Chapter VII: Part I (2)

_Chlorides of phosphorus._—By the action of dry chlorine on an excess of heated amorphous phosphorus, trichloride is formed (PCl₃), a liquid having a sharp smell and causing lachrymation, which fumes in the air, and in presence of water decomposes into phosphorous acid and hydrochloric acid. On heating with dry oxidising substances it forms phosphorus oxychloride (see below), which is used for the production of acid chlorides. By continuous treatment with chlorine it becomes converted into phosphorus pentachloride (PCl₅), which also is conveniently prepared by passing chlorine through a solution of phosphorus in carbon bisulphide, the solution being kept cold; it is crystalline, smells strongly, and attacks the eyes and lungs. With excess of water it decomposes into phosphoric acid and hydrochloric acid: with slight addition of water it forms phosphorus oxychloride (POCl₃). On the large scale this is prepared by reduction of phosphate of lime in the presence of chlorine with carbon or carbonic oxide. Phosphorus oxychloride, a colourless liquid, fumes in the air and is decomposed by water into phosphoric acid and hydrochloric acid.

In the preparation of chlorides of phosphorus, apart from the danger of chlorine gas and hydrochloric acid, the poisonous effect of phosphorus and its compounds (see Phosphorus) and even of carbon disulphide (as the solvent of phosphorus) and of carbonic oxide (in the preparation of phosphorus oxychloride) have to be taken into account.

Further, the halogen compounds of phosphorus exert irritant action on the eyes and lungs similar to chloride of sulphur as a result of their splitting up on the moist mucous membranes into hydrochloric acid and an oxyacid of phosphorus.[4]

Unless, therefore, special measures are taken, the persons employed in the manufacture of phosphorus chlorides suffer markedly from the injurious emanations given off.[5]

Leymann[6] mentions one case of poisoning by phosphorus chloride as having occurred in the factory described by him. By a defect in the outlet arrangement phosphorus oxychloride flowed into a workroom. Symptoms of poisoning (sensation of suffocation, difficulty of breathing, lachrymation, &c.) at once attacked the occupants; before much gas had escaped, the workers rushed out. Nevertheless, they suffered from severe illness of the respiratory organs (bronchial catarrh and inflammation of the lungs, with frothy, blood-stained expectoration, &c.).[7]

_Chlorides of sulphur._—Monochloride of sulphur (S₂Cl₂) is made by passing dried, washed chlorine gas into molten heated sulphur. The oily, brown, fuming liquid thus made is distilled over into a cooled condenser and by redistillation purified from the sulphur carried over with it. Sulphur monochloride can take up much sulphur, and when saturated is used in the vulcanisation of indiarubber, and, further, is used to convert linseed and beetroot oil into a rubber substitute. Monochloride of sulphur is decomposed by water into sulphur dioxide, hydrochloric acid, and sulphur. By further action of chlorine on the monochloride, sulphur dichloride (SCl₂) and the tetrachloride (SCl₄) are formed.

In its preparation and use (see also Indiarubber Manufacture) the injurious action of chlorine, of hydrochloric acid, and of sulphur dioxide comes into play.

The monochloride has very irritating effects. Leymann cites an industrial case of poisoning by it. In the German factory inspectors’ reports for 1897 a fatal case is recorded. The shirt of a worker became saturated with the material owing to the bursting of a bottle. First aid was rendered by pouring water over him, thereby increasing the symptoms, which proved fatal the next day. Thus the decomposition brought about by water already referred to aggravated the symptoms.

_Zinc chloride_ (ZnCl₂) is formed by heating zinc in presence of chlorine. It is obtained pure by dissolving pure zinc in hydrochloric acid and treating this solution with chlorine. Zinc chloride is obtained on the large scale by dissolving furnace calamine (zinc oxide) in hydrochloric acid. Zinc chloride is corrosive. It is used for impregnating wood and in weighting goods. Besides possible injury to health from chlorine and hydrogen chloride, risk of arseniuretted hydrogen poisoning is present in the manufacture if the raw materials contain arsenic. Eulenburg considers that in soldering oppressive zinc chloride fumes may come off if the metal to be soldered is first wiped with hydrochloric acid and then treated with the soldering iron.

_Rock salt._—Mention may be made that even to salt in combination with other chlorides (calcium chloride, magnesium chloride, &c.) injurious effects are ascribed. Ulcers and perforation of the septum of the nose in salt-grinders and packers who were working in a room charged with salt dust are described.[8] These effects are similar to those produced by the bichromates.

Organic Chlorine Compounds

_Carbon oxychloride_ (COCl₂, carbonyl dichloride, phosgene) is produced by direct combination of chlorine and carbonic oxide in presence of animal charcoal. Phosgene is itself a very poisonous gas which, in addition to the poisonous qualities of carbonic oxide (which have to be borne in mind in view of the method of manufacture), acts as an irritant of the mucous membranes. Commercially it is in solution in toluene and xylene, from which the gas is readily driven off by heating. It is used in the production of various colours, such as crystal violet, Victoria blue, auramine, &c.

A fatal case of phosgene gas poisoning in the report of the Union of Chemical Industry for 1905 deserves mention. The phosgene was kept in a liquefied state in iron bottles provided with a valve under 2·3 atm. pressure. The valve of one of these bottles leaked, allowing large escape into the workroom. Two workers tried but failed to secure the valve. The cylinder was therefore removed by a worker, by order of the manager, and placed in a cooling mixture, as phosgene boils at 8° C. The man in question wore a helmet into which air was pumped from the compressed air supply in the factory. As the helmet became obscured through moisture after five minutes the worker took it off. A foreman next put on the cleaned mask, and kept the cylinder surrounded with ice and salt for three-quarters of an hour, thus stopping the escape of gas. Meanwhile, the first worker had again entered the room, wearing a cloth soaked in dilute alcohol before his mouth, in order to take a sack of salt to the foreman. An hour and a half later he complained of being very ill, became worse during the night, and died the following morning. Although the deceased may have been extremely susceptible, the case affords sufficient proof of the dangerous nature of the gas, which in presence of moisture had decomposed into carbonic acid and hydrochloric acid; the latter had acutely attacked the mucous membrane of the respiratory passages and set up fatal bronchitis. Further, it was found that the leaden plugs of the valves had been eroded by the phosgene.

