VIRGINIA BARTOW University of Illinois, Urbana, Illinois
Annom the family possessions, Professor H. N. Hillebrand, former chairman of the Department of English of the University of Illinois, found fifty-one letters (9) written by his father between the years 1881-85. They were addressed to Dr. S. F. Emmons who was the geologist in charge of the newly created Rocky Mountain Division of the U. S. Geological Survey. These letters were written in the clear, old-fashioned script used before assistance from typists made writing less of an art. They begin with the formal salutation, "I have the honor," and end with the proper, "Very respectfully, Your obedient servant," as was the custom of the time. These informal communications have considerable inteiest to analytical chemists. They appear to be personal comments about early analytical problems in this country, which were written in addition to the required monthly reports to the Washington oEce. The notes describe the perfectmg of analytical methods and emphasize the keen mind and intellectual attitude of the author. The account of the discoveries of new minerals in the recently opened country has a fascination for any research worker. They contain speculations and interpretations which would be impossible in material to be presented for publication. They were composed early in the career of the man who became the acknowledged leader and greatest force in mineral chemistry in the United States. Many comments are prophetic since they indicate the now well-known direction which Dr. Hillebrand's accomplishments would take. Dr. Hillebrand's connection with th'e U. S. Geological Survey began almost a t the time of its orgd.nization (8) under a law which was passed by Congress on March 3, 1879. The duties of the director were to oversee the classification of public lands, examine geological stmcture, mineral resources and products. No personal or private interest in mineral wealth or lands could be served. For ease of administration, the country was divided into geological units, one of which was the Rocky Mountain Division, comprising New Mexico, Colorado, Wyoming, Montana, Western Nebraska, and southwest Dakota. Although inspections of this alea had been made prior to this law for such puiposes as military esploration, international boundary determinations, and railroad surveys, the new enactment accomplished a consolidation of such enterprises. In 1879 Dr. Hiiebrand had just returned to this country Presented before the Division of History of Chemistry, at the 115th Meeting of the American Chemical Society in San Francisco, March 27, 1949. 367
after his excellent training a t Heidelberg under Bunseu and Kirchhoff and a t Strasburg under Fittig (11, 13). Knowing of this newly created Geological Survey and realizing its need for chemical analysts, Dr. Hillebrand applied for a position with the organiztion, but he was not employed. Still certain that the western part of the country offered splendid opportunities for the development of his interests, the young chemist petitioned for and did obtain a position as analyst a t Leadville, Colorado. The Survey bulletins (9) show the extraordinary growth of this locality. With the discovery of three productive surface mines, active prospecting had begun in 1877. The nucleus of the city first known as Agassiz, later to be called Leadville, with a few cabins and less than two hundred inhabitants had been built. When the great richness of the mineral resources of the area were realized, geological field work was carried on in the neighborhood until the winter snows prohibited further prospecting. By 1880 there were 15,000 inhabitants in Leadville and twenty-eight miles of streets, part of them lighted by gas. All the attendant public buildings, including opera house and theaters, were finished. The assessable property was valued a t $30,000,000. The Survey by this time had built and equipped a laboratory there, but iiiany private companies, which were booming, needed the services of a trained analytical chemist. The famous "Ten Mile District" near Leadville, a t an altitude of 11,000 to 13,000 feet, still remained one of the chief interests of Dr. Hillebrand after he left. In 1880 Dr. Hillebrand was invited do join the Survey staff in the position for which he had been a candidate, at a salary of $2000. His name appears on the roster of the Rocky Mountain division (8) as the only chemist in a list of thirty-nine names. Dr. Hillebrand, whom few could equal both for quality and quantity of laboratory work, published with his assietants a t least a dozen papers in the next five and a half years. In addition, with Whitman Cross, a 109-page bulletin was compiled, "in their spare time." The Survey bulletins themselves were impersonal, although Hillebrand's individual work appears a t intervals. In these bulletins there is little difficulty in detecting that the so-called "chemic" work was always regarded as subordinate to the "geologid' (10).
