Document 0NXwBvwEOXddqoE2KJVZ2VvJ

Report DC-83 Project Humber 11-3 \o Humber of Fages 401 RESEARCH LABORATORIES DIVISION GENERAL MOTORS CORPORATION Detroit, Michigan THE EARLY HISTORY OF`ETHYL GASOLINE Reported by: T. A. Boyd Organic Chemistry Department Approved by: T. A. Boyd, Head of Department H. C. Mougey, Technical Director June 8, 1943 ETC 36795 Rerort OC--83 >'OKE?/ORD This history of the development of Ethyl Gasoline and of the early years of its commercialization is based mostly upon records, reports, and correspondence in the files of the Research Laboratories Division, General Hotors Corporation. It represents a revision and extension of matter first prepared in 1938 and 1939 from a search made for another purpose. The object has been to write a comprehensive account for the record, not a popular story* However, this matter might well serve as source material for such a story, if one should be written later on. The order of sequence is roughly chronological, and the text is divided into chapters. But the purpose of this division is chiefly to break up a long story into parts. An outline of CONTENTS, which can serve as a guide in finding items of interest, begins on page 379, and a list of ILLUSTRATIONS on page 397. ETc 36796 Report OC-83 CHAPTER I THE BEGINNING In 1916, Charles F. Kettering set up an institution called the Dayton Research Laboratories Company. And, at Hr. Ket tering's invitation, Dr. F. 0. Clements, who fifteen years before had been his instructor in chemistry at the Ohio State University, resigned his job as chief chemist of the National Cash Register Company to become the technical director of the new organization. This institution was organized to undertake the kind of pioneering research that Hr. Kettering had found it difficult to get done at the Dayton Engineering Laboratories Company (Delco). That organi zation had become a manufacturing company with the usual host of commercial problems to solve. It was thus to get the isolation needed for pioneering research that hr. Kettering founded the new organization completely removed from manufacturing problems. The subject of fuel was the one in which L!r. Kettering's interest primarily lay. Before the New York Section of the S.A.E. in February, 1919, he spoke as follows about the founding of the new laboratory: "Some three or four years ago, we started a little laboratory over home, just a sort of playhouse in which to study, from various angles, the application of fuel to an engine. We in tended to do this studying in about the same spirit as a nan plays golf, but I don't think we used the same proportion of profanity as is used in that game*" L ETC 36797 Report 0C--83 Thomas Hidgley, Jr., was employed as the first member of the technical staff of the nev; laboratory. Prior to this, on a trip v.'hich Dr. Clements had made to Cornell University in search of personnel for the National Cash Register Company, he had chosen lidgley from the men graduating that year as a suitable man for a place on the staff at "The Cash," and Kidgley had later been given a job there by general manager E. A. Deeds. However, just before he was assigned to the Dayton Research Laboratories as the first member of its staff, Llidgley had been work ing on mercury-cooled exhaust valves for !ir. Kettering at the Domes tic Engineering Company (later the Delco-Light Company). It yv_.3 o there also that he first began to investigate the bugbear of fuel knock in engines; and it was partly ns a. result of early events in this study that Lr. Kettering decided to found the new research laboratory. Lidgley's first work in the study of knock was done with the aid of a Dobbie-Ilclnnes engine indicator made in England, which Llr. Kettering had bought earlier and stored away against the time when it could be put to just that use. For the problem of knock in engines was one which had first troubled iir. Kettering about 1911 in connection with his work on bat tery ignition for cars. Because of the rapid increase just then in number of cars in use and the consequent need to make more gasoline out of each barrel of crude oil refined, gasoline became less vola tile and at the same time worse in degree of freedom from knock. So the magneto makers, with whom llr. Kettering was competing, made the claim that the cause of the knock was his new battery ignition. Report DC-83 2 Thomas Liidgley, Jr., was employed as the first member of the technical staff of the new laboratory. Prior to this, on a trip which Dr. Clements had made to Cornell University in search of personnel for the National Cash Register Company, he had chosen Hidgley from the men graduating that year as a suitable nan for a place on the staff at "The Cash," and liidgley had later been given a job there by general- manager E. A. Deeds. Hov.-ever, just before he was assigned to the Dayton Research Laboratories as the first member of its staff, Uidgley had been work ing on mercury-cooled exhaust valves for Ur. Kettering at the Domes tic Engineering Company (later the Delco-Light Company). It was there also that he first began to investigate the bugbear of fuel knock in engines; and it was partly as a result of early events in this study that la*. Kettering decided to found the new research laboratory. Uidgley's first work in the study of knock was done vdth the aid of a Dobbie-Uclnnes engine indicator made in England, which Ur. Kettering had bought earlier and stored away against the time when it could be put to just that use. For the problem of knock in engines was one which had first troubled Hr. Kettering about 1911 in connection with his work on bat tery ignition for cars. Because of the rapid increase just then in number of cars in use and the consequent need to make more gasoline out of each barrel of crude oil refined, gasoline became less vola tile and at the same time worse in degree of freedom from knock. So the magneto makers, with whom Hr. Kettering was competing, made the claim that the cause of the knock was his new battery ignition. ETC 36799 Report 0C-S3 3 And now age.in, 5 years later, in the effort that he was then making to develop a farm-power engine to run on kerosine, knock was troubling Ur. Kettering once more, and to an even greater degree. This came about because, in order to comply with the re quirement of the fire underwriters that no more than one gallon of gasoline be kept at a private residence, he had to run an engine on kerosine that originally had been intended to bum gasoline. This meant that, if knock was to be avoided, the compression of the en gine would have to be reduced, with corresponding loss in power and efficiency. And so, vath the nev/ly developed Delco-Light engine and an indicator, Uidgley began to study the knock. The object was of course to find out how to eliminate it. With his indicator--he soon made a modified one after some of his own ideas--Uidgley got his first indicator card, a pressure-volume one, on November 16, 1916, The first such card showing knock he got the next day, on November 17. This card demonstrated that knock was not due to, or was not accompanied by, preignition, as had been generally supposed, but that the disturbance of knock came several degrees later than the ignition spark. Tliis observation is well illustrated by the indi cator cards. Figure 1, page k, but taken at a later date. Compare the pressure-time record of knock (middle card at the left) with that of preignition (bottom card at the left). In speculating about why kerosine knocked so much worse than gasoline as it was observed to do, Kettering and Uidgley reasoned as follows: The chief difference between a kerosine and ETC 3 6 800  PO" oc - a > 4 FIGUKE I SOVIE '- = iC4L CA^DS TAKEN WITH THE MIDGLET OPTICAL GAS ENGINE I NO IC* TOK , AND SHOWING ClFFERENCES BETWEEN NONKNOCKING COMBUSTION, knck.ng cc'3j:tion, anc combustion in which preignition is present. etc 36801 Report OC-S3 5 a gasoline, so long :s both were made from the same crude oil, was in respect to readiness to vaporize. They supposed that gasoline evaporated easily and completely as it entered the combustion chamber, forming there a homogenous mixture with air, which accordingly burned smoothly and uniformly. But kerosine, being less volatile than gaso line, they supposed to persist in part as minute droplets, even during a portion of the combustion period. They then isggined that at the point where the piston began to recede on the expansion stroke, and so to relieve the pressure somewhat, all the minute globules of kerosine'vaporized rapidly or all at once under the high tempera ture present at that time, and thus burned at the same instant. It was that instantaneous combustion, they thought, which produced the knock. On this basis tfoy reasoned that if the droplets were to be dyed some dark color--like the rusty leaves of the trailing arbutus, which blooms in the spring even before the snow has gone--the fuel fog would then absorb more radiant energy, and so should be vapor ized soon enough to prevent the trouble of knock. Iodine, the First Antiknock Agent It so happened--and fortunately, as will later appear-- that when Liidgley attempted to test out this theory no oil-soluble dyes were to be had. He went over to H.;R. ?,Tolf's chemical labora tory at Delco to try to get such a dye, and told his problem to Fred 1. Chase, who happened to be the only one there just then. Fred could find no oil-soluble dyes, but he reached up on the shelf, took down a bottle of iodine, and made the suggestion that iodine would probably color kerosine red. So iodine was tried and found to work ETC 36802 Report OC-33 6 woll as s dye. And v:hen kerosine that had been made red with iodine s ^ in the engine the knock did die out completely, and the first antiknock compound had been discovered. The date of this discovery is said to have been December 2, 1916. This date is taken from the chronology in Figure 2, page 7, which is a copy of a large chart prepared by Midgley about 1922 for use in a discussion of developments in the research on antiknock agents up to that tine. Some of the later dates given on this chart are not in precise agreement with records kept at the time* So all the dates given there are presumed to be merely approxi mately chronological. "Piping out knock by the simple expedient of dyeing the fuel red seemed so simple as to be hardly credible. So to make sure Midgley next got from H. C. Kcugey at the Lowe Brothers Paint Com pany some true dyes that were soluble in kerosine. None of these, he found, reduced the knock to any degree whatsoever, no matter how deeply the kerosine was dyed. The fine theory about the value of a dye for absorbing radiation, and so preventing the knock, was thus demolished. But there remained the important discovery that iodine did stop the knock. 127 North Ludlow Street The new research institution had for some time no place of its own in which to carry on its endeavors. The discovery of iodine as the first antiknock compound was made in the early engine laboratory located at the Domestic Engineering Company on the second floor of an etc 36803 RLPORT OC-83 DEVELOPMENT OF FUEL RESEARCH WORK Oct/,17/6 Storted v/ on mdicotbr Nov t6J7/6 Past Press-/a/ cord token Nov 17.17/6 P/rst Press - /a/ cord sAonny AnocA TA/s esfoA//sAed tAef the AnocA pos notprcyniAon as common/y supposed Dec. Z.17/6 P/ementot iodine tees discovered to Ae an anAAnocA compound TA/s esfaA/istied Hat a smo// amount of motenof cou/d A* odded to o p/e/ and prevent Anoc/my Jut/15. PI7 Nev indicator Aui/t to /aa/ifate warA Oct. /. P/7 Co-operation storied m/A Dureau o/ Af/nes an aviation /vet /or tear evarA Oct 22.P17 Cycto-tiexone teas Army firepared Cyc/o-Aexone run n a motor and /ot/nd to Ae a per/eef A/yA com/oress/on /us/.. Nov ft N/7 ioryer production of cyc/o-Aexone sforfed Discovery Mat fAy/ Iodide pas an entiAnocA June ft, 17/8 Pirst dbnomometor test mtti cyc/o-Aerone at Ate CooA /te/d. ZOO* compression. June Xtt/6 P/rst /AyAts vtM cycto-tiexone at ZOO* compression Any. I, P/8 PhyAfS m/A cyc/o-Aerone at Sou/A P/e/d Sept I, 17/8 PAoAt tnlA cyc/o -Aerane at NdAur Wr/oAt P/e/d jO/scoveru /Aat om/m pas an anAAnocA Discovery Mat artAo-jb/indine and xyttine pare asAtmaAt PeA to Jtmi Spent Aymy to yet cAaqe, so/uA/a onAAnecAtnf mtieyenoas compounds Jk/ty / /fit Co-aeerotiom at DuPbnt Co. osAed to secure ctieqe source a/ anAAnocA Jon. 15.1720 Dutint Co. storied researcA an/tome propayatievr, Don DmcA cor on /be/ cy/ disti/tote and anAAnocA Conception a* xr/ector me/tiod JuAy 15.1770 In/ector deveApment soAs/octory/or srsto/bAan on severs/ears Auy. IS, I7Z0 In/eeflon mc/Aod yenerady unsatislactory to mast users Srtomum orycAtortde discovered to Ae pover/u/ ontiAnocA Di-elAy/-to/turide discovered to Ae poper/u/ anAAnocA Hoy / IfZl Production at eti-e/Ay/- to/tonde storted Periodic /unction a/ anAAnocA moMr/o/s conceived Systematic nvestiyotion o/penodc /unction stortitd Hoy /7. fTZt 7 to I compression ratio CAerro/et comptofed Tn-fefto-e/ny/ discovered to Ae on anAAnocA conthary to expectations Oct JO, tftt 7esfS of CAevro/et 7-1 compression ratio c&npAtod and prove IOO % increase o/ mitooye Oct 20. tTZt Du/bnts /tome prvpayoAon resu/fo analyzed and dis eased the cause o/ the AnocA. Lead-tofta-e/Ayt discovery Jtbdy q/ production e/ Asad- tefto- etoyt storted 7 FIGURE 2 APPROXIMATE CHRONOLOGY OF EVENTS IN THE SEARCH FOR A PRACTICAL ANTIKNOCK AGENT ETC 36804 Report CC-S3 8 cid building in Dayton across Second Street from the main factory of Delco. Figure 3, pnge 9, is a picture, taken in 1939, of the building in which the iodine discovery v;as made. In the first half of 1917 a new plant, built at Moraine City as a hone for the Domestic Engineering Company, became avaiLable and it was intend ed to establish the laboratory in a corner of that building. But just then the United States entered the War in Europe and the new building had to be devoted to the making of airplanes by the Dayton-Wright Airplane Company, And so a large old residence at 127 Worth Ludlow Street in Dayton was rented and converted into a lab oratory. A building to house a machine shop was then constructed at the rear of the laboratory. Figure U, page 10, is the only known contemporary picture of the laboratory at 127 Worth Ludlow Street, The name of the institution was changed at that time from the Dayton Research Laboratories Company to the Research Di vision of the Dayton Metal Products Company. One reason for the change was the difficulty, amounting almost to an impossibility, experienced in securing the things necessary to outfit and operate the laboratory in the days at the outset of our participation in the World War. The Dayton Lietai Products Company, which was manufactur ing military supplies exclusively, had the priority classification necessary to command what was needed. The second member of the laboratory staff was H. C. Mougey, who had been for several years at the Lowe Brothers Paint Company, and who it was that gave Midgley the dyes to test after the discov- ery of iodine as an antiknock agent, as already related. It was on ETC 36805 r --o : '> FIGUkE. 3 IGGI,\E, AS THE FIRST ANTIKNOCK COMPOUND, VMS DIS COVERED i <4 bUILO Irii CN LAST SECOND STREET, DAYTON, OHIO. ETC 36806 Report OC-83 11 August 1, 1917, that Mougey joined the staff, and when he arrived at 127 N* Ludlow Street he found the new laboratory just in the process of being fitted out. There the fuel research was done for the most part in what had been the kitchen and the dining room of the ."lain residence, the engines having been located in the kitchen. Figure 5, P 12, and the dining room and butler's pantry having been the chemical laboratory. t iwfeiiMm tin >r ni ETC 36808 FIGURE 5 OELCO-tlOHT TEST ENII* IN THE KITCHEN ENGINE ROOM AT 127 NOSTWlUDLO* SUHEET. feXMYEO Olt/THE ENGINE > AN EARLY VIOOEL Of THCJttMK.1T OWl^l^CATOR^rHC P-vLSSURE ELE MENT or whi'fJfrooaajE-iicrNNEs incicaton. - f ...1 >-m' ; r Report OC-83 13 CHAPTER II THE VJORLD "JAR--AND "HECTER" The United States being then in the World War, there was an insistent demand for a better fuel for our fighting planes. Enough reputation from their researches on fuel and knock had al ready come to Messrs. Kettering ind Midgley to cause the Bureau of Mines, with the backing of the War Department, to enlist their aid in searching for a more nearly knock-free airplane fuel. Messrs* E. W. Dean and Clarence Netzen of the Bureau of Mines, in their pa per, "An Investigation of Airplane Fuels" (S.A.E. Jour., , 126, August, 1919), published about two years later, said this: "The work of the Dayton Research Laboratory had shown the necessary characteristics of fuels capable of standing higher compressions . . . and it seemed that this investigation could be applied with great advantage to the aviation fuel problem. It was arranged that the Bureau of Mines and the research division of the Dayton Metal Products Co, should cooperate in ascertaining what fuels cap-, able of standing high compressions were most de sirable and most practical." And so, with the moral and financial support of the War Department, the Research Division of the Dayton Metal Products Coa* pany began a cooperative endeavor with men from the U. S. Bureau of Mines (Messrs, E. W. Dean, Chester Naraaore, Clarence Netzen, and John P. Smootz) in the search for a better airplane fuel than the straight-run Pennsylvania-base gasoline , of about 55 octane number then used. This arrangement is understood to have become effect ive on October 1, 1917. 3681 etc Report OC-83 14 Just prior to this date, Dr. A. R. Albright, an organic chemist, had been added to the staff of the Research Division to helo Midgley in his endeavors. The first entry in Dr. Albright's record (Record 1)* is headed "Preliminary Work" and relates to a test, made in a one-cylinder Liberty engine at the Dayton Engineer ing Laboratories Company, of TOT added to gasoline as a possible means of boosting' power. The TOT experiment did not yield any useful result.- But aany other fuels and combinations of fuels collected from a variety of sources were tested both in the Delco-Light engine at 127 N. Lud low Street and in the one-cylinder Liberty engine at Delco supplied by the War Department and operated by Netzen and Smootz of the Bur eau of Mines. This engine is pictured in Figure 6, page 15. The many fuels tested in this survey included gasolines from several types of crude, both domestic and foreign; gasolines made by differ ent cracking processes; blends of alcohol in gasoline, of benzene in gasoline, and of alcohol, benzene, and gasoline; as well as differ ent alcohols, ethers, and aromatic hydrocarbons without admixture. Among the many fuels tested was one from Henry Ford called "H. Ford's Knocknocker." Where Mr. Ford got such a fuel is not known, but being highly unsaturated--it was yellow in color and had a high ly cracked odor--it was fairly free from knock. From this survey it was found,- in brief, that of fuels which could be had commercially at the time some California gaso lines would have permitted a boost in engine compression of over * The records referred to by number in parenthetical references tiu.iv numbered record ETC 36811 figuke o ONE -C ^ i rii. Eft LIBERTY ENGINE AT DELCO, USCO 8V BUREAU OF MINES MEN for TESTING AVIATION ENGINE FUELS OUR INS THE WORLD WAR, 1917-Id. THE ENGINE IS FITTED WITH THE EARLY MOOEL OF THE MlDGLEY OPTICAL INDICATOR, AS PICTURED IN FIGURE 5. ETC 36812 ne ratio, as would also some cracked gasolines. Blends of ben-- zcnG no*r alcohol with aviation gasoline would have permitted larger boosts still. For use in airplane engines, however, each of these acre nearly knock-free fuels, except the California gasoline, had certain drawbacks. Thus benzene freezes at about 2+0 deg. F., and it is so high in carbon content that by itself it did not always bum clean; and so there was fear that it might cause spark plugs to short out from deposits of fluff carbon. Alcohol was too low in B.t.u, per pound. The cracked gasolines of the time were thought too liable to oxidation and gumming. It was accordingly recommended that California gasoline be used for fighting grade airplane fuel* But for some reason, not easy to understand, that reconnendation was not acted upon. Just after the joint investigation had been begun, gaso I line from a German airplane captured by the French was examined on the other side and reported to contain cyclohexane. This informa tion was cabled across the Atlantic; and, because German airplane engines were known to have higher compressions than ours, an effort to make some cyclohexane for test by hydrogenating benzene was begun immediately. It was later found that, although the German gasoline did apparently contain some naphthene hydrocarbons, very little cyclohexane was included. In the Bureau of Uines paper mentioned above (S.A.E. Jour*, 5, 128, August, 1919), the following is said: "A review of the properties of this hydrocarbon (cyclohexane) indicated that it might be exactly the fuel that was required for high compression engines. It was believed that in spite of their reputed ef ficiency the German engineers had 'missed a bet.' Experimental work on the hydrogenation of benzol ... developed shortly into an activity that proved highly interesting and important.1' Report OC-83 17 It was at 5 P.M. on October 22, 1917, that work was be gun In an effort to make cyclohexane by hydrogenating benzene (Record 1). Nickel oxide was used as catalyst, and ordinary com mercial benzene was the raw material. But the record was "No re sult-," although Kidgley, Netzen, Sraootz, and Albright worked all night-. This failure appeared to bear out a prediction made by Dr. Leo H. Baekeland, who, as a member of the Naval Consulting Board along with Mr. Kettering, had contact with the endeavor. Dr. Baekeland had advised against the attempt and offered to give the group a wooden medal if they could make a pint of cyclohexane. But on October 25 Dr. Albright went to The Ohio State University to look up methods of hydrogenation in the library there. And on October 26 a second trial was made* This time the benzene used had been carefully purified by washing in acid and alkali, and the catalyst used was nickel oxide spread on pumice.' A yield of "about 2355" cyclohexane was obtained.. Then on November 7 some of the cyclohexane produced was run in the Delco-light engine and gave "no knock." On November 8 a freezing curve of cyclohexane and of its mixtures with benzene was determined. Cyclohexane by itself o. was found to freeze at about the same temperature as benzene, i*0 P.j but at 80 cyclohexane and 20% benzene an eutectic of freezing point 400 below, zero was found. This eutectic mixture was given the name "Hecter." A larger hydrogenating tube was built and on December U the 10th gallon of 80% cyclohexane (was) finished about 10 P.M." Incidentally, from the first cyclohexane made, a liter bottle of it was presented to Dr. Baekeland in a plush lined mahog- ETC 36814 Report OC-33 17 It was at 5 P.U. on October 22, 1917, that work was be gun in an effort to make cyclohexane by hydrogenating benzene O (Record l). Nickel oxide was used as catalyst, and ordinary com mercial benzene was the raw material. But the record was nNo re sult-," although liidgley, Netzen, Sraootz, and Albright worked all night-* This failure appeared to bear out a prediction made by Dr. Leo H. Baekeland, who, as a member of the Naval Consulting Board along with Mr. Kettering, had contact with the endeavor. Dr. Baekeland had advised against the attempt and offered to give the group a wooden medal if they could make a pint of cyclohexane. But on October 25 Dr. Albright went to The Ohio State University to look up methods of hydrogenation in the library there. And on October 26 a second trial was made. This time the benzene used had been carefully purified by washing in acid and alkali, and the catalyst used was nickel oxide spread on pumice.' A yield of "about 23?" cyclohexane was obtained.'. Then on November 7 some of the cyclohexane produced' was run in the Delco-light engine and gave "no knock." On November 8 a freezing curve of cyclohexane and of its mixtures with benzene was determined. Cyclohexane by itself o. was found to freeze at about the same temperature as benzene, U0 F.j but at 80? cyclohexane and 20? benzene an eutectic of freezing point 40 below, zero was found. This eutectic mixture was given the name "Hecter." A larger hydrogenating tube was built and on December U the 10th gallon of 80? cyclohexane (was) finished about 10 P.M." Incidentally, from the first cyclohexane made, a liter bottle of it was presented to Dr. Baekeland in a plush lined mahog- Etc 3 6 *is Report OC-83 18 any box, which is still one of his prized possessions. At the same time he was given a suggested design for the wooden medal he had promised to present to the group. This design is copied as Figure 7, PaS* W. On January 7 it was decided to build a still larger hy drogenation furnace, and on February 18 hydrogenation work was be gun again. The new furnace was located in the northwest room down stairs at 127 N. Ludlow St*--in the room which had been the kitchen of the north apartment of the old residence. Figure 8, page 20, is a picture of the hydrogenation furnace and controls taken at a later time. Russell Wells was the operator. But Midgley and the men from the Bureau of tines were busy with many things, and the effort to hydrogenate benzene did not go at all well, the amount of cyclohexane made having been far below that expected. So, on June 6, 1918, T. A. Boyd, who six weeks before had been added to the staff of the Research Division, was taken off the physical testing of airplane parts and put to work on fuel problems. Ke was asked to make the hydrogenation of benzene to cyclohexane work successfully on the 5-gallon-per-day scale then being attempted. (Just prior to this Dr. A. R. Albright had left to go to the Du Pont Company.) The reasons why very little output was being obtained were that the two difficulties, (1) that of purifying the benzene and (2) that of preparing a suitable catalyst and keeping it active, had not been overcome. However, it proved possible to solve both of these problems rather well in about six weeks. The problem of purification ETC 36816 r rpORT OC-83 19 FIGURE 7 DESIGN SUGGESTED TO DR. LEO H. BAEKELAND FOR THE WOODEN MEDAL HE PROMISED TO GIVE MR. KETTERING IF HIS MEN COULD MAKE A PINT OF CYCLOHEXANE. IT WAS HANDED TO HIM ALONG WITH A LITER BOTTLE OF CYCLOHEXANE IN A PLUSH-LINED MAHOGANY BOX, AND IS INTENDED TO SUGGEST THE PLACE OF CATALYSIS IN THE HYDROGENATION OF BENZENE. -- ETC 36 811 ETC 36818 r? Report OC-83 21 was solved by passing benzene through spent catalyst--called a "dead catn__under hydrogenating conditions but without any hydrogenation of benzene occurring (Record A, p. 15, July 9, 1916), followed by washing with sulphuric acid and alkali. Later on, temperatures some what higher than that used for hydrogenation were found to give more perfect purification. New tests to determine the freedom of the treated benzene from sulphur were sought out and used also. The problem of catalyst was solved by the painstaking preparation of nickel oxide by persistently heating nickel nitrate until completely free of nitric oxide. Nickel silicate was being used at the start of Boyd's work, although nickel oxide had been used earlier. Experiments were made also with palladium, iron oxide, nickel oxide+cobalt oxide, nickel oxidefcerium oxide, and nickel ox ide tcopper oxide. But the most effective catalyst found was made from Uallinckrodt's commercial nickel nitrate. Catalysts prepared from Baker's c. p. nickel nitrate had, by comparison with those made from the commercial nickel nitrate, very low degrees of activity. The commercial nickel nitrate contained copper, iron, and cobalt as im purities. The percentages of cobalt and copper present were experi mentally increased at different times, but however with no apparent improvement in the effectiveness of the catalyst. On July 9, 1918, 50 gallons of Hecter (80 parts cyclohex ane and 20 parts benzene) was shipped to the Bureau of Standards for use in engine tests in their altitude chamber, leaving 30 gallons still on hand. Later, larger amounts were sent o_f to various places: over 200 gallons to licCook Field, 100 gallons to South Field, and 100 gal lons to Wilbur Wright Field. During the latter part of the endeavor ETC 36819 jtaport C&-&3 22 Hecter contained only 70 per cent cyclohexane, the change in compo sition having been made because of preignition difficulties experi enced in full-scale engine tests at McCook Field with the 80 per cent mixture of cyclohexane (S.A,E. Jour., 5, 129, August, 1919). The to tal amount of Hecter produced and used in airplane engine tests was around 650 to 700 gallons of 70 per cent cyclohexane (Record 4, pp, 15 and 41). The best yield of Hecter (70 cyclohexane) obtained in any one 24-hour run was about 28 gallons (Record 7, Nov. 7, 1918). This production was obtained in a furnace designed originally to pro duce 5 gallons per day. The Hecter thus made was subjected to a variety of tests in airplane engines; to dynamometer tests at McCook Field and at the U. S. Bureau of Standards; to flight tests at McCook Field, Wilbur Wright Field, and South Field; and later on to altitude chamber tests at the U. S. Bureau of Standards (Report No. 90, N.A.C.A,). It was found that the use of Hecter would allow a boost in the compression of airplane engines from 55sl, then generally used, to about 8:1. From the results of all these tests, Hecter was judged to be so far superior to the conventional aviation gasoline of the time that in early November, 1918, plans were completed for building a plant large enough to produce 300 gallons of Hecter per day, and capable of extension to any amount desired. But the Armistice, which came just at that time, caused the plan to be dropped. It was estimated that the cost of producing Hecter would not be above 50 cents per gallon, and that it would probably be around 40 cents per gallon. In cidentally, it was in connection with the tests of Hecter at McCook ETC 36820 23 Field that the high-compression engine was run on gasoline, thereby producing the historic damaged pistons and connecting rod, Figure 9, page 24. On Nov. 7, 1918, the following entry was made in the cy- clohexane log book: "Cyclohexane will never win this war." Also in the log for November 11, 1918 (Armistice Day), is carefully printed the following entry: "Shut down 10 P.M., November 11, to 8:30 A. U., ----Vo. 12, acc. holiday." And Jotted just above this was the fol- "Some holiday--Russ Wells." Following the Armistice in November, 1918, the work on ane was continued for a while, chiefly in the making of pure ane (about 70 gallons of substantially 100 per cent cyclohex- prepared), and in the fractionation of 100 per cent cyclohex- ind what other hydrocarbons might be present. Of the various items of written matter relating to the k during the War, including the cyclohexane endeavor, the prehensive was the unpublished treatise: "A Report of Fuel Work by the Research Division of the Dayton Uetal Products and the U. S, Bureau of liines,' Dayton, Ohio, July 27, 191." e important items of information included in this report was sical observation that ethyl ether and normal butyl alcohol, ve precisely the same ultimate chemical composition, C^HjqO, inctly different chemical constitutions, differ widely in f freedom from knock. Zther knocks badly, whereas butyl alco- ery good in respect to freedom from knock. These same com- llustrated the important fact that a very volatile fuel (ether) <- ETC 36821 i . ETC 36822 Report OC-83 25 nay knock more than one not so volatile (butyl alcohol). Some of the results of these fuel studies and the cyclohexane endeavor were later published.* The unpublished treatise, BA Report of Fuel Research Work by the Research Division of the Dayton Metal Products Company and the U. S. Bureau of Mines," July 27, 1918, contained a section entitled "General Description of Fuel Research Work*" From that section it nay be worth while to quote the following, because it shows that the problem of eliminating knock, and the advantages of improved power and economy to be gained by doing so, were pretty clearly understood at the outset: "Engineers have heretofore believed knocking to be the unavoidable result of too high a compression, and while the fact that alcohol did not knock at extremely high compressions was well known, it was attributed to its extremely high ignition point. That higher com pressions are desirable from the standpoint of output and economy has been universally recognized by engin eers. It was also believed that compressions higher than those now in use on airplane motors could not be used with fuels of high heating value, because of vio lent knocking. From the results of our investigation we seriously doubted the truth of the above accepted belief. Attention was then turned to the effect of various hydrocarbons and other compounds on the knock, and it was soon discovered that the chemical structure of the fuel played a much more important part on the knock than the volatility, although the latter exerts a very large influence on fuels belonging to the same series of hydrocarbons." *"More Efficient Utilization of Fuel," Charles F. Kettering, S.A.E* Jour., A, 263 (April, 1919); Statement of Mr. Kettering, S.A.E. Jour., 5., 197 (September, 1919); and "The Combustion of Fuels in the Internal-Combustion Engine," Thomas Midgley, Jr., S.A.E. Jour., Z 189 (December, 1920). Also the following U. S. patents relate to the cyclohexane endeavor: 1,446,984, February 27* 1923, Thomas Midgley, Jr., Method of Revivifying Spent Catalysts and Apparatus Therefor; 1,467,905, September 11, 1923, Thomas Midgley, Jr., Hy drogenation Furnace; 1,491,998, April 29, 1924, Thomas Midgley, Jr., Fuel. ETC 36823 Report OC-63 24 From this quotation it is apparent that the objective of the research on the elimination of knock was considered to be a gen eral one. From the start of the research on knock initiated by Mr. Kettering, the interest was not limited to solving the then immedi ate problem of knocking in the Delco-Light engine. It was recog nized that the problem applied to automobile engines and airplane engines as well. For, as before said, it was in the automobile that lir. Kettering first experienced the bugbear of knock. That was around 1911 during his introduction of battery ignition and the elec tric self-starter. But, just at the time when the above was written in the World War year 1918, the research was, of course, aimed pri marily at eliminating knock from airplane engines. There was an interesting sequence to the preparation of the before-mentioned treatise dated July 27, "A Report of Fuel Re search Work by the Research Division of the Dayton Metal Products Company and the U. S. Bureau of Mines." As before said, this report was not published, it having been prepared during the War for the information of the aviation branch of the Army. Of the several copies made, two were however sent to the aircraft authorities in England. One went to the Aeronautical Inspection Dept. Laboratories in London,and one to the Chief Chemist, Department "H", Royal Air craft Establishment, South Fairborough, Hants, England. Aside from the description of the research on cyclohexane, this report had in it a great deal of intimate information on the relationship of fuel composition or structure to freedom from knock. It was surmised that the report was seen by Harry R. Ricardo, who was attached to the Air ETC 3682A liinistry* 40(1 that he used it as a or inspiration for the ^ which he did later with the support of the Asiatic Petroleum Company and published in the Automobile Engineer (London) as a series of 7 papers beginning early in 1921 (11, 51), entitled "The Influence of Various Fuels on the Performance of Internal Combustion Engines." This work of Ricardo's purported to be an altogether original and pioneer endeavor, and thus caused some re sentment on the part of some of the men who participated in the early fuel studies mentioned above. Of the men who worked on the cyclohexane endeavor, John P. Smootz is now with the Standard Oil Comoany of Ohio, Clarence Netzen died of flu in December, 1918, and Russ ?Tells died about 1934. A. R. Albright is now with the Hecker Products Cor poration in Indianapolis. Another man who operated the hydrogena tion furnace a short time on one of the shifts was W. A. Goechal,. whose present whereabouts is not known. Still another man who worked on the hydrogenation fur nace during the summer and fall of 1918, when it was being run 24 hours a day was VT, K. Gilkey. One night, when Gilkey was there alone, he spilled concentrated sulphuric acid on his trouser legs due to the breaking of a 5-pint bottle of the acid. Instead of stripping the trousers off and wiping off the acid first, as he should have known to do, he ran water on the trouser leg right away in the effort to wash the acid off. The result was that the acid, heeted by the water, burned his legs so badly that he was laid up for some considerable time. ETC 36825 Report OC-83 28 There was another man too, mention of whom should not fail to be made, Carroll A. (Ted) Hochwalt. Hochwalt worked in the laboratory and on the cyclohexane endeavor during his summer vacation in 1918. He was back again at the Christmas vacation. and also during the summer of 1919t Then in June, 1920, when he graduated from college, Hochwalt Joined the Fuel Department staff as a regular member and made important contributions to be men- also on this jotb that Uidgley met with an acinteresting outcome. One of the fusible plugs : (bismuth, tin, and lead) accidentally blew out, 0 particles of the finely divided metal into the is eyes. He went to the eye doctor, who told him too widely scattered and that it was located in cate to be picked out. The doctor tried treate cornea, but with little benefit, "and," quoting une 26, 1919, which Midgley wrote to E. J* Crane, f his and now editor of Chemical Abstracts, "after of nuisance, I decided that there were two possible ut quickly: one of which was to heat them up until he other was to use mercury and dissolve them out. th my doctor in the matter, he felt sure that the [ to melt them out would destroy the cornea; so this er attempted. He gave his consent to the use of sed in an eye cup, redistilling and cleansing the inary way with dilute nitric acid and using fresh ETC 36826 Report OC-83 29 mercury at each application. This procedure gave immediate relief from irritation and, inside of two weeks, every piece was out and gy eye was restored to normal condition." This story impressed E. J. Crane so much that he wrote an account of the accident and its interesting outcome and published it in Industrial and Engin eering Chemistry (11, 892, September, 1919). The making of cyclohexane by hydrogenating benzene was discontinued on November 18, 1918, one week after the Armistice and somewhat over a year after it had been begun. But, as before said, the work on preparing a quantity of pure cyclohexane and on deter mining by means of fractional distillation what other hydrocarbons were present in the product of hydrogenating benzol was continued on into January, 1919, and even later. As supplementing fractionation in the effort to determine what other hydrocarbons were pres ent in cyclohexane, the method of T.C.D's, or temperatures of criti cal dissolution with aniline, was used. This method, which was in tended to distinguish among paraffin, olefin, naphthene, and aro matic hydrocarbons was based on the War work of Chavanne, Simon, and Dort, as published in Conptes rendus, 168, 1111 (1919), but was given to us prior to publication by Ur. Robert G. Dort, who by that time had returned from France and was located at UcCook Field, All the work on cyclohexane soon came to an end, how ever, and meanwhile other lines of endeavor were gradually taken up. Thus at the end of December, 1918, work was begun in the search for flux and for a core sand binder which would permit the casting of engine cylinders with copper fins. However, these experiments. $ .< ETC 36827 Report OC-83 30 which were thus begun as a side-issue at the outset of the extensive work in the development of a copper-cooled engine, were not pursued very long in the Fuel Section. The problem of making copper-finned cylinders was given to another group, which solved it successfully. In the period, November, 1918, to January, 1919, prac tical tests were made of a 50-50 mixture of kerosine and benzol as an automobile fuel. The car tests were run by John Sheats in his 1917 model Dodge and later laboratory tests were made by Boyd. In the report of these tests, January 10, 1919, it was said that the performance of the engine was the same as it was on the gasoline of the time, but with two exceptions, viz, that at 0F the benzene froze and separated from the mixture and that the engine did not idle so well on the blend as on gasoline. A patent on the use of mixtures of kerosine and benzol as a fuel for internal-combustion engines had been applied for on January 7, 1913, by Thomas Midgley, Jr.- It was issued on ilarch 11, 1919, No. 1,296,832. Incidentally, the ''Liberty Fuel" proposed by the Bureau of Standards in 1918 is believed to have been a mixture of kerosine, about 65 parts, and benzol, about 35 parts (Record 9, page 65). Other Events of the War Period During the period of research on cyclohexane some work was done also in searching for an antiknock agent similar to iodine but not suffering from the defects of iodine. On December 29, 1917, (Record 1), Dr. Albright tried iodoform, but made no record of its effect except this: "something wrong with intake." Then on April 9, ^918, sixteen months after the discovery of the antiknock effect of TC 36828 Report OC-83 31 iodine, Dr. Albright recorded: ''Mixture of small percentage of ethyl iodide in kerosine found to depress greatly fuel knock in 75 lb. compression head engine" (Record 4). Within the period after October 1, 1917, when, as before said. Record 1 of the Fuel Section begins and before the record about the effect of ethyl io dide just mentioned, Dr. Albright's records show that he tried the effect upon knock of camphor, ethyl acetate, nitrobenzene, halowax oil, cresol, aluminum chloride, ethyl chloride, and diphenylamine* He recorded that camphor seemed to help knock slightly. How he missed finding the considerable antiknock effect of diphenylamine, which was later found to be an effective antiknock agent, is not known. But in his record of the testing of diphenylamine on Janu ary 23, 1918, he did not mention it as having antiknock effect, and he apparently did not report it otherwise. Dr. Albright tried also the effect upon knock of plating cjiinder heads with copper and with nickel. According to his entries in Record 1, he tested also the following "colloidal" metals made by arcing between poles of the metal immersed in kerosine: copper, nickel, cadmium, and tin. Of copper and nickel he recorded once (March 7, 1918) that knock was decreased. He there indicated that this test was observed also by Messrs. Thomas Kidgley, Jr., F, 0. Clements, and J. H. Hunt. But later, April 8, 1918, with "concen trated" solutions of copper, cadmium, nickel, and tin he recorded: "knock not appreciably affected." However, Dr. Albright seems to have concluded that the colloidal metals were effective antiknock agents. On June 30, 1926, ^ ETC 29 Report OC-83 32 he wrote a letter to the editor of Industrial and Engineering Chem istry, (18, 985* September, 1926), in comment upon a paper about spectroscopic work by Clark and Thee in which he said: "The princi pal fact here to be recorded is the discovery by the writer that finely divided metals do exert a positive repressing action upon detonation of gaseous mixtures in gasoline engines," There he says also that "A large number of metals were tried; all the common ones, and several of the rarer," He says, further, that "colloidal" cop per gave the most promising results. There were two other events that occurred during the period when Dr. Albright was on the staff that are perhaps worthy of mention.i One was his making for Orville Wright a manometer 12 feet in length. It was Orville's intention to use in this manometer two liquids differing in specific gravity by only 0,1. And one of the early jobs given to Boyd after he joined the Fuel Department in June, 1918, was to search for suitable liquids to use in this man ometer. Several were tried, and the two settled upon were water for one side and a mixture of halowax oil and kerosine of sp. gr. 1,100 for the other. These liquids were partially successful, but the problem not solved was how to keep the manometer tube in such con dition that the dissimilar liquids would not begin to stick to it in parts touched alternately by one and the other. The other event was the trip of Uidgley and Netzen to Terre Haute, Indiana, on November 2, 1917, to investigate the pro cess of some alleged inventor there who said he was making gasoline i ETC 36830 Report OC-83 33 out of kerosine. His process was apparently nothing more than to pass natural gas through kerosine. The investigators suspected the common deception of a secret valve and hidden source of gaso-- line, of course, and so they stayed by the process continuously day and night, only one of them going away at a time for meals. Finally the "inventor" broke down and said: "I cant make this process work if you fellows are going to stick around here all the time." And so Midgley and Netzen went back to Dayton to make Hec- ter instead. vidgley Indicator Improved and Manufactured for Sale In the summer of 1917 an improved form of the indicator on which ULdgley had done his early work was constructed. It was an optical indicator so made as to project pressure-time cards on a glass screen at the front by means of a beam of light. This is presumably the indicator shown in Figure 5, page 12, mounted on a Delco-Light engine in the kitchen engine room at 127 N, Ludlow Street, and also mounted on the one-cylinder liberty engine at Del-* co, Figure 6, page 15, used in the war work of Netzen and Smoots, ("A Report on Fuel Research Work," etc., July 27, 1918). Some of the cards taken with this indicator are contained in the report just cited and in the paper, "More Efficient Utilization of Fuel," by Charles F. Kettering, S.A.S. Jour., k, 263 (April, 1919). While this indicator was very useful, it stiffred con siderably from inertia effects, and so gave rough, jagged cards. Later, during 19IS and 1919, a further improvement was made in it idiich was worked out through the help of John Sheats. Figure 10, 3L, is a picture of the indicator as finally developed, mounted ETC 36831 Report 0C-S3 3-5 on a one*-cylinder engine. This new indicator was much freer from inertia effects than any made up to that tine. It gave the kind of cards, both pressure-tine and pressure-volune, shown in Figure 1 page 4, and was used extensively in the studies of knock for a period of several years. It was named the ildgley Optical Gas En gine Indicator. A fine leather-covered descriptive booklet, "The Hidgley Gas Engine Indicator," was prepared and printed during the lat ter part of 1919. The preparation of this booklet took some night work on the part of the Fuel Depr ment staff, and it also inter fered somewhat with the search for an improved fuel. The Midgley Indicator was later manufactured for sale at a price of $750.00. A considerable number of them were sold, a special group in charge of 71* S. V.'hittaker, who is now general manager of the Inland Manu facturing Company, having handled the distribution and servicing of them. The Midgley Indicator was described too in a published paper, "High Speed Indicators," Thomas Midgley, Jr., S.A.E. Jour., 15, 317 (April, 1920). The indicator was patentedF*l,490,223, April 15, 1924, Thomas Midgley, Jr., Indicator. Also in December, 1925, the Franklin Institute awarded to Midgley for this develop ment the Edward Longstreth Medal (Jour. Franklin Institute, 201, 123, January, 1926). ETC 36833 Report OC-83 34 CHAPTER III SEARCH FOR All ANTIKNOCK AGENT RESUMED The search for effective knock suppressors, an endeavor 0n which nothing had been done for the several months during which the work on production of cyclohexane and Hecter was so intensively pursued, was taken up Again at the middle of December, 1918. The first compounds tested were a mixture of rosin and one of oleic acid in kerosine. Neither of these proved to be antiknock compounds. A large number of tests on various concentrations of methyl iodide and of ethyl iodide in kerosine were then made, partly for Boyd to gain experience in running the Delco-Light test engine and in observing degree of knock. At this stage in the search for an antiknock compound, degree of knock was judged by ear for the most part, although in special cases the Midgley optical indicator was used as an aid. The tests were made by the "Edisorian" method of "cut and try," as there was as yet no information upon which to base any other system of search. In selecting substances to try, oil soluble compounds were preferred. Solubility in kerosine was in fact an essential re quirement for such tests, unless the material was a liquid that could be fed to the engine independent of the fuel. A great many solid com pounds were tried, however. But tests of solid materials were never very satisfactory, beer-use ol the clogging of inlet passages and of the depositing of soli-ls on tl:a valves; and so compounds that were, soluble in kerosine or that wers themselves liquid were employed rever possible. Report OC-83 37 On December 20, 1918, water admitted as a liquid inde pendent of the gasoline was found to be a fairly effective knock suppressor. On December 31 liver of antimony dissolved in kerosine was found to be a very mild suppressor of knock. On January 29, 1919, the first metallic alkyl was run. It was zinc ethyl, made synthetically by Boyd, and was found to have no knock-sup pressing effect. At the same time another alkyl compound, also prepared synthetically and thought to be antimony methyl or trimethyl stibine, was tested and recorded as having had no antiknock effect. But this failure to find that antimony was an effective antiknock agent was an error, for antimony alkyls were later found to be more effective than aniline. Only 1.5 cc of the supposed trimethyl stibine was available, however, and it nay not have been the compound it was thought to be, or else the observation itself was wrong. At any rate, triphenyl stibine was later found to be an antiknock more effective than aniline on a molecular basis (Record 13, page 170), and it was patented, L. S. 1,575,439, Thom as Midgley, Jr., March 2, 1926. One cf the compounds tested early, on December 20, 1918, was hydrogen peroxide. The record made of the test of hydrogen peroxide in keresme was that thf engine knocked at every stroke (Record 8, page 6). So this was apparently the first instance of a knock inducer/ of wttch --everal were later discovered; although, perhaps due to low solubil^ ty of hydrogen peroxide in kerosine, it not then rav/vaina 1 is s Ion. cx inducer. Report OC-83 38 Th- Discoveiy On January 30, 1919, a very important observation or dis covery we* made, namely, that aniline is an effective knock sup pressor* The observation was first made by Boyd working alone and then checked in the presence of llessrs. Sheats, Gilkey, and Goechal. In tests of aniline run the next day, Midgley also was an observer of its effectiveness as an antiknock agent. (Record 8, page 17.) A'copy of the original laboratory record of these tests is included as Figure 11, page 39 Aniline was thus the second real antiknock compound to be discovered, Iodine--or iodine and its compounds--having been the I first, as already related. In a later comparison of the antiknock effectiveness of aniline by comparison with that of iodine, it was found that 2 cc of aniline was equivalent in effectiveness to 1 gram of iodine (Record 13, page 24). It is perhaps peculiar that the discovery of aniline as an antiknock compound was not made earlier, or right away at the middle of December, 1918, when the search for an antiknock compound was resumed. This seems to be strange because during the five or six weeks intervening, in which many compounds were run in the en gine in the search for an effective knock suppressor, aniline had en used in the T.C.D. method of examining hydrocarbons. method, as related earlier, aniline was employed as a means ing th? -cmpc3:Vioi. j*. '.he hydrocarbons other than cydo- Bresar.t in camp'e'-ely li/.'.r-wnated benzene. Aniline was. e available and it was known to be soluble in kerosine to Tee. But for some reason it did not get included among the ;* ETC 36836 39 m of JE/e/nente /ispfnocH fft/ce-Lifkr* Afo+*r. Preventers /*/f Otto - 7V*/- ;+~3o,m # > Obs***** *v/ 0 00 90 P i^T ^22 .At4 * ^ iUiSfti /_**r ^v*4ye4 Aitx> FIGURE I! COPY OF PAGE 17 OF LABORATORY RECORD NO. 8 ON WHICH THE DISCOVERY OF ANILINE AS AN ANTIKNOCK AGENT WAS RECORDED. ETC 36837 Report OC-83 4D compounds tested until the date given above. Mention may also be made again of the fact that, accord ing to his record, A. R. Albright tested diphenylaiaine on January 23, 1918/ just about a year before the discovery of aniline as an effective antiknock agent. But for some unexplained reason. Dr. Albright missed finding the considerable antiknock effect of diphenylamine, which as found later is about one and one-half times that of aniline. There is an impression that the discovery of aniline as an antiknock compound, although it did not itself ultimately turn out to be a thoroughly practical solution of the knock problem, did save the search for such an agent from being abandoned prema turely; It was understood that, since there were other things that needed badly to be done and since the search for an antiknock com pound better and more practical than iodine had so far shown no encouraging signs of success and might after all be merely a "wild goose chase," liidgley had been given instructions to the effect that the search for an antiknock compound might continue only for a short time more. Two weeks is understood to have been the period of grace set. If nothing promising were to be discovered within that time, the decision was that the search would have to be aban doned. It is Interesting to note here also that for one reason or another, as Records 8 and 9 show, no engine tests in the search for an antiknock compound had been made within the period from Janu ary- 1 to January 29, 1919. One reason for this condition, as well ETC 36838 hgeport CC-Q3 41 las for the two-weeks limit on further search, is perhaps implied in the following quotation from the monthly report of Dr. Clements to l). H. E. Talbott, Sr., of February 4, 1919: "Ur. Uidgley has ten aciously adhered to the opinion that it was possible to secure a socalled 'pill' to overcome motor knocks. The balance of the organi sation has given him very little encouragement," The various endeavors which interfered with engine testa during January, 1919, were those already mentioned* the search for a flux and core sand binder to permit casting copper-finned cylin ders; the purification and analysis of cyclohexane; the tests of 'mixtures of kerosine and benzol as a motor fuel; and in addition a [preliminary effort to make alcohols out of olefins in gasoline and ! kerosine by treatment with sulphuric acid and subsequent hydrolysis, as well as an effort to synthesize zinc ethyl and trimethyl antimony as possible antiknock compounds. But, in view of the verdict setting a time limit upon how much further the search for an antiknock com pound might continue, work was resumed at once in making engine teats of whatever further compounds happened to be available on the shelves [of the laboratory, downstairs and up, or which could be gotten readily, i It was on the second day of this "must" search that the antiknock ef fect of aniline was discovered. The event thus marks one of the sev eral occasions on which the element of luck has appeared to enter [largely into the history of Ethyl gasoline. Following the important discovery of the antiknock effect [of aniline, an immediate effort to get a semi-quantitative measure >f its effectiveness was made, and it was concluded (Record 8, page l>) that 3.5 per cent of aniline added to kerosine made a fuel etc 36839 Report OC-83 42 equivalent in degree of freedom from knock to the regular automo bile gasoline of the time (Ohio Red Crown). And, because the solui* bility of aniline in kerosine was so low that a 3.5 per cent mix ture of aniline in kerosine began to separate around 35 deg. F., a search was made for a suitable solvent to hold it in solution down to lower temperatures. Of the many materials tried for this purpose, amyl alcohol and amyl acetate were found to be best (Rec ord A, pages 101 and 102). Also the amine of toluene, toluidine, was prepared and found, as expected, to be somewhat more soluble in kerosine. Toluidine was also found to have an antiknock effec tiveness about equal to that of aniline. ' Attempts to prepare other nitrogen compounds were made, some successful and some not. Phenyl hydrazine was prepared and found to be an antiknock compound, and an attempt--unsuccessful-- was made to add amino groups to the unsaturated constituents of cracked gasoline by passing vapor-phase cracked gasoline (Ramage) and ammonia through a copper tube heated in an electric furnace, with and without catalysts. It is perhaps of interest to record, in passing, that the Ramage gasoline used in this attempt, which was a sample sent to Ur. Kettering for test, was some of the.early output of the process that later on became the basis of the "Qyro* cracking process operated by the Pure Oil Company and others* Bad Luck on Lead in 1919 And then on February 13 and 14* 1919, only two weeks after the discovery of aniline as an antiknock agent, occurred what was . perhaps one of the most unlucky events of the whole research that resulted finally in Ethyl. This was the complete failure of the m m m "mug ETC 36840 attempt made at that time to prepare an alkyl compound of lead in order to get an oil-soluble compound to test the antiknock effec- ,. A small amount of lead-sodium alloy was first nade by fusing the two metals together in a metallurgical muffle furnace. The product was then heated for a time in a flask with ethyl bromide. Next, the ethyl bromide was distilled off, and the residue was extracted with ether. But no ethyl lead was obtained. It is now known that if ethyl iodide had been used instead of ethyl bromide, which latter needs a catalyst to make it react, and if the product had been extracted with wet ether or if water had been added and the product then distilled out in the presence of steam, some lead ethyl would almost certainly have been obtaI*._-d. There would then have been a chance to observe the marvelously ef fective antiknock action of tetraethyl lead almost three years be fore the discovery was actually made in December, 1921. A further.- attempt to prepare tetraethyl lead was not made at that time, partly because there was then no particular reason to think that lead might be a good knock suppressor, but mostly for another reason. The other reason was that the man who made the alloy of sodium and lead did so in the muffle furnace up stairs in the center room at 127 N. Ludlow Street. This furnace was a part of the equipment used by H. C. Mougey* s department in making receiving inspections on the materials purchased by the sev eral companies which they were serving, including the Dayton-Wright Airplane Company. And, during the work on the preparation of the active alloy of sodium and lead, the operator had let the thermoco'iple in the furnace get into the sodium-lead melt and had ruined ETC 36841 Report OC-83 4* 1 it thereby rendering the furnace inoperative for a time, as there wa8 no other thermocouple available. This, as he soon found out, was an error utterly inexcusable to the men who had the furnace in charge. So inexcusable was it that he was not at all welcome to use the furnace any further. And so, since no particular brief could then be held for lead compounds as antiknock agents anyway, the investigation passed on to the testing of other materials, and the chance to discover the effectiveness as an antiknock agent of the essential ingredient of Ethyl gasoline almost three years be fore it was made was thereby missed. It is perhaps worth noting here that at least as early as January, 1919, when the record shown in Figure 11, page 39, was made, it was the intention to test suitable compounds of the various elements. This may be seen from the heading, TESTS OF ELEMENTS AS KNOCK SUPPRESSORS. It explains why the effort to get an oil-soluble compound of lead, as just related, was made so early in the search. For a while after the discovery of the antiknock effec tiveness of aniline a considerable amount of work was done in the effort to make amines by some cheap method. A few of the ideas ex perimented with, none of which produced useful results, were these (Record 9): Attempts to react anhydrous ammonia with olefins, with alcohols, with brominated and chlorinated hydrocarbons under pres sure, with the sludge obtained by treating olefins with sulphuric acid, and with kerosene in the presence of aluminum chloride. Experiments on Cracking Although not related to the search for an antiknock com pound, a great deal of work on cracking kerosene and gas oils was ETc 3684 2 Report OC-83 45 done during the same period also, it having been begun in March, 1919, and pursued at various times. These cracking experiments were carried out for the most part in electrically-heated tube furnaces of special design, and almost altogether in the vapor phase. In the fall of 1919 a large amount of experimentation was done on the cracking of kerosine, in which possible cracking cata lysts or "pills" were added to the kerosine before subjecting it to the cracking treatment (Report, week October 20, 1919, et seq). The materials whose possible effects as catalysts were tried con sisted of known antiknock agents, as well as many other compounds. Many different schemes were tried, including a plan to hydrogenate the olefins formed in the cracking process by means of hydrogen produced by passing water over hot carbon in a water-gas reaction* In the latter phases of this work (November, 1919),^the du Pont Company sent one of their men, Mr. H. A. Lewis, to the laboratory to carry out a series of experiments of this kind on their behalf. An extensive literature -study of cracking was made also which in cluded abstracts of all the literature, both patents and scientific papers, from 1907 up to October, 1919. No practical result came of all this work, except a use ful knowledge of cracking problems and some understanding of the effects of heat upon hydrocarbons. The cracking furnace was used also in preparing diphenyl by cracking benzene at very high teoperaItures. Later on, around 1923, after the antiknock properties of seIlenium had been discovered, Midgley and Hochwalt experimented with he effects of some compounds of selenium as cracking catalysts. ij'--** ETC 36843 Report 0C-&3 46 notably ferrous selenide, and they found such compounds to have a definite catalytic effect upon cracking, particularly in producing a high content of aromatic hydrocarbons. The results of this work were published as a paper, Ind. Eng. Cheo., 16, 365 (1924), and also patented, U. S. 1,721,523, Thomas Hidgiey, Jr., July 23, 1929. antiknock Agents Furnished to Others for the First Timd It was apparently during the week following Uarch 17, 1919, that aniline was first given to persons outside the labora tory for use as an antiknock agent. A mixture of 3.5 per cent aniline in gasoline was put into Ur. W. A. Chryst*s Essex car, in which he was having trouble from knocking. Knocking was a trouble that was characteristic of the Essex car which first came out that year, the engine having h'd higher compression than was usual for the time. Because of the good results in Ur. Chryst's car, there was then a further request to send some of the knock suppressing mixture to the Hudson Uotor Car Company, makers of the Essex car. And so a gallon of mixture containing the following ingredients was prepared for the Hudson people: Aniline Amyl alcohol Camphor Benzol to 1325 cc. 380 80 1 gallon The materials other than aniline were added to increase the solu- bility of the mixture in gasoline, and perhaps also to disguise the eonposition somewhat. The low solubility of aniline in gasoline is .jM*- -j.c. ETC 36844 47 iqiQ enough aniline mixture to treat 5 gallons of On U'.rcn 24, .ont over to the Domestic Engineering Company, fuel was als0 s papers of Delco-Light engines. As a matter of interest, record should be made of the fact that men at ilcCook Field and others were supplied with con siderable amounts of a fluid to be used as an aid in-starting cold engines, which was a very real problem around 1919 when the vola tility of gasoline was the lowest it has ever been. This mixture, suggested by Ur. Kettering, was called Kettering's Priming Fluid. It had the following approximate composition, and under proper con- * ditions was quite an effective aid in starting cold engines: petroleum ether 1335 cc. Benzol 2450 Total 1 gallon Later the composition was changed to the following: petroleum ether, 5065; sulphuric ether, 205?; benzol, 30% (Record 10, page 274). Beginning in April, 1919, and continuing for some time, a large amount of work was done in an effort to prepare cyanamide,- CN.NH2, or other nitrogen compound soluble in kerosine, from cal cium cyanamide. Calcium cyan;"ride was a nitrogen compound consser- cirlly available at comparatively low cost, being manufactured at Niagara Palls for use as an ingredient of fertilizers. It was ^'oug^t likely that if cyanamide could be obtained from calcium cyanamide it would be an effective antiknock agent and one that sight be made cheaply. But, although a great deal of ingenuity nd effort were applied to the problem over a period of several i, at times to the exclusion of all other work, no useful re- twas obtained. The reason why so much work was done on calcium TC 36845 Report 0C-3 48 cyanamide in the search for a cheap source of a nitrogen-containing antiknock compound was that at the then current price for aniline, 15 to 20 cents per pound, the direct material cost of adding 3.5 per cent of aniline to gasoline would have been of the order of 3i5 to hi5 cents per gallon of treated gasoline. Dr. W. C. Ebaugh, professor of chemistry at Dennison Uni versity, Granville, Ohio, joined the Fuel Section staff for the sumoer months of 1919. He engaged himself busily at work relating to the search for antiknock compounds, his various endeavors having included the following: assembling theoretical thermocheraical data on the addition products of benzene; joining in the experiments on calcium cyanamid by making a careful quantitative analysis of the raw material, b'r treating calcium cyanamid with benzene sulphonic acid, and by electrolysis of calcium cyanamid in water solu tion; and making a study of shale oil as a possible source of nitro gen compounds for use as antiknock agents. Dr. Ebaugh also brought from the stock of chemicals at Dennison a group of compounds to be tested as possible antiknock agents, among them diphenylamine which `\ was found to be quite an effective antiknockt, agent. This is the compound among those tested by Dr. Ai R; Albright during the winter [of 1917-18 which should have shown antiknock effect, but which ef fect--as mentioned earlier--he failed to find for some reason. The organization of the whole Research Division of the Jn Metal Products Company at about this time, the middle of 1919, shown in Figure 12, page 49 which .is a r jpy rf . extemporary or ation chart. etc 368 46 REPORT OC-83 '7CZ17S H. c. ICCl'SST ?^ad Cher-let lr uhirge of iuicral Chemi cal ork ani the Toutiae Testing Le.bcre.cries CHSKICAl. iirrrao La2C?