Three further cases of industrial phosgene poisoning have been reported,[9] one a severe case in which there was bronchitis with blood-stained expectoration, great dyspnœa, and weakness of the heart’s action. The affected person was successfully treated with ether and oxygen inhalations. Phosgene may act either as the whole molecule, or is inhaled to such degree that the carbonic oxide element plays a part.

In another case of industrial phosgene poisoning the symptoms were those of severe irritation of the bronchial mucous membrane and difficulty of breathing.[10] The case recovered, although sensitiveness of the air passages lasted a long time.

_Carbon chlorine compounds_ (_aliphatic series_).—_Methyl chloride_ (CH₃Cl) or chlormethane is prepared from methyl alcohol and hydrochloric acid (with chloride of zinc) or methyl alcohol, salt, and sulphuric acid. It is prepared in France on a large scale from beetroot _vinasse_ by dry distillation of the evaporation residue. The distillate, which contains methyl alcohol, trimethylamine, and other methylated amines, is heated with hydrochloric acid; the methyl chloride so obtained is purified, dried and compressed. It is used in the preparation of pure chloroform, in the coal-tar dye industry, and in surgery (as a local anæsthetic). In the preparation of methyl chloride there is risk from methyl alcohol, trimethylamine, &c. Methyl chloride itself is injurious to health.

_Methylene chloride_ (CH₂Cl₂, dichlormethane) is prepared in a similar way. It is very poisonous.

_Carbon tetrachloride_ (CCl₄, tetrachlormethane) is technically important. It is prepared by passing chlorine gas into carbon bisulphide with antimony or aluminium chloride. Carbon tetrachloride is a liquid suitable for the extraction of fat or grease (as in chemical cleaning), and has the advantage of being non-inflammable. Carbon tetrachloride, so far as its poisonous qualities are concerned, is to be preferred to other extractives (see Carbon Bisulphide, Benzine, &c.); for the rest it causes unconsciousness similar to chloroform.

When manufactured industrially, in addition to the poisonous effect of chlorine, the poisonous carbon bisulphide has also to be borne in mind.

_Ethyl chloride_ (C₂H₅Cl) is made in a way analogous to methyl chloride by the action of hydrochloric acid on ethyl alcohol and chloride of zinc. It is used in medicine as a narcotic.

_Monochloracetic acid._—In the preparation of monochloracetic acid hydrochloric acid is developed in large quantity. From it and anthranilic acid artificial indigo is prepared (according to Heuman) by means of caustic potash.

_Chloral_ (CCl₃CHO, trichloracetaldehyde) is produced by chlorinating alcohol. Chloral is used in the preparation of pure chloroform and (by addition of water) of chloral hydrate (trichloracetaldehyde hydrate), the well-known soporific.

_Chloroform_ (CHCl₃, trichlormethane).—Some methods for the preparation of chloroform have been already mentioned (Chloral, Methyl Chloride). Technically it is prepared by distillation of alcohol or acetone with bleaching powder. The workers employed are said to be affected by the stupefying vapours. Further, there is the risk of chlorine gas from use of chloride of lime.

_Chloride of nitrogen_ (NCl₃) is an oily, volatile, very explosive, strongly smelling substance, which irritates the eyes and nose violently and is in every respect dangerous; it is obtained from the action of chlorine or hypochlorous acid on sal-ammoniac. The poisonous nature of these substances may come into play. Risk of formation of chloride of nitrogen can arise in the production of gunpowder from nitre containing chlorine.

_Cyanogen chloride_ (CNCl).—Cyanogen chloride is made from hydrocyanic acid or cyanide of mercury and chlorine. Cyanogen chloride itself is an extremely poisonous and irritating gas, and all the substances from which it is made are also poisonous. According to Albrecht cyanogen chloride can arise in the preparation of red prussiate of potash (by passage of chlorine gas into a solution of the yellow prussiate) if the solution is treated with chlorine in excess; the workers may thus be exposed to great danger.

_Chlorobenzene._—In his paper referred to Leymann cites three cases of poisoning by chlorobenzene, one by dinitrochlorobenzene, and, further, three cases of burning by chlorobenzene and one by benzoyl chloride (C₆H₅COCl). The last named is made by treating benzaldehyde with chlorine, and irritates severely the mucous membranes, while decomposing into hydrochloric acid and benzoic acid.[11] Benzal chloride (C₆H₅CHCl₂), benzo trichloride (C₆H₅CCl₃), and benzyl chloride (C₆H₅CH₂Cl) are obtained by action of chlorine on boiling toluene. The vapours of these volatile products irritate the respiratory passages. In the manufacture there is risk from the effect of chlorine gas and toluene vapour (see Benzene, Toluene).

Leymann[12] describes in detail six cases of poisoning in persons employed in a chlorobenzene industry, of which two were due to nitrochlorobenzene. Symptoms of poisoning—headache, cyanosis, fainting, &c.—were noted in a person working for three weeks with chlorobenzene.[13]

In Lehmann’s opinion chlorine rash, the well-recognised skin affection of chlorine workers, may be due to contact with substances of the chlorbenzol group.[14]

_Iodine and iodine compounds._—Formerly iodine was obtained almost exclusively from the liquor formed by lixiviation of the ash of seaweed (kelp, &c.); now the principal sources are the mother liquors from Chili saltpetre and other salt industries. From the concentrated liquor the iodine is set free by means of chlorine or oxidising substances and purified by distillation and sublimation. Iodine is used for the preparation of photographic and pharmaceutical preparations, especially iodoform (tri-iodomethane, CHI₃), which is made by acting with iodine and caustic potash on alcohol, aldehyde, acetone, &c.

Apart from possible injurious action of chlorine when used in the preparation of iodine, workers are exposed to the possibility of chronic iodine poisoning. According to Ascher[15] irritation effects, nervous symptoms, and gastric ulceration occur in iodine manufacture and use. He considers that bromide of iodine used in photography produces these irritating effects most markedly. Layet and also Chevallier in older literature have made the same observations.

The Swiss Factory Inspectors’ Report for 1890-1 describes two acute cases of iodine poisoning in a factory where organic iodine compounds were made; one terminated fatally (severe cerebral symptoms, giddiness, diplopia, and collapse).

