Sulfate solutions

As an example of the application of the method, Neumann and Tanner [54] followed the variation with time of the surface tension of aqueous sodium dode-cyl sulfate solutions. Their results are shown in Fig. 11-15, and it is seen that a slow but considerable change occurred. 

Fig. 11-15. Variation with time of aqueous sodium dodecyl sulfate solutions of various concentrations (from Ref. 54). See Ref. 56 for later data with highly purified materials.

Fig. in-12. Verification of the Gibbs equation by the radioactive trace method. Observed (o) and calculated (line) values for for aqueous sodium dodecyl sulfate solutions. (From Ref. 108.)... 

Standard EDTA Solutions. Disodium dihydrogen ethylenediaminetetraacetate dihydrate is available commercially of analytical reagent purity. After drying at 80°C for at least 24 hr, its composition agrees exactly with the dihydrate formula (molecular weight 372.25). It may be weighed directly. If an additional check on the concentration is required, it may be standardized by titration with nearly neutralized zinc chloride or zinc sulfate solution. 

Fehling s solution (sugar detection and estimation) (a) Copper sulfate solution dissolve 34.639 g of CUSO4 5H2O in water and dilute to 500 mL. (b) Alkaline tartrate solution dissolve 173 g of rochelle salts (KNaC40g dHjO) and 125 g of KOH in water and dilute to 500 mL. Equal volumes of the two solutions are mixed just prior to use. The Methods of the Assoc, of Official Agricultural Chemists give 50 g of NaOH in place of the 125 g KOH. 

Lehman, T. A. Everett, W. W. Solubility of Lead Sulfate in Water and in Sodium Sulfate Solutions, /. Chem. Educ. 1982, 59, 797. 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

Purification. Extraction from aluminum or 2inc ores produces cmde galHum metal or concentrates. These concentrates are transformed to sodium gallate, galHum chloride, or galHum sulfate solutions which are purified, then electroly2ed. GalHum is deposited as a Hquid. 

The products of reaction are pumped to a filter press for separation into a sodium sulfate solution and a filter cake having a low moisture content. The filter cake is then ready to be processed for the recovery of lead. The filtrate from the process contains an excess of sodium carbonate, and can be neutralized using the sulfuric acid drained from the batteries. 

The sodium sulfate solution may be discharged or further treated to recover sodium sulfate crystals or converted to other sodium salts for sale. 

In another development (32), the sodium sulfate solution produced during the desulfurization of paste with caustic soda is electrolyzed in a membrane ceU to produce caustic soda and high purity sulfuric acid. The caustic soda is recycled to the desulfurization stage the sulfuric acid, after concentration, can be reused in battery production. 

Copper-containing lead alloys undergo less corrosion in sulfuric acid or sulfate solutions than pure lead or other lead alloys. The uniformly dispersed copper particles give rise to local cells in which lead forms the anode and copper forms the cathode. Through this anodic corrosion of the lead, an insoluble film of lead sulfate forms on the surface of the lead, passivating it and preventing further corrosion. The film, if damaged, rapidly reforms. 

Lead shows excellent resistance to phosphoric and sulfuric acid in almost all concentrations and at elevated temperatures, as well as to sulfide, sulfite, and sulfate solutions. The corrosion film is insoluble lead sulfate which rapidly reforms if it is damaged. Lead is also resistant to chlorides, fluorides, and bromates at low concentrations and low temperatures. However, because lead is soluble in nitric and acetic acids, it is not resistant to these acids. 

Economic Aspects. Epsom salt is usuaUy shipped in bulk or in 45-kg bags. Magnesium sulfate solution can be shipped in bulk, in either totes or dmms. In January 1995 prices for a tmcHoad in doUars per 100 kg were MgSO 2 technical, 10% Mg, in bags 37.49— 40.79, works in bulk 35.28 ... 

EMD is prepared from the electrolysis of acidified manganese sulfate solution and can be summarized as follows ... 

Electrowinning from Aqueous Solutions. Electrowinriing is the recovery of a metal by electrochemical reduction of one of its compounds dissolved in a suitable electrolyte. Various types of solutions can be used, but sulfuric acid and sulfate solutions are preferred because these are less corrosive than others and the reagents are fairly cheap. From an electrochemical viewpoint, the high mobiUty of the hydrogen ion leads to high conductivity and low ohmic losses, and the sulfate ion is electrochemicaHy inert under normal conditions. 

The nickel sulfide is refined by conversion to a sulfate solution and reduction with hydrogen to produce a high purity nickel powder. 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Possible interferences and variation of results from modified techniques can be avoided by titrating the sample in exacdy the same way and by employing approximately the same amounts of materials as in the initial standardization of the ferrous sulfate against a known quantity of nitric acid. The ferrous sulfate solution is added in a thin stream until the initially yellowish solution turns brown. The titration is complete when the faint brownish-tinged end point is reached. 

Production. Commercial production of Hthopone started in the first half of the nineteenth century, and continued to grow until the middle of the twentieth century when titanium dioxide started to dominate the white, inorganic pigment market. Lithopone is prepared by combining barium sulfide and 2inc sulfate solutions at 50—60°C ... 

The amount of impurities present in the 2inc sulfate solution is determined by the local source of 2inc-containing material used in the above reaction. To get a good quaUty Hthopone, the impurities must be removed from the solution. 

The seeds are transferred to tanks containing scrap iron and a ferrous sulfate solution, and the mixture is heated to a temperature between 70 and 90°C. While the seeds circulate over the scrap iron, air is bubbled through the medium causing the seeds to grow. The process can be described by the following reactions ... 

