title: In Silico Alkaline Hydrolysis of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine: Density Functional Theory Investigation.
abstract: HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), an energetic material used in military applications, may be released to the environment during manufacturing, transportation, storage, training, and disposal. A detailed investigation of a possible mechanism of alkaline hydrolysis, as one of the most promising methods for HMX remediation, was performed by computational study at PCM(Pauling)/M06-2X/6-311++G(d,p) level. Obtained results suggest that HMX hydrolysis at pH 10 represents a highly exothermic multistep process involving initial deprotonation and nitrite elimination, hydroxide attachment accompanied by cycle cleavage, and further decomposition of cycle-opened intermediate to the products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of HMX hydrolysis such as nitrite, 4-nitro-2,4-diazabutanal, formaldehyde, nitrous oxide, formate, and ammonia correspond to experimentally observed species. Based on computed reaction pathways for HMX decomposition by alkaline hydrolysis, the kinetics of the entire process was modeled. Very low efficiency of this reaction at pH 10 was observed. Computations predict significant increases (orders of magnitude) of the hydrolysis rate for hydrolysis reactions undertaken at pH 11, 12, and 13.
authors: Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University , Dnipropetrovsk 49000, Ukraine.
authors: Liudmyla K
authors: LK
authors: Sviatenko
authors: HX5 , Vicksburg, Mississippi 39180, United States.
authors: Leonid
authors: L
authors: Gorb
authors: U.S. Army Engineer Research and Development Center , Vicksburg, Mississippi 39180, United States.
authors: Frances C
authors: FC
authors: Hill
authors: Danuta
authors: D
authors: Leszczynska
authors: U.S. Army Engineer Research and Development Center , Vicksburg, Mississippi 39180, United States.
authors: Manoj K
authors: MK
authors: Shukla
authors: Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University , Dnipropetrovsk 49000, Ukraine.
authors: Sergiy I
authors: SI
authors: Okovytyy
authors: Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine , 150 Zabolotny Street, Kyiv 03143, Ukraine.
authors: Dmytro
authors: D
authors: Hovorun
authors: Jerzy
authors: J
authors: Leszczynski
mesh_terms: D003198:Computer Simulation; D006573:Heterocyclic Compounds, 1-Ring; D006868:Hydrolysis; D007700:Kinetics; D009573:Nitrites
chemical_list: D006573:Heterocyclic Compounds, 1-Ring; D009573:Nitrites