Falloff curves and mechanism of thermal decomposition of CF₃I in shock waves
The falloff curves of the unimolecular dissociation CF₃I (+Ar) → CF₃ + I (+Ar) are modelled by combining quantum-chemical characterizations of the potential energy surface for the reaction, standard unimolecular rate theory, and experimental information on the average energy transferred per collisio...
| Autores: | , , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2019 |
| País: | Argentina |
| Recursos: | Universidad Nacional de La Plata |
| Repositorio: | SEDICI (UNLP) |
| Idioma: | inglés |
| OAI Identifier: | oai:sedici.unlp.edu.ar:10915/138272 |
| Acesso em linha: | http://sedici.unlp.edu.ar/handle/10915/138272 |
| Access Level: | acceso abierto |
| Palavra-chave: | Física Química Falloff curves Unimolecular dissociation Decomposition mechanism |
| Resumo: | The falloff curves of the unimolecular dissociation CF₃I (+Ar) → CF₃ + I (+Ar) are modelled by combining quantum-chemical characterizations of the potential energy surface for the reaction, standard unimolecular rate theory, and experimental information on the average energy transferred per collision between excited CF₃I and Ar. The (essentially) parameter-free theoretical modelling gives results in satisfactory agreement with data deduced from earlier shock wave experiments employing a variety of reactant concentrations (between a few ppm and a few percent in the bath gas Ar). New experiments recording absorption-time signals of CF₃I, I₂, CF₂ and (possibly) IF at 450-500 and 200-300 nm are reported. By analysing the decomposition mechanism, besides the unimolecular dissociation of CF₃I, these provide insight into the influence of secondary reactions on the experimental observations. |
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