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Title: Secondary channels in the thermal decomposition of monomethylhydrazine (CH3NHNH2)

Journal Article · · RSC Advances
DOI:https://doi.org/10.1039/c4ra13131b· OSTI ID:1396037
 [1];  [2];  [2];  [3];  [3]
  1. Department of Mechanical Engineering; The Hong Kong Polytechnic University; Hong Kong
  2. Chemical Sciences and Engineering Division; Argonne National Laboratory; Argonne, USA
  3. Department of Mechanical and Aerospace Engineering; Princeton University; Princeton, USA
+ Show Author Affiliations

Mass spectrometric observations in a very low pressure pyrolysis study of the decomposition of the prototypical rocket fuel monomethylhydrazine (MMH) indicated a dominant role for the molecular channels producing NH3 and H2 and their coproducts. In contrast, a recent ab initio transition state theory based master equation theoretical study indicated that simple N–N and C–N bond fissions dominate the kinetics. In this work, the possible role of molecular decomposition channels in MMH is explored further through additional investigations of the potential energy surface. These investigations consider the role of triplet channels, of roaming radical channels, and of some previously unexplored pathways for molecular decomposition. New ab initio transition state theory based master equation calculations provide revised predictions for the temperature and pressure dependence of the MMH decomposition kinetics that are in excellent agreement with recent shock tube measurements. These calculations continue to suggest only a very limited contribution from the molecular elimination channels. A roaming pathway is suggested to provide the dominant route for direct formation of ammonia. The possible role of secondary abstraction reactions in the very-low-pressure pyrolysis experiments is briefly discussed.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
DOE Contract Number:
SC0001198; AC02-06CH11357; W911NF1310251
OSTI ID:
1396037
Journal Information:
RSC Advances, Vol. 4, Issue 108; ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

References (47)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ab initio
decomposition
intersystem crossing
kinetics
master equation
monomethydrazine
roaming reaction
theory
training state theory