handbook of preparative inorganic chemistry brauer

HANDBOOK OF PREPARATIVE INORGANIC CHEMISTRY VOLUME 1 • SECOND EDITION Edited by GEORG BRAUER PROFESSOR OF INORGANIC CHEMISTRY UNIVERSITY OF FREIBURG TRANSLATED BY SCRIPTA TECHNICA, INC. TRANSLATION EDITOR REED F. RILEY ASSOCIATE PROFESSOR OF CHEMISTRY POLYTECHNIC INSTITUTE OF BROOKLYN 1963 ACADEMIC PRESS • New York • London COPYRIGHT © 1963 BY ACADEMIC PRESS INC. ALL RIGHTS RESERVED NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM BY PHOTOSTAT, MICROFILM, OR ANY OTHER MEANS, WITHOUT WRITTEN PERMISSION FROM THE PUBLISHERS. ACADEMIC PRESS INC. Ill FIFTH AVENUE NEW YORK 3, N. Y. United Kingdom Edition Published by ACADEMIC PRESS INC. (LONDON) LTD. BERKELEY SQUARE HOUSE, LONDON W. 1 Library of Congress Catalog Card Number: 63-14307 Translated from the German HANDBUCH DER PRAPARATIVEN ANORGANISCHEN CHEMIE BD. 1, 884 pp., 1960 Published by FERDINAND ENKE VERLAG, STUTTGART PRINTED IN THE UNITED STATES OF AMERICA From the Preface to the First Edition For many years, the inorganic section of the "Handbook of Preparative Chemistry" by L. Vanino was a laboratory standard. By 1940, however, the third (and last) edition of the handbook was no longer in print. Rather than simply reissue the Vanino manual, the Ferdinand Enke Press projected a completely new book: in contrast to the old, the new work would be written by a number of inorganic chemists, each a specialist in the given field. As editor, the publishers were able to obtain the services of Prof. Robert Schwartz. It was Prof. Schwartz who laid down what was to be the fundamental guideline for all subsequent work: that only those procedures were to be included which had been tested and confirmed in laboratory practice. Concerning the choice of sub- stances, while not pretending to be exhaustive, the book would cover most of the compounds of inherent scientific interest or of importance for purposes of instruction. At the same time, it was clearly apparent that the common commercial chemicals, as well as those whose preparations require only the simplest chemical operations, need not be included. The organization of the work took account of the broad scope and varied nature of contemporary preparative inorganic chemistry. The increasingly rigorous purity requirements, the use of unstable substances and those sensitive to air and moisture, the employ- ment of ultralow and ultrahigh temperatures and pressures, etc., have increasingly complicated the experimental apparatus and techniques. Thus, in the introductory part (Preparative Methods) the authors have endeavored to assemble a number of experimental techniques and special apparatus that can be extended to applications much more general than the original purposes for which they were designed. This is complemented by an Index of Techniques at the end of the work. This index links the contents of Part I with the various experimental procedures distributed throughout the work. Space considerations have forced abridgments in several places. Thus, a literature reference must often take the place of a more detailed description. Occasionally, different researchers have solved a given problem by different experimental techniques. Here again a reference to the literature is in order. Naturally, the choice of preferred method is always a subjective decision of the individual experimenter. Thus, our own selection may not always seem correct or adequate to every inorganic chemist. As is customary, please forward any pertinent criticism to either the editor or publisher. It will be gratefully received. Vi PREFACE TO THE SECOND EDITION