Analysis of the unimolecular reaction N 2 O 5 + M ⇌ NO 2 + NO 3 + M

Recent experimental results on the thermal decomposition of N 2 O 5 in N 2 are evaluated in terms of unimolecular rate theory. A theoretically consistent set of fall‐off curves is constructed which allows to identify experimental errors or misinterpretations. Limiting rate constants k 0 = [N 2 ] 2.2 × 10 −3 ( T /300) −4.4 exp(−11,080/ T ) cm 3 /molec·s over the range of 220–300 K, k ∞ = 9.7 × 10 14 ( T /300) +0.1 exp(−11,080/ T ) s −1 over the range of 220–300 K, and broadening factors of the fall‐off curve F cent = exp(‐ T /250) + exp(−1050/ T ) over the range of 220–520 K have been derived. NO 2 + NO 3 recombination rate constants over the range of 200–300 K are k rec,0 = [N 2 ] 3.7 × 10 −30 ( T /300) −4.1 cm 6 /molec 2 ·s and k rec,∞ = 1.6 × 10 −12 ( T /300) +0.2 cm 3 /molec·s.