Ernest A. LeSueur Pioneer Canadian Chemical Engineer Hugh J. Anderson
Memorial University, St. John's, Newfoundland A1 B 3x7, Canada February 1993 was the 100th anniversary of the first commercially-operating porous diaphragm electrolytic cell in North America. This cell was also much more efficient than the only operating European one. The Canadian inventor of the cell was in his late teens when he designed it, and he was 21 when the first patents were granted. Ernest Arthur LeSueur was born in Ottawa, Ontario, in 1869, the son of William D. LeSueur, a prominent civil s e r v a n t a n d writer, whose forebears came from t h e Channel Islands. After high school he entered Electrical Engineering a t the Massachusetts Institute of Technology in Boston (1, 2). For his graduating thesis, Charles R. Cross gave him permission to investigate the percentages of useful decomposition of a brine solution undergoing electrolysis. This was a topic h e had already investigated a t home during his vacations. Cross told him that none of the faculty knew anything about the subject, so h e was free to explore it himself. He was determined that he would, a s a separate project, also design a cell to produce chlorine and caustic soda rather than a weak solution of hypochlorite (3). His first work on the latter project, during his second vacation from M.I.T., involved a supported mercury cathode cell which gave him a saturated solution of sodium hydroxide, as he found out when he burned his tongue in testing it. However, he decided that the mercury cell was too expensive to operate. As well, there was no market for highpurity caustic. The soap industry preferred it to contain about 10% salt (4,5).He soon had a new idea. Observing that the cathode solution must not reach the anode of the cell, but that it did not matter whether the anode solution reached the cathode, he decided upon a design (Fig. 1) that took advantage of these facts. He installed a porous diaphragm between the electrodes and their solutions and applied a pressure to the anode side. Initially the diaphragm was a vertical one that made quite a compact cell, but he found that a nearly horizontal placement of the diaphragm enabled a uniform pressure to be applied a t all points and to control the flow of salt solution through it for optimum results. Together with Charles N. Waite, who ran a small chemical works, LeSueur tried out his designs in the winter of 1887-1888 a t Waite's establishment in Newton Upper Falls, Massachusetts, where a test run was made by two
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Journal of Chemical Education
Ernest E. LeSueur
Photo counesy of the Socety of Chemlcal Industry
professors from M.I.T. (4).Then, from October 1890 to May 1891, they operated a commercial-size pilot plant in a paver mill a t Bellows Falls. Vermont. He avvlied for his first il. S. and lJ. K. patents in April 1891, u,h;lestill ufritmghls thesis on a somewhat dilyerent cell. The first diaohramn cell patent was awarded to a n American, Isaiah Rdbert:, a few months earlier, but LeSueur's was first into operation by many years (6-8).He obtained four U. S patents in 1891; in each he assigned one-half to Waite (9). His first Canadian Patent was granted the following year (10).
CHLORIN,E OUTLET HYDROGE OUTLCT
ANODE CERAMIC ANOLVTE CONTAINER IRON
CATHOLYTE CONTAINER
ASBEST& C ~ T H O D EIRON PAPER WIRE SCREEN DIAPHRAGM
Figure 1. Original LeSueur Cell. Adapted from Ref. 7, p 87, with permission. Copyright 1972 Robert E. Kruger. Three British Patents were granted in 1891but later withdrawn. Experiments showed that it was necessary to have a mechanicallv. ".not "iust molecularlv. norous d i a n h r a m so that there was a n actual flow of Gdlyte into the c&holyte to counter diffusion of the hydroxide ion. The cathode was a n iron wire screen supported by a perforated metal plate. This, in turn, supported a n asbestos paper diaphragm that lasted an average of seven weeks under industrial operating conditions before needing replacement. The cathode an> diaphragm sealed the m&theof a stoneware bell containing anolyte. The anodes were massive pieces of retort carbon set in metal. but later fine wires of a n l a t i n d i r i d ium alloy mounted in glass was used until, finally, electric furnace eraohite was used. The oressure andied bv the slant of the anode sorutik was controlled by iis depth. diaphragm was sufficient to allow hydrogen to escape (4). I n May 1891, when his British patents had been accented. he took a