INDUSTRIAL POISONING

FROM FUMES, GASES AND POISONS
OF MANUFACTURING PROCESSES

BY THE SAME AUTHOR

LEAD POISONING
AND LEAD ABSORPTION:

THE SYMPTOMS, PATHOLOGY AND PREVENTION, WITH SPECIAL REFERENCE TO THEIR INDUSTRIAL ORIGIN AND AN ACCOUNT OF THE PRINCIPAL PROCESSES INVOLVING RISK.

By THOMAS M. LEGGE M.D. (Oxon.), D.P.H. (Cantab.), H.M. Medical Inspector of Factories; Lecturer on Factory Hygiene, University of Manchester; and KENNETH W. GOADBY, D.P.H. (Cantab.), Pathologist and Lecturer on Bacteriology, National Dental Hospital. Illustrated. viii+308 pp. 12s. 6d. net.

London: EDWARD ARNOLD.

INDUSTRIAL POISONING

FROM FUMES, GASES AND POISONS
OF MANUFACTURING PROCESSES

BY
DR. J. RAMBOUSEK
PROFESSOR OF FACTORY HYGIENE,
AND CHIEF STATE HEALTH OFFICER, PRAGUE

TRANSLATED AND EDITED BY
THOMAS M. LEGGE, M.D., D.P.H.
H.M. MEDICAL INSPECTOR OF FACTORIES
JOINT AUTHOR OF ‘LEAD POISONING AND LEAD ABSORPTION’

WITH ILLUSTRATIONS

LONDON
EDWARD ARNOLD
1913

TRANSLATOR’S PREFACE

I undertook the translation of Dr. Rambousek’s book because it seemed to me to treat the subject of industrial poisons in as novel, comprehensive, and systematic a manner as was possible within the compass of a single volume. Having learnt much myself from Continental writings on industrial diseases and factory hygiene, I was anxious to let others also see how wide a field they had covered and how thorough were the regulations for dangerous trades abroad, especially in Germany. A praiseworthy feature of Dr. Rambousek’s book was the wealth of references to the work of foreign writers which is made on almost every page. To have left these names and references, however, in the text as he has done would have made the translation tedious reading, and therefore for the sake of those who desire to pursue inquiry further I have adopted the course of collecting the great majority and placing them all together in an appendix at the end of the volume.

Dr. Rambousek as a medical man, a chemist, and a government official having control of industrial matters, is equipped with the very special knowledge required to describe the manufacturing processes giving rise to injurious effects, the pathology of the lesions set up, and the preventive measures necessary to combat them. In his references to work done in this country he has relied largely on abstracts which have appeared in medical and technical journals published on the Continent. I have only thought it necessary to amplify his statements when important work carried out here on industrial poisoning,—such as that on nickel carbonyl and on ferro-silicon—had been insufficiently noted. Such additions are introduced in square brackets or in footnotes.

In his preface Dr. Rambousek says ‘the book is intended for all who are, or are obliged to be, or ought to be, interested in industrial poisoning.’ No words could better describe the scope of the book.

The work of translation would never have been begun but for the assistance given me in Parts II and III by my sister, Miss H. Edith Legge. To her, and to Mr. H. E. Brothers, F.I.C., who has been to the trouble of reading the proofs and correcting many mistakes which my technical knowledge was insufficient to enable me to detect, my best thanks are due.

I am indebted to Messrs. Davidson & Co., Belfast, for permission to use figs. 46 and 48; to Messrs. Locke, Lancaster & Co., Millwall, for fig. 27; to Mr. R. Jacobson, for figs. 30, 33, 37, 38, and 43; to Messrs. Siebe, Gorman & Co., for figs. 32, 39, and 40; to Messrs. Blackman & Co. for fig. 47; to Messrs. Matthews & Yates for fig. 54; to H.M. Controller of the Stationery Office for permission to reproduce figs. 52, 53, and 54, and the diagrams on p. 284; and lastly to my publisher, for figs. 41, 42, 43, and 49, which are taken from the book by Dr. K. W. Goadby and myself on ‘Lead Poisoning and Lead Absorption.’

T. M. L.

Hampstead, May 1913.

CONTENTS

INTRODUCTION

The attempt to systematise from the scientific standpoint the mass of material that has been collected about poisons is a very heavy task, even for the toxicologist who desires to treat his subject comprehensively. How much greater is the difficulty of writing a systematic book on industrial poisoning keeping practical application in the forefront!

Technical considerations which are decisive in the causation and prevention of industrial poisoning are here of especial moment, and must naturally influence classification of the subject-matter when the object is to assist those concerned in factory hygiene.

Bearing this in mind, I have divided the subject into three parts. The arrangement of the first, which gives as complete a statement as possible of the occurrence of industrial poisoning, into industries and processes was determined on technical grounds. The second, which amplifies the first, attempts to summarise the pathology or symptoms of the various forms of poisoning. The references to the literature of the particular subjects—as exhaustive as I could make them—will lighten further study. To these two parts, following on knowledge of causation and symptoms, the third, in which preventive measures are outlined, is linked.

The apparent drawback in use of the book is that one form of poisoning has often to be referred to in three places. But, I hope, this is more than counterbalanced by the completeness of the scheme which results from the subdivision of the subject.

The pathology of industrial poisoning necessitates frequent repetition when describing the branches of industry giving rise to the intoxication, as one and the same form can occur in the most varied processes. The numerous instances of actual cases of poisoning quoted must therefore be regarded as conforming to the same pathological type. Similarly, preventive measures require separate systematic treatment in order to avoid constant repetition which would otherwise obscure the general survey. Quite a number of means of prevention apply equally to several industries in which the same cause is at work. The success attained by thus simplifying the issues is the greater because such common measures are the easier to carry through and to supervise.

