Title page for ETD etd-04182009-041418
|Type of Document
||Influence of cation size and surface coverage upon the infrared spectrum of carbon monoxide
||Master of Science
|Anderson, Mark R.
|Tanko, James M.
|Wightman, James P.
|Date of Defense
Adsorbed carbon monoxide is utilized as a double layer probe molecule
because of its strong absorption in infrared region and because of the high sensitivity
of the carbon-oxygen bond to changes in the environment local to the electrode
surface. Potential Difference Infrared Spectroscopy was used to investigate the
structural behavior of CO adsorbed on a platinum electrode. Carbon monoxide was
found to be exclusively linear-bonded on platinum electrode in the presence of tetran-
alkylammonium perchlorate/acetonitrile. No bridge-bonded species were
observed. It was also found that the IR peak position of adsorbed CO is linearly
dependent upon applied electrode potential, in agreement with Electrochemical Stark
effect. The Stark tuning rate of adsorbed CO was determined to be inversely
proportional to electrolyte cation size. This quantitative relationship between the
Stark tuning rate and cation size is the first time that this has been experimentally
demonstrated. Statistical treatment proved that surface coverage influences the rate
of infrared peak position shift. The effect of surface coverage upon the
conformation of tetra-n-octylammonium cation was also observed. Data suggested
that tetra-n-octylammonium cation changes its conformation with surface coverage
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