From the Kissinger equation to model-free kinetics: reaction kinetics of thermally initiated solid-state reactions

Schulz, Henrik

doi:10.1007/s40828-018-0062-3

Cited by 18 publications

(37 citation statements)

References 23 publications

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“…Molar concentration, typically used in the kinetics of liquids and gasses is not suitable for solid reactions [23]. The conversion of a substance À 1…”

Section: Non-isothermal Reaction Kineticsmentioning

confidence: 99%

“…By measuring conversion over time, some of the kinetic parameters can estimated by determining the relationship between the initial rate of reaction and the apparent rate constant. These methods, however, assume that the reaction rate constant is independent of conversion, and the kinetic equations are derived from principles for homogenous fluid reactions 23 …”

Section: Introductionmentioning

confidence: 99%

“…In light of the complexity of melt grafting, it may be useful to explore the reaction mechanism in a model‐free way. This would allow determination of relevant kinetic parameters (activation energy and pre‐exponential factor) without explicit knowledge of the concrete reaction mechanism 23 . Typically, a series of isothermal experiments are required to determine these parameters based on the Arrhenius equation.…”

Section: Introductionmentioning

confidence: 99%

“…These methods, however, assume that the reaction rate constant is independent of conversion, and the kinetic equations are derived from principles for homogenous fluid reactions. 23 In light of the complexity of melt grafting, it may be useful to explore the reaction mechanism in a model-free way. This would allow determination of relevant kinetic parameters (activation energy and pre-exponential factor) without explicit knowledge of the concrete reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…This would allow determination of relevant kinetic parameters (activation energy and pre-exponential factor) without explicit knowledge of the concrete reaction mechanism. 23 Typically, a series of isothermal experiments are required to determine these parameters based on the Arrhenius equation. Because melt grafting is in the condensed-phase, it may be simpler to use nonisothermal techniques such as differential scanning calorimetry (DSC) to study the reaction kinetics.…”

Section: Introductionmentioning

confidence: 99%

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Functionalization of poly(butylene adipate‐co‐terephthalate) with itaconic anhydride through graft copolymerization

Verbeek

Smith

2022

J of Applied Polymer Sci

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Poly(butylene adipate-co-terephthalate) (PBAT) was functionalised with itaconic anhydride (IA) via melt grafting in a batch mixer, initiated by dicumyl peroxide (DCP). It was found that the ratio of IA to DCP is critical to avoid undesired side reactions, such as crosslinking and chain scission. PBAT and other polyesters with low aliphatic hydrocarbon content are relatively unreactive toward radical graft modification, providing relatively low degree of grafting. Using 2 wt% IA and 1.2 wt% DCP gave the highest degree of grafting (1%), with little indication of crosslinking or chain scission. The complex reaction mechanism of grafting presents a clear competition between grafting, homopolymerization, crosslinking, and chain scission. Using nonisothermal kinetic modeling, it was shown that the reaction is not first order, and that models making this assumption leads to incorrect results. Using the Vyazovkin model-free method, the effective rate constant was predicted over a typical melt processing temperature range. Low reagent concentration resulted in the lowest effective rate constant, and it was shown that the activation energy changes with conversion and is also affected by reagent concentration.

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“…Molar concentration, typically used in the kinetics of liquids and gasses is not suitable for solid reactions [23]. The conversion of a substance À 1…”

Section: Non-isothermal Reaction Kineticsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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