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Abstract  

A differential method is proposed which uses local heating rates to evaluate non-isothermal kinetic parameters. The method allows to study the influence of the deviation of the true heating rate with respect to the programmed one on the values of the kinetic parameters. For application, the kinetic parameters of the following solid-gas decomposition reaction were evaluated: [Ni(NH3)6]Br2(s)→[Ni(NH3)2]Br2(s)+4NH3(g). The results obtained revealed significant differences between the values of the non-isothermal kinetic parameters obtained by using local heating rates and those obtained by using the programmed heating rate. It was also demonstrated that the kinetic equation which makes use of the local heating rates permits a better description of the experimental (α, t) data than the kinetic equation which uses the programmed constant heating rate.

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Abstract  

The paper deals with the influence of the deviation of the true heating rate with respect to the programmed one on the values of non-isothermal kinetic parameters for the solid-gas thermal decompositions of CaC2O4.H2O and [Ni(NH3)6]Br2. An original method, based on integration over small ranges of the variables and making use of local heating rates, was applied in order to determine the non-isothermal kinetic parameter values. The results show significant differences between values of non-isothermal kinetic parameters obtained by using true local heating rates and those obtained by using the programmed heating rate.

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