Sensitivity and selectivity of switchable reagent ion soft chemical ionization mass spectrometry for the detection of picric acid
Research output: Contribution to journal › Article › peer-review
We have investigated the reactions of NO+, H3O+, O2+, and Kr+ with picric acid (2,4,6 trinitrophenol, C6H3N3O7, PiA) using a time-of-flight mass spectrometer with a switchable reagent ion source. NO+ forms a simple adduct ion PiA·NO+, while H3O+ reacts with PiA via nondissociative proton transfer to form PiAH+. In contrast, both O2+ and Kr+ react with PiA by nondissociative charge transfer to produce PiA+. For Kr+, we also observe dissociation of PiA, producing NO2+ with a branching percentage of approximately 40%. For the reagent ions H3O+ and O2+ (and operating the drift tube with normal laboratory air), we find that the intensities of the PiAH+ and PiA+ ions both exhibit a peak at a given drift-tube voltage (which is humidity dependent). This unusual behavior implies a peak in the detection sensitivity of PiA as a function of the drift-tube voltage (and hence E/N). Aided by electronic-structure calculations and our previous studies of trinitrotoluene and trinitrobenzene, we provide a possible explanation for the observed peak in the detection sensitivity of PiA.
|Number of pages||8|
|Journal||The Journal of Physical Chemistry A|
|Early online date||17 Mar 2014|
|Publication status||Published - 18 Sep 2014|