Crystallization. Acidified aluminum sulfate solutions can be supercooled 10 °C or more below the saturation point. However, once nucleation begins, the crystallization rate is rapid and the supersaturated solution sets up. The onset of nucleation in a gentiy stirred supersaturated solution is marked by the appearance of silky, curling streamers of microscopic nuclei resulting from orientation effects of hydraulic currents on the thin, platelike crystals. Without agitation, nucleation in an acidified solution, in glass tubes, can yield extended crystalline membranes of such thinness to exhibit colors resulting from optical interference. 

Sodium alum occurs naturally as the mineral mendo2ite. Commercially, it is produced by the addition of a sodium sulfate solution to aluminum sulfate. Small amounts of potassium sulfate, sodium siUcate, and soda ash can be added to improve product handling and performance. After adjustment of the ratio of aluminum sulfate to sodium sulfate, water is evaporated to give a hard cake ia the cooling pans. This cake is further heated ia roasters and ground to a fineness of 99% through a 100-mesh (- 150 fiva) sieve. 

Aqueous ammonia also acts as a base precipitating metallic hydroxides from solutions of their salts, and in forming complex ions in the presence of excess ammonia. For example, using copper sulfate solution, cupric hydroxide, which is at first precipitated, redissolves in excess ammonia because of the formation of the complex tetramminecopper(TT) ion. 

Some companies have used the Merseburg process to manufacture ammonium sulfate from gypsum, but the process is only economically attractive where sulfur is unavailable or very expensive (32), and is thus not used in the United States. Ammonium carbonate, formed by the reaction of ammonia and carbon dioxide in an aqueous medium, reacts with suspended, finely ground gypsum. Insoluble calcium carbonate and an ammonium sulfate solution are formed. 

Another process, which also generates elemental sulfur as a by-product, has been patented by Envirotech Research Center in Salt Lake City (29). In the Electroslurry process, a ball mill finely grinds a chalcopyrite concentrate, which reacts with an acidic copper sulfate solution for iron removal. The Hquor is electrolyzed and the iron is oxidized to the ferric form. This latter step leaches copper from the copper sulfide for deposition on the cathode. Elemental sulfur is recovered at the same time. 

NKK s Bio-SR process is another iron-based redox process which instead of chelates, uses Thiobacillusferroidans )2iQ. - 2i to regenerate the solution (9). This process absorbs hydrogen sulfide from a gas stream into a ferric sulfate solution. The solution reacts with the hydrogen sulfide to produce elemental sulfur and ferrous sulfate. The sulfur is separated via mechanical means, such as filtering. The solution is regenerated to the active ferric form by the bacteria. 

First, the tar acids were removed from the naphtha fractions of light oils and, in the case of CVR tars, carboHc oil. The oils were then mixed with 25—35% sulfuric acid. After separation of the sulfates, the aqueous solution was diluted with water and the resinous material skimmed off. The diluted sulfate solution was boiled to expel any neutral oils, dried by the addition of soHd caustic soda or a2eotropically with ben2ene, and fractionated to yield pyridine, 2-methylpyridine (a-picoline), and a fraction referred to as 90/140 bases, which consisted mainly of 3- and 4-methylpyridines and 2,6-dimethylpyridine (2,6-lutidine). Higher boiling fractions were termed 90/160 and 90/180 bases because 90% of the product distilled at 160 and 180°C, respectively. 

Production and Economic Aspects. Thallium is obtained commercially as a by-product in the roasting of zinc, copper, and lead ores. The thallium is collected in the flue dust in the form of oxide or sulfate with other by-product metals, eg, cadmium, indium, germanium, selenium, and tellurium. The thallium content of the flue dust is low and further enrichment steps are required. If the thallium compounds present are soluble, ie, as oxides or sulfates, direct leaching with water or dilute acid separates them from the other insoluble metals. Otherwise, the thallium compound is solubilized with oxidizing roasts, by sulfatization, or by treatment with alkaU. The thallium precipitates from these solutions as thaUium(I) chloride [7791 -12-0]. Electrolysis of the thaUium(I) sulfate [7446-18-6] solution affords thallium metal in high purity (5,6). The sulfate solution must be acidified with sulfuric acid to avoid cathodic separation of zinc and anodic deposition of thaUium(III) oxide [1314-32-5]. The metal deposited on the cathode is removed, kneaded into lumps, and dried. It is then compressed into blocks, melted under hydrogen, and cast into sticks. 

Titanium Phosphates. Titanium(III) phosphate [24704-65-2] (titanous phosphate) is a purple soHd, soluble ia dilute acid, giving relatively stable solutions. It can be prepared by adding a soluble phosphate to titanous chloride or sulfate solution and raising the pH until precipitation occurs. 

Titanium Sulfates. Solutions of titanous sulfate [10343-61-0] ate readily made by reduction of titanium(IV) sulfate ia sulfuric acid solutioa by electrolytic or chemical means, eg, by reduction with ziac, ziac amalgam, or chromium (IT) chloride. The reaction is the basis of the most used titrimetric procedure for the determination of titanium. Titanous sulfate solutions are violet and, unless protected, can slowly oxidize ia coatact with the atmosphere. If all the titanium has been reduced to the trivalent form and the solution is then evaporated, crystals of an acid sulfate 3 Ti2(S0 2 [10343-61-0] ate produced. This purple salt, stable ia air at aormal temperatures, dissolves ia water to give a stable violet solutioa. Whea heated ia air, it decomposes to Ti02, water, sulfuric acid, and sulfur dioxide. 

Dicarboxyhc acids, eg, succinic or adipic, do not dissolve titanic acid. A phthalate has been prepared by adding acidic titanium sulfate solution to sodium phthalate solution. 

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