--T02Y C. L. Petty Labora tory ASf't R. J. Vfirs-.ing is.'t Chcrdet l . C. Croms Aef't Chemist Cc-op. Student Fred Thaman Ass't Chemist Co-on. Student Franklin Stephens Helper PHYSIC.2. TEST ING LA30E;.?C?.Y THCii.s I2iiiEY. JR.. ITechar icel Rnffineer Greer E.Uarecha In charge of Dr Sting Room*, L' (chine Shop, Patent Att^X- Fuel Research, Refrigerator Re iearch, and General !iochani :al Prebleme. COBTROL A39 SHOP KEAECLjARISRS REFRIGEsATIOM S3SEARCH 1.HRCS2HS RESEARCH PURCHASES B.R.Sheibenb- C. >. GesVty J. G. Eing --In Charge Research Object: to de ger ternlne the Auditor G. h. leach Ase't Foreman C. P. H-Jdlpg Lech: r.ic C. ?.. Pope Kechnalc Engineer principles un derlying satis H. George factory utili Refrigeration sation of Design Heavy Fuels in the Internel- i'OTOB RESEARCH COEbU8tlOB Hotor. Clara Kramer Bookkeeper C. F. Spats P. A. and Re-v eeivlag Clerk Herman Baeye Mechanic Luther Doren Apprentice Charles Lee Superintendent Plant Thre. &'. B. Sarnahsv To collect data 0FFIC2 uertalnlng to The Ultivxte iicbel s. Greene Fuel of the Private See** ' Future" i Stenographer.. R. IT. Annla DRAFTING ROCK 2.Y.Hutchinton Ass't Mechenical Engineer --In oharge of all meter t<.ct ing. Dr.V.C.Ebeugh Industrial Chain Heliesa Stocked Stenographer Thomas A. Boyd Organic Chen. 9. Steenrod Stenographer Engineer in J. P. A-idrcx Robert licllary Charge of SeetLrc'n Zngi- R. D. Telle Keeeenger Design nnor o:. Solder ! Helper -I. 2. Korehouec D.F. Alexander W. E. Gllkey Motor Deeign Reeeerch Engi H-iner 3. IT. Deem aleotriolaa R. J. Thompson Phon. '"ranh neer or. Solder lne lie th ode ' C. A. Hochwalt Joan itoseiT* Deslrn Reiner Tatefcoien Florence Burns Detaller DISTr.ISUTIC:; CF EMPLOYEES J. A. Yalautlne Janitor (Head}'' Glennard Fry Letp.ilox Laboretorlea Overhead Fuel Kotor Research Drafting Refrigeration Shop Patent Attprne :. " Total------ T. H. Slier. V. Janitor (A$a*tli j . Vf>i^ . ' . . V-,- **4 FIGURE 12 ORCAN I SAT I ON CHART, RESEARCH OIVISION, OAYTON METAL PROOUCTS COMPANY, SUMMER 1919. ETC 36847 Report CC-83 50 On June 20, 1919, Dr. William E. McPherson of The Ohio State University made a visit to the laboratory and he was re tained as a consultant to give whatever help he could in the search for a practical knock suppressor. He in turn enlisted the aid of Prof. C. E. Boord, a colleague of his at the University. On July 23, Dr. Boord came to the laboratory with about 50 com pounds and mixtures to be tested for possible antiknock effects. Some of these had been tested before and some had not. They con sisted of aromatic amines, aliphatic and aromatic alcohols, es ters, chlorine and bromine derivatives of benzene, various homologues of benzene, and unsaturated derivatives of petroleum. No new or unknown types of antiknock agents were found among these compounds. Again on September 13, 1919, Drs. McPherson and Boord came to the laboratory with more than 20 further compounds for similar test. These included additional esters, various azo de rivatives, terpenes, and further homologues of aniline. Only the latter compounds showed any considerable effect as knock sup pressors. In the search for effective knock suppressors, it was of course natural that the alkyl amines should be tested for effect by comparison with the aromatic amines, such as aniline. And so . as soon as suitable alkyl amines could be had they were run; but in every case they were found to be inferior in antiknock effect to compounds of the aniline trpe (Reports, weeks of May 20, and July 28, 1919, and Record 10, page 243)* Thus it was found that 10$ ethylamine by volume in kerosine did not give as much suppresin of knock as did 35$ aniline. ETC 3 6848 Report OC-83 51 Work on Decarbonizers It was early in the effort to eliminate knock that the idea of removing carbon by some means_ ruch as by the action of powerful solvents, was given consideration. And some work was done on the idea in the spring of 1919. The first thing done, though, was to filter some dark fuel oil through Fuller's earth until it was nearly water-white and to run the clean oil in a Delco-Light engine by comparison with the original oil. No less ening in carbon deposited was observed. Carbon deposit from an engine was then extracted in a soxhlet tube with a series of sol vents. Among the most effective of the carbon solvents found in this way were diphenyl and aniline (Record 12, pages 24 and 25) Next a considerable amount of work was done (by D. F. Alexander) on the ultimate analysis of carbon deposit. In these analyses it was very difficult to get check results. So that composition was not established with any precision. However, it was established that engine carbon is not really carbon at all, but is a complex J1 mixture of tars, carbon or coke, and ash-giving solids (Record 12, page 27). Some experiments were made too on adding various materials to the fuel as a "pill" to see whether they would reduce carbon form ation (Record 12, page 41). This work was inconclusive, but shortly the important discovery was made that if a piston coated with hard carbon and with rings cemented tight in the grooves were soaked for a short time in hot aniline, the carbon was so softened and loosened that it could be wiped off easily and the rings were entirely freed. ETC 36849 Report 0C-S3 52 It was found also that aniline placed directly in the cylinder of an engine had a marked effect in softening and loosening the car bon deposited there (Report, week July 28, 1919). This discovery, after further experimentation was patented--U. S. 1,787,419, Thom as Hidgley, Jr., and Carroll A. Hodhwalt, filed April 15, 1922, issued December 30, 1930* In the summer of 1919 a comprehensive list of ring com pounds containing nitrogen in the forms of NH2 and NH was prepared to be used as a list of possible antiknock agents. Then, as a means of extending further the information about the antiknock qualities of homologues of aniline, Boyd em barked on a program of collecting and testing the various alkyl and other derivatives of aniline in a systematic manner. Some of these compounds were synthesized by heating aniline hydrochloride with less than the theoretical amount of each of a number of alco hols in a sealed glass tube at 150 deg* C. for about 15 hours. (Report, week Aug. 18, 19190 Several explosions of these tubes occurred. But the heating was done in an electric furnace especi ally fitted for such work, and so no harm was done. The results of this study in respect to antiknock effect arranged themselves with a curious consistency, as may be seen from the chart, Figure 13, page 53. It is there seen that aniline--plotted at the ex treme left--is ona^of the better of the antiknock compounds of ni-- toogen, but not the best, A paper based upon this work was pub lished later on, "Relative Effects of Some Nitrogen Compounds upon ^Detonation in Engines" by T. A. Boyd (Ind. Eng. Chem., 16, 893, ptember, 1924)* ETC 36850 tfP<*T 0C'83 53 FIGURE 13 CHART SHOWING THE INFLUENCE ON THE ANTIKNOCK EFFECT OF ANILINE OF SUBSTITUTING VARIOUS ORGANIC RAO I CALS FOR HYOROGEN IN THE RING AND IN THE AMINE GROUP. ETC 36851 Report 0C-S3 54 first Cooperation with Du Pont It was on August 13, 1919 that cooperation with the Du Pont Company, or their participation in the program which led finally to Ethyl gasoline, began. On that day. Dr. C.M.A. Stine, at that time Asst. Chemical Director of Du Pont (Dr. C. Li Reese was still chemi cal director then), and John Marshall, Manager of the Miscellaneous Division of the Eastern Laboratory, first visited the laboratory. They were then made familiar with the work done up to that time toward the solution of the problem of knock. A complete list of compounds tried as possible antiknock agents was later sent to Mr. Marshall, and he was requested to send us certain of the homologues of aniline* H. A. Lewis came to the laboratory to participate in some of the ex periments on cracking, as previously mentioned. And Midgley visited the Du Pont Company in November for a conference on the antiknock program, at which on the basis of Du Pont price quotations it was estimated that for each per cent of aniline added to gasoline the material cost would be 1.25 cents per gallon and for each per cent of xylidine 3dded to gasoline the cost would be 2*75 cents per gal lon. Later on (December, 1919) the men at Du Pont made a study and submitted a report on the possibility of producing enough alcohol to serve as automobile fuel. One of the conclusions of that report was that it would take about 55-60 per cent of the combined sugar and grain crop of the country to make enough alcohol to replace the gasoline consumption of that time. In 1920 a formal or written contract was entered into with the Du Pont Company under which they were to study combustion and 53 is a closed bomb fitted with a window and a camera with film for recording the explosions. This work, which was done at the Eastern Laboratory by llessrs. Woodbury, Lewis, and Canby, vras actively pursued for a time but was discontinued in the early fall of 1920 due to the financial stringency which developed that year. The work was done on a cost-plus basis, and the cost of it turned out to be something over thirty thousand dollars. The results obtained were presented in a report submitted by the Eastern Laboratory on October, 1920, "Motor Fuels, Rate of Flame propagation." These results also formed the basis of a paper pre sented to the S.A.2., "The Nature of Flame Movement in a Closed Cylinder," by C. A. Woodbury, H. A. Lewis, and A. T. Canby (S.A.E. Jour., 8,209, March, 1921), The work was incomplete, but photo graphs were obtained which showed the rate of flame travel with a few fuels, and which furthermore showed that sulphuric ether gave a characteristic self-ignition during the latter part of the com bustion of the charge in the bomb, whereas under the same con ditions petroleum ether was free from such a disturbance. The Detonation-Wave Theory of Knock The Du Pont work just reported formed the basis of an analytical paper published later by Midgley, "Molecular Movements During Combustion in Closed Systems," (S.A.E. Jour., 10, 357, May, 1922). It is interesting to note that it was from the 1920 Winter Meeting of the S.A.E. at which the paper of Fbodbury, Lewis, and Canby had been presented that Midgley returned with the detonation-- 'w theory of knock. This theory was to the effect that a ETC 36853 Report OC--83 56 detonation wave, which is known to accelerate to a maximum, is or iginated and supported by a decomposition of the fuel molecules which release an amount of energy that varies from one type of fuel compound Lo another. It was thought that the magnitude of this released energy determined the tendency of a fuel to knock. A great deal of work was then done in computing the relationships arcong different types'of fuels in terms of heating value. That is' to say, the changes in heating value as molecular size in the par affin series increases were compared, and the values of paraffins versus olefins, etc., were compared in the light of known differ ences in degree of freedom from knock. But the results of all these computations were not thoroughly conclusive. And so a series of paraffin hydrocarbons, pentane, hexane, heptane, octane, and nonane were prepared in as pure condition as practicable by fractionation from high-test gas oline, and these--along with benzene, toluene, and xylene and a number of alcohols--were rated relatively in terms of tendency to knock by finding how much of each had to be mixed with kerosine to make a mixture a.b free from knock as gasoline. It was thus found, by the rough means of test available, that the paraffins increased uniformly intendency to knock from pentane to nonane (impure though the samples were), that toluene is freer from knock than benzene and xylene than toluene, and that cyclohexane was better than pentane under the conditions of test. It is interesting to note in this connection that the ob servation mentioned just above that toluene was freer from knock ETc 36854 Report OC-83 57 than benzene and xylene than toluene gave Midgley the idea that iso paraffins, or paraffin hydrocarbons having methyl groups as side chains might be freer from knock than normal or straight-chain . paraffins. To check this point work was started in the attempt to fractionate out of casinghead gasoline iso-pentane and possibly other hydrocarbons having methyl groups as side chains (Record 10, page 249)* Some attempt was made also to synthesize such hydrocar bons by chemical means (Record 10, page 251). But this investiga tion was not at that time pursued far enough to establish the va lidity of the idea. One reason why that investigation was dropped so prematurely was perhaps because a cut from gasoline, boiling from 63 to 65 deg. C. and thought to contain considerable amounts of iso-hexane, did not prove to be freer from knock than another cut thought to be normal hexane. But the 63-65 cut was probably largely normal hexane, for it wa3 noted that its sp. gr. did not agree with tha value given in the literature for iso-hexane. And so it was not until the work of Graham Edgar and of Wheeler G. Lovell and John M. Campbell several years later that the great superiority in respect to freedom from knock of paraffin hydrocar bons closely compacted in space arrangement over paraffin hydrocar bons of the same molecular size but having extended or straightchain structure was established (Edgar, Ind* Eng. Chem., 19. 145* 1927J Lovell, Campbell, and Boyd, ibid, 23, 26, 1931, and later pa pers). The various items of work mentioned above did not fully explain the mechanism of knock. However, Midgley continued to ETC 36855 perr^ 53 adhere to and to develop further the detonation-wave theory of knock This theory appears in a number of the papers published later, but has in recent years had to be modified in view of the observation from photographic studies of engine combustion that knock arises from a self-ignition of a portion of the charge (Ind. Eng. Chem., 23, 539 May, 1931). However, in the light of this later informa tion obtained directly in engines, it is seen that the inference that knock is due to, or is accompanied by, self-ignition of a por tion of the charge might have been made from the records obtained in the bomb experiments at du Pont. Further contacts with the Du Pont people will be mentioned later on* It should be mentioned in passing, that during the fall of 1919 a considerable amount of effort was put into the develop ment of improved laboratory-size fractionating columns, and into an attempt to devise a special means of measuring the specific gra vities of liquids. Neither of these endeavors, however, were pur sued beyond the experimental stage. Among other miscellaneous en deavors engaged in at the close of 1919 and the beginning of 1920 were a study of the viscosities of fuels and of the surface tension of fuels and possible means of controlling it. The chart. Figure 14, page 59, is of interest in this connection, since it shows for the fore-part of November, 1919, both the personnel of the Fuel Sec tion and a list of the various endeavors which were then being pur sued or were in mind for the immediate future. A Temporary Change in Objective However, in the early part of December, 1919, the emphasis in respect to the research of the Fuel Section was changed somewhat ETC 36856 KEPOKT oc-di 59 C. F. lettering Chief "agin*** . C. Sblagh, Ph.B. eel of Sepirtal of Chemistry Pealsoa Cniverelty. Oeassltlag Chealat for Fuel leetareh Department. Cbtoleal and phys* leal examination *t eerboa deposits, lolTtots and "loos* atrt* for eerboa deposits. F. 0. Cleaents Dlreotor of 111 Research Thome* I'ldglay, Jr. Engineer in Charge of Fael Beeereh T. li Boyd General FupervlTsfr-of Fael Beseoroh li B07* J, Pa>i Aa ndre* D. F. Alexander B. bBJ. telle Abetrait and oorrel- Development of I Kaminatloa of ex* Conetruetlea lat* literature oa dlatlllatloa and hauat gates froa aad operation the oraoking of oils. epeeIflo gravity the motor. of eraoklag apparatao. apparatus. Motor testing to de Investigation of termine the effeota Examination of the the poeslblllty of Storage and of ontlknook materiale product* of varlou* preparing an anti* disposal of oa the power output eraoklag prooeatee, knook material ells and gasoline, aad the fuel economy, directly froa the and oa the amount of Solvents and orude petroleua. Eeduotlon of oarboa deposit* "looseners" for fire hatar4 aad eerbon deposits; Preparation of oar* of fir* Beterminatlon of the new antlknook extlagulehlag eoenoDloal range for atarials. apparatas. gaaolla* dletlllt-tne la rlew of the aao of aatlknook materials, Aeoumulotlon of data oa ratea of flaao propagation, orltloal preaauree, surface tenoloa, and vlsooalty of Tarloue fuel*. FIGUKE 14 PERSONNEL OF FUEL DEPARTMENT WITH PROVISIONAL WORK ASSIGN MENTS, NOVEMBER, I9U. ETC 36857 OC-83 60 in that it was decided to divert the main trend of the fuel work from the search for a practicable antiknock compound into an effort to improve the possible fineness of atomization of heavy fuels, hoping thus to be able to burn heavy fuels satisfactorily and with ccmoarative freedom from carbon and crankcase dilution. It was hoped then that the knocking difficulty might be taken care of by means of decomposition products of water in a suction burner or by introducing a percentage of exhaust gas (Record 10, p. 213). This change was brought about by the following events: 1. T. A. Boyd with John Marshall of Du Pont visited E. W. Dean at the Bureau of Mines, Pittsburgh Station, to ask for his opinion about what changes in the distil lation curve of gasoline would represent unit in creases in the amount of gasoline produced. Dr. Dean's opinion was that each degree Centigrade of rise in the temperature at which the gasoline cut was made would represent an increased production of gasoline of about one per cent (Record 10, page 211)* 2* It was found by test that, on the basis of the figure given by Dr. Dean, a comparison of the gasolines then being sold with the average on the basis of which he spoke indicated that a considerable increase of pro duction over the then current 25 average from the crude was already being put into effect by refiners, and that at the same time gasoline storage was full. It thus appeared that there was little likelihood of an ii Lx w> i ETC 36858 jjeport OC-83 61 jjuaediate shortage of light fuel, and that refiners were being able to sell lower grades of gasoline than the average of that time without serious trouble from knocking. And so it was decided "that work on antiknock materials done with a view toward making possible the use of low-grade fuels in internal-combustion engines is not very urgent at the present time." Thus it is seen that the primary idea back of the search for an antiknock compound had up to that time been that the^gasoline supply was in danger of being inadequate and that to use a heavier fuel, such as kerosine, an antiknock agent was needed to keep down its tendency to knock. But, of course, antiknock agents had already been added to automobile gasoline, and it was known that in some cars, notably in the Essex, knock was greater than some drivers wanted to tolerate. And so with this start the ideas apparently came around gradually, first to the use of an antiknock agent to make it possible to put a larger percentage of the crude into the motor fuel fraction, and then to the need for an antiknock agent, even though gasoline did not include a deeper cut into the crude. ^ The first of these stages in the evolution of ideas about the place of this research in respect to the fuel situation is shown by the discussion of "The Motor Fuel Problem," Appendix 1. The mat ter in Appendix 1, prepared in May,. 1920, is a part of the first of four quarterly -reports on the fuel situation mentioned later on in . this history. It is there concluded that the best solution of the ootor fuel problem would be to make available for use in gasoline ngines a larger percentage of the crude oil, and a plan of research , $I ETC 36859 jiepoft OC--S3 62 directed toward that end is presented in which the use of antiknock compounds has again a prominent place. But for a time beginning in December, 1919, the search for an antiknock agent was discontinued for the most part, and work was concentrated instead upon the effort to atomize and dis tribute heavy or non-volatile fuels, A great deal of work was done on this project over a period of months. Many schemes of atomization were tried, with and without heat. Engine runs were nade, including the operation of liidgley's car for a time, and the effect of degree of atomization upon the amount of carbon deposited in a given tinr1 was. determined. But since nothing directly useful came out of the endeavor, it will not be reported further here. Water as an Anti'cnock Agent The supplementary idea of using water as a knock suppres sor had already been experimented with to some considerable degree. Beginning in October, 1919, an extensive series of engine tests of the effect of water as an antiknock agent were run. The observation was that it required the admission of about one-third as much water as kerosine to a Delco-Light engine to be equivalent to 3.5 per cent aniline in decreasing knock, and that if the water were admitted as steam it was less effective than as .a liquid (Report, week October 20). a study of the possibility of emulsifying water with kerosine was then made also (Record 10, page 231 et seq.). It was found pos sible to make fairly stable emulsions by suitable means, but emul sions did not meter at all well through carburetor jets, although the Delco-Light mixing valve would handle them to good advantage. The ul- ?c 36*6q Report 0C-83 63 ti/nate result of the work on water as a possible knock suppressor ^as to abandon it altogether, both because of the difficulties men tioned, because water would freeze in winter, and because there is no supply of pure water available to engine operators--all they have usually is hard water, which is a solution of various salts in water. Mention should be made of the fact that it was during the work on the atomization of non-volatile fuels that Charles P. (Char- ^55' : xcg: ' ..T'T. lie) Harding began to work in the Fuel Section. He had been working at the laboratory for several months preceding, having been located in the shop at the rear of 127 N. Ludlow Street. First Use of an Antiknock Agent in the Army Air Service , In February, 1920, 3.5 gallons of xylidine was supplied to Maj. G.E.A. Hallett of McCook Field for use in a high altitude flight by Uaj. R. TC. Schroeder. Maj. Schroeder used this material as an anti knock agent in his flight of February 27, 1920, during which he reached the then very high record altitude of 36,020 feet. The xylidine was added to his fuel to overcome an apparent condition of preignition previously encountered with gasoline alone when attempt ing to supercharge at high altitudes. Maj. Schroeder reported to Hidgley that in the flight test made after the xylidine had been added that he could not make the motor preignite and that it "ran like a sewing machine." It was in this flight that Uaj. Schroeder became unconscious from lack of oxygen and fell with his plane for some miles before he revived, righted the plane, and landed safely. Tests had previously been made on the Delco-Light engine, from the results of which it was estimated that the xylidj:..: shcr^d be used ETC 36861 6U concentration of 3.5 per cent in the 68-degree aviation gasoline anployed. m early March, 1920, the first work was done in develop ing a system of demonstrating and studying detonation in a glass tube. By experiment an arrangement consisting of a glass tube closed at one end and open at the other, with a means of charging the tube from the closed end with a suitable mixture of gas and air, snd a spark for igniting it, was worked out which either would or would not develop the detonating type of combustion with a sharp crack and shattering effect upon the end of the glass tube, depend ing upon the fuel supplied to it. A mixture of acetylene, oxygen, and air was developed by trial which of itself would give detona tion but which in the presence of ethyl iodide vapor would bum quietly. This was first developed for use by Midgley in a lecture given at the Dayton Engineers' Club on March 16, 1920, and later on in Buffalo. The demonstration worked well--except at the lecture at the Engineers' Club, where for some reason it failed completely, to the great embarrassment of those trying to make the demonstra tion. This same experiment, with subsequent refinements, was used later on also, as will appear. ETC 36862 65 CHAPTER IV AFFILIATION "JlTH GENERAL MOTORS AND MOVE TO MORAINE CITY In the early part of 1920, an important change occurred in the status of the Research Division of the Dayton Metal Products Company. This was its absorption by General Motors Corporation in accordance with an arrangement by which the Corporation purchased and assumed control of the various Dayton interests of Charles F. Kettering and those associated with him. An important part of this arrangement was an agreement that Mr. Kettering would organize around the existing nucleus, called the Research Division of the Bright Division of General Motors Corporation. This arrangement was a temporary one which began about March, 1920, and which lasted only until the research laboratory was given separate status as the Gen eral Motors Research Corporation, incorporated on June 12, 1920. In the short period within which the research laboratory was a part of the Dayton-Bright Division of General Motors Corpora tion it was moved from 127 N. Ludlow Street, and from the site on West Third Street (Plant 3) where the Inland Manufacturing Company is now located"into which the mechanical portion of the laboratory had been expanded following the close of war activities, to tho large building at Moraine City which during the Bar had been occu pied by the Dayton-ttrignt Airplane Company. Figure 15, page 66, is ETc 36863 p.eport 0C-&3 67 a contemporary picture of the new laboratory building. This build ing, it is interesting to note, was the same one in a corner of which Ur. Kettering had originally intended to locate his new re search laboratory in 1917 when, as already related, the necessities of the War prevented the plan from being carried out. But this en larged research institution of General Motors could not now be housed in a corner of the building, large though it was. The new laboratory occupied about two-thirds of the floor space of the building, which was nearly 300 feet wide and 1000 feet long. A lay-out of the laboratory of the Fuel Section as it was first con structed in the new location is shown as Figure 16, page 68. It was in February, 1920, that these new laboratory plans first began to be drawn, and the actual move to the new laboratory was made in April or Hay of that year. It was originally intended to construct also in the new location, as an adjunct to the research facilities of the Fuel Sec tion, a small or serai-works refinery, similar to those which some petroleum refineries had at the time. Boyd made a trip to the Sin clair Refinery in East Chicago, and to the refinery of the Standard Oil Company of Indiana at ?fhiting, to inspect two such semi-works refineries. Suitable plans for a small refining unit were drawn up, and equipment consisting of stills--the largest 100 gallons, the smallest 5 gallons--condensers, pumps, and agitator were designed and ordered. But other things intervened, and the small refinery as not actually built. A record of the cost of the work on fuels and on the search fer a practical antiknock compound during the period from July 1, 1917* ETC 36865 fuels, as given there, was about forty-two thousand dollars. Beginning in Hay, 1920, and continuing to June, 1921, a series of five quarterly reports on the motor fuel situation were it was thought that they might be useful. The discussion which is presented as Appendix I, and which gives an outline of the motor fuel problem as it was thought to be in 1920, is a portion of the "is to increase the available supply of fuels suitable for use in motor vehicles and, at the same time, to conserve the fuel resour ces of the country, in order to insure the present and future use fulness of motor-driven vehicles." Through these bulletins an at tempt was made to establish what was called the "General Motors Fuel Service," to give information, and practical assistance where pos sible, to General Motors engineers and others interested. sive treatise on the testing of gasoline and on how to interpret the results in terms of service. This bulletin was based both upon ex perience accumulated up to that time, and upon an expensive investi gation conducted d-tring the spring and early summer of i.921 to refine ETC 36867 some of the methods so as to make them usable by others and practi cally useful to them. This final bulletin of the series was per haps the most practical and the most useful of all of them. At the request of the editors of Automotive Industries, it was later interest in, and some investigation was made of, the possibility of getting motor fuels from vegetation. This activity was, of course, occasioned by the fear, which still persisted, that the supply of gasoline from petroleum might soon become inadequate. It consist ed chiefly of these two items: First, was the work that Hochwalt did on the preparation of furfuraldehyde from com stalks, straw, and com cobs, and in the attempt to hydrogenate it to the furfuryl alcohol, and also on the hydrolysis of wood to produce sug^ars which might be converted to alcohol by fermentation. As a motor fuel, furfuraldehyde was found to suffer from the difficul ty of preignition. Second, was the library study of cellulose con ducted by Boyd at Tale University, consisting of daily conferences with Dr. Harold KLbbert ar.i of a study of the literature in the University library relating to cellulose, which was as extensive as could be made within the few week3 devoted to it. Dr. Hibbert, who is now professor of industrial and cellulose chemistry at Mc Gill University, was retained after a survey had b?*.; made of the various men in the country who were active in thj field of cellulose ETC 36868 Report OC-83 71 chemistry had suggested him as best fitted for the purpose. He gave a series of lecture-conferences designed to cover in so far as pos sible the existing knowledge on the subject of cellulose chemistry, particularly in respect to the basis of the effort he was then mak ing to synthesize cellulose. On July 20, 1920, Boyd wrote to Midgley from New Haven: nl find that it will be impossible to cover the literature of the subject of cellulose in such a way as to gather the previously ob tained information on the subject in four weeks, even counting ten hours a day. In fact, I believe that it would take from four to six months to do the job thoroughly. But I am trying to cover as much of the territory as is at all possible while I am here. If you are up this way, I hope you will arrange to spend a day or two here seeing what Dr. Hibbert and I are doing." Midgley did pay a visit there within a week after that letter was written. Inci dentally, he had previously asked Boyd to make some search of the literature for further information on cyanamide. This he did be cause at Moraine City additional investigation of this compound, which had been studied so extensively the previous year, was then in progress. After the discontinuance of the paper studies of cellu lose at Tale, not a great deal further of that kind was done in the effort to make motor fuel out of.cellulose. Midgley was anxious for Boyd to get back to the laboratory, because his help was thought to be needed on the other endeavors then under way, orx of these having been the effort, now to be described, to develop an injector for- ETC 36869 pepr^ 72 feeding aniline or other antiknock compound to the engine as needed* Interest in the subject of getting gasoline out of plants continued, however, and Hochwalt carried on an investigation of the hydrolysis 0f cellulose and wood which lasted until March, 1921 (Record 14). also some economic studies were made and a paper entitled "Motor Fuel from Vegetation" was published later on (Ind. Eng. Chem,, 13, 636, September, 1921). The Aniline Injector Because of the high cost of antiknock agents of the ani line type--which, as has already been indicated, was of the order 3 to 4 cents per gallon of gasoline for 3.5 per cent aniline and about twice that much for an equivalent concentration of xylidine-- and also because of the belief that not enough aniline to treat all gasoline could be had at any price, work was begun in the early sum mer of 1920 in an effort to develop a device to inject aniline in just the amount needed to eliminate knock, and not to consume any aniline at all when none was needed. It was believed, on the basis of experiments made then that injecting aniline only as required would reduce the amount consumed to about one-tenth that used when the aniline was put directly into the gasoline so that it would be consumed at part throttle as well as at full. The background of this endeavor was explained in some detail in a letter which llidgley vjrote to Dr. Charles L. Reese of the du Pont Company on June 9, 1920, and which is included as Appendix III. In connection with this letter and with thw /cork on the development of an aniline injector, it is interrsvvng t<- note here ETC 36870 jjeport OC--83 73 three items of information: first, that the decision to discontinue research on antiknock compounds, which had been reached six months before, had now been abandoned; second, that it was then thought unlikely that a better antiknock agent than aniline would be found; and, third, that it was then believed that the supply of petroleum was so limited that, as l&dgley said in his letter to Dr. Reese, "This year will see the maxi mum production of petroleum that this country will ever know." A large amount of work on the development of an aniline injector was done throughout the rest of 1920 and the early part of 1921. Tliis work consisted not only of the effort to develop a practical mechanical injector, but also of determining the relation ship between knock and degree of vacuum in the intake systems of en gines, of making viscosity studies on aniline and its homologues at various temperatures, of making studies of the solubility of aniline in solvents such as benzene at low temperatures, and of trying to prevent the gumming of aniline which developed in injectors after continued use. An effort was made also to find some means of des troying the unpleasant odor of aniline, which asserted itself both before entering the engine and in the exhaust gas. There was so much of the peculiar stuffy odor from aniline in the exhaust of an engine using it that the presence of a car using aniline or one of its homologues was sometimes unpleasantly apparent. A large number of perfumes and aromatic oils--such as camphor, pennyroyal, citro- uella, and the like--were added to aniline in an ef to disguise these odors, but without appreciable benefit. A great cieal of Heprt 00-83 74 was aaoboouut the mast satisfactory valve material found, but there was trouble from the aniline gumming in injectors after they had been in service for a tine. Some of the injectors were put into operation on cars and it was planned to build a combined carburetor, suction burner (for warm-up), and aniline injector. g<rst Plan to Market an Antiknock Agent In spite of the difficulties met with, liidgley held a con ference with men at the Du Pont Company in August, 1920, at which the following rather definite plans were made (as quoted from let ter of August 5, 1920, llidgley to Dr. Reese): "I understand that the Du Pont Company will co operate with our company in placing aniline on the market for use as an anti-knock material, in connec tion with the aniline injector which we are develop ing. The first phase of this program would consist in one of the General Motors Companies marketing an aniline injector through the ordinary channels of ac cessory dealers. The Du Pont Company would simul taneously put aniline in small quantities, such as pints, or quarts, or perhaps, gallons, which could be sold in conjunction with the injector. A further working out of this program would comprise the sale of aniline in bulk by the Du Pont Company through some satisfactory distributing agency, such as has been suggested by the Standard Oil Company, who could give aniline national distribution, similar to lubri cating oil, selling same in bulk at the filling sta tions* this plan was not put into effect, however. In December, 1920, an extension of the injector idea was d in the initiation of an effort to develop sue;* c device for ETC 36872 M as*. Report OC-63 75 the men at McCook Field, chiefly Maj. G. E. A. Hallett, who had shown a great interest in the possibilities of using antiknock agents as a means of eliminating knock, which was a barrier alike to higher com pressions and to greater degrees of supercharging. The development of an injector for airplane engines involved an aneroid for control ling the flow of aniline with altitude as well as the customary means for varying the amount injected with manifold vacuum. The same problems were encountered in the effort to make an injector for airplane engines as were being encountered in the work on an injector for automobile engines, and some additional ones as well. The plan to inject an antiknock agent into airplane engines met with some measure of success, however. And in March, 1921, 500 gallons of a mixture of 70 parts ortho-toluidine and 30 parts benzol, called Antiknock No. 1, was sold to McCook Field for use there. This material had been purchased from the Du Pont Company* ' Four hundred gallons of Antiknock No. 1 were sold also to the Navy De partment at about the same time. During the year 1921, a considerable amount of antiknock agent consisting of the mixture.of ortho-toluidine and benzol was in fact either sold, or given in small amounts, to a good many dif ferent people. No attempt will be made to give a list of these. But mention may be made of one of them, Edsel Ford, who on December 1, 1921, wrote to Mr. Kettering as follows: "In conversation with Colonel Hall day be fore yesterday, he mentioned the fad that you were selling your anti-knock solution, and if this is true we would li!:i ^ have you send a few gallons for trial in our experimental engine shop." ETC 36873 -4 Report OC-83 76 To this letter Liidgley responded on December 3, saying that at Mr. Kettering's request he was sending Edsel 5 gallons of the antiknock compound* The work on an aniline injector for automobile engines was continued on into 1921. These devices were successful enough to be used to some degree and to be patented. Two U. S. patents on aniline injectors were issued, as follows! 1,501,568, July 15,- 1924, Thomas ilidgley, Jr., Aniline Injector; 1,467,222, September 4, 1923* Fred S. Aseltine, Method and Means for Incorporating an Antiknock Substance with a Motor Fuel Mixture* Dark Hour Before a Break in the Clouds But by the spring of 1921 the problems of using aniline as an antiknock agent, either added directly to the fuel or sepa rately injected as needed, began to make it appear that the use of compounds of the aniline type might not be practicable. In a let ter of April 2, 1921, to Dr. C. M. A. Stine of the Du Pont Company, ilidgley said: "There are one or two problems connected with the use of antiknock that, while they have been men tioned in the past, are now assuming very serious proportions and unless they can be overcome, our engineering results may never be realized in prac tice. The outstanding problem which faces us at the present time is the odor of unburned aniline, or partially burned aniline, coming out of the ex haust. I doubt if humanity, even to doubling their fuel economy, will put up with this smell." There was also the danger arising from the tcxicity of aniline, and the difficulty of the action of the alk.'iir.e compounds f the aniline type on metals with which the fuel cam? into contact* ETC 36874 J?eprfc 0C-S3 77 Thi3 latter was a factor that had caused trouble in the work on in jectors, the gunning difficulty having already been mentioned. The .airplane people at McCook Field made a series of tests to measure the effect of such antiknock agents on metals. Their findings were published in Automotive Industries, March 23, 1922. They found that "aluminum and zinc are very slightly affected, if at all, by the doped fuels, but-copper, brass, terne plate and iron are badly af fected." So the first of April, 1921, came--more than two years after the discovery of the antiknock effect of aniline. And, al though some small success had been had in using aniline compounds as antiknock agents, the accumulation of difficulties which appeared to be insurmountable made it appear that there was very little prosoect of commercializing such compounds successfully. Enthusiasm of those working on the antiknock endeavor was accordingly at a low ebb, some even thinking that the antiknock endeavor-might have to be abandoned. Mr. Kettering has related that Midgley came to him about this time and suggested that possibly it might not be worth while to pursue the antiknock endeavor much further. No better anti knock agent than aniline had been found, it did not then seem likely that rny better one would be found (see Midgley's letter to Dr. Reese, Appendix III) and the use of aniline-type compounds had.met with difficulties that seemed insurmountable. ETC 36875 jtepor* 00-83 CHAPTER V SELENIUM DISCOVERY OPENS NET FIELD 78 On April 6, 1921, a very important discovery was made-- the discovery that a compound of selenium, selenium oxychloride, was a great deal more effective as an antiknock agent than any thing tested up to that time. This amazing result (Record 13, page 25; Record 20, page 2) seemed all the more remarkable since it was known that, in general, compounds containing oxygen or chlorine--and selenium oxychloride contains both--are knock in ducers.' Sulphur oxychloride, as a similar compound, was in fact tested at the same time as selenium oxychloride and found to be an inducer of knock. So it is easy to understand that the dis covery of the remarkable antiknock effect of selenium oxychloride was an exciting event. Selenium oxychloride had first cone to attention in Hay, 1920, the year prior to the discovery just mentioned. There had been newspaper stories about it then, these having been based . upon the work of Prof. Victor Lenher at the University of Wiscon sin. He was investigating selenium and tellurium under the spon sorship of the National Research Council, and at the instigation of copper, lead, and silver producers. These producers had sel enium and tellurium as by-products of their smelters, without having found much use for them. In one phase of Di. leiiher's work he had made some selenium oxychloride, and in the summer of 1920 had described its effectiveness as a solvent. ETC 36876 Report OC-83 79 As the tests on carbon solvents previously mentioned were then in progress, Midgley wrote to Dr. Lenher on May 15, 1920, ask ing how some of this new compound might be obtained. One of the purposes in trying to get a compound called a "universal solvent" was of course to test it as a carbon solvent. The other was to try it as a possible antiknock agent, in accordance with the cus tom of testing every available compound in the engine. But Dr. Lenher replied that selenium oxychloride was not yet on the market. Interest in the compound was not then sufficient to cause us to try to prepare it ourselves, especially so since that was a very busy time just after the removal of the laboratory from 127 N. Lud low Street to Moraine City. And thus nothing further in respect to selenium happened until the early part of 1921> when, following further publications relating to Dr. Lenher's work on selenium oxychloride (Jour. Am. Chem. Soc; 42, 29, 1921), a letter was written to Dr. Lenher on March 14, 1921, asking again where some of the compound might be obtained. The reply said that it could then be purchased from Baker and Adamson and from Eimer and Amend. And so a small amount was bought from Eimer and Amend; and on April 6, 1921, it was tested for possible effect as a knock suppressor, with the surpris ing results already reported, namely, that it was a much more ef fective antiknock agent than any discovered up to that time. The following interesting story about selenium oxychlor ide, related to Boyd by Mr. Kettering, January 17, may be in serted here. About the time when the search for a practical anti knock agent reached its lowest ebb in the spring of 1921, as already ETC 36877 Beport OC-63 80 recounted, Mr. Kettering went on a trip to New York. All the while he was gone the question of what should be done about the search for gn antiknock agent was on his mind. Because so much effort and ex pense had been put into it already, and because he did not want, therefore, to drop the work unwisely, he was greatly concerned about what decision should be reached in regard to it. Coming back to Dayton from New York, he was thinking about this problem; and in the evening when the porter came to make up the berths in his drawing room, he and Mrs. Kettering went out of the room and sat in one of the seats at the end of the car. As Ur. Kettering sat down he picked up a paper that was lying there, and his eye happened to fall on a news item in it^ which was to the effect that Dr. Victor Lenher of the University of Wisconsin had discovered what was termed a "universal solvent" in the compound called selenium oxychloride. Because Ur. Kettering just happened to know a funny story about a universal solvent, he was interested enough to read the item; and, as he did so, it occurred to him that here was a compound that had not, so far as he knew, been tried for effect on knock, in spite of the fact that a very large number had been investigated. Figure 17, page 81, is a copy of a newspaper item about selenium oxychloride which appeared around that time, but it is probably not the particular one which Mr. Kettering saw on the train that"night. The story about the universal solvent that was in Mr. Ket-': 4 tering's mind was to the effect that a man who had car trouble on the road one day went to a small building near by in search of a telephone. There he found two men busily engaged in making chemical ETC 36878 REPORT OC-83 NEW CHEMICAL SOLVENT. Watt* By-Prod ud if Caspar Rtfln t I* Ramarkakl* Reagent. x m* i.iemlnl rcaccnt vhMi ha* proven ta b art o( (to moat llrlkljif eotvent* dlacevered In recent 7Hn ana contain* poaalblllltea of eitenele* Indio trial in hao recently boon worked out In the chmleal taboraiorlo* of tho Unl- 'criltjr of tVlaconntn, Tim dtacovonr woo announced at th# mootlna of tlm American iTumltil Korlety In m. Imula roerntiy by Rrofmaor Victor Uanhee. tho chomlat who dli'Ov*rod It. Th* now *ol'ont U tochnloally known aa aolonlum oaichlorld*. and It la mado of a commvieial byproduct of which hundroda of tol*a ao to waatc. .ta a chemical recent. thla now aubatonco PotttfatM th* property of a'-tiny a* an aicollant aolvant tor auane nf in* moat tnaolubl* au balance*. auch aa loounr. aaphalt. and th* bltumlnoua material hi oft coal. Tho reaaent la an cacoitent oobrent for unaatumu-d oryanlc aubatancaa. Th* unaatumtad hydiocarbona, mb aa acetylene. bans.n* toluone. Ac., dmowtva readily In It whila the paraffin hydro carbon*. aueh aa (aaollno. krruoa. . a M>* <tlW mineral waaa*. vaaeMa* tad paraffin, are unaffected. T. . . . . table olla are acted upon, many with violence, and linaeed ail forma a thlrb oaccedincly mucllaaenoua and rubberIlk* maa*. Uakclita. redmanoL th* waterproof Inaoluble raaaln ffluo ued la a in-tconatructlon. pure rubber, eulcoalced rubber, aaphalt and bitumen all dla*!;* with eaae. Th* bltumlnoua nutferial In.aoft cool can be d.a. olved oneleevine a carbonaceoua raialur. and la U probability toms Information aa to (be character of th* naturally occurring yphaiu lud bitunaiu van be tihfofnru bythw oee of tbit m solvent. The Rdcmani from which the solvent made i* a by-product In the tmtrd* lytif refining or copper, a aubituct for which ihcrc ia now no market. although hundred* of thoaiaiidi of potal* of It are annually rolnf to wasted Uurl| tnc late aar. when manganese waa not obtainable fo the pui poor, .wlenSuoi ao used for the dlsrotorisaUon of glass, and a very considerable quantity *ae irodu*vd fur this purpose. Hut now that manganese Is again obtain able. piuct.i-sUy no selenium U being put on tin market. A smell amount is need for the preparation of light sensi tive teli*. but tne amount ucd la InilRtieaunnl fiom the ptoduulon stand point. A commutes of th N'ethmal H -urrh i'ouncll. of which Professor Leaker of the I'ulviTiity of Wisconsin v.Hn-*ti> deportment is a member, lisa been aorktng for more than t >-nr on (he question of finding a maiket for the (-r.ormuus e mount of ihis element now going to waste, but nothing remarkable nits developed until this vary recent dl^ cowry by l*r. Lrnher. The method of preparath^o of tho new compound la simple* according to tho discoverer. Tli.s a oik has developed a remarkuMn degree of intereel among chemists, and. by request. i>r. Uiihsr presooted tbn rflultn of this------------- 81 FIGURE 17 ONE OF THE NEWSPAPER ITEMS ABOUT SELENIUM OXYCHLORIDE AS A "UNIVERSAL SOLVENT" WHICH, AS RELATED IN THE TEXT, PLAYED A PART IN THE 0 ISCOVERY OF SELENIUM AS AN ANTI KNOCK AGENT HAVING A NEW AND HIGHER OROER OF EFFECTIVE NESS. IT WAS THIS DISCOVERY THAT SET THE SEARCH FOR A PRACTICAL ANTIKNOCK AGENT OFF ON ITS FINAL, AND MORE - :;:v- ETC 36819 Report OC--83 82 experiments. While he waited around, he learned that they were try ing to discover a universal solvent--something that would dissolve everything it touched. After pondering the matter a little while, the stranded traveler said to the two experimenters, "Of course it's none of my business, but I have just been wondering what you are going to keep that stuff in when you get it." It was just about the time that Ur. Kettering got back to Dayton, or shortly thereafter, that the sample of selenium oxy chloride was obtained, as previously related, and tested with the remarkable results mentioned. But selenium oxychloride is a compound highly corrosive to metals, one that fumes when exposed to the air. In its disinte grating effect upon engines, it would be almost as bad as the uni versal solvent mentioned in the press at the time in connection with it. This, coupled with the fact that its content of oxygen and chlorine woul'd seem to keep it from being the most effective compound of selenium, caused an immediate search to be begun for a better and more effective compound of selenium. It was, how ever, found possible at the time to make first an alkyl compound of the similar element tellurium, diethyl telluride (Record 14, page 75). This happened because, following the letter which Midgley wrote Dr. Lenher in Kay, 1920, some tellurium had been sent to us from Omaha by the American Smelting and Refining Com pany, and so was readily at hand to work with. Using this tel lurium as starting material, Hochwalt made some diethyl telluride by preparing an alloy of tellurium and potassium and then reacting it with ethyl chloride under pressure. ETC 3G880 Report OC-83 83 The diethyl telluride thus made was first tested by Boyd for effect as an antiknock agent on April 8, 1921, and found to be several times more effective still than the selenium oxychloride which two days before had been found to have what was then thought to be such a remarkable effect (Record 13, page 26; Record 20, page /,), Later diethyl selenide was prepared and found to be consider ably more effective than selenium oxychloride, but not so effec tive as diethyl telluride (Record 13, page 27). It finally turned out that on a volume basis diethyl selenide was about five times as effective an antiknock agent as compounds-of the aniline type and that diethyl telluride was about twenty times as effective as aniline. These discoveries naturally put an entirely different as pect on the antiknock endeavor, and gave a new lease of life to the investigation. On April 15, 1921, Midgley wrote to Dr. C.MJl. Stine of the du Pont Company a letter the tone of which was quite different from that of his letter of April 2, quoted on page 7$. "I know you will be interested," he wrote, "in hearing that we have re cently discovered an antiknock material which is twenty-four times as strong as aniline, volumetrically. The material looks very, very practical and I feel sure that this Is going to radically change our previous plans, obsoleting the injector; in fact obsoleting the use of aniline or coal tar products in any way, shape, or form, except, possibly as carbon removers." TC 3688 Report OC--83 eu Miscellaneous Events of 1920 and 1921 Before proceeding to recount the events which followed these important new discoveries, it seems desirable to digress long enough to tell about some earlier events, which were passed over in order to till the story of the development of the aniline injector in continuous fashion. In December, 1920, and January, 1921, work was done on a project which is of interest because it formed at least a part of the development of the crankcase ventilators now used almost uni versally on American cars. This work consisted of experiments on the removal of low-boiling materials from the oil in the crankcase by means of a stream of exhaust gas (Record 13, page 5 et seq.). The experiments consisted both of bench tests of various kinds and of tests directly in engines, and they showed that it was possible to remove considerable amounts of volatile material from crankcase oil containing such material. During the first half of 1921 the hydrogenation furnace and other equipment in the semi-works laboratory--called 'Refinery?' in Figure 16, page 6$--were used in preparing a series of compounds on a small scale for the Eastman Kodak Company. This work was done at -he request of Eastman, and the furnaces were operated by Russ Wells. The following is a list of these compounds and how each was made: Sec-butyl alcohol, by hydrogenating methyl ethyl ketone Heptyl aJ .ohol, by hydrogenating heptaldehyde Cyclohexancl, by hydrogenating phenol Hexahydrocresol, by hydrogenating cresol Hexahydrotoluene, by hydrogenating toluene Hexahydrocymene, by hydrogenating p-cymene Amylene, by dehydrating amyl alcohol Report OC-83 85 It was in January, 1921, that the members of the Fuel Section had their first practical contact with the sticking of engine parts from gummy gasoline (Record 13, page 7). Mr. Charles H. Fox of the Ahrens-Fox Fire Engine Company and Mr. Campbell of the Cincinnati Fire Department enlisted the aid of jjr. Kettering to help solve the problem of the sticking of car buretors on some of their fire engines, which trouble in some in stances got so bad that engines could not be started due to the freezing of throttle valves. They brought to the laboratory samples of the gasolines being used. They brought along also a carburetor having a considerable amount of the characteristic brown vamieh-like gum in its passages. They feared that the troubles had been occasioned by some malicious person having put acid in their gasoline storage tanks. By examination of the samples of gasoline and by quizzing Messrs. Fox and Campbell, together with a representative of the gasoline supplier, Mr. L. S. Bale, it was possible to clear up the mystery by finding that the gunning of the gas >line and consequent sticking of en gine parts was caused by using a cracked gasoline in too adverse a manner. The fuel tanks on infrequently used fire equipment were kept full and the equipment stood nearly all the time in a heated engine house. Some pieces of equipment used so little gasoline that the supply in the fuel tank sometimes did not get changed completely for a very long time--for a time long enough to allow harmful amounts of gum to form in the gasoline. So their trouble was easily cured, and the men in the Fuel Section peport OC-83 86 irere glad to have had a hand in finding the cause of.it and how to cure it* In January, 1921, Ur. Kettering assigned to the Fuel Sec tion the job of investigating three devices which had been proposed to him by P. G. Tisraer of Tompkinsville, New York. Tismer, who was a most peculiar character, spent a great deal of time, around the laboratory advising how to design and build his devices for appli cation to a Delco-Light engine. His three devices consisted of a ringless piston, clearance 0.001" to 0.002", a lubricator for the piston, and an igniter to facilitate starting from the cold on kerosine. Broad claims were made for these devices, of course. But, after building samples with Tismer*s advice and giving them suitable tests, it was concluded that, in view of the difficul ties experienced with them and the lack of benefits from their use, Tismer*s devices were at least of no interest to General Motors. The program covered-a period of about two months, and the results as well as drawings of the apparatus were presented in a formal report dated March 12, 1921, a copy of which is still in the Fuel Section files. It seems appropriate to mention here, as the one who made the drawings for the Tismer devices, another of the men who participated in the early activities of the Fuel Department,. R. J. (Tim) Thompson. The drawings, and some of the designs, for other mechanical elements which entered into the early research on fuels were made by Thompson also, such as the Uidgley Optical Gas Engine Indicator, the aniline injectors, and the like. ETC 36884 Report 0C-S3 *3. 87 Thompson was for some time a member of the Fuel Section staff di rectly. Since 1925 he has been with Frigidaire and Kinetic Chem icals, Inc. Further rork on Selenium and Tellurium Now that these miscellaneous happenings have been men- tioried, it is possible to return to the events which followed the important discovery of the remarkable antiknock effects of com pounds of selenium and tellurium, as made in early April, 1921. This discovery naturally resulted in an intensive effort to in vestigate similar compounds, and consequently in the substantial abandonment of further research on c'impounds of the aniline type. (In respect to aniline compounds, however, see the discussion of the high-compression Chevrolet which follows below. Gasoline treated with ortho-toluidine was used as fuel in this" car during the summer of 1921.) Other oil-soluble compounds of both selenium and tellu rium were made and tested just as rapidly as possible. These in cluded the methyl, the ethyl, the propyl, and the phenyl compounds. All were found to be quite effective as knock suppressors (Rec. 20, pp. 2-10); and, by the approximate methods of test then available, tellurium compounds appeared to be about four times as effective as equivalent compounds of selenium (Rec. 13, p. 30). An immediate effort was made to find out also whether, in case the use of selenium and tellurium as antiknock agents should prove to be practical, the supply would be adequate to permit any considerable proportion of the gasoline used to be treated. For ETC 36885 Report OC-83 88 this purpose Midgley and Eoyd attended the spring meeting of the American Chemical Society in Rochester, K. Y., about April 25, 1921, at which a conference on the subject was held with Dr. Victor Lenher. This survey of resources showed that the largest estimated production of tellurium from any one producer was 30 tons per year by the Raritan Copper Storks, whereas to add even one one-hundredth of one per cent to the gasoline consumed then would have required 1,500 tons per year. And so the potential supply of tellurium was judged to be inadequate (letter, August 4, 1921, Boyd to Dr. Victor Lenher). The cost of the compound was low enough, however, and its effectiveness as a knock suppressor was high enough that, if it had not been for the problem of availability and one other men tioned in the next paragraph, tellurium as an antiknock agent might have become commercial. It was at the Rochester meeting of the Chemical Society that knowledge of the discovery of the remarkable effects of sel enium and tellurium began to be spread around. This resulted, first, from conversations about the discovery with men at Roches ter, and, second, from the impression.1ft on those with whom we came in contact there by an unusual and disagreeable property of selenium and tellurium, and particularly of tellurium, which was apparent wherever we went. Any one wh-> worked with volatile compounds of tellurium got an affliction called tellurium poisoning. This is not conventional poisoning, but just a bad odor imparted to the victim. Some one spoke of the odor as a Satanic garlic smell, and that is what we carried to Rochester with us. "There was no getting rid of it (Ifidgiey, Motor, January, 1925, p. 92). Report OC-33 89 jt was so powerful that a change of clothes and a bath at the end of the day did not reduce your ability as a tellurium broadcasting station. Nor did the odor grow much weaker when several days were passed in absence from the laboratory." Incidentally, this quota tion from Midgley may be broken here to insert the observation that when these notes were prepared in September, 1938, 17 years after the work on tellurium, the familiar odor of tellurium was apparent on the hands of the writer from having handled the rec ords of the time. This odor was the more pronounced on that par ticular day because it was a humid one, and the tellurium odor is greatly accentuated by dampness. "However," Midgley's story about the tellurium odor con tinued, "my family quickly became accustomed to it. and those at the laboratory were likewise imune. Going out at night, however, was a problem, although I found one neat solution. V-hen we went to the movies, I would look around until I found a man of Medi terranean extraction, and we would sit down beside him. Present ly people would scowl at him from all directions as they got my perfume, but we were secure and comfortable." After returning from a visit to the laboratory one day in May, 1921, Harry 1. Horning of the Waukesha Motor Company wrote to Midgley: "This is to let you know that I reached home safely and that every one is greeting me with gas masks on." At the outset of our work on selenium and tellurium there was, however, concern about whether the compounds night produce poisoning of a more harmful nature. In the laboratory care was accordingly taken to work in the hood. Later on, in the fall or Report OC-83 90 1921 when a quantity of diethyl selenide was to be made up for the Air Service to use in experiments at McCook Field, Dr. Victor Len der and some of the producers of selenium and tellurium were asked ab->ut possible dangers from poisoning. All the reports were that no trouble from the poisoning of workers had ever been experienced; Dr. Lenher wrote (letter of November 3, 1921): '*?'e have had a large force of men working with selenium on rather a large scale for a university for the past few years and we have had no symptoms whatever of selenium poisoning of any kind." Nevertheless, when some years later Doctor Lenher died from an undiagnosed ailment, it was commonly supposed that selenium* with which he had worked for many years* might well have had something to do with it. But we had no poisoning, aside from the bad odor, which to some degree afflicted every one who worked in the laboratory, regardless of whether they came into direct contact with any of the compounds. First High-Compression Car--''The Goat" During that summer of 1921 the compression of an FB Chev rolet engine with a displacement of 223 cu. in. was boosted to 7:1 from the normal value of L.l:l. The car which contained this en gine, a Chevrolet "Baby Grand," driven on gasoline alone before the boost in compression and on gasoline containing 9 per cent of ortho-toluidine by volume after the boost, gave the relative re sults summarized in the following tabulation (Report for July, 1921, August 3, 1921): ETC 36888 Report 0C-S3 91 Standard Compression High Compression Compression ratio 4.1:1 Acceleration, 5 to 30 miles per hr. 13 seconds Miles per gallon Maximum . . 24 . . Touring ; . : Town driving i . .. 16 . 12 .. Knock suppressor none 7.0:1 9 seconds . 34 .. 25 20 9% ortho' toluidine A picture of the "Baby Grand'* Chevrolet cah used in the tests just reported is included as Figure 18, page 92. It was dubbed "The Goat." This name was given the car, and it appeared appropriate, first, because of its mountain-climbing ability (its high horsepower), and, second, because of the musty smell of orthotoluidine which always hovered around it and which issued from the exhaust pipe whenever the car was driven. At the summer meeting of the S.A.E. at fhite Sulphur Springs in June, 1921, Midgley presented comnent on "Mileage In- i crease and Antiknock Materials" as discussion of a formal paper by Fred C. Ziesenheim on "Developing a High-Compression Engine" (S.A.E. Jour., 9> 270, October, 1921). In this discussion Uidgley gave comparative fuel economies based on the data in the above tabulation. He also reported approximate figures on the relative degrees of effectiveness for a number of antiknock compounds, in cluding diethyl selenide and diethyl telluride. The Periodic System Becomes the Guide The discovery of the remarkable knock suppressing effects of compounds of selenium and tellurium inaugurated an important ETC 36889 FlttlsE 18 chcvroce* car used in riRsr mich-compress.on tests, it ias O'jasen TMC boat," aw has an engine itm compression RATIO SOOSTEO FROM 4.I UP TO 7. Report OC-83 93 was a systemization of the search in terns of the periodic group ing of the elements. Up to that time the selection of compounds to test had been made altogether by the Edisonian method of "cut and try." But the discovery of the effects of selenium and tel lurium, when taken together with the information already obtained on compounds of iodine and nitrogen, and then viewed in the light of a special periodic arrangement of the elements to which we had access, suggested that the antiknock property might be a periodic function. The arrangement of the periodic system referred to was one made by R. E. VTilson based upon the Langmuir-Lewis Theory of Atomic Structure. The type of chart used in this phase of the research is shown in Figure 19, page 94. There the elements are arranged not alone in terms of number of electrons in the outer shell, as grouped by Langmuir, but also in terms of number of vacant spaces in the outer shell. And, from the knowledge obtained in the search up to that time, it was noted, first, that all the elements yet found effective as knock suppressors were located at the far right in the lower group. It was observed, second, that the valence of the element in the compounds which were effective corresponded to the number of vacant spaces in the outer shell: viz, iodine, one; selenium and tellurium, two; and nitrogen, three. From the knowl edge that bromine increased knock while iodine reduced it, and that tellurium was much more powerful than selenium as a knock sup pressor, it was surmised also that antiknock effect increased toward the bottom of each column. The search was thus turned into a systematic "fox hunt" (llidgley's term). ETC 36891 REPORT OC-83 sVJTl' Ja33`.7ZJJsr ^yS7T?.tf O.V TVTf **yV&*f/SJP 7y/fa?y-<3F^7Z7SfSt7`7V?&C,77AT- 94 AZM&fA**`2*47X0*3SMMV'S* tTST2 \a/S\e 17 ' G's\a'-J\g\/\t7 Sf/U j\A's\P\7\a 3 Jt? *s Z?2S2<r y? J" &0 i 3 1 1 Am )i1 ! ! t ;Jit f yr'Ap Am Ft - i i t^yfihSt7>'y'v*itiir/e V/cZsz tSr & i [ft A 3 'C^s'ffAx JVSZVir&SShiZTJdTe \S Xr f>\Sr.SSt&V'\X 2T* ZF 6 Xe&A/Sr'iZa&Si'- ii**y\Sr ar Z4)(Si/FX',M Mi & i3`7X*ZS$f* lTl- L_P& 1V'7S\ SlrU- 1 Jj _1_L_ ju_____ 7r^s ejfa.^enroMTAe. AMSS. itm: T3FCM. A PeBmasikoooieomSmtstnin Lanbmuia TUmomv or Atomic SrmiCTvA aao am Aasamgkmkat by R.E. Wilson Numb** or Elbctbohs m Curmm 5mua. Snu 0 1 2 3 4 -S 6,7 a 9 H \!2 !3 M B A t7 \/ \ 8 20 2! 22 23 2* 23 26'2T 23 29 <30 31 32 / a* "k*m* * '1 JI i` I: ;1 1 i1 ` !1 ! |I i 1 1 1 . ! .1 -- Oa %&&.&.'LL& :i1 an At Ha dg A! at it fit at Si &) 3 3 % | a. -*tT mM tt* mt\. _____________________ 1 St inSonra A3XB K M. CAJa/ sAeil fmtj V MJ &Mn& AM Mil ill* So <Atf fti Mm AAil BAM Ml ll A NM Pmo.t>&<!( mo Hr SLM Mb (i Sr r VtZr iu COMO BMi "&&&&&& &> &h A L& N T <au mcf SM ta.BMNA HAT Si n7m J^nBI tva & & Ba ui 5* A m * &il & n ho&S- tS/tL*u w *" * 'jw A.4ir< ma Ati mi_ "* ap .M " mm pro ttt ~ Ac Th U>U V 1' ;| . i!i |! i ' i! ! 14 I" Ij 1 ' & Tr A A. Ml NB1 U Bi LTft &. m A/ m * 2^ AMU ; FIORE 19 SPECIAL ARRANGEMENT OF THE PERIODIC SYSTEM OF THE ELEMENTS WHICH WAS USED AS A GUIDE IN THE FINAL VOX HUNT" THAT LEC TO THE OISCOVERY OF THE REMARKABLE EFFECTIVENESS OF LFAD AS AN ANTIKNOCK AGENT. IN THE BOX AT THE TOP OF THE PAGE IS THE ORIGINAL GROUPING AS MADE.BY R. E. WILSON. THE MODIFIED ARRANGEMENT IN THE LOWER BOX IS THAT USED IN THIS SEARCH, AND THE most SIGNIFICANT PART OF IT IS ENCLOSCD BT THE DASHED LINES AT THE LOWER RIGHT. ETC 36892 Report OC-83 95 7/ork was begun at once on the synthesis of the ethyl and phenyl derivatives, of other elements at the right ih the lower grouping of Figure 19, such as phosphors, arsenic, and antimony. A special project entitled "Periodic function of ele ments with respect to antiknock quality" was set up to cover this new phase of the investigation (Monthly report, August 3, 1921) The first of the compounds made were tested as soon as obtained. These tests were made by the customary procedure used up to that time, which was to run in the Delco-Light engine a solution of the compound in kerosine and to note either by ear alone or by observing the pressure-time card of the Midgley indi- . cator whether the knock was reduced by comparison with kerosine alone. If it was reduced, some quantitative idea of the rela tive effectiveness of the compound was then obtained by comparing its antiknock effect with that of aniline or ortho-toluidine-- the latter more easily soluble in kerosine than the former--by the same listening or looking pricess,I I Bouncing-Pin Indicator Developed But these procedures, although they had served the pur pose very well up to that time, were not very precise. And, now that small differences in effect upon knock needed to be measured ] if the periodic function was to be evaluated properly, some more precise and reproducible procedure for making measurements of knock was needed. The effort to solve this problem began in the early summer of 1921. The experimental work was done by Boyd with |the active collaboration of Midgley. On June 2, 1921, (Rec. 13, |p. 48) a search for a fuel that could be need a* a />! ETC 36893 Report OC-83 96 ence in knock measurements was begun. Experiments were made with various mixtures of benzol, petroleum ether, sulfuric ether, pen tane, hexane, acetone, ethyl and methyl alcohols, various anti knock agents of the aniline type, and knock inducers such as Diethyl nitrate. The Midgley indicator was used in these tests Volatility effects and varying effects with changes in mixture ratio caused results to be erratic, however, and the use of the Midgley optical indicator was open to too much error in observa tion to be good enough for the purpose (Rec. 13, p. 55). Next, a temperature method then in use by the Standard Oil Company of New Jersey was investigated (Rec. 13, p. 55). In this method a thermocouple inserted in a plug screwed into an opening in the cylinder head was used to register the rise in temperature. An attempt was made first to measure the vari ations in temperature with a potentiometer. But, when thia method of measurement did not prove to be very successful, the potentiometer was replaced by a sensitive galvanometer borrowed from J. H. Hunt. It was found, though, that this method of measurement was erratic and could not be relied upon to indicate reliably even fairly large differences in knocking tendency. And then began what turned out to be one of the im portant developments in the series of discoveries which led up to Ethyl gasoline. At a meeting of the S.A.E. which Midgley had attended. Dr. H. C. Dickinson of the Bureau of Standards had de scribed a device which he had used to detect whether or not an airplane engine was knocking, such engines being usually so noisy ETC 36894 Report OC-83 V that the sound of knock was too obscure to be observed by ear. This device, which Dr* Dickinson called a "diddle pin," con sisted simply of a free pin held loosely in a guide with its lower end resting on the cylinder head of the engine, as illus trated in the top sketch, Figure 20, page 98. When knock was present the violence of the explosion was such that it made the pin jump off the cylinder head momentarily. But, when knock was absent, the pin did not Jump but rested continuously on the cyl inder head. This pin in the hands of Doctor Dickinson had been only a qualitative device which had been employed merely for detecting the presence of knock. In an effort to utilize the idea embodied in Doctor Dickinson's pin in developing a quanti tative instrument for measuring knock, it was incorporated with the pressure element of the Midgley optical gas engine indicator by removing the shaft which ran from the piston to the mirror arm and putting in its place a free pin held in guides top and bottom. The pin was connected in an electric circuit, and, using the lower end of the pin and the piston on which it rested as contact points, an attempt was made to measure degree of knock by means of a galvanometer in the circuit. But that did not work, partly because of the fouling of the contact points. Various changes were then made in the arrangement to give at last the circuit illustrated at the bottom in Figure 20, page 98, which is a copy of page 57 and a part of page 56 of Laboratory Record 13. It is worth noting that at this time the contact points were continuously in contact, except as they were separated ~.-v;;-*'5 ET c 36895 Keport 0C-3J 3, Uaj*. ft~ "fiLjJJU. **JU& TSU ^ ^ ^ t^4- uJ^ ^Cx V'^~~~N Wyf--^-U4~ 9w* *-- |fnr ^ Ana a^. a<SK i . - ^ - > -*^C Wi o. * ^% ev * J <Jr-A f--_ * 57 /^f......... '"-'* ^ f n 11 n -*- '- f/ -*y "'< r> jTi k(. tf~- <ls a *f jL-*rtz ^ ; Xr ~J*A t* w.*>-4. tA`X *-i/V /r< / 4-jf|-- y?* ^ ' |Tcmm tfc ~. *JL -- * >*i. t)t- ^T^'^SSrsr^-ir^ ~ r2x 1-fij /T, p* X./, c---. ,8.7. V.3^ 98 i>.-4t. a* -*Xf ^ |it~ /y<, I\ 4 . J Pt.m*i j( *i6% ,A44y^fcL^ <*--^ ^7tS^fcr- FIGURE 20 COPIES OP THE ORIGINAL NOTES IN LABORATORY RECORO 13 RE LATING TO THE DEVELOPMENT OP THE BOUNCING-3IN INDICATOR. ETC 36896 Report OC-83 99 by the motion of the pin resulting from knock. From this point on the apparatus and technique were con sistently improved as experimentation continued. On July 22, 1921, the elaborate wheatstone bridge circuit shown at the bottom of page 96 was abandoned and replaced by a simple direct-current cir cuit embodying a resistance, and an electrolytic cell instead of a potentiometer (Record 13, page 60). Then on August k the contact ing mechanism was changed in such a way that the points were nor mally separated, instead of being in contact as before, and they were closed only momentarily when the pin was propelled upwards during knock (Record 13, page 79). The circuit, contacting mechan ism, and pin arrangement thus arrived at are shown in the drawing. Figure 21, page 100, This drawing was made after the system had been developed into a thoroughly usable one and after it had proved extremely useful in pursuing the periodic antiknock function of the elements, as related below. As a description of the development of this new instru ment, a paper on "Methods of Measuring Detonation in Engines" by Thomas Midgley, Jr., and T. A. Boyd was prepared and presented at the Winter Meeting of the S.A.E. in January, 1922 (S.A.E. Jour., 10. 7, January, 1922). It was in connection with the preparation of this paper that Boyd suggested that the instrument be called the bouncing-pin indicator, by which name it has been known ever since# The bouncing-pin indicator as thus developed is substanti ally the same instrument which is now used universally in. making knock ratings. About 1926, at the suggestion of Robert Janeway, now of the Chrysler Corporation, the piston of the pressure element ETC 36897 I?P0RT OC-83 +If0 V.- D.C. <> <> P9 1 100 =-/ =-j =H 1 I -/0%/fcSO, FIGURE 21 THE 30UNCING-PIN INDICATOR AS DEVELOPED IN 1921, SHOWINtt THE CIRCUIT, THE PIN ARRANGEMENT, THE CONTACTING MECHANISM, and THE ELECTROLYTIC CELL. Report OC--83 101 *as changed to a diaphragm, which further improved the consistency of the instrument, A picture of the first cabinet form of the in strument with the element mounted on a Delco-Light engine, and taken in 1923, is shown <>s Figure 22, page 102. The later development, in which the bouncing-pin indicator was applied to a variable-compres sion engine with a double-float device for regulating mixture ratio by adjusting the flow of fuel to the engine by hydrostatic level is pictured in Figure 23, page 103. This picture, taken in 1927, just a year before the organization of the Detonation Subcommittee of the Cooperative Fuel Research Committee which developed the present official knock-testing method, thus shows several of the features which were finally incorporated in the official method: the bouncingpin indicator, a variable-compression engine, and a double-bowl hy drostatic-level carburetor for making measurements by the method of matching fuels, as had been done in this work from the first. Others of the features incorporated in the official method, such as the knockmeter which was substituted for the electrolytic cell and the synchronous motor for absorbing engine output and holding the speed constant, were first used by the Ethyl Gasoline Corporation, in the course of the large amount of work which they did on problems ref lating to the precise knock-rating of fuels. Still another important item in respect to knock testing, which came out of the later work of the Ethyl Gasoline Corporation and which may be mentioned here in passing, was the suggestion to use heptane and iso-octane as a basic scale of antiknock quality (Graham Edgar, I'lleasurement of Knock Characteristics of Gasoline in Terms of a Standard Fuel," Ind. Eng. Chem., 19, 145 January, 1927). 