Identifying the Molecular Properties that Drive Explosive Sensitivity in a Series of Nitrate Esters
Abstract
Energetic materials undergo hundreds of chemical reactions during exothermic runaway, generally beginning with the breaking of the weakest chemical bond, the “trigger linkage.” Herein we report the syntheses of a series of pentaerythritol tetranitrate (PETN) derivatives in which the energetic nitrate ester groups are systematically substituted by hydroxyl groups. Because all the PETN derivatives have the same nitrate ester-based trigger linkages, quantum molecular dynamics (QMD) simulations show very similar Arrhenius kinetics for the first reactions. However, handling sensitivity testing conducted using drop weight impact indicates that sensitivity decreases precipitously as nitrate esters are replaced by hydroxyl groups. These experimental results are supported by QMD simulations that show systematic decreases in the final temperatures of the products and the energy release as the nitrate ester functional groups are removed. To better interpret these results, we derive a simple model based only on the specific enthalpy of explosion and the kinetics of trigger linkage rupture that accounts qualitatively for the decrease in sensitivity as nitrate ester groups are removed.
- Authors:
-
[1];
[2];
[2];
[1]
- High Explosives Science & Technology, Los Alamos National Laboratory, Los Alamos, New Mexico87545, United States
- Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico87545, United States
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1890526
- Alternate Identifier(s):
- OSTI ID: 1907784
- Report Number(s):
- LA-UR-22-28697
Journal ID: ISSN 1948-7185
- Grant/Contract Number:
- KC0302020; 89233218CNA000001
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry Letters Journal Volume: 13 Journal Issue: 40; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lease, Nicholas, Klamborowski, Lisa M., Perriot, Romain, Cawkwell, Marc J., and Manner, Virginia W. Identifying the Molecular Properties that Drive Explosive Sensitivity in a Series of Nitrate Esters. United States: N. p., 2022.
Web. doi:10.1021/acs.jpclett.2c02701.
Lease, Nicholas, Klamborowski, Lisa M., Perriot, Romain, Cawkwell, Marc J., & Manner, Virginia W. Identifying the Molecular Properties that Drive Explosive Sensitivity in a Series of Nitrate Esters. United States. https://doi.org/10.1021/acs.jpclett.2c02701
Lease, Nicholas, Klamborowski, Lisa M., Perriot, Romain, Cawkwell, Marc J., and Manner, Virginia W. Mon .
"Identifying the Molecular Properties that Drive Explosive Sensitivity in a Series of Nitrate Esters". United States. https://doi.org/10.1021/acs.jpclett.2c02701.
@article{osti_1890526,
title = {Identifying the Molecular Properties that Drive Explosive Sensitivity in a Series of Nitrate Esters},
author = {Lease, Nicholas and Klamborowski, Lisa M. and Perriot, Romain and Cawkwell, Marc J. and Manner, Virginia W.},
abstractNote = {Energetic materials undergo hundreds of chemical reactions during exothermic runaway, generally beginning with the breaking of the weakest chemical bond, the “trigger linkage.” Herein we report the syntheses of a series of pentaerythritol tetranitrate (PETN) derivatives in which the energetic nitrate ester groups are systematically substituted by hydroxyl groups. Because all the PETN derivatives have the same nitrate ester-based trigger linkages, quantum molecular dynamics (QMD) simulations show very similar Arrhenius kinetics for the first reactions. However, handling sensitivity testing conducted using drop weight impact indicates that sensitivity decreases precipitously as nitrate esters are replaced by hydroxyl groups. These experimental results are supported by QMD simulations that show systematic decreases in the final temperatures of the products and the energy release as the nitrate ester functional groups are removed. To better interpret these results, we derive a simple model based only on the specific enthalpy of explosion and the kinetics of trigger linkage rupture that accounts qualitatively for the decrease in sensitivity as nitrate ester groups are removed.},
doi = {10.1021/acs.jpclett.2c02701},
journal = {Journal of Physical Chemistry Letters},
number = 40,
volume = 13,
place = {United States},
year = {Mon Oct 03 00:00:00 EDT 2022},
month = {Mon Oct 03 00:00:00 EDT 2022}
}
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