- Email: [email protected]
Spectrochemical analysis
Spectrorhimica
Acre, Vol. 44A, No. I I. pp. 1229-1231, 1988.
Pergamon Press pk. Printed in Great Britain.
BOOK REVIEWS A HANDBOOK OF NUCLEAR MAGNETIC RESONANCE, by R. FREEMAN. Longman, U.K., 1988, 312 pp., f 18.95.
at work in alpine villages where the ‘. . normal flow of skiers down the slope . ’ is a relaxation process. Such descriptions convey much about the subject. Even when the topic is not illustrated by an appropriate story the text has an uncommon style. For example, phrases like ‘spin gymnastics’ and ‘spin choreography’ are used to describe the behaviour of nuclear spins in pulsed NMR experiments. Any text book needs to be judged on more than just the selection of topics and the elegance of the style. It is, of course, of paramount importance that the text be accurate and, ideally, accessible to a wide readership. As far as I can judge, Freeman’s book satisfies both criteria, as one might have expected from a handbook by one of the leading workers in the NMR field. The idea of providing a pictorial and, for many entries, a non-mathematical description works well. I will use this book not only for my benefit but also for the benefit of the students I teach. Freeman says in the preface that ‘. the handbook will have achieved its aim if it sits on the spectrometer console. rather than on the library shelf’. My copy will sit in my office; I will buy a second copy for the spectrometer.
In recent years there has been a deluge of books about NMR spectroscopy aimed at all levels of the market: undergraduates, research workers, chemists, biologists and so on. Many of the books are useful but few are unique. The book by Freeman is undoubtedly both useful and unique. The author has eschewed the conventional approach for describing NMR. Instead he has given an account of a diverse range of topics organized under 59 headings in alphabetical order: from Adiabatic Fast Passage to Zero Filling, and taking in subjects such as Composite Pulses, Intensities, Rotating Frame and Two-Dimensional Spectroscopy along the way. The book resembles a selective, but extensive, dictionary or encylopedia rather than the usual text-book format. The choice of topics should include something for all NMR practitioners. I was particularly pleased to see a section on Product Operator Formalism, which is something I have found difficult to understand. Throughout the book the engaging style of the author is apparent, not only in the many cartoons which illustrate the text, but also in the text itself. Examples are: in the section on Spin-Spin Relaxation we read of ‘A client . . trying to negotiate a loan from the pawnbroker. . ‘, the Nuclear Overhauser Effect is introduced with a discussion of ski-lifts
School of Chemical Sciences, University of East Anglia, Norwich, U.K.
SPECTROCHEMICAL ANALYSIS, JAMES D. INGLE, JR. and STANLEY R. CROUCH. Prentice Hall, Englewood Cliffs, New Jersey, 1988, xv+ 590 pp., $52.00, ISBN O-13-826876-2. analysis spectrochemical methods of Optical (u.v.-visible-i.r.) rank prominently amongst all analytical methods for their frequency of use, yet comprehensive coverage of their methodologies in a single treatise is rare. This book is intended to fill this gap and was conceived as a textbook for graduate and advanced undergraduate students. The level is aimed intermediate between the survey coverage of spectrochemical methods found in general instrumental analysis texts and the comprehensive coverage afforded by monographs devoted to one or two such techniques. Both atomic and molecular spectroscopy are addressed but written to be used independently of one another. IUPAC terminology has been used and consistent sets of units maintained. The book is divided into five main sections. The first six chapters introduce fundamental concepts. These encompass a brief introduction to the nature of spectrochemical information and measurements, analytical methodology, instrumentation used in optical spectrometers and signal-to-noise ratio (S/N) considerations. Specific topics addressed include basic information concerning radiation-matter interactions; the quantitative mathematical relationships governing the measured signals and S/N ratios obtained and their relationship to instrumental factors; basic optical relationships and imaging; optical radiation sources and transducers as well as signal processing and readout. General principles and concepts as well as fundamental equations pertaining to atomic spectroscopic techniques are
G. MOORE
covered in Chapter 7. These include a discussion of spectral line shapes and intensities for emission, absorption and fluorescence. In an attempt to keep with one of the objectives of this text, i.e. “to emphasize the chemistry which accompanies spectrochemical analysis”, a brief consideration of sample introduction and atomization processes is given along with attendant potential interference effects. These subject areas suffer from rather shallow treatment and are little developed. Chapters 8-11 cover specific atomic spectroscopic methods including flame, plasma, arc and spark emission as well as atomic absorption and fluorescence spectrometry. Each chapter gives consideration to pertinent sources/atomizers, instrumentation, quantitative S/N expressions and performance characteristics. Each chapter concludes with a brief discussion of specific methodology and applications. These latter aspects are not developed in any detail and are of little use other than to place the technique in perspective. This completes that portion of the text formally devoted to atomic spectrometry. Chapter 12 serves to introduce molecular spectroscopy through consideration of electronic and vibronic absorption and luminescence processes. This material lays the foundation for subsequent chapters covering specific molecular techniques such as u.v.