Spontaneous ionization

Chapters 1 and 2. Most C—H bonds are very weakly acidic and have no tendency to ionize spontaneously to form carbanions. Reactions that involve carbanion intermediates are therefore usually carried out in the presence of a base which can generate the reactive carbanion intermediate. Base-catalyzed condensation reactions of carbonyl compounds provide many examples of this type of reaction. The reaction between acetophenone and benzaldehyde, which was considered in Section 4.2, for example, requires a basic catalyst to proceed, and the kinetics of the reaction show that the rate is proportional to the catalyst concentration. This is because the neutral acetophenone molecule is not nucleophihc and does not react with benzaldehyde. The much more nucleophilic enolate (carbanion) formed by deprotonation is the reactive nucleophile. 

Figure B2.3.8. Energy-level sehemes deseribing various optieal methods for state-seleetively deteeting ehemieal reaetion produets left-hand side, laser-indueed fluoreseenee (LIF) eentre, resonanee-enlianeed multiphoton ionization (REMPI) and right-hand side, eoherent anti-Stokes Raman speetroseopy (CARS). The ionization oontinuiim is denoted by a shaded area. The dashed lines indieate virtual eleetronie states. Straight arrows indieate eoherent radiation, while a wavy arrow denotes spontaneous emission.

Auto ionization. Occurs when an internally supraexcited atom or molecular moiety loses an electron spontaneously without further interaction with an energy source. (The state of the atom or molecular moiety is known as a pre-ionization state.)... 

Fig. 11. Reaction of ionized coupler and oxidized developer (Dev ) to produce the intermediate leuco dye. If X is a good leaving group, the reaction proceeds spontaneously to dye, and the coupler is said to be two-equivalent. If oxidation by a second molecule of oxidized developer is required, the...

Experiments and calculations both indicate that electron transfer from potassium to water is spontaneous and rapid, whereas electron transfer from silver to water does not occur. In redox terms, potassium oxidizes easily, but silver resists oxidation. Because oxidation involves the loss of electrons, these differences in reactivity of silver and potassium can be traced to how easily each metal loses electrons to become an aqueous cation. One obvious factor is their first ionization energies, which show that it takes much more energy to remove an electron from silver than from potassium 731 kJ/mol for Ag and 419 kJ/mol for K. The other alkali metals with low first ionization energies, Na, Rb, Cs, and Fr, all react violently with water. 

Figure 1T2 shows anodic d cathodic polarization curves for the partial CD of dissolution 4 and deposition 4 of the metal and for the partial CD of ionization 4 and evolution 4 of hydrogen, as well as curves for the overall reaction current densities involving the metal (4) and the hydrogen (4). The spontaneous dissolution current density 4 evidently is determined by the point of intersection. A, of these combined curves. 

In contrast to the equilibrium electrode potential, the mixed potential is given by a non-equilibrium state of two different electrode processes and is accompanied by a spontaneous change in the system. Besides an electrode reaction, the rate-controlling step of one of these processes can be a transport process. For example, in the dissolution of mercury in nitric acid, the cathodic process is the reduction of nitric acid to nitrous acid and the anodic process is the ionization of mercury. The anodic process is controlled by the transport of mercuric ions from the electrode this process is accelerated, for example, by stirring (see Fig. 5.54B), resulting in a shift of the mixed potential to a more negative value, E mix. 

Gas-phase ion chemistry is a broad field which has many applications and which encompasses various branches of chemistry and physics. An application that draws together many of these branches is the synthesis of molecules in interstellar clouds (Herbst). This was part of the motivation for studies on the neutralization of ions by electrons (Johnsen and Mitchell) and on isomerization in ion-neutral associations (Adams and Fisher). The results of investigations of particular aspects of ion dynamics are presented in these association studies, in studies of the intermediates of binary ion-molecule Sn2 reactions (Hase, Wang, and Peslherbe), and in those of excited states of ions and their associated neutrals (Richard, Lu, Walker, and Weisshaar). Solvation in ion-molecule reactions is discussed (Castleman) and extended to include multiply charged ions by the application of electrospray techniques (Klassen, Ho, Blades, and Kebarle). These studies also provide a wealth of information on reaction thermodynamics which is critical in determining reaction spontaneity and availability of reaction channels. More focused studies relating to the ionization process and its nature are presented in the final chapter (Harland and Vallance). 

Although the work discussed thus far has covered primarily neutral organic radicals, there are many types of cation and anion radicals that are stabilized on the surface. Some of these ion radicals are formed through photochemical processes however, many others are spontaneously generated on a surface. The type of radical ion that is formed depends on the oxidizing or reducing character of particular sites on the surface, as well as on the ionization potential and the electronegativity of the adsorbed molecule. 

The mere exposure of diphenyl-polyenes (DPP) to medium pore acidic ZSM-5 was found to induce spontaneous ionization with radical cation formation and subsequent charge transfer to stabilize electron-hole pair. Diffuse reflectance UV-visible absorption and EPR spectroscopies provide evidence of the sorption process and point out charge separation with ultra stable electron hole pair formation. The tight fit between DPP and zeolite pore size combined with efficient polarizing effect of proton and aluminium electron trapping sites appear to be the most important factors responsible for the stabilization of charge separated state that hinder efficiently the charge recombination. 

The second spectrum (figure 3b) displays the spectral features of DPP+ radical cation and provides evidence of DPP spontaneous ionization DPB + HZSM-5 -> DPB + HZSM-5 " (eq. 2). The third spectrum (fig. 3c) exhibits a broad band at 425 nm and is assigned to electron-hole pair formation DPB + HZSM-5 " - DPB HZSM-5 + (eq. 3). 

DPB as well as other DPP molecules (t-stilbene, diphenyl-hexatriene) with relatively low ionization potential (7.4-7.8 eV) and low vapor pressure was successfully incorporated in the straight channel of acidic ZSM-5 zeolite. DPP lies in the intersection of straight channel and zigzag channel in the vicinity of proton in close proximity of Al framework atom. The mere exposure of DPP powder to Bronsted acidic ZSM-5 crystallites under dry and inert atmosphere induced a sequence of reactions that takes place during more than 1 year to reach a stable system which is characterized by the molecule in its neutral form adsorbed in the channel zeolite. Spontaneous ionization that is first observed is followed by the radical cation recombination according to two paths. The characterization of this phenomenon shows that the ejected electron is localized near the Al framework atom. The reversibility of the spontaneous ionization is highlighted by the recombination of the radical cation or the electron-hole pair. The availability of the ejected electron shows that ionization does not proceed as a simple oxidation but stands for a real charge separated state. 

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