Thermochemistry and Its Applications to Chemical and Biochemical Systems : The Thermochemistry of Molecules, Ionic Species and Free Radicals in Relation to the Understanding of Chemical and Biochemical Systems

The chapters in this book were written by the review lecturers at the NATO Advanced Study Institute on "Thermochemistry Today and Its RoZe in the Immediate Futu:t>e", held in Viana do Casix M. A. V. Ribeiro da Silva (ed.), Thermochemistry and Its Applications to Chemical and Biochemical Systems, ix-x. Front Matter....Pages i-x Techniques and Theory of Titration Calorimetry....Pages 1-16 Applications of Titration Calorimetry....Pages 17-30 Microcalorimetry....Pages 31-46 Differential Scanning Calorimetry....Pages 47-60 An Oxygen Flow Calorimeter for Determining the Heating Value of Kilogram-Size Samples of Municipal Solid Waste....Pages 61-76 Thermogenesis by Heat Conduction Calorimetry....Pages 77-126 The Measurement of Vapour Pressure....Pages 127-141 The Use of a Simultaneous Torsion and Mass-Loss Effusion Apparatus for Determining Vapour Pressures and Enthalpies of Sublimation....Pages 143-156 Vaporization Studies by Knudsen Cell — Mass Spectrometry and Thermodynamic Stability of High Temperature Gaseous Species....Pages 157-181 Transpiration Mass Spectrometry—A New Thermochemical Tool....Pages 183-233 Thermodynamic Activity and Vapor Pressure Models for Silicate Systems Including Coal Slags....Pages 235-251 Metal-Ligand Heats and Related Thermodynamic Quantities by Titration Calorimetry....Pages 253-273 Measurement of Complexing Constants and Enthalpies of Complexing by Batch Calorimetry....Pages 275-287 Metal Ligand Bond Strengths and Bonding Theory....Pages 289-315 Thermochemistry of β-Diketones and Metal-β-Diketonates. Metal-Oxygen Bond Enthalpies....Pages 317-338 Thermochemistry of Metal-Polyamine Complexes....Pages 339-352 Thermochemistry of Main-Group Organometallic Compounds....Pages 353-366 Experimental Thermochemistry of Transition-Metal Organometallic Compounds....Pages 367-382 Thermochemistry of Molecular Transition Metal Compounds....Pages 383-391 Measurement of Enthalpies of Solution of Electrolytes....Pages 393-409 Hydrophobic Hydration of Alkylammonium Bromides in Aqueous Mixed Solvents....Pages 411-424 Solvation of Alcohols, Amines, Ureas and Amides in Mixed Solvents....Pages 425-437 Microcalorimetry as an Analytical Tool in Biology....Pages 439-460 Application of Calorimetry to the Life Sciences....Pages 461-488 Superhelicity and Energetics of Structural Transitions of Nucleic Acids....Pages 489-509 Calorimetric Studies in Binding Reactions in Biochemistry....Pages 511-530 Cellular Thermochemistry: Resting State and Stimulation....Pages 531-540 Differential Scanning Calorimetry Applications to Protein Solutions....Pages 541-568 Thermochemistry of Molecules, Molecule-Ions, and Free Radicals. Factors Influencing Bond Energies in these Species....Pages 569-600 Experimental Methods to Study the Thermochemistry of Gas Phase Ions and Ion-Molecule Reactions....Pages 601-626 The Thermochemistry of Gas Phase Ion-Molecule Reactions....Pages 627-651 The Application of Low-Temperature Calorimetry to Some Contemporary Problems in Solid State Chemistry....Pages 653-670 Thermodynamics of Crystals — 1982....Pages 671-694 Calorimetry of Phase, Schottky and other Transitions....Pages 695-718 Thermophysics of Mineral and Rock Systems....Pages 719-744 Computerized Adiabatic Thermophysical Calorimetry....Pages 745-767 Lectures on Thermochemistry and Kinetics....Pages 769-787 Barriers to Internal Rotation in Inorganic Species....Pages 789-802 Critical Evaluation of Thermodynamic Data — A Research Activity....Pages 803-814 Thermochemistry Today and Its Role in the Immediate Future....Pages 815-821 Back Matter....Pages 823-845 The progress that has recently been made in the field and applications of thermochemistry, having as a consequence an in crease in the interest of the subject, undoubtedly can be con sidered highly remarkable. Traditionally, the thermochemist has provided accurate ther mal data on chemicaZ compounds of practicaZ importance, mainly by calorimetric and by equilibrium studies. The scope has been considerably extended in recent years, following the development of microcalorimetric techniques, of flow calorimetry, of titra tion calorimetry, and of high temperature calorimetry. The im pact has been most noticeable in biochemical studies, in metallur gical studies, and in organometallic and inorganic thermochemis try. A parallel development has led to increasing output of signi ficant thermal data on gas-phase transient species (e.g. free ra dicals, radical ions) by kineticists, and by use of photoioniza tion spectroscopy, mass spectroscopy and ion-cyclotron resonance spectroscopy. These species are outside the scope of traditional calorimetric study, but as more data on them become available they vastly add to the value of traditional thermochemical data and enable bond energies to be evaluated, and the inter-relation of molecular structure and bonding energy to be more closely exa mined Proceedings of the NATO Advanced Study Institute on Thermochemistry Today and Its Role in the Immediate Future, Viano do Castelo, Portugal, July 5-15, 1982