_Bromine and bromine compounds._—Bromine is obtained (as in the case of iodine) principally from the mother liquors of salt works (especially Stassfurt saline deposits) by the action of chlorine or nascent oxygen on the bromides of the alkalis and alkaline earths in the liquors. They are chiefly used in photography (silver bromide), in medicine (potassium bromide, &c.), and in the coal-tar dye industry.

The danger of bromine poisoning (especially of the chronic form) is present in its manufacture and use, but there is no positive evidence of the appearance of the bromine rash among the workers. On the other hand, instances are recorded of poisoning by methyl bromide, and the injurious effect of bromide of iodine has been referred to.

_Methyl iodide and methyl bromide._—Methyl iodide (CH₃I), a volatile fluid, is obtained by distillation of wood spirit with amorphous phosphorus and iodine; it is used in the production of methylated tar colours and for the production of various methylene compounds. Grandhomme describes, in the paper already referred to, six cases, some very severe, of poisoning by the vapour of methyl iodide among workers engaged in the preparation of antipyrin, which is obtained by the action of aceto-acetic ether on phenyl hydrazine, treatment of the pyrazolone so obtained with methyl iodide, and decomposition of the product with caustic soda. A case of methyl iodide poisoning is described in a factory operative, who showed symptoms similar to those described for methyl bromide except that the psychical disturbance was more marked.[16]

Three cases of methyl bromide (CH₃Br) poisoning are described in persons preparing the compound.[17] One of these terminated fatally. There is some doubt as to whether these cases were really methyl bromide poisoning. But later cases of methyl bromide poisoning are known, and hence the dangerous nature of this chemical compound is undoubted. Thus the Report of the Union of Chemical Industry for 1904 gives the following instance: Two workers who had to deal with an ethereal solution of methyl bromide became ill with symptoms of alcoholic intoxication. One suffered for a long time from nervous excitability, attacks of giddiness, and drowsiness. Other cases of poisoning from methyl bromide vapour are recorded with severe nervous symptoms and even collapse.

_Fluorine compounds._—_Hydrogen fluoride_ (HFl) commercially is a watery solution, which is prepared by decomposition of powdered fluorspar by sulphuric acid in cast-iron vessels with lead hoods. The escaping fumes are collected in leaden condensers surrounded with water; sometimes to get a very pure product it is redistilled in platinum vessels.

Hydrogen fluoride is used in the preparation of the fluorides of antimony, of which antimony fluoride ammonium sulphate (SbFl₃(NH₄)₂SO₄) has wide use in dyeing as a substitute for tartar emetic. It is produced by dissolving oxide of antimony in hydrofluoric acid with addition of ammonium sulphate and subsequent concentration and crystallisation. Hydrofluoric acid is used for etching glass (see also Glass Industry).

In brewing, an unpurified silico-fluoric acid mixed with silicic acid, clay, oxide of iron, and oxide of zinc called Salufer is used as a disinfectant and preservative.

_Hydrofluoric acid and silicofluoric acid_ (H₂SiFl₆) arise further in the superphosphate industry by the action of sulphuric acid on the phosphorites whereby silicofluoric acid is obtained as a bye-product (see also Manufacture of Artificial Manure). Hydrofluoric acid and its derivatives both in their manufacture and use and in the superphosphate industry affect the health of the workers.

If hydrogen fluoride or its compounds escape into the atmosphere they attack the respiratory passages and set up inflammation of the eyes; further, workers handling the watery solutions are prone to skin affections (ulceration).

The following are examples of the effects produced.[18] A worker in an art establishment upset a bottle of hydrofluoric acid and wetted the inner side of a finger of the right hand. Although he immediately washed his hands, a painful inflammation with formation of blisters similar to a burn of the second degree came on within a few hours. The blister became infected and suppurated.

A man and his wife wished to obliterate the printing on the top of porcelain beer bottle stoppers with hydrofluoric acid. The man took a cloth, moistened a corner of it, and then rubbed the writing off. After a short time he noticed a slight burning sensation and stopped. His wife, who wore an old kid glove in doing the work, suffered from the same symptoms, the pain from which in the night became unbearable, and in spite of medical treatment gangrene of the finger-tips ensued. Healing took place with suppuration and loss of the finger-nails.

Injury of the respiratory passages by hydrofluoric acid has often been reported. In one factory for its manufacture the hydrofluoric acid vapour was so great that all the windows to a height of 8 metres were etched dull.

Several cases of poisoning by hydrofluoric acid were noted by me when examining the certificates of the Sick Insurance Society of Bohemia. In 1906 there were four due to inhalation of vapour of hydrofluoric acid in a hydrofluoric acid factory, with symptoms of corrosive action on the mucous membrane of the respiratory tract. In 1907 there was a severe case in the etching of glass.[19]

NITRIC ACID.

MANUFACTURE AND USES.—_Nitric acid_ (HNO₃) is obtained by distillation when Chili saltpetre (sodium nitrate) is decomposed by sulphuric acid in cast-iron retorts according to the equation:

NaNO₃ + H₂SO₄ = NaHSO₄ + HNO₃.

Condensation takes place in fireclay Woulff bottles connected to a coke tower in the same way as has been described in the manufacture of hydrochloric acid.

Lunge-Rohrmann plate towers are also used instead of the coke tower. Earthenware fans—as is the case with acid gases generally—serve to aspirate the nitrous fumes.

To free the nitric acid of the accompanying lower oxides of nitrogen (as well as chlorine, compounds of chlorine and other impurities) air is blown into the hot acid. The mixture of sodium sulphate and sodium bisulphate remaining in the retorts is either converted into sulphate by addition of salt or used in the manufacture of glass.

The nitric acid obtained is used either as such or mixed with sulphuric acid or with hydrochloric acid.

Pure nitric acid cannot at ordinary atmospheric pressure be distilled unaltered, becomes coloured on distillation, and turns red when exposed to light. It is extremely dangerous to handle, as it sets light to straw, for example, if long in contact with it. It must be packed, therefore, in kieselguhr earth, and when in glass carboys forwarded only in trains for transport of inflammable material.

Red, _fuming nitric acid_, a crude nitric acid, contains much nitrous and nitric oxides. It is produced if in the distillation process less sulphuric acid and a higher temperature are employed or (by reduction) if starch meal is added.

