Experimental and quantum mechanics investigations of early reactions of monomethylhydrazine with mixtures of NO2 and N2O4

Wei Guang Liu, Shiqing Wang, Siddharth Dasgupta, Stefan Thynell, William A. Goddard, Sergey Zybin, Richard A. Yetter

Research output: Contribution to journalArticle

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Abstract

The gas-phase chemistry of the hypergolic system CH3NHNH2 - monomethylhydrazine (MMH), with oxidizers NO2/N2O4 at room temperature and 1atm N2 was investigated experimentally using a gold-coated chamber reactor, coupled with a Fourier transform infrared (FTIR) spectrometer. The IR-active species identified in the early reactions include HONO, monomethylhydrazinium nitrite (MMH·HONO), methyl diazene (CH3NNH), methyl nitrate (CH3ONO2), methyl nitrite (CH3ONO), nitromethane (CH3NO2), methyl azide (CH3N3), H2O, N2O and NO. In order to elucidate the mechanisms by which these observed products are formed, we carried out quantum mechanics calculations [CCSD(T)/M06-2X] for the possible reaction pathways. Based on these studies, we propose that the oxidation of MMH in an atmosphere of NO2 occurs via two mechanisms: (1) sequential H-abstraction and HONO formation, and (2) reaction of MMH with asymmetric ONONO2, leading to formation of methyl nitrate. These mechanisms successfully explain all intermediates observed experimentally. We conclude that the formation of asymmetric ONONO2 is assisted by an aerosol formed by HONO and MMH that provides a large surface area for ONONO2 to condense, leading to the generation of methyl nitrate. Thus we propose that the overall pre-ignition process involves both gas-phase and aerosol-phase reactions.

Original languageEnglish (US)
Pages (from-to)970-981
Number of pages12
JournalCombustion and Flame
Volume160
Issue number5
DOIs
StatePublished - May 1 2013

Fingerprint

Monomethylhydrazine
monomethylhydrazines
methyl nitrate
Quantum theory
quantum mechanics
Nitrates
Aerosols
nitrites
aerosols
Infrared spectrometers
Gases
vapor phases
nitromethane
oxidizers
Azides
Ignition
infrared spectrometers
Fourier transforms
Gold
ignition

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Physics and Astronomy(all)

Cite this

Liu, Wei Guang ; Wang, Shiqing ; Dasgupta, Siddharth ; Thynell, Stefan ; Goddard, William A. ; Zybin, Sergey ; Yetter, Richard A. / Experimental and quantum mechanics investigations of early reactions of monomethylhydrazine with mixtures of NO2 and N2O4. In: Combustion and Flame. 2013 ; Vol. 160, No. 5. pp. 970-981.
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Experimental and quantum mechanics investigations of early reactions of monomethylhydrazine with mixtures of NO2 and N2O4. / Liu, Wei Guang; Wang, Shiqing; Dasgupta, Siddharth; Thynell, Stefan; Goddard, William A.; Zybin, Sergey; Yetter, Richard A.

In: Combustion and Flame, Vol. 160, No. 5, 01.05.2013, p. 970-981.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Experimental and quantum mechanics investigations of early reactions of monomethylhydrazine with mixtures of NO2 and N2O4

AU - Liu, Wei Guang

AU - Wang, Shiqing

AU - Dasgupta, Siddharth

AU - Thynell, Stefan

AU - Goddard, William A.

AU - Zybin, Sergey

AU - Yetter, Richard A.

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N2 - The gas-phase chemistry of the hypergolic system CH3NHNH2 - monomethylhydrazine (MMH), with oxidizers NO2/N2O4 at room temperature and 1atm N2 was investigated experimentally using a gold-coated chamber reactor, coupled with a Fourier transform infrared (FTIR) spectrometer. The IR-active species identified in the early reactions include HONO, monomethylhydrazinium nitrite (MMH·HONO), methyl diazene (CH3NNH), methyl nitrate (CH3ONO2), methyl nitrite (CH3ONO), nitromethane (CH3NO2), methyl azide (CH3N3), H2O, N2O and NO. In order to elucidate the mechanisms by which these observed products are formed, we carried out quantum mechanics calculations [CCSD(T)/M06-2X] for the possible reaction pathways. Based on these studies, we propose that the oxidation of MMH in an atmosphere of NO2 occurs via two mechanisms: (1) sequential H-abstraction and HONO formation, and (2) reaction of MMH with asymmetric ONONO2, leading to formation of methyl nitrate. These mechanisms successfully explain all intermediates observed experimentally. We conclude that the formation of asymmetric ONONO2 is assisted by an aerosol formed by HONO and MMH that provides a large surface area for ONONO2 to condense, leading to the generation of methyl nitrate. Thus we propose that the overall pre-ignition process involves both gas-phase and aerosol-phase reactions.

AB - The gas-phase chemistry of the hypergolic system CH3NHNH2 - monomethylhydrazine (MMH), with oxidizers NO2/N2O4 at room temperature and 1atm N2 was investigated experimentally using a gold-coated chamber reactor, coupled with a Fourier transform infrared (FTIR) spectrometer. The IR-active species identified in the early reactions include HONO, monomethylhydrazinium nitrite (MMH·HONO), methyl diazene (CH3NNH), methyl nitrate (CH3ONO2), methyl nitrite (CH3ONO), nitromethane (CH3NO2), methyl azide (CH3N3), H2O, N2O and NO. In order to elucidate the mechanisms by which these observed products are formed, we carried out quantum mechanics calculations [CCSD(T)/M06-2X] for the possible reaction pathways. Based on these studies, we propose that the oxidation of MMH in an atmosphere of NO2 occurs via two mechanisms: (1) sequential H-abstraction and HONO formation, and (2) reaction of MMH with asymmetric ONONO2, leading to formation of methyl nitrate. These mechanisms successfully explain all intermediates observed experimentally. We conclude that the formation of asymmetric ONONO2 is assisted by an aerosol formed by HONO and MMH that provides a large surface area for ONONO2 to condense, leading to the generation of methyl nitrate. Thus we propose that the overall pre-ignition process involves both gas-phase and aerosol-phase reactions.

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