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Title: Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces

Abstract

Large complex formation involved in the thermal decomposition of hydrazine (N2H4) is studied here using transition state theory based theoretical kinetics. A comprehensive analysis of the N3H5 and N4H6 potential energy surfaces was performed at the CCSD(T)-F12a/aug-cc-pVTZ//ωB97x-D3/6-311++G(3df,3pd) level of theory, and pressure-dependent rate coefficients were determined. There are no low-barrier unimolecular decomposition pathways for triazane (n-N3H5), and its formation becomes more significant as the pressure increases; it is the primary product of N2H3 + NH2 below 550, 800, 1150, and 1600 K at 0.1, 1, 10, and 100 bar, respectively. The N4H6 surface has two important entry channels, N2H4 + H2NN and N2H3 + N2H3, each with different primary products. Interestingly, N2H4 + H2NN primarily form N2H3 + N2H3, while disproportionation of N2H3 + N3H3 predominantly leads to the other N2H2 isomer, HNNH. Stabilized tetrazane (n-N4H6) formation from N2H3 + N2H3 becomes significant only at relatively high pressures and low temperatures due to fall-off back into N2H3 + N2H3. Pressure-dependent rate coefficients for all considered reactions as well as thermodynamic properties of triazane and tetrazane, which should be considered for kinetic modeling of chemical processes involving nitrogen- and hydrogen-containing species, are reported.

Authors:
 [1];  [2];  [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1510335
Alternate Identifier(s):
OSTI ID: 1531171
Grant/Contract Number:  
SC0014901; W911NF1710531; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 123; Journal Issue: 22; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Grinberg Dana, Alon, Moore, Kevin Bruce, Jasper, Ahren Ward, and Green, William H. Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces. United States: N. p., 2019. Web. doi:10.1021/acs.jpca.9b02217.
Grinberg Dana, Alon, Moore, Kevin Bruce, Jasper, Ahren Ward, & Green, William H. Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces. United States. doi:10.1021/acs.jpca.9b02217.
Grinberg Dana, Alon, Moore, Kevin Bruce, Jasper, Ahren Ward, and Green, William H. Thu . "Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces". United States. doi:10.1021/acs.jpca.9b02217. https://www.osti.gov/servlets/purl/1510335.
@article{osti_1510335,
title = {Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces},
author = {Grinberg Dana, Alon and Moore, Kevin Bruce and Jasper, Ahren Ward and Green, William H.},
abstractNote = {Large complex formation involved in the thermal decomposition of hydrazine (N2H4) is studied here using transition state theory based theoretical kinetics. A comprehensive analysis of the N3H5 and N4H6 potential energy surfaces was performed at the CCSD(T)-F12a/aug-cc-pVTZ//ωB97x-D3/6-311++G(3df,3pd) level of theory, and pressure-dependent rate coefficients were determined. There are no low-barrier unimolecular decomposition pathways for triazane (n-N3H5), and its formation becomes more significant as the pressure increases; it is the primary product of N2H3 + NH2 below 550, 800, 1150, and 1600 K at 0.1, 1, 10, and 100 bar, respectively. The N4H6 surface has two important entry channels, N2H4 + H2NN and N2H3 + N2H3, each with different primary products. Interestingly, N2H4 + H2NN primarily form N2H3 + N2H3, while disproportionation of N2H3 + N3H3 predominantly leads to the other N2H2 isomer, HNNH. Stabilized tetrazane (n-N4H6) formation from N2H3 + N2H3 becomes significant only at relatively high pressures and low temperatures due to fall-off back into N2H3 + N2H3. Pressure-dependent rate coefficients for all considered reactions as well as thermodynamic properties of triazane and tetrazane, which should be considered for kinetic modeling of chemical processes involving nitrogen- and hydrogen-containing species, are reported.},
doi = {10.1021/acs.jpca.9b02217},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 22,
volume = 123,
place = {United States},
year = {2019},
month = {5}
}

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