Oxygen reactions with nonmetals

Like oxygen, sulfur gains two electrons and forms the sulfide ion (S ) when it reacts with metals or with hydrogen. But in its reactions with nonmetals, sulfur can have other oxidation numbers. Much of the sulfur produced in the United States is taken from deposits of elemental sulfur by the Frasch process, shown in Figure 8.8. 

Phosphoms shows a range of oxidation states from —3 to +5 by virtue of its electronic configuration. Elemental P is oxidized easily by nonmetals such as oxygen, sulfur, and halides to form compounds such as 2 5 2 5 reduced upon reaction with metals to generate phosphides. The... 

Mark A. Barteau is Robert L. Pigford Professor and Chair of the Department of Chemical Engineering at the University of Delaware. He received his B.S. degree from Washington University in 1976 and his M.S. (1977) and Ph.D. (1981) from Stanford University. His research area is chemical engineering with specialized interests in application of surface techniques to reactions on nonmetals, hydrocarbon and oxygenate chemistry on metals and metal oxides, scanning probe microscopies, and catalysis by metal oxides. 

Metals react with nonmetals. These reactions are oxidation-reduction reactions. (See Chapters 4 and 18). Oxidation of the metal occurs in conjunction with reduction of the nonmetal. In most cases, only simple compounds will form. For example, oxygen, 02, reacts with nearly all metals to form oxides (compounds containing O2-). Exceptions are the reaction with sodium where sodium peroxide, Na202, forms and the reaction with potassium, rubidium, and cesium where the superoxides, K02, Rb02, and Cs02 form. 

In the first reaction, we have the combination of an active metal with an active nonmetal to form a stable ionic compound. The very active oxygen reacts with hydrogen to form the stable compound water. The hydrogen and potassium are undergoing oxidation, while the oxygen and chlorine are undergoing reduction. 

Iron reacts with nonmetals forming their binary compounds. It combines readily with halogens. Reaction is vigorous with chlorine at moderate temperature. With oxygen, it readily forms iron oxides at moderate temperatures. In a finely divided state, the metal is pyrophoric. Iron combines partially with nitrogen only at elevated temperatures. It reacts with carbon, sulfur, phosphorus, arsenic, and silicon at elevated temperatures in the absence of air, forming their binary compounds. 

Chapter 13. For now we will be satisfied with some general guidelines to help us keep track of electrons in oxidation-reduction reactions. The nonmetals with the highest attraction for shared electrons are in the upper right-hand corner of the periodic table. They are fluorine, oxygen, nitrogen, and chlorine. The relative ability of these atoms to attract shared electrons is... 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

Oxygen forms binary compounds with nearly all elements. Most may be obtained by direct reaction, although other methods (such as the thermal decomposition of carbonates or hydroxides) are sometimes more convenient (see Topic B6). Oxides may be broadly classified as molecular, polymeric or ionic (see Topics B1 and B2). Covalent oxides are formed with nonmetals, and may contain terminal (E=0) or bridging (E-O-E) oxygen. Especially strong double bonds are formed with C, N and S. Bridging is more common with heavier elements and leads to the formation of many polymeric structures such as Si02 (see Topics FT and F4). 

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