FLASH PYROLYSIS IR LASER JET SPECTROSCOPY OF KETENE DERIVATIVES
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Date
2000
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Journal ISSN
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Publisher
Ohio State University
Abstract
We have used the flash pyrolysis technique, introduced by Chen and $co-workers^{a}$, to generate free radicals and other short lived species for diode laser absorption spectroscopy in a supersonic $jet^{b}$. The flash pyrolysis technique has proved to be particularly useful for producing ketene derivatives and we have recorded the carbonyl antisymmetric stretching modes of chloroketene (ClHCCO), methyl ketene $(CH_{3}HCCO)$ and propadienoe $(H_{2}C_{3}O)$. The $\nu_{2}$ band of ClHCCO was measured between 2153 and $2161 cm^{-1}$. The molecule was formed by pyrolysis of chloroacetyl chloride at 1500 K. Over 200 lines of $^{35} ClHCCO$ were fitted, fixing the ground state constants to the microwave $values^{c}$. We obtained $A=1.201028(64), B=0.100399(3)$ and $C=0.092530(3) cm^{-1}$ and a band origin of $\nu_{2} = 2157.19238(16) cm^{-1}$. We have also measured many lines of methyl ketene and propadienone generated from propionyl chloride and acrylic anhydride respectively. Their analysis is currently in progress.
Description
$^{a}$ P. Chen, S. D. Colson, W. A. Chupka and J. A. Berson, J. Phys. Chem., 90, 2319 (1986). $^{b}$ Z. Liu, R. J. Livingstone and P. B. Davies, Chem. Phys. Lett., 291 480 (1998). $^{c}$ M. C. L. Gerry, W. Lewis-Bevan and N. P. C. Westwood, J. Chem. Phys., 79 4655 (1983).
Author Institution: Department of Chemistry, University of Cambridge; Department of Chemistry, University of Auckland
Author Institution: Department of Chemistry, University of Cambridge; Department of Chemistry, University of Auckland