Advanced Chemical Methods for Soil and Clay Minerals Research: Proceedings of the NATO Advanced Study Institute held at the University of Illinois, July 23 – August 4, 1979

478 Pages·1980·10.165 MB·English

by  Bernard A. Goodman (auth.), J. W. Stucki, W. L. Banwart (eds.)

Advanced Chemical Methods for Soil and Clay Minerals Research
NATO ADVANCED STUDY INSTITUTES SERIES
Proceedings of the Advanced Study Institute Programme, which aims
at the dissemination ofa dvanced knowledge and
the formation of contacts among scientists from different countries
The series is published by an international board of publishers in conjunction
with NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht, Boston and London
D Behavioural and Sijthoff & Noordhoff International
Social Sciences Publishers
E Applied Sciences Alphen aan den Rijn and Germantown
U.S.A.
Series C - Mathematical and Physical Sciences
Volume 63 - Advanced Chemical Methods for Soil and Clay Minerals Research
Advanced Chemical
Methods for Soil and
Clay Minerals Research
Proceedings of the NATO Advanced Study Institute
held at the University ofI llinois,
July 23 - August 4, 1979
edited by
J. W. STUCKI and W. L. BANWART
Univer$ity of1 1linoi$, Urbana, Rlinoi$, U.S.A.
D. Reidel Publishing Company
Dordrecht : Holland / Boston: U.S.A. / London: England
Published in cooperation with NATO Scientific Affairs Division
library of Congress Cataloging in Publication Data
Main entry under title:
Advanced chemical methods for soil and clay minerals research.
(NATO advanced study institutes series: Series C, Mathematical and
physical sciences; v. 63)
"Published in cooperation with NATO Scientific Affairs Division."
Includes index.
1. Soil mineralogy-Methodology-Congresses. 2. Clay minerals
Research-Congresses. 3. Soils-Analysis-Congresses. 4. Clay-Analysis
Congresses. I. Stucki, J. W. II. Banwart, Wayne L. III. Illinois.
University at Urbana-Champaign. IV. North Atlantic Treaty Organization.
Division of Scientific Affairs. V. Series.
S592.55.A38 631.4'16 80-23081
ISBN-I3: 978-94-009-9096-8 e-ISBN-I3: 978-94-009-9094-4
DOl: 10.1007/978-94-009-9094-4
Published by D. Reidel Publishing Company
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Copyright © 1980 by D. Reidel Publishing Company, Dordrecht, Holland
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TABLE OF CONTENTS
PREFACE ..................................................... )vii
1. MOSSBAUER SPECTROSCOPY - Bernard A. Goodman
1-1. I ntroduction to the Mossbauer Effect .... 1
1-2. Basic PrinCiples of Mossbauer Spectroscopy .. 7
1-3. Instrumentation and Experimental Procedures. 19
1-4. Application of Mossbauer Spectroscopy to the
Study of Silicate Minerals .......... . 28
1-5. The Study of Mineral Alteration Reactions 45
1-6. Iron Oxides and their Characterization in Soils 65
1-7. Critical Assessment of the Potential of Mossbauer
Spectroscopy, and its Application to Nuclei
Other than I ron 80
References . . . . . . . . . . . . . . . . . . . . 90
2. NEUTRON SCATTERING METHODS OF INVESTIGATING
CLAY SYSTEMS- D.K. Ross and P.L. Hall 93
2-1. Introduction . . . . . . . . . . . . . . . . . . . 93
2-2. Elementary Neutron Scattering Theory ..... 99
2-3. Neutron Scattering Instrumentation and Methods 130
2-4. Applications of Neutron Spectroscopy to Studies
of Clay Minerals ............ . 138
Appendix 2-1. Macroscopic Cross Section for a
Montmorillonite-Water System ...... . 160
Appendix 2-2. Calculation of Incoherent Scatt'ering Intensity
Ratios for a Clay-Water System 162
References . . . . . . . . . . . . . . . . . . . . . 163
3. INTRODUCTION TO X-RAY PHOTOELECTRON
SPECTROSCOPY- C. Defosse and P.G. Rouxhet 169
3-1. Introduction ..... 169
3-2. Trend of XPS Spectra 171
3-3. Instrumentation 175
3-4. Peak Position . 177
3-5. Explored Depth 182
3-6. Peak Intensity 185
3-7. Overview of Methods of Characterization of Solids
Based on X-ray, Electron and Ion Beams 193
References . . . . . . . . . . . . . . . . . . . . . . . . 201
vi TABLE OF CONTENTS
4. APPLICATION OF X-RAY PHOTOELECTRON SPECTROSCOPY TO THE
STUDY OF MINERAL SURFACE CHEMISTRY - M.H. Koppelman 205
