Reactions of 1-Naphthyl Radicals with Acetylene. Single-Pulse Shock Tube Experiments and Quantum Chemical Calculations. Differences and Similarities in the Reaction with Ethylene

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2009-10, Vol.113 (39), p.10446-10451
• Main Authors: Lifshitz, Assa, Tamburu, Carmen, Dubnikova, Faina
• Format: Article
• Language: English
• Subjects: A: Kinetics, Spectroscopy
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp905448g

The reactions of 1-naphthyl radicals with acetylene were studied behind reflected shock waves in a single-pulse shock tube, covering the temperature range 950−1200 K at overall densities behind the reflected shocks of ∼2.5 × 10−5 mol/cm3. 1-Iodonaphthalene served as the source for 1-naphthyl radicals. The [acetylene]/[1-iodonaphthalene] ratio in all of the experiments was ∼100 to channel the free radicals into reactions with acetylene rather than iodonaphthalene. Only two major products resulting from the reactions of 1-naphthyl radicals with acetylene and with hydrogen atoms were found in the post shock samples. They were acenaphthylene and naphthalene. Some low molecular weight aliphatic products at rather low concentrations, resulting from an attack of various free radicals on acetylene, were also found in the shocked samples. In view of the relatively low temperatures employed in the present experiments, the unimolecular decomposition rate of acetylene is negligible. One potential energy surface describes the production of acenaphthylene and 1-naphthyl acetylene, although the latter was not found experimentally due to the high barrier (calculated) required for its production. Using quantum chemical methods, the rate constants for three unimolecular elementary steps on the surface were calculated using transition state theory. A kinetics scheme containing 16 elementary steps was constructed, and computer modeling was performed. An excellent agreement between the experimental yields of the two major products and the calculated yields was obtained. Differences and similarities in the potential energy surfaces of 1-naphthyl radical + acetylene and those of ethylene are presented, and the kinetics mechanisms are discussed.