small model of his cell to Eneland and tged to sell the patent to Ludwig Mond of ~ r u & e r ,Mond and to Ferdinand Hurter of United Alkali Company without success. Both companies were suffering through the competition of Solvay soda with the still struggling LeBlanc operations. LeSueur was able to obtain marginal caoitalization in New England. and the Electro-Chemical cdmpany was establishek Ch&les L. Parsons, later the long-time Secretary of the American Chemical Society, was one of the members of the Company and described the history and operations in a n 1898 article (8). The first cell (Fig. 2) began to operate commercially in February 1893 a t Rumford Falls, Maine, then the end of railway in that region. A 130-ft waterfall on the Androscoggin river powered the operation. Beginning with one 200kW dynamo, they added three more the following year. The three tanks were iron with a concrete liner, supported by a wooden frame. Each tank was 5 ft x 9 ft x 1.5 ft and contained 18bell-type earthenware units. Later, eight larger units of slate on a spruce frame were used. The tanks took 1200 amps each. The Canadian patent of 1892 shows a mechanism to interrupt the electric current when the diaphragm failed (10). The chlorine produced was converted to bleaching powder by passing it over calcium oxide. Rumford, however, was a poor site to do business because i t was too remote and freight costs were high (4). Durine the oneration of the d i a o h r a w cell a nearlv saturate;d cool k n e solution was a d d e i continuously tb the anolyte where the chlorine formed. Hydrochloric acid was added to the brine solution to maintain the pH a t 3 4 under normal conditions. At the cathode the alkali and hydrogen were continuously removed. Any back-migration of hydroxide ion led to several nossible reactions that might a t times he useful:
~e
/ DUPHRAGM IRON WIRE SCREEN CATHODE
Figure 2. LeSueur Cell. Adapted from Ref. 7, p 87, with permission. Copyright 1972 Roben E. Kruger
HOCl $ Hf
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At Rumford some of the chlorine was used to make calcium hypochlorite solution, but i t was cheaper to ship bleaching powder. During the Spanish-American war of 1898 a shortage of chlorates developed and LeSueur rapidly adapted the hypochlorite operation to produce potassium chlorate on a large scale. The reaction was
LeSueur was considered too young to he the plant operator, so he returned to Ottawa. While success initially led to the increase in size of the operation, local modifications to his desim and the fall in orice of the oroducts. caused bv dumpinfiof b l e ~ c h i npowher ~ and rauitic soda by ~ n ~ l a n h and Gerrnnnv concwn(,d to avoid the nossible loss of the $2 m i ~ l i o d ~ e a r ~ oAmerican rth market:led to loss of much of the oriknal caoital. LeSueur was recalled to manage the plant in 1896 a i d put it on its feet. By this time bleaching powder prices had fallen from $45 to $30 then to 5201ton. and caustic soda from $74 to $36/ton, so the plant was sold to the Burgess Sulphite Fibre Company, a subsidiary of the Brown Company, late in 1898. The cells were moved to Berlin, New Hampshire, and began operations soon after. Unfortunatelv. LeSueur had taken advice from oatent attorneys who gad no idea of the process and so the'necessity of mechanical transoort through the d i a n h r a w was not specified. Later he sold his too che'aply-to the Electro-Chemical Comoanv and lost them when the comnanv was sold (11, 12).*As result he was never properiy rewarded for his oatents (4.5). By 1940 the okginal ceils were still producing more than a million oounds oer week of caustic soda and chlorine. They ceased operakon in June 1965 after 75 years service. Several of LeSueur's colleagues designed other diaphragm cells, and by 1904 all North American cells used the LeSueur-type diaphragm. In 1918 the Dow Co. combined their pressure technology with the LeSueur diaphragm giving a very efficient cell. While the plant was under construction a t Rumford Falls, LeSueur was investigating the recovery of copper from ore tailings in Northern Michigan. As the copper amounted to less than 0.5% and was mainly finely divided metal, he reasoned that a copper(I1) solution in aqueous ammonia would oxidize the metal and bring it into solution a s the copper(1) complex:
As
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ful and he soon found that any ammonium salt would do. The solution rapidly took up oxygen from the air to form the copper(I1) complex.
