The Rare Earths: Their Occurrence, Chemistry, and Technology

PART I. _occurrence of the Rare Earths_

OCCURRENCE OF THE RARE EARTHS

CHAPTER PAGE

I. THE NATURE OF THE MINERALS AND THEIR MODE OF OCCURRENCE 1

II. THE SILICATES 30

(a) Silicates of Yttrium and Cerium Metals--Cerite; Gadolinite, Glowing of Minerals; Allanite, Hellandite, Thalénite and Thortveitite; etc.

(b) Silicates of Thorium and Zirconium--Thorite, Zircon, Naegite; etc.

(c) Mixed Silicates--Eudialyte, Beckelite; etc.

III. THE TITANO-SILICATES AND TITANATES 52

(a) Titano-silicates--Yttrotitanite, Titanite; etc.

(b) Titanates--Yttrocrasite, Delorenzite, Ilmenite; etc.

IV. THE TANTALO-COLUMBATES 60

(a) Containing no Titanium Dioxide--Samarskite (Annerödite), Plumboniobite, Yttrotantalite, Fergusonite, Sipylite; etc.

(b) Containing Titanium Dioxide--Æschynite; the isodimorphous series Euxenite, Polycrase, Blomstrandine, Priorite; Risörite, Wiikite; etc.

V. THE OXIDES AND CARBONATES 72

(a) Oxides--Uraninite, Thorianite, Baddeleyite; Rutile, Anatase and Brookite; etc.

(b) Carbonates--Lanthanite; Parisite (Synchisite), Cordylite; etc.

VI. THE PHOSPHATES AND HALIDES 82

(a) Phosphates--Monazite, Xenotime (Hussakite); etc.

(b) Halides--Yttrocerite, Yttrofluorite; etc.

VII. THE MONAZITE SANDS 90

VIII. RADIOACTIVITY OF THE MINERALS 99

PART II. _the Chemistry of the Elements_

THE CHEMISTRY OF THE ELEMENTS

IX. GENERAL PROPERTIES OF THE CERIUM AND YTTRIUM GROUPS 111

X. GENERAL METHODS OF SEPARATION 142

XI. THE CERIUM GROUP--CERIUM 156

XII. THE CERIUM GROUP (CONTINUED)--LANTHANUM, PRASEODYMIUM, NEODYMIUM, AND SAMARIUM 168

XIII. THE TERBIUM GROUP 184

XIV. THE ERBIUM AND YTTERBIUM GROUPS--YTTRIUM AND SCANDIUM 194

XV. THE GROUP IVA ELEMENTS--TITANIUM 219

XVI. THE GROUP IVA ELEMENTS (CONTINUED)--ZIRCONIUM AND THORIUM 238

PART III. _the Technology of the Elements_

THE TECHNOLOGY OF THE ELEMENTS

XVII. THE INCANDESCENT MANTLE INDUSTRY--HISTORICAL AND GENERAL INTRODUCTION 265

XVIII. THE CHEMICAL TREATMENT OF MONAZITE 275

XIX. THE MANUFACTURE OF MANTLES FROM COTTON AND RAMIE 291

XX. ARTIFICIAL SILK--ITS PRODUCTION AND USE IN THE MANTLE INDUSTRY 301

XXI. OTHER TECHNOLOGICAL USES OF THE CERIUM AND YTTRIUM ELEMENTS, ZIRCONIUM AND THORIUM 313

XXII. THE INDUSTRIAL APPLICATIONS OF TITANIUM AND ITS COMPOUNDS 325

INDEX 342

TABLE OF ABBREVIATIONS EMPLOYED IN THE REFERENCES

Abstr. Chem. Soc. Abstracts in Journal of the Chemical Society.

Amer. Chem. J. American Chemical Journal.

Amer. J. Sci. American Journal of Science.

Annalen Justus Liebig’s Annalen der Chemie.

Ann. Chim. Phys. Annales de Chimie et de Physique.

Astrophys. J. Astrophysical Journal.

Ber. Berichte der Deutschen chemischen Gesellschaft.

Berz. Jahres. Berzelius’ Jahresbericht über die Fortschritte der Chemie und Mineralogie.

Bull. Imp. Inst. Bulletin of the Imperial Institute.

