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Crystal Chemistry of Beryllium

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Crystal Chemistry of Beryllium Crystal Chemistry of Beryllium 5 GEOLOGICAL SURVEY PROFESSIONAL PAPER 468 Crystal Chemistry of Beryllium By MALCOLM ROSS GEOLOGICAL SURVEY PROFESSIONAL PAPER 468 A detailed discussion of the crystal chemistry of all the known beryllium minerals UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1964 UNITED STATES DEPARTMENT OF THE INTERIOR STEW ART L. UDALL, Secretary GEOLOGICAL SURVEY Thomas B. Nolan, Director The U.S. Geological Survey Library has cataloged this publication as follows: Ross, Malcolm, 1929- Crystal chemistry of beryllium. Washington, U.S. Govt. Print. Off., 1964. iv, 30 p. illus., diagrs., tables. 29 em. (U.S. Geological Survey. Professional paper 468) Bibliography : p. 28-30. 1. Beryllium. 2. Crystallization. I. Title. (Series) For safe by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 CONTENTS Page Page Abstract __________________________________________ _ 1 The beryllium minerals-continued 16 Introduction ______________________________________ _ 1 Gu~aite ________ ------------------------------- The beryllium minerals _____________________________ _ leucophanite _ -- __ -------------------------­ 16 1 16 Amino.ffite ____________________________________ _ meliphanite __ - __ --------------------------- 2 18 Barylite ______________________________________ _ Milarite ______ --_------------------------------ 2 Moraesite _____________________________________ _ 19 Bavenite ______________________________________ _ 3 Bearsite _____ ---------------------------------- 19 Bertrandite ___________________________________ _ 3 Phenakite _____________________________________ _ 20 Beryl------------------------------------------ 5 Rhodizite ____ ---------------------------------- 20 Bazzite _______________________________________ _ Roscherite ____________________________________ _ 6 20 Beryllite ______________________________________ _ 20 6 Spherobertrandite------------------------------­ Beryllonite ____________________________________ _ 21 7 TaaffeiteSwedenbor~te---------------------------------- ______________________________________ _ Beryllosodalite ________________________________ _ 21 7 Tengerite _____________________________________ _ Bityite _______________________________________ _ 22 8 Trimerite _____________________________________ _ Bromellite ____________________________________ _ 22 8 Vayrynenite ___________________________________ _ 22 Chkalovite ___________________________________ - _ 9 23 Chrysoberyl ___________________________________ _ Euclase ____ ------------------------------------ 9 The ·beryllium compounds __ ------------------------­ 23 Epididymite __________________________________ - _ 23 9 Be(H20)4S04----------------------------------­ Eudidymite ___________________________________ _ 10 24 Faheyite ______________________________________ _ ~-Be(OH)2------------------------------------- 10 BeS04----------------------------------------­ 24 Gelbertrandite _________________________________ _ 10 BeGe04---------------------------------'------­ 24 24 Ilamber~te------------------------------------ 10 BeSeBeS--------------------------------------~---- _________________________________________ _ 24 IIarsti~te _______________________________ -- ___ -- 11 BeTe _________________________________________ _ Helvite _______________________________________ _ 24 11 J)analite ______________________________________ _ BeSiN2---------------------------------------­ 24 11 BeC12----------------------------------------- 24 Genthelvite ___________________________________ _ 11 24 Herderite _____________________________________ _ Be(CHah- ------------------------------------­ 13 Basic beryllium acetate, Be40(CHaC00)&---------- 25 Gadolinite ____________________________________ _ 13 Beryllium phthalocyanine, Be Cs2H t6N s----- ------ -- 25 Hsianghualite _________________________________ _ 14 The beryllium fluorides ___ ----------------------- 25 Conclusions _______________________________________ _ IIurlbutite ____________________________________ _ 14 27 ]{arpinskyite __________________________________ _ 16 References _______ -_--------------------------:..-.