Handbook of Preparative Inorganic Chemistry

877 Pages·1965·17.964 MB·English

by  Brauer G.

PREPARED IN COLLABORATION WITH
M. Baudler, Cologne R. Klement, Munich
H. J. Becher, Stuttgart W. Kwasnik, Leverkusen
E. Donges, Gersthofen H. Lux, Munich
P. Ehrlich, Giessen W. Rudorff, Tubingen
F. Feher, Cologne H. Sauer, Hofhefm/Ts.
O. Glemser, Gottingen P. W. Schenk, Berlin
H. Grube, Hanau M. Schmeisser, Aachen
B. Grainer, Wiesbaden R. Scholder, Karlsruhe
F. Hein, Jena F. Seel, Stuttgart
S. Herzog, Greifswald F. Wagenknecht, Sprend-
lingen/Offenbach am Main
U. Hofmann, Heidelberg
R. Wagner, Stuttgart
G. Jander, Berlin
R. Juza, Kiel H. v. Wartenberg, Gottingen
K. Wetzel, Leipzig
HANDBOOK O F
PREPARATIV E
INORGANI C
CHEMISTR Y
VOLUME 2 • SECOND EDITION
Edited by GEORG BRAUE R
PROFESSOR OF INORGANIC CHEMISTRY
UNIVERSITY OF FREIBURG
TRANSLATED BY SCRIPTA TECHNICA, INC.
TRANSLATION EDITOR
PAUL G. STECHER
MERCK SHARP & DOHME RESEARCH LABORATORIES
1965
ACADEMIC PRESS • New York • London
COPYRIGHT0 1965 BY ACADEMIC PRESS INC.
• ••
ALL RIGHTS RESERVED
NOPARTOF THIS BOOK MAY BE REPRODUCED IN ANY FORM
BY PHOTOSTAT, MICROFILM, OR ANY OTHER MEANS,
WITHOUT WRITTEN PERMISSION FROM THE PUBLISHERS
ACADEMIC PRESS INC.
111 FIFTH AVENUE
New Yom, NEW York 10003
United-Kingdom Edition
Published by
ACADEMICPRESS INC. (LONDON) LTD.
BERKELEYSQUARE HOUSE, LONDON W. 1
Library of Congress Catalog Card Number:63-14307
Translated from the German
HANDBUCH DER PRAPARATIVEN ANORGANISCHEN CHEMIE
BD. 2,pp. 885-1611, 1962
Published by
FERDINAND ENKE VERLAG, STUTTGART
PRINTED IN THE UNITED
STATES OF AMERICA
Translation Editor's Preface
The English version of Volume II of Brauer's "Handbook" follows
the path of the very well received translation of Volume I . Again,
some of the material and particularly the bibliography has been
corrected and brought up to date. The nomenclature has been re-
vised where necessary, with the Stock and the Stock-Werner systems
(the practice of using Roman numerals to define oxidation states of
atoms) adopted as much as possible . This conforms with current
I. U. P. A. C. and Chemical Abstracts practice [for details of this,
see Robert C. Brasted, J. Chem. Education 35, 136 (1948)]. The
references to laboratory equipment and techniques reflect current
U.S. usage, but useful European methods have been retained.
It is hoped that this volume will be as well received as the pre -
ceding one. Comments from users are invited to help improve
future editions.
Paul G. Steoher
Rahway, N. J.
