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The contributions to this volume focus on selected chemical aspects of rare-earth materials. The topics covered range from a basic treatment of crystalline electric-field effects and chemical interactions in organic solvents, to separation processes, electrochemical beaviors which impact corrosion, oxidation resistance, chemical energy storage and sensor technology, and to analytical procedures. Underlying the most subtle chemical and optical properties of these elements and their compounds in the condensed state are the crystal field effects. This phenomenon in non-metallic compounds is discussed in chapter six. The volume opens with a review of important new solvent extraction procedures as well as emerging alternative separation processes such as photochemical separation, precipitation stripping and supercritical extraction. Scientific and industrial procedures are illustrated. In a further chapter eight major analytical techniques of obtaining accurate trace analysis are examined, tabulated and assessed. The most effective procedures of each are also reviewed. Chapter two considers a wide variety of methods using rare-earth solutions and slats to modify advantageously the costly deterioration of metals and alloys. This topic is expanded in the following chapter, paying particular attention to protection against high-temperature oxidation, sulfidization and hot-salt corrosion. The following two chapters are concerned with the versatility of the rare earths in addressing current technical problems such the use of rare-earth intermetallics, principally LaNi3-based materials, to provide the skyrocketing need for environmetally friendly, usually portable, battery power. The final chapter is a review of the solvation, interaction and coordination of rare-earth salts in a variety of organic solvents including dimethylacetamide, dimethylsulfoxide, various alcohols, acetonitrile and propylenecarbonate under strict anhydrous conditions. A contrast of these interactions with those in which water is present with organic solvents is also made.
Volume 15 in this series continues the voyage of discovery started almost a decade ago. Chapter 98 adds significantly to an evaluation of systematic, experimental low-temperature studies of the ambivalent behaviours of cerium (ferromagnetism, antiferromagnetism, spin glass, superconductivity etc.) which depend upon its environment in materials. The conclusions arrived at should provide new data against which the theory can be advanced. The next chapter provides a review of rare earth carbides, emphasizing the thermodynamics, phase diagrams, crystal structures and physical properties. The binary rare earth carbides present an exceptionally wide range of compositions and structures both as solids and gas-phase molecules. Complex carbides with additional metal and non-metal components also receive attention. Metal-rich halides (i.e. compounds with an X/R ratio <2) are the subject of the next chapter. The compounds are classified according to their structure and chemical bonding characteristics and their electrical and magnetic properties are also reviewed. Chapter 101 deals with the preparation, structure, chemical and physical properties of heavy-metal fluoride glasses. Large amounts of rare earths can be added into these, and they possess a great potential for optical applications in the mid-infrared range as fiber optic glasses for communication and transmission of information, optical wave guides, fiber lasers and sensors. The following chapter explores the chemical kinetics of solvent and ligand exchange in aqueous lanthanide solutions. A wealth of tabulated information on rate and equilibrium constants is provided in textual and tabular form. Chapter 103 considers the fundamentally important reactions of the lanthanide ions with water. These interactions are discussed for both solids and solutions. The hydrated species are considered in detail for the aqueous solution, revealing the consequences of the lanthanide series sequence. The concluding chapter reviews macrocyclic complexes formed by rare earth and dioxouranium ions as templates. Synthetic trends and reactivity are considered as well as potential uses of these intriguing wrap-around structures.
This continuing authoritative series deals with the chemistry,
materials science, physics and technology of the rare earth
elements. Volume 38 of the Handbook on the Physics and Chemistry of
Rare Earth incorporates a recapitulation of the scientific
achievements and contributions made by the late Professor LeRoy
Eyring (1919-2005) to the science of the lanthanide oxides in which
the lanthanide element has a valence equal to or greater than
three.
This volume differs somewhat from the previous volumes in the
series in that there is a strong emphasis on the physical aspects
and not so much on the chemical aspects of intermetallic compounds.
Two of the chapters are concerned with relatively new experimental
methods of studying rare earth metallic phases - high energy
neutron spectroscopy and light scattering. In these chapters the
authors explain the new kinds of information one obtains from these
techniques and how this complements the knowledge previously
gleaned from the more common measurements - such as NMR, heat
capacities, magnetic susceptibility, transport and elastic
properties. One of the remaining three chapters deals with NMR
studies of rare earth intermetallics and the final two chapters are
concerned, not so much with a particular experimental technique,
but with physical phenomena that occur in these compounds: the
electron-phonon interaction and heavy fermion behavior.
The rare earths play a unique role in science. These seventeen
related elements afford a panoply of subtle variations deriving
from the systematic development of their electronic configurations,
allowing a test of theory with excellent resolution. In contrast
they find widespread use in even the most mundane processes such as
steel making, for polishing materials and gasoline cracking
catalysts. In between are exotic uses such as TV screen phosphors,
lasers, high strength permanent magnets and chemical probes.
This continuing authoritative series deals with the chemistry,
materials science, physics and technology of the rare earth
elements in an integrated manner. Each chapter is a comprehensive,
up-to-date, critical review of a particular segment of the field.
