George
B. Kauffman
California State College at Fresno Frerno, California 93726
Platinum Metal Pioneer: James Lewis Howe (1859-1955)
A
number of prominent late nineteenthearly twentieth century coordination chemists entered the field of inorganic chemistry through the back door, so to speak. Sophus Mads J#rgensen ( I ) , Lev Aleksandrovich Chugaev ( 2 ) , and, most prominent of all, Alfred Werner (3) were all trained as organic chemists. In our own time, the example of John C. Bailar, Jr., who obtained his degree under the direction of Moses Gomberg, springs readily to mind. James Lewis Howe, for many years Professor of Chemistry and Head of the Chemistry Department at Washington and Lee University, fits into this pattern. -
~
mention to Frank Wigglesworth Clarke (1847-1931), the eminent geochemist, that he was looking for a new research topic. Clarke told him that he could not understand why chemists persisted in devoting themselves so exclusively to carbon, an element with so few oxidation states, when so much more real chemistry could be learned from the elements of the platinum group, some of which possess as many as eight different oxidation states. This chance remark made a deep impression on Howe, who began eagerly to read the literature of the platinum metals. He decided that the most interesting and least known metal of the group was ruthenium, which Mary Elvira Weeks (7) has called" the little Benjamin of the platinum family" since it saw the light of day so much later than its older brothers. Within a remarkably short time, Howe became not only the one outstanding American authority on and bibliographer of the platinum metals in general but also the undisputed world authority on the chemistry of ruthenium in particular. Life (8)
A recently deceased American authority on the platinum metals, Raleigh Gilchrist of the National Bureau of Standards, has related the circumstances leading to Howe's entry into the inorganic field (4). Young Howe had recently returned from the University of Gottingen, where he had obtained his 11I.A. and Ph.D. degrees under the direction of Hans Hiibner, whose main research interest lay in the area of aromatic compounds. Howe's dissertation naturally dealt with an organic topic, and his first two publications (5, 6) constituted an extension of this work. Absolutely nothing in Howe's background indicated that he would go against the mainstream of the time and leave the field of organic chemistry which was at the zenith of its development while inorganic chemistry languished in the doldrums. Then, a t a meeting of the American Association for the Advancement of Science, he happened to Presented before the Division of the History of Chemistry at the 153rd National Meeting of the American Chemical Society, Miami Beach, Fla., April, 1467.
804 / Journol of Chemical Education
James Lewis Howe was born in Newburyport, Mass., on August 4, 1859, the son of Dr. Francis Augustine Howe and Mary Frances Lewis Howe. His parents were noted for their progressive outlook, as we may deduce from even a pair of isolated examples-James attended pre-kindergarten a t age four during a time when nursery school education was rare, and the Howe home was the first in Newburyport to have a telephone. I t is not surprising, then, that a progressive and liberal view~ointcharacterized James Lewis Howe throughout his life. The Howe family was also noted for its longevity; James had an uncle who lived to be 105 and a sister who lived to the age of 100. Howe himself lived to be 96 and almost created an illusion of immortality. One of his students remarked, "I should not have been surprised [when he died]. Actually I was, for I had come to feel that we would always have him with us" (8g). Comparisons are always dangerous, yet I cannot refrain from comparing James Lewis Howe in chemistry with Charles Camille Saint-Saens in music. This illustrious French composer, who lived to the age of eightysix, was born a mere seven years after the death of Beethoven, the last of the classicists. Yet he was acquainted with Berlioz, Gounod, Liszt,, Verdi, Wagner, and other composers of the romantic period, and even lived to hear the works of such modern composers as Schonberg and Stravinsky. I n an even more striking manner, Howe's life likewise spanned epochs. Born a year before the Civil War began, he lived through the Spanish-American War, two world wars, and the Korean conflict, the last of which is within the lifetime
of even the youngest of our freshman students. It is thus easy to forget that he was horn in the same year as Arrhenius, one year after Icekul6 proposed theselflinking of carbon atoms and one year before the first international chemical conference a t Karlsruhe. During Howe's lifetime, chemists whom we today regard as historical figures were alive and active-men such as Faraday, Dumas, Mitscherlich, Liehig, Wohler, Graham, Bunsen, and Mendeleev, to mention but a few. As we shall see, Howe put his years of experience to good use in instilling a feeling forhistory in his students. Howe originally intended to follow in his father's footsteps and become a physician, but during his years at Brown High School in Newburyport, he became interested in chemistry. He continued his study of chemistry, together with his other favorite subject, German, at Amherst College, Amherst, Mass., his father's alma mater. At Amherst he also studied physics under Elihu Root "who opened to me," Howe was to remark some sixty years later, "the search for truth for truth's sake." When he received his B.A. degree in 1880, he was chosen for "excellence in his field" to speak a t commencement. I n his addressUTheScientific Method and Religion," Howe attempted to reconcile the two primary motivating forces in his life and to show that their goals are the same, via., the search for truth (9). As was the custom in those days, after graduation Howe went to Germany to complete his studies. From 1880 to 1882 he studied a t the