1 The Chemistry and Literature of Beryllium BY CHARLES LATHROP PARSONS, B. S. PROFESSOR OF INORGANIC CHEMISTRY IN NEW HAMPSHIRE COLLEGE EASTON, PA.: THE CHEMICAL PUBLISHING CO. LONDON, ENGLAND : WILLIAMS & NORGATE 14 HENRIETTA STREET, COVENT GARDEN, W. C. COPYRIGHT, 1909, BY EDWARD HART. PREFACE. This book is written with the main object in view of saving preliminary study and labor to future investigators of beryllium and to point out some pf the peculiarities of this interesting ele- ment which are apt to lead the novitiate toward erroneous con- clusions. Especially is it desired to call attention to the fact that a large proportion of its accredited compounds are in reality but indefinite solid solutions. This condition of the literature of beryllium is due to the abnormal extent to which its hydroxide is soluble in solutions of its normal salts, giving rise to solids of almost any degree of basicity or to solutions with decreased osmotic effects. Accordingly, results of analysis, freezing points, etc., give little evidence of the true nature of its compounds, un- less accompanied by proved definiteness of composition, a proof too often omitted throughout the whole field of inorganic chem- istry, but nowhere more than in studying beryllium and its com- pounds. More labor has been expended upon the bibliography than its limited extent may seem to indicate. It is believed that it will be found to contain references to all or nearly all the original articles on beryllium and that the references to abstracts will also be found fairly complete through 1902. Since 1902 the original articles and chief abstracts have alone been entered. It has been deemed advisable to include a brief abstract, at times critical in tone, of each article, but it is not claimed that these abstracts al- ways cover the full subject matter of the original, although nothing important is intentionally omitted. The Journals examined are approximately the same as those listed in James Lewis Howe's unexcelled Bibliography of the Platinum Metals and the plan followed is in general the same as outlined by him. The abbreviations used are familiar to all chemists. Grateful acknowledgments are due especially to the libraries IV PREFACE of the Massachusetts Institute of Technology, the Library of Harvard University, the Boston Public Library and to the Library of the American Academy of Arts and Sciences. Also to the Boston Atheneum and to the libraries of Columbia University, N. Y., and the Surgeon General's Office and the Patent Office in Washington. The author also desires to express his thanks and appreciation of a grant allowed him by the American Asso- ciation for the Advancement of Science toward expenses incurred in the preparation of the Bibliography. CHARLES L. PARSONS. Durham, N. H., Oct. i, 1908. TABLE OF CONTENTS. PART I. Chapter I. Introduction i-io Discovery, name, history, occurrence, preparation from beryl, detection, separation, determination. Chapter II. Metallic Beryllium 1 1-16 Preparation, properties, valency, alloys. Chapter III. Normal Compounds of Beryllium X 7~44 Discussion, fluoride, chloride, bromide, iodide, oxide, sulphide, selenide, telluride, trinitride, phosphide, cyan- ide, carbide, borocarbide, silicide, hydroxide, chlorate, bromate, iodate, sulphates, sulphite, thiosulphite, dithion- ate, sulphocyanate, selenate, selenite, tellurate, tellurite, chromite,chromate, molybdate, nitrate, nitrite, phosphate, hypophosphate, pyrophosphate, phosphite, pyrophos- phite, vanadate, arsenate, antimonate, columbate, carbon- ate, silicates, silicotungstate, fluosilicate, aluminate, fer- rocyanide, ferricyanide, nitro prusside, beryllium ethyl, beryllium methyl, beryllium propyl, formate, acetate, propionate, acetylacetonate, oxalates, tartrates, succin- ate, picrate, alpha-bromcamphor sulphonaie, rhodizon- ate, kroconate, citraconate, fumarate, maleate. Chapter IV. Acid Salts of Beryllium 45*4^ Discussion, mono acid phosphate, acid arsenate, acid selenites, acid oxalate, acid molybdate. Chapter V. Double Salts of Beryllium 47-60 Discussion, double chlorides, fluorides, iodides, sulphides, cyanides, sulphates, sulphites, nitrites, phosphates, car- bonates, oxalates, tartrates, racemates, malates. Chapter VI. Basic Compounds of Beryllium 61-71 Discussion, basic acetate, basic formate, basic propionate, basic isobutyrate, basic butyrate, basic isovalerate, in- definite basic solid phases, basic sulphates, basic oxalates, basic carbonates, miscellaneous basic solid phases. PART II. Bibliography of Beryllium 72-168 Authors' Index Subject Index PART I. CHAPTER I. INTRODUCTION. Discovery. In 1797 L. N. Vauquelin undertook to prove the chemical identity of the emerald and beryl, which had already been suspected by Haiiy, and in the course of his analytical research, discovered that a portion of the precipitate which had previously been supposed to be aluminium hydroxide, was thrown out of its solution in potassium hydroxide on boiling. He also found that this new hydroxide was soluble in ammonium car- bonate, formed no alum and was in many ways different from aluminum. These observations led him to announce in a paper read before the Institute on Feb. 14, 1898 (1798; i), 1 the dis- covery of a new "earth." Name. In his first articles on the subject (1798; i, 2 and 3), Vauquelin refers to the newly discovered oxide as "la terre du Beril," which was translated into German as "Beryllerde," from which the name Beryllium took its rise. At the end of Vauque- lin's first article, the editors of the Annales de Chimie suggested the name "glucine," for the new oxide, and Vauquelin in his fourth publication (1798; 4) adopts the suggestion prefacing its use with the remark "on a donne le nom de glucine." As early as 1799, Link (1799; 3) had objected to the use of this term as too closely resembling "glycine," already in use, and indeed. Vauquelin, himself (1798; 3) seems to have accepted it with reluctance. In 1800 Klaproth (1800; i) objected to its use because the salts of the yttrium earths were also sweet and Ekeberg (1802; i) agrees with this idea. The name "Beryl- lium" itself was used when, in 1828, Wohler, (1828; 2) for the first time, separated the metal. For the sake of uniformity in general usage which is overwhelmingly in favor of the name 1 References are to Bibliography, Part II. 2 CHEMISTRY OF BERYLLIUM derived from beryl, and as "glucine" grew into use in French literature without being proposed by the discoverer, much as "beryllerde" in Germany, and for the reasons set forth in 1904, 1 1 and 1905, 2, it has been deemed advisable to adopt the name "Beryllium," already in use by far the majority of chemists. History. Following the discovery of the element, Vauquelin studied and announced the properties of some of its chief com- pounds. In 1828 the metal itself was produced in a very impure form by both Wohler (1828; 2) and Bussy (1828; 3). Awdejew (1842; 2) added materially to the literature of the subject and made the first determinations of the atomic weight that have any claim to accuracy. Weeren (1854; i) and Debray (1855; i) also carried on extensive investigations of the metal, its atomic weight and chief compounds. Joy (1863; i) undertook an ex- tended research on the preparation of its compounds from beryl and published a fairly complete bibliography of the subject to his day. Atterberg and Nilson and Pettersson in the years be- tween 1873 and 1885, made large additions to the chemistry of beryllium, and during these years a long, earnest and interesting discussion, which had begun as early as Awde Jew's time, was carried on by Nilson and Pettersson, Humpidge, Reynolds, Hart- ley, Lothar Meyer, Brauner, and others regarding the valency of beryllium and its place in the periodic system. The discus- sion has continued up to the present day, but was in reality settled when Nilson and Pettersson (1884; 7, 8) determined the vapor density of the chloride, and Humpidge (1886; i) showed that at high temperatures the specific heat of beryllium ap- proached very closely to normal. Kruss and Moraht (1890; 4 and 5) made a re-determination of the atomic weight in 1890, and between the years 1895 and 1899, Lebeau published an important series of articles which are summed up by him (1899; n) in one of the very best articles on beryllium and its compounds. Urbain and Lacombe (1901; 2) and Lacombe (1902; 3) dis- covered the remarkable basic salts of the acetic acid series and Parsons re-determined the atomic weight by new methods (1904; 5, 1905; 5) and studied many compounds, especially the so-called basic salts of some of the earlier writers (1904; 10, 1906; i, 2, INTRODUCTION 3 3, 4, 13, 1907; 3, 10, n). Numerous other investigators as will be seen from the bibliography, have also contributed to the chemistry of beryllium. Occurrence. The chief form in which beryllium is found in nature is the silicate, beryl, Be 3 Al 2 (SiO 3 ) 6 , (BeO, 13.5 per cent.) including its gem forms, emerald and aqua marine and from this mineral most of the beryllium investigators have de- rived their material. Beryllium compounds have also been de- rived from gadolinite, Be,F 3 (YO) 2 (SiO 4 ) 2 , (BeO, 10 per cent.) and leucophane, Na(BeF)Ca(SiO 3 ) 2 , (BeO, 10.3 per cent). Other important minerals containing this element are chryso- beryl, Be(AlO 2 ) 2 , (BeO, 19.2 per cent.); phenacite, Be 2 SiO 4 , (BeO, 45.5 per cent.) ; euclase, Be(AlOH)SiO 4 , (BeO, 17.3 per cent.) ;bertrandite,H 2 Be 4 Si 2 O 9 , (BeO, 42.1 per cent.) ;and eudidy- mite, HNaBeSi 3 O 8 , (BeO, 10.2 per cent). Helvite, danalite, epididymite, crytolite, erdmanite, muromontite, alvite, foresite arrhmite, siphlite, trimerite and meliphanite, are rare and complex silicates, while beryllonite, NaBePO 4 , (BeO, 19.7 per cent.) ; herderite, (CaF)BePO 4 , (BeO, 15.4 per cent.); hambergite, Be 2 (OH)BO 3 , (BeO, 53.3 per cent), are interesting merely from a mineralogical standpoint as natural occurrence of the element. Beryllium has also been noted in some natural waters, in mon- azite sand, and in some aluminous schists. It is quite probable that it would have been found more frequently in rock analysis if some simple method of separating it from aluminum had been earlier known. Preparation from Beryl. Since beryl is not directly attacked by any acid, except, perhaps, by hydrofluoric when ground to a dust, it must first be fused with some flux or be heated in the electric furnace to a temperature (Lebeau, 1895; 5) which volatilizes some of the silica and leaves a residue easily attacked by hydro- fluoric acid. For those having the facilities, this latter method presents many advantages. Among the fluxes which can be suc- cessfully used are sodium and potassium carbonates, calcium flu- oride, potassium fluoride, calcium oxide, and sodium and potas- sium hydroxide. The fluorides possess the advantage in subse- quent treatment, in the comparative ease of removal of the large 4 CHEMISTRY OF BERYLUUM excess of silica, but for other reasons have been seldom used. Under average conditions the caustic alkalies, preferably potas- sium hydroxide, give the most satisfactory results. Beryl is readily attacked by about its own weight of potassium hydroxide at a comparatively low heat in a silver or nickel cru- cible, although a salamandar or carborundum crucible can be used. Clay, graphite or iron crucibles are not available as they are immediately attacked. The fused mass should be broken up, just covered with water, strong sulphuric acid added until present in slight excess and the now gelatinous mass heated and broken up until fumes of sulphuric acid are given off and the whole has the appearance of a fine white powder. The residue is next treated with hot water when the sulphates of beryllium, alumi- num, iron and potassium pass into solution and on evaporation most of the aluminum separates out as alum and can be removed. The mother liquors, containing all of the beryllium together with impurities, should be oxidized by boiling with nitric acid to con- vert the iron into the ferric condition, neutralized with ammonia and enough sodium bicarbonate crystals added to saturate the so- lution. The liquid should now be warmed and shaken frequent- ly during a period of twenty-four hours, when most of the beryl- lium will pass into solution almost perfectly free from aluminum and also from iron unless other salts are present, which is some- times the case. By again dissolving and re-treating the residue left after filtration, practically all the beryllium will be found in the bicarbonate solution. To this solution ammonium sulphide is added to remove any dissolved iron and the whole diluted to five times its original volume. By blowing steam through this solution to the boiling point the beryllium will be precipitated usually as a fine, granular basic carbonate easily filtered and washed. The basic carbonate will be found to be quite pure (1906 ; 2) save for some two per cent, of occluded sodium salt, but its CO 2 content and the ease of filtration will vary great- ly with the conditions of the hydrolysis and the length of the heating process. The method employed by Pollok (1904; i) possesses some advantages in that he uses sodium hy- droxide, dissolves in hydrochloric acid and after filtering off INTRODUCTION 5 the main part of the silica, without evaporation, passes hydro- chloric acid gas through the filtrate, to the saturation point, where- by most of the aluminum is removed as the tetrahydrated chlo- ride together with the remainder of the silica, and in a form which permits of easy washing. The beryllium may then be recovered, after oxidation of the iron, by its solubility in boiling acid so- dium carbonate, in which the impurities ordinarily present are entirely insoluble, or it may be obtained in a less pure form by its solubility in ammonium carbonate, which is the method up to the present time almost universally employed. The final separation by ammonium carbonate has the disadvan- tage that notable quantities of aluminum and iron also dissolve and the use, in large quantities, of a somewhat expensive reagent. It has the advantage of yielding the basic carbonate in a form which is easily washed from all impurities except ammonia. As is the case when acid sodium carbonate is used, solution takes place much more readily in the strongly saturated reagent, and the subsequent partial hydrolysis is greatly hastened by large- ly increasing the mass of the water present and is in both cases practically complete on diluting to a two per cent, solution and heating to the boiling point. Steam is much more preferable than direct heating as the violent and almost explosive "bump- ing" which is unavoidable in the latter case is thereby entirely prevented. Although not noted until very recently, (1906; 4) the basic carbonate produced in this manner contains about two and one-half per cent, of ammonia which can be removed by long boiling in pure water, which also gradually removes the carbon dioxide and leaves the beryllium in the form of the hydroxide, no more readily washed than if it had been precipitated as such. In practice a much better method is to heat the basic carbonate in contact with many times its weight of water, to momentary boiling with steam, filter and repeat several times with fresh water. This method is much more productive of results than washing with hot water, and the carbon dioxide is for the most part retained. The comparatively small amount of iron that dis- solves in acid sodium or ammonium carbonate may be removed by adding ammonium sulphide, shaking and filtering off the fer- CHEMISTRY OF BERYLLIUM rous sulphide with special precaution as to its oxidation during- the filtration. The hydroxide or basic carbonate thus produced is the best form to use as a starting point in the production of other beryllium compounds. Special purification from all other metallic elements can be most readily secured by conversion into the basic acetate and re- crystallization from hot glacial acetic acid (1906; i). On the other hand, the material prepared by the sodium bicarbonate method (1906; 2) is pure except for a small amount of sodium which can not be washed out. This can be removed by re-solu- tion in acid and precipitation with ammonia. Other methods for the removal of iron, aluminum, etc., will be noted under analysis. SEPARATION AND DETERMINATION. Except in the case of such pure salts as can be directly ig- nited to the oxide, beryllium is precipitated as the hydroxide, by ammonia or ammonium sulphide, washed with water to which a little ammonium acetate or nitrate has been added (1906; 2) and ignited to the oxide. When alone, its determination presents no difficulty except the great tendency of the hydroxide to pass through the filter in the colloidal state when washed with pure water. This is, however, entirely overcome by the use of ammonium acetate or nitrate as already noted. Detection. Follow the customary procedure of qualitative analysis until the sulphides insoluble in HC1 have been removed. Concentrate the filtrate so obtained to 25 cubic centimeters and when cold add two grams solid Na 2 O 2 , boil and filter. Acidify the filtrate with HNO 3 and add ammonia in excess. If no pre- cipitate is obtained beryllium is absent. Wash any precipi- tate formed and add it together with two to three grams solid NaHCO 3 to 20 cubic centimeters (10 per cent, solution) of water in a test-tube or casserole and bring rapidly to boiling. Boil for one-half minute only and filter to remove all aluminum. Dilute the filtrate with 10 volumes of water (one per cent, so- lution) and boil. Beryllium hydroxide containing a little car- bonate will precipitate if present. Other elements do not in- terfere. INTRODUCTION 7 Separation. In minerals and in admixture with other ele- ments, the ordinary treatment to separate aluminum and iron should be followed and the beryllium will be found together with these two elements in their final separation. It is quite probable that beryllium has been weighed and calculated as alu- minum in many mineral and rock analyses. Many methods of separation of beryllium from iron and from aluminum, have been followed, although most reported analyses depend on the solubility of beryllium hydroxide in ammonium carbonate. Vauquelin (1798; i) proposed the use of ammonium carbonate, but his first separation depended upon the solubility of beryllium hydroxide in potassium hydroxide and its precipi- tation on boiling. Gmelin (1840; i) and SchafFgotsch (1840; 2) both used this same method, but it is very far from being ac- curate. Scheerer (1842; 3) first proposed the separation of the last traces of iron from the ammonium carbonate solution by means of ammonium sulphide. Berthier (1843; 2 ) suggested the use of ammonium sulphite as a reagent, but the method was shown to be valueless by Bottinger (1844; i). In 1850, Rivot (1850; i) proposed the ignition of the mixed oxides in a current of hydrogen, whereby the iron was reduced to metal and could be dissolved out with dilute nitric acid, or its mass determined by the loss in weight. Debray (1855; i) developed a separation dependent upon the action of zinc on the mixed sulphates, pre- cipitating the aluminum as a basic sulphate, but the method was never claimed to be quantitative. Joy (1863; i) made a com- parative study of all methods proposed to his time. Gibbs (1864; 3) first suggests the use of sodium fluoride, to quantitatively separate aluminum from beryllium, and Pollok (1904; i) shows that the fluoride separation is exceedingly sharp. Cooke (1866; i ) after reducing the iron in hydrogen, volatilizes it in a current of hydrochloric acid gas. Havens and Way (1899; 5) accomplished the same result without previous reduction of the oxide. Ross- ler (1878; 9) succeeded in separating beryllium from small amounts of aluminum by precipitating with ammonium phosphate in presence of citric acid. Vincent (1880; 2) uses dimethylamine to precipitate beryllium salts and finds that the aluminum com- 8 CHEMISTRY OF BERYLLIUM pound is soluble in excess of the reagent; iron acts like beryl- lium. Renz (1903; 4) confirms this, states the same to be true of methyl, ethyl, and diethylamine and claims the results to be quantitatively accurate. Zimmermann (1887; 5) returns to the old potassium hydroxide method without any special addition. JSchleier (1892; 6), Atkinson and Smith (1895; 9), and Burgass (1896; 7) separate iron quantitatively from beryllium by nitroso- beta-naphthol. Lebeau precipitates the iron in nitric acid solu- tion with ferrocyanide, the excess of ferrocyanide with copper nitrate and the copper as sulphide. Hart ( 1895 ; 6) removes the major part of both iron and aluminum by careful precipita- tion of the sulphates with sodium carbonate, the beryllium being the last to precipitate, owing to the great solubility of its own hydroxide in its own sulphate. Havens (1897; 4) separates beryllium from aluminum quantitatively by the insolubility of aluminum chloride tetrahydrate in a mixture of hydrochloric acid and ether, which has been saturated with hydrochloric acid gas, and Follok, (1904; i) uses this same method for preparation purposes, omitting the ether. WyroubofF (1902; 2) precipitates beryllium as the double oxalate with potassium from hydrochlo- ric acid solution. Classen (1881; 3) electrolyzes in presence of oxalate of ammonium, the beryllium being dissolved in the car- bonate of ammonium formed. Haber and Van Oordt (1904; 4) dissolve basic beryllium acetate in chloroform, leaving iron and aluminum acetates behind. Myers (1904; 7) removes iron electrolytically from a slightly acid solution of the sulphate, using a mercury cathode. Parsons and Robinson (1906; i) sep- arate basic beryllium acetate in a pure state from other acetates, by means of its ready solubility in hot glacial acetic acid and comparative insolubility in the same reagent when cold. Par- sons and Barnes (1906; 2) show the solubility of beryllium hy- droxide in a saturated solution of acid sodium carbonate, and the insolubility of the hydroxide of iron and aluminum in the same reagent. Glassmann (1906; 8) rediscovers the sulphite separation of Berthier (1843; 2 ) Bottinger (1844; i) and Joy (1863; i), and the fact that the method is old is pointed out by Friedheim (1906; 12), Noyes, Bray and Spear (1908; 2) give accurate methods for its separation and detection. INTRODUCTION 9 Determination. In the opinion of the author, the separation by means of acid sodium carbonate offers the quickest, most direct and best method for estimating beryllium in admixture with other elements. The method of Havens (1897; 4) is equally accurate if care is taken to fully saturate with hydro- chloric acid gas. The first portion of the analysis will be the regular procedure, followed to obtain the hydroxides of iron and aluminum if present and the beryllium will be found also as an hydroxide in this precipitate. The mixed hydroxides of which less than one gram should be present, are dissolved in as little as possible hydrochloric acid, oxidized by a little nitric acid, ammonia added to nearly neutralize and evaporated to about 25 cubic centimeters. This solution is then heated to boiling and added with stirring to 75 cubic centimeters of hot (75) water, containing 12 to 15 grams of the pure crystallized acid sodium carbonate. The beaker which contained the chloride is rinsed with a little hot water and the whole brought immediately to boiling and held there for one-half minute. Care must be taken not to confuse the evolution of carbon dioxide with the actual boiling of the liquid, which must take place. Under these conditions the beryl- lium hydroxide passes into solution, and the aluminum and ferric hydroxides are precipitated carrying with them a small amount of beryllium. 1 The liquid is allowed to cool and settle and is filtered into a liter beaker and washed three times with a hot (75") solution of acid sodium carbonate containing 100 grams to the liter. The precipitate is now redissolved in hydrochloric acid and treated as before, allowing the filtrates and washings to run into the same beaker as first used. The filtrate is now carefully acidified with hydrochloric acid, the beaker being covered to prevent loss by spattering, is boiled to remove all carbon dioxide and the beryllium precipitated as hydroxide by ammonia, avoiding any large excess. The precipitate is allowed to settle, the supernatant liquid decanted through the filter and the precipitate washed twice with hot water, redissolved in a lit- 1 Uranium may interfere as has been pointed out ( 1908; 2) but it is sel- dom present with beryllium and may be easily detected by ferrocyanide and its separation presents no difficulty. 10 CHEMISTRY 01? BERYLLIUM tie hydrochloric acid and again precipitated with ammonia to remove sodium salts invariably occluded in the first precipitation. The precipitate is now washed with hot water containing two per cent, ammonium acetate or nitrate until the washings give no chlorine reaction. The hydroxide is ignited to the oxide in a platinum crucible without previous drying, and weighed. CHAPTER II. METALLIC BERYLLIUM. Preparation. 'Beryllium was first prepared in the elementary state by Wohler (1828; 2) and by Bussy (1828; 3), acting in- dependently, by the action of potassium on the anhydrous chloride. Davy (1809; i) had previously attempted to reduce the oxide without success and Stromeyer (1812; i) claimed to have re- duced the oxide by a mixture of carbon, iron and linseed oil in 1812. Wohler according to the records has priority over Bussy and deserves further credit in that he made a careful study of his product, which being very impure led him to announce some properties since shown to be erroneous. Debray ( 1855 ; i ) substituted sodium for potassium and passed his chloride, in the sublimed state, over the melted metal. Menier (1867; i) exhibited a sample of metallic beryllium at the Paris Exposition, which he had prepared by the action of sodium upon a mixture of ben-Ilium chloride and the double fluorides of beryllium and potassium in a crucible of pure aluminum. Reynolds (1876; 3) reduced the chloride by sodium, and Nilson and Pettersson (1878; 3 and 4) used the same method and succeeded in obtain- ing a metal of 87 per cent, purity by fusing under a salt cover in a crucible of iron tightly closed. Again (1880; 6 and 7) the same authors succeeded in procuring a metal of 94 per cent, purity but it was not until Humpidge (1885; I, 1886; i) made his final specific heat determinations in 1885, that a metal of as high a degree of purity as 99.2 per cent, was obtained. Wink- ler (1890; 3) claimed to have reduced the oxide by magnesium and Goldsmith (1898; 14) by aluminum, but both chemists were undoubtedly mistaken. Kriiss and Moraht (1890; 4 and 5) re- duced the double fluoride of beryllium and potassium with sodium, obtaining their metal in hexagonal plates. Pollok (1904; i and 9) again produced the metal by decomposition of the chloride with sodium, and states that he was unable to fuse to- 12 CHEMISTRY OF BERYLLIUM gether the dark gray powder formed for the reason that it probably volatilizes at ordinary temperatures without passing through the liquid condition. It was left to Lebeau (1898; 3) to develop an apparently sim- ple and easy method for producing the metal almost free from admixture, which he did by electrolyzing the double fluoride of beryllium and of potassium or of sodium in a nickel crucible. It is true that Warren (1895; 10) had claimed to manufacture the metal by the electrolysis of the bromide which does not conduct electricity, and Borchers (1895; n) had proposed the prepara- tion by means of electrolyzing the chloride, mixed with an alkali chloride but apparently without result. Lebeau proved that the halides of beryllium did not conduct electricity so he added sodium fluoride to beryllium fluoride, melted the mass in a nickel crucible which itself became the cathode, and using a carbon anode, passed a current from a dynamo yielding normally 20 amperes at 80 volts. Care was exercised to keep the heat but little above tne melting point and metal was obtained in hex- agonal crystals. Some patents of Liebermann (1898; 15 and 16) and Kiihne (1907; 2) for the production of beryllium would appear to be of very doubtful value. Physical Properties. Beryllium is a hard ; dark steel gray metal, which especially in its crystal form has a bright metallic luster. The crystals produced by electrolysis (Lebeau, 1898; 3, 1899; n) are hexagonal lamallae, placed one on the other and according to Brogger and Flink (1884; 4) occur in two forms, prismatic and tabular, belonging to the holohedral division of the hexagonal system and having an axis relation of a:c=i : 1.5802. The specific gravity of the crystals is 1.73 at 15 (Lebeau, 1899 ; n), of the metal produced by reduction with, sodium 1.85 at 20" (Humpidge, 1886; i). Other published figures were on im- pure material and need not be given. The melting point is not, known for at ordinary pressures and in an inert atmosphere it volatilizes without fusion, (Pollok; 1904; i). Under pressure it can be fused (Nilson and Fetters- METALLIC BERYLLIUM 13 son, 1878; 3) but no determinations of the temperature have been made. The specific heat at ordinary temperatures is abnormal as in the case of boron, carbon and silicon, but Humpidge (1885; I, 1886; i) has shown that between 400 and 500 it remains practically constant at about 0.62. The matter was one of long controversy and the low results obtained by Nilson and Petters- son (1878; 3) and others was the chief cause of the belief in the trivalency of beryllium. According to Humpidge (1885; i and 6, 1886; i) the relation between specific heat and tem- peratures can be expressed by the empirical formula: K, = 0.3756 + 0.00106 t 0.00000114 /*. According to Thalen (1869; 2 ) w ^ was fi rst to study the spectra of beryllium it is characterized by a line 4572.0 in the blue and 4488.5 in the indigo of about equal intensity. Lockyer (1878; 10) finds beryllium lines in the sun's spectra. Hartley (1883; 5) makes a careful study of the arc spectra of the chlo- ride and publishes a chart of the spectra of beryllium, which besides the two lines in the visible spectra noted above by Thalen, he finds the lines 3320.5, 3130.2, 2649.4, 2493.2, 2477.7 * which 3130.2 is the strongest and most persistent. Rowland and Tat- nall (1895; 4) in their exhaustive study of the arc spectra of the elements, found the most prominent lines for beryllium be- tween 2100 and 4600 to be 2348.697 2650.414 3321.218 2350.855 2651.042 3321.486 2494.53 2 3130.556 4572.869 2494.960 3131-200 These observations were made with a grating of 21^/2 feet radius and 20,000 lines to the inch on a photographic plate 19 inches in length and are unsurpassed for accuracy. Formanek (1900; 3) finds that the chloride treated with Alkanna tincture presents a strong orange red fluorescence and yields three ab- sorption bands. Soret (1878; 11) finds that solutions of the chloride give no absorption spectra and only a feeble bluish iluorescence. Crookes (1881; 4) found that beryllium oxide, in high vacuo, gave a beautiful blue phosphorescence, but 14 CHEMISTRY OF BERYLLIUM no spectral rays. Hartley (1901 ; i) finds that the lines x 3130.3 and 2478.1 are still visible in solutions of beryllium salts when the concentration has fallen so low as o.oooooi per cent. The atomic ivcight of beryllium is very close to 9.1. The first determination was made by Berzelius (1815; i) early in the last century and were little more than approximations. The cor- rected results of other investigators with the ratio determined are as follows: Mean O = 16 Awdejew ( 1842 ; 2 ) BeO : BaSO 4 9 .34 Weeren (1854 ; i) BeO : BaSO 4 9.27 Debray (1855 ; i) BeO : 4CO 2 9.34 Klatzo ( 1869 ; i ) BeO : BaSO 4 9. 28 Nilson and Pettersson (1880 ; 6) BeSO 4 4H,O : BeO . 9.104 Kriiss and Moraht (1890 ; 5) BeSO 4 -4H 2 O : BeO . 9.05 fBe(C 6 H 7 O a )r-BeO. 9- "3 Parsons (1904 ; 5 ) JBe 4 O(C 2 H s O 2 ) 6 : BeO 9.113 f Algebraic combina- Parsons (1905 ; 5) ] tion of above. Be 9.112 (. and C unknown Chemical Properties. Chemically, beryllium is a metal slight- ly less basic in its nature than magnesium. According to Brau- ner (1881; i) the chemical nature of beryllium may be summed up by the three statements : Si : Be = Be : B, Si : Na = Be : Mg = B : Al, Si : Mg = Be : Al = = B : Si. Beryllium is not altered in dry air nor in oxygen at ordinary temperatures but takes fire when highly heated and if finely divided yields bright sparks in the flame of a Bunsen burner. (Lebeau, 1899; n). It combines directly and easily with fluorine, chlorine and bromine (Lebeau, 1898; 3) and with iodine when heated in its vapor (Wohler, 1828; 2) and (Debray, 1855; i). Wohler claimed to make a sulphide by heating in sulphur vapor but Fremy, (1853; i) and Debray, (1855; i) were unable to get the two elements to combine directly and it has not since been produced in this manner. Strong sulphuric acid attacks beryllium, giving off sulphur dioxide. Hydrochloric acid and dilute sulphuric acid as well as solutions of the caustic alkalies METALLIC BERYLLIUM 15 attack the metal with evolution of hydrogen. The gaseous hy- dracids attack it violently if passed over the heated metal. Strong nitric acid has little effect upon the metal but weaker acid attacks it giving off nitric oxide. It is but little acted upon by cold water, but is slowly converted into the hydroxide by boiling water. Beryllium acts upon methyl and ethyl iodides, (Cahours, 1860; i) replacing the iodine and forming beryllium ethyl and beryl- lium methyl. It also replaces mercury in its analogous com- pound and in mercury propyl, (Cahours, 1873; I, Lawroff, 1884; 3). Wohler ( 1828 ; 2 ) thought he had prepared the selenide, telluride, arsenide and phosphide by fusing with the respective elements but his observations have not been confirmed. Beryllium has probably never been obtained in combination with hydrogen although Winkler, (1891 ; 3) thought he had produced a hydride. Beryllium unites directly with carbon, boron and silicon at the heat of the electric furnace (Lebeau, 1895; 2, 1898; 7, 1899; I] 0- it reduces SiCl 4 when heated, (Rauter, 1892; 2). Valency. 'The valency of beryllium was long in doubt and gave rise to an animated discussion extending over many years and calling forth much research. The question was in reality settled when Nilson and Pettersson, (1884; 7) and (1885; 3), against all their previous contentions, found the vapor density of beryllium chloride to be entirely in accord with the divalency of the metal. Their determinations were made between 490 and 1520 C, and above 1000, their results are quite constant for the formula BeCl 2 . The divalency was confirmed by Humpidge by the specific heat at high temperatures and by the \iapor den- sity of both chloride and bromide, (1886; i), by Coombes, (1894; 6) by the vapor density of the acetylacetonate, and by Urbain and Lacombe, (1901; 2) by the vapor density of the basic acetate. Rosenheim and Woge (1897; 4) also found the formula for the chloride to be BeCl 2 by the rise of the boiling point of its solution in pyridine. Alloys of Beryllium. Our knowledge of the alloys of beryl- lium is confined solely to the work of Lebeau (1897; 8, 1898; l6 CHEMISTRY OF BERYLLIUM 4, 1899; n) and, although he produced alloys with the common metals and Cr, Mo and W, he describes those of copper only. His alloys were made either by heating the mixed oxides of beryllium and the metal to be alloyed with an intimate mixture of carbon to a very high temperature in the electric furnace, or they are produced simultaneously with the electrolytic produc- tion of beryllium, by substituting a graphite for the nickel cru- cible and fusing in this the metal to be alloyed, while the double fluoride of beryllium and sodium was being electrolyzed in the same crucible. Alloys of about 10 per cent. Be to 90 per cent. Cu are pale yellow, nearly white. Alloys of 5 per cent. Be are yellow, easily polished and malleable, cold or hot. They are not oxidized in the air, but are tarnished by hydrogen sulphide. They are dissolved by nitric acid with difficulty. As little as 0.5 per cent, of beryllium changes very noticeably the appear- ance of the copper and makes it decidedly sonorous. An alloy containing 1.32 per cent, of beryllium has the color of gold and is very sonorous. Tt is easily polished and can be readily forged. CHAPTER III. NORMAL COMPOUNDS OF BERYLLIUM. All normal compounds of beryllium which are soluble in water are strongly acid in reaction to litmus, dissolve notable quanti- ties of their own hydroxide which increases in amount with the concentration of the solution, set free carbon dioxide from carbonates and attack certain metals. In short, they act in many respects like the acids themselves would act from which they are derived. In spite of these facts they show less hydrolysis, and consequent smaller concentration of hydrogen ions, at least in the case of the chloride, nitrate and sulphate, (.Leys, 1899; 10 and Brunner, 1900; i) when treated by the well-known method of sugar inversion, than the corresponding salts of iron and aluminum. By the same method of determina- tion, the hydrogen ions are thrown back into the undissociated condition when but a small fraction of the beryllium hydroxide has been dissolved which the normal salt is capable of holding in solution, (Parsons, 1904; 10). The reasons for these phe- nomena are not at present understood. The sulphate has been recently studied with a view to a solution of this problem, (1907; 10) and it has been shown that the addition of beryllium hydroxide to a solution of the sulphate, raises the freezing point and diminishes the conductivity; that no beryllium enters into the formation of a complex anion and that while the hydroxide can be partially removed by dialysis if dialyzed into pure water, there is little evidence of a colloid being present. It has been suggested that we may have here a new instance of solution, wherein the solid, when once dissolved, acts as a true solvent for its own oxide or hydroxide, and there are some analogies which point strongly to this view, (1907; n). To this same cause, whatever it may be, is due the fact that no normal carbonate or nitrite is known, and that the chloride, bromide, iodide and nitrate lose their anion so readily when in contact with water that they can only be prepared with l8 CHEMISTRY OF BERYLLIUM special precaution against hydrolysis and solution of the hydrox- ide formed. BERYLLIUM HALIDES. The halides of beryllium, with the exception of the chloride, were little known until Lebeau gave them most careful study. They are, excepting the fluoride, only pre- pared pure in the absence of all water. By careful evaporation of the fluoride in the presence of ammonium fluoride or in an atmosphere of hydrofluoric acid gas, it can apparently be kept from hydrolytic action, (Lebeau, 1899; n) but this is not true of any of the other halides. On evaporating their solutions in water they lose more or less of the gaseous hydracids, the residue becoming more and more basic and remaining soluble until a surprising degree of basicity is reached. This hydrolytic action is comparatively small in the case of the fluoride, but is practically complete in the case of the chloride, bromide and io- dide. By careful manipulation residues of almost any degree of basicity can be obtained and these mixtures of base and normal salt have given rise to claims for numerous oxyfluorides and cxyMorides for the existence of which there is no other evi- dence than the analysis of the variable residues obtained. Beryllium Fluoride, BeF 2 . The first experiments on the relation of fluorine to beryllium were made by Gay Lussac and Thenard in 1811 (1811; i). Later in 1823, Berzelius (1823; i) made the fluoride by dis- solving the oxide in hydrofluoric acid and described the proper- ties of the solution so produced and the residue left on evapora- tion, the basic nature of which he recognized. Klatzo (1869; i) made a short study of the fluoride, but the pure salt was not produced until Lebeau (1898; 8, 1899; IT ) made it by heating the double fluoride of ammonium and beryllium, which had pre- viously been dried over phosphoric anhydride, in a current of dry carbon dioxide and cooled in an atmosphere of the same gas. He also prepared it by the action of hydrofluoric acid gas on the carbide. Properties. According to Lebeau the pure fluoride is a glassy, transparent mass having a specific gravity of 2.01 at 15. It NORMAL COMPOUNDS OF BERYLLIUM 19 becomes fluid towards 800, passing through a viscous condition, but above 800 it begins to volatilize, yielding white and very deliquescent crystals. It dissolves in all proportions in water, is only slightly soluble in absolute alcohol, but dissolves read- ily in 90 per cent, alcohol. By cooling an alcoholic solution to 23, one obtains a white crystalline mass which, however, melts easily on rise of temperature. It is also soluble in a mixture of ether and alcohol. The majority of metalloids are without action on the fluoride. It is insoluble in anhydrous hydrofluoric acid and is not altered by it, rendering the existence of an acid salt quite improbable. It is readily attacked by sulphuric acid. The alkali metals and magnesium reduce it, but the difficulty of fu- sion and hydroscopicity renders the preparation of pure metal dif- ficult. With potassium the reaction begins below 500. Lith- ium and magnesium act at about 650. Aluminum fuses with- out alteration. Beryllium Chloride, BeCl 2 . Although Vauquelin (1798; 5) obtained the chloride in solution, the pure salt was not made until Rose (1827; i) prepared it in the sublimed anhydrous state by passing chlorine gas over a heated mixture of carbon and beryllium oxide. Wohler (1828; 2), Awdejew (1842; 2), Debray (1855; i), Klatzo (1869; i), Nilson and Pettersson (1880; 6, 7, and 8, 1885; 3), Pollok (1904; 12) and others used the same method of preparation. Nilson and Pettersson (1885; 3) prepared the chloride in very pure form for the purpose of determining its vapor density by the action of dry hydrochloric acid gas on the metal. Lebeau (1895; 2, 1899; u) utilized the carbide which is readily attacked when heated by both chlorine and gaseous hydrochloric acid. Lothar Meyer (1887; i) obtained the chloride by passing car- bon tetrachloride vapor over heated beryllium oxide. Bourion (1907; 7) prepares the chloride by the action of a stream of mixed Cl .Mid S 2 C1.