Computational study of the structure of dinitraminic acid, HN(NO2)2, and the energetics of some possible decomposition steps

Politzer, Peter; Seminario, Jorge M.

doi:10.1016/0009-2614(93)90107-c

Cited by 45 publications

(18 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, Mebel et al found that the energy for nitro elimination from HN(NO 2 ) 2 was about 38.4 kcal/mol using higher levels of theory, including the G1 method. 26 This compares to an earlier BAC-MP4 value of 46.6 kcal/mol. 27 The Politzer group has studied the energetics of the N-N bond-breaking in the dinitramide anion and concluded that the elimination of NO 2 as a neutral species is the lowest energy dissociation process (45.5 kcal/mol).…”

Section: Introductionmentioning

confidence: 77%

Ab Initio Calculation of the Heats of Formation of Nitrosamides: Comparison with Nitramides

Chen

Hamilton

1999

J. Phys. Chem. A

View full text Add to dashboard Cite

Ab initio calculations of the structures and energies of the mono-, di-, and trinitrosamides are compared to mono-, di-, and trinitramides. Highly accurate standard heats of formation of this series of nitramides and nitrosamides are calculated using isodesmic reactions and high-level theories. The nitrosamides have heats of formation at 0 K that are 20-40 kcal/mol higher than the analogous nitramides. The N-N bond strengths are comparable whether a NO or NO 2 group is bonded to the central nitrogen atom. The data suggest that converting the nitro groups to nitroso groups will result in compounds that have lower weight, shorter N-N bond lengths, and higher energy content, at the expense of lower oxygen balance. This suggests that nitrosamides are potentially useful high-energy materials. A revised ∆H f°f or NH 2 NO 2 is proposed to be 3.8 kcal/mol at 0 K, in close agreement with previous theory and very different from experiment. Recommended values for ∆H f°a re 34 and 71 kcal/mol for di-and trinitramide, respectively, and 22, 65, and 112 kcal/mol for mono-, di-and trinitrosamide, respectively. The errors in the monosubstituted molecules are estimated at 1 kcal/mol, and the errors are estimated at (2 and (3 kcal/mol for the di-and trisubstituted molecules, respectively. Nitrosamides have bond strengths comparable to those of the nitramides.

show abstract

Section: Introductionmentioning

confidence: 77%

Ab Initio Calculation of the Heats of Formation of Nitrosamides: Comparison with Nitramides

Chen

Hamilton

1999

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…There exists some theoretical and experimental evidence for acid-catalyzed decomposition [21,27,55] of ADN. Thermal decomposition of the ADN melt was found to be self-accelerated at the initial stage owing to HNO 3 accumulation.…”

Section: Thermal Decomposition Kineticsmentioning

confidence: 98%

“…Many theoretical [22,23,47,55,59] and experimental [21,[24][25][26][27][28][29][33][34][35][36][37][38] investigations have been performed to study the mechanisms of thermal decomposition of ADN. Mebel et al [23] considered the structures and decomposition products of ADN in the gas phase theoretically and described the potential energy surface of early decomposition reactions.…”

Section: Initial Thermal-decomposition Reactionsmentioning

confidence: 99%

Thermal Decomposition and Combustion of Ammonium Dinitramide (Review)

Yang

Thakre

Yang

2005

Combust Explos Shock Waves

View full text Add to dashboard Cite

A comprehensive review of thermal decomposition and combustion of ammonium dinitramide (ADN) has been conducted. The basic thermal properties, chemical pathways, and reaction products in both the condensed and gas phases are analyzed over a broad range of ambient conditions. Detailed combustion-wave structures and burning-rate characteristics are discussed. Prominent features of ADN combustion are identified and compared with other types of energetic materials. In particular, the influence of various condensed-and gas-phase processes in dictating the pressure and temperature sensitivities of the burning rate is examined. In the condensed phase, decomposition proceeds through the mechanisms ADN → NH 4 NO 3 + N 2 O and ADN → NH 3 + HNO 3 + N 2 O, the former mechanism being the basic one. In the gas phase, the mechanisms ADN → NH 3 + HDN and ADN → NH 3 + HNO 3 + N 2 O are prevalent. The gas-phase combustion-wave structure in the range of 5-20 atm consists of a near-surface primary flame followed by a dark-zone temperature plateau at 600-1000 • C and a secondary flame followed by another dark-zone temperature plateau at 1000-1400 • C. At higher pressures (60 atm and above), a final flame is observed at about 1800 • C without the existence of any dark-zone temperature plateau. ADN combustion is stable in the range of 5-20 atm and the pressure sensitivity of the burning rate has the form r b = 20.72p 0.604 [mm/sec] (p = 0.5-2.0 MPa). The burning characteristics are controlled by exothermic decomposition in the condensed phase. Above 100 atm, the burning rate is well correlated with pressure as r b = 8.50p 0.608 [mm/sec] (p = 10-36 MPa). Combustion is stable, and intensive heat feedback from the gas phase dictates the burning rate. The pressure dependence of the burning rate, however, becomes irregular in the range of 20-100 atm. This phenomenon may be attributed to the competing influence of the condensed-phase and gas-phase exothermic reactions in determining the propellant surface conditions and the associated burning rate.

show abstract

“…ADN is thought to decompose via this same mechanism [15,16,21]. Including the acid-base dissociation (ADN → HDN + NH 3 ), the YNU-L2.0 model contains possible reaction paths reported in the previous studies [8,15,16,21,46]. However, the detailed kinetic model revealed that molten ADN appears to directly decompose without acid-base dissociation.…”

Section: Resultsmentioning

confidence: 98%

Detailed kinetic model for ammonium dinitramide decomposition

Izato

Miyake

2018

Combustion and Flame

View full text Add to dashboard Cite

Ammonium dinitramide (ADN; [NH4]+[N(NO2)2]-) is the most promising oxidizer for use with future green solid and liquid propellants for spacecraft applications. To allow the effective development and use of ADN-based propellants, it is important to understand ADN reaction mechanisms. This work presents a detailed chemical kinetics model for the liquid phase reactions of ADN based on quantum chemical calculations. The thermal corrections, entropies, and heat capacities of chemical species were calculated from the partition function using statistical machinery based on the G4 level of theory. Rate coefficients were also determined to allow the application of transition state theory and variational transition state theory to reactions identified in our previous study. The new model employed herein simulates the thermal decomposition of ADN under specific heating conditions and successfully predicts heats of reaction and the gases that result from decomposition under those conditions. The thermal behaviour predicted from the new model was an excellent match with the experimental behaviour observed from thermal analysis using differential scanning calorimetry and Raman spectroscopy. The new kinetic model reveals the mechanism for the decomposition of ADN.

show abstract

Computational study of the structure of dinitraminic acid, HN(NO2)2, and the energetics of some possible decomposition steps

Cited by 45 publications

References 13 publications

Ab Initio Calculation of the Heats of Formation of Nitrosamides: Comparison with Nitramides

Ab Initio Calculation of the Heats of Formation of Nitrosamides: Comparison with Nitramides

Thermal Decomposition and Combustion of Ammonium Dinitramide (Review)

Detailed kinetic model for ammonium dinitramide decomposition

Contact Info

Product

Resources

About