handbook of preparative inorganic chemistry brauer

FROM THE PREFACE TO THE F I R S T EDITION v PREFACE TO THE SECOND EDITION vi TRANSLATION EDITOR'S PREFACE vii CONVERSION OF CONCENTRATION UNITS v i i i Part I Preparative Methods PREPARA

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

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

I l l FIFTH AVENUE NEW YORK 3, N Y.

United Kingdom Edition

Published byACADEMIC 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 ofPreparative 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 P r e s s projected a completely new book: incontrast to the old, the new work would be written by a number ofinorganic chemists, each a specialist in the given field

As editor, the publishers were able to obtain the services ofProf Robert Schwartz It was Prof Schwartz who laid down whatwas to be the fundamental guideline for all subsequent work: thatonly those procedures were to be included which had been testedand confirmed in laboratory practice Concerning the choice of sub-stances, while not pretending to be exhaustive, the book wouldcover most of the compounds of inherent scientific interest or ofimportance for purposes of instruction At the same time, itwas clearly apparent that the common commercial chemicals,

as well as those whose preparations require only the simplestchemical operations, need not be included

The organization of the work took account of the broad scopeand varied nature of contemporary preparative inorganic chemistry.The increasingly rigorous purity requirements, the use of unstablesubstances and those sensitive to air and moisture, the employ-ment of ultralow and ultrahigh temperatures and pressures, etc.,have increasingly complicated the experimental apparatus andtechniques Thus, in the introductory part (Preparative Methods)the authors have endeavored to assemble a number of experimentaltechniques and special apparatus that can be extended to applicationsmuch more general than the original purposes for which they weredesigned This is complemented by an Index of Techniques atthe end of the work This index links the contents of Part I withthe various experimental procedures distributed throughout thework Space considerations have forced abridgments in severalplaces Thus, a literature reference must often take the place

of a more detailed description Occasionally, different researchershave 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 ofthe individual experimenter Thus, our own selection may notalways seem correct or adequate to every inorganic chemist

As is customary, please forward any pertinent criticism to eitherthe editor or publisher It will be gratefully received

What has been said above also holds true for Part II (Elementsand Compounds) and even more so for Part III (Special Groups ofSubstances) In every case the decision as to inclusion or omissionwas dictated by considerations of available space Here, again, theeditor would be grateful for any suggestions or criticisms.

Preface to the Second Edition

The first edition of the Handbook of Preparative InorganicChemistry was intended to fill a gap in the existing literature.Because it accomplished its mission so well, it has won widerespect and readership Thus, the authors have been persuaded toissue a second, revised and enlarged edition, even though a relativelybrief period has elapsed since the appearance of the first

The present edition is much more than a revision of the previouswork

Several sections had to be completely rewritten; in a number ofcases, the choice of compounds to be included has been changed;above all, recently developed processes, methods and apparatuscould not be neglected The reader will note also that several newauthors have cooperated in this venture

Thus, we are presenting what is in many respects a pletely new work Most of the preparative methods presented herehave either been verified by repetition in the author's own laboratory

com-or checked and rechecked in those of our collabcom-oratcom-ors We trustthat the reader will benefit from the improved reliability andreproducibility that this affords

The editorial work could not have been completed without theinvaluable help of Dr H B'arninghausen, Miss G Boos, and mywife, Doris Brauer Credit for the careful layout of the more thaneighty new or revised drawings found in the book goes to Mrs U.Sporkert To all of my co-workers, advisers, colleagues andfriends who have given their assistance, I wish to extend myheartfelt thanks

Freiburg, April 1960 G Brauer

Translation Editor's Preface

The Handbook of Preparative Inorganic Chemistry byG Brauerhas been a valuable addition to the detailed preparative literaturefor some years largely because of the number and diversity of me-thods which are contained in its pages The translation of thiswork, therefore, will simplify the task of synthesis for chemistswhose German is less than proficient

Because laboratory practice, as outlined in Part I of the book, is in some ways different from laboratory practice in theUnited States a number of additions and omissions have been made

Hand-in the translated text These Hand-include: (1) the removal of the names

of German suppliers and trade names and the substitution of ican trade names and suppliers, the latter only occasionally, (2)conversion of German glass and ground-glass joint sizes to theirAmerican equivalents, (3) substitution throughout the text of "liquidnitrogen" for "liquid a i r " , (4) improvement in the nomenclaturewhere it was judged unclear In addition, certain brief sectionshave been omitted or rewritten when the practice or equipment de-scribed was outmoded or so different as to be inapplicable in theUnited States