The method therefore has been adopted only after serious reflection and has been directed mainly by practical considerations.

Recent cases which have either been reported or come to the knowledge of the author have been given, with particulars as exact as possible. Cases dating back some time have been omitted intentionally so as to exclude everything which did not correspond with the present conditions of industry and trade. Historical facts only receive consideration in so far as they are fundamentally important and necessary for the sake of completeness.

The details given in Part I of actual instances will supply material for fresh efforts, renewed investigation, and new points of attack.

INDUSTRIAL POISONING

PART I
DESCRIPTION OF THE INDUSTRIES AND PROCESSES ATTENDED WITH RISK OF POISONING; INCIDENCE OF SUCH POISONING

I. THE CHEMICAL INDUSTRY

GENERAL CONSIDERATIONS AS TO INCIDENCE OF INDUSTRIAL POISONING

The chemical industry offers naturally a wide field for the occurrence of industrial poisoning. Daily contact with the actual poisonous substances to be prepared, used, stored, and despatched in large quantity gives opportunity for either acute or chronic poisoning—in the former case from sudden accidental entrance into the system of fairly large doses, as the result of defective or careless manipulation, and, in the latter, constant gradual absorption (often unsuspected) of the poison in small amount.

The industry, however, can take credit for the way in which incidence of industrial poisoning has been kept down in view of the magnitude and variety of the risks which often threaten. This is attributable to the comprehensive hygienic measures enforced in large chemical works keeping abreast of modern advance in technical knowledge. A section of this book deals with the principles underlying these measures. Nevertheless, despite all regulations, risk of poisoning cannot be wholly banished. Again and again accidents and illness occur for which industrial poisoning is responsible. Wholly to prevent this is as impossible as entirely to prevent accidents by mechanical guarding of machinery.

Owing to the unknown sources of danger, successful measures to ward it off are often difficult. The rapid advance of this branch of industry, the constant development of new processes and reactions, the frequent discovery of new materials (with properties at first unknown, and for a long time insufficiently understood, but nevertheless indispensable), constantly give rise to new dangers and possibilities of danger, of which an accident or some disease with hitherto unknown symptoms is the first indication. Further, even when the dangerous effects are recognised, there may often be difficulty in devising appropriate precautions, as circumstances may prevent immediate recognition of the action of the poison. We cannot always tell, for instance, with the substances used or produced in the processes, which is responsible for the poisoning, because, not infrequently, the substances in question are not chemically pure, but may be either raw products, bye-products, &c., producing mixtures of different bodies or liberating different chemical compounds as impurities.

Hence difficulty often arises in the strict scientific explanation of particular cases of poisoning, and, in a text-book such as this, difficulty also of description. A rather full treatment of the technical processes may make the task easier and help to give a connected picture of the risks of poisoning in the chemical industry. Such a procedure may be especially useful to readers insufficiently acquainted with chemical technology.

We are indebted to Leymann[1] and Grandhomme[2] especially for knowledge of incidence of industrial poisoning in this industry. The statistical data furnished by them are the most important proof that poisoning, at any rate in large factories, is not of very frequent occurrence.

Leymann’s statistics relate to a large modern works in which the number employed during the twenty-three years of observation increased from 640 in the year 1891 to 1562 in 1904, giving an average of about 1000 yearly, one-half of whom might properly be defined as ‘chemical workers.’ The factory is concerned in the manufacture of sulphuric, nitric, and hydrochloric acids, alkali, bichromates, aniline, trinitro-phenol, bleaching powder, organic chlorine compounds, and potassium permanganate.

These statistics are usefully complemented by those of Grandhomme drawn from the colour works at Höchst a-M. This large aniline works employs from 2600 to 2700 workers; the raw materials are principally benzene and its homologues, naphthalene and anthracene. The manufacture includes the production of coal-tar colours, nitro- and dinitro-benzene, aniline, rosaniline, fuchsine, and other aniline colours, and finally such pharmaceutical preparations as antipyrin, dermatol, sanoform, &c. Of the 2700 employed, 1400 are chemical workers and the remainder labourers.

These two series of statistics based on exact observations and covering allied chemical manufacture are taken together. They seek to give the answer to the question—How many and what industrial poisonings are found?

The figures of Leymann (on an average of 1000 workers employed per annum) show 285 cases of poisoning reported between the years 1881 and 1904. Of these 275 were caused by aniline, toluidine, nitro- and dinitro-benzene, nitrophenol, nitrochloro and dinitrochloro benzene. Three were fatal and several involved lengthy invalidity (from 30 to 134 days, owing to secondary pneumonia). Included further are one severe case of chrome (bichromate) poisoning (with nephritis as a sequela), five cases of lead poisoning, three of chlorine, and one of sulphuretted hydrogen gas. In the Höchst a-M. factory (employing about 2500 workers) there were, in the ten years 1883-92, only 129 cases of poisoning, of which 109 were due to aniline. Later figures for the years 1893-5 showed 122 cases, of which 43 were due to aniline and 76 to lead (contracted mostly in the nitrating house). Grandhomme mentions further hyperidrosis among persons employed on solutions of calcium chloride, injury to health from inhalation of methyl iodide vapour in the antipyrin department, a fatal case of benzene poisoning (entering an empty vessel in which materials had previously been extracted with benzene), and finally ulceration and perforation of the septum of the nose in several chrome workers.

