Electrochemistry, Past and Present - ACS Publications - American

Chapter 35

Gibbs, LeSueur, and Willson

Downloaded by UNIV OF CALIFORNIA SAN DIEGO on April 5, 2016 | http://pubs.acs.org Publication Date: January 1, 1989 | doi: 10.1021/bk-1989-0390.ch035

Pioneers of Industrial Electrochemistry Robert V. V. Nicholls Department of Chemistry, McGill University, Montréal, Quebéc H 3 A 2K6, Canada William T. Gibbs (1868-1910) migrated from England to Buckingham, Que. There in 1893 he perfected electrolytic methods for the production of chlorates and dichromates, and an electrothermal method for phosphorus. The latter process may have been an example of simultaneous invention. Ernest L. LeSueur (1869-1953) was born in Ottawa. While enrolled in M.I.T.'s Electrical Engineering course, he invented a diaphragm cell for the electrolysis of salt, which was widely used. Thomas L. Willson (1860-1915) grew up in Princeton,Ont. Moving to Spray, N.C.,he discovered by chance in 1892 an electrothermal method for making calcium carbide, starting material for acetylene, cyanamide, etc. Thomas Leopold Willson (l,2,3) was born at Princeton, a village between Brantford and Woodstock, Ont., on March 14, 1860. He enrolled at Hamilton Collegiate Institute. After graduation he was apprenticed to a blacksmith, John Rodgers, who allowed him to work in the loft of the smithy. There he built a dynamo, then a novel source of direct current. He used the machine to produce an arc light. So spectacular was the result that a local merchant gave him a contract to illuminate his factory. There was even some talk of lighting the public park with electricity. However, at this time John J. Wright, having solved the problem of automatic feed for the carbons, was erecting lights along Yonge and other streets in Toronto. Wright had patented his device and Willson wisely abandoned further effort. Failing to find satisfying . work in Ontario the young man emigrated to the United States in 1881. He continued to be interested keenly in the potentialities of abundant and cheap electricity. In 1891 he met Maj. James Turner Morehead, who owned a cotton mill and water rights at Spray, N.C. (4). Together they formed the Willson Aluminum Company "for the manufacture of aluminum .... in an electric furnace". Apparently their intention was to obtain the metal from aluminum oxide or a salt, such as the chloride, by reduction with calcium. Presumably, they were aware that about five years before the British Aluminium Company had built a plant to accomplish 0097-6156/89/0390-0525$06.00/0 © 1989 American Chemical Society

Stock and Orna; Electrochemistry, Past and Present ACS Symposium Series; American Chemical Society: Washington, DC, 1989.


