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optimize the microstructure. Phase transformations occur during both isothermal and non-isothermal annealing, involving several nucleation and growth mechanisms as summarized by Kempen et al. [ 1 ], for example. The most important kinetic parameters

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Determination of the kinetic parameters of polyvinylchloride

I. Dehydrochlorination at low conversions

Journal of Thermal Analysis and Calorimetry
Authors:
I. Agherghinei
,
A. Airinei
,
E. Buruiană
, and
A. Caraculacu
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Abstract  

The thermal properties of four heteropoly complexes α-K3H3[SiW11Ni(H2O)O39]·11.5H2O (I), α-K3H2[SiW11Fe(H2O)O39]·9H2O (II), α-[(C4H9)4N]3.5H1.5[SiW11Fe(H2O)O39]·4.5H2O (III) and α-[(C4H9)4N]3.5H2.5[SiW11Cu(H2O)O39]·6H2O (IV) were studied by means of TG, DTA and DSC. The activation energy and reaction order of the thermal decomposition reaction of these complexes have been calculated.

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Kinetic parameters of decomposition of some selenites

Generalized perturbation theory of chemical reactivity

Journal of Thermal Analysis and Calorimetry
Authors:
L Vlaev
,
V Georgieva
, and
S Genieva

Abstract  

Studying the kinetics of isothermal decomposition of thirteen selenites at isothermal heating, the values of activation energy E of the process, pre-exponential factor A in Arrhenius equation and changes of entropy for the formation of the activated complex of the reagent were calculated. Direct dependence between the thermal stability of the selenites and their cation radii on their 'hardness' or 'softness' was found. The dependence was interpreted in the terms of the generalized perturbation theory of chemical reactivity. Kinetic compensation effect was observed only for the selenites, which thermally decompose by the same mechanism.

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Abstract  

The thermal behaviour of wool, untreated and chlorinated to various extents, was investigated. The kinetic parameters of the water loss and pyrolysis processes were computed and, based on their values, the way chlorination treatment affects wool fibre is discussed. As it appears, the chlorination process affects the fibre only superficially and not its internal chemical composition, as the values of the kinetic parameters of the thermal decomposition of wool fibre do not seem to be influenced at all by the treatment.

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Abstract  

Iron(III) complexes of o-vanillin oxime have been synthesized and characterized by different physicochemical techniques. The complexes containing thiocyanate, iodide and sulphate ionshave been subjected to non-isothermal decomposition studies in N2 using TGand DTG techniques. The kinetic parameters for both stages of decomposition of these complexes were evaluated by weighted least-squares method using the general approach as well as the Coats–Redfern and Horowitz–Metzger equations. The results indicate that the values of kinetic parameters obtained by these three different approaches agree well.

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It is known that experimental parameters may affect peak characteristics in DSC studies. Kinetic parameters calculated from isothermal and dynamic runs, can also be affected by the choice of experimental conditions.

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Abstract  

The kinetic parameters of dehydration were determined under non-isothermal conditions for different polystyrenedivinylbenzene sulfonic acid type cationites (DVB) and their dependence on the degree of cross-linking granulation, porosity, specific surface, content of SO3M groups (M=Li, Na, K, Rb), nature of the alkali metal in partially neutralized -SO3H groups and heating rate was investigated.

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A consecutive model of surface reaction, consisting of two steps (desorption and diffusion) was applied. It was concluded that diffusion modifies the temperature programmed desorption spectra, although the single peak curves appear. The differential method for calculation of kinetic parameters based on thesT M shift give values close to predicted ones only in the cases when particular steps are rate limiting. Generally, the desorption process have to be considered as a complex reaction, with the overall kinetic parameters. As a consequence of diffusion influence, the overall kinetic parameters are smaller than those for desorption step was obtained.

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Journal of Thermal Analysis and Calorimetry
Authors:
M. Villetti
,
J. Crespo
,
M. Soldi
,
A. Pires
,
R. Borsali
, and
V. Soldi

Abstract  

The thermal degradation of sodium hyaluronate, xanthan and methylcellulose was evaluated by thermogravimetric and infrared analysis. Kinetic parameters such as activation energy and pre-exponential factor were determined considering the Ozawa and Freeman–Carroll methods. The results suggest changes in the degradation mechanism with the fraction of mass loss for both the studied polysaccharides. The activation energy values determined by the Freeman–Carroll method are higher than those obtained by the Ozawa method under the same conditions, probably because in the first method a first order reaction was assumed and the thermal history effects were eliminated since only one TG curve was used to determine the kinetic parameters. Low thermal stability was observed for polyanions e.g. sodium hyaluronate (Na-Hy) and xanthan(XT) in comparison with methylcellulose (MC) which is a neutral polysaccharide. By infrared spectroscopy, it was observed that at low temperatures there occured only the scission of the exocyclic groups for both polysaccharides and that the scission of strong links in the backbone occurred at high temperatures, in agreement with the kinetic parameters determined for the degradation reaction.

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