> on the oxide at a red heat. No matter what method is used the materials must be absolutely dry if a pure chloride is to be obtained. Awdejew (1842; 2) and Atter- berg (1873; 7) thought they had produced a hydrous chloride, BeCl 2 4H 2 O, by evaporating the chloride slowly over sulphuric acid, but Parsons (1904; 5) shows that the procedure recom- 2O CHEMISTRY OF BERYLLIUM mended invariably yields basic mixtures of varying degrees of hydration. Atterberg's results are easily explained when one considers that his formula depended solely on an analysis for chlorine alone, and although Awdejew gives no details of his analytical results, it is probable he was led to his undoubtedly erroneous conclusion in the same way. Properties. The anhydrous chloride is a white crystalline solid having a melting point about 440 (Lebeau, 1899; n, Pollok, 1904; 12). Carnalley (1879; I, 1880; I, 1884; 9, 1884; 10) obtained much higher figures, but was certainly in error. The boiling point is about 520 as shown by Nilson and Petters- son and confirmed by Pollok (1904; i). Its vapor density first determined by Xilson and Pettersson (1884; 7, 1885; 3) between 490 and 1520, is in entire accord with the formula BeCl 2 . This was confirmed by Humpidge (1886; i). Rosenheim and Woge (1897; 4) showed that the molecular weight as determined by the raising of the boiling point of a solution of beryllium chlo- ride in pyridine, was in agreement with the same formula. Its molecular heat of solution is 44.5K and its molecular heat of formation is I55K (Pollok, 1904; 9). Its magnetic suscept- ibility was determined by Meyer (1899; 3). The fused chloride does not conduct the electric current, (Lebeau) but its alcoholic solution is a conductor (Pollok, 1904; i). Beryllium chloride dissolves in water with great avidity and, unless special precautions are taken, with loss of chlorine as hydrochloric acid. On evaporation the solution loses hydrochlo- ric acid more or less readily according to conditions, and the residue left, which may be of almost any degree of basicity, has been mistaken for an oxychloride by Atterberg (1873; 7, 1875; 4). With ether it forms the compound BeCl,.2[ (C 2 H,) 2 O], (Atterberg, 1875; 4). It also forms a white crystalline com- pound containing the chloride with both hydrochloric acid and ether (Parsons, 1904; 5), the exact composition of which has not been determined.* It is also readily soluble in alcohol, and yields a crystalline compound with it, but is almost insoluble in benzene, chloroform, carbon tetrachloride and sulphur dichlo- * Since this went to press a letter from H. Steimnetz informs me that tfiese crystals are in reality BeCl 8 .4H 7 O. It is accordingly certain from the conditions that this com- pound was never made by Atterberg. Its indentifiration belongs to Steinmetz My in- correct observation was qualitative only and made in the course of another investigation. THE AUTHOR. NORMAL COMPOUNDS OF BERYLLIUM 21 ride (Lebeau, 1899; n). It combines with ammonia gas and with phosphine. Lebeau (1899; n) claims that it forms many crystalline compounds with the organic bases, but Renz (1903; 3) was only able to obtain the compound, BeCl 2 .(C 9 H 7 N 2 ) 2 -f- -H 2 O, with quinoline. By experiments on the chloride and sul- phate, Hober and Kieson (1898; 9) were able to show that their taste was due to the cation. The chloride forms many double salts (vidi, Double Salts). According to Brunner (1900; i) and Leys (1899; 10), beryllium chloride solutions are less hydro- hzed than those of aluminum and iron, although about two per cent, of the molecules are so decomposed. Awdejew (1842; 2) and Nilson and Pettersson (1884; 7, 1885; 3) claim that the sub- limed chloride attacks glass, but Parsons (1904; 5) states that this is probably incorrect. Beryllium Bromide. The bromide was first prepared by Wohler (1828; 2) by the action of bromine vapor on the metal and also upon a mixture of carbon and beryllium oxide. Ber- themot (1831 ; i) obtained it in solution by dissolving the oxide in hydrobromic acid. Humpidge (1883; 7) also prepared it by acting on a mixture of the oxide and carbon with dry bromine. Lebeau (1899; n) prepared it by the action of bromine and gaseous hydrobromic acid on the carbide. Properties. The anhydrous bromide is obtained always by sublimation and in colorless white crystals. Its vapor density determined by Humpidge (1886; i) is in accord with the for- mula BeBr 2 . Its melting point was determined by Carnalley and Williams (1879; i, 1880; i, 1884; 9 and 10) but the values obtained were much too high, as shown by Lebeau (1899; 11), who states that it fuses at about 490 and begins to sublime some- what below this temperature. The fused salt does not conduct electricity, although Warren (1895; 10) claimed to make the metal in some quantity by electrolyzing it. For a knowledge of its chemical properties we are indebted almost wholly to Lebeau (1899; u) who states that it acts much the same as the chloride. It dissolves in water with avidity, losing hydro- bromic acid on evaporation. It is soluble in absolute alcohol 22 CHEMISTRY OF BERYLLIUM and forms a crystalline compound therewith. It combines with ammonia and with the organic bases. Beryllium Iodide, BeI 2 . Wohler (1828; 2) and Debray (1855; ] ) prepared the iodide by the action of iodine upon the metal, but we are indebted almost solely to Lebeau (1898; 6, 1899; n), who prepared it in some quantity by the action of gaseous hydri- odic acid, or a mixture of hydrogen and iodine vapor, on the carbide at about 700, for a knowledge of its properties. Properties. According to Lebeau (1899; JI )> beryllium io- dide, as obtained in the sublimed state, consists of colorless crystals, which are quickly decomposed in moist air. Their spe- cific. gravity at 15 is close to 4.20. They begin to sublime below their melting point which is 510. The melted iodide boils be- tween 585 and 595. It is insoluble in benzene, toluene, spirits of turpentine, and but slightly soluble in carbon disulphide. The slightest trace of water attacks it immediately, but it is not quite so sensitive after fusion, probably because less sur- face is exposed. It can be distilled without alteration in dry hy- drogen, nitrogen or carbon dioxide. Its iodine is readily re- placed by chlorine or bromine. Fluorine forms fluorides of both beryllium and of iodine. Fluorine and chlorine both attack it even when cold, giving off heat and light. Cyanogen acts upon it at about a red heat, producing a white material, less volatile than the iodide, which with water gives a clear solution reacting for cyanides. Heated in oxygen, it takes fire at about a red heat and the vapor itself will burn even in air. Heated with sulphur it yields a sulphide of beryllium, readily decomposed by water. The vapor of phosphorus also attacks it, probably forming a phosphide of beryllium. Sodium, potassium and lithium re- duce it at about 350. Magnesium reduces it at about 450. Aluminum, silver, copper and mercury are without ac- tion below the temperature of the softening of glass. Hydrogen sulphide acts upon it, but only at elevated temperatures and yields a white sulphide. It absorbs large amounts of ammonia gas and forms compounds which melt easily and can be crystallized on cooling. It reacts with a large number of organic compounds. It is soluble in alcohol and pro- NORMAL COMPOUNDS OF BERYLLIUM 2J duces a crystalline compound therewith. It also combines with ether. It differs from the iodide of aluminum in not reacting with cold tetrachloride of carbon. It also does not act upon C 2 C1 4 , Acetic anhydride and anhydrous chloral give energetic reactions with beryllium iodide. Ammonium compounds and organic bases, especially aniline and pyridine, produce crystalline com- pounds with it. BERYLLIUM OXIDE. Preparation. The oxide is prepared by heating the nitrate, sulphate, oxalate, hydroxide, basic carbonate or other salt of beryllium containing a volatile acid radical, and even the chlo- ride, bromide and iodide yield practically all of their metal as oxide when evaporated from solution and heated. By evaporat- ing to dryness a mixed solution of beryllium chloride and ammo- nium chloride and heating in air, an oxide so light and feathery is produced that it is difficult to retain it in the containing ves- sel. Properties. The oxide is a white powder as ordinarily pro- duced which can be volatilized and crystallized at high tempera- ture. According to Levi-Malvano (1905; 7) a blue oxide is obtained by igniting the hexahydrated sulphate (vidi sulphates). 1 In the electric furnace, (Lebeau, 1896; 6, 1899; u) it can be fused and even volatilized and yields a crystalline mass slightly harder than corundum. The crystals are hexagonal (Lebeau, 1899; n). Mallard, (1887; 4) states that they are positive and unaxial and he measured parameters a :h= 1 : 1.6305. He fur- ther states they are isomorphous with zinc oxide, and Ebelmen (1851; i) states that they are isomorphous with aluminum ox- ide. The oxide is diamagnetic (Nilson and Pettersson, 1880; 9) and its magnetic susceptibility has been determined by Meyer (1899; 3). The specific gravity was first determined by Ekeberg (1802; i) as 2.967. Rose (1848; 2) found 3.021 to 3.09, claiming the lower figure was obtained by high heating. Ebelmen (1851; i) reported 3.058; Nilson and Pettersson (1880; 9, 1880; 10) ob- 1 Repeated attempts by the author of this book to reproduce this oxide or even the hexahydrated sulphate have met with failure. 24 CHEMISTRY OF BERYLUUM tained 3.016 and Grandeau (1886; 2) 3.18. Later results on very pure material gave Kriiss and Moraht (1890; 7) 2.9644; Lebeau (1896; 6, 1899; n) at o, 3.01-3.025; Parsons (1904; 5) at 4, 2.9640. According to Lebeau, fusing the oxide had very little effect on the specific gravity. The specific heat of beryllium oxide is 0.247 between o and 100 (Nilson and Pettersson, 1880; 9 and 10). According to Tanatar it is 0.2898 between 100-117. Crystals of the oxide have been produced by melting in the electric furnace (Lebeau, 1896; 6), by fusing a mixture of beryl- lium silicate and potassium carbonate (Ebelmen, 1851; i), by fusing a mixture of sulphate of potassium and sulphate of beryl- lium (Debray, 1855; i), by fusing a mixture of sulphate of po- tassium and phosphate of beryllium (Grandeau, 1886; 2), by dissolving the oxide in fused beryllium leucite (Hautefeuille and Perrey, 1890; 9) and by fusing the sulphate with silicic acid (Hautefeuille and Perrey, 1890; 14). Beryllium oxide is not reduced by hydrogen, magnesium, so- dium, potassium or aluminum (Lebeau, 1896; 6, 1899; n). Ac- cording to Franck (1898; 20), aluminum does form alloys at high temperature by heating with beryllium oxide. It is re- duced by carbon at high temperatures in the presence of other metals, such as copper, forming alloys therewith, or, when treat- ed alone at high temperatures with either carbon, boron or silicon it is reduced, forming the carbide, borocarbide or silicide (Le- beau, 1899; n). It is not acted upon by water or carbon di- oxide. Ballard (1834; i) states that bromine water, especially under the influence of sunlight partly dissolves beryllium oxide, but Lebeau (1899; it) finds that it is not affected by bromine, chlorine, iodine or others of the non-metals except fluorine, which attacks it directly with the formation of a fluoride. Mixed with carbon and heated in a current of a halogen gaS the correspond- ing halide is formed and Meyer (1887; i) found that the anhy- drous chloride was formed if the oxide was heated in a current of carbon tetrachloride vapor. Bourion (1907; 7) found that it was also acted upon by S 2 C1 2 at a red heat with the formation of the chloride. NORMAL COMPOUNDS OF BERYLLIUM 25 The gaseous hydracids have no action on the oxide, even at high temperatures. Strong hydrochloric and nitric acids dis- solve the oxide slowly. Strong sulphuric acid attacks it readily forming the anhydrous sulphate which dissolves only slowly on dilution with water as hydration progresses. Rose (1848; 3, 1855; 2 ) states that beryllium oxide partially decomposes solu- tions of NH 4 C1, but loses this property if heated. Atterberg (1873; 7) states that the oxide is not soluble in fused potassium hydroxide. According to Ebelmen (1851 ; i), it is readily solu- ble in potassium bisulphate. Beryllium Sulphide. Wohler (1828; 2) supposed he had made a sulphide by heating the metal with sulphur, but Fremy (1853; i) states that it was the only sulphide he could not produce by passing the vapor of carbon disulphide over the hot oxide. De- bray (1855; an d Nilson and Pettersson (1873; 3) state that beryllium and sulphur do not combine when heated together. Berzelius (1826; 2) supposed he produced a double sulphide of beryllium and tungsten, but his results lack confirmation. Lebeau (1899; n) at last made the sulphide by heating the anhydrous chloride and iodide with sulphur or with hydrogen sulphide. Also by the action of sulphur vapor on the carbide at a high temperature. The sulphide is a white solid, immediately decom- posed by water. No other details are given nor further study of this compound been made. Beryllium Selenide, Beryllium Telluride. Preparation claimed by Wohler (1828; 2), but probably he was mistaken. Beryllium Trinitride. Attempts to make the trinitride (Curtius and Rissom, 1898; 12) by the action of a solution of beryllium sulphate on barium trinitride failed, as it immediately broke down to beryllium hydroxide and hydronitric acid. Beryllium Phosphide. Claimed by Wohler (1828; 2), by the action of phosphorus on the metal, but unconfirmed by this method. Lebeau, however, (1899; n) prepared a compound of beryllium and phosphorus, which he did not analyze or describe, by means of the action of phosphorus vapor on anhydrous beryl- lium chloride and iodide. 26 CHEMISTRY OF BERYLUUM Beryllium Cyanide. By the action of cyanogen gas on beryl- lium iodide, Lebeau (1898; 6, 1899; n) produced a cyanide compound of beryllium which he neither studied nor analyzed. Beryllium Carbide, Be 2 C. The carbide of beryllium has been produced by Lebeau (1895; 2, 1899; n) by heating a mixture of one part carbon and two parts beryllium oxide in an electric furnace, using a current of 950 amperes and 50 volts for about ten minutes. Lebeau first gave it the formula Be 4 C 3 , but after Henry (1895; 8) called his attention to his error, he adopted the formula Be 2 C. Its properties are quite similar to those of aluminum carbide. At 15 its specific gravity is 1.9. It is so hard it scratches quartz easily. It consists of yellowish brown transparent crystals. Fluorine, chlorine and bromine attack it readily if heated, forming the corresponding halide and leaving a residue of carbon. Iodine is without action at 800. Oxygen attacks it only superficially when heated. The vapor of sulphur reacts at about 1000, forming the sulphide. Hydrofluoric acid gas attacks it at about 450, forming the fluoride. Hydrochloric acid gas forms the chloride at about 600 and sets free carbon and hydrogen. Hydriodic acid gas attacks it at about 750, yielding the iodide. Beryllium carbide slowly decomposes water yielding beryllium hydroxide and pure methane. The reaction is much more rapid in solution of potassium hydroxide. The carbide reduces concentrated sulphuric acid, although it is but slowly attacked by concentrated nitric and hydrochloric acids. These same acids diluted dissolve it completely after a few hours. Fused potash attacks it with incandescence and it is oxidized by potassium permanganate and peroxide of lead. The chlorate and nitrate of potassium do not attack it. Beryllium Borocarbide, 3Be 2 C.B 6 C. By heating a mixture of boron and beryllium oxide in a carbon tube by means of a cur- rent of 150 amperes and 45 volts, Lebeau (1898; 7, 1899; n) produced some bright metallic crystals to which he gave the for- mula Be 6 B 6 C 4 . The borocarbide has a specific gravity of 2.4 at 15. It is not altered in air unless heated and then oxidizes only superficially. Fluorine, chlorine, bromine and iodine, as well as their hydracids, act much the same as on the pure carbide. Sulphur NORMAL COMPOUNDS OF BfcRYLUUM 27 attacks it only superficially at a red heat. Mineral acids and es- pecially nitric acid dissolve it rapidly. Beryllium Silicide. Lebeau (1899; n) also obtained a silicide of beryllium, but was unable to purify it sufficiently to deter- mine its properties or formula. Beryllium Hydroxide, Be(OH) 2 . Beryllium hydroxide is a white gelatinous mass physically indistinguishable from alu- minum hydroxide and resembling it very closely from a chem- ical standpoint. It is precipitated from solutions of beryllium salts by ammonia, ammonium sulphide, caustic alkalies and ba- rium carbonate. It is also precipitated by methyl, dimethyl, ethyl, and diethyl amines (Vincent, 1880; 2, Renz, 1903; 4). Soluble normal carbonates throw down a basic mass which con- sists largely of the hydroxide together with some carbonate. The latter may, however, be almost entirely eliminated by boil- ing. It is readily attacked by solutions of acids. It dissolves slowly in concentrated solutions of ammonium carbonate (Vau- quelin, 1798; i, et al.) and sodium bicarbonate. It is imme- diately soluble in a saturated boiling solution of sodium bicar- bonate (Parsons and Barnes, 1906; 2). It is, however, almost insoluble in a dilute solution and a strong solution which has dissolved the hydroxide, on dilution (two per cent, or less NaHCO 3 ) slowly hydrolyzes in the cold and throws out the! basic carbonate or does so immediately on boiling. It is almost insoluble in normal sodium carbonate. It is soluble in sodium and potassium hydroxides forming beryllonates which are hy- drolytically decomposed on boiling. This decomposition is com- plete if excess of base is not present, but may be partially or entirely prevented by increasing the mass of the soluble hydrox- ide. It is soluble in solutions of its own salts and in proportion to the concentration of the particular salt used. From concen- trated solution in its own salts, it is precipitated by dilution, but such precipitation is never complete. It is insoluble in ex- cess of ammonium sulphide, ammonia, and methyl, ethyl, di- methyl and diethyl amines (Vincent, 1880; 2, Renz, 1903; 4). When washed with pure water it slowly passes through the filter in colloidal solution (Parsons and Barnes, 1906; 2). Beryl- 28 CHEMISTRY OF BERYLLIUM Hum hydroxide, like aluminum hydroxide, is more susceptible to reaction when freshly precipitated (Haber and Van Oordt, 1904; 2). This is more especially apparent in the case of car- bon dioxide, for when freshly precipitated it will absorb about one third of an equivalent of this gas, but if allowed to stand sometime and especially if first heated, it almost entirely loses this property (Parsons and Roberts, 1906; 4). Leys (1899; IO ) states that it is n times as basic as aluminum hydroxide. It has, like most other gelatinous hydroxides, a very great tendency to occlude other substances which may be present when it is pre- cipitated and it is almost impossible to remove these substances by washing. It is nearly insoluble in water charged with car- bon dioxide (Sestini, 1891 ; 6) and according to Toczynski (1871 ; 2) in hydrocyanic acid. Van Bemmelen (1882; 2) distinguishes two forms of the hy- droxide, first alpha, precipitated from potassium beryllonates by boiling which form is easily washed and, he claims, is the only one of definite composition being readily dried to the formula Be (OH) 2 , and second beta, which is the gelatinous mass pre- cipitated by alkalies which is always more or less hydrated. At- terberg (1873; 7) gives formulas for some of these hydrated oxides, but there is little in his work or that of Van Bemmelen (1882; 2) to show that this extra water is other than mechani- cally held. Reubenbauer (1902; 5) found that sodium hydrox- ide dissolves beryllium hydroxide in proportion to its concentra- tion. Van Bemmelen (1898; 19) studied the effects of heat on his two forms of the hydroxide. Meyer (1899; 3) deter- mined the magnetic susceptibility of the hydroxide. It is read- ily, although slowly, decomposed by boiling with solutions of ammonium salts (Rose, 1848; 3), Debray (1855; i), Joy (1863; i), Parsons (1904; 5, et al.). v. Kobell (1832; i) states that calcium carbonate will not precipitate beryllium hydroxide in the cold, but does so on boiling. Prudhummer (1895 ; 7) states that beryllium hydroxide does not act as a mordant. The heat of neutralization of beryllium hydroxide as found by Thomsen (1871; I, 1874; 2) is NORMAL COMPOUNDS OF BERYLUUM 29 Be(OH) 2 +H 2 SO 4 +Aq=i6ioo calories. Be(OH) 2 +2HCl-f Aq=i3640 calories. Pettersson (1890; 8) found Be(OH) 2 -f2HF+Aq=i9683 calories. Gmelin (1840; i), Schaffgotsch (1840; 2), Weeren (1854; i) and Debray ( 1855 ; i ) have also studied the properties of beryl- lium hydroxide. Beryllium Chlorate, Bromate, lodate, and compounds of beryl- lium with oxygen and a halide. Traube (1894; 3) gives the molecular solution volume of Be(ClO 3 ) 2 , but no details as to the salt itself. Atterberg (1873; 7) prepared the perchlorate, Be(ClO 4 ) 2 .4H 2 O, and a periodate to which he gave a very improbable formula. He could not make the chlorate. Marignac (1873; 2) tried to make the bro- mate and iodate as well, but obtained only indefinite gummy masses. He states further that the perchlorate only takes the crystalline form after concentration to a thick syrup and is very deliquescent. Marignac was probably the nearest correct and it is doubtful if any of these compounds have been made as distinct individuals. Beryllium Sulphates. Six normal sulphates of beryllium find place in chemical literature : BeS0 4 , BeSO 4 .H 2 O, BeSO 4 .2H 2 O, BeSO 4 .4H 2 O, BeS0 4 .6H 2 0, BeSO 4 .7H 2 O, of which the heptahydrate certainly has no existence, in fact. Anhydrous Beryllium Sulphate, BeSO 4 . Nilson and Petters- son (1880; 9) prepared a product very close to the composition BeSO 4 by heating the dihydrate at 250. The sulphate so pre- pared had a specific gravity=2.443 and a specific heat=o.i978. Lebeau (1896; 6, 1899; u) prepared the anhydrous sulphate by the action of strong sulphuric acid on the oxide and evaporation of the excess of acid. Parsons (1904; 10) states that while 30 CHEMISTRY OF BERYLLIUM the product obtained by either of the foregoing methods is un- doubtedly the anhydrous sulphate, it is a very difficult matter to get it pure, owing to the fact that the loss of the last trace of water on heating is very close to the point where sulphur trioxide begins to be given off if indeed the two do not go to- gether. Levi-Malvano (1905; 7) claims that this is a mistake and that he completely eliminated all water at 218 to 220. The anhydrous sulphate is stable in dry air, is itself insoluble in water, but slowly hydrates and goes into solution as the tetra- hydrate. It loses sulphuric anhydride even below a red heat, but the last traces are only driven off at a full white heat. Beryllium Sulphate Monohydrate, BeSO 4 .H,O. Levi-Malva- no (1905; 7) claims the dihydrate melts at 158 and goes over into the monohydrate. Beryllium Sulphate Dihydrate, BeSO 4 .2H 2 O, is prepared by drying the tetrahydrate at 100 and is stable in dry air below this temperature. Nilson and Pettersson (1880; 6), Kriiss and Moraht (1890; 7), Parsons (1904; 5, 1904; 10), Levi-Malvano (1905; 7). It dissolves readily in water passing back into the tetrahydrate. Beryllium Sulphate Tetrahydrate, BeSO 4 4H 2 O. The tetra- hydrate was first prepared by Berzelius, (1815; i) who con- sidered it to be an acid salt. Awdejew, (1842; 2) first deter- mined its true character and used the salt to determine the atomic weight of beryllium. It was also employed for this purpose by Weeren (1854; i), Klatzo (1869; i), Nilson and Pettersson (1880; 6) and Kriiss and Moraht (1890; 7). Parsons (1904; 5) showed that the sulphate lost water continuously over phosphoric anhydride and discarded it as a means of determining the atomic weight of the element. This salt of beryllium has been studied more than any other compound of the metal. Preparation. It is best prepared by dissolving beryllium ox- ide, carbonate or hydroxide in excess of sulphuric -acid, evapo- rating in platinum and heating below a red heat until the larger part, but not all, of the white fumes of sulphuric acid have been driven off, dissolving in water, evaporating to a syrup and turning into strong 95 per cent, alcohol. By this procedure a NORMAL COMPOUNDS OF BERYLLIUM 3! milky solution is produced which does not immediately crystal- lize, but after a few hours the sulphate will have almost entirely separated. To insure perfect freedom from acid two more crystallizations from alcohol are necessary and the salt should finally be crystallized from water to insure the right degree of hydration. The salt may also be prepared more directly and in a fair state of purity by evaporating the sulphuric acid solu- tion to dryness and heating on a sand bath until white fumes cease to come off, taking especial care not to use too high a tem- perature. The anhydrous sulphate may then be allowed to stand for some time, with occasional stirring, in contact with cold \vater filtered and the solution evaporated to crystallization. Properties. Beryllium sulphate tetrahydrate consists of color- less octahedral crystals belonging to the tetragonal system. Ac- cording to Topsoe (1872; i) and Topsoe and Christiansen (1873; 9) the crystals are unaxial and optically negative. Observed iorms (on). (no); a:c=i 10.9461. Mean indices of refraction C = 1.4374 C = 1.4691 e D =1.4395 w 0=1.4720 F = 1.4450 F = 1-4779 Wulff (1889; 4) states further that the crystals give strong double refraction. Gladstone and Hibbert (,1897; 6) compared the molecular refraction of the solid sulphate, 47.41 with the same in solution, 47.94. Jahn (.1891; 5) found the specific rotation for the sulphate as 0.28895. The solution friction was studied by Wagner (1890; 12). Meyer (1899; 3) studied the magnetic susceptibility. Traube (1894; 3) determined the molec- ular solution volume. Hober (1898; 9) found that the sul- phate and chloride have same sweet taste at equal cation con- centrations. According to Leys (1899; 10) and Brunner (1900; i) the sulphate is less hydrolyzed in solution than the sulphates of aluminum and iron. Brunner gives this hydrolysis in N/4 to N/20 solution as 0.52 per cent, to 0.68 per cent. According to Weeren (1854; i) the crystals lose one-third of their water of crystallization at 35. Parsons (1904; 5) by tensimeter ex- periments found the vapor tension of the crystals at 20 to equal a pressure of 20 millimeters of olive oil and to increase rapidly 32 CHEMISTRY OF BERYLLIUM with the temperature. Over phosphoric acid the crystals lose water slowly at ordinary temperatures. By dissolving one mol BeSO 4 .4H 2 O in 400 mols of water Thomsen (1873; 4) found the heat of solution =-j- IIO - Pollok (1904; 9) gives the heat of solution as o.85K. The specific gravity has been determined as follows: Topsoe (1872; i) (1873; 6) 1.725; Nilson and Fettersson (1880; 9) 1.713; Stallo (Clark's "Constants of Nature") 1.6743 at 22; Kriiss and Moraht (1890; 7) 1.7125. Beryllium sulphate tetrahydrate is soluble in about its own weight of water, but is insoluble in absolute alcohol. Its solu- tion is strongly acid to indicators, attacks zinc with evolution of hydrogen and when fully concentrated dissolves two equiva- lents of its own hydroxide. On dilution the main portion of the hydroxide is thrown down, but approximately one-half of an equivalent remains dissolved at infinite dilution. It should be crystallized from a neutral or acid solution, for although the crystals can be obtained from a basic solution (1906; 5) it is impossible to separate them therefrom. The taste of the salt is a mixed acid and sweet. Beryllium Sulphate Hexahydrate. Marignac (1873; i), in at- tempting to repeat Klatzo's work (1869; i) on the heptahydrate, after many attempts obtained only once, by evaporating a super- saturated solution of sodium sulphate and beryllium sulphate,, a mass of prismatic crystals which he thought contained six molecules of water. They immediately effloresced on exposure to air and could not have been the hexahydrate described by Levi-Malvano (1905; 7). According to the last named author he obtained crystals of the hexahydrate from a commercial source and after repeated trials was able to produce the salt it- self by treating an excess of but a little diluted sulphuric acid with enough beryllium hydroxide or carbonate at ordinary tem- peratures to insure a state of supersaturation of the sulphate formed and suddenly shaking the mass. The solution itself should contain excess of acid, and inoculation with crystals of the hexahydrate previously produced was apparently of no as- sistance. Crystallization in the cold did not seem to especially favor the formation of the hexahydrate, but the one condition NORMAL COMPOUNDS OF BERYLLIUM 33 seemed to be supersaturation. Still having once produced the hexahydrate it could be crystallized out of aqueous solution at temperatures as high as 50 and he even threw it out of solu- tion at 90 by addition of boiling alcohol. On the other hand when at 30 the cryohydrate was reached, the hexahydrate was present mixed with ice. According to Levi-Malvano the hexahydrate is stable in air. The finely pulverized salt melted at 78.8, but on removing the source of heat and cooling, the solidification point of the syrupy liquid was found to be 68.4. This was probably due to a mixture of crystals of a lower hy- drate. The solubility curve of the hexahydrate which is given cuts that of the dihydrate at 774. The hexahydrate on igni- tion loses water and yields a blue oxide. Parsons and Fuller (1906; 5) made many attempts to produce the hexahydrate, but without success and think that some con- dition besides supersaturation must be essential. An order sent to the dealers from whom Levi-Malvano first obtained his salt brought a bottle labeled "hexahydrate," but which on examina- tion proved to be nothing but the regular tetrahydrate. Beryllium Sulphate Heptahydrate. Klatzo (1869; i) thought he had produced a hydrate with seven molecules of water of crystallization. His work is unconfirmed and the conditions which he gives, would in themselves, seem to render its produc- tion improbable, if not impossible. Parsons (1904; 10) states that this hydrate undoubtedly does not exist. It should be re- membered also that Marignac (1873; i) found Klatzo's work to be incorrect in many particulars. Beryllium Sulphite, BeSO 3 . The normal salt has been pro- duced only by Kruss and Moraht (1890; 5) who prepared it by adding freshly precipitated beryllium hydroxide w r hich had been dried by washing with alcohol, to alcohol saturated with sulphur dioxide and evaporating over phosphoric anhydride. It con- sists of colorless hexagonal plates which are immediately de- composed by water yielding sulphur dioxide and beryllium hy- droxide. For several so-called basic compounds see basic salts. Atterberg (1873; 7) could not produce a sulphite. 