526

ELECTROCHEMISTRY, PAST AND PRESENT

the same result using sodium, recently made available in guantity by the Hamilton-Young-Castner Process. They may not have given sufficient weight to the significance of Charles Martin Hall's invention just at this time of a method of producing aluminum by the electrolysis of aluminum oxide in molten cryolite, which by 1889 was being exploited by the Pittsburgh Reduction Company. Be that as it may Willson certainly tried to devise a route for the manufacture of calcium metal in guantity by heating calcium oxide (lime) with carbon (coke). He had moved to Spray in the autumn of 1891 and built a small hydroelectric plant and an electric-arc furnace. On May 2, 1892, the initial experiment was performed. At the high temperature of the arc a brown liguid flowed from the furnace and solidified on cooling. When brought into contact with water the solid produced a gas. Clearly it was not the hoped-for hydrogen as it would have been had the solid been calcium. The flame was sooty, suggesting that the gas was a hydrocarbon. Could it be acetylene, then still a laboratory curiosity, which had been first prepared by Friedrich Wöhler in 1862? A sample of the solid was sent to Lord Kelvin at Glasgow University. In due course his reply, dated October 3, was received. The gas was acetylene. With a minimum of delay Willson applied for American, Canadian, British and other patents. Just in time he obtained protection for his invention, beating Henri Moissan, the eminent French electrochemist, by the narrowest of margins. Typical of those patents was U.S. Patent 541 137, June 18, 1895. It claims "An Improved Calcium-Carbide Process". The electric furnace is described. An intimate 35:65 mixture of finely powdered coke and lime is to be heated. The calcium carbide is obtained by raising one electrode to which it adheres or by tapping the carbon-lined furnace at the bottom. The applicant emphasizes the advantage of using an alternating current, because thereby the charge readily and automatically feeds between the electrodes. Willson sold his American patents to the Union Carbide Company, which exploited the invention by operating a large plant at Niagara Falls. It eventually prospered. Not so its competitors (5). Willson Sells American Patents and Returns to Canada Willson returned to Canada as guickly as possible in 1896. The Canadian Patent Act reguired that an invention be used within two years or the patent would be revoked. He obtained permission to harness the power of the excess water from Locks 8, 9 and 10 of the Welland Canal, at Merriton, near St. Catherines. The fall at each of these locks was121/2feet. The potential electrical horsepower was 1,650. Using $ 90,000 of his own money he erected a power plant (housing a 400-h.p. General Electric single-phase, alternating-current generator) and a carbide plant (housing two furnaces with room for eight more). The arc of each furnace operated at 75 volts and 1,000 to 2,000 amperes. It produced four 500-pound pigs of carbide in twentyfour hours. The surfaces of the pigs were trimmed giving impure flake. The pure cores were broken into lumps. At that time the sole use of calcium carbide was to provide acetylene as an illuminant in homes and factories, and for bicycles, car-



35. NICHOLLS


527

riages and trains. Willson set out with vigor to develop these and other uses. Since sad experience had shown that the gas could not be compressed safely in cylinders, it had to be made when and where required. Soon a number of cleverly-designed generators appeared on the market. The Merriton works commenced operation on April 13, 1896. The first, 200-lb., trimmed pig was ready on August 15. The first export shipment left in December. "Carbide" Willson incorporated a second enterprise, the Ottawa Carbide Company, in 1900 and took up residence in the Capital a year later. A plant was built on Victoria Island in the Ottawa River. Power was purchased from the nearby hydroelectric plant of Ahern and Soper's Ottawa Electric Company. In 1903 Ernest LeSueur, of whom more below, with characteristic originality, devised a novel method of shipping acetylene. Useing the flakes chipped from the pigs at the Ottawa works he generated acetylene, compressed it to 8 p.s.i. (10 p.s.i. was accepted as the safe upper limit), and by rapid expansion converted the gas into a solid, in a manner now familiar for the conversion of compressed carbon dioxide into Dry Ice. The solid acetylene was then shipped by express train in containers insulated by feathers the 35 miles to the Town of Maxville. There the streets were illuminated in this fashion for a number of years until electricity became more economical and convenient. At this time (1901) the Shawinigan Carbide Company was formed with J. W. Pike as president and T. L. Willson as vice-president. Three years before the Shawinigan Water & Power Company had been incorporated to exploit the hydroelectric power of the St.Maurice River at Shawinigan Falls, Que., and upstream. A year later 10,000 h.p. became available but, because there was an oversupply of carbide, the Carbide Company did not start production until two years later. Meanwhile, a very important, new use for acetylene had been developed, oxy-acetylene welding and cutting. The oxy-acetylene became popular because it gave a temperature of 6,000 to 7,000° F. contrasted with 4,000, the maximum attainable with the oxy-hydrogen flame. This application stimulated the invention of a safe method of compression acetylene to facilitate its storage and shipment. The challenge was met by the Prest-O-Lite Company, who devised a method involving the compression of acetylene to 300 p.s.i. into a cylinder packed with a solid absorbent saturated with acetone. To give an account of the employment of calcium carbide for the fixation of atmospheric nitrogen through its conversion to calcium cyanamide and of acetylene as a versatile, raw material for organic synthses is to digress from the accomplishments of "Carbide" Willson. Willson was not to be free from accusations of patent infringement. Particularly notable was his protracted litigation with L. M. Bullier. In 1908 Shawinigan Water & Power purchased control of Shawinigan Carbide and three years later the Canada Carbide Company was formed to acquire all of Willson's manufacturing rights under his carbide patents. The works at Merriton, Ottawa and Shawinigan Falls were purchased outright. The Merriton plant continued in operation until 1924 when it was sold to Union Carbide. The Ottawa plant was closed in 1908 when it was found that power at that city could be more ad-


