Combined study of thermochemical properties of nitroform and its salts

Kon’kova, T. S.; Matyushin, Yu. N.

doi:10.1007/bf02641536

Cited by 7 publications

(8 citation statements)

References 3 publications

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“…Using the values α = 28.0 (kcal nm)/mol and β = 12.4 kcal/mol initially derived by Jenkins, we obtained the lattice enthalpy Δ H lat = 125.7 kcal/mol. The corresponding standard state formation enthalpy of HNF was estimated to be Δ f H 0 = 5.5 kcal/mol in harsh disagreement with the experimental value (−18.4 ± 0.3 kcal/mol) …”

Section: Resultsmentioning

confidence: 55%

“…This fact agrees well with the absence of HNF among the gas-phase decomposition products, whereas 1 and 3 were detected instead. ,,, Moreover, experimental data on the sublimation of HNF support this conclusion as well. As mentioned above, the standard state of HNF is the crystal one with Δ f H 0 = −18.4 ± 0.3 kcal/mol . The temperature dependence of the HNF vapor has been measured at the temperature range 34.4−67.7 °C and approximated by the Clausius−Clapeyron equation ln P = − β R T + C The value of β was found to be 23.2 kcal/mol.…”

Section: Resultsmentioning

confidence: 94%

“…In addition, an empirical correction formula was proposed to account for the differences between predicted and experimental total volumes due to flat shapes of the ions . The lattice enthalpy of HNF calculated using these improved parameters is equal to 150.8 kcal/mol, and the estimated formation enthalpy is Δ f H 0 = −19.6 kcal/mol in perfect agreement with experiment (Δ f H 0 = −18.4 ± 0.3 kcal/mol) . Nevertheless, it should be noted that such correlation formulas must be handled with care.…”

Section: Resultsmentioning

confidence: 99%

“…As mentioned above, the standard state of HNF is the crystal one with ∆ f H 0 ) -18.4 ( 0.3 kcal/mol. 69 The temperature dependence of the HNF vapor has been measured at the temperature range 34.4-67.7 °C37 and approximated by the Clausius-Clapeyron equation…”

Section: Resultsmentioning

confidence: 99%

“…The corresponding standard state formation enthalpy of HNF was estimated to be ∆ f H 0 ) 5.5 kcal/mol in harsh disagreement with the experimental value (-18.4 ( 0.3 kcal/mol). 69 However, Dixon et al have recently pointed out 73 an insufficient performance of empirical lattice energy estimations 71,72 for certain classes of compounds. The authors 73 proposed another parametrization (R ) 19.9 (kcal nm)/mol and β ) 37.6 kcal/ mol) particularly for salts containing ammonium, alkylammonium, and hydrazinium cations.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical Study of the Primary Processes in the Thermal Decomposition of Hydrazinium Nitroformate

Kiselev

Gritsan

2009

J. Phys. Chem. A

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The primary reactions of the thermal decomposition of hydrazinium nitroformate (HNF) as well as ammonium nitroformate (ANF) were investigated theoretically using the G3 multilevel procedure. Calculations were performed for the reactions in the gas phase and in the melt using a simplified model of the latter. The influence of the melt on the reaction barriers was taken into account by calculation of the solvation free energies using a PCM model. In contrast with many other energetic salts, the ionic salt structures of the HNF and ANF were found to be minima on the PES. However, the most energetically favorable structures of the HNF and ANF in the gas phase are H-bonded complexes. In the melt, on the contrary, the ionic structure is lowest in free energy because of solvation effects. In both the gas phase and melt, the HNF decomposes preferably to nitroform and hydrazine. This fact agrees well with the experimentally observed absence of HNF among the gas-phase decomposition products. Thermolysis of HNF occurs mainly through the intermediacy of nitroform; computations do not support the suggestion that the aci-nitroform is an important intermediate of HNF thermolysis. The primary dissociation reactions of ANF resemble those of the HNF.

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Section: Resultsmentioning

confidence: 55%

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical Study of the Primary Processes in the Thermal Decomposition of Hydrazinium Nitroformate

Kiselev

Gritsan

2009

J. Phys. Chem. A

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Synthesis and Characterization of New Energetic Nitroformate Salts

et al. 2007

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New energetic nitroformate salts that contain high‐nitrogen cations were synthesized by taking advantage of the relatively high acidity of nitroform. All of the new salts have been characterized by elemental, spectral, and thermal analyses. Single‐crystal X‐ray analysis of 2 shows that it is a co‐crystal of a neutral 4‐amino‐1,2,4‐triazole molecule with the 4‐amino‐1,2,4‐triazolium nitroformate ion pair. The presence of the neutral molecule appears to lend stability to the salt. The structure of 3,6‐diguanidino‐1,2,4,5‐tetrazinium nitroformate (10) was also confirmed by single‐crystal X‐ray analysis. Theoretical performance calculations indicate that these materials have properties which compare favorably with hydrazinium nitroformate, TNT and Tetryl suggesting potential applications as eco‐friendly oxidizers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Potassium‐, Ammonium‐, Hydrazinium‐, Guanidinium‐, Aminoguanidinium‐, Diaminoguanidinium‐, Triaminoguanidinium‐ and Melaminiumnitroformate – Synthesis, Characterization and Energetic Properties

Göbel

Klapötke

2007

Zeitschrift anorg allge chemie

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Energetic salts containing the nitroformate (trinitromethanide) anion with several nitrogen‐rich cations were investigated, including ammonium nitroformate (ANF), melaminium nitroformate (MNF), guanidinium nitroformate monohydrate (GNFH), aminoguanidinium nitroformate (AGNF), diaminoguanidinium nitroformate (DAGNF) as well as triaminoguanidinium nitroformate (TAGNF). All salts were characterized using vibrational spectroscopy (IR, Raman), mass spectrometry, multinuclear NMR spectroscopy and elemental analysis. The thermal decomposition of the salts was monitored using differential scanning calorimetry. In addition, the impact, friction and electrostatic sensitivity data were determined. Theoretical calculations were carried out in order to predict performance data such as detonation velocities and detonation pressures. The crystal structures of ANF, MNF, GNFH, AGNF, DAGNF and TAGNF were determined using single crystal X‐ray diffraction. In addition, a second polymorph of MNF was determined crystallographically as well as the crystal structures of MNF with methanol and MNF with dimethylsulfoxide. Finally, new polymorphs of potassium nitroformate (KNF) and hydrazinium nitroformate (HNF) were characterized using single crystal X‐ray diffraction.

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Combined study of thermochemical properties of nitroform and its salts

Cited by 7 publications

References 3 publications

Theoretical Study of the Primary Processes in the Thermal Decomposition of Hydrazinium Nitroformate

Theoretical Study of the Primary Processes in the Thermal Decomposition of Hydrazinium Nitroformate

Synthesis and Characterization of New Energetic Nitroformate Salts

Potassium‐, Ammonium‐, Hydrazinium‐, Guanidinium‐, Aminoguanidinium‐, Diaminoguanidinium‐, Triaminoguanidinium‐ and Melaminiumnitroformate – Synthesis, Characterization and Energetic Properties

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