Methods using mercury compounds

Many other methods available for hydrogen sulphide determinations have not been applied in routine work. Potentiometric titration with HgQ2 (Bouligue, 1981) or gravimetric methods, e.g., precipitation of HgS (Dyrssen et al., 19%) should be avoided because of detrimental effects on the environment. In Sweden such methods are not allowed in environmental routine work and will probably be illegal in other EU countries. 

Parsons, T.R., Maita, Y., Lalli, C.M. (1984), A Manual of Chemical and Biological Methods for Seawater Analysis. Oxford Pergamon Press, 1984 pp.149-153. 

Skopintsev, RA., Karpov, A.V., Vershinina, O.A. (1959), Transact. Mar. Hydrophys Inst., Academy of Sciences of the USSR., Translated and produced by Scripta Technica Inc. tor the American Geophysical Union pp. 55-72. 

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Methyl ketones are important intermediates for the synthesis of methyl alkyl carbinols, annulation reagents, and cyclic compounds. A common synthetic method for the preparation of methyl ketones is the alkylation of acetone derivatives, but the method suffers limitations such as low yields and lack of regioselectivity. Preparation of methyl ketones from olefins and acetylenes using mercury compounds is a better method. For example, hydration of terminal acetylenes using HgSO gives methyl ketones cleanly. Oxymercuration of 1-olefins and subsequent oxidation with chromic oxide is... 

D.M. Sanchez, R. Martin, R. Morante, J. Marin, and M.L. Munuera. Preconcentration speciation method for mercury compounds in water samples using solid phase extraction followed by reversed-phase high-performance liquid chromatography. Talanta 52 671-679, 2000. 

Magnesium haUde and alkyl magnesium haUde precipitate and the alkyl magnesium compound remains in solution. Filtration (qv) followed by drying the filtrate yields soHd magnesium alkyl (11). Another preparation method is that of metal exchange using mercury alkyl in ether. 

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. 

When the mercury present in the atmosphere is primarily in the form of an organic mercury compound, it may be preferable to utilise an aqueous scmbber. This method is particularly useful for control of emissions from reactors and from dryers. For efficient and economical operation, an aqueous solution of caustic soda, sodium hypochlorite, or sodium sulfide is reckculated through the scmbber until the solution is saturated with the mercury compound. 

Another method of removing mercury compounds from aqueous solution is to treat them with water-soluble reducing agents, thus hberating metallic mercury (26). The use of formaldehyde (qv) at a pH of 10—12 also is recommended. 

Atomic absorption spectroscopy is more suited to samples where the number of metals is small, because it is essentially a single-element technique. The conventional air—acetylene flame is used for most metals however, elements that form refractory compounds, eg, Al, Si, V, etc, require the hotter nitrous oxide—acetylene flame. The use of a graphite furnace provides detection limits much lower than either of the flames. A cold-vapor-generation technique combined with atomic absorption is considered the most suitable method for mercury analysis (34). 

MDHS 14 General method for the gravimetric determination of respirable and total dust MDHS 15 Carbon disulphide MDHS 16 Mercury vapour in air Laboratory method using hopcalite adsorbent tubes, and acid dissolution with cold vapour atomic absorption spectrometric analysis MDHS 17 Benzene in air Laboratory method using charcoal adsorbent tubes, solvent desorption and gas chromatography MDHS 18 Tetra alkyl lead compounds in air Continuous on-site monitoring method using PAC Check atomic absorption spirometry... 

Dining interaction at ambient temperature in a bomb to produce poly (carbon monofluoride), admission of fluorine beyond a pressure of 13.6 bar must be extremely slow and carefully controlled to avoid a violently exothermic explosion [1], Previously it had been shown that explosive interaction of carbon and fluorine was due to the formation and decomposition of the graphite intercalation compound, poly (carbon monofluoride) [2], Presence of mercury compounds prevents explosion during interaction of charcoal and fluorine [3], Reaction of surplus fluorine with graphite or carbon pellets was formerly used as a disposal method, but is no longer recommended. Violent reactions observed when an exhausted trap was opened usually involved external impact on the metal trap, prodding the trap contents to empty the trap, or possibly ingress of moist air... 

A number of analytical methods for the separation of organic mercury compounds use an initial extraction of the organic materials with an organic solvent. Klisenko and Shmigidina [83] then converted both the inorganic mercury held in the aqueous fraction and the organic mercury in the chloroform extract to dithizonate, separated the components on chromatographic columns, and determined the concentration of the various fractions by comparison with reference standards. This method is semi-quantitative at best. 

Differentiation of inorganic and organic mercury can be achieved in a number of different ways, many of which depend upon the reduction and vapourisation of the inorganic mercury, followed by reduction [84] or oxidation [85,86] of the organic mercury compounds, and a final measurement by atomic absorption or mass spectrometry. Similar methods of separation of the inorganic and organic components are used in the pretreatment of samples where the final analysis for mercury is to be made by neutron activation analysis [87,88]. 

Several other methods of generating dihalocarbenes in solution have been reported the most useful of these appears to be the thermolysis of phenyltrihalo-metkyl mercury compounds as reported by Seyferth and co-workers 3 7a although other organometallic precursors have also been employed 37b ... 

