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wt-book of Inorganic Chemistry, Vol. VI , Purl V.}
[Frontispiece.
9
1 "
CA ;
> r-H CO ^ 01
CM CO
A TEXT-BOOK OF
INORGANIC CHEMISTRY.
EDITED BY
J. NEWTON FRIEND, D.Sc., PH.D., F.I.C.,
RXKC.ri-: GOLD MEDALLIST.
VOLUME VI., PART V.
ANTIMONY AND BISMUTH.
BY
W. E. THORXEYCROFT. B.Sc.
L (.) X D X :
CHARLES GRIFFIN & COMPANY, LIMITED,
42 DJIUUY LANE, W.C. 2.
1 930.
Pnnte.-.l m Cheat Britain by
\~EILL <i Co., LTD., EDINBURGH.
GENERAL INTRODUCTION TO THE SERIES.
DURING the past few years the civilised world has begun to realise the
advantages accruing to scientific research, with the result that an ever-
increasing amount of time and thought is being devoted to various
branches of science.
No study has progressed more rapidly than chemistry. This
science may be divided roughly into several branches : namely, Organic,
Physical, Inorganic, and Analytical Chemistry. It is impossible to
write any single text-book which shall contain within its two covers a
thorough treatment of any one of these branches, owing to the vast
amount of information that has been accumulated. The need is rather
for a series of text-books dealing more or less comprehensively with
each branch of chemistry. This has already been attempted by
enterprising firms, so far as physical and analytical chemistry are
concerned ; and the present series is designed to meet the needs of
inorganic chemists. One great advantage of this procedure lies in
the fact that our knowledge of the different sections of science does not
progress at the same rate. Consequently, as soon as any particular
part advances out of proportion to others, the volume dealing with
that section may be easily revised or rewritten as occasion requires.
Some method of classifying the elements for treatment in this way
is clearly essential, and we have adopted the Periodic Classification
with slight alterations, devoting a whole volume to the consideration
of the elements in each vertical column, as will be evident from a glance
&
at the scheme in the Frontispiece.
In the original scheme, in addition to a detailed account of the
elements of Group 0, the general principles of Inorganic and Physical
Chemistry were discussed in Volume I. It was later felt, however, that
this arrangement was hardly satisfactory, and an Introduction to these
principles is now afforded by my Text-book of Physical Chemistry,
Volumes I. and II. (1932-35), whilst in future editions Volume I. of this
Series will deal with the Inert (rases alone.
Hydrogen and the ammonium salts arc dealt with in Volume II. ,
along with the elements of Group I. The position of the rare earth
metals in the Periodic Classification has for many years been a source
of difficulty. They have all been included in Volume IV., along with
the elements of Group III., as this was found to be the most suitable
place for them.
Many alloys and compounds have an equal claim to be considered
in two or more volumes of this scries, but this would entail unnecessary
duplication. For example, alloys of copper and tin might be dealt
with in Volumes II. and V. respectively. Similarly, certain double
salts _, -li, for example, as ferrous ammonium sulphate might very
logically be included in Volume II. under ammonium, and in Volume IX.
x AXTIMOXY AXD BISMUTH.
under iron. As a general rule this difficulty has been overcome by
treating complex substances, containing two or more metals or bases,
in that volume dealing with the metal or base which belongs to the
highest group of the Periodic Table. For example, the alloys of copper
and tin are detailed in Volume V. along with tin, since copper occurs
earlier, namely, in Volume II. Similarly, ferrous ammonium sulphate
is discussed in Volume IX. under iron, and not under ammonium in
Volume II. The ferrocyanides are likewise dealt with in Volume IX.
But even with this arrangement it has not always been found easy
to adopt a perfectly logical line of treatment. For example, in the
chromates and permanganates the chromium arid manganese function
as part of the acid radicals and are analogous to sulphur and chlorine
in sulphates and perchlorates ; so that they should be treated in the
volume dealing with the metal acting as base, namely, in the case
of potassium permanganate, under potassium in Volume II. But- the
alkali permanganates possess such close analogies with one another
that separate treatment of these salts hardly seems desirable. They
are therefore considered in Volume VIII.
Numerous other little irregularities of a like nature occur, but it is
hoped that, by means of carefully compiled indexes and frequent cross-
referencing to the texts of the separate volumes, the student will
experience 110 difficulty in finding the information he requires.
Particular care has been taken with the sections dealing with the
atomic weights of the elements in question. The figures given are not
necessarily those to be found in the original memoirs, but have been
recalculated, except where otherwise stated, using the following-
fundamental values :
Hydrogen = 1-00702. Oxygen = 10-000.
Sodium = 22-096. Sulphur = 32-065.
Potassium = 39-100. Fluorine = 19-015.
Silver 107-880. Chlorine 35-457.
Carbon = 12-003. Bromine = 79-916.
Nitrogen --= 14-008. Iodine = 126-920.
By adopting this method it is easy to compare directly the results of
earlier investigators with those of more recent date, and, moreover, it
renders the data for the different elements strictly comparable through-
out the whole series.
Since the original scheme was drawn up in 1912, enormous progress
has been made in all branches of chemistry, and the original intention
of devoting one book only to each Vertical Group in the Periodic Table
has had to be abandoned. In several cases it has been necessary to
devote a whole book to a single clement, us, for example, in the cases
of oxygon, nitrogen, phosphorus and arsenic. Further, a separate
volume has been devoted to the Metal- Am mines and a comprehensive
account of the Organomctallic Derivatives is given in Volume XL, which
is being issued in ('our parts.
The Editor would draw attention to the unsatisfactory state of the
nomenclature of organomctallic compounds in general. The designa-
tions of compounds in Volume XI. arc those used in the original memoirs,
since any attempt to alter these in a work of that description would only
complicate matters.
Our aim has not been to make the volumes absolutely exhaustive,
GENERAL INTRODUCTION TO THE SERIES. xi
as this would render them unnecessarily bulky and expensive ; rather
has it been to contribute concise and suggestive accounts of the various
topics, and to append numerous references to the leading works and
memoirs dealing with the same. Every effort has been made to render
these references accurate and reliable, and it is hoped that they will
prove a useful feature of the series. The more important abbreviations,
which are substantially the same as those adopted by the Chemical
Society, are detailed in the subjoined lists, pp. xvii-xix.
The addition of the Table of Dates of Issue of Journals (pp. xxi-xxviii)
will, it is hoped, enhance the value of this series. It is believed that
the list is perfectly correct, as all the figures have been checked against
the volumes on the shelves of the library of the Chemical Society by
Mr. F. W. Clifford and his staff. To these gentlemen the Editor and
the Authors desire to express their deep indebtedness.
In order that the series shall attain the maximum utility, it is
necessary to arrange for a certain amount of uniformity throughout,
and this involves the suppression of the personality of the individual
author to a corresponding extent for the sake of the common welfare.
It is at once my duty and my pleasure to express my sincere appre-
ciation of the kind and ready manner in which the Authors have
accommodated themselves to this task, which, without their hearty
co-operation, could never have been successful. Finally, I wish to
acknowledge the unfailing courtesy of the publishers, Messrs. Charles
Griffin & Co., who have done everything in their power to render the
work straightforward and easy.
J. NEWTON FRIEND.
September 1930.
PREFACE.
ACCORDING to the Oxford English Dictionary, the origin of both names
antimony and bismuth is unknown, and, unfortunately, something of this
obscurity appears to overshadow many of the problems connected
with the chemistry of these two elements and their compounds. It is
possible that this arises from their position as the last two elements
of Sub-group B of Group V. of the Periodic Classification. In accord-
ance with that position, although they retain many of the character-
istics of the group as a whole (which have been considered in Part I.
of this Volume), they possess in addition definite basigenic properties.
Thus, many of their compounds readily undergo hydrolysis, but fre-
quently the hydrolysis is not complete, intermediate products of great
complexity being produced, the natures of which have not yet been
fully established. Moreover, there is evidence to show that the process
of hydrolysis is not always continuous, but is complicated by secondary
reactions between the hydrolytic products and the solutions from
which they are formed. These factors have rendered it extremely
difficult to obtain compounds of these two elements in a state of purity,
the perplexities arising from this being exemplified in the controversies
concerning the atomic weights of the two elements, which have been
concluded satisfactorily only within the last twenty years.
Another feature of these two elements is the tendency of both to
form complexes. In some cases these complexes have been shown to
partake of the nature of anions; in others, their true nature is not fully
known. The study of these questions involves the conception of
valency, but, in this book, it has been deemed advisable to discuss the
compounds of the two elements in the light of the older valency theories,
in which these elements were regarded as existing in one of the two
states ter- or quinquc-valcnt. Further study of antimony and bismuth
in combination should throw considerable light on valency relationships
and should prove of great value not merely in elucidating the chemistry
of the two elements themselves, but in advancing the knowledge of
structural chemistry in general.
In the metallic state antimony and bismuth arc not very widely
employed, in industry or the arts, although the former clement is an
essential component of some exceedingly important alloys, such as type
metal and bearing metal, the many varieties of which play such a con-
spicuous part in modern civilisation. Bismuth is chiefly valuable as
a component of fusible alloys; this is perhaps due not so much to its
own low melting point as to its great tendency to form cutcctics. It
is noteworthy that bismuth docs not enter largely into combination,
nor into solid solution, with other metals.
The anisotropic nature of the crystals of these two metals has
attracted considerable attention from physicists; with the development
of the technique for the production of single crystals the examination
xiv ANTIMONY AXD BISMUTH.
of the physical properties of bismuth in particular has been very exten-
sive. Many of the published results, however, must be accepted with
reserve, as the investigators did not appear to appreciate fully that
the physical condition of the material employed was of as much import-
ance as the chemical purity. The close alliance which has arisen in
recent years between physicists and metallurgists cannot fail to bear
fruit in this field of research; and it is possible that a careful examina-
tion of the physical properties of the two elements antimony and
bismuth may throw considerable light on the nature of the metallic
state, in spite of the fact that they themselves are such imperfect
metals.
An attempt has been made in this book to describe the state of
knowledge of the chemistry of the two elements and their compounds
up to the end of 1934. Many themes of a physico-chemical nature
have received but a mere mention; it is hoped, however, that references
to original sources will enable the reader to follow up those themes
with a minimum of labour.
In addition to the literature cited, much assistance has been obtained
from Gmelin-Kraut, " Handbuch der anorganischen Chemie" and from
il A Comprehensive Inorganic Chemistry'' by J. W. Mellor.
Finally, the author very gratefully acknowledges his indebtedness
to Messrs. Cooke. Troughton and Sirnms, Ltd., of York, for permission
to reproduce the Plate showing the macrostructure of antimony (from
a photograph by Mr. M. C. Oldham of the English Steel Corporation);
to Dr. E. B. R. Prideaux and Mr. R. H. Vallance for their valuable
assistance in proof-reading; and to the General Editor of the Series,
Dr. J. Newton Friend, not only for the sympathy and courtesy with
which he has smoothed over many difficulties during the preparation
of this book, but also for his active co-operation in certain sections,
notably in those on the atomic weights.
W. E. THORXEYCROFT.
WoLLASToy, STOUKBRTDG E .
September 1936.
CONTENTS. .
THE PERIODIC TAIJLE (Frontispiece] .....
GENERAL INTRODUCTION TO THE SERIES ....
PREFACE .......-
LIST or ABBREVIATIONS .......
TABLE OF DATES OF ISSUE OF JOURNALS ....
CHAPTER I. Antimony and its Alloys ....
OCCURRENCE Early History Extraction Physical Properties Allot.ro pit;
Forms .............
RHOMBOHEDRAL, OR a-ANTJMONY Crystal Structure Density Compressi-
bility Thermal Expansion Hardness Mechanical Properties Specilie J leal.
Melting Point Latent Heat of Fusion Physical Properties of Liquid.
Antimony Thermal Conductivity Electrical Properties Magnetic Proper ties
Refractive Index ...........
EXPLOSIVE, AMORPHOUS OR /'-ANTIMONY--- -Preparation- Phase Diagram
and Transition to .Rhomhohedral Antimony Physical Properties- .
YELLOW ANTIMONY ..........
SPECTRUM- Arc Spectrum Spark Spectrum Absorption Spectrum -
Fluorescence Absorption Spectrum of Solutions of Anlimonv Trichloride
X-ray Spectrum ..........
SINGLE CRYSTALS or ANTIMONY ........
CHEMICAL PROPERTIES Reactions vnth Non-meta.Is and Non-metallie
Compounds Reactions with Metals and Metallic. Compounds -At omiciiy
Electrode Potential The Antimony Electrode ......
ATOMIC WEIGHT OT ANTIMONY Approximate Atomic Weight--- Exact
Atomic Weight Atomic Weight of Antimony from "Different Sources - Tsotopcs
ALLOYS OF ANTIMONY Commercial Alloys Binary Alloy Systems -
Ternary Alloys . . . . . . " . .
CHAPTER II. Compounds of Antimony
GENERAL Physiological Aciion of Antimony and its Compounds
ANTIMONY AND HYDROGEN Di-anlimony .Dihydride Antimony Tri-
hydridc .
ANTIMONY AND TIH<; II A.LOC;I';NS Antimony Tnfluoridc-- Antimony IVnta-
fluoridc Antimony Trichloride Oxychloridcs of Te.rvalent Antimony
Antimony Tetra.chloride Antimony ! Vntachlonde Chloroant imonic. Acids
Antimonyl Perch loraie Antimony Tn bromide- An( irnon y Ox v bromides
Antimony Tot rabromide ATitjinony Pent. a bromide - - Anf.imon y ' Tri iodide
Antimony Oxy iodide- Antimony Thioiodido Ani i ninny I odoryanido.s Mixed
'Halides of Ant.imony
ANTIMONY AND OXYGEN (ienoral Ant nnony Trioxide -II yd rated Anti-
mony Trioxidc Ani imomto* Ani imony Tct roxule - Ant imonv I'ent oxide
llydrated Ant.imony IN-ntoxide Antinu.ma.1es
ANTTMONY AND SrLi>i-n;n General Ant imony Trisulpliide - -Thioa.nt.i-
monites Antimony Tetrasulphiclc Antimony Pentasulpliidt^ Tlno;uiti-
monatcs- Antimony Snlphatc Stibiothiosulphate*
xv
xvi ANTIMONY AND BISMUTH.
ANTIMONY AND SELENIUM Antimony Triselenidc Antimony Solcnitcs and
Selenates Selenoantimonites and Sclenoantimonates .....
ANTIMONY AND TELLUIIIUM Antimony Tritelluride ....
ANTIMONY AND NTTROOEN Antimony Nitride Antimony Nitrate .
ANTIMONY AND PHOSPHORUS ........
ANTIMONY AND AKSENLC .........
DETECTION AND ESTIMATION OF ANTIMONY ....
CHAPTER III. Bismuth and its Alloys
OCCURRENCE Early History Extraction ......
PHYSICAL PROPERTIES Allotropy Crystal Structure Single Cryst als
Density Thermal Expansion Compressibility Hardness Mechanical Pro-
perties Specific Heat Melting Point Latent Heat of Fusion Volume
Change on Fusion Properties of Liquid Bismuth Boiling Point Vapour
Pressure Thermal Conductivity Electrical Properties Magnetic Properties
Optical Properties ...........
SPECTRUM. Arc Spectrum -Spark Spectrum Absorption Spectrum
Spark Spectrum of Dilute Solutions of Bismuth Trichloride X-ray Spectrum .
CHEMICAL PROPERTIES Reactions with Non-metals and Non -metallic
Compounds Electrochemical Properties Electrode Potential Colloidal Bis-
muth .............
ATOMIC WEIGHT OF BISMUTH ........
ALLOYS or BISMUTH -Fusible. Alloys Binary Alloy Systems -Ternary and
Quaternary Alloys ...........
CHAPTER IV. Compounds of Bismuth
GENERAL Physiological Action of Bismuth and its Compounds
BISMUTH AND HYDROGEN Bismuth Dihydride Bismuth Trihydricle
BISMUTH AND THE HALOGENS Bismuth Trifluoride Bismuthyi Fluoride
Higher Fluorides of Bismuth and other Oxylluoridcs Bismuth Bichloride
Bismuth Trichloride Chlorobismuthous Acid Chlorobismuthites Bismuthyi
Chloride Bismuthyi Chlorate Bismuth and Bismuthyi Perchlorates Bis-
muth Thiochloriclc Bismuth Selenochloride Bismuth Dibromide- Bismuth
Tribromidc Bismuth Oxybromide Bismuth Thiobromide Bismuth Di-
iodide- Bismuth Triiodide lodobismuthous Acid Bismuth Oxyiodide -Bis-
muth lodate Bismuth Thioiodidc ........
BISMUTH AND OXYGEN Bismuth Monoxide Bismuth Trioxidc Hydratcd
Bismuth Trioxicle Higher Oxides of Bismuth ......
BISMUTH AND SULPHUR Bismuth Monosulphide Bismuth Trisulphidc
Thiobismuthitcs Bismuth, Oxygen and Sulphur .....
BISMUTH AND SELENIUM Bismuth Selenides Bismuth Selenites and
Selcnates ............
BISMUTH AND TELLURIUM ...... .
BISMUTH AND CHROMIUM ......
BrsMUTii AND MOLYBDENUM, ETC. .....
BISMUTH AND NITROGEN Bismuth Nitride Bismuthyi Xitntc and Com-
plex Bismuth Nitrites Bismuth Nitrates ......
BISMUTH AND PHOSPHORUS . . ....
BISMUTH AND ARSENIC . . .....
BISMUTH AND ANTIMONY .........
BISMUTH AND CARBON Bismuth Carbonates- --Complex Bismuth -Cyanides
Bismuth Thiocyanate ..........
BISMUTH AND SILICON .........
DETECTION AND ESTIMATION OF BISMUTH ......
NAME INDEX
SUBJECT INDEX
PATENT INDEX
LIST OF CHIEF ABBREVIATIONS EMPLOYED
IN THE REFERENCES.
ABBREVIATED TITLE.
AfhandL Fys. Kem.
Amer. Cham. J . .
Amer. J. Sci.
Anal. Fis. Quim.
Analyst .
A?malen .
Ann. Chim.
Ann. Chim. anal.
Ann. Chim. Pk/ji.
Ann. 31'ines
Ann. Pharm.
Ann. Pfiys. Chem.
Ann. Phiitiik
Ann. Physik, Beibl .
Ann. Sci. Univ. Jassy
Arbeittn Kaiserl. Gcxundhei+s-
amte ....
Arch. exp. Pathol. Pharmak,.
Arch. Pharm.
Arch. Sci. phys. nat.
A til Ace. T 01 inn .
Alii R. Accad. I/mcei .
B.A. Report*
Per. .....
Ber. A had. Bar. .
Bar. deut. pharm. Ges.
Jlcr. deut. phyxikaL 6V,<?.
Bot. Zc.it. . ' .
Bui. Soc. S tunic. Cln.j. .
Bull. A cad. ray. Bdfj.
Bull. Acad. Sci. Cracow
Bull, dc J3elg.
Bull. Sci. Pharmacol .
Bull. Soc. chirti. .
Bull. Soc. franc. 3 iin. .
Bull. Soc. mi/I, de Prance
Bit II. U.S. Gcol. Survey
Centr. Min.
Chem. Lnd.
C/Lcr/i. Sews
Chcm. WccJM'ul .
( Item. Zcil.
C/iC'iii. Zni.tr.
Compt. rend.
Cr til's Anjialc.n .
DingL poly. J.
JOURNAL.
Afhandlingat i Fysik, Kemi ocli Mineralogi.
American Chemical Journal.
American Journal of Science.
Analcs de la Socieclad Espanola .Kisica y Quimica.
The Analyst.
Justus Licbig" s Annalcn dcr Chemic.
Armales dc Chimie (1719-1815, and 1914-f ).
Annales dc Chimie analytiquc appliquee a 1" Industrie, a
1' Agriculture, a la Pharmacie, et a la Biologic.
Annales de Chimie ct dc Physique (Pans) (1SU>-1913).
Annales des Mines.
Annalen der Pharmacic (1832-1 839).
Annalcn der Physik und Chemie (1819-1899).
Annalen der Physik (1799-1818, and 1900 ).
Annalen der Physik, Beiblattos.
Annales scientifiques de 1'Universite de Jassy.
Arbeitcn aus dcm Kaiscrlichen (losundheitsamte.
Archiv fur experimentelle Pathologic und Pharinakologie.
Archiv der Pharmazie.
Archives dcs Sciences physique ct naturelles, Geneve.
Atti della Re ale Accaclcmia delle Science di Torino.
Atti della Reale Accademia .Lincei.
British Association Reports.
Berichtc der deutschen chemischen OcsclLschaft.
See Sitzunysber. K. Akad. Wiss. Berlin.
l^eriehtc dor deutschen phairnazeutischen GesellschafL
Berichte der dcutsoheri pliysikalischen (icscllschaft.
.Ixjtarnsche Zeitung.
Bule.tinul Socictatei de Stlintc din Cluj.
Academic royalc de -Bclgique Bulletin de la Chisse des
Sciences.
.Bulletin international de 1' Academic dcs Sciences de
Cracovic.
.Bulletin de la Societe chimiquc Bel<zique.
Bulletin dcs Sciences Pharmacologiques.
Bulletin dc la Societe chimique do France.
Bulletin de la Societe francai.se de Minoralo^ie.
Bulletin de la Societe mmeralogiquo de Franc(^.
J^ulletins of the United States Geological Survey.
Centralblatt fur Miner alogic.
Die Chemisehe Industrie.
Chemical News.
Chcmisoh AVeekblad.
Chennkei- Zeitung (Cot-hen).
Chemise lies Zentralblatt.
Comptcs rendus liebdomadaircs dcs Seances dc F Academic
des Sciences (Paris).
Chemische Annalen fur die Freunde der Naturlehre, von
L. Crelle.
Dingier' s polytcchnischcs Journal,
xvii
VOL. vi. : Y.
ANTIMONY AND BISMUTH.
ABBREVIATED TITLE.
Drv.de' s Annalen
Electroch. Met, Ind.
Eng. and Min. J.
Gazzetta ....
Gehleris allg. J. Chem.
Geol. Mag.
Gilbert's Annalen
Giorn. di Scienze Nalurali ed
Econ. ....
Helv. Chim. Ada
Int. Zeitsch. Metallographie .
Jahrb. Ick. geol. Reichsaiisl. .
Jahrb. Miner.
Jahresber. ....
Jenaische Zeitsch.
J. Arncr. Cham. Soc.
J. Chem. Soc.
J. Chim. phys. .
J. Gasbeleuchtung
J. Geology ....
J. Ind. Eng. Chem.
J. Insl. Metals .
J. Miner. Soc.
J. Pharm. Ghim
J. Physical Chem.
J. Physique
J. prakt. Chem. .
J. Rass. Phys. Chem. Soc. .
J. Soc. Chem. Ind.
Landio. Jahrb.
Mem. Coll. 3d. Kyoto.
Mem. Pans A cad.
Monatsh. ....
Mon. scieni.
Munch. Mad. }Voch<inxchr. .
Nature ....
Nuoi'o Ciffi.
Oc*terr. Chem. Zeit.
Ofvcrs. K. Vct.-Akad. Fork. .
Pflugcr's Archiu .
Pharm. Post
Pliarm. Zentr.-h..
Phil. May
Phil. Trans.
Phys. Review
Physi.kal. Zeitsch.
Poijfj. Annalen .
P)oc. C ha in. Soc.
Proc. K. A had. Wdcnsch.
A inslcrdaiii, .
Proc. Roy. J rUh Acad..
Pioc. Hoy. Phil. Soc. Glasgow
Proc. Roy. Soc. .
Proc. Roy. Soc. Edin. ,
JOURNAL.
Annalen der Physik (1900-1906).
Electrochemical and Metallurgical Industry.
Engineering and Mining Journal.
Gazzetta chimica italiana.
AUgemeines Journal der Chemie.
Geological Magazine.
Annalen der Physik (1799-1824).
Giornale di Scienze Natural! ed Economiche.
Helvetica Chim. Acta.
Internationale Zeitschrift fur Metallograpliie
Jahrbuch der kaiserlich-koniglichen geologischen Reichsan-
stalt.
Jahrbuch iiir Mineralogie.
Jahresbericht iiber die Fortschritte der Chemie.
Jenaisclie Zeitschrift f ur Naturwisscnschaft.
Journal oi the American Chemical Society.
Journal of the Chemical Society.
Journal de Chimie physique.
Journal fiir Gasbeleuchtung.
Journal of Geology.
Journal of Industrial and Engineering Chemistry.
Journal of the Institute of Metals.
Mineralogical Magazine and Journal of the Mineralogical
Society.
Journal de Pharmacie et de Chimie.
Journal of Physical Chemistry,
Journal de Physique.
Journal fur praktische Chemie.
Journal of the Physical and Chemical Society of Russia
(Pelrograd).
Journal of the Society of Chemical Industry.
Laiid\virtschaftliche Jahrbucher.
Memoirs of the College of Science, Kyoto Imperial
University.
Memoirs presenters par divers savants a
Sciences de Tlnstitut de France.
Monatshefte fur Chemie und verwandte
Wisscnschaften.
^Monitcur scientifique.
Munchencr Medizinisclie Wochenschrift.
Nature.
II nuovo Cimento.
Oesterreiclnsche Chemiker-Zcitung.
Ofversigt af Kongliga Vetenskaps-Akademiens Forhand-
lingar.
Archiv fur die gesammte Physiologic dcs Mcnschen und
der Thiere.
Pharmazcutische Post.
Pharmazeutische Zentralhalle.
Philosophical Maaazine (The London, Edinburgh, and
Dublin).
Philosophical Transactions of the Royal Society of
London.
Physical Review.
Physikalische Zeitschrift.
Pogscndorffs Annalen der Physik und Chemie (1824-
^1877).
Proceedings t")f the Chemical Society.
Koninkhjki 1 Akadomie van Welonschappon tc Amsterdam
Proceedings (English Version).
Proceedings of the Royal Irish Academy.
Proceedings of the Royal Philosophical Society of Glasgow.
Proceedings of the Royal Society of London.
Proceedings of the Royal Society of Edinburgh.
1' Academic de
Theile anderer
LIST OF CHIEF ABBREVIATIONS.
xis
ABBREVIATED TITLE.
Rec. Trav. chim.
Roy. Inst. Reports
Schiv rigger's J. .
Sci. Proc. Roy. Dubl. Soc. .
Sitzungsbsr. K. Akad. Wiss.
Berlin.
Sitzungsber. K. Akad. Wiss.
Wien ....
Techn. Jahresbcr.
Trans. Amer. Electrochem. Soc.
Trans. Chem. Soc.
Trans. Inst. Min. Eng.
Trav. et Mem. du Bureau
intern, des Poids et Mes.
Verh. Ges. deul. Naturforsch.
Aerzte.
W ied. Annalen .
W issenschaftl. Abhandl. phijs.-
tech. Reichsanst. .
Zeitsch. anal. Chem.
Zeitsch. angew. Chem. .
Zeitsch,. anorg. Chem. .
Zeitsch. Chem.
Zeitsch. Chem. I?id. Koll-oide .
Zeitsch. Elektrochem. .
Zeitsch. Kryst. Min.
Zeitsch. Nahr. Genuss-m.
Zeitsch. physikaL Chem.
Zeitsch. phi/siol. Ghem,.
Zeitsch. miss. P/iotochcm.
JOURNAL.
Recueil des Travaux chimiqucs des Pay-Bas et de la
Belgique.
Reports of the Ro3 r al Institution.
Journal fiir Chemie und Physik.
Scientific Proceedings of the Royal Dublin Society.
Sitzungsberichtc dcr Koniglich-Prcussischen Akademie de
Wissenschaften zu Berlin.
Sitzungsberichte der Koniglich-Bayerischen Akademie
der Wissenschaften zu Wien.
Jahresbericht uber die Leistungen der Chemischen
Technologic.
Transactions of the American Electrochemical Society.
Transactions of the Chemical Society.
Transactions of the Institution of Mining Engineers.
Travaux et Memoires du Bureau International des Poids
et Mesures.
Verhandlung dcr Cesellschaft deutscher Katurforscher und
Aerzte.
Wiedemann's Annalen der Physik und Chemie (1877-
1899).
Wissenschaftlichc Abhandlungen der physikalisch-tech-
nischen Reichsanstalt.
Zeitschrift fiir analytische Chemie.
Zeitschrift fiir angewandte Chemie.
Zeitschrift fiir anorganische Chemie.
Kntische Zeitschrift fiir Chemie.
Zeitschrift fiir Chemie und Industrie des Kolloide (con-
tinued as Kolloid-Zcitschrift).
Zeitschrift fiir Elektrochemie.
Zeitschrift fiir Krystallographie und Minoralogic.
Zeitschrift fiir Untersuchung der Nahrungs- und Gcnuss-
mittel.
Zeitschrift fur physikalische Chemie, .Stochiometrie unu
Vcrwandtschaftslehre.
Hoppc-Scylcr's Zeitschrift fiir physiologische Chemie.
Zeitschrift fiir wisscnschaftlichc Photographie, Photo-
physik, und Photochcmie.
TABLE OF DATES OF ISSUE OF JOURNALS.
FOR the sake of easy reference, a list is appended of the more
important journals in chronological order, giving the dates of issue of
their corresponding series and volumes. In certain cases the volumes
have appeared with considerable irregularity ; in others it has occa-
sionally happened that volumes begun in one calendar year have
extended into the next year, even when this has not been the general
habit of the series. To complicate matters still further, the title-pages
in some of these latter volumes bear the later date a most illogical
procedure. In such cases the volume number appears in the accom-
panying columns opposite both years. In a short summary of this kind
it is impossible to give full details in each case, but the foregoing
remarks will serve to explain several apparent anomalies.
r^
[
.5 _-
si _;
S . !
~
y : Amer. . g ^ . Ann ^ g , T ."
1 Cell. 'TO' 1 ^ > T n "^ 3 '"" 1
: J Sci. ; Mm. ^ J -c
11
5.S j Phil.
Phil. ";;
Trans. H ;
1SOO
. (1)32-35! ... i -. j ...
4-6
... ! 5-8
90
1
36-39 : ... i ... j ...
7-9
... ; 8-11
91
9
40-43: ... : ... : ...
10-12
... ; 11-14
92
3
44-47 ' . : ... !
13-15
14-17
93
4
1 "1 '' !
j 4b-ol . j
16-18
... : 17-20
94
1805
' 52-55 ... ... j
19-21
: 20-23
95
6
56-60 ... ... ' ...
22-24
'.'.. '. 23-26
96
7
. ; 61-64 :
25-27
... ; 26-29
97
S
65-68
28-30
29-32
98
9
. ' 69-72 . ... | 31-33
(1) 1* ! 33, 34
99
1810
! 73-76 ...
34-36
2 35, 36
100
11
77-80 ' ... 37-39
3 I 37, 38
101
12 : .
81-84 ' ... ... ... 40-42
4 39, 40
102
13
S5-SS 1 ! ... i ... 43-45
5 i 41,42
103 ... ,
14
89-92 : ... ... ... 46-48
6 ; 43, 44
104
1815
! 93-96 ' ... ... ; ... 49-51
(2) 1 45, 46
105
16
: (2) 1-3 . .. ! ... , ... 52-54
2 ' 47, 48
106
17
4-6 , 1, 2 55-57
3 49, 50
107
18
i 7-913 ... ; ... 58-60
4 : 51, 52
108
19 ! (1) 1 _ 10-12 , 4 ... : ... 61-63
5 53, 54
109
1820 i 2 13-1.5 : 5 ... 1-3 64-66
6 55, 56
no : ...
21 ! ,
3 16-18' 6 ... 4-6 67-69
7 57, 58
in
22 4,
5 19-21 7 1,2 7-9 ,70-72
S ; 59, 60
112
23 (
> 22-24 ' 8 3-6 10-12 73-75
9 ! 61, 62
113
24 7,
8 25-27 9 7-10 13-15 76
10 ; 63, 64
114 1, 2
1825 i
) i 28-30 10, 11 ' 11-14 1G-13 ^
11 ' 65, 66
115 ' 3-5
26 10.
11 : 31-33 12, 13 ,15-19 '19-22 = JS
12 67,68
116 ; 6-8
27 1
2 ; 34-36 (2)1,2 120-23 23-26 .-5 ^ 2
13 (2)1, 2
117 9-11
28 13,
14: 37-39' 3,4 ! 24-26 27-30 5 ^
14 3, 4
118 12-14
29 15,
16 40-42 5.6 : 27-30^31-34 O "^
15 5, 6
119 .15-17
i
First series known as Bulletin de
XS11
ANTIMONY AND BISMUTH.
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TABLE OF DATES OF ISSUE OF JOURNALS. xxiii
CO Oi O r 01 CO
CM "V CO CO i i
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<M -rti CO OC O
CM TT tc co :
CO O CM -rfi CC
IS 8 n-r^ys^ tCcT^-w-o i>-v:v~fi
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TABLE OF DATES OF ISSUE OF JOURNALS. xxv
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^C OO O C-5
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TABLE OF DATES OF ISSUE OF JOURNALS.
Ci T CO vo *
i. CC V.C t O5
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c^Oicr. cTicni cvcr:C5CT:c: o
A TEXT-BOOK OF
INORGANIC CHEMISTRY.
VOLUME VI. PART V.
A TEXT-BOOK OF
INORGANIC CHEMISTRY
VOL. VI. PART V.
ANTIMONY AND BISMUTH.
CHAPTER I.
ANTIMONY AND ITS ALLOYS.
Symbol, Sb. Atomic Number, 5]. Atomic Weight, 121-76 (O=16).
Occurrence. The principal ores of antimony contain the mineral
known variously as stibnite, antimonite or antimony glance, Sb 9 S 3 .
Stibnitc is found principally in France, 1 Italy, Algeria and China, and
to a smaller extent in Czechoslovakia, Spain, Portugal and Japan. In
India, stibnitc lodes in gneissose granite occur in the Punjab, and with
ccrvantitc in the Northern Shan states, while the tetrahedrite in Slee-
manabad copper lodes is highly antimonial. The ores frequently
contain gold, silver and arsenic, and are associated with galena, iron
pyrites, spathic iron ore, quartz, calcite and barytes.
Other antimony minerals occasionally found in ores that are com-
mercially valuable include cervantite or antimony ochre, Sb 2 O 4 , kermesite,
2Sb 2 S 3 .Sb 2 3 , valentinite, white antimony or antimony bloom,, Sb 2 O 3
(rhombic), and senarmonlite, Sb 2 O 8 (cubic).
Native antimony occurs in too small quantity to be commercially
valuable. 2
Many other antimony minerals have been described. These are
mainly complex sulphide minerals which may be regarded as thio-
antimonitcs or thioantimonatcs, oxidised "minerals which may be
antimonitcs or antimonates, and a few miscellaneous minerals difficult
to classify. In. the following list the formulas ascribed to the various
minerals arc intended to convey the approximate composition of the
mineral; it is not suggested that they represent definite chemical
compounds in all ca.scs. 3
Antimony has also been found in animal tissues. 4
1 Churrin, (li-nic.nvil, 1032, 100, 3M.
2 \Van<i, '' Aniunc.mj" (Griffin, J919), p. 46.
:5 In Addition 1o 1 he lil.eralure cited, reference may also be made to Shannon, Amer.
MintmL, 19JS, 3, 23; Sehaller, Bull. U.S. Geol. Survey, 1916, 610, 104; Halsc, '''Antimony
Ore*, Monograph, on Mineral Resources with Special .Reference to the British Empire"
(Murray, J925); Voskuil, '"'Minerals in Modern Industry'" (Wiley and Sons, 1930), p. 260.
4 Chapman, Xature, 1930, 126, 76].
3
ANTIMONY AXD BISMUTH.
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ANTIMONY AND ITS ALLOYS.
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ANTIMONY AND ITS ALLOYS.
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AXTIMOXY AND ITS ALLOYS. 13
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AXTIMOXY AND BISMUTH.
History. There can be little doubt, that antimony was
icient times, either in the form of the metal or in compounds.
3 were acquainted with the metal five thousand years ago ;
references in the Old Testament (II Kings, 9, 30; Ezekiel,
:emiah, 4, 30) have been considered by most commentators
itibnite or sulphide of antimony.
bronzes discovered by archaeologists in many parts of the
been found to contain antimony ; a vase found by M. de
'ells in Chaldea consisted of almost pure antimony; 1 and
i copper ewer and basin of the Fifth or Sixth Dynasty has
to be plated with antimony. 2
een suggested that the knowledge of antimony passed from
irough Arabia into Europe by the agency of the Arabic
iber or Geber, who lived in the eighth century. References
Y in the literature of the Middle Ages are extremely con-
ever, and it is not until towards the end of the sixteenth
it the obscurity is dispersed. 3 Robert Boyle 4 was clearly
:h the starred appearance of the cast metal, to which he
:he starry regiilus of Mars and antimony " (see Plate),
[fusion which exists with regard to the early history of
; to a great extent due to the ambiguity of the origin and
the words antimonium and stibium. Both words appear to
>mplo} r ed to indicate in some cases the metal, in others the
neral stibnite. In addition, the metal itself was regarded
:horities as a semi-metal, by others as a mixture of metals,
c writings the mineral stibnite is referred to as kohl, a word
11 retained, with a very different meaning, in alcohol. This
10! " is used for stibnite in some Latin writings, but is more
found in the Spanish. The more usual Latin term was
he origin of the term antimonium is more difficult to trace,
hat it arose from the accidental poisoning of some monks
nisscd on linguistic grounds. The word was used by Basil
and as in the original copy of his work (which was written
it always appears in italics, it is probably of Latin origin.
s supported by the fact that one of the earliest recorded
the use of the word is in the Latin writings of Geber, who
e thirteenth century. (This author is not to be confused
L-abic chemist with a similar name, who flourished in the
,ny.) The word stibium appears to have been more gcner-
xl. although both words survived until the time of Lavoisier ;
Liscd indiscriminately to describe the metal and stibnite.
of the available knowledge of antimonv up to the bcolnnino'
o ./I & <~>
;ecnth century is to be found in the works of Basil Valentine. 5
ilot, CompL rend., 1887, 104, 265.
v and A. H. Kopp, Metropolitan Museum til.udies, 193:>, 4, 1(53.
us, "Akhymia" (Frankofurti, 159;"); 2nd Ed., 1(500).
)n the Unsuccossf ulncss of Experiments," Opera, 1772, i, 325.
hnrni. J., 1928, [4], 67, 397. .See also Valentine, "'Tin: TriH-m-^mnl Chariot
English Translation (London, J001); Pliny, J/ixtoria rifttnrdlix, 33, *H;
inolcria '/nc-.chca, 5, 49: A.aricola, ^ DC re. rnHaUica"' ( Basilia?, J55C)), Kn.ulish
"Hidon, 1912), p. 428; Erckor, '* Jlr-whrMUHnf/ a./lc.r funif- )nxl<->i. inint'.ruiisclic.
hvercksarten.'"' (t'ra^r, 1574); Sala, '* Anato-mla (rnlimonn" (Francol'urti,
L Suchteri, li Mysteria, yemina antimonii." (Xiirnberg, 1G80); Ch-ymiw.hc.
nkfurt, 1680), pp. 229, 267; Lcmery, " Traite de, Vanlimoine" (Paris,
:el, "' Vollstandiges Laboratorium chymicum'^ (Berlin, 1716); Morhof,
Text-Book of Inorganic Chemistry, Vol. VI, Part V .} [To face page. 14.
AXTBIOXY AXD ITS ALLOYS. 15
Antimony compounds were largely employed in medicinal prepara-
tions in the Middle Ages. Paracelsus was one of the first to use them,
having made butter of antimony (antimony trichloride) by distilling
corrosive sublimate with antimony sulphide. Treatment with water
yielded mercurius vitce (an oxychloride) a preparation that was
popularised by the Veronese physician Algarotus or Algaroth, and
hence became known as " Powder of Algaroth" Sulphide of antimony
was itself used considerably for a time, but was practically discontinued
after considerable discussion by the medical profession. Tartar emetic,
the most widely employed antimony compound, was also probably used
in early times. In ancient times wine was permitted to stand overnight
in antimony goblets, and was taken medicinally on the following day.
This practice persisted up to the time of Boyle, but was then super-
seded by the introduction of metallic pills of antimony. 1
Extraction. 2 Antimony is extracted mainly from ores containing
antimony trisulphide in the form of stibnite. Rich ores are first sub-
jected to liquation, whereby the fusible sulphide is removed from the
gangue and concentrated. The concentrate is then reduced to metal
by smelting with wrought iron in pots, in reverberatory furnaces or
sometimes in blast furnaces, 3
Sb 2 S 3 -f 3Fe = 2Sb + 3FeS
The reduction in pots is carried out in three stages : (1) A mixture
of liquated ore, wrought iron and common salt is fused together and a
crude product obtained containing about 90 per cent, antimony and
7 to 8 per cent, iron ; (2) this is again remelted with more liquated ore
and common salt, the bulk of the iron being thereby removed ; (3)
finally this second product is remelted with a special flux made by
fusing together three parts of commercial potassium carbonate with
two parts of liquated ore.
The reduction in reverberatory furnaces is carried out in two stages :
(1) Fusion of liquated ore with scrap iron to produce crude metal, and
(2) refining the crude metal. In the first stage the liquated ore is
smelted with a flux containing soda ash, salt cake and common salt.
This results in the production of a slag of low density containing sulphide
of iron and sulphide of sodium, from which the crude antimony can
settle fairly readily. The crude product contains 94 to 95 per cent.
antimony mixed with iron, sulphur, lead and arsenic. This is refined
by melting carefully under a llux of sodium carbonate. After a time
the impurities can be skimmed off and then a mixture containing
antimony oxide, antimonyl sulphide, sodium carbonate and a little coal
is added. The refined metal is then ladled out and cast as " star
antimony," the surface of the cakes showing a well-defined crystal
ist or (Lubcck, 17 J 4), i, 84; Littre, Diction.naire de, la Languefrancaisc (Paris, 1873),
i, 156; Helm and Hilprccht, Chem. Zc.it., 1901, 25, 2/50; Homrncl, Zcitsch. angcw. Chem.,
1912, 25, 97; Chem. Zc.it., 1012, 36, 918; Hyman, C'hc.in. and Jud. llcvi<-n\ 1924, 2, 1006;
A mien, ibid.. 1132.
1 .Dv.son, lor. r./l., pp. f>20, ,~>90.
- \\ : an<r, lc. ciL, p. 07 ; Gotland, '"The Mc.tulhi.rfjy of the. N(>n.'F<-rro-us Jl/V-ta/.v" (Griffin),
p. f>fif>. Sec. also YVano, Proc. World Kiifj. Congr. Tokyo, 1<J29, J931, 35, 185; J^nginccnt/.g,
1929, 128, 720; Brazciiall, Chcm. Ena. Mining R&v'., 1932, 24, 312, 344; Tai'cl, Mctallnnd
Erz, 1931, 28, 503; Kai Ho, Science (China}, 1933, 17, 16.
3 Schoeller, Trans. l.nsl. Mm. Met., 1918, 27, 237; Brazcnall, The Chemical Age,
Metallurgical Section, 1932, 27, 12.
16 ANTIMONY AND BISMUTH.
structure. A method has also been suggested for refining electrolytic-
ally 1 using an electrolyte containing antimony trifluoride with about
100 grams of free sulphuric acid and 20 grams of free hydrofluoric acid
per litre.
Low-grade ores, which generally contain oxidised minerals in addi-
tion to sulphides, are first roasted to produce either the non-volatile
tetroxide or the volatile trioxide. With oxidised ores recovery of
antimony is incomplete unless anthracite is added to the charge. Thus,
treated at 900 C. without anthracite, only the antimony present as
sulphide is recovered, while with anthracite almost complete recovery
has been effected. Using an ore containing 3-3 per cent, antimony,
partly sulphidic and partly oxidised, the average anthracite consump-
tion was 15 to 20 per cent, of the charge, of which 5 to 8 per cent, was
used as reducer and 10 to 12 per cent, as fuel. 2 The oxides obtained are
reduced to metal by carbon in crucibles or reverberatory furnaces, using
an alkaline flux containing soda ash, salt cake and common salt.
For roasting sulphide ores two methods are used, viz., simple roasting
yielding mainly antimony tetroxide, and volatilisation roasting yielding
mainly antimony trioxide. In the former, reverberatory furnaces arc
employed, the flue gases passing through a condensing plant for the
recovery of any antimony trioxide that may be formed. For volatilisa-
tion roasting either the Herrenschmidt or the Chatillon process is used.
In. the Herrenschmidt process, the furnace is a rectangular shaft of fire-
brick with fire-bars arranged in steps. The gases from this furnace are
cooled by passing them through a scries of iron pipes into a wooden
tower packed with coke down which water trickles. The water is
collected at the bottom of the tower in tanks in which the oxide is
allowed to settle. In the Chatillon process a double cupola type of
furnace is employed. The flue gases containing volatilised oxide pass
through a condensing plant (which consists of sheet iron tanks so
disposed that the flue gases can pass all round them), and arc then
forced into a filtration chamber which is fitted with bags of coarse cotton
canvas or of woollen material.
The volatilisation and oxidation of antimony trisulphicle have been
studied in detail. 3 From the results it is suggested that rich or con-
centrated ores which do not contain precious metals, arsenic or lead
should be roasted to antimony tetroxide, while poorer ores, and ores
containing precious metals, should be roasted to antimony trioxide. It
is further suggested that it is inadvisable to extract antimony from rich
ores by fusing the sulphide with iron on account of the high fusion
temperature required ; if this process is adopted a reducing atmosphere
should be employed and the dust in the flue gases recovered.
The reduction of oxides of antimony may also be effected by the
action of arsenic on. fused sodium hydroxide in the presence of the
oxide. 4
Various wet methods for the extraction of antimony have been
suggested but do not appear to have been successful. 5 Electrolytic
1 Koscher, U.S. Patent, 1930, 1780944.
~ Slobodska, Tsvchmie MfdaL, 1932, Xos. 7-8, 10S.
" Shakov and Slobodska, Tzvet. Met., 1930, 1294; Chiniie d, Industrie, 1931, 25, 1.120.
See also this Volume, pp. 101, 102.
* French Patent, 1930, 694283.
' Coolbangh and .Read, U.S. Patent, 1926, 1597018. See also Wan?, luc. cil.; Gow~
land, loc. cit.
AXTIMOXY AND ITS ALLOYS. 17
methods have, however, been developed and it is claimed that compact
antimony of great purity can be obtained by these methods. 1 ' 2
Chemically pure antimony has been prepared 3 by converting
antimony trichloride, purified by distillation, into chlorantimonic acid,
which, after purification by recrystallisation, is hydrolysed to antimonic
acid. The antimonic acid is finally reduced to metal by fusion with
potassium cyanide.
The production of " secondary antimony ? ' (i.e. the recovery of
antimony from alloys and residues) forms an important means of
obtaining the metal. In the United States of America in 1928, between
170,000 and 180,000 tons of old lead accumulators containing 3 per cent,
antimony were available. 4 For the treatment of lead- antimony alloys
the Harris process is largely employed in England and some other
countries. 5 In this process the scrap metal is melted with an oxidising
alkaline flux. Arsenic, antimony and tin are then removed by skim-
ming as sodium arsenate, antimonate and stannatc. The sodium antimon-
ate is separated from these by lixiviation, and is reduced to antimony
by treatment with carbonaceous material. 6 In another method that
has been suggested, the alloy is treated with metallic sodium in order to
form an alloy of sodium and antimony. This is dissolved in molten
caustic soda, and the antimony separated by treatment with water. 7
More than three-quarters of the world's supply of antimony ore
are obtained from the province of Hunan, China. In France, the ore
deposits at La Lucette yield an annual production of 3,000 tons of
antimony. 8 About 1,000 tons of antlmonial lead, containing 21 per cent,
antimony, arc also produced annually in Burma. 9 The total world
production of antimony ore, returned as tons of metal content, is given
in the following table : 10
1926. 1027. 1928. 1929. 1930. 1931.
Lono- Tons 31,400 30,000 30,000 ' 31,000 23,000 27,000
Physical Properties of Antimony.
Numerous varieties of antimony have been described by various
workers, but the existence of definite allotropic forms, and their relation-
ship to one another, have not yet been fully established. According
1 Enrrclharclt, Zeitsch. Elektroelicm., 1931, 37, 813; Izgaruishev and Plclencv, ibid.,
365; van Erckelcns, Eng. Mining J., 1931, 132, 160.
2 Katz, " Mineral JKefiources of the, United States, 1927" (Washington, Government
Printing Offices, 1930), p. 40. Sec also En.g. Mining J., 1927, 123, 432 ; Vocl, Metallborse,
1930, 20, 537, 651. :! GroschulT, Zeitsch. anorg. (Jlu-m., 1918, 103, 16-1.
MViison, Metal Industry (New York], 1930, 28, 162.
5 Bruehhold, Bol. niine.ro, .1929, 28, 191; Winter, Eng. Mining J., 1928, 125, 893, 969;
Fr(:ii.f:h Pa/ent, 1928, 665174; Ivirsebom, British Patent, 1928, 3158.11; Short, Metal
Itidxxlry (London], 1929, 34, 42.
6 See also Voael, Mttallh6r.se., 1929, 19, 2441, 2499, 2555.
7 Hanak, U.S. Patent, 1930, 1786908.
8 Charnn, Gznia civil, 1032, 100, 314.
'' Paseoe, Records Geol. Survey India, 3930, 64, 26.
10 "Mineral Resources of the British Empire and Foreign Countries," Statistical Sum-
mary (London, H.M.S.O., 1933), p. 27. For a review of the antimony industry from 1913-
1933, see Kai Ho, Science (Chma\, 1933, 17, 16.
VOL. VI. : V. 2
18 ANTIMONY AND BISMUTH.
to Cohen and his co-workers, 1 two forms of antimony, a and /5, can
exist, a, or rhombohedral antimony, is more stable than /3, amorphous
or explosive antimony, at all temperatures below the melting point. 2
A very unstable yellow modification has also been described. 3
Irregularities in the dilatometric curve at 96 C. and 101 C. were
formerly taken to indicate allotropic transformations, 4 but it is probable
that they are due to mechanical deformation. Similar irregularities in
the electrical resistance curve disappeared after tempering at 600 C.,
and X-ray observations taken at room temperature, 150 C. and 200 C.,
indicated no change in structure. 5
Rhombohedral Antimony or a -Antimony is the ordinary form
of the element. It is a white, lustrous metal, crystallising in the holo-
hedral class of the rhombohedral division of the hexagonal system 6
a: c = \: 1-3236, a=8658'
From X-ray analysis it is deduced that the structure consists of two
interpenetrating face-centred lattices, the symmetry being that of a
rhombohedron. The unit rhomb contains eight atoms ; the length of
the edge of a unit rhomb is 6-20 A., and the shortest distance between
two atoms 2*92 A. The angle between aiw two edges of the rhombo-
hedron is 8658',and the angle between the (ioo)and (010) faces is 9253'.
There is very perfect cleavage at right-angles to the trigonal axis and
parallel to the (111) planes, and a less perfect cleavage parallel to the
(110) planes. 7 The crystal forms of electrolytic antimony, 8 and of
native antimony, 9 have also been investigated.
The density io is 6-081. at 25 C. ; that calculated from X-ray data T1
is 6-73.
The average compressibility 12 at 20 C. between 100 and 500 mega-
bars 13 is 2-4 xl(T G .
The linear thermal expansion 14 between the temperatures -190 C.
and 17 C. is given by the expression
1 Cohen, J. 8oc. Chc.m. hid., 1929, 48, (54; Cohen and Ringer, Zatsch. physilcal. Chcm.,
1904, 47, 1; Cohen, Collins and Stren^cr.s, ibid., 1905, 50, 29.) ; Cohen and Strenirors,
ibid.', 1905, 52, 129.
- See also Friend, i: A Tc.xl- Boole, of Physical Chemistry" (Griffin, 1932), Vol. I, p. 179.
3 Sec p. 25.
4 Cohen and van den Bosch, I* roc. K. Wd-c.iisch. Amsterdam, 1914, 17, (545; Zrit.wh.
phi/aikat. Chcm., 19.15, 89, 757; Janecke, ibid., 19] 5, 90. 337.
>:> Schulze and Graf, Mclulltrirl-.schafL 1933, 12, 19; Schulze, Zc.itxch. phy^i/caL Ch<>.m.,
1933, 165 A, 188.
r ' Lnspeyres, ZciterJi. cj<\oL Cc.idL, 1875, 27, 574; Kahlbaum, Zc.ilst'.h. (tnory. Chon..,
\ 902, 29, 292.
7 James and Tunstall, PhiL May., 1920, [6], 40, 233; ()^, Phil. May., 1921, [6|,
42. 163; Solomon and Morns Jones, Pfiil. Mag., 1930, [7], io, 470; Xeuburger, Zfiitsch.
KrisL, 1931, 80, 103.
8 M'irata, Elc-.c,. J^-rlc.w (Japtrn], I 928, 16, 051.
y Carpenter and Tamura, Bull. hi*l.. Mmi-nfj J//:/,, 1928, 282, 1.
10 Ln'u-ru'dional Crilicnl Tables, 1926, i, 102. Sec also Cohen and van dun Boscli,
Zcitsc.h. phy.^ikal. Ckc-m., 19.15, 89, 757; Lincke, ibid., 1908, 56, 393; Cuineha.nl and
Chretien, Gow.pl. ra/r/., I !)()(>, 142, 709; Kahlbaum, Roth and Siedler, Zc.it nek. atiortj.
Chcm., 1902, 29, 177.
11 Iiitt-nuitio-ndl (Jriiirnl Table*, 192(5, I, 3-10.
'- Kichards and \Vlnt.c\ ./. Ainct. (,'h,c>n.. *SW;., 192S, 50, 33MO.
!:! 1 me^abar--- I O fi dynes per sq. cm.
11 Vuh'mimT and \Vallol, Vc.tlt. -plujfiikaL (!<^. ttc.rlin, 191 I, 16, 757, Crunciscn, Ann.
I'hyxik, 1910, 33, 33, 65. See also .I'izoau, Ann. Chim. Phyx., 1866, [-1], 8, 335; Com.pt.
rend., 1869, 68, 1125; Dorsey, Phys. Review, 1907, 25, 88; Lussano, Nuovo dwc.nlo,
1910, IQ, 182; ilidnert and Kndcr, Phm. Jtevicw, 1932, 42, OIL
AXTLMOXY AND ITS ALLOYS.
19
and between the temperatures 17 C. and 100 C. by
l t =l (I-~ 0-000010880
The cubical coefficient of expansion 1 lies between 0-0000316 and
0-000033. The thermal expansion of single crystals has also been
determined. 2
The hardness of antimony on Mohs' scale lies between 3-0 and 3-5.
The Brincll hardness number 3 is 58-0, but higher values have been
obtained. The ultimate tensile strength 4 ' is 1-1 kilograms per square
millimetre; Young's modulus is 7,950 kilograms per square milli-
metre, and the modulus of elasticity in shear 2,020 kilograms per square
millimetre.
The specific heat 5 is 0-05. Within the temperature range 412 C.
to 460 C. the heat capacity 6 is given by
H = 0-0534496 -0-4522 x!0~ 2 / + 0-7944 x lO" 5 / 2 gram-calories per gram
The heat capacity at low temperatures has also been determined and is
as follows : 7
Temperature, C. . ; 20-2 \
Heat capacity . 6-073 j
(Gram-calories per j
gram-atom) : j
Temperature, C. . - 80-0
Heat capacity . 5-789
(Gram-calories per
gram-atom)
4-6
6-043
- 20-1 i - 32-4 - 46-0 j - 58-5
5 923 5-943 5-8931 5-878
-91-1 -103-0 -133-3 -158-2 -179-9 -197-3 -207-0 j
5-726 5-691 5-431 5-224 4-700 4-337 3917
From this the entropies have been calculated.
The melting point 8 is 630-5 C., the metal being very susceptible to
supercooling.
1 Matthiesscn, Porjrj. Annalen,, 1838, 43, 390; Kopp, Aiinalen, 1852, 81, 1; Poyy.
Annals, 1852, 86, 156.
2 Bndgman, Proc. Nat. A. cad. Sciences, 1924, 10, 411; Bracsco, Coin.pt. mid., 1920,
170, 103. "
3 Kdwards and Herbert, ./. Insl. Melalt, 1921, 25, 175; Metal Industry, London, 1921,
18, 221.. Sec also Sauenvald, Zcitxch. Metallkunde, 1924, 16, 315.
1 .BridgTYian, Phy*. Her I'M, 1917, 9, 138.
5 A \vberry and Griffiths, Proc. Phys. tiac., 1926, 38, 378. See also Dulong and .Petit,
Ann. Chim.. Phyx., 1818, [2], 7, 140; Re.irnault, ibid., 1840, [2], 73, 42; Kopp, ibid., 1852,
[3], 34, 339; Aunahn, 1852, Si, 34: Xaccari, Gazzetta, 1888, 18, 13; Laborde, CompL
ra-nd., 1890, 123, 227; 'Bchn, Ann. Phyxik, 1900, I, 257; Ivahlbaum, Roth and Siedler,
Tif'.itxcti. (Otorg. Clion,., 1902, 29, 177; Richards and Jackson, Zcitsch. physikfd. Chew.,
1910, 70, 414; Schimpil, ibid., 1910, 71, 257; Dewar, Proc. Roy. Soc., 1913, ASg, 158:
Schubel, Zvittcli. anory. Cham., 1.914, 87, 81; Ewald, Ann. Wiysik, 1914, 44, 1213; Wust,
Mouthcn and Durrer, "Die, Ttmpc.ratur Warmvihaltskwrveu dw tc.climschwichtifjp.n Mtlalla,*'''
Berlin, 1918; Gunthcr, Ann. Phytik, 1920, [4], 63, 470; Simon and Ruhcmann, Zeitsch.
phyxikdl. Chun., 1927, 129, 321.
c .Bottema and Jaeger, Proc. Ac.ad. Sci. Amstf-rdaw, 1932, 35, 916.
7 Anderson, J. Ani(.-r. Chun. Sue., 1930, 52, 2712. See also Kclley, Bur. Mines Bull.,
1932, p. 350.
8 A\\'borrv and ( Jriflit hs, lac. at. See also lleycoek and Xeville, ,7. Chc.m. Roc., 1895,
67, 1SG; (JuulitT, (:<n.}>t. rend., 1890, 123, 1)2;" Callendar, Phil. May., 1899, [5], 48,
519: llolborn and Day, Ann. Phyxik, .1900, [4], 2, 534: van Anbel, Cmnpt. rend., 1901.
132, 12()(i; 1-^.y and Ashley, Amu. Chan. J., L902, 27, 95; KrafTt, Her., 1903, 36, 1712;
Chretien, Conipt. rtn.d., 190(3, 142, 1340; Laschtschenko, J. Russ. Phys. Chem. tioc., 1914,
46, 311. 9 Reinders, Zeitsch. anory. Chem., 1900, 25, 119.
20 AXTTMOXY AXD BISMUTH.
When molten antimony is cooled its colour diminishes in brightness
in a normal manner until the solidification point is reached ; at this
point a sudden increase in brightness occurs, accompanied by an increase
in temperature. As this phenomenon occurs in an atmosphere of
hydrogen as well as in a vacuum, it cannot be ascribed to oxidation,
and is considered to be an instance of crystal luminescence. 1 The ratio
of the spontaneous crystallising power to the linear velocity of crystallisa-
tion 2 increases with the velocity of cooling in the temperature range
between 600 C. and 70 C. As the spontaneous crystallising power
diminishes at low temperatures, it may be possible to obtain amorphous
antimony by very drastic supercooling.
The latent heat of fusion is 38-84 calories per gram. 3
The values obtained by earlier workers for the volume change on
solidification are confusing, the general, conclusion being that the change
is very small, antimony probably resembling bismuth in expanding
on solidification. Toepler 4 concluded that there was a shrinkage on
solidification to the extent of 1-4 per cent, or 0-0022 c.c. per gram. A
more recent investigation, however, has revealed an expansion on
solidification of 0-95 per cent., a result which appears to have been
confirmed. 5
The density of molten antimony is shown in the following table,
though different investigators have obtained slightly different results : 6
Temperature, C G, . . 640 700 800 970
Density .... 6-49 6-45 6-38 6-29
The variation of surface tension, cr, of molten antimony with tem-
perature is as follows :
Temperature, C. . 640 675 700 800 974
a (dynes per cm.) . 348 350 350 348 342
From a consideration of these values it is deduced that antimony
in the molten state is probably highly associated. 7 The observed
parachor 8 varies from 76-8 to 83-9, the calculated value being 66-0.
The wean specific heat of the liquid 9 is 0-16.
The coefficient of viscosity,' 10 measured in grams per cm. per sec., is
as follows :
Temperature. C. . . 702 801 902 1002
Viscosity . . . 0-01304 0-01113 0-01010 0-00905
1 Karrcr, Phys. Review, 1922, 19, 437.
- Bckicr, Zeitsch. anorg. Chem., 1912, 78, 178.
3 International Critical Tables, 1927, 2, 458. See also Awberry and C4riffiths, 'loc. cit.:
Laschtschenko, loc. cit.
4 Toepler, Ann. Phys. Chem., 1894, [2], 53, 343.
5 Matsuyama, Science, Piep. Toholcu Imp. Univ., 1928, 17, 1. See also Parlitz, tilt-
zmtyxber. Natiirjorscher. Gcs. L'niv. Tartu, 1929, 35, 121; Bronicwski, Itist. Intern Phy*
c ' -'-ay, 4th Consul, 1924, 1927, 185.
6 Quinckc, Poyg. Annalcn, 1868, 135, 621 ; Guinchant and Chretien, Compt. rend., 1906,
:, 709; Pascal and Joiiniaux, Compt. rend., 1914, 158, 41-1; Borneinann and Saucnvald,
..tsch. Metallkundc, 1922, 14, 254; .Bircumshaw, Phil. Mag., 1927, [7], 3, 1290;
latsuyama, Science. Rep Tohol:n I'/np. Univ., 1929, 18, 737.
7 Bircumshaw, Phil. Mag., 1927, [7], 3, 1286. Sec also Smith, ,/. In.d. Metnl^ H)M,
2, 168; Drath and Sauerwald, Zeitsch. anorg. Chun.., 1927, 162, 301; AntonofT, Xf/tarc'
(i->V' TOT OO '
12
192S, 121, 93.
8 Sugden and \Vilkins, J. Chem. Soc., 1929, 132, 1291.
tj Awberrj- and Griffiths, loc. cit.
10 Biciiias and Sauerwald, Zeitsch. anorg. Chem., 1927, 161, 51.
AXTD10XY AND ITS ALLOYS. 21
The boiling point under atmospheric pressure 1 is 1635 C. 8 C.
This value is much higher than that given by previous investigators,
as will be seen from the following data for the vapour pressure of
antimony : 2
Temperature, C. . 1075 1135 1175 1225 1265 1325 1330
Pressure (mm.) . 54 107 206 302 398 745 760
Under reduced pressure 3 volatilisation is said to take place at tem-
peratures as low as 292 C.
The vapour density of antimony indicates that at high temperatures
the vapour is probably monatomic, 4 association taking place at lower
temperatures. 5
The thermal conductivity of solid antimony lies between 0-038 and
0-050 gram-calories per em. per sec. ; the probable mean value 6 is
0-044. The effects of pressure 7 and of temperature 8 upon the thermal
conductivity have been investigated.
The electrical resistance at various temperatures is shown in the
follow! no- table : 9
Temperature, c C.
Resistance
(ohm-cm.). -^/-^V
15
8-
28
X
10 _4
1
08
.'T.
66
X
10~ 4
1
00
-191
9.
03
X
io- 4
265
- 242
4
0-
606
X
io- 4
0909
-268
8
0-
580
X
io- 4
0760
The influence of strong magnetic fields 10 upon the electrical resistance
has also been investigated ; while the electrical resistance of molten
antimony at the melting point is 115-0 xlO~ 6 ohm-cm. 11 Both the
1 Lcitgebcl, Ze-ttvch. an.org. Chctn., 1931, 202, 30-5.
2 Ruif arid Bergdahl, Zeitsch. cm.org. Che-m., 1919, 106, 76. See also Carnelley and
Williams, J. Cham. Soc , 1879, 35, 563; Meyer and Mensehmg, Annalen, 1887, 240, 321;
#>-./., 1887, 20, 500, 1833; Meyer and Biltz^Uer., 1889, 22, 725; Zeitech. physical. Chc.ni.,
1889,4,249; Greenwood, ./^rJc. Roy. Soc., 1909, 82, 396; Zeitsch. tilektrocfwm., .19J2, 18,
3L9; van Liempt, ZeUsc/i. anorn. Chem., J920, 114, 105; 1920, in, 280.
: " J IvraiTt and Bergfeld, Bar'., 1905, 38, 258; Krallt, ibid., J903, 36, 1704; Schuller,
Wu'.d. Annalen, 1883, 18, 321; Demarcay, Cow.pl. rend., 1882, 95, 183. See also Zenghehs,
Zcitxch. phi/si leal Chcrn,., 1906, 57, 90.
1 von Wartenberg, Zeitsch. anorg. Chc/ni., 1907, 56, 320.
5 Meyer and Bikz, loc. c-it. See also Kuil and Mugdan, Zcilxch. a/iory. Chew., 1921,
117, 147"; Rufl and .Benrdahl, loc. cit.
fi International Critical Table.*, 1929, 5, 220. See also Eueken and Gehlhoff, J3er.
dcn.t,. phy.nkal Gfis., 1912, 14, 169; GehlhoiV and Xeuineier, ibid., 19.13, 15, 876, Euekou
and Xeumann, Zc-.Ufich. phy&ikal. Chew., 1924, in, 43.1.
7 Bridgman, Proc. Awcr. Acad. Artti and Sciences, 1922, 57, 77; 1923, 59, 119.
8 Lorentz, Pocjfj. Amialc/i, 1872, 147, 429; Wicd. Annalen, 1881, 13, 422, 582; Janettaz,
Ann. Chim. Phys'., 1873, [4], 29, 38; Matthiessen, -ibid., .1858, [3], 54, 255; Gehlhotl and
Xeuineier, Btr* dcul.. pJi.y^ihd. Gc<*., 1913, 15, 1069.
u .McLennan, Xivcn and Willielm, Phil. Mug., 1928, [7], 6, 666. Sec also Mcissner,
Zcilxch. Gas. Kallc-lnd., 1929, 36, 62; Meissner and Voigt, Ann. Pkyti!:,, 1930, [5], 7, 892.
10 Kapitza, Proc. Roy. &oc., 1929, A 123, 292.
11 Matsuyama, Kinsoku no Xenko, 1926, [4], 3, 254; Trans. A-rncr. tioc. Stcd Trc.alnu'.n.t,
1926, io, 31S. See also Matthiessen, loc. cd.; Krharcl, Wwd. Annalen, 1881, 14, 504;
Gehlhoff and Xeumcier, Bcr. deuL phyxikal. Gas., 1913, 15, 876; Xortlirup and Suyclam,
J. Franklin Inst., 1913, 175, 153; Bridgman, Proc. Amcr. Acad. Arls and Sciences, 1933,
68, 95; Allen, Phys. Review, 1933, 43, 569.
22 ANTIMONY AXD BISMUTH.
temperature coefficient and the pressure coefficient 1 have been deter-
mined.
For an anthiwny-platininn couph\ if the cold junction is maintained
at C., the tlienno- electromotive force in microvolts may be calculated
for any temperature between C. and 630 C. from the equation : 2
si,#pt= 46-24.J-!- 0-0313/ 2 - 0-00004-77/ 3
and the thermo-electric power, in microvolts per degree centigrade, from
the equation :
s,, Qn = -16-24 + 0-0636* - 0-00001438^
The magnetic susceptibility, using a Held lying between 1029 and
13,680 gauss, is -0-8138 x 10~ 6 . This value appears to be independent
of the field strength. 3 For a single crystal the mean magnetic suscepti-
bility 4 is -0-80 x 10~ 6 , the susceptibility depending upon the position
of the crystallographie axis with respect to the direction in which the
susceptibility is measured. There is little variation in the susceptibility
between room temperature and that of liquid air. The magnetic
anisotropy is ascribed to the unequal valency group in this clement. 5
The influence of particle size upon the diamagnetic susceptibility of
antimony has been examined. According to some investigators G the
diamagnetic susceptibility falls as the size of particle decreases, tending
to become constant at a diameter less than 0-5/z. It has also been
stated, however, that the size of particle is practically without effect. 7
The Hall effect 8 at 20 3 C. in a magnetic field lying between 4 and 16
kilogauss is +19-2 x 10~ 9 volt-cm, per ampere-gauss. The variation of
Hall effect with temperature, 9 and with variation of the magnetic field, 10
has been investigated. The Corbino effect, ll Ettingshausen effect, 12 Nernst
effect 13 and Righi-Leduc effect u have also been examined.
The refractive index 15 varies from 3-04 to 3-17, according to wave-
length, the corresponding absorption coefficients varying from 1-63 to
1-56.
Explosive, Amorphous or /5- Antimony is usually obtained by
the electrolysis of solutions of antimony trichloride. It was first
I Bridgman, Proc. Arner. Acad. Arts and Sciences, 1917, 52, 573; 1922, 57, 48.
- International Critical Tables, 1929, 6, 214; Pelabon, Ann. physique, 1920, 13, 169;
Com.pt. rend., 1923, 176, 1309.
3 Isnardi and Gans, Ann. Pkysik, 1920, [4], 61, 585; Owen, ibid., 1912, [4"j, 37, Gf>7;
Honda, Ann. Physik, 1910, [4], 32, 1027.
1 McLennan and Cohen, Trans. Roy. Soc. Can., 1929, Section III, |3"j, 23, 159. See
also de Haas and van Alphen, Proc. Acad. Sci. Amsterdam, 1933, 36, 263.
5 Vaidyanathan, Indian J. Physics, 1930, 5, 559.
Rao, Indian J. Physics, 1931, 6, 241; Nature, 193], 128, 153; Vaidyanathan, lor.
cit.; Nature, 1930, 125, 672.
7 Verma and Mathur, /. Indian Che.rn. &oc., 1933, 10, 321.
8 Ettingshausen and Xernst, Sitzunysbcr. K. A /cad. Wis*: Wien, 1886, 94 II, 5(i();
Barlow, Ann. Pkysik, 1903, 12, 897; Zahn, ibid., 1904, 14, 886; Alterthuni, ib>d. 1912
39, 933.
9 Alterthuni, loc. cit.; Barlow, loc. cit.
10 Barlow, loc. cit.; Cantonc and Bossa, Mem. accad. Italia, Pis. 2, 1930, Xo. 1.
II Adams and Chapman, Phil. Mag., 1914, [6], 28, 692; Chapman, ibid., 19 L6, (GJ, 32,
303.
12 Zahn, loc. cit.; Barlow, loc. cit.
13 Zahn, loc. cit.; Barlow, loc. cit.; Xernst, Wied. Annalen, 1887, 31, 760.
14 Zahn, loc. at.; Badow, loc. cit.; Alpheus W. Smith and Alva W. Smith, Phys
Review, 1915, [2], 5, 35.
13 Drude, Wied. Annalen, 1890, 39, 481.
AXTIMOXY AND ITS ALLOYS. 23
prepared by Gore 1 in October 1854 from solutions of antimony tri-
chloride, tribromide and triiodidc. The product obtained in each case
was different, and in each case was contaminated with the corresponding
halide, that I'roni the solution of antimony trichloride containing about
6 per cent, of lialide, and that from the solution of antimony triiodidc
about 22-2 per cent. Two specimens obtained from the electrolysis
of antimony trichloride gave the following analysis :
Sb .... 93-36 93-51
SbCL .... 5-98 6-03
IIC1 .... 0-46 0-21
99-80 99-75
Gore concluded that this variety of antimony was either capable of
forming an unstable compound of indefinite composition with antimony
haiides, or that it was an amorphous variety in which the halide was
mechanically entangled.
Both crystalline and amorphous antimony may be obtained by
electrodeposition from solutions of antimony trichloride in hydrochloric
acid, the nature .of the deposit depending upon the temperature, con-
centration and current density, 2 increase in temperature and decrease
in current density favouring the formation of the crystalline modification.
Cathodes of platinum, copper, manganin, graphite, zinc and mercury
have been employed. 3 X-ray examination of the deposit obtained
from solutions of antimony trichloride in glacial acetic acid, using a
copper cathode, indicates that the nature of the deposit is not affected
by a change in current density from 0-1 to 0-7 ampere per square centi-
metre ; that for a given concentration amorphous antimony is deposited
at a higher temperature than from aqueous solutions (particularly at
lower concentration), while at a given temperature amorphous anti-
mony is deposited at lower concentrations than from aqueous solutions. 4
Amorphous antimony is deposited from solutions in glacial acetic acid
containing 10 grams SbCl 3 in 100 grams solution below 40 C., and from
solutions containing 50 grams SbCl 3 in 100 grams solution below 55 C.
Within this range a mixed deposit is obtained.
Thin layers of antimony deposited on cellulose nitrate films show,
from electron diffraction patterns, an amorphous structure if the deposit
is not too thick, while thick deposits show only a crystalline structure.
With very thin layers the amorphous structure persists indefinitely,
while with deposits of medium thickness crystalline spots appear after
a time and gradually spread throughout the deposit. 5
A black, amorphous modification of antimony, probably identical
with that described by Cohen, has been prepared by the action of oxygen
or air on liquid antimony trihydridc cooled to about 40 C. ; and also
by the rapid cooling of antimony vapour. 6 A similar product has been
obtained by the reduction of antimony compounds in the presence of
1 Gore, Phil. J/^/., 1855, [4], 9, 73; Phil. Tra-nx., 1858, 148, 185, 797; 1862, 152, 323;
J. Cham. Svc.., 1863, 16, 365.
- Kerstcn, Ph.yxws, 1932, 2, 276; Cohen and Coffin, Zcitech. physikul. Chc-m., 1930,
149 A, 417; .Boiim, Zeitsch. an.onj. Chcm., 1925, 149, 217.
3 von Steimvchr and Schulzc, ZatscJi. Phywk, 1930, 63, 815.
4 Srillwcll and Audrieth, J. Amer. Chem. tioc., .1932, 54, 472.
5 Prins, Nature, 1933, 131, 7GO.
Stock and Sicbert, Her., 1905, 38, 3837.
24 AKTIMOKY AXD BISMUTH.
antimony trichloride. 1 In the absence of the trichloride, however, only
the crystalline modification is obtained.
By heating antimony in a stream of nitrogen a substance resembling
amorphous antimony has been obtained : 2 it is stated, however, to be a
mixture of antimony with antimony trioxide, 3 and was not obtained
when pure antimony and pure nitrogen were used.
A vitreous amorphous form of antimony has also been formed 4 by
the rapid quenching of small drops of antimony which has been fused
with antimony trisclenidc. The presence of antimony triselenide
retards the crystallisation of antimony considerably. These amorphous
Transition
*\ point
M.pt
Temperature
FJC:. 1. Vapour Pressure Curves of Antimony.
pellets are moderately stable even when heated to 500 C., but crystallise
much more rapidly at o 4 2() C.
Amorphous or /3-antimony is metastable at all temperatures below
the melting point. The transformation to the stable rhombohedral or
a-form takes place very slowly at ordinary temperatures, particularly
in the absence of any external stimulus. If the /3-allotrope is scratched,
however, the transformation takes place much more rapidly, and may
even approach explosive violence. The system is probably mono-
tropic ; the conditions of equilibrium are represented diagramatically 5
in lig. 1. It will be seen that the vapour pressure of the /3-allotropc
is always higher than that oC the more stable a-form, and that the two
vapour pressure curves intersect at a point (the "transition point")
above the melting points of both allotropcs.
1 Levi ami Chiron, Atti It. Acaid. Li-ncci, 1933, [G|, 17, f)65.
- Mora rcl, C'titn/if.. mid., 1888, 107, 420.
:i Cohen and Olic, Zdl^ch. yhyxikaL GYte?/v., 11)08, 61, 088.
4 r ramniarni and iMullcr, Zc.itsc.h. <uior<j. Chrtn., 19,34, 221, 100.
5 Cohen, J. *SV^. Chc.tn. I/id., 1921K 48, 102; Friend, "A Text-Book of Physical Chemistry "
(Crii'lin, 11)32), Vol. I, p. 179.
ANTDIOXY AXD ITS ALLOYS. 25
Amorphous antimony obtained by electrolysis is always contamin-
ated by antimony halides, and it has been shown that the halides arc not
held mechanically ; l it is assumed that these preparations are solid
solutions of antimony halide in the meta stable /3-allotrope, 2 and on this
assumption it is possible to formulate an explanation of the explosive
nature of the transformation from j8 to a. When amorphous antimony
is scratched, the heat developed by the scratch is sufficient to accelerate
appreciably the rate of transformation. As the transformation itself is
exothermic (see below), the surrounding material becomes heated, and
thus the transformation progresses almost instantaneously throughout
the mass. Allowing for heat losses by radiation, etc., the rise in tem-
perature is sufficient to volatilise the contaminating antimony halide,
and this rapid volatilisation is responsible for the explosive effect. It
should be stated, however, that a transition temperature of 96 to 100 C.
for the transformation, from /3- to a-antimony has recently been reported. 3
Photomicrographs of explosive antimony (deposited electrolytically)
have been examined before and after the " explosion." (The Ci ex-
plosion " was effected by a spark from an induction coil or from a
Ley den jar, or by touching the film with a hot needle). The polished
surface before the explosion resembles that of any other soft bright
metal. After the explosion, a very large number of fine lines is,
however, developed, parallel in that part of the film remote from the
origin of the explosion, but arranged in concentric circles around that
origin. These lines apparently are not a surface effect. 4
The heat of trans formation is 20 gram-calories per gram. 5
The heat capacity 6 between 150 C. and 411 C. is given by
// =0-0535656 -0-1-6635 x 10~H -f- 0-15497 x 10~ 6 Z 2 gram-calories per gram.
The specific electrical resistance 1 is 50,000 to 90,000 times greater
than that of rhombohedral antimony.
Yellow Antimony, an unstable allotropc, has been prepared by the
action of oxygen on antimony trihydride at - 90 C., and by the action
of antimony trihydride on chlorine dissolved in ethane at -100 C. in
red light. 8 It has only been obtained in very minute quantities,
reverting (above -90 C.) to the black (probably amorphous) modifica-
tion. It is believed to be isomorplious with yellow phosphorus and
yellow arsenic.
By condensing the vapour of antimony obtained by cathode splutter-
ing, the metal can be obtained in a form which has an extremely high
electrical resistance. 9 In this condition the characteristic X-ray
patterns are no longer obtained, thus suggesting that the metal is now
amorphous. By heating to 173 C. the normal form of the metal is
again obtained.
Spectrum. Antimony compounds impart no characteristic colora-
tion to the Bunscn flame. The wavelengths of the principal lines of the
arc spectrum, measured in Angstrom units [1 A. =10~ 8 cm.], are given
1 Cohen and Ringer, Zdtxch. physikcil. Chun., 1904, 47, 1.
- Cohen and Strengors, ibnl., 1905, 52, 129.
3 von Steimvehr and ISchulxc, he. cit. Sec also Lcvi and Ghiron, loc. at.; JSchulzc
and Graf, MttallwiHscliuft, 1933, 12, 19; Schulze, Ztitscli. -phmikul. Chan., 1933, 165, 188.
26 ANTIMONY AND BISMUTH.
below. The numbers in parenthesis indicate the relative intensities of
the lines, the lowest numbers indicating the weakest intensities. Wave-
lengths marked (a) are those of lines emitted by the neutral atom, those
marked R are of lines that arc easily reversed. 1
11864(4), 11208(4), 10840(5), 10743(5), 10678(10), 10587(5),
10263 (4), 10080 (4), 7924-6 (6), 7844-4 (4), 6806-3 (6), 6778-4 (6),
6129-9(6), 6079-6(6), 6005-0(6), 5730-4(4), 5632-0(4), 4033-5 (6 a),
3722-8 (8 a), 3637-8 (9 a), 3383-2 (5 a), 3267-48 (8 a R), 3232-52 (8 a 11),
3029-8 (8 a R), 2877-920 (10 a R), 2851-1 (4), 2769-95 (10 a R), 2727-22
(5 R), 2682-77 (4 R), 2670-67 (5 a R), 2598-076 (10 a R), 2528-53
(6aR), 2373-7 (4 R), 2311-5 (6 a R), 2306-5 (5 R), 2179-25 (4 R),
2175-88 (5 a R), 2068-38 (4 a R).
The principal lines of the spark spectrum are :
5639-7 (5), 4693-0 (10), 4591-8 (5), 4352-2 (10), 4265-0 (10),
4195-1 (8), 4033-5 (4 a), 3722-8 (5 a), 3637-8 (6 a), 3504-5 (10 a),
3498-5 (10), 3473-9 (10), 3267-5 (10 a), 3241-2 (10), 3232-5 (10 a),
3040-7 (10), 3029-8 (10 a), 2913-3 (5), 2877-920 (10 a R), 2851-1 (4),
2790-4(10), 2769-95 (10 a R), 2727-22(8), 2718-90(10), 2682-77(5),
2670-67 (5 a), 2652-60 (8), 2612-32 (8), 2598-076 (10 a R), 2590-29 (10),
2528-54 (10 a R), 2478-34 (6), 2445-55 (6 a), 2383-64 (4), 2311-5
(10 a R), 2306-5 (4), 2054-0 (6), 2039-7 (5), 2023-9 (4), 1926-6 (5),
1870-6 (10), 1867 (8), 1810 (5), 1783 (10), 1762 (10), 1731 (5), 1725 (6),
1712 (6), 1585 (8), 1566-3 (8), 1514 (10), 1438 (10), 1307 (10), 1225 (10),
1211 (10), 1205 (10), 1193 (10), 1171 (10), 1168 (10), 1162 (10), 1048
(10), 1042 (10), 1012 (10), 981 (10), 976 (10), 861 (6), 805 (5).
The most persistent lines emitted by the neutral atom, together with
the combinations of spectral terms (energy states) from which they arise
are: 2 2068-38( 4 S - 4 1%), 2175-88( 4 S, - 4 1 3 2 ), 2311-50( 4 S -*I\), 2528-53
( 2 D 3 - 2 P 2 ), 2598-08( 2 D 2 - 2 P 1 ), 3232-52( 2 P' 2 - 2 P 2 ), 3267-48( 2 F 1 -*1\).
The absorption spectrum of antimony vapour shows a banded
structure extending from A 2305 to A 2250 A. with a constant interval of
nearly 15 A. At higher temperatures another banded structure occurs
in the region A 2830 to A 3000 A. Fine lines have also been observed at
A 2312 and A 2306 A. and at higher temperatures at A 2770 A., but
subsequent investigation failed to reveal these lines. 3
From a study of the absorption spectrum 4 it has been suggested
that three types of diatomic molecules can exist in the vapour of
antimony and that they occur in the proportions
(Sb 121 ) 2 : Sb l21 .Sb 123 : (Sb 123 ) 2 =5 : 8 : 3
In the accompanying bibliography references are given to the more
important researches dealing with the arc spectrum,* and deductions
1 International Critical Tables, 1929, 5, 312. A bibliography is included.
- Interrtfdioml Critical Tabhs, 1929, 5, 324.
3 Fraync and Smith, Phil. JUV/f/., 1926, [7], I, 732. 800 also Xarayan, ibid., 1925,
[G!, 50, 645; Debbie and Fox, Proc.'jtoy. &w., 1920, 98 A, 147; Charola, Phyxikal. Zc.it M/I.',
.1930, 31, -157; lluark, jMohler, Foote and Chenault, LJ./S. llureau of titandurdti, Mcw/icv
Papers, 1924, 19, Xo. 490, 463; Xakamura and Shidci, Japan J. Physic*, 1935, 10, 11.
4 8. >1. Naude, Phyv. Rwirw, 1934, 45, 280.
5 Kretzcr, Zaiixc.h. wixx* Photocficm., 1910, 8, 45; Green and Lorin^, Phy*. Jit'.vic.w,
1928, 31, 707; Charola, lor,, dt.; Univ. La Plata, Etstudia* Cic.-ncia^ 1929, 89, 205;
Malurkar, Proc. Camb. J'hil. Soc., 1928, 24, 85; McLennan and McLay, T-mua. Roy. tioc.
Canada, 1928, [3j, 21, 111, 63; Ruark, Mohlcr, Foote and Chenault, foe. cit.; Pj'na de
Kubies and Barques, Zcitsch. anorg. Chem., 1933, 215, 205; Kracincr, Ztitsch. anal.
Chew., 1934, 97, 89.
AXTIMOXY AND ITS ALLOYS. 27
from it regarding sub-atomic structure, 1 the spark spectrum,,- the flame
spectrum* the ultra-violet spectrum^ series spectra,* the ultimate rcnjs^
the Zeeniaun effect, 1 and the critical potential, resonance potential and
thermionic discharge spectra.*
From the spark spectra, of antimony in various degrees of ionisation
it is calculated that the ionisation potential for singly ionised antimony 9
is 18 volts (or 18-8 volts), and that for doubly ionised antimony 10
24-7 volts. 11
By illuminating the vapour of diatomic antimony by a mercury arc
of high luminosity, a rather strong fluorescence has been obtained,
excited by four mercury lines and possibly by two others. 12
The wavelengths of the most persistent lines in the spark spectrum
of solutions of antimony chloride, together with the dilution at which
the lines persist, 13 are as follows :
; 1 per cent, to
0-1 per cent. Sir -
0-1 per cent, to > 0-01 per cent, to \
0-01 per cent. Sb^+ 0-001 per cent. Sir -'- :
1 3739-95
1
3597-51
3504-51
3337-15
3267-53
3232-54
3029-86
3029-86
i 2877-92
2877-92 2877-92
: 2790-39
2790-39
2598-08
2598-08 2598-08 :
2528-54
2528-54
2311-48
1 McLennan and McLay, toe. cit.; Green and Lanu', J^ruc. Nat. A cad. /Scie/ice, 11)28, 14,
706.
- Krctzer, loc. cit.; Dhavale, Nature, 1930, 126, <)7; Lang, Phys. Review, 1930, [2],
35, 44,1; Campetti, Nuovo Cim., 1928, 5, 291; Soulhlon, Com.pt. rend., 1929, 188, 1103;
Pattabhiramiah and Rao, 1-udian J. Physics, 1929, 3, -437. a Krctzer, loc. cit.
4 Bloch, Cuwpt. rend., 1924, 178, 472; 1920, 171, 709.
5 Lang, Proc. NaL Acad. 8c.ience, 1027, 13, 341; van Lohnigen, Proc. K. A hid.
Wctcritich. Amsterdam, 1912, 15, 31.
de Gramont, CompL rend., 1908, 146, 1260.
7 van cler llarst, Arch. Neerlaiul, 192-1, [3 AJ, 9, J ; Proc. K. Akad. WetenxrJi. Amster-
dam, 1920, 22, 300; Purvis, Proc. Camb. Phil. Soc. t 1907, 14, 217; Loxventhal, Zedsch.
Phyfik, 1929, 57, 822; Green and Lorin^, loc. cit.
6 Ruark, Mohlcr, Foote and Chcnault, loc. cit.; Siksna, Coin/pt. rend., 1933, 196, 1986.
For further reference to the spectra of antimony, see Gibbs, Vieweg and Gartlem, PJiys.
Re'cleu:, 1929, 34, 406; Gibbs and Vicwcg, loc. cit., p. 400; Xegresco, J. Chim. phys.,
1928, 25, 363; Green and Lang, Nature, 1928, 122, 241; Zumstein, Phys. Review, 1927,
29, 209.
9 Lang and Ve.strme, Phy*: Review, 1932, 42, 233; Dhavale, Pwc. Roy. Soc., 1931,
A 13 1, 109. 10 Lang, 'Phys. Review, 1930, 35, 445.
11 ISee also Badami, Proc. Phys. &oc. London, 1931, 43, 538; Lang, Phys. Review, 1932,
39, 538; Ricardi, Atti R. Accad Lined, 1927, [6], 6, 428.
12 Genard, Nature., 1933, 131, 132; Phys. Review, 1933, 44, 468. See also Siksna,
Compt. rend., 1933, 196, 1986.
13 Baly, " Spectroscopy " (Longmans, 1927), \'ol. II, p. 144.
28 ANTIMONY AND BISMUTH.
The X-ray spectrum has also been examined, the lines in the K
series 1 and the L series 2 having been recorded.
Single crystals of antimony have been prepared, the methods
adopted being, in general, similar to those employed Tor bismuth (see
page 131). Among the properties of such single crystals that have been
investigated are the mechanical properties, 3 the electrical resistance^ the
thermo-electric properties, 5 and the magnetic susceptibility. 6
Chemical Properties of Antimony.
Antimony does not combine directly with hydrogen, and can be
volatilised by heating in a stream of that gas. 7 Antimony compounds
are reduced by nascent hydrogen in acid (but riot in alkaline) solution
forming antimony trihydride or stibine. Metallic antimony is pre-
cipitated from solutions by hydrogen at high temperature and pressure. 8
With solutions of antimony trichloride of concentrations up to 50 per
cent., and hydrogen at a pressure up to 150 atmospheres, the quantity
of precipitated material is proportional to the pressure. The reaction
is of the first order with pressures between 15 and 150 atmospheres and
concentrations less than normal. It is calculated that from a normal
solution of antimony chloride at 20 C., with hydrogen at a pressure of
"100 atmospheres, the precipitation of 1 per cent, of metal would require
1 (>() years. Increase of hydrogen ion retards the precipitation of
antimony. From the behaviour of antimony as a catalyst in the silent
reaction between hydrogen and oxygen, the metal does not appear to
absorb hydrogen. 10
Antimony is not appreciably affected by exposure to dry air, but in
(he presence of light li and moisture oxidation takes place. 12 It burns
brilliantly even in very dry oxygen. 13 It is oxidised to antimony
pcnloxidr by ozone. 1 ' 1
It decomposes steam only at very high temperatures, hydrogen and
1 Cork and St.ephrnson, rhyx. Hcrir.w, 192(5, [2], 27, 530; Leide, Compt. rend., 192.1,
180, 1203; Hay, /'/<//. Mn<j., 1924, [(>], 48, 707; Walter, Ze.itxcli. Pliyxik, 1924, 30, 357;
Sir.'-Uihn, Jar/ib. Hml. lUektron., 11)1(5, 13, 29(5.
; ' Ilirata, I'n>c. /toy. AW 1 ., 1024, A 105, 40; Kellstrom, Zcitxch. Pkyxik, 1927, 44,
:N ), Pokrow.sky, Zcitxr/i. I 'h I/HI/:, 1926, 35, 390; Ray, loc. cit.; Dauvillier, Cftwpt.. rc:n<\.,
1121, r/^ 115S; Coster and Mulder, Zritfich. /V/v/.s?//, 102(5, 38, 2(54; Lindsay, Cow/,/.
'/., 1922, 175, 150; Hjalinar, Zcitwh. /V/.y.sv/,-, J<)2(), 3, 302; Druyvesleyn, ZrilM.h.
//-.//.-. 1927, 43, 707; Coster, r/nl. May.* 1922, [(}], 43, 107S. See also Chamberlain,
itui,, 1921, 114, ;">()(), /V;//.s. fii-ricir, I92f), (2j, 26, 525; ('haniherlain and Lindsay,
//' /'"'" "\ 1927, [2j, 30,' :$(}!>; Blake and Duane, Phy*. Renew, 1917, [2|, 10, (><)7;
!i and Cox, /'roc. Hoi/. Nor.. 1 9.')0, A 127, 4,'Jl.
r>M.l"inan, I'mc. Autir. Acatt. A ;-/.s and Xcir.Hrrx, 1 929, 63, ,'55 1 .
r.ri.l-'nian, Inc. rit.\ I'ruc. Xdt. Arm/. /SV/., 192.S, 14, 9-13.
MI-LITHIUM and Cohen, 7'/v///x. /'n//. Xuc. (<'(tndd(i, J929, [.'{], 23, III, 159; .Nu.slw.um,
/:, n, u , 19L'7, 29, 905.
\ atid( \cldc, Hull. Acini. />//;/., 1S95, [;jj, 30, 7S; Bottler, J.'jiralct. Chevi., ISO!),
I:L
ljuln-\ and Nikolairv, ./. Hux. /'hyx. Chetn. Nor., 1920, 58, (59S.
Ip.ittfv, jun , //>/'., I'J.'il, 646, 2725; Ij>atiev and Tredoroviteh, ,/. (le.n. Cheni. A'.s\v.,
, :, 7 :. M J ;'/>''/'., 19.'{2, 658, 575.
K;. ."<-r, /r//.s<-/<. (umftj. Chi i/i., liKJO, 194, T.\.
>,-Jinn!M'in, ['<><!<j. Annnltn, 1K1K, 75, 3(52; ,/. pnifct. Chein., LS55, 66, 272.
i;. r/..d;ti;-, Xchwt t(Wr** <) '., \^, 6, 14-1; ISIS, 22, (59; Proust, (li-klvtSs Ally. J.
.. 1S(K>. '), 51.'>; (i'ilbirt\t Anntilcji, 1S()(5, 25, 1S(5.
r.,ii-..-r and Dixon, /W. Roy. >S'or., 1SSS, 45, 1.
AXTIMOXY AXD ITS ALLOYS. 21
antimony trioxidc being formed : l precipitated antimony reacts more
readily. 2 Neutral hydrogen peroxide is without action, but in the
presence of an alkali antimonates are formed. 3
Antimony burns vigorously in fluorine ; 4 it also combines directh
with chlorine, bromine and iodine, 5 with the first even when very dry.*
Hydrofluoric acid is without action, while hydrochloric acid attacks
antimony only in the presence of air. 7 The solvent action of hydro-
chloric acid is increased by the addition of a little nitric acid ; 8 aqu?
regia converts the metal completely to antimony trichloride and anti-
mony pentachloridc. With nitrosyl chloride the compound SbCl 5 .NOC
is obtained. 9
When antimony is fused with sulphur, combination takes place witr.
the formation of antimony trisulphide. (It is doubtful whether eithei
a higher or a lower sulphide is also formed.) The elements will alsc
combine when heated together with water in a sealed tube to 200 C. ; 1C
and when a powdered mixture is subjected to high pressures. 11 Dry
hydrogen sulphide attacks antimony at 360 C. and above, antimonv
trisulphide being formed ; when the metal is heated moderately in
a stream of sulphur dioxide, a mixture of antimony trioxidc and
antimony trisulphide is obtained. 12 Warm concentrated sulphuric acid
attacks antimony forming antimony sulphate, but both dilute and
cold acid are without action.
When antimony is heated with the vapour of thionyl chloride, the
latter is decomposed with formation of antimony trichloride. 13 Sulphui
monoxide is also formed and it is suggested that the reaction proceeds
according to the equation :
3SOC1 2 +2Sb =2SbCI 3 +3SO
When, antimony is heated in a stream of sulphury! chloride (diluted
with carbon dioxide) the metal is converted to the trichloride. 14
Antimony does not combine with nitrogen. It is attacked by nitric
acid with evolution of.' nitric oxide, the remaining products depending
upon the concentration and temperature of the acid. The action takes
place only slowly in the absence of nitrous acid. 15 Antimony nitrate
may be formed when cold, dilute acid is used : but more generally n
1 Bcrzclius, Joe. at.: Renault, Ann. Chim. Phys., 1836, [2], 62, 362.
- .Ditte, Compt. rend., 1S92, 115, 939. See also Thiele, 'Annahn, 1891, 263, 301
RufT and Albert, Her., 1905, 38, 54; Cohen and Ringer, Zedsch . physical. Chcm., 1901
3 Clark, J. Chc.m. Soc., 1893, 63, 886.
1 IMoissan, Ann. Chim. Phys., 1887, [6], 12, 523; 1891, [G], 24, 247.
"' Floresco, B-ul. Fac. Stiinte Cerrt-auti, 1.929, 3, 2-4; Chem. Zentr., 1931, I, 1586.
fi Cowpcr, r7. Chc.m. Snc., 1883, 43, 153.
7 Ditte and Metzncr, Compt. rend., 1893, 115, 936. See also Clasen, ,7. prakt. Ck&rn.
1804, 92, 477; von dcr Planitz, Bull. Soc. chim., 1875, [2], 24, 69.
8 Cooke, 7Voc. Amw. Acrid. Arts and Sciences, 1877, 13, IS; Pxolnquct, Ann. Chi'in.
Phy*., 1817, [2], 4, .165.
<n Sndborough, ,7. Chc.m. Soc., 1891, 59, 655.
Oeitner, An-ualcn, 1864, 129, 359.
1 Spring, Bcr., 1883, 16, 999.
- Uhl, Jlc.r., 1890, 23, 2154. See, however, Scliiff, Annsikn, 1S6I, 117, 95; Goitner
:i Sehenek and Platz, Zc'tlxch. anonj. Chc.ni., 1933, 215, 1.13.
1 Danneel arid SeldoUrnann, Zeitvch. anory. Cham., 1933, 212, 225. For the aetior
of compounds eontainine chlorine and sulphur, see Hcumann and Koeblin, Bar., 1882
15, 419, 1737; 1883, i6^'482, 1625.
15 Millon, Ann. Chim. Phys., 1842, [3], 6, 101.
AXTIMOXY AXD ITS ALLOYS. 31
theoretical calculation based upon van der Waal's equation indicated
that the molecule of antimony may contain about twelve atoms. 1
The normal electrode potential, 2 Sb/Sb~ HH ~, is +0-244 volt measured
on the hydrogen scale at summer temperature. In a 10 A 7 solution of
potassium hydroxide at 20 C. the electrode potential 3 is given by
0-058 .
E = -0-675 + log Csbo 2 -
the process of solution being represented by
Sb + 40H- + 30 > SbO 2 ~ + 2H 2 O
If the reaction proceeds according to the equation
Sb0 2 "+20H-+2 >SbO 3 "+H 2 O .
then the potential is given by
E= -0-589 4-^P log (Csio 3 -/Csb0 2 -)
Passivity of the antimony anode is not attained unless the current
density exceeds 7-5 amperes per sq. dm.
The antimony electrode has recently received considerable attention. 4
The electrode consists of a rod of metal connected by a copper wire to a
calomel cell. The rod should be clean, and should dip into a solution
containing suspended purified antimony trioxidc, which should be
stirred continuously. Cast antimony appears to be preferable to
electrolytic metal. 5 The value of E is given as 6
E= + 0-030 +0-05915>H
The temperature coefficient is stated to be 0-0013 volt per degree in
1 von Laar, Proc. K. A hid. WHen.wk. Am-th-rda-m, 1016, 19, 2.
- Jcllmek and Gordon, Zeitsch. phyxihd. Cham., 1.024, 112, 207.
:! Grubc and fSehwcigardt, Zfiitwh. EleJdrocheni.., 1023, 29, 257.
4 Femvick and Oilman, J. Riol. Chc.m., 1020. 84, 605; Westenbrink and Peters,
X<>.(lwla>td. 'fijdM.hr. Gcneevkunde, 1020, 73, 1, 2073; Brmkman, Ibid., 1020, 73, 11,
5000; Harrison and Vriclhacbiilam, Mem. Jh.pt. Ayr. India, Cham, tier., 1920, 10, 157;
llano, 7>V/-. Ohara Lust, landw. Forsc.h. Japan, 1020, [2], 4, 100, 273; Shukov arid Gorlikov,
J. ltu*x. L>hyx. Chc.m. Soc., 1020, 61, 2055; Z(yi^cL''j':icJcf.rochf>m., 1030, 35, 853; Vogcl,
J. Xoc.. Chain. Ind., 1030, 49, 207 T; Hahn, Zc.itscJi. anr/ew. Chem., 1030, 43, 712; L.ava
anil Hc^rnedcs, Philippine Ayr., 1028, 17, 337; Vies and Vellin^er, Arch. phy*. bio!., 1027,
6, 38, 02; Brinkman and Buytendijk, Bioclwm. Zc.it., .1028, 199, 387: Brewer and Mon-
tillon, TKUIS. Amcr. Elc.ctroclidm. S'or:., 1000, 55; Buytendijk, Arch, -nwland. phyxio'!.,
1027, 12, 310; Roberts and Fenwick, ,7. Amer. Ckc.iri. ;S'or., 1028, 50, 2125; Lindcman,
M(ddinfjp.r Norycx La-ndbrul, 1026, 6, 302; Snyder, Soil Sci.encs-, 1.028 ? 26, 107; Kolthoff
and Furrnan, " Potc.nUoinc.tric Titrtilion.t*' (Xe\v York), 1020, 225; Vellingcr, Chi-mie. H
J-ndnMriC'., 1033, Special Xo., June, 21.8: Ann. cornbuxliblt liquid, \\Yte, 9, 673; Parkes
and l>eard, J. Phyn. Chew.., 1033, 37, 821; Bodforso and Kolmquist, Zeitsch. phyxi-Icdl.
Chcni., 1032, 161, 61; Catonacci, L'lml. MM. Hal., 1031, 24, Xo. 8; Int. Svr/ar /., 1032, 34,
185; Roche and .Roche, Arch. -phys. b/.oL, 1032, 9, 273; King, Ind. Eng. Chem., A ual. Ed.,
1033, 5, 323; Leclerc, 'Hull. awor.. ing. dec. (Li.ct/c}, 1032, IO, 210; t'eniura and Sucda,
Bull. ('hem. Xor. Japan., 1033, 8, 1 ; ihbbard, J. A^oc. Official Af/r. Chtni., 1033, 16, 103;
Oysmck, Arc/tit;. Xmkc.r-hid. Xcdnl.-f ndie., 1!)32, \\\\, Mod. IO, 7J1.
5 1-iritton and Robinson, J. Clicm.. .SVy., 1!)31, 134, -15S; KolthoiV and Funnan, /or.
nf-.; Catonacci, Inc.. ciL- Cex, Arch. phy. btol., 1031,9, 110; di Gloria, Ki^'rlf-l. A'uzl*'-
-nihiycl:., 1!)3(), 33, 103; Jtano, loc.. ciL
30 ANTIMONY A3TD BISMUTH.
mixture of oxides of antimony is obtained. 1 The metal will not burn
in the vapour of nitric acid. 2 It will dissolve in nitric acid to which
has been added tartaric acid or certain other organic acids, 3 and the
solution remains clear on warming. 4
Molten antimony combines readily with phosphorus. It reduces
both phosphorus trioxidc and phosphorus trisulphide when heated for
a long time with those substances ; it reacts quantitatively with
phosphorus trichloride. 5 When heated with phosphorus pentachloridc,
a mixture of antimony trichloride and phosphorus trichloride is obtained. 6
The trichloride, trioxidc and trisulphide of arsenic react similarly with
antimony.
When antimony is heated in a current of carbon dioxide a reaction
takes place, beginning at 830 C., and which, at 1100 C., may be
represented by the equation 7
2Sb +3CO 2 =Sb 2 O 3 +3CO
Antimony will react with the alkali metals forming antimonidcs. 8
It is attacked by solutions of alkalis and of alkali salts. 9 As has been
stated above, antimony acts as a reducing agent under certain con-
ditions ; it will reduce the following salts, at least partially : ferric
chloride, 10 ferric sulphate, potassium ferricyanide, potassium nitrate, 11
and potassium permanganate (forming manganese dioxide). 12 The
reduction of silver nitrate depends upon the concentration of the
solution : from a Q-oN or 0-25A 7 solution silver may be precipitated
quantitatively, but with a weaker solution (0-OoA 7 ) the reduction is
incomplete, and a compound, 2Sb 2 O 3 .N 2 O 5 , is formed. 13 Gold chloride
is completely reduced by antimony. 14 Antimony compounds arc
reduced to the metal by the action of Bettendorf s reagent (a mixture
of stannous chloride and hydrochloric acid). 15 Metallic antimony reacts
with iron at the melting point of the former. 16
The atomicity of antimony docs not appear to be known with
certainty. From a calculation of the heat of evaporation it has been
deduced that antimony, between the boiling point and melting point, is
monatomie, 17 remaining in that condition when cooled to 357 C. At
lower temperatures, polymerisation takes place. On the other hand, a
1 Rose, Por/ff. Annalcn, 1841, 53, 1.6 L; Lefort, J. Phann. Chint., I8f>f>, [3], 28, 93.
- Austen, G/iern. JWw.v, 1889, 59, 208.
;! Strong, Di-nrjl. poly. J., 18,19, 151, 389; Ozenvek, Zcitvch. anal. Chcm., 190(5, 45, 505.
4 .For the action of other nitrogen compounds on antimony, see Curtiu.s and Darnpski,
,/. prakt. Chcm., 1900, [2], 61, 408; Sabatier and Senderens, llnll. Hoc., c/ii-m., 1S92, [3|, 7,
504: Dalietos, Praklihi, 1931, 6, 92; Chr.ni. Zc.-nfr., 1931, ii, 1687.
5 KrafTt and Xeumann, Jir.r., 1901, 34, 565; Miohaolix, ,/. prakt. Chvm., 187 1, [2], 4, -12.").
(i Baudrimont, An-n. Chh/i. Phi/x., 1864, ['4|, 2, 12. For the action of phosphoric acid,
soo Portev.in and Sanfoui'che, (lowpl. rend., 1931, 192, 1563.
7 de Baelio, 3loii(it*k., 191 G, 37, 119.
8 Lebeau, Hull. tioc. chiin., 1900, [3j, 23, 250; Com.pt. rc.tid., 1900, 130, ,102.
9 Ruit and Albert, lor., clt.
Attlield, ZrMwli. anal. Chem., 1870, 9, 107.
1 Hottirer, ,/. praU. Clic.m., 1S7--1, [2], 9, 195.
- Sla{(>r, ',] . prahl. Chcm., 1853, 60, 217.
;; Scndorens, />////. Hoc. chun., 189(i, J3j, 15, 21,8. Sec also Polork and Thunimcl,
/>c ., 1883, 16, 244(5; Scndi-rens, Cnntpt. rrtid., 1SS7, 104, 501.
1 Doxter, Po<j<j. Ann<t!cn, 1857, 100, 568.
f) I'n^niollo, '/iolL Ckim. F<mu. 9 J914, 53, (><89.
(; Tjinimann. and .Schearvvaehter, Zf.iffsch. anory. CJu-m., 1027, 167, 401.
17 Jouniaux, Bull. Soc. chim., 1924, [4J, 35, 463.
32 AXTIMOXY AXD BISMUTH.
soils of varying ptl value, 1 while the -pH value against a standard
calomel electrode varies according to the following : 2
E +0-026 + ( -18)0-00016
P ~ = 0-0542 +(*- 18)0-000275
The electrode gives a linear relation between the observed, e.m.f. and
the plU values 3 with a probable error of 0-01 to 0-08 pH. 4 It compares
satisfactorily with the hydrogen and the quinhydrone electrodes, 5 and
has been recommended for use in connection with the examination of
acids and alkalis, soils, blood, sugar liquors, etc. 6 It docs not appear to
be suitable for use in connection with the leather industry. 7
The e.m.f. of the cell :
Explosive Sb SbCL> solution | Rhombohedral Sb
is 0-014 volt, the temperature coefficient -^= being 6-8 x 10~ 5 volt per
degree. If the current exceeds a certain limiting value the cell
explodes. 8
Antimony exhibits the valve effect in nearly all electrolytes even at
600 to 700 volts. 9 This is due to the formation of a layer of oxide on the
surface of the anode.
The potential difference between antimony and air 10 is 0-16 volt.
Atomic Weight of Antimony.
Approximate Atomic Weight. That the atomic weight of
antimony is approximately 122, and not a multiple or submultiplc of
this amount, is indicated by several considerations :
The specific heat of antimony between and 100 C. averages 0-05
calorie. Assuming a mean atomic heat of 6-4, the atomic weight,
according to Dulong and Petit's Law, is approximately 128.
The properties of antimony indicate that the most appropriate
position in the Periodic Table for this element lies immediately below
arsenic, in the fifth group. This places it between tin (At. wt. 118-7)
and tellurium (At. wt. 127-61), so that its atomic weight should lie
between these values.
The atomic number of antimony, namely 51, confirms its position
between tin (At. No. 50) and tellurium (At. No. 52).
1 du Toit, 8. African. J. Science, 1930, 27, 227.
2 Avseevitsch and Shukov, J. Gen. Ckem. Ruxs.. 1031, i, 109; Zeitsch. Elektrochc'in.,
1031,37,771.
:> - Fosbindcr, J. Lab. din. Med., 1931, 16, 411; llano, loc. cit.; King, Jnd. En<j.
Chem. (Anal.}, 1933, 5, 323. See, however, di Gleria, loc. cit.
4 Gcx, loc. cit.: Galvez, Philippine Ayr., 1930, 19, 219; Fosbinder, loc. cit.
5 Itano and Araka\va, Bc-.r. Ohara 2-ti^t. landic. Forsch. Japan, 1930, [4], Xo. 3, 3S3;
Vcrain and Mile. Toussaint, Corn.pt. rend. xoc. biol., 1930, 103, Oil ; Bntlon and Robinson,
loc. ciL
G Bottger and von Szebelledy, Zriltc.h. EhUrochem., 1932, 38, 737; A-nif-.r. Dy^iuff
Rc.-ptr., 1932, 21, 432; Houghoudt, Verxlar/. la.ndb. Ondc.rznc-.lc.. Rijkxlandhou-wproef,<t(t .,
1930, 35, 162; Barnes and Simon, ,/. Atnp.r. tioc. Ayron-., 1932, 24, JoG; Lakshnianro\v,
Current Science, 1932, i, 34; Shukov and Bulhinov, J. Gen. Chcm. Ru**., 1932, 2, 407;
du Toit, loc. cit.; Shukov and Gort.ikov, J. Jlu.<*. Phy*. Ohc.m. Sor.., ] 929, 61, 20r)r ); Zc-ilvc.h.
Klf-lctrochcin., 1930, 35, 853. 7 ' Pleass, Arch, phys, biol., 1932, 9, 2()7,
8 von Steinwehr and Schulxe, Zeitsch. Physik, 1930, 63, 815,
9 Schulze, Ann. Physik, 1907, [4], 24, 43.
10 Andauer, Zeitsch. physical, Chem., 1928, 138 A, 357.
AXTIMOXY AND ITS ALLOYS. 33
Application of Avogadro's hypothesis to the results of vapour
density determinations of volatile antimony compounds indicates that
the atomic weight of antimony is approximately 122.
The mass spectrum of antimony consists of two strong lines, 121 and
123 respectively, so that the atomic weight of the element must lie
between these two values (sec p. 38).
Exact Atomic Weight.- -The dissatisfaction expressed by Berze-
lius in the words " Ich habe niemals mil einer Materie, wo es so ausser-
ordentlich schwer gezvesen ist, konstante Eesultate zu erhalten, gearbeitet"
has been experienced by many workers on the atomic weight of antimony,
and few elements have proved so troublesome in this respect. It is on'lv
during the last few years that consistent values have been obtained ;
therefore, in the accompanying table, it will suffice merely to mention
in most cases the mean, results of the earlier researches. All the atomic
weight values have been recalculated from the ratios given, using in
addition to the antecedent data quoted in the Introduction, p. x, the
following values : Cu, 63-57 ; Ba, 137-6.