Universitat Gottingen under Professors Hans Hiibner, J. Post, and the legendary Friedrich Wohler. His doctoral dissertation (1882), " ~ b e rdie ~thylderivatedes Anhydrobensdiamidobenzols und iiber ein Nitril desselben," was based on research carried out under Hiibner's direction. I t bears the dedicationl'Herrn Professor Dr. F. P. Venable als Zeichen aufrichtiger Freundschaft gewidmet." Howe was later to collaborate with Venable (18561939), who was at one time President of the University of North Carolina, in the composition of a popular general chemistry text (10). I n 1932, the Uoiversitat Gottingen honored Howe's achievements in chemistry by presenting him with a diploma marking the fiftieth anniversary of the awarding of his doctorate. In the Spring of 1882 Howe left Gottingen to attend the Universitat Berlin where he studied under Liehermann, Liebreich, Sell, Baumann, Tiemann, Paulsen, Curtius, Gabriel, and Dohner. He participated in that sine qua non of nineteenth century German academic life, the dueling society, and he maintained his membership in a t least two of these through World War 11. On his return from Germany, Howe accepted his first teaching position-Instructor of Science a t the Brooks Military Academy in Cleveland, Ohio, where he remained for a year. I n 1883, Howe moved to the South, which was to be his home for the rest of his long and fruitful life. He accepted a position as Professor of Chemistry (later of Physics and Geology as well) at Central University, Richmond, Icy., where he remained for eleven years. On December 27, 1883, he married Henrietta Leavenworth Marvine of Scranton, Pa. This marked the beginning of a marriage of sixty years' duration. The Howes became the parents of two daughters, Guendolen and Frances, and a son, James Lewis. Jr. Mrs. Howe died in 1944, after which time
Guendolen became her father's constant companion and housekeeper. During his stay in Kentucky, Howe simultaneously held positions with the Polytechnic Society of Kentucky, the Louisville Hospital College of Medicine, and the 1,ouisville College of Dentistry. I n 1886, he was awarded an honorary M.D. degree from the Hospital College of Medicine, a not uncommon occurrence a t that time. The greater part of Howe's career was spent at Washington and Lee University in Lexington, Va.. one of the South's leading liberal arts colleges for men. He accepted the chair of chemistry in 1894, and for almost half a century he was an institution on the campus which the English poet and playwright John Drinkwater has described as the most beautiful college setting in America. For the first fifteen years of his tenure Howe was a one-man chemistrv denartment. The entire chemistrv laboratory was nothing more than a single room located over the power plant with Howe's office and a balance room partitioned off at one end and a small research laboratory at the ot,her. I t was in these cramped and noisy quarters that Howe carried out the research on the element with which his namc is so closely identifiedruthenium. The dividing line in the laboratory bctween beginning and advanced students mas spat,ially a purely imaginary one, but it. was sharply defined by certain privileges granted to the upperclassmen. More important and highly prized than the privilege of smoking was the privilege of working in closc associa t'~ o n with Howe, who was regarded as a personal friend by his students. Howe's lecture stylc was informal. Although he was sparing in his use of demonstrations, he made liberal use of anecdotes and reminiscences. Professor John F. Baxter, a former colleague of Howe's, relates how he atatendedHowe's course in the Development of Chemical Thought:
" .
I am sure the sophomores found it horing, but I f o m d it. Emeinating. I t was organized, hot there wm also a lot of delightfd rambling. I can st,ill hear [IIowe] say, "Since I had a little time in Stockholm, I called up Arrhenius on the telephone" or "Bwsen invited me down to IIcidelherg to see his laboratories."
Baxter also reports Howe's recollections of Wohler: Howe was doing some work in analytical chemistry, and i t seems that luckily he had just cleaned up his part of the lahoratory so i t was spick-andqxn when in wandered the old professor, who stood and watched IIowe for a few minutes, rocked hack and . I have told many of forth on his heels, and then said "Seh6n." my own chemistry classes that one of my teaching colleagues had been in the laboratory with Wiihler so that one man's life has linked them with the synthesis of urea hack in 1824.
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As a well-known bibliographer, Howe was naturally a wide reader, and he kept his lectures thoroughly up to date with the latest chemical advances. He felt that chemistry had to be learned in the laboratory rather than from books and lectures, doubtless an attitude ingrained by his experience a t Gottingen. He insisted on personally supervising laboratory work, and he was rigorous in his standards and firm in his discipline. He was never known to lose his temper or to exhibit openly any negative emotion; a slight frown of displeasure was a sufficient reprimand to even the most obstreperous student. Howe's "Bibliography of the Metals of the Platinum Group," together with his unchallenged position as the Volume 45, Number 12, December 1968
