Fundamentals of radiochemistry

439 Pages·1993·19.29 MB·English

by  Adloff

FUNDAMENTALS
OF
RADIOCHEMISTRY

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Library of Congress Cataloging-in-Publication Data
Adloff, J.-P. (Jean-Pierre)
Fundamentals of radiochemistry / Jean-Pierre Adloff, Robert Guillaumont.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-4244-9
1. Radiochemistry. I. Guillaumont, R. (Robert) II. Title.
QD601.2.A35 1993
541.3’8--dc20 92-29544
A Library of Congress record exists under LC control number: 92029544
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ISBN 13: 978-1-315-89309-9 (hbk)
ISBN 13: 978-1-351-07219-9 (ebk)
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FOREWORD
Very few books devoted to the basis of radiochemistry have been published
in the last two decades. During this period the orientation of the subject has
changed very substantially. A new work, with a different approach is to be
welcomed wholeheartedly.
The classical treatises on this subject devoted much of their text to the
properties of radiation and the measurement of radioactivity. The behavior
of species present at tracer concentrations was usually treated in a rather
descriptive manner aimed mainly at the separation and concentration of the
trace species.
In this book it is assumed that the methods of measurement of radioactivity
are known. Its principal objective is to demonstrate the usefulness of radio-
chemistry in most areas of chemistry and to describe the physicochemical
behavior of systems containing one or more compounds at tracer or sub-tracer
concentration.
The authors have carried out a critical and thorough analysis of the principles
and applications of radiochemical methods and have emphasized many aspects
of radioactivity and chemistry that are often overlooked.
This may be the first book to treat the question of what chemical information
can be obtained with sub-tracer amounts, i.e., systems containing a few,
perhaps only one, radioactive atom.
The topic of speciation, identification of chemical form, of radionuclides
present at tracer concentrations, has achieved considerable importance in
recent years, because of its relevance to the control of nuclear wastes. In this
book, speciation of the radioactive component is treated as the main objective
of radiochemical operations.
The pedigree of this book is impeccable: Professor Adloff was a pupil of
Marguerite Perey at the University of Strasbourg and Professor Guillaumont
studied at the Institut du Radium and at the Arcueil Laboratories in Paris
under the guidance of MOIse Haissinsky and Georges Bouissieres.
The authors have succeeded in their ambition to present a modem and
original view of radiochemistry and their extensive practical experience en-
sures that their approach to the subject is successful.
Alfred G. Maddock
University Chemical Laboratory
Cambridge, U.K.

