Oxygen and Sulfur

Oxygen is by far the most abundant element in Earth s crust, constituting about 46 percent of its mass. In addition, the atmosphere contains about 21 percent molecular oxygen by volume (23 percent by mass). Like nitrogen, oxygen in the free state is a diatomic molecule (O,). In the laboratory, oxygen gas can be obtained by heating potassium chlorate  

The reaction is usually catalyzed by manganese(IV) dioxide (Mn02). Pure oxygen gas can be prepared by electrolyzing water (page 781). Industrially, oxygen gas is prepared by the fractional distillation of liquefied air. Oxygen gas is colorless and odorless. 

Oxygen is a building block of practically all biomolecules, accounting for about a fourth of the atoms in living matter. Molecular oxygen i.s the essential oxidant in the metabolic breakdown of food molecules. Without it, a human being cannot survive for more than a few minutes. 

Although oxygen has two allotropes, O2 and O3, when we speak of molecular oxygen, we normally mean O2. Ozone (O3) is less stable than O2. The O2 molecule is paramagnetic because it contains two unpaired electrons (see Section 10.7). 

Oxygen forms three types of oxides the normal oxide (or simply the oxide), which contains the O ion the peroxide, which contains the Oi ion and the superoxide, which contains the O2 ion  

The ions are all strong Brpnsted bases and react with water as follows  

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This reaction was first described by Gabriel in 1910 (40), when he warmed an acylaminoketone (197a) with an equimolecular amount of phosphorus pentasulfide. The reaction (Scheme 103) is similar to the preparation of other five-membered oxygen- and sulfur-containing rings from 1,4-dicarbonyl compounds. 

The most widely used industrial synthesis of phenol is based on isopropylbenzene (cumene) as the starting material and is shown m the third entry of Table 24 3 The eco nomically attractive features of this process are its use of cheap reagents (oxygen and sulfuric acid) and the fact that it yields two high volume industrial chemicals phenol and acetone The mechanism of this novel synthesis forms the basis of Problem 24 29 at the end of this chapter... 

Ligands Other than Oxygen and Sulfur. See Sec. 3.1.7, Coordination Compounds, for acids containing ligands other than oxygen and sulfur (selenium and tellurium). 

The complex nature of coal as a molecular entity (2,3,24,25,35,37,53) has resulted ia the chemical explanations of coal combustion being confined to the carbon ia the system. The hydrogen and other elements have received much less attention but the system is extremely complex and the heteroatoms, eg, nitrogen, oxygen, and sulfur, exert an influence on the combustion. It is this latter that influences environmental aspects. 

Several oxygen- and sulfur-substituted boranes have been reported (125—130). 1,3,2-Benzodioxaborole [274-07-7] (catecholborane, CB) (15) is the one best studied. It is commercially available or can be prepared by the reaction of catechol with borane-THF (57,131), or by other procedures (132). The product is a Hquid existing as a monomer, remarkably stable to disproportionation. No... 

Fig. 14. Choleic acid inclusion chemistry (a) crystal stmcture of DCA inclusion compound with phenanthrene (b) view along a DCA inclusion helix accommodating DMSO and water guest molecules (oxygen and sulfur atoms and methyl groups are represented by open circles and large and small black...

Pure iron is a silvery white, relatively soft metal and is rarely used commercially. Typical properties are Hsted in Table 1. Electrolytic (99.9% pure) iron is used for magnetic cores (2) (see Magnetic materials, bulk). Native metallic iron is rarely found in nature because iron which commonly exhibits valences of +2 and +3 combines readily with oxygen and sulfur. Iron oxides are the most prevalent form of iron (see Iron compounds). Generally, these iron oxides (iron ores) are reduced to iron and melted in a blast furnace. The hot metal (pig iron) from the blast furnace is refined in steelmaking furnaces to make steel... 

Metallurgy. The strong affinity for oxygen and sulfur makes the rare-earth metals useflil in metallurgy (qv). Mischmetal acts as a trap for these Group 16 (VIA) elements, which are usually detrimental to the properties of steel (qv) or cast iron (qv). Resistance to high temperature oxidation and thermomechanical properties of several metals and alloys are thus significantly improved by the addition of small amounts of mischmetal or its siUcide (16,17). 

The alkylation desctibed in this article is the substitution of a hydrogen atom bonded to the carbon atom of a paraffin or aromatic ring by an alkyl group. The alkylations of nitrogen, oxygen, and sulfur are described in separate articles (see Amines Ethers). 

Hydroxy-, Hydroxyall l-, and Aminoall lpyridines. A full discussion of the tautomerism occurring in heterocycles with oxygen and sulfur substituents has been pubUshed (38). Equation 2 shows the tautomerism expected in 2-pyridone (16) and 4-pyridone (38). 

Occurrence ndPreparation. Carbonyl sulfide is formed by many high temperature reactions of carbon compounds with donors of oxygen and sulfur. A principal route is the foUowiag reaction (30) ... 

Titanium triiodide can be made by direct combination of the elements or by reducing the tetraiodide with aluminum at 280°C in a sealed tube. Til reacts with nitrogen, oxygen, and sulfur donor ligands to give the corresponding adducts (148). 

Od-fumace blacks used by the mbber iadustry contain over 97% elemental carbon. Thermal and acetylene black consist of over 99% carbon. The ultimate analysis of mbber-grade blacks is shown ia Table 2. The elements other than carbon ia furnace black are hydrogen, oxygen, and sulfur, and there are mineral oxides and salts and traces of adsorbed hydrocarbons. The oxygen content is located on the surface of the aggregates as C O complexes. The... 

In bulk form cerium is a reactive metal that has a high affinity for oxygen and sulfur. It has a face centered cubic crystal stmcture, mp 798°C, bp 3443°C, density 6.77 g/mL, and a metallic radius of 182 pm. Detailed chemical and physical property information can be found in the Hterature (1,2). 

Flame Temperature. The adiabatic flame temperature, or theoretical flame temperature, is the maximum temperature attained by the products when the reaction goes to completion and the heat fiberated during the reaction is used to raise the temperature of the products. Flame temperatures, as a function of the equivalence ratio, are usually calculated from thermodynamic data when a fuel is burned adiabaticaHy with air. To calculate the adiabatic flame temperature (AFT) without dissociation, for lean to stoichiometric mixtures, complete combustion is assumed. This implies that the products of combustion contain only carbon dioxide, water, nitrogen, oxygen, and sulfur dioxide. 

The less common heteroatoms are those other than nitrogen, oxygen and sulfur (arid selenium and tellurium which are treated alongside sulfur), i.e. phosphorus, arsenic, antimony, bismuth, the halogens, silicon, germanium, tin, lead, boron and the transition metals. 

Part 2 (Volumes 2 and 3) deals with mono- and poly-cyclic compounds with one or more six-membered heterocyclic ring, with nitrogen, oxygen and sulfur as the heteroatoms. Volume 2 contains the six-membered rings with one nitrogen atom (Part 2A) and Volume... 

The 17% ferritic steels are easier to fabricate than the martensitic grades. They are used extensively in equipment for nitric acid production. The oxygen- and sulfur-resistant 30% chromium steel can be used at temperatures up to 1150°C but only for lightly loaded and well-supported furnace items because of its poor creep and brittlement properties when equipment is down to ambient temperatures [18]. 

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