Amer-It is hoped that these changes have been consistent and wise spite the diffusion of responsibility for the production of a book ofthis size

de-Reed F RileyBrooklyn, New York

August, 1963

vii

D st = density of solvent

D s n = density of solution

D s e = density of solute

M s t = molecular weight of solvent

M s e = molecular weight of solute

100 • a • D s n ( 1 0 0 D s t ) + a 100- a (100 • D,,,.) + a

b

b - D s t b

100 • b D s n 100+ b

100 b 100+ b

c

100 c • Djt (100 • D s n ) - c

100 • c (100 • D s n ) - c c c Dsn

d

100 • d D st 100—d

1 0 0 - d 100-d

d D s n d

d - D s n

100 /lOO—d\M se

1 ' \ d / M s t

e

e D s e

D s n e 100A°0.Dsn \ Ms e

X e • D s e 7 Ms t

f 100 /•I 00— f W s t

1 ' \ f / M s e

100 D s n /D s e /lOO-f\Mst

1 'V f / M s e 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 carbondisulfide (15°C, given Ds n = 1.35, Ds t=1.26, Ds e = 2.07) is 24.0 g.S/100 ml CS8 or 19.05 g S/100 g CS2 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

FROM THE PREFACE TO THE F I R S T EDITION v PREFACE TO THE SECOND EDITION vi TRANSLATION EDITOR'S PREFACE vii CONVERSION OF CONCENTRATION UNITS v i i i

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, W A T E R Ill

Hydrogen H Ill

Pure Water 117 Deuterium and Deuterium Compounds 119

ix

Hydrogen Deuteride HD 126Deuterium Fluoride DF 127Deuterium Chloride DC1 129Deuterium Bromide DBr 131Deuterium Iodide DI 133

Chlorine Trioxide Fluoride C1O3F 166Chlorine Tetroxide Fluoride C1O4F 167

Thionyl Chloride Fluoride SOC1F 174Sulfuryl Chloride Fluoride SO3C1F 175Sulfuryl Bromide Fluoride SOaBrF 176

CONTENTS l

Nitrosyl Fluoride NOF 184

Phosphorus (V) Fluoride P F 190Phosphorus Dichloride Fluoride PClaF 191Phosphorus Dichloride Trifluoride P C laFa 192Phosphorus Oxide Trifluoride POF3 193Tetrachlorophosphonium Hexafluorophosphate (V)

Phosphonitrilic Fluorides (PNFa)3, (PNFS)4 194Ammonium Hexafluorophosphate (V) N H ^ F g 195Ammonium Difluorophosphate (V) NH^POgFa 196Potassium Hexafluorophosphate (V) KPFa 196

Antimony Dichloride Trifluoride SbClaF3 200

Carbonyl Chlorofluoride COC1F 208Carbonyl Bromofluoride COBrF 210Carbonyl Iodofluoride COIF 211

Potassium Hexafluorogermanate K3GeF6 216

Gallium (III) Fluoride GaF3 227Ammonium Hexafluorogallate (NH4)3(GaF6) 228

Ammonium Hexafluoroindate (NH4)3(InFs) 229Thallium (I) Fluoride T1F 230

Lithium Fluoride LiF 235Sodium Fluoride NaF 235Potassium Fluoride KF 236Potassium Hydrogen Fluoride KF • HF 237Potassium Tetrafluorobromate (III) K B r F4 237Potassium Hexafluoroiodate (V) KIFS 238Copper (II) Fluoride CuF 238

Silver Fluoride AgF 240

Potassium Heptafluoroniobate (V) KaNbF7 255

Potassium Heptafluorotantalate (V) KsTaF 256

CONTENTS X l l l

Potassium Hexafluoromanganate (IV) K3MnFs 264

Nickel (II) Fluoride NiF 269Potassium Hexafluoronickelate (IV) K3NiFs 269

SECTION 5 CHLORINE, BROMINE, IODINE 272

Polyhalides 293

Cesium Dichlorobromide CsBrClg ' 294

Potassium Tetrachloroiodide KIC14 298Tetrachloroiodic Acid HIC14 • 4 HaO 299

Potassium Hypobromite KBrO • 3 H8O 311Sodium Chlorite NaClOa • 3 HaO 312

Barium Chlorate Ba(ClO3)a • HaO 314

Barium Bromate Ba(BrO3)a H8O 316

Alkaline Earth Perchlorates 320

Sodium Periodates Na3HaIOs, NaIO4 323

Barium Periodate BagH^IOg), 326

Dipyridineiodine (I) Perchlorate [I(CBHBN)3]C1O4 327Bromine (III) Nitrate Br(NO3)3 328

Iodine (III) Sulfate I^SO^g 329Iodine (III) Perchlorate IfClO^a 330Iodine (III) Iodate I(IO3)3 or I4Og 331Oxoiodine (III) Sulfate (IO)3SO4 • HaO 332Diiodine Tetroxide IO • IO3 or IaO4 333SECTION 6 OXYGEN, OZONE 334

Sodium Dithionate NaaSaOs • 2 HaO 395Barium Dithionate BaS8O6 • 2 HaO 397Potassium Trithionate KaS3Os 398Potassium Tetrathionate KaS4Oe 399Potassium Pentathionate K8SBO6 • 1.5 H8O 401Potassium Hexathionate KaSsOs 403Wackenroder Liquid 405Polythionic Acids HaSxO3, HaSxO8 405Nitrosyl Hydrogen Sulfate (NO)HSO4 406Tetrasulfur Tetranitride 84^4 406