The successful production of nitric acid from the air must be referred to. It is effected by electric discharges in special furnaces from which the air charged with nitrous gas is led into towers where the nitric oxide is further oxidised (to tetroxide), and finally, by contact with water, converted into nitric acid.

Nitric acid is used in the manufacture of phosphoric acid, arsenious acid, and sulphuric acid, nitro-glycerin and nitrocellulose, smokeless powder, &c. (see the section on Explosives), in the preparation of nitrobenzenes, picric acid, and other nitro-compounds (see Tar Products, &c.). The diluted acid serves for the solution and etching of metals, also for the preparation of nitrates, such as the nitrates of mercury, silver, &c.

EFFECTS ON HEALTH.—Leymann considers that the average number of cases and duration of sickness among persons employed in the nitric acid industry are generally on the increase; the increase relates almost entirely to burns which can hardly be avoided with so strongly corrosive an acid. The number of burns amounts almost to 12 per cent. according to Leymann’s figures (i.e. on an average 12 burns per 100 workers), while among the packers, day labourers, &c., in the same industry the proportion is only 1 per cent. Affections of the respiratory tract are fairly frequent (11·8 per cent. as compared with 8·8 per cent. of other workers), which is no doubt to be ascribed to the corrosive action of nitrous fumes on the mucous membranes. Escape of acid fumes can occur in the manufacture of nitric acid though leaky retorts, pipes, &c., and injurious acid fumes may be developed in the workrooms from the bisulphate when withdrawn from the retorts, which is especially the case when excess of sulphuric acid is used. The poisonous nature of these fumes is very great, as is shown by cases in which severe poisoning has been reported from merely carrying a vessel containing fuming nitric acid.[1]

Frequent accidents occur through the corrosive action of the acid or from breathing the acid fumes—apart from the dangers mentioned in the manufacture—in filling, packing, and despatching the acid—especially if appropriate vessels are not used and they break. Of such accidents several are reported.

Further, reports of severe poisoning from the use of nitric acid are numerous. Inhalation of nitrous fumes (nitrous and nitric oxides, &c.) does not immediately cause severe symptoms or death; severe symptoms tend to come on some hours later, as the examples cited below show.

Occurrence of such poisoning has already been referred to when describing the sulphuric acid industry. In the superphosphate industry also poisoning has occurred by accidental development of nitric oxide fumes on sodium nitrate mixing with very acid superphosphate.

Not unfrequently poisoning arises in pickling metals (belt making, pickling brass; cf. the chapter on Treatment of Metals). Poisoning by nitrous fumes has frequently been reported from the action of nitric acid on organic substances whereby the lower oxides of nitrogen—nitrous and nitric oxides—are given off. Such action of nitric acid or of a mixture of nitric and sulphuric acid on organic substances is used for nitrating purposes (see Nitroglycerin; Explosives; Nitrobenzol).

Through want of care, therefore, poisoning can arise in these industries. Again, this danger is present on accidental contact of escaping acid with organic substances (wood, paper, leather, &c.), as shown especially by fires thus created.[2]

Thus, in a cellar were five large iron vessels containing a mixture of sulphuric and nitric acids. One of the vessels was found one morning to be leaking. The manager directed that smoke helmets should be fetched, intending to pump out the acid, and two plumbers went into the cellar to fix the pump, staying there about twenty-five minutes. They used cotton waste and handkerchiefs as respirators, but did not put on the smoke helmets. One plumber suffered only from cough, but the other died the same evening with symptoms of great dyspnœa. At the autopsy severe inflammation and swelling of the mucous membrane of the palate, pharynx and air passages, and congestion of the lungs were found.

Two further fatal cases in the nitrating room are described by Holtzmann. One of the two complained only a few hours after entering the room of pains in the chest and giddiness. He died two days later. The other died the day after entering the factory, where he had only worked for three hours. In both cases intense swelling and inflammation of the mucous membrane was found.

Holtzmann mentions cases of poisoning by nitrous fumes in the heating of an artificial manure consisting of a mixture of saltpetre, brown coal containing sulphur, and wool waste. Fatalities have been reported in workers who had tried to mop up the spilt nitric acid with shavings.[3] We quote the following other instances[4]:

(1) Fatal poisoning of a fireman who had rescued several persons from a room filled with nitrous fumes the result of a fire occasioned by the upsetting of a carboy. The rescued suffered from bronchial catarrh, the rescuer dying from inflammation and congestion of the lungs twenty-nine hours after the inhalation of the gas.

(2) At a fire in a chemical factory three officers and fifty-seven firemen became affected from inhalation of nitrous fumes, of whom one died.

(3) In Elberfeld on an open piece of ground fifty carboys were stored. One burst and started a fire. As a strong wind was blowing the firemen were little affected by the volumes of reddish fumes. Soon afterwards at the same spot some fifty to sixty carboys were destroyed. Fifteen men successfully extinguished the fire in a relatively still atmosphere in less than half an hour. At first hardly any symptoms of discomfort were felt. Three hours later all were seized with violent suffocative attacks, which in one case proved fatal and in the rest entailed nine to ten days’ illness from affection of the respiratory organs.

The Report of the Union for Chemical Industry for 1908 describes a similar accident in a nitro-cellulose factory.

Of those engaged in extinguishing the fire twenty-two were affected, and in spite of medical treatment and use of the oxygen apparatus three died.

From the same source we quote the following examples:

In a denitrating installation (see Nitro-glycerin; Explosives) a man was engaged in blowing, by means of compressed air, weak nitric acid from a stoneware vessel sunk in the ground into a washing tower. As the whole system was already under high pressure the vessel suddenly exploded, and in doing so smashed a wooden vat containing similar acid, which spilt on the ground with sudden development of tetroxide vapours. The man inhaled much gas, but except for pains in the chest felt no serious symptoms at the time and continued to work the following day. Death occurred the next evening from severe dyspnœa.

A somewhat similar case occurred in the nitrating room of a dynamite factory in connection with the cleaning of a waste acid egg; the vessel had for several days been repeatedly washed out with water made alkaline with unslaked lime. Two men then in turn got into the egg in order to remove the lime and lead deposit, compressed air being continuously blown in through the manhole. The foreman remained about a quarter of an hour and finished the cleaning without feeling unwell. Difficulty of breathing came on in the evening, and death ensued on the following day.