Of the researches prior to 1921, those of Cooke alone need be
mentioned.
Cooke x attempted to exercise the same care in his work as Stas had
done in his classical determinations. He worked, however, with small
quantities, whereas Stas sometimes used more than 100 grams. Cooke
therefore reduced the error due to occlusion of solution by the pre-
cipitate by employing much more dilute solutions. In his initial work
he employed four methods.
(a) Synthesis of Antimony Trisulphide. Balls of antimony were
treated with hydrochloric acid containing a little nitric acid, and the
solution boiled until it became colourless. The balls were then removed,
washed, dried and weighed ; the loss in weight gave the amount of
antimony dissolved. The solution was diluted with aqueous tartaric
acid, and antimony trisulphide precipitated by means of water saturated
with hydrogen sulphide. The washed precipitate was dried at 130 C.
The analysis of this gave 2Sb : 3S --=71 1-269 : 28-5731, whence Sb =
120-22. On heating to 210 the red trisulphidc changed into the black
variety. This gave UK- nrtio 2Sb : 3S -71--I818 : 28-5182 ; whence
Sb- 120-50.
(b) A)inli/,\'is of Antini.onij Trichloride. The material was purified
by distillation and by crystallisation from carbon disulphide. The
analysis was carried out by dissolving the trichloride in aqueous tartaric
acid and sideling silver nitrate solution. The ratio SbCl 3 : 3AgCl
53-000 : 100 gives a, value for antimony, 121-82, almost identical with
that obtained by Dumas, using the same method. Cooke. however, was
not satisfied with the result since it did not agree with certain of his other
determinations, lie advanced the suggestion that the high result was
due to the presence of sonic oxychloridc in the trichloride ; this, however,
is not supported by the evidence of his own work.
(c) .hifdt/xix of A-nlhnonij Tribromlde. - The tribromide was pre-
pared by the action of powdered metallic antimony upon bromine in
carbon disulphide solution. It was purified by distillation over finely
powdered antimony and crystallised from carbon disulphide. The
ratio Sl)Hr ;5 : 3A<>Br 03-830 f 100 gave Sb -119-863.
1 Cooke, l*rw. Antcr. Acad. Ail* Xci , 1877, 13, 1; 1880, 15, iMl; 1SSJ, 17, J; Bar.,
JSSO, 13, 9f>J.
34
AXTLMOXY AXD BISMUTH.
DETERMINATIONS OF THE ATOMIC WEIGHT OF
ANTIMONY.
Authority.
Ratio Determined.
i Xo. I Atomic
: of Weight of
: Expts.| Antimony.
Kessler 2 (1855-1860).
Schneider 3 (1856)
Weber 1 (1856) .
Dexter 5 (1857) .
Dumas c (1859) .
Unger 7 (1871) .
Cooke 8 (1877) .
Cookc 9 (.1880-1 881) .
Schneider 10 (1880)' .
Pfcifer 31 (1881).
Bonsfartz 12 (1883)
Popper 13 (18S6)
Friend and Smith ll
(1901)
Willard and Me A] pine 15
(1921)
Muzaffar 16 (1923)
Knop 17 (1923) .
Honigschmid, etc. 1S
(1924)
Wcatherill 10 (1.924) .
Krishnas\yami 20 (1927)
2Sb:Sb 2 4 = 100: 124-8
Various methods from which he deduced
the mean value . . .
2Sb: 38=71-480: 28-520
One analysis of SbCl 3
2Sb: Sbo0 4 "= 79-283: 100
SbCl 3 : 3Ae = 70-512 : 100
Analysis of Schlippe's Salt, Xa 3 SbS 1 .9H, )
2Sb: 38 = 71-4818: 28-5182
SbCl 3 : 3AgCl. = 53-066 : 100
SbBr n : 3AgBr = 63-830 : 100
Sbl 3 : 3Al =71-060: 100
SbBr 3 : 3 Ag = 111-114: 100
2Sb: 38 = 71-459: 28-541
3Cu:2Sb = 100: 128-259
3Ag : Sb = 100: 37-485
2Sb : 3BaS0 4 = 100 : 290-306
3Ag : Sb = 100: 37-434
CjHJCSbOf : KC1 = 100 : 23-0484
SbBr 3 : 3 AgBr = 35-69757 : 55-63121
3SbCl 3 : KBr0 3 (see p. 37)
2Sb : Sbo0 4 = 2-7250 : 3-4395
SbCl 3 :"3Ag = 70-488 : 100
SbBr 3 : 3 Ag = 1.1 1-699 : 100
SbCl 3 :3Ag = 100: 70-4864
SbBr 3 : 3Ag (see p. 37)
129-0
122-37
8
120-55
1
120-7
13
122-46
7
121-83
1
119-8
11
120-56
17
121-82
15
119-863
/
119-786
5
119-861
3
120-42
3
122-23
7
121-32
12
120-62
15
121-15 ;
8
, 120-34
8
i 121-768
32
[I 121-138 to
V .122-400
6
122-06 '
8
, 121-76
8
: 121-76
8
121-748
21
[ 121-716 to
\ 121-758
Berzelms, Afhandl.in.gar i Fysik, Kc/mi, etc., V, 41)0; K. Vf-l. Akad. Ua-ndl., 1812, 189;
rf.s Anna I en, 181.2, 42, 283'; Schwe.igger's J., 1812, 6, 155; 1818, 22, 70; 1818, 23,
Pofjq. Annahn, 1826, 8, .1.
Kessler, Poyg. Annahn, 1855, 95, 204; 1860, 113, 134.
Schneider, Awnnhn, 1856, 97, 483; 1856, 98, 293.
Weber. See Rose, Annahn, 1856, 98, 455.
Dexter, Annahn, 1857, 100, 563.
Dumas, Ann. Chim. Phys., 1859, [3], 55, 175.
Unger, Archiv Pharm., 1871, 197, 194.
Cooke, Proc. Anier. Acad. Arts Sci., 1877, 13, 1; 1880, 15, 251; Her., J 880, 13.
Schneider, J. ^rnkt. Cham., 1880, [2], 22, 131.
Pfejfer, An-iialr-.ii, 1.881, 209, 174. (Electrochemical method.)
Bongartz, iV/-., 1883 ; 16, 1942.
Popper, A'ft'rtnlF.n, 1886, 233, 153. (Elcctrochemjc-al method.)
G. C. Friend and E. F. Smith, J. A-mf-r. Chi-tii. Sor., 1901, 23. 502.
Willard and McAlpmc, ibid., .1921, 43, 797.
Muzali'ar, il,i<L, 1923, 45, 2009.
Kuop, Zt'itwh.. niinl. Che,//.., l!)23, 63, 181.
Hoiiigschnud, Zmtl and Lmhard, Zeit..wh. anrtry. CIio/i.. 1924, 136, 257.
ANTIMOXY AND ITS ALLOYS. 35
(d) Analysis of Antimony Triiodide. The analysis was carried out
in the same way as those of the tribromide and trichloride. The ratio
SbI 3 : 3AgI= 71-060 : 100 gave Sb - 119-786.
In the years 1880 and 1881 Cooke carried out his final determina-
tions using antimony tribromide. The material was repeatedly distilled
from metallic antimony, recrystallised several times from carbon
disulphide, subjected to repeated fractional distillation, and finally
twice sublimed in a current of carbon dioxide. It is probable that Cooke
would have obtained better results had his process of purification been
less prolonged. Working without modern refinements in the handling
of highly hygroscopic materials, the introduction of a trace of moisture
was inevitable ; thus the carbon dioxide, though described as absolutely
dry, was only subjected to the action of calcium chloride and sulphuric
acid. It is clear, therefore, that the resublimed product was much more
likely to contain hydrogen bromide than antimony oxybromide, the
impurity which Cooke feared. Willard and McAlpine, 1 as a result of a
critical study of Cooke's papers, consider that his material may have
contained as much as 1 per cent, of hydrogen bromide.
Turning now to the values given in the table (p. 34), it will be
observed that, with certain early exceptions, the values recorded fall
into two groups, those approximating to 120 and 122 respectively. On
the basis of the work of Kessler, Dexter and Dumas the value 122 was
adopted, although Schneider's results pointed to the lower value. After
the laborious investigation carried out by Cooke, which gave results of
such striking concordance, the number 120 was immediately adopted.
The electrochemical studies of Pfeifer and Popper indicated the higher
value once more, but so great was the prejudice in favour of Cooke's
work that no alteration was made ; moreover the electrochemical work
was adversely criticised by Cohen, Collins and Strengers, 2 on the
ground that the method did not give constant results. The work of
Friend and Smith, however, indicated that Cooke's results were some-
what too low, so that after 1902 the number 120-2 was adopted; an
unjustifiable compromise which was obviously unsatisfactory. The
controversy continued ; certain workers on antimony appeared to find
the value. J20-2 satisfactory/' Others, however, obtained results point-
ing to the higher value, 4 and expressed the opinion that the older
value, 122, was the more correct.
The; insecurity of the basis for the atomic weight led Willard and
MeAlpinc in 1921 to rcinvesfigate the whole question. 5 They prepared
pure antimony fribroinidc with careful exclusion of moisture. In an
all-glass apparatus, three different preparations of antimony were
combined with bromine, the product twice distilled at a pressure of 5 to
"10 mm., then distilled a. third time at less than 1 mm. into a scries
of small bulbs which were sealed oft' from each other as individual
< llmann,
I if/ions,
a dwell,
30 AXTDIONY AND BISMUTH.
samples. From the time the pure dry materials were placed in the
apparatus until the bulbs were broken under tartaric acid solution, only
inert gases came into contact with the preparation. The resulting
product was analysed for bromine in two ways : first, volumetrically,
by finding the amount of silver, dissolved in nitric acid, equivalent to
the sample, using a nephelometric end point ; second, gravimetrically,
by adding excess of silver nitrate, then filtering out and weighing the
silver bromide. The precautions taken and corrections applied included
all those which had been described within recent years on similar work.
In eight of the best volumetric analyses, a total of 35-69757 grams of
antimony bromide formed 55-63121 grams of silver bromide, from which
the atomic weight of antimony is 121-768. By taking into consideration
the three slightly less satisfactory volumetric analyses, and eight gravi-
metric analyses, Willard and McAlpine gave the mean value 121-773.
The former value, however, is the more trustworthy and has therefore
been included in the table.
Knop l obtained an appreciably higher value. He treated pure
antimony with nitric acid and converted the product into the tetroxide
by ignition at 850 to 900 C., at which temperature the pentoxide is
fully reduced to the tetroxide, but the latter is not further reduced.
The purity of the product was established by the iodine-thiosulphatc
method. The results gave a mean value Sb = 122-06, or 121-96 when
reduced to vacuum.*
Honigschmid, Zintl and Linhard 2 hydrolysed chloroantimonic acid,
HSbCl 6 , 4-5H 2 O (prepared from antimony pentasulphide) and reduced
the resulting antimonic acid in hydrogen at 500 C. The metal was
converted into the chloride or bromide by heating in a current of the
halogen, and the halides fractionally distilled, first in pure nitrogen and
then in a vacuum. The silver equivalent of each halidc was determined
by gravimetric titration and weighing the silver halide formed. The
mean of thirty- two very concordant results gave Sb =121-76.
Weatherill 3 applied Willard and Me Alpine's method to the trichloride.
Kahlbaum's purest antimony was twice fused in hydrogen, combined
with pure chlorine, and the product repeatedly distilled in an evacuated
glass apparatus, considerable head and tail fractions being rejected in
each distillation. The mean of 8 analyses gave the ratio SbCl 3 : 3Ag
as 0-704864, from which the atomic weight of antimony is 121-748.
This is slightly lower than the values obtained by Willard and McAlpinc,
and by Honigschmid, but agrees remarkably well with that of Krishna s-
wami (see below).
The discovery of non-radioactive isotopes of certain elements lias
taught that elements from different localities may conceivably possess
their constituent isotopes in different proportions, so that their atomic
weights may vary. A review of the earlier work on the atomic weight
of antimony led Muzaffar 4 to inquire whether or not such might be
the case with this clement. Stibnite was obtained from Peru, Bolivia,,
Borneo and JTuno-ary. After purifying nil samples by the same method,
K.710p,
Knop
3 \Veathcr
. fitted. Ch(-ni.< 1923, 63, 181.
s the mean values of 122-04 and 121-1)4 respectively. The above vali,
are calculated from the ratio ^iven in the table, which ^ives the total weights ot antimony
an died in the .six experiments.
mid, Zintl and Linhard, ZcAtscJi. (inortj. Che.ni.., 1924, 136, 2.V
11, /. Amer. Chem. ;S'oc.,'l924, 46, 2437.
Muzaffar, J. Amw. Chcm. Soc., 1923, 45, 2009.
ANTIMONY AND ITS ALLOYS. 37
the antimony was converted into trichloride and the ratio between
antimony trichloride and potassium bromate determined by titration :
3SbCl 3 + KBr0 3 +6HCl = 3SbCl 3 +KBr -f 3H 2 O
TJie results were as follows :
. Source of Stibnite.
Ratio 3Sb : KBr0 3 .
: No. of
Experiments.
Atomic Weight
of Antimony. ;
Hungary
2-17592
7
121-138
Borneo .
2-1836
7
121-565
Peru .
2-1862
7
121-710
Bolivia .
2-1986
11
122-400
Excellent concordance was obtained in the first set of results using
Hungarian material, and the low value for the atomic weight is remark-
able.
More recently 1 specimens of stibnite have been obtained from the
same sources as those used by Muzaffar. The metal was extracted, and
the densities compared with that of a specimen of Kahlbaum's antimony.
In addition, solutions were titrated with solutions of potassium bromate
and the ratio KBr0 3 /3Sb was determined. It was found that the
densities of the specimens were all within 0-1 per cent, of each other ;
and that the ratios KBr0 3 /3Sb agreed to 0-05 per cent. The evidence
of variation in the atomic weight of antimony from different sources does
not therefore appear to have been confirmed.
Krishnaswami 2 directed attention to certain disadvantages occur-
ring in practice when Muzaffar's method is adopted, and gave the
results of determining the atomic weight of antimony from four ores of
Indian and Burmese origin, using Willard and McAlpine's method in
its entirety. His results were as follows :
! Source of Material. Katio SbBr 3 : 3AgBr. v Xo : of ' Atomic Weight
J e Experiments. of Antimony.
i Kahlbaum's
Sb 2 O 3 .
0-641664
6 121-758
Mysore
stibnite
0-641647
4 121-748
Mysore
i cervantite .
0-641647
3
121-748
Am hers t 1
i stibnite
0-641652
5
121-751
Shan States
; stibnite
0-64159
! 3
121-716
A close agreement between the values from the Mysore stibnite and
cervantite was of course to be expected since the latter is an alteration
product of the former. The results do not indicate any appreciable
difference between the samples.
1 XlcAlpine, J. Amer. Chem. Soc., 1929, 51, 1745.
2 Krishnaswami, J. Chem. Soc., 1927, p. 253-i.
38 AXTIMOXY AND BISMI7TH.
The International Committee on Atomic Weights for 1936 has
adopted the value
Sb-121-76
The Council of the Chemical Society had, in 1019, .recommended this
value and it has been retained until the present time (1936).
Isotopes. Two isotopes of antimony have been discovered, with
atomic masses 121 and 123. The ratio Sb 121 : Sb 123 is provisionally given
as 100:78-5, thus indicating a mean mass of 121-88 and an isotopic
moment of 0-96. Though the packing fraction has not been determined,
it is assumed to lie between those of tin and xenon, and on this assump-
tion the calculated atomic weight is 121-79, which compares very
favourably with the value obtained by chemical methods. 1 Owing to
the unsuitability of antimony tri hydride for the determination of the
isotopic constitution, antimony methyl was employed in the more
recent work. A nuclear moment 2 of 5/2 has been assigned to Sb 121 ,
and one of 7/2 to Sb 123 . The atomic radius 3 calculated from the
structure of antimony tribromide is 1-25 A., and from antimony tri-
chloride, 1-21 A. An inner potential 4 of 12 volts has been deduced
from the refraction due to the reflection of high-speed electrons from
cleavage faces of antimony.
From the fluorescence of antimony excited by several mercury lines,
the value 2-21 A. has been obtained for the nuclear separation in di-
atomic molecules, and the value 489 x 10~ 40 gram-cm. 2 for the moment
of inertia. 5
Alloys of Antimony.
Antimony enters into the composition of a large number of com-
mercial alloys, including antimonial lead (lead containing up to 4 per
cent, of antimony) which is used for the framework of accumulator
plates, lead shot (in which antimony replaces the more usual alloying
element arsenic), lead anodes for chromium plating and other purposes,
type metal (consisting of alloys of lead, antimony, tin and sometimes
copper), Britannia metal and pewter (alloys of tin, antimony, lead and
sometimes copper and bismuth), and antifriction metals, such as
Babbitt metal (a wide range of alloys, a number of which contain tin,
lead, antimony and copper). 6 In general, antimony acts as a hardening
metal, and excess is liable to induce brittleness. It has been stated that
alloys of antimony with iron and certain other metals are resistant to
acid. 7
A number of alloy systems with antimony as one of the components
has been examined thermally and microscopically, by means of X-ravs,
1 Aston, Prac. 'Roy. Soc., 1931, 132 A, 492; Phil. Ma<j., 1923, [6], 45, 943; Nature,
1922,iio,732.
2 Badami, Nature, 1932, 130, (597; Zeilsch. Phytik, 1932, 79, 206. See also Tolansky,
Proc. Roy. Soc., 1934, 146 A, 182; Crawford and Bateson, Canctd. J. Research, J 934, 10,
693.
3 Bergmann and Engcl, J. Physical Chwti., 1931, 138, 247. See also Goldselnmdt,
Zeilsch. phijsikal. Chem.^lSZS, 133, 397.
- 1 Darbyshire, Phil. May., 1933, 16, 761.
5 Gcnarcl, Phys. Review, 1933, [2], 44, 46S. See also Sen, Zettsch. awry. Cke/ti., 1933,
212, 410.
G Roekaert, Acie-rs speciaux, 1929, 4, 470.
7 Prisoner, French Patent, 1931, 725448.
ANTIMONY AXD ITS ALLOYS. 39
and by the correlation of physical properties with composition. The
bibliographies which accompany these brief accounts deal mainly with
the physico-chemical constitution of the alloys; references to method
of manufacture, treatment, working or uses of the alloys have not, in
general, been included. 1
Antimony-Sodium Alloys. 2 -Two compounds arc formed,
Xa 3 Sb (M.pt. 823 C.) and XaSb (AI.pt. 503 C.), which enter into the
formation of three eutectics, at 0-5 per cent, antimony (AI.pt. 95 C.),
80 per cent, antimony (AI.pt. 430 C.), and 90-6 per cent, antimony
(M.pt. 404 C.). There is no range of solid solution. The e.m.fs. of
these alloys have also been investigated. 3 Substances of the composi-
tion Xa 3 Sb 7 , Xa 3 Sb 7 .XH 3 and Xa 3 Sb 7 .6XH 3 have been obtained by
extracting an alloy of sodium and antimony with liquid ammonia. 4
Antimony -Potassium Alloys. 5 Two compounds are formed,
K 3 Sb (Al.pt. 812 C.) and KSb (Al.pt. 605 C.), which enter into the
formation of three eutectics inciting at 63 C., 400 C. and 485 C,
respectively.
Antimony -Copper Alloys. 6 Two definite compounds are formed :
Cu 5 Sb 2 (Al.pt. 680 C.) and Cu 2 Sb (decomposing at 580 C.); it is
possible that a third compound, Cu 3 Sb, may exist below 430 C. There
are two eutectics, namely at 23 per cent, copper (AI.pt. 535 C.) and
72 per cent, copper (Al.pt. 634 C.). Copper forms a solid solution in
antimony up to 1-2 per cent., and antimony dissolves in copper up to
7 per cent. Transformations in the solid state occur at 430 C. (when
the compound Cu 5 Sb 2 undergoes decomposition), and in copper-rich
alloys at 450 C. Other physical properties that have been examined
are the heats of mixing, 7 which at 1,200 C. reach a maximum of +903
gram-calories at 57-4 atomic per cent, copper, and variations in e.m.f. 8
X-ray examinations of this system have been carried out. 9
Antimony- Silver Alloys. 10 One compound, Ag 3 Sb, is formed,
decomposing at 560 C., and one eutectic containing 55 per cent, silver
(Al.pt. 482 C.). The solid solubility of antimony in silver is 6 per cent. ;
silver appears to be insoluble in antimony in the solid state. The heat
of mixing (at 1,050 C.) rises to a maximum of -f 1,192 gram-calories at
71-6 atomic per cent, silver. 11
1 Constitutional diagrams of many of the systems cited will be found in International
Critical TabUs, 1927, 2^4.01-427.
2 Mathewson, Zcittc/t. anorg. Chem., 1906, 50, 171; Peck, J. A-ni<-r. Chan. &oc., J91S,
40, 335.
3 Ivremann and Pileiderer, Zc.-itsch. MelallJcu,/uh, 1921., 13, 19.
1 Zintl and Harder, Zeitxch. phy.-iikal. Chem., 1932, B 16, 183, 206.
5 Parrava.no, Gazzttta, 1915, 45, i, 485.
6 Carpenter, Z, clinch. Me.taU/cunde,, 1913, 4, 300; Heycoek and Xeville, Phil. Trans.,
1897, A 189, 25; Reimarm, Zeitsch. Metallkunde, 1920, 12, 321; Parravano andViviani,
Atli R. Accad. JAn.cti, 1910, [5], 19, i, ]97, 243, 343, 835; ii, 69; Humc-Kothory, IMabbott
and Channel Evans, Phil. Trans., 1 ( J3-J, 233 A, 1; Arehbutt and Prythereh, J. Jnxt. Met.,
1931,45,265.
7 Kawakami, ticicncfi 'Reports Tohuku Imp. Univ., 1930, 19, 521.
8 .Pace, Gazz. di'-.m. itaL, 1930, 60, 811.
u Howells and Morris Jones, Phil. Mag., 1930, [7], 9, 993; Wcstgren, Hagg and
Eriksson, Zeitach. phyaikal. Che/u., 1929, 64, 453; Morris Jones and Evans, Phil. Mag.,
1927, [7], 4, 1302.
10 Petrenko, Zuilscli. anorg. Chem., 1906, 50, 133; Kremann and Bayer, Mon.ntsh.,
1926, 46, 649. For X-ray examination, see Broderiek and Ehret, /. Phy*. Chtm., 1931,
35, 2627.
"'' '
40 ANTIMONY AND BISMUTH.
Antimony-Gold Alloys. 1 One compound, AuSb 2 , 2 is formed,
Avhich exists in three modifications with transition points at 355-2 C.
and 405 C. ; it probably decomposes at 460 C. There is a maximum
on the Hquidus curve at 55 per cent, gold (492 C.) and two cutectics
occur, namely at 46 per cent, gold (M.pt. 480 C.) and at 75 per cent,
gold (M.pt. 370 C.). There appears to be no range of solid solution.
Electrical conductivity curves agree with the results of thermal
analysis. 3
Antimony-Magnesium Alloys. 4 One compound, Mg 3 Sb 2 (M.pt.
1,228 C.) is known, which forms two eutectics, at 86 atomic per cent,
antimony (M.pt. 579 C.) and 10 atomic per cent, antimony (M.pt.
629 D C.)." The compound Mg 3 Sb 2 undergoes a transformation at 930 C.
and enters into solid solution with magnesium. The temperature of the
transformation falls slightly throughout the range of solid solubility.
Antimony -Calcium Alloys. 5 Only the antimony-rich alloys
appear to have been studied. There is a eutectic at 8 per cent, calcium
(M.pt. 585 C.).
Antimony -Zinc Alloys. 6 Two compounds are formed, Zn 3 Sb 2
(M.pt. 568 C.) and ZnSb (decomposing at 534 C.), forming two eutectics
at 1-7 per cent, antimony (M.pt. 412 C.) and at 80 per cent, antimony
(M.pt. 505 C.). At room temperature the compound Zn 3 Sb 2 de-
composes into metallic zinc and the compound ZnSb. A discontinuity
in the curve for the magnetic susceptibility 7 indicates the formation of
the compound ZnSb, which has also been examined by X-rays.
Antimony -Cadmium Alloys. 8 It is probable that two com-
pounds are formed, 9 Cd 3 Sb 2 (decomposing at 410 C.) and CdSb (M.pt.
455 C.), although the existence of the former has been queried. 10 Three
other compounds have been indicated 11 for which the following formulae
have been proposed : Cd 5 Sb 3 , Cd 4 Sb 5 and Cd 3 Sb s . There arc two
eutectics, at 40 per cent, cadmium (M.pt. 445 C.) and 93 per cent,
cadmium (M.pt. 290 C.). The magnetic susceptibility has been
studied, 12 while the heat of mixture (at 800 C.) shows a maximum of
-829 gram-calorics at 4-6-7 atomic per cent, antimony.
1 Vogel, Zeitsch. anorg. Chum., 1006, 50, 145; Grigoriev, Ann. Inst. Platine, 1929, 7, 32.
For X-rav examination, sec Xiall, Almin and Westgren, Zeitsch. physikal. Che.ru., 1931,
Bi 4 , 81."
~ Bottema and Jaeger, Proc. Acad. Sci. Amsterdam, 1932, 35, 916, 929; Eec. Trav.
chim., 1933, 52, 89.
3 Grigoricv, Zeitsch. an.org. Chem., 1932, 209, 2S9.
4 Grube and Bornhak, Zeitsch. ElektrocJiein., 1934, 40, 140; Leitgebel, Zeitsch. anon/.
Cham.., 1931, 202, 305; Grube, ibid., 1906, 49, 72.
5 Donski, Zeitsch. anorg. Chem., 1908, 57, 185.
6 Zhcmclmzhnui, Zeitsch. anory. Chem., 1913, 4, 228; Krcmann, Ortner and Markl,
Monatsh., 1924, 44, 401; Sauenvald, Zeitsch. Metallkundc, 1922, 14, 457. For X-ray
examination, see Halla, Xowotny and Tompa, Zeitsch. anorg. Chem., 1933, 214, ]96.
7 Mcara, Physic*, } 932, 2, 33.
8 Kurnakov and Konslantmov, Zeitsch. a.vorg. Chem., 1908, 58, 1; J. Puss. Phys.
Chem. Soc., 1908, 40, 227; ivremann. and Groachl-Pammer, Intern. Zeitsch,. J\I<dallo<j rapine,
J920, 12, 241; Fischer and Pflcidercr, Ges. Abhandi. Kennt. Kohle, 1919, 4, 440; Kucken
and Gehlofl, JJer. de.ut. physi.kal. Ges., 1912, 14, 169.
<J Halla, Xowotny and Tompa, Zeitsch. anorg. Chem., 1933, 214, 196; Halla and
Adler, Zeitsch. anorg. Chem., 1929, 185, 184.
10 Chikashige and Yamamoto, "Anniversary Volume,"" Kyoto Imp. Univ., 1930, 195;
Abel, Redlich and Adler, Zeitsch. anorg. Chem., 1928, 174, 257; Abel, Adler, Halla and
Redlich, Zeitsch. anorg. Chem., 1932, 205, 398.
11 Volfson and Ro.shdcstvenski, /. Exp. Theor. Phys., U.S.S.R., 1933, 3, 447.
12 Mcara, loc. cit.
ANTIMONY AND ITS ALLOYS. 41
Antimony -Aluminium Alloys. 1 It is difficult to obtain equi-
librium with these alloys. The solid solubility of antimony in
aluminium is less than 0-10 per cent, at 645 C. ; a euteetic is formed at
1-1 per cent, antimony (657 C.) and a maximum on the liquidus curve
at 1,080 C. corresponds to the compound AlSb. The liquidus curve
shows another maximum at 32 per cent, antimony (984 C.) and a
minimum at 35 per cent, antimony (942 C.) There appear to be two
cutectics. The compound AlSb decomposes in moist air, aluminium
hydroxide being formed.
Antimony-Thallium Alloys. 2 One compound is formed, Tl 3 Sb
(decomposing at 187 C.), which gives solid solutions with thallium but
not with antimony. A euteetic is formed at 19 per cent, antimony
(M.pt. 196 C.), while the thallium-rich alloys undergo a transformation
(probably connected with the allotropy of thallium) at 226 C. Another
compound, Tl 7 Sb 2 . has also been reported. 3
Antimony -Silicon Alloys. 4 Antimony and silicon show only slight
solid solubility ; the euteetic melts at 630 C. No compounds are formed.
Antimony -Tin Alloys. 5 This system is complex, a number of
solid solutions being formed. There are two compounds, SnSb (decom-
posing at 427 C.) and Sn 3 Sb 2 (decomposing at 319 C.). A trans-
formation occurs in the range 30 to 70 per cent, antimony, which is
connected with a polymorphic change in the /3-solid solution. An X-ray
examination of these alloys has been made, and it is suggested that the
compound SnSb has the structure of a simple cube of the KC1 type
a very unusual structure for an intermctallic compound. 6 The unit cell
contains 4 molecules, with =6-120A. The more usual structure of a
body-centred cube, with a =^6-13 A. has, however, also been proposed for
this compound, 7 and further, as the result of a more recent investigation,
the structure has been described as of the KC1 type, but deformed. 8
This compound is also unusual in dissolving both antimony and tin.
The existence of the compound SnSb is also indicated on the curve of
magnetic susceptibility. 9
Antimony-Lead Alloys. 10 These metals form a cutcctifcrous
1 Veszelka, Mitt. bc.ry.-Jiutl MIDI dim. ALl. 'UiKjar. Jfoc/tschulc J>tr(j.-l"oiisw. Sopron, 1931,
3, 193; Chc.m. Ze.nir., 1932, ], 2230; .Bonarctti, "Melalli Uggiwi^ 1931, 29; Dix, Keller
and Wjlloy, Ain.cr. Just. Mmmy tiny., 1930, Tech. Pub. Ko. 356; Campbell and Matthews,
,/. Amer. CfiMn. /S'oc., 1902, 24, 253; Kreniann and Dcllachcr, jMonalsh., 1926, 46, 547;
ttauerwald, loc. c,it..; Guertler and Bergmann, Zc.itxck. Melallku-mh, 1933, 25, 81, 111.
'- YVinogorov and Petrenko, Zfttxch. cmory. Chcin., 192(5, 150, 258: Kremann and
Lobinirer, Intern. Zc.it wh. MctaUoyraphic, 1920, 12, 240; Chun. Zenir., 1921, i, 123;
Bolder, Chc.mi.k l\,lld, 1917, 15, 119; Chetn. Zentr., 1918, i, 1000; Williams, Zcitxch.
anartj. Chr.ni., 1907, 55, I.
3 '.Morrall and Western, tirr.nxlc XMH. TidxJcr., 193-1, 46, 153.
4 Jet-K; and Cchrrt, -/. Ckc-tn. Phyticx, 1933, I, 753; Williams, loc. c.iL
5 Iwasi, Aoki and Osawa, tin me.?. Rc/porlx Tohoku J-t/rp. [hi it:., 1931, [1], 20, 353;
Kiiizoku-tio-Kc.nkyu. (.1. for Study of Metals), 1930, 7, 147; Gticrtlcr, " MetaUoympliie"
1910; Williams, loc. ell.; Leroux, C rmi.pt. . rc.-nd., 1913, 156, 1764; Konstantinov and
>Smirnov, J. RUM. /%,.. Chc.ui. AV^., 191K 43, 1201.
(i Morris Jones and Howen, Xuture, 1930, 126, 846; 'Phil. Mag., 1931, 12, 441; van
Klooster and Debarher, M vials and Alloys, 1933, 4, 23; Twasi, Aoki and Osawa, loc.. at.
7 von Sehwarx and Suinina, Zcilwh. Mr-tallhihdc., 1933, 25, 95.
8 Hagg and Hybinctte, Phil. Mag., 1935, [71, 20, 913.
9 Meara, /V/y/.s-Ir.s% 1932, 2, 33.
10 Dean, .Hudson and Fooler, I-ndust.rtul and tfnyineeiiny Ch+.in.ixlry, 1925, 17, 12-10;
1'isc.lier, Z(:il,#ch. tcc.h. Physik., 1925, 6, 14.0; Gontcrmann, Zcdtscli. anory. Chew., 1907,
55, 419; .Dean, J. Amn. Chem. Soc., 1923, 45, 1683; Muzaifar, Tram. Faraday >S'oc.,
1923, 19, 56; Leroux, loc. cit.; Stephens, Phil. Mag., 1930, [7], 9, 547.
42 ANTIMONY AND BISMUTH.
series of alloys with a eutectic at 87 per cent, lead (M.pt. 247 C.). A
more recent examination of these alloys after very slow cooling suggests
that the eutectic contains 11-4 to 11-5 per cent, antimony. 1 It is
suggested that a compound Pb 2 Sb is formed which is soluble in liquid
antimony, and that it forms a solid solution in monatomic molecules of
lead at all temperatures between 25 C. and the melting point of pure
lead. 2 A maximum is found on the boiling point curve. 3 The hardness 4
and specific heats 5 have been determined, the specific heat between G
and 100 C. being given by the expression
s =0-04965 -0-0001884>
where p is the percentage of lead in the alloy. These alloys have been
examined by X-rays, 6 and from the results it is deduced that the solid
solubility of antimony in lead cannot be more than 0-5 per cent. From
electrical conductivity experiments 7 it is concluded, however, that at
249 C. the solid solubility of lead in antimony is 5-8 atomic per cent.,
and that of antimony in lead is 1-5 atomic per cent.
Antimony -Arsenic Alloys. 8 These elements form a continuous
series of solid solutions up to 40 per cent, arsenic. There is a minimum
on the liquidus curve at 17-5 per cent, arsenic (612 C.).
Antimony-Bismuth Alloys. 9 These metals form a continuous
series of solid solutions, the liquidus curve lying wholly between the
melting points of the two metals, and the solidus being practically
horizontal between and 60 per cent, antimony. Some evidence for the
existence of Bi 3 molecules has been obtained, and the anomalous form
of the solidus curve has been ascribed to this. 10 The hardness 11 has
been determined. The boiling point curve shows a maximum. 12 These
alloys have been examined by X-rays, homogeneity being obtained by
prolonged annealing at 280 C. The lattice edge of the rhombohedral
crystals varies almost linearly with composition. 13
Antimony -Chromium Alloys. 14 Two compounds are formed,
CrSb (M.pt. 1,110 C.) and CrSb 2 (decomposing at 675 C.), and two
eutectics, at 2 per cent, chromium (M.pt. 620 C.) and 38 per cent,
chromium (M.pt. 1,100 C.). Antimony is soluble in chromium to the
extent of 12 per cent.
Antimony -Selenium Alloys. 15 One compound, Se 3 Sb 2 (M.pt.
1 Quadrat and Jiristc, Chim. ct !n.d., 1934, Special 'Number (April], 485.
2 JcfFciy, Trans. Faraday Soc., 1032, 28, ,567; sec, however, Chu-Phay Yap, Amcr.
Jnst. Min. Met. Eng., Inst. 'Metals Division, 1931.
3 Leitgebel, Zettsch. anorg. Chem., 1931, 202, 305.
1 Saposhnikov and Kanewsky, J. Russ. PJiys. Chem. Soc., 1907, 39, 901.
5 Durrer, Physikal. Zeitsch., 1918, 19, 86.
a Solomon and Morris Jones, Phil. Mag., 1930, [71, 10, 470; Obinata, Metallwirtxchaft,
1933, 12, 101.
7 Le Blanc and Schopcl, Zeitsch. tilektroch&m., 1933, 39, 695.
8 Parravano and de Cesans, Intern.. Zeitsch. Metalloyraphie, 1912, 2, 70.
9 Cook, J. Insl. Metals, 1922, 28, 421; Otani, Sci. Rep. Tohoku Imp. Univ., 1925, 13,
293; Parravano and Viviani, Atli R. Accad. Lincei, 1910, [5], 19, i, 835; Ehret and
Abramson, J. Amer. Chem. Soc., 1934, 56, 385.
Chu-Phay Yap, loc. cit.
1 Saposhnikov, J. Russ. Pliys. Chem. Sue., 1908, 40, 665.
- Leitgebel, loc. cit.
3 Bowen and Morris Jones, Phil. Mag., 1932, [7], 13, 1029.
1 Williams, loc. cit.
Chikashige and Fujiia, Mem. Coll. Sci. Kyoto Imp. Univ., 1917, 2, 233; 'Parravano,
Gazzdla, 19.13, 43, i, 210.
ANTIMONY AND ITS ALLOYS. 43
570 C.) is formed, and t\vo eutectics, at 47 per cent, selenium (M.pt.
493 C.) and at 99-7 per cent, selenium (M.pt. 210 C,).
Antimony -Tellurium Alloys. 1 These alloys are described as
forming a series of " mixed crystals."
Antimony -Manganese Alloys. 2 Three compounds have been
described : MiiSb (M.pt. 809 C.), Mn 3 Sb 2 (decomposing at 872 C.) and
Mn 2 Sb (M.pt. 971 C.). Two eutectics are also formed, at 9-5 per cent,
manganese (M.pt. 570 C.) and at 55 per cent, manganese (922 C.).
Ranges of solid solution exist between 32 to 41 and 45 to 50 per cent,
manganese. Some of the alloys show paramagnetism.
Antimony-Iron Alloys X Two compounds have been described,
Fe 3 Sb 2 (M.pt. 1015 C.) and FeSb 2 . There are two eutectics, at 50-5 per
cent, antimony (M.pt. 1,002 C.) and at 92-5 per cent, antimony (M.pt.
628 C.). The eutectic range in the iron-rich alloys extends from 5 to 52
per cent, antimony, and throughout this range there is a transformation
at 798 C. corresponding to the change from y-iron to a-iron. The
solid solubility of antimony in iron is reported to be 6-5 per cent. ; X-ray
examination, however, 4 suggests that the solid solubility of antimony in
iron is higher. There is also a range of solid solution between 55 and 65
per cent, antimony with a maximum on the liquidus curve at 63-5 per
cent, antimony (1,018 C.) corresponding with the compound Fe 5 Sb 4 . 5
It is possible that the so-called compound Fe 3 Sb 2 may not be a separate
chemical entity. The crystal structure of FeSb 2 is rhombic, with
a =3-189 A., Z>= 5-819 A. and 6'- 0-520 A. The unit cell contains two
molecules of FcSb 2 . It is claimed that some of these alloys are resistant
to acids, particularly to hydrochloric acid. 6
Antimony -Cobalt Alloys. 7 Two compounds are formed, CoSb
(M.pt. 1,190 C.) and CoSb 2 (decomposing at 900 C.), with eutectics at
39 per cent, antimony (M.pt. 1,090 C.) and at 99 per cent, antimony
(M.pt. 620 C.). Antimony is soluble in cobalt to the extent of 13 per
cent., and the alloys, within this range, arc magnetic, losing their
magnetism at temperatures varying from 1,132 C. for pure cobalt to
927 C. for the 13 per cent, antimony alloy.
Antimony -Nickel Alloys. 8 Two compounds are formed, NiSb
(M.pt. 1,160 C.) and Ni 5 Sb 2 (M.pt. 1,170 C.), with eutectics at 3-2 per
cent, nickel (M.pt. 612 C.),"at 47 per cent, nickel (M.pt. 1,072 C.) and
at 65 per cent, nickel (M.pt. 1,100 C.). There are three solid solutions :
a, between 33 and 40 per cent, nickel, jS, between 92 and 100 per cent,
nickel above 330 C., and y, between 67 and 100 per cent, nickel below
330 C. Magnetic alloys arc found in the range 92 -to 100 per cent,
nickel below 330 C., the magnetic transformation taking place at that
temperature. The compound Ni 5 Sb 2 is formed from another compound
Xi 4 Sb at 677 C. Within the range 55 to 67 per cent, nickel, both
compounds appear to be stable at ordinary temperatures.
1 Dreifuss, Zaihcfi. VMctror.htni., 1922, 28, 100, 224.
2 Murakami and Malta, Science LttporlH Toholc.u Imp. 'Univ., 1933, []], 22, 88; Williams,
lor-. ril. ; Wedekind, 7>V,r., 11)07, 40, 125!).
3 Kurnakov and Kon.stanlinov, Zvilwh. an.org. Ckem., 1908, 58, 1; Portevin, llevue de
Mclallurf/ie, 19.1 J, 8, 312.
4 -Ha^, Nova A eta Jtc.yiw Hoc. Xci. Upsalicnsix, 1929, [4], 7> ^o. 1.
5 Vogel and Dannolil, Arch, fiiwnhuttenw., 1934-5, 8, 39.
(i tfrischer, French. Patent, 1931, 725448.
7 Losscv, J. HUM. l*hys. Cham. Soc., 1911, 43, 375; Lewkonja, Zeitsch. anorg. Chem.,
1908, 59, 293.
8 Losscv, Ztitsch. anon/. Chem., 1906, 49, 58; Vigouroux, Compt. rend., 1908, 147, 976.
44 ANTIMONY AND BISMUTH.
Antimony -Palladium Alloys. 1 Several compounds of these
metals have been described, including PdSb<> (decomposing at 680 C.),
PdSb (M.pt. 799 C.), Pd 5 Sb 3J Pd 2 Sb (decomposing at 830 C.) and
Pd r> Sb (M.pt. 1,182 C.). The existence of the compound Pd 5 Sb 3 lias
not, however, been confirmed. Eutectics are formed at 9-7 per cent,
palladium (M.pt. 586 C.), at 55 per cent, palladium (M.pt. 734 C.) and
at 77 per cent, palladium (M.pt. 1.070 C.). Solid solutions are formed
of antimony in palladium (up to 15 per cent, antimony), and of antimony
in the compound Pd 3 Sb (between 68-5 and 72-5 per cent, palladium).
Antimony -Platinum Alloys. 2 A number of intermetallic com-
pounds of these two metals has been reported, but the existence of
one only, PtSb 2 (M.pt. 1,225 C.), has been definitely confirmed. It is
possible that two others exist, namely, Pt 4 Sb and PtSb, with transition
points at 670 C. and 660 C., respectively ; the compound Pt 5 Sb 2 pre-
viously reported has not been confirmed. Two cutectics are formed,
one containing- a trace of platinum (M.pt. 630 C.), and the other
containing 77 per cent, platinum (M.pt. 670 C.).
A number of ternary alloy systems containing- antimony have been
at least partially examined. Among them may be mentioned antimony-
copper-silver, 3 antimony-copper-cadmium, 4 antimony-copper-tin, 5 anti-
mony-copper-lead, 6 antimony-copper-bismuth, 7 antimony-copper-iron, 8
antimony-silver-cadmium, 9 antimony-silver-zinc, 10 a ntimony-zinc-lcad, 11
antimony-zinc-bismuth, 12 antimony-magnesium-aluminium, 13 and anti-
mony-tin-lead. 14 The last-mentioned system includes the industrial
alloys known as type-metals. 15
1 Sander, Zcitsch. anorg. Cheni,., 1912, 75, 97; Grigoriev, Ann. Inxl. Platinc, 1929, 7,
32; Zcitsch. anorg. C7iew.,'l932, 209, 308.
- Xemilov and Voronov, Ann. lust. Plalme, 1935, 12, 17; Friedrich and Leroux,
Meiallurgie, 1909, 6, 1.
a Guertler and Koscnthall, Zeil.sch. Metallkunde, 1932, 24, 7, 30.
4 Sleicher, Intern. Zd.lsch. MeJallograpfde, 1913, 3, 102.
5 Tasaki, Mtm. Coll. Sci. Kyoto Imp. Univ., 1929, 12 A, 227.
Schack, Zcitsch. anorg. Cliem., 1923, 132, 265.
7 Parravano and Viviani, Atti R. Accad. Lined, 1910, [5], 19, i, 835.
8 Vogel and Dannohl, Arch. Eifio/nhuLlniw., 1934-5, 8, 83.
<J Guertler and Roscnthall, lac. cit.
10 Guertler and llosenthall, loc. cit.
11 Tammann and Dahl, Z-zitw.h,. anortj. Chan.., 11)25, 144, I.
12 Kremaim, Langsbauer and .Ranch, Zeitsch. anorg. Chem., 1923, 127, 229.
13 Loofs-Rassow, Jrlauszeit V.A.W. Erjtwcrk A.G. Aluminium, 1931, 3, 20; Gnertler
and Bcrgmann, Zcitsch. Mctallkundc, 1933, 25, 81, 111.
11 Iwasi and Aoki, Kinzoku-no-Kcnkyu, 193 L, 8, 253; Aoki and Waki, Nar/cdL-n,
Inmtsii-kyaku .Kcn.yujo Chosa Hokoku, 1930, No. 21, 1, 37, 47.
15 See also Wehenhoff, "Report of Technical j)irc.ctor, U.ti. (h>rA. Printimj Office';
"Appendix to An.n. Report of Public Printer.,''' 1930, 105; HcrU-1 and Deinincr, Mrlall-
loirtsch'ij't, 193 L, 10, Xo. 7, 125; Weaver, J. InxL McLalx, 1935, 56, 209.
CHAPTER II.
COMPOUNDS OF ANTIMONY.
General. The compounds of antimony conform, in general, to the
types expected from the position of the metal in the Periodic Classifica-
tion. Antimony exhibits two valencies only, being tervalent in some
compounds and quinquevalent in others. Several substances, such as
the suboxide, in which antimony shows an apparent valency of less than
three, have been described ; but either these have been shown not to be
true compounds, or their constitutions have not been fully elucidated.
In accordance with its position in the Periodic Table, antimony shows
electropositive properties more definitely than arsenic, forming true salts
such as the halides and the sulphate ; the salts, however, undergo
hydrolysis, producing ultimately oxides or hydrated oxides. As might
be expected, hydrolysis does not take place so readily, or proceed so
completely, as with the compounds of arsenic, and several stable inter-
mediate products are formed.
Antimony, like arsenic, forms a hydride ; stibine, however, can only
be formed by the evolution method in acid solutions. It is more easily
decomposed by heat than arsinc.
Antimony halides are characteristic. There arc two fluorides, the
tri fluoride and the peiita fluoride, both of which are soluble in water and
hydrolysed only slowly. Antimony trilluoridc is not hydrolysed below
30 C. The corresponding chlorides hydrolysc more rapidly, the tri-
chloride yielding oxyc.hlorides, and ultimately (by hydrolysis at 150 C.)
trioxide, and the pentachloridc yielding hydrated antimony pcntoxide
(the so-called untimonic acid). Antimony pentachloridc dissociates on
heating. A third chloride, antimony tetrachlorido, appears to exist in
complex compounds only; it lias not been isolated. Antimony tri-
bromide is the only bromide thai: has as yet been isolated. The pcnta-
bromide is unknown, but compounds have been obtained that may
be regarded as derived from it. It is also possible that compounds
of a, hypothetical antimony tetra bromide may exist. Antimony tri-
bromide is very readily hydrolysed. The only iodide known is the
tri iodide, a well-defined salt which readily hydro! yses. Complex
compounds of quiiKjuevalcnt antimony which contain fluorine and
iodine have, however, been prepared.
The halides of antimony readily form double compounds, par-
heularlv wilh the halides of alkali and alkaline earth metals. In many
eases there is definite evidence of I he formation of complex anions of
which antimony forms a constituent. Thus compounds are derived
from antimony pentachloride which may be regarded as salts of ortho-,
pyro- and nieta-chloroantiinonic acids, II 3 SbCl 8 , H 2 SbCl 7 and HSbCl G .
Of these acids mcta-chloroantimonic acid has alone been isolated. From
45
46 ANTIMONY AND BISMUTH.
antimony tribromidc, salts of the type M 2 Sb 3 Br 1:L have been prepared,
in which M represents a monovaletit metal. From antimony penta-
bromide salts of the bromantimonic acids have been obtained, and nieta-
bromantimonic acid, HSbBr 6 .3H 2 O, has been isolated. Many other
complex compounds of antimony halides have been prepared, the con-
stitutions of which have not been fully elucidated. Most of them arc
decomposed by water, frequently with hydrolysis.
The chlorides and bromides of antimony are soluble in many organic
solvents, and in many cases complexes are formed. 1
Three oxides are known. Of these, antimony trioxide is amphoteric,
forming both antimony salts and antimonites ; its basic properties,
however, predominate. Antimony tetroxide is neutral or only faintly
acidic, and may best be considered as a salt, antimony antimonate,
SbSbO 4 . Antimony pentoxi.de is acidic, forming antimonates. It is
doubtful, however, if a true antirnonic acid has been isolated, aiitimony
resembling tin in this respect.
The heats of formation of the oxides are :
Antimony trioxide 163,000 calories
Antimony tetroxide 209,800
Antimony pentoxide 229,600 ,,
Of the compounds in which antimony is a constituent of the anion,
antimonites are known, principally in the form of meta-antimonites,
such as sodium meta-antimonite, XaSb0 2 . Ortho- and pyro-anti-
monitcs may exist, but the latter in particular are doubtful. The free
acids have not been isolated.
Mcta-hypoantimonic acid, H 2 Sb 2 5 , and its salts, derived from
Sb 2 O 4 , arc known. They may be regarded as mixed antimonites and
antimonates.
Ortho- and meta-antimonates are known, the majority of the salts
being cither acid ortho-antimonates of the type KH 2 SbO 4 , or mcta-
antimonates of the type KSbO 3 . It has also been suggested that the
formula for antinionic acid is HSb(OH) 6 .
It may also be noted that antimony pentoxide docs not liberate
chlorine from hydrochloric acid ; it will, however, liberate iodine from
hydriodie acid.
Three sulphides of antimony are known, corresponding to the three
oxides ; but the pcntasulphide is very dillicult to prepare in the pure
state, most of the preparations formerly regarded as antimony pcnta-
sulphide being mixtures, probably of antimony tetrasulpludc and
sulphur. The presence of tcrvalent antimony can usually be shown
in such preparations. Complex sulphur compounds, notably with the
halides, arc also known. They correspond roughly with the oxyhalidcs.
Of the other inorganic compounds of antimony, the sulphate and the
nitrate have been reported, but both arc more readily obtained as basic
salts. The existence of the latter is somewhat doubtful. It is interest-
ing to note, however, that antimony selrna.te is insoluble in water and is
not" decomposed by it.
Physiological Action of Antimony and its Compounds. In the
seventeenth and eighteenth centuries many medicinal preparations con-
taining antimony were in vogue, but the utility of most of these is
extremely doubtful. In the days of antiquity, antirnonial wine was
1 See this Series, Vol. XI, Part III.
COMPOUNDS OF ANTIMONY. 47
frequently employed as an emetic. The use of antimonial preparations
in medicine declined steadily, however, until comparatively recent years,
when their applicability to the treatment of certain tropical and allied
diseases w r as discovered.
In many ways the physiological action of antimony resembles that
of arsenic, but the former element differs principally in that it is absorbed
less easily and has a more irritating effect upon the alimentary canal.
The principal compound employed is tartar emetic, potassium
antimonyl tartrate, K(SbO)C 4 H 4 6 , but oxides and sulphides have also
been used. Many organic compounds have been prepared ; they have
a more powerful effect than tartar emetic, but they are more toxic and
are difficult to administer.
The action of antimony is principally that of an emetic ; it appears
to act by producing local irritation of the stomach, but its mode of
action is not confined to this, since vomiting is also produced by
intravenous or subcutaneous injections. It is, however, dangerous to
use, as the consequent severe depression may lead to collapse. Anti-
mony compounds also produce expectoration and perspiration.
When introduced into the stomach, antimony is slowly liberated
from the compound in the form of tervalent ion, and this, in the presence
of acids, produces the observed effects. When used in ointments
antimony produces an irritation of the skin ; this also is probably due
to liberation of tervalent antimony ion.
Stibine is very poisonous, but although its effects appear to resemble
those of arsine, its action is largely unknown.
Antimony trichloride has a caustic action, and combines with
albumen in the same way as compounds of the heavy metals.
In recent years antimony has been found to exert a remarkable
poisoning effect on trypanosomes and certain other protozoa. This
has led to its recommendation, in the form of injections, in the treat-
ment of certain tropical and allied diseases. 1
Antimonial poisoning has been diagnosed in many cases, instances
having been, found in connection with the enamel and printing trades. 2
Legislation lias been introduced in some countries regulating the use of
antimony in enamels, in which it acts as an opacifier. Criminal cases arc
also known, the effects of doses of antimony given at intervals frequently
being mistaken for symptoms of disease. Antimony is, as a, rule, found
only in traces in the stomach after fmtimouiat poisoning, the greater part
being expelled by vcxrmfekjgv - . ... _ . . ^ ...
It is thouo-ht that antimony, in. tbe qui'nqvieva'lcrtl* C'oiiditi.pn is com-
paratively non-poisonous. 3
ANTIMONY AND TlYnnooLN.
The only compound of antimony with hydrogen that is known with
certainty is the gaseous antimony trihydride, or stibine, SbII r A solid
1 (hishny, "vl Tc.rl- Hook' of l y fi(ir)D(ir.olo<jy and 'I'/i.crfrpc/Htic.x'' (London, .11)28, 9th Ld.),
p. (>7(>; Dixon, " .-I .Wuii'nal of I'harniaccjlof}!/'' ( London), 11)29, 7th Ivl., p. !>83; Uhlenlmth,
Klin. Wochxchr., I!W, 10, l' I ,">:*, 1201; Uidenhuih and SeilYert, Zdilr. Halcl. I'araxitcnk.,
1931, 122, f)I; Myers and Throne, ./. Lab. (,'li.n. Mcd., I IKK), 16, li.'W; Schmidt, Zdtwfi.
IUHJCW. ('fi-fni^ I {:'{(), 43, <)<>:{; van llork, I'-<irhi-n />,/., I9H2, 37, 17-11); 38, -'1,'), Dyson,
I 'h firm. ./., 1928, [! |, 67, f)i)(i.
- Oliver, />'///. M nL ./., ID.'i:}, I, JOJM; Mrt>i*trij of llntlik (London.}, \\YM, Memo.
171 (M(ul.).
:} BIyth and Hlyth, "yV;/,s-ort.s-, Thc.lr KfJ'c.dfi and DcM'wn" (.London, 1906, 4th Ed.),
p. (JOG; Leschko, Mtinc.h. mcd. Wo<:hwhr,, 1932, 79, 57, J40; Mclzcr, Glashutte, 1929,59, 865.
4B ANTIMONY AKD BISMUTH.
substance, described as di-antimony dihydride, Sb 2 H 2 , is stated to
have been obtained by various electrolytic methods and by the reduction
of antimony compounds by nascent hydrogen. 1 It is a brownish-black
substance, soluble in fairly concentrated nitric acid, but not in other
mineral acids ; it is insoluble in solutions of caustic alkalis. It is decom-
posed when heated in a current of hydrogen, and reacts vigorously with
fused potassium nitrate. 2 On the other hand, this substance may be
merely metallic antimony in a line state of division, containing a trace
of adsorbed hydrogen. 3 Some investigators doubt the existence of a
solid antimony hydride. 4
Antimony Trihydride, or Stibine, SbH 3 . This was first obtained
in 183T. 5 It maybe prepared by the action of nascent hydrogen upon
a solution of an antimony salt, the gas obtained being mixed with a large
excess of hydrogen. The reaction is most conveniently carried out by
the addition to a solution of an antimony salt of metallic zinc or alumin-
ium and a mineral acid. When iron is used no antimony trihydride
appears to be formed ; 7 with tin the yield is very small. If the reaction
is carried out in alkaline solution, no hydride is formed. 8 In this manner
antimony trihydride differs from the corresponding hydride of arsenic.
Antimony trihydride may also be prepared by the action of dilute
mineral acids upon alloys of antimony, convenient alloys being those of
antimony with zinc, 9 magnesium, 10 sodium amalgam, 11 potassium 12 and
calcium. If, however, the alloys of antimony and calcium are chemi-
cally pure, no hydride is obtained. 13 Alloys with strontium and barium
act less readily. Alloys of antimony and lead may be used with con-
centrated hydrochloric acid 14 or hydrobromic acid. 10 Alloys of antimony
with lithium, 10 aluminium, thallium and iron are unsuitable. The most
satisfactory results are obtained with alloys of zinc or magnesium. The
1 Weckes and Druce, Rev. Trav. chim., 192"), 44, 970; J. Chem. Soc., 1925, 127, 1069;
Bruce, Chem. Listy, 1925, 19, 150; Humped, J. pralct. Chem., 1865, 94, 398; \Viederhold,
Pogg. Annalcn, 1864, 122, 481; Marchand, J. prakt. Chcm., 1845, 34, ,38 J ; Ruliland,
Schweiggers ,/., 1815, 15, 418.
2 Weekcs and Druce, J. Chem. Soe,., 1925, 127, 1069.
3 Grant, J. Che.m. Soc,., 1928, 131, 1987; Sand, Grant and Lloyd, ibid., J927, 130, 393.
4 .Ueckleben and Scheiber, Zeitsch. anorq. Chtni., 1911, 70, 275; Slock and Guttmann,
Ber., 1904, 37, 885; Bollgcr, J. prakt.. Chem,., 185(5, 68, 374; Pogg. Annalcn, 1856, 97,
333; 1858, 104, 292.
5 Thompson, Phil, liny., 1837, 10, 353: J. prakt. Chan., 1837, n, 369; PfafT, Pogg.
Anualen, 1837, 42, 339.
B Scubert and Schmidt, Ahnalcn, 1892, 267, 237; Thick-, 'ibid., 1891, 265, 62;
Fluckiger, Arch. Pharni., 1889, [3], 27, 27; Bottler, Jahre^er., 1880, 1.279; Skey, Chc.m.
News, 1870, 34, 147; Koussin, ZeU^ch. anal. Chcm., 1867, 6, 100; J . Pharm. Chim., .1866,
[4], 3, 413; Bottger, J. prakt. Chem., 1856, 68, 374; FJeitmann, Anna/en, 1851, 77, 126;
Jacqudain, Compt. rend., 1843, 16, 30; Vogel, J. prakt. Chem., 1838, 13, 57; Simon,
Pofjfj. Aiinale.n, 1837, 42, 563; Thompson, loc. cit.; PfarY, lor., c/l.
1 Dupasquior, Compt. rend., 1842, 14, 514; Thii'le, loc. c-tt.
8 rioitmann, loc,. cit.; Gatehouse, Chew.. i\ew,-i, 1872, 27, 189; Mager, Zcil+ch. ana!.
Chcm., 1872, n, 82.
9 Stock and Dohl, Jlc.r., 1 901 , 34, 2339; J 902, 35, 2270 ; Bartcls, [-namjnral, J)i,w:rt.(il.ion,
Jl<\rlin, 1899; Bortliclot and Petit, A-nn.. Chim. 7%-s., 1889, |6], 18, 65; Olsxewski,
Monat.m.., 188(>, 7, 373: Lassaigne, J. Chim. 'mtdic.alc,^ Paris, 1840, | 2 ], 6, 638; 1841, [2|,
7, 440; Capitaino, J. Phnnn. Chrni., 1839, [2], 25, 516; Vogcl, loc.. c.it.; Thompson, for. cit.
1(1 Stock and l.)oht, foe. cit.; Hiunp(^rt, J. prnkl. Oicui., 1S65, 94, 39S.
11 van ByJort, Her., 1890, 23, 296S; Pok-ck and Thununc-1, /^/., ISS.'J, 16, 2144.
'- Sohic-1, Aitndlen, IS57, 104, 223.
1:1 ^loi.ssan, CompL rend., .1898, I2J, 58k
11 von der Planitz, tter., 1874, 7, 1664.
1G Harding, ibieL, 1881, 14, 2092.
]() Lcbcau, Conipt. rend., 1902, 134, 284.
COMPOUNDS OF ANTIMONY. 49
state of division of the alloy, and the temperature at which the reaction
takes place, greatly influence the yield, the best results being obtained
by allowing small portions of finely-divided alloy to fall gradually into
cold dilute, oxygen-free hydrochloric acid.
Attempts have been made to prepare antimony trihydride by
electrolytic processes. Xewbury found appreciable quantities of this
gas in the hydrogen liberated from an antimony cathode in acid solution. 1
Later investigations have been carried out using both acid and alkaline
solutions. No stibine is produced at low concentrations, while with
increasing concentrations the gas is decomposed almost as soon as it is
formed, particularly in alkaline solutions. The yield decreases with rise
of temperature. 2 The electrolytic formation of stibine has been studied
quantitatively, and equations have been adduced correlating the per-
centage yield of stibine at an antimony electrode in solutions of caustic
alkali with temperature, with hydrogen-ion concentration, and with the
voltage between a hydrogen electrode immersed in the experimental
solution and a saturated calomel electrode ; 3 similar equations for
solutions of sodium carbonate or sodium sulphate have also been
obtained. In acid solutions, however, stibine is formed only with
difficulty, the required current density being sufficiently high to cause
elevation of the temperature of the electrolyte to an inhibitive degree. 4
Alkaline solutions appear to be more favourable to stibine formation,
but it is necessary to remove rapidly any stibine produced by blowing a
current of hydrogen past the electrode ; failing this the stibine is at once
decomposed with precipitation of metallic antimony. It has also been
suggested that, although the electrolytic method of preparation is not
practical, the best conditions arc obtained by using a concentrated
aqueous solution of sodium acetate containing acetic acid, with an
antimony cathode. 5 The best yield is obtained with a current density
of 14 amps, per sq. dm., increase in current increasing the yield and
increase in voltage diminishing it.
The gas is most conveniently dried by passing over calcium chloride
or phosphorus pcntoxidc, then collecting over mercury ; other desiccat-
ing agents cause decomposition. 6 It may be separated from hydrogen,
by liquefaction.
Antimony trihydride is a colourless gas with a very characteristic
smell, described as faintly resembling that of hydrogen sulphide ; ' its
taste is extremely unpleasant, 8 and it is very poisonous. Its vapour
density at 15 C. and 754 mm. is 4-36 (air=l), 9 in agreement with the
formula S1)II :J . It shows appreciable deviation from the gas laws. 10
When cooled in liquid ethylcnc it solidifies to a snow-white mass, crystals
being formed in liquid air. 11 The solid melts at -88 C., forming a
colourless liquid which boils at -17 C. The density of the liquid is
I Xowbcrry, ,/. Cfian. Hoc,., J916, 109, 1361; Pancth, Ztitsch. Elektrockcm., 1020, 26,
<ir>3.
- Sand, \Vookc-s and WonvJI, J. C'/MM. Soc., 1923, 123, 45C.
3 WVokrs, AYr. Trur. cliim., 192-1, 43, (>49; 1925, 44, 201, 795.
l Sand, (Jranl, and Lloyd, J. Clton. tioc., 1027, 130, 389.
6 Hlasko and Maslowski, RuczniL'i Clui.ni., 1930, 10, 2-10.
(i St.oo.k and (Uittmann, />Vr., 190-1, 37, 885; JJrunn, /^>\, 1881), 22, 3205.
7 Stock and Dohl., tier., 1901, 34, 2339.
8 Jones, ,/. Chc.m. tfor.., 187(>, 29, (Ml.
y Slock and (uitlnianri, loc. ciL
10 Stock, Kchcandia and Voi^l, Her., 1908, 41, 130!).
II OLszcw.ski, Monalxh., 1886, 7, 373; Stock and Doht, tier., 1902, 35, 2270.
\7(\\ \'T V -('
50 AXTBIOXY AXD BISMUTH.
2-26 at -25 C C. and 2-34 at -50 C. 1 The gas is slightly soluble in
water (to the extent of 0-2 volume in. 1 volume of water) ; the solution
in water free from air is fairly stable. It is more soluble in alcohol (15
volumes in 1) and is very soluble in carbon disulphide (250 volumes in 1).
It is also fairly soluble in other organic solvents, but such solutions are
in general less stable than aqueous solutions. 2
In its physiological effects the gas strongly resembles arsenic tri-
hydride ; exposure to an atmosphere containing 1 per cent, is fatal to
mice in a few seconds. 3 Although opinions as to the physiological effect
of stibine are conflicting, especially among the earlier workers, it is prob-
able that its action upon human blood is similar to that of arsine, in that
the oxy haemoglobin is reduced. 4
Antimony trihydride is an endothermic compound ; the heat of
formation, determined by decomposing the gas into its elements by
means of the electric spark, is -33,980 gram-calories at constant
pressure, and -34,270 gram-calorics at constant volume. 5 From an
investigation of the electrolytic formation of stibine, the free energy of
the reaction 2Sb +3H 2 = 2SbH 3 has been calculated to be 62,100 gram-
calories for two moles of the gas in an acid solution, and 62,000 gram-
calorics for two moles in an alkaline solution. 6
Stibine is readily decomposed into its elements ; if the gas is pure
and dry, however, it remains fairly stable when kept in a thoroughly
clean glass vessel. Air and aerated water produce some decomposition,
but water free from air appears to be without action. 7 Decomposition
does not appear to be caused by light. 8 The velocity of the de-
composition depends considerably upon the nature of the surface in
contact with the gas, an etched surface, or one coated with an anti-
mony mirror, acting catalytically. The presence of hydrogen does not
affect the rate of decomposition ; oxygen poisons the antimony mirror
which, however, recovers its activity after some hours. It is probable
that the effect of oxygen is to oxidise the hydride, not the mirror itself.
The rate of decomposition is also affected by the nature of the surface
of the antimony mirror. 9
By the action of heat alone stibine is decomposed more readily than
arsine, rapid decomposition occurring at temperatures above i,5() C 1 .
If the reaction is carried out in a clean glass tube heated locally, an
antimony mirror is deposited on both sides of the heated part ; this
reaction is employed in the well-known Marsh's test. 10
Liquid stibine is partially decomposed even at low temperatures,
decomposition beginning between - 65 V. and - 56 C. Decomposition
takes place more rapidly in the liquid than in the gaseous state,
1 Stock and GuUniann, lor,, clt. - Stock and GuUmann, loc. cit.
3 Slock and Guttmann, loc,. cit.
4 Joly and do Xabais, Gwn-pL mid., 1800, no, 667; Stock, Guttmann and "Ber^oll,
Jlrr., 1904, 37, 803; Jones, J. Chf.m. Sor,., 187(5, 29, 641.
5 Stock and Wrcde, Bc.r., 1908, 41, 540.
G Sand, AVeekes and Worrell, ,/. Chcm. Soc. 9 1023, 123, 456. See also Berthelot and
Petit, Compt. rend., 1880, 108, 546.
7 Stock and Doht, tier., 1001, 34, 23-J3.
8 Lassai^ne, loc. cit.; Stock and Dohi ,, loc. cii.; Stock and Cut! mann, Inc.. cit.
y Stock, Kcheandia and Voi<xt, 7>V/-., J008, 41, 1300; Stock, Grmolka and Hcynemann,
ibid, 1007, 40, f>32; Stock and Bodcnstoin, ibid., 1007, 40, .170; Stock and Guttmann,'
ih'nL, 1004, 37, 001, .1057.
10 Brunn, 7>Y./\, 1880, 22, 3202; Stock and Doht, Her., 1001, 34, 2273, 23-13; van
Kijlorl, B<>r., 1800, 23, 2068; .Bottgor, J. ymkl. Chem'., .1838, 13, 57.
COMPOUNDS OF ANTIMONY. 51
but no evidence lias been obtained of the formation of a lower hydride
as one. of the products of decomposition. 1
Stibine is oxidised by air or oxygen even at low temperatures
according to the equation
4SbH 3 + 3O 2 = -1-Sb - 6II 2
Under ordinary conditions black antimony is deposited, but at -90 C.
the yellow modification is obtained. Liquid air does not cause oxida-
tion. When burned in air, antimony trioxidc is obtained instead of the
metal.
Stibinc is readily decomposed at the ordinary temperature by the
halogens, forming antimony halides and halogen acids. 2
Sulphur reacts slowly with a mixture of stibine and hydrogen heated
to 100 C., antimony trisulphidc and hydrogen sulphide being formed ;
the action is accelerated by light. 3 Pure stibine reacts readily with
finely divided sulphur. 4 Hydrogen sulphide appears to be without
action at the ordinary temperature. 5 When stibine is passed into
concentrated sulphuric acid a black precipitate is obtained which is
probably metallic antimony. 6
Neither nitrogen nor ammonia reacts with stibine. 7 The gas is
oxidised by oxides of nitrogen 8 and by nitric, acid. 9 Phosphorus
trichloride lias no action, while the pcntachloride reacts only slowly. 10
The iodides of phosphorus and the halides of antimony react with
decomposition of the gas. 11
Stibinc is oxidised when an electric spark is passed through a mixture
of the gas with carbon dioxide, according to the equation : 12
2S1)H 3 +3CO 2 = 2Sb +3BUO +3CO
Decomposition is also induced by the action of potassium hydroxide 13
and other alkali and alkaline earth hydroxides. 14
The action of stibine on a number of aqueous salt solutions has been
studied. 15 Stibinc resembles arsine in its action on an aqueous solution
of potassium pcnnano-anatc. 16 The precipitated manganese sesquioxide.
Mn, >().{, is more (locculent when stibine is used, and the solution contains
1 Slock and Gntt.rnann, lor.. cit..; Olszewski, loc. cit.
- St.ock and GtiU.mann, lor., cit.; Brunn, loc. cit.; llusson, Cornpl. rend., 1868, 67, 50;
Vo.uel, ,/. -jtrnlcf. (-linn., 1838, 13, 57; Buchner, Jicycrlnrhun. Pfamnacic. Xurnbrrg, 1838,
63, 183s.
" -I ones, loc. ell. ' Stock and Gtittmann, Inc. at.
r ' Slock a.nd Gnltmann, loc. ciL: see, however, Brunn, loc. cit.: Jones, foe. c.il.
( > Hinnpert, loc. o/./.: Barlels, Ln.niujnrtd l)>,w.rlrtttn)i, Ilulht, 1889; .Brunn, Inc.. c.ii.
For the action of other sulphur compounds, see Jones, loc. cit.: Seine], Auiinlcii. .1.857,
104, HX.
~ Simon, loc. n'f..; Ba.rl els, loc. at.; Stock a.nd Guttmann, loc. cit.
s Stock and Guttniann, loc. c/t. () Ansell, ./. 'Chtm. ;SV,r., 1852, 5, 210.
!l) Ma.hn, Jcmi'ixchc. Z<-it.'h., ISOO, 5, 162.
J1 Stock and (Jut trnann, loc. n't. ] - Stock and Guttniann, Inc.. at.
i:t Ua.i-1-els, Iint-ny. Diwildti.oii, Berlin, 1899; Dra^endorfT, Ztd-xch. a>"iL (Jlicni., 1866,
5, 200; Mei.^sncM- ami HankeJ, J. pralcl. C/u-iti., 1812, 25, 243.
11 Lionel, ( '.out.nl. rend , 1879, 89, 440.
15 Bar! els. Inc. c/t.: Dou'/.ard, J. Ckcrn. Soc., J901, 79, 715; Malm, Inc.. c,L\ Jaciiuelain,
<:t>i,ijt. re ,,<!., IS-1.3, 16, 13.
"' Jones, ,/. ('hem. >V,r., I S78, 33, 98. l r or the action v/ith other oxidising agents,
see l;cmonlt, (-mn^L /T/I</., 1 !)()!, 139, 478. Bartels, loc. c/t.: Flnckiir ( ^ drr//. Pli'trni.,
ISS9, |3I, 27, 20; Zctlxc/t nnnl. (-Ju-ni.., 1S91, 30, 117, Varerni'.- and Ilcrhc. Hull. Xoc.
chini\, IS77, {2|, 28, .")23; Zdtxr/i.. annl. C/iati., 1878, 17, 349; Schohk r , ./. 'pi'ttfcl. Ch'.'ni.,
lS7(;j,2l, 14, 291; Hull. >S'or. cft.ini., 1877, |2|, 28, 523; Maycneoii and Bcrueret, Co, apt.
r<-n<L, 1S7I, 79, .US.
52 ANTIMOXY AND BISMUTH.
potassium antimoiiafce and a trace of manganese. The reaction may be
represented by the equation :
2KMnO 4 -rSbH 3 =Mn 2 3 + K 2 HSbO 4 +H 2 O
The reaction between stibine and an aqueous solution of silver
nitrate has received considerable attention. The black precipitate that
is formed was formerly 1 thought to be silver antimonide, Ag 3 Sb. The
reaction was therefore thought to be different from that with arsine, but
subsequent investigation has shown that the proportion of antimony in
the precipitate does not correspond to that required by silver antimonide.
It is now considered that the action of stibine closely resembles that of
arsine, and may perhaps be represented by the equations :
SbH 3 +3AgX0 3 =Ag 3 Sb +3HXO 3
Ag 3 Sb -f- 3AgXO 3 + 3H 2 6 - 6Ag + Sb(OH) 3 '+ 3HX0 3
The second reaction occurs with excess of silver nitrate. 2 The hydratcd
antimony oxide is almost completely insoluble in the resultant liquid
and is thus precipitated with the silver. In this way the action differs
from that of arsine. The precipitate is also stated to contain a little
metallic antimony. The antimony oxide can. be dissolved out of the
precipitate by treatment with hot concentrated hydrochloric acid or
with tartaric acid. By the action of stibine on a concentrated aqueous
solution of silver nitrate a greenish-yellow coloration is obtained, hut
the substance producing this colour has not been isolated. It is
suggested 3 that this compound may be Ag 3 Sb.3AgX0 3 , corresponding
to the similar compounds of phosphorus and arsenic produced by the
action of phosphine and arsine respectively on solutions of silver nitrate,
and the suggestion is supported by the results of approximate analysis
of the coloured mixture. On this assumption the action of stibine may
be represented by the equations :
SbII 3 -r 6AgXO 3 =Ag 3 Sb.3AgXO 3 +3HXO,
Ag 3 Sb.3AgNO 3 +3H 2 6 =6Ag -rSb(OH) 3 +3HX0 3
thus further emphasising the resemblance between phosphine, arsine and
stibine. It has also been suggested that the greenish-yellow coloration
may be due to the formation of the compound Ag(SbH 3 )XO 3 , analo-
gous to Ag(XH 3 )Cl, but there appears to be 110 confirmation of this. 4
The reaction with silver nitrate has been suggested for the detection
of traces of stibine. 5
When stibine acts upon sodium auri chloride, a violet stain is pro-
duced ; similar stains are obtained with phosphine and arsine, but not
with hydrogen.. This reaction is suggested as a sensitive test for these
hydrides. Organic matter must be destroyed prior to the test ; hydrogen
sulphide also interferes. 6
1 Lassaigne, J. Chim. med., 1840, 17, 443.
2 Recklcbcn and Giittich, Zcit&ch. anal. Choti., 1910, 49, 73; Rcckleben, Bcr., 1009,
42, 1-158; GiiUich, fnauy. Dissertation, Lc.ipziy, 1000; Vitali, L'Orosi, 1802, 397.
:5 Poleck iu id TJmmmcl, Bcr., 1S83, 16, 2435.
4 Bciru-ls, Jnnwj. //i,ssr;;7., Berlin, 1889.
5 AVeckc'.s, Chan . Xew#, ] 923, 126, 275. For f urtlier lil era! urc\ sco Frcsonius, :: ,-
ziir qn.ali talli'c.ii chtt/u'xc/icn- A.itulyf>&'' > (Braxinschweio;), Gtli Rd., 1895, p. 2-18;
Inc. cit-.; .Mouzeaii, Co/npl. r(</id., 1872, 75, 1823; ^'Zc.itsch. anal. Uiifni., 1873,
J-Iumpcrf, J. 'prald. Chem., 1865, 94, 398; Kofjnann, Anti'tlr./i, I S(>0, 115, 287;
ibid., 1S37, 42, 563; Pfaii, i6^.,"l837, 42, 563.
G Zimmcrmann, Apothekcr-Zeitung, 1921, 36, 26.
COMPOUNDS OF ANTIMONY. 53
The best absorbents for stibine arc solutions of silver salts, iodine
and iodic acid. 1
A number of organic substitution compounds of stibine have been
prepared and described. 2 They are for the most part more stable than
stibine itself.
ANTIMONY AND THE HALOGENS.
Antimony and Fluorine.
Two compounds of antimony and fluorine are known ; antimony
tri fluoride, SbF 3 , and antimony pentailuoridc, SbF 5 . Two other
compounds have been reported, 3 but it is probable that these are
double compounds having the formulae SbF 5 .2SbF 3 and SbF 5 .3SbF 3 .
Antimony Trifluoride, SbF 3? was first prepared by Berzelius in
1824- by evaporating a solution of antimony trioxide in hydrofluoric
acid ; 4 Dumas prepared the same compound in 1826 by distilling a
mixture of mercuric fluoride and powdered antimony. 5 It has also
been prepared by heating antimony trichloride with hydrofluoric acid
in the presence of an organic solvent. 6 Metallic antimony docs not
dissolve in concentrated hydrofluoric acid. 7
Antimony trifluoride is most conveniently prepared by the method
of Berzelius. Pure antimony trioxide is dissolved in excess of hydro-
fluoric acid, and the solution is evaporated until a film forms on the
surface. On cooling, long, needle-shaped crystals separate out. These
may be dried between filter-paper and stored in vessels of gutta-percha
or platinum. 8
Antimony trifluoride forms colourless, transparent, rhombic crystals
of density 9 (at 20-9 C.) 4-379. Its melting point is 292 C. or slightly
lower ; 10 it sublimes when heated in a platinum vessel. 11 The solubility
in water is as follows :
t C 20 25 30
SbF 3 (grams per 100 grams water) 384-7 451-0 494-0 5G5-G
The solubility is increased bv the presence of hvdroiluoric acid and of
alkali salts. 12 "
The heat of formation of antimony trifluoride is ] 14,300 gram-
calories. 13 It docs not fume in air, but when heated it volatilises with
partial, decomposition, leaving a residue of antimony trioxide. It is
very hygroscopic. If an aqueous solution is evaporated without the
addition of hydrofluoric acid, some antimony! fluoride is obtained ; no
hydrolysis is apparent, however, below 30 C. 14
] Reckleben and GuUich, loc. cit. - This Series, Vol. XI, Part 111.
:1 Ruff, Plato and Graf, Btr., 1904, 37, 673.
4 Berzelius, Poyy. Annalcn, 1824, i, 34.
' Dumas, .4 nn. Ghim. Pkys., 1826, [2], 31, 433.
(; Kinetic Chemicals, Inc., Frwch Puttut, 1931, 720589; German Palnit., 1934, (>02()97.
7 Pluckier, J'oyy. Auit(.tlcn, 1852, 87, 249; An-ufdan, 1852, 84, 248; Arm,. C/inn.
7%.v., 1853r[3], 39, 495.
8 Guntz, A'tin. Chun. Ph.y*., 1884, [6], 3, 47. See also Posenheim and Grunbaum,
Zc.itecL an.org. Cham., 1909, 61, 187.
Ruff, Plato and Graf, Bvr., .190-1, 37, 073.
10 Carnelley, J . Ckem. Soc., 1878, 33, 275.
11 Swart/, "Bull. A cad. roy. Btl'j., 1892, [3], 24, 310.
32 Posenheirn and. Griinbaum, Zcitsck. auorg. Clic.in., 1909, 61, 187.
13 Guntz, loc. c,it.\ Coinpt. rand., 1884, 98, 303, 512.
54 ANTIMOXY AX.D BISMUTH.
Chlorine reacts with antimony tri fluoride forming tlic compound !
2SbF 5 .SbCl 5 .
Liquid ammonia reacts with antimony tri fluoride to form the
di-(minwniate, SbF.,.2XH 3 . This is a yellow powder \vhich loses
ammonia in the presence of moist air. 2
Antimony triiluoride shows a tendency to form double and complex
salts. From the thermochemical examination of solutions in hydro-
fluoric acid, Guiitz concluded that an acid fluoride is formed, but was
unable to isolate it. 3 Beck 4 concluded that the most stable complex
formation is of the type MSbF 4 or SbF ; >.MF, in which the antimony is
tervalent.
Numerous double compounds are formed with alkali fluorides, either
by crystallisation from solutions of the mixed salts, or by addition of
alkali carbonate to a solution of antimony trioxide in hydroiluoric acid.
Salts in which the ratio SbF a : MF has the following values have been
obtained : 4 : 3, 3 : 1, 2 : 1. T": 4, 1 : 1, 1 : 2 and 1 : 3. They are colour-
less, crystalline compounds and contain no combined water ; they are
fairly stable in air, and dissolve readily in water without producing
turbidity ; the solutions arc acid, and attack glass. The salts can be
regained from these solutions by evaporation. 5
Double compounds with alkali chlorides and sulphates have also
been obtained, having the general formulae MCl.SbF 3 , M SO 4 .SbF. } ,
;j.M.SO.,.!SbK : , and M 2 S() 1 .2SbF,, where M represents a" univaleiit
metal. They may be prepared by the first method mentioned above,
by the action of basic antimony sulphate on the corresponding fluoride,
or by the action of alkali sulphate upon antimony trifluoridc in the
presence of hydrochloric acid.' 5 In general they crystallise fairly well,
without combined water; they arc fairly stable and not hygroscopic.
Their solutions in water are strongly acid and attack glass.
Other double compounds ha.ve also been obtained. In some cases
there is evidence for the existence of a complex ion in solution, but
not in others. Solutions containing potassium nitrate, potassium
sulphate or oxalic acid give no c\ idcncc of a complex ion: while
solutions containing' normal sodium oxalalc or tartrate, ammonium
o\ala!e or potassium aiitimoiivl tart rate indicate decidedly the forma-
tion of such ions. The follouing er\stalline compounds have been
obtained : 7 :JK NO,.SbF,, !( N ! I., ),('.,'( ) l .i'S!)F :j , 'JXa.C.O^SbF, and
K ; .SI>()((y>Jo.S!>SVsII.,<>.
Salts containing aninuonv triiluoride h.a\c been used a.s mordants;
bnl onl\ (hose salts \\lueli vicld complex ions m dilute solution are
sin i n 1 >le !'or sueii j >u rposc. s
1 I lull, Sia.iU-i am! <IM!, /.'if-ift nn<>,tj. ('/,</// , I'.MIS, 58, i^.").
HUN, H,- , /;<>-., iDirn, ;;<>, i:;jn.
' t iunl/, ( ';/////. /</"/., ISS I, 98. :;<)(). Sec ;il>o iJcdcM/, .lirli. I'lnt/m., IS'.IS, 236, L^M.
; r.cck, '/.id fit. nimnj. ('h- in , I'.I^S, 17^, III.
- Flu. -KI MT, /r.r. < .'/.;' \nn l!a:il ;ui<l i IJIUMT, Ho , IS'.M), 23. IN-i Vl^\ <ini<in I'ttlt-,,1,
j.^vS, .,o:isl, I-'idirii, /; / , IS'.U, 24, Itri. 170. dunnn I'ahnt, I S'.IO, fi.'W 1 S ; Kjjliraini
,
-y, K.-I. 'Jl!:-: <;<.>nt'Hi /'////</, IS'.IJ, 7<;ii;s, \o;i l!;i;ul, /;/., ISIKJ, 29, Kef. ,'{21; (icnmin
/'.-/' /.,'. I M> 1, S.")(J2>.
- i;,,. .-nlirini aii-1 ( ii unl.iuisi, l,-. rl(. Sic aUo Fr ( ,ln-h, ll<r., Is!)(i, 29, Kef. 417;
(,'- t/r-ni /'nil //-. isi) I, s;r,(;s.
i lo.-fiilu'ini ami ( ii'unbauin, l<x'. cil.
CTOIPOUXDS OF AXTD10XY. 55
Antimony Pentafluoride, SbF 5 , was first reported by Berzelius in
1824, who obtained it by the action of hydrofluoric acid on autimonic
acid ; l for sonic time the existence of this compound was denied, 2
until in 1867 Marignac confirmed the results of Berzelius, including the
preparation of a number of double compounds. 3 In 1891 Moissan
prepared the compound by direct union of the elements. 4
Antimony pentailuoride is most conveniently prepared either by the
method of Berzelius or by the action of anhydrous hydrogen fluoride
upon antimony pentachloride. 5 The latter method is carried out by
heating a mixture of hydrogen fluoride and antimony pentachloride at
25 to 30 C. until no more hydrochloric acid is evolved ; after a con-
siderable time the boiling point of the mixture rises to 150 to 155 C.,
at which temperature antimony pentafluoride distils over.
The pentafluoride is a colourless, thick, oily liquid which boils at
149 to 150 C. Its density at 22-7 C. is 2-993." It is soluble in water
and is hygroscopic. It has a drastic action upon the skin. 6
The 'dihydrate, SbF 5 .2H 2 O, has also been prepared.
Chlorine appears to have no action upon antimony pentafluoride ;
bromine reacts to form a viscid, dark brown mass of indefinite com-
position, which may contain the compound SbF 5 Br. Iodine forms two
compounds. With excess of antimony pentafluoride at 160 to 220 C.
a dark, bluish-green substance, (SbF 5 ) 2 I, is formed, melting at 110 to
135 C. It does not lose iodine when heated to 240 C., but it is readily
decomposed by water. When antimony pentafluoride is heated with
excess of iodine at a temperature above the boiling point of iodine, a
dark brown compound, SbF 5 I, is formed, melting at 80 C. This com-
pound is decomposed when heated above 260 C. with evolution of iodine,
but it is not so readily decomposed by water as the Cornier compound.
Sulphur dissolves in antimony pcntafluoridc to form a dark bine
solution from which the compound SbF 5 S -can be separated. This
melts at 230 C., is very hygroscopic, and is decomposed by water and
moist air. The decomposition by water is probably represented by
the equations :
2SbF 5 S + IIoO = 2SbF, + S -r SOF, ~ 2IIF
SOF. 2 +lIoO=SO 2 +2lIF
Antimony pcntafluoridc is decomposed when a current of hydrogen
sulphide is passed over it, the products being sulphur, hydrogen fluoride
and antimony thio-Iluondc. An aqueous solution reacts with hydrogen
sulphide only when it is warmed.
The pen ta fluoride reacts with nitrogen sulphide, sulphur dichloride
and chromyl chloride ; also with molybdenum pcntachloride and
tungsten hexachloride forming respectively a molybdenum fluoride and
tungsten hexafluoride, together with double compounds with antimony
pcnta fluoride. .
When dry ammonia is passed over the pentafluoride the latter
1 Berzelius, loc. at.
54, 2-18.
1867, [2], 8, 323; A,ui. Chim. Phys., 1867, [-1], 10, 371;
2 IfJuckiiicr, Att'/ialcn 18.~)2,
181)1, [6], 24, 247.
RulT, Plato and Graf, Bcr., 1904, 37/673; Kuii, Graf, Heller and Knoch, Bcr., 1906,
39,4310.
G For a discussion of the space chemistry of this compound, sec Hull, Ebert and
Menzcl, Ztitsch. anorcj. Chei/i., 1932, 207, 46.
56 ANTIMONY AND BISMUTH.
becomes coated with a yellowish-red crust of indefinite composition ;
the action is vigorous until the protective coat is formed, which then
prevents further action. When heated with liquid ammonia at 100 C.
in a platinum tube a white powder is formed which is probably the
complex substance NlI(SbF 3 .NII 2 .HF) 2 . It is readily decomposed by
moist air ; its solution is acid towards litmus and it is slowly acted upon
by water \vit3i the formation of antimonic acid.
Antimony pcntafluoride reacts with phosphorus forming a yellow
vapour, with phosphorus trichloride forming phosphorus tri fluoride,
and with phosphorus pentoxide forming phosphorus oxyfluoride. 1
With arsenic trifluoride a series of crystalline compounds is formed ;
and with antimony trifluoride, a series of compounds ranging from
SbF 5 .2SbF 3 to SbF 5 .5SbF 3 . These may be prepared by distilling a
mixture of antimony pcntafluoride and antimony trifluoride. The
compound SbF 5 .2SbF 3 is a colourless, transparent, crystalline sub-
stance ; its density at 21 C. is 4-188 ; it boils at 390 C. and it is hygro-
scopic. The compound SbF 5 .5SbF 3 boils at about 384 C. 2
Antimony pentailuoridc reacts with the tetraehlorides of tin,
titanium and silicon with evolution of hydrogen chloride in each case.
When warmed with colloidal silicic acid, antimonic acid and silicon
tetrafluoridc arc formed.
]\lany carbonaceous materials arc attacked by the pentafluoridc,
including filter-paper, cork, wood, india-rubber, benzene, ether, alcohol,
acetone, glacial acetic acid, ethyl acetate, carbon disulphidc, light
petroleum and chloroform. With chloroform an easily liquefiable gas
(probably CC1 3 F) is formed.
Antimony pcntafluoride when dry docs not react with the majority
of metals. When heated with sodium a violent reaction occurs and a
white vapour is formed. It is reduced to the trifluoride when heated
with powdered antimony.
The penladuoride can be converted quantitatively into sodium
hydrogen pyronnfimonate by the addition of sodium hydroxide or
sodium carbonate. 3
A double compound of antimony pcntafluoride and antimony pcnta-
chloride, 2Sl)F r) .Sl)(1 5 , is obtained by the action of chlorine on antimony
( rilluoride. 4 Several other double compounds of these two pentahalides
are indicated by the results of an investigation of the freezing point
curves of mixtures of the two. 5 Four of these compounds have been
isolated: 2SbI<YS^\( /; f 3-08), SbF 5 .SbCl 5 , 2SbF 5 .3SbCl 5 (/)f 2-79),
and SbI<V3SbCl-(//; u 2-73) ; two other compounds, 3SbF 5 .SbCl 5 and
SbF f) .-iSbri r> , arc also believed to exist. They arc all decomposed
on fusion. Molecular weight determinations have been made in
solutions in sulphuryl chloride: the compounds 2SbF 5 .3SbCl 5 and
SbI<\ r> .3S{)C ( lr ) gi\'c values which arc only about one-third of the theoretical
molecular weight, while the compound 2SbF 5 .SbCl 5 docs not appear to
dissociate in 10 per (tent, or more concentrated solution. The mole-
cular volumes of some of these compounds indicate that there is a
considerable decrca.se in volume when the compounds arc formed from
uiY, Graf, .Heller and Knooh, loc. cit.
ulT, IMat-o and Graf, lor. cit.
nil, Graf, I Idler and Knoch, loc. cit.
nil, Stiiuhcr and Graf, Z,c.itM".h. anorg. Chem. y 1908, 58, .325.
COMPOUNDS OP ANTIMONY. 57
their constituents. Chemically the compounds closely resemble corre-
sponding mixtures of the two binary compounds. Bromine reacts
with all of them. When the compound 2S'bF 5 .SbCl 5 is mixed .with
nitrosyl fluoride at -80 C., aud the mixture allowed to warm up, the
compound SbF 5 .NOF is obtained as slender, colourless, needle-shaped
crystals. This compound may also be obtained by the action of nitrosyl
tluoriclc on antimony pcntafluoride, and by the action of antimony
pentailuoride on the corresponding arsenic compound, AsF 5 .NOF. The
compound SbF 5 .XOF sublimes below red heat without decomposition ;
it is very hygroscopic and is decomposed by water and by alcohol. It
reacts with potassium fluoride with the formation of a double compound
of potassium fluoride and antimony pentafluoride and separation of
nitrosyl fluoride. 1
Antimony pentafluoride forms a number of double compounds with
alkali chlorides and fluorides of the general type SbF 5 .MF and SbF 5 .2MF.
These may be prepared by the addition of alkali hydroxide to an acid
solution of antimony pentafluoride, or by the solution of alkali antimon-
atc in hydrofluoric acid. They are all deliquescent and soluble in water,
but arc stable when dry. Their solutions in water evolve hydrogen
fluoride, and on evaporation yield oxyiluorides. The solutions will
react with hydrogen sulphide only after prolonged treatment.
Certain compounds of antimony pentafluoride with organic bases
have also been obtained. 2
Antimony and Chlorine.
Two chlorides of antimony, namely the trichloride and pentachloride,
are known with certainty ; the tetrachloride has also been reported.
Antimony Trichloride, SbCl 3 , has been known for a long time,
having been prepared by Basil Valentine by distilling a mixture of
antimony trisulphide and. mercuric chloride ; it was at one time thought
that, the" substance was a compound of mercury, but Glauber disproved
1 his i n 1 18. That the trichloride is decomposed by water was known to
Basil Valentine, while the oxychloride produced was called by Paracelsus
nierruri'Uti vitac, in the belief that it was related to mercury. At the end
of the sixteenth century the trichloride (probably admixed with oxy-
chloride) was introduced into medicinal preparations by Victor Algaro-
t us of Verona, under the name of pulvis angelicus*
Ant iniony trichloride is most conveniently prepared by the action of
coMoonl.rn.tcci hydrochloric acid upon antimony trisulphide; when^all
I ho hydrogen sulphide has been evolved, the residue is distilled ; after
rejecting the first distillate, which contains most of the volatile im-
puri tiesrthe final distillate is collected as a white, pasty mass of antimony
trichloride. 4
J Ruff, Staubcr a.nd Graf, Loc. cl!.
'' 1-Vr/rlius, !or. cU.; Mari^nac, l<>c. c.iL-, Rcdenz, Arch. Pharm., 189b, 236, 26/.
: ' Busilius Vulonfmus, ''The Triumphant Chariot of Antimony" English Translation,
ondon,' KU51 ; dauber, V^-.m c.hymlca (Frankfurt am Main), 1658, English Translation
London), Hisi); see also J)yson, 'Pharmaceutical Journal and Pharmacist, 1928, [41, 67,
1892,
1HSS, 27, Ki2; Lang,
58 ANTIMONY AND BISMUTH.
Numerous chemical reactions resulting in the formation of antimony
trichloride have been described. It may be obtained from metallic
antimony by the action of chlorine, 1 acid chlorides, 2 magnesium chloride 3
and other metallic chlorides. 4 Hydrochloric acid, free from air, does
not attack antimony, but in the presence of air, antimony trichloride
is formed slovdy ; the action is accelerated by the presence of a little
nitric acid. 5
Antimony trioxide is converted into the trichloride by the action of
chlorine, 6 chlorides of non-metals 7 and by dissolution in hydrochloric
acid. 8 Antimony pentoxide reacts in a somewhat similar manner. 9
From antimony trisulphide the trichloride may be obtained by the
action of chlorine, 10 hydrogen chloride (either in the gaseous form or in
solution as described above), thionyl chloride, 11 sulphury 1 chloride 12 and
ammonium chloride. 13 Concentrated hydrochloric acid reacts with
antimony pentasulphide with formation of the trichloride. 14 It is of
interest to note that the trichloride, has also been obtained by the dis-
tillation of a mixture of antimony sulphate and sodium chloride. 15
Antimony pentachloride is reduced to the trichloride by heating with
antimony. 16
Stibine may be converted to antimony trichloride by the action of
chlorine or phosphorus pentachloride. 17
A pure solution of antimony trichloride may be prepared by dis-
solving antimony oxyehloricle in hydrochloric acid ; crystals may be
obtained by evaporation from a solution of the trichloride in carbon
disulplnde 18 or in sulphuryl chloride, by sublimation of the trichloride
in a current of carbon dioxide, and by solidification after fusion.
Antimony trichloride can exist in three distinct crystalline modifica-
tions 19 with transition points at 65 C. and 69-5 C. respectively. The
modification stable at the ordinary temperature crystallises in the
rhombic system, forming colourless, transparent, prismatic or octahedral
crystals. 20 Its density 21 at 25 C. is 3-1-1. Its molecular volume 22
1 Hensgen, Cham. Zoilr., 1891, 958.
* lleumann and Koohlin, tier., 1882, 15, 419, 17,37; 1883, 16, 482, 1625; Michael!*,
J. 'prukL Ch.nn.. 187.1, [2], 4, 425; Baudrimont, Ann. Ckim. Phys., 1804, [4], 2, 12.
3 L'Holo, Cow.pt. rend., 1884, 98, 1491.
- 1 AtUield, ZU'IMJI.. anal. Chan., J870, 9, .1.07; Dexter, Poyy. Annalen, .1857, 100, 568.
5 Cooke, Proc. A-m.fr. Acad. Arts tici., 1877, 13, 1.8; Kobiquet, Ann. C/iim. Phys., 181.7,
[2], 4, l(>f>.
" \Vehor, Poyy. An.n-nlcn, 1861, 112, 625.
7 Oddo and Scrra, Gazzeltu, 1899, 29, H, 355; Michaelis, loc. ciL; .Ranter, A/r/talc//,
1892, 270, 251. 8 Kobiquet, loc. cit.
u Weber, Inc. ciL; Rose, Poyy. Annalm, 1858, 105, 571; Miehaelis, J. prakt. Cheat.,
1871, 4, 454; Hauler, foe. at.; Trin/, An.naleii, 1884, 223, 358.
10 Rose, J'oyy. An-nalai, 1824, 3, 445.
11 JVinz, loc/.cit.. l ~ KufT, her., 1901, 34, 1752.
1:J Fre.senius, ZziUch. a/tal. ChcM., 1886, 25, 200; de Clermont, Compt. rend., 1879, 88,
972.
14 Seherer, ZaMi. anal. Chcm., 1864, [3], 206.
15 Berzeliiis, fic.hwriyyc.r's J., 1812, 6, 144. 1G Hensgen, loc. cit.
17 8toek and 0-utt-inann, Be.r., 190-1, 37, 885; Vogcl, J '. prakt. Chon., 1838, 13, 57.
18 Cooke, Proc. AvK-r. Acad. Arts /.S'fi/., 1877, 13, 38, 72.
10 Kendall, Criltcnden and Miller, ./. Amer. Chcm. Soc., 1923, 45, 963.
- Topsoc, KitzuiHjtiltf.r. K. A /cad. WiM. Wien, 1872, 66, 42; Cooke, loc. ell.; Grotli,
Che.tn. Kry$t. 3 1, 227. l^or the spatial structure, sec Bergmann and Engel, Zeitech. pJiysikal.
C/K'.M.., 1931, 138, 232.
- 1 International Critical Tables, 1926, I, 111. See also Cohen and Strengers, Zeilscli.
phy^ikal. Chan., 1905, 52, 164; Cooke, loc. cit.
Bdtz, Sapper and Wunncnbcrg, ZtilscJi. anonj. Che/n., 1932, 203, 277.
COMPOUNDS OF ANTIMONY. 59
(calculated from the density at -104 0. and the coefltcient of ex-
pansion) is 08-5. It melts at 73 --I ('., Jbrini.no- a colourless or yellowish
oil. 1 The existence of.' the lirst transition point slightly below the
melting point is indicated when the substance is heated gradually, for,
in the neighbourhood of the melting point the crystals change to a
heavy powder. The latent heat of fusion is 3,030 gram-calories per
mole. 2 The density of the liquid, and the surface tension (cr), at various
temperatures, are as follows :
Temperature,
Density (D\)
o- (dyr.es per cm.)
C. 109-5
127-5
148-5
166-5
2-599
2-558
! 2-511
2-471
11.) 44-51
41-84
| 39-43
37-38
The variation of the density of the liquid with temperature (t) ;
109 C. and 166 C. is thus given by the expression
; between
expression
= 2-844 -0-00224/
The calculated mean value for the parachor is 227-4.
Liquid antimony trichloride boils 4 at 220-2 C., its latent heat of
vaporisation 5 being 10,700 calories per mole. The critical temperature
is 524 C.. the ratio of the boiling point to the critical temperature (on the
absolute scale) thus being 0-619.
Antimony trichloride may be distilled from solutions containing
sulphuric acid provided that hydrobromic acid is dropped slowly into
the solution, which latter should be kept at 180 C. 7 On distilling a
solution of antimony trichloride in hydrochloric acid, hydrogen chloride
distils over first, followed by a mixture of hydrogen chloride and anti-
mony chloride, and finally antimony chloride alone. 8 The volatility of
antimony trichloride is reduced by the addition of ferrous chloride. 9
The trichloride does not volatilise when a current of hydrogen chloride
is passed through a hot, dilute solution. 10
The solubility of antimony trichloride in water and the effect of
temperature upon solubility is as follows : li
I Kendal, Cnltcnden and Miller, /or. aL See also Oooke, loc. cit.; Kopp, A'trnalcn,
IS.")."), 95, 348; Capitaine, J. pra/cL Ch.tm.., 183!), 18, 440.
- Tolloczko, Bull. Acad. ticl. Cracow, 11)0.1, 1; Tolloczko and Arcyer, CJic.ru. Zailr.,
l!HO, ii, 1024. For the specific heat, sec Pebal and Jalm, Po(j<j. Ahnaltn, 1880, [2], 27,
f>84.
' Sudden, ,/. Chf.ni.. ^'or., .1927, 130, 1 173. See also fnt.f-.riintional Critical Table.*, 1 028,
3, 23: Jvurnakov, Perlnnitfer and Kanov, A-trnulex da rJ-nMih.it. Polytc.cJi'ntfiuc. Pierrc.-lf-
(Jratid, Pelroijrad, .10.15, 24, 300; Klemensiewiecz, Jhill. Ac.ad. Sci. Cracow, LOOS, 48").
- 1 Maier, 'llwrcfin of Mint* 7Yt7t. Pa. per, L02T), 30(1. See also Capitaine, loc. cit.\ Cooke,
loc. cit.; Cai'nelley and AY'illiams, ./. Churn. &oc., 1878, 33, 281; Anschuiz and Evans,
,/. Che ni,. tine.., L88 r (), 49, 708; Jlu:, .1886, 19, 1004; Aniialut, .1.880, 253, 101.
5 Maier, /or. <:,/.
r> l\olin]an/, and Suehodski, Z,?tt*ch. pkij^ikal. CJicni., 1014, 87, G35. See also van
Aubol, Jhift. Acad. roy. Hdy., 1 ( ,)22, 7, -100.
7 .Rohi-e, Zc.ii.wh. anal. Chc.m., 1024, 65, 100; Bottger, Ocsterr. CJitm. ZtiL, 102-1, 27, 24.
8 Hose, Poyy. A)i'n<il<'ii, J8.")8, 105, o70; Schleier-, Inauy. 'Dix^crlalion, Erlangc-ii, J802.
<J Fischer, Annalcn, J8S1, 208, J80.
10 llufsclimidt, Be r., 1884, 17, 2245; Goocli, Browning and Grtiencr, Zc.itxtfi. anal.
Chan.., 1803, 32, 473.
II van .Bern-melon, Xoodi and Mcerburg, Zeitsch. wnory. Chcm., 1003, 33, 272. Sec
also de Tamv, J^'^c/iatiun, rirccht, 1022.
60 ANTIMONY AND BISMUTH.
Temperature, C. . j 15 20 ' 25 ; 30 l 35 | 40 50 00 i 72
Solubility i j : ; ! | ' i
(Grams SbCl., in 100 ! | : ' ! ! ]
urams' water) i 601-1 815-8 920-8 '. 988-1 ' 1008 J 152 ; 1368 , 1917 : 4531 ' cr.
When excess of water is employed, hydrolysis sets in rapidly,
antimony trichloride thus resembling the other trichlorides of this group.
The solubilities of the trichloride in aqueous solutions of hydrochloric
acid at various concentrations at 20 C. are as follows (the concentration
of each solute is given in grams per 100 grams of water) : 1
HC1
! SbCl 3
910-1
4-86
805-4
12-34
879-0
16-80
857-6
18-41
866-4
23-68
856-3
58-08 ;
789-8 '
The trichloride is soluble in many other solvents including ether, 2
carbon disulphide, 3 absolute alcohol, acetone, 4 chloroform, 5 and to some
extent in liquid cyanogen. 6 It is insoluble in carbon tetrachloride.
The molal conductivity of solutions of antimony trichloride in
bromine 7 suggests that double molecules of Sb 2 Cl 6 exist, which dis-
sociate into Sb 2 Cl 3 + " r " ! ' and 3C1~ ions. This view is supported by elec-
trolysis experiments. 8
The dielectric constant 9 has been determined for a series of dilute
solutions of antimony trichloride in benzene. At 25 C. the value
varies with dilution from 2-377 to 2-588, and at 40 C. from 2-340 to
2-534. From this the calculated value of the dipole moment 10 is
3-75 xlO- 18 c.s.u.
The chlorides of potassium, rubidium, ammonium and thallium will
dissolve in purified liquid antimony trichloride. When the concentra-
tion of the solution is above 0-lA r , the conductivity is less than that of a
corresponding aqueous solution ; for more dilute solutions the con-
ductivity is greater. The conductivity increases regularly with rise of
temperature from 70 C. to 200 C. It is probable that the degree of
lonisation is less for solutions in antimony trichloride than for solutions
in water, but that for the dilute solutions the ionic velocity is greater. ll
Solutions of the bromides of potassium, ammonium and thallium in
1 Seiclel, tw Solubilities of Inorganic and Organic Sub^tancex*' (Xcw York), 2nd Kd.,
1920, p. 88; Meerburg, Zeitsch. anortj. Chem., 1903, 33, 290.
- Usanovitsch and Terpugov, J. (Jen. Chem. H-uss., 1932, 2, 447; Zcifxc.h. ph-ijtiikul.
Chem., 1933, 165 A, 39.
:j Cooke, loc. cd.
- 1 Naumann, tier., 1904, 37, 4332.
5 Sabanejew, Zeitsch. Chem., 1871, 7, 204.
<; Centnerawer, tier, rusx. Ph-i's. Otd. 9 1901, 33, 545; Bull, tioc. c/u-tn., 190.1, [3], 28,
405.
7 PJotnikov and Kudra, Zettxc/1. physilcal. Chcm., 1929, 145 A, 2G5.
8 For tlic conductivities of solutions of antimony trichloride in other solvents, see
Kahlenburg and Lincoln, J. 1'hy steal Chem., 1899, 3, 20; Lincoln, ibid., 190l, 5, 503.
9 Smith, Proc. J-toy. Sue., 1932, 136 A, 256.
10 Slightly different values have also been obtained, according to the method of calcula-
tion adopted. See Malone and .Ferguson, J. Chem. Phy&ics, 1934, 2, 94; J3ergmann and
Engel, Phyaikal. Zeitsch., 1931, 32, 507; Zdtxch. physikal. Cham., 1931, 13 B, 232; Werner,
Ztitseh. a.norfj. Chtm., 1929, 181, 154; Sehlundt, /. Physical Chcm., 1901, 5, 1.57, 503; 1909,
13, 669.
11 Klemensiewiecz, loc. cit. See also Erycz and Tolloczko, Chem. Ze?Ur., 1913, i, 91.
COMPOUNDS OF ANTIMONY. 61
antimony trichloride have also been examined and their conductivities
determined. 1
The viscosity of antimony trichloride from 80 to 200 C. has been
determined, 2 and the curve obtained by plotting the fluidity against the
temperature appears to show a break at 120 C.
The Raman spectrum, 3 which consists of four lines, suggests the
existence of eo-valent linkages.
The refractive index 4 for the sodium D line is 1-460.
The vapour pressure of antimony trichloride 5 is as follows :
1
t c C. .
i p (mm.)
. ! 120
. ; 29
;
130
43
140
64
150
92
160
127
Determinations of the vapour density of antimony trichloride c arc
in agreement with the molecular formula, SbCl 3 ; this formula is also
confirmed bv a number of determinations of the molecular weight in
o
solution by the freezing point method. 7
The heat of formation of antimony trichloride 8 is 91,390 gram-
calorics per mole.
The trichloride can be distilled without decomposition in a current
of hydrogen. 9
The reaction between antimony trichloride and hydrogen has been
investigated by passing a current of hydrogen at the rate of two litres
per hour over the chloride. 10 By means of a transformer a pressure of
15,000 volts was applied to the reaction chamber, and an antimony
mirror was obtained.
The trichloride is stated to absorb oxygen when exposed to the air ;
certainly it deliquesces rapidly in air, forming a cloudy liquid, while a
solution of antimony trichloride in hydrochloric acid readily absorbs
1 KlcmcnsJexviccz and Baloima, Roc,zw-ki Chi-tit.., 19.3], u, 083; 1930, 10, -181.
~ Klcmensiewiecz, Bull. A end. ScL Cracoic, 1908, 485.
:! Daurc, Com.pl. rend., 1928, 187, 940; Krishnaniurti, Xalurc., 1930, 125, 892.
4 J3ccqucrcl, Ann. Ohim. Plnjx., 1.877, [5], 59, 122.
r> Inter ndt'wiia.l Critical Table*, 1928, 3, 213. >See also Rotinjanx and Suehodski,
Zritwh. yhyxibil. C'hem., 19J4, 87, (135.
'' Mitscherlich, J. praJcf. C/H-HI.., I8-1O, jl], 19, -ir>5; Worcester, l y ror,. Amer. Aaul. Arls
XcL, 1883, 1 8, 01.
7 Raoult, Zc.if.Kf.h. phyiiikaL Ghc.-ni.., 1888, 2, 371: Lespiaii, Cwttpl. 'ic-iid., 1897, 125,
1094; Tollo(;xko, 7jC.it.ach. phyxikal-. (Jhc.-ni., 1899, 30, 705. ^cc, however, Wakloii (Ze.it.M'h.
atiorrj. Clieiri., .1902, 29, 377; Zr.Uwh. yhyxikaL Clic.rn., 1!)03, 43, 437), wlio obtained higher
results by the: free/ing point method.
For further information concerning the physical properties of antimony trichloride,
see Werner, Zc'i/.xc.li. finorg. Chc/iu., .1929, 181, lo-l; CJnprnan and Me.fntosh, Procccdrayx
and T'rftnvr/c.tioHti of I lie. Noia Scotia, .In^lilule of faic.-nc.r., .1928, 16. 189; von Mullen lieim,
Zcitw/i. (inorg. Ch.f.m., 1928, 176, 1, Quani and Wilkinson, /. A-mrr. Chvn. tide.., J92r>,
47, 989: Schuster, Zr.iixc.fi. (cnonj. 0/i.p.m., 192r>, 146, 299: Gossniann, Zc.il.xck. Ph.yxik,
1921, 22, 273: Macbeth and Maxwell, ./. (.'hem. ,SV:., 1923, 123, 370; .Billx, Zr.ilwh.
plti/xiL-'iL C/H>),I., 1922, 100, Jf>2; l^ideal, Phil. Mn<j., 1921., |(i|, 42, I5(); Crymbal, ]>roc.
Chun >SV., 191-1,30, 179; Pascal, />V//. A'or. chun., I ( .)12, \ I |, II,2()I; Scliiuridt , ./. /V/.^/Vv//
C/H-HI., 1901, 5, r(>3.
s Thoinscn, />r/-., I8S3, 16, 39. Sct> also Omit/, Ann. ('linn. /%x., IS81, |'(Jj, 3, T>3 ;
Tolloexko, /jcilxch. '/ihyxikdf. Chon., I SI)!), 30, 70.1; 'I'olloczko and M'CVT, A'o,v///ox, 11)10,
35, (Ml; Thomlinson,' Client. Xcic*, 1909, 99, 133.
'' Cooke, Pioc. A-nwr. A cad. Art* tici.., 1877, 13, GO, 72.
J0 Miyamoto, </. Chem. Soc. Japan, 1932, 53, 788.