10. > FIQJh 22 ~t*ST CABINET rORM OT THE BOUNCINC-PIN INDICATOR. ETC 36 9(3 0 ETC 36901 Report OC--83 104 This suggestion was adopted by the Cooperative Fuel Research Committee in 193O, came into general use in 1931, and has been used universally ever since, altogether supplanting the arbitrary standards necessarily employed prior to that time. Finding the Periodic Function of Antiknock Effect By the latter part of August, 1921, the bouncing-pin indicator and the method of making knock ratings by its aid had reached a stage of development at which it was thought suitable to begin rating the several compounds prepared during the summer to be used in investigating the peri odic function of the elements in respect to effect upon the fuel knock. The plan, sb before said, was to test in a systematic manner suitable eon- pounds of all the elements at the extreme right in the lower grouping of the special arrangement of the periodic system shown as Figure 19, page 94. The investigation was centered in the first four groups, which, lifted from the arrangement. Figure 19, and expanded with explanatory matter, are as follows: 4 Carbon Group C Carbon 3 Nitrogen Group N Nitrogen 2 Oxygen Group 0 Oxygen 1 Fluorine Group F Fluorine SI Silicon P Phosphorus S Sulphur Cl Chlorine Ge Germanium Sn Tin Pb Lead As Arsenic SB Antimony Bl Bismuth Se Selenium Te Tellurium 8r Bromine 1 Iodine TC 36902 Report OC-83 105 The compounds which had already been prepared for test. or which were prepared as the tests proceeded, were rated in the order given immediately below. All were ethyl, amyl, or phenyl compounds of the respective elements. The primary period of these tests extended from August 25, 1921, to December 7, 1921, although extensions and refinements in the ratings were made later, as will subsequently appear. Element Compound Tested Page Recorded in Record No. 13 Oxygen Bromine Iodine Chlorine Tellurium Selenium Fluorine phenyl ether phenyl bromide amyl bromide amyl iodide phenyl chloride amyl chloride diethyl telluride diphenyl telluride diethyl selenide diphenyl selenide phenyl fluoride 125 126 and 150 129 129 131 133 135 137 138 lU 142 Sulphur Oxygen diethyl sulphide diethyl ether 145 149 Nitrogen Phosphorus triethyl amine . triphenyl amine triethyl phosphine " triphenyl phosphine 155 157 159 161 Antimony Arsenic Tin triphenyl stibine triethyl stibine triphenyl arsine triethyl arsine tetraethyl tin 171 172 (takes fire spontaneously 1 173 175 177 Induced per preignition t rtA ETC 36903 Report OC-83 106 Some of these compounds--Such as those of chlorine, bro mine, iodine, selenium, and tellurium--had of course been tested before. But they were included in the present program anyway, be cause now the object was to get really accurate ratings of equiva lent compounds of the various elements under comparable conditions. As each rating was obtained it was plotted on a 3-dimensional graph called "The Peg-Board." This consisted of a square board in which a peg was set at the point corresponding to the location of each element as arranged in Figure 19> page 94, or more elaborately in the text above, the height of each peg being made to conform with the degree of effectiveness as a knock suppressor of the element for which it stood. On this gra.h it soon became apparent that, as suspected from prior results, there is a periodic function of the elements with respect to effect upon knock, in that degree of ef fectiveness increased as the bottom of each column was approached. Interest in the results was accordingly so intense that the ratings for arsenic, antimony, and tin were telegraphed to Midgley who hap pened to be visiting at the time at his father's home in Massa chusetts. It was on October 28 and 29, 1921, that the ratings of tetraethyl tin were made. These showed that tin, the first element in the 4-column or the Carbon Group to be tested, was an effective antiknock-agent. This was so in spite of the fact that the presence of the tin compound induced preignition in the engine, and thus made ratings difficult and results a little uncertain in a quantitative sense. The discovery, based on ratings made on successive days, that tin is an effective antiknock element was considered to be ex tremely important. This was so because it pointed to lead, the ele- ETC 36904 Report <T-83 107 oent iar.ediately below tin in the Carbon Group, as very likely to be a powerful knock suppressor. ETC 36905 r Report OC-83 1Q8 CHAPTER VI THEN CAME LEAD And so the effort to make tetraethyl lead as a possible antiknock agent, which as already related had been abandoned near ly three years before when Gilkey damaged the thermocouple of the muffle furnace in Mougey's laboratory, was soon taken 'up again. This time another method of synthesis was tried. This method was old also, having been used by Buckton in 1859 and by Frankland and Lawrence in 1879. The procedure was to prepare zinc ethyl and then to drop it on lead chloride. It was by this procedure--the same as had been used previously in making some of the alkyl com pounds already tested--that C. A. Hochwalt prepared on December 8 and 9, 1921, the first tetraethyl lead obtained, just a few cubic centimeters. Then on December 9, 1921, in the presence of Midgley and Hochwalt, Boyd made the first engine test of this historic product (Record 13, p. 200). For the first exploratory test, a solution of 1 per cent tetraethyl lead by volume in kerosine was prepared.* The intention was to compare this solution with 2 per cent aniline in kerosine and 1 per cent aniline in kerosine as bracketing reference fuels. But right away it was seen that the tetraethyl lead mixture was much too free from knock to be tested by comparison with these fuels. Successively weaker solutions of Kerosine rather than gasoline was used as fuel in most of the early work on testing antiknock agents, chiefly because it was more prone to knock than gasoline, but also because in the mixing valve with which the Delco-Light engines used for testing were fitted kerosine mni*o nnl fnrw arH st ant nni*atlna than nn'ne> msolines. ETC 36906 Report OC-83 109 tetraethyl lead in kerosine were accordingly made by diluting the original mixture, until at last it was decided from the results that a solution containing one-fortieth of one per cent tetraethyl lead in kerosine could be compared with the reference fuels--that is to say, this mixture lay in degree of freedom from knock somei' I where between the two aniline mixtures. The customary quantita tive rating by means of the recently developed procedure employ ing the bouncing-pin indicator was then run, and showed that onefortieth of one per cent tetraethyl lead in kerosine was equiva lent to 1.3 per cent aniline in kerosine. A copy of the page from Record 13 on which the original data of this test were recorded is included as Figure 24, page 110. Figure 24-A, page 111, is a copy of the plot of these data made at the time, which shows that onefortieth of one per cent of tetraethyl lead in kerosine turned out to be equivalent in knock-suppressing effect to 1.3 per cent ani line in kerosine. This amazing and exciting result was then checked by another and still more careful determination, using both one-eight ieth and one-fortieth per cent tetraethyl lead in kerosine (Rec. 13, p. 202), and these ratings agreed well with the first. Thus the as tounding result obtained was that on the volume basis tetraethyl lead was about 50 times as powerful as aniline for suppressing knock, and that on the molecular basis one mol of tetraethyl lead was equivalent in antiknock effect to about 120 mols of aniline. It is easy to understand that the excitement produced by this discovery was great.. At the first.opportunity, the result was ETC 36907 REPORT OC-63 I COPY OF ORIGINAL LABORATORY RECORD OF THE FIRST TEST OF TETRAETHYL LEAD IN AN ENGINE IN WHICH THE DISCOVERY OF THE REMARKABLE EFFECTIVE NESS OF LEAD AS AN ANTIKNOCK AGENT WAS MADE. REPORT jC-4' COPY 'HE OK IG;HAL PLOT OF THE RESULTS OF THE FIRST TEST OF TETRAETHYL LEAD AS AN ANTIKNOCK AGENT, SHOWING THAT ONE-FORTI ETH OF ONE PER CENT TETRAETHYL LEAO WAS AS EFFECTIVE AS I.3 PER CENT ANILINE ETC 36909 Report OC-83 112 *i demonstrated to Mr. Kettering and to Dr. Clements, of course. From the time of the first discovery of an antiknock agent, it had been the practice of Mr. Kettering to demonstrate for the benefit of visitors the striking effect of eliminating knock in a running en gine by the simple means of adding a little of the antiknock agent to the knocking fuel. The demonstration was usually made by running the Delco-Light engine on kerosine fed from a supply in a 4-ounce sample bottle; and, when the engine was knocking loudly, some easily soluble antiknock agent such as toluidine was added in small amount to the kerosine in the bottle, thus stopping the knock completely. Now that in tetraethyl lead an eliminator of knock which was so ex tremely powerful that only a drop or two of it need be added to the bottle to quiet a knocking engine, the demonstration became much more striking; and Mr. Kettering accordingly showed it to his visi tors all the more frequently. Incidentally, the practice of showing the discovery to so many people had long been deplored by the men in the patent department. But lr. Kettering went ahead with the demon strations anyway, and no bad results ever came of them. It may be of interest to note here also a feature of the bouncing-pin indicator which was very useful in such demonstrations, as well as in making approximate measurements of antiknock quality, but which was not mentioned in the account of the bouncing-pin indi cator given earlier. Employed then as a resistance in the electrical circuit was a mazda lamp. This lamp is indicated in the drawing. Figure 21, page 100, and it may be seen in the cabinets, Figures 22 and 23, pages 102 and 103. Whenever knock occurred, this lamp would light up intermittently from the current then flowing in the circuit. ETC 36910 Report 00--83 113 and the intensity with which it glowed was an excellent visual in dicator of the degree of knock occurring. In demonstrations of knock and of the effect of antiknock agents, it thus served so ef fectively as an aid to the ear as to make such a demonstration quit e impressive. The discovery of the marvelous effectiveness of lead com pounds as antiknock agents thus further established the validity of the periodic function of the elements, so far as those in the sec tion of the arrangement represented by the fluorine, oxygen, nitro gen, and carbon groups were concerned (Figure 19, page-94). The three-dimensional peg board plot, previously mentioned, is no longer in existence, but would not lend itself well to representa tion in a photograph anyway. And so the effect is shown as well as may be in the two graphs. Figure 25, page 114, and Figure 26, page 115. These graphs, which were prepared at a little later time, have had an interesting history, as will be related further on in this story. In Figure 25 the antiknock effects of the elements in each of the four groups are shown, each to a different scale. There the increase in antiknock effect' toward the right, which is toward the bottom of the corresponding column in the periodic ar rangement, Figure 19, page 94, ia apparent. Then in Figure 26 the antiknock effects for three of the four groups are plotted all to i the same scale. There the great height to which lead towers above fall the other elements considered is readily seen. Another picture [of some of these relative effects is snown in Figure 27, page 116. ETC 36911 REPORT OC-33 FIGURE 25 PLOT OF THE ANTIKNOCK EFFECTS OF THE ELEMENTS IN FOUR GROUPS OF THE SPECIAL PERIODIC SYSTEM USED AS A GUIOE IN THIS SEARCH. THE VERTICAL SCALES ARE DIFFERENT, BUT THE RISING ANTIKNOCK EFFECT TOWARD THE RIGHT IN EACH GROUP IS APPARENT. fci" V* REPORT OC-83 Atomic Number FIGURE 26 THE OUTSTANDING ANTIKNOCK EFFECT OF LEAD IS APPARENT HERE, Y-HERE THE RELATIVE EFFECTS OF THE ELEMENTS IN THREE OF THE GROUPS SHOWN IN FIGURE 25 ARE PLOTTED TO THE SAME SCALE FIGURE 27 HERE THE MINUTE AMOUIT OF TETRAETHYL LEAD NEEDED FOR A SIVEN ANTIKNOCK EFFECT BY COMPARISON MITM SOME OTHER COMPOUNDS IS PICTURED IN ANOTHER f.'AY. ETC 36914 Report 0C-S3 117 Of the many materials tested in the search for an anti knock agent, which led finally to the discoveries just described, only a few have thus far been mentioned. Appendix IV is accord ingly included to give some idea of the extent of the testing that was done during the course of the endeavor. The several-page list, Appendix IV, was prepared in 1925, and thus contains a few compounds tested after the time of the discoveries described above. Early Contacts with the Standard Oil Development Company Another interruption in the main thread of the story may be made at this point to tell about some supplementary events of the year 1921. The first of these relates to a further effort made during the summer of 1921 to produce antiknock agents directly in the gasoline. This was an idea upon which experiments were made at different times in the course of this research. The present attempt was commented upon on June 10. 1921, in a letter from Midgley to Frank A. Howard of the Standard Oil Development Company, as fol lows: "I am planning to be east the week after next . . . and I am hoping at that time that I may have some of the fundamental chem istry towards producing our antiknock material in gasoline at the refinery. I feel that our greatest hope for commercialization now lies in this direction. Diethyl teiluride is a wonderful antiknock material, but the tellurium poisoning, which is nothing more than a very obnoxious odor, makes diethyl teiluride a highly disagreeable material and there are really but very small quantities of tellu rium available. These two factors apparently knock tellurium out as a possibility, and we are going ahead attempting to eventually y ETC 36915 r Report <T-83 118 nitrate and reduce natural compounds to make antiknock materials therefrom." Such compounds, if obtained by the process of nitra tion and reduction, would of course be of the amine or aniline type; and, as has already been said, these are not free from dif ficulties either (bad odor, attack on metals, toxicity). But the work was not confined to the nitration and re duction of compounds in gasoline. Attempts were made also to pro duce compounds of selenium directly in gasoline. No such compounds were obtained in a practical way, but the investigation did lead to the discovery, mentioned earlier in this account, that iron selenide is a catalyst for the cracking or oils (monthly reportj Sep tember 30, 1921), and particularly for aiding the formation of hy drocarbons of the aromatic type. Some of the results of this par ticular discovery were published in a paper by Uidgley and Hochwalt (Ind. Eng Chera., 16, 365, 1924), and also patented by Midgley (U. S. 1,721,523, July 23, 1929)* The letter of June 10, 1921, from Midgley to Frank A. Howard of the Standard Oil Company of New Jersey Development De partment, quoted above in part, shows that in the summer of 1921 there was contact with men in that company on matters relating to knock suppressors, and specifically in respect to the possibility of making such compounds in the refinery. This contact was con tinued and later resulted in a plan for a definite written agree ment relating to collaboration on making antiknock compounds in the refinery, as well as on other matters relating to antiknock com pounds, The state of affairs in this regard in the early part of 1922 is suggested in Figure 28, page 119, which is a copy of a letter L ETC 36916 V- RE.PCHT OC-33 STAXl>Altl> Oil. ('OMl'.VXY lhlVRI.ni*MKWT On>AMTMBirr M HMnwr nuni.aw<u XkvYokk lank 1. Ifa. I 19 Ir. Thoae* Blili;. Jr., Oenarel Kotor* Raaoareh Cork., I*/ton. 0. Hr loar Kr. IU|lir: Vllaon of 'Took* ijut Saturday olth a* la Illiahoth and toll at than that rn *nl I ma to h*r* gottaa oar *lr** oroooal oa tha 'knock* propoattloa ahleh * dltoaaool la Cbloag*. t ea aaro that I aa to bleu* for thl*. I ha! expaete! to aa* 70a l har* /oa s**t car pacpl* on tk* la*t la/ cf tha Beating hat *aa T want to look /oa ap I fount /oa hal alraad/ left. I talkal to ** of car effloar* anl director* ahe vara la Chleage at tha tla* aal tha/ eeuld aaa ae poaalhl* eb^aatloa to tha arrangeaant ahloh a* had dlacaaaad. T hal tha Izpraaaloa that it aaa agraal bataaaa oa that /oa aeuld am** a* to a daflolta lln* of laralopcaat aerk okleh aa a*ra to undertake with tha Idea of aorklng oat a aathol c! coat* of producing an antl-knoer botor foal acoordlng to /oar pita Ic tha raflaar/. V* aara than to either aooapt or ra'aot thl* apaolfla oropcaal. Tf accepted It *** to h* ae th* teal* that thla Coapary ould occur* a Ucanaa for ltaalf aa oeaaanaatlcn for l*r*lo[lng the raflrar/ cr rrodoetlen anl. Tf e* dacllr.ad the apaolfla propoaltlCB. /on ear* to fc* fro* to leal with It la aa/ aa/ /oa thought fit. Vllaon tall* e* that It aaa Me lapraaaloa frea hla talk* arltk hoth cf tie that I aaa join/ to /roper* a general oc.ntraot and th* oal/ after thla ooatraot aaa exaoutet ear* /oa te antalt a dafialt* prepcaal. Tf thla la tha undemanding cf th* aettar ahlcn /ca hal, plaaaa aooapt a/ apolcgla* for lala/lag ae long, do /oa tan, t hal alraad/ aacored appreral U too propcaltlcn* froa cs paopla along thla llna ml after oar '.aid la Chicago, I aa aura that thar* *111 ha ao difficulty la getting through anything cf thl* aort ahloh /oa and I agree apoa. la T get it frea /oa. th* laportaat thing at th# praaaet tla* aaa to har* aa gat hue/ aa a definite lln* ahloh jam hollar* Juatlflaa th* laaadlat* attention of a r*floor. T har* haan oat In California also* th* latter cart of January anl bar* Juet returned. I a threatened otth oca* rather prclcnrel aboencaa daring th* eealng fear tenth*, t aa rar/ anzlOB# to gat thla this* cleared ap anl th* oork ahloh /oa hal la atal atartal at th* aarltaat aoaant. If /oa *111 alrla* ohat aoall h* naoaaaar/ for to tc do doon har*. I rill onlartok* to gat It aoeoa* pllahad promptly and If you think It aoull orpodlt* th* final orraegasanta. I can core oat to Da/tee *lth an/ propcaltlcn along tha llnaa ehlch a* dlaeaeaal ehtch yon rant te har* la feraal ahap* froa aa and try to aattl* It an otth /oar paepl* at obo* ae I can b* ear* that sny future ahaaneaa of aln* *111 not Ida/ th* aorklng oat of thla aeat lr.portnt arohlra. *11on hat .'not atartal hla aerk *lth aa la ce-eperatloa *lth /oar paopla and T fled It 1* eartolnly a }tj to bar* hla co-oparatlng. Do /oa not thlak ** oould hoth at* hla to agreetag* In thla antl-kr.cck oork* Tnoept for /curaalf, Vllaon lo the flrat nan I har* oat ohoa* Bind corked otth abaclat* clarity oa thla probla*. ** har* had acta little ouecaaa alth ecu* laboratory oork In oodlfylng tha pro par tie a of ell* daring th* peat fa* acatha end t hop* that ** *111 be abl* to aak* too* azparlaanta oa a largo teal* oa thla aeon. It oould be a great ad rentage if ** ceoll ?*t oar arrangement *lth /oa oeaplated *0 that a* oould open ap In all oa both all** on thla natter anl parhap* har* th* benefit of Vllaon'* rle* aa call. Vlth beat legerla. Vary truly your*, 7 C l-h***^ FIGURE 28 LETTER FROM FRANK A. HOWARD TO MIDGLEY RELATING TO 0 I SCUSS'ONS OF POSSIBLE COOPERATION BETWEEN THE GENERAL MOTORS RESEARCH CORPORATION ANC THE STANDARD OIL DEVELOP MENT COMPANY. ETC 36917 neuurr. nC--8J 120 of March 14, 1922, from F. A. Howard to Midgley. It was between the time of the conversations in Chicago mentioned in Mr. Howard's letter (presumably at the time of the 1921 Annual Meeting of the American Petroleum Institute) and the writing of his letter in March. 1922, that the discovery of the remarkable antiknock effect of lead was made. This discovery changed matters so profoundly that on Larch 16, 1922, Midgley wrote to Howard as follows (in part): "Very shortly after seeing you in Chicago, our research work took a very sudden turn in a di rection that would indicate that it would be a mistake both on your part and on ours to enter into an agreement such as we dis cussed at that time" (Letters, page 41)* Thus it was not until more than two years later, after the lead discovery had been put on the market, that an agreement was entered into between General Motors Corporation and the Standard Oil Company of New Jersey. However, it may be worth ?/hile to go still further back and to include here also a brief outline of the earlier contacts between the Standard Oil Company of New Jersey and Mr* Kettering's group. Contact began first in 1919 right after the publication of Mr. Kettering's paper, "More Efficient Utilization of Fuel" (S.A*E. Journal, 4_, 263, April, 1919). Frank A. Howard, who was then a patent attorney in Chicago, having read Mr. Kettering's paper, wrote E M. Clark of the Standard Oil Company of New Jersey tell ing him how important he thought the paper and the disclosures nade in it were from the viewpoint of the oil industry. In May, L919, Hr. Howard visited Mr. Kettering at his laboratory in Dayton *This and subsequent similar references in this report refer to a group of photostats in the records of the Fuel Department, "Copies of Matter Selected from Correspondence Files*" Report OC-83 121 and was much impressed. He wrote a long report to Mr. Clark about his visit, and suggested that a research labiratory similar to Mr. Kettering's be established by Mr. Clark's company. Mr. Clark then sent two of his own men, Dr. Marie Heacham and F. C Fyke, to visit Ur. Kettering's laboratory. They likewise were impressed with the great pioneering importance of Mr. Kettering's endeavors and recom mended the establishment of such a research laboratory by the Stand ard Oil Company of New Jersey. Right away, in June, 1919, as a step in that direction, the Standard Oil Company of New Jersey ordered a Midgley indicator. The result of the events mentioned in the preceding para graph was that in the fall of 1919 Mr. Clark employed Mr. Howard and assigned him the job of organizing a research laboratory for the Standard Oil Company of New jersey. The following paragraph from a letter, written April 27, 1927, by Frank A. Howard to "llliam Benham of the Department of Justice, gives in Hr. Howard's own words an ac count of events following his new connections "In the fall of 1919, I entered the service of the Stand ard Oil Co. of New Jersey as Manager of Development for them, and was assigned the task of building up the research labora tories of the Company. One of my first steps in this work was to again get in touch with Mr. Kettering and Mr. Midgley and ask their advice on how best to proceed along the line of re search in the field in which Mr. Kettering had pioneered. These gentlemen very generously gave me the benefit of much of their experience in this connection and actually supplied for the Standard Oil Co. of New Jersey, at cost to them, three experimental engines especially adapted for this work and some additional scientific equipment which they had devised. From this time on, the personnel of our laboratory, which was lo cated at Bayway, N. J., kept in general touch with the person nel of Mr. Kettering's laboratory and exchanged views and in formation which it was thought would be mutually helpful," ETC 36919 Report OC-83 122 The Spectroscope Applied to Studies of Combustion The second of the supplementary events of the year.1921 to be mentioned was the work done by Midgley with the aid of W. K. Gilkey on the use of the spectroscope to observe combustion in an engine, and especially knocking combustion. The object was to get what in formation was possible by such means on the temperatures and the pressures within the combustion chamber and on the chemical reac tions occurring there. Observation was through a small glass wind ow placed in the shell of a spark plug which was screwed into the combustion chamber opposite the spark plug. A special spectroscope was built for this investigation with the aid of Henry C. Lord, pro fessor of astronomy at the Ohio State University. This instrument had a particularly wide dispersion due to the fact that it' combined the effects of a prism and a grating fir dispersion. The course of this spectographic research need not be reported here, as it did not enter in an important way into the search for an antiknock agent* But a raper by Thomas Midgley, Jr., and K. Gilkey relating to this investigation and entitled "Spectroscopic Investigation of In ternal Combustion" was presented before the S.A.E. at the Annual Meeting in 1922 and was published later in the S.A*E. Journal, 10, 218 (March, 1922). Further Aid to the Army The third supplementary event of the year 1921 relates to the continued effort of the men in the Army Air Service at McCook Field to get an antiknock agent that would be usable in airplane fuels. As related earlier, they had not found the soluble compounds TC 36920 f Report OC-83 123 of the aniline type (toluidines and xylidines) and their use in in jectors to be very practical. One reason for this was the attack which such compounds made on metals, as was mentioned earlier in this story. Another was the probability that in time of war such compounds c~>uld not be had, because the toluene and the xylene from which they are made have to be had for explosives. On the evening of October 25, 1921, Captain G.5.A. Hallett visited Midgley at his home and, quoting from the notes made later by Captain Hallett (Let ters, page U6)> "It was agreed that the General Motors Corporation would make up samples of three anti-knocks in sufficient quantities to mix with three hundred gallons of gasoline in each case," The. antiknock compounds to be supplied were diethyl selenide, ethyl ani line, and come of the naphthylaraines, t'.? .latter only if `.hey could be made coxuble enough. A considerable amount of work was according ly done during November, 1921, chiefly by Hochwalt, in preparing di ethyl selenide to meet this demand. The ethyl aniline was purchased from, du Pont. As further indicated in Captain HaJlott's notes, it was his intention to incorporate the most promising of the antiknock agents in all the Army Air Service fuel specifications. But of course the problem was not really solved until the discovery of the effect of tetraethyl lead shortly thereafter. Intensive Research on How to Make Tetraethyl Lead Returning now to the important discovery of the antiknock effectiveness of tetraethyl lead, as made on December 9, 1921, it may be of interest to quote what was said about it in the regular monthly progress report dated December 29, 1921: k ETC 36921 Report X-83 124 "The outstanding development of the past month was the discovery of the remarkable effectiveness of organic com pounds of lead for the suppression of detonation in the com bustion of highly compressed mixtures of gasoline and air. This discovery was made as a result of the systematic in vestigation of compounds of the chemical elements which we have been conducting for some time.. Preliminary measurements of the effectiveness of tetraethyl lead indicate that it is roughly 50 times as effective as aniline for the sup pression of detonation. This material (tetraethyl lead) has only a faint but rather pleasant odor; it imparts no notice able odor to the exhaust when run in sufficient concentration to permit a compression ratio of 7:1 to be used; it is very soluble in gasoline; it is colorless; and, while there has not yet been sufficient time to thoroughly test the stability of the material in gasoline solution, references to the -com pound in the literature indicate that it is very stable in air, and even in pure oxygen. The raw materials for the preparation of the material are cheap and plentiful. It is necessary to develop a satisfactory process for making the proper organic compounds of lead, and intensive work is now being done with this end in view." In the intensive research or -ncthcit- of maHr.g .etraethyl lead, as Just mentioned, several methods were soon trid. In ad dition to the reaction between zinc ethyl and lead chloride by which the tetraethyl lead first tested had been made, these included the fol] ow? ng: 1. Refluxing various alloys of sodium and lea.: and of mag nesium and lead with ethyl sulphate, with ethyl carbon ate, and with ethyl benzoate. 2. Treating zinc-copper couple with ethyl iodide and lead chloride directly, that is, without making zinc ethyl as an intermediate. 3. Electrolysis of acetone in 20 per cent sulphuric acid solution, using lead electrodes. (This method was later studied at ilassachusetts Institute of Technology.) L ETC 36922 Report OC-33 125 U. Grignard reaction, trying both methyl chloride and ethyl chloride with magnesium and with ether as solvent (pen tane tried as solvent also), and.then adding lead chlor ide in theoretical amount. 5. Reformatsky's synthesis, a one-stage reaction in which ethyl chloride was treated with lead chloride, using zinc as a condensing agent. 6. Refluxing various alkylating agents--ethyl sulphate, ethyl benzoate, ethyl acetate, and ethyl alcohol--with magnesium and lead chloride. 7. Heating lead with ethyl iodide in the presence of alumi num chloride (Friedel and Crafts* reaction), and heating lead chloride and ethyl ioi5.de vr.ih sodium iret ~ i (fj.ttig's reaction). Some of these several trials net with fair success, but none seemed to offer more promise than the method of preparing zinc ethyl and reacting it vd.th lead chloride, as employed in preparing the tetraethyl lead on which the tests reported above were made. So, during the week of January 1, 1922, the effort to make tetraethyl lead began to be concentrated on this method. In brief, the process (.Lead Diary, page 7)* consisted in making a zinc-copper couple (105? copper, later reduced to 1%) by heating a mixture of 30 mesh zinc and* 1 ^Beginning in February, 1922, with a summary cf the work done up to that tine on lead as an antiknock agent, a daily record of all the work done on lead in the Fuel Department was written by Boyd. This special record is No. 13 in the Fuel Department files and it was called the "Lead Diary," It is in three volumes and extends to May 1, 1923. etc 36923 Report OC-83 126 copper powder, the latter prepared by reducing copper oxide; in re acting the resulting couple with ethyl iodide; in distilling out the zinc ethyl formed, and collecting it in an inactive atmosphere of carbon dioxide; and then in slowly adding to the zinc ethyl under a reflux condenser lead chloride in theoretical amount. After having allowed the mixture to stand for several hours, water was added slow ly with cooling to the mud-like product at that stage, and the tetra ethyl lead formed in the reaction was then distilled out. As a result of many experiments, the technique of the method was rapidly improved, and in early February, 1922, a larger apparatus--one intended to yield about one gallon of tetraethyl lead per day--was constructed. The two pieces of equipment built especi ally for the synthesis of zinc ethyl on thos scale are pictured in Figure 29, page 127 and Figure 30,. page 128. Then in early March, 1922, after much experimentation in glass apparatus as well as in the larger metal apparatus, a second semi-works outfit for making zinc ethyl was built. This was called the "pan apparatus", and as later modified is pictured in Figure 31, page 129. In this appa ratus each batch was on the basis of about 5 pounds ethyl iodide, and the yields of zinc ethyl were up to 82 per cent on the basis of the ethyl iodide used and not recovered, although the average yield was not nearly so high* Then on April 3, 1922, a plan was made for a plant to pro duce 100 gallons of tetraethyl lead per day by the zinc ethyl method. This lay-out, as later put into definite form is shown as in Figure 32, page 130. The processes indicated there for recovering iodine and for ETC 36924 ETC 36925 VESSEL FMt NMtlNV ETt^fVUSEN IN THE CMLY UCINQ TTnUCTKYL LEAD etc 36926 w ETC 36927 r REPORT OC-83 Total ftrvcs tmcmt /loop Cost Pea G**-loh $40,000 3.500 So Ft $/.SO 30" 30 130 Piecs m Process - &HC3 or TruCmiHO FIGURE 32 LAYOUT Of PROPOSED PLANT FOR MAKING IOO GALLONS OF TETRAETHYL LEAD PER DAY BY THE ZINC ETHYL ROUTE, THE METHOD UNDER CON- ETC 36928 Report OC-83 131 converting it again into ethyl iodide had been developed, chiefly by James ?.. Andrew, simultaneously with the work on the making of zinc ethyl done by C. A. Hochwalt and described above. By the zinc ethyl process, it was then expected to make tetraethyl lead at a cost of about $7.50 per gallon. But on April 4, 1922, Uidgley and Hochwalt left for Bir mingham, Alabama, to attend the spring meeting of the American Chemical Society. Events which happened there, to be related presently, changed the course of the research on making tetra ethyl lead. But, before telling of these events, a digression will be made to tell about the beginning of research on lead prob lems in the Research Laboratory of Applied Chemistry at Massachu setts Institute of Technology. The Participation of M.I.T. Begins R. E. V'ilson and C. S. Venable, respectively director and assistant director of the Research Laboratory of Applied Chem istry at M IT., ^pent February 8 and 9, 1922, at the laboratory at Dayton. The visit was made for the purpose of becoming familiar with the work that had been done up to that time on the problem of making a liquid compound of lead suitable for use as an antiknock agent,. The laboratory at L'.I.T. had for some time previous been conducting a research on lubrication which had been supported in part by the General Motors Research Corporation. Now, in view of the apparent magnitude of the problem of making lead compounds for use as antiknock agents, it was thought that the group at li.I.T. might be of assistance in solving it in a thoroughly commercial' man ner. So an initial expenditure of 2400 was authorized bv the ETC 36929 r Report QC-83 132 General Motors Research Corporation to cover five months of research at I'.I.T. on the preparation of lead compounds. R. E. Wilson was destined to play an important part in the later developments relating to tetraethyl lead as an antiknock agent, which will appear as this account proceeds. C. S. Venable did not have such an important part in the endeavor, however, for a few months after his visit to the laboratory at Dayton he left U.I.T, to become director of research for The Viscose Company. After going over various ideas on possible methods of making lead alkyls during the visit of Wilson and Venable, it was agreed that it would be best for them to investigate the possibility of making a suitable compound by the electrolysis of acetone in sul phuric scid solution using lead electrodes, a method described in the chemical literature and already mentioned The product, so obtained was tetraisopropyl lead. Although a great deal of fine work on this method was done at M.I.T., and although the endeavor, which was con tinued to the end of April, 1922, progressed past the stage at which preliminary estimates were made for n full-scale plant (Lead Diary, page 88), that particular phase of the work did not come to any prac tical conclusion. Among the reasons for this were that the tetraiso propyl lead produced was found to be highly unstable, that its ef- \ fectiveness as an antiknock agent by comparison with tetraethyl lead was low, and that the work at Dayton soon yielded what appeared to be a thoroughly practical method of making tetraethyl lead. Besides Wil son and Venable, one other man worked on the electrolytic research at M.I.T. in 1922. This was Dr. '"illiam G. Horsch, who for several years i ETq 36930  Report QC-83 133 has been a research chemist in the research laboratory of the SoconyVacuura Oil Company at Paulsboro, New Jersey. The Executive Committee Asks for Rome Information In late January, 1922, the President of General Motors Cor poration, L!r. P. S. du Pont, sent Mr. Kettering an "Advice of Action" of the Executive Committee to the effect that, $120,000 having been expended in fuel research since the laboratory had become a part of the Corporation, the President had been requested to ask for several items of information on progress in the development of an antiknock agent. These related to probable cost, expected beneficial effects, steps taken toward commercialization, and the like. In answer, liidgley prepared a report under date of February 2, 1922, in v/hich he out lined the expected usefulness of an effective antiknock agent in giving more miles per gallon and so conserving fuel suoplies, gave a resame of progress up to that time in the search for a practical antiknock agent, and included specific answers to each of the ques tions asked in the "Advice of Action," In his answers, L'idgley estimated that tetraethyl lead could probably be made for less than $20 per gallon and that on the basis of its value it could be sold fc- $30. Ke told what progress had been made up to that time cn methods of making tetraethyl lead, and esti mated that to satisfy the existing potential market for such an anti knock agent a total investment of $2,000,000 would be needed. It was just one year after this report was vrri'ten at the request of the Ex ecutive Committee that the sale of tetraethyl lead to the public as an antiknock agent began; but, as will subsequently appear, it was more than 5 years later before any profit was realized from the en- ETC 36931 Report OC-83 134 CHAPTER VII THE SODIUM-LEAD METHOD OF MAKING TETRAETHYL LEAD Returning now to the events which caused the research at Dayton on the making of tetraethyl lead to be diverted from the zinc ethyl method, the turning point was a conversation between Midgley and Dr. Charles H. Milligan (now manager of research and develop ment, American Agricultural Chemical Company). This conversation occurred on the train returning from the Birmingham meeting of the American Chemical Society. The essential item was a remark by Dr. Milligan that he had found isopropyl compounds unstable and very difficult to make by comparison with the corresponding normal propyl compounds. Midgley had tried a month earlier to get isopropyl iodide to react with sodium-lead alloy; but with very little success, al though he had used ethyl acetate as a catalyst. He had also tried to combine ethyl iodide with sodium-lead alloy, apparently without any success whatever (letter Midgley to R. E. V.'ilsor., March 2, 1922; Lead Diary, pages 48 and 49). The method of making lead alkyls by the use of sodium-lead alloys was an old one, having first been used by L'dwig and described in the literature about 1853 (Lead Diary, page 167). It was this method which Vi. K. Gilkey had followed in his historic but unsuccessful attempt to prepare lead ethyl in Febru ary, 1919, as already related. . The result cf Dr. Milligan's hint that normal propyl com pounds formed more readily than isopropyl compounds was that `the day after Midgley and Hochwalt returned from Birmingham on Friday, April 7, ETc 36932 Report OC-83 135 Hochwalt began the preparation of some normal propyl iodide. Then on Monday, April 10, 1922, the propyl iodide so obtained was treated with the alloy of lead and sodium, Naj^b. "A violent reaction en sued, in which much gas was evolved" (Lead Diary, page 125)* Some tetra-normal-propyl lead was obtained in this reaction, which in the engine test made immediately proved to be of about the same effec tiveness as tetraethyl lead for suppressing knock. Reasoning that methyl iodide would probably behave more like the normal propyl io dide than would ethyl iodide, which as related above had already been tried without success, methyl iodide was tried but showed no activity. However, it was then fiund that ethyl acetate would cata lyze the reaction to some degree and that aniline was still more ef fective as a catalyst (Letter Midgley to Wilson, April 12, 1922). And so aniline was next tried a3 a means of making ethyl iodide re act with sodium-lead to form tetraethyl lead. This last was on April 11, and the next day Midgley wrote R. E. Wilson as follovrs: "We are contemplating very seriously aban doning the zinc ethyl method of making the lead compound,- the reason being that we have been able to make the sodium-lead reaction go. . By using the sodium-lead method we reduce our material cost on the basis of equal yields from $10,20' to $2.60 per gallon." (The $10.20 mentioned here is more, of course, than the $7.50"previously mentioned on the basis of a 100 gallon per day basis, but considerably less than the estimate of $20 included in Midgley*s report to Mr, P. S. du Pont.) Within a few days after Midgley wrote to Wilson as just quoted, the zinc ethyl method was discontinued. ETC 36933 r Report OC-83 136 Many substanoes were tried as catalysts for bringing about the union between ethyl iodide and sodium-lead to form tetra ethyl lead. A number of these--including aniline, ethyl acetate, diethyl aniline, and later pyridine--proved to be effective. As the research proceeded, the ability to control the process and the yields of tetraethyl lead obtained were consistently improved. James P. Andrew and 77. K. Gilkey worked on the preparation of the sodium-lead alloy--which at the time was confined, to the Na^Fb alloy. This, as was discovered later, did not happen to be the best alloy to use, for it was so highly reactive that under some conditions it took fire in air and had to be prepared and handled in an atmosphere of carbon dioxide or nitrogen. Also, it left too much unreacted sodium in the reactor which had to be combined with water afterwards. Hochwait and Midgley conducted the experiments on treating the sodium-lead alloy with ethyl iodide to form tetra ethyl lead. In general the procedure was to prepare the mixture of ethyl iodide and sodium-lead alloy, together with the catalyst, and to apply heat to it for a time. Then, either immediately af terwards, or after having allowed the mixture to stand for some tine, v.-ater was added slowly with cooling to decompose the mixture and to combine with the unreacted sodium. Afterwards any unused ethyl iodide was distilled out in the presence of steam formed by the water present, followed by the tetraethyl lead produced. The tetraethyl lead had to be distilled out with steam to keep the dis tillation temperature lew enough to prevent it from decomposing. A i ETC 36934 r Report OC-83 137 chart showing the process in outline, as taken from a report pre pared for J. W. Morrison by Boyd on April 26, 1922, is included as Figure 33> page 138. Sometimes at the outset, or before proper control was de-- veloped, a rapid decomposition or ''deflagration" occurred during the addition cf the water or during the subsequent period of distilla tion, in which the batch was lost. Through suitable control, the deflagration trouble was^vercome, but the cause of it was not un derstood. Later the theory was proposed by the men at M.I.T. that the violent reaction called deflagration was the result of the formation first in the reaction of diethyl lead, which subsequently de composed with the evolution of heat to give tetraethyl lead and some free lead (Lead Diary, page 374). If the conditions under which the diethyl lead was formed were such that a considerable amount of it could accumulate before the breaking down to tetraethyl lead oc curred, the decomposition reaction would run away, the theory said. This seems to be a likely explanation, but it is understood of course to consist at least in large part of speculation. Cn April 18, 1922, less than two weeks after the work on the sodium-lead process had been begun, an experiment was made in which ethyl bromide was substituted for ethyl iodide, with dimethyl aniline as catalyst. In still another experiment ethyl chloride was substituted. The ethyl bromide experiment was successful, but the yield of tetraethyl lead was small, and it was more than two months after this before a shift was made to ethyl bromide as the agent for i ethylating lead. The experiment with ethyl chloride was altogether ETC 3693 kEPORT OC-33 13d Ha 4-Pb ga Pi) Refluxed with excess of EtI in presence of catalyst. A number of catalysts have been tried, of which alkylated aromatic amines, such as diethyl aniline, are the best so far tried Hydrolyzed witli water, accompanied by coincident cooling Cut 1 EtI Distilled in presence of excess of water 1 Cut 2 EtI PbEtJ --r-4 Fractionally distilled r _J_ --I EtI PbEt. I Cut 3 PbEt. Residue containing gal, gaOH, and a material the compo sition of which has not yet been deter mined rr 60-80$ of theory The best process for the recovery of iodine from this residue has not yet been worked out. So far as it has been worked out, however, it is as follows: The gal and gaOH are extracted with water, the gaOH neutralized with iodine, the solution evaporated to dryness, the gal treated with HC1 in alcoholic solution for the preparation of Eti, and the iodine not recovered in this way precipi tated with chlorine, as given in the outline of the zinc ethyl process. FIGURE 33 Outline: or procedure tor making tetraethvl lead by means OF TKE SODIUM-LEAD PROCESS, AS IT EXISTED IN APRIL, 1922. ETC 36936 r Report OC-83 139 unsuccessful as to any yield of tetraethyl lead. This is now under standable in the light of the work of Dr. Charles A. Kraus at Clark University, on the basis of which, ethyl chloride is now being used in the manufacture of tetraethyl lead. Dr. Kraus found that, to get ethyl chloride to combine with lead, the sodium-lead alloy used must not be the NaAPb employed in these experiments, but an alloy of only 10% Na and 90% Fb. Contact with Dr. E. E. Reid When liidgley and Hcchwalt returned on April 7 from the Birmingham meeting of the American Chemical Society, they were ac companied by Dr. E. E. Reid, professor of organic chemistry at Johns Hopkins University. Dr.. Reid, who came to the laboratory on Midgley's invitation, spent the better part of the day looking over the progress that had been made in investigating lead as an antiknock agent, and was given as complete a picture of the work as possible. At Midgley's suggestion that he help in the synthesis program in an advisory capacity, he promised to think about whether he could prop erly do so in view of his duties at Johns Hopkins and of his con tract with the du Pont Company, for whom he was already acting in a consulting capacity. Because of his du Pont contract. Doctor Reid did not enter into an agreement with us, but he did later help with the endeavor to the extent of making a critical examination of the chemical literature on the subject of organic compounds of lead and of reporting his results, and also in advising that after studying the problem he considered that, for making tetraethyl lead "the leadsodium method or some modification of it is the most promising." (Lead Diary, page 193) ETC 36937 Report OC-83 140 Incidentally, it is understood that one reason why Dr. Reid consented to return to Baltimore from Birmingham via Dayton and to spend the day in consultation there was because liidgley had promised to have him taken up at Dayton for his first ride in an airplane. From the flying field beside the laboratory "Bernie" V.'halen took Doctor Reid up in the enclosed cabin plane called the "Honeymoon Express.* Much against his will, Midgley went up with them. It was just before a thunder storm and the ride was very b'jmpy. Midgley said afterwards that he v/as mighty glad to get down; but Dr. Reid, he said, enjoyed the ride thoroughly and showed no concern whatever, Later Dr. Reid wrote Uidgley: "Thank you and Mr. Kettering for a most pleasant day in and above your plant." (Lead Diary, page 252). The high place assigned to Dr. Reid in liidgley's estimation is suggested by the v.ire he sent to Boyd from Birmingham asking that the laboratories be spruced up in ad vance, especially Russ 'Veils' room, which was perpetually in need of straightening and cleaning.. The research on making tetraethyl lead by the action of ethyl iodide on sodium-lead alloy was continued by using larger and larger amounts in each charge. In one of these experiments, begun on April 28, 1922, Na2?b was used as the alloy, instead of the Ka/^pb usually employed. The alloy lower in sodium gave a good yield of tetraethyl lead, but in this first run with Na2?b not quite as high a yield as was by that time being obtained with the Na4Pb (Lead Diary, pages 19^ and 200). And so the use of Na4Pb was con tinued for some time. ETC 3 6938 Report OC-63 141 The First One-Gallon Lead Plant On May 5 and 6, 1922, the first run was made in an appara tus which had been designed to produce a gallon of tetraethyl lead in one batch (Lead Diary, page 210). This apparatus in its first form is shown in the photograph, Figure 34, page 142, the man in the picture being Russell Wells. The cooker, shown sitting in the frame on the scales, had inside it a coil of pipe for heating with steam or for cooling with water as needed and a motor-driven stir ring device. (This cooker was later modified in some respects, one of the changes providing for charging the alloy of sodium and lead to the cooker in the ingot form and so making grinding outside un necessary, Lead Diary, pages 299 and 300), The charge was about 30 pounds pulverized Na^Pb, nearly 47 pounds ethyl iodide, and 2.5 pounds diethyl aniline. The heating of the batch v>as begun at 7:30 P. on Friday, Hay 5. The temperature was maintained at 155-160 deg. F. and meanwhile the batch was stirred continuously until 2:30 the next afternoon, Saturday. The excess sodium in the alloy vras then removed by the gradual addition of water over a period of 3 hours. At 5:30 P.L. on Saturday, Hay 6, the distilla tion of the product was begun. It was finished about midnight, and the yield of technical grade tetraethyl lead was 3200 cc., or Just about a pint less than a gallon. So important was this first large-scale trial thought to be that almost every member of the group working on the Job of making tetraethyl lead was present during a large part of the 30-hour trial. This group consisted of Siidgley, Hochwalt, Andrew, and Boyd, together ETC 36939 f FIGURE 34 N 'His quickly-constructed apparatus, the making of tetraethyl j -F.il 3 ' 'I-E SOD I try-i-EAD '-IEThOO /.AS BOOSTED FROM A LABORATORY Sla-: to a on. - ."Allo;< basis, actjai_ yield in the first run, o. 9t.a - russell jellS is the operator. L ETC 36940 f Report OC-J33 U3 with C. P. Harding and James Taylor, who had done the work on prepar ing and pulverizing the alloy of sodium and lead. Ur. Kettering also spent a large part of Saturday evening on the scene during the final distillation. At midnight on Saturday everyone went home frt>m the long stand pretty well encouraged with the success of the initial large-scale trial. Then on Uay 11, James P. Andrew was asked to begin work on the design of a plant to make 100 gallons of tetraethyl lead per day by the sodium-lead method. Ethyl iodide wa3 to have been used as the ethylating agent, and the iodine was to be recovered afterwards, converted into ethyl iodide, and used over again, according to the general scheme outlined in Figure 33, page 138, and more completely in Figure 35, page 144, prepared a little later. Iodine being so expensive and so scarce, the recovery of the iodine--the almost complete recovery of it--was of course neces sary to the success of the process. But 8 pounds of iodine was lost in the first large-scale trial just described (Lead Diary, page 222). So an intensive investigation of means of conserving and recovering iodine was undertaken, and an Improved scheme for the recovery of iodine over that given in Figure 33, page 138, was later worked out (Lead Diary, page 262). The effects of time and temperature, as well as of other variables, upon the making of tetraethyl lead by the reaction of ethyl iodide with sodium-lead alloy were investigated also in a series of small-scale experiments. Ueanwhile the costliness of iodine, and the difficulties involved in recovering it completely, caused some 4 ETC 36941 REPORT OC-83 4Na + Pb Fuse in Atmos phere of COg 144 Charge to Auction Still atone with Erl, Diethyl Aniline at Cataiysr- Hydrolyze at 60G. with Coincident Stirring and Crushing Distill in Steam ________ I________ Residue m SmA. PbEta+Dietktl Amutte Neutralize with HCi Treat with 10% H^SO^ I Add Zinc Pb.ETa Diethyl AmuntSmrm fractionally Distill Treat vv>A AbOH Filter Antiknock No. 500 Dienm AmmB Residue Boil in Weak HC! I Filter Residue On targe Saji, flecowr Ltad Solution --Solution Alcohol aho Aqueous HCl I Evaporate to Dryness WMi-ZnU Mixture or Alcohol-*-- aho Aqueous HCL Some impunity m MaCi ordZnCk Pass in HCi as Gas I_________ --------- 1 I------------ Charge to Sti/i along with snail amount SnOf Distill ________ I_________ Residue m Still Distillate Pass in Chlorine I JFilter Solution Distill in Steam /opine Iodine aho Water Add Aqueous Hd Loweh Layer. tI Some irOas knpurity --d Limn Layer, Alcohol ms HCl 2 Add Zinc zU z-rti* zr FIGURE 35 FLOW DIAGRAM OF PROCESSES IN PROPOSED METHOD OF MANU FACTURING TETRAETHYL LEAD BY REACTION BETWEEN ETHYL i IODIDE AND SODIUM-LEAD ALLOY, MAY, 1922. 3 6 942 Report OC-33 145 effort to be directed toward finding other means of getting ethyl radicals to join with lead to make tetraethyl lead. One of these attempts, in particular, should not fail to be mentioned. This was the effort to get ethyl nitrite to combine with sodium-lead alloy. A test-tube experiment had been made (Lead Diary, page 238) which seemed to shov; that iso-propyl nitrite would combine with sodium-lead alloy to give tetra-isopropyl lead, the same compound as was being made in the electrolytic experiments at LM.T, And so some ethyl nitrite was prepared for use in an effort to make tetraethyl lead in the same way. A preliminary test-tube experiment with ethyl nitrite was not successful, but the failure was thought to be due to the low boiling point of the ethyl com pound, by comparison with the isopropyl used before. About 50 cc of ethyl nitrite was accordingly mixed with Ka^Pb in a small auto clave or pressure vessel made out of a short piece of 1-1/2" iron pipe. The autoclave^was fitted with a pressure gauge, and, for sup posed safety, with a convenient hand-operated relief valve. The reaction in this vessel had proceeded for a short time with the pressure rising slowly and then being maintained uni formly at about 10 pounds. Then all at once the pressure began to rise rapidly. The operator reached for the relief valve t-* open it; but, before he could even get his hand to the valve, there was a ter rific explosion which blew the lower end out of the autoclave and the pressure gauge off the upper end. So violent was the concussion that about 50 panes of glass in the windows and partitions of the room were shattered, as well as some of the glass apparatus inside the work benches. This large breakage of glass occurred in spite of the ETC 36943 Report OC-83 146 fact that the windows were open, it having been summer, May 25, 1922. The lucky thing--a very lucky thing--about it all was that, although three of the men were standing immediately in front of the apparatus at the tine of the explosion, all escaped with nothing more than minor scratches. ConclusiorTOf Effort at H.I.T. to ?Zake Tetraethyl Lead by Elec trolysis of Acetone The investigation going on at H.I.T., which when it was left, several pages back, in the early part of April, 1922, was being concentrated on the making of tetra-isopropyl lead by the electrolysis of acetone in dilute sulphuric acid solution, went - forward on that line until the end of April. At that time R. E. Wilson wrote to Uidgley: "I an inclined to agree with you that we should stop work on this process for the present, in view of the much greater promise of your new process" (Lead Diary, p. 196). He was referring, of course, to the sodium-lead and ethyl iodide process of making tetraethyllead. For a time there was uncertainty about what ought to be done at H.I.T. But on Hay 18 and 19, 1922, Dr. Venable visited the laboratory in Dayton and was given a complete account of the progress made there up to that time. It was agreed then that at M.I.T.. they should prepare a report on the electrolytic experi ments, and among other things try to find a method of making tet raethyl lead without using the alkyl halides, and also try to de termine under what conditions ethyl chloride or ethyl bromide could be substituted for ethyl iodide in making tetraethyl lead. The fi nal report on the electrolytic preparation of lead alkyls at M.I.T. WAS iVim iff &A am T... in**** ETc 36944 Report OC-83 147 Attempt to Substitute Sthyi Bromide for Ethyl Iodide Returning to the research at Dayton on making tetraethyl lead, an important move was made on June 29, 1922. This was a sys tematic attempt to substitute ethyl bromide for ethyl iodide, the first trial of which had been made in April, as previously related. Work was now begun not on a laboratory scale, but in the apparatus intended to produce 1 gallon of tetraethyl lead at a time, diethyl aniline having been used as catalyst (Lead Diary, page 311). The reaction went to a considerable degree, but the yield of tetraethyl lead was definitely lower than that then being obtained with ethyl iodide. Following this, the large-scale apparatus was run from time to time using ethyl iodide and sodium-lead alloy, and the pos sibility of substituting ethyl bromide for ethyl iodide was actively investigated in small batches in the laboratory. After this program had gone on for two weeks, or until June 13, 1922, the men who had been working on the project--Hochwalt, Andrew, Gilkey, and W. H. Charch, the latter doing summer work at the laboratory--all con centrated their endeavors upon finding catalysts or conditions which would make the use of ethyl bromide as efficient as ethyl io dide. A great many such experiments were non, and, of all the ma terials tested as catalysts, pyridine proved to be the best. Pyri dine was effective enough, in fact, to bring the yields of tetra ethyl lead when using ethyl bromide up to, or nearly up to, those obtained when ethyl iodide was used. ETC 36945 Report OC-83 148 Du Pont Comes in On the Manufacturing Problem The time was now toward the end of July, 1922. And ano ther important event in the history of this endeavor then occurred. On July 22, Messrs. W. F. Harrington, E. K. Bolton, and ff. S. Calcott of the du Pont Company visited the laboratory. They came at the invitation of Ur. Kettering to study the process of making tet raethyl lead and to see whether the manufacture of the compound could be carried out in the dye plant of the du Pont Company. Ur. Kettering had visited the du Pont Company a week before, and had taken with him the diagram reproduced as Figure 35, page 144* This diagram was the result of consideration given by our whole group since July 8 to the possibility of building a plant to pro-! duce 100 gallons of tetraethyl lead per day by the sodium-lead and ethyl iodide process (Lead Diary, page 329)* As a part of this analysis, a memorandum also had been prepared for Hr. Kettering on the cost and availability of chemi cals for producing tetraethyl lead, in which it was estimated that by this process tetraethyl lead could be made at a cost for materi als of about $5*25 per gallon (Lead Diary, page 333). But in this same report the fact was recognized that ethyl bromide might later be substituted for ethyl iodide; and it was estimated that such a substitution, if it could be made, would reduce the cost of ma terials per gallon of tetraethyl lead from $5.25 to about $4. By the time the du Pont men made their visit to the lab oratory on July 22, the use of ethyl bromide instead of ethyl io dide had begun to look so promising that the process detailed to them was that using ethyl bromide. Just as much information as ETC 36946 Report OC-83 149 possible was given the du Pont men during their stay. A digression should perhaps be made here to explain the neaning of the term in Figure 35, "Antiknock Wo. 500." This term stood for tetraethyl lead in a decimal system devised on June 6, 1922, (being a revision of an earlier one given in Lead Diary, page 159), to designate the various known antiknock agents without actually naming them in such a way as to disclose their compo sitions. In about a week after the visit of the men from the du Pont - Company, a letter was received from Doctor Bolton, saying, among other things, the following: "During the past week we have carried out laboratory experiments on tetraethyl lead by the ethyl bromide method, according to the recipe which you gave us, and have not found any difficulty in duplicating your results of 60. We are assembling equipment at the present time to carry out semiworks operations in order to have actual experience with the mechanical difficulties of this process before attempting to go to a larger scale. .... We are carrying out the manufacture of the sodium lead alloy under a very thin film of molten caustic and find that when the material is ladled out for casting into molds there is not any great danger in firing when the surface of the liquid is broken." (Lead Diary, page 378). Changes in the Research at M.I.T. Returning again briefly to the work at M.I.T., the in vestigation there had been actively prosecuted since the visit of Venable to Dayton in May, when the course of their endeavor had ETC 36947 Report OC-83 150 been changed. Y.'ith the discontinuance of the electrolysis work. Dr. Horsch dropped out of the investigation. On July 8, 1922, George Calingaert and Brian Head began to work on lead problems, the supervision remaining with Venable and '-'ilson. However, in August Valter G. Whitman took over Venable's part, and shortly thereafter Venable went to the Viscose Company, as previously mentioned. The new activities at LI.I,T. included the effort to substitute ethyl chloride for ethyl iodide in making tetraethyl lead, the making of tetrabutyl and tetra-phenyl lead for test, some experiments on the use of alcohol instead of water for hydrolysis, and the investiga tion of the course of the reactions in the making of tetraethyl lead and of the composition of the intermediate lead compound formed during the process. As already said, this latter study led to the belief that diethyl lead was the intermediate compound, and that it was the decomposition of this diethyl lead to tetraethyl lead which accounted for the deflagration troubles experienced in the early experiments at Dayton (Lead Diary, page 374). A Conference Brings Some Changes In the laboratory at Dayton there was during August, 1922, active investigation of still another method of raking tetraethyl lead; It consisted in reacting ethyl iodide v:ith powdered lead in the presence of granular zinc, all under a layer if a solution of sodium hydroxide (caustic soda). The first trial by this method had been made on July 3, 1922, by J. P. Andrew (Lead Diary, page 321). The method was now being actively experimented with (Lead Diary, page 382 et seq). By the end of August ethyl bromide was being substituted ETC 36948 Report '*'-83 151 f-,r ethyl iodide, and the granulated zinc was being coated with lead by precipitation from a lead salt. Midgley became so enthusiastic t about this modified method that he arranged for the men at du Pont and at M.I.T. to come to Dayton for a conference about it. On Aug ust 28 Midgley wrote R. E. Viilson: "This reaction sounds so good that we believe it will be the opinion of the conference with you and du Pont that we should abandon the sodium method and concentrate on this new reaction." The conference as called was held at the laboratory in Day- ton, or Moraine City, on August 29, 1922 (Lead Diary, page 406), Calcott from du Pont and hitman and Calingaert from M.I.T. at tended it. Out of this conference came a very important decision, but as it finally turned out it did not involve a change from the sodium-lead to the zinc-]ead method of making tetraethyl -lead. The decision reached was that research on the making of tetraethyl lead in our laboratory should be dropped at thr.t point, and that all our i ! efforts should be concentrated on the problems of utilization. The { investigation of utilization problems, not yet reported but to be described below, had already been going on for some months, conduct i 1 ed chiefly by Boyd. Further work on the making of tetraethyl lead, i* it was decided, should be carried out at the du Pont Company, with j, tne men at M.I.T. continuing to investigate some of the more import ant problems incident to such production. The work at du Pont on recking tetraethyl lead had already by this tine progressed to the stage at which they had begun to shir; tetraethyl lead to Dayton, ; seventy pounds at one time and forty-six at another (Lead Diary, ^ page 400). Calcott went back home that night to continue research on ETC 36949 Report OC-83 152 CHAPTER VIII PR0ELEL5S OF USING TETRAETHYL LEAD INVESTIGATED Simultaneously with the extensive research on means of making tetraethyl lead, described in the several pages just pre ceding, matters relating to utilizing it as a practical antiknock agent had been under active investigation also. These endeavors were chiefly four in number, as follows? 1. Measuring the antiknock effectiveness of tetra ethyl lead and other lead compounds in various concentrations in different fuels, and finding the influence of added agents upon It. 2. Studying the stability of tetraethyl lead in stor age, both by itself and when mixed with gasoline, and trying to improve the resistance of the com pound to the decomposing action of light. 3. Making an intensive effort to find a way to cor rect the spark plug corrosion and exhaust valve deposition difficulties soon seen to be connect ed with the burning of tetraethyl lead in engines. 4. Taking the first steps toward investigating pos sible toxic hazards in the use of tetraethyl lead as an antiknock agent. ilso, ore of the first tests to which tetraethyl lead was subjected after the 1aa ' discovery rms for i:s degree of solubility in kerosene and gasoline. It was found,in short, that tetraethyl ETC 36950 Report X-Q3 153 lead was extremely soluble in these fuels. Thus in kerosene tetra ethyl lead was so soluble that a 1 per cent solution of it had not begun to separate at 40 degrees below zero F. (Record 13, page 204). Following the discovery of the remarkable effectiveness of tetraethyl lead in December, 1921, other lead compounds were natu rally tested for antiknock effect. In the several ratings of.tetra- methyi lead that were made (Record 13* page 207, et seq.), that com pound also was found to be a very effective antiknodk agent; but lead oleate, a different kind of lead compound, was found to have no anti knock effect whatever, even in a concentration as large as 1 per cent (Record 13, page 204). The tetraisopropyl lead made at M.I.T. was found to be only about one-half as effective as tetraethyl lead, but tetra-normal-propyl lead proved to have about the same effectiveness as tetraethyl lead. Also the samples of tetrabutyl and the tetra- phenyl lead made at M.I.T. were rated and f->und in each instance to be about one-half as effective as tetraethyl lead (Record 13, pages HO and 207). The first tests were made, too, in which the degree of effectiveness of tetraethyl lead as antiknock agent was found to change with mixture ratio (Lead Diary, page 13). It was in January, 1922, that the first tests were made in determining how much tetraethyl lead need be added to one gasoline to make it match another in degree of freedom from knock. The object was to find how much tetraethyl lead to add, first, to the export grade naphtha of t,ha Vacuum jil -Icmrany, and, second, to the 66-63 degree naphw'.-H of the sarit any, to make each equal in degree of freedom from knock to the Shell spirit with which they had to compete abroad. ETC 36951 Report OC-83 15U After a number of the most careful determinations that could then be made, it was concluded that to equal Shell spirit, the export naphtha needed 1/20 per cent tetraethyl lead and the 66-68 naphtha 1/30 per cent. Three gallons of the former fuel and about four gallons of the latter were treated accordingly and shipped to the Vacuum Oil Company on January 30, 1922. The men in the Vacuum Oil Company with whem we were in contact with regard t-> these tests were Messrs. F. B. Killian and G. A, Round, both of whom are still active in what is now the Socony-Vacuua Oil Company. A particularly important one of the early jobs of rating was done as a result of experience with the various cars run on gas oline containing tetraethyl lead, some of which had compression ratios boosted as high as 7.5:1. It was observed that apparently the amount of tetraethyl lead needed to prevent knock did not in crease directly with compression ratio (Monthly Report for April, 1922). On this account, careful measurements of the effectiveness of tetraethyl lead in kerosene were made by comparison with xylidine in kerosene over a wide range of concentration. The results of these measurements are shown in Figure 36, page 155 (Lead Diary, page 206). There the continual decrease in increment of antiknock effectiveness as the concentration of tetraethyl lead was increased, particularly above one-tenth of one per ce.it by volume, is apparent. This is a characteristic that was to have an important effect upon the future usefvlr .ss of :.he roepourd. It. was ir ' a ser ies of tests just described that another important observation was namely, that the degree of effective ness of tetraethyl lead is greater in some fuels than in others. ETC 36952 REPORT 00-83 155 FIGURE 36 PLOT OF EARLY MEASUREMENTS WHICH SHOWED THAT THE EFFECT IVENESS OF EACH UNIT OF TETRAETHYL LEAD AS AN ANTIKNOCK AGENT DECREASES AS CONCENTRATION RISES. THUS, FROM THE ABOVE CURVE, THE FIRST 0.1 PER CENT OF TETRAETHYL LEAD IS EQUIVALENT IN ANTIKNOCK EFFECT TO 3.5 PER CENT XYLIDINE, BUT THE SECOND 0.1 PER CENT TO ONLY HALF AS MUCH XYLIDINE. ETC 36953 Report OT-83 156 Thus tetraethyl lead was found then to be 20 per cent more effect ive in the gasoline used than in the kerosine (Lead Diary, page 207). This was the first observation of a characteristic which, as is now known, can vary in the case of tetraethyl lead from an antiknock effect in some fuels of 10 tines the usual magnitude to a large negative or knock-inducing effect in other fuels, the dif ferent degrees of effectiveness depending only upon the composi tion of the fuels to which the tetraethyl lead is added (Antiknock Effect of Tetraethyl Lead, Campbell, Signaigo, Lovell, and Boyd, Ind. Eng. Chem., 27, 593, May, 1935). Another considerable job of knock rating done during this period was the extensive measurements made on mixtures with kero sene and gasoline of benzene, toluene, xylene, and ethyl alcohol by comparison with mixtures of xylidine in kerosene as reference fuels (Record 13, pages 246-285). In a series of about 65 ratings the knocking characteristics of these fuels were established ex tensively enough to form the basis of tvn published papers, as follows: 1. Detonation Characteristics of Blends of Aromatic and Paraffin Hydrocarbons Thomas Midgley, Jr., and T. A. Boyd Ind. Eng. Chem., 14, 589 (July, 1922). 