Creating a New Rainbow: Dyes after Perkin

On Thursday 14th February 2008 the Royal Society of Chemistry Historical Group held a joint meeting with the Chilterns and Middlesex Section of the Royal Society of Chemistry to celebrate the award of the 2007 Sidney M. Edelstein Award for Outstanding Achievement in the History of Chemistry to Anthony S. Travis of the Hebrew University, Jerusalem.

The first paper was given by Chris Cooksey and was entitled “Peter Griess – the azo dye chemist.” Although azobenzene was discovered by Mitscherlich in 1834, and related compounds were prepared by Zinin and Hofmann, the potentialities of the class were not realized until Johann Peter Griess (1829-1888) began his work. Griess studied in Jena and Marburg, serving as Kolbe's assistant in Marburg and then as Hofmann's as­sistant at the Royal College of Chemistry in London. He moved on to the position of chemist in the Allsopp and Sons brewery in Burton-on-Trent in 1862 where he remained until his death in 1888. His duties at the brewery allowed him some spare time to pursue his interest in azo compounds. Griess had begun to study the azo com­pounds while still with Kolbe and discovered in 1858 that the reaction of aromatic amines with half an equivalent of nitrous acid gave coloured azo compounds, the forerunners of an historic class of fabric and leather dyes. This diazotization reaction was extended to the coupling with phenols in 1870 and with different amines in 1876. Commercially useful dyes began to emerge, oranges in 1876 derived from sulfanilic acid and reds for cotton from benzidine in 1884. Over the years, Griess published about 140 papers about azo compounds and just one concerned with brewing. While commercial success eluded Griess and by now most, but not all, of the early azo dyes have been consigned to history, he is still remembered in the forensic science field for the Griess test for explosive residues which was extensively used until recently.

J. Sérgio Seixas de Melo from the Department of Chemistry, University of Coimbra spoke on “Indigo and Mauveine: Molecules with Chemistry and History.” Indigo and violet are two colours of the rainbow that are also the colours of two molecules charged with history. Indigo is the oldest source of blue and is believed in many cultures to possess unique talismanic properties. Although initially extracted from Indigofera plants, the chemical synthesis of this fascinating blue dye by Adolf von Bayer in 1878 (started in 1865) is associated with the genesis of the German chemical industry. The synthesis of mauveine in 1856 by W. H. Perkin is a landmark in the history of science and is properly associated with the birth of the chemical dye industry. In spite of the importance of mauveine, recent discoveries of new mauveine structures in historical samples show that this molecule still has mysteries to unveil.

J. Sérgio Seixas de Melo presented a study of the analysis of mauveine samples from different provenances collected by Peter Morris from the collection at the Science Museum, London. In addition to the known Mauveine A, B, B2 and C forms, new structures responsible by the violet colour of mauveine, found in historical samples, were presented. The origins of these were considered based on analysis of the percentage distribution of the different mauveines and the counter-ions present, etc. This work suggests that although one of the samples was marked as a sample of the original mauveine dye manufactured by Perkin it dated instead from 1862. Furthermore, the historical samples contained not two but at least thirteen different compounds

The final paper in the morning session was given by David H. Leaback of Biolink Technology and was entitled “Pioneering Post-Mauveine Synthetic Dyestuffs from Newington & Hackney Wick.” David Leaback outlined how William Perkin’s exploitation of the discovery of mauveine triggered a remarkable burst of innovative British chemical and industrial development, much of which resulted from Perkin’s refusal to work on his dye with A.W. Hofmann and E.C. Nicholson, thus provoking the creation of a formidable academic alliance with the new rival firm of Simpson, Maule & Nicholson. Perkin & Sons and Nicholson’s firm displayed their dye products at the 1862 London Exhibition. As adjudicator, A.W. Hofmann, praised both exhibits and predicted Britain’s world domination of this brilliant new industry. However it was Nicholson’s display of a dazzling Imperial Crown of gleaming roseaniline crystals that attracted the crowds. Hofmann undoubtedly knew that Nicholson had already made important advances in chemistry leading to whole families of colour-modulated new dyes such as Hofmann Violets and aniline blues. By this point the craze for mauveine was now clearly over, and Perkin’s financial problems were such that he was planning to sell or leave Perkin & Sons of Brentford. However he then discovered industrial processes to make artificial alizarin, which launched Perkin & Sons into four more years of prosperity. Moreover, with that red colour, Perkin and Nicholson ‘ReWove the Rainbow’ with synthetic dyes in just 13 years.