62 ANTIMONY AND BISMUTH.
oxygen. 1 Oxidation occurs under the influence of sunlight, and it
is suggested that a peroxide is formed at an intermediate stage. 2
As already stated, the trichloride will dissolve in a minimum quantity
of water without decomposition, but if the molecular proportion of
II 9 O to SbCl 3 exceeds 2 to 1. oxychlorides are formed, the compositions
of which depend upon the temperature and the concentration. 3 (For
the hydrolysis of antimony trichloride, see p. 66.)
Fluorine displaces chlorine from antimony trichloride, the action
being vigorous. 4
Thermal examination of the system SbCl 3 - C1 2 indicates the presence
of a compound, 5 SbCl 3 .2Cl 2 , which freezes at -81-5 C. Antimony
pcntachloride is also formed. With nitrosyl chloride the compound 6
SbClg.NOCl has been obtained. No compound of antimony trichloride
with bromine is indicated by thermal examination.
Antimony trichloride is decomposed when heated with sulphur, grey
antimony trisulphicle, Sb. 2 S 3 , being formed ; 7 a solution of the tri-
chloride in hydrochloric acid is not affected, however, when heated with
sulphur. 8
Hydrogen sulphide reacts with the vapour of antimony trichloride
to form antimony trisulphicle ; J) reddish-brown crystals of antimony
thiochloride, SbSCl, arc also formed by this reaction at a slightly lower
temperature. 10 Amorphous antimony trisulphide is precipitated when
hydrogen sulphide is passed through a solution of antimony trichloride
in hydrochloric acid to which tartaric. acid has been added ; ll in the
absence, of tartaric acid a thiochloride is formed. 12 Precipitation may
also be effected from an ammoniacal solution containing tartaric. acid, 1 " 3
but not from a solution in acetone. 1 ' 1 Antimony trichloride dissolves
in liquid hydrogen sulphide, the solution possessing appreciable con-
ductivity ; the properties of this solution suggest that complex com-
pounds of antimony trichloride and hydrogen sulphide arc formed. 13
Concentrated sulphuric, acid has very little action in the cold, but on
warming, antimony sulphate is formed with evolution of hydrogen
chloride. ]fi When, a mixture of sulphuric- acid and a solution of antimony
trichloride in hydrochloric acid is distilled, hydrochloric acid distils over-
first, followed by antimony trichloride : when finally sulphuric acid
distils over, no antimony is found in the distillate, there being a residue
of antimony sulphate. By repeated distillations, however, it is possible
to obtain all the antimony as trichloride. 17
1 Cooko, CJic/m. Nrw*, 1.880, 44, 221.
- JSruhl and Schla^ol, Zf-ifxf/t.. fni.org. Ch<-)n., 193-4, 217, 401.
:! .Brandos, 8r7i.w<-i(/'jfr\v ,/., 1827, 51, 437; Wobor, Potf/. Annnlcn, I S(>f>, 125, 87;
Sabanejew, Zr-itsrh. Cfit-m., 1S71, 7, 20-1; />////. Soc. cht-w., 1871, \'2'\, 16, 71); Jxiudnmonl,
Cfiinpt rend., ISoO, 42, 803; J. -prakt . Ch<- /;/.., 18f>f>, 69, 2.12.
1 Mojssan, A- mi. Cklni. '/%*., .1801, |fi], 24, 2f>7.
5 Biltz and Jeep, Zcitxch. an^rc;. Ckcui., 1.927, 162, 32.
Gall and. Mcn^dabl, Bcr., 1027, 60 B, 86. 7 Vo^cl, Xclui'c.lyjcr'x J., 1817, 21, 70.
s Vortniann and Padber^:, J$r-r., 1889, 22, 204-1.
9 Durochcr, CwiipL rend., ISoI, 32, 823; ArcLow.ski, Zcttcft,. <ui(>r<i. Chan., !89r>, 8, 220.
" Ouvrard, Carn.pt. mid., 1893, 116, .l.")]7.
! Rose, PI>M. A'-nnalc.-n, 18.13, 89, 123.
- Duflos, .i trh ir Ai><itltt'l:f-n-cn-ii<x n(,r'1. Df-iifxrlldtirf, 1828, 31, 9-1; 1829, 36, 278;
M K'f'if/f/ct-'* J., 1830, 22, 190; Zt.vh. tinfiL Clou., 1871, 10, 343.
:! Finla-iier, ./. Hor. Chan. I,"!., 1889, 8, 733. !1 Xaumann, />V/-., 190-1, 37, -1332.
COMPOUNDS OF AXTIMOXY. 63
When a solution of antimony tri sulphide in boiling antimony
trichloride is allowed to cool, a double compound, SbSCl.TSbCL,
separates out in the form of yellow, transparent, rhombic prisms. 1 This
substance is deliquescent, and is readily decomposed by heating or by
the addition of water.
A number of compounds of antimony trichloride with alkyl sulphides
and with alkyl sulphides and halides together have been prepared cither
by heating the components in a sealed tube at 90 to 120 C., or by
heating them in calculated proportions gently under a reflux condenser. 2
Ammonia reacts with molten antimony trichloride 3 to form two
ammoniates, namely SbCl 3 .NH 3 , from which all the ammonia can be
removed by heating, and SbCl 3 .2XH 3 , a yellowish- white, crystalline
substance which is stable and volatile. The former of these is much less
deliquescent than the trichloride. From these compounds the corre-
sponding double salts SbCl 3 .XH 4 Cl and SbCl ;3 .2XH 4 Cl may be formed
by the action of hydrochloric acid. 4 A tri-amrnon-iate, SbCl 3 .3XII 3 , has
been prepared by the action of ammonia on a solution of antimony
trichloride in acetone. 5 It is a white solid, stable in air ; on heating it
loses ammonia. 6 More recently, however, it has been shown that when
treated with liquid ammonia, one molecule of antimony trichloride
absorbs rather more than three molecules of ammonia without appearing
to form a definite ammoniatc. 7 With liquid ammonia, in fact, antimony
trichloride yields a yellow compound 8 to which the formula Sb(XIT)Cl
lias been ascribed. On further treatment an orange nitride, SbX, is
obtained (p. 113).
When potassium cyan ate is added to an aqueous solution of antimony
trichloride, 9 a crystalline precipitate of antimonic acid is obtained.
This is ascribed to the ammonia arising from the reaction
KCXO -;- 211 oO - KHCOy -i- XH 3
Nitric oxide, free from nitrogen peroxide, is without action upon a
solution of antimony trichloride in chloroform, but in the presence of a
trace of the peroxide, a complex crystalline precipitate is obtained.
Solid antimony trichloride absorbs nitric oxide, the mixture becoming
liquid. From this liquid all the nitric oxide can be removed by treat-
ment in a vacuum. 10
Antimony trichloride is oxidised by nitric, acid, antimonic acid being
formed. 11 When a solution of antimony trichloride in nitric acid is
distilled, the first distillate, consists of a mixture of hydrochloric acid
and nitric- acid ; towards the end some antimony pcntachloridc distils
with partial decomposition : antimony pcntoxide remains. 12
1 Schneider, Poyy. Annalm-, lSf>8, 108, 407.
- .Ray, Adhikari'and Ray, J. Indian. Cfic.ni. tivc.., 1931, 8, 2,")!, 71.1. Sec this Scdus,
Vol. XI," Part- III. ' :! See also this Series, Vol. X.
* Deherain, CoinpL rc.nd., 1861, 52, 73-1.
c> Naumann, her., 1904, 37, -13,32.
r> See also Jaequelam, Ann. Chitn. /'%,>., 1837, 66, 128: Poiiiiiaif', Ounijtt. rend., I8-M,
20, 1180; Annnlc.n., 1845,56,243; Wemland and Schmid, />er., lUO-l, 38, J084; Rose,
Ami. Ch'nn. /Vi?/*., 1830, [2], 62, 322.
7 Sch war/ and Jeanmaire, />Yr., 19152, 656, J()62.
8 Soluvar/ and .Jeamnaire, lor. cit.
9 Daliolos, I'raL'tiha (A hid. Alkcn'trt), 1931, 6, 9'2; X<'.it*ch. tn.orf/. Chnn., 1934, 217,
38 1 .
10 Thomas, Contjtl. i<-n<(., IS9~), 120, 1 I I ."> ; !S9(i, 123, .")! ; Bessoti, ibid., 1 889, 108, 1012.
11 Vo.irel, Sr/i.icfujffft-'^ ./., 1817, 21, 70.
'- Rose, Ann. Ckun. /V///x., 1830, [2], 62, 322.
64 AXTIMONY AND BISMUTH.
When phosphine is passed through molten antimony trichloride, a
black complex substance of indefinite composition is obtained. l
Phosphorus pcntachloride 2 reacts with formation of the double
compound PCl 5 .SbCl 5 . A reaction also occurs with phosphorus tri-
iodicle. 3
When antimony trichloride is heated with alcohol under pressure,
oxy chlorides are formed ; 4 the reactions with ether, 5 acetone, 6 di-
methylamine, 7 benzene, 8 aniline 9 and many other organic compounds 10
have also been described. 11
Antimony trichloride reacts with stannic iodide, 12 double decomposi-
tion taking place. Double decomposition occurs when antimony
trichloride is heated with germanium tetraiodide. 13
A violet compound of copper, Cu 2 Sb, is obtained by the action of a
hydrochloric acid solution of antimony trichloride containing cuprous
chloride upon metallic copper. The reactants should be protected from
the air. 14 A similar reaction occurs between antimony trichloride and
metallic tin, 15 the compound Sb 2 Sn being formed. Xo reaction has been
observed with bismuth.
Reactions also occur with nickel 16 and cobalt, 17 a mono-antimonide
being produced in each case.
Among the uses for which antimony trichloride has been suggested
is that of an addition to a hydrocarbon fuel to act as an " antiknock."
About 18 grains per gallon of petrol arc recommended. 18
Double and Complex Compounds. When a current oi.' hydrogen
chloride is passed into a saturated aqueous solution of antimony tri-
chloride at C., until no more of the gas can be absorbed, a compound
1 Mahn, Jctiaische Ztitscli., 1869, 5, 160.
2 Weber, Pogg. Annaten, 1865, 125, 78.
3 Karantassis, Ann. Chim., 1927, 8, 71.
J Scbailcr, Annalen, 1869, 152, 135; Btr. y 1868, i, 135; Cooke, Proc. Amcr. Acad.
Arts Sci., 1877, 13, 63, 105.
5 Xickles, Compt. rend., 1861, 52, 396; Sabanejow, Zeif^ch. anal. Ch(-n>., 1871, 10,
205; Kurnakov, Perl mutter and Kunov, J. Russ. Phys. Chew. tioc., 1910, 48, 1058.
fi Ivurnakov, Perlmuttcr and Kanov, loc. cit.
1 Vincent, Zeitsch. anal. Chem., 1880, 19, 479.
8 Kosenhcim and Stcllrnann, Bc.r., )901, 34, 3383; Menschut-kin, Clu-.-m. Zt-nlr., 1010, ii,
378; /. Chim. Phys., 1911, 9, 314.
9 Hiirbcc, Amtr. Chew. J., 1900, 23, 150; Menschutkin, J. Jiuw. Pky*. Ckcni. >S'or\,
1912, 44; 1128.
10 Smith, Btr., 1879, 12, 1420; GodeiYroy, Zcit.-ich. anal. Chem., 1877, 16, 24-4 ; Smith and
Davis, J. Chf-.m. Sac., 1882, 41, 411; Claesson, Bull. 8oc.. <:him., 1876, [2J, 25, 185; Kohlor,
B?.r. y 1881, 14, 1626; Causse, Bull. &oc. chim., 1892, [31, 7, 242; Menschuikm, ,/. Rut*.
Phys. Chem. A'oc., 101 J, 43, 1275, 1303, 1329, 1785/1805; 1912, 44, 1079, 1102, 1108,
1113, 1.137; 1913, 45, 1710; Dunning and Reid, J. Amer. C/iem. tioc., 1927, 49, 2S(>9,
von Euler and Hellsbrom, Svcnfsk Kc,m. Tids., 1929, 41, 11; von Eulor and \Villstardf,
Archiv Kcrni, MmzraL, GeoL, 1.929, 108, Xo. 9, 1; Montmnic, Bull. Hoc. rhnn , 1929,
45, 302; Raudnitz, Bar., 1927, 60 B, 743; Gray, ,/. Ohcm. Kot\, 1926, 129, 317-1 ; Vjuistonc,
ibid., 1914, 105, 1.491; 1925, 127, 550; Vasilicf, J . RUM. Phys. Ck"in. ,SV., 1917, 49,
428; Bdladen and Astcngo, Aiti R. Ar.cad. Linen- , 1923, 15], 32, i, 491, Vanmo and
Muss^nuir, Bcr.< 1 9 1.7, 50, 21; May, J. Chew.. Soc., 1912, 101,' 1037.
JJ SecAdso this Sc^nc^s, Vol. X; Vol. X f, Part, 1IL
'- Karantassis, Ann. Chun., 1927, 8, 71.
1:5 Kararilassjs, Cuutpl. rc.nd., 1933, 196, 1891.
11 iMaz/.iH-c-helli and VVn.-illo, Alii R. Accad. Linc.cl, 1925, | 0], I, 231); Arrivaul, Coin},!,
rend., 19MO, 190, 1506.
15 Maz/.ucc.lu'lh and Wrcillo. hie. cit.
COMPOUNDS OF ANTIMONY. 65
2SbCl 3 .HC1.2H 2 O is obtained in the form of deliquescent crystals melting
at 16 C. It loses hydrogen chloride on heating. 1
Many double salts with chlorides of the metals of Groups I, II and
III have been described, among them being the following :
2LiCl.SbCl ;3 .5H 2 O and 2LiCl.SbCl 3 .6H 2 O. 2
NaCl.SbCl 3 . 3 It is possible that complexes, yielding ions of H 3 SbCl 6 ,
are also formed when antimony trichloride is dissolved in solutions of
sodium chloride. 4
2KCl.SbCl ; >, dimorphic, crystallising in the hexagonal 5 and the
monoclinic systems. 6 Crystals of the latter system have the following
elements : a \ b : c = 0-7241 : I : 0-7222 ; /3 = 111 3'. An hydratcd form,
2KCLSbCl 3 .2H 2 O, has also been described. 7 2KCl.SbCl 3 .SbOCl, pris-
matic crystals of the monoclinic system. 8
KBr.SbClo.HoO, bright yellow octahedra ; 3KBr.2SbCl 3 .2lI 2 O,
bright yellow rhombic crystals ; 3KBr.SbCl 3 .l-5H 2 0, yellow crystals
of the tetragonal system : 9 a : c =1 : 0-7620.
RbC1.2SbCl 3 .HoO, long, colourless crystals (M.pt. 77 C.) of the
monoclinic system : 10 a:'b: c =1-699 : 1 : 0-820 ; fj =90 31}'. RbCl.
SbCl 3 , colourless crystals (no definite M.pt.), monoclinic system: 11
a : b : c = 1-732 : 1 : 1-085 ; /? = 114 26'. 3llbC1.2SbCl 3 , pale yellow
crystals, trigonal rhombohcdral system : 12 a: c = 1 : 0-5625 ; a = 110 54'.
2RbCl.SbCl 3 .SbOCL 13
3CsC1.2SbCl 3 , white or pale yellow prismatic crystals. 14
BaCl 2 .SbCl 3 .2-5lI 2 O, fine, star-shaped crystals. 15
CaCl 2 .SbCl 3 .8H 2 O, large, colourless, tabular crystals, probably of
the triclinic system. 16
MgClo.2SbCl v l()HoO 17 and MgCU.SbCl.,.5lIoO. 18
13cCC.SbClj.3HoO and BcCU-SbCf-j.-llIob. 39 "
3TlCl.SbCl.j, light yellow scales. 20 '
17CdCU.SbCl. r "l8li O, relatively stable, colourless ; 17CoCL 2 .SbCl 3 .
32II 2 O, violet ; AlCl,.3SbCl 3 .GlI 2 0>, very hygroscopic, unstable.* 1
1 Engel, Cow.pt. rend., .1888, 106, 1797; Berthelot, Ann. Chlm. Phys., 1887, [0], 10,
133; Ditto, ibid., 1881, [f>], 22, 557.
~ "Ephraim, titr. f 1903, 36, J82J.
3 Po^iale, Cow.pt. mid., L845, 20, 11 SO; A n/ialcn, 1845, 56, 24-1; Licbig, ^ttand-
wort(-.:rb'uch df.r rr.inc.'u, u-nd, aiKjc.wa.u.dte.n, Chc/mie " (Bra.uii.sc'liwcJLf, 1.837), Vol. I, p. 423.
'" >Saylor, '"Fifth Colloid Sy-Hipoxium J\I o-fiograph," 1927, p. 49.
5 Benedict, Pruc. Amer. Acad. Art* Xc,i., 1894, 22, 2L2.
r ' Benedict, lac,. r/L; Pogcrialo, Compt. rand., 1.845, 20, 1J80; Annul, 18-15, 56, 243.
7 See also Herly, Amcr. Cfie.m. J., 1894, 16, 495; Wells and Foote, A/,u>r. J. tici.,
1897, [4], 3, 4(5 1; ,!ordis, tier., .1903, 36. 2539; Miyakc, Mem. Coll. tiny. Kyaxhn, 1925,
3, 187. 8 Benedict, loc. at.
9 Atkinson, ./. Chan.. &oc. f 1S83, 43, 289; Iferty, loc. cit.
10 Wheeler, Amr.r. J. *SV./., 1893, [3 |, 46, 2(39; 7j(>.il.Mli. an.org. C/i.f-.m., 1893, 5, 253.
n \\'lieelei% lor,. cil..\ H.onisen and -Saunders, Ainc,r. C'hc-.'tn. J., 18!)2, l^j, 155.
1 " \Vheeler, lor.. ciL; .Hemsen and ISaunders, loc. ciL See also Godeilroy, Kc-.r., 1875,
8, II; Wells and Footo, lor,. c,it.
K! Wells and Foote, Loc.. c,it.
14 CodefTroy, for., 1874,7,375; 1875,8,9; F^omscn anrl Saundcrs, loc,. clt. ; ftcilcrhcr^,
Ofrc.r* K.-Vcl.-Akud. Fork., 1862, 6, 20; Muthmnnn, Her., 1893, 26, 1-125; Behrens,
Zcitfir./i. final. C/init., 1891, 30, 103.
1;< Poica'ia.le, loc.. cit.
1(; l^enediet, Proc,. Awr.r. Acad. Arlx Set., 1895, 30, 9; Z(<ilxc.h.. nr,.o,g. Cknn.. 1895, 8, 234.
J7 Kphra.im, Joe. o'L; J^^Lnale, Inc.. r/L
18 Ephraim, loc. clt. ]:) Kphrairn, loc. r/l.
20 Ephrairn and I^arteczko, Zailsch.. anorg. Cham., 1.909, 61, 238.
- l Saueiue, Bull. Soc. Cklm. Rowiii.ia, 1931, 13, 23.
66 AXT1MOXY AND BISMUTH.
Thermal examination of a number of binary systems, involving
antimony trichloride as one of the components, has been made. Among
them the following may be mentioned :
SbCl 3 -LiCl, SbCl 3 -XaCl, SbCl.-KCl, 1 SbOU-KBr, 2 SbCl 3 -XH 4 Cl,
SbCU-CuCl. SbCl 3 -Ao-Cl; 3 SbCl 3 -BaClo, SbCl 3 -HgCl 2 , SbCl 3 -HgBr 2 :
SbCI 3 -AlCl 3 ; SbC'l 3 -SnClo, SbCl 3 -SnCl 4 , 4 SbCl 3 ~SnBr 4 , 5 SbCl 3 -SnI 4 ; 6
SbCl.,-AsCl 3 , SbCl 3 -AsBiC, 7 SbCl 3 -SbCl 5 , 8 SbCl 3 -SbBr 3 , Sbti 3 -SbI 3 , 9
SbCl 3 -BiCl 3 . 10
Oxychlorides of Tervalent Antimony. Many substances of a
complex nature, obtained by different investigators, have been described
as oxychlorides of tervalent antimony ; 11 a study of the hydrolysis of
antimony trichloride, however, suggests that only two of these, namely
SbOCl and Sb 4 O 5 Cl 2 , are true compounds, although unstable inter-
mediate products may be formed. The hydrolysis does not appear to
be progressive, as was thought by early workers. It is probable that by
the addition of sufficient water antimony trichloride is completely
hydrolysed to a hydrated form of antimony trioxide and hydrochloric
acid, the former of which forms a bulky, white, amorphous precipitate.
On standing, this precipitate tends to adsorb hydrochloric acid, the
composition of the resulting product depending upon the concentration
of the supernatant solution. This adsorption product tends to change
on standing for a considerable time into a very finely crystalline sub-
stance, the needle-shaped crystals of which may have the composition
Sb 4 O 3 (OH) 3 Cl 3 ; these in turn are transformed to the oxychloride
SbOCl. From the table on p. 07 it will be seen that the solid phase in
equilibrium with concentrated mixtures of antimony trichloride and
water is the oxychloride SbOCl, while that in equilibrium with more
dilute mixtures is the oxychloride Sb 4 O 5 Cl 2 . The two oxychlorides can
be readily distinguished from one another by their crystalline form. It
is suggested that, the intermediate substance Sb 4 O 3 (OH) 3 Cl 3 reacts in
accordance with the equations
Sb 4 O 3 (OII),Cl 3 +IICJ = 4SbOCl +2II O
Sb 4 O 3 (OH) 3 Cl 3 = SI). t 5 Cl 2 +HoO -f-HCl
It is possible that another intermediate unstable crystalline product,
Sb 4 3 (OH) 5 Cl, may also be formed. The transition from SbOCl to
Sb 4 5 Cl 2 takes place when the concentration of chlorine in the solution
is approximately 8-OA 7 : and the transition from antimony trioxide
to an oxychloride when the chlorine concentration is about 0-1 A 7 .
Examination of the equilibrium of the system Sb O 3 -IICl -IL,O at
1 Kendal, Crittenden and Miller, J. Amrr. Ohf-m. tioc., 1923, 45, 963.
- Tolloczko, Zciifc-h. phynl'ul. Chc,>/>., 1899, 30, 705.
3 Kcndal, Crittenden and Miller, he. cil.
4 Kcndal, Crittenden and Miller, loc. cil.; Tolloezko, Bulletin inUr nationals de
racafltmie dcs Sciences <lc. Craa>r.H>, 190], i, 1.
5 Tolloczko, he. ctt.
r> Bcckmann, Zcitwh. <iu<>r<j. Chcni., I(K)(>, 51, 9C>.
7 Tolloc/ko, he., ctt.: Can-Hi and P.assam, Adi. II. Accn<{. Linca, 1901, 101. 2~>~>.
8 Atcn, Zc.it Heh. phytikaL C/trm.. 1909, 68, 41 ; Moles, v7//V/., 191.",, 90, 70.
'* "Ix-rnardis, Alti. R. Accrtd. Linen, \\\\-> \ ~> \ 21 li -13S
1(1 Tolloczko, he. cit.
11 Schneider, Pogg. Annalr.-n, 1S.19, 108, 407; Sabanejcu , Zctlxcli. C/u-m., 1871, [2], 7,
204,- Williams, Chem. News, IS7J, 24, 224; Cookc, Pruc. Amcr. Aaul. Arts Set., 1877,
13.. 63, JOo: .Frcnzel, J ahre.*b".r 1877, 31, 1286; Morz and Weith, Bcr., 1880, 13, 210.
COMPOUNDS OF AXTIMONY.
67
25 C. revealed no transition points corresponding to the formation of
oxychlorides. 1
EQUILIBRIUM IN THE SYSTEM Sb 2 O 3 -HCl-H,O
AT 25 C.
Chlorine,
gram- atoms per litre.
Antimony,
gram-atoms per litre.
Chlorine,
<j;ram-atoms per litre.
Antimony,
<iram-atoms per litre.'
0-198
0-00012
2-10
0-0522
0-402
0-000172
2-29
0-0755
0-601
0-000298
2-54
0-120
0-709
0-000610
2-81
0-177 j
1-02
0-00124
3-36
0-309
1-32
0-00565
3-85
0-440
1-56
0-0116
4-79
0-745
1-74
0-0194
5-93
1-13
; 1-90
0-0299
EQUILIBRIUM IN THE SYSTEM SbCl 3 -H 2 O AT 25 C.
Solid and Liquid Phases in Equilibrium at Different
Concentrations .
Liquid Phase.
Solid Phase.
Antimony,
per cent.
Chlorine,
per cent.
Antimony,
per cent.
Chlorine,
per cent.
44-0
41-9
69-9
20-7
39-4
38-8
70-0
20-6
33-0
34-5
69-8
20-7
28-7
31-6
70-0
20-6
27-1
30-4
69-9
20-6 ;
23-8
27-9
70-1
20-7
21-2
25-8
70-0
20-7
18-7
23-7
20-7
16-2
21-4
Mixture of Crvstals
14-8
20-7
11-3
11-3
17-5 76-1 11-2
7-5 i 14-3 76-1 | 11-2
4-5
11-7 76-1 11-3
.1-9
9-0 ! 76-0 11-1
1-7 8-9 : 76-2 : 11-2 :
Xote. SbOCl contains Sb 70-29 per cent.; Cl 20-47 per cent.
SbiO.r/'-lo contains Sb 76-34 per cent.; 01 11-lf) per cent.
1 Lea and Wood, ./. Chc.tn. tioc.., 15)24, 125, 137. .See also van .Bemmelen, Xooclt and
Meerburir, ZaitM'.h. an.org. Ghtm., 1903, 33, 272, 289; Berlhclot, An-n. Chim. Phys., 1887,
[C], 10, 133; JLe Chatelicr, Coin/pi, rcnrf., 18S"), 100, 737; 188G, 102, 1388: Diite, ibid.,
1874, 79, 950.
68
AXTTMOXY AXD BISMUTH.
As the conditions of equilibrium within the system SbCl 3 H 2 O-
HC1 (or of the more complete system Sb 2 O 3 -H 2 0-HCl) do not appear
to have been fully elucidated, it may be desirable to include here the
results of investigations by previous workers. In the table below
data are included for three different temperatures, namely 15 C., 1
20 C. 2 and 50 C. 3 For each temperature the formulae of the stable
solid phases are stated, together with the composition, or range of com-
position, of the liquid phase in equilibrium therewith. 4 It will be noted
that the existence of an oxychloride Sb 3 2 Cl r) or SbCl 3 . (SbOCl ) 2 ,
indicated by these investigations, has not been confirmed by the more
recent work of Lea and Wood referred to on p. 67.
EQUILIBRIUM IN THE SYSTEM SbCl 3 -HCl-H 2 O.
(The composition of the liquid phase in each case is recorded as moles of
solute in 100 moles of water.)
Solid Phases.
SbOCl
Sb 4 5 CJ 2
Liquid Phase.
Temperature 15
fHCl 3-66 4-40
\SbCl 3 0-08 0-27
fHCl 0-425 0-46
ISbClo 0-0009 0-0015
Temperature 20 C.
L5 C.
4-78
4-85
5-20
5-24
0-89
2-50
4-75
6-68
2-0
2-76
5 0-0029
0-0167
SbCl 3 ; SboO,
oCi 5 { , i
3-b
Sb 3 O 2 Cl 5 : SbOCl j* 1 ^ ^
SbCl 3
fHCl
\SbCl 3
2-4 6-1 8
71-2 69-9 68
-3 8-2
2 C8-7
Sb 3 2 Cl-
fHCl
\SbCL
6-7 7-8 8
G4 50 35
2
SbOCl
JIIC1
(SbCL
7-3 8-4
8-6 19-7
Temperature 50
C.
SbOCl
fHCl
(SbCl,
3-35 3-82
0-172 0-396
4-24
2-640
Sb 4 5 Cl 2
fHCl
\SbCJ 3
0-18 1-58
0-0008 0-008
2-00
0-012
9-1
68-9
n-7
68-1
28-7
G2-8
2-76
0-046
Hydrolytic dissociation is retarded and. may be inhibited by the
presence of hydrogen chloride, the chlorides of alkali and alkaline earth
metals, and tartaric acid. 5
1 Lc 1 Chatelier, !<>c-. cif.. " van .Benmielen, Xoocll and Meor'bur^, Inc.. r.iL
:t Lo Ch;i teller, Inc.. ?:/{.
1 Abc-L^, ~ Jlandb'i.ch dc/r A-Horyan.ifsc.hcii- Clicmic.^ (Leipzig), 1917, Vol. Ill, Part I],
p. r>9(>.
5 "\Vatson, /. Soc. Chem. Ind., 1886, 5, 590; Watson, Chem. News, .1888, 58, 297;
Sanderson, German Patent, 1890, 54219; Causse, Compt. rend., 1891, 113, 1042.
COMPOUNDS OF ANTIMONY. 69
Antimony Oxy chloride, or Antimonyl Chloride, SbOCl, is obtained as
an amorphous white powder, or in the form of small rhombohedral
crystals, by the hydrolysis of antimony trichloride at the ordinary
temperature as already described, eare being taken to avoid exeess of
water. 1 By heating antimony triehloride with aleohol in a sealed tube
at 160 C., antimony oxyehloricle is also obtained in the form of colour-
less crystals of the monoclinic system:' 2 a : b : c =0-8934 : 1 : 0-7577;
=103 29'.
The heat of formation from the elements is 89,700 gram- calories
per mole. 3
When heated this oxychloride decomposes, yielding first Sb. 4 5 Cl 2
and SbCl 3 , ultimately, with strong heating, passing into a mixture of
antimony tri oxide and antimony trichloride. Volatilisation of antimony
trichloride begins at 170 C. 4 Hot water converts airtimonyl chloride
into Sb 4 O 5 Cl 2 . 5
Antimonyl chloride is insoluble in alcohol and ether, but soluble in
carbon disulphidc, chloroform and benzene, as well as in hydrochloric
acid and in a solution of tartaric acid.
The oxychloride Sb 4 0-Cl 2 may conveniently be prepared by methods
similar to those adopted for SbOCl, using a moderate excess of \vatcr
for hydrolysis, or by heating with alcohol at 140 to 150 C. 6
This second oxychloride is obtained in the form of minute prismatic
crystals of the monoclinic system : 7 a:b : c~ 1-234 : 1 : 3-081 ;
j3 = 1212 / . Its density is 5-0] 4. It melts without decomposition;
but at a higher temperature it is decomposed into a mixture of the
trichloride and the tri oxide. It is not affected by cold water, but it
loses chlorine when treated repeatedly with boiling water, while water
at 150 C. decomposes it completely, antimony trioxide being formed. 8
It is also converted into the oxide by treatment with alkali solutions.
Mineral acids convert it into the corresponding normal salts, oxalic acid
into a basic oxalatc. 9 When heated with sulphur it is converted into
black antimony tri sulphide, with evolution of sulphur dioxide ; inter-
mediate products may also be formed. 30 The heat of formation from
the elements is 328,800 gram-calorics. 11
The following compounds of tcrvalct.it antimony, chlorine and
sulphur, in addition to those previously mentioned (sec p. 62), have
been described. 32 Some of them may perhaps be thiochloridcs :
SbSCl.SbCl 3 , Sb 4 S 5 CL, Sb 5 S G Cl 3 and Sb 8 S n Cl 2 .
1 Sabanejcw, loc. clt.; 'Pcli^oi, Ann. Chini. Phy*-. 9 1847, [ 3j, 2O, 288; Annaltn, 1847,
64, 281: Williams, loc. ciL; Cookc, loc. ciL; i'rcnzcl, loc. cif.; SchaiTer, Annale.ii, 1869,
152., 135; Btr., J868, I, 135.
- Schafler, loc. ciL; Cookc, lac. ciL 3 Gunlx, Ann. Chnn. PAv/.s 1 ., 1884, [GJ, 3, 56.
1 Schailer, loc. at.; 8a.baneje\v, Joe. ciL; Cookc, loc. at.
' Sabanejcw, loc. clt.
r> Sabancjcw, loc. cit.; .Johnston, New ttdi-uburyh Philosophical Journal, 1835, 18, 40;
.7. '}ir(t l;t. Chun.., 1835, 6, 55; Mala^uti, Ann. Ckim. Phy.*.., J835, 59, 220; /. pm/ti. Chun..,
J83"), 6, 253; Pcligot, Joe. a.L; Mac-Ivor, Ohon.. Nawx, 1875, 32, 229; ScJiaiTer, loc. ctL;
Cookc, loc. cit.
"' Sabanejcw, loc. ciL; Cookc, loc. ciL
8 1-Lcnvy,' J. Pftarm., 1820, 12, 79; .Dufio.-s, ^chwc/Kjtjc.r'^ J., J833, 67, 2(38; Malagulj,
loc. <:il., Debray, Com.pt. rend., 1864, 58, 1209; J. pralct. Chem., 1866, 98, 1.51.
9 Bcbrens, Ztdtach. anal. Chc-m,., 1891, 30, J63; fScliaii'cr, loc. cif..; Sabancjew, loc. cil.
]() Grouvcllo, ScJiwei(j(/cr''s /., 1821, 33, 431.
11 G untz, loc. cd.
1J Ouvrard, Compt. read., 1893, 116, 1517; KuM and Fischer, B&r., 1904, 37, 4515;
Tavernc, Chew. Weelcblad, 1908, 5, 19.
70 AXTIMONY AND BISMUTH.
Antimony Tetrachloride, SbCl 4 .- This compound does not yet
appear to have been isolated, but many double compounds formed from
it have been obtained, including 2CsCl.SbCl 4 , 2RbCl.SbCl 4 , TlCl.SbCJ 4
and possibly 3KC1.2SbCl 4 . Many other compounds contain both ter-
valent and quadrivalent antimony ; while still more are known only
in the form of isomorphous mixtures with corresponding compounds
such as platinum tetraehloride and tin tetrachloride. All these com-
pounds are dark brown or deep violet in colour, a darkening of colour
being an indication of the presence of quadrivalent antimony. 1 All
these double compounds, with the exception of one containing both
thallic and thallous chlorides, 2 with the probable formula T1C1.T1C1 3 .
2SbCl 4 , tend to decompose into mixtures of compounds containing
tervalent and quinquevalent antimony. 3 The equilibrium, in solution,
SbCl 3 +SbCl 5 =^2SbCl 4
appears to be greatly dependent upon the temperature and the possi-
bility of ionisation. 4 . The presence of sulphuric acid and of salts favours
the formation of antimony tetrachloride, and the mixture becomes
darker, indicating an increasing proportion of the tetrachloride, upon
addition of hydrochloric acid, or with stronger heating.
Antimony Pentachloride, SbCl 5 . This compound was first
obtained by Rose by the direct union of the elements, powdered anti-
mony combining spontaneously with chlorine, with incandescence. No
antimony trichloride is formed. 5 It is usually prepared by saturating
molten antimony trichloride with chlorine, and distilling under reduced
pressure. 6
Antimony pentachloride is a colourless or faintly yellow liquid,
possessing a sharp odour ; it fumes strongly in air. It melts 7 at 3 C C.,
and yields, at lower temperatures, needle-shaped crystals. 8 Between
15 and 68 C. the density is stated to be given by 9
7)4=2-392 -0-00204J
Under reduced pressure it can be boiled without decomposition, the boil-
ing point at different pressures being indicated in the following table : 1()
i !
Pressure (mm.) . . j 14 j 22 68
i B.pt. ( C C.) . . ! 68 : 79 102-103
1 Weinland and Schmid, Bar., 1905, 38, 1080; Wells and Metier, Amer. Che-m. J.,
1906, 26, 268. See also Bosc-.k, J. Chem. Soc., 1895, 67, 516.
~ Ephraim and Barteczko, Zeitsch. anorg. Chem., 1900, 61, 238.
3 Ephraira and Weinberg, Bar., 1909, 42, 4447.
4 Epliraim and Weinberg, loc. oil. 5 Rose, Pogg. An.n.alen, 1824, 3, 443.
b Anschutz and Evans, tter., 1886, 19, 1994. Sec also Rose, Pogg. An.nukn, 1858,
105, 571 ; Langgutli, Chimie el Industrie, 1931, 25, 22.
7 Moles, Anal. Fix. Quiw., 1914, 12, 314. 8 Kammerer, Ber., 1875, 8, 507.
IJ Sudden, J. Clitin. iSoc., 1927, 130, 1173; Moles, loc. ciL; llaagen, Puyg. A/ihalc/t.,
1867, 131, 122; Ruff and Plato, Ber., 1904, 37, 679.
10 Anschutz and Evans, A-nnalen, 1889, 253, 95. See also Moles, Zcitsck. phyxtkaL
Cheni.., 1915, 90, 70. For other physical properties, see Bccquerel, Ami. Chim. P/LI/J.,
1877, [5], 12, 34; Sehlundt, J. Physical Chem., 1901, 5, 503; Bleekrode, Wic.d. Anna ten,
J878, 3, 179; Walclen, Zcitsch. anorg. Chem., 1900, 25, 219; Zdteck. pkyxikaL Chem.,
1903, 43, 435; Beckmann, Zeitsch. anorg. Chem., 1906, 51, 99; Anschutz arid Evans,
Annalen, 1887, 239, 288; Xasu, Bull. Chem. Soc. Japan, 1934, 9, 198.
COMPOUNDS OF ANTIMONY. 71
The dipole moment, 1 calculated from values obtained for the di-
electric constant, is 1-14 xlQ- 18 c.s.u. (In connection with this the
molecular structure has been discussed.)
The Raman effect has been investigated, 2 both for antimony penta-
chloridc and tor chlorantimonic acid HSbCl G .
Investigation of the boiling ])oints of solutions of antimony penta-
chloride in carbon tctrachloridc and in chloroform indicates that some
dissociation occurs in dilute solutions. 3
The chemiluminescence produced when antimony powder is dropped
into chlorine has been investigated. 4 Two continuous bands were
observed, at 6250 -5200 A. (max. 5950 A.) and 4950 -3930 A. (max.
4650 A.). No antimony lines could be detected.
The behaviour of antimony pentachloridc as a solvent has been
investigated. 5 Chlorine, bromine, stannic chloride, chromyl chloride
and chromic acid dissolve in normal fashion ; iodine trichloride and gold
trichloride undergo dissociation, and iodine, stannic bromide and stannic
iodide react with the solvent.
The heat of formation of antimony pentachloride 6 is as follows :
Sb (solid) +5C1 (gas) =SbCl s (liquid) + 104,900 gram-calories
SbCl a (solid) +2C1 (gas) =SbCl 5 (liquid) -I- 13,800 gram-calories
By exposure to moist air, or by the addition of the required amount
of water, a crystalline monohydrate, SbCl 5 .H 2 O, is obtained ; 7 this
hydrate may be purified by recrystallisation from chloroform. Its
melting point lies between 87 and 92 C. ; under reduced pressure it
can be distilled with decomposition, the pentachloride being evolved at
first, followed by a little trichloride ; a non-volatile residue is left.
When heated under atmospheric pressure chlorine is evolved. 8 The
hydrate is decomposed by water and by a solution of sodium carbonate.
When heated with chloroform or carbon tetrachloride, phosgene is
formed.
A tetralujdratc, SbCl 5 .4H 2 0, has been obtained either by evaporating
a saturated aqueous solution of the pentachloride over concentrated
sulphuric acid, 9 or by precipitation from a solution in chloroform. 10
With excess of water hydrolysis of the pentachloride occurs, with
formation of antimonic and hydrochloric acids ; this hydrolysis can be
prevented by the addition of concentrated hydrochloric acid, or of a
solution of tnrtaric acid ; in the former case, however, chlorantimonic
acid is formed.
Antimony pentachloride dissociates on heating, forming the tri-
chloride and chlorine, 11 the dissociation being slow at 120 C. but
I .BeriitnaMti and Kn^cl, Zcitsch. physikal. Chew., 193.1, 13 B, 232.
- RedJicl), XutwiMHMnschftflcn, 1932, 20, 365; Rcdlich, Kurz and Rosenfekl, Zeitsch.
pliifs'tktil. Chem., J932, 19 B, 231.
' : * Moles, Z(-it*ch. phyxikul. Cham., 191"), 90, 70.
l Bluitna^ar and Mathur, ZtUsch. phy.n/cal Chun., 1930, 9 B, 229.
5 Moles, loc. cit.
6 Thomson, tier., 1883, 16, 40. See also Braune and Tiedje, Zeitsch. anon/. Chem.,
1920, 152, 39.
7 AnscliuLz and Evans, Aunahn, 1887, 239, 287.
s Daubnuva, Ann.alcn, 1877, 186, 118.
<J \Veber, Pof/g. Ann.alcn, 1865, 125, 86.
10 Ansohtit.x and Kvans, Ivc,. cit. ticc also Kosmann, Chem. Zcit., 1887, n, lOoS.
II Hrauiiu and Tiedje, loo. cit.
72 AXTLMOXY AXD BISMUTH.
complete just above 300 C. Between 120 and 260 C. the dissociation
constant is given by
log A' -9-74-
The heat of the reaction is given as 16,320 gram-calories.
With iodine, three main reactions can take place, all of which are
probably complex. 1 When less than 1-5 per cent, of iodine is dissolved
in antimony pentachloride the reaction may provisionally be represented
by
SbCl 5 +2l^SbCl 3 -f2lCl
O o
but iodine trichloride, antimony triiodide and a chloroiodide of quinque-
valent antimony may also be formed. There is, however, no evidence
for the formation of the compound SbCl 5 I. Two double compounds,
SbCl 5 .2lCl and SbCl 5 .3lCl, may also be obtained according to the
equations
2SbCl 5 + 21 = SbCl 5 .2lCl + SbCl 3
3SbCl 5 + 41 = SbCl 5 .3lCl + 2SbCl 3 -f- IC1
These reactions may be carried out by heating the equivalent proportions
of antimony pentachloride and iodine at a temperature of 30 to 35 C.
under a pressure of 15 mm. The existence of these double compounds
has been confirmed by thermal examination.
When dry hydrogen sulphide acts upon antimony pentachloride a
white crystalline compound, SbSCl 3 , is formed. 2 It has a low melting
point and is stable in dry air ; it is decomposed by water into antimony
oxy chloride and sulphur, and by strongly heating into antimony
trichloride and sulphur. It is attacked slowly by concentrated sulphuric
acid with evolution of hydrogen chloride ; 3 ~ it reacts also with chlor-
sulphonic acid.
Antimony pentachloride will react with sulphur monochloride, 4
forming the compound SbCl 5 .SCl 4 . A mixture of equal volumes of
antimony pentachloridc and sulphur monochloride is dissolved in
sulphuryl chloride and the solution dried over phosphorus pcntoxidc.
The equation is
5SbCl 5 -rSoClo =2(SbCl 5 .SCl 4 ) +3SbCJ 3
The compound is obtained in the form of yellow-amber cubes with
octahedral facets ; it fumes strongly on exposure to air, becoming liquid
with separation of sulphur. It melts at 157 to 163 C. It lias no
salt-like properties and is non-polar. A similar compound has been
prepared by the action of sulphur tetraehloridc 5 on antimony penta-
chloride, and by chlorine on antimony trisulphide. 6
The corresponding compounds with selenium tetrachloride, 7 SbCl 5 .
SeCl 4 , and with tellurium tetrachloride, 8 SbCl 5 .TeCl 4 , have been obtained
by the action of dry chlorine upon a fused mixture of antimony and
selenium, or antimony and tellurium. The compound SbCl-.SeOCU has
also been described. 9
1 Ruff, Zedncr and riceht, Bar., 19 15, 48, 2068.
- Cloez, Ann. Chi)//. Phys. t 1850, [3], 30, 374.
3 Clausmzcr, Annahn, 1870, 196, 295; Friedrich, MonatsJi., 1893, 14, 519.
4 Partington, J. CJic.iii. Soc., J929, 132, 2573.
3 Ruff arid Plato, Eer., ]901, 34, 1749; 1904, 37, 4515.
c Rose, Pogg. Annalen, 1837, 42, 532; Weber, Fogg. Annahn, 1865, 125, 78.
T Weber, Poyg. Annalen, 1865, 125, 81, 328.
8 Moles, loc. cit. fl Weber, loc. cit.
COMPOUNDS OF ANTIMONY. 73
Several addition compounds are formed with ammonia, 1 including
a red triannnoniate, SbCl 5 .3XH 3 , a white, volatile tetrammoniate,
SbC] 5 .4XiI,. and a hexammoniatc, SbCl 5 .6XH 3 . The Jirst two of these
ammonia tes react with hydrochloric acid to ibrin the corresponding
ammonium chloride compound. The compound SbCl 5 .XH 4 Cl may be
obtained by heating together equivalent proportions of the binary
compounds in a sealed tube. 2 The monohydrate, SbCl 5 .NH- 4 Cl.H 2 O,
has also been obtained. 3 It crystallises in the rhombic system, and may
be regarded as ammonium metachlorantimonatc. Its crystal elements
are : \i :b: c -0-8909 : 1 : 0-7748.
Antimony pentachloride reacts with nitric oxide and with nitrogen
tetroxidc forming the yellow, crystalline compounds 2SbCl 5 .XO and
3SbCl 5 .2X0 2 respectively. In each case the reactions are accompanied
by considerable evolution of heat. 4
With nitrosyl chloride, the compounds SbCl 5 .XOCl and 2SbCl 5 .
5XOC1 have been obtained. 5
Pliosphinc 6 reacts with antimony pentachloride, hydrogen chloride
being evolved according to the equation
PH 3 4- 4SbCl 5 = 4SbCl 3 + PC1 5 -f 3HC1
A mixture of the pentachloride and phosphonium iodide explodes
violently in air, but when heated in a sealed tube a complex reaction
takes place which may be represented by the equation 7
;3SbCl 5 -t- 3PH 4 I - SbI 3 -r 2SbCl, -i- 9HC1 -f PII 3 + P 2
Antimony pentachloride combines directly with phosphorus penta-
chloride, s and with phosphorus oxychloride, 9 forming the double
compounds SbCl 5 .PCl 5 and SbCl 5 .POCl 3 respectively.
Reactions between, antimony pentachloride and antimony pcnta-
fluoride have already been discussed (see p. 56).
With carbon disulphidc a vigorous reaction takes place, 30 which may
be represented by the equation
2SbCl 5 -i- CS 2 = CC1 4 - 2SbCl 3 -r 2S
If, however, the mixture is kept cold, the compound SbSCl 3 is obtained. ll
Antimony pentachloride is reduced to the trichloride by the action
ot'silicomethane. 12
Wlien antimony pentachloride is heated with germanium tctraiodidc
1 Rose, P >gg. An-tHtlr.n, 1831, 24, 16;!; Persoz, Aim. Chun,. Phy*., 1830, [2 J, 44, 322;
Dchorain, Ccmpt. rend., 1861, 52, 73-4. Soo also Kosonhciin and Jacobsohn, Zeitach.
ivnofg. Chui. 1906, 50, 307.
J Fironai , J. Amw. Cham. ,S'oc., 1904, 26, 741.
:! \\'einlai (1 and Kcigc, Her., ]003, 36, 251; Woinland and .SchJogclnnlcii, Jiu:, 1901,
34, 2633.
I Bossori, ('(iiii.pi. rtiid., 1889, 109, 1012.
G \\'eber, Pogg. Aniiahn, 1864, 123, 347; Hudborough, J. Ckciu. tioc., 1891, 59, 661;
\'a.n I-lotcreji, Zc/dxck. uiiorg. Ckwu., 1900, 22, 278.
II .Malm, Jv<fn.ich<i Zet.tack., 1869, 5, 1.5'J; Rose, Pogg. Annuls, 1831, 24, 165.
7 Fireman, Amc.r. Chem. J., 1903, 30, .1 18.
8 Weber, 'P(>gg. A'ntin.ltn, 3865, 125, 78; Kohlcr, />(/., 1880, 13, 875.
<J \\'eber, loc'. 'at.
10 .Hofmann, A nnalc.ii, 1861, 115, 264.
" .Be.rtrand and JFmot, Bull. &oc. chim., 1880, [-]> 34> -01. See also Husemann,
An.n.'daii y 1861, 117, 229.
l ~ .Malm, JtfM-mche Zcitscli., 1869, 5, 248.
74 ANTIMONY AND BISMUTH.
a reaction occurs which results in the formation of antimony triiodide
and the liberation of iodine : l
4SbCl 5 + 5GeI 4 =4SbI 3 + 1L> + 5GeCl 4
Thermal investigation of the binary system TiCl 4 -SbCl 5 indicates
the formation of a. euteetic 2 containing approximately 40 per cent.
antimony pentachloride (M.pt. -50 C.).
Gold chloride will dissolve in antimony pentachloride, but no
compound appears to be formed. 3
The parachor for antimony pentachloride is 26 units below the sum
of the atomic constants ; 4 it is assumed, therefore, that there are two
singlet linkages, and the formula,
n 6
- ci 6 ci 6
/ \
CF CF
is analogous to that ascribed to phosphorus pentachloride. 5 In this
formula each bond indicates a shared electron, while the superscript
figures give the number of unshared electrons. In certain organic
compounds antimony pentachloride is thought to exhibit an
asymmetrical configuration. 6
Chloroantimonic Acids. Complex compounds arc known to which
the formulae HSbCl G , H 2 SbCl 7 and H 3 SbCl 8 have been ascribed ; these
may be regarded as meta-, pyro- and ortho-chlorantimonic acids
respectively, 7 analogous to the corresponding oxyacids, HSb0 3 , H 4 Sb 2 O 7
and H 3 SbO 4 , respectively. Neither the ortho- nor the pyro-chloranti-
monic acid appears to have been isolated, although salts are known.
Meta-chlorantimonic acid has been obtained by dissolving antimony
trioxide in concentrated hydrochloric acid and saturating the solution
with chlorine. The solution darkens at first, afterwards changing to a
bright greenish-yellow colour. Crystals can be obtained by concentrat-
ing slightly over a water-bath, adding hydrochloric acid and leaving
over sulphuric acid, the temperature not being allowed to exceed C.
The crystals are very hygroscopic ; they are soluble in cold water,
alcohol, acetone and glacial acetic acid. The solution in water under-
goes hydrolysis, especially on warming, hyd rated antimony pentoxide
separating out. Hydrolysis is prevented", however, by hydrochloric
acid, and to some extent by nitric acid. The solutions in. organic
solvents arc more stable. As a precipitate is not formed immediately
on adding silver nitrate to a nitric acid solution, it is suggested that the
1 Karantassis, Cowpt. rtnd., 1933, 196, 1804.
~ Nasu, BulL Chew. Sor,. Japan, 1933, 8, 105.
:i Linclet, Com.pt. rend. 1885, 101, 1494.
1 Sugden, J. Ckem. Hoc., 1927, 130, 1173.
5 Prideaux, Chem. and J-nd., 1923, 42, 672.
(; Fjscher and Taurmsch, Zc-itsch. anorcj. Che'/n., 1932, 205, 309.
Por the action of antimony pentachloride as a catalyst, see Whit by and Katz, J.
Amcr. Cttf.m. Sac., 1928, 50, 1160; Bothandcy, Trans. Faraday Soc., 1928, 24, 47; Knoll
and Co. and Schmidt, British Patent, 1925, 250897.
7 Weinland and Feige, Her., 1903, 36, 244; Weinland and Sehmid, Ztitxch. anorcj.
Chem., 1905, 44, 37.
COMPOUNDS OF ANTIMONY. 75
chlorine and antimony combine to form a complex ion. 1 On the
grounds of the behaviour of the chromium salts of ortho- and mcta-
chlorantimonic acids towards hydrogen sulphide and towards silver
nitrate, and also on account of the resemblance of these salts to the
corresponding hydrated chlorides of chromium, the formulae suggested
for the complex chlorides of chromium and antimony are 2
[Cr(II 2 0) c ][SbCl ] 3 +rH,0
and
[Cr(H 2 O) 4 Cl 2 ][SbCl 6 ] -r GH 2 O
Salts of all these chlorantimonie acids are prepared in a similar
manner ; in general, a mixture of the metallic chloride and antimony
trichloride (or pentachloride) in dilute hydrochloric acid is saturated
with chloryfTe ; crystallisation is effected over sulphuric acid. All the salts
are hydrolysed by cold water, with the exception of those of the alkali
and alkaline earth metals, and even these yield antimony pentoxide on
warming. The presence of hydrochloric acid renders the solutions
more stable.
Salts which have been obtained are given in the following table,
together with their crystallographic characteristics. 3
(A) Salts of ortho-chlorantimonic acid.
CrSbC-l 8 .1ori 2 O Grey, hygroscopic plates.
FeSbCl 8 .8HoO Yellow, hygroscopic, four-sided tablets, tetragonal
system \a : c = 1 : 1-013 2).
(13) Salts of pyro-chlorantimonic acid.
MgSbCl 7 .9TL>O Greenish-yello\v, hygroscopic tablets ; trielinic
system"^/ : b : c =0-714 I- : 1 : 2-595 ; a -100 2l> / ,
(C) Salts of mcta-chlorantimome acid.
LiSbCl G .4lIoO Square, hygroscopic tablets.
KSbCl 6 .Il 2 (3 Greenish-yellow, six-sided, hexagonal plates ; rhom-
bic system (a : 1) : c -0-8889 : 1 : 0-7794).
RbSbClg Thin, six-sided, yellowish-green tablets, rhombic
system (a : b : c = 0-6719 :"l : 0-8136).
XII.jSbCly.HoO Isomorphous with the potassium, salt (a : b : c
0-8909 : 1 : 0-8136).
Bc(SbCl G ) 2 .l()H 2 O Small, yellowish, hygroscopic needles.
Ca(SbC] 6 ) 2 .9H 2 6 Long, hygroscopic needles.
) 2 .5I1 2 O Unstable.
J.j.15li 2 O Greenish-yellow, hygroscopic needles.
Cr(SbCl G ) 3 .1.'3lT 2 O Grey-violet, flat, hygroscopic needles.
The following complex compounds have also been prepared, their
properties determined and their formulae discussed:' 1 XaSbCl 6 .
31-LO.XaU; Cu(SbCl 6 )o.3HoO.HSbCl 6 .5HoO; Cd(SbCl Jo.12(MCU'>IIoO;
SbCl 5 .C 5 H 5 X.HCl ; SbCl 5 .C 9 H 7 X.HCl.
I Weinland and Sehmid, loc. cit.
- Pfeifi'er, 7j(:ittich. (inory. Che.rn., 1003, 36, 340.
3 Weinland and Fcige, loc. cit.; Saueiuc, Bull. Soc. CJilm. Romania, 1931, 13, 23.
II Saueiuc, Ball. Soc. Chhti. Romania, 1930, 12, 3G.
76 AXTDIOXY AND BISMUTH.
The following compounds with ammonia l have also been obtained,
in addition to a number of compounds with organic bases :
5NH.,: A-rSbCl 8 .-2XH 3 ; Zn(SbCl 8 ) s .-tXH 3 : """'"
Antimony! Perchlorate. When a hot solution of antimony trioxide
in excess of perehlorie aeid is allowed to eool, crystals of basic antimony
pcrchlorate, or antimony! perehlorate, SbO.ClO' 4 .2H 2 ; separate out as
small needles.' 2
Antimony and Bromine.
Antimony Tribromicie, SbBr 3 , is formed spontaneously, and with
incandescence, by the direct union of powdered antimony and bromine.
For its preparation, bromine is placed in a retort, and excess of powdered
antimony is added gradually, the mixture being kept cool until all the
antimony has been added, after which the resulting antimony iri-
bromide is distilled. It has also been prepared by the action of excess
of antimony upon a solution of bromine in carbon disulphide. It may
be purified by crystallisation from solution in the same solvent. 3
Antimony tri bromide forms colourless, acicular rhombic crystals
a : b : c =0-817 : 1 : 0-8C9
Its density is 4-148 : it melts at 96-0 C. and boils between 270 and
280 C. 4
The molecular volume, 5 calculated from the density at -191- C 1 .,
is 79-9.
The dipole moment (in solutions with organic solvents) 6 is
2-4-7 x 10~ 18 e.s.u.
Antimony tribromide absorbs moisture from the air, and is immedi-
ately decomposed by it with the formation of an oxybromide. The
formation of this oxybromide is prevented by addition of tartaric acid.
The tribromide is not attacked by either nitric acid or sulphuric acid in
the cold, but on warming bromine is liberated in each ea.se. 7 It. is
partially soluble in ether, forming two liquid lavcrs, the lower of which
contains a compound of the two substances. It is soluble in boron
tribromide. 8 Nitric oxide is without action, but with nitrogen tetroxidc a,
compound, 2Sb 2 5 .X 2 5 , is formed. 9 The heat of formation 10 is o-Jvcn by
Sb (solid) -}-3Br (gas) = SbBr 3 (solid) -f- 76,900 gram-calorics
1 Weinland and Schmid, loc. at.
2 Fichtcr and Jenny, Helv. Clam. Ada, 1923, 6, 225.
3 Serullas, Ann. Cfii-m. Plvys., 1828, 38, 322; Pogg. AnnaUti, 1828, 14, 112: Xicklrs
J. PJiarm. Client., 1862, [3], 41, 145; Cookc, Pror. Ami-r. Avid. Arls Xci JS77 i? ;V>-
fie/-., 1880, 13, 951.
4 International Critical Tablet, ]926, I, 111. Sec also Kopp, Annul? n, 1855, 95, 3.12;
Maclvor, Cham. Ntw*, 1874, 29, 179; Anschutz and Wcyor, Annah'/i, KS5)1, 261, 297.
For other physical properties, see Pebal and Jahn, ll'icd. An.-unlc.n, I88(i, 27,'
Russ. Phy*. Che t/i. Sac., 10] o, 47, 558; 49, 585.
5 Biltz, Sapper and AVnnnenberg, Zeit.sch. a/iorg. Cha/i., 1932, 203, 277.
6 IVlalone and Ferguson, J. Chcrn. Physic*, 1934, 2, 94.
7 Lowig, Reperloriw/if'irr die Pharniacie, 1828, 29, 266.
8 Tanblc, Compt. rend., 1901, 132, 204.
9 Thomas, Compt. rend., 1895, 120, 1116. 10 Guntz, CompL rend., 1885, 101, 101.
OF AXTTMOXV. 77
<> t r. Compounds of Antinionij Tribroinide. A complex acid,
L , has been prepared by the act. ion of hydrochloric, acid on the
salt KoSb.jBr-jj (see below). Jt. is also obtained by the action of hydro-
bromic acid on a solution of antimony tribromide in acetone. It forms
yellow crystals. Corresponding to this acid numerous salts of the
alkali metals, the alkaline earth metals a.nd cadmium have been pre-
pared from solutions of (he mixed bromides in acetone. 1 To these has
been ascribed the % eneral formula, M 2 Sb 3 Br n , where M=K, Xa, Li,
NH^IIoO), a.nd M 2 Ba(2lI 2 O), del." Many of these salts arc de-
composed by water. From an examination of the electrolysis of their
solutions- evidence has been obtained of the existence of the complex
anion Sb.>Br n which subsequently dissociates into 3SbBr 3 and Br 2 .
The compounds KoSb :! Br 9 F 2 , KoSb-jHr^U, SrSb 3 Br 9 Cl 2 , and II.gSb r) Br 18 l 2
have also been obt ained.
Bv substituting potassium nitrate 1 , ])otassium thioeyanatc or
sodiinu a./.ide for the alka.li ha.lide, the com])ounds K 2 Sb 3 Br (NO 3 ) 2 ,
K,,Sb.,Br<,(('NS),, and NaSb 3 Br N 3 have been obtained. The last is a
white, ervstalline substance.
In a. similar manner the ammonium compound, (NH 4 ) 2 Sl)Br 5 .2l:I 2 O,
is obtained in the form of hexagonal prisms.
A vanadium compound, SbBr n . VBr^.TlUO, has been obtained in the
form of black, pointed prisms. It. is hygroscopic and is decomposed
by water.
A complex jim Id compound, f>H bBr.SbBr ;i /2 AuBr 3 , has been prepared.
It is a. black substance, soluble in water a.nd in hydrobromic acid. It
contains no univalent 0*0 Id.* 1
Complex alkyl compounds have been obtained by treatment of
ant imonv t ribromide wit h mixt ures of a.lkyl halides and alkyl sulphides. 4
They appear to have t he const it ut ion | H ,,S |S1
Antimony Oxybromides. Two oxybromides have been described:
(tnt'unoiuil hnnnldt\ SbOBr, obtained by the a.etion of li^ht and air upon
a solution of antimony tribromide in carbon disulphidc, and Sb ;1 () r) Br 2 ,
obtained either bv hydrolysis of a.nt imony tribromide, 7 or by heating
together antimony t ribromide and absolute alcohol in a sealed tube. 8
Ant 5mon\ 1 bromide is a brownish powder (the colour possibly beinn- due
to impurities) which on heating separates into two other substa.noes.
Coiiiinued hcatin<>- con\'erts it entirely into antimony trioxide. The
compound SbjOJ'r., may be obtained in ( he form of monoclinic crystals,
or as a white powder, u hich decomposes on heating, yielding antimony
tribromide and antimony Irioxide.
\\'hilc antimony letrabromide does not appear to have been
isolated, a complex compound of this subsla.nee with ammonium
' ' ' " " bromine and
1S77, 1.^, 101.
(//., IS71, 29, 171); Sc
78 ANTIMONY AND BISMUTH.
bromic acid. 1 It forms black octahcdra of composition corresponding
to (XH 4 ) 2 SbBr 6 . The rubidium salt. Rb 2 SbBr 6 , has also been obtained,
in the form of black, pointed, hygroscopic prisms. It is decomposed
by water. 2
Antimony Pentabromide, SbBr-, has not yet been isolated ; its
existence, however, is indicated by the action of antimony tri hydride
upon an aqueous solution of a mixture of bromine and potassium
bromide, 3 while molecular weight determinations on solutions in
bromine by the boiling point method 4 also suggest the existence of
this compound. Complex compounds with organic bases have been
prepared, 5 in addition to many complex inorganic salts ; these may
perhaps be regarded as salts of bromoantimonic acids.
Of the three possible acids only one has been obtained in the free
state. By crystallisation from a solution containing antimony tri-
bromide, bromine and either hydrobromic or sulphuric acid the com-
pound meta-bromoantimonic acid, HSbBr 6 .3H 2 O, has been prepared in
the form of hygroscopic, irregular, six-sided, black tablets. It de-
composes readily, with evolution of bromine, leaving a residue of
antimony tribromide. 6 The following salts, corresponding to this acid,
have also been prepared :
LiSbBr 6 .4H 2 O Black, square, hygroscopic tablets.
KSbBr 6 .H 2 Stout, six-sided, "black tablets.
NH 4 SbBr 6 .H 2 O Resembles the potassium salt.
Fe(SbBr 6 ) 3 .14H 2 O Black, irregular, six-sided tablets ; very hygro-
scopic.
Ni(SbBr 6 ) 2 .12H 2 O Black, glistening, irregular, six-sided tablets.
Other complex salts that have been described include :
2SbBr 5 .3CsBr.2H 2 Black, microcrystallinc powder.
3SbBr 5 .2BeBr 2 .18H 2 O Black, glistening prisms.
5SbBr 5 .2AlBr 3 ".24H 2 b Black, glistening, stout prisms.
Some of the organic compounds suggest relationship with pyro-
bromoantimonic acid .
Antimony and Iodine.
Antimony Triiodide, SbI 3 , is the only compound of antimony and
iodine that is known to exist with certainty ; a pcntaiodicie has been
reported 7 but subsequent investigations have failed to confirm its
existence. 8
Antimony triiodklc may be obtained by synthesis ; the combination
of antimony with iodine is effected by triturating the two elements
1 Ephraim and Wcinbenr, J>cr., 1909, 42, 4447.
2 Weinlcind and Fei^e. Her., 11)03, 36, 244.
3 Bcrthelot and Petit', Cowpf. rmd.< 1889, 108, 546; Ami. GInm. Phy*., 1889, [6],
18, 67.
4 .Beckmunn. ZrifM'h. plu/NikaL Chc-rn.^ 1 903, 46, 853.
5 .Rosenheim and Sielhnann, 7>Yr.. 1901, 34, 3377.
r> Wcinland and Fci^o, Her., 1903, 36. '24-\.
7 van dor Espt, Arr.k. l*h(tnn... ISO I, \2\, 117, lir>.
8 .MacLvor, Ghr-ui. Xnn, 1002, 86, 1^3; ,J . Clirtn. Nor., 1870, 29, 328; IVmlk-ton,
Gbcm. J\>?/>-, JSS3, 48, 97; Doornbosoli, Prw. K. Al;a<L Wctcnwh. A-wxlf-rdaw, 1911, 14,
025; Jaeger and Doornbosoh, Zcitxch. an.org. G'hcm., .1912, 75, 261; Qucrcigh, AUi It.
Accad. Lust. Vencto Sci., 1912, /o, ii, 667.
COMPOUNDS OF ANTIMOXY. 79
together in a mortar ; the heat generated by the reaction is usually
sufficient to volatilise the triiodide produced, and the reaction may even
become violently explosive if large quantities of materials are employed.
The synthesis is more conveniently carried out by adding an excess of
finely divided antimony gradually to iodine maintained at a gentle
heat. 1 Combination of the two elements has also been effected by
triturating with alcohol, 2 and by adding finely divided antimony to a
solution of iodine in carbon disulphide. In the latter method the
mixture is warmed until the colour of the iodine disappears and the tri-
iodide is obtained by crystallisation from the solution. 3
The compound has also been obtained by heating together equivalent
proportions of antimony trisulphide and iodine, some thioiodide also
being formed, 4 and by adding potassium iodide cither to a solution of
antimony trichloride in acetone, 5 or to an aqueous solution in the
presence of dilute sulphuric acid. 6
Four modifications of antimony triiodide have been described.
Three of these are crystalline and one amorphous. The crystalline
forms belong to the trigonal, rhombic and monoclinic systems respec-
tively. The trigonal form appears to be the most stable at ordinary
temperatures, but the conditions of equilibrium of the system are not
fully understood. Transition points occur at 114 and 125 C., the
former indicating an enantiomorphic change from trigonal form to the
rhombic form, and the latter the transition from monoclinic to trigonal. 7
Cohen, however, states that antimony triiodide is monotropic and the
transition point at 114 C. is purely fortuitous. 8 According to this view
the rhombic form, which is obtained by sublimation, is a metastable
phase which may exist unchanged for long periods even at low r
temperatures.
Trigonal antimony triiodide is obtained as reddish, hexagonal crystals
whose colour varies with the method of preparation :
a= 7-466 A., c= 20-892 A.
There are six molecules in the unit cell. 9 Its density is 4-848 ; it melts at
167 C., and boils 30 between 414 and 427 C. It "will dissolve in cold,
concentrated hydrochloric acid ; the solution on. hydrolysis yields an
oxyiodide. If, however, the solution in hydrochloric acid is boiled for
a few seconds, the triiodide is converted into the trichloride and the
solution on hydrolysis then yields an oxychloride. The triiodide is
readily soluble in hydriodic acid, and from this solution a, yellow oxy-
iodide is precipitated by hydrolysis. It is also soluble in boiling benzene,
1 MacTvor, J. Chcm. Soc., 1876, 29, 328; Cham. Nc,ws, 1874, 29, 255; Brandos, Arch.
Phurm., 1838, [2], 14, 135; 1839, ['2], 17, 283; 1840, [2], 21, 319; Scrullas, J. Pharm.
Chim., 1828, 14, 19; Berthemot, ibid, 1828, 14, 615.
2 Perrier and Lebrument, Bvll. Chi-m. apphcec, 1862, 4, 254.
3 Cooke, Proc. Amer. Acad. Arts Sci-., 1877, 13, 55, 77; Xickles, J. Pharm. Chim.,
1862, [3], 41, 147.
1 Schneider, Pogg. Annalen, I860, 109, 610.
5 Xaumann, Bcr., 1904, 37/4333. Also risk, Amc.r. Mineral., 1930, 15, 263.
G Francois, CornpL rc.nd., 1933, 196, 1398.
7 l-HlcnwHonal. Critical Tables, 1926, I, 111; Cooke, Proc. Amr-r. Acad. Arl.x Kci.,
1878, 5., 1, 72.
8 Cohen and Bruins, Zc.if.firh. physikftl. Chan.., 1920, 94, -165.
Braekken, A'f/L Xortkfi Vidtuskub. Sdxkab*. Forh., 1929, .1930, No. 34, 123; Zcilsch.
Krist. y 1930, 74, 67.
10 Carnelley and Williams, J. Cham. Soc., 1878, 33, 281; Cookc and Bennett, Chem.
News, 1881, 44, 255.
80 AXTDIOXY AXD BISMUTH.
in carbon disulphide, in mcthylene iodide, in an aqueous solution of
tartaric acid, and in arsenic tribromide : the solution in the last solvent
is. however, unstable. With hexachlorethane it forms a dark brown
solution which on cooling deposits first a lemon-yellow mass which
ultimately changes to a red, crystalline substance. The triiodide is
almost insoluble in chloroform, carbon tetrachloride and turpentine. 1
The dielectric constant 2 of solid antimony triiodide at 20 C. is 0-1 ;
that of the liquid at 175 C. is 13-9. The dipole moment (in organic
solvents) 3 is 1-58 x 10~ 1S e.s.u.
The variation of the vapour pressure of liquid antimony triiodide
with temperature is as follows : 4
j Temperature, C. .
j Vapour pressure (mm.)
1
. j 250
. ; 23
; 2G5
35
280 205
53 80
310 325
115 106
Trigonal antimony triiodide is stable in air at ordinary temperatures.
It sublimes quite readily ; if the sublimation is carried out in the
presence of air some decomposition occurs, iodine being liberated and
some oxyiodidc formed. It can be sublimed without decomposition in
an atmosphere of hydrogen or carbon dioxide. It burns when heated
in an atmosphere of oxygen, antimony trioxide being formed. In
common with the other halides of antimony it is readily hydrolyscd by
water, yielding an insoluble, yellow oxyiodide ; 5 the reddish liquid
which is also formed is stated to be a solution of antimony triiodide in
hydriodic acid.
The triiodide reacts readily with chlorine with the formation of
antimony trichloride and iodine monochloride ; with bromine, antimony
tribromide and iodine monobromide are similarly formed. By treat-
ment with molten iodine monochloride the triiodide is converted into
antimony trichloride and free iodine.
Cold, dilute sulphuric acid has very little action upon antimony
triiodide, but if the acid is gently warmed a reaction takes place which
results in the liberation of iodine and the formation of antimony sulphate.
With hydrogen sulphide a reaction occurs at 150 C. and antimony
thioiodide is formed.
Antimony triiodide is readily attacked by concentrated nitric acid
and is converted to antimony trioxide ; free iodine and oxides of
nitrogen are evolved. Dilute acid acts similarly, but more slowly. By
reaction with ammonium hydroxide the triiodide is converted' into a,
yellowish-white powder. Nitric oxide appears to have no ac.tion upon
a mixture of the triiodide and chloroform, but nitrogen tet.roxidc
attacks a mixture of the triiodide and ether with the formation of the
compound 2Sb 2 5 .X 2 O 5 . The triiodide is completely converted into
trioxide by the action of alkali hydroxides and carbonates.
Ztitsch. physikaJ. Chvn., 1893, n, 340.
2 International Critical Tablw, 1929, 6, 7(5.
s M alone and Fermison, ./. Chf-w. 'Ph.y*i'\A, J034, 2, i)4.
4 RoTinjnn/ and Sueliodski, 7jf.itsr.li. physikal. Che. in , 1914, 87, (i.'Jf). For
physical properties, see Worcester, Proc.. Amer. Ac.ad. Arts ,SW., 1SS3/J2J, 10, 01;
tapper and Wurmenberg, Zeitsch. anorg. Cfu-m., 1932, 203, 277.
5 Francois, Compt. re/id., 1933, 196, 1398.
c Thomas, Compt. rend., 1895, 120, 117.
COMPOUNDS OF ANTIMONY. 81
Antimony triiodide is partially soluble in both alcohol and ether,
but the chief effect of both reagents is to convert it into an oxyiodide.
The molecular weight of antimony triiodide, determined by the
elevation of the boiling point of various solvents, is abnormally low. 1
The solvents employed were the trichlorides of phosphorus, arsenic and
antimony, and tin tetrachloride. Cryoscopic measurements using
solutions in methylene iodide also }aelded a low result. 2 This may be
due to the formation of chemical compounds between the solvents and
the solute, or to ionisation of the latter. It is interesting to note that a
solution of antimony triiodide in arsenic triiodide has an appreciable
conductivity, suggesting that ionisation has taken, place. 3
The heat of formation of trigonal antimony triiodide 4 is 44,205
gram- calorics.
When trigonal antimony triiodide is sublimed at a temperature of
114 C. or above, it is converted into the rhombic variety, which is
obtained as small, greenish-yellow lamella?, isomorphous with the
corresponding trichloride and tribromide.
When a solution of the trigonal modification in carbon disulphide
is exposed to bright sunlight for several hours, monoclinic antimony
triiodide is obtained. Some oxyiodide and free iodine are formed at
the same time. The monoclinic modification forms greenish-yellow,
prismatic crystals :
a : b : c = 1-6408 : 1 : 0-6682 ; fi = 109 44'.
Its density (Z)f ) is 4-768. When heated to 125 C. it reverts to the
trigonal modification.
Amorphous antimony triiodide 5 is obtained by cooling a hot con-
centrated solution of the trigonal modification in glycerol. It may
also be prepared by warming the trigonal modification with a small
quantity of potassium acetate and excess of acetic acid ; or by heating
a mixture of antimony tri oxide and potassium iodide with excess of
acetic acid at 100 C. It is a yellow powder which melts at 172 C.
Double compounds of antimony triiodide and ammonium iodide
have been prepared. 6 The compounds 3NH 4 I.4SbI 3 .9H 2 O (bright
red, rectangular prisms), 3XH 4 I.2SbI 3 .SH 2 O (thin rectangular or
tetragonal leaves or plates of a dark reddish-brown, or red colour), 7
lNH 4 LSbI 3 .3H 2 O (large, black, rectangular prisms), arc formed by
crystallisation from a mixed aqueous solution of the two iodides : in
addition, the compound NH 4 I.SbI 3 .2H 2 O (red, tetragonal prisms) is
obtained by the action of iodine on a saturated solution of ammonium
chloride in contact with metallic antimony. 8
Antimony triiodide also forms double salts with iodides of the alkali
metals, the alkaline earth metals, and aluminium. They are usually
prepared by dissolving the triiodide in a solution of the second iodide
and crystallising out from the mixture, 9 or by the action of antimony
1 Beckmann, Zcil.xch. anvrg. Ckem., 1906, 51, 06.
- Garclli and Bassani, Gazzdl.a, .1001, [1], 31, 407.
3 Waldcn, Zeitwh. anorg. Chem., 1902, 29, 371.
4 J-ntcrnniiOiial Critical Tablcx, 1929, 5, ISO.
5 Vournazos, Compt. rend., J9IS, 166, 520.
c 8 chaffer, Pogg. Annahn, I860, 109, Gl.'J.
7 Caven, Proc.'Chfini. Soc., 1905, 21, 187.
s Xickles, Compt. rend., 1860, 51, 1097.
9 SchafTer, Pogg. Anvabn, 1860, 109, 610; Welkow, Her., 1874, 7, 804.
VOL. vi. : v, 6
82 AXTIMOXY AND BISMUTH.
upon a solution of iodine in alcohol in the presence of the second iodide. 1
For example, the compound SbI 3 .2KI.H 2 O has been, obtained by the
former method. 2 They are obtained as reddish-black, transparent
crystals, which are decomposed by heat, by water and by concentrated
sulphuric acid ; they will dissolve in hydrochloric and acetic acids.
Salts of a complex antimony iodohydrobromic acid, HSbBrI 3 , have
been obtained 3 by triturating cquimolecular proportions of antimony
triiodide and metallic bromide with a non-aqueous substance such as
acetic acid or xylene. In this way orange-yellow crystals of sodium
antimoniodobromide, NaSbBrI 3 , and potassium antimoiiiodobromide,
KSbBrI 3 , have been obtained. The corresponding salts of ammonium
and lithium, NH 4 SbBrI 3 and LiSbBrI 3 , are darker in colour, while the
zinc salt, Zn(SbBrI 3 ) 2 , is obtained as brown, tabular crystals which arc
only slowly decomposed by water. The free acid has not been isolated.
Complex compounds of the type R 3 S.SbI 4 (where R represents an
alkyl radical) have been obtained by the interaction of alkyl iodides,
alkyl sulphides and antimony iodide. They are rather unstable ; they
dissolve in acetone, giving coloured solutions. Conductivity experi-
ments suggest the presence in their solutions of complex ions, which,
however, readily undergo dissociation. 4
The following binary systems have been examined by thermal
analysis : antimony triiodide-phosphorus triiodide, 5 antimony tri-
iodi de-arsenic triiodide, 6 antimony triiodide-arsenic tribromide, 7 anti-
mony triiodide-antimony trichloride, 8 antimony triiodi de-antimony
pcntachloride. 9
Antimony Oxyiodide, or Antimonyl Iodide, SbOI, is obtained when
a solution of antimony triiodide in carbon clisulphide is exposed to
bright sunlight in the presence of air. Xo action takes place in the
dark unless ozone is present. It is an amorphous yellow powder, which
decomposes at 150 C., at which temperature antimony triiodide
sublimes ; sublimation ceases at 200 C., the residue, another oxyiodide,
Sb 4 5 I 2 , remaining stable up to 350 C. 10 The oxyiodide Sb 4 O 5 I 2 is
also obtained when a solution of antimoiw triiodide in hyclriodie acid
is poured into boiling water. 11 It is a yellow powder which dissolves
slowly in tartaric acid. It is decomposed when heated to a red heat,
antimony triiodide being removed by sublimation, leaving a residue oi'
antimony trioxide. 12 If a solution of potassium iodide is added to a very
dilute solution of antimony trichloride in water containing a little
sulphuric acid, a bright red precipitate of antimony triiodide is obtained.
If insufficient sulphuric, acid is present, however/ an orange precipitate
of 2Sb 2 3 .SbI 3 is obtained by hydrolysis. 13
Xickles, loc. cit. - Francois, Compt. rp.ad., 193;">, 200, 393.
Voumazos, Compt. rend., 1922, 174, 164.
P. C. Ray, Adhikari and A. X. Ray, J. Indian Chrm. Soc., 1931, 8 7 2ol.
Jaeger and Doornboscb, Zeitsch. anon/, Ckcm., 1912, 75, 2(31.
Jaeger and Doornbosch, loc. til.; Qu'erciiib, At.ti Jl. Accad. Lined, 1912, 21 I, 415;
lief, ./. liuss. Phys. Chcm. Sac., 1910, 44, J07(5.
Walden, Inc.. riL
Bernardis, Atti R. Accad. Lined, 1012, [>], 2 i II, 438.
Beckmann, Znlsch. tcnory. C'h(-m., 190?', 55, 17.1; Moles, Zc.i'.lscJ/.. -phiis-lb-il. Chmi.,
90, 70.
COMPOUNDS OF ANTIMONY. 83
The product obtained by the action of water upon antimony tri-
iodidc is of variable composition depending upon the temperature and
concentration. 1 There is some indication that a complex acid,
H 2 (SbOI 3 ), is formed, the mercuric and cupric salts of this acid having
been obtained. Mercuric antimony oxyiodide, HgSbOI 3 , is prepared by
warming a mixture of equimolecular proportions of mercuric cyanide
and antimony triiodide in moist amyl alcohol upon a water-bath for
four or six hours. It melts at 78 C. and is decomposed by concentrated
acids and by alkalis. It can, however, be rccrystalliscd from solution
in cold, dilute, hydrochloric acid. Cupric antimony oxyiodide, CuSbOI 3 ,
is obtained by a similar reaction between cupric acetate and antimony
triiodide. 2
Another complex acid, [Sb(IO 3 ) 3 (OH) 3 ]H, is stated to have been
obtained by the action of antimony pentachloride upon an excess of
iodic acid. 3
Antimony Thioiodide, SbSI, is obtained by the action of antimony
trisulphide on antimony triiodide, 4 by the action of iodine upon anti-
mony trisulphide, 5 or by the action of hydrogen sulphide upon antimony
triiodide heated to 150 C. 6 It crystallises in small, dark red, lustrous,
needle-shaped crystals of a form similar to those of kermesite. It melts
at 392 C. and above this temperature decomposes forming a mixture of
trisulphide and triiodide. It is not decomposed by hot or cold water,
or by dilute acids. Hydrogen sulphide is set free by the action of
concentrated hydrochloric acid ; sulphur and iodine by the action of
concentrated nitric acid. Alkali hydroxides and carbonates remove
iodine, leaving a residue of thioantimonites.
Several antimony iodocyanides have been obtained. 7 By heating
mercuric cyanide and antimony triiodide in dry xylene, mercuric
antimony iodocyanide, Hg[SbI 3 (CX) 2 ], is obtained. Further heating
results in the formation of tri mercuric antimony iodocyanidc,
Hgy[Sb 2 I ( .(CN) 6 ] : while the corresponding cuprous compound,
Cu G [Sl) 2 I 6 (CX) G |, is obtained in a similar manner.
Mixed Halides. Several compounds which may be described as
mixed halides have already been mentioned. Others have been pre-
pared by various methods. The halidcs of the elements phosphorus,
arsenic, antimony, titanium, tin and perhaps germanium, when mixed
together, readily undergo reactions which involve an interchange of
halogen atoms. The mixed halidcs so formed, however, have not been
isolated. 8
Ajitimony TrifLuorodichloride, SbF 3 Cl 2 , may be prepared by the
action of chlorine upon antimony trifluoridc 9 at a temperature above
70 C. The antimony trifluoridc should be dissolved in antimony
trichloride, pcntachloridc or tribromidc. IT treated with bromine or
1 Scrullas, LOG. cit.; Bcrlhomol, J. Pharm. CUin., .1828, [2|, 14, 615; Bottger and
Brandos Inc. cit.
rnnms, CunipL />//'/., 1020, 170, 1250.
lay and S. X. Kay, -/. .Indian, dhcnf. Nor., 102(1, 3, 110.
Sot
ncidcr, Pofjfj. A/i.na [<:n, .1800, no, 150.
: Tan], Com.pl. mid., 1S03, 117, 108; Sr.lmeider, Pofjfj. An mil en, 1 8(iO, 109, 010.
: if-.ois, Co'/npL ri\nd., UJ.'M, 198, 100-1; Ouvrard, loc. ciL
rnazos, lor,. ci.L
8 Racder, Kyi. Norsle Vulensbtb. Sckkabs. 8/crifler, 1920, No. 3, 1.
u Henne, British Patml, 1933, 389619; United States Patent, 1934, 1984480.
84 AXTIMOXY AND BISMUTH.
iodine, the corresponding compounds 1 antimony trifluorodibroimdc,
SbF JBr 2 , and antimony trifluorodiiodide, SbF 3 I 2 , are formed.
Antimony BromocUiodide, SbBrI 2 , is formed by adding a solution of
bromine in chloroform to a solution of ethyldiiodostibine in chloroform.
It is obtained as long yellow crystals 2 melting at 88 C.
By the interaction' of mercuric bromide with antimony triiodidc
(preferably in the presence of a suitable organic solvent), 3 the complex
compound antimony mercuribromoiodide, SbI 3 .6HgBr 2 , has been
obtained.
ANTIMONY AND OXYGEN.
Three oxides of antimony are known with certainty, namely anti-
mony trioxide, Sb 2 3 , antimony tetroxide, Sb 2 O 4 , and antimony
pentoxide, Sb 2 O 5 ; a complex oxide, Sb 6 13 , may also exist. 4 It is
probable that some of the confusion which existed among earlier
workers in connection with certain of the oxides of antimony may have
been clue to the extreme slowness with which equilibrium is obtained
between antimony pentoxide and its decomposition products. 5 Three
of the oxides resemble one another very closely in crystal structure, one
modification of each of them possessing a cubic lattice of the diamond
type. The oxide Sb 6 13 may have a tetragonal lattice. 6
Lower oxides of antimony have been described by early writers, but
the evidence for the existence of these does not appear to have been
confirmed. 7
Antimony Trioxide, Sb 2 3 . This substance was known in ancient
times ; it is probably referred to by Pliny under the name of stibia
femina. and by Basil Valentine under the name flores Antimonii. The
latter name was subsequently applied to the product derived from the
roasting of antimony sulphide. Antimony trioxide occurs naturally in
the minerals senarmontite and valentinite, and in certain other more
complex minerals (see p. 9).
The trioxide may be prepared by the direct oxidation of antimony,
by heating in air or in water vapour ; 8 by the action of concentrated
nitric acid, in which case a mixture of oxides is obtained ; 9 or by fusion
with potassium nitrate and potassium bisulphatc. 10 The higher oxides
of antimony may be reduced to the trioxide by the action of sulphur
dioxide u or hydriodic acid. 12
When antimony trisulphide is roasted, a mixture of oxides of
antimony is obtained, from which the trioxide can be separated by
1 Friddaire Co., French Patent, 1932, 732320.
2 Clark, J. Chem. Soc., 1930, 133, 2737.
3 Vournazos, J. prakt. Chem., 1933, 136, 41.
4 Simon and Thaler, Zeitsch. anory. Chem., 1927, 162, 253.
5 Simon and Thaler, loc. tit.
c Dehlinger and Glocker, Zcitsck. nnorij. Chem., 1927, 165, 41; Simon, Zcittch. anorg.
Chem., 1927,' 165, 31; Dehlinsrer, Zeitsch. Krist., 1927, 66, 108; Bozorth, J. Amer.
Chem. Soc,. f 1923, 45, 162] ; Dehlinger, Zcitsch. phy-nkal. Chem., 1929, B. 6, 127.
7 Berzelius, Schweigcjer's J., 1812, 6, 144; 1818, 22, 69; Jones, J. Chem. Hoc.., 1876,
29, 642; Marchand, J. prald. Chem., 184."), 34, 381 ; Bottler, ibid., 1856, 68, 372; Proust'
Gilbert's Aminlen, 1807, 25, 186.
8 Baker and Dixon, Prc>c. Jioy. Nor.., 1888, 45, 1 ; Roonault, Arm. Ch>ni. /'/r//.v 183(5
[2], 62, 362; Do bray, Compt. rend., 1864, 58,' 1209.
Brandos, Arch. Pliarm., 1840, [2], 21, 1,36; Preuss, Annalen, 1839, 31, l!)7; I-fosc,
Pogg. Aniialen, 184], 53, 161; Borxelius, Scluw<j(jct''s J., 1812, 6, J44; 18 IS, 22, (\\).
10 Preuss, loc. cit.
11 von Knorre, Zeitsch. angeu: Chem., 1888, I, 155.
12 Bunsen, Annalen, 1858, 106, 1.
COMPOUNDS OF ANTIMONY. 85
fusion with more antimony trisulphide. 1 The trioxide may also be
obtained from the trisulphide by treatment with concentrated sulphuric
acid, followed by the addition of an alkali carbonate to the solution
obtained. 2
Many antimony compounds may be decomposed by suitable reagents,
yielding antimony trioxide. Thus, antimony 1 chloride is completely
converted to the trioxide by treatment with water at 150 C. ; 3 anti-
mony salts are decomposed by alkali hydroxides and carbonates, and
potassium antimonyl tartrate is decomposed by the action of salts of
weak acids such as borates, acetates, thiosulphates, phosphates, sulphites,
etc., 4 trioxide being formed in each case.
Technical antimony trioxide, as used in the manufacture of paints,
is frequently obtained direct from antimony ores or concentrates. 5
Antimony trioxide is dimorphous, the two modifications crystallising
in the cubic and rhombic systems respectively. Both modifications
occur naturally, the cubic as senarmontite and the rhombic as valentin-
ite ; both can also be produced artificially, the cubic by sublimation and
the rhombic by the hydrolysis of solutions of antimony trichloride. 6
Although both modifications can exist unchanged for long periods at the
ordinary temperature, the cubic modification is the stable form, the
rhombic form being stable at higher temperatures. In support of this
view, it is found that a specimen of antimony trioxide after prolonged
heating at 550 C. yields cubic crystals only ; after similar treatment at
590 C. rhombic crystals only are obtained. Rhombic crystals separate
from the melt on crystallisation, but these are completely converted
to cubic crystals by prolonged heating at 550 C. At a temperature
of about 570 C. both cubic and rhombic crystals are in equilibrium
under the pressure of their own vapour. The transition temperature
is therefore at approximately 570 C., the cubic modification being
stable below this temperature and the rhombic above. 7 Further
support for this view is afforded by an examination of the vapour
pressure curves of the two modifications (fig. 2) ; 8 the computed
transition point, however, appears to be slightly lower than the value
recorded above.
Cubic antimony trioxide (senarmontite) contains eight molecules of
Sb 4 G in the unit cell 9
a = 11-14 A.
Its density determined by pyknometer 10 is 5-19, by X-rays, 5-49. Its
hardness on Mohs' scale is 2-6 to 2-5. The specific heat n is 0-093 gram-
I Bor/.clius, luc. ctt.; Shakhov and Slobodska, Tzvet. Met., 1930, 1294; Chimie et
Industrie, 1931, 25, 1126.
- IIomuML', ./. Pharm. Chim., 1848, [3], 13, 355; Lindner, Zeitsch. Chem., 1869, 5, 442;
J>ull. Hue., chim., J869, [1 ], 12, 455; Durand, /. Pharm. Chim., 1842, [3], 2, 364.
:1 Dcbray, Co-mpt. rand., 1864, 58, 1.209; J. prakl. Chem., 1866, 98, 151.
l JLoii,"J. Awc,r. Chem. Soc., 1895, 17, 87.
5 Ust rat, U.S. Pulen.t, 1932, 1873774; Antimon Berg- und Huttcn\verke A.-G.,
Pratch PdtcM, 1930, 706371; Deutsche Sclimelz- und Raffinierwerke A.-G. and H. W.
Gnmm, Ihitinh Patc.nt, 1930, 348138; French Patent, 1930, 696448.
(; Torrcil, Ann. Chita. Phy*., 1866, [4-j, 7, 350; Pasteur, ibid., J848, [3], 24, 442; 1850,
[3J, 28, 56; I85J, |"3], 31, 67; Mitschcrlich, J. prakt. Chem., 1840, 19, 455; Rose, Poyg.
Ann.ul.(-H; 1832, 26, 180; von Bonsdorif and Mitscherlich, ibid., 1828, 15, 453.
7 Roberts and Femvick, J. Amir. Chem. Soc., 1928, 50, 2134.
8 Ilinekc, -ibid., 1930, 52, 3869. 9 Dehlinger, Zeitsch. Kn*t. y 1927, 66, 108.
10 Simon, Zt-Mxch. anory. Chem., 1927, 165, 31.
II liittrnatioiiul Critical Tables, 1929, 5, 95. Sec also Neumann, Ann. Physik, 1865,
126, 123; Rcgnault, Ann Chim. Phys., 1841, i, 129.
ANTIMONY AND BISMUTH.
calories per gram. The melting point is approximately 650 C. and
the calculated molar latent heat of fusion (assuming the molecule to
450
650
500 550 600
Temperature, C,
FIG. 2. Vapour Pressure Curve of Antimony Trioxidc.
700
be Sb^e) 1 is 29,490 gram-calories. The vapour pressure (in millimetres)
below the melting point is given by '
log, -12-195 -1
The dielectric constant 2 is 12-8, and is not affected bv hi,* field
strengths. 3 - to Lm
1 Hincke, loc. cit.
2 Giinther-Schulze and Keller, Zcltsch. Physik, 193? vq 73
3 Giinther-Schulze and Betz, ibid., 1931, 71, 1Q6. ' ""'
COMPOUNDS OF AXTIMOXY. 87
VAPOUR PRESSURE OF ANTIMONY TRIOXIDE.
l^einpmituro, ('.
: Pressure
(mm. Mercury).
Modification of SbA)^.
450
0-
010
Rhombic (metastable)
450
0-0075
Cubic (stable)
475
0-
0224
. ?
500
0-
0625
?J
550
0-
406
557
0-
525
Ckibic and rhombic (stable)
575
! 0-
90S
Rhombic (stable)
GOO
2-
42
. ,
0*25
3-
91
. ?
G42
7'
43
Cubic (metastable)
(550
7*
60
Rhombic (stable)
G55
8-
50
.,
675
10-
42
Liquid
700
13-
32
, .
750
20-
78
,,
1456
760
lihombic antimony trioxidc, in the form of the mineral valentinite,
liu.s -the crystallographic axial ratios 1
a:b: c= 0-3910 : 1 : 0-3364
Tlie density of the synthetic form 2 at 27-4 C. is 5-99; that ot the
mineral is 5-57. The hardness of the mineral on Mohs' scale is 2-5 to
**<). The molar ]icat capacity of the prepared form at low temperatures
(n.s suming the molecule to be SboO : >) is as follows :
IVm poruture, C. . -213-2 -198-3 -182-4 - 104-3^ - 120-7 -92-0
U >! a. i* lical capacity
(-r<Lin-calories) ". 6-893 9-114 1097 13-11 10-97 19-0,:
-!-!() -i-17-")
3-57 24-49
I^Iic; calculated molar latent heat of fusion 3 is 13,250 gram-calorics.
TIio vapour pressure (in, millimetres) is given by
9,625
:i iid the molar heat of vaporisation is 22,040 gram-calories. The molar
hcn.t ol! transition from the cubic to the rhombic modification is 1,620
<_> rj \, m -calorics. 4
1 .La.spoyrcs, Zc.itvch. Krysl., 1884, 9, 102; 13rczina, Ann. j\IuaeiLin Witn., 1880, I, J45;
<. ; r x)<,Ii, ./V/r/. An;ii<il(:ii, ]8(39, 137, 429.
~ Anderson, J. Anto.r. Chc-.m. Sue., 1930, 52, 27 J 2. 3 Hincke, luc. ciL
' l Sec also Roberts and Pcmvick, J. Amc.r. Chun. Soc., 1928, 50, 2140.
.For oilier physical properties, see Sclmhmarm, J. Anif-r. C'hf-.m. Soc., 1924, 46, D2 :
( ; r ipponberg, ibid., J91.I, 33, 1701; Jaeger, Zeitsck. Kryxt. Mm., 1907, 44, -15; Bill/.,
Xr.iixch. pliysikdl. Cham., 1896, 19, 385; J3iltc and >let/.ner, Compt. rand., 1892, 115, 930;
1C. ideal, 7>V,/., 1880, 19, 589; Gitntz, Compt. rend., 1880, 98, 589; Hensgen, Jtc-.c.. Trar.
<-}iim ,, 1885, 4, 401; Grosse-Bohlc, Zcitsch. KryxL, 1881, 5, 222; Meyer and Menschhig,
38 ANTIMONY AND BISMUTH.
Antimony trioxide, when heated in air, undergoes no change at
temperatures below 860 C. Above that temperature it absorbs oxygen l
and is converted into the tetroxidc. At a higher temperature the
tetroxide dissociates into trioxide and oxygen ; the dissociation begins
at about 900 C, and is complete at 1,030 C.
Antimony trioxide is almost insoluble in both hot and eold water,
and also in dilute nitric and sulphuric aeids ; it will dissolve in dilute
hydrochloric acid. 2 It is oxidised by concentrated nitric acid, a mixture
of oxides being formed in which antimony pentoxide predominates. 3
With concentrated sulphuric acid, antimony sulphate is formed. 4 The
trioxide is soluble in alkaline solutions, forming antimonites ; 5 it is
also soluble in tartaric acid, 6 in lactic acid, 7 and in certain other organic
compounds. 8 The statement that antimony trioxide is oxidised when
boiled with aqueous alcohol has been contradicted. 10
At a red heat antimony trioxide is reduced by hydrogen ; reduction
also occurs on treatment with hydrogen under the influence of the silent
electric discharge. 11 Hydrogen peroxide is without action.
A complex reaction occurs when the oxide is heated with chlorine,
antimony tri- and penta-ehlorides being formed in addition to antimony
tetroxide. The last is decomposed on further treatment with chlorine. 12
When antimony trioxide is melted with a little sulphur, a mixture
of antimony trisulphide and antimony trioxide, known as " antimony
glass,' 5 is obtained ; with excess of sulphur, antimony trisulphide and
sulphur dioxide are formed. A reaction also occurs between antimony
trioxide and antimony trisulphide resulting in the formation of metallic
antimony. 13 Thermal investigation of the system Sb 2 O 3 -Sb 2 S 3
indicates the formation of a compound Sb 2 O 3 .5Sb 2 S 3 or Sb 4 OS 5 (fig. 4). 14
When a current of hydrogen sulphide is passed over the trioxide a yellow
coloration is produced in the cold ; when heated an oxysulphide is
obtained. 15 With ammonium sulphide the trioxide reacts with the
formation first of an orange-coloured oxysulphide which passes ulti-
mately into the trisulphide. With sulphur monochloride, antimony
trichloride is obtained : 1G
6S 2 Cl 2 +2Sb 2 O 3 =4SbCl 3 +3S0 2 +9S
Jier., 1879, 12, 1282: Groth, Pogg. Annalen, 1869, 137, 426; Fizeau, Ann. Chim.
Pkys., 1866, [4], 8, 360; Playfair and Joule, J. Chem. Soc., 1846, 3, 83; liegnault, Ann.
Chim. Phys., 1836, [2], 62, 362; Karstcn, Schwtiggtr's J., 1832, 65, 394; Boullay, Ann.
Chim. Phys., 1830, [2], 43, 266.
1 Carnellcy and Walker, J. Chem. Soc., 1888, 53, 86; Shakhov and Slobodska, loc. ci(.
2 Terrell, Ann. Chim. Phys., 1866, [4|, 7, 380.
' a Pchgot, Compt. rend., iS46, 23, 709. - 1 Schultz-Sellack, Ber., 1871, 4, 13.
5 Mitscherlich, J. prakt. Chem., 1840, 19, 455; Cormimboeuf, Compt. rend., 1892, 115,
1305. G Schulze, J. prakt. Chem., 1883, [2], 27, 322.
7 Kretschmar, Chem. Zcit., 1888, 943; Waitc, Ttchn. Jakresber., 1887, 1161.
8 Vogcl, Ber., 1885, 18, 38: Henderson and Prentice, J. Chem. Soc., 1895, 67, 1030;
1902, 81, 658; Rosenheim and Bierbrauer, Zeitsch. anorg. Chem., 1899, 20, 281: Jordis,
ZcitscJi. angew. Chem., 1902, 15, 906: Kohlcr, Dingl. poly. J., 1885, 258, 520.
9 Tingle, J. Amer. Chem. Soc., 1911, 33, 1762,'
10 Edgerton, ibid., 1913, 35, 1769.
11 Miyamoto, J. Chem. Soc. Japan, 1932, 53, 788.
12 Weber, Pogg. Annalen, 1861, 112, 625; Willgerodt, J. prakt. Chem., 1885, 31, 539.
13 Schoellcr, J. Soc. Chem. Ind., 1914, 33, 169; 1915, 34, 6; sec also Milbauer, Chem.
Zeit.. 1916, 40, 108.
14 International Critical Tables, 1928, 4, 46; Quercigb, Atti R. Accad. Lincti, 1912,
21 I, 415. 15 Schumann, Annalen, 1877, 187, 312.
16 Oddo and Serra, Gazzetta, 1899, 29, II, 355; Prinz, Annalen, 1884, 223, 356.
COMPOUNDS OF ANTIMONY. 89
Phosphorus trichloride is decomposed by antimony trioxide with
the formation of red phosphorus. 1 The oxide dissolves slightly in
phosphoric acid, some phosphate being formed.
The trioxide is reduced when heated with carbon and certain carbon
compounds such as carbon monoxide, potassium cyanide, sodium
formate, etc. 2 From an examination of the equilibrium conditions of
the reduction by carbon monoxide, according to the equation
Sb 2 O 3 +3CO ^ 2Sb -r3CO 2
between 502 and 596 C. the change in free energy 3 is given by
A F = - 33,461 -f 34-2862" log T - 0-Olllor 2 + 0-00000093T 3 - 88-65T
Reduction of the trioxide is complete at 500 C. 4
Antimony trioxide reacts also with silicon tetrachloride 5 forming
antimony trichloride and silicon ; and with silicochloroform 6 in the
presence of sodium hydroxide, in which case metallic antimony and
hydratcd silica arc obtained. It may be reduced to metal by the action
ol' boron nitride. 7
The more active metals such as potassium, magnesium and alu-
minium act as reducing agents ; fusion with alkali nitrates results in the
formation of! aiitimonates. When fused with caustic soda and sulphur
a mixture of antimonate and thioantimonate is formed, 8 but fusion
witli sodium hydroxide and arsenic leads to reduction to the metal. 9
The heat of formation of cubic antimony trioxide 10 is 149,690 200
gram-calorics per mole.
Hydrated Antimony Trioxide has not been obtained by direct
methods, but three substances, obtained by indirect methods, have been
described as ortko-, pyro- and meta-antimonious acids, respectively,
with the formula H 3 Sbb 3 , II 4 Sb 2 5 and HSbO 2 . The first, which may
also be regarded as antimony hydroxide, is obtained by the action of
dilute sulphuric acid on a double tartratc of antimony and barium. 11
The substance, formerly known as pyro-antimonious acid, which is
obtained when antimony trisulphide is heated with a solution of
potassium hydroxide, and copper sulphate then added to the mixture, 12
was subsequently 13 shown to be ortho-antimonic acid, H 3 SbO 4 . The
substance described as mcta-antimonious acid, HSbO 2 , is obtained by
the- decomposition of a double tartrate of potassium and antimony,
using an alkali carbonate, phosphate or acetate. 14
There is, however, no conclusive evidence for the existence of these
hydraled forms of antimony trioxide. No evidence for the existence
1 Michaelis, /. prald. Chun., 1871, [2], 4, 449; Bull. Soc. cliim., ]S72, [1J, 17, 205.
- NVhssL'ii, Hull. Ac'.vl. roy. Mel?/., 1887, [3], 13, 258.
:! YYatanabe, Bull. Intl. Pkyx. Chem. Ibma-rcli, Tokyo, 1929, 8, 973.
4 \Vatanabe, *S'n.. Jic.p. Jwp. Univ. Tohoku, 1933, 22, 407.
6 Uaiuer, Anna Ian, 1892, 270, 251.
< ; liuft and Albert, Btr., J905, 38, 2234.
7 Mosor and Eidmann, Bcr., 1902, 35, 535.
8 MiLschciiieli, ,/. pra/d. Cftcm., 1840, 19, 455. Sec also Factor, Pharm. Post, 1905,
38, 527; ISrctt, Phil. May., 1837, [3J, 10, 97.
<J Kirsebom, Frc.nch Patent, 1930, 694283.
RoberU and Fcjiwick, loc. cit. Sec also Mixter, Amer. J. Sci., 1909, [4], 28, 103.
1 Clarke and Stallo, JJer., 1880, 13, 1787; Guntz, Compt. rend., 1886, 102, 1472;
m-lley and Walker, ,/. Clmm. Soc., 1888, 53, 60.
- Schailner, Aniialtn,, 1844, 51, 182.
:1 Scrono, Cazzetta, 1894, 24, II, 274.
1 Long, J. Amc.r. Cficm. tioc., 1895, 17, 87.
90 ANTIMONY AND BISMUTH.
of definite hydrates has been obtained from dehydration curves, 1 and it
seems probable that the various substances described are colloidal
modifications of hydrated antimony tri oxide differing in linencss of
division. 2
Antimonites. Antimony trioxide is aniphoteric 1 , its basic, pro-
perties being the more highly developed. Most antimony salts derived
from this oxide are, however, hydrolyscd by cold water, the exceptions
being the trifluoride and some salts of organic acids. Its acidic pro-
perties are shown by the formation of antinionites by the action of
solutions of alkali and possibly of alkaline earth hydroxides. These arc
mainly meta-antimonites, derived from the hypothetical acid HSbCX ;
but other more complex substances have been obtained.
Sodium meta-antimonite, XaSb0 2 , may be taken as typical. It is
obtained by fusing together antimony trioxide and excess of sodium
carbonate ; 3 a trihydrate has also been obtained. 4 It is oxidised by
fusion with caustic soda in contact with air, by hydrogen peroxide, and
by the halogens. 5 By treatment with hydrogen sulphide a tbioanti-
monite is formed; 6 and with sodium thiosulphate a mixture of sodium
pyroantimonate and thioantimonate is formed, the thiosulphate being
reduced to sulphite. 7 In solution the sodium salt reacts with solutions
of many metallic salts. With copper salts it yields a precipitate, prob-
ably of copper antimonite, soluble in nitric acid. 8 With an ammoniucal
solution of barium chloride, with solutions of mercurous salts, mereurie
chloride and leael and ferric salts precipitates are formed in. each case,
while with ferric salts a reddish solution is ultimately formed. With
silver nitrate a complex reaction occurs yielding a black precipitate,
which is a mixture of silver oxide, silver and antimony ; 9 while with
gold chloride a black precipitate is obtained which is possibly gold
antimonite. 10
A solution of sodium antimonite is reduced by stannous chloride, and
is oxidised by potassium permanganate, potassium dichromatc or
potassium ferri cyanide. 31
Other, and in many cases more complex, antinionites that have been
formed include the sodium salt XaSb 3 O 5 , which is obtained by the
prolonged boiling of a mixture of excess of antimony trioxide and a,
solution of sodium hydroxide, 12 and the salt Xa 2 Sb 4 O 7 . A potassium
salt of indefinite composition has been describee! by a number of t In-
early observers. 13 The two salts KSb 3 5 and K 2 Sbj Pl Oo 5 .7ll 2 O have
1 Simon and Poehlrnann, Zeitsch. anorg. Che//i., 1925, 149, 101.
- See also Lea and Wood, J. Chem. Soc., 1923, 123, 259; Mitschciiiuh, ,/. /,/>//,/ (<hnn
1840, 19, 445. '
Mitscherlich, J. prakt. Chem., 1840, [1], 19, 455.
4 Terrell, Ann. Chim. Phys., I860, [4], 7, 352; Cormimb(x>uf, Com.pt. n'tid., 1892, 115,
loOo.
5 Rose, Pogg. Atmaltn, 1824, 3, 441; Fremy, Ann. Chim. Phys., 3848, 131 2? -{()!
J. prah. Chem., 1848, [1], 45, 209; Mitsclierlich, he. cit.; Hagcr, Znttck. anal <://,/ '
187 r' "'. 8 i-' , , r G Ten-oil, /oc. ell.
' vveinland and Gutmaun, Zeitsch. a/iorg. Chem., 1898, 17, 413.
8 Terrell, loc. cit.; Harding, Zeit.sch. anory. Chem., 1899 20 235
9 PiUitz, Zeitscfi. anal Chem., 1882, 21, 27, 49G; see' also ~Teri-eii, loc. cit Rns<>
loc. cu.\ isuusen, Annalui, 1858, 106, 1.
^ Harding, loc. cit.- Rose, loc. cit. " Q.uincke, Zeitsck. anal. Chem,., 189 fc >- 31 35
l ~ Cormimboeut, loc. cit.; Terrell, loc. cit.
^ Berzelius, Schweiggers J., 1812, 6, 144; Brandos, ibid., 1831, 62 199- Rose and
\^ientT^p Pogg.Annalen, 1839, 47, 326; von Liebig, Poggendorlf and Wohlcr -'//,/^/-
ch far remc,i und ungcivandten Chemie" (Braunschwei") 1837 i 414 '
COMPOUNDS OF ANTIMONY. 91
been obtained, the former as minute, prismatic crystals. 1 Antimonites
of copper have been obtained by a fusion method, 2 while the mineral
tkrombolite probably also contains a compound ol % this type. 3 Anti-
monitcs of the alkaline earth metals have not been isolated, but indica-
tions of their existence have been obtained, 4 while the mineral romeite
may contain an antimomte of calcium. 5 Antimonites of zinc, mag-
nesium and lead, 6 and of iron, cobalt and nickel, 7 have been obtained.
In addition, complex compounds of antimony trioxide and alkali
molybdatcs and tungstates have been described". 8 Of the tungstates,
the " following may perhaps be mentioned: 9 2BaO.Sb 2 3 .llW0 3 .
18H 2 O ; 6(XH 4 ) 2 O.Sb 2 0,.18W0 3 .38H 2 0; 6(CH 6 N 3 ) 2 O.Sb 3 .18W0 3 .
SlHoO ; 8KoO.SboO 3 .19W0 3 .3TH 9 ; 2j-(NH 4 ) 0.2Sb^0 3 .10WO,.
12EUO ; 3Ko6.2Sb 2 O 3 .10WO 3 .6H 2 6 ; 2i-(CH 6 N 3 );0.2Sb;O 3 .10W0 3 .
6H 2 6; 2JBa6.2Sb 2 O 3 .10W0 3 .18H 2 0.
Antimony trioxide is used under various trade names, such as cc Luv
extra," " Leukonin " and i: Timonox," as an opacifier mixed with paints.
The commercial product is usually a mixture of oxides. It can be used
with all colours and oxides except those containing lead. The durability,
hardness and speed of drying of antimony white paints are stated to be
less than for zinc white paints. 10 The trioxide is also employed in
enamels, but certain countries have introduced legislation curtailing
its use on food, receptacles on account of its poisonous nature. It
has been shown that whilst antimony in the quinquevalent form is
comparatively harmless, it is poisonous in the tervalent form since it
is then soluble in dilute acids - 11 (sec p. 46).
Antimony Tetroxide, Sb 2 O 4 , or Antimony Dioxide, Sb0 2 , is found
naturally as the mineral ccrvantite. It may be obtained by a variety of
methods, such as by the prolonged heating of antimony trioxide in air,
or by the calci nation of antimony pcntoxide, 12 or by heating the trioxide
with excess o:f mercuric oxide. 13 It is usually prepared by heating
antimony or antimony trisulphide with nitric acid and igniting the
residue at a dull red heat until the weight is constant. 14 An impure
form may be obtained by the careful roasting of antimony trisulphide,
at a temperature below the melting point, until no more sulphur dioxide
is evolved. 10
I Cormimbauif, foe. ci.t.
- Tammann, Zc.ittidi. anonj. C/LCVI., 1925, 149, 68; 1927, 160, 101; Balareff, ibid.,
1927, 160, 92.
3 Breithaupt, J . pra/d. Ghent.., 1838, [1], 15, 320; Schrauf, Zci.tach. KrysL, 1880, 4,
28; Domcyko, " 1C In nun lot* da JMiiitraloyw" (Santiago), 1871.
l Tammann, loc. af..; BalaretT, loc. at.
5 Damour, An.u. Mines, 1841, |3], 20, 247; Groth, ; ' Tabdlar indie, Uebersicht der Miner -
alien" (Braunschweig), 1^9, 7J ; "Schallcr, Jhdl. U.ti. Gaol. Survey, 1916, 610; Pelloux,
Ann. Mus. Gloria. A'aL Goic.m, 1913, [,3J, 6, :22; Schroder, " Goldschmidt's Atlas der Kris-
tdllfortntn," 1913, i, .121; H usaak, Ccntr. Min., 1905, 24.0.
(i Tammann, /oc. cU.; .BalafciT, loc. cM.
