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Spring 2002: ‘Analysis in Industry’
Spring 2001: ‘History of Electro-chemistry’
Autumn 2001: ‘French Chemistry’
‘Analysis in Industry’
23 May 2002, Science Museum, London
The Society held a meeting on 23 May 2002 in the Conference Room of the Science Museum and Imperial College Library entitled “Analysis in Industry”. Papers were given by Peter Reed, John Hudson, Dr Ray Anderson and Dr Tony Travis.
Peter Reed’s paper was entitled “Artisans to Professional Chemists: Analysis in the Alkali Industry, 1820-1920”. The Leblanc process, introduced into Britain in the first two decades of the 19th century, was crude and unsophisticated in both its concept and its operation; there was little recycling of by-products and the operation involved very limited controls for determining the optimum operating conditions to make the process efficient in its use of raw materials for maximum yield of alkali. Professional chemists made little or no contribution until the Alkali Works Act 1863 imposed statutory requirements for pollution control on the manufacturers. The Alkali Inspectors provided peripatetic consulting services alongside enforcement of the law, and the manufacturers flirted with chemical analysis at least to the point of ensuring they remained within the law. Nevertheless, the main operation of the Leblanc process was left in the hands of the “artisan” foreman and his co-workers using their long experience and “know-how” of the process with only limited recourse to chemical analysis techniques such as simple alkalimetric or chlorimetric titrations. These analyses could be undertaken by the “artisan” workers with little or no understanding of the underlying chemistry. The alkali industry proved a double-edged sword for analytical chemists as Russell, Coley and Roberts have pointed out – good opportunities but a threat to their professional standing.
From the 1870s, with steadily increasing competition from the Ammonia-soda process (1874) and the electrolytic process (1897), the Leblanc manufacturers set to work diversifying their product-range based on the chlorine and metallic residues derived as by-products from their process. An extensive repertoire of chemical analyses was available to the alkali industry but discrepancies had arisen between Tyneside and Lancashire manufacturers in expressing the purity of soda. In 1884, Lunge and Hurter published The Alkali Makers Pocket Book to provide uniformity in analytic methods. The development of the Central Laboratory in 1891 under its chief chemist, Ferdinand Hurter, brought together process and product development with analytical chemistry across a wide spectrum of the chemical products under the day-to-day guidance of professional chemists. However, but for this period when in its dying throes, the Leblanc process proved to be no better than a “craft” activity with an uncomfortable relationship with analytical chemistry.
John Hudson’s paper was “Analysis on the Rails: Analytical Chemists in the Railway Industry, 1833-1923”. Although it might seem surprising that the industry was an employer of chemists, the railway companies were commissioning analyses as early as 1833, three years after the opening of the Liverpool and Manchester Railway. The first analyses were mainly of water, fuels or timber preservatives. Over the next 30 years some well-known chemists consulted for the railways, among them Robert Angus Smith and Edward Frankland.
In 1864 the London and North Western opened its own chemistry laboratory at Crewe. Its prime function was to monitor the composition of the raw materials entering the company’s newly opened Bessemer steelworks and the composition of the steel produced. The laboratory also analysed samples of water, and before long it was analysing a wide variety of other materials purchased by the company to establish that they were of an acceptable quality.
During the latter part of the 19th century, improved methods were developed for the rapid analysis of oils, fuels, impurities in copper, and the composition of steel and other alloys. At the same time, trains were becoming heavier and were travelling faster, boiler pressures were increasing, and lubricants had to perform under more hostile conditions. Close adherence to specification was becoming ever more vital to prevent materials failing in service. Furthermore, the continuing expansion of the railway industry in terms of the number of passengers and the quantity of freight carried meant that the railways were purchasing materials in ever-increasing quantities, with a consequent greater need for chemical analysis. In 1876 the second company laboratory was established, and thereafter the number steadily increased.
The role of the railway laboratory gradually expanded. The railway chemists advised on the transport of hazardous goods, investigated the validity of claims against the company, and were involved in a wide variety of research projects, from the prevention of weed growing in water troughs to finding the best copper-based alloys to use in the fabrication of boiler tubes and firebox plates in steam locomotives.
By 1923, when the railways in Britain were reorganised, all the large companies possessed their own laboratories and employed their own chemists. The larger laboratories, situated at Swindon, Derby and Crewe, each employed around 12 chemists. It can be argued that one of the criteria for a company to be considered a major player in the railway industry was the possession of a chemical laboratory.
