Stable solvated electrons

OCV conditions, by a newly formed SEI is expected to be a slow process. The SEI is necessary in PE systems in order to prevent the entry of solvated electrons to the electrolyte and to minimize the direct reaction between the lithium anode and the electrolyte. SEI-free Li/PE batteries are not practical. The SEI cannot be a pure polymer, but must consist of thermodynamically stable inorganic reduction products of... 

Reduction of benzenoid hydrocarbons with solvated electrons generated by the solution of an alkali metal in liquid ammonia, the Birch reaction [34], involves homogeneous electron addition to the lowest unoccupied 7t-molecular orbital. Protonation of the radical-anion leads to a radical intermediate, which accepts a further electron. Protonation of the delocalised carbanion then occurs at the point of highest charge density and a non-conjugated cyclohexadiene 6 is formed by reduction of the benzene ring. An alcohol is usually added to the reaction mixture and acts as a proton source. The non-conjugated cyclohexadiene is stable in the presence of... 

It was also observed, in 1973, that the fast reduction of Cu ions by solvated electrons in liquid ammonia did not yield the metal and that, instead, molecular hydrogen was evolved [11]. These results were explained by assigning to the quasi-atomic state of the nascent metal, specific thermodynamical properties distinct from those of the bulk metal, which is stable under the same conditions. This concept implied that, as soon as formed, atoms and small clusters of a metal, even a noble metal, may exhibit much stronger reducing properties than the bulk metal, and may be spontaneously corroded by the solvent with simultaneous hydrogen evolution. It also implied that for a given metal the thermodynamics depended on the particle nuclearity (number of atoms reduced per particle), and it therefore provided a rationalized interpretation of other previous data [7,9,10]. Furthermore, experiments on the photoionization of silver atoms in solution demonstrated that their ionization potential was much lower than that of the bulk metal [12]. Moreover, it was shown that the redox potential of isolated silver atoms in water must... 

Although the mechanism of the photo-induced generation of mono- and bimetallic metal clusters, except for the photographic application (Section 20.6), has been studied with considerably less detail than for the radiolytic route, some stable clusters, mostly of noble metals (Ag, Au, Pt, Pd, Rh), have also been prepared by UV excitation of metal ion solutions [129-141]. Generally, halides and pseudo-halides counter anions are known to release, when excited, solvated electrons, which reduce the metal ions up to the zerovalent state. Oxalate excitation yields the strong reducing carbonyl radical COO [30]. Photosensitizers are likewise often added [142]. Metal clusters are photo-induced as well at the surface of photo-excited semiconductors in contact with metal ions [143,144]. 

In strongly basic solvents like HMPA, amines and liquid ammonia, solvated electrons are relatively stable. In these solvents, if the supporting electrolyte is the salt of Li+ or Na+, blue solvated electrons, esm are generated from the surface of the platinum electrode polarized at a very negative potential ... 

Jhe discovery by radiation chemists of solvated electrons in a variety of solvents (5, 16, 20, 22, 23) has renewed interest in stable solutions of solvated electrons produced by dissolving active metals in ammonia, amines, ethers, etc. The use of pulsed radiolysis has permitted workers to study the kinetics of fast reactions of solvated electrons with rate constants up to the diffusion-controlled limit (21). The study of slow reactions frequently is made difficult because the necessarily low concentrations of electrons magnify the problems caused by impurities, while higher concentrations frequently introduce complicating second-order processes (9). The upper time limit in such studies is set by the reaction with the solvent itself. 

The ferrocyanide ion, stable at neutral pH, shows well understood optical transitions in the visible and near u.v. It carries four negative charges, which should facilitate solvated electron formation. A survey of its known photochemistry indicated that at neutral pH we may hope that solvated electron formation will be the only photochemical primary process. Indeed, after we commenced the work, Matheson, Mulac, and Rabani (31) found on flash photolysis the absorption spectrum of e aq in aqueous solutions of ferrocyanide. 

We cannot see any significant conceptual difference between the hydrated and, e.g. naphthalenated electron, and we would therefore urge the reader to think of solvated electrons as radical anions of solvent molecules in some environments the solvent radical anions are stable (ammonia, amines, HMPA), in some not (protic solvents), and that is exactly the same kind of behaviour exhibited by more conventional radical anions (Szwarc, 1968, 1969). 

Solvated electrons can also be produced in water based glasses by irradiation, but they are not as stable... 

