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Handbook of Extractive Metallurgy
Edited by Fathi Habashi
Weinheim • Chichester • New York • Toronto • Brisbane • Singapore ©VCH Verlagsgesellschaft mbH, Weinheim, Federal Republic of Germany, 1997
MATTHIAS SIMON (§§ 1 7 . 1 - 1 7 . 1 0 , 1 7 . 1 3 - 1 7 . 1 4 ) ; PETER JÖNK (RETIRED) (§ 1 7 . 1 1 ) ; GABRIELE WÜHL-COUTURIER (§ 1 7 . 1 2 ) ; M A X DAUNDERER (§ 17.14)
17.1 Introduction 17.2 Properties
17.2.1 17.2.2 Physical Properties C h e m i c a l Properties Deposits Secondary Sources
Resources and Raw Materials
17.4.1 18.104.22.168 22.214.171.124 126.96.36.199 17.4.2 17.4.3 17.4.4
17.6 891 17.7 892 17.8 893 17.9 893 895 17.10 8 9 5 17.11
188.8.131.52 Water Purification
Quality Specifications Chemical Analysis Storage and Transportation Uses Mercury Alloys Compounds
906 906 907 907 908 910
910 911 913 913 914
Extraction from Primary Sources 895 Beneficiation 895 Processing to Metallic Mercury 895 Furnace Systems 896 Extraction from Secondary Sources 897 Condensation o f Mercury from Furnace Off-Gas 898 Treatment o f t h e Stupp 900
1 7 . 1 1 . 1 Mercury 1 7 . 1 1 . 2 Mercury
1 7 . 1 1 . 3 Mercury Pseudohalides 1 7 . 1 1 . 4 Acetates, Nitrates, Sulfates 1 7 . 1 1 . 5 Mercury-Nitrogen C o m p o u n d s
1 7 . 1 1 . 6 Analysis, Storage, and Transportation; Protective Measures 914
17.5 Environmental Protection
1 7 . 5 . 1 Natural Distribution o f M e r c u r y 184.108.40.206 Mercury in Soil, Plants, and Animals 220.127.116.11 Mercury in Food 1 7 . 5 . 2 M e r c u r y Emissions 18.104.22.168 Gas Purification
901 901 902 904 904
17.12 Selected Organic Compounds 1 7 . 1 3 Economic Aspects 17.14 Toxicology and Occupational Health 17.15 References
915 915 917 920
Mercury (also called quicksilver), symbol Hg from the Greek νδραρ = water and αργνρος = silver, was known as early as 1000 B . C . because of its liquid state at room tem perature ( mp -38.89 °C). The discovery in 1938 of 1 kg of the metal in 2500-year-old sand layers on the eastern coast of Greece in dicates that mercury was used in the extraction of gold at an early date . Mercury was men tioned about 200 B . C . in India as well as in China (Han dynasty).
As early as 1556, GEORGES BAUER, known
Because of the considerable vapor pressure of mercury even at room temperature and the toxicity of its vapors, particularly safe and re liable methods must be used in the extraction of mercury to avoid releasing even the slight est trace of the metal into the environment. The problem of gas and water purification is therefore particularly important.
17.2.1 Physical Properties
Mercury is a silvery-white, shiny metal, which is liquid at room temperature. The most important physical properties are listed below:
Isotope masses (ordered according 2 0 2 , 2 0 0 , 1 9 9 , 2 0 1 t o decreasing abundance) 198 204, 196
mp bp ( 1 0 1 . 3 kPa) - 3 8 . 8 9 °C 357.3 °C
as AGRICOLA, reported five different methods for extracting mercury from its ores . He also realized that mercury vapors are heavier than air and that they could therefore conve niently be trapped in condensers beneath the reaction vessel.
Density (0 °C) 13.5956 g/cm 3 Specific heat capacity c p (0 °C) 0.1397 J g - l K - 1
Heat of fusion Heat of evaporation (357.3 °C) Thermal conductivity (17 °C) Thermal expansion coefficient β (0-100 °C) Electrical conductivity (0 °C) Crystal structure Viscosity (0 °C) Surface tension tcritt pcritt Critical density Evaporation number (25 °C)
11.807 J/g 59.453 kJ/mol 0.082 W cm K 1.826 x 10
-4 -4 -1 -1
The surface tension of mercury is ca. six times greater than that of water, which is the reason for its poor wettability by water.
1.063 x 10
rhombohedral 1.685 mPa •s 480.3 x 10 N/cm 1450 °C 105.5 MPa 5 g/cm
3 -1 -2 -5
The dynamic viscosity η of mercury (Table 17.3) is of the same order of magnitude as that of water . Some other metals, such as gold, silver, and zinc, dissolve readily in mercury to form amalgams. The solubility of mercury in water is strongly temperature dependent . At room temperature, the solubility is ca. 60 μg/L; at 50 °C, ca. 250 μg/L; and at 90 °C, ca. 1100 μg/L. At low temperature, the addition of sodium chloride reduces the water solubil ity.
0.085 mg K cm
Mercury has a relatively high vapor pres sure, even at room temperature. Saturation va por pressures at 0-100 °C are listed in Table 17.1 (corresponding to a specified mercury content in air). The temperature dependence of the density of mercury is given in Table 17.2. Mercury vapor is excited to a state of lumi nescence by electrical discharge (mercury va por lamps). Ultraviolet radiation is released primarily, it can be used to start and to pro mote chemical reactions.
Table 17.1: Saturation vapor pressure of mercury at dif ferent temperatures. t, °C 0 10 20 30 100 p, Pa 0.026 0.070 0.170 0.390 36.841 Hg content in air, g/m3 0.00238 0.00604 0.01406 0.03144 2.40400
Mercury exists in the oxidation states 0, 1+, and 2+; monovalent mercury is found only in Hg-Hg bonds. The redox potentials E 0 at 298.15 K and 101.325 kPa relative to the stan dard hydrogen electrode are as follows :
Hg2+ + 2e2Hg Hg
+ 2e + 2e
+0.920 V +0.797 V 2Hg + 2CH COO 3
Hg (CH COO) + 2e2 3 2
Table 17.2: Density of mercury as a function of tempera ture. t, °C -38.89 0 50 100 150 Density, g/cm3 13.6902 13.5956 13.4733 13.3524 13.2327 t, °C Density, g/cm3 200 250 300 350 13.1139 12.9957 12.8778 12.7640
Table 17.3: Temperature dependence of the dynamic vis cosity of mercury. t, °C -20 -10 0 10 20 30 40 Density, g/cm 3 1.855 1.764 1.685 1.615 1.554 1.499 1.450 t, °C Density, g/cm3 60 80 100 200 300 340 1.367 1.298 1.240 1.052 0.950 0.921
The standard potentials show that mercury is a relatively noble metal. Metallic mercury dissolves in nitric acid, aqua regia, warm concentrated hydrochloric acid and sulfuric acid. It is sparingly soluble in dilute HC1, HBr, and HI as well as in cold sulfuric acid. Most of its chemical compounds have densities of 5-9 g/cm . The oxide of mercury (HgO) decomposes at 400-500 °C. This effect is utilized in the extraction of mercury from oxidic sources. Mercury forms monovalent and divalent compounds with the halogens fluorine, chlorine, bromine, and iodine. It also forms monovalent and divalent compounds with sulfur.
This deposit was probably known to the Celts and Phoenicians. These deposits have been worked since 1497. marl. and finally reverted to Yugoslavia after World War II.473 kg of mercury. The Siele mine recommenced operation only in 1846. to the benefit of the Spanish mines at Almadén. Since then the mines have been under state management. Because mercury ores lie close to the earth's surface. The tectonics of this region are complicated. In 1988 Almadén produced ca. The richest strata contained 12-14% mercury at a depth of 170-200 m. The mines were under Austrian ownership from 1580 to 1918. Although these deposits had been mined by the Etruscans. 90 % of world mining production.6].8% mercury. Minas de Almadén y Arrayanes SA. The third largest mercury deposits in Europe are situated in Idrija in Slovenia. Additional deposits in Yugoslavia are located at Maškara in Croatia. A roughly 25-km-wide. antimonite.5% mercury content in the ore). in 1898. sandstone. Former Yugoslavia. the average mercury content being ca. China.5% mercury. by the Spanish royal house. at present still the largest. bituminous shale. Berg Avala to the south of Beograd in Serbia. Algeria. Needles of coarsely crystalline cinnabar as well as metallic mercury in lenticular ore-bearing bodies are also found over a roughly 20-km stretch in the valley of the Valdeazogues river. and realgar. The gangue consists largely of clay or dolomite. Mining is carried out today at a depth of 500 m. they were not intensively worked by the Romans. 1 %. About 60 t mercury was mined in 1986. and from 1525-1645 by the Fuggers.3. The ore is extracted in several mines (San Pedro y San Diego. and the Abbadia San Salvatore mine. The ore contains ca. then by the orders of knights.C. Mercury occurs as cinnabar and metacinnabarite in pyrites. and typically contain admixtures of pyrites. mainly in Eocene sediments (shale. and Montenegro. San Francisco. marcasite. Mercury extraction is organized by the Monte Amiata works. From 1449 (when production records start) to the present. its latent production capacity being up to 2000 t/a. ca. Because of the low price of mercury the plant operates for only a few months of the year. corresponding to a 3. Spain. Idrija has a capacity of about 600 t/a. The overwhelming proportion of mercury has always been produced in Europe. Silurian quartzite) that contain mercury sulfide (cinnabar). The operating company. Spain. San Nicolas). about 40 km west of Ljubljana. and the United States have accounted for ca. some of the most important deposits are listed below. on the northern edge of the Sierra Morena. Over the last ten years. 0. Turkey. the mining depth is ca.3 Resources and Raw Materials 17.Mercury 893 17. 1 t of ore yields about one flask of mercury (= 34. . These mines were subsequently worked by the Moors. Neumarkt in the Karavanken.2-0.1 Deposits All known mercury ores are relatively lowgrade ores. 50-km-long belt running from Monte Amiata to the coast in southern Tuscany contains many closed mines as well as some that are still operating. 300 000 t of mercury has been mined. gypsum. and was mined by the Romans from 150 B. Shell marl and shale are impregnated with cinnabar and native mercury. 1380 t of mercury. 800 m at most. limestone) under a covering layer of trachyte. The ore-bearing deposits are porous sedimentary rocks (sandstone. about 200 km from Madrid. Italy. No mercury has been mined since 1983. Almadén is situated in the southwest of the province of Ciudad Real in New Castile. and bitumen. then under Italian ownership. the former Soviet Union. is state-owned [5. The ores contain on average 0. The deposits at Almadén have been mined for more than 2000 years. The ore-bearing body has an average mercury content of 5%.
25% mercury). Japan. total mercury production is some 500 t/a. Whereas 149 mines were operating in 1965. Additional ore deposits are mined in the . South America. Algeria has become the second largest mercury producer in the western hemisphere after Spain. Small amounts of mercury are mined in Venezuela and Bolivia.. and Queretaro. Canada. Finland. The Santa Barbara mine at Huancavelica in Peru is now exhausted. 40% of the Turkish reserves of mercury . In Turkey about 220 t of mercury is obtained annually from mining operations. South America is of only minor importance as a mercury producer. China has important deposits in the provinces of Yunnan.23% mercury). A U. because of its low price. which belong to the state-owned Etibank. and Konya-Sizma (1. Mercury ore deposits are situated in the west of Canada in British Columbia at Pinchi Lake and in the vicinity of Vancouver (Kamloops. Durango. The most important mines are in the provinces of Zacatecas. Three important deposits exist: at Kotrbachy. Bridge River). and in 1986 ca. At present. Per year about 400 t of mercury is produced there from an antimonite ore containing 0. Cinnabar deposits have recently been discovered in the Crimea. China. Urals. a subsidiary of the Canadian company Placer Development. mercury is extracted from only two mines. Hunan. Altai Mountains. estimate made in 1983 gave the following amounts of mercury extracted by mining operations : Spain China Soviet Union Yugoslavia 50 000 t 17 200 t 17 200 t 17 200 t Former Soviet Union. The 200 known mercury ore deposits are distributed over 20 states. 99% of production. The number of mines in the United States has decreased considerably in the last 20 years. This production ceased in 1937. mercury has been obtained in the region between Mernik and Vranov since the end of the 17th century.25% mercury. only 3 mines were still operating by 1981. Fahl ore containing 1. Germany. 760 t of mercury in 1987. In Japan. Romania.4% mercury. although no further details are available.S. Austria. The most important deposits in the former Soviet Union are at Nikotovka in the Ukraine. was uneconomical. mercury is obtained as a by-product of a fahl ore. accounts for ca.894 Handbook of Extractive Metallurgy Algeria. containing only 0.15 x 10 t of ore containing 0. Guerero. These deposits alone account for ca.3— 0. 6 6 Northern Caucasus. Outokumpu obtains about 100 t of mercury per year from the processing of zinc concentrates. Former Czechoslovakia. Mined production was ca. Placer. Turkey. The mines at Wanschantschang and Patschai are well known. San Luis Potosi Aguascalientes. and Kweitschan. Guanajuato. United States. mercury is extracted on the island of Hokkaido. Chile occupies first place among the mercury-producing countries. 690 t of mercury was produced. Romania has mercury ores at Zlatna and Baboja in Transylvania. Other deposits at Dollach on the Drava are no longer mined. Inc. Finally. The deposits are at Izmir-Odemis-Halikoy (1 X 10 t of ore containing 0. although it supplied substantial amounts of mercury in the 17th and 18th centuries: some 50 000 t was used for precious-metal extraction. and in Turkestan and Dagestan. Mexico. In 1936 a modern mercury works was built at Landsberg near Obermoschel in the northern Pfalz (Palatinate). which had to be closed in 1942 because working the very low-grade ore. The principal mining regions are California and Nevada. The average mercury content in the ore is 0. Chihuahua.5%. Konya-Ladik. Cinnabar is found southwest of Gelnica in a workable ore containing 0.8% mercury is mined in small amounts at Schwaz in the Tyrol.1 % Hg. Mining production in 1986 was ca. 400 t and falling.