528

ELECTROCHEMISTRY, PAST A N D PRESENT

vantageously used for other purposes. The facilities of Canada Carbide were further improved and expanded.


Willson's Interest in Ferro-Alloys and Fertilizers The large-scale manufacture of ferro-alloys in Canada originated in this century when electric-furnace capacity had expanded beyond the lagging demand for calcium carbide, This situation focused attention on alternative uses for the furnaces, including the production of these alloys. Typically, Willson became involved. His participation led to the organization of the Electro-Metallurgical Company of Canada in 1906. A year later the Company erected at Welland Canada's first plant for the production of ferro-silicon. During the Great War it consumed as much as 50,000 h.p. to manufacture 85 per cent alloy, to the order of the British Admiralty for the making of hydrogen for the inflation of balloons. At that time it was the largest in the British Empire. Within a couple of years of taking up residence at 188 Metcalfe St., Ottawa, Willson completed a laboratory in its basement. In the words of his daughter, Mrs. Marion S. Roberts (6), "He wrote glowingly that he had equipped the finest laboratory on the continent for its purpose. It was his dream to do scientific research on nitrogen." To elucidate the cryptic phrase, "on nitrogen", will require further study. Could she have been referring to cyanamide? The Willsons' association with the Gatineau River Valley, which is close to the Capital, began in 1904, when they rented a cottage on Meech's Lake. Within five years they had bought considerable land and built a house. What is important for our purpose is that the property included the falls on Meech Creek. There, to the consternation of some of their neighbors, Willson constructed a dam, a powerhouse and a double-superphosphate plant, which required the processing of phosphoric acid. The devising of novel methods for the manufacture of phosphatic fertilizers became his consuming passion. This passion was to lead to his financial ruin. The enormous potential of the Saguenay River for hydroelectric-power production had captured his imagination. As early as 1900 he had secured from the Quebec Government very favorable rights. Now he needed customers for the power. Naturally, since obstacles to the long-distance transmission had yet to be overcome, he had difficulty in persuading industry to establish itself in such a remote place. Pulp-and-paper mills and carbide works were considered. I will quote from his daughter again. "The fertilizer appeared to be reaching the stage of practical, commercial production In order to get the first capital he sold all his companies, and mortgaged all his patents, property and waterpower rights to James Buchanan Duke, the 'tobacco king'. He was unable to meet the time limit on the mortgages and in one sweep Duke took all Willson's assets It was supposed that Willson's patents covering the entire world were gone. But it turned out that Newfoundland was not covered." He applied for the necessary protection, formed the Newfoundland Products Corporation, secured the required legislation from the Colonial Government, and by July, 1914, had raised millions on the London market. War was declared in August! Export of British capital was forbidden. While in New York City, searching for alternative support, "Carbide" Willson died of a heart attack on December 20, 1915.