The letters (9) present a very hnman record and create a variety of impressions. If not of absorbing interest, they are part of the solid base upon which American chemistry was erected. They are the concrete evidence of the labor, hopes, and ideas of a young
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man whose later distinguished career carried out the promise indicated in his early research. Perhaps the letters had been kept by the family because they represented those busy early days which were the preparation for the future. Even though the letters are but a minute part of the whole tale, they call to mind the vivid history of the settlers. Here is a portion of the story of the search for new and valued mineral resources, undertaken by the Geological Survey as a government agency. For the chemist they represent not only noteworthy records of the successes and failures so well known to every research man but also a remarkable example of the h e understanding and selfdiscipline so essential to scientific endeavor. In Denver, far from the center of chemical activity and in a new lahoratory, one of the initial problems mentioned by Dr. Hillebrand was the consideration of required equipment. Because the sum which he had to spend was not large the need for economy was often expressed. The first letters discuss the importance of a solution of high specific gravity to separate the different mineral constituents in the heterogeneous rocky material. Goldschmidt's method, the Thoulet solution, and a borotungstate solution were proposed. The l a b ter took two or three weeks to prepare hut Dr. Hillebrand assured Dr. Emmons that by varying the temperature more adequate separations could be made. In the end, time would he used more efficiently. Dr. Hiilebrand was evidently handicapped the first few months by lack of a spectroscope, which a student of Bunsen could not fail to consider essential. The instrument finally arrived a t a cost of $81with $4 extra for the express. That seemed exorbitant but the chemicals ordered a t the same time were about $4 less than expected. The kind of battery to be adopted was discussed in several letters. Although the type which used sulfuric acid alone for the conduction liquid was available, the chromic acid unit was selected as more practical. An electromagnet with a rheostat for separations, the desired quantity of p!atinum dishes, and a drying oven to maintain regulated high temperatures were gradually added to the laboratory.? This oven was needed to determine the so-called basic water in minerals, in contrast to the water that was lost to sulfuric acid as a dehydrating agent in a desiccator. The purity of the reagents had to be determined with skill, patience, and time before they were used. While doing this Dr. Hillebrand discovered and reported that acids from a well-known supply house had too much iron, calcium, and magnesium to be used for silicate tests. He remarked that he would in the future buy no more from this company. Later, he ascertained that the lead acetate which he had been using had had enough silver in it to give unreliable results. He found imperfections in the furnaces and impurity in the bone ash cupels. No wonder that he then began his vigorous action against faulty reagents and equipment for chemical analysis which had rendered valueless days and weeks of labor. Retarded operations were regretfully recorded in the
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letters. Not all postponements and delays were due to chemical problems. Fortunately, illness came rarely. In connection with the laboratory property, boundary disputes and new construction problems were delegated to the chemist. Since the building was located near a stream Dr. Hillebrand wisely supervised the erection of pilings some twelve feet out from the shore in order to fill in more land. This proved to have been prudent since a flood mentioned later did not damage the laboratory proper. Sometimes the arrival of equipment was delayed. Large crucibles for a type of assay which "gave the greatest accuracy for the least time expended" failed to appear as promised. Once the pressure of the gas mains was so low for a matter of weeks that some work could not be done a t all, and what v a s done took three or four times as long. At the end of his assignment in Colorado, Dr. Hillebrand wrote askmg for "a clear month here to finish the mineralogical work that I am now on. This month in that respect has been one of the most unfortunate ones in which, notwithstanding the greatest care, everything a t times seems to go wrong; beakers break, something is spilled, causing exasperating delay which it does not do to fret about or something else is sure to happen." The comments on the analytical work were not ahout routine determinations