-visible molecular absorption (Chapter 13); dispersive and FT-i.r. (absorption/reflection/emission-chapter 14); molecular luminescence (fluorescence, phosphorescence, chemiluminescence and polarization techniques-chapter 15) and molecular scattering techniques (resonance and non-linear Raman, turbidity, nephelometry and laser scattering methods-Chapter 16). Subject handling parallels that used for atomic methods, i.e. a discussion of specific instrumentation, quantitative signal and S/N expressions, some data manipulation considerations, per-
1229
t230
Book Reviews
formance characteristics and applications. In general, applications are given somewhat better treatment than their atomic spectrometry counterparts. Chapter 17, “Spectrochemical Techniques on the Horizon”, deals not so much with newly emerging techniques but those atomic and molecular methods that are becoming or should become standard tools of the trade. These include photoacoustic and thermal lensing spectrometry, laser atomic ionization methods, intracavity absorption, molecular multiphoton ionization and doppler-free absorption techniques. Although discussion of these topics is brief, their introduction here does serve to produce a well-rounded text. The last section of this book consists of six appendices which contain additional information about statistical concepts, optical materials and filters, photomultiplier tubes, sample preparation methods and the interrelationships between experimental and fundamental spectroscopic variables. Of these, the appendix devoted to sample preparation appears rather incongruous in this text and despite the author’s intention of treating the chemical side of speetrochemical analysis, this section is too short to be of any use whatsoever. Informative tables of units, conversion factors and symbols along with a useful and comprehensive subject index conclude this text. Throughout this book the authors have attempted to stress principles and concepts by presenting them first before the details of a given topic are introduced. Liberal use of
figures with extended captions and summary tables which compliment textual information aid in achieving this aim. Bold face type has also been utilized as a highlight whenever new terminology is introduced. The brief set of cited literature appended to each chapter highlights selected sources of general references covering the subjects considered in the text and of specialized references providing additional details on specific topics. The authors have been able to draw significantly from their first hand experience in many of the fundamental and practical aspects covered in this book, permitting them to offer concise yet lucid discussions of many abstract concepts. As well, their considerable teaching experience has given them the foresight to format the material so as to make it an appealing course companion. That the book is intended primarily for use as a graduate course text is also evident from the probing sets of problems which accompany each chapter. Overall, the volume is durably bound, relatively free of typographical errors and is attractively priced for its intended use. Although the book is primarily recommended as a text for a course on spectrochemical analysis, it will also appeal to practicing spectroscopists as a useful reference source and valued addition to a personal library.
AND REACTION DYNAMICS MOLECULAR CHEMICAL REACTIVITY by R. D. LEVINE and R. B.
section not undergoing major changes. As well as new examples for older topics we find totally new material such as picosecond measurements, multiphoton absorption and a discussion of the molecular orbital basis for steric effects. The final three chapters replace the last two of the earlier work and represent a major rewrite and re-ordering of these, with a huge increase in the material covered. These chapters cover the areas of experimental and theoretical techniques, molecular energy transfer, reaction dynamics and chemical reactivity. It here that we find the new topics introduced in most detail and the authors have done an excellent job in tying together so many disparate strands into a cohesive whole. Of the original material it is the topics of curve crossings and suprisal analysis that has been most extended to reflect their growing importance. The new material includes topics such as multiphoton absorption/ionization, molecular beam-surface interactions, bimolecular emission spectroscapy, laser-assisted collisions, clusters and cluster chemistry, stereo-specific dynamics, orientation, alignment and orbital control. Many of these areas are still in their infancy and it is particularly welcome to see their inclusion here. In a book of this type., where a large degree of selectivity is required, it is always possible to quibble about particular inclusions or omissions but overall the coverage is extensive, fair and representative of the field as a whole. The book is a welcome addition to the area and a worthy successor to the original work.