What has been said above also holds true for Part II (Elements and Compounds) and even more so for Part III (Special Groups of Substances). In every case the decision as to inclusion or omission was dictated by considerations of available space. Here, again, the editor would be grateful for any suggestions or criticisms. Preface to the Second Edition The first edition of the Handbook of Preparative Inorganic Chemistry was intended to fill a gap in the existing literature. Because it accomplished its mission so well, it has won wide respect and readership. Thus, the authors have been persuaded to issue a second, revised and enlarged edition, even though a relatively brief period has elapsed since the appearance of the first. The present edition is much more than a revision of the previous work. Several sections had to be completely rewritten; in a number of cases, the choice of compounds to be included has been changed; above all, recently developed processes, methods and apparatus could not be neglected. The reader will note also that several new authors have cooperated in this venture. Thus, we are presenting what is in many respects a com- pletely new work. Most of the preparative methods presented here have either been verified by repetition in the author's own laboratory or checked and rechecked in those of our collaborators. We trust that the reader will benefit from the improved reliability and reproducibility that this affords. The editorial work could not have been completed without the invaluable help of Dr. H. B'arninghausen, Miss G. Boos, and my wife, Doris Brauer. Credit for the careful layout of the more than eighty new or revised drawings found in the book goes to Mrs. U. Sporkert. To all of my co-workers, advisers, colleagues and friends who have given their assistance, I wish to extend my heartfelt thanks. Freiburg, April 1960 G. Brauer Translation Editor's Preface The Handbook of Preparative Inorganic Chemistry byG. Brauer has been a valuable addition to the detailed preparative literature for some years largely because of the number and diversity of me- thods which are contained in its pages. The translation of this work, therefore, will simplify the task of synthesis for chemists whose German is less than proficient. Because laboratory practice, as outlined in Part I of the Hand- book, is in some ways different from laboratory practice in the United States a number of additions and omissions have been made in the translated text. These include: (1) the removal of the names of German suppliers and trade names and the substitution of Amer- ican trade names and suppliers, the latter only occasionally, (2) conversion of German glass and ground-glass joint sizes to their American equivalents, (3) substitution throughout the text of "liquid nitrogen" for "liquid air", (4) improvement in the nomenclature where it was judged unclear. In addition, certain brief sections have been omitted or rewritten when the practice or equipment de- scribed was outmoded or so different as to be inapplicable in the United States. It is hoped that these changes have been consistent and wise de- spite the diffusion of responsibility for the production of a book of this size. Reed F. Riley Brooklyn, New York August, 1963 vii Conversion of Concentration Units D st = density of solvent D sn = density of solution D se = density of solute M s t = molecular weight of solvent M se = molecular weight of solute a b c d Unit g./lOO ml. solvent g./lOOg. solvent g./100 ml. solution g. /100 g. solution (wt. %) a a a 100 • a • D sn (100.D st )+a 100- a (100 • D,,,.) + a b b-D st b 100 • b . D