Experimental Investigation of the Thermal Decomposition Pathways and Kinetics of TATB by Isotopic Substitution

Koroglu, Batikan; Crowhurst, Jonathan C.; Kahl, Evan M.; Moore, Jason S.; Racoveanu, Ana; Mason, Harris E.; Weisz, David G.; Reynolds, John G.; Burnham, Alan K.

doi:10.1002/prep.202100082

Experimental Investigation of the Thermal Decomposition Pathways and Kinetics of TATB by Isotopic Substitution

Journal Article · Tue Jun 08 00:00:00 EDT 2021 · Propellants, Explosives, Pyrotechnics

DOI:https://doi.org/10.1002/prep.202100082· OSTI ID:1818412

^[1]; Crowhurst, Jonathan C. ^[1]; Kahl, Evan M. ^[1]; Moore, Jason S. ^[1]; Racoveanu, Ana ^[1]; Mason, Harris E. ^[1]; Weisz, David G. ^[1]; Reynolds, John G. ^[1]; Burnham, Alan K. ^[2]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); M.H. Chew and Associates, Livermore, CA (United States)

Real-time measurements of the product gases arising from the thermal decomposition of triamino-trinitro benzene (TATB), its deuterated analogue, and plastically bonded TATB (LX-17) are presented in this study. Gas-phase decomposition products are identified by IR absorption spectroscopy. The frequency shifts in rovibrational spectra due to isotopic substitution and the change in rate of formation of decomposition products due to the kinetic-isotope-effect (KIE) help elucidate the decomposition pathways. The formation of H₂O precedes other molecules (e.g., HCN, HNCO) during decomposition. After the concentrations of HCN and HNCO molecules reach a peak, their amounts gradually decrease. The concentrations of the other decomposition products (e.g., NH₃ and CO₂) rapidly rise after an induction period, which is attributed to the presence of autocatalytic reactions. The trends of chemical evolution are similar for all the samples, but their kinetic behaviors are different. This indicates the rates of consistent pathways are changed during thermal decomposition. Additionally, the kinetics of deuterated TATB decomposition is slower than that of unsubstituted TATB due to the KIE (kH/kD~1.41). The rate of LX-17 decomposition is slightly lower than unsubstituted TATB (k_TATB/k_LX-17~1.15). The KIE is more pronounced during the early stage of decomposition, which is attributed to the first steps of TATB decomposition involving water formation (i.e., H vs D transfer). The KIE slows down the formation of all gases, including those lacking hydrogen (e.g., CO₂). These results suggest the TATB thermal decomposition mechanism might involve a series of pathways rather than a set of independent and parallel reactions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1818412

Report Number(s):: LLNL-JRNL--820018; 1030501

Journal Information:: Propellants, Explosives, Pyrotechnics, Journal Name: Propellants, Explosives, Pyrotechnics Journal Issue: 9 Vol. 46; ISSN 0721-3115

