Condensed arsenates

Arsenic [7440-38-2] M 74.9, m 816°. Heated under vacuum at 350° to sublime oxides, then sealed in a Pyrex tube under vacuum and sublimed at 600°, the arsenic condensing in the cooler parts of the tube. Stored under vacuum [Shih and Peretti J Am Chem Soc 75 608 1953], POISONOUS. 

The working time of HT-probes decreases quickly over glass meltings with increasing temperature [55]. Vapors of the oxides, above all of sodium, potassium, silicium, lead, an-timon and arsen condense on the probe material in the temperature gradient from the inside to the outside of the tank wall. The condensed substances penetrate into the ceramic material over grain boundaries and lead to tube bursts. Thereby the stabilized zirconium dioxid is more sensitive than alumina. Componenu which contain Si02 must not be used in HT-probes [56]. 

Solid arsenic occurs like phosphorus in different modifications. Cray or metallic arsenic is stable. Its structure is rhombohedral with a = 4.13 A. a = 54.2 . If vaporized and condensed at the temperature of liquid air. ydloiv arsenic is formed. At room temperature, yellow arsenic is transformed to metallic arsenic. Condensed on surfaces at 100-20(rC. black arsenic ( arsenic mirror ) is formed. 

As shown in Table 2.4, atomic absorption is extremely sensitive. It is particularly suited to the analyses of arsenic and lead in gasolines, for sodium in fuel oils (where it is the only reliable method) and for mercury in gas condensates. 

Not all molecules striking a surface necessarily condense, and Z in Eq. VII-2 gives an upper limit to the rate of condensation and hence to the rate of evaporation. Alternatively, actual measurement of the evaporation rate gives, through Eq. VII-2, an effective vapor pressure Pe that may be less than the actual vapor pressure P. The ratio Pe/P is called the vaporization coefficient a. As a perhaps extreme example, a is only 8.3 X 10" for (111) surfaces of arsenic [11]. 

Arsenic and antimony resemble phosphorus in having several allotropic modifications. Both have an unstable yellow allotrope. These allotropes can be obtained by rapid condensation of the vapours which presumably, like phosphorus vapour, contain AS4 and Sb4 molecules respectively. No such yellow allotrope is known for bismuth. The ordinary form of arsenic, stable at room temperature, is a grey metallic-looking brittle solid which has some power to conduct. Under ordinary conditions antimony and bismuth are silvery white and reddish white metallic elements respectively. 

In view of the high reactivity and sensitivity to oxidation of o-phenylone-diamine, the normal experimental conditions of the Skraup reaction are modified the condensation is carried out hi the presence of glycerol, arsenic acid solution and dilute sulphuric acid. 

Metafile arsenic can be obtained by the direct smelting of the minerals arsenopyrite or loeUingite. The arsenic vapor is sublimed when these minerals are heated to about 650—700°C in the absence of air. The metal can also be prepared commercially by the reduction of arsenic trioxide with charcoal. The oxide and charcoal are mixed and placed into a horizontal steel retort jacketed with fire-brick which is then gas-fired. The reduced arsenic vapor is collected in a water-cooled condenser (5). In a process used by Bofiden Aktiebolag (6), the steel retort, heated to 700—800°C in an electric furnace, is equipped with a demountable air-cooled condenser. The off-gases are cleaned in a sembber system. The yield of metallic arsenic from the reduction of arsenic trioxide with carbon and carbon monoxide has been studied (7) and a process has been patented describing the gaseous reduction of arsenic trioxide to metal (8). 

Phosphorized deoxidized arsenical copper (alloy 142 (23)) is used for heat exchangers and condenser tubes. Copper-arsenical leaded Muntz metal (alloy 366), Admiralty brass (alloy 443), naval brass (alloy 465), and aluminum brass (alloy 687), all find use in condensers, evaporators, ferrules, and heat exchanger and distillation tubes. The composition of these alloys is Hsted in Table 5. 

