The significance of “compensation effects” appearing in data published in “computational aspects of kinetic analysis”: ICTAC project, 2000

Brown, Michael E.; Galwey, Andrew K.

doi:10.1016/s0040-6031(01)00841-3

Cited by 107 publications

(52 citation statements)

References 18 publications

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“…Therefore, in this study, it was verified that the amount of mass of PET in the increased up to a limit of 1% limit. The decomposition reaction mechanism for all the samples was the same, as is observed from the sloped straight line for the relationship between ln A and E a [27][28][29][30][31][32][33]. …”

Section: Kinetic Parameterssupporting

confidence: 58%

Evaluation by thermogravimetry of the interaction of the poly(ethylene terephthalate) with oil-based paint

et al. 2016

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Abstract:The recycling of post-consumer soft-drink bottles poly (ethylene terephthalate) (PET) has been used as an additive in paint containing alkyd resin. Samples of paint containing PET (PPET) were applied in a film form on slides, and its thermal properties were evaluated for thermogravimetry (TG). The thermal behavior of PPET, it was possible to identify that the maximum of PET added to the paint without a change in the film properties was 1%. The kinetic parameters such as activation energy (E a ) and pre-exponential factor (A) were calculated using the isoconversional Flynn -Wall -Ozawa method for samples containing 0.5 to 1.0% of PET. The kinetic analysis indicates that there was a variation in E a values. The kinetic compensation effect (KCE), represented by the equation ln A = 0.105E -0.21 for the first stage of thermal decomposition. ..

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Section: Kinetic Parameterssupporting

confidence: 58%

Evaluation by thermogravimetry of the interaction of the poly(ethylene terephthalate) with oil-based paint

et al. 2016

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“…Such a classification through common features/criteria might then enable reasons for the appearance of compensation to be identified and explained. This view is expanded here and is developed with supporting illustrative examples, from a classification scheme previously proposed [5], to distinguish the following types of data sets (H -heterogeneous reactions). [6], rather than to reactions from the literature concerned with heterogeneous catalysis.…”

Section: Characteristics Of a Compensation Effectmentioning

confidence: 99%

Compensation effects and compensation defects in kinetic and mechanistic interpretations of heterogeneous chemical reactions

Galwey

Mortimer

2006

Int J of Chemical Kinetics

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A case is presented for kinetic compensation effects (KCEs) reported for sets of heterogeneous rate processes to be classified. Because many of these KCEs do not conform to the ideal of isokinetic behavior, a quantitative method for describing the degree of compensation (κ) is introduced. In the case of solid-promoted catalytic reactions, it is suggested that (unlike simple homogeneous reactions) the effective concentrations and dispositions of surface intermediates can vary with temperature. Thus, the rate constants vary differently with temperature for the individual reactions of a set and, thereby, influence apparent magnitudes of the measured Arrhenius parameters. As a consequence, compensation is observed for sets of chemically related reactions occurring within a common temperature interval. KCEs are thus linked to mechanistic information and, depending on the magnitude of κ, for identifying shared features of catalytic rate controls. In this respect, the classification of KCEs is useful and can be based on similarities or differences between the reactants, catalysts, or experimental conditions in a given set of measurements. These ideas are demonstrated for selected sets of catalytic reactions. KCEs reported from a range of thermal decompositions of solids are also discussed. It is argued that, for mathematical as well as term definition reasons, compensation in this type

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“…It is well known that the nonisothermal thermogravimetric analysis may successfully be used for determination of the kinetic triplet: the apparent activation E A , the pre-exponential factor A in the Arrhenius equation, and the shape of the most probable mechanism function f (α) for some heterogeneous reactions [1][2][3][4]. If the kinetic studies are carried out on similar compounds and with a correctly chosen mechanism function f (α), a linear relationship between the logarithm of the pre-exponential factors and activation energies exists, known as the kinetic compensation effect (KCE), isokinetic effect, or theta rule [5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Kinetics of Nonisothermal Degradation of Some Polymer Composites: Change of Entropy at the Formation of the Activated Complex from the Reagents

Turmanova

Genieva

Vlaev

2011

Journal of Thermodynamics

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Studying the nonisothermal kinetics of degradation of rice husks in air or nitrogen atmosphere, polypropylene and tetrafluoroethylene-ethylene copolymer filled with different quantities of rice husks flour or the products of its thermal degradation, namely "white" or "black" rice husks ash, a linear dependence was observed between the ln A and E A , known as the kinetic compensation effect or theta rule. A linear relationship was also established between E A and the change of the entropy ΔS / = for the formation of the activated complex from the reagents. These dependences are related to the assumption of identical kinetic mechanisms of thermal degradation of the composites studied. The negative values of ΔS / = obtained show that the activated complex is a "more organized" structure than the initial reactants and that these reactions may be classified as "slow" ones. It may be concluded that the products of the thermal degradation of rice husks in a fluidized bed reactor can successfully replace the more expensive synthetic fillers to obtain different polymer composites. These polymer composites can lead to the futuristic "organic-inorganic hybrid materials" with specific properties.

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The significance of “compensation effects” appearing in data published in “computational aspects of kinetic analysis”: ICTAC project, 2000

Cited by 107 publications

References 18 publications

Evaluation by thermogravimetry of the interaction of the poly(ethylene terephthalate) with oil-based paint

Evaluation by thermogravimetry of the interaction of the poly(ethylene terephthalate) with oil-based paint

Compensation effects and compensation defects in kinetic and mechanistic interpretations of heterogeneous chemical reactions

Kinetics of Nonisothermal Degradation of Some Polymer Composites: Change of Entropy at the Formation of the Activated Complex from the Reagents

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