Characterization of cyclotrimethylenetrinitramine (RDX) by N,H isotope analyses with pyrolysis–atmospheric pressure ionization tandem mass spectrometry

Abstract

Pyrolysis-atmospheric pressure chemical ionization was used to study the thermal decomposition of the energetic material cyclotrimethylenetrinitramine (RDX) and characterization of the individual molecular ion products was accomplished by tandem mass spectrometry. The analysis was aided with pyrolysis mass spectra of the (''N)-and perdeuterated RDX isotopes, and molecular formulae were derived for the m/z 46, 60, 74, 75, 85 and 98 molecular ions in the RDX pyrolysis mass spectrum. Equivalent fragments between the daughter ion mass spectra of the unlabeled and labeled RDX were determined in order to define a structure for each pyrolysis feature. Daughter ion mass spectra of pure reference compounds confirmed the identity of five of the six molecular ions, Perdeuterated RDX analyses provided evidence that m/z 74 and 75 are N,N-dimethylformamide and N-nitrosodimethylamine, respectively; m/z 46, 60 and 85 were identified as the protonated forms of formamide, N-methylformamide and dimethylaminoacetonitrile, respectively.

The study of thermal decomposition of RDX by corona discharge-ion mobility spectrometry-mass spectrometry

“…It has been already mentioned by Liebman [16]) and Snyder [29]) in atmospheric pressure ionization (API) studies. This fragment has been postulated as triazine (C 3 H 7 N 3 ).…”

“…2b). Snyder [29]), who focused on characterization of RDX by pyrolysis-atmospheric pressure ionization -tandem mass spectrometry detected a Fig. 2 Response to RDX sample evaporated at 473 K at1.66 ppb concentration.…”

“…Another IMS peak formed (t d = 9.76 ms, K 0 = 2.18 cm 2 V −1 s −1 and m/z 88 Da) we attributed according to Yinon et al to = 10.54 ms, K 0 =2.01 cm 2 V −1 s −1 and m/z 98 Da) we also associate to RDX fragment in IMS. Stals [30], Snyder [29] and Yinon and Hass [35] identified it as C 3 H 4 N 3 O − and their appearance is result of pyrolysis, negative ion chemical ionization or collisional induced dissociation. Finally, we have detected in the IMS spectrum peak at t d = 14.1 ms (K 0 =1.51 cm 2 V −1 s −1 and m/z 257 Da), please look at Fig.…”

Ion spectrometric detection technologies for ultra‐traces of explosives: A review

“…Generally, various (Burrows, 1994) deuterated reagent gases for RDX, (Zitrin, 1982) hydrogen and deuterium (Gillis, Lacey, & Shannon, 1974), water (Yinon, 1974), isobutene (Yinon, 1980), and ammonia (Vouros et al, 1977) for various explosives have been investigated. Pyrolysis APCI has been used to analyze HMX and RDX (Snyder et al, 1989(Snyder et al, , 1990(Snyder et al, , 1991. Negative mode APCI has been used to investigate DNT isomers (Asselin & Paré, 1981).…”

Structure-Thermolysis Relationships for Energetic Materials

“…This suggests that HNCO may be evolved from the nonvolatile residue that forms while the initial gas generation is taking place. This residue is undoubtedly a mixture of components, but it contains various ami des and polymer ized products [55][56][57][58].…”