3 34 CHEMISTRY OF BERYLLIUM Beryllium Thiosulphite. Factor (1901 ; 5) claims to have pro- duced the salt, BeS 2 Q 3 .iiH 2 O, by the action of a solution of sodium thiosulphate on a solution of beryllium sulphate. Some experiments by the author lead him to believe that this is incorrect for in his hands an admixture of these two solutions always precipitates sulphur and gives off sulphur dioxide as was to be expected. Marignac (1875; i) and Atterberg (1873; 7) could not obtain the salt. Beryllium Dithionate. The normal salt has not been produced. Beryllium Sulphocyanate, Be(CyS) 2 . Hermes (1866; 2) con- cluded that the somewhat illy denned residue obtained by the action of the acid on beryllium carbonate was the sulphocyanate. Found it to be soluble in alcohol. Toczynski (1871; 2) was unable to prepare the sulphocyanate with any definiteness and Atterberg (1873 ; 7) had no better success. Beryllium Selenate, BeSeO 4 4H 2 O. Beryllium selenate was first prepared by Atterberg (1873; 7 and 8) and has been also studied by Topsoe (1872; i). It is isomorphous with the sul- phate and like the sulphate, loses water at 100 forming a di- hydrate. According to Topsoe (1872; i) and Topsoe and Christiansen (1873; 9), it crystallizes in the rhombohedrai system, a:b:c=i : 0.9602 : 0.9027, observed forms (on), (101), (021), (in), (ooi). Its mean indices of refraction are Pa V-b PC C 1.4992 1-4973 1-4639 D 1.5027 1.5017 1.4664 F 1.5101 1.5084 i.47 2 5 Its specific gravity (Topsoe) is 2.029. Roozeboom (1891; i) and Topsoe (1872; i) have both discussed the significance of the mixed crystals of the sulphate and selenate. Beryllium Selenite, BeSeO 3 -]-Aq. Two normal selenites find place in literature, BeSeO 3 .H 2 O, prepared by Atterberg (1873; 7) and BeSeO 3 .2H 2 O, prepared by Nilson (1875; 2). Nilson states that his salt loses one molecule of water at 100. It was a gummy mass decomposable by water and made by evaporating the constituents together. Formula arrived at by analysis of gummy mass and no evidence of individual ex- NORMAL COMPOUNDS OF BERYLLIUM 35 istence. Acid selenites (see acid salts) and so-called basic selenites (see basic salts) have been prepared in much the same way. None of these salts should be accepted without confirma- tion. Beryllium Tellurates and Tellurites. Berzelius (1833; 2) pre- cipitated beryllium tellurate and tellurite from solution by means of the corresponding potassium salt. They were obtained as white voluminous flakes, and were probably basic mixtures but i;o details are given. Beryllium Chroniite, BeCr 2 O 4 . A crystalline compound made by Ebelmen by fusing chromic oxide, beryllium oxide and boric anhydride together and treating with hydrochloric acid. De- scribed by Mallard (1887; 4). Beryllium Chromate. Atterberg (1873; 7) attempted to pro- duce a neutral chromate but was not successful. The author of this summary and his students have repeatedly attempted to produce a chromate of definite composition, by crystallizing from aqueous solutions of very varied acid concentration treated with basic carbonate, to all degrees of saturation, and evaporated both in vacuo and in the air, but without success. If chromic acid was present in excess it crystallized out first and no separation of another definite compound could be obtained, although it was of course a simple matter to obtain residues containing any de- sired ratio between the beryllium and chromic acid. If car- bonate was added to saturation or even in excess of the equiva- lent amount and long before the solution was neutralized only the usual indefinite gummy basic chromates were obtained on evaporation. On the other hand Glassmann (1907; 4) claims to have made a neutral chromate, BeCrO 4 .H 2 O, by "neutraliz- ing" a chromic acid solution with basic carbonate and evaporat- ing, which he states are reddish yellow monoclinic crystals, de- composed by water. Beryllium Molybdate, BeMoO 3 .2H 2 O. prepared by Rosen- heim and Woge (1897; 4) by boiling equivalents of molybdic acid and beryllium hydroxide suspended in water. An oily liquid layer so obtained was separated in a separatory funnel and after standing two weeks in the cold of winter solidified to an aggre- 36 CHEMISTRY OF BERYLLIUM gate of needle like crystals. Analysis shows decided basicity which they attribute to admixture of beryllium hydroxide im- possible to remove. Beryllium Nitrate. The normal nitrate was an article of com- merce before it found place in literature. Ordway (1858; I, 1859; 2) made a special study of the nitrates and found, as had been the case with Vauquelin (1798; 5) and Gmelin (1801; i) that they are extremely difficult to crystallize. By precipitating a solution of beryllium sulphate with barium nitrate and evap- orating the solution over sulphuric acid, Ordway produced a solid mass that approached the normal nitrate in composition, but still basic as would necessarily result from any method in- volving the presence of water in quantity. Ordway shows how readily the nitrate loses nitric anhydride and Parsons (1904; 5) has shown that by evaporating a solution of the nitrate it be- comes strongly basic below 50, and on slowly drying to 175 it has become a solid which has already lost 75 per cent, of its nitric anhydride. Atterberg (1873; 7) could make no nitrate. The commercial crystallized nitrate, which can be obtained almost perfectly pure, as it is used in the incandescent mantle industry, smells strongly of nitric anhydride, melts with very little heat in its own water of crystallization and immediately begins to show bubbles of escaping gas. On slowly increasing the heat, the nitric anhydride is rapidly evolved leaving behind a viscous glucose like mass, which is still readily soluble in water when it has reached the tribasic condition. Even below 175 it has become tetrabasic and loses all of its nitric anhydride below a red heat. The resultant oxide contains a small amount of occluded oxygen and nitrogen, which if the decomposition has been gradually brought about, is equivalent to approximately 0.35 cubic centimeter (Parsons, 1904; 5) of mixed gases, of which approximately two-thirds are nitrogen, per gram of oxide. The nitrate is, of course, strongly acid in reaction. According to Brunner (1900; i), a solution of the nitrate of normality N/io to N/4O is hydrolyzed from 1.8 per cent, to 1.9 per cent. The nitrate is easily made (1906; 13) by saturating nitric acid with basic beryllium carbonate, evaporating to a syrupy con- NORMAL COMPOUNDS OF BERYLLIUM 37 sistency, adding strong nitric acid in excess and crystallizing therefrom. The crystals obtained are definite in composition and have the composition, Be(NO 3 ) 2 .4H 2 O. They are highly deliquescent, lose nitric acid readily, and are stable only in presence of strong nitric acid or in equilibrium with its vapor. They melt in their own water of crystallization at 60.5 and are soluble in alcohol and acetone. Beryllium Nitrite. Beryllium nitrite has never been prepared. The efforts of Vogel (1903; 2) proving fruitless as the solution immediately hydrolyzed with loss of the oxides of nitrogen. It may possibly be prepared in non-aqueous solutions. Beryllium Phosphate. The literature of the normal phosphates of beryllium is very far from clear, as the few investigators who have taken up the matter have found the material they produced of a gelatinous nature and difficult to identify as an individual salt. Sestini (1890; 2), by boiling an acetic acid solution of beryllium phosphate, obtained a flocculent precipitate to which he gave the formula, Be 3 (PO 4 ) 2 .3H 2 O-[-Aq. Atterberg (1873; 7) obtained, by adding sodium orthophosphate to a soluble beryl- lium salt, a flocculent precipitate to which he assigned the for- mula, Be 3 (PO 4 ) 2 .6H 2 O. Prepared by precipitating a phosphoric acid solution of beryllium hydroxide with alcohol it contained 7H 2 0. Beryllium Hypophosphate, 2BePO 3 -(-3H 2 O. Rammelsberg (1891; 4) .in his studies of the hypophosphates threw down a hot solution of beryllium sulphate with sodium hypophosphace and obtained a white precipitate having the composition, 2BePO 3 -h3H 2 O, which on heating to 23O-25O lost one-half of its water. Beryllium Pyrophosphate, Be 2 P 2 O 7 -5H 2 O. By precipitating a solution of sodium pyrophosphate with a basic solution of beryl- lium nitrate, Scheffer (1859; 3) obtained a white pulverulent pre- cipitate which, on analysis, yielded results close to the theoreti- cal formula for the pyrophosphate. Atterberg (1873; 7) studied the reaction, but did not identify the salt. Beryllium Phosphite and Hypophosphite. Rose (1827; i) pre- 38 CHEMISTRY OF BERYLLIUM cipitated a solution of beryllium chloride with a solution of phos- phorus trichloride in ammonia and again (1828; i) saturated hypophosphorous acid with beryllium hydroxide, obtaining a gummy mass. Probably neither precipitate was the normal salt and no formula was -assigned. Beryllium Vanadate. Berzelius (1831; 3) in his researches on the vanadates obtained a yellow, neutral, difficultly soluble beryllium vanadate which was not studied and to which no for- mula was assigned. Beryllium Arsenate, Be 3 (AsO 4 ) 2 .6H 2 O. Prepared by Atter- berg (1875; 4). Made in the same way as the corresponding phosphate which it resembled. Almost no other details. Beryllium Antimonate, Be(SbO 3 ) 2 .6H 2 O. This salt was pre- pared by Ebel (1887; 2) by adding a soluble beryllium salt to a hot solution of sodium metantimonate. Beryllium Columbate. By precipitating beryllium chloride with potassium columbate and fusing the precipitate in boric anhydride Larsson (1896; 10) succeeded in obtaining a crystalline colum- bate containing 6.24 per cent. BeO and 89.60 per cent. Cb,O.;. Beryllium Carbonate. No normal carbonate of beryllium is known. The carbonate, BeCO 3 .4H 2 O, claimed by Klatzo (1869; i), was a mistake and has never been made, and can not be made unless from non-aqueous solution. The so-called basic carbon- ates are important and several double carbonates are known (see basic salts and double carbonates). Beryllium Silicates. The work on the normal silicates of beryllium has been confined to the artificial production of a meta silicate, BeSiO 3 , phenacite, Be 2 SiO 4 , and beryl, Be 3 Al 2 (SiO) . Phenacite was first prepared by Ebelmen (1887; 4) by fusing together silicon dioxide, beryllium oxide and borax in right pro- portions. Later Hautefeuille and Perrey (1888; 4) prepared it by fusing SiO 2 and BeO together using lithium vanadate and carbonate as a mineralizing agent, and still later (1890; 14, and 1893; by fusing beryllium sulphate and silicic acid. Beryl was first prepared by Williams (1873; 3), by directly fusing to- gether its constituents and later, Hautefeuille and Perrey (1888; 4) prepared it by fusing together its constituents in acid lithium NORMAL COMPOUNDS OF BERYLLIUM 39- molybdate. Stein (1907; 9) by fusing in a carbon tube the nec- essary quantities of BeO and SiO 2 at 2000 obtained a meta silicate, BeSiO 3 with density 2.35 and an ortho silicate with den- sity 2.46. Beryllium Silicotungstate. Wyrouboff (1896; i) prepared a crystalline silicotungstate to which he gave the incomprehensible formula, Be 4 (W 12 SiO 40 ) 3 .93H 2 O, when c ystallized below 45. Crystallized above 45 it becomes rhombohedral with 87H 2 O. In presence of nitric acid at 30 a 45H 2 O compound is obtained. Beryllium Fluosilicate. Berzelius (1823; i) prepared a fluo- silicate by the action of fluosilicic acid on beryllium hydroxide, but did not analyze or give details, and both Atterberg (1873 ; 7) and Marignac (1873; i) state that it can be irrde only in solu- tion. Beryllium Aluminate, Be(AlO 2 ) 2 . Occurs in nature as chryso- beryl (cymophane, alexandrite) and prepared artificially by Ebel- men (1851; 3) by fusing theoretical portions of alumina and beryllia in boric anhydrid and later, by Hautefeuille and Perrey by fusing a mixture of the oxides of aluminum and beryllium in leucite or nephelite. Beryllium Ferrocyanide and Ferricyanide. Toczynski (1871; 2) prepared beryllium ferrocyanide by adding beryllium sulphate to barium ferrocyanide as a light green mass. By oxidizing with chlorine, he obtained the ferricyanide as an olive green material. Both were poorly defined and probably basic in nature as Atterberg (1873; 7) has pointed out. Beryllium Nitroprusside. Toczynski (1871; 2) was not able to prepare a nitroprusside. Beryllium Methyl, Be(CH 3 ) 2 ; Beryllium Ethyl, Be(C 2 H 5 ) 2 ; Beryllium Propyl, Be(C 3 H 7 ) 2 . Beryllium ethyl was first pre- pared by Cahours (1860; i) by the action of metallic beryllium on ethyl iodide in a sealed tube. In later experiments, (1873; i), he produced enough to study by the action of beryllium on mercury ethyl. Found it to be a colorless liquid boiling at 185- 188. It is spontaneously combustible in air and is decomposed by water. It can be distilled in an atmosphere of carbon diox- ide. Beryllium propyl was also prepared by Cahours (1873; i) 40 CHEMISTRY OF BERYLLIUM in a similar manner by the action of beryllium on mercury pro- pyl in a sealed tube at I3O-I35. It was also a liquid boiling at 244-246 with properties similar to beryllium ethyl. Beryllium methyl was later prepared by Lavroff (1884; 3) m a similar manner by the action of metallic beryllium on mercury methyl in a sealed tube at 130. It is a white volatile crystalline substance decomposed by water with evolution of light, into methane and beryllium hydroxide. Beryllium Formate, Acetate, Propionate, Etc. Although many attempts were made by Vauquelin (1798; 5), Urbain and Lacombe (1901 ;2, 190253) and others, no normal salt of beryllium with any member of the fatty acids was made until Steinmetz (1907; 5) finally succeeded in preparing the normal acetate, Be(C 2 H 3 O 2 ) 2 , by heating equal parts of basic acetate, Be 4 O(C 2 H 3 O 2 ) 6 , and glacial acetic acid with five to six parts of acetic anhydride for two hours in a sealed tube at 140. He obtained under these con- ditions crystals of the normal acetate, as small double refracting leaflets, which were insoluble in water, alcohol, ether, and other organic solvents. They melted with decomposition at 300 yield- ing a sublimate of the basic acetate. They were also slowly hy- drolyzed by boiling water. Tanatar (1907; 12) claims to make the normal formate, Be(CHO 2 ) 2 , by slowly evaporating over sulphuric acid a solution of formic acid neutralized with the basic carbonate. He also claims to make the basic formate, Be 4 O(CHO 2 ) 6 , by mixing the calculated weights and boiling in water. While it is a simple matter to get a mass under these conditions that will give almost any desired per cent, of BeO, which was his appar- ent criterion, anyone familiar with the real properties of the element would know that neither of these salts could possibly be made under these conditions. Tanatar apparently did, how- ever, make the normal propionate, Be(C 3 H 5 O 2 ) 2 , by heating, at 150, the basic propionate with propionic acid mixed with it:; anhydrid. It is little affected by solvents as Steinmetz (1907; 5) found to be the case with the acetate. Beryllium Acetylacetonate, Be(C H 7 O 2 ) 2 . Beryllium acetyl- acetonate is one of the most interesting of the salts of beryllium. It was first prepared by Combes (1894; 6) by the action of NORMAL COMPOUNDS OF BERYLLIUM 4! acetylacetone on a solution in equivalent quantities of beryllium hydroxide in acetic acid. He found it to be a white crystal- line solid melting at 108, easily sublimed, and boiling at 270. Two determinations of its vapor density showed its molecular weight to correspond with the formula, Be(C 5 H 7 O 2 ) 2 . Parsons (1904; 5) who used this salt as a basis in his atomic weight determinations made a careful study of the compound. He found it to be most readily prepared by the direct action of acetylacetone on basic beryllium carbonate or hydroxide. Accord- ing to this author, the specific gravity of beryllium acetylaceton- ate is 1.168 compared to water at 4. It is a perfectly white crys- talline substance which is slightly soluble in cold water, more soluble in hot water and slowly hydrolyzed by boiling water with loss of acetylacetone and precipitation of beryllium hydrox- ide. It is readily soluble in alcohol and is easily crystallized therefrom in rhombic plates. It is soluble in benzene, toluene, xylene, naphtha, and all petroleum distillates, chloroform, tur- pentine, methyl alcohol, amyl alcohol, ether, ethyl acetate, ace- tone and carbon disulphide. It sublimes many degrees below its boiling point and begins to sublime even below the boiling point of water. The sublimed crystals are light and flocculent with a marked resemblance to flakes of snow. It is soluble in acids setting free acetylacetone. Beryllium Oxalate Trihydrate, BeC 2 O 4 .3H 2 O. Although early attempts were made by Vauquelin (1798; 5), Debray (1855; i) and Atterberg (1873; /) to produce the normal oxalate, they were not successful and it was first made by Rosenheim and \\oge (1897; 4). \Vyrouboff (1902; i) confirms the results of Rosenheim and Woge, and Parsons and Robinson (1906; i) made a study of the system, BeO :C 2 O 3 :H,O, also producing the normal oxalate. All three authors produced their oxalate by adding basic beryllium carbonate or hydroxide to excess of oxalic acid and crystallizing the oxalate therefrom. It was found al- most impossible to get the salt absolutely free from excess of oxalic acid by crystallization and to procure the perfectly neu- tral salt. Parsons and Robinson added the necessary measured quantity of beryllium basic carbonate. Any excess of base pre- 42 CHEMISTRY OF BERYUJUM vented crystallization. The crystals of the trihydrate were de- scribed by Wyrouboff (1902; i). The crystals were figured in the article of Parsons and Robinson and the measurements made by Penfield and Heath ( 1906 ; I ) showed the crystals to be ortho- rhombic. The forms observed c(ooi), d(ioi), p(in). The angles P AP'", in A iii = 74i6' PAP, inAin = 9o 6' CAP, ooi A in = 683o' Calculated 682o / The first two measurements yielded the axial ratio a :b :<:= 0.853 : i.o : 1.645. ^ T distinct cleavage was observed. The c axis is a bisectrix and the plane of the optical axis is the brachypinacoid. In the crystal examined, the interference fig- ure was indistinct and the axial angle so large that the hyper- bolas opened out beyond the field of view. Beryllium oxalate trihydrate is stable at room temperature. It is soluble in less than its own weight of boiling water and is but little less soluble at ordinary temperatures. It is strongly acid in reaction and in concentrated solution dissolves 1.85 equiv- alents of its own carbonate or hydroxide. It has a sharp sweet- ish taste. Heated at 100-105 it loses two thirds of its water of crystallization forming the monohydrate. Beryllium Oxalate Monohydrate. Prepared by Rosenheim and Woge (1897; 4)> Wyrouboff (1902; i) and by Parsons and Robinson (1906; i). Is made by heating the trihydrate at 100-105. Heated much above this temperature it begins to lose water, at first slowly, but more rapidly as the thermometer reaches 220, at which temperature the oxalate begins to de- compose and at 350 is completely converted into the oxide. Beryllium Tartrate, BeC 4 H 4 O 6 +3H 2 O. Vauquelin (1898; 5) and Toczynski (1871 ; i) attempted the production of the normal tartrate, but it was first reported by Atterberg who gave to it the formula, BeC 4 H 4 O 6 -f 3H 2 O. Atterberg gives few details, but the salt is confirmed by Rosenheim and Itzig (1899; 15) who simply state the fact. The chief characteristic of the tartratcs. of beryllium and a fact which gives them especial interest is NORMAL COMPOUNDS OF BERYLLIUM 45 their abnormally great rotatory power. This fact was first brought out by Biot (1838; i) on a tartrate of unstated com- position prepared by Berthier, who found the beryllium tartrate to have the largest specific rotatory power of any tartrate ex- amined, viz., in 100 millimeters +41.134 to +43.992. Rosenheim and Itzig (1899; 13) in their work on some double tartrates, (which see) confirm this fact and found the rotation of polar- ized light, both right and left, was greatly increased by the in- corporation of beryllium in the molecule. By saturating tar- taric acid with freshly precipitated beryllium hydroxide at boil- ing heat and evaporation, they obtained a basic uncrystallizable glassy mass whose analysis led to the formula, Be 3 C 4 H 2 O 7 +7H 2 O, which had a very high rotatory power, their four experiments giving [M J^-j- 171 to +176.8. The rotatory power showed a change on dilution owing to hydrolysis and the authors were inclined to believe they had here a beryllium salt of diberyllium tartrate, similar to potassium diberyllium tartrate, to be described later. Beryllium Succinate, BeC 4 H 4 O 4 +2H 2 O. Atterberg (1893; 7) obtained this salt by dissolving the hydrate or carbonate in excess of succinic acid and concentrating at a thick syrup fiom which small crystals separated. These crystals lost their water of crystallization at 100. They are only stable in pres- ence of an excess of succinic acid. Beryllium Picrate. Lea (1858; 2) reports a golden yellow crystalline picrate made by dissolving basic beryllium carbon- ate in picric acid. No analysis, and it was probably basic. Glassmann, (1907; 6) by "neutralizing" picric acid solution with basic beryllium carbonate obtained yellow scales which he dried in the air and assigned the formula, Be (C 6 H 2 O 7 N 3 ) 2 .3H 2 O. By wash- ing with ether, he dried it somewhat and assigned Be(C 6 H 2 O 7 N 3 ) 2 .2H 2 O to the product, and since by drying at I2O-I3O he obtained a product which gave a molecular lowering- in acetophenone corresponding to 465 and a BeO content nearly theoretical, he assumed he had anhydrous Be(C 6 H 2 O 7 .N 3 ), 2 . He apparently measured his lowering only to the second decimal and a slight error would have given a very different result, 44 CHEMISTRY OF BERYLLIUM especially as it has been shown (1907; 10) that dissolving beryl- lium hydroxide in solutions of its normal salts raises the freezing point, if he obtained a "neutral" solution these are the only conditions that could have prevailed. As he, himself, claims that water (in which it was made) decomposes the picrate and as oxide content is no criterion of composition, especially with beryllium salts, his results need confirmation before being ac- cepted. Beryllium Alpha Brom Camphor Sulphonate, Be(C 10 H 14 BrO. SO 2 .O) 2 , was prepared by Walden (1894; 7) and although he gives no detail of the salt itself, he studied its optical rotation m comparison with the analogous magnesium, zinc and barium salt in dilute solution and found for same molecular concentration essentially the same rotation. Concluded that the beryllium ions were therefore inactive. Biot (1838; i) and Rosenheim and Itzig (1899; 13) would seem to be led to a contrary conclu- sion in the case of the tartrate unless, as indeed Rosenheim and Itzig indicate, a complex ion is formed. Beryllium Rhodizonate, Be(H 2 C 3 O 5 ) ; Beryllium Kroconate, Be(HC 5 O 4 ). Two substances reported by Heller (1837; i). The first was a brown powder and the second yellow crystals. Both made by treating an alcoholic solution of the correspond- ing acid with beryllium acetate. Beryllium Citraconate, BeC 5 H 4 O 4 ; Beryllium Fumarate, Beryl- lium Maleate, BeC 4 H 2 O 4 . Have no basis for a claim to existence except the BeO content of a substance made by Tanatar (1907; 12), b> f treating the corresponding acid with basic carbonate and evaporating. There is nothing to indicate that they are not the usual indefinite basic mixtures obtained under these conditions. CHAPTER IV ACID SALTS OF BERYLLIUM. Beryllium has very little tendency to form acid salts and only an acid oxalate, an acid molybdate, an acid phosphate, an acid arsenate and four acid selenites have place in chemical litera- ture. The first has been shown to be a simple mixture of the normal oxalate and oxalic acid, and the molybdate and selenites were little more than the residues left on evaporating the con- stituents with little of detail in their study. The phosphate was non-crystalline. These salts need confirmation although from the well known tendencies of phosphoric acid, the existence of an acid phosphate would seem as probable as any acid salt of beryllium. Beryllium Monoacid Phosphate, BeHPO 4 .3H 2 O. Sheffer ( T 859; 3) precipitated a nitric acid solution of beryllium with disodium acid phosphate, obtaining a white non-crystalline pow- der, and gave the formula, BeHPO 4 .3H 2 O, to the precipitate formed. He found it lost two molecules of water on drying. Atterberg ( 1875 ; 4) also obtained the same substance by solu- tion of the hydroxide in phosphoric acid and precipitating with alcohol. A viscous mass was obtained which analyzed near to the above formula. By dissolving in phosphoric acid and pre- cipitating with alcohol, Sheffer thought the mass formed had the composition, 5BeO.2P,O 5 4H 2 O. Beryllium Acid Arsenate, BeHAsO 4 .2H 2 O. Reported by At- terberg (1875; 4) as resembling the corresponding phosphate and made in the same way. Beryllium Acid Selenites. Nilson (1875; 2. and 1875; 3) re- ported four beryllium selenites apparently acid in nature, Be- SeO 3 .H 2 SeO 3 , BeSeO 3 .2H 2 SeO 3 , 5BeO.8SeO 2 .5H 2 O and 3BeO. 7SeO 2 .5H 2 O. Whether these substances are mixtures or def- inite individuals needs confirmation, as they were little more than the residues left on evaporating the constituents together. 46 CHEMISTRY OF BERYLLIUM Atterberg (1873; 7) did not succeed in making any acid selen- ites, although he obtained the usual basic mixture. Beryllium Acid Oxalate. Rosenheim and Woge (1897; 4) re- ported the compound, 2BeC 2 O 4 .H 2 C 2 O 4 .5H 2 O. This was in- vestigated by Parsons and Robinson (1906; i) who showed that the substance is simply a mixture of the normal oxalate and oxalic acid. All attempts to make it as a distinct substance met with failure. Beryllium Acid Molybdate. Atterberg (1873; 7) reported an acid molybdate, BeMoO 4 -f MoO 3 + xAq, but gives little detail. CHAPTER V DOUBLE SALTS OF BERYLLIUM. 1 Many well defined and crystalline double salts of beryllium have been made. In many cases the double salts are readily prepared and are quite stable when the normal single salt can not be produced at all or only in the absence of water. This is notably true in the case of the double carbonates, chlorides, io- dides, nitrites and sulphites. In general these salts have been but little studied, their discoverers being content with their identification and analysis. Being less subject to the confusing action of hydrolysis than either the normal or basic salts of beryllium, their description and identity can, as a rule, be de- pended upon when found in literature. DOUBLE CHLORIDES. Potassium Beryllium Chloride, BeCl 2 .2KCl. Enumerated by H. L. Wells (1901; 3) in his list of double halides. Authority has not been found. Welkow (1874; 6) could not obtain a double chloride with either potassium or sodium. Mercury Beryllium Chloride, 2BeCl 2 .3HgCl 2 -f-6H 2 O. A double chloride with mercury has been reported by two observers, Hrst by Bonsdorff (1828; 4) who simply states it was obtained in rhombic prisms, but gives no analysis or formula, and second by Atterberg (1873; 7) who obtained it in large tabular hydro- scopic crystals by evaporation of like equivalents of the two chlorides in excess of strong hydrochloric acid. Marignac (1873; i) could not obtain the double salt and states that it is a mistake and the HgCl, crystallizes out alone. Auric Beryllium Chloride, BeCl 2 .AuCl 3 and BeCl 2 .2AuCl 3 . Obtained by Atterberg (1873; 7) together from a solution of like equivalent, allowed to stand for a long time over sulphuric acid. The first crystallized as tetragonal double pyramids and iater the crystals of the second form settled out. 1 Some salts are included here which are possibly not true double salts but salts of a complex acid. 4 CHEMISTRY OF BERYUJUM Stannic Beryllium Chloride, BeCl 2 .SuCl 4 .8H 2 O. - Atterberg (^73 > 7)> by dissolving tin chloride and beryllium oxide in excess of hydrochloric acid and evaporating over sulphuric acid, obtained some ill defined rhombic pyramids. They deliquesced easily in air. Marignac (1873; i) was not able to obtain any double salt with tin. Ferric Beryllium Chloride, BeCL.FeCl 3 +H 2 O. Orange yel- low crystals obtained by adding beryllium chloride to warm concentrated hydrochloric acid (1.19 specific gravity) to which a large amount of ferric chloride had already been added and allowing the solution to cool. Neumann (1888; i). Chromic Beryllium Chloride, BeCl 2 .CrCl 3 .H 2 O. Prepared as violet hydroscopic crystals by Neumann (1888; i) by dissolv- ing chromic chloride in strong alcohol, adding some beryllium chloride and passing hydrochloric acid gas through the heated mixture. Thallic Beryllium Chloride, 3BeCl 2 .Tl 2 Cl 6 . By dissolving thallium oxide and beryllium chloride in strong hydrochloric acid and oxidizing with chlorine, Neumann (1888; i) obtained rhombic tabular crystals of the above formula. lodic Beryllium Chloride, BeCl 2 .2lCl 3 .8H,O. Obtained by Weinland and Schlegelmilch by passing a current of chlorine through a cold strong hydrochloric acid solution of beryllium chloride to which an excess of iodine had been added. Gold yellow needles, very unstable and hydroscopic. Platinous Beryllium Chloride, BeCl 2 .PtCl 2 .5H 2 O. Nilson (1876; 2) prepared the beryllium chlorplatinate by evaporating together platinum dichloride and beryllium chloride in hydrochlo- ric acid solution. Obtained dark red crystals soluble in water, which at 100 lost both water and hydrochloric acid. Platinic Beryllium Chloride, BeCl 2 .PtCl 4 .8H,O. First pre- pared by Thomsen (1870; i) by dissolving beryllium hydroxide in a hydrochloric acid solution of platinic chloride and crystal- lizing. Thomsen assigned 9H 2 O, but was corrected by Marig- nac (1873; 3). Further by heating at 120, he found his crys- tals lost water and then had the composition, BeCl 2 .PtCl 4 .4H 2 O. It was later prepared by Welkow (1873; 5). The crystals are DOUBLE SALTS OF BERYLLIUM 49 dark yellow or orange, four, six, or eight-sided prisms, soluble in alcohol and very hydroscopic. Palladous Beryllium Chloride, BeCl 2 .PdCl 2 .6H 2 O. Welkow (1874; 6), by heating a concentrated solution of beryllium pal- ladic chloride, caused it to lose chlorine and obtained brown tabular, hydroscopic crystals having the above formula and readily soluble in water and alcohol. Palladia Beryllium Chloride, BeCl 2 .PdCl 4 .8H,O. Obtained by Welkow (1874; 3) as small, dark, reddish brown, quadratic tables by evaporating a solution of the constituents over sulphur- ic acid. It is isomorphous with the corresponding platinum salt, but loses all of its water at 130. DOUBLE FLUORIDES. Potassium Beryllium Fluoride, BeF 2 .KF and BeF 2 .2KF. Two double fluorides of potassium are known. The second of these was produced as early as 1811 by Gay Lussac and Thenard and again in 1823 by Berzelius, but they made no analyses. Awdejew (1842; 2) prepared and studied BeF 2 .2KF and Debray (1855; i), BeF 2 .KF. Gibbs (1864; 3), Marignac (1873; 2), and finally Lebeau (1898; 8, 1899; n) confirmed the salts and Marignac fully described the crystals of BeF 2 .2KF, but the other salt yielded no well defined crystals. Crystals of BeF 2 .2KF are readily thrown down by evaporation of a mixture of the constitu- ents. It is soluble in 19 parts of boiling water and 50 parts of water at 20. It decrepitates slightly when heated and fuses at a red heat. If large excess of BeF 2 is present, a mass, hav- ing approximate composition, BeF 2 .KF, is formed, which on be- ing again crystallized yields the first named salt. Its individ- uality as a definite double salt seems somewhat doubtful. Klatzo (1869; i) claims these salts can not be made, but Lebeau (1899; n) confirms Marignac. Sodium Beryllium Fluorides, BeF 2 .NaF, BeF 2 .2NaF. Two sodium beryllium fluorides have been described by Marignac (1873; 2) and Lebeau (1899; n), entirely analogous to the potassium salts. They were made in a similar way by the simple evaporation of their constituents, and again it is the disodium salt that is obtained most easily and in definite crystals. BeF 2 . 4 5O CHEMISTRY OF BERYLLIUM 2NaF is easily obtained by evaporation in small, hard, brilliant dimorphous crystals, both forms of crystals being rhombohedral prisms, but of different angle. The salt is soluble in 68 parts of water at 18 and in 34 parts at 100. Marignac gives draw- ings and measurements of the crystals of BeF 2 .2NaF and could get no definite crystals of the other salt, which like the corre- sponding potassium compound, seems to be of doubtful existence as a definite compound. Ammonium Beryllium Fluoride, BeF 2 .2NH 4 F. First prepared by Marignac, (1873; 2) and later studied by v. Helmholt (1893; 2) and Lebeau (1899; n). Obtained by evaporating the con- stituents as small colorless needles or rhombic prisms. It is isomorphous with the corresponding potassium salt. Lebeau used it as a means to prepare pure beryllium fluoride. Marignac figures the crystals and gives full measurements. DOUBLE IODIDES. Welkow (1874; 6) obtained a double iodide of beryllium -with bismuth and one with antimony, but was unable to separate them from the mother liquors and identify the salts. Mosnier (1897; 7) produced a double beryllium lead iodide l)y saturating a hydriodic acid solution of beryllium iodide with lead iodide. He obtained fine yellow needles decomposed by -water, the analysis of which agreed fairly well with the formula, 13eI 2 .PbI 2 .3H 2 O, although Mosnier preferred to consider beryl- lium as a triad. DOUBLE SULPHIDES. Berzelius (1826; 2) reported a double sulphide with tungsten but did not identify the salt. DOUBLE CYANIDES. Beryllium Platinum Cyanide, BePtCy 4 4H 2 O. Toczynski (1871; 2) made beryllium platino cyanide in gold yellow crys- tals by the action of beryllium sulphate on barium platino cy- anide and crystallization from alcohol. Atterberg (1873; 7) confirmed his results. By mixing this with the corresponding magnesium salt and recrystallizing, Toczynski obtained crys- tals to which he assigned the formula, BeMg 2 Pt 3 Cy 1 ..4-i6H 2 O. DOUBLE SALTS OF BERYLLIUM 51 Beryllium Platibromo Cyanide, BePtBr 2 (Cy) 4 . Obtained by Holtz (1873; 10) as thin plates. DOUBLE SULPHATES. Beryllium Potassium -Sulphate, BeSO 4 .K 2 SO 4 .2R,O. This sulphate was probably first prepared by Vauquelin (1798; 2), but was first described by Awdejew (1842; 2) and later by Debray (1855; i), Klatzo (1869; i), Marignac (1873; 2) and Atterberg (1873; 7), all of whom agree essentially as to formu- la and details. It is prepared by the simple evaporation of its constituents in like proportions. The crystals are small and colorless and even Marignac was unable to determine their form. They are much more soluble in hot than in cold water. Klatzo thought they contained 3H 2 O when crystallized between 2 and -3 C. Beryllium Acid Potassium Sulphate, BeSO 4 .K 2 SO 4 .2HKSO 4 . 4H 2 O. Atterberg (1873; 7) by evaporating a strongly acid so- lution of like equivalents of beryllium sulphate and potassium sulphate, obtained a mass of fine needle-shaped prisms to which he assigned the above formula. Sodium Beryllium Sulphate, 3BeSO 4 .2Na 2 SO 4 .i2H,O. Re- ported by Atterberg (1873; 7) as fine needle-shaped crystals forming in radiating star-shaped groups and obtained by evapo- rating a solution containing three equivalents of beryllium sul- phate and one of sodium sulphate, to a thick syrup. Loses 7H 2 O at 100. Ammonium Beryllium Sulphate, BeSO 4 .(NH 4 ) 2 SO 4 .2H 2 O. - Obtained by Atterberg (1873; 7) by evaporating like equiva- lents of the two sulphates first by heat and then over sulphuric acid to a thick syrup. On stirring, the syrup became a crys- talline mass and by pouring out the mother liquor, he obtained the crystals to which he assigned the above formula. They lost all their water at 110. DOUBLE SULPHITES. Potassium Beryllium Sulphite, 2BeSO 3 .K 2 SO 3 .9H,O. Rosen- heim and Woge (1897; 4J obtained this salt in the crystalline form by saturating acid potassium sulphite with beryllium hy- droxide and after filtering, passing in excess of sulphur diox- 52 CHEMISTRY OF BERYLLIUM ide and evaporating the solution in a desiccator in an atmosphere of sulphur dioxide. No description of the salt is given other than its analysis and the fact that it lost sulphur dioxide easily when exposed to the air. Ammonium Beryllium Sulphite, 2BeSO 3 .(NH 4 ) 2 SO 3 .4H 2 O. Prepared by Rosenheim and Woge ( 1897 ; 4) in the same man- ner as the potassium salt and had similar properties. On ex- posure to air lost ammonium sulphite as well as sulphur diox- ide. Sodium Beryllium Sulphite. Rosenheim and Woge (1897; 4) failed to prepare this salt, obtaining only an uncrystallizable syrup. Double Beryllium Molybdates. Rosenheim and Woge (1897; 4) were unable to obtain any double salt with either potassium sodium or ammonium molybdate. DOUBLE NITRITE. Beryllium Diplatonitrite, BePt(NO 2 ) 4 .PtO.9H 2 O. Was pre- pared by Nilson (1876; 3) by treating barium platonitrite with barium sulphate and evaporating in a vacuum. Obtained small bright red crystals which are probably not a true double salt, as in solutions of these salts the platinum ion is apparently not present. Beryllium Platino-di-iodo-nitrite. Prepared by Nilson (1878; 7) in the form of small, quadrangular, yellow tables which de- composed at 100. Crystals were very deliquescent and very soluble in water. DOUBLE PHOSPHATES. Potassium Beryllium Orthophosphate, BeKPO 4 . Grandeau (1886; 2) first prepared this phosphate by fusing the sulphate of beryllium with acid potassium phosphate. Ouvrard (1890; 1 1 ) by fusing beryllium oxide with either meta-, ortho- or pyro- phosphate obtained the same compound in rhombic prisms. Sodium Beryllium Orthophosphate, BeNaPO 4 and BeNa 4 (PO 4 ) 2 . Wallroth (1883; i) first obtained this phosphate by fusing beryllium oxide in sodium metaphosphate. The crystals ob- tained were in the form of hexagonal plates. Ouvrard (1890; 1 1 ) obtained the same salt in the same manner and also by us- ing sodium pyrophosphate. He states that his crystals were DOUBLE SALTS OF BERYLLIUM 53 identical with those of beryllonite. By using sodium ortho- phosphate instead of meta- or pyrophosphate, he obtained the second phosphate, Na 4 Be(PO 4 ) 2 , in lamellae. Ammonium Beryllium Phosphate. Rossler (1878; 9) has shown that a crystalline precipitate, similar to ammonium mag- nesium phosphate can be produced by adding an excess of am- monium phosphate to a beryllium salt, adding hydrochloric acid and just neutralizing with ammonia, but states that this pre- cipitate varies in composition. M. Austin (1899; 8) has also worked with this precipitate in an attempt to obtain an analyt- ical method for beryllium, but agrees that the. results are inaccu- rate. Ammonium Sodium Beryllium Phosphate, Be(Na) 2 (NH 4 ) 2 - (PO 4 ) 2 . Prepared according to Scheffer (1859; 3) by precip- itating beryllium nitrate with sodium phosphate in the presence of ammonium chloride. DOUBLE CARBONATES. Ammonium Beryllium Carbonate. By precipitating an ammo- nium carbonate solution of beryllium hydroxide with alcohol, a white deposit is obtained which is fairly stable and the compo- sition of which depends upon the relative amounts of the con- stituents present and especially upon the mass of the carbon di- oxide component. If such a solution is boiled previous to the addition of the alcohol and the latter added at the point where the beryllium begins to separate as a basic carbonate, the precip- itate has the composition, 3BeCO 3 .Be(OH) 2 +3(NH 4 ),CO 3 , ac- cording to Debray (1855; i) and Klatzo (1869; i), while Hum- pidge (1886; i) assigns to it the formula, 2(BeCO 3 .(NH 4 ) 2 CO 3 > ). Be(OH) 2 .2H 2 O. This slowly loses ammonia and carbon dioxide in the cold and quickly on heating. Potassium Beryllium Carbonate. By a similar procedure to the preceding, Debray obtained a double salt or a mixture to which he assigned the analogous formula, 3(BeCO 3 .K 2 CO 3 ). Be(OH) 2 . It was obtained in the form of a white precipitate by adding alcohol to a solution of beryllium hydroxide in potas- sium carbonate. 54 CHEMISTRY OF BERYLLIUM DOUBLE SILICATES. Potassium Beryllium Silicate. Hautefeuille and Perrey (1888; 5, 1893; i) obtained crystals of a potassium beryllium silicate of indefinite composition by fusing the constituents of a beryllium leucite in excess of potassium vanadate. They concluded that these heterogeneous crystals were mixtures of simpler types. Friedel and Sarasin (1892; i) obtained a beryllium aluminum potassium silicate in hexagonal prisms by fusing the oxides of the first two in potassium silicate. Duboin (1896; 5) obtained crystals of a double silicate varying in composition between 2K 2 O.3BeO.5SiO 2 and 2K 2 O.3BeO.7SiO 2 by dissolving beryl- lium oxide and silicon dioxide in potassium fluoride and then submitting to long fusion with potassium chloride. Sodium Beryllium Silicate. Hautefeuille and Perrey (1890; II and 1893; i) in manner analogous to their corresponding potassium compounds by fusing the constituents of a beryllium nephelene in excess of sodium vanadate, .obtain crystals of a silicate varying between wide limits and which they concluded were mixtures of simpler types. Lithium Beryllium Silicate. Friedel (1901; 4) by fusing to- gether the constituents, obtained a silicate which he considered a mixture of Li 2 SiO 3 and Be 2 SiO 4 showing an isomorphism similar to that between albite and anorthite. Aluminum Beryllium Silicate, Be 3 Al 2 (SiO 3 ) 6 . Artificial beryl has been made by both Williams (1873; 3) and by Hautefeuille and Perrey (1888; 4) by fusing together the proper mixture of beryllium, aluminum and silicon oxides, the latter authors using acid lithium molybdate as a mineralizing agent. The natural color of emeralds may be given by means of chromium, using a reducing flame. Although Williams fused his beryl in the oxy- hydrogen flame, the flame is scarcely hot enough to make even fairly imitative emeralds, the necessary mixture of gases to give a clear fusion developing bubbles and oxidizing the color. DOUBLE OXALATES. Potassium Beryllium Oxalate, BeC,O 4 .K 2 C 2 O 4 . Debray (1855; i) first obtained this oxalate by evaporating the constituents to- gether, and his work has since been corroborated by Rosenheim DOUBLE SALTS OF BERYLLIUM 55 and Woge (1897; 4) and Wyrouboff (1902; i). Rosenheim and Woge also obtained it with one molecule of water of crys- tallization. Wyrouboff was unable to measure the crystals, but states that owing to its comparative insolubility it is a promising' means of separating beryllium from iron and aluminum. In a later article (1902; 2) he actually uses this property to separate beryllium from beryl, precipitating by means of acid potassium oxalate. Potassium Diberyllium Oxalate, K 2 O.2BeO.C 2 C 3 +2^H 2 O. Prepared by Philipp (1883; 2) by saturating acid potassium oxalate with beryllium hydroxide. Rosenheim and W r oge (1897; 4) by the same method did not get regular results as the beryl- lium hydroxide dissolved varied with the condition. By saturat- ing at the boiling point, diluting somewhat and allowing to stand the excess of beryllium hydroxide was deposited and on filtering the solution and evaporating over sulphuric acid distinct crystals separated out having the above composition. Sodium Beryllium Oxalate, BeC 2 O 4 .Na 2 C 2 O 4 .H 2 O. Prepared by Rosenheim and W 7 oge (1897; 4) and by Wyrouboff (1902; i ) in the same manner as the analogous potassium compound and resembling it closely. It gives off but part of its water at 120 and is comparatively insoluble in water. Sodium Diberyllium Oxalate, Na 2 O.2BeO.2C 2 O 3 +5H 2 O. Pre- pared by Rosenheim and Woge (1897; 4) in the same manner as the corresponding potassium salt. It differs from it in being crystallized only from much more concentrated solution. Ammonium Beryllium Oxalate, BeC 2 O 4 .