He could then precipitate copper carbonate by treatment with carbon dioxide. LeSueur patented the process in 1899. The Calumet and Hecla Company that had sponsored the research did not immediately take up the patent but did so about 15 years later (2,5). Returning to Ottawa from Rumford, he was engaged by the Consolidated Lake Superior Company of Sault Ste. Marie, Ontario, late in 1899 to study the recovery of oxygen from liquid air. The company, one of several in a n industrial complex built up by a n American entrepreneur, James Clergue, wished to make nickel-steel of very low sulfur content for the Krupp Company. Air had been used to roast the pyrite and nickel ores. The sulfur dioxide produced was to be liquified and shipped to the Company's Espanola pulp mill. However, the gas was too dilute for liquefaction when air was used, so more oxygen was desired for the project. I n 1897, Sir James Dewar, having liauefied air himself, had ~ r e d i d e dthat any fractional limefaition of air would not chHnge its composition. In April 1901, LeSueur took out a patent on a design for the extraction of methane from natural gas by partial liquefaction (13).He then was able to show that the higher the pressure for partial liquefaction of air the lower the oxygen content of the condensate. Soon he was able to show that the reverse was true. He then fractionallv liouefied air usine 110 osi. (su~oliedbv an ordinary mining air compressor),a muchlower pressure than Dewar had used. As well. LeSueur used a somewhat hieher ., temperature providt:d l)?a boiling ~ % ~ t uofr ae ~ r~ch r m oxyeen. 111sliouid v ~ ~ d ubv c t 1903contained well over 403 oxvgen (14).h e apparatus"was "homemade" because ~leq$e was then suffering from a cash-flow problem. This was the beginning of a fmancial crisis for the company,and the project had to be abandoned. Leaving Sault Ste. Marie, LeSueur worked for a couple of years on the oxygen concentration problem a s a member of the private staff of the laboratory of George Westinghouse in Pittsburgh (5).There a de Laval turbine was adapted to abstract as much energy a s possible from the expanding gaseous residue. As well, a counter-current heat exchanger cooled the incoming air. He was later able to sell his patents, which used the novel expansion turbine for pre-cooling the incoming air (15, 16), to Georges Claude's company, La SociBt6 L'Air Liquide, and he became a consultant to them when they set up in Montreal in 1910. Claude referred generously of LeSueur's work in his book "Liquid Air, Oxygen and Nitrogen" (5, 17). LeSueur estimated that the cost of 40% oxygen in air would be about 14 centslcubic ft if about one million cubic ftlday was processed. Later, in 1903, he was asked by Thomas "Carbide" Willson to tackle the problem of using acetylene to light a village. LeSueur decided to solidify the acetylene and ship it in insulated containers. He used the scrap crusts that were chipped from "pigs" of calcium carbide prepared a t Willson's Ottawa Carbide Company to generate the acetylene and then solidified it. Acetylene has a high latent heat of fusion and h e used double-jacketed feather-down insulated containers. These were adequate for eight hours which was twice the time needed for delivery (18).I t was s h i ~ o e dbv Dassenwr exoress train to Maxdle. about 50 km'east o ~ d t t a w a , \ h e r ~it was used for several until electricity arrived there. A safety valve with a 10-lb limit gas to escape, together with a large excess of air, through a safety screen of wire mesh. This provided protection from gas build up (3, 17). "
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LeSueur began patenting wax-based explosives in 1905, and by 1906 he had developed a n explosive that he named "R. R. Virite" (19).Five parts of paraffin wax were melted and four of ground sulfur and 22 of sodium nitrate stirred in. Then the mixture was cooled and grained. This was not a n explosive mixture, nor would it continue to bum. When eight parts of powdered potassium chlorate was dusted over the grains it was ready to use. I t had a low speed of detonation that made it very useful for clearing land and breakine rock. I t was used extensivelv bv the Canadian ort the& Railway Company in constkccon work, possibly including the blasting for the railway tunnel under Mount Royal, north of Montreal. I n a speech to the 1913 annual meeting of the American Institute of Chemical Engineers, LeSueur described seeing a blast near the Quebec -New Brunswick border t h a t used 1000 50-lb cases of Virite. The enormous mass of broken rock and earth continued to mount into the air for three seconds after the blast and looked like a vast and spreading black tree (20). However, explosives factories do have their problems. In May 1910, while LeSueur was manager of the three-year old plant of General Explosives in Hull, Quebec, a fire that began in a shed after hours attracted a very large crowd. Despite efforts of police and firemen to keep them back, many were too close when mercury fulminate detonators stored in the shed exploded and the shock wave csused the detonation of about four tons of Virite in a neighboring bunker. [It was revealed in the