The Case of the Poisonous Socks

Tales from Chemistry

William H Brock

• Publisher: Royal Society of Chemistry
• Year: 2015
• ISBN:
  9781782625353
• Edition: 1
• Topic: History
• Subtopic: Science History
• Index: History

In 1868, The Times reported that poisons contained in dyes were affecting the public's health. A doctor informed a London magistrate that brilliantly coloured socks had caused severe "constitutional and local complaint" to several of his patients. In one case, a patient's foot had become so swollen that his boots had to be cut off. Respected chemist, William Crookes, offered to identify the poison if doctors would send him samples of the deadly socks. The story of how he solved the mystery gives this book its title and forms the basis of the first chapter. Written by a respected science historian and established author, this collection of essays contains 42 tales of chemists and their discoveries from the nineteenth and twentieth centuries. Other topics covered include: the quirky beliefs of American philanthropist, George Hodgkins; the development of the chemical laboratory since the 1830s, and the career of C.P. Snow before he became a novelist. Its broad coverage and modern approach makes it of interest to chemists, teachers, historians and laypeople with an interest in science. Written with a light style and presented in a series of unconnected vignettes the book is easy to dip into at leisure.

Part 1: Chemical Futures

Following previous years in which the work of astronomers and physicists had been celebrated, the United Nations designated 2011 as the International Year of Chemistry (IYC). During the year the achievements of chemists and chemistry’s contributions to the well-being of human society were celebrated all over the world. The principal theme chosen for highlight was “chemistry: our life, our future”, and this theme provides the underlying thread for the seven varied stories that make up the first section of this book. They bear testimony to the promise—first adumbrated by the alchemists—that chemistry is the science that can deliver a brighter and better future for mankind. On the way, however, there can be stumbling blocks and risks which chemists and society itself have to monitor and negotiate. William Crookes, who appears in the first story as a detective searching for the cause of skin irritation caused by the recent introduction of vividly-hued synthetic dyestuffs into the hosiery industry, was a journalist as well as a productive research chemist. He repeatedly used his weekly journal Chemical News to publicise and extol the fact that chemistry was improving the human condition. This optimism for a future enriched by chemists culminated shortly after his death in 1919 with Du Pont’s catching advertising slogan, “Better Things for Better Living Through Chemistry”. This slogan had been no better demonstrated than by Crookes’s teacher, the Anglo-German chemist August Wilhelm Hofmann, the subject of the third essay. His transformation of coal tar waste products into beautiful colours exemplifies all that is wonderful and powerful about chemistry.

Although Crookes’s predecessor, the London medical chemist William Prout, was more interested in the theoretical basis of our chemical senses, he too looked forward to a time when chemists would understand the principles of nutrition sufficiently to prepare foodstuffs that would transform what and how we eat and drink—as the research of the Japanese chemist Ikeda was to show. Indeed, in later studies, it was Prout who proposed the division of foodstuffs into carbohydrates, fats and proteins, and who developed one of the first biochemical models of the digestive process. The close connection between the chemistry of food and commerce is highlighted in the example of the great nineteenth-century organic chemist, Justus von Liebig, whose work in applied chemistry helped create the modern convenience food industry.

Using chemistry to create a better future is dependent on the funding of fundamental, as well as, applied research. We usually think of such research as being provided by the state, or by industrial or pharmaceutical companies. But as the curious story of George Hodgkins’s bequests to the Royal Institution and the Smithsonian Institution in the 1890s reveals, private philanthropy has also had a significant, and sometimes unexpected, role to play. As the individual sciences emerged in their modern form in the nineteenth century, it was inevitable that chemists should have pondered what the future held for their science in the next century and what particular field of chemistry—inorganic, organic or physical—would prove of most value educationally and for research. Although the general view in 1900–1901 was that physical chemistry was the front runner (as turned out to be the case), spokesmen also emphasized the role that history should play in the future education of chemists and the practice of chemistry. This rather surprising conclusion was also underlined in the first part of the twentieth century by the increasing interest in the history of alchemy among both scientists and laymen as the new physics and chemistry of radioactivity revealed the deep structure of the atom. The formation in 1912 of an Alchemical Society, which was treated by Nature like any other bona fide scientific society, forms the final essay in this section. In the chemistry of the future, chemists were to hand over the atomic nucleus to physicists while retaining the electron as their particular province for enhancing and transforming human lives and futures.

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).

Figure 1.1 Sir William Crookes (1832–1919) portrayed in a Vanity Fair cartoon at the height of his fame in 1905. (Wellcome Images)

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 ...