Field Induced Fragmentation (Fif) Spectra of Oxygen Containing Volatile Organic Compounds with Reactive Stage Tandem Ion Mobility Spectrometry and Functional Group Classification by Neural Network Analysis.

Mobility isolated spectra were obtained for protonated monomers of 42 volatile oxygen containing organic compounds at ambient pressure using a tandem ion mobility spectrometer with a reactive stage between drift regions. Fragment ions of protonated monomers of alcohols, acetates, aldehydes, ketones, and ethers were produced in the reactive stage using a 3.3 MHz symmetrical sinusoidal waveform with an amplitude of 1.4 kV and mobility analyzed in a 19 mm long drift region. The resultant field induced fragmentation (FIF) spectra included residual intensities for protonated monomers and fragment ions with characteristic drift times and peak intensities, associated with ion mass and chemical class. High efficiency of fragmentation was observed with single bond cleavage of alcohols and in six-member ring rearrangements of acetates. Fragmentation was not observed, or seen weakly, with aldehydes, ethers, and ketones due to their strained four-member ring transition states. Neural networks were trained to categorize spectra by chemical class and tested with FIF spectra of both familiar and unfamiliar compounds. Rates of categorization were class dependent with best performance for alcohols and acetates, moderate performance for ketones, and worst performance for ethers and aldehydes. Trends in the rates of categorization within a chemical family can be understood as steric influences on the energy of activation for ion fragmentation. Electric fields greater than 129 Td or new designs of reactive stages with improved efficiency of fragmentation will be needed to extend the practice of reactive stage tandem IMS to an expanded selection of volatile organic compounds.

Dissociation Enthalpies of Chloride Adducts of Nitrate and Nitrite Explosives Determined by Ion Mobility Spectrometry.

The kinetics for thermal dissociations of the chloride adducts of the nitrate explosives 1,3-dinitroglycerin (1,3-NG), 1,2-dinitroglycerin (1,2-NG), the nitrite explosive 3,4-dinitrotoluene (3,4-DNT), and the explosive taggant 2,3-dimethyl-2,3-dinitrobutane (DMNB) have been studied by atmospheric pressure ion mobility spectrometry. Both 1,3-NG·Cl(-) and1,2-NG·Cl(-) decompose in a gas-phase SN2 reaction in which Cl(-) displaces NO3(-) while 3,4-DNT·Cl(-) and DMNB·Cl(-) decompose by loss of Cl(-). The determined activation energy (kJ mol(-1)) and pre-exponential factor (s(-1)) values for the dissociations respectively are 1,3-NG·Cl(-), 86 ± 2 and 2.2 × 10(12); 1,2-NG·Cl(-), 97 ± 2 and 3.5 × 10(12); 3,4-DNT·Cl(-), 81 ± 2 and 4.8 × 10(13); and DMNB·Cl(-), 68 ± 2 and 9.7 × 10(11). Calculations by density functional theory show the structures of the nitrate ester adducts involve three hydrogen bonds: one from the hydroxyl group and the other two from the two nitrated carbons. The relative Cl(-) dissociation energies of the nitrates together with the previously reported smaller value for glycerol trinitrate and the calculated highest value for glycerol 1-mononitrate are explicable in terms of the number of hydroxyl hydrogen bond participants. The theoretical enthalpy changes for the nitrate ester displacement reactions are in agreement with those derived from the experimental activation energies but considerably higher for the nitro compounds.

Decomposition kinetics of nitroglycerine·Cl(-)(g) in air at ambient pressure with a tandem ion mobility spectrometer.

A dual-shutter ion mobility spectrometer operating at atmospheric pressure and interfaced to a gas chromatograph for sample introduction has been used to study the reaction of Cl(-) with explosives. Of particular interest was an investigation of the formation of NO3(-) from the reaction of the Cl(-) with nitroglycerin (NG). The adduct NG·Cl(-) together with NO3(-) and NG·NO3(-) compose the mobility spectrum. Over the temperature range 111 to 122 °C, NG·NO3(-) is stable, but NG·Cl(-) decomposes to NO3(-) and 1,2-dinitro-3-chloropropane (DNClP). The activation energy and pre-exponential factor for this first order decomposition are 80 ± 3 kJ mol(-1) and 1.3 × 10(12) s(-1), respectively. Ab initio calculation shows that the reaction is a substitution reaction occurring over a two well potential energy profile with stable ion-molecule complexes NG·Cl(-) and DNClP·NO3(-).

