Reagent gases, mass

T.G. (2002) Determination of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls by gas chromatography/ mass spectrometry in the negative chemical ionization mode with different reagent gases. Mass Spectrom. Rev., 21, 373-387. 

Figure 4. Swept double resonance experiment on perdeutero-fluorene using H2180 as a reagent gas. Mass 174 was monitored as masses from 15 to 21 amu were sequentially ejected at 0.2 amu intervals.

Decomposition (fragmentation) of a proportion of the molecular ions (M +) to form fragment ions (A B+, etc.) occurs mostly in the ion source, and the assembly of ions (M +, A+, etc.) is injected into the mass analyzer. For chemical ionization (Cl), the Initial ionization step is the same as in El, but the subsequent steps are different (Figure 1.1). For Cl, the gas pressure in the ion source is typically increased to 10 mbar (and sometimes even up to atmospheric pressure) by injecting a reagent gas (R in Figure 1.1). 

If the substrate (M) is more basic than NHj, then proton transfer occurs, but if it is less basic, then addition of NH4 occurs. Sometimes the basicity of M is such that both reactions occur, and the mass spectrum contains ions corresponding to both [M + H]+ and [M + NH4]. Sometimes the reagent gas ions can form quasi-molecular ions in which a proton has been removed from, rather than added to, the molecule (M), as shown in Figure 1.5c. In these cases, the quasi-molecular ions have one mass unit less than the true molecular mass. 

Some substances under El conditions fragment so readily that either no molecular ions survive or so few survive that it is difficult to be sure that the ones observed do not represent some impurity. Therefore, there is either no molecular mass information or it is uncertain. Under Cl conditions, very little fragmentation occurs and, depending on the reagent gas, ions [M + X]+ (X = H, NH4, NO, etc.) or [M - H] or [M - H]" or [M -1- X] (X = F, Cl, OH, O, etc.) are the abundant quasi-molecular ions, which do give molecular mass information. 

Much of the energy deposited in a sample by a laser pulse or beam ablates as neutral material and not ions. Ordinarily, the neutral substances are simply pumped away, and the ions are analyzed by the mass spectrometer. To increase the number of ions formed, there is often a second ion source to produce ions from the neutral materials, thereby enhancing the total ion yield. This secondary or additional mode of ionization can be effected by electrons (electron ionization, El), reagent gases (chemical ionization. Cl), a plasma torch, or even a second laser pulse. The additional ionization is often organized as a pulse (electrons, reagent gas, or laser) that follows very shortly after the... 

As each mixture component elutes and appears in the ion source, it is normally ionized either by an electron beam (see Chapter 3, Electron Ionization ) or by a reagent gas (see Chapter I, Chemical Ionization ), and the resulting ions are analyzed by the mass spectrometer to give a mass spectmm (Figure 36.4). 

Figure 3.2 Piocesses occurring in chemical ionization mass spectrometry using methane as the reagent gas.

These arise either by an analogous process to that described above for Cl, i.e. the adduction of a negatively charged species such as Cl , and the abstraction of a proton to generate an (M — H) ion, or by electron attachment to generate an M ion. The ions observed in the mass spectrum are dependent on the species generated by the reagent gas and the relative reactivities of these with each other and with the analyte molecule. 

Cl is an efficient, and relatively mild, method of ionization which takes place at a relatively high pressure, when compared to other methods of ionization used in mass spectrometry. The kinetics of the ion-molecule reactions involved would suggest that ultimate sensitivity should be obtained when ionization takes place at atmospheric pressure. It is not possible, however, to use the conventional source of electrons, a heated metallic filament, to effect the initial ionization of a reagent gas at such pressures, and an alternative, such as Ni, a emitter, or a corona discharge, must be employed. The corona discharge is used in commercially available APCI systems as it gives greater sensitivity and is less hazardous than the alternative. 

The appearance and reproducibility of chemical ionization mass spectra depends on the ionizing conditions, principally the source temperature and presstire and the purity of the reagent gas. Chemical ionization mass spectra are generally not as reproducible as electron impact spectra. 

