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Reactions of Charged Species in Supercritical Xenon as Studied by Pulse Radiolysis†
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Abstract
The results of an initial study of the pulse radiolysis of supercritical xenon are reported. In pure xenon, transients are formed that absorb broadly throughout the visible. These transients are assigned to excimer species, Xe2*, on the basis of lifetime and kinetic data. The formation of excimers by electron−ion recombination was time-resolved by pulse−probe measurements. The excimers can be quenched by adding small amounts of ethane, which then facilitates detection of other transients by absorption spectroscopy. The added ethane also accelerates the thermalization of electrons and allows measurements of fast reaction rates of thermal electrons. Electron attachment to hexafluorobenzene occurs near the maximum rate at high pressures in xenon−ethane mixtures. The C6F6- anion formed absorbs with a maximum at 500 nm and disappears by second-order kinetics. The mobility of this anion, as measured by conductivity, indicates sizable clusters of solvent around the ion at all pressures, which are of maximum size near critical density. The rate of electron transfer from C6F6- to benzoquinone exceeds 1 × 1011 m-1 s-1 at most pressures. The rate maximizes near 62 bar at 21.4 °C. A maximum at this pressure is predicted by diffusion. The maximum is related to the increase in cluster size around the anion, which occurs at this pressure.
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This article has been cited by 2 ACS Journal articles (2 most recent appear below).
Energetics and Volume Changes in Electron Attachment to Pyrazine in Supercritical Xenon
Richard A. Holroyd and Jack M. Preses, Masaru Nishikawa, Kengo ItohThe Journal of Physical Chemistry B2007 111 (24), 6684-6689Energetics and Volume Changes in Electron Attachment to Pyrazine in Supercritical Xenon
Richard A. Holroyd and Jack M. Preses, Masaru Nishikawa, Kengo ItohThe Journal of Physical Chemistry B2007 111 (24), 6684-6689The attachment of electrons to pyrazine occurs reversibly over a wide range of pressures at and above room temperature in supercritical xenon. The rate constant for attachment increases with pressure at low pressures, passes through a maximum, and levels ...
Properties and Reactions of Charged Species in Nonpolar Supercritical Fluids
Richard Holroyd, Masaru Nishikawa, Kengo ItohThe Journal of Physical Chemistry B2005 109 (7), 2478-2486Properties and Reactions of Charged Species in Nonpolar Supercritical Fluids
Richard Holroyd, Masaru Nishikawa, Kengo ItohThe Journal of Physical Chemistry B2005 109 (7), 2478-2486This review focuses on the properties and reactions of charged species in supercritical fluids. The techniques of pulse conductivity and transient absorption are used to follow the behavior of charged species. We begin with a discussion of the mobilities, ...
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History
- Published In Issue July 31, 2003
- Received January 8, 2003
Revised March 4, 2003
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