Quantitative response to nitrite from field-induced decomposition of the chloride adduct of RDX by reactive stage tandem ion mobility spectrometry.

An additional dimension of selectivity for the determination of RDX by ion mobility spectrometry (IMS) was introduced through field-induced decomposition of RDX·Cl- to NO2- on a spectral baseline free of interfering peaks. In this variant of reactive stage tandem IMS, the explosive ion is decomposed selectively in the presence of an interferent and from significantly convolved peaks which were mobility isolated within a narrow range of drift times using dual ion shutters. Field-induced decomposition at 170 °C and field strength of 112 Td (∼16 kV cm-1) provided 15% decomposition yield and RDX, amid interferent, was detected decisively even when peaks differed in reduced mobility coefficients (Ko) by only 0.02 cm2 V-1 s-1. A nitrite peak with S/N of 8.5 was observed with vapour concentrations of 54 ppb for RDX and 329 ppb for Interferent A in the ionization volume corresponding to 2 ng of RDX and 100 ng of Interferent A deposited on sample traps in the thermal desorption inlet. Findings on quantitative response suggest the presence of excessive amounts of interferent caused ionization suppression of RDX. Still, RDX was determined quantitatively using sequential processing of ions by mobility isolation, selective field induced decomposition, and mobility analysis in a second drift region.

Reactive Tandem Ion Mobility Spectrometry with Electric Field Fragmentation of Alcohols at Ambient Pressure.

A tandem ion mobility spectrometer at ambient pressure with a reactive stage produced fragment ions by water elimination from protonated monomers of alcohols with carbon numbers three to nine. Protonated monomers of individual alcohols were mobility isolated in a first drift region and were fragmented to carbocations at 64 to 128 Td and 45 to 89°C. Precursor and fragment ions were mobility characterized in a second drift region. Enthalpies for fragmentation of ROH2+ to primary carbocations were calculated as 76 to 97 kJ/mol and enthalpies for subsequent charge migration to 2° carbocations were -49 to -58 kJ/mol. Plots of drift times for pairs of protonated monomer and fragment ions from alcohols, esters, alkanes, and aldehydes produced distinctive trend lines attributed to fragmentation paths characteristic of chemical class. Specific combinations of drift times for fragments and precursor ions provide additional chemical information for spectral interpretation in ion mobility spectrometry.

Tandem ion mobility spectrometry at ambient pressure and field decomposition of mobility selected ions of explosives and interferences.

A tandem ion mobility spectrometer at ambient pressure included a thermal desorption inlet, two drift regions, dual ion shutters, and a wire grid assembly in the second drift region. An ion swarm could be mobility isolated in the first drift region using synchronized dual ion shutters and decomposed in a wire grid assembly using electric fields of 1.80 × 104 V cm-1 (118 Td) from a 1.8 MHz sinusoidal waveform. Mobility selected ions that underwent field induced decomposition were NO3-, from PETN·Cl- and NG·Cl-, and NO2- from RDX·Cl-. The extent of decomposition ranged from 60 to 90%, depending on gas temperature, field strength, and ion identity, introducing additional controls to improve selectivity in trace determination of explosives. Ion transmission through the wire grid assembly ranged from 80 to >95% with losses increasing for increased field strength. Studies with pairs of explosives and interfering substances demonstrated decisive detection of explosives and portend reduced rates of false positive using tandem ion mobility spectrometers with a reactive stage.