35. NICHOLLS


529


Le Sueur Perfects a Diaphragm Cell The practical application of electrolytic decomposition had its origin in the work of Humphry Davy in England. In the second Bakerian Lecture (1807) he summed up its primitive state and announced that he had accomplished in his laboratory the isolation of the two metals, sodium and potassium, by passing a current through fused soda or potash. In 1851 Charles Watt received a British patent, which described the preparation of caustic soda and chlorine from salt by a process which is essentially the one used today. For many years the exploitation of electrolytical decomposition on an industrial scale was inhibited by the lack of a source of cheap and abundant direct current. This lack was satisfied by the development of the dynamo by Siemens Gramme in the 1870's. Malthes and Webe were the first to electrolyse brine in a diaphragm cell, which they patented in 1886. The firm of Chemische Fabrik Griesheim bought the patents, made the process continuous, improved the carbon electrodes and opened a plant at Bitterfeld in 1890. However, the electrical efficiency of the cells left much to be desired. Ernest Arthur LeSueur was born in Ottawa on February 3, 1869 (7). He attended public school there, finishing at the Ottawa Collegiate Institute. Then he enrolled in the Massachusetts Institute of Technology and graduated with a bachelor's degree in electric engineering. (A Canadian university (McGill) was not to offer a similar degree until a year later.) In 1888, while still a student, he became interested in the electro-decomposition of salt solutions. First he built a cell with a supported-mercury cathode. There is some evidence to suggest that significant experiments were performed in Ottawa durinq the following summer vacation. In 1889 he turned his attention to the porous-diaphragm type and submitted the results as part of his graduation thesis. Many years later (1940), when in a reminiscent mood, during an address before the Toronto Branch of the Canadian Institute of Chemistry (8), he said "When Professor Charles R. Cross gave me permission to embark upon an investigation of the percentages of useful decomposition, under various conditions, of solutions undergoing electrolysis, he told me I should be quite free from leading strings, seeing that neither he nor anyone on the staff knew the first thing about such matters" ! Be that as it may LeSueur applied for his first patent in the year of his graduation, when 22 years old. Again let LeSueur speak for himself. "After experimenting for some time I came to realize that although cathodic solution reaching the anode meant 'death' to the decomposition efficiency, it was a matter of almost indifference (at least as regards such efficiency) for the anolyte to reach the cathode It seemed, therefore, that the solution of the problem would be to apply a pressure on the anode side of the diaphragm Subject to the employment of this principle there is no limit to the variety of cell constructions that can be used successfully I adopted the arrangement of a horizontal or nearly horizontal diaphragm instead of the obvious and in respect to compactness, much more advantageous vertical one, because of one's ability to get the same .... pressure and transfer at all points .... a more rugged construction .... and the advantage of the anolyte pressure offsetting the tendency of the hydrogen beneath the diaphragm to bulge it upwardly. "



530


After demonstrations during 1890-91 at Newton Upper Falls, Mass. and Bellows Falls, Vt., and with capital obtained in Boston, the youthful LeSueur formed the Rumford Falls Electrochemical Company. The site of the first plant in North America for the electro-decomposition of salt was selected in 1892, at a 130-foot fall on the Androscoggin River in Maine. Operation started a year later. Four circuits of cells consumed about 750 kw. of power (9). In order to keep the chronology of brine electrolysis to the forefront one should mention that the Castner Electrolytic Alkali Co. started at Niagara Falls, N.Y. in 1897; the Dow Chemical Co. at Midland, Mich. in the same year; and Pennsalt Co. at Wyandotte, Mich. in 1901. The LeSueur design was licensed to the Electrochemical Company and to several American firms, notably paper-making ones, who needed a cheap supply of chlorine for bleaching. In 1898 the Company, including LeSueur's patents, was purchased by the Burgess Sulphite Fibre Company. The plant was moved to Berlin, N.H. LeSueur was "out" He was always to regret his self-imposed exclusion from further developments in the electrochemical field. He returned to Canada and became a very successful consultant in chemical engineering. But that is another story. Let it suffice to state that he was retained by the Consolidated Lake Superior Corporation to obtain oxygen-enriched liquid-air for steel smelting at Sault Ste.Marie, Ont.; in 1903 he produced solid acetylene (as has been recounted already); after 1905 he became interested in explosives in association with General Explosives Ltd. of Hull, Que., an interest which continued into the Great War; he designed and installed a phosphorus sesquisulphide plant for the Eddy Match Company. He continued as a very active and highly regarded practioner until his death in Ottawa in 1953. Ernest LeSueur was a founding member of the American Society of Chemical Engineers (1908) and of the Canadian Institute of Chemistry (1920). He received the Canada Medal of the Canadian Section, Society of Chemical Industry, and that society established a medal in his honor. And what of the original LeSueur cells? The Brown Company, successor to Burgess Fibre, operated them, and others like them, for more than fify years -- in competition with later designs of diaphragm cells, such as, the Townsend-Hooker (first used in 1906), the Billiter (1907) and the Gibbs. Of the last named more anon. William Gibbs; Electrolytic Chlorates and Dichromates William Taylor Gibbs was born on a farm at North Stoke, near Bath, England (10). He enrolled in the Merchant Venturers School in Bristol and in due course won a scholarship in chemistry and geology at the Royal College of Science, London. On graduation he engaged in electrolysis research in East London. In 1890 he came to Buckingham, Que., to be chemist at one of the British-owned apatite (tricalcium phosphate) mining companies. Shortly afterwards the phosphate boom in that area collapsed due to the inroads of Tennessee and Florida rock. William Gibbs saw the possibilities of cheap, local power and began experimenting with electrochemical processes. On the Liève River, which flows into the Ottawa River, 25 miles below Canada's capital, there were two readily accessible falls. The nearer one had the poStock and Orna; Electrochemistry, Past and Present ACS Symposium Series; American Chemical Society: Washington, DC, 1989.


