Table Of ContentClay Mineralogy:
Spectroscopic and Chemical
Determinative Methods
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Clay Mineralogy:
Spectroscopic and Chemical
Determinative Methods
Edited by
J.
M. Wilson
FRSE
Head, Division of Soils
Macaulay Land Use Research Institute
Craigiebuckler
Aberdeen, UK
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V
First edition 1994
Reprinted 1995,1996
© 1994 Springer Science+Business Media Dordrecht
Origina1ly published by Chapman & HalI in 1994
Softcover reprint ofthe hardcover Ist edition1994
Typeset in 1O/12pt Palatino by Pure Tech Corporation, Pondicherry, India
ISBN 978-94-010-4313-7 ISBN 978-94-011-0727-3 (eBook)
DOI 10.1007/978-94-011-0727-3
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Contents
Preface ix
List of contributors xi
1 Molecular spectroscopy: introduction and general 1
principles (B. A. Goodman)
1.1 Background 1
1.2 Absorption spectroscopy 3
1.3 Emission spectroscopy 4
1.4 Spectral intensity 4
1.5 Spectral peak widths 5
1.6 Spectral resolution 5
1.7 Signal-to-noise optimization 7
1.8 Spectral editing and analysis 8
Acknowledgement 10
2 Infrared methods 0. D. Russell and A. R. Fraser) 11
2.1 Introduction 11
2.2 Principles 11
2.3 Instrumental requirements 12
2.4 Preparative methods and pretreatments 15
2.5 Identification and characterization of clay minerals and
associated minerals 18
2.6 Interpreting the IR spectra of clay materials 57
2.7 Quantitative analysis 61
2.8 Computer-aided methods 62
Acknowledgement 64
References 64
3 Mossbauer spectroscopy (B. A. Goodman) 68
3.1 Introduction 68
3.2 Principles of M6ssbauer spectroscopy 70
3.3 Instrumentation and experimental techniques 77
3.4 M6ssbauer spectroscopy of oxide minerals 82
3.5 M6ssbauer spectroscopy of aluminosilicate minerals 96
3.6 Phosphate minerals 110
VI Contents
3.7 Applications of M6ssbauer spectroscopy in archaeology
and art 111
3.8 Conclusions 112
Acknowledgements 114
References 114
4 Nuclear magnetic resonance spectroscopy
( B. A. Goodman and J. A. Chudek) 120
4.1 Introduction 120
4.2 Principles of NMR spectroscopy 122
4.3 Experimental techniques 134
4.4 General features of MAS NMR spectra of minerals 142
4.5 High-resolution NMR spectroscopy of clay minerals 149
4.6 Clay surface studies 157
4.7 Structural distribution of paramagnetic ions 165
4.8 Conclusions 167
Acknowledgements 168
References 169
5 Electron paramagnetic resonance spectroscopy
(B. A. Goodman and P. L. Hall) 173
5.1 Introduction to electron paramagnetic resonance 173
5.2 Electrons in transition metal ions 178
5.3 The case of two or more unpaired electrons: fine structure 183
5.4 Nuclear hyperfine coupling 193
5.5 Experimental procedures 195
5.6 Applications 200
5.7 Conclusions 219
Acknowledgements 221
References 221
6 X-ray photoelectron spectroscopy (E. Paterson and
R. Swaffield) 226
6.1 Introduction 226
6.2 Fundamental aspects 227
6.3 Experimental aspects 230
6.4 Information content 240
6.5 Applications in clay mineralogy 247
6.6 Conclusions 255
Acknowledgements 255
References 255
7 X-ray fluorescence spectroscopy and microanalysis
(D. C. Bain, W. J. McHardy and E. E. Lachowski) 260
7.1 Introduction 260
Contents vii
7.2 General principles 261
7.3 X-ray fluorescence spectrometry 265
7.4 Microanalysis with SEM 273
7.5 Analytical electron microscopy 281
7.6 Conclusions 294
Acknowledgement 294
References 294
8 Chemical analysis (D. C. Bain and B. F. L. Smith) 300
8.1 Introduction 300
8.2 Sample preparation 301
8.3 Methods of major elemental analysis 304
8.4 Analysis for ferrous iron 308
8.5 Exchange capacity 312
8.6 Determination of a structural formula 317
References 327
9 Characterization of poorly ordered minerals by selective
chemical methods (B. F. L. Smith) 333
9.1 Introduction 333
9.2 Principles 334
9.3 Selective chemical methods 335
9.4 Comparison of methods 350
References 353
Index 359
Preface
A knowledge of clay is important in many spheres of scientific endeav
our, particularly in natural sciences such as geology, mineralogy and soil
science, but also in more applied areas like environmental and mater
ials science. Over the last two decades research into clay mineralogy has
been strongly influenced by the development and application of a num
ber of spectroscopic techniques which are now able to yield information
about clay materials at a level of detail that previously would have
seemed inconceivable. This information relates not only to the precise
characterization of the individual clay components themselves, but also
to the ways in which these components interact with a whole range of
absorbate molecules. At present, however, the fruits of this research are