7 Bcrzoliux, loc. clt.; Tammann, loc. c/L.; .Balaieir, loc. cit.
8 Gibbs, A mar. Ch.cni. ,/., 1885, 7, 313, 392.
y Koscnheim <uid. WoliT, Zcitxch. anortj. Chc.m., 1930, 193, 64.
" Miillcr, Glax/rultc, .1932, 62, 320; Jiikcr, Atntr. Paint /., ]933, 17, Xo. 39, 47; Koike,
Farbf.n Zcilwiy, 1033, 38, 67(5; Hanpt and Topp, Ktrani. Rundschau, 1927, 35, 221;
van Hock, Furbvtt, Zut.u-!i</, 1932, 37, 1222, 1255; 38, 43, 1749.
II Vlelzer, GlaxhiitU:, 11)29, 59, 865; .Haupt and Popp, loc. at.; Koike, loc. at.
l - Bcrzehus, tichw.itjtjc.rx J., 1812, 6, 144. ::! Bunsen, Antialun, 1878, 192, 31o.
14 von Szilajryi, Zcttvck. anal. Cha,i. y 1918, 57, 23; Dexter, Pogy. Annalen, 18o/, 100,
503; Bunsen, loc. cit.
~
92 ANTIMONY AND BISMUTH.
Antimony tetroxide is a refractory, white powder, massive as a
mineral ; it becomes yellowish on heating*, reverting- to white when cold.
The crystal lattice is cubic, 1 with = 10-22 A. The density oi.' the
synthetic substance 2 at 23-8 C. is given as 0-47. Tins value is con-
siderably higher than that given for the mineral (see p. 9). The specific
heat is 6-0951 ; 3 the molar heat capacity at low temperatures is given
in the following table (in gram-calories per mole) : 4
^ , .. - 200-2 j- 182-4! -130-4
Heat capacity. I 8-317 ! 10-02 i 14-72
Temp., C.
-129-2! -79-3
16-57 ! 21-37
-72-1! -16-6: -M -1-11-9 i
21-74 i 25-23 23-10 27-17 \
The tetroxide is stable at a red heat, but loses oxygen when heated
more strongly. 5
The crystal structure of antimony tetroxide suggests that the
antimony atoms are not all equivalent, 6 and from a comparison with the
structure of the similarly constituted antimonates of lead and calcium it
is suggested that the oxide may be antimony antimouate, Sb' n Sb A 4 .
Antimony tetroxide is soluble with great difficulty in water and in
acids. It is slightly acidic, imparting a faint reddish colour to moistened
litmus. 7 It is only slightly attacked when heated with hydrochloric
acid, but dissolves in hydrochloric acid containing hydriodic acid, with
liberation of iodine, according to the equation
Sb 2 O 4 + 6HC1 + 2HI - 2SbCl 3 -f 4lI 2 + 1 2
This reaction may be employed for the estimation of antimony tetroxide. 8
When heated with a little sulphur an oxysulphide or Ci antimony
glass " is formed ; with more sulphur the trisulphide is obtained. 9
Alkali hydrosulphides have no action in the cold, but when warmed they
act as solvents, hydrogen sulphide being evolved.
The tetroxide can be reduced to the metal by heating with carbon,
potassium cyanide or the alkali metals ; the trioxide is obtained on
heating with antimony. The tetroxide will also react with antimony
trisulphide : when excess of the tetroxide is employed the trioxide is
formed with liberation of sulphur dioxide :
9Sb 2 O 4 -f Sb 2 S 3 = 10Sb 2 3 -f 3S0 2
With excess of the sulphide, ''antimony glass" is formed.
The heat of formation from the elements 10 is 209,800 gram-calories.
A hydrated form, Sb 2 O 4 .II 2 O or II 2 Sb 2 5 , is found in the mineral
stibiconite. It is acidic, and the free acid, meta-lujpoantimonic add, may
J Dehlingcr, Zeiixch. KrisL, 1927, 66, 108.
- Anderson, /. A-m&r. Cham. Soc., 1930, 52, 2712. See also Karston, Schwciygers J.,
1832, 65, 394; Playfair and Joule, Memoirs Chem. Soc., 1845, 2, 401.
3 Regnault, Ann. Cktm. Phy*\ } 1841, [3], I, 129; Pogy. Annakti, 1841, 53, 73.
4 Anderson, loc. cit.
5 Foote and Smith, J. A-mtr. Chem. Soc., 1908, 30, 1344: Dexter, loc. cit.; Eaubi^ny,
Coni-pt. rend., 1897, 124, 560; Brunck, Zcitsch. anal. Chcm., 1895, 34, 171: Read, J. Gfi.tiii.
Soc., 1894, 65, 313: Carnellev and Walker, ibid., 1888, 53, 86: Guntz, C um.pt. read., 1S85,
101, 161.
6 Xatia and Baccaredda, Zcitsch. Krist., 1933, 85, 271.
7 Rose, Pogg. Annalen, 1824, 3, 441.
8 von Szilagyi, loc. cit.
s Proust, Gehleris ally. J. Chem., 1805, 5, 543; Gilbert's Annah,i, 1807, 25, 186.
10 Mixter, Amer. J. Science, 1909, [4], 28, 103.
COMPOUNDS OF ANTIMONY. 93
be prepared as a white, flocculent powder by decomposing solutions of
its salts by acids. The potassium salt may be obtained by heating
antimony or antimony trisulphide with potassium sulphate or b
sulphate : other salts may be prepared by double decomposition. It
has been suggested, however, that these salts are mixtures of antimonites
and antimonates. 1
Antimony Pentoxide, Sb 2 O 5 . Antimony pentoxide and its
derivatives were employed in the sixteenth and seventeenth centuries
as diaphoretics. 2 A potassium salt was described by Basil Valentine by
the name of " antimonium- diapJioreticum, ablutum " ; it was prepared
by deflagrating a mixture of antimony and saltpetre and washing the
residue with water and alcohol. A similar substance was c; antimmiium
diaphoreticum non ablutum." The acid, or oxide, was probably obtained
by the action of acids upon the above substances, and was used medicin-
ally under the name of Ci materia perlata Kerkringii." Glauber obtained
a similar product, which he called " benzoardicum miner ale" by the
action of nitric acid upon antimony trichloride. 3
Antimony pentoxide may be prepared by heating antimony, or a
lower oxide of antimony, with nitric acid or aqua regia. 4 It may also
, be obtained by ignition of the hydrated pentoxide (antimonic "acid),
which may, in its turn, be prepared by the hydrolysis of antimony
pentachloridc. It is formed in a variety of reactions, many of which,
however, are not suitable for its preparation. Among these reactions
may be mentioned the action of alkaline hydrogen peroxide upon
antimony 5 or antimony trioxide ; (5 and the deflagration of a mixture
of antimony, antimony trioxide, antimony trisulphide or potassium
antimony! tartrate with potassium nitrate.
Antimony pentoxide is a pale, lemon-yellow powder, without taste.
Its density is 3-78. It crystallises in the cubic system, with a lattice
constant similar to that of the tetroxide. 7 The arrangement of the
oxygen atoms in the lattice, and the effect of adding oxygen atoms
within the range Sb 2 O 4 to Sb 2 5 , affords a possible explanation for the
development of colour in the neighbourhood of Sb 6 13 . 8 The pentoxide
is insoluble in alcohol, but soluble in tartaric acid. 9
The heat of formation, calculated from thermal data obtained in the
1 For the chemical properties of antimony tetroxide., see also Berzelius, Schwciggcr's J.,
1812,6, 144 ; 1818, 22, 69 ; Delffs, -/. prakt. Chew.., 1847, 40, 318; Schnabel, Pogy. Annahn,
18f>8, 105, 346; Cnmenge, Ann. Mines, 1851, [4], 20, 80; Frenzel, Zeitsch. Kryst. Min.,
1.877, 2, 629; Santos, Cham. News, 1877, 36, 167; Rammelsberg, " Ha-ndworterbvch des
cJtMH-ifichen Theils der Mincralogic^ (Leipzig), 1875, 175, 188; Fremy, Ann. Chim. Phys..
18-1-1, [3], 12, 498; von Licbig, loc. cii, 1/414; Websky, Zeitsch. anal Chcm., 1872, n, 124.
- A diaphoretic is used for promoting or increasing perspiration.
3 'Dyson, Pharmawuiicul J. and Pharmacist, 1928, [4], 67, 521; Kopp, " Geschichie
dc-.r Cficmic^ (Braunschweig), 1843-1847, 4, 108; Libavius, "Alchymia'''' (Francofurti),
159;!; Lemcry, "Cours d(> Chimic" (Paris), 1675; Basil Valentine, "The Triumphant
Chariot of A~i!t'twony," London, 16()1; Croll, "Basilica chymica" (Frankfurt), 1609;
Glauber, " I'h'i.rniacopw.ft. ppdqyric.n"' (Amstelodani), 1650-1670.
l Berzeliu.s, loc. c-it.i Bourson, J. pnikt. Chcm., 1839, 17, 238; Conrad, Chcm. New*,
1879, 40, 197; Bosek, J. Chcm. Hoc., 1895, 67, 515; MilJon, Ann. Chim. Phys., 1842, [3],
6, JO I ; Rose, J\>(/r/. An-n.ftff.ti, 18-11, 53, 161; Lefort, J. Pharm. Chim., 1855, [3], 28, 93.
"' Clark, Chrni.' Xcwx, 1893, 67, 24 ( .>.
<; ZamMLi and Luz/aito, Arch. Pharm., 1886, |2|, 224, 772; Hampe, Chr-m. Zrit.,
1891, 1 8, 1899.
7 Dch linger, Zc.ilM'.h. A'/-is7., 1927, 66, 108.
8 Delilin^er, Znlsch. phijfiikal. Chcm., .1929, 6 B, 127.
a J'layfair and Joule, Slcmoirs Chcm. 6'oc., 1845, 2, 401; Boullay, Ann. Chim. Phyx.,
1830, \2], 43, 266.
ji4 AXTIMOXY AXD BISMUTH.
oxidation of the clement or lower oxides by means of sodium peroxide, 1
is 22f),()0() oTam-calories. The molar heat capacity at low tempera-
tures (in oTam-calories per mole) calculated from determinations of
specific heat on two hydrated forms 2 is given in the following table :
-3
26-54
The pentoxide is decomposed on heating, decomposition beginning
at about 300 C. with the formation of antimony tetrox-ide, 3 and also by
hydrogen under the influence of the silent electric discharge. 4 With
chlorine it forms antimony trichloride ; 5 hydrochloric acid has a slight
solvent action, but no chlorine is evolved. It is reduced by phosphorus
trichloride. 6 Hydriodic acid reduces it to antimony trioxidc with
liberation of iodine. 7 This reaction affords a delicate qualitative test
for antimony. 8 The reaction
SboO, -f 4HI Sbo0 3 +2EUO +2I 9
- o ^ o 2.
is reversible, and the equilibrium conditions have been studied with
reference to the influence of varying concentrations of the reacting '
substances and of the presence of certain other substances. 9 Reduction
3f the antimony pentoxide is practically complete in the presence of
:-xcess of potassium iodide or hydrochloric acid, the latter being the more
MTective. The presence of tartaric acid reduces the amount of iodine
;ct free ; cadmium iodide acts similarly ; but the presence of neutral
-alts, or a rise in temperature, increases the amount.
Antimony pentoxide reacts with sulphur to form antimony trioxide,
>r antimony trisulphide, according to the proportion of sulphur, 10 the
cactions being represented by the following equations :
SboO, +S= SboO., -f-SOo
2Sb 2 CL + US = 2SboS3 -f 5SO 2
Vhen heated in a current of hydrogen sulphide a black oxysulphide,
h 4 OS 5 , is formed ; ll an orange-red precipitate of antimony pcnhi-
ulphide is obtained with a solution of hydrogen sulphide. This prc-
ipitate is soluble in warm alkali sulphides, and very slowly soluble in
mmonium sulphide. Sulphuric acid, both dilute and concentrated,
issolvcs antimony pentoxide only slowly and after prolonged action,
he pentoxide reacts with sulphur monochloride 12 with the formation
f antimony trichloride :
6S 2 Clo -2Sb 2 5 =4SbClo -f 5SOo - TS
- Mixtcr, Arncr J Sri., 1909, [4], 28, 103. 2 Anderson, loc. cii.
3 Duuhrawa. Annahn, 1877, 186, US.
1 Miyamoto, J". C'/tr-w. ,SV.. JY/;w/?, 1932, 53, 788.
"' \Vebcr, /V^/. Annril(-n, 1SG1, 112, G2o'
G Michaelis, J. ^7.V. 67^:/w.. J871, 4, 43J,
I-iunscn, Annnkn, 1S.~>S, 106, i.
^ KIdn irr//. /V^/;,,,., ISSi), 227, 922; Giraud, ^.//. Hoc.. Mm., 1S86, [21, 46 504-
"-i: ami (,nu ; n, t -, ^-,/.r7/. r/^/7. Vhn*., 1S93, 32, 471; Well,,-, Anna'
^' K<'n?-!^i ^'rm'lrib''^ ] ? 8 "' 4S 1<)! ^ R hn ^ r '.^ r " J!M)I ' 34- lr ^5.
10 Kamnielsber^, / ; oj7j7. A-nnalen, 1841 52 -">41
'- 1 Schumann, .4a7e N , 1877, 187, 312. '~" u Prmz> ^, m ^^
COMPOUNDS OF AXTIMOXY. 95
Antimony pentoxide is partially reduced when heated with carbon
ui the blowpipe (lame, but for complete reduction admixture with
sodium carbonate is necessary. Carbon disulphide l and silicon tetra-
c-hloride 2 also act as reducing agents, chlorine being evolved in the
latter case.
Aqueous alkali solutions have only a slight solvent action, but
antimonates are formed on fusion with alkalis. Reduction occurs on
fusion with potassium cyanide, potassium formate, the sulphides of lead,
copper and silver, 3 antimony and antimony trisulphide.
Antimony pentoxide liberates chlorine from potassium chloride 4
and iodine from potassium iodide. 5 in both cases on heating in the
presence of oxygen.
Stannous chloride produces a darkening of the colour of antimony
pentoxide, the resulting product containing stannous oxide. 6 The
pcntoxide is reduced to antimony by the action of tin and hydrochloric
acid. 7
The hydration of antimony pentoxide has been studied by many
investigators, and, while earlier workers reported a number of definite
hydrates, more recent work suggests that the hydrates of antimony pent-
oxide resemble those of stannic oxide in being colloidal. Three of the
so-called hydrates have been studied, being prepared respectively by
(1) the hydrolysis of antimony pentachloride at to 1 C., (2) the
hydrolysis of antimony pentachloride at 100 C., and (3) the oxidation
of antimony trichloride by nitric acid and hydrolysis of the product at
()() C. The results suggested that gels were formed in each case, the
behaviour of these depending upon grain size, this in turn varying with
t he method of preparation. The three products contained the following
molecules of water per molecule of antimony pentoxide after treatment
as described : 8
(1) ( 2 ) (3)
Dried on porous plate . . . 30-57 9-97 7-91
Dried over sulphuric acid . . 3-68 2-17 0-60
Dried at. 105 C 2-4-3 1-02 0-45
Alcoo'ds of antimony pent-oxide have also been prepared, and their
de-aieoholation curves were found to be similar.
Sols have been obtained by the hydrolysis of concentrated aqueous
solutions of antimony pentachloride at C. Freezing point determina-
lions of these solutions suggest analogies with soap solutions, while pll
values indicate that, on subsequent dilution, the micelles decompose
further and ionise. Certain of the more stable solutions suggest a
molecular weight of a very high order. The soluble products arc acidic,
and are probably hydrosols of low stability. It is probable that the
ortho-, pyro- and mcta-antimoiric acids have no free existence. Towards
alkalis, these hydrates show marked selective adsorption, forming
amorphous substances, probably antimonatcs, of indefinite composition.
1 Mullcr, />(/(/. Anna Icii, ISfiO, 127, 40 I.
' Hu.uicr, An-iiulm, 1S<):>, 270, 2f>0.
:i Ka minclshcru,, lac . r/l.
1 Scliul/.o, ,/. 7//Y//V. ('/if-ni., iScSO, 21, 4;>7.
"' Srlionl>cin, /'<></(/. Aunnlcn, \ S4), 78, f) I \\.
96 AXT1MOXY AXD BISMUTH.
Certain crystalline antimonates may also be obtained by dissolution in
concentrated alkali solutions, followed by careful evaporation at low
temperature. 1
Evidence has been obtained for the existence of the definite hydrate
3Sb 2 O 5 .5H 2 O from a study of the behaviour of gels obtained by the
hydrolysis of antimony pentachloride, 2 and also for the existence of a
dihydrate and a hemihydrate. The formula HSb(OH) 6 has also been
suggested for antimonic acid. 3 Earlier investigators have described
several hydrates obtained by the following methods : by the decom-
position of a solution of potassium antimonate by nitric acid ; 4 by the
hydrolysis of antimony pentachloride ; 5 by the repeated action of
aqua regia on antimony ; 6 by the action of nitric acid upon antimony
trichloride. 7
Much confusion exists as to the nature of the many antimonates
that have been obtained and described. It seems fairly certain that only
in a few instances notabh' the salts of iron and aluminium arc normal
ortho-antimonates obtained, the majority oP the salts being either acid
ortho-antimonates of the type KH 2 Sb0 4 , or meta-antimonates of the
type KSb0 3 . The elucidation of the constitution of these salts is
handicapped by the difficulty experienced in determining the true
water content of the solid substances. From conductivity determina-
tions in solution it appears probable that both the potassium and the
sodium salts are acid ortho-antimonates of the above type. 8 The
following compounds have been obtained by the interaction of a con-
centrated solution of a salt of the metal with a concentrated solution of
sodium antimonate : 9
Oriho-antimonates Fe. 2 O 3 .Sb 2 O 5 .7H ; AU0 3 .Sb 9 O s .9HoO.
Meta-antimonates CuSboO 6 .oH 2 O ; " Ag Sb 2 O 6 .3HoO ; " BeSb,0 G .
6H 2 0; BaSb 2 O 6 .5H 2 O ; ZnSb 9 O 6 .5H,0 ; CdSb O 6 .6lI 6 : PbSb^O,.
5H 2 O ; MnSb 2 O G .5H 2 O ; XiSb" 2 O 6 .6lf 2 O ; CoSb" 2 O 6 .6HoO. The last
two have also been obtained with 12 molecules of water of hydration. 10
In man}' cases the proportion of water retained in the molecule
depends upon the conditions of preparation. In general, this water is
1 Jander, Kolloid Zeitsch., 1018, 23, 122; Lottennoser, Zeitsch. Elelctrochcm., 1927,
33, 514.
2 Simon and Thaler, Zeitsch. anorg. Ghent.., 1927, 161, 113.
3 Pauling, /. Amer. Chcm. Soc., 1933, 55, 1895; 1933, 55, 3052; H.animott, "Solutions
of Electrolytes" (New York), 1929, 108; Brintzinirer and YVallach, Angcw. Chcm., 1934,
47, 61.
4 Heffter, Pogg. Annalen, 1852, 86, 419.
5 Daubrawa, Annalen., 1877, 186, 110.
6 Conrad, Ch.em. News, 1879, 40, 197.
7 Senderens, Bull. Soc. chim., 1899, [3], 21, 47. For the properties of these products,
see also Geuther. J. prakt. Chcm., 1871, 4, 438; Fremy, ibid., 1848, 45, 21.1; Baubigny,
Compt. rend., 1897, 124, 499; Capitaine, J. Pharm. Ghvm., 1839, 25, 516; -7. prakt. Che/n.,
1839, 18, 449; Beilstein and von Blase, Bull. Acad. St. Petersburg. 1889, [4], I, 97, 20 J, 209;
Chew.. Zentr., 1889, I, 803; 1890, I, 350; Schiff, Annalen, 'l857, 102, 111; Luckow,
Zeitsr.h. anal. Chem., 1897, 26, 14; Delacroix, J. Pharm. Chim.., 1897, [6], 6, 337;' Bull. Soc.
cfiim., 1899, [3], 21, 1049; 1901, 25, 288; Lottcrmoscr, Zeitsch. Eleldrochcm., 1927, 33, 514.
8 Tomula, Zeitsch. anorg. Chem.., 1921, 118, 81; Delacroix, Bull. Soc. chim., 1S09, [3],
21, 1049; J. Pharm., 1897, [fi], 6, 337; Senderens, Bull. Sac. chim., 1899, [3], 21, 47;
Baubigny, Compt. re/id. , 1897, 124, 499; Beilstein and von Blase, Chc.m. Zf.ii.tr., \ 8S9,
I, 803 1 1890, I, 350; von Knorre and Olschewsky, ./>/-., 1885, 18, 2353; 1887, 20, 3043;
Raschrg, -ibid., 1885, 18, 2743; Fremy, Anm. Chim. Phi/s., 1844, [3], 12, 490; J84S, 22, 404.
9 EbeJ, Bcr., 1889, 22, 3044; Inavg. JJis.wtnt-tou, Hcrlm, 1890- Chcm Zc.ntr L891 II
414.
10 See also Schiff, Annalen, 1861, 120, 55; Schneider, Pogg. Annalen, 1850, 98, 304;
Heffter, ibid., 1852, 86, 418,
COMPOUNDS OF ANTIMONY. 97
removed completely by heating to 100 C. or by drying over concentrated
sulphuric acid. In the case of potassium antimonate it is much more
difficult to remove the water, and the suggestion has been put forward
that in this case a pyro-antimonate may be formed.
Alkali antimonates are to some extent soluble in water, but anti-
monates of the heavy metals are, in. general, soluble onh^ with difficulty.
The solubility of sodium meta-antimonate (expressed in milligrams
Xa 2 O.Sb 2 O 5 .6H 2 O in 100 c.c. of solution) is 56-4 in water at 18 C., 0-1
in a mixture of equal volumes of water and ethyl alcohol, and 3-1 in a
2-5 per cent, solution of sodium acetate. 1
Most antimonates are decomposed by concentrated acids with the
formation of hydrated antimony pentoxide. Solutions of alkali anti-
monates react slowly with sulphuretted hydrogen in the absence of other
alkali salts, an orange-red precipitate of antimony pentasulphide being
formed ; they react with carbon dioxide to form a white precipitate of
an acid alkali antimonate. 2
A number of naturally occurring antimonates has been examined
and the constitutions have been discussed. 3
ANTIMONY AND SULPHUR.
Three sulphides of antimony have been described : the trisulphide,
SboS^, the tetrasulphide, Sb 2 S 4 , and the pentasulphide, Sb 2 S 5 . Some
doubt has been expressed concerning the existence of the tetrasulphide
as a true compound, and it is probable that the pentasulphide has not
yet been obtained in a pure condition. Early investigators described
a subsulphide, Sb 2 S 2 , obtained by fusion, but this was quickly proved
to be a mixture, or solid solution, of antimony and antimony trisulphide.' 1
Thermal examination of the system antimony-sulphur indicates
the existence of one compound only antimony trisulphide, Sb 2 S ;r
which gives rise to a maximum on the free/ing point curve at 546 C.
One eutcctic is obtained, containing 57-5 atomic per cent, of sulphur,
and melting at 520 C. A second eutcctic has been reported, containing
61-3 per cent, sulphur and melting at 51 9 C. Two liquid layers arc
obtained at each end of the system, at 530 C. for the sulphur end, and
at 615 C. for the antimony end. 5 (See fig. 3, p. 98.)
Antimony Trisulphide, Sb S 3 , has been, known from very early
times, under a, variety of names, such as antimoniurn, crudum, grey
antimony ore, antimony glance,, antimony glass, stilnite* Until the
eighteenth century it was frequently confused with antimony metal.
It exists in at least three forms, a crystalline form and two amorphous
forms, each of which may be obtained in a variety of ways.
1 Tom u la, Joe. at.
~ von Knorrc and Olschewsky, luc,. ciL For .further chemical properties of antimonates,
see Brunek, Zc.itxc.h. auaf. Chem.", 1895, 34, 171; Unger, Arch. Phann,., 187 I, [2J, 147, 193;
.Rose, Por/r/. Annalc/i, 1824, 3, 44]; 1848, 73, 582; 1853, 90, 201. For the electrolytic
behaviour of solutions of potassium antimonate, see Schmucker, Ze.tf.xrh. anonj. Chr-m.,
1894, 5, 199; Smith and Wallace, -ibid., 1893, 4, 273.
3 Schaller, Bull. l;.X. Gc.oL tinrwy, 1916, 610, 104. See also Xatta and Baccaredda,
Zc-ifxc.h. K As'/., 1933, 85, 271.
4 Fara lay, /V /f y. A-irndlcii, 1831, 23, 314; Bcr/elius, ibid., 1830, 37, 103; IVlabon,
Cfnnyt. re.-) d\ 190^ 138 A, 277; Cuinehant and Chretien, ibid., 1906, 142, 709; Unger,
Arch. Pka >/v., 187J, [_2j, 147, 199; 1871, |2J, 148, 2.
5 1-n.lw luiional Critical Tables,, 1928, 4, 25; Jaeger and van Klooster, Z(-il*cJi. anorg.
C'h<-m., 1912, 78, 245; Guinchant and Chretien, Compt. rend., 1904, 138, 1269; 1904,
139, 288; 1906, 142, 708; Britxke and Zactev, MineralnoeSnirc., 1931., 5, 816.
VOL. VI. : V. 7
98
AXTDIOXY AXD BISMUTH.
Crystalline antimony trisulphide may be formed by fusing together
the elements ; by subjecting a mixture of the elements to high pressure ; 1
or by heating the elements with water under pressure. 2 It may also be
formed from antimony by the action of sulphur dioxide, 3 and from
antimony trioxide, or from antimonates, by fusion with sulphur. 4 It
is also obtained by the action of hydrogen sulphide on the vapour
of antimony trichloride 5 or other antimony compounds, 6 and by the
prolonged heating at a high temperature of potassium antimony]
tartrate with a solution of ammonium thiocyanate, 7 or with potassium
tbiocyanate 8 in the presence of tartaric acid. In the latter case the
VDU
600
550
c..
500
^
450
400
i
\<6-57
\
\
^ /o
615C.
\
57-5%^"
\607a (54
?r.)
i
i
!
i
70 20 30 40 50 60 70 80 SO WO
Sb Atom/c per cent. Sulphur. 8
FIG/ 3. Antimony-Sulphur System.
amorphous variety is obtained at lower temperatures, the crystalline
at higher.
From antimony pcntasulphidc the crystalline trisulphide may be
obtained by heating at 200 to :300 C. in a current of carbon dioxide ;
by the prolonged action of sunlight on a dilute solution in hydrochloric
acid containing hydrogen sulphide : 30 or by heating in a tube at 250 (!.
with a solution of sodium bicarbonate. n
1 Spring, J1cr., 1883, 16, 999.
2 Celt nor, Annah?i t J864, 129, 359.
3 Gcitner, loc. cit.
4 Jannasch and Rcmmlcr, Jlrr., 1893, 26, 1425; Unsror, Arch. /Vwm., 1871, [21 147
193. ' ' ^
5 Diirochcr, Cornpt. rr.-nd., 1851, 32, 823; Arctowski, Zc.itscli. (merry. Cham., 1895, 8, 220.
fi Carnoi, Ccnnpt. rend., 1879, 89, 169.
7 \Veinsehenk, Zfif.^h. A'ry/.v/. Min., 1890, 17, 499.
s \Varren, Chun. New, 1892, 66, 287.
9 Rose, l '*n(i-nrll>itch dcr analytixc.hr.n C/if-.m-ia" (Berlin, 18(>7-7I), Oth Ed., Vol. II,
p. 295; Viuil, Zc-ilsch. anal.. Chem., 1892, 31, 539.
COMPOUNDS OF ANTIMONY. 99
From antimonic solutions the trisulphide is obtained by the action
of hydrogen sulphide at 70 C. in the presence of chromic chloride ; the
presence of the latter is essential for the formation, of the black modifica-
tion of antimony trisulphide in a pure condition. 1 Preparation may
also be effected by alternating current electrolysis of sodium thio-
sulphatc solutions using antimony electrodes. 2
The amorphous variety may be transformed into the crystalline by
heating in a neutral atmosphere; 3 by heating with water at 200 to
300 C. in a closed tube, 4 or by heating with hydrogen sulphide. 5 The
transformation is also effected by the action of dilute acids, especially
hydrochloric acid. 6
Amorphous antimony trisulphide is said to be formed by quenching
the molten substance rapidly. 7 A much purer product is obtained by
distilling the trisulphide in a stream of nitrogen and condensing the
vapour rapidly ; admixed sulphur may be removed by treatment with
carbon disulphidc. 8
The amorphous form is also obtained by the action of sodium thio-
sulphate upon solutions of antimony salts. 9 The technical product is
obtained by this method. A solution of sodium thiosulphate containing
sodium hydroxide is added to one of antimony trichloride ; the colour
of the resulting red product is influenced by the proportion of sodium
hydroxide, becoming yellower with increase of this reagent. 10 The
reaction may be represented by the equations :
SbCl 3 +3Na S 3 =Xa 3 Sb(S 2 O 3 ) 3 +3NaCl
~
The product is generally contaminated with oxide.
A more usual laboratory method of preparation, however, is by
precipitation from solutions of antimony salts by hydrogen sulphide.
Tartaric acid should be present to prevent the formation of thio-salts. 11
An investigation into the separation of antimony and tin by hydrogen
sulphide in hot hydrochloric acid solution, indicated that, with a con-
centration of.' 30 c.c. concentrated acid in 100 c.c. solution precipitation
of antimony trisulphide began at 95 C., that of antimony pcntasulphide
at 80 C. ; the presence of ammonium chloride in the solution lowered
1 Bosck, J. Chcm. Hoc., ]S95, 67, 515; Brauncr, loc. cti.
2 Toeccx Kazz(-.lf.a, 1924, 54, 23.
a Rose, Porjrj.AvnalcH., 1853, 89, 131; Cooke, Proc. Amer. Ac.ad. Arts 8ci., 1877, 13, 27;
Mourlot, Cornpl. rc.ud., 1 81)6, 123, 54.
4 Sehiirmann, Ann aim, .1889, 249, 33G; cle Senarmont, loc. ciL; Kosc, loc. cit.
'' Carnot, loc... cit.
Rose, /V/r/. An-nrdc.n, 1853, 89, 132, 138; Lang, far., 1885, 18, 271.6; Ditto, Cowpt.
rm<L, 1886, 102, 212.
7 Fuclis, Cornpl. r(-mL, 1834, 31, 578; Rose, Porjg. Annalcn, .1853, 89, .123. Sec,
however, Dittc, loc. cit.
8 Gumchant and OhnUion, Compt. rc.nd., 1904, 139, 51.
11 Vortmann, Her., 1889, 22, 231.1; Vohl, Annalc.n, 1855, 96, 240; Lenssen, Annalm,
'18()0, 114, 118; Frosjcnins, ". 4 tile. ituii g zur qv.antitativtn. cJicmischcn Analyse,*''* (.Braunsch-
wei.ii'), .1873-1877, (51 h Kd., I, 640, Lesser, Jnau(/. Dissertation, Jlc.rlin, 1880; Orlowski,
Zcilwh.. ana/.. (J/t.fm., I8S3, 22, 358; Vortmann, JMonatxli.., 1886, 7, 421; Carnot, Compt.
read., 1880, 103. 258.
10 llansen, /<( ttwh. ttixjnr. CJirw., 1932, 45, 505, 521; Kurtenacker and Furstcnau,
7,(-iltick. <nio;(j. Cfif'Hi.., 1933, 215, 257.
11 Sliarplos, Clic.m. New*, 1870, 22, 190; Ztitxch. anal. Chc-.m., 1871, 10, 343; .Rose,
loc. cd.\ Duilos, SchwM/yf-rfi J., 1830, 62, 210; 1833, 67, 269; Finkener, J. Soc. Chem.
Ind., 1889, 8, 733; Chem. Zed., 1SS9, 13, 'Rep. 201; Chem. Zentr., 18S9, ii, 380.
100 AXTDIOXY AND BISMUTH.
the temperature at which precipitation began in each case. 1 It is
probable that the precipitate of antimony sulphide obtained from
hydrochloric acid solution by hydrogen sulphide is seldom pure, being
contaminated with antimony oxychloride. The precipitate should be
heated in an atmosphere of carbon dioxide at 250 C. in order to convert
it to the black variety. 2
For commercial purposes crude antimony trisulphidc is usually
obtained by liquation from antimony ores. The chief impurities are
arsenic, 3 lead, 4 iron, copper and other metals. Purer products are
obtained by melting together a mixture of finely divided refined anti-
mony and sulphur, 5 or by saturating a solution of antimony trioxide in
dilute hydrochloric acid with hydrogen sulphide and passing carbon
dioxide through the boiling liquid. 6
Polymorphic forms of antimony trisulphidc that have been in-
vestigated are the red precipitated form, the black crystalline form and
the natural stibnitc. The two latter appear to differ only in density. 7
The densities of the three varieties arc :
Red precipitated form .... 4-1205 to 4-121
Greyish-black form 4-2906
Stibnite 4-6353
Stibnite crystallises in the rhombic system 8
a: b : c = 0-9926: 1 : 1-0179
Prom X-ray examination, however, the lengths of the edges of the
rhombic cell are given as 9
a = ll-39A., & =31-48 A. and c =3-80 A.
giving as axial ratios
a: b : c =0-992 : 1 : 0-338
There are four molecules of Sb 2 S 3 in the unit cell. 10
Transformation from the orange-red to the black variety takes place
on heating at just over 200 C., with evolution of heat. 11 The influence
of a number of substances on the transformation point, including carbon
dioxide, hydrogen sulphide, ammonium chloride, antimony trichloride,
metallic silver, potassium nitrate, sodium chloride, ammonium sulphate,
and acids of different concentrations, has been investigated. 12 In the
presence of water and various ions, 13 raising the temperature to 75 C.
hastens the change, the order of effectiveness of various ions and water
1 Luff, Chem. ZeiL, 1921, 45, 221), 249, 254, 274; "Prim, /./>/., 1917, 41, 41-1.
2 Yputz, J. Amcr. Chem. Sac., 1908, 30, 375; Beckett, Chem. Naws, 1910, 102, 101.
3 Wackenrocler, Arch. Pharm., .1852, [2], 71, 257; Reicli.irdl, Arch Ph'trm J857 '>!
91,136. - '' ''
- 1 Wittstcin. Repertonum Pharmacie, 1850, [3], 5, 67; Keichnrdt, loc. at.
5 von Liebig, Magazindcr Pharmacic, 1831, 35, 120; 'Avnal.cn, i$M 7 1- 1859 71 57
6 Mitchell, CJif.in. Neics, 1893, 67, 291. '
7 Zarri, Bull. A cad. roy. fitly., 1909, 1109.
8 .Dana, " Kyttc.m of Mineralogy" (Xe\v York and London), 1899, (5th Kd., p. :{<;
Dana, Amcr. J. Sc-i., 1883, [3], 26, 214; Talacho and Modill, Awc.r. Mi-crul 1930 15
365: fiofmann, Zeitsr.h. /Om/,, 1933, 86, 225; 1 hnizo, /hid., 1882,6,410.
9 Gottfried, Zcitsck. Kri,*t., 1927, 65, 428; Allbniilit, 7%.-?. Jtcnr.ir, 1931, 37, -ins.
10 Hfni
COMPOUNDS OF ANTIMONY.
101
being (in diminishing order) : anions, S'~, water, XO 3 , Cl , SO/%
( 1 2 HoO 2 ~ : cations, Il r , water, Xa' r , XI I 4 . In aqueous hydrochloric
acid the times taken for complete transformation in solutions of con-
centrations 12A r , TA r and N were 0-5 day, 1 day and 10-5 days
respectively. The effect of temperature on the time taken for the
transformation (using a 20 per cent, solution of hydrogen chloride) was
as follows :
Temp., c C.
1 Time required .
26-5
44 hrs.
30
29 hrs.
35
16 hrs.
40
9 hrs.
68-5
62 mins.
r~s - O
/
32 mins.
In a corresponding solution of hydrogen bromide no change occurred
after 20 hours at 75 C.
The hardness of stibnite on Mobs' scale is 2 to 2-5. Its density 1 and
that of the prepared variety 2 have already been given. Its melting-
point is about 550 C. 3 It can be distilled, the boiling point being 1090
to 1150 C. ; some decomposition takes place. 4 Antimony trisulphide
begins to volatilise at 650 C. ; volatilisation is rapid at 800 to 850 C.
and is complete at 917 C. The electrical conductivity of single crystals
is not purely electronic, electrolytic decomposition accompanying pro-
longed passage of current. 5
Amorphous antimony trisulphide varies in properties according to
the method of preparation. In colour it ranges from red to greyish-
black. Most specimens contain water, and it has been suggested that
a hydrate is formed ; also that the black form is anhydrous and the red
form hydrated. 6 It has been observed, however, that the loss in weight
which occurs when the red variety is heated to 100 C. is not due so much
to loss of water as to secondary reactions involving absorption of
oxygen and loss of sulphur dioxide. 7 When the sulphide is precipitated
from a solution free from chlorides it does not suffer any loss in weight
on prolonged heating at 250 C. in a current of carbon dioxide. 8 The
densities of different specimens vary from 4-120 to 4-421. An investiga-
1 Neumann, Pwjy. An-Hule-n, 1831, 23, 1; Schroder, JahiMbcr., 1879, 54.
2 Dittc, Comvt. rc;n.d., 1880, 102, 212; Rose, Poyy. Annalui, 1853, 89, 131; Karstcn,
tich-weiggcr'x J '., 1832, 65, 395; Cooke, Proc,. A-nicr. Acad. Arts Sci., 1877, 12, 127; Guin-
chaTil and Chretien, Co-nipt, rend., 1906, 142, 709.
3 Pelabon, (Jo-nipt, rend., J 904, 138, 277; Guinchant and Chretien, Hid., J 904, 138,
1269.
4 Brit/.ke and Zaetev, M incralnoc tiuir'c, 193J, 5, 816; Kohhneyer, Mc.tall nnd Erz,
] 932, 29, 105, 408; Shakhov and Slobodska, Tzvct. Met., 1930, 1294;" Chiviic, a Induslru'.,
193J, 25, 112(3.
5 Frey, Ark.lc K^ni, Min.cmL, GcoL, 1932, n A, No. 4, 1.
L ; or other pliysical properties, see Pelabon, Oorn.pt. rc.-nd., 1905, 140, 1389; Re^naull,
Pofjy. Ann'tlm, 1841, 53, 75; Xeurnann, Jahret<l( j .r., 1864, 50; Olio, -Jim. and Kruyt,
Proc. K. A/cad. Wc.tctiw./i. Amsterdam, 1912, 14, 740; Voi^t, Zcitxch. Pliynik, 1929, 57,
154; Cissar/, Scwa* Yahrb. Mm.., 193], A 64, 137; Chew. Zcnlr., 1932, i, 512; Yaraaguti,
Proc. J'hyx.-Matk. tioc. Japan, 1932, 14, 1.
Ditto, loc. cit.; Wittstein, Ztitxch. anal. Chc/n., 1870, 9, 264; Rose, Pogg. Antiale.n,
1 853, 89, 137 ; Frcscmus, " Anleitung zur quantila.tiu&n cliemische.n Analyse" (Braunschweig),
1873-1877, 6th Ed., 2, 812; Dexter, Amtr. J. tici., 1868, [2], 45, 78; Xilsson, Zettsch. anal.
Cht.rn., 1877, 16, 418; Cooke, Proc. Amer. Acad. Arts Sol., 1877, 12, 127; linger, Arch.
Phann., 1871, [2J, 148, 11.
7 Zani, lor. cd.
8 Yout/, J. Afner. Cftfim. tioc., 1.908, 30, 375.
9 Tuchs, Po(jy. Aiitiulen, 1834, 31, 578; Rose, toe. cit.; Cooke, loc. at.; Guinchant
and Chretien, Compt. rend., 1904, 139, 51.
102 ANTIMONY AND BISMUTH.
tion of the heat of formation of different specimens reveals only very
slio-bt differences. 1 The calculated heat of formation, (from sulphur
vapour and solid antimony) 2 is 86,490 gram-calories, and that from
rhombic sulphur and solid antimony 38,300 gram-calories (both calcula-
tions refer to black antimony trisulphide). 3
The chemical properties of all varieties of the trisulphide are similar,
but the amorphous form is the most active. All varieties are decom-
posed when heated, metallic antimony being formed. 4
Antimony trisulphide is reduced by hydrogen, reduction beginning
at 360 C. The reaction
Sb 2 S 3 +3H 2 ^: 2Sb+3H 2 S
is reversible. 5 From a study of the equilibrium between antimony
trisulphide and hydrogen the dissociation pressures of the trisulphide
have been calculated, 6 and it is found that log p is a linear function of T,
where p is the partial pressure of the sulphur vapour and T the absolute
temperature. 7 At temperatures up to the melting point, the partial
pressure of hydrogen sulphide is proportional to the temperature ; 8
above the melting point the equilibrium is disturbed owing to the
solubility of metallic antimony in molten antimony sulphide, the com-
position of the gas then depending not only on the temperature, but
also on the concentration of the solution of antimony in antimony
trisulphide. If antimony is present in excess, the solution is, of course,
always saturated, and again the equilibrium is determined by tem-
perature alone. Antimony trisulphide reacts "with hydrogen under the
influence of the silent electric discharge (15,000 volts), the products
being an antimony mirror and hydrogen sulphide. 9
Antimony trisulphide burns in oxygen with the formation of sulphur
dioxide and a mixture of antimony trioxide and tetroxidc. 10 The heat
of reaction has been calculated ll and is given, in gram-calories, by the
equation
Sb 2 S 3 + 4-5O 2 =Sb 2 O 3 +3SO 2 +328,400
The conditions of roasting antimony trisulphide have also been studied, 12
together with the conditions of oxidation to antimony trioxide and
antimony tetroxide, and the dissociation of the latter. At 100 C.
oxidation to antimony trioxide begins, the action becoming rapid at
340 C. and complete at 445 C. Above this temperature oxidation to
antimony tetroxide takes place, and continues up to 900 C 1 .., at which
temperature dissociation of the latter into antimony trioxide begins and
1 Gumchanl and Chretien, toe. clt.; Berthelot, Ann. Ckini. Phy*., 1887, [Gj, 10, 135;
Co-nipt, rend., 1904, 139, 97.
- Britzke and Kapustinski, Tzvet. Met., 1931, 1147.
;} Britzke and Kapustinski, J. Phys. Chem., U.8.SJL, 1934, 5, 80.
4 Mourlot, Compt. rend., 1896, 123, 55; Ann. Chun. Phy*., 1899, [ 7 |, 17, f>]().
Rose, Pofjg. Annale/i, 1824, 3, 443; Schneider, ibid., 18.16, 98, 296; ,/. pra/cf. Chc.ni.,
1880, [2], 22, 137.
(i .Britzke and Kapustinski, loc. cil.; Ztit.sck. anory. (Jkc.in., '1930, 194, 323.
7 See also Kohlmeyer, Met-all uud Krz, 1932, 29, 105, 481.
8 Pelabon, Coutpt. rend., 1900, 130, 911.
9 Miyamoto, J. Che-f/i. Soc. Japan, 1932, 53, 788.
10 Capitainc, J. Pharrn. Chim., 1839, [3|, 25, 516; Janriaseh, Zc.itxc.h. unory. Ch.c.in.,
1894, 6, 303: Haidinger, Pogg. Annalen, 1827, n, 178; Kakle, Ztitack. Kryxt.,' 1894, 24,
581; Laspeyres, ibid., 1884, 9, 186.
11 Britzke and Kapustinski, Tzvet. Mtl., 1931, 1147.
l - Sliakhov and Slobodska, ibid., 1930, 1294; Chimie et Industrie, 1931, 25, 1126.
COMPOUNDS OF ANTD10XY. 103
is complete at 1130 C. By the action of ozone, antimony trisulpliide
is converted into antimony sulphate. 1
By prolonged digestion with water the amorphous trisulpliide de-
composes, yielding antimony tri oxide and hydrogen sulphide. 2 It reacts
with steam to form an oxysulphidc. 3 It is oxidised by hydrogen peroxide
to sulphate, 4 and even to pentoxide ; 5 ammoniacal solutions of hydrogen
peroxide and sodium peroxide react to form antimonates. 6
Antimony trisulpliide reacts vigorously with fluorine in the cold,
yielding the trifluoride. 7 Chlorine reacts less vigorously with the heated
sulphide, which, however, is decomposed by hydrogen chloride. 8 The
trisulpliide will dissolve in aqueous hydrochloric acid, the solubility
depending upon the concentration of the acid and of the hydrogen
sulphide in the solution. If the pressure of hydrogen sulphide over the
solution is increased, the action is reversed and antimony trisulpliide is
precipitated. Complete dissolution can be obtained by removal of
hydrogen sulphide. 9 Antimony trisulpliide is also decomposed by
bromine 10 and by iodine. 11 (For the influence of the halogen acids upon
the transformation of the amorphous into the crystalline variety, see
P- 101.)
Thermal examination of a number of binary sulphide systems in
which antimony trisulpliide forms one component has been made.
This includes the systems with bismuth trisulpliide, 12 lead sulphide, 13
tin sulphide, M cuprous sulphide, 15 silver sulphide. 1G The ternary systems
copper antimony sulphur 17 and nickel antimony sulphur 18 have been
examined.
Sulphur dioxide has very little action on antimony trisulpliide. 19 The
1 Mailt'ert, Compl. rend., 1882, 94, 1186.
- Geiger and Hesse, Anna ten., 18,33, 7, 19; Vogel, J. Pharm., 1822, 8, 148; de Clcr-
mont and Trommel, Ann. Chlm.. Phyx., 1879, [5],"l8, 198; CompL rend., 1878, 86, 828;
1878, 87, 330; Fibers, Chem. Zeit., 1888, 12, 355; Lesser, I-n.augu.ral Dissertation, lit.rlui,
1880; Lang, '#/-., .1885, 18, 2715; Doltcr, Monatsh., 1890, n, 149.
:! Regnault, Ann. Chim. Pkyx., 1836, [2], 62, 383.
1 Classen and Bauer, Ber., 1883, 16, 1007; Thcnarcl, Ann. Chim., 1800, 32, 257.
5 Zambelli and Luz/atto, Ann. chi-rn. farm., 1880, [4J, 3, 229.
t: Hampe, Chem. Zc.lL, 1895, 18, 1899.
7 Moissan, Ann. Chim. ./%*., 1891, [OJ, 24, 202.
8 Tookey, J. Chem. Soc., 1802, 15, 462; de Koninck and Lecrcnier, Zeilsch. anal.
Chem., 1888, 27, 402.
9 Lang, Ber., 1885, 18, 2714; Lang and Carson, J. Soc. Chem. Ind., 1902, 21, 101 S;
Warren, Chem. New*, 1892, 65, 232. For the application of this reaction in analysis, see
Field, Chem. JV'ew.s 1 , 1801, 3, 114; Lesser, Inaugural ]) is serial. Ion, Berlin-, 1880; StTomcyer,
Zeilsch. anal. Chem., 1870, 9, 204; Kohler, ibid., 1890, 29, 192; Xeher, ibid., 1893, 32/50;
Loviton, J. Pharm. Chim., 1888, [5J ? 17, 301; Zeltsch. anal. Chem., 1890, 29, 345; Schleier,
Inauijwral J)luxerlati.on, Erlanyen, .1.892.
10 Jannasch and Remmler, Bar., 1893, 26, 1422; Bartley, American Chemist, 1.875, 5,
430.
11 Schneider, Poc/y. Ann-aten, 1850, 99, 470; 1800, 109, 010; 1800, HO, 150; Bolton,
Chem. News, 1878, 38, KiS.
12 Takahashi, Mem. Coll. XcL Kyoto, 1920, 4, 47.
13 .Jaeger and van Kloostcr, Zeltsch. anorg. Chem., 1912, 78, 245; litsuka, Mem. Coll.
Sei. Kyoto, 1920, 4, 01.
1 Farravano and dc Cesaris, Alii R. Aeead. Llneel, 1912, [5J, 21, i, 535.
: > Chikashige and Yamanchi, Mem. Coll. Set. Kyoto, 1910, I, 341.
Jaeger and van Kloostcr, loc. at.; Konno, Mem,. Coll. Sci. Kyoto, 1920, 4, 51.
7 Guertler and Mcissner, Mdatt und Erz, 1921, 18, 410.
8 Guertler and Schack, Melall und Erz, 1923, 20, 102.
9 Berthier, Ann. Chlm. Phyt., 1823, [2], 22, 239; Guerout, CompL rend., 1872, 75,
1270. Sec also .Bunsen, Annalen, 1858, 106, 8; 1878, 192, 305; Xilson, Zeilsch. anal.
Chem., 1877, 16, 419; 1879, 18, 106.
104 AXTIMOXY AND BISMUTH.
trisulphide is dissolved slowly by concentrated sulphuric acid, yielding
an acid antimony sulphate, sulphur dioxide and sulphur. 1 Dilute
sulphuric acid assists the transformation from the amorphous variety
to the crystalline. By heating with potassium sulphate, potassium
aiitimonate is obtained. 2 The trisulphide reacts with both sulphury 1
chloride and thionyl chloride, antimony trichloride being formed in each
case. 3
Antimony trisulphide is appreciably soluble in aqueous ammonia,
the solubility increasing with rise of temperature. In solutions of
ammonium carbonate, however, it is practically insoluble. 4 Treatment
with concentrated nitric acid yields a mixture of antimony nitrate and
sulphate, and with fuming nitric acid a mixture of antimony pentoxide
and sulphuric acid. 5 Hydrogen sulphide is evolved by the action of
slightly diluted nitric acid (6A r ) ; this action is retarded by the presence
of hydrazine. In the presence of the latter a number of secondary
reactions also occurs. 6 The trisulphide is completely converted to
trichloride by heating with a mixture of ammonium chloride and
ammonium nitrate. 7
A complex reaction takes place w r hen antimony trisulphide is heated
in a current of phosphine, the products being phosphorus, antimony and
hydrogen sulphide. 8
Antimony trisulphide is reduced to metallic antimony when heated
with carbon, carbon disulphide also being formed ; 9 it is partially
reduced by heating in a current of carbon monoxide at red heat. 10 In
the reaction
equilibrium moves to the right with rise of temperature. 11 Antimony
trisulphide also reacts with carbon dioxide at a dull red heat, the
products including sulphur dioxide, carbon monoxide and carbonvi
sulphide. 12
When antimony trisulphide is fused with excess of alkali, a mixture
of alkali antimonite and thioantimonite is produced ; but if excess of the
trisulphidc is used, antimony oxysuiphide is obtained instead of alkali
antimonite ; 13 some metallic antimony may be precipitated if the fusion
is carried out at a high temperature. Amorphous antimony trisulphide
is soluble in excess of an aqueous solution of potassium hydroxide, but
is reprecipitated on the addition of hydrochloric acid ; the crystalline
form behaves similarly on warming. 14 When heated with potassium
1 Hensgen, Jlc.c. Truv. c/t.i-t/i., 1885, 4, 401.
- Wcbsky, Zcltsch. anal. Chun.., 1872, n, 121.
3 lYinz, Annatcn, 1.884, 223, 364; RuiT, tier., 1.901, 34, 1752.
-' Epik, Z&'dsch. anal. Cham., 1932, 89, 17; Garot, ,/. prakt. Ckam., 1843, 29, 83;
Gamier, J. Phrmn. Ch-int., 1893, [_f>], 28, 97; Capitaine, ibid., 1839, [3J, 25, 510; J. pratt.
Chcm., 1839, 18, 449.
3 Bunsen, Anjial.vii, 1858, 106, 3.
(i Kcsans, Laimj. Univ. JiakMi, 1933, 2, 311, 317.
7 Pre.senms, Ztiltsch. anal. Chcm., 1886, 25, 200; de Clcrmont, Co-nipt, rvnd., 1879, 88,
972.
s Rose, Puijfj. A-iM'dcn., 1830, 20, 336.
'' Bcrthicr, Ann. Ohlm. Phyx., ]823, 22, 239.
Gobcl, -/. pmld. Chtm., 1835, 6, 388.
1 Uritzke and Zactev, J\I. ineralnoe Suir'e, 193J, 5, 816.
- de Bacho, Mo/i.atsh., 1916, 37, 85.
3 Berzelius, Sckwvigytr's J., 1822, 34, 58; Poyy. AnnaUn, 1830, 20, 365; 1836, 37, 163.
1 See iih-so \\'cppcn, Bw., 1875, 8, 525; Terrell, Bull. Soc. chim., 1876, [2], 25, 98.
COMPOUNDS OF ANTIMONY. 105
cyanide, partial reduction takes place ; 1 on. heating with a mixture of
potassium cyanide and sodium carbonate a mirror is obtained when the
reaction is conducted in a current of hydrogen, but not when carbon
dioxide is substituted for hydrogen. 2
Antimony trisulphide is reduced by heating with many metals,
metallic antimony being formed, which combines with excess of the
metal to form antimoiiid.es. 3
Sols of antimony trisulphide have been obtained by the action, of
hydrogen sulphide upon water saturated with antimony trioxide : 4
or upon a dilute solution of potassium antimonyl tartrate ; 5 or by
the addition of a few drops of a solution of potassium sulphide to a
suspension of amorphous antimony trisulphide in water. 6 These sols
vary in colour from blood-red to yellow. They may be purified by
dialysis, tartaric acid, however, being difficult to separate. Sols free
from foreign matter are stable even on warming. Many acids and their
salts cause precipitation of the trisulphide, the efficiency of a salt in
this respect increasing with the valency of the cation. (Iron, however,
appears to act exceptionally. 7 )
Two hydrates of antimony trisulphide, namely Sb 2 S 3 .2H 2 O and
SboSg.HoO, have been described, but their existence docs not appear
to have been established definitely. 8
From an examination of the precipitates obtained by the action of
hydrogen sulphide upon potassium antimonyl tartrate it has been
assumed that compounds of antimony trisulphide with hydrogen
sulphide may exist. The precipitates, however, are of variable com-
position. 9
Compounds of antimony trisulphide with metallic sulphides have
been described. These have generally been assumed to be complex
thioantimonites, related to a number of hypothetical, and complex, thio-
antimonious acids. Compounds of the types Na 3 SbS 3 , Na 2 Sb 4 S 7 ,
Xa G Sb 4 S 9 , NaSbS 2 and NaHSb 4 S 7 have been described. Many of them
occur naturally (see pp. 4-8). They may be prepared by fusion, or by the
action of antimony trisulphidc upon solutions of the metallic sulphides.
Alkali thioantimonitcs may be prepared by the action of alkali hydroxide,
1 Kose, Pocjfj. Annalw, 1853, 90, 204.
- Frescnius, "Artie-Hung zur qualitativen che-mischan Analyse-" (Braunschweig), 1919,
p. 314.
u l ; or the chemical reactions of antimony trisulphide with other metallic compounds,
see Ephrairn, Zeiltich. anory. Che-u\. 9 1905, 44, 195; Bottgcr, Jahrexber., 1869, 1065;
Yemeni], Cvmpt. rend., 1886, 103, 600; Bccqucrel, Com.pt. rend., 1888, 107, 895; Zsig-
mondy, J)t)i(jL poly. J., 1889, 273, 29; Schiirmann, Annalen, 1889, 249, 341; Lindner,
Zeitsch. Chem., 1869, 44'2; Bunscn, Annalcn, 1858, 106, 4.
4 Capitainc, J. Pfiarm., 1839, 25, 516; J. prakt. Chcm., 1839, 18, 49; Schulze, J.
prakt. C/iem., 1880, [2_L 27, 320.
5 L'icton, J. G he-)ii. tioc. y 1892, 61, 137; Scliulze-, luc. cit.
6 Ditto., Co)iipt. roul., 1886, 102, 109.
7 See a^o Biltz and Geibel, " Abha-ndiunywi der Koniyhchtn Gescttscha/t tier WIMC.H.-
schajttn zu Goltinfjtn," 1906, 141; 1904, 1 ; Lubavin, J. liuss. Cheni. Soc., 18S9, 21, 397;
Sabanejew, Wtcd. Annalen, 1891, 15, 755; Jablczynski and Przezdziecka-Jedrzejowska,
JluU. ,b'oc. chim., 1925, [4], 37, (.508; Rocz. Chem., 1925, 5, 173; Ghosh and Dhar, KolloidZe.it.,
1925, 36, 129; JScn, Ganguly and Dhar, J. Physical Chun., 1924, 28, 313; Clemente and
1-Jwei-Pu Tsai, Univ. Philippine.. 1 } Natural Applied Science. Bulletin, 193J, I, 319; Joshi
and Prabhu, J. Indian Chan. Soc., 1931, 8, 11; Jablczynski, Kotloid ZciL, 1931, 54, JG4.
8 Dittc, Coin.pt. rend., 1886, 102, 214; Dexter, Zeitxch. anal. Chcm., 1870, 9, 264;
A\'ittstcin, ibid., 1870, 9, 267; Xilson, ibid.', 1877, 16, 418; Matthiew-Plessy, Bulletin de la
Societc industrielle de. Mulhouse, 1855, Xo. 130.
9 Linder and Picton, /. C/it/n. Sue., 1892, 61, 133.
106 ANTIMONY AND BISMUTH.
carbonate or sulphide upon antimony trisulphide ; or by the action of
alkali sulphide upon antimony trichloride. Corresponding compounds
of the heavy metals may be obtained by double decomposition. 1 Thio-
antimonites of alkali and alkaline earth metals (formerly known as
t; liver of antimony ") vary in colour from yellow to reddish-brown,
those containing the greater proportion of' antimony trisulphide having
the darker colour. Crystalline specimens can be prepared. They melt
at a low temperature, and are fairly stable when gently heated out of
contact with air ; they decompose when heated strongly, being con-
verted into thioantimonates. When heated in air they burn. Thio-
antimonites of the heavy metals are grey to black in colour, the natural
products being crystalline, synthetic products amorphous. Some of
them can be melted without decomposition when heated in the absence
of air ; but for the most part they decompose readily, forming a sub-
limate of antimony trisulphide. Heated in air, they are converted to
oxides, with evolution of sulphur dioxide.
Only the thioantimonites of the alkali and alkaline earth metals are
soluble in water. They are for the most part hygroscopic, and many
are decomposed, as are also their solutions, on exposure to air. The
natural thioantimonites are decomposed by the action of nitric acid and
other oxidising agents, and in some cases by hydrochloric acid. 2 They
arc completely decomposed by solutions of alkali sulphides. 3
The existence of antimony tetrasulphide, Sb 2 S 4 , which has been
described as a reddish-yellow or red powder, does not appear to have
been fully established. Several methods for the preparation of this
powder have been described, including the action of hydrogen sulphide
upon a hydrochloric acid solution of antimony tetroxide, or potassium
meta-hypoantimonate, K 2 Sb 2 O 5 , or upon a solution of the complex
compound 3KC1.2SbCl 4 ; 4 and the action of carbon disulphidc upon
antimony pentasulphide. 5 On heating it is converted to antimony
trisulphide. It dissolves in hydrochloric acid yielding hydrogen
sulphide ; it also dissolves in ammonia forming a yellow solution.
More recently it has been suggested that golden antimony sulphide,
generally regarded as impure antimony pentasulphide, is really a mixture
1 Bcrzchus, Schweiyyers J., 1812, 6, 144; 1818, 22, 69; 1822, 34, 58; Poyy. AtinaUn.,
1830, 20, 365; 1836, 37, 1.63; Ditto, Cornet, rend., 1886, 102, JOS, 212; Poimet, ibid.,
1898, 126, 1144; Ann. Chim. Phys., 1899, 18, 524; Stanek, Zritxc.h. nnortj. Chew., J8D8,
17, 117; Cngcr, Arch. Pharm., 1871, [2J, 147, 198; 187J, |2J, 148, 2; BerUio.lol, Ann.
Chim. Phys., 1887, [6], 10, 133; Duflos, Sc.hwtifj(jer'a J., 1831, 62, 2 JO; 1833, 67, 269;
Kammelsberir, Poyg. Annaltn, 1841, 52, 204; Somnierlad, Zc.itxrh. a/iory. Ghcm 1897
15, 173; 1S98, 18, 420.
2 Pouget, Cotn.pt. rend., 1897, 124, 1445; 1.898, 126, 1792; Classen, lJe,r., 1894, 27,
2074; Hampe, Ze-itxch. anal. Chcm., 1892, 31, 320; Jannaseh, ,/. prakt. Chc.ru., 1889, (2!,
40, 230; Ztitsch. anal. Chun., 1894, 33, 214; Berthelol, Ann. Chim. 7%,s., J8SO, (0|, 10,
134; Bolton, Chcrn. News, 1878, 37, 99; 38, 108; Miiller, Payy. Annalcj/.,' 1800,
127, 413; Marx, Schiwiyyvr's J., 1830, 59, 251; Kohl, Archiv dc.x A-polhr.kr.rH'.rt'.inti I.-HI.
nordlichcn Dautschland, 1826, 17, 259; Berliner, Ann. Chun. Phya., 1823, 22, 239; 1824,
25, 379.
3 Dolior, Monatxh,., 1890, 1 1, 150; Terrell, Compt. mid., 1870, 69, 1360. Sec also
Pouget, ibid., 1897, 124, 1445; 1899, 129, 103; Poleek, Jict., 1894, 27, 1052; fterono,
Guzzetla, 1894, 24, 11, 274; Smith, Her., 1890, 23, 2276; Borglund, Bcr., 1.884, 17, 95;
Heumanii, Annaleti, 1874, 173, 33.
* Bosek, /. Chem. tioc., 1895, 67, 516.
5 IMitsclierhch, J. pralti. Chc-m., 1840, 19, 455; Wilm, Zail^c.h. anal. Chc.ni., 1891, 30,
438; Brauner, /. Ghcm. Soc., 1895, 67, 540.
G Capitaine, /. Pharm., 1839, 25, 510; /. prakt. Ghtm., 1839, 18, 449. See also
Websky, Zeitsch. anal. Cham., 1872, n, 124.
COMPOUNDS OF ANTIMONY. 107
of antimony tetrasulphide, antimony trisulphide and free sulphur ; it is
further claimed that pure antimony tetrasulphide may be obtained by
decomposing zinc thioantimonate with dilute hydrochloric acid, accord-
ing to the equation.
= Sb 2 S 4 +3ZnCl 2 +H 2 S 2 + 2H 2 S -
The tetrasulphide is regarded as being of the type M^SbSj),,, in the
special case when M =Sb and x y. 1
Antimony Pentasulphide, Sb 2 S 5 , appears to have been first
described by Basil Valentine. Early writers knew it as sulphur auratum,
while Glauber (1654) described it in his "Pharmacopoeia spagyrica" as
Panacea Antimonialis. 2 -
It is doubtful if pure antimony pentasulphide has been prepared, most
samples, and certainly all commercial products, containing free sulphur;
possibly no higher sulphide exists than antimony tetrasulphide. 3 A
fairly pure product may be obtained by passing hydrogen sulphide
through a solution containing antimony pentachloride (free from
tervalent antimony) and 12 to 15 per cent, free hydrochloric acid. 4
After treatment with carbon disulphide the resulting substance has a
composition corresponding to Sb 2 S 5 , and does not react with ammoniacal
silver nitrate.
Commercial antimony pentasulphide, or " golden antimony
sulphide," is as already stated always impure, and is generally supposed
to be a mixture of antimony tetrasulphide and free sulphur. The usual
method of preparation is by the decomposition of an alkali thioantimon-
ate, such as Schlippe's salt, Xa 3 SbS 4 , by means of dilute acid :
2Na 3 SbS 4 -;-3HoSO 4 = (Sb S 4 + S) + 3Na SO 4 H-3BUS
2Xa 3 SbS 4 -r 6HC1 = (Sb~S 4 + S) -f GNaCl + 3lI 2 S "
Sulphurous acid has also been suggested, 5 and is recommended in
preference to the stronger acids since the evolution of hydrogen sul-
phide by the latter is objectionable. When sulphurous acid is used, the
formation of excess of free sulphur (which would contaminate the
product) may be prevented by the careful addition of sodium sulphite.
In order to avoid the production of brownish products the solution must
be kept acid. 7
Antimony pentasulphide is a reddish-yellow or brown powder with
a faint smell and a sweetish taste. When heated it loses sulphur,
darkens in colour, and at 170 C. is gradually converted into antimony
1 Kirchliof, Zcitech
2 Dyson, Pkarni. J. a
3 Kirchhof, ZeUscli. a
1922, 63, 379; J. Soc. CI
4 Schurmann and Be
.or<j . Cham., 1920, 112, 67.
(//Pharmacist, 1929, [4], 67, 397, 520.
.ory. Chem., 1920, 112, 67; Short and Sliarpe, India- rubber J.,
eni Ind., 1922, 41, 109 T.
Kaulachuk, } 930, 6, 70, 91, 136. See also Ullmaun, "Ktizy-
klopadie, der ttclimsclitn Chemit" (Berlin and Vienna), 1928, 2nd Ed., I, 548.
5 Farbenind. (Hanson), German Patent, 1926, 49208(5.
fi ITanscn, Zutsch. antjnv. Cham., 1932, 45. 505, 521.
7 See also Bcrtscli and llarmsen, Gc-rinan Patent, .1896, 94124; Ztitsck. diujtw. Chew ,
1897, 641; Souviron, French Patent, 1925, 605401; Halm, U.S. Patent, 1928, 1671203;
Stark, U.S. Patent, 1927, 1633754: Berzclius, Schweigger'sJ., 1822, 34, 58; Poyg. Annalen,
1830, 20, 365; 1836, 37, 163; Rose, ibid., 1824, 3, 441; Bosek, J. Chem. /S'oc., 1895, 67,
515; Klenker, J. prakL Chc.m., 1899, [2], 59, 150, 353; Bunsen, Annahn, 1878, 192, 317;
Wittstein, Viertel.yahrexfichri.ft.fur pmktisclw. Pharmacia, 1869, 18, 531; Classen and Bauer,
Ber., 1883, 16, 1067; Wibn, Zcilsch. anal Chem., 1891, 30, 444; Thiele, Annalen, 1891,
263, 371; Brauner, /. Chem. Sac., 1895, 67, 527; Prunier, J. PJmnii. Chim., 1896, [6],
3, 289.
108 ANTIMONY AND BISMUTH.
trisulphide. 1 When heated in air it is oxidised to antimony trioxide, 2
which volatilises. It is reduced to metal by heating in a current of
hydrogen, and is decomposed by exposure to moist air, antimony
trioxide being formed. 3 It is only partially oxidised by treatment with
ammoniacal hydrogen peroxide. 4
The pentasulphide is partially soluble in ammonium hydroxide,
forming a yellowish solution and leaving as residue a mixture of anti-
mony trisulphide and sulphur. 5 It is decomposed by nitric, acid, and
by hydrochloric acid (density 1-12) forming antimony trichloride,
sulphur and hydrogen sulphide ; 7 treatment with sulphuryl chloride
converts it into antimony pentachloride. 8
From most commercial samples of antimony pentasulphide sulphur
can be removed by treatment with carbon disulphide, or other solvents
of sulphur, the proportion removed depending upon the method of
preparation of the pentasulphide. 9
-Alkali hydroxides and carbonates react with antimony pentasulphide
with formation of a mixture of alkali antimonates and thioantimonates,
the former being precipitated. From the solutions obtained ou
filtering, antimony pentasulphide is reprecipitated by the addition
of acids ; while from solutions in alkali carbonate the precipitate consists
of antimony trisulphide. Barium and strontium hydroxides behave in
a somewhat similar manner. 10 Fusion with potassium cyanide causes
partial reduction, some potassium thioantimonite being formed. 11
Commercial antimony pentasulphide is a mixture of variable com-
position depending upon the method of manufacture. It is employed
extensively in the rubber industry, and many methods of assay have
been proposed. 12
Thioantimonates. Compounds of antimony pentasulphide are
known to occur naturally; they have also been prepared in a variety
of ways. They may be regarded as normal thioantimonates, or salts
of an unknown acid, thioantimonic acid, II 3 SbS 4 . Salts of the heavy
metals are best prepared from those of the alkali metals by double
decomposition. The most important of these salts is sodium thio-
antimonate, Na 3 SbS 4 , known also as Schlippe's salt. It is prepared by
1 Hose, Pogg. Aunalai, 1853, 89, 141; Heflter, ibid., 1852, 86, 421; Paul, Zcitxch. mud.
Chan/., 1892, 31, 533.
2 Classen and Bauer, Bar., 1883, 16, 1071; "Ungcr, Arch. Pharm., 1871, [2], 147, 196.
3 Otto, Aniialfii, 1838, 26, 88; Jahn, Archiv des Apothckcrt'crcins i'tn 'iiordlichai
Deut*chla.7)d. 1828, 22, 43.
- 1 Classen and Bauer, Btr., 1883, 16, 1067.
5 Gei^cr, ^lagazin, der Pharmacie, 1830, 29, 241.
G Pagenstcebcr, Troinrnsdorffx 'Neucs Journal der Phunnucic, 1.820, 3,
Ztitsch. anal. Chew., 1891, 30, 444.
7 Scherer, Ze-it^ch. anal. Chan-., 1804,3,206. See also Classen and
Bunsen, Loc. cll.\ Wittstein, loc. cit.
8 llufl, er., 1901, 34, 1752.
9 Mitseherlieh, J. pmkt. C/ICM., 1840, 19, 455; Wilm, loc. ctt.; ^Bosek,
melsberg, loc. cit.; Classen, loc. cit.; Selmrmaim and Bohm, loc. at.;
Ivlenker, 'foe. at.
]u Mitsehcrlieh, he. cit.; Kaininelsbet-o, j OCm c /t. ; Koit and Ktibiorschkv, /ic.r., 1888, 21,
1660.
11 Rose, Pixjfj. Atihalt.H, 1853, 90, 207.
12 flock, Knutxchuk, 1925, I, 11; Chiappero, Gu>rn. Chun. Ind. Appl., 1926, 8, 1020;
LufT and Pomtt, /. Soc. Chan. Ind., .1921, 40, 275; Xirehhof, Ze.itxch. unary. Chrm.., 1920,
114, 266: van Kossem and Dckker, liidm-rubbt-f J., 1920, 60, 905; Huti'n, An-n. (Jhrj/i.
anal., 1916, 21, 3, 32; Lehmann and Berdau, Chc.m. Zait.r., 1914, i, 1699; AU-ock, ,/.
Pharm., 1913, 91, 213; Jacobsohn, Chem. Zeii., 1908, 32, 984; Chan. ZaUr., 1908, i, 763;
Gumvii Ztit., 1908, 22, 368; 1909, 23, 1046.
COMPOUNDS OF AXTBIONY. 109
the gradual addition of a mixture of antimony trisulphide and sulphur
to a boiling solution of sodium hydroxide, ] according to the equation
4Sb 2 S 3 + 8S -!- ISXaOH - 5Xa 3 SbS 4 + 3XaSbO 3 4- 9H 2 O
The. sodium antimonate formed at the same time is almost completely
precipitated. This reaction may be employed for the preparation of
other metallic thioantimonates since carbonates or sulphides of the
alkali metals, or hydroxides, carbonates or sulphides of the alkaline earth
metals may be used in place of sodium hydroxide. 2
Thioantimonates may also be prepared by the fusion of antimony
pcntasulphidc (or a mixture of antimony trisulphide and sulphur) with
the sulphide or carbonate of an alkali metal, 3 or with sodium thio-
sulphate.' 1 They arc also obtained by the action of hydrogen sulphide
upon, solutions of alkali ortho-antimonatcs. 5
Thioantimonates of.' the alkali or alkaline earth metals arc cither
colourless or slightly yellowish ; those of the heavier metals arc darker
in colour. Salts of the alkali and alkaline earth metals can be heated to
red heat, in the absence of air, without decomposition ; but in air they
decompose gradually. The}" are soluble in water, but insoluble in
alcohol : the aqueous solutions decompose on standing, and also on the
addition of acids, or of carbon dioxide. Some solid thioantimonates of
the heavier metals are decomposed by the action of mineral acids, with
formation of antimony pen tasulp hide. 6
When a solution of a thioantimonate of an alkali metal is boiled with
powdered sulphur, alkali thioantimonite is obtained. 7
Some metallic sulphides, among them being the sulphides of copper,
cadmium, mercury and iron, arc slightly soluble in solutions of alkali
thioantimonates. 8
A number of hydra ted forms of thioantimonates of alkali metals has
been prepa.red and described. 9
Thermal analysis of the system antimony trioxidc-antimony tri-
sulphidc (fig. 4) indicates the presence of an. oxysulphide of antimony,
Sb 4 OS 5 , which decomposes at 522 C. This compound has also been
obtained by the action of dry hydrogen sulphide upon antimony pcnt-
oxidc. 10 The mineral kerme.site* 2Sb 2 S 3 .Sb 2 O 3 or Sb ( .O 3 S 6 , corresponds
Wilson, 6V/ //ttflW I'ftfwl, I 92-4, 25250;*.
7 Dullos, Arrfr/r drx ApotJif/^.yrcreitis -im iKirdlichrn. DtnlxcMand, ] S30, 31, 04; 1831,
6, 27S.
8 Storch, />(-/., ISSr'J, 16, 2<H5. .For Hie action of sodium thioant imonnte on other
iK'tallic salt solutions, sec Lannhans, Zi.it^cfi. (t-nal. GJic.'i'n.., 102J, 60, 1)1.
Donk, Che-m. \VccJ:blad, J90S, 5, 529; 1008, 5, 629.
10 Qucrciah, Atfi. R. Acc/td. Llncc.i, 19.12, [5]. 21, i, 415; Schumann, An-iuilc.H, 1877, 187,
;12.
110
AXTIMOXY AND BISMUTH.
in composition to the cutcctic of antimony trioxide and the above-
mentioned oxysulphide. 1 This substance is also stated to be formed
by heating antimony trisulphidc to a red heat in an atmosphere of
steam, 2 by the action of dry hydrogen sulphide upon antimony
trioxide, and by boiling antimony thioiodide, SbSI, with zinc oxide
and water. 3 The natural mineral is a cherry-red or bright red, brilliant,
700
600
5
t.
400
300
488C.
522 C.
10 20 30 40 50 60 70 80 dO 700
Mols. per cent. S^S^
FIG. 4. Freezing Point Curve of the System Sb 2 3 -Sb 2 S 3 .
crystalline substance belonging to the monoclinic system, 4 having
pseudo-rhombic symmetry :
a : b : c= 3-9650 : 1 : 0-8535 ; /3=90 C 0'
Its hardness on Mohs' scale is 1-0 to 1-5, its density 4-5 to 4-6. It melts
easily when heated in the blowpipe flame. It is decomposed when
heated in a current of hydrogen ; 5 it is soluble in hydrochloric acid, and
in a solution of potassium hydroxide, but is insoluble in a dilute solution
of tartaric acid. 6
Antimonyl Thioantimonate, (SbO) 3 SbS 4 , is obtained by the action
of sodium thioantimonate on potassium antimonyl tartrate. 7
If the fused oxysulphides of antimony are cooled quickly, they are
converted into glass-like substances, known sometimes as "antimony
glass."
Many of the substances that have been described as oxysulphidcs
of antimony are most probably mixtures. 8 Some of these, known
as kermes mineral, were formerly used medicinally. They were very
1 Quercigh, lor., cif.
- '.Regnaiilt, Ann. Chim. Pliyx., 1836, 62, 383.
3 Schneider, Pogg. Annalm, .1800, no, 151.
4 Pjanitski, ' Zc.-itech. Kryst. Min., 1891, 20, 422.
5 Hose, Porjg. A nwnJ <>.," \S~24, 3, 482; 1853, 89, 318.
' Baubigny, Co/npl. rend., ]8 ( .)4, 119, 737.
7 Rammelsbcrg, /V/f7- A-)> nnltu, I84-.1, 52, 2!>G.
8 Faktor, P/iarni. Post, 1900, 33, 233; J 'roust, (lilberCs Atinnhn, 1807,
Berzelius, Snhweigyc.r's J., 1822, 34, 58; Poyg. Annalen, 1830, 20, 365; 183(>,
\Vcrner, J. pmlct. Cher//., 1837, 12, 53; Soubeiran, J.Pharm., 1824, 10, 528; "^
Fonderie cTAntimonio," German Patent, 1905, ] 601 10.
25, 186;
37, 103;
iniei'c et
COMPOUNDS OF ANTIMONY. Ill
variable in composition. Many methods of preparation were em-
ployed. 1 A somewhat similar preparation was given in the British
Pharmacopoeia, under the name of Antimonium Sulphur a turn,, but has
been omitted since 1932.
Allied to these oxysulphides is a potassium compound, K 2 HSb0 2 S 2 .
2H 2 O (the only metallic compound of this nature that has been
described), which may be obtained in the form of yellowish, needle-like
crystals by the action of a moderately concentrated solution of potassium
hydroxide upon antimony pentasulphidc, 2 or upon a mixture of anti-
mony trisulphidc and sulphur. 3
The existence of sulphite of antimony is doubtful. 4
Normal Antimony Sulphate, Sb 2 (SO 4 ) 3 , may be obtained by
crystallisation from a hot solution of antimony trioxide in concentrated
sulphuric acid, 5 or by the action of concentrated sulphuric acid upon
antimony trisulphide or antimony sulphide ore. 6 It crystallises in thin,
four-sided prisms, density 3-6246. It is stable in dry air, but deliquesces
in moist air. It is decomposed by water, forming a variety of basic
compounds. It absorbs dry hydrogen chloride, and may perhaps form
a complex chlorosulphate. 7 It forms double salts, of the general
formula SbM / (SO 4 ) 2 , with the sulphates of the alkali metals, the alkaline
earth metals and silver. 8
Many basic sulphates of antimony have been described, among
them being the compounds 7Sb 2 O 3 .SO 3 ; 7Sb 2 O 3 .2SO 3 ; 2Sb 2 O 3 .SO 3 ;
1 See Polacci, 23allct,mo chimico farmaccutico Mailand, 1906, 45, 401; Bougoult, J.
Pharm.. Chim., 1003, 6, 18, 509, 547; Compt. rend., 1903, 137, 497; Long, J. Am&r. Chem.
Soc., 1896, 18, 342; Baubieny, Compt. rend., J894, 119, 687; CSLTUO^ ibid., 1886, 103,
258; Zc.itsch. anal. Chem., 1888, 27, 651 ; Tcclu, Dingl. poly. J., 1880, 236, 336; Weppen,
Bw. 9 1875, 8, 523; Tcrrcil, Compt. rvnd., 1873, 77, 1500; Ridl. Soc. chim., 1876, [2], 25,
98; Wilson, ZritfirJi. anal. Chem., 1877, 16, 424; Ungor, Arch. Pharm., 1871, [2], 145, 15;
Akermann, Offers. K. Vet. A lead. Porh., 1861, 235; J. prukt. Chem., 1862, 86, 57; Mchu,
,/. Pharm. Chim., 1868, [41, 8, 99; Wagner, Wagner's Jahresber., 1858, 235; 1862, 331;
Rickher, Ncucs Jah-rb. Pharm., 1856, 6, 260; Bottgcr, J. prakt. Chem., 1857, 70, 437 ; Petten-
kofer and Unpx;r, Diwjl. poly. J., 1849, 113, 215;' Himly, Annalan, 1842, 43, 150; Strohl,
,/. Pharm. Chim., .1849, [3J, 16, 11; Soubeiran, J. Pharm., 1841, 27, 294; Kosmann,
,7. Pharm. Chim., 1850, [3], 18, 321; Buehholz, Berlinisches Jahrbuch der Pharmacic,
1839, 29, ], 26; Rose, Pogg. Annalc.n,, 1829, 17, 324; 1833, 28, 481; 1839, 47, 323;
.Bnuules, Archlv drs ApoLhcL'crre.rerns im, nor ditch en Dcutscliland, 1831, 37, 257; Sch-
?ai/ i 7f/er',s' J., 183), 62, 209; J^uchncr, Jic.pcrtonum fur die Pharmacic, 1822, 13, 169, 203;
,/. Pharm. Chim., 1830, [2], 16, 51; Buflos, Archiv des ApothRkwve.reins im nvrdlichtn
Dwtfichlmid* 1829, 31, <)4; "183J, 36, 278; fichw rigger's J., 1831, 62, 210; 1833, 67, 269;
AicMrfurd\'c.yr*rr.ni[(iA r alnrhhrfi, 1830, 19, 61, 289; Gay-Lussac, Ann. Chim. Phys., } 829,
42, 87; tic/i.w{'if/yr.r\<i J., 1829, 57, 252; Pogy. Anna] en, 1829, 17, 320; Gci^er, Rcperlorium
fur ({ic. Plmr-mnc.ic, \ 829, 9, 274; von Liebig, J\Iayazin dcr Pharmacia, 1831, 35, 120; Annalen,
'l833, 7, I; .1839, 31, 57; Ilennsniann, Tasr.henbuch fur Scfiaidekunstler und Apothekcr,
1822, 1S4; Ht'iiry, J. Pharm., J82S, 14, 145; Pagcnsteclicr, Repcrlorium fur die Phar-
n/arir,, J822, 14, 'll)4, 545; Phillips, Annals of Philosophy, 1825, 25, 378; Vogcl, Sch-
v.-cigr/ffx J., 1822, 33, 291; Thomson, Schw&iy gar's J., 1815, 17, 396; Ann. Chim., 1815,
93,'J:J8; Kobiquet, Ann. Chim., 1812, 81, 317; Schradcr, Gehlcris ally. J. Chem., 1807,
3, 151); Cluxol, Ann. Chim., 1807, 63, 155; Thenard, Ann. Chim., 1800, 32, 257; Foucroy,
Crrir* Anna I en, .1778, I, 423; GcoJTroy, Mem. Paris Acad., 1734, 593; 1735, 94.
- J^ammelsberg, Pagg. Annalc.n, f841, 52, 199; Schiff, Annalcn, 1860, 114, 202;
Mf(.:a,y, Amcr. Chr.m. .//,'.! 896, 17, 770.
-' Weinland ami Gu1.ma.nn, Zr->f.Mh. wnorn. Chem., 1898, 17, 414.
- 1 Rohrig, ,/. prrtkl. Chr.m., 188R, [2J, 37, 241.
5 .Dexter, ,/. pr./:f.. Cham., I8(i9, 106, 134; Sehuliz-Sellack, LV:r., 1S7I, 4, 13; HenspMi,
ttrr. Trar. cfum., I SS4, 4, 101; Aclie, ./. Chf-m. Hoc., 1890, 57, ~A(}.
' J-Iensiren, Inc. c.-it.; .Metxl, Zcifw.h. fn/nrg. Chem., 1906, 48, 1-46; German Patent, 190-1- ,
161776. T Ilcnsgcn, loc. cit.
8 Ciitmaim, Arch. Pharm., 1898, 236, 477; 1908, 246, 187; Metzl, loc. ciL; Knhl,
Zcitsch. anorg. Chem., 1907, 54, 256.
112 AXTBIOXY AXD BISMUTH.
(SbO) 2 S04; 3Sb 2 O 3 .5SO 3 ; Sb 2 3 .2S0 3 . They arc obtained by the
decomposition of normal antimony sulphate by water. 1 Basic sulphates
have also been obtained by fusing either antimony or antimony tri-
sulphide with potassium hydrogen sulphate. 2
Bv the action of fuming sulphuric acid on. antimony trioxide, an
acid sulphate, Sb 2 3 .4SCL, has been obtained in the form of small,
brilliant, granular crystals, readily decomposed by water. 3
By adding a hydrochloric acid solution of antimony trioxide to one
containing a mixture of sodium thiosulphatc and the chloride of an
alkali or alkaline earth metal, several metallic antimony thiosulphates,
or stibiothiosulphates, have been obtained. 4 The mixture is maintained
at a temperature of about 3 C. These salts, with the exception of those
of sodium, calcium and strontium, may be crystallised out by the
addition of alcohol.
Potassium Stibiothiosulphate, K 3 Sb(S 2 O 3 ) 3 , forms silk-like,
needle-shaped crystals resembling asbestos. It is very soluble in water,
but decomposes on boiling, with formation of the orange-red oxysulphide
Sb 6 3 S 6 . The rubidium and barium salts have also been obtained.
The salts of sodium, calcium and strontium exist only in solution. The
potassium salt appears to have the constitution represented by the
formula Sb[S.SO 2 .OK] 3 .
By the hydrolysis of these alkali stibiothiosulphates fairly stable
sols of antimony pentasulphide may be obtained. 5
ANTIMONY AND SELENIUM.
Several compounds of antimony and selenium have been reported,
but it is probable that the only true compound is antimony triselenide,
Sb Se a . Thermal analysis, supported by thermoelectric and micro-
scopical examination, suggests that the so-called compound Sb 2 Se 7 is a
mixture of antimony triselenide with selenium, and that the existence of
the compounds Sb 4 Sc 5 and Sb a Sc 4 is doubtful. Some evidence in favour
of the existence of the compound SbSe has been adduced from micro-
scopic investigation and investigations of electromotive behaviour. 7
Antimony triselenide is obtained by the action of a saturated solution
of hydrogen sclenidc upon a solution of an antimony salt. 8 It is a
brown powder, melting at 572 C. and soluble in hot alkali solutions. It
forms compounds with other metallic sclenidcs. 9
Antimony pentasclenidc is said to be formed by the action of hot
hydrochloric acid upon a solution of sodium sclcnoantimonatc, Na 3 SbSo 4 .
The pentaselenide has not been obtained, however, by precipitation
with hydrogen sclenidc. ]0
1 Metzl, loc. oil..; Aelie, loc. ciL; Dexter, loc. cit.; Peligot, Ann. Chim. Phi/s., 1847,
[3], 20. 283.
2 AVebsky, Zeilsch. anal Chew., ]S72, n, 124.
3 Schultz-Sellack, B<-.r. t ]871, 4, 112.
4 von Szilagyi, Zc"it.<sch. nriory. Chc.'iH.., 1020, 113, 00.
5 von HahnY Kolhid Zdt., 11)22, 31, 200.
c > Parravano, Gazze.ttfi, 1013, 43, i, 210; Pelabon, J. Chi HI. Phys., 1004, 2, 321; ConipL
jfti'J., .100(5, 142, 207: 1011, 153, 343; 1014, 158, 1(5(50; A-nn. Ckiw.., 1020, [0], 13, 121;
lloiackor, An-nulcn, J858, 107, (5; ("'hretien, ('o)npt. rc.titl., li)0li, 142, 1330, 1-112; Ohika-
slii.iro and Fujila, Mf-m. Cull. >s>/. Ki/fil.o, 10J7, 2, 233.
7 Krermuin aiul Wittek, 7,nt.xc.h.' Mtiadhrndv., 1021, 13, 00.
8 Moser and Atynski, Monatsh., 1025, 45, 23.1; Uclsniann, Anntilrn, 18(50, 116, 124.
Pclabon, Compt. rend., 1008, 146, 075. See also Padoa, G<izzeUa,-\.WH, 57, 300.
10 J-Ioi'ackcr, loc. cit.; Moser and Atynski. loc. at.
COMPOUNDS OF ANTIMONY. 113
Two antimony selenites, Sb 2 Se 2 O 7 and Sb 2 Se 4 O n , have been
described ; both were obtained by the action of selenium dioxide upon
antimony trioxide. 1
Antimony Selenate, Sb 2 (SeO 4 ) 3 , is obtained as small, white,
crystalline prisms by dissolving antimony in hot selenic acid. It is not
decomposed by water, nor will it dissolve in water ; it is soluble in hot
selenic acid, but only slightly soluble in other acids. 2
Two compounds of antimony, sulphur and selenium, Sb S 2 Se and
SboS 3 Se 2 , have also been described. 3
Complex selenoantimonites and selenoantimonates (corre-
sponding to the thioantimonites and thioantimonates) of sodium,
potassium, and possibly of manganese, have been prepared. 4 The
selenoantimonites, Xa 3 SbSe 3 .9lI 2 O, K 3 SbSe 3 .9H 2 O, Xa 2 Sb 4 Se 7 ,
K 2 Sb 4 Se 7 .3H 2 O, are obtained by the action of antimony triselenide
upon the corresponding alkali selenide. Sodium selenoantimonate,
Xa.jSbSe 4 .9H 2 O 5 is obtained by fusing together antimony triselenide,
selenium, sodium carbonate and carbon, extracting the melt with
water and treating the solution so obtained with more selenium. Trans-
parent, orange-yellow crystals, isomorphous with those of sodium
thioantimonate, arc obtained.
Still more complex compounds of sodium and potassium with
antimony, sulphur and selenium have been described. 5
ANTIMONY AND TELLURIUM.
Kxami nation of the system antimony tellurium indicates the
existence of antimony tritelluride, Sb 2 Te 3 , which can be incited
without decomposition. 6 Antimony tritelluride has also been prepared
from solutions of antimony salts by precipitation with hydrogen
tclluride. 7
ANTIMONY AND NITROGEN.
It is doubtful if direct combination occurs between antimony and
nitrogen, although an unstable powder is formed when antimony is
heated at a dull red heat in a current of nitrogen. 8 Antimony nitride
is said to be formed by the action of antimony trichloride on liquid
ammonia. It is described as an orange substance, extremely sensitive
to moisture ; it is decomposed into the elements on heating to 500 C.
A basic nitrate of antimony, possibly 2Sb 2 3 .X 2 0-, is obtained,
mixed with the oxides of antimony, by the action of nitric acid upon
antimony, the formation of the nitrate being favoured by using cold
acid a.s dilute as possible. 10 The presence of nitrous acid accelerates the
1 X l*on, null. Soc. clihn., 1875, [2], 23, 499.
- Cc rncron and Macallan, Proc. Roy. ,S'oc., 1889, 46, 33.
n vcn Gcrichten, JUvr., .1874, 7, 30; Hofackcr, loc. cit.
\\ u<iet, Ann. Chrnt. Phi/,-'., 1899, [7J, 18, 550; Hofackcr, Annalw, 1858, 107, 6.
I\ uL r ct, loc. cit.: Hofackcr, loc. cit.
\:
i
B ukl, Mnnnlxh., I924, 45, 47 J.
II -rani, Co //////. rcn-d., 1888, 107, 420.
Srh \vttiv. and /K-anrnairc, lic.r., 1932, 658, 100:2.
l-Juchliol/, Taxchnibuch- fur Schc-idf.-kutwlUr und A-ji<>ffickcr, 1S()0, 89; IVui^ot, Ami.
>.. Phyx., 1847,1.3], 20, 283; Anna-ten, 1847, 64, 281; Rose, 7V/ : y. An union, 1841, 53,
Cht
1C I
. .
J>cfort, ' J. Phann. Chim., 1855, [3], 28, 93,
114 AXTLMOXY AND BISMUTH.
action. 1 A somewhat similar compound is obtained by the reduction
of a solution of silver nitrate with metallic antimony. 2
It is stated that normal antimony nitrate, Sb(NO n ) 3? may be
obtained by the action of silver nitrate upon a solution of antimony
trichloride in acetone. 3 The normal nitrate, however, does not appear
to have been isolated.
A compound of quinquevalent antimony, 2Sb 2 O 5 .X 2 O 5 , has been
obtained by the action of nitrogen tetroxide upon a solution of antimony
tribromidc in chloroform, or of antimony triiodide in ether. It is a
white, crystalline substance, not decomposed by water. 4
AXTIMONY AND PHOSPHORUS.
Antimony Phosphide, SbP, has been obtained by the fusion of
antimony with metaphosphoric acid 5 or phosphorus/ 5 The substance
obtained by the action of phosphorus upon a, solution of antimony
tribromide in carbon disulphide may perhaps be antimony phosphide. 7
Antimonyl Dihydrogen Phosphite, (SbO)H 2 PO 3 , has been
obtained by the action of phosphorous acid upon antimony trioxide, 8
and also by the action of potassium antimony 1 tartratc upon an
ammoniacal solution of phosphorus trichloride. 9 It is a white powder,
which, in solution in dilute hydrochloric, acid, is capable of acting as a
reducing agent.
Antimony Phosphate is said to be obtained by heating together
either antimony or antimony trichloride and crystalline phosphoric acid ;
the product may be purified by treatment with acid ammonium phosphate.
A dihydrate has been described, which is slightly soluble both in water
and alcohol, and which is not hydrolysed when warmed with water. 10
Antimony Pyrophosphate, 2Sb 2 O.j.:3P 2 O-, is obtained by dissolv-
ing antimony trioxide in orthophosphoric acid ; 1] and by boiling the
trioxide with a solution of sodium pyrophosphate. 12 By hydrolysis
two other substances are obtained, 4Sb 2 O 3 .P 2 O r> and 2Sb 2 6 :v P 2 O 5 . "
Antimony Thiophosphate, SbPS d , is obtained as a residue, after
the evolution of antimony thiochloride and phosphorus pentachloridc,
on heating together antimony trichloride (or antimony trisulphide) and
phosphorus pcntasulphide. 13 It is a yellow powder which has an odour
of hydrogen sulphide. It is decomposed by heating. It is insoluble in
water, dilute hydrochloric and sulphuric acids and various organ ie
solvents, but it is decomposed by treatment with concentrated sulphuric
acid, alkalis or even ammonium hydroxide.
1 Mill
- Son lerens, Mull. Hoc. rhhn., .1S ( .)(C I:J], 15, 2 IS
X;
1 The
IV11
(Jr
I >
>n, Ann. Chlm. />/>//*., 1 842, [;*], 6, 101.
lorons, Hull. Hoc. chhn., 1S ( .)(), [_:$], 15, 2 IS.
matni, Her., Ji)()4, 37, 4,'j:5,3.
tins, (In-nipt, rend., 18!)5, 120, 11 JO.
>t,u>r, Ami. Chhn., L7!)2, [1], 13, 132.
I.UTrbo, tic/twf-.ir/r/ri'x J , fS2S, 53, 40!)
isny a,nd Maol.vor, />/-., 1 S7.*}, 6, i:j(>2; sec, hmvever, Rairir, Orxli-rr. Ulir-ni. Zc.it.,
(."
/.ncr, Arch. P!;<inn., 1SD7, 235, ()!)!.
-" lira
'- Sc.h
ANTIMONY AND ARSENIC.
A compound of antimony and arsenic, Sb 2 As, has been described, 1
but a more recent study of the system, antimony-arsenic has failed to
confirm its existence. 2 Arsenic is frequently associated with native
antimonv, as in the mineral allemontite?
DETECTION AND ESTIMATION OF ANTIMONY.
Dry Reactions. Antimony compounds, when heated on charcoal in
the blowpipe (lame, are reduced to metal (particularly if previously
mixed with fusion mixture), but the metal volatilises and burns to
antimony trioxide. By depositing the oxide on a glazed porcelain
surface, adding a spot of silver nitrate, and blowing a current of gaseous
ammonia on to the silver nitrate a black stain is obtained. Alter-
natively, if the white incrustation which remains on the charcoal is
moistened with ammonium sulphide solution, a deep orange stain is
produced.
Wet Reactions. When a current of hydrogen sulphide is passed
through a solution containing antimony ions, an orange-coloured
precipitate of antimony sulphide is obtained, the composition of which
varies according to the state of oxidation of the antimony. This pre-
cipitate is more soluble than the corresponding arsenic sulphide, but less
so than tin sulphide. It is soluble in alkalis and alkali sulphides (in-
cluding ammonium polysulphide), and reprecipitated from solution by
the addition of acid. Arsenic and tin sulphides behave similarly, but
antimony may be separated from these elements and identified by one
of the following methods :
(a) Marsh's test (see p. 116) is applied, and the evolved gases passed
into a neutral solution of silver nitrate. The precipitate is filtered off,
washed, and treated with concentrated hydrochloric acid to dissolve
any silver antimonide formed. Antimony can then be identified in this
solution by dilution and treatment with Ivydrogcn sulphide.
(b) Antimony and tin sulphides are soluble in concentrated hydro-
chloric acid, but arsenic sulphide is not appreciably so. If a piece of
platinum foil and a little zinc are placed in this solution the presence of
antimony is indicated by the formation of a black stain on the platinum,
which docs not disappear on removal of the zinc.
(c) Arsenic sulphide may be separated as in (b) by treatment with
concentrated hydrochloric acid ; antimony and tin are detected in the
solution by making use of the different solubilities of their sulphides in
the acid. 4
(d) Arsenic and antimony may be detected in an acid solution
containing an excess of tin by the addition of a little stannous chloride,
followed by sodium bisulphite or sulphurous acid a drop at a time. The
hydrogen sulphide thus liberated first precipitates arsenic trisulphide,
1 I)fsca.rn]-)s, C<,tpL rend., 1878, 86, 1000.
- Parrav.'iiio and do CVsuris, in.lfrnaL Zcil^c.//,. M (tdlloynt pJiic, I 9 I '2, 2, 70.
'' r{ainmcl.-J)or.L!, /V/f/. Aniinlc.ii, 1.8-14, 62, J,'J7; Couth, 'A mar. J. Fci., 1 802, \2], 33,
P.M.); Br/arri, dnzztf.lu, 188G, 15, IU1).
4 Tread well and Hall, "Analytical Ghe.m-i*try" (Xeu- York), 5th" Ed., 1921, I,
293.
11G ANTIMONY AND BISMUTH.
and afterwards antimony trisulphide. Under these conditions no tin
sulphide is precipitated. 1
An important test for antimony is Marsh's test, which is carried out
in a manner similar to that employed for arsenic (see this Series, Vol.
VI, Part IV). Stibinc, which is produced in this test, is decomposed at
a lower temperature than arsine, and the antimony mirror is usually
formed in front of the constriction in. the heated tube ; this antimony
mirror is not readily soluble in bleaching powder solution. (It is
important that the bleaching powder solution should be freshly prepared,
as old solutions always contain some chlorite, in which the antimony
deposit is soluble. 2 ) The deposits produced by arsenic and antimony
in this test may be identified individually by passing a current of hydro-
gen sulphide through the heated tube in the reverse direction to that
taken by the gases evolved from the generating flask ; a yellow deposit
indicates arsenic, while an orange-red deposit indicates antimony.
Further confirmation may be obtained by passing a current of drv
hydrogen chloride through the tube ; the antimony sulphide is removed
while the arsenic sulphide remains. Marsh's test for antimony is
sensitive to 0-0002 mg. 3
Antimony compounds arc readily hydrolysed, yielding, with cold
water, insoluble basic salts. If boiling water is used, hydrolysis some-
times proceeds a further stage with the formation of antimonie acid or
hydrated antimony oxides. The insoluble residues are, in general,
redissolved on acidifying.
The more difficultly soluble antimony salts may be dissolved in
liquids containing tartaric acid or tartratcs, the resulting solutions
being stable only when neutral or alkaline ; on acidifying, insoluble
hydroxides or hydrated oxides are produced.
Antimonious compounds may be distinguished from antimonie
compounds by the action of hydriodic acid, or potassium iodide in acid
solution ; iodine is liberated by antimonie compounds but not by
antimonious compounds. 4
Gravimetric Methods. The method most usually adopted for I he
estimation of antimony is by precipitation of the trisulphide. 5 The
sulphide, which is precipitated from a cold, acid solution (the solution
being raised to boiling towards the end of the precipitation ). is i horoughly
washed, dried and converted to black crystalline antimony trisnlphide
(by heating in a current of carbon dioxide), in which form it is weighed. 6
The black, crystalline product may be produced direct if the precipita-
tion is carried out in a hot solution rendered strongly acid with hydro-
chloric acid. 7
Antimony may also be estimated as Letroxidc 8 by precipitating iirst
1 Doimth, CJifim. ZtiL, 1932, 56, 483.
- Vaiibcl and Knocke, Chew. ZciL, 19L6, 40, 209.
3 Scheucher, Mo-nat^h., 1921, 42, 411. Also Santrer and GiLson, J. #ot
1907, 26, 58/5.
4 Sec also Dufjaionois, Corn-pi . rend., 1933, 197, 339; Gallic and Viol, ibi
"' Ilcnx, Zctlwli. f//u-f/. Chi'in., 1903, 37, IS.
(; Paul, Zatsc.li. anal. Clu-m., 1892, 31, /1 10.
7 Vorlni.-iNii and Met '/I, Z( itwh. (t/i(tl. Cl/c//i., 19()f>. 44, r>20. S-i> ;sN;o Maiu-iiot ,
(rassl and Sclnvc'oci^cr, Zc.it*<'/i. dual. C/K'in., 192."), 67, .177.
b Bun^cn. A-iiH'tlt'-ft, I 858, 106, 3; 1878, 192, 310; Brunck, Z'-ilwh. until, ('ln-m., 189"),
34, 171; KossiiiLi, -ibid., J902, 41, 9; Hcnz, loc. ciL; JLJuubigiiy, CowpL rw.d., 1897, 124,
499.
COMPOUNDS OF AXTIMONY. 117
as trioxidc, oxidising this precipitate with nitric acid and igniting the
residue carefully at 800 C.
In the presence of: sodium potassium tartrate, and in faintly acid
solution, pyroo-allol I will precipitate antimony quantitatively. 2
Volumetric Methods. 3 (a) Potassium Br ornate Method. In this
method, tervalent antimony is oxidised to quinquevalcnt by the action
of potassium bromate :
KBrO 3 + 3SbCl 3 + 6HC1 - 3SbCl 5 -f KBr + 3II 2 O
The substance containing antimony is dissolved in concentrated hydro-
chloric acid to which bromine lias been added. Excess of bromine is
removed by boiling, and the solution reduced by the addition of sodium
sulphite solution. The hot solution is then titrated with standard
potassium bromate solution until the colour of methyl orange is de-
stroyed. The presence of calcium, magnesium and ammonium salts in
quantity tends to give high results, while excess of copper obscures the
end-point. If copper is present in any quantity, it is advisable to
remove it before estimating the antimony. 4 Solutions containing
antimony in the quinquevalcnt condition may be completely reduced bv
mercury in the presence of 3 to 4-A r ITC1. The reduction should be
carried out in an atmosphere of carbon dioxide. The antimony may
then be estimated in such solutions by the bromate method. 5
(b) Potassium Iodide Method. In this method the sample is dis-
solved in hydrochloric acid to which a little potassium chlorate has been
added. Excess of chlorine is removed and potassium iodide added ;
the liberated iodine is then titrated with a standard solution of sodium
thiosulphatc.
(c) Iodine jMetliod. The solution is made in hydrochloric acid ;
tartaric acid is added and the mixture neutralised with sodium carbonate.
The solution is now made faintly acid, a saturated solution of sodium
bicarbonate is added and the mixture is titrated with standard iodine
solution. 6
Other volumetric methods have been suggested involving the use
of the following solutions : potassium permanganate, 7 potassium di-
chromatc, 8 cerium sulphate 9 and titanium chloride. 10 Chloramine-T
(sodium y;-toluenesulphoncehloramide) may also be employed either for
potcntioiuetric or visual titration of antimony. 11 A. hydrochloric acid
1 Fei^l, Zalxch. anal. Ckw.. 3 1024, 64, 41.
- See also Wen^er and Paraud, Ann. Chim. anal., 1923, [2'1, 5, 230; Darling, Chcm.
Ewj., 11)11), 27, ]1," 63; Chan.. ZaiL, 1919, ii, 890; 1920, li, 750; Cohen and Morgan,
Analyst, 1000, 34, 3.
3 'Schmidt', 67^y,,. Zc.it., 1010, 34, -153.
4 Cyory, Zriter./L. cum!. Chc.w-., 1893, 32, 415; Duncan, Cham. News, 1007, 95, 49;
Xissenson and Siedler, Chun. Zr.-iL, ] 903, 27, 749; llowcll, J. tioc. Chem. Ind., 190G, 25,
1181 ; Xikasono and Inoko, J. Chun. Soc. Japan, 192G, 47, 20; Prcschar, Phar-m. Zentr.-'k.,
1924, 65, ()] ; Zinil and Wallenberg, ]><-r., .1923, 568, -172; Jarviness, Z&itsch. anal.
Cher,!.., 1023, 62, 18-5; Kvans, An,aly*(., 1032, 57, 554.
5 McCay, Jnd. Ewj Chc.m.., Anal Ed., 1033, 5, 1.
Brukf, M-ikntc.hc.'tin.c, 1923, I, 54; Ivolb and Formhals, Zeitsch. anorg. Chem., 1908,
58, 202; Szcbollecly, Ztilach. anal. Ckcm., 1030, 81, 36.
7 Collenbere and Bakka, Zdtsch. anal. Chem., .1923, 63, 229; Knop, ibid., 1923, 63,
81; :\Inck, Ckcm. Zeit., 1022, 46, 790.
8 FJo\-shcr, J. Arn.e.r. Chan. Soc., 1924, 46, 2725.
9 Furman, -tlid., 1932, 54, 4235.
10 Oliver!?, Ann. cliim. applicata, 1931, 21, 211.
11 Tomicck and Sucliarda, Casopis Ccskoslov Lehirnidva, 1931, n, 285, 309, 320.
118 ANTIMONY AND BISMUTH.
solution is used, with, in the case of visual titration, methyl red as
indicator.
Electrolytic Titration of antimony 1 may be carried out in a boiling
solution in dilute hydrochloric acid containing hydroxylamine hydro-
chloride. The initial current should be 3-20 amperes at a pressure of
2 volts.
Electrolytic Methods. The quantitative clectrodeposition of
antimony from acid solutions presents considerable difficulties, but the
method has been employed for the estimation of the metal. 2 Solutions
of sodium or ammonium thioantimonite or thioantimonate are more
usually employed. The presence of polysulphides interferes seriously
with the deposition, but their influence may be minimised by the
addition of sodium sulphite 3 or potassium cyanide. 4
Microanalytical Methods for antimony have also been described. 5
1 Grosset, Bull. Soc. chim. Belg., 1933, 42, 269.
2 Lukas and Jilek, Chem. Listy, 1926, 20, 63, 130, 170; Schleicher, Toussaint and
Troquay, Zeitsch. anal. Chem.., 1926, 69, 39; Scliock and Brown, Eighth Intern. Cong.
App. Chem.., 1912, 21, 81.
3 Lecrenier, Chem. ZeiL, 1889, 13, 1219.
4 Fischer, Jler., 1903, 36, 2048; Zeitxch. anorg. Chem., 1904, 42, 363; Holiard, Bull
Soc. chim., 1900, [3], 23, 292; Henz, Zeitsch. anorg. Chem., 1903, 37, 31. Also Ost and
Klapproth, Zeitack. angew. Chem., 1900, 13, 828; Foerster and Wolf, Zeitsch. EleJctrochem.,
1907, 13, 205; Dormaar, Chem. IVeekblad, 1907, 4, 55; Schecn, Zeitsch. Elefarochem.,
1908, 14,257; Cohen, Zeitach. Elektrochem. t 1908, 14, 301; Mazzucchelli and Tonini,
Atti li. Accad. Lined, 1923, [5], 32, ii, 290; Lassieur, Compt. rend., 1923, 177, 263; Parodi
and Mascazzini, Zeitsch. anal. Chem., 1879, 18, 587; Luckow, ibid., 1880, 19, 13; Classen
and Keiss, Btr., 188], 14, J629; 1884, 17, 2474; 1885, 18, 408; 1894, 27, 2074.
5 Ordosen and Rcssy, Bull. Soc. chim., 1923, [5], 33, 991; Brukl, loc. cit.; Sjollcma,
Chem. Weekblad, 1908, 5, 11; Schoorl, Zeitsch. anal Chem., 1908, 47, 367.
CHAPTER III.
BISMUTH AND ITS ALLOYS.
Symbol, Bi. Atomic Number, 83. Atomic Weight, 209-00 (O=16).
Occurrence. Although numerous minerals containing bismuth have
been described, very few occur in sufficient quantity to be of economic
importance. In general they occur in metalliferous veins associated
with ores of cobalt, nickel, lead, zinc, tin, silver, etc. The more im-
portant ores are those containing native bismuth, bismuthinite or bismuth
glance, Bi 2 S 3 , tetradymite (sulphide and telluride of bismuth), bismite or
bismuth ochre, Bi 2 O 3 , and bismutite, Bi 2 3 .CO 2 .H 2 O. Deposits occur in
many parts of the world, those of Bolivia being the most productive
on account of the bismuth minerals in the mountain of Tazna situated in
that country. 1 The deposits in Germany, 2 Czechoslovakia and Hungary
are mainly of historical importance. Deposits have also been found in
Spain. 3 Bismuth-bearing minerals have so far been found only in small
quantities in the British Empire, but attempts have been made to
develop those of Australia. Native bismuth and bismuthinitc have
been found in the wolfram- and cassiterite-bcaring veins of Lower
Burma. 4 The compositions of some minerals from Vasko ( Hungary)
are given in the following table : 5
COMPOSITION OF SOME BISMUTH MINERALS
FROM HUNGARY.
j
Bismuthinite,
j Bi 2 S 3 .
Corsalile,
PboBi,,Sr, or
2PbS.Bi 2 S a .
41-75
Re/banyitc,
Cu,,L > b Bi 10 S lf) or
Cuj3.3tbS.5Bi 2 8 3 .
Bismuth
80-04
76-74
59-28
59-22
Copper .
Silver .
0-57
0-93
3-41
0-32
4-17
4-09
Lead
0-69
3-29
37-68
18-38
18-10
Iron
0-40
0-11
0-68
0-46
0-42
Sulphur .
Silica
Total
18-46
18-62
0-43
15-92
17-85
17-86
0-12
100-16
100-12
99-76
100-14
99-81
.9. - Kuhne, Chem. Erde., .19,32, 7, 503.
1930, 28.
1930,47, 219, 227; Ctnlr. Mineral.
120
ANTIMONY AND BISMUTH.
om
-y,
j
i!
ce ~
V
or
2 c c
I II
a
P . o
yj -
t- -r c;
n n
^ m cr-
y P
r/T ^ o>' ^' ^ .JT 1 ^:,
-4 1 CA --' ^ ^ V" ~ XX -/^
1C
P^: .J' - X^ 03 ^ -i -. -
BIS^IUTH AXD ITS ALLOYS.
121
!>3 CO -*
X, X
o o
p
CO CO
c o
ANTIMONY AXD BISMUTH.
O
BISMUTH AND ITS ALLOYS.
I C--
O 5
j C
, S
-5 r^ " *
124
AXTTMOXY AXD BISMUTH.
w
ID
& - s s
^J M"
O COfT
c- o
6
co
/< ~ ^Q f- ~s ^^ ^ ~
^. = . ~ ^ -f-* 1 ^ "5 sTn oTE; c^ '^ "d ^
^ ^~2 x ~r ^^^^^-^^r^^~si"x; J^ ^ ^ oc ^ - 1: "" ^ ~"^
^'^ '|s ^<|8^^^-5^l5 ^^-" i-^I sV : *^<^
^^^^^ . 1 = si^ si^: ^ri M<5|.= ;? ^ ^- =^^:^' --- v:
BISMUTH AXD ITS ALLOYS. 125
An examination of the geological formation of the deposits in South
America ! suggested that as native bismuth was found in the upper
oxidised portions of the deposit, it should be regarded as of secondary
formation, the primary material being bismuthinite.