Sodium Hydrogen Selenide NaHSe 419Sodium Selenide, Potassium Selenide Na8Se, K8Se 421

Selenous Acid (anhydrous) HsSeO3 430Sodium Selenite Na3SeO3 • 5 H8O 431

Sodium Selenopentathionate NasSeS4Os • 3HSO 434

Selenium Nitride S e ^ * 435Tellurium Te 437Colloidal Tellurium Solution 438

Sodium Tetrahydrogentellurate (VI) Na3H4TeO8 453

Sodium Telluropentathionate Na3TeS4Oa • 2 H3O 454

Potassium Hydrazinedisulfonate H3N3(SO3K)3 509Potassium Azodisulfonate NS(SO3K)3 510Hydroxylamineisomonosulfonic Acid NH3SO4 510Nitrosyl Chloride NOC1 511Nitrosyl Bromide NOBr 513

Diphosphorus Pentasulfide PaS 6 567Monothiophosphoric Acid H3PO3S 568Sodium Monothiophosphate Na3PO3S • 12 H3O 569Sodium Dithiophosphate Na3PO3Sa • 11 H3O 570Barium Dithiophosphate Ba3(PO3Sa)3 • 8 H3O 571Sodium Trithiophosphate Na3POS3 • 11H8O 571Sodium Tetrathiophosphate Na3PS4 8 HaO 572Tetraphosphorus Triselenide P4Se3 573Triphosphorus Pentanitride P3NB 574Phosphonitrilic Chlorides (PNCls)n 575Phosphonitrilic Bromides (PNBrs)n 578Monoamidophosphoric Acid HaPOgNH3 579Disodium Monoamidophosphate Na3PO3NHa • 6 HaO 581Diamidophosphoric Acid HP03(NH3) S 582

Thiophosphoryl Triamide PS(NH3) 3 587Pyrophosphoryl Tetramide P3O3(NH3) 4 588Tetrasodium Imidodiphosphate Na^sOgNH-lO H3O 589

SECTION IO ARSENIC, ANTIMONY, BISMUTH 591

Arsenic As 591

CONTENTS X i x

Sodium Dihydrogen Arsenide NaAsH3 595

Diarsenic Trioxide As3O3(As4Os) 600Orthoarsenic Acid HaAsO* 601Sodium Dihydrogen Orthoarsenate NaHsAsO4.H8O 602Ammonium Orthoarsenate (NH4>3AsO4'3 HaO 602Tetraarsenic Tetrasulfide As 4S 4 603

Ammonium Thioarsenate (NH^sAsS^ 604Sodium Thioarsenate Na3AsS4-8 HaO 604Sodium Monothioorthoarsenate Na3AsO3S» 12 HSO 605Sodium Dithioorthoarsenate Na3AsO3S3-11 HaO 605Antimony Sb 606

Antimony (III) Oxide Chloride SbOCl 611Hexachloroantimonic (V) Acid HSbCls • 4.5 H8O 611Nitrosyl Chloroantimonate (V) NO(SbCla) 612

Ammonium Hexabromoantimonate (IV) ( N H ^ S b B r g 615

Hydrated Antimony (V) Oxide Sb3OB (H3O)X 617

Antimony (III) Oxide Sulfate (SbO)3SO4 619Sodium Thioantimonate (V) Na3SbS4«9 H8O 619Bismuth Bi 620

Bismuth Oxide Chloride BiOCl 622

Bismuth Oxide Bromide BiOBr 624

Bismuth Oxide Iodide BiOI 625

Bismuth (III) Borate BiBO3 • 2 H3O 627

SECTION I I CARBON 630 A) ELEMENTAL CARBON 630

Pure Carbon 630Special Carbon Preparations 631Surface Compounds of Carbon 633

B) G R A P H I T E COMPOUNDS 635

Alkali Graphite Compounds 635Alkali Ammine Graphite Compounds 637Graphite Oxide 638Carbon Monofluoride 640Tetracarbon Monofluoride 641Graphite Salts 642Bromine Graphite 643Metal Halide Graphite Compounds 644

c) VOLATILE CARBON COMPOUNDS 645

Ammonium Trithiocarbonate (NH4)3CS3 674

SECTION 12 SILICON AND GERMANIUM 676

Silicon Si 676Silanes SiH4 (SiaHs, Si3H8) 679

Higher Silicon Chlorides 684

Chlorosilanes SiHCl3, SiH8Cl8, SiH3Cl 691

Dimethyldichlorosilane (CH3)3SiCla 694

CONTENTS XXi

Chlorosiloxanes Si4O4Cl8, SinOn_ iCla n + s 695Silicon Monoxide SiO 696Silicic Acids 697

Silicon Tetraacetate Si(CH3COO)4 701Silicon Cyanate and Silicon Isocyanate

Tetraethoxysilane, Tetramethoxysilane

Silicates 704Germanium 706

Germanium (II) Oxide GeO 711Metallic Germanium Ge 712Germanium Hydrides GeH4 (GeaH8, Ge3Ha) 713