sn 100+ b 100 . b 100+ b c 100 . c • Djt (100 • D sn )-c 100 • c (100 • D sn )-c c c Dsn d 100 • d . D st 100—d 100-d 100-d d.D sn d d e f g./lOO g. solution (wt. %) ml./100 ml. solution (vol. %) moles/100 moles solution (mole %) d d d - D sn 100 /lOO—d\M se 1 '\ d /M st e e.D se D sn e 100 A°0.D sn \M se X e • D se 7 M st f 100 /•I 00— fW st 1 '\ f /M se 100 . D sn /D se /lOO-f\Mst 1 'V f /M se f mole fraction = moles of solute/total moles =7™ molality = moles of solute/1000 g. of solvent = - molarity = moles of solute/1000 ml. of solution = *° * c Example: The concentration of a solution of sulfur in carbon disulfide (15°C, given D sn = 1.35, D st =1.26, D se = 2.07) is 24.0 g. S/100 ml. CS 8 or 19.05 g. S/100 g. CS 2 or 21.6 g. S/100 ml. solution or 16.0 g. S /100 g. solution or 16.0 wt. % or 10.4 vol. % or 31.2 mole %. viii Contents FROM THE PREFACE TO THE FIRST EDITION v PREFACE TO THE SECOND EDITION vi TRANSLATION EDITOR'S PREFACE vii CONVERSION OF CONCENTRATION UNITS viii Part I Preparative Methods PREPARATIVE METHODS 3 Assembly of Apparatus 4 Glass 5 Ceramic Materials 12 Metals 17 Plastics 25 Pure Solvents 25 Mercury 27 Sealing Materials and Lubricants 28 High Temperatures 32 Low Temperatures 42 Constant Temperature 45 Temperature Measurement 49 High Vacuum and Exclusion of Air 53 Special Vacuum Systems 66 Gases 77 Liquefied Gases as Solvent Media 86 Electrical Discharges 90 Purification of Substances 91 Analysis of Purity 100 Powder Reactions 103 Part II Elements and Compounds SECTION I. HYDROGEN, DEUTERIUM, WATER Ill Hydrogen H Ill Pure Water 117 Deuterium and Deuterium Compounds 119 Deuterium D s 121 ix X CONTENTS Hydrogen Deuteride HD 126 Deuterium Fluoride DF 127 Deuterium Chloride DC1 129 Deuterium Bromide DBr 131 Deuterium Iodide DI 133 Deuterium Sulfide D a S 134 Deuterosulfuric Acid D 8 SO 4 135 Deuteroammonia ND 3 137 Deuterophosphoric Acid DgPO^ 138 SECTION 2. HYDROGEN PEROXIDE 140 Hydrogen Peroxide H 3 O a 140 SECTION 3. FLUORINE, HYDROGEN FLUORIDE 143 Fluorine F 3 143 Hydrogen Fluoride HF 145 SECTION 4. FLUORINE COMPOUNDS 150 General Remarks 150 Chlorine Monofluoride C1F 153 Chlorine Trifluoride C1F 3 155 Bromine Trifluoride BrF 3 156 Bromine Pentafluoride BrF B 158 Iodine Pentafluoride IF B 159 Iodine Heptafluoride IF 7 160 Dioxygen Difluoride O s F a 162 Oxygen Difluoride OF S 163 Chlorine Dioxide Fluoride C1O S F 165 Chlorine Trioxide Fluoride C1O 3 F 166 Chlorine Tetroxide Fluoride C1O 4 F 167 Sulfur Tetrafluoride SF 4 168 Sulfur Hexafluoride SF S 169 Thionyl Fluoride SOF 3 170 Thionyl Tetrafluoride SOF 4 171 Sulfuryl Fluoride SO 3 F 173 Trisulfuryl Fluoride S 3 O S F 174 Thionyl Chloride Fluoride SOC1F 174 Sulfuryl Chloride Fluoride SO 3 C1F 175 Sulfuryl Bromide Fluoride SO a BrF 176 Fluorosulfonic Acid HSO 3 F 177 Potassium Fluorosulfinate KSO a F 178 Selenium Hexafluoride SeF s 179 Selenium Tetrafluoride SeF 4 . 180 Tellurium Hexafluoride TeF s 180 Nitrogen Trifluoride NF 3 181 Ammonium Fluoride NH 4 F 183 Ammonium Hydrogen Fluoride NH^ • HF 183 CONTENTS X l Nitrosyl Fluoride NOF 184 Nitrososulfuryl Fluoride FSO a NO 186 Nitryl Fluoride NO S F 186 Fluorine Nitrate NO 3 F 187 Phosphorus (IE) Fluoride PF 3 189 Phosphorus (V) Fluoride PF 190 Phosphorus Dichloride Fluoride PCl a F 191 Phosphorus Dichloride Trifluoride PCl a F a 192 Phosphorus Oxide Trifluoride POF 3 193 Tetrachlorophosphonium Hexafluorophosphate (V) PC1 4 • PF S 193 Phosphonitrilic Fluorides (PNF a ) 3 , (PNF S ) 4 194 Ammonium Hexafluorophosphate (V) NH^Fg 195 Ammonium Difluorophosphate (V) NH^POgFa 196 Potassium Hexafluorophosphate (V) KPF a 196 Arsenic (III) Fluoride AsF 3 197 