thermometer breakage. it is nonpoisonous and can be stored and transported without any problem. The overall reaction in the absence of oxygen is as follows: 4HgS + 4CaO 3CaS + CaSO + 4Hg 4 In the presence of oxygen. mercury fluorescent tubes.075 mm (200 mesh) in the case of antimony and 0. 7 0 % . After purification. greatly dependent on current world market prices. butyl xanthate.1 Beneficiation SO + Hg 2 Preliminary concentration is desirable. Too low returns have led in recent years to a number of mines being closed. The coarsely ground ore is processed in directly or indirecdy heated furnaces. 17. 3 2 2 2 7 Only a coarse preliminary grinding to ca.2 Secondary Sources Like primary ores. The majority of plants used in chlor-alkali electrolysis employ liquid mercury cathodes. industrial waste containing mercury also contributes to its production. Reaction with oxygen begins at 300 °C. the ores are comminuted to grain sizes of 0.Mercury 895 Italy United States Other countries World total 12 100 12 100 29 000 154 800 t t t t Mining activities and exploitation of deposits are. Separation of the antimony and arsenic fractions is particularly important. retorts. iron oxides can also be used: . and Quicklime can be added as flux to bind the sulfur in solid form. The end concentrate has a mercury content of ca. as with most base metals. 50-mm grain size is necessary for high-concentration mercury sulfide ores. electrical switches. mercury batteries. lead(II) nitrate [Pb(NO ) ]. Another way of concentrating mercury by flotation is to add potassium oleate as collector . or muffles. cinnabarite).2 Processing to Metallic Mercury [11. Another method of concentration is the use of a flotation stage to increase the mercury content. the ore particles burst because of the high vapor pressure.1. Crystalline mercury sulfide in brittle ore can be concentrated by using settling tables. according to HgS + O 2 17. 17.4 Production 17.4. resulting in residues containing 10% mercury or more.3. Potassium dichromate (K Cr O ) is added as reactant. Because of the brittleness of cinnabar. 50% antimony is obtained. and obsolete rectifiers should be regarded as mercury sources.5 mm (25 mesh) in the case of arsenic. and pine oil are added to the first flotation stage. and a concentrate of ca.1 Extraction from Primary Sources 17. After comminution. During subsequent thermal treatment. mercury is selectively floated. Although the overall production of mercury has decreased over the last 20 years. This is often performed in the mine by classification.4. sufficient potential uses and thus secondary sources remain for the foreseeable future. resulting in further comminution.1.1.12] The most important starting material for mercury extraction is mercury sulfide (cinnabar. In addition to this major secondary source. Flotation is performed at pH 7. thanks to the unique properties of this metal. especially for working low-grade ores. which has resulted in a concentration of plants (less plants with increased production).4. pieces of ore break easily at the mercury sulfide veins. the reaction is HgS + CaO + / O 2 3 2 Hg + CaSO 4 Addition of metallic iron in the form of iron filings enables the following reaction to occur: HgS + Fe FeS + Hg Instead of metallic iron.
in the case of mercury. The amount of flue dust is thereby lowered (0. Cast steels with additions of titanium. a mercury-containing powder).9 8 ore 77 21 L oil Quicksilver Mines 5. have had to be shut down. The Bustamente furnace is still used in Spain (Almadén) . in some cases. With regard to environmental protection.4 shows some operational examples of multiple-hearth furnaces. multiple-hearth furnaces are relatively difficult to make gastight and. Table 17. the ore does not have to be specially preheated. gas. The hearths and outer walls of the furnaces are built of shaped fire- clay bricks. a lower amount of gas can be passed through the furnace. An attempt is made to keep the flow velocities for the reaction gas low (maximally 3 m/s) by skillful feeding of the material (if possible by special sliding surfaces at the throats in the case of small hearth interspacings) and by separately installed gas passageways. By accurate metering of the inlet air. Directly Heated Furnaces. The furnaces are lined with sheet steel. Mercury in vapor form condenses to some extent on the small dust particles which act as condensation nuclei. Addition of combustion air through the insulated hollow shaft and raking arm and. Rotary kilns have been used since 1913 to extract mercury. and the sulfur dioxide formed can be converted in a downstream wet scrubber.4. chromium. sulfur-resistant steel should be used as construction material. t/d Fuel consumption per tonne of material 4.15 m wood 3 .4: Operational data for multiple-hearth furnaces for mercury extraction. preheating of the fuel oil both reduce fuel consumption. Because of the presence of combustion air in the furnace. or stupp.2-3% of the feedstock). 5 m. Table 17. The cylindrical vessel is heated outside the shaft. A historical feature is that mercury vapors are condensed in air-cooled terracotta pipes.3 Furnace Systems Mercury sulfide-containing ores are processed pyrometallurgically. The greater the formation of dust in the furnace. and nickel have proved suitable for internal structural elements (stirrer shaft. The multiple-hearth furnace is advantageous for working up rich concentrates.896 Handbook of Extractive Metallurgy 7HgS + 2Fe O 2 3 4FeS + 3SO + 7Hg 2 For this reason. has a diameter of ca. Cylindrical Bustamente furnaces. Distinction is made between directly and indirectly heated furnaces. Another difference between directly and indirectly heated furnaces is that mercury vapor in indirectly heated systems is more highly concentrated because it is not diluted by combustion gases. and contains up to 16 hearths that are heated with wood.1. This kind of furnace has been used for many decades in various mercury mines in North America. New Pershing Almadén Furnace diameter. only the combustion gases come into contact with the ore.9 6 ore 38 47 L oil 4. the greater is the occurrence of stupp. and the capacity of the subsequent condensation unit can be reduced.5 6 ore 50 0. mercury waste of a similar type. and the formation of stupp is minimized. Processing is normally performed with the addition of air. multiple-hearth furnaces. This is important because the formation of stupp cannot be avoided in pyrometallurgical processing (the word stupp is an Austrian expression that simply means powder. directly heated furnaces generally create more dust than indirectly heated ones. or oil (mainly the upper and lower hearths). A modern furnace is up to 10 m high. raking arm). 17. and material throughput can be regulated. Rotary kilns and rotary drum furnaces provide a high mercury yield with a good throughput rate of the ore because the reaction temperature can be controlled accurately. and rotary kilns are used. if necessary. and in Almadén most of the ore extracted since 1961 has been processed in multiple-hearth furnaces. m Number of hearths Worked material Throughput.
5: Operational data for rotary kilns for mercury extraction. Gelnica Furnace length. Active carbon slurries from the effluent concentration resulting from chlor-alkali electrolysis constitute the major proportion of mercury residues that must be reprocessed. Several proposals for processing mercurycontaining material in indirectly heated furnaces have been made. A rotary kiln constructed from two concentric tubes was developed several years later. % Time for one revolution. % Grain size of ore.6-0. the processing of fluorescent bulbs. The subsequent condensation of mercury from the furnace off-gas is treated later.4. gastight silicon carbide is used as cladding. charcoal. vessels lined with fireclay or ceramics. m Thickness for lining. coal. A disadvantage of rotary kilns is the dust formed by the intense material movement.92 18.Mercury MinSalvatore Indria silver Mines silver Mines ing Company 16 1. centrally Table 17.75-6% of the ore feedstock by weight is observed. and patents have been issued [13-15].2 0. In many cases.2 50 40 3 100 m (STP) gas 100 kg wood + 0. is becoming increasingly important. Without the addition of coal as flux. Flue dust amounting to 0. Storage of slurry-like residues is complicated and expensive. Quick. The basic advantage of indirect heating is the lower gas velocity in the reactor and the higher mercury concentration of the process gas. mm Ore throughput.22 14 1. spent products must be reprocessed to a large extent. this corresponds to up to 30 L of oil or 250 m (STP) of fuel gas per tonne of ore throughput.Mercury 897 The ore is ground to about 65-mm particle size before it is charged. m Internal diameter. or by electricity and consist in some cases of clay muffles. Krupp-Grusonwerk AG has arranged several tubular individual muffles in a rotary kiln around a thermally insulated. % Hg content of ore.22 21 1. which leads to increased stupp formation in subsequent condensation and can cause stoppage in the waste-gas line. the outer tube is heated. The furnaces are operated at 320-400 °C at the charging head and 700-800 °C at the discharge end. The ore passes continuously through the inner tube. mm Gradient.25 200 5 17 1.5 250 4 72 5-10 0. Lime.2 Extraction from Secondary Sources Because of the relatively high toxicity of metallic mercury and some of its compounds. dust formation can be reduced by fluxes having a sintering effect. or low-temperature coke may be added as fluxes. s Moisture content of ore. heat consumption is (1 to 1. Several plants dealing specifically with the disposal of these lamps already exist in Germany .25) x 10 kJ per tonne of throughput. which contain about 1550 mg of metallic mercury per lamp. 6 3 aligned shaft.5. and is governed by the limited storage capacity of the closed mines. For normal furnace sizes and ores.22 150 4 42 0. or iron vessels lined with silicon carbide. and the furnaces are heated directly by oil or gas. Indirectly Heated Furnaces.5 L oil 40 45 30 L oil 50 45 29 L oil 45 50 12.3 m wood . Some operating examples of older rotary kilns are listed in Table 17.Pershing. A highly thermally conducting.3 1. F. The furnaces are heated by gas. Quick. t/d Fuel consumption per tonne of ore 3 Abbadia San New Nevada.8 5 100 125 19L oil 64 40 26. In addition to these residues. 17.
Because mercury can be precipitated 17.898 Handbook of Extractive Metallurgy from waste gas most efficiently by adsorption on activated carbon or similar substances. 0 . A hydrometallurgical reprocessing treatment has been investigated on a pilot scale in a research project [ 2 4 ] . which can remove mercury by treatment in rotary kilns or in a distillation chamber. starting from a level of 1 % [ 1 7 ] . Germany [ 1 9 . 2 0 ] .1: Reduction of mercury in primary batteries in Germany : a) Mercury in sold primary batteries. the mercury content of batteries will be reduced to 0 . The method does not appear to be economically practical at present because of the relatively expensive reactants involved. 1 5 % by 1 9 9 0 (Figure 1 7 . 5 V .1 . which are inadequately identified and. zinc-mercury(II) oxide batteries are also widely used as round cells. have the same external dimensions for different electrochemical systems.. mercury-containing charcoal from waste gas purification will also require reprocessing in the future. which must be recovered. and can be added to the conventional extraction processes. Another company converts the residue to metallic mercury in a rotary kiln by adding lime fluxes. 3 kPa can be determined from the . in some cases. In Germany. Mercury is extracted in the form of mercury(II) oxide and sulfide. Mercury in concentrations of ca. The individual types of batteries do not have to be sorted beforehand. has been reprocessed in a multiple-hearth furnace in which the mercury fraction is evaporated [ 2 2 ] . Mercurycontaining older printing inks are another source. can generally be worked up by conventional distillation methods [ 2 5 .3 Condensation of Mercury from Furnace Off-Gas The vapor pressure p (mbar of mercury) can be calculated according to a relationship given by BARIN and KNACKE [ 2 9 ] : where T is measured in kelvin.g. and a mixture of batteries can be processed. and other countries . The mercury content of normal zinc-manganese dioxide batteries has been reduced considerably over the last few years (addition of mercury inhibits the formation of gas by zinc). and amalgams. 3 0 % mercury. Additional secondary sources. A comprehensive monograph on the topic of evaporation and thermal dissociation of mercury sulfide is available [ 2 7 ] . electric switches. as sealants). waste gases must be treated and burned if necessary. with a relatively inert residue remaining behind [ 2 3 ] . In addition to zinc-manganese dioxide batteries. 26]. Because batteries also include a large number of plastics (e. b) Mercury in domestic refuse. which occurs as a slurry. The mercury-selenium residue formed in the primary smelting of mercury-containing sulfidic ores requires special reprocessing.9 5 % mercury and < 1 0 % gold are deposited at 1 . Figure 17. such as thermometer breakage. These contain ca. The degree of saturation s (kg of mercury per cubic meter) of the gas at t ( ° C ) or T ( K ) and p = 1 0 1 . A particular problem in reprocessing batteries is grading and sorting the various types. Because a proportion of spent batteries end up in domestic refuse. high mercury concentrations can be found in waste gas from domestic refuse combustion. 1% is also found in zinc-silver(II) oxide and zinc-oxygen batteries. Treatment processes have been developed in Japan [ 1 8 ] .4. 1 ) . Electrolysis has been proposed for the removal of mercury from gold-containing solutions: 9 0 . This substance.
