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Homogeneous Catalysis. The Applications and Chemistry of Catalysis by Soluble Transition Metal Complexes
430
Book
Reviews
information on analytical methods, with a heavy emphasis on gas chromatography techniques. Valuable discussions on limits of detection for volatile and semivolatile organic compounds, QA/QC protocols, and a glossary are also included. Chapter 4 by L. Barber and Chap. 5 by Hughes et al. are particularly effective in demonstrating the necessity to use a variety of analytical techniques when tracing groundwater plumes in the saturated and unsaturated zones. While QA/QC procedures often seem excessive to the practicing environmental analytical chemist, the authors repeatedly demonstrate the importance of good protocols. These chapters also indicate that we must continually strive to bring state-of-the-art analytical chemistry techniques to studies that delineate transport of hazardous chemicals in groundwater. While there have been impressive improvements in both sampling and analytical methodologies over the past decade, detection limits reported here, compared to those achievable for surface waters, are woefully inadequate. Whereas .ug/L and mg/L levels are reported in this book, a state-of-the-art analytical objective should be pg/L and pg/L. The ability to analyze at these levels is particularly relevant for many metals (Pb, Hg, Cd, and Cu) and is necessary to describe rigorously subsurface behavior of hy_drophobic organic substances(PCBs, PCDDs, and PCDFs). Information presented in Chap 6-10 is intended to provide answers to such practical questions as: What parameters should be measured when one studies severity and extent of contamination due to petroleum refining, oil and gasoline tank leaks and wood preservative treatment activities? What chemical parameters are most illustrative when designing a national reconnaissance study of hazardous waste sites? What statistical tools are best when choosing the optimum (minimum?) number of samples to define the extent of contamination? In an information-rich chapter, R. Plumb tells us that dichloromethane is most frequently found in hazardous waste sites and VOCs are the most informative chemical parameters in diagnosing the extent of groundwater pollution in the U.S. Chapters 1 l-13 present case studies on
sites in the U.S., Canada and Western Australia. Here we learn about the comparative behaviors of chlorinated phenols, PAHs, TNT, DNAPLs and other organic compounds. These studies represent long-term efforts and clearly demonstrate the importance of attaching multidisciplinary teams to evaluate extensively contaminated hazardous waste sites. The final chapters, entitled “Geochemical Investigators,” do a good job of presenting unifying principles. The authors explain how mineral-water equilibrium concepts may be applied to interpret the behavior of chemicals in groundwater. Although fairly modest in terms of chemical sophistication, several conceptual models are discussed regarding their application to describe the behavior of PCBs, CFCs, metal sulfides, and DNAPLs. Overall, the authors have done a good editing job. It would have been nice if the authors could have put information on the number of hazardous waste sites for various countries in the introductory chapter. Such data were presented by Schleger et a[. in their chapter regarding sites in Germany and could have been useful to give the reader an idea about the magnitude of the problem. Finally, although the book is mainly aimed at practitioners in the field, educators should also use an important message that is implicit in this book. Academic curricula designed to train students in this area should provide students the opportunity to work in multidisciplinary teams involving scientists from analytical chemistry, transport phenomena, statistics, etc. While many academic departments pay lip service to this approach, there is very little evidence that, other than taking classes outside their department, students actually get field experience in a multidisciplinary setting. This book provides an ideal template for a great curriculum.
