2013Chemistry Central JournalOpen access

Clarifications regarding the use of model-fitting methods of kinetic analysis for determining the activation energy from a single non-isothermal curve

Pedro E. Sánchez‐Jiménez, Luis A. Pérez‐Maqueda, Antonio Perejón, José M. Criado

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Abstract

BACKGROUND: This paper provides some clarifications regarding the use of model-fitting methods of kinetic analysis for estimating the activation energy of a process, in response to some results recently published in Chemistry Central journal. FINDINGS: The model fitting methods of Arrhenius and Savata are used to determine the activation energy of a single simulated curve. It is shown that most kinetic models correctly fit the data, each providing a different value for the activation energy. Therefore it is not really possible to determine the correct activation energy from a single non-isothermal curve. On the other hand, when a set of curves are recorded under different heating schedules are used, the correct kinetic parameters can be clearly discerned. CONCLUSIONS: Here, it is shown that the activation energy and the kinetic model cannot be unambiguously determined from a single experimental curve recorded under non isothermal conditions. Thus, the use of a set of curves recorded under different heating schedules is mandatory if model-fitting methods are employed.

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BACKGROUND: This paper provides some clarifications regarding the use of model-fitting methods of kinetic analysis for estimating the activation energy of a process, in response to some results recently published in Chemistry Central journal. FINDINGS: The model fitting methods of Arrhenius and Savata are used to determine the activation energy of a single simulated curve. It is shown that most kinetic models correctly fit the data, each providing a different value for the activation energy. Therefore it is not really possible to determine the correct activation energy from a single non-isothermal curve. On the other hand, when a set of curves are recorded under different heating schedules are used, the correct kinetic parameters can be clearly discerned. CONCLUSIONS: Here, it is shown that the activation energy and the kinetic model cannot be unambiguously determined from a single experimental curve recorded under non isothermal conditions. Thus, the use of a set of curves recorded under different heating schedules is mandatory if model-fitting methods are employed.

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Available abstract

BACKGROUND: This paper provides some clarifications regarding the use of model-fitting methods of kinetic analysis for estimating the activation energy of a process, in response to some results recently published in Chemistry Central journal. FINDINGS: The model fitting methods of Arrhenius and Savata are used to determine the activation energy of a single simulated curve. It is shown that most kinetic models correctly fit the data, each providing a different value for the activation energy. Therefore it is not really possible to determine the correct activation energy from a single non-isothermal curve. On the other hand, when a set of curves are recorded under different heating schedules are used, the correct kinetic parameters can be clearly discerned. CONCLUSIONS: Here, it is shown that the activation energy and the kinetic model cannot be unambiguously determined from a single experimental curve recorded under non isothermal conditions. Thus, the use of a set of curves recorded under different heating schedules is mandatory if model-fitting methods are employed.

Key concepts: Kinetic energy, Chemistry, Isothermal process, Activation energy, Thermodynamics, Energy (signal processing), Physical chemistry, Statistics

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