The Case of the Poisonous Socks: Tales from Chemistry

The Case of the Poisonous Socks: Tales from Chemistry

by William H Brock

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ISBN-13: 9781849733243
Publisher: Royal Society of Chemistry, The
Publication date: 09/12/2011
Pages: 362
Product dimensions: 6.00(w) x 8.90(h) x 1.00(d)

About the Author

William H. Brock is a retired Professor of the History of Science. He read Chemistry at UCL before studying the History of Science at the University of Leicester where he later became a lecturer then a professor. He has published many papers and books including The Fontana History of Chemistry.

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The Case of the Poisonous Socks

Tales from Chemistry


By William H. Brock

The Royal Society of Chemistry

Copyright © 2011 William H. Brock
All rights reserved.
ISBN: 978-1-84973-324-3



CHAPTER 1

The Case of the Poisonous Socks


On 30 September 1868 The Times published a police report that poisons contained in dyes were affecting the public's health. A certain Dr Webber had complained to a City of London magistrate that brilliantly coloured socks which were being sold locally had caused severe "constitutional and local complaint" to several of his patients. In one case, a patient's foot had become so swollen after wearing such socks that his boots had had to be cut off. Since Webber did not know the nature of the poison, he had been unable to recommend an antidote, though he found the application of glycerine gave relief. Red and light brown socks striped transversely with bright orange and bordered in violet and black were shown to the magistrate. It seemed that it was the orange dye that caused the intense irritation. Webber had made some investigations and found that the orange dye was made from a new acid and that the dye workers were unable to work on the substance for more than six months at a time and that when they "retired" their arms were covered with sores. Webber had complained to the sock maker, who immediately stopped an export order for 6,000 pairs of socks, and returned to using "old wood dyes".

As this reference to natural dyestuffs reminds us, there was nothing new about coloured socks and stockings. Naturally dyed silk or worsted hose had been available to the wealthy since the seventeenth century, while white, grey and black stocking and hose were worn by the majority. Embroidered and coloured "clock goves" (the triangular piece let into the ankle of a sock or stocking) were bought by fashionable gentile society throughout the eighteenth century. Blue dye, produced by using imported indigo bulked out with native woad, was used in the stockings made fashionable by members of the Society of Literati. It was for that reason that satirists described its female members as "blue stockings". By the mid-1850s, dynastic hosiers such as John Morley and Nathaniel Corah seized on the opportunities presented by the new colourful dyes synthesized from aniline to produce the hosiery that Webber complained about.

The magistrate revealed that he was partial to coloured socks himself and had suffered no harm from wearing them. Although urged not to alarm the public unnecessarily, Webber proceeded to reveal that purchasers of the socks in Oxford and Cambridge were also complaining of skin sores. The trouble had even spread to Paris, where English hosiery was on sale. The Lancet, in taking up the story, recalled that the previous year a dancer at the Drury Lane Theatre had bought a "gorgeous" pair of socks and ended up in hospital with unpleasant eruptions. The medical journal rightly deduced that the poisoning had something to do with hot sweaty feet causing a chemical reaction with an unknown dyestuff. Obviously, beneath their drab black trousers and skirts, Victorian gentlemen and gentlewomen were secretly cross-gartered Malvolios of fashion!

A few days later, a knowledgeable Coventry physician named McVeigh reported cases of severe eczema (resembling erysipelas) he had seen in the Midlands and blamed aniline dyes retailed as "Marquis of Hastings" colours. The usual symptoms were itchy, swollen, painful, red-hot and blistered feet which also discharged. McVeigh had consulted a recently translated German treatise by Max Reimann, On Aniline and its Derivatives. A Treatise upon the Manufacture of Aniline and its Colors (1868), from which he deduced that picric acid was the culprit. This was the cue for the translator of Reimann's book to take up the correspondence. This was none other than the 36-year old chemist, William Crookes who, despite achieving a Fellowship of the Royal Society and an international reputation for the discovery of thallium in 1861, was still struggling to establish a career as chemical consultant and independent researcher. By 1868 he was engaged in a mixture of activities ranging from a long project to determine the atomic weight of thallium with great accuracy, the exploitation of patents for using sodium amalgam in silver and gold mining and a carbolic disinfectant, as well as literary activities that ranged from editing the weekly Chemical News and the Quarterly Journal of Science to making translations of German technical works. As Reimann's translator, he seized upon the controversy to demonstrate his expertise to readers of the Times (Figure 1.1).