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leading American authority on the chemistry of the platinum metals ( I l ) , led directly to his appointment in 1917 as Chairman of a special sub-committee on platinum of the National Research Council. American chemists and the United States government had become concerned ahout the platinum shortage, especially when imports from Russia, the world's principal source of the metal, ceased after the collapse of the Russian government. Howe's committee, working in cooperation with the Bureau of Standards, the Bureau of Mines, the Geological Survey, and other governmental scientific organizations, was charged with "looking up the whole question of the platinum supply and thc possibility of providing satisfactory platinum suhstitutes in the various fields where platinum is now regarded as essential . . . [and preparing] a summarized report setting forth the exact situation and the best remedies therefor" (12). With his genial, commanding personality and limitless energy, Howe, now in Washington, attacked the problem in two major ways. He encouraged the search for substitute metals and alloys, of which a number came into limited use, and he initiated a campaign for the purchase of platinum jewelry arid scrap from the public and from jewelers. These various additions to the national supply, plus the increased production in Colombia stimulated by the fixed, high price, were sufficient to meet governmcnt needs until thc war ended. Howe's service with the government was apparently satisfactory, for he subscquently received presidential appointments on thrce occasions t o commissions for assaying the coinage of the United States. Howe was a member and officer of a number of professional and honorary organizations, including thc Chemical Society, the Society of Chemical Industry, the Washington Academy of Sciences, the Deutsche Chemische Gesellschaft, t,he American Association for the Advancement of Science, and the Virginia Academy of Sciences. H e joined the American Chemical Society in 1893, and for a number of years contributed his well-known annual reviews of "Recent Work in Inorganic Chemistry" for the societ,yJsjournal (IS). At the timc of his death he was one of the American Chemical Society's oldest members. Howe's unflagging energy and enthusiasm were manifested by his many extra-scientific activities. He served as deacon and elder of the Lexington Presbyterian church, and his son, James Lewis, Jr., himself a chemist who spent a number of years in China involved in missionary work, always felt that his father placed his religion above his secular life. Howe was an active AIason, and he also held positions in the Lexington Town Council, and t,he People's National Rank of Lexington. At scientific gatherings, Howe might easily have becn mistaken for a t,ypical Southern gentleman and aristocrat of the old school, so thoroughly had he adopted the gracious customs of Virginia. Yet by ancestry, birth, and education he was a New Englander. A man who loved life and knew how t o delight in simple pleasures, Howe liked t o eat well and enjoyed cigars and a favorite pipe. A bottle of beer before retiring was a daily ritual. One of Howe's most outstanding physical charactcristics was his booming voice. Being slightly deaf in 806
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later life, he talked as though other people were slightly deaf also. Sitting on his front porch reading aloud t o his wife in the evening, he could be heard a "country mile." While he may have had some trouble in hearing people, he never allowed this handicap to interfere with his deep personal interest in the problems of others. "Howdy" Howe, as he was known t o most citizens of Lexington, always had a smile and a low bow for everyone. He was sought after for friendly advice by students and townspeople alike. Howe retired from teaching in 1938 but remained active in a variety of ways. His bibliography, of course, consumed much of his time. I n his capacity as University Historian, he produced a number of studies on local lore and frequently spoke on historical topics. An avid philatelist from the age of ten, Howe continued collecting stamps from Great Britain, British Colonies, and the United States. I n his late seventies, he purchased a piano and began to learn to play it. Some idea of how dynamic he must have been during his youth may he gleaned from the fact that he was still astonishingly active in his eighties and was addicted t o such youthful garb as light-colored clothing and tennis sneakers. During World War 11, t,he university recalled Howe t o teach classes in German and chemistry. He retired again in 1946, whereupon Washington and Lee honored him with an honorary Doctor of Science degree. As during his first retirement,, he remained active during his second retirement, and until the very end of his life he continued to attend meetings of the numerous organizat,ions of which he was a member. At four o'clock on the morning of December 20, 19.55, only three days after unexpectedly entering Lexington's Stonewall .Jackson Hospit,al, Jamcs J,ewis Howc died a t thc age of ninety-six. The Bibliography
Despite his fundamental research on the chemistry of ruthenium, Howe's inapum opus and best known contribution to chemistry is his "Bibliography of the Metals of the Platinum Group" (14-16), which covers the literature from 1748, when platinum was first described ( l 7 ) , up to the end of 1950. This monumental bibliography was cited ns the major basis on which Howe was awarded in 1937 the American Chemical Society Georgia Section's Charles H. Herty Medal for the advancement of science in the southern states. Prof. M. Guy Mellon of Purdue University, long a recognized authority on the literature of chemistry, always referred to Howe's work as a n ideal bibliography. Howe completed the first volume of his bibliography (1748-1896) (14) less than three years after publishing his first research paper on ruthenium (IS), a truly remarkable achievement in view of the obvious painstaking and meticulous care expended in its compilation. He was aided in this immense task by referring to a rare monograph (19) by Carl Ernst Claus (17961864), the discoverer of ruthenium, which contained a fairly complete critical bibliography through 1861.' Only 300 copies of Claos' pamphlet were printed, and according to Ilonald XleDonsld ( N ) ,a specialist on the history of the platinmn metals, the only copy still in exist,ence in 1946 outside the USSR wm IIowe's own copy in the library of the Washington and Lee Chemistry Ilepnrtrnent.