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Preheating Sensitization of a TATB Composition Part one: Chemical Evolution Belmas, Robert; Bry, Alain; David, Claire Propellants, Explosives, Pyrotechnics, Vol. 29, Issue 5 https://doi.org/10.1002/prep.200400059	journal	October 2004
Spectroscopic and thermal studies on the decomposition of l,3,5-triamino-2,4,6-trinitrobenzene (TATB) Makashir, P. S.; Kurian, E. M. Journal of Thermal Analysis, Vol. 46, Issue 1 https://doi.org/10.1007/BF01979963	journal	January 1996
XPS study of UV and shock decomposed triamino-trinitrobenzene Sharma, J.; Owens, F. J. Chemical Physics Letters, Vol. 61, Issue 2 https://doi.org/10.1016/0009-2614(79)80644-2	journal	February 1979
Thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene Farber, Milton; Srivastava, R. D. Combustion and Flame, Vol. 42 https://doi.org/10.1016/0010-2180(81)90155-3	journal	January 1981
Infrared spectra and isomerization of CHNO species in rare gas matrices Bondybey, V. E.; English, J. H.; Mathews, C. Weldon Journal of Molecular Spectroscopy, Vol. 92, Issue 2 https://doi.org/10.1016/0022-2852(82)90113-8	journal	April 1982
Inversion doubling in the ν2 vibration-rotation band of NH2D and ND2H Coudert, L.; Valentin, A.; Henry, L. Journal of Molecular Spectroscopy, Vol. 120, Issue 1 https://doi.org/10.1016/0022-2852(86)90081-0	journal	November 1986
Rotational analysis of the ν2 band of NH2D Job, V. A.; Kartha, S. B.; Kartha, V. B. Journal of Molecular Spectroscopy, Vol. 120, Issue 1 https://doi.org/10.1016/0022-2852(86)90082-2	journal	November 1986
Inversion-rotation interaction in NH2D: Intensity perturbations in the ν2 band Job, V. A.; Kartha, S. B.; Singh, Kuldip Journal of Molecular Spectroscopy, Vol. 126, Issue 2 https://doi.org/10.1016/0022-2852(87)90238-4	journal	December 1987
Measurement and interpretation of the absolute infrared intensities of NH3 and ND3 Koops, Th.; Visser, T.; Smit, W. M. A. Journal of Molecular Structure, Vol. 96, Issue 3-4 https://doi.org/10.1016/0022-2860(83)90049-2	journal	January 1983
Application of scanning calorimetry to the study of chemical kinetics Rogers, R. N.; Smith, L. C. Thermochimica Acta, Vol. 1, Issue 1 https://doi.org/10.1016/0040-6031(70)85023-7	journal	March 1970
Thermochemistry of explosives Rogers, Raymond N. Thermochimica Acta, Vol. 11, Issue 2 https://doi.org/10.1016/0040-6031(75)80016-5	journal	February 1975
Kinetic-isotope effects in thermal explosions Rogers, R. N.; Janney, J. L.; Ebinger, M. H. Thermochimica Acta, Vol. 59, Issue 3 https://doi.org/10.1016/0040-6031(82)87151-7	journal	December 1982
An enthalpic study of the thermal decomposition of unconfined triaminotrinitrobenzene Catalano, Edward; Crawford, Patricia C. Thermochimica Acta, Vol. 61, Issue 1-2 https://doi.org/10.1016/0040-6031(83)80301-3	journal	February 1983
A study of the thermal decomposition of confined triaminotrinitrobenzene. The gaseous products and kinetics of evolution Catalano, Edward; Rolon, Claudia E. Thermochimica Acta, Vol. 61, Issue 1-2 https://doi.org/10.1016/0040-6031(83)80302-5	journal	February 1983
The infra-red absorption spectrum of DNCO Ashby, R. A.; Werner, R. L. Spectrochimica Acta, Vol. 22, Issue 7 https://doi.org/10.1016/0371-1951(66)80038-3	journal	July 1966
High-resolution spectra of the ν2 and 2ν2 bands of HCN and DCN Wang, Victor K.; Overend, J. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 29, Issue 4 https://doi.org/10.1016/0584-8539(73)80099-6	journal	April 1973
Vibrational spectrum of 1,3,5-triamino-2,4,6-trinitrobenzene Towns, Theodore G. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 39, Issue 9 https://doi.org/10.1016/0584-8539(83)80020-8	journal	January 1983
