skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Vapor Pressures of RDX and HMX Explosives Measured at and Near Room Temperature: 1,3,5-Trinitro-1,3,5-triazinane and 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane

Journal Article · · Journal of Physical Chemistry A

Knowing accurate saturated vapor pressures of explosives at ambient conditions is imperative to provide realistic boundaries on available vapor for ultra-trace detection. In quantifying vapor content emanating from low-volatility explosives, we observed discrepancies between the quantity of explosive expected based on literature vapor pressure values and the amount detected near ambient temperatures. Most vapor pressure measurements for low-volatility explosives, such as RDX (1,3,5-trinitro-1,3,5-triazinane) and HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), have been made at temperatures far exceeding 25 °C and linear extrapolation of these higher temperature trends appears to underestimate vapor pressures near room temperature. Our goal was to measure vapor pressures as a function of temperature closer to ambient conditions. We used saturated RDX and HMX vapor sources at controlled temperatures to produce vapors that were then collected and analyzed via atmospheric flow tube-mass spectrometry (AFT-MS). The parts-per-quadrillion (ppqv) sensitivity of AFT-MS enabled measurement of RDX vapor pressures at temperatures as low as 7 °C and HMX vapor pressures at temperatures as low as 40 °C for the first time. Furthermore, these vapor pressures were corroborated with analysis of vapor generated by nebulizing low concentration solutions of RDX and HMX. We report updated vapor pressure values for both RDX and HMX. Based on our measurements, the vapor pressure of RDX at 25 °C is 3 ± 1 x 10-11 atm (i.e. 30 parts per trillion by volume, pptv), the vapor pressure of HMX is 1.0 ± 0.6 x 10-14 atm (10 ppqv) at 40 °C and, with extrapolation, HMX has a vapor pressure of 1.0 ± 0.6 x 10-15 atm (1.0 ppqv) at 25 °C.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1767163
Report Number(s):
PNNL-SA-157995
Journal Information:
Journal of Physical Chemistry A, Vol. 125, Issue 5
Country of Publication:
United States
Language:
English

References (23)

Direct Real-Time Detection of RDX Vapors Under Ambient Conditions journal December 2012
Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry journal November 2015
Direct Real-Time Detection of Vapors from Explosive Compounds journal October 2013
Secondary electrospray ionization (SESI) of ambient vapors for explosive detection at concentrations below parts per trillion journal February 2009
Optimizing detection of RDX vapors using designed experiments for remote sensing journal January 2014
Detection of Inorganic Salt-Based Homemade Explosives (HME) by Atmospheric Flow Tube–Mass Spectrometry journal May 2018
Vapor pressure of explosives journal January 1986
Experimental Vapor Pressures of Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and Hexahydro‐1,3,5‐trinitroso‐1,3,5‐triazine (TNX) journal July 2020
Vapour pressure measurements on some organic high explosives
  • Cundall, Robert B.; Frank Palmer, T.; Wood, Colin E. C.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 74, Issue 0 https://doi.org/10.1039/F19787401339
journal January 1978
Vapour pressure and enthalpy of sublimation of 1,3,5,7-tetranitro-1,3,5,7-tetra-azacyclo-octane (HMX)
  • Taylor, John Watson; Crookes, Roy J.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0 https://doi.org/10.1039/f19767200723
journal January 1976
The vapour pressure of cyclo-trimethylene-trinitramine (cyclonite) and pentaerythritol-tetranitrate journal January 1953
Vapor pressures and heats of sublimation of some high-melting organic explosives journal January 1969
Vapor pressure determination by thermogravimetry journal March 2001
Assessment of systematic errors in measurement of vapor pressures by thermogravimetric analysis journal August 2007
Estimating Ambient Vapor Pressures of Low Volatility Explosives by Rising-Temperature Thermogravimetry journal April 2012
Estimations of Vapor Pressures by Thermogravimetric Analysis of the Insensitive Munitions IMX-101, IMX-104, and Individual Components journal December 2013
The vapor pressures of explosives journal January 2013
Vapor-generation methods for explosives-detection research journal December 2012
Combined secondary electrospray and corona discharge ionization (SECDI) for improved detection of explosive vapors using drift tube ion mobility spectrometry journal March 2020
Trace Explosives Vapor Generation and Quantitation at Parts per Quadrillion Concentrations journal March 2016
Historical development of the vapor pressure equation from dalton to antoine journal November 2001
Non-contact vapor detection of illicit drugs via atmospheric flow tube-mass spectrometry journal January 2020
Selective Reagent Ions for the Direct Vapor Detection of Organophosphorus Compounds Below Parts-per-Trillion Levels journal May 2018