but concerned with unusual items which came to the laboratory. They are very stimulating reading for a man starting a similar career. The technique was as flawless as could be devised for the time when it was used. Dr. Hillebrand introduced few original methods but left none which he used uninlproved in the interest of accuracy. He emphasized to his superiors the need to take the added time for duplicate and even triplicate analyses, noted the magnification of experimental error when the size of the sample was too small, described days of search with the microscope to obtain pure samples, and frequently questioned the accuracy of the work of others. At times Dr. Hillebrand discussed published formulas for minerals which were in no way substantiated by the accompanying analysis. He pointed out why baryta had been missed by earlier workers in the Rocky Mountain District. During his last year in Denver he demonstrated the utter impossibility by known methods to separate and identify quantitatively what he called the mixtures of columbic, tantalic, and titanic acids from the Leucite Hills. In his last contribution, the book by Hillebrand and.Lundel1 which was published in 1929 after Dr. Hillehwnd's death, it is stated that the separation of columbium and tantalum when present together is beset with the greatest obstacles. Dr. Hillebrand described the simple expedient of dissolving the free sulfur in a mineral sample in which the ratio of sulfur to metal content appeared to be faulty by using carbon disulfide. The percentage of sulfur after the removal of the uncombmed element was in agreement with the theoretical values for the metals present. Naturally, the wealth of mineral matter in the great region which the laboratory served yielded from time to time samples which gave promise of being new to the
JULY, 1949 region, the United States, or science. Such investigations were perhaps the most stimulating and rewarding which were done. All the suppressed excitement of the trained, conservative research man is evident in the lines which Dr. Hillebrand wrote about such 6ndmgs. Among the number new to the area or to the country was gadolmite found near Pikes Peak which was said to be "hitherto known only in Norway and one or two places in Germany." Samarskite which was interesting in view of the newly devised Periodic Table was identified. Then, as now, uranium ores were rare. Zircon, allanite, an opaline, and phosphates of the rare earths were recognized. For months the letters refer t o an effort to define accurately an elusive new mineral. Tentatively, Dr. Hillebrand thought that he had someth'mg unique and wanted to name it Emmonsite for his chief. Then he felt forced to withdraw his claims and suppress his hopes. Later he tried to find a second sample on an expedition away from the laboratory. Having no success in the time which he allowed for the trip, he wrote that he did not pursue the search since it would have required an extra day which he did not feel a t liberty to take. Somewhat later the name Emmonsite was used by Dr. Hillebrand to designate a new ferric telluride said t o be the first of the natural tellurides. Unusual formations led t o a discussion of the origin of iron near Leadville and of meterorites. The letters contain little further speculation about geological theories, although the analytical work which was being carried out in the chemical laboratory with its exact notations of the localities from which the samples were obtained were an integral part of the history of the rock formation in that area. Dr. Hillebrand presented some arguments that a certain iron oxide was a product of the decomposition of a sulfide. The crystals were not a t all large and the sulfide seemed to be permeated with the oxide. The distinction between original rock matter and disintegration or alteration products was, when required, painstakingly ascertained. In connection with the discovery of a new lead and arsenic sulfide, Dr. Hillebrand offered his deductions. A t J F t time it was thought that metallic sulfides were deposited from solution in the cavities or fissures of rock material or were replacements of certain or all constituents in rocks. Since this new ore was one-half the volume of the lead arsenic sulfide and its crystals distinct and unattached it seemed unlikely that they were deposited by precipitation. Of several alternatives, Dr. Hillebrand suggested that the ZnS might a t one time have been in plastic or liquid state and formed under heat and pressure. The pressure would have been required or the sulfur and arsenic would have been expelled. Therefore from this plastic magma the new mineral, which was named zunite, could have crystallized. Dr. Hillebrand concludes his suggestion to the geologist, Dr. Emmons, by writing, "The remarks may not possess much value but I give them for what they are worth." To conform with government regulations, requests to read papers before the Colorado Scientific Society in which Dr. Hillebrand was active had to be submitted to
