Mercury and compounds

Representative Chemicaes Aldrin (CAS 309-00-2) Dieldrin (CAS 60-57-1) Alkyl-lead (CAS 7439-92-1) Benzo(d )pyrene (CAS 50-32-8) Chlordane (CAS 57-74-9) Dichlorodiphenyltrichloroethane (DDT) (CAS 50-29-3) Hexachlorobenzene (CAS 118-74-1) Mercury and compounds (CAS 7439-97-6) Mirex (CAS 2385-85-5) Octachlorostyrene (CAS 29082-74-4) Polychlorinated biphenyls (PCBs) (CAS 11097-69-1 for Arochlor 1254) 2,3, 7,8-Tetrachlorodibenzo-/7-dioxin (TCDD) (CAS 1746-01-6) and chemically similar compounds collectively known as dioxins and furans Camp-hechlor (toxaphene) (CAS 8001-35-2)... 

Hydrogen chloride (98) Hydrogen cyanide (133) Hydrogen sulfide (135) Mercury and compounds (52) Methanol (137)... 

Mercury and compounds Methanol Methyl ethyl ketone... 

Methods for the detection of toxic substances in air. Booklet No. 13 Mercury and Compounds of Mercury. Her Majesties Stationary Office, London. (1957). 

The more noble metals (for example copper, mercury and silver) can form oxides, and exhibit variable oxidation state in such compounds (for example CU2O, CuO), but it is not easy to prepare such oxides by direct action of oxygen on the metal, and elevated temperatures are necessary. Moreover, in the case of silver and mercury, loss of oxygen from the oxide by heating is easy. The oxidesare, however, basic (for example Ag20 - Ag, CuO - Cu in acids). 

Mercury(I) compounds in solution give a white precipitate with chloride ion. blackened by ammonia (p. 437) alkalis and reducing agents generally produce black or grey mercury from mercury(I) compounds. 

The analytical reagent grade is suitable for most purposes. The commercial substance may be purifled by shaking for 3 hours with three portions of potassium permanganate solution (5 g. per litre), twice for 6 hours with mercury, and Anally with a solution of mercuric sulphate (2-5 g. per litre). It is then dried over anhydrous calcium chloride, and fractionated from a water bath at 55-65°. The pure compound boils at 46-5°/760 mm. 

Laser isotope separation techniques have been demonstrated for many elements, including hydrogen, boron, carbon, nitrogen, oxygen, sHicon, sulfur, chlorine, titanium, selenium, bromine, molybdenum, barium, osmium, mercury, and some of the rare-earth elements. The most significant separation involves uranium, separating uranium-235 [15117-96-1], from uranium-238 [7440-61-1], (see Uranium and uranium compounds). The... 

Regulations. In order to decrease the amount of anthropogenic release of mercury in the United States, the EPA has limited both use and disposal of mercury. In 1992, the EPA banned land disposal of high mercury content wastes generated from the electrolytic production of chlorine—caustic soda (14), accompanied by a one-year variance owing to a lack of available waste treatment faciUties in the United States. A thermal treatment process meeting EPA standards for these wastes was developed by 1993. The use of mercury and mercury compounds as biocides in agricultural products and paints has also been banned by the EPA. 

The biochemical basis for the toxicity of mercury and mercury compounds results from its ability to form covalent bonds readily with sulfur. Prior to reaction with sulfur, however, the mercury must be metabolized to the divalent cation. When the sulfur is in the form of a sulfhydryl (— SH) group, divalent mercury replaces the hydrogen atom to form mercaptides, X—Hg— SR and Hg(SR)2, where X is an electronegative radical and R is protein (36). Sulfhydryl compounds are called mercaptans because of their ability to capture mercury. Even in low concentrations divalent mercury is capable of inactivating sulfhydryl enzymes and thus causes interference with cellular metaboHsm and function (31—34). Mercury also combines with other ligands of physiological importance such as phosphoryl, carboxyl, amide, and amine groups. It is unclear whether these latter interactions contribute to its toxicity (31,36). 

Use of mercury and mercury compounds for agricultural purposes was banned by the EPA in 1978, and use in paper and pulp is beUeved to have been discontinued. 

By 1992, use of mercury and mercury compounds in paints was completely baimed by the EPA. 

The toxic nature of mercury and its compounds has caused concern over environmental pollution, and governmental agencies have imposed severe restrictions on release of mercury compounds to waterways and the air (see Mercury). Methods of precipitation and agglomeration of mercurial wastes from process water have been developed. These methods generally depend on the formation of relatively insoluble compounds such as mercury sulfides, oxides, and thiocarbamates. MetaUic mercury is invariably formed as a by-product. The use of coprecipitants, which adsorb mercury on their surfaces facihtating removal, is frequent. 

The covalent character of mercury compounds and the corresponding abiUty to complex with various organic compounds explains the unusually wide solubihty characteristics. Mercury compounds are soluble in alcohols, ethyl ether, benzene, and other organic solvents. Moreover, small amounts of chemicals such as amines, ammonia (qv), and ammonium acetate can have a profound solubilizing effect (see COORDINATION COMPOUNDS). The solubihty of mercury and a wide variety of mercury salts and complexes in water and aqueous electrolyte solutions has been well outlined (5). 

Mercury Telluride. Compounds of mercury with tellurium have gained importance as semiconductors with appHcations in infrared detection (9) and solar cells (10). The ratio of the components is varied, and other elements such as cadmium, zinc, and indium are added to modify the electronic characteristics. 

The toxic effects of mercury and mercury compounds as well as their medicinal properties have been known for many centuries. In the first century AD, Pliny indicated the use of mercuric sulfide (cinnabar or vermilion) in medicine and in cosmetics. This compound was probably known to the Greeks in the time of Aristotle (13). 

Galen, a physician whose views outUved him by about a thousand years, died about 200 AD. He beUeved that mercurials were toxic, and did not use any mercury compound therapeutically. However, as a result of Arabian influence, the therapeutic uses of mercury were slowly recognized by Western Europe. In the thirteenth century mercury ointments were prescribed for treating chronic diseases of the skin. Mercury and its compounds, such as mercurous chloride, mercuric oxide, mercuric chloride, and mercuric sulfide, were used widely from the fifteenth to the nineteenth centuries, and to some extent in the twentieth century. During the first half of the twentieth century, the primary therapeutic uses of mercury included bactericidal preparations, such as mercuric chloride, mercuric oxycyanide, and mercuric oxide and diuretics, such as aryl HgX (Novasural) and mercurated ahyl derivatives (14). 

Toxicity. Inorganic mercury compounds, aryl mercury compounds, and alkoxy mercurials are generahy considered to be quite similar in their toxicity. Alkyl mercury compounds are considered to be substantiahy more toxic and hazardous. Mercury and its compounds can be absorbed by ingestion, absorption through the skin, or by inhalation of the vapor. The metal itself, however, rarely produces any harmful effects when ingested (16). 

A -Pyrazolines such as (410) are oxidized by iodine, mercury(II) acetate and trityl chloride to pyrazolium salts (411), and compound (410) even reduces silver nitrate to Ag° (69JOU1480). Electrochemical oxidation of l,3,5-triaryl-2-pyrazolines has been studied in detail (74BSF768, 79CHE115). They Undergo oxidative dimerization and subsequent transformation into the pyrazole derivative (412). 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

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