Homogeneous Catalysis. The Applications and Chemistry of Catalysis by Soluble Transition Metal Complexes. By G. W. PARSHALL and S. D. ITTEL. 2nd Edition, Wiley, 1992
cations. From their viewpoint at the Experimental Station of the duPont Company, Parshall and Ittel have unique insights to offer in their fascinating book on homogeneous catalysis. The subtitle signals the emphasis on applications and the basis is an up-to-date bibliography that includes many patents that are evaluated in relation to actual or possible markets and processes. Perhaps the best chapters are those that emphasise the role of the catalyst in the control of structure, molecular weight and dispersity of polymers. This must surely be the best short account to have appeared since the inception of fluidised bed linear low density polyethylene. We are given a review of duPont’s own processes for the dihydrocyanation of butadiene which has seemed quite impenetrable to the outsider on the basis of the voluminous and daunting patent literature. Many examples relate to chiral synthesis of pharmaceutical products. Anyone concerned with either the search for new profitable processes or the search for new grants in the area of process chemistry will wish to possess this book. The volume is less strong in relation to the development of our understanding of reaction mechanisms which could have been distinguished more clearly from the ubiquitous rationalisations based upon a set of rules that must surely be too facile. Polynuclear complexes barely get a look in. The free
The details of the Wacker process for the production of acetaldehyde from ethylene, published in 1957, were a major influence in the direction of chemical research. Homogeneous catalysis gave a push to the resurgence of inorganic chemistry, especially through rapid advances in our knowledge of the reactions of organometallic complexes. A new body of literature accumulated rapidly and our understanding of molecular processes at discrete sites in soluble complexes rapidly outstripped that of active sites on catalytic surfaces1 It became possible to pursue targets in organic synthesis in new ways that were rational, useful and at the time exciting. Unsurprisingly, most firms in the process industry soon established groups to work in the area. Successes (acetic acid, adiponitrile and hydroformylation) and failures (vinyl acetate and ethylene glycol) were both spectacular. By 1970, the distinguished group at Monsanto had pointed to a subtle approach to fine chemical synthesis through asymmetric induction in their process for L-DOPA production. The more recent night from commodity chemicals into specialty products, from which hopes of profits abound, has greatly widened the scope for commercial appli-
ANDERS
ANDREN
Water
Chemistry Prvgram University of Wisconsin Madison, WI 53706. U.S.A.
Book Reviews radical gets its due in the chapter on hydrocarbon oxidation but otherwise scarcely makes an appearance. It is a paradox that homogeneous catalysts with potential for selective stereochemical and chiral control may nevertheless involve catalyst centres modified by minor by-products found in such systems.
Bubbles, Drops, and Particles in Non-Newtonian Fluids. By R. P. CHHABRA. CRC Press, Boca Raton, FL, 1993 The study of the motion of bubbles, drops and particles in a viscous fluid has always been a central preoccupation of practitioners of fluid dynamics. Until recent times, this endeavor has been largely confined to the realm of Newtonian fluids. However, many fluids of scientific and technological interest (including polymeric fluids of interest to chemical engineers) are non-Newtonian. Understandably, the past four decades have witnessed significant research activity in non-Newtonian fluid mechanics. This book provides an excellent overview of the current state of affairs in this important endeavor. Non-Newtonian is an “exclusive”, rather than descriptive, terminology for all it does is eliminate Newtonian behavior from consideration; so understandably, non-Newtonian fluid mechanics is a vast field of endeavor. Considering that the motion of bubbles, drops and particles in a Newtonian fluid-is still an active area of research today, one can appreciate the magnitude of the undertaking to describe motions in a non-Newtonian setting. Every relevant issue in bubble/drop/particle dynamics has to be repeated for each major category of rheological behavior. Accordingly, the author organizes fluid behavior into three major groupings: purely viscous, viscoplastic and viscoelastic. The first category includes all the familiar models of inelastic fluids with shear-rate-dependent viscosities: power law, Carreau, Ellis, and so forth. Under the heading of viscoplastic fluids, we find the familiar models with a yield stress such as the Bingham and Casson models. Models of viscoelastic behavior demand a significantly higher level of mathematical sophistication, which the book avoids by directing the reader to the major references in non-Newtonian fluid mechanics. We may now envision a matrix consisting of three columns (the three major categories of fluid behavior) and many rows (flow phenomena of interest). For each entry in this array, the description of the phenomena is in general far more intricate in comparison to the standard Newtonian case. This book thus represenls a great service to all those with interests in fluid mechanics and fluid engineering. The contents of the book are as follows. Chapter 2 presents a general overview of concepts in rheology and nonNewtonian fluid mechanics. The sign convention for the stress tensor follows that of 7’ransport Phenomena by Bird et al. Chapter 3 deals with the motion of rigid spheres in steady flow fields. A special note should be made about the rich
431
Department of Chemical Engineering Uniuersity of Edinburgh King’s Buildings Mayfield Road Edinburgh EH9 3JL. U.K.