May 1965
Content s
TRANSLATION EDITOR'S PREFACE
Part II (continued)
Elements and Compounds
SECTION 19. COPPER, SILVER, GOLD 1003
Copper (Pure Metal) 1003
Colloidal Copper 1003
Copper Hydride CuH 1004
Copper (I) Chloride CuCl 1005
Copper (I) Bromide CuBr 1006
Copper (I) Iodide CuI 1007
Copper (II) Chloride CuC12 1008
Copper (II) Bromide CuBr2 1009
Copper Oxychloride CuC12 • Cu(OH)2 1010
Copper (I) Oxide Cu20 1011
Copper (II) Oxide CuO 1012
Copper (II) Hydroxide Cu(OH)2 1013
Potassium Cuprate (III) KCuO2 1014
Schweizer's Reagent 1016
Copper (I) Sulfide Cu2S 1016
Copper (II) Sulfide CuS 1017
Copper (I) Selenide Cu2Se 1019
Copper (I) Telluride CugTe 1019
Copper (I) Sulfate CuSO4 • • • • • • • • • • • • • • • • • • • . 1020
Tetraamminecopper (II) Sulfate (Cu(NH3)4)SO4 • H2O 1021
Copper (I) Nitride Cu3N 1021
Copper (II) Azide Cu(N3)2 1022
Copper Phosphide Cu3P 1023
Copper Diphosphide CuP2 1024
Basic Copper Carbonates CuCO3 • Cu(OH)2 (Green
Cupric Carbonate) 1024
2 CuCO3 • Cu(OH)2 (Blue Cupric Carbonate) 1025
Copper (I) Acetylide Cu2C2 • H2O 1026
Paris Green (Copper Acetoarsenite) 1027
Fehling's Solution 1027
Very Pure Silver 1028
Silver Powder 1029
Silver from Residues 1029
Silver Mirrors 1031
Colloidal Silver 1034
Silver Iodide AgI 1035
Silver Chlorate AgC1O3 1037
vii
CONTENTS
1037
Sliver Oxide Aga() '" 1038
Silver Peroxide Ag202 " 039
Sodium Orthoargentite Na3AgO2 1 1039
Silver (I) Sulfide Ag2S 1041
Silver (1) Selenide Ag2Se , , 1042
Silver (I) Telluride Ag2Te 1042
Silver Sulfate Ag2SO4 1043
Silver Sulfite Ag2SO3 1043
Silver Amide AgNH2 1045
Silver Azide AgN3 1045
Silver Nitride Ag3N • • • • • • • • 1047
Silver Acetylide Ag2C2 , 1047
Silver Cyanamide Ag2CN2 ' 1048
Silver Carbonate Ag2CO3
1048
Silver Nitrite AgNO2
1049
Silver Tartrate Ag2CiH4Oe • • • • • • • • • •
o-Phenanthrolinesilver (II) Persulfate [Ag phen2]S20e 1050
Tris- , n '-dipyridylsilver (II) Perchlorate
1050
[Ag(dlpyr)3](C1O4) 2 1052
Very Pure Gold
1053
Colloidal Gold
Gold from Residues 1054
Gold (I) Chloride AuC1 1055
Gold (III) Chloride AuCl3 1056
Hydrogen Tetrachloroaurate (III) HAuC1 4 • 4 H2O 1057
Potassium Tetrachloroaurate (III) KAuC14 . 1/2 H20 1058
Gold (III) Oxide Au203 1059
Gold (III) Hydroxide Au(OH)3 1060
Potassium Aurate KAuO2 • 3 H2O 1061
Gold (I) Sulfide Au2S 1061
Gold (II) Sulfide AuS 1062
Gold (III) Sulfide Au2S3 1063
Gold (1) Acetylide Au2C2 1063
Gold (I) Cyanide AuCN 1064
Potassium Dicyanoaurate (I) K[Au(CN)2] 1065
SECTION 20. ZINC, CADMIUM, MERCURY 1067
Zinc Zn 1067
Zinc Hydride ZnH2 1069
Zinc Chloride ZnC12 1070
Zinc Hydroxychloride Zn(OH)Cl 1071
Ammonium Tetrachlorozincate (NH4)2ZnC14 1072
Zinc Bromide ZnBr2 1072
Zinc Iodide ZnI2 • • 1073
Zinc Hydroxide (crystalline) (-ZnOOHC2 1074
Zinc Sulfide ZnS 1075
Zinc Vormaldehydesulfoxylate Zn(SO2 • CH20H)2 1076
CONTENTS
Ammonium Zinc Sulfate (NH4)2Zn(SO4)a • 6H2O 1077
Zinc Selenide ZnSe 1078
Zinc Amide Zn(NH2)5 1019
Zinc Nitride Zn3N2 1080
Zinc Phosphides Zn3P2, ZnP2 1080
Zinc Phosphate Zn3(PO4)2 • 4HaO 1081
Zinc Hydroxyphosphate Zn2(OH)PO4 1082
Zinc Arsenides Zn3Asa, ZnAsa 1083
Zinc Thioantimonate Z n3(SbS4)2 1083
Diethylzinc Zn(CaHs)a 1084
Zinc Carbonate ZnCO3 1086
Zinc Acetate Zn(CH3COO)2 1087