71 x 10-4 3.3727 2.100 0.919 x 10-4 8.71 m 3 oc curs.2894 3. There it is cooled to 20 °C (293 K) (s = 0.8359 1. and with oil firing 6.2 20 °C by a factor of 4.110 21.625 x 10-3 0.3% Hg is worked up.42 0.478 8.012138 0.71 x 0.514 x 10-4 1. the mercury residual content in waste gas. Directly heated mechanical roasting furnaces Figure 17. at 140 °C.2545 0. With a condensation end temperature of 20 °C at which the gas still contains 0. this corresponds to about 470 m (STP) with wood or generator gas firing and 375 m3 (STP) with oil firing.0 9021.906 14. p. a loss of 1.35 % Hg. the loss increases to 0.75 g/m3 (STP). Mercury losses during condensation can be calculated as follows: 1 m3 of saturated vapor at 140 °C (413 K) enters the condensation unit laden with 14.1568 0.Mercury 899 pressure and density of mercury vapor (3. increases with a temperature increase of 10 °C by a factor of 2.2 x 10 kJ per tonne of ore. With 5 % wa ter content in the ore.02150 0. In general. If an ore containing 0.5 3909. compared to the amount at 20 °C.404 3. Figure 17.464 g of mercury.2457 0.558 14.8743 32.65 879.915 3.1325 0. kPa 7.1 3 0.2: Vapor pressure p and saturation content s (g/m3) as a function of temperature. The loss of uncondensed mercury re moved with the waste gas is thus 0. The saturated vapor leaving the unit therefore contains 0.1-1.25 2921.32 Generator gas Oil 6 The degree of saturation s of mercury vapor calculated according to this formula for differ ent temperatures is summarized in Table 17.21-0.464 21. 70 m 3 (STP) of steam is produced in addition.6: Saturation content of mercury vapor at various temperatures.4695 0.2 shows p and s plotted as a function of 1/T on a semilogarithmic scale.187 9.06154 0. and a volume contraction to 293/413 = 0.03489 0.808 101.03144 0.01508 0.56 g/m 3 (STP).06612 0.5893 1.25% mer cury occurs. 1.3 T.1585 0.440 2. .906 6.00604 0. K 283 293 303 313 323 333 343 353 363 373 383 393 403 413 423 473 523 573 630 Saturation content. s s saturation content under standard conditions [g/m3 (STP)].761 x 10-3 3.03 x 10-5 1.7 g/m (STP) 0.1 In practical operation the mercury content in the hot reaction waste gases is always far below the saturation limit because the theoret ical vapor-liquid equilibrium is not reached. and at a condensation end tem perature of 40 °C.07588 0.284 5.3104 0.97 1391. The following amounts of waste 3 gas [in m (STP)] are produced per 1000 kJ for the different fuels with 20% excess of air: Wood 0.385 33. the mercury content with wood or gas firing is 5.0141 = 0.0141 g of mercury per cubic meter corresponding to the saturation limit a loss of 0. With a condensation end tem perature of 40 °C and otherwise identical con ditions. Table 17.081 1.00626 0.417 117.03690 0.175 203.3 % mercury from the waste gas occurs.01 g of mercury.01406 0.387 0.6. s g/m 3 Per tonne of ore.07% of the initial amount.486 x 10-3 6.9091 3 kg/m at 357 °C) (α = 1/273): require a heat input of ca.0141 g/m3).65 458.
g.4. or (4) wetting of ore that is too dry. for the other cooling stages. The tubes are sprinkled with water. Several practical requirements must be met for satisfactory operation: (1) The ore should be as dry as possible. (2) The amount of waste gas produced by the fuel should be low.. (3) When the gas enters the condenser. A conveniendy arranged condensation system for a directly heated mercury smelting plant operating with mechanical roasting furnaces consists of the following parts: • Dust separator in the form of a cyclone. The ratio of tube cross section to fan output must be matched so that the gas flow velocity is maximally 0. (3) predrying of ore that is too wet.75 m/s in narrow parts of the tubular condenser. its temperature should be only 1 0 . 7 8 . each with eight inverted U-tubes of elliptical cross section whose arms terminate in acutely taper- ing. stupp-collecting tanks are also constructed of concrete. when processing highbituminous ore. (4) The outlet temperature should be as low as possible. The mutually corresponding tubes of all the individual trains in each case end in a common box. the reaction gas should pass through an afterpurification section.900 Handbook of Extractive Metallurgy 30 °C by a factor of 9. The overall unit must be designed so that half of the tube trains can be decommissioned for cleaning and repair. When the plant is operating continuously. all places prone to thick deposits must be mechanically cleaned once a week.4 40 °C by a factor of 18. Gate valves in each train enable the draft to be regulated or even permit the train to be separately disengaged. water-filled deflection boxes. To ensure sufficient mercury condensation.9 1 % of the . of Monel Metal) • Cooling unit for mercury condensation • Afterpurification chamber for mercury residues separating • Injection chamber for separating traces of mercury • Fan (e. whereas the remaining tube trains ensure satisfactory cooling of the reaction gas while maintaining draft conditions in the furnace. the gas must pass through a succession of water curtains. (5) Before entering the stack. In a plant that processes an ore with 5% moisture content. water is circulated and recycled through suitably dimensioned settling tanks. which slopes so that any leakage can be detected and escaping mercury collected. if possible. The last stage operates with fresh water.1 50 °C by a factor of 33. and consists of tubular condensers (CERMAK type) formed from six to ten trains arranged in parallel. (2) separate processing of finegrain classes of ore. the remaining areas can be cleaned at longer intervals. or a combination of both • Fan (e. of Monel Metal) The cooling unit is itself in many cases also constructed of monel metal.. The tanks stand on feet on a smooth cement floor. The flue dust should be separated as completely as possible from the still hot reaction gas before it enters the mercury condensation unit. Fewer parallel tubes of larger diameter are used in the cooling unit for directly heated furnaces. for example.4 Thus efficient cooling of the waste gas is necessary. and in this way the stupp can be classified.g. 17.4 Treatment of the Stupp The amount of mercury contained in the stupp may represent a substantial proportion of production. as much as 5 0 % of the cooler capacity is used for condensation of evaporated moisture alone. an electrostatic precipitator. Gases from indirectly heated furnaces that contain only a small amount of flue dust can be condensed by spraying water directly into the mercury-containing waste-gas stream. without the steam originating from fuel combustion being taken into account. All setting tanks within the condensation unit have sloping floors and connecting pipes through which mercury metal flows to the lowest part of the system. The material for these tanks is wood or cast iron. In Idrija. Stupp formation can be kept low by (1) indirect heating.2 0 °C above the mercury dew point.
This very effective method of separating mer cury enables the waste material to be dumped directly onto the waste tip in certain cases. with suitable air movement.1.005-0. 37]: Meadowland in Arable land in Vineyards in the Reed belt on the Niederösterreich Niederösterreich Burgenland Neusiedlersee 0. 0. distribution.8% humus) in Kremsmünster Woodland (10. metallic mercury disperses relatively quickly into the atmosphere and. is taken up by plants and animals. Generally.104 0. For regularly occurring large amounts of stupp.Mercury 901 mercury is extracted from the stupp and only 9-22% is extracted directly. Mercury is thus one of earth's relatively rare elements. saponifies any fats present. wind erosion.3 μg/g (generally < 0. Amounts of mercury used for seed treatment or soil disinfection are as follows: Grain (wheat) ca.2% humus) in Kremsmünster Garden soil in England Rice field slurry in Japan Fields for agricultural use in Niedersachsen.01 μg/g).05 μg/g .249-1. 17. 7 g/ha added as seed treatment agent to the soil per 150 kg of seed material/ha Sugar beet (seed material in pill form) ca.001-0. soil. which can generally be achieved by kneading and pressing the mass. A comprehensive list of mercury in the environment appears in . degassing) 25-100 000 t/a Natural mercury emission in water (weathering in rivers) 5000 t/a Use of fossil fuels (minerals. and utilization of mercury is given in the following material : Arable land (3 % humus) in Kremsmünster 0. the utilization of mercury is rela tively small. and the atmo sphere.039 0. with the re sult that the low-mercury fraction must be re turned to the smelting process.06 ng/m3 .1 Mercury in Soil. individual mercury drop lets must be coagulated. and degassing constitute the largest proportion of emitted mercury. and chemically reduces mercury sulfate. 0. The natural mercury content of the atmosphere is 0. Addition of quicklime to the stupp neutralizes any acids contained in the conden sate.0 0. deposits) 8-10 000 t/a Use of mercury and its compounds 6000 t/a Natural air emissions from mechanical ac tivity.340 17.080 0.25-15. Mercury and dust can also be mechanically separated by simple wash treatment with wa ter. 1 g/ha added as seed treatment agent to the soil per 200 000 pills/ha Cotton (seed treatment and disinfection) ca. 20 g/ha . in certain cases. and in meat. A tenfold mercury enrichment from the stupp by flotation was described in 1929 . although this should not mini mize or obscure the danger of mercury at high concentration. a special furnace unit is worthwhile (retorts or multiplehearth furnace). and Animals Relatively large amounts of mercury are circulated due to the constant exchange of mercury among water.070 0. absorbs a large proportion of the water. Some of this migrating mercury is re tained in the soil in the form of humus compounds and. in plants. Mercury content of the oceans 70 000 000 t Mercury content of the earth's crust (1-m-thick layer) 100 000 000 t Natural atmospheric mercury emission (volcanoes.08 ppm and in seawater 3 x 10-5 ppm.1 Natural Distribution of Mercury Because of its high vapor pressure.065 Meadowland (4. Germany Woodland in Niedersachsen. To extract mer cury from the stupp.170 0. extraction of mercury from the stupp is not so effective. Stirring the stupp with sievelike perfo rated rakes in iron vessels also gives good re sults.5. however. A quantitative summary of the occurrence.180 0. wind erosion.40-1.5.5 Environmental Protection 17. is also con centrated .672 120 g/ha Organically bound mercury is also added to the soil with seeds as a seed treatment agent (fungicide).001-0. Plants.8 0. Germany Mean mercury value for Europe (10-cm-thick humus layer) 0. By contrast. The mercury content of various soils in Austria unless otherwise stated (mg per kilogram of soil) is as follows [36.055-0. The average concentration in the earth's crust is 0.
pike) contain higher than normal levels of mercury only if they preferentially feed on dabbling fish. 80 g/ha However.g. The mercury content in soil is higher in geothermal or ore-containing regions and can be as high as several parts per million.l ) in the soil . Predatory fish (e. the latter can absorb and concentrate mercury from the local soil. Under the assumption that the values found in museum preparations constitute a lower limit—some of the mercury might well have evaporated over the course of time—the fact that present-day values are the same as previous values means that no concentration has occurred.3).022 and 0. especially atmospheric. the mercury content of fungi and mushrooms increases considerably .5. Mercury uptake in warm.55 ppm (mean value 0. the mercury content of soil varies between 0. without any "recognizable" effect due to human activity .19). exhibit a high mercury content . tropical waters is higher than in cold northern waters . where trout have been found with a mercury content of > 1 mg of mercury per kilogram of fish. the Zentrale Erfassungs. With more serious contamination. where no large cities or industrial regions are to be found. mercury is often used as a tracer metal in geological exploration . Because of the concentration of mercury in sediment. point to factors other than industrialization.und Bewertungsstelle für Umweltchemikalien (central office for collecting and evaluating data on . Mercury-rich fungi and mushrooms are found everywhere. The high mercury concentration in the liver of seals in the northern section of the east coast of North America (Labrador). The mercury content in the soil and in the lichen decreases sharply with increasing distance from the mine. Because of the affinity of mercury for the sulfur-containing constituents of fungi. Mine waste gases and worked ore are the main sources of emission . The controversy surrounding canned tuna in the United States has revealed that tuna preparations in the Smithonian Institute from ca. Mercury in Fish and Seals. Lawns (disinfection) ca. 45].2 Mercury in Food Many investigations were carried out on foods from the 1920s and 1930s onward . As pot tests have shown.3: Microcirculation of mercury (in g h a . is attributed to underwater volcanic emissions. Figure 17.l a .1. 17. The fleshy parts of fungi and mushrooms can contain unexpectedly high concentrations of mercury [44. The mercury content in fish varies depending on type and habitat . Thus. absorb more mercury than nondabbling fish. nor plants grown on such soils. The assumption that fish concentrate mercury to 2000 times its concentration in the ambient medium is neither valid nor statistically relevant and has no significance as a rule of thumb . The amount of residue passing into groundwater is insignificant  (Figure 17. 39].. dabbling fish. Mercury in Fungi and Mushrooms. According to investigations carried out in Norway. 1880 have the same mercury concentration as present-day fish. Mercury content has been investigated in soil and lichen in the mercury mining region around Monte Amiata (Italy). the mercury is partly retained in the humus and partly evaporates from the soil [38. In Germany. which collect their food from the bottom of the water. neither soils that have received mercury-treated seeds for many years. Data from the Danube upstream of large cities and industrial regions.902 Handbook of Extractive Metallurgy regardless of whether the soil has been anthropogenically contaminated .