to be found principally in a somewhat widely dispersed form in the
scientific journals, and it was thus considered to be an appropriate time
to bring together a compilation of these spectroscopic techniques in a
way which would make them more accessible to the non-specialist. This
is the primary aim of this book. The authors of the various chapters first
describe the principles and instrumentation of the individual spectro
scopic techniques, assuming a minimum of prior knowledge, and then
go on to show how these methods have been usefully applied to clay
mineralogy in its broadest context. The book concludes with two chap
ters describing a purely chemical approach to the characterization of
clays which, although somewhat traditional, is nevertheless considered
to be a useful adjunct to the sophisticated physical techniques described
beforehand. The philosophy throughout the book has been to try to
strike a balance between an introductory text and a research compen
dium so that it may be useful to scientists with no previous experience of
clays as well as to those who are familiar with the problems of investigat
ing these difficult materials. This approach is similar to that adopted in a
previous book of this kind (A Handbook of Determinative Methods in Clay
Mineralogy, 1987, edited by M. J. Wilson, Blackie, Glasgow) which is now
out of print, and in fact Chapters 2, 8 and 9 are updated versions from
this work. All other chapters are, however, completely new.
Most of the authors are, or have been, associated with the Macaulay
Land Use Research Institute in Aberdeen, which has had a long and
distinguished history of research into soil mineralogy. Despite recent
x Preface
difficulties occasioned by financial constraints, soil mineralogy is identi
fied in the Institute's mission statement as an area which it is regarded as
important to develop in an international context. It is hoped that this
book may be of some assistance in the fulfilment of this aspiration.
Finally, we are most grateful to the Director of MLURI, Professor
T. J. Maxwell, for allowing us to undertake and complete this book with
the minimum of formalities. We also thank Mrs. Aileen Stewart for the
time and effort she has devoted to processing the manuscript.
M. J. Wilson
Macaulay Land Use Research Institute
Aberdeen
Contributors
D. C. Bain, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
J. A. Chudek, Department of Chemistry, University of Dundee, Dundee
DD14HN
A. R. Fraser, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
B. A. Goodman, Scottish Crops Research Institute, Invergowrie, Dundee
DD25DA.
P. L. Hall, Schlumberger, PO Box 153, Cambridge CB2 3BE.
E. E. Lachowski, Department of Chemistry, University of Aberdeen
AB92UE
W. J. McHardy, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
E. Paterson, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
J. D. Russell, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
B. F. L. Smith, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
R. Swaffield, Macaulay Land Use Institute, Craigiebuckler, Aberdeen
AB92QJ.
CHAPTER 1
Molecular spectroscopy:
introduction and general
principles
B. A. Goodman
1.1 BACKGROUND
Molecular spectroscopy involves the interaction of electromagnetic radi
ation with materials in order to produce an absorption pattern (i.e. a
spectrum) from which structural or compositional information can be
deduced. Electromagnetic radiation is conventionally, and rather arbi
trarily, divided into a number of distinct regions, each of which covers a
range of energies that corresponds to a different type of molecular pro
cess (Figure 1.1). In order of increasing frequency these are:
1. Radiofrequency (c. 105 - 109 Hz). This corresponds to the energy in
volved in changing the direction of spin of a nucleus (nuclear mag
netic resonance, NMR).
2. Microwave (c. 109 to 3 X 1010 Hz). This range covers the energy in
volved in changing the direction of electron spin (electron paramag
netic resonance, EPR, also known as electron spin resonance, ESR)
and the separations between rotational energy levels of gaseous
molecules.
3. Infrared (c. 3 x 1010 to 3 X 1014 Hz). Separations between vibrational
energy states occur in this region, in which the techniques of infrared
absorption and Raman spectroscopy occur.
4. Visible and ultraviolet (c. 3 x 1014 to 3 X 1016 Hz). This region cor
responds to the separations between the energy levels of valence
electrons.
Clay Mineralogy: Spectroscopic and Chemical Determinative Methods.
Edited by M. J. Wilson. Published in 1994 by Chapman & Hall, London.
ISBN 0 412 53380 4.
