A search for mode-selective chemistry: The unimolecular dissociation of t-butyl hydroperoxide induced by vibrational overtone excitation
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Source and publish data:
Journal of Chemical Physics p. 4447 - 4458 (1982)
Update date:2022-08-16
Topics:
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Authors:
Chandler, David W.
Farneth, William E.
Zare, Richard N.
Article abstract of DOI:10.1063/1.444447
The use of optoacoustic spectroscopy permits both the monitoring of the overtone excitation of t-butylhydroperoxide (t-BuOOH) and the in situ detection of the resulting reaction product t-butanol (t-BuOH).The sample is contained in a reaction cell, equippedwith a microphone, in which all surfaces have been specially passivated.The cell is placed inside the cavity of a dye laser tuned to excite the 5-0 O-H stretch of the t-BuOOH at 619.0 nm.The dissociation process yields directly OH and t-BuO, and the latter readily abstracts a hydrogen atom from a parent molecule to form t-butanol (t-BuOH).The appearance rate of t-BuOH is obtained by ratioing the area under the 5-0 O-H stretch of tBuOH to that of a combination band of t-BuOOH.At low pressures, below 40 Torr, a plot of the reciprocal of the t-BuOH appearance rate versus total pressure shows near linear behavior.This linearlity can be well described by a statistical model (RRKM) when careful averaging of the dissociation rate over the thermal energy distribution of the photoactivated molecules is included.At pressures above 40 Torr, a marked deviation from linearity appears.This deviation is fit to a kinetic model in which the dissociation rate of an energy nonrandomized molecule competes with the rate of intramolecular energy relaxation.This places a lower bound of >= 5.0*1011 s-1 on the rate of energy randomization.A discussion of this model in the context of other possible kinetic schemes as well as other photoactivated and chemically activated systems is presented.
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Full text of DOI:10.1063/1.444447
A search for modeselective chemistry: The unimolecular dissociation of t
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Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
Downloaded 02 Oct 2012 to 128.143.23.241. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