In another case a worker was engaged in washing nitroxylene when, through a leak, a portion of the contents collected in a pit below. He then climbed into the pit and scooped the nitroxylene which had escaped into jars. This work took about three-quarters of an hour, and afterwards he complained of difficulty of breathing and died thirty-six hours later.[5]

A worker again had to control a valve regulating the flow to two large vessels serving to heat or cool the nitrated liquid. Both vessels were provided with pressure gauges and open at the top. Through carelessness one of the vessels ran over, and instead of leaving the room after closing the valve, the man tried to get rid of the traces of his error, remaining in the atmosphere charged with the fumes,[6] and was poisoned.

Nitric and Nitrous Salts and Compounds

When dissolving in nitric acid the substances necessary for making the various nitrates, nitric and nitrous oxides escape. In certain cases nitric and hydrochloric acids are used together to dissolve metals such as platinum and gold and ferric oxides, when chlorine as well as nitrous oxide escapes. Mention is necessary of the following:

_Barium nitrate_ (Ba(NO₃)₂) is prepared as a colourless crystalline substance by acting on barium carbonate or barium sulphide with nitric acid. Use is made of it in fireworks (green fire) and explosives. In analogous way strontium nitrate (Sr(NO₃)₂) is made and used for red fire.

_Ammonium nitrate_ (NH₄NO₃), a colourless crystalline substance, is obtained by neutralising nitric acid with ammonia or ammonium carbonate, and is also made by dissolving iron or tin in nitric acid. It is used in the manufacture of explosives.

_Lead nitrate_ (Pb(NO₃)₂), a colourless crystalline substance, is made by dissolving lead oxide or carbonate in nitric acid. It is used in dyeing and calico printing, in the preparation of chrome yellow and other lead compounds, and mixed with lead peroxide (obtained by treatment of red lead with nitric acid) in the manufacture of lucifer matches. Apart from risk from nitrous fumes (common to all these salts) there is risk also of chronic lead poisoning.

_Nitrate of iron_ (Fe(NO₃)₂), forming green crystals, is made by dissolving sulphide of iron or iron in cold dilute nitric acid. The so-called nitrate of iron commonly used in dyeing consists of basic sulphate of iron (used largely in the black dyeing of silk).

_Copper nitrate_ (Cu(NO₃)₂), prepared in a similar way, is also used in dyeing.

_Mercurous nitrate_ (Hg₂(NO₃)₂) is of great importance industrially, and is produced by the action of cold dilute nitric acid on an excess of mercury. It is used for ‘carotting’ rabbit skins in felt hat making, for colouring horn, for etching, and for forming an amalgam with metals, in making a black bronze on brass (art metal), in painting on porcelain, &c.

_Mercuric nitrate_ (Hg(NO₃)₂) is made by dissolving mercury in nitric acid or by treating mercury with excess of warm nitric acid. Both the mercurous and mercuric salts act as corrosives and are strongly poisonous (see also Mercury and Hat Manufacture).

_Nitrate of silver_ (AgNO₃) is obtained by dissolving silver in nitric acid and is used commercially as a caustic in the well-known crystalline pencils (lunar caustic). Its absorption into the system leads to accumulation of silver in the skin—the so-called argyria (see Silver). Such cases of chronic poisoning are recorded by Lewin.[7] Argyria occurs among photographers and especially in the silvering of glass pearls owing to introduction of a silver nitrate solution into the string of pearls by suction. In northern Bohemia, where the glass pearl industry is carried on in the homes of the workers, I saw a typical case. The cases are now rare, as air pumps are used instead of the mouth.

_Sodium nitrite_ (NaNO₂) is obtained by melting Chili saltpetre with metallic lead in cast-iron vessels. The mass is lixiviated and the crystals obtained on evaporation. The lead oxide produced is specially suitable for making red lead. Cases of lead poisoning are frequent and sometimes severe. Roth[8] mentions a factory where among 100 employed there were 211 attacks in a year.

_Amyl nitrite_ (C₅H₁₁NO₂) is made by leading nitrous fumes into iso-amyl alcohol and distilling amyl alcohol with potassium nitrite and sulphuric acid. It is a yellowish fluid, the fumes of which when inhaled produce throbbing of the bloodvessels in the head and rapid pulse.

For other nitric acid compounds see the following section on Explosives and the section on Manufacture of Tar Products (Nitro-benzene, &c.).

Explosives

Numerous explosives are made with aid of nitric acid or a mixture of nitric and sulphuric acids. Injury to health and poisoning—especially through development of nitrous fumes—can be caused. Further, some explosives are themselves industrial poisons, especially those giving off volatile fumes or dust.

The most important are:

_Fulminate of mercury_ (HgC₂N₂O₂) is probably to be regarded as the mercury salt of fulminic acid, an isomer of cyanic acid. It is used to make caps for detonating gunpowder and explosives, and is made by dissolving mercury in nitric acid and adding alcohol. The heavy white crystals of mercury fulminate are filtered off and dried. Very injurious fumes are produced in the reaction, containing ethyl acetate, acetic acid, ethyl nitrate, nitrous acid, volatile hydrocyanic acid compounds, hydrocyanic acid, ethyl cyanide, cyanic acid; death consequently can immediately ensue on inhalation of large quantities. The fulminate is itself poisonous, and risk is present in filtering, pressing, drying, and granulating it. Further, in filling the caps in the huts numerous cases of poisoning occur. Heinzerling thinks here that mercury fumes are developed by tiny explosions in the pressing and filling. In a factory in Nuremburg 40 per cent. of the women employed are said to have suffered from mercurial poisoning. Several cases in a factory at Marseilles are recorded by Neisser.[9] In addition to the risk from the salt there is even more from nitrous fumes, which are produced in large quantity in the fulminate department.

_Nitro-glycerin_ (C₃H₅(O—NO₂)₃, dynamite, explosive gelatine).—Nitro-glycerin is made by action of a mixture of nitric and sulphuric acids on anhydrous glycerin. The method of manufacture is as follows (see fig. 10): glycerin is allowed to flow into the acid mixture in leaden vessels; it is agitated by compressed air and care taken that the temperature remains at about 22° C., as above 25° there may be risk. The liquid is then run off and separates into two layers, the lighter nitro-glycerin floating on the top of the acid. The process is watched through glass windows. The nitro-glycerin thus separated is run off, washed by agitation with compressed air, then neutralised (with soda solution) and again washed and lastly filtered. The acid mixture which was run off is carefully separated by standing, as any explosive oil contained in it will rise up. The waste acid freed from nitro-glycerin is recovered in special apparatus, being denitrified by hot air and steam blown through it. The nitrous fumes are condensed to nitric acid. The sulphuric acid is evaporated.

