Inorganic Syntheses, Volume 5

316 Pages·1957·76.197 MB·English

Inorganic Syntheses
VOLUME V
Inorganic Syntheses
VOLUME V
EDITOR-IN-CHIEF
THERALD MOELLER
University of Illinois
ASSOCIATE EDITORS
GEORGE H. CADY EUGENE G. ROCHOW
University of Washington Haruard University
HENRY F. HOLTZCLAW, JR. WALTER SCHUMB
C.
University of Nebraska Massachusetts Institute of Technology
JACOB KLEINBERG JANET D. SCOTT
University of Kasas G. & C. Merriam Company
ADVISORY BOARD
LUDWIG F. AUDRIETH WARREN C. JOHNSON
University of IUinois University of Chicago
JOHN C. BAILAR, JR. HERMAN I. SCHLESINGER
University oj IUirwia University of Chicago
COKARD FERNELIUS RALPH C. YOUNG
w.
The Pennsylvania State University Massachusetts Institute of Technology
RIIcGRAW-HILL BOOK COMPANY, INC.
New York Toronto London
1957
INORGANIC SYNTHESES, VOLUME
V
Copyright @ by the McGraw-Hill Book Company, Inc. Printed in thr
1957
United States of America. All rights reserved. This book, or parts thereof,
may not be reproduced in any form without permission of the publishers.
Library of Congress Catalog Card Number
39-23015
THE MAPLE PRESS COMPANY, YORK, PA.
To
Raymond Eller Kirk
(1890-1 957)
and
Arthur Alphonzo Blanchard
(1876-1956)
PREFACE
The enthusiastic reception accorded earlier volumes in
this series and the continuing interest expressed in them
have encouraged the Board of Editors of INORGANIC
SYNTHESEtoS continue the series in the present volume.
The rapidly expanding interest in inorganic chemistry, as
reflected by increased publication of the results of funda-
mental research, by greater emphasis upon instruction at
the advanced level, and by development of new industrial
processes, indicates clearly the necessity for making avail-
able exact and t,ested procedures for the preparation of
inorganic substances. It is hoped that the material in
these volumes will both aid in the solving of specific prob-
lems and stimulate additional interest in, and investigation
of, other problems in the inorganic area.
The policy of having each synthesis carefully checked in
at least one independent laboratory has been continued.
This has provided a means of determining the exactness
and correctness of each procedure and often a means of
increasing the usefulness of the procedure through incor-
poration of the findings of the checker. Each synthesis
has been edited after checking and approved in final form
by both submitter and checker before publication. That
many of the procedures either originated or were checked
in industrial laboratories may be taken as indicative that
the material here is of both technical and fundamental
interest. The Board of Editors is particularly happy to
point out that many of the procedures have come from
abroad.
In accordance with the convention established in earlier
vii
viii PREFACE
volumes, the syntheses in Volume V are arranged by chap-
ters on the basis of the Xlendeleev periodic classification.
Further subdivision into A and B families has been effected
also. A few brief survey articles have been included at
pertinent places to broaden the scope of the treatment.
The system of nomenclature is that followed in Volumes
I1 to IV. The volume has been cross-referenced liberally,
and the subject and formula indexes are cumulative for all
five volumes.
Contributions are now being accepted for publication in
Volume VI of the series. All manuscripts should be for-
warded to Prof. Eugene G.R ochow, of Harvard University,
who will serve as editor-in-chief of Volume VI. All such
manuscripts should be submitted in triplicate and should
follow, as nearly as possible, the style used in earlier vol-
umes. Each manuscript should include in order a brief
introduction summarizing reported methods of synthesis, a
detailed procedure written in the present passive, a brief
summation of important physical and chemical properties.
and an accurate compilation of pertinent references listed
with initials of the authors. Analytical methods which are
distinctive should be included in a separate section after
Procedure. Numerical data on yields and analytical
results are essential in all possible cases.
The Board of Editors takes great pleasure in announcing
the election to membership on the Editorial Board of Dr.
Eugene 0. Brimm, of Linde Air Products Company; Dr.
Joseph J. Katz, of the Argonne National Laboratory; and
Prof. Geoffrey Wilkinson, of the Imperial College, London.
The editors wish, again, to call attention to the fact that
INORGANICS YNTHESEisS a periodical publication and that
a reference to an article appearing in any volume should
include the names of the authors of that article and not
the name of the editor-in-chief of the volume.
The editor-in-chief is most grateful to his associates on
the Editorial and Advisory Boards for their assistance and
advice in the preparation of Volume V. Miss Janet D.
PREFACE ix
Scott has been particularly helpful in handling all the prob-
lems of nomenclature and indexing. The editor wishes
also to thank Mrs. Marie C. Hall for her aid in preparing
the manuscript and Mr. Valentine D. Galasyn for his
invaluable help in editing the manuscript and checking
proof.
The editors will be most grateful to readers and users of
this and other volumes of INORGANISCY NTHESEfoSr infor-
mation concerning any errors or omissions.