Crookes argued that picric acid (aniline yellow), which had been used by synthetic dyers of silk and wool for over twenty years, was harmless even if the workmen who made it had skins "as yellow as guineas, and their hair of a beautiful green". The present problem, he suggested, might stem from the fact that manufacturers had recently taken to saturating picric acid with alkali before use. Consequently, if the wool was imperfectly washed, alkali would cause the irritation. If this were the explanation, he warned, manufacturers were in danger of blowing themselves up since alkaline picric acid was as explosive as nitroglycerine. One such factory had already been destroyed with the loss of life. In mock heroic fashion he said the sock wearers might vary the excitement of poisoning by exploding their toes instead! More seriously, he doubted that picric acid was really the culprit. Rather, it was probably the "Victoria Orange" and "Manchester Yellow" (dinitroparacresol, or 2,4-dinitro-1-naphthol discovered by Carl Martius in 1864) that had been rapidly developed commercially for rendering silk and wool a golden yellow, and the dinitroaniline, chloroxynaphthalic acid and nitrophenylenediamine used in making brilliant reds. Their "chromatic brilliancy" bore "no relation to the euphony of their names". He then offered to identify the poison if Webber and McVeigh would send him samples of the deadly socks.

Other Times readers poured out their troubles over coloured hosiery, leading "Barefoot of Taunton" to suggest that abandoning socks and stockings, as he had done, was the obvious remedy. Another English doctor practising in Le Havre then reported that he had warned about coloured socks the year before but his warning had been turned down for publication by The Lancet. The new feature of his precise observation was, that in the case he had seen, the weeping stripes on his patient's foot corresponded exactly to where the transverse stripes of red colouring were in the socks. The offending socks had been taken to the French government's laboratory at Rouen where they were professionally analysed. From analyst Bidard's report we learn that the coloured bands were in fact made of dyed silk that had been sewn into the violet ground of the woollen stocking. The violet of the main sock, which was the "aniline violet" first prepared by August Wilhelm Hofmann at the Royal College of Chemistry in London, was absolutely harmless, while the silk was dyed with fuchsine (aniline red). It was the latter that was causing the problem. Fuchsine had, in fact, been used in the dyeing trade for a good ten years, but hitherto had only been used in external clothing that did not particularly come into contact with the wearer's skin. In socks, however, the fuchsine was brought into close skin contact by shoe pressure. The French laboratory reported that because fuchsine was soluble in weak acids, it would therefore react with perspiration. The case of the poisoned socks seemed closed — it was due to fuchsine and sweaty feet.

The French intervention must have taken the wind out of Crookes's sails. He had offered to analyse the socks only to discover that it had already been done by a foreign government analyst. However, this did not deter Crookes, who completed the case a week later with a humorously written letter on poisonous dyes and a different conclusion. From the letters he had received, Crookes had been surprised how far the taste for gaudy hose had penetrated. There must be several hundred dozen pairs of these "chromatic torpedoes" in the public domain, he noted. Their male and female owners had no need to panic. There was really no reason why "young men and maidens should not continue to indulge in attire as startling and varied a colour as their good taste may permit". Rumours that the irritation was caused by arsenic poisoning were quite untrue. He had been assured by the largest aniline dyes maker in Europe (presumably the Atlas Works of Brooke, Simpson & Spiller in London's East End) that arsenic was no longer used in the manufacture of magenta. He identified the culprit as a new orange dye that was different from all the dyes he had previously dealt with. It was an acidic dye, insoluble in water, but soluble in alkalis. He had been unable to work out its composition and "sesquipedalian nomenclature".

