Thermal decomposition of gaseous ammonium dinitramide at low pressure: Kinetic modeling of product formation with ab initio MO/cVRRKM calculations

J. Park; D. Chakraborty; Ming-Chang Lin

doi:10.1016/S0082-0784(98)80086-6

Thermal decomposition of gaseous ammonium dinitramide at low pressure: Kinetic modeling of product formation with ab initio MO/cVRRKM calculations

J. Park^*, D. Chakraborty, Ming-Chang Lin

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Conference article › peer-review

41 Scopus citations

Abstract

The thermal decomposition of ammonium dinitramide, NH₄N(NO ₂)₂ (ADN), in the gas phase has been studied at 373-920 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor. The reaction of the sublimed mixture of NH3 and HN(NO₂) ₂ (dinitraminic acid, DN) was found to be initiated by the unimolecular decomposition of DN, HN(NO₂)₂ → HNNO₂ + NO₂, followed by the rapid decomposition reaction, HNNO₂ + M →N₂O + OH + M. The measured absolute yields of NH₃, H₂O, N₂, and N₂O, calibrated with standard mixtures, could be satisfactorily modeled at 10 Torr He carrier gas pressure by employing the theoretically computed values of k ₂ = 6.79 × 10⁴⁸ T^-11.0 exp(-21780/T) s^-1 and k₃ = 7.53 × 10²⁴ T^-2.9 exp(-12958/T) cm³/(mol s) by high-level ab initio molecular orbital and canonical variational Rice-Ramsperger-Kassel-Marcus (MO/cVRRKM) calculations. The key reactions with recommended rate constants are presented.

Original language	English
Pages (from-to)	2351-2357
Number of pages	7
Journal	Symposium (International) on Combustion
Volume	27
Issue number	2
DOIs	https://doi.org/10.1016/S0082-0784(98)80086-6
State	Published - 1 Jan 1998
Event	27th International Symposium on Combustion - Boulder, CO, United States Duration: 2 Aug 1998 → 7 Aug 1998

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@article{77b941d2cdbc4235adfb31d4c37a0cc5,

title = "Thermal decomposition of gaseous ammonium dinitramide at low pressure: Kinetic modeling of product formation with ab initio MO/cVRRKM calculations",

abstract = "The thermal decomposition of ammonium dinitramide, NH4N(NO 2)2 (ADN), in the gas phase has been studied at 373-920 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor. The reaction of the sublimed mixture of NH3 and HN(NO2) 2 (dinitraminic acid, DN) was found to be initiated by the unimolecular decomposition of DN, HN(NO2)2 → HNNO2 + NO2, followed by the rapid decomposition reaction, HNNO2 + M →N2O + OH + M. The measured absolute yields of NH3, H2O, N2, and N2O, calibrated with standard mixtures, could be satisfactorily modeled at 10 Torr He carrier gas pressure by employing the theoretically computed values of k 2 = 6.79 × 1048 T-11.0 exp(-21780/T) s-1 and k3 = 7.53 × 1024 T-2.9 exp(-12958/T) cm3/(mol s) by high-level ab initio molecular orbital and canonical variational Rice-Ramsperger-Kassel-Marcus (MO/cVRRKM) calculations. The key reactions with recommended rate constants are presented.",

author = "J. Park and D. Chakraborty and Ming-Chang Lin",

year = "1998",

month = jan,

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doi = "10.1016/S0082-0784(98)80086-6",

language = "English",

volume = "27",

pages = "2351--2357",

journal = "Symposium (International) on Combustion",

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note = "27th International Symposium on Combustion ; Conference date: 02-08-1998 Through 07-08-1998",

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T1 - Thermal decomposition of gaseous ammonium dinitramide at low pressure

T2 - 27th International Symposium on Combustion

AU - Park, J.

AU - Chakraborty, D.

AU - Lin, Ming-Chang

PY - 1998/1/1

Y1 - 1998/1/1

N2 - The thermal decomposition of ammonium dinitramide, NH4N(NO 2)2 (ADN), in the gas phase has been studied at 373-920 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor. The reaction of the sublimed mixture of NH3 and HN(NO2) 2 (dinitraminic acid, DN) was found to be initiated by the unimolecular decomposition of DN, HN(NO2)2 → HNNO2 + NO2, followed by the rapid decomposition reaction, HNNO2 + M →N2O + OH + M. The measured absolute yields of NH3, H2O, N2, and N2O, calibrated with standard mixtures, could be satisfactorily modeled at 10 Torr He carrier gas pressure by employing the theoretically computed values of k 2 = 6.79 × 1048 T-11.0 exp(-21780/T) s-1 and k3 = 7.53 × 1024 T-2.9 exp(-12958/T) cm3/(mol s) by high-level ab initio molecular orbital and canonical variational Rice-Ramsperger-Kassel-Marcus (MO/cVRRKM) calculations. The key reactions with recommended rate constants are presented.

AB - The thermal decomposition of ammonium dinitramide, NH4N(NO 2)2 (ADN), in the gas phase has been studied at 373-920 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor. The reaction of the sublimed mixture of NH3 and HN(NO2) 2 (dinitraminic acid, DN) was found to be initiated by the unimolecular decomposition of DN, HN(NO2)2 → HNNO2 + NO2, followed by the rapid decomposition reaction, HNNO2 + M →N2O + OH + M. The measured absolute yields of NH3, H2O, N2, and N2O, calibrated with standard mixtures, could be satisfactorily modeled at 10 Torr He carrier gas pressure by employing the theoretically computed values of k 2 = 6.79 × 1048 T-11.0 exp(-21780/T) s-1 and k3 = 7.53 × 1024 T-2.9 exp(-12958/T) cm3/(mol s) by high-level ab initio molecular orbital and canonical variational Rice-Ramsperger-Kassel-Marcus (MO/cVRRKM) calculations. The key reactions with recommended rate constants are presented.

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U2 - 10.1016/S0082-0784(98)80086-6

DO - 10.1016/S0082-0784(98)80086-6

M3 - Conference article

AN - SCOPUS:0032265629

SN - 0082-0784

VL - 27

SP - 2351

EP - 2357

JO - Symposium (International) on Combustion

JF - Symposium (International) on Combustion

IS - 2

Y2 - 2 August 1998 through 7 August 1998

ER -

Thermal decomposition of gaseous ammonium dinitramide at low pressure: Kinetic modeling of product formation with ab initio MO/cVRRKM calculations

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