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Washington. Once, when the decision to report on some of the work was made too late for a reply by letter, this conscientious man asked that denial, if i t was made, should be telegraphed to him a t his expense. This scientist who devoted himself to his work with an integrity that did not allow him to hunt for a second possible sample of a "new" mineral because to do so would take him away from his laboratory "a day longer" was to miss the discovery of helium from the mineral clevite which he was examining. His ability and observational powers were not a t fault. He did see the unfamiliar lines in the s ~ e c t r u mbut his duties a t the time seemed to preclude fulther search. The letter which he wrote to Sir William Ramay, who made the discovery, is said to he one of the 6nest and most generous to a colleague to whom the great honor went when Hillebrand as he himself said "missed his chance" (1.8). Not infrequently, sample ores which they hoped would prove valuable were sent in to the laboratory by an individual in spite of the fact that work was not done there for private interests. Dr. Hillebrand did perform one such analysis which was "wholly in the interest of science." The account of another sample with all the earmarks of deception was quite eng~ossiug. This was a clayey material from New Mexico about which Dr. Hillebrand wrote at length. He would have done nothing with it except he thought that if fraud were suspected he should "unearth i t for the public good." He wrote: "With the specimens there was a long description of the various claims made by a French and an American Company, who were said to have taken up thousands of acres of placer workings and spent much time in perfecting a secret method for extracting the larger quantities of silver, gold, s n d platinum in the earth metals whioh no known process of,anslysis or assay will detect, as they are present in hitherto unknown compounds. T. W. Morgan Draper is the head of the American Company with a certain Tyler, while a. French count is connected with the other. They claim fabulous quantities of gold in their diggings. The connection of Draper with the affair does not lessen my disbelief in the existence of the bonanm. From the published accounts it seems as if a great fraud were about to be perpetrated and great crowds are beginning to flock to tho region. For my own edification, I examined the specimens in such a way that there could be no possible loss by volatilization and could find neither silver, gold, nor platinum. Tin I did not look for. The appearance of the specimens is in themselves enough to condemn them. I t may be that the companies know of deposits or veins whioh are really metalliferous but the specimens sent are claimed to be identical with those which are said to be rich." He t,hm asked. "If further soocimens are sent accom-
I n February, 1883, Dr. Hillebrand had a request from Mr. Emmons to investigate the Colorado coal fields. His reply indicates the thoughtful study which he always made. He wrote: ''I am not aware that any elementary analyses of coals from this state have been made. Owners of mines and consumen being equally content with knowing the proportions of ash, volstile and fixed combustible matter and water. For a complete knowledge of eosls with regard to classification and applicability to different uses it is important and in fact necessary that the
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370 proportions of C, H, 0,N, S, and composition of ash should be known, moreover the absolute specific and pyrometric heating d u e s . If it is merely desired to know where to place them, whether among lignites, bituminous, or anthracite coals, it is generally sufficient to know the portions of C, H, and 0 in them. But in order to find the oxygen, and that only approximrttely, it is neeessarv , to determine fimt the carbon and oxveen . .. and also irrqurnlly the nitmgrn nhirll mar art!rm.r to 2 per w r i t
that by remaining here, I should not be at liberty to devote all my time by any means to work of this kind but opportunities for it would undoubtedly offer as in the past. The experienoe gained already in this line has been of great value to me and a year or two more of work on such rare and difficultsubstances to analyze as have already come under my observation in number would, I think, go far toward making me one of the most euwrienced analvsts in the country, and k t class analysts in this field are by nomeans very plent;: By remaining here for a time at least, I think I should be able to do both myself and the Survey more credit than by being put upon the perhaps somewhat less pleasing though certainly not less important work in Washington which you mention. At the same time, I know full well that