2 Letonation Characteristics of Some Blended Motor Fuels Thomas Liidg.iey. Jr., and T. A. Boyd S.A.E. Jour., 10, 451 (June, 1922). These two papers were based on the same data, and were therefore similr.; ir '-jptar.t, '-y.cspt that the second contained the data on ethyl i-iuoh'-l, ncoe of jvhj.cn was included in the first. The former ETC 36954 Report OC-83 157 paper was presented at the meeting of the American Chemical Society in Birmingham, which Jlidgley and Hochwalt attended, as previously recorded. The latter was presented at the summer meeting of the S.A.E. at VJhite Sulphur Springs in June, 1922. Among the items of information contained in these papers was the observation that toluene is more effective as a knock suppressor than benzene, and that xylene in turn is more effective than toluene. First Studies on the Stability of Tetraethyl Lead in Storage It was only a few days after the effectiveness of tetra ethyl lead as an antiknock agent was discovered, in December, 1921, that Boyd began tests to see whether tetraethyl lead was stable in storage. The first tests were made on the same kerosine solution as was used for the first measurements of antiknock quality on De cember 9, 1921. ' That solution was filtered clear and set on. the shelf above a laboratory work table in an Srlenmeyer flask. Short ly thereafter, similar tests were begun on tetraethyl lead by it self (Record 13, cage 220). It was soon found that if tetraethyl lead, either alone or in solution in kerosine or gasoline, were kept away from the light, in a dark glass bottle or in a can, no break-down in it occurred. But the compound is light-sensitive, and if any white light can get to it a slow decomposition occurs with the depositing of lead oxide on the bottom of the vessel. This decomposition in light apeeared to be somewhat faster in tet raethyl lead by itself than in the dilute solution of the compound in a fuel such r.s uf->\ine or kerosine. ETC 36955 Report OC-83 158 Because Mr. P. S. du Pont had expressed the fear that tetraethyl lead night possibly not be stable enough, even when stored away from the light in metal containers, to permit the compound to be packaged and shipped successfully, a special series of tests were undertaken to find out about that. Samples were put into containers, each with a connected nanometer to re cord pressure changes. It was found that, when tetraethyl lead was stored in metal containers that protected it from all light, it underwent s-> little change that no measurable rise or fall in pressure had recorded on the manometer after a year of storage (Record 13, page 287 and Record 19, page 80). If not protected from the light, however, tetraethyl lead did decompose slowly with the depositing of a solid and the evolution of a hydrocarbon gas. Because it was then thought de sirable to make the compound stable in white light if possible, a long search was conducted for some material that could be added to it to make it resist light. In this work, which extend ed over many weeks, the effect of more than 150 addition agents to tetraethyl lead was tried (Lead Diary, page 184). The tests were conducted by exposing the samples to light, and sometimes to di rect sunlight, in clear glass containers. A few of the compounds tried did exert a stabilizing effect, but this was apparently due in some instances to the effect of color imparted to the mixture by the compound in reducing light penetration. In the case of one of the compounds which appeared to be most effective as a stabil izer, cresol, it was f'und that the effect was only apparent. ETC 36956 Report OC-83 159 Although even in direct sunlight the mixture of tetraethyl lead and cresol would remain clear for several days, it was later found that meanwhile a gas was being given off. The evolution of gas was so slow as not to be perceptible in an open vessel, but it was found that if, after standing for some time in light, the mixture were poured into gasoline it was no longer completely soluble, but threw down a voluminous precipitate of solid matter not miscible with the gasoline. A quantity of the gas given off by the mixture of tetra ethyl lead and cresol, even though the solution remained clear, was collected and found to be mainly a saturated hydrocarbon, either ethane or butane or a mixture of the two. Thus the long search for a means of stabilizing tetra ethyl lead against slow decomposition in light did not prove to be very successful, except to the small extent that the following com pounds, best of those found, served: turpentine, terebene, allyl alcohol, and dimethyl aniline (Lead Diary., page 398). however, colored substances did protect tetraethyl lead and its mixtures to a considerable degree, for they filtered out much of the white light. And, as later experience showed, no more protection than that was really needed in practice. First VTork on Spark Plug Corrosion and Exhaust Valve Deposit Prob lems The third and perhaps the most important of the supple mentary items of investigation carried along during the first eight months of 1922, simultaneously with the research on how to make tetraethyl lead, was the effort to find a way to correct the spark ETC 36957 Report OC-83 160 plug and exhaust valve troubles seen to be connected with running en gines on gasoline containing tetraethyl lead. The spark plug troubles--erosion of electrode wires and melting in blobs on the porcelain causing the porcelain to crack and pieces of it to split out--were first observed on April 1, 1922 (Lead Diary, page 107). The observation was made in the high-compression "FB" Chevrolet, called "The Goat" and mentioned earlier, which had then been run fcr some time on gasoline treated with 10 cc. tetraethyl lead per gallon. This car was put back into condition and continued to be run on the same lead-treated fuel. It was not until later on that trouble from the depositing of lead oxide or. exhaust valves was ex perienced (Lead Diary, page 234). But by the middle of April, 1922, at least three other cars were being run on gasoline containing tet raethyl lead, as follows (Lead Diary, page 149; Letters, page 35)* A company Cadillac, 7:1 compression ratio, 15 cc. tetra ethyl lead per gal, Harold Talbott's Packard, 5.8:1 compression ratio, 5 cc. tetraethyl lead per gal. Midgley's Buick, 8:1 compression ratio, 30 cc. tetraethyl lead per gal. In the light of present knowledge, it is not surprising that, with such large concentrations of tetraethyl lead as 30 cc. per gallon, spark plug and exhaust valve troubles in the engines should develop in a short time. And so they did. By the time a month more had passed, it was quite apparent that here was-a prob lem that would have to be solved if lead-treated gasolines were ever to be used in automobile engines. ETC 36958 Report OC-83 161 In the latter part of ijay, 1922, Boyd was therefore as signed the still further Job of trying to find a means of correcting these spark plug and exhaust valve troubles. It was thought at first that the difficulties might be caused by an impurity of ethyl iodide in the tetraethyl lead. Eth"l iodide was then being used in raking tetraethyl lead, and the product did therefore contain a minute amount of ethyl iodide. (As it later turned out, however, ethyl iodide proved not to be a harmful material but a mild cor rective agent.) A quantity of tetraethyl lead was accordingly puri fied by various means and a number of runs were made in engines using gasoline treated with the carefully purified tetraethyl lea^ These tests were made in one-cylinder "copper cooled" engines in the dynamometer room of the research laboratories, which was under the supervision of William B. Earnshaw. But the man who actually operated the engines for the most part was E. E. Gold, an ex-member of the U. S. Coast Guard and of the crew of the famous revenue cutter "Bear". Gold ran engines for these tests throughout the more than two years over which the investigation extended, after a while de voting his entire time to it. I I The engine tests using tetraethyl lead purified to any content of ethyl iodide turned out to be just as bad in respect to effects on spark plugs and exhaust valves as had those in which the original tetraethyl lead was used. Work was then begun on adding different compounds to the gasoline along with tetraethyl lead in the hope that during the combustion the lead would be converted to a compound other than lead oxide--to a compound which would not have ETC 36959 162 bad effects on spark plugs and exhaust valves. There was no basis for selecting compounds to try other than the old one of "cut and try." Hence that method was followed. By this means it was found on June 16, 1922, that the presence of the chlorine compound, chlorobenzene, improved the condition of the spark plug to a marked degree, but the exhaust valve was damaged some possibly be cause too much chlorine had been used for the tetraethyl lead present (Lead Diary, page 295; Record 19, page 95). And thus, just a few days after the tests began, one compound had been found which effected a considerable improvement. As rapidly as could be, other compounds were tried for effects as possible corrective agents. And meanwhile a careful literature study of lead oxide was made (Lead Diary, page 295), and some laboratory experiments were conducted on the effects of sulphur dioxide and chlorine upon lead oxide (Lead Diary, page 298). Sulphur compounds and other chlorine compounds were among the several materials tested as rapidly as possible, two one-cyl inder engines being used for the tests'. Some of the tests on chlorine showed excellent results (Lead Diary, page 304-5, 318)# Also a run was soon made with bromine a3 bromobenzene. But for some reason this first run on bromine, which element later proved to be the best corrective agent of all, did not turn out as well as it should (Record 19, page 97). Later, however, on July 11, 1922, bromine as ethylene dibromide was added to the leadtreated gasoline end showed excellent results as a corrective agent (Record 19, page 101; Lead Diary, page 333). ETC 36960 Report OC-83 10; This hunt for a corrective agent could not go faster than the engine tests gave results. But it was pursued intensively, and a third engine was soon put into service. Most of the engine tests were made with a concentration of 10ca tetraethyl lead per gallon of gasoline. By the end of August, 1922, when, as before said, it was decided that the laboratory at Dayton should stop experiments on methods of making tetraethyl lead and that everyone should con centrate his endeavor on the solution of the problems of running engines on gasoline containing tetraethyl lead, the status of mat ters was as follows: 1. It had been found on the basis of a great many tests th&t chlorine compounds corrected the spark plug troubles rather well, but were apparently not effective.in re moving completely the deposit that formed on exhaust valves. 2* It had been found that bromine compounds were quite ef fective for correcting the spark plug troubles (Record 19, page 101), but specific information about effect for keeping exhaust valves clean had not yet been got ten at that time, 3. It had been found that the presence of chloroform or carbon tetrachloride in amount sufficient to contain theoretical amounts of chlorine for the tetraethyl lead present reduced somewhat the effectiveness of tetraethyl lead as a knock suppressor (Lead Diary, page 328). ETc 36961 Report OC-83 164 4. It had been found that tetraethyl lead was light sensi tive, but that when protected from the light it was quite stable. Some preliminary tests on the stability of mix tures of tetraethyl lead and carbon tetrachloride had been made also (Lead Diary, page 358). 5. Some tests to find whether lead oxide formed by burning tetraethyl lead in engines increased the wear on piston rings had shown, in a preliminary way at least, that it did not (Record 19, page 134). First Attention to Possible Health Hazards The fourth one of the utilization problems mentioned, namely, the possibility that putting lead into gasoline might in troduce hazards to healthy was also given consideration early. One of the first things done by R. E. after the arrangement with M.I.T. in early February, 1922 (Lead Diary, page 19), was to consult Dr. Reid Hunt of the Harvard Medical School to get his opinion about any possible poisonous effects of tetraethyl lead in dilute solution in gasoline, and t> ask whether he would be willing to undertake an investigation of the subject. This was done with Uidgley's approval, of course. The result, as extracted from R. E. YJilson's letter of February 20, 1922, to Midgley (Lead Diary, page 38) was as follows: 1. Dr. Hunt "has very grave fears as to the toxicity of the lead alkyl compounds, even in the very dilute solutions with which we would ordinarily deal." 2. "He was quite skeptical as to the effectiveness of any antidote." ETC 36962 Report OC-83 165 3. "He thinks it quite possible that the lead alkyl com pounds could be assimilated through the skin." 4. "He feels that the best men to undertake a study of the compounds and get quick results would be Hender son and Haggard of Yale." 5. In a later letter, Wilson to Midgley (Lead Diary* page 53): "Dr* Hunt was concerned with the building up of the lead content of the dust in our city streets by the material coming from the exhaust." Midgley next asked Wilson to inquire of Dr. Yandell Hend erson at Yale University whether he would be willing to investigate tetraethyl lead from the viewpoint of possible health hazardst In reply, Dr* Henderson wrote Wilson on March 16, 1922, (Lead Diary, page 75), in part as follows: "As a preliminary opinion I would say that I should expect the exhaust gas under the conditions you mention to constitute an extremely serious health hazard. ... It appears to me that the risk of poisoning would amount almost to a certainty for every one around garages and for the part of the public which will use vehicular tunnels. There will be a distinct risk even for people living and working around such congested streets as Fifth Avenue, New York City. Of course these state ments are provisional. ... My associate, Dr. H. W. Haggard, and I will undertake the investigation for you. I believe that we could get it done in about two and a half months. If so our charge would be $5,000. If, because of the raising of additional points for investigation, the work was continued thereafter, the rate of our charge would be $2,000 per month* This would cover all expenses." On this letter from Dr. Henderson, Wilson in a letter to Midgley, March 18, 1922, (Lead Diary, page 77), commented as follows, in part: "The price mentioned seems somewhat high, but it undoubtedly covers the work of a considerable number of men. ... As to his excessive fear of injury by the exhaust gases, I think part of this may be based on the assumption that some of the undecomposed lead alkyls will pass out through the exhaust." ETC 36963 Report ^C-S3 166 Hidgley then wrote Wilson, March 24, 1922, (Letters, page 34), in part: "Have talked over the proposition of Dr. Henderson with Mr, Kettering. I am inclined to agree with you that his price seems high. However, if we could arrange with him that he would agree to being called upon at a later date, free of any other charge than his expenses, to refute any false propaganda which might be started against the use of lead compounds that it might be possible to get together." There was apparently one further letter from Dr. Hender son to Wilson at this time, written in the latter part of March, 1922. In it he said, among other things, the following (Lead Diary, page 89) "The more I think on the topic of introducing lead alkyls . into autonobile fuel, the more seriously I am concerned re garding the situation which vdll arise. , . . The use of lead in this way would, I believe, result in wide-spread lead poisoning among chauffers and garage workers. . . Chronic lead , . is one of the worst diseases known. In deed, if one had his choice between (1) partial asphyxi ation, (2) syphilis, (3) tuberculosis, and (4) chronic lead, he would be well advised to choose in this orderi" But Dr. Yondell Henderson was not retained to investigate the problem of possible toxicity. And nothing more on the subject happened during the extremely busy summer of 1922, However, the sug gestion made in Midgley's letter quoted above about the part which Dr. Henderson might later play in refuting propaganda about the haz ards of putting lead compounds into gasoline is particularly inter esting in the light of subsequent events, to be recounted when the time comes; for, as it turned out. Dr. Henderson became not the re- futer of such propaganda but the active disseminator of it. ETC 36964 Report OC-83 167 Other Events During 1922 Except for a number of miscellaneous events, this brings the story of the lead research up to the end of August, 1922* One of the incidental events was that in June, 1922, Midgley conducted experiments on making "solid" tetraethyl lead and on making a lead "pill" by coating a quantity of this "solid" tetraethyl lead with a protective layer of paraffin (Lead Diary, page 290). It was found that, if tetraethyl lead was nixed with melted para-toluidine, a solid containing as much as 50 per cent of tetraethyl lead could be obtained upon cooling to room temperature. This material could then be coated with a protective layer of paraffin--and an appa ratus and means for doing this were worked out. In this way a smooth cake of material was obtained containing a large percentage of tetraethyl lead and having all its ingredients soluble in gaso line * The results of these experiments were never applied in a prac tical way, but they are covered by U. S Patent 1,592,953, July 20, 1926, Method and Means for Treating Motor Fuels, Thomas Midgley* Jr* J. Yl. Morrison, who some time prior to 1922 began to take care of the patent phases of the antiknock research, had formerly been with the B. F. Goodrich Company in Akron. In the summer of 1922 Morrison wrote to H. L. Trumbull at Goodrich and inquired about the experiments that had been made there on tetraethyl lead as a possible vulcanization accelerator. (As later published, in 1925, George Oenslager at Goodrich had tried tetraethyl lead as a possible vulcanization accelerator in 1906, and had found it to have ETC 36965 neport OC-83 168 mild accelerating effect. Ind. Eng. Chem., 17, 395, 1925.) As a result of this contact and later ones, four ounces of each of the following lead compounds were prepared and sent to George Oenslager in early November, 1922i tetraethyl lead, lead triethyl sulphide, and lead triethyl hydroxide. These compounds were test ed by Oenslager as possible vulcanization accelerators and showed some accelerating effect. But to the vulcanized product they im parted a very disagreeable odor. Oenslager said the vulcanized pieces smelled like garlic; but Midgley said no, they smelled like mercaptans--which compounds have, if possible, a still more dis agreeable odor than garlic, Oenslager, who was the original discoverer of organic vulcanization accelerators for rubber, as well as of the value of high percentages of carbon black for making long-wearing tread stocks, was in 1932 awarded the Perkin Medal by the Society of Chemical Industry for his achievements. And there is an interest ing parallelism between his research on vulcanization accelerators conducted around 1906 and the search for an antiknock agent which began 10 years later. The first active accelerator of the vulcan ization reaction discivered by Oenslager was an iodine compound, mercuric iodide (Ind. Eng. Chem., 17, 393, 1925). And, as diready related, the first antiknock agent was iodine too. The second vul canization accelerator discovered by Oenslager was aniline. So also the second antiknock compound discovered was aniline. At one stage of the search for an antiknock agent, it was accordingly be lieved that there was possibly a close relationship between anti knock compounds and vulcanization accelerators. It was partly due ETC 3696 Report X-83 169 to that sunrise that the lead compounds were sent to Oenslager for test, as related above. In April, 1922, attention was first given to a method of determining the lead content of tetraethyl lead. The method of analysis as then proposed (Lead Diary, page 136) consisted in add ing a weighed amount of tetraethyl lead to an alcohol solution of iodine, driving off the alcohol, treating the residue with strong sulphuric acid to convert the lead to lead sulphate, driving off the excess acid, and weighing the lead sulphate present. The methods of analysis for tetraethyl lead and for tetraethyl lead in gasoline as used today were developed later on, however. In the summer of 1922* t7. H. Charch made sobe nickel car bonyl and attempted to prepare also an oil-siluble compound of bis muth, triphenyl bismuthine. This was done in further pursuance of the program of measuring the antiknock properties of the elements in the periodic system, which, as already related at some length, had led to the discovery of lead as an antiknock compound. The nickel carbonyl was tested on August 15, 1922, (Record 19, page 130) and was found to be a powerful antiknock agent, about onefourth as effective as tetraethyl lead. This led to the intensive effort to make the carbonyl compound of iron and the important se quence to it, which will be related further on. The triphenyl bis muthine made at this time was impure, but showed nevertheless that bismuth is an effective antiknock agent (Record 19, page 130). It was in the summer of 1922 that the first known effort was made by an outsider to capitalize on the discovery of antiknock TC 36967 Report OC-83 170 compounds. The Raritan Aniline ^orks, Hew Brunswick, N. J., began then to distribute aniline as an antiknock agent. They tried to sell it to the public through filling stations in Hew Jersey, ilidgley and Sanford Brown of the Condensite Company of America visited one of these stations, located at Hill Street and River Road in Belleville, N. J., and purchased a quart of motor aniline (Letters, page 26). nothing further was done about it apparently, but the sale of aniline by the Raritan people was soon discon tinued anyway; In the summer of 1922 came also the first one of the complaints from a user of tetraethyl lead that it caused troubles with which it had nothing whatever to do, but for whidh it got blamed because it happened to be new and perhaps a little mys terious. This is the kind of resistance that any new product has to face, of course, but which persisted longer in the case of tet raethyl lead than is usual with new things. Mr. Kettering had given some tetraethyl lead to Ward Cromer who used it on a long automobile trip that he took. Upon his return, Mr. Cromer report ed that the lead compound had eaten the coating of shellac off his carburetor float, and that it would accordingly no longer float in gasoline. So a test-was begun to see whether the presence of tet raethyl in Mr. Cromer's gasoline could have had anything to do with the trouble. But after many days no action on shellac coatings could be detected (Lead Diary, page 399). In view of subsequent events, it is of interest to record here that the first order for any considerable amount of tetraethyl lead-->10 gallons of it--came from the Sun Company (now the Sun Oil Etc 369g8 Report 0C-S3 171 Company) in a letter of July 15, 1922, from A. Ludlow Clayden to Midgley. When Midgley attended the S.A.E. Summer Meeting at White Sulphur Springs in June, 1922, he described and demonstrated the effects of tetraethyl lead to a number of those in attendance. Herbert Chase, in his report of that meeting in Automotive Indus tries, 46, 1412, June 29, 1922), said: "Among the most interesting things which developed at the Research Session was the statement by Thomas Midgley, Jr., of the General Motors Research Laboratory to the effect that his organization has discovered and developed a process for making an anti-knock substance which can be added to gasoline and will thereby prevent detonation even when an engine of very high compression is employed. .... The writer was given an opportunity to ride in a car which when pulling knocked badly on ordinary gasoline, but which ceased to knock entirely everi on heavy pulls when the new dope was employed; Included in the story by Mr. Chase was a picture of several men gathered around watching a demonstration--Clayden kneeling directly opposite Midgley--and underneath the picture was this legend: "This is not a crap game, but a group of engineers observing the cremation of tetraethyl lead, the new fuel `dope* which Midgley exhibited." Clayden was sufficiently impressed by what he saw at White Sulphur Springs that June to give Midgley a verbal order for 10 gallons of "Anti-Knock," which he later con firmed by his letter of July 15, already mentioned. "I would like to get a gallon of it as soon as possible," Glayden wrote, "and as to the rest there is no hurry whatever." Whether Clayden ever got the ten gallons of tetraethyl lead that he ordered then is not now known, but he could have had it many times over, of course. Report OC-83 172 CHAPTER IX THE FIRST PAPER ON TETRAETHYL LEAD V/hile Midgiey was at the Birmingham Meeting of the Ameri can Chemical Society in April, 1922, he received an invitation to present a paper on the antiknock research before the American Chemi cal Society at its meeting to be held in Pittsburgh in September* And on April 12 he wrote to Dr. H. E. Howe, editor of Industrial and Engineering Chemistry in part as followst "Upon my return to Dayton I took up the matter of presenting our antiknock work before the American Chemical Society meeting in Pittsburgh and found a very enthusiastic attitude toward this on the part of Mr* Kettering, which assures us being able to do the job thoroughly. "We are making our plans to present this subject. At the present time we would like to suggest the title, The Chemical Control of Gaseous Detonation with Par> ticular Reference to the Internal-Combustion Engine,' paper by Thomas Midgiey, Jr., and T. A. Boyd. "We would start the presentation with a demon stration in glass tubes of normal combustion and detonation, showing the removal of the detonation by the addition of a small amount of antiknock ma terial with a few remarks as to the limitation of this method of investigation. We would then use a large sized demonstrating chart of the gaseous move' ments during enclosed combustion and show how high pressure waves are generated during high velocity com bustion. Following this will be a mot jr demonstration which would evidence detonation both b; instrumentation and audibility ... * we would operate this motor on detonating and non-detonating fuels and (on) detonating fuel compared to detonating fuel plus antiknock material.. This is a rather striking demonstration of the antiknock property. ... We would then close the paper by pre senting graphically with slides the periodic variation of the antiknock value among the 18 elements that show this characteristic." Etc 36970 Report OC-83 173 The above quotation is given at such length because the outline of the proposed presentation contained there is just what was actually prepared and presented. Or rather this is true ex cept for the last sentence quoted, which promised a discussion of the systematic variation of the antiknock property with the peri odic arrangement of the elements, as based on the research de scribed some time earlier in this account. Because of objections from the patent section, however, this part of the proposed pre sentation was not included. The objection from Mr. Morrison to publishing any of the antiknock story at that time was in fact so great that it was only after much persuasion by Boyd during the preparation of the paper that the inclusion of any quantitative data whatever on the effects of antiknock agents was allowed to be incorporated in it. But finally the quantitative data forming Table II of the paper and the discussion of it were allowed to go in (Ind. Eng. Chenu, lilt, 894, October, 1922). This is mentioned as perhaps being of particular importance, because, without such data, the paper would have lost almost altogether its effect as a scientific presentation. And, as it later turned out, this was the paper upon which Midgley was awarded the William H. Nichols Medal by the New York Section of the American Chemical Society. On May 5, 1922, Dr. A. C. Fieldner, who was chairman of the program committee for the meeting in Pittsburgh, wrote Midgley as follows (in part): "The committee was unanimously in favor of accepting your paper for presentation before th*- general meeting of the society. * (It was a special honor to have the paper sched uled for the general meeting, as most papers are presented at sec-- ET? 36971 Report oc-83 174 tional meetings.) "Colonel Church, President of the Carnegie Ins titute, was a little shocked when I told him we wanted to put a gasoline engine on the stage in connection with one of the papers I suppose it seemed sacrilegious to him to have a gasoline engine on the boards where Lladam Schumann-Heink, Fritz Kreislerj and others usually perform," But the matter was referred to Ur. Cun ningham, superintendent of the buildings of the Carnegie Institute, and suitable arrangements were made to use the stage for the pre sentation. "Our committee was very much impressed," wrote Dr. Fieldner also, "with the publicity value of your paper. Everyone is interested in automobiles and the newspaper men would give this a lot of space which would result in good publicity for the rest of the meeting." With the plans thus made, it was only necessary to pre pare the demonstrations in suitable form and to write the paper in such shape that it could be published later. The difficulty met with in preparing a paper considered as proper for presentation on the occasion has already been mentioned. A request was received from Dr. H. E. Howe, editor of Industrial and Engineering Chemis try, to prepare a supplementary paper to be published ahead of the one to be presented at Pittsburgh and outlining -he background of the work on antiknock agents, or suggesting the reasons why the investigation was important. This was done, and a paper, "The Ap plication of Chemistry to the Conservation of Motor Fuels" by Thomas liidgley, Jr., and T, A. Boyd, was prepared and published (Ind. Eng. Chem., 14, 849, September, 1922). etc 36972 Report OC-63 175 The two most striking demonstrations planned for the pre sentation at Pittsburgh were the one to show detonation in an open glass tube and the removal of it by means of an added antiknock agent, and the one consisting of the engine tests showing knock and its removal by means of tetraethyl lead. Engine demonstra tions had been made so often that little preparation was needed for them. But the tube experiment was completely overhauled to substitute diethyl selenide for the ethyl iodide formerly used as an antidetonant and to make the demonstration more certain to work as intended. The embarrassment when, as related earlier, a similar experiment failed completely during an attempt to present it at the Engineers' Club in Dayton had not been forgotten. So the system illustrated in Figure 37, page 176, which incorporated semi-automatic metering of gases to the explosion tube and auto matic ignition when the valve was closed, was developed. To make doubly sure that the presentation would go off as planned and that it was a suitable one, arrangements were made to give a dress re hearsal of it on August 22, 1922, before a special meeting of the Engineers' Club of Dayton to which were invited the members of the Cincinnati Section of the American Chemical Society (which then included the Dayton area). This meeting was v.i-U. attended and went off in good style. Then on Monday, September 4, 1922, Midgley, Boyd, Hochwalt, and V7. II. (Mac) Welsh (mechanic for the Fuel Department) ar rived in Pittsburgh for the meeting of the Ai-eri-.-'in Chemical So ciety. The engine, the explosion tube, and other demonstration ETC 36973 REPORT OC-83 I 76 FIGURE 37 DIAGRAMMATIC SKETCH OF APPARATUS USED AT PITTSBURGH MEETING, AMERICAN CHEMICAL SOCIETY, FOR SHOWING DET ONATION IN AN OPEN GLASS TUBE AND FOR DEMONSTRATING ITS REMOVAL BY THE ADDITION OF AN ANTIKNOCK AGENT. ETC 36974 Report OC-83 177 equipment had been shipped to the Carnegie Institute in advance. The engine was a Delco-Light equipped with bouncing-pin indicator, having a nazda lamp in the circuit, all as pictured in Figure 22, page 102. The entire day Monday was spent setting up the appa ratus and getting it into shape. Or rather it should be said that the latter part of the day was so spent. For, it having been La bor Day, there was no help around the Institute to move the pieces to the stage, nor could a truck be found. So we had to carry each piece, some of them having been very heavy, for the long distance from the place where they were stored, through hallways and doors, and up and down stairways until at last with great relief it could be set down on the stage. But finally, after having solved the transportation problem in this fashion and having repaired such parts as were broken in transit, everything appeared to be in place, and i- good order. The presentation of the paper and the demonstrations which accompanied it were to be made as the first item on the pro gram in the afternoon on Tuesday, September 5. The hall was in use during the forenoon. But during the noon intermission we all went up *n the big stage to check everything over a sain. There was only a little time, for the forenoon session had net - dimmed until late. After having adjusted everything else, we cane at last to the engine and decided to run it a few minutes to make sure every thing was all right and to get it warm, so that it could be wanned up more quickly to the operating temperature di'-'.ng the presenta tion. ETC 36975 Report X-83 178 And then happened one of the most unlucky events--or per haps it was a very lucky one--of the whole endeavor. The engine had only been run a minute or two when out blew a cylinder head gasket, followed by the loud hissing of escaping gas at each stroke. Here was a pretty kettle of fish! Because no such thing had ever happened before in all our experience, we had not thought to bring along a spare gasket. But it was apparent that the cru cial engine demonstration of knock and its removal by means of tetraethyl lead or diethyl selenide could not be made without a new gasket. And already it was so near to the time for the pro gram to begin that the audience was gathering. But there was no gasket and we did not know where in Pittsburgh to get such an un common article as a cylinder head gasket for a Delco-Light engine. Then it was that Mac Telsh performed one of the greatest services of his career. He jumped down off the stage, ran up the aisle and out to Forbes Street in front of the Institute. There he spied a car with a sticker on the windshield identifying it as a courtesy car of the Pittsburgh Section of the Chemical Society, He told his problem to the driver of the car. And, as luck would have it, the driver just happened to know about the distributor of Dolcc-Light engines in that area, and where he was located some distance from there in East Pittsburgh. They drove to his store as fast as possible, were lucky enough to find the proper gasket, and then raced back to the Carnegie Institute. V.Vieh came running triumphantly down the aisle with the gasket md iur.ped up on the stage just as fast as he had left it some time before, for by then it was past time for the meeting t-> begin. But to put the new gasket ETC 36976 Report OC-83 179 in place took only a very few minutes, and the .meeting1 got under way at once with the introduction of Midgley by Dr. Edgar Fahs Smith, then president of the Society. From what roint on, things went off without any further hitch. Midgley's presentation was excellent, the explosion tube demonstration did not fail, and the engine demonstration of knock and its removal with antiknock agents, was enthusiastically re ceived by the audience. In fact the presentation, so elaborate and so striking, was such a great success that in chemical circles L'idgley got there the high reputation for showmanship which he still retains. The presentation later received favorable mention in the official Society report of the Pittsburgh meeting (Ind. Eng. Chen., 14, 885, October, 1922). And later still Midgley was awarded for this paper and outstanding presentation the 'Villiam H. Nichols Medal by the New York Section of the American Chemical Society. Substantially the same matter as that given at the Pitts burgh meeting of the American Chemical Society was later presented, about October 27, 1922, before the Ohio State University Chapter of Sigma Xi, and on December 7, 1922, before the 'marican Petroleum In stitute at the meeting in the Statler Hotel, St. Louis (Bulletin Am erican Petroleum Institute, 84, December 3<., 1922). This paper, with its successful prejw.itation and later publication, had extraordinary importance. This was so, not only on account of the medal awarded for it, but alvo because of the ef fect it had a few years afterwards when the audition of tetraethyl lead to gasoline was under attack by those who claimed.that it would ETC 36977 Report X-83 180 poison the whole nation, '`.'hen that time came, as is brought out later on, those in technical circles, having been informed about the development and sympathetic to it, demanded and got a factual rather than a hysterical consideration of the case. ETC 36978 Report OC-83 181 CHAPTER X WORK ON EXHAUST VALVE AND SPARK PLUG PROBLEMS RESUMED As stated some, pages previously, the status of the Ethyl gasoline development at the end of August, 1922, was as follows: 1. Research on means of making tetraethyl lead had just been transferred to the du Pont Company, where the sodiumlead method as developed in the work at Dayton and at M.I.T. was to be pursued further and put on a commercial scale* 2. Research on the reactions involved in the synthe sis of tetraethyl lead by the sodium-lead route was being continued at M.I.T. 3. The research at Dayton *.vas now to be concentrated altogether up->n the solution of the spark plug and exhaust valve deposit and erosion.problem* The considerable work done up to that time on the spark plug and exhaust valve problem had shov.71 that additions of compounds of chlorine or bromine were very beneficial in lessening the erosion and deposit troubles so far as spark plugs were concerned, and of material benefit also in reducing deposits on exhaust valves. It was now thought that maybe if the chlorine or bromine were to be added as an integral part of the tetraethyl lea'' molecule its ef fect might be still greater. Hence work was begun to prepare lead triethylchioride and lead triethylbromicie (Lead Diary, 409) It was found readily possible to make these compounds. Other compounds of the same type prepared included these: lead triethylhydroxide. Report 0C-S3 182 lead triethylacetate, lead triethylsulphate, lead triethyloleate, lead triethylcyanide, and lead triethylsulphide. In preparing to test lead triethylchloride in the engine, the compound was found to have a very low degree of solubility in gasoline (Lead Diary, 415), and in the engine tests some of it some times separated out in the carburetor. Lead triethyibromide seemed to give better results than the corresponding chloride in respect to valve and spark plug condition, and late in September, 1922, (Lead Diary, 436), a 100-hour engine test of the compound was be gun in one of the single-cylinder test engines. At the same time another engine was run on untreated gasoline for comparison. The full 100-hour run was completed, but the spark plug electrode in the engine running on the treated gasoline was by that time badly corroded. The exhaust valve, however, was in pretty good condition. A second run was then begun using well purified lead triethyibromide (Lead Diary, 447), and this test was run about 120 hours with some what better results, although about midway in the test the spark plug porcelain was broken by a wrench and a new one had to be put in at that point, thus invalidating to some extent the spark plug test, Hov:ever, at the end of 120 hours, the spark plug in the engine run on the lead-containing fuel was about like that in the engine on straight gasoline (Lead Diary, 451). Another interesting observation from this run was that the engine operated on the lead-containing fuel appeared to contain less carbon than the other (Lead Diary, 451). This same observation was made also on later occasions; but, carbon deposits being usually so erratic, the observation was never ETC 36980 Report OC-83 183 deemed definite enough to justify any conclusion that the presence of lead reduced carbon deposits. The antiknock effectiveness of lead triethylbroraide was measured and found to be only about three-fourths that of tetra ethyl lead (lead Diary, 446 and 486). This observation, coupled with the fact that the presence of the bromine within the molecule materially reduced the solubility in gasoline, caused the men. at M.I.T. to be asked to undertake the preparation of a compound in which one ethyl radical of tetraethyl lead would be replaced not by bromine alone but by an organic compound of bromine, such as C2 Br (Monthly Report, November 1, 1922). But this attempt did not prove to be very successful. Meanwhile, the tests of other possible corrective agents added along with tetraethyl lead were being continued as opportunity offered, and a great many were tested (Rec. 19, p. 145 et seq.). These included carbon tetrachloride and many other compounds of ` chlorine, as well as chlorinated lubricating oil and chlorinated oleic acid. Ethyl carbonate was another one of the many possible corrective agents tried and one that looked quite promising for awhile. So promising did ethyl carbonate look as a corrective agent that car tests of it were begun by Joe Butz. But in the end these tests did not turn out well. Of all the many addition materials tested, those containing chlorine and bromine were the only ones that showed consistent improvement. Here it is interesting to note that, in all the testa made during the intensive program pursued during the last four months of 1922, no separate bromine compounds were apparently used tffC Report y'-BJ 184 as addition agents. And this suggests how strong was the belief at that time that bromine was too scarce and costly to be practical, for tests reported earlier had shown bromine to be a powerful cor rective agent. So far as bromine was concerned, the tests during the fall of 1922 were confined to lead triethylbromide. But, al though bromine in that form showed pronounced corrective effect, the amount of combined bromine present in lead triethylbromide was not sufficient to overcome the spark plug and valve troubles com pletely enough. This was shown conclusively by car tests (Lead Diary, 490 and 494). Right at the end of 1922, therefore, the amount of corrective compound began to be increased by adding to the gasoline in addition to lead triethylbromide a small amount of chlorinated lubricating oil. But soon carbon tetrachloride was substituted for the chlorinated lubricating oil. Sale to the Public Decided Upon The result of the road tests of lead triethylbromide fol lowing this addition of chlorine, although not having shown perfect correction of the lead effects in respect to spark plugs and valves, were nevertheless thought to be good enough that in January, 1923, a decision was reached to begin selling the material to the public in a small way. This decision was a cause of considerable concern to some of the men active in the development who were struggling with the shortcomings of the compound, they having felt that the material was not yet ready for the market. But nevertheless the decision to put it out was in accord with Mr. Kettering's phil osophy that the commercialization of a product should not wait on Report OC-83 185 its being altogether perfected. And, as it turned out, the decision to begin selling it then was not a mistake, for the product was rap idly improved further as the investigation proceeded. Miscellaneous Events During Fall of 1922 Before proceeding to give an account of the first sales of tetraethyl lead to the public, some other events of the five months following August, 1922, will be recounted, A supplementary effort was made to develop a laboratory method" as a substitute for the en gine test for finding whether a compound would be effective as a corrective agent for the spark plug and exhaust valve troubles re sulting from the presence of lead in the gasoline (Lead Diary, 4724). Many confounds were studied, but the results were not reliable enough to make such tests a suitable substitute for those run direct ly in the engine. If lead triethylbromide was to be used as an antiknock agent, it demanded of course that some suitable means of producing the compound be developed. The job of finding such a means was given to J. P. Andrew, and he began work on it in September, 1922 (Lead Diary, 435). After a great deal of experimentation, during which he made the small amounts of lead triethylbromide needed for use in the current test program, he settled on a method of prepara tion which consisted in passing hydrobroraic acid gas into a solution of tetraethyl lead in kerosene (Lead Diary, 490). This method, which worked well, was finally carried out in the apparatus shown in Figure 38, page 186. In this large laboratory-scale apparatus was made later on all the lead triethylbromide used in the first two months of the sale of Ethyl Gasoline to the public. ETC 36983 AOPAKA7JS F O.-t CONVERTING THl compound usfd in the IS JAMES P. ANDREW. TETRAETHYL LEAD INTO first ethyl gasoline LEAD TR I E T HYL BROW IDE, sold, the operator ETC 3698* Report OC-83 187 Tests were made also on the stability of lead triethylbromide in gasoline solution. And again, as in the case of tetraethyl lead reported earlier, a long search was made for a material that could be added to the solution to make it decompose less readily (Record 19, page 142 et seq). But it was found that, after having been purified by fractional crystallization, lead triethylbromide dissolved in gasoline was stable enough of itself in the absence of white light for all practical purposes (Record 19, page 146). On October 16, 1922, Messrs. A. Felix du Pont, R. G* Woodbridge, and F. W. Brading of the du Pont Company visited the laboratory to inquire whether antiknock compounds such as tetra ethyl lead might possibly have any usefulness for controlling the burning rate of gun powder. They were made acquainted with the re sults obtained by W. H. Charch in which tetraphenyl lead and tetra ethyl lead mixed with black powder apparently affected the nature of the resulting explosion in a gun in such a way that the noise was lessened. They were also supplied with a few grams of each of the following compounds (Lead Diary, 455): lead triethylchloride, lead triethylsulphate, and tetraphenyl lead. W. H. Charch, who had worked at the laboratory during the sunnier of 1922, returned in October to the Ohio State University to pursue work toward his doctor's degree; and, through the patent de partment, a contract was made with him by which he was to work on the antiknock problem under a kind of fellowship arrangement. Under this arrangement, he made up a number of special lead compounds for test of knock suppressing effect, and began his studies of the con- ETC 36985 Report OC-83 188 ductivity of the gases in an engine and of the effect upon it of the presence of knock and of antiknock compounds (Lead Diary, i88). He also continued the long effort to make iron carbonyl (Lead Diary, 5O6 and 550) which turned out finally to be unsuccessful at atmos pheric pressure. A considerable number of new materials were tested for knock suppressing effect (Monthly Report, December 30, 1922). These included several new compounds of lead, and some of tin, ti tanium, and gold. Several of the compounds proved to have antiknock effect, but none was superior to tetraethyl lead. Two items of correspondence during the fall of 1922 may be mentioned. First, in early September came a letter from Harry Spears of the Spears and Riddle Company, Wheeling, W. Va.j asking that when the new compound about which he had read in the August number of Motor became available his company be allowed a chance to market it. Later Spears and Riddle did become one of the earliest distributors of gasoline treated with tetraethyl lead. And, as it turned out, the sale of Ethyl Gasoline in West Virginia by Spears and Riddle had some influence in getting the Standard Oil Company of New Jersey to decide to sell it also. Second, was a letter from F. E. Moskovics of the Kordyke and Marmon Company asking for more of the tetraethyl lead of which Mr. Kettering had previously given him a sample. Midgley wrote back telling Mr. Moskovics about the spark plug and exhaust valve problems, and suggesting that he wait for a further supply until the problem had been more nearly solved. But back came a letter from Mr, Mos kovics saying, "As bad as it is, I should like to get some more," ETc 3^s6 Report OC-83 189 At the du Pont Company, development work on the making of tetraethyl lead continued to go forward successfully. V.'ithin a few weeks they were getting yields by phe sodium-lead process of better than 85 per cent of theory. This was accomplished by virtue of making use of the Na2Pb4 alloy which had come out of the work at M.I.T. (Lead Diary, 376 and 381), and of controlling the degree of alkalinity of the reaction mixture * The latter was effected by using calcium chloride to precipitate the excess of hydroxide. By the end of September a stock of 70 gallons of tetraethyl lead had been accumulated at Dayton, and this was gradually increased as the work at du Pont went forward (Monthly Report, October U, 1922). By the middle of November, Midgley was able to report to Mr. Ketter ing ("Summary of Present Situation on Antiknock Material," November 20, 1922) that the production "phase of the tetraethyl lead problem seems to be pretty well solved and we have the assurance of the du Pont Company in the form of a contract that they will produce tet raethyl lead at a price that renders it quite commercial." Further Report of TVork at M.I.T. Meanwhile, at M.I.T. work on various items, chiefly re lating to methods of synthesis, was going forward. The methods of making tetraethyl studied included some not previously mentioned, such as the effort to use silicon and phosphorus in the synthesis. Some additional lead compounds were prepared also and sent to Dayton for test of antiknock effect. There was at M.I.T., too, some col laboration with Midgley in the work which he and Hochwalt did in November in the preparation of a special ethyl compound of lead. ETC 36987 Report OC-83 190 by the electrolysis of lead triethylhydroxide in alcoholic solution (Lead Diary, 481 and 483). Results of this study were later published ("A New Metallo-Organic Compound: Diplumbic Hexaethyl," Thomas Midgley, Jr., C. A. Hochwalt, and George Calingaert, J. Am. Chera. Soc., 45, 1820, 1923). And later on a great deal of work was done at M.I.T. in examining the deposits on spark plugs and valves. The Dayton laboratory cooperated in this work to the extent of supplying deposits and parts obtained by running engines on tetraethyl lead plus various corrective agents, chiefly chlor ine, bromine, and sulphur. The results appeared to show that bro mine owed its superiority over chlorine as a corrective agent either to more complete reactivity with lead or to yielding a more volatile compound (Lead Diary, 515, 542, and 544). But bromine was not substituted for chlorine as a corrective agent until quite some time later when it could be bought at a lower price and when events had dispelled somewhat the then current fears about the inadequacy of the supply of bromine. The Toxicity Problem Again There were also during the fall of 1922 some further inci dents relating to the possible toxic hazards arising from tetraethyl lead. First, was a letter from Dr. Eric Krause of the Institute of Technology, Potsdam, Germany, written at the request of the men at M.I.T. (Lead Diary, 49l). This was the Dr, Krause of Gr\ittner and Krause, who had published several papers jointly and individually on organic compounds of lead, chiefly lead alkyls. In his letter. Dr. Krause expressed the belief that the organic compounds of lead ETC 36988 Report OC-33 191 are exceedingly dangerous. He told of the elaborate precautions which were taken in his work to guard against possible lead pois oning, and said that in spite of this he was at that time being forced to take many vacations from lead work because of damage to his health. He gave it as his opinion that the health of Drs. Gnittner and Tafel, both of whom had died some years before, had been seriously affected by their work with lead compounds. Second, was a letter of December 20, 1922, from U. S. Surgeon General Hugh S. Cumming to Mr. Pierre S. du Pont (Letters p. 51). A member of the staff of the U. S. Public Health Service, said Dr. Cumming had been detailed to attend a meeting of the New , York Section of the American Chemical Society on November 10, 1922, at which the discovery of tetraethyl lead as an antiknock compound was discussed in the lecture of the evening by Midgley. (The raember of the Public Health Service staff who attended the meeting was Surgeon Norman Roberts. There is a copy of his report to Doctor Cumming, November 13, 1922, among the letters at the front of Vol. 3 of the Lead Diary.) Doctor Cumming expressed his concern about the possible hazard that would be introduced by finely di vided lead in engine exhausts if tetraethyl lead should be put into gasoline. The letter from Doctor Cumming to Mr. du Pont was sent on to Mr. Kettering, and Midgley responded to it on December 30, c* , i 1922. In his reply ilidgley expressed confidence that no health 1 | hazard to the public would result, but said that the exhaust probleml l had not yet been investigated, partly because in engine tests made . ETC 3698g Report OC-83 192 in the Dayton laboratory up to that time it had not been possible to separate from the exhaust more than a fraction of the lead en tering the engine. "We expect in the near future," Uidgley con cluded, "to place a small quantity of this lead compound on the market in some districts* There will not be enough lead used in the early stages of this development to present any health hazard whatsoever and during this period we propose to investigate the toxicity of these exhaust gases very thoroughly^ as to determine just what the ultimate limit to the use of lead compounds actually is. Y?e hope to secure your most hearty cooperation in carrying on this work." What Uidgley referred to in the sentence just quoted was a proposed investigation of the possible toxicity of the engine ex haust by the Bureau of Mines, he having already some time before that been in contact with Dr. A. C Fieldner about it (Summary of Present Situation on Antiknock Material, November 20, 1922. Also correspondence with A. C. Fieldner, Bureau of Mines, October, 1922.) The possible hazard thought of here was not from tetraethyl lead itself but from finely divided lead compounds in engine ex hausts. Relating to the more active tetraethyl lead itself, it may be noted that Midgley and Hochwalt had been having digestive derangements, subnormal body temperature, and reduced blood pres sure, which were thought to have been caused by the too intimate contact with lead compounds that they had been having for some months past. Also in a letter of December 22, 1922, (Lead Diary, 497), Calingaert said that he and Mead were taking a little vaca tion for the rest of the year because they had absorbed somewhat ETC 36990 Report CC-83 193 more lead than they ought. Shortly thereafter the men at M.I.T. were under treatment by Doctor J. C. Aub of the Harvard Medical School, although continuing their work. Also, as is related be low, Midgley -went to Florida in February for a month of rest. Nichols Medal Award to Midgley An outstanding event of December, 1922, was the award to Midgley by the New York Section of the American Chemical So ciety of the William H. Nichols Medal. This award was for the two years 1921 and 1922 and was made for.the work reported in the paper on ''The Chemical Control of Gaseous Detonation with Particular Reference to the Internal-Combustion Engine,'1 which had been presented before the American Chemical Society at Pitts burgh in September and published in Industrial and Engineering Chemistry in October. Among the many letters of congratulation on the award that Uidgley received was one from R. E. Wilson, then at the Standard Oil Company of Indiana, in which was ex pressed the belief that the Nichols Medal was just the beginning of the recognition Midgley would receive for this work. And that opinion turned out to be a correct one. Among these later items of recognition was the award of the Perkin Medal to Midgley in 1937 by the American Section of the Society of Chemical Industry; of the Priestley Medal by the American Chemical Society in 19A1, highest honor the Society can confer; and of the important Willard Gibbs Medal by the Chicago Section of the Society in 1942* At the presentation of the Perkin Medal in New York on January 8, 1937, ETC 36991 Report OC-33 194 R, E. Wilson, now by that time promoted to President of the Pan Am erican Petroleum and Transport Company, made a fine address about Uidgley and his accomplishments and about Wilson's own association with him (Ind. Eng. Chera., 29, 239, February, 1937). ETC 36992 Report OC-33 CHAPTER XI SALE OF ETHYL GASOLINE TO THE BU3LIC BEGINS 195 In preparation for the sale to the public of gasoline treated with tetraethyl lead, a name for the product was chosen and arrangements were made with a gasoline retailer to sell it. The name selected was "Ethyl Gasoline," the suggestion having been made by Ur, Kettering from the ethyl in tetraethyl lead on which it was based. At the outset the name was however customarily ab breviated to "Ethyl Gas." Arrangements were made with The Refiners Oil Company, an independent gasoline distributor in Dayton of which Willard Talbott was manager, to experiment with selling the product in one of its stations, that located-at Sixth and Main Streets. There one dispensing pump and the underground tank with which it connected was set aside for the new product. At the beginning of February, 1923, the experimental sale was started. The storage tank contained "New Navy" gasoline to which had been added lead triethylbromide and carbon tetrachloride in the amount of 7 grams of the former and 1.5 grams of the latter per gallon. The addition had been made by dissolving in benzol, to a total volume of U gallons, enough of the lead triethylbromide and carbon tetrachloride to treat 1,000 gallons of gasoline, and then blending that solution with the gasoline by running it in along with the stream of gasoline as it went into the storage tank from the tank wagon. ETC 36993 Report OC-83 196 The retail prices of the four gasolines sold at the sta tion at the outset of the sale were as follows: "New Navy" gasoline.......................... . . 20 cents per gallon Aviation (high test) gasoline , ... 24 Benzol gas, 40$ benzol-60^ gasoline . 27 Ethyl Gasoline , ........................ ...,.24 The prices of all except the Benzol gas were raised 1 cent a gal lon each on February 10, and again on February 24* The product was advertised there by two signs about 5 ft. X 1 ft. in size placed above the driveway as shown in the picture of the station. Figure 39, page 197, and lettered as follows: "ETHYL GAS Antiknock Gasoline, Product of the General Motors Research Corporation" There was also an illuminated face at the top of the vending pump bearing the words, "ETHYL GASOLINE" in the center with "The General Motors Research Corporation" arranged in a circle surrounding it* At 10 o'clock the first morning not a single sale of the new product had been made. Then the research laboratory representa tive on duty at the station began to approach customers as they came into the station telling them about the new product, without exaggerating its merits. In that way 70 gallons were disposed of during the succeeding three hours. The first customer for the product bought only 2 gallons, saying that he would take a chance on that much (Letters, page 4). After the evening newspapers came out bearing a news item about the new product (copy in Appendix VIII),. the sales showed a steady increase. And, by the time the meters were read at the customary time the next morning, 10 A.M., 408 gal lons .had been sold. ETC 36994 FIGU-E 59 contemporary photograph of the first station in which F T H ' L CASOLINE WAS ;OLD TO THE PU8LIC. IT WAS DIS PENSED THROUGH THE SECONC PUMP FROM THE RIGHT. ETC 36995 Report 03-83 198 The representatives of the research laboratory on duty at the station were R. D. Wells and A. R. Brubaker. One or the other of these men was there all the time during the early weeks of the experimental sale. Besides answering questions and talking to cus tomers about the new product when opportunity offered, they kept a record of each sale in such a way as to give the following items of information! date, gallons purchased, license number of car. These records were kept by a special system which enabled them to tell at a glance whether any customer had bought Ethyl Gasoline be fore. And here it may be noted that the customer to whom the first sale was made, saying that he 'would take a chance on 2 gallons," bought Ethyl Gasoline twice again within a week. On the second day. the sales of Ethyl Gasoline jumped to 838 gallonsj and on the next day following, which was Saturday, to 1,057 gallons. From that point on the general trend during Febru ary was downward. This may be seen from the graphical sales record for February, Figure 40, page 199, which shows also, for comparison, the sales of the other gasolines distributed at the station. Aside from the customary falling off in the case of a product that was not advertised, there was the factor that on February 4 the weather got extremely cold and stayed cold almost throughout the month. This caused some complaints about hard starting from users of the new gasoline, for the base of New Navy gasoline was of low volatility, even for that time. The total amount of the new product sold -- in February was 8,375 gallons, llarch sales were down to 4,175 gal lons. In April there was an increase again to 6,187 gallons, al though on one day in April, the 13th, only 47 gallons of Ethyl ETC 36996 OC-33 199 FIGURE 40 daily sales of ethyl gasoline at the pioneer station ouring the first month, February 1923. sales of other GASOLINES AT THE STATION ARE PLOTTED ALSO FOR COM- L ETC 36997 . .sr Report 00-83 200 Gasoline were sold. Starting about February 3, Midgley was absent for more than a month, he having taken a trip to Miami Beach, Florida, for a rest. This he did in an effort to get rid of the lead effects which he had suffered from too intimate contact with the stuff during the experiments of the previous several months, chiefly on methods of making tetraethyl lead. The symptoms of his difficulty were the subnormal temperature and the reduced blood pressure spoken of previously. The outcome of his rest he reported in a letter written to R. E. Wilson on March 15 after his return, as follows: "I had a very fine month in the south. ... I am much improved in health so far as the way I feel is concerned, but my temperature is not yet back to normal." On February 7 Midgley wired Boyd from Miami Beach: "Suggest you try three cubic centimeters tetraethyl lead and two cubic centimeters carbon tetrachloride per gallon in the Buick for two thousand miles." The next day he sent a supplementary wire saying: "Reason for wishing to run Buick on tetraethyl lead is to replace the bromide with it if humanly possible to do iso and as quickly as possible. This would mean quick production and reduced cost both of which are needed." This suggested car test of tetra ethyl lead and carbon tetrachloride was not a "wild stab." It was based upon the results of a recent series of the laboratory engine tests being conducted by Boyd and E. E. Gold (Record 19, 145 et seq.). The Buick car test was run for a distance not of 2,000 miles but of 8,500 miles, at the end of which the spark plugs "were still in 36998 Report OC-83 201 satisfactory operating condition, the electrodes being burned to only a small degree and the porcelains being dark but whole'1 (Month ly Report, March 31, 1923). First Change in Formula The result of the test just mentioned was that during March, 1923* the composition of Ethyl fluid was changed from lead triethyl bromide plus carbon tetrachloride to the following: Tetraethyl lead . .... 3 parts by volume Carbon tetrachloride , , 2 parts by volume It was expected that this mixture would have the following advan tages over that in use initially: 1. About 25 per cent increase in antiknock effect 2. Lower cost 3. Greater solubility 4. Lesser tendency to decompose The use of this composition was continued until about October 1, 1923; but because of the troubles experienced with it, which will be described later, carbon tetrachloride was then replaced with another compound of chlorine. At the end of February, 1923, Boyd went to Chicago at the request of Mr. Kettering and made arrangements with Mr, Harry Croninger of the Yellow Cab Manufacturing Company to furnish them enough of the antiknock compound or Ethyl fluid to treat 500 gal lons of gasoline per day. It was arranged that the compound was to be sent to three of the Yellow Cab Companies: Chicago, Cincinnati, and Buffalo. The use of the compound by the Yellow Cab companies was however discontinued after a short time. Report OC-83 202 Nichols Medal Conferred Another one of the several pnblems with which Boyd was struggling during Midgley's stay in Florida was the preparation .of a paper to serve as Midgley*s address on the occasion of his re ceipt of the Nichols Medal, which was to be presented to him at the Chemists' Club in New York on March 9, 1923. It was intended, of course, that this should be a scientific paper worthy of the occasion. And so the assembling of data for the paper was begun in December right away after word came that the medal had been awarded. The hope was to use some of the scientific data accumu lated in tjje search for a practical antiknock compound, particu larly the matter showing the relationship of antiknock effect to position in the periodic system, as already shown in Figures 25, 26, and 27, pages 114, 115, 116. These charts were in fact pre pared at that time and for this specific purpose* A strenuous effort was made to get the further experimental data needed to round out the story which Midgley wished to present. On February 5, Bcyd wrote to Midgley: "I am devoting my wtnle time to the paper." . V7ithin a few days a copy of a tentative draft was sent down to Midgley and simultaneously one was dispatched to J. W. Morrison for review from the patent standpoint. Midgley seemed well enough pleased with the product, but Morrison took a-differ ent view. All the tables, all the figures, all reference to spec ific compounds, and much of the text must come out, he said, leav ing really nothing in the way of a scientific paper. Upon receipt ETC 37000 Report OH-83 203 of this word, Uidgley wired Morrison his contrary view and also wired Boyd, telling him to "take this stand and fight." But after conferences, letters, and more telegrams the upshot of the matter was that for his Nichols Medal address Uidgley had to give what was pretty much a repetition of the matter that had been presented in Pittsburgh to the American Chemical Society. The matter pub lished afterwards was consequently quite brief and contained very little that was new (Ind. Eng. Chem., 15, 421, April, 1923) The data so laboriously assembled for the paper was not then published until 14 years later, when it was included in Uidgley's Perkin Medal address (Ind. Eng. Chem., 29, 239, February, 1937). Uidgley went directly from Florida to New York for the meeting at the Chemists* Club on March 9 at which the Medal was presented. The various demonstrating equipment needed had been sent on in advance.. Everybody was so busy during the day getting it into shape that no one thought to inquire whether a lantern had been provided to show the slides, as had been duly requested in ad vance. But after the dinner and just before the meeting it became knc'.vn that there was no lantern. Because a lantern was really quite necessary to the presentation, there was much scurrying around by the men who had the meeting in charge. Finally a lantern with its operator appeared, but not until after Dr. Wilder D. Bancroft, who had been delegated to speak on the medalist and his accomplishments, had talked for a solid hour to fill in the time. From that point on however the meeting went off well. At any rate, Uidgley retained the reputation for showmanship which he had acquired in the meeting at Pittsburgh. In the absence of Dr. William H. Nichols on a trip EtC 3?0qi Report 0C-S3 204 abroad, the presentation of the medal was made by Dr. Charles H Herty, former president of the American Chemical Society, and at that time editor of Industrial ard Engineering Chemistry. personnel of Fuel Section. April, 1923 The personnel of the Fuel Section of the General Motors Research Corporation in April, 1923, was as follows: Thomas Uidgley, Jr. James P. (Jimmy) Andrew F. E. (Fred) Aseltine A. M. Babitch Y7. G. (Doc) Berry T. A. (Tab) B-*yd A. R. (Art) Brubaker Ruth DombuschH. S. Gerdes Y7. K. (Gilk) Gilkey C. P. (Pat) Harding C. A. (Ted) Hochwalt R. N. (Bob) Janeway R. D. (Russ or Shorty) Tfells Of the above persons not previously accounted for in this history, Fred Aseltine and A. M. Babitch were working on carburetor research and on producing a- fuel system for a kerosene-burning tractor. Aseltine is now at Delco-Remy and Babitch is at the A. C. Spark Plug Company. Ruth Dombusch was then secretary of the Fuel Sec tion, and is now at the Thomas and Hochwalt Laboratories in Dayton. H. S. Gerdes was working with Harding on the mechanical and the en gine-testing endeavors. Bob Janeway was working not on Ethyl Gaso line but on a project called "Theoretical Study of Combustion." Ha is now at the Chrysler Corporation. TC 37002 Report OC-83 205 CHAPTER XII GENERAL MOTORS CHEMICAL COMPANY In the Monthly Report for March, 1923, occurs the follow ing: "The arrangements for distributing Ethyl Gas Fluid on a larger scale which are in charge of Messrs. Sloan, Mott, Kettering and Midgley are being rapidly rounded into shape. An apparatus for metering Ethyl Gas Fluid into gasoline in the proper proportion is being de veloped." A part of these arrangements was the founding of the Gen eral Motors Chemical Company, which was incorporated under the laws of Delaware on April 23, 1923, to take over the manufacture and sale of Ethyl fluid. The total authorized capital stock of this new cor- poration was $100,000. The directors were: Charles F. Kettering Thomas Midgley, Jr. Charles S. Mott Alfred P. Sloan, Jr. Earle W. Webb At the first meeting of the directors held in Detroit on May 3, 1923, the following were elected officers of the General Motors Chemical Company: President Charles F. Kettering Vice President Thomas Midgley, Jr, Secretary T. S. Merrill Asst. Secretary F. 0. Clements Treasurer M. L. Prentis Asst. Treasurer H. G. Guimaraea Comptroller Frank Turner Asst. Comptroller H. G. Guimaraes On March 29, 1923, Midgley sent to W. F. Harrington of the du Pont Company a wire which contained the following: ETC 37003 Report OC-83 206 "It was officially decided this morning to go ahead with the antiknock program as rapidly as possible. Consequently this constitutes official notification that you are to get out one hundred gallons of tet raethyl lead per day as soon as possible." In the effort to extend the outlets for Ethyl gasoline, Hidgley visited on April 3 and 4, 1923, three of the eastern oil companies: the Atlantic Refining Company, the Tide Water Oil Com pany, and the Standard Oil Company of New Jersey. All showed in terest, but none made any definite commitments (Letters, page 33) Atlantic, through Dr. T. G. Delbridge, said that when convinced of the merit of the compound they would like to have Pennsylvania and Delaware as exclusive territory for a period of five years. Tide Water, through Byron Benson, said they would like to have New York City as exclusive territory for a year. But neither com pany sold Ethyl Gasoline until some years later. First Knowledge of Research on Lead at Standard of New Jersey At the Standard Oil Company of New Jersey, Frank Howard was the man seen. .His company, he said, would like to treat their entire production of gasoline with an antiknock agent at a cost of not more than one cent a gallon and without telling the public any thing about it. Further Hr. Howard informed Uidgley that they were making application for a patent on making tetraethyl lead by the sodium-lead method using ethyl chloride under pressure as the alkyl ating agent, and that they were sure they could make tetraethyl lead for six dollars per gallon--less than one-fourth the price the du Pont Company was then being paid for it at two dollars a pound. The process to which Hr. Howard referred, as became known later, was ETC 37004 Report OC-83 207 developed by Dr. C. A. Kraus at Clark University (Dr. Kraus is now at Brown University) with the assistance of Dr. C. C. Callis. The work of Doctor Kraus was subsidized by Ur. Howard's Company, and was begun after it became known that tetraethyl lead was a prac tical antiknock agent, although in past years Doctor Kraus had done a great deal of work in investigating the making and properties of alkyl compounds of other metals. (For his extensive work on the alkyl metals, including that on how to make tetraethyl lead by the use of ethyl chloride, Dr. Kraus was awarded the Nichols Medal for 1923, the year following the award to Midgley.) It was at this time also that a definite suggestion was made that General Motors and Standard of New Jersey join hands to commercialize Ethyl. In a memorandum of April 9', 1923 (Letters, p. 33), Midgley said this about its "Mr. Howard suggested that the General Motors and Standard Oil Company of New Jersey pool interests in regard to antiknock gasoline and Mr. Howard felt that his patent for making tetraethyl had opened the door to such negotiations. It cannot be denied that from our standpoint it would be a very desir able thing to have the New Jersey Company lined up with us." The ideas advanced here were later to result in the form ation of the. Ethyl Gasoline Corporation. But, although there fol lowed other meetings with men in the Standard Oil Company of New Jersey, this did not come about until several months later (in Aug ust, 1924), after Ethyl Gasoline had been on the market for some con siderable time. A previous attempt to set up a Joint arrangement be tween the Standard Oil Company of New Jersey and the General Motors Research Corporation has already been mentioned (page 120). ETC 37005 Report OC-83 208 Standard of Indiana Becomes First Large Distributor In hia search for a wider outlet for Ethyl Gasoline it was natural that Midgley should see also R. E, Wilson, who had gone to Whiting as director of research of the Standard Oil Contpany of Indiana, As a result of these contacts with Wilson, with Dr. William 11. Burton, then president of the Standard Oil Company of Indiana, and later oh with vice-president Allan Jackson, Wil son was sent to Dayton to observe the sale of Ethyl Gasoline in the single station from which it was then to be had. After lunch at the Engineers' Club, Midgley and Wilson went over to the filling station and, as luck would have it, they saw there a string of five cars lined up waiting turns at the one Ethyl pump. There was much joking then between Wilson and Midgley about how perfectly Midgley had staged the affair, and they still recall it on occasion. But nevertheless the unusual rush of demand that developed just then, although purely accidental, may well have had an influence on the decision under which in the lat ter part of 1923 the Standard Oil Company of Indiana became a dis tributor of Ethyl Gasoline. They did so under an agreement which gave them the exclusive right to sell the product in the eleven states of their territory for a period of eighteen months. This, having been the first one of the major oil companies to take on the sale of Ethyl Gasoline, it was of course a very cheer ing and an extremely important event. Even the prospect of it called for a conference at the du Pont Company, June 16, 1923, on how. to step up the projected production of 100 gallons of tetraethyl lead ETC 37006 Report OC-83 209 per day to the larger amount which it was expected this promising new contract would call for when it went into effect. The further activities relating to sales in 1923 resulted in extending the distribution of the initial distributor, the Re finers Oil Company, to Cincinnati, where sale of Ethyl Gasoline was begun in the early summer. Spears and Riddle Company, the West Virginia jobbers, already spoken of, also became distributors in 1923, with "Fleet-Wing Ethyl." How the number of distributors then grew in the years following is shown in Figure 41, page 210* That none were added in 1923 was due to the poisoning episode of November, 1924, as related further on* This episode resulted in the product being taken off the market from the summer of 1925 until early 1926, while it was undergoing the searching investiga tion by the Surgeon General's Committee to be described later. But Ethyl Gasoline came out of that investigation with a clean bill of health. (There is a slight error in the list of distributors of Ethyl gasoline. Figure 41, in that Gulf Refining Company, not men tioned there, was distributing Ethyl gasoline in 1924 in certain states*) First Efforts to Measure the Lead Requirements of Gasolines It was for the Standard Oil Company of Indiana that the first regular work was begun on rating gasolines or on measuring. y the amount of tetraethyl lead needed per gallon to get a given de gree of freedom from knock. The first of this work was done in April, 1923 (Record 21, page 2). And on July 10 several samples of gasoline from the Standard Oil Company of Indiana were rated. There ETC 37007 ^3OUT OC-83 r mrm tWff.WJJJUIUJIU* 2IC ETDIVL IS EVEIIYWIIEME 1 PUMP IN 5 NOW HAS IT MILLIONS OF MOTORISTS BUY IT LIGHTLY mere than tight years age, one loot S service station as telling Elhyl CeM>line. Today 100 oil refiners <*11 it through their on and dealrr sta tions, and through thousands of independent (oral oil companies. Ethy I Caeolioe has become the largest selling brand of motor fuel in the Lnitrd Slates and Canada. There must be a reason for such sucre**. There is! im gallon of Ethyl Caroline U good ga^line. tested for all the qualities that make a gasoline good, plus Etbyi fluid, tbe ingredient that refunds combustion. Ethyl fluid prevents the uoevea explosions of gasoline that cause po*er-a*tc. harmful ''knock" and ox re heating. h delivers added po*er to the pision* itb a smoothly inereasing pressure that brings nut tlie best performance of 0117 nr. Try Ethyl in your ear. Whatever its age or make. Ethyl sill tmproreiu performance'and you sill effect a real sax ing in operating costs in the long run. Ethyl is a premium-priced gasoline by the gallon, but it is the most economical motor fuel you ean bus by the year. Ethy l Gasoline Corporation. New York City. NAMES MAKE INcVldlkl C\Af C I HfKARttHC MAMS OF WIAOINQ OIL fFINING COMPANIOLSTIO in THt OtOU M WHICH THCY STABrcfi TO SCU ftHTL GASOUF ETHYL GASOLINE rikawaMti FIGURE 41 COPY Or ADVERT I SE.ML NT SHOWING HOW THE DISTR I8UT0RS OF ETHYL GASOLINE WERE ADDED TO FROV YEAR TO YEAR UP TO 1931. ETC 37008 Report OC-83 211 was at that time no definite standard fuel, of course; but the gas olines "were compared with our stock gasoline by determining rough ly the amount of PbEt/, (tetraethyl lead) necessary to add to each sample to make it equivalent in knocking tendency to 3 cc. PbEt^ per gal. of our gasoline" (Record 21, page 33). The matches were made by comparing the intensity of the light in the lamp in the cir cuit of the bouncing-pin apparatus. Also 20 per eent of kerosene was added to each gasoline after it had been treated with the given amount of tetraethyl lead. This was done to produce a suitable de gree of knock in the engine. The ratings as thus made were as fol lows: Source of Sample cc. Tetraethyl Lead Per Gallon to Make Sample Equivalent to Stock Gasoline plus 3 cc. Tetraethyl Lead per Gallon Whiting Sugar Creek Wood River Casper, No, 1 Graybill Casper, No,. 