Gas phase ionisation

The mass spectra of mixtures are often too complex to be interpreted unambiguously, thus favouring the separation of the components of mixtures before examination by mass spectrometry. Nevertheless, direct polymer/additive mixture analysis has been reported [22,23], which is greatly aided by tandem MS. Coupling of mass spectrometry and a flowing liquid stream involves vaporisation and solvent stripping before introduction of the solute into an ion source for gas-phase ionisation (Section 1.33.2). Widespread LC-MS interfaces are thermospray (TSP), continuous-flow fast atom bombardment (CF-FAB), electrospray (ESP), etc. Also, supercritical fluids have been linked to mass spectrometry (SFE-MS, SFC-MS). A mass spectrometer may have more than one inlet (total inlet systems). 

Typical gas phase ionisation methods (vaporisation followed by ionisation) are El, Cl, FI, MPI desorption/ionisation methods for nonvolatile samples (ions formed in the condensed phase) are FD, PD, SIMS, FAB, DCI, TSP, LD-SIMS, MALD, ESP/ISP. 

Principles and Characteristics In metastable atom bombardment (MAB), a metastable atom beam, generated by a gun external to the ion volume, is used to bombard the sample. MAB, based on Penning ionisation, offers unique features for gas-phase ionisation. The energy available for ionisation and fragmentation is discrete (excitation energy of the atom, from 8 to 20 eV),... 

Ionisation in an API source can take place in a variety of ways depending on the type of applications, namely by gas-phase ionisation, liquid- and plasma-based ionisation. At present, there are three major application areas of API-MS air or gas analysis (industrial emissions), on-line LC-MS (largest commercial application), and ICP-MS. A wide variety of sample introduction devices are available for gas analysis by API-MS. For use in ICP-MS, ions are sampled directly from the inductively... 

Gas-phase ionisation-atmospheric pressure chemical ionisation... 

Most dyes, including sulfonated azo dyes, are nonvolatile or thermally unstable, and therefore are not amenable to GC or gas-phase ionisation processes. Therefore, GC-MS techniques cannot be used. GC-MS and TGA were applied for the identification of acrylated polyurethanes in coatings on optical fibres [295]. Although GC-MS is not suited for the analysis of polymers, the technique can be used for the study of the products of pyrolysis in air, e.g. related to smoke behaviour of CPVC/ABS and PVC/ABS blends [263],... 

The mobile phase in LC-MS may play several roles active carrier (to be removed prior to MS), transfer medium (for nonvolatile and/or thermally labile analytes from the liquid to the gas state), or essential constituent (analyte ionisation). As LC is often selected for the separation of involatile and thermally labile samples, ionisation methods different from those predominantly used in GC-MS are required. Only a few of the ionisation methods originally developed in MS, notably El and Cl, have found application in LC-MS, whereas other methods have been modified (e.g. FAB, PI) or remained incompatible (e.g. FD). Other ionisation methods (TSP, ESI, APCI, SSI) have even emerged in close relationship to LC-MS interfacing. With these methods, ion formation is achieved within the LC-MS interface, i.e. during the liquid- to gas-phase transition process. LC-MS ionisation processes involve either gas-phase ionisation (El), gas-phase chemical reactions (Cl, APCI) or ion evaporation (TSP, ESP, SSI). Van Baar [519] has reviewed ionisation methods (TSP, APCI, ESI and CF-FAB) in LC-MS. 

Electrospray has been successful for numerous azo dyes that are not ionic salts. Several anthraquinone dyes have been analysed by LC-ESI-MS [552]. Electrospray achieves the best sensitivity for compounds that are precharged in solution (e.g. ionic species or compounds that can be (de)protonated by pH adjustment). Consequently, LC-ESI-MS has focused on ionic dyes such as sulfonated azo dyes which have eluded analysis by particle-beam or thermospray LC-MS [594,617,618]. Techniques like LC-PB-MS and GC-MS, based on gas-phase ionisation, are not suitable for nonvolatile components such as sulfonated azo dyes. LC-TSP-MS on... 

Protonic solvents such as methanol or acetonitrile are commonly employed, often with the addition of formic or acetic acid or bases such as hexylamine, to aid gas phase ionisation. 

Gas-phase ionisation by electron impact (and by other means, see later) generates many more positive ions than negative ions and conventional EIMS measurements therefore concentrate on the positive ions. Newer mass spectrometers offer the option of negative-ion EIMS, which can have some advantages such as cleaner spectra (less background - fewer peaks near the baseline) and intense [M- 1] peaks. 

