Kinetics of destruction of diisopropyl methylphosphonate in corona discharge

Abstract

The kinetics of the destruction of diisopropyl methylphosphonate (DIMP) in corona discharge has been studied using a flow tubular coaxial wire dielectric barrier corona discharge reactor. The identification and quantitative determination of DIMP, its destruction intermediates, and phosphorus-containing destruction products were performed using molecular beam mass spectrometry and gas chromatography/mass spectrometry. Active discharge power was varied in the range 0.01-5 W. The destruction products such as isopropyl methylphosphonate, methylphosphonic acid, and orthophosphoric acid were found on the reactor walls. The dependence of the extent of the destruction, D(D = 1 − X /X 0 , where X and X 0 are DIMP mole fractions at the outlet and the inlet of the reactor), on the specific energy deposition E x (E x = PF −1 X 0 −1 , where F is the carrier gas flow and P is the power dissipated in discharge reactor) was measured over the DIMP mole fraction range 60-500 ppm at the pressure of 1 bar and the temperature of 340 K. Over the range of the experimental conditions studied the destruction obeys the "pseudo-first-order" kinetic law: ln(1 − D) = −KE x . Plausible mechanisms of the destruction are discussed. It was concluded that ion mechanism is the major one responsible for the destruction process.

Atmospheric plasma-driven catalysis for the low temperature decomposition of dilute aromatic compounds

“…Therefore, the kinetics for the gas removal using plasma reactors has been expressed as a function of energy (dC/dE) in contrast to the conventional method, which express the gas removal as a function of time (dC/dt). Many published studies indicate that the dominant kinetics of the gas-phase plasma reaction is firstorder in the concentration [16][17][18][19][20]. Similar first-order kinetics was also reported in an early study on the NO x removal [21] and recent studies for the decomposition of VOCs [22][23][24][25] using an electron-beam generated gas-phase plasma.…”

“…Good carbon balances in the PDC reactor also indicate that the formation of other reaction by-products, such as aerosols and smaller organic compounds was negligible. In our previous work, we reported that a large amount of nanometresized aerosol was produced from the decomposition of benzene with gas-phase plasma reactors, where the carbon balance was also poor at 63-90% [19]. The good carbon balance with the PDC reactor also showed that the contribution of adsorption to the benzene removal could be ignored.…”

Rapid Laser-Induced Temperature Jump Decomposition of the Nerve Agent Simulant Diisopropyl Methylphosphonate under Atmospheric Conditions

“…Previous investigations into the thermal destruction of DIMP have consistently identified a number of products including propene, IPA, and ethylene. These studies include destruction via pyrolysis, combustion, exposure to a corona discharge, dissociative adsorption, laser ablation, and so forth. ,,,− While this provides a reasonable set of products to look for, the current work represents the first direct study of rapid laser heating (on the order of 10 11 K s –1 ) of adsorbed liquid DIMP under atmospheric pressure and oxygen-depleted conditions. It is therefore necessary to firmly establish the full range of products before attempting to assess branching ratios; this was done using ex situ FTIR.…”

“…Because of the threat chemical warfare agents (CWAs) pose to the global community, there is considerable interest in detecting, destroying existing stockpiles, and decontaminating areas affected by these compounds. , Current large-scale destruction techniques include incineration and neutralization by base hydrolysis, but these strategies come with additional challenges regarding safe transport and toxic byproducts . Therefore, it remains critical to continue developing new strategies and to understand the exact chemistry of agents’ destruction in both vapor and condensed phases.…”

Medium Vacuum Electron Emitter as Soft Atmospheric Pressure Chemical Ionization Source for Organic Molecules

“…By McLafferty rearrangement with O–C cleavage and neutral losses of propylene molecules (42 u), daughter ions of m / z 139 and m / z 97 are formed, as presented in Table . By additional collision-induced dissociation inside the ion trap, ions with m / z 79 and m / z 47 could be generated for further identification as well. − …”