Kinetic Analysis of Single or Multi-Step Decomposition Processes; Limits introduced by statistical analysis

A kinetic study on decomposition processes of some penicillin and some commercial drugs was carried out. As expected by the complex structures of penicillins, several steps with different activation energies occurred in their decomposition processes. Model-fitting and model-free kinetic approach were applied to non-isothermal and isothermal data. In the model-fitting methods the kinetic triplets (f(α), A and E _a) that defines a single reaction step resulted in being at variance with the multi-step nature of penicillins decomposition. The model-free approach represented by isothermal and non-isothermal isoconversional methods, gave dependences of the activation energies on the extent of conversion. The complex nature of the multi-step process of the studied compounds was more easily revealed using a broader temperature range in non-isothermal isoconversional method. The failure in the model fitting method did not allow calculating storage times. Model-fitting and model-free methods, both isothermal and non-isothermal, showed that F1 mechanism is able to describe decomposition processes for drugs (having Phosphomycin salts as active component) for which a single decomposition process occurs. Statistical analysis allowed us to select reliable kinetic parameters related to the decomposition processes for these last compounds. This procedure showed that the values obtained by extrapolation, outside the temperature range where the processes occurred must be used with caution. Indeed half-life and shelf-life values, commonly extrapoled at room temperature, seemed to be unrealistic. This revised version was published online in August 2006 with corrections to the Cover Date.