3 Laramie, No, 2 3 2.75 2.5 3 2.5 2.5 2.5 Thus there was at this time no standard fuel of definite degree of freedom from knock and nothing more than an elementary method for matching it had been developed as yet * But some of the later improvements in respect to knock rating and reference fuels have already been mentioned in the section ori "Eouncing-Pin Indica tor Developed," beginning on page 95. Advertising of Ethyl Gasoline Begins It was in the summer of 1923 that the first advertising of Ethyl Gasoline was done. The initial program was put into the ETC 37009 Report OC-83 212 nands of the Campbell-Ewald Company of Detroit, who assigned Webb Taylor to the job. The Ethyl emblem or trade mark design was sug gested and sketched then by Henry Ewald himself. After it had been drawn up and approved, a series of newspaper advertisements were prepared to be used first in Cincinnati and Dayton. A copy of the first one of the advertisements put into the Cincinnati papers is included as Figure 42, page 213- The emblem as designed by Mr* Ewald is reproduced at the top in Figure 42. It was printed in colors, where that was possible, among which yellow was prominent, and was placed on the illuminated face at the top of filling sta tion pump, as may be seen in Figure 48, page 221 When the ads first appeared in Dayton in May, 1923, the sales of Ethyl Gaso line in the one filling station at which it was then being dis tributed in Dayton rose from 1,796 gallons the week before the ad vertisements appeared to 2,666 gallons the week they were run first (Monthly Report, May 29, 1923). This later increased to 3,500 gal lons per week for -the one station (Monthly Report, July 2, 1923). Mixing Meters or "Ethylizers" Providing an apparatus for metering the Ethyl fluid into the gasoline, as before mentioned, was one of the important activi ties begun in the spring of 1923. Development work in this field continued for more than a year, and the progress of the endeavor can be followed to some degree by the series of photographs includ ed as Figures 43 to 48 following. The first model of these devices, called "ethylizers" and later mixing meters, is shown in Figure 43, page 214. The Ethyl fluid was then supplied to the meter in a 5-gal lon sheet steel container which was inverted in a chicken-feed TC 37010 *T OC-83 ETHYL GAS IW: 'J1 ............. ' GENERAL MOTORS introduces ETHYL GAS jfBetter Fud torMotors Ztmm- kMte|> TM>-*>*'bariM>*te Write teW ttetteriwaritei M Urite^S Wrii|riiltteMMw 211 riowc 42 ETC 37011 -C-Ai <. I 4 i FIGURE 43 or orfirst thc scries *cthylizers" or keans for METERI NO ETHYL FLU10 INTO 6AS0LINC AS IT WAS eeiNS PUMPED INTO THC CUSTOMER'S TANK. ONLY A Few or THIS FIRST UOOCL WERE BUILT ANO THOSE WERE USED IN CINCINNATI ONLY. A ETC 37012 Report OC-83 215 reservoir in the body of the unit. At the top was a gasoline meter and a bucket wheel for putting the fluid into the gasoline at the proper rate as it ran out of the meter into the hose. These first meters were used only in Cincinnati, and they were soon changed to the next model pictured in Figure 44, page 216. This new device was greatly simplified and cheapened over the first model. It consisted of a graduated sight glass placed above the hose coupling at the top, and a reservoir and manually operated pump below by means of which the desired amount of Ethyl fluid was elevated to the sight glass just before delivery of gas oline to the customer. The Ethyl fluid was now contained in a 5liter sheet steel can called an "arayliter." From the sight glass the fluid automatically entered the stream of gasoline as it passed through the hose to the customer's fuel tank. The visible feature was thought to be an advantage from the viewpoint of the customer by enabling him to see that he was getting the proper amount of Ethyl fluid and from the viewpoint of the General Motors Chemical Company by making the customer one of its inspectors. This form of mixing meter was patented (U. S. 1,544,922, Thomas Midgley, Jr., July 7, 1925). One of these devices installed in an actual filling station is shown in Figure 45, page 217. This was the station of the Refiners Oil Company at the comer of Far Hills Avenue and the Cincinnati Pike in Oakwood, suburb of Dayton, and was the second station through which Ethyl Gasoline was sold in Dayton. Figure 46, page 218, is a copy of the inside spread of a leaflet prepared by the General Motors Chemical Company for the Standard Oil Company of ETC 37013 ETC ETC 37015 report oc-a3 218 Hou'Ethyl Red Crown is sold Drive your car to a Standard Oil Company (Indiana) service station. Ask the attendant for Ethyl Red Crown. He will serve you from a gasoline pump through the regular hose. This simple method of supplying Ethyl Red Crown is made-possible by a device called the Ethylizer. Tlu* Ktlnliwr The Ethylizer is a device designed by the General Motors Chemical Company, which automatically mixes the Ethyl Fluid with gasoline to make Ethyl Red Crown. This device, shown in the illustration, is attached to the ordinary gasoline pump. It contains a graduated glass tube, in which the filling station attendant pumps a sufficient quantity of the Ethyl Fluid to mix with the amount of gasoline asked fc; by the customer. This tube is ir. plain sight of the customer, so it makes visible the supply of Ethyl Fluid, - thus offering protection and a guarantee to the purchaser. The proper quantity of Ethyl Fluid is pumped into this glass tube, then the station attendant pumps the regular quantity of gasoline from the gasoline pump which, as it flows through the hose into your car, is automatically mixed with this Ethyl Fluid so that it is finally deposited into the '$0\S tank of your car properly mixed, full-powered Ethly Red Crown Gasoline. In some cases where the sales of Ethyl Red Crown are very large, an entire tank and pump are devoted to its use, and it is therefore put into the owner's car from a regular gasoline pump without an Ethylizer attached. In either case the car owner is fully assured that he is purchasing genuine Ethyl Red Crown. Colorinj' Upon observing the Ethyl Fluid flow into this glass tube, you will notice that it has a wine color. This coloring matter is put into the fluid for your protection so that it may be easily recognizable. Of course, when the very small amount of Ethyl Fluid required to mix with gasoline to make Ethyl Red Crown is so' mixed, the dilution affects this color so that when Ethyl Red Crown flows into the tank this wine color is very much lighter than it appears when the Ethyl Fluid is standing in the glass tube. Inspection The Ethylizing devices that are attached to the gasoline pumps at the service stations are regularly inspected by representatives of the General Motors Chemical Company. These inspections are to see that the Ethyl izer is kept continually in perfect working order. Ethyl Fluid is delivered in special cans to the service stations by the General Motors Chemical Company. FIGURE 46 CENTER SPREAD OF FOLOER PREPARED BY THE GENERAL MOTORS CHEMICAL COMPANY FOR THE FIRST LARGE DISTRIBUTOR OF ETHYL GASOLINE, THE STANDARD OIL COMPANY OF INDIANA, EXPLAINING HOW ETHYL GASOLINE WAS BEING SOLO IN 1923. ETC 37016 F.eport OC-83 219 Indiana. The text explains how Ethyl gasoline was then delivered to the customer by means of the sytem pictured in Figure 44 Soon another change in the ethylizer or mixing meter was made to the device pictured in Figure 47, page 220. A later model of the same meter, designed for production at Delco, is shown in Figure 48, page 221, as it was mounted on the gasoline pump with direct connection to the gasoline hose. In this modification, the Ethyl fluid was contained in a one-liter sheet steel can called a "methyliter" inverted in the top portion of the mixing meter itself. It was then metered into the sight glass in proper amount by turning the crank which is visible in the pictures. There was a counter connected to the crank to serve as a check on the station operator. The steel "methyliter" cans and the method of boxing them for shipment is shown in Figure 49, page 222. One of the troublesome problems met with in connection with the gravity-feed type of mixing meter, such as is pictured in Figures 47 and 48; was leakage or creeping of the Ethyl fluid through the valves and even through an apparently tight joint made by two metal surfaces in contact, in spite of the fact that a gask et was employed. But, as a result of considerable experimentation, it was discovered that a film of the material called "carbalold" not only sealed the valves and joints against leaking of the Ethyl fluid, but also served to lubricate the rotary valve in the meter (Monthly Report, November 1, 1923)* The ethylizers or mixing meters were put into the hands of distributors of Ethyl Gasoline under an arrangement by which they ETC 37017 r.lPOn"- oC-r3 ilO l <Ii F I GU.m - 7 THIkD MODEl. of mixing meter, DEVELOPED IN I 9i3. THIS MOOEL DIO A./AT * I ~rt THE PUMP AND DEPENDED UPON GRAVITY FE-D TrIROJJH A METER OPERATED BY THE CRANK SHOV.N. THE SIGHT GLASS WAS RETAINED ETC 37018 figure 4a MOO IF I CO FORM OF THC THtltO UOOCL OT HIKING METtR, AS DCSItNCO FOR QUANTITY PRODUCTION, SHOMM in place on a gasoline pump. ETC 37019 ~ I GUhL ~~i 3i-_;--a S'EEL CjNTAiKEkS r0r E T H i'L FLUID, CALLED rEAS," SHOV. i NG ho* T h y /.E*E PACKED TCP SHIPMENT, I . IN A CASE. TC 37 020 Report OC-83 223 remained the property of the General Motors Chemical Company. But for each ethylizer received the distributor paid to the Company $30 in the way of a deposit on, or rental for, the use of the ma chine. The problem of blending the Ethyl fluid and packing it in the containers in which it was shipped to the filling stations was another one that had to be met. The first plant for doing this was built in the southwest corner of the room in the labora tory marked "Motor Room" in Figure 16, page 68. The capacity was 160 gallons of Ethyl fluid per day. Elementary precautions in re spect to ventilation and handling to prevent poisoning hazard were incorporated, but these were greatly improved in similar plants built later. This first blending and canning plant was put into service about August 1, 1923, and was operated by R. D. Veils, As illustrations of later developments in the blending and packaging of Ethyl fluid the pictures. Figure 50 and 51, pages 224 and 225, are included. The machine shown in Figure 50 -was de veloped in the laboratory at Dayton as an automatic means of fill ing the methyliter cans. The enclosure in which it was operated for safety reasons is pictured in Figure 51. This plant was lo cated in the north end of the laboratory building at Moraine City. These elaborate precautions were taken to prevent the poisoning haz ard from the handling of Ethyl fluid. Under methods of blending in use before this, several cases of poisoning had occurred among the men who worked at blending the fluid. Some of these proved to be fatal, the men having died under distressing circumstances. It was TC 37021 . *.'`5'swr* . :'v^ ':4'-^ -v^'v - a m iI ETC 37023 Report OC-33 226 at that time, surnner of 1921, that Dr. Robert A. Kehoe of the Uni versity of Cincinnati was retained to try to find a solution for these problems, and he has served in the cause of Ethyl Gasoline ever since. Later on all the blending and packaging activities were moved to the lead plant of the du Pont Company. There developed gradually also the blending of Ethyl fluid with gasoline in bulk, or before it was distributed to the filling station* For use in this method of distribution was de veloped also what was called the "bulk ethylizer," an early model of which is pictured in Figure 52, page 227. For such bulk dis tribution the Ethyl fluid soon began to be shipped in drums, how ever, and some years later still in tank cars. The bulk method of ethylizing gradually displaced the small mixing meter method; and, when in 1926 Ethyl Gasoline came back on the market after its year of withdrawal for the Surgeon General's investigation, as will be related further on, the individual mixing meter method was abandoned altogether* There were made also in 1923 a few strong steel contain ers with screw caps called a "tourist ethylizer." The aim in the marketing of Ethyl Gasoline was to get national distribution just as quickly as possible, in order that the user who might have his engine fitted with high-compression so as to take full advantage of Ethyl could get the product everywhere. But, because this was of course not possible all at once, the idea of the tourist ethyl izer was to take care of the man who had to drive where there was no general distribution of Ethyl. But it was never used. . ETC 37024 V a $ 1y 4 FIGLhE 52 CAriLV 400l OF BULK NIX INC METt-r, USE? FOR PUTTINS ETHYL FLUIO INTO &AS.OL hE IN QUANTITY. I i =# 'rfi-. ETC 3 70 2 5 Report OC-83 228 Proposal to Dye Ethyl Gasoline In May, 1923# Boyd made the suggestion that Ethyl Gasoline be dyed (Record 21, page 13). It was thought that this might have the following advantages, as quoted from the Monthly Report for May, 1923: 1. It will permit estimation of the amount of Ethyl Gas Fluid in the fuel by the very simple method of direct color comparison. 2. The psychological effect on the customer will be good, in that the gasoline will be noticeably dif ferent after it has been passed through the "Ethylizer,* 3. It will improve the stability both of the Ethyl Gas and the Ethyl Gas Fluid against light. This will be especially desirable if Ethyl Gas is al lowed to stand in the light, such as in the usual type of vending pump. 4. A distinctive color will simplify the prevention ef the use of Ethyl Gas as a dry cleaner or wash ing medium. The prevention of the use of Ethyl Gas in this way is very essential, 5. An attractive color may act as a stimulus to sales, especially if it is delivered from visible vending pumps. Some dyes that appeared to be suitable for the purpose were obtained from the du Pont Company; and, after some experimentation, the suggestion was put into effect using the red dye called Sudan IV. No automobile gasoline had yet been dyed at this time, although during the World War fighting grade aviation gasoline had been colored for identification. Only part of the anticipated advantages of dyeing Ethyl gas oline, as enumerated above, worked out however. Although a method for inspecting the gasoline for content of Ethyl fluid by simple color ETc 37026 Report 0C-83 229 observation was developed, it proved to be impractical, and for a reason that was not then anticipated. It was found that the slow decomposition which occurred in the Ethyl fluid of that time grad ually carried the dye out of solution, so that the intensity of color was not permanent enough for the observation of color to be useful as a means of inspection* The Problem of Stability in Storage This brings up the serious problem of decomposition in the Ethyl fluid which was one of the principal items of investi gation during the summer of 1923. It was noted that, with the mix ture of tetraethyl lead and carbon tetrachloride then being used, gas was sometimes generated which built up pressure in sealed con tainers of Ethyl fluid. This was therefore not the same as the decomposition of tetraethyl lead in white light, previously dis cussed, Taking up the investigation of this problem on May 1, 1923, (Record 21, page 6), Boyd sealed a gallon of Ethyl fluid in a metal can fitted with a pressure gage. Nothing appeared to hap pen for some time, possibly because the.generated gas was meanwhile being dissolved by the fluid. Soon however pressure began to build up in the container. It was thought that the gas which produced the pressure came from a decomposition of tetraethyl lead, brought about in turn perhaps by a hydrolysis of carbon tetrachloride. Such decomposition, in the presence of traces of water, could give hydrochloric acid and thus convert tetraethyl lead to lead triethylchloride, with the simultaneous formation of a hydrocarbon gas. At any rate, the pressure in the can soon built up to more than 5 pounds ETC 37027 Report OC-83 230 on the gage. At that point the seal was broken and a tube was at tached to the can in such a way that the generated gas was to have been collected in a 2000-cc graduate serving as a gasometer.. But this arrangement, left for the week end, was destroyed by the vio lent bursting of the container--fortunately at a time when every one was absent from the laboratory--scattering the contents over the room* No such serious difficulties from gassing were experi enced in the field however, possibly because the fluid was being used up too fast. But that the explosion mentioned above was not simply a freak case is shown by a letter from Guido Behn which 0* lee Harrison received and passed on to Ur. Kettering in August, from which the following is quoted? Please tell Kettering for me that the anti knock in addition to being a good remedy for knocks in motors is also very effective as a bomb. The bottle you left with ms has been standing on my desk ever since you were here, and yesterday while I was telephoning the bottle blew up. Pieces of the bottle went in all directions. Fortunately not into my eyes and the liquid flooded my desk and everything on it. You cautioned me against getting the stuff on my hands but I not only got it on iay hands but on my face and for itching it has poison ivy beat a mile. Also a can of the unstable Ethyl fluid of that time, sit- ting in the garage of John J. Raskob, not only burst but also in flamed spontaneously, setting fire to the garage and doing consid erable damage. Again, as reported more than once through the course of this record, an effort was made to find some addition agent that would stabilize the mixture. But, as in the past, this effort did t/" , etc 3?028 Report OC-83 231 not prove to be successful. However, extensive tests of organic chlorine compounds other than carbon tetrachloride, which were made also, showed that some of them did give great improvement in the stability matter (Record 21, page U2). This resulted in Sep tember, 1923> in a change being made in the chlorine compound used for making Ethyl fluid from carbon tetrachloride to trichlorethylene (Monthly Report, October 1, 1923) And fortunately this change, although adding somewhat to the cost of Ethyl fluid, completely solved the gassing and decomposition problem. During the spring and summer of 1923 some further work was done at Dayton on methods of making tetraethyl lead, chiefly in studying catalysts for the process. Also, after the report by Frank Howard of their success in making tetraethyl lead by using ethyl chloride instead of ethyl bromide some work was done in in** vestigating the possibilities of an ethyl chloride process. Sev eral other possible antiknock compounds were tested also, but these are included in the list. Appendix IV, Further Work on Decarbonizers Some further work was done, too, in the effort to pro duce an effective liquid decarbonizing agent. This was done under the belief that "the ability to remove carbon easily is quite essen tial to any program into which high compression engines enter" (Monthly Report, July 2, 1923). Mixtures of alcohol, naphthalene, benzol, and pyridine (also aniline) were found to be fairly effec tive and resulted in the obtaining of a patent, (U. S. 1,736,860, December 30, 1930, Thomas Midgley, Jr,, and Carroll A. Hochwalt). ETC 37029 Report CC-83 232 During the fall of 1923 such carbon remover liquids were given a practical trial by the Chicago Yellow Cab Company, where they were applied with some success to about 200 engines at the Huron Street Garage. These trials were supervised by C. A. Hochwalt. However, the coming of cold weather introduced starting difficulties in some instances (Monthly Reports, November 30 and December 29, 1923). These were overcome to a fairly satisfactory degree, but at the cost of diluting the carbon remover with gasoline and so reducing its effectiveness. Later, when summer came, it was found that the harder coke-like carbon formed then did not yield so readily* to the action of the oorapound as had the softer winter carbon. Due to these difficulties and to the rush of other problems which inter fered with the experiments, the use of the decarbonizer was discon tinued (Monthly Report, July, 1924) at that time. But later on the research on decarbonizer was taken up again in other quarters, and pursued in a more detailed and extensive manner. More About the Research at M.I.T. The work done at M.I.T. during the summer of 1923 and through to the spring of 1924 consisted primarily of the following items: (M.I.T. Reports on the Antiknock Problem): Study of the reactions involved in the manufacture of tetraethyl lead from ethyl bromide by substitution, that is, without the use of reducing agents. Study of the possible catalyzers for the reaction between ethyl halides and sodium-lead. Of the 30 com pounds studied, alkyl cyanides were found to be best, and better than the pyridine which had been in use at du Pont. Study of hydrolysis in the sodium-lead process. etc 37030 Report OC-83 233 Comparative study of the reaction of sodium-lead with ethyl bromide and ethyl chloride. It was not there found possible to get as good yields with ethyl chloride as with ethyl bromide. But it later became known that the secret of the success of Kraus and Callis with ethyl chloride was the use of an alloy containing only 1 part sodium and 9 parts lead. Laboratory investigation of the spark plug and valve problem. Results were in general agreement with those obtained in the engine tests at Dayton. The investigation at M.I.T. during this period was under the supervision of W* G. Whitman and R. T. Haslara, and those who worked on the problems at various times that year were the fol lowing: George Calingaert, J. C. Pope, Alan C. Johnston, and J. Lurie. ETC 37031 Report OC-83 234 CHAPTER XIII CONCLUDING WORK ON EXHAUST VALVE AND SPARK PLUG PROBLEMS By the summer of 1923, some of the problems discussed above having been got out of the way and the use of chlorine com pounds as corrective agents not having solved the spark plug and exhaust valve problems as completely as could be desired, the search for a more perfect corrective agent was actively taken up again (Record 21, pages 8 and 27). By the early fall of 1923 the work on this problem had reached an intensive stage. The twelve one-cylinder engines shown in Figure 1 of Appendix 5, had been in stalled in the room next the Fuel Section office in the Dayton Lab oratory, and a program of tests which lasted about a year and which were run 24 hours a day for much of the time was under way. The typical test on a formula was run for 48 hours, and a new exhaust valve and spark plug were used for each test. In the early stages, condition of the exhaust valve and spark plug was noted simply by visual observation. Later the weight of deposit on the valve was determined by removal and weighing, and later still both the weight and composition of the deposit was determined* It soon became apparent from these tests that bromine was a distinctly superior corrective agent. And so in early November, 1923, Boyd made a trip up to Midland, Michigan, to see the Dow Chem ical Company about possible supplies of bromine. There he talked . with the late Dr* H. H. Dow, president of the company, as well as to L. C. Camp and E. 0. Barstow. They were only mildly interested in the matter and in our request for compounds of bromine, or of ETC 3703 Report OC-83 235 bromine and chlorine combined, which would combine stability from our standpoint with relatively low cost. But they were nevertheless frill ing to sell bromine. Upon returning to Dayton, a sample of Ethyl fluid was sent to Doctor Dow for him to try in his car. On November 21, shortly after this trip to Midland, the following telegram was sent to Mr. Camp of the Dow Chemical Company: How are your facilities for making ethyl bromide by this time? If General Motors Chemical Company should place order for twenty-five thousand pounds at what rate could you make deliveries? In response came a wire saying that they could begin deliveries in about six weeks at the rate of a thousand pounds per day and at a price ef 50 cents per pound. But the situation as it was seen on November 30, 1923, is- outlined in the following, taken from the Monthly Report prepared on that day: The use of bromine compounds in conjunction with lead tetraethyl appears to solve the depositing trouble. Bromine suffers from some serious defects, though, that will make its use in a large way out of the question. The maximum amount of bromine that could be obtained would be utterly inadequate to take care of the situation, because not over 10,000,000 gallons of gasoline could be ethylized per month. The other major trouble with bromine is its prohibitive cost. VTe are therefore concentrating on an effort to influence the behavior of chlorine so that it will give the same effect as bromine. This effort to enhance the corrective effect of chlorine was pursued in an intensive manner for several months following, and involved thousands of hours of testing in the 12 engines shown in Figure 1 of Appendix V. r' ETC 37033 Report OC-83 236 But meanwhile, beginning in the late fall of 1923* prac tical tests of Ethyl Gasoline containing bromine instead of chlorine as a corrective agent were run by the Dayton Power and Light Company in all their cars and trucks. These tests turned out well from the viewpoint of righting the exhaust valve and spark plug difficulties, and they were reported also to have lowered the operating and main tenance cost of their transportation. From this time on for some years, incidentally, the Dayton Power and Light Company served as & kind of proving ground for new developments in Ethyl Gasoline. The fleet there was under the charge of 0. B. Remelin, general superin tendent, and its direct supervisor was at first William Schreiver and later F. 0. (Fred) Lewis. Dr. Wilder D. Bancroft Retained as Consultant Early in 1924 Dr. Wilder D. Bancroft of Cornell University was retained as a consultant for any aid that he might give in solv ing the spark plug and exhaust valve problem. The current effort to enhance the corrective effect of chlorine to make it as effective as bromine was explained to.him, and he thought the endeavor might pos sibly meet with success. He suggested that the effect of copper com pounds be tried as an aid to this end, and also that sulphur be test ed again, both of which were done, but without success. In the case of sulphur, a road test was run also. This showed some protection of exhaust valves, but none in respect to erosion of spark plug elec trodes, A series of engine tests were made meanwhile to determine by chemical means the actual composition of the products formed when ETC 37034 Report OC-83 237 organic halogen-compounds were burned in the engine, both with and without the presence of tetraethyl lead. These tests, which involved careful examination of the exhaust by C. J. Allen, showed that during combustion the halogen compounds were converted in each instance to the corresponding acid, either hydrochloric, or hydrobromic, and that a more perfect union with lead occurred in the case of bromine than in that of chlorine (Monthly Report, April, 1924). This latter was found to be true also in tests conducted in a heated glass tube in the laboratory (Monthly Report, February, 1924). This laboratory and engine work was supplemented also by literature studies, some of which were made by W. H. Charch at the Ohio State University. Dr. Graham Edgar Arrives About the first of June, 1924, Dr. Graham Edgar came to Dayton, Midgley having employed him to take the position of research di rector of the General Motors Chemical Company. He came from the Uni versity of Virginia, where for some years he had been professor of physical chemistry. The General Motors Chemical Company had not yet at that time established a separate laboratory. C; A. Hochwalt had however been transferred to the payroll of the Chemical Company, but was still working in the laboratory of the Fuel Section. Giving his attention to the spark plug and exhaust valve problem, which was being pursued so actively then. Doctor Edgar, using the information obtained in the engine tests described above, computed on theoretical chemical grounds that there was perhaps little chance of chlorine being made as effective as bromine, because lead chloride is too highly dissociated by water vapor which is always ETC 37035 Report '"'C-83 238 present in engines. This finding was checked also by the men at U.I.T. And, because it agreed with the results of the several months of unsuccessful effort to enhance the effect of chlorine, it was decided to discontinue this phase of the endeavor at that point. There were, however, two other elements of importance which entered into this decision. The first of these was that a further analysis of bromine resources had been made, which, as will be reported later on, showed that the possible supply of bromine was much greater than had previously been supposed. The second element was that, on the basis of the superior corrective effect of bromine over chlorine which this long series of tests had so clearly demonstrated, the corrective agent in Ethyl Gaso line had already been changed from the all-chlorine compound, tri chloroethylene, to the one-half bromine compound, ethylene chloro- bronvide (Monthly Report, July, 1924). This was Ethyl fluid 3-E. The further endeavor on the spark plug and- exhaust valve problem may now be related rather briefly by means of quotations from succeeding monthly reports as follows: From the report for August, 1924* "The most outstanding development of the past month has been the decision ... to begin the use.of bro mine compounds for correcting valve trouble as had been recommended. This has meant the termination of research looking to the discovery of other materials to serve this purpose, and the concentration of ef fort on securing thoroughly reliable data on brominechlorine mixtures and on bromine alone. At the be ginning of August the road work was turned over to Dr, Edgar.1' ^ ETC 37036 Report OC--83 239 From the report for September, 1924. We have been 'mopping up' on this investigation by collecting data to fill in the gaps in the chemical and physical results of using bromine and chlorine in various amounts." From the report for October, 1924. .y "The laboratory and single-cylinder engine investi gation of these problems (exhaust valve and spark plug problems) have been completed and the final re port is about ready for submission. The summarized results of the work as quoted from this report are as follows: "It has been found that bromine compounds are the only materials that prevent the depositing of lead compounds on exhaust valves, and at the same time correct the erosion of spark plugs to a satisfac tory degree. Chlorine is fairly effective, but un less used in .high concentration relative to the lead present it does not prevent the deposition of lead oxide on exhaust valves, although it seems to pro tect the spark plug electrodes fairly well." , From the report for November, 1924. "As a result of the findings of this investigation the decision has definitely been made to abandon the use of chlorine and go over entirely to bromine in the Ethyl Gas program." (Further findings about the bromine supply situation to be discussed in the chapter following were involved in this decision al so.) ^ Because of the importance of the work it covers, the summary report on the investigation of the exhaust valve and spark plug prob- lems is included in full as Appendix V. The amount of bromine as ethylene bromide used initially was 1.55 times that theoretically required to convert the lead pres ent to lead bromide. This was reduced to 1,25 equivalents for a time, but was soon changed to 1.5 equivalents of bromine plus a small amount of halowax oil (chlorinated naphthalene). The halowax oil was added after car tests made by the Ethyl Gasoline Corporation during late ETC 37037 Report OC-83 240 1924 and early 1925 had appeared to show that it functioned as an exhaust valve lubricant. Later on, about 1928, an extensive series of further car tests was undertaken by the Ethyl Gasoline Corpora tion. These tests showed that, with the intervening improvements in spark plugs and exhaust valves, it was then possible to reduce the bromine in Ethyl fluid to 1.15 equivalents of the lead present plus a snail amount of halowax oil. Later the bromine was reduced to 1.00 equivalent, still retaining the halowax oil. Some time af terwards the halowax oil was discontinued and the corrective agent was changed to 0.85 equivalents of bromine and 0.30 of chlorine, and later still to Ok75 bromine and 0,4 chlorine. In September, 1933, the corrective agent became 0.70 equivalents of bromine and 0,45 of chlorine. Still more recently, in 1942, the composition of the corrective agent was changed once more to 0.5 equivalents of bromine and 1.0 of chlorine. All of these changes were of course based upon extensive car tests by the Ethyl Gasoline Corporation. The Ethyl fluid used in aviation gasoline is. however, a special mixture containing 1.0 equivalent of bromine as ethylene dibromide for the tetraethyl lead present. ETC Report OC-83 241 CHAPTER XIV THE FINAL SEARCH FOR BROMINE The available supply and the cost of bromine were factors that entered into the decision about whether to use it as a correct ive agent. And, as already mentioned, it was the belief that bro mine was too scarce and therefore fundamentally too costly which delayed for so long the decision to use it as the corrective agent. The story of the first negotiations with the Dow Chemical Company about bromine in the fall of 1923, and the resulting conclusion that not enough bromine could be obtained is given in the preceding chap- ' ter. By June of 1924 it became apparent from the long series of tests conducted meanwhile and already reported that not only was bromine the best corrective agent found, but also that there was ap parently no other material which could take its place* Hence, a further analysis of possible bromine supplies was made, including a literature survey of the bromine resources of the world. The literature survey was based chiefly' on Bulletin 695 of the U. S. Geological Survey, "Data of Geo-chemistry," by F. W. Clarke. The result of this further analysis, as quoted from the Monthly Re port for June, 1924, was this: "Briefly we find that the supplies of bromine are much greater than we had been led to believe. The Dow Chemical Company is willing to agree to supply the Chemical Company with all the bromine needed if they will contract in advance for four years' supply at present prices. Then, although we are informed that for some reason the du Pont people do not con sider it as available, we have computed that there is enough bromine in the water of the Dead Sea to ethylize all the gasoline consumed in the United States (1923 rate of consumption) for over 15,000 years. ", ETC 37039 Report CC-83 242 Some time in July or early August, 1924, Messrs. Kettering and Midgley accompanied by H.GM. Fischer of the Standard Oil Com pany of New Jersey (General Motors and Standard of New Jersey were then in process of joining interests to form the Ethyl Gasoline Cor poration, as related further on) went up to Midland to consult fur ther with the Dow people about the problem of assuring an adequate supply of bromine. They took along from the staff of the Standard Oil Company of New Jersey an experienced oil well driller, thinking that possibly the application of the technique of drilling oil wells to the sinking of brine wells might increase the supply of bromine, or reduce its cost. Out of that conference came the opinion that the only source of bromine in really adequate amounts available in this country would be the water of the ocean. But the Dow people said that-, without first concentrating sea water--a thing which would be far too costly to think of--they could not possibly extract bro mine from it, any more than blood can be got out of a turnip. Why, they said, there is far more bromine in our brine after we get all through processing it for the extraction of bromine than there is in sea water in the first place! As a means of effecting the concentration considered nec essary, Dr. H. H. Dow made the following suggestion. He proposed that a pipe line be built from the Pacific Ocean right up over the mountains and down into one of the deserts on this side, so that sea water pumped over the mountains could evaporate there in the hot sun until the brine got strong enough to be worked for bromine. Since this suggestion did not appear to be at all practical, the meeting broke up with no apparent solution of the bromine problem in view. ^ V ETC 37040 Report OC-83 243 Midgley tells that, while sitting in the smoking compart ment on the train returning from Midland, he said to Fischer, "I have just had one of the best ideas that ever came to me.M This idea as Midgley explained it was that it was not really necessary to get bromine out of sea water as bromine. What was wanted in Ethyl gasoline was not bromine itself but an organic compound of bromine. And he asked whether if sea water were to be treated first with chlorine and then with ethylene the bromine could not be sepa rated and got out as ethylene dibromide. His thought was to build a wall across a bay in the ocean so that it would fill with water when the tide came up. And then at low tide to treat.the water with chlorine and ethylene, run the water out and sponge up the ethylene dibromide. But, when upon returning to Dayton he looked up the solubility of ethylene dibromide in water, it was quite ap parent that far too much would stay in the sea water for such a pro cess to work, even if the compound formed under such conditions would be ethylene dibromide, about which there is some question. But nevertheless in August, 1924, all the men in the Fuel Section and those in the newly formed research laboratory of the Ethyl Gasoline Corporation (established August 1, 1924) were set simultaneously to searching for some means of getting bromine out of sea water as an oil-soluble bromide, T.'e did not even wait to have water shipped in from the ocean to work on, but used instead a synthetic sea water made up in the laboratory from the knowledge that ocean water contains about 0.0065 per cent of bromine, or about 65 parts per million. Doctor Edgar, after making a study of the solubilities of organic compounds of bromine in water, suggested Report OC-83 244 that the bromine might possibly bs removed by causing it to react with phenol. This suggestion of phenol was later changed, on the basis of experiments, to aniline. And trial showed that, when the bromine had first been set free in the sea water by chlorine, the addition of aniline (or aniline sulphate) to the solution made it possible to remove about half the bromine as the compound, tribrooaniline. And so a great many experiments were made to find the proper degree of acidity and the best means of separating the tribromaniline from the sea water. But at the outset the difficulty with this process was that no more than half of the very minute amount of bromine in sea water could be got out in one operation. The reason for this was that, when the aniline and bromine reacted, only half of the bro mine combined with the aniline. The other half reacted with the hydrogen released in the reaction to form hydrobromic acid, which of course remained in the sea water. Because the concentration of bromine in sea water initially was so minute, the amount recovered was thus too small to make the process practical. Then one morning James P. Andrew came into the laboratory with the suggestion that, if, in setting the bromine free with chlor ine, twice the amount of chlorine theoretically required were used, the hydrogen released from aniline when the bromine reacted with it might possibly satisfy itself with the excess chlorine present, and thus leave all the bromine free to combine with the aniline to form the tribromaniline desired. As luck would have it, this idea did work out, and so gave a process by means of which the tiny trace of ETC 37042 Report 0C-S3 245 bromine present in sea water could be got out in high percentage yield, at least in the laboratory. $ The compound, tribromaniline, was however a solid--not a liquid. But engine tests showed it to be just as effective as a corrective agent as were other bromine compounds. Being a solid, though, it would separate at any points where the gasoline evap orated completely, as at small leaks around the carburetor. Nev ertheless, it was concluded that the compound could be made to serve the purpose of a practical corrective agent. The two ideas on which the success of the process mainly hinged were then pat ented, as follows: U.S. 1,662, 305, Graham Edgar, liarch 13, 1928, on the use of aniline as a means of removing bromine. U.S. 1,662,355, James P. Andrew, liarch 13, 1928, on the use of twice the theoretical amount of chlorine. . Du Pont Builds Semi-VTorks Plant to Extract Bromine from Sea Water The next step was to see whether the new process would work on a larger scale. This being rightfully a problem for experienced chemical manufacturers, the aid of the du Pont Company was enlisted in the endeavor.' ?/hen in November, 1924, the new method was first explained to the men at du Pont, they were skep tical about whether it would work. And not until they had found from laboratory trials of their own that the reactions did go as represented did they proceed. They were to build first a semiworks plant, which they constructed on the shore at Ocean City, Ud. This phase of the work was undertaken by du Pont for a fee from the Ethyl Gasoline Corporation of $20,000 to cover administration, ex pense, and necessary experimentation. But, when trouble was ex- ETC 37043 Report OC-83 246 perienced in the semi-works plant with the method of separating the tribromaniline by flotation, which had been successful in the lab oratory, another $20,000 was added to the appropriation. Meanwhile, in the late fall of 1924, Mr. Kettering was in gurope; and, in company with men from the du Pont Company (P. H. Chase), he went to Tunis in northern Africa to inspect there the war-time bromine plant at Ain-es-Serah, then inoperative, which the French interests controlling it proposed to lease or sell to be op erated by du Pont on behalf of the Ethyl Gasoline Corporation, or else to re-open and operate it themselves on a cost-plus basis. But, after a great deal of consideration, conferences, and corres pondence, this proposal came to naught. At about the same time also H.G.M. Fischer of the Standard Oil Company of New Jersey made a trip to Palestine to inspect the Dead Sea. Through the office of Mr. W. 0. Kennington in London, some steps were taken later to try to get a favorable concession to operate the waters of the Dead Sea for bromine. Among the prominent Britishers who figured in these negotiations were Sir Herbert Samuel and Sir Josiah Stamp. But nothing came of it, partly perhaps because the granting of any such concession was strenuously objected to by Sir Alfred Mond, chairman of the British chemical company, Brunner-Mond. Also Dr. E. B. Peck and Ur. Adams of the Standard Oil Com pany of New Jersey were sent to Mexico to inspect the possibilities of getting bromine out of the salt water from oil wells. But it was concluded that the prospects there were not as promising as those in Tunis mentioned above (Annual Report of the Officers, Ethyl Gasoline etc 37044 Report OC--S3 247 Corporation, 1924). One other thing that worked against commitments abroad was a duty of 10 cents per pound on bromine. Accordingly, in the fall of 1924 a contract was made with the Dow Chemical Company to supply ethylene dibromide at the rate of 100,000 pounds monthly for 5 years at a price of 58 cents per pound the first year, and re ducing yearly until a price of 49 cents per pound was reached (An nual Report of Officers, Ethyl Gasoline Corporation, 1924)* The semi-works operation by the du Pont Company at Ocean City on the process of extracting bromine from sea water developed by the two laboratories at Dayton proved to be reasonably success ful. Put it brought up a new set of problems. These were how to keep sand and suspended solids out of the water entering the works, and how to insure a supply of sea water not diluted by surface wa ters or effluent water from the plant. The Good Ship Ethyl To solve these problems Hr. Irenee du Pont suggested that the full-scale plant, for which the directors of the Ethyl Gasoline Corporation appropriated $150,000 in December, 1924, be put not in a building along the shore, but on a ship which could sail out to sea away from the dirt and other troubles of the shore. And that was done. A cargo ship 254 feet- long, one of the many built by the Emergency Fleet Corporation during the World War, was bought from the U. S. Government. It had been built on the Great Lakes and or iginally christened the Lake Harralnia. But it was renamed the Ethyl. end on it the Bethlehem Shipbuilding Corporation installed a fullscale bromine plant designed by du Pont on the basis of the tests ETC 37045 Report OC-83 248 at Ocean City. A photograph of the steamship Ethyl is included as Figure 53, page 249. This ocean-going plant was expected to put 3ea water through the process at the rate of 8,OCX) gallons each minute. From the 480,000 gallons of sea water thus treated each hour the plant was expected to produce about 200 pounds of bromine. Near the end of April, 1925, the good ship Ethyl put to sea to glean brorine out of the water through which she sailed, like a big whale straining her dinner out of the ocean she swims in. She sailed southeast into the Gulf Stream, about 250 miles due east of the Virginia capes, and then southwest along the axis s of the Gulf Stream until she got as far south as the latitude of Wilmington, North Carolina. There the ship turned north again and came finally back up the Delaware River to Wilmington and home. The actual cost of the endeavor turned out to be about half a million dollars. But the ship brought back a cargo of bromine, although not quite as large as it might have been. The reason for the deficiency was not so much that the process did not work out as that the landlubbers who were operating it often got too seasick to work. An account of this endeavor, as carried out by the du Pont Company, is given in a published paper by Dr. Charles M. A. Stine, "Recovery of Bromine from Sea Water," Ind. Eng. Chem,, 21, 434 (May, 1929). But when the steamship Ethyl came home she was forgotten for several months, because just then the Ethyl Gasoline Corpora tion was passing through one of its greatest tribulations, and there was no assurance that there would be any money to pay for ETC 3704 etc 3 ?04 7 Report OC-83 250 further work. The trouble referred to was that arising out of the ooisoning episode previously mentioned, and to be described in some detail later on. When some months afterwards, in early 1926, Ethyl gasoline came back on the market after having been given a clean bill of health by the Surgeon General's investigating committee, the demand for bromine was revived. Now Dr. H. H. Dow, who all along had been kept fully informed of progress in the effort to get bromine out of the sea, had continued to insist that it could not be done, that the job was impossible. The success of the cruise of the steamship Ethyl had therefore been a surprise to him. Perhaps with the fear of losing his profitable bromine business through this joint Ethyl Gasoline-du Pont endeavor. Dr. Dow came forward at once with the offer of bromine at a lower price, and with assurances that he would be able to supply the demand from Michigan wells for some time to come. The uncertainty of the tines was still such that the Ethyl Gasoline Corporation decided to accept Dr. Dow's offer and to let the steamship Ethyl stay at her pier, particularly so since she was now to be paid for through the lower bromine prices which she had helped to win. Dr. Dow Overhauls His Bromine Process But the cruise of the steamship Ethyl had had still another important effect up at Midland. Dr. Dow had called in his chemists and instructed them to find out just how it came that the Dow process would not work on sea water when the General Motors, Ethyl Gasoline, and du Pont people were doing the job so successfully. After a ETC 37048 Report 0C-B3 251 great deal of effort the men at Dow found out that, if only they would control very precisely the pH or the degree of acidity of the brine, they could extract bromine from sea water by their pro cess after all. And thus it developed that in their case the difference between ia-possible and possible was nothing more than a tiny trace of acid. This was a very important discovery, because the Dow process had the great advantage of getting the bromine out, not as a compound of bromine but as bromine itself. Thus it could then be made into the precise compound best suited to put into gasoline, which would of course be a liquid, not a solid. Dr. Dow then wired the Ethyl people asking them to come up to Midland. Wien they got there, he said: "We have it." The outcome was a proposal that the Ethyl Gasoline Corporation and the Dow Chemical Company join forces and use this improved process of Dow's to extract bromine from sea water. The Ethyl Gasoline Corp oration was glad enough to do this because they greatly preferred to have the bromine for Ethyl Gasoline in the liquid compound which could be produced by the Dow process, rather than in the solid com pound, tribromaniline. Before the event recorded in this paragraph, however, consideration had been given by men within the Ethyl Gas oline Corporation to building a small plant to produce tribromaniline from sea water as a supplementary source of bromine (Minutes Ethyl Gasoline Technical Committee, July 18, 1927)* etc 3 704 9 Report OC-83 252 First Bromine Plant at Kure Beach Now, just as had been so with the tribromaniline process, it was decided to build first a small plant to try out this new process of Dow's on a semi-works scale. With the difficulties which the du Pont people had experienced from surface water and suspended dirt in mind, and also with a recollection of the help less crew of seasick chemical workers aboard the steamship Ethyl, a very careful search was made for a suitable shore site. At one stage of the bromine-from-sea-water endeavor-- possibly somewhat earlier than this--Charles A. Thomas, (then with the Ethyl Gasoline Corporation, now with Monsanto Chemical Company) went down along the Carolina coast and collected samples of sea water at several points in the general vicinity of Albemarle Sound. The purpose was to find by analysing the samples at what location the sea water contained the maximum concentration of bromine,. Re turning through Norfolk with his samples, Thomas was arrested by pro hibition enforcement officers because of the suspicious character of his heavy baggage full of bottles. But of course sea water did not smell or taste enough like alcohol for him to be held for long. A suitable site for the bromine plant was finally found at Kure Beach on the Carolina coast in a long, narrow peninsula running south from Wilmington, North Carolina, between the Cape Fear River and the ocean. There clean sea water could be pumped in from the ocean on one side and, after treatment, discharged into the river on the other side. * ETC 37050 Report OC-83 253 The Ethyl-Dow Chemical Company The pilot plant was built in 1931 on the site selected, and was then operated successfully for a period of six months. The results were so encouraging that in July, 1933, in the face of mounting demands for bromine, the Ethyl-Dow Chemical Company was incorporated jointly by the Ethyl Gasoline Corporation and the Dow Chemical Company, and construction of a full-scale plant on the same site was decided upon. This plant was intended to produce about 6 million pounds of bromine a year, or. about 6.5 million pounds of ethylene dibromide. Put in the summer time when the sea water was warmer it was found that the process worked so well that the plant could be operated at a rate corresponding to about 9 mil lion pounds of bromine per year. In 1933, when this plant was built; was just the time when lead began to be put also into regular-price gasolines, as will be mentioned later. The demand for bromine thus generated mounted so fast that the size of the plant soon had to be doubled. Then in 1938 the plant was enlarged again, until it was three times as big as the original, and could be run at a rate of about 40 mil lion pounds of bromine per year. Furthermore, it is understood that bromine was being extracted from sea water there at lower cost than it can be got out of the strong brine up at Midland. A photo graph of the plant is included as Figure 54, page 254. Later still another plant for getting bromine out of the sea-was built cm the coast of the Gulf of Mexico. ETC 37051 :pOr(T OC-33 254 FIGURE 54 Fairchild Aerial Surreys, Inc. THE PLAN1T AT KURE BEACH, NEAR WILMINGTON, NORTH CAROLINA, FOR EXTRACTING BROMINE FROM SEA WATER. WATER IS PUMPEO IN FROM THE OCEAN AT THE UPPER RIGHT, AND, AFTER REMOVAL OF ITS BROMINE, IT IS DISCHARGED INTO THE RIVER THROUGH A FLUME EMPTYING JUST BELOW THE DOCK AT THE LEFT. Efc 3?052 Report OC-83 255 After the first bromine plant had been built down there on the Carolina coast, it was thought that because the operation of army and navy aircraft depends so vitally nowadays on lead-treated gasolines, it might be well to call the attention of the Army auth orities to the location and importance of the plant. They night, it was thought, want to work out some plan of defending it in case of war. Soon came a letter from an important Army official, which said among other things that it was most unfortunate that they had not been advised of this endeavor before the plant was built. If only that had been done, he said, the Army would have recommended that the plant to get bromine out of sea water be located not there be side the sea where sea water could be had, but 200 miles back from the coast. Brief Description of Process for Extracting Bromine fron Sea Water Without going into detail, the process put into operation at the Sthyl-Dow bromine plant was briefly this. Water from the At lantic Ocean was pumped into the plant through a settling basin at the rate of about 100,000 gallons or so per minute. As the column of sea water entered the plant through rubber-lined pipes it was treated automatically with the right amount of sulphuric acid and chlorine gas. This set the bromine free in an extremely dilute solu tion. The bromine was then blown out of the water with counter-cur rent air in tall towers. Next in other towers the bromine was ab sorbed out of the air by passing it up through a spray of soda ash solution. This solution of washing soda was circulated round and round until a liquor strong in bromine had been obtained. Then, ETC 37053 Report OC--83 256 v/hen this strong liquqr was treated with sulphuric acid and blown with steam, it gave up bromine as a red liquid more than 3 times as heavy as water. Next, the separated bromine was reacted with ethylene gas, and so gave ethylene dibromide which is the liquid bromine compound that is put into Ethyl fluid. A technical de scription of the original plant and process by Leroy C. Stewart of the Dow Chemical Company was published in 193k (Ind. Eng. Chem., 26, 361, April, 1934). ETC 37054 Report OC--83 257 CHAPTER XV THE ETHyi, GASOLINE CORPORATION Incidental mention has already been made of the formation of the Ethyl Gasoline Corporation, jointly by General Motors Cor poration and Standard Oil Company of New Jersey, as well as of some of the events which led up to the idea of such a joint enterprise. Early in 192k the Standard Oil Company began to distribute Ethyl Gasoline in Washington and Baltimore under a contract with the Gen eral Motors Chemical Company. And this distribution was later ex tended to other areas. Meanwhile the Standard Oil Company of New Jersey was experimenting further with the Kraus and Callis process of making tetraethyl lead by using ethyl chloride instead of ethyl bromide, as previously mentioned. Events thus shaped themselves so that the two companies which had discussed some such joint endeavor off and on ever since 1921, got together and on August 18, 1924, the Ethyl Gasoline Cor poration (name changed in 1942 to the Ethyl Corporation) was incor porated tinder the laws of the State of Delaware, with an authorized capitalization of 50,000 shares of common stock, par value $100. The Standard Oil Company of New Jersey and General Motors Corpora tion each subscribed iritially to 3,750 shares at par. Later--on October 20, 1924--each of the sponsoring companies subscribed to an additional 2,000 shares of common stock at par, thus making the paidin capital $1,150,000. Report OC-83 258 The agreement between General Motors Corporation and Stand ard Oil Company of New Jersey under which this joint endeavor was undertaken provided among other things for the following: The Ethyl Gasoline Corporation was to be owned one-half by each of the two companies entering into the contract. All the patents on anti knock agents and fuel improvers or methods of making such compounds then held by either, together with any further discoveries of like character made or acquired prior to August 1, 1%0, were to became the property of the Ethyl C-asoline Corporation. Profits of the business were to be divided equally. However, because the dis covery of the antiknock agent in Ethyl Gasoline upon which the business was founded had been made by General Motors Corporation after long search, it was provided that a sum equal to one-fourth the yearly profits resulting from the distribution and sale of Ethyl fluid should first be paid to General Motors Corporation as a royalty. It was provided also that the newly formed Ethyl Gaso line Corporation should take over the physical assets of the Gen eral Motors Chemical Company at their replacement cost. (This fig ure was later set at $362,767.19.) The Board of Directors of the new Corporation was to be composed of an even number of men, onehalf to be elected by the Standard Oil Company of Mew Jersey and one-half by General Motors Corporation. The directors of the Ethyl Gasoline Corporation, as thus elected at the outset, were as follows: ETC 37056 Report OC-83 259 From General Motors From Standard Oil Alfred P. Sloan, Jr. Donaldson Brown John Thomas Smith Charles F. Kettering Thomas Midgley, Jr. W. C. Teagle J. A. Moffett, Jr. E. M. Clark F. A. Howard A. M. Maxwell In December, 192M, John Thomas Smith resigned as director and was replaced by Irenee du Pont. At the first meeting of the Board of Directors on August 28, 192M, the following officers were elected: President 1st Vice President 2nd Vice President and Gen. Mgr. 3rd Vice President and Sales Mgr. Sec*y and Treasurer General Counsel Charles F. Kettering F. A. Howard Thomas Midgley, Jr. A. M. Maxwell' A.E. Mittnacht Chester 0. Swain' As the presidency of the new corporation demanded more time than Mr. Kettering, with all his manifold activities, was able to give it, Earle W. Webb from the legal department of General Motors Corpora tion was soon made president. And he has filled that position with distinction ever since. Vhen the Ethyl Gasoline Corporation was organized there existed a manufacturing contract with the du Pont Comparer for 1,100,000 pounds of tetraethyl lead at $2.00 per pound, one-half of which had already been fulfilled. A new contract was drawn then by. which the balance due on the $2.00 contract was to be delivered at that rate, any further amount manufactured prior to April 15, 1925, was to be delivered at $1.66 a pound, but after April 15 the price was to become $1.17 per pound, (Later on the price was still fur ther reduced, of course.) These reductions were made possible by ETC 37057 Report OC-33 260 the building of a new lead plant and by the adoption at the du Pont Company of the ethyl chloride modification of the sodium-lead pro cess initiated by Kraus and Callis for the Standard Oil Company of New Jersey, as mentioned elsewhere. Manufacture by du Pont under this modified process was begun early in January, 1925. In the early days of making tetraethyl lead, the cost of plant and equip ment were figured on the basis of amortization in one year, f About August 1, 1924, a separate research laboratory was set up for the Ethyl Gasoline Corporation in the northeast corner of the main laboratory building at Moraine City. This laboratory was in charge of Graham Edgar, whose coming to Dayton in June, 1924, as director of research for the General Motors Chemical Company has already been mentioned. Some of the first men added to the staff were Charles A. Thomas, who had been working in the Fuel Section of the General Motors Research Corporation for more than a year, C. A. Hochwalt, Fred Thamann, and B. B. Owen. Without attempting to give an account of the subsequent history of this laboratory, or of its extensive activities, it may be mentioned that at the end of 1925 it was moved to Yonkers, N. Y. Then in November, 1927, the mechani cal department, which Dr. Edgar had established at Yonkers under Earl Bartholomew who came to the job from a teaching position at Harvard University, was moved to Detroit. Again in December, 1932, the chemical department of the research laboratory also was brought to Detroit and was put in charge of Dr. George Calingaert, who, as previously related, had worked on lead problems at M.I.T. ETC 37058 Report OC--83 261 Shortly after the formation of the Ethyl Gasoline Corpora tion, the Ethyl emblem and trade mark was changed from that shown at the top in Figure 42, page 213, to the emblem shown as Figure 55, page 262. Giving advice in respect to this change was Ur. E. S. Rogers, famous trade mark attorney of Chicago. ETC 37059 r;P0RT OC-83 262 FIGURE 55 THE ETHYL EMBLEM AND TRADE MARK AS IT WAS MODIFIED AFTER THE FORMATION OF THE ETHYL GASOLINE CORPORATION. IN THE ACTUAL EMBLEM THE RAYS ARE BLUE IN COLOR, THE TRIANGLE AND THE LET TERS ON THE PENNANT ARE BLACK, AND THE LETTERS ON THE TRIANGLE AND THE BACKGROUND OF THE PENNANT ARE YELLOW. ETC 37060 Report OC--83 263 CHAPTER XVI THE HEALTH HAZARD QUESTION So far the subject of toxicity in respect to Ethyl Gaso line has only been touched upon lightly, such as to relate the con tacts with Drs. Reid Hunt of Harvard and Yandell Henderson of Yale, mentioned on pages 165 and 166, and to refer to the fears of Dr. Sric Krause and Surgeon General Cunning on page 191. At the out set the concern about possible poisoning hazards was confined chief ly to the products exhausted by engines burning lead. The exhaust did not, however, prove to be the source of the poisoning difficul ties actually experienced, for those came from the handling of the tetraethyl lead itself in concentrated fora. But the belief that the hazard, if any, would come from lead compounds blown out in the exhaust explains why the early endeavors related almost altogether to possible hazards arising from exhaust products. In the summer of 1923 tests on the exhaust of engines running on Ethyl gasoline were begun in the laboratory at Dayton* In the first of these a 4-cylinder engine was run at half load and 1000 r.p.m. for over a hundred hours, during which time the exhaust gas was first cooled and then passed through distilled water in an effort to get a measure of the amount of lead in the exhaust. How ever, this test did not prove to be very quantitative; for, in spite of the pains taken to recover all the lead, it was possible to ac count for only about half of it (Monthly Report, August 29, 1923)* TC 37061 Report OC-83 264 A more extensive test was accordingly undertaken, this time to determine how much lead would be deposited as floor dust in the garage of the Research Laboratory when all the cars kept there used Ethyl Gasoline. A request was made that each car using the garage burn Ethyl Gasoline during the period of the test. The company trucks and service cars kept in the garage were run on Ethyl Gasoline too. In addition, a Chevrolet car was placed in the garage, the en gine of which was kept running on Ethyl Gasoline throughout the work ing day. This test was conducted for 30 working days. The garage floor was swept just before the test began. And, although it was not swept again during the entire 30-day period, the amount of lead found in the sweepings collected at the end of the test was so small that a person would have had to absorb each day all the lead from about 4.5 grams of floor dirt in order to be in danger of develop ing lead poisoning according to the tolerance of 6 milligrams per day as given by Dr. J. C. Aub of Harvard Medical School (Report, "Accumulation of Lead in Garages Where Ethyl Gas is Used," Septem ber 30, 1923). The Bureau of Mines Investigations Meanwhile the previously mentioned arrangements were being made under which the U. S. Bureau of Mines conducted a com prehensive investigation of the possible hazards from the exhaust of engines running on Ethyl Gasoline. In these tests, which were begun in the fall of 1923, the Bureau utilized the large chamber that had been employed in the studies they had previously made to determine the ventilation required for the Holland Vehicular Tunnel New York City.. A copy of the agreement signed on October 19. ETC 37062 Report OC-33 265 1923, under which this work was undertaken is included as Figure 56, page 266 (from Bur. Mines report to the General Motors Research Cor poration and the Ethyl Gasoline Corporation, "Experimental Studies on the Effect of Ethyl Gasoline and Its Combustion Products," 1927). The then superintendent of the Pittsburgh Station of the Bureau of Mines, with whom the arrangements were made and under whose supervision the investigation was conducted, was Dri A. C. Fieldner, now chief of the Technological Branch of the Bureau. As before said, it was Doctor Fieldner who arranged for the presenta tion of the paper at the Pittsburgh meeting of the American Chemi cal Society on the basis of which KLdgley was later awarded the Nichols Medal. Here it may be mentioned also that during a visit which he made to the Research Laboratories of General Motors in De cember, 1938, Doctor Fieldner said that he consideredthe work which he did in investigating Ethyl Gasoline as the high spot of his. whole career# In direct charge of the investigation at the Bureau was ff. P. Yant, now director of research of the Mines Safety Appliances Company. The medical aspects of the tests were under the super vision of Dr. R. R. Sayers, who was then chief surgeon of the U.S# Bureau of Mines and also surgeon of the U.S. Public Health Service and who is now Director of the Bureau of Mines. Dr. Sayers was as sisted by Dr. W. J. McConnell, assistant surgeon of the U. S. Public Health Service. Pathological studies were made by B.G.H. Thomas. Other men taking part in the endeavor were G. W. Jones, R. D. Leitch, D. W, Meyers, J. ff, Farren, and L. B. Berger. ETC 37063 REPORT OC-83 COPT OF. AGREEMENT. Between the Deeaetmest or the Ikteeks akb Cekexal Morons Research Coeeolation* Datton, Ohio. 266 WHEREAS, The Department of the Interior, acting through the Bureau of Miner (hereinafter referred to as the Bureau), is conducting investigations on the more efficient utilization of fuels and in determining the amount of air required to ventilate mines and tunnels contaminated with motor exhaust gases, and WHERE.AS. The Genera] Motors Research Corporation (hereinafter referred to as the Corporation), is also interested in the same subjects, and in particular in whether there is any increase in the toxicity of motor exhaust gases due to the addition to the fuel of certain special chemical substances known as "antMtnock* compounds which enable the use of higher compression engines, thus increasing the mileage from a gallon of gasoline and conserving the liquid fuel resources of the country, and desires to cooperate with the Bureau in this research. NOW THEREFORE, it is agreed: (1) That the Bureau and the Corporation will cooperate in planning and di recting an investigation on the toxicity of exhaust gas from motors using tetraethyl lead and certain halogen compounds as anti-knock materials in the fua according to the general plan outlined in appendix A [not included in this report] of this agreement. It is understood that this plan may be modified during the progress of the work as mutually agreed upon. (2) The Bureau will furnish such laboratory facilities and apparatus as are at hand. heat, light, power, technical supervision of chemists, physiologists and physicists, including actual assistance of pathologist. (3) The Corporation shall pay the salary of an assistant chemist to carry on the analytical work incident to this research for a period estimated at six months and shall provide additional assistance as needed and mutually agreed upon by the contracting parties. (4) The Corporation shall pay all expenses incurred in the purchase of supplies, repairs, and special equipment not available at the Bureau or provided by the Corporation. These expenses are to be paid direct by the Corporation on vouchers approved by the Director of the Bureau or his authorized agent; likewise the salary of the assistant chemist shall be paid in a similar manner. (5) The investigation shall be carried on under the direction of the Superim tendent of the Pittsburgh Experiment Station in a manner satisfactory to both parties of the agreement. (6) Publication of the results of this investigation shall be under the control of the Director of the Bureau. All manuscripts, before publication, will be sub mitted to the Corporation for comment and criticism. Due acknowledgment will be made in the publications to the cooperation of the Corporation. No progress reports will be given out for publication before the investigation is completed without mutual consent of both parties of this agreement. Upon the approval of the Secretary of the Interior, this agreement shall remain in force until June 30, 1924. The actual experimental work is rstimated to cover a period of six months. IN WITNESS WHEREOF, the parties hasp hereunto set their hands by their duly authorized officers. WITNESSES: (Signed) I. A. Hurr (Signed) W. F. Whelan BUREAU OF MINES. (Signed) H. Fostei Bam. Dirtetcr. GENERAL MOTORS RESEARCH CORPORATION. Signed) Thomas Midclet, Jb. Signed) T. A. Born. (Signed) C F. Kettbinc, President. DEPARTMENT OF THE INTERIOR. / pproved Oct 19,1921. l.igncd) E. C Finnet, First Assistant Secretary. FIGURE 56 COPY or riRST AGREEMENT WITH THE BUREAU or MINES UNDER WHICH THE BUREAU INVESTI GATED THE QUESTION OF WHETHER THE EX HAUST FROM ENGINES RUNNING ON ETHYL GAS OLINE MIGHT CONSTITUTE A HEALTH HAZARD. ETC 37064 Report OC--83 267 For the General Motors Research Corporation the tests were followed by Boyd and Dr. E. R. Hayhurst. Frequent trips to Pitts burgh were made for this purpose. Dr. Hayhurst was a professor in the Medical College of the Ohio State University and a member of the Ohio State Department of Health concerned with industrial di seases. He was retained on the recommendation of Dr. J. C. Aub of the Harvard Medical School, who himself visited the Bureau and in spected the endeavor on at least one occasion. For these tests a Delco-Light engine, sent to the Bureau from Dayton, and run on Ethyl Gasoline, was arranged to pour all its exhaust into the 1000-cu. ft. chamber, previously mentioned. The plan of the investigation, as quoted from the official report of this phase of the endeavor by the Bureau of Mines (R.I., Serial No. 2661, "Exhaust Gases from Engines Using Ethyl Gasoline," Decem ber, 1924), was as follows: "Various types of animals were exposed for certain periods of each day to a definite concentration of exhaust gas from an engine using ethyl gasoline. These exposures were made to simulate the worst con ditions, as to time of exposure and concentration of gas in the air, to which people could be exposed without being poisoned by the carbon monoxide in the exhaust gases. The tests were continued over a period of 8 months in order to bring out cumulative effects. Animals of several species, sizes, and ages were used to take care of a possible tolerance or susceptibility." Among the animals thus exposed to the exhaust from the en gine running on Ethyl Gasoline were a number of dogs. During the period of the test, five puppies were actually bom in the chamber. These the men dubbed "The Ethyl Gas Hounds," and they went back into the chamber with their mother each day during the remaining period 37065 etc Report OC-83 263 of the test, without harm of any kind. A photograph of these puppies is included as Figure 57, page 269. The man at the* center in the picture is W. P. Yant, who was in direct charge of the tests. At the end of this investigation, during which the most careful and elaborate medical, pathological, and chemical tests were made on the animals exposed to the engine exhaust, the conclu sion reached was as follows (R.I. 2661, December, 1924)s "In summing up the investigation it can be stated that there has been no indication of plumbism 3n any of the animals used, though they were expor-ed for 188 days during a period of approximately 3 months to exhaust gases from ethyl gasoline in concentra tions with respect to lead content that are several times that allowable from the standpoint of the car bon monoxide." As there was no evidence of lead poisoning in any of the animals at the end of the period reported, a second campaign of the same kind was begun in July, 1924,. using now 5 times the commercial concentration of tetraethyl lead in the gasoline. This program was continued until August, 1925, a period of 12 months. It was found that the 5-fold concentration used was close to the maximum permis sible for monkeys, dogs, rabbits and guinea pigs, in that some of the animals began to show lead storage "though not a comparatively large amount," (Experimental Studies on the Effect of Ethyl Gaso line and Its Combustion Products, U. S. Bureau of Mines, 1927, p. 16). After the expiration of the original contract between the General Motors Research Corporation and the Bureau of Mines, a new contract was made with the Bureau by the Ethyl Gasoline Corporation. ETC 37066 PUPPIES BORN IN THE EXPOSURE CHAMBER AT THE BUREAU OF MINES CURING THE TESTS 0( THE QUESTION OF WHETHER THE EXHAJST FROM AN ENGINE RUNNING ON ETHYL GASOLINE CONSTITUTED * HEALTH HAZARD. THESE PUPS WERE 0UB8ED "THE ETHYL GAS HOUNDS," AND THEY STAYED IN the chamber with their MOTrt* each day during the remaining period of the tests, ALTOGETHER WITHOUT harm. etc 37067 Report OC-83 270 This arrangement, which extended from September 15, 1924, to June 30, 1925, called also for the investigation of possible hazards from breathing the vapors of Ethyl Gasoline and from exposing the skin to Ethyl Gasoline under conditions similar to those that might oc cur in its distribution and use. The tests were not confined to Ethyl Gasoline, however, but other motor fuels were included as well, including white (unleaded) gasolines and benzol blends. Those who followed these later tests for the General Motors Chemical Company and the Ethyl Gasoline Corporation were, first. Dr. Graham Edgar, whose first actual endeavor in his position as direct or of research of the General Motors Chemical Company was on June 2, 1924, when on his way to Dayton he stopped in Pittsburgh and attend ed a conference at the Bureau of Mines. Second, was Dr. Robert A. Kehoe, Department of Physiology, University of Cincinnati, who be gan his long and effective service for Ethyl Gasoline during the summer of 1924, the most of which summer he spent in Dayton. Dr, Kehoe, incidentally, came to Dayton to take under observation the men at the Ethyl blending plant and to make studies of the hazards which existed or might exist there, previously mentioned. Others who followed these tests were Dr. 77. Gilman Thompson for the Standard Oil Company of Hew Jersey and Dr. A. K. Smith for the du Pont Company. The gayway Episode It was while these further tests at the Bureau of Mines were in progress that the upsetting poisoning episode at Bayway, mentioned previously, occurred. In August, 1924, a trial on the semiworks scale of the method of manufacturing tetraethyl lead employing ethyl chloride as alkylating agent, instead of the ethyl bromide then TC 37068 Report OC--83 271 used at du Pont, had been begun at 3ayway by the Standard Oil Com pany, the plant having been operated for the account of the Ethyl Gasoline Corporation. This was of course a trial of the Kraus and Call!