Therald Moeller
CONTENTS
Preface . . . . . . . . . . . . . . . vii
CHAPTER IA
1. Lithium Hydroperoxide 1-Hydrate, Lithium Peroxide,
and Lithium Oxide . . . . . . . . . 1
2. Sodium Dispersions . . . . . . . . . . 6
3. Sodium Hydride . . , . . . . . . . . 10
CHAPTER JB
4. Dichloro(d i-2-pyrid ylamine) copper (II ) and Bis(di-2-
pyridylamine)copper(II) Chloride. . . . . . 14
5. Diiodocuprate(1) . . 16
Bis(ethylenediamine)copper(II)
6. Disilver Fluoride . . . . . . . . . . . 18
CHAPTER IIA
7. Beryllium Chloride. . . . . . . . . . . 22
CHAPTER IIIA
8. Boron Halide-Amine Coordination Compounds . . 26
A. Boron Fluoride-Trimethylamine . . . . . 26
B. Boron Chloride-Trimethylamine . . . 27
9. Ethyl Orthoborate . . . . . . . . . . . 29
CHAPTER IIIB
10. Isolation of Samarium, Europium, and Ytterbium
Materials by Means of Sodium Amnlgam . 32
A. General Procedure . . , . . . . . . 33
B. Separation of Samarium and Europium . 35
11. Anhydrous Lanthanon Nitrates . . . . . . . 37
CHAPTER IVA
12. Cyanogen . . . . . . . . . . . . . 43
xi
xii CON TENTS
13. Allophanyl Hydrazide . . . . . . . . . . 48
A. Alkyl Allophanates . . . . . . . . . 49
B. Allophanyl Hydrazide . . . . . . . . 50
14. Urazole . . . . . . . . . . . . . . 52
A. Preparation from Methyl Allophanate . . . 53
B . Preparation from Ethyl Allophanate . . . . 54
15. Silica Gel (Correction) . . . . . . . . . . 55
16 . Organosilazane Compounds . . . . . . . . 55
A. Hexamethyldisilazane . . . . . . . . 56
B. N-methylhexamethyldisilazane . . . . . 58
C . Trimethyl (ani1ino)silane . . . . . . . 59
D . Hexamethylcyclotrisilazane and Octamethylcy-
clotetrasilazane . . . . . . . . . 61
17. Organogermanium Compounds . . . . . . .
64
18. Tetraphenylgermane . . . . . . . . . . 70
19. Hexaphenyldigermane . . . . . . . . . . 72
20 . Diphenylgermane . . . . . . . . . . . 74
21 . Triphenylbromogermane and Triphenylgermane . . 76
CHAPTER IVB
22 . Extraction of Titanium(1V) Oxide from Ilmenite . . 79
A. Decomposition of the Mineral . . . . . . 80
B. Removal of Iron . . . . . . . . . . 80
C . Recovery of Titanium(1V) Oxide . . . . . 81
23 . Titanium(1V) Sulfide . . . . . . . . . . 82
CHAPTER VA
24 . Nitrogen(1V) Oxide . . . . . . . . . . 87
.
25 l,l,l -Trisubstituted Hydrazonium Chlorides . . . 91
A. The Chloramide Generator . . . . . . . 92
B . l,l,l -Trimethylhydrazonium Chloride . . . 94
C . l,l,l -Triethylhydrazonium Chloride . . . . 94
26 . Phosphorus(II1) Fluoride . . . . . . . . . 95
27 . Hexaguanidonium Tetraphosphate l-Hydrate . . . 97
A . Purification of Sodium Tetrametaphosphate . . 98
B . Hydrolysis of Tetrametaphosphate to Tetra-
phosphate . . . . . . . . . . . . 99
C . Precipitation of Hexaguanidonium Tetraphos-
phate . . . . . . . . . . . . . 1 00
.
28 Sodium Monothiophosphate . . . . . . . . 1 02
CONTENTS xiii
CHAPTER VB
29. Preparation of Metal Derivatives of 1,3-Diketones . 105
30. Vanadium(1V) Oxy(acety1acetonate) . . . . . 113
A. Preparation from Vanadium(V) Oxide through
Prior Reduction to Oxyvanadium(1V) Ion . . 114
B. Direct Preparation from Vanadium(V) Oxide . 115
CHAPTER VIA
31. . . . . . 117
N-Nitrosohydroxylamine-N-sulfonates
A. Potassium . 117
N-Nitrosohydroxylamine-N-sulfonate
B. . 119
SodiumN-Nitrosohydroxylamine-N-sulfonate
C. by Meta-
N-Nitrosohydroxylamine-N-sulfonates
thesis . . . . . . . . . . . . . 120
32. Hydroxylamine-0-sulfonic Acid . . . . . . . 122
33. Selenium(1V) Chloride. . . . . . . . . . 125
CHAPTER VIB
34. Chromium(II1) Iodide. . . . . . . . . . 128
35. Chromium(II1) Acetyhcetonate . . . . . . . 130
36. Aquopentammine- and Acidopentamminechromium-
(111) Salts. . . . . . . . . . . . . 131
A. Aquopentamminechromium(1 11) Ammonium Ni-
trate . . . . . . . . . . . . . 132
B. Nitropentamminechromium(II1) Nitrate . . . 133
C. Nitratopentamminechromium(II1) Nitrate . . 133
D. Bromide . . 134
Bromopentamminechromium(I1I)
37. Tungsten Hexacarbonyl . . . . . . 1 35
38. Tripotassium . . . . 139
Enneachloroditungstate(II1)
39. Uranium(1V) Chloride. . . . . . . . . . 143
40. Uranium(II1) Chloride. . . . . . . . . . 145
41. Uranyl Chloride . . . . . . . . . . . 148
42. Uranyl Hydrogen Orthophosphate 4-Hydrate . . . 150
CHAPTER VIIA
43. Anhydrous Metal Chlorides . . . . . . . . 153
44. Chlorine(1) Compounds . . . . . . . . . 156
A. Chlorine(1) Oxide . . . . . . 1 56
B. Chlorine(1) Oxide in Carbon Tetrachloride Solu-
tion . . . . . . . . , . . . . 158
C. Hypochlorous Acid . . . . . . . . . 160
D. Calcium Hypochlorite . . . . . . . . 161