Shock tube study on the mechanism of hydrogenation and pyrolysis of acetylene.

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概要

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• Mixtures of acetylene and deuterium have been subjected to shock heating in a single-pulse shock tube in the temperature range 1000–1600 K. The reaction products were quite the same as those obtained from the pyrolysis of acetylene alone, with a considerable increase in the yields of the minor products. The predominance of 1-buten-3-yne formation and no appreciable dependence of its rate on the concentration of deuterium suggest that the initiation step is the same as that proposed in the pyrolysis of acetylene by itself, <I>viz</I>. 2C<SUB>2</SUB>H<SUB>2</SUB>→C<SUB>4</SUB>H<SUB>3</SUB>+H, the initiation step of the bimolecular reaction of C<SUB>2</SUB>H<SUB>2</SUB> with D<SUB>2</SUB> not being important. A complementary analysis of the isotopic distributions of 1-buten-3-yne, ethylene, and acetylene shows that hydrogenation also occurs by a free-radical chain mechanism, and the C<SUB>4</SUB>H<SUB>3</SUB> radical and H atom generated by the initiation step are mainly responsible for the formation of 1-buten-3-yne and ethylene, respectively. The ethylene formation was of first-order in both acetylene and deuterium, and the second-order rate constant was obtained as<BR>k(cm^3 mol^-1 s^-1)=(4.9±1.3)×10^11exp((-34900±600)/RT).

• 公益社団法人 日本化学会の論文

著者

• Ogura Hiroo

  Institute of Space and Aeronautical Science, The University of Tokyo

関連論文

• Shock tube study on the mechanism of hydrogenation and pyrolysis of acetylene.
• Effect of hydrogen chloride on the pyrolysis of acetylene as studied with a single-pulse shock tube.
• Shock tube study of the H-D exchange reaction between acetylene and deuterium.

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