Species mass spectrometry

Few of the naturally occurring elements have significant amounts of radioactive isotopes, but there are many artificially produced radioactive species. Mass spectrometry can measure both radioactive and nonradioactive isotope ratios, but there are health and safety issues for the radioactive ones. However, modem isotope instmments are becoming so sensitive that only very small amounts of sample are needed. Where radioactive isotopes are a serious issue, the radioactive hazards can be minimized by using special inlet systems and ion pumps in place of rotary pumps for maintaining a vacuum. For example, mass spectrometry is now used in the analysis of Pu/ Pu ratios. 

The species produced through ionization of an electron from a ir-orbital (such as from a C-H or a C-C bond of an alkane in mass spectrometry) cannot be represented at all by a connection table, yet the RAMSES notation can account for it as shown in Figure 2-59. 

Molecular ion (Section 13 22) In mass spectrometry the species formed by loss of an electron from a molecule Molecular orbital theory (Section 2 4) Theory of chemical bonding in which electrons are assumed to occupy orbitals in molecules much as they occupy orbitals in atoms The molecular orbitals are descnbed as combinations of the or bitals of all of the atoms that make up the molecule Molecularity (Section 4 8) The number of species that react to gether in the same elementary step of a reaction mechanism... 

Following the movement of airborne pollutants requires a natural or artificial tracer (a species specific to the source of the airborne pollutants) that can be experimentally measured at sites distant from the source. Limitations placed on the tracer, therefore, governed the design of the experimental procedure. These limitations included cost, the need to detect small quantities of the tracer, and the absence of the tracer from other natural sources. In addition, aerosols are emitted from high-temperature combustion sources that produce an abundance of very reactive species. The tracer, therefore, had to be both thermally and chemically stable. On the basis of these criteria, rare earth isotopes, such as those of Nd, were selected as tracers. The choice of tracer, in turn, dictated the analytical method (thermal ionization mass spectrometry, or TIMS) for measuring the isotopic abundances of... 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

Analytical Approaches. Different analytical techniques have been appHed to each fraction to determine its molecular composition. As the molecular weight increases, complexity increasingly shifts the level of analytical detail from quantification of most individual species in the naphtha to average molecular descriptions in the vacuum residuum. For the naphtha, classical techniques allow the isolation and identification of individual compounds by physical properties. Gas chromatographic (gc) resolution allows almost every compound having less than eight carbon atoms to be measured separately. The combination of gc with mass spectrometry (gc/ms) can be used for quantitation purposes when compounds are not well-resolved by gc. 

Tandem mass spectrometry or ms/ms was first introduced in the 1970s and gained rapid acceptance in the analytical community. The technique has been used for stmcture elucidation of unknowns (26) and has the abiUty to provide sensitive and selective analysis of complex mixtures with minimal sample clean-up (27). Developments in the mid-1980s advancing the popularity of ms/ms included the availabiUty of powerhil data systems capable of controlling the ms/ms experiment and the viabiUty of soft ionisation techniques which essentially yield only molecular ion species. 

Hypochlorous acid and chlorine monoxide coexist in the vapor phase (78—81). Vapor pressure measurements of aqueous HOCl solutions show that HOCl is the main chlorine species in the vapor phase over <1% solutions (82), whereas at higher concentrations, CI2O becomes dominant (83). The equihbtium constant at 25°C for the gas-phase reaction, determined by ir and uv spectrophotometry and mass spectrometry, is ca 0.08 (9,66,67,69). The forward reaction is much slower than the reverse reaction. 

Hypochlorous acid can be distinguished from other chlorine species by amperometry using a membrane electrode (135). Spectrophotometry can also be used to measure HOCl via its absorbance maximum at 235 nm. Gaseous mixtures of CI2, CI2O, HOCl can be analyzed by mass spectrometry. 

High resolution mass spectrometry (qv) has been used with extracts of a series of coals to indicate the association of different heteroatoms (27). Various types of chromatography (qv) have also been used to identify the smaller species that can be extracted from coal. 

Mass Spectrometer. The mass spectrometer is the principal analytical tool of direct process control for the estimation of tritium. Gas samples are taken from several process points and analy2ed rapidly and continually to ensure proper operation of the system. Mass spectrometry is particularly useful in the detection of diatomic hydrogen species such as HD, HT, and DT. Mass spectrometric detection of helium-3 formed by radioactive decay of tritium is still another way to detect low levels of tritium (65). Accelerator mass spectroscopy (ams) has also been used for the detection of tritium and carbon-14 at extremely low levels. The principal appHcation of ams as of this writing has been in archeology and the geosciences, but this technique is expected to faciUtate the use of tritium in biomedical research, various clinical appHcations, and in environmental investigations (66). 

In looking for the mechanism, many intermediates are assumed. Some of these are stable molecules in pure form but very active in reacting systems. Other intermediates are in very low concentration and can be identified only by special analytical methods, like mass spectrometry (the atomic species of hydrogen and halogens, for example). These are at times referred to as active centers. Others are in transition states that the reacting cheimicals form with atoms or radicals these rarely can be isolated. In heterogeneous catalytic reaction, the absorbed reactant can... 

Static Secondary Ion Mass Spectrometry (SIMS) involves the bombardment of a sample with an energetic (typically 1-10 keV) beam of particles, which may be either ions or neutrals. As a result of the interaction of these primary particles with the sample, species are ejected that have become ionized. These ejected species, known as secondary ions, are the analytical signal in SIMS. 

In Laser Ionization Mass Spectrometry (LIMS, also LAMMA, LAMMS, and LIMA), a vacuum-compatible solid sample is irradiated with short pulses ("10 ns) of ultraviolet laser light. The laser pulse vaporizes a microvolume of material, and a fraction of the vaporized species are ionized and accelerated into a time-of-flight mass spectrometer which measures the signal intensity of the mass-separated ions. The instrument acquires a complete mass spectrum, typically covering the range 0— 250 atomic mass units (amu), with each laser pulse. A survey analysis of the material is performed in this way. The relative intensities of the signals can be converted to concentrations with the use of appropriate standards, and quantitative or semi-quantitative analyses are possible with the use of such standards. 

Molecular ion (Section 13.22) In mass spectrometry, the species formed by loss of an electron from a molecule. 

In 1913, J. J. Thomson4 demonstrated that neon consists of different atomic species (isotopes) having atomic weights of 20 and 22 g/mole. Thomson is considered to be the father of mass spectrometry. His work rests on Goldstein s (1886) discovery of positively charged entities and Wein s (1898) demonstration that positively charged ions can be deflected by electrical and magnetic fields. 

His researches and those of his pupils led to his formulation in the twenties of the concept of active catalytic centers and the heterogeneity of catalytic and adsorptive surfaces. His catalytic studies were supplemented by researches carried out simultaneously on kinetics of homogeneous gas reactions and photochemistry. The thirties saw Hugh Taylor utilizing more and more of the techniques developed by physicists. Thermal conductivity for ortho-para hydrogen analysis resulted in his use of these species for surface characterization. The discovery of deuterium prompted him to set up production of this isotope by electrolysis on a large scale of several cubic centimeters. This gave him and others a supply of this valuable tracer for catalytic studies. For analysis he invoked not only thermal conductivity, but infrared spectroscopy and mass spectrometry. To ex-... 

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