Germanium Dichloride GeCl 716

Trichlorogermane 721Methylgermanium Triiodide CH3GeI3 722

Germanium Monosulfide GeS 724Tetraethoxygermane Ge(OCsHB)4 725Germanium Tetraacetate Ge(CH3COO)4 726SECTION 13 TIN AND LEAD 727Tin Sn 727Tin (II) Chloride SnCl 728

Hexachlorostannic Acid H3SnCla • 6 HaO 730Ammonium Hexachlorostannate, Potassium

Hexachlorostannate (NH^jSnClg, KaSnCls 731

Tin (IV) Bromide SnBr^ 733Tin (II) Iodide SnI 734

Tin (II) Oxide SnO 736

Tin (II) Sulfide SnS 739

Sodium Metathiostannate NaaSnS3 • 8 HaO 742Sodium Tetrathiostannate (IV) Na4SnS4.18 HaO 743

Tin (IV) Sulfate SnCSO^ 2HSO 744

Lead Pb 748Lead (IV) Chloride P b C l ^ 750Ammonium Hexachloroplumbate (NHjgPbClg 751Potassium Hexachloroplumbate KaPbCle 753Potassium Iodoplumbite KPbI3 • 2 HaO 754

Lead (IV) Oxide PbO 757

Sodium Orthoplumbate N a ^ b O * 759

Lead Sulfide PbS 760Lead (IV) Sulfate P ^ S O ^ g 761

Neutral and Basic Lead Carbonate

SECTION 14 BORON 770Boron 770

Sodium Trimethoxyborohydride NaHB(OCH3)3 777Borine Trimethylaminate BH3 • N(CH3)3 778

CONTENTS xxiii

Sodium Pentaborate NaBBO9 • 5 H3O 795

Lindemann Glass (Lithium Beryllium Borate) 796

Tri-n-Butylboroxine (n-C4HgBO)3 801n-Butylboronic Acid n-C4H9B(OH)8 801n-Butylboron Difluoride n-C4HgBF3 802Sodium Tetraphenylborate Na[B(CsH5)j 803

SECTION 15 ALUMINUM 805

Polymeric Aluminum Hydride (AlH3)n • x O(C8H5)3 807Aluminum Chlorohydride A1SC13H3 808Aluminum Hydride Trimethylaminate

A1H3 • 2 N(CH3)3> A1H3 • N(CH3)3 809Diethylaluminum Bromide Al(CaHe)aBr 809

Triethylaluminum Etherate A1(CSH5)3 • O(C3HB)a 811Diethylaluminum Hydride Al(CaH5)aH 811

Aluminum Chloride Hydrate A1C13 • 6 HaO 815Sodium Tetrachloroaluminate NaALCl* 816Tetrachloroaluminic Acid Dietherate HA1C14 • 2 O(CaH5)a 816Aluminum Chloride Ammoniate A1C13 NH3 817Aluminum Chloride-Sulfur Dioxide Adduct A1C13 • SO8 817Aluminum Chloride-Thionyl Chloride Adduct

Aluminum Sulfite 824

Aluminum Nitride A1N 827Lithium Aluminum Nitride Li3AlN3 828

Aluminum Phosphide A1P 829Lithium Aluminum Phosphide Li3AlP8 830

Aluminum Arsenide AlAs 831

Lithium Aluminum Cyanide LiAl(CN)4 833

Aluminum Ethoxide A1(OC8HS)3 834Aluminum Triethanolaminate A1(OC8H4)3N 835Aluminum Acetate A1(O8CCH3)3 835Aluminum Acetylacetonate Al(CsH7Oa)3 836

SECTION 16 GALLIUM, INDIUM, THALLIUM 837

Gallium Ga 837Trimethylgallium, Tetramethyldigallane, Digallane

Ga(CH3)3, GasHa(CH3) <, GasH8 840Lithium Tetrahydrogallate LiGaH4 842

Gallium (II) Chloride and Gallium (II) Bromide GaCls,

Gallium Hydroxide Ga(OH) 3, GaO(OH) 847Gallium (III) Oxide a-GaaO3, j8-Ga3O3 848

Gallium (IT) Sulfide GaS 851

Ammonium Gallium (III) Sulfate NH 4<Gra(SO4) 9 • 12 HaO 854Gallium Selenide GasSe3, GaSe, GaaSe 854

Gallium Nitride GaN 855

Gallium Phosphide, Arsenide and Antimonide GaP, GaAs,GaSb 857Indium In 857

Indium (II) Chloride, Bromide and Iodide InCla, InBra, Inla 861Indium (I) Chloride, Bromide and Iodide InCl, InBr, Inl 862

Cesium Nonachlorodithallate (III) Cs3(TlsCl9) 874Thallium (III) Bromide TlBr3 • 4 H3O 874Thallium (I) Tetrabromothallate (III) Tl(TlBr4) 875Thallium (1) Hexabromothallate (III) Tl3(TlBra) 875Rubidium Hexabromothallate (III) Rb3(TlBr6) • 8A HSO 876Thallium Triiodide Til • I3, T1I3 876