Details of some of the more important bismuth minerals are given in
the tables on pages 120-123. in which the various minerals are grouped
together according to their composition. The formula?, are included to
give some indication of the composition, and do not necessarily represent
definite chemical compounds. 2
Early History.' Apparently the first mention of bismuth as a true
metal was made by Agricola in the sixteenth century ; 3 he describes it
as a form of lead and outlines a process of extraction by liquation.
Bismuth was probably known at a much earlier date, but as it was
frequently referred to as m area site a name used for many different
materials the early history is confused. Paracelsus in the early
sixteenth century regarded bismuth as a semi-metal. It was found
associated with, ores of tin in Saxony, and during extraction bismuth and
tin were melted together, the tin thus becoming brittle and hard.
Reference to the discovery of bismuth in Europe was made by a South
American priest in a report prepared by him on the metal resources of
South, America.. 4 He wrote : " Bismuth was discovered a few years
ago, in the Sudnos Mountains of Bohemia ; it is a metal somewhat like
a cross between Tin and Lead, without being cither of the two."
The metal appears to have been used chiefly in the manufacture of
pewter, the addition of bismuth making the metal more sonorous.
The chemistry of bismuth and its compounds was investigated by
Lcmcry, 5 Pott. 6 Geoff roy, 7 Bcrgmann, 8 Davy, 9 Lagcrhjelm. 10 Muir and
his collaborators, and others.
The origin of the name is not known with certainty. It has been
derived conjecturaily from Arabic and from Persian, but it is possibly
of German origin, connected with a miners' term ids mai (weis.se masse)
meaning ''white mass. v - 11
Extraction. Formerlv bismuth was extracted principally from
J KiMl, J-fer. Alini-.ni. tioc. Ar(jc.nlina 31 i-iicrtt- 6'cW. (Jjnuws J/Ve*), 1 930. 2, I.
- For further mincralouieal data and analysis, sen.' Dana, "A tiysl.c.-m of 31 iitf-/fi'oy// ''
(London and New York), (5th Fd., IS!);); Appf-.ia lui /, 180!); Appc.ndu: If. 1909; Apptndlt
///, !919. The economic aspect is discussed by Allen, " J/o/;or//v//;/?, <-,/>. 31 inf-.t'ol. lt(--<ourc(.'.s
iri/h X-jxTJul ttfff-f'ni.cr. to the, IrrUi+h /;/'/ ;;//v, A'o. 1H, .ttixm /////,' On-.* "' (London), 1!)2,">. A
bjbliO.uTaph v is (} ti ached.
'' Auricola, " l)c. re. m.f-ldJlic.ci,'''' J5asili'C, LloS, 41)!); translated by Hoover (London),
\\}\'2: '])(' vaf.wrd. j'o.^i.'l inni^ Basditc, 1;")8, 337. See also Matthositis, I1f.rf/-J>oxldl,
Xurnherii, ]~)(>'2, 395; Jjibaviu.s, " J)c. tuilnni nic-iallaruiii^'' u^rancofui'ti, 1000.
l ]>arbn, "./:'/ A rfc, dc. /o.s- ..'1/e/w/^.v" (Sj)ain), 1040; translation by J^oui^la.'S and ^laiheu'-
son (Xe\v York), .1923, p. fa.
:> Lcmcry, " Ca-nrx dc, Ch inn e" : (Pan's), 1G75.
'' Poll, " Ob^f-.rva! iOii.U'tti c-.l ait.i)/i f i(l>;ti SiO'ii'iun. (.iliy'inicurn dc witihi.uth-*" (.Berohni), 1739.
7 UeolTroy, J/r>/,-. Acnd., 17"):j, 21)6.
8 ixM'iimann, " Dc. ')fi.>ii(r<t.r>i.i)i dociinc^ln LiUiniIci" (I'psala), 1.7SO.
u Davy, l>htl. 7'/vn/.s-., 1812, 102, 1C!).
1:) La.jj-erlijehn, Ann. ('linn. VV/v/.s-., ISIS, [('I, 9/j, 101. See also Kopp, ' ; rtrw'/i.ichl.r. d( r
C/tt in>':'- (IJi'-aiinscIuvc-i.^), IS!;'* I o ISi", 4, liO; Lipprnann, "!>u: Ucw'kic.hlc, f/'-.v WiHHmlfi
:.in<clini. / /f)0 'Had JSf/fj" 1 (Berlin), I ( ,),'j(). l-'ur a.n his! nncal aecounl, ol t.he use of bismuth
in },hannai-v, see !)y.-.on, I'lnirm. J ., I!l28, 120, 242.
11 von Lipinnann, "Enl,--l< hi.i.inj mxl A u*f>-/-< il.mnj <l< )' A IrJu >;//<; " (Berlin), ID! 9, p. 0-12;
Ihntxc, " Jld.t'llnic.h. '(h / M ,n(:rl >(]>(-.'' (i,eij)xi,ii) ? V.;()f, i, 123; J ioit nuain, AYv/r,s Jnhi b.
Mm.. 1878, 291 : von !\obell, '' (*' whir /tie. dcr 31 ttiwtlvyic" (Miiiiclic-n), 18G4, 004; Kular.cl,
"Ltxtcuit, alcliL-riiit'' (Lraiicoi'urti), JG.L2: Matthe^ius, loc. Ctt.
126 ANTIMONY AXD BISMUTH.
native ores by the process of liquation. The ore was heated in inclined
cylindrical furnaces and the molten bismuth allowed to flow away from
the gangue. This crude bismuth was afterwards refined by an oxidising
fusion, sometimes followed by poling. As native ores are, however,
always associated with oxide or sulphide minerals, or both, neither of
which can be treated satisfactorily by liquation.the process is now obsolete.
Bismuth ores do not occur commonly in sufficient quantities to
justify direct treatment, but in such cases the main principles under-
lying the extraction are, firstly, the maintaining of a low temperature on
account of the volatility of the metal, and secondly, the use of fluxes
suitable for the formation of." a fusible slag of a sufficiently low density
to enable the metal to separate. The operation may be carried out
either in crucibles or in reverberatory furnaces. (1) In the case of
oxide ores which are comparatively unimportant charcoal or other
form of carbon is used as the reducing agent, the fluxes being sodium
carbonate, lime and oxide of iron or oxide of manganese. (2) In the
case of sulphide ores, particularly if associated with sulphides of arsenic
and antimony, the ore is first roasted ; arsenic and antimony are thus
converted info oxides, partly volatilised and partly removed as scum,
while bismuth is converted into a mixture of oxide and sulphate.
Reduction to metal is carried out as for oxide ores with the addition of
a little iron to remove sulphur. In Bolivia, where the sulphide ore is
sufficiently rich and plentiful to be of economic value, smelting with iron
is practised, either with or without a preliminary roasting. If there is
a preliminary roasting, some bismuth is liable to be converted into
bismuth sulphate, which ultimately will tend to pass into a matte. The
fusion is carried out in crucibles and reverberatory furnaces, the fused
products consisting of crude metallic bismuth, a matte containing
copper with 5 to 8 per cent, bismuth, and slag. The matte is sub-
sequently treated in a similar manner until its bismuth content is
reduced to 2 to 3 per cent. Both metal and final matte arc then refined. 1
The roasting of bismuth sulphide ores presents some difficulty, as the
elimination of sulphur is usually incomplete unless cither an excess of
oxide is present, or special precautions are taken. 2
The crude metal obtained in this manner may be refined by an
oxidising fusion which removes lead arid other easily oxidised metals ;
the addition of bismuth sulphide assists in the removal of copper as
sulphide. The resulting metal is then poled. Frequently bismuth vl
chloride is used as a flux in this refining process. A considerable
quantity of crude bismuth, however, is converted directly into pharma-
ceutical products, and for this purpose wet methods are usually
employed. Electrolytic refining processes are now more general for
the purpose of obtaining pure metallic bismuth (see p. 146).
As has been mentioned, in most localities bismuth ores arc associated
with ores of other metals, notably lead, tin, 3 copper, nickel, cobalt,
antimony, arsenic, gold and silver. From these ores the bulk of the
world's supply is now obtained, and the method adopted for the extrac-
tion of the bismuth depends lo a large extent upon the na.furc of the
1 Sclmaljcl (translated hy "II. Louis), '' IhonlLr^lc. of Mtl<iUur<j>j'' (London), 2nd I'M.,
.1007, 2, -1f)5; Gotland, "Thr-. Mf-lalluryy of the. 2f(tti-F(-rrous Mr-ldlx** (London, 191-i),
p. -1G(>; ."Friek, Mcl'dl v.nd J-Jrz, I 028, 25/550'.
- Schcnck and .Spoeknuirnu Zutxch. a/Lory. C/tnii.., 19:52, 206, 378; Koldtneyer, (Jc.rimin,
Patent, 1930, 554337; Schocller, J. Soc. Cfie.rn. Ind., 1915, 34, {>. {See also p.' 198.
3 "Mineral Resources of the United .Slates of America," 1928, Part 1, A 18.
BISMUTH AND ITS ALLOYS. 127
associated minerals, although in some cases the ores may be concentrated
by the usual mechanical processes and the bismuth concentrates treated
separately. Lead-bismuth ores are usually treated as for the extraction
of lead, and the crude product subsequently desilverised by the Parkes
process ; much of the bismuth is retained in the desilverised lead. This
is then subjected to the Tredinnick-Pattinson process a modification
of the Pattinson process for the desirverising of lead Avhcreby the
bismuth is concentrated in a small quantity of lead. 1 The bismuth-lead
alloy is then treated by the Bctts electrolytic process. 2 In this process
the electrolyte is composed of an acid solution of lead fluosilicatc con-
taining free hydrofluosilicic acid; the cells are of concrete Avith a lining
of asphalt and are arranged in cascade, there being usually seven cells
in cascade. The general arrangement is similar to that employed for
the electrolytic refining of copper. The current density is 1-8 to 1*9
amperes per square decimetre, and the potential drop between electrodes
is 0-35 to 0-4 volt at the beginning, rising to 0-65 to 0-70 volt at the
eighth day. The electrolyte is made to circulate through the cells.
The anodes are composed of crude lead containing 2 per cent, of im-
purities, including bismuth. Antimony is usually present, and is an
advantage, as it adheres to the anode, and during the process forms
with lead a protectiA^e network which remains in position after the bulk
of the lead has been dissolved, thus holding the slime, which can be
Avithdrawn with, the used anode. Bismuth is found in these slimes, the
treatment of Avhich depends A*ery largely upon their composition. This
treatment has not been fully published. In one process the slimes arc
fused Avith alkalies under oxidising conditions, with the addition of
sodium sulphide if copper is present. Arsenic, lead and copper pass into
the slag and the bismuth, Avith gold and silver, is cast into anodes. 3 In
a second process if gold and silver arc present these arc removed first,
followed by antimony, which is partly converted into lead antimonitc
slag. By a further oxidation fusion copper is oxidised, and copper oxide
and bismuth collect as a slag, from which the bismuth can be obtained
clee.trolyticn.lly. 4 In the electrolytic refining of the slimes, the electro-
lyte is cither a solution of bismuth methyl sulphate (1 per cent.) con-
taining methyl hydrogen sulphate (K) per cent.), or a solution of bismuth
chloride with sufficient hydrochloric acid (10 per cent.) to prevent
hydrolysis. 5 In the latter case the current density is 1 -5 to 3-3 amperes
per square decimetre and the potential drop 0-5 to 1 volt. G
Many other processes have also been suggested for the recovery of
bismuth both from ores and alloy residues. 7
1 Xewmim, Trans. Amer. lust. Min. ting., 1.917, 57, 584.
2 Bctts, U.S. Patent, 1902, 713277; ''Lead Rtfmmg by Electrolysis''' (New York),
1908; Finland, Trans. Amer. EleclrocJieni. Sac., i.930, 57, 1.77. Sec also Schachterle
and 1'ieeke, Metall nnd Erz, 1928, 25, 637.
:i Hay ward, "An Outline, of Metallurgical Practice''' (New York, 1929), p. 329.
4 .Finland, loc. cif..
5 Betts, loc. oil., p. 89; van Krckelens, Eny. Mi.rdiKj J ., 1931, 132, 100; "Donahue,
Trans. Ain.c.r. J'llf'c.lrocJic.rn. Sot;., 1930, 57, 153; Kern a,nd Jones, v/j /''/., 255.
(>) ITa.yu'ard, loc. cit.
7 Finalaml, Tumbull nml Mc.Intyro, U.S. I'tilf-nl, 1931, 1801339; J932, ]8 10028;
IVtierton, U.S. J'afc-nf, 1932, ] 85353-1, 1853535, 1 85353(5; Smil.h, U.S. 7V/,".///, 1932,
JS70388, .1870470; Fnijjand, Ttirnbull and Melnlyre, (lan.adian Pateiil, 1932, 324755;
Colin, Tranv. Awr. Etcrlrnclimi. Hoc.. 1931, 59, 107;' Kmll, Metall and Krz, 1922, ig. 3,18;
U.S. Pa/r[, 1922, M2S011 ; Greene, U.H. J'nl.cnt, 1931. 1821034; Smith, U.S. Palc.nl, 1931,
1809871; Smith and Mank, Jun., U.S. Pale.ni, 1931, 1816620; Donahue, U.S. Patent, 1930,
128
ANTIMONY AND BISMUTH.
ANALYSIS OF ANODES OF CRUDE BISMUTH
(As used for Electrolytic Refining). 1
Tcru.
Australia.
Bismuth
93-37 94-10
90-45
95-03
91-00
Antimony
. i 4-57 2-62
0-19
Trace ! -
0-11
Arsenic .
0-92
0-26
Trace ;
Copper .
; Lead
2-06 1-94
3-71
1-32
2-97
0-87 i
0-48
2-20
i Sulphur .
Iron
0-43
0-99
1-31
0-21
0-45
! Silver
.
186-1 oz.
156-1 oz.
3-20
i
per ton
per ton
An earlier method for the extraction of bismuth from bismuth-lead
ores involved the process of cupcllation. Bismuth will not oxidise until
all the lead is oxidised ; part of it, therefore, during cupcllation, will
pass into the silver, and part into the Final litharge produced. Bismuth
may be recovered from the latter by dissolving in hydrochloric acid and
precipitating as bismuthyl chloride, which, in turn, may either be used
as such, or may be reduced by heating with charcoal and sodium
carbonate. Gold and silver may be removed from bismuth by the
addition of a little zinc to the molten metal and treating as in the
Parkcs desilvcrising process.
Wet processes are seldom used for the extraction of the metal but
arc mainly employed for the preparation of medicinal and pharma-
ceutical products. In general, the ore is dissolved in hydrochloric acid,
aqua regia or sulphuric acid, and .from the solution bismuth is pre-
cipitated by iron. If hydrochloric acid is used as the solvent, bismuthyl
chloride is precipitated, and from this the metal is obtained as previously
described. 2 The impure bismuth may be refined by liquation, dissolved
in nitric acid, precipitated as baste nitrate, rcdissolvcd in nitric acid and
precipitated as hydroxide by ammonia : this bismuth hydroxide, after
washing and drying, may be reduced by hydrogen. Most pharma-
ceutical preparations are to-day made .From refined bismuth.
The method employed in Norway by the Norsk Ilydro-Elcctrisk
Kvnclstof Aktieselskab 3 involves the treatment of bismuth ores with
crude nitric acid obtained by the solution of oxides of nitrogen in water.
If the ore contains bismuth trioxiclc the action is simple neutralisation
according to the equation
The action is more complicated when sulphide ores are treated. The
ore is first part.ially roasted, ground finely, and added to the crude; nitric
1 Kern and Jones, T-mn-f. A/nrr. Klf-clw/if-.m. A'or., 1030, 57, 2-17.
" ilrru-l, Mrlull vxd J'Jrz, ] !)o(), 27, r>f>7; I.G. Karbonind. A.G., (}<-n,ia,i. /V/r,,/, ]<j27,
-laSDiM: Gu^rnhcini Bros.., Ucrm'in Patent, 1928, /50,'JSOG; Kuh-Chemio A.C.i., (h-nn.'Ui
1'ulrnL 1929, ;1-14933.
BISMUTH AXD ITS ALLOYS. 129
acid. The main reaction may perhaps be represented by the equation
Bi 2 S 3 + 8HNO 3 = 2Bi(NO 3 ) 3 + 2XO + 4H 2 O + 3S
When the acid is almost completely neutralised, the lye is removed,
concentrated and poured into milk of lime. Bismuth trioxide is thus
precipitated and calcium nitrate remains in solution :
2Bi(NO 3 ) 3 + 3Ca(OH) 2 =Bi 2 O 3 +3Ca(NO 3 ) 2 +3H 2 O
This process is used mainly for the production of salts of bismuth.
Pure bismuth may also be obtained by converting the nitrate into
oxide and reducing the oxide by fusion with potassium cyanide. A
further purification may be effected by liquation. Bismuth containing
less than 0-01 per cent, of impurities (the chief of which is copper)
has been obtained. 1 Below are given the upper and lower limits
of the impurities present in six samples of bismuth examined spectro-
graphically. 2
Copper .... 0-001 to 0-006 per cent.
Silver .... 0-006 to 0-04-6
Tellurium . . . 0-000 to 0-004-
Thallium .... 0-000 to 0-005
Lead .... 0-002 to 0-061
Total 0-009 to 0-122
Physical Properties of Bismuth.
It is possible that bismuth can. exist in several allotropic forms, but
the evidence at present available is not conclusive. Transition points
have been reported, occurring at 75 C., 3 112 C. and 116 C. 4 In
addition, it has been suggested that a cubic modification of bismuth
exists at temperatures just below the melting point, changing into the
hexagonal form at a slightly lower temperature. 5 Xo direct evidence
has been obtained for the existence of cubic bismuth, but a transforma-
tion of tin's order might possibly afford an explanation of the cracks
which arc set up during the growth of a single bismuth crystal ; evidence
for the existence of such cracks is abundant, 6 but it is more probable
that they arc due to impurities. 7 A comparison of the electrical
resistance of unannealed bismuth with that of the slowly-cooled metal
indicates that a, transformation occurs 8 between 100 and 180 C.
Investigation of the thermal and electrical properties of very pure
bismuth, containing less than 0-01 per cent, of impurities (consisting of
platinum, silver and iron), failed to reveal any transition point at 75 C.
1 Mylms and GrosoluifY, Z-cltsch. (in.org. Chun., 1910, 96, 237. For a. general account
of the occurrence, extraction, recovery, re-fining and economics of bismuth, sec U.S.
Jhtrr-rtu of Standard.-*, 1930, drt'idar No" 382; St-rom, ting. Mining ,/., ] 935, 136, 20.
2 Goetz and Focke, Phy*. Jiwic-.w, 1934, 45, 170.
;i Cohen and Moesveld, 'Zr-il*r.]>. p/n/xika.l. Ch.f-.rn., 19] 3, 85, 41.9; Ghrm. \VcMlctd, 1913,
10, 656.
J -Kinecke, Zfif^ck. -phyxihil. Chf-.-m., 19.15, 90, 313.
5 Kapjt/.a, Proc. Roy. Xoc.. t 1928, 119 A, 358.
< Sehneider, 7%-v. 'Rcric.w, 1928, [2], 31, 251; "Boydston, ibid., 1.927, [2], 30, 911;
Bndgrnan, P-roc. Amc.r. Acad. Art a ticL, 1925, 60, 36J ; 1929, 63, 3.1J ; .Borclius and Lindl),
Ann* Ph.y*-d\ 1910, 51, 607.
7 Webster, Proc. Hoy. tioc,.. 1931, 133 A, 1(>2.
8 Pictenpol and Miley, Phys. Jici'ici.r, 1929, [2J, 34, 1588.
130 AXTIMOXY AXD BISMUTH.
or near the melting point. The temperature-resistance curve shows no
inflections between -190 and 271 C. Photomicrographs failed to
show any difference in the structure of bismuth chilled at various
temperatures. 1 Evidence derived from the investigation of the thermal
expansion of a bismuth single crystal has yielded interesting results
with reference to the possible allotropic change at 75 C. When the
thermal expansion is determined by ordinary methods there is a definite
discontinuity on the temperature-expansion curve at 75 C. No such
discontinuity was at first observed when measurements were made on
the crystal lattice by X-rays, 2 but a later investigation 3 revealed a
small but definite increase in the coefficient of expansion between 70 C
and 80 C. It is possible, therefore, that an allotropic change docs occur
at approximately 75 C., but the nature of the change, if it exists, has
not been determined. It is probable that another modification of
bismuth is obtained at the ordinary temperature by the application of
pressure of the order of 25,000 kilograms per sq. cm. Since the
transition to this new form is accompanied by a reduction in volume of
about 9 per cent., it is deduced that this modification should be formed
from the liquid with a contraction of the order of 4 per cent. This new
form of bismuth appears to be analogous to the high-pressure modifica-
tion of ice. 4
Bismuth is a white metal, having a slight reddish tinge and a brilliant
metallic lustre. It is very brittle and can easily be powdered ; it can,
however, be worked to a very slight extent by very careful hammering.
It crystallises in rhombohedra belonging to the hexagonal system 5
a:c = I: 1-3035 ; a =87 34'
The examination of bismuth crystals by X-rays indicates that the
metal crystallises in the di-hexagonal class of the hexagonal system :
the structure is that of a face-centred lattice, the bismuth atoms lying
on two interpenetrating face-centred rhombohedral lattices.' 3 The unit
rhomb contains eight atoms, the length of the edge lying between
6-52 x 10~ 8 cm. and 6-57 x 10~ 8 cm. The length of the edge of unit
structure is 3-28 x 10~ 8 cm. The three edges of the rhombohedron meet
in the trigonal axis, and the angle between any two of the edges is
87 34'. The angles between the faces have been determined. The
crystals have perfect cleavage parallel to the (111) plane and perpen-
dicular to the trigonal axis, but the cleavage is not so good parallel to
1 Schulzc, Zeilsch. MelalUmnde, 1930, 22, 194; Zeitsch. tech. Physik, .1930, 10, l(i.
2 Goctz and Henrenrothcr, Pkys. Review, 1932, 40, 6-4-3.
3 Jay, Proc. 'Roy. 8oc., 1934, 143 A, 465.
4 Bridgman, P'hys. Raview, 1934, [2], 45, 841. For further dismission of the allotropy
of bismuth, sco Gociz and Hasler, Phys. Review, 1930, 36, .1752; Cartw right, Review Ka.
J-nstrumcnt?, 1932, 3, 73; Tammann and Kohlhaas, Zr.i.fsch. anorg. Chan., 1!)31, 199,
209: Bridgman, Proc. Amer. Acad. Art.? Sci., 1921, 56, 115; Cohen' and .Moosfdd, Vr-./.v/.
Akml. WeicnncJi. Amxlerdutii, .1920, 28, 762: \Yurschmidt, Jahrb. Mt-n., 1917, i, .ReL '2;
tier. deuLpfujfiikal Gc.s., 1913, 15, 1027; 1914, 16, 799; Cohen, /W. X. Alwd. \V ((( wli.
Amslf.rdam, 1915, 17, .1236; Curie, J. J^iyxiquc., 1895, 4, 206; Aoyama and Alonna, ScL
Rep. Tohoku hnp. L r ';nc. 7 193 1, 23, 52.
5 Grot-h, Chc.rn. Kryxl'illogra.pliic,, 1906, I, 18, 22; Pusliin, Zrit.xrh. diior/j. Ckc/,i.,
1 903, 36, 243: Marc-hand and Schcerer, J. prali. Chcm., 1883, [2 |, 27, 193; St.olbai J. -pniL-l.
Cficm., 1865, 96, 183; .Rose, Poyy. An-nale-n, 1849, 77, 143; Quosnovillc, J. Phnnn., 1830,
1 6, 554.
Goklschmidt. Zeitwh. phijsikal. C'hern., 1928, 133, 397; Hassol and Mark, Kc.-itsc-k.
Physik, 1924, 23, 269; 0-g, Pkil Mag., 1921, [6], 42, 163; James, ibid., p. 193; Johnson,
Centr. iMin., J916, 385,
BISMUTH AND ITS ALLOYS. 131
the (111) planes. The ;i atomic diameter/' or closest approach of two
atoms, 1 is 3-llxlO~ 8 cm. Bismuth crystallises from the melt in
skeleton rhombohedra of the form indicated. 2 The structures of
spluttered and evaporated bismuth films 3 and of electrolytic bismuth 4
have also been described. Native bismuth probably has not preserved
its primary structure. 5 The spontaneous crystallising power of bismuth
has been investigated. 6 X-rays do not appear to alter the structure
of bismuth during crystallisation. 7 Investigation of the variation of
certain physical properties of bismuth with crystal deformation has
suggested that a secondary or :c mosaic " structure is superimposed
upon the lattice, and that this " mosaic " structure, which is perfectly
regular, is capable of undergoing deformation without alteration of the
crystal lattice itself. 8
Single crystals of bismuth have been prepared 9 and their properties
examined.. On account of their anisotropic nature they have received
considerable attention. The different values that have been obtained
by different investigators for some of the properties may be clue to
imperfections in the crystal, for it is claimed that slight strains set up
during the growth of a bismuth crystal have a great influence on the
orientation of the trigonal axis of the crystal lattice ; in addition, as has
been mentioned previously, cracks may develop in the crystal at a
temperature just below the melting point. The effect of a magnetic
field upon the growth of a bismuth single crystal has been examined, 10
and the results of these investigations lend support to the theory of
" mosaic " structure.
The density 11 of bismuth (Df) is 9-80. That of single crystals 12
grown under normal conditions is 0-82 to 0-83 : it is affected by the
presence of a magnetic field during the growth of the crystal.
The coefficient of thermal expansion (linear) 13 is 12-08 x 10~ G between
1 Sec Braocr, Phil. Mag., ] 020, [(>], 40, 160.
2 For further discussion of crystal structure, sec also -Jones, Proc. Roy. Soc., 1934,
147 A, 40-1; A<l'molt\,JR(-nc1. Accad. Sci. NapoU, 1930, [3], 36, 69; Davcy, Phys. Rwitw,
1925, 25, 7f)3; MeKcchan, J. Franklin Intf.., 1.923, 195, 51.
3 Kahlcr, Pln/i*. Rf.rio.w, 1921, 18, 210. Sec also Bnsscm, Gross and Herrmann, Zcit.tch.
Phyxilc, 1930, 64, 537.
'* Snlhvell and Andrieth, J. Awcr. Cham. Soc., 1932, 54, 472; Hirata, EJc.c. Review
(Japan], 1 928, 16, 051, 701.
5 Carpenter and Tamura, Bull. Just. j\f-i.rirny and jMc.iall'urgij, 1928, No. 282.
Bekicr. Zc.if.*ch. <i;norn. Chan., 1912, 78, 178.
7 Kostanni, Alii 11. Accad. Lined, 1928, [01, 7, 046; Adinolfi, -ibid., 1925, [6], i, 382;
1928, [Oj, 8, 381.
8 Xwicky, Proc. NftL A cad. Sci.. 1929, 15, 810; Goetz, Pliys. Rn-lew, 1930, 35, 193;
Goof/ and Ha si or, ihid., 1930, 36, 1752; Goetz and J^ocke, 7%*. Review, 1931, 37, 10-14.
See also >Sie\vart anri. ,Morro\v, Phys. Review, 1927, 30, 232.
von Compel 1 /, Zr.it.tich. Physik, 1922, 8, 184; Obrcirnov and Shubnikov, Trans.
Phtfft. J\rr/i. Lab, Lr-.'in-narad, 1925, 100, 21; Shubnikov, Proc. Acrid. Sci. Amsterdam,
1930, 33, 327, (;ootx, l^'iys.'lir-.mc.w, .1930, 35, 193.
10 Ticri and IVrcios, L-inc.. R(-nd., 1921, 30, 464; Goetz and Hauler, Proc. Nat.. Acc.d.
/S'c/.. 1029, 16, (MO; lac. c,/L; Goetz, Joe. cit.; Goetz and Focko, lor,, cit.; Goclz and H.crgen-
i-olhcr, Phi/x. Jtcr/Mt;, M)32, 40, 1.37.
11 l-ntr-.r national Critical Tables, .1927, 2, 450. See also Davcy, /V/yx. Hcvic.w, 1924,
23, 292: Kndo, J. fml. M rial*, 1923, 30, 121; Lowry and Parker, J. 'Ckun. Xoc., 1915,
107, I0()5; Johnston and Adams, J. Aimr. Chw. or.., 1912, 34, 5(13 ; Kahlhaum, Rolh
and Sicdlcr, Zfilxch. nnT(i. C'//f/n., .1902, 29, 2i) 1 ; .Mareliand and Scliecrer, J. prahL
(;]>c.ni., 188;> ; , F "2j, 27, 193. ' ]2 Goet// and Focke, Inc. at.
13 J-.iltrnationfil Critical Tubhfi, 1927, 2, 400; Grunciscn, Ann. Plu/xilc, 1910, 33, 05.
See also Friend and Vallancc, J. I-nnf,. MclaU, 1924, 31, 79 (Discussion); Dorsey, Ph.ys.
litm&w, 1907, 25, 88.
132
AXTIMOXY AXD BISMUTH.
-183 and 15 C., and 13-45 x 10~ 6 between 19 and 101 C. For a
single crystal the coefficient 1 at the ordinary temperature is 13-96 x 10~ 6
parallel to the trigonal axis, and 10-36 x 10~ 6 perpendicular to that axis,
the mean coefficient 2 between 20 and 240 C. being 16*6 x 10~ 6 parallel
to the trigonal axis, and (12-0 0-2) x 10~ 6 perpendicular to that axis ;
between 240 C. and the melting point the coefficient falls off very
markedly. 3 The effect of a magnetic field upon the coefficient of
thermal expansion (linear) of a single crystal has been determined. 4
The coefficient of thermal expansion (cubical) 5 is 39-6 x 10~ 6 .
The mean compressibility 6 is 3-0 x 10~ 6 for the pressure range between
100 and 500 megabars. 7 This value decreases at very high pressures.
The compressibility of single crystals has also been determined. 8
The hardness on Mobs' scale 9 is 2-5 ; the Brinell hardness number 10
(using a 6-35 mm. ball and a load of 40-3 kg. at 15-5 C.) is 7-3.
Young's modulus is 0-32 x 10 6 kg. per sq. cm., and the tensile strength
about 450 kg. per sq. cm. 11
The specific heat at the ordinary temperature 12 lies between 0-03023
and 0-0303, and the variation with temperature is given approximately
by 13
c= 0-030 +0-000013J
(where t is the temperature in degrees Centigrade), but there is an
| |
Temperature, C. . . 27
77 i 127 i 177
227
267 272-7
327-2
371-1
1 i
(hq.)
(liq.)
(Hq.)
Atomic Heat at Constant !
i
Pressure . . . ! 6-15
6-31 , 646 6-60
6-73
6-83
7-217
7-119 6-995
Atomic Heat at Constant i
i
Volume . . . 6-OS
6-22 | 6-35 6-48
6-60
6-70
_. .
1 Brideman, Proc. Nat. A cad. Sci., 1924, 10, 411. See also Fizeau, Compt. rend.,
1869,68,1125.
2 Jay, Proc. Roy. Soc., 1934, 143 A, 465; Goctz and Hergenrother, loc. cit.; Phys.
Review, 1931,38,2075.
3 Roberts, Proc. Roy. Soc., 1924, 106 A, 385; Jay, loc. cit.
* Kaye and Higgins, Phil. 3 fag., 1929, [7], 8, 1057.
5 Endo, loc. cit.' See also Kopp, Pogg. Annalen, 1852, 86, 156; Matthiesscn, ibid.,
1867, 130, 50.
15 Richards, J. Amcr. Chem. Soc., 1915, 37, 1643; Adams, Williamson and Johnston,
ibid., 1919, 41, 12. See also Gruncison, Ann. Physik, 1908, 25, 825; Bridgman, Proc.
Amer. Acad. Arts Sci., 1923, 58, 166; 1924, 59, 109.
' Sec p. 18.
8 Bridgman, Proc. Amer. Acad. Art* Sci., 1925, 60, 305.
n Ryd'berg, Zeitsch. physikal. Chem., 1900, 33, 353.
10 Hargreavcs, J. Inst. "Metals, 1928, 39, 314.
11 Mallock, Proc. Roy. Inst. Great Britain, 1921, 23, 377; Proc. Roy. Soc., 1919, 95 A,
429; Schulze, Sitzber. Ges. Marburg, 1903, 80, 94: Voigt, Wied. Annalen, 1893, 48, 674.
For the mechanical properties of single crystals, see Schmid, Metallwirt-xcha/f., 1.928, 7,
1011; Proc. First International Congress of Applied Mechanics, 1924, 324: Bridgman,
Proc. Amer. Acad. Art,? Sci., 1925, 60, 305; Proc. Xat. Acad. Sci., 1924, 10, 411 ; Georgieff
and Schmid, Zeitsch. Physik, 1926, 36, 759; Haase and Schmirl, -ibid., 1925, 33, 413;
von Gomperx, ibid., 1922, 8, 184.
12 Rosta.cni, Atti R. Accacl. Lincei, 1928, [G], 7, 649. See also Awborry and Griffiths,
Proc. Phys. Sue., 1926, 38, 378: Adinolii, Attt. //. Ar.cad. Lincei, 192S, [6], 8, 381; Denizot,
Physikal. Ber., 1927, 8, 1584; .Bull. Sor,. Amis sci. Poznan, 1926," 2, 1: Umino, Sci.
Rep. Tohoku Imp. Unir., 1926, [1], 15, 597; litaka, ibid., 1919, 8, 99; Schimprl, Zeitsch.
physikal. Chem., 1910, 71, 257; Ivahlbauni, Roth and Siedler, Zellsch. anorg. Chew.,
1902, 29, 294.
13 International Critical Tables, 1929, 5, 93.
BISMUTH AND ITS ALLOYS.
1'33
anomalous increase when the temperature is 20 to 30 C. below the
melting point. 1 The atomic heats (in calorics per gram-atom) at high
temperatures are as in table 011 p. 132. The atomic heats at low
temperatures are : 2
: Atomic Heat
Temp., c C. (calories per
gram-atom).
Temp., C.
Atomic Heat
(calories per
gram-atom).
Temp., C.
Atomic Heat
(calories per
gram-atom).
-270 0-0102 3
-161-8
5-674
-64-2
5-974
-253 2-05 3
-147-9
5-813
-54-2
5-980
-212-2 4-631
-135-8
5-761
-14-9
5-874
-209-6 4-851
-123-8
5-817
- 6-7 i 6-058
-208-3 4-771
-110-5
5-869
- 0-2 6-083
-201-9 5-040
- 96-2
5-899
H-12-3 6-139
-198-4 5-216
- 85-3
5-924
H-22-2 6-089
-171-7 5-464
- 74-1
5-976
4-25-2 6-104
The metal employed was very pure, and contained no lead, arsenic or
antimony. The specific heat of bismuth is -increased by chilling, and
after exposure to X-rays. 4
The melting point 5 is usually given as 271 C., but values as low as
269 C. have been recorded. The metal is very susceptible to super-
cooling, and it has been shown that the degree of supercooling at which
the bismuth nuclei begin to recrystallise is definitely related to the
degree of superheating to which the metal has been submitted ; and
also, that the crystal nuclei tend to persist after melting and are only
slowly destroyed on superheating. 6 If a single crystal of bismuth
is heated to 10 C. above the melting point, and cooled slowlv, the
re-formed solid shows the same ciyst allograph! e orientation as the
original crystal ; when heated to a higher temperature, however, and
then re-solidified, a random orientation results. 7 The linear velocity of
crystallisation reaches a maximum value of 2 cm. per minute with 2
of supercooling. 8
The latent heat of fusion 9 is 13 calories per gram.
Bismuth contracts considerably on passing from the solid to the
liquid state, the percentage contraction 10 being 3-47. The metal further
resembles water in that the liquid attains a maximum density at a
1 Carpenter and Harlc, Proc. Roy. Soc., 1932, 136 A, 248.
2 Anderson, J. Amcr. Chem. Soc., 1930, 52, 2720.
:{ Kccsom and van den Ende, Proc. Acad. Sci. Amsterdam, 1931, 34, 210; 1930, 33,
243; van den Ende, M etallvjirtschaft, 1933, 10, (576.
1 Aclinolfi, loc. cit.
'> liiternntiaiial Critical Tables, 1927, i, 103. Sec also Awbcrry arid Griffiths, loc. cit.;
Kndo, ,/. I-iiM. Mdul.% 1923, 30, 121; Janecke, Zeitsch. pJiysikal. C/iem., IU31, 156 A, 161 ;
Bi^i;lo\v and Rykenboer, J. Phi/s. Chem., 1917, 21, 474; Mylius and Grosclmff, Zeitsch.
aiiorcj. Cham., 1904, 40, ;>1.
6 Webster, Proc. Roy. tivc., 1933, 140 A, 6.53.
7 Don at and Stjcrsladt, Ann. Piiysih, 1933, 17, 897.
8 Tammann and Kocha, Zdtsc/i. anorg. Chun., 1933, 216, 17.
9 Au'berry and Grifliths, loc. at. See also Uinino, loc. cit.; litaka, loc. cil.
10 Goodrich, Trans. Fa-iuday Soc., 1929, 25, 531. See also Endo, loc. cit.; Bornemann
and Siebe, Zfitttch. Metullkunde, 1922, 14, 329; Johnston and Adams, loc. cit.; Hesd, Ber.
deut.phys. Ges., 1906, 3, 403; Tocplcr, Ann. Plajtik, 1894, [2J, 53, 343; VincenLini, Atti
134 ANTIMONY AND BISMUTH.
temperature just above the melting point. 1 It is probable, however,
that at very high pressures a modification of bismuth exists whose
density is greater than that of the corresponding liquid phase (see p. 138).
The density of liquid bismuth 2 is given by
]) = 10-07 - ()-00125( - 200)
where t is the temperature in degrees Centigrade. Between 420 and
1100 C. the relationship between the specific volume, v t , and the
temperature, t C., is given by 3
z; t =0-1011 -f (128 xlO- 7 )(/-420)
Between 420 and 271 C., however, this relationship does not hold, the
specific volume decreasing less rapidly with fall of temperature below
420 C. From this, from a consideration of the effect of bismuth on
the melting points of other metals, and from the surface tension, it is
calculated that the molecular weight of bismuth is constant at approxi-
mately 209 between 420 and 1400 C., increasing sharply above that
temperature and attaining a value of 334 at 1500 C. "At 2100 C.
bismuth again becomes monatomic (sec also p. 136).
.The specific heat of the liquid 4 at 369 C. is 0-019.
The surface tension of liquid bismuth has been determined by a
number of investigators, 5 and the more recent results showing the
variation with temperature are as follows :
Temp., C. 269 . 300 320 ; 365 1 400 426 i 472 : 583 j 600
;" 378 ' . . 375 371 . . 367 ' 365 ; . . i . .
<7 i . '!:.,.!
, -, . . i . . . . ' , .-.:)-i !
i i
779 1 802 962
344
Hogncss.
arid ID rath.
Birkumshaw.
(dvnes -
P 61 ' 6 " 1 -' !' .. ISSS: ..
1
. . 380 ..... 1 .. | 307
! :
. . : 353 ; 340
From his results, Birkumshaw deduces that liquid bismuth is associated.
For the parachor, calculated from the results of Hogness and Birkum-
shaw, the values 02-0 and 94-4 have been obtained. 6 The atomic
parachor, determined by measurements on covalent compounds, is
80-0 ; there are thus positive anomalies of 12-0 and 14-4 respectively.
Since, if a double bond joins two atoms, the parachor (calculated for one
atom) will show a positive anomaly of 11-6, it is deduced that, for
bismuth in liquid form, the molecule contains two atoms which share
four electrons. 7
The viscosity of liquid bismuth 8 decreases from about 0-0168 at
300 C. to about 0-01 at 600 C.
1 Luck-king, Ann. Plys. Gkcm., 1888, [2|, 34, 21.
- Hogness, J. Ai/ier. Chr-.m. Soc. 9 1921, 43, 1021. See also Borncmarm and Saucrwald,
Zeittch. Jldalll'itrtdc. 1922, 14, 145; Borncmann and Sicbe, ibid., 1922, 14, 329; Plus*,
Zf-.iitch. a-twrg. Cha/n., 1915, 93, 1.
3 Jouniaux, Bull. Sac. chi-m., 1932, 51, 677. See also Matsuvama, Bull. Liist. Pky-<.
Clitm. ll<xvirdi (Tokyo), 1928, 7, 1054; ScL ftep. Tohoku Imp. Un<v., 1920, 18, 19.
4 Awbcrry and Griffiths, LUC. at.
5 HogJiess, loc. c'd.\ Sauenvtild and Drath, Zelt^ch. itn.org. Ghcm., L92G, 154, 79;
BirknmshaTv-, Phil. May., 1927, [7], 3, 12SG; "Matsuyaraa, Sc,i. Rtp. Tohoku Imp. Univ.,
]927, 16, 555; Smith, J. Intt. MUal^ 1914, 12, 16S"; Sicdcntopf, W-icd. An-nalen, 7897,
61, 235; Quinckc, Pogg. Aimalai, 1869, 138, 141.
Sugden, " The Parachor and Valency" (London, 1930), p. 174.
7 See also Joimiaux, loc. at.
8 Satierwald and Topler, Zeilsch. anorg. Chetn., 1926, 157, 117. Por the viscosity of
solid bismuth, see Karris, Phys. Review, 1912, 35, 95.
BISMUTH. AXD ITS ALLOYS.
135
The boiling point 1 lies between 1440 and 1500 C. It varies con-
siderably with pressure, as the. following data show :
j
i
1
i Pressure (mm.)
102
2,57
TOO
4788 !
8S92
1 Boiling point ( C.) . 1200
1310
1 500
1870 ;
2100
From these elata the latent heat of vaporisation of bismuth 2 is found by
calculation to be 42,700 gram-calories per mole. The variation of the
vapour pressure of bismuth with temperature is given as follows : 3
r i
Temperature ( C.) .
1210
1290
1385
1410 I 1490
Pressure (mm.)
63
126
300
406 | 760
i
Between 827 and 947 C. the vapour pressure of bismuth may be
calculated from the expression 4
52-23x195-26
where P is the vapour pressure in millimetres and T the absolute
temperature.
The vapour of bismuth at 2000 C. is monatomic, 5 although at lower
temperatures it is possible that both monatomie and diatomic molecules
exist. 6 It has been stated that the vapour at 851 C. contains 40 per
cent, of Bi molecules and 60 per cent, of Bi 9 molecules, 7 while at 827 C.
approximately 2 per cent, of Bi 8 molecules were deteeted in addition
to Bi and Bi 2 . No evidence has yet been obtained for the existence
of molecules of different constitution, such as Bi.,, Bi 4 or Bi G . The
heat of dissociation 8 of diatomic molecules of bismuth is stated to
be 77,1 00 17- 1200 gram-calories per mole.
Chiefly on account of the anisotropic nature of crystalline bismuth,
the thermal, electrical and magnetic properties have received consider-
able attention.
Bismuth is a poor conductor of heat and of electricity ; the relative
thermal conduc.lwity 9 is 1-8, that of silver being 1.00. The variation of
tliermal conductivity with temperature 10 of solid bismuth is as follows :
1 Greenwoud, /Vor, AY;//. Soc.., 19 10, 83 A, -183; 100!), 82 A, 39(5. See also Rufl' and
, 202, :ior>.
2 Greenwood, Chf.-ni. T.m-.s, 11)11, 104, 31, 42; Zcitdch. physthd. Chain., 1911, 76,,
4S-1.
3 Hull and Berirdahl, I'M',, ell.
4 Ko, J. l"r<t.,i.l;ii'n, fn.il., 1934, 217, 173.
' von YVarlenbero, Zutjc.k. anon;. Clic.m.., .1907, 56, 320.
G BiLtz and ^leyer, loc. c,il.
7 Zartmarm, Phys. Rc.-ciew, 1931, [21, 37, 383. 8 Ko, loc. clt.
<J \\''iedernanii and Franz, Pocjrj. Annulen, 1853, 89, 497.
10 Konno, Phil. Mwj., 1920, [GJ, 40, 542.
136
AXI1MOXY AND BISMUTH.
Temperature, C.
18
89
160
I
! 222
233
I
256
Thermal conductivity
s 0-0104
0-0181
0-0170
! 0-0177 0-0177
0-0183 i
1
i
i
That of liquid bismuth is :
Temperature, C. . |
Thermal conductivity
286 298
0-0400 0-0418
376 484
0-0378 0-0372
i !
i
584 !
I 0-0369
The conductivity in all the above cases is measured in gram-calories per
cm. per sec. per degree Centigrade. It will be observed that the thermal
conductivity of solid bismuth decreases to a minimum with rise of
temperature, afterwards rising to the melting point ; that of liquid
bismuth is nearly constant above 300 C., whilst at the melting point
there is a very considerable increase. Bismuth differs from most metals
in this respect, although antimony also shows a slight increase in thermal
conductivity on melting. 1 The effects of pressure 2 and of a magnetic
field 3 upon the thermal conductivity have been determined. The
thermal conductivities of a single crystal of bismuth are : 4
o
Perpendicular to the trigonal
axis .....
Parallel to the trigonal axis
Mean value (assuming a random
distribution of crystals)
0-0221 calories per cm. per sec. per C.
0-0159
0-0195
The electrical resistance 5 is 106-5 x 10~ 6 ohm-cm, at C., and the
variation with temperature is given by
# = 106-5[1 -f 0-00391Z-f 0-0000058/ 2 ] x 10~ 6 ohm-cm.
where t is the temperature in degrees Centigrade. The mean tempera-
ture coefficient of resistance between and 100 C. is 446 x 10~ 5 . At
the melting point the resistance of solid bismuth is 267 x 10~ G ohm-cm. :
that of liquid bismuth at the same temperature is 127-5 x 10~ G ohm-cm. 6
Bismuth is not superconducting at 268-84 C. The resistance at low
temperatures is as follows, being given as a ratio between that at the
temperature stated (R) and that at C. (R ). 7
1 For thermal conduct! vit}-', see also Jaeger and Dicssclhorst, Wissenscriaftl. Abhandl.
phys. tech. Rcicksanst., 1900, 3, 269; Giebc, Inaiujiiral Dissertation, Berlin, 1903; Verh.
deut. physikal. Gcs., 1903, 5, 60; Lorenz, Wied. Ann.aleu, 1881, 13, 422, 582.
2 Bnclcman, Proc. Amer. Acad. Arts Set., 1922, 57, 77.
3 Ward, Phd. May., 1924, [61, 48, 97J ; Knapp, Phys. Review, 1932, 39, 550.
4 Kayc and Pvoberls, Proc. Roy. Soc., 1923, 104 A, 98. See also Bridgrnan, Proc..
Amer. Acad. Arts Set., 1926, 61, 101; Proc. Nat. Acad. Sci., 1925, u, 608; Kayo and
Hiins, Pldl. Muy., 1929, [7], 8, 10r>6; do Haas and Capcl, Phyaica, 193-J, i, 929. "
1 iilernatioivd Critical Tables, 1929, 6, 136. See also .Devrar and Fleming, Proc.
. Acad. Scl. Amsterdam^ 1930, 33,
, , , . . , .
Roy. Soc., 1897, 60, 72; Shubnikov and de Haas, Proc. Acad. Scl. Amsterdam^ 1930, 33,
350; Xortlirup and Scydaiu, J. Franklin Inst., 1913, 175, 153; Xorthrup, Tra/iv. A/ner.
Electrochein. Soc., 1914, 25, 375.
See also Matsuvama, Sci. Rep. Tolioku Imp. Unlu., 1927, i6,447; Kinzolcu-no-Kenlcyu,
1926, [4], 3, 254; Trans. Artier. Soc. Steel Treatment, 1926, 10, 318; Pietenpol and Miley,
For bibliography, see ibid., p. 134.
, , , .
Phys. Review, 1929, 33, 294.
7 International Critical Tables, 1929, 6, 125.
BISMUTH AXD ITS ALLOYS.
137
ELECTRICAL RESISTANCE OF BISMUTH AT LOW
TEMPERATURES.
Temperature, C.
1007?
Temperature, C.
WOR
jR '
^0 *
-103-71
63-649
-204-68
36-064
-139-88
52-865
-216-01
33-014
-164-05
46-246
-253-01
22-329
-182-73
41-435
-255-34
21-388
-195-17
38-478
-258-86
19-574
The effects on electrical resistance of pressure, 1 of tension, 2 and of a
magnetic field 3 have been investigated. The specific electrical resist-
ance of a single crystal of bismuth is 1-38 x 10~ 4 ohm-cm, parallel to the
trigonal axis, and 1-07 xlO~ 4 ohm-cm, perpendicular to that axis. 4 At
low temperatures the variation of electrical resistance of a single crystal
with temperature 5 is as follows (the value for the resistance is given
as a ratio between the actual resistance at the temperature stated (R)
and that at C. (R Q )).
ELECTRICAL RESISTANCE OF SINGLE CRYSTALS OF
BISMUTH AT LOW TEMPERATURES.
Parallel to Trigonal
Axis.
Perpendicular
to Trigonal Axis.
Temperature, C.
10022
Temperature, C.
100/2
R '
*o '
- 90-1
72-0
- 92-1
C6-3
-]24-l
66-9
-128-1
57T
-161-1
00-2
-149-1
50-5
-157-1
47-2
The influence of a magnetic field upon the electrical resistance of a single
crystal has been investigated 6 at low temperatures. 7
1 Bridgman, Proc. Nat. Acad. Sci., 1020, 6, 505.
2 Zavattiero, Alii R. Accad. Lined, 1920, 29, I, 48; Bridgman, Proc. Amcr. Acad.
Art* Sci., 1922, 57, 41; Rolniek, Phys. Review, 1930, 36, 506.
3 Corbino, Atti R. Accad. Lineal, 1920, 28, I, 49; McAlpinc, Ply*. Review, 1929, 33,
284; 1931, 37, 624; Altmann, SUzung fiber. Naturforsch.-Ges. Univ. Tarka, 1928, 35, 8;
.Becker and Curtis, Phys. Review, 1920, 15, 457. Sec also Carpini, Atti R. Accad. Lin-cei,
J904, [5], 13, II, 159;* Grunraach and Wcidert, Physikal. Zeitsch., 1.906, 7, 729; Dewar
and Fleming, Phil. Nag., 1895, 39, 019; Gross, Ztitxch. Pliysik, 1930, 64, 520.
- 1 Kapitza, Proc. Roy. 8oc., 1928, 119 A, 358, 387, 401; 1929, 123 A, 292, 342;
Schneider, Phys. Review, 1928, 31, 251.
; "> International Critical Tables, 1929, 6, 125.
<5 Kapitza, loc. cit.
7 Slvubmkov and dc Haas, Proc. Acad. Sci. Amsterdam, 1930, 33, 130, 363, 433.
133 ANTIMONY AND BISMUTH.
The thermal electromotive force of bismuth with respect to platinum l
is given (in mierovolts) by
between and 268 C. Y r allies have also been obtained for couples with
copper, 2 cons tan tan 3 and lead. 4 The thermoelectric force between
stressed and unstressed bismuth has been measured. 5 Several investi-
gators have drawn attention to a discontinuity in the thermoelectric
power of bismuth at a temperature near the melting point. The effect
of orientation on the thermal electromotive force of a single crystal of
bismuth with reference to copper 6 between 20 and 100 C. (expressed
in microvolts) is as follows :
EFFECT OF ORIENTATION ON THERMAL B.M.F. OF
SINGLE CRYSTALS OF BISMUTH WITH REFERENCE
TO COPPER.
Angle between Basal Cleavage Plane ' ^ ;
and Direction of Current. ! Thermal L.M.l .
0' ! - 55 (t~ ~ t L ) - 0-031 2(/ 2 - t
5 5' ! -56-6(f 2 -t 1 ) -
10 0' ; -61-i^ 2 -/ 1 ) -
17 7 f \ -61-4(/ 2 -t 1 ) -0-0625(/- -t 1 ) 2
21 1' ' -6M(f 2 - t 1 ) -0-()8T5(f 2 -t 1 )' 2
Bismuth is diamagnctic. The specific magnetic susceptibility 7 is
-1-346 xl()~ G . The effect of temperature has been studied 8 and the
magnetic susceptibility of molten bismuth is found to be approximately
one-hundredth that of solid bismuth just below the melting point.
1 Jntc.r national Critical Table,*, 1929, 6, 214. See also Pelabon, Compl. rend., 1923,
176, 1305: Ann. physique, 1920, 13, 169; Wanner, Ann. Pliysil:, 1908, [4], 27, 955; Jaeger
and Diesselhorst, \V tsstnschaftL Abhandl. phys. tech. Reiclisanst., 1900, 3, 269; DC war and
.Fleming, Phil. Mag. 1S95, [5], 40, 95.
~ van A ubcl, hull. Acad. roy. Bdy., 1926, [>], 12, 559.
;J Boydston, Phyx. Rwic.w, 1927, 30, Oil.
1 rntkrnatiou.nl Cruicdl Tables, loc. ell. See aLso Todeseo, A III R. Accad. LinC(.,i, 1927,
f(i'l, 5, -134; Xuovo dm.. 1927, 4, 94.; Tenula, Tanaka and Kysaba, Proc. Jmp. Acad.
Tokyo, 1927, 3, 132, 200; Brid,mnan, Proc. Nat. Acad. ScL, 1925, n, 60S; J3orclius and
.Linclh, Ann. Pfiyslk, 1917, 63, 97; Darliim and Grace, Proc. Phy*. 8oc. Load., 1916, 29,
S2; Koeni.^sber^er, Ann. P/iy*ik, 1915, 47, 563; -Jordan, Phil. lf(ty., 1911, 21, 454;
Caswell, Phy*. Rwlc.w, 1911, 33, 381; Lownds, Ann. Pliysik, 1901, 6, 146; Perrot, Arch.
*S'c/. -phys. nat., 1898, 6, 105, 229, 899; 7, 149.
"' VV'a^nei', l.oc. cit.
' Brid^inan, Proc,. Amcr. Acad. Arts ,S'r/., 1918, 53, 2(59; 1926, 61, 101; 1929, 63, 351;
Pluj*. Ji<:tie;u\ 1917, 9, 269; J>roc. Neil. Acnd. XcL, 1928, 14, 943. See also I/Uernali.on-al
Critical Tables, lac. cif..; Boydston, loc. cit.; Terada, Tanaka and Kysaba, Joe. c/.L
7 Lsnardi and Cans, Ann. Physlk., 1920, [4-1, 61, 585. See also Endo, Sa. R<'.p.
Toko/cu I nip. Unu'., 1927, 16, 201: Ehrenfesi , Physica, 1925, 5, 388; Oiines and Perrier,
P-toc. K. A bad. Wctensch. Ani.slc,rda)n., 1910, 12, 799; 1911, 13, 115; 19]2, 14, 674; 1914,
16, 894, 901; Owen, Ann. Phyxik, 1912, 37, 657; Meslm, Ann. Clum. Phys., 1906, [8J,
7, 145; Wills, Phil. May., 1898, |5|, 45, 432; Pkys. Review, 1905, 20, 188; Curie, Co-nipt.
rend., 1892, 115, 1292;' 1893, 116, 136; J. Physique, 1895, 4, 197; Lombard!, Mem. R.
Accad-. Torino, 1897, [2], 47, 1; Fleming and Dewar, Proc. Roy. Soc., 1896, 60, 283;
1898, 63, 311; von Ettin^shausen, W-ied. ^Annalen, 1882, 17, 272.
8 Honda, 'Ann. Physik, 1910, [4], 32, 1027.
BISMUTH AXD ITS ALLOYS. 139
The susceptibility is independent of the field strength at ordinary
temperatures, but at temperatures of -250 C. or -200 C. it decreases
at higher field strengths. 1 It is also decreased by cold working.' 2 The
magnetic properties of colloidal bismuth have been investigated with a
view to determining the effect of particle size. 3 Although the results of
these investigations do not appear to be conclusive, it is suggested that
the high diamagnctism of bismuth is a property of the crystal rather
than of the atom. 4 The magnetic susceptibility of a single crystal of
bismuth 5 in a direction perpendicular to the principal erystallographic
axis is - (1-482 dzO-Ol-l) x ICr 6 , and in a direction parallel to this axis
-(1-0530-010) xlO- 6 . The mean value is - 1-340 xKH 5 . From
this it may be deduced that the magnetic susceptibility of a poly-
crystalline "aggregate is - (1-340:0-()13) x 10~ 6 , The effect of tem-
perature 6 and of field strength 7 on the magnetic susceptibility of single
crystals has been investigated.
The various galvanometric and thcrmomagnetic effects in bismuth,
such as the Hall effect, the Corbino effect, the Ettingshausen effect, the
Nernst effect, the Kighi-Leduc effect, etc., have been studied at great
length. 8 The Hall effect is negative and increases in a negative direction
as the magnetic field increases, apparently approaching a limiting value ;
the Hall coefficient decreases as the temperature rises, becoming zero at
the melting point ; the crystalline structure and the orientation of the
principal crystallographic axis to the primary current and to the
magnetic field greatly influence the magnitude of the Hall effect ; it is
probably for this reason that many published results are discordant.
The Hall effect in a single crystal has also been investigated. 9 The
Xernst effect is positive.
It is known that a substance may be caused to emit electrons when,
it is illuminated by light of sufficiently high frequency ; the longest
wavelength capable of producing this effect is called the photoelectric
threshold. 10 The value for polycrystalliuc bismuth lies between A 2080 A
and A 3300 A : that for a single crystal between A 280-1- A. and A 2891 A.
The optical properties of.' bismuth in the massive condition, 11 in the
1 cle "Haas and van Alphen. ./'roc. Acad. SM. A)nsltrda'tn, 1930, 33, 080; do Haas,
N<tiun\ .1931, 127, 33">.
~ Lcnvance and Constant., Phyx. I\.(-ULC-LI:, 1931, 38, 1547.
- i^owance ana i^onsiani, JL ft-y$. i\( : /;ic,v;, i^>i, 30, LO-H.
:] Vcrnia and 'Mathtir, J. Indian Chan, tioc., 1931, 6, 181.; .1933, 10, 321; l\ao, Indian
J. rtujtir.x, 1931, 6, 241; .1932, 7, 35; Nature, 1931, 128, 153; Bhatnagar, ,/. I -mil an
Chc.in. >S'or;., 1930, 7, 957; Vaidyanathan, I ndutn, J. Phyxic*, 1930, 5, 559; Nature, 1930,
1927, 54, 001.
tj McLennan and Cohen, 7'/v//i,v. Hoy. tioc. Canada, 1929, 111, [3;, 23, 15'J; Donat and
y .Heaps, /V'v/x. Ha'ic.w, 1927, [2], 30, 61.
10 l-ni(;?n<iti<itt'il Critic.nl Table.*, 1929, 6, 68. See also llamcr, Htt\ tic't. 1 ntinuntnts,
1924, 9, 25 [; Tarniley, ./Viy.y. Rcv-ir-w, 1927, 29, 202; 30, 656; Hughes, P/W. Trans.,
1912, 312, 205; Richardson and Compton, y j /(i/. J/t/.r/., 1912, 24, 575; Schari, Ztdtck.
Plinth, 1928, 49, 827.
11 Mayej-, .-l/i/4. Phy*ik, 1910, 31, 1017; Hagen and Rubens, iiitZ., 1900, I, 352.
140 AXTDIOXY AND BISMUTH.
form of opaque films, 1 in the molten condition 2 and in the form of single
crystals 3 have been investigated. 4
Spectrum. Bismuth compounds impart no characteristic colora-
tion to the Bunsen flame. The wavelengths of the principal lines in the
arc spectrum are as follows. 5 (The numbers in parenthesis indicate the
relative intensities of the lines, the lowest numbers indicating the
weakest intensities. 6 )
11711 (10), 9657-2 (10), 8210-8 (10), 6134-85 (5), 5742-55 (6),
5552-24(8), 4722-7(8), 4722-5(10), 4722-2(10), 4121-85(6),
4121-52 (6), 3510-85 (6), 3397-21 (5), 3067-73 (9), 3024-64 (8),
2993-34(9), 2989-04(9), 2938-31(10), 2897-98(10), 2809-63(8),
2780-52(7), 2730-50(5), 2696-76(6),' 2627-93(8), 2524-52(7),
2515-68 (6), 2489-4 (5), 2400-89 (8), 2276-57 (5), 2230-62 (8),
2228-25 (6), 2189-59 (6), 2177-3 (6), 2152-9 (7), 2134-4 (8),
2133-6 (7), 2110-3 (8), 2061-71 (8), 1533-7 (5).
The wavelengths of the most persistent lines in the arc spectrum,
such as ma} r be used for spectrochemical purposes, are as follows. (The
expressions in parenthesis are the spectral terms allotted to the particular
lines, adopting the usual notation.)
2061-71 (*S - 4 P 3 ), 2276-57 ( 4 S - 4 Po), 2780-52 ( 2 D ),
2809-63 ( 2 D~ 3 - 2 P 9 ), 2897-98 ( 2 D - 2 P*i), 2938-31 ( 2 D 3 ),
2989-04 ( 2 D 2 ), " 3067-73 ( 4 S/- 4 P 1 ).
The " raie ultime," or most persistent line, 7 has the wavelength
3067-73 A.
The wavelengths of the principal lines in the spark spectrum are as
follows. (The numbers in parenthesis indicate the relative intensities
of the lines.)
6809-1 (7), 6600-1 (7), 5209-28 (10), 5144-50 (6), 4722-7 (8),
4722-5 (8), 4722-2 (5), 4561-15 (8), 4302-13 (10), 4259-04 (10)
4079-22 (10), 3792-9 (8), 3695-53 (8), 3510-85 (5), 3067-73 (6),
2989-04 (5), 2938-3 (8), 2897-98 (5), 1346 (10), 1317 (15),
1306 (10), 1051 (10), 1045 (10).
The second and third order spectra have also been investigated, 8
and it is indicated that the spectrum of singly ionised bismuth is that of
1 Hulburt, Astrophys. J., 1915, 42, 205.
2 Aster, Phys. lieview, 1922, 20, 349.
3 Rouse, Phys. Revieu', 1926, 27, 247; Dix and Rouse, J. Optical Soc. Amer., 1927,
14, 304.
1 For a discussion of the relationship between the physical properties and the structure
of bismuth, see Jones, Proc. Roy. Sac., 1934, 147 A, 404.
5 For tables of wavelengths and sensibilities for use in spectrum analysis, see Tina
de Rubies and Bargues, Zeitich. anorg. Chem., 1933, 215, 205; Kramer, Zeilxch. anal.
Chem., 1934, 97, 89.
6 International Critical Tables, 1929, 5, 2S4.
7 International Critical Tables, 1929, 5, 323.
8 ".McLennan, McLay and Crawford, Proc,. Roy. tioc., 1930, 129 A, 579. See also
Kishen, Current /Science, 1933, i, 312; Zumstein, Phys. Review, 1931, 38, 2214; Green
arid WulfT, ibid., 1931, 38, 2186; Green, ibid., 1931, 37, 16S7; Fisher and Goudsmit,
ibid., 1931, 37, 51; Arvidson, Nature, 1930, 126, 565; Lang, Phys. Review, 1928, 32, 737;
Rao and Xarayan, Proc. Fifteenth Indian &d. Cong., 1928, 80.
BISMUTH AXD ITS ALLOYS. 141
the two-electron spectrum, and that of doubly ionised bismuth a simple
one-electron doubled spectrum. The bismuth nucleus has a resultant
moment of momentum 1
4--J7?.
-^ (h Planck's constant)
The ionisation 'potential for singly ionised bismuth is about 14 volts, that
for doubly ionised bismuth 25-4 volts and that for Bi v 55-7 volts. 2
The arc 3 and spark 4 spectra in the ultra-violet region have been
studied in some detail, and in the latter case the spectrum has been
extended to a wavelength of A 200 A. 5
The Zceman effect has been studied. 6
In the absorption spectrum of bismuth vapour both lines and bands
are found, in addition to the cc raie ultime " (A 3067-73 A.). The bands
appear in groups, occurring in the ultra-violet, and at higher tem-
peratures, in the visible region. Each group consists of bands degraded
towards the red. The approximate wavelengths of the bands in the
ultra-violet region are (in A.) 2859-9, 2842-9, 2828-2, 2813-5, 2799-8,
2785-0, 2772-7, 2759-6, 2744-8, 2732-6, 2722-0, 2712-3, 2701-9, 2693-2,
2681-5, 2670-0. The lines 2276, 2230 and 2228 are also strongly
absorbed, and there are other absorption lines of wavelength 2110, 2062
and 2021 A. At 800 C. fine absorption lines appear in the spectrum,
the wavelengths of which do not appear to have been determined, while
another banded structure is revealed at a lower wavelength. At about
1200 C. a banded structure is observed in the visible region extending
from A 4500 to A 6500 A. The interval between the bands in this
spectrum differs from about 35 A. at the violet end to about 90 A. at the
red end. At higher temperatures the bands tend bo merge into one
continuous band. 7
The following arc the wavelengths of absorption lines which are
1 Back and Goudsmit, Ztitsch. Physik, 1928, 47, 194.
2 Por the hyperfinc structure of the spark spectra of bismuth, and deductions concern-
ing the nuclear structure, see also Schoepfle, Phys. Review, 1935, 47, 232; McLay and
Crawford, Proc. Roy. Soc., 1934, 143 A, 540; Phys. Review, 1933, 44, 986; Mohammed
and Sharma, Phil. *Mag., 1932, 14, 977, 1143; Bacher and WulfY, Phys. Re.vtc.ic, 1932,
40, 123; McLennan, McLay and Crawford, Proc. Roy. Soc., 1931, 133 A, 652; Zeeman,
Back and Goudsmit ., Zfittxch. Phy.nk, 1930, 66, 1; Back and WullT, ibtd., p. 10; White,
Plnjf*. J-tc.vic-.w, 1929, 34, 1404; Back and Goudsmit., Phys. Itevi.ew, 1928, 31, 1 125; Xagaoka
and Ahshirna, Proc. Jaip. Acrid. Ja-pa.ti, 1926, 2, 249; Ivuark and Chenault, Phil. ^Marj.,
1925, 50, 937; ,Joos, Phyalhil. Zcitfich., 1925, 26, 380; Xagaoka and Sutruira, Astrophys.
,/., 1921, 53, 339; Darbyshire, PldL Mag., 1933, 16, 701. "
:! .MoLennan, Youn,^ and l.reton, Proc. Roy. tioc., 1921, 98 A, 101.
4 Arvidson, Aim. J'h-ysik, 1932, 12, 787; Mohammed :ind Sharma, 'loc. ciL: Zumstein,
loc. cit.\ Lano, Phil. Tran^., 1924, 224, 4)8; Bloch and BJoch, Coni.pt. rend.', .1914, 158,
14K); 1920, 170, 320; 1920, 171, 709; 1.924, 178, 472; J. Phys. Radium, 1921, 2, 229.
5 Por the infra-red spectrum, sec Walters, Bureau of Standards Scientific J*apcrs,
1921, No. 411, 161; Lubovich and Pearen, J > )oc. Tran.fi. Roy. Soc. Canada, 1922, [3J,
16, 195.
Back and Goudsnut, Phys. JRw-itw, 1928, 31, 1125. For bjbhography to 1927,
see 1-ntcr-ii.ahuii.al Critical Tfi.blw, 1929, 5, 420.
7 Frayne and Smith, Phil. May., 1926, | 7], i, 735; Rao, Pruc. Piuy. Sue. , 1925, 107 A,
7(iO; Xarayan and Rao, Ph.il. Mag., 1925, [6], 50, C-17; AVilliams, Phy.nk/iL. 'Zc.itfich.., 1932,
33, 152; Bari'atl and Bonar, Phil. Mar/.', '.1930, [7], 9, 519; Charola, Unio. la Plata,
J-;h.idio CitncMtx, 1929, 89, 205; PhymkaL Zcltxch., 1.930, 31, 457; Zumstein, Phys. Jitviem,
.1926, 27, 562; Ruark, Mohler, Foote and Chenault, L'.ti. Bureau of Standards /Scientific
Paper*, 1924, No. 490, 463; Nature, 1923, 112, 831; Grotrian, Zcitsch. Physik, 1923,
18, 169.
142 ANTIMONY AND BISMUTH.
observed in the under- water spark spectrum ; they correspond with
those which are reversed in the arc spectrum : x
3596-11, 3510-85, 3405-23, 3397-21, 3067-73, 3024-64, 2993-31,
2989-04, 2938-31, 2897-98, 2809-63, 2780-52, 2730-5, 2696-76,
2627-93, 2524-52, 2515-68, 2400-89, 2276-57, 2230-62, 2228-25,
2189-59, 2177-3, 2164-1, 2156-9, 2153-5, ' 2152-9, 2134-4,
2133-6, 211.0-3, 2061-71.
At 1500 C to 1600 C. bismuth vapour emits fluorescent radiation,
orange-yellow in colour. 2 The fluorescence spectrum shows a banded
structure which is more or less the exact complement of the absorption
spectrum in the region examined. The wavelengths of bands that have
been measured are :
6533-0, 616i-5, 6389-0, 6319-5, 6248-5, 6187-5, 6117-5, -6052-0,
5991-5, 5940-5, 5886-5, 5831-5, 5776-5, 5726-0, 5680-0, 5640-0.
It is convenient here to include a description of the spark spectrum
of dilute solutions of bismuth trichloride. The wavelengths of the most
persistent lines in this spectrum, and the minimum concentration of the
solution in the spectrum of which they appear, are given on p. 143. These
lines may be employed in quantitative analysis. 3
The X-ray spectrum of bismuth has been studied, and measurements
obtained for the K, 4 L. 5 M 6 and X 7 series.
Chemical Properties of Bismuth.
Bismuth is not readily attacked by air at ordinary temperatures,
but on heating in air it is converted to trioxide. 8 When heated in air
to its boiling point it burns with a faint bluish-white flame, forming
bismuth trioxide, which condenses as a yellow deposit of cc flowers of
bismuth ; ' (flares bismuti) upon a cold surface placed in the flame. It
reacts slowly at ordinary temperatures with water from which carbon
dioxide has been expelled, becoming coated with an hydralcd oxide : 9
and at red heat there is some evidence to indicate that it decomposes
steam slowly. 10
Bismuth is not attacked by hydrochloric acid in the absence of air,
1 Hulburt, Pliys. Review, 1924, 24, 120.
2 Rao, loc. cit. See also McLennan, Walerstein and Smith, Phil. May.. 1927, [7], 3,
390; Terenin, Zeitscli. Physik, 1925, 31, 26; Xarayan and Rao, Xal-ure, 192-1, 114, 045;
Franck, Physika.1. Zcilsch.', 1923, 24, 450.
. * Hartley, PM. Trans., 1884, 175, 327; Baly, " Speci-rosc-opy" (London, 1927), 2, M4.
4 Stephcnson and Cork, PJt.ys. Review, 1926, 27, 138; Rechou, Compl. rend., 1925,
180, 1107: Duane, Fricke and Stenstrom, Proc. Xal. Acad. Sci. t 1920, 6, 607.
3 8icba,hn and Friman, Phy,s-ikal. Zeitsch., 1916, 17, 17; Cosier, Zc.ifuch. Phy^ik,
1921. 4, 178; Friman, ibid., 1920, 39, 813; Eddy and Turner, Proc. Roy. tin., 1927,
1 14 A, 605; Williams, Phya. Review, 1934, 45, 7J ; Duanc and Patterson, Proc. Xat.
Aaid. Set., 1920, 6, 518.
f; Hjalmar, Compt. rend., 1922, 175, 878; Zr-.ilxch. Phys'tl:, .1923, 15, 05.
' Dolejsek, Zaitsch. Phy.<ik, 1924, 21, 111; I-Ijalmar, ibid.. ] 92I>, 15, 05. I-"or fnrijier
literature dealing with the X-ray .spectrum, see also Robinson, Proc. Roy. tior., 1923,
104 A, 455; Alien, Phys. Review, 1924, 24, 1; Robinson and Cassie, Proc. Uny. Sor..
1920, 113 A, 282; Kimrira and Xakamura, Japan. J. Phyticfi, 1924, 3, 29; Duane and
Patterson, Proc. Xc/f. Acrid. ScL, J922, 8, 85; J ntcrnuiionnl Critical Tuhl<<^ i!)29, 6, 70.
s Th.omson, Proc. Phil. 8oc. G'lasyow, 1S4J-2, I, 4; Iicintz, Porjcj. A ftm/ai, 1844,
63, 38.
{) von Bonsdor.fi, Pogg. An/mien, 1837, 41, 305.
10 R-egnault, Ann. Chim. Phys., 1836, [21 62, 363.
BISMUTH AKD ITS ALLOYS.
143
SPARK SPECTRUM OF DILUTE SOLUTIONS OF
BISMUTH TRICHLORIDE.
1 per cent. Solution.
0-1 per cent. Solution.
0-01 per cent. Solution.
3792-9
3695-5
3595-7
3510-8
3430-9
3396-7
3067-7
3067-7
3067-7
3023-8
3023-8
2992-2
2992-2
2989-0
2938-3
2897-9
2897-9
. .
2854-8
2854-8
2846-1
2846-1
2414-8
but in the presence of air it is slowly dissolved. No hydrogen is evolved.
It is readily dissolved by cold nitric acid or aqua, regia, and by hot
concentrated sulphuric acid ; it is possible that the solvent action of
nitric acid is due to the presence of nitrous acid. 1 The nitrous acid is
presumed to act eatalytically. and the reaction may possibly be repre-
sented by the equation
In the presence oC nitric acid, any bismuth nitrite formed is at once
converted to bismuth nitrate with the production of oxides of nitrogen.
Bismuth thus resembles silver, mercury and copper in this reaction.
With nitric acid of density 1-2, and at a temperature of 65 C.. bismuth
reacts with instantaneous evolution of nitrogen tetr oxide (even in an
atmosphere of hydrogen), and evolution of this gas continues until all
the metal is dissolved. Neither ammonia nor hydroxylaminc is pro-
duced by the action of nitric acid on bismuth under any conditions.
Bismuth does not react ^vith phosphoric acid, either in dilute or con-
centrated solution. 2 It is .oxidised slowly by chloric" acid and the
product is only partially soluble 3 in water.
Metallic bismuth does not react with -hydrogen even when heated.
A black powder, described as pyrophoric bismuth, can be prepared by
the reduction of bismuth compounds with hydrogen. 4 From solutions
of its compounds, bismuth may be displaced by hydrogen under pressure.
From solutions of bismuth trichloride up to normal concentration, and
with pressures between 15 and 250 atmospheres and temperatures
1 Stansbio, J. tioc.. Chew. Jnd., 1 90S, 27, :JGr>; Divers, ihi'L, I 004, 23, 1 182; J. Ch(-m.
., .188.""), 47, 230; 1883, 43, 443. See also this Series, Vol. VI, Pan I, p.
,Soc., 188.""), 47, 230; 1883, 43, 443. See also this Seru
2 Portevin and Sanfourcho, Compf.. rend., 1931, 19:
3 Jicndrjxson, ,/. Aimr. Chc>m. Soc., 1904, 26, 747.
1 Vanino and IVIenzel, Zeitsch. atiorg. Chew., 1925,
, .
1931, 192, Io63.
149, 18.
144 ANTIMONY AND BISMUTH.
between 150 and 200 C., this displacement may be represented by the
expression
1 a r;r
log = K
dp te a - x
From this it is calculated that from a normal solution of bismuth
trichloride at 20 C. and with hydrogen at 100 atmospheres pressure,
one per cent, of bismuth would be precipitated in thirty-seven years.
There are reasons for believing that the reaction is ionic. Precipitation
of bismuth from acetic acid solutions takes place more rapidly than
from solutions in hydrochloric acid. Hydrogen under a pressure of
60 atmospheres will also displace bismuth from the triphenyl derivative
dissolved in xylene, according to the equation
2(C 6 H 5 ) s Bi + 8H 2 =6C.H 9 +2Bi
At 225 C. this reaction is complete. 1
Bismuth does not react readily with the halogens when the latter are
perfectly dry ; the presence of moisture, however, greatly accelerates
reaction. The metal is attacked only superficially by fluorine even at
red heat ; it reacts with chlorine, bromine and iodine to form in each
case an impure halide, which may possibly be a mixture of the di-halide
with the tri-halide. 2
Bismuth is oxidised by ozone, the product being a mixture of oxides. 3
The metal combines directly with sulphur, selenium and tellurium
when melted with those elements. It combines with sulphur when a
mixture of the two elements is submitted to pressure. 4 It does not
react with dry sulphur dioxide even on heating, but when heated with
sulphurous acid under pressure bismuth trisulphide is formed. 5
Bismuth does not combine directly with nitrogen, and with phos-
phorus only with difficulty. With arsenic and antimony it forms
alloys ; it is doubtful if intermetallic compounds are formed with
either (see, however, p. 214). It is oxidised to trioxide by the action
of nitric oxide 6 at 200 C. It is very slowly attacked by ammonium
nitrate. 7
Bismuth will dissolve to a slight extent in solutions of alkalis, and
evidence has been obtained of the formation of alkali bismuthites. 8
The position of bismuth in the electromotive series is a little doubtful ;
in the series as usually given its position is anomalous, since it lies
between antimony and arsenic, thus :
1 Ipaticv, Jan., Bcr., 1931, 646, 2725; Ipatiev, Jun., Molentin and Teodorovich,
Bar., 193.1, 64 B, 1964; Ipatiev and Razuvaev, Ber., 1930, 63, 1110. For the action of
the free radicals methvl and ethyl on bismuth, see Paneth, Trans. Faraday Soc., 1934,
30, 179.
- Thomas and Dupais, Compt. rend., 1906, 143, 282; Cowper, J. C/iem. Soc., 1883,
43, 153; Chcm. Ncics, 1883, 47, 70; Thoinsen, Ber., 1883, 16, 40; Muir, J. Chew.. Soc.,
1876, 29, 144; Deherain, Bull. Soc. cJiim., 1862, 4, 22; Weber, Pogg. Annnhn, 1859, 107,
598; Schneider, ibid., 1855, 96, 130: Heintz, ibid., 1844, 63, 60; Moissan, Ann. Chini.
Phys., 1891, [6], 24, 247.
3 Schonbein, J. pra/ct. Chem., 1864, 93, 59.
4 Spring, Ber., 1883, 16, 100] .
5 Gcitner, A-n.<iltn, 1864, 129, 354; Uhl, Bar., 1S90, 23, 2154; ScbilT, AniiaJc.n., 1861,
117, 95.
(l Muller and Barck, Ztitsch. anorg. Chcm., 1923, 129, 309.
7 Tammann, -ibid., 1922, 121, 275.
8 Grube and Schweigardt. Zeitsch. Elektrochem., 1923, 29, 257.
BISMUTH AXD ITS ALLOYS. 145
Cs . . . Zn, Cd, Fe, Co, Xi, Sn, Pb, H, Sb, Bi, As, Cu, Kg, Ag,
Pd 3 Pt, Au . . . F
If the elements are arranged in the order of the heats of formation of the
chlorides the following series is obtained :
+Hg, Tl, Pb, Bi, Sn, Sb, As, P, Te, Se, S~
which is in fair agreement with the order of the electrode potentials.
All the elements in this scries are electronegative to elements which are
truly electropositive, such as the alkali metals, and are electropositive
to those which are truly electronegative, such as the halogen elements.
They may be regarded as amphoteric, a view that is supported by the
behaviour of their compounds with alkali metals. 1 Many of these
compounds are metallic in character, and are decomposed by water,
probably hydrolytically, with the formation of a hydride of the more
electronegative element. (Evidence for this has been obtained in the
case of sodium stanni.de.) These compounds with alkali metals are,
however, soluble without decomposition in liquid ammonia, and the
solutions behave as electrolytic conductors. Thus in a solution of
sodium bismuthi.de in liquid ammonia it is probable that the anion is
composed of a group of bismuth atoms, sodium forming the cation,
since these solutions behave similarly to those of ordinary salts, and
show no metallic properties. The electromotive series for these am-
photeric elements corresponds with the series given above derived from
the heats of formation of their chlorides, although the position of
bismuth and phosphorus is doubtful owing to the sluggish action of their
alkali compounds in solution in liquid ammonia. 2 From the decom-
position voltages of metallic bromides dissolved in aluminium bromide
the electromotive series is found to be 3
+A1, Zn, Cd, Ilg, Sb, Bi~
In the electrolysis of fused alloys of copper, tin and bismuth at 1000 C.
copper migrates to the cathode and tin and bismuth to the anode. 4
Bismuth can be precipitated from solution completely by tin, zinc,
cadmium, iron, manganese and magnesium, 5 but only partially by lead
and copper. 6
The electrode potential of bismuth has been determined with respect
to various cells. The normal potential between bismuth and a normal
solution of a bismuth salt in the cell 7
Hg | KC1 ! N Bismuth salt | Bi
is, for bismuth sulphate -0-490 volt, for bismuth chloride -0-315 volt
and for bismuth nitrate 0-500 volt. By calculation from the hydrogcn-
bismuth cell, using hydrochloric acid, the specific, potential 8 is 0-1635
1 Kraiis, Trans. AVIW. .ElectrocJic.ni. Soc., 192-1, 45, 175.
- Burgstrorn, J. Amcr. Chem. Soc., 1925, 47, 1503. For the relationship of bismuth
to the radioactive elements, see Joliot, J. Chltn.. phyx., 1930, 27, 119.
3 Isbekow, Z(>.t.f.*cJi. 'i)lnjs-\L(d. Ofic.m.., 1925, 116, 304. >Sco also Isbckow, Zdlscli. anorg.
Chciti,., 1930 185, 324.
1 Krenuum and Seheibel, .Maiiatdi., 1931, 57, 2-11.
5 Pro linger, M tmatxft.., 1893, 14, 309; .Fuktor, Plumn. Poxl, 1905, 38, 153. See also
Kroll, M dail -and Erz, .1922, 19, 317.
u Juequelain, ,/. prald. Ckcm., 183S, 14, 1; Reinseh, ibid., KSJ], 24, 248.
7 Neumann, r /j(dtw.h. 'phyvikal. C/ietn., 1894, 14, 193.
8 Xoycs and Chow, ./. Airier. Chcm. Soc., .1918, 40, 739. Sec also Jellinek and Kiihri,
Zeitsc/t. physikaL Chan., 1923, 105, 337.
VOL. vi. : v. 1Q
146 AXTIMOXY AND BISMUTH.
volt at 15 C., -0-1599 volt at 25 C. and -0-1563 volt at 35 C. In
molar solutions of bismuth per chlorate the bismuth may be present
either as BiO^ or as BiOH~ ; . The electrode potential has been calcu-
lated from e.m.f. measurements upon such solutions using a bismuth
electrode. 1 Assuming that all the bismuth is present as BiO ! the
potential is - 0-314 volt ; assuming that it is all present as BiOH~' ; the
potential is -0-298 volt.
Smooth crystalline cathode deposits of bismuth can be obtained by
electrolysis of a solution of bismuth perchlorate. 2 The recommended
solution contains 4 grams of bismuth trioxide and 10-4 grams of per-
chloric acid in 100 c.c. of solution, with, as addition reagents, 0-03 per
cent, of glue and 0-08 per cent, of cresol. In the absence of addition
reagents, the decomposition, voltage of bismuth perchlorate is 1-62 volts ;
for deposition a current density of 3-1 amperes per square decimetre is
recommended. At present there appears to be very little practical
demand for electro-deposited bismuth, but it is possible that the process
may be applicable to the manufacture of certain components for
electrical and magnetic apparatus. 3 The process does not appear to be
suitable for the refining of bismuth.
In a normal solution of bismuth silicofluoride 4 the electrode
potential, compared with the hydrogen electrode, is 0-295 volt. It is
reported that a Japanese company employs a solution of this nature for
the refining of bismuth. 5
The overvoltage for bismuth 6 in 2N H 9 SO 4 at 25 C. is 0-388iO-0(H
volt.
The anodic corrosion of bismuth in nitrate solutions has been studied : 7
under suitable conditions bismuthyl nitrate is formed. In alkaline
solutions bismuth dissolves aiiodically to form alkali bismuthite. When
the concentration of the solution exceeds one gram of bismuth per litre
the anode becomes passive as a result of the formation of a coating of
oxides of bismuth. 8 Bismuth also dissolves at. the cathode in alkaline
solution. 9
Sols of bismuth have been prepared in a variety of ways. In the
earlier methods, organic salts of bismuth were reduced in very dilute
solution, as for the preparation of bismuth monoxide. 10 The electric
pulverisation method has also been employed. 11 More recently, in-
vestigators have employed chiefly reduction methods, formaldehyde,
sodium bisulphite and sodium thiosulphatc being used as reducing
agents. The sols produced arc frequently very unstable, but the
stability is greatly increased by the addition of protective colloids.
Smith, J. Amcr. Chem. Soc., 1923, 45, 360; Swift, ibid., p. 371.
Harbaugh and Mathers, Trans. Amer. Eltctroclie.m. Soc., 1933, 64, 293.
See further, Fink and Gray, ibid., 1932, 62, 123.
.Forster and Schwabe, ZciiscJi. Elelctrochcm., 1910, 16, 279.
tiny. Mining ,/., 1929, 128, 89.
Thicl and Hammcrschmidt, Zerlsch. anory. Che.m., 1923, 132, .15. See also Lloyd,
Tru
ix. Faraday Soc,., 1929, 25, 525.
Prideaux and .Hev/is, J. Soc. Chcm. Ind., 1922, 41, 176.
C-.Vube and Seli\vei<_ r ardi, Zcit.<<ch. Elcldrcx-ltan., 1923, 29, 257. See also Xewbcrry,
Ju-nt. tioc.., I OK), 109, 1 0(1(5.
Paneth, Zcil*ch.. Ehlctrochcin., 1925, 31, 572.
Vanino and Treubert, 7>V., 1 899, 32, 1072; Vanino, PJumn. 7,<nlr.-h., 1899, 40,
27(i; Lottcrnioser, J . pratt. Chc.m., 1899, 59, 4 Si); Gutbicr and Hofmeier 1 , Zeitxch. auoi-y.
C/ic.-ni., 1905, 44, 225.
11 Bredig, Zntsch. Elclctrochtm., 1897, 4, 51-1; Zeilsch. angew. Chcm., 1898, II, 951;
"Bredig and JHaber, Bcr., 1898, 31, 2741; Svcdberg, Ber., 1905, 38, 3616: 1906, 39, 170o'.
BISMUTH AND ITS ALLOYS. 147
There is evidence that many of these sols are contaminated by oxide. 1
Evidencc of sol formation has been observed during electrolysis of
distilled water between bismuth electrodes using a low voltage. 2
Atomic Weight of Bismuth.
[A~o/e. The bracketed numbers refer to list of references under table on p. 148.]
Until comparatively recent years the values obtained for the atomic
weight of bismuth by different investigators varied considerably. This
was, in general, due to two causes : firstly, the difficulty of obtaining
pure bismuth compounds, and secondly, the tendency for inorganic
salts of bismuth to form basic complexes through hydrolysis. The
earliest values were obtained by Lager hj elm, (1) who converted metallic
bismuth into oxide, sulphide and sulphate respectively and determined
the ratios 2Bi : Bi 2 O 3 , 2Bi : Bi 2 S 3 , and 2Bi : Bi 2 (S0 4 ) 3 . Subsequently
many investigators repeated these determinations and obtained values
varying from 208 to 210. Dumas (3) converted the metal into chloride
and determined the ratio 3Ag : BiCl 3 . Marignac (4) "prepared bismuth
trioxide from bismuth nitrate. The nitrate was first purified and then
converted into basic nitrate, the latter being converted into the oxide
by heating. In one series he reduced the oxide to metal by heating in a
current of hydrogen and determined the ratio 2Bi : Bi 2 O 3 ; in another
he converted the oxide into the sulphate and determined the ratio
Bi 2 O.j : Bi 2 (SO 4 ) 3 . Classen, (6) in 1890, realising the difficulty of obtain-
ing pure bismuth, purified the metal electrolytically ; from the ratio
2Bi : Bi 3 he obtained the A r alue 208-92, which approximates closely to
that now generally accepted. Later, Gutbier (s)> (9)> (10) and his collabora-
tors adopted a variety of methods and obtained values all of which were
in the neighbourhood of 208. More recently, Honigschmid and Bircken-
bach (13) prepared specimens of the chloride and bromide of bismuth with
great care, taking special precautions to exclude all moisture, and from
their analyses of these salts obtained a mean value of 209. Classen (12)> (14)
and his collaborators concluded that organic compounds of bismuth
would be more suitable for atomic weight determinations as they were
Jess liable to form basic complexes. They prepared specimens of
bismuth triphcnyl, and from the ratio 2BiPh ; > : Bi 2 O 3 derived the mean
value 209-00. The chief values obtained by different investigators arc
recorded in the table on p. 148.
In 1921 the value adopted by the International Committee was
208-00 ; at present (1936) the accepted value is 209-00. This is in
agreement with the work of Aston, 3 who determined the mass number
of bismuth to be 209.
Bismuth is a simple element, no inactive isotopes having been
discovered. 4 Radioactive isotopes, such as thorium C, arc known,
however.
1 Gutbier, Ottenslein and Adam, 7jtit sell, a/iorg. Clicm., 1927, 164, 287; Gutbier,
illd., 1920, 151, l.">*5; Gutbier, Kautter and Gctiicr, ihid., 1925, 149, 107; Gutbier and
KauUer, ibid, I92r>, 146, JGG; Lapenta and Reislcr, (J.ti. Palciit, 1027, 1GI522G; Paal
and di Pol, 7;Vr., 1920, ^9 B, 877; I lugounenq and Loiselenr, Compt. rc.tid., J92(>, 182,
sr>i.
- Pa\Jov, l\dU(/,d ZtitficJi.., 192I-, 34, 100. See also Morigueln, J. (Jlu-in. Hoc.. Japan,
P.:>3, 54, I<;i7.
:: Aston, Xatnrr., 192-1, 114, 717; /V/,/7. M.'J., 1925, 49, 1191.
4 Aston, he. cil. Sec, however, Allison and .Bishop, PJiy*. liwic.uj, J933, 43, 48;
Chcmisches \Verk Ivlopfer, G.M.B.H., German Patent, 1930, 0-40983.
ANTIMONY AND BISMUTH.
THE ATOMIC WEIGHT OF BISMUTH.
Authority.
Ratio Determined.
xo. i
of
Expts.i
Atomic
Weight.
Lager hj elm (1) (1814)
2Bi : Bi 2 S 3 -100 : 122-32
2Bi : Bi 2 O 3 = 100 : 111-3285
4
2
215
211-8
Schneider (2) (1851) .
2Bi :Bi 2 3 = 89-6552 : 100
8
208-00
Dumas (3) (1859)
3Ag : BiCl 3 =100 : 98-003
9
210-806
Marignac (4) (1883) .
2Bi : Bi 2 O 3 = 89-682 100
Bi 2 O 3 : Bi 2 (S0 4 ) 3 -1(0: 151-726
6
6
208-60 i
208-18
Lowe (5) (1883).
2Bi : Bi 2 O 3 = 89-648 100
2
207-84 ,
i Classen (G) (1890)
Schneider (7) (1894) .
2Bi : Bi 2 O 3 = 89-696 100
2Bi : Bi 2 O 3 = 89-657 100
9
6
208-92
208-04
Gutbier and Bircken-
bach (8) (1908)
2Bi :Bi,O 3 = 89-656 100
=89-662 100
10
6
208-02
208-15
Gutbier and Mchler (<J)
(1908)
BiBr 3 : 3AgBr =79-467 : 100
8
207-959
Gutbier and Jans-
sen (IO) (1908)
i 2Bi : Bi 2 (SO 4 ) 3 =59-084 : 100
6
208-081
de Co n i nek and
Gerard (n) (3916)
BiCl 3 : Bi = 2-1400 : 1-4165
4
208-40
i Classen and Nev (12)
! (1920)
2BiPh 3 : Bi 2 3 = 188-954 : 100
10
208-949
and BiCl 3 : SAgCl =73-3420 : 100
Birekenbach (13 > =73-3399 : 100
(1921) BiBr 3 : 3AgBr =79-6474 : 100
BiBr 3 : 3Ag =138-655 : 100
; Classen and Strmich (l4) 2BiPh 3 : Bi.>0 3 = 188-902 : 100
(1924) '
20 | 209-01
15 209-00
208-98
209-00
14
10
15 209-029
Lagerhjclm, Annals of Philosophy, 1814, 4, ,358.
Schneider, Poyrj. An;iuiUii, 1851, 82, 303.
Diiinas, Ann. Chirn. Pkys., 1859, 55, 176.
Marignac, Arch. Sci. phys.nat., 1883, [3], 10, 10. See Bailey, J. Chun. 6'oc.. 1887,
51," G7(>.
Lo\ve, Zcitsch. anal. Chew-., 1883, 22, 4-98.
Classen, B&r., 1890, 23, 938.
Schneider, J. praJ:L Chun., 1894, 50, 461.
Gutbier and Birekenbach, ibid., 1908, 77, 457.
Gutbier and Mehler, ibid., 1908, 78, 409.
BISMUTH AND ITS ALLOYS.
149
Alloys of Bismuth.
Alloys of bismuth arc not used to a great extent in industry. The
low melting point of the metal, and the fact that it forms simple eutecti-
ferous series of alloys vrith certain other metals, enables it to be used,
however, in the manufacture of " fusible alloys. 55 1 These are mainly
ternary or quaternary alloys of bismuth, tin, lead and cadmium ; some
typical analyses arc as follows :
COMPOSITIONS
OF SOME "FUSIBLE ALLOYS.' 1
Xame.
Bi.
Pb.
Sn.
Cd.
M.pl. ( C.).
Newton's .
50
31
19
95
Rose's
50
28
22
100
Dareet's .
50
25
25
93
Wood's
50
24
14
12
71
Lipowitz/
50
27
13
10 1
M.pt. 70 C.,
softens at
CO C.
The free/ing point diagrams, and in some cases the conditions of
equilibrium, of a number of binary alloys of bismuth have been in-
vestigated. They may be described briefly as follows : 2
Bismuth -Lithium. 3 Two compounds are formed : Li 3 Bi (M.pt.
1145 C.) and LiBi (formed by a peritcctic reaction at 415 C.). The
latter is dimorphous, with a transition point at 400 C. Xo ranges of
solid solution have been observed. There arc two eutectics, at 14 atoms
per cent, lithium (M.pt. 243 C.), between Bi and a LiBi, and at 97-5
atoms per cent, lithium (M.pt. 175 C.), between Li andLi 3 Bi. Primary
crystals of /3 LiBi are formed only between 35 and 37 atoms per cent,
lithium.
Bismuth- Sodium. 4 Two intcrmctallic compounds arc indicated:
Xa 3 Bi (M.pt. 790 C.) and XaBi (decomposing at 450 C.). A eutcctic
is formed at 97-5 per cent, bismuth (M.pt. 218 C.). The compound
XaBi crystallises with a tetragonal, body-centred lattice: =3-46 A.,
c =4-80 A. The unit cell contains one atom of each element, the lattice
containing no complexes of bismuth atoms. Complexes, such as
Xa 3 Bi. V c7?XH 3 , arc however formed with liquid ammonia, which, on
removal of ammonia, yield mixtures of XaBi and bismuth. 5
Bismuth-Potassium. 6 Two compounds are formed: KBi 2 (M.pt.
553 C.) and K ;j Bi 2 (M.pt. 673 C.). A transformation occurs in the
latter at 281 C. A eutcetic is formed at the bismuth end of the system,
melting at 64 C., and the liquidus curve shows discontinuities at 18 per
1 Thews, MclalWortic., 1930, 20, 1097, 1 Lf>3, 1211; Rurc.au of Standard,^ 1930, Circular
Xo. 388; Pamivano and JSirovioh, Gazzdla, 1912, 42 I, 030;' JHommel, 'Zulxck. Mciall-
hwmlt, 1921, 13, 456, 511, o()5.
- International Critical Tables, 1927, 2, 419.
:5 Grube, Vosskiihler and Schlccht, Zcitxch. Elvktrochcm., 1934, 40, 270.
- 1 Mathcwson, Zutsch. anorg. Chan., 1906, 50, 171.
5 Zintl and Dullenkopf, Ztitscli. physical. Chcm., 1932, B 1 6, 183.
Smith, Zcitsch. anorg. Chcm., 1908, 56, 109.
150 AXTIMOXY AXD BISMUTH,
cent, bismuth (373 C.), 24 per cent, bismuth (423 C.) and 79 per
cent, bismuth (281 C.). The compound KBi 2 crystallises with a cubic,
lace-centred lattice : a = 9-501 0-005 A. There are eight molecules in
the unit cell. 1
Bismuth -Copper. 2 These metals form a simple cutectiferous
scries of alloys with the eutcctic close to the bismuth end, melting at
268 C. X-ray analysis reveals that the lattice of each metal remains
unchanged and indicates that the mutual solubility is very low. The
influence of bismuth on the mechanical properties of copper is con-
siderable, the presence of 0-05 per cent, producing brittleness. The
addition of arsenic mitigates to some extent the effect of bismuth.
With more than 0-005 per cent, bismuth, copper is unsuitable for wire
drawing. 3
Bismuth -Silver. 4 Xo compounds are formed. A eutcctic is
found at 2-5 per cent, silver (melting at 260 C.), and the maximum solid
solubility of bismuth in silver is about 5-5 per cent. These results are
confirmed by X-ray analysis.
Bismuth -Gold. 5 A eutectic is formed at 83 per cent, bismuth
(240 C. ) ; the solid solubility of bismuth in gold is approximately 4-5 per
cent. Although neither bismuth nor gold exhibits the phenomenon
of superconductivity, the eutectic mixture becomes superconducting
at -271-1 to -271-6 C. It is stated that the superconductivity is
localised in the solid solution phase. 6
Bismuth -Magnesium. 7 One compound is formed, Mg 3 Bi 2 (M.pt.
823 C.), which exists in two modifications, a and f$, the transition
temperature being 700 C. for the pure compound and slightly lower for
alloys containing a slight excess of magnesium. There appears to be a
slight range of solid solution of magnesium in the compound. Two
eutectics are formed, at 14-3 atoms per cent, bismuth (M.pt. 551 C.)
and at 95-7 atoms per cent, bismuth (M.pt. 260 C.).
Bismuth -Calcium. 8 Two compounds are formed : CaBi 3 (de-
composing at 506 C.) and Ca 3 Bi 2 (M.pt. 928 C.). A third compound,
CaBi, may also exist. There are two eutectics, at 0-5 per cent, calcium
(M.pt. 270 C.) and at 88 per cent, calcium (M.pt. 785 C.). The heat of
formation of the compound Ca 3 Bi 2 at 21-5 C. is 51,600 gram-calories
per mole.
Bismuth -Zinc. 9 A eutcctic is formed at 97 per cent, bismuth
(M.pt. 250 C.). Within the range of composition between 1 and 70
1 Zintl and Harder, Zeitecfi. physical. Chem., 1932, B 16, 206.
2 Jeriomin, Zeitech. anorg. C/io/i., 1907, 55, 412; Ehrct and .Fine, PklL l\Iuy., 1930,
[7], 10, 551.
;! Freude, MctaUborse, 1928, 18, 818; Johnson, J. Inst. Mtlals, 1912, 7, 240.
1 Pctrenko, Ztitsch. anorg. C/iem., 1906, 50, 133; Brodcrick and Ehret, J. Phi/s. Chan.,
1931,35, 2627, 3322.
5 Vogel, Zeitsch. anorg. Chem., 1906, 50, 145.
G de Haas and Jurriaansc, Proc. Acad. Sci. Amsterdam, 1932, 35, 748; Xaturtuifme.ii-
schaften, 1931, 19, 706; de Haas, Mdallwirtsch.aft, 1930, 9, 149; Naturwiascnachaftcn,
1929, 17, 85; de Haas, van Aubel and Vooud, Proc. Acad. Sci. Amsterdam, 1929" 32,
226, 724.
7 Grubc, Mohi- and Bornhak, Ze-'dsch. 'Ehkiroclierm., 1934, 40, 143; Kawakami, Sci. flap.
TohoJcu Imp. Univ., 1930, 19, 521; Grubc, Zeitsck. anorg. Chcm., 1906,49, 72.
8 Kurzynicc, Bull. Acad. polonaise, 1931 A, 31. See also Donski, Ztitsck. anorg.
Chc.ni., 1908, 57, 185; Kremann, AV r astall and Schopper, for&chungsa/beitat, zur
Metullhundc, 1922, [5]: /. In*L lUclals, 1924, 32, 529.
a Curry, J. Phys. Ckcm., 1909, 13, 589; Honda, and Ishigaki, tici. Rtp. Tohoku
Imp. Univ., 1925, 14, 219; Mathewson and Scott, Zeitsch. MdallkumU, 1914, 5, 1.
BISMUTH AND ITS ALLOYS. 151
per cent, bismuth the melt, above -117 C., consists of two immiscible
liquids.
Bismuth -Cadmium. 1 These metals form a simple eutectiferous
system with a euteetie at 40 per cent, cadmium (M.pt. 149 C.).
Bismuth -Mercury.' 2 The two metals are mutually insoluble in,
"the solid state ; a euteetie is formed very close to the mercury end of
the series (M.pt. -39C.).
Bismuth -Aluminium. 3 Within the range of composition between
3 and 98-7 per cent, bismuth the melt, above 650 C., consists of two
immiscible liquids. The addition of small amounts of bismuth to
aluminium causes a slight depression of the melting point, the maxi-
mum depression being 3-5 C. Bismuth is slightly soluble in aluminium
in. the solid state, but aluminium appears to be insoluble in bismuth.
Bismuth -Gallium. 4 In this system there is a range of com-
position within which the melt consists of two immiscible liquids. The
maximum solid solubility of gallium in bismuth is 11 per cent.
Bismuth -Thallium. 5 In this sj'stern maxima occur on the
liqxiiclus curve at 10 per cent, bismuth (307 C.) and at 62 per cent,
bismuth (220 C.); the latter corresponds to the compound Tl 3 Bi 5 .
Eutectics are found at 5 per cent, bismuth (M.pt. 300 C.), at 46 per cent,
"bismuth (M.pt. 180 C.), and at 78 per cent, bismuth (M.pt. 200 C.).
There are three ranges of solid solution : a between and 4 per cent,
bismuth, J3 between 5-5 and 32 per cent, bismuth, and 7 between
57 and 65 per cent, bismuth. The last contains the compound Tl 3 Bi 5 .
Tliis compound becomes superconducting G at 266-8 C.
Bismuth- Silicon. 7 In this system, within the range of com-
position between 2 and approximately 100 per cent, silicon the melt,
tvbovc 1415 C., consists of two immiscible liquids. A euteetie is formed
ivt O8 per cent, silicon (M.pt. 204 C.). Solid solution occurs to only a
very slight extent.
Bismuth-Cerium. 8 The following 1 compounds are formed:
Cc 3 Bi (decomposing at 1395 C.), Cc 4 13i 3 (M.pt. ]630 C.), CeBi (decom-
posing at 1520 C.) and CeBu (decomposing at 870 C.). Eutectics arc
found at 5-3 per cent, bisrmith (M.pt. 757 C.) and at approximately
TOO per cent, bismuth (M.pt. 270 C.). Discontinuities occur on the
Jiquidus curve at 33 per cent, bismuth (1359 C.), at 69 per cent, bismuth
(1520 C.) and at 82 per cent, bismuth (870 C.).
Bismuth -Tin. A euteetie occurs at 58 per cent, tin (M.pt. 135 C.) 3
1 .Fi.schw, Z(-.itdC/t. ttchtuKchti J } liyvik, 1925, 6, 140; Tammaiiu and Hemzel, Zdtsch.
crnory. G'hcm., J92S, 176, 147.
2 Pushin, Zeitsc/i. anorg. Chun., 1903, 36, 201.
:J Gwyer, Zeiixck. anury. Chcni.., 1000, 49, 31 J ; Hanson and Biumcnthal, Mdallwirl-
xc'hajl, J93J, 10, 925.
* Pushin, Siepanovic and Slajic, ZcUscli. awry. Ghtm., 1932, 209, 329; Kroll, Metall-
'irirt.xchaft, 1932, u, 435.
Kurnakov and Agccva, Ann. List. Anal. Phys. Cham., 1935, 7, 49; dander, ZaUsch.
J\rtKt., 1934, 89, 89; Zeit.tich. physikal. Chc.m., .1934, 169, 260; Kurnakov, Zhemchu/hnui
;A,iid Tarann, ZeUxclt. anory. Chew,., J914, 83, 200.
do J-Iaas, JlctailwirL^ha/t, 1930, 9, 149; NaturwitiMnachaflcti, 1929, 17, 85; de Haas,
van Aubcl and Voogd, Vc.rsluy. Akad. \Valtnsdiappc.ti Amsterdam, 1928, 37, TOG.
7 Ehret and Abramson, J. Amcr. Chcm. Sue., 1934, 56, 385; Jcttc and Gcbert, J.
CJheui. Physics, 1933, I, 753; Williams, Zcitsch. anory. Cficm., 1907, 55, 1.
8 Vogcl, ibcd., J914, 84, 323.
Thomas and Evans, 'Plul. May., 1934, 17, 65; Bucher, Zcitfsch. anory. Chan., 1910,
98, 97; Kapp, Ann. Physih, 1901, <5, 754; Solomon and Morris Jones, PluL Mag., 1931,
n, 1090.
152
and
Bismuth-Lead. 2 There
125 C. and
,. ,
solid
T cent.
*
frm a
series
composition. (See p 42 )
Joismuth- Selenium 6 _ T,,^
' 6 2 C ""' ' Bj
linearly
?
A bove 12
at 8,3
the melt
1 de K*,a.s,M e tallwirtschaJt 9 1930 o 1 49
Cowan, U 1C rs and Edwards jf 4 S 'V - v
/^ m ^?' , Burmu f Standards J Research' i ofn ^^ ^ /etofe Handbook," 1930 718-
BISMUTH AXD ITS ALLOYS. 153
Bismuth-Cobalt. 1 A eutectic is formed at 97 per cent, bismuth
(M.pt. 260 C.). Above 1350 C. and within the range of composition
from 9 to 95 per cent, bismuth the melt consists of two immiscible
liquids.
Bismuth -Nickel. 2 Two compounds are formed, NiBi 3 (decom-
posing at 560 C.) and XiBi (decomposing at 720 C.). There is a
eutectic at 0-7 per cent, nickel. Discontinuities occur on the liquidus
curve at 4 per cent, nickel (560 C.) and 12 per cent, nickel (720 C.).
The solid solubility of bismuth in nickel is 5 per cent. ; this solid solution
is magnetic below the temperature range from 360 to 396 C.
Bismuth -Rhodium. 3 Three compounds are formed, RhEi 4 ,
RhBi 2 and RhBi, At 433 C. the compound RhBi 4 is decomposed and
RhBio formed. There are three eutectics, at 7 per cent, rhodium
(M.pt" 260 C.), at 19-8 per cent, rhodium (M.pt. 772 C.), and at 31-5
per cent, rhodium (M.pt. 995 C.).
A few ternary alloy systems containing bismuth as one of the com-
ponents have also been investigated. Among them may be mentioned
the systems bismuth-zinc-cadmium, 4 bismuth-tin-zinc, 5 and
bismuth-tin-lead. 6 In the last system a ternary eutectic is formed
containing 52 per cent, bismuth, 16 per cent, tin and 32 per cent, lead ;
it melts at 96 C. It has also been suggested that a ternary compound,
Bi 2 SnPb, is formed as a result of a reaction in the solid phase. This
compound is stable below 76 C., but above that temperature it decom-
poses, forming three solid solutions. 7
The quaternary system bismuth-cadmium-tin-lead has also been
investigated. 8 A quaternary eutectic is formed containing 49-5 per
cent, bismuth, 10-10 per cent, cadmium, 13-13 per cent, tin and 27-27
per cent. lead. It melts at 70 C. (See table, p. 149.)
1 Lewccmja, Zc.it sch. anory. Chcm., 1908, 59, 293.
2 Voss, ibid., 1908, 57, 34; Hag? and Funkc, Zeitsch. physical. Cham., 1930, 6, 272.
3 It ode, Ann. Intt. Plati-nt, 1929, Xo. 7, 21.
4 MathcAvson and Scott, Zeitsch. M etallkunde, 1914, 5, 1.
5 MuzaiTar, J. Chcm. Soc., 1923, 123, 2341.
fi Mazzotto, Zeitsch. M etallkunde, 1913, 4, 273; Shepherd, J.Phys. CJiem., 1902, 6,
519; Charpy, Cow.pt. rand., 1898, 126, 1569.
7 Tsihara, tici. Rep. Tohoku Imp. Univ., 1929, 18, 715.
8 Pai-ravano and Sirovich, Gazzetta, 1912, 42 I, 630; Hommel, Zeitsch. MetaUkunde,
1921, 13, 511, 565.
CHAPTER IV.
COMPOUNDS OF BISMUTH.
General. In accordance with its position in the Periodic Table,
bismuth shows more metallic properties than any other element of this
sub -group ; it resembles the other members in showing- variable valency,
but compounds other than tervalent are, in general, either unstable or of
doubtful existence. Five oxides have been described, viz. bismuth
monoxide Bi 2 O 2 , trioxide Bi 2 O 3 , tetroxide Bi 2 4 , pentoxide Bi 2 O 5 , and
hexoxide Bi 2 O 6 . The lower oxides are definitely basic, although only
the halides and some organic compounds of bivalent bismuth have been
described, while the higher oxides show feeble acidic properties. No
definite acid has been isolated, but alkali bismuthates, derived from
quadri- and quinquevalent bismuth, have been prepared. These are,
however, very unstable, being decomposed by water with evolution of
oxygen. Salts of tervalent bismuth are readily hydrolysed by water,
many intermediate products of great complexity being formed, the
structure and composition of which are still to some extent uncertain ;
the hydrolysis is, however, incomplete, as the final product is, in
each case, an oxy-salt of the type BiOX, e.g. BiOCl. A characteristic
feature of tervalent compounds, particularly the halides, is the tendency
to form complex compounds with halogen acids. In these complexes
the bismuth atom appears to become quinquevalent and to enter a
complex anion. 1
The Physiological Action of Bismuth and its Compounds.
Bismuth compounds are not appreciably absorbed into the system
when taken internally ; absorption appears to take place more readily,
however, when applied externally, as in a dusting powder. The salts
are used mainly on account of their local action. Bismuth sub nitrate
(bismuthyl nitrate) is considered to be an astringent and an antiseptic,
its action probably being due to hydrolysis causing the liberation of
nitric acid.
When taken by the mouth, bismuth preparations form a protective
coating on the stomach and intestines. They arc used largely in the
treatment of gastric affections and diarrhoea. Recently they have
been used in the treatment of syphilis and similar diseases, sodium
potassium bismuthyl tartrate being most commonly employed. Bis-
muth oleate is used for intramuscular injections.
Bismuth subnitrate is believed to lessen the secretion of acid in the
stomach ; it has been known, to cause constipation.
