Tin in water

Smith [117] discussed the determination of tin in water. In the determination of low concentrations of the order of 40 ng of trialkyltin chlorides in sea water it has been observed that these compounds are very volatile and are easily lost upon evaporation with acid. Quantitative recovery of tin is, however, obtained in the absence of chloride ion during evaporation with acid. Preliminary removal of chlorides from sea water by passage down a column of IRA 400 resin before digestion with acid completely overcame loss of tin on subsequent evaporation, with acid giving a tin recovery of 90%. 

Tin in water may partition to soils and sediments. Cations such as Sn and Sn will generally be adsorbed by soils to some extent, which reduces their mobility. Tin is generally regarded as being relatively immobile in the environment (WHO 1980). However, tin may be transported in water if it partitions to suspended sediments (Cooney 1988), but the significance of this mechanism has not been studied in detail. 

Methods for determining tin in water, air, and waste samples with excellent selectivity and sensitivity are well developed and undergoing constant improvement. 

Maguire RJ, Tkacz RJ, Sartor DL. 1985. Butyltin species and inorganic tin in water and sediment of the Detroit and St. Clair Rivers. J Great Lakes Res 11 320-327. 

Yuan, Ch. G., G.B. Jiang, B. He, and J.F. Liu. 2005. Preconcentration and determination of tin in water samples by using cloud point extraction and graphite furnace atomic absorption spectrometry. Microchim. Acta 150 329-334. 

The Pyrocatechol Violet method has been used for determining tin in biological materials [5], foods [5,89], organic substances [2], rocks and ores [12], copper alloys [90], and steel [33]. Traces of tin in water and in lake sediments were determined with the aid of PV and CTA after preconcentration on polyurethane foam impregnated with dithiol [91]. Tin was also determined by the PV method in alloys after extractive isolation with the aid of tris(2-ethylhexyl)phosphate [92]. 

On account of the very low levels of tin in water it is first necessary to concentrate the tin by precipitation. This is done using hydrated manganese (IV) oxide as a trace trap. 

Sun, H. Liang, S. Li, L. Zhang, W. Highly sensitive spectrophotometric determination of trace amounts tin in water by using Sn(IV)-XO-PVA system. Guangpuxue GuangpuFenxi2003,23,594—596 Chem. Abstr. 2003,139, 105982. 

Soderguist and Crosby have developed a method for the simultaneous determination of triphenyltin hydroxide and its possible degradation products tetraphenyltin, diphenyltin oxide, benzenestan-noic acid, (and inorganic tin) in water. The method is rapid (one sample set per hour), sensitive to less than 0.01 g/ml for most of the tin species and exhibits no cross-interferences between the phenyltins. The phenyltins are detected by electron capture gas-liquid chromatography after conversion to their hydride derivatives, while inorganic tin is determined by a procedure which responds to tin (IV) oxide as well as aqueous tin (IV). ... 

Tin IV) chloride, SnCU, stannic chloride. M.p. — 33" C, b.p. 1I4°C. Colourless fuming liquid (Sn plus CI2) hydrolysed in water but forms SnCl4,5H20 and [SnCl p" from acid solutions, soluble in organic solvents. Used as a mordant. 

Tin(IV) oxide is insoluble in water, but if fused with sodium hydroxide and the mass extracted with water, sodium hexahydroxo-stannate(IV) is formed in solution ... 

Place 2 1 ml. (measured from a micro-burette) of nitro-benzene and 5 g. of granulated tin in a 150 ml. round-bottomed flask fitted with a small reflux water-condenser. (A large flask is employed because the mixture when subsequently boiled may bump violently.) Pour 10 ml. of cone. HCl down the condenser on this scale the reaction is not sufficiently vigorous to get out of control. Heat over a gauze for 15 minutes. Cool the flask and add a solution of 7 5 8- of NaOH in 10 ml. of water to redissolve the initial precipitate. Add about... 

Note on the laboratory preparation of monoethylaniline. Although the laboratory preparation of monomethyl- or monoethyl-aniline is hardly worth whUe, the following experimental details may be useful to those who wish to prepare pure monoethylaniline directly from amline. In a flask, fitted with a double surface reflux condenser, place 50 g. (49 ml.) of aniline and 65 g. of ethyl bromide, and boU gently for 2 hours or until the mixture has almost entirely sohdified. Dissolve it in water and boil off the small quantity of unreacted ethyl bromide. Render the mixture alkaUne with concentrated sodium hydroxide solution, extract the precipitated bases with three 50 ml. portions of ether, and distil off the ether. The residual oil contains anihne, mono- and di-ethylaniline. Dissolve it in excess of dilute hydrochloric acid (say, 100 ml. of concentrated acid and 400 ml. of water), cool in ice, and add with stirring a solution of 37 g. of sodium nitrite in 100 ml. of water do not allow the temperature to rise above 10°. Tnis leads to the formation of a solution of phenyl diazonium chloride, of N-nitrosoethylaniline and of p-nitrosodiethylaniline. The nitrosoethylaniline separates as a dark coloured oil. Extract the oil with ether, distil off the ether, and reduce the nitrosoamine with tin and hydrochloric acid (see above). The yield of ethylaniline is 20 g. 

