Resonance Raman Spectroscopy of Reaction Intermediates by a Rapid Mixing, Continuous Flow Technique

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Abstract:

Raman spectroscopy is potentially of great value in elucidating the structure of intermediates in chemical reactions. However, its utility in this regard has been limited because of the time required to scan a spectrum using a conventional spectrometer and static sample techniques. If one wishes to obtain a spectrum of an aliquot of a reaction mixture, while negligible concentration changes occur in the reactants, intermediates, and products, then clearly the half-life of the chemical reaction must be long compared to the spectral scan time. Since 10 min may be considered a typical time required to scan a 1000 cm−1 Raman spectrum, ordinary (static) sample handling techniques will yield satisfactory spectra of intermediates only for very slow reactions. Another disadvantage of static sample techniques, in Raman spectroscopy of reaction intermediates, occurs when one attempts to exploit the resonance Raman effect. In this situation, localized sample heating by the exciting radiation will generally cause a manifold increase in reaction rate and a concomitant decrease in the lifetimes of the intermediates. We now report a technique which allows one to obtain Raman spectra of reaction intermediates, with little determent due to reaction rate or sample heating.

Keywords: Instrumentation, Raman; Raman spectroscopy; Reaction intermediates; Resonance Raman

Document Type: Short Communication

DOI: http://dx.doi.org/10.1366/000370274774331886

Affiliations: Department of Chemistry, Princeton University, Princeton, New Jersey 08540

Publication date: November 1, 1974

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