The title of Ray Anderson’s paper was “From Saccharometer to Hartong Number: Analysis in the Brewing Industry, 1780-1940”. The introduction of a uniquely calibrated hydrometer, the saccharometer, in the 1780s provided brewers with a means of assessing the best ways of using their primary raw material, malted barley. The analytical determination of the yield of ‘extract’ from malt was to remain of great commercial importance in the burgeoning brewing industry of the 19th century. The growing output of breweries; the switch away from crude dark heavy beers to more delicate and more difficult to produce styles; the advent of all year round brewing with the introduction of artificial refrigeration from the 1870s; all encouraged the application of science in brewing. By the 1880s various levels of sophistication in analysis could be identified in UK breweries. At a minimum, measurement of specific gravities was required for Excise purposes and thorough visual inspection of raw materials, casks, etc., was considered essential. A step up from this was the provision of a bench or table in the brewers’ room to accommodate a microscope for checking yeast purity and perhaps an assortment of glassware for simple testing of water and malt. In some breweries analysis by brewers who had received training in chemical/microbiological techniques as part of their pupilage or apprenticeship extended far beyond this to more extensive testing of water, malt, hops, wort, sugars and beer in relatively well equipped laboratories. Specialist analytical chemists had been engaged by only a handful of the largest breweries by the 1880s, with the Burton brewers leading the way with the employment of particularly talented men who carried out research as well as routine duties. Four of the Burton chemists were to be elected Fellows of the Royal Society. But Burton was unusual; most brewers relied upon consulting chemists for expert analytical services, particularly when they were outside the normal run and in times of difficulty. The arsenic poisoning episode of 1900 when contaminated beer caused many deaths was the most spectacular and tragic example. Consulting chemists retained a central role in brewing analysis well into the 20th century, even as the number of companies employing specialist analysts increased. Analysts drawn into the brewing industry in the 19th century had predominantly received their scientific education in London or Germany, but with the establishment of specialist brewing schools in Birmingham and Edinburgh at the start of the 20th century; recruitment from these sources became common. The average head chemist by the 1920s ranked someway below the head brewer in the hierarchy of the brewery with a salary intermediate between that of the 2nd or 3rd brewer. He had a status equivalent to that of the head bookkeeper.
Outside the UK, brewers sought to meet their analytical requirements in a variety of ways. In Germany specialist brewing testing and experimental stations attached to higher education establishments in major cities provided analytical services and few breweries employed specialist analysts even in the 20th century. The USA followed the English model, although German immigrants largely ran the industry there; consulting chemists operated in Chicago, New York and elsewhere and leading brewers also employed chemists. Consulting chemists were also to be found Denmark; however two companies, Carlsberg and Tuborg, dominated and established sophisticated laboratories.
By the 1930s the emphasis on raw materials, which had until then been the dominant feature of brewing analysis internationally, began to be diluted with the rise in sales of bottled beer requiring more attention to be paid to aspects of beer flavour, shelf-life and appearance (clarity, foam and sparkle). Analysis thus became increasingly a tool in seeking competitive advantage in the marketplace, complementing its long-standing role as a guide to production integrity and efficiency.
Tony Travis spoke on “Analysts in the Dye and Allied Industries: Calco Chemical Company and American Cyanamid, 1930-1960”. The Calco Chemical Company, of Bound Brook, New Jersey, opened in 1915, was a leading U.S. manufacturer of synthetic dyestuffs. In order to ensure the smooth integration of relatively complex aromatic products and processes, Calco created a formal Research Department in 1927. Two years later, the firm was acquired by the American Cyanamid Company. Studies into textile coloration and standardisation of dyes were notable features of Bound Brook research, with contributions from a dedicated physics research group. There was a mix of instrumental methods, physics of colour, and physical and organic chemistry. Novel, and expensive, instruments were purchased, including the Hardy recording spectrophotometer, introduced in 1935 by General Electric.
Instrumental analysis enabled a better understanding of, and improvements in, dye application, and facilitated pioneering studies on quantitative measurement of colour, most notably by Edwin Ira Stearns. Standardisation of dyes and pigments moved from instrumental colorimetry to spectrophotometry after Stearns demonstrated the overwhelming superiority of the latter. Bound Brook was noted for analysis in the ultraviolet region.
R. Bowling Barnes at the American Cyanamid Stamford research centre (opened in 1937) made notable advances in infrared analysis. Significantly, the first factory of Perkin-Elmer, founded by Richard S. Perkin and Charles W. Elmer in 1938 to manufacture advanced optical systems, was almost adjacent to the Stamford centre, and there was considerable cooperation. No doubt, the practical application of spectrophotometry was advanced more than in any academic laboratory by American Cyanamid scientists Stearns and Barnes.