Solvent for Electrolytic Reactions. Dimethyl sulfoxide has been widely used as a solvent for polarographic studies and a more negative cathode potential can be used in it than in water. In DMSO, cations can be successfully reduced to metals that react with water. Thus, the following metals have been electrodeposited from their salts in DMSO cerium, actinides, iron, nickel, cobalt, and manganese as amorphous deposits zinc, cadmium, tin, and bismuth as crystalline deposits and chromium, silver, lead, copper, and titanium (96—103). Generally, no metal less noble than zinc can be deposited from DMSO. 

Tin ores and concentrates can be brought into solution by fusing at red heat in a nickel cmcible with sodium carbonate and sodium peroxide, leaching in water, acidifying with hydrochloric acid, and digesting with nickel sheet. The solution is cooled in carbon dioxide, and titrated with a standard potassium iodate—iodide solution using starch as an indicator. 

The determination of tin in metals containing over 75 wt % tin (eg, ingot tin) requites a special procedure (17). A 5-g sample is dissolved in hydrochloric acid, reduced with nickel, and cooled in CO2. A calculated weight of pure potassium iodate (dried at 100°C) and an excess of potassium iodide (1 3) are dissolved in water and added to the reduced solution to oxidize 96—98 wt % of the stannous chloride present. The reaction is completed by titration with 0.1 Af KIO —KI solution to a blue color using starch as the indicator. 

Anhydrous stannous chloride, a water-soluble white soHd, is the most economical source of stannous tin and is especially important in redox and plating reactions. Preparation of the anhydrous salt may be by direct reaction of chlorine and molten tin, heating tin in hydrogen chloride gas, or reducing stannic chloride solution with tin metal, followed by dehydration. It is soluble in a number of organic solvents (g/100 g solvent at 23°C) acetone 42.7, ethyl alcohol 54.4, methyl isobutyl carbinol 10.45, isopropyl alcohol 9.61, methyl ethyl ketone 9.43 isoamyl acetate 3.76, diethyl ether 0.49, and mineral spirits 0.03 it is insoluble in petroleum naphtha and xylene (2). 

Stannic Chloride. Stannic chloride is available commercially as anhydrous stannic chloride, SnCl (tin(IV) chloride) stannic chloride pentahydrate, SnCl 5H20 and in proprietary solutions for special appHcations. Anhydrous stannic chloride, a colorless Aiming Hquid, fumes only in moist air, with the subsequent hydrolysis producing finely divided hydrated tin oxide or basic chloride. It is soluble in water, carbon tetrachloride, benzene, toluene, kerosene, gasoline, methanol, and many other organic solvents. With water, it forms a number of hydrates, of which the most important is the pentahydrate. Although stannic chloride is an almost perfect electrical insulator, traces of water make it a weak conductor. 

Stannous Oxide. Stannous oxide, SnO ((tin(II) oxide), mol wt 134.70, sp gr 6.5) is a stable, blue-black, crystalline product that decomposes at above 385°C. It is insoluble in water or methanol, but is readily soluble in acids and concentrated alkaHes. It is generally prepared from the precipitation of a stannous oxide hydrate from a solution of stannous chloride with alkaH. Treatment at controUed pH in water near the boiling point converts the hydrate to the oxide. Stannous oxide reacts readily with organic acids and mineral acids, which accounts and for its primary use as an intermediate in the manufacture of other tin compounds. Minor uses of stannous oxide are in the preparation of gold—tin and copper—tin mby glass. 

Stannic Oxide. Stannic oxide tin(IV) oxide, white crystals, mol wt 150.69, mp > 1600° C, sp gr 6.9, is insoluble in water, methanol, or acids but slowly dissolves in hot, concentrated alkaH solutions. In nature, it occurs as the mineral cassiterite. It is prepared industrially by blowing hot air over molten tin, by atomizing tin with high pressure steam and burning the finely divided metal, or by calcination of the hydrated oxide. Other methods of preparation include treating stannic chloride at high temperature with steam, treatment of granular tin at room temperature with nitric acid, or neutralization of stannic chloride with a base. 

