Analytical Sciences

Thermodynamic Studies on a Hydrogen Bonded Acidic 3,5-Bis(trifluoromethyl)phenol-functionalized Polymer as a Gas Chromatography Stationary Phase for Selectively Speciating Chemical Warfare Agents

Douglas H. READ,*1 Komandoor E. ACHYUTHAN,*2 Cory S. FIX,*3 Ronald P. MANGINELL,*2 Matthew W. MOORMAN,*2 Robert J. SIMONSON,*4 David R. WHEELER,*5 and Joshua J. WHITING*2

*1 FENG & Tube Lifecycle Engineering Department, Sandia National Laboratories, Albuquerque, NM 87185, USA
*2 Nano & Micro Sensors Department, Sandia National Laboratories, Albuquerque, NM 87185, USA
*3 CBRNE Defense, Battelle Memorial Institute, Columbus, OH 43201, USA
*4 Sandia National Laboratories, Albuquerque, NM 87185, USA (retired)
*5 Special Technologies Department, Sandia National Laboratories, Albuquerque, NM 87185, USA

We describe for the first time hydrogen bonded acid (HBA) polymer, poly{methyl[3-(2-hydroxyl, 4,6-bistrifluoromethyl)phenyl]propylsiloxane}, (DKAP), as stationary phase for gas chromatography (μGC) of organophosphate (OP), chemical warfare agent (CWA) surrogates, dimethylmethylphosphonate (DMMP), diisopropylmethylphosphonate (DIMP), diethylmethylphosphonate (DEMP), and trimethylphosphate (TMP), with high selectivity. Absorption of OPs to DKAP was one-to-several orders of magnitude higher relative to commercial polar, mid-polar, and nonpolar stationary phases. We also present for the first-time thermodynamic studies on the absorption of OP vapors and quantitative binding energy data for interactions with various stationary phases. These data help to identify the best pair of hetero-polar columns for a two-dimensional GC system, employing a nonpolar stationary phase as GC1 and DKAP as the GC2 stationary phase, for selective and rapid field detection of CWAs.

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