(NH 4 ) 2 C 2 O 4 . Pre- pared first by Deb ray (1855; i) by crystallizing the constituents together from water solution and used by him in his determina- tions of the atomic weight of beryllium. Philipp (1883; 2) considers this salt characteristic for beryllium and of probable use in separating the element. Rosenheim and Woge (1897; 4) also produced the salt. Its analysis is about the only detail given. Ammonium Diberyllium Oxalate, (NH 4 ) 2 O.2BeO.2C 2 O s . 2^H 2 O. Prepared by Rosenheim and Woge (1897; 4) strict- ly analogous in composition and method of preparation to the 56 CHEMISTRY OF BERYLLIUM corresponding potassium salt. Crystallizable only from a very concentrated solution. Rubidium Beryllium Oxalate, BeC 2 O 4 .Rb 2 C 2 O 4 . Prepared by Wyrouboff (1902; i) in well defined triclinic crystals which he measured and described. Axial ratio 1.0814:1:1.2575, be 78 40', ac=86 46', ab=io$ 40'. It is more readily soluble in water than the potassium or sodium salt. Lithium Beryllium Oxalate, BeC 2 O 4 .Li 2 C 2 O 4 .2H 2 O. Prepared by Wyrouboff (1902; i) in thin monoclimc tables which are very soluble in water and lose their water of crystallization at 110. Crystals were measured 0.6163:1:1.5445, ac=gi 42'. DOUBLE TARTRATES. These salts have been studied by Toczynski (1871; 2), Ros- enheim and Woge (1897; 4) and Rosenheim and Itzig (1899; 13) and show some remarkable properties especially in that the beryllium appears to take the place of the hydrogen of the organic group as well as the acid hydrogen. The compounds thus obtained have exceptionally great molecular rotation. Toc- zynski reports two potassium beryllium tartrates, KBeC 4 H 3 O,, 4- Aq and KBe 2 C 4 HO 6 +Aq. The first separated in small spheres after crystallizing out some tartaric acid from a mixture of two molecules of acid potassium tartrate and one molecule of beryllium hydrate. The second crystallized in hemimorphous prisms from solution of acid potassium tartrate saturated by boiling with excess of beryllium hydroxide. It should be iden- tical with the potassium diberyllium tartrate of Rosenheim and Woge. Toczynski also obtained some glassy uncrystallizable masses of antimony beryllium tartrate by treating tartaric acid with antimony and beryllium oxides, but they were too indefinite to be given place among the compounds of beryllium. The double tartrates of beryllium and the alkalies have been made the subject of an extended research by Rosenheim and Woge (1897; 4) and Rosenheim and Itzig (1899; 13) and have been carefully systematized by these authors. According to them beryllium forms two series of compounds with the alkalies, the monoberyllium alkali tartrates and the diberyllium alkali tar- trates. DOUBLE SALTS OF BERYLLIUM 57 Diberyllium Alkali Tartrates, K 2 Be 4 C 8 H 4 O 13 +7H 2 O, Na 2 Be 4 - Be Be/ | CHCK X OHC COOBe O BeOOC. In their opinion the salts are largely dissociated even in com- paratively concentrated solution, and the complex anion is unusual- ly stable and subject but little to hydrolysis as the molecular ro- tation changes but little on dilution. They found the molecu- lar rotation of these salts extraordinarily high. They were cal- culated on the basis of the water free simplest formulas. KBe,C 4 H 3 7 - + 225.3 NaBe 2 C 4 H 3 O 7 = -f 225.1 NH 4 Be 2 C 4 H 3 7 = + 241.7. Also the molecular conductivity was determined K(K 2 Be 4 C 8 H 4 ls + 7H 2 0),A=/x 1024 /A32 = 63.9 43-6-20.3, ^(Na 2 Be 4 C 8 H 4 13 + ioH 2 O), A=^ 1024 ,x 32 = 59.3 38.6 = 20.7. They made no migration tests for the presence of the anion. Monoberyllium Alkali Tartrates, K 2 Be 2 C 8 H 8 O 13 + 2H 2 O, (NH 4 ) 2 Be 2 C 8 H 8 O 13 +2H 2 O, Na 2 Be 2 C 8 H 8 O 1 ,-{-3H 2 O, are rather more indefinite than the diberyllium salts as they are not ob- tained as distinct crystals. By treating a slight excess of al- kali bitartrate with the calculated amount of beryllium hydrox- 5 CHEMISTRY OF BERYLLIUM ide, boiling and concentration, the excess of alkali tartrate crys- tallizes out and on further evaporation a thick syrup is obtained, which on cooling solidifies to a mass of apparently constant composition. The authors assign the double formula also to these residues corresponding with the type COOR ROOC CHOH HOHC I I CHOH HOHC I I COOBe O BeOOC and believe it contains the complex anion, Be 2 C 8 H 8 O I3 . This anion like that of the diberyllium salts is very stable and not hy- drolyzed on dilution. The molecular rotation was determined for the potassium and ammonium salts only as they were not able to obtain the sodium salt in sufficient quantity free from excess of bitartrate. The results of many closely agreeing de- terminations in solutions of varying dilution yielded for the molecular rotation, calculated on the water free molecule, # (K 2 Be.,C 8 H 8 13 ) = 124-7 #((NHJ,BeAH 8 ls )= 125.8. Ammonium Diberyllium Racemate, (NH 4 ) 2 Be 4 C 8 H 4 O 13 + ioH 2 O; Ammonium Monoberyllium Racemate, (NH 4 ) 2 Be 2 C 8 H 8 - O 13 +2H 2 O. These two salts were also prepared by Rosenheim and Itzig (1899; 13) and were found to be in every way analo- gous to the corresponding tartrates except, as was to be expected, they were optically inactive. This of course shows that beryl- lium has the same effect of increasing the regular rotation when substituted in the molecule of the laevo-tartrates as has been shown to be the" case with the dextro-tartrates. The result of the introduction of beryllium into the tartrate molecule is well shown by the following table : MOLECULAR ROTATION [M]^ OF Bitartrate Tartrate Monoberyllium Diberyllium Tartrate Tartrate Ammonium f 42.8 +63.0 4-125.8 +241.7 Potassium 42-5 6 4-4 124.7 225.3 Sodium 41.2 59-9 225.1 DOUBLE: SALTS OF BERYLLIUM 59 DOUBLE MALAXES. Rosenheim and Itzig (1899; 13) by saturating laevo-alkali acid malates with freshly precipitated beryllium hydroxide at boiling temperature, obtained excellently crystallized diberyllium malates in small prismatic crystals. These crystals were much less soluble in water than the corresponding tartrates and con- sequently separated from comparatively dilute solution. They prepared Potassium Diberyllium Malate, K 2 Be 4 C 8 H 6 O 12 -f 5H 2 O. Sodium Diberyllium Malate, Na 2 Be 4 C 8 H 6 O 12 -f 7H 2 O. Ammonium Diberyllium Malate, (NH 4 ) 2 Be 4 C 8 H 6 O 12 +4H 2 O. By precipitating any one of these salts with dilute barium chloride solution, a precipitate formed of needle-shaped crystals of Barium Diberyllium Malate, BaBe 4 C 8 H 6 O 12 -f 6 or i2H 2 O The precipitation of this salt seems to lend additional evidence of the existence of these complex tartrates and malates as definite compounds. Mercury, lead and silver salts threw down only amorphous precipitates. Rosenheim and Itzig determined the molecular rotation ^(K 2 Be 4 C 8 H 6 12 ) = 198.9, ^(Na 2 Be 4 C 8 H 6 12 ) = 202.2, ^(NH 4 Be 4 C 8 H 6 12 ) = 200.9. They also determined the molecular conductivity and found for ^(K 2 Be 4 C 8 H 6 12 ), A = ^ 1024 ^ = 63.8 45-5 == 18.3, }^(Na 2 Be 4 C 8 H 6 O 12 ), A = /* 1024 /x 32 55.5 36.2 = 19.3. They argue that these salts contain the stable anion, Be 4 C 8 H 6 O 12) and that the molecule is structurally according to the type COOR ROOC I I CH, H,C I I CHO Be O Be OHC COO Be O Be OOC. Ammonium Monoberyllium Malate, (NH 4 ) 2 Be 2 C 8 H 8 O 11 -f-H 2 O. This salt was also prepared and studied by Rosenheim and 60 CHEMISTRY OF BERYLLIUM Itzig (1899; 13) by the same method as used for the corre- sponding tartrate. The sodium and potassium salts could not be separated from an excess of bimalate. The salt was obtained simply as a non-crystalline mass left on evaporation. By analy- sis this mass corresponded to the formula given above. The molecular rotation was determined and found for ^(NH 4 ) 2 Be 2 C 8 H 8 O n to be 106.3. The strong influence which beryllium exerts upon the polariza- tion of the malates is shown by the following table: MOLECULAR ROTATION [M]#. Bimalate Neutral Monoberyllium Diberyllium Malate Malate Malate Ammonium 9.89 - i3- 2 7 106.3 -200.9 Potassium 9.68 -14.26 -198.9 Sodium 10.02 14.31 202.2 CHAPTER VI BASIC COMPOUNDS OF BERYLLIUM. Some of the most interesting problems of the chemistry of beryllium lie in the equilibrium relations between its oxide and the various acid radicals. It is certainly true that many of these acids can hold in solution phenominally large amounts of beryl- lium oxide extending in the case of the acetate to six equiva- lents (Ordway, 1858; i), while the chloride can hold four, the sulphate three and the oxalate nearly three equivalents. These solutions on being diluted with water throw down precipitates of a highly basic nature or on evaporation leave gummy masses, the basicity of which depends upon the concentration of the acid used which determines the amount of dissolved oxide, or rather hydroxide, while they differ physically but little. Both the pre- cipitated bodies and the residues of evaporation are amor- phous and glassy in structure and vary widely in compo- sition according to the concentration of the solutions from which they were precipitated and the extent to which the acid had dis- solved the base. The basic precipitates on washing with water ap- proach the hydroxide in composition, although the last traces of the acid radical are almost impossible to remove. These facts have given rise in literature to a large number of so-called com- pounds of beryllium which in reality have no existence as inde- pendent individuals, but were obtained by the analysis of the indefinite mixture or solid solution which the particular con- ditions happened to yield, and in many cases, indeed, have no further basis for individuality than the per cent, of BeO they were found to contain. Equilibrium experiments, or repeated crystallization without change of composition, are necessary to establish the identity of individuals, for freezing point determina- tions may lead to erroneous conclusions since the addition of Be (OH) 2 to solutions of the normal salt raises their freezing point (1907; 10 and n). t>2 CHEMISTRY OF BERYLLIUM It is indeed difficult to understand how the solution of the. normal sulphate and nitrate can dissolve several equivalents of their own hydroxide, attack metals and carbonates almost as if they were sulphuric or nitric acid themselves, yielding these bas- ic substances and still be less hydrolyzed (Leys, 1899; i, Brun- ner, 1900; i) than the corresponding salts of iron and aluminum- Certainly it seems to be true that all of the so-called basic compounds of beryllium, produced in the presence of water by adding the hydroxide or basic carbonate to a solution of an acid or a normal salt, have no real existence as such, but come only in the domain of homogeneous phases of variable composition. To this some double salts, especially the tartrates and malates of Rosenheim and Itzig (1899; 13), may seem to be an ex- ception, for at least some of them are obtained crystalline and of apparent definite composition. It must not be forgotten, how- ever, that the authors claim these to be not basic in nature, but complex and that the excess of beryllium replaces hydrogen in the acid radical, giving rise to complex anions to which their abnormal optical properties are due. In contradistinction to the above substance we have, however, the truly phenominal and actually basic compounds of beryl- lium which are produced pure, only in contact with anhydrous acid or so nearly anhydrous that the mass of the water present becomes negligible to produce hydrolysis. The true basic com- pounds so far obtained belong solely to the fatty acid series. Their solubility increases with the molecular weight. Basic Beryllium Acetate, Be 4 O(C 2 H 3 O 2 ) . This unique and interesting chemical compound appears to be peculiar to beryl- lium alone. It was discovered by Urbain and Lacombe ( 1901 ; 2) who studied it and described its properties. Parsons (1904; 5) used it as a means of determining the atomic weight of beryllium. Haber and Van Oordt (1904; 4) used its solubility in chloroform as a means of separating and purifying beryllium compounds, and Parsons (1904; 5) and Parsons and Robertson (1906; i) used its property of ready crystallization from hot glacial acetic acid for the same purpose. BASIC COMPOUNDS OF BERYLLIUM 63 Basic beryllium acetate melts at 283 -284 and boils at 330- 331, and is readily sublimed without decomposition. It has a vapor density agreeing with the formula, Be 4 O(C 2 H 3 O 2 ) 2 . It is itself almost insoluble in water, but is slowly hydrolyzed by cold water and quickly by hot, after which it dissolves. It is easily soluble in absolute alcohol and in chloro- iorm, and is soluble in benzene, toluene, xylene, naphtha and all petroleum distillates, turpentine, methyl alcohol, amyl alco- hol, ether, ethyl acetate, acetone and carbon disulphide. It is also soluble in acetic anhydride and glacial acetic acid and is on- ly converted to the normal salt by a mixture of these reagents on heating to 150 in a closed tube (Steinmetz, 1907; 5). Al- though a basic compound, its solution in glacial acetic acid can be saturated with hydrochloric acid gas and remain unchanged, it is unaffected in dry air. Ordinary acids attack it setting free acetic acid, probably through the agency of water they contain. It is much more soluble in boiling glacial acetic acid than in cold and is most readily crystallized in this manner. On cool- ing, it separates from boiling glacial acetic acid as small shin- ing grains which, under a magnifying glass, are seen to be al- most perfect octahedrons. The specific gravity of the basic ace- tate is 1.362 referred to water at 4 (Parsons, 1904; 5). It is best prepared by dissolving the carbonate or hydroxide in acetic acid, evaporating off all water and drying the residue. The residue is then boiled in pure glacial acetic acid which dis- solves it completely and on cooling a mass of small glistening octahedral crystals of the basic acetate are deposited. These may be recrystallized from hot acid as many times as desired. Vauquelin (1798; 5) and Ordway (1858; i) both attempted to make the acetate of beryllium but obtained the ordinary gum- my form through not being able to understand the fact that the presence of water made its preparation impossible. Tanatar (1904; 3) also studied the basic acetate and conclud- ed that its peculiar properties led to the supposition that beryl- lium is a tetravalent element with an atomic weight of 18.2. His belief is apparently not shared by others as the valency of 64 CHEMISTRY OF BERYLLIUM beryllium was long ago established from the vapor density of the chloride and bromide. Basic Beryllium Formate, Be 4 O(CHO 2 ) 6 . This compound was first prepared by Lacombe (1902; 3) by the action of an- hydrous formic acid in excess on the carbonate and sublima- tion of the product under diminished pressure. Parsons (1904; 5) attempted to use it for atomic weight determination, but found its sublimation and purification too difficult, as even un- der much diminished pressure it was partly decomposed. According to Lacombe it is insoluble in all solvents and as it sublimes without fusion, he did not determine its melting or boiling point. Tanatar (1907; 12) claimed to make it by mix- ing the calculated amounts of carbonate and acid and boiling in water, which is impossible. Basic Beryllium Propionate, Be 4 O(C 3 H 5 O 2 ) 6 . Was prepared by Lacombe (1902; 3) in the same way as the acetate. It is a solid having a melting point of H9-I2O and a boiling point of 339-34i. It sublimes at 221 under 19 millimeters pressure. No other details given. Tanatar (1907; 12) by treating with acetyl chloride obtained crystals of Be 4 O(C 3 H 5 - O 2 ) 3 (C 2 H,O 2 ) 3 with melting point 127 and boiling point 330. Boiling without decomposition. Soluble in ether and benzene. Basic Beryllium Isobutyrate, Be 4 O(C 4 H 7 O 2 ) 6 . 'Prepared by Lacombe (1902; 3) in manner analogous to the acetate, is a solid melting at 76 and boiling at 336-337. Under 19 mil- limeters pressure :t sublimes at 216. No other details given. Basic Beryllium Butyrate, Be 4 O(C 4 H 7 O 2 ) 6 . Is a liquid pre- pared in the same way as the acetate by Lacombe (1902; 3) which boils at 239 under 19 millimeters pressure. No other oetails given. Tanatar (1907; 12), by treating this with acetyl chloride, obtained Be 4 O(C 4 H 7 O 2 ) 4 .(C 2 H 3 O 2 ) 2 a liquid soluble in benzene and ether, melting at 15 and boiling at 351. Basic Beryllium Isovalerianate, Be 4 O(C 5 t! 9 O 2 ) 6 . Is a liquid prepared by Lacombe (1902; 3) in the same way as the acetate. Jt boils at 254 under 19 millimeters pressure. No other de- tails given. BASIC COMPOUNDS OF BERYUJUM 65 INDEFINITE BASIC BERYLLIUM SOLID PHASES. Among the basic beryllium substances which are of variable composition, but to which formulas have been assigned, the sulphates, oxalates and carbonates have been most studied and in the first two cases they have been shown to be simply solid solutions of the hydroxide and the normal salt. These three only are worthy of separate mention. BASIC SULPHATES. Berzelius (1815; i) first showed that beryllium sulphate dis- solves its own hydroxide in quantity although Vauquelin (1898; 5) and Gmeiin (1801; i) had already produced a gummy sul- phate. Berzelius assigned the formulas, 3BeO.SO 3 and 2BeO. SO 3 , to the evaporated residue of the corresponding solution for no other apparent reason than that they represented whole equivalents, although he must have known that any interme- diate ratio between 3BeO.SO 3 and BeO.SO 3 was as easily ob- tained and that any one of these residues had as good claim to the dignity of being a compound. To the basic precipitate ob- tained by diluting the concentrated solution of 3BeO.SO 3 with water, Berzelius gave the formula, 6BeO.SO 3 .3H 2 O. Debray (1855; i), many years later, used these basic sulphates as a method of separation from aluminum but assigned no formulas. Atterberg (1873; 7) also obtained precipitates by diluting with water the strong solution of BeSO 4 saturated with Be(OH) 2 and assigned formulas, BeSO 4 .5Be(OH) 2 -f 2H 2 O and BeSO 4 . 7Be(OH) 2 -(-H 2 O. He also again 'evaporated solutions con- taining three and two equivalents of the oxide to one of acid and of course obtained residues of that ratio corresponding to the first two formulas assigned by Berzelius. Parsons (1904; 10) attacked this problem by means of equilibrium experiments in a large specially constructed thermostat and showed that the precipitates obtained by diluting the more basic solutions con- sisted of a single phase, that they had a ratio when equilibrium was reached as high as 25BeO to iSO 3 , that they varied in com- position and that, therefore, they could only be a solid solution of the hydroxide containing a small amount of the normal salt. He also studied the basic liquid solution and showed that there 5 66 CHEMISTRY OF BERYLLIUM was nothing characteristic in the residue obtained by evapo- rating any particular ratio of acid to base. Parsons and Robinson and Fuller (1906; 3, 1907; 10) again took up the question of the solution of Be(OH) 2 in BeSO 4 solution and showed that the freezing point was raised and the conductivity lowered thereby, and that no anion containing beryllium was formed. They also showed that on dialyzing such solutions into water, beryllium hydroxide invariably sep- arated out and the solution left behind always had a higher basic ratio than that which had passed through the parchment. All these facts prove that none of these substances are true compounds, but merely solutions of some form or other. It seems quite probable that beryllium sulphate once dissolved acts simply as a liquid in which its own hydroxide is soluble (1907; ii). BASIC OXALATES. These substances hold a strictly analogous position to the sulphates already mentioned. Vauquelin (1798; 5) and Debray (1855; i) had obtained simply gummy basic masses and appar- ently realizing that they were not true compounds gave them no formulas. Atterberg (1873; 7) had the same experience, but assigned the formula, BeC 2 O 4 .Be(OH) 2 .H 2 O, to the mass obtained by evaporating the solution of one equivalent of the hydroxide in one equivalent of the normal oxalate and the for- mula, BeC 2 O 4 .6Be(OH) 2 .6H 2 O, to the highly basic precipitate obtained by diluting the solution of the first with a large ex- cess of water. Parsons and Robinson (1906; i) studied these basic oxalates by phase rule considerations, by the same method as had been used on the basic sulphates and showed that when equilibrium was reached the precipitated basic oxalates had a ratio as high as 25BeO to iC 2 O 4 , that they varied in composi- tion, that they consisted of a single phase and must, therefore, be simply a solid solution of the oxalate in the hydroxide or the simple hydroxide occluding some of the normal salt. The basic solutions like the sulphate appear to be a case of simple solution of the hydroxide in a mixed solvent consisting of water and beryllium oxalate. When the concentration of beryllium ox- BASIC COMPOUNDS OF BERYLUUM 67 alate in such a solution reaches its maximum, it will dissolve 1.85 equivalents of beryllium hydroxide. BASIC CARBONATE. When salts of beryllium are precipitated with sodium or potas- sium carbonates or when an ammonium carbonate or sodium bi- carbonate solution of beryllium hydroxide is boiled, a highly basic precipitate is thrown down to which the following formulas have been assigned. 2BeCO.,7Be(OH) 2 .2H 2 O, ( Schaffgotsch, 1840; 2). 2Be- C0 8 .7Be(OH) 2 .3H 2 O and 4BeCO 3 .8Be(OH) 2 .5H 2 O (Weer- en, 1854; i). BeC0 3 .2Be(OH) 2 . 3 H 2 0, (Debray, 1855; i), (Klatzo, 1869; i). BeC0 3 .2Be(OH) 2 .Aq (Parkman, 1862; i). BeC0 3 .5Be(OH) 2 . 3 H 2 O, (Seubert and Elten 1893; 4). BeCO 3 . 2Be(OH) 2 .2H 2 O, (Pollok, 1904; i). These formulas represent little else than an approximation at equilibrium between BeO, CO 2 and H 2 O under the conditions present. In the presence of the largest possible amount of the carbon dioxide the composition is approximately represented by one equivalent of the carbonate to two of the hydroxide, but boiling which not only increases hydrolysis, but removes car- bon dioxide from the system, slowly causes the solid phase to approach the pure hydroxide. There is nothing in literature to indicate that anyone of the intermediate stages represents a true compound and this is apparently realized by one or two of the authors. Chemically the basic precipitate is much the same whether it is thrown down by a soluble carbonate or by boiling an ammo- nium carbonate or diluted acid sodium carbonate solution. In either case it occludes notable quantities of the precipitant, which can not be removed by washing and the author has never found less thati two per cent, so contained. This fact is not generally realized, but is of decided importance when this sub- stance is to be used as a basis for the preparation of other compounds. In the case of occluded ammonia it can be re- moved by prolonged boiling or by intermittently passing car- bon dioxide through the precipitate suspended in water, filter- ing off the liquid and repeating. Many hours boiling is required by the first procedure and the residue left is almost the pure 68 CHEMISTRY OF BERYLLIUM hydroxide, while if the second method is used the purification is a matter of days, but the residue is about as rich in the CO 2 com- ponent as when first precipitated. Passing carbon dioxide through the boiling liquid has little effect on the result as would natural- ly be expected. The ammonia may be removed with but little loss of carbon dioxide, by momentarily boiling with steam, filter- ing, addition of fresh cold water and repeating several times. Ordinary washing with hot water does not seem to be effective. Drying at 100 does not remove the occluded ammonia, but its odor becomes immediately apparent on heating to the point where the carbon dioxide begins to be evolved. Physically the precipitates thrown down by alkaline carbon- ates are quite different from the precipitate on boiling an am- monium carbonate solution; the first being gelatinous and dif- ficult to wash while the latter comes down in granular condi- tion and filters most readily. A saturated solution of ammo- nium carbonate will dissolve an amount of freshly precipitated beryllium carbonate or hydroxide equivalent to 22 grams BeO in 1000 cubic centimeters (Pollok, 1904; i). On boiling this solution, carbon dioxide and ammonia escape rapidly and soon the basic carbonate precipitate begins to appear in fine white granular form. The boiling is best done by means of steam as otherwise very violent bumping takes place which continuous stirring will not entirely prevent. The first portions of the precipitate thrown down by boiling a solution saturated with ammonium carbonate are rather richer in carbon dioxide than those that follow having a composition approximating BeCO s .- BeCO 3 .sBe(OH) 2 .3H 2 O, (Seubert and Elten 1893; 4). BeCO 3 the boiling is continued in such a solution until precipitation is complete the composition is approximately BeCO 3 .+2H 2 O (Parsons, 1904; 5). If, on the other hand, the solu- tion is diluted, some four or five times hydrolysis of the whole material present takes place with very little boiling, and the granular carbonate thrown down appears to have the approx- imate composition BeCO 3 .2Be(OH) 2 +Aq. This material can be dried at 150 without notable loss of carbon dioxide. Fur- ther boiling causes gradual loss of carbon dioxide and eventual- BASIC COMPOUNDS OF BERYUJUM 69 ly only the hydroxide is left. Attempts by the writer to in- crease the carbon dioxide component in the precipitate, be- yond that already indicated by passing the gas under pressure over the precipitate and also over freshly precipitated hydroxide have so far proven unavailing. The basic carbonate obtained by boiling the ammonium car- bonate solution, while of no definite composition, is quite pro- perly a favorite material to be used as a basis for the production of beryllium salts since it dissolves readily in acids and if care is taken to remove all the occluded ammonia a pure salt is ob- tained at once. Acid sodium carbonate is an equally good sol- vent and on diluting a saturated solution some four or five times and boiling the basic carbonate is thrown down, but is more difficult to obtain in granular form. The occluded so- dium carbonate moreover can not, of course, be volatilized off. MISCELLANEOUS BASIC SOLID PHASES. Besides the basic sulphates, oxalates and carbonates, already enumerated, many other gummy precipitates and residues of evaporation have been assigned formulas as definite compounds and find place in the literature of beryllium. They are all prepared in much the same way and generally by saturating the solution of an acid or of a normal salt with beryllium hydroxide or carbonate and by evaporation or diluting with water obtaining a solid phase which is generally more or less changed by fur- ther washing with water. In the opinion of the writer none of these "so-called" compounds, appearing in literature, of which the following is a list, have any proven claim for individual existence, but are in reality solid solutions of the normal salt with the hy- droxide or, what is much the same thing, the hydroxide with more or less occluded normal salt. Basic sulphites: 2BeSO 3 .9Be(OH) 2 .6H 2 O, Seubert and Elten, 1893; 4. BeS0 3 .Be(OH) 2 .2H 2 0, Atterberg, 1873; 7. BeSO 3 .Be(OH) 2 .Aq, Kriiss and Moraht, 1890; 4. 3BeS0 4 .Be(OH) 2 .Aq Basic Dithionate: 2BeS 2 O 6 .3Be(OH) 2 +i4H 2 O, Kluss, 1888; 2. 7O CHEMISTRY OF BERYLLIUM Basic chlorides: 3BeCl 2 .2Be(OH) 2 , Atterberg, 1873; 7. BeCl,.3Be(OH) 2 , Atterberg, 1873; 7. BeCl 2 .i2Be(OH) 2 +ioH 8 O, Atterberg, 1873; 7. BeCl 2 .i2Be(OH) 2 4-4H 2 O, Atterberg, 1873; 7. Be(OH)Cl, Atterberg, 1875; 4. Basic selenites: 2BeSeO 3 .Be(OH) 2 +2H 2 O, Atterberg, 1873; 7. BeSe0 3 .Be(OH) 2 .H 2 O, Atterberg, 1873; 7. 2BeSeO 3 .3Be(OH) 2 .7H 2 O, Nilson, 1875; 2. Basic borates: Be(BO 3 ) 2 .2Be(OH) 2 +Aq, Kriiss and Moraht, 1890; 4. Basic nitrate: Be(N0 3 ) 2 .Be(OH) 2 .2H 2 O, Ordway, 1858; i. Basic chr ornate : BeCrO 4 .i3Be(OH) 2 +ioH 2 O, Atterberg, 1873; 7. BeCrO 4 .6Be(OH) 2 , Glassmann, 1907; 4. Basic molybdate: BeMo0 4 .Be(OH) 2 .2H 2 O, Atterberg, 1873; 7. Basic succinate : BeC 4 H 4 O 4 .Be(OH) 2 -U 2 H 2 O, Atterberg, 1873; 7. basic ferro cyanide : Be 2 FeCy 6 .4Be(OH) 2 +7H 2 O, Atterberg, 1873; 7. Also basic salts of the formula Be 4 O(Ac) 6 or Be 2 O(Ac) 2 claimed to be obtained by adding the carbonate to aqueous solution of the acid and evaporating. Basic crotonate: Be 4 O(C 4 H 6 O 2 ) 6 , Tanatar (1907; 12). Basic isocrotonate : Be 4 0(C 4 H 5 2 ) 6 ; Tanatar (1907; 12). Basic laevulinate : Be 4 O(C 5 H 7 O 8 )6, Tanatar (1907; 12). Basic succinate : Be 4 O(C 4 H 4 O 4 ) 3 , Tanatar (1907; 12). Basic cyanacetate: Be 4 O(C 2 H 2 CNO 2 ) 6 , Glassmann, (1908; i). Basic dichloracetate : BASIC COMPOUNDS OF BERYLLIUM 71 Be 4 O(C 2 HCl 2 O 2 ) 6 , Glassmann, (1908; i). Basic monochloracetate: Be 4 O(C 2 H 2 ClO 2 ) 6 , Glassmann, (1908; i). Basic monobromacetate : Be 4 O(C 2 H 2 BrO 2 ) 6 , Glassmann, (1908; i). Basic monobrompropionate : Be 4 O(C 3 H 4 BrO 2 ) 6 , Glassmann, (1908; i). Basic lactate: Be 2 O(C 3 H 5 O 3 ) 2 .H 2 O, Glassmann, (1908;!). Basic glycolate : Be 2 O(C 2 H 3 O 3 ) 2 .H 2 O, Glassmann, 1908; i). Basic trichloracetate : Be 2 O(C 2 Cl 3 O 2 ) 2 , Glassmann, (1908; i). Basic ethyl glycolate : Be 2 O(C 2 H 5 C 2 H 2 O 3 ) 2 .H,O, Glassmann, (1908; i). Basic phenyl glycolate : Be 2 O(C 6 H 5 C 2 H 2 O 3 ) 2 , Glassmann, (1908; i). Basic chloropropionate : Be 2 O(C 3 H 4 ClO 2 ) 2 .H 2 O, GUassman, (1908; i). Basic salicylate: Be 2 O(C 7 H 5 O 3 ) 2 , Glassmann, (1908; i). Basic beryllium chlorides (Vauquelin, 1798; 5, Gmelin, 1801 ; i), Nitrates (Vauquelin, 1798; 6, Gmelin, 1801 ; i). Hypophosphites (Rose, 1828; i), V derates (Trommsdorff, J 833; i), Oxalates, citrates, tartrates and acetates (Vauquelin T 798; 5) to which no formulas were assigned nor analyses made. PART II. BIBLIOGRAPHY OF BERYLLIUM. 1798; i. Vauquelin, L. N. De 1'Aigue marine, ou Beril; et decouverte d'une terre nouvelle dans cette pierre. Read at the Institute 26 Pluviose, An 6 (Feb. 14, 1898). Announces the discovery of a new earth, "la terre du Beril," separated from aluminum by the pre- cipitation of Be (OH) 2 from KOH solution on boiling. Differs from aluminum in its salts being sweet, having a greater affinity for acids, giving no alum, soluble in (NH 4 ) 2 CO 3 , soluble and not being precipitated by K 2 C 2 O 4 or K 2 C 4 H 4 O 6 . Editors suggest name "glucine" in foot note. Ann. de chim., 26 (1798) 155-170; Allg. J. Chem., i, (1798) 341; . Nicholson's J., 2, 358; Chem. Ann. (Crell), 14, 422. 1798; 2. Vauquelin, L. N. Sur la terre du Beril; pour ser- vir au premier memoire sur le meme object. Studies new earth and gives following specific char- acters, sweet and astringent salts, very soluble in H 2 - SO 4 , decomposes salts of aluminum, soluble in NH 4 OH, affinity for acids between magnesium and aluminum, soluble in fixed alkalies, infusible, soluble in acids ex- cept carbonic and phosphoric, fusible with borax, ab- sorbs one-fourth of its weight of CO 2 , not precipitated by saturated hydrosulphides. Ann. de chim., 26, 170-177; Nicholson's J., 2, 393 ; Chem. Ann. (Crell), 14, 434. 3- Vauquelin, L. N. Same as 1798; i. Again read before the French Society of Mines, and Vauquelin, in a foot note, refers to the proposed name glucine, but does not adopt it in text. J. des mines, 8, 553"5 6 4- BIBLIOGRAPHY OF BERYLLIUM 73 1798; 4. Vauquelin, L. N. Analyse de 1'emeraude du Peron. Shows identity of beryl and emerald and uses word glucine for first time, saying "on a donne le nom de giucine." Ann. de chim., 26, 259. Allg. J. Chem. (Scherer), I, 361. X 798; 5- Vauquelin, L. N. Ueber die Verhaltnisse der Glu- cine zu den Saueren. Made sulphate, nitrate, chloride, phosphate, carbon- ate, citrate, tartrate, acetate, mostly in gummy basic masses. Purified from iron by means of KHS. Allg. J. Chem. (Scherer), I, 590-596. 1799; i. Vauquelin, L. N. Sur Tanalyse des pierres en gen- eral et resultats de plusieurs de ces analyses faites au laboratoire de 1'ecole des mines depuis quelques mois. Points out how to recognize beryllium in rocks. Ann. de chim., 30, 82. 1799; 2. Vauquelin, L. N. Anleitung zur Zerlegung der Fossilien. Allg. J. Chem. (Scherer), 3, 430. 1799; 3. Link, H. F. "Correspondence." Objects to name glucine because it resembles glycine, already in use. Allg. J. Chem. (Scherer), 3, 603. 1800; i. Klaproth, M. H. In the third volume, page 78 of his Beitrage Zur Kentniss der Mineralkorper, he refers to a paper read by himself before the royal Academy of Sciences of Berlin on Sept. 11, 1800, in which he argues against the name "Glycine," proposed for Vau- quelin'"s earth, on the ground that sweetness is not unique to that element, but is also possessed by the yttrium earth and further is too much like "Glycine" which Link had already pointed out. Claims "Beryl- lerde'' should be used. 1801; i. Gmelin, H. R. Zerlegung des Berylls von Nert- schink in Sibirien und Priifung der daraus erhalten Susserde. 74 CHEMISTRY OF BERYLLIUM Confirms Vauquelin's discovery. Short unimpor- tant study of nitrate, chloride and sulphate. Chem. Ann. (Crell), 17, 89. 1 80 1 ; 2. Schaub, T. Chemische Untersuchung des blauen siberischen Berills. Fuses beryl with NaOH and KOH in silver cru- cible. Confirms Vauquelin's discovery. Chem. Ann. (Crell), 17, 174. 1802; i. Ekeberg, A. G. Sur quelques proprietes de 1'yttria compares avec celles de la glucine. Beryllium is precipitated from solution by the succin- ates, colorless salts, soluble in KOH, and not precip- itated by alkaline prussates. Chief differences from yttria. Specific gravity 660=2.967. J. des mines, 12, 245. 1809; i. Davy, Humphrey. On some new electro-chemical researches on various Objects, particularly the metal- lic bodies from the alkalies, an earths, and on some Combinations of Hydrogen. Attempted to reduce BeO in platinum tube by potas- sium vapor without certain result. On fusing BeO in clay crucible with iron filings and potassium ob- tained a semi-malleable mass. Phil. Trans., London, 100, 59. Ann. der Phys. (Gilbert), 32, 395. Ann. d. chim., (i) 75, 150. Phil. Mag., 32, 152, 203. 1811; i. Gay-Lussac, L. J., and Thenard, L. J. Recherches Physico-ch'imique. Made a fluoride of beryllium by precipitating HKF 2 with beryllium oxide dissolved in hydrochloric acid. Ann. d. chim., (i) 78, 275. 181 1 ; 2. John, J. F. Ueber einige unbekannte Verbindung;en der Chromsauere mit verschiedenen Basen. Dissolved basic carbonate in chromic acid, but could not crystallize any salt. BIBLIOGRAPHY OF BERYLLIUM 75 1812; i. Stromeyer, F. Du memoire stir la reduction de la terre silicee, operee par le moyen du charbon et du fer. Claimed that he reduced magnesium and beryllium with great success by mixing the oxides with carbon, iron and linseed oil to a paste and melting in closed crucible, obtaining alloys with iron. Stromeyer was mistaken. Ann. d. chim., (i) 81, 257. 1815; i. Berzelius, J. J. Versuch durch Anwendung der Elek- trochemische ( Theorie und der chemischen Propor 1 - tion Lehre Analyse der Beryllerde. Prepared crystals for the first time of BeSO 4 4H 2 O, which he considered an acid salt. By dissolving one and two equivalents of beryllium carbonate in this salt, he obtained on evaporation gummy masses con- taining the ratios 2BeO.SO 3 and 3BeO.SO 3 respec- tively. The first of these he considered the normal sulphate and the second a basic salt. On diluting the last with water he obtained a white precipitate to which he assigned the ratio 6BeO.SO 3 . He also de- termined the atomic weight of beryllium from BeSO 4 . 4H 2 O and analyzed an impure chloride. J. .fur Chem. (Schweigger), 15, 296. 1823; i. Berzelius, J. J. Untersuchungen iiber die Fluss- spathesaure und deren merkwurdigsten Verbindungen. Vet. Akad. Handl. (Stockholm), 1823, 302. Ann. der Phys. (Pogg), i, 22, 196. Annals of Phil. (Thomson), 24, 330. Made and described BeF 2 . Dissolved BeO in HF. Obtained an easily soluble substance which dries to a gummy mass and which loses H 2 O at 100, becoming milk white and foamy. Loses part of its HF on ig- nition. Yields double salts with alkalies of which the potassium salt is very insoluble. Obtained a beryl- lium fluosilicate by action of fluosilicic acid. 76 CHEMISTRY OF BERYLLIUM 1823; 2. Du Menil. Analyse des Sibirischen hellblaulichen Berylls ( Aquamarine ) . J. fur Chem. (Schweigger), 39, 487. Details method of analysis. 1825 ; i. Berzelius, J. J. Ueber die Schwefelsalze. Kongl. Vet. Acad. Hand!., 1825, 253; 275, 288, 311. Ann. d. Phys. (Pogg), 6, 453; 7, 23, 144, 273. Was not able to produce a sulphide of Be in solution. 1826; I. Berzelius, J. J. Ueber die Bestimmung der relativen Anzahl von emfachen Atomen in chemischen Verbind- ungen. Ann. d. Phys. (Pogg), 8, 187. Valueless data on atomic weight, as he used a very basic sulphate. Gives oxides as Be,O 3 . 1826; 2. Berzelius, J. J. Ueber die Schwefelsalze. Kongl. Vet. Acad. Handl, 1826, part I, 53. Ann. d. Phys. (Pogg), 8, 279. Thought he made a double sulphide of tungsten and beryllium by precipitating the double sulphide of po- tassium and tungsten with a beryllium salt. No for- mula or details. 