BERNSTEIN,E25. The field of molecular reaction dynamics has expanded at a phenomenal rate over the last two decades-and shows no sign of abating; there is thus a real need.for books that can present the wealth of new material in a form accessible to third-year undergraduate/post-graduate students. One of the mainstays has been “Molecular Reaction Dynamics”, by the same authors, which is now twelve years old. The present book is a replacement to that work and represents a major rewrite and extension of the earlier text. Indeed the extent of this can be judged from the fact that the book has doubled in length to over 500 pages and in many ways it should be considered an entirely new work. The book follows the ambitious aim of the previous work in trying to provide an introduction to the entire field of molecular reaction dynamics. The approach is to emphasize the important essence of the phenomena and their interpretation with enough accompanying detail to enable the interested reader to pursue the matter to greater depths-via the extensive reading lists provided for each section. This is not to suggest that the authors are shy of introducing a rigorous and quantitative treatment where necessary or advantageous. The first four chapters follow the original text in covering the basic ideas of molecular collisions, dynamics, cross sections, energy partitioning, elastrc, inelastic and reactive scattering, kinematics, potential energy surfaces, microscopic rate constants, classical trajectories, the role of angular momentum and theories of energy disposal. These chapters have been extensively updated and expanded with hardly any
Division CJ~Chemistry,
RALPH STURGEON
National Research Council of Canada, Ottawa, Canada KlA OR9
Department of Chemistry, University of Manchester, Man&ester, Ml3 9PL. U.K.
P. A. GORRY
Acre, Vol. 44A, No. I I. pp. 1229-1231, 1988.
Pergamon Press pk. Printed in Great Britain.
BOOK REVIEWS A HANDBOOK OF NUCLEAR MAGNETIC RESONANCE, by R. FREEMAN. Longman, U.K., 1988, 312 pp., f 18.95.
at work in alpine villages where the ‘. . normal flow of skiers down the slope . ’ is a relaxation process. Such descriptions convey much about the subject. Even when the topic is not illustrated by an appropriate story the text has an uncommon style. For example, phrases like ‘spin gymnastics’ and ‘spin choreography’ are used to describe the behaviour of nuclear spins in pulsed NMR experiments. Any text book needs to be judged on more than just the selection of topics and the elegance of the style. It is, of course, of paramount importance that the text be accurate and, ideally, accessible to a wide readership. As far as I can judge, Freeman’s book satisfies both criteria, as one might have expected from a handbook by one of the leading workers in the NMR field. The idea of providing a pictorial and, for many entries, a non-mathematical description works well. I will use this book not only for my benefit but also for the benefit of the students I teach. Freeman says in the preface that ‘. the handbook will have achieved its aim if it sits on the spectrometer console. rather than on the library shelf’. My copy will sit in my office; I will buy a second copy for the spectrometer.
In recent years there has been a deluge of books about NMR spectroscopy aimed at all levels of the market: undergraduates, research workers, chemists, biologists and so on. Many of the books are useful but few are unique. The book by Freeman is undoubtedly both useful and unique. The author has eschewed the conventional approach for describing NMR. Instead he has given an account of a diverse range of topics organized under 59 headings in alphabetical order: from Adiabatic Fast Passage to Zero Filling, and taking in subjects such as Composite Pulses, Intensities, Rotating Frame and Two-Dimensional Spectroscopy along the way. The book resembles a selective, but extensive, dictionary or encylopedia rather than the usual text-book format. The choice of topics should include something for all NMR practitioners. I was particularly pleased to see a section on Product Operator Formalism, which is something I have found difficult to understand. Throughout the book the engaging style of the author is apparent, not only in the many cartoons which illustrate the text, but also in the text itself. Examples are: in the section on Spin-Spin Relaxation we read of ‘A client . . trying to negotiate a loan from the pawnbroker. . ‘, the Nuclear Overhauser Effect is introduced with a discussion of ski-lifts
School of Chemical Sciences, University of East Anglia, Norwich, U.K.