Howe's first volume met with great success, and in 1919 a second volume (15), coauthored with Dr. Hendrick Coenraad Holtz and covering t,he period 1748-1917, was published. Like its predecessor, it quickly established itself as the standard bibliography on the subject. Twenty-eight years were to elapse before the third volume, entitled "Bibliography of the Platinum Metals" and covering the years 1918-1930 (Ifi), was published in 1947 by Baker & Co., Inc. (now Engelhard Industries, Inc.), the leading commercial interest in the field. Since then, two further HoweBaker decennial bibliographies (1931-1940, 1941-1950) have appeared (16) in the same attractive format with the lettering on the cover stamped in palladium leaf. Howe was scrupulous in keeping up with the literature; except when deterred by illness and the infirmities of old age, he could be found late a t night in his upstairs room at the typewriter under a bare lightbulb preparing cards for the next decennial volume of the bibliography which was to cover the period 1951-1960. He continued this activity until as late as the fall of 1955, and upon his death in December of that year his daughter Guendolen presented the cards to Baker & Co. so that another volume is not at all unlikely. Indeed, the continuation of the decennial bibliographies would constitute a fitting and perpetual tribute to the patience and foresight of the man who initiated the series. Miscellaneous Research
I n his first two publications (5, 6), his sole works in the organic field, Howe continued the research that he had undertaken a t Gottingen for his doctoral dissertation. The work dealt with derivatives of one of Hans Hubner's so-called anhydro bases (21) which had been extensively studied a t Gottingen, viz., the compound
described his analysis of water from Chiehan-Ranab (Little Sea), an almost unknown lake in the interior of the Yucatin peninsula in southeastern Mexico. Home's article on the action of Lexington, Va.'s hard wat,er on metals (28) underscores his interest in bot,h practical chemistry and municipal affairs. Although the various allotropes present in solid and liquid sulfur have been known for many years (29, 30) and are considered in most elementary descriptive chemistry texts, Howe was unable to find any consensus among chemists as to the color of sulfur vapor. In a series of incomplete qualitative experiments with the crudest of apparatus (51), he attributed the discrepancies to the general difficulty of describing the colors of vapors, the mistaking of condensed vapor for the vapor itself, and the variation of the color with temperature. More accurate quantitative measurements of the species present in sulfur vapor have since been made (52-54), but Howe's original observations remain qualitatively correct. The tendency of tripositive metal sulfates to crystallize with alkali metal sulfates or ammonium sulfate is so pronounced and characteristic that alum formation has been used to establish oxidation state. Since the existence of tripositive manganese was then disputed, in 1898 Howe (35) attempted to use this method in order to establish the existence of Rfn(II1). By employing the oxidizing action of an electric current upon a solution of manganese(I1) sulfate in the presence of ammonium, rubidium, and cesium sulfates and excess sulfuric acid, he attempted to obtain crystalline Mn(II1) alums. Although he was unsuccessful, he was able to prepare the ammonium, potassium, rubidium, and cesium alums of iron(III), the rubidium and cesium alums of cobalt,(III), and ammonium chromium(II1) alum. Piccini (%), working at approximately the same time, succeeded in preparing cesium manganese alum by an electrolytic process similar to Howe's in which the temperature was maintained below 1 5 T . Ruthenium Compounds (37-40) Nitrosochlorides
variously called anhydrobenzdiamidobenzene (Hubner) and benzenylphenyleneamidine (Beilstein). Except for a short note concerning the action of nitric acid on mercuric sulfide (22), the name of James Lewis Howe did not appear again in the literature for more than a decade. The first paper (25) that he published from Washington and Lee Universit,y concerned a problem that may have been related to his earlier position as Professor of Medical Chemistry and Toxicology at the Ifiuisville Hospital College of Medicine-the detection of arsenic and antimony in organic tissues. Although admittedly simpler and more convenient than the better known Marsh test ( 2 4 , the Reinsch t,est (25, 26) had been questioned both as to sensitivity and as t,o accuracy in distinguishing between arsenic and antimony. Howe (25) verified Reinsch's claim (2fi) t,hat, the test was capable of detecting arsenic in a solution of one part per million, and he also showed t,hat the arsenic sublimate could easily be distinguished from that of antimony by the naked eye. Another area of analytical chemistry that engaged Howe's attention mas t,hat of natural water and its analysis. I n a short note (27) published during t,he same year as the work on arsenic and ant,imony, he
In his first work on the chemistry of ruthenium (IS), dated March, 1894, Howe was seeking a simple reproducible way of preparing the except,ionally st,able socalled ruthenium "tetrachloride" described by Claus, the discoverer of ruthenium (41). Joly (42) had shown that Claus' compound contained nitrogen and that it should be formulated as RuC13N0 rather than RuC14,a conclusion which Howe verified (18). Claus' analytical error lay in the fact that he had not directly determined the percentage of evolved chlorine but had merely assumed that the weight loss on heating was due entirely to chlorine (theoretical 4C1/RuC14=58.40%), whereas it was actually due to nitric oxide and chlorine (NOCld RuNOCla=57.40%). The relative difference amounts to only 1.74%. When the uncertainties in the at,omic weight of ruthenium prevailing in Claus' time are considered (104.57 in contrast to today's accepted value of 101.07), his error is certainly understandable. Even today, the atomic weight of ruthenium is among the least certain for all the elements, since no really suitable compounds for its determination exist. Nevertheless, the necessity for complete analytical data, i.e., the direct determination of every constituent in deducing the formula of a compound should be obvious, and this Volume 45, Number 12, December 7 968
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necessity was emphasized by Briggs (45) and by Howe himself (&) As we shall see, incomplete analytical data have contributed to much of the uncertainty encountered in determining the formulas of ruthenium compounds. Another problem encountered by workers in the field that is exemplified by the compound under discussion is the question of the oxidation state (valence) of ruthenium, especially in its simple and complex chlorides. The problem is further complicated in the case of nitrosyl compounds, for nitric oxide, being a molecule with an odd number of electrons can form coordination compounds in three different ways: (1) loss of the odd electron followed by coordination of the resulting NO+ group, (2) coordination of the neutral S O molecule, or (3) gain of an electron followed by coordination of the resulting NO- group (45, 46). For example, in the compound Ru(NO)CI,, these three possible methods of combination would lead to oxidation states of (II), (111), or (IV), respectively, for the ruthenium atom. The question of the oxidation state of ruthenium in these and similar nitrosyls has been discussed by various workers (47-54), but a definite decision satisfactory to all has not been reached. Similar controversies arose in the case of the chloroaquo salts, as we shall soon see. Claus' error in ascribing the formula RuCla to what was actually RuCIJNO was carried over to the double salts (actually complex salts) of the supposed tetrachloride, known as "Claus' red salts." Thus he (41) attributed the formula 2MCl.RuClr (in modern formulation, J12[RuCls])to what Joly (42) later showed to be 2MC1.RuC1,NO (in modern formulation, AI2[Ru(ITO)CI6]). Howe (18) confirmed Joly's results in the case of the potassium and ammonium salts, and he prepared for the first time the corresponding anhydrous and dihydrated rubidium and cesium salts. He also investigated the reactions of uitrosochloride solutions ( [ R U ( N O ) C ~ ~ ]with ~ - ) various reagents and devised means for distinguishing them from hexachkoride ([RuCI6l3-) solutions. Cyanide Complexes
In contrast to the nitrosyl compounds, the chemistry of the cyanide complexes of ruthenium, the ruthenocyanides or hexacyanoruthenates(II), is well understood (55, 56). The best known representative of the series, via., IO Dechlorinated Hexa salt Howe Series plains t,he divergence in analytical results of Standing several 7-salt (Aoyama) different investigators. Indeed, the difficulty hovrs in sol". of complete interconversion of the salts of the HCI 540"-560three series, R12Ru1VC16, R12Ru'V(OH)C15, and R12Ru"'(H20)C16 was undoubtedly reK;RuCI, spoosihle for many of the discrepancies in Hexa Salt analyses.