Zinc Cyanide Zn(CN) a 1087
Potassium Tetracyanozincate K2Zn(CN)4 1088
Zinc Silicate ZnaSiO4 1089
Zinc Fluorosilicate ZnSiF0 • 61120 1090
Zinc Ferrate (III) ZnFe204 1090
Rinmann's Green 1092
Cadmium (needles) Cd 1092
Cadmium Chloride CdCl2 1093
Cadmium Hydroxychloride Cd(OH)Cl 1094
Potassium Cadmium Chloride CdC12 • KC1 • H20 1095
Cadmium Bromide CdBr2 1096
Cadmium Iodide CdI2 1096
Cadmium Hydroxide Cd(OH) 2 1097
Cadmium Sulfide CdS 1098
Cadmium Nitride Cd3N2 1100
Cadmium Amide Cd(NH2)2 1100
Cadmium Phosphides Cd3P2, CdP2, CdP4 1101
Cadmium Arsenides Cd3As 2, CdAs2 1103
Diethylcadmium Cd(C 2H5)a • • • • • • • • • • • • • 1103
Cadmium Carbonate CdCO3 • • • • • • • • • • • • • • • • • • • 1104
Cadmium Acetate Cd(CH3COO)2 1105
Cadmium Cyanide Cd(CN) 2 1105
Potassium Tetracyanocadmate K2Cd(CN)4 1106
Cadmium Thiocyanate Cd(SCN) 2 1106
Cadmium Silicate Cd2SiO4 1107
Cadmium Ferrate (III) CdFe 2O4 1107
Mercury (H) Oxychloride HgC12 • 4HgO 1108
Mercury (II) Bromide HgBr2 . . . . . 1108'
Potassium Triiodomercurate (II) KHgI3 • H2O.- 111,.0
Copper (I) Tetraiodomercurate (U) Cu2HgI4 • • . • - • • - X110
Mercury (II) Sulfide HgS 11;.-7;1
Mercury (II) Selenide HgSe ;1.113
Mercury (11) Amide Chloride HgNH2CI- 1144
Diamminemeroury (II) Dichloride HgCl2 • 2 N113 . 1 '
Mercury (II) Iminobromide Hg2(NH)Br2
CONTENTS
1116
MMbBireleolrrimoccuunirrd'syye B ((o1Uaf) s) MeT T NhihlilHoioonngni'atistrO roBHosasysy•le alxa tNHteeHa[O[HgH g3•gBa(.(rNN SS))a2]x)x• • • • • • •• •• •• •• •• • • 1111111111117788
Diethylmercury Hg(CaHz)a
1120
Mercury O Acetate Hga(CH3000)2
Mercury (II) Acetate Hg(CH3COO)a • • 1120
1121
Mercury (II) Cyanide Hg(CN) a • • • • • • • • • • •
Potassium Tetracyanomercurate (II) K2Hg(CN)4 • 1122
1122
Mercury (I) Thiocyanate Hga(SCN) a
Mercury (II) Thiocyanate Hg(SCN)2 1123
Potassium Tetrathiocyanomercurate (II) K2Hg(SCN)4 1124
SECTION 21 . SCANDIUM. YTTRIUM, RARE EARTHS 1125
Pure Scandium Compounds
Treatment of Monazite Sand 1127
Treatment of Gadolinite . . . 1129
Pure La, Pr and Nd Compounds from Cerium Earths by
Ion Exchange 1131
Pure Cerium Compounds 1132
Pure Samarium Compounds 1135
Pure Europium Compounds 1136
Pure Ytterbium Compounds 1138
Metallic Rare Earths 1141
Rare Earth Trichlorides LnC13 (anhydrous) 1146
Rare Earth Tribromides LnBr3 (anhydrous) 1148
Rare Earth Triiodides LnI3 (anhydrous) 1149
Rare Earth Dihalides LnX2 (anhydrous) 1150
Cerium (III) Oxide Ce203 1151
Praseodymium (IV) Oxide PrO2 1151
Rare Earth Hydroxides Ln(OH)3 (crystalline) 1152
Lanthanum Sulfide La3S3 • 1153
Lanthanum Selenides La2Se3 , La2Se4 1154
La, Ce, Pr and Nd Monochalcogenides LnS, LnSe, LnTe 1155
Europium (II) Chalcogenides EuS, EuSe, EuTe 1155
Rare Earth Sulfates Ln2(SO4)3 • nH2O 1156
Rare Earth Nitrides LnN . . . . 1157
Rare Earth Nitrates Ln(NO3)3 (anhydrous) 1158
Rare Earth Cyclopentadienides Ln(C5H5)3 • • 1159
SECTION 22. TITANIUM, ZIRCONIUM, HAFNIUM, THORIUM . 1161
Titanium Ti
• 1161
Zirconium, Hafnium Zr, Hf 1172
Thorium Th . . . . 1174
Separation of Zirconium and Hafnium 1179
Titanium, Zirconium and Thorium Hydrides 1184
TitTatla nium.(II) Chloride; Bromide and Iodide TiC1a, TiBr a,
1185
CONTENTS
Titanium (III) Chloride, Bromide and Iodide TiC13.