---- 28 ILLUSTRATIONS Page 4 F1 GURE 1. The crystal structure of barylite________________________ ---------------------------------------------- 4 2. The crystal structure of bertrandite (after Ito and West)------------------------------------------------ 3. The crystal structure of bertrandite (after Solovieva and Belov)------------------------------------------ 5 4.. The crystal structure of beryl __________________________ - ---------------- ----------------- ------------ 6 7 5. The structure of the Si60 1s ring in beryL ______________ -_--------------- ... ------------------------------ 6. The crystal structure of beryllonite _____________________ ---------------------------------------------- 8 7. The arrangement of tetrahedra and octahedra in layers I and II of chrysoberyL- --------------------------- 10 8. The crystal structure of hambergite _____________________ ---------------------------------------------- 12 U. The crystal structure of herderite ___________________ -------------------------------------------------- 13 13 10. The arrangement of the calcium polyhedra in herderite ____ ---------------------------------------------- 11. The arrangement of the yttrium and iron polyhedra in gadolinite ________________________________________ _ 14 12. The crystal structure of hurlbutite ______________________ ---------------------------------------------- 15 13. The crystal structure of melilite ____________________ - _------------------------------------------------ 16 17 14. The arrangement of the calcium polyhedra in melilite_-------------------------------------------------- 18 15. The crystal structure of milarite projected on (1010)---------------------------------------------------­ m IV CONTENTS FIGURE 16. The crystal structure of milarite projected on (0001)---------------------------------------------------- 18 17. A comparison of the beryl and milarite structures_______________________________________________________ 19 18. The crystal structure of swedenborgite________________________________________________________________ 21 19. A comparison of the vayrynenite and euclase structures_________________________________________________ 23 20. The beryllium phthalocyanine molecule_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 25 TABLES Page TABLE 1. The berylli urn minerals____ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 2 2. Chemical composition of Bavenite _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3 3. Charge distribution on the oxygen atoms in hurlbutite and danburite______________________________________ 15 4. Bond lengths in the hurlbutite structure_______________________________________________________________ 15 5. Crystallography of gugiaite, leucophanite, meliphanite, and the related minerals melilite and hardystonite _ _ _ _ _ 16 6. Chemical composition of gugiaite, leucophanite, and meliphanite_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 17 7. Bond lengths in milarite_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 19 8. The beryllium compounds __ ------------------------------------------------------------------------- 23 9. The beryllium fluoride compounds and their structural analogs-------------------""----------------------- 26 10. The beryllium-anion bond lengths ____________________________________________ ..:._______________________ 27 CRYSTAL CHEMISTRY OF BERYLLIUM By MALCOLM Ross ABSTRACT The beryllium ion (Be2+) has a radius of 0.33 A The present study is a compilation of the X-ray crystallogra­ (Green, 1959) and appears to be of a size that will per­ phy, chemistry, and crystal chemistry of all the known minerals mit it to readily substitute for tetrahedral Si4+, AP+, containing essential amounts of beryllium. These minerals are: P 5+ and S 6+. If such a substitution occurs, the deficiency aminoffite, barylite, bavenite, bazzite, bearsite, bertrandite, beryl, beryllite, beryllonite, beryllosodalite, bityite, bromellite, of positive charge must be adjusted for by replacement chkalovite, chrysoberyl, danalite, epididymite, euclase, eudidy­ of other cations with ones of higher charge. For ex­ mite, faheyite, gadolinite, gelbertrandite, genthelvite, gugiaite, ample, Rankama and Sahama ( 1950, p. 126) postulate hambergite, harstigite, helvite, herderite, hsianghualite, hurl­ that the small content of lanthanum sometimes present butite, karpinskyite, leucophanite, meliphanite, milarite, morae­ in potassium feldspar is a result of the substitution of site, phenakite, rhodizite, roscherite, spherobertrandite, sweden­ La3+ for K+ simultaneously with Be2+ for Si4+. As will borgite, taa:ffeite, tengerite, trimerite, and vayrynenite. The X­ ray crystallography and crystal structure of the following in­ be discussed later, such substitution mechanisms, if they organic and organic beryllium compounds are also given: do occur, occur only to a very limited extent. This is Be(H20)4S04, ,8-Be(OH)2, BeS04, BeGe04, BeS, BeSe, BeTe, probably because of the rather unsatisfactory distribu­ BeSiN
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