Experimental and Kinetic Modeling Study of Nitroethane Pyrolysis at a Low Pressure: Competition Reactions in the Primary Decomposition

The pyrolysis of
nitroethane has been investigated over the temperature
range of 682–1423 K in a plug flow reactor at a low pressure.
The major species in the pyrolysis process have been identified and
quantified using tunable synchrotron vacuum ultraviolet photoionization
mass spectrometry and molecular beam sampling techniques. The rate
constants for the primary pyrolysis of nitroethane as well as those
for the decomposition of the secondary product CH3CHNO2 have been obtained via ab initio calculations.
These results have been adopted in a detailed chemical kinetic model,
which contains 95 species and 737 reactions. The model was validated
against the experimental results with satisfactory agreement for most
of the identified and quantified species. Further analysis on the
results indicates that both the concerted molecular elimination and
C–N bond rupture are significant in the primary pyrolysis of
nitroethane, with the latter channel being more important at high
temperatures. The adoption of new decomposition pathways of CH3CHNO2 has resulted in reasonable predictions for
relevant intermediates.