Evaluation of rate constants from thermogravimetric data

Fuoss, Raymond M.; Salyer, I. O.; Wilson, Harry S.

doi:10.1002/pol.1964.100021132

Cited by 3 publications

(3 citation statements)

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“…The TG curves of ligand PTTA and its complexes were compared in order to determine the influence of metal ion on the thermal stability. Thermal stabilities have been compared on the basis of initial decomposition temperature, residual percentage by weight at a particular temperature, and energy of activation (E) calculated by Fuoss method [17]. PTTA and its complexes with Ni(II)-Sal and Cu(II)-Sal show stepwise degradation whereas PTTA-Co(II)-Sal complex exhibits continuous degradation above 250 ∘ C, and the weight becomes constant above 550 ∘ C in all the cases.…”

Section: Thermogravimetric Analysismentioning

confidence: 99%

Condensation Polymers of Terephthalic Acid and 1,4-Diaminobutane and Their Schiff Base Complexes

Rai

Bajpai²,

Lokhandwala

2013

Journal of Polymers

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Amino-terminated oligomeric poly(tetramethylene terephthalamide) (PTTA) was prepared by condensation of terephthalic acid and 1,4-diaminobutane using phosphorylation technique. Schiff base complexes of this polyamide were synthesized with salicylaldehyde and 2-hydroxy-1-naphthaldehyde complexes of Co(II), Ni(II), and Cu(II). The polyamide as well as Schiff base complexes were characterized by elemental analysis, IR spectroscopy, and magnetic susceptibility measurements. Thermal stabilities of ligand and its various complexes were compared by thermogravimetric analysis.

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Section: Thermogravimetric Analysismentioning

confidence: 99%

Condensation Polymers of Terephthalic Acid and 1,4-Diaminobutane and Their Schiff Base Complexes

Rai

Bajpai²,

Lokhandwala

2013

Journal of Polymers

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“…The second model was developed during this study to describe the pyrolysis kinetics on a more fundamental basis. This model incorporates a statistical reaction pathway model, which has successfully been applied to Bockhorn and Knü mann (1993) 200-600 0-50 1.1 8.3 × 10 19 310 c,b Cascaval (1970) 355-810 0 83 a,d 355-810 1 90 a,d Fuoss et al (1964) 394 1 5.0 × 10 24 323 d Jellinek (1950) 348-400 0 10 13.1 188 a,d,e Kishore et al (1976) 290-390 50-90 0 134 c,b Kokta et al (1973) 200-500 1 100-140 g 200-500 1 190-230 g Kuroki et al (1982) 310-390 1 1.8 × 10 11 152 b Madorsky (1953) 335-355 1 9.0 × 10 15 244 a Malhotra et al (1975) 180-390 1 189-440 b Mehmet and Roche (1976) 200-700 1 10 14.5 -10 15 219-229 a,i Mertens et al (1982) 500-800 1 92 c Risby et al (1982) Mw 100.000 g/mol 200-600 1 3.6 × 10 13 176 Mw 390.000 g/mol 200-600 1 6.1 × 10 12 165 Sato et al (1983) 100-600 0.75 3.5 × 10 11 177 b Wu et al (1993) 367-487 0.5 5.0 × 10 10 173 c this study 365-400 70-90 1 3.3 × 10 13 204…”

Section: Random Chain Dissociationmentioning

confidence: 99%

Kinetics of the Low-Temperature Pyrolysis of Polyethene, Polypropene, and Polystyrene Modeling, Experimental Determination, and Comparison with Literature Models and Data

Westerhout

Waanders

Kuipers

et al. 1997

Ind. Eng. Chem. Res.

299

176

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The pyrolysis kinetics of low-density polyethylene, high-density polyethylene, polypropylene, and polystyrene has been studied at temperatures below 450°C. In addition, a literature review on the low-temperature pyrolysis of these polymers has been conducted and has revealed that the scatter in the reported kinetic data is significant, which is most probably due to the use of simple first-order kinetic models to interpret the experimental data. This model type is only applicable in a small conversion range, but was used by many authors over a much wider conversion range. In this investigation the pyrolysis kinetics of the forementioned polymers and a mixture of polymers has been studied at temperatures below 450°C by performing isothermal thermogravimetric analysis (TGA) experiments. The TGA experimental data was used to determine the kinetic parameters on the basis of a simple first-order model for high conversions (70-90%) and a model developed in the present study, termed the random chain dissociation (RCD) model, for the entire conversion range. The influence of important parameters, such as molecular weight, extent of branching and-scission on the pyrolysis kinetics was studied with the RCD model. This model was also used to calculate the primary product spectrum of the pyrolysis process. The effect of the extent of branching and the initial molecular weight on the pyrolysis process was also studied experimentally. The effect of the extent of branching was found to be quite significant, but the effect of the initial molecular weight was minor. These results were found to agree quite well with the predictions obtained from the RCD model. Finally, the behavior of mixtures of the aforementioned polymers was studied and it was found that the pyrolysis kinetics of the polymers in the mixture remains unaltered in comparison with the pyrolysis kinetics of the pure polymers.

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“…All of the activation energies calculated from the rate analysis of the thermal degradation of polymers in the literature are higher than 30kcal/mol [26,[28][29][30][31][32][33][34]. That is, the thermal degradation of polymers is a rate process in which a chemical reaction plays the role of rate controlling step.…”

Section: Gas-liquid Interface In Working Reactor and The Rate Control...mentioning

confidence: 99%

Mechanistic consideration for the thermal degradation of polymers based on continuous flow operation

Murata

2022

Energy

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In this study, the author investigated the validity of the radical transfer mechanism for thermal degradation of polymers based on experimental facts and macroscopic considerations. There are various insufficiencies in the radical transfer mechanism which cannot provide any mechanistic explanation, such as the existence of gas-liquid interface in the chemical reaction dominant field, the effect of pressure on the thermal degradation behavior of polymers, and the temperature drop from liquid to gas phase in the reactor.These insufficiencies indicate that the radical transfer mechanism alone cannot explain the entire process of the thermal degradation of polymers. The generation of volatile products requires a different mechanism than the radical transfer. The author proposed a hydrogen transfer mechanism for breaking the chain-end that produces the volatile, and discussed its

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Evaluation of rate constants from thermogravimetric data

Cited by 3 publications

References 0 publications

Condensation Polymers of Terephthalic Acid and 1,4-Diaminobutane and Their Schiff Base Complexes

Condensation Polymers of Terephthalic Acid and 1,4-Diaminobutane and Their Schiff Base Complexes

Kinetics of the Low-Temperature Pyrolysis of Polyethene, Polypropene, and Polystyrene Modeling, Experimental Determination, and Comparison with Literature Models and Data

Mechanistic consideration for the thermal degradation of polymers based on continuous flow operation

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