Fig. 6.—Preparation of Chlorine—Diaphragm Method (after Ost)
Hydrochloric acid is first introduced into the chlorine still (vessels about 3 m. in height, of Yorkshire flag or fireclay), next the Weldon mud gradually, and finally steam to bring the whole to boiling; chlorine comes off in a uniform stream. The manganous chloride still liquor is run into settling tanks. The regeneration of the manganous chloride liquor takes place in an oxidiser which consists of a vertical iron cylinder in which air is blown into the heated mixture of manganous chloride and milk of lime. The dark precipitate so formed, ‘Weldon mud,’ as described, is used over again, while the calcium chloride liquor runs away.
The Deacon process depends mainly on leading the stream of hydrochloric acid gas evolved from a saltcake pot mixed with air and heated into a tower containing broken bricks of the size of a nut saturated with copper chloride. Chlorine is evolved according to the equation:
Fig. 7.—Preparation of Chlorine—Bell Method (after Ost)
The electrolytic production of chlorine with simultaneous production of caustic alkali is increasing and depends on the splitting up of alkaline chlorides by a current of electricity. The chlorine evolved at the anode and the alkaline liquor formed at the cathode must be kept apart to prevent secondary formation of hypochlorite and chlorate (see below). This separation is generally effected in one of three ways: (1) In the diaphragm process (Griesheim-Elektron chemical works) the anode and cathode are kept separate by porous earthenware diaphragms arranged as illustrated in fig. 6. The anode consists of gas carbon, or is made by pressing and firing a mixture of charcoal and tar; it lies inside the diaphragm. The chlorine developed in the anodal cell is carried away by a pipe. The metal vessel serves as the cathode. The alkali, which, since it contains chloride, is recovered as caustic soda after evaporation and crystallisation, collects in the cathodal space lying outside the diaphragm. (2) By the Bell method (chemical factory at Aussig) the anodal and cathodal fluids, which keep apart by their different specific weights, are separated by a stoneware bell; the poles consist of sheet iron and carbon. The containing vessel is of stoneware. (3) In the mercury process (England) sodium chloride is electrolysed without a diaphragm, mercury serving as the cathode. This takes up the sodium, which is afterwards recovered from the amalgam formed by means of water.
If chlorate or hypochlorite is to be obtained electrolytically, electrodes of the very resistant but expensive platinum iridium are used without a diaphragm. Chlorine is developed—not free, but combined with the caustic potash. The bleaching fluid obtained electrolytically in this way is a rival of bleaching powder.
Bleaching powder is made from chlorine obtained by the Weldon or Deacon process. Its preparation depends on the fact that calcium hydrate takes up chlorine in the cold with formation of calcium hypochlorite after the equation:
The resulting product contains from 35 to 36 per cent. chlorine, which is given off again when treated with acids.
The preparation of chloride of lime takes place in bleaching powder chambers made of sheets of lead and Yorkshire flagstones. The lime is spread out on the floors of these and chlorine introduced. Before the process is complete the lime must be turned occasionally.
In the manufacture of bleaching powder from Deacon chlorine, Hasenclever has constructed a special cylindrical apparatus (fig. 8), consisting of several superimposed cast-iron cylinders in which are worm arrangements carrying the lime along, while chlorine gas passes over in an opposite direction. This continuous process is, however, only possible for the Deacon chlorine strongly diluted with nitrogen and oxygen and not for undiluted Weldon gas.
Liquid chlorine can be obtained by pressure and cooling from concentrated almost pure Weldon chlorine gas.
Potassium chlorate, which, as has been said, is now mostly obtained electrolytically, was formerly obtained by passing Deacon chlorine into milk of lime and decomposing the calcium chlorate formed by potassium chloride.
Chlorine and chloride of lime are used for bleaching; chlorine further is used in the manufacture of colours; chloride of lime as a mordant in cloth printing and in the preparation of chloroform; the chlorates are oxidising agents and used in making safety matches. The manufacture of organic chlorine products will be dealt with later.
Fig. 8.—Preparation of Bleaching Powder. Apparatus of Hasenclever (after Ost)
A Hopper for slaked lime; W Worm conveying lime; Z Toothed wheels; K Movable covers; C Entrance for chlorine gas; D Pipe for escape of chlorine-free gas; B Outlet shoot for bleaching powder
Effects on Health.—In these industries the possibility of injury to health and poisoning by inhalation of chlorine gas is prominent. Leymann has shown that persons employed in the manufacture of chlorine and bleaching powder suffer from diseases of the respiratory organs 17·8 per cent., as contrasted with 8·8 per cent. in other workers: and this is without doubt attributable to the injurious effect of chlorine gas, which it is hardly possible to avoid despite the fact that Leymann’s figures refer to a model factory. But the figures show also that as the industry became perfected the number of cases of sickness steadily diminished.
