Several factors which affect the transport of pyridine, quinoline and acridine (aza-arenes) in saturated porous media were investigated in laboratory experiments in order to provide data for input into coupled models that may be applied to predicting the fate of these compounds in groundwater. The effect of pH and ligand type and concentration on acridine solubility was studied in a series of batch and pH-stat experiments. There was a decrease in acridine solubility below the compound's pKₐ due to acridine/ligand precipitate formation. The reaction stoichiometry and solute/sorbent interactions of aza-arene adsorbed to porous silica were determined from batch adsorption and Raman spectroscopy experiments. The neutral aza-arene was hydrogen bonded to surface sites above the compound's pKₐ and there was a cation/ClO₄⁻ complex interacting with surface sites through dipole-dipole interactions below the pKₐ of the compound. The effect of pH, temperature, ligand type, average linear velocity and initial aqueous phase solute concentration on the adsorption of aza-arenes to porous silica was investigated in a series of column experiments. The extent of adsorption followed the trend pyridine < quinoline < acridine due to greater overlap of the molecule with adsorption sites as the number of rings increases. The extent of adsorption was greater below the compound's pKₐ than above because the complex was able to optimize its orientation with the surface. The extent of adsorption of neutral acridine was enhanced when carbonate was used as a buffer relative to phosphate due to carbonate's more exothermic hydration enthalpy. The isotherms were non-linear above and below the pKₐ of acridine. The enthalpy of the adsorption reaction was less exothermic below the compound's pKₐ than above due to the stronger hydrogen bonds formed between the surface and the neutral molecule compared to the dipole-dipole interactions that bond the complex to the surface below the pKₐ. Non-equilibrium effects on the adsorption reaction were minor. Adsorption-desorption was on the order of seconds to minutes. Kinetic effects became more important as temperature decreased.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/191179 |
| Date | January 1993 |
| Creators | Matzner, Robert Allan. |
| Contributors | Bales, Roger, Neuman, Shlomo, Conklin, Martha, Burke, Mike, Pemberton, Jeanne |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | English |
| Detected Language | English |
| Type | Dissertation-Reproduction (electronic), text |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
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