From Crookes's brief description it sounds as if it was an azo-dye rather than fuchsine. On consulting Maurice Fox's wonderful compendium, Dye-Makers of Great Britain, it appears most likely that the offending dye was Field's Orange (also known as Field's Yellow), an amino-azo-benzene hydrochloride that Frederick Field prepared from aniline and developed at the Atlas Works in the 1860s. It is possible that the scare over poisonous socks in 1868 inhibited its use with textiles for, according to Fox, its main use was found in the coloration of varnishes and foodstuffs. Crookes put the risks in perspective. The number of cases of irritation had been few compared to the numbers of socks sold. The dye only affected wearers whose perspiration was alkaline (as opposed to the more normal acidic secretion to which the French had referred). Even so, he recommended that the particular orange dye's use should be restricted to articles of clothing that did not come into contact with the skin. There were plenty of harmless colourful dyestuffs, including phosphine (chrysaniline), aurine, Manchester Yellow, flavine and picric acid. Meanwhile, the hapless owners of poisonous socks should not throw them away. When washed with soap and soda they would "lose their stimulating action, both on the feet and on the optic nerve".

It was another twenty years before striped socks were made safe for sensitive skins when hosiery firms like Morley developed an oxidizing process that stabilised synthetic dyes. Widely advertised as "sanitary" or "hygienic dyes", hosiers were, at last, able to guarantee their coloured socks were stainless and proof against human perspiration.

Interestingly, a century later a closely related azo-dyestuff became implicated in another health scare. This was tartrazine, which had become widely used in the food industry as a colouring agent since its synthesis by Ziegler in 1884. Following the formation of the European Union in the 1950s, food additives that had passed stringent safety tests were identified by an E(urope) number. Tartrazine, for example, became identified on labels as E102. Synthetic colorants appealed to the food industry because they were cheaper than natural dyes, more stable, and usually more dramatic in their visual appeal. However, by the early 1960s there were a growing number of reports from parents who had noticed dramatic mood swings after their children had consumed brightly coloured sweets, cakes and soft drinks. A medical report published in 1975 identified colouring agents used in foodstuffs, as well as stabilising agents such as sodium benzoate, as a cause of hyperactivity and attention deficit in school children. It was not, however, until 2009 that the UK Food Standards Agency moved to ban such colorants from foodstuffs. Despite this recommendation, the European Food Safety Authority has remained adamant that E-number additives are safe. Nevertheless, most responsible food manufacturers have voluntarily removed substances like tartrazine from the food chain.

CHAPTER 2

Taste, Smell and Flavour


An essay written by William Prout (1785–1850) when he was a medical student at the University of Edinburgh shows that he was committed to a belief in the unity of matter several years before the publication of the two famous anonymous papers which contained "Prout's hypothesis" suggesting that all of the known elements might really be polymers of hydrogen. The student essay, De facultate sentiendi, a quarto manuscript of 26 pages is in English, despite the Latin title. It is an extraordinary example of the power and pitfall of analogical reasoning that is unguided by experiment. Prout's aim was to argue that sensation, like matter, was basically one thing. The five senses — touch, taste, smell, hearing and vision — were regarded by Prout as the peculiar sensations produced on specialized nervous apparatuses by the contact of a unique matter that was aggregated into the five different physical forms, solid, liquid, gaseous, ethereal and luciform. Tactile feelings, tastes, smells, sounds, and colours, he concluded, were all ultimately dependent "upon the different sizes, &c. of the aggregated particles of the same matter".

Prout's programme to reduce the number of sensations has never been realized, for in searching for analogies between sensations, he missed significant differences and over-emphasized superficial or accidental similarities. The notes on taste, smell and flavour, which closed his essay, are those that have best stood the course of time. Here it is noteworthy that Prout's discussion was based firmly on experience, and that these same notes formed the basis for his first publication in a London medical journal in 1812 (Figure 2.1).

Prout had noticed that taste was commonly confused with flavour, which physiologists believed to be the principle in a sapid substance that excited taste. Instead, he suggested, taste and flavour were physiologically different sensations. "Taste is that modification of sensation which is caused by the contact of certain substance soluble in water or saliva with the tongue, the nostrils being at the same time closed and the tongue not being in contact with any other part of the mouth". In his student essay Prout mentioned for the first time experiments which supported his opinions, in this case a definition of gustation. If substances like nutmeg were placed upon the tongue and the nostrils closed or plugged, then only a slight pungency was experienced. This was in fact the experimental justification for Prout's contention expressed in the main essay that the number of tastes was limited to acid, alkaline, bitter, sweet and "perhaps one or two more". In fact, nineteenth-century physiologists identified four tastes (sweet, sour, bitter and salty) so it is interesting (as we shall see below) that Prout should allow for the possibility of others. Since substances that excited taste usually also excited sensations when placed in contact with the body stripped of its cutis, he concluded incorrectly that all substances which excited taste were stimulants. But this fitted in with his conception that taste was similar to touch, even though it was the most limited and imperfect of all sensations.

