Cooley's Cyclopaedia of Practical Receipts Volume Ii Part 242

=SULPHOFORM.= _Syn._ SULPOFORMUM. An oily liquid obtained by distilling one part of iodoform with three of sulphide of mercury.

=SULPHOPHE'NIC ACID.= A synonym of sulphocarbolic acid. See SULPHOCARBOLATES.

=SULPHOVIN'IC ACID.= C_{2}H_{5}HSO_{4}. _Syn._ SULPHETHYLIC ACID; ACIDUM SULPHOVINIc.u.m, L. This substance is formed by the action of heat on a mixture of alcohol and sulphuric acid; it is the intermediate product which is developed in the preparation of ether. The salts are called sulphovinates or sulphothylates.

=SUL'PHUR.= [Eng., L.] _Syn._ BRIMSTONE; SOUFRE, Fr. An elementary substance. That of commerce is chiefly imported from Sicily and Italy, and is a volcanic production.

_Var._ The princ.i.p.al of these are:

AMORPHOUS SULPHUR, BROWN S.; SULPHUR AMORPHUM, S. FUSc.u.m, S. INFORME, S.

RUBRUM, L. Prepared from sublimed sulphur, by melting it, increasing the heat to from 320 to 350 Fahr., and continuing it at that temperature for about half an hour, or until it becomes brown and viscid, and then pouring it into water. In this state it is ductile, like wax, may be easily moulded in any form, is much heavier than usual, and when it has cooled does not again become fluid until heated to above 600 Fahr. The same effect is produced more rapidly by at once raising the temperature of the melted ma.s.s to from 430 to 480 Fahr.

PRECIPITATED SULPHUR, HYDRATE OF SULPHUR, MILK OF S.; SULPHURIS HYDRAS, LAC SULPHURIS, SULPHUR PRaeCIPITATUM (Ph. L.). _Prep._ 1. From sublimed sulphur, 1 part; dry and recently slaked lime, 2 parts; water, 25 parts, or q. s.; boil for 2 or 3 hours, dilute with 25 parts more of water, filter, and precipitate with dilute hydrochloric acid; drain, and well wash the precipitate, and dry it by a gentle heat. Resembles sublimed sulphur in its general properties, but is much paler, and in a finer state of division.

2. (B. Ph.) Sublimed sulphur, 5 oz.; slaked lime, 3 oz.; hydrochloric acid, 3 fl. oz., or q. s.; distilled water, q. s. Heat the sulphur and lime, previously well mixed, in 1 pint of water, stirring diligently with a wooden spatula, boil for 15 minutes and filter. Boil the residue again in 1/2 pint of water and filter. Let the united filtrates cool, dilute with 2 pints of water, and in an open place, or under a chimney, add in successive quant.i.ties the hydrochloric acid previously diluted with 1 pint of water until effervescence ceases, and the mixture acquires an acid reaction. Allow the precipitate to settle, decant off the supernatant liquid, pour on fresh distilled water, and continue the purification by affusion of distilled water and subsidence, until the fluid ceases to have an acid reaction, and to precipitate with oxalate of ammonia. Collect the precipitated sulphur on a calico filter, wash it once with distilled water, and dry it at a temperature not exceeding 120 Fahr.

_Prop._ A greyish-yellow powder free from grittiness, and with no smell of sulphuretted hydrogen.

_Obs._ Many pharmacists regard LAC SULPHURIS and SULPHUR PRECIPITATUM as distinct substances, and a.s.sume that by milk of sulphur is intended a preparation made by an old pharmacopial process, in which sulphuric acid being employed, the sulphur so precipitated contains from 50 to 75 per cent. of sulphate of lime. Pareira, Royle, Atfield, and some other authorities, hold that LAC SULPHURIS and SULPHUR PRECIPITATUM are synonymous; whilst others, including Professor Redwood (one of the compilers of the B. P.) entertain a contrary opinion.

ROLL SULPHUR, CANE S., STICK S.; SULPHUR IN BACCULIS, S. IN ROTULIS, S.

ROTUNDUM, L. This is crude sulphur, purified by melting and skimming it, and then pouring it into moulds. That obtained during the roasting of copper pyrites, and which forms the common roll sulphur of England, frequently contains from 3 to 7% of yellow a.r.s.enic.

SUBLIMED SULPHUR, FLOWERS OF SULPHUR; FLORES SULPHURIS, SULPHUR (Ph. L.), SULPHUR SUBLIMATUM (B. P., Ph. E. & D.), L. Prepared by subliming sulphur in iron vessels. For medical purposes, it is ordered to be well washed with water, and dried by a gentle heat. "A slightly gritty powder, of a fine greenish-yellow colour, without taste and without odour till heated." (B. P.)