In 1956, the first volume of the second edition of the dyer’s and colorist’s bible, the Colour Index, appeared. American Cyanamid’s reputation in dye development and instrumental color measurement was reflected in the composition of the U.S. editorial committee, which included five Bound Brook scientists out of a total of 13 members. Moreover, publications in The Review of Scientific Instruments, Journal of Applied Physics, andAnalytical Chemistry, as well as review articles and chapters in books on the newer instrumental techniques of analytical chemistry, attested to the cutting-edge studies carried out at both Bound Brook and Stamford. To this day, Stearns’s The Practice of Absorption Spectrophotometry (Wiley) remains recommended reading for students.
John Hudson
History of Electro-chemistry – a meeting to mark the bicentenary of Humphry Davy’s taking up the Professorship of Chemistry at the Royal Institution
23 March 2001, The Royal Institution, London
The meeting was organised jointly by the Royal Institution, the Historical Group of the Royal Society of Chemistry, and the Society for the History of Alchemy and Chemistry. Speakers were Professor David Knight, Dr Frank James, and Dr Mary Archer.
David Knight called his paper, “New understanding, new elements: Davy’s electrochemistry”. Gravity is universal; but chemical affinity is elective – some substances react together and others don’t. In 1800, chemistry had recently acquired a new vocabulary and a theory of burning from Antoine Lavoisier but awaited its Newton, who would explain affinity simply, in terms of forces. Then Alessandro Volta announced that when two different metals are separated by wet cardboard, an electric current flows. Davy (1778-1829), a young Cornishman working in Bristol, believed that this could not be due to mere contact – a chemical reaction must be generating electricity. Appointed, in 1801 to the Royal Institution in London, Davy attracted audiences that maintained his research laboratory.
At first made to work on tanning and agriculture, by 1806 Davy could undertake blue skies research. When wires from a big version of Volta’s battery were dipped into water, oxygen and about twice its volume of hydrogen bubbled around them. Davy was sure that the ratio should be exact (as when water was formed), without by-products. Using apparatus of silver, gold and agate, he confirmed this hunch; concluding that electricity and chemical affinity were manifestations of one power. Researching in autumnal bursts, the following year he tried using electric currents to break down other substances, notably caustic potash and soda. With molten potash and sparks flying, he obtained globules of a light and highly reactive ‘potagen’ like the alchemists’ long-sought alkahest. He danced about the laboratory in ecstatic delight. Experiments on the soft material, which floated on water, bursting into flames, convinced him that it was a metal; and he renamed it ‘potassium’. From soda, he obtained the analogous sodium, afterwards isolating calcium and other metals also. More systematic chemists, J.J.Berzelius and Davy’s assistant Michael Faraday, brought new order into chemistry by developing Davy’s Newtonian insight that affinity was electrical.
Frank James’ paper was entitled “….’a model to teach him what he should avoid’: Faraday and Davy’s electro-chemistry”. Faraday’s knowledge of electro-chemistry derived from Davy – very early on during the European tour they tried to use electricity from a torpedo to decompose water electro-chemically. In the 1820s Faraday was involved in Davy’s unsuccessful project to protect ships bottoms electro-chemically. It was debacles such as this that presumably prompted Faraday to remark to Henry Bence Jones that in Davy he had “a model to teach him what he should avoid”. Indeed, electro-chemistry was not a major concern of Faraday’s until 1831, when he discovered electromagnetic induction. He needed to establish the identity of all forms of electricity. As he developed better ways of producing electricity from magnetism he continued, unsuccessfully at first, to show that it could produce electro-chemical decomposition.
The early 1830s was a very creative period for Faraday. In Series 5 of Experimental Researches on Electricity, he criticised the two-fluid theory of electricity and also previous theories of electro-chemical action. replacing this with a theory of ‘internal corpuscular action’. In Series 6, dated 30 November 1833, he developed a sophisticated atomic/molecular theory. Almost immediately afterwards he started the experiments for what would become Series 7 in which he drew back from the atomic theory in an abrupt manner – maybe with Davy’s example in mind. He quickly decided that his new theory required a new language with which to express it and adopted the terms anode, cathode, anion and cation, and ion. Within this framework that Faraday enunciated his laws of electrolysis, although his first law had been stated in an earlier form in Series 3. He also withdrew into a severely operational view of electro-chemistry, by, for the first time, publicly attacking the atomic theory. Faraday’s electro-chemical work thus played a crucial role in turning him away from the atomic theory, and set him on a path that would culminate ultimately in the field theory of electro-magnetism.
Mary Archer’s paper, entitled “Beyond metal electrodes, Semiconductors, space charge layers and surface states”, brought the meeting right up to date in an area of contemporary electrochemistry; an area in which Dr Archer herself worked at the Royal Institution with George Porter.