What was usually taken for taste, said Prout, was flavour, which was really a combination of taste and smell. People with colds, who lost their sense of smell (anosmia) also lost their sense of "taste", i.e., flavour; and people born without a tongue, or who had accidentally lost the tongue, could legitimately claim to "taste". "Smell", he wrote, "is that modification of compound sensation which is excited by various states of matter either in an aeriform state or in a state of extremely fine mechanical division when these are drawn in the air through the nose". The sensory mechanism of the nose, like the tongue, was chemical or galvanic. Flavour was another modification of sensation produced by the union of taste with smell. "Substances in general have the strongest flavour that are volatizable or partly soluble in air as well as water".

In his published paper Prout gave flavour the definition which has since passed into physiological literature. "Flavour is that sensation which is produced when substances under certain circumstances are introduced into the mouth, the nostrils being at the same time open". Olfaction was independent of gustation, but not of flavour. Olfaction could be influenced by strong flavours, as when vinegar was held in the mouth and masked the odour of ammonia held to the nose. The reverse experiment did not work, Prout explained, because ammonia had little flavour due to its great solubility in water. The seat of flavour was more extensive than that of taste and included the palate, the fauces and rear of the nose, the pharynx and the upper oesophagus.

As previously stated, these notes of taste, smell and flavour were published anonymously by Prout in 1812. Later the distinctions he had drawn were noted by his close friend John Elliotson (a fellow student at Edinburgh) and published in the latter's translation of Blumenbach's Physiology (1815). In this way Prout's analysis passed into the general literature of the physiology of sensation; curiously, however, his name has never been attached to it.


(Continues...)

Excerpted from The Case of the Poisonous Socks by William H. Brock. Copyright © 2011 William H. Brock. Excerpted by permission of The Royal Society of Chemistry.
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Table of Contents

Preface; Part 1: Chemical Futures; 1. The Case of the Poisonous Socks; 2. Taste, Smell and Flavour; 3. Tales of Hofmann; 4. Liebig on Toast; 5. The Future of Research at the Royal Institution (London) and the Smithsonian Institution (Washington); 6. The Future of Chemistry in 1901; 7. The Alchemical Society 1912-1915; Part 2: Organizing Chemistry; 8. Putting the "S" into the "Three R's"; 9. The London Chemical Society; 10. The State of Chemistry in Britain in 1846; 11. The Laboratory Before and After Liebig; 12. The Chemical Origins of Practical Physics; 13. Chemical Algebra; 14. The B Club; 15. Chemistry By Discovery in a Phrase; Part 3: A Cluster of Chemists; 16. Amedeo Avogadro; 17. Creating a Path through the Dark Forest of Organic Chemistry; 18. August Kekulé (1829-96): Theoretical Chemist; 19. The Don Quixote of Chemistry: Sir Benjamin Collins Brodie (1817-1880); 20. The Epistle of Henry the Chemist; 21. He Knew He Was Right - Fritz Haber; 22. J. R. Partington (1886-1965): Physical Chemistry in Deed and Word; 23. Henry Crookes, Founder of Crookes Laboratories; 24. A Life of Magic Chemistry; Part 4: Women in Alchemy and Chemistry; 25. Women in Alchemy; 26. Teaching Chemistry to Women; 27. Musical Affinities; 28. Edith Hilda Usherwood (1898-1988) and the Ingold Partnership; Part 5: Chemical Books and Journal; 29. The Fate of Eponymous Chemical Journals; 30. The Lamp of Learning; 31. "The Greatest Work which England has ever Produced": Henry Watts and the Dictionary of Chemistry; 32. Chemistry in the Aquarium; 33. Insurance Chemistry; 34. Math for Chemists; 35. The Chemistry of Pottery; 36. Baker's Dozen; Part 6: Lost to Chemistry; 37. They Also Ran; 38. Who Was Crookes's Musician-Chemist?; 39. The Chemist from Hanwell Asylum; 40. George Du Maurier (1834-96); 41. Sir Stafford Cripps; 42. C. P. Snow as a Physical Chemist; Sources, Acknowledgements and Further Reading; Index

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