* process previously mentioned. On Saturday, October 25, 1924, five of the 45 men working the plant in three shifts were taken seri ously ill. This happened in spite of the fact that all had meanwhile been under medical observation. They were taken to the Reconstruc tion Hospital in New York for treatment. The sickness was however a new one which acted not like conventional lead poisoning but more like delerium tremens. The men affected developed various symptoms, including sleeplessness, low blood pressure, subnormal temperature, low pulse rate, loss of appetite, nausea, muscular weakness, headache, dizziness, and distorted dreams. In the worst cases the victims went out of their heads and had to be put into straight jackets. There was front-page publicity in the New York papers and in almost every newspaper of the country. On the morning of October 27, a story in the New York Times was headlined ODD GAS KILLS ONE, MAKES FOUR INSANE. "Four men were under treatment for delirium in Reconstruction Hospit al here yesterday," the story began, "and another was dead from the effects of breathing a gas used to increase th6 efficiency of gaso line in experiments at the research laboratory of the Bayway plant of the Standard Oil Company at Elizabeth, N. J." Some more expressive writer in another paper dubbed the stuff "looney gas." The Health Board of the State of New Jersey requested that the manufacture of tetraethyl lead in that state be discontinued (the du Pont lead plant was at Deepwater, New Jersey), and that the sale ETC 37069 Report OC-83 272 of Ethyl Gasoline be'temporarily discontinued. The Health Boards of Philadelphia and !Jew York City asked discontinuance of sale also. The Gulf Refining Company, one of the distributors of Ethyl Gasoline at that time, temporarily stopped the sale of it altogether. Hidg1ley and A. M. Maxwell were kept busy visiting boards of health and explaining the difference between the nature of the concentrated tetraethyl lead or Ethyl fluid and the very dilute form represented by Ethyl Gasoline, which then had already been on the market for 18 months without ill effects anywhere. Dispensing of Ethyl fluid through the small ethylizers was discontinued at that time, however, and ethylizing was limited to the bulk form. That this was a courageous thing to do may be apparent from the fact that by that time about 17,000 individual ethylizers were in use. The advertisement reproduced as Figure 58, page 273, was prepared and sent to all distributors of Ethyl Gasoline T/ith the re quest that each publish it in his territory at the expense of the Ethyl Gasoline Corporation. The Bureau of Mines very kindly, gave out a memorandum to the press for release on October 31 in which the difference between Ethyl Gasoline and the concentrated fluid was pointed out, the tests which they were then conducting were enumer ated, and the absence of danger from lead in the exhaust which their tests had already demonstrated was reported to the public for the first time. This naturally helped a great deal to clear the air; but the Bureau could not yet at that time report their results on any dangers that there might be from breathing the vapor of Ethyl Gasoline itself, or from getting the gasoline on the skin while hand ling it. --------------- --:--------------- ------------------------- :------------ etc 3?070 REPORT OC-83 ETHYLIZED GASOLINE 273 For one year and nine months ethylized gasoline has been on sale. It is now being distributed through about 20,000 filling stations covering one-third of the territory of the United States. About 200,000,000 gallons have been used by more than 1,000,000 motorists with complete safety and satisfaction. Recently a distressing accident occurred at an experimental plant, where a new process for the manufacture of tetraethyl lead, one of the constituents used in ethylizing gasoline, wasi under development. Tetraethyl lead is a poison, as are many raw materials which enter into the manufacture of harmless compounds. Ethylized gasoline con sists of 1300 parts of ordinary gasoline containing less than one part of tetraethyl lead. This statement is issued to make plain the all-important difference between tetraethyl lead, the raw material, and ethylized gasoline, the commercial product. Ethylized gasoline is more than an improved fuel, giving smooth ness to the motor and eliminating knocks: it is a scientific discovery which, in its ultimate development, will contribute largely to the con servation of the world's supply of gasoline. Exhaustive tests have been conducted which have established the safety of ethylized gasoline when used properly as a motor fuel. These tests have been confirmed by the United States Bureau of Mines, which is making additional studies to determine whether any possible injury can result from continued contact when used for other than motor pur poses. Scientific data based on these studies will be submitted to any health commissioner or other public health official on request. ETHYL GASOLINE CORPORATION 25 BROADWAY NEW YORK CITY FIGURE 58 COPY OF ADVERTISEMENT RUN DURING THE POPULAR HYSTERIA ABOUT THE SUPPOSED DANGERS OF ETHYL GASOLINE, FOLLOWING THE BAY WAY POISONING EPISODE AND THE RESULTING PUBLICITY IN THE NEWSPAPERS. ETC 37071 Report DC-83 m In contrast to the criticise, and adverse propaganda in the popular press, the technical journals almost universally took an im partial or unprejudiced position. Dr. H. S. Howe, editor of Indus trial and Engineering Chemistry, for instance, published in the De cember, 1924, number of that journal a fine editorial on the sub ject (reproduced in Appendix VI). Also Dr. H. C. Parmelee, editor of Chemical and Metallurgical Engineering, tried to help calm the hysteria of the moment about Ethyl Gasoline. But nevertheless the propaganda against the product con tinued, fostered chiefly in the press by the New York World, but also by some labor union publications. This campaign was aided in no small degree by Dr. Yandell Henderson of Yale University, who, when R. E. Wilson had approached him in 1922 about the matter, as related earlier, said that he thought lead-treated gasoline would "constitute an extremely serious health hazard," but offered to in vestigate the subject for a retainer of $2,000 per month. Some idea of the part that Dr. Henderson and the New York World played in the campaign of adverse propaganda against Ethyl Gasoline may be got from the several copies of representative newspaper clippings of the time which are included as Appendix VI. The Surgeon-General's Conference So great was the effect of the events and of the flood of propaganda upon the public and upon boards of health that in Hay, 1925, Surgeon General Cumming felt compelled to call a conference of interested people in Washington to consider what ought to be done. ETC 37072 Re?ort OC--83 275 g3ily in I-Iay the Ethyl Gasoline Corporation had announced that mean-- v/hile t^ie sa-*-e Ethyl gasoline would be discontinued voluntarily until such time as the various investigations then in progress and yet to be made could show whether any hazard to the public was really involved in the sale of the product as an automobile fuel, At the time Ethyl Gasoline v.-as temporarily withdrawn from sale, it had been on the market more than 2 years and 300,000,000 gallons had been sold with no known bad effects. The Surgeon-General's conference met in Washington on May 20, 1925, and was attended by about 75 persons (Appendix VI). "Under the skillful guidance of the Surgeon General, clinical and experimental facts were presented on the industrial and the public health aspects, followed by a free discussion of the whole natter. Fortunately, there was no acrimonious debate, though some of the statements made might better have been left unsaid,w (quoted from editorial, Ind. Eng. Chem., 17, 552, June, 1925). Of the pertinent data presented to the conference, the most important was that from the three sources fostered by the Ethyl Gasoline Corporation itself. First, was that from the Bureau of Mines. Second, was the results of an investigation which had been in progress at Columbia Univer sity under the direction of Dr. Frederick B. Flinn. And, third, was the results of investigation which Dr. Robert A. Kehoe had for some months been conducting at Dayton. A full report of this conference and what was said there are contained in Public Health Bulletin Ko. 158, August, 1925. Among the approximately 75 persons present were many who were antag onistic to the product under consideration, such as the Dr. Yandell ETC 37073 Report OC-83 276 Henderson of Yale, previously spoken of; Dr. Alice Hamilton of Har vard, who had been **jriting and speaking against the product; N. P. Deppe of Deppe Motors Company, who had long been suing General Motors on carburetion systems; John M. Klein and Lee Sonneborn of the American Oil Company, Baltimore, distributors of benzol-con taining gasolines; and a number of labor representatives, univer sity professors, and public health men. Present on behalf of the Ethyl Gasoline Corporation were Messrs. Kettering, Webb, Uidgley,' Maxwell, Edgar, and Kehoe; also Messrs. C. 0. Johns, E. 1. Clark, R. A. Van Eaton, F. A. Howard, and Gilman Thompson of the Standard Oil Company of New Jersey; and Messrs. Irenee du Pont, W. F. Har rington, Charles K. V?eston, and Charles L. Reese of the du Pont Company. It was during an intermission at this conference that Dr. Alice Hamilton, assistant professor of industrial medicine at Har vard Medical School, and a vociferous opponent of putting lead into gasoline, went up to Mr. Kettering and with fire in her eye told him that he was nothing but a murderer. Why, there are thousands of things better than lead to put into gasoline, she said. "I will give you twice your salary," Mr. Kettering of fered, "if you will name just one such material.* "Oh, I wouldn*t work for youl" was her weak and unpro fessional response. The Surgeon General*s conference came to a close with the adoption of this resolution* "It is the sense of this conference that the Surgeon General of the United States Public Health Service appoint a committee of 3even recognized authorities ETC 37074 Report OC-83 277 in clinical medicine, physiology, and industrial hy giene to present to him, if possible by January 1 next, a statement as to the health hazard involved in the retail distribution and general use of tetra ethyl lead gasoline motor fuel, and that this con ference endorses as wise the decision of the cor poration to discontinue temporarily the sale of tetraethyl gasoline." This resolution, which was first introduced by Dr. Haven Emerson of Columbia and Dr. ii. Nicoll, Jr., commissioner of health of the State of New York, was adopted after much debate. As origi nally presented, the last clause was this: "and that until such time distribution of this substance be discontinued," It was only after Dr. Henry F. Vaughan, of Detroit, president of the American Public Health Association, had protested that it was not possible to discontinue the sale of a product already voluntarily discon tinued that the clause was changed to the form in which the reso lution was adopted. Investigation by the Surgeon-Generals Committee of Seven The committee of investigation, thus authorized and later appointed by Surgeon General Curaming, consisted of the following men: William H. Howell, professor of physiology at the Johns Hopkins Schoo*' of Hygiene and Public Health, chairman. A. J. Chesley, executive state health officer of Minnesota. David L. Edsall, dean of Harvard Medical School and chief of the Medical Clinic, Massachusetts General Hospital. Reid Hunt, professor of pharmacology. Harvard Medi cal School. W. S. Leathers, professor of preventive medicine, Vanderbilt University. ETC 37075 ?.eport OC-83 278 Julius Stieglitz, professor of chemistry, University of Chicago* C.E.A. Winslow, professor of public health, Yale Medi cal School. Immediately after the committee had been named, Mr. Webb, on behalf of the Ethyl Gasoline Corporation, tendered personally and in writing to Surgeon-General Gumming "compliments upon the ex cellence of the committee appointed and our full and unreserved co operation with him and his committee throughout their investigation. The Surgeon-General replied that there will probably be many occa sions during the committee's deliberation when it will become neces sary to get certain information and data from us and he would be pleased to communicate to the committee that ive, at all times, would be at their service" (Minutes, Special Meeting Board of Directors, Ethyl Gasoline Corporation, June 16, 1925). The actual conduct of the investigation was put in charge of Dr. J. P. Leake, surgeon of the United States Public Health Ser vice. Dr. Leake organized a corps of workers consisting of the fol lowing: Lawrence Kolb, Louis Schwartz, Gleason C. Lake, Charles Arm strong, and W. T. Harrison, surgeons; Claude W. Mitchell, past as sistant surgeon; William Mansfield Clark, professor of chemistry; Elias Elvove, chemist; C. G. Remsburg, assistant chemist; Conrad Kinyoun, assistant bacteriologist; J. J. Bloomfield, assistant phj^ sical chemist; Wallace Hall, assistant chemist; and William A. Simkins, Junior chemist. This group received assistance also from many others, including surgeons G. V7, McCoy, L. R, Thompson, and R. R, Sayers of the U. S. Public Health Service; Dr. Lawrence T. Fairhall of the Harvard School of Public Health; W. P. Yant of the Bureau of etc 3?0?6 Report OC-83 279 Mines; and Graham Edgar of the Ethyl Gasoline Corporation. Although the general sale of Ethyl Gasoline to the pub lic had been voluntarily discontinued by the Ethyl Gasoline Cor poration on May 5, 1925, this group was enabled to conduct- an in vestigation of the product under conditions of actual usage by virtue of the fact that in southwestern Ohio "a supply of ethyl fluid was still in the hands of certain consumers and would be continued in use" (Report of the Committee of Seven, January 17, 1926), Public Health Bulletin No. 163, page 103). As a matter of fact, Ethyl Gasoline remained on sale continuously at certain sta tions in Ohio and rest Virginia. These were the stations of the Refiners Oil Company and those of Spears and Riddle, distributors of the product since early in 1923. During this investigation as conducted, 252 persons were examined in an elaborate program of particulars. The men were composed of 5 groups, as follows: Group A. A control group, 36 men, drivers of cars out of the municipal garage of the City of Dayton, using no Ethyl Gasoline. Group B. Test group, 77 men, drivers of cars out of the garage of a Dayton public-service corporation (Dayton Power and Light Company) using Ethyl Gasoline exclusively since July, 1923* Group C. Control group, 21 men, workers in garages using no Ethyl Gasoline, and gasoline truckers and filling station men who did not handle Ethyl Gasoline. Group D. Test group, 57 men, workers in garages using Ethyl Gasoline, and gasoline truckers and fill ing station men handling Ethyl Gasoline. Group E. Control group, 61 men, employed in two indus trial plants in which there was 'nown to be serious exposure to lead dust. ' ETC 37077 Report OC-33 280 Each individual was subjected to a careful clinical exanv- ination by four physicians who worked independently and also "blind," that is without knowing the nature of the individual's exposure to lead, if any. In addition smears were made of the subject's blood, for hemoglobin estimation, red-cell count, and count for stippled cells. Also a specimen of each subject's feces was collected and elaborately examined to determine the amount of lead elimination in his case. Reports of the Committee of Seven and the Bureau of tilnes The general conclusions from this investigation by the Committee of Seven were as follows (Public Health Bulletin, No. 163, "The Use of Tetraethyl Lead Gasoline in Its Relation to Publie Health," 1926, page 109): 1. Drivers of cars using ethyl gasoline as a fuel and in which the concentration of tetraethyl lead was not greater than 1 part to 1,300 parts by volume of gas oline shoved no definite signs of lead absorption after exposures approximating two years. 2. Employees of garages engaged in the handling and re pairing of automobiles and employees of automobile service stations may show evidence of lead absorption and storage, as indicated by the lead content of the feces and the appearance of stippled cells in the blood. In garages and stations in which ethyl gaso line was used the amount of apparent absorption and storage was somewhat increased, but the effect was slight in comparison with that shown by workers in other industries where there was a severe lead haz ard (Group E) and for the periods of exposure studied was not sufficient to produce detectable symptoms of lead poisoning. 3. In the regions in which ethyl gasoline has been used to the greatest extent as a motor fuel for a period of between two and three years no definite cases have been discovered of recognizable lead poisoning or other disease resulting from the use of ethyl gasoline. ETc 37078 r Report OC-83 281 On the basis of the results of this elaborate program of test, so expeditiously conducted under the able guidance of Dr. Leake, the Committee of Seven reported to Surgeon-General Cunning on January 17, 1926, as follows (Public Health Bulletin, No. 163* page 110): "Your committee begs to report that in theiropinion there are at present no good grounds for prohibiting the use of ethyl gasoline of the composition speci fied as a motor fuel, provided that its distribution and use are controlled by proper regulations." Meanwhile, in the summer of 1925 the Bureau of Mines had concluded the further work which it had in progress, as already out lined. Doctor Kehoe had also been pursuing his studies in the field.' For the purposes of this history, the work of Dr. Kehoe and the fur ther studies at the Bureau of Mines are sufficiently summarized in the following editorial comment on the just-mentioned report to the Surgeon-General (Ind. Eng. Chem., 18, 112, February, 1926): "The report . . . confirms the excellent piece of work done some time ago by the Bureau of Mines under the direction of Dr. R. R. Sayre (Sayers) and also the re sults reported by Dr. R. A. Kehoe of the University of Cincinnati. The results of these investigations had. previously been severely criticised and it is, there fore, a pleasure to record the confirmation of their work by the present committee," The official report of the Bureau of Mines to the General Motors Research Corporation and the Ethyl Gasoline Corporation was issued in full in 1927 under the title "Experimental Studies on the Effect of Ethyl Gasoline and Its Combustion Products." Incidentally, Dr. Kehoe had, in his early work referred to here, made a new and surprising observation, which was that men in normal occupations not having any abnormal exposure to lead showed considerable elimination t ETC 37079 Report OC--83 282 of lead (Public Health Bulletin, No. 158, page 20), and he later es tablished this by extensive experiments, even to studying men in primitive society. The Surgeon-General^ Regulations "The Regulations Proposed Following the Tetraethyl Lead In-? itigation" were issued promptly by the Surgeon-General. And, under i guidance of Dr. Kehoe and his staff they have ever since been .igiously followed by the Ethyl Gasoline Corporation and its licen- !S. The regulations consisted of four sections, as follows (Public ilth Bulletin, No. 163, 1926)t I. Proposed regulations for the manufacture of tetra ethyl lead and the blending of the latter to make ethyl fluid. II. Proposed regulations for mixing. III. Proposed regulations for distribution of ethyl gasoline.IV. IV. Proposed regulations for automobile garages, repair shops, service stations, and filling stations. The first one of the Proposed Regulations for Mixing nas s: "The maximum content of tetraethyl lead in commercial ethyl gasoline shall be in the proportion of 1:1,260 by volume for commercial tetraethyl lead, or 1:1,300 for Pb (02115)4 C.P," Later, in 1928, there was issued "Changes in the Regulations posed for Tetraethyl Lead Gasoline" (Reprint No; 1260 from the Pub- Health Reports, November 30, 1928). The changes related to the tion dealing with distribution, and gave more details concerning i placing of signs on filling station pumps and on all containers of . etc 37080 Report OC-83 283 Ethyl Gasoline sold to consumers. The sign designated to go in a orominent position bn each filling station pump dispensing Ethyl Gasoline was to bear the following, which as later events proved was to be placed on about three-fourths of all the filling station pumps in the country, either as such or as some modification of it: "Contains Lead (tetraethyl) and is to be used as motor fuel only, not for cleaning or any other use. Avoid spilling" The investigation of the possible lead hazards associated with the distribution and use of gasoline containing tetraethyl lead, similar to that made by Dr. Leake for the Surgeon-Generals committee, was continued afterwards on a larger scale by Doctor Kehoe and his group. During 1927 there were between 400 and 500 persons under ob servation. Reporting on still further observations made in 1929, Doctor Kehoe concluded thus (Kehoe, Thamann, and Cholak, Jour. Ind. Hygiene, 16, 100, Harch, 1934)* Three hundred and one men who had incurred the severest and longest exposure to leaded gasoline and its combus tion products were studied as to their physical fitness and their lead excretion, during the winter months of 1929-30. No clinical evidences of lead absorption or of lead intoxication were found in any individual, and no indication of lead absorption, as a consequence of the exposure, was detected when the subjects were com pared as to their lead excretion with corresponding groups of unexpos'ed persons who had been studied pre viously. ***** In view of the negative evidence obtained in this study of persons whose exposure to leaded gasoline and its combustion products was magnified to a p->int well above that which is possible in the general population, there is no reason to fear the existence of danger to the pub lic health from the distribution and use of leaded gasoline. ETC 37081 Report OC-83 2QU It should be said further that the subject of possible health hazards from leaded gasolines was again fought out in Eng land when Ethyl Gasoline was introduced there in 1928. After vio lent attacks against the product in the press and elsewhere, a De partmental Committee on Ethyl Petrol was appointed by the Minister of Health upon authorization by Parliament. This group of disting uished men studied the reports of all the investigations made on this side; they interviewed Doctor Leake, Surgeon-General Cumming, Doctor Kehoe, Doctor Edgar, and A. II. Maxwell from this side; and they conducted a series of investigations of their own. Number 1 of the conclusions which they reached was this: The results of our experiments agree with the results of the experiments carried out in the United States of America, whether on behalf of the United States Government Committee or of the Ethyl Gasoline Corpora tion, and fully confim the view we expressed in our Interim Report that the findings of the United States Government Committee were justified. (Interim Report of the Departmental Committee on Ethyl Petrol, H. M. Stationery Office, 1928; Final Report of the Departmental Committee on Ethyl Petrol, same, 1930). Etc 3?082 Report OC-83 28$ CHAPTER XVH "ETHYL IS BACK" The report of the Surgeon-General's Committee, as issued in January, 1926, was generally accepted. And arrangements were made by the Ethyl Gasoline Corporation to resume the sale of Ethyl Gasoline at once. This was done in strict cimpliance with the regu lations proposed by the Surgeon-General, but so far as is known no state passed a law to enforce the regulations. Only in the City of New York, where a resolution prohibiting the sale of Ethyl Gasoline had been passed by the City Board of Health in 1924 and which re mained in force until June, 1928, was there restriction on the sale of the product. Expansion of the distribution from that point on was therefore rapid. How rapid it was is indicated by the growing list of distributors contained in Figure 41, page 210. Thus it was almost exactly three years after the.sale of Ethyl gasoline had been begun in February, 1923, and nearly ten years after the beginning of the search for an antiknock agent, that it be gan to recover from its tribulations and to move forward toward the great success it later achieved. By this time the deficit of the Ethyl Gasoline Corporation had mounted up nearly to $3,OCX),000. This did not, of course, include the original development expense. And so Ethyl Gasoline was between three and four million dollars in the red before it got into the black, and much work had yet to be done before any black ink began to appear at the end of its financial statements. But that is a story which will not be followed here. ETC 37083 Report OC-83 1 286 It may however be mentioned that after the coming of the "Q Brand'* in 1933, in which tetraethyl lead was put into regular-price gaso lines, the use of the compound expanded rapidly until about threefourths of all the gasoline sold in the country contains tetraethyl lead. This expansion was aided by the wise and liberal policy of the management of the Ethyl Gasoline Corporation in respect to the prices distributors were charged for the tetraethyl lead. How, as it became possible to do so, the price charged gasoline producers for tetraethyl lead was gradually and voluntari ly lowered is shown below. 1923 to Oct., 1928 -- No gallonage charge, 1 c per. c.c. Oct. 1, 1928 to Aug. 15, 1929 -- C.7c gallonage charge, 0.5c per c.c. Aug. 15, 1929 to Jan. 1, 1930 -- 0,6c gallonage charge, 0.4c per c.c. Jan. 1, 1930 to July 1, 1930 -- 0,6c gallonage charge, 0.35c per c.c. July 1, 1930 to March 1, 1932 -- 0.5c gallonage charge, 0,35c per c.c. March 1, 1932 to July 15, 1933 -- 0.425c gallonage charge, 0,35c per c.c. July 15, 1933 to Jan. 1, 1934 -- 0,2c gallonage charge, 0,35c per c.c. Jan. 1, 1934 to Dec, 1, 1934 -- No gallonage charge, 0,33c per c.c. Dec, 1, 1934 to Nov. 1,. 1935 -- No gallonage charge, 0,30c per c.c, Nov, 1, 1935 to July 1, 1936 -- No gallonage charge, 0.28c per c.c-. July 1, 1936 to July 1, 1939 -- No gallonage charge, 0.26c per c.c. ETC 37084 L< r Report OC-83 ? July 1, 1939 to May 15, 1940 -- No gallonage charge, 0.25c perc.c. May 15, 1940 to April 1, 1941 -- No gallonage charge, 0.23 c per c.c. April 1, 141 to April 1, 1942 -- No gallonage charge, 0,20c per c.c. April 1, 1942 to -- 0.18c per c.c-. -- No gallonage charge, 287 The upward trend of octane number during recent years, particularly after tetraethyl lead was made available for addition to regular-price gasolines around 1933, is shown in Figure 59, page 288. The curves there, which show the averages for the three grades of gasoline are those given by William H. Hubner of the Ethyl Gaso line Corporation (S.A.E. Jour., 4, 409, October, 1940). Tetraethyl lead began to be added to third-grade gasolines about 1938, and the steep rise in average octane number resulting from it is seen on the chart also. Ethyl in Aviation Brief mention should perhaps be made also of the large place which tetraethyl lead has played in aviation. As before re lated, the first purchasers of antiknock agents in any considerable amounts were the aircraft branches of the Army and the Navy, That was back in 1920, Ever since tetraethyl lead has been available it has been used to some degree by military and commercial aircraft. When the Surgeon-General's conference was held in May, 1925, as al ready related, one of those who attended and put in a plea for the continuance of tetraethyl lead as a much needed material was an of ficer of the Bureau of Aeronautics of the Navy Department. 1 ETC 37085 REPORT OC-33 233 FIGURE 59 THE UPWARD TREND IN THE AVERAGE OCTANE NUMBER OF AUTO MOBILE GASOLINE IN THE UNITED STATES SHOWN FOR EACH OF THE THREE GRADES. PARTICULARLY APPARENT IS THE STEEP RISE IN THE REGULAR-GRADE CURVE AFTER 1933 WHEN TETRA ETHYL LEAD BEGAN TO BE ADDED TO SUCH GASOLINES, AND THE SIMILAR RISE IN THE THIRD-GRADE CURVE AFTER 1938 WHEN TETRAEfriVL LEAD BEGAN TO BE PUT INTO LOW-PRICE GASOLINES. ETC 37086 Report OC-83 289 At Wright Field in Dayton, one of those concerned with adapting the airplane engines of the Army to use the higher octane fuels made possible by tetraethyl lead was S. D. (Sam) Heron, who now for some years has been a valued member of the staff of the Ethyl Gasoline Corporation. The high-octane gasolines so necessary in military planes and in commercial aircraft have in large measure been made possible by tetraethyl lead* This is particularly so in respect to the 100-octane gasolines containing considerable amounts of synthetic hydrocarbons, for in such hydrocarbons tetraethyl lead is much more effective as an antiknock agent than it is in conven tional gasolines. The use of Ethyl fluid for boosting octane num ber--by permitting, as it does, the dilution of precious synthetics with large amounts of base gasoline much lower in octane number-- has made it possible to produce a great deal more high-octane avi ation gasoline than would have been possible otherwise. Iron Carbonyl During all these years, the only compound that appeared to threaten in any wise the exclusive place of tetraethyl lead as an antiknock agent was iron carbonyl. When on August 15, 1922, nickel carbonyl was found to be an effective antiknock compound (Record 19, page 130), and when later cobalt carbonyl was found to be effective also it was inferred that iron carbonyl would be an effective anti knock agent as well. The nickel carbonyl had been prepared by W. H. Charch, and he made many efforts to prepare also or to buy some iron carbonyl for test. But, although these efforts of his extended over many months, they were altogether unsuccessful, so far as yielding ETC 37087 Report OC-83 290 any iron carbonyl for test was concerned. This, as later developed, was because iron carbonyl can not be made except under high pressure, suitable apparatus for which had not been at Charch's disposal. On the 18th of November, 1924, Jasper E. Crane, European Manager for the du Pont Company, wrote Mr. Kettering.at his Paris address (Mr. Kettering, as previously related, was at about that time in Tunis investigating the bromine possibilities there). Mr, Crane's letter was to the following effect: A director of the Badische Company of Germany (Badische Anilin und Soda Fabrik) had recently been in Wilmington and had told Mr, Harrington and Mr, Pickard of the du Pont Company about a wonderful new antiknock agent which his company had developed. A cable had been sent to Mr. Crane who had then gone to Cologne, Germany, to see Dr. Carl Bosch of Badische about the matter. Dr. Bosch gave Mr. Crane no very specific information, except that they had such a compound and that they should be willing to dispose of it under favorable terms* After Mr. Kettering got back to Paris, he and Mr. Crane went to Ludwigshafen, Germany, to investigate the matter further. During two days time, November 28 and 29, 1924, they saw Dr. Wil helm Gaus, Dr. L'ueller-Cunradi, and Dr. Carl Bosch. The antiknock effectiveness of the compound was demonstrated to them. The Badische men did not disclose the composition of the compound, but Mr. Ket tering guessed that it was iron carbonyl and told Doctor Bosch so. And this, as it later developed, was the composition of the compound* They had been able to make iron carbonyl easily in connection with the manufacture of ammonia and methyl alcohol by the method of syn thesis under high pressure which was being conducted there. The . Report OC-83 291 compound was, in fact, an unavoidable by-product. Dr. Bosch and his nen reported that cars had been run as much as 10,000 miles on gaso line treated with the product, that the compound could be made for less than 25 cents a pound in any amount needed, and that it required no corrective agent as did tetraethyl lead. The proposal of the Bad- i ische people was that an agreement be made by which the Ethyl Gaso line Corporation would replace the tetraethyl lead in Ethyl gasoline with iron carbonyl and that the resulting savings be divided equally between Badische and Ethyl as profit. The Badische people were very secretive about the material and extremely reluctant to send any of it over for test on this side. But, when they came to realize that no commitments of any kind would be made without such tests, they did send over a quantity of the com pound, and laboratory engine tests of it were begun in the Fuel Sec tion of General Motors Research Corporation in February, 1925 (Month ly Report, February, 1925). It was thus quickly found that, although no noticeable wear of piston rings in the one-cylinder engines reisulted from the iron oxide produced by the burning of the compound, the spark plug was quickly shorted out by the conductive coating of iron oxide deposited on the porcelain between the skirt and the cen ter electrode. So a search was begun at once for a possible correc tive agent, using the same engines and technique as had been success ful in the case of tetraethyl lead. A great many materials were tried, but altogether without success in stopping the shorting of spark plugs. Then in April, 1925* Dr. Mittasch and Dr. Mueller-Cunradi from Badische came to the laboratory. The difficulties found here etc A.*, Report OC-83 1 292 were explained to them. This, they said, was most peculiar, as no spark plug troubles had been experienced during their work in Ger many. But Dr. Kueller-Cunradi could and would remain at the labora tory for a time to find a solution for the problem. The next day he gave us a list of suggested corrective agents to try. As it turned out, most of these had already been tested, and the others when tried did not prove at all effective. Accordingly, Dr. MuellerCunradi soon went on back to Germany, The results of all these tests are covered in a memorandum prepared by James P. Andrew on April 21, 1925, "Results Obtained in Effort to Prevent the Depositing of Iron Oxide in Engines Run on Gasoline Treated with Iron Carbonyl." Dr. Mueller-Cunradi seemed to have had an unflattering opinion of the capabilities of the men on this side. This is per haps illustrated by the following story. When Dr. Uueller-Cunradi met Doctor Edgar, he asked Dr. Edgar when he was in Germany. "I am sorry that I have never been in Germany at all." "You are Doctor Edgar, are you not?" "Oh, yes, I got my doctor's degree at Yale University, in New Haven," 'TJhy," said Dr. Mueller-Cunradi, "I did not know that doc tors degrees were given anywhere except in Germanyl" In the Patent Office our application relating *to nickel car bonyl and other volatile metal carbonyls ran into interference with the Badische application on iron carbonyl. The interference was com posed by agreement betv/een the Ethyl Gascline Corporation and the Badische Anilin und Soda Fabrik which in brief was as follows: First, ETC 37090 Report OC-83 293 since Badische had an earlier date on iron carbonyl for reduction to practice, the patent on iron carbonyl was to go to them, and was later issued as U.S..1,646,011*, M. Mueller-Cunradi and W. Wilke, October 18, 1928. Second, Badische's right to distribute iron carbonyl was however to be limited to Germany, the rights to iron carbonyl for the U. S. England, and Canada going to the Ethyl Gasoline Corpora tion. There was then issued to Midgley the patent, U. S. 1,662,323, March, 1928, claim 4 of which reads broadly as follows: "A motor fuel containing a volatile carbonyl of a metal other than iron.'1 Later on, in 1928, the Research Laboratory of the Ethyl Gas oline Corporation made an extensive series of car tests of iron car bonyl to find out for sure whether the compound could be used in practice. This further investigation was undertaken because of a report from Roy T. Hurley of the Lfoto-lleter Gauge and Equipment Com pany, saying that the addition to iron carbonyl of a small percent age of tetraethyl lead greatly reduced the occurrence of spark plug difficulties experienced with iron carbonyl alone. (This suggestion may not have been an original idea of Mr. Hurley's, however, as there is a British patent, 252,018 issued in 1927 and owned by the Badische Company of Germany, which relates to the same subject.) An extensive program of tests was carried out, the results of which showed that, whatever the effect of adding a percentage of tetraethyl lead may have been, the spark plug troubles were again experienced. Experi enced also in these tests was increased engine wear, which was so large as to render the use of iron carbonyl definitely impractical. TC 37091 Report OC-83 294 These later tests by the Ethyl Gasoline Corporation in cluded also an effort to improve the stability of iron carbonyl to light, the compound being naturally extremely sensitive to decompo sition by light. But this effort did not prove to be more than moderately successful either. And thus, in spite of extensive ef forts to make it so, iron carbonyl has not been found' to be a prac tical antiknock agent. Fuels containing the compound were, how ever, sold in Germany for some years under the name "Motolin," But even there the use of iron carbonyl is understood to have been altogether discontinued some years ago. However, a number of ef forts have recently been made by unauthorized persons to market iron carbonyl as an antiknock agent on this side. Complaints From the beginning of the sale of Ethyl gasoline there was opposition to it on the part of various people, on the ground that it damaged engines, notably by causing exhaust valves to bum out. This opposition came chiefly from service stations, garage mechanics, automobile makers--and also, of course, from competitors of Ethyl, And in the early days of the sale of the product there were grounds for the complaints. The effort to combat this opposition began in the days of the General Motors Chemical Company, before the Ethyl Gasoline Corporation was organized in 1924. Issued then was "General Motors Chemical Company Service Bulletin No. 1 - Valves." The purpose of the folder was "to familiarize users and garage men alike" with the changed appearance of exhaust valves when using Ethyl gasoline and to assure them that they need not worry about it. Later on the Ethyl ETc 37092 Report OC-83 295 Gasoline Corporation prepared at least two booklets, called "primers," for use in coabating these complaints and propaganda---one in 1927* "Information about Ethyl Gasoline"; the other in 1931, "The Inside Story of Ethyl Gasoline." The steel used for exhaust valves in the early days of Ethyl Gasoline was not resistant enough to oxidation to withstand even the effects of burning regular gasoline for very long. But slowly matters in this regard v/ere improved as car makers adopted oxidation-resisting alloys for exhaust valves, such as that known as silichrome No. 1. After some time it became possible to get automobile makers formally to approve the use of Ethyl Gasoline in their cars. Thus in the February, 1927, number of The Cadillac Service Han was this item: ETHYL GASOLINE APPROVED FOR USE IN CADILLAC CARS Frequent inquiries are received by the Service Department regarding the suitability of Ethyl gasoline for Cadillac cars. For the benefit of those who have occasion to answer similar inquiries in the service station, we inform our readers that the Cadillac Motor Car Company approves the use of Ethyl Gasoline in cars manufactured by them. But the opposition to gasolines containing tetraethyl lead continued in many quarters, and in some it. still does persist even to day, although it has long ago ceased to be a factor of any consider able .importance. The fact is that cars run much further on lead-treat ed gasolines nowadays without attention to valves than it used to be ETC 37093 Report OC-83 296 possible to run them on plain gasolines. An example of the continu ing opposition to lead-treated gasolines is the persistent campaign waged against them for some years in the publications of the Con sumers Union. Thus in the July, 1939, number of Consumers Union Re ports was this item: CU must repeat its previous warnings as to the health hazard offered by any leaded gasoline. Although the U. S. Public Health Service has claimed it found no harmful effects from the exhaust fumes given off by engines using lead ed gasolines, in CU's opinion the possibility of such a hazard remains and is, in fact, in creasing with the wider use of leaded fuels. Difficulties in Airplane and How Overcome In aircraft some definite difficulties from the use of leaded gasolines were experienced. These were chiefly the burning of exhaust valves under the very severe conditions of airplane en gine operation, rusting of engines in storage after use, and attack on exhaust systems that resulted in scaling. This scaling--it was believed--caused some planes to be set on fire, by incandescent part icles carried back on wings and fuselages before the days of all-metal planes. Nevertheless, the attitude of the army aviation people*was like that of Hr. F. E. Hoskovics, mentioned earlier, when he wrote about tetraethyl lead before a suitable corrective agent had been found: "As bad as it is I should like to get some more." Just so in the face of the difficulties which existed the aircraft people continued to use lead-treated gasolines. In a paper published in 193^, S. D. (Sam) Heron, then at Wright Field, said this (A.S.U.E. Transactions, Aeronautical Engineering, October-December,1930, page 233.): ETC 37094 I Report OC-83 297 It is the viewpoint of the Materiel Division that doped fuel of some type is here to stay for high-performance military aircraft en gines and that the difficulties attending the use of such fuel can be overcome, as they have been in automobile engines. These difficulties were gradually overcome by various developments, such as better alloys, stellite-faced exhaust valves and seats, and sodium-cooled or salt-cooled exhaust valves. In fact Sam Heron himself had no small part in solving the problems mentioned. Patents. Although some of the patents taken out during the research which culminated in Ethyl Gasoline have been mentioned from time to time in this history, not all have been included. And so a list of the nearly 30 such patents, as assigned to the General Motors Research Corporation, is incorporated as Appendix VII. Because of its im portance, mention should be made also of the first patent issued to Kraus and Callis, in their work for the Standard Oil Company of Hew Jersey, covering the method of making tetraethyl lead by using ethyl chloride as a substitute for the ethyl bromide previously employed, U. S. 1,612,131, December 28, 1926. Conclusion This seems to be the point where The Early History of Ethyl Gasoline ought to end. The story covers a period of about 10 years. That period runs from the time when the investigation of knock and the i. etc 37095 Report OC-83 298 search for a way to cure it began, until--with the end of all the trials endured in answering, to the satisfaction of everyone con cerned, the question about whether the presence of tetraethyl lead in gasoline would poison people or not--the use of Ethyl fluid as an antiknock agent had surmounted its last major hurdle, and the endeavor began to be a success. In view of all the difficulties and uncertainties encountered, and of the years of hard work that had to be done during that time, and in view also of the 3 million dollars in red figures on the book3 at the end of that 10-year period, the title of this story--like that of many another pioneering endeavor --might well have been stated thus: "It's the First Ten Years That Are the Hardest." A fitting conclusion to the story would perhaps be to list some of the concrete effects of the Ethyl development, as enumerated by Thomas Midgley, Jr., in a recent paper of his, "Problem + Research + Capital Progress" (Ind. Eng. Chem., 31> 504, May, 1939): Tetraethyl lead broke down one of the barriers that was blocking the road to automotive progress--the barrier of knock. It has thus added to the power and performance of over fifty million automobiles. It has contributed to the constant improvements in quality and the steadily decreasing price of bil lions of gallons of gasoline annually. It has made possible the present peaks in perform ance of airplanes. It has strengthened our national defense. It has lowered costs in power farming and truck transport. It has caused the construction of millions of dol lars worth of factories, laboratories, transportation. ETC 37096 r Report OC-83 299 and blending facilities, for its manufacture, distri bution and use. It has given temporary and permanent employment to many. It has uncovered fresh sources of mineral -wealth by "mining" the waters of the ocean successfully.1 It has aided oil companies in the conservation of petroleum in their gasoline refining processes. It has paid taxes toward the support of government. It has made a orofit for those corporations that had the courage to go through a long and difficult "shirt losing period" because they believed that antiknock gasoline would eventually succeed. i i ETC 37097 f Report OC-83 300 1 * f 1 r APPENDIX I Extract from Report of Hay 15* 1920, entitled "The liotor Fuel Problem" \ ) \ f \ i{V . t ! j ETC 37098 Report OC-83 AFnENDIX I 301 !>( - </*' ^ f THE MOTOR FUEL PROBLEM The problem is to increase the available supply of fuels suitable for use in motor vehicles and, at the same time, to conserve the fuel resources of the country, in order to insure the present and future usefulness of motor-driven vehicles. Possible means of increasing the supply of liquid motor fuels are: (1) Production of alcohol for motor fuel (2) Production of motor fuels from coal (3) Production of motor fuels from oil shale (4) Making available for use in motor vehicles a larger percentage of petroleum than can be used at present. Alcohol has only two-thirds as much heating value per gallon as has gasoline. Forty-six per cent (462) of all food stuffs pro duced in the United States in 1918 would have been required to yield enough alcohol to take the place of the gasoline produced in 1919. (See Note 1) On the basis that all the bituminous coal mined in 1916 could have been coked in by-product ovens and that seventy-five per cent (752) of the light oil so produced couldhave been made available for use as a motor fuel, theyield would have beeh about twentyfive per cent (252) of the gasoline produced during that year. In 1919, the actual production of material from coal, suitable for motor fuel, was about two per cent (22) of the gasoline produced. (See Note 2) The shale deposits in this country are enormous. But, for refin ing oil shale, large initial investment and construction on a very large scale would be necessary. It would be several years before the industry could come into quantity production, and an increase in available motor fuel must come within the near future if the use of motor-driven vehicles is not to be curtailed. The deposits of oil shale should be considered as a future source of motor fuel but a source which cannot possibly be available for several years. Note 1: Total possible production alcohol, 1918, gals.-----12,820,400,000 Production of gasoline, 1919, gallons--------------------- 3,957*857,097 Ratio heating value of 80,000 b.t.u. per gal. _ 2 alcohol to that of gasolirelSCi 000 b.t.u.per gal. ~ 3 ' Note 2t Data from "Internal Combustion Engine Fuels" by E. W. Dean, etc 3?099 i Report OC-83 ATENDH I < 302 While some motor fuel may be obtained from the sources given imme diately above, petroleum is the cheapest, most abundant, and best source of such fuel. Doctor E. W. Dean, Petroleum Chemist, United States Bureau of Mines, says, "The nation certainly needs to in crease its engine-fuel resources and no step in this direction should be hindered. It should be recognized, however, that pet roleum gasoline is a type of fuel for which present equipment has been designed and for which it is eminently satisfactory." (See Note 3) The best solution of the motor fuel problem is to make available for use in gasoline motors a much larger percentage of the crude oil than the twenty-five which is now used. This may be done by: (a) Cracking the heavy petroleum distillates. (b) Making it possible to burn straight petroleum dis tillates of a much higher end point than it is now possible to run in motors of standard compressions. Cracking is very wasteful from a fuel-conservation standpoint, and it is not profitable unless there is a vri.de margin between the price of fuel oil and that of gasoline. The best means of increasing the available fuel supply and, at the same time; of conserving the nation's fuel resources is to burn larger percentages of the crude oil in motors in the form of straight distillates. Such a prar-dure would both simplify and cheapen refining, but the burning of distillates of high boiling range presents difficulties from knocking at normal compressions, in starting, in atomization and distribution, from crankcase dilu tion, and from carbonization. Work so far conducted in this laboratory has shown that: (1) High boiling petroleum distillates, even up to f\iel oil, may be run in motors of standard compressions without knocking. This result may be obtained in a number of ways, the best of which is to add to the fuel a small percentage of "anti-knock", of which aniline, toluidine, and xylidine are the most practical. (2) Motors can be started on high boiling petroleum distil lates by use of the Good suction burner, or by priming the cylinders with small amounts of volatile fuel. (3) Heavy fuel can be finely atomized by mechanical means, and it can be properly distributed by making use of the Good suction burner. I I Note 2 (continued): " -------- l Jour. S.A.E., February 192C, page 117, and from article in | "Oil and Gas Journal", April 9, 1920, by A. W. Ambrose, U. S. I Bureau of Mines. I Note 3: I Quoted from the first reference given -in Note 2. ETC 37100 ort OC-83 303 APPENDIX II Cost of Fuel P.esearch from July 1, 1917, to February 29, 1920 TC 37101 Report OC-83 AP'EIJDIX II 304 FUEL COSTS FOR PERIOD JULY 1, 1917 to FEBRUARY 29, 1920 JULY 1 to DEC* 31, 1917 Direct Salaries for above period Direct Overhead 198;96$ 113 hours Laboratory work at .811 per hour JANUARY & FEBRUARY 1918 Direct Salaries Direct Supplies Direct Overhead 66,6266$ iaRCH 1918 Direct Salaries Direct Supplies Direct Overhead 48.625$ APRIL 1918 Direct Salaries Direct Supplies Direct Overhead 63*217$ HAY 1918 Direct Salaries Direct Supplies Direct Overhead 63.7396$ JUNE 1918 Direct Salaries Direct Supplies Direct Overhead 50.677 JULY 1918 Direct Salaries Direct Supplies Direct Overhead AUGUST 1918 Direct Salaries Direct Supplies Direct Overhead 60.256$ 1)958*70 3j397.09 430.95 6,286.74 630.00 31.95 419.59 1,081.54 372.50 486.51 181.08 1,040.C", 400.00 114.38 252.88 767.26 466*50 496.84 297.35 1,260.69 322.50 196.19 163.43 682.12 410.00 381.85 206.15 998.00 493.50 528.79 297.36 1,319.65 ETC 37102 Report OC-83 APPENDIX II SEPTEMBER 1918 Direct Salaries Direct Supplies Direct Overhead 56.0706* OCTOBER 1918 Direct Salaries 3onus paid for previous 6 months Direct Supplies Direct Overhead NOVEMBER 1918 Direct Salaries Direct Supplies Direct Overhead 47.4105* DECEMBER 1918 Direct Salaries Direct Supplies Direct Overhead 70.8313* JANUARY 1919 Direct Salaries Direct Supplies Direct Overhead FEBRUARY 1919 Direct Salaries Direct Supplies Direct Overhead MARCH 1919 Direct Salaries Direct Supplies Direct Overhead APRIL 1919 Direct Salaries Direct Supplies Direct Overhead MAY 1919 Direct Salaries Direct Supplies Direct Overhead 305 388.08 734.28 217.60 1,339.96 800.00 152.88 712.24 490.41 2,155.53 565.00 731*29 267.87 1,564.16 571.09 626.70 404.51 1,602.30 506.25 399.82 421.36 1,327.43 372.50 205-.90 463.57 1,041.97 360.26 . 372.09 396.28 1,128.63 680.00 270.96 825.20 1,776.16 360.00 278.18 595.87 1,234.05 ETC 37103 Report OC-63 APPENDIX II 306 JUNE 1919 Direct Salaries Direct Supplies Direct Overhead 405.00 80.34 489.67 975.01 JULY 1919 Direct Salaries Direct Supplies Direct Overhead 845.00 212.53 1.122,60 2 180.13 AUG. 1st to SEPT. 15* 1919 Direct Salaries Direct Supplies 405.00 80.34 485.34 SEPT. 15 TO DEC. 31, 1919 Direct Salaries Direct Supplies Direct Overhead General Overhead 1/250.00 2,204.16 2,071.35 1.765.06 7 290.47 JANUARY & FEBRUARY 1920 (RESEARCH DIV) Direct Salaries Direct Supplies Direct Overhead General Overhead 1,447.50 173.04 2,077.16 553.24 4 250.94 JANUARY & FEBRUARY 1920 (PLANT NO. 3) Direct Salaries Direct Supplies Direct Overhead General Overhead 18.90 13.48 32.87 7.22 72.47 Plus Expense connected with Oil Deal in 7est chargeable against fuel work 11 506.29 Plus Cost on Fuel Pump 4 Trap Job for Fuel Work 1 073.06 TOTAL 54 439.99 SUOART Direct. Salaries Direct Supplies Overhead Bonus paid applicable to job Oil Deal Fuel Pump & Trap Job 14,028,28 9,762.71 17,916.77 152.88 11,506.29 1.073.06 TOTAL 54,439.99 ETC 37104 Report OC-83 APPENDIX III Copy of Letter Vfritten to Charles L. Reese of the DuPont Company by Thomas Midgley, Jr. June 9, 1920 p.eport OC-83 APPENDIX III COPY GENERAL MOTORS RESEARCH CORnORATION DAYTON, OHIO June 9> 1920 308 Yx, Charles L. Reese, du Pont Chemical Co., y.'ilnington, Del. Dear Ur. Reese: File Rv;-126-4 I am in receipt of your favor of June 1st, and have gone over this matter pretty thoroughly with our research men with re gard to the general situation covering aniline. *7e thoroughly ap preciate that, should a requirement for some odd number of millions of gallons of aniline suddenly come into existence, the du Pont Chemical Company, or for that matter the entire chemical industry could not possibly meet this sudden demand. It does not seem, however, that such a tremendous de mand can be created by any of the methods which we consider prac tical for the introduction of aniline as an aid in solving our motor fuel problem. First. Let us consider the rather impossible method of introducing aniline at the refinery as an integral part of our motor fuel. To give relief to our present gasoline situation some 80 million gallons of aniline per year would be necessary. This amount is entirely outside of the limits of possibility for some years to come. Second. Consider the use of aniline as being added to heavier distillates for special use in tractors and possibly some trucks. This program would necessitate not only the addition of aniline to the fuel, but special devices which could only be em bodied in new tractors and trucks; therefore, we could see the use of aniline growing as these cars were manufactured and sold. This total requirement might some day become a million or more gallons of aniline per year, but this demand could not come suddenly. Third. The possible use of aniline by injecting the an iline separately from the fuel, in which the injection is accomplished only at the tine the addition of aniline is necessary, thereby re sulting in the use of about one-tenth the amount of aniline used in the first and second methods. Consequently to handle our present fuel consumption would result in a maximum demand for 8,000,000 gal lons of aniline per year. v.'e realize that this is a rather large quantity of aniline, which could only be produced by the additional investment of capital, but we do not see how we can possibly effect a sudden equipment of all the present automobiles. In fact, prob ably less than 505? of our automobiles need this device; of these 50 ETc 37106 Report OC-83 APPENDIX III 309 some two-fifths are at present operating on gasoline which does not need the addition of aniline in the present equipment; and of the remaining 30 we doubt if more than one-third could be sold in jector equipment, which would bring the total requirement for an iline on this basis to some 800,000 gallons, which we do not be lieve would be difficult for a good sized aniline plant to produce per year. Understand that this demand could not come suddenly, but would have to grow. Fourth. Were the method outlined under No. 3 complete unto itself, it would scarcely be worth the trouble of alleviating the motoring public in this manner, but when the small package dis tribution of aniline and its use by the injector method has been established, it will be possible to place on the market a motor of considerably higher compression than those now in use, and obtain thereby much greater economy of operation. As we are inclined to feel that economy must necessarily be the keynote of motor car de velopment of the future, we believe that such a use of aniline is highly to be desired and therefore encouraged with present equip ment. Answering your letter in detail; The above outlines our view point at this time on the use of aniline as a fuel improver. Our experiments upon the ihjector are progressing satisfactorily. We are fairly certain of the figures above, (i.e., one-tenth of the amount needed when in jecting as is needed when aniline is mixed directly with the fuel), will come very close to the quantity necessary. v.'ith regard to estimating how much aniline may be required for this purpose in the next six months, you will readily see from the plan of I!o. 3, that it would probably be necessary only "to stock dealers with this material at various points. TJhat this amount of aniline would be we do not know. It would depend upon the size of the package, etc., and we would scarcely expect it to exceed a few thousand gallons. With regard to placing aniline on the market, we have not formulated any program whatsoever. "Te must first determine almost our entire fuel campaign in the future, in order to know what is the right thing to do, and the determination of this rests very largely with the demands upon the General Ik)tors Corporation by the public. We have not brought to issue as yet any patents covering the use of aniline as a. knock suppressor. We have, however, in the patent office at the present- time some applications on the use of knock suppressors, among which are claims covering the use of aniline. There are broad claims covering the addition of anti-knock material to the fuel, which cover any anti-knock material which may be so added. ETC 37107 Report OC-83 APPENDIX Hi 310 V7e do not believe these applications would protect .the du Pont Company, as they are confined to the use of aniline and not to its production, and while we believe we could stop other people from using aniline, it would be difficult to specify any particular make of aniline. However, we believe this is a mat ter for our respective patent attorneys to decide, as they are better qualified to give an opinion upon a point of this kind. Regarding the possibility of a better knock suppressor than aniline making its appearance, this is always and must al ways be a potential possibility, but I think we can remove it as a probability. If our theories covering the cause of knocking are correct, then we can at once eliminate the possibility of any compound being a reasonably active suppressor that does not con tain a benzene ring. Therefore aniline is the logical material, ;However, if our theories concerning knocking are incorrect, it is difficult to conceive of an organic compound we have not already tried which could be produced at anything like the cost of aniline. With regard to inorganic knock suppressors, these would not seem very likely to give us trouble, since the necessary physical prop erties of successful anti-knock materials are not found in many in organic compounds. V,Te have found but one, namely iodine, which is entirely too expensive, so that while we readily admit .the possi bility of a knock suppressor being discovered which would be better than aniline, we do not believe it is likely--certainly not within the next year or two. With regard to a search being made of the literature and patent files, that search has been properly conducted and no sug gestions concerning anti-knock materials have ever been discovered. Of course it has been well known for years that the injection of water performed similarly to the way in which our anti-knock mater ials do, but not in the same degree. In so far as we have been able to learn no one else has ever worked on the development of a knock suppressor. As nearly as we can ascertain the motor fuel situation is about as follows: This year will see the maximum production-of petroleum that this country will ever know. The demand for gasoline, how ever, is increasing approximately at the rate of hO% per year. No serious steps have been taken to curtail this demand"and it is recognized by all who are familiar at all with the fuel situation that a serious shortage is probable. The practice in the past has been for the oil companies to raise the end point of gasoline whenever a shortage was impending. At the present time, however, this is impractical, not because motors vould not handle this fuel in a semi-satisfactory manner, but Report OC-83 Appendix III 3U because other petroleum products such as kerosene, gas oil, etc., are likewise in demand and the supply of gasoline could more profitably be increased by cracking the fuel oil out than it could be increased at the expense of the kerosene cut. Therefore it seems reasonable to expect that a shortage of gasoline will de velop within a year from this summer, but that the quality of gas oline will scarcely be altered. However, the gasoline situation is such a shifting kaleidoscope that while this is the outlook at present, it is very difficult to be sure of what the situation may change into in the next few months. There seems to be only one thing fairly definitely established, and that is that the quality of the gasoline will not materially change. It is barely possible that it may change for the better, due to the extensive cracking programs on the part of some of the large oil companies. Trusting this letter contains the information you desire, beg to remain Very truly yours. TU Jr./AN Thomas Midgley, Jr, Asst. Director of Re search. L ETc 37109 Report 0083 312 APPENDIX IV Partial List of the Compounds Testedin the Search for an Antiknock Agent ETc 371,0 ^ Report OC-83 APFENDtX IV 313 f LIST OF MATERIALS TESTED T/HICH SUPPRESS KNOCK Prepared June, 1925 yetalli-0 clement _ _Compound lead Lead triethyl phenyl .......................... Lead hexaethyl? ..................................... Lead triethyl mercaptan .... Lead diethyl di-iodide .... Diplumbic hexaethide .......................... Triethyl lead mono-dichlor acetate Triethyl lead mono-trichlor acetate Triethyl lead mono-raonobromacetate Lead triethyl methyl ..... Lead triethyl propyl ..... Lead triethyl bromide .... Lead diethyl diphenyl ........................ Trixylyl lead . ................................ Lead diphenyl dibromide .... Lead diphenyl di-iodide .... Lead diphenyl dichloride ... Lead diphenyl dimethyl . . . Lead diethyl dichloride . . . Lead xanthate .......................... , Tetra-n-propyl lead ..... Tetrabutyj. lead................................ Tetraphenyi lead . . . . Lead tetraethyl............................... , Tetra-methyl lead . . . . . . Tetra isopropyl lead ..... Aluminum Aluminum ethyl iodide ... Bismuth Trimethyl bismuthine ..... Triphenyl bismuthine . . . . i Titanium Titanium tetrachloride .... Tin Tin diethyl di-iodide .... Tin tetra-iodide . ............................ j. Tin tetra-chloride ...... j Stannic ethide (tin tetraethyl) . r * Selenium Selenium tetra chloride .... Selenium bromide (Se2Br2) . . . Selenium oxychloride .......................... Diphenyl selenide ................................ Dipropyl selenide ................................ Diethyl selenide ................................ Effect on Knock Record & Page Powerful . 19-152 Powerful . 19-157 Powerful . 19-157 Powerful . 19-166 Powerful . 19-166 Antiknock . 19-180 Antiknock 19-183 Antiknock . 19-188 Powerful . 19-190 Powerful . 19-191 Powerful . 19-204 Powerful . 19-206 Powerful . * Charch Antiknock.. Charch Powerful .. C Charch Antiknock . Charch Powerful * Charch Powerful . ' Charch Some suppression Charch Powerful . 19-32 Powerful i 19-110 Powerful . 19,110,207 Powerful . 13-200 Powerful . * 13-207 Powerful . 13-280 light suppression Charch Powerful . * Charch Suppressed * 19-130 Antiknock . 19-208 Antiknock . Charch Antiknock . Charch Antiknock . Charch Suppressed 13-177 Powerful . Charch Antiknock . 21-60 Powerful . 13-25 Powerful . 13-28 Powerful . 13-28 Powerful . 13-28 ETC 37111 Report OC-83 f i Metallic element APPENDIX IV Conoound Effect on Knock 314 Record & Page Iron Iron penta-carbonyl ................................ Powerful Antimony Antimony (metal) . Liver of antimony Slight suppression 8-9 Suppressed . . 8-11 Triphenyl arsine . Triethyl arsine . Suppressed . . 13-173 Suppressed . . 13-174 Diethyl teliuride Dipropyl teliuride Diphenyl teliuride Dimethyl teliuride Power, suppression 13-26 Power.suppression 13-27 Suppressed . . 13-30 Powerful suppres. 20-10 Nickel Nickel xanthate Nickel carbonyl . Some suppression Charch Powerful suppres. 19-130 Potassium Potassium iodide (solid) Lessened . . . 8-10 Cobalt Cobalt xanthate . . . Some suppression. Charch Zinc Zinc xanthate .... Some suppression. Charch Non-Metallic Elements Compound Chlorine Phenyl chloride . . ............................ Amyl chloride ... .. .. Halowax oil (10) ..................................... Iodine Iodine (element) ....................................... Etliyl iodide . ....................................... Potassium iodide (solid) .... Phenyl iodide ........................................ Anyl iodide .................................................. Fluorine Phenyl fluoride ....... Nitrogen Diphenylamine ....................................... Alpha naphthylamine . . . Beta naphthylamine . . . . . Ortho, meta, and para toluidines Liono-methyl aniline . . . . , Dimethyl aniline . . . . . Paratoluidine ....................................... Orthotoluidine . .......................... Acetanilide ........ Eenzanilide ........................................... Alpha naphthylamine .......................... Beta naphthylamine . . . . . Effect on Knock Record & Page Some suppression. 13-131 Very slight sup. 13-132 Suppressed . , -- Suppressed . Suppressed . Suppressed . Suppressed . Suppressed . . . 8-8 . . 4-1 . . 8-8 . . 13-27 . . 13-129 Slight suppressionl3--142 Suppressed . 10-107 Suppressed . 13-U Suppressed . 13-11 Suppressed . Suppressed . Slight suppres 13-10 1100--6666--66'r,, Suppressed . Suppressed . 10-66-6', 10-66-6', Very slight supp. 10-66-6T Very slight supp. 10-66-6: Very slight supp. 10-66-6' Suppressed . . . 10-66-6', ETc 12 Report OC-83 APPENDIX IV 315 Non-Metallic > Elements Compound Nitrogen Phenylene diamine (saturated) Amyl aniline . . . .v . Butyl aniline . . .' . Propyl aniline .......................... Ethyl aniline . . . Ethyl phenylamine . . . . Amyl phenylamine.......................... k Xylidine . . . . . . . i$ Methyl toluidine . . . . I Methyl xylidine . . . Diethyl aniline .... Curaidine ....................................... Allyl amine . . .. Ethyl amine ................................. Azobenzene ...... Azoxybenzene ..... O-tolyl azophenol .... O-tolyl azophenol acetate . Diazoamidebenzene .... Amide azo benzene .... Uono-nethylaniline . . llono-ethylani line .... Toluene uiamine ..... m-Toluicine ................................. b--Map} ithylaoine .... Meta-xyiidine ..... Triethyl -mire .......................... Ethyl benzyl anixine . , . Monoethyl a-naohthylanine . Phenyl a-naphthylamine . . Aniline ......................................... Ortho amino phenol ... Phenyl methyl nitrosaraine . Triethyl amine ..... Diethyl amine .......................... Effect on Record Knock__________& Page Suppressed 9 10-66-67 Suppressed 9 10-95 Suppressed 9 10-115 Suppressed 9 10-108 Suppressed 0 10-104 Suppressed 0 10-108 Suppressed 0 10-110 Suppressed 9 10-110-113 Suppressed 9 10-114 Suppressed 10-116 Suppressed 10-116 Suppressed 10-138 Suppressed 10-267 Suppressed 10-15 Very slight eff. 10-130 Very slight eff. 10-130 Very slight eff. 10-130 Very slight eff. 10-130 Slight effect 10-130 Slight effect 10-130 Suppressed 10-131 Suppressed 0 10-131 Suppressed 10-271 Suppressed 13-10 Suppressed 13-11 Suppressed 13-13 Slight suppression 13-154 Very slight supp. 13-210 Suppressed . . 13-210 Suppressed . . 13-210 . Suppressed . . 8-17 . Some suppression 20-2 . Some suppression . 20-2 . Very slight . . 20-12 . Suppressed , -- Hydrogen and Carbon Hydrogen ............................................. Isoprene (11?!) ...... Toluene (125) ........................ Dimethyl benzene (ortho) (125) Dimethyl benzene (para) (125) Cyclohexane (125) . . . . . Diphenylmethane .............................. Triphenylmethane . . . . . Triphenyl ethyl methane . . . Diphenyl methane .......................... Diphenyl diethyl methane . Suppressed . 1-2 .Slight suppression. 1-about 3* .Slight suppression. 10-68 .Slight suppression. 