Ionization decomposition

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). 

Metastable ions yield valuable information on fragmentation in mass spectrometry, providing insight into molecular structure. In electron ionization, metastable ions appear naturally along with the much more abundant normal ions. Abundances of metastable ions can be enhanced by collisionally induced decomposition. 

There are methods for vaporizing solids of low volatility by placing them on a thin wire, which is then raised to a high temperature within a fraction of a second (direct chemical ionization, DCI). This rapid heating allows some vaporization without decomposition, but with the development of later ionization methods, it is now rarely used. 

Peroxophosphoric Acids and Their Salts. In its usual impure form (H PO is the main contaminant), peroxomonophosphoric acid [13598-52-2] (5), is a viscous, coloress Hquid. The three ionization constants for peroxomonophosphoric acid are pifj = 1.1, P-A2 = 5.5, and pK (peroxide proton) = 12.8 (44). Oxidations comparable to those of peroxomonosulfuric acid, H2SO, occur in acid solutions of ca pH 2, but at higher pH values, H PO becomes less reactive as an oxidant and more unstable with respect to decomposition (44). The stmcture of H PO is probably similar to that of... 

All of the atomic species which may be produced by photon decomposition are present in plasma as well as the ionized states. The number of possible reactions is therefore also increased. As an example, die plasma decomposition of silane, SiH4, leads to the formation of the species, SiH3, SiHa, H, SiH, SiH3+ and H2+. Recombination reactions may occur between the ionized states and electrons to produce dissociated molecules either direcdy, or tlrrough the intermediate formation of excited state molecules. 

Low ionizing potentials or soft ionization methods are necessary to observe the parent ions in the mass spectra of many S-N compounds because of their facile thermal decomposition. Mass spectrometry has been used to investigate the thermal breakdown of S4N4 in connection with the formation of the polymer (SN). On the basis of the appearance potentials of various S Ny fragments, two important steps were identified ... 

A comparison of the electron impact (El) and chemical ionization (Cl-methane) mass spectra of 1//-azepine-1-carboxylates and l-(arylsulfonyl)-l//-azepines reveals that in the El spectra at low temperature the azepines retain their 8 -electron ring structure prior to fragmentation, whereas the Cl spectra are complicated by high temperature thermal decompositions.90 It has been concluded that Cl mass spectrometry is not an efficient technique for studying azepines, and that there is no apparent correlation between the thermal and photo-induced rearrangements of 1//-azepines and their mass spectral behavior. 

In fact, considerable thermal decomposition may precede ionization as suggested by the fact that only the relatively volatile 2,2-dimethylthiirene dioxide gave any evidence for the molecular ion. Retention of the positive charge with the sulfone function is responsible for the ion at m/e 64 (S027). 

The problem of the successful ionization of thermally labile molecules has been addressed by the introduction of energy-sudden techniques, such as fast-atom bombardment (FAB), which rely on the fact that energy may be provided to the molecule so rapidly that desorption takes place before decomposition may occur. 

The APCl ionization regime is much more harsh that ESI and this precludes its use for the study of large biomolecules, with the mass limit for APCl being generally considered as below 2000 Da. Having said this, as will be shown later, the technique may still be used for the analysis of many thermally labile compounds without their decomposition, and small peptides have been studied. 

The specificity of the ions/decompositions must be considered. Both electrospray ionization and APCI are soft ionization techniques and the resulting mass... 

Energy-sudden ionization technique One in which energy is provided to a thermally labile molecule so rapidly that it is desorbed and ionized before decomposition takes place. 

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