A readily applicable empirical formula is obtained for the collisional efficiency for energy transfer between a highly vibrationally excited reactant and a seasoned (usually quartz) wall, in terms of the molecular weight, potential well depth and dipole moment of the reactant. This expression is used to examine corrections due to nonunit wall collision efficiency in the high-pressure rate parameters obtained from very low-pressure pyrolysis experiments. It is found that these corrections are up to ca. 2 5 kJ/mol in the high-pressure activation energy and a factor of ca. 2 in the high-pressure frequency factor, for molecules with molecular weight less than ca. 100 and where experiments are carried out at temperatures exceeding 1000 K.

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Mit der angegebenen empirischen Formel für die Stoßwirksamkeit des Energietransfers zwischen hochschwingungsangeregten Molekülen und der Reaktorwand können Korrekturen für die Umrechnung von Niederdruck‐Pyrolyseexperimenten auf Hochdruck‐Geschwindigkeitsparameter ermittelt werden.

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