Infrared spectrum of solid isocyanic acid (HNCO): vibrational assignments and integrated band intensities Lowenthal, M. S.; Khanna, R. K.; Moore, Marla H. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 58, Issue 1 https://doi.org/10.1016/S1386-1425(01)00524-8	journal	January 2002
Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices Singh, Arjun; Sharma, Tirupati C.; Kumar, Mahesh Defence Technology, Vol. 13, Issue 1 https://doi.org/10.1016/j.dt.2016.11.005	journal	February 2017
The NH and ND stretching fundamentals of 14NH2D Snels, Marcel; Hollenstein, Hans; Quack, Martin Journal of Molecular Spectroscopy, Vol. 237, Issue 2 https://doi.org/10.1016/j.jms.2006.03.006	journal	June 2006
The HITRAN2012 molecular spectroscopic database Rothman, L. S.; Gordon, I. E.; Babikov, Y. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 130, p. 4-50 https://doi.org/10.1016/j.jqsrt.2013.07.002	journal	November 2013
Kinetics of thermal degradation of explosive binders Viton A, Estane, and Kel-F Burnham, Alan K.; Weese, Randall K. Thermochimica Acta, Vol. 426, Issue 1-2 https://doi.org/10.1016/j.tca.2004.07.009	journal	February 2005
Measurement of moisture outgassing of the plastic-bonded TATB explosive LX-17 Small, Ward; Glascoe, Elizabeth A.; Overturf, George E. Thermochimica Acta, Vol. 545 https://doi.org/10.1016/j.tca.2012.06.033	journal	October 2012
Effect of pressure on TATB and LX-17 thermal decomposition Burnham, Alan K.; Stanford, Victoria L.; Vyazovkin, Sergey Thermochimica Acta, Vol. 699 https://doi.org/10.1016/j.tca.2021.178908	journal	May 2021
Sigmoidal Nucleation and Growth Curves Across Nature Fit by the Finke–Watzky Model of Slow Continuous Nucleation and Autocatalytic Growth: Explicit Formulas for the Lag and Growth Times Plus Other Key Insights Bentea, Lucian; Watzky, Murielle A.; Finke, Richard G. The Journal of Physical Chemistry C, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpcc.6b12021	journal	February 2017
Silver Nanoparticles Synthesized by Microwave Heating: A Kinetic and Mechanistic Re-Analysis and Re-Interpretation Özkar, Saim; Finke, Richard G. The Journal of Physical Chemistry C, Vol. 121, Issue 49 https://doi.org/10.1021/acs.jpcc.7b06323	journal	December 2017
Hydrogen/Deuterium (H/D) Exchange Catalysis in Alkanes Sattler, Aaron ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b04201	journal	January 2018
Kinetics and mechanisms of thermal decomposition of nitroaromatic explosives Brill, Thomas B.; James, Kenneth J. Chemical Reviews, Vol. 93, Issue 8 https://doi.org/10.1021/cr00024a005	journal	December 1993
Thermal decomposition of energetic materials. 61. Perfidy in the amino-2,4,6-trinitrobenzene series of explosives Brill, T. B.; James, K. J. The Journal of Physical Chemistry, Vol. 97, Issue 34 https://doi.org/10.1021/j100136a017	journal	August 1993
Correlation of impact sensitivity with electronic levels and structure of molecules Sharma, J.; Beard, Bruce C.; Chaykovsky, M. The Journal of Physical Chemistry, Vol. 95, Issue 3 https://doi.org/10.1021/j100156a032	journal	February 1991
X-ray photoelectron study of electronic structure, ultraviolet, and isothermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene Sharma, J.; Garrett, W. L.; Owens, F. J. The Journal of Physical Chemistry, Vol. 86, Issue 9 https://doi.org/10.1021/j100206a034	journal	April 1982
The physical and chemical nature of sensitization centers left from hot spots caused in triaminotrinitrobenzene by shock or impact Sharma, J.; Forbes, J. W.; Coffey, C. S. The Journal of Physical Chemistry, Vol. 91, Issue 19 https://doi.org/10.1021/j100303a053	journal	September 1987
Ring Closure Mediated by Intramolecular Hydrogen Transfer in the Decomposition of a Push−Pull Nitroaromatic: TATB Wu, Christine J.; Fried, Laurence E. The Journal of Physical Chemistry A, Vol. 104, Issue 27 https://doi.org/10.1021/jp001019r	journal	July 2000
