Redox reactions, atmospheric

The last chapter in this introductory part covers the basic physical chemistry that is required for using the rest of the book. The main ideas of this chapter relate to basic thermodynamics and kinetics. The thermodynamic conditions determine whether a reaction will occur spontaneously, and if so whether the reaction releases energy and how much of the products are produced compared to the amount of reactants once the system reaches thermodynamic equilibrium. Kinetics, on the other hand, determine how fast a reaction occurs if it is thermodynamically favorable. In the natural environment, we have systems for which reactions would be thermodynamically favorable, but the kinetics are so slow that the system remains in a state of perpetual disequilibrium. A good example of one such system is our atmosphere, as is also covered later in Chapter 7. As part of the presentation of thermodynamics, a section on oxidation-reduction (redox) is included in this chapter. This is meant primarily as preparation for Chapter 16, but it is important to keep this material in mind for the rest of the book as well, since redox reactions are responsible for many of the elemental transitions in biogeochemical cycles. 

Owing to the high availability of O2 in air, redox reactions there are extremely one-sided, with reduced compounds that may enter the atmosphere becoming oxidized at various rates. How-... 

The base was being prepared by distilling a mixture of hydroxylamine hydrochloride and sodium hydroxide in methanol under reduced pressure, and a violent explosion occurred towards the end of distillation [1], probably owing to an increase in pressure above 53 mbar. It explodes when heated under atmospheric pressure [2], Traces of hydroxylamine remaining after reaction with acetonitrile to form acetamide oxime caused an explosion during evaporation of solvent. Traces can be removed by treatment with diacetyl monoxime and ammoniacal nickel sulfate, forming nickel dimethylglyoxime [3], An account of an extremely violent explosion towards the end of vacuum distillation had been published previously [4], Anhydrous hydroxylamine is usually stored at 10°C to prevent internal oxidation-reduction reactions which occur at ambient temperature [5], See other REDOX REACTIONS... 

Fe-S complexes have important functions in today s living systems, in enzymes such as the ferredoxins and oxidoreductases, as well as in electron transport proteins. It is striking that these redox reactions mainly involve elements and compounds such as CO, H2 and N2, which were probably also components of the primeval Earth s atmosphere. Thus, the assumption of an active involvement of Fe-S clusters in a (hypothetical) Fe-S world in processes which finally led to biogenesis appears completely reasonable We now have a background to the theory of the chemoau-totrophic origin of life . 

Hydrogen peroxide plays an important role in many processes in the atmosphere and in natural aqueous systems. It affects numerous redox reactions, which in turn influence the stability and transport of other chemical substances, e.g., pollutants. In the atmosphere, hydrogen peroxide is believed to be involved in several important oxidation reactions, e.g., conversion of sulfur dioxide to sulfuric acid... 

A solution of the isolated platinum blue compound usually contains several chemical species described in the previous section. Such complicated behaviors had long been unexplored, but were gradually unveiled as a result of the detailed equilibrium and kinetic studies in recent years. The basic reactions can be classified into four categories (l)HH-HT isomerization (2) redox disproportionation reactions (3) ligand substitution reactions, especially at the axial coordination sites of both Pt(3.0+)2 and Pt(2.5+)4 and (4) redox reactions with coexisting solvents and atmosphere, such as water and 02. In this chapter, reactions 1-4 are summarized. 

At the same time, this redox lability makes Mo well suited as a cofactor in enzymes that catalyze redox reactions. An example is the prominence of Mo in nitrogen fixation. This prokaryotic metabolism, the dominant pathway for conversion of atmospheric Nj to biologically-useful NH, utilizes Mo (along with Fe) in the active site of the nitrogenase enzyme that catalyzes Nj reduction. Alternative nitrogenases that do not incorporate Mo have been identified, but are markedly less efficient (Miller and Eady 1988 Eady 1996). 

Faust, B. C., A Review of the Photochemical Redox Reactions of Iron(III) Species in Atmospheric, Oceanic, and Surface Waters Influences on Geochemical Cycles and Oxidant Formation, in Aquatic and Surface Photochemistry (G. Helz, R. Zepp, and D. Crosby, Eds.), Chap, f, pp. 3-37, Lewis, Boca Raton, FL, 1994b. 

In this new process the H2S/SO2 reaction is carried out in liquid sulfur at pressures in excess of five atmospheres. Typical Claus catalysts are still employed but temperatures are lower (below the dewpoint of sulfur) and thus the redox reaction occurs in the liquid sulfur phase at the surface of the catalyst. Vapor losses due to sulfur mist entrainment are reduced and interstage condensers in the tradition Claus train are not required thus avoiding wasteful heat transfer problems. The authors claim that overall sulfur recoveries in excess of 99% are possible without the use of tail gas clean up units. 

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