The number of severe cases is not large, but it must be remembered that the factories to which the figures relate are in every respect models of their kind, amply provided with safety appliances and arrangements for the welfare of the workers. The relatively small amount of poisoning is to be attributed without doubt to the precautionary measures taken. Further, in the statistics referred to only those cases are included in which the symptoms were definite, or so severe as to necessitate medical treatment. Absorption of the poison in small amount without producing characteristic symptoms, as is often the case with irritating or corrosive fumes, and such as involve only temporary indisposition, are not included. Leymann himself refers to this when dealing with illness observed in the mineral acid department (especially sulphuric acid), and calls attention to the frequency of affections of the respiratory organs among the persons employed, attributing them rightly to the irritating and corrosive effect of the acid vapour. Elsewhere he refers to the frequency of digestive disturbance among persons coming into contact with sodium sulphide, and thinks that this may be due to the action of sulphuretted hydrogen gas.

Nevertheless, the effect of industrial poisons on the health of workers in chemical factories ought on no account to be made light of. The admirable results cited are due to a proper recognition of the danger, with consequent care to guard against it. Not only have Grandhomme and Leymann[A] rendered great services by their work, but the firms in question also, by allowing such full and careful inquiries to be undertaken and published.

SULPHURIC ACID (SULPHUR DIOXIDE)

Manufacture.—Sulphur dioxide, generally obtained by roasting pyrites in furnaces of various constructions, or, more rarely, by burning brimstone or sulphur from the spent oxide of gas-works, serves as the raw material for the manufacture of sulphuric acid. Before roasting the pyrites is crushed, the ‘lump ore’ then separated from the ‘smalls,’ the former roasted in ‘lump-burners’ or kilns (generally several roasting furnace hearths united into one system), and the latter preferably in Malétra and Malétra-Schaffner shelf-burners ([fig. 1]) composed of several superimposed firebrick shelves. The pyrites is charged on to the uppermost shelf and gradually worked downwards. Pyrites residues are not suitable for direct recovery of iron, but copper can be recovered from residues sufficiently rich in metal by the wet process; the residues thus freed of copper and sulphur are then smelted for recovery of iron.

Fig. 1.—Pyrites Burner for Smalls (after Lueger)

Utilisation for sulphuric acid manufacture of the sulphur dioxide given off in the calcining of zinc blende (see Spelter works), impracticable in reverberatory furnaces, has been made possible at the Rhenania factory by introduction of muffle furnaces (several superimposed), because by this means the gases led off are sufficiently concentrated, as they are not diluted with the gases and smoke from the heating fires. This method, like any other which utilises the gases from roasting furnaces, has great hygienic, in addition to economical, advantages, because escape of sulphur dioxide gas is avoided. Furnace gases, too poor in sulphur dioxide to serve for direct production of sulphuric acid, can with advantage be made to produce liquid anhydrous sulphur dioxide. Thus, the sulphur dioxide gas from the furnaces is first absorbed by water, driven off again by boiling, cooled, dried, and liquefied by pressure.

The gaseous sulphur dioxide obtained by any of the methods described is converted into sulphuric acid either by (a) the chamber process or (b) the contact process.

In the lead chamber process the furnace gases pass through flues in which the flue dust and a portion of the arsenious acid are deposited into the Glover tower at a temperature of about 300° C., and from there into the lead chambers where oxidation of the sulphur dioxide into sulphuric acid takes place, in the presence of sufficient water, by transference of the oxygen of the air through the intervention of the oxides of nitrogen. The gases containing oxides of nitrogen, &c., which are drawn out of the lead chambers, have the nitrous fumes absorbed in the Gay-Lussac tower (of which there are one or two in series), by passage through sulphuric acid which is made to trickle down the tower. The sulphuric acid so obtained, rich in oxides of nitrogen, and the chamber acid are led to the Glover tower for the purpose of denitration and concentration, so that all the sulphuric acid leaves the Glover as Glover acid of about 136-144° Tw. Losses in nitrous fumes are best made up by addition of nitric acid at the Glover or introduction into the first chamber. The deficiency is also frequently made good from nitre-pots.

The lead chambers ([fig. 2]) are usually constructed entirely—sides, roof, and floor—of lead sheets, which are joined together by means of a hydrogen blowpipe. The sheets forming the roof and walls are supported, independent of the bottom, on a framework of wood. The capacity varies from 35,000 to 80,000 cubic feet. The floor forms a flat collecting surface for the chamber acid which lutes the chamber from the outer air. The necessary water is introduced into the chamber as steam or fine water spray.

The Glover and Gay-Lussac towers are lead towers. The Glover is lined with acid-proof bricks and filled with acid-proof packing to increase the amount of contact. The Gay-Lussac is filled with coke over which the concentrated sulphuric acid referred to above flows, forming, after absorption of the nitrous fumes, nitro-sulphuric acid.

Fig. 2a.—Lead Chamber System—Section through X X (after Ost)

Fig. 2b.—Lead Chamber System—Plan

• A Pyrites Burner
• B Glover Tower
• C Draft Regulator
• D, D´ Lead Chambers
• E Air Shaft
• F, F,´ F,´´ F´´´ Acid Reservoirs
• G Acid Egg
• H Cooler
• J Gay-Lussac Tower

As already stated, two Gay-Lussac towers are usually connected together, or where there are several lead-chamber systems there is, apart from the Gay-Lussac attached to each, a central Gay-Lussac in addition, common to the whole series. The introduction of several Gay-Lussac towers has the advantage of preventing loss of the nitrous fumes as much as possible—mainly on economical grounds, as nitric acid is expensive. But this arrangement is at the same time advantageous on hygienic grounds, as escape of poisonous gases containing nitrous fumes, &c., is effectually avoided. The acids are driven to the top of the towers by compressed air. The whole system—chambers and towers—is connected by means of wide lead conduits. Frequently, for the purpose of quickening the chamber process (by increasing the number of condensing surfaces) Lunge-Rohrmann plate towers are inserted in the system—tall towers lined with lead in which square perforated plates are hung horizontally, and down which diluted sulphuric acid trickles.