Ultrafast Shock Compression and Shock-Induced Decomposition of 1,3,5-Triamino-2,4,6-trinitrobenzene Subjected to a Subnanosecond-Duration Shock: An Analysis of Decomposition Products Carter, Jeffrey A.; Zaug, Joseph M.; Nelson, A. J. The Journal of Physical Chemistry A, Vol. 116, Issue 20 https://doi.org/10.1021/jp301771y	journal	May 2012
Moisture Desorption Rates from TATB Formulations: Experiments and Kinetic Models Glascoe, Elizabeth A.; Dinh, Long N.; Small, Ward The Journal of Physical Chemistry A, Vol. 116, Issue 22 https://doi.org/10.1021/jp303074g	journal	May 2012
Nanosecond Time-Resolved and Steady-State Infrared Studies of Photoinduced Decomposition of TATB at Ambient and Elevated Pressure Glascoe, Elizabeth A.; Zaug, Joseph M.; Armstrong, Michael R. The Journal of Physical Chemistry A, Vol. 113, Issue 20 https://doi.org/10.1021/jp809418a	journal	April 2009
Mechanism of the Gas-Phase HO + H ₂ O → H ₂ O + OH Reaction and Several Associated Isotope Exchange Reactions: A Canonical Variational Transition State Theory Plus Multidimensional Tunneling Calculation Masgrau, Laura; González-Lafont, Angels; Lluch, José M. The Journal of Physical Chemistry A, Vol. 103, Issue 8 https://doi.org/10.1021/jp983749t	journal	February 1999
Vibration Spectra of 1,3,5‐Triamino‐2,4,6‐trinitrobenzene Deopura, B. L.; Gupta, V. D. The Journal of Chemical Physics, Vol. 54, Issue 9 https://doi.org/10.1063/1.1675458	journal	May 1971
Low‐Temperature Infrared Study of Intermediates in the Photolysis of HNCO and DNCO Jacox, Marilyn E.; Milligan, Dolphus E. The Journal of Chemical Physics, Vol. 40, Issue 9 https://doi.org/10.1063/1.1725546	journal	May 1964
Infrared Spectra of Hydrogen Cyanide and Deuterium Cyanide Allen, Harry C.; Tidwell, Eugene D.; Plyler, Earle K. The Journal of Chemical Physics, Vol. 25, Issue 2 https://doi.org/10.1063/1.1742876	journal	August 1956
Shock induced sub-detonation chemical reactions in 1,3,5-triamino-2,4,6-trinitrobenzene Östmark, Henric Proceedings of the conference of the American Physical Society topical group on shock compression of condensed matter, AIP Conference Proceedings https://doi.org/10.1063/1.50841	conference	January 1996
Characterization of solid residue formation in LX-17 exposed to abnormal thermal environments Kahl, Evan M.; Muetterties, Nicholas K.; Nelson, A. J. SHOCK COMPRESSION OF CONDENSED MATTER - 2019: Proceedings of the Conference of the American Physical Society Topical Group on Shock Compression of Condensed Matter, AIP Conference Proceedings https://doi.org/10.1063/12.0000948	conference	January 2020
Gas-Grain Modeling of Isocyanic acid (Hnco), Cyanic acid (Hocn), Fulminic acid (Hcno), and Isofulminic acid (Honc) in Assorted Interstellar Environments Quan, Donghui; Herbst, Eric; Osamura, Yoshihiro The Astrophysical Journal, Vol. 725, Issue 2 https://doi.org/10.1088/0004-637X/725/2/2101	journal	December 2010
The Infrared Absorption Spectra of the Linear Molecules Carbonyl Sulphide and Deuterium Cyanide Bartunek, Paul F.; Barker, E. F. Physical Review, Vol. 48, Issue 6 https://doi.org/10.1103/PhysRev.48.516	journal	September 1935
Influence of metals on the thermal decomposition of s-triaminotrinitrobenzene (TATB) Loughran, E. D.; Wewerka, E. M.; Rogers, R. N. https://doi.org/10.2172/7321145	report	July 1977
The insensitive high explosive triaminotrinitrobenzene (TATB): Development and characterization, 1888 to 1994 Dobratz, B. M. https://doi.org/10.2172/90370	report	August 1995

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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thermal decomposition

Experimental Investigation of the Thermal Decomposition Pathways and Kinetics of TATB by Isotopic Substitution

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