SPECTROCHEMICAL ANALYSIS, JAMES D. INGLE, JR. and STANLEY R. CROUCH. Prentice Hall, Englewood Cliffs, New Jersey, 1988, xv+ 590 pp., $52.00, ISBN O-13-826876-2. analysis spectrochemical methods of Optical (u.v.-visible-i.r.) rank prominently amongst all analytical methods for their frequency of use, yet comprehensive coverage of their methodologies in a single treatise is rare. This book is intended to fill this gap and was conceived as a textbook for graduate and advanced undergraduate students. The level is aimed intermediate between the survey coverage of spectrochemical methods found in general instrumental analysis texts and the comprehensive coverage afforded by monographs devoted to one or two such techniques. Both atomic and molecular spectroscopy are addressed but written to be used independently of one another. IUPAC terminology has been used and consistent sets of units maintained. The book is divided into five main sections. The first six chapters introduce fundamental concepts. These encompass a brief introduction to the nature of spectrochemical information and measurements, analytical methodology, instrumentation used in optical spectrometers and signal-to-noise ratio (S/N) considerations. Specific topics addressed include basic information concerning radiation-matter interactions; the quantitative mathematical relationships governing the measured signals and S/N ratios obtained and their relationship to instrumental factors; basic optical relationships and imaging; optical radiation sources and transducers as well as signal processing and readout. General principles and concepts as well as fundamental equations pertaining to atomic spectroscopic techniques are
G. MOORE
covered in Chapter 7. These include a discussion of spectral line shapes and intensities for emission, absorption and fluorescence. In an attempt to keep with one of the objectives of this text, i.e. “to emphasize the chemistry which accompanies spectrochemical analysis”, a brief consideration of sample introduction and atomization processes is given along with attendant potential interference effects. These subject areas suffer from rather shallow treatment and are little developed. Chapters 8-11 cover specific atomic spectroscopic methods including flame, plasma, arc and spark emission as well as atomic absorption and fluorescence spectrometry. Each chapter gives consideration to pertinent sources/atomizers, instrumentation, quantitative S/N expressions and performance characteristics. Each chapter concludes with a brief discussion of specific methodology and applications. These latter aspects are not developed in any detail and are of little use other than to place the technique in perspective. This completes that portion of the text formally devoted to atomic spectrometry. Chapter 12 serves to introduce molecular spectroscopy through consideration of electronic and vibronic absorption and luminescence processes. This material lays the foundation for subsequent chapters covering specific molecular techniques such as u.v.-visible molecular absorption (Chapter 13); dispersive and FT-i.r. (absorption/reflection/emission-chapter 14); molecular luminescence (fluorescence, phosphorescence, chemiluminescence and polarization techniques-chapter 15) and molecular scattering techniques (resonance and non-linear Raman, turbidity, nephelometry and laser scattering methods-Chapter 16). Subject handling parallels that used for atomic methods, i.e. a discussion of specific instrumentation, quantitative signal and S/N expressions, some data manipulation considerations, per-
1229
t230
Book Reviews
formance characteristics and applications. In general, applications are given somewhat better treatment than their atomic spectrometry counterparts. Chapter 17, “Spectrochemical Techniques on the Horizon”, deals not so much with newly emerging techniques but those atomic and molecular methods that are becoming or should become standard tools of the trade. These include photoacoustic and thermal lensing spectrometry, laser atomic ionization methods, intracavity absorption, molecular multiphoton ionization and doppler-free absorption techniques. Although discussion of these topics is brief, their introduction here does serve to produce a well-rounded text. The last section of this book consists of six appendices which contain additional information about statistical concepts, optical materials and filters, photomultiplier tubes, sample preparation methods and the interrelationships between experimental and fundamental spectroscopic variables. Of these, the appendix devoted to sample preparation appears rather incongruous in this text and despite the author’s intention of treating the chemical side of speetrochemical analysis, this section is too short to be of any use whatsoever. Informative tables of units, conversion factors and symbols along with a useful and comprehensive subject index conclude this text. Throughout this book the authors have attempted to stress principles and concepts by presenting them first before the details of a given topic are introduced. Liberal use of
