Arthur E. Martell - Böcker

This monograph consists of manuscripts submitted by invited speakers who participated in the symposium "Industrial Environmental Chemistry: Waste Minimization in Industrial Processes and Remediation of Hazardous Waste," held March 24-26, 1992, at Texas A&M University. This meeting was the tenth annual international symposium sponsored by the Texas A&M Industry-University Cooperative Chemistry Program (IUCCP). The program was developed by an academic-industrial steering committee consisting of the co-chairmen, Professors Donald T. Sawyer and Arthur E. Martell of the Texas A&M University Chemistry Department, and members appointed by the sponsoring companies: Bernie A. Allen, Jr., Dow Chemical USA; Kirk W. Brown, Texas A&M University; Abraham Clearfield, Texas A&M University; Greg Leyes, Monsanto Company; Jay Warner, Hoechst-Celanese Corporation; Paul M. Zakriski, BF Goodrich Company; and Emile A. Schweikert, Texas A&M University (IUCCP Coordinator). The subject of this conference reflects the interest that has developed in academic institutions and industry for technological solutions to environmental contamination by industrial wastes. Progress is most likely with strategies that minimize waste production from industrial processes. Clearly the key to the protection and preservation of the environment will be through R&D that optimizes chemical processes to minimize or eliminate waste streams. Eleven of the papers are directed to waste minimization. An additional ten papers discuss chemical and biological remediation strategies for hazardous wastes that contaminate soils, sludges, and water.

This monograph consists of the proceedings of the Fifth International Symposium on the Activation of Dioxygen and Homogeneous Catalytic Oxidation, held in College Station, Texas, March 14-19, 1993. Readers who may wish to know more about the subjects presented in abstract form are invited to communicate directly with the authors of the abstracts.

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.

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.

This monograph consists of the proceedings of the Fifth International Symposium on the Activation of Dioxygen and Homogeneous Catalytic Oxidation, held in College Station, Texas, March 14-19, 1993. It contains an introductory chapter authored by Professors D. H. R. Barton and D. T. Sawyer, and twenty-nine chapters describing presentations by the plenary lecturers and invited speakers. One of the invited speakers, who could not submit a manuscript for reasons beyond his control, is represented by an abstract of his lecture. Also included are abstracts of forty-seven posters contributed by participants in the symposium. Readers who may wish to know more about the subjects presented in abstract form are invited to communicate directly with the authors of the abstracts. This is the fifth international symposium that has been held on this subject. The first was hosted by the CNRS, May 21-29, 1979, in Bendor, France (on the Island of Bandol). The second meeting was organized as a NATO workshop in Padova, Italy, June 24-27, 1984. This was followed by a meeting in Tsukuba, Japan, July 12-16, 1987. The fourth symposium was held at Balatonfured, Hungary, September 10-14, 1990. The sixth meeting is scheduled to take place in Delft, The Netherlands (late Spring, 1996); the organizer and host will be Professor R. A. Sheldon.

Over the past twenty five years the Commission on Equilibrium Data of the Analytical Division of the International Union of Pure and Applied Chemistry has been sponsoring a noncritical compilation of metal complex formation constants and related equilibrium constants. This work was extensive in scope and resulted in publication of two large volumes of Stability Constants by the Chemical Society (London). The first volume, edited by L. G. Sillen (for inorganic ligands) and by A. E. Martell (for organic ligands), was published in 1964 and covered the literature through 1962. The second volume, subtitled Supplement No. 1, edited by L. G. Sillen and E. Hogfeldt (for inorganic ligands), and A. E. Martell and R. M. Smith (for organic ligands), was published in 1971 and covered the literature up to 1969. These two large compilations attempted to cover all papers in the field related to metal complex equilibria (heats, entropies, and free energies). Most recently a noncritical compilation of organic ligands by D. D. Perrin (Pergamon Press) extended coverage of the literature through 1973 and a similar volume for inorganic ligands by E. Hogfeldt covered through 1974. Since it was the policy of the Commission during that period to avoid decisions concerning the quality and reliability of the published work, th~ compilation would frequently contain from ten to twenty values for a single equilibrium constant.

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.