Most cases occur from unsatisfactory conditions in the production of chloride of lime, especially if the chloride of lime chambers leak, if the lime is turned over while the chlorine is being let in, by too early entrance into chambers insufficiently ventilated, and by careless and unsuitable methods of emptying the finished bleaching powder.
The possibility of injury is naturally greater from the concentrated gas prepared by the Weldon process than from the diluted gas of the Deacon process—the more so as in the latter the bleaching powder is made in the Hasenclever closed-in cylindrical apparatus in which the chlorine is completely taken up by the lime. The safest process of all is the electrolytic, as, if properly arranged, there should be no escape of chlorine gas. The chlorine developed in the cells (when carried out on the large scale) is drawn away by fans and conducted in closed pipes to the place where it is used.
Many researches have been published as to the character of the skin affection well known under the name of chlorine rash (chlorakne). Some maintain that it is not due to chlorine at all, but is an eczema set up by tar. Others maintain that it is due to a combined action of chlorine and tar. Support to this view is given by the observation that cases of chlorine rash, formerly of constant occurrence in a factory for electrolytic manufacture of chlorine, disappeared entirely on substitution of magnetite at the anode for carbon.1 The conclusion seems justified that the constituents of the carbon or of the surrounding material set up the condition.
Chlorine rash has been observed in an alkali works where chlorine was not produced electrolytically, and under conditions which suggested that compounds of tar and chlorine were the cause. In this factory for the production of salt cake by the Hargreaves’ process cakes of rock salt were prepared and, for the purpose of drying, conveyed on an endless metal band through a stove. To prevent formation of crusts the band was tarred. The salt blocks are decomposed in the usual way by sulphur dioxide, steam, and oxygen of the air, and the hydrochloric acid vapour led through Deacon towers in which the decomposition of the hydrochloric acid into chlorine and water is effected by metal salts in the manner characteristic of the Deacon process. These salts are introduced in small earthenware trays which periodically have to be removed and renewed; the persons engaged in doing this were those affected. The explanation was probably that the tar sticking to the salt blocks distilled in the saltcake furnaces and formed a compound with the chlorine which condensed on the earthenware trays. When contact with these trays was recognised as the cause, the danger was met by observance of the greatest cleanliness in opening and emptying the Deacon towers.
Leymann2 is certain that the rash is due to chlorinated products which emanate from the tar used in the construction of the cells. And the affection has been found to be much more prevalent when the contents of the cells are emptied while the contents are still hot than when they are first allowed to get cold.
Lehmann3 has approached the subject on the experimental side, and is of opinion that probably chlorinated tar derivatives (chlorinated phenols) are the cause of the trouble. Both he and Roth think that the affection is due not to external irritation of the skin, but to absorption of the poisonous substances into the system and their elimination by way of the glands of the skin.
In the section on manganese poisoning detailed reference is made to the form of illness recently described in persons employed in drying the regenerated Weldon mud.
Mercurial poisoning is possible when mercury is used in the production of chlorine electrolytically.
In the manufacture of chlorates and hypochlorite, bleaching fluids, &c., injury to health from chlorine is possible in the same way as has been described above.
Chlorine is used for the production of a number of organic chlorine compounds, and in the manufacture of bromine and iodine, processes which give rise to the possibility of injury to health and poisoning by chlorine; further, several of the substances so prepared are themselves corrosive or irritating or otherwise poisonous. Nevertheless, severe poisoning and injurious effects can be almost entirely avoided by adoption of suitable precautions. In the factory to which Leymann’s figures refer, where daily several thousand kilos of chlorine and organic chlorine compounds are prepared, a relatively very favourable state of health of the persons employed was noted. At all events the preparation of chlorine by the electrolytic process takes place in closed vessels admirably adapted to avoid any escape of chlorine gas except as the result of breakage of the apparatus or pipes. When this happens, however, the pipes conducting the gas can be immediately disconnected and the chlorine led into other apparatus or into the bleaching powder factory.
As such complete precautionary arrangements are not everywhere to be found, we describe briefly the most important of the industries in question and the poisoning recognised in them.
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
Leymann6 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.
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).
Leymann12 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 Ascher15 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
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:
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.
Fig. 9.—Preparation of Nitric Acid (after Ost)
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 instances4 :
(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.
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. Roth8 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.).
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.