Absence of oxygen

Pasteur effect Yeast and other cells can break down sugar in the presence of oxygen (eventually to CO2 and H2O) or in its absence (to CO2 and ethanol). The decomposition of sugar is often greater in the absence of oxygen than in its presence, i.e. the Pasteur effect. With oxygen, less toxic products (alcohol) are produced and the breakdown is more efficient in terms of energy production. 

In the absence of oxygen, gallium and indium are unaffected by water. Thallium, the most metallic element in Group III, reacts slowly with hot water and readily with steam to produce thallium(I) oxide, TI2O. 

Furfural is very thermally stable in the absence of oxygen. At temperatures as high as 230°C, exposure for many hours is required to produce detectable changes in the physical properties of furfural, with the exception of color (17). However, accelerating rate calorimetric data shows that a temperature above 250°C, in a closed system, furfural will spontaneously and exothermically decompose to furan and carbon monoxide with a substantial increase in pressure. The pressure may increase to 5000 psi or more, sufficient to shatter the container (18). 

Acrylonitrile will polymerize violendy in the absence of oxygen if initiated by heat, light, pressure, peroxide, or strong acids and bases. It is unstable in the presence of bromine, ammonia, amines, and copper or copper alloys. Neat acrylonitrile is generally stabilized against polymerization with trace levels of hydroquinone monomethyl ether and water. 

Radiation Effects. Polytetrafluoroethylene is attacked by radiation. In the absence of oxygen, stable secondary radicals are produced. An increase in stiffness in material irradiated in vacuum indicates cross-linking (84). Degradation is due to random scission of the chain the relative stabiUty of the radicals in vacuum protects the materials from rapid deterioration. Reactions take place in air or oxygen and accelerated scission and rapid degradation occur. 

The degree to which radiation exposure affects FEP resins is determined by the energy absorbed, regardless of the type of radiation. Changes in mechanical properties depend on total dosage, but ate independent of dose rate. The radiation tolerance of FEP in the presence or absence of oxygen is higher than that of PTFE by a factor of 10 1. 

More recent work reports the onset of thermal degradation at lower temperatures and provides a clearer picture of the role of oxygen (73—75). In the presence of oxygen, backbone oxidation and subsequent cleavage reactions initiate decomposition. In the absence of oxygen, dehydrofluorination eventually occurs, but at significantly higher temperatures. 

Coal can be converted to gas by several routes (2,6—11), but often a particular process is a combination of options chosen on the basis of the product desired, ie, low, medium, or high heat-value gas. In a very general sense, coal gas is the term appHed to the mixture of gaseous constituents that are produced during the thermal decomposition of coal at temperatures in excess of 500°C (>930°F), often in the absence of oxygen (air) (see Coal CONVERSION PROCESSES, gasification) (3). A soHd residue (coke, char), tars, and other Hquids are also produced in the process ... 

Germanium monoxide [20619-16-3], GeO, can best be prepared in pure form by heating a mixture of Ge and Ge02, in the absence of oxygen. At temperatures above 7I0°C, GeO sublimes from the mixture and condenses as a glassy deposit in the cooler part of the reaction vessel. Germanium monoxide is stable at room temperature. 

Pyrolysis. Heating in the absence of oxygen releases moisture at low temperatures, carbon dioxide at temperatures >200° C, and a variety of gaseous products at very high temperatures. Acid washing of the raw coal is used to remove extractable cations, followed by treatment with selected cations. Yields of CO2, CO, CH, H2, and H2O depend on the amounts of inorganic species in the coal (42). 

Thermal decomposition of hydrocarbons is carried out ia the absence of oxygen and at a high temperature required to break the carbon—hydrogen... 

Noranda Process. When pyrites are heated to about 540°C in the absence of oxygen, about half of the sulfur content in the pyrites evolves in the elemental form. Noranda Mines Ltd. and BatteUe Memorial Institute developed a process based on this property to recover elemental sulfur from pyrite (27). The first commercial plant was built at Welland, Ontario, in 1954 but operated on an experimental basis for only a few years before being closed for economic reasons. 

Chemical Properties. Anhydrous sodium dithionite is combustible and can decompose exothermically if subjected to moisture. Sulfur dioxide is given off violentiy if the dry salt is heated above 190°C. At room temperature, in the absence of oxygen, alkaline (pH 9—12) aqueous solutions of dithionite decompose slowly over a matter of days. Increased temperature dramatically increases the decomposition rate. A representation of the decomposition chemistry is as follows ... 

In the alkanethiol case, the reaction may be considered formally as an oxidative addition of the S—H bond to the gold surface, followed by a reductive elimination of the hydrogen. When a clean gold surface is used, the proton probably ends as a molecule. Monolayers can be formed from the gas phase (241,255,256), in the complete absence of oxygen ... 