The method used to dissolve samples may have an important impact on the quality of the data for some elements. Obviously, if the sample has not been fully dissolved, then quantification will give less than the true yield for some or all elements. Some individual elements may also form insoluble species or complexes during dissolution (e.g., Sn, Cr), and special precautions are necessary to ensure that such complexes are dissolved. Mercury in solution will often be absorbed onto the surface of glass vessels. Quantification will also be less than expected where volatile elements or their compounds are lost a process which may be aggravated if heating in an open vessel. 

A method [62] has been described for the determination of down to 2.5pg kg-1 alkylmercury compounds and inorganic mercury in river sediments. This method uses steam distillation to separate methylmercury in the distillate and inorganic mercury in the residue. The methylmercury is then determined by flameless atomic absorption spectrophotometry and the inorganic mercury by the same technique after wet digestion with nitric acid and potassium permanganate [63]. The well known adsorptive properties of clays for alkylmercury compounds does not cause a problem in the above method. The presence of humic acid in the sediment did not depress the recovery of alkylmercury compounds by more than 20%. In the presence of metallic sulphides in the sediment sample the recovery of alkylmercury compounds decreased when more than lmg of sulphur was present in the distillate. The addition of 4M hydrochloric acid, instead of 2M hydrochloric acid before distillation completely, eliminated this effect giving a recovery of 90-100%. 

Production of ammonia (NH ) Anhydrous (dry) ammonia is the fifth most produced industrial compound. The Haber-Bosch process uses steam on hot coke, which is mostly used in South Africa. In the United States, it is mostly produced from partial combustion of natural gas (methane) or by combining several gases using steam. Other methods use coke-oven gas, refinery gas (mostly methane), or even solar energy. Ammonia is toxic if inhaled and has a high pH value when mixed with water (hydration) to form ammonium hydroxide (NH OH), which has many uses, including as a household cleaner. Ammonia forms many compounds, including ammonium nitrate in fertilizer, rocket fuel, and explosives. Ammonia is also explosive when mixed with mercury or silver or when mixed as part of nitrocellulose. 

The hydration of alkenes is one important method of synthesizing alcohols. Industrially, sulfuric acid is used as a catalyst, while small-scale preparations often utilize toxic mercury compounds. (Definitely not the kind of stuff you want to drink.)... 

Mercury(II) coordination compounds containing Se or Te donor atoms constitute a rather neglected area of coordination chemistry. Often the species show similarities to the corresponding sulfur compounds (see Table 17). Mercury(II) selenide, HgSe, and mercury(II) telluride, HgTe, are simply formed by direct combination of the elements.4 Single crystals are available by chemical transport methods using a pure H2 or Ar stream.402 X-Ray diffraction... 

Mercury represents a serious environmental risk, and the study of removal of mercury from wastewater has received considerable attention in recent years. Mercury concentration was usually reduced by deposition on a cathode with high surface area. Removal of mercury is studied using extended surface electrolysis which reduces the level of mercury to below acceptable concentrations of 0.01 ppm in wastes by employing a Swiss roll cell with a cadmium-coated, stainless-steel cathode. An industrial cell with a fluidized bed electrode has also been studied. Graphite, as an efficient porous electrode, has been used to remove traces of mercuric ions form aqueous electrolyte solutions. In order to apply the electrochemical method for some effluents, it is necessary to use sodium hypochlorite to convert elemental mercury and less soluble mercury compounds to water-soluble mercuric-chloride complex ions. 

Mercury may be present in air in different chemical states such as the elemental form (as a vapour or adsorbed on particular matter) or in the form of volatile mercury compounds (mercury chloride, methyl-mercuric chloride, and dimethyl mercury). Although elemental mercury is only one of the mercury forms which is not as toxic as its organic or ionic forms, analytical determination of elemental mercury is of special importance. Such analysis is used not only for determination of elemental mercury in environment, but also as a method for determination of other forms of mercury after reductive treatment. 

The commercial production of mercury fungicides from organolead compounds is based on patents by Kharasch 184,185). The mercury compounds are used in the disinfection of seeds and grains. Typical compounds are ethylmercuric chloride, ethylmercuric sulfate, ethyl-mercuric phosphate, phenylmercuric acetate, and compounds derived from substituted phenols and ureas. The manufacture of these compounds was reviewed by Whelen in 1957 310>. The alkylation reaction is a general reaction, and a number of additional patents has been issued on methods similar to Whelen s. A representative equation is ... 

Both lead and mercury speciation has been performed by Shum and coworkers [43]. Direct injection nebulization and an ion-pair separation with a microbore LC column were used with ICP-MS detection. A mobile phase of 20 80% v/v ace-tonitrile/water with 5 mM ammonium pentanesulfonate ion pairing reagent at pH 3.4 was used to separate inorganic lead, inorganic mercury, and three organomer-cury species. Detection limits, based on peak area calculations, were 0.2 pg of Pb for all the lead compounds and 7-18 pg of Hg for the mercury compounds. Spiked urine samples were analyzed to evaluate the performance of the method. 

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