To increase the draught in the whole system a chimney is usual at the end, and, in addition, a fan of hard lead or earthenware may be introduced in front of the first chamber or between the two Gay-Lussac towers. Maintenance of a constant uniform draught is not only necessary for technical reasons, but has hygienic interest, since escape of injurious gases is avoided (see also Part III).

The chamber acid (of 110°-120° Tw. = 63-70 %) and the stronger Glover acid (of 136°-144° Tw. = 75-82 %) contain impurities. In order to obtain for certain purposes pure strong acid the chamber acid is purified and concentrated. The impurities are notably arsenious and nitrous acids (Glover acid is N free), lead, copper, and iron. Concentration (apart from that to Glover acid in the Glover tower) is effected by evaporation in lead pans to 140° Tw. and finally in glass balloons or platinum stills to 168° Tw. (= 97 %). The lead pans are generally heated by utilising the waste heat from the furnaces or by steam coils in the acid itself, or even by direct firing.

Production of sulphuric acid by the contact method depends on the fact that a mixture of sulphur dioxide and excess of oxygen (air) combines to form sulphur trioxide at a moderate heat in presence of a contact substance such as platinised asbestos or oxide of iron. The sulphur dioxide must be carefully cleaned and dried, and with the excess of air is passed through the contact substance. If asbestos carrying a small percentage of finely divided platinum is the contact substance, it is generally used in the form of pipes; oxide of iron (the residue of pyrites), if used, is charged into a furnace. Cooling by a coil of pipes and condensation in washing towers supplied with concentrated sulphuric acid always forms a part of the process. A fan draws the gases from the roasting furnaces and drives them through the system. The end product is a fuming sulphuric acid containing 20-30 per cent. SO₃. From this by distillation a concentrated acid and a pure anhydride are obtained. From a health point of view it is of importance to know that all sulphuric acid derived from this anhydride is pure and free from arsenic.

The most important uses of sulphuric acid are the following: as chamber acid (110°-120° Tw.) in the superphosphate, ammonium sulphate, and alum industries; as Glover acid (140°-150° Tw.) in the Leblanc process, i.e. saltcake and manufacture of hydrochloric acid, and to etch metals; as sulphuric acid of 168° Tw. in colour and explosives manufacture (nitric acid, nitro-benzene, nitro-glycerine, gun-cotton, &c.); as concentrated sulphuric acid and anhydride for the production of organic sulphonic acids (for the alizarin and naphthol industry) and in the refining of petroleum and other oils. Completely de-arsenicated sulphuric acid is used in making starch, sugar, pharmaceutical preparations, and in electrical accumulator manufacture.

Effects on Health.—The health of sulphuric acid workers cannot in general be described as unfavourable.

In comparison with chemical workers they have, it is said, relatively the lowest morbidity. Although in this industrial occupation no special factors are at work which injure in general the health of the workers, there is a characteristic effect, without doubt due to the occupation—namely, disease of the respiratory organs. Leymann’s figures are sufficiently large to show that the number of cases of diseases of the respiratory organs is decidedly greater in the sulphuric acid industry than among other chemical workers. He attributes this to the irritating and corrosive effect of sulphur dioxide and sulphuric acid vapour on the mucous membrane of the respiratory tract, as inhalation of these gases can never be quite avoided, because the draught in the furnace and chamber system varies, and the working is not always uniform. Strongly irritating vapours escape again in making a high percentage acid in platinum vessels, which in consequence are difficult to keep air-tight. Of greater importance than these injurious effects from frequent inhalation of small quantities of acid vapours, or employment in workrooms in which the air is slightly charged with acid, is the accidental sudden inhalation of large quantities of acid gases, which may arise in the manufacture, especially by careless attendance. Formerly this was common in charging the roasting furnaces when the draught in the furnace, on addition of the pyrites, was not strengthened at the same time. This can be easily avoided by artificial regulation of the draught.

Accidents through inhalation of acid gases occur further when entering the lead chambers or acid tanks, and in emptying the towers. Heinzerling relates several cases taken from factory inspectors’ reports. Thus, in a sulphuric acid factory the deposit (lead oxysulphate) which had collected on the floor of a chamber was being removed: to effect this the lead chambers were opened at the side. Two of the workers, who had probably been exposed too long to the acid vapours evolved in stirring up the deposit, died a short time after they had finished the work. A similar fatality occurred in cleaning out a nitro-sulphuric acid tank, the required neutralisation of the acid by lime before entering having been omitted. Of the two workers who entered, one died the next day; the other remained unaffected. The deceased had, as the post mortem showed, already suffered previously from pleurisy. A fatality from breathing nitrous fumes is described fully in the report of the Union of Chemical Industry for the year 1905. The worker was engaged with two others in fixing a fan to a lead chamber; the workers omitted to wait for the arrival of the foreman who was to have supervised the operation. Although the men used moist sponges as respirators, one of them inhaled nitrous fumes escaping from the chamber in such quantity that he died the following day.

Similar accidents have occurred in cleaning out the Gay-Lussac towers. Such poisonings have repeatedly occurred in Germany. Fatal poisoning is recorded in the report of the Union of Chemical Industry, in the emptying and cleaning of a Gay-Lussac tower despite careful precautions. The tower, filled with coke, had been previously well washed with water, and during the operation of emptying, air had been constantly blown through by means of a Körting’s injector. The affected worker had been in the tower about an hour; two hours later symptoms of poisoning set in which proved fatal in an hour despite immediate medical attention. As such accidents kept on recurring, the Union of Chemical Industry drew up special precautions to be adopted in the emptying of these towers, which are printed in Part III.