Temperature. The temperature for combustion processes must be balanced between the minimum temperature required to combust the original contaminants and any intermediate by-products completely and the maximum temperature at which the ash becomes molten. Typical operating temperatures for thermal processes are incineration (750—1650°C), catalytic incineration (315—550°C), pyrolysis (475—815°C), and wet air oxidation (150—260°C at 10,350 kPa) (15). Pyrolysis is thermal decomposition in the absence of oxygen or with less than the stoichiometric amount of oxygen required. Because exhaust gases from pyrolytic operations are somewhat "dirty" with particulate matter and organics, pyrolysis is not often used for hazardous wastes. 

At higher temperatures the stable form is valentinite, which consists of infinite double chains. The orthorhombic modification is metastable below 570 °C however, it is sufficientiy stable to exist as a mineral. Antimony trioxide melts in the absence of oxygen at 656°C and partially sublimes before reaching the boiling temperature, 1425°C. The vapor at 1500°C consists largely of Sb O molecules, but these dissociate at higher temperatures to form Sb202 molecules. 

Chlorine and bromine add to benzene in the absence of oxygen and presence of light to yield hexachloro- [27154-44-5] and hexabromocyclohexane [30105-41-0] CgHgBr. Technical benzene hexachloride is produced by either batch or continuous methods at 15—25°C in glass reactors. Five stereoisomers are produced in the reaction and these are separated by fractional crystallization. The gamma isomer (BHC), which composes 12—14% of the reaction product, was formerly used as an insecticide. Benzene hexachloride [608-73-17, C HgCl, is converted into hexachlorobenzene [118-74-17, C Clg, upon reaction with ferric chloride in chlorobenzene solution. 

At ambient temperatures beryUium is quite resistant to oxidation highly poHshed surfaces retain the brilliance for years. At 700°C oxidation becomes noticeable in the form of interference films, but is slow enough to permit the working of bare beryUium in air at 780°C. Above 850°C oxidation is rapid to a loosely adherent white oxide. The oxidation rate at 700°C is paraboHc but may become linear at this temperature after 24—48 hours of exposure. In the presence of moisture this breakaway oxidation occurs more rapidly and more extensively. BeryUium oxide [1304-56-9] BeO, forms rather than beryUium nitride [1304-54-7] Be2N2, but in the absence of oxygen, nitrogen attacks beryUium above 900°C. 

Beryllium Nitride. BeryUium nitride [1304-54-7], Be N2, is prepared by the reaction of metaUic beryUium and ammonia gas at 1100°C. It is a white crystalline material melting at 2200°C with decomposition. The sublimation rate becomes appreciable in a vacuum at 2000°C. Be2N2 is rapidly oxidized by air at 600°C and like the carbide is hydrolyzed by moisture. The oxide forms on beryllium metal in air at elevated temperatures, but in the absence of oxygen, beryllium reacts with nitrogen to form the nitride. When hot pressing mixtures of beryUium nitride and sUicon nitride, Si N, at 1700°C, beryllium sUicon nitride [12265-44-0], BeSiN2, is obtained. BeSiN2 may have appHcation as a ceramic material. 

A Japanese process developed by Taogosei Chemical Co. chlorinates ethylene directly in the absence of oxygen at 811 kPa (8 atm) and 100—130°C (32). The products ate tetrachlorethanes and pentachloroethane [76-01-7J, which ate then thermally cracked at 912 kPa (9 atm) and 429—451°C to produce a mixture of trichloroethylene, perchloroethylene [127-18-4] and hydrochloric acid. 

Copper Oxides. Coppet(I) oxide [1317-39-17 is a cubic or octahedral naturally occurring mineral known as cuprite [1308-76-5]. It is ted or reddish brown in color. Commercially prepared coppet(I) oxides vary in color from yellow to orange to ted to purple as particle size increases. Usually coppet(I) oxide is prepared by pytometaHutgical methods. It is prepared by heating copper powder in air above 1030°C or by blending coppet(II) oxide with carbon and heating to 750°C in an inert atmosphere. A particularly air-stable coppet(I) oxide is produced when a stoichiometric blend of coppet(II) oxide and copper powder ate heated to 800—900°C in the absence of oxygen. Lower temperatures can be used if ammonia is added to the gas stream (27-29). 

Anodic Inhibitors. Passivating or anodic inhibitors produce a large positive shift in the corrosion potential of a metal. There are two classes of anodic inhibitors which are used for metals and alloys where the anodic shift in potential promotes passivation, ie, anodic protection. The fkst class includes oxidking anions that can passivate a metal in the absence of oxygen. Chromate is a classical example of an oxidking anodic inhibitor for the passivation of steels. 

Polymer units formed by either 3,4- or 1,4-addition do not evolve hydrogen chloride under these conditions in the absence of oxygen. Also, chain scission resulting in the formation of lower molecular weight polymers does not occur (104). 

Ah these polymerizations proceed only in the absence of oxygen or water, which react with the highly reactive propagating species. Polymerization is usuahy carried out in an inert, hydrocarbon solvent and under a nitrogen blanket. Under these conditions, polymers with narrow molecular-weight distributions and precise molecular weights can be produced in stoichiometric amounts. 

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