On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research

Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non-equilibrium plasmas.

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Plasma-liquid interactions: A review and roadmap

Proton-transfer-reaction mass spectrometry (PTR-MS) allows real-time measurements of volatile organic compounds (VOCs) in air with a high sensitivity and a fast time response. The use of PTR-MS in atmospheric research has expanded rapidly in recent years, and much has been learned about the instrument response and specificity of the technique in the analysis of air from different regions of the atmosphere. This paper aims to review the progress that has been made. The theory of operation is described and allows the response of the instrument to be described for different operating conditions. More accurate determinations of the instrument response involve calibrations using standard mixtures, and some results are shown. Much has been learned about the specificity of PTR-MS from inter-comparison studies as well the coupling of PTR-MS with a gas chromatographic interface. The literature on this issue is reviewed and summarized for many VOCs of atmospheric interest. Some highlights of airborne measurements by PTR-MS are presented, including the results obtained in fresh and aged forest-fire and urban plumes. Finally, the recent work that is focused on improving the technique is discussed.

Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry.

Transport Properties of Gaseous Ions over a Wide Energy Range

Selected ion flow tube mass spectrometry (SIFT-MS) is a new analytical technique for the real-time quantification of several trace gases simultaneously in air and breath. It relies on chemical ionization of the trace gas molecules in air/breath samples introduced into helium carrier gas using H(3)O(+), NO(+), and O(2) (+.) precursor ions. Reactions between the precursor ions and trace gas molecules proceed for an accurately defined time, the precursor and product ions being detected and counted by a downstream mass spectrometer, thus effecting quantification. Absolute concentrations of trace gases in single breath exhalation can be determined by SIFT-MS down to ppb levels, obviating sample collection and calibration. Illustrative examples of SIFT-MS studies include (i) analysis of gases from combustion engines, animals and their waste, and food; (ii) breath and urinary headspace studies of metabolites, ethanol metabolism, elevated acetone during ovulation, and exogenous compounds; and (iii) urinary infection and the presence of tumors, the influence of dialysis on breath ammonia, acetone, and isoprene, and acetaldehyde released by cancer cells in vitro. Flowing afterglow mass spectrometry (FA-MS) is briefly described, which allows on-line quantification of deuterium in breath water vapor.

Selected ion flow tube mass spectrometry (SIFT-MS) for on-line trace gas analysis

Tables of transport collision integrals for (n, 6, 4) ion-neutral potentials

New measurements of the mobility of Li+ ions in He gas at 300°K are reported for a wide range of E/N, the ratio of the electric field strength to the gas number density. These data are used in conjunction with kinetic theory to test various Li+–He interaction potentials over a wide range of separation distance. It is shown that the ab initio potential of Hariharan and Staemmler gives mobility values in excellent agreement with experiment at low and moderate E/N, but that significant discrepancies exist at high E/N. The mobility data are also directly inverted to give the Li+–He interaction potential. This directly determined potential is in excellent agreement with the ab initio at intermediate and long range, but differs significantly in the short‐range region. In the latter region, however, it is in agreement with the potential obtained by analysis of beam‐scattering experiments.

The Li+–He interaction potential

Gaseous ion mobilities are mainly dependent on ion–neutral collision energies in the range 0.03–1 eV and, using a recently developed kinetic theory method, can be directly related to ion–neutral interaction potentials. In this paper, experimental mobilities are used to test recent theoretical calculations based on the electron–gas model of the interaction potentials for the twelve combinations of Li+, Na+, K+, and Rb+ with He, Ne, and Ar. The model potentials are quite good, but some systematic discrepancies with experimental mobilities exist. These discrepancies are analyzed in terms of the relation between the mobility and the ion–atom potential.

Tests of alkali ion‐inert gas interaction potentials by gaseous ion mobility experiments

The mobility of Li+ ions in He has been measured at a gas temperature of 300 °K over a wide range of E/N, where E is the electric field intensity and N is the gas number density. A new theory of ion mobility is used to calculate from these data the standard Ω integral ?(1,1) of kinetic theory for Li+ in He over a range of effective gas temperature extending from 300 to 28 700 °K. The ab initio quantum mechanical interaction potential for the Li+–He system computed by Catlow et al. is also used to calculate ?(1,1) as a function of Teff. A comparison of the two sets of data serves as a test of the Catlow potential. The test is extended to still higher effective temperatures (up to 60 000 °K) by comparison with values of ?(1,1) computed from the short‐range repulsive potential derived from Li+ beam scattering experiments in helium. The Catlow potential reproduces the general features of the dependence of the ’’experimental’’ Ω integral on Teff over the entire range of the test. However, significant discrepan...

L. A. Viehland

Papers

Transport Properties of Gaseous Ions over a Wide Energy Range

Tables of transport collision integrals for (n, 6, 4) ion-neutral potentials

The Li+–He interaction potential

Tests of alkali ion‐inert gas interaction potentials by gaseous ion mobility experiments

Test of the Li+–He interaction potential