Bull. Soc. chim. Bulletin de la Société chimique de France.

Bull. Soc. franc. Min. Bulletin de la Société française de Minéralogie.

Bull. Soc. franc. Photog. Bulletin de la Société française de Photographie.

Bull. U. S. Geol. Survey Bulletin of the United States Geological Survey.

Cass. Mag. Cassier’s Magazine.

Centr. Min. Centralblatt für Mineralogie, Geologie und Paläontologie.

Chem. Eng. Chemical Engineer.

Chem. Ind. Chemische Industrie.

Chem. News Chemical News.

Chem. Zeitg. Chemiker Zeitung.

Chem. Zentr. Chemisches Zentralblatt.

Compt. rend. Comptes rendus hebdomadaires des Séances de l’Académie des Sciences.

Dingl. Polyt. J. Dingler’s Polytechnisches Journal.

D. R. P. Deutsche Reichspatentschrift.

E. English Patent Specification.

Elect. chem. Ind. Electrochemical Industry (since 1904, Electrochemical and Metallurgical Industry).

F. Brevet d’Invention de la République Française.

J. Amer. Chem. Soc. Journal of the American Chemical Society.

J. Gasbel. Journal für Gasbeleuchtung.

J. Gaslighting Journal of Gaslighting.

J. Ind. Eng. Chem. Journal of Industrial and Engineering Chemistry.

J. pr. Chem. Journal für practische Chemie.

J. Russ. Phys. Chem. Soc. Journal of the Physical and Chemical Society of Russia.

J. Soc. Chem. Ind. Journal of the Society of Chemical Industry.

Met. Chem. Eng. Metallurgical and Chemical Engineering.

Min. Mag. Mineralogical Magazine and Journal of the Mineralogical Society.

Monats. Monatshefte für Chemie und verwandte Theile anderer Wissenschaften.

Phil. Mag. Philosophical Magazine.

Phil. Trans. Philosophical Transactions of the Royal Society of London.

Pogg. Ann. Poggendorff’s Annalen der Physik und Chemie.

Proc. Amer. Acad. Proceedings of the American Academy.

Proc. Chem. Soc. Proceedings of the Chemical Society.

Proc. Roy. Soc. Proceedings of the Royal Society.

Prog. Age Progressive Age (now Gas Age).

Publ. Astrophys. Observ. Publikationen des Astrophysikalischen Potsdam Observatoriums zu Potsdam.

Schweigg. J. Schweigger’s Journal für Chemie und Physik.

Sitzungsber. kaiserl. Akad. Sitzungsberichte der kaiserlich Akademie Wiss. Wien der Wissenschaften zu Wien.

Sitzungsber. königl. Akad. Sitzungsberichte der königlich Akademie Preussischen Wiss. Berlin der Wissenschaften zu Berlin.

Stahl Eisen Stahl und Eisen.

Trans. Amer. El. chem. Soc. Transactions of the American Electrochemical Society.

Trans. Amer. Inst. Min. Transactions of the American Institute Eng. of Mining Engineers.

Trans. Chem. Soc. Transactions of the Chemical Society.

Tsch. Min. Mitt. Tschermak’s Mineralogische Mittheilungen.

U. S. Geol. Survey United States Geological Survey--Mineral Resources of the United States.

U. S. P. United States Patent Specification.

Zeitsch. anal. Chem. Zeitschrift für analytische Chemie.

Zeitsch. angew. Chem. Zeitschrift für angewandte Chemie.

Zeitsch. anorg. Chem. Zeitschrift für anorganische Chemie.

Zeitsch. Elektrochem. Zeitschrift für Elektrochemie.

Zeitsch. Kryst. Min. Zeitschrift für Krystallographie und Mineralogie.

Zeitsch. physikal. Chem. Zeitschrift für physikalische Chemie, Stöchiometrie und Verwandtschaftslehre.

Zeitsch. pr. Geol. Zeitschrift für praktische Geologie.

Zeitsch. wiss. Photochem. Zeitschrift für wissenschaftliche Photographie, Photophysik und Photochemie.

INTRODUCTION

By SIR WILLIAM CROOKES, O.M., F.E.S.