Finally, all plans for the move were made a t a time when the most of the work was done for the season and before the winter might make transportation hazardous. Dr. Hillebrand had writ,ten that as long as he had had but two weeks' vacation that year he hoped that it would he possible for them to allow him the other sixteen days t o pack his household goods. He also expressed appreciation for help in locating a house. He drote: "I shall want one with three bedrooms besides that for the girl. Thirty dollars will probably be the highest figure I shall he able to pay and then only if nothing a t all suitable for a lo~verprice can be obtained." After Dr. Hillebrand transferred to Washington he remained with the Survey until he was appointed the chief chemist of the Bureau of Standards in June, 1908 (1). His attainments and his position made him one of the most influential men in his field of analytical chemistry. The gradual expansion of his beneficial domination developed directly from his western experience. He exerted this influence in three general ways. His published papers were models of simplicity (5) and excellence for his readers to follow. He was frequently made not only a member but the chairman of authoritative committees to oversee analytical procedures. His supervision of the chemical publications in his field continued a lifelong vigilance over analytical chemistry. His colleagues felt that he did as much as any man in American chemistry to place analytical work on a sound basis. .. Dr. ~illebraLdjoined the American Chemical Society in 1893 (2) a t the time when the society was expanding into an organization of national scope. His contributions to the society began at once with a paper (4) delivered before the Baltimoremeeting in December of the year he joined and entitled "A Plea for Greater Completeness in Rock Analysis." This paper was the first of a number on the general subject of raising the standards of analytical work, which was a project for which he had the passion of a crusader. He pointed out the uselessness of much contemporary analytical writing, the want of appreciation oT the significance of small quantities of impurities which were often neglected by analysts, the variability of analyses done a t different times, and urged greater accuracy and microscopic examination before chemical investigation. I n this plea all his wide knowledge of current methods and his practical work in the West supported his statements. His later published addresses (few in number, since he was a man of works and not words) comment fully upon the same themes. When he was awarded the Chandler Medal in 1916 his address was on the subject of his heF ~ ~(q, ~ ~ loved azAnalytical chemistry and Here again was an entreaty for superb In addition he emphasized the value of precise technique
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in the practice of electrochemistry, physical chemical measurements, metallurgy, and rare-element studies. He concluded with an appeal for teaching rigorous discipline in connection with analysis. These remarks of a mature expert toward the end of his career repeat the philosophy of the early letters and offer a creed for analytical chemists. As was natural and inevitable, when his talents developed in Denver were recognized, Dr. Hillebrand was appointed to membership in the committees of the American Chemical Society (8). These appointments which followed one another rapidly are recorded in the proceedings. In 1896 he was made a member of the committee on coal analysis. In 1899 he was elected to the council and in 1902 placed on a committee to report on the quality of analytical reagents furnished by dealers in this country. The committee changed its name to 'Committee on Purity of ReagentsJ' in 1904. The membership is impressive with J. H. Long, H. P. Talbot, Charles Baskerville, and L. M. Dennis, in addition to Dr. Hillehrand. Meanwhile, another committee for "Uniformity in Technical Analysis" was formed with Dr. Hillebrand as chairman. It was a cherished idea of his that standard samples should be prepared which could be furnished to those who wished them. Cooperation with the Bureau of Standards was enlisted and a limestone sample was advertised in February, 1905. Other samples were added as time permitted their preparation. To ensure the high standard of all analytical work reported by members of the society, the Committee on Standard Methods of Analysis was firmly established by 1910 with Dr. Hillebrand as chairman. No paper containing analytical material could