauss .....• 895
Solubilization by Nonionic Surfactants in the HLB-
Temperature Range
S. Friberg, I. Buraczewska, and J. C. Ravey. . 901
The Effect of Lysoplasmalogen on Some Physical Properties
of Dipalmitoyllecithin Bilayers: A Fluorescent Probe
Study
D. A. N. Morris and J. K. Thomas 913
Concluding Remarks. . • 927
About the Contributors. 931
Subject Index . . . . . 939
CONTENTS OF VOLUME 1
PART I: GENERAL PAPERS
The Wide World of Micelles
K. L. Mittal and P. Mukerjee. 1
Micelles - Retrospect and Prospect
G. S. Hartley ..... . 23
~1icellization, Solubilization, and Microemulsions
L. H. Prince. . . . . . . . . . 45
Biological Implications of Micelle Formation
A. T. Florence.. .... 55
Fluorescent Probes for Micellar Systems
N. J. Turro, M. W. Geiger, R. R. Hautala and
N. E. Schore. .....• • . . . . 75
Micellar Solutions for Improved Oil Recovery
V. K. Bansal and D. o. Shah 87
Discussion .. .. ' 115
PART II. THERHODYNMlICS AND KINETICS OF MICELLIZATION
IN AQUEOUS MEDIA
Thermodynamics of ~licellization of Simple Amphiphiles
in Aqueous Media
C. Tanford •....•............. 119
Thermodynamics of Amphiphilar Aggregation into ~licelles
and Vesicles
E. Ruckenstein and R. Nagarajan 133
Thermodynamics of Hice11e Formation
K. S. Birdi ....•...•. 151
xiii