SULPHUR VIVUM, BLACK SULPHUR, CRUDE S., HORSE BRIMSTONE; SULPHUR NIGRUM, S. CABALLINUM, S. GRISEUM, L. This is crude native sulphur. It is a grey or mouse-coloured powder. The residuum in the subliming pots from the preparation of flowers of sulphur is now commonly subst.i.tuted for it. It generally contains much a.r.s.enic, and is consequently very poisonous.

_Pur._ The sublimed sulphur of the shops is now, in general, of respectable quality, but the precipitated sulphur frequently contains about 2/3 of its weight of sulphate of lime (plaster of Paris), owing to the subst.i.tution of sulphuric acid for hydrochloric acid in its manufacture.[211] This is readily detected by strongly heating a little of the suspected sample in an iron spoon or shovel, when the sulphur is burnt or volatilised, and leaves behind the sulphate of lime as a white ash; this, when mixed with water, and gently dried, gives the amount of the adulteration. A still simpler plan is to dissolve out the sulphur in the sample with a little hot oil of turpentine or liquor of pota.s.sa; the undissolved portion is foreign matter.

[Footnote 211: See PRECIPITATED SULPHUR, above.]

_Prop._ Sulphur melts to a clear thin fluid, and volatilises at about 232 Fahr., and in open vessels rapidly takes fire, burning with a bluish flame. It is insoluble in both water and alcohol; it is soluble in oil of turpentine and the fatty oils, and freely so in bisulphide of carbon and hot liquor of pota.s.sa. With oxygen it unites to form sulphurous anhydride, and with the metals to form sulphides. Sp. gr. 1982 to 2015.

_Estim._ The determination of the quant.i.ty of sulphur, phosphorus, and chlorine, in a state of combination, especially in organic mixtures, is often rather troublesome. The proportion of sulphur is best determined by oxidising a known weight of the substances by strong nitric acid, or by fusing it in a silver vessel with 10 or 12 times its weight of pure hydrate of pota.s.sa and about half as much nitre. The sulphur is thus converted into sulphuric acid, the quant.i.ty of which can be determined by dissolving the fused ma.s.s in water, acidulating the solution with nitric acid, adding a salt of baryta, and weighing the resulting sulphate.

Phosphorus is, in like manner, oxidised to phosphoric acid, the quant.i.ty of which is determined by precipitation in combination with sesquioxide of iron, or otherwise. The chlorine is correctly determined by placing a small weighed portion in a combustion-tube, which is afterwards filled with fragments of pure quicklime. The lime is then brought to a red heat, and the vapour of the liquid driven over it, when chloride of calcium is formed. The contents of the tube, when cold, are dissolved in dilute nitric acid, filtered, the chlorine precipitated by nitrate of silver, and the chlorine weighed under the form of chloride of silver. See ORGANIC SUBSTANCES.

_Uses, &c._ Sulphur is extensively used in the manufacture of gunpowder, in bleaching, &c., &c. When swallowed, it acts as a mild laxative and stimulating diaph.o.r.etic; and has hence been long taken in various chronic skin diseases, in pulmonary, rheumatic, and gouty affections, and as a mild purgative in piles, prolapsus ani, &c. Externally, it is extensively used in skin diseases, especially the itch, for which it appears to be a specific.--_Dose_, 20 to 63 gr., in sugar, honey, treacle, or milk.

=Sulphur, Chlo"rides of.= Several of these compounds exist but the following are the most important. 1. (DICHLORIDE, S_{2}Cl_{2}.) Prepared by pa.s.sing dry chlorine gas over the surface of sulphur melted in a bulbed-tube or small retort connected with a well-cooled receiver. The product is a deep orange-yellow and very mobile liquid, which possesses a disagreeable odour, and boils at 280 Fahr. It is soluble in bisulphide of carbon, and in benzol, without decomposing. It dissolves sulphur in large quant.i.ties, especially when heated. A solution of the dichloride with excess of sulphur in crude benzol is used for vulcanising caoutchouc.

2. (CHLORIDE, HYPOCHLORIDE, or HYPOCHLORITE of the shops; SULPHURIS CHLORIDUM, S. HYPOCHLORIDUM, S. HYPOCHLORITIS, L.) This is prepared by spreading washed sulphur thinly on the bottom of a wooden box, or other chamber, and pa.s.sing chlorine gas slowly over until it ceases to be absorbed.