marized all the experimental data known about the strange phenomenon, including some work that we have not yet considered. To complicate matters further, Aoyama (65) had described what he considered a third isomer of KpRuCls,formed by heating ILRuCI, in a current of dry hydrogen chloride a t 540'-56O0, i.e., by dechlorinating it. He called this compound the y salt to distinguish it from Miolati's (70) normal and Howe's (59)aquo salt, which he designated as a and p salt, respectively. Guthier and Niemanu (71) repeated Aoyama's work and concluded that his y salt was identical with the dehydrated 0 salt, since both p and y salts, when dissolved in dilute hydrochloric acid, crystallize out as aquo salt. This fact was confirmed by Howe (69). The most important relationships among the ruthenium chloride complexes are summarized in the diagram below:
1
t
1
\
/4'
Interrelotion$hipr among ruthenium chloride complerer.
The first attempt to explain the isomerism was made by S. H. C. Briggs (72), who considered the normal (a) salt a monohydrate, K2RuC15.Hz0but assigned to the aquo (0) salt the formula 2K2RuC1,.3H,0, which was based on inaorrect analyses. The next explanation for the isomerism, the one that proved to be correct, was offered by Raymond Charonnat (66), who proposed that the 0 salts were indeed aquo salts of tripositive ruthenium, M2[Ru"'(H20)Clj] (in modern n o m e n c l a t u r e , pentachloroaquoruthenates(III)), whereas the a salts were hydroxo salts of tetrapositive ruthenium, M,[RU'~(OH)CI~] (in modern nomenclature, pentachlorohydroxoruthenates(1V)). In short, according to this interpretation, the salts were not isomeric at all. The reason for the confusion, however, is obvious if the theoretical compositions for the t,wo compounds are compared (1964 atomic weights) : 110 KC1 3C1 Wt. Loss
Calcd. for K2Ru(H20)C16(%) 27.00 39.82 28 40 4.81 (H20)
t
Calcd. for KaRu(OH)CId%) 27.09 39.03 28.48 4 . .5G (OH)
Charonnat based his conclusions on three experimental facts: (1) the a but not the 0 salts liberate iodine from potassium iodide, (2) the 0 salt is formed by treatment of potassium trioxalat,oruthenate(III), un-
Analytical Chemistry
Claus, the discoverer of ruthenium, had shown as far hack as 1860 (75) that ruthenium is volatilized as ruthenium(VII1) oxide when fused with caustic alkalies and the melt treated with chlorine. Several years later, Schonbein (74) mentioned the soluhility of ruthenium metal in hypochlorite solutions, a similar reaction. Yet, although Claus' process for purifying ruthenium and Schonbein's method for cleaning apparatus on which ruthenium was precipitated had been in general use for more than sixty years, no one had subjected these reactions to a detailed critical study or had investigated whether they were suitable for the quantitative separations that were sorely needed in ruthenium chemistry. Howe (75) found that it was possible to separate ruthenium from all other platinum metals except osmium, which also forms a volatile tetraoxide, by dissolving the ruthenium compound in sodium hypochlorite solution whereu~on sodium ruthenate(V1) is formed. If osmium i i present, it is removed ' b i distillation with nitric acid. Chlorine is bubbled into the solution, forming ruthenium(VII1) oxide (76), which is separated quantitatively by distillation. Inasmuch as Howe was unable to collect the oxide for weighing or to precipitate the ruthenium quantitatively in a form that would be free of the alkali present, he devised a volumetric method (77, 78). The distillate containing the ruthenium(VII1) oxide was condensed in cold concenVolume 45, Number 12, December 1968
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trated hydrochloric acid, and the resulting hexachlororuthenic(1V) acid is titrated with tin(I1) chloride. Although the method did not qualify for the accurate quantitative determination of ruthenium, in the course of its development, as we have seen, Howe found that titrations with SnCL of K,RuCI, and of K,Ru(OH)Cl, (Miolati's a salt) both gave identical results, indicative of the presence of ruthenium(1V) in both compounds (75). This led to the explanation of the apparent "isomerism" among the chloride complexes of ruthenium (63). Ruthenium (11) Chloride