Dissociation of proton bound ketone dimers in asymmetric electric fields with differential mobility spectrometry and in uniform electric fields with linear ion mobility spectrometry.

The kinetics for the decomposition of the symmetrical proton-bound dimers of a series of 2-ketones (M) from acetone to 2-nonanone have been determined at ambient pressure by linear ion mobility spectrometry (IMS) and by differential mobility spectrometry (DMS). Decomposition, M2H(+) →MH(+) + M, in the IMS instrument, observed under thermal conditions over the temperature range 147 to 172 °C, yielded almost identical Arrhenius parameters Ea = 122 kJ mol(-1) and ln A = 38.8 for the dimers of 2-pentanone, 2-heptanone, and 2-nonanone. Ion decomposition in the DMS instrument was due to a combination of thermal and electric field energies at an effective ion internal temperature whose value was estimated by reference to the IMS kinetic parameters. Decomposition was observed with radio frequency (RF) fields with maximum intensities in the range 10 kV cm(-1) to 30 kV cm(-1) and gas temperatures from 30 to 110 °C, which yielded effective temperatures that were higher than the gas temperature by 260° at 30 °C and 100° at 110 °C. There was a mass dependence of the field for the onset of decomposition: the higher the ion mass, the higher the required field at a given gas temperature, which is ascribed to the associated increasing heat capacity with the increasing carbon number, but similar, internal vibrations and rotations.

A study of the performance of an ion shutter for drift tubes in atmospheric pressure ion mobility spectrometry: computer models and experimental findings.

Ion mobility spectra are initiated when ions, derived from a sample, are pulsed or injected through ion shutters into a drift region. The effect on signal intensity from electric fields arising from the shutter grids (E(s)) and a superimposed electric field of the drift tube (E(d)) was determined experimentally and simulated computationally for ion motion at ambient pressure. The combination of these two fields influenced shutter performance in three ways: (1) intensity of an ion peak was suppressed by increased current in the baseline due to continuous leakage of ions into the drift region from insufficient E(s) to block ion motion when needed, at a given value of E(d); (2) the ion shutter provided maximum peak intensity with some optimal ratio of E(s)/E(d) when ions were fully blocked except using the injection time; (c) the signal intensity was reduced when the blocking voltage of the ion shutter exceeded this optimal E(s)/E(d) ratio from ion depletion at the shutter grids. The optimal ratio from the computer models was equal to 1.50, whereas a value of 2.50 was obtained from the experimental findings. This difference was attributed to nonideal geometry with the grids of the shutter and the conducting elements in the drift tube establishing both E(s) and E(d). As both the experimental and modeling results demonstrated, a mobility dependence of ion yield from the ionization source was found to cause a mobility dependent ion signal at the collector electrode.

Miniature differential mobility spectrometry using atmospheric pressure photoionization.

Positive and negative ion spectra have been obtained with a miniature differential mobility spectrometer equipped with a photoionization source operating at atmospheric pressure. With benzene as a dopant, providing C6H6+ as reactant ion, protonated molecular ions and proton-bound dimer ions were obtained with dimethyl methylphosphonate and butanone. The spectra obtained from gas chromatographic injections of aromatic hydrocarbons, benzene, toluene, and the xylenes, produced the molecular ions when the moisture level was very low, but at a high level the hydrated proton was also present. Possible mechanisms for the formation of protonated products are discussed. Negative ions were produced from electron capture by sulfur hexafluoride using benzene or acetone as dopant. Photoionization of nitrogen dioxide led to the formation of the nitrate ion whose yield was a nonlinear function of concentration. The use of a suitable dopant enhanced ion formation by up to 2 orders of magnitude, and limits of detection in both the positive and negative modes were all at the sub ppm(v) level. The study makes a strong case for the use of a photoionization source as an alternative to the radioactive 63Ni source.