540-72-7 sodium thiocyanate

Note. Thiourea hydrolyses slowly under the above conditions. With 25-30% NaOH solution it gives ammonia, sodium sulphide and some sodium thiocyanate. 

Alkyl thiocyanates. From potassium or sodium thiocyanate and the alkyl halide in alcoholic solution, for example ... 

It is essential to use an excess of sodium, otherwise if sulphur and nitrogen are both present sodium thiocyanate, NaCNS, may be produced in the test for nitrogen it may give a red coloration with ferric iron but no Prussian blue since there will be no free cyanide ions. With excess of sodium the thiocyanate, if formed, will be decomposed ... 

The first reported synthesis of acrylonitrile [107-13-1] (qv) and polyacrylonitrile [25014-41-9] (PAN) was in 1894. The polymer received Htde attention for a number of years, until shortly before World War II, because there were no known solvents and the polymer decomposes before reaching its melting point. The first breakthrough in developing solvents for PAN occurred at I. G. Farbenindustrie where fibers made from the polymer were dissolved in aqueous solutions of quaternary ammonium compounds, such as ben2ylpyridinium chloride, or of metal salts, such as lithium bromide, sodium thiocyanate, and aluminum perchlorate. Early interest in acrylonitrile polymers (qv), however, was based primarily on its use in synthetic mbber (see Elastomers, synthetic). 

Dimethylformamide [68-12-2] (DME) and dimethyl sulfoxide [67-68-5] (DMSO) are the most commonly used commercial organic solvents, although polymerizations ia y-butyrolactoae, ethyleae carboaate, and dimethyl acetamide [127-19-5] (DMAC) are reported ia the hterature. Examples of suitable inorganic salts are aqueous solutioas of ziac chloride and aqueous sodium thiocyanate solutions. The homogeneous solution polymerization of acrylonitrile foUows the conventional kinetic scheme developed for vinyl monomers (12) (see Polymers). 

Physical and Chemical Properties. Sodium thiocyanate [540-72-7] NaSCN, is a colorless dehquescent crystalline soHd (mp 323°C). It is soluble in water to the extent of 58 wt % NaSCN at 25°C and 69 wt % at 100°C. It is also highly soluble in methanol and ethanol, and moderately soluble in acetone. Potassium thiocyanate [333-20-0] KSCN, is also a colorless crystalline soHd (mp 172°C) and is soluble in water to the extent of 217 g/100 g of water at 20°C and in acetone and alcohols. Much of the chemistry of sodium and potassium thiocyanates is that of the thiocyanate anion (372—375). 

Manufacture, Shipment, and Analysis. In the United States, sodium and potassium thiocyanates are made by adding caustic soda or potash to ammonium thiocyanate, followed by evaporation of the ammonia and water. The products are sold either as 50—55 wt % aqueous solutions, in the case of sodium thiocyanate, or as the crystalline soHds with one grade containing 5 wt % water and a higher assay grade containing a maximum of 2 wt % water. In Europe, the thiocyanates may be made by direct sulfurization of the corresponding cyanide. The acute LD q (rat, oral) of sodium thiocyanate is 764 mg/kg, accompanied by convulsions and respiratory failure LD q (mouse, oral) is 362 mg/kg. The lowest pubhshed toxic dose for potassium thiocyanate is 80—428 mg/kg, with hallucinations, convulsions, or muscular weakness. The acute LD q (rat, oral) for potassium thiocyanate is 854 mg/kg, with convulsions and respiratory failure. 

Shipping, analysis, and safety factors are similar to those of ammonium thiocyanate, except that the alkaU thiocyanates are more thermally stable. Sodium thiocyanate is best handled in 316 stainless steel. At room temperature where some iron contamination can be tolerated, type 304 can be used. Aluminum corrodes more rapidly than stainless steel, but some alloys can be used below 60°C. Some but not all mbber equipment is satisfactory. 

Economic Aspects. Capacity for sodium thiocyanate in the United States is substantially the same as that for ammonium thiocyanate because both products can be made in the same plants, but production is estimated at only slightly over 1000 t. The rate of growth is slight. The price on a 100 wt % basis in 1995 was 2.10/kg. Most sodium thiocyanate is sold as the solution. Potassium thiocyanate is a much lower volume product. 

Uses. The largest use for sodium thiocyanate is as the 50—60 wt % aqueous solution, as a component of the spinning solvent for acryUc fibers (see Fibers, acrylic Acrylonitrile polymers). Other textile appHcations are as a fiber swelling agent and as a dyeing and printing assist. A newer commercial use for sodium thiocyanate is as an additive to cement in order to impart early strength to concrete (376). 

Lesser amounts of sodium thiocyanate are used in color toning photographic paper, as a stabilizer in rapid film development, and as a sensitizing agent in color negative-film emulsions. It is also used as a brightener in copper electroplating. 