J. M. DAVIDSON
number of citations, especially to experimental work. The __.. .. _ _. revtew ot the hterature on yieldstress measurements should give students an idea of the experiments1 difficulties and uncertainties concerning this important material property. Viscoelastic fluids are covered in Chap. 4, and in addition to the extensive literature on the rigid sphere, a collection of references on nonspherical particles is included. The discussion here of the simplest of all problems, a single sphere moving through an unbounded domain, gives readers an inkling of the difficulties in computational modeling of viscoelastic fluids. From rigid particles, we turn to bubbles and drops in the next chapter. Many of the issues familiar to Newtonian fluid mechanics (such as bubble growth, and drop breakup and coalescence) are discussed in the nonNewtonian context. The work presented in this chapter has technological ramifications, e.g. the evolution of encapsulated bubbles in foaming plastics. The next two chapters turn our attention from the analysis of single particles to a far more difficult system, namely the Bow of non-Newtonian fluids through packed beds, and fluidization and sedimentation problems with non-Newtonian fluids. Chapter 8 is a concise summary of the present state of affairs in heat and mass transfer from bubbles and drops in non-Newtonian fluids. The book closes with a,chapter that could have come earlier, dealing with the application of the motion of a single particle to rheometry, i.e. the characterization of the rheology of the carrier fluid. There are some nice features that merit special mention. Each chapter concludes with a concise summary of the main ideas. The extensive references to the vast literature on this subject will be of great use to both the novice and experienced workers in this field. The author’s approach to controversial subjects would be best described as “neutral”, the reader is directed to work by both sides. This approach has obvious advantages and disadvantages from a pedagogical point of view. Finally, this book would he an excellent addition to the reading list in a typical graduate-level course on non-Newtonian fluid mechanics and a good starting point for ideas for term projects that are usually associated with such advanced courses. SANGTAE Rheology Research Center and Department of Chemical University oj Wisconsin Madison, WI 53706, U.S.A.
Engineering
KIM
Book
Reviews
information on analytical methods, with a heavy emphasis on gas chromatography techniques. Valuable discussions on limits of detection for volatile and semivolatile organic compounds, QA/QC protocols, and a glossary are also included. Chapter 4 by L. Barber and Chap. 5 by Hughes et al. are particularly effective in demonstrating the necessity to use a variety of analytical techniques when tracing groundwater plumes in the saturated and unsaturated zones. While QA/QC procedures often seem excessive to the practicing environmental analytical chemist, the authors repeatedly demonstrate the importance of good protocols. These chapters also indicate that we must continually strive to bring state-of-the-art analytical chemistry techniques to studies that delineate transport of hazardous chemicals in groundwater. While there have been impressive improvements in both sampling and analytical methodologies over the past decade, detection limits reported here, compared to those achievable for surface waters, are woefully inadequate. Whereas .ug/L and mg/L levels are reported in this book, a state-of-the-art analytical objective should be pg/L and pg/L. The ability to analyze at these levels is particularly relevant for many metals (Pb, Hg, Cd, and Cu) and is necessary to describe rigorously subsurface behavior of hy_drophobic organic substances(PCBs, PCDDs, and PCDFs). Information presented in Chap 6-10 is intended to provide answers to such practical questions as: What parameters should be measured when one studies severity and extent of contamination due to petroleum refining, oil and gasoline tank leaks and wood preservative treatment activities? What chemical parameters are most illustrative when designing a national reconnaissance study of hazardous waste sites? What statistical tools are best when choosing the optimum (minimum?) number of samples to define the extent of contamination? In an information-rich chapter, R. Plumb tells us that dichloromethane is most frequently found in hazardous waste sites and VOCs are the most informative chemical parameters in diagnosing the extent of groundwater pollution in the U.S. Chapters 1 l-13 present case studies on
