Kinetic modeling of hypergolic ignition of N2H4-NTO mixtures at low temperatures and the sawyer-glassman experiment on reactions of N2H4 with NOx(x = 1, 2) at high temperatures

Bi Ren Gu, P. Raghunath, Gary C. Cheng, Y. S. Chen, Jong-Shinn Wu, Ming-Chang Lin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


In this collaborative study on the hypergolic reaction of N2H4 with N2O4, we have kinetically modeled the temperature and pressure behaviors of the system upon mixing at high temperatures under the conditions employed by Sawyer and Glassman in 1967 and at low temperature in the gas phase as well as in N2H4 solution. The kinetics reported by Sawyer and Glassman using their adiabatic flow reactor study at 800-1000 K under atmospheric pressure measured with a thermocouple for temperature change, attributed to NO2 + N2H4 and NO + N2H4 reactions, could only be qualitatively accounted for by modeling with our full mechanism containing 41 species and 196 reactions. At 300 K, our modeling of the mixtures containing 16 Torr and 1 atm each of the reagents indicates that the hypergolic ignition resulted entirely from the NO2 + N2H4 → HONO + N2H3 reaction, whereas in the N2H4 solution, the bimolecular reaction of N2H4 with ONONO2as proposed by Lai et al. in 2012 is responsible for the initiation reaction and the formation of the energetic hydrazinium nitrate (N2H5 +NO3 -) salt which was detected previously in different condensed-phase reaction studies.

Original languageEnglish
Pages (from-to)357-379
Number of pages23
JournalInternational Journal of Energetic Materials and Chemical Propulsion
Issue number5
StatePublished - 1 Jan 2015


  • Gas-phase reactions
  • Kinetic modeling
  • NH-NO reaction
  • Quantum chemical calculations
  • Solution reactions

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