Naturally, in all these cases it is difficult to say exactly which of the acid gases arising in the production of sulphuric acid was responsible for the poisoning. In the fatal cases cited, probably nitrous fumes played the more important part.

Poisoning has occurred in the transport of sulphuric acid. In some of the cases, at all events, gaseous impurities, especially arseniuretted hydrogen, were present.

Thus, in the reports of the German Union of Chemical Industry for the year 1901, a worker succumbed through inhalation of poisonous gases in cleaning out a tank waggon for the transport of sulphuric acid. The tank was cleaned of the adhering mud, as had been the custom for years, by a man who climbed into it. No injurious effects had been noted previously at the work, and no further precautions were taken than that one worker relieved another at short intervals, and the work was carried on under supervision. On the occasion in question, however, there was an unusually large quantity of deposit, although the quality of the sulphuric acid was the same, and work had to be continued longer. The worker who remained longest in the tank became ill on his way home and died in hospital the following day; the other workers were only slightly affected. The sulphuric acid used by the firm in question immediately before the accident came from a newly built factory in which anhydrous sulphuric acid had been prepared by a special process. The acid was Glover acid, and it is possible that selenium and arsenic compounds were present in the residues. Arseniuretted hydrogen might have been generated in digging up the mud. Two similar fatalities are described in the report of the same Union for the year 1905. They happened similarly in cleaning out a sulphuric acid tank waggon, and in them the arsenic in the acid was the cause. Preliminary swilling out with water diluted the remainder of the sulphuric acid, but, nevertheless, it acted on the iron of the container. Generation of hydrogen gas is the condition for the reduction of the arsenious acid present in sulphuric acid with formation of arseniuretted hydrogen. In portions of the viscera arsenic was found. Lately in the annual reports of the Union of Chemical Industry for 1908 several cases of poisoning are described which were caused by sulphuric acid. A worker took a sample out of a vessel of sulphuric acid containing sulphuretted hydrogen gas. Instead of using the prescribed cock, he opened the man-hole and put his head inside, inhaling concentrated sulphuretted hydrogen gas. He became immediately unconscious and died. Through ignorance no use was made of the oxygen apparatus.

Another fatality occurred through a foreman directing some workers, contrary to the regulations against accidents from nitrous gases, to clean a vessel containing nitric and sulphuric acids. They wore no air helmets: one died shortly after from inhalation of nitrous fumes. Under certain circumstances even the breaking of carboys filled with sulphuric acid may give rise to severe poisoning through inhalation of acid gases. Thus a fatality[1] occurred to the occupier of a workroom next some premises in which sulphuric acid carboys had been accidentally broken. Severe symptoms developed the same night, and he succumbed the next morning in spite of treatment with oxygen. A worker in the factory became seriously ill but recovered.

A similar case is described[2] in a factory where concentrated sulphuric acid had been spilt. The workers covered the spot with shavings, which resulted in strong development of sulphur dioxide, leading to unconsciousness in one worker.

The frequent observation of the injurious effect of acid gases on the teeth of workers requires mention; inflammation of the eyes of workers also is attributed to the effects of sulphuric acid.

Leymann’s statistics show corrosions and burns among sulphuric acid workers to be more than five times that among other classes. Such burns happen most frequently from carelessness. Thus, in the reports of the Union of Chemical Industry for 1901, three severe accidents are mentioned which occurred from use of compressed air. In two cases the acid had been introduced before the compressed air had been turned off; in the third the worker let the compressed air into the vessel and forgot to turn off the inlet valve. Although the valves were provided with lead guards, some of the acid squirted into the worker’s face. In one case complete blindness followed, in a second blindness in one eye, and in the third blindness in one eye and impaired vision of the other.

Besides these dangers from the raw material, bye-products, and products of the manufacture, lead poisoning has been reported in the erection and repair of lead chambers. The lead burners generally use a hydrogen flame; the necessary hydrogen is usually made from zinc and sulphuric acid and is led to the iron by a tube. If the zinc and sulphuric acid contain arsenic, the very dangerous arseniuretted hydrogen is formed, which escapes through leakages in the piping, or is burnt in the flame to arsenious acid.

Further, the lead burners and plumbers are exposed to the danger of chronic lead poisoning from insufficient observance of the personal precautionary measures necessary to guard against it (see Part III). Those who are constantly engaged in burning the lead sheets and pipes of the chambers suffer not infrequently from severe symptoms. Unfortunately, the work requires skill and experience, and hence alternation of employment is hardly possible.

Finally, mention should be made of poisoning by arseniuretted hydrogen gas from vessels filled with sulphuric acid containing arsenic as an impurity, and by sulphuretted hydrogen gas in purifying the acid itself. In the manufacture of liquid sulphur dioxide, injury to health can arise from inhalation of the acid escaping from the apparatus. The most frequent cause for such escape of sulphur dioxide is erosion of the walls of the compressor pumps and of the transport vessels, in consequence of the gas being insufficiently dried, as, when moist, it attacks iron.

Sulphur dioxide will come up for further consideration when describing the industrial processes giving rise to it, or in which it is used.

HYDROCHLORIC ACID, SALTCAKE, AND SODA

Manufacture.—The production of hydrochloric acid (HCl), sodium sulphate (Na₂SO₄), and sodium sulphide (Na₂S) forms part of the manufacture of soda (Na₂CO₃) by the Leblanc process. The products first named increase in importance, while the Leblanc soda process is being replaced more and more by the manufacture of soda by the Solvay ammonia process, so much so that on the Continent the latter method predominates and only in England does the Leblanc process hold its ground.

