Macro-ion Characterization. From Dilute Solutions to Complex Fluids

547 Pages·1994·45.71 MB·English

by  Kenneth S. Schmitz (Eds.)

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In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
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In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
548
ACS S Y M P O S I UM SERIES
Macro-ion Characterization
From Dilute Solutions to Complex Fluids
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4-0 Kenneth S. Schmitz, EDITOR
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1 University of Missouri—Kansas City
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p://pubs.acs.org ember 13, 1993 |
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12 | e: D Developed from a symposium sponsored
20Dat by the Divisions of Polymer Chemistry, Inc.,
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August 1ublicatio anda tC thoell o2i0d5 atnhd N Sautirofnaacle MCheeemtinisgt ry
P of the American Chemical Society,
Denver, Colorado,
March 28-April 2, 1993
American Chemical Society, Washington, DC 1994
In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
Library of Congress Cataloging-in-Publication Data
Macro-ion characterization: from dilute solutions to complex fluids /
Kenneth S. Schmitz, editor.
p. cm.—(ACS symposium series, ISSN 0097-6156; 548)
"Developed from a symposium sponsored by the divisions of Polymer
Chemistry, Inc., and Colloid and Surface Chemistry at the 205th
National Meeting of the American Chemical Society, Denver, Colorado,
March 28-April 2, 1993."
Includes bibliographical references and index.
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w ISBN 0-8412-2770-5
8.f
54 1. Polyelectrolytes—Congresses.
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94- I. Schmitz, Kenneth S., 1943- . II. American Chemical Society.
19 Division of Polymer Chemistry. III. American Chemical Society.
k- Division of Colloid and Surface Chemistry. IV. Series.
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02 QD382.P64M33 1994
0.1 547.7'04572—dc20 93-39732
1 CIP
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In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
1993 Advisory Board
ACS Symposium Series
M. Joan Comstock, Series Editor
V. Dean Adams Bonnie Lawlor
University of Nevada— Institute for Scientific Information
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In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
Foreword
1HE ACS SYMPOSIUM SERIES was first published in 1974 to
provide a mechanism for publishing symposia quickly in book
form. The purpose of this series is to publish comprehensive
1 books developed from symposia, which are usually "snapshots
0
w0 in time" of the current research being done on a topic, plus
8.f some review material on the topic. For this reason, it is neces­
4
05 sary that the papers be published as quickly as possible.
4-
9 Before a symposium-based book is put under contract, the
9
1
k- proposed table of contents is reviewed for appropriateness to
b
1/ the topic and for comprehensiveness of the collection. Some
2
0
1 papers are excluded at this point, and others are added to
0.
doi: 1 rpoaupnerd oisu tp teheer -rsecvoipeew oedf thper iovro ltuom fei.n aIln aacdcdeiptitaonnc, ea dorra frt eojefc etiaocnh.
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12 | e: D who check that all necessary revisions have been made.
20Dat As a rule, only original research papers and original re­
11, on view papers are included in the volumes. Verbatim reproduc­
August ublicati tions of previously published papers are not accepted.
P