Atmospheric pressure chemical ionisation (APCI) is a technique that also creates gas phase ions from the liquid sample. It too takes place at atmospheric pressure and uses a similar interface to that in ESI. As in ESI, the sample solution is mixed with a nebulising gas and the sample arrives in the spray chamber as a fine mist of droplets or spray. In APCI, an extra component - a corona discharge - is used to further ionise the analyte droplets in a manner similar to straightforward Cl (Figure 2.34). While a small amount of fragmentation may occur, the technique is still considered to be a soft ionisation one. The gas-phase ionisation in APCI is more effective than ESI for analysing less polar species. ESI and APCI are complementary methods. 

For many routine applications, a solid or liquid sample may be introduced to the source of the spectrometer by direct mechanical insertion, i.e. it is held on the end of metal probe which is inserted into the source via a system of air-locks. All of the sample is presented to the source simultaneously, allowing no separation of the components, and the resulting spectrum is a function of the whole of the sample. For gas-phase ionisation techniques an added level of discrimination may be obtained by selectively vaporising the components of the sample. Volatility discrimination is achieved by acquiring data as a function of time while the... 

The calculation of the rates of these elementary reactions in aqueous solution using the I8M poses a new problem. This method calculates the electronic parameter, m in eq. (11.11), from the gas-phase ionisation energies and electron affinities, which may not be adequate for reactions in aqueous solution. In fact, it is not the acmal /p and in aqueous solution that is relevant, but their changes due to differential solvation. The simplest way to circumvent this problem is to rescale the method by using an empirical value of a, fitted to... 

Reviews of gas-phase kinetics (59) and ionisation energies (60) have also Hsted some of the advantages SF enjoys ia service as a gaseous dielectric. 

Little effect is exerted by ionisation of the gas phase on corrosion rate. 

In this chapter, we have chosen from the scientific literature accounts of symposia published at intervals during the period 1920 1990. They are personal choices illustrating what we believe reflect significant developments in experimental techniques and concepts during this time. Initially there was a dependence on gas-phase pressure measurements and the construction of adsorption isotherms, followed by the development of mass spectrometry for gas analysis, surface spectroscopies with infrared spectroscopy dominant, but soon to be followed by Auger and photoelectron spectroscopy, field emission, field ionisation and diffraction methods. 

C, is one of the most critical parameters in TSP operation, and should be optimised for different samples, wherever possible. This is considered to be a considerable drawback in routine operation of unknown polymer/additive extracts. Too low a vaporiser temperature results in the solute and solvent spraying into the ionisation source in their liquid form, without formation of gas-phase ions. Too high a vaporiser temperature causes premature evaporation of the solute and solvent before the outlet of the capillary is reached. This causes an unstable, pulsing ion beam. As ion formation in TSP operation depends very critically on the extent of desolvation and the energy of the nebulised droplets, it is clear that an inappropriate vaporiser temperature will cause loss of sensitivity. 

Ionisation processes in IMS occur in the gas phase through chemical reactions between sample molecules and a reservoir of reactive ions, i.e. the reactant ions. Formation of product ions in IMS bears resemblance to the chemistry in both APCI-MS and ECD technologies. Much yet needs to be learned about the kinetics of proton transfers and the structures of protonated gas-phase ions. Parallels have been drawn between IMS and CI-MS [277]. However, there are essential differences in ion identities between IMS, APCI-MS and CI-MS (see ref. [278]). The limited availability of IMS-MS (or IMMS) instruments during the last 35 years has impeded development of a comprehensive model for APCI. At the present time, the underlying basis of APCI and other ion-molecule events that occur in IMS remains vague. Rival techniques are MS and GC-MS. There are vast differences in the principles of ion separation in MS versus IMS. 

LC-APCI-MS is a derivative of discharge-assisted thermospray, where the eluent is ionised at atmospheric pressure. In an atmospheric pressure chemical ionisation (APCI) interface, the column effluent is nebulised, e.g. by pneumatic or thermospray nebulisation, into a heated tube, which vaporises nearly all of the solvent. The solvent vapour acts as a reagent gas and enters the APCI source, where ions are generated with the help of electrons from a corona discharge source. The analytes are ionised by common gas-phase ion-molecule reactions, such as proton transfer. This is the second-most common LC-MS interface in use today (despite its recent introduction) and most manufacturers offer a combined ESI/APCI source. LC-APCI-MS interfaces are easy to operate, robust and do not require extensive optimisation of experimental parameters. They can be used with a wide variety of solvent compositions, including pure aqueous solvents, and with liquid flow-rates up to 2mLmin-1. 

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