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 Title: Volumetric considerations in thermodynamic solution modeling Author(s): Hansen, Allen Royce Doctoral Committee Chair(s): Eckert, Charles A. Department / Program: Chemical and Biomolecular Engineering Discipline: Chemical Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Engineering, Chemical Abstract: Current thermodynamic solution models are generally incapable of cross predicting excess properties and usually have limited applicability. One reason for this may be due to the volumetric considerations which are ignored or improperly represented in the models. In this work, the thermodynamic utility of the abundant data base of volumetric information is evaluated by developing new models and acquiring more data.A new model which interrelates the liquid phase excess Gibbs energy, enthalpy, and volume is developed. The model is based upon the fact that most mixtures are immiscible in the solid phases, and, therefore, have steep solid phase boundaries. This single assumption allows the model potentially to be applied to all types of mixtures, including organic, metallic, electrolytic, and polymeric solutions. The model predicts that the excess properties are related to each other through various fusion properties, pure component volumes and enthalpies of fusion in particular, and has been applied to a wide variety of organic and liquid metal mixtures. The results show qualitative validity without the use of adjustable parameters, and more quantitative ability when effective fusion properties are utilized. The model is also shown to rationalize some sign, magnitude, and shape phenomena.Also, by use of a direct Archimedes' technique, volumetric data for some pure liquid metals and mixtures of Bi-Zn, In-Sb, Pb-Sb, and Mg-Sb were determined from near the liquidus up to as much as 1000$\sp\circ$C. The excess volumes for the alloys studied are presented and discussed. A simple, semiempirical model, based upon valence electron densities, was developed for excess volumes for noncompound-forming liquid alloys.Finally, new experimental equipment have been developed and used to determine volumetric properties of some liquid metals at temperatures up to 800$\sp\circ$C and pressures up to 4 kbar using a dilatometric technique. The results for liquid mercury, tin, lead, and bismuth are presented. Also, the significance of data of this sort is described with particular reference to our new modeling efforts. Issue Date: 1990 Type: Text Language: English URI: http://hdl.handle.net/2142/18945 Rights Information: Copyright 1990 Hansen, Allen Royce Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9114259 OCLC Identifier: (UMI)AAI9114259
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