Department of Chemistry  


A Notebook for Topics in Thermodynamics of Solutions and Liquid MixturesOver three hundred Topics in Thermodynamics (which can addressed individually) describe the thermodynamic properties of aqueous solutions and aqueous mixtures. The Gibbs energies of these systems are discussed leading through successive differential operations to enthalpies, volumes, heat capacities, compressibilities (isobaric and isentropic) and expansibilities. These properties are linked quantitatively to corresponding partial molar properties including chemical potentials and generally partial molar volumes, partial molar enthalpies, partial molar heat capacities, partial molar expansibilities and compressibilities. Key equations link experimentally determined variables (e.g. densities) and partial molar properties ( e.g. partial molar volumes) of the components in an aqueous solution/mixture. Extensive references are given to published papers describing application of the equations described in The Topics. Further Topics describe application of thermodynamic equations to descriptions of chemical equilibria for many classes of systems together with the dependences of equilibrium constants on temperature and pressure. The analysis is extended to a consideration of rate constants for chemical reactions between solutes in solution. The theoretical basis is described for the DebyeHuckel treatment of salt solutions, Bjerrum equation for ion association, Euler’s theorem, Legendre (thermodynamic) transformations, Lewisian variables, L’Hospital’s Rules. Related Topics describe electrical units, axioms , equilibrium and frozen properties. In each Topic, special attention is given to the units of parameters involved in equations, ensuring that the derived property has self consistent units as required in the SI system. Related Topics describe electrical units, axioms and both equilibrium and frozen properties. The thermodynamic analysis is extended to a consideration of several special Topics including thermodynamic stability, the Law of Mass Action, Adsorption, Isochoric and Equilibrium properties, extrathermodynamic analysis of acid strengths and solvent polarities, Hildebrand Solubility parameters, internal pressure of liquids, ion association, surfactants, Gibbs Adsorption Isotherm, Phase Rule, thermal stability and hydrogen ions in aqueous systems. In the context of quantitative description of aqueous systems, key references are given to the properties of water including molar volume, viscosity, relative permittivity and selfdissociation. Cross references are given to relevant subject matter in other Topics.

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Last updated: 29 August 2004