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Inorganic Syntheses Volumei1

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Inorganic Syntheses Volumei1 INORGANIC SYNTHESES VOLUMEI1 The quality of the maierials used in the manujacture of this book is governed by continued postwar shortages. Inorganic Syntheses Volume I1 EDITOR-IN-CHIEF W. CONARD FERNELIUS Syracuse Universitg ASSOCIATE EDITORS LUDWIG F. AUDRIETH University of Illinois JOHN C. BAILAR, JR. University of Illinois HAROLD S. BOOTH Western Reserve University WARREN C. JOHNSON University of Chicago RAYMOND E. KIRK The Polytechnic Institute of Brooklyn WALTER C. SCHUMB Mmsmhusetts Institute of Technology CONSULTANT ON NOMENCLATURE AND INDEXING JANET D. SCOTT The Interscience Encyclopedia, Inc., Brooklyn First Edition Third Impression New York London MCGRAW-HILLBOOK COMPANY, INC. 1946 INORGANIC SYNTHESESl VOLUME I1 COPYRIGHT,1946, BY THE MCGKATV-HILLBOOK COMPANY, INC. PRINTED IN THE UNITED STATES OF AMERICA All rights reserved. This book, or parts thereof, may not be reproduced in any form without permission of the publishers. TO the countless unknown but valiant soldiers of science upon whose labors Inorganic Syntheses are based, this series of volumes is dedicated in the hope that it will ease the toil of future legions. PREFACE The present volume is the second of a series giving detailed and tested methods for the synthesis of inorganic substances. The reception given the earlier volume and the support extended this one are convincing evidence of the need for this type of compilation. In the present volume the practices adopted in assembling Volume I have been continued. Each synthesis has been carefully checked in a laboratory other than that in which it was developed. All drawings and procedures have been critically edited by the Board of Editors. Where it was thought helpful, the synthesis has been introduced by a critical survey of known methods and concluded by a sum- mary of the more common properties of the substance to guide the user of the method. The references are intended to be suggestive rather than exhaustive. For convenience the book is arranged in chapters numbered according to the groups in the Mendeleev periodic table. Experience gained in producing Volume I indicated the need for adopting certain additional policies. Since every chemical compound consists of at least two elements, the inclusion of any synthesis in a given chapter on .the basis of the periodic table is somewhat arbitrary. Hence, at the beginning of each chapter is given a list of syntheses which are presented in other chapters but which might have been included in that one. In certain instances of groups of closely related syntheses in the present volume, it was deemed advisable to incorporate general summaries of the fields involved. No one today can work in the inorganic field for long without realizing the great need for an exten- sive systematization of inorganic nomenclature. This problem has been carefully studied, and the best practices have been adopted. These are explained fully in the Appendix. The index is cumulative for Volumes I and 11. Vii ... Vlll PREFACE Inasmuch as the syntheses in INORGANICSYNTHESES originate from individual contributors, the editors have been perturbed to find specific references to Volume I that do not mention the individual contributor. The editors prefer that INORGANICSYNTHESES be considered as a periodical when references are given and that credit be given to the contributor. Since the publication of Volume I, Dr. W. C. Schumb has been added to the Board of Editors and Miss Janet D. Scott has consented to serve as consultant on nomenclature and indexing. Professor L. F. Audrieth, of the University of Illinois, will serve as editor-in-chief of Volume I11 of INORGANICSYNTHESES. The collection and checking of syntheses for this volume are now under way, and con- tributions should be sent directly to Professor Audrieth. The Board asks contributors to adhere to the style followed in previous volumes and to submit drawings and manu- scripts in triplicate. It is hoped that future volumes can appear at intervals of two to three years. The editors wish to express their appreciation to those who have contributed and checked the syntheses in Volume I1 and ask for their continued cooperation. They likewise take this occasion to thank Dr. Austin F. Patterson and Dr. E. J. Crane for their helpful suggestions concerning nomenclature. The editor-in-chief is grateful to his associates for their vigorous enthusiasm and tireless labor in the preparation of Volume 11. Further, he wishes to acknowledge his great indebtedness to his wartime colleagues, Dr. C. L. Rollinson, Dr. L. E. Marchi, and Dr. E. M. Larsen, who have given unstintingly of their time and energy to help in the editing of this volume. Without their support its publication would have been further delayed. The editors will deem it a favor if readers will call their attention to any errors or omissions. WESTLAFAYETTE, INDILVA. W. CONARDFERNELIUS. August, 1946. CONTENTS PA?! Preface ................................. ...... v11 CHAPTER I 1. Copper(1) Chloride. .................. .......... i 2. Silver Chlorate.. ..................... .......... 