PREFACE
Many books have been written on the subjects of the nucleus and radio-
activity, delineating their importance in various fields of fundamental or
applied science. Some of these treatises deal specifically with relationships
between radioactivity and chemistry, introducing with various degrees of
pertinence and precision the term "radiochemistry" in an effort to establish
useful interdisciplinary connections. Unfortunately, the result frequently leads
to confusion; as yet, only a few authors have effectively succeeded in outlining
the true scope of radiochemistry and defining its position within the larger
context of chemistry in general. A ware of this need, we have attempted to
overcome at least part of the difficulty in the present book. This original
treatise is the result of a critical consideration of the fields of chemistry covered
by radiochemistry, which is examined in its own right on the basis of its
fundamental principles, objectives, and methods.
Modem radiochemistry is defined as the study of chemical properties of
matter under conditions for which the classical methods of physical chemistry
no longer apply and recourse to techniques of radioactivity is required. This
is particularly true for elements that are present at extremely high dilution
and which can only be detected and investigated with the aid of characteristic
radiations emitted by representative radionuclides. In other terms, radiochem-
istry embodies the use of radioactivity in the elucidation of chemical phe-
nomena.
The fields and concepts described are essentially those that are less familiar
to chemists in general, and examples are provided that include the chemistry
of ephemeral radionuclides, actinides of high atomic number, positronium,
and thermodynamic and kinetic considerations at the tracer level and at the
scale of only one or several atoms.
Radiochemical methods are defined in terms of analysis of chemical in-
formation conveyed by radiation; they are considered and discussed in a
unified manner adapted primarily to situations encountered in radiochemistry,
but which can also be extended to other fields. It is shown how this information
has already contributed to various aspects of fundamental physical chemistry
and how it can be applied to problems of speciation in systems relative to
the environment.
This book is addressed to a wide range of chemists and environmental
scientists not having specialized knowledge in the field. Characteristics of
radioactivity and radioactive matter are presented that are useful to the chem-
ist. The treatise is also recommended for practitioners in radiochemistry re-
quiring to update their knowledge. It is of particular interest to research
workers dealing with fundamental and applied aspects of matter at extreme
dilution as encountered in the dissemination of stable and radioactive wastes,
in living organisms and in space. The material has been presented in a form
suitable for use as a textbook or aid for special courses in physical and
analytical chemistry.
Our conception of radiochemistry is the result of numerous discussions and
exchanges with our colleagues from the international community of radio-
chemistry and nuclear chemistry. One of us acknowledges the continuing
intellectual support of close collaborators of the Group of Radiochemistry at
the Institut de Physique Nucleaire in Orsay.
We wish to express our deep gratitude to Professor Alfred G. Maddock for
having accepted, with enthusiasm, revision of the manuscript. His critical
insight and numerous constructive comments have largely contributed to the
achievement of our endeavor.
Throughout the two years during the preparation of the manuscript we were
assisted by Dr. John MacCordick. Tirelessly, with a rare degree of patience
and conscientiousness, he corrected and amended the successive versions and
helped us to avoid many errors. It is our pleasant duty to thank him for his
linguistic expertise and for many fruitful discussions. Whatever errors remain
are, of course, the responsibility of the authors.
The sections on positron and positronium have been prepared with com-
petence by Dr. Gilles Duplatre, a recognized expert in the field. We gratefully
acknowledge his valuable contribution.
Special thanks are due to Dr. Xavier Talmont for providing recent data and
to Mrs. Simone Bouby for careful preparation of the illustrations.
Jean-Pierre Adloff
Strasbourg, France
Robert Guillaumont
Orsay, France
THE AUTHORS
Jean-Pierre Adloff, D.Se., is titular Professor of Nuclear Chemistry at
the University Louis Pasteur in Strasbourg, France and former Vice-Director
of the Nuclear Research Center and Director of the Laboratory of Nuclear
Chemistry in Strasbourg.
He received a diploma in Chemical Engineering from the Higher School
of Chemistry in Strasbourg in 1951 and a D.Sc. from the University of
Strasbourg in 1958. He prepared his doctorate with Marguerite Perey, dis-
coverer of the element francium, and former assistant of Marie Curie.
J.-P. Adloff is author or co-author of 130 papers on radiochemistry, hot
atom chemistry, radiation chemistry, and Mossbauer spectroscopy. His in-
terest encompasses all aspects of fundamental and applied radiochemistry and
education in these fields. He is co-author with M. Haissinsky of Radiochem-
ical Survey of the Elements and with I. and Z. Draganic of Radiation and
Radioactivity on Earth and Beyond. He is co-editor of the Handbook of Hot
Atom Chemistry and of the journal Radiochimica Acta.
As a participant in international educative programs of UNESCO and IAEA,
he has given extensive courses on radiochemistry in Mexico, Brazil, Paraguay,
Ecuador, Kenya, and Thailand. He has acted as an expert of IAEA for
development of research in radiochemistry at the Universities of Chiang Mai
in Thailand and of Asuncion in Paraguay. He was a UNESCO expert at the
University of Viscosa in Brazil.
J.-P. Adloff is a member of the division of Nuclear Chemistry of the
American Chemical Society, of the French Chemical Society, and of the
French Society for Nuclear Energy. He is a member of several international
committees for conferences on Radiochemistry and Hot Atom Chemistry, and
of the committee of the biennial Mexican Symposium on Radiochemistry.
J.-P. Adloff has received an award from the French Academy of Science
and has been nominated Dr. Honoris Causa of the University of Asuncion.
He is presently Chairman of the IUPAC commission on Radiochemistry and
Nuclear Techniques.