Chapter 75

SULPHUR.

Examine brimstone, flowers of sulphur, pyrite, chalcopyrite, sphalerite, galenite, gypsum, barite.

182. Separation.

Experiment 103.--To a solution of 2 g. of sodium sulphide,, Na2S2 in 10 cc. H2O add 3 or 4cc. HCl, and look for a ppt. Filter, and examine the residue. It is lac sulphur, or milk of sulphur.

183. Crystals from Fusion.

Experiment 104.--In a beaker of 25 or 50 cc. capacity put 20 g. brimstone. Place this over a flame with asbestos paper interposed, and melt it slowly. Note the color of the liquid, then let it cool, watching for crystals. When partly solidified pour the liquid portion into an evapo- rating-dish of water, and observe the crystals of S forming in the beaker (Fig. 42). The hard mass may be separated from the glass by a little HNO3 and a thin knife-blade, or by CS2.

184. Allotropy.

Experiment 105.--Place in a t.t. 15g of brimstone, then heat slowly till it melts. Notice the thin amber-colored liquid. The temperature is now a little above 100 degrees. As the heat increases, notice that it grows darker till it becomes black and so viscid that it cannot be poured out. It is now above 200 degrees. Still heat, and observe that it changes to a slightly lighter color, and is again a thin liquid. At this time it is above 300 degrees. Now pour a little into an evaporating dish containing water. Examine this, noticing that it can be stretched like rubber. Leave it in the water till it becomes hard. Continue heating thebrimstone in the t.t. till it boils at about 450 degrees, and note the color of the escaping vapor. Just above this point it takes fire. Cool the t.t., holding it in the light meantime, and look for a sublimate of S on the sides.

185. Solution.

Experiment 106.--Place in an evaporating-dish a gram of powdered brimstone, and add 5cc, CS2, carbon disulphide. Stir, and see whether S is dissolved. Put this in a draft of air, and note the evaporation of the liquid CS2, and the deposit of S crystals. These crystals are different in form from those resulting from cooling from fusion.

186. Theory of Allotropy.--The last three experiments well illustrate allotropy. We found S to crystallize in two different ways. Substances can crystallize in seven different systems, and usually a given substance is found in one of these systems only; e.g. galena is invariably cubical. An element having two such forms is said to be dimorphous. If it crystallizes in three systems, it is trimorphous. A crystal has a definite arrangement of its molecules. If without crystalline form, a substance is called amorphous. An illustration of amorphism was S after it had been poured into water. Thus S has at least three allotropic forms, and the gradations between these probably represent others. Allotropy seems to be due to varied molecular structure. We know but little of the molecular condition of solids and liquids, since we have no law to guide us like Avogadro's in gases; but, from the density of S vapor at different temperatures, we infer that liquids and solids have their molecules very differently made up from those of gases. The least combining weight of S is 32. Its vapor density at 1,000 degrees is 32; hence its molecular weight is 64, i.e. vapor density x 2; and there are 2 atoms in its molecule at that temperature, molecular weight / atomic weight. At 500 degrees, however, the vapor density is 96and the molecular weight 192. At this degree the molecule must contain 6 atoms. How many it has in the allotropic forms, as a solid, is beyond our knowledge; but it seems quite likely that allotropy is due to some change of molecular structure.

The above experiments show two modes of obtaining crystals, by fusion and by solution.

187. Occurrence and Purification.--Sulphur occurs both free and combined, and is a very common element. It is found free in all volcanic regions, but Sicily furnishes most of it. Great quantities are thrown up from the interior of the earth during an eruption. The heat of volcanic action probably separates it from its compound, which may be CaSO4. Vast quantities of the poisonous SO2 gas are also liberated during an eruption, this being, in volume of gases evolved, next to H2O. S is crudely separated from its earthy impurities in Sicily by piling it into heaps, covering to prevent access of air, and igniting, when some of the S burns, and the rest melts and is collected. After removal from the island it is further purified by distilling in retorts connected with large chambers where it sublimes on the sides as flowers of sulphur (Fig. 43). This is melted and run into molds, forming roll brimstone. S also occurs as a constituent of animal and vegetable compounds, as in mustard, hair, eggs, etc. The tarnishing of silver spoons by eggs is due to the formation of silver sulphide, Ag2S. The yellow color of eggs, however, is due to oils, not to S.

The main compounds of S are sulphides and sulphates. What acids do they respectively represent? Metallic sulphides are as common as oxides; e.g. FeS2, or pyrite, PbS, or galenite, ZnS, or sphalerite, CuFeS2, or chalcopyrite, etc. The most abundant sulphate is CaSO4, or gypsum. BaSO4, or barite, and Na2SO4, or Glauber's salt, are others.

The only one of these compounds that is utilized for its S is FeS2. In Europe this furnishes a great deal of the S for H2SO4. S is obtained by roasting FeS2. 3 FeS2 = Fe3S4 + 2 S.

188. Uses. -The greatest use of S is in the manufacture of H2SO4. A great deal is used in making gunpowder, matches, vulcanized rubber, and the artificial sulphides, like HgS, H2S, CS2, etc. The last is a very volatile, ill- smelling liquid, made by the combination of two solids, S being passed over red-hot charcoal. It dissolves S, P, rubber, gums, and many other substances insoluble in H2O.

189. Sulphur Dioxide, SO2, has been made in many experiments. It is a bleaching agent, a disinfectant, and a very active compound, having great affinity for water, but it will not support combustion. Like most disinfectants, it is very injurious to the system. It is used to bleach silk and wool--animal substances-- and straw goods, which Cl would injure; but the color can be restored, as the coloring molecule seems not to be broken up, but to combine with SO2, which is again separated by reagents. Goods bleached with SO2 often turn yellow after a time.

190. SO2 a Bleacher.

Experiment 107.-Test its bleaching power by burning S under a receiver under which a wet rose or a green leaf is also placed.