Forty years before the discovery of ruthenium, Fourcroy and Vauquelin (79, 80) noticed the blue color produced by the action of reducing agents on solutions containing platinum metals. Claus (81) later attributed this color to the formation of a dichloride RuC12,but he did not isolate the compound. Since that time the literature conceruing dipositive ruthenium has been not only voluminoua but also extremely polemical and contradictory (58, 40, 83-86), Even though the exact nature of the blue substance in solution has been much disputed, there is little doubt that i t contains some form of dipositive ruthenium. In an early paper (59), Howe prepared an easily oxidizable dark greenish blue double or complex salt of dipositive ruthenium by adding a concentrated cesium chloride solution to a freshly prepared blue solution of RuC12. According to his analytical results, Howe admitted that no definite well-defined compound existed; the chlorine content was too high for Ru(I1) but too low for Ru(II1). He suggested the formula 3CsCl.2RuCl2. 2H10, but in a later paper (87), he proposed the formula CslRuC14.nHI0 as being more probable. More recently (@), tetrachlororuthenate(I1) salts of organic bases (ethylenediamine, a, a'-dipyridyl, and pyridine) have been prepared. Since it had never been shown that the blue color produced by the reduction of tripositive ruthenium (77) is due to the same cause as that given by dissolving and extracting with alcohol the ruthenium chloride formed by chlorinating metallic ruthenium in the presence of carbon monoxide, Howe (65, 87) undertook such a study. He showed by titrimetric analysis that both solutions contained dipositive ruthenium. Ruthenium (11) chloride has not yet been obtained in crystalline form, and the crystallographic data of Goldschmidt, et al. (89) imply that the compound they examined was very similar to or identical with the trichloride. Conclusion
James Lewis Howe's name is perpetuated on the Washington and Lee campus by Howe Hall, which was built in 1924 and completely modernized in 1962 and which houses the instructional and research facilities of the chemistry and geology departments. His memory is also honored by the American Chemical Society's Blue Ridge Section, which presents annually an award to the best undergraduate chemistry students in the colleges of the area. For a period of more than four decades, Washington and Lee alumni recall having used Howe's "Inorganic Chemistry" (10) as a freshman text. I n the words of one of his former students, "However much they may have forgotten what was in the 81'0
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Journal of Chemical Education
book, they will never forget the man who wrote and taught it." (89). Howe's "universal interest in science, in church, in humanity; his absolute lack of any petty qualities; his unfailing optimism and unflagging energy; his ability to awaken enthusiasm in all of his hearers, linked him indissolubly to students and colleagues alike. With him the spirit of service has always been foremost. This [gave] to the South. . .one of its most brilliant teachers of chemistry and has brought to Howe that satisfacti0.n which comes when well-rendered service meets its full share of appreciation." (8b). Acknowledgments
The author is grateful for biographical information obtained from the following persons, many of whom are friends, students, colleagues, or relatives of Professor Howe: Mr. James Lewis Howe, Jr., Miss Guendolen Howe, Prof. John F. Baxter, Dr. Frederick E. Carter, Mrs. Lucius Junius Desha, Miss Rena Durkan, Prof. Edward F. Furtsch, Mr. Robert F. Gould, Prof. Dr. Oskar Glemser, Mr. Curtis C. Humphris, Mr. R. N. Latture, Miss Laura A. Magistrate, Mr. Hans Nussbaum, Dr. S. C. Ogburn, Jr., Mr. Martin A. Paul, Mr. Matthew W. Paxton, Prof. J. P. Phillips, Dr. E. F. Rosenhlatt, Mrs. G. M. Rosswick, Mrs. Mary H. Stahl, Prof. George S. Whitney, and Dr. Edward Wichers. He is especially indebted to Mr. Robert D. Epperson for assistance in collecting biographical and bibliographical data. Financial support was provided by the History and Philosophy of Science Program, Division of Social Sciences of the National Science Foundation (Grant GS-1580), the donors of the Petroleum Research Fund, administered by the American Chemical Society (Grant 1152-B), and the California State College a t Fresno Research Committee. Literature Cited