Bismuth, when absorbed, is stored up in the liver.
1 Miiller and Kiirthy, Biockem. Zcit., 1924, 147, 385; Jellinek and Kiilm, Zeitsch.
pJiysikal. Chem., 1923, 105, 337; Noyes, Hall and Beattie, J. Amer. Chem. Soc., 1917,
39, 2526.
154:
COMPOUNDS OF BISMUTH. 155
Large quantities of bismuth can be administered without producing
poisoning symptoms. Cases of poisoning have been reported, though
in the older eases the poisoning was probably due to impurities, such
as arsenic, in the bismuth. Cases of poisoning arc indicated first by
ulcerations in 1: lie mouth, followed by vomiting and diarrhoea. Death
ensues very rarely. 1
BISMUTH AND HYDROGEN.
From the position of bismuth in the Periodic Table it is to be expected
that a stable hydride of bismuth would be formed only with difficulty.
Until comparatively recently the existence of bismuth hydride was
doubtful, but later investigations have revealed that a gaseous tri-
hydride can exist, and that it resembles in many ways the trihydrides
of antimony and arsenic. A solid hydride has also been reported. 2
Hydrogen is not absorbed by bismuth in the electric discharge tube. 3
A substance described as bismuth dihydride, Bi 2 H 2 , has been
obtained by the action of zinc and hydrochloric acid upon bismuth
trichloride. It is a grey solid which decomposes when heated in vacuo
or in a current of hydrogen. 4 The true nature of this substance is,
however, not fully established.
Bismuth Trihydride, BiH 3 , was first obtained in small quantities
by the action of dilute hydrochloric acid (O2A r ) on an alloy of mag-
nesium and thorium C (a radioactive isotope of bismuth). 6 It has
since been obtained from a non-radio alloy of bismuth and magnesium
by the action of:' more concentrated hydrochloric acid (4A r ). The best
results appear to be obtained when the magnesium is not completely
alloved with the bismuth but only superficially coated with that metal. 7
With non-radio material approximately 5 x 1()~ 5 of the bismuth used is
converted into the hydride ; this is about one-twentieth of the yield
obtained when radio materials arc employed. The formation of the
trihydridc could not be detected when active hydrogen reacted with
powdered bismuth. 8 It is formed by an oscillating discharge between
bismuth electrodes in an atmosphere of hydrogen. 9 In the latter
method it is essential that the products should be removed and cooled
to room temperature as rapidly as possible, and there must be a complete
absence of organic substances.
Bismuth trihydride is a gaseous compound 10 which is almost as
stable as antimony trihydridc at ordinary temperatures but is readily
1 JDixon, *'' Ma-mud t>J Pharmacohyy'''' (London, 1929), 7th Eel., 408; Cusliny, ''A Text-
Book of Pli'ir)iinc(jl<>fjii iiiid Therapeutics," translated by Edmunds and Gunn (London,
1928), 9th Ed., 073.' ' Eor bibliography, see Anon, Analyst, 1933, 58, 607.
2 For early rei'ercnees to bismuth hydride, see JLluhland, Schwciyyc.r~'s </., 1815, 15,
417; .Meurer,' -f'J>c/z. Phaini., 184.3, [2J, 36, 33; Schlossbergcr and Fresenius, Annalen,
1844, 51, 418.
a -Xewman, Proc. Phys. Soc. London, 1921, 33, 73.
4 AVeekes and Druoe, Lite. Trav. chim., 1925, 44, 970; J. Chtm. &oc., 1925, 127, 1799;
Nature., 1925, 116, 710.
"' Strcckcr and Daniel, tier., 192G, 596, 1091; AYeekes and Druce, Chem. News, 1920,
133, 243.
' Panet-h, Ber., J918, 51, 1704; Zeitsch. EteJdrochcm., 1.918, 24, 298.
7 Pancth and VVintcrnitz, Bar., 1918, 51, 1704, 1728.
b Pearson, Kobinson and Stoddart, Proc. Roy. /S'oc., 1933, 142 A, 275.
IJ Forcsti and Mascarctti, Gazzetta, 1930, 60, 745. fcsee also Paneth, Matlhies and
Schmidt- Hebbel, 7Je/\, 1922, 556, 775.
10 For the spectrum of bismuth hydride, see Hulthen and Hcimer, Nature, 1931, 127,
557; 1932, 129, 399; Hulthen, ibid., 1932, 129, 50.
156 ANTIMONY AND BISMUTH.
decomposed on heating. At 160 C. the amount of undecomposed
hydride is 35 per cent., at 250 C. 9 per cent, and at 350 C. G to 7 per cent.
At red heat decomposition is complete. In the heated tube employed
in the Marsh test, a mirror similar to the antimony mirror is produced :
a strong brown mirror is obtained in front of the heated spot and a
fainter ring behind it. The hydride is completely decomposed by con-
centrated sulphuric acid. The best absorption reagent for the gas is
0-4 A 7 solution of silver nitrate; it is also partially absorbed by normal
potassium hydroxide solution, 0-4A 7 solution of sodium carbonate,
4A T solution of sulphuric acid, and water saturated with hydrogen
sulphide. Drying agents such as soda-lime and calcium chloride may
also be used for its absorption, but water alone does not absorb it well.
Bismuth trihydride can be distinguished from antimony trihydride
by a luminescence method. 1 The gas from the Marsh test is ignited,
and bismuth is deposited on a small fragment of calcium carbonate held
in the flame. If the calcium carbonate, after cooling, is placed on the
edge of a hydrogen flame the bismuth on it will impart to the flame a
cornflower blue coloration. Antimony in similar circumstances imparts
an azure blue coloration. 2
BISMUTH AND THE HALOGENS.
In the principal compounds of bismuth with the halogens, the
bismuth is tervalcnt. It is possible that an unstable pcntafluoride, or
an oxy-triiluoride, exists at low temperatures, but there is 110 evidence
HALIDES AND OXYHALIDES OF BISMUTH.
Fluorine.
Chlorine.
Bromine.
Iodine.
[BiClJ
[BiBr 2 ]
[BiI 2 ]
BiF 3
H 8 BiF 6
BiCl 3
[HBiClJ
[H,BiCl 5 ]
[HBioCL]
BiBr,
|HBiBv] 4
[H 2 BiBr 5 |
Bil.,
[HBiI 4 ]
fH.BiI s l
[H 3 BiJ 9 ]
BiOF
BiOCl
BiOBr
BiOI
B1OF.2HF
[Bi,O s CL>]
[Bi 3 O 2 Cy
[Bi 4 o 3 cy
[Bi 5 3 I 4 ]
[BiF 8 ]
[BiOF 3 ]
[Bi 8 15 Br 6 ]
[Bi n 13 Br 7 ]
1 Paneth and W inter nitz, loc. cit.
2 See also Muacllim, Boll. Ckim. farm., 1929, 68, 10S6; Paneth, Johannsen and
Matthies, J3er., 1922, 55 B, 769: Paneth, Zcitsch. EleJdrochtm., 1920, 26, 452; Vanino and
Zumbusch, Arch. Pharm., 1911, 249, 483. For a comparison of the properties of the
hydrides of elements of the fifth group, see Durrant, Pearson and Robinson, -/. Chcni. Soc.,
1934, 137, 730; Pearson and Robinson, ibid., p. 736.
COMPOUNDS OF BISMUTH. 157
for the existence of other quinqucvalent compounds except perhaps in
complexes. Bivalent compounds of bismuth with the halogens (with
the exception of fluorine) have been reported, but it is doubtful if these
have been obtained in a pure state, and they are not very stable. With
the exception of the fluorides, the halides are all hydrolysed bv water,
but the hydrolysis is not complete, the final product being an oxyhalide.
The halides tend to form complexes with the corresponding halogen
acid ; these complexes are themselves acidic, and in all cases except
the fluoride, stable salts have been obtained.
Bismuth and Fluorine.
Of the two fluorides of bismuth that have been reported, the tri-
fluoride is the only one known to exist with certainty. It is possible
that an unstable pentafluoride may exist at low temperatures, but it has
not yet been isolated.
Bismuth Trifluoride, BiF 3 , is obtained by the addition of a con-
centrated solution of potassium fluoride to a neutral solution of bismuth
nitrate ; 1 or by the action of hydrofluoric acid upon bismuth trioxide. 2
In the latter case the mixture is warmed, and hydrofluoric acid is added
as evaporation takes place. When the action ceases, the liquid is
decanted and evaporated ; the residue is then heated until no more
fumes of hydrofluoric acid are evolved.
Bismuth trifluoride is a heavy, greyish- white, crystalline powder.
The crystal has a face-centred cubic structure with four molecules in the
unit cell : 3
a -5-853 0-004 A.
Its density 4 is 5-32 at 20 C. It is the most stable halide of bismuth.
It melts without decomposition, and is only slightly volatile even when
strongly heated. It is almost insoluble in both water and alcohol, and
is not hydrolysed by cold or boiling water. 5 It is decomposed by,
and dissolves in, hot mineral acids. It does not react with sulphur, or
with the oxides of nitrogen. It dissolves readily on boiling in a con-
centrated solution of potassium fluoride, but it has not been possible
to isolate a complex salt from this solution. 7
If, when preparing bismuth trifluoride by the action of hydrofluoric
acid upon bismuth hydroxide, the residue is only gently heated, a
substance is produced which appears to be a complex hydrofluobis-
muthic acid, II 3 BiF 6 or BiF 3 .3HF. It is a greyish-white, crystalline,
deliquescent substance ; on heating it loses hydrofluoric acid, and on
heating with water it is decomposed with the formation of bismuthyl
fluoride, BiOF, an intermediate compound BiOF.2HF being formed.
which is decomposed on washing with water. 8 Xo salts of this acid
are known.
If a boiling concentrated solution of ammonium fluoride is saturated
with precipitated bismuth hydroxide, and the solution allowed to stand
] Coil and Aluir, Chc.m. Xc.ws, 1887, 56, 2o7; J. Chc.tn. Soc,., LSS8, 53, 137.
- .Muir, IlolTnicister and Kobbs, J. Ch.(-.tn. Sue., 1881, 39, 33.
:! I lasso] and Xilssen, Z'-ifxck. u-norij. Chun., !!):>!), l8l, 172.
-1 The density calculated from crystal structure is stated to be S-7.">.
"' Her/ and V>ulla, Zc.tivcli.. ttnorf/. Ch,<-m., l ( .)0i), 6l, 3S7.
1 The density calculated from crystal structure is state
"' Her/ and V>ulla, Zc.tivcli.. ttnorf/. Ch,<-m., l ( .)0i), 6l, 3S7.
< ; Fnllerlon, Avttt . J. ScL, 1877, [))], 14, 281.
158 ANTIMONY AND BISMUTH.
for a long time, on cooling, small, transparent, rhombic, or monoclinic
crystals of ammonium fluobismuthate or bismuth ammonium
fluoride, (NH 4 )BiF 4 , separate out. The crystals are easily decomposed
by water, yielding bismuthyl fluoride ; and they dissolve in hot moder-
ately dilute acids. 1
Bismuthyl Fluoride or Bismuth Oxy fluoride, BiOF, can be obtained
by the decomposition of BiF 3 .3HF or of BiOF.2HF as described above ;
or by adding freshly precipitated bismuth hydroxide to hydrofluoric
acid until the acid is just neutralised. 2 It is described as a heavy, white
powder, of density 7-5 at 20 C., not deliquescent, decomposed when
heated to bright redness.
Bismuth trifluoride does not combine with fluorine except perhaps in
traces at - 80 C. 3 If so-called " bismuthic acid " or potassium bismuth-
ate is added to 40 per cent, hydrofluoric acid at -10 C., a colourless,
very unstable solution is obtained which probably contains a compound
of quinquevalent bismuth. 4 The compound has not been isolated, as
it decomposes when the solution is evaporated. It may be bismuth
peiitafluoride, BiF 5? but it appears more probable that it is mainly
bismuth oxytrifluoride, BiOF 3 . The solution has strong oxidising
properties, as shown by its action on hydrochloric acid, potassium iodide
and alcohol (the latter being oxidised to aldehyde). If potassium
fluoride is added to the solution before evaporation, the substance
Bi 3 O 4 F 7 .3KF separates out as small, yellow crystals ; with excess of
potassium fluoride, a double compound of bismuth oxytrifluoride and
potassium fluoride, BiOF 3 .3KF, is obtained as well-formed, colourless,
prismatic crystals which decompose in moist air, becoming yellow.
Bismuth and Chlorine.
Although the chief compound of bismuth and chlorine is bismuth
trichloride, BiCl 3 , many of the older investigators held that a lower
chloride, bismuth dichloride, BiCl 2 or Bi 2 Cl 4 , also existed. It is
stated that this compound is formed as a black substance when a slow
current of chlorine is passed over powdered bismuth heated nearly to the
melting point ; after prolonged treatment it changes to a light amber
liquid from which the trichloride can be obtained by sublimation. 5 It
is claimed that bismuth dichloride may also be obtained by heating a
mixture of bismuth and mercurous chloride to between 230 and 250 C.,
by heating bismuth ammonium chloride in a current of hydrogen at
300 C., 6 by the reduction of bismuth trichloride by bismuth, phosphorus,
zinc, tin, mercury and certain organic compounds 7 or by hydrogen, 8
and by heating bismuth trichloride with phosphorus trichloride.
More recently, thermal investigations of the system Bi~BiCL have been
undertaken, but the evidence obtained concerning the existence of the
1 von Hclmont, loc. cit.
~ Gott and iMuir, lor.. c.iL
- Ruif, Knoch and Zcdner, ZciLwh. n.n<n(j. Chf-tn., IOCS, 57, 320.
1 Wemland and La.uenst.cm, Ze.it *ch. a-tiortj. Chert/.., 1899, 20, 40.
:> -Mair, J. Ghtiri. >SV:., 1876, 29, J4-.I ; Weber, J'rxjy. A ii)ialc/>,. 18.1!), 107, 5',M'j; I VI ir rain,
Bull. Soc. chim., 1862., [11, 4, 22; Thomas, Ann. Chim. Wujs., I SOS, [71, 13, 1 if,.
Schneider, I'vyy. An-nale.ii., 185"), 96, 130.
"< Weber, loc. cit.
s Muir, loc. cit. See also, however, Hcintz, Pogg. An/i.alen, 1844, 63, 55.
<J Michaelis, J. praJcl. Chcm., 1871, [2], 4, 454.
COMPOUNDS OF BISMUTH.
159
dichloride is conflicting. Herz and Guttmann found a maximum on the
liquidus curve at a composition corresponding to BiCl 2 , the melting
point being 163 C. and the density 4-85 to 4-88 (the latter value being
lower than the density of the equivalent mixture of bismuth and
bismuth trichloride) ; I while Eggink could find no evidence for the
existence of BiCl 2 but suggested that both Bid and BiCl 4 (see fig. 5)
were formed. 2 According to Marino and Becarelli, the so-called bis-
muth dichloride is really a solid solution ; but although the melting
point of this solution is higher than that of either bismuth or bismuth
35U
320C. f
V
/
inn
;\
/
\
c
v
-\
1
5*.
?E
j
-
2
32 C.-
Qc
5 Q
o
^
\" a
9nn
<
"T
\
7 r/>
-
209C
\
\
\ \
206C\
700
1
80 70 60 50 40 30 20
Bismuth, Atoms per cent.
70
FIG. 5. Freezing Point Curve of the System Bismuth-Chlorine.
trichloride, they were unable to determine any maxima on the liquidus
curve on account of sublimation. This solid solution undergoes a trans-
formation into a /3- variety, the change being accompanied by a. marked
evolution of heat ; on fusion and cooling, these jS-crystals change into
a-crystals of different composition and two liquid phases separate out. 3
An investigation into the free energy of fused bismuth trichloride did
not afford any evidence in favour ol' the existence of a lower chloride. 4
The compound has certainly not been obtained pure, although by
cooling the melt obtained by heating bismuth trichloride with bismuth,
black, needle-shaped crystals have been obtained. 5 The impure
substance is dull black, and very hygroscopic ; it melts readily. Many
of the reactions ascribed to it could almost equally well be ascribed to a
mixture of bismuth and its trichloride. When heated to about 300 C.
1 'Her/ and Guttmann, Zfilxrh. (inury. Ckc.w.., 1008, 56, -422.
2 Ivjoink, Zc.-dxch.. -plujxtkaL Client,.^ 1908, 64, 4-1!). See also Hcrz, Zc.'txch. <utc,r<j.
67^;//,./l909, 61, .Hi).
3 Marino and Bccavelli, Ath R. Ac.utd. Linn-i, 11)15, |v], 24, ii, (525; MJKi, [v|, 25,
i, 221, 320.
4 Devoto and Gu/zi, CuzzMn., J929, 59, 708,
5 Weber, loc. cit.
160 AXTIMONY AXD BISMUTH.
in the absence of air the substance decomposes into bismuth and bis-
muth trichloride. 1 Heated in air it forms a mixture of bismuth,
bismuth trioxide and bismuthyl chloride. 2 It is readily decomposed
by water according to the equation
3BiCl 2 + 2H 2 =Bi +4HC1 +2BiOCl
It combines with chlorine to form the trichloride. With a concentrated
solution of potassium hydroxide the so-called black bismuth suboxide is
obtained, which rapidly oxidises to the yellow trioxide. 3 Dilute acids
decompose it yielding salts of tervalent bismuth and metallic bismuth.
The substance does not combine with ammonia. 4 It has been
suggested, however, that a double compound with ammonium chloride
is formed having the composition BiCl 2 .XH 4 Cl, 5 although the dichloride
is decomposed by a concentrated solution of ammonium chloride. 6
Bismuth Trichloride, BiCl 3 , appears to have been prepared first
by Boyle in 1664, 7 and later by Poli in 1713, 8 by heating a mixture of
bismuth and mercuric chloride. It may also be "obtained by the direct
union of the elements ; 9 by the action of hydrochloric acid upon
bismuth in the presence of air, 10 concentrated hydrochloric acid upon
bismuth trioxide, pent oxide or trisulphide, or aqua regia upon bismuth ; u
by heating bismuth trioxide, pentoxide 12 or trisulphide 13 in a current of
chlorine, the oxides in a current of hydrogen chloride, 14 or bismuth with
phosphorus trichloride ; 15 or by the" action of silicon tetrachloride 16 or
sulphur monochloride 17 on bismuth trioxide.
The trichloride is usually prepared by heating bismuth in a rapid
current of chlorine and subliming the product in an atmosphere of carbon
dioxide ; by dissolving bismuth in aqua regia, evaporating the solution
to dryness and distilling the residue in an atmosphere of carbon dioxide :
or by dissolving bismuth trioxide in hydrochloric acid and proceeding
as in the previous method.
Bismuth trichloride forms a snow-white opaque mass which can be
crystallised by sublimation, the crystalline mass darkening on exposure
to light. 18 Its density 19 is 4-75 at 20 G C. ; the thermal "coefficient of
expansion 20 between 20 and 120 C. is approximately 167 xlO~ 6 ; and
1 Schneider, loc. tit.
~ Thomas, Joe. cit.; Dcherain, loc. cit.
3 Schneider, loc. cit.
4 Deherain, loc. cit.
5 Schneider, loc. cit.
r> Weber, loc. cit.
7 Boyle, '''Experiments and Considerations concerning Colour''" (London), 1664.
8 Poli, "JMimoires de VAcademie des Sciences : ' (Pans), 1713, p. 40.
9 Davy, Phil Trans., 1812, 102, 169; Weber, Pogg. An.nalen, 1859, 107, 596; Deherain,
Bull Soc. chim., 1S62, [1], 4, 22; Muir, J. Chem. Soc., 1876, 29, 144; Cowper, J. Ch<>m.
Soc., 1883, 43, 153; Thomsen, Ber., 1883, 16, 4.0.
10 Ditte and Metzner, Compt. rend., 1892, 115, 1303; Ann. Chim. Phys., 1893, 29,
389; Heintz, Pogg. Annalen, 1844, 63, 55, 559.
1 Tanatar, Zeitsch. anorg. Chem., 1901, 27, 437.
2 Muir, HoiTmeister and Robbs, J. Chem. Soc., 1881, 39, 32.
3 Muir and 'Eagles, J. Cham. Soc., 1895, 67, 92; Rammler, Ber. t 1891, 24, 354.
' Bird Mover, J. Anter. Che.m. Soc., 1897, 18, 1029.
Michaelis, J. pmU. Chem., 1871, [2], 4, 454.
Ranter, Annalen, 1892, 270, 25].
Oddo and Scrra, Gazzctta, 1899, 29, IT, 355.
8 Liesegang, Photograph. Arch., 1893, 34, 177.
<J Honigschmid and Birckenbach, Bar., 1921, 54 B, 1873.
20 Klcrum, Tilk and Miillenheim, Zeitsch. anorg. Chem,, 1928, 176, 1.
COMPOUNDS OF BISMUTH.
161
the molecular volume at low temperatures, 1 calculated from the density
at -194 C. and the thermal coefficient of expansion, is 64-2.
The melting point 2 is 232 C. The density of the molten trichloride
varies linearly between 250 C. and 350 C. according to the expression 3
D[ = 4-438 -0-00229*
The surface tension, determined by the method of maximum bubble
pressure in an atmosphere of nitrogen, and other data, for the density, are
as follows : 4
1 T ~ ^^
\ lemp., " C. .
| Density, D\ .
j Surface Tension
(dynes per cm.)
271
3-811
66-2
304
3-735
61-8
331
3-682
58-1
353
3-621
382
3-554
52-0
The variation of the viscosity of fused bismuth trichloride 5 with
temperature is given below.
Temp., C.
Viscosity x 10 2
260 j 270 280 290
300
310 320
330 34-0
. (grams per em.
per sec.)
i
32-0 \ 29-5 27-0 25-0
23-0
21-5 , 20-5
19-0 18-0
The vapour pressure of bismuth trichloride 6 has been determined,
and the boiling point 7 is 447 C. The heat of vaporisation is 18,000
gram-calories per mole. 8 The vapour density (air = l) is 11-35, the
calculated vapour density 9 being 10-89.
A band spectrum of the vapour of bismuth trichloride has been
observed 10 in the region between the wavelengths 4300 A. and 5500 A.
The emitter appears to be Bid ; the bands are degraded towards the
longer wavelengths, and isotropic effects (due to chlorine) have been
observed.
Bismuth trichloride sublimes without decomposition in an atmo-
sphere of carbon dioxide ; in air, however, a portion only sublimes
J Billz, Sapper and Wunnenbcrg, Zc.itsch. anon/. Chr-m., 1932, 203, 277.
- Inter nation <d Critical Tables, 1926, I, .106. Sec also Muir, J. Cham. 8oc., 187G, 29,
144.
:J I-vlcrnati anal Critical Tabl, 1928, 3, 329; Voigt and. Biltz, Zcif.sch. anrmj. Ch.r-in.,
1924, 133, 277. Sec also Aien, Zcitxc.k. phy.wkaL Chun., 11)09, 66, 641; .Jaeger and Kahn,
Proc,. K. A /cad. Wcff-.nwh. A-inHtcrdaw., 1916, 19, 397; -Jaeger, Ztitsr.h. n.n.ory. Chan., 19.1.7,
101, 1.
I f Jaeger, Joe. ciL
5 1-nl'c.rn.ational Critical Table.*, 1930, 7, 212; Atcn, Joe. cit.
II Evncvitsch and Suchoclski, J. Jiusx. Pliys. Clic.in. 8oc., 1929, 61, lo()3.
7 International Critical Tables, .1928, 3, 329. See also >laier, Burc.au of Mines Trrli-no-
Jonlcal Papf.r, HJ2;~>, 360, 1; Carnelley and Williams, J. Chc.w. Soc., 1878, 33, 281 ; Meyer-
ami Krause, An-nalrn, 1891, 264, 124; Ansehulz and AVeyer, -ibid., 1891, 261, 207; Meyer
and Freyor, Zc.-H^rh. a nary. Ch.f-rn., 1892, 2, 4. 1'or the. elevation of the boiling point,
produced by various solutes in bismuth irichloridc, see Rugheimer and Kudolli, A-iinn'/cn,
P.M!,-), 339, 311.
s .Maier, loc.. ciL
'' Jaequelam, A-nn.. C/ttw. Pliy*., 1837, [2], 66, 113; J. prakt. Clicm., 1S3S, 14. I.
K) c- m^,. o, .,.,,:.,. idol U^T i T i o
162 ANTIMONY AND BISMUTH.
unaltered, the remainder being converted into non- volatile, colourless,
mica-like leaflets of bismuth oxychloride. 1
It will dissolve in hydrochloric acid, alcohol, acetone, liquid
ammonia, 2 and to a slight extent in liquid hydrogen sulphide. 3 The
solution in acetone behaves like an aqueous solution towards many
reagents, 4 and the solution in hydrogen sulphide does not conduct
electricity. 5
The absorption spectrum of very dilute solutions (iV/1 0,000) of
bismuth trichloride in hydrochloric acid is characterised by a very strong
selective action ; 6 a deep band with its head at A = 3250 A. is prominent.
Similar solutions of arsenic trichloride and antimony trichloride show
general absorption only. The Raman spectrum of a solution of bismuth
trichloride in hydrochloric acid consists of four lines, the fourth of which
is exceptionally strong. 7
The heat of formation of the trichloride from the elements 8 is
00,630 gram-calories per mole.
The reduction of bismuth trichloride has already been discussed
(p. 158). In addition to the reactions given, reduction may be carried
out by passing the vapour of the trichloride over magnesium heated to
the melting point ; metallic bismuth is precipitated. 9
The trichloride is deliquescent, and is decomposed by water forming
bismuth oxychloride; 10 with excess of water the reaction is complete,
whilst it is hindered by the presence of hydrochloric acid or alkali
chlorides. 11
No reaction takes place when bismuth trichloride is heated with
sulphur monochloride or chromyl chloride. 12
Bismuth trichloride reacts immediately with liquid hydrogen
sulphide, even at low temperatures, forming an orange-red solid, which,
after drying in a desiccator over sulphuric acid, has the formula
BiSCLBiCl 3 . 13
The trichloride reacts with hydrogen sulphide in the dry way with
the formation of bismuth thiochloride, BiSCl. 14 Bismuth thiophosphate,
BiPS 4 , is formed by the action of phosphorus pentasulphide. 15
When heated in nitric oxide, bismuth trichloride forms a yellow
crystalline substance BiCl 3 .XO, which is decomposed by water. 16 This
substance can be melted in a sealed tube without decomposition, and is
very hygroscopic. 17 Bismuth trichloride also absorbs nitrogen peroxide
1 Jacquelain, loc. cit. 2 Gore, Proc. Roy. Soc., 1873, 21, 140.
3 Antoni and Magri, Gazzetta, 1905, 35, I, 206.
4 Naumann and Schulz, Ber., 1904, 37, 4331.
5 Quam and Wilkinson, Proc. Iowa Acad. Sci., 1925, 32, 324.
6 Macbeth and Maxwell, J. Chc.m. ,S'oc., 1923, 123, 370. Sec also Schafer and Hem,
Zeitsch-. annrg. Che.m., 1917, 100, 249.
7 Daure, Compt. rend., 192S, 187, 940.
8 Thomson, "Thermochemistry" (London), 1908, p. 236.
Seubert and Schmidt, AnnaJen, 1892, 267, 238; Paktor, Pharm. Post, 1904, 38, 153;
Chem. Zentr., 1905, i, 1305.
10 Jacquelain, Ann. Chim. Phys., .1837, 66, 113; Heintz, Pogg. Ann (den, 1844, 63, 71 ;
MacTvor, Chem. JVY;w;.?, 1875, 32. 222; Merz and Weith, B&r., .1880, 13, 210.
1 Oansse, Compt. rc.r.d., 189], 112, 1220; 113, 547; ' Chem. Zcnlr., 1892, T, 53.
- Muir, J. Chem. Soc., 1878, 33, 193.
a Ralston and Wilkinson, J. Ame/r. Ch,f:.m. Soc., 1928, 50, 258.
1 Schneider, Pogg. Annulvn., 1854, 93, 464; Aluir and Eagles, ./. Chew. Soc., 1895, 67,
Che.m. News, 1895, 71, 35.
5 Glatscl, Zeitsch. anorg. Chem., 1893, 4, J86.
i; Wesson, Compt. rend., 1889, 108, 1012.
7 Thomas, Compt. rend., 1895, 121, 129.
COMPOUNDS OF BISMUTH. 163
at the ordinary temperature, forming a yellow mass of the composition
BiCl 3 .XO 2 , stable in dry air. At higher temperatures this is oxidised,
but it does not evolve nitrogen peroxide in vacua. In moist air it is
decomposed with evolution, of nitrogen peroxide, while water converts
it to bismuthyl chloride with a violent evolution of gas. 1 Xitrosyl
chloride reacts violently with bismuth trichloride at the ordinary
temperature, and from the resulting solution the compound BiCl 3 .NOCl
separates as an orange-coloured powder, which is deliquescent and
decomposed by water. 2
The trichloride is converted into trioxide on heating with mercuric
oxide. 3 It will react with carbon compounds in a manner similar to
ferric chloride ; it will dissolve in many hydrocarbons, but on heating it
is possibly reduced to the dichloride. 4
Investigation of the hydrolytic dissociation of bismuth trichloride
shows that in the reaction
BiCl 3 +H 2 = BiOCl + 2HCI
the ratio BiCl 3 /[HCl] 2 remains constant for a considerable range of
temperature, but tends to increase somewhat at high concentra-
tions. The presence of alkali chlorides, and more particularly alkali
bromides, reduces the extent of dissociation, while alkali nitrates
have a smaller influence. Sodium sulphate is practically without
influence on the hydrolysis. The effect of increase of temperature is
to reduce the amount of dissociation. 5 From a study of the system
Bi 2 O 3 -HCl-H 2 O (see tables, p. 164) it appears that in certain
solutions bismuthyl chloride is the stable phase, in others bismuthyl
hydroxide ; in the presence of alkali the solid phase BiOCl is quanti-
tatively converted into the hydroxide BiO.OH (p. 1 68). From measure-
ments of the concentrations of the ions H + , Cl~ and Bi~ u r + in hydrochloric
acid solution saturated with bismuthyl chloride it has been shown that
the reaction
Bi ' J + HoO + Cr ^ BiOCl H- 2H-
obeys the law of mass action. 6
By dissolving bismuth trioxide in excess of hydrochloric acid and
evaporating the solution, .One needle-shaped crystals of hydr cited bismuth
trichloride, BiCl 3 .2H 2 O, are deposited. 7 When water is saturated with
bismuth trichloride and hydrochloric acid at 20 C. and cooled to C.,
ciystals arc deposited which have the composition 2BiCl 3 .IICJ.3H 2 O.
These crystals are stable at the ordinary temperature. 8
Chiorobismuthous Acid. Bismuth trichloride is very soluble in
concentrated hydrochloric acid, and there arc indications of the forma-
tion of a, double compound ; from measurements of the electrical
1 Thomas, Com pi. rc/nd., .1896, 122, 611. See also Besson, loc. cil.
- .Sudborouc;h, J. Che.m. $GC., 189], 59, 602. See also PJieinboldt and Wasserfuhr,
Jicr, 1027, 60 B, 732.
3 YoJhnrd, Ann. 67m//. Phnrm., 1870, 198, 331; Smith and Heyl, Ztitsch. anon].
Chan., 1 894. 7, 87.
' Thomas, for. r/f.
"' Her/ and Bulla, Zf-ft.rl,.. nnor<j. CUi'-),,., 1000, 61, 387: 1000, 63, ,10; 'Dubnsay, Corn-pi,
raid., 1909, i/|8, 830.
(1 .Jdlinok and Kulm, Zf-ilwJi. -physical . Chew., 1023, 105, 337.
7 Kn <:cl, Cfn.-j,L rc.nd., 1888, 106, .1707. See also Arppc, Pofjrj. Annul en, 1845, 64,
237; Heintz, ,/. praU. C/tr-.tn.., 1848, 45, 102.
s 'Engel, Compf. rend., 1.S88, 106, 1797.
Date, Compt. rend., 1880, 91, 086.
AXTB10XY AXD BISMUTH.
EQUILIBRIUM IN THE SYSTEM Bi 2 O 3 -HCl-H 2 O.
Solubility at 18 C.
(Moles per 100 moles Water).
HC1.
Solid Phase.
0-71
0-0018 ]
0-74
0-0021
0-89
0-0056
1-18
1-28
0-0165
0-0247
> BiOCl
1-36
0-0315
2-20
0-1185
3-81
0-2835 J
Authority: Jellinek and Kiihn.
Solubility (Grams per 100 grams Saturated Solution).
At 25 C.
At
30 n C.
1
HC1. ! Bi 2 3 . Solid Phase.
HC1.
Bi 2 3 .
i Solid Phase,
2-50 0-6 BiOCl
2-40
0-60
BiOCLH 2 O
4-22 2-60
5-69
5-35
35
10-68 11-40
13-02
14-52
J5
13-43 16-41
21-70
30-10
55
18-47 26-42
31-50
54-70
7 J
30-23 50-74 ^
32-80
56-00
BiOCl
33-67 58-72 EiCl 3
33-00
58-50
BiCl. 3 .2HoO
35-14 58-59
33-80
56-60
BiCl 3 +BiCl 3 !2H.>0
34-90
56-25
BiCl 3 " !
35-90
55-9
BiC],.HCl
Waris, J . Indian Chem. Soc.
1925, 1, 307.
Jacobs, Chem. Weekblad., 1917,
14, 208.
conductivity of solutions of bismuth trichloride in aqueous hydro-
chloric acid the composition of this acid would appear to be cither
HBiCl 4 or H 2 BiCl 5 , while investigations using solutions of bismuthyl
chloride in hydrochloric acid (see following table) indicate that
H 2 BiCl 5 predominates when excess of the acid is present in dilute
solution, while HBiCl 4 predominates in more concentrated solution
with a lower concentration of acid. 1
1 Xoyes, Hall and Beattie, J. Amer. Chun. Soc., 1917, 39, 2f>2G.
COMPOUNDS OF BISMUTH.
165
SOLUBILITY OF BISMUTHYL CHLORIDE IN HYDRO-
CHLORIC ACID AT 25 C.
(Gram-atoms per 1000 grams Water.)
I
. Chlorine
! Content.
Bismuth
Content.
; Hydrogen
1 Content
j (calc.).
Chlorine
Content.
Bismuth
Content.
!
Hydrogen
Content
(calc.). :
i
' 0-3477
0-00130
j
0-3438
1-2270
0*1177 0-8746 !
0-4350
0-00376
0-4237
1-2724
0*1324 0-8752
; 0-4414
0-00396
! 0-4295
1-4348
0-1620 0-9488 '
1 0-4892
0-00646
: 0-4698
1-5321
0-1810
0-9891
1 0-5221
0-00869
0-4960
1-6235
0-2025
1-016
0-5276
0-00899
i 0-5006
1-6350
0-2050
1-020
0-5796
0-01323
! 0-5399
1-7706
0-2352
1-065
0-6244
0-01767
0-5714
1-9021
0-2657
1-105
0-6299
0-01856
| 0-5742
2-5578
0-4216
1-293 ;
0-7038
0-02720
1 0-6222
3-1865
0-5685
1-481
0-7375
0-03138
, 0-6434
3-6366
0-6792
1-599
0-7579
0-03473
0-6537
4-2552
0-8324
1-758
0-8824
0-05338
! 0-7223
4-5056
0-9022
1-799
0-9125
0-05936
' 0-7343
5-325
1-100
2-025 i
1-0760
0-08937
, 0-8079
6-066
1-317
2-115 :
The true nature of these compounds has not yet been fully
ascertained. From physical investigations I it is inferred that the com-
plex may conform to one of the following two formula? :
r
Bid.
Olio
or
Organic compounds corresponding to both of these have been prepared.
From the examination of substituted ammonium compounds of chloro-
bismuthous acid 2 it appears possible that three types of organic com-
pounds may exist, to which have been allotted the following names and
general formuhe :
(a) Hexachlorobismutkites, [XH 3 R] :} fBiCl 6 ] ;
(b) p-Dichloro-octachloro-dibismuthites, [XHR 3 ] 4 [Bi 2 Cl 10 ] ;
(c) p-TricMoro-hexachloro-dibismuthites, [XH 3 ll] 3 [Bi 2 Cl 9 ].
The elucidation of the constitution of these compounds is, however,
rendered extremely diflicult. owing to their instability in aqueous
solutions.
Chlorobismuthites. Bismuth trichloride forms a number of
complex or double salts with alkali chlorides ; some of these are
described below. With lithium chloride 3 is obtained the compound
2LiCl.BiCl 3 . With sodium, chloride the compound NaCl.BiCL.3H 2 O is
1 Schafer and Hem, Z, at Inch, anorg. Chem., 1917, 100, 249.
- Gutbier and Midler, Zeitxch. (inury. Chem., 1923, 128, 137.
166 AXTIMOXY AXD BISMUTH.
formed as a deliquescent substance crystallising in needles ; x other
sodium compounds that have been described are 2XaCl.BiCl 3 .2H 2 2
and 2NaCl.BiCl 3 . 8 With potassium chloride the following compounds
are said to exist : 2KCl.BiCl 3 .2lI O 5 4 KCl.BiCl 3 .H O 5 and KCl.BiCl 3 .
2H 2 0. 6 The rubidium compounds RbCl.BiCl 3 .H 2 O and RbCl.BiCL
have been described; 7 also the cces-ium compounds 3CsC1.2BiCl 3 and
3CsCl.BiCl 3 . 8 With thallium chloride the compounds 3TlCl.BiCl 3 and
6TlCl.BiCl 3 have been obtained, both in the form of large, thin, colour-
less plates. 9 Mixed halogen compounds of bismuth chloride and
potassium halides have also been described, among them being KBr.KCL
BiCl 3 , 2KBr.BiCl 3 . 10
The following compounds with ammonium chloride have been
described : The hydrate 2X.H f Cl.BiCl 3 .2H 2 O forms crystals of the
rhombic system, isomorphous with those of the corresponding bromide
and those of the potassium double salt ; II the anhydrous salt forms
double six-sided pyramids, and is isomorphous with the correspond-
ing antimony compound. 12 The compound 3XH 4 Cl.BiCl 3 forms large,
tabular crystals of the rhombic system. 13 Another compound, to which
the formula 5XH 4 C1.2BiCl 3 has been given, is probably formed as one
of the products when a solution containing equimolecular proportions
of ammonium chloride and bismuth trichloride is crystallised (the other
product being 2XH 4 Cl.BiCl 3 , described above) ; this compound forms
line, tabular crystals of the rhombohedral system. 14
A systematic investigation of the compounds of bismuth trichloride
with chlorides of bivalent metals revealed the following types of com-
pounds : (1) BiCl 3 .M ;/ Cl 2 j corresponding with the series BiCl 3 .2M'Cl
(where M' is an alkali metal) ; salts of this type are regarded as deriva-
tives of pcntachlorobismuthous acid, H 2 [BiCl 5 ]. The following have been
examined : BiCl 3 .MgCl 2 .8H 2 O, stout, rectangular plates ; BiCl 3 .
BaCl 2 .4lI 2 O, rhombic plates; BiCl 3 .CoCl 2 .6H 2 O, pale red prisms;
BiCl 3 ~XiClo.6H 2 O, green needles. (2) 2BiCl 3 .M"C] 2 , corresponding to
the series BiCL.M'Cl (where M' is an alkali metal) ; salts of this type arc
regarded as derivatives of tetrachlorobismuthous acid, HfBiClJ. The
following have been examined: 2BiCl 3 .CaCl 2 .7lI 2 O, colourless needles;
2Bi( 1 .l.j.SrClo.7lI 2 O, stout needles ; 2BiCl 3 .BaCl 2 .5lI 2 O, slender needles.
(3) l.BiCLj.M'TU, corresponding with the scries 2BiCf 3 .]VrCl (where M' is
an alkali metal) ; salts of this type are regarded as derivatives of
hcptachlorodibisimithous acid, H[Bi 2 Cl 7 J. The following have been
1 Jacquelam, ,/. pi'tkt. C/u-.in., 1838, 14, 1.
- Pliny .Bri^ham, ,/. A-nu-.r. Chc.,,1. Xoc., 1892, 14, 164.
:i Aloy and Frebault, loc. cit.
1 Aloy and Frcbault, lac., cit.
r > IlemHcn, ,/. Atnc.r. (-kct/i.. /SV., 1S92, 14, 81.
6 Pliny Bri^liain, loc. cil.
7 Pliny Brigham, lac. cit.
8 Rcnisen, loc. cit.
<J Ephraim and .Burlcczko, Zutsch. anory. Cham., 1909, 61, 238. See also Scarpa,
Atti R. Accad. Li-ncc/i, 1912, [v], 21, li, 719. For compounds with chlorides ot the alkali
metals, sec also Arppe, Poyy. Annalen, 1845, 64. 237; Ram nieLs berg, ibid., 1S59, 106,
jor.
Field, J. Chtni. Soc., 1S93, 63, 540; Atkinson, ibid, 1883, 43, 289.
1 llammelsberg, "' Ihvndbuch Krysl. Cliem." 1855, 215; Poyg. A-it.nah.iL, 1859, 106,
1-1"; Groth, Chem. Kryxt., 1906, I, 431.
- Jae({iielain, Ann. Chim. Phys., 1832, [2J, 66, 113. See also Deherain, loc. cil.
3 Arppc, Po(jfj. A'/t'/idle/i, 1845, 64, 247.
1 Kainmelsberg, Pogg. Annaitn, 1859, 106, 147; Groth, Che.ni. Kryst., 1906, 1, 429.
COMPOUNDS OP BISMUTH. 107
examined : 4BiCl 3 .Mo-CU.16H O, six-sided leaflets ; 4BiCl 3 .SrCU.
12H 2 O, six-sided leaflets^; 4BiCI 3 .MuCI 2 .12H 2 O, flesh-coloured, six-
sided plates ; 4BiCl 3 .FeCl 9 .12H 2 O, faintly yellowish-red plates ;
4BiCl 3 .CoCl 2 .12H 2 0, red, six-sided plates ; 4BiCl 3 .NiCL 2 .12H 2 O, pale
green, six-sided plates. 1
Ammoniates. It has long been known that bismuth trichloride
absorbs ammonia when heated gently in its presence, 2 the reaction
yielding one easily volatile addition compound, BiCl 3 .3NH 3 , and two
non-volatile compounds, 2BiCl 3 .XH 3 and BiCl 3 .2NH 3 . 3 BiCl 3 .3NH 3
is a colourless substance which volatilises in a current of ammonia ;
when acted upon by hydrogen chloride it yields the double compound
3XH 4 Cl.BiCl 3 . 2BiCl 3 .NH 3 is a red, moderately stable substance
which can be melted and crystallised by solidification, but which is
attacked by moisture ; with hydrogen chloride it forms nearly colour-
less, deliquescent needles of the double compound XH 4 C1.2BiCl 3 . The
third compound, BiCl 3 .2NH 3 , is difficult to obtain pure, usually being
mixed with 2BiCl 3 .XH 3 . It is a greenish-grey substance, and its
composition is deduced from the fact that with hydrogen chloride it
forms the compound 2NH 4 Cl.BiCl 3 .
With organic bases, bismuth trichloride forms many crystalline
complexes. 4
Attempts to obtain a higher chloride of bismuth by the action of
chlorine on molten bismuth trichloride, or by passing chlorine over a
heated mixture of bismuthyl chloride and charcoal, have been un-
successful. 5
Bismuthyl Chloride, or Bismuth Oxy chloride, BiOCl. An oxy-
chloridc, which is probably bismuthyl chloride, occurs in the mineral
daubreit, which is found in Bolivia. 6
Bismuthyl chloride is the product obtained by the reaction of
bismuth trichloride with water, the decomposition being effected by
the action of either hot or cold water on the solid, or by the addition
of water to a moderately concentrated solution in hydrochloric acid.
It is also obtained by the addition of a solution of an alkali chloride
to a solution of bismuth nitrate. 7 Many other methods may also be
adopted for the preparation of this substance. (]) When bismuth
trichloride is heated in steam, bismuthyl chloride is left as a residue. 8
(2) It is formed in small quantities when bismuth trichloride is sublimed
in air. 9 (3) It is the stable compound always produced by the action
of water, sulphur dioxide, chromyl chloride, nitrogen peroxide and
1 Weinland, Alber and Schu'eiirer, Arch. Pharni-., 10.16, 254, 521.
~ Persoz, Ann. Clnui. Pkyx., 1830, 44, 315.
3 Delicrain, Coai.pl. rend., 1802, 54, 724. Sec also Arppe, Poyy. A-niudc,ii, 1845, 64,
237.
* Vanino and Mauser, Bar., 1900, 33, 2271, 1901, 34, 416; 1902, 35, 663; 1903, 36,
3082; Montoraartini, (tazzctta, 1900, 30, 11, 493; Schiff, .Her., 1901, 34, 804; Vanino and
Hartl, Arch. Phann., 1907, 244, 216; Pasturcau, Compt. re/id., 1898, 127, 485; Pfeiiier,
Zeitficfi. anorrj. Chem., 1900, 24, 279; Smith, Her., 1879, 12, 1421.
5 Muir, J. Chew. Soc., 1876, 29, 140. See also Hutch ins and Lcnker, J. Amer. Chem.
Sue., 1907, 29, 31.
'' Domeyko, Compt. r(.n.d., 1870, 82, 922.
7 Phillips, Phil. Mag. and Annals, 1S30, 8, 456; Heintz, Pogy. AnnaU,i, 1844, 63,
72; Arppc, -/62V/., 18-15, 64, 240; Kosc, ibid., 1800, no, 425; Huge, J. pra/d. Chem., 1865,
96, 133.
8 Jacquelain, Ann. Phys. Cfiem., 1837, [2], 66, 113.
9 Jacquelain, Zoc. oil.
168 ANTIMONY AND BISMUTH.
other oxidising agents upon bismuth trichloride. 1 (!) It is Formed by
the action of dilute hydrochloric acid on bismuth trioxide ; thus
Bi 2 O 3 +2HC1 =2BiOCl +H 2 O
Colourless tetragonal crystals may be obtained by a suitable modi-
fication of this method.* (5) When bismuth sulphate is heated with
sodium chloride and the mixture treated with water, bismuthyl chloride
remains undissolved. 3
Eismuthyl chloride is a white, crystalline powder. 4 On heating,
the colour changes to yellow, and in parts brown, this disappearing
only partially on cooling ; the colour change thus appears to be
partly physical and partly chemical. The compound also darkens on
exposure to light. 5 The crystals belong to the tetragonal system, have
a density G of 7-717 at 15 C. and a molecular volume of 33-7 ; the density
of the precipitated form 7 is 7-2 at 20 C. Melting occurs at red heat
\vithout decomposition, and on solidifying a pale yellow, crystalline
mass is formed. Prolonged heating at a high temperature causes slight
volatilisation, possibly of bismuth trichloride, 8 although it is also sug-
gested that true sublimation occurs to a slight degree. 9 The oxychloride
is almost insoluble in water 10 and in liquid ammonia. 11 It dissolves
readily in both hydrochloric and sulphuric acids, with the formation
of the trichloride and sulphate respectively ; it also dissolves in nitric
acid on heating, and from this solution it is re-deposited by evaporation.
It reacts with alkalis, especially when the solutions are concentrated. 12
It. is probable that with a dilute solution of potassium hydroxide a
reversible reaction takes place according to the equation
BiOC'l + KOH =^= BiO.OH -f KC1
Wit h concentrated solutions the action is much more complex. 13 When
heated with mercuric, oxide it is partially converted to bismuth trioxide. 14
It is reduced to metal by fusion with potassium cyanide, and also by
hcnlino- in n current of hydrogen; in the latter case some trichloride
volatilises. I5
Two hydrates have been reported: the monohydrate^ BiOCl.JI 2 0,
and the trihydrdtc, Hi()('1.3lI 2 O, both of which have been stated to
become anhydrous at 100 C.; but from a study of the equilibrium of
the system Bi 2 O. r I IC1- II 2 it would appear that no hydrate of
bismnthyl chloride can exist at 25 C. ; the stable phase which sepa-
rates out from solutions containing 25 to 33-07 per cent. 1IC1 (up to the
1 Thomas, Ann. (!/tini. /'//?/*., 181)8, [7], 13, 1-15; Cow pi. raid., 1890, 122, (51 J.
" Muir, ./. Chan. Nor-., ISs'l, 39, 30; do Schulten, Hull. Hoc. chi/n., 1900, |3J, 23, 1.50.
' Lrba'i'.'tir, -/. riiann. Chitn., 1801, |31, 39, 108.
; ilcnil'/, r</tj. Atinalcn, 1814, 63, 72; Rutft', / yrakl. Chan., 1 80;"), 96, 13;}.
; ' Her-/., /.i-ilxch. (i nary, (.-'hern., 1903, 36, 3-10.
() i!c Sclmlt on, lor. nf.
lir, -/. Chan. Hoc., 1881, 39, 37.
r_ic, lac. r//.; Arppo, loc. at.
r/., lac. al.
.sr, lac. at.
and Kraus, Anicr. (J/u-m. J., 1898, 20, 827.
in, lac. rit.; St,ronu\ver, Pi^/g. Annalai, 1832, 26, o-10; AVai'ington, Phil
K//.S 1831, 9, 30.
1 Muhs, Zcttach. finorg. Chew., 1901,39, 11").
id Hcyl, '/jcitxch. ananj. Chan., 1894, 7, 87.
>d(i. Airindai, 18(J(), HO, 4l ) .").
fidlai, 1844, 63, f)f).
COMPOUNDS OP BISMUTH. 160
point 33-7 per cent. HC], 58-7 per cent. Bi 2 O 3 , 7-G per cent. II 2 O) being
anhydrous bismuthyl chloride. 1 (See p. 16-1.) The solubility product
of the monohydrate 2 is, however, stated to be 1-58 x 10 3I .
The existence of other oxyehlorides to -which the formulae Bi 2 O 3 Cl 2 ,
Bi 3 2 Cl 3 and Bi 4 O 3 Cl 4 have been ascribed has been suggested from
time to time, but it has not been definitely established that these are
chemical entities. 3 A study of the hydrolytic dissociation of bismuth
trichloride indicates that only one oxychloride exists. 4
From the experimental result shown by the equation
BiCl 3 +Aq. > BiOCl -7830 gram-calories
the heat of formation of bismuthyl chloride is calculated to be 88,180
gram -calories. 5
Bismuth Chlorate. Bismuth chlorate does not appear to have
been isolated, for although bismuth hydroxide dissolves readily in
dilute chloric acid, the solution decomposes on concentration. 6 When
a hot aqueous solution of bismuth nitrate and sodium chlorate is cooled,
long, glistening prisms of bismuthyl chlorate, BiOClO 3 , separate.
This substance does not appear to react when warmed with either
carbon or a mixture of carbon and sulphur ; but it detonates on heating
with potassium cyanide. 7
Bismuth and Bismuthyl Perchlorates. Muir, in one of his
early investigations on bismuth compounds, claimed to have prepared
bismuthyl perchlorate, BiOClO 4 , by heating powdered bismuth in a
dilute solution of perchloric acid. 8 The solution of bismuth in per-
chloric acid is, however, accompanied by the reduction of the acid to
chloric, acid and the liberation of the explosive chlorine dioxide ; hence
the experiment can be carried out safely only by employing small
quantities of 40 per cent, acid and heating very carefully. A similar
product is obtained by dissolving bismuth oxide in the acid. The
normal perchlorate can also be obtained by careful employment of
the latter method. 9 In this way the pentahydratc, Bi(ClC) 4 ) 3 .5H 2 O,
has been obtained in the form of small, hexagonal plates, which are
extremely reactive to water, vieldino- a bismuthvl salt. An unstable
~ , . u '
irllujdrate of bismuthyl perchlorate, BiOClO 4 .'3rI O, is obtained by
evaporating a solution of bismuth oxide in a more dilute acid, or by
adding water to the normal salt and evaporating over calcium chloride ;
this passes readily into well-formed hygroscopic rhombohedra of the
nionokydrate, BiOClO 4 .H 2 O, which is the most stable body of this
scries. By careful drying at 80 to 100 C., the anhydrous perchlorate
is obtained as a white powder. All these oxychlorates are soluble in
water, yielding clear solutions, without appreciable hydrolysis. 10 A
1 \Vfiris, ,/. Indian C/i-cm. Soc., 1925, I, 307.
- Foilknecht, Ileh. Ckim. Ada, 1933, 16, 1302.
.lacqiiehun, loc. c.if.; .Dcherain, Bull. Soc. cJii'm., 1 8(>2, 4, 23; Muir, J. C/U-.KL. *S'oc.,
1877, 32, 133; 1878, 33, 11)3: 188], 39, 32; Merz and \Veith, Ihr., 1880, 13, 210; Thomas,
Co/apt, rc.nd., 189(), 122, 01.1.
4 Dubnsay, Cu-mpt. rent!..., 1909, 149, 122; Hcrz and Bulla, ZeittcJi. a/tory. CJiv/fi.,
1909, 61, 387^ '
:> Thomson, Ba\, 1883, 16, 39.
i; Wachicr, A-nnah-n, 1.S44, 52, 233.
7 Vjmino and Mussgnug, Jlcr., 19.1.7, 50, 323.
J .Muir, Chc,m. Tev6\v, 187(5, 33, 15.
'' J ; icluor and Jenny, Hc-.h. Chim. Ada, 1923, 6, 225.
170 ANTIMONY AND BISMUTH.
basic per chlorate, whose composition approximates to the formula
BiOH.ClO 4 .H 2 O, lias been obtained by saturating concentrated
perchloric acid with bismuth trioxide. 1
Conductivity measurements on solutions of bismuth perchlorate
indicate that a very soluble basic salt, Bi(OH) 2 .ClO 4 , is stable even in
the presence of a moderate excess of perchloric acid, and that it is
converted into less basic salts such as Bi(OH)(C10 4 ) 2 or Bi(C10 4 ) 3 only
slowly on addition of excess of acid. The first compound has the
conductivity of a non-hydrolysed univalent salt 2 (see p. 146).
Bismuth Thiochloride, BiSCl, was first obtained by Schneider by
heating bismuth ammonium chloride either with sulphur or in a current
of hydrogen sulphide. 3 It has also been obtained by heating bismuth
trichloride with sulphur, 4 by the action of hydrogen sulphide on
bismuth trichloride at the ordinary temperature, or at temperatures
below red heat, 5
BiCl 3 + H 2 S = BiSCl + 2HC1
and by the action of chlorine on bismuth trisulphide at temperatures
below red heat : 6
Bi 2 S 3 + 6C1 = BiSCl +BiCl 3 +S 2 C1 2
The thiochloride crystallises in dark grey, metallic needles, which
appear ruby-coloured under the microscope. It is decomposed on
heating in air, bismuth trichloride and sulphur dioxide volatilising,
leaving a residue of oxychloride and basic sulphate ; on heating in. a
current of carbon dioxide, bismuth trichloride volatilises, leaving a
residue of bismuth trisulphide ; in a current of hydrogen, bismuth
trichloride, hydrogen chloride and hydrogen sulphide are volatilised,
leaving bismuth contaminated with a little chlorine and sulphur. By
strongly heating in a current of hydrogen sulphide it is converted into
bismuth trisulphide. It is not attacked by water or dilute mineral
acids, even on boiling ; but it is decomposed by concentrated acids,
hydrogen sulphide being liberated by hydrochloric acid, and sulphur
by nitric acid. Potassium hydroxide (and weaker bases more slowly),
decomposes it with liberation of chlorine.
Bismuth Selenochloride, BiSeCl, is obtained in the form of small,
dark grey, metallic needles by the action of bismuth selenidc on molten
ammonium bismuth chloride. 7 It is decomposed into bismuth tri-
chloride and bismuth selenide on heating in a current of carbon dioxide.
It is not attacked by water, and hardly at all by concentrated hydro-
chloric acid ; concentrated nitric acid decomposes it with liberation
of selenium. Chlorine is liberated by the action of potassium hydroxide,
and more slowly by weaker bases.
Bismuth and Bromine.
Bromine combines with bismuth less readily than does chlorine,
but if arsenic be present a reaction takes place at the ordinary tem-
perature. 8
1 Eichter and Jenny, loc. cit. 2 Smith, loc. cit.
3 Schneider, Pogg. Annalen, 1854, 93, 464; Ami. Phys. Chem., 1854, 93, 64.
4 Muir, J. Chew,. Soc., 1877, 32, 177.
5 Muir and Eagles, J. Chem. Soc., .1895, 67, 92. See also Schneider, loc. cit.
6 Muir and Eagles, loc. cit. 7 Schneider, Pogg. Annalen, 1855, 94, 628.
8 Serullas, Ann. CMm. Phys., 1828, [2], 38, 318.
COMPOUNDS OF BISMUTH.
171
Bismuth Dibromide, BiBr 2 . The evidence for the existence of
this compound is as unsatisfactory as that for the existence of the
corresponding chlorine compound. Similar methods have been sug-
gested for its preparation, and it is stated to be a brown, or grey,
substance, crystallising in needles. 1 Muir thought it probable that "a
lower bromide was formed by the reduction of the tribromide by
hydrogen, but was unable to isolate the substance owing to its in-
stability. 2 Attempts to elucidate this problem by means of thermal
investigation have also been undertaken. 3 Herz and Guttmaim state
that the dibromide is a gre}-ish-black substance with a density of 5-9
and a melting point of 198 C. ; while Marino and Beearelli contend
ouu
V 285
\ '
nc-i
\X^^
j \
o rr>
i i \
^
zou
-
y\
5
^
^
>^
-2/8C.
inn
*
ZUU
r cr\
-
205C.
\
/OU
inn
-
JOO SO 80 70 60 50 40 30 20
Bismuth, Atoms per cent.
10
FTC. 6. Freezing Point Curve of the System Bismuth-Bromine.
that no compound is formed in the system Bi-BiBr ;J , but a series of
solid solutions only. The latter investigators find the system similar
to that of Bi-BiCLj, the solid solution undergoing transformation into
first a /3-lbrm and then a y-form, the melting point of the y-form always
being higher than that of cither bismuth or bismuth tribromide. On
fusion and cooling, the y-crystals decompose and deposit a-crystals of
different composition, and two liquid layers are formed.
Bismuth Tribromide, BiBr 3 , is the only compound of bismuth and
bromine indicated on the freezing point curve (fig. 6). 4 It may be
obtained by the direct union of the two elements, an excess of bromine
being employed. 5 A variety of methods has been used by different
investigators, the following being some of the more important. Bis-
muth is heated in bromine vapour ; G the two elements are heated
1 AVebor, Pof/g. AnnaUn, 1S59, 107, 599, 600.
- Muir, J. C'hem. Soc., 1876, 29, 145; 1SS1, 39, S3.
:i E^-ink, Zeit.sc/i. -plujtikal. Chan, 1908, 64, 449; Herz and Guttmann, Zeitsch.
nnorg. Chem., 1908, 56, 422; Marino and Beearelli, Aiii R. Accad. Lincei, 1915, [v], 24, li,
025; 191.6, [v], 25, i, 105.
- 1 International Critical Table*, 192S, 4, 23.
; ' Serullas, Ann. Chim,. Phys., 1.828, [2], 38, 323; Pocjg. Annalen, 1828, 14, 113.
G Ar,,1w^,. & A.:->.-., f ,lr..:-> IC'.-XO r/-.>7 /thn. AfniV njifl'm V/^y.c 1^7;"> ?? '277.
172 ANTIMONY AND BISMUTH.
together in a scaled tube ; l powdered bismuth is added to bromine
and the mixture allowed to stand for several days, then being distilled
and the tribromide purified by repeated distillation ; 2 or bromine may
be dissolved in an organic solvent, such as ether, powdered bismuth
added, the mixture filtered after standing for a time, and the solution
evaporated in vacuo*
Bismuth tribromide may also be obtained from bismuth trioxide or
bismuth trisulphide by heating in bromine vapour. In the former case
some oxybromide is also formed, and in the latter some thiobromide. 4
Bismuth tribromide, by slow distillation, can be obtained in the form
of large, flat, golden-yellow crystals. 5 Its density is 5-604 at 20 C.,
and its molecular volume at 273 C. (calculated from the density at
- 194 C. and the coefficient of expansion) 6 is 77-0. It melts at 218 C.,
forming a red liquid : the density of the liquid 7 between 272 and 330 C.
is given by the expression
i)\ = 5-248 -0-002C*
The surface tensions, together with other data for the density, 8 at various
temperatures, are as follows :
Temperature, C. . 250 281 299 320 346 ,370 389 417 442
Density, D^ . . 4-598 4-525 4-471 4-416 4-348 4-286 4-237 4- 104 4-099
Surface Tension
(dynes per cm.) . 66-5 63-6 Cl-6 59-5 56-7 53-8 52-0 48-9 46-2
The boiling point 9 lies between 454 and 498 C., or 278 C. under a
pressure of 11 mm. mercury ; 10 the vapour is deep red in colour.
Bismuth tribromide is not soluble in water but is decomposed by it.
It is soluble in both hydrochloric and hydrobromic acids, but it is
decomposed by nitric acid. It will also dissolve in alcohol, ether, and
to a certain extent in some hydrocarbons, but it is almost insoluble in
most other organic solvents. 11 It is also said to dissolve in heated
arsenic tribromide 12 and in certain fused metallic halidcs. 13
It sublimes in air almost without change, there remaining only a
small non-volatile residue, probably of bismuthyl bromide. 14 It absorbs
moisture from the air, and is decomposed by excess of water (brining
3 Maclvor, Cham. Newa, 1874, 30, J \)(l
~ Clever, AnnaUn, 1891, 264, 122.
:! Xickles, Compt. rend., 1855, 48, 837: ./. prakt. Chan., 1859, 79, 14.
3 Muir, Hoft'meistcr and Kobbs, J. C/n-ni. >SV>r... 1881, 39, 21; Jannarch, Jlcr., 1891, 24,
3746; Zedwk. anory. Chcm., 1895, 9, 194.
5 Muir, /. Chew. Soc., 1876, 29, 145.
J Biltz, Sapper and Wimnenbcnr, Zc/l-^cJ/. n<>Kj. Chf-.t/i., 1932, 203, 277.
7 Jiiicrnational Critical Table.*, 1928, 3, 23.
8 I'ntt-.r national Critical Tahlf.^ 1928, 4, 424; Jao-er and Kalin, Proc. K. A lead.
We1.e>ix<:h. Amsterdam, 1916, 19, 397; .Jtie^cr, Zcil^c/t,. awmj. Ckc.in., 1917, 101, 16.
>J Carnelley and \\'illia,rns, J. Chcm. ,S'oc., 1.878, 33, 283. See also Evnevitsch and
Suehodski, /." Ihtxs. Phys. Ckt.-nt. .SW 1 ., 1929, 61, 1503; Mover and Krause, Annali-.n,
1891, 264, 124.
11(1 Ansclititz and AVeyer, Aunah-n- y 1891, 261, 297.
n Cavazzi and Tivofi, GazztUu, .1891, 21, n, 300; Xicklcs, loc. cit.
'- .Retgers, Zei/.sch. phytikuL Che.ni., 1893, n, 340.
13 Isbekov, Zeitsch. phyHtkaL Chew., 1925, 116, 304; Zeiltich. anon/. Chf-.rn., 1930, 185,
324.
14 Thomas, Cutnpt. rend., 1896, 122, 1060; Muir, J. Chtm. tioc., 1876, 30, 12; 1877,
32, 137.
COMPOUNDS OF BISMUTH. 173
bismuthyl bromide. Variation of temperature appears to have but
little effect upon the hydrolysis of bismuth tribromide, and only one
oxy bromide is produced. 1
Nitrogen tetroxide reacts even at the ordinary temperature, pro-
ducing bismuth oxybromide. 2 The tribromide forms a number of
ammoniates, among them being an olive-green compound, BiBr 3 .
2NH 3 , and a light, straw-coloured, amorphous powder, BiBr 3 .3NH 3 ,
both of which are decomposed by water, probably with formation of
oxybromide. A third compound, 2BiBr 3 .5NH 3 , is said to be formed as
a greyish-green sublimate by the action of dry ammonia upon heated
bismuth oxybromide ; it is not deliquescent, nor is it decomposed by
water. All these compounds react readily with hydrochloric acid,
forming double salts of bismuth bromide and ammonium chloride :
BiBr 3 .2NH 4 C1.3H 2 0, BiBr 3 .3NH 4 Cl.H 2 O, and 2BiBr 3 .5XH 4 Cl.H 2 O.
In addition, an ash-grey, crystalline substance has been obtained which
is stated to have the composition BiN 2 Br. 3
When an ether solution of bismuth tribromide is gradually added to
dry phosphine, a lustrous, black substance is formed which probablv
has the composition PBrH(BiBr 2 ) 3 or 2BiBr 3 .HBr.BiP :
8BiBr 3 4-PH 3 =2HBr+PBrH(BiBr 2 ) 3
It is hygroscopic, and is decomposed by water with liberation of bismuth
and formation of phosphine, hydrobromic and phosphoric acids. It is
decomposed by a solution of potassium hydroxide with evolution of
hydrogen, and phosphine, and formation of potassium bromide and
phosphate. Concentrated sulphuric acid attacks it only when heated,
but concentrated nitric acid acts upon it very violently. It decomposes
with violence when heated in air, yielding bromine, bismuth bromide
and phosphorus pentoxidc, but is stable when heated to 220 C. in a
current of carbon dioxide. 4
Bismuth tribromide docs not react readily with sulphur ; on heating,
only a small quantity of thiobromide, BiSBr, is obtained. 5 It reacts
with hydrogen sulphide at the ordinary temperature ; at moderate
temperatures bismuth thiobromide, BiSBr, and at higher temperatures
bismuth trisulpbide, Bi 2 S 3 , is formed. 6 The tribromide is not altered
by heating with sulphur dioxide.
The decomposition potential of bismuth tribromide in solution in
fused zinc chloride 7 is 0-40 volt. This places bismuth below mercury
in the electrochemical scries.
Double and Complex Salts. If a saturated solution of bismuth
tribromide in concentrated hydrobromic acid is cooled to -10 C., a
complex substance of an acidic nature separates out as yellow needles.
Its composition is BiBr 3 .2lIBr.4H 2 O or H 2 BiBr 5; 4H 2 O. "it is extremely
deliquescent and unstable, losing hydrogen bromide when exposed to air. 8
1 Dubnsay, Compt. n-.ud., 1000, 149, l'2'2; Kcrz and Bulla, Z<dt#ch. a-nory. Chcm.,
1909, 61, :>87~ 1000,63,59.
2 -
is, oc. c-t
J . (,'!LCIH. Sac , 187<i, 29, -IS; 1870, 30, 14; 1877, 31, 27. See also Field,
'-' 4
3 .Mm , J. ('kcin. #oc , 1870, 29, -18; 1870, 30, 14;
Clx-in. S'or., 1803, 63, 547; Ch< -m. 'S(-wx, 1803, 67, 157.
- 1 C'av 77.1 and Tivoli, (IttzzHl'i, 1801, 21, ii, 30(5.
r> Mm , HofhiKMsic-r and Kohbs, ,/. ('Hon. X<,c . JSSI, 39, 35.
' Mm and Katies, Chrtti. AV-?/:x, IS05, 71, 35.
' Isl)ekov, Z,(:\isc.h. a iiorti. CJn-ni., 1030, 185, 324-.
174 ANTIMONY AND BISMUTH.
Two organic compounds l have also been obtained, with the com-
positions H 2 BiBr 5 .4O(C 2 H 5 ) 2 and II 2 BiBr 5 .10O(C 2 H 5 ) 2 ; both are
hygroscopic and -unstable. The alkali .salts, Li 2 BiBr 5 , Na 2 BiBr 5 and
K BiBr 5 , and the thallium salt, Tl 2 BiBr 5 (the latter forming lemon-
yellow crystalline plates ), 2 have been isolated. In addition, the ammonium
salt, (NH 4 ) 2 BiBr 5 .2H 2 O, has been obtained by heating bismuth bromide
and ammonium bromide with alcohol and a little ammonium acetate in
a sealed tube ; 3 it is a greenish-yellow, transparent substance, crystallis-
ing in the rhombic system and isomorphous with the corresponding
chloride and with the double chloride of potassium and bismuth. It
loses combined water completely when heated to 100 C. ; it is dis-
sociated when, strongly heated, and is decomposed by water forming
bismuthyl bromide. Several mixed halides of similar composition have
also been, reported, among them being K BiClBr 4 , 4 K 2 BiCl 3 Br 2 , 5
K 2 BiCl 4 Br, 6 and (NH 4 ) 2 Bi(Cl, Br) 3 Br 2 . 7 Evidence for the existence
of a complex of the type H 2 BiBr 5 is also obtained from a study of the
absorption spectrum of a solution of bismuth tribromide in hydrobromic
acid. 8
An ammonium compound, NH 4 BiBr 4 .H 2 O, which corresponds to
the hypothetical complex acid HBiBr 4 , has also been obtained by the
action of bromine on bismuth in alcohol in the presence of ammonium
bromide. 9 It forms yellow, needle-like crystals of the rhombic system,
soluble in alcohol, but decomposed by water. From thermal analysis
there is evidence for the existence of the aluminium compound 10 AlBiBr 6 ,
but this substance does not appear to have been isolated. A very
complex triple salt, Rb 5 Au 2 BiBr 14 or 5llbBr.2AuBr 3 .BiBr a , has been
prepared, 11 in which the gold is present in the tervalent form. It is a
black substance, soluble in hydrobromic acid. It is also possible that
complex compounds of bismuth and bromine of the type K 2 Bi 3 Br n ,
etc., similar to the corresponding compounds of antimony (see p. 77)
may exist, but they have not yet been isolated. 12
Bismuth Oxybromide, or Bismuthyl Bromide, BiOBr, can be
obtained bv the action of water on a solution of bismuth tribromide in
hvdrobromic acid ; it is also believed to be formed by heating together
bismuth tribromide and bismuth trioxide. 13 By a suitable modification
of the former method, the crystalline oxybromide may be obtained. 34
The precipitated substance is obtained as a snow-white, amorphous
powder of density (at 20 C.) 15 6-7. The crystalline form is colourless
and transparent, density (at 15 C.) 8-082. It melts at a bright red
heat, at which temperature bismuth tribromide volatilises ; it darkens
1 Schafer and Hdn, Zt-ilsch. annrg. Cham., 1917, 100, 249.
- Canncri and Perina, Oazzctta, 1922, 52, I, 23J.
3 Xicklcs, J. PJm.rm. Chnu., .1861, [3], 39, 118; Groth, C/icni. K-rysL, 1906, J, 431.
4 Field, J. Chem. Soc., 1893, 63, 546.
-> Atkinson, J. Chew. Soc., J883, 43, 292.
r> Field, Inc. cit.
7 .Vickies, J. Phunn. Chim., 1861, [3], 40, 191.
8 Schafer and Hem, Inc. cit.
' Xickles, Cmn.pt.. rend., I860, 51, 1097.
COMPOUNDS OF BISMUTH. 175
on exposure to light ; x it is insoluble in water, but dissolves in moder-
ately dilute hydrobromic acid ; it is decomposed by potassium hydroxide
as follows : 2
BiOBr + KOH ^ BiO.OH + KBr
Two other oxy bromides have been reported, namely, Bi 8 15 Br 6
and Bi n 13 Br 7 (or 7BiOBr.2Bi 2 O 3 ), but their identities have not been
confirmed. 3
Bismuth oxybromides are partially reduced to metal when heated to
a dull red heat in a current of dry ammonia (see also p. 173).
A basic salt, bismuth oxybromate, or bismuthyl bromate, BiOBrO 3 ,
has been obtained (mixed with some bismuthyl hydroxide, BiO.OH)
by the prolonged action of an aqueous solution of bromic acid upon
bismuth hydroxide. The mixture is a white, amorphous, insoluble
powder which loses water between 150 and 200 C. and decomposes
violently when strongly heated, leaving a residue of bismuth oxy-
bromide. At the same time there is formed a soluble product, the
solution, of which decomposes on evaporation, with evolution of bromine,
while the small amount of residue which is obtained decomposes at
once in the air. 4
Bismuth Thiobromide, BiSBr, has been obtained by heating
together a mixture of bismuth tribromide and sulphur. 5 It may be
obtained more readily by the action of hydrogen sulphide on bismuth
tribromide, or by the action of bromine upon dried, precipitated
bismuth trisulphide. In each case the action must be carefully
regulated. The former reaction, when carried out at temperatures up
to a very low red heat, may be represented by the equation G
BiBr 3 +H 2 S = BiSBr +2HBr
while at full red heat the following occurs :
2BiBr 3 +3H 2 S =Bi 2 S 3 +6HBr
The second reaction is carried out at a low red heat, and may be
represented by the equation
Bi 2 S 3 + 2Br 2 = BiSBr + BiBr 3 + 2S
Bismuth and Iodine.
Bismuth Diiodide. As with other bivalent compounds of
bismuth, the question of the diiodidc has given rise to much dis-
cussion. An early attempt was made to prepare this substance by
melting together bismuth triiodide and bismuth, but the results were
inconclusive. 7 Later, the thermal investigation of the system bismuth
triiodide-bismuth appeared to afford evidence of the existence of the
compound BiI 2 , which crystallised with metallic lustre, had a density
1 Her/, ZritM'h. anon/. CJu-.m., 1003, 36, 3-46.
- Herz and Mulis, Zfiil^c.h. (cu.org. C/KML, 1904, 39, 115.
3 .Muir, ./. Chun. >S'oc., 1.87(5, 30/12; 1877, 31, 27; 1877,32,137; 1881,39,22. Soe also
Thomas,, CompL rtnd., 180(5, 122, 1060.
' Rammclsberg, Pocjg. An-nahn, 1842, 55, 70.
5 Muir, Hoft'meister and Robbs, /. Che-m. Soc., 1881, 39, 33.
6 Muir and Eagles, J. Chem. Soc., 1895, 67, 90.
7 \Veber, Pogg~ Annalen, 1859, 107, 601.
176
AXTIMOXY AND BISMUTH.
of 6-5, and decomposed below its melting point. 1 A study of the
system bismuth-iodine (fig. 7) by thermal analysis, however, failed to
yield evidence for any compound other than the triiodide. 2 More
recently, a similar investigation, while providing no evidence of the
existence of bismuth diiodide, indicated a reaction at 281 C. which
400
700
10 20 30 40 50 60 70 80 30 700
Atoms per cerrtjodine.
Fie. 7. Freezing Point Curve of the System Bismuth-Iodine.
was attributed to the formation of a compound, Bil, from bismuth
triiodide and liquid. 3
Bismuth diioclide is said to be obtained by distilling methyl iodide
through bismuth monoxide/ 1 The monoxide is prepared by the method
of Tanatar (see p. 183 ), 5 and the distillation is carried out in stages, at
a maximum temperature of 202 C., the monoxide being maintained at
the same maximum temperature at each stage ; between each stage
the apparatus is cooled down to the ordinary temperature. 6 Three
products are obtained :
(1) A non-volatile, brick-red homogeneous powder which remains
in the reaction vessel. This substance, bismuth suboxyiodide,
"Her/ and Guttmann, Zc.i.ftch. a/iorg. C'hc;n}., 1008, 56, 422.
- Marino and Beearelli, Atli R. Acc.ad. Lniri-l, 1912, [vj, 21, (>!).">.
:i van Klooslor, Zcikc/i. (mmy. Chun., 1913, 80, KM.
' Den ham, J. Ant.fr. Chf-m. Soc., 1921. 43, 2307.
COMPOUNDS OF BISMUTH. 177
2BiI 2 .3BiO, is stable in air, non- volatile at 300 C. but decomposed
above 350 C. probably into bismuth and bismuth oxyiodide. A
saturated aqueous solution of this substance, after filtration, reacts
only very faintly with both hydrogen sulphide and silver nitrate, but
the substance is decomposed into bismuth and the tervalent salt by
sulphuric acid, acetic acid, hydrochloric acid and sodium hydroxide.
It is insoluble both in alcohol and in an aqueous solution of potassium
iodide. It is a reducing- agent, reducing an acid solution of potassium
permanganate. The identity of this compound and its distinction
from bismuth oxyiodide. BiOI, have been confirmed by comparing the
conductivities of its solutions with those of the oxyiodide ; the resistance
of the latter was 745 15 ohms and that of the former 9000 + 900 ohms.
(2) A red, volatile product which condenses in the cool part of the
apparatus. It is claimed that this substance is bismuth diiodide, BiI 2 .
It crystallises in bright red, long needles, of the rhombic system. Its
solution in water, free from oxygen, yields much stronger reactions for
bismuth ion and iodide ion than the afore-mentioned suboxyiodide.
In the absence of oxygen it dissolves in alcohol and in methyl iodide,
forming in both cases a clear yellow liquid ; it dissolves readily in an
aqueous solution of potassium iodide. It is a reducing agent, rapidly
reducing a solution of iodine, and an acid solution of potassium per-
manganate : it decomposes above 400 C. into bismuth triiodide, which
volatilises, leaving a residue of bismuth.
(3) The distillate, a pale yellow liquid, is considered to contain a
mixture of bismuth diiodide and bismuth dimethyl, Bi(CH 3 ) 2 ; the
evidence for this is inconclusive, but the distillate oxidises readily,
producing a strongly reducing substance which is thought to be di-
mcthoxybismuth, Bi"(OCH : j) 2 /"
In connection with this preparation, hoAvcver, it must be remembered
that the evidence for the existence of bismuth monoxide itself has been
criticised. 1
X-ray examination has failed to reveal the existence of a lower
iodide than bismuth triiodide. 2 This evidence is, however, not
conclusive.
Bismuth Triiodide, Bil :j . was probably first prepared by Berthcmot
by synthesis Irom the elements ; 3 this synthesis has since been
effected in a variety of ways. 4 Owing to the small reactivity of the
elements, however, combination is effected only with difficulty. The
iodide may be purified by sublimation in a slow current of hydrogen.
It may also be obtained by precipitation from a solution of a bismuth
salt in acetic acid with potassium iodide, 3 by the action of concentrated
hydriodic acid on bismuth ti'ioxide at the ordinary temperature, 6 or
on bismuth oxychloridc, 7
3BiO( 1 -f GUI = 2BiI 3 -Bid, + 3II.O
1 Xctissor, Z'-lltrli. aiiory Chcin., 1924, 135, 31 3 ; 1924, 138, 180.
- Caiiiioti, (,'azzcUa, 1930, 60, 933.
:! Berthemot, -/. J'ti.rtnii.., 1828, 14, GIG.
' Kanimelsberu, /V/f/- A n.nalt.n, 1839, 48, 100; lleintz, ihltL, 18-1-1, 63, 7;~; We
ilml., 18.~>9, 107, GOO; Xirkles, Cum./jf. rend., 1800,50,872; Muir, I loll'moist'or and Ro
J. <}><,. &o<:., 1881, 39, 33; Schneider, J. /,,-ftkt. Chr.ni., 189-1, J2], 50, 403.
178 AXTB10XY AND BISMUTH.
or by the action of hydrochloric acid on bismuth oxyiodide, 1
4BiOI + 9HC1 = BiI 3 + 3BiCl 3 + HI + 4H 2 O
or
SBiOI -f 6HC1 = BiI 3 + 2BiCl 3 + 3H 2 O
When a mixture of bismuth trisulphide and iodine is heated, bismuth
triiodide sublimes, leaving a residue of bismuth thioioclide ; 2 according
to another authority, bismuth triiodide and sulphur only are produced 3
in accordance with the reaction
Bi 2 S 3 -f6l=2BiI 3 +3S
Bismuth triiodide is also formed by the action of ethyl iodide on bismuth
trichloride in the presence of ethyl chloride. 4
Crystalline bismuth triiodide may be obtained by saturating a
solution of Bettendorff s reagent (a solution, of stannous chloride in
hydrochloric acid) with iodine and adding a solution of bismuth trioxide
or bismuth oxychloride in hydrochloric acid. 5 The size of the crystals
depends on the concentration of the solution ; they can be purified by
drying and heating carefully in an evacuated tube to below the melting
point, finally subliming in carbon dioxide or hydrogen.
Bismuth triiodide crystallises in the hexagonal system :
a= 7-498 A., c- 20-676 A.
The unit cell contains six molecules. 6 Its colour is variously described
as dark green, black and grey-black ; in the powdered form it is dark
brown. Its density, 7 D\ , is 5-7, and the molecular volume at
-273 C., calculated from the density at -191 C. and the coefficient
of expansion. 8 is 08-6. Its melting point is 410 to 439 C.
It volatilises at slightly higher temperatures, forming a red-brown
vapour. It sublimes unchanged when, heated in an atmosphere of
carbon dioxide or hydrogen, but evidence of thermal dissociation has
been obtained spcctroseopically. 10
It is stable in air, but volatilises with partial decomposition when
healed in air, leaving a, non-volatile residue of oxyiodide or trioxide. 11
It is not hygroscopic, but is decomposed by water.
It is soluble in hydrochloric acid and in hydriodic acid, slightly
soluble in absolute alcohol, and more soluble in benzene, toluene and
xylenc. It is a.lso soluble in arsenic tribronmlo. 32 The solubility in
organic solvents is greatly increased by the presence of arsenic tri-
1 Muir, ./. C/inn. /SV>r., JS78, 33, 2()J ; Muir, HofYmeistor and Robbs, lor. cil.
- Schneider, Pof/r/. Aiinnh-n, .1854, 93, 04; 1850, 99, 470: 1800, no, 147.
:! Muir and 'ivujes, J . Chr.m. ,S'or., .1895, 67, 92.
1 Aimer, (-fi-ttipf. rend., 1904, 139, 071.
: ' Birrkenbaeh, 7>Yr., 190", 40, 1404.
(; Brarkken, /jc-itxch. A'r
Helpers, Keltic h. (niofj. Ch< it
1800, 79, 421.
s Bill/,, Sapper and AVun
'' I ulcj national Critical 7
, 40, 1404.
sV., 19:^0, 74, 07. See also Linck, />Y/-., 1907, 40, 1105;
., 189;>. 3, :^45; Xiekles, lor. r//.; Schneider, ,/. praht. Chan..,
7 InliTnationaL Crihral 'Tahlf.^ 1920, I, 111.
//;//'.v, 1920, I, 111; Carnelley and \VilIiams, ./. Cf,<w. .S'or.,
;so, 37, 125.
111 Neuiniin, l^njxihil. Zcitxc.h. frnrji-.l-muon, 1932, 2, ^22.
11 'I'lionias, Conipt. rend., 180(5, 123, .1000; Muir, Iloflmeisler and I\obbs, Inc. r/i.
12 I^ei^ers, Zf:if*r/ t .. (rno></. Chan., 180,'i, 3, :M5; Zct'twh. phyxihtl. 67/r-///., .1.893, n, 3-10.
3:5 Niekles. /or. at,
COMPOUNDS OF BISMUTH. 179
Bismuth triiodidc is hydrolysed slowly by cold water, slightly more
rapidly by hot water. 1 The rate of hydrolysis, however, at 25 C. and
at 50 C. is so slow that the conditions of equilibrium have not been
determined. 2 Two products of hydrolysis have been described : 3 a
black compound, which is formed when, water is first added to the
triiodide, and a brick-red substance which is obtained when the con-
centration of bismuth in the liquid phase falls below 0-002 gram-atom
per litre and which has the composition of bismuth oxyiodide, BiOI.
The black substance has not been obtained pure, but analysis indicates
a composition corresponding to Bi 2 3 .5HI or 2BiOI.3HI.H 2 O.
Bismuth triiodide does not appear to react with hydrogen sulphide
when heated in a current of that gas. 4
When the triiodide is heated with dry ammonia, a brick-red com-
pound, BiI 3 .3NH 3 , is formed. This substance is decomposed by water
with the separation of ammonium iodide. 5
Bismuth triiodide is decomposed by nitric acid, with the liberation
of iodine. Muir stated that it reacted on heating with nitrogen peroxide
and was partially converted into oxyiodide ; this action was, however,
much less complete than the corresponding reaction with either bismuth
trichloride or tribromide. It has since been shown that at the ordinary
temperature the triiodide is converted to trioxide by reaction with
nitrogen peroxide, no oxyiodide being formed unless air is present. 6
By reaction with caustic alkalis (and less readily with alkali car-
bonates) it is converted to trioxide, admixed with a little bismuth
iodate. The reaction proceeds by stages. Taking the action of a
solution of potassium hydroxide as typical, when the concentration of
the alkali is less than 0-375 mole per litre the main product is the oxy-
iodide, BiOI. When the concentration is greater than this, this oxy-
iodide by a further reaction is transformed into the white compound
BiOI.2Bi 2 O 3 ; with excess of alkali the main product is bismuth trioxide. 7
The triiodidc reacts with alkali sulphides to form bismuth trisulphidc.
When heated with excess of mercuric oxide, or of mercuric sulphide, it
is converted to the trioxide or the trisulphidc, respectively.
The molecular weight of bismuth triiodide, 8 as determined from a
solution in fenehonc, is in accordance with the formula BiI 3 .
The triiodidc resembles the trichloride and the tribromide in
Conning a number oC complex compounds and double salts. An
iodobismuthous acid, HBiI 4 .#H 2 or BiI 3 .HI.#H 2 O (where x = 3 or I),
is reported to have been obtained in the form of rhombic, pyramidal
crystals from a solution of the triiodide in concentrated hydriodic acid
by evaporation over sulphuric acid. This dissolves in a solution of
potassium iodide, but is decomposed by water forming bismuth
oxyiodide.
An examination of cercbrospinal fluid and brain containing bismuth
1 Corf, and M'uir, loc. rif.
~ Her/, and Hulla, Zc-itxrh. (tnory. Ch<w., .1909, 61, 387; 63, 59.
3 Dnbrisav, Co-nipt, mid.. 1909^ 149, 451.
- 1 Muir and Hades, ,/. Chon.. &oc., 1895, 67, 90.
5 Ramme'lsbora-, /V/f/. A n.)i!r-n, 1839,48, 168.
15 Thomas, CompL rr-'ud., I 890, 123, LOGO; Muiv, ,/. Chc-ui. fine., 187S, 33, 200; Kointz,
/'of/'/- A H in'ilr-t/ , 181-1, 63, 7f>.
' 7 Monti-anii', />'<///. ,SV>r. r// ////.., 193-1, ! .">], I, <.>!)2; Franvo-is and DcKvaulle, itid., 193:5,
L'-i'i. 53, no'-i.
8 Hi mini and OH van, Alii H. Acca<l. Linr,c,i, 1907, [5 1 , 16, I, GC5.
Arppc, Poyg. Annulen, 1845, 64, 250.
180 AXTIMOXY AND BISMUTH.
indicated that the bismuth was present in the anion. 1 From a study of
ionic migration in the compound Xa 2 BiI 5 it is found that the bismuth
occurs in the complex anion BiI 5 = . Compounds of the form RBiI 4
and R 3 BiI 6 , in which II represents an organic radical, have been
obtained. 2
Among inorganic complex or double salts which have been reported
are the following :
The sodium salt XaBiI 4 .H 2 O, prepared by the action of iodine on
bismuth in a saturated solution of sodium chloride ; it forms brownish-
black crystals belonging to the monoclinic system : 3 a : b : c =
0-864 : 1 : ' 0-717; /3=102 21'. Xa 2 BiI 5 .4H 2 0, prepared by the action
of anhydrous sodium iodide upon bismuth chloride in ethyl acetate; 4
it has a density of 3-33, melts at 93 to 94 C. and is soluble in water
and various organic solvents, but undergoes hydrolysis with excess of
the former solvent. Xa 3 Bi 2 I 9 .12H 2 O, which separates out from a
concentrated solution of sodium iodide saturated with bismuth tri-
iodide. 5
Xumerous potassium double salts have been reported, including 6
KI.2BiI 3 , KLBiI 3 .H 2 O, 2KI.BiI 3 , 2KLBiI 3 .4H O, SKI.BiL,
3KI.2BiI 3 .2H 2 O, 4KLBiI 3 , 4KI.BiI 3 .HI, 4KI.2BiI 3 and 6KI.2BiI 3 .
Investigation of the condition of equilibrium at 15, 35 and 55 C. within
the system BiI 3 -KI-H O revealed the existence 7 of two compounds
only,"KI.BiI 3 .H 2 O or KBiI 4 .H 2 O and 2KI.BiI 3 .H 2 or K 2 BiI 5 .H 2 0;
the former of these crystallises as bright red monoclinic prisms and the
latter as deep red flat quadratic prisms with pyramidal ends. Both
compounds can be dehydrated by treatment -in vacuo over sulphuric acid.
The c cesium salt,* Cs 3 Bi 2 I 9 , is prepared by the action of a solution
of bismuth hydroxide, bisrnuthyl carbonate or bismuth oxyiodide in
hydriodic acid upon caesium nitrate, or by the interaction of caesium
iodide with bismuth triiodide. It forms hexagonal crystals, hydrolyscd
slowly in cold water, rapidly in hot water. It is fairly stable when
heated and its use has been suggested for the quantitative determina-
tion of caesium.
Somewhat similar compounds of barium., calcium, 'magnesium,
beryllium and aluminium have also been reported. 9
Most of the foregoing compounds form red or dark red crystals:
they are all hydrolysed by water, yielding bismuthyl iodide. 10
Two ammonium compounds have also been obtained and examined.
The salt NII 4 BiI 4 .IIoO is obtained as a precipitate when iodine reacts
on bismuth in a concentrated aqueous solution of ammonium iodide;
1 Gure.hot, Ilanzlik and Spanieling, J. L'kuntutc.ul., .1032, 45, -\'21 .
2 Bartholomew and Burrows, ,/. l*rt,c. Roy. Xor.. .AY.?/; tiouth. ll'alw, 1020, 60, COS. For
other compounds with organic bases, see Kraut, Ann-dlcn, 1881, 210, 310; Jor^ensen,
Jahrcfibcr., 1869, 717.
:! .Xk'kles, J. rhnrw. Chltn.., 18(51, [",'}], 40. 321; Groth, Ckc.m. AY//.s7., 1006, I, 440.
1 Ourehot, Manxlik and Spauldin<r, loc. n'L See also Xieklos, ,/. Ph.ttn/i. Ckim., 18(51,
[.'*], 40, 324; 1802, [3,i, 41, 148; Cotnpt. rend., ISOO, 50, 872; DnurendorlT, Pkarin.
Zf-.i.t., IS(i(5, 5, 82: Astrc, C<rtii.-pt. rc.ruL, KS'JO. no, ")25, 1137; .Jurist and Christ kin.sen,
,/. A-nic.r. Phnnn. '-Hoc.. 1034, 23, If).
Arppe and Lma
Molard, ('ompt.
Meloche ami C
Art/i'llrii, 1S(>(), III, 2-11.
1034, 198, ():")"); AsLre, ihi<L, 180O, 110, ")2:")
"
Ainmh-n, 181."., 64, 2f)0.
Dolwauflo, Cnn,}t. rc.nd., 1034, 199, 1) IS
J. Am.w. (Jhcni. ^<>c,., 1030., 52,
Chem. J., J.S07, [4], 3, 40 1.
<J Welkow, Btr.y 1874, 7, 804. J0 See alyo Canncri and Tcrina, Cfazzctta, 1922, 52, 1, 231.
COMPOUNDS OF BISMUTH. 181
it may also be obtained by the action of iodine on bismuth in alcohol
in the presence of ammonium iodide. 1 It forms black, needle-shaped
crystals of the rhombic system. Another compound, (NH 4 ) 4 BiI 7 .3HO,
is obtained when a warm, concentrated solution of ammonium iodide is
saturated with bismuth triiodide. On evaporation, large, dark reddish-
brown, rectangular prismatic crystals separate. They appear to be
isomorphous with the corresponding double salt of antimony ; they are
hygroscopic and are decomposed by water. 2
A solution made by adding excess of a solution of potassium iodide
to a solution of bismuth nitrate is known as Dragendorff* s reagent. It
contains a complex iodide of bismuth and potassium and is used in
testing for alkaloids. 3
Complex compounds of bismuth iodide and organic bases have also
been described. 4
Bismuth Oxyiodide, or Rismuthyl Iodide, BiOI, is most readily
obtained by the hydrolysis of bismuth triiodide. Various other methods
for its preparation have been described, including the oxidation of
bismuth triiodide, the action of heat upon a mixture of bismuth triiodide
and bismuth trioxide, or the direct combination of those compounds
in a solution of potassium iodide at the ordinary temperature, 5 and
the distillation of methyl iodide through bismuth trioxide. 6
It is a red, crystalline powder ; the crystals are variously described
as brick-red, cubic microerystals, 7 or as copper-red, rhombic leaflets. 8
The density 9 at I5 C C. is 7-022.
The oxyiodide is stable in air, melting at red heat without decom-
position. When heated in the absence of air it sublimes with partial
decomposition, and when more strongly heated it is converted to
bismuth trioxicle. It is only slightly attacked by water, but readily
by dilute mineral acids with the formation of bismuth triiodide. It
dissolves in concentrated hydrochloric, acid, forming a yellow solution.
It is decomposed by both concentrated sulphuric acid and concentrated
nitric acid with evolution of iodine. It is not attacked to any appreci-
able extent by dilute alkaline solutions, even on warming ; but it is
converted to trioxide by the action of a concentrated solution of
potassium hydroxide. It is not attacked by a solution of potassium
chloride. It is completely converted into trisulphide by the action of
a mixture of potassium hydroxide and ammonium sulphide.
Various other oxyiodidcs have been reported from time to time,
but their existence lias not been confirmed (see also p. 1.70). 10
Bismuth lodate. Normal bismuth iodate, Bi(I0 3 ) 3 , can be obtained
as a white powder, insoluble in water and acetic acid, by treating a
solution of bismuth acetate with iodic acid; ll in the presence of acetic
acid the precipitation is quantitative.
1 Xickles, CumpL rcn'i., J 8(50, 51, 1097; J. PJiann. C/um., 18(51, [3], 40, 322.
- Linau, Poyrj. Annnltn., I860, III, 242.
3 UragcndortT, "Plaid Analysis'''' (London, 1884), p. 54; Mangini, Guzzctta, 1882, 12,
ir>r>; Thresh, Pfiarni. ,/., 1880, (3), 10, (54.1, 809; Yvon, ibid. y 187-jC [3J, 4, 1014.
- 1 VaTiino and Hauler, Bu\, 1902, 35, 663.
' Francois and Dehvaulle, Conipt. rc./id., 1933, 196, 1731.
6 Dcnham, J. A-mar. Cham. ,S'oc., 1921, 43, 2367.
7 Fischer, "JJie nr-.-ua/i A-rzntiirnLld" 1893, p. 25.
8 Schneider, J. prakl. Chun., I860, 79, 424.
182 AKTIMONY AXD BISMUTH.
When iodic acid and potassium iodate are added to a solution of
bismuth nitrate, a white precipitate is produced. 1 A white precipitate?
is also obtained by precipitating basic bismuth nitrate from a solution
of the normal salt and treating the filtrate from this with sodium iodate.
The white powder obtained can be dried at 100 C. and is stated to be
insoluble in both nitric acid and water. On heating it loses both oxygen
and iodine, leaving a residue which is probably bismuth oxyiodide. 2
Bismuth Thioiodide, BiSI, is obtained by dissolution of bismuth
trisulphide in molten bismuth triiodide, 3 by heating together bismuth
trisulphide and iodine, 4 by heating together bismuth trisulphide, iodine
and sulphur for a long time, 5 or by the action of thioacetic acid on
bismuth triiodide in the cold : 6
BiI 3 + CIIgCOSH + H 2 O - BiSI + CH 3 COOH + 2HI
It crystallises in small, steel-grey, metallic needles resembling bismuth
glance. It is decomposed on heating to the melting point into bismuth
trisulphide and triiodide. It is not acted upon by water or dilute
mineral acids even on boiling ; concentrated hydrochloric acid de-
composes it with evolution of hydrogen sulphide, concentrated nitric
acid with evolution of iodine and sulphur, iodine also being liberated
bv the action of warm potassium hydroxide (ammonia and other weak
bases act in a similar manner, but more slowly and less completely).
BISMUTH. AND OXYGEN.
Several oxides of bismuth have been, reported : they include,
bismuth monoxide, BiO, trioxide. Bi 2 3 , tetroxidc (or dioxide), Bi 2 O 4 ,
pentoxidc, Bi 2 O 5 , and hexoxicle, Bi 2 O G . The most stable of these is
the trioxide, which is mainly basic in its reactions, possessing only very
feeble acidic properties. Bismuth monoxide is stated to be weakly
basic, and halidc salts derived from this oxide have been reported
(pp. 158. 171, 175). The higher oxides are unstable and very slightly
acidic ; alkali bismuthates, derived from the pentoxidc, are however
more stable, and are employed as oxidising agents.
Bismuth Monoxide, BiO. Various methods for the preparation
of bismuth monoxide were described by early investjgators, who
frequently referred to it as a suboxidc, but in most eases the product
was cither impure or later proved to he a mixture of bismuth and its
trioxide. It is probable that the monoxide was first obtained in a
fairly pure condition by dissolving equivalent proportions of bismuth
trioxide and stannous chloride in hydrochloric acid, pouring the mixture
into a moderately concentrated solution of potassium hydroxide,
filtering and washing the precipitate with a cold solution of potassium
hydroxide. The product should be dried in a vacuum over sulphuric acid. 7
1 Pleisehl, Sch-wciyytr' fi J., 1838, 15, J.
- Rammelsberg, Poyy. An-nalc.-n, 1838, 44, 568.
a Schneider, Poyy. A-irnrtlun, i860, no, .1.47; J. -pnikt. Chcm., J860, 79, 422; Aluir and
Kagles, J. Chun, tioc., .1895, 67, 92. - 1 Schnejcler, he. at.
5 Linau, Pogg. An-nafan, 18(50, no, 148. (; Tarugi, Gazzdta, 1.897, 27, 1, 310.
7 Schneider, 'Poyy. An-nalc-n, 1844, 63, 53; J846, 68, 49; 1853, 88, 45. See also Aluir,
J. Cham. Hoc., 1877, 31, 050; 32, 128; Berzelius, t; Lehrbuch" (Dresden, 1826), 2, 273;
Thomson, Proc. Hoy. Phil. Soc. Glasyow, 1842, I, 4; Hciiiiz, Poyy. A'litiaU-n, 184-1, 63, 55,
559; Arppe, ibid., 1845, 64, 237; Schiff, Amialtn, 1861, 119, 331; Bunson, ibid., 18GG, 138,
277; Vogcl, Kastner's Archiv, 1868, 23, 86.
COMPOUNDS OF BISMUTH. 183
The substance produced when one of the basic oxalates of bismuth,
_Bi 2 O(CoO 4 ) 2r is heated is a mixture, probably of bismuth monoxide
and bismuth, but when the basic oxalatc Bi 2 O 2 .C 2 4 is heated in a
current of carbon dioxide, bismuth monoxide alone is stated to be
obtained : l
Bi 2 2 .C.,O 4 - 2BiO -f 2C02
This method of Tanatar is now usually employed.
Bismuth trioxide is reduced by heating in a current of hydrogen -
at 267 C., or in carbon monoxide. In the former case it is possible
that the monoxide is formed. In the latter case, the reduction being
carried out at 800 C., it will be seen from the following data and the
accompanying time-reduction curve (fig. 8) 3 that there is a break at
Bi 2 3
3-000-
.9 12 75 78
Time (hours)
FIG. 8. Reduction of Bismuth Trioxide by Carbon Monoxide at 300 C.
a point at which the composition of the reduction product corresponds
approximately to that of bismuth monoxide.
Time (hours) . ] 3 : 4-1- ! . 6 9 ! 12 ; 15
Weight of Bi.,O,j : " j
(grams) . " 1 i 3-000 | 2-934 j 2-920 2-890 2-868 2-850 2-831 ,
The above methods and conclusions have, however, been criticised,
and considerable doubt has been thrown on the existence of an oxide
of bismuth lower than the trioxide. 4
Bismuth monoxide is described as a greyish-black, finely crystalline
powder, having a mean density 5 of 7-5 at 20 C., values lying between
7-17 and 8-55 having been reported. This value is lower than that of a
corresponding mixture of bismuth trioxide. and bismuth; but this does
not prove the existence of a separate compound, as the low density may
be due to the presence of hydroxide in the samples investigated. 6
When dry, the oxide is quite stable in air, but in the presence of
1 Tanatar, Zeltach. art.ory. Chcm., 100 J, 27, 437; Denhain, J. Artier. Chc-ni. ftoc., 1921,
43, 23G7.
- Muir, J-Iofi'meistcr and Robbs, J. Chcm. Sue., 1881, 39, 21.
3 BiLslee, J. Che-m. &oc., 1908, 93, 154.
J Xeus.ser, Zcttxch. anwrj. Chew.., 1924, 135, 313; 138, ISO; Vanino and Troubcrt,
B(.-.r., 1898, 31, 1113, 2267; ' 1899, 32, 1072. See also Herz and Guttmann, ZeitscJi. anal
Cham., 191;"), 54, 113, 413; Zdtsch. anorg. Chtm., 1907, 53, 63.
5 I.!iUritaiional Critical Table*, 1926, I, 111. See also Treubert and Vanino, Ztitech.
anal. Chcm., 1914, 53, oG4; 1915, 54, 255; Tanatar, loc. cit.
Xcusser, loc. cit.
184 ANTIMONY AND BIS^rUTH.
moist air it is slowly oxidised to a white hydra ted trioxidc, Bi 2 O 3 .2lIoCX
It is also oxidised" on heating in air, oxidation beginning at about
180 C. It is decomposed slowly by cold water, and more rapidly on
boiling.
It is attacked by warm dilute acids with formation of salts of tervalent
bismuth and precipitation of bismuth. 1 With hydrochloric acid this
reaction may be represented by
3BiO -r 6HC1 = 2BiCl 3 -f Bi -t- 311 2
It is oxidised by nitric acid, but in the presence of excess of add the
reaction proceeds as with hydrochloric acid.
When heated in oxygen, oxidation begins at 140 C. and is complete
at 240 C. The oxide is also oxidised slowly when heated in a current
of carbon dioxide. It is easily reduced to metal by heating on a char-
coal block, or in a current of hydrogen or carbon monoxide ; reduction
in. hydrogen takes place at 300 to 310 C., and in carbon monoxide
begins at about 250 C.
The monoxide is readily oxidised on boiling with a solution of
potassium hydroxide and bromine with the formation of the pentoxide,
BioO 5 ,^H 2 0, It is converted to metal by reaction with aqueous
potassium hydroxide alone. It will reduce Fehling's solution, and
potassium permanganate.
It is weakly basic : the halide salts and the sulphide are the only
salts derived from it that have been reported. They are unstable and
difficult to obtain pure.
By comparing the heats of reaction of hydrochloric acid with
bismuth monoxide and with a corresponding mixture oi' bismuth and
bismuth trioxide, the calculated heat of formation of one .mole of
monoxide 2 is given as 3938 gram-calories, that is :
Bi 2 0, -r Bi = 3BiO + 11,814 calorics
As has been stated previously, most of the facts enumerated here
have been adversely criticised. Arguments have been brought .forward
in favour of the view that, on theoretical grounds, it is very improbable
that bismuth monoxide can exist. 3 Comparisons have been made
between bismuth monoxide, prepared by various methods, and a
corresponding mixture of bismuth and its trioxidc ; and the numerical
values obtained for the heat evolved in the reaction with hydrochloric
acid, the solubility in an aqueous solution of sodium hydroxide and
the specific magnetic susceptibility 4 have been found to be approxi-
mately identical in each case. In. further support of this view, it is
stated that metallic bismuth can be extracted from bismuth monoxide
by shaking with mercury ; and that the monoxide reacts with dry
hydrogen sulphide as if it were a mixture of bismuth, bismuth trioxide
and bismuth hydroxide. 5 When prepared by the action of potassium
hydroxide upon a solution of bismuth trioxide and stannous chloride
in hydrochloric acid, it reacts with sulphur dioxide to form basic
bismuth sulphate, 4Bi 2 O 3 .3S0 3 . Since this substance is also obtained
COMPOUNDS OF BISMUTH. 185
by the action of sulphur dioxide upon bismuth trioxide, it has been
suggested that bismuth monoxide may be a compound Bi.Bi 2 3 , but
the possibility of its being merely a mixture of bismuth and trioxide
is not eliminated. 1
Much of the confusion regarding the existence of bismuth monoxide
undoubtedly arises from the difficulties encountered in the preparation
and purification of specimens of the substance ; the products obtained
by the various methods described frequently vary in composition. In
addition, these products arc for the most part unstable, especially in
the presence of moisture. 2
Bismuth Trioxide or Bismuth Sesquioxide, Bi 2 O 3 . Bismuth tri-
oxide is found naturally as bismuth ochre. It is the product obtained
when bismuth burns in air ("\flores bismuti "), 3 or when steam is decom-
posed by metallic bismuth at white heat. 4 It is usually obtained by the
prolonged heating of molten bismuth in air, or by the action of heat
upon the carbonate, sulphate or basic nitrate. 5 Bismuth monoxide
when heated in air yields the trioxide. The crystalline form is obtained
by melting the powdered form with potassium hydroxide, 6 by boiling
the hydroxide with potassium or sodium hydroxide, 7 by the action of
potassium cyanide on a nitric acid solution of bismuth nitrate, 8 or by
adding sodium nitrate intermittently to a molten mixture of sodium
hydroxide, bismuth and potassium ehromate 9 at 350 C. The oxide
is also obtained when chlorine is passed into a fused mixture of bismuth
and silver nitrate. 10
The mineral, bismuth ochre, occurs in massive form with an uneven,
earthy fracture ; its colour is yellowish-grey or green : it is very soft and
friable. The crystalline form of the oxide, prepared as described above,
is obtained in the form of bright yellow, transparent rhombic prisms : 11
a : b : c= 0-817 : 1 : 1-005
More usually, bismuth trioxide is obtained as a lemon-yellow powder
which becomes darker on heating. When pure it is insensitive to light. 12
The various values that have been given for the density and melting
point of this oxide arc probably due to the existence of polymorphism.
Three varieties have been described. The first variety has a melting-
point at 820 C. and density 8-0. On cooling it passes to the second
variety at 70-1- C. (density 8-2) : supercooling frequently occurs at this
transformation, followed by rccalescenee. This second variety varies
from yellow to brown in colour. The third variety, melting at 860 C.,
and of density 8-5, is formed by heating the trioxide strongly in a
porcelain crucible. Both the first and third varieties crystallise in the
1 Harnimck, ,/. Chan. .W., 1017, in, 383.
- Sec also Variino and Zumbussch, Arch. Phar/ti., 1910, 248, 665; Goldschmidt, British
Patent, 1922, 189706.
:! v. Bonsdorjl, Pofjfj. An.n.'ilf.-.n, 1837, 41, 30.").
4 JUi.irnuulfc, An-n. Ck,m. 7%*., 1836, |.2j, 62, 2G3.
r ' Smith, J. Anu.r. Ckc.tn. &oc., 1923, 45, 360.
(; .Xordenskiold, / J {/.'/ An-nalc.:n, J861, 114, 622.
7 Stronicyer, Pogtj. Amui-ltn, .1832, 26, 533.
8 Aluir and lluichinson, J. Chem. tioc., 1889, 55, 1-13.
51 Ta\vara, Japanese Patc-nt, 1931, 93504.
1(1 Darlma, L;.$. Patent, 1920, 1354806.
n Xordenskiokl, Poyy. Annalcn, 1861, 114, 622; Groth, Chem. KrysL, 1906, i, ]00, 109.
^ Schill, Annaicn, 1861, 119, 335; Schneider, J. prakt. Chem., 1881, [2], 23, 86.
186 ANTIMONY AND BISMUTH.
rhombic system, but the first modification cannot exist at ordinary
temperatures. 1
The variation of the specific heat of bismuth trioxide with the
temperature is shown by the following data :
Temperature, C.
Specific heat 2 .
50
0-0569 |
100 ;
0-0593
200
0-0617
300
0-0631
400 !
0-0641 !
Temp., C. . : +16-3 j -10-9J -59-7 | - 106-6; - 160-0- - 204-3 - 212-4
Specific heat 3 , 0-0563 0-0561 0-0512 ! 0-0447 | 0-0350 j 0-0241 0-0204
The variation of electrical resistivity with temperature 4 is :
Temperature, C. .
Resistivity (ohm-cm.)
225
2-34 xlO 8
425
1-44 xlO 5
645
6-01 xlO 3
The thermoelectric power with reference to lead, between 500 and
800 C. and with the cold junction at C., is given by
Thermoelectric power (1-946 -1-862) x 10~ 6 volt per degree C.
where t is the temperature ( C.). 5 The specific magnetic susceptibility G
is -0-170 x 10~ 6 . The dielectric constant 7 is 18-2 and appears to be
independent of the field strength.
Bismuth trioxide is volatile at high temperatures, the calculated
boiling point being 1890 C. Volatilisation 8 begins at 950 C.
In the spectrum of bismuth trioxide 9 four band systems are found
between 4300 and 6700 A.
The heat of formation of the trioxide from its elements is 136,600
gram-calories per mole. 10 The heats of formation of the hydrated forms
of bismuth trioxide have also been calculated (see, however, p. ISO). 11
The trioxide does not decompose when heated to 1750 C. 12 It is
1 Guertler, Zeitsch. anory. Chcm., 1903, 37, 222.
2 Expressed as gram-calories per gram. Hauser arid Stcger, Zeitsch. anorg. Clieni.,
1913, 80, 1. Sec also Regnault, Ann. Chim. Phys., 1841, i, 129.
3 Anderson, J. Amer. Clitm. Soc., 1930, 52, 2720. See also Kelley, Bureau Mines
Bulletin, 1932, 350.
4 Horton, Phil. Mag., 1906, n, 505.
"' Bichvell, Phys. Rwitw, 1914, 3, 204.
6 Endo, tici. Rep. Toho'ku Imp. Univ.) 1925, 14, 79.
7 Gunther-Schiilze and Keller, Zeitsch. Physik, 1932, 75, 78; Giinthcr-Schulze and
Betz, ibid., 1.931, 71, 106.
8 Teiser, Mctall und Erz, 1930, 27, 585. See also Bailey, ,/. Cham. Soc., 1887, 51,
680; Hempel, Zeitsch. anal. Cham., 1881, 20, 449.
9 Ghosh, Zeitsch. Physilc, 1933, 86, 241.
10 Mixier, Amer. J. Sci., 1909, [4], 28, 103.
11 Thomsen, Ci Thermochemistry'-' (London), 1908, p. 230.
12 Read. /. Chzrn. Sec.. 1894. 6*. 313.
COMPOUNDS OF BISMUTH. 1ST
reduced, partially or completely, by a number of reducing agents, such
as hydrogen, 1 carbon, carbon monoxide, 2 silicon, 3 sodium, potassium,
methane, 4 ammonia, ammonium chloride, potassium cyanide, 5 aluminium
carbide, 6 and an alkaline stannous solution. It is oxidised by ozone
to bismuth pentoxide, and by ozone in the presence of alkalies to
bismuthates ; 7 it is only slightly oxidised by alkaline permanganate
solution.