4-1. Uniqueness of XPS for the Investigation of Mineral
Surface Phenomena - Probing Depth .......... 205
4-2. Sample Handling Techniques. . . . . . . . . . . . . . . 206
4-3. Analytical Applications ................. 211
4-4. Electron Take-Off (Grazing) Angle Analysis Applications 216
4-5. Qualitative Bonding Investigations 220
4-6. Summary 241
References . . . . . . . . . . . . . . . 242
5. THE APPLICATION OF NMR TO THE STUDY OF
CLAY MINERALS - J.J. Fripiat ..... 245
5-1. Introduction: Fundamentals of NMR 245
5-2. The Bloch Equations ........ . 254
5-3. Line Shape . . . . . . . . . . . . . . 262
5-4. Relaxation Mechanisms ...... . 282
5-5. Review of Some Problems: Order and Disorder
in Adsorbed Water Molecules 303
References . . . . . . . . . . . . . . . . . . . . . . 314
6. DISTRIBUTION OF IONS IN THE OCTAHEDRAL SHEET OF
MICAS - W.E.E. Stone and J. Sanz 317
6-1. Introduction . . . . . . . 317
6-2. Influence of the Fe2+ Ions 318
6-3. H+ Spectra of Phlogopites 319
6-4. H+ Spectra of Biotites .. 321
6-5. F- Spectra . . . . . . . . 322
6-6. Correlation with I. R. Results . 324
References . . . . . . . . . . . . . 328
7. GENERAL THEORY AND EXPERIMENTAL ASPECTS OF
ELECTRON SPIN RESONANCE - Jacques C. Vedrine 331
7-1. Introduction .... . 331
7-2. G-Factor Tensor ... . 340
7-3. Hyperfine Interaction . 353
7-4. Analysis of ESR Spectra 362
7-5. Fine Structure .... . 368
7-6. Summary ....... . 373
Appendix 7-1 375
Appendix 7-2 377
Appendix 7-3 381
References . . 386
TABLE OF CONTENTS vii
8. APPLICATIONS OF ESR SPECTROSCOPY TO INORGANIC-CLAY
SYSTEMS - Thomas J. Pinnavaia 391
8-1. Introduction . . . . . . . . . . . 391
8-2. Surface-Bound Metal Ions .... 391
8-3. Framework Paramagnetic Centers 407
References . . . . . . . . . . . . . . . 419
9. APPLICATION OF SPIN PROBES TO ESR STUDIES OF
ORGANIC-CLAY SYSTEMS - Murray B. McBride 423
9-1. Nitroxide Spin Probes - Origin of
the ESR Spectrum . . . . ..... . 423
9-2. Nitroxides in Low-Viscosity Media -
Rapid Isotropic Motion ...... . 427
9-3. Nitroxides in High-Viscosity Media 429
9-4. Nitroxides Adsorbed on Clay Surfaces 437
9-5. Experimental Considerations in Using
Nitroxide Spin Probes 447
References . . . . . . . . . . . . . . . . . 449
10. APPLICATIONS OF PHOTOACOUSTIC SPECTROSCOPY TO THE STUDY
OF SOILS AND CLAY MINERALS - Raymond L. Schmidt 451
10-1. Introduction. . 451
10-2. Instrumentation 454
10-3. Results 456
10-4. Conclusions 463
References . . . . 465
INDEX. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 467
PREFACE
During the past few years there has been a marked increase in the use of
advanced chemical methods in studies of soil and clay mineral systems, but only a
relatively small number of soil and clay scientists have become intimately associ
ated and acquainted with these new techniques. Perhaps the most important
obstacles to technology transfer in this area are: 1) many soil and clay chemists
have had insufficient opportunities to explore in depth the working principles of
more recent spectroscopic developments, and therefore are unable to exploit the
vast wealth of information that is available through the application of such ad
vanced technology to soil chemical research; and 2) the necessary equipment gen
erally is unavailable unless collaborative projects are undertaken with chemists and
physicists who already have the instruments. The objective of the NATO Advanced
Study Institute held at the University of Illinois from July 23 to August 4, 1979,
was to partially alleviate these obstacles. This volume, which is an extensively
edited and reviewed version of the proceedings of that Advanced Study Institute, is
an essential aspect of that purpose. Herein are summarized the theory and most
current applications of six different spectroscopic methods to soil and/or clay
mineral systems. The instrumental methods examined are Mossbauer, neutron
scattering, x-ray photoelectron (XPS, ESCA), nuclear magnetic resonance (NMR),
electron spin resonance (ESR, EPR), and photoacoustic spectroscopy. Contributing
authors were also lecturers at the Advanced Study Institute, and are each well
known and respected authorities in their respective disciplines.
