Gas Analysis by Electron Ionization Combined with Chemical Ionization in a Compact FTICR Mass Spectrometer.

In this Article, a compact Fourier transform ion cyclotron resonance (FTICR) mass spectrometer based on a permanent magnet is presented. This instrument has been developed for real-time analysis of gas emissions. The instrument is well-suited to industrial applications or analysis of toxic and complex samples where the concentrations can vary rapidly on a wide range. The novelty of this instrument is the ability to use either electron ionization (EI) or chemical ionization (CI) individually or both of them alternatively. Also in CI mode, different precursor ions can be used alternatively. Volatile organic compounds (VOCs) from the ppb level to very high concentrations (% level) can be detected by CI or EI. The magnet is composed of three Halbach arrays, and the nominal field achieved is 1.5 T. The ICR cell is a 3 cm side length cubic cell. The mass range is 12-200 u with a broad band detection. The mass accuracy of 0.005 u and the resolving power allow the separation of isobaric ions such as C3H8+ and CO2+. Gas introduction via controlled gas pulses, electron ionization, ion-molecule reactions, ion selection, and detection are all performed in the ICR cell. The potential of the instrument will be illustrated by an analysis of a gas mixture containing trace components at ppm level (VOCs) and components in the 0.5-100% range (N2, alkanes, and CO2).

Detailed characterization of 2-heptanone conversion by dielectric barrier discharge in N(2) and N(2)/O(2) mixtures.

The products of 2-heptanone conversion by dielectric barrier discharge plasma are analyzed under different conditions: alternating current (ac) or pulsed mode of excitation, variable energy, variable composition of the carrier gas. The efficiency of the conversion is higher using a pulse excitation mode than an ac mode. With a small oxygen percentage (about 2-3%) added to nitrogen, 2-heptanone is about 30% more efficiently removed than in pure nitrogen, while the 2-heptanone removal decreases with an oxygen percentage higher than 3%. A new analysis method, based on chemical ionization mass spectrometry, is used for volatile organic compound detection along with chromatography. Several products issued from 2-heptanone conversion with ac excitation are identified in nitrogen and in air, and a chemical scheme is proposed to explain their formation and their treatment by the discharge. It appears that byproducts are issued not only from oxidation reactions, but also from C-C bond cleavage by collisions with electrons or nitrogen excited states.

Infrared spectra of homogeneous and heterogeneous proton-bound dimers in the gas phase.

Infrared multiphoton dissociation spectra of three homogeneous and two heterogeneous proton-bound dimers were recorded in the gas phase. Comparison of the experimental infrared spectra recorded in the fingerprint region of the proton-bound dimers with spectra predicted by electronic structure calculations shows that all modes which are observed contain motion of the proton oscillating between the two monomers. The O-H-O asymmetric stretch for the homogeneous dimers is shown to occur at around 800 cm-1. As expected, the O-H-O asymmetric stretching modes for the heterogeneous proton-bound dimers are observed to shift to significantly higher energy with respect to those for the homogeneous proton-bound dimers due to the asymmetry of the O-H-O moeity. This shift is shown to be predictable from the difference in proton affinities between the two monomers. Density functional predictions of the infrared spectra based on the harmonic oscillator model are demonstrated to predict the observed spectra of the homogeneous proton-bound dimers with reasonable accuracy. Calculations of the structure and infrared spectrum of protonated diglyme at the B3LYP/6-31+G** level and basis also agree well with an infrared spectrum recorded previously. For both heterogeneous proton-bound dimers, however, the predicted spectra are blue-shifted with respect to experiment.

Infrared multiphoton dissociation spectroscopy of gas-phase mass-selected hydrocarbon-Fe+ complexes.

Infrared spectra in the mid-infrared region (800-1600 cm(-1)) of highly unsaturated Fe(+)-hydrocarbon complexes isolated in the gas phase are presented. These organometallic complexes were selectively prepared by ion-molecule reactions in a Fourier transform ion cycloton mass spectrometer (FTICR-MS). The infrared multiphoton dissociation (IRMPD) technique has been employed using the free electron laser facility CLIO (Orsay, France) to record the infrared spectra of the mass selected complexes. The experimental IRMPD spectra present the main features of the corresponding IR absorption spectra calculated ab initio. As predicted by these calculations, the experimental spectra of three selectively prepared isomers of Fe+(butene) present differences in the 800-1100 cm(-1) range. On the basis of the comparison with calculated IR spectra, the IRMPD spectrum of Fe(butadiene)(+) suggests that the ligand presents the s-trans isomeric form. This study further confirms the potentialities of IRMPD spectroscopy for the structural characterization of organometallic ionic highly reactive intermediates in the gas phase. In conjunction with soft ionization techniques such as electrospray, this opens the door to the gas-phase characterization of reactive intermediates associated with condensed phase catalysts.