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A STUDY OF THE HYDROGEN BONDING CHARACTERISTICS OF HYDROGEN PEROXIDE BY MATRIX ISOLATION VIBRATIONAL SPECTROSCOPY
| Title: | A STUDY OF THE HYDROGEN BONDING CHARACTERISTICS OF HYDROGEN PEROXIDE BY MATRIX ISOLATION VIBRATIONAL SPECTROSCOPY |
| Author: | Goebel, James Robert |
| Description: | Employing a recently developed source of solvent-free hydrogen peroxide, 1:1 complexes of H2O2 with a series of Lewis bases have been formed and characterized. The infrared spectrum of the H2O2(O(CH3)2 complex in argon matrices has been obtained and assigned. Assignments have been confirmed by deuterium substitution on both subunits in the complex. The hydrogen-bonded O-H stretch is shifted 234 cm-1 to lower energy whereas the O-O-H bending mode is shifted 45 cm-1 to higher energy. In a similar fashion hydrogen peroxide complexes were also formed and characterized using the following first row Lewis bases: acetone, ethyl isopropyl ether, water, trifluoroethylamine, ammonia, and trimethylamine. Only limited studies were performed on ethyl isopropyl ether and trifluoroethylamine, but complete studies were performed on the other Lewis bases including isotopic substitution studies. In the water, ammonia, and trimethylamine studies nitrogen was employed as the matrix to improve complex yield and signal/noise. In all these complexes the O-H stretching band was identified as well as other product bands. In another series of experiments hydrogen peroxide complexes were formed and characterized using the following second row Lewis bases: trimethylphosphine, phosphine, dimethyl sulfide, and hydrogen sulfide. All of these complexes were completely studied using isotopic substitution and concentration studies. Comparisons between second and first bases were drawn. A study of hydrogen peroxide as a hydrogen bond acceptor with HCl as the donor was conducted. The 1:1 complex of HCl with H2O2 was formed and characterized in both argon and nitrogen matrices. Once again isotopic substitution and concentration studies were performed and the all the product bands were assigned. The correlation between proton affinities and O-H stretch shifts for all the first and second row bases studied was investigated. And finally, the results of ab initio calculations for all the complexes (except acetone, ethyl isopropyl ether, and trfifluoroethyl amine) were compared to the experimental results. |
| Permanent Link: |
http://rave.ohiolink.edu/etdc/view?acc_num=ucin971366564
http://hdl.handle.net/2374.OX/11131 |
| Date: | 2000 |
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