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Chemical ionization of the nitrate ester explosives EGDN and PETN by trimethylsilyl cation and comparison of the reactivity of nitrate ester and nitro explosives toward trimethylsilyl cation

Crellin, Kevin C. and Dalleska, Nathan and Beauchamp, J. L. (1997) Chemical ionization of the nitrate ester explosives EGDN and PETN by trimethylsilyl cation and comparison of the reactivity of nitrate ester and nitro explosives toward trimethylsilyl cation. International Journal of Mass Spectrometry and Ion Processes, 165-166 . pp. 641-653. ISSN 0168-1176. https://resolver.caltech.edu/CaltechAUTHORS:20150622-144456537

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Abstract

Fourier transform ion cyclotron resonance mass spectrometry has been used to examine the reactions of Si(CH_3)_3)^+ with EGDN and PETN. In addition, the reactions of Si(CH_3)_3^+ with EGDN and PETN was examined in a magnetic sector mass spectrometer. No adduct formation was observed with either EGDN or PETN in the Fourier transform ion cyclotron resonance mass spectrometer, but characteristic fragment ions are seen. Both EGDN and PETN form adducts with Si(CH_3)_3^+ in the sector mass spectrometer. The bimolecular rate constant for the reaction of Si(CH_3)_3^+ with EGDN is measured to be 0.91 × 10^(−10) cm^3 s^(−1) molecule^(−1), and the bimolecular rate constant for the reaction of Si(CH_3)_3^+ with PETN is estimated to be 8 × 10^(−10) cm^3 s^(−1) molecule^−1). Collision-induced dissociation experiments were performed on the major fragment ion products to characterize the observed fragmentation patterns. The fragment ions observed in both cases are characteristic of each explosive and could be useful in the analytical detection and identification of EGDN and especially PETN. Reaction coordinate diagrams for the reactions of EGDN and PETN with Si(CH3)3+ are derived (from known thermochemistry and semi-empirical calculations on the involved species). The reactivity of nitro and nitrate ester explosives with Si(CH_3)_3^+ is compared and reasons for their different chemical behavior are discussed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/S0168-1176(97)00189-4DOIArticle
http://www.sciencedirect.com/science/article/pii/S0168117697001894PublisherArticle
ORCID:
AuthorORCID
Dalleska, Nathan0000-0002-2059-1587
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 1997 Elsevier. Received 12 June 1997; accepted 7 July 1997. We wish to acknowledge the Federal Aviation Administration for support of this work under grant 93-G-060 and the Beckman Foundation and Institute for continuing support of the FT-ICR research facility. We also wish to acknowledge Professor William A. Goddard, III and the Beckman Institute Materials and Process Simulations Center for supporting some of our theoretical calculations.
Funders:
Funding AgencyGrant Number
Federal Aviation Administration (FAA)95-G-060
Arnold and Mabel Beckman FoundationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Subject Keywords:EGDN; PETN; Si(CH_3)_3^+; FT-ICR; Chemical ionization
Record Number:CaltechAUTHORS:20150622-144456537
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150622-144456537
Official Citation:Kevin C. Crellin, Nathan Dalleska, J.L. Beauchamp, Chemical ionization of the nitrate ester explosives EGDN and PETN by trimethylsilyl cation and comparison of the reactivity of nitrate ester and nitro explosives toward trimethylsilyl cation, International Journal of Mass Spectrometry and Ion Processes, Volumes 165–166, November 1997, Pages 641-653, ISSN 0168-1176, http://dx.doi.org/10.1016/S0168-1176(97)00189-4. (http://www.sciencedirect.com/science/article/pii/S0168117697001894)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58415
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:22 Jun 2015 22:46
Last Modified:03 Oct 2019 08:35

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