Thermodynamics of molecular species

An updated and fresh perspective of the subject based on the concepts that the thermodynamic properties of a system are independent whether composition is specified in terms of formal components or molecular species and that the laws of thermodynamics are independent of the observational time-scale. By applying these concepts, the author has derived approximately 20 general theorems concerned with the thermodynamic properties of molecular species and their relationships to those of the formal components. Grunwald defines molecular species to include all participants in reaction mechanisms. Proved theories are supplemented with verbal explanations and explicit examples. Applications chapters include environmental isomers in liquids and thermodynamic properties of water and aqueous systems. Extra thermodynamic chapters feature interionic attraction theory and structure-energy correlation. Booknews Grunwald (chemistry, Brandeis U.) updates the concepts of chemical thermodynamics to recognize modern technologies. The foundation of his scheme is the flexible composition model, which specifies composition by listing the formal components of the system, the molecular species that stem from the components, and if necessary any subspecies derived from the molecular species. The flexibility arises from listing only those molecular species that are chemically or stoichiometrically significant and changing that list as the understanding of the chemistry in the system improves. Annotation c. by Book News, Inc., Portland, Or. Reflecting the current operational practice of chemistry, this unique book provides an important update of traditional chemical thermodynamics, especially the thermodynamics of liquid solutions. Using a flexible composition model that enumerates both the formal components of a system and the molecular species derived from them, Thermodynamics of Molecular Species introduces a set of general theorems and proofs that address a range of significant phenomena beyond the reach of traditional chemical thermodynamics, such as enthalpy-entropy compensation, molar shifts, and thermodynamic error tolerance. Dr. Grunwald's novel approach creates a natural framework for mechanistic studies of molecular phenomena, while at the same time avoiding some of the complexity of statistical thermodynamics Thermodynamic Components and Molecular Species. Gibbs Free Energy, Chemical Equilibrium, and Correspondence Theorems. Dilute Solutions, Standard Partial Free Energies, and the Stability Theorem. Displacements from Equilibrium and Error Tolerance. Linear Free-Energy Relationships, Transition-State Theory, and Error Tolerance. Enthalpy-Entropy Compensation and Dormant Interactions. Effect of Molar Shifts on State Functions. Molar-Shift Terms in Dilute Solutions. Hard-Sphere and Potential-Energy Cages Around Molecules in Liquids. Environmental Isomers, Molecular Complexes and Cage Exchange in Liquids. Solvation in Dilute Solutions. Thermodynamics of Ionic Species.