Sodium, sulphide

Bright yellow needles m.p. 45 C, b.p. 2 4°C. Prepared together with 4-nitrophenol by careful nitration of phenol. Sodium sulphide reduces it to 2-aminophenol which is used in dyestuffs and photographic processes. 

Sodium sulphide, NajS, formed by reduction Na2S04 with CO or H2- Aqueous solutions are oxidized to sodium thiosulphate. 

Required Sulphur, 4 2 g. sodium sulphide, 16 g. m-dinitro-benzene, to g. 

The crystalline sodium sulphide (NajS,9H20) used to prepare the disulphide is very deliquescent, and only a sample which has been kept in a well-stoppered bottle and therefore reasonably dry should be used. A sample from a badly-stoppered bottle may contain, in addition to the crystals, a certain amount of aqueous solution, in which hydrolysis and partial decomposition will have occurred such a sample should therefore be rejected. Add 4 2 g. of finely powdered sulphur to a solution of 16 g. of the crystalline sodium sulphide in 60 ml. of water, and boil the mixture gently for a few minutes until a clear solution of the disulphide is obtained. 

Sodium mlphanilate.—Burns with difficulty, leaving a residue of (chiefly) sodium sulphide. Add dil. HCl, and confirm without delay the evolution of HjS by means of a filter-pa per moistened with lead acetate solution. Typical of salts of the sulphonic acids. Acetone sodium bisulphite.—Almost non-inflammable, leaving a colourless residue of sodium sulphite and sulphate. Transfer residue to a test-tube, add dil. HCl, warm, and confirm the SO2 evolved. 

Sulphur. THE LASSAIGNE SODIUM TEST. The sodium fusion will have converted any sulphur present in the original compounds to sodium sulphide. Dissolve a few crystals of sodium nitroprusside, Na8[Fe(CN)5NO],zH20, in water, and add the solution to the third portion of the filtrate obtained from the sodium fusion. A brilliant purple coloration (resembling permanganate) indicates sulphur the coloration slowly fades on standing. Note, (i) Sodium nitroprusside is unstable in aqueous solution and therefore the solution should be freshly prepared on each occasion, (ii) This is a very delicate test for sulphides, and it is essential therefore that all apparatus, particularly test-tubes, should be quite clean. 

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

Removal of sulphur as sodium sulphide. Dissolve about 0 i g. of c> stine in a few ml. of 10% NaOH solution. Add a few drops of lead acetate solution and boil for 1 minute. The solution darkens owing to the formation of lead sulphide. 

These solutions are obtained by dissolving 40 g. of the solid in water so that the final volume of the cold solution is 100 ml. With pure sodium hydroxide, the alkaline solution should be quite clear and free from insoluble material. The sodium sulphide used is the crystalline Na,S, qHjO. 

Anhydrous sodium sulphide. The hydrated salt, NajS.QH O, is heated in a Pyrex distilling flask or retort in a stream of hydrogen or of nitrogen until water ceases to be evolved. The solid cake of anhydrous sodium sulphide is removed from the vessel with the aid of a copper wire hook or by other suitable means. No attempt should be made to fuse the sodium sulphide since at high temperatiues sodium sulphide is readily oxidised to sodium sulphate. 

The alkyl sulphides or thioethers, the sulphur analogues of the ethers, are conveniently obtained by boiling alkyl halides with anhydrous sodium sulphide in alcoholic solution, for example ... 

Place 56 g. of finely-powdered, anhydrous sodium sulphide ( fused sodium sulphide) and 100 ml. of rectified spirit in a 500 ml. round-bottomed flask equipped with a reflux condenser. To the boiling mixture... 

Di-n-hexyl sulphide. Use 83 g. (71 ml.) of n-hexyl bromide (Section III.37), 56 g. of finely-powdered, anhydrous sodium sulphide and 100 ml. of rectified spirit. Reflux on a water bath for 20 hours. Distil ofiF the alcohol from a water bath very Uttle sulphide is obtained upon adding excess of water to the distiUate. Add excess of water to the residue in the flask and separate the upper layer of crude n-hexyl sulphide. Purify as for n-propyl sulphide, but distil under reduced pressure. CoUectthe n-hexyl sulphide at 113-114°/4 mm. The yield is 45 g. 

Crystallised sodium sulphide NajS,9HjO is very deliquescent, and only a sample which has been kept in a tightly-stoppered bottle should be used crystals as dry as possible should be selected. Altemativelj, an equivalent amount of analysed fused sodium sulphide may be employed this dis.solves somewhat more slowly in alcohol. 