After pointing out that some of the early workers were unwittingly using semiconductor electrodes because of the contamination of metal surfaces with oxide or sulphide layers, Dr Archer outlined some key historical landmarks. She commenced with Edmond Becquerel’s observation of 1839 of a photoelectrochemical effect using a platinum electrode coated with silver halide. Other key events included the double layer at metal electrodes (Gouy and Chapman 1910), the band structure of solids (Brillouin, 1920s), the theory of electrolyte solutions (Debye and Hückel, 1923), metal-semiconductor junctions (Schottky 1938), the point-contact transistor (Bardeen and Brattain, 1947), and the electronic structure of doped transistors (Shockley, 1949).
Dr Archer then contrasted the space-charge layers existing at a metal electrode-solution interface and a semiconductor-electrode-solution interface. The early semiconductor electrode research was complicated by impurities, but work in the Bell Telephone Laboratories reduced these difficulties, with the production of high quality doped germanium. Ensuing key events included Brattain, Garrett and Dewald’s work on the principles of semiconductor electrochemistry (1960), Gerischer’s work in the 1960s on the kinetics of electron transfer between valence and conduction bands, the photoelectrolysis of water (Fujishima and Honda, 1972), and the early demonstrations of solar photoelectrochemistry by Memming, Heller and Lewis in 1974. More recent developments resulted in efficient (12%) photoelectrochemical water splitting by Turner in 1999.
Dr Archer then outlined the mechanism of photoeffects at electrodes, showing how an illuminated n-type semiconductor drives an oxidation process, and a p-type semiconductor a reduction process. Surface states – crystalline defects or islands of platinum on a semiconductor surface – can be a nuisance or can promote the desired reaction. Such electrodes hold out prospects for the photo-oxidation of pollutants such as PCBs. The photosensitisation of semiconductor electrode surfaces presents problems – a monolayer of dye gives poor light absorption, a thick layer quenches the desired reaction, but a nanocrystalline sensitised layer on glass may be the solution. Dr Archer concluded by outlining some current and possible future applications. These included various solar energy conversion devices, and the prospect of light-activated self-cleaning surfaces consisting of a bed of semiconductor particles and titanium dioxide. Organic surface contaminants would be oxidised, and wiping down the kitchen tiles might no longer be necessary!
John Hudson, Hon Secretary, SHAC Anglia Polytechnic University
French Chemistry
22 November 2001, Science Museum London
The Society for the History of Alchemy and Chemistry held a meeting on 22 November 2001 in the Conference Room of the Science Museum and Imperial College Library entitled “French Chemistry”. The meeting was held to honour the memory of Dr W.A. Smeaton, a former Chairman of the Society, who died earlier in the year.
The meeting opened with the personal appreciation of Bill Smeaton that was given by Professor Robert Siegfried when the Dexter Award of the American Chemical Society was posthumously awarded to Bill in August. Professor Siegfried was unable to come to London to give the appreciation to the memorial meeting, so it was presented by the current Chairman of the Society, Professor W.H. Brock. Siegfried recounted some of the occasions on which he had met Bill, and described how enjoyable and fruitful he had found these encounters.
The first paper, “The Lavoisier ‘School’ and the Society of Arcueil” was given by Professor Maurice Crosland. Professor Crosland opened by remarking that it seemed appropriate to commemorate Bill Smeaton by speaking about French chemistry in the late 18th century and the early 19th century. Bill’s scholarly publications explored the life and work of Lavoisier and he wrote a book on Fourcroy, but most of his research was directed towards another of Lavoisier’s collaborators, Guyton de Morveau. The combination of these names gives rise to the question of whether there was a Lavoisier ‘school’, a term used by Fourcroy in his little-known éloge of his former colleague. Certainly it is worth looking at Lavoisier’s associates, several of whose help he formally acknowledged. The question was raised as to why Lavoisier was so successful in founding a new chemistry. Part of the answer must lie in the help and support he received from various colleagues. Yet probably the first real school of chemistry is to be found in the Society of Arcueil, which met just outside Paris under the rule of Napoleon and under the patronage of Berthollet, who provided scarce laboratory facilities for a group of talented young men including Gay-Lussac, Thenard and Dulong. Under the new French system of higher education in science the research schools of J.B. Dumas and Adolphe Wurtz made important contributions to chemical education and have been studied by Leo Klosterman and Ana Carneiro respectively at the University of Kent at Canterbury. This has helped to provide a French dimension to what is traditionally regarded as the most famous research school of the 19th century, that of Justus Liebig at Giessen.
