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- W2024117665 abstract "The kinetics of thermal decomposition of cuneane2) (1) in the gas phase have been investigated in the temperature range 180–220°C. The reaction is a clean first-order homogeneous process leading to the formation of two C8H8 isomers, viz., semibullvalene3) (2) and cyclooctatetraene (3). The rate constant varies with temperature according to the Arrhenius equation log(k/S−1) = (13.82 ± 0.09) – (37.7 ± 0.2 kcal mol−1)/RT In10. The Arrhenius parameters are consistent with a biradical mechanism leading to the formation of semibullvalene (2). The product proportions are pressure-dependent which strongly suggests that semibullvalene (2) is initially formed with high vibrational energy content (ca. 74 kcal mol−1) and can react further to give cyclooctatetraene (3). Das Thermolyseverhalten von C5H8-Kohlenwasserstoffen. — Gasphasen-Thermolyse von Cuncan, ein neues Beispiel für die Freisetzung hoher Spannungsenergie Die Kinetik der Gasphasenthermolyse von Cunean2) (1) wurde im Temperaturbereich von 180–220°C untersucht. Es handelt sich um eine Reaktion erster Ordnung, die zu zwei C8H8-Isomeren führt, zu Semibullvalen (2) und Cyclooctatetraen (3). Die Geschwindigkeitskonstante ist abhängig von der Temperatur entsprechend der Arrhenius-Gleichung log(k/s−1) = (13.82 ± 0.09) – (37.7 ± 0.2 kcal mol−1)/RT In10. Die Arrheniusparameter stimmen mit einem biradikalischen Mechanismus überein, der zur Bildung von Semibullvalen (2) führt. Die Produktverteilung ist druckabhängig. Dies deutet darauf hin, daß das zuerst gebildete Semibullvalen (2) hoch schwingungsangeregt (ca. 74 kcal mol−1) ist und zu Cyclooctatetraen (3) weiterreagiert." @default.
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- W2024117665 date "1988-02-01" @default.
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- W2024117665 title "Thermal Behaviour of C <sub>8</sub> H <sub>8</sub> Hydrocarbons Gas‐Phase Thermolysis of Cuneane, a New Example of a High‐Strain Energy Release Process" @default.
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- W2024117665 doi "https://doi.org/10.1002/cber.19881210225" @default.
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