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I. A Nuclear Magnetic Resonance Study of Metal Carbonlys in the Solid State, and II. Studies of the Surface Chemistry of Rhodium Supported on Alumina


Gleeson, James William (1982) I. A Nuclear Magnetic Resonance Study of Metal Carbonlys in the Solid State, and II. Studies of the Surface Chemistry of Rhodium Supported on Alumina. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/vmgw-qf86.


Part I

The principal components of the 13C nuclear magnetic resonance chemical shift tensors of metal carbonyls containing between one and six metal atoms were determined from the powder patterns of the solid compounds. The tensors of terminally-bound CO groups are highly anisotropic (380 ± 60 ppm) and nearly axially symmetric. The tensors of bridging CO groups are much less anisotropic, due to significant asymmetry in the electron orbitals about the CO internuclear axis. The tensors vary only slightly for different transition metals. There is no intramolecular rearrangement of the metal carbonyls in the solid state at frequencies ≳ 10kHz, except in Fe3(CO)12.

Part II

The surface chemistry of rhodium supported on alumina was studied using infrared spectroscopy and quantitative measurements of the gases adsorbed and evolved during various procedures. First, the behavior of alumina-supported Rh upon heating in the presence of CO, CO2, O2 and H2 was studied. The loss in the capacity to adsorb CO after heating to 525 K increases in the order O2, H2, vacuum < CO2 < CO. Upon heating in CO, some CO is oxidized to CO2 with oxygen from the surface, while the dicarbonyl-forming RhI is reduced to Rh°. The Rh° agglomerates, accounting for the substantial loss in capacity to adsorb CO. Upon heating in CO2, the dicarbonyl-forming RhI is also deactivated. There is little loss in the capacity to adsorb CO upon heating in H2, O2 or vacuum.

Second, the adsorption of H2S and its interaction with CO on Rh supported on alumina was studied. The dissociation of H2S on the Rh at 300 K produces H2 and is inhibited by preadsorbed CO. Rh also facilitates the reaction of H2S with surface oxygen below or at 373 K, in which water is produced. After exposure of the Rh to H2S, CO adsorbs in the linear, but not in the dicarbonyl or bridging modes. Exposure of a CO-precovered surface to H2S displaces much of the bridging CO, but only slowly removes the dicarbonyl and linear CO. Exposure to H2S strongly inhibits the removal of adsorbed CO by O2, but exchange of adsorbed and gas phase CO occurs readily.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Beauchamp, Jesse L.
Thesis Committee:
  • Beauchamp, Jesse L. (chair)
  • Weinberg, William Henry
  • Chan, Sunney I.
  • Grubbs, Robert H.
Defense Date:17 November 1981
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-77-F-0008
Office of Naval Research (ONR)N00014-79-F-0014
Record Number:CaltechTHESIS:05152018-092853858
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10887
Deposited By: Mel Ray
Deposited On:15 May 2018 18:54
Last Modified:19 Apr 2021 22:34

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