After a few faint stirrings of interest in ion-molecule reactions during the early days of mass spectrometry, the subject was almost completely neglected for many years. There was a renascence of interest in the subject following pioneering experiments by Tal'roze in Russia and independently by Steven- son and Schissler and Field, Franklin, and Lampe in this country. Since that time, interest in the subject has continued to grow and the number of papers published to expand almost exponentially during the past 15 years. The result is a body of literature that is now almost beyond any single individual's capacity for encompassing in his reading and research activities. Thus, it seemed timely to prepare a book giving in some detail a comprehen- sive review of the field. Ideally, such a book would be written by one or possibly two authors. Unfortunately, the sheer bulk and variety of the studies of ion-molecule reactions has made it impractical for a single person to prepare a book on the subject in a time that would permit it to be issued before the material covered was obsolete.
Consequently, the only practical, although surely not the ideal, solution is to issue a multiauthor volume. The present book represents our best efforts to accomplish this goal. We have secured from 18 authors material representing the most advanced work in the field and the resulting compilation is presented herein.
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Springer Science+Business Media
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978-0-306-30551-1 (9780306305511)
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Schweitzer Klassifikation
of Volume 1.- 1. Introduction.- 2. Positive-Ion-Molecule Reaction Studies in a Single Electron-Impact Source.- 1. The Continuous Ion Extraction Source.- 2. Establishment of Ion-Molecule Reactions.- 3. Reaction Kinetics.- 4. The Pulsed Ion Source.- 5. Energy Effects in Ion-Molecule Reactions.- 6. Rate Method of Identifying Two Precursors of a Single Product.- 7. Reactions and Reaction Kinetics at Elevated Pressures.- 8. Reactions of Electronically Excited Ions.- 9. Residence Times from Mobilities.- 10. Energy Distribution in Products of Ion-Molecule Reactions.- 11. Proton Affinities.- References.- 3. Ion-Molecule Reactions by Photoionization Techniques.- 1. Introduction.- 2. Experimental Technique.- 2.1. Optical Monochromator.- 2.2. Light Sources.- 2.3. Mass Spectrometers.- 2.4. Ion Sources and Reaction Chambers.- 2.5. Pulse Techniques.- 3. Photoionization Theory.- 3.1. General.- 3.2. Direct Ionization.- 3.3. Autoionization.- 3.4. Ion-Pair Formation.- 3.5. Preparation of Pure Ion Species.- 3.6. Identification of Reactant Ions.- 3.7. Preparation of Ions in States of Known Internal Energy.- 4. Reactions of Pure Ion Preparations.- 4.1. Reactions in Propylene and 1,3-Butadiene.- 4.2. Reactions in Methane.- 4.3. The Pulse Experiments of Warneck.- 4.4. High-Pressure Photoionization; Reactions of C4H 8+.- 4.5. Endoergic Reactions; Determination of Heats of Formation from Thresholds.- 5. Reactions of Ions with Known Internal Energies.- 5.1. Reactions of NH3+ with NH3 and H2O.- 5.2. Reactions of H2+ with H2.- 5.3. Reactions of H2+ with He, Ne, and Ar.- 5.4. Charge Transfer in H2.- References.- 4. Negative-Ion-Neutral Reactions.- 1. Introduction.- 2. Sources of Negative Ions.- 2.1. Dissociative Attachment.- 2.2. Three-Body Attachment.- 2.3. Ion-Pair Production.- 2.4. Radiative Attachment.- 2.5. Ion-Neutral Reactions.- 3. Experimental Techniques.- 3.1. Ion-Source Method.