Sodium cyanide, when fused with sulfur or a polysulftde, is converted into sodium thiocyanate [574-32-7], this compound is also formed when a solution of sodium cyanide is boiled with sulfur or a polysulftde ... 

Sodium thiocyanate has also been recrystd from water, acetonitrile or from MeOH using Et20 for washing, then dried at 130°, or dried under vacuum at 60° for 2 days. [Strasser et al. J Am Chem Soc 107 789 1985 Szezygiel et al. J Am Chem Soc 91 1252 1987.] (The latter purification removes material reacting with iodine.) Sodium thiocyanate solns can be freed from traces of iron by repeated batch extractions with Et20. 

Replacement of iodine in (perfluoroalkyl)ethyl iodides predominates over the usual conversion to olefins when the reagent is very nucleophilic and weakly basic Soft nucleophiles like sodium thiocyanate and sodium thiolates react well in displacements [46, 47] (equation 42)... 

Thiophene has been thiocyanomethylated to a mixture of 2-thenyl-thiocyanate and 2-thenylisothiocyanate in 20% yield by the use of sodium thiocyanate, formalin, and dilute sulfuric acid, ... 

Rhodan-ion, n. thiocyanogen ion, CNS -kali, -kalium, n, potassium thiocyanate, -kalzium, n. calcium thiocyanate, -kupfer, n. cupric thiocyanate, copper(II) thiocyanate. -iSsung, /. thiocyanate solution, -metall, n. (metallic) thiocyanate, -methyl, n. methyl thiocyanate, -natrium, n, sodium thiocyanate, -nickel, m. nickel thiocyanate, -quecksilber, n. mercury thiocyanate, -salz, n. thiocyanate, -sdure, /. (Org. Chem.) thiocyan(at)o acid, -tonerde, /. aluminum thiocyanate. 

The majority of the literature reports deal with the reaction of calixarenes with Group I and II cations. Polymeric calixarenes have been the subject of a more recent innovation. Harris et al. [23] have prepared a calix[4]ar-ene methacrylate, its polymerization, and Na complex-ation (Scheme 3). They concluded that both monomers and polymers form stable complexes with sodium thiocyanate. 

Discussion. Potassium may be precipitated with excess of sodium tetraphenyl-borate solution as potassium tetraphenylborate. The excess of reagent is determined by titration with mercury(II) nitrate solution. The indicator consists of a mixture of iron(III) nitrate and dilute sodium thiocyanate solution. The end-point is revealed by the decolorisation of the iron(III)-thiocyanate complex due to the formation of the colourless mercury(II) thiocyanate. The reaction between mercury( II) nitrate and sodium tetraphenylborate under the experimental conditions used is not quite stoichiometric hence it is necessary to determine the volume in mL of Hg(N03)2 solution equivalent to 1 mL of a NaB(C6H5)4 solution. Halides must be absent. 

Standardisation. Pipette 10.0 mL of the sodium tetraphenylborate solution into a 250 mL beaker and add 90 mL water, 2.5 mL 0.1 M nitric acid, 1.0 mL iron(III) nitrate solution, and 10.0 mL sodium thiocyanate solution. Without delay stir the solution mechanically, then slowly add from a burette 10 drops of mercury(II) nitrate solution. Continue the titration by adding the mercury(II) nitrate solution at a rate of 1-2 drops per second until the colour of the indicator is temporarily discharged. Continue the titration more slowly, but maintain the rapid state of stirring. The end point is arbitrarily defined as the point when the indicator colour is discharged and fails to reappear for 1 minute. Perform at least three titrations, and calculate the mean volume of mercury(II) nitrate solution equivalent to 10.0 mL of the sodium tetraphenylborate solution. 

Pipette 25.0 mL of the potassium ion solution (about 10 mg K + ) into a 50 mL graduated flask, add 0.5 mL 1M nitric acid and mix. Introduce 20.0 mL of the sodium tetraphenylborate solution, dilute to the mark, mix, then pour the mixture into a 150mL flask provided with a ground stopper. Shake the stoppered flask for 5 minutes on a mechanical shaker to coagulate the precipitate, then filter most of the solution through a dry Whatman No. 40 filter paper into a dry beaker. Transfer 25.0 mL of the filtrate into a 250 mL conical flask and add 75 mL of water, 1.0 mL of iron(III) nitrate solution, and 1.0 mL of sodium thiocyanate solution. Titrate with the mercury(II) nitrate solution as described above. 

Sodium aluminium sulphate Sodium bisulphate Sodium hypochlorite Sodium perchlorate Sodium thiocyanate Stannic ammonium chloride Stannic chloride Stannous chloride Uranyl nitrate Zinc chloride Zinc fluorosilicate... 

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