M. Joan Comstock
Series Editor
In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
Preface
POLYELECTROLYTES remain one of the least-understood states of con­
densed matter, in contrast to neutral polymer solutions. Although bulk
properties like osmotic pressure and viscosity have been studied for many
years, an understanding of the behavior of polyelectrolytes is lacking.
This problem is especially critical because of the fundamental importance
of many of the prototypical polyelectrolytes such as, for example, DNA.
Few meetings have focused on polyelectrolytes since the NATO meet­
ing two decades ago. Consequently, the response to the symposium on
01 which this book is based was overwhelming. The participants represented
0
pr a scientific diversity that covered both theory and experiment, from syn­
8.
4 thesis to physical properties in (and of) gels, and from nonperturbative
5
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4- methods to the application of external electric fields. The backgrounds of
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19 the participants spanned academia and industry; synthetic polymers and
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b biopolymers; and the departments of physics, chemistry, polymers,
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02 material sciences, and biological sciences. The participants came from all
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0. parts of the world.
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oi: The chapters are divided into six major subject areas: theory, syn­
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g 3 | thesis and characterization, condensation and complexation, solution
s.or199 structure, surface adsorption and interfaces, and gels. The objective in
s.ac13, making these classifications was to proceed from the more fundamental
uber and simplest cases to the most complex system, with respect both to the
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ugublic Acknowledgments
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Paul Dubin and Ray Farinato put in a tremendous effort in originating
and organizing the symposium on which this book is based. I also ack­
nowledge the cooperation of everyone involved in bringing this volume
into existence, including the authors, the reviewers, and the people at the
American Chemical Society Books Department. I give special thanks to
Anne Wilson, whose electronic-mail messages were inspirational. I also
thank Julie Fisher for designing and drawing the roller coaster illustration
in Chapter 1. Finally, I acknowledge those who were also influential in
xi
In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
the organization of this volume: Candace, wherever she may be; Julie
Fisher, for her courage; and DAX, may his principles survive.
KENNETH S. SCHMITZ
Department of Chemistry
University of Missouri
Kansas City, MO 64110
August 6, 1993
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xii
In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
Chapter 1
An Overview of Polyelectrolytes
Six Topics in Search of an Author
Kenneth S. Schmitz
Department of Chemistry, University of Missouri—Kansas City,
Kansas City, MO 64110
1
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8. Interests in solutions and suspension of macroions has been renewed in
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5 the past few years, as evidenced by the mini symposium upon which
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4- this present volume is based. Presented in this introductory chapter is a
9
9 brief presentation of a selection of six topics that I believe deserves
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k- further consideration regarding these complex systems: 1) the
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0 pairwise electrostatic energy between macroions; 3) the phenomenon
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0. of counterion condensation and its application to specific molecular
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oi: geometry; 4) the use of the Gibbs versus the Helmholtz free energy in
d describing the thermodynamics of these charged systems; 5) the
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s.ac13, by dynamic light scattering measurements.
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1, 2n D sometimes even being thrown for a loop when unexpected results are obtained.
1o Eventually, however, the excursion through the field of polyelectrolytes returns one to
ust cati the starting point. To illustrate the above metaphor one only has to follow the history
ugbli of a simple basic question: "Is the interaction between the charged macroions
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In 1938 Langmuir treated a solution of micelles in a manner similar to that of a
simple salt crystal. He thus considered the counterions between the micelles as part of
the interaction energy, which led to a major result (7):
The interaction of these charges, just as in the sodium chloride crystal,
gives an excess of attractive force and in order to have equilibrium it
will be necessary not to have an additional attractive force, such as the
van der Waals force postulated by Hamaker, but some new kind of
repulsive force.
In contrast to the conclusion of Langmuir, the currently accepted paradigm for
the majority of the practitioners in the colloid field is the DLVO (Derjaguin-Landau-
0097-6156/94/0548-0001$06.50/0
© 1994 American Chemical Society
In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
2 MACRO-ION CHARACTERIZATION
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99 Verwey-Overbeek) model (2). The attractive part of the DLVO potential is the van
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1/b than 20 A. The repulsive part of the DLVO potential is a pairwise screened Coulomb
02 interaction between two colloidal particles of radius Rs and charge qp = Zpq (qe is
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0. the magnitude of the electron charge) separated by a distance R is,
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s.acs.org 13, 1993 | U£meLl ec Vv0n = IEt(l +e KKDDHHRRs sJ ^ e4 Qnp £ *~RKD HR = x2 DN L V° ^£Q £\£ pR"K DHR (1)
pubber where the Debye-Huckel screening parameter KH is defined by the mdd different
p://em species of added electrolyte ions at conceDntrations <nj>u [unaiform (bulk)
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where £ is the dielectric constant, kfi is Boltzmann's constant, and X is the Bjerrum
B
length. Note that only the added electrolyte ions contribute to the screening
parameter in the DLVO theory as in the Debye-Huckel theory of simple salts, which
is why the subscript "DH" is include in equation 2. The reason for the apparent
universal acceptance of the DLVO potential lies in its qualitative success in
explaining most phenomena in colloidal systems even though the apparent charge
required to fit the data is generally smaller than the anticipated value of the charge
based on the chemical composition of the macroion.
For more than two decades, however, Ise and co-workers (3-10) have
emphasized that there exists some form of long range attractive interaction between
macroions that is not consistent with the standard DLVO potential. More specifically,
video movies taken through an ultramicroscope clearly showed two distinct regions in
a suspension of latex particles; a highly kinetic region in which the particles undergo
Brownian motion, and a relatively static ordered region (5, 9) which has embedded
regions of stable voids (9). Sogami and Ise (77) thus developed a model based on the
Gibbs free energy that exhibited a stable minimum at macroion separation distances
In Macro-ion Characterization; Schmitz, K.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1993.