35. NICHOLLS


531

tential of producing 10,000 h.p. Gibbs gave his attention to the manufacture of potassium chlorate via the electrolysis of the chloride in alkaline solution. He also developed an electrolytic method for the conversion of sodium chromate into dichromate, with recovery of half of the sodium as carbonate. The chlorate process was refined and patented (Can. Patent 42 429, 1893). With the financial assistance of Stanislaus P. Franchot and Alexander MacLaren, a plant was built at Masson, at the junction of the rivers. After a year of successful operation it was totally destroyed by fire. Gibbs, Franchot and others formed the National Electrolyte Company and, using a later design of cell, established a works at Niagara Falls, N.Y.,for the manufacture of chlorates and dichromates. Franchot, an American citizen and co-director with Gibbs, moved to superintend its operation. Gibbs and Electrothermal Phosphorus and Ferro-Chromium Gibbs, rather surprisingly, decided not to accompany Franchot. Instead he saw an opportunity to use electricity to exploit the local phosphate rock. With a partially-built 10,000-h.p. powerhouse nearby and awaiting a purchaser, he had no great difficulty in persuading Walter A. Williams to become a partner with him. He invented a method for the production of yellow phosphorus, which involved the heating of a mixture of mineral phosphate, carbon and silica. He successfully adapted a furnace of the Siemens type by using jointed, carbon electrodes, to insure their complete utilization and continuous operation. Phosphorus distilled off and a calcium-silicate slag drained away. Using 500 h.p. production began in 1896. Reguiring further capital, Gibbs and Williams secured it a year later from the Anglo-Continental Gold Syndicate, with headguarters in London. A corporation, Electric Reduction Company, was formed in November with an authorized capital of & 40,000. The Syndicate held a 50-percent share; Gibbs and Williams the remainder. (One should note that Gibbs retained his interest in National Electrolyte.) (Hambly, Fred T. A History of the Electric Reduction Company of Canada, Ltd., Buckingham, Quebec, 1897-1951, unpublished manuscript) At the beginning of the enterprise the furnace was charged with calcined alumina phosphate (imported from the West Indies), lime phosphate (obtained locally), coke and sand. After about 1900 local phosjphate was replaced by ore from Tennessee and then Florida. Alumina phosphate was dispensed with after 1910. A decision was reached by the British shareholders to extend the power facilities and, pending the development of an enlarged market for phosphorus, to use the power for another purpose. International interest in the manufacture of stainless steel had recently arisen and this incentive, coupled with the existence of chrome-iron ore at Black Lake, Que., suggested the appropriateness of embarking upon the production of ferro-chromium. Experiments were successful and in 1899 an alloy averaging 63 percent chromium was made in a carbide-type furnace. Upwards of 1,000 tons of the alloy were produced and exported to Sheffield, England, up to 1906, when mining operations were suspended at Black Lake due to the exhaustion of the ore. From experience gained from the design and frunning of the ferro-chromium furnace, it was found possible to tap the molten alloy directly. This improvement had an interesting sequel. When Gibbs became technical



