Rapid estimation of thermodynamic parameters and vapor pressures of volatile materials at nanoscale

Walid M. Hikal, Jeffrey T. Paden, Brandon L. Weeks

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Non-isothermal measurements of thermodynamic parameters and vapor pressures of low-volatile materials are favored when time is a crucial factor to be considered, such as in the case of detection of hazardous materials. In this article, we demonstrate that optical absorbance spectroscopy can be used non-isothermally to estimate the thermodynamic properties and vapor pressures of volatile materials with good accuracy. This is the first method to determine such parameters in nanoscale in just minutes. Trinitrotoluene (TNT) is chosen because of its low melting temperature, which makes it impossible to determine its thermodynamic parameter by other rising-temperature techniques, such as thermogravimetric analysis (TGA). The well-characterized vapor pressure of benzoic acid is used to calibrate the spectrometer in order to determine the vapor pressure of low-volatile TNT. The estimated thermodynamic properties of both benzoic acid and TNT are in excellent agreement with the literature. The estimated vapor pressure of TNT is one order of magnitude larger than that determined isothermally using the same method. However, the values are still within the range reported in the literature. The data indicate the high potential for use of rising-temperature absorbance spectroscopy in determining vapor pressures of materials at nanometer scale in minutes instead of hours or days. Heat up: Absorbance spectroscopy is used to non-isothermally determine the Arrhenius parameters of TNT at nanoscale accurately without the need of modeling (see picture). In addition, we show that the spectrometer can be calibrated to determine the vapor pressures and heats of sublimation of TNT under the same conditions.

Original languageEnglish
Pages (from-to)2729-2733
Number of pages5
Issue number11
StatePublished - Aug 6 2012


  • activation energy
  • explosives
  • frequency factor
  • optical absorbance spectroscopy
  • vapor pressure


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