Thiocyanate, ammonium

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Ammonium thiocyanate is reacted with ethylenediamine, which is used as a feedstock in the production of ETU accelerator. 

Ammonium thiocyanate is commonly used as a fixing agent in photography. It is also used as a fungicide and as a brightener in silver plating. 

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When the potassium cyanate used in the above preparation is replaced by potassium thiocyanate (or sulphocyanide), the ammonium thiocyanate formed undergoes partial rearrangement to thiourea (or sulpho-urea). Even above... 

Add a known volume ofo oaM.AgNOj solution (in excess) and boil the solution until the silver chloride has coagulated. Filter through a conical 5 cm. funnel, ensuring that the filter-paper does not protrude above the r m of the funnel. Wash the silver chloride and the filter-paper several times with a fine jet of distilled water. To the united filtrate and washings add i ml. of saturated ferric alum solution. The solution should be almost colourless if it is more than faintly coloured, add a few drops of concentrated nitric acid. Then titrate with 0 02M-ammonium thiocyanate solution until the permanent colour of ferric thiocyanate is just perceptible. (Alternatively the chloride may be determined potentiometrically.)... 

Clearly it is not necessary to know the exact concentration of the ammonium thiocyanate solution, for it can be titrated against a known volume of the o ozA<7.AgN03 solution, and this ratio used in the calculation.)... 

Thiourea (II) may be obtained from ammonium thiocyanate (I) by an isomeric change analogous to ammonium cyanate, but the equilibrium relationship is very different (compare Section 111,133) ... 

Place 50 g. of ammonium thiocyanate in a small round-bottomed flask and immerse a thermometer in the substance. Heat in an oil bath until the temperature rises to 170° and maintain it at this temperature for 1 hour. Allow the melt to cool and extract it with 60-70 ml. of hot water. Filter the solution and allow to cool when crude thiourea separates the unchanged ammonium thiocyanate remains in the solution. Filter ofiF the crude product and recrystallise it from a little hot water. The yield of thiourea, m.p. 172°, is 8 g. 

Hantzsch and Weber began their description with the compound which led them indirectly to the discovery of the thiazoles the a-thiocyanoacetone imine ( Rhodanpropimin ) of J. Tcherniac and C. H. Norton. C4H6N2S. obtained by reaction of ammonium thiocyanate with chloroacetone. After Tcherniac and Norton (18), the a thiocyanoacetone... 

In 1877, Nencki (22) condensing ammonium thiocyanate with chloroacetic acid, attributed the name rhodaninic acid (Rhodaninsaure) to the compound he obtained. He noted the ability of rhodaninic acid to give colored derivatives with ferric salts. 

The reaction is carried out at low temperature in aqueous medium and then allowed to stand overnight (221). Ammonium thiocarbamate is prepared from a cold saturated solution of ammonium thiocyanate, which is gradually added to dilute sulfuric acid at 25°C. The liberated carbonyl sulfide is passed into a saturated solution of alcoholic ammonia at about 10°C (221). The fairly low yield indicates that the reaction has not been greatly developed. 

Compounds of type 184 were prepared similarly with R, = methyl and R2 = alkanoic esters (136, 229, 304) or carboxyethyl (4, 10, 13, 22, 220) (Table 11-27). Dichloroacetone reacts with ammonium thiocyanate, but... 

The cyclization of a-mercaptoketones with ammonium thiocyanate leads to the corresponding 2-mercaptothiazoles (144). For example, 2-mercapto-3-pentanone in ethereal solution with sulfuric acid gives 4-ethyl-5-methyl-2-mercaptothiazole (10), Ri = SH, R2 = Et, R3 = Me, when allowed to stand for 3 hr without heating with ammonium thiocyanate. 

Physical Properties. Ammonium thiocyanate [1762-95-4] NH SCN, is a hygroscopic crystalline soHd which deHquesces at high humidities (375,376). It melts at 149°C with partial isomerization to thiourea. It is soluble in water to the extent of 65 wt % at 25°C and 77 wt % at 60°C. It is also soluble to 35 wt % in methanol and 20 wt % in ethanol at 25°C. It is highly soluble in Hquid ammonia and Hquid sulfur dioxide, and moderately soluble in acetonitrile. 

Chemical Properties. Ammonium thiocyanate rearranges upon heating to an equiHbrium mixture with thiourea 30.3 wt % thiourea at 150°C, 25.3 wt % thiourea at 180°C (373,375). At 190—200°C, dry ammonium thiocyanate decomposes to hydrogen sulfide, ammonia, and carbon disulfide, leaving guanidine thiocyanate [56960-89-5] as a residue. Aqueous solutions of ammonium thiocyanate are weakly acidic a 5 wt % solution has a pH of 4—6. 