he presented without passing the scrutiny of this group. Subordinate committees having any relationship to analytical work were responsible to them. Another valuable service of the committee was the prevention of needless duplication. Smce the supervisory power and the prestige of the committee were recognized by all members of the society, Dr. Pillebrand must have had great personal pleasure in realizing his dream of establishing superior analytical metho% by this means. It was very fortunate for the American Chemical Society that a man of Dr. Hillebrand's scholarly outlook gave so generously of his time and energy. Through his tireless effortto promote chemical publications of real merit in this country Dr. Hillehrand enhanced the reputation of the American Chemical Society. He accepted the responsibility of a reviewer on mineralogical and geological chemistry for the "Review of American Chemical Research." He was made a member of the Committee on Papers and Publications of the 5th International Congress of Applied Chemistry. At this time there was increasing sentiment among American chemists that a journal comparable to the'foreign abstract periodicals should he started for the use of the members and subscribers. The scheme to have such a publication was recorded in the society proceedings for 1906. The committee for the investigation of the problems connected with the
establishment of Chemical Abstracts were, in addition to Dr. Hillehrand, A. D. Little, Edward Hart, and W. A. Noyes. When Dr. Hillebrand was elected president of the American Chemical Society in 1906 he dropped membership in this committee, which had been called the Committee on Publication. In 1908, with the presidential duties fulfiued, he became an associate editor of the newly established Journal of Industrial and Engineering Chemistry. In 1909 he was made a member of the committee on Organization and Nomenclature and joined the board of associate editors of the Journal o j the American Chemical Society for mineral and geological chemistry. A year later he was on the executive committee of the Division of Physical and Inorganic Chemistry. As a past president he was a member of the American Chemical Society council for life. We 6nd that the minutes of the meetings rarely omit hisname as among those present to champion the interests of sound fundamental science as he had done from the time of the Colorado period. The honors which Dr. Hillebrand attained have been . listed elsewhembit they do not always mention the new mineral found in Mexico about 1909, a rare hydrated calcium silicate, CazSiO~H?Owhich was given the name of Hillebrandite by proteges of his, as he had years before named a new mineral Emmonsite for the man under whose direction he was working (IS). The Washington section awards an annual "Hillebrand Prize" (7) for the best paper presented before it during the preceding year. Such an award could not be more appropriately named. Nothing except the highest caliber of research ever came from the laboratory of the man whose name i t carries. . In additioq, to the letters &other item associated with Dr. Hillebrand is found a t the University of Illinois. It is an elegant set of analytical apparatus made by a German firm and presented by Dr. Hillebrand to Dr. William Albert Noyes, who gave it to the University laboratory. From the beautiful wooden box to the last tiny platinnm spooh and dish, among the dozens of pieces of diminutive equipment, it is an example of beautiful workmanship. It is a miniature analytical laboratory which can be carried by hand wherever the owner travels. This substantiates old reports that an analytical chemist carried his equipment on his back. Modem instruments may have superseded those used by Dr. Hillehrand. Nevertheless, the standards now adopted rest upon the results of the type of exact analytical work of which Dr. Hillebrand was the master. ~
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LITERATURE CITED (1) ALLEN,E. T.,J. CEEM. EDUC., 9, 73 (1932). (2) Am. Chem. Sac. Proc., 58 (1893); 22 (1896); 24 (1899); 91 (1902); 7 (1903); 23,71 (1904); 34 (1905); 58 (1906); 87 (1908); 31, 61, 109 (1909); 23, 51, 105 (1910). (3) HILLEBRAND, W. F., ''Fifty-one Letters Written to Dr. S.
F. Emmons." (4) HILLEBRAND, W. F., J . Am. Chem. Soe., 16, 90 (1894) (5) HILLEBIMND, W. F., ibid., 29, 1 (1907).
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372 (6) HILLEBRAND, R. F., J. Ind. Eng. Chem., 9 , 170 (1917). (7) Ind. Eng. Chem., 14, 138 (1936). (8) U. S. GEOL. SURVEY,1st Annual Report, 1880, pp. 3, 13. (9) Ibid., 2nd Annual Report, 1880-81, p. 209.
(10) (11) (12) (13)
Ibid., 7th Annual Report, 1885-86, p. 35 WATERS,C. E., Science, 61, 251 (1925). W A ~ R SC., E., Am. Chem. Soe. Proe., 53 (1925) WRIGHT,F. E., Am. J . Sci., 26, 545 (1908).