1827; I. Rose, H. Ueber die Verbindungen des Phosphors mit den Wasserstoffe und den Metallen. Ann. d. Phys. (Pogg), 9, 39. Berzelius Jsb., 8, 174. Ann. des Mines, (2) 3, 146. Made BeCl 2 anhydrous for the first time. Passed chlorine over a heated mixture of the oxide and carbon and sublimed the product. Made beryllium phosphite by precipitating BeCl 2 with a saturated solution of PC1 8 in NH 4 OH. 1828; i. Rose, H. Ueber die unter Phosphorichtsauren Salze. Ann. der Phys. (Pogg), 12, 86. By saturating the acid with beryllium hydroxide ob- tained only a non-crystallizable gummy mass. BIBLIOGRAPHY OF BERYLLIUM 77 1828; 2. Wohler, F. Ueber das Beryllium und Yttrium. Ann. d. Phys. (Pogg), 13, 577- Berzelius Jsb., 9, 96. Mag. fur Pharm., 26, 257. Ann. des Mines, (2) 5, 133. Ann. chim. phys., (2) 39, 77. Reduced sublimed BeCl 2 with potassium in platinum crucible and for the first time obtained metallic beryl- lium as a dark grey powder. Gives following proper- ties, not all of which are sustained by later investiga- tors : Burns in air and oxygen to BeO when heated on platinum. Dissolves in concentrated H 2 SO 4 , yielding SO 2 . Dissolves in dilute H 2 SO 4 , HC1 and KOH, giv- ing off hydrogen. Dissolves in dilute HNO 3 giving off nitric oxide. Not affected by NH 4 OH. Burns in chlorine and bromine to BeCl 2 and BeBr 2 , both easily volatile and soluble with evolution of much heat. Burns in iodine gas and sublimes as BeI 2 with properties sim- ilar to BeCl 2 and BeBr 2 . BeS, made by heating in sul- phur vapor is a grey infusible mass difficultly soluble in H 2 O which yields H 2 S with acids. BeSe, made by heating in melted Se is fusible, but difficultly soluble. BeTe, a grey powder. Made beryl- lium phosphide by heating with phosphorous and beryl- lium arsenide by fusing with arsenic. 1828; 3. Bussy. Preparation du glucinium. Read at Acad. Roy. de Medic, Aug. 16, 1828. J. chim. medicale, 4, 453. J. fur Chem. (Schweigger), 54, 241. Berzelius Jsb., 9, 97. J. de pharm., 1828, 486. Polyt. J. (Dingier), 29, 466. Prepared beryllium almost simultaneously with Woh- ler and by the same method. Obtained an impure pro- duct, but did not study its properties extensively. 1828; 4. v. Bonsdorff, P. A. Beitrage sur Beantwortung der Frage ob Chlor, Jod und mehrere andere Metalloide, 78 CHEMISTRY OF BERYLLIUM saueren und basenbilden Korper wie der Sauestoffe sind. Kongl. Vet. Acad. Handl., 1828, 174. Ann. d. Phys. (Pogg), 17, 136. Made a double chloride of mercury and beryllium in rhombic prisms, but gives no analysis or formula. 1831 ; i. Berthemot. Beitrage sur Geschicte der Bromure. Archiv. der Pharm., 37, 332. J. de pharm., 26, 649. Made bromide by dissolving BeO in HBr, but could not crystallize. 1831 ; 2. Becquerel, A. C. Considerations generates sur les Decomposition electro-chimique et la Reduction de 1'oxide de fer, de la zircon et de la magnesie, a 1'aid de forces electrique pen energiques. Ann. chim. et phys., 48, 350. Pharm. CentrbL, 1832, 527. Thought he reduced by the current BeCl 2 which was impure with iron, but could not reduce pure BeCl 2 . 1831 ; 3. Berzelius, J. J. Ueber das Vanadin und seine Eig- enschatten. Ann. der Phys. (Pogg), 22, 58. Obtained a yellow, neutral, difficultly soluble, pow- dered beryllium vanadate. 1832; i. v. Kobell, Fr. Vermuthung iiber die Zusammenset- zung der Beryllerde. J. fur Chem. (Schweigger), 64, 191. J. prakt. Chem., i, 92. Claims that while CaCO 3 will precipitate the sesquiox- ides in the cold, it will not throw down manganese, zinc, iron or beryllium, but that beryllium is thrown out when the solution is heated near to boiling. Therefore, beryllium is bivalent. BIBLIOGRAPHY OP BERYLLIUM 79 1833; ! Trommsdorff, J. B. Ueber die Valeriansaure und ihre Verbindungen Valeriansaure Beryllerde. Ann. der Chem. (Liebig), 6, 194. Ann. der Phys. (Pogg), 29, 159. Pharm. Centrbl., 1832, 310. Beryllium valerianate, made by dissolving carbonate in acid, dries to a sweet, gummy mass, unchangeable in air. (See Lacombe, 1902). 1833; 2. Berzelius, J. J. Untersuchung iiber die Eigenschaft- en des Tellurs. Kongl. Vet. Acad. Handl., 1833. Ann. der Phys. (Pogg), 32, 594, 607. Neutral beryllium tellurates and tellurites were precip- itated by potassium tellurate or tellurite as white volu- minous flakes. 1834; i. Balard, A. G. Ueber Verbindungen des Broms mit Sauerstoff. J. prakt. Chem., 4, 165. Pharm. Centrbl., 1835, 349. Bibl. Univ., 1834, 372. Claims that bromine water partly dissolves BeO and that light has an apparent influence on the reaction. 1834; 2. Berzelius, J. J. Ueber die Destinations products der Traubensaiire. Kongl. Vet. Acad. Handl., 1834. Ann. der Phys. (Pogg), 36, 17. . Pharm. Centrbl., 1836, 41. 1837. i. Heller, J. F. Rhodizonsaiire, eine neue Oxidations stufe des Kohlenstoffes und die Krokonsaiire. J. prakt. Chem., 12, 227, 237. Pharm. Centrbl., 1837, 828, 833. Berzelius Jsb., 18, 521. Beryllium rhodonate, Be(H 2 C 3 O 5 ), is a brown pow- der and was made by boiling an alcoholic solution of the acid with beryllium acetate. Beryllium krokonate, Be(HC 5 O 4 ), formed in yellow crystals was made same as preceding. 80 CHEMISTRY OF BERYLLIUM 1858; I. Biot. J. B. Des combinations fluides formes par 1'acide tartrique, la glucine et Teau. Comptes. rend., 6, 158. Used a tartrate of beryllium made by Berthier and found specific rotary power 100 millimeters to be + 41.134 to +43.992, largest of any tartrate tried (see 1899; 13). 1840; I. Gmelin, L. New Methode die Beryllerde von der Thonerde zu trennen. Ann. der Phys. (Pogg), 50, 175-181. Pharm. Centrbl., 2, 427. Berzelius Jsb., 21, 141. Ann. der Chem., 36, 207. Ann. des mines, (4) 2, 70. Chem. Gaz., i, 9. Separates iron, beryllium and aluminum as follows: The nearly neutral HC1 solution is precipitated by cold KOH and digested in excess until the separated Fe- (OH) 3 has a clear brown color. The fluid is then di- luted with water and boiled fifteen minutes. All beryl- lium separates out carrying some iron. Aluminum is determined in filtrate. Beryllium precipitate is ignited, dissolved and retreated to remove iron. 1840; 2. Schaffgotsch, F. Beitrage zur Kenntniss der Beryl- lerde. Ann. der Phys. (Pogg), 50, 183-188. Pharm. Centrbl., 2, 438. Berzelius Jsb., 21, 95, 127, 141. Ann. der Chem., 36, 206. Ann. des mines, (4) 2, 170. J. prakt. Chem., (i) 20, 376. Phil. Mag., (3) 21, 284. Chem. Gaz., i, 9. Analyzed the hydroxides and gives them with very doubtful amounts of H 2 O. The carbonate precipitated from ammonium carbonate solution and dried at 100 gave 47.53 per cent. BeO, 17.57 per cent. CO 2 , 34.90 BIBLIOGRAPHY OF BERYIJJUM 8l per cent. H 2 O (by dif.). Shows some relations of Be(OH) 2 to KOH as Gmelin (1840; i) and may have priority. KOH must be neither too strong nor too weak. Says precipitate when well washed with .H 2 O is again soluble in KOH. 1840, 3. Scheerer, T. Untersuchung des Allanit, Orthit, Cer- in und Gadolinit. Ann. der Phys. (Pogg), 51, 472. Was unable to obtain good results by method of Gme- lin and of Schaffgotsch. 1842; i. Rose, H. Die Zusammensetzung der Beryllerde. Berichte der Akad. der Wis. (Berlin), 1842, 138-141. J. prakt. Chem., 27, 120. Berzelius Jsb., 22, 102. Preliminary announcement and discussion of the re- sults of Awdejew which were obtained under his direc- tion. 1842; 2. Awdejew, v. Ueber das Beryllium und dessen Ver- bindungen. Ann. der Phys. (Pogg), 56, 100-124. Centrbl., 13, 627. Berzelius Jsb., 23, 112 and 185. Ann. d. Chem. (L,iebig), 44, 269. Ann. de chim. et phys., (3) 7, 155-173. Phil. Mag., (3) 21, 284. Berg u. Hut. Ztg., i, 830. Chem. Gaz., i, 9. An extended and valuable research. Found the con- ditions for the preparation of BeSO 4 4H 2 O, purified it and correctly described its composition. Was the first to determine the atomic weight with even approximate accuracy. Determined atomic weight by analysis of sulphate. Was unsuccessful with chloride on account of its decomposition by water. Discusses the question of the valency of Be and came to the conclusion that it was a diad mainly from a study of the double salts of beryllium and potassium. Made the double fluoride 82 CHEMISTRY OF BERYLUUM 2KF.BeF 2 . Gave the symbol BeCl 2 to the chloride and thought he made BeCl 2 -{-4H 2 O by evaporation in vacuo which is undoubtedly a mistake. 1842; 3. Scheerer Th. Erste Fortsetzung der Untersuchung- en iiber Gadolinit, Allanit und damit verwandte Min- eralien. Ann. der Phys. (Fogg), 56, 479. J. prakt Chem., 27, 76 and 80. Centrbl., 1843, 208. Berzelius Jsb., 23, 293. Chem. Gaz., i, 177. Arch de pharm., 29, 214. Read at Stockholm, July 15, 1842. Separation of beryllium from iron. Uses ammonium sulphide to separate the small amount of iron dissolved by ammonium carbonate. First to propose this sepa- ration. Did not obtain good results by Schaffgotsch method of separation. 1843; i- R se > H. Ueber die Ytterde. Ber. der Akad. der Wiss. Berlin, 1843, 143. Ann. der Phys. (Pogg), 56, 105. Separates beryllium from yttrium by volatility of the chloride on treating heated oxides mixed with carbon and with chlorine gas. The residue had to be dissolved in acid precipitated by ammonia and three times ig- nited with carbon and chlorine to remove all the vola- tile chlorides, but these chlorides contained no yttrium. 1843; 2 - Berthier, P. Sur quelques separations operees au moyen de 1'acide sulfureaux en des sulfites alcaline. Ann. de chim. et de phys., (3) 7, 74. Ann. der Chem. (Liebig), 46, 182. J. prakt. Chem., (i), 29, 68. Centrbl., 1843, 37 8 - Separates ben-Ilium from aluminum, cerium and yttri- um after removal of most of the aluminum, as alum, by means of ammonium sulphite and boiling until no BIBLIOGRAPHY OF BERYLLIUM 83 more SO, comes off. Aluminum, cerium and yttrium are precipitated, but beryllium remains dissolved. 1843; 3- Damour, A. Nouvelles analyses sur le cymophane de Haddam. Ann. de chim. et de phys., (3) 7, 173. Centrbl., 1843, 783- Discusses the formulas BeO and Be 2 O 3 as applied to cymophane from basis of Awde Jew's work. 1844; J - Bottinger, Heinrich. Ueber die von Berthier vorge- schlagene Anwendung der schwefligen Saure in der chemischen Analyse. Ann. der Chem. (Liebig), 51, 397. Attempted to make quantitative separation of beryllium and aluminum by Berthier's method with sulphurous acid, but invariably found beryllium present with his aluminum. 1845; l - Riess, P. Ueber das elektrische Leitungsvermogen eineger stoffe. Ann. der Phys. (Pogg), 64, 53. 1847; I - Peroz, J. Note sur les pyrophosphates doubles. Ann. de chim. et de phys., (3) 20, 326. Simply states that he made compounds of the alkaline pyrophosphates with beryllium pyrophosphate. No de- tails. 1848; i. Play fair, Lyon andn Joule, J. P. Researches on Atom- ic Voflume and Specific Gravity. J. Chem. Soc. (London), 3, 93. Discussion of relation of atomic volume to specific gravity. No new results. 1848; 2. Rose, Heinrich. Ueber das Specifische Gewichte der Thonerde, der Beryllerde, der Magnesia und des Eisenoxyds. Ber. der. Akad. d. Wiss. (Berlin), 1848, 165-170. Centrbl., 1848, 485. Ann. der Phys. (Pogg), 74, 433- Jsb. Chem., i, 398. 84 CHEMISTRY OF BERYUJUM J. prakt. Chem., 44, 226. llnst. (Paris), 1848, 368. Ann. der. Chem. u. Pharm. (Liebig), 68, 167. Beryllium oxide made by heating the basic carbonate over an alcohol lamp showed specific gravity =3. 083- 3.09. By heating to very high temperatures in por- celain oven became six-sided crystals and specific grav- ityr=3.o2i. By heat hydroxide precipitated by ammo- nia, specific gravity = 3. 096. Same to much higher temperature, specific gravity =3. 027. 1848; 3. Rose, Heinrich. Ueber die Anwendung des Salmi- akes in der Analytische Chemie. Ber. der. Akad. der Wiss. (Berlin), 1848, 202. Centrbl., (1848) 19, 602. J. prakt. Chem., 45, 116. Ann. der. Phys. (Pogg), 83, 145. Beryllium carbonate, oxide, etc., are only partly de- composed by heating with ammonium chloride. 1850; i. Rivot, L. E. De Temploe de 1'hydrogene dans les analyses des substances minerales. Ann. de chim. et de phys., (3) 30, 188. Ann. Chem. u. Pharm. (Liebig), 78, 212. J. prakt. Chem., 51, 338. Centrbl., 1850, 908. Jsb. Chem., 3, 599. Chem. Gaz., 9, 76. Separates iron oxide from beryllium oxide by igniting in hydrogen and dissolving out iron in dilute nitric acid (1-30) or determines per cent, of iron from loss on ignition in hydrogen. 1851 ; i. Ebelmen, J. J. Recherches sur la cristallization par voie seche. Comptes rend., 33, 526. Ann. Chem. (Liebig), 80, 211. Crystallized beryllium oxide from an alkali silicate and obtained six-sided prisms with a density of 3.058. Hard enough to scratch glass, insoluble in acids, although BIBLIOGRAPHY OF BERYLLIUM 85 slightly in hot concentrated H 2 SO 4 . Easily soluble in HKSO 4 . Claims perfectly isomorphous with crystals of A1 2 O 3 . 1851; 2. Ebelmen, J. J. Ueber die Krystallization auf trock- nem Wege. J. prakt. Chem., 55, 342. Centrbl., 1851, 529, 899. Jsb. Chem., 4, 15. 1'Inst. (Paris), 1851, 179, 369. Same as 1851; i, but separately transmitted by author. 1851; 3. Ebelmen, J. J. Sur une nouvelle methode pour ob- tenir des combinaisons cristallisees par la voie seche (sur la cymophane). Ann. de chim. et de phys., (3) 33, 40. Made cymophane artificially by fusing together A1 2 - O 3 , BeO and B 2 O 3 . 1853; i. Fremy, E. Recherches sur les sulfures decompos- ables par Teau; suive de considerations generates sur la production des eaux sulfureuses et siliceuses. Comptes rend., 36, 178. Centrbl., 1853, 113- Says sulphide of beryllium was the only sulphide he could not make by passing CS 2 over hot base. 1853; 2. Miiller, EL Mineralanalysen. J. prakt. Chem., 58, 181. Several analyses of beryl with methods used but em- bodying nothing new. 1854; i. Weeren, Julius. Einige Beitrage zur Kenntniss der Beryllerde. Ann. der Phys. (Pogg), 92, 91-128. J. prakt. Chem., 62, 301. Ann. Chem. (Liebig), 92, 262. Centrbl., 1854, 705. Jsb. Chem., 7, 336 and 728. Chem. Gaz., 12, 408. Amer. J. Sci., (2), 18, 414. An extended and careful research on beryllium. De- 86 CHEMISTRY OF BERYLLIUM termined atomic weight by ratio BeO : SO 3 in care- fully purified sulphate. Compared different methods of preparation. Considered methods by use of (NH 4 ) 2 - CO 3 and by NH 4 C1 best. Gives special precautions for latter. Studied Be(OH) 2 critically and gives properties. Studied carbonates and found no definite composition, but varying proportions of carbonate and hydroxide according to treatment. Gives formulas for some of these as obtained, all showing a high ratio of base to acid. Found the sulphate lost one third of its water of crys- tallization at 35 C. 1854; 2. Debray, Henri. Du glucyum et de ses composes. Academic Dissertation, Paris. Comptes rend., 38, 784. CentrbL, 1854, 44& Jsb. Chem., 7, 336. J. prakt. Chem., 62, 180. Ann. Chim., (Liebig), 92, 261. Chem. Gaz., 12, 204; 13, 386. Chemist, I, 558. Arch, ph. nat, 26, 181. rinstitute, (Paris), 1854- 142. Arch, der Pharm., 142, 44. First announcement to French academy of results much more fully described in 1855; i. 1855; * Debray, Henri. Du glucinum et de ses composes. Academic Dissertation, Paris, 1855. Ann de. chim. et de phys., (3), 44, 1-41. CentrbL, 1855, 549- Jsb. Chem, 8, 356. Chem. Gaz., 13, 386. J. Chem. Soc., ( London), 8, 242. Extended research. Made beryllium by reduction of chloride by sodium as a white metal, specific gravity 2.1. and describes properties. Could not make the sulphide BIBLIOGRAPHY OF BERYLLIUM 87 as Wohler did. Made and .described BeO, BeCl 2 , BeI 2 , BeF 2 .KF, BeSO 4 .4H 2 O, K 2 SO.BeSO 4 .2H 2 O. Made rather indefinite basic carbonates, obtaining quantities equivalent to 2Be(OH) 2 .BeCO 3 .3H 2 O as one of his products. Also made double carbonates with ammo- nium and potassium. Could not make crystalline oxal- ates but easily prepared the double oxalates, BeC 2 O 4 . K 2 C 2 O 4 , and BeC 2 O 4 .(NH 4 ) 2 C 2 O 4 . Studied the prop- erties of the hydrate, (Be(OH) 2 . Decomposed his beryl by fusing with lime. Gives a new method of separation from aluminum by the action of zinc on mixed sulphates, hydrogen being evolved, and the alu- minum precipitated as a basic sulphate. Favored bi- valency of beryllium. 1855 > 2. Rose, Heinrich. Ueber des Verhalten der verschie- denen Basen gegen Losungen amoniacalischer Salze und namentlich gegen die Losung von chlorammonium. Ber. Akad. d. Wiss. (Berlin), 1855, 334- Centrbl., 1855, 612. Found that beryllium oxide could decompose solutions of ammonium chloride but lost this property when very strongly heated. This property belongs to bases RO and not R 2 O 3 . 1855 ; 3. Rose, Heinrich. Ueber die atomische Zusammen- setzung der Beryllerde. Ber. Akad. d. Wiss. (Berlin), 1855, 581. Ann. der Phys. (Pogg), 96, 445. J. prakt. Chem., 64, 182. Centrbl., 1855, 73, 733- Jsb. Chem., 8, 361. 1'Insntitute (Paris), 1856, in. Chem. Gaz., 13, 466. Discussion of previous work, (1848; 2) and concludes that from atomic volume considerations, constitution of oxide must be R 2 O 3 in spite of results with ammo- nium chloride (1855; 4). 88 CHEMISTRY OF BERYLLIUM 1857; i. Lewy, B. Recherches sur la formation et la com- position des emeraudes. Cmptes rend., 45, 877. Concluded color of emerald was due to organic mat- ter and not to chromium. 1858; i. Ordway, John M. Examination of soluble basic sesqui salts. Amer. J. of Sci., (2) 26, 197. J. prakt. Chem., 76, 22. Jsb. Chem., n, 114. Discusses the formation of the nitrate but finds it very difficult to crystallize. Made basic compounds by drying solution of nitrate. 1858 ; 2. Lea, M. Carey. On picric acid and some of its salts. Amer. J. of Sci., (2) 26, 382. Centrbl., 1859, I2I Carbonate of beryllium dissolves readily in hot aqueous picric acid and by evaporation yields golden yellow crystalline crusts. 1858; 3. Deville, St. Claire and Caron, H. Sur. un nuveau mode de production a 1'etat cristallise d'une certain nomber d'especes chimiques et mineralogiques. Comptes rend., 46, 765 . Chemist, (3) 5, 5H- Fused equal equivalents of fluorides of aluminum and beryllium under high heat in boric acid. 1859; l - Hofmeister. Uber die Trennung der Beryllerde von der Alaunerde, nebst der Analyse szweier Beryll. J. prakt. Chem., 76, i. Rep. chem. pure, i, 301. Jsb. Chem., 12, 675. Archiv. der Pharm., 101, 177. Used ammonium carbonate method and proposed a number of fractional precipitations to remove all alumi- num. BIBLIOGRAPHY OP B^RYUJUM 89 1859; 2. Ordway, John M. Some facts respecting the nitrates. Amer. Jour. Sci., (2) 57, 18. J. prakt. Chem., 76, 22. Solid nitrate of beryllium melts as low as 140 F., and may be cooled as low as 85 F., before it begins to solidify. Boiled as low as 285F., continuing to boil and remaining clear to 320 F., giving off acid all the time. The highly basic residue did not solidify on cooling to 6iF., on adding strong nitric acid solidified and temperature rose to 142 F. Dilution with a "basic salt'' has therefore same effect as dilution with H 2 O. 1859; 3. Scheffer, G. Beitrage zur Kenntniss der Beryllerde. Ann. Chem. (Liebig), 109, 144. J. prakt. Chem., 77, 79. N. arch. ph. nat., 5, 180. Ann. chim. et phys., (3) 56, 112. Rep. chim. pur., i, 317. Archiv. der Pharm., 33, 144. Jsb. Chem., 12, 139. Le Moniteur scientifique, 2, 862. Phil. Mag., (4) 18, 455- Scheffer claims to have decomposed his beryl by heat- ing in a lead dish at 100-200 with CaF 2 and concen- trated H 2 SO 4 . Made an acid phosphate, BeHPO 4 . 3H 2 O which on drying yielded BeHPO 4 .H 2 O and a gummy phosphate, 5BeO.2P 2 O 5 + 8H 2 O which on di- lution with water yielded a white precipitate, 2BeO. Pa^5+5H 2 O. These results are interesting as -they are quite analogous to the basic sulphate action while in reality they are acid compounds if phosphoric acid is tribasic. Claimed to make a nitrate by evaporating BeO and HNO 3 to dryness at I2O-I5O. Claimed it then lost no H 2 O or N 2 O 5 (which is not true of any nitrate of beryllium. Obtained first class results by Debray's method of separation with zinc. By precip- itating basic beryllium nitrate with Na 4 P 2 O 7 obtained a pulverulent precipitate, the analysis of which would 9O CHEMISTRY OF BERYUJUM yield the formula, Be 2 P 2 O 7 .5H 2 O. Made a triple salt, BeNa 2 (NH 4 ) 2 (PO 4 ) 2 7H 2 O by adding NH 4 C1 be- fore precipitating with sodium phosphate. 1860; i. Cahours, Aug. Recherches sur les radicaux organo- metallique, "Glucinium ethyl." Ann. chim. et phys., (3) 58, 22. Made beryllium ethyl by action of metallic beryllium on C 2 H 5 1 in sealed tube. Appeared analogous to alu- minum ethyl, but did not have enough to study. 1861 ; i. Frankland, E. On organo-metallic bodies. J. Chem. Soc. (London), 13, 181, 194. Discusses briefly conclusions of Cahours (1860; i) on beryllium ethyl. 1862; i. Parkman, Theodore. On the carbonates of Alumina, Glucina and the sesquioxides of Iron, Chromium and Uranium. Amer. J. of Sci., (2) 34, 326. Centrbl., 1863, 465, 468. Chem. News, 7, 122. By precipitating BeSO 4 with Na 2 CO 3 in slight excess he obtained a basic carbonate containing the approxi- mate ratio of 3BeO :iCO 2 . 1863; i. Joy, Charles A. On Glucinum and its Compounds. Amer. J. of Sci., (2) 36, 83. Chem. News, 8, 183-197. J. prakt. Chem., 92, 232. Jsb. Chem., 16, 676. Centrbl., 1864, 1119. Bull. soc. chim., (2) 2, 351. An extended and excellent study of the methods of de- composing beryl and separating beryllium from alu- minum including an extended bibliography of the sub- ject and of the minerals containing beryllium. Tried the following methods of decomposing beryl : i. By passing chlorine over calcined beryl, oil and lamp-black in hot porcelain tube. Chloride of iron, alu- minum and beryllium volatilized together. BIBLIOGRAPHY O* BERYLLIUM 9! 2. By treating beryl with concentrated HF and H 2 SO 4 . Claimed to succeed if beryl was very finely pulverized. 3. By digesting seven parts beryl, 13 parts CaF 2 in 18 parts H 2 SO 4 . Decomposed but large amount of cal- cium compounds proved a great disadvantage. 4. By fusing beryl with three parts of KF and digest- ing with H 2 SO 4 . Fine method except for cost of KF. SiF 4 is driven off at low heat. 5. By NH 4 P\ ditto. 6. By digesting in H 2 SO 4 and fusing with potassium ferrocyanide and salt. Complete failure. 7. By fusing with CaF 2 . Attacked crucible badly and large amount of calcium compounds caused complica- tions. 8. By fusing two parts beryl with one part CaO in Hessian crucible. Attacked crucible, but claimed de- cided advantages if suitable crucible could be found. 9. By fusing with litharge. Not so good as with K 2 C0 3 . 10. By fusing with MnO 2 . Decomposed but no advan- tage. 11. By fusing a mixture of two parts Na 2 CO 3 and three parts K 2 CO 3 . Worked well, but preferred the follow- ing. 12. By fusing one part beryl with two parts K 2 CO 3 . Preferred this method to any of the others. Fused mass decomposed with H 2 SO 4 , evaporated to get rid of silica, crystallized out alum, etc. Joy also tried the following for separating beryllium from aluminum : 1. By NH 4 C1. Precipitated by NH 4 OH and digested in concentrated solution of NH 4 C1 with addition of evaporated water. Iron and aluminum remain insol- uble and beryllium goes into solution. Tedious, but accurate. 2. By carbonate of ammonium. Some aluminum al- so goes into solution, although it does not when alone. 92 CHEMISTRY OF BERYUJUM 3. By caustic potash. Mixed solution in HC1 is pre- cipitated with KOH which is gradually added in ex- cess until precipitate dissolves, then diluted with 10 volumes of water and boiled. Beryllium precipitates partially and fairly free from aluminum and iron, but much loss of beryllium. 4. By sulphurous acid. Did not succeed as some ber- yllium was always thrown down with the basic sul- phite of aluminum. 5. By BaCO.,. Both precipitated. 6. By Na 2 S 2 O 3 . Both precipitated. 7. By decomposing the nitrates heated to 200 to 250. Both acted the same. 8. By acetate of soda. Beryllium, aluminum and iron act the same. 9. By fusion with KOH. Act alike. 10. By ammonium formate. Act alike. 11. By decomposition of sulphates. Act alike. 12. By formation of alum. Considers this best. 1864; I- Wohler, F., and Rose, G. Sur la nature colorante des emeraudes. Comptes rend., 58, 1180. Chem. News, 10, 22. Deny coloring matter of emerald due to organic mat- ter and heated to prove. Imitate color in glass by a small amount of chromium. 1864; 2 - Gibbs, Wolcott. On the quantitative separation of cerium from yttrium, aluminum, glucinum, manganese, iron and uranium. Amer. Jour, of Sci., (2) 37, 354- J. prakt. Chem., 94, 121. Chem. News, 10, 195. Ztschr. f. Chem., 1865, 15. Separates beryllium from cerium group by its solubil- ity in saturated sodium sulphate ; from yttrium group by oxalate of ammonia. BIBLIOGRAPHY Otf BERYLLIUM 93 1864; 3. Gibbs, Wolcott. On the employment of fluohydrate of fluoride of potassium in analysis. Amer. J. of Sci., (2) 37, 356. CentrbL, 1864, 990. Jsb. Chem., 17, 684. J. prakt. Chem., 94, 121. Ztschr. f. Chem., 1865, 16. Chem. News, 10, 37 and 39. Bull. soc. chim., (2) 4, 359. States that fusing crude BeO with HF. KF and treat- ing the fused mass with boiling water and slight amount of HF and recrystallization is the best known (1864) method of producing a chemically pure salt of beryl- lium. Under these conditionss the aluminum is sepa- rated as the very insoluble A1F 3 ;3KF. Also states that NaF precipitates the aluminum probably quantitative- ly from a mixture of the fluorides of aluminum and beryllium. 1864; 4. Gibbs, Wolcott. Beitrage zur Chemie aus dem Lab- oratorium der Lawrence Scientific School. Ztschr. anal. Chem., 3, 397, 399. Same as 1864, 2 and 3. 1865; i. Delafontaine, Marc. Metals in Gadolinite. Chem. News, u, 159. Archiv. d. sci. phys. and nat. Geneva, 97, 101. 1866; i. Cooke, J. P. On Danalite, a New Mineral Species from the Granite of Rockland, Mass. Amer. J. Sci., (2) 42, 78. Ztschr. anal. Chem., 6, 226. Gives method of analysis and discusses method of St. Clair Deville (Annales., 38). Says it is one of the most accurate in analytical chemistry. Separates beryllium from iron by reducing iron in platinum tube in a cur- rent of hydrogen and then volatilizing in a current of HC1. Aluminum and beryllium not effected. See 1850, Rivot. 94 CHEMISTRY OF BERYLLIUM 1866; 2. Hermes, O. Beitrage zur Kenntniss der Schweifel- cyan verbindungen. J. prakt. Chem., 97, 475. CentrbL, 1867, 112. Made Be(CyS) 2 by action of H(CyS) on carbonate. Soluble in alcohol. Salt poorly defined and doubtful. 1867; i. Debray, H. Report to the Societe chimique de Paris on beryllium on exhibition at the Paris Exposition. Bull. soc. chim., (2) 7, 465. Simple statement (no details) that Debray reported on metallic beryllium exhibited at the Paris exposition, which was manufactured by M. Menier by heating with sodium, a mixture of BeCl 2 and the double fluorides of beryllium and potassium in a crucible of pure alum- inum. 1869; I. Klatzo, Georg. Die Constitution der Beryllerde. Academic Dissertation, Dorpat. Ztschr. f. Chem., 12, 129. Centrbl., 1869, 832. Bull. soc. chim., (2) 12, 131. N. arch. phys. nat, 34, 354. Jsb. Chem., 12, 203; 13, 256. J. prakt. Chem., 106, 227-244. Tids. for Phys. og. Chem., 8, 167. Ztschr. anal. Chem., 8, 202 and 523. Chem. News, 19, 227. J. Frank. Inst., 89, 260. An extended article full of erroneous work as shown by Marignac and others. Studied sulphates and claimed to make a new sulphate, BeSO 4 .7H.,O. By saturating the basic carbonate with CO 2 in water and evaporating in an atmosphere of CO 2 , he claimed to obtain crystals of BeCO 3 4H 2 O which formed double salts with alkaline carbonates. By precipitating ammonium carbonate solution with al- cohol, claimed to make the compound 3BeCO 3 .BeO, BIBLIOGRAPHY OF BERYLLIUM 95 H 2 O+3(NH 4 ) 2 CO 8 . Made a basic carbonate of for- mula similar, to that obtained by Debray. Determined the atomic weight by ignition of sulphate. Studied the chloride and fluoride. 1869; 2. Thalen, Rob. Memoire sur la determination des lonqueurs d'onde des raies metalliques. Nova Acta Reg. Soc. Sc. Upsal. (3) vol. 6. Ann. chim. et phys., (4) 18, 228. Found the wave length of the bright rays of the Beryl- lium spectra to be 4572 in the blue and 4488.5 in the indigo. 1870; i. Thomsen, Julius. Ueber Berylliumplatinchlorid. Berichte, 1870, 827. Centrbl., 1870, 690. Jsb. Chem., 1870, 318. J. Chem. Soc. (London), 24, 202. Bull. soc. chim., (2) 15, 50. Ztschr. f. Chem., 14, 46. Chem. News, 22, 263. J. Applied Chem., 5, 185. Made BePtCl 6 .8H 2 O. 1871; i. Thomsen, J. Die Warmeentwickelung der Neutra- lization. Ann. der Phys. (Pogg), 143, 497. Berichte, 4 (1871), 586. Bull. soc. chim., (2) 16, 63. Jsb. Chem., 1871, 102. Determined among many others, the heat of neutraliza- tion of Be (OH) 2 with sulphuric and hydrochloric acid. Found Be(OH) 2 + H 2 SO 4 +Aq= 16100, Be(OH) 2 + 2HCl-}-Aq=: 13640. 1871 ; 2. Toczyknski, F. Ueber die Platincyanide und Tar- trate des Beryllium. Ztschr. f. Chem., 15, 275.. Inaugural Dissertation, Dorpat, 1871. Bull. soc. chim., (2) 16, 254. Centrbl., 1871, 564; 1872, 517. Jsb. Chem., 1871, 286, 359. 96 CHEMISTRY OF BERYUJUM Pharm. Ztschr. f. Russl., n, 166, 204. J. Chem. Soc. (Lon.), 24, 1013. Chem. News, 24, 158. Made green ferrocyanide of Beryllium by precipitating barium salt with BeSO 4 . Made ferricyanide by oxidiz- ing ferrocyanide with Cl, olive green. Could not separate the sulphocyanate and nitroprusside. Made BePtCy 4 +4H 2 O by precipitating barium salt in crystals, changing on heating through gold, yellow, orange red. Made BeMg 2 Pt 3 Cy 12 .i6H 2 O by crystallizing the two cyanides together. Made several very complicated and basic double tar- trates to which he gave formulas. 1872; i. Topsoe, Haldor. Krystallographische-chemische Un- tersuchungen. Stizber. d. k. Akad. Wiss. Wein, 66, II, 5. Jsb. Chem., 1872, 163. N. arch. sci. phys. nat., 45, (1872), 76. BeSO 4 4H 2 O, tetragonal a : c = 1 10.9461 . Observed form (on). (no) uniaxial, negative, specific gravity 1725- BeSeO 4 .4H 2 O, at 100 loses two molecules H 2 O, spe- cific gravity 2.029. Rhombohedral, a :b :c=i 10.9602: 0.90275. Observed forms (oil).(lOl).(O2l).(lIl). (ooi). Also made isomorphous mixtures of the sulphate and selenate and studied crystals of same. 1873; i. Cahours, A. Recherches sur de nouveaux derives du propyle. Comptes rend., 76, 1383. Centrbl., 1873, 482. Jsb. Chem., 1873, 520. Berichte, 6, 821. J. Chem. Soc. (London), 26, 871. J. Russ. Phys. and Chem. Soc., 5, 274. Made beryllium propyl by acting on mercury propyl at BIBLIOGRAPHY OF BE)RYIJJUM 97 130-135 in sealed tube. Beryllium propyl was dis- tilled in atmosphere of CO 2 to a colorless liquid boil- ing at 244-246. Fumes in air and is spontaneously combustible. Thick oil at 17. Decomposed by H 2 O. Also confirms earlier experiments 1860; i on beryllium ethyl and prepared same in like manner to above with boiling point 185-188 and properties similar. 1873; 2. Marignac, C. de. Notices chimiques et cristallogra- phiques sur quelques sels de glucine et des metaux de la cerite. N. arch. d. sci. phys. nat., 46, 193. Ann. chim. et phys., (4) 30, 45-69. Jsb. Chem., 1873, 259. Chem. News, 28, 45. J. Chem. Soc. (London), 27, 24. J. Russ. Phys. and Chem. Soc., 5, II, 303. Confirms Awdejew (1842; 2) 2KF.BeF 2 and made also KF.BeF 2 , 2NaF.BeF 2 , NaF.BeF 2 , 2NH 4 F.BeF 2 . Con- firms K 2 SO 4 .BeSO 4 .2H 2 O. Concluded that beryllium is not isomorphous with Al or Mg group. Gives forms of crystals and finds many differences from Klatzo, (1869; i). 1873; 3. Williams, C. Grenville. Researches on Emeralds and Beryls. I. On the coloring matter of the emerald, Phil. Mag., (4) 46, 314. Proc. Roy. Soc., 21, 409. Fused emeralds and beryls in oxyhydrogen blow-pipe and made artificial emeralds and beryls by simply fus- ing constituents together. Concluded coloring matter to be due to chromic oxide. 1873; 4. Thomsen, Julius. Untersuchung uber die Warmton- ung beim Auflosen verscheidener fester fliissiger und liiftformiger Korper in Wasser. Berichte, 6, 712. By dissolving one molecule BeSO 4 4H 2 O in 400 mole- cules of water, found heat of solution = -f- 1 100. 9 CHEMISTRY OF BERYLLIUM 1873; 5. Welkow, A. Beryllium Platinchloride. Berichte, 6, 1288. Centrbl., 1874, 50. Bull. soc. chim., (2) 21, 273. Amer. Chem., 4, 390. Jsb. Chem., 1873, 258. J. Chem. Soc. (London), 27, 229. Chem. News, 29, 51. Made BePtCl .8H 2 O, tetragonal, dark yellow crystals see Thomsen, 1870; i. 1873; 6. Topsoe, Haldor. Tabelle iiber die specifischen Gew- ichte, Moleculargewichte, und Molecularvolumen ver- schiedene Salze. Centrbl., 1873, 76. Contains summary of his work 1872; I and also calcu- lates molecular volume from data then given. 1873; 7. Atterberg, Albert. Undersokningar ofver Metallen Berylliums Foreningar. Kongl. Svenska Vetenskaps-Akademiens. Handlingar, 12, 1-38. Chem. Centrbl., 1874, 33O. Berichte, 7, 472. Atterberg especially calls attention to the tendency of beryllium to form substances of a highly basic nature and claims to have made the following compounds: Be(OH) 2 . 3 Be(OH) 2 .H 2 0, 3 Be(OH) 2 . 7 H 2 0. BeS0 4 .2H 2 0, BeSO 4 .4H 2 O, BeSO 4 .Be(OH) 2 .2H 2 O, BeSO 4 .2Be(OH) 2 .2H 2 O, BeSO 4 .7Be(OH) 2 .2H 2 O, BeK 2 (SO 4 ) 2 .2H 2 O, BeK 2 ( SO 4 ) 2 -f 2KHSO 4 +4H A 3BeSO 4 .2Na 2 SO 4 .i2H 2 O, BeS0 4 .(NH 4 ) 2 S0 4 .2H 2 0, BIBLIOGRAPHY Otf BERYUJUM 99 BeSe0 4 .4H 2 O, BeS0 3 .Be(OH) 2 .2H 2 O, BeSeO 3 .H 2 O, 2(BeSeO 3 .H 2 O).Be(OH) 2 , 2BeSeO 3 .Be(OH) 2 .5H 2 O, BeSeO 3 .Be(OH) 2 .H 2 O, BeSe0 3 .Be(OH) 2 .3H 2 O, BeCrO 4 .i3Be(OH) 2 +ioH 2 O, BeMoO 4 .Be(OH) 2 -f2H 2 O, BeMoO 4 .MoO 3 .H 2 O, 2BeCl 2 .3HgCl 2 .6H 2 O, BeC 4 H 4 O 4 .2H 2 O (succinate), BeC 4 H 4 O 4 .Be ( OH ) 2 .2H 2 O, BeCl 2 .4H 2 O, BeCl 2 .3Be(OH) 2 , BeCl 2 .i2Be(OH) 2 -f-ioH 2 O, BeCl 2 .SnCl 4 .8H 2 O. BeCl 2 .AuCl 3 , Be(C10 4 ) 2 . 4 H 2 0, Be 3 (10 4 ) 2 +iiH 2 0+i 3 H 2 0, Be 3 (P0 4 ),7H 2 0, BeC 2 O 4 .Be(OH) 2 .H 2 O, BeC 2 O 4 .6Be(OH) 2 .6H 2 O, BeC 4 H 4 6 . 3 H 2 0, Many of which, in fact, have no existence as definite compounds. 1873; 8. Atterberg, A. Faits pour servier a Thistoire der glucinium. Bull. soc. chim., 19, 497. Jsb. Chem., 1873, 257. Chem. Centrbl., 1873, 53O- J. Chem. Soc. (London), 26, 1003. J. Russ. Phys. and Chem. Soc., 5, II, 303. Separately transmitted, but contains nothing not in 1873 ; 7, except BeSO 4 .5Be(OH) 2 .2H 2 O. 9. Topsoe, H and Christiansen, C. Recherches optiques sur quelques series de substances isomorphes. TOO CHEMISTRY OF BERYLLIUM Ann. chim. et phys., (5) I, 5. Complete from Vidensky, Selsk., 1873, 9, 625. Ann. der Phys. (Pogg), Erganz-Bd., 6, 499. Chem. Centrbl., 1874, 258. BeSO 4 4H 2 O, optically negative. Tetragonal a :c=i 10.9461. Mean values indices of refraction. C =--1.4374 0=1.4691 e D= 1.4395 w D =1.4720 F = 1.4450 F =1.4779 BeSeO 4 4H 2 O, rhombohedral. a :b :c= i '.0.9602 -.0.9027. Mean indices. V-a P-b V* c 1.4992 1.4973 1.4639 D 1.5027 1.5007 1.4664 F 1.5101 1.5084 1.4725 1873; 10. Hoist, N. O. Bidrag till Kannedomen om Platinas Cyanforeningar. Ars-skrift. Univ. Lund., 10, II, No. 6. Bull. soc. chim., (2) 22, 349. Chem. Centrbl., 1874, 786. Benchte, 8, 125. Jsb. Chem., 1875, 238. Made the salt BePtBr 2 Cy 4 in crystals. 1874; I. Atterberg, Albert. Sur les combinaisons du glucinium. Bull. soc. chim., (2) 21, 157. Berichte, 7, 472. J. Chem. Soc. (London), 27, 658. Ztschr. anal. Chem., 13, 316. J. Russ. Chem. and Phys. Soc., 6, II, 84. Separately transmitted, but contains nothing not in 1873; 7- 1874; 2. Thomsen, J. Die Neutralizationswarme der oxyde des Lanthans, Ceriums, Didyms, Yttriums and Erbium. Berichte, 7, 33. Uses his previously obtained figures for Be(OH) 2 in discussion. 1874; 3. Welkow, A. Beryllium-Palladiumchlorid. Berichte, 7, 38. BIBLIOGRAPHY OF BERYLLIUM IOI Chcm. Centrbl., 1874, 5, 245. Jsb. Chem., 1874, 254. J. Chem. Soc. (London), 27, 443. Amer. Chem., 4, 469. Chem. News, 29, 155. Gaz. chim. ital., 4, 278. Bull. soc. chim., 2, (21) 273. Made BePdCl 6 +8H 2 O, dark red brown crystals, loses all of its water at 130. Isomorphous with BePd- C1 6 +8H 2 0. 1874; 4. Thomsen, J. Beryllium-Platinchlorid. Berichte, 7, 75. Chem. Centrbl., 1874, 245. Note to the effect that he had priority over Welkow and that Marignac had corrected his 9H 2 O to 8H 2 O which he found correct. 1874; 5. Welkow, A. Aluminum-Platinchlorid. Berichte, 7, 306. Bull. soc. chim., (2) 22, 153. Gaz. chim. ital., 4, 302. Chem. Centrbl., 1874, 292. States that his comparisons with the beryllium salt show no crystallographic resemblance and does not lead to placing Be in Al group. 1874; 6. Welkow, A. Beryllium- Palladiumchloriir. Berichte, 7, 803. Chem. Centrbl, 1874, 476. Jsb. Chem., 1874, 254. J. Chem. Soc. (London), 27, 1065. Amer. Chemist, 5, 264. Bull. soc. chim., (2), 22, 499. Gaz. chim. ital., 5, 61. By heating cone, solution of BePdCle-SH^O chlorine is evolved and BePdCl 4 .6H 2 O left in soluble, brown tabular crystals. Also obtained a double iodide of Be and Sb, and Be and Bi which were so unstable, he could not assign a satisfactory formula, but found no re- 102 CHEMISTRY OF BERYLUUM semblance to corresponding Al compound. Could not make double chlorides with alkali metals. 1875; I. Bunsen, R. W. Spectral Analytische Untersuchung. Ann. d. Phys. (Pogg), 155, 230, 366. Ztschr. anal. Chem., 15, 92. Short reference to spectra of Be. 1875; 2. Nilson, L,. F. Zur Frage iiber die Valenz der selten Erdmetalle. Berichte, 8, 655. Chem. Centrbl., 1875, 449. Claims to have made the following salts, 5BeO.2SeO 2 + ioH 2 O, BeSeO 3 .2H 2 O, BeSeO 3 H 2 SeO 3 , BeSeO 3 .2H 2 - SeO 3 , which, he says, indicate the BeO rather than Be 2 O 3 formula. 1875; 3. Nilson, L. F. Recherches sur les selenites. Nova Acta reg. Soc. Sci. Upsala 1875, transmitted by Cleve to Bull. soc. chim., (2), 23, 355. Same as 1875 ; 2, but separately transmitted and con- tains besides those enumerated there, 5Be0.8SeO 2 .5H 2 O, 3 Be0.7Se0 2 . 5 H 2 0. 1875; 4. Atterberg, A. Nagra Ytterligare bidrag till Kanne- domen om Beryllium foresingarna. Ofvrvsgt. Kongl. Vet. Akad. Forhand, 1875, No. 7, 32. Hull. soc. chim. (2), 24, 358. Chem. Centrbl, 1876, 35. Berichte, 9, 856. Jour. Chem. Soc. (London), 30, 382. Gaz. chim. ital., 6, 159. Communicated through M. Cleve, prepared BeCl 2 . 2( (C 2 H 5 ) 2 O). Claims that his previously given formula, 3BeCl 2 .2Be(OH) 2 , was incorrect and should be BeO.HCl. Also made BeHPO 4 .3H 2 O, Be 3 (PO 4 ) 2 . 6 or 7 H 2 O 4 Be 8 (AsO 4 ) 2 .6H 2 O, BeHAsO 4 .2H 2 O. BIBLIOGRAPHY OF BERYLLIUM IO3 1876; I. Nilson, L. F. Zur Frage iiber die Valenz der seltenen Erdmetalle. Berichte, 9, 1056, 1145. Jsb. Chem., 1876, 292. Bull. soc. chim. (2), 27, 206. J. Russ. Phys. and Chem Sec., 9, II, 98. Amer. Chemist, 7, 242. J. prakt. Chem., 15, 177. Discusses the work of others on BePtCl 6 .8H 2 O, and makes BePtCl 4 .5H 2 O. Again places Be in divalent metals. 1876; 2. Nilson, L. F. Untersuchung iiber Chlorosalze tmd Doppel nitrite des Platins. (Beryllium plato and di- platonitrite). Nov. Acta. Soc. Sci. Upsala (3) vol. extra, (1877), number 15. Ofvst. Akad. Handl. (Stockholm), 33, number 23. Berichte, 9, 1722. J. prakt. Chem. (2), 16, 264. Chem. Centrbl., 1878, 211. Chem. News, 34, 270; 37, 31. Jsb. Chem., 1876, 295, 1877, 31- Bull. soc. chim. (2), 27, 210, 245. Treated BeSO 4 4H,O with barium plato nitrite, filtered and evaporated in vacuum. Obtained Be(2NO 2 .Pt) 2 .