Infrared Spectra and Binding Energies of Chemical Warfare Nerve Agent Simulants on the Surface of Amorphous Silica
ARMY EDGEWOOD CHEMICAL BIOLOGICAL CENTER APG MD RESEARCH AND TECHNOLOGY DIR
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The fundamental interactions of a series of chemical warfare agent CWA simulants on amorphous silica particulates have been investigated with transmission infrared spectroscopy and temperature-programmed desorption TPD. The simulants methyl dichlorophosphate MDCP, dimethyl cholorophosphate DMCP, trimethyl phosphate TMP, dimethyl methylphosphonate DMMP, and diisopropyl methylphosphonate DIMP were chosen to help develop a comprehensive understanding for how the structure and functionality of CWA surrogate compounds affect uptake and hydrogen-bond strengths at the gas surface interface. Each simulant was found to adsorb molecularly to silica through the formation of strong hydrogen bonds primarily between isolated surface silanol groups and the oxygen atom of the P O moiety in the adsorbate. The TPD data revealed that the activation energy for desorption of a single simulant molecule from amorphous silica varied slightly with coverage. In the limit of zero coverage and the absence of significant surface defects, the activation energies for desorption were found to follow the trend MDCP DMCP TMP DMMP DIMP. This trend demonstrates the critical role of electron-withdrawing substituents in determining the adsorption energies through hydrogen-bonding interactions. The infrared spectra for each adsorbed species, recorded during uptake, showed a significant shift in the frequency of the vSiO-H mode as the hydrogen bonds formed. A clear linear relationship between the desorption energy and the shift of the surface vSiO-H mode across this series of adsorbates demonstrates that the Badger Bauer relationship, established originally for solute solvent interactions, effectively extends to gas surface interactions.
- Organic Chemistry
- Physical Chemistry
- Chemical, Biological and Radiological Warfare
- Atomic and Molecular Physics and Spectroscopy