Thallium (I) Hydroxide TlOH 877Thallium (II) Oxide T13O3, Tl3O3 • x H30 879Thallium Sulfides 880Thallium (I, III) Selenide Tl3Se • TlaSe3, TISe 881

Disulfatothallic (III) Acid HTl(SO4)s • 4 H3O 882Thallium (III) Hydroxide Sulfate Tl(OH)SO4 • 2 H3O 882

Thallium (II) Formate, Thallium (I) Malonate, Clerici'sSolution 884

SECTION 17 ALKALINE EARTH METALS 887

Beryllium Be 887

Beryllium Oxide and Beryllium Carbonate BeO, BeCO3 893

Sodium Beryllates 895Beryllium Sulfide BeS 895Beryllium Selenide and Beryllium Telluride BeSe, BeTe 897

Beryllium Carbides Be3C, BeC8 899

Basic Beryllium Acetate Be4O(CH3COO)8 901Magnesium Mg 903

Magnesium Oxide MgO 911

Magnesium Sulfide MgS 913Magnesium Selenide MgSe 915Magnesium Telluride MgTe 915

Magnesium Phosphide and Magnesium Arsenide Mg3P3,

Strontium Hydroxide Sr(OH)3 • 8 H3O, SrO • 9 H3O 935Calcium, Strontium, Barium Peroxides CaO8, SrO3, BaO3 936Calcium, Strontium, Barium Sulfides CaS, SrS, BaS 938Calcium, Strontium, Barium Selenides CaSe, SrSe, BaSe 939Calcium, Strontium, Barium Nitrides Ca3Na, Sr 3N3, Ba3N3 940

Calcium Germanide CaGe 948

SECTION 18 ALKALI METALS 950

Alkali Metal Compounds from Minerals 950Free Alkali Metals 956Alkali Hydrides NaH, KH, RbH, CsH and LiH 971Alkali Metal Oxides Li3O, Na3O, KSO, Rb3O, CssO 974Lithium and Sodium Peroxides Li3Oa and Na3O3 979Alkali Dioxides 980Lithium Hydroxide LiOH • H3O, LiOH 982

Part I Preparative Methods

P W SCHENK AND G BRAUER

This part of the book describes special methods and devices forinorganic preparations We do not intend to present a compre-hensive, thorough compilation of all the known methods of prepara-tive inorganic chemistry, such as given in handbooks An enterprise

of that kind would require too much space, and the appropriatebooks are already available Even through the several-volumetreatise by Stock, Staehler, Tiede and Richter is by now partlyoutdated, many references, methods and descriptions of apparatus,useful for solving experimental problems, can be found in special-ized books, such as those by Von Angerer, Dodd and Robinson,Grubitsch, Klemenc, Kohlrausch, Lux and Ostwald-Luther [1],

to name but a few These texts can thus be consulted when the needarises

In Part I, only a more or less subjective selection of methodsand devices is presented This selection was governed by certainprinciples Increased emphasis on greater purity of preparationsand the advent of extreme experimental conditions have imposedmore rigorous demands on the experimental equipment Porcelaindishes and beakers must increasingly be complemented or replaced

by more complicated apparatus for the preparation of unstable oroxidizable substances Such special demands placed on individualpreparatory steps have often led to the development of generalprocedures which can be applied to a larger number of preparationsthan was originally contemplated An effort has been made to ex-tract such standard methods and techniques from later sections and

to summarize them in this first part Whenever a too detailed scription had to be omitted because of space limitations, at leastthe original literature reference is given In addition to briefdescriptions of the more commonly used and well-known specialequipment, an attempt has also been made to describe some ofthe experimental "art," namely, those little tricks and short-cutswhich with the passage of time have become traditional in almostevery laboratory, but which somehow never seem to find theirway into the literature

de-4 P W SCHENK AND G BRAUER

Assembly of Apparatus

The classic Bunsen support with its clamps and brackets isstill the most frequently used framework for assembling apparatus.There are various newer variations of it which eliminate themovement of the clamps when the brackets are tightened

It is best to assemble a permanent support so that the entirestructure can be easily carried about without having to dismantle iteach time and so that it can be set aside when not in use Such anarrangement is especially useful with the most commonly usedpieces of apparatus, e.g., pump assemblies consisting offorepump,mercury traps and vacuum measuring instruments, or apparatusused for the preparation, purification and drying of inert or otherfrequently used gases To construct more extensive assemblies,

it is best to interconnect individual uprights with round steel rods

13 mm in diameter, and to increase the stability of the whole, theuprights are fastened to similar rods, cemented into the wall