_Dynamite_ is made by mixing nitro-glycerin with infusorial earth previously heated to redness and purified.

_Blasting gelatine_ is made by dissolving gun cotton (collodion wool, nitro-cellulose) in nitro-glycerin. Both are pressed into cartridge shape.

Nitro-glycerin itself is a strong poison which can be absorbed both through the skin and from the alimentary canal. Kobert describes a case where the rubbing of a single drop into the skin caused symptoms lasting for ten hours. Workmen engaged in washing out nitro-glycerin from the kieselguhr earth, having in doing so their bare arms immersed in the liquid, suffered. Although it be granted that nitro-glycerin workers become to a large extent acclimatised, cases of poisoning constantly occur in explosives factories referable to the effect of nitro-glycerin.

Persons mixing and sieving dynamite suffer from ulcers under the nails and at the finger-tips which are difficult to heal. Further, where the apparatus employed is not completely enclosed nitrous fumes escape and become a source of danger. Formerly this danger was constantly present in the nitrating house where nitration was effected in open vessels. Now that this is usually done in closed nitrating apparatus with glass covers the danger is mainly limited to the acid separating house, wash house, and especially the room in which denitration of the waste acids is effected.

A Glycerine reservoir; C Fume flue; D Acid supply pipe; E, G Compressed air supply; H, J Cooling coil.]

A fatal case in a nitro-glycerin factory was reported in 1902 where, through carelessness, a separator had overflowed. The workman who tried to wash away the acid with water inhaled so much of the nitrous fumes that he succumbed sixteen hours later.

Other cases of poisoning by nitrous fumes occurring in the denitrating department are described in detail in the section on the use of nitric acid.

One of these occurred to a man forcing dilute nitric acid from an earthenware egg by means of compressed air into a washing tower. The egg burst and broke an acid tank. The workman died on the following day.

A fatal case occurred in a dynamite factory in cleaning out a storage tank for waste acid in spite of previous swilling and ventilation.

_Gun cotton_ (_pyroxyline_) and its use.—Pyroxyline is the collective name for all products of the action of nitric acid on cellulose (cotton wool and similar material); these products form nitric acid ester of cellulose (nitro-cellulose).

Gun cotton is formed by the action of strong nitric acid on cellulose (cotton wool). A mixture of sulphuric and nitric acids is allowed to act on cotton wool (previously freed from grease, purified, and dried), with subsequent pressing and centrifugalising. In the nitrating centrifugal machine (in the Selvig-Lange method) both processes are effected at the same time.

The interior of this apparatus is filled with nitric acid, cotton wool is introduced, the acid fumes exhausted through earthenware pipes, and the remainder of the acid removed by the centrifugal machine; the nitrated material is then washed, teazed in teazing machines, again washed, neutralised with calcium carbonate, again centrifugalised, and dried. Since drying in drying stoves is a great source of danger of explosion, dehydration is effected with alcohol, and the gun cotton intended for the production of smokeless powder carried directly to the gelatinising vessels (see Smokeless Powder).

Gun cotton, apart from its use for smokeless powder, is pressed in prisms and used for charging torpedoes and sea mines.

_Collodion cotton_ is a partially nitrated cellulose. It is prepared generally in the same way as gun cotton, except that it is treated with a more dilute acid. It is soluble (in contradistinction to gun cotton) in alcohol-ether, and the solution is known as collodion (as used in surgery, photography, and to impregnate incandescent gas mantles). Mixed with camphor and heated collodion forms celluloid.

In Chardonnet’s method for making artificial silk collodion is used by forcing it through fine glass tubes and drawing and spinning it. The alcohol-ether vapours are carried away by fans and the spun material is de-nitrated by ammonium sulphide.

_Smokeless powder_ is a gun cotton powder—that is gun cotton the explosive power of which is utilised by bringing it into a gelatinous condition. This is effected by gelatinising the gun cotton with alcohol-ether or acetone (sometimes with addition of camphor, resin, &c.). A doughy, pasty mass results, which is then rolled, washed, dried, and pressed into rods. Nobel’s nitroleum (artillery powder) consists half of nitro-glycerin and half of collodion cotton. In the production of gun cotton and collodion cotton the workers are affected and endangered by nitric and nitrous fumes unless the nitrating apparatus is completely airtight.

Erosion of the incisor teeth is general, but use of the new nitrating apparatus, especially of the nitrating centrifugal machines already described, has greatly diminished the evil. In making collodion, celluloid and artificial silk, in addition to the risks referred to in the production of gun cotton, the vapour from the solvents, ether, alcohol, acetone, acetic-ether, and camphor, comes into consideration, but there is no account of such poisoning in the literature of the subject.

Other explosives which belong to the aromatic series are described in the chapter on Tar Derivatives, especially picric acid.

PHOSPHORUS AND PHOSPHORUS MATCHES

The total production of _phosphorus_ is not large. Formerly it was prepared from bone ash. Now it is made from phosphorite, which, as in the super-phosphate industry, is decomposed by means of sulphuric acid, soluble phosphate and calcium sulphate being formed; the latter is removed, the solution evaporated, mixed with coal or coke powder, distilled in clay retorts, and received in water.

Phosphorus is also obtained electro-chemically from a mixture of tricalcium phosphate, carbon, and silicic acid, re-distilled for further purification, and finally poured under water into stick form.

_Red phosphorus_ (amorphous phosphorus) is obtained by heating yellow phosphorus in the absence of air and subsequently extracting with carbon bisulphide.

_Phosphorus matches_ are made by first fixing the wooden splints in frames and then dipping the ends either into paraffin or sulphur which serve to carry the flame to the wood. Then follows dipping in the phosphorus paste proper, for which suitable dipping machines are now used. The phosphorus paste consists of yellow phosphorus, an oxidising agent (red lead, lead nitrate, nitre, or manganese dioxide) and a binding substance (dextrine, gum); finally the matches are dried and packed.