When dry bismuth trioxide is heated in a current of dry chlorine,
a white, crystalline, deliquescent sublimate of bismuth trichloride is
formed. When heated with an excess of bromine for several hours, and
after exposing the product to the air, an oxybromide, Bi 11 O 13 Br 7 , is
obtained as a non-deliquescent, cream-coloured powder. 8
When heated with manganese dioxide, slight reaction takes place
between 300 and 500 C. A violet-grey powder is formed, but the
nature of the reaction has not been fully established. 9
Bismuth trioxide reacts with sulphur to form bismuth trisulphide,
and with hydrogen sulphide to form a sulphide 10 to which has been
ascribed the formula Bi 4 S 3 . A rather complex reaction occurs with
sulphur dioxide, among the products being a basic bismuth sulphate,
and, possibly, bismuth monoxide. 11 The reaction may possibly be
represented by the equation
7Bi 2 O 3 +3SO 2 = 6BiO +4Bi 2 O 3 .3SO 3
It begins at a temperature below visible red heat. At first a dark grey
or black powder is formed ; this, on prolonged heating, is converted into
the white, crystalline, basic sulphate, 4Bi 2 O 3 .3SO 3 . A little sulphur
trioxide is also evolved. The dark grey powder contains a sulphate,
but not a sulphide. It is not completely soluble in hydrochloric acid,
and the black residue so produced is mainly bismuth. From this it is
conjectured that the dark grey powder contains bismuth monoxide.
Bismuth trioxide does not appear to react with nitrogen, even when
heated. 12 It is reduced to metal by heating with ammonia at 250 C.
There is no indication of the formation of a bismuth nitride, but as some
water is produced during the reaction it would appear that sonic of the
ammonia is decomposed. 13 The reduction is accelerated in the presence
of silver and quartz sand. With phosphorus trichloride at 160 C. a
complex reaction takes place, the products including bismuth oxy-
chloride, bismuth phosphate, phosphorus oxy chloride and perhaps
bismuth dichloridc. 11 The trioxide is reduced by arsenic in the presence
1 Schneider, Poyy. A/uudtn,, 18f)l, 82, 312; Muir, Hoft'meislcr and Robbs, J. Chtm.
Hoc., 1881, 39, 28.
- Muir, Jrlofimeister and Robbs, loc. oil.; Brislec, /. Che/n. Soc., 190S, 93, 163.
3 Kahlenbur^ and Traulman, f j''mn.$. Anicr. Electrochem. Soc., 1951, 39, 412.
J Midler, Porjfj. Annaltu, 1864, 122, 145.
5 Rose, Poyfj. An/tialcn, 1853, 90, 199.
G Pnng, J. Ckwn. &oc., 1905, 87, 1530.
7 Mailfcrt, Corn.pt. rend., 1882, 94, 863.
a Muir, J. Cham, &oc. t 1877, 31, 26.
;) de Carh, Alii tt. Accad. Lined, 192(5, [6], 4, 577.
10 Schumann, Annalun, 1877, 187, 313.
11 J-Iamrnick, .7. Ckc/m. Soc., 1917, in, 385.
12 Muir, loc. cit., p. 647.
la Muir, loc. cit., p. 28. See also Gutbier and Birckenbach, Zettscli. 'Eleldrocham., 1905,
n, 831.
11 Michaelis, J. nrakt. Ckem.. 1871, [2], 4, 454.
188 ANTIMONY AXD BISMUTH.
of molten sodium hydroxide. 1 It reacts readily with bismuth tri-
sulphidc according to the equation
2Bi 2 O :{ -hBi 2 S :J =6.Bi-f3SO 2
The reaction begins at quite low temperatures in a current of carbon
dioxide ; it can also be conducted under molten sodium chloride.
There remains, in addition, a residue which gives the reactions for a
sulphate ; probably partial reduction also takes place according to the
equation 2
Bismuth trioxide, when heated with silicon, tetrachloride, yields
bismuth trichloride and silica. 3
It reacts with potassium thiocyanatc 4 with the formation of bismuth
trisulphide and a complex compound. K 2 Bi 2 S 4 .
Thermal examination of the system Bi 2 3 -PbO reveals the possible
existence of the compounds 4Bi O. B .PbO (decomposing at 690 C.),
3BioO s .2PbO (M.pt. 686 C.) and Bi O r 2PbO (M.pt, 625 C.) (see
fig. 9)>
Bismuth trioxide does not attack platinum below 1200 C. in a
neutral atmosphere. At 1300 C. it is slowly decomposed and the
liberated bismuth gradually absorbed by the platinum with the forma-
tion of a brittle, fusible alloy. At 1400 C. this action becomes rapid,
and a platinum vessel is completely destroyed when, heated with bismuth
trioxide at this temperature. 6
Bismuth trioxide reacts mainly as a basic oxide, forming bismuth
salts which, in most cases, are readily hydrolyscd yielding, as the dual
product, basic salts. That, under certain conditions, it also exhibits
very feeble acidic properties is shown by its slight solubility in aqueous
solutions of alkali hydroxides, as indicated by the following data 7 for
the solubility in solutions of sodium hydroxide :
I Concentration of NaO.ll (moles per ;
litre solution) . . . . 1-0
Solubility of .BioO 3 (lirams per
100 c.c. solution)
0-0013 ^0 0002 0-0020 : ;-_ 0-0002 0-0049 , L 0-0005
The solutions, in each case, give no indication of being colloidal. It
will be seen that the solubility increases approximately in proportion
to the concentration of the alkali. The feeble acidity of bismuth
trioxide is further supported by the fact that in the solid state it will
react with barium oxide when heated, but not with oxides less basic. 8
Mixtures of bismuth trioxide and iron oxide (containing from 3 to
4 per cent, of bismuth trioxide) have been suggested as substitutes for
1 Kirscbom, Fre.-ncJi Patent, 1030, 694283.
2 Schocllcr, ,/. Soc. Cham. Ind., 1915, 34, 6.
3 JRauter, A'n;nu.hn-, 1892, 270, 251.
- 1 Milbaucr, Ztitsch. anortj. Chc.ni., 1905, 42, 433.
5 Belladen, GazzcUa, 1922, 52, II, 100.
COMPOUNDS OF BISMUTH.
ISO
platinum gauze in the process for the catalytic oxidation of ammonia. 1
Similar mixtures of bismuth trioxide and cobalt oxide have also been
employed. These oxide mixtures arc used in the form of a loose,
granular powder ; they are active at about the same temperature as
platinum gair/c. but they act more slowly and their life is not so long. 2
900-\
400
JO 20 30 40 50 60 70 80 90 WO
Pb o Mois. Bi 2 3 per cent. /,0 :J
Fro. 9. Free/in^ Point Diagram of the System Bi.-,0 3 -Pb().
Bismuth Hydroxide or Hydrated Bismuth Trioxide. Three
hydrated forms of bismuth trioxide have been described. They are
the trUnjdrate, or bismuth hydroxide, Bi 2 O,.3H 2 or Bi(OH) 3 ", the
di hydrate, jBioO r 2lL>O, and the monohi/drate, also known as bismuth}'!
hydroxide, Bl 2 6 : ,.HoO or BiO(OII). there is no doubt that hydrated
forms of the trioxide can be prepared by a. variety of methods, but their
existence as definite chemical compounds has been criticised. From a
study of the dehydration of hydrated bismuth trioxide at a constant
pressure of 30 mm. mercury, it. was determined that water is removed
in three stages. Assuming the original hydrated oxide to be the tn-
hydratc, water is removed from this continuously as the temperature
.rises until the composition approximates to that of the dihyclrate. At
about 320 C. water is removed suddenly and the composition approaches
that of the monohydrate. The remaining water is again removed
continuously, a temperature higher than 120 C. being required for
complete removal. 3 An earlier investigation on the dehydration of the
hydrated oxide by heating 4 revealed a slight break in the dehydration
190 AXTIMOXY AND BISMUTH.
curve between 340 and 415 C., but no substance corresponding in
composition to a definite hydrate was obtained. If the hydrated oxide
is dried over sulphuric acid, dehydration proceeds continuously and
there is no indication of a definite hydrate. 1 Further, recent attempts to
prepare by various methods a substance that could be identified as the
definite compound bismuth hydroxide, Bi(OH) 3 , have proved unsuccess-
ful. 2 It is probable, therefore, that if definite hydrates of bismuth
trioxide do exist, they are extremely unstable. The substance as
usually prepared, and technically known as " bismuth hydroxide," is of
indefinite composition. Among the methods adopted for its preparation
may be mentioned precipitation from solutions of bismuth salts by
ammonium hydroxide, followed by washing with a succession of volatile
solvents and evaporation, 3 and electrolysis of a dilute solution of
sodium chlorate, containing carbon dioxide, using bismuth anodes and
cathodes of carbon, zinc, iron or aluminium. 4 A description follows of
the three hydroxides that have been reported.
Bismuth Trihydrate, Bi 2 O 3 .3H 2 O or Bi(OH) 3 , is most conveniently
prepared by adding a solution of a bismuth salt containing glycerol
to one of sodium hydroxide, and neutralising the excess of alkali with
nitric or acetic acid. The product is frequently contaminated with
traces of the bismuth salt employed and with the carbonate (through
absorption of carbon dioxide). 5 The hydrate is not precipitated from
solutions by alkalis in the presence of tartaric acid 6 or citric acid. 7
It is a white substance, and is converted to yellow bismuth trioxide on
boiling with alkalis : 8 at lower temperatures, in contact with alkalis,
it is said to be converted to the monohydrate. At 20 C. it is practically
insoluble in a normal solution of sodium hydroxide and more dilute
solutions : the solubility is slightly higher in 4JV XaOH, and increases
appreciably with higher concentrations ; it is greater at 100 C., but still
low in dilute solutions. 10 Thus bismuth hydroxide resembles the tri-
oxide in possessing only very slight acidic properties. It is soluble in
sodium hydroxide in glycerol, 11 and by heating this solution, and those
in tartaric or citric acid, with grape sugar, the hydroxide is reduced to
metal.
The so-called diliydrate, Bi 2 3 .2H 2 O, is prepared as a pale yellowish-
white, floceulcnt body by precipitation from a solution of so-called bis-
nmthic acid in hydrochloric acid by potassium hydroxide after passing
a current of sulphur dioxide through the liquid. When, however,
sulphuric acid is used in place of hydrochloric acid, the precipitate is
1 Moser, ZeitscJi. anorg. Chem., 1909, 61, 379. See, however, Thibault, J. Pimm/.,
1900, [6], 12, 559.
- H'ackspill and KiciTcr, Ann. CJiim., 1930, [10], 14, 227.
3 I.G. Farhenind. A. G., British Patent, 1928, 332504.
' Carreras, British Patent, 1927,298587; French Patent, 1929,040346; German Patent
1927,538286.
"' Moscr, Joe. cil.; Stromcyer, Pogg. Anmden, 1832, 26, 553; Muir and Carnegie,
J. Chem. Soc., 1887, 51, 79 , Carnclley and Walker, Joe. c/'L
G Schneider, .Pogg. Annftl.cn, 1854, 93, 312; Xylander, Zeitxch. anal. Chem,., 188-1, 23,
440: Schmucker, Zeifsch. an-org. Chem., 1894. 5, 206.
7 Smith and Frankel, Ame.r. Chf-m. J. 7 1890, 12, 428; Lottermosor, J. prakl. Cham..,
1899, [2], 59, 489; Rosenheim and Vogelsang, Zcilwh. a/iorg. Clic.tn,., 190(>, 48, 20S.
8 SiromcycT, lor,, eil.
J Moser, iuc. cit. See, Iio \vever, Corfiold and Wood \\-ard, Ch<:nuxl ann, J)ru.(jnixt, 192-1,
COMPOUNDS OF BISMUTH. 191
more probably the monohydrate. 1 Two dimorphous forms of the
dihydrate have been described. 2
The monohydrate^ or bis?nuthyl hydroxide, or " bismuthi hydroxidwn"
Bi 2 O 3 .H 2 O or BiO(OH), is prepared by pouring a solution of bismuth
nitrate in dilute nitric acid rapidly into ammonium hydroxide and
drying the precipitate at a temperature not exceeding 70 C. 3 This
method has, however, been criticised on the grounds that the hydroxide
always contains either an oxy-sa.lt or the trioxide ; it is also stated that
the only true hydroxide is the trihydrate, Bi O 3 .3H 2 O. On heating to
110 C. the trihydrate loses water, the residue containing 94 per cent, of
the trioxide. 4 The monohydrate is soluble in ordinary distilled water
to the extent of 1-44 milligrams per litre at 20 C. 5 It will precipitate
the hydroxides of aluminium, chromium and ferric iron from neutral
solutions of their salts, but is apparently without effect upon solutions
of copper, zinc, ferrous iron, nickel, cobalt, manganese and lead ; 6 but
according to other investigators the monohydrate precipitates most
metals as oxides or basic salts. It can be oxidised iri alkaline solution
by many oxidising agents and is reduced by stannous solution to
bismuth monoxide.
Colloidal hydrated bismuth oxides, known as " bismon,'' have been
obtained, 7 while hydrosols have also been prepared. 8
Higher Oxides of Bismuth.
Various higher oxides of bismuth have been described from time
to time, although in. many cases it is uncertain that the substances
obtained were pure. Three of these oxides will be discussed here,
namely, bismuth tetr oxide, Bi 2 O 4 , bismuth pentoxide, Bi 2 O 5 , and bismuth
hex oxide, Bi 2 O 6 .
As early as 1818 an oxide of bismuth containing more oxygen than
the trioxide was prepared, 9 but this, and many of the preparations
subsequently described by other investigators, were probably mixtures
of the tct.roxi.dc and the pentoxidc, and may even in some cases have
contained an alkali bismuthatc. In most cases the higher oxide was
prepared by the action of an oxidising agent upon a suspension of the
trioxide in an alkaline solution. Oxidising agents that have been
employed include ozone, 10 hydrogen peroxide, 11 potassium persulphate, 12
I Muir, J. Che.m. Soc., 1877, 31, 647.
- Closer, Joe,, c.il.
3 '* Hrilixh Pharmaceutical CorUx" 1923, p. 207; Arppc, Poyg. Annnkn, 1864, 64, 237;
Thibault, J. Pharm. Chim., 1000, [6], 12, 559; Minr, J. 'Chum, Soc., 1877, 31, 648.
' Corfidd and 'Woodward, Pharm. J., ]924, 113, 83, 128; Chemist and Druggixl, 1924,
101, 134.
5 Almkvisl, Zritsch. anorg. Chun., 1918, 103, 240.
<> .Lcbaigne, J. Pharm., 1803, [3], 39, 51.
7 Taal and di Pol, Bar., 1926, 59 B, 874.
8 Biltz, Her.. 1902, 35, 4434; Kulin and Pirsch, Kolloid Zc.it., 1925, 36 (Zsiijmondy-
Fr-xt*chrifl.}, 3.10; TIaissinsky, Compt. rend., 1934, 198, 580.
II Bucholx and Brandos, tich-irc.i'jgrfs J., 1818, 22, 23.
10 Sehonbein, J. pra./cf. (Jhr.in... 1864, 93, 59; Mail'fert, Cnmpt. rend., 1882, 94, S63.
11 riasi-broek, Itrr., 1S87, 20, 213; .laimasch and collaborators, J.kr., '1893, 26, MOO,
2908; 1894, 27, 2227; 189"), 28, 004, 1408; Zc.it fich. anory. Cfwm., 1895, 8, 302; Alorath
and JjOrcli, inn IKJ. .I)/s^crl(iiiCiii, J\{'U.ncJien, 1893; Rnpp and Scliauniann, Zc.i.t^ch.. anal.
(Jhem., 1903, 42, 732; Hanger and Vanino, Zciltch. a-/iorg. Chcr/i., 190-1, 39, 381; Moscr,
Zeitsck. rmurrj. Chein., J 906, 50, 33.
l ~ Dcichlcr, Zeilxch. anorg. Chem., 1899, 20, 81; Rupp, Zeitsch. anal. Chern., 1903, 42,
732.
192 ANTIMONY AXD BISMUTH.
alkali hypochlorite, 1 chlorine, bromine, 2 and potassium ferrieyanide. 3
Molten bismuth tri oxide has also been oxidised by air, potassium
chlorate and potassium nitrate. 4 In addition, higher oxides have been
obtained by electrolytic methods. 5
Many of the methods just mentioned, involving the oxidation of
bismuth trioxide in. the presence of alkalis, have been repeated, 6 but
in no case was a compound of uniform composition obtained ; and the
compound previously considered to be bismuthie acid, HBiO ;} , 7 always
contained less oxygen than corresponds with this formula and was not
uniform in composition, and further the. product shows no sign of salt
formation with a concentrated solution of potassium hydroxide.
Probably the product obtained is a mixture of higher oxides which
possess no acidic properties. Attempts to obtain a uniform product
by electrolytic methods have also proved unsuccessful. 8
Bismuth Tetroxide, Bi 2 O 4 , hyd rated with one or two molecules
of water, is formed when sodium bismuthate is decomposed with nitric
acid ; the anhydrous substance has not been obtained by this method,
as oxygen is lost when water is removed. 9
Four different modifications have been obtained by the action of
various oxidising agents upon a suspension of bismuth trioxide in
boiling solutions of dilute alkali hydroxides. 10 Two of these modi-
fications are anhydrous, the others being modifications of the mono-
hydrate, Bi 2 O 4 .H 2 O. A dihydrate, Bi 2 6 4 .2l-I 2 O, is obtained by the
action of chlorine upon a suspension of trioxide in a boiling, concen-
trated solution of alkali hydroxide : it is always contaminated with a
hydratcd pentoxide. from which it can be separated by treatment with
boiling, concentrated nitric acid.
Anhydrous bismuth tctroxide is brown or purplish-black. Its
density "(at 20 C.) is 5-60 to 5-75, that of the dihydrate being 5-80.
The anhydrous substance is stable at 100 C., but loses oxygen at 1.00 t .
The monohydratcs begin to lose water at 100 C., and arc decomposed
at 16() c C., whilst the dihydrate is decomposed at 100 C.. losing both
oxygen and water. The tctroxide is not attacked by dilute nitric, or
1 Brandcs, Schwf'iyyf.-r' 1 * J., 1833, 69, 158; Siroineyer, Pof/fj. A-mnilfn., 1832, 26, 540;
Jacquclain, Ann. Chim. Phys., 1837, [21, 66, H3; ,7. pralct. '(-hdii-., 1838, 14, I; Arppc,
J J of/g. Anna Jen, 1 845, 64, 2,38; Sclirarlor^l^We/^ 1862, 121, 20-1; So.hifT, Ann<ilc,>, 1801,
119, 342; Rupp, Ze./l*ch. a-nal. Cha/i., 1903, 42, 732; Foster, Ifr-r., 1871), 12, 84(5.
- Jacquelain, 'loc. cit.: Arppo, Joe. ciL; Hemtz, l } <>(](j. A-mxik-n^ 1844, 63, 55, 550;
Schiff, Joe. n(.; Schrader, loc.. cit.; .Hoffmann, A-nuah-n, 1884, 223, 1 K); .Miur, J . Ch/ni.
Snr.. J876, 29, 149; Hilger and van Hcherpenborg, Millcilu-ixjc.n uu* df-r Krlnnfjfr J'hrnm.
7/v-v/'., 1889, II, 4, 7; Morath and Lorch, lor,. ci.f..\ Dcichlor/Zt//.^//, nnory. ('//,., 1800,
20, 81, 103: Andre, Compt. re-nd., 1801, 113, 800; 1.802, 114, 350.
3 .Hauscr and Vanino, loc. at.
1 Bucholz and Brandos, lor., cit.; Jacquclain, loc. ci.L; I-'roni}', Cotttpt. r<:n<L, 1812, 15.
1108; Schneider, JMonateh., J888, 9, 252; Bottger, J. prakt. Chcni., 1858, 73, 41)!-.
5 Luckow, DifKjl. poly. J., 1865, 177, 231: \Vemieke, Poyy. Aii.>t.n{r,i, 1870, 141, 117;
Schucht, J3crg- Uiid Hulten-iiUin'rusc.kr. Zeituny, Leipzig, 1880, 121; Deichler, \<><\ al.;
1005, 44, 237.
100(5, 50.
210; 1007, 52, .124; Xilzn<jHl)f-ric/d('/pft.yUML-m(.-d. Xor.'. Erlantjcn, 1000,40, 00; Ulicm.
Zc.iiir., 1000, i, 732.
T Muir, tlotYnu'i.sler and KobUs, /. Cite in. >8'or., 1881, 39, 22; Dciclilc-r, Inc. nl
s GuLbu-r and Bun/., Zcitsch. (tnaxj. ('hem.., 100(5, 48, 204. Sec also Muir, .7. Clif-ni.
Snr., 1870, 29, 151.
11 Coriieki and Woodward, I'h/t /-;/?. J., 1023, [-1 '!, 56, 80; Ckcm^t. and Di '/f/f//-s/, IU23,
COMPOUNDS OF BISMUTH. 193
sulphuric acid. The crude substance as usually prepared is partially dis-
solved by more concentrated nitric acid (density 1-2) at 70 to 00 C.,
with evolution of oxygen, the insoluble residue having a. composi-
tion corresponding to that of bismuth tetroxide. From this it is
deduced that the usual preparations arc mixtures, probably of tetroxide
and pcntoxide. The tetroxide reacts with concentrated oxygen acids
to form tcrvalent bismuth salts with evolution of oxygen. It is very
sparingly soluble in. alkali hydroxide.
Bismuth tetroxide can be reduced by hydrogen and by carbon
monoxide. Hydrogen peroxide is decomposed by it. 1 It is a powerful
oxidising agent ; hydrochloric acid is oxidised to chlorine even at
-15 C., and manganous salts are oxidised to permanganate immedi-
ately in the cold in the presence of nitric acid.
With hydrochloric acid there is no indication of the formation of a
chloride of quadrivalent bismuth. 2
Bismuth Pentoxide, Bi 2 5 , or a hydrated form of this compound,
is probably formed, mixed with tetroxide, by most of the methods
already mentioned. Bismuthic acid, HBiO 3 , is said to be formed
when a solution of bismuth oxytrifluoride, BiOF 3 , is decomposed by
water and nitric acid, and evidence of the formation of sodium bis-
muthate was also obtained when the same compound was treated
with sodium hydroxide. 3 A hydrated oxide, Bi 2 O 5 .H 2 0, is obtained
cither by the action of chlorine on bismuth trioxide suspended
in a boiling concentrated solution of alkali hydroxide or, in small
quantities, by the action of ammonium persulphate on the trioxide
suspended in dilute alkali at 10 to 00 C. for five or six hours. In
both cases the pcntoxide is mixed with hydrated tetroxide. Two
varieties of the monohydrate of the pentoxidc have been described, a
red or brown variety soluble only with dinic.nl ty in concentrated nitric
acid, and a. brown variety, obtained from commercial sodium bismuthatc
after repeatedly grinding Avith glacial acetic acid, which is readily
soluble in nitric acid (density 1-2). The hydrate rapidly decomposes
at 100 C., leaving a residue of trioxide and tetroxide. It is possible
that the anhydrous form is incapable of existence. 4
Bismuth pentoxidc is described as a dark red powder of density
(at 20 C.) 5-10 ; on heating it loses oxygen, yielding first the tetroxide
and finally the trioxide. It is reduced by hydrogen and by carbon
monoxide : it is an oxidising agent, but has only feeble acidic, properties.
Bismuthates of sodium and potassium ha.ve been described. Sodium
bismuthate can be prepared by adding basic bismuth nitrate gradually
to caustic soda heated to redness ; sodium peroxide is then added and
the ('used mass is allowed to cool. 5 Many earlier investigators mentioned
and described alkali bismuthates, obtained by the methods outlined
for the preparation of higher oxides, but it is doubtful whether the
substances obtained were purr, or were even true compounds. 6 Sodium
bismuthate as made commercially is a very unstable substance, being
1 Schojiboin, J. innkl. C/icm., ISC, 4-, 93, ."><).
- Manser an I Vanino, Zc.ifxch. aiinry. ('hc.in., IH04, 39, I>S1.
(c-li and ZrdiK-r, Putsch. <\>n><(\. ('//</., 1!)()S, 57, L^O. Soi\ liou'cvcr,
i 'holer, Zrtlvrh. (inni-1}. Cli<-m., I'.iOS, 59, M:>.
id Robertson, J. Cfn-m. >sVx- , 1!)^(), 117, (>;J.
nd .Kjniiaiio, J. Ch<m,. >SV,., IS!">, 67, 271; Corfield and \Vood\vurd,
li)-i AXTIMOXY AXD BISMUTH.
decomposed by hot water and by dilute acids. It is used as an oxidising
agent in the analytical determination of manganese in iron and steel
alloys, the manganese being oxidised in the cold to permanganate in
the presence of nitric acid.
Bismuth Hexoxide, Bi 2 O 6 , has been obtained in small quantities
by the action of ammonium persulphate or potassium ferricyanide upon
a suspension of trioxide in a boiling concentrated solution of alkali
hydroxide. Bismuth tetroxide is formed at the same time, and
separation may be effected by treatment with warm nitric acid
(density 1-2). It may also be obtained by the oxidation of bismuth
tetroxide. It is a pale brown, anhydrous substance, which loses
ox\^gcii slowly at the ordinary temperature. 1
Evidence suggesting the existence of another oxide, Bi 4 7 , has
been obtained from a study of the electrode Bi/Bi 2 O 3 in solutions of
sodium hydroxide in the presence of oxidising agents. 2 This oxide
docs not appear to have been isolated, however.
BISMUTH AXD SULPHUR.
Bismuth and sulphur combine when heated together. Two sulphides
have been described ; they are, bismuth monosulphidc, BiS or Bi 2 S 2 ,
and bismuth trisulphiclc, Bi 2 S 3 . No evidence has yet been obtained in
favour of a sulphide higher than the trisulphide. 3 Bismuth trisulphicle
is the more stable compound of the two ; indeed, the view has been put
forward that the monosulphide is really a mixture of the trisulphide
and metal. 4 An examination of the free/ing point curve of mixtures of
bismuth and sulphur (fig. 10) fails to reveal any indication of the
existence of bismuth monosulphidc. 5 A brief description of the results
of investigations on this substance, however, follows.
Bismuth Monosulphide, BiS, is stated to be formed when hydrogen
sulphide acts upon bismuth monoxide, cither directly or in a solution
containing sta.nnous compounds and tarta.ric acid ; G also by heating
a, mixture of bismuth hydroxide with an aqueous solution of potassium
cyanide and thiocyanatc. 7 Crystals have been obtained by melting
together bismuth and sulphur and cooling the melt quickly. These
crystals are stated by some to be bismuth monosulphide and by others
to be a mixture of trisulphide and metal. 8
When prepared in the dry way, the product is a slate-grey powder
with a density of 7-0 to 7-8 at 20'' C. : prepared in the wet way it is a
black, dull powder, which can be obta.ined in the anhydrous form by
drving over sulphuric acid. When dried over a water-bath some water
is still retained. 9
bertson, /or. rit.
., 19,'M, 40, 582.
, 541, f>Sl.
Pelabon, Ann. Chun. /V^/x., 11)09, 17, 526;
Co-nipt. ?r/,"/., 1003, 137, (54S; Men, Zrit.srh. anoiff. Chan., 1905, 47, 380; Jlcrz and
(lui.t niiinn, -ibid., 1907, 53, 71.
' Schneider, ./. i>ntl:t. ('h'-m., IS90, [2|, 60, 521; /V/f/. Atinnlrn, 1 85C>, 97, -ISO; Her/,
and CuUmium, Zat^'/i. (uiorrj. Chan , 19O7, 53, 71.
7 Holl'mann, A-miuh //, I SS 1,223, l; ^-
K U'crtlicr, ,/. ynikl. Chan., 1S12, 27, (>5; Hcinl/., /'<><J'J. A unfilc.n, 1814, 63, 57;
Schneider, J'of/y. Annulc'n, .1854, 91, 40 1-; .Rose, 1\><J<J. A-nnnk-n, 1S54, 91, 401; Vaniuo
and Trcubert,' 'tier., 1890, 32, 1078; Schneider, ,/. ')>ral:l. Chan., 1899, [2|, 60, 524; ITerz
and Outtmanii, he. cit. Scdini'ider, /Vyjy. A-nnalcn, 1850, 97, 480.
COMPOUNDS OF BISMUTH.
The monosulphidc is moderately stable in air, but it
193
sulphur
id, b" th
formed "^ solution and spongy metallic bismuth pre-
in
Bismuth Trisulphide, or Bismuth Sesquisulphide, Bi.S, is found
free in nature as bumutkinite, or bismuth glance. It may 'be made
500
400
300
Bi 261-
200
^700
^
^ 60
^ 400
a- 300
DI 268"
-
^
i; q .+Bi^\
1
-Te
v x x
LI^K,
Te 3
Eutectic
Se
S
,.. Eutectic (Bi+B
2 Te 3 )
(Te+Bi
2 Te ^
-
6881C.
^^x^
i
\
\
\
V8C.i '
' 422C
BiSe
BiSefi
^F
Q Bi 2 Sej
72%
fr
96% \
/
/
L/q.+
BiSeoc
BiSect
BL 2 Se 2
200
700
600 -
500 -
400-
300 I
Bi 971+
, _Eutectic(Bi+BiSe_d)
^
/
I
Eutectic (
Se+Bi 2 Se^)
^
x"^
Liq. +Bi 2
%
200
Eutectic (BI +Bi 2 63}
i
JO 20 30 40 50 60 70 M 90 WO
Atoms non-metal per cent.
IMC. 10. Frecxin.a Point Diagrams of the Systems Bi-S, Bi-Sc, Bi-Te.
artificially in a variety of ways, such as by melting together bismuth and
sulphur, by subjecting a mixture of bismuth and "sulphur in po^ er
o m to h,gh jH-essurc^by precipitation from a solution of a bismuth
salt by hydrogen sulph.de or alkali sulphide, bv the action of sodium
th.osulphate on a neutral solution of a bismuth salt," or bv heatin<"
Bismuth tnoxide with potassium thioeyaaate." In addition, it may ]>e
n , r ; ;1 -- ei ^i tlm ; M< ;</(,> f.< ./., .1810, 17, 417; dossier, Z.-il^h. a,,or<j. Cl,,,,, | 8'I5 o
-1-1; Al.cn, /."ilxcl,. <i,n, nj. diem.., I !)().">. 47 ;!,S6 "", Jft.io, 9,
- Npring, Ht.r., IHS.'i, 16, .1001.
3 Faklor, Phnrm. J'nst, 1900, 33, 301.
4 ililbauer, Zeitsch. anorrj. Chum., 1905, 42 441.
196 ANTIMONY AND BISMUTH.
prepared from bismuth halides by the methods described on pp. 173,
181. It may be obtained in the crystalline form by the interaction
of the vapour of bismuth trichloride with hydrogen sulphide. 1
Bismuth trisulphide crystallises in the rhombic system, although
other crystal forms have been described. 2 The crystal elements of the
mineral bismuthinite are : 3
a :b : c= 0-9862 : 1 : 1-0493
By X-ray examination it is deduced that the unit cell contains four
molecules. The parameters 4 have been determined to be :
ff. = ll-13A., 2> = 11-27A. 9 c=3-97A.
giving as axial ratios :
a : b: c = 0-9876 : 1 : 0-3523
As usually prepared the sulphide is a grey or black powder, which
can be converted into a microcrystalline mass by heat, by pressure, or by
heating in a solution of alkali sulphide. 5 It has a density of 7-00 to
7-81 ; that of bismuthinite is 7-4 at 20 C.
The melting point 6 is 718 C. By heating strongly in an atmosphere
of carbon dioxide it can be volatilised in small quantities without
decomposition. 7
The compressibility of bismuthinite 8 has been measured. The heat
capacity 9 is 0-06 gram-caloric per gram. When examined with light
from an electric arc, bismuth trisulphide shows very great photo-
conductivity (i.e. an alteration in electrical conductivity on exposure to
light). 10
Bismuth trisulphide is only very slightly soluble in water, the
solubility, 11 measured by a conductivity method, being 0-35 x 10~ 6 mole
per litre. It is slightly soluble in dilute hydrochloric acid, the solubility
increasing rapidly with rise of temperature. With dilute acid hydrogen
sulphide is evolved at about 70 C., but the temperature of evolution is
dependent on the concentration of the acid. The trisulphide is readily
soluble in concentrated hydrochloric acid. 12 It is readily attacked by
dilute nitric acid, sulphur being precipitated. It is decomposed by
heating with sulphuric acid, sulphur dioxide being evolved. It is
slightly soluble in sulphurous acid, 13 but insoluble in an aqueous solu-
tion of sodium sulphite. It is insoluble in aqueous solutions of alkali
hydroxides, but is soluble in solutions of alkali sulphides, the solubility
increasing rapidly with increase in concentration of the alkali sulphide.
From the accompanying table it will be seen that this solubility is
1 Durochor, Couipl. rc.nrl., 18f>l, 32, 823.
- Phillips, Pfjf/fj. An/)alcn., 1827, II, 476; Ro.sslcr, Zcitwh <ior<j. Client., I Si),"), 9, 3J.
a Peacock, Zi'.itsc.h. Krixt., 1033, 86, 203.
1 Hofmann, Zeitxcli. Krist., 1<)33, 86, 225.
f) Spring, Zf-it^ch. ph.yxilcal. ('/Km , ISO;"), 18, of)(); Senurniont , Ann. Chun. P/n/x , 1ST)],
[3], 32, ' \'2\): .Ditto, (?<,mpt. ?vW., IS!);"), 120, ISfi.
t; Bor^stroni, NanJ J\< itHxhtioh t, 1!>2S, 10!).
7 Sc'luu-idiT, r<>ij(j. Aiin'ilcii, IS.~)|, 91, li'i).
COMPOUNDS OF BISMUTH.
197
increased by the presence of alkali hydroxides. 1 Bismuth trisulphide is,
however, insoluble in alkali hydrosulphides : this is demonstrated by
the fact that when a solution of the trisulphide in a solution of alkali
sulphide is saturated with hydrogen sulphide, the trisulphide is com-
pletely repreeipitated. The trisulphide is also insoluble in solutions of
ammonium sulphide. In addition, the solubility in solutions of sodium
clisulphide is very much less than in corresponding solutions of sodium
monosulphide. It is probable, therefore, that the solubility of bismuth
trisulphide in solutions of alkali sulphides is due to the formation of
complex anions with the sulphide ion, S "\ and that complex anions with
either the hydrosulphide ion, SH~~, or the hydroxyl ion, Oil", are not
formed.
Bismuth does not appear to form a hydrosulphide. 2
SOLUBILITY OF BISMUTH TRISULPHIDE IN AQUEOUS
SOLUTIONS OF ALKALI SULPHIDES AT 25 C.
Concentration of Aqueous Solutions used as Solvents
Sodium
Monosulphide.
(Moles per litre).
Solubility of .Bismuth
Trisulphide
(Grams per 100 c.c.
Solution).
Sodium I Potassium. Potassium
Hydroxide. ' Monosulphide. Kydroxide.
0-5
0-0040
1-0
0-0238
1-5
0-1023
0-5
1-0
0-0185
1-0
1-0
0-0838
0-5
0-0042
1-0
0-0337
i 1-.5
0-0630
: 0-5 1-0
0-0240
1-0 1-0 0-1230
1 1-25 ; 1-25 0-235 1-
Bismuth trisulphidc is stable in air at temperatures up to 100 C. ; 3
above that temperature it begins to lose weight ; sulphur is removed on
melting, and on cooling crystals of bismuth can be detected in the mass ; 4
it is completely desulphurised by heating in the electric furnace. 5 It is
very slowly reduced by heating in a current of hydrogen, 6 and the con-
ditions of equilibrium between bismuth trisulphidc and hydrogen 7 have
1 Knox, J. Chcni. ti'ic.., 1<)09, 95, 1760. See also Abcgg, ZcM*ch. anorg. Che-m.., 1904,
30, Abegg and Bodlander, /hid., 1899, 20, 4f>3; Stillman, /. Amu. Chf-m. *SV., 1896,
83; Stone, -ilnd., 1896, 18, 101)1.
Under and Pieton, ./. Cke.tn. >SV,., 1892, 61, 132.
llo.se, Po(j(j. Aiit'.-nh'n, 1860, 1 10, 136.
Marx, X(:hwf-i(/r/r-r\-< J., 1830, 58, 472; 1830, 59, 114; Schneider, POCJCJ. Annnh.n,
, 91, 420. See also Schoeller, J. Soc. Chun, hid., 191"), 34, C, 9.
Mourlot, Compt. rc-nd., 1897, 124, 768.
Rose, Pocj(j. Annaicn, 1860, no, 136.
Brilske and Kapustinski, Tzrtt. Met., 1931, 1147; ZcitiicJi. anorg. Chan., 1930, 194,
198 AXTIMOXY AND BISMUTH.
been studied between 400 and 1000 C. The effect of the presence of
alkaline earth sulphides upon the equilibrium
Bi 2 S 3 +3H 2 ^ 2Bi +31-1 2 S
has also been studied. 1 Calcium sulphide appears to be without effect,
but the presence of sulphides of strontium and barium retards the
decomposition of bismuth trisulphide.
The trisulphide is oxidised when heated in air or oxygen ; it is
difficult, however, to eliminate all the sulphur unless the heating is
carried out in vacuo. 2 The presence of excess of bismuth trioxide also
facilitates the removal of sulphur. The calculated heat of oxidation of
bismuth trisulphide 3 is :
Bi 2 S 3 + 4-5O 2 = Bi 2 O 3 + 3S0 2 + 278,500 calories
The trisulphide, when red hot, will decompose steam ; the products
of the reaction are bismuth, bismuth trioxide and hydrogen sulphide. 4
No reaction occurs on heating with ammonium chloride. 5
The trisulphide is reduced by phosphine to metallic bismuth ;
phosphorus and hydrogen sulphide are also formed by this reaction. 6
Reduction to the metal occurs by heating on a charcoal block, the
reduction being accelerated by the presence of sodium carbonate. On
passing a mixture of air and carbon tetraehloridc over heated bismuth
trisulphide, bismuth trichloride volatilises. 7
When heated with sulphur dioxide, bismuth sulphate and metallic
bismuth are formed. 8
The sulphide does not react with a solution of potassium cyanide, 9
but it is completely reduced to metal when heated in the dry state with
that salt. 10
Freshly precipitated bismuth trisulphide reacts when boiled with an
aqueous solution of cuprous chloride and sodium chloride to form
bismuth trichloride and cuprous sulphide ; the trichloride is sub-
sequently hydrolysed. When boiled with a dilute aqueous solution of
cupric chloride, cupric sulphide and bismuth trichloride are formed in
a similar manner. In each case the bismuth trichloride may be partiallv
hydrolysed. 11 An investigation into the action of solutions of various
metallic salts upon various metallic sulphides including bismuth
trisulphide indicated that the affinity of bismuth for sulphur is greater
than that of any other element in the fifth group of the Periodic Classi-
fication, and is also greater than that of lead. 12
By treatment of bismuth trisulphide with a cold, saturated,
ammoniacal solution of mercuric cyanide, bismuth cyanide and mercuric,
sulphide are formed ; the latter is volatilised on heating, and the
1 kSchcnck and J'ardun, Z(.'.i(.*c.h. aiior'j. ('hem , 19,'W, 211, :*()!).
2 Schcnck and JSpeckmann, Zcit-wh. anoifj. ('/ten/.., 1932, 206, 378.
3 Britske and Kapustinski, toe. <nt.
4 "Regnault, Ann. Cknn. Phy*., 1830, [2j, 62, 382.
'' do Clcrmont, Conipl, r^/id., 1879, 88, 971).
11 Rose. Poaa. AtifL(il(:n. ISXO. 20. M.'Ui.
COMPOUNDS OF BISMUTH. 199
former decomposed, the resultant bismuth metal being oxidised to
trioxide by heating in air. 1
The trisulphide reacts with ferric chloride in a sealed tube ; bismuth
trichloride and ferrous chloride arc formed and some sulphur is set free. 2
With ferric sulphate a reaction takes place according to the equation
Bi 2 S 3 +3Fe 2 (S0 4 ) 3 =Bi 2 (S0 4 ) 3 + 6FeSO 4 +3S
The ferrous sulphate thus formed can be estimated by titration with
potassium permanganate and the method used for the volumetric
estimation of the trisulphide. 3
The following heats of formation from solid bismuth and sulphur
vapour, and from solid bismuth and solid (rhombic) sulphur, have been
calculated : 4
2Bi (solid) +1-JS 2 (vapour) =Bi 2 S 3 + 111,540 calories
2Bi (solid) -I- 3S (rhombic) = BigS 3 + 67,200 calories
Colloidal bismuth trisulphide may be obtained by passing hydrogen
sulphide through a very weak solution of bismuth nitrate, acidified
with acetic acid, and dialysing. 5
Thiobismuthites. Several compounds of bismuth trisulphide
with other metallic sulphides have been described, and certain minerals
which contain bismuth sulphide in. association with sulphides of copper,
silver or lead are stated to be complex compounds of this type ; some
of these have been made artificially. 6 By melting together metallic
bismuth, sulphur and alkali carbonate, Schneider claimed to have
produced complex sulphides with alkalis, 7 but attempts to repeat this
preparation proved unsuccessful. 8 On the other hand, reactions have
been described between bismuth trisulphide and sulphides of the
alkaline earth metals 9 which have resulted in the formation of the
thiobismuthitcs SrBi 2 S 4 and BaBi 2 S 4 . The corresponding compound
of calcium has not been obtained. The calculated heat of formation
of the strontium compound is 4173 gram-calories, that of the barium
compound being 13,380 grain- calories per mole.
Thermal examinations of binary systems of bismuth trisulphide
with other metallic compounds have been made, including the system
with antimony trisulphide, 10 bismuth telluridc ll and silver sclenide. 12
The results are summarised 13 in fig. 11.
1 Schmidt, Btr. t 1894, 27, 225.
- Carnmerer, Jh-.ry. J/uttc.n. Zc-i/.u/iy, 1S9J, 50, 21)5; Chc-ia. Zenlr., 1801, ii, 525.
:1 Hanus, ZcilMli. anory. Chaw., 1898, 17, 111.
4 Britske and Kapusunski, Ze.itacli. awry. Chem., 1930, 194, 323; Tzvct. Jl/e/.,
1931, 1147.
5 Wiussiiiger, Hull. Acad. Bely., 1888, [3], 15, 403.
(> Schneider, J. pnikt. Chttn., 1889, [21, 40, 504; Rosslcr, Zeitach. a-n-ory. Chem., 1895,
9, 47.
7 Schneider, I'oyy. Annahn, 1869, 136, 464; 1869, 138, 309.
8 Muir, J. Chc.w. Soc., 1878, 33, 199. See also Ditte, Com.pt. rend., 1895, 120, ISO;
Mdbauer, ZfAtach. an-ory. Clic/m., 1905, 42, 441.
9 Schenck and l^rdun, Zeitxch. a-iiorg. Cha/i., 1933, 211, 209. See also Schenck, ibid.,
1933, 211, 203.
10 Takahashi, Mttn. Coll. Sci. Kyoto, 1919, 4, 47.
11 Aimulori, Alii 11. Ac.cad. Lined, 1915, 24, II, 200.
12 Pehxbon. Coinnt. rend.. 1908. 146. 975.
200 AXTTMOXY AND BISMUTH.
The ternary system bismuth-sulj^hiir-tellurium has also been in-
vestigated, 1 the results pointing to the existence of one ternary com-
pound only, Bi 4 S t? Tc 3 or Bi 2 S 3 .Bi 2 Te s . Several minerals are 'known
Sb 2 S 3
BLS, 650
700 90 80 70 60 50 40 30 20 10
Mois. BL 2 <5j per cent.
FK:. I I. Freezing Point. Cur\cs of the Systems l>i.,S. ! -Sb.,S. , Bi,S.-Bi To
containing bismuth, sulphur and tellurium, but their constitution is
unknown. Orurtitc, to which the formula Bi s S t r iV has been ascribed
is revealed as a mixture (or solid solution) when examined by X-rays.
] n, Ca ^^ Amadon, Alt! R. Acrml. Line*'*, lOIS, 27,
y^li. plnj# t kl. Cheln., JSJ)7, 22, 609.' cc \ij.so 7/l/lV/^/^L'// Crfhwl VV^^l^S, 1 ^
COMPOUNDS OF BISMUTH. 201
Bismuth, Oxygen and Sulphur.
Numerous compounds of bismuth with oxygen and sulphur have
been described. The majority of these are basic salts of uncertain
constitution. Certain naturally-occurring minerals may possibly be
oxysulphides, such as karelinite l and bolivite, 2 but the evidence does
not appear to be sufficient to decide their true nature. A substance of
composition corresponding to Bi 2 O 3 S has been obtained as a greyish-
black powder by the action of dry hydrogen sulphide upon bismuth
pentoxidc (the latter probably containing tetroxide), and by passing
hydrogen sulphide through a suspension of bismuth pentoxide in
boiling benzine. It is stable in air up to 120 C. 5 but when heated above
that temperature is converted into bismuth trioxide and sulphur
dioxide. It dissolves in hydrochloric acid with evolution of hydrogen
sulphide. 3
Bismuth Sulphites. -Normal bismuth sulphite has not yet been
obtained, but a number of basic compounds have been obtained. They
are all white, powdery substances obtained by the action of a solution
of bismuth nitrate in nitric acid upon a solution of sodium sulphite.
The nature of the product depends upon the temperature and con-
centration of the solutions. 4 Among the sulphites that have been
described arc: 9(BiO) SO 3 .(BiOH)SO 3 .2HoO, 4(BiO)oSO 3 .(BiOH)SO,.
5H 2 0, 2(BiO)oSO r 3(BiOH)S0 3 .2H O, " 3(BiO)oSO v 7(BiOH)SO 3 .
1()H. 2 ; (BiO) 2 SOV3(BiOH)S0 3 .H 2 0. "By the actWof hot sulphurous
acid upon bismuth trioxide, a white, powdery compound has been ob-
tained to which is ascribed 'the formula (Bid) 2 S0 3 .2(BiOH)SO 3 .4H 2 O.
It is stable in air, insoluble in water, but slightly soluble in sulphurous
acid, from which it may be reprceipitated by dilution. 5
Bismuth Sulphate. In addition to the normal sulphate, a number
of other compounds, most of which arc basic, has been obtained. The
products obtained by crystallisation from solutions of bismuth trioxide
in sulphuric acid vary in composition according to the temperature and
concentration of the solution employed. 6 From an investigation of the
equilibrium of the system Bi 2 3 .4S0 3 -H 2 SO 4 -II 2 ; it is" found that
the solid phase in equilibrium with liquid containing CO to 90 per cent,
of sulphuric acid is Bi 2 3 .4SO 3 : when the concentration of the liquid
phase falls below 47-5 per cent, of sulphuric acid the solid phase in
equilibrium is Bi 2 O 3 .2SO 3 , when the concentration falls below 1-37 per
cent, acid the solid phase is a mixture of Bi<>O 3 .S0 3 and Bi 2 O 3 .2S0 3 ,
and when the concentration falls below 1-09 per cent, acid Bi 2 3 .S0 3
alone remains as the solid phase. 7
Normal bismuth sulphate may be obtained by dissolving bismuth
trioxide, bismuth trisulphide or bismuth nitrate in excess of concentrated
sulphuric acid, evaporating the solution to dryncss and heating the
1 kamnu'LsL'ero;, J\I mcnilcfu-.-m.., KS7f>, i, 195; Hermann, J. prakt. Ch-c./n., 1858, 75,
4-1S: Groth, "TaicUc-n^ 4th Kd., p. 49.
- Crotli, !<. (-,( , p. IS; Doinoyko, C</n<p{. rc-nd., 1877, 85, 977.
3 Gmdin-lvraurs ^ IJandbnch df-r unrtrytnischkn Chcr/uc." (Heidelberg, 19()S), Vol. Ill,
Pail '2, ]). 979.
1 Sen boil and. Klten, Zf./f^rh. an ore/. Chart , 189,3, 4, 72. See also Caglioti and Malossi,
Ail i It. Arrail. Linc+i, 1929, [(>], 10, 97.
' .RoJiri.ir, ,/. prakt. Chc'm., 1888, [2], 37, 2-11.
202 ANTIMONY AND BISMUTH.
residue very carefully. 1 It is a white, powdery or finely crystalline
substance, very hygroscopic, forming a hydrate Bi 2 (SO 4 ) 3; 7H 2 6, which
loses water at'lOO C., becoming a dihydratc. Bi 2 (SO 4 ) 3 .2H 2 O" It can
be heated to 400 C. without decomposition, but above that temperature
decomposition sets in, basic salts being produced. On strongly heating,
Bi 2 O 3 .SO 3 is obtained, 2 while at red heat all the sulphuric anhydride is
driven off. 3 It can be reduced to metal by heating in a current of
hydrogen 4 or ammonia. 5 It is hydrolysecl slowly by cold water, more
rapidly by hot water, forming in each case 6 Bi 2 O 3 .SO 3 . With hydrogen
chloride it forms addition compounds, 7 the following having been
obtained : Bi 2 (S0 4 ) 3 .4HCl, Bi 2 (SO 4 ) 3 .2HCl, Bi 2 (SO 4 ) 3 .HCl. It forms
double salts with the sulphates of the alkali metals and ammonium.
With lithium sulphate two compounds have been described, 8 Li 3 Bi(SO 4 ) 3 .
2lI 2 O and Li(BiO)S0 4 .H 2 O. With sodium sulphate 9 the compound
Bi 2 (SO 4 ) 3 .Xa 2 SO 4 has been described; with potassium sulphate 10 the
double salt Bi 2 (SO 4 ) 3 .3K 2 SO 4 is obtained in the form of hexagonal
crystals ; the existence of the compound Bi 2 (SO 4 ) 3 .K 2 SO 4 , which had
previously been described, 11 has not been confirmed. The ammonium
compound Bi 2 (SO 4 ) 3 .(NH 4 ) 2 SO 4 has also been described. 12 Two com-
pounds with cerium sulphate,Bi(OH)S0 4 .Ce(SO 4 ) 2 .5H 2 arid 2Bi 2 (SO 4 ) 3 .
( 1 e(SO 4 )o.l5lI 2 O, have been described, and solid solutions are also
found iu this system. 13
Bismuth sulphate- is isomorphous with the sulphates of yttrium,
lanthanum and " didymium." 14 It is said to be able to confer upon
certain other substances the property of phosphorescence. 15
Acid liivmuth Sulphate, Bi 2 3 .4SO 3 .7H 2 O, is obtained by the action
of moderately concentrated sulphuric acid upon bismuth trioxidc, the
basic sulphate first formed being rcdissolved in a large excess of sulphuric
acid. 16
In addition to the foregoing, several other sulphates, both acid and
basic, have been described ; it is possible 1 that many of them are mixtures
of the normal sulphate, bismuth oxide 1 and water. The following may
be mentioned : HuO,.SO. { , Hi.,O.,.SO v 2lI 2 O, Bi 2 O r S() r 3H 0, 17 3BUO.,.
S( ),,.:*! I ,,(>, 1H 5Bi/),.'llSO,.17lL,O, Bi t) () v -l.SO,j.IIoO/Bi.,6 3 .4SO r llo6,
HLO.1.1SO.J. I0ll.ro>
1 La-el hjdni, Hc/nrnyjo'ti ./-, 1817, 17, 41(5; Leist, An-n(il-<:n., 1871, 160, 29; Scluiltz-
Sclla.-k, tin., 1S71, 4, I.'*; '.Mari^nai-, Ann. (!fnm. /Y*//.v., 188-1, [()], I, 294; ,/. prakL Ghr.tn..,
I Shi, (2j, 30, 2-1-1, Hrns<_'rn, Rcc. Tr<u: rhini., 1885, 4, 409; .Bailey, J- Chnn. ,S'oc., 1S87,
.Si, H7H; (Max-en, ./. I'tnkt. Chun., 1 H91 , [2 J, 43, m.
' llcini/,, !*<>'/<[. Ati/ialf n, 1N-1-1, 63, 77.
'' P.aih-y, luc'. 'at .\ Schmidt, Jin:, IK94, 27, 2,'M.
1 Ai[\('(lson, ruijij. An null-it, 1S24, I, 74.
Hod.'kiijsoii and 'IVcnch, C/tn/i. -Vn/',s, 1 W92, 66, 22.'{. (; Hcns^cn, loc. at.
. />'/., 192(5, 598, 790, Hcn.s.L'cn, /or. cit.
Alii A'. Accnil. Linen, 19.'U, [(>), 13, 77f>.
c, Annul* //, 1SOO, 140, 277.
uid Stolfi, Attt A'. Accail. Linen, J9:>7, [<5j, 5, S9(i.
. ('/ion. ./.. 1892, 14, 81.
nitloi, 18(5(5, 140, 277. Sec, liowc.vor, ( 'a.^liot.i and Malossi, Attl ft.
[(>], io, 97.
>nainiiu, f><r.::< ila, 192I5, 53, 7(51.
. (inonj. ('hnn., 1901, 27, 2f>4.
(.'nntpt. mid., 188(5, 103, (>29, 10(54; IS87, 104, 1(580; 1887, 105, 45,
I.i-U, Inc. cit.; Adic, lac. cil.; Allan, luc. cit.
Hi-int'/, /'f'i/:/. Annalni, 184-1, 63, 55.
Athanascscu, Coinpt. roul., 188(5, 103, 271. 1<J Adic, he. cit.
COMPOUNDS OE BISMUTH. 203
Bismuth Thiosulphates. Bismuth thiosulphate itself has not yet
been prepared. Addition of a, thiosulphate to a bismuth solution results
in the precipitation of bismuth trisulphide, a reaction which has been
recommended for the separation and detection of bismuth. 1 Several
complex compounds containing bismuth and alkali or alkaline earth
thiosulphates have been described, however ; solutions of these are in
general acid, and do not respond to the usual reactions for thiosulphates
unless they are made neutral ; 2 it is suggested that they contain an
unstable anion Bi(S 2 O 3 ) 3 =.
Sodium Bismuth Thiosulphate, Na 3 Bi(S 2 O 3 ) 3 , is obtained in the form
of orange-yellow crystals when bismuth nitrate is rubbed with excess of
sodium thiosulphate. The mixture is extracted with aqueous alcohol,
and the compound precipitated as a yellow oil by addition of more
alcohol, crystals being obtained by drying over sulphuric acid. 3 A
solution of this salt has been suggested as a reagent for the detection and
estimation of potassium, 4 but has been found unsatisfactory for the
purpose, as the potassium salt precipitated is always contaminated with
the sodium salt. 5 A crystalline precipitate of sodium bismuth thio-
sulphate has also been obtained by the action of aniline and alcohol on
a solution containing bismuth oxynitrate, acetic acid and sodium thio-
sulphate. 6 By the interaction of a solution of bismuth nitrate in
maimitol 7 and sodium thiosulphate in the presence of manganese
chloride a compound, more stable than, that described by Hauser, has
been obtained in the form of small octahedra 8 to which the formula
XaJBi(S 2 O 3 ) 3 has been ascribed.
Potassium- Bismuth Thio sulphate, K 3 Bi(S 2 O 3 ) 3 , is obtained by pre-
cipitation from a solution of the sodium salt on adding a potassium
salt and alcohol, 9 or by the addition of solutions of potassium chloride
and sodium thiosulphate to one of bismuth trioxide in hydrochloric acid. 10
It may be obtained in the anhydrous and hydrated forms. The corre-
sponding salts of rubidium and caesium, Rb 3 Bi(S 2 O ;3 ) 3 and Cs 3 Bi(S 2 O 3 ) 3 ,
both of which arc yellow, crystalline powders, ammonium, (NH 4 ) 3
Bi(S 2 3 ) 3 , strontium, Sr 3 [Bi(S 2 O 3 ) 3 ] 2 , barium, Ba 3 [Bi(S 2 O 3 ) 3 ] 2 , silver
and copper have been prepared in a similar manner. 11 The barium and
strontium salts arc readily hydrolyscd by water, the silver salt decom-
poses in a few seconds with the formation of a black compound, while
the copper salt is precipitated only on the addition of alcohol.
By the interaction of the double thiosulphate of sodium and thallium
with bismuth trichloride, a thallium bismuth thiosulphate, Tl 3 Bi(S 2 O 3 ) 3 ,
is obtained. It may also be prepared by the interaction of a thallous
salt with potassium bismuthothiosiilphate, but it is soluble in excess of
the latter. 12 It is a sparingly soluble, microcrystalline yellow powder.
Although moderately stable in neutral solutions, it is readily decomposed
1 Vortmann, Mo-nuMi., 1880, 7, A 18; Faklor, Pkann,. Povl, 1900, 33, 301, 317.
- Hauler, Zcitsch. a-nory. Chcm., 1003, 35, 1; Cuisinicr, Bull. Soc. chim., 1922, 31, 1064.
3 Hauser, foe. cit.
4 Carnot, Covi.pl. rend., 1876, 83, 338, 390; 1877, 84, 1504; 1878, 86, 478.
5 Kusier and Crutcrs, Zuf.xch. anorg. Chem., 1903, 36, 325; Cuisinicr, lac. cit.
r> Sanchez, Bull. Soc. cMm., 1912, [iv], n, 440. See also Cuisinier, luc. cit.
7 Vanmo and Hauser, Zeitxch. anorg. Chem., 1901, 28, 210.
8 Yamno and Mussgnug, Arch, rharni., 1919, 257, 264.
9 Carnot, Comvt. rer/rf ./1876, 83, 338. 390.
204 AXTDIOXY AXD BISMUTH.
by acids with evolution of sulphur dioxide and precipitation of bismuth
trisnlphidc, the latter being quantitative.
Attempts to obtain bismuth dithionate and bismuth trithionate
have proved unsuccessful. 1
BISMUTH AXD SELRXIUM.
Three compounds of bismuth and selenium have been reported.
Bi 2 Se, BiSc and Bi 2 Se ;5 . Of these BiSc and Bi 2 Sc 3 are probably true
compounds, 2 the latter being the more stable. Octahedral crystals of
bismuth subselenide, BioSc. arc stated to be formed, when selenium is
melted with a large excess of bismuth. 3 The existence of this compound,
however, has not been confirmed. The melting point curve of the
system Bi-Se indicates the formation of the monoselenide, BiSe, which
decomposes at 602 C. (sec fig. 10, p. 195). This compound is di-
morphous, with a transition point at 422 C. On heating bismuth with
excess of selenium, the triselenide, Bi 2 Se 3 , is formed.' 1 The mineral
silaonite, found in Mexico, to which the formula Bi 8 Se a was formerly
given, 5 is more probably a mixture of the triselenide Bi 2 Se ; , with
bismuth.
Bismuth Triselenide is found in the minerals guannjudtite and
Jre-ttzelite. It .may be obtained by melting together the elements, but
on account of the case with which selenium volatilises, to obtain the pure
compound it is necessary to add more; selenium to the product first
formed and remelt in the absence of air. 7 It is formed when hydrogen
sclcnide is passed into a solution of bismuth nitrate from which excess
acid has been almost completely removed, 8 or by the addition of a solu-
tion of a bismuth salt to a. saturated solution of hydrogen selenide.
The hydrogen selenide is best prepared by I he ac.tion of hydrochloric
acid on magnesium sclcnide in the absence of air. If is probable that
by the last-mentioned process bismuth selenide is obtained free from
deposited metal and from complexes. :)
In the mineral form bismuth triselenide is isomorphous with the
minerals bismut hinite and ant inumite. 10 Its hardness on Molls' scale is
2-5 to .'J-;5, and its density (r"2 to (>(): it is commonly associated with
sulphur minerals, and indeed sulphur may partially replace selenium.
In the prepared form it is a. black or grey powder with a. density of 0-S2.
When heated it loses selenium and absorbs oxygen. 1(. is only ycry
slightly attacked by concentrated hydrochloric acid even on boiling;
dilute nitric acid has little action, but concentrated nitric acid ami
aqua regia decompose it completely with partial separation ol selenium.
It is insoluble in solutions of potassium hydroxide or potassium sulphide.
It is oxidised to the trioxide when fused with pota.ssium nitrate,
potassium selenate being formed at the same time. It reacts with the
1 Vanino ;i iicl Mu.^mit
" I 'an a vano and ( 1 aiJ
:1 Rossler, Znlsr/i n'nu
1 IV-lahon, ./. C/ntt, jihi/x, 1!M>1, 2, :^ 1 ; I'a rr;i \ a no, Cir-dtn, li)i:i, 43, I,
Tomoshiur, MI 1/1 ('nil. N(,.' A //o/o, l'.)|'.), 4, f>7. See also I titrfunlintitil Cndnil Tuhlt-
IDliS, 4, L.T,. ' '' Mallet, Jft/nh. Miner., 1SSO, Mil).
(; Brims, f /,ril.<th. Kii/.^f Mm , ISS-J, 6, !K>.
7 Seiineidcf, I'otjtj Annnhn, 1 So"), 94, <i^S ; \.\\\\i\Animlfii, \ So*), 1 12, '2 1 '.}.
8 t'elsmann, Annahn, IS(1(), 116, \'2~>.
<J iMoscr and Atvnski. .Mannish.. 1112."). /m. ^!M.
COMPOUNDS OF BISMUTH. 205
double chloride of bismuth and ammonium when melted, with forma-
tion of bismuth selenochloride, BiScCl.
Thermal investigation of the system Bi 2 S ;i -Ag 2 Se has been under-
taken, 1 and from the melting point curve it is deduced that a double
compound 3AgoSc.4Bi.,S ;i is obtained, the melting point being 773 C.
(see fig. 11, p/200).
Two selenites of bismuth have been described, the first, Bi 9 O 3 .
4-Se0 2 , being formed by the addition of selenious acid to bismuth
carbonate, and the second, Ei 2 3 .oSeO 2 .H 2 O, by the action of excess
of selenious acid upon bismuth hydroxide. 2
A compound which may be bismuth selenate is obtained in the
form of very small, colourless prisms by boiling bismuth carbonate with
excess of sclenic acid and removing the excess acid by heating. 3 It is
insoluble in water and is not decomposed by boiling water ; it dissolves
in mineral acids, but is decomposed by alkalies. The existence of
selenites and selenates of bismuth has not, however, been confirmed.
BISMUTH AND TELLURIUM.
By the action of hydrogen telluride or sodium telluride upon a salt of
bismuth, a monotelluride, BiTe, has been obtained. 4 which is described
as being unstable in air, as having reducing properties and as being
soluble in acids. No evidence for the existence of this compound has,
however, been obtained from thermal (see fig. 10, p. 195) and micro-
scopic examinations of the system Bi-Tc, bismuth tritelluride,
Bi 2 Te 3 , being the only definite compound of the two elements indicated. 5
Bismuth telluride occurs in certain minerals, while a thiotelluride,
Bi 2 Tc 2 S, occurs as tetradymite. It is probable that the mineral mon-
tanite 6 contains a bismuth tellurate, (BiO) 2 Tc0 4 , in a hydrated form.
No compound of this type appears, however, to have been obtained
artificially.
Compounds described as thiotelhiritcs, of doubtful composition, were
mentioned by Bcr/clius. 7 Such compounds do not appear to have been
examined subsequently.
BISMUTH AND CHROMIUM.
Bismuth Chromite, 3Bi 2 O 3 .2Cr 2 O 35 is prepared by heating
bismuth oxychloridc with chromium trioxidc and water for several
hours. 8 It is a brown powder which is insoluble in water, in acids
(including aqua regia) and in alkalis.
Many chromates and dichromates of bismuth have from time to
time been described/' but all except two are probably mixtures. These
1 lY'labon, Conipt. rund., 1008, 146, 07;").
- Xilson, Bull. xS'or. c/uw., .1875, [2|, 23, 408.
;! Cameron and Mat-Allan, J'roc. Roy. Xoc , 18SO, 46, .13.
Brukl, M<,/il.*/t.., 1025, 45, 471.
ru, <,/i.*t.., , 45, .
5 Monkemevrr, Zcilxch. (in.nry. Ch<-)ii., 1005, 46, 415; Pelabon, An.,ti. Cfia//. /V,',.yx.,
1000, 17, 52('> ; "Amadon, Afli />'. Arcfifl. Linen, 1018, 27, I, 131 : Cfi"lf(t, .19 IS, 48, II, 42;
ndo, ,S'o. /!</,. Taliokn .Imp. run:, 1025, 14, -170; 1027, 16, 201. Sec also I nt<-rnfttt<>n<d
nl/rnl. Tdhir*, 10i>S, 4, 28.
(l (it-nth, A ///</: J. Nr/., I SiS, |2j, 45, 300.
7 Ht-r/diiis, 'J.rhHmr/,^ IS20. ^' 8 Bri.u.LiS, ./. d/i'-m. Nor., 102!), 132, 212.
11 Lowe, J. pralcl. Cltf-ni., 1S5C>, 67, 288, 4(53; Pearson, 1'kd. Alntj., 185(5, [4j, II, 204;
uir, J. Chciti. A'oc., J87(), 30, 15: 1877, 31, 24; Sclnnid, 1/t/t ><(j. Jh.wrtttlntti. E/Uttirjen.,
.Mu, . . ., , ,
1801. See also Briggs, loc. cit.
206 AXTIMOXY AND BISMUTH.
two compounds may be obtained by the action of chromic acid upon
bismuth trioxide. If the concentration of the acid exceeds 7-8 moles
per litre the substance Bi 2 O 3 .4-Cr0 3 is obtained as a stable salt ; if
the concentration falls below that figure, this salt is hydrolysed and
the substance Bi 2 O 3 .2CrO 3 is obtained. 1 The former is an orange-
scarlet powder and is perhaps a mixed dichromate and chromate,
Bi 2 Cr 2 7 (CrO 4 ) 2 ; the latter is a basic salt, and is obtained as an orange-
yellow powder. It may also be prepared by the action of potassium
chromate or dichromate on a nearly neutral solution of bismuth nitrate. 2
Several double chromates with alkali compounds have also been
described. 3
BISMUTH AXD MOLYBDENUM. ETC.
Bismuth compounds react with molybdates, phosphomolybclates
and tungstates to form insoluble substances. 4
BISMUTH AND NITROGEN.
Bismuth Nitride, BiN. When potassamide is added to a solution
of bismuth tribromide or triiodide in liquid ammonia, a dark brown
precipitate of bismuth nitride, BiN, is formed ; it is very unstable,
decomposing explosively when acted on by water, or when heated. 5 It
has been used as a nitriding agent. 6
Bismuthyl Nitrite, or Basic Bismuth Nitrite, 2BiON0 2 .H 2 0, is
obtained as a yellowish-white precipitate when sodium nitrite is added
to an aqueous solution of normal bismuth nitrate and mannitol. The
anhydrous salt can be obtained by drying over sulphuric acid in a
vacuum desiccator. 7 The salt decomposes when heated above 60 C.,
with evolution of nitrogen tetroxide.
Although attempts to prepare pure normal bismuth nitrite have not
proved successful, a number of complex nitrites, or bismuthinitrites,
have been obtained. 8 They may be prepared by precipitation from a
strong solution of alkali nitrite by bismuth nitrate or a mixture of the
nitrates of a third metal and bismuth. Two groups of salts have been
prepared, the simple bismuthinitrites, for which the general formula is
M 3 Bi(NO 2 ) 6 , and the mixed bismuthinitrites, having a general formula
M 2 M / Bi(NO 2 ) 6 , where M represents ammonium, potassium, rubidium,
caesium or thallium, and M' represents one of the three metals lithium,
sodium or silver. All possible compounds of the first type, except that
of ammomum. have been obtained, as also have all possible compounds
of the second type. All the salts are highly crystalline, the simple type
forming orange or yellow hexagonal plates, but the mixed type pale
yellow to red crystals, probably octahedral. The simple bismuthinitrites
of caesium and thallium differ somewhat in constitution from the normal
type, the ccesium compound, Cs 3 Bi(N0 2 ) 6 .Bi(NO 2 ) 3 , containing an
additional molecule of bismuth nitrite, while that of thallium,
1 Cox, Zf-itsdi. anorcj. Gkf.rn., 1906, 50, 22(5.
- Muir, loc. c'lt.
3 See this Series, Vol. V.I I, Part 111, p. 48.
' Caspar y Arnal, Ann. Chini. apjjl., 192!), II, 97.
and lira nates 'of bismuth, see this Henes, Vol. VJI, Part; ill, pp. MO, 21 5, :*
COMPOUNDS OF BISMUTH. 207
Tl 3 Bi(XO 2 ) 6 .TlNO 2 .H O, contains an additional molecule of thallous
nitrite. 1 All compounds that have been prepared are readily hydrolysed
by water ; the simple bismuthinitrites are generally less stable and more
soluble than the mixed salts. Attempts to prepare compounds con-
taining two metals of the M group, or two of the M' group, have proved
unsuccessful ; so also have attempts to prepare salts of the type
M / 3 Bi(XO 2 ) 6 , thus, sodium bismuthinitrite has not been, obtained in the
solid form, but is probably produced in solution when bismuth nitrate
is added to a solution of sodium nitrite. The reagent prepared in
this way has been suggested for use in the detection and separation of
rubidium and caesium, while the solution obtained by adding the nitrates
of bismuth and caesium to a solution of potassium nitrite has been used
for the estimation of sodium, owing to the formation of sodium ccesium
bismuthinitrite, which is soluble only with difficulty. This substance,
however, appears to vary in composition according to the method of
preparation. 2
In addition, a number of bismuthinitrites containing nickel have
been prepared by the addition of a salt of any of the metals of the
M group to a solution containing nickel nitrate, bismuth nitrate, and
sodium or lithium nitrite. 3 The composition of these compounds has
not in. all cases been definitely established.
By the addition of a saturated solution of bismuth nitrate, in vary-
ing proportions, to a saturated solution of sodium cobaltinitrite, three
distinct bismuth oxycobaltinitrites, or bismuthyl cobaltinitrites, have been
obtained, 4 ranging in colour from brick-red to yellow and having the
compositions (BiO) 3 Co(XO 2 ) 6 , (BiOJ 3 Co(XO 2 ) r J and (BiO) 3 Co(NO 2 ) 4 ,
respectively. These compounds are all very hygroscopic. They are
decomposed by water on standing, arc readily decomposed by acids with
evolution of nitrogen peroxide, and by solutions of sodium and ammon-
ium hydroxides. They are insoluble in ether and only slightly soluble
in alcohol. The following co-ordination formulae have been suggested :
[Co(X0 2 ) 6 ]3BiO, [Co(X0 2 ) 5 (BiO)]2BiO, and [Co(NO 2 ) 4 (BiO) 2 ]BiO.
Normal Bismuth Nitrate, Bi(XO 3 ) 3 .5lI 2 O, is obtained by dis-
solving powdered bismuth in nitric acid ; on crystallising from solution,
large, prismatic, tri clinic crystals having the elements
a : b : c = 0-8053 : 1 : 0-6172 ; a -90 4' ; /J = 10'J. 26' ; y =79 6'
are formed, 5 being isomorphous with those of the corresponding but
labile nitrates of the rare earth metals ncodymium and praseodymium. 6
Its density is 2-7 to 2-8. 7 On exposure to dry air at the ordinary tem-
perature the nitrate disintegrates and is gradually converted into a basic
nitrate. 8 It cannot be dehydrated completely by phosphorus pent-
oxide, as decomposition sets in. 9 The action of heat on the normal salt
is extremely complex, and the results obtained by different investigators
] Ball and Abram, J. Che.ni. Soc , 11)13, 103, 2110.
- Ball, J. Chem. 8oc,., 1900, 95, 2126; 1910, 97, 140S.
3 Ball and Abra.ni, loc. cit.., p. 2120.
' l Oo-burn, /. An).f). Ch<m. ,SV,r., 1923, 45, (Ml.
r> HannneLsbcM'^, I Iditdhuc.h, I SSI, 1, 3(U>.
c Bodman, 7>V/-., I89S, 31, 1237: Zcitxch. a-nory. Chcm., 1901, 27, 25-1 ; Urbain and
Laeombe, ,/. Chhn. phi/*., 1900, 4, .105; tYiend, ,/. 'CJif-m. Soc., .193;"), 138, 824, M31.
7 .Playfair and Joule, Memo,,* C/if-nt. ,S'or., 1845, 2, 401; Clarke, Amc.r. J. XcL, 1877,
[31, 14, 2SJ.
8 Kugc, /. 'prakt. Chf.m., 1865, 96, J 17.
9 Picon, Hull. Soc. ch'im., 1925, 37, 1365; CompL rend., 1925, 181, olG.
208 AXTBIOXY AND BISMUTH.
are conflicting. 1 Rutten 2 observed that at 72 C. a little liquid is
formed, but that maintaining the mass at that temperature does not
produce more liquid. The remaining crystals, freed from liquid, melt
at 75-5 C., giving basic salt and liquid. The trioxide results at 425 C. 3
Earlier workers, however, stated that the anhydrous oxide was formed
at as low a temperature as 260 C. The First product of decomposition
appears to be the basic nitrate, 2BiONO ;V II 2 0, but several other pro-
ducts have been reported.
Bismuth nitrate is soluble in water, but excess of water must be
avoided ; the solution, which is acid in consequence of hydrolysis,
rapidly decomposes 4 with the formation of oxynitrate, BiOXO 3 . It is
soluble in nitric acid, and the refractive power of the solution has been
studied. 5 It is insoluble in anhydrous hydrofluoric acid, 6 but readily
soluble in an. aqueous solution of mannitol, 7 forming a clear solution
which probably contains complex compounds. 8 This solution may be
employed for the preparation of many bismuth salts.
The sesquihydrate, 2Bi(XO 3 ) 3 .3H 2 6, is obtained by treating Bi 2 3 or
the normal pentahydrated salt with fuming nitric acid. It is very
deliquescent. 9 A dihydrate, Bi(X0 3 ) 3 .2H2O, has also been prepared.
Many double nitrates have been obtained 10 of the type 3M(X0 3 ) 9 .
2Bi(XO 3 ) 3 .24H 2 0, in which M represents magnesium, zinc, nickel,
cobalt or manganese. They are prepared by dissolving the simple
nitrates in the smallest quantity of hot, fairly concentrated nitric acid,
and allowing the solution to crystallise. These double salts are iso-
morphous with the similar double nitrates obtained by substituting
metals of the rare earths for bismuth. They are all decomposed by
water. Magnesium bismuth nitrate, Mg 3 Bi 2 (XO 3 ) 12; 24lI 2 O, is colourless ;
its density is 2-32, and it melts with decomposition at 71 C. Zinc
bismuth nitrate, Zn 3 Bi 2 (X0 3 ) J2 .2lJI 2 0, is colourless; its density is
2-75, and it melts with decomposition at 67-5 C. Nickel bismuth nitrate,
Ni 3 Bio(XO 3 ) 12 .24H 2 0, is green ; its density is 2-51, and it melts without
decomposition at 69 C. Cobalt bismuth nitrate, Co a Bi 2 (NO 3 ) 12 .'24lI.>0,
is orange-red ; its density is 2-48, and it melts without decomposition at
58 C. Manganese bismutJt, nitrate, Mn 3 Bi 2 (XO 3 ) 12 .2 I-II 2 O, is pale red;
its density is 2-42, and it melts without decomposition, at 1-3 to 4 1- C.
In addition, mercury bismuth nitrate, IIg 3 Bi 2 (XO 3 ) 12 .24lI 2 O, has been
obtained; 31 it forms solid solutions with magnesium bismuth nitrate
containing up to 25 per cent, of the mercury salt. Magnesium bismuth
nitrate has been employed for the separation of the metals of the rare
earths. 12
From an examination of the behaviour of normal bismuth nitrate,
1 Berzelius, Gilbert''* A-nnulc-.n., 18.12, 40, 28(>; Gladstone, ./. }irnL'L Cfi.f-.nt., 1835, 44,
179; Graham, Annul, .18.39, 29, 10; Vvon, C'nn/pt. rend., 1877, 84, 1 J (5 1 ; Bito, Aoyanm
and JMatsui, J. tioc*. Chc.m. hid., Japan, 1932, 35, J9.~>. For more complete bibliography
and discussion, see Picon, loc. at.
- .Rut ten, Zdtsch. a-norg. Chcm., 1902, 30, 342. :{ 1'ieoii, loc (lit.
* Grouvello, An.n. Chin/.. /V/v/.v., 1821, [2], 19, 111; Duflos, Xchirnf/yrr'* J., 1833, 68,
19; Antoni and Giidi, Uttzzfltu, 'l898, 28, 248.
5 Baden- P(\vell', !'<./(/. Annnlcn, 184(>, 69, 110; Diisclieincr, Htl:;ntnjbrr. A'. Ahnl.
'\\"IK*. \V-i<-n, 18()4, 49, 32(i.
(; l^redetiha^en and Cadenbaeh, Zalxch. [>hii.<ihul. C/n-tti., 1930, A 146, 21-").
7 Varnno and Marti, ZrUxck. (iu<>r<j. Chun.,' 1 90 1 , 28, 2<)l.
8 DC; Carli, Ann. ('him. (t]>j>lic<it<i, 1 ( .)31, 21, 172.
'' Rutten, toe. ci.t. 1() L'rbain and Lac-ombe, ('<>*}>( rr,,n., 1903, 137, ."OS.
COMPOUNDS OF BISMUTH. 209
and of compounds of this salt with certain sugars and other organic
substances, 1 it has been suggested that the co-ordination formula
should be
i (IT 2 0),1X0 3 .H 2
X0 3 jXO,.H 2
From a solution of bismuth nitrate in aqueous ammonium nitrate
there is obtained by crystallisation a double compound which may be
represented by
r Bi (Nir 1 xo 3 ) 3 nxo 3
L NO, JXO-j
Basic Bismuth Nitrate. The earliest investigators were well
aware that bismuth nitrate is decomposed by water ; indeed a cosmetic
known as "Spanish White" was prepared in tin's way. 2 Many sub-
stances have been described as resulting from the hydrolysis of bismuth
nitrate, but there can be little doubt that main' of these are mixtures.
The composition of the product obtained depends upon a number of
factors, such as the quantity and temperature of the water employed,
the time that the precipitated substance stands in contact with the
liquid, the process of washing, etc. 3
The system Bi 2 O ; >-N 2 O 5 -II 2 O has been systematically in-
vestigated, 4 and the various compounds produced by hydrolysis have
been examined by analysis and by titri metric measurements, and from
the results co-ordination formula have been given. 5 The first product
obtained by the action of cold water, or very dilute nitric, acid, upon
normal hydratcd bismuth nitrate is the compound Bi O ;J .XoO 5 /2ri 2 O,
or BiONOo.rioO, which forms very thin crystalline 'plates showing
double refraction. When this body is treated with a little warm water,
or when it is allowed to stand in contact with liquid containing not
more than six per cent, of nitrogen pentoxide, monoclinic crystals of
the basic salt Bi 2 0,.N 2 O 5 .II 2 O oi ; [BiO(NO,).Bi(OiI)o]XO, are" formed.
This compound may also be obtained in the form of thin hexagonal
prisms by the action of heat upon the hydratcd normal nitrate, which
decomposes at about 72 C. Its solubility in water falls with rise of
temperature. When the compound BiON T O ;J .IL,O is allowed to slandin
contact with very dilute solution, or when the normal nitrate is decom-
posed by n large excess of water, rhombic crystals of a complex compound
6Bi 2 3 .5X.,O r ,.0(8)II 2 or l 2 n;} 2 ^
arc obtained. The same compound is obtained in the form of hexagonal
plates when the basic compound .13i 2 O ;i .N.,0 5 .iI 2 O is acted upon by excess
of warm water. The final product obtained by hydrolysis, using boiling
1 Hcpncr and Likicrnik, Arch. Phann., 192G, 264, 46.
2 Ivopp, " Geschichtc. dc/r C hernia*'' (BraunschnviLr, 1847), Vol. TV, p. HO.
3 Schamclluuit, ./. Pharui-. Px-Pj(>., 1929, II, 21 ; J-lc-rbcrm'T, R.c.pc.rlarhi,m. fiir dir>. Phar-
mac c, 1836, 55, 281), 300; Ulteren, hc.rzdiH* J(ihr<>*h<-r'u'hl(-, 183!), 17, 101); DiiHos, Arch.
Phu-ui., 1840, [2], 23, 307; llomfz, J. -prali. O/ifui.. JS4S, 45, 102; < Hadstono, 3/r.moirs
Che n. >S"or:., J 84 5-1847, 3, 480; ,/. ?,m/,7. (;k<-m., 18-48, 44, 179; Rcctkcr, Arch. I'fut.-nn.,
1S-1'\ [-1,55, h 1 -- ) ; 1S.V1, 12|, 79, 1; Janssc-n, Arch. Phnm, , l.sr,!, |2|, 68, 1, 129, 'Duik,
Pep rLnn-iDiifur 'he. Phdrmddc, \ S H , } 2 j, 33, 1; Lii(l(lc(;kr, .-1 /<//</////, 1 S<iU, 140, 227 ; Dil.ic,
Cwi pf. read., IS74, 79, 0;")6; Knusscau and Tii<\ C(nn(. rc/i'l., IS92, 115, 17 1-; Yvoii,
hull. Xuc. rh'nn., 1877, f, 491.
1 van l^ominolon and KuLlen, Pror,. K . AI:nd. \Vf.l f-.ti^rh. Ahuli-nlam, 1900, 3, 19(5;
Rutten, Zuttich. (tnory. Chu,i. 7 1902, 30, 342. .See also Ditto, />/., 1S74 ; 7, 1044; Allan,
J. Aincr. Chem. /S'oc., 1903, 25, 307. 5 Jfcpncr, Arch. J'harm.., 192G, 264, 55.
VOL. VI. : V. T '
210
AXTBIOXY AXD BISMUTH.
is 2Bi 2 Oo.X 2 G 5 .H 2
water,
hexagonal crystals.
or
BiO(NO 3 ).BiO(OII), which forms
By precipitation from solutions of bismuth nitrate with ammonium
hydroxide, the basic nitrate (Bi 2 3 )o.N 2 O 5 .XI 2 O is obtained. 1 Similarly
the basic nitrates Bi 2 O 3 .XoO 5 and 2Bi 2 O 3 .N 2 O 5 are obtained by the
action of sodium acetate upon solutions of bismuth nitrate. 2
From measurements of electrical conductivity it has been shown that
hvdrolvsis of bismuth nitrate occurs even in the presence of excess of
10 20 30 40 50
Grams N 2 5 per WO grams Solution
60
nitric acid ; 3 from these measurements it; is also deduced that the
compound BioO.>.No0 5 .2lI>O js nob produced directly, but that an
intermediate compound, which may perhaps be .BiOII(XO ; >)o, is formed
first. This compound docs not appear to have been isolated.
Basic, bismuth nitrate combines with certain sugars to form com-
pounds in which the NO., group is not ionised.' 1
In addition to the above-mentioned substances, two oilier basic
compounds have been obtained, .Hi 2 O r 2X 2 O 5 .2l! 2 O and "l()Hi 2 O.,.
<)X O v 7lIoO. Other basic salts mentioned in the literal uro would
appear to be mixtures. 5
In the following tables are given (he solubilities of the basic and
normal nitrates of bismuth at. different, temperatures in various con-
centrations of nitric acid. The solubilities arc expressed as gra.ms of
BLO.J and NoO f) respectively per TOO grains of solul ion.
1 Ilarkspill and KiH'lVr, An;i. <"/////;., lU.'iO, [ HH, 14, 'I'll.
~ Kliartnaiidaryan. ,/. ]\H.<H. riii/* ( 'hcin . ^<>r.^ IDl'S, 60, 1177.
:> ' (Juariai-olli, (,'(i:~rtlfi, 1 !)!.'>, 43, i, 1)7.
' llrpncr atui I,ikiemik, Aic.h. I'li'trni., J!)'J(), 264, -1(5.
COMPOUNDS OF BISMUTH. 211
SOLUBILITIES OF BASIC BISMUTH NITRATES.
Solid Phase.
J3i 2 O 3 .
I
Authority.
20 j Bi 2 O 3 .X 2 O 5 .H 2
Ei,0,.N O v 2H
65
Bi.,Oo.XoO. v HoO
Grains. Grams.
13-67 12-50 i Ruttcn, Zeitsch. anor".
14-85 13-31
Chem., 1902, 30, 342.
18-74
15-90
23-50 *
19-25 *
27-15
20-96
28-11
21-64
29-50
22-53
30-19
22-90
31-48
23-70
0-063
0-554
Smith. ,7. Amer. Chem.
0-335
1-163
Soc'., 1923, 45, 360.
1-126
2-368
2-23
3-61
3-49
4-84
5-03
6-21
5-55
7-44
Rutten, loc. cit.
26-72
22-46
* Mean of two separate experiments.
SOLUBILITIES OF BISMUTH NITRATE PENTA-
HYDRATE, Bi(NO 3 ),,.5H 2 O.
Temp., .... ()
I Q -OloUo.
X,0 5 . ! Authority.
Temp.,
0.
BJ 2 3 .
X 2 5 .
Authority. \
i Grams.
Grams. '
Grams.
Grams.
! 1.0-71
27-11 'F. and H.*
30
32-13
27-15
F. and II. .
14-17
30-03
28-20
29-60
Ruttcn.
I , 8-57
38-02
17-50
41-10
F. and II.
5-30
47-17
16-10
47-70
Ruttcn.
5-92
56-37
18-18
50-67
F. and II.
i 20 32-97 t
24-85 t lluttcji.
50
35-63
30-76
F. and IT.
32-63 t
24-65f
30-85
35-06
32-24
24-68
28-21
40-00
30-29 y
25-22-f
29-79
43-69
24-16
28-25
16-62
35-40
65
37-82
35-80
Ruttcn.
12-17
43-37
11-66
46-62
11-10
49-79Y
15-20
3t -no
20-76
53-75
212 AXTDIOXY AXD BISMUTH.
The results contained in this second table are shown diagrammatically
in fig. 12.
SOLUBILITIES OF BISMUTH NITRATE SESQUI-
HYDRATE, 2Bi(NO 3 ) 3 .3H 2 O.
(Rutten.)
' At
20
C.
Bi
A ...
8
58 grams
i 4-05 grains
N,
,O 5 . . .
68
28
74-90 ; ,
: At
65
c.
Bi
A . - .
4
59 ;
\
,O- . . .
/ / c
00
!
The quadruple points corresponding to the coexistence in equi-
librium of the phases Bi 2 0.>.X 2 5 .H 2 O-E.i(XO 3 ) 3 .5H 2 O- -Solution-
Vapour, at various temperatures, are as follows :
BASIC QUADRUPLE POINTS.
Point in
Fig. 12.
Temp.,
C C.
Bi,0 a .
! X 2 5 .
i
i Autliority.
Grams.
Grams.
A
30-8
22-8
Friend and Hall.
B
9
3M
23-85
Rutten.
C
20
32-97
24-85
i .,
D : 30
34-2
20-5
i
E i 50 ;
36-9
28-9
E ! 50
37-7
29-0
i Friend and Hull. .
F 65
40-8
31-6
i Rutten.
These points appear to be fairly \vcll established, some. 1 of them having been
obtained by extrapolation from a considerable number of solubility data.
The following quadruple points are inven by Uutlen and correspond
to the coexistence in equilibrium of the following phases : Hi(X().,).,.
5lI 2 O-2Bi(XO 3 ) 3 .OlI 2 0-Solution Vapour. These points are open to
criticism in that the data from which they were derived appear
somewhat scanty. For this reason the curves connectino-
data in these regions arc shown as broken lines in (i<f. V2.
ACID QUADRUPLE POINTS.
(Button, loc. cit.}
Point in
FJI:. 12.
Temp.,
COMPOUNDS OF BISMUTH. 213
The conditions of equilibria above 65 C. arc very uncertain, for the
dihydrate, Bi(NO ; ,) J .2H 2 0, appears, and the experimental diflieulties
are considerable.
BISMUTH AND PHOSPHORUS.
Bismuth Phosphide. -No definite compound of bismuth and
phosphorus appears to have been obtained in a pure condition. It has
been suggested that a small quantity of the monophosphide, BiP, may"
be formed when the two elements are melted together, 1 and that this is
also formed as a black substance when dry phosphine acts upon bismuth
trichloride, 2 or when phosphine is passed into a solution of bismuth
nitrate. 3 It is completely decomposed when heated.
Bismuth Hypophosphite, Bi(H 2 P0 2 ) 3 .H 2 O, is obtained as a
white crystalline powder by the action of potassium or barium hypo-
phosphitc upon a solution of bismuth nitrate. 4 It is decomposed very
readily by beat, phosphine being evolved at temperatures a little above
100 C. At higher temperatures some metallic bismuth is formed, and
the reaction may possibly be represented by the equation
3Bi(H. 2 P0 2 )3=2Bi-f-Bi(P0 3 )3-i-6P-r9lI 2
It is also readily decomposed by water. 5
The use of bismuth hypophosphite in conjunction with hydrogen
peroxide has been suggested for the quantitative separation of bismuth
from other metals. 6
A basic hypophosphite, BiO.H 2 P0 2 , has also been described as
resulting from the action of bismuthyl hydroxide, BiO.OII, upon
hypophosphorous acid. 7 It also is unstable and appears to resemble
closely the normal hypophosphite.
Bismuth Phosphite, Bi 2 (HPO 3 ) 3 .3H 2 O, is precipitated from a
solution of ammonium phosphite by the addition oi' bismuth trichloride,
by neutralising phosphorous acid with bismuth trioxide or hydroxide, 8
or by the action of phosphorous acid upon an aqueous solution of
bismuth nitrate and mannitol. 9 The white needle-like crystals arc only
slightly soluble in water.
Bismuth Orthophosphate. The normal salt only, BiPO 4 , is
obtained by the addition of disodium phosphate to a nitric acid solution
of bismuth nitrate. 10 Ac-id salts do not appear to have been prepared. u
The microscopic, monoclinic prisms of the normal salt have a density
of 0-328 at 1 5 C. The substance is slightly soluble in bismuth trichloride,
and from molecular weight determinations in this solvent the Formula
appears to he BiPO 4 . 12 It is reduced by heating in a current oi' hydrogen, 13
but not by carbon monoxide. It is not hydrolysed by water, even after
1 .Marx, Hchiw'Kjfjc-fs ,/., 1830, 58, -171. 2 Cava/zi, Gdzzr-.tta, 188-1, 14, 219.
3 Berzdius, " Lchrbuch," 1826; Lanclgrcbc, SchiM>ffi/(-rs -/., 1828, 53, -160.
4 Hada, -/. Chan, tioc., 1.805, 67, 229;" Vanino and '.Hartl, ZttL-ich. anunj. Cht)n., 1000,
[2], 74, U2.
Calca^
Vnmi
Grui '/A
Van i
w.('d. (Buenos Aires), 1928, 35, 1042.
7, 30, 2001: Vanino and Treuberi, Btr., 1898, 31, 121).
or, Arch. J'hanx., 1897, 235, 093.
and Hard, J. prakt. Chun., 1 1)0(5, [2], 74, 142. Sec aLso Calea^no, loc. cit.
]() Chancel, Coitipl. rw.L, I860, 50, 410; 51, 882; de Schulten, Bail. ;S'oc. ch-mi., 1903,
[3], 29, 720; Calea^no, An miles oficnui qu'nn.. provliicla, (Buenos Airo.s), 1928, 2, 1.
11 Monteniartnu'and E^idi, Gdzztllu, 1(300, 30, .11, 377, 421.
12 Cavcjti and Hill, J. Soc. Chtni. ItuL, 1897, 16, 29; Kuglieimer, Anu'dtn, 1905, 339,
349. ia Hcintz, Poyy. Annultn, 1844, 63, 507.
214 ANTIMONY AND BISMUTH.
prolonged boiling. 1 A trihydrate, BiPO 4 .3H 2 0, has been prepared, 2 and
also a white, insoluble basic salt, 2BiPO 4 .3Bi 2 O :) . 3 Investigation of the
solubility of bismuth orthophospluite in hydrochloric acid 4 at 25 C ('.
indicated that it was conditioned by the concentration of the chloride ion
and oi' the hydrogen ion, but was independent, of the concentration of
phosphoric acid. It is suggested that the main reaction which occurs
on solution may be represented by
BiPO 4 +3HC1 =H[BiCl 3 .H 2 P0 4 ]
It has been stated that pyrophosphate and metaphosphate of bis-
muth cannot be prepared in the wet way owing to their rapid conversion
into orthophosphate by the action of water. 5
Bismuth Pyrophosphate, Bi 4 (P 2 O 7 ) 3 , has, ho\vcver, been prepared
by the action of bismuth trioxide on molten mierocosmic salt. 6 It. is a
white, amorphous powder, almost insoluble in water but decomposed by it.
A complex salt, sodium &^smi^/z^^ro^os7J/^//^,Xa(BiP 2 O 7 ).3H 2 O 5 has been
prepared by dissolving bismuth pyrophosphate in sodium pyrophosphate.
In this compound the bismuth appears to form part of the anion. 7
Bismuth Thiophosphate is formed by the action of phosphorus
pentasulphide on bismuth trichloride. 8 It is a reddish-brown or black
substance which is readily fusible without apparent decomposition and
can be crystallised from the melt. It is not readily soluble in the usual
solvents. It is decomposed by dilute hydrochloric acid with evolution
of hydrogen sulphide ; it is first oxidised and then dissolved by nitric
acid. It is not attacked by solutions of alkalies.
A very unstable substance, which may be bismuth dithiophosphate,
BiPS 2 O 2 , is obtained by the action of magnesium dithiophosphate
upon a bismuth salt. It is, however, readily decomposed even in ice-cold
water and in alcohol. 9
BISMUTH AND AKSEXIC.
Bismuth Arsenide may be obtained by passing ursine through
a solution of bismuth trichloride containing a minimum quantity of.'
hydrochloric acid. 10 It is a black substance, unattackcd by water,
dilute acids or alkalis, but decomposed by concentrated hydrochloric
acid with formation of arsine. It is an active reducing a^ent.
Bismuth Arsenite. When arscnions acid acts upon a solution of
sodium bismuth chloride, a white precipitate is formed, which is stated
to be bismuth arsenitc, BiAs0 3 .5H 2 0. The substance has not been
obtained pure. 11
Bismuth Arsenate probably occurs naturally in the minerals
atelestite, rhagite, Kalpurgite and inixlte. It may be obtained as a white
crystalline substance by the action of arsenic acid or alkali arsenate
upon a nitric acid solution of bismuth nitrate. 12 The hemikydrate,
1 Caven and Hill, loc. ciL See, however, Moniemartini and E<Jdi, loc. c/L
- Vanino and liartl, l(;C. ciL 3 Cavazzi, Gazzttla, 18S-1, 14, 281).
4 Jensen, ZtilscJi. auory. Cham., 1934, 219, 238.
5 Moniemartmi and Egidi, loc. c/L
6 Wallrolh, .thill . Soc. rh-un.., 1883, [2], 39, 3.1(5.
7 J-loscnhcini and Triantaphvllidcs, tttr.. 1915, -
COMPOUNDS OF BISMUTH. 215
BiAs0 4 .JH 2 O, which loses water only when heated strongly, forms
microscopic monoclinic prisms, density (at 15 C.) 7-1 t'2 ; it is tasteless
and melts only with difficulty. A basic arsenate, 2BiAs0 4 .^Bi.>O 3 ,
lias also been prepared by the action of.' sodium arsenate upon an
ammoniaeal solution of bismuth citrate. 1 It Forms a gelatinous pre-
cipitate, which resembles the corresponding phosphate in its chemical
properties.
BISMUTH AXD ANTIMONY.
No binary compound of bismuth and antimony has as yet been
obtained : the two metals form a continuous series of solid solutions. 2
Two antimonates of bismuth have been prepared by the addition
of a concentrated solution of potassium meta-antimonatc to a solution of
bismuth ammonium citrate. 3 The first, which is variously described as
bismuth oxymeta-antimonate, (BiO)SbO 3 , or bismuth orthoanti-
monate, BiSb0 4 . is obtained as an amorphous white precipitate ; while,
in the presence of excess of ammonia, a basic orthoantimonate,
(2BiO) 3 Sb0 4 .H 2 O, is obtained as a gelatinous precipitate. The com-
position of the latter docs not appear to have been definitely ascertained. 4
BISMUTH AND CARBON.
Carbon will not dissolve in bismuth. 5
Bismuth Carbonate. The normal salt is unknown ; a basic
carbonate, (BiO) 2 CO 3 , is precipitated, however, as a white powder when
sodium carbonate is added to a solution of bismuth nitrate. When
dried it retains from one-hair to one molecule of water. The density
of the product varies with the concentration and temperature of the
solutions ; the product of lowest density 7 is obtained at 45 C. The
basic carbonate may also be prepared .from a solution of bismuth nitrate
containing mannitol. An electrolytic method has also been described. 8
The electrolyte is a :3 per cent, solution of sodium chlorate charged with
excess of carbon dioxide ; the anode is of bismuth and the cathode of
carbon, zinc, iron or aluminium.
It has been suggested that the composition of basic bismuth car-
bonate is in most cases !j more accurately represented by the formula
CO(O.BiO).,.
It is insoluble in water even in the presence of carbon dioxide ; it
is also insoluble in alkalis, but is slightly soluble in alkali carbonates.
From these solutions it may be reprceipitatcd either by boiling, or by
the addition of an alkali. It darkens in colour on exposure to light. 10
It is used principally in medicinal preparations.
Basic bismuth carbonate occurs naturally in the minerals bismutite,
basobivmutite and bismutospkue.rite.
Cyanides. When, potassium cyanide is added to a solution of
1 Cava/./i, GazzcUa, 1884, 14, 28!).
- Huttner and Tummuim, Zr-ilxcJi. unary. Chc'/u,., 11)05, 44, 131. See also pp. -'12, 152.
3 Cavazzi, GazzcUa, 1 8S5, 15, 37.
4 See also Hampe, Z<', t .txch.. anal. Chan., 187-1, 13, 192.
5 Moissaii, Corn-jit, read., 1890> 122, 1.462.
(; Seubert and Klton, Zf-itwh. cttwrtj. Clic.m., 1893, 4, 4-1; Lcfort, CompL rend., 1.848,
27, 208. See also Picon, Bull. tioc. ch-hn., 1929, 45, 1050 ; Slickings and Coupland, Chc-nnsl
and .Drurjrjist, 1928, 108, (305. 7 Jones, Phu-ni. ,/., 1925, 115, 143.
8 Carreras, K-ritwh Pate ill, 1927, 298587.
9 Vanino, Pkann. Zeiil-r.-h., 11)11, 52, 701.
10 Taplcy and Gicsy, J. A-mcr. Pliarm. Asscc., 1.92(3, 15, 40.
210 AXTIMOXY AXD BISMUTH.
bismuth nitrate a brown precipitate is obtained, the composition of
-which is doubtful. Early investigators considered it to be an oxide,
probably a peroxide, of bismuth. 1 but it was found to contain sulphur,
which may have been due to impurities in the potassium cyanide. 2
By triturating calculated amounts of bismuth bromide and potassium
cyanide with small quantities of xylene a reaction occurs from which
a complex salt, potassium bis'nnithobromo cyanide, K 3 [BiBr 3 (CN).J, is
obtained. This compound is decomposed by cold water, but is soluble
in dilute hydrochloric acid, the solution however decomposing rapidly.
When heated out of contact with air, potassium bromide and metallic
bismuth are obtained. In a similar manner other complex salts have
been obtained, such as the orange-yellow silver salt, Ag y [BiBr 3 (CN) 3 ],
the greenish-grey cuprous salt, Cu 3 [BiBr 3 (CX) 3 ], and a mercury salt,
Hg 3 [BiBr 3 (CX) 3 ] 2 , which is at first sulphur-yellow, but changes to white
prismatic needles. These salts are all decomposed by water. 3
Other complex cyanides that have been obtained are bismuth,
ferrocyanide, Bi 4 [Fe(CN) 6 ] 3 , which is formed by precipitation with
potassium ferrocyanide ; 4 bismuth f err icy anide,^ bismuth cobalticyanide,
BiCo(CN) 6 .5lI 2 O, a greenish-white crystalline substance which turns
blue on drying, and when dried over sulphuric acid has the formula
2BiCo(CN) 6 .7H 2 O. 6
Bismuth Thiocyanate, Bi(CXS) 3 , is obtained when thiocyanic
acid is neutralised with bismuth hydroxide. 7 It is possible that a basic
compound is also obtained. 8 Dilute thiocyanic acid solution must he
used ; basic substances are probably formed first, but on cooling, bright
orange or amber-coloured rhombic crystals of normal bismuth thio-
cyanate separate, having the elements
a : b : c =0-76134 : 1 : 0-28423
The crystals are decomposed by water, and on heating. The hydrate
Bi(CXS) 3 .14-H 1 >O is obtained in the form of deep-red transparent
needles by the action of excess of thiocyanic acid upon bismuth carbon-
ate ; when the acid is saturated with bismuth carbonate, basic bismuth
thiocyanate, Bi(CXS) 2 OH.5H 2 0, separates in glistening plates on
addition of alcohol.
Bismuth Chromothiocyanate, Bi[Cr(CXS) G ], has also been
described. 10
When a solution of potassium thiocyanate is added to a solution
of bismuth thiocyanatc. an orange-red coloration, is obtained ; various
considerations have led to the vie\v that solutions of bismuth thio-
cyanate in thiocyanic acid contain bismuth othiocyanic acids. It is
suggested that in concentrated solutions an acid of the formula
1 Fresenius and 1-laidlcn, Aiinulcii, 18-12, 43, 135; Bodecker and Deichmann, Aii.rtdku,
18C2, 123, 61 ; Muir, TIoiTineister and "Robbs, J. Clitiii. Sue., 1881, 39, 25.
2 .Hotlmain), Jnnakn, 1884, 223, 131.
3 Yournazos, CompL rend., 1921, 172, 535.
4 Werner, Zntsch. a-nal. Chc.iti., 1919, 58, 23. Hoc also Atterber<r, Bull. Soc. cktm.,
1875, [2], 24, 355; AVyrubolI, Ann. Chun. Fhyx., 1870, |5"J, 8, 448; Muir, J. Chc/m. Soc.,
1877, 31, 051; 1877, 32, 40.
5 See this Series, Vol. IX, Tad, 11.
(: Fischer and Cuntze, Chf-.m. Zcit., 1902, 26, 872; filler and Matthews, J. Amer.
C/i(-'in,. ,S'oc., 1.900, 22, 02; Matthews, J. Aincr. Chcm. Soc., 1900, 22, 274.
7 Bender, Btr., 1887, 20, 723. 8 MeitzendoriT, Poyy. Aiuialc-n, 1842, 56, 63.
COMPOUNDS OF BISMUTH.
217
H[Bi(CNS) 4 ] is obtained, while in dilute solutions the tribasie acid,
II 3 [Bi(CNS) 6 ], is formed; in view of this, the formula of bismuth
thiocyanate itself may be regarded as Bi[Bi(CNS) 6 "J. In sup|)ort of tliis
hypothesis, a number of complex thiocyanates have been prepared,
whieh can be represented as salts of tribasie bismuthothiocyanie acid. 1
By adding potassium thioeyanate to an aqueous solution of bismuth
nitrate and mannitol, precipitating the mannitol and potassium nitrate
by addition of alcohol, and crystallising from the filtrate, red, non-
hygroscopic crystals of potassium bismuthothiocyanate, K 3 [Bi(CXS) 6 ],
are formed. Another potassium salt, K 3 Bi(CXS) G .3KCXS, has also
been obtained. In a similar manner corresponding salts of sodium and
ammonium have been prepared, although not in a pure condition. 2
By adding thallium acetate to potassium bismuthothiocyanate in
appropriate proportions two complex salts of -potassium and thallium
have been obtained, namely, the orange-yellow salt K 2 TlBi(CXS) G , and
the pale yellow salt KTl 2 Bi(CXS) G . Attempts to make the pure
thallium salt failed. 3 Among other salts of this type that have been
obtained are the zinc salt, Zn 3 [Bi(CXS) 6 ] 2 , as large, non-hygroscopic,
orange-red crystals ; the cobalt salt, Co 3 [Bi(CXS) 6 ] 2 .15H 2 O J reddish-
brown crystals, the colour of this salt supporting the view that a com-
plex bismuth anion is formed, since Bi 2 [Co(CXS) 4 ] 3 would presumably
be dark blue ; the nickel salt, Xi 3 [Bi(CXS) 6 ] 2 .10H 2 O, greenish-yellow ;
the vanadyl salt, (VO) 3 [Bi(CXS) 6 ] 2 .7H 2 O, a reddish-violet powder ; and
the /erne salt, Fe[Bi(CXS) 6 ], lustrous green crystals. The thallium salt
of monobasic bismuthothiocyanie acid, Tl[Bi(CXS)J, has also been
formed as red crystals. 4
BISMUTH AND SILICOX.
Bismuth Orthosilicate, 2Bi 2 3 .3Si0 2 , is found in nature in the
minerals culytite and agricolite, the former crystallising in the tetra-
hedral system and the latter in the monoclinie. Thermal and micro-
scopical examination of mixtures of bismuth trioxidc and silica revealed
the existence of several silicates which have since been synthesiscd. 5
These are indicated below.
Formula. i M.pt. ( C.).
Density (20 C.). :
Bi 2 (K.8Si0 2 I 002 6-623
Bi 0- 3SiO 3 847
8-107 i
Bi 2 : j.2Si0 2 873
8-657 '
2Bi 3 .3SiO.> : 736 to 877
8-084
BioOij.SiO/ I 772 to 800
8-024
3Bio03.2Si6.> ! 701
8-388 ;
2BioO; 3 .SiO/ i 803 to 843
0-138
&I3io0 3 .Si(X : 822
8-807 i
IGBioO'ij.SiO^ i 832
0-136 !
1 Paciello and J'oa, Gazzrlta, 1023, 53, 5:20.
2 Va.nino and Hauscr, Zettsch. an.org. Chem., 1901, 28, 219.
3 Carmeri and J^rina, Gazzclla* 1922. 52, 1, 231.
ANTIMONY AND BISMUTH.
X AND ESTIMATION ()!' .BlSMLTlf.
Detection. Dt'ij Tests. Bismuth. compounds, when healed on. a,
charcoal block, are' reduced : a brittle globule of metallic bismuth is
obtained, with a yellow incrustation of bismuth trioxide. If the
original compound is mixed with powdered charcoal, potassium iodide
and sulphur, and the mixture heated on a charcoal block, a scarlet;
incrustation is obtained.
When a mixture of metals containing bismuth is heated in a hard
o-lass tube under a hard vacuum, a characteristic ring is formed on the
tube indicating the presence of bismuth. 1 With a vacuum of 0-001 mm.
the presence of 0-01 per cent, of bismuth can be detected by this method.
Wet Tests. Bismuth is usually identified in solution by precipitation
as brown trisulphidc. The precipitation is effected by passing a current
of hydrogen sulphide through a warm solution acidified with hydro-
chloric acid. The precipitate is insoluble in yellow ammonium sulphide.
but is soluble in hot, dilute nitric acid and in sulphuric acid. The
presence of bismuth may be confirmed by dissolving the precipitate of
trisulphidein dilute nitric acid, reprecipitating the bismuth as hydroxide
with ammonium hydroxide, redissolving the hydroxide in dilute hydro-
chloric acid, and allowing the clear solution of bismuth trichloride
to drop slowly into excess of water. A copious white precipitate of
bismuth oxychloridc is obtained by hydrolysis.
Bismuth compounds are readily reduced by reducing agents such as
formaldehyde in alkaline solution, hypophosphorous acid, or sodium or
potassium stannite. In each case a black stain or residue is obtained,
by means of which the presence of bismuth may be determined.
Potassium iodide reacts with solutions of bismuth salts to form black
bismuth triiodide, which readily dissolves in excess of the reagent to
form a yellow or orange solution which probably contains potassi
iodobismuthatc. This reaction may be employed as a spot test for
detection of traces of bismuth in the presence of copper,
cadmium. 2
An electrolytic method has been suggested for the detection of bis-
muth in slags. A piece of the slag is connected to the positive polo of a
battery and an aluminium plate to the negative pole. If a, filter paper,
saturated with a solution of potassium iodide, is pressed between the
slag and the aluminium plate, the presence of bismuth is indicated by
the formation of a reddish-yellow coloration on the filter paper. 3
Bismuth may be detected in gold alloys by employing the streak
test. The streak is dissolved in aqua regia", the" metals arc'precipita.l rd
as sulphides by hydrogen sulphide, the sulphide precipitates are digesf cd
with yellow ammonium sulphide and finally dissolved in nitric" acid
The presence of bismuth is detected by adding to a minute drop of I his
solution a drop of solution of potassium sulphate, when the ch " '
sulphate of bismuth and potassium is precipitated. 4
.Many organic reagents have been employed for the dctectioi
bismuth A 2 per cent, solution of 8-hydroxyquinolinc contain,
nitric acid or sulphuric acid is mixed with a 4 per cent, solution
190, ,->;
COMPOUNDS OF BISMUTH. 219
potassium iodide immediately before use. This reagent produces a
llocciilent ora.nge precipitate when added to a solution containing
bismuth if the concentration of the bismuth exceeds 1 part in 1.00,000.
The precipitate is soluble in a mixture of acetone and ammonium acetate,
and in cv/c'/ohexaiie, and these solutions may be employed in the colori-
mctric determination of bismuth. 1
Other reagents that have been employed are methylephredine
methiodide, 2 viscose 3 and sodium alizarinsulphonate. 4
Estimation. Gravimetric Methods. (I) As bismuth trioxide.
Bismuth is precipitated from solution as basic bismuth carbonate, the
reagent being ammonium carbonate. The precipitate is then ignited
and weighed as bismuth trioxide. This method is not suitable for
solutions which contain hydrochloric acid or sulphuric acid.
(2) As bismuth oxy chloride. In this method the solution contain-
ing bismuth, which is faintly acid, is just neutralised by ammonium
hydroxide, care being taken to avoid precipitation. The solution after
neutralisation may be opalescent. A small quantity of dilute hydro-
chloric acid is now added, and the precipitated oxychloride allowed to
settle for a considerable time. The precipitate is finally dried at 100 C.
and weighed as oxychloride.
(3) As bismuth trisulphide. Hydrogen sulphide is passed through
a warm, acid solution containing the bismuth, the trisulphide being
precipitated. The precipitate is washed successively with a solution
of hydrogen sulphide, alcohol, and freshly distilled carbon disulphide.
Final washings are made with alcohol and ether, after which the pre-
cipitate is dried at 100 C. and weighed as trisulphide.
(4) As metal, (a) The method of Rose. 5 Bismuth is precipitated
as basic bismuth carbonate and. the dried precipitate is reduced by fusion
with potassium cyanide. The salts formed are dissolved out with water
and the metal collected. (Precautions must be taken as the crucible
is liable to be attacked during fusion.)