532


director of Shawinigan Carbide, acting jointly with R. A. Witherspoon, he applied this continuous method of discharging to carbide production. Apparently, Gibbs was unaware that a method for the manufacture of yellow phosphorus, very similar to his own, had been patented by J. B. Readman in England in 1888. The Readman patent (together with similar Parker-Robinson one) had been acquired and exploited (in 1890) by The Phosphorus Company, formed for that purpose. After negotiations Albright'sboughtTheCompany and within two years had moved the operation from Widnesfield to Oldbury. Albright's had enjoyed a virtual monopoly of white-phosphorus manufacture in Britain and a lucrative oversea trade for many years, using a batchwise procedure (heating of the mixture in iron retorts by coal as first then by coal gas). So advantageous was the new, continuous electrothermal process that Albright's terminated the use of retorts in 1895 (11). Gibbs did not learn of the Readman patent until Fred J. Hambly came from Aberdeen in 1898 and directed his attention to Readman's papers in the 1890 issues of the Journal of the Society of Chemical Industry. In 1900 Albright's filed suit in a Canadian court alleging infringement of their Canadian patent on the part of Electric Reduction. After giving consideration to many factors Albright's withdrew their suit and purchased the controling share held by the Syndicate. Gibbs declined to enter into this out-of-court settlement. He held his share until his death in November, 1910 (from a heart attack following upon a hunting accident). Williams held his until his retirement in 1914. Arthur Gibbs and Another Diaphragm Cell This paper ends with a "footnote". William Gibbs' brother, Arthur E., had joined the Pennsylvania Salt Manufacturing Company (Pennsalt). William recommended to Arthur that he undertake research directed to improving the diaphragm cell, designed for the electrolysis of brine to produce caustic soda and chlorine. I do not know whether William's help went beyond this initial advice. I do not know when the work was performed. I do know that it was very fruitful. From it emerged the Gibbs cell. It was patented in many countries (Can. Patent 110 604, 1908). Pennsalt had established an electrolysis works at Wyandotte, Mich., in 1898, where it eventually used Gibbs cells. They were first used in Canada by the Canadian Salt Company in 1911, adjacent to its mine at Sandwich, Ont. The cell was of the vertical, cylindrical diaphragm type. Literature Cited 1. Langford, M. W. M.A. Thesis, Carleton University, Ottawa, 1977 2. Warrington, C. J.; Nicholls, R. V. V. A History of Chemistry in Canada; Pitman: Toronto, 1949, p 167 3. Willson, T. L. Letters, pamphlets, articles, patents, clipPublic Archives of Canada, Ottawa; MG 30, A85 4. Morehead, J. Motley James Turner Morehead; An address delivered before the International Acetylene Association, Chicago, October 27, 1922 5. Willson, T. L.; Suckert, J. J. J. Franklin Inst. 1895, 139,21


35. NICHOLLS 6. 7. 8.


9. 10. 11.


533

Roberts, M Up The Gatineau, Historical Society of the Gatineau, 1976, 2, 16 Warrington; Nicholls. Ibid, p 344 LeSueur, E. A. Can. Chemistry Process Industries 1940, 24, 113 LeSueur, E. A. Trans. Electrochemical Soc. 1933, 63, 188 Warrington, Nicholls, Ibid, p 80 Threlfall, R. E., The Story of 100 Years of Phosphorus Making, 1851-1951; Albright & Wilson: Oldbury, 1951

RECEIVED August 12, 1988


Electrochemistry, Past and Present - ACS Publications - American

Recommend Documents