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Proceedings Paper

Enhanced Kinetic Ftir Observation Of Transient Species Generated In SITU By Pulsed Laser Photolysis
Author(s): M. S. Paquette; H. D. Gafney; M. S. Darsillo
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Paper Abstract

Modern, rapid scanning FTIR spectrometers allow efficient real time sampling of time dependent phenomena such as chromatographic peak elution and chemical reactions. We have particular interest in kinetic and mechanistic studies of catalytic reactions as well as rapid chemical reactions. Using appropriate reactor-cells, we have the potential for observing in situ the existence and fate of short lived species. However, these transient materials, by virtue of their reactivity, are usually difficult to observe in their unenhanced amounts. We have developed techniques which employ ultraviolet, visible, and infrared laser pulses to stimulate reactions in solutions and on surfaces enhancing the occurrence of reactive species. We will present results of an in situ FTIR study of the laser photolysis of iron pentacarbonyl in homogeneous solu-tion and on a porous vycor glass support. An analysis of spectral data from several experiments enabled us to identify reactive iron subcarbonyl species as well as stable compounds and clusters. Spectral stripping procedures were used to quantitate individual components in the kinetic FTIR spectra yielding catalyst lifetimes as short as 0.2 sec. From these experiments we have postulated comprehensive models describing chemical, photochemical, and physical processes in stoichiometric and catalytic reactions of iron carbonyl complexes.

Paper Details

Date Published: 20 December 1985
PDF: 3 pages
Proc. SPIE 0553, Fourier and Computerized Infrared Spectroscopy, (20 December 1985); doi: 10.1117/12.970906
Show Author Affiliations
M. S. Paquette, Dow Chemical Company (United States)
H. D. Gafney, City University of New York (United States)
M. S. Darsillo, City University of New York (United States)

Published in SPIE Proceedings Vol. 0553:
Fourier and Computerized Infrared Spectroscopy
David G. Cameron; Jeannette G. Grasselli, Editor(s)

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