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Kinetics of thermal decomposition of cubic ammonium perchlorate

Journal Article · · Chemistry of Materials
DOI:https://doi.org/10.1021/cm9904382· OSTI ID:20004038

The methods of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used to study the thermal decomposition of ammonium perchlorate (AP).l TGA curves obtained under both isothermal and nonisothermal conditions show a characteristic slowdown at the extents of conversion, {alpha} = 030--0.35. DSC demonstrates that in this region the process changes from an exothermic to an endothermic regime. The latter is ascribed to dissociative sublimation of AP.A new computational technique (advanced isoconversional method) has been used to determine the dependence of the effective activation energy (E{sub {alpha}}) on {alpha} for isothermal and nonisothermal TGA data. At {alpha} {gt} 0.1, the E{sub {alpha}} dependencies obtained from isothermal and nonisothermal data are similar. By the completion of decomposition ({alpha} {r{underscore}arrow} 1) the activation energy for the isothermal and nonisothermal decomposition respectively rises to {approximately}110 and {approximately}130 kJ mol{sup {minus}1}, which are assigned to the activation energy of sublimation. The initial decomposition ({alpha} {r{underscore}arrow} 0) shows the activation energy of 90 kJ mol{sup {minus}1} for the isothermal decomposition and 130 kJ mol{sup {minus}1} for the nonisothermal decomposition. The difference is explained by different rate-limiting steps, which are nucleation and nuclei growth for isothermal and nonisothermal decompositions, respectively.

Research Organization:
Univ. of Utah, Salt Lake City, UT (US)
Sponsoring Organization:
US Department of Energy; Office of Naval Research
OSTI ID:
20004038
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 11; ISSN CMATEX; ISSN 0897-4756
Country of Publication:
United States
Language:
English

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