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Stability constants are fundamental to understanding the behavior of metal ions in aqueous solution. Such understanding is important in a wide variety of areas, such as metal ions in biology, biomedical applications, metal ions in the environment, extraction metallurgy, food chemistry, and metal ions in many industrial processes. In spite of this importance, it appears that many inorganic chemists have lost an appreciation for the importance of stability constants, and the thermodynamic aspects of complex formation, with attention focused over the last thirty years on newer areas, such as organometallic chemistry. This book is an attempt to show the richness of chemistry that can be revealed by stability constants, when measured as part of an overall strategy aimed at understanding the complexing properties of a particular ligand or metal ion. Thus, for example, there are numerous crystal structures of the Li+ ion with crown ethers. What do these indicate to us about the chemistry of Li+ with crown ethers? In fact, most of these crystal structures are in a sense misleading, in that the Li+ ion forms no complexes, or at best very weak complexes, with familiar crown ethers such as l2-crown-4, in any known solvent. Thus, without the stability constants, our understanding of the chemistry of a metal ion with any particular ligand must be regarded as incomplete. In this book we attempt to show how stability constants can reveal factors in ligand design which could not readily be deduced from any other physical technique.
Based on a translated Japanese title published in 2012, this book provides fundamental aspects of experimental and computational methods, the properties and structure of solvents, ion solvation and equilibria and reactions of metal complexes in solution. It includes state-of-the-art details on metal complexes in newly developing sustainable liquids and applications in real life. Appealing to researchers working in coordination chemistry, including students and industrialists, the text uses exercises, tables and figures to help the reader with their understanding of the topic.
Emphasises on contemporary applications and an intuitive problem-solving approach that helps students discover the exciting potential of chemical science. This book incorporates fresh applications from the three major areas of modern research: materials, environmental chemistry, and biological science.
An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory; dπ -pπ bonds; Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions; Trends in stepwise constants; Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand; Chelate effect and its thermodynamic origin; Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes; Mechanisms for ligand replacement reactions; Formation of complexes from aquo ions; Ligand displacement reactions in octahedral complexes- acid hydrolysis, base hydrolysis; Racemization of tris chelate complexes; Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes; The trans effect; Theories of trans effect; Mechanism of electron transfer reactions – types; outer sphere electron transfer mechanism and inner sphere electron transfer mechanism; Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory; Molecular orbital theory: octahedral, tetrahedral or square planar complexes; π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals; Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states); Calculation of Dq, B and β parameters; Effect of distortion on the d-orbital energy levels; Structural evidence from electronic spectrum; John-Tellar effect; Spectrochemical and nephalauxetic series; Charge transfer spectra; Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry; Guoy’s method for determination of magnetic susceptibility; Calculation of magnetic moments; Magnetic properties of free ions; Orbital contribution, effect of ligand-field; Application of magneto-chemistry in structure determination; Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes; Wade’s rules; Carboranes; Metal carbonyl clusters - low nuclearity carbonyl clusters; Total electron count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls: structure and bonding; Vibrational spectra of metal carbonyls for bonding and structure elucidation; Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.
PRINCIPLES OF MODERN CHEMISTRY has dominated the honors and high mainstream general chemistry courses and is considered the standard for the course. The fifth edition is a substantial revision that maintains the rigor of previous editions but reflects the exciting modern developments taking place in chemistry today. Authors David W. Oxtoby and H. P. Gillis provide a unique approach to learning chemical principles that emphasizes the total scientific process'from observation to application'placing general chemistry into a complete perspective for serious-minded science and engineering students. Chemical principles are illustrated by the use of modern materials, comparable to equipment found in the scientific industry. Students are therefore exposed to chemistry and its applications beyond the classroom. This text is perfect for those instructors who are looking for a more advanced general chemistry textbook.