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(, 1.) KAUFFMAN, G. B.. J. CHEM.EDUC., (1959): Chwnio, . 36,521 . 6 , 180 (1960). G. B., J. CHEM.EDUC., 40,656 (1963). ( 2 ) KAUFFMAN, I.?) G. B.., "Alfred Werner. Founder of Coordination ~ -KAUFFMAN'. , ,~ Chemistry," Springer-Verlag, Berlin, Heidelberg, New York, 1966; J. CHEM.EDUC.,43, 155, 677 (1966); Chem isby, 39 (12), 14 (1966); Edue. Chem., 4 , 11 (1967). R., Chem. Revs.,32,277 (1943). ( 4 ) GILCHRIST, ( 5 ) HOWE,J. L., Amer. Chem. J., 5,415 (1883). ( 6 ) HOWE,J. L., A m . Chem. J., 5,418 (1883). (7) WEEKS,M. E., "Discovery of the Elements"(6th ed.), Journ d of Chemical Education, Easton, Pa., 1956, p. 440. ( 8 ) ( a ) "Who's Who in America," Marquis Publishing Co., Chicago, 1901-1902; ( b ) 1 . 1 ~S.~ C.. . Ind. and Eng. Chem., 18, 434 (1926); ( e ) Alumni News, Amherst College, 1955; ( d ) Lexington Gazette, Dee. 21, 1955; ( e ) Rockbridge County News, Dec. 22, 1955; (f) Chem. Eng. News, 34, 482 (Jan. 30, 1956); (g) The Alumni Magazine, Waahington m d Lee University, Jan., 1956, p. 16. ( 9 ) HOWE,J. L., "The Scientific Method and Religion," undated, holograph manuscript. (10) VENARLE, F. P., A N D HOWE,J. L., "Inorgsnic Chemistry According to Periodic Law," The Chemical Publishing' Co., Easton, Pa., 1898; HOWE,J. L.,"Inorgrtnic Chem-. istry for Schools and Colleges," The Chemical Publishing Co., Easton, Pa., 1907; 2nd ed., 1920. (11) HOWE,J . L.,PYOC. Am. Assoe. Ado. Sn'., 49.83 (1900); Science, 59,510 (1924); Science, 66,220 (1927). (12) BOGERT, M. T . (Chairman of the Chemistry Committee of the National Research Council), letter of July 21, 1917 to G . E. Hale (Chairman of the National Research Council). (13) HOWE,J. L., J. Am. C h m . Soe., 29, 382 (1907); 31, 1284 (1909); 33, 166 (1911); 34, 147 (1912); 35, 184 (1913); 36,230 (1914); 37,536 (1915). ~
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Group: Platinum, Palladium, Iridium, Rhodium, Osmium, Ruthenium, 1748-1896," Smithsonian Miscellaneous Collections, Vol. 38 (No. 1084), Smithsonian Institution, Washington, 1897,.qetavo, 318 pp. HOWE,J. L., A N D HOLTZ,H. C., "Bibliography of theMetala of the Platinum Group: Platinum, Palladium, Iridium, Rhodium, Osmium, Ruthenium, 1748-1917," Department of the Interior, U. S. Geological Survey, Bulletin 694, Government Printing Office, Weahington, 1919, 558 pp. HOWE,J. L., A N D STAFFOF BAKER& CO., INC.,"Bibliography of the Platinum Metala 1918-1930," Baker & Co., Inc., Newark, N. J., 1947; "Bibliography of the Platinum Metals 1931-1940," Baker & Co., Inc., Newark, N. J., 1949; "Bibliography of t,he Platinum Metals 19411950," Baker & Co., Ino., Newark, N. J., 1956. DE ULLOA,A,, "Relaci6n Hist6rica del Viage & la America Meridional," Antonio Marin, Madrid, 1748, Vol. 1, Book 6, Chap. 10, p. 606. HOSE, J. L., J . Am. Chem. Sac., 16,388 (1894). CLAUS,C., "Fragment einer Monog?aphie des Platin's und der Platinmetalle, 186.5-1883," Cammissionirc der Kaiserlichen Akademie der Wisaenschaften, St. Peteraburp, 1883.
1201 TI.. Platinum Metals Reuiew. 8. 67 (1964), ~ --McD0NnL.D. ~ - ~, (21) HtinNEn, H:, A&., 208,278 (1881); 210,>28 (1881). ' (22) HOWE,J . L., Amer. Chem. J . , 8 , 7 5 (1886). (23) HOWE,J. I,., A N D INERTINS,P. S., J . Am. Chem. Sac., 18, 953 (1896). (24) MARSH.J., Edinburgh New Phil. ,Journal, 21, 229 (1836); Ann., 23,207 (1837). (25) REINSCH, H., J. pham. Chem., 2,361 (1842). (26) REINSCH,H., J. prakt. Chem., 24, 244 11842). (27) HOITE,J. L., A N D CAMPBELL, H. I)., Amer. J . Sci., [iv] 2, 41:i 11XqRI .-. ~-~...,~ (28) HOWE,J. L., AND MORRISON, J. L., J . Am. Chem. Soe., 21, 422 (1899). (29) BRODIE,B. C., Proc. Roy. Inst., 1852, i, 201; 1854, i, 449. (30) SMITS,A,, "The Theory of Allat,rapy," Longmans, Green & Co., London, New York, 1922; "Die Theorie der Kom~ l e x i t i tnnd der Allotrouie." Verlar- Chemie G.m.b.H., ~ e r l i n ,1938. (31) HOWE,J. L., A N D HAMNER, S. G., J. Am. Chem. Sac., 20, 757 (1898). (32) PREUNER, G., A N D SCHUPP, W., Z. physik. Chem., 68, 129 (1909). (33) NEUMANN, K.. Z. physik. Chem., A171, 399,416 (1934). (34) XLEMM, W., .AND K I L I ~ NH., , Z. phwik. Chem., B49, 279 (1941). (351 , A,. J . Am, Chem. Sac., 20, . . HOSE. J. L.. A N D O ' N E ~ LE. 759'(1898). (36) PICCINI,A,. Z. anorg. Chem., 17, 355 (1898); 20, 12 (1889). (37) MELLOR,J. W., "A Comprehensive Treatise on Inorganic and Theoretical Chemistry," Val. 15, Longmnns, Green and Co., London, 1936, Chap. 69. (38) "Grnelins Handbuch der anorganischen Chemie" (8th ed.). System No. 63, Verlag Chemie GMBH, Weinheim/Bergst,rasse and Berlin. 