E.C. Nicholson, meanwhile, realised he had to rebuild his burgeoning business in larger improved premises and chose Hackney Wick in East London. He completed this mammoth task in three years, but then sold his enterprise to Brooke, Simpson & Spiller, a new firm headed by Edward Brooke a wealthy, non-chemist, self-aggrandising merchant of dyes. Six years later, he also bought Perkin & Sons, but not having scrutinised its operations, he soon came to regret the purchase. Chastened, the Greenford assets were stripped, and experienced chemists such as Prof. Ralph Meldola were appointed, not only to research new dyes, but also to advise on management at Hackney Wick. Work recovered there for a while, but their chemists complained of inadequate investment in the business and the firm ceased trading in 1904. Dr Leaback concluded by arguing that Perkin & Nicholson were rare exceptions to what could be considered the usual British malaise of failing to exploit great discoveries commercially. In both of these cases the two talented chemists worked closely with effective businessmen like T.D. Perkin and George Maule in relationships, which merchant Edward Brooke failed to establish in his ill-informed, ill-considered and ill-fated purchase of Perkin & Sons in 1874.

Alan Dronsfield introduced the afternoon session and the lecture which Tony Travis had given as his Edelstein address: “‘What a wonderful Empire is the Organic Chemistry.’” Brushing aside norms of historical accounts of the synthetic dye industry, and reverting to past visions and seemingly unrelated disciplines and ideologies, this paper ventured different, and novel, perspectives of the industry. Through the lives of four individuals, the remarkable and spectacular status that the dye industry once held was acknowledged. The main protagonists are: Theodor Herzl, founder of political Zionism; Heinrich Caro, industrial research leader at BASF of Ludwigshafen; Raphael Meldola, British dye chemist and disciple of Charles Darwin; and Carl Schorlemmer, first British professor of organic chemistry and avowed socialist. The title of the lecture came from a short story by Theodor Herzl, “The Aniline Inn,” which first appeared in 1896. In this allegorical account a professor of philosophy is disillusioned with life and goes out for a walk, contemplating suicide in a nearby river. Next to the river is a factory engaged in the manufacture of aniline dyestuffs. The story of how coal tar waste was processed to produce these valuable commodities provides a symbol of hope to the professor. As the professor saw that even from discarded waste there can be obtained much that is good and useful, the journalist Theodor Herzl, was now destined to adapt his life to serve the needs of the vast discarded waste of the oppressed Jewish people.

The next protagonist discussed was Heinrich Caro (1836-1910), who is best known for his work on the synthesis of artificial alizarin and as research director at BASF. In 1891 Caro produced his own epic and celebratory narrative of the dye industry which remains the most complete history of the industry during its formative years. In contrast, the British dye chemist, Raphael Meldola (1849-1915) used the notion of the survival of the fittest to articulate his own interpretation of the dye industry. His well-researched history served his agenda of concerns over the neglect of technical education, a perspective that resulted from his second period of employment in the dye industry at Brooke, Simpson and Spiller. Finally Carl Schorlemmer (1834-1892), a German born organic chemist who worked in the Manchester dye industry and became the first professor of organic chemistry at Owens College, Manchester, in 1874 was discussed. He wrote a short but widely acclaimed history of organic chemistry which became a model for future histories of science and became a metaphor for later political and academic ideologies by emphasising the wider impact of the manufacture of coal-tar products. In contrast, nowadays, the story of the dye industry is almost forgotten, with the industry having all but disappeared from countries in Western Europe. The sesquicentenary of the discovery of Perkin’s mauve in 2006 had a low profile compared to the Einstein celebrations of 2005, the tercentenary of Carl Linnaeus’s Birth in 2007 and the commemorations planned for the bicentenary of Darwin’s birth and the 150 years since the publication of the Origin of the Species in 2009.

Tony Travis lecture is printed in full in the Bulletin of the History of Chemistry, vol. 33, no. 1, 2008 and can be found online. Please click HERE for the PDF.

Peter J. T. Morris of the Science Museum then spoke on “Interesting Perkin and Post-Perkin Dyes from the Science Museum's Collections.” From various sources, notably the Colour Museum in Bradford, the Science Museum has built up a major collection of synthetic dyes. As well as shedding light on the history of the dyes themselves, the dye jars give valuable information about the dye-makers. There are also plenty of obsolete dyes to be found - including AGFA's Aurantia (the ammonium salt of hexanitrodiphenylamine).

The corporate history of the dye industry was illustrated through dyes such as those from the firm of Weiler-ter-Meer, founded in 1877 and which became part of IG Farben in 1925.The fate of A Leonhardt & Co of Mulheim am Main, near Frankfurt is less clear. An early partnership broke up, but it was listed as a limited company in 1895 and it appears to have been taken over by IG Farben in the 1920s, although evidence is lacking. Midori Blue (a form of Prussian Blue) was produced by G Siegle & Co of Stuttgart. In 1873 the firm was acquired by BASF to act as a sales arm but in 1889 Siegle purchased the firm back again. The dyes collected also provide an insight into changes in the manufacturing procedure. In the collection there are six muslin samples dyed with natural indigo and donated by the Behar (sic) Planting Association in 1914. Adolf Baeyer first synthesised indigo in the laboratory in 1878, but its industrial synthesis proved more difficult, although natural indigo was eventually superseded.