Other Arsenic Hydrides. Diarsine [15942-63-9] AS2H4, occurs as a by-product in the preparation of arsine by treatment of a magnesium aluminum arsenide alloy with dilute sulfuric acid and also may be prepared by passing arsine at low pressure through an ozonizer-type discharge tube (19). Diarsine is fairly stable as a gas but quite unstable (above — 100°C) in condensed phases. The for diarsine is +117 4 kJ/mol (28 1 kcal/mol) and... 

Arsenic pentafluoride (arsenic(V) fluoride), AsF, is a colorless gas that condenses to a yellow Hquid its dielectric constant is 12.8 at 20 °C. It is formed by reaction of a mixture of bromine and antimony pentafluoride with arsenic trifluoride. The molecule is a trigonal bipyramid and is somewhat dissociated as indicated by vapor density measurements. 

Admiralty Brass and Naval Brass are 30 and 40% zinc alloys, respectively, to which a 1% tin addition has been added. Resistance to dezincification of Cu—Zn alloys is increased by tin additions. Therefore, these alloys are important for thein corrosion resistance in condenser tube appHcations. In these, as weU as the other higher zinc compositions, it is common to use other alloying additives to enhance corrosion resistance. In particular, a small amount (0.02—0.10 wt %) of arsenic (C443), antimony (C444), or phosphoms (C445) is added to control dezincification. When any of these elements are used, the alloy is referred as being "inhibited." For good stress corrosion resistance, it is recommended that these alloys be used in the fiiUy annealed condition or in the cold worked plus stress reHef annealed condition. 

Many shell-and-tube condensers use copper alloy tubes, such as admiralty brasses (those containing small concentrations of arsenic, phosphorus, or antimony are called inhibited grades), aluminum brasses, and cupronickel austenitic stainless steel and titanium are also often used. Utility surface condensers have used and continue to use these alloys routinely. Titanium is gaining wider acceptance for use in sea water and severe service environments but often is rejected based on perceived economic disadvantages. 

The production of cobalt is usually subsidiary to that of copper or nickel and the methods employed differ widely, depending on which of these it is associated with. In general the ore is subjected to appropriate roasting treatment so as to remove gangue material as a slag and produce a speiss of mixed metal and oxides. In the case of arsenical ores, AS2O6 is condensed and provides a valuable byproduct. In the case of copper ores, the primary process... 

In early times 70/30 brass condenser tubes failed by dezincification and Admiralty brass (70Cu-29Zn-lSn) was brought into use. This proved little better, but some time later the addition of arsenic was found to inhibit dezincification. Failures of Admiralty brass by impingement attack became a serious problem, particularly as cooling water speeds increased with the development of the steam turbine. The introduction of alloys resistant to this type of attack was a great step forward and immediately reduced the incidences of failure. 

In the former Soviet Union much use is made of industrial by-products to prepare acid inhibitors. The PB class is obtained by treating technical butyraldehyde with ammonia and polymerising the resulting aldehyde-ammonia. PB-5, for example, with O-Ol-O-15% of an arsenic salt is used in 20-25% HCl. A mixture of urotropine (hexamethyleneimine, hexamine) with potassium iodide, a regulator and a foaming agent is the ChM inhibitor. BA-6 is prepared from the condensation product of hexamine with aniline. A more recent development is the Katapin series which consists of /7-alkyl benzyl pyridine chlorides Katapin A, for example, is the /7-dodecyl compound. 

Sublimation. This process is employed to separate volatile substances from non-volatile impurities. Iodine, arsenic(III) oxide, ammonium chloride and a number of organic compounds can be purified in this way. The material to be purified is gently heated in a porcelain dish, and the vapour produced is condensed on a flask which is kept cool by circulating cold water inside it. 

The compound, formed by condensation of its vapour at —95°C explodes suddenly at — 67°C. Prepared in another way, it is stable under water but explodes violently in contact with phosphorus or arsenic. 

The stable form of arsenic is the gray or metallic form, although other forms are known. Cooling the vapor rapidly produces yellow arsenic, and an orthorhombic form is obtained if the vapor is condensed in the presence of mercury. Arsenic compounds are used in insecticides, herbicides, medicines, and pigments, and arsenic is used in alloys with copper and lead. A small amount of arsenic increases the surface tension of lead, which allows droplets of molten lead to assume a spherical shape, and this fact is utilized in the production of lead shot. 

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