Advanced Isoconversional Kinetic Analysis for the Elucidation of Complex Reaction Mechanisms: A New Method for the Identification of Rate-Limiting Steps
Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled p...
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| Veröffentlicht in: | Molecules (Basel, Switzerland) Jg. 24; H. 9; S. 1683 - 1699 |
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30.04.2019
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| Schriftenreihe: | Special Issue “Thermal Analysis Kinetics for Understanding Materials Behavior” |
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| ISSN: | 1420-3049, 1420-3049 |
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| Abstract | Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman’s method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given α value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation. |
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| AbstractList | Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman's method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given α value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation.Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman's method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given α value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation. Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman's method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given α value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation. Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman's method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation. Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman's method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation. |
| Author | Sbirrazzuoli, Nicolas |
| AuthorAffiliation | University Côte d’Azur, Institute of Chemistry of Nice, UMR CNRS 7272, 06100 Nice, France; Nicolas.SBIRRAZZUOLI@unice.fr or Nicolas.SBIRRAZZUOLI@univ-cotedazur.fr |
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| Author_xml | – sequence: 1 givenname: Nicolas orcidid: 0000-0002-6031-5448 surname: Sbirrazzuoli fullname: Sbirrazzuoli, Nicolas |
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| Keywords | isoconversional methods DSC epoxy kinetic analysis curing polymerization mechanisms thermoanalytical techniques |
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| SubjectTerms | Chemical Sciences curing DSC Energy epoxy Heat isoconversional methods kinetic analysis Kinetics Material chemistry Mathematical functions Methods Molecular weight Polymerization polymerization mechanisms Software thermoanalytical techniques Viscosity |
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| Title | Advanced Isoconversional Kinetic Analysis for the Elucidation of Complex Reaction Mechanisms: A New Method for the Identification of Rate-Limiting Steps |
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