Electron transfer reactions positive charge

Constants for Electron Transfer Reactions Positively Charged Reactants °... 

Several processes are unique to ions. A common reaction type in which no chemical rearrangement occurs but rather an electron is transferred to a positive ion or from a negative ion is tenued charge transfer or electron transfer. Proton transfer is also conunon in both positive and negative ion reactions. Many proton- and electron-transfer reactions occur at or near the collision rate [72]. A reaction pertaining only to negative ions is associative detaclunent [73, 74],... 

We now consider a slightly different cell in which the copper half-cell is the positive pole. Perhaps the negative electrode is zinc metal in contact with Zn2+ ions. If the cell discharges spontaneously, then the electron-transfer reaction is the reduction reaction in Equation (7.7) as depicted in the strip cartoon in Figure 7.8. A bond forms between the surface of the copper electrode and a Cu2+ cation in the solution The electrons needed to reduce the cation come from the electrode, imparting a net positive charge to its surface. 

Electron-transfer processes play many very important roles in chemistry and biology. Because the present work is focused on electron-transfer events occurring within positively charged gas-phase peptides as they occur in ETD and ECD mass spectrometry experiments, it is not appropriate or feasible to review the myriad of other places electron-transfer reactions occur in chemistry. Chapter 10 of the graduate level textbook by Schatz and Ratner [12] gives a nice introduction to the main kinds of electron-transfer events that chemists usually study as well as to the theoretical underpinnings. They also give, at the end of Chapter 10, several literature references to selected seminal papers on these subjects. 

This reaction profile of the polymer complex has some similarities with the phenomenon of the polyelectrolyte-catalyzed reactions. It has been reported that the reactions between two positively charged species in aqueous solution are drastically accelerated in the presence of polyanionsS2 84 For example, the electron-transfer reaction between [Co(IIIXen)2(Py)Cl]2+ and [Fe(IIXOH2)6]2+ is very slow because the reaction occurs between two cations however, the addition of a small amount of poly(styrenesulfonate) accelerates the reaction by a factor of 103 84). This result is also interpreted as indicating that the two positively charged reactants are both concentrated in the polyanion domain, so that they encounter each other more frequently [Fig. 17(b)]. 

Here (3 is the cathodic symmetry factor of the rate-determining step and v is a positive integral number indicating how many times the RDS is occurring in the global electron-transfer reaction (mostly v=l). The parameter r takes into account a homogeneous chemical reaction, the rate of which is not dependent on the potential, as RDS when the RDS is a charge-transfer step, r=l applies, and for a chemical RDS, r=0. 

Photo-induced electron transfer between [Ru(bpy)3]2+-like centres covalently bound to positively-charged polymers (N-ethylated copolymers of vinylpyridine and [Ru(bpy)2(MVbpy)]2+) and viologens or Fe (III) has been studied using laser flash photolysis techniques. It is found that the backbone affects the rates of excited state quenching, the cage escape yield, and the back electron transfer rate because of both electrostatic and hydrophobic interactions. The effect of ionic strength on the reactions has been studied. Data on the electron transfer reactions of [Ru(bpy)3]2+ bound electrostatically or covalently to polystyrenesulphonate are also presented. 

Hydrogen atoms and hydroxyl radicals react with aliphatic compounds mainly by H-abstraction from the chain, although reactions with certain substituents are also important. With hydrated electrons the functioned group is the only site of reaction and its nature determines the reactivity. The reactions of hydrated electrons are by definition electron transfer reactions. The rate of reaction of a certain substrate will depend on its ability to accommodate an additional electron. For example, in an unsaturated compound the rate may depend on the presence of a site with a partial positive charge. Thus acrylonitrile and benzonitrile are three orders of magnitude more reactive toward e q than are ethylene and benzene. On the other hand, this large difference does not exist in the case of addition of H and OH. 

Next we turn to the interpretation of the rate constants for electron-transfer reactions of cytochrome c that are accompanied by a net chemical change (Tables III and IV). The rate constants for the reaction of cytochrome c with both negatively charged (Fe(CN)5L3" and Ru[-(OSO30)2phen]34 ) and positively charged (Fe(bipy)2(CN)2+ and Ru(bipy)32+) complexes can be very great. 

The reaction centre found in many purple non-sulphur bacteria is a simple example of a group of proteins that are natureis solar batteries. The reaction centre uses the energy of sunlight to generate positive and negative charges on opposite sides of the bacterial cytoplasmic membrane. This potential difference drives a circuit of electron transfer reactions that are linked to proton translocation across this membrane. 

The occurrence of a reaction at each electrode is tantamount to removal of equal amounts of positive and negative charge from the solution. Hence, when electron-transfer reactions occur at the electrodes, ionic drift does not lead to segregation of charges and the building up of an electroneutrality field (opposite to the applied field). Thus, the flow of charge can continue i.e., the solution conducts. It is an ionic conductor. 

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