and eggs.0 0. < 0. has collected data from 1975. . dogfish.3 (Hg methyl) 1. beer. blue ling. canned fish (8.5 0.271 0. in most cases.047 0. % a a 0.2%).070 0. Hg-susceptible fish include: mackerel shark.9%). covering 1978-1982.058 0. or root vegetables and canned vegetables. The 1982 values essentially confirm the analytical data of 1979. The legal limits are given in Table 17.041 1979 0.6%). % a Germany WHO recommendation Table 17. and beverages such as wine. except Hg-susceptible fish Hg-susceptible fish Fish products Canned fish Wheat Coffee a Content.11 0. or canned fruit. wheat (12. shell.17 mg of Hg per 50 kg of body weight 0.8%).9.17 a Women (58 kg) mg/week Proportion of W G O figure. Fish.1%).196 1. and the fatty tissue of nursing mothers .) Table 17. turbot. blood serum.246 0. Foods contain the major proportion as follows: drinking water (14. vegetable oils and fats. sausages.. calves kidneys. potatoes (6. The major proportion of mercury is absorbed from animal foods . Total uptake. fruit and vegetable juices. pomaceous. 1. rice. fruit.859 0.0 leafy. condensed milk.0%). calves liver.8: Mercury in food. berry.0%).Mercury 903 environmental chemicals. pork.7: Legal limiting values for total uptake of mercury (1980). The most recent ZEBS investigations . citrus. cheese.2%). kg/kg of fresh substance 1982 0. According to these data.e. and zinc content of breast milk. coffee (7. fish with a high Hg content may be legally rejected.003 The median values of toxic substance levels were taken into account. rye.9 with the limiting values specified by WHO. and potatoes. Hg W H O value mg/week (70 kg) mg/week (58 kg) Men (70kg) mg/week Proportion o f W H O figure. 0.1229 35. and meat products. are presented in Tables 17. ZEBS) of the Federal Ministry of Health in Berlin in particular.015 0. if average consumption patterns are assumed.4 (Hg) 0. mg/kg Switzerland Japan United States Sweden 0. mercury uptake in 1979 was about 0.052 mg per week for the "average" inhabitant of Germany (i. and 1982.0033 mg/kg ofbody weight (Hg methyl) no limit (lakes that contain fish with more than 1 ppm Hg are placed on ablacklist).8 and 17. only about one-sixth of the upper limit recommended by WHO).208 0.206 0.005 mg/kg ofbody weight (Hg) 0.010 mg/kg.077 0. 1979. halibut. milk (10.260 0.188 0. The values for milk. and Greenland shark.35 (0. Food Cow's liver Pig's liver Cow's kidneys Pig's kidneys Freshwater fish Saltwater fish. mineral water (8.290) 0. poultry.0933 32.9: Uptake amounts of mercury in absolute figures and as a proportion of W H O values. magnesium.3 (max. Another detailed investigation carried out by ZEBS is concerned with the mercury.021 0.020 mg of mercury per kilogram of fresh substance and. and chocolate are all < 0.7. stone. veal. and fish (5.066 0.127 0.257 0.026 0. The average amounts of mercury actually absorbed per week are compared in Table 17. mg/week Table 17. black halibut. sprouting. beef.
4: Specific mercury load distribution in the Bamberg refuse heating and power station with TMT-15 precipitation. and the Hg values of the waste gas are 0. The largest amounts of secondary mercury occur in the smelting of sulfidic ores.02-0. Fine purification is performed by afterpurification with sodium sulfide .1 Mercury Emissions Gas Purification In a large number of combustion processes. mercury is transferred to the gaseous phase and must be removed again by subsequent treatment. waste gas containing mercury and sulfur dioxide is treated with a wash solution containing Cu and Hg ions in addition to H S 0 (200-300 g/L) and HC1 (5 g/L). 2 2 3 In a third method. At present. Mercury is removed from the wash liquid by treatment with sodium sulfide.5.2 17. 2+ 2+ 2 4 + 0 3 Figure 17. the cooled and dusted roast gas is treated with a mercury(II) chloride solution. Mercury in the vapor is thereby oxidized to Hg . with and without sludge combustion .2. and mercury precipitates as mercury(I) chloride (Hg Cl ). 56].05 mg/m . two methods are primarily used for waste-gas purification. In the second method.5.05-0. Part of the mercury(I) chloride produced is oxidized to mercury(II) chloride with gaseous chlorine and returned to the process. the gas is treated with sulfuric acid (90%) at 200 °C. Mercury which is present as mercury sulfide is released during roasting.904 Handbook of Extractive Metallurgy 17. In the first method. The final level of mercury in the waste gas is 0. .1 mg/m [55. The mercury(I) sulfate formed is deposited in wash towers.
Most of the mercury passes into the residue to be dumped. the flue ash contained in flue gases adsorbs mercury(II) chloride and reduces it to mercury(I) chloride. The compound is stable up to 210 °C and is only sparingly soluble in the elution test (a test to determine the soluble components of a solid material). 0. Below ca. Reduced mercury is added together with the wash water to an evaporation device and is expelled by passage of stripping gas at elevated temperature. and mercury is depos ited as an amalgam.Mercury 905 Another source of mercury emission is refuse combustion.5. The initial mercury concentration should be between 0. It decreases with decreasing temperature and can be reduced further by addition of salts (e. The percentage distribution of mercury in a typical refuse combustion plant is shown schemati cally in Figure 17.25 DM per tonne of refuse. The copper powder cathode is held in suspension by the flowing solution.g. The mercury con tent of domestic refuse is 3-5 g/t . and batteries in domestic refuse. The active substance of the additive consists of trimercapto. ion exchangers. The additional costs involved in TMT-15 precipitation amount to ca. which re move mercury from the solution in the form of a mercury sulfide compound. switches. Tin(II) chloride dissolved in dilute hydrochloric acid has been proposed for treat ing mercury ion-containing wash water from combustion units. The level of 10-30 mg of mercury per liter in wastewater from chlor-alkali electrolysis can be reduced to 0. The carbon has a grain size of 5-100 μm [64. sodium chlo ride). 150 °C. Copper fluidized-bed electrolysis provides another method for mercury separation. mercury can be concentrated in the oil phase. Condensation is ef fected by cooling the gas stream. Mercury can also be removed from solution by addition of suitable reagents.0 mg/L .4 mg/kg after filtration . The oil is sepa rated by centrifugation. sulfur-containing sub stances are used as active groups. fluorescent tubes. Examples are activated carbon filters. The fine purification of crude phosphoric acid can be performed at pH 0. 71]. The initial mercury content of ca. Active carbon or active carbon impregnated with iodine compounds can also be used as a mercury adsorbent [59-62].5 and 2. 65]. The mercury content is thus reduced from 5 mg/L to < 0. a distinction can be made between reusable and disposable ones [65-67]. Mercury occurs in the form of thermometer breakage.. 17. In some cases. the ad ditive TMT-15 developed by Degussa is used in some cases on an industrial scale (Figure 17. The mercury content is reduced from ca. For ion exchangers. The reducing agent tin(II) chloride is added in above-stoichiometric quantities. A whole range of equipment and devices can be used in purification methods to remove mercury from water. Investigations have shown that mer cury in flue gases is present as mercury(II) chloride . and electrolysis systems. Carbon is dispersed in the water and then filtered.1 mg/L. The mer cury content of the purified aqueous solution is in some cases < 10 μg/L. and line purification is carried out by using a conventional oil-water emulsion splitting unit. To purify flue gas wash water from refuse combined heating and power stations.5-1.1 mg/L by using activated carbon and graphite powder.4. Mercury can be removed from concen trated sodium hydroxide solution by the use of ultrasound when the solution is filtered.4).2.2 Water Purification The solubility of mercury in water depends strongly on the temperature. 20 mg/kg of aqueous sodium hydroxide is reduced to ca. Mercury is bound as C 6 N 6 S 6 Hg 3 . 4 mg/L to < 0. By adding small amounts of oil which are dispersed in the aqueous solution.5 by using a diorganodithiophosphorus compound in . The copper amalgam is purified by distillation . 0. all types of activated carbon can be used for the fine purification of mercury-containing water.05 mg/L [70. depending on the concentration of tin(II) chloride . In principle.S -triazine in the form of a sodium salt.
zinc. The ore sample is weighed in a porcelain crucible. which is sprayed from above with cooling water. In many cases. silicon. Perchloric acid con taining mercury oxide serves as the electro lyte. adapted to the relevant processes. magnesium oxide. Most of the mercury on the market is 4N mate rial (99. mercury must be distilled repeatedly to achieve the desired purity.99% mercury). mer cury is dissolved by adding nitric. although this would give rise to difficulties with regard to the apparatus. Mercury can be evaporated un der atmospheric pressure or in vacuo. 17. Good dispersion of the mercury is ex tremely important in this method. aluminum. all the mer cury has been collected. or sulfuric acid with dichromate. are available for purifying and working up larger amounts of mercury [77. permanganate. the accuracy could be improved by in creasing the amount of sample. 78]. • Electrolytic Refining. A plant for the wet purification of mercury has been described . particularly if it is 17. and then covered with a layer of zinc oxide. mercury is distilled and deposits on the underside of the cover. no stan dard methods exist for removing mercury from sulfuric acid . Parallel gravimetric determination of the excess of po tassium iodate precipitation agent is possible with thiosulfate after the mother liquor has been acidified with sulfuric acid and potas- .02 μg/g of solution . Atpresent. The final mercury concentration is < 0. intimately mixed with iron filings. They can be removed by filtration. calcium. Additional methods. Impurities in the form of gold ppm) are manifested as dark particles a f ter dissolution in nitric acid.7 Chemical Analysis The oldest and simplest method for deter mining mercury in minerals is described by E S C H K A . hydro chloric. The aqueous solution can be separated from the mercury by decanting. A method for precipitating monovalent mercury as an iodate from a neutral or weakly acidic solution (nitric acid) is described in .906 Handbook of Extractive Metallurgy conjunction with activated carbon as adsor bent. which also condense on the gold foil. to oxidize impu rities.6 Quality Specifications Fine Purification of Metallic Mercury . to be used to produce cadmium-mercury telluride. and traces of water can be removed with calcium oxide. The reliably detectable minimum mercury content is between 10 and 50 ppm. Distil lation can be carried out in normal steel vessels or in a glass apparatus. Measurements can be affected by cadmium and arsenic. it involves a gravimetric method in which mercury is precipitated as an amalgam . The cru cible is closed with a tightly fitting cover of gold foil having a cup-shaped depression in the middle. or calcium oxide. or peroxide. • Wet Oxidation. In an aqueous medium. The ox ides formed have a lower density than mer cury and float on its surface.Only a few purifi cation methods exist. Elements with a lower vapor pressure than mercury can be separated in this way. In this method. Higher purity is sel dom required. • Distillation. and sodium can be removed by passing air or oxygen through the liquid metal. • Dry Oxidation . whose technique greatly affects the accuracy and reproducibility of the results. or with drawing the mercury through an opening in the bottom. copper. scooping. When a constant weight is reached at the gold foil. Mercury can be determined gravimetrically after the mercury(I) iodate precipitate is washed with ethanol and diethyl ether. This method of mercury determination requires a high level of experimental skill and care on the part of the analyst. readily oxidizable constituents such as magnesium. On careful heating of the sam ple. Theoreti cally.
