Pyrolysis of Nitrites and Nitrates

The alkyl nitrate and nitrite esters contain four different elements and as such may be expected to show a very complex kinetic behavior. This is certainly the case with the nitrate esters, the pyrolysis of which is accompanied by varying amounts of oxidation. For the nitrites, however, the pyrolysis seems to be less complex. The principal reaction products from the pyrolysis of C HsONO are CH3CHO + NO together with lesser amounts of N2O + H2O and much smaller amounts of C2H6OH, HCN, CO, and CII2O. 

On applying stationary states for HNO, CH3, and C2H6O, we find (neglecting reaction 5 compared to reactions 6 and 4)  

Since it is found that adding NO has little if any effect on the rate of loss of EtONO and initially CII3CHO accounts for more than 80 per cent of the carbon balance, then 4(NO) kz, so that the rate expression becomes in the presence of added NO 

This is exactly the behavior found for the decomposition in the presence of added NO, a first-order rate of disappearance of the ester. It is found that the empirical rate constant /co is given by 

Added acetaldehyde is found to accelerate the rate, and in excess it completely inhibits N2O. This can be explained by adding the following steps to the scheme  

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