Flash photolysis of misonidazole, metronidazole, and nitrobenzothiazoles has been carried out in [1369-1371], Laser flash-photolysis (355 nm) allows to determine relatively stable anion-radicals of misonidazole and metronidazole in aqueous solutions [1370], Solvated electrons have been formed at harder irradiation, the result of which interaction with nitroimidazole molecules is generation of their radical anions [1372], The authors [1372] have also found that fluorescence intensity of metronidazole is about 20 times more than that of misonidazole in same conditions. Photochromic properties of benzothiazole derivatives containing nitro and methyl groups in the ortho positions with respect to each other were studied by flash photolysis [1371], The application of the thermodynamic approach to predict the kinetic stability of formed nitronic acids is limited owing to specific intramolecular interactions. The lifetime of photoinduced nitronic acid anions tends to increase with rise in the chemical shift of the methyl protons. The rate constants photoinduced nitronic acids and their anions increase as the CH3C-CN02 bond becomes longer [1371],... 

The chemistry of gold is more diversified than that of silver. Six oxidation states, from -I to III and V, occur in its chemistry. Gold(-I) and Auv have no counterparts in the chemistry of silver. Solvated electrons in liquid ammonia can reduce gold to give the Au" ion which is stable in liquid ammonia (E° = -2.15 V). In the series of binary compounds MAu (M = Na, K, Rb, Cs), the metallic character decreases from Na to Cs. CsAu is a semiconductor with the CsCl structure and is best described as an ionic compound, Cs+Au . The electron affinity of gold (—222.7 kJ mol"1) is comparable to that of iodine (-295.3 kJ mol-1). Gold in the oxidation state -I is also found in the oxides (M+ Au O2 (M = Rb, Cs) these, too, have semiconducting properties.1... 

There is something very appealing about the simple mechanism of electron transfer either directly between species or else indirectly via dissolved, stable electrons in the solvent. The classic example of the blue solutions of the alkali metals in liquid NHa certainly indicates the feasibility of having solvated electrons in a solution. 

The stability of the solvated electron in the various solvents varies greatly depending on the reactivity of the electron with the solvent. In liquid ammonia solvated electrons are stable for long periods in the blue solutions of alkali metals in ammonla(45). In watjr, eaq decays slowly by reaction (9) with a rate constant of 16 M s (46)... 

Since 1962, when it was first characterized by pulse radiolysis transient absorption measurements in water, the solvated electron has been widely studied in numerous solvents. The solvated electron, denoted by e, is a thermodynamically stable radical, but like most free radicals, it has a short lifetime due to its high chemical reactivity. The solvated electron is a unique chemical moiety whose properties may be compared in many solvents and are not dependent on the method creating the solvated electron. The solvated electron is an important reactive species as it is the simplest electron donor, its reactions correspond to electron transfer reactions and its reactivity may be used to probe electron transfer properties of acceptors. During the last 40 years, due to its optical absorption properties, the... 

In radiolysis, one of the most important reactions of solvated electrons is recombination with positive ions and radicals that are simultaneously produced in close proximity inside small volumes called spurs. These spurs are formed through further ionization and excitation of the solvent molecules. Thus, in competition with diffusion into the bulk, leading to a homogeneous solution, the solvated electron may react within the spurs. Geminate recombinations and spur reactions have been widely studied in water, both experimentally and theoretically, ° and also in a few other solvents. " Typically, recombinations occur on a timescale of tens to hundreds of picoseconds. In general, the primary cation undergoes a fast proton transfer reaction with a solvent molecule to produce the stable solvated proton and the free radical. Consequently, the... 

The way in which this solvent modification occurs is suggested by the pattern of hyperfine constants for (which is one of the few solvated electron species sufficiently stable to obtain its NMR spectrum). The Knight shift of NMR lines is due to the contact Fermi (isotropic) hyperfine interaction of the excess electron with the magnetic nuclei (X) in the solvent molecules it is the measure of spin density, (0) in the r-type atomic orbitals centered on a given nucleus X ... 

The solvated electron in liquid ammonia was discovered in 1864 by Weyl, and was identified in 1908 by Kraus as an electron, e am, in a cavity surrounded by ammonia molecules. It is prepared when an alkali metal, for example sodium, is dissolved in ammonia, to form a stable blue color under these conditions the electron is present in equilibrium with the metal atom and cation [34]. By contrast, e am produced by pulse radiolysis of liquid ammonia is unstable due to its reactions with other radiolysis products for example, in pure ammonia at —45 °C, its lifetime is ca. 7 ps [35], The major decay reactions are thought to involve the oxidizing radicals NH2 and NH [36], because addition of potassium ethoxide stabilizes e am this is explicable, since ethoxide ion is expected to scavenge these radicals [36a]. 

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