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Dissertation
A study on the hydrated systems of H₂SO₄,(H₂SO₄)₂,NH₃·H₂SO₄,SO₃ and its atmospheric implications
Doctor of Philosophy (Ph.D.), Drexel University
Nov 1998
DOI:
https://doi.org/10.17918/00001481
Abstract
An ab initio quantum mechanical and density functional theory study was performed on H₂SO₄·nH₂O, n=0-7, (H₂SO₄)₂·nH₂O, n=0-6, NH₃·H₂SO₄·nH₂O, n=0-5, and SO₃·nH₂O, n=0-5. A comparison is performed on selected quantum mechanical theories (Hartree-Fock and Moller-Plesset Perturbation) and a recent density functional theory (Becke's Hybrid Functional using the correlation correction of Lee, Yang and Parr) at various sized basis sets (6-311 G**, 6-311+G(2d,p) and 6-311 G++G(2d,2p)). Optimized geometries, dipoles, heat capacities, rotational constants and harmonic frequencies are reported for selected molecular clusters. Internal energy, enthalpy, entropy and free energy changes are reported for the hydration reactions of the above selected compounds at various temperatures found in the troposphere and stratosphere. Isomerization enthalpies, entropies and free energies are reported for reactions of H₂SO₄·nH₂O [double-ended arrow] HSO₄⁻·(n-1)H₂O·H₃O⁺, n=3-6. NH₃·H₂SO₄·nH₂O [double-ended arrow] NH₄⁺·nH₂O·HSO₄⁻, n=2-5. SO₃·nH₂O [double-ended arrow] H₂SO₄·(n-1)H₂O, n=1-5. The ab initio quantum mechanical and density functional theory results are used to implement two chemical kinetic models. The kinetic models compare quite well with the reported experimental results, considering that the rate constants in the models were not fit to experimental data.
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Details
- Title
- A study on the hydrated systems of H₂SO₄,(H₂SO₄)₂,NH₃·H₂SO₄,SO₃ and its atmospheric implications
- Creators
- James C. Ianni
- Contributors
- Alan R. Bandy (Advisor)
- Awarding Institution
- Drexel University
- Degree Awarded
- Doctor of Philosophy (Ph.D.)
- Publisher
- Drexel University; Philadelphia, Pennsylvania
- Number of pages
- xii, 228 pages
- Resource Type
- Dissertation
- Language
- English
- Academic Unit
- College of Arts and Sciences; Chemistry; Drexel University
- Other Identifier
- 991014970318604721