Hydrated Stannic Oxide. Hydrated stannic oxide of variable water content is obtained by the hydrolysis of stannates. Acidification of a sodium stannate solution precipitates the hydrate as a flocculent white mass. The colloidal solution, which is obtained by washing the mass free of water-soluble ions and peptization with potassium hydroxide, is stable below 50°C and forms the basis for the patented Tin Sol process for replenishing tin in staimate tin-plating baths. A similar type of solution (Staimasol A and B) is prepared by the direct electrolysis of concentrated potassium staimate solutions (26). 

Potassium staimate, K2Sn(OH) (mol wt 298.93), and sodium stannate [12058-66-17, Na2Sn(OH), mol wt 266.71, are colorless crystals and are soluble in water. The solubiUty of potassium stannate in water is 110.5 g/100 mL water at 15°C and that of sodium stannate is 61.5 g/100 mL water at 15°C. The solubihty of sodium stannate decreases with increasing temperature, whereas the solubiUty of potassium stannate increases with increasing temperature. The solubihty of either sodium or potassium stannate decreases as the concentration of the respective free caustic increases. Hydrolysis of stannates yields hydrated stannic oxides and is the basis of the Tin Sol solution, which is used to replenish tin in stannate tin-plating baths (28,29). 

Stannous Sulfate. Stannous sulfate (tin(Il) sulfate), mol wt 214.75, SnSO, is a white crystalline powder which decomposes above 360°C. Because of internal redox reactions and a residue of acid moisture, the commercial product tends to discolor and degrade at ca 60°C. It is soluble in concentrated sulfuric acid and in water (330 g/L at 25°C). The solubihty in sulfuric acid solutions decreases as the concentration of free sulfuric acid increases. Stannous sulfate can be prepared from the reaction of excess sulfuric acid (specific gravity 1.53) and granulated tin for several days at 100°C until the reaction has ceased. Stannous sulfate is extracted with water and the aqueous solution evaporates in vacuo. Methanol is used to remove excess acid. It is also prepared by reaction of stannous oxide and sulfuric acid and by the direct electrolysis of high grade tin metal in sulfuric acid solutions of moderate strength in cells with anion-exchange membranes (36). 

Reaction.—Make a solution of 4 grams stannous chloride in TO c.c. cone, hydrochloric acid, add 2 grams aminoazobenzene, and boil for a few minutes. On cooling ciystals of the hydrochlorides of aniline and yi-phenylenediamine separate out. The liquid is filtered and washed with a little cone, hydrochloric acid to remove the tin salts. If the precipitate is dissolved in water and made alkaline with caustic soda, a mixture of liquid aniline and solid/-phenylenediamine is precipitated, from which the former may be removed by filtering, washing, and draining on a porous plate. 

Sn02, cassiterite, is the main ore of tin and it crystallizes with a rutile-type structure (p. 961). It is insoluble in water and dilute acids or alkalis but dissolves readily in fused alkali hydroxides to form stannates M Sn(OH)6. Conversely, aqueous solutions of tin(IV) salts hydrolyse to give a white precipitate of hydrous tin(IV) oxide which is readily soluble in both acids and alkalis thereby demonstrating the amphoteric nature of tin(IV). Sn(OH)4 itself is not known, but a reproducible product of empirical formula Sn02.H20 can be obtained by drying the hydrous gel at 110°, and further dehydration... 

N-cyclohexyl-1-chlorophthalimlde (250 g) was dissolved in glacial acetic acid (2.5 8),concentrated hydrochloric acid (555 ml) and tin (27B g) were added and the suspension was heated on a steam bath for 16 hours. The cooled solution was filtered and concentrated to dryness in vacuo to give a white solid. This solid was dissolved in water and the precipitated oil extracted with chloroform. The chloroform solution was dried and concentrated in vacuo to give a solid which, after recrystal I izat ion, yielded 5-chloro-2-cyclohexylisoindolin-1-one (43%), MP 140°Cto 142°C. 

Dimethyl carbonate (DMC) is a colorless liquid with a pleasant odor. It is soluble in most organic solvents but insoluble in water. The classical synthesis of DMC is the reaction of methanol with phosgene. Because phosgene is toxic, a non-phosgene-route may be preferred. The new route reacts methanol with urea over a tin catalyst. However, the yield is low. Using electron donor solvents such as trimethylene glycol dimethyl ether and continually distilling off the product increases the yield. ... 

As indicated above, the bicarbonate ion inhibits the process, which does not occur, therefore, in many supply waters attack is most likely in waters which by nature or as a result of treatment have a low bicarbonate content and relatively high chloride, sulphate or nitrate content. The number of points of attack increases with the concentration of aggressive anions and ultimately slow general corrosion may occur. During exposure of 99-75% tin to sea-water for 4 years, a corrosion rate of 0-0023 mm/y was observed . Corrosion in soil usually produces slow general corrosion with the production of crusts of oxides and basic salts this has no industrial importance but is occasionally of interest in archaeological work. 

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