- O.9H 2 O (diplatonitrite), but could not make the plato- nitrite. Makes BePtCl 4 +5H,O. 1876; 3. Reynolds, J. Emerson. On Glucinum, its atomic weight and specific heat. (Read April TO, 1876). Phil. Mag., (5) 3, 38-42. Bull. soc. chim., (2) 28, 161. Chem. Centrbl., 1877, 210. Chem. News, 35, 119. J. Chem. Soc. (London), 31, 579. Berichte, 9, 1806. J. Russ. Phys., and Chem. Soc., 9, II, 244. Reduced BeCl 2 , made from beryl, by Na in platinum crucible below fusion and determined specific heat com- 104 CHEMISTRY OF BERYIJJUM pared to siver in special calorimeter. Found specific heat = 0.642 at TOO, at. heat 5.91. Concluded at. wt. therefore to be 9.2. 1877; i. Williams, C. Grenville. Researches on Emeralds and Beryls. II. Chem. News, 35, 257. Analysis and study of separation of Be and Al. Noth- ing especially new. 1877; 2. Cossa and Pecile. Einwirkung von Fluormagnesium auf des sulphate des Aluminums und Berylliums. Berichte, 10, 1099. Formed fluoride of both metals. 1878; i. Smith, Edgar F. Beryll um borate. Proc. Amer. Chem. Soc., 2, 114. Found that if BeCl 2 was precipitated with excess of borax and precipitate washed with hot water, only Be(OH) 2 was left 1878; 2. Nilson, L. F. and Pettersson, Otto. Ueber die specifische Warme des Berylliums. Berichte, n, 381. Tids Krift, 17, 109. Short report to German Chem. Soc. of 1878; 3 and 1878; 4. 1878; 3. Nilson, L. F. and Pettersson, Otto. Ueber Darstel- lung und Valenz des Berylliums. Ann. der Phys. (Wied), 4, 554-5^5- Nova Acta. Soc. Sci. Upsala, 10, (1879), number 9, Chem. Centrbl., 1878, 275, 610. Jsb. Chem., 1878, 70, 241. Amer. Jour. Sci. (3), 15, 386; 16, 384. Chem. News., 37, 225. Very complete article. Historical review, preparation of (87 per cent.) metal by decomposition of chloride by sodium. Fused metal under salt in closed iron crucible. Properties of metal and list of "all well characterized' 1 compounds made up to that time. List contains many of very doubtful composition and omits some that prob- BIBLIOGRAPHY OF BRYWJUM 105 ably do exist. Concluded Be to be trivalent. Specific gravity Be=i.64, specific heat at 6 =0.2471. Could not make sulphide. 1878; 4. Nilson, L. F. and Pettersson, Otto. Sur ies prop- rieties physiques et sur la chaleur specifique de glucin- ium. Comptes rend., 83, 823. Ann. die chim. et de phys. (5), 14, 426. Bull. soc. chim. (2), 31, 442. Separately presented by M. Berthelot. Complete in Annales. Same as 1878; 3. 1878; 5. Meyer, Lothar. Ueber das Atomgewicht des Beryl- liums. Berichte, n, 576. Chem. Centrbl., 1878, 370. Chem. News, 38, 9. J. Chem. Soc. (London), 34, 557. J. Russ. Phys. and Chem. Soc., n, II, 40,. Discusses 1878; 3 and 4 and questions conclusion that Be is trivalent. 1878; 6. Brauner, B. Ueber das Atomgewicht des Berylliums Berichte, n, 872. Chem. Centrbl, 1878, 467. Jsb. Chem., 1878, 70. Chem. News., 38, 59. J. Chem. Soc. (London), 34, 704. J. Russ. Phys. and Chem. Soc., n, II, 49. Discusses N.. and P. (1878; 3), work on specific heat and predicts that if determined at higher temperature and density of BeCl 2 be found, Be will be found to be divalent. 1878; 7. Nilson, L. F. Om jodhaltiga derivat of platonitrit, (Beryllium platojodonitrite). Ofvsgt, Akad. For. Stockholm, 35, number 3, 51. Nova Acta Soc. Sci. Upsala, 10, (1879), number 16. Berichte, u, 884. J. prakt. Chem., 21, 172, (complete). 106 CHEMISTRY OF BERYUJUM Bull. soc. chim., (2), 31, 361. Chem. News., 38, 49. J. Chem. Soc. (London), 34, 706. Chem. CentrbL, 1880, 261. Jsb. Chem., 1878, 312. J. Russ. Chem. Soc., n, II, 305. Made BePtI 2 (NO 2 ) 2 +6H 2 O. 1878; 8. Nilson, L. F. and Pettersson, Otto. Ueber das Atomgewicht des Berylliums, (Erwidering an Lothar Meyer) . Berichte, n, 906. J. Russ. Phys. and Chem. Soc., n, II, 49. Discussion of 1876; 3 and 1878; 5. 1878; 9. Rossler, C. Ueber die Nachweisung des Berylliums. Ztschr. anal. Chem., 17, 148. Chem. CentrbL, 1878, 600. Jsb. Chem., 1878, 1059. Chem. tech. Rep., 1878, 422. J. Chem. Soc. (London), 34, 606. Bull. soc. chim. (2), 32, 365. J. Russ. Phys. and Chem. Soc., II, 83. By adding an excess of ammonium phosphate to a beryl- lium salt, dissolving the precipitate in HC1, adding NH 4 - OH to neutral reaction, avoiding excess, and heating to boiling, precipitate becomes crystalline and settles quickly. Na phosphate not applicable. Serves to separate from small amounts of Al if citric acid is present. Larger amounts of Al must first be removed by heating to 180 n sealed tube with excess of saturated solution of K 2 SO 4 . His phosphate was analagous to the similar magnesium compound, but varied somewhat in com- position so he did not assign formula. 1878; 10. Lockyer, V. N. Researches in spectrum analysis in connection with the spectrum of the sun. Proc. Roy. Soc. (London), 27, 279. Includes Be in table of elements probably present in sun. BIBLIOGRAPHY OF BERYLLIUM IO7 1878; ii. Sorret, J. L. Recherches sur 1' absorption des rayons ultra violets. Arch des sci. phys. et nat. de Geneve, (2), 63, 108, 1878 and (3), 4, 290, 1880. Solutions of BeCl 2 give no absorption bands but partially absorb the ultra violet light, the absorption increasing with the refrangability. Ultra violet light from an induction spark gives a faint blue fluorescence to a solution of beryllium chloride. 1879; I. Carnalley, T. Influence of atomic weight on physical properties of compounds. (Melting points of BeCl 2 and BeBr 2 ). Phil. Mag., (5),, 8, 281. Chem. News., 39, 281. Chem. Centrbl., 1880, 339. Jsb. Chem., 1879, l8 - J. Chem. Soc. (London), 37, 125. Obtained melting point of BeCl 2 and BeBr 2 , between 858-890, which are in reality several hundred degrees too high. 1879; 2. Mendeleef, D. La Loi Periodique de^ Elementes chimiques. Moniteur scientifique, 39, 691. Chem. News., 40, 303. Place of beryllium in system. 1880; i. Carnalley, T. and Carleton, Williams, W. The melt- ing and boiling points of certain inorganic solvents. J. Chem. Soc. (London), 37, 125. Apparently again determined the melting points of BeCl, and BeBr 2 as between 585-617, but on next page repeats his old figures of 858-890, both of which are much too high. 1880; 2. Vincent, Camille. Note sur les reactions produits par la di-methylamine aqueuse sur les dissolutions metalliques. Bull. soc. chim., 33, 157. Chem. Centrbl., 1880, 278. Zcit. anal. Chem., 17, 479. 108 CHEMISTRY OF BERYLLIUM Dimethyl amine precipitates beryllium from solutions of its salts as a white precipitate insoluble in excess, (also Fe," F/" and Zr). Says like precipitate from Al salts is soluble in excess. See also Renz, 1903. 1880; 3. Humpidge, T. S. Atomic weight of beryllium. Chem. News., 42, 261. Chem. Centrbl., 1881, 36. Jsb. Chem., 1880, 290. Berichte, 13, 2412. Agrees with Nilson and Petersson that Be is trivalent. 1880; 4. Reynolds, J. Emerson. Atomic weight of beryllium, note on. Chem. News., 42, 273. Chem. Centrbl., 1881, 68. Jsb. Chem., 1880, 289. Berichte, 13, 2412. 1880; 5. Ciamician, G. L. Uber des Spectrum des Berylliums Sitzber, Akad. Wein (2), 82, 425. Monatshefte fur Chemie, I, 662. Ztschr. anal Chem., 20, 411. Spark spectra between beryllium electrodes is homol- ogous with spectra of C. B and Mg. Obtained only a spectra of second order, a three-fold line 2 c : 509.7 ; 508.8; 508., in green and an intense violet line 3 c, 401.5. 1880; 6. Nilson, L. F., and Pettersson, Otto. Om beryl- liums atomwigt och vasendtliga egenskaper (atomic weight and essential properties). Ofers. af. K. Sven. Vet. Akad. Forh., 1880, No. 6, page 33. Berichte, 13, 1451-59. Chem. Centrbl., 1880, 612. Jsb. Chem., 1880; 4, 238. Jour. Chem. Soc. (London), 38, 850. Chem. News, 45, 13. Jour. Russ. Phys. and Chem. Soc., 13, II, 273. Ztschr. anal. Chem., 21, 483. BIBLIOGRAPHY OF BERYUJUM IO9 Determined atomic weight by ignition of hydrous sul- phate. Sulphate made from sublimed chloride and crystallized three times from excess of H 2 SO 4 . Dried between blotting paper. Made metal 94 per cent, pure and determined specific heat at 300 =5056. Long discussion favoring trivalency of beryllium. 1880; 7. Nilson, L. F., and Pettersson, Otto. On the Essen- tial Properties and Chemical Characters of Beryllium. Read before Royal Soc., Nov. 18, 1880. Chem. News, 42, 297. Berichte, 14, 259. J. Chem. Soc. (London), 40, 511. Separate presentation of 1880; 6. 1880; 8. Nilson, L. F. and Pettersson, Otto. Sur le poids atomique eat les proprietes principales da glucinum. Comptes rend., 91, 168. J. Chem. Soc. (London), 38, 792. Separate report to French Academy of 1880; 6, but not so complete as in Berichte, 13, 1451. 1880; 9. Nilson, L. F., and Pettersson, Otto. Om de sallsyn- ta jordarternas och deras sulfats molkylarvarme och- volym. (The molecular heat and molecular volume of the rare earths and their sulphates). Of. af. K. Sv. Akad. Forh., 1880, No. 6, p. 45. Berichte, .13, U59- Jsb. Chem., 1880, 291. Found the following figures based on trivalency of Be: Be 2 . Molecular weight, 75.3; specific gravity, 3.016; specific heat, 2471; molecular heat, 18.61 Be 2 (SO 4 ) 3 . Molecular weight, 315.3; specific gravity, 2.443; spe- cific heat, 0.1978. Be,(SO 4 )3+i2H 2 O. Molecular weight, 531.3; specific gravity, I.7I3 Be 2 O 3 diamagnetic. 110 CHEMISTRY OF BERYLLIUM ^ 1880; 10. Nilson, L. F., and Pettersson, Otto. Sur les chal- eur et le volume moleculaires des terres rare et de leur sulfates. Comptes rend., 91, 232. Separate report to the French Academy of 1880; 9. 1880; ii. Meyer, Lothar. Ueber das Atomgewicht des Beryl- lium. Berichte, 13, 1780. Bull. soc. chim.. (2) 36, 152. Chem. Centrbl., 1880, 1789. Arch, der Pharm., 218, 68. Chem. Ztg., 4, 752. Chem. News, 46, 159. J. Russ. Phys. and Chem. Soc., 13, II, 273. J. Chem. Soc. (London), 40, 139. Amer. Chem. J., 2, 360. Discussion of results of Nilson and Pettersson and others and comes to the conclusion that Be is divalent. 1880; 12. Nilson, L. F. Zur Frage nach dem Atomgewicht des Berylliums. Berichte, 13, 2035. J. Chem. Soc. (London), 40, 140. Chem. Centrbl., 1881, 36. Amer. Chem. J., 2, 433. Reply to 1880; ii. 1881 ; i. Brauner, Bohuslav. Ueber das Atomgewichte des Berylliums. Berichte, 14, 53. Chem. Centrbl.. 1881, 298. Jsb. Chem., 1881, 4. Phil. Mag., (5) ii, 65. J. Chem. Soc., 40, 224. Chem. Ztg., 5, 79- J. Russ. Phys. and Chem. Soc., 14, II, 63. Excellent discussion of the probable valency of Beryl- lium and favors divalency. BIBLIOGRAPHY OF BERYLLIUM III 1 88 1 ; 2. Reinsch, H. Ueber die Erkennung und Untersch- heidung der Kiesel-Thon, und Beryllerde, der Borsaure der Alkalien und einiger Metalle durch das Mikroskop. Berichte, 14, 2325. Chem. Cenrbl., 1882, 56. Jsb. Chem., 1881, 1183. Bull. soc. chim., (2) 37, 525. Chemisches Ind., 4, 428. Arch. der. pharm., 220, 68. Says that the sulphate forms very characteristic crys- tals under the microscope which enables it to be iden- tified at once. 1 88 1 ; 3. Classen, Alex. Elektrolytische Bestimmung und Trennung. Berichte, 14, 2782. Chem. Centrbl., 1882, 233. Jsb. Chem., 1882, 1152. Ding. Poly. J., 242, 440. Bull. soc. chim., (2) 37, 526. Ztschr. anal. Chem., 22, 440. Separates Fe and Al from Be by electrolysis in ammo- nium oxalate solution. Iron reduced. Aluminum pre- cipitated by use of stronger current, as hydroxide by ammonium carbonate produced and beryllium left in solution. 1 88 1 ; 4. Crookes, W. On Discontinuous Phosphorescent Spectra in High Vacuo. Proc. Roy. Soc., 32, 206. Chem. News, 43, 237. Annales chim. et phys., (5) 23, 555 (complete). Comptes rend., 92, 1281. Jsb. Chem., 1881, 130. Carefully prepared BeO gave a fluorescence of a beau- tiful blue, but no spectral rays. Under conditions giv- en it shows only a concentration of light in the blue. 112 CHEMISTRY OF BERYLUUM 1882; i. Blake, James. Atomic weight of beryllium as de- termined by its physiological actions. Chem. News, 45, HI. Jsb. Chem., 1882, 15. J. Chem. Soc. (London), 42, 701. Found that physiological action of sulphate injected in- to the blood was analogous to members of aluminum family, from which he concludes that beryllium is trivalent. 1882; 2. v. Bemmelen, J. M. Die Hydrate des Btrylloxyds. J. prakt. Chem., (2) 26, 227-246. Bull. soc. chim., (2) 39, 514. Chem. Centrbl., 1883, 36. Jsb. Chem., 1882, 275. Berichte, 15, 2902. Chem. News, 46, 291. J. Chem. Soc. (London), 44, 291. Rec. trav. chim. de Pays Bas., I, 271. J. Russ. Phys. and Chem. Soc., 15, II, 453. A long study of the hydroxides of beryllium. Dis- tinguishes two hydroxides, 1st. Alpha, made by boiling KOH solution, and 2nd. Beta, made by precipitating salts with ammonia. Only the first has definite com- position. 1882; 3. de Boisbaudran, Lecoq. Separation du gallium. Comptes rend., 94, 1439. Jsb. Chem., 1882, 1295. Separated from beryllium by precipitating gallium by potassium ferrocyanide in acid solution. 1883; i. Wallroth, K. A. Action du sel de phosphore sur divers oxydes. Bull. soc. chim., 39, 316. Chem. Centrbl., 1883, 290. Obtained BeNaPO 4 by fusing BeO in sodium meta- phosphate. Insoluble hexagonal plates. BIBLIOGRAPHY OF BERYUJUM 113 1883; 2. Philipp, Jul. Ueber basisches Beryllium-Kalium Ox- alate. Berichte, 16, 752. Jsb. Chem., 1883, 1045. Bull. soc. chim., (2) 40, 373. Mentions Debray's BeC 2 O 4 .3K 3 C 2 O 4 and Be(C 2 O 4 ). 3(NH 4 ) 2 C 2 O 4 and states that last salt is characteristic in its crystallization for beryllium and is valuable in purification. Made a new salt to which he gave the trivalent formula Be 2 (C 2 O 4 ) 3 .3K 2 C 2 O 4 .Be 2 (OH) 6 + 5H 2 O, by saturating acid potassium oxalate with Be (OH) 2 , evaporating and cooling in desiccator. J 883; 3. Donath, Ed. and Mayrhofer, J. Bemerkungen iiber Affinitat und deren Beziehungen zu Atomvolum, At- omgewicht und specific Gewicht. Berichte, 16, 1590. Jsb. Chem., 1883, 26. Uses determinations of others on beryllium in his dis- cussion. 1883 ; 4. Clarke, F. W. A recalculation of the Atomic Weights. (Glucinium). Chem. News, 48, 289. (From Constants of Nature). Chem. Ztg., 8, 21. A recalculation of all determinations of atomic weight of beryllium up to 1883 and discussion of same. 1883; 5. Hartly, W. N. On the Spectrum of Beryllium with observations relative to the position of the metal among the elements. J. Chem. Soc. (London), 43, 316. Chem. Centrbl., 1883, 380. Jsb. Chem., 1883, 246. Bull. soc. chim., (2) 41, 642. Chem. News, 47, 201. J. Amer. Chem. Soc., 5, 115. J. Russ. Phys. and Chem. Soc., 16, II, 63. Studies spectrum of beryllium and concludes that con- clusion of Nilson and Pettersson is wrong as to tri- 8 114 CHEMISTRY OF valency of beryllium and claims that its spectra shows it to be the first member of a dyad series of which, in all probability, Ca, Ba, and Sr are homologues. Ar- ticle contains fine chart of spectra of beryllium. 1883 ; 6. Haushofer, K. Beitrage zur mikroskopischen Analyse Sitzungsberichte 'd. Kon. Bayr. Akad. der Wiss., 1883, p. 436; 1884, p. 690. Ztschr. fur Kryst, n, 166;, 13, 173. Berichte, 18, 238. Jsb. Chem., 1885, 1880. Recommends beryllium platinum chloride, which is easily soluble in water as microscopic test for Be. Made by action of PtCl 4 on beryllium salt and evaporation in desiccator. Tetragonal crystals. 1883; 7. Humpidge, T. S. On the Atomic Weight of Glu- cinum. Chem. News, 47, 181. Froc. Roy. Soc. (London), 35, 137. Trans. Roy. Soc. (London), 174, 601. Chem. Centrbl., 1883, 380. Jsb. Chem., 1883, 35. Chem. Ztg., 7, 648. Berichte, 16, 2494. Determined specific heat as 4453 from a 94 per cent, metal made by action of Na on BeCl 2 . Speaks of the possibility of electrolyzing double fluoride of K and Be, but says material is very impure from fluorine at- tacking containing vessel. Gives many properties of Be and BeO not consistent with those of later inves- tigators. Main study was evidently on specific heat, which being obtained at low temperatures, lead him to the belief in trivalent beryllium. 1883; 8. Reynolds, J. Emerson. Atomic Weight of Berylli- um, Note on. Chem. News, 47, 251. Proc. Roy. Soc. (Lon.), 35, 248. Chem, Centrbl., 1883, 471. BIBLIOGRAPHY OF BERYUJUM 115 Jsb. Chem., 1883, 36. Jour. Chem. Soc. (Lon.), 46, 261. Berichte, 16, 2494. 1883; 9. Humpidge, T. S. Reply to a note by J. E. Reynolds on the Atomic Weight of Glucinum or Beryllium. Chem. News, 47, 297. Proc. Roy. Soc. (Lon.), 35, 358. Chem. Centrbl., 1883, 501. Jsb. Chem., 1883, 35- Chem. Ztg., 7, 873. Berichte, 16, 2659. 1883; 10. Reynolds, J. Emerson. Note in Regard to Hum- pidge's "Reply" on Beryllium. Chem. News, 48, 9. 1884; i- Penfield, Sam'l L. On the occurrence of alkalies in Beryl. Amer. J. of Sci., (3) 28, 25. Found Na, Li and H 2 O present, also Cs in two samples. Gives method of analysis used. 1884; 2. Lavroff, V. L'action du beryllium metalique sur le mercure-dimethyle, (Preliminary announcement of 1884; 3). Bull. soc. chim., (2) 41, 548. 1884; 3. Lavroff, V. Beryllium Methyl. J. Russ. Phys. and Chem. Soc.. 16, 93. By the action of metallic beryllium on mercury methyl in sealed tubes at 130, he obtained a white volatile crystalline substance, decomposed by water with evo- lution of light into methane and Be(OH) 2 . 1884; 4- Brogger, W. C., and Flink, Gust. Ueber Krystalle von Beryllium und Vanadium. Ztschr. fur Kryst, 9, 228-236. Berichte, 17, 849. Chem. Ztg., 8, 670. Bui. de la soc. franc, d. min., 7, 412. Bull. soc. chim., (2) 43, 561. J. Chem. Soc. (Lon.), 46, 1092. Il6 CHEMISTRY OF BERYLLIUM Used the beryllium crystals made by Nilson and Pet- tersson by action of Na on BeCl 2 . System Hexagonal and holohedral. Type I. Prismatic crystals. ooP : ooP' ==59, 59^', oo p' : oo P" = 60, n#', ooP : oP =89, 55^'. Type II. Tabular crystals. P : P = 57, 3i', P' : F = 56, 20', (poor) P : ooP = 28, n'. Axis relation a:c=i : i. 5802. Also examined crystals made by T. S. Humpidge and found them to belong to the holohedric division of Hex- agonal System. 1884; 5. Hartley, W. N. The Atomic Weight of Beryllium, Remarks on. Proc. Roy. Soc. (Lon.), 36, 462. Chem. News, 49, 171. Jsb. Chem., 1884, 49. J. Chem. Soc. (Lon.), 48, 484 . Discussion of his previous work on Spectra of Beryllium and its position among the elements. 1884; 6. Genth, F. A. On Herderite. Proc. Amer. Phil. Soc., 21, 694. Chem. News, 51, 86. Points out that BeO is slightly soluble in a boiling solu- tion of NH 4 C1, and discusses methods of determining BeO. 1884; 7. Nilson, L. F., and Pettersson, Otto. Ueber die Dampfdichte des Chlorberylliums. Berichte, 17, 987. Jsb. Chem., 1884, 61. Chem. Ztg., 8, 669. Bull. soc. chim., 44, 32. BIBLIOGRAPHY OF BgRYLUUM 117 Amer. J. ScL, (3) 28, 149. Tidskrift, 23, 310. Arch. der. Pharm., 222, 462. Amer. Chem. J., 6, 215. Found the density of BeCl 2 at different points between 490 and 812, overthrew all their previous ideas of the subject and proved the divalency of beryllium. Full details of preparation, apparatus and method used. 1884; 8. Nilson, L. F. and Pettersson, Otto. Determinations de la densite des vapeurs du chlorur de glucinium. Comptes rend., 98, 988. Chem. News, 49, 255. J. Chem. Soc. (Lon.), 46, 820. Chem. Centrbl., 1884, 452. Separately transmitted to French academy. Same as 1884, 7. " 1884; 9- Carnalley, T. Applications of Melting and Boiling points to the classification of the Atomic Weights of Elements. Phil. Mag. (5), 18, 21. Uses same result of previous work, (1879; i) in dis- cussion. 1884; 10. Carnalley, T. Ueber die Schmelzpunkte von Chlor und Bromberyllium. Berichte, 17, 1357. J. Chem. Soc. (Lon.), 46, 962. Repeats with careful precaution his earlier work and defends his previous results (1879; *) which are much too high. 1885 ; i. Humpidge, T. S. On the Atomic Weight of Glucinium. Proc. Roy. Soc. (Lon.), 38, 188. Chem. News, 51, 121. Jsb. Chem., 1885, 32. J. Am. Chem. Soc., 7, 113. J. Chem. Soc. (Lon.), 48, 1184. Berichte, 18, 258. Advance report of 1886; i. Il8 CHEMISTRY OF BERYUJUM 1885; 2. Tammann, G. Ueber die Dampftensionen von Salz- losungen. Ann. der. Phys. (Wied.), 24, 554. Mem. de 1'academy imp. de St. Pets'bg. 35, No. 9, 1887. Ztschr. phys. Chem., 2, 45. Jsb. Chem, 1888, 185. Gives figures on the lowering of the vapor tension by beryllium sulphate in comparison with other sulphates. Shows its molecular weight to be represented by BeSO 4 4H 2 O. Gives results also for chloride, brom- ide and nitrate. 1885; 3. Nilson, L. F. and Pettersson, Otto. Ueber ein Neues mit exacter Temperature Bestimmung verbun- denes Verfahren zur Feststellung der Dampfdichte fliichtiger Korper. Read at Kon. Ak. der. Wiss. Stockholm, Sept. 16, 1885. Jr. prakt. Chem. (2), 33, 1-17, (complete). Ann. de chim. et de phys. (6), 9, 554, (complete). Chem. Centrbl, 1886, 130. Jsb. Chem., 1886, 59. J. Russ. Chem. and Phys. Soc., 18, II, 92. Prepared BeCl 2 in platinum by action of dry HC1 on Be and redetermined density between 490 and 1520 C. Obtained quite closely agreeing results above 1000. Interesting description of apparatus used to prevent the chloride coming in contact with water or glass. Decided addition to previous work. 1886; i. Humpidge, T. S. Atomic weight of beryllium. Proc. Roy. Soc. (Lon.), 39, i. Jsb. Chem., 1886, 44. J. Chem. Soc. (Lon.), 50, 506. Berichte, 19, 202. J. Russ. Phys. and Chem. Soc, 18, II, in. Determined specific heat of Be on a specimen 99.2 per cent, pure at temperatures up to 450. The curve representing relation between specific heat and tempera- BIBLIOGRAPHY OF BERYUJUM 119 ture reaches a maximum at 400 and remains practically constant between 400 and 500. Figures obtained places Be with C. B. and Si, as accordant with law of Du- long and Petit at high temperature. Also determine density of BeCl 2 and BeBr 2 . Also made a double carbonate of evidently indefinite composition to which he gives the formula: 2(BeCO 3 .- (NH 4 ) 2 CO 3 ) Be(OH) 2 +2H 2 O. 1886; 2. Grandeau, H. De 1'action du sulfate de potasse a temperature elevee sur les phosphates metalliques. Ann. de chim. et de phys. (6), 8, 212. Jsb. Chem., 1886, 358. Made K 2 Be 2 (PO 4 ) 2 by fusing the sulphate and phos- phates together. Specific gravity BeO=3.i8. 1886; 3. Strohecker, R. Berylloxyd in diluvialen Thonen. J. prakt. Chem., (2) 33, 132. Jsb. Chem., 1886, 407. Chem. News, 53, 136; 54, 207. 1886; 4. Penfield, S. L. and Harper, D. N. Chemical composi- tion of Herderite and Beryl. Am. J. Sci., (3) 32, 107. Chem. News, 54, 90. Berichte, 19, 797. Chem. Industrie, 10, 366. Analysis and discussion of methods of separation of beryllium from aluminum. 1886; 5. Chabrie, C. Note preliminaire sur les fluosilicates d'aluminium et de glucinium. Bull. soc. chim., (2) 46, 284. Chem. Centrbl., 1886, 771. Jsb. Chem., 1886, 399. J. Chem. Soc., 50, 981. Berichte, 19, 871. 1886; 6. Cooke, J. P. On Danalite, a new Mineral Species from the Granite of Rockland, Mass. Amer. J. Sci. (2), 42, 78. Ztschr. and Chem. 6, 226. 120 CHEMISTRY OF BERYLLIUM Gives method of analysis and separated iron from beryllium by reducing the former in a current of hy- drogen and volatilizing it in a current of hydrochloric acid gas. 1887; J - Meyer, Lothar. Ueber die Einwirkung von Chlor kolenstoff auf Oxyde. Berichte, 20, 68 1. Jsb. Chem., 1887, 379- Found he could make many metallic chlorides by pass- ing CC1 4 over oxides when heated, among them BeCl 2 . 1887; 2 - Ebel, Fr. Ueber antimonsaure Salze. Berichte, 22, 3044. J. Chem. Soc. (Lon.), 58, 216. Made BeSb 2 O 6 .6H 2 O by dissolving Na 2 H 2 Sb 2 O 7 .7H 2 O in boiling water and adding a soluble beryllium salt. 1887; 3- Crookes, W. Radiant Matter Spectroscopy. Ex- amination of the residual glow. Proc. Roy Soc., 42, in. J. Chem. Soc. (Lon.), 52, 1066. Examined BeO among other oxides. Found it to give a rich blue, but no residual glow. 1887 ; 4. Mallard, E. Sur quelques substances cristallisees pre- parees par Ebelmen. Bui. de la soc franc, de min., n, 305. Ztschr. f. Kryst., 14, 605; 15, 650. Ann. d. mines, 12, 427, 460. Comptes rend., 105, 1260. Jsb. Chem., 1887, 384. J. Chem. Soc. (Lon.), 54, 349. By fusing chromic oxide and BeO in presence of boric anhydride and calcium carbonate Ebelmen obtained a product which, after treatment with hydrochloric acid, left a crystalline chromite analagous to Alex- andrite. From crystals of BeO prepared by Ebelmen, he obtain- ed parameters a : h = I ; 1.6305, isomorphous with ZnO, positive and uniaxial. Made artificial phenacite BIBLIOGRAPHY OF BERYLLIUM 121 Be 2 SiO 4 by fusing silica, beryllia and borax together in optically positive hexagonal prisms. 1887 ; 5. Zimmermann, A. Ueber die Trennung der Thonerde und Beryllerde. Inaugural Dissertation, Berlin, 1887. Ztschr. f. anorg. Chem., 15, 285. Ztschr. f. anal. Chem., 27, 61. Chem. News, 58, 49. J. Chem. Soc. (Lon.), 54, 323. Separated by boiling a solution in KOH. Also recom- mends separation by boiling with sodium thiosulphate after neutralization with Na 2 CO 3 . Not new and separations far from perfect. 1888; i. Neumann, G. Ueber Doppelsalze von Sesquichloriden mit anderen Metallchloriden. Ann. der Chem. (Liebig.), 244, 335. Chem. Centrbl., 1888, 709. Made BeCl 2 .FeCl 3 + H 2 O and BeCl 2 .CrCl 3 + H 2 O 3 BeCl 2 .Tl 2 Cl 6 . 1888; 2. Kluss, K. Zur Kentniss der Unterschwefelsauren Salze. Unterschwefelsaures Beryllium. Ann. der Chem. (Liebig.), 246, 195. Bull. soc. chim., (3) 2, 14. 5BeO.2S 2 O 3 -|-i4H 2 O. Basic salt, colorless gummy mass. Loses H 2 O and SO 2 on heating. Made by carefully evaporating a solution of Be(OH) 2 in dithionic acid. (Probably an indefinite solid solution). 1888; 3. Sestine, F. Ueber einige selten in Planzen vorkom- mende und seither noch nicht darin gefundene chemis- che Elemente, Spezielle iiber Beryllium mit Riicksicht auf einige Kultwerke Planzen. Chem. Centrbl., 1888, 1622. From. Staz. Sperim. Agrar., 15, 290-298. Jsb. Chem., 1888, 2556. Found beryllium in ash of plants which had been fed with BeSO 4 , instead of MgSO 4 . Also in plants from beryllium containing soils. 122 CHEMISTRY OF BERYLUUM 1888; 4. Hautefeuille, P. and Perrey, A. Sur 1'action mineral- istetrice des sulfures alcalins. Comptes rend., 106, 487, 1800. Jsb. Chem., 1888, 555, 557, 558. Chem. News, 58, 24. Ztschr. f. Kryst, 18, 322. Berichte, 21, 175, 599. Prepared artificial phenacite and emerald. 1888; 5. Hautefeuille, P. and Perrey, A. Sur les combinasions silicates de la glucine. Comptes rend., 107, 786. Chem. CentrbL, 1888, 1569. Ztschr. f. Kryst., 18, 328. J. Chem. Soc., 56, 104. Berichte, 21, 887. If constituents of a beryllium leucite are fused at 6oo-8oo in excess of potassium vanadate, crystals are obtained of heterogeneous composition and which he concludes may be considered as mixtures of the fol- lowing : 2K 2 O.Be 2 O s -8SiO 2 , K 2 O.Be 2 O v4 Si0 2 , 2K 2 O.Be 2 6 3 .ioSiO 2 , K 2 O.Be 2 3 . 5 Si0 2 . Claims Be can replace Al in above and also in ortho clase. 1889; i. Stolba, Fr. Aufschliessung des Berylls mit Atzlauge Listy chemicke, (Prag.), 13, 117. Chem. Centrbl., 1889, I, 297. Claimed to act upon finely divided beryl with 10 per cent. NaOH solution so that it was decomposed by HC1. 2. Dana, E. S. and Wells, H. L. New Mineral, Beryllonite. Am. J. Sci., (3) 37, 23-32. Chem. Centrbl., 1889, I, 141 ; 1890, I, 337. Ztschr. f. Kryst., 17, 592. Gives method of analysis in brief. BIBLIOGRAPHY OF BERYLLIUM 123 1889; 3- Mendeleeff. The Periodic Law of the Chemical Ele- ments (Faraday Lecture, June '4, 1889). J. Chem. Soc., 55, 650. Discussion of the place of beryllium among the ele- ments and the interesting controversy finally settled in favor of the periodic law. 1889; 4. Wulff, G. Optische Studien an pseudosymmetrischen Krystallen. Das Beryllium Sulfat. Ztschr. f. Kryst., 17, 592. Cnem. Centrbl., 1890, II, 73. Beryllium sulphate is strongly double refractive, is negative and uniaxial. 1890; i. Moraht, Hermann. Untersuchungen iiber das Beryllium. Inaugural Dissertation, Munich, 1890. See 1890; 5 and 1890; 7. 1890; 2. Sestini, Fausto. Proprieta di aleuni sali di berillio e die corrispondenti composti di alluminio. Gazzetta chim. ital., 20, 313. Chem. Centrbl., 1890 II, 542. J. Chem. Soc. (Lon.), 60, 151. Berichte, 23, 482. J. Russ. Phys. and Chem. Soc., 22, II, 131. Rather general work upon the phosphate and carbonate. Obtained a precipitate to which he gave the formula: 3BeO.P 2 O 5 .3H 2 O+Ag. Compared the solubility of Be (OH) 2 and A1(OH) 3 in carbonated waters. Slight- ly greater solubility of Be(OH) 2 in carbonate water. 1890; 3. Winkler, Clemens. Ueber die Reduction von Sauer- stoffverbindungen durch Magnesium. Berichte, 23, 120. J. Chem. Soc. (Lon.), 58, 451. Reduced (only partially) BeO by Mg. Reduction very doubtful. 1890; 4. Kruss, Gerhard and Moraht, Hermann. Unter- suchungen iiber das Beryllium. Berichte, 23, 727. Preliminary communication to German Chemical Society. For complete details see 1890; 5. 124 CHEMISTRY OF 1890; 5. Kruss, Gerhard and Moraht, Hermann. Untersuch- ung iiber das Beryllium I. Ann. der Chem., 260, 161. Chem. CentrbL, 1890, I, 794, II, 734, 989. Jsb. Chem., 1890, 538. Bull. soc. chim., (3) 4, 377, 833. Chem. News, 65, 12. J. Chem. Soc. (Lon.), 58, 697. J. Amer. Chem. Soc., 12, 154. Ztschr. anal. Chem., 31, 693. J. Russ, Phys. and Chem. Soc., 22, II, 130. Prepared impure Be in hexagonal plates by reduction of K 2 BeFl 4 with sodium. Made Be(OK) 2 impure which was easily decomposed by C0 2 . Made BeSO 3 (in absolute alcohol) and gave the formulas BeO.BeSO 3 and BeO.3BeSO 5 to some basic substances obtained. Made 5BeO.B 2 O 3 (dried at 110). Research was car- ried on to show the weak basic character of Be. 1890; 6. Kruss, Gerhard and Moraht, Hermann. Untersuch- ungen iiber das Beryllium. Berichte, 23, 2552. Advance communication of 1890; 7. 1890; 7. Kruss, Gerhard and Moraht, Hermann. Untersuch- ung iiber das Beryllium, II. Ann. der Ohem.. 262, 38-61. Chem. Centrbl., I, 569. Jsb. Chem., 1891, 491. Bull. soc. chim., (3) 8, 51. Ztschr. phys. Chem., 7, 226. Chem. News, 67, 242. J. Chem. Soc., (Lon.), 58, 697; 60, 881. J. Amer. Chem. Soc., 12, 154. Ztschr. Anal. Chem., 30, 530. J. Russ. Phys. and Chem. Soc., 22, II, 132. Prepared BeSO 4 4H 2 O with great care and of a high de- BIBLIOGRAPHY OF BERYLUUM 125 gree of purity. Material from several sources. Deter- mined the atomic weight by ignition of sulphate after drying over phosphorus pentoxide. Mean of fourteen determinations using large quantities of material gave 9.027 (O=i6). Specific gravity of BeSO 4 4H 2 O found to be 17125. Specific gravity 660=2.9644. 1.7125. Specific gravity 660=2.9644. 1890; 8. Petersen, Emil. Neutralizationsphanomene des Alu- minium und Beryllium Fluorid. Ztschr. phys. Chem., 5, 259-266. Chem. Centrbl, 1890, I, 892. Berichte, 23, 270. J. Chem. Soc. (London), 58, 680. Heat of neutralization of Be(OH) 2 +2HF.Aq=i9683 calories. 1890; 9. Haute feuille, P, and Perrey, A. Sur la cristallization de 1'alumine et de la glucine. Bull, de la soc. franc, de min., 13, 149. Ztschr. f. Kryst, 21, 306. J. Russ. Phys. and Chem. Soc., 22, II, 133. Chem. Centrbl., 1890, II, 716. Prepared crystals of beryllium oxide, by dissolving the oxide in fused leucite. Also prepared chrysoberyl. 1890; 10. Hautefeuille, P. and Perrey, A. Sur les silico glucinates de soude. Comptes rend., no, 344. Jsb. Chem., 1890, 143. Chem. Centrbl., 1890, I, 668, II, 716. J. Chem. Soc. (London), 58, 562. Berichte, 23, 288. On fusing a mixture of BeO, SiO 2 and Na 2 O (in same proportion as in a beryllium nephylene) in excess of sodium vanadate at about 800 C, crystals to which they gave the following formula, Na,O, Be 2 O,, 3SiO 2 were obtained. Also obtained substances to which they assigned the following formulas: Na 2 O, Be 2 O 3 .6SiO 2 , 126 CHEMISTRY OF BERYLUUM 2Na 2 O, 3Be 2 O s . (20.67-22.41) SiO 2 , 3Na 2 O,2Be 2 6 s .i5SiO 2 , 3Na 2 O, 2Be :i O 3 .i8SiO 2 , 3Na 2 O, 1890; ii. Ouvrard, L. Sur quelques phosphates de lithine, de glucine, de plomb et d'urane. Comptes rend., no, 1333-36. Chem. Centrbl., 1890, II, 203. Chem. News., 62, 25. Bull. soc. chim., (3) 5, 80. J. Chem. Soc. (London), 58, 1055. Berichte, 23, 550. By fusing with potassium, meta, pyro and orthophos- phate, obtained K 2 O.2BeO.P 2 O 5 in rhombic prisms. With sodium meta and pyrophosphate, obtained Na^O.- 2BeO.P 2 O 5 , in hexagonal plates identical with beryl- lonite. From sodium orthophosphate 2Na 2 O.BeO.P 2 O c in lamellae. 1890; 12. Wagner, J. Untersuchung iiber die innere Reibung von Flussigkeiten. Ztschr. phys. Chem., 5, 34. Uses BeSO 4 .4H 2 O as one of the salts of the series studied. 1890; 13. Rydberg, J. R. Ueber den Bau der Linienspektren der chemischen Grundstoffe. Ztschr. phys. Chem., 5, 231. Refers in discussion to lines for beryllium. 1890; 14. Hautefeuille, P. and Perry, A. Uber verschiedene Silikatverbindungen der Oxyde von Kobalt, Zinc, Mag- nesium and Beryllium. Chem. Centrbl., 1890, II, 716. Bull, de la soc. franc, de min., 13, 149. By fusing beryllium sulphate with silicic acid obtained hexagonal crystals of beryllium oxide. Also obtained phenacite and a silicate of the composition, 3BeO.2SiO 2 . BIBLIOGRAPHY OF BERYLUUM 1 27 1891 ; i. Roozeboom, H. W. Bakhuis. Ueber die Loslichkeit von Mischkrystallin. Ztschr. phys. Chem., 8, 528. Discussion of the significance of the mixed crystals of BeSO 4 .4H 2 O and BeSeO 4 4H 2 O. 1891 ; 2. Behrens, H. Beitrage zur mikrochemischen Analyse. Ztschr. f. Anal. Chem., 30, 139. Chem. News, 64, 41. Detects beryllium by means of the crystals of its double oxalate with potassium. 1891 ; 3. Winkler, Clemens. Ueber die Reduction von Sauer- stoffverbindungen durch Magnesium. Berichte, 24, 1966. Bull. soc. chim., (3) 6, 724. J Chem. Soc. (London), 60, 115-5. Claimed to make a very impure BeH by heating a mix- ture of BeO and Mg in H for four hours. Results rather uncertain. 1891 ; 4. Rammelsberg, C. Ueber einige Salze der Unter- phosphorsaure. Sitzber. Akad. Wiss. (Berlin), 1891, 369-76. J. prakt. Chem., (2) 45, 158. Chem. Centrbl., 1891, II, 790. Bull. soc. chim., (3) 8, 686. J. Chem. Soc. (London), 62, 404. Hot solution of BeSO 4 .4H 2 O when precipitated with normal Na 2 PO 3 , yields 2BePO 3 +3H 2 O which loses ^2 of its water at 23O-25o. I &9 1 ; 5. Jahn, Hans. Ueber die electromagnetische Drehung der Polarizationsebene in Flussigkeiten, besonders in Salzlosungen. Ann. der Phys. (Wied), 43, 284. Found the specific rotation for BeSO 4 =o.28895. 1891 ; 6. Sestini, Fausto. Experiments with wheat on the sub- stitution of Beryllium for Magnesium. 128 CHEMISTRY OF J. Chem. Soc. (London), abs. from Staz. sperim. agrar. Ital., 20, 256. Jsb. Chem., 1891, 2702. Experiments indicate that beryllium may take the place of magnesium in growth of wheat but is not a complete substitute for magnesium in production of seed. 1892; i. Friedel, Ch. and Sarasin. Production artificelle de divers mineraux. Bibliothique Universelle, Arch. phys. nat., 27, 145. Chem. Centrbl., 1892, I, 864. Jsb. Chem., 1892, 520. Obtained a beryllium aluminum potassium silicate by fusing the oxide of the first two with potassium silicate. 1892; 2. Rauter, Gustav. Ueber das Siliciumtetrachlorid. Ann. der Chem., 270, 244. Jsb. Chem., 1892, 645. Heated SiCl 4 and powdered metallic beryllium in a closed tube for three hours at 240 -250 and found that a partial double decomposition took place yielding as a result a mixture of SiCl 4 , BeCl 2 , Be and Si. 1892 ; 3. Gratzel von Gratz, A. Verfahren zur Gewinnung von Bor, Silicum, Aluminium, Beryllium und Magnesium. D. Pat., 58600. Chem. Ind., 14, 499. Ding, polyt. J., 283, 129. Jsb. Chem., 1892, 2651. Proposes to mix the oxide of beryllium with the chloride of a more electro positive element and by passing cur- rent to obtain metal at one pole and oxygen at the other. 1892; 4. McMahon, C. A. Microchemical Analyses of rock forming mineral. Min. Mag. and J. of Min. Soc., 10, 79-122. Says the double salt BeK 2 (SO 4 ) 2 .2H 2 O is very char- acteristic. Does not use the oxalate as recommended by Behrens (1891 ; 2). BIBLIOGRAPHY OF BERYLUUM I2<) 1892; 5. Karnojitsky, A. Ueber die optische Anomalie des Beryls. Ztschr. f. Kryst, 19, 209-219. Chem. Centrbl., 1892, I, 492. Studied the optical properties of beryl. 1892 ; 6. Schleir, M. Zur Anwendung des Nitroso-/?-Naphthols in der quantitative Analyse. Trennung von Eisen und Berylliums. Chem. Ztg., 16, 420. Chem. Centrbl., 1892, I, 717. Jsb. Chem., 1892, 2540. Ztschr. f. anorg. Chem., 3, 84. Ztschr. anal. Chem., 36, 699. Gives details for analysis of a mixture of iron and beryl- lium salts by precipitating the former with nitroso-/?- naphthol. Excellent quantitative results obtained. Says that it is the best method of removing last trace of iron from beryllium. 1893; i. Haute feuille, P. and Perrey, A. Annales de chim. et de phys., (6) 20, 447-474. Artificially produced phenacite, beryl and a number of uncertain sodium and potassium beryllium silicates and basic beryllium silicates. 1893; 2. v. Helmolt, Hans. Ueber Einige Doppelfluoride. Ztschr. f. anorg. Chem., 3, 115-152. Jsb. Chem., 1893, 409. Obtained BeF 2 .2NH 4 F in fine crystals. Crystallizes in small colorless needles and prisms. Prepared by dissolving Be(OH) 2 in HNH 4 F to saturation and evap- orating. 3- Gibson, John. J. Chem. Soc. (London), 63, 909. Chem. Centrbl., 1893, I, 512, II, 319. Jsb. Chem., 1893, 474. Chem. News, 67, 66. Chem. Ztg , 17, 210. 130 CHEMISTRY OF BERYLLIUM Ztschr. anorg. Chem., 5, 240. Bull. soc. chim., 12, 117. J. Russ. Phys. and Chem. Soc., 25, II, 165. Recommends the preparation of BeO by igniting beryl with ammonium hydrogen fluoride, which takes place at a low temperature, and dissolving out with water. 1893; 4. Seubert, Karl and Elten, M. Zur Kenntniss der basischen Metalsulfite. Ztschr. f. anorg. Chem., 4, 52-74, 78-81. Jsb. Chem., 1893, 312. J. Chem. Soc. (London), 64, 456. Made a basic sulphite which came near the formula 2BeSO 3 .9Be(OH) 2 .6H 2 O and a basic carbonate BeC0 3 . 5 Be(OH) 2 . 3 H 2 0. 1894; I. Traube, H. Ueber die Kunstliche Darstellung des Beryll. Jahrb. f. Min., 1894, I ; Mem., 275. J. Chem. Soc. (London), 66, 284. Added sodium silicate to a solution containing 3 mols BeSO 4 and one mol A1 2 (SO 4 ) 3 and fused the dried precipitate so obtained with B 2 O 3 in platinum crucible at 1700 for three days. Obtained beryl crystals. 1894; 2. Smith, Edgar F. and Heyl, Paul. Ueber die Ver- wendung von Quicksilber Oxyd bei der Analyse. Ztschr. f. anorg. Chem., 7, 88. Could not separate Fe and Al quantitatively from beryl- lium by HgO. 1894; 3. Traube, H. Das atomare und molecular Losungs- volumen. Ztschr. f. anorg. Chem., 8, 12. Berichte, 27, 3 1 73-7& J. Chem. Soc. (London), 68, II, 70. Molecular solutions volume of BeSO 4 and Be(ClO 3 ) 2 . 1894; 4. Borchers, W. Apparate zur Abschiedung von Mag- nesium, Lithium und Beryllium aus geschmolzenen Haloidsalzen. BIBLIOGRAPHY OF BERYLLIUM 13! Ztschr. Elektrotech and Elektrochem., 1894, 361. Chem. Centrbl., 1895, I, 579. 1894; 5. Wyrouboff, G. Silicotungstates. Bull. soc. chem., (3) n, 1106. Preliminary note of work on silicotungstates in which he argues for trivalency of beryllium. 1894; 6. Combes, Alph. Sur la valence der glucinium et la formule de la glucine. Comptes rend., 119, 1221. Mon. sci., (4) 9, 154. Ztschr. anorg. Chem., 9, 245-. Chem. News, 71, 38. Chem. Centrbl., 1895, I, 320. J. Chem. Soc. (London), 68, 224. Berichte, 28, 10. Bull. soc. chim., (3) 13, 3. Made beryllium acetylacetonate, Be(C 5 H 7 O 2 ) 2 , by action of acetyl acetone on beryllium acetate and gives its properties. Melts at 108, sublimes as low as 100, boils at 270 without decomposition. Two determina- tions of density gave figures in accord with divalency of beryllium. 