The importance and timeliness of using modern chemical methods in soil and
clay research was emphasized recently by Dr. R.C. McKenzie in his plenary address
at the Sixth International Clay Conference (Oxford, 1978), in which he referred to
several of these methods as holding much promise for opening new horizons. This
importance was also recognized in a symposium on "New Methods in Soil Min
eralogical Investigations," sponsored by the Soil Science Society of America in
1977, in which two of these methods were discussed. The number of scientific
publications using these methods to study soils and clays is increasing at a rapid
rate, and the time is right to collect into one volume a detailed discussion of all of
these methods. It is hoped that in doing this, a critical void in the scientific
literature will be filled, and that the ability of earth scientists to take advantage of
a greater variety of research instruments for solving difficult problems will thereby
be increased.
Special acknowledgement is made to the following publishers for their gener
osity in permitting reproduction of figures: Academic Press, Inc.; Almquist and
Wiksell International; American Chemical Society; American Institute of Physics;
American Mineralogist; American Physical Society; American Society of Agron-
ix
J. It!. Stucki and W. L. Banwart reds.), Advanced Chemical Methods for Soil and Clay Minerals Research, ix-x.
Copyright © 1980 by D. Reidel Publishing Company.
x PREFACE
omy; American Vacuum Society; Blackwell Scientific Publications, Ltd.; Cam
bridge University Press; The Chemical Society; The Clay Minerals Society; Elevier
Scientific Publishing Company; Gauthier-Villars; Harper and Row Publishers, Inc.;
Institut Max von Laue-Paul Langevin; International Atomic Energy Agency; John
Wiley and Sons, Inc.; The Macauley Institute for Soil Research; Macmillan (Jour
nals) Ltd.; McGraw-Hili Book Company; Masson; The Mineralogical Society; Min
eralogical Society of America; North-Holland Publishing Co.; Oxford University
Press; Pergamon Press, Inc.; Plenum Publishing Corporation; Program for Scientific
Translation; Societe Chimique de France; Springer-Verlag; United Kingdom Atomic
Energy Authority; and Zeitschrift fur Kristallographie.
The editors express deep and sincere gratitude to Judith Kutzko for type
setting the camera-ready manuscript; and to Sandra Ripplinger who spent many
hours proofreading and correcting the individual chapters. We acknowledge the
support and magnificent assistance of Dr. Carol Holden and the Division of Con
ferences and Institutes at the University of Illinois, without whom the Advanced
Study Institute and this volume could never have become reality. We also express
appreciation to Dr. R.W. Howell, Head of the Agronomy Department, and to other
members of the Department who offered much encouragement during the many
weeks of preparing this work. Finally, we again thank the authors who contributed
so generously of their time and talents to make this work worthwhile.
J.W. Stucki
W. L. Banwart
July, 1980
Chapter 1
MOSSBAUE R SPECTROSCOPY
Bernard A. Goodman
Department of Spectrochemistry
The Macaulay Institute for Soil Research
Aberdeen AB9 20J, United Kingdom
1-1. INTRODUCTION TO THE MOSSBAUER EFFECT
The 'Y-radiation emitted by nuclei in excited states, formed as a result of
radioactive decay of unstable parent nuclei, may subsequently be reabsorbed by
other nuclei of the same type. If the emitting nucleus is assumed to be moving with
a velocity, V, so that the linear momentum of the system is mY, where m is the
mass of the nucleus, then, after emission of the 'Y-ray, the linear momentum of the
system, which comprises the 'Y-ray plus de-excited nucleus, must still equal mV
(conservation of momentum). Thus the momentum of the 'Y-ray, E/c, must be
balanced by a change in the velocity of the nucleus so that,
mV = E'Y/c + m(V+v) [ 1-11
and v is thus equal to --E'Y/mc and is independent of the initial velocity of the
atom.
Also considering the conservation of energy, the kinetic energy of the nu
cleus before emission of the 'Y-ray is %mV2 and after emission is %m(V+v)2. Thus
the difference in energy, /j E, between the nuclear transition energy and that of the
emitted 'Y-ray is given by
/j E = %mv2 + m Vv [1-21
%mv2 = E 2/2mc2 = E [1-31
'Y r
where Er is the free atom recoil energy and is independent of the velocity of the
nucleus. Recoil of the nucleus also occurs on absorption of radiation and resonant
absorption can only occur if overlap exists between the energy profiles of the
emitted and absorbed 'Y-rays.
With free atoms the recoil energy, Er, is much greater than the widths of
these absorption profiles (Fig. 1-11. If the nuclei are held in a lattice in which the
characteristic energy of the lattice vibrations (the phonon energy) is greater than
J. W. Stucki and W. L. Banwart (eds.), Advanced Chemical Methods for Soil and Clay Minerals Research, 1-92.
Copyright © 1980 by D. Reidel Publishing Company.