A spectroscopic investigation of the thermodynamic properties of liquid organic mixtures
Karachewski, Anne Marie
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https://hdl.handle.net/2142/19175
Description
Title
A spectroscopic investigation of the thermodynamic properties of liquid organic mixtures
Author(s)
Karachewski, Anne Marie
Issue Date
1990
Doctoral Committee Chair(s)
Eckert, Charles A.
Department of Study
Chemical and Biomolecular Engineering
Discipline
Chemical Engineering
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Engineering, Chemical
Language
eng
Abstract
Several thermodynamic models for liquid organics have been developed and will be discussed in this thesis. In addition, recommendations are made for new areas to explore in order to further enhance our understanding of solution properties.
Two chemical-physical models (AVEC - Association with Variable Equilibrium Constant; SAVEC - Solvation and Association with Variable Equilibrium Constant) have been developed for associating mixtures. Hydrogen bonding, a localized and very directional specific interaction has been investigated in various alcohol mixtures using Fourier Transform NMR to measure the number of complexed species in solution. The AVEC and SAVEC model parameters are kept to a minimum and are independently measured by this non-thermodynamic technique. The distinguishing feature of the AVEC and SAVEC models is that the species in solution do not have equal probability of forming and depend on the size of the complex, yet require only a single chemical interaction parameter determined from fitting NMR data and one physical interaction parameter determined from infinite dilution activity coefficients. The AVEC and SAVEC models successfully predict vapor-liquid equilibrium, excess enthalpy as well as liquid-liquid equilibrium.
MOSCED (Modified Separation of Cohesive Energy Density), a chemical-physical predictive model for infinite dilution activity coefficients, has been improved. Recently measured spectroscopic and other physico-chemical data have become available and have been used to improve greatly the quantitative evaluation of the various molecular interactions in solution. This extensive physico-chemical database has been used to substantially reduce the number of adjustable parameters needed to characterize the various interactions with no significant change in accuracy. Currently, the MOSCED model is able to calculate the various solution nonidealities, using only pure component parameters. Using these pure component parameters has lead to a better fundamental understanding of solution properties.
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