10-68 .Slight suppression, 10-68 iSlight suppression. 10-68 .Slight suppression. 19-273 Slight suppression. 19-274 .Slight suppression. 19-275 Slight suppression. 19-276 .Slight suppression. 19-286 ETC 37113 I'l Report OC-83 APPENDIX IV 316 Uon-^etallic Elements________________ Compound Effect on Knock Record & Page arbon. Hydro- Alcohols & Hydroxy Compounds gen and Oxygen Llerck's cresol .... Water ....... Ethyl alcohol (5^). . . Eutyl alcohol (6^). Aioyl alcohol .... Phenol .................................. m-Cresol ................................... Xylenol 1;3:4 .... Veratrol ...... Benzyl alcohol (1255) . . Diethyl methyl-carbinol . Hydroxybenzene .... Hydroxybenzene benzoate . o-tolyl azophenol . . . o-tolyl azophenol acetate Steam . . ............................ Anisole ...... Phenol. ....... . Suppressed . . . . Suppressed . . 8-14 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 . Slight suppression 10-67 , Very slight effect 10-130 . Very slight effect 10-130 . Very slight effect 10-130 . Very slight effect 10-130 . Suppressed . . . 10-175 . Slight suppression 20-12 . Some suppression 20-12 Ethers Diphenyl ether . . . . . Some suppression . 13-123 Organic acetates Methyl acetate (1235) -. . . . Slight suppression 10-69 Aryl acetate (1255) . . . . Slight suppression 10-69 Camphor .... . . . . Slight suppression 1-47 Phosphorus Triethyl phosphine ... Slight suppression 13-153 Triphenyl phosphine . . . . Suppressed . . . 13-160 ETC 37114 f Report OC-83 APFENDIX IV 317 LIST OF MATERIALS TESTED FOR ANTI-KNOCK EFFECT AND FOUND TO BE NEUTRAL Metallic element Compound Effect on Knock Record 4 Page Lead Lead tetra-stearate .... f None . . 19-166 Di-ammonium lead hexachloride. No effect Charch Lead diphenyl diacetate . . Not an antiknock Charch Colloidal lead . . . . .. , Not an antiknock Charch Pb2Fe(CN)6N03 ...... No effect Charch Benzaldehyde lead ..... No effect Tharch Lead ferricyanide .......................... No effect Charch Mercury Mercuric xanthate . ... . No effect Charch Calomel (solid). .' . . . None . . 8-8 Mercuric chloride ..... None . . 8-9 Mercurous acetate (solid) . . None . 8-9 Diphenyl mercury ..... No effect f 9 13-27-250 Mercuric chloride ......................... No effect 8-1? Aluminum Aluminum triethyl ..... None . , 19-157 Aluminum stearate ......................... No effect t 21-46 Aluminum sulfate (solution) . e No effect 20-4 Aluminum nitrate (solution) No effect 20--6 Bismuth Triphenyl bismuthine dichloride Little,if any, effect Charch Triphenyl bismuthine dibromide Little,if any, effect Charch Bismuth nitrate (solution). No effect t 20-4 Bismuth chloride (solution) . e No effect 20-4 Tin Tin tetra-bromide . . , .. Almost neutral Charch Tin dioxide . . . . . . . 21-46 Colloidal Sn . ............................ No effect . * 1-about 100 Iron Colloidal iron .................................. :k Charch Ferric sulphocyanate . . .' . No effect . Charch Ferrous dimethylglyoxime . . No suppression Charch Ferric xanthate ............................ No effect . Charch Gold Gold trichloride ..... Charch Zirconium Zirconium tetrachloride . . No effect observed 21-4 Arsenic Arsenic tetraethyl hydroxide . No effect Arsenic tet"aet;:yl iodide . . No effect . * Ammonium arsenite (solid) . None . Arsenioc.s acid ...... Arsenic trioxide (solution) No effect . 21-16 21-17 8-9 8-9 20-4 Platinum H2?tCl6 6H20.................................................................. Flatinum chloride .... 21-18 Charch ETC 37U5 Report 0C-S3 appendix rv 318 Metallic Element Comcound (Cont'd) Flatinura Dicarbonyl chloroplatinite . Effect on Knock Ho effect Record & Pape Chareh Tungsten Tungsten hexachloride . . . No effect Charch Vanadium Vanadium oxide (V2O5) . . Mo effect 21-46 Nickel Thorium Nickel dimethyl plyoxime . 9 Ni(ON)2C6H5NH2NH3 . . . . Hi(CN)2C6H5NH3 ............................ Colloidal Ni ................................ Chloride (ThCl4) . . No effect No suppression IJo suppression No effect 0 9 0 0 No effect 21-57 Charch Charch 1-about IOC 21-91 Germanium Germanium tetra-ethyl . . No effect e 9 21-91 Copper Copper dimethyl glyoxime Colloidal Cu ................................ CUCO3 (solid) ........................... Copper salt of monobutyl phthalate Copper acetate ........................... Copper sulfate (solution) Copper chloride (solution) . No suppression No effect t None . . 9 No effect No effect No effect No effect 9 9 0 Charch 0 1-about 100 8-8 19-46 8-17 20-6 0 20--6 Cobalt Cobalt succinimide . . Cobalt carbonate . . . . Cobalt nitrate (solution) . Cobalt chloride (solution) . No effect 0 0 Charch No effect 0 8-8 No effect 9 20-6 No effect 0 20-6 Sodium Sodium xanthate ... Sodium ber.soate (solid) . 9 Sodium cyanide ......................... Alcoholic, sodium hydroxide. No effect 0 None . . 0 No effect 0 No effect 9 Charch 8-10 10-21 10-92 Zinc Zinc ethyl .................................. No effect 9 9-64 Silver Silver nitrate . . . . Cadmium Colloidal Cd .............................. No effect 0 8-17 No effect p 0 1-about IOC Antimony Antimony methyl .... None . . ** 8-16 Eariura ' Barium nitrate........................... No effect 0 20-4 Cerium Cerous oxalate ............................ Cerium nitrate (solution) No effect 10-198 No effect 20-6 Fluorine Amyl fluoride ........................... No effect 19-196 Hydrogen fluoride . Practically no effect 19-232 Helium Helium ........................................... Dilution effect 21-18 k ETC 37116 f Report OC-33 APPENDIX IV Element (Confd) Argon Argoi Compound Sulphur Benzyl sulphide t * Phosphorus Phosphorus oxychloride rirogen & Oxygen 319 Effect on Record Knock & Page Dilution effect 21-29 No effect . Chareh No effect , 20-10 No effect . 19-178 Not an antiknock 19-291 No effect . e Charch No effect . 21-97 Alcohols and Hydroxy Compounds Alpha and beta naphthols. Glycerol None . . . e No effect . 10-67 No effect . 10-67 No effect . 10-67 No effect , 10-130 Organic acetates Sulphur Suiphanilic acid Diphenyl sulphide Ho report , 1-47 No effect m 10-142 None . . . 8-8 None . . 0-- No effect . 13-146 Very slight. 20-12 No effect . 20-14 Acids Boric i Arsenic Tannic Formic Molybdic acid (solution). Acetic acid ......................... None ... 8-7 None . . . 8-9 None . . 8-9 No effect . 19-33 No effect . 10-129 No effect. . 10-129 No effect . 8-17 No effect . 20-6 No effect . -- aldehydes Propaldehyde Furfuraldehyde ......................................... No effect 10-129 Very little, if any effec" Little effect . In large % inducer pre-ignition. . Little or no effect. In large percentages induces preignition. Silicon Silicon tetraethyl Very slight if any effect 13-198 ETC 37117 Report OC-33 APPENDIX IV 320 Element (Cont*d) Compound Effect on Knock Record & Page Miscellaneous Materials Beechwood creosote .... Terebene ... . Blandol ............................................. Acetone (60%) .............................. Kerosene treated vdth AICI3 . Residue from cracked turpentine Rosin ................................................ Ammonia (very slightly soluble) Vague report 1-about 47 No effect 1-about 50 No effect 1-about 50 Pre-ignition -- No effect Stopped motor -- None . . . 13-25 No apprec. eff. 10-13 "Bachite" (catalytic carbcn) du Pont's "White Oil" . . "Resin C" (Barnett) . . "Resin G" (Barnett) . . Divinylacetylene .... Borax (solution) .... Mo effect No effect No effect No effect No effect No effect . . . . . . 10-198 10-222 13-26 13-26 19-152 20--6 Chlorine Chloroform ...... * No effect t 1-about Chlorinated kerosene , . No effect 1-about Ethyl chloride .... Very slighteffect 1 NaCl (solid) ........................... None . . . 8-8 Calomel (solid) .... None . . . 8-8 Mercuric chloride . None . . 8-9 Monochlor benzene (12%) . No effect. . 10-68 Ortho dichlor benzene . . e No effect. . 10-68 Pinene hydrochloride . . e No effect. . 10-130 Chloral hydrate .... No effect. . 10-194 Stannous chloride . No effect. . 10-198 Mercuric chloride . . . . 8-17 Barium chloride (solution) e No effect. . 20-4 Chloral hydrate .... No effect. .10-194 Bismuth chloride (solution) No effect. . 20-4 Calcium chloride (solution) No effect. . 20--6 Cadmium chloride . . No effect. 20--6 Cobalt chloride (solution) No effect. * 20-6 Copper chloride (solution) No effect. 20--6 Phosphorus oxychloride. . No effect. 20--10 Phenyl chloride (vapor in air inlet) No effect. . 20-14 Bromine Ethyl bromide . . . . . Choked engine .4-7 Ethylene bromide .... (,Tendency to stop engine" 4-8 Ethylene bromide . . . . Power reduced - Potassium bromide (solid) . Mono brora benzene (12%; . , Para dibrora benzene . . . * f Dimethyl dibrom benzene . . Ethyl bromide ..................................................... None . . No effect . No effect . No effect , No effect . . 8-10 . 10-68 . 10-68 . 10-68 . 10-21 Bromine (5% in kerosene) . 4 No effect . . 8-17 Iodine Cyanogen iodide No effect . . 10-21 ETC 37118 Report OC-83 APPENDIX IV 321 Element (Cont d) Compound Effect on Knock Nitrogen Nitrobenzene ...... No effect . Benzidine . , ............................ None . . . Orthonitrophenol.. . . . . No noticeable effect Sulphanilic acid............................ None . , . Pyridine ......................................... None . Methyl cyanide ............................ None . , Benzonitrile .................................. None . . Benzidine . . ............................ No suppression. 9 Piperidine......................................... Beta-anino-anthraquinone , . . No effect. 9 No effect. Cyanogen iodide ............................ Quinoline .................................. , Acetonitrile .................................. No effect. e No effect. e No effect. Acetamide .................................. ....... Propaldehydecyanhydrin. . . No effect. e No effect. Nitrobenzene ...... Little if any effect Triphenyl amine ...................................................... No effect. Anthranilic acid...................................................... Phenyl hydrazine. .... No effect. No effect. e . Furfuramide ................................................................... No effect. Nitrates & Nitrites Ort honitrophenol............................ No noticeable effect Cobalt nitrate (solution). , No effect . Hydrogen k Carbon Naphthalene ...... Phenanthrene ................................... Diphenyl ... ...................................................... Phenyl toluene ..... Ethyl benzene (1255). . . Pinene ............................................................................................. No effect. No effect. No effect. No effect. No effect. No effect. 9 Potassium Potassium bichromate (solid) Potassium chromate (solid). . Potassium ferrocyanide (solid. Potassium nitrate (solid) . . ` Potassium carbonate (solid) Potassium bromide (solid) . . None None . None . None . None . None . Record k Page 1-47 -- 20-2 10-A8 10-78 10-66-67 10-138 10-222 10-21 10-24 10-48 10-129 10-129 13-3 13-156 20-2 20-2 20-12 20-2 20-6 10-68 10-68 10-68 10-68 10-68 10-130 8-10 8-10 8-10 8-10 8-10 8-10 ETC 37119 r Report OC--83 APPENDIX IV 322 LIST OF MATERIALS TESTED VTTICH INDUCE KNOCK Compound Effect on Knock Record & Page 19 152 Mercury diethyl ......... Knock inducer 288,290 Uranyl chloride ....................................................... Knock inducer 19,297 Antimony triethyl oxide. ............................ . Knock inducer 21-4 Antimony tetraethyl hydroxide .... Knock inducer 21-15 Boron trichloride ......................................... . Slight inducer Charch Allyl isothicyanate. . . ............................ Slight inducer Charch Phosphorus trisulphide......................................... Inducer Charch Nitrogen sulphide K^Sj,......................................... Powerful indue.Charch Sulphur oxychloride................................................... Increased . 13-25 Diethyl sulphide ............................................ Increased . . 13-144 Phosphorus Phosphorus trisulphide .................................. Inducer . . . Charch nitrogen Ammonia . . ............................................................ Slight inducer 19-224 Diazobenzeneimide ..................................... , . Inducer Charcn Orthonitrotoluene...................................................Increased . --<- Ethyl nitrate . ....... . Induced ... -- Propyl nitrite ..... Induced . , . 13-49 Chlorine Carbon tetrachloride ............................................ Increased . . 8-3 Sulphur oxychloride...............................................Increased . . 13-25 Chlorine (gas in air inlet) ... . Increased . . 20-12 Carbon tetrachloride (vapor in air inlet) Increased . . 20-12 Chloroform (vapor in air inlet) . . . Increased . ; 20-12 Bromine Nitrates & Nitrites Phenyl bromide ......................................................... Increased . Ethyl bromide.................................. Increased . . Amyl Eromide .............................................................. Increased . . Bromine (vapor in air inlet) .... Increased 1 Orthonitrotoluene ......................................... . Increased . . Ethyl nitrate................................Induced ... Propyl nitrite. .....................................................Induced ... 13-126 13-128 13-128 20-14 -- -- 13-49 Carbon. Hy Ethers drogen & Oxy' - Diethyl ether* .......... Increased . gen Organic acetates CH3COCH2COOC2H5 (12?) ................................... . Increased . . 13-148 10-69 Copper Copper resinate ......... Increased . . 8-4 ETC 37120 Report OC-83 323 APPENDIX V SUL2ARY REPORT THE INVESTIGATION OF THE SPARK PLUG CORROSION AND EX HAUST VALVE DEPOSIT PROBLEM >c 3 7j Report OC-83 Appendix V 324 REPORT ON CORRECTION OF SPARK PLUG EROSION AND VALVE DEPOSITING TROUBLES INCIDENT TO TREATING GASOLINE WITH _______________________ _________ LEAD COMPOUNDS___ gy T. A. Boyd, J. P. Andrew, and C. J. Allen, October 25, 1924, T'-JF PROBLEM TO BE SOLVED r y/hen an alkyl lead compound is burned in a gasoline engine, the lead goes mainly to PbO. In the finely divided state in which it is formed PbO frits at 700C., and its melting point has been variously given as 776, 879, 808 and 906C. Thus two problems are intro duced in the internal combustion engine. 1. An erosion of the spark plug electrodes, which are made of a nickel containing alloy, and a gradual softening of the porcelain, which forms the electrical insulation of most spark plugs. 2. A deposition of solid lead compounds, mostly PbO, on the faces and stem of the exhaust valves. The effect of this, of course, is to hold the valve a small distance off its seat permitting a leakage to occur, thus cutting down the power of the engine, and in time injuring the valve seat. It was to find some means of preventing depositing on valves and erosion of spark plugs that this investigation was conducted. THE RESULTS OBTAINED It has been found that bromine compounds are the only materials that prevent the depositing of lead compounds on exhaust valves, and at the same time correct the erosion of spark plugs to a satisfactory degree. Chlorine is fairly effective, but unless used in high concen tration relative to the lead present it does not prevent the deposition of }ead oxide on exhaust valves although it seems to protect the spark ETC 37127 Report OC-33 APPENDIX V 325 plug electrodes fairly well. Fluorine and iodine are effective also* but not so good as bromine. Sulphur, too, shows some reactivity with . lead in the engine, but in its ultimate effect it exerts very little protection either to exhaust valves or to spark plugs. Of all other materials tested, of which there were many, as may be seen from the list giver, on the last few pages of this Appendix, none was found that exerted an appreciable protective action; BRIEF ACCOUNT OF THE METHODS USED IH THE INVESTIGATION At the outset in the study of this problem there seemed to be two possible ways of solving it. These were: (a) To introduce some material into the combustion reaction that would cause the formation of a lead compound of very high fusion point, so as to prevent its sticking to the exhaust valve or fluxing away the spark plug electrodes, (b) To introduce some material into the reaction to cause the formation of a lead compound of sufficient volatility to vaporize from the hot exhaust valve and to correct the spark plug erosion at the sane time. In either case, of course, the compound must have sufficient reactivity with lead in the form in which it exists in the combustion reaction to form the suitable compound. The actual investigation was begun in June, 1922, by running single cylinder engines on gasoline treated with the tetraethyl lead plus dif ferent amounts of other materials added as possible corrective agents. The engines were run for a given period, the lengths of which varied at different times during the investigation from 8 to 48 hours, on each mixture. At the close of each run the exhaust valve and spark plug were ETC 37123 Report OC-33 APPENDIX 7 326 removed and examined. During the early stages of the work the obser vations were largely qualitative in character, but as the investigation progressed a more quantitative examination was made, particularly of the exhaust valves. The weight of material deposited on the exhaust valve was determined for each mixture, and the thickness of the de posit on the seat of the exhaust valve was measured! Finally, after it had been found that chlorine and bromine were the only materials that offered any possibility of commercial application, careful deter minations were made of the weights and chemical composition of material deposited when various combinations of chlorine and bromine were used. Air cooled engines were employed throughout the laboratory investi gation. Up until October 19, 1923, the runs were all made on the en gines in the regular dynamometer room of the laboratory. After this date all of the single cylinder engine tests were made on the twelve engines located in room five of the Fuel Section and shown on a later page, in Figure 1 of this Appendix. These are 600-watt copper cooled Delco-Light engines, standard, except for the fact that each engine is equipped with a 3/4" adjustable Schebler carburetor. The tests on these engines were run 24 hours a day, and for the most part the period of each run was 48 hours. A new spark plug and a new exhaust valve were used in every test. The runs were usually made in duplicate, and fre quent tests were run on straight gasoline and on gasoline treated with tetraethyl lead alone to serve as a basis of comparison. During the course of this investigation a great many road tests were run also. These were conducted by the Research Garage. No report will be made of this work herein, other than to say that in general the results obtained on the road checked those secured in the laboratory to ETC 37124 Report OC-33 APPENDIX V 327 a reasonable degree. The most valuable information was obtained by the methods outlined above. But the study was conducted in the laboratory in a number of other ways also, the principal investigations having been as follows: 1. Study of the combustion of various mixtures of tetraethyl lead and other compounds by means of blow torch flames impinging on steel plates. This investigation did not yield results of value, chiefly on account of the inability to make a blow torch operate steadily on gasoline containing lead tetraethyl. The lead compound decomposed in the hot nozzle where the gasoline was vaporized, thus gradually stopping it up and changing the character of the flame. This investigation was pursued to a greater extent at Ifass. Inst, of Tech, than here, but even there the results obtained did not add anything to the data ob tained in the laboratory engine tests, and in some cases they did not agree with the results obtained in practice. Z Study of the combustion of gasoline treated with tetraethyl lead and various halides in a steel bomb, using oxygen as the combustion medium. The data collected consisted of the com position of the products of combustion, both in the. gas and as a solid deposit in the bomb. On account of inability to prevent excessive corrosion of the bomb by the halogen acid and water formed in the combustion, with consequent diffi culties of analysis, this work did not yield anything of par ticular value over and above that gained from the engines, and hence it will not be reported further herein. Report OC-83 APPENDIX V 328 3* Quantitative examination of the products formed by burning lead tetraethyl and organic halides in an engine. This work, (covered in detail in a-previous report), yielded the following facts as its most valuable information. (a) When any one of several organic chlorides, and even molecular chlorine itself, is admitted to the engine in amounts up to 5% of the fuel the product exhausted by the engine contains no free chlorine, but only HCl. (b) When organic bromides are burned in the engine as in (a) there is no free bromine in the exhaust. (c) When small amounts of molecular bromine are admitted to the engine with the inlet air, none of it appears in the exhaust as free bromine. But when the amount is increased to some larger, although not quantita tively determined ratio, bromine does appear in the engine exhaust as such* (d) VJhen the fuel contains both lead tetraethyl and an organic halide the amount of hydrogen halide formed indicates that the lead is converted into lead halide roughly in accordance tvith the following table: Amt. of Organic Halide Present in Relation to the Lead as PbX2 Percentage of the Lead Present Converted to the Halide V/ith Chlorine With Bromine1 1 theory 1.5 theories 2 theories 55 55 75 60 90 etc 37126 Report OC-83 APPENDIX V 329 PRESENTATION AND DISCUSSION OF RESISTS OF ENGINE TESTS Efforts to solve the problem along the first of the lines, (a), as per page 325, did not prove successful. The highest fusing lead salt whose formation seemed possible was lead sulphate, which fuses at 10Q0C. (Although FbS fuses at a higher temperature 1035, it is apparently oxidized to PbSO^ on the valve.) In motor tests using sulphur compounds it was found that heavy deposits of lead sulfate were formed on exhaust valves, but that sulfur compounds were not sufficiently reactive with lead to protect the spark plug electrodes. Research along the second line, (b), as per page 325, has shown that the halogens are the only elements that give lead compounds of sufficient volatility to vaporize from exhaust valves, and that have at the same time the necessary degree of reactivity with lead to pro tect spark plugs. Vapor pressure data on lead chloride and lead bro mide are shown graphically in Figure 2 of this Appendix. The differ ence in volatility between the chloride and the bromide does not have much significance in this case, though, because as will be seen later PbCl2 is sufficiently volatile to be removed from exhaust valves al most completely. It was found further that bromine is the only one of the halides that is sufficiently reactive with lead to prevent to a satisfactory degree the formation of the undesirable lead oxide. This may be seen from the figures in the following tabulation: Fuel Mixture Weight of Deposit on Exhaust Valve in Grams After 48 hours Continuous Running on Gasoline Plus 6 c.c. pbEtk Per Gallon Straight lead in gasoline 3.0 Lead plus fluorine (2 theories) in gasoline 2.15 Lead plus chlorine (2 theories) in gasoline 0.fi5 ETC 37127 J Report OC-83 APPENDIX V 330 Fuel fixture (Confd) Weight of Deposit, etc. (Cont'd) Lead plus chlorobromide (1.6 theories) in gasoline 0.45 Lead plus iodine (2 theories) in gasoline 0.25 Lead plus bromine (1.5 theories) in gasoline 0.10 Straight gasoline 0.10 A great deal of work was done during the course of the investiga tion in an effort to catalyze the action of chlorine in some way so as to make it as reactive as bromine. Upon hypothetical grounds it seemed that this should have been possible (see previous reports). It was found, however, that no noticeable effect was produced by any of the large number of materials that were tried, and which are listed later on in this Appendix. The results of the systematic and careful examination of the de posits from exhaust valves from engines run on various mixtures of chlorine, of chlorobromide, and of bromine with lead tetraethyl in gasoline are shown graphically on the later pages, Figures 3 to 7 in clusive. Each point on the curves represents the average of the deposit from at least six engines, and many of them give the average of 12 engines. Each engine was run 48 hours continuously on 6 c.c. of lead tetraethyl per gallon, (twice the amount used in practice), and the halide as indicated on the abscissa scale in theories of amount required for PbX2 The horizontal dotted lines at the bottoms of Figures 3 to 6 inclusive indicate the average total weight of deposit scraped from the exhaust valves that were run on straight gasoline as fuel. Ethyl Fluid 3-E, which was run in various concentrations as per Figure 7, was composed of three parts tetraethyl lead and two ETC 37128 Report OC-83 APrENDIX V 331 parts ethylene chlorobronide (1*6 theories) by volume. VTith this brief explanation the charts on later pages of this Appendix are self-explan atory. Figures 8 and 9 of this Appendix are photographs giving some idea of the appearance of exhaust valves and spark plugs after 48 hours con tinuous running on - (a) Straight gasoline. (b) Gasoline plus 6 c.c. PbEt^ alone per gallon. (c) Gasoline plus 6 c.c. PbEt/, per gallon plus 2 theories chlorine. (d) Gasoline plus 6 c.c. PbEtz. per gallon plus 1.5 theories bromine. Note that the center electrode of one of the spark plugs run with gas oline plus 6 c.c. tetraethyl lead alone per gallon is entirely gone, and the porcelain is covered with a thick brown glass. The electrodes of the other spark plug run with lead alone are in bad shape also. On the other hand it may be seen that all the other spark plugs are still in good shape. Although, the pictures are necessarily small, the char acteristic differences in the conditions of the exhaust valve with the various mixtures may easily be seen. ETC 37129 APPENCIX V >>' i FIG. I , AP?E.'tf)IX V BATTERY OF 12 ONE-CYLINDER, AIR-COOLED, DELCO-LIGHT ENGINES USED IN THE LONG SEARCH FOR Al AGENT TO CORRECT THE SPARK-P-JG EROSION ANO EXHAUST-VALVE DEPOSIT TROUBLES EXPERIENCED WITH TETRAETHYL LEAD 3Y ITSELF. ETC 37130 FIG. 2 APPENDIX V PLOT OF THE RELATIVE VAPOR I RESSURFS OF LEAD BROMIDE AND LEAD CHLORIDE, SHOWING THAT THE BROMIDE VAPOR I~ES MORE READILY THAN THE CHLORIOE. ETC 37131 i ;-o;" oc-33 APPENDIX V PLOT OF THE EFFECTIVENESS OF A COMPOUN3 CONTAINING CHORINE ALONE FOR RLDUCIKG DEPOSITS OF LEAD ON EXHAUST VALVES. AL THOUGH WEIGHT OF DEPOSIT FALLS RAPIDLY WITH INCREASING AMOUNT OF TRICHLOROETHYLENE, IT IS NOT ALL REWOVEO EVEN WHEN CHLORINE IS PRESENT IN TWICE THE CONCENTRATION NEEDED THEORETICALLY TO FORM LEAD CHLORIDE- ETC 31132 gpOKT OC-33 APPENDIX V 335 FIG. 4. APPENDIX V PLOT OF THE EFFECTIVENESS OF A COMPOUND CONTAINING HALF CHLOR INE AND HALF BROMINE FOR REDUCIN'.- DEPOSITS OF LEAD ON EXHAUST VALVES. COMPARISON. WITH FIGURE 3 SHOWS THAT REPLACING HALF THE CHLORINE IN THE CORRECTIVE AGENT WITH BROMINE IMPROVED ITS EFFECTIVENESS. ETC 37133 r rE;PORT OC-83 APPENDIX V -. H --r-- = I \ VV \\ V: * : "T \ \ \a T" \v --\ | : w\ \ `v i \\ l V\ grWwL*vvwm r )>s /k m SBUXx rtdi rm 1 ft} "q-| v r l. ft | ! --`r-t5 bp i 'i ; Zx&ft ~ Ay, woo? mq// T --iI__ i ; i : III : :i - 1 : l- j i !I ; : --^ AW i i ;! L: 1 j : ' 1 I j j i . 1I - : \ JI : ! !I i: i f /B ii : j f. ' i 1 i \ i * j j 4i ._v_. ---- 1--i ---- -- ----r-- ---- -Vh- --;-- \y *\ : j ! 1 ': V \\ \v ----- :i \\ i1 J -- ~-"I iy\ j_ i i ' .....-.. i . ......... --H~ ----- "" --- -- --: - - ' .. -- -- - --L- --j-- --- -- --;-- -- 7 .Yn c 1 ^> -- J ---i-- i t . ---- 1 1- # -; 1 | \V --! - sAj __ ii__ I. --i--- :--i j j i iJ i --T~ : 7.. : j. 1 :. i i' !- i i 1 . i. . OYr*il . JJD 7^737 T : 'T8 1":: - -i :> SOJu -- ; j i ' -j- A * t A\ i i -i J- ---- r-- !: ,'i i i.: Tteava offlty/mr cf/-Jfra/ff/dr i/j&/ 1 MM ^m * FIG. 5, APPENDIX V PLOT OF THE LFFECI IVLJESS OF A CORRECTIVE AGENT CONTAINING BRO MINE ALONE FOR REDUCING DEPOSITS OF LEAD ON EXHAUST VALVES. COMPARISON V.'ITh -"IGURES 3 ANO 4 SHOAS THAT COMPLETE SUBSTITUTION OF BROMINE FOR CHLORINE IN THE CORRECTIVE AGENT IMPROVED EFFECT IVENESS STILL FURTHER. ETC 37134 hLPOKT OC-83 APPENDIX V 337 FIG. 6, APPENDIX V DIRECT COMPARISON OF DEGREES OF EFFECTIVENESS OF CORRECTIVE AGENTS CONTAINING CHLORINE ALONE, HALF CHLORINE AND HALF BRO MINE, AND BROMINE ALONE. ETC 37135 ] REPORT 0C-S3 APPENDIX V ^33 FIG. 7, APPENDIX V CHART SHOEING, FOR ETHV|_ FLJIO 3-E, HOW WEIGHT OF DEPOSIT ON THE EXHAUST VALVE INCREASED WITH NUMBER OF CtfS OF ETHYL FLUID PEK GALLON OF GASOLINE. ETHYL FLUID 3-E CONTAINED BY VOLUME 3 PARTS TETRAETHYL LEAD AND 2 PARTS ETHYLENE CHLOROBROMIOE. L ETC 37136 ^EPXT OC-33 appendix V nHH ya JwtewfftENT Progress iaffmetotf SparkPlugfranco aadtiataeiDrpostt Gcubies.. Sample sparkph^t rodoAnutiaHer/fmtsingt cylinderagbaaikrrunning contmuoady at 1400rpm. tbr48hoursoa tWious furls. 33^ FIG. 3, APPENDIX V CONDITIONS OF EXHAUST VALVES AND SPARK PLUGS AFTER 48 HOURS CONTINUOUS RUNNING ON FUELS OF THE FOUR DIFFERENT COMPOSITIONS GIVEN ON THE CAROS AT THE BOTTOM. ETC 37137 J; l 4 ` I l . * w . ^Jr; x-n- il >? i?3?iS5'* 2t^Cu- -iYiJSJoV -git jsvr^.^ 7%$7C '& ?iqp i; ^2>ivj i7ll: *7. r *) O^DirX? i. r 'V='-z .-U'-JXtfiUH . ' J - ^5?; `J- .tr>yii ^<7_*'TJ'.i ?rz> * -Jj C-JTil tVy"*?T ^Ti ttis-^y: i;T; -<Y^' jjapaa ,'!/* *? *?' rp i^ry?1 <^*- * -T*^ i ^i^i ^m> V- rt);J i "Q i> * <V'' K-j r<^=K- ;lvTi>>iIi.' ' iii. 'i?V 5Vvv;1} 0 ^i'5iK*-5y :!X4*>?0*^35^! iij . . i) * Jki; r.-Vi) iTiuVkfflTt p i:`-}'s?hsis^m ^ >"tT/cw.?)'-e r ? K.nrty Tn .''Ao- i 'iKii^V'- ; '5v?iD3D 7u >! D-I*] i ; v7"J- - 'iVA; -S532) x $>49s^jas&a? ^242^W5>?Dii :Ji.l323& SiiSS>i'i ?isjii)5Ii ~T'- tvtpt.-. nVkvi^o^^L>~ysi,t^v " uferr;jt>XY ~rJrC)lyvyi'. ^arr^y^T) ETC 37139 TT: < v>Ti *J i . *' fc * C'j * -' *iV^V-V :l?li,!i 4 -i Uv7- 3?lj>:-X5 ., 2r-i^iVV.V- . SLil^p t -'*** 4 ' v* '* ` `J: -*-- n-1!~* i t'tj;' ^: T ti- 11?. - : . jL!i^rDllivl2GiL>?> ;; .. ml** v --vT3XSS) $ ^*'*53 y ^ sisi ijE; i>ymyfc1 "ii ->?& 0 >?)(> J :) as ) ''?.;<L.i:'ijQ>: frjg^ty .31 3i)105Lli*tt` !>j>=S*i> u ''5a^|SJl>3 iiSi* ]?> iSkifcS*!! ? S&H33-4' IB& ' :) 37 V1>> v ~iili ti* ;v5 VniVJVjZzfV-ji fWj iUW J j'.tfi-.yS)3 ^sSrsBUife) 4 aii?*v "i.-asd3S> a tl iL iBU^3 n i a>10!f DEEPS' r `J TJ ffjVi'iVcl^Ct ?i?.s,SSjj5 n } ^S^jbiEL- tE522&> if .i/iasaso^ ,/ 'riiIi}*E' ri3^3T^.? A kj*2lS 'jL\^:13E) ;Y .Uv *1 t jTi- ^ . ijyj ^m_L 1i_u "^f>" u ' *f 5s 2&3iie <** ^yi^sv* ``"'vy/Li* VM2LfHsit^3y -;.t.:L'i:i1..vr,T'-^`<:i Itikrii>i<gi .\ Jjy^y.vaa-'t iiilifiSlW, > L ETC 37141 W-- r 'it1 1 xV*HlL , ^ ' V r _. t ) >v;y! ili.30 1 vf,' :*- -' ^* ic 't Mi; *- -J. 1' ' -^iLf.1'-* `` j r v L* *' ^. r!VtJ i! ^ r^7l^l l \*}'4tV *j Jj a* T^''?=:*T- *2SL` riti.T >.*23? ^J-Sh ?; '`.sljfelbi 507? 7*$35 frjfrTr ryirTV ra 7*i v-^vzjw ?? ^ BSiiia* 0A& "SSPl ^2t?3D J&l&l *a!5 ' ?, 7*f ^~y*i-lj yiV fiy. iTTt g Z- |V k*^Tl iil'-. j?' .''TO:)j3 ` * : *" .75T' -?J35Av^3it5 --Vrit; 7- y :':'*i .-7l,.V.7inrl7- DiriitiVZ ATkYjl 'y'Tl'TZt :^fe>VrJ*i^fCT\ yj>*i; v -- ' <V ^ " '-- ~-'V _ ..............:S * ' l'.t . -=: A.iaan$^SgLiiWP 'S_:r*s:r- ETC 37143 .V -4- To- From ETC 37144 FS#*' Report OC-83 3L7 APPENDIX VI REPRESENTATIVE ITEL5 FROM THE PUBLICITY ABOUT THE BAYWAY.POISONING EPISODE etc 37145 I REPORT OC-33 APPENDIX VI 343 MM l rtMor A. J. r>M to kaiio--ta Ptoto It war *atd th#_____________ nttnu*d hi# ln*"*tl#*t00 to OVcO'r* hlM mad* to hand)* th* lr# I hqIIii FROM INMSAANNITDYIECS ASSissSisWBi"" hi* .-if--- ;1* mob# a *____________ . . rtfortH lAat nt inudlndlT uonr*tMe td 111* lad i >|in, im that it hovld U cnaitail to #r#t Htrar-l ou lh* unF-M gr^tonaH rigc(1iwlf . S'.at tfl aMU- fom the. pio-ltot nslfUi hr SU-ie --seiutely Mil. *.*h"r tbrr* ha4 beta any criminal i>* ciur*n*v. 'I !*# fi--d ! om ththf,'' he ttM. <n.i it.ot I# that theo drslho Inch n-A ** th* ream* to etowUnmi* i-ti in th" *! to B^nulhiH'*. TV .'IfBrUtd l*.l i.'a'Pini It Ihlr hUll Lr could *tonto pool pwwoi frma thto MrretalmiM mkeUaeo. Mu .om: haraunNnl? to N ro* if ran w ar< df|#*r cn*toan*. r'*#tyfi** nm wrr* "taani in th* rtpriiw nuiloa. **npto#lna to thro* ihlh* --f ftft**n n*a roch. All w*r* mixing othr chawdhal* with* ` alia* I w#*itbh*>*rTt*" I to |h - *ont" !aftu*ac*i from ros* I th* ** w aa*. Th-- that tonb 111 oiaaW mM lilerti siatg oN Nmea. | eh# rfrirtra*)' # th* laiolto*. Thto i> --i IlffvinH riaipoo*. Vet la t*. it proiwet tb# 4aA|troi foi m j game cm ta diMtioa. aec th" ad *%prtm*at." r-p-alor pro. cr*l f*ir #? firM.an toaoenat#. tl^n n*n't-al r "!"***#. lowrrM Mow po*^ Eight Other Standard Oil Work in Suffering From Poison Said to Be Tetra-Ethyt Lead. hrlhf asof ta-l Cv brtnc voiattUaed. WVUiof Ih C*4tar thu* trntod as* t*>* l*xd la iairod-- pwlchljr tot# th# j hetnf aul-i is tahUaheO New 4r--y baa not hr## Mood moMl lh# lup end rah** Ha Th* i_t_a_e__w_t_o_#.! Oil `IMO* #f S< *.. a*-l Iwtllr bruin riu(rtiM. la ou** tn*ianr* th* ISIn"# cam# mga4)> : lr. it a# to rvn>ulaitY *h#ra*t*r. h-M pmcr*#**d * rradually a* ta attark a* liw brain Ml nm `a no ha*# rofTerwl from wwjUa a null of hm'tiinf th* n* to ihta ha*-* Had |M MM1 * ufo fom." \kru tbto JlhrlP Jto Is.JefMT deued that it <> ton fvtlm to - xp* T>" m*dtrl #p*rtal- n*#1g"fbr ta a Mat##* at Uu*l front tn tiien- did not bau** alam"H th* (Mil offto .1 A Rroodao) yratrr- ;l lat Tnr#dar. and th*n tolwrd lr. Thto tai*ao#nt th*> Pvi ii- otrur.r* malady %H m Tor ** -ra! mi* pt*r ih> itorWp- h.#d 'm il :#t haturday. wb#n a i#J<ha rr*K detanamt to th* Riandard uu turn tad no* men'e Ilf". L*ampaa> to Svw Jor# <#. ion tor th- * Df. lman *al Tlnirnaao aaU two EXPERT ISSUES WARNING leidihre to tn# foremooi nbratote ant* mfmooee #htat#hto. ha# h**n #ncaa*>t Or. ^ ..... , Ytntfafl Htndhrton tff#r*4 permanent dam*#*." Ur. lltadenM Hid that Mild*# nH r load poummi hl t Pnml>U sad .cbor rvet? ipniplWM, Ml krnthei* Shi .f *mall amaia toCM wRw I-- in aa effort to find a eetoaacr which <oalfl V tarat nafall* #a#d with etrtlfk' ga##lih# ta #n*r#*on# crrlaia laherrot lifftotilUr# to mot## car operation. tVhca nrh a ouMian vto daew*r*4 Monseo to Public In Um of Ufor |inpt*<na - it> it #vt#td# %af#M vorkui a ton# Thl* ta an# of Ut Mat danger#a# iinttar ha*# th# ^tdoaarat depart- tome* to th* trrtry today." U ni<Li *ii*at h#'*ara litr'rand In th* p#*#iHI- fd>r#rtan* a-t* on :i.. crnusl all t:>* Hot* at th* KDtabrth plant. tarloUne a Mtff to ar--. -n * *r|n>*)- hoardtaL hd aa amhoi.nr* oriro heHHnt roi:~nt* '* .."4**.. <-itl*r |n th- ett* h-ukitil to inttihth .*r ta X*w T>*rh h**Ht*ln. Ko**.> to th* fwtr-flw **n I aa striM4 Han ly f- ftn*r la blnoi |w***urr. or into TV f*w form to P4Mtlo. FEARS ITS USE IN AUTOS jlrlTel* JifehnattM # ttviit *M)ort* saffi44 iiihHiM thto I* th* flm ' Losd in Gasolina. * V"*tnat haa mew--a oidtly kaeia. th*r# t Htttil oiVr atiwitor rati m^r#kt tot_h_# -i--u-- m---a--n_ia **#w..b..e..--.. > Th#r# u auch oa oath--ab 1. a plant bteft | ian#tH liberty to dlactoa*. ^' -j tMv ,'ro# tnl infnnnattm that lh* Standard Oil Company. while tt had tttos af Ha iMaatoaMar# w wi#n a* tuiniliPa. A temporary laboratory ## dutpp#d tm lb# r*# arrh huOdlnc at th# Marar punt and trora wa# h#ftin th#r M#ul And- I"It *u rUaa*d ta ua# thca# aaartcr* far ala month* nl>. to th. *d to wUf h Use# tt vte expert#d that eanfli would hare hota learned about th# pror## t. warrant th# ictton to ------- ' < I ' I ' (. ' what *u iu* raw** to d*uth In two i atjv*t al to Ulnraa to a*v*w ocfvru. TV Ptandard Ott <*nmpany to X*w J*n*-y haa hod to ff**t for maap y#or an oplc W"lfaro plan rulttn^ for # nuttu. hrnrfHa and tnouranea for n*rnon# injured or billed whll* M th# #tm>. tony'a a*#n-W". TH# famtHo to th# two */ Inm .. ^ tUUmtat .. Denying h|,_ i hoa* to Tori thtiast*hkaui-thmUteilt ntolv n other for nauMfcial produrtlea. .. _____ n-n who <W. H wo# uJi would mam I aueotly b* rarrd for toad no numry k .. iHgHfdnwa ... , . _____ All CtllftttP| Moioe. In mr arlhlon. etu*a Mb* Ne* \nrh <*Ht dvikf tab* Mtwptfc meaw taataU%#iy d#c.rd*d t# cm rack a build > * would h* ifM In traaiiaf th# noth au lac at Checaco if the nrdimwtl work .. . _m ____ Imployaa to Bd laamlnud tr-o t ?rft*et lh*m--Hr-- aiHRH th# ceUc oa at Sa>w> Mbaud a law**- Mnm wnh-a t* tnsov#* tn ihta. bI aolutlOH to >own uauaual wtaoufa*-- TH* family to William X#hwtn*y. or to tv virtue*, at K**.natrurta*u lino II an euldmokih from aaolV# Plat* i-tixi. *o. hc hm la % nrahJacVt i ' ' u-iny thto car *h#eld l*ar# enclv iroubl* Aa tn lh# production to Maaoi. aNro "*- omifl*.| to coo* to- th* hnopHal a1##* fifth A*#>** sad --ioaa* titan* pmdM and certain other HkjuuI >*>rdy hnioc* there tea il.itoar to Tt* Htaad death Jraen. in*att>"Cfh : to gto wlth'th. l*nl mlttur*. H; tobutane--. th* maattooeturo to th# a*w a fa (to vmetaaUon. hut N wp# |at*e durllto ty n a. ' taad.NL OH ,,-TS * *toM h* HVIy to u-- *** potoofithf i fluM hreivu rcrtaln f*re. Aral** repo--M that ho *u tmaraud. ""7 Rl to# .uataia ta p *,, MMiwa ta i#imm atone iV a* cm#. I tho-- encT pmrauUon waa tahro by ih* TH* Standard OU'a *voia--o*uf Uh> nisahelh. X. J. u Mportrd fra |; n to thu kfal w*f* nhaoed la a I duealan--cn drponm*nt Tb* foro non tn*--. u-h#r* tha jaMtlof ott-- t'rdafc. Th# rlrum was Walter d>. r-*c*. rmhN*- hat" dl--v aoihorttr m a--upattonal <ita*a--a. att- *. m <wmir mm u OK T1'* lac aa nabctl conauttant to lh* Mand CoTipoay to X#W J*r*CT < -- Sew tn too Ri . ...i oidrb-h# had h--n rewemed fro-- Din- - fan*"* or* danfrou#. A* tn# rymp-1______j and th* loral ph)to#iav >*wta. hu --------------- ______--. poo .1. not nrcur Imm"dlatrfy. he do** j Itfwar plant la mah* ih# work ufe. r u know hi# danc-t and the Oamac* Tb* doctor# aironcto f-r fr#ycnt *nat- .lh ho-- to In- Orient*, who dltd %ja>y uk> plan# lat*r. I-natl-o--n---a----t--o----a---l-l tho--e# u-h--a w- o^rbol ~tat t,h# to tb* deadly IU m Saturday "Durtoc tv fovmifntloo of thla rah laboratory a>l k-- oefo'P look*-- for Forty mep, way *p--d to th# j orlerd % tab* a at-th* nlaat today, li^^tovofortad that s' M..i _________________________?..!# a a-iahr to Isvcnifaton. tMw ajm--tomo n*#Uar to a# ptoaonlnc- ' ** *M * itodrr ^ r-, ^ h%v,, a^R pniaovd. I Whan Uln*< th# atokil rsamin*-- n*pert*d n itl|W dpo of pnlaontr-- tn orvo--l raaer It timtarai al tho VI--oomrostion Mon- |.ue*'i li * a (natter of tttal Impw Itaa*. th# m*o affortod u**# wa reported that many otVro *n u total. %l| mor# or Icso drrmn#*d from l .or- that th* heol(fh authnnorritU-- to X# Uuufmex to otlior work. owabkuroh Mpt#d it.o kh.amomo --auc-h- 1^-rkum,atty'.. #hVunitahUouptrodt*ecat yt.a" V aont to nowwtrwt-- II--octal f-- teeatm"nt hot thi# waa --toed. TV. C. O. John*. INraetw to tV -i*- --a tofcct on th# h-- and u*. y ,m* mid ba wo# c #^n*r polntoU out horro No--. Cblto Mtowni Scam- {* * '.'"ZTT'n hr#, aa-- h uuopoctad ft--n th# Dr. li#U'Wo*u la on# to th# tr--tot "Oo Puturdo> winM lh1 undor retoil t*r* ba wl# HI. TH# awdt--1 departdiairiy duel th# laboratoryi ttk#n*w laboratory', waa ah#d aha-- a --pun ttat #ia rat# avi #ia ptc#--* u#**l to i*t tv 0a #H lb# laboratory ** ope--si had all dVW * 1 non t fenow about that.'* ho mid. ' #MB* that death had boon cntnwd aothoritim on u>U #uh>#rt and I b*lto*# d that o mwr# mm b------ b**yi*rt RMgero to HI Oserry per**#, . tMnokvi uto --.t (* .otoM ala TS1 *-- Tr P*1 "* *U,.tT hod rwcnlod no crtdrwci ao put. H# td tto dnaettou to 4--tha f-- Wod taal what !# aay# fe wfTHl't --to Dr. XmU "Within Uk" Into att w*b# I, i.Rs* n**n w.rw*d that thor# to a mow- r to thi* bind, hr* (a* at wo havol Ml they* prpdlf-- thu COU-i| chtoon to on laor--tcattaa of th# rau-- ! to to# inpraa. ft# patimt# *i> sent --* ntitketk. pok word tn tv laboratory three n*rh acn hreauao of Ulno-- on# haw (tore ker confined to h*d at hd ho--#. M*--hero to bio family --M v m n m. m <-. --. w.s w. *^^ta,AJsr2sa"SL`lusrsa" Mtttal cMMMiT -- OM U|K^,5Sl?5L"S*citr. ***4 to# Hacunptnwusu. Ildul In X"! Tor* CMy to tin them tb* h*ot paaoihi* day Ho had aitowu no Vprwr--e-- and ti*l he rnotlnuaHy #--npt.kt* that v h and. ^ tn! ~l Ha** h**n Inform-- ihat th*y har#} aWentton. On# to tv weii*rUe* to- ilbeon puttttot *o tv mnrbot hi 1 Iplncea a faaoltna centa--Inc about aom*j ft perl tb-- faro* to nManioc he that n*to "in" that hand to >4i<hti awn#.** /V-ffiV yb/PAr 7'/i*S,***(*- < nt to lead and that. -- my opinion, tat ma opp#oi to a* hrmn* whil* woib- Dr. %ndtol Hut-- ftifaiii to n"# a aafo pntourt. *--*ctolly In M*t Inc alo*--#M dUeM* wM have b--amu --- --------------------e.t.V.s. -- .rite, in wMh *u"h uwnntlU## to can a#* np--iianf--#ii0 at Tam. M# aw# -- at-ehar*d *-- the air fta-- ----Ot* QL Anoth*# t that th* umuUUv* rf- f--1 lh* Um#." f*t to >m#Twprrt-ii eitaa-- t* turn-- ha* kern imp--Mbit to l#t#rt-- wtfl n/CMAir, OCTOBE* 29. J92+. VHr fathah Mat Vet, titnmu o*ta in. |*. Xorrto #aM h# would raft an tb# "Aa In ath*r M# --dptortm. th# --andsrd oa t'ompony to .Vet Jew*) haa ^unton OQ Ho uM tho ftmdird OM rimp any to fumtoh aH p*iu* hlt--dii belli-- on th# ll*M no* to drwth to th# mop who died to bet--. --d that ho i--tod It an ona tv* rlfy. "Out pea*trwtar# and oth*fo who may to tta CWM MM* to Bh. heoltb o ht rfrtikil proto to th# ran-- to -.th win bar* to. wait paaelhty a me >-raw to th* "Irene romplt fy to eo rhmtrul anaiyato no#a#*ary bict tiandard OS tfftotol --ukd bo' i *otaWwh l*ad ft* pot--alnc- *V**'tfmt#d joloItv..LffUlBtM--#--at*oHo Uaf|h.--buotwan ` ft * K. Uto*. bon-- luriua at tb* b*pt a larc* fmr# to phyatvtna and h*miaa w--hn#d to raperhwaeal tudWo. a-- to whdvb aro aimw--uty attended wnh uan*r. Ker thto rrbaam " cl*** a crrol dal to pl--htb-- to #af#ty nuwie and N raj #*r hew uurH t# aafrct--rd ________ acnlnm Ittn--o or eerliwu. ftot #urh aa arrtknt the#* 4*0tha --r--red to pH* to h--tutkto la C--lip depl--d by th# cuo^pany." ft wua uyhMH that th* Muni **'-^VfrtMato--mihrt.--VIlmtutotiieardtwh#kavitanaa--cm>eo,mrH,hiaawnaca-hI'MoT*--V-.-.-t---- tftl ii* afl doing toerly.** V --M. Minora nHe*t --s.4M N wa.a wirua# that t--b* nd our "tpertatinn- I* that they *dk eV" rN*"ons*rrr. fra--r th* um*t part they oor* 5T521 rttamol. Vlt Urt *131 horr fit# to hi- L**' w *Vi. --ftot--t^bad --own ***, V* trxT effhhpt9 to ihlo newly kwei--d r-- tin* laiiitoaai-- mad* It I--toe for autou--(tv# powerful e.,....................... _ nd (--< toan# /** p--line i . _ _ In* on IV morhto hoe* odruwcod #e, uhaneuu' ty nlth th* rUiftoiU aw IV1 HhiMitomhrantlMS- <-- M tt*. M ETc 3 7146 KEPOKT OC-33 APPENDIX VI 349 BARETHYL GASOLINE AS 5TH VICTIM DIES City Health Authorities Forbid Its Use--Sold in 10,000 Filling Stations. asserted that the absence of reports o. Injury due to breathing this gas In au tomobile exhaust fumes was no indica tion that those fumes were not danger ous. He said that this poison *i so Insidious that the breakdown in health mtgnt occur long after the brealhiac of iiie poison so tnst insanity or milder *>mptoms might not be connected with the true cause. ; < 1 , Thirty-two of the employes of the plant were at the Reconstruction Hos pital yesterday. Some of them have de- velopd b*ov*d eno to symptoms at the hospital all and were reonly as a pre | sulton. | Hon.' which, with the Standard OU Com pany hf New Jersey, owns the Ethyl Gasoline Corporation. Not only had the employes of the | Dayton research plant been under ob- servatlon after handling tbe fluid; two I of these case* proving fatal, but similar J difficulties in 'reeling adequate safe-j guards for employes had been met with, at the du Pent laboratories. Mr. .Mldgley | revealed. He said that the experience. In combatting the effects of the tetra ethyl had been general wherever the process had been carried out. Without, he raid, desiring to attach any blame to the employee, it had been found at the "Some of them are suffering from j Payton plant that the men. regardless headaches." said Dr. C. K. Flint, house "it warning* and provision for their pro- physician of the hospital. "Other* have ' tcciion, had failed to appreciate the dan- pome mental disturbance. It might be . ger* of constant absorption of the fluid bailed a mild delirium, or might be celltd by their hands and arras. dreams. Lssw blood pressure Is another Symptom by which Injuby from the gaa Ifanafaetare Net Perfected. DENIES IT'S "MYSTERY GAS" la detected. None of the thirty-two here at present Is in a serious condition and We expect no mors fatal results." Dr. J. Gllmaa Thompson, consulting phyxSdaa for tho Standard Ofl Company, Nervousness a gjmptam. who was present at this Interview, gave out the following Typewritten statement Inventor of Compound Declare* Extreme nenrouslneoo In one of the | on tho subject: early symptoms, but It is difficult In f "Tetraethyl lead la a substance first Dangerous Nature Was bom* -irt to discrlmnate between ner- I known to ehemlsts in 1954. Since that rnnen caused by tbe gas and that I time It frequently has been experiment- Long Known. HAD CAUSED DEATH BEFORE Bus to anxiety naturally experienced by ed with In chemical laboratories where tone who have been exposed to It. ac cording to !>r. Flint. It was known to b, in concentrated form, <fThese patients are being treated with poison. It Is o compound of metallic Intravenous injections hyposulphite of ; lead and one of the alcohol chemical poda which Is believed to combine with the lead and produce harmless sub stances, but the fir* deaths si the hos- series. Its recently discovered use for greatly promoting the efficiency of gas Oil Officials 8a/ Workers Wsrs Warned, and That It Is Fital on successive days have diminished oline engines has led to its manufacture he prestige of this remedy. Dr. Flint said, however, that it la thought to bo beaefidal -to then* now receiving the on a till commercial scale more or less In a through processes staeg of develop treatment. mtnt This has occasioned unforeseen Harmlssa In Dilution. Herbert JTueon of SIS Grier Avenue, Xlixabeth. N. J., died la a atralght Then# deaths, together with the warn* nga of Yaadeli Henderson and other Inrftlgators of the alleged dancers, lurk accidents which as processes and appa ratus are further perfected should be I , catling oflsing to the use of the tetraethyl leads avoidable in (he future. One of these called.the. a pedal meet has ben the niddn escape of fumes from Ks' nf the Board of Health of New York. St which this resolution was adopted: : large retort* and the Inhalation of sack "Whereas tt hi.* been brought to the fumea gives rise to' acute symptoms, jacket violently Insane at Reconstruct tJoa Hospital yesterday morning, the fifth victim of the deadly tetraethyl lead fumea generated In the Standard Oil Slant at Elisabeth. X. J.. where the tetraethyl lead waa beIns added to Car attention of the Board of Health (hat particularly congestion of tho brain, pro fcompounds of lead or other deleterious ubtianess are being added to gasoline ducing a condition not unlike delirium n tanks of motor vehicle* and motor tremens. Although there Is lead la tho engines generally for the purpose of in compound, these acute symptoms are creasing and. gasoline or motor efficiency: | wholly unlike those of chronic lead poi "Whereas It Is the opinion of the soning such as painters often have. oline to increase Its efficiency. The ptoilne thus treated with tetra ethyl lead waa harried from New York Board of Health that such mixtures of 'There Is no obscurity whatever about Rsollne, containing lead rious substances may or other deli be liable to - the cffecta of the poison and charact prove detrimental and dangerous to theerising the substance * "mystery gas" City as a public menace by resolution of the Board of Health yesterday, and similar action waa taken In various health and lives of the community, par 'or "Insanity gaa" Is grossly mirleaillng. ticularly when motor vehicles released as exhaust and motor engines; from be u "In the recent eases of poisoning or- "Resolved. That the Board of Health ' curring among employes of the Stand peril of New Jersey. ThirtywU persona were under treat ment or observation In hospital# and eight In their homes yesterday becauso of exposure ts the grna, With the fin dead, this made n total of forty-nlno does hereby prohibit and forbid the use of gasoline for any of the shove pur- ose# to which either compounds con- ' ard Oil Company of New were five which resulted Jersey, there fatally before Lining lead or other deleterious sub- the delirium could bo controlled. Tbe E:ancns hsve been added, and also does other prulent* wer* affected In mild Pereby prohibit and forbid the addition - degree. but promptly were brought to of substances to gasoline Intended to be'the. Reconstruction Hospital In. New used for such purposes. ' York, because that Institution is devoted persona who had been placed In tba Health Commissioner Prank J. Mon I exclusively to the treatment ami Inves peril of this insanity-producing u^ stance. aghan afterward held a conference with tigation of industrial diseases and ac o number of health officials from New cidents. H*rr new methods of curative Jersey at which It was decided to make treatment hsve been discovered which la an official statement yesterday the a further study of the ff'i* of tetra- : ore proving highly succes-fuL Standard Oil Company of New Jcriey denied that the poison which has Wrought this havoc waa n "mystery tth\l lead in automob:le engine* to dis "It should be emphasised that the cover Whether It presented a menace In product as destined for final use In garages, repair shops and eongestrd .gasoline engine* ha* to he greatly dt- Streets, as has been alleged hv scien . luted, usually with 1.000 parts of g**o- gaa" and said that Its qualities were Well known. It was admitted that It Was known that this gaa had collected l previous tool of death and Insanity jbefore the forty-nine employes were ex posed to It at the Elisabeth plant. Thta tists and denied by the manufacturer*. llne. This extremely diluted product The health officer* In l*nln founty here all requested by Prosecutor David to stop tho sale of gasoline combined With lead. has been for mor** than a year In public use in over lO.Orth filling stations and garages, and no ill effects thus far have I been reported." | Standard Oil officials expressed the Defended by levswtse. opinion that the Bayway plant, closed after the fatalllle*. probably would not plant continued to be closed yesterday.! Thomas MMgety 3r.. discoverer of ihe he reopened. The work on which the and tbe investigation of County Prose tutor David of Elisabeth Into the pos*. gee of tetrv-ethyl Wad foe Increasing .men who were stricken were engaged bower In gasoline, defended his com* will be |tt arma carried sold. on ol the du Pont plant. klMe criminal aspects of tbe case con- lound at an Interview yfr-terxlay at the Unuod. offices of the standard OH Company, at Betters Ike Men Knew Danger. Coed la li.OOb Station#, h Broadway. To prove that the sub- Asked what would be the reaction of lienee, ws not dangerous In small the Standard on Company to possible Although the perils Involved tn making I tuantltls* be rubbed conw of the ter*- claims of families of men who died from the load-gasoline were admitted by the ! Standard OU Company yesterday. It do- ; rJiv| lead on hi* hand*. He sold thnt lo fatalities from the use of the subitance had occurred at the Dayton plaint the poison that the stricken never aware of ths extent mm were of danger hied that ouch perils existed In the use * t-f tbe General Motors Chemical Com- Involved In their work, official* of the of this gas In automobiles, buck gas l | any. which also haa been making this company replied that the rejection of oline. greatly diluted. Is In use than 10.000 fining stations and In more garages ; * i paseline compound. _ Mr. Mldgley said the Bureau of Mines ha t beecn asked to make a most thoc- many men as physically unfit to enimg* In ihe work at the Raywny plant, dairy physical examinations, constant admo and no 111 affects hsve thus far been I ou*h tnvsilgatton of the effects of nitions as to wearing rubber glove* end reported, according to tbe standard Oil ; telrs-ethyl th- bureau lead gas poisoning, and that using gas masks and not wearing away had been conducting tests In from the plant cioihing worn during Company. Acting on Information that | this connection for about ten months. work hour* should have been sufficient this produce was dangerous, however. 1 According to an official of the Standard Indication' to every nmn In the plant Ua health authorities of this city barred ! 1 o i Company, the bureau will omke a that he was > (element on the results of thebe tests dertaking." engaged "In a oian'a un IIt yesterday. Dr. Yandel) Henderson of I ir. two nr ores da vs. The t*ts ere be- Tale, wboss opinion on tbe actiop of the l Jng made. Mr. Mldgley said, n; the r. New YOBX T/MESgas on human breathers was ought by I >t of U.t GvAvial iloiot* .corpora- O 3/,tha. manufacturers and the ctober ETC 37147 KEPORT OC-83 APPENDIX VI 350 NO PERIL TO PUBLIC SEEN IN ETHYL CAS Bureau of Mines Reports After Long Experiments With Motor Exhausts. MORE DEATHS ARE UNLIKELY All the 34- at Reconstruction Hospital Are Believed to Be Out of Danger. LITTLE USED IN THE CITY Tctri'Ethyl Compound Sold to Only Two Firms. Which Art experi menting, Ssys Standard Oil. for uoe In gasoline. Tho tetraethyl by the snlmals wax similar to that which lead la sold in Us pure form, however, to the garages and filling stations, o would result from exhaust gases of an average automobile using etnyl gasoline ilufed pn as to contain about four parts that It is handKi legally at thousands r carbon monoxide 1<* i*n thou, and of places. Elaborate directions and warnings are seat out to those who xfts of air (the permissible spocure Tor on* hour from the .standpoint f i-rirben monoxide no1sonine>. Th| was handle U>e substance In Its concentrated a considerably higher concentreiton form. It is mixed with a red coloring to serve as a warning of the care neces sary in handling and to prevent Its use exhaust gas h*n r <>nld online HI; occur. `The animats were observed through out the entire test period for symptoms for cleaning and other purposes for of t*ad Dolsoniag. as colic, paralysis, t-hich ordinary gasoline is used in the loss of appetite and loss of weight. Also home. a careful examination of the blood was Philadelphia yesterday followed the rttppie of New foit City by prohibit ing the sale of gasoline containing the made for characteristic signs of lead poisoning. At various times animals tetraethyl lead. At the same time a were killed and the entire tissues ex -port of the Bureau of Mines was made public at Washington with th conclu sion that the danger to the public from 1*ad in the .xhaust of automobiles Is amined for effects of lead and analyaed for stored-up lead. "After a period of approximately eight "seemingly remote." Tho report does not deal with the dangers In handling the sobstaoes at the service stations or other risks aside from that incurred by months dally exposure to the above con ditions there was no Indication of lead poisoning. The animals continued to the general publlo m breathing air con grow and mature at a normal rate. One taminated by automobtioa. of the dugs gave birth to five purpl**.. The Bureau of Mines carried on its There srere continued on teat with the investigation at Pittsburgh, where a mother and in the course of the test number of compounds supposed to tn- matured normally. The absence of lead re*** the efficiency of gasoline were poisoning may be due to the mail jtested. amount of lead present In the exhaust "One of the commonly used anti gas air .ulxture. Furthermore, observe- knock' compounds." the report said, "la lions made on man showed that moat of known as tetraethyl l*wL This is added the lead in exhaust gases coming from io gasoline In quantity of less than one ; ethyl gasoline when Inhaled Is again ex-; ran or tetraethyl lead in one thousand i haled. | Aarts of gasoline by volume and tMs I "The Investigation carried out lndl-j mixture auld on tho market as ethyl | cate* the danger of sufficient lead aecn-r gasoline. mutation In the streets through the die- fisMtm Belotiag to Health. i charging of scale from automobile | motors to be seemingly remote. "The problems of tho health haaard j 1 Tl>* Investigation of the possible I due to (ho use of tetraethyl lead may; haxards of lead poisoning from exhaust I gases is being continued at the Pttte-. jbe divided Into three parts: j bhrgh station of the Bureau of Mines,. "1. The haaard In the manufacturing together with the first two ptmses of and handling of the concentrated te- j this study." None of the scrvlvlnr sufferers from tttrthy| lesd poisoning appears to he In serious denser am* It i believed that, the death lift of five will not be In-1 reaped. according to reports from Re construction Hospital. Four new patients were added to this group. making a total of thirty-six at the hospital, but two of these were dts- j charged later as being' entirely free ; jfrom symptoms of the poison. | ' The patients here now appear to be out of danger." said Dr. C, K. Flint, j jhouse physician of the hospital. "Soma i of them have no symptoms and are here for observation only, and none has de- > vriopM any serious trouble. We are hopeful of full recovery In all these case*." f>r. Flint said it had hot been estab lished certainly whether the lead or the higher alcohol in the tetraethyl leal was th* cause of the illness and deaths. The lesd Is combined with one of tho ehehol group. .According to Dr. T. A. Wallace of 141 Fifth Avenue, the gaa. f tt<r being breathed into the lungs, ould be reduced in' the blood stream to pure alcohol, producing a form of acute .-icoholhm. Brtj. Oa Amos O. Fries. hief of the Army Chemical Warfare >*rv1ee. reported, on the other hand, that en InvretJgatloo of the use of this gaa for poison gaa warfare had shown that I- ad waa the agent which produced thd poisoning. Samples of the so-called "loony gaa" were used at the Egdewood Arsenal six months ago to see whether this reason- destroyer had sny promising possibilities for war. and also to dtscover antidotes trarthji lead. This haaard occurs In the , Little si It I w4 Here. mi rafacturing plane I ,,*. The possible haaard in handling | The resolution of the Board of Health, i ethyl gasoline tone part of tetrm- prohibiting the sale cf ethylized gasoline 'ihvl lead to one thousand parts of i m the city, will have no Immediate ef u*oltneK This possible liaxart may! effect those handling ethyl gasoline. | fect. as tiure have been no sales of the "3. The possible haaard due to the *a product here, the only deliveries in New hauit gases from . automobiles using * ib\l gasoHne. This possible haaard j concern# tho entire public. York City having been those io three automobile companies which wanted to The scope of the work undertaken; make teats on their cars, according to ;.v the Bureau uf Mines Included on in- the Standard Oil Company of New M-ilgation of all possible haaarda as Jeraey. mitlined io the above. The first two | At tbe offices of the company It was parts, namely, that of the danger la the stated yesterday that the sale of ethyl- manufacture and handling of ilte con-; ixed gasoline has been more general In I'ntrated tetraethyl lead and the poaat-: other parts of the country, particularly ble risk in handling the ethyl gasoline: In the Middle West, where the Standard. ,i4 sold to the automobile driver, ore} Oil Comiwny of 'Indiana-has been a. ;iow b*tng investigated. Sufficient data} large distributer through Us own **r-1 have not been obtained to draw condu- j vice stations. Because of (he demand, jons to date. As soon as (his invest!- for th* product, it was explained, sup-1 fnation haa been completed the results! ills* have been inadequate to supply the ' will be ma<le nubile. oeal territory. `The last part of the above outlined A number of other companies here* prebh-ma. namely, the possible haaard been marketing ethyl fluid in cvnjunc-. l>w to the exhaust gases frem autnnio- tton with gasoline. The Standard Oil Ujr- ulne ethyl gasoline as ordinarily Company of New Jersey, which is equal sold, has been carried on for more than ; owner with the tlrncral Motors t*om-i t- n months. I "The plan of .Investigation wm that i of vaporing \artou* tyn*a of animals j i pica guinea pigs, rabbit*, dog* and nenkeya. over |<m in alii, to a definite 'cnrentratlon of exhaust gaa from an-1 uglne using Ethyl gnaolinv. The con- 1 .-ntrstkm of exhaust gas in air used, was that which when coming from th* pany of th* Klh>l Caroline Curporathtn. owners of the patents on the r.ul<L has' cut it* marketing welt under way lh the! South Atlantic t'omt dletrl.'t in Mary land. Virginia and the District of Colurre bia. The company Is now starting to* introduce It at the service stations in New Jersey. :>\<rage automobile would h* four parts arbon monoxide in ten thousand po^s /YJSW YottX 77MGS, of air: this concentration would be al lowable for but s period of one hour's fiO/EMBERh Jf2# exposure from the standpoint of rerbon monoxide. (The concentration of ex haust gas In air used was ryrh as to exceed that known to exist In ordinary traffic of a city street.) The carburetor was adjusted *o that lie carbon dmms* He content of the exhaust gas from tho engine ovd was less them me-half :'hai found In the average automobile exhaust Showed No tig* of fdnaiag. and other protection* against IL Jt was The animals were divided Into three f-Mind that It .was dangerous unless the representative groups. * The dreg two greatest precautions were taken la han grood* were exposed for periods of threo dling It. and six hours respectively, nod the eat la Fats Fans to Caragswi The tetraethyl lead, which la dlspeaard from 10.000 filling stations at , present, according to the Standard Oil i`orupAor, la diluted about l.pw time* third group not exposed but used as uotrela The animal- were-thus dally mposed for three and six hour* over a total period of approximately eight month* to a known concentratlow of ex haust gm*. These exposure* were such ins* 'b' lvd *ew*n cf iV ale hrvathed| ETC 37l48 REPORT OC-33 APPENDIX VI 351 NEW YOMC WORLD NOV 2 71024 STANDARD CEASES prtrataly yoataiday, taatractloaa had boaa (Ivan to dtanaatla tha plaat Theaa offlolala, who refused to **V. their Borneo, aald aa aooa aa a attr could bo selected. tha plaat would ho MAKING ETHYL GAS oat up la tho Mlddia W< aad tha *--1maaufaoture ot ethyl (aaoltao ooa Oetaoldoat with Dr. Mohrldds re 1 IN IERSEY PIM port, the Anwrlcaa Chemical Society aaaouoced the resulVWrawpndoat laraatlfatioo by Dr. HarrUoo (. How* at Waahlnptoa. Dr. Hows de clared ha "found no avideoca to jus tify even tha aceaataaal demand that Bayway Work to B Removed ao noro ethyl reeoCne bo looutaotured." Ho aald bo* "the petes tar to Middle Watt aa tha Result aa Irepcrunt eeoaomle adraaea haa ban paid." tt would ha "tally" aat ' ef Five Deaths From Poison. to coanose. , Dr. McBride's report ' aald ha waa noBaaed ta aay attempt ta rreeufeo. tura Utra-etbyl load by tha aaam SAFE WAYS OF HANDLING methoda seed to tha past. aa "asps neooa haa demonstrated workmen NOW KNOWN, SAYS CHEMIST caoaot be eateduerdad adalaat tha atrecu of poteoaona contact." At `the 1same time. Dr. Mifirlde etrreeed that the Staadard Oil Company had com- _ ___ Dr. Howe of the American plied with the Stele aaaltary laws la taa.aaa.aaa ranon# at cthyi (saoitae every particular. have beaa seed by tha public la tha Chemical Society Says Gas Dr. McBride pouted out that aedl- act two yuan. ead It haf been sold et aery uuilmta eaaaat ha atpintid to h.aaa tinad atatlaas "without appar- la Tee Valuable to Abandon. Dee aueeaaafully tha methoda ta pro tect thamaatvaa thet aktllod oeUatlata aat tnfury ar laaa at Ufa." The repert aald "uaduostloaaMy tha oh ores It all the protective appara menutnetare of tstrs-ethyl lead ta tus ta furnished than. daafuruM." It potato aat that this Tho paaductlea of tstffekthyi Mad Tha report coacluded. *T have baea bajord ta as (raster thaa la many has baas dlaeontlaued. probably par. assured by a representative of the maautacturln( procomm. aad ouaa- maaeatly. bF tha Baywar. ,\\ j.. Baywiy plant that tha old preceie win facturo under atrlat control aad ads- plaat at tha Staadard Oil Company not ho used asala; aad no effort wjll coals aupervlelon u now possible. at Haw Jersey. it was ruled yester he mods to manufactaro this malarial Tetre-ethyt lead has baea distributed day by Dr. Andrew F. McBride. Slate without llrat neilfylnt tha Department la the term ot ethyl fluid, the reports Commissioner of Labor.. la a report of Labor of New Jersey of the fast." aald. ta small eylladsra sealed with a to Go.. 8llr, (triad tha results air The report covered In addition the tin cap. which ta Puertored by a apths hla Invaeti patios at the laaautactaro E. L du Pont do Nemours Compear, before K la poured Into the deUvcty at looaar raa'* aad tha eeaaoaoaat at Carney'# Point. . J. where throe boss at a earviea etatlea. Aay haaard Oath of In amplcreaa at tha Bayway workmen died, with ffmllar fiadtaea. taeotved la dlatithuttoa la this way. ptaat. Aooorduu to the report at lbs At tha Bayway (hat. officials aald American Chemical Society merothaa Its the eaalahtaff patac kjffalA'hTT EXPRESS NOV a 7 l2 Folly tq Stop Looney Gas mes rsfaimt ta the work err an to* I formed ami r crlre run tornpea- Manufacture, Chemist Says mttoa. Their roadlllaa 1 rarrfaDy watched Iiv phystriaaa. This type of , poisoning dlffm from that of othrr I Dr. Harrison E. Howe insists danger no greater trad compound, la (hat Ihr true-I rthyt lead arrma to rater Ihrrufh I than risks in many processes. fatty tlaaare aad to hr drpcsitrd aa I each la varlou. pane of thr body, hr tocXlarr* Yaotrkl.eiXranv-r.th!yll(Ale.aPd, )e--oMcaallsesd- MMYhmTSiilbi&uSmS wvnuiweT. "?! rtlBodrlnli(ipiblr" Praia, wbm II rrmalaa I Xavertbrloss. thr report aulatataa.! looser res. should Dot be dlruoir , stated. Ila >|V. hUa?.7I I . the dangers are "ao arretrv thoa la j U*lTKt.^?d'lnhI 5yy*-l-"r->!^' **** Important ernaomk ad- many a ide maaafariarhm that by thr primeears" aad'1 liar I hr tied' '* onhrr polatrd out that nartw ibr tnntrrls:." ibe haaard la ?:r^TortotH,hVopf' radarrd ic-ac nr th* vealehlaa point Ijr Jllotloa. that la thr fotsrr i*SIMl1*!*** i2taS.`,lu JS dm Sundl^nu **" * 25 Ut# wiilauyt apfrwat injury or ' * l'>"- I "Oute.kaet.ly. the maautariurr of t.-ra-rthyi had la no ethyl flold will b" sold aa each, bet ethyl palotlac. ready for oar. wtB ho received aad dtspoaead aa la aay atanaera Oil compose. baaardou.. ib njon luita "the ETC 37149 KEPOKT OC-83 1313 APPENDIX VI IS ItrsTHl.tL J.vn KXHISKKkl.W CIIKVISTkr KDITORIALS &eeetaV,mJ. M1,.iN9oZ. 1+3 Tetraethyl Lead mvow to mt*e thr*Mcli fatty Issim aisl t Ir .dpitlnl an Nu ll in vsrtaiu- isftmf the Ixsly. us'luding ilr learn, wbrte it PL1.UWIW, the unfortunsic Ion* 4 life imi i* ntMiis unchanged. It dors rst apjeor Ui Is* mttmlalive and jAuvee* uf the StaiHUnHhl Ctu|iiv at Hayaar. N. J., liNi|>]s'sr> by a*v >4 |i-c*|r*l*4> ami Issly fluid* if lie nun s arinu* accounts uf ninth have a|is<nnv| m On* daily anadffected ** |emi|tflv sasunl fnait mtsrt aith lie malmal. Urhaical pw*. iljrrr w many tiMiofHiiuw id liNMia n*c mm nisi k*4 llwir Uv*-* were examined frc-jurotly in ahirh a few arwotifie now had a |urt. K*etuna!Hy, f*r |iluniis><u and firty utlwrs sffwtcd at ilie same time ham other irnUaU were in a |sm(b In jierviiit lia.*tjr attorn Iseei uvnl The haianb, moreover, are is* gn-atcr than in and made remarksMy tbar ir]vis he tin |*o|rr guidaDra many manufacturing |efsc. Hy marking is ewpIrtHjr of trardr of health. It warns sell to set ifowo here a few rkssd y*tmw safety i* t4amIAr. ami (rthafv tlw grealcot of Ibo fart* in the pml ItaxAfd w the mdifforeme ahirb mt isily aoriium Iart even 1TetPaethji trod. liocim-mj in 1V|, haa long Im knon rlarmt eieue t lime he ibiipf*** *ici arth alurh they aa a uglily tour suUUik*. It p in no mb# a myitmum are familiar. Imbnl. tlw ethyl fluid is -culnced to |WMt subsume, although nanml mystery gas" by the daily mm fruui using it s* tlrr tie any dlat ga**4mr fe wash pwa Id cuorratrstni form it p aUmt ocotttriijrth aa ing hanb. It lias Ism dmiunstrati-L Imovr, that maan* potent aa bichloride of mercury, and one twcotv-fifth aa fartura uiwk-c strict *iirvA m |*mmI4p awl, a* adeyuato toxic aa mu>lard gae. Tlie dpetnery that its uee in gasnlim wpcrvisioo is runiantly wtriwl and tbr <hnoo are knuwn, would permit the employment of muturs of murh htglier we must k>4 funlier fur liaaards affst-tuig large uumbera. oompremsoa, and focaryurntly of miproml emrueuy, Ita* Dtstnlaitmti <d ethyl fluid invuftev a large Minbf of mm niade it a substance of great rawoortur imiswtanre. Data who ale very bkrlv in 1* earvhos. To dale injury to noun indicate that with an engine deigned for high rveupmisioo of time tnm njafatmc taenty thousand filling italinne dim aa much aa twonty*fiva par cant of our petroleum ran be tnbutuHi ethjH gauime hn Iwen repurteil. Xn irtheiraa, coomrvad and the amount of carbno monoxide mlurrd, the haaard m redured l*y ddutino to *o near the tanidling owing to the Imarnrd conauaptiuD of furl per motor. point that m future no ethyl fluid wiO ! sdd as meh, but Tetraethyl lead * manufactmed by one uf our largest and ethyl gmolinr ready for mw will Iw received and dispmuwd moat egpenenerd aiakm uf chemicals, who haa drmomtratml as w any other ga ulinr. that thn compound can be produced aitb safety to all who The mutorwt meets no haaard in the tow uf ethyl cm and am engaged in the proram. During the developmental wort clearly ha aharm only such hatards as may tluoaim thn three men have been lost, but with a better undentanduig general puldir. The puldk wanu to know bow liable it in of the effects of tetraethyl lead, illoeea hae beeo steadily to lead |weM?e*g from the discharge into the atonphrm f reduced among the workmen until, Uka many other tone soar two or three Urns of lend rompuuiMh* per uiHine pHono materials, it can now be produced in large quantity wuk of ethyl gmiJinr burned. But the |aiUk ia not nearly an safety. eooratned aa are the manufartuim. who reaiiae to whnt Ethyl fluid is tht form m which trtrarthyi lead baa been extent tlwy would be the subfect of attnrk should it develop djatnbuted. This ia tetraethyl lead dissolved in aa organic that tht public ia mdangered by tbe me of ihia fwL Comm bfomidc or chionda, such an ethyleor dibromide. Tbit queotly, a year ago mvmtigaiioole were begun at tbr requant advent ia alao toxic, and ethyl fluid haa until now been of the maaufarturera at the MasMchuwtta laatitirto d dispensed in small cylinder! sealed with a Un enp and punc Technology and Columbia Cnivemty, and mdependratiy nt tured by a spike when the cylinder w inverted mar an iron the Bureau of Mines. In addition, the ri--panj eooliemd cup on the delivery bom at the mrviro station. ita own research. Ooe iai-estigatioo allowed that the dm* m Ethyl gasoline ia the material used by the motor**. 11 the riemity of tht Grand Central Station in Xew York, proportion of tetraethyl lend to fWinf is from one in coo where ethyl gaa haa never been uard, eootaian mart lend thousand to one in fourteen hundred, a dilution which makes than dual from Detroit, where thia fud haa baaa m onee a perfectly safe nurture. Such gasoline haa been m publie two )vx Tbe Bureau of Mines has announced tbe trmih use for two yean and two hundred gallons have been of iu careful iaveatigaiion. during which morn than one bi dispensed by twenty thousand filling Mattons in twroty-tww died animab of various typra were trpuard to a drfinitn states without apparent mjury or toes of life. concentration of exhaust gaa from an eagiso using ethyl The products uf combustson contain lead compounds, gneotiae. care Heine taken to adjust the caHairetor to lower principally the oxide, murh of which remains in various tie content uf carbon monoxide to Im tliaa one half that pans of the engine and iu exhaust system, but a part of found in the average autucuohile exhaust- Variom eiamina which a thrown into the air. tiooa acre madr frura lime to time foe symptoms of lend Obviously, three are hasanls involved: these being, find, pornoing, such as colic, paraly-w. of appetite, and baa in manufacture; ncoed, ta diitrihuimti and handling; third, of weight, tbe ronditmo of tbe Uuud, and tha poisihdity of in the use uf the treated gmuhne; and finally, tie possible tored-up lead in vanous ImIv tWuea. After a pmod of haaard to the publie on account of the lead mm|nunds approximately eigfit molls' daily capuoufe to them rondi thrown into tbe atmosphere. What dues the evidence on tioos there o no indirals<e f lead fawniing. Tie snauab them haaavda mdirate* continued to grow and mature at a normal rate. One of thn CnqucstibueUy the manafartuie of tetraethyl lead is dog* gave birth to 6ve puppim. Throe worn rontmwd on haaardoue. The men engaged m Ibis wek are so informed test with the mother and is the rourw of the tart maturad and receive extra ramprwsatiua. Tlwtr condition is carefully normally. The alwrore of bad poisoning may be due to thn watched by phyainana. This type of differs from samll amount of bod pmcot in the ealiaust gae-aw mattwo. that of other lead rompnmidr m that the tetraethyl lead Furthermore, oUwrvatirms mads on man by'thn Burma d Mines showed that asst *4 tie bad in rtlaiiU lies newmg tact the puldir Mainsl the deadly rgho raanuh which fn*m ethyl gmuhna d ililwM again rvhahal. Tie; in* take* its frrquent victima. However, the me s nA Hnmd veetigatinn mdiratrw tlic danger *4 nflireal bad aceumub- and the ifixc-tgtstinn ia being rant inusd hy the Bums rf tmn m the slfccts ihnsigl the bwlt*rgr i4 scab frian autw Mmra aol otlwri equipfwd to wslwt mi httgintlrm BHiliib mnWaa |i tw s< minglT rmstr, The literature shows that lend is a sulAance tn he watched Wc fail t find nihsr, tletd'W. tn jietifjr cua tie* carefully. Legg* and Goadly, in one d the fulrertntirmnl casmnal ifcmand that re rmw ethyl gw4ine lr manufas* htedind Monograph Arm on bad pnasaung and bad ih tURd. Wc iwufuumfly Hint sorptim, stems the toxicity of all bad romfaamds and Adi that the rbvrlnpmcai 4 tf that lend coming m contact with the nrmhmnea of (larto economically hn|aotant rntw piratory system is far more dsngrnnu than nghid Val rtisie Imc nog tie lib <4 any Ckuft But in our inrestigaiion of pntrwtaal bad paisrmang fw tb one. and it iket not sftra the bluw lo those bmavni to point out that all pirnsring liae laew aerranpaoird Ah a luw of life. Tbe |wirw having now ben paid, and !