Influence of the physical state of an explosive on its sensitivity. Is nitromethane sensitive or insensitive?

Odiot, S.; Blain, M.; Vauthier, E.; Fliszár, Sándor

doi:10.1016/0166-1280(93)90071-i

Cited by 15 publications

(3 citation statements)

References 38 publications

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“…Ab initio calculations have been performed for a system of three NM molecules, 58 arranged in the geometry of the crystalline solid. These calculations suggest that the CN bond of the central molecule will actually be strengthened slightly by the presence of the other two molecules.…”

Section: Comprehensive Interpretation Of the Experimental Resultsmentioning

confidence: 99%

Shock-Induced Chemical Changes in Neat Nitromethane: Use of Time-Resolved Raman Spectroscopy

Winey

Gupta

1997

J. Phys. Chem. B

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Time-resolved Raman spectroscopy was used to examine chemical changes in neat liquid nitromethane subjected to stepwise loading to peak pressures of 14−17 GPa. After a peak pressure at 14 GPa was reached, no changes in the CN (917 cm-1), NO2 (1400 cm-1), and CH3 (2968 cm-1) symmetric stretching modes were observed. After a peak pressure at 16 GPa was reached, time-dependent changes were observed during the induction period reported in previous absorption experiments. At this peak pressure, the extent of reaction was small, and the observed changes in the CH3 and CN modes indicated prereaction changes in the sample bulk. After a peak pressure at 17 GPa was reached (980 K peak temperature), all three peaks disappeared, indicating that the extent of reaction was substantial under these conditions. The broadening of the CH3 peak and the softening of the CN mode observed in this work suggest strong intermolecular interactions. These interactions lead to a reaction precursor involving proposed head-to-tail intermolecular associations with decomposition proposed to follow through a bimolecular reaction, put forward by Bardo, which forms nitrosomethane and nitromethanol. Confirmation of these ideas will require different spectroscopic methods, since Raman measurements are primarily useful for probing initial changes in the sample.

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Section: Comprehensive Interpretation Of the Experimental Resultsmentioning

confidence: 99%

Shock-Induced Chemical Changes in Neat Nitromethane: Use of Time-Resolved Raman Spectroscopy

Winey

Gupta

1997

J. Phys. Chem. B

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“…Based on these results, BDE/E could be considered as a reasonably practical indicator of explosive sensitivity. According to Odiot, [23] however, based on self-consistent field calculations, it was found that the crystalline environment could significantly reinforce the CAN bond in nitromethane by about 4.7 kcal mol À1 compared to a gas phase molecule. It was further found by Odiot's et al that one should be wary of relying on an oversimplified oneto-one correspondence between sensitivity and molecular structure in the context of safety rules, as changes in bond dissociation energies (BDEs) are dependent on the physical state of a substance.…”

Section: Bond Dissociation Energy Methodsmentioning

confidence: 99%

Theoretical evaluation of sensitivity and thermal stability for high explosives based on quantum chemistry methods: A brief review

Yan

Zeman

2012

Int J of Quantum Chemistry

114

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Over the past 20 years, a number of scientists have conducted numerous fundamental investigations based on quantum chemistry theory into various mechanistic processes that seems to contribute to the sensitivity of energetic materials. A large number of theoretical methods that have been used to predict their mechanical and spark sensitivity are summarized in this article, in which the advantages and disadvantages of these methods, together with their scope of use are clarified. In addition, the theoretical models for thermal stability of explosives are briefly introduced as a supplement. It has been concluded that the current ability to predict sensitivity is merely based on a series of empirical rules, such as simple oxygen balance, molecular properties, and the ratios of C and H to oxygen for different classes of explosive compounds. These are valid only for organic classes of explosives, though some special models have been proposed for inorganic explosives, such as azides. An exact standard for sensitivity should be established experimentally by some new techniques for both energetic compounds and their mixtures. © 2013 Wiley Periodicals, Inc.

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“…Be-cause nitromethane can detonate and cause serious harm to people, in order to handle this solvent uneventfully, some unsafe conditions should be avoided during its uses. [4] In some cases, for example, when it is mixed with a few percent of certain compounds such as amines, acids, and bases, nitromethane is "sensitized" and can be easily detonated. However, because of its specific effect exhibited in some organic reactions, [5] the risk does not seem noticeable for many researchers who are using this solvent in combination with strong acidic catalysts.…”

Section: Introductionmentioning

confidence: 99%

An Alternative to Nitromethane as Solvent: The Promoting Influence of Nitro‐Functionalized Imidazolium Salts for Synthesis and Catalysis

Ren

Yang

et al. 2011

Adv Synth Catal

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Nitromethane, a volatile and toxic organic compound, is commonly used as solvent for organic and catalytic reactions. In order to find an alternative for this specific nitro-containing organic solvent, the performance of some nitro-functionalized imidazolium salts such as 1-methyl-3-(4-nitrobenzyl)imidazolium hexafluorophosphate, 1-methyl-3-(4-nitrobenz-A C H T U N G T R E N N U N G yl)imidazolium tetrafluoroborate, 1-methyl-3-(4-nitrobenzyl)imidazolium bis(trifluoromethanesulfonyl)-A C H T U N G T R E N N U N G amide and 1,2-dimethyl-3-(4-nitrobenzyl)imidazolium hexafluorophosphate, was examined in some reactions including trimethylsilylation of alcohols with hexamethyldisilazane, ring-opening reactions of 2-aryl-3,4-dihydropyrans with thiophenols or thiols, and a copper-mediated oxidative coupling of alkynes. As expected, these imidazolium salts can indeed replace nitromethane in these reactions. Particularly, the imidazolium salt along with the metal catalyst, if involved, can be easily recovered and reused without significant loss of activity. The use of these nitro-functionalized imidazolium salts as alternative solvents for nitromethane not only confers a green aspect to the reaction system, but also facilitates a rational design of a catalytic system with the concept of green chemistry.

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Influence of the physical state of an explosive on its sensitivity. Is nitromethane sensitive or insensitive?

Cited by 15 publications

References 38 publications

Shock-Induced Chemical Changes in Neat Nitromethane: Use of Time-Resolved Raman Spectroscopy

Shock-Induced Chemical Changes in Neat Nitromethane: Use of Time-Resolved Raman Spectroscopy

Theoretical evaluation of sensitivity and thermal stability for high explosives based on quantum chemistry methods: A brief review

An Alternative to Nitromethane as Solvent: The Promoting Influence of Nitro‐Functionalized Imidazolium Salts for Synthesis and Catalysis

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