Thermodynamics of Molecular Species

  • ID: 2174412
  • Book
  • 324 Pages
  • John Wiley and Sons Ltd
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A much–needed expansion of traditional chemical thermodynamic concepts––essential reading for today′s advanced students and research professionals

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. The book′s features include:

∗ A broad definition of molecular species that includes all participants in reaction mechanisms: reactants, products, substrates, catalysts, reactive intermediates, and transition states

∗ Solid experimental evidence supported by explicit examples across a breadth of areas––including solvation, water and aqueous solutions, environmental isomers, ions, and ion pairs

∗ Thermodynamic aspects of interionic attraction theory and of structure–energy correlations

∗ Almost 100 figures and diagrams that express abstract and mathematical ideas in clear and concrete terms
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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.


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ERNEST GRUNWALD, PhD, is Professor Emeritus of Chemistry at Brandeis University. Coauthor of numerous books and a member of the National Academy of Sciences, he has received many honors and awards for his work, including the Pure Chemistry Award of the American Chemical Society and Guggenheim and Sloan Fellowships.
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