_Safety matches_ are made in the same way, except that there is no phosphorus. The paste consists of potassium chlorate, sulphur, or antimony sulphide, potassium bichromate, solution of gum or dextrine, and different admixtures such as glass powder, &c. These matches are saturated with paraffin or ammonium phosphate. To strike them a special friction surface is required containing red phosphorus, antimony sulphide, and dextrine. In the act of striking the heat generated converts a trace of the red phosphorus into the yellow variety which takes fire.

Danger to health arises from the poisonous gases evolved in the decomposition of the calcined bones by sulphuric acid. When phosphorus is made from phosphorite the same dangers to health are present as in the production of super-phosphate artificial manure, which is characterised by the generation of hydrofluoric and fluosilicic acids. In the distillation of phosphorus phosphoretted hydrogen and phosphorus fumes may escape and prove dangerous.

Industrial poisoning from the use of white phosphorus in the manufacture of matches has greater interest than its occurrence in the production of phosphorus itself. Already in 1845 chronic phosphorus poisoning (phosphorus necrosis) had been observed by Lorinser, and carefully described by Bibra and Geist in 1847. In the early years of its use phosphorus necrosis must have been fairly frequent in lucifer match factories, and not infrequently have led to death. This necessitated preventive measures in various States (see Part III); cases became fewer, but did not disappear altogether.

Especially dangerous is the preparation of the paste, dipping, and manipulations connected with drying and filling the matches into boxes. According to the reports of the Austrian factory inspectors there are about 4500 lucifer match workers in that country, among whom seventy-four cases of necrosis are known to have occurred between the years 1900 and 1908 inclusive.

Teleky[1] considers these figures much too small, and from inquiries undertaken himself ascertained that 156 cases occurred in Austria between 1896 and 1906, while factory inspectors’ reports dealt with only seventy-five. He was of opinion that his own figures were not complete, and thinks that in the ten years 1896 to 1905 there must have been from 350 to 400 cases of phosphorus necrosis in the whole of Austria. Despite strict regulations, modern equipment of the factories, introduction of improved machinery, and limitation of the white phosphorus match industry to large factories, it has not been possible to banish the risk, and the same is true of Bohemia, where there is always a succession of cases. Valuable statistics of phosphorus necrosis in Hungary are available.[2] In 1908 there were sixteen factories employing 1882 workers of whom 30 per cent. were young—children even were employed. The industry is carried on in primitive fashion without hygienic arrangements anywhere. It is strange that, notwithstanding these bad conditions, among a large number of the workers examined only fourteen active cases were found, in addition to two commencing, and fifteen cured—altogether thirty-one cases (excluding fifty-five cases in which there was some other pathological change in the mouth). Altogether ninety-three cases since 1900 were traced in Hungary, and in view of the unsatisfactory situation preventive measures, short of prohibition of the use of white phosphorus, would be useless.

In England among 4000 lucifer match workers there were thirteen cases in the years 1900 to 1907 inclusive. Diminution in the number was due to improved methods of manufacture and periodical dental examination prescribed under Special Rules.

Phosphorus necrosis is not the only sign of industrial phosphorus poisoning, as the condition of fragilitas ossium is recognised.[3] From what has been said it is evident that preventive measures against phosphorus poisoning, although they diminish the number, are not able to get rid of phosphorus necrosis, and so civilised States have gradually been driven to prohibit the use of white phosphorus (for the history of this see Part III).

Use of chrome salts (especially potassium bichromate) in the preparation of the paste causes risk of poisoning in premises where ‘Swedish’ matches are made. Attention has been called to the frequency of chrome ulceration.[4] The paste used consists of 3-6 per cent. chrome salt, so that each match head contains about ½ mg. Wodtke found among eighty-four workers early perforation of the septum in thirteen. Severe eczema also has been noted.

It is even alleged that red phosphorus is not entirely free from danger. Such cachexia as has been noted may be referable to the absorption of potassium chlorate.

Other Uses of Phosphorus and Compounds of Phosphorus

Isolated cases of phosphorus poisoning have been observed in the manufacture of phosphor-bronze. This consists of 90 parts copper, 9 parts tin, and 0·5 to 0·75 phosphorus.

_Sulphides of phosphorus_ (P₂S₅, P₄S₃, P₂S₃) are made by melting together red phosphorus and sulphur. They make a satisfactory substitute for the poisonous yellow phosphorus and are considered non-poisonous, but the fact remains that they give off annoying sulphuretted hydrogen gas.

_Phosphoretted hydrogen gas_ (PH₃) rarely gives rise to industrial poisoning. It may come off in small amounts in the preparation of acetylene and in the preparation of, and manipulations with, white phosphorus. It is stated that in acetylene made of American calcium carbide 0·04 per cent. of phosphoretted hydrogen is present, and in acetylene from Swedish calcium carbide 0·02 per cent.; Lunge and Cederkreutz found an acetylene containing 0·06 per cent. These amounts might cause poisoning if the gas were diffused in confined spaces. Poisoning, in part attributable to phosphoretted hydrogen gas, is brought about through ferro-silicon (see under Ferro-silicon).

Superphosphate and Artificial Manure

_Superphosphate_, an artificial manure, is prepared from various raw materials having a high proportion of insoluble basic calcium phosphate (tricalcium phosphate), which by treatment with sulphuric acid are converted into the soluble acid calcium phosphate (monocalcium phosphate) and calcium sulphate. Mineral substances such as phosphorites, coprolites, guano, bone ash, &c., serve as the starting-point. Chamber acid, or sometimes the waste acid from the preparation of nitro-benzene or purification of petroleum, are used in the conversion. The raw materials are ground in closed-in apparatus, under negative pressure, and mixed with the sulphuric acid in wooden lead-lined boxes or walled receptacles. The product is then stored until the completion of the reaction in ‘dens,’ dried, and pulverised in disintegrators.

In the manufacture of bone meal extraction of the fat from the bones with benzine precedes treatment with acid.

A further source of artificial manure is _basic slag_—the slag left in the manufacture of steel by the Gilchrist-Thomas method—which contains 10-25 per cent. of readily soluble phosphoric acid. It requires, therefore, only to be ground into a very fine powder to serve as a suitable manure.