MILS-16 provides an up-to-date review of the impact of alkali metal ions on life. Their bioinorganic chemistry and analytical determination, the solid state structures of bio-ligand complexes and the properties of alkali metal ions in solution in the context of all kinds of biologically relevant ligands are covered, this includes proteins (enzymes) and nucleic acids (G-quadruplexes). Minerals containing sodium (Na+) and potassium (K+) are abundant in the Earth's crust, making Na+ and K+ easily available. In contrast, the alkali elements lithium (Li+), rubidium, and cesium are rare and the radioactive francium occurs only in traces. Since the intra- and extracellular, as well as the compartmental concentrations of Na+ and K+ differ significantly, homeostasis and active transport of these ions are important; this involves transporters/carriers and pore-forming ion channel proteins. Systems like Na+/K+-ATPases, H+/K+-ATPases or Na+/H+ antiporters are thoroughly discussed. The role of K+ in photosynthesis and the role of Na+ in charging the "battery of life" are pointed out. Also, the relationships between alkali metal ions and diseases (e.g., Parkinson or traumatic brain injury) are covered and the relevance of Li+ salts in medicine (pharmacology and mechanism) is reviewed. This and more is treated in an authoritative and timely manner in the 16 stimulating chapters of Volume 16, The Alkali Metal Ions: Their Role for Life, which are written by 44 internationally recognized experts from 12 nations. The impact of this vibrant research area is manifested in nearly 3000 references, over 30 tables and more than 150 illustrations (two thirds in color). MILS-16 also provides excellent information for teaching. Astrid Sigel, Helmut Sigel, and Roland K. O. Sigel have long-standing interests in Biological Inorganic Chemistry. Their research focuses on metal ion interactions with nucleotides and nucleic acids and on related topics. They edited previously 44 volumes in the series Metal Ions in Biological Systems.
Critical Survey of Stability Constants of EDTA Complexes focuses on the computations, values, and characteristics of stability constants. The book emphasizes that for a critical discussion of experimentally determined stability constants, it is important to consider the precision of the values that manifests the self-consistency of the constant, taking into consideration the random errors. The publication reviews the stability constants of metal complexes. The numerical calculations affirm the reactions and transformations of metal ions when exposed to varying conditions. The text also presents a list of enthalpies of reactions with (ethylenedinitrito)tetra-acetic acid (EDTA) obtained by direct calorimetric measurements. The book also notes that in order to identify reliable metal complex stability constants for a ligand, it is important to know the formation constants of protonated species. The text is a dependable reference for readers wanting to dig deeper into the stability constants of EDTA complexes.
This book describes potentiometric methods for determining stability constants and explains how these constants can be used to describe metal ion speciation in complex environmental and biological systems. It also provides three original computer programs on a disk for calculating stability constants and for using stability constants to calculate concentrations of molecular species in solution. The author gives examples of calculations for simple metal chelates, for metal complexes of large organic molecules, and for mixtures containing several metal ions and complexing agents in aqueous solution. They also describe common errors in calculating stability constants and how to avoid them. This carefully revised second edition is now even more useful to the reader, and, in particular, to those who make use of the program disk. Each program has been revised to improve speed, control, and error trapping.
Endlich ein Fachbuch, das die Theorie, Methoden und die verschiedenen Arten von Metall-Ionen-Komplexen in Wasser (Hydrolyse) umfassend behandelt. Geschrieben wurde dieses Referenzwerk von einem Kernchemiker aus dem Hochschulbereich und einem Geochemiker aus der Industrie. Behandelt werden Kationen- und Anionen-Komplexe sowie die Metall-Ionen-Hydrolyse, zu der zunächst Hintergrundinformationen geliefert werden, bevor eine Beschreibung der Dissoziation von Wasser, aller verschiedenen Hydrolysekomplexe und Verbindungen von Metall und Wasser folgt. Ein Muss für Wissenschaftler im universitären Umfeld und in der Industrie, die sich mit diesem interdisziplinären Thema beschäftigen.