The main features of DCI-MS and DCI-MS/MS are given in Table 6.14. DCI has gained rapid popularity because it is relatively simple to adapt to almost any mass spectrometer and gives results similar to FD, but in a more simple manner. It is not a substitute for FD, but it is less expensive and generally produces more fragmentation information than FD. For many compounds, molecular ions will be obtained where conventional solids probes would not do the job. DCI is known for the specificity provided by choosing reagent gas with different proton affinities. The major... 

In the deformulation of PE/additive systems by mass spectrometry, much less fragmentation was observed with DCI-MS/MS using ammonia as a reagent gas, than with FAB-MS [69]. FAB did not detect all the additives in the extracts. The softness and the lack of matrix effect make ammonia DCI a better ionisation technique than FAB for the analysis of additives directly from the extracts. Applications of hyphenated FAB-MS techniques are described elsewhere low-flow LC-MS (Section 7.3.3.2) and CE-MS (Section 7.3.6.1) for polar nonvolatile organics, and TLC-MS (Section 7.3.5.4). 

Selection of a suitable ionisation method is important in the success of mixture analysis by MS/MS, as clearly shown by Chen and Her [23]. Ideally, only molecular ions should be produced for each of the compounds in the mixture. For this reason, the softest ionisation technique is often the best choice in the analysis of mixtures with MS/MS. In addition to softness , selectivity is an important factor in the selection of the ionisation technique. In polymer/additive analysis it is better to choose an ionisation technique which responds preferentially to the analytes over the matrix, because the polymer extract often consists of additives as well as a low-MW polymer matrix (oligomers). Few other reports deal with direct tandem MS analysis of extracts of polymer samples [229,231,232], DCI-MS/MS (B/E linked scan with CID) was used for direct analysis of polymer extracts and solids [69]. In comparison with FAB-MS, much less fragmentation was observed with DCI using NH3 as a reagent gas. The softness and lack of matrix effect make ammonia DCI a better ionisation technique than FAB for the analysis of additives directly from the extracts. Most likely due to higher collision energy, product ion mass spectra acquired with a double-focusing mass spectrometer provided more structural information than the spectra obtained with a triple quadrupole mass spectrometer. 

Representative mass spectral conditions (negative chemical ionization) ion source temperature, 150°C ionizing current, 0.20 mamp electron energy, 70 eV methane reagent gas (source pressure 0.5 to 1 torr). 

The Mass Spectrometer Module houses the vacuum system, capillary interface assembly, and ion-trap mass spectrometer in approximately half of the module. Also included are the reagent gas and calibration gas subassembly (a temperature-controlled housing that ensures consistent gas pressures). The other half contains the electronic printed circuit boards, power supplies, and instrument control computer. 

Figure 4. Ion source and reaction chamber for ion-molecule equilibria. Solution to be electrosprayed flows through elestrospray capillary ESC at 1 -2 pL/min. Spray and ions enter pressure reduction capillary PRC and emerge into forechamber FCH maintained at 10 torr by pump PL. Ions in gas jet, which exits PRC, drift towards interface plate IN under influence of drift field imposed between FCH and IN. Ions enter the reaction chamber RCH through an orifice in IN and can react with reagents in the reagent gas mixture RG. This flows into RCH and out of RCH to FCH where it is pumped away. Ions leaking out of RCH through orifice OR are detected with a mass spectrometer. To reduce the inflow of solvent vapors into the pressure reduction capillary PRC, a stream of dry air is directed through the pipe Al, at 60 L/min, and pure N2 is directed at SG into the annular space at the entrance of the pressure reduction capillary, PRC. From Klassen, J. S. Blades, A. T. Kebarle, P. J. Phys. Chem. 1995, 99, 1509, with permission.

Where reactions are to be studied, specific ions may be selected using a quadrupole or a magnetic sector and the ions passed through a reaction cell containing the reactant gas, generally diluted with an inert gas. With ion traps, all the ions enter the cell and are mass selected and reacted with the reagent gas. 

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