_Obs._ This last compound is of variable and undetermined const.i.tution. It has been recommended for internal use, by Derksengi, in old gouty affections, combined with pains in the stomach, and in severe nervous fever.--_Dose_, 1/2 to 2 gr.; dissolved in ether, and taken with old Hungary wine. It is also used externally in _psoriasis inveterata_, and other skin diseases.

=Sulphur, I'odide of.= S_{2}I_{2}. _Syn._ BINIODIDE OF SULPHUR; SULPHURIS IODIDUM (Ph. L.), SULPHUR IODATUM (Ph. D.), L. _Prep._ Into a gla.s.s flask put 1 part of sublimed sulphur, and over it place 4 parts of iodine; insert the cork loosely, and place the flask in a water bath; as soon as its contents melt, stir them with a gla.s.s rod, replace the cork, remove the bath from the fire, and let the whole cool together. When cold, break the iodide into pieces, and place it in a wide-mouthed stoppered bottle.

In this way a beautiful semi-crystalline, dark grey ma.s.s, resembling antimony, is obtained. The formulae of the B. P., Ph. L., E., & D., Ph. U.

S., & P. Cod., are essentially similar. The Ph. D. orders the two substances to be powdered and mixed before heating them.

_Uses, &c._ It is stimulant and alterative. An ointment made of it has been recommended by Biett and others in tuberculous affections of the skin, in lepra, psoriasis, lupus, porrigo, &c.

Iodide of sulphur stains the skin like iodine, and is readily decomposed by contact with organic substances.

=SULPHURA'TION.= The process by which silk, cotton, and woollen goods, straw plait, &c., are subjected to the fumes of burning sulphur, or sulphurous acid, for the purpose of bleaching or decolouring them. On the large scale, this is effected in closed apartments, called 'sulphuring rooms,' to which sufficient air only is admitted to keep up the slow combustion of the sulphur. On the small scale, as for straw hats, bonnets, &c., a large wooden chest is frequently employed in the same way.

=SUL'PHURET.= _Syn._ SULPHIDE; SULPHURETUM, SULPHIDUM, L. See SULPHIDE.

=SULPHURET'TED HY'DROGEN= (H_{2}S). _Syn._ HYDROGEN SULPHIDE, DIHYDRIC SULPHIDE, HYDRIC SULPHIDE; HYDROSULPHURIC ACID. Sulphuretted hydrogen occurs in nature amongst the gaseous products given off by volcanoes, as well as in many mineral waters, amongst which may be instanced those of Harrogate, in England, of Moffat, in Scotland, and of Bareges, Eaux Bonnes, St. Sauveur, &c., in the Pyrenees. It is also evolved from decaying animal matter containing alb.u.men, such as white-of-egg, as well as from putrisable animal and vegetable substances, when in contact with a soluble sulphate, and is always one of the gases present in the air of drains and sewers. Sulphuretted hydrogen may be procured by the direct union of hydrogen and sulphur, as by pa.s.sing hydrogen into boiling sulphur. But this method of procuring it is rarely, if ever, adopted. The much readier process of acting upon a metallic sulphide by an acid const.i.tutes the means by which the chemist almost invariably obtains this gas.

The details of the process are as follows:

1. About an ounce of ferrous sulphide, previously reduced to small pieces, is placed in a bottle, and then there is poured on to it a fluid ounce of sulphuric acid diluted with 8 times its bulk of water, when the following reaction ensues:--FeS + H_{2}SO_{4} = H_{2}S + FeSO_{4}.

The gas which is immediately and copiously given off may be collected in an apparatus, a drawing and description of which are given below.

[Ill.u.s.tration]

The diluted acid, having become cool, is poured through the bulb-shaped aperture down the gla.s.s tube upon the ferrous sulphide, and the evolved gas pa.s.sing through the small intermediate wash-bottle into the bottle at the reader's right hand, is absorbed by the water therein contained, the operation being continued until the water has become saturated with the gas. The gla.s.s tubes are connected with vulcanised india rubber, as shown in the above plate. Diluted hydrochloric acid is frequently subst.i.tuted for sulphuric.

2. In the above process, the gas obtained, owing to the contamination of the iron sulphide, is more or less impure. When sulphuretted hydrogen is required in a state of purity, 1 oz. of antimonious sulphide must be employed instead of the iron sulphide, and instead of sulphuric 3 or 4 parts of hydrochloric acid. As heat must be applied to the mixture, it will be necessary to subst.i.tute a flask for the larger bottle, and to support it on a retort stand. In other respects the apparatus needs no alteration.