It is also very helpful to attach strong wooden strips, about 10 cm.wide, horizontally along the wall above the working benches (onestrip about 30 cm., the other about 80 cm above the bench surface).The rods holding the uprights in place can then be screwed intowall receptacles (1/4" size, available in hardware supply stores)which are fastened to the wooden strips These round wall r e -ceptacles can also be fastened with screws to the work bench tohold the vertical rods, thus replacing the base plate of the support.The cross braces fastened to the wall, or else suitable clamps,allow the work bench supports to be eliminated, and the entireapparatus can then be mounted directly on the wall This has theconsiderable advantage of leaving the table space free, so that itcan be kept clean more easily, and so that spilled mercury can bereadily wiped up If the apparatus is very tall, a "gallows* frame(Fig 1) can be used, mounted on a table about 60 cm above the floor.This frame is free standing and, as a result, the experimentalapparatus can easily be reached from all sides Similar structurescan be built on the free-standing center benches of the laboratory

by attaching four vertical rods to the two short sides of a benchand connecting them horizontally with matching round rods Suitableperforated structural steel angles with corresponding bolts and nutsare available for the various setups, even those built up from thefloor These perforated angles can be assembled into very stablestructures resembling those which children build from Erector sets.Additional suggestions and details about frame materials can befound in G C Monch [2] In assembling the apparatus, special care

is required in selecting the right location and the proper supporting clamps Too many clamps, causing stresses whichare liable to break the apparatus, are just as bad as too fewclamps

-760-Fig 1 Frame for setting up a free-standing experimental appa- ratus (measurements in cm.).

Glassware is identified by a special brand number and by the trademark of the firm manufacturing it A helpful characteristic

93 • 10~7 (25°C)

33 • 10~7 (0—300°)

8 • 10-7 (0—300°)

5 • 10-7 (0-300°)

is the color of the glass, the "hue," which can clearly be seen

by transmitted light on a freshly broken end piece The mostcommon colors vary from yellow to green

Table 2Chemical Composition of Some Types of Glass

4

4

K S O 0.6

<0.1

<0.1

CaO 5.6

<0.1

<0.1

BaO 2.0

MgO 4.0

AlsOs2.8

solu-to alkali, as shown in Tables 3 and 4

Many more details about the types of glass can be found inthe descriptive literature of the manufacturers

The various parts of a glass apparatus are assembled into aunit by using ground glass joints, rubber tubing, stoppers, ad-hesives and especially by sealing glass tubing together with handtorches The handling of these torches can be easily learned even

by one having no previous knowledge of glass blowing A glass seal

Table 3Hydrolytic Resistance

of powderedglass

7.8

0.26

Weightloss,

1 Use glass tubing and other necessary glass from the samemanufacturer

2 Protect glass from dust and store it horizontally; if it isnecessary to store it vertically due to lack of space, cover theopenings

3 Before using, clean the glass tubing by pushing or blowingthrough a moist piece of cotton; clean tubes of larger diameterswith a moist rag pulled through on a string; never clean the in-terior surfaces of glass tubing with an iron or steel wire or anotherpiece of glass tubing Ignoring this rule is a common cause ofcracked tubing during heating

4 Only freshly cut surfaces, not touched by fingers, should besealed When it is impossible to trim an end piece in order toobtain a freshly cut surface, heat the area with a torch and pull offsome glass with the aid of a glass rod, or melt the glass, blow thisarea into a thin-wall bubble and strip it off

5 When working with hard borosilicate glass (Pyrex), oxygen

is added to the a ir stream through a tee-connector tube.* Thedifficulty of working at higher temperatures notwithstanding,

•Blowtorches and hand torches equipped with a valve for oxygenaddition are commercially available

8 P W SCHENK AND G BRAUER

borosilicate glasses are more amenable to glass blowing than the soft glasses because they are much less likely to crack when un- evenly heated.

Base Resistance5% NaOH at 100°C5% NaOH at 100°C

6 hr

6 hr

Weight loss,mg./cm.2

0.0045

0 0005

1.4 0.9

Industrial fusion of pure quartz yields clear quartz glass or vitreous silica It has the following advantages: low 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 Oxy- hydrogen 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, manipu- lation of quartz is no more difficult than that of ordinary glass However, the following hints will be useful for those working with quartz glass:

1 Holes often do not close completely in the molten glass; fine capillaries usually remain open Such spots must be repeatedly remelted or drawn together with a thin quartz rod.

2 Since SiO and SiOs vaporize, quartz glass becomes cloudy

in the melted area Remedy: After completing the main sealing operation, remelt the whole area until it is clear, using a large but not too hot oxy-hydrogen flame; if necessary, follow with a rinse of dilute hydrofluoric acid.

3 Rapid blowing is essential because the viscosity tends to crease rapidly on cooling; blowing is best done with a rubber tube.

in-4 On cooling or on prolonged exposure to heat, there exists the danger of devitrification; that is, conversion of the meta- stable, glassy form to cristobalite may occur Once it has started, this process rapidly leads to mechanical failure of the apparatus The failure starts preferentially at the externally adhering impurity

centers and proceeds very rapidly, especially at temperatures inexcess of 1000°C Consequently, those parts of quartz glasswarewhich are to be heated and which have already been thoroughlycleaned (with aqueous solutions or organic liquids such as alcohol,acetone, etc.) must not be touched prior to heating because perspira-tion (NaCl) acts as a devitrifying agent.