TiC13 • 6 H2O; TiBr3, TiBr3 • 6 H2O; T1I3 1187
Titanium (IV) Chloride TiC14 1195
Ammonium Hexachlorotitanate (NH 4)a(TiCl e) 1199
Titanium (IV) Bromide TiBr4. . . 1201
Zirconium (N), Hafnium (N)and Thorium (IV) Chlorides
and Bromides ZrC14, HfC14, ThC14; ZrBr4, HfBr4,
ThBr4 1203
Thorium Chloride ThC14 • 8 11 20 1204
Titanium (IV), Zirconium (IV) and Thorium (IV) Iodides
TiI4 (ZrI4, Th14) 1205
Titanium (III) Oxychloride TiOC1 1209
Titanium (N) Oxychloride TiOC12 1209
Zirconium Oxychloride ZrOCl 2 • 8 H2O 1210
Hafnium Oxychloride 1213
Lower Titanium Oxides TiO, Ti203 1214
Titanium (IV) Oxide TiO2 1216
Titanium (IV) Oxide Hydrate TiO 2 • n H2O 1218
Peroxotitanic Acid H4TiO5 1219
Zirconium (IV) Oxide ZrO2 1220
Hafnium (N) Oxide HfO2 1221
Thorium (IV) Oxide ThO 2 1221
Titanium, Zirconium and Thorium Sulfides TIS3, TIS2,
TiS<a 1222
Zirconium Sulfides 1226
Thorium Sulfides 1226
Titanium (III) Sulfate Ti2(SO4)3 1226
Titanoxy Sulfate TiOSO4 1228
Zirconium Sulfates . . . 1231
Purification of Zr Salts via the Tetrahydrate 1232
Titanium, Zirconium andHafniumNitrides TIN, ZrN, HfN 1233
Thorium Nitride Th3N4 1236
Titanium Tetranitrate Ti(NO3)4 1237
Thorium Nitrate Th(NO3)4 • n H2O 1238
Titanium Oxonitrate, Zirconium Oxonitrate T10(NO3)2,
ZrO(NO3)2 1241
Titanium Phosphide, Zirconium Phosphides, Thorium
Phosphide TIP, ZrP2, ZrP, Th3P4 1241
Zirconium and Hafnium Phosphates 1244
Titanium, Zirconium and Hafnium Carbides TIC, ZrC,
HfC 1245
Thorium Carbides ThC,ThC 2 12451
Titanium, Zirconium and Thorium Silicides TM.2, ZrSi2,
1;244
ThSi2
SECTION 23. VANADIUM, NIOBIUM, TANTALUM .~ ~.:< 1252r
Vanadium V
CONTENTS
xii
1255
VVaannaaddiiuumm ((HIII)) C ChhlloorriiddeeVVCC1l2s VC13 • 6 H2O • • • • • 11225569
VVaannaaddiiuumm ((IIVI)) BCrholomriiddee VVCBr124 • • • 11226600
Vanadium (III) Bromide VBr3 • • 1261
Vanadium (II) Iodide VI2 • 1262
Vanadium (III) Iodide Via • • • • • . 1262
Vanadium Oxychloride VOC1 • • • • . .
Vanadium Oxydichloride VOC12 • • 1263
Vanadium Oxytrichloride VOC13 • • 1264
Vanadium Dioxychloride V02CI 1265
1266
Lower Vanadium Oxides
Vanadium (III) Hydroxide V(OH)3 1268
Vanadium (V) Oxide V205 1270
Ammonium Metavanadate NH4VO3 1272
Alkali Vanadates 1273
Vanadium Sulfides 1274
Vanadium Selenides 1276
Vanadium (II) Sulfate VSO4 •• 6 H2O 1277
Hydrogen Disulfatovanadate (III) HV(SO4)2 • 4 H2O• 1282
Ammonium and Potassium Disulfatovanadate (III)
NH4V(SO4)2, KV(SO4)2 1283
Vanadium (IV) Oxysulfate (Vanadyl Sulfate) VOSO4 1285
Vanadium Nitrides 1286
Vanadium Phosphides VP2, VP, VP<1 1287
Vanadium Carbides VC, V2C 1288
Dibenzenevanadium (0) V(C6H6)2 1289
Potassium Hexathiocyanatovanadate• (III) K3V(SCN) 6 1291
Niobium Metal, Tantalum Metal 1292
Vanadium, Niobium and Tantalum Hydrides 1295
Niobium (II) Chloride NbC12 1296
Niobium (III) Chloride NbC13 1297
Niobium (IV) Chloride NbC14 1299
Tantalum (IV) Chloride TaC14 1301
Niobium (V) and Tantalum (V) ChloridesNbCls, TaC16 1302
Niobium Oxytrichloride NbOC13 • 1307
Niobium (III) Bromide NbBr3 • • 1309
Tantalum (IV) Bromide TaBr4 1310
Niobium (V) and Tantalum (V) Bromides NbBr5,
TaBrs 1311
Niobium Oxytribromide NbOBrs
. . . 1313
Niobium (IV), Niobium (III) and Niobium (II)• Iodides
NbI4, NbI3, Nola , . . . . . . . 1314
Niobimm (V) Iodide NbIs
1315
Taalum(V)Iodide TaIs • . . . . . 1316
Ntabimm (II) Oxide NbO ,
1317
Niobium (IV)Oxide NbO2
1318