1 ng/m with the Coleman mercury analyzer system (based on a very selective cold vapor atomic absorption). Mercury is frequently used in pressure gauges and for thermal content measurements. The result of the analysis is available immediately and simpli fies the monitoring of a production plant. mercury oxide. only 5 % of the mer cury was present after 21 d. iron.9 Uses Because of its special properties. Modern operational monitoring employs physical analytical methods and test tube methods suitable for quick detection. ca. Mercury in the air can be detected down to 3 0. 86]. Further investigations on the storage of mer cury in dilute solution are discussed in . When storing liquids that contain ex tremely low levels of mercury (μg/g-ng/g range) in plastic containers. One analysis takes about 3 min . as well as a list of addresses of the relevant authorities (throughout Europe) for information pur poses. DORIAS presents a detailed description of the properties. Both Xray fluorescence spectroscopy and atomic ab sorption spectroscopy (AAS) have proved suitable for quantitative and qualitative mer cury determination. mercury losses occur with a large number of plastics. normal-quality steel.02 μg/L can be measured. 863. to an accuracy of 10%. are available. and 18 % had evaporated.8 Storage and Transportation A classification for the transportation of mercury. which in turn disproportionate to Hg0 and 2+ 3+ Hg . and a range of plastics are suitable for storing mer cury. mercury is deter mined by the black precipitate formed on dropwise addition of a Sn2+ solution . 17. Addition of Au ions in trace amounts is sometimes recommended . which indicate the atmospheric mercury concentration as an ana log or digital display after a short warm-up time of the spectrometer. which is practically insoluble in ethyl alcohol or diethyl ether . The measurement value can also be recorded con tinuously at stationary measurement sites with a recorder. 868). mercury(I) chloride. Both methods give good results. handling. the resultant solution is oxidized with a drop of bromine (the solution must not turn yellow) and then boiled with a few milliliters of the reagent (10 g of KI and 100 g of NaOH in 100 mL of H 2 0 ) and filtered. This complexes with copper diethylenediamine sulfate to form violet crystals of the complex double salt copper diethylenediamine mercury iodide. The Hg ions are assumed to be reduced to Hg + ions. A mercury con centration of 0. In general. and mercury(II) chloride is given in  (specification sheets 831. 17. Differential pulse anodic stripping voltammetry in conjunction with a gold electrode can be used to detect copper and mercury in natu ral water and wine [85.Mercury 907 sium iodide has been added. Portable atomic absorption spectrometers. 865. and transporta tion of dangerous substances . A quick method for determining mercury(II) is based on the fact that a complex is formed when an excess of potassium iodide is added to a neutral or weakly ammoniacal mer cury solution. The detection limit for these methods is so low that the maximum workplace concentration values can be moni tored precisely . mercury has had a number of uses for a long time. glass. for example. containers of stainless steel. Approximately 77 % of the mercury had been adsorbed on the 2+ side walls. ceramics. 1 g of the substance to be tested is digested with acid. The conventional application is the thermometer. When water containing 5 ng/g of mercury was stored in polyethylene bottles. In the filtrate. storage. The influence of interfering factors in AAS determination is discussed in . . In a rapid classical qualitative method for detecting mercury. The provisions differ from country to country and must be ascertained from the rele vant authorities.
g. substitution possible largely through electronic components exploitation of scrap refuse combustion demand for fluorescent lamp breakage tubes increasing. plastic. Table 17. removal of old paint coats declining. electronics) refuse combustion declining. mercury alloys have a wide range of applications. reagents compound Alkali-manganese batteries Mercury oxide batteries Pesticides chloride/metal oxide 37 20 27 Medicinal sector Dental amalgams metal Disinfection compound Fungicides for paints Catalysts Thermometers. Because mercury forms alloys with a large number of metals. oscillators. Mercury is used as a liquid cathode in the production of chlorine and sodium hydroxide by chlor-alkali electrolysis. separate collection declining distribution now only for seed treatment. in some cases restrictions on use Chemicals. total use increasing refuse combustion declining Electrical engineer.metal ing components interval switches Fluorescent tubes metal 6 3 Pigments sulfide 1 In mechanical engineering. or liquid at room temperature. Among electrical components.. Solid amalgams may contain liquid-phase inclusions. mercury is used in mercury vapor diffusion pumps for producing a high vacuum. Solid amalgams are intermediary phases. An amalgam is sometimes difficult to identify experimentally. mercury switches.908 Handbook of Extractive Metallurgy Table 17. One important area of use is the lighting industry. manometers compound 26 10 compound metal 8 8 chemical industry declining instrument and ap. substitutes are available refuse combustion separate collection possible weathering exploitation.10 summarizes the areas of use of mercury and its compounds. Area of use Form Approximate amount. which contain up to 30% mercury. whereas plastic amalgams are suspensions of solid particles of the alloying partners in mercury or a saturated mercury solution. JANGG has suggested a suitable apparatus for synthesizing and analyzing amalgams . barometers. where mercury is added to various types of bulbs. waste elimination Remarks largely impossible to find suitable replacement. environmental damage can be reduced by other measures refuse combustion reduced emission by separate collection possible refuse combustion alternatives still too expensive. often mixed with alloying partners or their primary mixed crystals. . 17. and primary batteries can be mentioned.refuse combustion replacement by other methods and processes paratus breakage possible (e. rectifiers. Liquid amalgams are true solutions of the alloying elements in mercury. t/a 40 Emissions laboratories Other sectors. despite reduction in mercury use per tube.10 Mercury Alloys The alloys of mercury (amalgams) occupy a special position among metal alloys because they can be solid.10: Uses of mercury and its compounds .
Many metals can be deposited from their aqueous solutions or from salt melts on mercury cathodes.62 ca. 10 virtually insoluble -5 Ammonium amalgam.4 Metal Mg Au Ag Cu Al Fe Si Solubility. gold).5 5. Mn) can be deposited from acid solutions. 4 . Figure 17. 0. silver. sodium) or endothermic (e. After surveying the literature.Mercury 909 The solubility of many metals in mercury depends strongly on temperature (Figure 17.g.11.131 0.5: Solubility of some metals in mercury as a function of temperature . The reaction rate of spontaneously occurring amalgam formation is determined by the degree of dispersion of the powder. they are preferably pulverized as master alloy in the desired weight ratio. Fe. Because of the high overvoltage of hydrogen on mercury or amalgam cathodes. The measurement range of mercury thermometers can be extended to .99 147 ca.g. Alkali amalgam is an important intermediate in chlor alkali electrolysis by the amalgam method. A comprehensive list of thermodynamic data on amalgam formation has been collected by GUMINSKI . % ca. Technically important amalgams are those of tin-copper precious metals used in conservative dental treatment. or tin amalgams are still used for much gold. 0. Gold. 0. Amalgams also play a role in the extraction of cadmium or aluminum . Metal Tl Cd Zn Pb Sn Na K Solubility. is an interesting case of the NH group acting as a metal-like alloying constituent. as well as for production of certain types of mirrors. the rate at which reactants diffuse into one another. which has been known for a long time. 0. % 42. by reacting a nonprecious amalgam with a noble-metal salt solution). If other components besides mercury are added simultaneously. he is of the opinion that liquid mercury greatly influences intermetallic compound formation. The solubility of some metals in mercury at room temperature is given in Table 17. Amalgam formation may be exothermic (e..0 1.035 ca.5 8 °C by addition of thallium to mercury. Production of Amalgams. Nonaqueous solutions may also be used (with Mg. The reactions are comparable to the solid-state formation of ionic and nonionic substances in liquids.002 ca.002 0. • Reaction with Sodium Amalgam. The powdered alloying components are mixed with mercury. Three methods are used for the industrial production of amalgams: • Powder Metallurgy Method. • Galvanic Method.. generally.9 0. The synthesis of tetramethylammonium amalgam is described in . Ti). Table 17.and silver-plating work. In many cases. the powder reacts with mercury more quickly in the presence of a salt of the element to be amalgamated.11: Solubility of some metals in mercury at 20 °C . and the wettability of the powder by liquid mercury. Metal exchange can occur in a fast and stoichiometric reaction through the phase boundary by reaction of sodium amalgam with the salt solution of a precious metal (or.5). with simultaneous formation of an amalgam. even nonprecious metals (Zn.3 0.
They can also be produced synthetically.g. the red one of crystals > 8 μm in diameter. Mercury(II) oxide is sparingly soluble in water and in ethanol.e. Whether the yellow or the red form is obtained depends on reaction con ditions: slow crystal growth during heating of mercury with oxygen or during thermal de composition of mercury(I) nitrate leads to rel atively large crystals (i.. Production.11 Compounds Mercury occupies a special position in group 12 of the periodic table. With excess anions they form complexes that are more soluble than the salts themselves. HgO. Most of the monovalent com pounds are sparingly soluble in water. un dergo considerable hydrolytic cleavage in wa ter. Compounds of monovalent mercury con tain ions in the unusual form Hg 2 + . Only the oxide and the sulfide are of practical im portance. The chalconides of divalent mercury exist in na . compounds of monovalent mercury can be prepared from those of the di valent element by reduction with metallic mercury. Under certain preparative conditions a hexagonal form ex ists. The other compounds can be obtained from the resulting oxidation product by further reaction. ture as minerals: the oxide HgO as montroydite. The more soluble salts. are par tially hydrolyzed in aqueous solution: after acidification of these solutions. The color depends on the size of the crystals: the yellow oxide con sists of crystals < 2 μm. In addition. and the telluride HgTe as coloradoite. Mercury(II) oxide can be pre pared via the anhydrous route by reaction of the elements at 350-420 °C under oxygen pressure or by thermal decomposition of mer cury nitrates at ca. the chloride and the cyanide. a method that can be used to prepare these salts. e. The crystal lattice is rhombic and identical for both forms. the selenide HgSe as tiemannite. chlorine or nitric acid. The former. the nitrate. Increasing the temperature leads to an intensification of the color: the yel low oxide becomes yellow-orange. pH.g. and 17. dark red. the red one. This modification has no practical impor tance and can be converted to the more stable rhombic form by heating above 200 °C. Rapid precipitation from solution gives finer parti cles (i. the yellow form). With dilute mineral ac ids. These com pounds are not very stable and disproportionate easily to form elemental mer cury and the corresponding divalent mercury derivative. Multistep processes are often necessary. Production via the wet route by precipitation is more important: the oxide is precipitated from solutions of mercury(II) salts by addition of caustic alkali [usually mercury(II) chloride solutions with sodium hydroxide].11. Samples with particle sizes between these two values appear yellowto red-orange. e. Nevertheless.1 Mercury Chalconides Chalconides of monovalent mercury are unknown: precipitation from a solution of mercury(I) nitrate with sodium hydroxide does not lead to the expected mercury(I) ox ide.e. it forms compounds in two valence states. e. Heating above 450 °C causes the oxide to decompose into elemental mercury and oxy gen. such as the sulfate and the nitrate.g. The weakly dissociated compounds..1 g/cm3.910 Handbook of Extractive Metallurgy 17. The compounds of divalent mercury can be divided into those that are strongly dissociated and those that are weakly dissociated. but rather to a mixture of finely divided elemental mercury and mercury(II) oxide. In contrast to the two other members of this group (zinc and cadmium).. the red form). de pending on the conditions during precipitation such as stirring speed.. solutions of the corresponding salts are formed. temperature. the poorly sol uble compounds can be obtained by precipita tion. Mercury(II) oxide. the sulfide HgS as cinnabar and metacinnabar. 320 °C. are less prone to hydrolysis by water. ρ 11. is a red or yellow powder. The starting material for all of these com pounds is elemental mercury: the metal is treated initially with a suitable oxidizing agent..