John Perkins gave a paper entitled “Chemistry in France, 1750-1800: Perspectives from the Provinces”. Most historians have perceived chemistry in eighteenth-century France as an exclusively Parisian practice. This was not so. Between 1750 and 1789 chemistry courses, mainly intended for a public audience, were set up in some 30 provincial French towns. They are the most visible manifestation of the growing public deployment of chemical expertise, not only in education, instruction and enlightenment, but also in various branches of industrial production, in commerce and agriculture, in public health, urban administration and justice. During these decades a new domain of scientific practice, chemistry, was created in the major cities and towns of the French provinces. Its creation was bound up with the development of urban cultural institutions, with the striking growth of a new cultural market, the need for new forms of expert knowledge in response to changing demands on urban governance, and with new industrial and commercial opportunities. But it also owed much to the private initiative of a number of chemical practitioners. Its creation was inseparable from the attempts of a number of apothecaries and physicians to build careers outside medicine and pharmacy. In making their public lives they made their private enthusiasms into a public science. By 1789 chemistry was a feature of the cultural landscapes of many provincial cities, evidence for a wider and more dynamic French chemical community than historians have hitherto suspected. Exploring this emergent chemical domain in the provinces and the processes through which it was constructed can throw new light on larger questions: the relationship between Paris and the provinces; between science and the Enlightenment; the shape and dynamics of the Chemical Revolution in France; between science and the state at the end of the Ancien Regime and during the Revolution; and the role of chemical knowledge and practice in technological change.
Dr Bob Ward paid tribute to Bill Smeaton’s qualities as a teacher and gave an account of the seminar group on the history of chemistry that met regularly in London for almost 40 years. He then delivered a paper on “P.-J. Pelletier’s Development of Vegetable Chemistry”. Towards the end of the eighteenth century it was realised that the most promising chemical method of investigating vegetable matter was to find what might be extracted from it with a range of solvents. Pharmacists played an important role in this, notably those associated with the School of Pharmacy in Paris. Nevertheless, a key discovery was made in Germany by Sertürner in 1817. He established that a crystalline substance obtainable from opium (which he named Morphium) was actually a base, the first example of what came to be known as alkaloids. In Paris Pelletier was already engaged in the analysis of medicinal plants, conducting his experiments with great care and subjecting the products to biological assay. Stimulated by the discovery of a vegetable base he rapidly isolated several others in collaboration with Caventou, including Quinine from Cinchona bark in 1820. In the form of its sulphate Quinine rapidly established itself in medical practice. During the year 1826 a total of 90,000 ounces were manufactured to meet the demand and this may be regarded as the start of the modern pharmaceutical industry. The proliferation of new alkaloids meant that they were not easy to distinguish from each other. This was a particular concern of Pelletier, who in the course of his work made increasing use of quantitative data to discriminate between substances, which contributed to the development of organic chemistry. Discussion arising from the paper focused on the issue of what is the basis on which one may claim to identify a new chemical substance. There is much scope for the historical study of how such claims have been made (and continue to be made) in different experimental contexts.
The meeting concluded with a paper by Dr Frank Greenaway entitled “A personal encounter with French chemistry: the 1950 French Scientific Instrument Exhibition at the Science Museum”. Dr Greenaway remarked that 1950 was the year in which Bill Smeaton began his own connection with the French science of a much earlier period. The exhibition was initiated by some French instrument manufacturers who had close connections with the leading French scientific institutions. Using contacts with British scientists who had worked in France, as well as diplomatic channels, they obtained agreement for the Science Museum to house an exhibition of modern instruments and to provide necessary services. Frank Greenaway, then an Assistant Keeper in the Chemistry Department of the Museum, was charged with overall liaison. The paper referred incidentally to many housekeeping problems, such as Customs and Excise clearance, and, on the technical side, the provision of power supplies. Many persons, now characters in the history of science of the past century, appear in the archives of the Exhibition as attending various related formal and social events. Of 190 exhibits about one in ten had a clear connection with chemistry, while many could obviously be used in chemical studies. Nearly half were contributed by the leading French research organisations: the long-established CNRS, the more recent ONERA, and the then young Commissariat à l’Energie Atomique. The other half were contributed by individual firms, some showing evidence of close collaboration with French Government organisations. Older connections can be noticed. One of the French organisers, exhibiting apparatus for testing explosives, is revealed as having worked during the War in the Ministry of Home Security. Scrutiny of the catalogue throws up many other small details that might repay further examination. Greenaway’s own recollection of the Exhibition is of the enjoyment of his first hands-on work in the physical evidence of the history of modern science and of the thrill of having his first contact, through letter of thanks, with a Nobel prize winner, Frédéric Joliot-Curie.
John Hudson
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