Predicting Impact Sensitivities of Nitro Compounds on the Basis of a Semi-empirical Rate Constant

Mathieu, Didier; Alaime, Thibaud

doi:10.1021/jp507057r

Cited by 54 publications

(61 citation statements)

References 41 publications

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“…Its value is estimated using the H 2 O−CO 2 arbitrary, 35 neglecting the formation enthalpy Δ f H 0 of the unreacted material and resorting to experimental formation enthalpies compiled in the NIST WebBook database 36 for the decomposition products. 29 Since k pr is defined up to a multiplicative constant, we may arbitrarily set Z C = 1 for prefactors associated with C−NO 2 bonds. On the other hand, standard D i data derived from density functional theory are used, as described in ref 29.…”

Section: Semiempirical Modelmentioning

confidence: 99%

“…29 Since k pr is defined up to a multiplicative constant, we may arbitrarily set Z C = 1 for prefactors associated with C−NO 2 bonds. On the other hand, standard D i data derived from density functional theory are used, as described in ref 29. For completeness, the values involved in the present study are reported in Table S2 in the Supporting Information.…”

Section: Semiempirical Modelmentioning

confidence: 99%

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Physics-Based Modeling of Chemical Hazards in a Regulatory Framework: Comparison with Quantitative Structure–Property Relationship (QSPR) Methods for Impact Sensitivities

Mathieu

2016

Ind. Eng. Chem. Res.

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A semiempirical model based on simple physical assumptions is rigorously compared to a combination of two recent state-of-the-art quantitative structure−property relationship (QSPR) methods for impact sensitivities of nitroaliphatic and nitramine compounds. For most datasets considered, it yields slightly better predictions than QSPR schemes, which is noteworthy, considering the fact that it relies only on three adjustable parameters and an equation developed independently of the data. Further advantages of this approach include physical interpretability, enhanced robustness, and wider applicability. Therefore, there is no doubt that such physics-based models provide valuable alternatives to the purely empirical relationships usually employed in regulatory contexts, especially in situations where experimental data are scarce.

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Section: Semiempirical Modelmentioning

confidence: 99%

Section: Semiempirical Modelmentioning

confidence: 99%

Physics-Based Modeling of Chemical Hazards in a Regulatory Framework: Comparison with Quantitative Structure–Property Relationship (QSPR) Methods for Impact Sensitivities

Mathieu

2016

Ind. Eng. Chem. Res.

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“…This value is the height from where a certain weight of a given mass is dropped over a small amount of the explosive. The chance of triggering the material from this stimulus in 50% of the drops is the h 50 of the material …”

Section: Introductionmentioning

confidence: 99%

On the molecular origin of the sensitivity to impact of cyclic nitramines

Oliveira

Borges

2018

Int J of Quantum Chemistry

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Nitramine explosives can combine relative insensitivity to initiation and great energy content. In this work, based on a previous approach developed for nitroaromatic explosives, we propose four mathematical models to correlate impact sensitivity, given by the h50 value, to molecular charge properties. Fourteen cyclic nitramines were studied using Density Functional Theory (DFT). Six molecules of the set have measured h50 values, which were used to evaluate the sensitivity models. Converged DFT charge densities of the molecules were partitioned and analyzed according to the distributed multipole analysis (DMA) atom‐centered method. The sensitivity models were based on the DMA electric multipole values. The electron withdrawing role of the nitro group and the strong polarization of the charges of the nitrogen atom in the amine group were clearly identified. The influence of the electronic properties on the sensitivity of the explosives was characterized by including in the sensitivity models the charge values of the nitro or the nitramine groups and electron delocalization, the latter quantified by the DMA quadrupole values of the ring atoms. Inclusion of electron delocalization effects can improve the prediction of h50 values for two out of the five strained‐ring nitramines in the set. The charge values of the nitramine groups are the most important molecular property affecting the impact sensitivity. The h50 values of eight nitramine explosives of the set not available experimentally were computed.

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“…leave-many-out (LMO) cross validations, via the Q 2 LOO, Q 2 10CV and Q 2 5CV coefficients (for LOO, 10-fold and 5-fold cross validations, respectively) (Gramatica, 2007;Mathieu and Alaime, 2014 (2) are 0.87 and 6.8%, respectively, which confirms a good fitting as compared to R 2 Ext = 0.87 (good stability) (Gao et al, 2014) and MAPE Ext = 7.0% of cross-validation result.…”

Section: (Iv) Comparison Of the New Model With Two Different Modelsmentioning

confidence: 70%

Reliable method for safety assessment of melting points of energetic compounds

Hamadanian

Keshavarz

Nazari

et al. 2016

Process Safety and Environmental Protection

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Predicting Impact Sensitivities of Nitro Compounds on the Basis of a Semi-empirical Rate Constant

Cited by 54 publications

References 41 publications

Physics-Based Modeling of Chemical Hazards in a Regulatory Framework: Comparison with Quantitative Structure–Property Relationship (QSPR) Methods for Impact Sensitivities

Physics-Based Modeling of Chemical Hazards in a Regulatory Framework: Comparison with Quantitative Structure–Property Relationship (QSPR) Methods for Impact Sensitivities

On the molecular origin of the sensitivity to impact of cyclic nitramines

Reliable method for safety assessment of melting points of energetic compounds

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