The work offers the researcher and graduate student a complete and
thorough coverage of this fascinating field.
This continuing authoritative series deals with the chemistry, materials science, physics and technology of the rare earth elements in an integrated manner. Each chapter is a comprehensive, up-to-date, critical review of a particular segment of the field. The work offers the researcher and graduate student a complete and thorough coverage of this fascinating field. Authoritative
Optical spectroscopy has been instrumental in the discovery of many
lanthanide elements. In return, these elements have always played a
prominent role in lighting devices and light conversion
technologies (Auer mantles, incandescent lamps, lasers, cathode-ray
and plasma displays). They are also presently used in highly
sensitive luminescent bio-analyses and cell imaging. This volume of
the Handbook on the Physics and Chemistry of Rare Earths is
entirely devoted to the photophysical properties of these elements.
It is dedicated to the late Professor William T (Bill) Carnall who
has pioneered the understanding of lanthanide spectra in the 1960 s
and starts with a Dedication to this scientist. The following five
chapters describe various aspects of lanthanide spectroscopy and
its applications. Chapters 231 presents state-of-the-art
theoretical calculations of lanthanide energy levels and transition
intensities. It is followed by a review (Chapter 232) on both
theoretical and experimental aspects of f-d transitions, a less
well known field of lanthanide spectroscopy, yet very important for
the design of new optical materials. Chapter 233 describes how
confinement effects act on the photophysical properties of
lanthanides when they are inserted into nanomaterials, including
nanoparticles, nanosheets, nanowires, nanotubes, insulating and
semiconductor nanocrystals. The use of lanthanide chelates for
biomedical analyses is presented in Chapter 234; long lifetimes of
the excited states of lanthanide ions allow the use of
time-resolved spectroscopy, which leads to highly sensitive
analyses devoid of background effect from the autofluorescence of
the samples. The last review (Chapter 235) provides a comprehensive
survey of near-infrared (NIR) emitting molecular probes and
devices, spanning an all range of compounds, from simple chelates
to macrocyclic complexes, heterometallic functional edifices,
coordination polymers and other extended structures. Applications
ranging from telecommunications to light-emitting diodes and
biomedical analyses are assessed.
This volume of the Handbook adds five new chapters to the science of rare earths. Two of the chapters deal with intermetallic compounds. An overview of ternary systems containing rare earths, transition metals and indium - Chapter 218 - opens the volume. It is followed by Chapter 219 sorting out relationships between superconductivity and magnetism. The next two chapters are dedicated to complex compounds of rare earths: Chapter 220 describes structural studies using circularly polarized luminescence spectroscopy of lanthanide systems, while Chapter 221 examines rare-earth metal-organic frameworks, also known as coordination polymers. The final Chapter 222 deals with the catalytic activity of rare earths in site-selective hydrolysis of DNA and RNA.
Even at the beginning of the new millenium the rare earths still
remain, to a certain extent, a mystery. The chapters in this volume
will help to unravel some of these. In the filling of the 4f
electronic orbitals the lanthanides defy the elementary aufbau
principle that underlies the periodic sequence of the elements, and
the authors of the first chapter introduce the readers to the basic
physics of the orbital collapse leading to that failure.
Furthermore an explanation is offered in terms of double-well
potentials. The phenomenon is illustrated using the valence
transitions observed in some of the rare earth atoms, including Sm
group metals and the higher oxides of cerium, praseodymium and
terbium. In the second chapter the synthesis and structure of the
many types of rare earth halides are described. They have been
described as simple, complex, binary, ternary and multinuclear
complex, and other categories needed to deal with the most studied
of the rare earth compounds. The structure types are skillfully
illustrated to show the elementary architecture of each type.
This volume of the Handbook on the Physics and Chemistry of Rare
Earth begins with a Dedication to late Professor LeRoy Eyring who
had been a committed co-editor of the first 32 volumes of this
series. This is followed by four chapters, the first two pertaining
to solid state physics and materials science, while the last two
chapters describe organic (and inorganic) reactions mediated by
tetravalent cerium-based oxidants and by divalent samarium-based
reductants. Chapter 227 is devoted to the description of the
crystal chemistry and physical properties of rare-earth
bismuthides, a class of compounds showing large similarities with
the rare-earth antimonides previously reviewed in volume 33 of this
series. The fascinating optical and electric properties of
rare-earth hydride films displaying a switchable mirror effect as a
function of hydrogen pressure, i.e. from a shiny metallic state to
a transparent insulating film with increasing pressure, are
described in Chapter 228, along with their fabrication methods.
Many chemical reactions take advantage of the tetravalent/trivalent
Ce(IV)/Ce(III) redox couple and many of its potential applications
are presented in Chapter 229, from analytical procedures, to
electrosynthesis, and organic and industrial (polymerization)
reactions. The last review (Chapter 230) focuses on the synthesis
and use of divalent samarium-based reductants in organic and
inorganic reactions, mainly on those containing iodide and
pentamethylcyclopentadienyl ligands.
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