Kinetic compensation effect as a mathematical consequence of the exponential rate constant

Koga, Nobuyoshi; Šesták, Jaroslav

doi:10.1016/0040-6031(91)80005-4

Cited by 125 publications

(74 citation statements)

References 43 publications

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“…The mystery of the compensation effect existence can be and was discussed extensively. Whether the effect is ''real'' or possible artifact as some assert [107][108][109][110][111][112], it was experimentally detected in numerous reactive systems and in kinetics of small molecules diffusion in polymers, and the present data apparently confirm these observations (Fig. 9).…”

Section: Compensation Effectsupporting

confidence: 90%

Kinetics of water vapor diffusion in resins

Krongauz

Bennett

Ling

2016

J Therm Anal Calorim

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The water vapor sorption and desorption kinetics were monitored in methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), bromobutyl, ethylenepropylene-butadiene monomer (EPDM) rubber, and butyl rubber at various temperatures by gravimetric method. Modified thermogravimetric analysis system was built and used. The geometry of the samples was approximating that of the infinite two-sided plane sheet of certain thickness. The coefficients of water vapor diffusion in polymers were deduced by comparing the experimentally monitored kinetics and kinetics computed using diffusion coefficients as adjustable parameters. The activation energies of water vapor diffusion in these polymers were deduced in the temperature range from 30 to 75°C. The activation energy of diffusion was 45.9 kJ mol -1 in bromobutyl rubber, 46.4 kJ mol -1 in butyl rubber, 60.3 kJ mol -1 in EPDM rubber, and 43.5 kJ mol -1 in MABS. Compensation effect was observed for water vapor diffusion in this series of polymers. Compensation effect parameters were determined to be, a = -23.9/ln(cm 2 s -1 ) and b = 0.49/(mol kJ -1 ) 9 ln(cm 2 s -1 ), in fair agreement with published data for water diffusion in polymers.

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Section: Compensation Effectsupporting

confidence: 90%

Kinetics of water vapor diffusion in resins

Krongauz

Bennett

Ling

2016

J Therm Anal Calorim

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“…pre-exponential term) are invariant. However if an increase in activation energy is accompanied by a corresponding increase in the pre-exponential factor then the rates of reaction may be invariant, and this is an example of a kinetic compensation effect [8,9]. This was observed in our study.…”

Section: A Luminum Powderssupporting

confidence: 43%

Low/high temperature relationships in dinitramide salts by DEA/DSC and study of oxidation of aluminum powders by DSC/TG

Tompa

Boswell

Skahan

et al. 1997

Journal of Thermal Analysis

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“…Although the linear dependence of the series of apparent Arrhenius parameters has widely been observed in the practical kinetic studies, it is very difficult to obtain the physicochemically meaningful preexponential factor by the present TA kinetics. On the other hand, the linear dependence of the Arrhenius parameters itself can be easily demonstrated as a simple mathematical consequence of the exponential form of the kinetic equation [36]. Sophistication of our kinetic procedure is required for the further detailed discussions about the KCE.…”

Section: Apparent Kinetic Parametersmentioning

confidence: 98%

Physico-geometric kinetics of solid-state reactions by thermal analyses

Koga

1997

Journal of Thermal Analysis

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The physico-geometric kinetics for the solid-state reactions by thermoanalytical (TA) measurements were reexamined by focusing some fundamental aspects: (1) the fundamental kinetic equation, (2) the kinetic model function, (3) the fractional reaction ct, and (4) the apparent kinetic parameters. It was pointed out that some pitfalls in the practical kinetic study are originated by the disagreement between the kinetic information from the TA measurements and the theory of the physico-geometric kinetics. In order to increase the degree of coordination between the theory and practice, several attempts were made from both the theoretical and experimental points of views. The significance of the apparent kinetic parameters was discussed with a possible orientation for obtaining the reliable kinetic parameters.

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Kinetic compensation effect as a mathematical consequence of the exponential rate constant

Cited by 125 publications

References 43 publications

Kinetics of water vapor diffusion in resins

Kinetics of water vapor diffusion in resins

Low/high temperature relationships in dinitramide salts by DEA/DSC and study of oxidation of aluminum powders by DSC/TG

Physico-geometric kinetics of solid-state reactions by thermal analyses

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