Spectral analysis of complex gas mixtures by isotope dilution. Part I. Determination of hydrogen

The spectral dependence of the relative quantum yield of certain metals (Cu, Ag, Au, Al, In, Sn, Ti, Fe, Ni, Zr, Nb, Mo, Ta, W, Pt) and nonmetals (ThO₂, ZrO₂, HfO₂, Sc₂O₃, Nb₂O₅, LiE, MgF₂, SrF₂, CsI, ZnS, SbS, BeO) has been investigated in the 95-20 nm region of the spectrum.     

Position-specific carbon isotope analysis of trichloroacetic acid by gas chromatography/isotope ratio mass spectrometry

Trichloroacetic acid (TCAA) is an important environmental contaminant present in soils, water and plants. A method for determining the carbon isotope signature of the trichloromethyl position in TCAA using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) was developed and tested with TCAA from different origins. Position-specific isotope analysis (PSIA) can provide direct information on the kinetic isotope effect for isotope substitution at a specific position in the molecule and/or help to distinguish different sources of a compound. The method is based on the degradation of TCAA into chloroform (CF) and CO? by thermal decarboxylation. Since thermal decarboxylation is associated with strong carbon isotope fractionation (ε = -34.6 ± 0.2‰) the reaction conditions were optimized to ensure full conversion. The combined isotope ratio of CF and CO? at the end of the reaction corresponded well to the isotope ratio of TCAA, confirming the reliability of the method. A method quantification limit (MQL) for TCAA of 18.6 μg/L was determined. Samples of TCAA produced by enzymatic and non-enzymatic chlorination of natural organic matter (NOM) and some industrially produced TCAA were used as exemplary sources. Significant different PSIA isotope ratios were observed between industrial TCAA and TCAA samples produced by chlorination of NOM. This highlights the potential of the method to study the origin and the fate of TCAA in the environment.     

Spectral characteristics of a barrier discharge in cadmium dihalide vapor-inert gas mixtures

Spectral characteristics of a barrier-discharge plasma produced in atmospheric-pressure mixtures of cadmium diiodide and cadmium dibromide vapors with neon, krypton, and xenon at a repetition rate of sine voltage pulses up to 130 kHz are studied. The emission from the discharge is studied within the spectral range 200–900 nm with a resolution of 0.05 nm. Emission of exciplex molecules CdI(B → X) and CdBr(C, B → X), and cadmium and inert gas atoms is revealed, as well as emission of exciplex molecules XeI(B → X, A) and XeBr(B → X, A) in xenon-containing mixtures. The emission of xenon halides prevails in the spectra at a mixture temperature up to 200°C. With a further temperature increase, the emission of cadmium halides becomes dominating. It is ascertained that the most intense emissions of CdI(B → X) and CdI₂/CdBr₂/Xe/Kr and CdBr(B → X) molecules are observed, respectively, in CdI₂/CdBr₂/Xe/Kr and CdI₂/CdBr₂/Xe mixtures. The cadmium dihalide-inert gas mixtures are of interest for the use as a radiating gas in a multiwavelength and broadband excilamp emitting in the UV and visible spectral ranges.     

Spectral separation of gaseous fluorocarbon mixtures and measurement of diffusion constants by F gas phase DOSY NMR

Diffusion-ordered (DOSY) NMR techniques have for the first time been applied to the spectral separation of mixtures of fluorinated gases by diffusion rates. A mixture of linear perfluoroalkanes from methane to hexane was readily separated at 25 °C in an ordinary experimental setup with standard DOSY pulse sequences. Partial separation of variously fluorinated ethanes was also achieved. The constants of self-diffusion of a set of pure perfluoroalkanes were obtained at pressures from 0.25 to 1.34 atm and temperatures from 20 to 122 °C. Under all conditions there was agreement within 20% of experimental self-diffusion constant D and values calculated by the semiempirical Fuller method.     

QEPAS for chemical analysis of multi-component gas mixtures

A gas sensor based on quartz-enhanced photoacoustic spectroscopy and using near-infrared, fiber-coupled diode lasers as an excitation source was developed for chemical analysis of gas mixtures containing H₂S, CO₂, and CH₄ at concentrations from 0 to 100%. Analysis of physical phenomena affecting the sensor operation is performed, the sensor performance is evaluated, and simple algorithms are developed to derive concentrations of the gases from detected electrical signals.     

Determination and analysis of opiates in complex mixtures by surface-ionization mass spectrometry

The results of studies of the analytical opportunities of surface-ionization mass spectrometry (SIMS) for high-sensitivity and selective detection and analysis of opiate mixtures—natural opium, crude heroin, and narcotic analgesic omnopon—are presented. The experiments were carried out using an MX-1320 chemical mass spectrometer modernized for studying surface ionization (SI). It was ascertained that the opiate mixtures are ionized by highly efficient surface ionization. The bands of M⁺ (for papaverine), (M-H)⁺, (M-H-2nH)⁺, (M-R)⁺, and (M-R-2nH)⁺ ions, where M is a molecule, H is a hydrogen atom, R is a radical, are observed in the mass spectra; they are the sum of the SI mass spectra of components of the mixtures. The series of bands of ions with m/z of 144 and 146 that is characteristic of SI-morphinelike molecules is the main one in the mass spectrum of crude heroin, while for omnopon and natural opium this series is the main at low temperatures of a thermionic emitter (up to ∼900 K). At high temperatures of the thermionic emitter, the band series with m/z of 218 and 220 is the main series. Studies of natural opium, crude heroin, and omnopon have shown that the SIMS method allows analyzing mixtures without preliminary chromatographic separation thereof. The study also contains the results of comparative analyses of opiate mixtures by SIMS and chromate- and mass spectrometry (HP-6890) with electronic ionization.     

A homodecoupled diffusion experiment for the analysis of complex mixtures by NMR

Diffusion ordered spectroscopy (DOSY) relies on differences in translation diffusion as a means to separate components in a solution mixture. However, the analysis of spectra of mixtures can be problematic because spectral overlap. It is the aim of this article to propose a pulse sequence and processing method that leads to a complete 2D homodecoupled-DOSY experiment. This experiment offers several advantages that could extend the range of applications to more complex mixtures by achieving important improvements in both signal dispersion and sensitivity.     

High-temperature emissivities of complex gas mixtures in the 4.8 μ region

Emissivities of dilute C-H-O and C-H-O-N gas mixtures have been measured in the 4.8 μ region behind reflected shock waves (2399≤T, °K≤3093) under near-equilibrium and equilibrium conditions. The emission may be satisfactorily accounted for in terms of emission from equilibrium mixtures of CO₂, CO and H₂O.     

Memory effects in combining isotope ratio monitoring with isotope dilution mass spectrometry

Combining isotope ratio monitoring with isotope dilution techniques provides very accurate results in the quantitative analysis of volatile organic chemical compounds by gas chromatography/mass spectrometry (GC/MS). However, this method requires that spikes highly enriched in (13)C be used. This may lead to memory effects which will be investigated in more detail. They occur when the component of the mixture to be investigated exhibits an isotope ratio which is different from that of the component eluted earlier from the column during the chromatographic separation process. A residue of this component, which is shown in the gas chromatogram as tailing, falsifies the result of the isotope ratio measurement. This also leads to false amount-of-substance measurement results. Memory effects can be avoided by using spikes of low (13)C content, by adjusting the composition of the reference solution to that of the sample, or by ensuring effective sample preparation, thus separating disturbing mixture components prior to the measurement. Copyright 1999 John Wiley & Sons, Ltd.