1894; 7. Walden, P. Ueber die optische Drehung der lonen. Ztschr. phys. Chem., 15, 202. Made Be(C 10 H 14 BrO.SO 2 .O) 2 , beryllium alpha brom camphor sulphonate and studied its optical rotation in comparison with similar salts of Mg, Zn, and Ba in dilute solution. Found the rotation essentially the same for all (compare 1899; J 3) an< ^ f r tne ac ^ itself. These ions therefore inactive. 1895-; I. Wyrouboff, G. Response to remarks of A. Combes on valence of beryllium. Bull. soc. chim., (3) 13, 4. 1895; 2. Lebeau, P. Sur un carbure du glucinium. Comptes rend., 121, 496. Ztschr. anorg. Chem., 13, 364. Chem. Centrbl., 1895, II, 959. 132 CHEMISTRY OF BERYLLIUM Bull, soc chim., (3) 13, 1065. Chem. News, 72, 209. Mon. sci., (4) 9, 806. Ztschr. f. Elektrochem., 2, 409. J. Soc. Chem. Ind., 15, 141. J. Chem Soc. (London), 70, 169. Berichte, 28, 899. BeO mixed with half its weight of sugar carbon and a little oil and heated in an electric furnace for 8-10 min- utes with 950 amperes at 40 volts. Obtained carbide which he calls Be 4 C 3 (which was undoubtedly Be 2 C) in crystals, harder than quartz, transparent. Specific gravity 1.9 at 15. Attacked at red heat by Cl, Br, HF, and HC1 with liberation of carbon and formation of halide. Slowly decomposed water, liberating CH 4 . Quickly decomposed by caustic alkalies. No other car- bide seems to exist. I 895 J 3- Lebeau, P. Sur 1'analyse de 1'emeraude. Comptes rend., 121, 601. Chem. News, 72, 245. Dissolved in KOH in silver crucible and afterward fol- lowed procedure of Debray. 1895; 4. Rowland, H. A. and Tatnall, R. R. The arc spectra of the elements. II. Boron and Beryllium. Astrophysical Journal, 1895, I, 16; II, 185. Gives as the most prominent lines for Be between 2100 and 4600 the following : 2348.697 2350.855 2494-532 2494.960 Observations made by means 2650.414 of a grating of 21^ feet 2651.042 radius and 20000 lines to the 3 I 3-556 inch on photographic plate 3131.200 19 inches in length. 3321.218 3321.486 4572.869 BIBLIOGRAPHY OF BERYUJUM 133 l &95 > 5- Lebeau, P. Sur la traitement de I'emeraude et la prep- aration de la glucine pure. Comptes rend., 121, 641. Ztschr. anorg. Chem., 13, 364. Bull. soc. chim., (3) 15, 166. Chem. News, 73, 3. Mon. sci., (4) 10, 71. Ztschr. f. Elektrochem., 2, 432. Chem. Centrbl., 1895, II, 1150. J. Chem. Soc. (London), 70, 168. Decomposed beryl by fusion with twice its weight of CaF 2 , when on pouring into water, a friable mass, easily attacked by H 2 SO 4 , was obtained. Most of the silica was thereby removed. Also fused beryl in an electric furnace and volatilized part of its silica when residue was easily attacked by a mixture of H 2 SO 4 and HF. Impure beryllium carbonate obtained by usual procedure was dissolved in HNO 3 , iron precipi- tated by ferrocyanide, the excess ferrocyanide by cop- per nitrate and the copper by H 2 S. The solution was then mixed with ammonia and the precipitate allowed to stand three days whereby the A1(OH) 3 became in- soluble in ammonium carbonate. 1895 ; 6. Hart, Edward. Note on the Purification of Glucinium Salts. J. Amer. Chem, Soc., 17, 604. Chem. Centrbl., 1895, II, 590. Bull. soc. chim., (3) 16, 226. Chem. News, 72, 77. J. Chem. Soc. (London), 70, 168. Separates beryllium from iron and aluminum by dissolv- ing in H 2 SO 4 and adding Na 2 CO 3 slowly, with boiling after each addition, until the liquid shows no yellow color. The beryllium remains in solution as a basic sul- phate while the iron and aluminum are precipitated. 134 CHEMISXRY OF BERYLUUM 1895; 7. Prudhomme, Maurice. Sur le mordant de glucine. Bull. soc. chim., (3) 13, 509. Mon. sci., (4) 9, 411. Ztschr. f. anorg. Chem., 10, 446. Chem. Centrbl., 1895, II, 264. J. Soc. Chem. Ind., 14, 802. Beryllium acts as a divalent, not as a trivalent element. 1895 ; 8. Henry Louis. Apropos un carbure du glucinium. Comptes rend., 121, 600. Ztschr. f. anorg. Chem., 13, 365. Bull. soc. chim., 15, 165, 475. Chem. Centrbl., 1895, II, 1067. Bull. acad. Belg., 30, 460-465. Chem. News, 72, 245. J. Chem. Soc. (London), 70, 169. Mon. sci., (4) 9, 857. Berichte, 28, 967. J. Soc. Chem. Ind., 15, 141. Criticises Lebeau (1895 ; 2) for giving formula Be 4 C 3 to his carbide and using atomic weight of 13.8 when analyses agreed with Be 2 C and valency of beryllium had been proven. 1895; 9. Atkinson, E. A. and Smith, E. F. The Separation of Iron from Beryllium. J. Amer. Chem. Soc., 17, 688. Chem. Centrbl., 1895, II, 844. Bull. soc. chim., (3) 16, 229. Ann. de chim. analytique, i, 118. J. Chem. Soc. (London), 70, 220. Analyst, 21, 23. Showed that iron and beryllium can be quantitatively separated by Nitroso--Naphthol. (Compare 1892; 6). 1895; 10. Warren, H. N. Manufacture and Commerical Sep- aration of Glucinium. Chem. News, 72, 310. Ztschr. f. anorg. Chem., 13, 364. Ztschr. f. Elektrochem., 2, 459. BIBLIOGRAPHY OF BERYLLIUM 135 Chem. Centrbl., 1896, I, 336. - J. Chem. Soc. (London), 70, 247. Proposed separation of the metal by electrolytic reduc- tion of the bromide. Bromide, however, is a non con- ductor. 1895-; ii. Borchers, W. Abschiedungsmethoden des Lithiums und des Berylliums. Ztschr. f. Elektrochem, 2, 3, 9. Chem. Centrbl., 1895, II, 13. J. Chem. Soc. (London), 70, 521. Ztschr. phys. Chem., 21, 517. Proposes to electrolyze a melted mixture of BeCl 2 with alkaline chlorides or alkaline earth chlorides. Makes mixture by evaporating mixed chlorides and adding a little NH 4 C1 to arrest conversion of BeCl 2 into BeO. Calcium and magnesium chlorides must be absent. No metal appears to have been made. 1895 ; 12. Rinne, F. Die Krystallform chemischen .einfacher Korper. Ztschr. phys. Chem., 16, 529. Gives crystal form data for Be and BeO in table with many other substances. 1896; I. Wyrouboff, G. Silicotungstates. Bull. soc. franc, d. min., 19, 219, 354. Ztschr. f. Kryst, 29, 676. J. Chem. Soc. (London), 72, 178. Made beryllium silico tungstate to which he gave the formula Be 1 (W 12 SiO 40 ) 3 . Crystallizes below 45- as a cubic hydrate containing 93 H 2 O; above 45, as a rhombohedral hydrate containing 87 H 2 O. In presence of nitric acid at 30 a 45 H 2 O is obtained. 1896; 2. Properties of Beryllium. Eng. and Mining J., 6, 162 from Electrical Review of London. Revue de chim. ind., 7, 323. Claims beryllium is on the market at $18 a pound and gives very improbable properties for metal. 136 CHEMISTRY OF BERYLLIUM 1896; 3. Liebermann, Louis. Verfahren zur Darst. von Beryl- lium in form seiner Legierungen. D. R. P. 94507, Sept. 22, '96, Patent bl. 18868. Chem. Ztg., 23, 253. Berg, in Hutten Ztg., 57, 149. Wagners Jsb., 43, 320. Ztschr. f. Elec., 4, 258. 1896; 4. Retgers, J. W. Beitrage zur Kenntniss des Isomor- phisms. Ztschr. f. phys. Chem., 20, 481. Ztschr. f. Kryst, 30, 635'. Amer. J. ScL, (4) 2, 448. J. Chem. Soc. (London), 72, 17. Berichte, 29, 1059. By discussion of the results of others and by crystalliz- ing mixtures of the sulphates of Cu, Ni, Fe, Mn and Be, Retgers comes to the conclusion that Be is not isomorphous with the metals of the Mg. group. 1896; 5. Duboin, Andre. Sur une methode de reproduction de silicates doubles de potasse et d'autres bases. Comptes rend., 123, 698. Chem. Centrbl., 1896, II, 1081. J. Chem. Soc. (London), 72, 96. Obtained crystals of a double silicate of Be and K which appear homogeneous but vary between 2K 2 O.3BeO.5SiO 2 and 2K 2 O.3BeO.7SiO 2 , made by dissolving a mixture of BeO and SiO 2 in fused KF and then submitting to long fusion with KC1. 1896; 6. Lebeau, P. Sur quelques proprieties de la glucine pure. Comptes rend., 123, 818. Chem. Centrbl., 1897, I, 16. Ztschr. anorg. Chem., 15, 472. Chem. Ztg., 20, 973; 21, 8. Chem. News, 74, 292. BIBLIOGRAPHY OF BERYLLIUM 137 J. Soc. Chem. Ind., 16, 72. J. Chem. Soc. (London), 72, 144. J. Russ. Phys. and Chem. Soc., 29, II, 58. Specific gravity BeO ignited at 44O=3,oi2, ignited at I2OO=3.OI. BeO fuses in electric arc and on cooling forms a white crystalline mass, slightly harder than rubies. BeO is attacked by fluorine when heated but not by other halo- gens or by sulphur or nitrogen. Potassium, sodium and aluminum have no action on the oxide at high temperatures and it is not reduced by magnesium even at the boiling point of that metal. BeO swells up in pure H 2 SO 4 and yields anhydrous sulphate which dissolves very slowly in boiling H 2 O. 1896; 7. Burgass Rob. Anwendung des Nitroso-/?-Naphthols in der anorganische Analyse. Ztschr. angwdte. Chem., 1896, 596. J. Chem. Soc. (London), 72, 163. Separates quantitatively iron from beryllium by means of Nitroso-#-Naphthol. Compare 1892; 6 and 1895; 9. 1896; 8. Glaser, Charles. Chemical Analysis of Monazite Sand. J. Amer. Chem. Soc., 18, 782 J. Chem. Soc. (London), 72, 191. Rev. Amer. Chem. Research, 2, 66. Gives his method for determining beryllium in monazite. 1896; 9. Anonymous. Beryllium instead of platinum for incandescent lamps. Elektrochem. Ztschr., 3, 70, from Journal des inven- teurs. Suggests use as indicated by title. Coefficient of expan- sion not given. 1896; 10. Larssow, Aksel. Untersuchung iiber Niob. Ztschr. f. anorg. Chem., 12, 188. J. Chem. Soc. (London), 70, 564. 138 CHEMISTRY OF BERYLUUM Made a crystalline beryllium columbate by fusing with boric anhydride, the precipitate obtained by precipitat- ing potassium columbate with beryllium chloride. Found composition, 6.24 per cent. BeO, 89.60 per cent. Cb 2 5 . 1896; ii. Gladstone, J. H. The Relation between the refrac- tion of elements and their chemical equivalents. Proc. Roy. Soc., 60, 140-146. Ztschr. phys. Chem., 22, 648. Specific refraction Be=-733. Atomic refraction Be=6.6. 1896; 12. Ortloff, W. Beitrage zur Kenntniss eutropischer Reihen. Ztschr. phys. Chem., 19, 201. Quote physical properties in discussion. 1897; I. Havens, Franke S. The Separation of Aluminium and Beryllium by the action of Hydrochloric Acid. Amer. J. of Sci., (4) 4, 111-114. Chem. Centrbl., 1897, II, 810. Bull. soc. chim., (3) 18, 1129. Chem. News, 76, in (complete). Analyst, 23, 109. Separates Be and Al quantitatively by means of the in- solubility of A1C1 3 .6H 2 O in ether and water (1:1), saturated wtih HC1 gas. 1897; 2. Havens, Franke S. Trennung von Aluminium und Beryllium durch Salzsaure. Ztschr. anorg. Chem., 16, 15-18. Chem. Centrbl., 1898, I, 476. Bull soc. chim., (3) 26, 163. J. Chem. Soc. (London), 74, 142. Same as 1897; i. 1897; 3. Woge, Paul. Ueber die Wertigkeit des Berylliums. Inaugural Dissertation, (Berlin), 1897. See 1897; 4. BIBLIOGRAPHY OF BERYUJUM 139 1897; 4. Rosenheim, A. and Woge, P. Ueber die Wertigkeit des Berylliums. Ztschr. f. anorg. Chem., 15, 283-318. Bull. soc. chim., (3) 20, 308. J. Phys. Chem., 2, 400. Chem. Centrbl., 1897, II, 1131. Chem. News, 78, 160. J. Chem. Soc. (London), 74, 71. Extensive research on the oxalates, tartrates, molybdates and sulphites of beryllium to show their differences from the corresponding salts of Al, Fe and Cr, ending with the preparation of BeCl 2 and the determination of its molecular weight in pyridine by the boiling point method. The following substances were prepared: K 2 O,2BeO,2C 2 O s -f 2^H 2 O,1 These were obtained in crystalline Na 2 O,2BeO,2C 2 O 3 + 5H 2 O, (.forms and seem to be definite basic (NH 4 ) 2 O,2BeO v 2C 2 O 3 -f 2>H 2 O, J compounds, K 2 O,BeO,2C 2 O 3 + H 2 O, Na 2 O, BeO,2C 2 O 3 + H 2 O, (NH 4 ) 2 O,BeO, 2C 2 O 3 , 2BeO.3C 2 O 3 + 6H 2 O, BeC 2 4 + 3 H 2 0, K 2 O,4BeO,2C 4 H 4 O 5 -f- 8H 2 O, NajCUBeCMC^Og -f 8H 2 O, (NH 4 ) 2 0,4BeO,2C 4 H 4 5 + 8H 2 O, K 2 O.2BeO,2C 4 H 4 O 5 + 2H,O, BeO,MoO 3 .2H 2 O, io(2BeO.MoO 3 ) + 2(NH 4 ) 2 O,3MoO 3 -f i8H 2 O, K 2 0,2BeO,3S0 2 + 9H,O, (NH 4 ) 2 0,2BeO,3S0 2 + 4H 2 O. l %97> 5- Heusler, Fr. Die Chemie bei der Temperature des elektrischen Lichtbogens. Ztschr. anorg. Chem., 14, 173. Compilation of the work on carbides including that of beryllium. 1897 ; 6. Gladstone, J. H. and Hibbert, W. The Molecular Refraction of dissolved Salts and Acids. J. Chem. Soc. (London), 71, 823. I4O CHEMISTRY OF BERYLLIUM Compared the molecular refraction of solid and dis- solved BeSO 4 4H,O. Molecular refraction of solid=47.4i. Molecular refraction of liquid=47.94. 1897; 7. Mosnier, A. Sur quelques combinaisons de 1'iodure de plomb avec d'autres iodures metalliques ou organi- ques. lodure double de plomb et de glucinium. Ann. de chim. et de phys., (7) 12, 374-426. J. Chem. Soc. (London), 76, 222. Treated carbonate of beryllium with concentrated HI, then added lead iodide as long as it dissolved. By cooling, obtained fine yellow needles decomposed by water. From analysis he calculates the formula Be 2 I 6 . 3 PbI 2 , ioH 2 0. 1897; 8. Lebeau, P. Sur la preparation des alliages de glucin- ium. Allaiges de glucinium et de cuivre. Comptes rend., 125, 1172. Bull. soc. chim., (3) 19, 54. Chem. Centrbl., 1898, I, 310. Chem. Ztg., 22, 17. Ztschr, anorg. Chem., 19, 351. J. de pharm. et de chim., (6) 7, 240. Chem. News, 77, 44. J. Chem. Soc. (London), 74, 292. J. Soc. Chem. Ind., 17, 1152. Owing to the ease with which Be and C. combine at high temperatures, the metal can not be reduced from its oxide in the electric arc. Alloys can be prepared however, by reducing BeO in this manner in contact with other metals or metallic oxides. Prepared alloys with Cu, Cr, Mo and W, but describes those of copper only. With 10 per cent, of Be the copper alloys are pale yellow, almost white. With 5 per cent. Be they are yellow, easily polished and malleable cold or hot. As low as 5 per cent. Be alters appearance of Cu and makes it sonorous. Alloy of 1.32 per cent, is golden yellow and can be easily filed and forged. BIBLIOGRAPHY OF BERYLUUM 14! 1898; i. Lebeau, P. Recherches sur le glucinium et ses com- poses. Academic Dissertation, Paris, 1898. 1898; 2. Lebeau, P. Sur un procede de preparation des bronzes de glucinium. Bull. soc. chim., (3) 19, 64. Chem. Centrbl., 1898, I, 496. See 1897; 8. 1898; 3. Lebeau, Paul. Preparation du glucinium par electro- lyze. Comptes rend., 126, 744. Chem. Centrbl., 1898, I, 879. Chem. News, 77, 173. J. Phys. Chem., 3, 185. Amer. J. Sci., (4) 7, 155. Zeit f. Elec., 5, 31. Bull. soc. chim., (3) 19, 409. Chem. Ztg., 22, 245. J. Chem. Soc. (London), 74, 511. J. de phar et de chim., (6) 7, 345. J. Soc. Chem. Ind., 17, 386. Obtained metallic beryllium by electrolysis of BeF 2 .NaF in nickel crucible. Melted over bunsen burner and then passed current of 6-9 amperes at 35-40 volts removing source of heat. Made salt by fusing exact equivalents i- 1 of the two fluorides. Nickel crucible negative pole and graphite stick positive pole. 1898; 4. Lebeau, Paul. Gewinnung von Beryllium durch Elec- trolyze. Beryllium Legierungen. Elektrochemische Zeitschrift, 5, in. Chem. Centrbl., 1898, II, 750. J. Soc. Chem. Ind., 17, 155. Amer. Chem. J., 27, 487. Article is fully as complete as 1898; 3 and much the same in character although a separate communication Says Nilson and Petterssen found BeCl 2 to be a non- conductor, which he confirmed and found same to be 142 CHEMISTRY OF BERYLLIUM true of the bromide and fluoride. Added NaF to make, mixture conduct electricity. Used nickel crucible and carbon anode with a current of 20 amperes and 80 volts (vide 1898; 3). Heated first with bunsen burner but later controlled heat by current alone. Kept at low redness. Fine hexagonal Be obtained free from iron and nickel \\ith a specific gravity of 1.73 at 15. Gives properties of beryllium. Made alloys with copper and gives their properties. One-half per cent. Be makes copper quite sonorous. 1.32 per cent. Be in copper is a gold yellow metal and finely sonorous. 1898; 5. Lebeau, Paul. Sur le traitement industriel de 1'emer- aude au feur electrique. Comptes rend., 126, 1202. Bull. soc. chim., (3) 19, 940. Ztschr. f. Elek., 5, 39. Chem. News, 77, 285. Chem. Ztg., 22, 380. Heated beryl in carbon tube in electric furnace at 95 amperes and 50 volts for ten minutes and dissolved in hydrofluoric acid. This removes silicon and alumin- um since A1F 3 is insoluble. Solution worked up for beryllium as ordinarily. 1898; 6. Lebeau, Paul. Sur 1'iodure de glucinium. Comptes rend., 126, 1272. Bull. soc. chim., (3) 19, 800. Chem. Centrbl., 1898, II, 85. Ztschr. phys. Chem., 28, 570. Chem. News., 77, 266. J. phar. ciiim., (6) 7, 59 2 - J. Chem. Soc. (London), 74, 580. Made BeI 2 by action of iodine on the carbide and stud- ied its properties exhaustively. Specific gravity 4.20, fuses at 510 and begins to sub- lime at once, boils 585-595. BIBLIOGRAPHY OF BERYUJUM 143 Insoluble in benzine and toluene, soluble in carbon disul- phide. Attacked violently by water and decomposed by flourine, chlorine and bromine. 1898; 7. Lebeau, Paul. Sur un borocarbure de glucinium. Comptes rend., 126, 1347. Bull. soc. chim., (3) 19, 823. Chem. Centrbl., 1898, II, 86. Chem. Ztg., 22, 425. Ztschr. f. Elek., 5, 91. Chem. News, 77, 289, (complete). J. Chem. Soc. (London), 74, 581. Prepared 3Be 2 C.Bo 6 C by heating a mixture of BeO and B in a carbon crucible in the electric furnace. Crys- talline with specific gravity of 2.4. 1898; 8. Lebeau, Paul. Sur la preparation et les proprieties du fluorure de glucinium anhydre et de 1'oxyfluorure de glucinium. Comptes rend., 126, 1418. Bull. soc. chim., (3) 19, 824. Chem. News, 77, 288, (complete). ' Ztschr. f. Elek., 5, 118. Made BeF 2 by evaporating a solution .of Be(OH) 2 in excess of HF and drying in HF gas in platinum tube, obtaining thereby a transparent glassy, deliquescent fluoride, if he raised heat to drive off all the water, he obtained a basic residue of approximate BeF.2BeO but different analyses did not agree closely. Made purest BeF 2 by heating BeF 2 .NH 4 F in platinum tube in CO 2 gas. Anhydrous, glassy, sublimes in little transparent crystals above 800, specific gravity 2.1. Soluble in H 2 O and in 90 per cent, alcohol. Attacked by H 2 SO 4 . 1898; 9. Hober, Rudolf and Kiesow, Friedrich. Ueber den Geschmack von Salzen und Laugen. Ztschr. phys. Chem., 27, 601. Chem. Centrbl., 1899, I, 332. 144 CHEMISTRY OF BERYLLIUM Found that BeCl 2 and BeSO 4 4H 2 O have the same sweet taste at equal cation concentrations. 1898; 10. Boudard, O. Sur les sables monazites de la Caro- lina du Nord. Bull. soc. chim., (3) 19, 10. Chem. Centrbl., 1898, I, 435. Gives method of analyzing monazite including separa- tion of beryllium. 1898; ii. de Gramont, A. Analyse spectrale des mineraux nonconducteurs par les sels fondus. Bull, de la soc. franc, de min., 21, 109. Comptes rend., 126, 1513. Ztschr. f. Kryst, 32, 637. J. Chem. Soc. (London), 74, 636. Obtains the blue line, 457.3 easily in spark spectra by fusing beryl with lithium carbonate. 1898; 12. Curtius and Rissom. Neue Untersuchungen iiber den Stickstoffewasserstoff N 3 H. J. f. prakt. Chem., 58, 292. J. Chem. Soc., 76, 92. Attempts to make (N 3 ) 2 Be by action of (N 3 ) 2 Ba upon BeSO 4 but failed as it immediately broke down into N 3 H and Be(OH) 2 . 1898; 13. Florence, W. Darstellung mikroskopischer Krystalle in Lothrohrperlen. Ztschr. f. Kryst, 33, 180. 1898; 14. Goldschmidt, Dr. Hans. Ueber em Neues Verfahren sur Darstellung von Metallen und Legeierungen und von Korund, sowie zur Erzielung hoher Temperaturen. Ztschr. angewandte Chem., 1898, 822. Claims that Lebeau is wrong and that BeO is at least reduced in part by Al but comes in fine powder mixed with the slag. His proof is, however, simply that the mass grows dark and on ignition becomes white again and is far from convincing. BIBLIOGRAPHY OF BERYUJUM 145 1898; 15. Liebermann, Louis. Verfahren sur Darstellung von Beryllium, D. R. P. 101326. Patent bl. 20, 193. Chem. Ztg., 23, 525. Ztschr. f. Elek., 5, 366. Chem. tech. Rep., 38, 120, 254. Electr. Chem. Ztg., 6, 81. Chem. Centrbl., 1899, I, 1096. Details of a patent of very doubtful value. 1898; 16. Liebermann, Louis. Verfahren zur Darstellung von Beryllium, D. R. P. 104632. Patent bl., 20, 816. Chem. Ztg., 23, 944. Ztschr. f. Elektr. Chem., 6, 284. Electro. Chem. Ztg., 6, 222. Ztschr. f. Elek., 5, 428. Chem. Tech. Rep., 38, 456 . Chem. Centrbl., 1899, II, 1073. Patent of very doubtful value. 1898; 17. Roman, R. J. Beryllium Legierungen. Chem. Ztg., 22, 83. Claims priority over both Liebermann and Lebeau. 1898; 18. Moissan. Electrolytische Darstellung von Beryllium und zeiner Legierungen und Darstellung von Beryllium Legierungen in Elektrischen Ofen. Chem. Ztg., 22, 650. Report of Lebeau's work before section on Elektro- chemistry of International Congress of Applied Chemis- try, Vienna 1898. 1898; 19. Van Bemmelen, J. M. Die Absorption. Unsetzung der Krystallinischen Hydrate in amorphe Substanzen. Ztschr. f. anorg. Chem., 18, 126. Effects of heat on the "crystalline" and colloidal beryl- lium hydrate. 1898; 20. Franck, Leon. Studien iiber Aluminium als Reduc- tionsmittel. Chem. Ztg., 22, 244. 10 146 CHEMISTRY OF BERYUJUM Claims that by heating BeO and Al in closed glass tube a reduction takes place, but gives no proof of the fact except that a gray mass, attacked by nitric acid, was formed. Probably incorrect as Lebeau has shown. 1899; I - Petersen, . Note on preparation of pure beryl- lium oxide. Chem. Ztg., 23, 439. 1899; 2. Meyer, Stefan. Ueber die Magnetischen Eigenschaf- ten der Elements (Beryllium). Monatshefte, 20, 372. Ann. der Phys. (Wied.), 68, 324. J. Chem. Soc. (London), 76, 587. Chem. Centrbl., 1899, II, 163, 740. Gives the magnetic susceptibility of beryllium as directly observed at 15 as -f 33.8 X io~ 6 in absolute units and atomic susceptibility for i gram per liter as -f -72X io~*. 1899; 3. Meyer, Stefan. Magnetisirungszahlen anorganische Verbindung. Monatshefte, 20, 799. Ann. der Phys. (Wied.), 69, 236. Chem. Centrbl., 1900, I, 5. J. Chem. Soc. (London), 78, 7. Determined the magnetic susceptibility of beryllium chloride, oxide, hydroxide, carbonate and sulphate. 1899; 4. Pozzie-Escot, M. E. Analyse microchimique. Ann. de chim. anal., 4, 377. Determines beryllium microscopically by crystals of the double oxalate of beryllium and potassium. Drawing of crystals given in original. 1899; 5. Havens, F. S. and Way, A. F. Separation of Iron from Chromium, Zirconium and Beryllium by the Action of Gaseous Hydrochloric Acid on the Oxides. Amer. J. of Sci., (4) 8, 217. J. Chem. Soc. (London), 78, 50. Removes iron by hydrochloric acid gas mixed with a little chlorine at temperatures so low as 200-300. BIBLIOGRAPHY OF BERYLLIUM 147 Higher temperatures act quicker but if much iron is present some of the beryllium may be carried away mechanically. 1899; 6. Havens, F. S. and Way, A. F. Die Trennung des Eisens, von Chrom, Zircon und Beryllium durch die Einwirkung von gasformiger Salzsaure auf die Oxyde. Ztschr. f. anorg. Chem., 21, 389. Review Amer. Chem. Research, 5, 102. Analyst., 25, 23. Same as 1899; 5 but separately transmitted. 1899; 7. Liebermann, L. Beryllium Legierungen. Chem. Ztg., 24, 43. Claims priority over Lebeau. 1899; 8. Austin, Martha. The double Ammonium Phosphates of Beryllium, Zinc and Cadmium in Analysis. Amer. J. of Sci., (4) 8, 206-216. Chem. Centrbl., 1899, II, 791. J. Chem. Soc. (London), 78, 49. Rev. Amer. Chem. Res., 5, 102. J. Soc. Chem. Ind., 19, 72. Shows that the precipitation of beryllium as ammonium beryllium phosphate and ignition to the pyrophosphate does not give uniform results. 1899; 9. Austin, Martha. Die Ammoniumdofpelphosphate von Beryllium, Zinc and Cadmium in analytische Bezie- hung. Ztschr. anorg. Chem., 22, 207-220. Chem. Centrbl., 1899, II, 1032. Same as 1899; 8 but separately transmitted. 1899; 10. Ley, H. Studien iiber die hydrolytische Dissocia- tion der Salzlosungen. Ztschr. phys. Chem., 30, II, 218. Chem. Centrbl., 1899, II, ion. J. Chem. Soc. (London), 78, II, 67. Says basicitv of Be(OH) 2 is eleven times as great as that of A1(OH) 3 . Found beryllium salts not so strongly 148 CHEMISTRY OF BERYLLIUM hydrolyzed as aluminum salts. Used inversion method. Worked on sulphate and chloride. 1899; ii. Lebeau, P. Recherches sur le glucinium et ses com- poses. Ann. die chim. et de phys., (7) 16, 457-503. Chem. Centrbl., 1899, I, 963. J. Phys. Chem., 4, 222. J. Chem. Soc. (London), 76, 554. Ztschr. anorg. Chem., 21, 86. Ztschr. f. Kryst, 34, 629. This is a resume of all of Lebeau's work on beryllium and is the best and most comprehensive article written on beryllium and its compounds. 1899; 12. Woulff, G. Optische Studien an pseudosymmetris- chen Krystallen, Das Beryllium Sulfat. Ztschr. f. Kryst., 17, 592. Chem. Centrbl., 1900, II, 73. BeSO 4 .4H 2 O is strongly double refractive. The crys- tals are negative and uniaxial. 1899; 13. Rosenheim, A. u. Itzig, H. Ueber einige complexe Salz der Weinsaure und Apfelsaure und ihr specifische Drehungsvermogen. Berichte, 32. 3424. Chem. Centrbl., 1900, I, 170. Bull. soc. chim., (3) 24, 520. J. Chem. Soc. (London), 78, 135. J. Russ. Phys. and Chem. Soc., 32, II, 57. Worked on the mono- and diberyllium tartrates of Ros- enheim and Woge (1898; 4) to determine their molecu- lar rotation and found that the introduction of beryl- lium into the molecule greatly increased the rotatory power whether right or left. Diberyllium tartrate showed a molecular rotatory power of 225-242 not effected by dilution. Monoberyiljlium tartrate gave ro- tation of 125. Made double mallates with beryllium to correspond to the tartrates before described. BIBLIOGRAPHY OF BERYLLIUM 149 Addition of beryllium sulphate does not effect rotatory power of dextrose, or chlorosuccinic acid. 1899; 14. Amphola and Ulpiani. Sull'azione viduttrice dei batteri dinitrificanti. Gazz. chim. Ital., 29, 49. Bull. soc. chim., (3) 24, 363. J. Chem. Soc. (London), 76, IE, 444. Studied the action of the denitrifying bacteria and found that B. denitrificans V. reduced beryllium nitrate and, in general, the more electro-positive the metal and the lower its atomic weight the more rapidly doesdenitri- fication take place. 1900; i. Bruner, Ludwig. Ueber die Hydrolyse der Salz- losungen. Ztscnr. phys. Chem., 32, 133. Chem. Centrbl., 1900, I, 532. Bull. soc. chim., (3) 26, 599. Gives figures for the hydrolysis of solutions of BeCl 2 , Be(NO 3 ) 2 , and BeSO 4 , compared with corresponding salts of iron and aluminum. The beryllium salt? showed smaller degree of hydrolysis than either of the others. 1900; 2. Nielsen, R. A. Gliihkorper aus Beryllerde. Danish patent No. 4278. 1900; 3. Formanek, J. Nachweis der Metallsalze mittelst der Absorptionsspectralanalyse unter Verwendung von Alkanna. Ztschr. anal. Chem., 39, 409. If one treats Alkanna tincture with neutral beryllium chloride or nitrate, solution is red violet and fluoresces strong orange red. The absorption spectra consists of three distinct bands with position varying according to conditions. 1901; i. Hartley, W. Noel. On the Quantitative Spectra of Beryllium. Proc. Roy. Soc., 1902, 283-285. Chem. News, 85, 25. 150 CHEMISTRY OF BERYUJUM J. Chem. Soc. (London), 82, 237. Chem. Ztg., 25, 1142. Am. J. Sci., (4) 13, 156. Solutions of beryllium salts of diminishing concentra- tion examined spectroscopically and the gradual extinc- tion of the several lines noted. Two lines A. 3130.3 and 2478.1 are still visible when the concentration has fallen as low as .00000 1 per cent. 1901 ; 2. Urbain, G. and Lacombe, H. Sur un nouveau sel de glucinium volatile. Comptes rend., 133, 874. Chem. Centrbl., 1902, I, 97. J. Phys. Chem., 6, 349. Chem. News, 84, 304. Chem. Ztg., 25, 1115-. J. Amer. Chem. Soc., 24, 201. Ztschr. anorg. Chem., 33, 227. Made Be 4 O(C 2 H 3 O 2 ) 6 by action of glacial acetic acid on dry acetate, excess of glacial acid being present. Melts at 283-284, distills under normal pressure at 330-331 and its vapor can be heated to 360 without decomposition. Density of vapor determined at boiling point of mercury 13.9. Not effected by solution in strongest acetic acid even if same is saturated with hy- drochloric acid gas and heated in closed tube to 150. 1901 ; 3. Wells, H. L. Generalizations on Double Halogen Salts. Amer. Chem. Jour., 26, 390. Chem. Centrbl., 1901, II, 1327. Includes 2KF.BeF 2 , KF.BeF 2 and 2KCl.BeCl 2 in his list of double halides. 1901 ; 4. Friedel, G. Sur un silicate de lithium crystallize. Bull. soc. franc, de min., 24, 141. Bull. soc. chim., (3) 25, 1008. Chem. Centrbl., 1901, II, 88. Sought to obtain some mixed crystals of L,i 2 SiO 8 and Be 2 SiO 4 and succeeded in doing so. Claimed an ex- BIBLIOGRAPHY OF BERYLLIUM 151 ample of isomorphism similar to that between albite and anorthite. 1901 ; 5. Factor. Ueber die Einwendung des Natrium thiosul- phate auf einige Metallsalze. Chem. Centrbl., 1901, II, 879, from Pharm. Post, 34, 485. J. Chem. Soc. (London), 82, II, 25. Claimed BeS 2 O 3 .nH 2 O. 1902; i. Wyrouboff, G. Sur quelques oxalates de glucine. Bull. soc. franc, de min., 25, 71. Chem. Centrbl., 1902, II, 631. Again makes claims for the completely disproved theory of trivalent beryllium. Made the normal oxalate BeC 2 O 4 .3H 2 O and gives crystal measurements. Made also double oxalates of beryllium with potassium, rubid- ium, sodium and lithium. 1902; 2. Wyrouboff, G. Sur la separation de la glucine. Bull. soc. chim., (3) 27, 733. Chem. Centrbl., 1902, II, 610. J. Chem. Soc. (London), 82, 605.. Analyst., 27, 287. Decomposes beryl with KOH, removes SiO 2 , evapo- rates solution of chloride to small volume and precipi- tates beryllium as a double oxalate by means of HKC 2 4 . 1902 ; 3. Lacombe, H. Sur un type de composes du glucinium, Comptes rend., 134, 772-74. Chem. Centrbl., 1902, I, 1087. Amer. J. Sci., (4) 13, 471. J. Chem. Soc. (London), 82, I, 418. Chem. News, 85, 215. Chem. Ztg., 26, 373. Made the basic formate, acetate, propionate, isobuty- rate, butyrate, and isovalerianate, all of the same type as the basic acetate, viz., Be 4 O(A) 6 . All made by action of anhydrous acid in excess on the carbonate I5 2 CHEMISTRY OF B^RYLUUM and sublimation under diminished pressure. All at- tempts to saturate and obtain the normal salt failed. Formate, insoluble in all solvents. Solubility increases with increased molecular weight of acid radicle. CONSTANTS. M. P. B. P. 760 mm. B.P. 19 mm. Basic formate, sublimes without fusion Basic acetate 283-284 330-331 sublimes Basic propionate 119-120 339-341 221 Basic isobutyrate 76 336-337 216 Basic butyrate liquid 239 Basic isovalerianate liquid 254 1902; 4. Weinland, R. F. and Schlegelmilch. Ueber Doppel- salze des Jodtrichlorids mit Chloridin zweiwertigen Metalle. Ztschr. f. anorg. Chem., 30, 140. J. Chem. Soc. (London), 82, 315. Prepared 2lCl 3 .BeCl 2 .8H 2 O by passing chlorine into a hydrochloric acid solution of BeCl 2 and iodine at 10. Gold yellow, very hydroscopic needles. Very unstable. 1902 ; 5. Reubenbauer, Jacob. Ueber die Loslichkeit von Schwermetallhydraten in Natron. Ztschr. anorg. Chem., 30, 334. J. Chem. Soc. (London), 82, II, 396. Found that NaOH dissolved Be(OH) 2 in proportion to the concentration of the NaOH. 1903; i. Freundlich, H. Uber das Ausfallen Kolloidaler Los- ungen durch Elektrolyte. Ztschr. f. phys. Chem., 44, 129. Chem. Centrbl., 1903, II, 232. Studied the action of BeCl 2 and BeSO 4 on colloidal As 2 S 8 . 1903; 2. Vogel, Fritz. Untersuchungen iiber Nitrite, (Beryl- lium nitrite). Ztschr. anorg. Chem., 35, 385. Chem. Centrbl., 1903, II, 327. Could not obtain a nitrite of beryllium by precipitating BIBLIOGRAPHY OF BERYLLIUM 1*3 sulphate with barium nitrite. Precipitate immediately hydrolyzed and lost oxides of nitrogen. His precipi- tated hydroxide contained but a small amount of nitrogen Be :NO 2 : :i 10.15. 1903; 3. Renz, Carl. Ueber Verbindungen von Metalhaloiden mit organischen Basen. Ztschr. anorg. Chem., 36, 100-118. Chem. Centrbl., 1903, II, 578. Succeeded in making but one compound of beryllium with the organic bases, viz., Beryllium chloride quin- oline, BeCl 2 (C 9 H 7 N 2 ) 2 +H 2 O. 1903 ; 4. Renz, Carl. Ueber die Loslichkeit der Hydroxide des Aluminiums, Berylliums und Indiums in Ammoniak und Aminbasen. Berichte, 36, 2751-55. Chem. Centrbl., 1903, II, 823. Beryllium hydroxide is quite insoluble in methyl, ethyl, dimethyl and diethyl amine. This gives a quick and accurate and quantitative separation from aluminum. So- lution of beryllium and aluminum are dissolved in dilute nitric acid, evaporated to remove acid, taken up in water, shaken up with large excess of ethyl-amine and the precipitated beryllium hydroxide carefully washed and aluminum determined in filtrate. I 93> 5- Van Oordt, G. Verfahren zur Reinabscheidung des Berylliums aus seinem Gemenge mit Aluminium und Eisen. German Patent No. 155,466. Chem. Centrbl., 1904, II, 1354. Separates the basic acetate by its solubility in chloro- form. 1904; i. Pollok, James Holms. On the Extraction of Gluci- num from Beryl. Trans. Royal. Dublin Society, (2) 8, 139-152. Extracted beryl by fusion with its own weight of sod- ium hydroxide in a salamander crucible. After separat- ing silica from hydochloric acid solution, he precipitated 154 CHEMISTRY OF BERYLLIUM with ammonia, filtered and dissolved the iron, aluminum and beryllium in hydrochloric acid and saturated with hydrochloric acid gas thereby separating the main quan- tity of aluminum. Separated from iron by ammonium carbonate and sulphide. Also in other experiments sep- arated aluminum as alum in the ordinary way. Made perfectly free from aluminum by precipitating same with HKF 2 in dilute HF solution. In strong solution some beryllium is also precipitated. Basic carbonate finds formula approximately BeCO 3 .- 2Be(OH) 2 .2H 2 O. Carbonate is soluble to the extent of 58 grams in one liter saturated ammonium carbonate. Sulphate and chloride made in the usual manner, gives melting point of BeCl 2 as about 400 and boiling point at about 500. Made impure metallic beryllium by action of Na on anhydrous chloride in nickel crucible. Dark gray powder. Could not fuse at atmospheric pressure. In atmosphere of H it volatilized without fusion. 1904; 2. Haber, F. and Van Oordt, G. Ueber Berylliumver- bindungen. I Mitteilung. Ueber Beryllium Hydrox- ide. Ztschr. anorg. Chem., 38, 377-398. Chem. Centrbl., 1904, I, 858. A study of the hydroxide of beryllium convinced them that it existed in two modifications, first, when freshly precipitated which is readily acted upon by reagents and a second or older form, produced by standing or by boiling which is much less readily attacked. >" 3- Tanatar, S. Studies upon the Valency and the Atomic Weight of Beryllium. J. Russ. Phys. and Chem. Soc., 36, 82-86. Chem. Centrbl., 1904, I, 1192. Repeats the work of Urbain and Lacombe (1901 ; 2) on the acetate and comes to the conclusion that Be is a tetravalent element with the atomic weight 18.2. BIBLIOGRAPHY OF BERYLLIUM 155 1904; 4. Haber, F. and Van Oordt. Berylliumverbindungen. II Mitteilung. Ztschr. anorg. Chem., 40, 465-. Chem. Centrbl., 1904, II, 688. Separates beryllium from aluminum and iron by the solubility of its basic acetate in chloroform. 1904 ; 5. Parsons, Charles Lathrop. A Revision of the Atomic Weight of Beryllium. Jour. Amer. Chem. Soc., 26, 721. Ztschr. anorg. Chem., 40, 400. Chem. News, 90, 61, 75. Chem. Centrbl., 1904, II, 820. Describes the preparation of pure material including the sulphate, chloride, acetyl-acetonate and basic ace- tate. States that the supposed new element noted by Kriiss and Moraht in beryllium compounds is a mixture of zinc and iron. Gives properties of the chloride, sul- phate, acetyl-acetonate and basic acetate. By the analy- sis of seven samples of beryllium acetyl-acetonate and nine of basic acetate, obtained the atomic weight 9.113. Results on sulphate unsatisfactory and the method un- reliable in the opinion of the author. 1904; 6. Neisch, A. C. A New Separation of Thorium from Cerium, Lanthanum and Didymium by Meta-nitroben- zoic acid. J. Amer. Chem. Soc., 26, 781. Chem. Centrbl., 1904, II, 848. Meta nitrobenzoic acid does not precipitate beryllium. 1904 ; 7. Myers, Ralph E. Results obtained in Electrochemical Analysis by the Use of a Mercury Cathode. J. Amer. Chem. Soc., 26, 1124. Chem Centrbl., 1904, II, 1338. Separation of beryllium from chromium and iron. By the use of a mercury cathode all the iron and chromium present in a slightly acid solution of the sulphates and beryllium sulphate can be deposited in the mercury, leav- ing pure beryllium sulphate behind. 156 CHEMISTRY OF BERYLLIUM 1904; 8. Wetherel, E. W. An Attempt to Explain the Irregu- larities of the Atomic Weights of Beryllium, Argon and Tellurium. Chem. News, 90, 260. Chem. Centrbl., 1905, I, 7. 1904; 9. Pollok, James Holms. The Heat of Formation of Glucinium Chloride. J. Chem. Soc. (London), 85, 603. Pro. Chem. Soc. (London), 20, 61. Chem. Centrbl., 1904, I, 1243, 1593. Describes the extraction of the oxide from beryl. For- mation and properties of anhydrous chloride. Melt- ing point of chloride about 400. Molecular heat of solution BeCl 2 =44.5 K, Molecular heat of solution BeSO 4 4H 2 O=o.85 K, Molecular heat of formation BeCl 2 =i55 K. Prepared metallic beryllium by action of sodium on chloride and obtained an impure product. Says metal volatilizes without fusion at ordinary pressure. 1904; 10. Parsons, Charles Lathrop. Equilibrium in the Sys- tem Beryllium Oxide, Sulphuric Anhydride and Water. J. Amer. Chem. Soc., 26, 1433. Ztschr. anorg. Chem., .42, 250. Chem. Centrbl., 1905, I, 2. Made a study of the various published sulphates of beryllium including the so-called basic sulphates and concludes that the only definite sulphates are the tetra- hydrate and dihydrate, and by the application of phase rule considerations, the basic sulphates are shown to be either the hydroxide or a solid solution of the sulphate in the hydroxide. 1904; ii. Parsons, Charles Lathrop. "Beryllium" or "Glu- cinium" Science, Dec. 9, 1904. Chem. News, 91, 75. Discussion of the proper name for element. Prefers beryllium. BIBLIOGRAPHY OF BERYLLIUM 157 1904; 12. Pollok, James Holms. The Composition of Beryl. Proc. Chem. Soc. (London), 20, 189. J. Chem. Soc. (London), 85, 1630-37. Chem. Centrbl., 1905, I, 556. By fractional sublimation of the chloride of beryllium, he obtained chlorides which on analysis yield equiva- lents for Be all the way from 4.77-18.74 and concluded the beryllium is really a mixture of two elements. Examined the oxides from the two chlorides spectro- scopically. 1905; I. Howe, James Lewis. "Glucinium" or "Beryllium." Science, Feb. 17, 1905. Chem. News, 91, 123. Reply to 1904; 10, Prefers glucinium. 1905; 2. Parsons, Charles Lathrop. "Beryllium" or "Glu- cinium." Science, Jan. 6, 1905. Chem. News, 91, 123. Chem. Centrbl., 1905, I, 1129. Reply to Howe 1905 ; i. 1905 ; 4. Parsons, Charles Lathrop. On the Complexity of Beryllium. J. Amer. Chem. Soc., 27, 233. Chem. News, 91, 92. Chem. Centrbl., 1905, I, 995, 1306. Discusses the work of Pollok (1905, 4) and claims that his results are easily explained by the action of water on beryllium chloride and that sufficient precautions were not taken to guard against its presence. 