and acetone. These cells are distinguished from other systems in that their voltage re mains very constant during discharge.1 g/cm3. Uses.15 g/cm3.2 Mercury Halides Halides of both mono. Synthe sis from mercury(II) oxide and sulfur tetrafluoride has been suggested . and (βHgS (metacinnabar) has a density of 7. forms colorless octahedral crystals with a cubic ionic lattice (fluorite type). ρ 7. and in alkali sulfide solutions.. The reaction of mercury and sulfur by heating with a solution of sodium polysulfide has been de scribed . Of the two sulfide minerals. the com pound is bright red and forms hexagonal crys tals.4. having a tetragonal molecular lattice.. The halides of monovalent mercury are sparingly soluble in water: the solubility of divalent mercury halides decreases with increasing molecular mass. The β-form slowly changes to α-HgS on heating. The elements re act slowly together even on mixing. only the fluorides are ionic compounds: they undergo hydrolysis with water. whereby a mixture of . In the former. is rarely found as a mineral in nature.and divalent mer cury are known. cinnabarite) has a density of 8. It can be converted to the more stable red form by heating in the presence of the mother liquor or with ammonium polysulfide solutions. When pure. Mercury halides form numer ous basic compounds. it can exist in two forms: α-HgS (cinnabar. Production by either the dry or the wet route is possible. Mercury(II) sulfide. such as [HgS 2 ] 2 . A black color occurs in ammonia solution.. mp 645 °C. Produc tion from aqueous solutions is more important. calomel. The substance is sparingly soluble in water.2).7 g/cm3. The latter sublimes at 583 °C. ethanol. for hearing devices.11. their melting and boiling points are low. pocket calculators. HgS. for eye ointment) has decreased. it exists as a heavy white powder or as colorless crystals with a silvery luster. Both have ex tremely low water solubility. Metacinnabar is black and forms cubic crystals (zinc blende lattice). Mercury(I) chloride. and secu rity installations. hydrolysis yields a yel low color.0 g/cm3. The compound is produced from mercury and fluorine at elevated temperature or from mercury(II) oxide and hydrogen fluoride un der oxygen pressure at 450 °C . digital watches. Its impor tance as an additive to antifouling paint for ships and in medicine (e. Mercury(II) fluoride is insoluble in organic solvents. or ammonium sulfide solutions. and as a reagent in analytical chemistry. above 400 °C the molecules decompose into a vapor composed of mercury and mercury(II) chloride. Initially.g. is the most impor tant starting material for mercury extraction. they are also in soluble in mineral acids and in caustic alkali. The other halides either are already composed of molecules in the crystal lattice or form these by dissolution or evaporation. Accordingly. Hg 2 Cl 2 . ex posure meters.Mercury 911 method of mixing the components. They dissolve only in aqua regia. Mercury(II) fluoride. cinnabar is the most important ore for the production of mercury (see Section 17. When pure. a mixture of mercury and sulfur is heated. to form thio complex-salt ions. HgF 2 . large crys tals can be obtained by the wet route and. ρ 9. alkali. The sulfide is precipitated from so lutions of mercury(II) salts by treatment with hydrogen sulfide.1. It is unstable in humid air. the red form is produced . therefore.g. they are used mainly as small button-shaped batteries. 17. mercury(I) fluoride simulta neously undergoes disproportionation. Of these. It sub limes at 385 °C. Red mercury(II) oxide in particular has become increasingly important for the production of galvanic cells with mercury ox ide anodes in combination with zinc or cad mium cathodes. The compound is used in organic synthesis as a fluorinating agent. e. diethyl ether. Additional uses of mercury(II) oxide include the following: for the production of mercury(II) salts by treat ment with the corresponding acids. to release sulfur. the black sulfide is formed.
at tached to cooled receivers in which calomel vapor condenses [105. ρ 6.. Very finely divided mercury(I) chloride can be obtained by precipitation from a dilute nitric acid solu tion of mercury(I) nitrate and sodium chloride . so lutions of chloro complex salts are formed. Uses. e. in tensive stirring is necessary. this process is used ana lytically to bind chloride ions in determining the COD of effluents. Mercury(II) sulfate. as a depolarizer in dry batteries. The sublimate is much more soluble in alkali chloride solution than in pure water. the name calomel. Mercury(II) bromide. in ether. and the evolving mercury(II) chloride vapor is condensed to a solid in receivers. bp 320 °C. Other uses (e. is an indication of the absence of calomel. The sublimate is readily soluble in organic solvents. the reaction is carried out with the appearance of flame at > 300 °C. for example. The chloride formed precipitates as crystals after the solu bility limit has been exceeded. bp 303 °C. Mercury(I) chloride finds application in calomel electrodes. 2[HgCl4] .. Formation of mercury(I) chloride is avoided by the use of ex cess chlorine . forms colorless crystals with a rhombic layered lattice. is a white. Its solubility increases sharply with increasing temperature: the saturation limit is 6.2% at 20 °C and 36. mixing Hg 2+ ions with Cl . the compound may therefore be purified by recrystallization from water. e. If an alkali chloride solution is used in place of water. the substance can. and as a re agent in analytical chemistry.g. it is also employed as a fungicide and insecticide in agriculture. Mercury(II) bromide is readily sol- . sublime under reduced pres sure. HgCl 2 . therefore. because of the formation of chloro complex ions. Mercury(II) chloride. mercury(II) iodide. Mercury and chlorine also react in the presence of water. which serve as standard electrodes for the measurement of electro chemical potential. Molecules of mercury(II) chloride exist as such in all solvents. Mercury(I) chloride is mixed with gold for painting on porcelain. At the melting point the vapor pressure is 560 kPa. mp 280 °C. The compound is used as a catalyst in the synthesis of vinyl chloride. so that a clear solution. for example.0% at 100 °C.05 g/cm3..g. Production. and as a catalyst in organic synthesis. Production.912 Handbook of Extractive Metallurgy finely divided elemental mercury and mercury(II) ammonium chloride is formed by disproportionation—hence. mercury(II) ammonium chloride. Its water solu bility is highly temperature dependent: the concentration limit is 0. as a pesticide or in seed treatment) have declined considerably. Aqueous solutions of sublimate are weakly acidic. An intimate mixture of mer cury and mercury(II) chloride is heated at 525 °C in closed iron or fused silica tubes. The sublimate is moderately soluble in cold water.g. corrosive sublimate.in aqueous solution leads immediately to undissociated mercury(II) chloride molecules. from the Greek word meaning beautiful black. mercury(II) oxide. The escaping sublimate va por is condensed in cooled receivers.43 g/cm3. mp 236 °C. ρ 5. HgBr 2 . in contrast to mercury(I) chloride. which are used mainly for the production of other compounds of divalent mercury . resulting from hydrolysis of a small amount of the chloride. crystalline powder with a rhombic crystal lattice. is heated in the dry state with sodium chloride. It has minor im portance as a wood preservative and retains some importance as a fungicide. 106]. where it settles as fine crystals. heavy. For the formation of mercury(II) chloride from the elements. in this case. mercury (I) chloride. Synthesis from the elements is also possible . Mercury(II) chloride is an important intermediate in the production of other mer cury compounds.6% at 25 °C and 18% at 100 °C. Mercury(II) chloride can also be prepared from other mercury compounds. mercury is oxidized with chlorine in heated retorts. the chloride separates as crystals on cooling. A warm sublimate solution is ob tained from the reaction of mercury(II) oxide and a stoichiometric amount of hydrochloric acid. and organic mercury compounds.
mp 70 °C. HgI 2 . and dried at 70 °C. mp 178 °C. on cooling. with the compound swelling to many times its normal volume.4 Acetates. numerous basic compounds are derived from them. and a dark-colored.68 g/cm3. it turns red. bp 354 °C. or by precipitation from a nitric acid solution of mercury(II) nitrate with addition of sodium bromide . voluminous residue is left. 17. A yellow product is formed by sublimation. from which the mercury(II) iodide crystallizes after a few hours. ρ 3. The com pound is produced from mercury and bromine in the presence of water. Mercury(II) acetate. therefore. Compounds of divalent mercury are readily soluble in dilute acid. Mercury(I) nitrate is the most readily available soluble salt of monovalent mercury and is. . in that they also exist in solution as undissociated molecules and form highly soluble complexes with an excess of the anion. The thiocyanate is sparingly soluble in cold water. Mercury(II) iodide. "Millons reagent".3 Mercury Pseudohalides The cyanides and thiocyanates of divalent mercury resemble the halides. The melt is used as a nonaqueous solvent. Red mercury(II) iodide is solu ble in diethyl ether. mp 259 °C. Nitrates. It is used as a reagent for ar senic and antimony. It is produced by dissolution of mercury(II) oxide in dilute acetic acid and concentration of the resulting solution. Mercury(I) nitrate. Uses. an important intermediate for other mercury(I) derivatives. is produced by dissolving mercury in cold dilute nitric acid and crystallizing the compound from the re sulting solution.27 g/cm3. sparingly solu ble compounds can easily be prepared from it by precipitation from aqueous solution. is prepared by dissolving mercury(II) iodide in a concentrated potas sium iodide solution. the poorly solu ble mercury(I) thiocyanate. ρ 3.12). Potassium mercury iodide. which forms colorless crys tals (monoclinic ionic lattice). exists in a red and a yellow form.11. The transition temperature is 127 °C. as an intermediate in the production of bromine-containing organomercury compounds (see Section 17. ρ 4. 17. The compound is produced by adding an aqueous solution of potassium iodide to an aqueous solution of mercury(II) chloride with stirring. chloroform. and methanol. Mercury(II) acetate is used for the synthesis of organomercury compounds. and as a catalyst in organic synthesis. (CH 3 COO) 2 Hg. Yellow mercury(II) iodide . a solution of mer cury nitrate and nitrous acid in dilute nitric . K 2 HgI 4 .Mercury 913 uble in diethyl ether and ethanol. is a white powder which is thermally unstable. and as a reagent in analytical chemistry. as a catalyst in organic polymerization reactions. Decomposition begins at 110 °C and becomes spontaneous at 165 °C.11. It is produced by precipitation from mercury(II) nitrate solution with a stoichiometric amount of potassium thiocyanate solution and is used as an analytical reagent and as an intensifier in photography. It is solu ble in diethyl ether and ethanol. nitrates. The acetate and the sulfate of monovalent mercury are sparingly soluble and the nitrate is quite soluble in dilute acid. is unstable at room temperature and is converted to the red form at the slightest touch or upon heating. Hg(SCN) 2 . and sulfates of mer cury are composed of ions and undergo hy drolysis with water. which can be obtained by precipitation from mercury(I) ni trate solution. Sulfates The acetates.71 3 g/cm . Hg 2 (N0 3 ) 2 2H 2 O. In air a blue flame appears. has no practical importance. the precipitate is then filtered off. Yellow mercury(II) iodide is prepared by pouring an alcoholic solution of the red form into cold water. Ther mal decomposition leads to red mercury(II) oxide. exists as a fine white pow der or colorless shiny crystal flakes. Mercury(I) cyanide is unknown. moreover. whereby a pale yellow emulsion is formed. washed. Mercury(II) thiocyanate. readily soluble in water. by dissolution of mercury(II) oxide in hydrobromic acid.
Mercury(II) nitrate. Many compounds are light-sensitive and must. Mercury(I) sulfate. only mercury(II) amidochloride has any practical im portance. It is prepared by fuming mercury with concen trated sulfuric acid or by dissolving mercury(II) oxide in dilute sulfuric acid and evaporating the resulting solution until the compound crystallizes.914 Handbook of Extractive Metallurgy acid. environmental protection necessitates appropriate precautions (see Section 17. Proper consideration must be given to the chemical and toxic properties of mercury compounds and the necessary pro tective measures. Hg2SO4. Hg(N0 3 ) 2 H 2 O. Storage and Transportation.11.5). is a fine. It is used as a depolarizer in stan dard cells after Clark and Weston. Uses include the production of other divalent mercury derivatives. as a nitrating agent in organic synthesis.11. It is insoluble in water and in ethanol. ρ 6.56 g/cm3. Mercury(II) amidochloride is used in the treatment of severe skin disease. ρ 7. ρ 3 5. to amine complexes or mercury(II) nitrogen compounds. Determination of the purity of mer cury compounds. and Transportation. is used as an analytical reagent for the in dication of tyrosine-containing proteins. and so dium thiosulfate solution. because of their toxicity. 17. Plastic-lined steel drums are normally employed for pack ing. which consists of the deter mination of trace amounts of foreign cations and anions. The compound is prepared by precipita tion from a solution of mercury(I) nitrate with sulfuric acid or sodium sulfate solution. Mercury(II) amidochloride. ammonium carbonate solution. Apart from the anhydrous salt and the monohydrate. Further more. Protective Measures. On heating it de composes without melting. The compound can be precipitated from mercury(II) chloride solution with an ammonia solution. this is particularly true in container labeling. is a white powder (rhombic crystal type). Storage. or by electrochemical oxidation of mercury in dilute sulfuric acid.g. for chemical labora tories) are usually placed in plastic or glass bottles.38 g/cm . as a catalyst in the production of acetaldehyde from acetylene and of anthraquinonesulfonic acids. depending on reac tion conditions. the resulting solution is concentrated and the nitrate crystallized by cooling. therefore.5 Mercury-Nitrogen Compounds Reaction of mercury(II) compounds with ammonia solution leads. white crystalline powder with a rhombic crystal lattice. as an eye ointment. is a colorless microcrystalline powder (monoclinic crystal system) that is very sensitive to light. Hg(NO 3 ) 2 or . Mercury(II) nitrate is produced by dissolving mercury in hot con centrated nitric acid. several other hydrates and basic compounds are known. involves specific reactions of these ions . its importance is declining because of the development of mer cury-free products. and as a depolar izer in galvanic elements. hygroscopic crystals. Small amounts (e. Mercury(II) sulfate is used in analytical chemistry to bind chloride ions in the determination of the COD of waste water .. require the same protective measures during production and processing as metallic mercury. and soluble in warm acid. H g S O4 . HgNH 2 Cl. Mercury(II) sulfate. and as a veterinary preparation. 17. forms colorless. . be adequately protected from light sources.49 g/cm3. conventional methods for the trace analysis of cations have been supple mented or replaced by methods involving the simultaneous determination of several ele ments by means of plasma emission spectros copy . Protective Measures Analysis. and as an analytical reagent. Of the numerous compounds known. Most mercury com pounds.6 Analysis.