3. Sulphuretted hydrogen is also obtainable when paraffin is heated at a moderately elevated temperature with sulphur, the reaction being attended with an abundant evolution of the gas, and a simultaneous separation of carbon.

? The solution of sulphuretted hydrogen, which is so indispensable to the chemist, and consequently in such constant requisition in the laboratory, unfortunately very quickly decomposes into water, and sulphur, which deposits at the bottom of the vessel containing it. To diminish as much as possible the tendency to deterioration, the solution should be made either with boiled water, or with the clear spoilt solution.

_Qualities, &c._ Sulphuretted hydrogen is a colourless inflammable gas, somewhat heavier than air, its specific gravity being 1174. When ignited, it burns with a bluish flame, to water and sulphurous anhydride if the combustion take place in a sufficient quant.i.ty of air, but if the supply of air be too limited, sulphur is deposited. Under a pressure of 17 atmospheres it is condensed to a colourless and very mobile fluid, which boils at 796 F., and freezes at 728 F. to a transparent solid. Both the gas and its aqueous solution exercise a feebly acid reaction on litmus.

Sulphuretted hydrogen is highly poisonous; when inhaled in any quant.i.ty it causes fainting; and in smaller quant.i.ties, even when considerably diluted by air, if breathed for any length of time, it acts as a dangerous depressant and insiduous poison. Upon the lower animals it acts with fatal rapidity, even if diluted with 800 or 1000 parts of atmospheric air.

Transmitted through tubes heated to redness, sulphuretted hydrogen becomes partially decomposed into its elements, hydrogen and sulphur. Water at 32 F. takes up 437 times its bulk of this gas, and at 59, 323 times its hulk, hence the importance of collecting it, over warm water, if required in the gaseous form.

In the presence of moisture, sulphurous anhydride and sulphuretted hydrogen, if equivalent quant.i.ties of each react upon each other, become decomposed into sulphur, water, and pentathronic acid; hence the value of sulphurous acid as a disinfectant. The deposited sulphur is found always to occur in the electro-positive condition. Chlorine, bromine, and iodine, also decompose sulphuretted hydrogen with deposition of sulphur, and formation of hydrochloric, hydrobromic, and hydriodic acids.

_Hydrosulphates or Sulphides._ Sulphuretted hydrogen or hydrosulphuric acid, as it is sometimes called, when brought into contact with bases in solution, gives rise to compounds, which by some chemists are regarded as hydrosulphates, or combinations of the base with hydrosulphuric acid; and by others as sulphides or combinations of the metal with sulphur, the latter reaction being attended with the elimination of water, as when a base is acted upon by hydrochloric acid. By those who hold the former view the reaction would be as follows:

K_{2}O + H_{2}S = K_{2}O_{1}H_{2}S.

In the latter case it would be thus represented:

K_{2}O + H_{2}S = K_{2}S + H_{2}O.

The latter is the more general opinion, and it receives support from the fact that when sulphuretted hydrogen is pa.s.sed into the solution of a metallic salt, an insoluble precipitate of a sulphide of the metal is thrown down. Thus, when the gas is pa.s.sed into a solution of cupric sulphate, the precipitate consists of hydrated cupric sulphide, the liberated sulphuric acid renders the liquid which was before neutral, acid. The larger number of sulphides so formed, combining with water at the instance of their precipitation, occur as hydrates.

There is also a cla.s.s of sulphides known as hydrosulphides, sulphydrates, or double sulphides, in which an equivalent of the metal is replaced by an equivalent of hydrogen. Examples of these are the pota.s.sic hydrosulphide (KHS), sodic hydrosulphide (NaHS), and ammonic hydrosulphide (H_{4}NHS).

No such combinations occur with hydrogen and the metals of the earth proper, and of the iron group.

_Tests._ Many of the hydrosulphates or sulphides may be detected, by dropping on them some hydrochloric acid, when the characteristic smell of sulphuretted hydrogen will be immediately evolved from them. Very small quant.i.ties of a sulphide may be detected as follows:--Place the suspected sulphide in a small test tube, on the upper part of which is inserted a piece of blotting paper moistened with a solution of plumbic acetate, then carefully pour some hydrochloric acid on to the substance, when, if it be a sulphide, the paper will become. immediately browned or blackened.

Many small quant.i.ties of the soluble sulphides are revealed in neutral or alkaline solutions by the rich purple colour which they form on the addition of a solution of sodic nitro-prusside. Most of them, when heated before the blow-pipe, give off the smell of sulphurous acid.