1905; 5. Parsons, Charles Lathrop. Note on the Atomic Weight of Carbon and Beryllium. J. Amer. Chem. Soc., 27, 1204. Ztschr. anorg. Chem., 46, 215. Chem. Centrbl., 1905, II, 956, 1155. Obtains new figures from his previously published analyse for the atomic weight of beryllium. By an algebraic calculation both the atomic weight of carbon 158 CHEMISTRY OF BERYUJUM and beryllium are independently obtained from the previously published figures. Atomic weight Be= 9.112. Atomic weight C =12.007. 1905 ; 6. Kahlbaum, G. W. A. and Sturm, E. Ueber die Ver- andlichkeit des Spezifischen Gewichtes. Ztschr. anorg Chem., 46, 237. Chem. Centrbl., 1905, II, 1068. Compares beryllium to other members of the same group and gives reasons why it was not used in his research. 1905 ; 7. Levi-Malvano, Mario. Gli idrati del solfato di berillio. Atti. R. Accad. die Lincei, Roma, (5) 14, II, 502-10. Ztschr. anorg. Chem., 48, 446. Chem. Centrbl., 1906, I, 321, 1223. Describes a sulphate hexahydrate of beryllium which he makes from supersaturated solution and states that it yields a blue oxide on ignition. Gives solubility curves of the hexahydrate and also the tetrahydrate. Con- cludes that a sulphate monohydrate and anhydrous sul- phate both exist. 1906; I. Parsons, Charles L. and Robinson, W. O. Equili- brium in the System Beryllium Oxide, Oxalic Anhy- dride and Water. J. Amer. Chem. Soc., 28, 555. Ztschr. anorg. Chem., 49, 178. Chem. Centrbl., 1906, II, 8. Made a study of the oxalates of beryllium in the same manner as the previous work, (1904, 10) on the sul- phate and concludes that an acid oxalate does not exist and the oxalates of beryllium alone are the mono and trihydrates. Further that all of the so-called basic oxalates are in reality solid solutions approaching the hydroxide in composition. Give a list and general discussion of basic beryllium compounds and state their belief that no definite basic compounds claimed to have been formed in presence of water have any real exist- BIBLIOGRAPHY OF BERYUJUM 159 ence as chemical compounds. Cut and drawing of crystals of the trihydrated oxalate. Purification of material by recrystallization of the basic acetate from glacial acetic acid. 1906; 2. Parsons, Charles L. and Barnes, Stuart K. The Sep- aration and Estimation of Beryllium. Science, 24, 240. J. Amer. Chem. Soc., 28, 1589. Chem. Centrbl, 1907, I, 67. Ztschr. f. anal. Chem., 46, 292. Chem. Centrbl., 1907, II, 96. J.. Chem. Soc., 92, 52. Chemical Abstracts, i, 27. Beryllium is separated from aluminum and iron by the complete solubility of its hydroxide in a hot saturated solution of acid sodium carbonate ferric hydroxide and aluminum hydroxide being completely insoluble. Dou- ble precipitation is essential. Beryllium hydroxide must be washed with water containing an electrolyte in so- lution, for when pure it rapidly washes through the filter in a colloidal condition. 1906; 3. Parsons, Charles L, and Robinson, W. O. The Basic Solutions of Beryllium Sulphate. Science, 24, 202. Freezing-point determinations, on both dilute and con- centrated solutions, show that, per mol of SO 3 , any increase in basic ratio over the normal salt raises the freezing-point. The osmotic effect of the sulphate is, therefore, always decreased by dissolving in it its own hydroxide. The electrical conductivity of the basic solutions is less than that of normal solutions contain- ing the same amount of SO 3 . Migration experiments show that beryllium forms no part of the anion. The basic solutions are not precipitated by crystalloids; but on dialysis hydroxide is left on the membrane, and the dialyzed solution has a lower basic ratio. l6o CHEMISTRY OF BERYLLIUM 1906; 4. Parsons, Charles L. and Roberts Edwin J. Beryllium Carbonate. Science, 24, 39. Normal beryllium carbonate can not be made at ordi- nary pressures in contact with water. BeCO 4 -f-4H 2 O described by Klatzo does not exist, and attempts to make it by his method yield only slightly carbonated hy- droxide. Basic beryllium carbonate appears to have no definite composition and can be almost completely con- verted into the hydroxide by boiling in water. All at- tempts to increase the proportion of the CCX components over the proportion 2Be(OH) 2 .BeCO 3 failed, although CO 2 was passed for three months through the basic car- bonate under slightly increased pressure. The basic car- bonates described in literature must have contained at least one or two per cent, of the carbonate used as a solvent or precipitant. 1906; 5. Parsons, Charles L. and Fuller, Carl T. Further Study of the Sulphates of Beryllium. Science, 24, 202. Crystals were obtained from solutions with a ratio as high as 3BeO/2SO 3 . These crystals are in every case the normal tetrahydrate, and by their separation the mother-liquors are rendered more basic. Repeated at- tempts to obtain the hexa-hydrate described by Levi- Malvano (Ztschr. anorg. Chemic, 48, 446,) have re- suited in failure. Although the conditions described by that author were faithfully followed and other meth- ods used, the tetrahydrate invariably separated. 1906; 6. Van Oordt, G. Verfahren Zur Uberfiihrung von Beryllium Hydroxide in einen nicht nur fur Alkali, sondern auch fur Saure schwerloslichen bejw. unlos- lichen Zustand. Kl. Patent, I2tn. No. 165,488 of Sept. 12, 1903. Chem. Centrbl., 1906, I, 108. A patent on the principle published by Haber and Van BIBLIOGRAPHY OF BERYLLIUM l6l Oordt (1904; 2) which he claims to apply to a method of separation. 1906; 7. Brail, F. and Van Oordt, G. Verfahren Zur Tren- nung der Beryllerde von Thonerde und eventuell Eisen. Kl. Patent, I2m. No. 175,452. Chern. Centrbl., 1906, II, 1370. Chemical Abstracts, I, 2316, 2514. A patent for the separation of beryllium on the princi- ple described in 1906; 2. 1906; 8. Glassmann, B. Zur quantitativen Trennung des Beryllium von Aluminium. Berichte, 39, 3366-67. Chem. Centrbl., 1906, II, 1584. Chem. Abs., i, 151. Claims to separate by essentially the same method as proposed by Berthier (1843; 2 ) an d discarded as early as 1844 0844; i) by Bottinger. 1906; 9. Glassmann, B. Zur quantitativen Bestimmung des Berylliums. Berichte, 39, 3368-69. Chem. Centrbl., 1906, II, 1584. Chem. Abs., i, 152. Precipitates beryllium hydroxide from neutral solution of pure salts by a mixture of potassium iodide and iodate after previous removal of iron and alumina. Has the advantage over NH 4 OH that the precipitate is easily washed. 1906 ; 10. Tanatar, S. Uber die Wertigkeit und das Atom- gewichte des Berylliums (Spezifische Warme des Beryl- liums oxyds). Jour. Russ. Phys. Chem. Ges., 38, 850-54. Chem. Centrbl, 1906, II, 1807. Determines the specific heat of the oxide at 100-117 as .2898 and calculates therefrom an abnormally low specific heat for the metal, and argues therefrom for the tetravalency of the element exactly as the well known ii l62 CHEMISTRY OF BERYIJJUM low specific heat of the element was formerly used as an argument for its trivalency. 1906; ii. Olmstead, Charles M. Die Bandenspektren nahe verwandte Verbindungen. Zeit. f. wiss. Photographic, Photophysic u. Photo- chemie, 4, 255-91. Chem. Centrbl., 1907, I, 147. Studied the band spectra of Ba, Sr, Ca and Mg. Could obtain no spectrum from beryllium chloride and thinks temperature was probably not high enough for this pur- pose. 1906; 12. Friedheim, Carl. Zur quantitativen Trennung des Berylliums und Aluminiums. Berichte, 39, 3868-69. Chem. Centrbl., 1907, I, 191. Chem. Abs., I, 277. Calls attention to the fact that Glassmann's (1906; 8) supposed new method had been proposed much earlier and tried by several authors. 1906; 13. Parsons, Charles L. Beryllium Nitrate. Science, 25, 402. Prepares Be(NO 3 ) 2 .4H 2 O by crystallizing from strong nitric acid. Crystals very deliquescent, lose their N 2 O 5 easily, are stable only in strong nitric acid or in air saturated with its vapor, melt in their own water of crystallization at 60.5, soluble in alcohol and in acetone. 1907 ; i. Glassmann, B. tJber die Konstitution der fettsauren Salze des Berylliums und sur Wertigkeit des letztern. Chem. Ztg., 31, 8-9. Chem. Centrbl., 1907, I, 707. J. Chem. Soc., 92, 109. Chem. Abs., i, 701. Criticises the conclusions of Tanatar (1904; 3) that the basic beryllium salts of the fatty acid series show beryl- lium to be tetravalent. Explains valency on divalency basis. BIBLIOGRAPHY OF BERYUJUM 163 1907; 2. Kiihne, K. A. Verfahren zur Darstellung von Metallen, u. s. w. Patent Kl 4oa, No. 179,403. Chem. Centrbl., 1907, I, 1474. Proposes to separate Be, Bo, Si, etc., by Goldschmidt's aluminum method by adding them to the mixture in the form of chlorates or perchlorates. 1907 ; 3. Parsons, Charles L. The Vagaries of Beryllium. Science, 26, 569-74. Chem. News, 96, 131. Address of the chairman of the Inorganic Section, To- ronto meeting, American Chemical Society. 1907 ; 4. Glassmann, B. Zur Kentniss der Chromate des Beryl- liums. Berichte, 40, 2602-4. Chem. Centrbl., 1907, II, 375. Chem. Abs., I, 2352. Claims to have made neutral chromate, BeCrO 4 .H 2 O by "neutralizing" a concentrated water solution of chromic acid with basic beryllium carbonate and evaporating. Obtained reddish yellow monoclinic crystals which are decomposed by water with separation of a basic chro- mate, to which he gives the formula, BeCrO 4 .6Be(OH), or by precipitation of ammonium chromate with BeSO 4 solution. (Other investigators who have tried to produce the chromate in this manner have obtained only indefinite basic mixtures.) I 97 ; 5 Steinmetz, Hermann. Uber Beryllium Acetate. Ztschr. f. anorg. Chem., 54, 217-22. Chem. Centrbl., 1907, II, 528. J. Chem. Soc., 92, 673. Chem. Abs., I, 2672. Basic beryllium acetate gives octahedral crystals, from organic solvents which on sublimation yield doubly re- fracting leaves and prisms. It forms an unstable com- pound, Be 4 O(Ac) 6 .3C 3 H 5 N in cold pyridine. He made 164 CHEMISTRY OF normal beryllium acetate, Be(C 2 H 3 O 2 ) 2 for the first time by heating equal parts of basic acetate and glacial acetic acid with 5-6 parts acetic anhydride for 2 hours in a sealed tube at 140. It forms double refracting small leaflets which are insoluble in water, alcohol, ether and organic solvents. They are hydrolyzed by continued boiling in water, melt with decomposition at 300 and yielding a sublimate of the basic acetate. 1907; 6. Glassmann, B. Ein Beitrage zur Bivalenz des Beryl- liums. Das Berylliumpikrat. Berichte, 40, 3059-60. Chem. Centrbl., 1907, II, 777. J. Chem. Soc., 92, 695. Chem. Abs., i, 2539. By "neutralizing" a water solution of picric acid with basic beryllium carbonate, obtained a substance in yellow scales to which he gave the formulas Be(C 6 H 2 O 7 N 3 ) 2 .3H 2 O by calculation from its BeO content. By treating with ether he states it loses one molecule of water. On drying all the water is removed and the residue was soluble in alcohol, acetone, and py- ridine but difficultly soluble in ether. In acetophenon it gave a freezing point lowering giving a molecular weight of 465. By the action of water it is hydrolyzed and yields a basic mass to which Glassmaun gives the formula Be(C 6 H 2 O 7 N 3 ) 2 .2oBe(OH) 2 . 1907; 7. Bourion, F. Action du chlor et du chlorur de soufre sur quelques oxydes. Comptes rend., 145, 62-64. Chem. Centrbl., 1907, II, 880. Chem. Abs., I, 2988. Beryllium oxide is converted into BeCl 2 by the action of a stream of Cl and S 2 C1 2 at a red heat. 1907; 8. Nicolardot, P. Glucinium ou Beryllium. Bull. soc. chim., (4) I, 675-81. Chem. Centrbl., 1907, II, 1152. Argues in favor of the French usage. BIBLIOGRAPHY OF BERYLUUM 165 1907; 9. Stein, Gerh. Uber die Darstellung einger Silicate. Ztschr. f. anorg. Chem., 55, 159-74. Chem. Centrbl., 1907, II, 1218. Obtained a meta silicate BeSiO 3 with a density 2.35 and an orthosilicate with density 2.46 by fusing the oxide with SiO 2 in a carbon tube oven electrically heated to above 2000. Melting point of each about 2000. 1907; 10. Parsons, C. L., Robinson, W. O. and Fuller, C. T. The Soluble Basic Sulphates of Beryllium. Journal of Physical Chemistry, n, 655. Chem. Centrbl., 1908, I. J. Chem. Soc., 94, 105. It is shown that a solution of beryllium hydroxide in a solution of beryllium sulphate raises the freezing point of the latter and lowers its conductivity. The solutions obtained are not colloidal nor does the beryllium enter into a complex anion as is shown to be the case when a berylonate is present. 1907; ii. Parsons, Charles L. Solution in a Dissolved Solid. Jour, of Phys. Chem., n, 660. Chem. Centrbl., 1908, I. J. Chem. Soc., 94, 89. An explanation presented with several analogous ex- periments to account for the solubility of Be(OH) 2 in solutions of beryllium salts. 1907 ; 12. Tanatar, S. and Kurowski, E. K. Uber einige Salze des Berylliums und Zirkoniums. J. Russ. Phys. Chem. Soc., 39, 936-43. Chem. Centrbl., 1908, I, 102. J. Chem. Soc., 92, 888. Adhering to his previously announced belief in the tetravalency of beryllium, he claims to have made salts of several organic acids by saturating their water solu- tions with basic beryllium carbonate. By evaporating these solutions and analyzing the solid obtained for BeO only, he calculates the formulas given below. Formate, Be(CHO 2 ) 2 , Basic Formate, Be 4 O(CHO 2 ). l66 CHEMISTRY OF BERYLUUM Crotonate, Be 4 O(C 4 H 15 O 2 ) , soluble in benzene and al- cohol, crystals, volatile with decomposition. Gives normal molecular weight in benzene. Isocrotonate, much the same as the crotonate. Laevulinate, Be 4 O(C 5 H 7 O 3 ) 6 , soluble in water, alcohol and benzene and freezing point in benzene corresponds to above. Succinate, Be 4 O(C 4 H 4 O 4 ) 3 , white powder insoluble in benzene and alcohol. Maleate and Fumarate, BeC 4 H 2 O 4 . Citraconate, BeC 5 H 4 O 4 . Also obtained derivatives of the basic butyrate and pro- prionate as follows by treating them with acetyl chloride, Be 4 O(C 4 H 7 O 2 ) 4 .(C 2 H 3 O 2 ) 2 , melting point 15, boiling point 351, soluble in benzene and ether. Be 4 0(C 4 H 5 2 ) 3 .(C 2 H 3 2 ) 3 , melting point 127, boil- point 330 without decomposition. Soluble in benzene and ether. (Note. While the acetyl derivatives of the well known butyrate and proprionate can probably be depended upon, the salts enumerated above need confirmation as it i? a perfectly simple matter to get residues of this char- acter with organic acids which will calculate almost any formula if their content of beryllium oxide is the only criterion. It should also be remembered that the ad- dition of basic beryllium carbonate to any organic acid beyond the amount necessary to form the normal salt causes solutions of the substance formed to have a higher freezing point than the solution of the normal salt, which might easily account for the molecular weights calculated within the limits of error of Tanatar's experiments. Certainly neither the normal formate nor the basic formate of Lacombe can be prepared in the presence of water, and many attempts at preparing the succinates by the compiler of this bibliography have resulted only in indefinite mixtures of variable com- BIBLIOGRAPHY OF BERYLLIUM 167 position, one of which could easily have been found to meet the description of Tanatar's succinate and still have been simply a solid solution.) 1907; 13. Tanatar, S. M. and Kurowski, E. K. Beryllium and Zirconium Benzoates. J. Russ. Phys. Chem. Soc., 1907, 39, 1630. J. Chem. Soc. (London), 94, 166. By action of water solution of sodium benzoate on a solution of beryllium acetate, he obtained a white amorphous substance, soluble in benzene and acetone which from its BeO content he assumes to be a ben- zoate of type Be 4 O(Ac) 6 and claims it is similar to a zirconium benzoate, similarly obtained as a further ar- gument for the tetravalency of beryllium. 1907; 14. Raikow, P. Weitere Untersuchungen iiber die Ein- wirkung der Kohlensaure auf die Hydrate der Metalle. Chem Ztg., 31, 55, 87. " Chem. Centrbl., 1907, I, 695. Chem. Abstracts, i, 825, 967. Beryllium forms no carbonate unless possibly a basic carbonate of composition BeCO 3 .3Be(OH) 2 . 1907; 15. Biltz, W. and Zimmermann, Fr. Ueber die Ein- wirkung von Silbernitrat and Mercurinitrat auf einige Anorganische Hydroxide. Berichte, 40, 4979-84. Chem. Centrbl., 1908, I, 444. Silver nitrate is without effect on beryllium hydroxide. Mercuric nitrate solution is colored yellowish red by the neutral hydroxide. Authors conclude from com- parison that Be (OH) 2 has an ion solubility of the high order of io~ 5 . 1908; i. Glassmann, B. Zur Konstitution der fettsauren Salze des Berylliums, iiber einige Neue Beryllium orthosalze und iiber Salze organische Orthosauren anderer Elements. Berichte, 41, 33. Argues for his constitutional formulas for organic l68 CHEMISTRY OF BERYLLIUM beryllium compounds as against Tanatar. Also offers the following new salts all of which need confirmation by equilibrium experiments before being accepted (See note 1907; 13): Lactate, Be 2 O(C 3 H 5 O 3 ) 2 .H 2 O, crystals, soluble in water ; Glycolate, Be 2 O(C 2 H 3 O 3 ) 2 .H 2 O, crystals, soluble in water ; Trichloracetate, Be,O(C 2 Cl 3 O 2 ) 2 , glassy mass; Ethylglycolate, Be 2 O(C 2 H 5 .C 2 H 2 O 3 ) 2 .H 2 O ; Phenylglycolate, Be 2 O(C 6 H 5 .C 2 H 2 O 3 ) 2 ; Chloroproprionate, Be 2 O(C 3 H 4 ClO 2 ) 2 .H 2 O ; Salicylate, Be 2 O(C 7 H 5 O 8 ) 2 ; Cyanacetate, Be 4 O(C 2 H 2 CNO 2 ) fl , glassy mass. Dichloracetate, Be 4 O(C 2 HCl 2 O 2 ) 6 , crystalline; Monobromacetate, Be 4 O(C 2 H 2 BrO 2 ) c , crystalline. Monochloracetate, Be 4 O(C 2 H 2 ClO 2 ) 6 , crystalline. Monobromproprionate, Be 4 O(C 3 H 4 BrO 2 ) 6 , crystalline. All the above "salts" are easily soluble in water, in- soluble in benzene and chloroform and all non-volatile. All were made by "neutralizing" the water solution of the acid with basic beryllium carbonate and evaporat- ing. The composition of the solid residue was in- ferred from the content of BeO found, adding water of crystallization where necessary to make the calcu- lated quantity of oxide agree therewith. 1908; 2. Noyes, A. A., Bray, W. C. and Spear, E. B. A Sys- tem of Qualitative Analysis for the Common Elements. Part III Analysis of the Aluminium and Iron Groups including Beryllium, Uranium, Vanadium, Titanium. Zirconium and Thallium. J. Amer. Chem. Soc., 30, 481 1908; 3. Cameron, F. K. and Robinson, W. O. The Action of Carbon Dioxide under Pressure upon a Few Metal Hydroxides at oC. Jour. Phys. Chem., 12, 562. The authors show that no definite carbonate of beryllium exists. INDEX OF AUTHORS. Ampola, G., 1899, 14. Atkinson, E. A., 1895, 9. Atterberg, Albert, 1873, 7, 8 ; 1874, i ; 1875, 4. Austin, Martha, 1899, 8, 9. v. Awdejew, 1842, 2. Balard, A. G., 1834, i. Becquerel, A. C., 1831, 2. Behrens, H., 1891, 2. Berthier, Pierre, 1843, 2. Berthemot, 1831, i. Berzelius, J. J., 1815, i ; 1823, i ; 1825, i ; 1826, i, 2; 1831, 3; 1833, 2 ; 1834, 2. Blake, James, 1882, i. Bilitz, W., 1907, 15. Biot, Jean Baptiste, 1838, i. de Boisbaudran, Lecoq, 1882, 3. Bondard, O, 1898, 10. v. Bonsdorff, P. A., 1828, 4. Borchers, W., 1894, 4 ; 1895, n. Bottinger, Heinrich, 1844, i. Bourion, F., 1907, 7. Brauner, B., 1878, 6 ; 1881, i. Braw, Frederick, 1906, 7. Bray, W. C., 1908, 2. Brogger, W. C., 1884, 4. Brunner, Ludwig, 1900, i. Bunsen, R. W., 1875, i. Burgass, Rob, 1896, 7. Bussy, Antoine Alexandre, 1828, 3. Cahours, A., 1860, i ; 1873, I - Cameron, Frank K., 1908, 3. Carlton-Williams, W., 1880, i. Carnelley, T., 1879, i ; 1880, i ; 1884, 9, 10. Caron, H., 1858, 3. Clarke, F. W., 1883, 4. Classen, A., 1881, 3. Chabrie, C., 1886, 5. Christiansen, C., 1873, 9- Ciamician, G. L., 1880, 5. Combes, Alph, 1894, 6. Cooke, J. P., 1886, 6. Cossa, A., 1877, 2. Crookes, W., 1881, 4; 1887, 3. Curtius, Th., 1898, 12. Damour, A., 1843, 3- Dana, E. S., 1889, 2. Davy, Humphrey, 1809, i. Debray, Henri, 1854, 2 ; 1855, i ; 1867, i. Delafontaine, M., 1865, i. Deville, St. Claire, 1858, 3. Donath, Ed., 1883, 3. Duboin, A., 1896, 5. Du Menil, 1823, 2. Ebel, Fr., 1887, 2. Ebelmen, J. J., 1851, i, 2, 3. Elten, M., 1893, 4- Ekeberg, A. G., 1802, i. Faktor, F., 1901, 5. Flink, G., 1884, 4. Florence, W., 1898, 13. Formanek, J., 1900, 3. Franck, L., 1898, 20. Frankland, E., 1861, i. Fremy, E., 1853, i. Freundlich, H., 1903, i. Friedel, Ch., 1892, 7. Friedel, G., 1901, 4. Friedheim, Carl, 1906, 12. Fuller, C. T., 1907, 10. Gay-Lussac, L,. J., 1811, i. Genth, F. A., 1884, 6. Gibbs, Walcott, 1864, 2, 3, 4. Gibson, John, 1893, 3. Gladstone, J. H., 1896, n; 1897, 6. INDEX OF AUTHORS Glaser, Charles, 1890, 8. Glassmann, B., 1906, 8, 9; 1907, i, 4, 6 ; 1908, i. Gmelin, L., 1801, i ; 1840, i. Goldschmidt, H., 1898, 14. de Gramont, H., 1898, 11. Grandeau, H., 1886, 2. Gratzel v. Gratz. A., 1892, 3. Haber, F., and Van Oordt, G., 1904, 2,4. Harper, D. N., 1886, 4. Hart, Edward, 1895, 6. Hartley, W. N., 1883, 5 ; 1884, 5 ; 1901, i. Haushofer, K., 1883, 6. Hautefeuille, P., 1888, 4, 5 ; 1890, 9, 10, 14; 1893, i. Havens, F. S., 1897, i, 2; 1899, 5, 6. Heller, J. F., 1837, i. v. Helmolt, Hans, 1893, 2. Henry, Louis, 1895, 8. Hermes, 1866, 2. Heusler, Fr., 1897, 5. Heyl, Paul, 1894, 2. Hibbert, W., 1897, 6. Hober, R., 1898, 9. Hoist, N. O M 1873, 10. Hofmeister, F., 1859, i. Howe, James L., 1905, i. Humpidge, T. S., 1880, 3 ; 1883, 5, 7 ; 1885, i ; 1886, i. Itzig, H., 1899, 13. Jahn, Hans, 1891, 5. John, J. F., 1811, 2. Joule, J. P., 1848, i. Joy, Chas., 1863, i. Karnojitsky, A., 1892, 5. Kahlbaum, G. W. A. and Sturm, E., 1905, 6. Klatzo, G., 1869, r. Kiesow, F., 1898, 9. Kliiss, K., 1888, 2. v. Kobell, Fr., 1832, i. Kriiss, Gerhard, 1890, 4, 5, 6, 7. Kiihne, K. A., 1907, 4. Kurowski, E., 1907, 12, 13. Lacombe, H., 1901, 2 ; 1902, 3. Larsson, Aksel, 1896, 10. Lavroff, V., 1884, 2, 3. Lea, M. Carey, 1858, 2. Lebeau, P., 1895, 2, 5; 1896,6; 1897, 8; 1898,2,3,4,5,6,711899, ii. Levi-Malvano, Mario, 1905, 7. Lewy, B., 1857, i. Ley, H., 1899, 10. Liebermann, L., 1896, 3 ; 1898, 15, 16 ; 1899, 7. Link, H. F., 1799, 3. Lockyer, V. N., 1878, 10. McMahon, C. A., 1892, 4. Mallard, E., 1887, 4. de Marignac, C., 1873, T - Mayrhofer, Jos., 1883, 3, Mendele"ef, D., 1879, 2 ; 1889, 3. Meyer, Lothar, 1878, 5 ; 1880, u ; 1887, i. Meyer, Stefan, 1899, 2, 3. Moissan, Henri, 1898, 18. Moraht, H., 1890, i, 4, 5, 7- Mosnier, A., 1897, 7. Miiller, H., 1853, 2. Myers, Ralph E., 1904, 7. Neisch, A. C., 1904, 6. Neumann, G., 1888, i. Nicolardot, P., 1907, 8. Nielsen, R. A., 1900, 2. Nilson, L. F., 1875, 2, 3; 1876, i, 2 ; 1878, 2, 3, 4, 7, 8 ; 1880, 6, 8, 9, 10, 12 ; 1884, 7, 8 ; 1885, 3. Noyes, A. A., 1908, 2. Olmstead, Charles L., 1906, u. Ordway, J. M., 1858, i; 1859, 2. Ortloff, W., 1896, 12. Ouvrard, L., 1890, n. Parkman, Theodore, 1862, i. Parsons, Charles Lathrop, 1904, 5; 1904, 10, n; 1905, 2, 4, 5; 1906, i, 13; 1907, 3, 10, u. Pecile, 1877, 2. Penfield, S. L., 1884, i; 1886, 4. INDEX OF AUTHORS Perrey, A., 1888, 4, 5; 1890, 9, 10; 1893, I- Peroz, J., 1847, i. Petersen, Emil, 1890, 8. Petersen, 1899, i. Pettersson, Otto, 1878, 2, 3, 4, 8; 1880, 6, 7, 8, 9. 10; 1884, 7, 8; 1885, 3. Philipp, J., 1883, 2. Playfair, L., 1848, i. Pollok, James Holms, 1904, 1,9, 12. Prudhomme, M., 1895, 7. Pozzi-Escot, M. E., 1899, 4. Raikow, P., 1907, 14. Rammelsberg, C., 1891, 4. Rauter, G., 1892, 2. Reinsch, H., 1881, 2. Renz, Carl, 1903, 3, 4. Retgers, J. \V M 1896, 4. Reynolds, J. E., 1876, 3; 1880, 4; 1883, 8, 10. Riess, P., 1845, i. Rinne, F., 1895, 12. Rissom, J., 1898, 12. Rivot, L. E., 1850, i. Robinson, W. O., 1906, i; 1907, 10; 1908,3. Roman, R. J., 1898, 17. Roozebooni, H. W. B., 1891, i. Rose, G., 1864, i. Rose, H., 1827, i; 1828, i; 1842, i; 1843, i; 1848, 2,3; 1855, 2,3. Rosenheim, A., 1897, 4; 1899, 1 3- Rossler, C., 1878, 9. Rowland, H. A., 1895, 4. Rubenbauer, J., 1902, 5. Rydberg, J. R., 1890, 13. Sarazin, C., 1892, i. Schaffgotsch, F., 1840, 2. Schaub, X., 1801, 2. Scheerer, T., 1840, 3; 1842, 3. Scheffer, G., 1859, 3- Schlegelmilch, F., 1902, 4 Schleier, M., 1892, 6. Sestini, F., 1888, 3; 1890, 2; 1891, 6. Seubert, K., 1893, 4. Smith, Edgar F., 1878, i; 1894, 2; 1895, 9- Spear, A. B., 1908, 2. Stein, Gerh., 1907, 9. Steinmetz, Hermann, 1907, 5. Stolba, Fr., 1889, i. Strohecker, R., 1886, 3. Stromeyer, F. , 1812, i. Sturm, E., 1905, 6. Talnast, R. R., 1895, 4. Tammann, G., 1885, 2. Tanatar, S. M., 1904, 3; 1906, 10; 1907, 12, 13. Thale"n, Rob., 1869, 2. Thenard, L. J., 1811, i. Thomsen, J., 1870, i; 1871, i; 1873, 3; 1874, 2, 4. Toczynski, F., 1871, 2. Topsoe, H., 1872, 2; 1873, 5, 9- Traube, H., 1894, i, 3. Trommsdorff, J. B., 1833, i. Ulpiani, C., 1899, 14. Urbain, G., 1901, 2. Van Bemmelen, J. M., 1882, 2; 1898, 19. Van Oordt, G., 1903, 5; 1904, 2, 4; 1906, 5, 7- Vauquelin, L. N., 1798, i, 2, 3, 4, 5; 1799, i, 2. Vincent, Camille, 1880, 2. Vogel, Fritz, 1903, 2. Wagner, J., 1890, 12. Walden, P., 1894, 7. Wall worth, K. A., 1883, i. Warren, H. N., 1895, 10. Way, A. F., 1899, 5, 6. Weeren, J., 1854, i. Weinland, R. F., 1902, 4. Welkow, A., 1873, 3, 4, 5, 6. Wells, H. L., 1889, 2; 1901, 3. Wetherel, E. W., 1904, 8. Williams, C. G., 1873, 2; 1877, i; 1880, i. Winkler, C., 1890, 3; 1891, 3. Woge, P., 1897, 3, 4- Wohler, F., 1828, 2; 1864 i Wulff, G., 1889, 4. Wyrouboff, G., 1894, 5; ^ I; 1896, i; 1902, i, 2 . Zimmermann, A., 1887, 5- INDEX. A Acetate, basic, prep, and prop., 62, 1798, 5; 1858, i; 1901, 2; 1902, 3; 1903, 5 ; 1904, 3, 4, 5 ; 1906, i. basic, double with basic butyrate, 64, 1907, 12. basic, double with basic propionate, 64, 1907, 12. normal, prep, and prop., 40, 1907, 5. Acetylacetonate, prep., prop, and analysis, 40, 1894, 6; 1904, 5. Acid Salts, discussion, 45. Absorption spectra, 13, 1900, 3. Alexandrite, artificial, 1887, 4. Alloys, prep., 15, 1896, 3 ; 1898, 17, 18; 1899, 7, u. with Cu., 15, 1897, 8 ; 1898, 2, 4. Aluminate, 39, 1851, 3. Aluminum plat, chloride, 1874, 5. Antitnonate, 38, 1887, 2. Apparatus for electrolytic prep., 12, 1894, 4. Arc spectra, 13, 1883, 5 ; 1895, 4. Arsenate, ortho, 38, 1875, 4. acid, 45, 1875, 4. Arsenide, prep., 15, 1828, 2. Atomic volume, oxide, 23, 1855, 3. Atomic weight, 14, 1815, i ; 1826, i ; 1842, 2 ; 1854, i ; 1855, i ; 1869, i ; 1876, 3 ; 1878, 5, 6, 8; 1880, 6, 7, 8, 11, 12 ; 1881, i ; 1882, i ; 1883, 4, 7, 8, 9, 10 ; 1884, 5 ; 1885, i ; 1886, i ; 1890, i, 6, 7 ; 1904, 3, 5, 8 ; 1905, 5. Bacteria, action on nitrates. Basic Acetate, 62, 1903, 5 ; 1904, 4, 5 ; 1906, i ; 1907, 5. prep., prop, and analysis, 1901, 2 ; 1902, 3 ; 1904, 5. Butyrate, prep, and prop., 64, 1902, 3 ; 1907, 12. Formate, prep, and prop., 64, 1902, 3; 1907, 12. Isobutyrate, prep, and prop., 64, 1902, 3. Isovalerate, prep, and prop., 64, 1902, 3. Oxalates, 66, 1906, i. Propionate, prep, and prop., 64, 1902, 3 ; 1907, 12. Sulphates, See Sulphate, basic. Basic Salts, discussion, 61, 1906, i ; 1907, 4. list of, 1906, i ; 1907, 4. Basic Solid Phases, indefinite, 65, 69. INDEX 173 Benzoate, basic, 71, 1907, 12. Beryl, artificial production, 1873, 3 ; 1893, I ; 1893, 4. preparation of beryllium compounds from, 4. Beryl, decomp. of, 1801, 2 ; 1855, i ; 1859, 3 ; 1863, i ; 1884, i ; 1889, i ; i893 > 3 ; 1895, 3, 5, 6 ; 1898, 5 ; 1902, 2. Beryllium ethyl, 39, prep, and prop., 1860, i ; 1861, i ; 1873, I. methyl, 39, 1884, 2, 3. metallic, preparation 12. See metal, chloride quinoline, 20, 1903, 3. propyl, 39, prep, and prop., 1873, i. Beryllonates, 27. Beryllonite, method of analysis, 1889, 2. Borate, basic, 70, 1878, i ; 1890, i, 4, 5. Borocarbide, 26, 1898, 7. Bromate, 29. Bromide, metal from, 11, 1895, 10. prep, and prop., 21, 1828, 2 ; 1831, i ; 1879, r 1880, i ; 1884, 9, 10 ; 1899, n. vapor density, 1886, i. Butyrate, basic, prep, and prop., 64, 1902, 3. basic, double with acetate, 64, 1907, 12. C Camphor Sulphonate, 44, 1894, 7. Carbide, discussion formula, 1895, 8. prep, and prop., 26, 1895, 2; 1897, 5 ; 1899, n. Carbonate, magnetic properties, 1899, 3- prep, and prop., 38, 67, 1798, 5 ; 1840, 2 ; 1854, i; 1855, i; 1862, i; 1869, i ; 1890, 2 ; 1893, 4; 1904, i; 1904, 5; 1906, 4 ; 1907, 14 ; 1908, 3. action of NH 4 C1 upon, 1848, 3. Carbonates, double with alkalies, 53, 1855, l \ J 869, i ; 1886, i. Chlorate, 29, molecular solution volume, 1894, 3. Chloride, 19. hydrolysis of 17, 21, 1899, Io > I 9> T - taste due to cation, 21, 1898, 9. basic, 70, 1873, 7, 8 ; 1875, 4. with ether, 20, 1875, 4. double with Tl, 48, 1888, i. anhydrous, prep, and prop., 19, 1827, i ; 1828, 2 ; 1842, 2 ; 1855, i ; 1869^ i ; 1880, 6, 7, 8; 1885, 3; i887; I ; 1897, i; 1898, 5; 1899, n; 1904, i; 1904, 5; 1904, 12. 174 INDEX Chloride, double with Hg, Sn, Au, 47, 48, 1873. 7> 8. hydrous, 20, 1842, 2 ; 1873, 7 ; 1873, 8. double of Hg and Be, 47, 1828, 4. double with Fe, 48, 1888, i. Cr, 48, 1888, i. I, 48, 1902, 4. reduction by electricity, 1831, 2. metal from, 11, 1895, u. fractional sublimation, 20, 1905, 3. melting point, 20, 1879, i; 1880, i; 1884,9, IO I I 94 J > 9- vapor density, 20, 1884, 7, 8; 1885, 3 ; 1886, i. basic, preparation, 1798, 5; 1801, i. heat of formation, 20, 1904, 9. heat of solution, 20, 1904, 9. action upon colloidal As 2 S 3 , 1903, i. magnetic prop., 1899, 3. molecular wt. in pyridine, 1897, 4. Chloropropionate, basic, 71, 1908, i. Citrate, basic preparation, 71, 1798, 5. Citraconate, 44, 1907, 12. Chromate, basic, 70, 1811, 2 ; 1873, 7, 8 ; 1907, 4. normal, 35, 1907, 4. Chromite, 35, 1887, 4. Columbate, 38, 1896, 10. Complexity of beryllium, 1904, 12; 1905, 4. Crystals in blowpipe bead, 1898, 13. Crysoberyl, prep., 1890, 9. Crotonate, basic, 70, 1907, 12. Cyanacetate, basic, 70, 1908, i. Cyanides, 26, 1871, 2; 1873, 1 \ l8 9^, 6; 1899, n. Cymophane, artificial production, 1851, 3. Detection, 6, 1799, i. Determination in beryl, 6-9, 1798, i, 3, 4; 1823, 2. Determination, in monazite, 1896, 8 ; 1898, 10. Determination, (See also Separation) 9, 1866, 3 ; 1880, 2 ; 1881, 3 ; 1897, 4 ; J93, 4 ; 1906, 2, 9. Dichloracetate, basic, 70, 1908, i. Dimethylamin, action on Be salts, 6, 1880, 2. Diplato-nitrite, 52, 1876, 2. Discovery, 1, 1798, i, 3. See also 1801, i, 2. Dithionate, 34, 69, 1888, 2. Double Salts, discussion, 47. INDEX 175 Emerald, artificial, 1877, i ; 1888, 4. coloring matter of, 1864, i ; 1873, 3. artificial production, 1873, 3. color of, 1857, i. Ethylglycolate, basic, 71, 1908, i. F Ferrocyanide, 39, 70. Ferricyanide, 39, 1871, 2 ; 1873, 7. Fluoride, prep, and prop., 18, 1823, i ; 1869, i ; 1898, 8 ; 1901, 3 ; 1904, i. prep, of metal from, 12, 1898, 3,' 4 ; 1899, u. double with K, Na or NH 4 , 49, 50, 1823, i; 1842, 2; 1855, i; 1864, 3; 1873, 2; 1893, 2; 1898, 3, 4; 1899, ii. Fluosilicate, prep., 39, 1823, i. Formate, basic, prep, and prop., 40, 64, 1902, 3; 1907, 12. Fumarate, basic, 44, 1907, 12. Glycolate, basic, 71, 1908, i. H Halides, double, 18, 1901, 3. History, 2. Hydride, 1891, 3. Hydroxide, 27. basicity of, 28, 1899, 10. Hydroxides, prep, and prop., 27-28, 1840, i, 2; 1854, i; 1855, J l ^T 1 . 2 J 1873, 7, 8; 1874, i; 1880, 2; 1882, 2; 1891, 6; 1895, 7; 1898, 19; 1902, 5; 1903, 4; 1904, 2. Hydroxide, magnetic, prop., 28, 1899, 3. heat of neutralization, 28, 1871, i; 1874, 2; 1890, 8. solubility in beryllium salts, 27, 1904, 10; 1906, i; 1907, 10, u. Hydrolysis of salts, 17, 1899, 10; 1900, i; 1904, 10. Hypophosphate, 37, 1891, 4. Hypophosphite, prep., 37, 1828, i. Incandescent oxide, 1900, 2. Iodide, prep, and prop., 22, 1828, 2; 1855, i; 1898, 6; 1899, 11. double with Pb, 50, 1897, 7. double with Bi, 50, 1874, 6. lodate, 29. Isomorphism of, 1896, 4. Isobutyrate, basic, prep, and prop., 64, 1902, 3. 176 INDEX Isocrotonate, basic, 70, 1907, 12. Isovalerate, basic, prep, and prop., 64, 1902, 3. K "Krokonate," 44, 1837, i. I* Lactate, basic, 71, 1908, i. Laevulinate, basic, 70, 1907, 12. M Magnetic properties, 1899, 2. Maleate, basic, 44, 1907, 12. Mallates, 59, 1899, 13. Mercury cathode, sep. by, 8, 1904, 7. Mercuric oxide, action on, 1894, 2. Metal, 11, 1898, i; 1899, n. by electrolysis, 11, 1895, 10, n; 1898, 3; 1899, 11. crystal from, 12, 1884, 4; 1895, 12. prep, and prop., 11, 14, 1809, i; 1812, i; 1828, 2, 3; 1855, i; 1867, i; 1876,3; 1878, 3, 4; 1880, 6, 7; 1883, 7; 1886, i; 1890, i, 3, 4, 5; 1892, 3; 1896, 2; 1898, i, 4, 14, 15, 16, 18; 1899, ii ; 1904, i, 9; 1907, 2. Sp. Gr., 12, 1855, i; 1878, 3, 4; 1886, i; 1898, 3; 1899, 11. Microscopical analysis, 1881, 2; 1883, 6; 1891, 2; 1892, 4; 1899, 4. Minerals, Chief, 3. Molybdates, basic, 70, 1873, 7, 8. double, 52. normal, 35, 1897, 4. acid, 46, 1873, 7. Monobromacetate, basic, 71, 1908, i. brompropionate, 71, 1908, i. chloracetate, 71, 1908, i. N Name, origin and discussion of, 1, 1798, i, 3, 4; 1799, 3; 1904, 11; 1905, i, 2; 1907, 8. Nitrate, hydrolysis of, 17, 1900, i. basic, preparation and prop., 70, 1798, 5; 1801, i; 1858, i; 1859, 2 < 3; 1904, 5- tetrahydrate, normal, 36, 1906, 13. Nitrite, 37, 1903, 2. Nitroprusside, 39, 1871, 2. Nitroso-/3-Naphthol, action on, 7, 1892, 6; 1895, 9; 1896, 7. Normal compound, discussion, 17. INDEX 177 O Occurrence, 3. Optical rotation of mallates, 58, 1899, 13. camphor sulphonate, 44, 1894, 7. tartrates, 57, 1899, 13. Optical properties, sulphate, 1889, 4. Oxalate, acid, 46, 1902, i; 1906, i. Oxalates, basic, 66, 1873, 7, 8; 1906, i. Oxalate, double with K, Na or NH 4 , 54, 1855, i; 1883, 2; 1897, 4. double with K, Rb, Na, Li, 54, 56, 1902, i. normal, 41, 1902, i; 1906, i. Oxide, 23, 1798, 2; 1851, 2; 1855, i; 1884, 6; 1896, 6. action of NH 4 C1 on, 25, 1848, 3; 1855, 2. action of CC1 4 upon, 24, 1887, i. action of bromine on, 24, 1834, i. action of Cl and S 2 C1 2 upon 24, 1907, 7. atomic volume, 1855, 3. composition, 1842, i. crystals, 23, 1851, i; 1855, i; 1886, 2; 1887,4; 1890, 9, 14; 1895, 12. extraction of from beryl, 4, 1893, 3; 1895, 5, 6; 1899, i; 1902, 2; 1904, i, 9. magnetic prop., 24, 1899, 3. presence in diluvian clays, 1886, 3. reduction by Mg, 24, 1890, 3; 1899, n. Al, 24, 1898, 14, 20; 1899, II. Sp. Gr., 23, 1802, i; 1848, 2; 1851, i; 1880, 9, 10; 1886, 2; 1890, 7. Sp. heat, 24, 1880, 9, 10; 1906, 10. P Palladio chloride, 49, 1874, 3, 6. Patent for prep, of Be, 1892, 3. Peculiarities of, 1907, 3. Perchlorate, 1873, 7, 8. Periodate, 1873, 7, 8. Periodic position, 15, 1879, 2; 1889, 3. Phenacite, artificial, 1887, 4; 1888, 4; 1890, 14; 1893, I - Phenylglycolate, basic, 71, 1908, i. Phosphates, with Na, 52, 1883, i; 1890, u. with K, 52, 1886, 2; 1890, ii. with NH 4 , 52, 1878, 9; 1899, 8, 9. Phosphate, acid, 45, 1859, 3; J 875, 4- ortho, 37, 1873, 7, 8; 1875, 4; 1890, 2. hypo, 37, 1891, 4. triple, Na and NH 4 , 53, 1859, 3. Phosphite, prep., 37, 1827, i. hypo, 37, 1828, i. *7 INDEX Phosphide, prep., 25, 1828, 2; 1899, u. Picrate, 43, 1858, 2; 1907, 6. Plant food, beryllium as, 1891, 6. Platino-chloride, 48, 1870, i; 1873, 2, 5; 1874, 4; 1876, 2. cyanide, 50, 1871, 2; 1873, 10. double with Mg, 50, 1871, 2. Plato-iodo-nitrite, 52, 1878, 7. Plato-nitrite, 52, 1876, 2. Potassium berylonate, 27, 1890, i, 4, 5. Presence in plants, 1888, 3. Propionate, 40. basic, prep, and prop., 64, 1902, 3. double with acetate, 64, 1907, 12. normal, 40, 1907, 12. Pyrophosphate, 37, 1859, 3; 1873, 7- double, 1847, i. Q Quinoline beryllium chloride, 21, 1903, 3. Racemates, 58. Refraction, atomic, 1896, 10. specific, 1896, 10. molecular, of sulphate, 31, 1897, 6. Rhodizonate, 44, 1837, i. Salicylate, basic, 71, 1908, i. Seed production, beryllium in, 1891, 6. elenate, crystals with sulphate, 1872, u; 1891, r. crystal character, 34, 1872, i; 1873, 6, 9. prep., 34, 1873, 7, 8. Selenide, prep, and prop., 25, 1828, 2. Selenites, basic, 70, 1873, 7, 8. Selenites, 34, 45, 1875, 2, 3. Separation, 6, 1840, i, 2, 3. electrolytic, 8, from Al and Fe, 1881, 3. from Al, 6, 1798, i, 3; 1840, i; 1843, 2; 1844, i; 1855, i; 1859, i, 35 1863, i; 1864, 3; 1877, i; 1878, 9; 1880, 2; 1886, 4; 1887, 5; 1895, 9; 1897, i, 2; J 903, 4, 5; J 904, i, 4; I96. i, 7, 8, 12. from Ce group, 1843, 2; 1864, 2. from Cr, 6, 1904, 7. from Fe, 6, 1840, i; 1842, 3; 1850, i; 1866, i; 1892, 6; 1894, 2; 1895, 9; 1896, 7; 1899, 5, 6; 1903, 5; 1904, i, 4, 7; 1906, i, 7. from Ga, 1882, 3. from Yt, 1802, i; 1843, i, 2; 1864, 2. INDEX 179 Silicate, with Al, 54. with Ivi, 54, 1901, 4. double with K, 54, 1888, 5; 1892, i; 1896, 5. Silicates, double with Na, 54, 1890, 10. production of, 38, 1890, 9, 14; 1893, i; 1907, 9. Silicide, 27. Silicon tetra chloride, effect on, 1892, 2. Silico-tungstate, 39, 1894, 5; 1896, T. Solution volume of sulphate and chlorate, 31, 1894, 3. Specific heat, 13, 1876, 3; 1878, 2, 3, 4; 1880, 6, 7, 8; 1883, 7; 1886, i. Specific rotation, malates, 60, 1899, 13. sulphate, 1891, 5. tartrate, 58, 1838, i; 1899, 13. Spectra, 13, 1869, 2; 1875, i; 1878, 10, n; 1881, 4; 1883, 5; 1887, 3; 1890, 13; 1895, 4; 1898, n; 1900, 3; 1901, i; 1905, 3; 1906, ii. Succinate, normal, 43, 1873, 7, 8. basic, 70, 1873, 7, 8; 1907, 12. Sulphate, anhydrous, 29, 1880, 9, 10; 1896, 6; 1899, n; 1904, 10; 1905, 7. Sulphate, basic, 65, 1798, 5; 1801, i; 1815, i; 1873, 7, 8; 1904, 10; 1907, 10, u. Sulphate dihydrate, 30, 1854, i; 1880, 6, 9, 10; 1890, 7; 1904, 5, 10; 1905, 7. Sulphate heptahydrate, 33, 1869, i; 1873, i; 1904, 10. Sulphate hexahydrate, 32, 1873, J I I 95. 75 1906, 5- Sulphate monohydrate, 30. Sulphate tetrahydrate, 30. crystals with selenate, 1872, i; 1873, 6; 1891, i. heat of solution, 32, 1873, 4> I 94> 9- hydrolysis of , 31, 1899, 10; 1900, i; 1904, 10. magnetic susceptibility, 31. mol. refraction, 31, 1897, 6. mol. solution volume, 31, 1894, 3. mol. volume 32, 1873, 6. mol. wt., 1880, 9, 10. prep, and prop., 30-32, 1815, i ; 1842,2; 1854, i; 1855, i; 1872, i; 1873, 7, 8, 9; 1880, 6, 9, 10; 1889, 4; 1890, 7; 1899, 3; 1903, i; 1904, i, 5, 9, 10, 12; 1905, 7. solution friction, 31, 1890, 12. solution in, 32, 1907, n. specific gravity, 32, 1872, i; 1873, 6; 1880, 9, 10; 1890, 7. specific rotation, 31, 1891, 5. taste due to cation, 31, 1898, 9. Sulphates, double with K, NaorNH 4 , 51, 1842, 2; 1855, i; 1869, i; 1873, 2 > 7. 8 - Sulphide, double, of Be and W, 50, 1826, 2. preparation, 25, 1825, i; 1828, 2; 1853, i; 1855, i; 1899, u. l8o INDEX Sulphite, normal, 33, 1890, i, 4, 5. basic, 69, 1873, 7, 8; 1890, 4; 1893, 4. double with K, 52, 1897, 4. NH 4 52, 1897, 4. Sulphocyanate, 34, 1866, 2; 1871, 2; 1873, 7- Sulphonate, 44, alpha brom camphor, optical rotation of, 1894, 7. T Tartrate, 42, 1871, 2; 1873, 7J l8 73> 8 - basic preparation, 71, 1798, 5. mono and di, 56, 57, 1899, 13. rotatory power, 1838, i; 1899, 13. double with K, Na, NH 4 , 1897, 4; 1899, 13. Tellurate, 35, 1833, 2. Telluride, 25, prep, and prop., 15, 1828, 2. Tellurite, 35, 1833, 2. Thiosulphate, 34, 1901, 5. Trichloracetate, basic, 71, 1908, i. Trinitride, 25, 1898, 12. V Valency discussion, 15, 1826, i; 1832, i; 1842, 2; 1843, 3; *%55> i, 2, 3; 1875, 2; 1876, i; 1878, 3, 4, 5, 6; 1880, 3, 4, 6, 7, 8, 11,12; 1881, i; 1882, i; 1883, 5; 1884, 7; 1894, 5, 6; 1895, i, 7, 8;i8 9 7, 4; 1902, i; 1904, 3; 1906, 10; 1907, i, 6. Valerate, 71, 1833, i. Vanidate, 38, 1831, 3. Vapor tension of solutions of Be salts, 1885, 2. Use in incandescent lamps, 1896, 9. SCIENTIFIC BOOKS PUBLISHED BY- The Chemical Publishing Company, Easton, Pa. BENEDICT Elementary Organic Analysis. Small 8vo. 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