C. Ekberg — Hydrolysis of Metal Ions (2016)

Автор: C. Ekberg
Название книги: Hydrolysis of Metal Ions (2016)
Формат: PDF
Жанр: Химия
Страницы: 945
Качество: Изначально компьютерное, E-book

Filling the need for a comprehensive treatment that covers the theory, methods and the different types of metal ion complexes with water (hydrolysis), this handbook and ready reference is authored by a nuclear chemist from academia and an industrial geochemist.
The book includes both cation and anion complexes, and approaches the topic of metal ion hydrolysis by first covering the background, before proceeding with an overview of the dissociation of water and then all different metal-water hydrolysis complexes and compounds.

If gold has been prized because it is themost inert element, changeless and
incorruptible,water is prized for the opposite reason – its fluidity, mobility,
changeabilitymake it a necessity and a metaphor for life itself. To value gold
over water is to value economy over ecology, that which can be locked up
over that which connects all things.
Rebecca Solnit – Storming the Gates of Paradise, Landscapes for Politics
Water is a weak acid.Theacidity ofwater molecules in the hydration sphere
of a metal ion is much larger than that of water itself. This enhancement
of the acidity may be interpreted qualitatively as the result of repulsion
of the protons of the water molecules by the positive charge of the metal
ion. The acidity will increase as the metal ion size decreases and its charge
increases.
Werner Stumm and James Morgan – Aquatic Chemistry
Numbers are the product of counting. Quantities are the product of
measurement. This means that numbers can conceivably be accurate
because there is a discontinuity between each integer and the next.
Between two and three there is a jump. In the case of quantity, there is
no such jump; and because jump is missing in the world of quantity, it is
impossible for any quantity to be exact. You can have exactly three tomatoes.
You can never have exactly three gallons of water. Always quantity is
approximate.
Gregory Bateson – Number is Different from Quantity
Water and metals are ever present. Water has the power to erode any material
that might contain themetals, thereby releasing them into the water.The liberated
metals can hydrolyse the water, releasing protons, the hydroxide binding to the
metal. All metals can undergo this process. Nature has conspired to make many
of these processes essential for life itself, utilising the unique features of some metal ions within essential mechanisms in plants and animals. Conversely, nature
also conspires to make just as many of these processes able to destroy life. Moreover,
the processes are important in many other scientific and industrial fields.
Consequently, knowledge of hydrolytic reactions and their magnitude is seen as
being essential.
The study of hydrolysis reactions was pioneered within two preeminent institutions.
The first was at the Royal Institute of Technology in Stockholm, Sweden,
founded by the work of Lars Gunnar Sillén. His group entitled their work ‘Studies
on the Hydrolysis of Metal Ions’. The second group hailed from the Oak Ridge
National Laboratory (ORNL) in the United States. The driving force of this work
was by Charles Baes and Bob Mesmer who wrote the seminal book ‘The Hydrolysis
of Cations’.This book has been an invaluable tool for aqueous chemists over
several scientific generations. Although hydrolysis work at ORNL preceded Baes
andMesmer, it was their work that cemented the institution as preeminent in the
field. Subsequently, their work was continued by Don Palmer and others. One of
the present authors had the pleasure to spend part of their PhD dissertation work
at ORNL under the guidance of Baes, Mesmer and Palmer.The title for this book
‘Hydrolysis of Metal Ions’ has been adopted in honour of the work of these two
groups.
About 20 years ago, the authors started their collaboration on the hydrolysis
of tetravalent metal ions and since then have continued to work together in
several areas of aqueous chemistry. Some 10 years ago, we realised that there
had been significant progress in the art of hydrolysis constant determination
and that many new studies were available. Thus, we decided to try to compile
the progress in the area. In our attempt to create a new ‘Baes and Mesmer’, we
have tried to approach hydrolysis from a thermodynamic standpoint, that is,
by first trying to go through the concept of activities instead of concentrations
and discuss the different models developed for assessing activities and inevitably
the method of obtaining activity coefficients. Using these activity coefficients,
the obtained stability constants can be calculated back to a standard state for
comparison and general utilisation, that is, infinite dilution at 25 ∘C and 105 Pa
pressure.
A comprehensive collection of data as presented in this book cannot be undertaken
without the help of many people.We would like to express our gratitude to
the personnel at the library of Chalmers University of Technology for their ability
to trace papers we never thought were available, Natallia Torapava and Artem
Matyskin for their help with translation of very important papers written in Russian
and Teodora Retegan for her help with finding papers as well as helping with
translations from Romanian and Italian.We would also like to sincerely thank our
families, Teodora, Susan, Tara and Liam, for their understanding and patience at
the very many long nights collating, interpreting and writing about stability and
solubility constant data. For those who helped and have not been mentioned, you
are still not forgotten. We hope that this book will provide a good companion to scientific work that
describes the hydrolysis of metal ions in the same way as Baes and Mesmer’s
version was helpful to us as we did our hydrolysis work over the last three
decades.
January 2016