Ammonium perchlorate decomposition: Neat and solution1

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Abstract
The thermal decomposition of ammonium perchlorate (AP) was examined over a broad temperature range (215°C to 385°C) in solution and condensed phase. Over the entire temperature range, the decomposition, as monitored by loss of ammonium ion, appeared first-order out to 70% decomposition. Up to about 350°C the decomposition of AP in methanol (5wt% AP) proceeded at a rate similar to neat AP, but the AP in aqueous solution (20wt%) decomposed considerably slower than the neat material. Activation energies and frequency factors were determined for each experimental condition. In addition, decomposition products, both gaseous and condensed phase, were identified and quantified. For neat AP decomposition, the following reaction stoichiometries were determined. At low temperatures, decomposition of ammonium perchlorate in methanol proceeded at a similar rate to that of neat AP. In contrast to decomposition of neat AP, the only nitrogen-containing decomposition product was nitrogen gas, while chlorine appeared only as chloride. The presence of CO and CO2 as decomposition gases and chromatographic analysis of the solvent indicated interaction between methanol and AP. The decomposition of AP in water was slowed, but product distribution was not significantly different than that of neat AP.