H + CH{sub 2}CO {yields} CH{sub 3} + CO at high temperature : a high pressure chemical activation reaction with positive barrier.

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The Laser Photolysis-Shock Tube (LP-ST) technique coupled with H-atom atomic resonance absorption spectrometry (ARAS) has been used to study reaction, H + CH{sub 2}CO {r_arrow} CH{sub 3} + CO, over the temperature range, 863-1400 K. The results can be represented by the Arrhenius expression, k = (4.85 {+-} 0.70) x 10{sup {minus}11} exp({minus}2328 {+-} 155 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The present data have been combined with the earlier low temperature flash photolysis-resonance fluorescence measurements to yield a joint three parameter expression, k = 5.44 x 10{sup {minus}14} T{sup 0.8513} exp({minus}1429 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. ... continued below

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Hranisavljevic, J.; Kumaran, S. S. & Michael, J. V. December 8, 1997.

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The Laser Photolysis-Shock Tube (LP-ST) technique coupled with H-atom atomic resonance absorption spectrometry (ARAS) has been used to study reaction, H + CH{sub 2}CO {r_arrow} CH{sub 3} + CO, over the temperature range, 863-1400 K. The results can be represented by the Arrhenius expression, k = (4.85 {+-} 0.70) x 10{sup {minus}11} exp({minus}2328 {+-} 155 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The present data have been combined with the earlier low temperature flash photolysis-resonance fluorescence measurements to yield a joint three parameter expression, k = 5.44 x 10{sup {minus}14} T{sup 0.8513} exp({minus}1429 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. This is a chemical activation process that proceeds through vibrationally excited acetyl radicals. However, due to the presence of a low lying forward dissociation channel to CH{sub 3} + CO, the present results refer to the high pressure limiting rate constants. Hence, transition state theory with Eckart tunneling is used to explain the data.

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20 p.

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OSTI as DE00008910

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  • 27th Symposium on Combustion, Boulder, CO (US), 08/02/1998--08/07/1998

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  • Report No.: ANL/CHM/CP-95085
  • Grant Number: W-31-109-ENG-38
  • Office of Scientific & Technical Information Report Number: 8910
  • Archival Resource Key: ark:/67531/metadc794544

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  • December 8, 1997

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  • Dec. 19, 2015, 7:14 p.m.

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Hranisavljevic, J.; Kumaran, S. S. & Michael, J. V. H + CH{sub 2}CO {yields} CH{sub 3} + CO at high temperature : a high pressure chemical activation reaction with positive barrier., article, December 8, 1997; Illinois. (digital.library.unt.edu/ark:/67531/metadc794544/: accessed February 15, 2019), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.