The final session was chaired by Chris Cooksey and began with a paper by Matthijs de Keijzer of the Netherlands Institute of Cultural Heritage entitled “The early synthetic organic dyes: patents and international competition on a global scale.” The Netherlands Institute for Cultural Heritage (ICN) is a leading, independent knowledge institute for the preservation and management of moveable cultural heritage. In 2003 the Research Department of ICN started the project “the early synthetic organic dyes” by choosing a selection of 65 well-known synthetic organics, covering all dye-classes, from 1850 till 1914.

This research project has two main aims.

To obtain a better idea of the history of the early synthetic organics it is of interest to understand the processes that influenced production in the most important dye producing countries in the second half of the 19 th century. Matthijs de Keijzer’s lecture resulted from a literature study and focused on the international competition between the countries, Germany, France, England, Switzerland and the United States of America in the period 1850-1914. In its first decade, Britain and France were the leading producers in the synthetic dye industry, but in the middle of the 1860s Germany came to dominate the global market until the outbreak of World War I with Switzerland in second place. The situation in each country was discussed and explanations were given as to why France and Britain lost their international position. The success of Germany was attributed to the following factors: the patent system, education and training, company and academic collaboration and political processes.

Ernst Homburg of the University of Maastricht spoke on “The Dye Chemists: prospects and problems concerning a new database.” Over the last ten years Peter Murmann and Ernst Homburg have constructed a File Maker Pro relational database of synthetic dyestuffs firms and plants from throughout the world, between 1848 (picric acid, Collas) and 1914. At present, there are 745 different firms (i.e. legal entities) in the firm database, and 613 different plants (i.e. material entities) in the plant database. The first results of the analysis of the data have been published in Johann Peter Murmann, Knowledge and Competitive Advantage: The Coevolution of Firms, Technology, and National Institutions (Cambridge University Press 2003), and in J.P. Murmann and E. Homburg, “Comparing evolutionary dynamics across different national settings: the case of the synthetic dye industry, 1857-1914,” Journal of Evolutionary Economics 11 (2001), 177-205.

In 2006 Murmann and Homburg also decided to construct a data base of dye chemists, with the aim of tracing their career mobility. This will help analyse the knowledge transfer between dyestuff firms as a result of the transfer of chemists, and also will obtain a more quantitative picture of the major university laboratories where the dyestuff chemists were trained at different points in time. As a first step, Murmann and Homburg have experimented with an automatic transfer of data from seven membership lists of the German Chemical Society (1870, 1877, 1886, 1892, 1901, 1906, and 1914) into the database. Peter Murmann together with the assistant Ruud Geven, developed the methodology on how to do this. As a result, the database constructed includes not only dyestuff chemists, but in fact all members of the German Chemical Society in the seven years mentioned. During the last few months Ruud Geven has enriched the database by entering a card system of several hundreds of dyestuffs chemists, which Ernst Homburg constructed in the 1980s. As a result on 15 September 2007 the database had entries for 10,676 different chemists. Ernst Homburg then spoke on the methodology developed for the automatic construction of the chemist database, and presented some first results of the analysis of the data.

The final paper was given by Carsten Reinhardt of the University of Bielefeld and was entitled “Innovation Spectrum. Dyestuffs Research, c. 1900.” Covering the whole spectrum was the major impetus for the innovation efforts of the synthetic dye industry. This did not only apply to colours, but also to other fields of application such as fastness, the applicability to the whole range of fabrics, etc. In order to achieve this, dyestuff companies tapped many “sources of innovation.” Among them were creativity, competitiveness, analogy, imitation, users' input, and academic collaborators. The talk analysed the interplay of this spectrum of innovative activities at two major German companies at the end of the nineteenth and the beginning of the twentieth centuries, with the objective of countering uniform stories about the sources of innovation.

Although not wanting to doubt the importance of the typical structure of the research system of a large chemical company around 1900, Carsten Reinhardt argued for a more careful consideration of technological and scientific creativity in industrial research. Many of the inventions that originated in industry were the products of specialised and experienced research chemists, and quite often research groups stood in fierce competition to be first. This competition closely resembles that of academic chemists which is so well known in the isolation, structural elucidation and synthesis of organic compounds. Examples include the decade long struggle of René Bohn at BASF with Robert E. Schmidt at Bayer (alizarin dyestuffs), and Conrad Schraube of BASF with Eduard Hepp of Kalle & Co. (indulines, a class of aniline dyestuffs). Patents had a crucial function in the development of an independent knowledge base of dyestuff chemistry. Together with the products of the competitors, patents served as guide and starting point for further research

Anna Simmons