Ammonium thiocyanate reacts with amines yielding thioureas, such as naphthyl thiourea [86-88-4] ... 

Manufacture. An extensive technology was developed initially ia the 1930s for isolation of ammonium thiocyanate from coke-oven gases, but this technology is no longer practiced ia the United States (372). However, such thiocyanate recovery processes are used iadustrially ia Europe. Likewise, the direct sulfurization of cyanides to thiocyanates is not practiced commercially ia the United States. The principal route used ia the United States is the reaction of carbon disulfide with aqueous ammonia, which proceeds by way of ammonium dithiocarbamate [513-74-6]. Upon heatiag, the ammonium dithiocarbamate decomposes to ammonium thiocyanate and hydrogen sulfide. 

This reaction can also be mn in a continuous fashion. In the initial reactor, agitation is needed until the carbon disulfide Hquid phase reacts fully. The solution can then be vented to a tower where ammonia and hydrogen sulfide are stripped countercurrendy by a flow of steam from boiling ammonium thiocyanate solution. Ammonium sulfide solution is made as a by-product. The stripped ammonium thiocyanate solution is normally boiled to a strength of 55—60 wt %, and much of it is sold at this concentration. The balance is concentrated and cooled to produce crystals, which are removed by centrifiigation. 

Shipment ndStora.ge. The crystalline material is shipped as a nonha2ardous material, in polyethylene-lined fiber dmms. The solution can be shipped in dmms or bulk. Suitable materials of constmction for handling ammonium thiocyanate are aluminum, 316 stainless steel, mbber, poly(vinyl chloride), and glass-reinforced epoxy. Steel, 304 stainless steel, and copper alloys should be avoided (375,376). 

Economic Aspects. Ammonium thiocyanate capacity in the United States is well in excess of 9000 t/yr on a 100% soHds basis, but production in the 1990s is substantially less than this capacity. In the United States only Witco produces ammonium thiocyanate. Production growth is small. The price of ammonium thiocyanate in mid-1995 was 2.02/kg. 

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. 

Carbon disulfide reacts with concentrated ammonia to give ammonium thiocyanate [1762-95-4] and ammonium trithiocarbonate [13453-08-2] in a reaction promoted by alumina catalysts ... 

At approximately 160°C, some of the ammonium thiocyanate is converted to thiourea [62-56-6] H2NCSNH2, iulow yield. With alcohoHc ammonia, ammonium dithiocarbamate [513-74-6] forms ... 

Aqueous salt solutions such as saturated 2inc chloride [7646-85-7] or calcium thiocyanate [2092-16-2] can dissolve limited amounts of cellulose (87). Two non-aqueous salt solutions are ammonium thiocyanate [1762-95-4]— uoamonia. and lithium chloride /744Z-4/A/—dimethyl acetamide [127-19-5]. Solutions up to about 15% can be made with these solvents. Trifluoroacetic acid [76-05-17—methylene chloride [75-09-2] and /V-methy1morpho1ine N-oxide [7529-22-8]—(92—94) are two other solvent systems that have been studied (95). 

Acid dyes can be ptinted on acetate, produciag prints with very good wetfastness and exceptional brightness. The print paste contains a solvent, urea, and ammonium thiocyanate, as a fiber swelling agent to aid ia diffusion of the dye. Again, fixation and scouting foUow the procedures for polyamide. 

Chloro-a,/3-unsaturated aldehydes condense with ammonium thiocyanate to give isothiazoles (76EGP122249). 2,3-Diphenylcyclopropenone reacts with iV-sulfinyl-cyclohexylamine in the presence of nickel tetracarbonyl to give the isothiazolin-3-one 1-oxide (197) (79SST(5)345). Cholesteryl acetate reacts with trithiazyl trichloride in pyridine to give the isothiazolo steroid (198) (77JCS(P1)916). 

Ammonium thiocyanate [1762-95-4] M 76.1, m 138°(dec), 149 (dec), pK -1.85 (for HSCN), 149. Crystd three times from dilute HCIO4, to give material optically transparent at wavelengths longer than 270nm. Has also been crystd from absolute MeOH and from acetonitrile. 

Guanidine Nitrate (Coll. Vol. i, 293) From ammonium thiocyanate, lead nitrate, and ammonia at 120°. Gockel, Z. angew. Chem. 48, 430 (1935). 

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