The upper temperature limit, when quartz glass is used in theabsence of a pressure differential, is 1250°C Unfortunately, evacu-ated quartz glass flasks start to deform in the 1150°C region Thedevitrification and warping phenomena make quartz glass vesselsunsuitable for experiments in which they must be exposed to tem-peratures higher than 1000°C over long periods of time

Glasses which cannot be directly sealed together can be connected by means of graded seals Seals having diameters of7—9 mm (O.D.) are commercially available They consist of aseries of very short tubes, each with a slightly different coefficient

inter-of expansion In this way, even sinter-oft glass can be connected toquartz 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 cleaned withCrO3-H8SO4 cleaning solution by allowing it to stand in the solu-tion for some time, and then rinsing with water Laug [2] cautions,however, that the glass absorbs CrO3 upon treatment with thiscleaning solution The CrO3 cannot be completely removed, even byboiling with water According to Laug, one gram of glass takes upabout 5 mg of CrO3, of which 0.2 mg remains in the glass even afterrepeated boiling with water In certain cases, it is preferable toclean the glassware with concentrated nitric acid Treatment withalkaline permanganate solution, followed by successive rinsingwith water, concentrated hydrochloric acid, and again with water

is also very effective

Glass tubing and apparatus parts which cannot be placed in adrying oven because of their size should not be dried by rinsingwith organic solvents (alcohol-ether, acetone); such solvents areoften contaminated with low-volatility impurities and these, ifleft on the glass walls, will cause trouble with sensitive substances,

or at high vacuum Instead, room air should be drawn through thetubes or apparatus by means of an aspirator, with only one openingaccessible to the air This opening should be protected againstdust with a cotton wad or a piece of soft filter paper

Apparatus that is to be taken apart should be provided withground glass connections One can use for this purpose standardtapered joints or ball joints The latter are now manufacturedwith great precision and are being used more and more In manycases flanged ground-face connections are advantageous (for detailssee Monch [2]) The great advantage of ball joints is their flexibility

10 P W SCHENKANDG BRAUER

and easy detachability; they are held together by simple clamps.Their price, on the other hand, is greater than that of the c o r r e -sponding tapered joints Ball joints designation includes the diam-eter of the tube The following sizes are available on the market:

12/5 18/7 18/9 28/12 28/15 35/20 35/25

50/30 65/40 75/50 102/75

In addition, the smallest size, with a ball 12 mm in diameter,

is available with capillaries of 1—3 mm

The designation of the tapered joints has been changed severaltimes Table 5 lists the present standards for the different series.All joints are ground with a taper of 1:10 [(larger diameter minussmaller diameter): length of ground portion = 1:10],

The question of which part of the apparatus should carry themale joint, and which the female, is often hard to decide The bestgeneral advice that can be given is to keep the reagents free fromcontamination Thus, if the ground joint is to be greased, the femaleshould be on top and the male below; in this case, however, cleaning

of the joint is usually more difficult A groove formed in the groundsurface of the male ("two-zone grinding") is very useful in prevent-ing penetration of the grease into the apparatus Parts which are

to be weighed on an analytical balance should carry the male, cause it can be cleaned more easily It is highly recommendedthat small hooks be attached to both parts of the joint, so that thelatter may be held together with springs or rubber bands

be-If joints of different materials are to be assembled and heat is

to be applied, the female should always be made of the materialwith the higher expansion coefficient This applies especially toglass-quartz joints In an assembly consisting of a glass male and

a quartz female, the latter will, as a rule, crack on immersion inboiling water

Greasing of stopcocks and other ground joints, as well assuitable lubricants and adhesives, will be discussed later In somecases, it is advantageous to make the connections by cementing andwithout using any ground joints This method is especially usefulwhen very large tubes are to be connected, since such cementedseals, if correctly prepared, can be removed without shifting theother parts of the apparatus The seal is made with a glass sleeve,

as shown in Fig 2 It is best to polish the two butting edges (sothat the cut on each is straight) and to interpose a narrow, annealedcopper ring, especially if the apparatus is to be evacuated; other-wise, the glass edges may splinter due to the compressive force

of atmospheric pressure To secure sufficient adhesive strength,

it is important that the cement be melted by warming the supportingglass This is especially important with metal cements, since in thiscase leaks cannot be easily detected To heat the places to be

Table 5 Designation and Measurements of American Standard Taper

Ground Joints (CS 21—39) *Long

Short 12/10 14/10 19/10 24/12 29/12 34/12 40/12 45/12 50/12 55/12 60/12 71/15

* The first number in the designation indicates the larger diameter of the ground section; the second, the length

of the ground section.

cemented, one can use a small pilot flame, 10—15 mm long, created

by a glass or metal tip.

If certain precautions are taken, metals can be easily and tightly sealed to glass This is especially true of Kovar tubing, which can

be sealed to Pyrex glass.