Health interests have exercised an important bearing on the development of the industries in question. At first, in the Leblanc process the hydrochloric acid gas was allowed to escape into the atmosphere, being regarded as a useless bye-product. Its destructive action on plant life and the inconvenience caused to the neighbourhood, in spite of erection of high chimneys, demanded intervention. In England the evils led to the enactment of the Alkali Acts—the oldest classical legislative measures bearing on factory hygiene—by which the Leblanc factories were required to condense the vapour by means of its absorption in water, and this solution of the acid is now a highly valued product. And, again, production of nuisance—inconvenience to the neighbourhood through the soda waste—was the main cause of ousting one of the oldest and most generally used methods of chemical industrial production. Although every effort was made to overcome the difficulties, the old classical Leblanc process is gradually but surely yielding place to the modern Solvay process, which has no drawback on grounds of health.

We outline next the main features of the Leblanc soda process, which includes, as has been mentioned, also the manufacture of hydrochloric acid, sodium sulphate and sulphide.

The first part of the process consists in the production of the sulphate from salt and sulphuric acid, during which hydrochloric acid is formed; this is carried out in two stages represented in the following formulæ:

• 1. NaCl + H₂SO₄ = NaHSO₄ + HCl.
• 2. NaCl + NaHSO₄ = Na₂SO₄ + HCl.

The first stage in which bisulphate is produced is carried out at a moderate heat, the second requires a red heat. The reactions, therefore, are made in a furnace combining a pan and muffle furnace.

This saltcake muffle furnace is so arranged that the pan can be shut off from the muffle by a sliding-door (D). The pan (A) and muffle (E) have separate flues for carrying off the hydrochloric acid developed (B, F). First, common salt is treated with sulphuric (Glover) acid in the cast-iron pan. When generation of hydrochloric acid vapour has ceased, the sliding-door is raised and the partly decomposed mixture is pushed through into the muffle, constructed of fire-resisting bricks and tiles, and surrounded by the fire gases. While the muffle is being raised to red heat, the sulphate must be repeatedly stirred with a rake in order, finally, while still hot and giving off acid vapour, to be drawn out at the working doors into iron boxes provided with doors, where the material cools. The acid vapour given off when cooling is drawn through the top of the box into the furnace.

Fig. 3.—Saltcake Muffle Furnace—Section (after Ost)

A Pan; B, F Pipes for hydrochloric acid vapour; D Shutter; E Muffle, O Coke fire.

Mechanical stirrers, despite their advantage from a health point of view, have not answered because of their short life.

The valuable bye-product of the sulphate process, hydrochloric acid, is led away separately from the pan and the muffle, as is seen, into one absorption system. The reason of the separation is that the gas from the pan is always the more concentrated. The arrangement of the absorbing apparatus is illustrated in [fig. 4].

Fig. 4a.—Preparation of Hydrochloric Acid—Plan (after Lueger)

• A, A´ Earthenware pipes
• B, B´ Sandstone cooling towers
• C, C Series of Woulff’s bottles
• D, E Condenser wash towers

Fig. 4b.—Elevation

The gases are led each through earthenware pipes or channels of stone pickled with tar (A´), first into small towers of Yorkshire flags (B), where they are cooled and freed from flue dust and impurities (sulphuric acid) by washing. They are next led through a series (over fifty) of Woulff bottles (bombonnes) one metre high, made of acid-resisting stoneware. The series is laid with a slight inclination towards the furnace, and water trickles through so that the gases coming from the wash towers are brought into contact with water in the one case already almost saturated, whilst the gas which is poorest in hydrochloric acid meets with fresh water. From the bombonne situated next to the wash tower the prepared acid is passed as a rule through another series. The last traces of hydrochloric acid are then removed by leading the gases from the Woulff bottles up two water towers of stoneware (D and E), which are filled partly with earthenware trays and partly with coke; above are tanks from which the water trickles down over the coke. The residual gases from both sets of absorbing apparatus now unite in a large Woulff bottle before finally being led away through a duct to the chimney stack.

Less frequently absorption of hydrochloric acid is effected without use of Woulff bottles, principally in wash towers such as the Lunge-Rohrmann plate tower.

In the purification of hydrochloric acid, de-arsenicating by sulphuretted hydrogen or by barium sulphide, &c., and separation of sulphuric acid by addition of barium chloride, have to be considered.

Another method for production of sulphate and hydrochloric acid, namely, the Hargreaves process, is referred to later.

We return now to the further working up of the sodium sulphate into sulphide and soda. The conversion of the sulphate into soda by the Leblanc method is effected by heating with coal and calcium carbonate, whereby, through the action of the coal, sodium sulphide forms first, which next with the calcium carbonate becomes converted into sodium carbonate and calcium sulphide.

The reactions are:

• Na₂SO₄ + 2C = Na₂S + 2CO₂
• Na₂S + CaCO₃ = Na₂CO₃ + CaS
• CaCO₃ + C = CaO + 2CO.

The reactions are carried out in small works in open reverberatory furnaces having two platforms on the hearth, and with continuous raking from one to the other which, as the equations show, cause escape of carbonic acid gas and carbonic oxide.

Such handworked furnaces, apart from their drawbacks on health grounds, have only a small capacity, and in large works their place is taken by revolving furnaces—closed, movable cylindrical furnaces—in which handwork is replaced by the mechanical revolution of the furnace and from which a considerably larger output and a product throughout good in quality are obtained.