1938. The literature is covered through the end of 1'937. (39) S r ~ o w r cN. ~ , V., "The Chemical ~ l d m e n t sand Their Compounds." Vol. 11, Clarendon Press, Oxford, 1950, pp. 1459-1489. (40) CHARONNAT, R., "Ruth6nium," in "Nouveau Trait4 de Chimie Minhrale (Editor: Pascal, P.) Vol. 19, Massan et Cie., Paris, 1958, pp. 21-171. The litemtnre is covered to 1955. (41) CLAUS,C., Bulletin de I'Aeaddmie Impdriale des Sciences de St. Pdtersbourg, [2] 5, 249 (1847); [3] 1, 103 (1860); J . prakl. Chem., 39,97 (1846); 79.35 (1860). (42) JOLT,A,, Compt. rend., 107,994 (1888); 108,854 (1889). (43) BRraGs, 8. H. C., J . Am. Chem. Soc., 48,2127 (1926). (44) HOWE,J. I,., J . Am. Chem. Soe., 48,2129 (1926). (45) SEEL,F., Z. anorg. allgem. Chem., 249,321 (1942). (46) MOELLER, T., J. CHEM.EDUC.,23, 441, 542 (1946); 24, 542 (1947). ~
(47) MANCHOT, W., A N D SCHMID, H., z. anOrg. allgem. Chem., 216, 99 (1934). (48) GLEU,K., A N D CUNTZE, W., Z. anorg. Chem., 237,189 (1938); GLEU,K., AND BODDECKER. . I.,. Z. anorg. Chem.,. 268,202 . (19.52). (49) MELLOR,D. P., AND CRAIG,D. P., J . Proc. Roy. SOC.N . S. Wales, 78,2.5 (1944). (50) MANcHoT, W., A N D DUSING,J., Z. anorg. Chem., 212, 109 ilu331~ (51) MORGAN, G. T., A N D BURSTALL, F. H., J. Chem. Soe., 1938, 3675. (52) WERNER, A,, Ber., 40,2614 (1907). (53) CHARONNAT, R., in "Trait6 de Chimie MinPrale" (Editon PASCAL, P.), Val. 11,,Massan et Cie., Psris, 1932, pp. 411, 416; Ann. chim., 1101 16,227 (1931). (54) HEIN,F., "Chemisehe Koardinationslehre," S. Hirzl, Zurich, 1950. (5.5) CLAWS, C., "heitriRe ZUL. Chemie der Platinmetalle," F&schrift Universitit Xasan, Dorpst, 1854, p. 97. (56) M n R ~ m s C. , A,, "Ueber die Cysnverbindungen der Platin\----,.
metalle," Inaugural Dissertation, Universitiit Gettinge", 1860. (57) HOVE,J. L., J. Am. Chem. Sac.. 18,981 (1896). C A M P B E E. L ~D., J . Am. Chem. Soe., 20, (58) HOSE, J. I.., .AND 29 (1898). (59) HOWE.J. L.. J . A m . Chem. Soe.. 23.775 11901). isoj CLAWS; ~ u l l~. h y smath. . Aeai. pdtersb., '3, 353 (184.5); Ann. Physik, 65,200 (1845). (61) G ~ n n s ,0.W., Am. J . Sci., [2] 34, 341 (1862); 37, 57 (1864). (62) . . HOSE. J. L.. J . Am. Chem. Soe.. 26.543 119041 (631 Chem. ~oc.:49.'2381'i19271 ~~, ~, HOWE: J. L.: .I.Am. ,~ , (64) XRAUSS, F., Z.anarg. C h e m l l i 7 , ill(1921). (65) AOYAMA, S., Z. anorg. Chem., 138,249 (1924). (66) CHARONNAT, R., Compt. rend., 180,1271 (192.5). (67) LIND,S. C., Thesis, hlassaohusetts Institute of Technology, 1902: LIND,S. C., A N D BLISS,F. W., 3 . Am. Chem. Soc., 31,868 (1909). (68) Howm, J. L., J. Am. Chem. Sac., 26, 942 (1904). (69) HOWE,J. L., AND HAYNES, L. P., J . Am. Chem. Soc., 47,2920 (1925). (70) Mlor,nTr, A., A N D TAGIURI,C. C., GOZZ.ehim. ztol., 30, 11, 511 (1900). W., Z. anorg. Chem.. 141, 312 (71) GUTBIER,A,, A N D NIEMANN, (192.5). . . (72) BRIGGS,S. H. C., J. Chem. Soc., 127,1042 (1925). (73) CLAUS,C., Bd1. de I'Aeaddmie Impdriale des Sciences de St. Pdtersbourg, 1, 97 (1860); Mdlanges phys. chim. mad. sei. St. Pdtersbowg, 4 , 2 0 (1860). (74) SCHBNREIN, C. F., Ann. ehim. phys., [4] 7, 103; 8, 465 (18661. (75) ~ d w J.~L., , AND MERCER,F. N.: J . Am. Chem. Sac., 47, 2926 (19253. (76) HOSE, j. L.,Chem. News, 78,269 (1898). (77) HOSE, J. L.,Science, 65,503 (1927). (78) H o u q J. L., J. Am. Chem. Soc., 49,2393 (1927). (79) F o u n c ~ o A. ~ , F., N D VAUQUELIN, L. N., Ann. chim., 49, 188,219 (1804); 50,R (1804). (80) YAUQUELIN, L. N., Ann. chim., 89, 150,225 (1814). (81) C ~ a u sC., , Ann., 56,238,260 (1846). (82) R b ~ u II., , A N D WAGNER. T., Bw., 60, 494 (1927). (83) ZINTI,,E., A N D Z A I M P., ~ , Rer., 60,842 (1927). (84) RBMY, H., Z. anorg. Chsm., 113, 229 (1920); Z. anrew. Chem., 42,2R9,291 (1929). (85) KRAUSS,F., Z. angew. Chem.. 41, 413 (1928). (86) GALL,I-I., Z.angew. Chem., 41,1070 (1928). (87) HOWE,J. L., Hnn'E, J. L., JR.,AND OGRURN, S. C., JR., J . Am. Chem. Soe., 46.335 (1924). (88) GODWARD, L. W. N., AND WARDLAW, W., J . Chem. Soc., 1938,1422. V. kf..BIRTH, T., HOLMSEN, D., LUND,G., (89) GOLDSCHMIDT,
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