Oxygen exchange and dehydration

3 HCIO4 CI2O7-1-HCIO4, H2O (followed by CI2O7 - CIO2, CI2 and O2) 

Decomposition of perchlorate salts has also been examined in molten systems. The rate-determining process in this case appears to be formation of chlorate and the step (4) has been proposed  

The reactions are first-order, after an induction period, and involve a small entropy of activation. The final products are KCl and oxygen. The rate parameters for reaction in solid phases are surprisingly close to those in melts, viz. 

In fused sodium hydroxide, the rate of decomposition is much higher (e.g. 10 ) than in fused sodium nitrate systems . The rate shows a significant, though much less than proportional, dependence on sodium hydroxide concentration in mixed nitrate-hydroxide melts, and the Arrhenius parameters differ 

The oxygen liberated in this system probably has peroxide as precursor. Low concentrations of the latter have been detected in decomposing systems. The mechanism proposed involves the reactions 

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