4 3. Recovery of Silver and Iodine from Silver Iodide Residues. ....................................... G CHAPTER I1 1. Metal Derivatives of 1,3-Diketones. .......... 10 5. Beryllium Acetylacetonate [Eis(2,4-pentanedion lium] ........... ............................. 17 6. Barium Bromate. .................. ... 20 CHAPTER I11 7. Porous Boron Oxide.. .............................. 22 S. Ammonium Tetrafluoborate. ........................ 23 A. Reaction in Aqueous Solution.. ........................... 23 B. Fusion Reaction.. ................ 9.9. AluminumAluminum AcetylacetonateAcetylacetonate [Tris(2,4-pentanediono)alu-[Tris( minum]minum] ......................................... ................. ..................... 25 10.10. Gallium(II1)Gallium(II1) PerchloratePerchlorate &Hydrate.6-Hydrate ...................... 2G 11.11. TheThe Rare Rare EarthEarth Elements Elements~ andand~ TheirTheir~~ Compounds..- ~~ s...... .... 29 12. The Extraction of Rare Earth Minerals. I. Monazite and Xenotime.. ........................ A. Cracking the Mineral.. .................................. B.B. RemovalRemoval ofof Thorium..Thorium ..................................................... 41 C. Recovery of Rare Earths.. ............................... D. Conversion to Oxides.. .................................. E.E. SubsequentSubsequent Treatment.Treatm .................................. 13. The Extraction of Rare Earth Minerals. 11. Allanite, Cerite, and Gadolinite (Separation of Cerium and Yttrium Earths by the Double Sulfate Met,hod)..... 44 A. Extraction. ........................ B. Precipitation o arths. .... .................. 46 C. Separation of Cerium and Yttrium Earths. 14, The Separation of Cerium from Rare Earth Mixtures. 48 A. Separation of Cerium. ................... 4s B. Recovery of Cerium.. ................... 51 15. Fractional Crystallization; The Magnesium Rare Earth Nitrates. ......................... .......... 52 A. Preparation of a Series.. ................................. 52 B. Fractional Crystallization.. .............................. 53 C. Modifications ........................................... 57 ix X CON TE.V TS 16. The Average Atomic Weight of Rare Earth Elements in PAGE a Mixture; Method Based on the Ratios. Oxslate: Oxide and Oxalate : Permanganate ................. 58 17. Rare Earth Bromates .............................. 62 A . Preparation of the Rare Earth Eulleate Solution ............. 63 B . Preparation of Rare Earth Bromates., .................... 64 18. Europium Amalgam; Separation of Europium from Rare Earth Mixtures .................................. 65 A . Preparation of Europium Amalgam ....................... 66 B . Separation of Europium from Other Rare Earths ............ 68 19. Europium(I1) Salts ................................ 69 A . Europiurn(I1) Sulfate .................................... 70 B . Europium(I1) Carbonate ................................. 71 C . Europium(1I) Chloride ................................... 71 CHAPTER IV 20 . Sugar Charcoal .................................... 74 21 . Mo\osodiurn Acetylide (Ethynylsodium) ............. 75 A . Purification of Reagents ........ .................. 76 Sodium Acetylide from Sodium a B . Sodium and Acetylene. , C . Sodium Acetglide from SodiumSo Amide and Scetylene. 22 . Carbon Monoxide ....... 23 . Ammonium Carbamate .. 24 . Alkali Metal Cyanates ... A . Potassium Cyanate ....... B . Sodium Cyanate ......... ................... 88 25 . Cyanogen Chloride ...... ................ 90 26 . Silica Gel .............. 27 . Disilicon Rexabromide (Hexabromodisilane) .......... 98 28 . Gerrnanium(I1) Sulfide (Precipitated) ................ 102 A . Reduction of Germanium(1V) Oxide ....................... 103 B . Reduction of Germanium(1V) Sulfide ...... .......... 104 29 . Germanium(I1) Iodide ....................... ... 106 30 . Gemaniurn(1V) Chloride ....... ................. 109 31 . Germanium(1V) Iodide ......... ................. 112 32. Titanium(1V) Bromide ............................. 114 33. Titanium(II1) Bromide ............................. 116 34. Bis[tris(2,4-pentanediono)titanium(IV)] Hexachloroti- tanate(1V) ...................................... 119 . Zirconium Acetylacetonate )- 35 zirconium] ......................................[Tetrakis(2,4-pentanediono 121 36 . Thorium Acetylacetonate )- thorium] ........................................[Tetrakis(2,4-~entanediono 123 CHAPTER V 37 . Nitric Oxide [Nitrogen(II)
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