sites in the U.S., Canada and Western Australia. Here we learn about the comparative behaviors of chlorinated phenols, PAHs, TNT, DNAPLs and other organic compounds. These studies represent long-term efforts and clearly demonstrate the importance of attaching multidisciplinary teams to evaluate extensively contaminated hazardous waste sites. The final chapters, entitled “Geochemical Investigators,” do a good job of presenting unifying principles. The authors explain how mineral-water equilibrium concepts may be applied to interpret the behavior of chemicals in groundwater. Although fairly modest in terms of chemical sophistication, several conceptual models are discussed regarding their application to describe the behavior of PCBs, CFCs, metal sulfides, and DNAPLs. Overall, the authors have done a good editing job. It would have been nice if the authors could have put information on the number of hazardous waste sites for various countries in the introductory chapter. Such data were presented by Schleger et a[. in their chapter regarding sites in Germany and could have been useful to give the reader an idea about the magnitude of the problem. Finally, although the book is mainly aimed at practitioners in the field, educators should also use an important message that is implicit in this book. Academic curricula designed to train students in this area should provide students the opportunity to work in multidisciplinary teams involving scientists from analytical chemistry, transport phenomena, statistics, etc. While many academic departments pay lip service to this approach, there is very little evidence that, other than taking classes outside their department, students actually get field experience in a multidisciplinary setting. This book provides an ideal template for a great curriculum.
Homogeneous Catalysis. The Applications and Chemistry of Catalysis by Soluble Transition Metal Complexes. By G. W. PARSHALL and S. D. ITTEL. 2nd Edition, Wiley, 1992
cations. From their viewpoint at the Experimental Station of the duPont Company, Parshall and Ittel have unique insights to offer in their fascinating book on homogeneous catalysis. The subtitle signals the emphasis on applications and the basis is an up-to-date bibliography that includes many patents that are evaluated in relation to actual or possible markets and processes. Perhaps the best chapters are those that emphasise the role of the catalyst in the control of structure, molecular weight and dispersity of polymers. This must surely be the best short account to have appeared since the inception of fluidised bed linear low density polyethylene. We are given a review of duPont’s own processes for the dihydrocyanation of butadiene which has seemed quite impenetrable to the outsider on the basis of the voluminous and daunting patent literature. Many examples relate to chiral synthesis of pharmaceutical products. Anyone concerned with either the search for new profitable processes or the search for new grants in the area of process chemistry will wish to possess this book. The volume is less strong in relation to the development of our understanding of reaction mechanisms which could have been distinguished more clearly from the ubiquitous rationalisations based upon a set of rules that must surely be too facile. Polynuclear complexes barely get a look in. The free
The details of the Wacker process for the production of acetaldehyde from ethylene, published in 1957, were a major influence in the direction of chemical research. Homogeneous catalysis gave a push to the resurgence of inorganic chemistry, especially through rapid advances in our knowledge of the reactions of organometallic complexes. A new body of literature accumulated rapidly and our understanding of molecular processes at discrete sites in soluble complexes rapidly outstripped that of active sites on catalytic surfaces1 It became possible to pursue targets in organic synthesis in new ways that were rational, useful and at the time exciting. Unsurprisingly, most firms in the process industry soon established groups to work in the area. Successes (acetic acid, adiponitrile and hydroformylation) and failures (vinyl acetate and ethylene glycol) were both spectacular. By 1970, the distinguished group at Monsanto had pointed to a subtle approach to fine chemical synthesis through asymmetric induction in their process for L-DOPA production. The more recent night from commodity chemicals into specialty products, from which hopes of profits abound, has greatly widened the scope for commercial appli-
ANDERS
ANDREN
Water
Chemistry Prvgram University of Wisconsin Madison, WI 53706. U.S.A.
Book Reviews radical gets its due in the chapter on hydrocarbon oxidation but otherwise scarcely makes an appearance. It is a paradox that homogeneous catalysts with potential for selective stereochemical and chiral control may nevertheless involve catalyst centres modified by minor by-products found in such systems.
