title: In silico kinetics of alkaline hydrolysis of 1,3,5-trinitro-1,3,5-triazinane (RDX): M06-2X investigation.
abstract: Alkaline hydrolysis of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), as one of the most promising methods for nitrocompound remediation, was investigated computationally at the PCM(Pauling)/M06-2X/6-311++G(d,p) level of theory. Computational simulation shows that RDX hydrolysis is a highly exothermic multistep process involving initial deprotonation and nitrite elimination, cycle cleavage, further transformation of cycle-opened intermediates to end products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of RDX hydrolysis such as nitrite, nitrous oxide, formaldehyde, formate, and ammonia correspond to experimentally observed ones. Accounting of specific hydration of hydroxide is critical to create an accurate kinetic model for alkaline hydrolysis. Simulated kinetics of the hydrolysis are in good agreement with available experimental data. A period of one month is necessary for 99% RDX decomposition at pH 10. Computations predict significant increases of the reaction rate of hydrolysis at pH 11, pH 12, and pH 13.
authors.affiliation: Department of General and Biological Chemistry N2, Donetsk National Medical University, 1 Velyka Perspectyvna Str., Kropyvnytskyi, 25015, Ukraine.
authors.forename: L K
authors.identifier: http://orcid.org/0000-0003-2145-707X
authors.initials: LK
authors.lastname: Sviatenko
authors.affiliation: HX5, LLC, Vicksburg, Mississippi, USA.
authors.forename: L
authors.initials: L
authors.lastname: Gorb
authors.affiliation: Interdisciplinary Center for Nanotoxicity, Department of Civil and Environmental Engineering, Jackson State University, Jackson, Mississippi 39217, USA.
authors.forename: D
authors.initials: D
authors.lastname: Leszczynska
authors.affiliation: Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University, Dnipropetrovsk, 49000, Ukraine.
authors.forename: S I
authors.initials: SI
authors.lastname: Okovytyy
authors.affiliation: US Army ERDC, Vicksburg, Mississippi 39180, USA.
authors.forename: M K
authors.initials: MK
authors.lastname: Shukla
authors.affiliation: Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi 39217, USA. jerzy@icnanotox.org.
authors.forename: J
authors.initials: J
authors.lastname: Leszczynski
mesh_terms: D000641:Ammonia / Q000737:chemistry; D003198:Computer Simulation; D052918:Environmental Restoration and Remediation; D005557:Formaldehyde / Q000737:chemistry; D005561:Formates / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D008956:Models, Chemical; D009573:Nitrites / Q000737:chemistry; D009609:Nitrous Oxide / Q000737:chemistry; D014227:Triazines / Q000737:chemistry*
chemical_list: D005561:Formates; D009573:Nitrites; D014227:Triazines; C030544:formic acid; D005557:Formaldehyde; D000641:Ammonia; D009609:Nitrous Oxide; C009160:cyclonite