>*** bamad whirh might nut lave bwn kwrord without it, nuukl it ont be fisOjr to dswnatmue the use .4 the material afire ueh aacnfirr? Wc ww no rra* public at Urge, bt ns not forget that there are many smarm After Dccemlwr 'JO. fires will Iw krated of bad dusts. Ws canoul singb cut tetraethyl bod hr nb tock but must Hrwwiihi tha me of bad paints m view af th-x-eatrenth fltmet a Due. Washingtnn. D. < Uw tlw wnwwewe d sire to call upm the It the data on the orrunrneo of bad in tha dust of the aiiingi city. We mould Ilr In urn a hrpr radar af thorn qualified tn conduct thomugh investlotions of the pomilility id bad* and w whea in Waal r^->-g bararae tnismutad in this particular prtidem, da offices ia the same Imi X4e the thrir work indtprudently, and nibmit their esita In ah impartial group far mxrpretntion. In the interim, tham ir*-l d the wetram arm u In nothing tn justdy the hysterical riatammt thnt un to diaruatinua tlw tw d we are threatened with the same fata whirh overtook thorn ethyl gasoline, for it hnsa ebon rorord m uw. If wo aadi tn m contact with the highly ranraoirated material H an nmtaare whare we wuuld do wet is keep om fart na thn do somrtliing really worth while, ht os find a way tn |- 352 etc 37150 kEPORT OC-33 APPENDIX VI 353 i 'nip. v rlf C*-* '''m dei/ahds fair play FOR ETHYL GASOUNE HvtUrim Should Not Bo Allowotf to Bor Thorough Toot of Product, Editor Soyo. CALLS FOR SANE OPINION Ion on Bolt of Burl M to Hoolth AtfvocottO 0/ Cor> <ill Prottuor. Dr. I. r, Pinnplp*. ^iter of Oirmleal MtUllyiftfll Cni;Brli|, appp^N to tiM rh^rntral lnduat7 ptalrrdar to demand flip play for eth*i. or leaded. ibmUi*. which u upd^r attack so % tu health. "On rhamhsal lAdutlrr." sai^ Dr. Ftfwttt, 'Van actftflf afford ta alt Idly hr nnd ' l<* with equanimity th raaaaJ manner in whirh-the fortunes of M of it# branches have been mdr-Jj throw into the balance by the hysteria f a nawtpaptr a4 a pkyftaloflat . h'batwtr th m*f1|g r dcawrHi f tnmethyl Wait and ethylteed guaattne, ha protucta should not ba summarily otndtmnad as a menace to health, nor should the manufacturers he plllerH aa IneraiMrraU prn/ltwrf. vllhaat a tiwh oughgolng investigation. "liia research and derojoptwM that predueH tetraethyl I>a4 were rofKrhrd In a fine spirit of industrial pf"n* looting toward the cnnwrv tlon of |i/- line ud ineteased efficiency of IMcm) rombastion fnntors- *H>e busbies* Iras no fly-br-night ventsre, aN Its krpva fcesards. were safeguarded ta Iba tow ar human ingenuity and ability. It* wn naiiha were negligible compared ta ha* man sacrifice in the devclnpmoat ad many ether industrial enterprise* "It Is little short of a calamity; therw fore, that the train of events nf the past two months has developed a public raw- i roverry w*f this product that has becw characterised by Inn--vpefcsrt and by** t-rical testimony. One ran Imagine how i`henkA) prefrees In the pest might hare been hampered by a similar erw- sade by self-appointed guardlans of the fublle health. <*tty gas and motor ea>ist at ill claim thsir victim* almost iiatly, hut escape the tender mlnlrlra- Con's ef the crusader. "What Is needed tn the present situa tion Is sanity and Judicial consideration., and for there elements we muet look to WASHINGTON. May DU PONT TELLS OF THE GAS. | Hi* Company Had Fatalities, bat Hag Lessened Dangers. 8ptvioi fe T%e Xrw York Tinea. WILMINGTON. DaL. OeC 30.--Death from poisonous gases encountered la the manufacture of motor fuels by the Standard Oil Company and the ptMsfbH* Ity of similar occurrences hers were commented upon today by Irtnde Du Tent. President of the . I. Du Pontd- Nemours Company. In sn Interview today he said that In' the earlier experimental stages of man ufacturing tetraethyl lead some aod derLa and fatalities had occurred, but when the experimental itace had been passed three accidents ceased. `Tetraethyl* lead..which the Du Pont Company la manufacturing on a com mercial- scale,** he said, "and which Is reported as the cause of the recent un fortunate accident at the Bayway plant nf the Standard Oil Company, should not be confused with ethyl gas. an im proved motor fuel which contains leas than one-tenth part of 1 per cent, of tetraethyl lead. "Tetraethyl lead Is poisonous and Its manufacture Involves risk, but no more o then many chemicals manufactured and used in enormously greater amounts. "The du Pont Company, during the experimental period, experienced much trouble with men becoming poisoned, even to the extent of fatalities. During the past year of production, when more than ion m*n have been employed con tinuously. the difficulty has diminished steadily. In the past several months, under full production, onlv slight diffi culties have been encountered. Experi ence has taught the necessary protec tion. both in plant ard medical care. "We find that workmen cumulatively poisoned by this material Invariably in dicate it in the incipient stages. before any harm Is done, by a marked symp tom. Doctors in the employ of the com pany i-ontinuaUy moke test on workara engaged In this process.** NgiV YoF?k 71MGS, Oc~roB&R 31, A baa on 1 sinidiiuastrryeetpwprarielelniUasdFeetnnncchitaal'Weuttmlidvv'7reeis**t*ps*h.oo*yffsW"itchiVao.nisa7a.*u~i<poenamutborUwnb'ltnwtlco-i *.^r'-If~Wlnn*a**and, 2SnJrgJ Although no evidence has been pem i. ... that lb. OMUii.hU.f- X tl u ^ parsonsWBBirB. FBI in- jury. . "The chemical industry has no desire to be either a nuisance nr a menace, bat It does want a suranee that it convicted by rIenl*acosomnmpaebtleentdeg,rWeeso!if forced (o abandon Its iegtttoiate ae, uits by misguided sonlots." Pth^ej_n_f_hoI'/'rJn_*Jt_gyA_na rt.hy,,aftf^.Tcwemulrrandemad..na1sunwtf_gahFeceartrouelluresttdaley.ttrfhOuiet-f -*-v fnNnredT sV> though believe* the majority wP eventually restered tu -------- *- health. i ETC 37151 REPORT OC- APPENDIX VI 35* \DANCEROUS LEADED GASOLINE (TETRAETHYL) SALE STOPPED AFTER FIGHT BY THE WORLD* 1 Corporation End* Trad* To* Day in Anawor to Appaal, Pandint Waatnntton Con* i foroMa an Poril ta Hoalth in tKa Eftytood FMd STATE HEALTH COUVCtL TO SIFT ISSUE TO-OAT TNCVAS WIDGiXY.it. Dr. YandaS Handaraon ol Yalai Took a Urfo Part m tha Crusado ^vTfY^rcxxHxirocxsSK1 r*.i+~** t, ck Tka Wettil mm kaklkOlyj * MrMUlt ___ttlw. ytMiao'at Mattie 1 MUM ml 10* roar* It la a nHk kaalUu tnnHM a at freak Ike BUrt UMim Ci aiae ! liiaItaly, kakfaiao ta4ay. Tkla tkW i at tka i at'tka oaay aao ta Ok ETC 37152 REPORT OC-33 APPENDIX VI 355 iVV.W*W <vr Toi*. PROF. HENDERSON I 'AUTO INDUSTRY PREY WANTS 1S. CURB OF LEADW POWERS ON DEADLY GASES 'SBtfARMblMY ` Prof. Handarton Say* IntaraatS IN ETHYL GASOLINELauding Successful Campaign* That Control Tatra-Ethyl Prod, uct Will Qrip Nation fay The World, He Points to Prof. Henderson Say* Thai HE FINOS BILUONS AT STAKE Gap in Safeguards to Health !$ in Prospect Xnr Hnn. Mar *---Prof.Mar TnM j Kendmon of Yale.' bead of the laboratory TETRAETHYL SALE AT END PENDING INVESTIGATION New Msvex May Yaodefl Header* i of Y*ie. bi^ of the labora tory of a *pUe| ph>M"btpV aatBrabdf |h* auhjre. uf ki*l*i g***Ime for au- IoimIuSc * ifae greatest I of applied physiology, said the subject if . traded gasoline .for autonvobOm "Is prob` obiy the greateat single question In the Reid of public health," aUi a statement to | the Yale News today. Dr. NIcolL Health Commit sloner, to Represent Now York Stato at Conference With a) of tetraethyl Itad(4 |U> lie* suspended throughout lb* cow try fNterdiy. u a result of the m* ads waged la the interest of pufelte health by Tha World, chemists pointed out the need of Federal leg* isletton to guard against just such a situation as has arisen In sale pf a product the safety of which is now In scJeottfle controversy* Though the Food and Drag Law of single qitNihe ui the field of puMic health." hi' * ruiomont to the Tale .V# r* to.*lay. lie Nhl that the >i* uf fii.aiH-Ml lni<t>H> involved la stupentiua "It u not s matter of mllUons or even hundreds of mitlfc'os. but lit erally of hUHittir* P~of. Iletideraon mhL in a portion desftti|itive \4 tit* preparation if lead-, eJ gasoline that. <c*vt in New York city and iu immediate neighborhood. It nan being uuroduced everywhere throughout the country as f*M ss It tan k supplied, lie elan said that it la now a>M "at little or no profit** and that the profit in the future will ron- aiet la control if the gaardlne hualnees and control of tbe automobile indus try. Frof. Henderson said: "The power er om)metiwe of i*r that hotda the pateata on tetru-ethyl laad mil he He Md the atse of Anaoctal Interests M j vulvrd "la stupendous. It la not a matter of millions or even hundred of nlHbna 1 but literally uf UUkss" Professor Henderson declared la par* * ifcm descriptive of the preparation at leaded gasoline mac. exerpt In New Yerk ' <lty and its Immediate neighborhood, h Win k ing introduced everywhere througB* in (hr country a* feet as tt ran bo np Hied. II*' iiKi aAperted It now is aold "M Utile ar no inii<ir and that tbe profit In the future njll i-omM to control uf Ibe gas oline liiminena and control of the *ttt^ iiHrlUle Industry. "The |a**wer ur <iti)iNnHtlwt of puwerw." hi- mud. "that holds the patents on tetre* (he fatted States Government pro tects the public against Impurities In food and drags, them la no law to protect agaJe*t danger in other arti tb* only au* that ml) k nMe to make I'srs that a* all mil buy. th* Improved r.irt for wImtH r w-iH tils- iard ihsoe m*w have. Thai ptwer mil iiiM cwuiml tb- only fuel on cle* of every-day commerce. whe-h itva* isrs Will run. The finan g^ib*Da sale twa Team cial -Make , le alrvaiet Iikviv*habl>' Local Health of&clala may bar the rthjl lend win Iw the.only one that vrfSI k .it)e to niaWe cars that we nD will want 1m i*u>. ibe Improved cars for which vlll discord those we .now have. That |to*rr will alsu iuntnil the only fuel on sbb'h Upiw rare will run. Tbe financial 1 Mtske I* fflntaffU hMnovitjiMjr yeti* ale of tetraethyl leaded gaeolbM nr other products dangerous or of doubtful safety, it is pointed out. but there Is no effective national agency to deal with the problem. Because of tbe lack of such an agency the Kthyl Gasoline Corpora In praising The World's campaign, tion has been able to sell Its product Prof. Headereoa called attention to for two years, although evidence the gap wbleh exists la the method favorable to It came chiefly from the of public protection against such company's own experiments and dancers. from an inconclusive investigation Columbia University. It was learned by the Called states Bureau of yesterday, has seat Its "progress ro- Hines. | port" to Burgeon General Curamlng. B*af*r**> Istft The W*H4 This term does not mono that the It continued selling the fluid after report rests on Incomplete selenitic sucb an authority as Frof- Ysndell data. Tbe flndlsgs are deflMta and Henderson of Yale had warned of detailed. What le lacking la a tabs the danger and after Drs. d*alt and latloa sad complete description st Drinker of Harvard had criticised the npwtneiu performed. The ro the method of ibe Bureau of Mines port deals only with the tUttfst at Investigation* It suspended sals the fluid as used la sitomobtlea, nod when Tbs World--aettna solsly as a net wtth eshsust fames or dlschargon private agency performing a public At n meeting of the State FiWa service, ss Frof. Henderson pointed Health Council here yesterday, D. out--began a cnasade to halt dis Mathias NIcolL State Health Coot tribution until the douht regarding missloner, was elected to sttead. tho safety had been cleared away and (WasblagtAa conference May 21 i when Columbia University experts - Since (be company has suspended found dilutions of tbe product highly : selev. the ceuarll took no action to dangerous. . ' bar the fleid in (his Piste. ETC 37153 ii i RPOKT 0C-d3 APPENDIX VI *56 ETC 37154 VI 37155 KEPOKT X-33 APPENDIX VI 353 i-eaaer 8pringft)d J.Uh 2 8 ms vhsievsr os th* iMfk*tt8| pottey ^MANUFACTURER REPLIES TO AN of that rorpontlon, an4 that, far from seeking to obtain any meaopto iy of the onto of ethyl imoiibo, the ATTACK AGAINST ETHYL GAS purpose* end policy were to license the entire petroleum Industry. At present. not only th* Standard Oil Company of New Jersey. but * auas- Cociidirmtioa of Public Health Should Have Bees Given, her of eompssttii both large e*4 Saja Statement--Makera Claim They Are 8eHing It mall. and la' a* way a**oclat*d ( Hh th* Standard OU Company of Wlthont Profit in Order to Introduce It. llaa.K*w Jersey, ar* HlllRf ethyl |s**< "Then* fact*. w* toiler*, ade quately meet the statement* made OfStfl for th# lilpMlIlK Of th*, rSe Ml lh#r#10f#r* almost -- by wDri. nHeenawda*raova ObeTatrnlaigg osa the | Hi! of .tnyl (ollno. (iMKinrll'.' k"ow" rt.mlc.1. to eaoolloo -oul, all**oe noaopollsllc parposo of the I at loaat. whir* hava h.. a.t, twa aaaafc. O__a__a_a__ra__l__H__o_t_a__r_a__C__a_r_p_o__rm___tl_a_a___a_a__O_the throuahoal tha Value Staua fcrl1 jth. EtRyl Oaoootla. rorporatloa. *>* poevllar lauuat ta a S! r<`*u'1 ** *lf*c*l* arT'*th#***r*c**5! 8SttaaandaarrCd OOHil fCaommppaannyr of !NCew Jer- J"'* -.'Ulilijjjjpebllehed MnV* aar. aa .tfacja* Utraaek tka athrl ihV .mommi.lldmtnr *aelaa buela.aa. wit* near* la m.nt of too attitude of th> r.rpor-j flt at Ion. made publta jo.t bo for. tha* tba ,h* battar `aobUa ladaatrp la uadoralandla* of tha D_r. Hend.a...r.e...o...a..s.......l..u.....t..t..m.......t..u.........c..o...n..#. rtnilAf th* attitude of tha Barbae ardor woo L...4, Th. at.ia.nt prabl.taa of aa1n. dr.lda aad tha of Mine*, on* enn drew only the aai l.ouni t.y Tbataaa Mlddl.r. Jr. pradurtloa af tnora .fflclootrodloo. tnf*renc* thnt h* wlehe* to tuantt air. pr...d.at aad ron.ral taao.prr aad bettor _motor .lu.La Th. .ole giatiiiotaly th* urtentlfte nrmo of of th. rorpofatlaa. a.nord, r. ovmn,nt..oPto . dldraetPbaod.ftt Kahlcdb dh. Ocareeraaml t*h** gofBas(, \tnhm* pprnomhttiyr th attach recently made on th* '/JJT wik wan *** haa new tone noeatlooed. corporalloa hr Prof. Tandrll M.a- ,>b ^,15! Jlfctt mV * Or- H.d.raaa wUhad lb. d.raon of th. dapanmrnt of applied I phr.lol.r. Of a1. Vr.lv,r.lty. p"0c'` PiJIEIriala MI o draw tha coaclaaloa Ibal .'"'`"bacauaa a part of lb. coat of a art- "Now Torb Bcwapapera rrctmlr could be added te caaaltae ta ac-n||flc iaaaatl,aa la defrayed b published if'dinn of the speech eCBpj|ii tha daetred raaolt It baa* sa industry which la interested la of Dr T*nri-lt/Hrndrr*on attsekiag ia4 hnra. no monopoly of tha |, tha roealta are to to regarded the RUtyl rudMtn* c'rpratinn. its mom 4rnctsat typ*e of meter* with suspicion. ho may with to *- produrfN.At^hhAider. method* of Whlehthin now feel will make pan- t*ia why It wa* that to btmeelf. dotn* business aad morals." th* siti*. indeed, ouch motors bar* beh eaaaeeeaafaliy sought a retainer statement said. 'Th* main topic of: |a pr Hn4raona spec* is, or should \ with apaelal faela tar many from the General Notora Corporator rmclas. aad aeronautical} uoa. te make each ea investigation, have keen, the coaaiderurion r ihej Uaad| eothkaer purrppoossees*. Ne basic pst*iOt8trti Motor* Corporatioe prefer- hassrd tn public heslth arising sat* oa such motor* ar* or eu b*|p*d to entrust such aa investigation from tha us# of *thly gaaolfno. If told by any company. to aa arm af the government than the statement had been eonfiaad **U may bo of lntr*at la this to a piivat* tnvesttgaor paid by it. 0 an esprrssloa of Dr. Henderson'* eonasctlotn to know thnt tha "Dr. Headetsoa 1* unit# right in opinion a nhl* subject there would h*ve h*ea so oceaeion for any etatement by tha Ethyl Oaaolina Corporation, nines Dr. Henderson's gm*a tor tho nlrshtp Bh*aandoabl etatlng that th* bustneaa of. the ar* of an effletont, high compr**-| Ethyl Gssoltn*'Gorpoirattoa la not aloa Packard aviation motor, and at present conducted 'at a profit, that the Shenandoah has for aoaa* Kelthsr waa there any hope of aa views o* tb<s point hava already been widely promulgated by hlmJ time past bean using, and 1* now using, ethyl ganelln*.,** totag the tmmadlaia profit ta tha rupandltures called'for by the year* of rs- The Ethyl Casoltna Corporation d4 fuel beat *utt*d for this typo of search work which the stockbold- ires, however, to make clear thsj facts concerning the other mattera ;tn eonnoctlotn with its huslnesaj vhkh war* di*eus*ed by Dr. Hea4| high afflclaacy motor*. Th* world'* speed record for automobile*, recently made by Tommy Ulltoa. tn California, waa obtained by tbo uas re of this corporation put tn. The Ethyl Oasolin* Corporatloa hope* mi believe* that It will at aoaso ume be able to conduct us buslncaa demon. "Pr. Henderson state* that | thal of ethyl gaaoltna. In a htgh-com^ at a profit, which profit, howwvcr. pre*s1an motor of another make. ' compared with the resultant sav- purpoa* of the Mnttreata' behind the! **>laay othar example* could M mg* of the puhite. the con* E'hvi Corporation tt.p produtiion of 1* to monopolise! motor ear* and| cited to pro** thoroughly vantage* ebtalaod by thb th* ad^ serration of gasoline, will ps laroauaa of atderable. It* atorhholdem do hope uel.^^tho uU of motor fuel. The facta arej m f*l io-: The product of the Elhyl| Ciinltnr Corporation la ethyl fluid th# ihmi<-l which, when added t ceeoMno la (he percentage of show one-ic-nth of 1 per cent, atopo th< d-tooei in* or 'haoek* which la *i j |b#n#>i< #g to a considerable eaten this fuel la such motor*. Such m iM-nefu in an indirect manner tor* ar* built by vartou* m*tor ard to the mm# extent to which the manufacturer* In no way associates with the Ethyl Oaaollae Corpora puMlc. th# petroleum Induetry. and tlon. the kuton^th Industry will all *Tha Standard Oil Compony of lenffit IhlVuKh the ennservatiun of Saw Jersey started on the mw *.,,tsr fuel. line of reeearrh work referred t* 1 when op#rations automobile motori |Uilrr rntfittons of hard aorrlce. as having toon Initiated by the Oea-i eral Motor* Corporation, somo two! ]The occurrence of this knock la , one important thing which has till fen year* later, *and followed this lino} of research ladepaadentty. but la' , a senerallon past prevented tha hutidins of more efficient ensine*. The General Motor* Cor do** cO'Operatloa wltb the Otniisl Motor* Corporation, until tho ansa mer of ifli At that ttaso, It van poration recosntsed this probien* eoacvlved to to not only to th* toot pome seven or eight year* ag* and larereat of the*# companion bt to started research in Its laboratorl** tha latsreot of th* moro vtpM at Dayton. Ohio, to determine the progr*** of this oogaomte Impfwoo- cause of this knock and any poa- ment -to merge those two llnao of athle means which might be used to effort, through tto *rgaaiaatlon of r..-t it aad thereby parmlt more tho Ethyl Goaollno Corporation effi. lent Mf* m h# built. The re-i the Oener.l Melon Cbepofhttou. bad swii sere* rear, of work *Jong>r*r,**1,r 1 v** antitihis line was the final discovery | ^ 1 hat the knwk as ca*uuas#ede hby* #e#e#r . sola of its ^ knock | tain combust ioa characteristic* of at tto time of the organIsaltaa of I gasoline, which^ as everyone knows the Ethyl Oaaotina Corporation, tto |ie the only fuel which may he relied Standard Oil Company of New Jer I upon K permanent and adeowat* for sey specialty stated that tto con the utmohlle. |r wa* furvher dls- nection with tto Ethyl dmUnt |r*'t>rol that th* addition of certain Gnrpcrsttoa wauld have no effeot, ETC 3T156 REPORT OC-33 APPENDIX VI i, / 7< o >' S-t0`7 THE NE VtK.i o*# Corporation. Glhnaa Thomp- ; hl#h-cr*rnpr**#ioii angi [SCIENTISTS TO PASS ft. iC-hh*aiirr*ma.n of MMIIccacnb InvveesaUti- ggUsa Commit!*: C. F. KhUrtflf. modnt; Thomas MlUjIey Mtw itriHMl: Do. Graham Ldiar, CbaailM. ftsrroo. be ir of bedfeog M to _ rapplr of tb landed S' olios wherwr K> If-avHa. It. h--a-* - -- W, n known^ tha-t-_h_igh ON TETRA-ETHYL GAS General Motor* Corporation. . _ compression fTMe'!f Inrnp*a4 the rfflet- HarvarJ t'oiveraiur. Dr. Joseph C. Imcy of rfthoUne. said Mr. Maxwell. Autk Medical bchooi: Dr. Cecil Brtnkec. | e only get 5 of * Pf w.t. ^ M . Pro?ee*aor of rhrsloloer: Dr. Dgvfd f gasoline under ordinary condition* ta- --------------------------- ;K4*]| School of Public Health; Dr. May. If complete combustion were_ oh- Washington Today toMit in u. c --. Alice Hamilton. Professor of lnd- Modi-''atnabte. on gallon of Caaolln* to a I ( Inf. Dr. Reid Hunt. FrehMOr of rbir- : .herKpoar n.otaf,, *mM drive aa * marology, automobile for I'd mile*. ' Ootormino Whtthor Its Ust John* Hopkins Uftl'*reJtr. Dr. W. M- "This great Waste of efflctoocy haa HoweU, Professor of Physiology. krhool been mtlurd for a lone time In tho Manaosa Public Hsafttu Of If)clew and Public Health; Dr. KU auteoiotltr Industry. Attempts have Marshall. Profe**>r nf Pharmacology. bc-t made to rmt^ly It with hiik<o<a* UHtoQ Institute. CrUeraltjr of Pitta* premiss engines. but, ahll# they o^ burgh, l>r. w. A. Grv*. Buraau of talned greater power par gallon from 1 Mine*: Dr. R. R. Havers 11.- aaroltfl'*. th. y alao Incr- aao tho MANY INTERESTS INVOLVED National Rraarch Council.. Dr Ludwig 'hiMrV` If the hlgh-empre*slo mature HecMoen. Chairman Dlvtjloa of Medical d*vriopr.] for ethyl gasoline were used *-irnr*n: R. W. Washburn. Division of with ordinary gasoline. the knock would , Chemistry and Chemical Technology. ' drive the platoo rtfht through the head Automotive Inductry Oeoply Cdft cirMd In Qucctlcn cf IU Cm* pleymant u Meter Fuel. Cpectol ro rh# .Yew Trk flnri. WASHINGTON. May lk.-Tbs confer* enca called by Kurgsoa Ooneyal Cummine of tha Public Health Service to ascertain whether tetraethyl fuoIlM b j dangerous to 1U oaera and handler will I be opened tonorrev and probably will |c*n*un*s all of that day and Thursday, National Safety Council. W. H. Ci-- eon. _ _ Navy Department. Bureau of Aenmas- llr, Lieutenant H. M. MuHInnia. Now York Academy of Modielna. Dr. Jamea B- Clemen*. , ,, . . Now York City Department af Health. Dr Prank J. Venae***. Cornndastener of Health; William H. Par*. Director Bureau of La beetori*e. New York BUta Department of Health. Dr. If. NlcolL Commissioner of Health; Prarvi* K Patleraon. Philadelphia Department of Ifeelth. Dr. C. M. Robinson. DlvUloa of Cheto- latry. _ ^. Srl^ntlflc American. Senator Khlpatead. Society of Automotive bngtoeem, Haro* Homing. S*vT*-iary. Bureau of Standard*. of tho cylinder. "The problem u to find *one way of makiac the combustion uniform* and ien. ao that It eaert*d a |HKh instead of a alap. The m h mrn i * at right up and down the line anonc <*' rhem* kal ami inej mn than 5.4'd com pounds. Final**. Mr Mtdgley dbfw- ereii the ffect of tetraethyl hat In making the e>ntbu*ilon eva and doing! away with tho flame-slap. \ *`Tclravth>l W^d Itad been known* rln^v but it ea purely a labora tory rurioaitjr with no known ueefuittru. Thetv u no nmethod of making It in quantity, end the price at flrat waa Pm a pound. Thu* led to further reaearrh vlth Ui aim ut making quhft tlty produriIon MPAwWllb. l*. I.V Stand, a_ rd j "1 Conj The fiorgooa General reiterated today that no. mailer what I,nq.ui.ries h_a_d___b_e_e"n i cuMaf.r Htr~7v>m>'anv of Indiana. Allan JartMA, Vlre^preapleot. ''standard Oil Company of New Jeraey. I made, he vw openmlf*ded ao (he mat* ' ^ ^ u John*, 0,1 Company of New Jersey made grvat etridea in this teeearrh. an<l_ the result aaa that that .umpanr nod the Gen eral Motor* '-ante r and formed ter and would govern hie Inquiry ec* t stale end Provincial Health Author!- the ISthr! .B^..|ine **.m|.,nv. **lt can be made ) clo' .pty now that .nr4tn(lr. H hJ4 >> rtncnlr tl. * MJ. *rm<rr .o-l Tlw- th.t If It rt.~!d b. found th. |(mudrt.k.r (<^rnor..lo,,. A. J. Cho- the eth>) gaenlinr can tw *o|rt st an liKnaor of otily thre- r-m a galVm tetraethyl gas waa delrterloue to the] it_e_c__p_n_*_t_ru_cUon .Hoepltal. Kr York public health, aocna subatltute ing the iama efficiency, but without any jCUy.'Dr. M. D. Touart ]j t^ntverrlty of Chicago, Profraaor C. * O. on orrftns'ry gasoline- Whll# It I* trwe that tragedh* liavc *--.'"urr.d in predoe. tax It, believe iliMt (he safeguards now in uee Muake it iM..i<ibl to pruduva bad effects, would be developed. l'nl-erstty of Wlemtn. Dr. l^wen- tt without great rK * Ail manner of laureate will be fepra- har*. profespor of physiology. ^ __ tinted whnr the conference start* work. Western Rraenre Medleal School. Cleveland. Piv-fresoe Gerald Sollman. Ineluding the automothra trufla. medical Yolo Vnlversity. W. H. Hscgard, laW arroclatlona. health commUsloaa. gaso oratory of applied physiology: Taaddl line manufacturera. unlvoraitlea which Henderson, professor of physiology; & A. Winslow, profrmor of public health. have roncemed themseivea with re search la cbnnrctloa with tho fuek tho Pees IIUIIoos of DoBssa Isvdwd navy and the chemical wmrfara acrvlo^ The scientists who will confer at Delegate Pipoet ad. Washington today with Burgeon Oe^ A Ust of the organlaallona and (hair eral Cummlng on the use of tHra-ethvt rrprrseataUves aapected follow: lead in gasoltna win have American Automobile Association, A. the fate of an Industrial devel< P. radsrlte. volrlng ''literally billions sf BoUara.** 1 Antertean Chemical bociety. Dr. D. C. according to professor YsndeO Homlrr Howe. son sT Tale, n landing opponent cf tho , American Ckrtn Chemical Bociety. use of the Colin C. Pink. Secrvuty. The efficiency of gnsoUne to oo gvontty American Federation of Labor. A. I* tnrrasssf by the addition of tetm-oCfcyf Berrea, Secretary Metal Trades Depart toad that It will bo unlversany ment: Mian Grace Burnham. Director wiU result In tbs general substltvMsn sf Workrra' Health Bureau. hlgtKomprrasIsn motors for those American Institute of Chemical Kn- In eatstenes. according to gineera. J. C. Olom, Seeretary. Hendsraen. providing the ose sf the lend American Medical Association, Dr. compound ie permitted. Such unlvamnl WUllam Puooy. Praaldena. use. the profeasor bolds, probably wonM American OB Campsny. Laster A. eaum widespread toad potooalng. which, ^Ameriran petrolruai Institute. Bnksrt in his opinion, to a wm dlasasn than tuberculosis. ^ ttrirh. berretary. While ihe tetra-eth>l lead ran he used American . iMMie Health Asaoclaflon, with a**anlBge In ordinary moists,.lha Dr. Henry Vaughan. Dr. leneral Motors Corporation, porihf fcqta-r. . .. . w | e a Mtxi ment made yaotenlay by A * Baltimore DepartBMat of Health. Dr. Maxwell, aatee manager of the Gthyl J. H. Hhmder. _^ . | Gasoline Corporation, to preparing to tn- I Hrown Cniverally. Prsfsaoor C. A- . iroduce portal motnra for the mesW I Kraus, ethyl or traded gasoline which will __ t'hrinical Warfare Ben-ice, S. B. the be-t mileage a callon of gwsollno wdl i Veddar. ___ _ give tndav. Mr. Msswet! said thoso bs- * Bureau of Chemtotry. Chicago, Com- irrertml In the product believed^iho S'd- nkiMtoner of Health. , _ entuts would find no cause m fear nay Cincinnati c,41eg% of Medicine. Dr. public health danger In its wee. Rnhrn A. Kehoe. ^ Introduction of special motors for aw otiku State ivpartmeni ofHealth. l)a ing the ethyl gasoline must waR, accwed- H l<- Hayhurat. _ Colunibta t'nlveratty. Haven Kmerwm Ing to Mr. Magweli. waitt the tmoled gasoline I* In general use. because tho Profri-.r ..f Publie Health: Frederick new hi*l-comprep*io motor* must bo B. FIinn, ivofmoor of rhysiology. , fueiel with ethyl gaenlla* only. The R. I du Pool de SVnMHjra A Caw trend <i _--_ wuf ..rdlnsry gas-JIno soon would Ju Pont. t\'. f. Harrington. I wreck Tho nwiohst itslag the 3S9 etc 3?157 Report OC--83 360 APPENDIX VII LIST OF GENERAL MOTORS CORPORATION PATENTS RELATING TO THE ETHYL ENDEAVOR ETC 37158 Report OC-63 APPENDIX VII 361 PATENTS RELATING TO ANTIKNOCK AGENTS As Assigned to General Motors Research Corporation U. S. 1,467,222, September 4, 1923, Fred E. Aseltine* Injector for antiknock agents. U. S. 1,501,568, July 15, 1924, Thomas Midgley, Jr. Aniline injector. U. S, 1,539,297, May 26, 1925, George H. F. Calingaert. Method for producing lead compounds. U. S* 1,544,922, July 7, 1925, Thomas Midgley, Jr. Ethylizer or fuel-mixing apparatus. U. S. 1,567,159, December 29, 1925, Brian Mead. Method for producing lead compounds. U. S. 1,571,862, February 2, 1926, Thomas Midgley, Jr. Prevention of fuel knock (aniline patent). U. S. 1,573,846, February 23, 1926, Thomas Midgley, Jr. Method and means for using motor fuels (first lead patent U. S, 1,575,436, March 2, 1926, Thomas Midgley, Jr* Method and means for using low-compression fuels (selenium patent). U. S. 1,575,437, March 2, 1926, Thomas Midgley, Jr. Method and means for using low-compression fuels (tellurium patent). U. S, 1,575,438, March 2, 1926, Thomas Midgley, Jr, Method and means for using low-compression fuels (arsenic patent). U.S. 1,575,439, March 2, 1926, Thomas Midgley, Jr. Method and means for using low-compression fuej.3 (antimony patent). U. S. 1,575,440, March 2, 1926, Thomas Midgley, Jr. Method and means for using low-compression fuels (phosphorus patent). U. S. 1,575,441, March 2, 1926, Thomas Midgley, Jr, Method and means for using low-compression fuels (cadmium patent). E:rc 3 7159 Report OC-83 APPENDIX VII 362 U. S. 1,575,442, March 2, 1926, Thomas Midgley, Jr* Method and means for using low-compression fuels (bismuth patent). U. S. 1,575,443, March 2, 1926, Thomas liidgley, Jr* Method and means for using lcw-coapression fuels (titanium patent). U. S. 1,575,444, March 2, 1926, Thomas Midgley, Jr. Method and means for using low-compression fuels (tin patent). U. S. 1,578,731, March 30, 1926, Carroll A. Hochwalt. Process of producing dialkyl selenides and tellurides U. S. 1,592,953, July 20, 1926, Thomas Midgley, Jr, Method and means for treating motor fuels ("solid" tetraethyl lead). D. S. 1,592,954, July 20, 1926, Thomas Midgley, Jr. Fuel (use of organic halides as corrective agents), U. S. 1,592,955, U. S. 1,605,663, July 20, 1926, Thomas Midgley, Jr, Motor fuel (phenyl lead patent). iiS1 November 2, 1926, Charles F. Kettering and Thomas Midgley, Jr. Motor fuel (second aniline patent). U. S. 1,605,664, November 2, 1926, Charles F. Kettering and Thomas Midgley, Jr. Motor fuel (naphthylamine patent). U. S. 1,622,228, March 22, 1927, Thomas Midgley, Jr. Process of making organic lead compounds. U. S. 1,622,233, March 22, 1927, George Calingaert. Process of producing alkyl compound of lead. U. S. 1,635,216, July 12, 1927, Charles F. Kettering and Thomas Midgley, Jr. Method and means for using low-com pression fuels (iodine patent). U. S. 1,662, 323, M arch 13, 1928, Thomas Midgley, Jr, Motor fuel (use of a volatile carbonyl of a metal other than iron). U. S. 1,662,355, torch 13, 1928, James P. Andrew. Bromine recovery (use of twice theoretical amount of chlorine). U. S. 1,668,022, May 1, 1928, Thomas Midgley, Jr. Motor fuel (use of halowax oil or halogenated lubricating oil). Report OC-83 APPENDIX VII 363 U. S. 1,787,419, December 30, 1930, Thomas Midgley, Jr. Method for using motor fuels (process patent on volatile compound of a metal). Trade-Mark 187,410, August 5, 1924. Ethyl. -|g - - ETC 37161 Report OC-83 364 APPENDIX VIII SOME SUPPLEMENTARY ILLUSTRATIONS TC 37162 PORT OC-83 APPENDIX VIM 365 ies New Compound Placed in AGED imi Gasoline to Add Power; TOB :otyper Tests WiOe Checked -Jita Practical use of the ethyl gas laboratories showed it to be high compound, developed at the Gen ly successful, it is said. eral Motors Research laboratory, Thomas F. Midgley, jr., one of to increase the mileage of gaso the men credited with originating n asked line and remove the "knock" is the compound, is supervising the ik Lamb, now being made by the Refiners tests conducted by the Refiners ier, who Oil Co., Sixth and Main sts. company. , ht in an The compound gives ordinary According to Mr. Midgley, L gasoline the features found now ethyl, gas in the gasoline -gives >out six only in so-called "high test" gaso greater strength to the mechanism ob on a line, it is said. It was held signif-. of a car especially when climbing ras cm icant that the price of the high hills ani in most instances elimi on the tost fuel dropped five cents in price nates the necessity of shifting of De Kalb Wednesday on the eve of the mar gears to make the grade. He also Mrs. Catha keting of the "compound" gasoline, said with its use the "knocks" are Hallman ved here, which is being sola at 25 cents a taken out of a motor, assuring " i auto in gallon. smoother riding. `bed into First sales of the gasoline con Refiners Oil Co. officials said <unt into taining the compound were made Wednesday should the ethyl gas severely, Thursday morning by the Refiners prove successful it will be installed , is being company. A check of all motorists at all of its stations which are laughter, using the fluid will be made to de located in 12 Ohio cities. The) reling at termine the actual value of the fluid was placed in 1000 gallons of: Dayton ar at the compound. gasoline at the Sixth and Main- Experiments conducted at the sts: station Wednesday afternoon No. 1 T oAytom 0/i*LY Ate/w. /, THIS HISTORIC ITEM ABOUT THE BEGINNING OF THE SALE OF ETHYL GASOLINE TO THE PUBLIC APPEARED IN THE DAYTON DAILY NEWS ON THE AFTERNOON OF FEBRUARY I, 1923. ETC 37163 CHAL.C . r . K: TTER I NG IN MORAINE CHr LABORATORY TIME THE ETH'_ GASOLINE FO nV-j. HIS OF L I CL AT THE IN 1924, ABOUT THE CORPORATION YAS ETC 37164 THQ/"S MICoLty, JR., A PHOTOGRAPH TAKEN A30 r he T I VIE OP THE DISCOVER-' >' TE'-AE ' -1 _ uE AD AS AiM ANTIKNOCK AGENT. ETC 37165 l?0: T OC-33 APPENDIX VIl DR. F. O. CLEMENTS (CENTER), /.HO /.AS TECHNICAL 'InECTO* 0T TL -E SEAR.' I LABORATORY FROM THE TI ME OF ITS ORGANIZATION by MR. KE*'E- N I 9it , THROUGHOUT THE PERIOD DURING >HICH EThyl GASOlINE .'.Ac Cl VE.O?' .. MJ V10 WAS ASSISTANT SECRETARY OF the GENE-AL .:.* o-C O'1 CAL COMPANY. THIS PHOTOGRAPH, ITH MR. KETTEhING ANT -'-v'L^i - ' AA S TAKEN IN 1939. D' 1 T* A* BOYD, A PHOTOGRAPH TAKEY ABOUT THE Time Oi- rHw ftORK >yt TETRAETHYL lead. ETC 37167 CA'RO- A. HOCHvVA'-T, a PHOTOGRAPH TAKEN A30UT THE T 1 '^E HE '.'.AS ASSISTING SO ET'ECTI V E L T IN THE CHEVICAl WORK ON TETKAETHTL LEAD. ETC 37168 I i '-ti ' CTURE OF THOMAS MI OGLE V, JR., C. F. Kt r"E-'`.G, ANO T. A. 30YD WAS TAKEN ON c"E3nUAr< ' , D.R!'i3 THE CELEBRATION AT VICGLEy's /.On Th- j-io, hove of the: twentieth a n \ i v r. o a * y :r t-e - -st sa^e qc ethy gasoline to "he rublic "-E ' C"JR E S SEEN IN THE BACKGROUND ARE ENlARGE- OF SOVE OF ~l~OSE INCLUDED IN This `'IS'OkY. ETc 37169 X 3- .IfVUC ! A * 3* MI DGL: * AMO FRED L. CHASE, P-O 'UGAPHD TOGETHER ON rEBRUARV 2, 194 3. CHASE AAS THE HAN HO THAT OAT BACK IN 1917 GAVE vidglev the iooine, ahich turned out to BE THE FIRST ANT I KNOCK AGENr, rTH THE SUGGESTION THAT IT OUGHT TO C YE KEROSENE THE RED COLOR HE RANTED. ETC 37170 REPORT o: PE ID U VIII ill STANDING 3ACK. OF MIDGLEY AND MR. KETTERING IN THIS GROUP, GATHERED AT MIDGLEy'S HOME ON FEB RUARY 2, 1943, FOR THE ANNIVERSARY CELE8RATI ON MENTIONED PREVIOCSu*, ARE, FROM THE LEFT, A. M. MAXWELL, OR. ROBERT A. KEHOE, EARLE W. WEBB, AND GRAHAM EDGAR. ETC 37171 -'l?3kT-0C-33 append IX V I M 3 74 BEHIND M I OGLE V A,-' \`R. KETTERING IN THIS PICTURE, ALSO TAKEN AT MIDGLEY'S HOME ON FEBRUARY 2, 1943, ARE THE FOLLOWING, READING FROM THE LEFT I HARRY MACK, CHARLES A. THOMAS, DR. R08ERT A. KEHOE, N. D. S I EBENTHAi_ER , JOE W. MORRISON, GRAHAM EDGAR, CHARLES P. HARDING, ROBERT JORDAN, AND CARROLL A. HOCHWALT. etc J REPORT OC-di appendia VIII '7b EtC Jit!3 j. :o- ETC 37174 :> APPE'CIX. V ! i ! ANOTHER CONTEMPORARY V . EV\ OF THE FILLING STATION OF Tr REFINERS OIL COMPANY AT SIX'* AND 4AIN STREETS, DA'CN, OH C, IN WHICH ETHYL GASOLINE WAS FIRST SCLC TO THE PUB-IC. the PUMP from WHICH ETHYL GASOLINE YAS DISPENSED IS SECOND FROM THE RIGHT. TC 37175 -_30k'' GC-si APPtNClA VI l I 1920a : ^plane in ahich, on February 27, , vaj. r. a. schroeeir ascesced 'ax mccook field a-.? hade an altitude recod of 36.020 feet, nearlt 7 2i.es, USING GASOLINE CONTAINING XYLIOINE AS ANTIKNOCK AGENT. this aas * lE ere a-53 biplane, powered bt a liberty engine, it is understood *0 HAVE BE-. J *H. FIRS' AlRP-ANE IN THE UNITED STATES TO BE EQUIPPED ' A TURBO-SUPERCHARGER, THE S JPERCHARGER HAVING BEEN MADE BY THE GEN EVA- ELECTRIC COMPANY. THE XYLIOINE, furnished BY UI OGLE ', AAS FOm;0 NECESSARY -0 PLi.i KNOCK AND PREIGNITION UNDER ThE CONDITIONS OF SUPER- C-A GE ACQUIRED for The -"light. This PICTURE AS 06 t A | NEC rHROLGH fh Ki.'.SNESS OF 14AJ. G. l. A. HALLETT, whO, AS CHIEF OF Th POWER PLANT SEC- T 'N.-.OOK FIELD, AT THE TIME OF MAJ. SCHROEDER'S FliChT, HAD MUCH TO :0 ITS S JCCESS. ETC 37116 Report OC-83 379 CONTENTS FOREWORD Page CHAPTER I THE BEGINNING........................... . . .f Charles F. Kettering organizes a new research laboratory* Dr. F. 0. Clements selected as its director * . . Thomas ilidgley, Jr., first member j)f the staff ... First research on knock r. ...... First engine indicator and indicator card .*..*. First theory of knock.................................. . ...... Iodine, the First Antiknock Agent ...................................................... Unsuccessful effort to duplicate with dyes ....- 127 North Ludlow Street .....................................................................' . H. C. Mougey, second member of the staff ...... I 1 1 2 2 3 3 5 6 6 8 CHAPTER II THE WORLD WAR--AND "HECTEH".................................. Aid enlisted by Bureau of Mines and U. S. Army .... All available fuels surveyed ............................................... California gasoline recommended as aircraft fuel ... Research on cyclohexane begun ............................................... ....... T. A. Boyd begins work on cyclohexane . . ............................ Service tests of Hecter (cyclohexane fuel) ..... Report made on joint fuel research with Bureau of Mines 13 13 14 16 16 18 22 23 ETC 37177 Report OC-83 CONTENTS Objectives and general description of fuel research i The men who worked on cyclohexane 4;.....* Injury to Uidgley's eye . ........................................... ...... Kerosene-benzol blends tested as automobile fuel 444 Other Events of ths. War Period . ..... 4 . 4 4 Tests of other possible antiknock agents 44444 Midgley Indicator Improved and Manufactured for Sale .44 Uidgley indicator booklet prepared . Longstreth Hedal of Franklin Institute to Uidgley . 380 Page 25 27 28 30 30 31 33 35 35 CHAPTER III SEARCH FOR AN ANTIKNOCK AGENT RESUMED * Methods of selecting compounds and testing them 4 * 1 Water as an antiknock agent .`....4.444 Hydrogen peroxide, the first knock inducer ..... The Aniline Discovery....................................................... .... How aniline saved antiknock search from being abandoned. Effectiveness of aniline as an antiknock agent. ... Bad Luck on Lead in 1919 ... Plan to test compounds of the various elements ... Experiments on Cracking ............. Iron selenide as cracking catalyst ....... Antiknock Agents Furnished to Others for the First Time . Kettering's priming fluid .......................... ..... Efforts to prepare cyanand.de............................................................. Prof. W. C. Ebaugh joins Fuel Section for summer ... Diphenylamino found to be antiknock agent . < , . . 36 36 37 37 38 40 41 42 44 44 46 46 47 47 48. 48 - __. , jr ` ETC 37178 Report OC-83 CONTENTS 381 Page Profs. Y/illiam McPherson and C. E. Boord ...< t 50 Alkyl amines as antiknock agents . . * 50 First Work on Decarbonizers ......................................... 51 Aniline as carbon remover ..............................................................*52 Relative antiknock effects of aniline derivatives .... 52 First Cooperation with du Pont.................................................................... .54 Contract with du Pont for combustion research .* 55 The Detonation-Wave Theory of Knock..............................................................55 Paraffin hydrocarbons tested for knocking behavior. . . 56 Relative knocking behaviors of benzene, toluene, and xylene. 56 A Temporary Change in Objective . ............................................. 58 Efforts to use high-boiling fuels............................................. . 60 . Water as an Antiknock Agent ............................................................. ...62 Charles P. Harding begins work in Fuel Section ..... 63 First Use of an Antiknock Agent in the Army Air Service ... 63 Altitude flight of Maj. R. W. Schroeder . . . ... .63 First detonation-tube experiments ....... . 64 CHAPTER IV AFFILIATION WITH GENERAL MOTORS AND MOVE TO MORAINE CITY. /. 65 General Motors Research Corporation formed ..... .65 Expenditures of original laboratory on fuel research ... 69 Vegetation Investigated as Possible Source of Motor Fuel . 70 Literature study at Yale University . . .-* 70 The Aniline Injector . . .. . .................................. ...... ... .72 Injector and other problems *dth aniline..............................73 First Plan to Market an Antiknock Agent . . . . . . ... . .74 | ":rr Tin* Report X-83 CONTENTS 382 Page Injector for airplane engines ... 74 Sale of Antiknock No. 1 to Army and Navy . . . 75 Dark Hour Before a Break in the Clouds 76 The odor problem with aniline 76 Question about further pursuit of antiknock research . * 77 CHAPTER V SELENIUM DISCOVERY OPENS NEV7 FIELD . . . . 78 Selenium oxychloride......................................................................................... 78 Mr. Kettering's story about selenium oxychloride ... 79 Diethyl telluii.de and diethyl selenide made and tested 83 - Miscellaneous Events of 1920 and 1921.......................................................84 Tests preceding crankcase ventilation .... 84 Making compounds for Eastman Kodak Company.................................. 84 First contact with the gumming of gasoline ..... 85 Further Work on Selenium and Tellurium .... ..................... 87 Investigation of possible supplies .................................................. 87 Tellurium poisoning, or odor.......................................... 88 First High-Compression Car--"The Goat" ......................................... .90 Its performance and fuel economy ...................................................... 91 The Periodic System Becomes the Guide.................................. 91 Bouncing-Fin indicator Developed.............................. '95 Experiments with temperature method............................................... 96 Bouncing-pin suggested by experience of Dr. Dickinson . 96 Bouncing-pin developed as quantitative instrument ... 99 Place of bouncing-pin in later knock-testing procedure 101 *,, ETC 3?180 Report 0C-S3 CONTENTS. 333 Finding the Feriodic Function of Antiknock Effect . . . . 104 Chemical elements of interest 104 Compounds tested . . . *............................................... 105 The peg-board .......................................................................................... * 106 Results on tin point to lead ................................................* 106 CHAFTER VI THEN CAME LEAD........................... ...... . . 108 The first engine test of tetraethyl lead........................... ...... 108 Effectiveness of tetraethyl lead compared with that of aniline........................................................................... 109 The periodic effect of the antiknock action verified . . 113 Early Contacts with the Standard Oil Development Company ... 117 Frank A. Howard visits Hr. Kettering in 1919............................120 Howard employed to organize laboratory for Std. Oil Co., N. J........................................................................................................................121 The SpectroscopeApplied to Studies of Combustion ........................... 122 Further Aid to the Anqy ...... .. .. ... 122 Diethyl selenide and other antiknock agents supplied to Array ..................................................................................................................... 123 Intensive Research on How to Make Tetraethyl Lead ............................ 123 List of the several methods of synthesis tried . 124 Zinc ethyl method selected for intensive investigation. 125 First plans for commercial-scale plant......................... ...... . 126 The Participation ofM.I.T. Begins .................................................................... 131 R. E. Wilson enters the lead endeavor .................................. ...... 132 Electrolysis of acetone with lead electrodes, first re search at U.I.T............................................. ...... 132 Report OC-83 CONTQJTS 384 Page The Executive Committee Asks for Some Information . * . . . 133 P. S* du Pont writes Mr. Kettering .... ..... 133 Response by Midgley............................................... 133 CHAPTER VII THE SODIUM-LEAD METHOD OF MAKING TETRAETHYL LEAD i . 134 Events causing change from zinc ethyl to sodium-lead method ..................................................... 134 Procedure using ethyl iodide and sodium-lead alloy . . 136 The"deflagration" difficulty ............................................................... 137 First successful substitution of ethyl bromide for ethyl iodide.................................................................................. 137 Contact with Dr. E. E. Reid . . 139 Dr. Reid's visit to laboratory and laterrecommendation 139 The First One-Gallon Lead Plant ............................................................. . 141 First run a success .................................................................................... 141 Work on designing plant to make 100 gallons.per day . . 143 Near-catastrophe with ethylnitrite . '... ........................................ 145 Conclusion of Effort to Make Tetraethyl Lead by Electrolysis of Acetone .............................................................................................................. 146 Attempt to Substitute Ethyl Bromide for Ethyl Iodide .... 147 Pyridine found most effective as catalyst . . . . . . 147 Du Pont Cooes in on' the Manufacturing Problem.................................. 148 Messrs. Harrington, Bolton, and Calcott visit -the lab oratory .................................................................. .... 148 First experiments at du Pont successful . . .... 149 Changes in Research atU.I.T...................................................................... ...... . 149 George Calingaert begins lead work......................................... 150 3" .i i ;v ETC 37182 w Report 0083 CONTENTS 385 Pago A Conference Brings Some Changes . * * t . . * . . 150 Decision to divert to du Pont experiments on manufacture . 151 CHAPTER VIP PROBLEMS CF USING TETRAETHYL LEAD INVESTIGATED * * .152 Tests of lead compounds other than lead tetraethyl . ; 153 Effectiveness of tetraethyl lead found to vary with mix ture ratio ................ 153 First matching of gasolines with tetraethyl lead .... 153 Discovery that effectiveness does not increase directly with concentration.......................................................................................154 Tetraethyl lead found more effective in some fuels than in others.............................................................................................................154 Ratings of benzene, toluene, xylene, and ethyl alcohol . 156 First Studies on the Stability of Tetraethyl Lead in Storage 157 Observation that in dark decomposition did not occur . 157 Search for means of making tetraethyl lead stable in light. 15.8 First Work on Spark Plug Corrosion and Exhaust Valve Deposit Prob lems ............................................... 159 Nature of spark plug and valve difficulties .............................. 160 Search for corrective agent begun ............................ ... . 161 Chlorine and bromine found effective ........................... ... 162 Status of lead research in August, 1922 ....... 163 First Attention to Possible Health Hazards. . ... . . 164 R. E. Wilson consults Dr. Reid Hunt ........ 164 Dr. Yandell Henderson gives views and offers to study problem 165 / Other Events During 1922 . . .......................................... ... 167 Uidgley makes "solid" tetraethyl lead ....... 167 Report OC-83 CCOTENTS j86 Page Lead compounds sent to George Oenslager at Goodrich . , . 168 Parallelism between vulcanization accelerators and anti knock agents . 4 . . . . ....... . 168 Nickel carbonyl and triphenyl bismuthine ...... 169 Raritan Aniline Works attempts sale of aniline to public ; 170 Complaint that tetraethyl lead damaged carburetor float* * 170 Sun Company orders 10 gallons tetraethyl lead . . * * * 170 Midgley demonstrates tetraethyl lead at White Sulphur Springs.................................. ................................. 1 ..*1t 171 CHAPTER IX THE FIRST PAPER ON TETRAETHYL LEAD .... Invitation to give paper before Am. Chem. Soc. accepted . Pains taken to prepare a paper in proper scientific form Supplementary paper on application of chemistry to fuel conservation........................................ * Detonation-tube experiment improved for presentation The near-failure of the presentation by an accident to the engine . Midgley*s lecture and demonstration a marked success * . Important after-effects of presentation and publication , 172 172 173 17h 175 176 179 179 CHAPTER X WORK ON EXHAUST VALVE AND SPARK PLUG PROBLEMS RESUMED . . 181 Corrective agent put directly into tetraethyl lead molecule 181 100-hour test of lead triethyl bromide . .. . . . - 182 Search for other corrective agents continued .............................. 183 ;,r ' . - V V;-V- .'-jU: - ETC 37184 Report OC-83 ccwTerrs 387 Sale to the Public Decided Upon .............................................................. Miscellaneous Events During Fall of 1922 ....... Method of making lead triethyl bromide developed . . . Experiments on the stability of lead triethyl bromide. , Visit of du Pont men regarding gunpowder ...... Charch's program at The Ohio State University .... Spears and Riddle ask to be distributor of the new product Letter from F. E. Moskovics.................................. ...... ... Progress in manufacture at du Pont ................................................ Further Report of Work at M.I.T............................................................ Work on diplumbic hexa-ethyl . . ................................................ Examination of spark plug deposptiT~. ~T ...... The Toxicity Problem Again ............. Letter from Dr. Erie Krause. ..... ............................ Letter from Surgeon-General Cumming to Mr. du Pont . . Reply to Mr. du Pont's letter .. . ................................. Plans for investigation at Bureau of Mines .. .. . Nichols Medal Award to Uidgley .......... Other awards received later .............................................................. . 184 . 185 . 185 . 187 . 187 . 187 188 . 188 . 189 . 189 /* . 190 . 190 . 190 . 190 . 191 . 191 . 192 . 193 . 193 CHAPTER XI SALE OF ETHYL GASOLINE TO THE PUBLIC BEGINS . . . 195 Selection of the name. Ethyl Gasoline ... 195 Refiners Oil Company first distributor ...... 195 Composition of first ethyl fluid .............................. ..... 195 ETC 37185 Report OC-83 CONTENTS 388 How the public reacted at first to Ethyl Gasoline . * . . , 196 Record kept of each sale . . ................................................. 198 Volume of daily sales at first . * * ....... . 198 Car test of tetraethyl lead plus carbon tetrachloride . . . 200 First Change in Formula , . . ........ . . . 201 Use planned by Yellow Cab Mfg. Company ...... . . 201 Nichols Medal Conferred ................................................................................. .... . 202 Efforts to prepare the medal award paper 202 Matter as prepared eliminated for patent reasons ............................ 203 Events on evening of presentation . . . . .. . .... 203 Personnel of Fuel Section, April, 1923 ... ..... 204 CHAPTER XII GENERAL MOTORS CHEMICAL COMPANY-............................205 The new company organized and incorporated.. . ..... 205 First set of officers .................................. ...... ................................................. 205 Decision to begin making 100 gal. tetraethyl lead per day . . 206 Efforts to get additional distributors .................................................... 206 First Knowledge of Research on Lead at Standard of New Jersey * . 206 The research of Kraus and Callis on making tetraethyl lead . . 207 First suggestion of union with Std. Oil Co., N,J7 . . . VT207 Standard of Indiana Becomes First Large Distributor ..... 208 Part played by R. E. Wilson .................................................................... ......... 208 Wilson and Midgley visit filling station in Dayton .... 208 Exclusive contract taken by Standard of Indiana ............................ . 208 Report OC-83 CONTENTS 389 Page Sales of Ethyl Gasoline extended to Cincinnati . . . . 209 Spears and Riddle become distributors................................................... 209 First Efforts to Measure the Lead Requirements of Gasoline . * 209 Advertising of Ethyl Gasoline Begins ... ........ 211 The Ethyl emblem designed .............. 212 Mixing Meters or "Ethylizers"............................................................... ... 212 Second model of mixing meter ........................................................................... 21$ Third model of mixing meter ............. 219 Arrangements under which mixing meters were furnished ... 219 The first Ethyl fluid blending plant.........................................................223 Automatic can-filling machine developed ............................................... 223 Poisoning of workers in blending plant ................................................ 223 Dr. Xehoe begins work on poisoning problems.................................. ....... 226 Bulk mixing meter............................................................................................ . 226 The "tourist ethylizer" .. .. ... .. . . . 226 Proposal to Dye Ethyl Gasoline...................................................................... ...... 228 Advantages expected from it....... ............................ 228 The Problem of Stability in Storage ..................................................................229 Pressure develops in containers ........... 229 Some containers burst .........................................................230 Search for stabilizing agent ............. 230 Trichloroethylene substituted for carbon tetrachloride in mix 231 Further Work on Decarbonizers ................................... 231 Some decarbonizing mixtures patented . . .' . . . . . 231 Decarbonizer experiments at Yellow Cab Company ...... 231 ETC 37187 Report 0C-S3 CONTENTS 390 Page More About the Research at M.I.T................................ * * . . . * 232 Alkyl cyanides found catalysts in tetraethyl lead synthesis, . 232 Men working on lead investigation at M.I.T, in 1924 .... 233 CHAPTER XIII CONCLUDING WORK ON EXHAUST VALVE AND SPARK PLUG PR0BLE3B . . 234 Intensive tests conducted in battery of twelve engines ... 234 Superiority of bromine as corrective agent established . . . 234 Belief that not enough bromine could be had.........................................233 Effort to improve the effectiveness of chlorine ..... 235 Experiments at Dayton Power and Light Con?)any.................................. 236 Dr. Wilder D. Bancroft Retained as Consultant . . .... . 236 Composition of combustion products studied ....... 236 Dr. Graham Edgar Arrives........................... ...... ....................................................... 237 Dr. Edgar gives first attention to valve and spark plug problems ,'............................................. ..... 237' Bromine supplies found greater than expected . . ............................ 238 Corrective agent changed to ethylene chlorobromide .... 238 Decision to go over entirely to bromine as corrective agent. . 239 Concentrations of corrective agent used .................................................. 239 CHAPTER XIV THE FINAL SEARCH FOR BRddNE ...... 241 Results of analysis of available supplies ... ..... 241 Delegation visits Dow Chemical Company .... .... 242 Sea water proposed as bromine source, but thought impractical. 242 ETC 37188 Report OC-83 CONTENTS 391 Midgley's first scheme for getting bromine out of sea water . 243 Intensive research begun on extracting bromine from the sea 243 Aniline proposed as combining agent..........................* . * 244 James P. Andrew proposes using two theories of chlorine . 244 Tribromoaniline found effective as corrective agent . . 245 Patents on extracting bromine from sea water 245 Du Pont Builds Semi-Works Plant to Extract Bromine from Sea Water 245 Mr. Kettering hunts bromine in Tunis .... .... 246 Dead Sea considered as a possible source of bromine ... 246 Salt water from Mexican oil wells considered ................................ 246 Contract made with Dow for ethylene dibromide........................... ...... 247 The Good Ship Ethyl ............................................................................ ...... 247 Voyage of steamship Ethyl and results of it.................................. 248 Dr. Dow Overhauls His Bromine Process ........................................... 250 Ethyl Gasoline Corporation and Dow conduct joint research. . 251 First Bromine Plant at Kure Beach ...... .... 252 Charles A. Thomas collects samples of sea water ..... 252 The Ethyl-Dow Chemical Company ....... ..... 253 Pilot plant proves successful and full-scale plant is built 253 Enlargements of bromine plant ............................ ...... 253 Another bromine plant built on Gulf of Mexico ..... 253 Attention of the Army is called to the bromine plant ... 255 Brief Description of Process for Extracting Bromine frpm Sea Water . ...........................................................................255 ETC 37189 r- Report OC-83 CONTENTS 392 Pag CHAPTER XV THE ETHYL GASOLINE CORPORATION ..... 257 Standard of New Jersey begins to distribute Ethyl Gasoline , 257 The Ethyl Gasoline Corporation incorporated . . . . . 257 Principal items in agreement ...... ............................ 258 Directors and officers......................................... ...... .. 259 Earle It, Webb succeeds Ur. Kettering as president .... 259 Agreement with du Pont on supply of Ethyl fluid ..... 259 Manufacture of tetraethyl lead by ethyl chloride process ' begun.................................. ...... ..........................................................................260 Research laboratory of the Ethyl Gasoline Corporation ... 260 The Ethyl emblem modified 261 CHAPTER XVI THE HEALTH HAZARD QUESTION ...... 263 First investigation of engine exhaust ........ 263 30-day test conducted in the Research garage ..... 264 The Bureau of Mines Investigations 264 Persons participating in Bureau of Mines tests ..... 265 Plan of the investigation .. . ......... 267 The conclusion reached . .................................................................... ...... 268 The second Bureau of Mines agreement ........ 268 The Bayway Episode ........ ........ 270 The extensive newspaper publicity . . . . . .... . 271 Uidgley and Maxwell visit Jiealth boards 272 Use of small ethylizers discontinued t...... 272. `V ! Report OC-33 Curran'S 393 Bureau of Mines issues memorandum.. .... . ... . . . . 272 Attitude of technical press . .. ........... .. . . 274 Campaign by New York World and Yandell Henderson ..... 274 The Surgeon-General's Conference .................................................................... 274 Sale of Ethyl Gasoline is voluntarily discontinued .... . 275 Those who attended the Surgeon-General's conference .... 275 Dr. Alice Hamilton accuses Mr. Kettering ....... 276 Resolution adopted by the conference . ................................... 276 Investigation by the Surgeon-General's Committee of Seven ... 277 Members of the Committee of Seven .............................................................. 277 Mr. Webb offers cooperation........................................................................... 278 Men who conducted the investigation ................................................ . 278 Method of the investigation .................................................................... ....... 279 Reports of the Committee of Seven and the Bureau of Mines . . .. 280 Conclusions reached.................................. ...... .................................. . 281* Official report of Bureau of- Mines ......................................................... 281 The Surgeon-General's Regulations .. ................................................... 282 Limit set on cc tetraethyl lead per gallon ..... 282 Sign for filling station pumps .................................................................... 283 Investigation of possible lead hazard continued by Dr._Kehoe 283 British investigation of Ethyl and their conclusion .... 284 CHAPTER XVII "ETHYL IS BACK* . . Ethyl Gasoline recovers from tribulations nQ Brand" is introduced . . . . . . . . . 285 . . . 285 . . . 286 ETC 37191 Report OC-83 CONTENTS 394 Page Schedule of reduction in prices of Ethyl fluid ............................ 286 Ethyl is put into third-grade gasolines .................................................. 287 Ethyl in Aviation...........................................................................................................287 Part played by S. D. Heron . . ................................................................289 Large contribution of Ethyl to aviation gasoline ..... 289, Iron Carbonyl .................................................................... ...... ................................. 289 Nickel and cobalt carbonyls as antiknock agents.................................. 289 Mr. Kettering goes to Germany at reouest Badische and du Pont . 290 Badische makes iron carbonyl as by-product ......................................... 290 Tests of iron carbonyl at Dayton and troubles experienced . . 291 Corrective agent sought ......................................................... ...... . . 291 Visit of Doctors Mittasch and Cunradi from Badische .... 291 Interference in Patent Office and how resolved .................................. 292 Later tests of iron carbonyl by Ethyl Gasoline Corporation . . 293 Iron carbonyl sold commercially in Germany.....................................* 294 Complaints ....................................................... 294 Service bulletins and primers .. ............................................................... 294 Use of Ethyl Gasoline finally approved by car makers .... 295 Difficulties in Airplane and How Overcome ........ 296 Historic paper by S.D. Heron ... ........................................................................ 296 Patents ....... ................................................................ 297 Conclusion 297 Midgley lists effects of the Ethyl development . . . . . 298 Report OC-83 CONTENTS 395 Page APPENDIX I ......................................... Extract from Report of May 15, 1920, Entitled "The Motor Fuel Problem." 300 APPENDIX II......................................... 303 Cost of Fuel Research from July 1, 1917, to February 29 1920. APPENDIX III ........ 307 Copy of Letter Written to Charles L. Reese of the Du Pont Company by Thomas Midgley, Jr., June 9, 1920 Views then on the use of aniline as an antiknock agent . . 308 Estimated amount of aniline needed . ............................................... 309 Possibility of finding a better antiknock agent. .. . . -. 310 APPENDIX IV ....... 312 Partial List of Compounds Tested in the Search for an Antiknock Agent Materials found to suppress knock ...................................................... 313 Materials found to be without effect ............................................... 317 Materials found to increase knock . . . ... . . ... 322 APFENDIX V . 323 Summary Report on the`Investigation of the Spark Plug Corro sion and Exhaust Valve Deposit Problem The problem to be solved......................................... ...... 324 Summary ofresults ...................................................................................... 324 The methods used 325 Supplementary methods of test............................................................. 327 Results of engine tests........................... ...... . List of materials tested . . . ..... . . . . 329 341 Report OC-83 CONTENTS 396 Page APPENDIX VI 347 Representative Items from the publicity About the Bayway Poison ing Episode APPENDIX VII 360 List of General Motors Corporation Patents Relating to the Ethyl Endeavor APPENDIX VIII 364 Some Supplementary Illustrations ETC 37194 Report OC-83 397 ILLUSTRATIONS Figure Number Pago 1 Typical indicator cards taken with the Midgley optical indicator.................................................................................................... 4 2 Approximate chronology of events in the search for a practical antiknock agent ............................................................. 7 3 Building in which iodine, the first antiknock compound, was discovered.......................................................................................... 9 4 The first research laboratory at 127 North Ludlow Street, Dayton ... 10 5 Deleo-Light engine at 127 N. Ludlow Street, with early model of Midgley indicator............................................. 12 6 One-cylinder Liberty engine used for testing aviation fuels during the Y/orld War...................................................... . 7 Suggested design for the wooden medal which Dr. Leo H. Baekeland promised Mr. Kettering if he could make a pint of cyclohexane............................................................ 19 8 Small-scale plant for making cyclohexane by hydrogenating benzene ....................................................................................................... 20 9 Damaged pistons and connecting rod from a high-compres sion Liberty engine after running on a knocking fuel 24 10 Thomas Midgley, Jr., and the final form of the Midgley optical gas engine indicator 34 11 Copy of the page in Laboratory Record 8 on which the discovery of aniline as an antiknock agent was recorded 39 12 Organization chart, Research Division, Dayton Metal Products Company, suzsner, 1919........ 49 13 Chart showing relative antiknock effects of various derivatives of aniline........................................................ ...... 53 14 Personnel and work assignments. Fuel Department, November, 1919....................................................................... 59 15 Building occupied by .General Motors Research Corpora tion at Moraine City........................................ . 66 16 Layout of Fuel Section space in the laboratory at Moraine City ............... 68 ETC 37195 Report OC-83 ILLUSTRATIONS 398 Figure Number Pag 17 Contemporary news item about selenium oxychloride .... 81 18 Chevrolet car, "The Goat," used in first high-coiiyression car tests...................................................... ...... .................................................92 19 Special arrangement of periodic system used in the "fox hunt" in which lead as an antiknock agent was discovered . 94 20 Copies of original entries in Laboratory Record 13 re lating to the development of the bouncing-pin indicator . . 98 21 The bouncing-pin indicator as developed in 1921 . . . 100 22 The first cabinet form of the bouncing-pin indicator . . . 102 23 Bouncing-pin indicator, variable-compression engine, and double-float carburetor, as used in knock testing in 1927 and before.................................. ...............................................................103 24 Copy of original entry in Laboratory Record 13 at first engine test of tetraethyllead 110 24-A Plot of results, first engine test of tetraethyl lead . . Ill 25 Plot of antiknock effects of the elements in four sig nificant groups of the periodic system ....... 114 26 Composite plot showing outstanding antiknock effect of lead by comparison with other elements ...... . 115 27 Bottles containing equivalent amounts of various anti knock agents by comparison with tetraethyl lead .... 116 28 Letter from Frank A. Howard to i!idgley relating to possible cooperative endeavor between their two organizations . 119 29 Apparatus for making zinc-copper couple . .................................. 127 30 Early apparatus for making zinc ethyl ....... 128 31 Third form of apparatus for making zinc ethyl . . ... . 129 32 Lay-out of proposed plant for making 100 gallons of tetra ethyl lead per day by the zinc ethyl route.................................. 130 33 Outline of early procedure for making tetraethyl lead hy the sodium-lead process. ....... ..... 138 34 First one-gallon tetraethyllead plant . . ..... 142 c 3?196 Report OC-33 ILLUSTRATIONS 399 Figure Number Page 35 Flow diagram'for making tetraethyl lead by reacting ethyl iodide with sodium-lead alloy.............................................................. 144 36 Plot of early measurements of antiknock effectiveness of tetraethyl lead by comparison with oxylidine .... 155 37 Diagrammatic sketch of detonation-tube apparatus . . . 176 38 Apparatus for converting tetraethyl lead into lead triethyl bromide, with James P. Andrew as operator .... 186 39 Contemporary photograph of first filling station in which Ethyl Gasoline was sold ............................................................. 197 . 40 Plot of daily sales of Ethyl Gasoline at the pioneer station during the first month . . ......................................... 199 41 Copy of advertisement shovdng how the distributors of Ethyl Gasoline were added to from year to year ..... 210 42 First newspaper advertisement of Ethyl Gasoline .... 213 43 The first mixing meter or "ethylizer" . . . . . . . 214 44 The second model of the mixing meter......................................... 216 45 A filling station with the second model of the mixing meter installed in it......................................................................................... 217 46 Center spread of advertising folder explaining the method of delivering Ethyl Gasoline in 1923 .................................. . 218 47 Third model of mixing meter . ...... 220 48 Third model of mixing meter as designed for production, installed on filling station pump . . . 221 49 Packing case in which one-liter containers of Ethyl fluid, called "methyliters," wereshipped................................................... 222 50 Automatic filling device for one-liter cans of Ethylfluid 224 51 Ventilated enclosure for automatic filling machines. . . 225 52 Early model of bulk mixing meter . 227 53 Steamship Ethyl, the first full-scale plant for extract ing bromine from the sea ......................................................................... 249 54 View of the bromine plant at Kure Beach, N.C. . . 254 etc 37l 97 'H, Report 0C^83 ILLUSTRATIONS 400 Figure Number Page 55 The Ethyl emblem as modified .......... 262 56 Copy of first agreement with the Bureau of Mines for investigating possible health hazards .................................. 266 57 "The Ethyl Gas Hounds," puppies born in the exposure chamber at the Bureau ofMines ... ...... 269 58 Copy of advertisement run to offset hysteria about the supposed dangers of EthylGasoline........ 273 59 Chart showing the upward trend in the octane numbers of motor gasolines and the influence of tetraethyl lead . 268 APPENDIX V 1 Battery of engines used in the search for a corrective agent................................................................................... 332 2. Plot of vapor pressures of lead bromide and chloride. . 3 Effectiveness of chlorine alone as a corrective agent . 4 Effectiveness of equal parts of bromine and chlorine as corrective agents ............................................................................. 5 Effectiveness of bromine alone as a corrective agent 6 Direct comparison, effectiveness of different halides as correctives ........................................................................................... 7 How weight of deposit increased with amount of fluid used 8 Exhaust valves and spark plugs after test .............................. 9 Exhaust valves and spark plugs after test, reverse view 333 334 335 336 337 338 339 340 APPENDIX VI 12 pages of selected newspaper items about Ethyl Gaso line as a possible health hazard ........ 348-359 ETC 37198 Report OC-83 ILLUSTRATIONS Ok 401 APPENDIX VII Page Newspaper account of first sale of Ethyl Gasoline to the public 365 Charles F. Kettering in his office in 1924 .................................. ...... . 366 Thomas Midgley, Jr., about the time of the lead discovery . . . 367 Dr. F. 0. Clements, with Mr. Kettering arid Orville Wright . . . 368 T. A. Boyd, about the time of the work on tetraethyl lead . . . 369 Carroll A. Hochwalt, about the time of his work on lead ... 370 Midgley, Kettering, and Boyd, photographed in 1943 . . ... 371 Midgley with Fred L. Chase ...................................................... ...... ... 372 Messrs, Maxwell, Kehoe, Webb, and Edgar, with Kettering and Midgley............................................................................................................................................................... 373\ Group picture of Messrs. Mack, Thomas, Kehoe, Siebenthaler, Morrison, Edgar, Harding, Jordan, Hochwalt, Midgley, and Kettering ............................................... 374 Engine in which tetraethyl lead was first tested . . . Engine used in studying We exhaust^from^thyl Gasoline . . . 375 . . . 376 Another contemporary view of the pioneer Ethyl station .... 377 Airplane in which an antiknock agent helped make the first al- titude record ... 378 6'7'C '7j 99