Oxidation-reduction reactions spontaneity

In electroless deposition, the substrate, prepared in the same manner as in electroplating (qv), is immersed in a solution containing the desired film components (see Electroless plating). The solutions generally used contain soluble nickel salts, hypophosphite, and organic compounds, and plating occurs by a spontaneous reduction of the metal ions by the hypophosphite at the substrate surface, which is presumed to catalyze the oxidation—reduction reaction. 

N204 also forms expl mixts with incompletely halogenated hydrocarbons, NGu, carbon disulfide, etc (Ref 33). The effect of spontaneous decompn by oxidation-reduction reactions when N204 is mixed with a number of fuels (hydrazine, gasoline, liq paraffin, etc) has resulted in its extensive use in liq propint rocket engines (Refs 12, 22, 27 35)... 

Examples of tunneling in physical phenomena occur in the spontaneous emission of an alpha particle by a nucleus, oxidation-reduction reactions, electrode reactions, and the umbrella inversion of the ammonia molecule. For these cases, the potential is not as simple as the one used here, but must be selected to approximate as closely as possible the actual potential. However, the basic qualitative results of the treatment here serve to explain the general concept of tunneling. 

The tarnish on silver, Ag2S, can be removed by boiling the silverware in slightly salty water (to improve the water s conductivity) in an aluminum pan. The reaction is an oxidation-reduction reaction that occurs spontaneously, similar to the redox reaction occurring in a voltaic cell. The Ag in Ag2S is reduced back to silver, while the A1 in the pan is oxidized to Al3+. 

One easily demonstrated electrical characteristic of moist soil is seen in the production of electricity when two different metals, namely, copper and zinc, are inserted into it. This is not unexpected because any salt-containing solution adsorbed in media, such as paper or cloth, and placed between these same two electrodes will cause a spontaneous reaction that produces electricity. The source of this flow of electrons is an oxidation-reduction reaction, represented as two half-reactions as shown in Figure 9.1 for copper and zinc. 

The thermodynamic criterion for spontaneity (feasibility) of a chemical and electrochemical reaction is that the change in free energy, AG have a negative value. Free-energy change in an oxidation-reduction reaction can be calculated from knowledge of the cell voltage ... 

The energy made available by this spontaneous electron flow (the free-energy change for the oxidation-reduction reaction) is proportional to AE ... 

While such a device has yet to be constructed, Debreczeny and co-workers have synthesized and studied a linear D-A, -A2 triad suitable for implementation in such a device.11641 In this system, compound 6, a 4-aminonaphthalene monoimide (AN I) electron donor is excited selectively with 400 nm laser pulses. Electron transfer from the excited state of ANI to Ai, naphthalene-1,8 4,5-diimide (NI), occurs across a 2,5-dimethylphenyl bridge with x = 420 ps and a quantum yield of 0.95. The dynamics of charge separation and recombination in these systems have been well characterized.11651 Spontaneous charge shift to A2, pyromellitimide (PI), is thermodynamically uphill and does not occur. The mechanism for switching makes use of the large absorption cross-section of the NI- anion radical at 480 nm, (e = 28,300). A second laser pulse at 480 nm can selectively excite this chromophore and provide the necessary energy to move the electron from NI- to PI. These systems do not rely on electrochemical oxidation-reduction reactions at an electrode. Thus, switching occurs on a subpicosecond time scale. 

Many oxidation-reduction reactions may be carried out in such a way as to generate electricity. These cells are known as voltaic (older term galvanic) cells. In principle, any spontaneous, oxidation-reduction reaction (aqueous) can be set up to generate electricity by the following requirements ... 

An oxidation-reduction reaction that is not spontaneous, for which the calculated cell potential is negative, may be induced by electrolysis. This reaction can be due to an external electrical potential to force electrons into the couple undergoing reduction and to extract electrons from the couple undergoing oxidation. The minimum external potential required for electrolysis is the value of the calculated cell potential for the reaction. 

One such combination of anode and cathode is called a cell. Theoretically, any spontaneous oxidation-reduction reaction can be made to produce a galvanic cell. A combination of cells is a battery. 

D) Acids do not spontaneously spit out a proton Despite our way of writing ionization equilibria as shown on the next page, acids do not give up a proton unless a base comes by to take the proton away. The reactions as drawn in the table should be considered half-reactions, just as the reactions in the electromotive series were half-reactions for balancing oxidation-reduction reactions in general chemistry. 

MUTAROTATION The a- and /T forms of monosaccharides are readily interconverted when dissolved in water. This spontaneous process, called mutarotation, produces an equilibrium mixture of a- and /1-forms in both furanose and pyranose ring structures. The proportion of each form differs with each sugar type. Glucose, for example, exists primarily as a mixture of a- (38%) and j8- (62%) pyranose forms (Figure 7.11). Fructose is predominantly found in the a-and /J-furanose forms. The open chain formed during mutarotation can participate in oxidation-reduction reactions. 

Electrochemistry is the branch of chemistry that deals with the interconversion of electrical energy and chemical energy. Electrochemical processes are redox (oxidation-reduction) reactions in which the energy released by a spontaneous reaction is converted to electricity or in which electrical energy is nsed to cause a nonspontaneous reaction to occur. Although redox reactions were discnssed in Chapter 4, it is helpful to review some of the basic concepts that will come np again in this chapter. 

Oxidation-reduction reactions with a positive AE have a negative AG and thus tend to proceed spontaneously. 

In the reduction of aqueous copper(II) ions by zinc metal, electrons flow from the zinc rod directly to copper(II) ions in the solution. If electron transfer from the zinc rod to the copper ions in solution could be directed through an external electrical circuit, this spontaneous oxidation-reduction reaction could be used to produce an electrical current that could perform some useful function. 

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