12 P W SCHENK AND G BRAUER

borer, well lubricated with glycerol, should be introduced betweenglass tube and stopper and the borer retracted several times, whileadding more glycerol

If rubber stoppers are to be bored, the borer should never beturned in one direction only; instead, the direction should be changedafter each half turn, withdrawing the borer several times in order

to add more glycerol Otherwise, the hole gets continually narrower,since the rubber core inside the borer also turns The hole isthen not cut by the sharp edge of the borer but, instead, the rubber

is torn out

Ceramic Materials

The refractory ceramic materials used in the laboratory can beclassified, as in Table 6, according to their properties and mainingredients Unlike glass vessels, their shaping is finished beforethe high-temperature treatment (firing) Only limited subsequenttreatment is possible and this is restricted to mechanical modifica-tion (grinding, cutting) Since firing is accompanied by shrink-age, close tolerances can be maintained to a limited extent only.These characteristics restrict ceramic laboratory ware to certain,usually standardized items, e.g., straight tubes, rods, crucibles,dishes, boats, etc

Group 1 These materials, which consist essentially of A1SO3and SiOa, are resistant to extended heating at higher temperatures,but are often not as gas-tight as pure SiO2, although some of themcome close in this respect Gas permeability depends very much onthe temperature and increases with rising temperature In addition

to the well-known laboratory porcelain ware, some manufacturershave developed special items which have higher chemical ortemperature resistances (cf synopsis in Table 11) The maximumuse temperature for these materials increases with the AlaO5content Again, because of the typical ceramic method of manufac-ure of these materials (shaping, firing), only some, usually stand-ardized, laboratory items can be made (straight tubes, rods,crucibles, dishes, boats, etc.) Glazes are applied only to porcelain.Ability to withstand temperature changes is much lower than withpure silica

Chemical resistance at high temperatures is poorest towardalkaline and strongly reducing materials (e.g., active metals).Again, chemical and thermal resistance increases in proportion

to the A1SO3 content

For special purposes (e.g., highchemcial resistance),materials

of Group 1 can be lined with substances which by themselvesare not suitable for ceramic manufacture (for example, MgO, CaO).For example, according to Goehrens [3], one can apply to the vessel

a paste made of a mixture of finely ground, weakly ignited and

Table 6Group

(silicate vitreous bond)

As l a , with special

vitreous bond; partly pure

Sintered alumina,magnesia, beryllia,zirconia and thoria

Fire clays, mullite,sillimantine, corun-dum (kaolin-bonded)Electrode carbon, retortgraphite, graphite (clay-bonded)

coarse, strongly ignited magnesia in a saturated MgCls solution.This is then transformed by drying and gradual heating into a well-adhering protective layer of MgO In order to deposit a CaO layer(which, among others, can also be applied to ferrous vessels)calcium oxide is made into apaste with calcium nitrate; or, accord-ing to W Jander [3], a paste of CaO and water is painted on to athickness of 0.3—0.4 cm Drying and subsequent heating shouldstart at 40°C and be increased very slowly up to red heat

Group 2 For work at very high temperatures, reaction vesselsmade of ceramic oxide compounds have proved especially suitable;this refers to vessels which have been made by sintering oxides ofhigh purity and of very high melting point Such materials excel

in their resistance to high temperatures and in their remarkabletolerance of a wide range of materials at high temperatures Foralmost every material to be melted there can be found an especiallysuitable ceramic oxide material, as is shown below Because ofthe difficulties encountered in ceramic manufacture, the bestthermal and chemical resistance characteristics can be achievedonly at some sacrifice of flexibility in the choice of ceramic shapes

14 P W SCHENK AND G BRAUER

In the following tables (7—11), which summarize the availablepractical experience and offer some suggestions for use, the mean-ings of the symbols are: +++not attacked; -H-very slightly attacked;+ slightly attacked; — strongly attacked; very strongly attacked;

—• completely destroyed.

In using the physical technique of vapor deposition of thin face layers, some knowledge has been gathered about compati-bility between the boat and crucible materials and the reagentsheated in these vessels (cf Auwarter [4]) Table 12 summarizesthese data

sur-Group 3 Besides the materials of sur-Groups 1 and 2, porousceramics are important These often are more resistant to

Table 7Behavior of Ceramic Oxide Apparatus with Fused Metals

+++

+++

++

* Only after previous coating of the crucible with molten LiF

** Vessels made of impure oxides are less resistant

Table 8Behavior of Ceramic Oxide Apparatus with Liquids

103

A12O3++

+ + ++

++

++

ZrO2

+ ++

++

temperature changes This latter characteristic is sometimes bined with higher maximum use temperatures Some of thesematerials are also available as pastes (insulating compounds).Group 4 In this group, use is made of the extremely high melt-ing point of carbon, which is usually not reached in practice

com-T a b l e 9

Behavior of C e r a m i c Oxide A p p a r a t u s with O x i d e s , H y d r o x i d e s ,

and C a r b o n a t e s Agent

10001000100013001250/ 1780

\ 1900

900 850

1900

800

16001600170015001600

600

A 1 2 O 3 +++