and water. Intervention by the former Soviet Union has seriously depressed the price of mercury to dumping price levels.R .C H = C H . In an organism it is easily converted to methylmercury ( C H .g. Organic mercury compounds can be determined quantitatively by atomic absorption spectroscopy. where R is aliphatic or aromatic and X is a halogen or an acid group. The best known diarylmercury derivative is diphenylmercury. sweet-smelling liquid. or alcoholic solutions [114.. In the presence of mercury the green solution turns orange..C H . ethyl iodide). Dialkyl. a colorless.or alkoxymercury derivatives can be obtained via the solvomercuration reaction (Hofmann-Sand reaction) by addition of mercury(II) compounds to alkenes in aqueous. organic mercury compounds can be produced by the reaction of sulfuric acids or their sodium salts with mercury(TI) halides : R-SO H + HgX 2 2 R-HgX + SO + HX 2 Hydroxy. diethylmercury).H g . production figures have changed only slightly. methylpropylmercury compounds) are less volatile than symmetrical dialkylmercury compounds (e. According to U. C H . Organometallic compounds of divalent mercury are stable toward air.g. (C H ) Hg. is very toxic. Synthesis of organic mercury compounds can be carried out by reaction of Grignard reagents with mercury halides [114. Organic mercury compounds may be analyzed in the following ways: they can be determined qualitatively (1) by digestion with concentrated sulfuric acid and 30% hydrogen peroxide or (2) by digestion with 10% sulfuric acid and subsequent addition of dithizone (diphenylthiocarbazone) in carbon tetrachloride solution. alkaline. 6 5 2 RMgX + HgX 2 RHgX + MgX 2 Furthermore. the mercury salt and the Grignard reagent must contain the same anion 1 2 1 2 tives. Dimethylmercury. After 1990. organic derivatives of monovalent mercury are unstable and can be prepared only at low temperature.S. 53% of the potential capacity.g. and is soluble in ethanol and diethyl ether. it has a density of 3. + 3 3 Diarylmercury Derivatives. leading to the diseases that have been caused by mercury and its derivatives. dialkylmercury compounds are hydrolyzed to monoalkylmercury deriva3 3 3 A detailed description of the development of production is given in the metal statistics of Metallgesellschaft AG. which is produced by direct mercuration. although this has been resisted by Spain and Algeria. In contrast.Mercury 915 17. Because of reduced demand many mines and smelting plants are no longer operating or have greatly cut back production. The change in the price of mercury . To obtain pure products. Mixed dialkylmercury compounds (e. These species can react with free S-H groups of biologically important molecules. bp 96 °C.12). Over the last ten years. Frankfurt  (Table 17.. 115].R + Hg(OAc) + R O H 2 1 2 3 Analysis.13 Economic Aspects (R O)CHR -CHR HgOAc + AcOH 3 1 2 Organic mercury compounds can be converted to other organometallic derivatives by electrolysis or transmetallization . Dimethylmercury is formed in organisms by enzymatic methylation of elementary mercury or a mercury compound. and compounds of the type R-Hg-X. 117]: R . use of organic mercury derivatives in Germany will be difficult because mercury will not be allowed in industrial effluent or wastewater.H g . In acidic aqueous solution. current production is ca.H g ) or methylmercury(II) chloride (CH -Hg-Cl). 17. where R and R are aliphatic or aromatic groups. estimates.or Alkoxyalkylmercury Compounds. 113] are among the oldest known organometallic compounds. Organomercury compounds can be divided into two major groups: compounds of the type R .069 g/cm . oxygen. Dialkylmercury derivatives are generally very reactive and can also undergo transalkylation with simple alkyl halides (e.12 Selected Organic Compounds Organic mercury derivatives [112.
Eastern-Bloc countries.14 . quotes production prices of $300 per flask. Guizhou Province contains five mines. The use of mercury in paints. The purchase of mercury by individual sectors has decreased sharply since 1980. in contrast to the high export level in 1986. once a large mercury producer. China claims to have the largest mercury resources in the world. 40 000 fl. The former Soviet Union produces ca. 90% of Chinese production. a large part of the production being exported to Brazil and Argentina. . 10 000 flasks) was extracted from mines in 1986. Table 17. The utilization of mercury in a highly industrialized country such as Germany is shown in Table 17. The production for 1988 is 14 000 flasks. Most of the Chinese production is exported to the United States. and former Yugoslavia. Belgium. followed by the alkali chloride industry. The main user of mercury is the electrical engineering industry. and pesticides has fallen sharply. and France. now imports mercury from Algeria. The capacity of production plants at the Anzob antimony mercury complex in Tajikistan has been doubled. In Mexico. Spanish mercury production is ca. 1984 Europe Spain Finland Yugoslavia Asia (Turkey) Africa (Algeria) America Dominican Republic Mexico United States Total Western countries Czechoslovakia USSR China b b a a 1985 1757 1539 130 88 226 801 965 1 394 570 3749 158 1200 800 2158 5907 1986 1693 1471 147 75 262 764 695 185 510 b 1987 1764 1553 144 67 211 756 264 124 140 2995 164 1200 900 2264 5259 1988 1704 1499 135 70 97 662 724 345 379 1989 1178 967 160 51 202 587 1065 651 414 1990 1140 962 141 37 60 639 1195 735 460 1991 135 52 74 9 b 1992 128 36 85 7 5 476 85 21 64 b 1993 734 636 98 1994 475 386 89 1672 1520 80 72 182 586 1043 2 384 657 3483 152 1220 800 2172 5655 25 431 398 340 58 b 459 82 12 70 1275 50 1700 468 2218 3493 400 80 10 70 955 50 1500 408 1958 2913 b b b b b b 3414 168 1200 850 2218 5632 3187 168 1180 900 2248 5435 3032 131 1180 1200 2511 5543 3034 126 2100 800 3026 6060 989 75 1900 780 2755 3744 694 60 1900 392 b Total Eastern countries Total world a b 2352 3046 Excluding Estimates. Entreprise nationale des non-ferreux et substances utiles (ENOF). and in large sectors no foreseeable substitute exists.13 . The Algerian mercury producer. pigments. 67 000 fl of mercury.916 Handbook of Extractive Metallurgy since 1979 is shown in Table 17. The main producers of mercury extracted by mining are as follows [ 121 ] (figures refer to flasks): Algeria China Finland Yugoslavia Mexico Spain Former Czechoslovakia Turkey Former Soviet Union United States 23 20 2 2 10 42 4 6 66 14 000 000 300 000 000 000 400 000 000 000 1 350 t of mercury (ca. accounting for ca. Italy. the Netherlands. 2000 fl of mercury is exported. The major proportion of former Yugoslav production of ca. The development of prices and production figures will certainly be influenced substantially by acceptance of the metal mercury. The main importers are the United States.12: Production of mercury in tonnes . A survey of previous mercury prices is included in . ca. almost the entire production is now reserved for domestic use. 1 The sole producer in the United States discontinued mining operations from the middle of 1987 to February 1988. Luxemburg.
10-3.2 24. methyl mercury and mercury(II) chloride cause a dose-dependent suppression of spermatogenesis.0 18.453 9.g. among other things. Metabolism.23 297.7 1984 31. Price $ per flask (34.3 45. in most cases.2 182.46 The toxicity of mercury is based upon its action as a general cell and protoplasmic poison. In foods.722 249.49-200.6 35.5 13.0 36.83-7.785 295.63 200.3 30.6 28.36 245.2 mg per 100 mL of blood.3 .7 86 6.2 99 10.5 24. The toxicity of mercury depends.473 kg) $/kg 310.3 7.2 6.5 247.32 £/kg U.0 99.33-119. Environmental contamination with mercury leads to a critical concentration effect in animals that occupy higher positions in the food chain (large fish and fish-eating sea fowl).49 246.1 33.9 30.2 31.7 55.1 100 14.0 12. dyes Pesticides Electrical engineering Control instruments and apparatus construction Chemicals and reagents Medicine Miscellaneous Total Total.51 5.0 53.0 1981 50.2 62 346.24-8.57 9.0 1978 87.55 5.0 127.7 27. 1973 Alkali chloride industry (without changes in stock levels) Catalysis Paints.13-7.41 5.6 28.4 24.6 12.4 13.8 26.8 325. Various mercury compounds are very potent poisons.8 4.2 261.e.85-173.510 194.5 0.9 0.5 1980 72.1 mg/m leads to severe chronic mercury poisoning.4 14.5 30.05 ppm. Compounds containing divalent mercury are generally more poisonous than monovalent ones.99-3. This leads to blocking of many enzyme systems.3 331.0 25.4 1982 46. European price Year 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 £ per flask (34.5 35.5 mg of mercury per kilogram.1 ppm.8 25.473 kg) 284.218 122.9 23.2 23.5 43.9 33. The kidneys and nervous system are especially vulnerable.9 256. in Germany. 0. i.6 192.5 26.68-5. In animal experiments.40 8. % (1980= 100%) 1974 1975 1976 1977 78.0 46.00-3.14: Breakdown of mercury use (in tonnes) in former West Germany according to sector .1 25. damaging membranes.7 42.9 3.5 9.6 26.03 3.73 8.24 187.15-7.5 84 17.7 110 11.44 126.0 23. concentrations of 10 ppm of mercury and more have been found: fish and clams originating in Japan's Minamata Bay contained up to 9.02-125.390 186..1 3.2 295. 0.3 1983 40.8 276.0 56.79 103.2 14.6 43. Mode of Action.1 73 4.2 65 3.14 Toxicology and Occupational Health  Uptake.4 10.5 16.0 45.35 107.6 8.0 5.8 51.2 24.0 19.0 89 4.3 24.22 3.3 9.02 6. denaturing proteins.81 7. Table 17.6 22.63 2.4 27.1 7. bonding to the sulfhydryl groups of proteins.43-261.S. In certain fish.3 291.1 54. in the United States.44-5.8 7.9 32.1 112 9.46 3.5 1979 87.0 19.6 216.0 15.02-293.0 313.7 40.23-119.0 103.7 33.64 8. Eggs of wild birds on the Finnish coast contained up to 3.35 7.1 22..13: Quoted prices for mercury in London and New York. on its state of aggregation and degree of dispersion.1 30.1 3.4 31.0 65.01 7. Daily 5-h exposure to inhaled mercury vapor concentrations of 0.0 94 27.3 30.8 31.2 30.1 24.2 17.6 14.1 17. they are less toxic than organic mercury compounds.0 45.5 30.517 287.23 3.424 201. 3 17.8 128.503 335.7 24. different mercury concentrations are tolerated: e.2 42.8 12.64-255.6 mg of mercury per kilogram. Acute poisoning occurs when mercury ion concentrations reach 0.0 1.Mercury 917 Table 17.5 26.62-9.0 44.84 5. Still. and reducing the RNA content of cells. Up to 270 mg of mercury per kilogram of organ tissue was found in dead seed-eating birds.0 106 18.1 53.8 117 29.17-310.05 103.6 40.59 5.6 1985 41. Both fine particulate dust containing mercury and mercury vapors are very toxic in comparison to the liquid metal.2 32.957 232.75 8.3 43. The toxicity of inorganic mercury compounds increases with increasing solubility.91-218.