Bubbles, Drops, and Particles in Non-Newtonian Fluids. By R. P. CHHABRA. CRC Press, Boca Raton, FL, 1993 The study of the motion of bubbles, drops and particles in a viscous fluid has always been a central preoccupation of practitioners of fluid dynamics. Until recent times, this endeavor has been largely confined to the realm of Newtonian fluids. However, many fluids of scientific and technological interest (including polymeric fluids of interest to chemical engineers) are non-Newtonian. Understandably, the past four decades have witnessed significant research activity in non-Newtonian fluid mechanics. This book provides an excellent overview of the current state of affairs in this important endeavor. Non-Newtonian is an “exclusive”, rather than descriptive, terminology for all it does is eliminate Newtonian behavior from consideration; so understandably, non-Newtonian fluid mechanics is a vast field of endeavor. Considering that the motion of bubbles, drops and particles in a Newtonian fluid-is still an active area of research today, one can appreciate the magnitude of the undertaking to describe motions in a non-Newtonian setting. Every relevant issue in bubble/drop/particle dynamics has to be repeated for each major category of rheological behavior. Accordingly, the author organizes fluid behavior into three major groupings: purely viscous, viscoplastic and viscoelastic. The first category includes all the familiar models of inelastic fluids with shear-rate-dependent viscosities: power law, Carreau, Ellis, and so forth. Under the heading of viscoplastic fluids, we find the familiar models with a yield stress such as the Bingham and Casson models. Models of viscoelastic behavior demand a significantly higher level of mathematical sophistication, which the book avoids by directing the reader to the major references in non-Newtonian fluid mechanics. We may now envision a matrix consisting of three columns (the three major categories of fluid behavior) and many rows (flow phenomena of interest). For each entry in this array, the description of the phenomena is in general far more intricate in comparison to the standard Newtonian case. This book thus represenls a great service to all those with interests in fluid mechanics and fluid engineering. The contents of the book are as follows. Chapter 2 presents a general overview of concepts in rheology and nonNewtonian fluid mechanics. The sign convention for the stress tensor follows that of 7’ransport Phenomena by Bird et al. Chapter 3 deals with the motion of rigid spheres in steady flow fields. A special note should be made about the rich
431
Department of Chemical Engineering Uniuersity of Edinburgh King’s Buildings Mayfield Road Edinburgh EH9 3JL. U.K.
J. M. DAVIDSON
number of citations, especially to experimental work. The __.. .. _ _. revtew ot the hterature on yieldstress measurements should give students an idea of the experiments1 difficulties and uncertainties concerning this important material property. Viscoelastic fluids are covered in Chap. 4, and in addition to the extensive literature on the rigid sphere, a collection of references on nonspherical particles is included. The discussion here of the simplest of all problems, a single sphere moving through an unbounded domain, gives readers an inkling of the difficulties in computational modeling of viscoelastic fluids. From rigid particles, we turn to bubbles and drops in the next chapter. Many of the issues familiar to Newtonian fluid mechanics (such as bubble growth, and drop breakup and coalescence) are discussed in the nonNewtonian context. The work presented in this chapter has technological ramifications, e.g. the evolution of encapsulated bubbles in foaming plastics. The next two chapters turn our attention from the analysis of single particles to a far more difficult system, namely the Bow of non-Newtonian fluids through packed beds, and fluidization and sedimentation problems with non-Newtonian fluids. Chapter 8 is a concise summary of the present state of affairs in heat and mass transfer from bubbles and drops in non-Newtonian fluids. The book closes with a,chapter that could have come earlier, dealing with the application of the motion of a single particle to rheometry, i.e. the characterization of the rheology of the carrier fluid. There are some nice features that merit special mention. Each chapter concludes with a concise summary of the main ideas. The extensive references to the vast literature on this subject will be of great use to both the novice and experienced workers in this field. The author’s approach to controversial subjects would be best described as “neutral”, the reader is directed to work by both sides. This approach has obvious advantages and disadvantages from a pedagogical point of view. Finally, this book would he an excellent addition to the reading list in a typical graduate-level course on non-Newtonian fluid mechanics and a good starting point for ideas for term projects that are usually associated with such advanced courses. SANGTAE Rheology Research Center and Department of Chemical University oj Wisconsin Madison, WI 53706, U.S.A.
Engineering
KIM