Ionization positive metal ions

If a positive potential is applied to the metal, as shown in Fig. 10.3, the ionization of the surface atoms will be promoted, and thus more metal ions will be produced at the surface. In the solution, water molecules, positive ions (cations), and negative ions (anions) drift around. The adsorbed layer of positive metal ions attracts nearby water dipoles in a preferential direction. The negative ions in the solution near the anode surface are also attracted toward the surface. The adsorbed fixed layer and the negative ion layer (Fig. 10.3) together are the so-called electrical double layer. Details about the double layer are available elsewhere [3]. Electrochemical reactions and mass transport for further electrochemical dissolution occur and pass through this double layer. 

In a metallic bond, the atoms are considered to be ionized, with the positive ions arranged in the lattice positions. The electrons are delocalized, that is, they are able to move essentially freely throughout the lattice. The bonding occurs by the electrostatic attraction between the electrons and the positive metal ions. Most metals can be considered as close-packed arrays of atoms held together by these delocalized electrons. The metallic bond contributes to the bonding of interstitial carbides and is described in more detail in Ch. 3. 

Ionization of Metals in a Plasma. A loss in spectrochemical sensitivity results when a free metal atom is split into a positive ion and an electron ... 

In the isoelectronic zirconates this absorption band is not observed [17]. The spectral position of these MMCT bands has been interpreted in terms of the relevant ionization potentials [17], an approach which runs parallel with the Hush theory [10]. The fact that the MMCT transition is at higher energy in the Cr(III)-Ti(IV) pair than in the Fe(II)-Ti(IV) pair is due to the more than 10 eV higher ionization potentials of the trivalent transition-metal ions compared to the divalent transition-metal ions. The fact that the MMCT absorption band is not observed in the zirconates in contradiction to the titanates is due to the higher ionization potential of the Ti(III) species ... 

The ionization probabilities It vary over some five decades across the elements in the periodic table. In addition, they vary also with the chemical environment of the element. This effect, usually referred to as the matrix effect, makes quantitation of SIMS spectra extremely difficult. As illustrated in Table 4.1, positive secondary ion yields from metal oxides are typically two orders of magnitude higher than those of the corresponding metals. A similar increase in yields from metals is observed after adsorption of gases such as oxygen or carbon monoxide. 

Expression (4-2) accounts qualitatively for the observed variations of secondary ion yields with ionization potential. It also describes correctly that the yields of positive secondary ions from metals increase when molecules such as CO or oxygen, which increase the work function, cover the surface. Although the model elegantly predicts a number of trends correctly, it is not detailed enough to be a basis for quantitative analysis of technical samples. 

Soma et al. (12) have generalized the trends for aromatic compound polymerization as follows (1) aromatic compounds with ionization potentials lower than approximately 9.7 eV formg radical cations upon adsorption in the interlayer of transition-metal ion-exchanged montmorillonites, (2) parasubstituted benzenes and biphenyls are sorbed as the radical cations and prevented from coupling reactions due to blockage of the para position, (3) monosubstituted benzenes react to 4,4 -substituted biphenyls which are stably sorbed, (4) benzene, biphenyl, and p-terphenyl polymerized, and (5) biphenyl methane, naphthalene, and anthracene are nonreactive due to hindered access to reaction sites. However, they observed a number of exceptions that did not fit this scheme and these were not explained. 

The FAB plasma provides conditions that allow to ionize molecules by either loss or addition of an electron to form positive molecular ions, M" , [52,89] or negative molecular ions, M, respectively. Alternatively, protonation or deprotonation may result in [Mh-H]" or [M-H] quasimolecular ions. Their occurrence is determined by the respective basicity or acidity of analyte and matrix. Cationization, preferably with alkali metal ions, is also frequently observed. Often, [Mh-H]" ions are accompanied by [MH-Na]" and [Mh-K]" ions as already noted with FD-MS (Chap. 8.5.7). Furthermore, it is not unusual to observe and [Mh-H]" ions in the same FAB spectmm. [52] In case of simple aromatic amines, for example, the peak intensity ratio M 7[Mh-H] increases as the ionization energy of the substrate decreases, whereas 4-substituted benzophenones show preferential formation of [Mh-H]" ions, regardless of the nature of the substituents. [90] It can be assumed that protonation is initiated when the benzophenone carbonyl groups form hydrogen bonds with the matrix. 

Excitation to the repulsive electronic state may also involve a multi-electron process. For example, creation of a core hole on a metal atom in an oxide may lead to an interatomic Auger transition which ultimately results in a positive oxygen ion which desorbs because it is now in a strongly repulsive Madelung well. Knotek and Feibelman have reported results which they interpret in this manner. Core ionization in the adsorbed molecule can also lead to an Auger process which leads to desorption. 

For ESP ionization, the analytes must be ionic, or have an ionizable functional group, or be able to form an ionic adduct in solution the analytes are commonly detected as deprotonated species or as cation adducts of a proton or an alkali metal ion. When using positive ion ESP ionization, use of ammonium acetate as a mobile-phase modifier is generally unsuitable. Instead, organic modi-... 

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