figures with extended captions and summary tables which compliment textual information aid in achieving this aim. Bold face type has also been utilized as a highlight whenever new terminology is introduced. The brief set of cited literature appended to each chapter highlights selected sources of general references covering the subjects considered in the text and of specialized references providing additional details on specific topics. The authors have been able to draw significantly from their first hand experience in many of the fundamental and practical aspects covered in this book, permitting them to offer concise yet lucid discussions of many abstract concepts. As well, their considerable teaching experience has given them the foresight to format the material so as to make it an appealing course companion. That the book is intended primarily for use as a graduate course text is also evident from the probing sets of problems which accompany each chapter. Overall, the volume is durably bound, relatively free of typographical errors and is attractively priced for its intended use. Although the book is primarily recommended as a text for a course on spectrochemical analysis, it will also appeal to practicing spectroscopists as a useful reference source and valued addition to a personal library.
AND REACTION DYNAMICS MOLECULAR CHEMICAL REACTIVITY by R. D. LEVINE and R. B.
section not undergoing major changes. As well as new examples for older topics we find totally new material such as picosecond measurements, multiphoton absorption and a discussion of the molecular orbital basis for steric effects. The final three chapters replace the last two of the earlier work and represent a major rewrite and re-ordering of these, with a huge increase in the material covered. These chapters cover the areas of experimental and theoretical techniques, molecular energy transfer, reaction dynamics and chemical reactivity. It here that we find the new topics introduced in most detail and the authors have done an excellent job in tying together so many disparate strands into a cohesive whole. Of the original material it is the topics of curve crossings and suprisal analysis that has been most extended to reflect their growing importance. The new material includes topics such as multiphoton absorption/ionization, molecular beam-surface interactions, bimolecular emission spectroscapy, laser-assisted collisions, clusters and cluster chemistry, stereo-specific dynamics, orientation, alignment and orbital control. Many of these areas are still in their infancy and it is particularly welcome to see their inclusion here. In a book of this type., where a large degree of selectivity is required, it is always possible to quibble about particular inclusions or omissions but overall the coverage is extensive, fair and representative of the field as a whole. The book is a welcome addition to the area and a worthy successor to the original work.
BERNSTEIN,E25. The field of molecular reaction dynamics has expanded at a phenomenal rate over the last two decades-and shows no sign of abating; there is thus a real need.for books that can present the wealth of new material in a form accessible to third-year undergraduate/post-graduate students. One of the mainstays has been “Molecular Reaction Dynamics”, by the same authors, which is now twelve years old. The present book is a replacement to that work and represents a major rewrite and extension of the earlier text. Indeed the extent of this can be judged from the fact that the book has doubled in length to over 500 pages and in many ways it should be considered an entirely new work. The book follows the ambitious aim of the previous work in trying to provide an introduction to the entire field of molecular reaction dynamics. The approach is to emphasize the important essence of the phenomena and their interpretation with enough accompanying detail to enable the interested reader to pursue the matter to greater depths-via the extensive reading lists provided for each section. This is not to suggest that the authors are shy of introducing a rigorous and quantitative treatment where necessary or advantageous. The first four chapters follow the original text in covering the basic ideas of molecular collisions, dynamics, cross sections, energy partitioning, elastrc, inelastic and reactive scattering, kinematics, potential energy surfaces, microscopic rate constants, classical trajectories, the role of angular momentum and theories of energy disposal. These chapters have been extensively updated and expanded with hardly any
Division CJ~Chemistry,
RALPH STURGEON
National Research Council of Canada, Ottawa, Canada KlA OR9
Department of Chemistry, University of Manchester, Man&ester, Ml3 9PL. U.K.
P. A. GORRY