Place 84 g. of iron filings and 340 ml. of water in a 1 - 5 or 2-litre bolt-head flask equipped with a mechanical stirrer. Heat the mixture to boiling, stir mechanically, and add the sodium m-nitrobenzenesulphonate in small portions during 1 hour. After each addition the mixture foams extensively a wet cloth should be applied to the neck of the flask if the mixture tends to froth over the sides. Replace from time to time the water which has evaporated so that the volume is approximately constant. When all the sodium salt has been introduced, boU the mixture for 20 minutes. Place a small drop of the suspension upon filter paper and observe the colour of the spot it should be a pale brown but not deep brown or deep yellow. If it is not appreciably coloured, add anhydrous sodium carbonate cautiously, stirring the mixture, until red litmus paper is turned blue and a test drop upon filter paper is not blackened by sodium sulphide solution. Filter at the pump and wash well with hot water. Concentrate the filtrate to about 200 ml., acidify with concentrated hydrochloric acid to Congo red, and allow to cool. Filter off the metanilic acid and dry upon filter paper. A further small quantity may be obtained by concentrating the mother liquid. The yield is 55 g. 

Prepare a saturated solution of sodium sulphide, preferably from the fused technical sodium polysulphide, and saturate it with sulphur the sulphur content should approximate to that of sodium tetrasulphide. To 50 ml. of the saturated sodium tetrasulphide solution contained in a 500 ml. round-bottomed flask provided with a reflux condenser, add 12 -5 ml. of ethylene dichloride, followed by 1 g. of magnesium oxide to act as catalyst. Heat the mixture until the ethylene dichloride commences to reflux and remove the flame. An exothermic reaction sets in and small particles of Thiokol are formed at the interface between the tetrasulphide solution and the ethylene chloride these float to the surface, agglomerate, and then sink to the bottom of the flask. Decant the hquid, and wash the sohd several times with water. Remove the Thiokol with forceps or tongs and test its rubber-like properties (stretching, etc.). 

In order to detect these elements in organic compounds, it is necessary to convert them into ionlsable inorganie substanees so that the ionic tests of inoiganio qualitative analysis may be applied. This conversion may be accomplished by several methods, but the best procedure is to fuse the organic compound with metallio sodium (Lassalgne s test). In this way sodium cyanide, sodium sulphide and sodium halides are formed, which are readily identified. Thus ... 

These materials have been prepared by polymerisation of p-halothiophenoxide metal compounds both in the solid state and in solution. They have also been prepared by condensation of p-dichlorobenzene with elemental sulphur in the presence of sodium carbonate while the commercial polymers are said to be produced by the reaction of p-dichlorobenzene with sodium sulphide in a polar solvent. 

Alternatively cellulose is produced from wood via wood pulp. A number of processes are used in which the overall effect is the removal of the bulk of the non-cellulosic matter. The most widely used are the sulphite process, which uses a solution of calcium bisulphite and sulphur dioxide, the soda process using sodium hydroxide and the sulphate process using a solution of sodium hydroxide and sodium sulphide. (The term sulphate process is used since sodium sulphate is the source of the sulphide.) For chemical purposes the sulphite process is most commonly used. As normally prepared these pulps contain about 88-90% alpha-cellulose but this may be increased by alkaline purification and bleaching. 

Niobium like tantalum relies for its corrosion resistance on a highly adherent passive oxide film it is however not as resistant as tantalum in the more aggressive media. In no case reported in the literature is niobium inert to corrosives that attack tantalum. Niobium has not therefore been used extensively for corrosion resistant applications and little information is available on its performance in service conditions. It is more susceptible than tantalum to embrittlement by hydrogen and to corrosion by many aqueous corrodants. Although it is possible to prevent hydrogen embrittlement of niobium under some conditions by contacting it with platinum the method does not seem to be broadly effective. Niobium is attacked at room temperature by hydrofluoric acid and at 100°C by concentrated hydrochloric, sulphuric and phosphoric acids. It is embrittled by sodium hydroxide presumably as the result of hydrogen absorption and it is not suited for use with sodium sulphide. 

Traces of many metals interfere in the determination of calcium and magnesium using solochrome black indicator, e.g. Co, Ni, Cu, Zn, Hg, and Mn. Their interference can be overcome by the addition of a little hydroxylammonium chloride (which reduces some of the metals to their lower oxidation states), or also of sodium cyanide or potassium cyanide which form very stable cyanide complexes ( masking ). Iron may be rendered harmless by the addition of a little sodium sulphide. 

Reactions of Sodium Sulphide. I. With Compounds Containing Hydroxyl Groups, J. Burden, J. D. Craggs, M. H. B. Hayes, and M. Stacey, Tetrahedron, 30 (1974) 2729-2733. 

Potassium sulphide Rhenium (VII) sulphide Silver sulphide Sodium disulphide Sodium polysulphide Sodium sulphide Tin (II) sulphide Tin (IV) sulphide Titanium (IV) sulphide Uranium (IV) sulphide... 

Dissolution of tellurium in sodium sulphide can be effected only by simultaneous addition of sulphur, when the tellurium will be oxidized to thiotellurite and dissolved . 

In one reported incident sodium sulphide was incorporated into residuary waters from some pulp wood processing, which contained sodium carbonate. This produced an unexplained explosion. 

Sodium sulphate forms, in the presence of aluminium at 800°C, sodium sulphide. The reaction usually proves to be explosive and the usual method of preparing sodium sulphide from the sulphate uses carbon as a reducing agent. 

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