The mysterious group of substances to which have been given the title of “rare earths” has long been the subject of my special study, and no one knows better the magnitude of the difficulties encountered in the investigation, or realises more clearly the comparative insignificance of the knowledge we have acquired. The rare earths constitute the most striking example of the association of chemical substances with others which are closely allied to themselves, and from which they are separable only with extreme difficulty. They form a group to themselves, sharply demarcated from the other elements, and it is my belief that by following the study of them to the utmost limits, we may arrive at the explanation of what the chemical elements really are and how they originated, and discover the reasons for their properties and mutual relations. When this knowledge has been wrested from Nature chemistry will be established upon an entirely new basis. We shall be set free from the need for experiment, knowing a priori what the result of each and every experiment must be; and our knowledge then will as much transcend our present scientific systems as the knowledge of the skilled mathematician of the present day exceeds that of primitive man, counting upon his fingers. The great problem of the nature and genesis of the elements is approaching solution, and when the consummation is reached it will undoubtedly be found that the study of the rare earths has been an important factor in bringing it about.

There has long been a need for a work in the English language dealing historically and descriptively with these substances, and Mr. Levy’s book is well fitted to fill the gap. The chapters on the technical applications of the rare earths are particularly valuable, and the chemical aspect of the incandescent lighting industry is admirably treated. The author is to be congratulated upon having successfully achieved an important and useful piece of work.

WILLIAM CROOKES.

December 1914.

THE RARE EARTHS

PART I. Occurrence of the Rare Earths

OCCURRENCE OF THE RARE EARTHS

CHAPTER I

THE NATURE OF THE MINERALS AND THEIR MODE OF OCCURRENCE

The history of the rare earth minerals begins in the year 1751, when the Swedish mineralogist Cronstedt described a new mineral, which he had found intimately mixed with chalcopyrite in the quarry of Bastnäs, near Ryddarhyttan, in the province of Westmannland, Sweden. Cronstedt gave the mineral the name Tung-sten (heavy stone); but as the name Tenn-spat (heavy spar, or heavy mineral) had already been selected by Wallerius (1747) for a new species from Bohemia, believed to contain tin, the choice was not a happy one. More than fifty years after its discovery, a new earth, now known as ceria, was isolated from Cronstedt’s mineral, for which at the same time the name Cerite was proposed. Meanwhile, however, the Finnish chemist Johann Gadolin had observed, in the year 1794, a new earth in a mineral discovered by Arrhenius at Ytterby in Sweden in 1788; he called the new oxide Ytterbia, and the mineral in which he observed it, Ytterbite. The discovery was confirmed in 1797 by Ekeberg, who suggested the names Yttria and Gadolinite for the oxide and mineral respectively; these names were accepted by Klaproth, and soon came into general use. Whilst then Cerite was the first of the rare earth minerals to be discovered, it was in Gadolinite that new elements were first recognised, and the chemistry of the rare earths began in 1794 with Gadolin’s observation.

Chalcopyrite, or Copper pyrites, is a mixed sulphide of iron and copper, of the approximate formula CuFeS₂.

For the history of the name Tungsten, see under the mineral Cerite, Ch. II.

The history of these names will be found somewhat more fully under Gadolinite, Ch. II.

During the nineteenth century a considerable number of rare earth minerals was discovered and analysed; the quantities of the minerals observed, however, were so small that the name ‘Rare earths,’ applied to the new oxides found, was in every sense justified. Until the year 1885, though by that time the scientific interest of the group had been fully demonstrated by the discovery of several new elements, it was supposed that the minerals were almost entirely confined to a few scattered localities in Scandinavia and the Ural mountains. In that year Dr. Auer von Welsbach announced his application of the rare earths to the manufacture of incandescent mantles. Immediately there was a great demand for raw material for the preparation of thoria and ceria. The agents of the Welsbach Company visited all the important mining centres of Europe and America, intent on a search which shortly made it clear that the metals of the so-called ‘rare earths’ are really quite widely distributed in nature. The chief commercial deposits are the monazite sands of the Carolinas, the Idaho basin, and Brazil, the gem-gravels of Ceylon, and the remarkable deposits of gadolinite and allied minerals at Barringer Hill in Texas.

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