The raw soda thus obtained in the black ash furnace is subjected to lixiviation by water in iron tanks in which the impurities or tank waste (see below) are deposited. The crude soda liquor so obtained is then further treated and converted into calcined soda, crystal soda, or caustic soda. In the production of calcined soda the crude soda liquor is first purified (‘oxidised’ and ‘carbonised’) by blowing through air and carbonic acid gas, pressed through a filter press, and crystallised by evaporation in pans and calcined, i.e. deprived of water by heat.

Fig. 5.—Revolving Black Ash Furnace—Elevation (after Lueger)

A Firing hearth; B Furnace; C Dust box.

Crystal soda is obtained from well-purified tank liquor by crystallising in cast-iron vessels.

Caustic soda is obtained by introducing lime suspended in iron cages into the soda liquor in iron caustic pots, heating with steam, and agitating by blowing in air.

The resulting clear solution is drawn off and evaporated in cast-iron pans.

As already mentioned, the tank waste in the Leblanc process, which remains behind—in amount about equal to the soda produced after lixiviation of the raw soda with water—constitutes a great nuisance. It forms mountains round the factories, and as it consists principally of calcium sulphide and calcium carbonate, it easily weathers under the influence of air and rain, forming soluble sulphur compounds and developing sulphuretted hydrogen gas—an intolerable source of annoyance to the district.

At the same time all the sulphur introduced into the industry as sulphuric acid is lost in the tank waste. This loss of valuable material and the nuisance created led to attempts—partially successful—to recover the sulphur.

The best results are obtained by the Chance-Claus method, in which the firebrick ‘Claus-kiln’ containing ferric oxide (previously heated to dull redness) is used. In this process calcium sulphide is acted on by carbonic acid with evolution of gas so rich in sulphuretted hydrogen that it can be burnt to sulphur dioxide and used in the lead chambers for making sulphuric acid. Sulphur also as such is obtained by the method.

These sulphur-recovery processes which have hardly been tried on the Continent—only the United Alkali Company in England employs the Chance-Claus on a large scale—were, as has been said, not in a position to prevent the downfall of the Leblanc soda industry. Before describing briefly the Solvay method a word is needed as to other processes for manufacture of sulphate and hydrochloric acid.

Hargreaves’ process produces sodium sulphate (without previous conversion of sulphur dioxide into sulphuric acid) directly by the passage of gases from the pyrites burners, air and steam, through salt blocks placed in vertical cast-iron retorts, a number of which are connected in series. A fan draws the gases through the system and leads the hydrochloric acid fumes to the condenser.

Sodium sulphate is used in the manufacture of glass, ultramarine, &c. Further, the sulphate is converted into Glauber’s salts by dissolving the anhydrous sulphate obtained in the muffle furnace, purifying with lime, and allowing the clear salt solution to crystallise out in pans.

A further use of the sulphate is the preparation of sodium sulphide, which is effected (as in the first part of the Leblanc soda process) by melting together sulphate and coal in a reverberatory furnace. If the acid sulphate (bisulphate) or sulphate containing bisulphate is used much sulphur dioxide gas comes off.

The mass is then lixiviated in the usual soda liquor vats and the lye either treated so as to obtain crystals or evaporated to strong sodium sulphide which is poured like caustic soda into metal drums where it solidifies.

In Solvay’s ammonia soda process ammonia recovered from the waste produced in the industry is led into a solution of salt until saturation is complete. This is effected generally in column apparatus such as is used in distillation of spirit. The solution is then driven automatically by compressed air to the carbonising apparatus in which the solution is saturated with carbonic acid; this apparatus is a cylindrical tower somewhat similar to the series of vessels used for saturating purposes in sugar factories through which carbonic acid gas passes. In this process crystalline bi-carbonate of soda is first formed, which is separated from the ammoniacal mother liquor by filtration, centrifugalisation, and washing. The carbonate is then obtained by heating (calcining in pans), during which carbonic acid gas escapes, and this, together with the carbonic acid produced in the lime kilns, is utilised for further carbonisation again. The lime formed during the production of carbonic acid in the lime kilns serves to drive the ammonia out of the ammoniacal mother liquor, so that the ammonia necessary for the process is recovered and used over and over again. The waste which results from the action of the lime on the ammonium chloride liquor is harmless—calcium chloride liquor.

The electrolytic manufacture of soda from salt requires mention, in which chlorine (at the anode) and caustic soda (at the cathode) are formed; the latter is treated with carbonic acid to make soda.

Effects on Health.—Leymann’s observations show that in the department concerned with the Leblanc soda process and production of sodium sulphide, relatively more sickness is noted than, for example, in the manufacture of sulphuric and nitric acids.

In the preparation of the sulphate, possibility of injury to health or poisoning arises from the fumes containing hydrochloric or sulphuric acid in operations at the muffle furnace; in Hargreaves’ process there may be exposure to the effect of sulphur dioxide. Hydrochloric and sulphuric acid vapours can escape from the muffle furnace when charging, from leakages in it, and especially when withdrawing the still hot sulphate. Large quantities of acid vapours escape from the glowing mass, especially if coal is not added freely and if it is not strongly calcined. Persons employed at the saltcake furnaces suffer, according to Jurisch, apart from injury to the lungs, from defective teeth. The teeth of English workers especially, it is said, from the practice of holding flannel in their mouths with the idea of protecting themselves from the effect of the vapours, are almost entirely eroded by the action of the hydrochloric acid absorbed by the saliva. Hydrochloric acid vapour, further, can escape from the absorbing apparatus if this is not kept entirely sealed, and the hydrochloric acid altogether absorbed—a difficult matter. Nevertheless, definite acute industrial poisoning from gaseous hydrochloric acid is rare, no doubt because the workers do not inhale it in concentrated form.

