Počet záznamů: 1
Isothermal and Isoconversional Modeling of Solid-State Nitroso Polymerization
- 1.0537763 - ÚOCHB 2021 RIV US eng J - Článek v odborném periodiku
Bibulić, P. - Rončević, Igor - Špadina, M. - Biljan, I. - Vančik, H.
Isothermal and Isoconversional Modeling of Solid-State Nitroso Polymerization.
Journal of Physical Chemistry A. Roč. 124, č. 51 (2020), s. 10726-10735. ISSN 1089-5639. E-ISSN 1520-5215
Institucionální podpora: RVO:61388963
Klíčová slova: activation energy model * kinetic analysis * crystallization kinetics
Obor OECD: Physical chemistry
Impakt faktor: 2.781, rok: 2020
Způsob publikování: Omezený přístup
https://doi.org/10.1021/acs.jpca.0c08382
The solid-state formation of azodioxide polymers from aromatic dinitroso compounds with different spacer groups was used as a model reaction for a comprehensive analysis that included bulk-based, mechanistic, and isoconversional kinetic methods. Dinitroso species were prepared in situ from azodioxides by UV cleavage under cryogenic conditions, after which their thermally induced conversion to azodioxides was followed by Fourier transform IR spectroscopy. The obtained data were used to calculate activation parameters and determine the influence of the spacer on the kinetics. Isoconversional models suggest a distribution of activation energies, pointing to an important (topochemical) effect of the local environment on the reactivity. In general, bulk-based and isoconversional kinetic models gave poorer fits but produced mutually consistent rate parameters. Similar energies and entropies of activation were obtained with all three approaches, suggesting that they all describe the same underlying physical phenomena, that is, the polymerization by bond-making is the dominant process.
Trvalý link: http://hdl.handle.net/11104/0316297
Počet záznamů: 1