Water half-reactions involving

Every redox reaction includes a reduction half-reaction and an oxidation halfreaction. A reduction half-reaction involving water, in which a chemical species accepts electrons, may be written in the form... 

There are a number of half-reactions involving nonmetals that lie above this value in the electrochemical series, and these will be reduced. In all of these cases, reaction will produce oxygen gas. For example, the dissolution of chlorine, CI2, in water will produce oxygen, although the unstable oxyacid, HOCl, forms as an intermediate. The reaction is ... 

In the electrolysis of a molten salt, the possible half-reactions are usually limited to those involving ions from the salt. When you electrolyze an aqueous solution of an ionic compound, however, you must consider the possibility that water is involved at one or both electrodes. Let us look at the possible half-reactions involving water. 

The Natural Reactor. Some two biUion years ago, uranium had a much higher (ca 3%) fraction of U than that of modem times (0.7%). There is a difference in half-hves of the two principal uranium isotopes, U having a half-life of 7.08 x 10 yr and U 4.43 x 10 yr. A natural reactor existed, long before the dinosaurs were extinct and before humans appeared on the earth, in the African state of Gabon, near Oklo. Conditions were favorable for a neutron chain reaction involving only uranium and water. Evidence that this process continued intermittently over thousands of years is provided by concentration measurements of fission products and plutonium isotopes. Usehil information about retention or migration of radioactive wastes can be gleaned from studies of this natural reactor and its products (12). 

Two major pathways exist for this reaction, one bypassing hydrogen peroxide (first pathway) and the other involving intermediate peroxide formation via reaction (15.21) (second pathway). The peroxide formed is either electrochemically reduced to water via reaction (15.22) or decomposed catalytically on the electrode surface via reaction (15.23), in which case half of the oxygen consumed to form it reemerges [in both cases the overall reaction corresponds to Eq. (15.20)]. 

It is not possible to prepare F2 by electrolysis of an aqueous NaF solution. In electrolysis, the most easily oxidized and reduced species are the ones involved. To prepare F2, the oxidation of F would have to occur. However, water is more easily oxidized than is F, as seen by its position in the standard reduction potential chart (Appendix J and below). By inspection, H20 is a stronger reducing agent than F because the reduction half-reaction has a less positive E°. So H20 s oxidation is preferable to F s oxidation. F2 can be prepared from molten NaF, but not aqueous NaF. 

Q O The combustion of ammonia in oxygen to form nitrogen dioxide and water vapour involves covalent molecules in the gas phase. The oxidation number method for balancing the equation was shown in an example in this section. Devise a half-reaction method for balancing the equation. Describe the assumptions you made in order to balance the equation. Also, describe why these assumptions did not affect the final result. 

Step 1 The Lh and Br concentrations are 1 mol/L, so use the standard reduction potentials for the half-reactions that involve these ions. Use the non-standard values for water. 

The midpoint potential of a half-reaction E, is the value when the concentrations of oxidized and reduced species are equal, [Aox] = [Aredl- In biological systems the standard redox potential of a compound is the reduction/oxidation potential measured under standard conditions, defined at pH = 7.0 versus the hydrogen electrode. On this scale, the potential of 02/water is +815 mV, and the potential of water/H2 is 414 mV. A characteristic of redox reactions involving hydrogen transfer is that the redox potential changes with pH. The oxidation of hydrogen H2 = 2H + 2e is an m = 2 reaction, for which the potential is —414 mV at pH 7, changing by 59.2 mV per pH unit at 30°C. 

Chlorine is released as HCl, which dissociates upon dissolution in water to generate Cl (aq). Sulfur is released as either H2S or SO2. Both are transformed into S04(aq) through chemical reactions involving oxidation by O2 and dissociation/dissolution in water. The amounts of primary magmatic volatiles that have been degassed thus far are given in Table 21.5. About half of the chlorine has been retained in the ocean and the other half has been converted into evaporite minerals. In comparison, virtually... 

The ready availability of electricity following the invention by Alssandro Volta of his famous pile in 1800 prompted, from an early date, the study of its effects on condensed matter and, most particularly, the decomposition of water by electrolysis involving chemical reactions at the electrodes. Work developed to the point where, by the middle of the second half of the nineteenth century, well-established industrial processes for the manufacture of aluminium and chlorine gas operated by electrolysis. 

Balancing the chemical equation for a redox reaction can be a real challenge, especially when water is involved in the reaction and we must include H20, H+, or OH-. In such cases, it can help to balance the reduction and oxidation half-reactions separately and then add the two balanced half-reactions together. For the latter step, we match the number of electrons released by oxidation with the number used in reduction. The number of electrons in the two half-reactions must match, because electrons are neither created nor destroyed in chemical reactions. The procedure is outlined in Toolbox 12.1 and illustrated in Examples 12.1 and 12.2. 

When an aqueous salt solution is electrolyzed, the electrode reactions may differ from those for electrolysis of the molten salt because water may be involved. In the electrolysis of aqueous sodium chloride, for example, the cathode half-reaction might be either the reduction of Na+ to sodium metal, as in the case of molten sodium chloride, or the reduction of water to hydrogen gas ... 

Several of the key issues are reflected in the debate over the appropriate use of pe to describe redox conditions in natural waters (129-131). The parameter is defined in terms of the activity of solvated electrons in solution (i.e., pe = - log e ), but the species e aq does not exist under environmental conditions to any significant degree. The related concept of pe (132), referring to the activity of electrons in the electrode material, may have a more realistic physical basis with respect to electrode potentials, but it does not provide an improved basis for describing redox transformations in solution. The fundamental problem is that the mechanisms of oxidation and reduction under environmental conditions do not involve electron transfer from solution (or from electrode materials, except in a few remediation applications). Instead, these mechanisms involve reactions with specific oxidant or reductant molecules, and it is these species that define the half-reactions on which estimates of environmental redox reactions should be based. 

Another type of photochemical reaction involving a pyrimidine base is the addition of a molecule of water across the 5,6 double bond of C to yield a 5,6-dihydro-6-hydroxy derivative called the cytosine hydrate. The quantum yield for the formation of cytosine hydrates in UV-irradiated DNA is greater in single-stranded than in duplex-DNA (45). Hydrates of cytosine, deoxycytidine, CMP, or dCMP are unstable, readily reverting to the parent form by rehydration (45). However, their half-life is dramatically increased in DNA, and cytosine hydrate may be the major nondimer C photoproduct. Cytosine hydrate can undergo deamination and dehydration to yield uracil (1). The hydrate of 5-methylcytosine may undergo deamination to yield 5-thymine hydrate, which can convert to thymine upon dehydration (1). 

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