House of Commons in its next session that there had been 24 tons of Virite in that bunker the day before]. Seven spectators were killed by falling rock and many others injured. Damage was widesoread in Ottawa and Hull (21). One conseauence was the e&it)lishment of an Ihplojives Division i n t h e Canadian Department of Mines,. to . vrovidr sufi:tv of'ex. insoections . ploiives factories. When war broke out in 1914 LeSueur was in charge of a n exolosives factorv a t Deseronto. Ontario. for Sir Donald D. a firm deeply involved in ~ a n of n ~ a c k e k i and e M-; construction of the Canadian Northern Railway. While there was no demand for TNT from Britain a t the beginning of the war, LeSueur had 10 or 11tons of dinitrotoluene on hand. After some test tube scale experiments, he proceeded to negotiate a contract with Belgium for 25,000 lb of TNT. Up to this time, no TNT had been made on a commercial scale in Canada. As the urgency was great, he set to work without building any plant, only a nitrator. He used a n existing steel storage tank and placed in it a helix of lead pipe on a wood frame that could be raised and lowered, thus churning the contents. Using rubber hose, either steam or ice cold water could be passed through the lead pipe. Other steps in the operation were similarly crude. The workmen were entirelv without vrevious exoerience. Nevertheless. the first bat& of TNT produced wfeighed 700 lb. After personally checkine that the oroduct did not e x ~ l o d ewhen olaced on a steel rail and struck w ~ t ha four-pound hammer, LeSueur cleurrd the factow and milled a 200-lb batch of the oruduct himself in a high speed steel grinder. The rest was then milled by unskilled laborers without incident (20). I n 1923. the world match cartel restricted the suvolv . . , of phosphorus sesquisulfide and the Eddy Company hin!d LcSuwr to desim and install the lirst Canadian olant to make i t a t ~ u l Quebec < (17). Later it was made by the Electric Reduction Co. a t Buckingham, Quebec. When the newly formed Canadian Section of the Societv of Chemical 1nd;stry first met in Ottawa, in ~ e b r u a & 1904, one of the papers was read by LeSueur (17). In 1946 he was awarded the gold medal of the Canadian Section of the Society (22). After his death the Canadian Section began the ~ & u e u rMemorial Lectures, to be given every sec-
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ond year. He was admitted as a Fellow of the Canadian Institute of Chemistry in 1919 and became one of the first Honorary Retired Fellows of the C.I.C. in 1932 (23). During the early 1920's, LeSueur was still designing and patenting electrochemical cells for the preparation of chlorate, hypochlorite, and perchlorate. There was also a patent on m n ~ o n i u mperchlor& preparation and its use in a wrutbased exolosive. Patents From 1927-1933 involvcd easfication and carbonization of fuels as well as a refrigeration and air-wnditioning machinery His last Canadian patents were taken out in 1936 and involved apparatus for drying wet bark and similar materials for fuels by a multi-layer heating pmcess (24,251.LeSueur died a t the end of March 1953a t the age of 85 (26).His wife of 60 years died soon after. ~
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Acknowledgement
My thanks to Joan Fitzsimmons and Glynn Michael, F.C.I.C. for providing information on LeSueur's relationship with the precursors of the Chemical Institute of Canada. I am also indebted to my colleagues Frank Smith for editorial advice and Charles Loader for technical assistance.
Literature Cited 1. Biography Index X I . Jan. 194WTuly 1949: H. W Wilson: NeuYork, 1949. 2. Wsmhpton. C. J.Chem. in Consdo. 1953, Aug, p 34. 3. LeSueur. E. A. Can. Ckzm. and Pmc. Ind. 1940.24.113. 4. LeSuour. E. A Chem and Ind., 1941. p 83. 5. Westman, L. E. C D Cham ~ end MetoNurgy 1922,6.5,22. 6. Leddy J. J.,pp 493494: Roberge, P R.,pp 5121114; Nicholls, R. V Y , pp 5 2 M 3 0 . InEiedmhemislry, Paat ondPmsent; Stoek, J.T m d Oma, M. V., E&.;Amelican Chemical Saeiety: Washington. DC. 1989. 7. Ereher, M. S. I" Chlon'n.; sconce, J. S., Ed.; Robe* E. Krieger: Huntingtan, New York,1972, p 87. 8. Parsons. C. R J A m r Chem Soc. 1898,20,868. 9. LeSueur. E. A United Stater Patents 1891 450.103: 450,104; 450.105. 10. LeSueur, E. A. Canadian Patent 1892 41,047. 11. LeSueur. E.A. Dana Eiectrachem. Soc. 1333.63.187. 12. Vorce, L. D. lhions. Electrochem. Soc. 1944.86.69, 13. LeSueul E. A. Canadian Patent 1901 71,161. 14. LeSueur, E. A. Canadian Patent 1904 90,674. 15. LeSueur. E. A. Metali. and Chrm. Eng 1910,8, 234. 16. LeSuew, E. A. Canadian Patent 1902 80,197. 17. Warringtan, C. J.; Nicholls, R. V V. A History of Chemistry in Camdo; Rtman: Toronto. 1949.
21. 22. 23. 24.
Ctfkn. 1910, ~
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& and 9 10. Can. Chem. o n d P m . Ind. IS&. h. oo 45-46 Michael, T H. G., personal communication. LeSueur, E. A. Chsm Ahsfr. 1937,31.6937,8270. Canadian Patents 1936 368,040: Ottawa
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25. LeSueur E. A. Chem Absfr 1987,31,4168. United States Patent 1931 2,078,952. 26. Oltama CitLcn 1953, Mar 30.
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