Owing to the considerable heat generated by the action of the sulphuric acid when mixed with the pulverised raw materials (especially in the conversion of the phosphorites) hydrofluoric and silicofluoric acid vapours are evolved in appreciable amount, and also carbonic and hydrochloric acid vapours, sulphur dioxide, and sulphuretted hydrogen gas. These gases—notably such as contain fluorine—if not effectually dealt with by air-tight apparatus and exhaust ventilation—may lead to serious annoyance and injury to the persons employed. Further, there is risk of erosion of the skin from contact with the acid, &c.

A case is described of pustular eczema on the scrotum of a worker engaged in drying sodium silicofluoride, due probably to conveyance of irritating matter by the hands. After the precaution of wearing gloves was adopted the affection disappeared.

A marked case of poisoning by nitrous fumes even is recorded in the manufacture of artificial manure from mixing Chili saltpetre with a very acid superphosphate.

Injurious fumes can be given off in the rooms where bones are stored and, in the absence of efficient ventilation, carbonic acid gas can accumulate to an amount that may be dangerous.

The fine dust produced in the grinding of _basic slag_ has, if inhaled, a markedly corrosive action on the respiratory mucous membrane attributed by some to the high proportion (about 50 per cent.) in it of quicklime. As a matter of fact numerous small ulcers are found on the mucous membranes of basic slag grinders and ulceration of the lung tissue has been observed. The opinion is expressed that this is due to corrosive action of the dust itself, and not merely to the sharp, jagged edged particles of dust inhaled. And in support of this view is cited the frequency with which epidemics of pneumonia have been noted among persons employed in basic slag works. Thus in Nantes thirteen cases of severe pneumonia followed one another in quick succession. And similar association has been noted in Middlesbrough, where the action of the basic slag dust was believed to injure the lung tissue and therefore to provide a favourable soil for the development of the pneumonia bacillus. Statistics collected by the Imperial Health Office showed that in the three years 1892, 1893, and 1894, 91·1 per cent., 108·9 per cent., and 91·3 per cent. respectively of the workers became ill, the proportion of respiratory diseases being 56·4 per cent., 54·4 per cent., and 54·3 per cent. respectively. A case of severe inflammation of the lungs is described in a labourer scattering basic slag in a high wind which drove some of it back in his face.

Lewin has described a case in which a worker scattering a mixture of basic slag and ammonium superphosphate suffered from an eczematous ulceration which, on being scratched by the patient, became infected and led to death from general blood poisoning. Lewin regarded the fatal issue as the sequela of the scattering of the manure.

Inflammation of the conjunctiva and of the eyelids has been recorded.

CHROMIUM COMPOUNDS AND THEIR USES

Chrome ironstone, lime, and soda are ground and intimately mixed. They are next roasted in reverberatory furnaces, neutral _sodium chromate_ being formed. This is lixiviated and converted into sodium bichromate (Na₂Cr₂O₇) by treatment with sulphuric acid. Concentration by evaporation follows; the concentrated liquor is crystallised in cast-iron tanks. The crystals are centrifugalised, dried, and packed. _Potassium bichromate_ may be made in the same way, or, as is usually the case, out of sodium bichromate and potassium chloride.

The bichromates are used in the preparation and oxidation of chrome colours, but their principal use is in dyeing and calico printing, bleaching palm oil, purifying wood spirit and brandy, in the preparation of ‘Swedish’ matches, in the manufacture of glass, in photography, in dyeing, in tanning, and in oxidation of anthracene to anthraquinone.

Lead Chromate and Chrome Colours

_Chrome yellow_ is neutral lead chromate (PbCrO₄). It is obtained by precipitating a solution of potassium bichromate with lead acetate or lead nitrate, or by digesting the bichromate solution with lead sulphate, and is used as a paint and in calico and cloth printing. With Paris or Berlin blue it forms a _chrome green_. _Chrome orange_, i.e. basic lead chromate (PbCrO₄Pb(OH)₂) is made by adding milk of lime to lead chromate and boiling.

_Chromium_ and _chromic acid salts_ are widely used in dyeing and printing, both as mordants and oxidising agents and as dyes (chrome yellow, chrome orange). In mordanting wool with potassium chromate the wool is boiled in a potassium chromate solution to which acids such as sulphuric, lactic, oxalic, or acetic are added.

In dyeing with chrome yellow, for instance, the following is the process. Cotton wool is saturated with nitrate or acetate of lead and dried, passed through lime water, ammonia, or sodium sulphate, and soaked in a warm solution of potassium bichromate. The yellow is converted into the orange colour by subsequent passage through milk of lime.

_Chrome tanning._—This method of producing chrome leather, first patented in America, is carried out by either the single or two bath process.

In the two bath process the material is first soaked in a saturated solution of bichromate and then treated with an acid solution of thiosulphate (sodium hyposulphite) so as to reduce completely the chromic acid. The process is completed even with the hardest skins in from two to three days.

In the single bath method basic chrome salts are used in highly concentrated form. The skins are passed from dilute into strong solutions. In this process also tanning is quickly effected.

EFFECTS ON HEALTH.—Among the persons employed in the bichromate factory of which Leymann has furnished detailed particulars, the number of sick days was greater than that among other workers.

Further, _erosion of the skin_ (_chrome holes_) is characteristic of the manufacture of bichromates. These are sluggish ulcers taking a long time to heal. This is the main cause of the increased general morbidity that has been observed. The well-known perforation of the septum of the nose without, however, causing ulterior effects, was observed by Leymann in all the workers in the factory. This coincides with the opinion of others who have found the occurrence of chrome holes, and especially perforation of the septum, as an extraordinarily frequent occurrence. Many such observations are recorded,[1] and also in workers manufacturing ‘Swedish’ matches. Thus of 237 bichromate workers, ulcers were present in 107 and perforation in 87. According to Lewin, who has paid special attention to the poisonous nature of chromium compounds, they can act in two ways: first, on the skin and mucous membrane, where the dust alights, on the alimentary tract by swallowing, and on the pharynx by inhalation. Secondly, by absorption into the blood, kidney disease may result.

The opinion that chromium, in addition to local, can have constitutional effect is supported by other authorities. Leymann describes a case of severe industrial chrome poisoning accompanied by nephritis in a worker who had inhaled and swallowed much chromate dust in cleaning out a vessel. Regulations for the manufacture of bichromates (see Part III) have no doubt improved the condition, but reports still show that perforation of the septum generally takes place.