Arsenic (V) Fluoride AsF B 198 Antimony (III) Fluoride SbF 3 199 Antimony (V) Fluoride SbF B 200 Antimony Dichloride Trifluoride SbCl a F 3 200 Bismuth (III) Fluoride BiF 3 201 Bismuth (V) Fluoride BiF B 202 Carbon Tetrafluoride CF 4 203 Trifluoromethane CHF 3 204 Trifluoroiodomethane CIF 3 205 Carbonyl Fluoride COF 3 206 Carbonyl Chlorofluoride COC1F 208 Carbonyl Bromofluoride COBrF 210 Carbonyl Iodofluoride COIF 211 Silicon Tetrafluoride SiF 4 212 Trifluorosilane SiHF 3 214 Hexafluorosilicic Acid H 8 SiF s 214 Germanium Tetrafluoride GeF 4 215 Potassium Hexafluorogermanate K 3 GeF 6 216 Tin (II) Fluoride SnF s 217 Tin (IV) Fluoride SnF 4 217 Lead (II) Fluoride PbF 8 218 Lead (IV) Fluoride PbF 4 219 Boron Trifluoride BF 3 219 Fluoroboric Acid HBF 4 221 Sodium Fluoroborate NaBF 4 222 Potassium Fluoroborate KBF 4 223 Potassium Hydroxyfluoroborate KBF 3 OH 223 Nitrosyl Fluoroborate NOBF 4 224 Aluminum Fluoride 225 Ammonium Hexafluoroaluminate (NH^gAlFg 226 Ammonium Tetrafluoroaluminate NH4A1F 4 227 Xll CONTENTS Gallium (III) Fluoride GaF 3 227 Ammonium Hexafluorogallate (NH4) 3 (GaF 6 ) 228 Indium (III) Fluoride InF 3 228 Ammonium Hexafluoroindate (NH4) 3 (InF s ) 229 Thallium (I) Fluoride T1F 230 Thallium (III) Fluoride T1F 3 230 Beryllium Fluoride BeF s 231 Ammonium Tetrafluoroberyllate (NH 4 ) 3 BeF 4 232 Magnesium Fluoride MgF s 232 Calcium Fluoride CaF 3 233 Strontium Fluoride SrF 3 234 Barium Fluoride BaF a 234 Lithium Fluoride LiF 235 Sodium Fluoride NaF 235 Potassium Fluoride KF 236 Potassium Hydrogen Fluoride KF • HF 237 Potassium Tetrafluorobromate (III) KBrF 4 237 Potassium Hexafluoroiodate (V) KIF S 238 Copper (II) Fluoride CuF 238 Silver Subfluoride Ag a F 239 Silver Fluoride AgF 240 Silver (II) Fluoride AgF a 241 Zinc Fluoride ZnF a 242 Cadmium Fluoride CdF a 243 Mercury (I) Fluoride Hg a F a 243 Mercury (II) Fluoride HgF s 244 Scandium Fluoride ScF 3 245 Yttrium Fluoride YF 3 .' 246 Lanthanum Fluoride LaF 3 246 Cerium (III) Fluoride CeF 3 247 Cerium (IV) Fluoride CeF 4 247 Europium (II)Fluoride EuF a 248 Titanium (III) Fluoride TiF 3 248 Titanium (IV) Fluoride TiF 4 250 Zirconium (IV) Fluoride ZrF 4 251 Vanadium (III) Fluoride VF 3 252 Vanadium (IV) Fluoride VF 4 252 Vanadium (V) Fluoride VF B 253 Niobium (V) Fluoride NbF B 254 Potassium Heptafluoroniobate (V) K a NbF 7 255 Tantalum (V) Fluoride TaF 5 255 Potassium Heptafluorotantalate (V) K s TaF 256 Chromium (II) Fluoride CrF s 256 Chromium (III) Fluoride CrF 3 257 Chromium (IV) Fluoride CrF 4 258 Chromyl Fluoride CrO a F a 258 Molybdenum (VI) Fluoride MoF 8 259 [...]... Preparative Methods P W SCHENK AND G BRAUER This part of the book describes special methods and devices for inorganic preparations We do not intend to present a comprehensive, thorough compilation of all the known methods of preparative inorganic chemistry, such as given in handbooks An enterprise of that kind would require too much space, and the appropriate books are already available Even through the... Antimonides and Bismuthides of Alkali Metals from the Elements Sodium and Lithium Carbides Na s C 3 , Li 3 C 3 Alkali Metal Carbonates of Highest Purity Silicides and Germanides of Alkali Metals from the Elements NaSi, KSi, RbSi, CsSi, NaGe, KGe, RbGe, CsGe 983 984 FORMULA INDEX 985 987 987 989 993 Part I Preparative Methods Preparative Methods P W SCHENK AND G BRAUER This part of the book describes special... clamps PREPARATIVE METHODS -760- Fig 1 Frame for setting up a free-standing experimental apparatus (measurements in cm.) Glass The important types of glass used in chemical work are shown in Table 1 The chemical composition of the