Handbook of Thermal Analysis and Calorimetry, Volume 2: Applications to inorganic and miscellaneous materials (Handbook of Thermal Analysis and Calorimetry)

943 Pages·2003·39.15 MB·English

by  Michael E. Brown

APPLICATIONS TO INORGANIC AND
MISCELLANEOUS MATERIALS
HANDBOOK OF
THERMAL ANALYSIS
AND CALORIMETRY
SERIES EDITOR
PATRICK K. GALLAGHER
DEPARTMENT OF CHEMISTRY
OHIO STATE UNIVERSITY
USA
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HANDBOOK OF
THERMAL ANALYSIS
AND CALORIMETRY
VOLUME 2
APPLICATIONS TO INORGANIC AND
MISCELLANEOUS MATERIALS
EDITED BY
MICHAEL E. BROWN
DEPARTMENT OF CHEMISTRY
RHODES UNIVERSITY
GRAHAMSTOWN 6140
SOUTH AFRICA
PATRICK K. GALLAGHER
DEPARTMENT OF CHEMISTRY
OHIO STATE UNIVERSITY
USA
2003
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FOREWORD
The applications and interest in thermal analysis and calorimetry have grown
enormously during the last half of the 20th century. The renaissance in these
methods has been fuelled by several influences. Certainly the revolution in
instrumentation brought on by the computer and automation has been a key
factor. Our imaginations and outlooks have also expanded to recognize the
tremendous versatility of these techniques. They have long been used to
characterize materials, decompositions, and transitions. We now appreciate the
fact that these techniques have greatly expanded their utility to studying many
processes such as catalysis, hazards evaluation, etc. or to measuring important
physical properties quickly, conveniently, and with markedly improved accuracy
over that in the past.
Consequently, thermal analysis and calorimetry have grown in stature and
more scientists and engineers have become, at least part time, practitioners. It is
very desirable that these people new to the field can have a source of
information describing the basic principles and current state of the art. Examples
of the current applications of these methods are also essential to spur recognition
of the potential for future uses. The application of these methods is highly
interdisciplinary and any adequate description must encompass a range of topics
well beyond the interests and capabilities of any single investigator. To this end,
we have produced a convenient four volume compendium of such information
(a handbook) prepared by recognized experts in various aspects of the topic.
Volume 1 describes the basic background information common to the broad
subject in general. Thermodynamic and kinetic principles are discussed along
with the instrumentation and methodology associated with thermoanalytical and
calorimetric techniques. The purpose is to collect the discussion of these general
principles and minimize redundancies in the subsequent volumes that are
concerned with the applications of these principles and methods. More unique
methods which pertain to specific processes or materials are covered in later
volumes.
The three subsequent volumes primarily describe applications and are divided
based on general categories of materials. Volume 2 concerns the wide range of
inorganic materials, e.g., chemicals, ceramics, metals, etc. It covers the
synthesis, characterization, and reactivity of such materials. Similarly, Volume 3
pertains to polymers and describes applications to these materials in an
appropriate manner. Lastly the many important biological applications are
described in Volume 4.
Each of these four volumes has an Editor, who has been active in the field for
many years and is an established expert in the material covered by that specific
volume. This team of Editors has chosen authors with great care in an effort to
produce a readable informative handbook on this broad topic. The chapters are
not intended to be a comprehensive review of the specific subject. The intent is
that they enable the reader to glean the essence of the subject and form the basis
for further critical reading or actual involvement in the topic. Our goal is to spur
your imaginations to recognize the potential application of these methods to
your specific goals and efforts. In addition we hope to anticipate and answer
your questions, to guide you in the selection of appropriate techniques, and to
help you to perform them in a proper and meaningful manner.
PATRICK K. GALLAGHER
Series Editor
vii
PREFACE TO VOLUME 2
This volume contains fifteen chapters on the applications of the techniques of
thermal analysis and calorimetry to the study of mainly inorganic materials.
Contributions were invited on the basis of the expertise of the authors in each
particular area. Some overlap between chapters has been unavoidable, but the
differences in points-of-view do add to the interest. In the absence of a better
way of arranging the chapters they have been placed in alphabetical order to
emphasize, at least, the vast range of materials - from adsorbents to
superconductors - to which the techniques of thermal analysis and calorimetry
have been successfully applied.
Production of the volume has been slow, for a variety of reasons, but it is hoped
that the final result will be worth the long wait. Some of the contributors joined
the project at an advanced stage after some of the original authors had
withdrawn for various reasons. To those model authors who worked entirely to
schedule and then had to wait for a long time for their work to appear, our
sincere apologies.
MICHAEL E. BROWN
PATRICK K. GALLAGHER
Volume Editors
This Page Intentionally Left Blank
CONTENTS
Foreword- P.K. Gallagher v
Preface - M.E. Brown and P.K. Gallagher vii
Contributors xxi
Acknowledgements
XXV
CHAPTER 1. APPLICATIONS OF THERMAL ANALYSIS AND
CALORIMETRY IN ADSORPTION AND SURFACE CHEMISTRY
(Philip L. Llewellyn)
1. INTRODUCTION 1
2. IMMERSION CALORIMETRY 1
2.1. Introduction 1
2.2. Immersion calorimetry for the estimation of the surface area of a solid:
the modified Harkins and Jura method 3
2.3. Immersion calorimetry for an evaluation of the chemical nature of the
surface 6
2.4. Immersion calorimetry for the evaluation of microporosity 7
2.5. Intrusion of non-wetting fluids 10
3. THERMOPOROMETRY 11
4. SAMPLE CONTROLLED THERMAL ANALYSIS (SCTA) 14
5. ISOTHERMAL ADSORPTION MICROCALORIMETRY 22
5.1. Introduction 22
5.2. Adsorption calorimetry for the characterisation of heterogeneous
adsorbents 30
5.3. Adsorption calorimetry for the characterisation of homogeneous
adsorbents 35
5.4. Adsorption calorimetry for the detection of adsorbate phase
transitions 37
5.5. Adsorption calorimetry to follow the various stages of micropore
filling 40
5.6. Adsorption calorimetry in capillary condensation 42
REFERENCES 43