TY - JOUR
T1 - Identification of liquid-phase decomposition species and reactions for guanidinium azotetrazolate
AU - Kumbhakarna, Neeraj R.
AU - Shah, Kaushal J.
AU - Chowdhury, Arindrajit
AU - Thynell, Stefan T.
N1 - Funding Information:
The authors acknowledge the support from the Air Force Office of Scientific Research under grant number FA9550-13-1-0004 . Also, this material is based upon work supported by, or in part by, the U.S. Army Research Laboratory and the U.S. Army Research Office under grant number W911NF-07-1-0083 . We are grateful to Dr. David Chavez of Los Alamos National Laboratory for the shipment of GzT.
PY - 2014/8/20
Y1 - 2014/8/20
N2 - The objective of this work is to analyze the decomposition of guanidinium azotetrazolate (GzT) in the liquid phase by using a combined experimental and computational approach. The experimental part involves the use of Fourier transform infrared (FTIR) spectroscopy to acquire the spectral transmittance of the evolved gas-phase species from rapid thermolysis, as well as to acquire spectral transmittance of the condensate and residue formed from the decomposition. Time-of-flight mass spectrometry (ToFMS) is also used to acquire mass spectra of the evolved gas-phase species. Sub-milligram samples of GzT were heated at rates of about 2000 K/s to a set temperature (553-573 K) where decomposition occurred under isothermal conditions. N2, NH 3, HCN, guanidine and melamine were identified as products of decomposition. The computational approach is based on using quantum mechanics for confirming the identity of the species observed in experiments and for identifying elementary chemical reactions that formed these species. In these ab initio techniques, various levels of theory and basis sets were used. Based on the calculated enthalpy and free energy values of various molecular structures, important reaction pathways were identified. Initiation of decomposition of GzT occurs via ring opening to release N2.
AB - The objective of this work is to analyze the decomposition of guanidinium azotetrazolate (GzT) in the liquid phase by using a combined experimental and computational approach. The experimental part involves the use of Fourier transform infrared (FTIR) spectroscopy to acquire the spectral transmittance of the evolved gas-phase species from rapid thermolysis, as well as to acquire spectral transmittance of the condensate and residue formed from the decomposition. Time-of-flight mass spectrometry (ToFMS) is also used to acquire mass spectra of the evolved gas-phase species. Sub-milligram samples of GzT were heated at rates of about 2000 K/s to a set temperature (553-573 K) where decomposition occurred under isothermal conditions. N2, NH 3, HCN, guanidine and melamine were identified as products of decomposition. The computational approach is based on using quantum mechanics for confirming the identity of the species observed in experiments and for identifying elementary chemical reactions that formed these species. In these ab initio techniques, various levels of theory and basis sets were used. Based on the calculated enthalpy and free energy values of various molecular structures, important reaction pathways were identified. Initiation of decomposition of GzT occurs via ring opening to release N2.
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U2 - 10.1016/j.tca.2014.06.005
DO - 10.1016/j.tca.2014.06.005
M3 - Article
AN - SCOPUS:84903214128
SN - 0040-6031
VL - 590
SP - 51
EP - 65
JO - Thermochimica Acta
JF - Thermochimica Acta
ER -