Injury to the skin from the acid absorbed in water may occur in filling, unloading, and transport, especially when in carboys, but the burns, if immediately washed, are very slight in comparison with those from sulphuric or nitric acids. Injury to health or inconvenience from sulphuretted hydrogen is at all events possible in the de-arsenicating process by means of sulphuretted hydrogen gas. At the saltcake furnace when worked by hand the fumes containing carbonic oxide gas may be troublesome. In the production of caustic soda severe corrosive action on the skin is frequent. Leymann found that 13·8 per cent. of the persons employed in the caustic soda department were reported as suffering from burns, and calls attention to the fact that on introducing the lime into the hot soda lye the contents of the vessel may easily froth over. Heinzerling refers to the not infrequent occurrence of eye injuries in the preparation of caustic soda, due to the spurting of lye or of solid particles of caustic soda.

The tank waste gives rise, as already stated, to inconvenience from the presence of sulphuretted hydrogen. In the recovery of the sulphur and treatment of the tank waste, sulphuretted hydrogen and sulphur dioxide gases are evolved. According to Leymann, workers employed in removing the waste and at the lye vats frequently suffer from inflammation of the eyes. Further, disturbance of digestion has been noted in persons treating the tank waste, which Leymann attributes to the unavoidable development of sulphuretted hydrogen gas.

In the manufacture of sodium sulphide similar conditions prevail. Leymann found in this branch relatively more cases of sickness than in any other; diseases of the digestive tract especially appeared to be more numerous. Leymann makes the suggestion that occurrence of disease of the digestive organs is either favoured by sodium sulphide when swallowed as dust, or that here again sulphuretted hydrogen gas plays a part. Further corrosive effect on the skin and burns may easily arise at work with the hot corrosive liquor.

In the Solvay ammonia process ammonia and carbonic acid gas are present, but, so far as I know, neither injury to health nor poisoning have been described among persons employed in the process. Indeed, the view is unanimous that this method of manufacture with its technical advantages has the merit also of being quite harmless. As may be seen from the preceding description of the process there is no chance of the escape of the gases named into the workrooms.

USE OF SULPHATE AND SULPHIDE

Ultramarine is made from a mixture of clay, sulphate (Glauber’s salts), and carbon—sulphate ultramarine; or clay, sulphur, and soda—soda ultramarine. These materials are crushed, ground, and burnt in muffle furnaces. On heating the mass in the furnace much sulphur dioxide escapes, which is a source of detriment to the workmen and the neighbourhood.

Sulphonal (CH₃)₂C(SO₂C₂H₅)₂, diethylsulphone dimethylmethane, used medically as a hypnotic, is obtained from mercaptan formed by distillation of ethyl sulphuric acid with sodium or potassium sulphide. The mercaptan is converted into mercaptol, and this by oxidation with potassium permanganate into sulphonal. The volatile mercaptan has a most disgusting odour, and clings for a long time even to the clothes of those merely passing through the room.

Diethyl sulphate ((C₂H₅)₂SO₄).—Diethyl sulphate obtained by the action of sulphuric acid on alcohol has led to poisoning characterised by corrosive action on the respiratory tract.[1] As the substance in the presence of water splits up into sulphuric acid and alcohol, this corrosive action is probably due to the acid. It is possible, however, that the molecule of diethyl sulphate as such has corrosive action.

Contact with diethyl sulphate is described as having led to fatal poisoning.[2]

A chemist when conducting a laboratory experiment dropped a glass flask containing about 40 c.c. of diethyl sulphate, thereby spilling some over his clothes. He went on working, and noticed burns after some time, quickly followed by hoarseness and pain in the throat. He died of severe inflammation of the lungs. A worker in another factory was dropping diethyl sulphate and stirring it into an at first solid, and later semi-liquid, mass for the purpose of ethylating a dye stuff. In doing so he was exposed to fumes, and at the end of the work complained of hoarseness and smarting of the eyes. He died of double pneumonia two days later. Post mortem very severe corrosive action on the respiratory tract was found, showing that the diethyl sulphuric acid had decomposed inside the body and that nascent sulphuric acid had given rise to the severe burns. The principal chemist who had superintended the process suffered severely from hoarseness at night, but no serious consequences followed.

It is stated also that workmen in chemical factories coming into contact with the fumes of diethyl sulphate ester suffer from eye affections.[3]

CHLORINE, CHLORIDE OF CALCIUM, AND CHLORATES

Manufacture.—The older processes depend on the preparation of chlorine and hydrochloric acid by an oxidation process in which the oxidising agent is either a compound rich in oxygen—usually common manganese dioxide (pyrolusite)—or the oxygen of the air in the presence of heated copper chloride (as catalytic agent). The former (Weldon process) is less used now than either the latter (Deacon process) or the electrolytic manufacture of chlorine.

In the Weldon process from the still liquors containing manganous chloride the manganese peroxide is regenerated, and this so regenerated Weldon mud, when mixed with fresh manganese dioxide, is used to initiate the process. This is carried out according to the equations:

• MnO₂ + 4HCl = MnCl₄ + 2H₂O
• MnCl₄ = MnCl₂ + Cl₂.

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:

• 2HCl + O = 2Cl + H₂O.

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:

• 2Ca(OH)₂ + 4Cl = Ca(ClO)₂ + CaCl₂ + 2H₂O.

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.

Leymann[2] 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.

Lehmann[3] 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.

OTHER CHLORINE COMPOUNDS. BROMINE, IODINE, AND FLUORINE

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]

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.

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 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.