- 3.2. Double Mass-Spectrometer Method.- 4. Experimental Results.- 4.1. Reactions of H- and D-.- 4.2. Reactions of C-.- 4.3. Reactions of O- with H2 and with O2.- 4.4. Reactions of O- with Some Triatomic Molecules.- 4.5. Additional Reactions with Diatomic and Triatomic Molecules.- 5. Postscript.- References.- 5. Rate Constants and Cross Sections.- 1. General Survey.- 1.1. Introduction.- 1.2. Accuracy-Present Status and Present Need.- 1.3. Nomenclature.- 1.4. The Ideal Experiment: Successive Refinement in the Determination of a Reaction Rate.- 1.5. Survey of Chapter Contents.- 2. Rate Constants and Cross Sections-Some Formal Considerations.- 2.1. The Relationship between Rate Constants and Cross Sections.- 2.2. Unfolding Procedures.- 2.3. Nonequilibrium Effects.- 2.4. Conclusions.- 3. Available Techniques.- 3.1. Survey and Organization.- 3.2. Some General Problems.- 3.3. Beam Techniques.- 3.4. Swarm Techniques.- 3.5. Plasma Techniques.- 3.6. Comparative Assessment of Techniques.- 4. Theoretical Prediction of Rate Parameters and Comparison with Experiment.- 4.1. Survey.- 4.2. Close-Collision Cross Sections.- 4.3. Trajectory Calculations over the Potential Energy Hypersurface.- 4.4. Statistical Models.- 4.5. Crossings between Potential Energy Surfaces.- 4.6. Direct Models at High Energies.- 5. Conclusion.- 5.1. Miscellaneous Topics.- 5.2. Recommendations for the Adoption of Standard Procedures.- 5.3. Survey and Prospects.- Notes Added in Proof.- Acknowledgments.- References.- 6. Chemical Ionization Mass Spectrometry.- 1. Introduction.- 2. Experimental.- 3. Mass Spectra of Different Compound Types.- 3.1. Alkanes.- 3.2. Cycloparaffins.- 3.3. Alkenes and Alkynes.- 3.4. Aromatics.- 3.5. C7H8 Isomers.- 3.6. Chemical Ionization of Benzene by Rare Gas Reactants.- 3.7. Esters.- 3.8. Alcohols.- 3.9. Miscellaneous Compounds.- 4. Temperature Effects in Chemical Ionization.- 4.1. Benzyl Acetate and t-Amyl Acetate Spectra at Various Temperatures.- 4.2. Mathematical Formulation of Chemical Ionization Kinetics.- 4.3. Kinetic Results for Benzyl Acetate and t-Amyl Acetate.- 4.4. Pressure Studies with Benzyl Acetate.- 4.5. Substituted Benzyl Acetates.- 4.6. Methoxymethyl Formate and Methoxymethyl Acetate.- 4.7. Methylthiomethyl Acetate and Methylthiomethyl Propionate.- 4.8. Equilibrium Reactions.- References.- 7. Higher-Order Reaction-Ion Clusters and Ion Solvation.- 1. Introduction.- 2. Ion-Molecule Reactions at Conventional Gas Kinetic Conditions.- 3. Apparatus for Mass Spectrometric Studies of Ion-Molecule Reactions at Pressures Above 1 Torr and Thermal Energies.- 4. Kinetics and Mechanism of Clustering Reactions. The Proton Hydrates. Applications.- 5. Ionic Clustering Equilibria-Determination of Enthalpy and Entropy Changes of Clustering Reactions.- 6. Ionic Solvation in the Gas Phase.- 6.1. Application of Gas-Phase Cluster Studies to Ion-Solvent Molecule Interactions and Heterolytic Organic Reactions.- 6.2. Gas-Phase Hydration of Alkali and Halide Ions..- 6.3. The Hydrated Proton in the Gas Phase.- 6.4. Competitive Solvation in the Gas Phase. H+ by Water and Methanol and by Water and Ammonia Molecules.- 6.5. Solvation of Negative Ions by Various Solvent Molecules. Correlation with Acidity.- 7. Entropy Changes of Ion-Clustering Reactions. Comparison between Experimental and Calculated Values.- 8. Determination of Cluster Dissociation Energies by Collisional Studies.- 9. Application of Ion-Cluster Studies to Processes in the Ionosphere, Radiation Chemistry, and Other Fields.- References.