more frequently used types of glass is shown in Table 2 The ordinary starting material for the manufacture of laboratory glassware and connectors consists of glass tubes of circular... loss, mg./cm.8 0.002 0.26 negligible at the ends of two glass tubes often can be formed in a shorter time than is required for careful connection of the tubes with rubber tubing The technique of glass blowing is best learned under the tutorship of an experienced individual; a description of manipulations can thus be omitted here However, a few hints will be offered: 1 Use glass tubing and other necessary... available with capillaries of 1—3 mm The designation of the tapered joints has been changed several times Table 5 lists the present standards for the different series All joints are ground with a taper of 1:10 [(larger diameter minus smaller diameter): length of ground portion = 1:10], The question of which part of the apparatus should carry the male joint, and which the female, is often hard to decide The... of graded seals Seals having diameters of 7—9 mm (O.D.) are commercially available They consist of a series of very short tubes, each with a slightly different coefficient of expansion In this way, even soft glass can be connected to quartz glass Sealing wires into glass is described in detail elsewhere [2] With quartz glass only molybdenum can be used Cleaning of glassware: Glass equipment is usually... store it vertically due to lack of space, cover the openings 3 Before using, clean the glass tubing by pushing or blowing through a moist piece of cotton; clean tubes of larger diameters with a moist rag pulled through on a string; never clean the interior surfaces of glass tubing with an iron or steel wire or another piece of glass tubing Ignoring this rule is a common cause of cracked tubing during heating... reproducibility of the machine-drawn tubing is considerably superior Glassware is identified by a special brand number and by the trademark of the firm manufacturing it A helpful characteristic Table 1 Type of glass Flint glass (Kimble) Pyrex glass Vycor glass Quartz glass Linear coefficient of expansion 7 93 • 10~7 (25°C) 33 • 10~ (0—300°) 7 8 • 10-7 (0—300°) 5 • 10- (0-300°) P W SCHENK AND G BRAUER is... temperature coefficient of expansion, transparency and relatively good, but strongly selective chemical resistance Tubing, ground joints, etc., of quartz glass can also be made in the laboratory Oxyhydrogen or hydrogen-air flames with additional oxygen are used In a pinch, a small industrial oxy-acetylene welding torch will suffice Despite the high softening temperature of 1500°C, manipulation of quartz is no... rinse of dilute hydrofluoric acid 3 Rapid blowing is essential because the viscosity tends to increase rapidly on cooling; blowing is best done with a rubber tube 4 On cooling or on prolonged exposure to heat, there exists the danger of devitrification; that is, conversion of the metastable, glassy form to cristobalite may occur Once it has started, this process rapidly leads to mechanical failure of . HANDBOOK OF PREPARATIVE INORGANIC CHEMISTRY VOLUME 1 • SECOND EDITION Edited by GEORG BRAUER PROFESSOR OF INORGANIC CHEMISTRY UNIVERSITY OF FREIBURG TRANSLATED BY. Preface The Handbook of Preparative Inorganic Chemistry byG. Brauer has been a valuable addition to the detailed preparative literature for some years largely because of the number and diversity of me- thods. organization of the work took account of the broad scope and varied nature of contemporary preparative inorganic chemistry. The increasingly rigorous purity requirements, the use of unstable substances