With < 0. One of nine patients died after five months as a result of the intoxication. Mercury uptake with food leads to concentrations in the kidney of < 0. Granulomas develop when mercury is injected into subcutaneous fat tissue. Acute Poisoning in Humans. Amalgam fillings are the most frequent cause of chronic mercury and tin intoxication. which is practically insoluble in the body. the LD in this case being of the order of 100 mg of mercury per kilogram . Toxicity of Metallic Mercury and Inorganic Mercury Compounds. Metallic Mercury. The toxicity of mercury(I) chloride (calomel) depends on its retention time in the gastrointestinal tract. which is highly poisonous even though it hardly dissociates.02-0. They resulted from skin absorption and from inhalation of the mercury that vaporized on the skin. especially when the 3 3 3 50 50 . Salts of divalent mercury are more toxic than monovalent ones. In animal experiments the LD after parenteral injection for divalent salts is ca. 0. an increase in subjective signs (micromercurialism) has been observed at 0.918 Handbook of Extractive Metallurgy Humans are estimated to consume 0. for adults. The lethal dosage for adults is generally 2-3 g. A total of 0. Acute inhalant poisoning is very dangerous.1-3 mg/kg. after surgical excision.2 g) are fatal.1 mg/m . Absorption occurs when the mercury depot is broken up into minuscule droplets.2 g introduced into the vagina can be fatal. 2 . Liquid mercury is not highly toxic. for children.1 g of mercury(I) chloride have led to death. Cyanide ions may enhance the toxicity. for example.4 g . The toxicity of mercury and its compounds depends predominantly on their solubility. therapeutically administered doses of 0. in former times. During chewing (gum) up to 26 mg/L of mercury and 0. However.1 mg of mercury per cubic meter. either suicidally [124. In sensitive persons. which determines absorption and distribution in the organism. An exception to this is mercury oxycyanide [Hg(CN) HgO]. after several hour's exposure to mercury vapor concentrations of 1-3 mg/m . The metal is transformed to highly toxic organic compounds by oral microorganisms. this can occur in suicide attempts or injuries to the hand caused by broken thermometers.2 mg of mercury weekly in their diet. Mercury(II) chloride (corrosive sublimate) is one of the strongest corrosive poisons. Chronic inhalant intoxication can be expected with mercury vapor concentrations of 0. with all grades of severity being encountered. the corresponding concentrations with intoxication are 10-70 mg/kg.1-1 mg/m . Thermometers that break in the rectum lead to mercury intoxication only if a wound is created and mercury is pressed into the tissues from which it is slowly absorbed. with the exception of red mercury sulfide. Strongly dissociated salts are more caustic and generally more toxic than less dissociated ones. After 15 min. Mercury embolisms resulted.50-1. oral doses of 0. they are much less toxic if administered orally. and some of the patients showed symptoms of intoxication. regardless of the route of administration. the mercury content of the respiratory air increased eightfold.3 mg/L tin may be set free. it was used as a treatment for ileus. As a result of their poor absorption. even though people have survived after ingesting 5 g. Mercury Salts. in earlier times. Administration of 1. Mercury vapor causes acute damage to the lungs and chronic damage to the central nervous system. acute pneumonitis resulted. 5 mg of mercury per kilogram.0 g (in several cases even 0. 125] or accidentally during intracardiac catheter studies when blood was drawn for blood gas analysis by using mercury-filled syringes. Antisyphilitic treatment with gray mercury ointment caused numerous intoxications. Blindness as a result of occlusion of the central artery also occurred. Occasionally liquid mercury has been injected intravenously.5 g of mercury oxycyanide was lethal. even mild intoxication is improbable. Mercury salts are caustic to the mucous membranes of the gastrointestinal tract and nephrotoxic when absorbed. In four cases. Thus metallic mercury and all mercury compounds are toxic.
5-4 mg of mercury would have resulted. arylmercury compounds are as toxic as alkylmercury compounds when administered parenterally. selenium can reduce the toxicity of inorganic and methyl mercury.and ethylmercury compounds is 10-30 mg of mer cury per kilogram. Mercury and selenium are an tagonists. The mothers belonged to the group of people heavily exposed to me thylmercury but did not show any clear symp toms of intoxication . however. in indus trial poisonings. as well as kidney damage. Mercury salts act as direct skin irritants. In animal experi ments. Furthermore. Daily ingestion of 5 μg of mercury per kilo gram of body weight in the form of methylmercury compounds is considered the minimal toxic dose . Concentrations > 0. Even after inges tion of 1. they are less toxic. phenylmercury and alkoxyalkylmercury compounds are metabo lized to inorganic mercury compounds and act like mercury salts. In animal experiments. selenium pre dominantly delays the appearance of intoxication symptoms but reduces the lethal ity only slightly.6 g/L are locally caustic . and estimated values are questionable.1-0. The bread weighed 220 g and had a water content of 31 %. Some of them vaporize easily and thus also act in the gaseous phase. In the organism. the first fatalities occurred six to eight weeks after distribution of the seed grain [126. The stable alkylmercury compounds are neurotoxic and embryotoxic. 127]. re spectively . Mercury is mutagenic. almost all alkylmercury poisoning has been caused by contaminated food. Organic mercury compounds can cause toxic dermati tis and. Thus.6%. almost all involved chronic poisoning. also occur. The fetus is three to four times more sensitive to methylmercury than the pregnant woman . The LD 50 in rats and mice of most methyl. Affected patients had mercury concentrations of 200-2000 μg/L in their blood and 50-500 mg/kg in their hair . In humans. In adults.Mercury 919 laxative effect did not occur. Minamata disease developed in fishermen and their family members who ate fish daily or at least several times a week. This holds true for parenteral and oral administration . Numerous tox icity studies on animals have been reported. administered orally. As a result of their instabil ity they act like a combination of organically bound mercury and mercury vapor. the dose in gested is unknown. a daily uptake of 1. Whether a high dietary sele nium content can protect against methylmercury poisoning is still open to ques tion: the fish that caused Minamata disease . the brain of patients who died contained > 5 mg of mercury per kilogram . teratogenic. Chronic intoxica tion with mercury salts is unusual. Arylmercury Compounds.25 g of mercury. 15 mg of mercury per kilogram of alkylmercury (mainly methylmercury) salt. Hypersensitivity reactions. especially mercury fulminate. can severely damage the central nervous system. and em bryotoxic. 120 mg was also tolerated without symptoms. within certain limits. Toxicity of Organic Mercury Compounds. Antagonism. ingestion of 100 mg of mercury in the form of phenylmercury nitrate led to abdominal pain and mild diarrhea. clinical chemistry values and kidney biopsy results were normal. Most organic mercury compounds are lipid soluble. Congenital brain damage occurred in 5-6% of the chil dren from Minamata Bay. especially in the form of alkylmer cury compounds [129. The average me thylmercury concentration of the fish eaten is not known (estimates: 5-20 mg of mercury per kilogram of fish). exposition to mercury vapors generally exists concomitantly. Affected adults are estimated to have eaten six to eight loaves per day. as a result of their lipid solubility. Mass poisoning in Iraq was caused by pita bread baked with flour made from seed grain. Alkylmercury Compounds. where the rate ex pected was 0. they are sensitizing. however. the grain contained ca. Mild symptoms are assumed to occur with concen trations of 100 μg of mercury per liter of blood and 30 mg of mercury per kilogram of hair. consuming 250500 g of fish with each meal. 130].
DE 3243813. H. Varta. Berlin.01 ppm). The special safety measures for handling and working with mercury-containing materials are given in the TRgA (Technische Regeln für gefährliche Arbeitsstoffe. A. mist. Mater. 2. Min. X. 389-395. Linden Chemical & Plastics. 2 1 . H. H. Nucl. 28. 10. Waller de Gruyter. 370-375. Plenum Press 8(181). 213-216. Leipzig 1951. Knacke: Thermochemical Properties of Inorganic Substances. F Pawlek: Metallhüttenkunde. EFVerlag. The legal requirements covering industrial safety and hygiene when working with mercury and its compounds depend on the laws of individual countries. J. T. Hirayama: Behandlung von Sonderabfall 1. R. 1987 (S. Sridhar). Lopatenko. U. N. Simsir. Lemattre. Harlingerode. H. P. Kulander: Behandlung von Sonderabfall 1. 4. M. Kelkheim 1986. MA. (1989) 2 4 . 30. Springer Verlag. L. MenloPark 1984. Heindryckx et al. far exceed this value. Hanusch. Gallant. 11. vol. in addition to large amounts of mercury.1 mg/m (0. or organic compounds containing < 0. 13 Oct.Y. F. p. 1983. L. N. 276-278. Lurgi. 64th ed. 7. 1989. EP 0042509. Sikander). Wu: Mineral Processing and Extractive Metallurgy. 16. Bur. Preussag AG Metall. Berlin. D. Kemal. G. The Institution of Mining and Metallurgy. and organic nonalkyl mercury compounds. inorganic mercury compounds. Tafel: Lehrbuch der Metallhüttenkunde 2nd ed. K. 7/8. EFVerlag.2 7 . Explanatory information and instructions for work and health safety are summarized in a comprehensive poisons list . technical regulations for dangerous substances). 26. DE 3609517. Suttill. M. Germany. internal report. Frankfurt 1986.05 mg/m . R. A. Am.. O. Weast. pp. P. which describes the technical and personal safety measures to be adopted . L. Rep. 14. K. 1979. Res. Mines 9191 (1988) 1-12. for mercury vapor the MAK value is 0. Sandberg. p. Sheya. S. 1. lecture held at the Technische Akademie Eßlingen. in: CEC 1974 Problems of the Contamination of Man and his Environment by . Verlag Stahleisen. DE 2406119. 18. no. The odor threshold for mercury is 13 mg/m . J. 590 ff. V. Portland Place. Inst. however. mercury values in urine should not exceed 150 μg/L. 1983. 10. Kulander. 29. 1982 (A. "Mercury and Cadmium in Belgian Aerosols". 44. a high proportion of selenium [128. 25. inorganic compounds containing < 0. 1982 (R. 10161018. London 1984. 131]. Techn. Pietsch. Berlin 1987. 27. Forschungsprojekt FKZ: 143 03 553. 9. 20.. DE 2558115. Eng. 11 (1984) 305-309. The measures adopted by a highly industrialized country such as Germany are described below. Met. BMFT-Forschungsbericht NTS 0103/0. Min. p. H. DE 3709570. 8. Düsseldorf 1973. Persons working with mercury should be monitored regularly.. März 1988. 12. J. G. Bundesministerium für Forschung und Technologie. G. 1973. Chem. A series of specification sheets for handling mercury has been published. Eng. Agricola: 12 Bücher des Bergbaus und des Hüttenwesens. 5. The theoretically possible vapor pressure concentration can. Non-Ferrous Met. W. Phys. L. Tsvetn. Desmet. Skrylio. Hirzel. Maier. 17. 6. D. 15. Barin. 1986. Chemical Economics Handbook. H. The working methods and procedures must basically be designed so that employees are not exposed to mercury vapor. 1975 (G. A.920 Handbook of Extractive Metallurgy contained. Berlin 1987. Maysilles. With metallic mercury. Elektro-Ofenbau Matthias Marcus. Sov. Development Soc. Preussag AG Metall. the limiting blood level is 75 μg/L. 3-25. 1973. Heyer). 24. no. Transl. Invest. C. F.S. I. Burkett). 5. J. Ch. A. L. Erzmetall 42 (1989) no. Bull. Lumalampan.): Handbook of Chemistry and Physics. R. F. Int. Forschungsprojekt FKZ: 143 0273/0. Metals Museum 10 (1985) no. or dust. Craddock. Erzmetall 35 (1982) no. The TWA of mercury is 0. Goslar.. Metall. 264(1929). M. 3. 10-18. 339. Nov. Outokumpu O. Z. Sin'kova. Wang. 22. 13. They do not cover mercury(II) sulfide. 3 3 3 3 17.05 mg/m .05 % mercury. Peters. Boston. The blood levels should be < 35 μg/L.) 13 (1985) no. World Conf. van Petegham. Hiller: Entsorgung von Gerätebatterien. 23. R.15 References 1. FL. pp. 3. (Engl. J. Puhl. 11. Pogorelyi. Bundesministerium für Forschung und Technologie. The MAK value for metallic mercury in Germany is presently 0.1 % mercury. 19. 1979. Further details are given in . With or ganic alkylmercury compounds. Hüls. G. 6. Sprechsaal 119 (1986) no. Laig-Hoerstebrock. Köse. Astle (eds. M. Targ. 186-187. Occupational Health. SRI International. 3 1 . CRC Press Boca Raton. Tysh.
Erzmetall 30 (1977) 556. London 1980. 1978. 8 (1979) no. Horak. Koronowski: Nebenwirkung von Quecksilberverbindungen auf Mensch und Tier. Eng. Eigenschaften. DD 139068. EP 278537. Anal. Norddeutsche Affinerie AG. 57. Naturwissenschaften 62 (1975)575-576. O. Acta 107 (1979) 159-167. Spectrochim. Semimetals 18 (1981) 21-45. Merz). J.8-14. Z Angew. 8 9 . 4. A. Nagel. van der Heiden. R. 6 0 . 76. Metzger. 2nd ed. EP 0091043. 4(1978) no. D. Metzger. Volcanol. 2 . 2. Eckert. McFarlane. M. Berlin-Göttingen-Heidelberg 1953. Kernforschungszentrum Karlsruhe. Reimann. Forsch. 1983 (H. Boliden AB. C. Wacker-Chemie.und Zinkgehalte in der Frauenmilch. GEMS Global Environmental Monitoring System. Bodenkultur 26 (1975) no. J. A. 189-198. Chem. H. 85. 1987 (M. Piotrowski. 39. M. 98 (1934) 3 3 1 . Kreutzberger). 2. 9. Dams. F. Bangler. M. 160 (1976) 303-312. Eng. Chem. Bombach. pp. Metzger. 2. M. G. und ZEBS-Berichte 1/79. Forsch. B. Balcerska. Acta Part B. Golimowski. 3) 36-37. 1984 (M. Chem. 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