A study of the solid-phase thermal decomposition of NTO using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS)

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The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log{sub 10} p(torr) = 12.5137 + 6,296.553(1/t{sub k}) and the {Delta}H{sub subl} = 28.71 {+-} 0.07 kcal/mol (120.01 {+-} 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products ... continued below

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13 p.

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Minier, L.; Behrens, R. & Burkey, T.J. January 1, 1997.

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  • Minier, L.
  • Behrens, R. Sandia National Labs., Livermore, CA (United States). Combustion Research Facility
  • Burkey, T.J. Univ. of Memphis, TN (United States). Chemistry Dept.

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Description

The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log{sub 10} p(torr) = 12.5137 + 6,296.553(1/t{sub k}) and the {Delta}H{sub subl} = 28.71 {+-} 0.07 kcal/mol (120.01 {+-} 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-{sup 13}C, NTO-1,2-{sup 15}N{sub 2} and NTO-{sup 2}H{sub 2}. Identification of the products show the major gaseous products to be N{sub 2}, CO{sub 2}, NO, HNCO, H{sub 2}O and some N{sub 2}O, CO, HCN and NH{sub 3}. The N{sub 2} is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO{sub 2} is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C{sub 2.1}H{sub .26}N{sub 2.9}O and FTIR analysis suggests that the residue is polyurea- and polycarbamate-like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H{sub 2}O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.

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13 p.

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OSTI as DE97051374

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  • 1996 JANNAF combustion subcommittee and propulsion systems: hazards subcommittee joint meeting, Monterey, CA (United States), 4-8 Nov 1996

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  • Other: DE97051374
  • Report No.: SAND--97-8423C
  • Report No.: CONF-961194--
  • Grant Number: AC04-94AL85000
  • Office of Scientific & Technical Information Report Number: 634007
  • Archival Resource Key: ark:/67531/metadc690036

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  • January 1, 1997

Added to The UNT Digital Library

  • Aug. 14, 2015, 8:43 a.m.

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  • Nov. 25, 2015, 4:12 p.m.

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Minier, L.; Behrens, R. & Burkey, T.J. A study of the solid-phase thermal decomposition of NTO using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS), article, January 1, 1997; United States. (digital.library.unt.edu/ark:/67531/metadc690036/: accessed October 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.