(/;) The method of Yanino and Trcubert. 6 The bismuth compound
in solution is reduced by the action of formaldehyde in the presence of
excess of sodium hydroxide. The bismuth may either be estimated
as metal, or preferably it may be rcdissolved in. nitric acid and estimated
as oxide (see method (1 )). This method can be employed in the presence
of hydrochloric and sulphuric acids. The results, however, are liable to
be high unless special precautions are taken.
(5) Bismuth may be precipitated from its solutions by means of
selenious acid. 7 The precipitation is effected in a nitric acid solution.
It is preferable to convert the bismuth selenite to bismuth trioxide
before weighing.
3 Sa/.erae and rouzergues, COID^L runt. Sue. tiivi., 1932, 109, 79, 370.
2 .Feng, J. Awe,,'. Pkann. Atxoc., 1.1)32, 21, 8.
3 Taincliyna, Ch^in. JAtly, 1930, 24, 31.
-1 Gennuth and 'Mitchell, Amtr. J. Pharm.., 1929, 101, -j(i. Sec also TougarmofT, Ann.
/S'oc. >S'a". Jiruxc.llef!, 1930, 50 B, .M5; Agost.mi, AH/I.. Chini. ay^licala, 1929, 19, JG-1-.
For further literature on. the detection of bismuth, sec Heller, JMikfocJivnii?., 19150,
8, 33; Heller and Krunihok, ibid., 1929, 7, 213; Gutzeit, Jldv. Ohlm. Ada, 1929, 12,
7J3; Tammann, Heinzel and Laars, Ztdlisch. a/i.ory. Cheta., 1928, 176, 143.
3 Ko.se, Po(j(j. A;i',tatc,n, I860, no, 425.
(i Vamno and Trcubert, BLT., 1898, 31, 1303; ixunp and Hainann, Zcitach. amiL
Chcm., .1931, 87, 32.
7 Tiinakoshi, J. Clic/m. Soc. Japan, 1932, 53, 433; Buoherer and Meier, Ztilsch. anal.
Cheni., 1931, 83, 352; Berg and Teitelbaum, ZtUach. anorg. Cht'ni., 1930, 189, 101.
220 ANTIMONY AND BISMUTH.
(6) Miscellaneous methods. Bismuth may be precipitated as a
brick-red, granular complex substance, bismuth chromium thiocyanate,
13i(Y(ONS) G , by the addition of potassium chromium thiocyanatc to a
solution of bismuth containing nitric acid. 1 The precipitate may be
dried at 120 to ltf(r ('. and weighed. This method may be employed
in the presence of iron, chromium and sulphuric acid, and it is claimed
that, in certain circumstances, it is to be preferred to the sclenious acid
method.
Triethylencdiarnine cobaltic chloride has also been used as a reagent
for the estimation of bismuth. 2 The solution of the bismuth compound
is made in dilute hydrochloric acid, and is treated with potassium iodide
to form potassium iodobismuthate. To this solution is added a con-
centrated solution of triethylenediaminc cobaltic chloride, the bismuth
being precipitated as a reddish-yellow, crystalline precipitate,
(Bii;) 2 (tocn 3 )I.
" Cupferron " may be employed for the estimation of bismuth m
either hydrochloric or nitric acid solution. The bismuth is ultimately
determined as trioxide. This method may be employed for the separa-
tion of bismuth from many other metals. 3
Volumetric Methods. Various methods of estimating bismuth
volumctrically have been described. A solution is made in nitric acid,
and from this, basic bismuth oxalate is precipitated with ammonium
oxalate. This precipitate is then dissolved in hydrochloric acid, the
solution neutralised with ammonium hydroxide, and any precipitated
hydroxide redissolved in sulphuric acid. This final solution is then
heated to 70 C. and titrated with a standard solution of potassium
permanganate.
The following indirect method may also be noted. To a fairly acid
solution containing bismuth, a solution of potassium bromide is added
until the precipitate of bismuth oxybromide which forms at first is
redissolved. The solution is now neutralised with sodium hydroxide
and a freshly prepared, saturated solution of [Cr(XII 3 ) ( .J(XO ; J ;5 is added
in excess. The precipitate is then distilled with a solution of sodium
hydroxide and the expelled ammonia collected in a known volume of
standard acid solution, the excess of which is ultimately titrated with
a standard solution of sodium hydroxide. In this reaction six molecules
of ammonia are equivalent to one atom of bismuth.' 1
Other volumetric methods are mentioned in the section on the
nucrochcmical estimation of bismuth.
Colorhnctric Methods. The yellow-orange or red colour produced by
the solution of bismuth triiodide in excess of potassium iodide is
frequently employed for the colorimetric estimation of bismuth. The
sample is dissolved in nitric acid, glycerine is added, followed by a solu-
tion of potassium iodide. Comparison is made by a similarly treated
standard solution containing bismuth. 5
1 ]\Jahr, Zc,it.<:ft. diior'j. Ckcm., 11)3:2, 208, 31;.).
~ Spacu and hhieiu, Zctfwh. nnuL C/wt/!., 1029, 79, KM).
3 Pinkus and Demies, Bull. S^r. rhrin. Bcly., .10:28, 37, 20
on the LI ran metric eslmiai ion of bismuth, sec Ishimaru, J. C-h
566: Lee, v'W., 1931,52,229, Galloway, Jim., J. A,w. Oj\(<:
Solodovnikov, ,SV.v. licp. tituic U nil. Kajtni* 1028, 88, -157.
4 Mahr, Zeitach. unal. Chc.-m.., 1933, 93, -133.
5 Thresh, Pharm. J., 18SO, [3], 10, 641. See also Yalyashko and Virup, Ukrainsbii
Kfitni. Z/i-u/'., 1930, 5, 275, 293; Prick and Engomann, Chem. Zeit., 1029, 53, 5U5; Porinov
and Skvorzov, Farm. Zhur., 1028, 534; Ck^ni. Ze/itr., 1929, i, 114.
COMPOUNDS OF BISMUTH. 221
Thiourea may also be employed in the colorimetric estimation of
bismuth. Solid thiourea is added to a bismuth solution containing
a slight exeess of acid. A yellow coloration is obtained, due to the
formation of various complex compounds, and may be compared with
the colour obtained with a standard solution containing bismuth. If
ferric iron is present, the solution should be boiled with hydraziuc
sulphate. 1
If a solution of bismuth nitrate is added to a solution of cinehoninc
potassium iodide a crimson or orange coloration is produced, the in-
tensity of the colour depending upon the amount of bismuth present.
Lead, arsenic, antimony and tin must first be removed, and the bismuth
solution must be added to the reagent. Comparison, is made with the
colour obtained with a standard bismuth solution. This method is
suitable for the estimation of small amounts of bismuth of the order of
0-00003 to 0-00015 gram. 2
Microchemical Methods. A volumetric method has been devised for
the micro-estimation of bismuth. The bismuth is precipitated as oxy-
iodi.de and the precipitate is decomposed by treatment with a solution
of potassium hydroxide. The iodide present is then oxidised to iodate
by the action of chlorine, potassium iodide is added and the liberated
iodine titrated with a standard solution of sodium thiosulphate. 3
A concentrated solution of /?Y/n.s-dithiocyanato-diethylencdiamino-
eobaltic thiocyanate reacts with a faintly acid solution of bismuth nitrate
(to which excess of potassium iodide has been added) to form the orange-
yellow compound di thiocyanato-dicthylencdiamino-eobaltic iodobis-
muthate, [Co en 2 (SCX) 2 ]BiI 4 . This reaction maybe employed both for
macro- and micro-estimation of bismuth. 4
Other reagents which have been suggested for use in the micro-
estimation of bismuth arc quinolinc, 5 a solution of pipcrazine in acetone, 6
viscose, 7 and hcxamcthylenc-tctranvi ne. 8
Electrolytic Methods. Bismuth may be estimated eleetrolytically in
acid solution. A nitric acid solution is frequently employed containing
not more than 2 per cent, of free acid. 9 Ilydra/Jne hydrate may be
employed as a reducing agent, the electrolysis being carried out at 80 to
85 C. using a ()()] A r HXO ; > j quinone auxiliary electrode, a current of
l-o amperes, and a. cathode potential (referred to the quinone electrode)
of -<)! 5 to -()(> volt. This method is suitable for the separation of
bismuth from lead. 10 A solution of bismuth trichloride may also be
used ; it is suggested that the solution should also contain sodium
chloride, calcium chloride or magnesium chloride. Additions of pyro-
gallol and rcsorcinol to the electrolyte improve the deposit, but additions
of hydroquinonc and benzoic acid arc not so effective. 11
g "bismuth, sec ISazerac
, 82, 3GG.
" Korenman, Pharm. Zc.iilr.-h., 1930, 71, 7G9.
(; Martini. M ilrochcnn^ 1928, 6, 2rt; Chan. Zmlr., 1928, i, ISO*!.
7 ''Pa rnehyna. Inc. a! .
s Koivnman, Dtann. Zcntr.-li., 1 92^), 70, 1. See also 'Koseni lialer, /Vw
4, 1272; Onmont a/nd lioniJIenne, Cm/ipl. rend. Xoc. li'ml., 192S, 99, 12-17.
'' Luesh] and l>arloeei, .-Iv?;?,. ('him. a'pjtlic.ntu, 1932, 22, 509.
10 Collin, Analyst, 1929, 54, (554.
JL Kern and Jones, Trans. Amcr. lectrochem. Sue., 1930, 57, 255.
. ZnL, 1929,
222 AXTDIOXY AND BISMUTH.
Good deposits of bismuth are obtained Prom an electrolyte of per-
chloric acid containing bismuth, with a little oil of cloves as an addition
agent. The electroh r sis is carried out at 40 C. with a current density of
1-2 to 3-6 amperes per square foot. If lead is present, however, both
lead and bismuth are deposited. 1
The dropping mercury electrode may also be employed for the
electrolytic estimation of bismuth. The electrolyte is composed of a
nitric acid solution, neutralised by sodium hydroxide, to which Rochelle
salt has been added. 2
Spectrographic Methods. In recent years spectrographic methods
have been adopted for the identification and the approximate estimation
of bismuth. These methods have been employed mainly in connection
with alloys, but they have also been adopted in the examinatioi of ash
from organic remains. 3
1 Fink and Gray, Tra-nx. Amer. EJertrnchem. $oc., 1932, 62, 189.
- Snchy, CoUr.ctio-ti Czrc.hoslov. Chem. Gom-m,., 1931, 3, 3o4. For further references to
the electrolytic estimation of bismuth, see Chetverikov, Tzvfit. 3/e/.., 1930, 5, 64f>;
Grosset, BvlL Soc. chim. J3eJg., 1933, 42, 269; Jilek and 'Lukas, Colkc.lwn GzccJiodov.
Chem. Comm., 1929, i, 369.
3 Eddy, CheTii. E-nrj. ^fining Hwio.w, 1932, 24, 239; Brownsden and van Soineren,
J. Jnst. Metal*, 1931, 46, 97; Lomakin, Zaitscli. anorg. Chem., 1930, 187, 75; Eddy arid
Laby, Proc. Roy. Soc., 1930, A 127, 20; Piccardi, AUi R. Accnd. Lmcti, 1929, 10, 2r>8.
XAME INDEX.
ABEOO, R., 68, 197.
Abel, E., 40.
Abram, H. H., 207.
Abramson, M. B., 42, 151.
Adam, P., 147.
Adams, E, P., 22.
Adams, L. H., 131, 132, 133.
Adhikari, X , 63, 77, 82.
Adic, R. H., Ill, 112, 201. 202.
Adinolii, E,, 131, 132, 133.
Adlcr, J., 40.
Ajreeva, A. V., 151.
Acostini, P., 219.
Acricola, G., 14, 215.
Ahlficld, P., 119.
Akcrmann, J., 131.
Alber, A., 167.
Albert, K., 29, 30, 89.
Alcock, P. H., 108.
Alrcaroth, V., .15.
Allan, P. B., 201, 202, 209.
Allbright, J. G., 100.
Allen'] R.,' 125.
Allen, 8. M. T., P12.
Allison, P., 147.
Almin, A., 40.
Almkvist, G., 191.
Aloy, J., 165, 1(56, 173.
Alpiien, P. M. van, 22, 139.
Alterthmn, IP, 22.
Altmann, A., 1 37.
Amadori, M., 199, 200, 207,.
Artdauer, AP, 32. '
Anderson, C. T., 19, 87, 92, 94, 133, ISO.
Andiv, G., 192.
Ansehutz, IP, 59, 70, 71, 70, JO I, 172.
Ansell, G. P., 51.
Antimon Ber^i- und lluitenwerko A.-G.,
85.
Anioni, U., 162, 208,
AnlonolT, G. X., 20.
Aoki, M., 41, 44.
Aoyama, K., 208.
.Aoyama, S., 1 30.
ArakaA\-a, S., 132.
Arehbuli, S. L,, 39.
Arctou'ski, 1 1 , 02, 98.
Arfvedson, J. A., 202,
Arnone, M., 152.
Arppo, A. K., 1(53, ! 00, 107, 108, 177, 179,
ISO, 1.82, 191, 192.
Arrivaut, G., 64.
Artini, E., 124.
Arvidson, G., .140, 141.
Ashley, H. E., 19.
Astcnao, R., 64.
Aster "A. K., 140.
Aston, P. AY., 38, 147.
Astro, C., 180.
Astro, L.. 180.
Aien, A. H. W., 66, 161, 194, 195, 200
Athenasescu, X., 202.
Atkinson, R. W., 65, 66, 174.
Aiterbcrff, A., 216.
Attfieid/J., 30, 58.
Atynski, K., 112, 204.
ArTbel, E. van, 19, 59, 138, 150, 151.
Anclcn, H. A.,' 15.
Andrieth, L. P., 23, 131.
Aufdcrhaar, H. C., 152,
Au^er, V., .178.
Austen, P. T., 30.
Avscevitsch, G. P., 32.
Awbcrry, .J.'"H. ? 19, 20, 132, 133, 134.
OA, M., 11, 92, 97.
'Backer, R. P., 141.
.Ha oho, P. di, 30, 35, 100, 10-1.
I^aok, E., 141.
Barlanii, ,). S., 27, 38.
BaclcTi- Powell, 208.
Hailey, G. H., 14S, 186, 2()2.
Baker, C. P., 124.
Baker, H . B., 28, 84.
.Bakka, G., 117.
BalareiT, D., 91.
Ball, W. C., 200, 207.
Balouna, Z., 01 .
Baly, E.'C. C., 27, 1-12.
Barba, A. A., 125.
Barek, IP, PJ4.
Barea, P. Castro, 124.
Barques, M. A., 26, 140.
Barlow, G., 22.
Barnes, E. P., 32.
Barratt, S., 141.
Bartee/.ko, P., Gf>, 70, HiO.
Bartels, Iv., -48, 51, 52.
Bartholomew, K. M., ISO.
P.artl(>y, K. II., 103.
Ba.rioc'c-.i, A., 221.
Barns, ('.., 135.
J'.a.ssani, V., 00, 81 .
Baleson, ,S., 38.
Baubi-ny, IP, 92, 90, 110, 111, 110.
ANTIMONY AXD BISMUTH.
Baudrimont, E., 30, 58, 62.
Bauer, 0., 103, 107, 108.
Baur, E., 194.
Bayer, K., 39.
Beard, H. C., 31.
Beat-tie, J. A., 154, 364.
Bccarelli, R., 159, 171, 176.
Beck, G., 54.
Becker, E., 209.
Becker, F., 109.
Becker, J. A., 137.
Beckett, E. G., 35, 100.
Beckmann, E., 66, 70, 78, 81, 82, 200.
Becquerel, A. E., 105.
Becquerel, H., 01, 70.
Behn, U., 19.
Behre, C. H., 4.
Behrens, T. H., 65, 69.
Beilstein, F. E., 96.
Bekier, E., 20, 41, 131.
Bell, J. M., 124.
Belladen, L., 64, 188.
Bemmelen, J. M. van, 59, 67, 68, 209, 210.
Bender, G., 216.
Benedict, , 65.
Bennett, W.'Z., 79.
Berdau, M., 108.
Berg, R., 219.
Bergdahl, B., 21, J35.
Bergell, P., 50.
Bergeret, M., 51.
Bergfeld, L., 2.1, 135.
Berg-kind, E., 106.
Berginann, A., 41, 44.
Bcrgmann, E., 38, 58, 60, 71.
Bergmai-m, T., .125.
Bergstrom, P. W., ]45.
Bcrnardis, G. B., 66, 82.
Berthelot, M. P. E., 14, 18, 50, 65, 67, 78,
102, J06.
Bert.lio.nio1, J. B., 79, 83, 177.
Bertliier, P., 103, 104, 106.
Bert rand. A., 73.
Bertseh, M., 107.
Berzelius, .J. ,J., 28, 29, 33, 34, 53, 55, 57,
58, 84, 85, 00, 9J, 93, 97, 104, 106, 107,
110, 182, 205, 208, 213, 21.4.
Bc-sson, J. A.} 63, 73, 162, 163.
Botterton, .1. ()., 127.
Betis, A. G., 127.
Bet/, II., SO, 180.
BImtnagar, S. S., 71, 139.
Bidwell, 0. C., 186.
Bit-mis, A., 20.
Bierbrauer, K., 88.
BigeloNr, S! L., 133.
Bi'jlert, A. van, 4S, 50.
Bilt.z, H., 21, 135.
Bill/, .]. II., 87.
Biltz, VV., 5S, 01, 02, 76, 80, .1.05, 161, 172,
17S, 191.
Birr.koMbar.h, L., 1-18, 100, 178, 187.
BimnnshjMv, L. I.., 20, 134.
Bishop, K. II., 1-17.
BiU), K., 208.
I Blase, 0. von, 96.
: Blake, F. C., 28.
Bleekrode, L., 70.
Bloch, E., 27, 141.
Bloch, L., 27, 1.41.
Blumenthal, B., 151.
Blyth, A. W., 47.
Blyth, M. W., 47.
Blythe, T, R., 181.
Bodenstein, M., 50.
Bodforso, S., 31.
Bodlander, G., 197.
Bodraan, G., 202, 207.
Bddecker, C. H. D., 216.
Bohm, ,L, 23.
Bdhm, W., 107, 108.
Bottser, R., 28, 30, 48, 50, 82, 83, 84,
: 111, 192.
1 Bottger, W., 32, 59.
' Boiebaudran, L. de, 202.
i Bolton, H. C., 103, 106.
. Bonamini, L., 202.
: Bonar, A. R., 1.41.
Bonaretti, A. W., 41.
Bongartz, J., 34.
Bonsdorfr, P. A. von, 85, 142, 185.
Borelius, G., 129, 138.
Borgstrom, L. H., 196.
Boriiemann, K., 20, 133, 134.
Bornhak, R., 40, 150.
Bosch, J. C. van den, IS.
, Bose, M., 192.
Bosck, 0., 70, 93, 99, 106, 107, 108.
' Bossa, E., 22.
! Bothamley, R. P., 74.
; Bottom a, J. A., 19, 25, 40.
Boucaulfc, J., 111.
Bouillenne, M., 221.
Boullay, P. F. G., 88, 93.
Botn'son, J., 93.
Bouzua/ou, A. C., 216.
Bowen, E. "C., 41, 42, 152.
Boydston, R. W., 129, 138.
Boyle, II. , 14, 15, 160.
Bozorth, R. M., 9, 84.
Braddock- Rogers, K., 198.
Brackken, H., 79, 178.
Braesco, P., 1.9.
'Bragg, W. L., 13L.
Brand, A., 114.
Brandcs, R., 57, (>2, 79, 82, 83, 84, 90,
114, 191, 192.
Bra one, >!., 71.
Brauner, B., 98, 99, 100, 107.
Bra zonal 1, W., 15.
Brcdia, G., MO.
J^reithaiipt, -J. F. A., 91, 124.
Brett, R. H., 89.
Brewer, R. K., 31.
Bre/.imi, A., S7.
Bridoman, P. VV., liJ, 21, 22, 28, 129,
132, 130, 137, 138.
Bnggs, S. 11. C., 20 1.
Bngham, (!. Pliny, 100.
Brink man, R., 31.
XAME IXDEX.
225
Brintzinger, H., 96.
Brislee, F. J., 183, 187.
Brit-ton, H. T. S., 31, 32.
Britzke, E. V., 97, 101, 102, 104, 197, 198,
199.
Broderick, S. J., 39, 150.
Broniewski, W., 20.
Brown, D. J., 118.
Brown, J. C., 124.
Browning, P. E., 59.
Brownsden, H. W., 222.
Bruchhold, C., 17.
Bruhl, W., 62.
Bruins, H. P., 79.
Brukl, A., 113, 117, 118, 205, 214.
Brunck, 0., 92, 97, 116.
Brunn, 0., 49, 50, 51.
Brims, H. D., 204.
Bucher, A., 151.
Bucherer, H. T., 219.
Buchholz, C. F., 113, 191, 192.
Buchholz, Jun., 109, 111.
Buchner, L. A., 51, 111.
Biinz, R., 192.
Biissein, W., 131.
Buisson, P. M. A., 181.
Bulk, A., 157, 163, 169, 173, 179.
Bultunov, J. A., 32.
Bunsen, R., 84, 90, 91, 94, 103, 104, 105,
107, 108, 116, 182.
Burkart, H. J., 124.
Burkser, E. S., 77, 174.
Burrows, C. J., 180.
Buytendijk, F. J. J., 31.
CADE:S:BACH, G., 208.
Cashoti, V., 152, 177, 201, 202, 204.
Caille, ,116.
Calcagno, 0., 213.
Callendar, H., 19.
Galloway, J., Jun., 220.
Cameron, C/A., 113, 205.
Cammerer, J. B., 199.
Campbell, L. L., 139.
Campbell, W., 41.
Campetta, A., 27.
Canneri, G., 174, 180, 203, 217.
Cantone, M., 22.
Capcl, W. H., 136.
Capitame, H., 48, 59, 91, 96, 102, 104, 105,
106.
Capua, C. di, 152.
Carli, F. de, 187, 1SS, 208.
Carnegie, D., 190.
Carnefley, T., 21, 53, 59, 79, 88, 89, 92, 135,
161, 172, 178, 189, 190.
Camot, A., 98, 99, 111, 124, 203.
Carobbi, G., 208.
Carpenter, PI. C. H., 18, 39, 131.
Carpenter, L. G., 133.
Carpini, C., 137.
Carrcras, R. S., 190, 215.
Carson, C. M., 57, 103.
Cartwright, C. H., 130.
Case, T. W., 196.
Cassie, A. M., 142.
| Castro, C., 5.
| Caswell, A. E., 138.
I Catenacci, X., 31.
Cattica, V., 202.
Causse, H. E., 64, 68, 162.
Cavazzi, A., 172, 173, 213, 214, 215.
i Caven, R. M., 81, 213, 214.
! Centners ver, M., 60.
; Cesaris, P. de, 42, 103, 115.
' Chamberlain, K., 28.
'; Chancel, G., 213.
! Channel Evans, K. M., 39.
: Chapman, A. C., 3.
i Chapman, A. K., 22.
Charola, F., 26, 141.
Charpy, G., 153.
Charrin, V., 3, 17.
Chatelier, H. le, 67, 68.
Chemisettes Werk Klopper, G. M. B. H.,.
147.
Chenault, R. L., 26, 27, 141.
Chetverikov, J. D., 222.
Chiappero, A., 108.
Chikashige, M., 40, 42, 103, 112.
Chipman, H. R., 61, 62.
Chow, M., 145.
Chretien, H., 19.
Chretien, P., 18, 20, 97, 99, 101, 102, 112,
Christiansen, W. G., 180.
Cissarz, A., 101.
Claesson, J. P., 64.
Clark, J., 29, 93.
Clark, P. V., 180.
Clark, R. E. D., 84.
Clarke, F. W., 89, 207.
Clasen, W. L., 29.
Classon, A., 103, 106, 107, 108, 109, 118 r
148, 202.
Clausnizer, F., 72.
Clemente, A., 105.
Clermont, P. de, 58, 103, 104, 198.
Cloc'z, S., 72.
Chisel, M., 111.
Coffin, C, C., 23, 25.
Cohen, E,, 18, 22, 23, 24, 25, 28, 29, 35, 58^
79, 117, US, 129, 130, 139.
Cohn, R, F., 127.
Collenbcnr, 0., 117.
Collin, E/'M., 221.
Collins, E., 18, 35.
Compton, K. T., 139.
Conmck, W. 0. de, 148.
Conrad, C. P., 93, 96.
Constant, F. W., 139.
Cook, M., 42, 152.
Cooke, J. P., 29, 33, 34, 35, 58, 59, 60, 61,
i 62, 64, 66, 69, 76, 77, 79, 82, 99, 101.
! Coolbaugh, >L F., 16.
i Corbino, 0. M., 137.
I Coriield, C. E., 190, 191, 192, 193.
Cork, J. M., 28, 142.
Cormimbocuf, H., 88, 90, 91.
i Coster, D., 28, 142.
i Couplancl, H. C., 215.
I Cowan, W. A., 152.
i Cowpcr, R., 29, 144, 160.
226
AXTIMOXY AXD BISMUTH.
Cox, A. J., 206.
Cox, H. L., 28.
Crawford, M. F., 38, 140, 141.
Crittenden, F. D., 58, 59, 66.
Croll, O., 93.
Crymball, C. R., 61.
Cuisinier, V., 203.
Cumenge, E., 93, 124.
Cuntze, A., 216.
Curie, P., 130, 138.
Curry, B. E., 150.
Curtis, L. F., 137.
Curtius, T., 30.
Cushny, A. R., 47, 155.
Czerwek, A., 30.
DAHL, 0., 44.
Dalietos, J., 30, 63.
Damour, A., 91.
Dana, E. S., 4-13, 100, 120-123, 125.
Dana, J. D., 4-13, 100, 120-123, 125.
Daneel, H., 29.
Daniel, W., 155.
Bannohl, W., 43, 44.
Barapski, A., 30.
Darbyshire, J. A., 38, 141.
Darling C. R., 138.
Darling, E. R., 117, 185.
Daubrauer. H., 71, 94, 96.
Daure, P., 61, 162.
Dauvillier, A., 28.
Davey, W. P., 131.
Davis, G., 64.
Davy, J., 125, 160.
Day! A. L., 19.
Dean, R. S., 41.
Debacher, M. 0., 41.
Debray, H., 69, 84, 85.
Deherain, P. P., 63, 73, 144, 158, 160, 166,
167, 169.
Dehlinger, U., 84, 85, 92, 93.
Deichler, C., 191, 192.
Deichmann, , 216.
Dekker, P., 108.
Delacroix, A. E., 96.
DelfTs, W., 93.
Dellacher, J., 41.
Dclwaullc, M. L., 179, 180, 181.
Demarcay, E. A., 21.
Demmer, A., 44.
Denharn, H. G., 176, 181, 183.
Deniszczukowna, Mile., 95.
Denizot, A., 132.
Bcrnies, J., 220.
Bescamps, A., 115.
Deutsche Schmelz- und Rafrinierwerke
A.-G., So.
Devoto, G.,. 159.
l)c war, J., 19, 136, 137, 138.
Dexter, W. P., 30, 34, 35, 58, 91, 92, 101,
10f>, 111, 112.
Dhar, X. P., 105.
Dhavale, D. G., 27.
Diessclhorst, H., 136, 138.
Discorides, 14.
Bitscheiner, L., 208.
Ditte, A., 29, 65, 67, 87, 99, 101, 105,
160, 163, 196, 199, 209.
Divers, E., 143.
Dix, E. H., 41.
Dix, F. E., 140.
Dixon, H. B., 28, 84.
Dixon, W. E., 47, 155.
Dobbie, J. J., 26.
Bolter, C., 103, 106.
Boht, W., 48, 49, 50.
Dolejsek, V., 142.
Domeyko, L, 91, 167, 201.
Donahue, T. H., 127.
Donat, E., 133, 139.
Donath, E., 109, 116.
Bonk, A. D., 109.
Donski, L., 40, 150.
Doornbosch, H. R., 78, 82.
Dormaar, J. M. M., 118.
Dorsey, H. G., 18, 131.
Douglas, R. E., 125.
Bowzard, E., 51.
Bragendorff, G., 51, 180, 181.
Drath, G., 20, 134.
Dreifuss, M., 43.
Dreyer, K. L., 218.
Bruce, J. G. F., 48, 155.
Drude, P., 22.
Druyvesteyn, M. J., 28.
Buane, W^, 28, 142,
Dubrisay, R., 163, 169, 173, 179.
Ducelliez, P., 64.
Duflos, A., 62, 69, 99, 106, 109, 111, :
209.
Bulk, F. P., 209.
Dullenkopf, W., 149.
Dulong, P. L., 19.
Dumas, J. B. A., 33, 34, 35, 53, 148.
Dumont, P., 221.
Duncan, J. B., 117.
Dunning, F., 64.
Bupais, P., 144.
Btipasquier, A., 48.
Duquenois. P., 116.
Burand, M., 85.
Bnrant, A. A., 156.
Burocher, J., 62, 98, 196.
Burrer, R., 19, 42.
Dyson, G. M., 14, 15, 47, 57, 93, 107,
128.
EAGLES, E, M., 160, 162, 170, 173, 175,
179, 382.
Eaklc, A. S., 102.
Ebel, F., 96.
Ebert, F., 55.
Ebler, E., 190.
Echiandia, E., 49, 50.
Eddy, C. E., 142, 222.
Edgerton, P., 88.
Edmunds, C. AY., 155.
Edwards, C. A., 19.
Edwards, F. W., 152.
Eceink, B. G., 159, 171.
Ecidi. U.. 213, 214.
XAME IXDEX.
Ehrcnfest, P., 138, 139.
Ehret, W. F., 39, 42, 150, 151.
Eidmann, \\., 89.
Elbers, W., 103.
Elton, M., 201, 215.
Ende, J. X. van den, 133.
Endo, H., 113, 131, 132, 133, 138, 186, 205.
Encel, L., 38, 58, 60, 71.
En^el, R,, 65, 163.
Engelhardt, V., .17.
Engeniann, , 220.
Ephraim, F., 54, 65, 70, 78, 105, 166, 202.
Epik, P. A., 104.
Erckelens, E. van, 17, 127.
Ercker, L., 14.
Erhard, T., 21.
Eriksson, S., 39.
Espt, E. van der, 78.
Ettincshausen, A. von, 22, 138.
Eucken, A., 21, 40.
Euler, H. von, 64.
Evans, B. S., 117.
Evans, E. J., 39.
Evans, E. T., 151.
Evans, P. X., 59, 70, 71.
Evnevitsch, E. V., 161, 172.
Ewald, R., 19.
FAKTOR, F. J., 89, 110, 145, 162, 195, 203.
Faraday, M., 97.
Fay, H", 19.
Feigc, C., 73, 74, 75, 78.
Feigl, F., 117.
Feiser, J., 186, 188.
Feit, \V., 108, 109.
Feitknccht, W., 169.
Feng, C. T., 219.
Fenwick, F., 31, 85, 87, 89.
Ferguson, A. L., 60, 76, 80.
Fernelius, W. C., 206.
Ferray, E. H., 181.
Fichtcr, F., 76, 169, 170.
Field, E., 166, 173, 174.
Field, F., 103.
Erne, R. D., 150.
Findancl, J. J., 127.
Fink, C. G., 14, 146, 222.
Finkenor, , 62, 99.
Finot, E., 73.
Fireman, P., 73.
Fischer, A., 118.
Fischer, B., 181.
"Fischer, E., 59.
Fischer, F., 40.
Fischer, G., 09.
Fischer, P., 151.
Fischer, T., 216.
Fischer, V., 41.
Fischer, W. M., 74.
Fisher, R. A., 140.
Fisk, \V. G., 79.
Fizeau, 11., IS, 88, 132.
Fleitmann, T., 48.
Fleming J. A., 136, 137, 138.
Floyslu-r, M. H., 117.
Fliuk, G., 124.
Floresco, X., 29.
Fluckiger, F. A., 48, 51, 53, 54, 55.
Foa X" '^17
Focke, A. B., 129, 131, 139.
Foerster, F., 118, 146.
Foder, M. F., 41.
Footc, H. W., 65, 92, 180.
Foote, P. D., 26, 27, 141.
Ford, W. E., 13.
Foresti, B., 155.
Formhals, R,, 35, 94, 117.
Forrest, J., 139.
Fosbinder, R. J., 32.
Foster, W., 192.
Foucroy, A. F. dc, 111.
Fox, J."j., 26.
Franck, J., 142.
Francois, F., 79, 80, 82, S3, 179, 181.
Frankel, L. K, 190.
Franklin, E. C., 168, 206.
Franz, R., 135.
Frayne, J. G., 26, 141.
Frebault, A., 165, 166, 173.
Fredenhasen, K., 208.
Fremy, ET, 90, 93, 96, 192.
Frenzel, A., 66, 69, 93, 124.
Fresenius, C. R., 52, 58, 99, 101, 104, K
155, 216.
Freude, F., 150.
Frey, G. S., 101.
Freyer, F., 161.
Frick, C., 126, 220.
Fricke, H., 142.
Friedrich, H., 62, 72.
Fnedrich, K., 44.
Friend, G. C., 34, 35.
Friend, J. A. X., 18, 24, 131, 207, 211.
Fngidaire Co., 84.
Fnman, E., 142.
Fnscher, H. } 38, 43.
Frohch, 0., 54.
Frommel, J., 103.
Frycz, K., 60.
Fuchs, J. X. von, 99, 101.
Fuchs, R., 196.
Fujita, M., 42, 112.
Fuller-ton, H. B., 157.
Fnnakoshi, 0., 219.
Funke, G., 153.
Furinan, X. H., 31, 117.
Furstenau, E., 99.
GALL, H., 62.
Galvez, X., 32.
Gan-uly, P. B., 105.
Gans, R., 22, 138.
Garelli, F., 66, 76, SI.
Gamier, L., 104.
Garot, M., 104.
Garrido, J., 124, 200.
Garllein, C, W., 27.
Gaspar y Arnal, T., 206.
Gatehouse, J. VV., 48.
Gamier, A., 19.
Gay-Lussac, J. L., 111.
Geber, 14.
228
ANTTMOKY AND BISMUTH.
Gebert, E. B., 41, 151.
Gehlhoff, G., 21, 40.
Geibel, W., 105.
Geiger, P. L., 57, 103, 108, 109, 111.
Geitner, C., 29, 98, 144.
Gemolka, F., 50.
Genard, J., 27, 38.
Genth, F. A., 115, 124, 205.
Geoffroy, C. J., Ill, 125.
Georgieff, M., 132.
Gerard, , 148.
Gerichten, E. von, 113.
Germuth, F. G., 219.
Gettner, B., 147.
Geuther, A., 96.
Gex, M., 31, 32.
Ghiron, D., 24, 25.
Ghosh, C., 186.
Ghosh, M. G., 214,
Ghosh, S., 105.
Gibbs, 0. W., 91.
Gibbs, R. C., 27.
Gibson, J. A., 116.
Giebe, E., 136.
Giesy, P. M., 215.
Gigli, G., 208.
Gilman, E., 31.
Giraud, H., 94.
Gladstone, J. H., 208, 209.
Glatzel, E., 114, 162, 214.
Glauber, J. R., 57, 93.
Glazunov, A., 218.
Gleria, J. di, 31, 32.
Glixelli, S., 95.
Glocker, R, 84.
Grnachl-Parnmer, J., 40.
Godeftroy, 64, 65.
Gobel, R, 57, 104.
Goetz, A., 129, 130, 131, 132, 139.
Goldschmidt, F., 185.
Goldschmidt, V. M., 38, 130.
Gomperz, E. von, 131, 132.
Gontermann, W., 41.
Gooch, F. A., 59, 94.
Goodrich, W. E., 133.
Gordon, H., 31.
Gore, G., 23, 162.
Gortikov, V. M., 31, 32.
Gossmann, 0., 61.
Gott, S., 157, 158, 177, 179.
Gottfried, C., 100.
Goudsmit, S., 140, 141.
Goush, H. J., 28.
Gowland, W., 15, 16, 126.
Grace, A. W., 138.
Graf, H., 53, 54, 55, 56, 57.
Graf, L., 18, 25.
Graham, T., 208.
Grammont, A. de, 27.
Grant, J., 48, 49.
Grassl, G., 116.
Gravino, P., 4.
Gray, 0. H., 146, 222.
Gray, W. H., 64.
Green, G., 217.
Green, J. B., 26, 27, 140.
Greene, G. V., 127.
Greenwood, H. C., 21, 135.
Griffiths, E., 19, 20, 132, 133, 134.
Grigoriev, A. T., 40, 44.
Grimm, H. \V., 85.
Grippenberg, W. S., 87.
GroschurT, E., 17, 129, 133.
Gross, F., 131, 137, 139.
Grosse-Bohle, A., 87.
Grosset, T., 118, 222.
Grosspietsch, 0., 124.
Groth, P., 58, 87, 88, 91, 130, 166, 174, 180,
185, 201.
Grotrian, W., 141.
Grouvelle, P., 69, 208.
Grube, G., 31, 40, 144, 146, 149, 150, 192.
Griinbaum, H., 53, 54.
Griineisen, E., 18, 131, 132.
Gruener, H. W., 59, 94.
Griiters, M., 203.
Griitzner, B., 114, 213.
Grunmach, L., 137.
Giinther-Schulze, A., 86, 186.
Guerout, A., 103, 196.
Guertler, W., 41, 44, 103, 152, 186.
Giittich, A., 52, 53.
Guggenheim, Bros., 128.
Guinchant, J. M., 18, 20, 97, 99, 101, 102,
Gunn, J. A., 155.
Gunther, P., 19.
Guntz, A., 53, 54, 61, 69, 76, 87, 89, 92.
Gurchot, C., 180.
Gutbier, A., 146, 147, 148, 165, 187, 192>
193.
Gutmann, August, 90, 111.
Guttmann, Artur, 159, 171, 176, 183, 194.
Guttmann, O., 48, 49, 50, 51, 58.
Gutzeit, G., 219.
Guzzi, A., 159.
Gwyer, A. G. C., 151.
Gy6ry> S., 117.
Gysinck, T., 31.
HAAGEX, A., 70.
Haas, W. J. de, 22, 136, 137, 139, 150, 151,.
152.
Haase, 0., 132.
Haber, F., 146.
Hackspill, L., 190, 210.
Hada, S., 213.
Haen, E. de, 54.
Hasg, G., 39, 41, 43, 152, 153.
Hagen, E., 139.
Hager, H., 48, 90.
Halm, F. L., 31.
Hahn, F. V. von, 112.
Hahri, X., 107.
Haidinger, W., 102.
Haidlen, ,216.
Haissinsky, H., 191.
Hall, D. A., 211.
Hall, F. W., 154, 164.
Hall, W. T., 115.
Halla, F., 40.
Hallmann, C., 35.
Halse, E., 3.
NAME INDEX.
Hamann, G., 219.
Hamer, R., 139.
Hammerschmidt, W., 146.
Hammett, L. P., 96.
Hammick, D. L., 185, 187.
Hampc, W., 93, 103, 106, 215.
Hanak, A., 17.
Hankel, ,51.
Hansen, C. J., 99, 107.
Hansen, M., 151.
Hanus, J., 199.
Hanzlik, P. J., 180.
Harbaurrh, M., 146.
HarderfA., 39, 150.
Harding, A., 48.
Harding, M. C., 90.
Hargreaves, F., 132.
Harle, T. P., 133.
Harmsen, M., 107.
Harris, J. E., 134.
Harrison, W. H., 31.
Harst, P. A. van der, 27.
Hartl, 0., 167, 206, 208, 213, 214.
Hartley, \V. X., 142.
Harwood, H. F., 124.
Haschimoto, V., 150.
Hasebroek, K., 191.
Hasler, M. P., 130, 131.
Hassel, 0., 130, 157.
Hasslacher, P., 54.
Hatra, A., 43.
Haupt, H., 91.
Hanser, G., 54.
Hanser, 0., 167, 181, 186, 191, 192, 193,
203, 217.
Hayward, C. R., 127.
Heaps, C. W., 139.
Hecht, L., 72.
Hefftcr, L., 96, 108.
Henri or, A.. 155.
Hem, F., 162, 165, 174.
Heintz, E. A., 158.
Hcintz, W., 142, 144, 160, 102, 103, 167,
168, 1.77, 179, 182, 192, 194, 202, 209,
213.
Heinzel, A., 151, 152, 219.
Heller, K., 219.
Heller, AY., 55, 56.
HclLstrom, H., 64.
Helm, 0., 15.'
Helmont, H. von, 157, 158.
Hemecles, E. D., 31.
Hempel, W., 186.
Henderson, G. G., 88.
Hendrixson, W. S., 143.
Henne, A. L., 83.
Hennsmann, P. J., 111.
Henry, X. E., 69.
Henry, 0., 111.
Hensiren, C., 58, 87, 104, 111, 202.
Henz, P., 35, 116, 118.
Hcpner, B., 209, 210.
Herard, F., 24, 113.
Herbe, E., 51.
Herberser, J. E., 209.
Herbert, A. M., 19.
Hergenrother, R. C., 130, 131, 132.
Hermann, K., 131.
Hermann, E., 201.
Herold, W., 152.
Herroun, P. E., 94.
Hertel, E., 44.
Hcrtel, W., 128.
Herty, C. H., 65.
Herz", W., 157, 159, 163, 168, 169, 171, 17;
175, 176, 179, 183, 194.
Hess, A., 133.
Hesse, L., 103.
Heteren, W. J. van, 73.
Heumann, K., 29, 58, 106.
Hems, H. W., 146.
Heycock, C. T., 19, 39.
Heyl, P., 163, 168,
Hey maim, L., 54.
Heynemann, H., 50.
Hibbard, P. L., 31.
Hidnert, P., 18.
Hiers, G. 0., 152.
Hisbee, H. H., 64.
Hieeins, W. P., 132, 136.
Hilditch, T. P., 189.
Hilser, A., 192.
Hill, H., 213, 214.
Hillebrand, W. P., 124.
Hilprecht, H. V., 1.5.
Himly, C., 111.
Hincke, W. B., 85, 86, 87.
I Hintze, C., 100, 125.
1 Hirata, H., 18, 28, 131.
Hjalmar, E., 28, 142.
: Hlasko, M., 49.
' Ho, Ivai, 15, 17.
Hock, L., 108.
i Hodirkinson, W. 11. E., 202.
Hock, C. P. van. 47, 91.
Honiffschmicl, 0., 34, 36, 148, 160.
Hofackcr, G., 112, 113.
rloiYmann, C,, 192, .194, 198, 216.
.Hoifmann, G., 125.
HofTmejstcr, G. B., 157, 160, 172, 173, 17
175, 177, 178, 183, 187, 192, 216.
: Hofmann, A. W., 52, 73.
rlofmann, W., 4, 100, 124, 196.
1 tiofmeicr, G., 146.
: Ho^ncss, T. R., 134.
Holborn, H., 19.
Hollard, A., 118, 192.
Holmquist, A., 31.
, Holzer, H., 218.
' Hommel, W., 15, .149, 153.
Honda, K., 22, 138, 150, 1.52.
Hoover, H. C., 125.
Hornunc:, E. G., 85.
: HorselCS. M., 114.
Horton, P., 186.
Hoiighhoudt., S. B., 32.
Houzeau, A., 52.
I Howells, E. V., 39.
: Hudson, W. E., 4-1.
Hnttig, G. P., 189.
Huttner, K., 215.
! Huf schmidt, P., 59.
230
AXTIMOXY AND BISMUTH.
Hughes, A. LI., 139.
Hugounenq, L., 147.
Hulburt, E. 0., 140, 142.
Hulthen, E., 155.
Hume-Rothery, W., 39.
Humpert, T., 48, 51, 52.
Husemaiin, A., 73.
Hussak, F., 91.
Husson, C., 51.
Hutchins, E. B., 167.
Hutchinson, A., 185.
Hutin, A., 108.
Hybinette, A. G., 41.
Hyman, H., 15.
I.G. EARBEXIXD. A. G., 107, 128, 190.
litaka, L, 132, 133.
Inoko, S., 117.
Ipatiev, V. X., 28.
Ipaticv, V. V., Jan., 28, 144.
Ireton, H. J. C., 141.
Isbekov, W., 76, 145, 172, 173, 174.
Ishigaki, T., 150, 152.
Ishimarii, S., 220.
Isihara, T., 153.
Isnardi, H., 22, 138.
Italic, A., 31, 32.
Iwasi, K., 41, 44.
Izgaruishev, X. A., 17.
JABLCZY^SKE, K., 105.
Jackson, F. G., 19.
Jacobs, W., 164.
Jacobsohn, F., 73, 108.
Jacquelain, V. A., 48, 51, 63, 145, 161, 162,
166, 167, 168, 169, 192, 193.
Jaeger, F. M., 19, 25, 40. 78, 82, 87, 97, 103,
161, 172.
Jaeger, W., 136, 138.
Janecke, E., IS, 129, 133.
Jar vi ness, K. K., 117.
Jahn, F., 108.
Jahn, H., 59, 76.
James, R. W., 18,. 130.
Jander, G., 95, 96.
Jancttaz, E., 21.
Jannasch, P. E., 98, 102, 103, 106, 172, 191.
Janssen, }., 209.
Janssen, R. L., 148.
Jay, A. H., 130, 132.
Jeanmairc, A., 63, 113.
Jeep, K., 62.
Jeffery, F. H., 42.
Jellinek, K., 31, 145, 154, 163, 164.
Jenny, E., 76, 169, 170.
Jensen, K. A., 214.
Jeriomin, K., 150.
Jette, E. R., 41, 151.
Jilek, A., 118, 222.
Jiriste, J., 42.
Jonsson, A., 28.
Jorgensen, S. M., 180.
Johannsen, A., 156.
John, R., 64.
Johnson, A., 130.
Johnson, F., 150.
Johnston, J., 131, 132, 133.
Johnston, J. E. W., 69.
Johnston, S., 25.
Joliot, F., 145.
Joly, F., 50.
Jones, A. G., 215.
Jones, F., 49, 50, 51, 84.
Jones, H., 131, 140.
Jones, T. R., 127, 128, 221.
Joos, G., 141.
! Jordan, F. W., 138.
; Jordis, E., 65, 88.
1 Joshi, S. S., 105.
1 Joule, J. P., 88, 92, 93, 207.
i Jonniaux, A., 20, 30, 134.
I Jurist, A. E., 180.
Jurriaanse, T., 150.
I
i KAHLBAUM, G. W. A., IS, 19, 131, 132.
I Kahlenburg, L., 60, 187.
Kahler, H., 131.
Kahn, J., 161, 172.
Kai Ho, 15, 17.
Kalie-Chemie A.G., 128.
Kammerer, F., 70.
Kanewsky, T., 42.
Kanov, K. P., 59, 64.
Kapitza, P., 21, 129, 137.
Kapp, A. W., 15.1.
Kapustinski, A. F., 102, 197, 198, 199.
Karantassis, T., 64, 74.
Karrer, E., 20.
Karsten, C. J. B., 88, 92, 101.
Katz, F. J., 17.
Katz, M., 74.
Kautter, T., 147.
Kawakami, M., 39, 150.
Kaye, G. W. C., 132, 136.
Keesom, W. H., 133.
Keller, F., 41, 86, 186.
Kellcy, K. K., 19, 186.
Kellstrom, G., 28.
Kendall, J., 58, 59, 66.
Kern, E. E., 127, 128, 221.
Kersten, H., 23.
Kesans, A., 104.
Kessler, F., 34, 35.
Kharmandaryan, M. 0., 210.
Kieft'er, A. P", 210.
Kimata, Y., 113.
Kimura, M., 142.
Kinetic Chemicals, Inc., 53.
King, X. J., 31, 32.
Ivirclihof, E., 107, 108.
Kirsebom, G. X'., 89, 188.
Kishen, J., 140.
Kittl, E., 125.
Klapproth, W., 118.
Klein, J., 94.
Klemensicwiecz, Z. 7 59, 60, 61.
Klemm, W., 160.
Klenker, 0., 107, 108.
Klooster, H. S. van, 41, 97, 103, 176.
Knapp, E. J., 136.
Knoch, M., 55, 56, 158, 193.
Knocke, A., 116.
NAME INDEX.
Knoevenagel, E., 190.
Knoll and Co., 74.
Knop, J., 34, 36, 117.
Knorre, G. von, 84, 96, 97.
Knox, J., 188, 197.
Ko, C. C., 135.
Kobel, F. von, 125.
Koch, S., 119.
Kochlin, P., 29, 58.
Kohler, H., 64, 73, 103.
Kohler, T., 88.
Koenig, G. A., 124.
Koenigsberger, J., 138.
Korber, F.,lo2.
Kohl, G., 106.
Kohlhaas, R., 130.
Kohlmeycr. E. J., 101, 102, 126, 127, 188.
Kolb, A", 35, 94, 117.
Koike, E., 91.
Kolthoff, I. >!., 31.
Koninck, L. L. cle, 57, 103.
Konno, K., 103.
Konno, S., 135.
Konstantinov, N. S., 40, 41, 43.
Kopp, A. H., 14.
Kopp, H., 19, 59, 76, 93, 125, 132, 209.
Korenman, J. M., 221.
Kosmann, C. P., 111.
Kosmann, H. B., 71.
Kostacni, A., 131.
Kraemar, W., 26, 140.
Krafft, F., 19, 21, 30, 135.
Kramer, J., 25.
Kraus, C. A., 145, 168.
Krause, A., 161, 172.
Kraut, K., 180.
Kremann, R., 39, 40, 41, 44, 112, 145, 150.
Kretschmar, M., 88.
Kretzer, A., 26, 27.
Kridcr, H. S., 18.
Krishnamurti, P., 61.
Krislmas\vami, K. R., 34, 37.
Kroscr, C., 28.
Kroll, W., 127, 145, 151.
Krotkov, D., 76.
Kruraholz, P., 219.
Kruyt, PL R., 101.
Kubierschky, C., 108, 109.
Kudra, 0. K., 60.
Kulm, W., 145, 154, 163, 164.
Kulme, R., 119.
Kurthv, L , 154.
Kuster, F. W., 203.
Kuhl, H., 111.
Kulm, A., 19.1.
Kunckel, J., 14.
Kurnakov, L, 76.
Kurnakov, X. S., 40, 43, 59, 64, 151.
Kurtenacker, A., 99.
Kurz, T., 71.
Kurzyniec, E., 150.
Kysaba, S., 138.
LAAR, J. J. vox, 31,
Laars, F., 219.
Laborde, J., 19.
! Laby, T. H., 222.
Lacombe, H., 207, 208.
Lacroix, A., 124.
; Lagerhjelm, D., 148, 195, 202.
; Lagerhjelm, P., 125.
! Lakshmanrow, T., 32.
Landcrebe, G., 114, 213.
Lang^J., 57, 99, 183.
Lang, R, J., 27, 140, 141.
Lang, W. R., 57, 103.
Langguth, S., 70.
! Langhans, A., 109.
i Langsbauer, A., 44.
Lapenta, V. A., 147.
Larocque, A., 57.
Laschtschenko, P. X., 19, 20.
i Laspeyres, E. A. H., 18, 87, 102, 124,
: Lassaigne, J. L., 48, 50, 52.
Lassieur, A., 118.
; Lattmann, W., 194.
; Lauenstein, 0., 158,
Lava, V. G., 31.
: Lavoisier, A. L., 14.
: Lea, C., 67, 90. '
Lebaigue, M., 168, 191.
Lebeau, P., 30, 48.
; Le Blanc, M., 42.
: Lebrument, M., 79.
' Leclerc, F., 31.
Lecrenier, A., 57, 103, 118.
Lee, K. W., 220.
: Lefort, J., 30, 93, 113, 215.
Lehmann, F., 108.
! Lehmann, P., 135.
Lehrrnann, L., 100.
. Leide, A., 28.
Lcist,'A., 202.
: Leitirebcl, W., 21, 40, 42, 135.
Lemcry, X., 14, 93, 125.
Lcmoult, P., 51.
Lenker, V., 167.
; Lenssen, E., 99.
Leroux, A., 44.
Lcroux, P., 41.
Leschkc, E., 47.
i Lcspiau, R., 61.
Lesser, E., 99, 103.
Levi, G. R., 24, 25.
Leivconja, K., 43, 153.
L ? Hote,'L. D., 58.
1 Libavius, A., 14. 93, 125.
Liebig, J. von, 65, 90, 93, 100, 109, 111.
Liempt, J. A. van, 21, 135.
Liesegano;, E., 160.
LikicrnilT, A., 209, 210.
Linau, W., ISO, 181, 182.
. Linck, G. E., 178.
. Lincke, G., 18.
i Lincoln, A. T., 60.
', Lindeman, J., 31.
i Linder, S. E., 105, 197.
1 Lindet, L., 74.
! Lindh, A. E., 129, 138.
. Lindner, A., 105.
1 Lindner, W., 85.
1 Lindroth, G. T., 124.
232
ANTIMOXY AXD BISMUTH.
Lindsay, G. A., 28.
Linhard, M., 34, 36.
Lionet, A., 51.
Lippmann, E. 0. von, 125.
Listrat, J. J., 85.
Little, G., 204.
Littre, E., 15.
Lloyd, W. V., 48, 49, 146.
Lobinger. A., 41.
Lochmann, G., 218.
Lowe, J., 148, 190, 205.
Lowenthal, H., 27.
Lowig, C., 76.
Lohnigen, T. van, 27.
Loiseleur, J., 147.
Lomakin, B. A., 222.
Lombard!, L., 138.
Long, J. H., 85, 89, 111.
Loofs-Rassov, E., 44.
Lorch, J., 191, 192.
Lorentz, L., 21, 136.
Loring, R. A., 26, 27.
Lossev, K., 43.
Lottermoser, A., 96, 146, 190.
Louis, H., 126.
Loviton, L., 103.
Lowance, F. E., 139.
Lownds, L., 138.
Lowry, T. M., 131.
Lubavin, N., 105.
Lubovich, V. P., 141.
Luckow, C., 96, 118, 192.
Lucshi, L., 221.
Liiddecke, W., 202, 209.
Liideking, C., 134.
Luff, G., 100, 108.
Lukas, J., 118, 222.
Lussano, S., 18.
Luzzatto, E., 93, 103.
MABBOTT, G. W., 39.
Macallan, J., 113, 205.
McAlpine, R, K., 34, 35, 37.
Me Alpine, W. W., 137.
Macbeth, A. K., 61, 162,
McCay, L. W., Ill, 117.
McCroskey, C. R,, 100.
Mclntosh, D., 61, 62,
Mclntyre, P. F., 127.
Maclvor, C. W. E., 69, 76, 77, 78.
Mack, P., 127.
McKeehan, L. W., 131.
Maclaren, M., 124.
McLay, A. B., 26, 27, 140, 141.
McLennan, J. C., 21, 22, 26, 27,
140, 14.1, .142.
Madeline, E,, 196.
Magri, GT, 162.
Malm, R., ol, 64, 73.
Mahr, C., 220, 221.
Maier, C. G., 59, 161.
Mailfert, A., 103, 187, 191.
Mala^uti, F. J., 69.
Mallet, J. W., 204.
Mallock, A., 132, 152.
Malone, M. G., 60, 76, 80.
] Malossi, L., 201, 202.
I Malurkar, S. L., 26.
| Manchot, W., 116.
Mangini, F., 181.
Marbach, H., 109.
Marchand, R, F., 48, 84, 130, 131.
Marcolongo, A., 208.
Marie, L., 4.
Marignac, J. C. G. de, 55, 57, 148, 202.
Marino, L., 159, 171, 176.
Mark, H., 130.
Markl, R., 40.
Martini, A., 221.
Marx, C. M., 106, 197, 213.
Mascaretti, M., 155.
Mascazzini, A., 118.
Masinsr, G., 152.
Maslowski, M., 49.
Mathers, F. C., 146.
Mathewson, C. H., 39, 149, 150, 153.
Mathewson, E. P., 125.
Mathur, K. G., 71.
Mathur, R, X., 22, 139.
Matsui, M., 208.
Matsuyama, Y., 20, 21, 134, 136.
Matthesius, J., 125.
Matthews, J., 41.
Matthews, J. A., 216.
Matthies, M., 1.55, 156.
Matthiessen, A., 19, 21, 132.
Matuvama, Y. See Matsuvama, Y.
Maxwell, X. L, 61, 162.
May, P., 64.
May en con, M., 51.
Mayer, T., 54.
Mayer, W., 139.
Mazzucchelli, A., 64, 118.
Means, A. H., 124.
Meara, F. L., 40, 41.
Meerbunr, P. A., 59, 60, 67, 68.
Mehler, H., 148.
Mehu, C., 111.
Meier, F. W., 219.
Meissncr, K. L., 103.
Meissner, W., 21, 51.
Meitzendorff, , 216.
Meloche, C. C., 180.
Melzer, H., 47, 91.
Moncdahl, H., 62,
79, 80. Mengin, M., 95.
Menschina, H., 21, 87.
1 Menschutkin, B. X., 64.
, Menzel, A., 143.
Menzel, W., 55.
28, 139, Merz, V., 66, 1.62, 169.
; Meslin, G., 138.
Mctzcer, F. J., 70.
: Metzf, A., 35, 116.
' Metzl, S., Ill, 112.
I Metzner, R,, 29, 87, 160.
Meurer, F., 155.
Meuthen, A., 19.
Meyer, M., 59, 61, 76.
Meyer, V., 21, 87, 135, 161, 172.
Michaehs, A., 30, 58, 89, 94, 158, 160,
' Micheler, M., 193.
XAME IXDEX.
Milbauer, J., 88, 188, 195, 198, 199.
Miley, H. A., 129, 136.
Miller, E. H., 216.
Miller, H. K., 58, 59, 66.
Millon, X. A. E., 29, 93, 114.
Miniere et Fonderie d'Antimonio, 110.
Mishima, T., 141.
Mitchell, C., 219.
Mitchell, C. A., 100.
Mitscherlich, E., 61, 85, 88, 89, 90, 106, 108,
109.
Mixter, W. G., 89, 92, 94, 186.
Miyake, S., 65.
Miyamoto, H. S., 61, 88, 94, 102.'
Modill, D., 100.
Monkemeyer, K., 152, 205.
Moser, L., 89.
Moesveld, A. L. T., 129, 130.
Mohammed, W., 141.
Mohler, F. L., 26, 27, 141.
Mohr, L., 150.
Moissan, H., 29, 48, 55, 62, 103, 144, 215.
Molentin, I. R., 144.
Moles, E., 66, 70, 71, 72, 82.
Monna, G., 130.
Montemartini, C., 167, 213, 214.
Montignie, E., 64, 179.
Montillon, G. H., 31.
Morath, , 191, 192.
Monran, G. T., 117.
Morhof, D. G., 14.
Moriszuchi, X., 147.
Morrall, F. R., 41.
Morris Jones, W., 18, 39, 41, 42, 151, 152.
Morrow, R, M., 131.
Moser, L., 112, 190, 191, 194, 204.
Motard, I)., 180.
Mom-lot, A., 99, 102, 197.
Mover, J. Bird, 160.
Muck, F. J., 117.
Mullcnheim, S. von, 61.
Mullenheim, V., 160.
Muller, A., 91, 154.
Muller, E., 144.
Miiller, M., 165.
Muller, W., 95, 106, 187.
Muller, W., 24.
Muirdan, S., 21, 135.
Mugellini, C., 156.
Muhs, G., 168, 175.
Muir, M. M. P., 125, 144, 157, 158, 160, 161,
162, 167, 168, 169, 170, 171, 172, 173,
174, 175, 177, 178, 179, 182, 183, 185,
187, 190, 191, 192, 193, 194, 199, 205,
206, 216.
Mulder, F. P., 28.
Murakami, T. 43.
Mussgnug, F., 64, 169, 203, 204.
Muthmann, W., 65, 124.
Muzaffar, S. D., 34, 36, 41, 153.
Myers, C. X., 47.
Mylius, F., 129, 133.
XABAIS, B. DE, 50.
Xaccari, A., 19.
Xarranka. PT._ 141 .
Xakamura, G., 26, 142.
Xarayan, A. L., 26, 140, 141, 142.
Xasu" H., 70, 74.
Xatta, G., 11, 92, 97.
Xaude, S. M., 26.
Xaumann, A., 60, 62, 63, 79, 114, 162.
Xegresco, T., 27.
Xeher, F., 103.
Xelisson, F., 89.
Xemilov, V. A., 44.
Xenadkevich, K. A., 124.
Xeogi, P., 214.
Xernst, W., 22.
Xeuburger, M. C., 18.
Xeuimin, H., 178.
Xeumann, B., 145.
Xeumann, C. F., 85.
Xeumann, F. E., 101.
Xeumann, 0., 21.
Xeumann, R., 30.
Xeumeier, F., 21.
X^eusser, E., 177, 183, 184, 194.
Xcville, F. H., 19, 39.
Xewberry, E., 49, 146.
Xewman, F. H., 155.
Xewnam, W. E., 127.
Xey, 0., 148.
Xiall, 0., 40.
Xickles, J., 64, 76, 79, 81, 82, 172, 174, ]
178, ISO, 181.
Xikasono, T., 117.
Xikolaiev, W., 28.
Xilson, L. F., 101, 103, 105, 111, ]
205.
Xilssen, S., 157.
Xissenson, H., 117.
Xiven, C. D., 21.
Xoodt, L T . H., 59, 67, 68.
Xordcnskiold, A. E., 185.
Xorthrup, E. F., 21, 136.
Xowotny, H., 40.
Xoycs, A. A., 145, 154, 164.
Xusbaum, C., 28, 139.
Xylander, E., 190.
OBIXATA, J., 42.
Obrcimov, L. V., 131.
Ocldo, G., 58, 88, 160.
Orrburn, S. C., 207.
Ogg, A., 18, 130.
Oksman, M., 76.
Olandcr, A., 151.
Ohe, J., Jim., 24, 101.
Olivari, F., 179.
Oliver, T./47.
Oliveris, A., 117.
Olschcwsky, P., 96, 97.
01szewski,"K., 48, 49, 51.
Onnes, H. K., 138.
Ordosen, A. P., 118.
Orlovski, A. L., 99.
Orlncr, H., 40.
Osawa, A., 41.
Ost, H., 118.
Otani, B., 42.
Otin. C. X.. 217.
234
AXTBIOXY AND BISMUTH.
Ottenstein, B., 147.
Otto, F. J., 108.
Ouvrard, L., 62, 69, 83.
Overlach, H., 152.
Owen, M., 22, 138.
PAAL, C., 147, 191.
Pace, E., 39.
Paciello, A., 217.
Padberg, C., 62.
Padoa, M., 112, 113.
Pagenstecher, J. S. F., 108, 111.
Pagniello, A., 30.
Palache, C., 100.
Palm, R., 109.
Paneth, F., 49, 144, 146, 155, 156.
Paracelsus, 15.
?arancl, G., 117.
Pardun, H., 198, 199.
Barker, R. G., 131.
Parkes, L. R,, 31.
Parlitz, H., 20.
Parmley, T. J., 139.
5 arodi, G., 118.
Parravano, N., 39. 42, 44, 103, 112, 115,
149, 152, 153, 204.
Darlington, J. R,, 72.
Pascal, P., 20, 61.
Pascoe, E. H., 17, 119.
Pasteur, L., 85.
Pastureau, J., 167.
Pattabhiramiah, R., 27.
^atterson, R. A., 142.
Paul, T., 98, 108, 116.
Pauling, L., 96.
Pauw, F. do, 59.
Pavel, 0., 109.
Pavlov, P. X., 147.
^acock, M. A., 124, 196.
Pearen, E. H., 141.
Pearson, R. W., 205.
Pearson, T. G., 155, 156.
Pcbal, L. von, 59, 76.
^ck, E. B., 39.
>elabon, H., 22, 97, 101, 102, 112, 138, 194,
199, 204, 205.
'eligot, E. M., 69, SS, 112, 113.
'elletier, B., 114.
'elloux, E., 91.
'endleton, /). H'., 78.
'ercies, E., 131.
'erlmuttcr, S. L, 59, 64.
'erimi, G., 174, 180, 217.
'crret, IT., 152.
errier, A.', 79, 138.
'errot, F. L., 138.
ersox, J., 73, 1.G7.
etej-s,' J. A. A., 31.
etors, J. J. L., 31.
etit, A. J., 19.
etit, P., 48, 50, 78.
etrenko, G., 41.
etrenko, G. L, 39, 150.
ettenkofer, M., 111.
ctterd, W. F./124.
Petzold, W., 77.
Pfaff, C. H., 4.8, 52.
Pfeifer, F., 34, 35.
Pfeiffer, P., 75, 167.
Pfleiderer, G., 39, 40.
Phillips, R,, 111, 167.
Phillips, W., 196.
Piccardi, G., 222.
Picon, M., 207, 208, 215.
Picton, H., 105, 197.
Pietenpol, W. B., 129, 136.
Pillitz, W., 90.
Pincus, A., 220.
Pirsch, H., 191.
Pjanitski, P., 110.
Planitz, H. von der, 29, 48.
Plato, W., 53, 55, 56, 70, 72.
Platz, H., 29.
Playfair, L., 88, 92, 93, 207.
Pleass, W. B., 32.
Plcischl, , 182.
Pletenev, S. A., 17.
Pliny, 14.
Plotnikov, W. A., 60, 76.
Pliiss, M., 134.
Poehlmann, H., 90.
Posrgendorff, J. C., 90.
Poggiale, A. B., 63, 65.
Pokrowsky, G. L, 28.
Pol, L. di,"l47, 191.
Polacci, E., 111.
Poleck, T., 30, 48, 52, 106.
Poli, M., 160.
Poni, P., 124.
Popp, G., 91.
Popper, A., 34, 35.
Porritt, B. 1)., 108.
Portevin, A., 30, 43, 143.
Port no v. A., 220.
Pott, J.'H., 125.
Pouiict, L, 106, 109, 113.
Pound, J. II., 124.
Pouzergucs, !'., 219, 221.
Prabhu, S. M., 105.
Prelinger, ()., 145.
Prentice, J)., 88.
Preschar, J., 117.
Preuss, J., 84.
Prideaux, E. 1>. R., 74, 146.
Prim. A., 100.
Prin-, J. X., 187.
Prins, J. A., 23.
Prinz, H., 58, 88, 94, 104.
Pri\vnoznik, E., 1.24.
Proust,,). L., 28, 84, 92, IK).
Prumer, L. L. A., 107, KM.).
Prythcrch, W. E., 39.
Przc/dziecka-Jcdrzcjow.ska, A., 105.
Purvis, J. E., 27.
Pushin, X. A., 130, 151.
QI:ADRAT, 0., 42.
Quani, G. X., 61, 162.
Quartarolli, A., 2K).
Quercigh, E., 78, 82, 88, 109, 110.
XAME IXDEX.
Q.uesneville, G. A., 130.
Quincke, G., 20, 134.
Quincko, J., 90.
EAAD, A. vois", 54.
Raeder, M. G., S3.
Racier, M., 114.
Ralston, A. W., 162.
Ramachandran, S., 196.
Eamajie, H., 193.
Rammelsberg, C. F., 93, 94, 95, 106, 108,
109, 110, 111, 115, 124, 166. 17,3. 177,
179, 1S2, 201, 207.
Ramon, 'C. V., 139.
Ramsay, W., 114.
Ransome, F. L., 124.
Eao, A. S., 27.
Eao, K. R., 140, 141, 142.
Eao, S. R,, 22, 139.
Eaonlt, F. M., 61.
Raschis, F., 96, 109, 19S.
Ranch, H., 44.
Rauclnitz, H., 64.
Rauter, G., 58, 89, 95, 160, 1SS.
Ray, A. X., 63, 77, 82.
Ray, B. B., 28.
Ray, P., 83.
Ray, P. C., 63, 77, 82.
Ray, S. X., S3.
Razuvaev, G. A., 144.
Read, A. A., 92, 186.
Read, T. B., 16.
Eechou, G., 142.
Recklebcn, H., 48, 52, 53.
Reddrop, J., 193.
Reclenz, P.. 54, 57.
Rcdlich, 0.', 40, 71.
Renault, H. V., 19, 29, 84, S5, SS, 92, 301,
" 103, 110, 142, 185, 1S6, 196. 108.
Reichardr, E., 100.
Reid, E. E., 64.
Reirnann, H., 39.
Reimann, L., 57.
Reinders, W., 19.
Reinsch, H., 145.
Reisler, S., 147.
Reiss, Al. A. von, 118.
Ecmmlcr, W., 98, 103, 160.
Remscn, L, 65, 166, 202.
Ressy, Al"., 118.
Retirers, J. W., 80, 172, 178.
Rhcinboldt, H., 163.
Rieardi, G., 27.
Richards, T. W., 18, 19, 132.
Richardson, 0. \V., 139.
Rickard, T. A., 124.
Eidcal, E. K., 61.
Rideal, S., 87.
Riccke, AY., 127.
Rieckher, T., 111.
Rieirel, E. R,, 189.
Riker, H. S., 91.
Rimini, E., 179.
Rinu-er, AY. E., 18, 25, 29.
Robbs, C. E., 157, 160, 172, 173, 174, 175,
i - -r 1 ~ o TOO 1C- 1 t \ O O 1 rt
Roberts, E. J., 31, 85, 87, 89.
Roberts, J. K., .132, 136.
Robertson, P. AY., 192, 193, 194.
Robinson, H. R., 142.
Robinson, P. L.. 155, 156.
Robinson, R, A., 31, 32.
Robiquet, P. J., 29, 58, 111.
Rocha, H. J., 133.
Roche, A., 31.
Roche, J., 31.
Rode, E. Y., 153.
Rohre. K., 59.
Rohrig, A., Ill, 201.
Roekaert, E., 38.
Rossincr, A., 116.
Rossler, F., 195, 196, 199, 204.
Rohmer, AL, 94.
Rolfink, W., 57.
Rolnick, H., 137.
Roscher, H., 16.
Rose, G., 124, 130, 194.
Rose, H., 30, 58, 59, 62, 63, 70. 72, 73, 84,
85, 90, 92. 93, 97, 98. 99. 101, 102, 104,
105, 107, 108, 110, 111, 113, 114. 167,
168, 187, 197, 198, 219.
Roscnfeld, P., 71.
Rosenheim, A., 53, 54, 64, 73, 78, 88, 01,
190, 214, 216.
Rosenthall, AY., 44.
Rosenthaller, I., 221.
Roshdestvenski, A'. X., 40.
Rossem, A. van, 108.
Rostacni, A., 132.
Roth,"K., 18, 19, 131, 132.
Rotinjanz, L., 59, 01, 76, 80.
Rouse, L. H., 140.
Rousseau, G., 209.
Roussin, Z., 48.
Rowcll, H. \V., 117.
Ruark, A. E., 26, 27, 141.
Rubens, JL, 139.
Rubies, S. Pnia do, 26, 124, 140.
Rublov, S. G., 77, 174.
Rudolii, E., 16J .
Ruchcimcr, L., 161, 213.
RuiT, 0., 21, 29, 30, 53, 54, 55, 56, 57, 58,
69. 70, 72, 89, 104, 108, 135, 158., 193.
Ru^e, E., 167, 168, 207.
Ru hem arm, M., 19.
Ruhland, R. L., 48, 155.
RtilancI, M., 125.
Rupp, E., 191, 192, 219.
Russell, A., 124.
Eydber?, J. E., 132.
Rykenbocr, E. A., 133.
, A., 60, 64, 66, 69, 105.
Sabatier, P., 30.
Saizec, M. cle, 14.
Sala, A., 14.
SalkoAvski, H., 214.
Sanchez, J. A., 203.
Sand, H. J. S., 48, 49, 50.
Sander, \V., 44.
Sanderson, T. C., 68.
ganger, C. R,, 116.
Santos, J. R., 93.
Saper, P. G., 161.
Saposhnikov, A. V., 42.
Sapper, A., 58, 76, 80, 161, 172, 178.
Sartorius, A., 109.
Sauciue, L. I., 65, 75.
Sauerwald, F., 19, 20, 40, 41, 134.
Saunders, A. P., 65.
Sayler, C. H., 65.
Sazcrac, R., 219, 221.
Scarpa, G., 166.
Schachterlc, P., 127.
Schack, H., 44, 103.
Schafer, K., 162, 165, 174.
Schafter, L., 64, 69, 81.
Schaffner, L., 89.
Schaller, W. T., 3, 91, 97, 124.
Schamelhaut, A., 209.
Scharf, K., 139.
Schaumaim, G., 191.
Schearwachter. K., 30.
Scheen, 0., 118.
Scheerer, T., 130, 131.
Scheibe, R., 1.24.
Scheibel, H., 145.
Scheiber, J., 48.
Schenck, P. W., 29.
Schenck, R,, 126, 198, 199.
Scherer, J. M., 58, 108.
Scherpenbenr, P. A. van, 192.
Scheucher, H., 116.
Schiel, J., 48, 51.
Schifr, H., 29, 95, 96, 111, 144, 167, 185,
192.
Schimpff, H., 19, 132.
Schlagel, H., 62.
Schlcclit, H., 149.
Schlegelmilch, F., 73.
Schleicher, A.. 4-1, 118.
Schleicr, 31., 59, 103.
Schlippc, K., 109.
Schlossberger, J., 155.
Schlottmann, P., 29.
Schlundt, H., GO, (51, 70, 76.
Schmid, E., 132.
Schniid, H., 63, 70, 74, 75, 76.
Schmid, W., 205.
Schmidt, A., 48, 162.
Schmidt, Euiren, 117.
Schmidt, P. W., 199, 202.
Schmidt, H., 47.
Schmidt-Hebbcl, E., 155.
Schmidt, K. P., 74.
Schmiicker, S. C., 97, 190.
Schnabel, C., 93/126.
Schneider, E. R., 34, 63, 66, 79, 83, 96, 102,
103, 110, 144, 148, 158, 160, 162, 170,
177, 178, 181, 182, 184, 185, 187, 190,
194, 196, 197, 199, 204.
Schneider, G, AY., 129, 137.
Schneider, L., 192.
Schobig, E., 51, 52.
School^ E. P., 118.
Schoeller, W. R., 15, 88, 126, 188, 197.
Schonbein, C. P., 28, 95, 144, 191, 193.
Schopel, H., 42.
Schoepfle, G. K., 141.
Schoorl, X., 118.
Schopper, H., 150.
Schrader, C., 192.
Schrader, J. C., 111.
Schrauf, A., 91, 124, 204.
Schreeberger, A., 116.
Schroder, E., 124.
Schroder, H., 101.
Schroder, R., 91.
Schucht, L., 192.
Schiibol, P., 19.
Schtirmann, E., 99, 105, 107, 108, 198.
Schuhmann, R., 87.
Schuller, A., 21.
Schulten, A. de, 168, 174, 181, 213, 214.
Schultz-Sellack, A. C., 88, 111, 112, 202.
Schulz, P., 162.
Schulze, A., IS, 23, 25, 32, 130.
Schulze, F. A., 132.
Schulze, G., 32.
Schulze, H. 0., 88, 95, 105.
Schumann, 0., 88, 94, 109, 187.
Schurman, I., 206.
Schuster, P., 61.
Schwabe, E., 146.
: Schwartz, G. U, 13.
Sclnvarz, M. von, 41.
Schwarz, P., 63, 1.13.
SchiAvarzeiiberg, A.. 114.
SchAveigardt, P., 31, 144, 146, 192.
Schweicer, J., 167.
Scott, W. M., 150, 153.
Scidel, A., 60.
Seiffert, W., 47.
Seitlitz, L., 11.
Sen, B. N., 38.
' Sen, K. C., 105.
Scnarmont, H. de, 98, 99, 196.
Sender-ens, J. B., 30, 96, 114.
i Serono, C., 89, 106.
Scrra, E., 08, 88, 160.
! .Serullas, G. S., 76, 77, 79, 82, 83, 170, 17
Setter bers;, C., 65.
' Scubert, K. P. 0., 48, 162, 201, 215.
i Seyclam, V. A., 136.
i Shakov, G. A., 16, 85, 88, 101, 102.
Shannon, E. V., 3, 124.
1 Sharma, P. X., 141.
: Sharnovski, A. M., 77, 174.
! Sharp, D., 189.
' Sharp, R. C., 124.
1 Shat-pe, F. H., 107.
i Sharpies, S. P., 99.
Shepherd, E. S., 153.
: Shidei, T., 26.
Short, A., 17, 107.
Shubnikov, L. V., 131, 136, 137.
Shukov, I. P, 31, 32.
Sicbc, P., 133, 134.
Siebert, W., 23, 25.
Siedentopf, H., 134.
Siedler, P., 18, 19, 117, 131, 132.
Siesbahn, .M., 28, 142.
Siksna, R., 27.
Simon, R. H., 32.
Sirovich, G., 149, 153.
Sjollema, B., 118.
Skey, W., 48.
Skvorzov, V., 220.
Slater, J. W., 30.
Slobodska, Y. Y., 16, 85, 88, 101, 102.
Smirnov, W. A., 41.
Smith, Alpheus W., 22, 26, 141.
Smith, Alva W., 22.
Smith, D. F., 146, 169, 170, 185, 211.
Smith, D. P., 149.
Smith, E. F., 34, 35, 97, 106, 163, 168, 190.
Smith, E. K., 92, 152.
Smith, H. G., 142.
Smith, J. W., 60.
Smith, S. W., 20, 134.
Smith, W., 64, 167.
Smith, W. C., 127.
Snyder, E. F., 31.
Solodovnikov, P. P., 220.
Solomon, D., 18, 42, 151, 152.
Soineren, E. H. S. van, 222.
Somerlad, H., 106.
Soret, C., 109.
Soubeiran, E., 110, 111.
Soullilon, R,, 27.
Souviron, P. J. F., 107.
Spacu, G., 217, 220, 221.
Spacu, P., 221.
Spaulding, J., 180.
Speckmann, F., 126, 198.
Spencer, J. F., 184.
Spencer, L, J., 124.
Spring, W., 29, 98, 144, 195, 196.
Stauber, K., 54, 56, 57.
Stajic, V., 151.
Stallo, H., 89.
Stanek, V., 106, 109.
Stansbie, J. H., 143.
Stark, K. E., 107.
Staudenmaier, L., 124.
Stavenhagen, A., 214.
Steger, W., 186.
Steiner, B., 189.
Steimvehr, H. von, 23, 25, 32.
Stcllmann, W., 64, 78.
Stcnstrom, W., 142.
Stcpanovic, S., 151.
Stephens, E., 41.
Stephenson, B. R., 28, 142.
Stewart, G. W., 131.
Stickings, R, W. E., 215.
Stierstadt, O., 133, 139.
Stillman, T., 197.
Stillwell, C. W., 23, 131.
Stock, A., 23, 25, 48, 49, 50, 51, 58.
Stoddart, E. M., 155.
Stolba, F., 130.
Stolfi, A., 202.
Stone, G. C., 197.
Storch, L., 109.
Straub, J., 221.
Strauch, G., 148.
Streng, A., 30.
Strensers, T., IS, 25, 35, 58.
StrohT, A., 111.
Strom, B. H., 129.
Stromeyer, A., 103, 168, 185, 190, 192.
Sucharda, B., 117.
Suchodski, V. A., 161, 172.
Suchodski, W., 59, 61, 76, 80.
Suchter, A. von, 14.
Suchy, K., 222.
Suciu, G., 220.
Sudborough, J. J., 29, 73, 163.
Sueda, H., 31.
Sugden, S., 20, 59, 70, 74, 134.
Suguira, I., 141.
Summa, 0., 41.
Sushchinski, P. P., 124.
Suydam, V. A., 21.
Svedberg, T., 146.
Swartz, T., 53.
Szebelledy, L., 32, 117.
Szilagyi, J. von, 91, 92, 112.
TAFEL, V., 15.
Takahashi, Y., 103, 199.
Tamchyna, J. V., 219, 221.
Tammann, G., 24, 30, 44, 91, 130, 133, 144,
151, 215, 218, 219.
Tamura, S., 18, 131.
Tanaka, S., 138.
Tanatar, S. M., 160, 176, 183, 184.
Tapley, M. W., 215.
Tararin, V., 151.
Tarible, J., 76.
Tarugi, W., 182.
Tasaki, >L, 44.
Taurinsch, A., 74.
Taverne, H. J., 69.
Tawara, Y., 185.
Teclu, X., 111.
Teitelbaum, M., 219, 221.
Teodorovich, V. P., 144.
Terada. T., 138.
Terenin, A., 142.
Terpugov, F., 60.
Terreil, A., 85, 88, 90, 104, 106, 111.
Thaler, E., 84, 96.
Thenard, L. J., 103, 111.
Thews, E. R., 149.
Thibault, P., 190, 191.
Thiel, A., 146.
Thiele, J., 29, 48, 107.
Thomas, V., 63, 76, 80, 114, 144, 158, 160,
162, 163, 168, 169, 172, 173, 175, 178,
179.
Thomas, W. R., 151.
Thomlmson, J. C., 61.
Thompson, L., 48.
Thomson, J., 61, 71, 144, 160, 162, 169,
186.
Thomson, J. G., 152.
Thomson, T., Ill, 142, 182.
Thresh, J. C., 181, 220.
Throne, B., 47.
238
AXTLMOXY AND BISMUTH.
Thummel, C., 48, 52.
Thummel, K., 30.
Tiecljc, W., 71.
Tieri, A., 131.
Tilk, W., 160.
Tingle, J. B., 88.
Tite, G., 209.
Tivoli, D., 172, 173.
Tocco, G., 99.
Todesco, G., 138.
Topler, K., 134.
Toepler, M., 20, 133.
Toit, >t. S. du, 32.
Tolansky, S., 38.
Tolloczko, S., 59, 60, 61, 66, 76.
Toinicek, 0., 117.
Tomoshige, X., 204.
Tompa, H., 40.
Tomula, E. S., 96, 97.
Tonini, L., 118.
Tookey, C., 57, 103.
Topsoe, H., 58.
Tougarinoff, B., 219.
Toussaint, L., 118.
Toussaint, Mile., 32.
Trautmann, W. J., 187.
Treadwell, F. P., 35, 115.
Tredorovitch, V. P., 28.
Trench, C. C., 202.
Treubert, F., 146, 183, 194, 213, 219.
Triantaphyllidcs, T., 214.
Troquay, P. H., 118.
Tsai, Hw-ei-Pu, 105.
Tsamados, D. M., 216.
Tsuji, T., 189.
Tucek, J., 198.
Tunstal], X., 18.
Turnbull, A. I)., 127.
Turner, A. H., 142.
"Cci-iiPA, S., 189.
Uelsmann, H., 112, 204.
Uemura, T., 3J.
Uhl, J., 29., 144.
Uhlcnhuth, P., 47.
Ullgren, C., 200.
Ornann, P., 107.
Umino, S., 132, 133.
Unger, B., 34, !)7, 98, 101, 10(5, 108, 111.
ITrbain, (L, 207, 208.
L'sanovit.sch, M., 60.
'AIDYA NATHAN, V. I., 22, 139.
alent.ine, Basil, 14, -17, 1)3.
alentiner, S., IS.
allam-e, R. H., 131.
alyashko. X. A , 220.
andeveLdc, A. ,!. ,1., 2S.
anino, L.,(54, 143, M(>, 156, 107, J (>9, 181,
183, 185, 191, 192, 193, 194, 203, 204,
206, 208, 213, 214, 215, 217, 2PJ.
;insl one, I']., (54.
irenne, 1*1., 5 1 .
ill-rent rapp, K., 90.
ief, A. M., (.54, 82.
tube!, \V., 110.
! Vellinger, E., 31.
Verain, M., 32.
! Vercillo, A., 64.
: Verma, M. R., 22, 139.
; Vcrncuil, A. V. L., 105.
I Vest rine, E. H., 27.
: Veszclka, J., 41.
! Viel, E., 116.
j Vieweg, A. M., 27. '
! Vigouroux, E., 43, 64.
j Vincent, C., 64.
! Vincent ini, G., 133.
! Virup, P. G., 220.
Vitali, D., 52.
Viviani, E., 39, 42, 44.
Vies, F., 3.1.
Vogel A., 182.
Vogel, F., 17.
Vogel, H. A. von, 48, 51, 58, 62, 63, 103
111.
Vogel, J. C., 31.
Vosel, R., 40, 43, 44, 150, 151.
Vogel, W., 88.
Vogelsang, W., 190, 216.
Votil, H.f99.
Voigt, A., 161.
Voigt, B., 21.
Voigt, K. H., 101.
Voigt, P. R., 49, 50.
Voigt, W., 132,
Volfson, B. X., 40.
Volharcl, J., 163.
Voogd, J., 150, 151.
Voronov, V. M., 44.
Vortinann, G., 35, 62, 99, 109, 116, 203.
Voskuil, W. H., 3.
Voss, G., 153.
Vosskiihler, H., 149.
Vournasos, A. C., 77, 81, 82, 83, 84 174
2.K).
V'ridhachalain, P. X., 31.
U'Ar-KF.XKODIvR, If. W. F., 100, 109.
Wachtt-r, , 1(59.
Wagnc-r, E., 138.
Wagner, -I. R., 111.
\Vagner, P. A., 124.
U'ailc, C. X., 88.
\Vaki, S., 44.
U'alden, P., 61, 70, 81, 82.
Walerstein, I., 142.
Walker, .1., cS8, 89, 92, 189, 190
U'aiker, T. L.,' 124.
Wallace^ I). I,., 1)7.
\ValIaeh, ,}., JK5.
\Vallot, J., IS.
\Vallrotli, K. A., 214.
Waher, B., 28.
Wallers, F. M., 141.
L', C 1 . V., 3, 15, 16.
ard, F. A., 136.
arininon, R., 168.
'ans,' C., 164, 109.
arren, H. X., 57, 98, 103.
allenberg, H. von, 21, .135.
serfuhr, K., 163.
NAME INDEX.
Wastall, H., 150.
Watanabe, W., 89.
Watson, G., 68.
"Watson, W., 68.
Wattenbcrg, H., 117.
Wayland, E. J., 124.
Weather-ill, P. F., 34, 36.
Weaver, F. D., 44.
Weber, R., 34/58, 62, 64, 71, 72, 73, SS, 94,
144, 158, 159, 160, 171, 175, 177.
Websky, C. F. M., 93, 104, 106, 112,
Webster, W. L., 129, 133.
Wedekind, E., 43.
Weekes, E. J., 48, 49, 50, 52, 155.
Wehenhoff, B. L., 44.
Weidert, F., 137.
Weigel, 0., 196.
Weinbenr, S. A., 70, 78.
Weinland, R. F., 63, 70, 73, 74, 75, 76, 78,
90, 111, 158, 167.
Weinschenk, E., 98.
Weisbach, A., 124.
Weith, W., 66, 162, 169.
Welkow, A., 81, 180.
Weller, A., 94.
Wells, H. L., 65, 70, 180.
Wenger, P., 117.
Weppen, H., 104, 111.
Werner, A., 110.
Werner, F. F., 216.
Werner, 0., 60, 61.
Wernicke, W., 192,
Werther, G., 194.
Westenbrink, H. G. K., 31.
Westermann, J. W., 188.
Westeren, A., 39, 40. 41.
Weyer, H., 76, 161, 172.
Wheeler, H. J., 65.
Whitby, C. S., 74.
White, H. E., 141.
White, J. D., 18.
Wiedemann, G., 135.
Wiederholt, E., 48.
Wilhelm, J. 0., 21.
Wilkms, H., 20.
Wilkinson, J. A., 61, 162.
Willard, H. H., 34, 35.
Willey, L. A., 41.
Willnerodt, C., 88.
Williams, A. T., 141.
Williams, E. V., 189.
Williams, J. H., 142.
Williams, R. S., 41, 42, 43, 151.
Williams, W. C., 21, 59, 66, 69, 79, 135,
161, 172, 178.
! Williamson, E. D., 132,
i Wills, A. R., 13S.
! Willstaedt, H., 64.
i Wilrn, T., 106, 107, 108.
Wilson, L., 17.
Wilson, N. E., 109.
Wilson, S., 100.
Winogorov, G., 41.
Winssinger, C., 199.
! Winter, R., 17.
Wintcmitz, E,, 155, 156.
: Wittek, R., 112.
Wittstem, G. C., 100, 101. 105, 107, 108.
Wohler, W., 90.
Wolf, J., 118.
Wolff, A., 91.
; Wood, J. K., 67, 90.
Woodward, E., 190, 191, 192, 193.
Worcester, C. P., 61, 76, 80.
Worrell, S. W., 49, 50.
Worsley, R. R. le G., 192, 193, 194.
Wrede/F., 50.
Wiinnenberg, E., 58, 76, 80, 161, 172, 17
Wurschmidt, J., 130.
Wulff, J., 140, 141.
Wust. F., 19.
Wyruboff, G. N., 216.
YAMAGUTI, T., 101.
Yamamoto, T., 40.
Yamanchi, Y., 103.
Yap, Chu-Phay, 42.
Younir, J. F. T., 141.
Youtz, L. A., 35, 94, 100, 101.
i Yvon, P., 181, 208, 209.
! ZAETEV, M. V., 97, 101, 104.
I Zahn, H., 22.
i Zambelli, L., 93, 103.
I Zani, V., 100, 101.
i Zartmann, I. F., 135.
i Zavattiero, E., 137.
' Zealley, E. A. V., 124.
; Zeclner, J., 56, 72, 158, 193.
' Zee man, P., 141.
Zcnglielis, C., 21.
. ZheiucLiuzhnui, S. P., 40, 151.
: Zhukov, I. I. See Sliukov.
Zimmermann, W., 52.
Zintl, E.. 34, 36, 39, 117, 149, 150.
. Zsio-mondy, R., 105.
; Zumbusch, E.. 1.56, 18,1.
' Zumstein. R. V., 27, 140, 141.
Zwicky, E., 131 .
SUBJECT INDEX.
AGRICOLTTE, 123, 217.
Aikinite, 120.
Alcohol, a- term used for stibnite, 14.
Algaroth, Powder of, 15.
Alkali antimonates, 96.
antimonites, 90.
bismuthates, 182.
)ismuthites, 144, 146.
elenoantimonites, 113.
,tibiothiosulphates, 112.
thioantimonates, 109.
thioantimonite, 109.
Allemontite, 13, 115.
Alloy systems:
Antimony-aluminium, 41.
,, -arsenic, 42.
-bismuth, 42, 152.
,, -cadmium, 40.
,, -calcium, 40.
,, -chromium, 42.
-cobalt, 43.
,, -copper, 39.
-gold, 40.
,, -iron, 43.
-lead, 41.
,, -magnesium, 40.
,, -manganese, 43.
-nickel, 43.
,, -palladium, 44.
,, -platinum, 44.
,, -potassium, 30.
,, -selenium, 42.
,, -silicon, 41.
-silver, 39.
,, -sodium, 3D.
,, -tellurium, 43.
,, -thallium, 41.
-tin, 41.
-zinc, 40.
Bismuth-aluminium, 151 .
,, -antimony, -12, 1-12.
,, -cadmium, 15 1.
,, -calcium, 150.
-cerium, lf)l.
-cobalt, lf>3.
,, -copper, 150.
,, -gallium, 151.
-gold, 150.
Alloy systems cant.
Bismuth-nickel, 153.
,, -potassium, 149.
,, -rhodium, 153.
,, -selenium, 152.
,, -silicon, 151.
j ,, -silver, 150.
' ,, -sodium, 149.
,, -tellurium, 152.
,, -thallium, 151.
-tin, 151.
,, -zinc, 150.
; Alloys, Antimony, Binary, 38-44.
1 , , Ternary, 44.
, Bismuth, Binary, 149-153.
, , Ternary, 153.
, , Quaternary, 153.
Ammiolite, 11.
Ammonium antimoniodobromide, 82.
bismuth thiosulphatc, 203.
fluobismuthate, 158.
hypobrornoantimonate, 78.
Andorite, 6.
Anodes for chromium plating, 38.
Antifriction metal, 38.
Antimonates, 3, 46, 89, 95, 96-97, 103
108.
Antimonial lead, 38.
poisoning, 47.
Antirnonic acids, 3(5, 63, 71, 95.
Antimonides, 30, 38-44, 6-4, 105.
Antimonious compounds, Analytical dis-
tinction from antiinonic, 1 16.
Antimonite, 3, 4.
Antimonites, ;$, II, 46, SS, 90-91.
Antinioniuw, 14.
cruduni, 97.
(liuphordiriiui. (iblnttnn, 93.
nan (iLlitt ii.tu, !),'>.
Hidpkiirdtinn, 111.
Antimony, Absorption of hydrogen by, 28..
-, Action of nitric acid on, 29-30.
, Allotropy of, 17- IS, 2-1-25.
alloys, 3S-4 I.
, Commercial, 3S.
, a-, IS. Sec also Khombohcdral
Ant imony.
---, Amorphous, IS, 22-25, 51.
SUBJECT IXDEX.
Antimony arsenide, 115.
, Atomicity of, 30.
, Atomic number, 32.
--, radius, IS.
--, wei.uiit., 32-38.
- , /;'-, 18, 22-25. See. also Amorphous
Antimony.
, Black, 51.
bloom, 3.
bromides, 45, 70-78.
bromoiodide, 84.
, Butter of, 15.
, Chemical properties, 28-32.
, Chemically pure, 17.
chlorides, 45, 57-76, 88.
chloroiodides, 72.
chlorosulphate, 111.
compounds, General, 45-4(5.
, Critical potential of, 27.
, Crystal luminescence, 20.
, Detection, Dry reactions, 115.
, , Wet reactions, 115.
dioxide, 91-93. See Antimony
tctroxide.
, Early history, 1.4-15.
electrode, 31-32.
, potential, 31.
, Estimation, Electrolytic methods, 118
, -, Gravimetric methods, 11(5.
, , Microanalytical methods, 118.
, , Volumetric methods, 117.
---, Explosive, ]S, 2225. See Amorphous
Antimony.
, Extraction, Electrolytic methods, 1(5-
17.
, - , Eurnace methods, 15-16.
, , Wet methods, 16, J 7.
fluorides, 45, .5357.
dance, 3, 97.
--- glass, 88, 1)2, 97, 110.
halides, 45.
, Mixed, 10, 83-84.
hydrides, 47-53.
- hydroxide;, 89.
- , Inner potential, 38.
iodides, 45, 7882.
-- lodocyanides, 83.
iodoh vdrobronn'c acid, 82.
\ Salts of, 82.
, lomsation potential, 27.
- , Isotopes, 36, 38.
---, Liquid, Boiling point, 21.
, , Coefficient of viscosity, 2().
, -, Density, 20.
- , , Electrical resistance, 2.1.
t ? .Specific heat, 2().
, , Surface tension, 20
, Liver of, 106.
- --, Mass spectrum, 33.
mcrcuribromoiodide, 84.
, Metallic pills of, J5.
methyl, 38.
- minerals, 3-1 3.
, Moment of inertia of diatomic mole-
cules, 38.
, Xative, 3, 4, 1.8.
Antimony nitrate, 29, 104, 113-114.
, Basic, 113.
, Xormal, 114.
nitride, 03, 113.
--, Xuclear moment, 38.
, separation in diatomic molecules, 38.
-, Occurrence, 3-13.
- ochre, 3.
ores, 3.
, World's production of, 17.
oxides, 30, 46, 84-97.
oxybromides, 77.
oxychlorides, 15, 64, 66-G9, 79.
oxyfluorides, 53.
oxyioclides, 79, 80, 81, 82-S3.
oxysulphides, 88, 94, 103, 104, 109-111,
112.
, Parachor, 20.
pentahromide, 78.
, Double and complex compounds of.
78.
pentachloride, 29, 70-74, 10S.
, Ammoniates, 73.
, Constitution of, 74.
, Dissociation of, 71.
, Double and complex compounds of,
72, 73, 74-76.
, Hydrolysis of, 71.
- , Monohydrate, 71.
, Parachor, 74.
, Solvent action of, 71.
pentailuondc, 55-57.
, Di hydrate, 55.
, Double and complex compounds of,
5657.
pentaioclide, 78.
pentaselenide, 112.
pcntasulphide, 30, 94, 97, 107-108, 109.
, Sols, 112.
pcntoxidc, 36, 03, 88, 93-90, 103, 104.
, Alcogcls, 95.
, Hydrates, 95-90, 97.
, Sols, 95.
phosphate, 114.
, Dihydrate, 114.
phosphide, 114.
, Physical properties, 17-28.
, Physiological action, 40-47.
, Precipitation of, from solutions, 28.
pyrophosphatc, 114.
, Pv educing action of, 30.
, Refining of, 15, 16.
, Resonance potential of, 27.
-, Rhornbohedral, 18-22.
-, , Compressibility, 18.
-, , Corbino effect, 22.
-, , Density, 18.
-. , Electrical resistance, 21.
-, , Entropy, 19.
, , Ettinirshauscn effect, 22.
-, , Hall cilccl, 22.
--, --, Hardness, 19.
-, , Heat capacity, 19.
--. , Latent heat of fusion, 20.
-, , Linear vclociiv of crystallisation,
20.
AXTiMOXY AXD BISMUTH.
Antimony, Pvlionibohcdral, ^Magnetic sus- ;
ceptibihty, 22. j
, , , Influence of particle size, i
2"-' i
, . Melting point, 19. !
, , Modulus of elasticity in shear, 19. ;
, , Xernst ctlcct, 22. :
, , Refractive index, 22.
, , Righi-Lcduc effect, 22.
, -, Specific heat, 19.
, , Spontaneous crystallising power, 20.
, , Tensile strength, 19.
, , Thermal conductivity, 21. '
, , expansion, 18, 19. '.
, , Thermo-electric properties, 22.
, , Transition point, 25.
- , , Young's modulus, 19. \
, Secondary, 17. '
selcnicies, 112.
selcnitcs, 113.
, Single crystals, 22, 28.
, Spectrum, 25-28.
, , Absorption, 26.
, , Arc, 25-26.
, , Flame, 27.
, -, Persistent lines, 26.
, , Series, 27.
.. , Spark, 26, 27.
, , Spectral terms, 2(5.
, , Ultimate rays, 27.
, , Ultra- violet',' 27.
, , X-ray, 28.
, Sub-atomic structure-, 27.
suboxide, 45.
subsulphidc, 97.
sulphate, 29,62, 80, 88, 103, 111-112.
/Acid, 104, 1.12.
, Basic, H 1-1 12.
, Xormal, 111.
, , Double salts of, 111.
- sulphide, Golden, 10(5, 1 07.
sulphides, 46, 97-108.
----- sulphite, 111.
ltd. rabromide, 77.
, Complex compounds of, 77-78.
- - fctrachloride, 70.
, Complex compounds of, 70.
tcfrasulphide, 106-107.
tetroxidc, .16, 3(5, 88, 91-93, !H, 102.
, Hydrated, 92.
, Thermionic, discharge spectra, 27.
thiochloride, (52, (59, 72.
t hioiluondo, 55.
thioiodide, 79, 80, 83.
thiophosphale, 1 14.
thiosulphatcs, Complex, 1 12.
tnbromide, J, 33, 35, 7(5-77, SO.
, Complex compounds of, 77.
trichloride, 15, 22, 2-1, 29, 30, 33, 3(5, 37,
f> 7-110, {)<), SO, 88, 89, 91-, 104, 1.08.
, Animoniates, 6.3.
, Binary systems containing (Thermal
examination), 6(5.
, Chemical properties, (51-64.
, Conductivity of solutions in molten,
60.
niimony trichloride, Double and compl
compounds of, 62, 63, 64-6t5.
- , Hydrolysis of, 60, 62, 66-68, 85.
, Physical properties, 58-61.
, Polymorphism, 58.
, Preparation, 57-58.
solutions, Spark spectrum of, 27.
, Spatial structure of, 58.
-trifluoriclc, 16, 53-54, 103.
, Double and complex compounds (
54.
- trjfluorodibronncle, 84.
- trirluorodiehlorielc, 83.
- trifluorodiiodide, 84.
- mhydride, 23, 25, 28, 38, 45, 48-53.
- , Action upon silver nitrate solutior
52.
- , Chemical properties, 50-53.
, Electrolytic production, 49.
- -, Physical properties, 49, 50.
- , Physiological action, 50.
- triiodide, 23, 35, 77-82.
- - . Amorphous, 81.
- , Binary systems containing (Therm
examination), 82.
- , Chemical properties, 80-81.
, Double and complex compoum
81-82.
- , Hydrolysis of, 79, 83.
, Molecular weight, 81.
, Monoclmic, 81 .
, Monotropism. of, 79.
, Physical properties, 79-80.
, Polymorphism, 79.
, Preparation, 78.
, Rhombic, 81.
, Trigonal, 79-81.
trioxidc, .1(5, 24, 31, (59, 77, SO, 81-!
94, 102, 108.
, Chemical properties, 88-89.
- , Complex compounds with alk
tun<fstatcs. 91.
, Cubic, 85-87.
-, M yd rated, 89.
, Physical properties, 85.
, Physiological action, 91.
, Polymorphism, 85.
-, Preparation, 8485.
--- , II hombic, 87.
- , Use in paints and enamels, 91.
--, Vapour pressure of, 80-S7.
trisclcindc, 21, 1 12.
tnsulphidc, 29, 33, (52, 83, 88, <) 1-, 9
100, 107.
, Amorphous, 99, lol .
- , Uiimry systems containing (Thi'rn
exa mmat ion), 103.
- , Chemical properties, 102-105.
, Compounds \vith hydrogen sulphic
105.
, Crystalline, 98-99, 1.00-101.
, Hydrates of, 105.
- , Physical properties, 100-102.
, Polymorphism, 97, 1 00.
, Precipitation by hydrogen sulphi*
99, 103.
SUBJECT INDEX.
243
Antimony trisulphide. Preparation, 98-100.
- , Red precipitated., 100.
, Roasting of, 102.
, Sols, 105.
tritelluride, 113.
, Valency, 45.
, Valve effect, 32.
, Vapour density, 21.
vapour, Fluorescence of, 27.
, Molecular constitution, 26.
, Volume chanirc on solidification, 20.
, White, 3.
, Yellow modification of, 25, 51.
, Zeeman effect, 27.
Antimonyl bromide, 77.
chloride, 69, 85.
di hydrogen phosphite, 114.
fluoride, 53.
iodide, 82.
pcrchlorate, 76.
thioaiitirnonatc, 110.
Arequipite, 12.
Arsenobisrnitc, 123.
Atelestite, 214.
Atopite, 11.
BABBITT metal, 38.
Badenitc, 123.
Barcenite, 10.
Barium bismuth thiosulphate, 203.
stibiothiosulphate, 112.
Basiiiite, 12.
Basobismutite, 122, 215.
Bcegerite, 121.
J3cnzoard'i.cu-r/i 'ni,i'n,erulc, 1)3.
Berthierite, 8.
Betts Electrolytic Refining Process, 127.
Bindhc unite, 12.
Bismite, 111), 122.
Bis in on, 191.
Bismuth, Action of nitric acid on, 143.
, Allotropy, 129-130.
, Alloys, Binary, 149-153.
, , Ternary, .1.49, 1-53.
, , Quaternary, 149, 1.53,
ammonium fluoride, 158.
, Analyses, 128, 129.
, Anodic corrosion, 146.
antimonatcs, 215.
arsenate, 214-215.
, Basic, 215.
, Hem i hydrate, 214.
arsenide, 214.
arsenite, 214.
, Atomic diameter, 131.
, heat, 133.
, weight, 147-148.
, Atomicity, 13-1, 135.
bromides, 170-174.
carbonate;, 215.
, Basic, 2J5.
, Chemical properties, 142-147.
chlorate, 169. '
chlorides, 1 58-1 67.
chromates, 205-206.
, Alkali, 206.
VOL. VT. : v.
Bismuth chromite, 205.
chromothiocyanate, 216.
cobalticyanide, 216.
, Colloidal, 146-147.
compounds, General, 154.
, Hydrolysis, 154.
, Physiological action, 154-155.
, Compressibility, 132.
, Corbino effect," 139.
, Crystalline form, 130.
, Crystallisation of, 131, 133.
cyanides, 198, 215-216.
, Complex, 216.
, Density, 131.
deposits, Geological formation of, in
S. America, 125.
, Detection, Dry reactions, 218.
, , Wet reactions, 218-219.
dibromide, 171.
dichloridc, 158-160, 187.
, Double compounds of, 160.
dichromates, 205-206.
dihydride, 155.
diiodide, 175-177.
dimethyl, 177.
dioxide, 182.
dithionate, 204.
dithiophosphate, 214.
, Early history, 125.
, Electrical properties, 136-137.
, Electrochemical properties, 144-146.
, Electrode potential, 145-146.
, Electrolytic deposition of, 127, 146.
, Estimation, Colorimetric methods, 220-
221.
, , Electrolytic methods, 221.
, , Gravimetric methods, 219-220.
, , Microchemical methods, 221-222.
, , Spectrograpkic methods, 222.
, , Volumetric methods, 220.
, Ettingshausen effect, 139.
, Extraction, 125-129.
, , Wet methods, 128-129.
ferricyamde, 216.
ferro cyanide, 216.
, Flowers of, 142. See also Florcs
bismuti.
fluorides, 157-158.
, Galvanometric effects, 139.
glance, 119, 195.
halides, 144, 156-182.
Hall effect, 139.
, Hardness, 132.
, Heat of dissociation of diatomic mole-
cules of, 135.
hexoxide, 194.
, Hisrh pressure modification of, 130.
, Higher oxides of, 191-194.
- hydride, Solid, 155.
hydrides, 155-156.
hydroxide, 190.
hypophosphite, 213.
, Basic, 213.
lodate, 179, 181.
iodides, J 75-182.
, lonisation potential, 141.
16*
244
ANTIMONY AND BISMUTH.
Bismuth, Isotopes, 147.
, Latent heat of fusion, 133.
, Liquid, Boiling point, 135.
, , Density, 134.
, , Effect of superheating on, 133.
, , Latent heat of vaporisation, 135.
, , Specific heat, .134.
, , Supercooling of, 133.
, , Surface tension, 134.
, , Vapour pressure, 1 35.
, , Velocity of crystallisation, 133.
, , Viscosity, 134.
, Magnetic properties, 138-139.
, Mass number, 147.
, Melting point, 133.
metapkosphatc, 214.
minerals, 119-125.
, Molecular weight, 134, 135.
molybdates, 206.
monoselenide, 204.
monosulphide, 194-195.
m onotellu ride, 205.
monoxide, 182-1.85, 187, 101.
, Mosaic structure, 131.
, Native, 110, 120, 131.
, Ncrnst effect, 130.
nitrate, Basic, 208, 209-210.
, , Complex compounds of, 210.
, , Solubility in aqueous nitric acid,
210-211.
, Co-ordination formula, 208-209.
, Dihydratc, 208, 213.
, Double salts of, 208.
1 Hydrolysis, 209.
, Normal", 207-208.
__ f Pentalmlrate, 207-208.
f __ ? Solubility of, 211.
, Scsquihydratc, 208.
, , Solubility of, 2 12.
nitride, 187, 206.
nitrite, 206.
- nucleus, Moment of momentum, L4J.
, Occurrence, 110-125.
ochre, 119, 122, 185.
oleate, 154.
, Optical properties, 139.
ores, 1 1 0.
orthoanfimonate, 215.
, Basic, 215.
orthopho.sphate, 21 3-2 J -4.
, Basic, 214.
, Trihydrate, 214.
orthosiheate, 217.
, Over-voltage, 14.6.
oxides, 144, .1.82-194.
1 Hydratocl, 189-191, 192, 193.
, , Colloidal, .191.
, , Hydrosols, 191.
oxybromatc, 175.
oxvbromides, 174175, 187.
oxychloridcs, 162, 107-109, 170, 187.
oxyeobaltinitritcs, 207.
oxyfluoride, 158.
oxyiodidcs, 177, 178, 179, 181, 182.
oxymeta-antimonate, 215.
oxynitrate, 208.
Bismuth oxysulphidcs, 201.
oxytri fluoride, 158.
, Parachor, 134.
pentafiuoridc, 156, 157, 158.
pentoxide, 184, 187, 193-194.
- pentoxide, Hydrated, 193.
perchlorate, 169-170.
_ s Basic, 170.
, Conductivity of aqueous solutions of,
170.
, Electrolysis of aqueous solutions of,
146, 222.
, Pcntahydrate, 169.
phosphate, 187, 213-214.
- phosphide, 213.
phosphite, 213.
, Photoelectric threshold, 130.
, Physical properties, 129-142.
, Physiological action, 154-155.
, Pvrophoric, 143.
, .Rctinmir of, 126, 128-129.
, , Electrolytic, 127, 146.
, Righi-Leduc cii'ect, 139.
selenate, 205.
sclemdes, 170, 204-205.
selenites, 205.
selenochloridc, 170, 205.
sesqmoxide, 185-191. See Bismuth
trioxide.
sesquisulphide, 195-199. Sec Bismuth
trisulphide.
silicates, 217.
, Single crystals, 131.
.skuttorudite, 123.
, Sols, 146.
-, Specific heat, 132.
, magnetic susceptibility, 138.
--, Spectrum, Absorption, 141.
, , Arc, 140.
, , , Rait nlll'in.c., 140.
, - , fluorescence, 142.
, , Second order, 140.
._, , Spark, 1-40.
, , Tlnrd order, MO.
, , Under- \vatei 1 spark, M2.
-, , X-ray, M2.
t Structure, 130-131.
subiodide. Sec Bismuth diiodide.
- subnitratc, 151.
suboxide, 100. Sec; a.lso Bismuth mon-
oxide.
su boxy iodide, 176.
subselenide, 204.
sulphate, Addition compounds of, 202.
, Dihydrute, 2()2.
, Double salts of, 202.
, Heptahydrate, 202.
, Isomorphism of, 202.
, Normal, 201-202.
sulphates, 188, 198, 199, 201-202.
-, Acid, 202.
, Basic, 170, 184, 187, 202.
sulphides, 194-199.
sulphites, 201.
, Basic, 201.
telluratc, 205.
SUBJECT INDEX.
245
Bismuth telluricles, 205.
9 Tensile strength, 132.
tetroxide, 192-193, 104.
, Thermal conductivity, 135-136
, e.m.f., 138.
y - expansion, 131-132.
, Thcrmoniagnetic effects, 139.
thiobromidc, 173, 175.
thiochloride, 162, 170.
, Complex, 162.
- thiocyanate, 216.
, Basic, 216.
tbioiodide, .178, JS2.
- thiophosphate, 162, 21-1.
thiosulphates, 203.
, Complex, 203-204.
thiotellmide, 200, 205.
- thiotellurites, 205.
-, Toxie properties, 15,1.
ti*ibromide, 171174.
, Ammoniates, 173.
, Complex compounds of, 173-174.
, Hydrolysis, 172.
, Preparation, 171-172.
, Properties, 172-173.
trichloride, 160-163, 170, 184, 187, 188,
195, 198, 199.
, Ammoniates, 167.
, Chemical properties, 161-163.
, Complex compounds of, 162, 163.
, - , with organic- bases, 165, 167.
, Hydra ted, 103.
, Hydrolysis, H>2, 163.
, Physical properties, 100-161.
, Preparation, 160.
, Spark spectrum of dilute aqueous
solutions of, 142.
tri fluoride, 157-158.
, Hydrolysis, 157.
trih.yd.ride, 155-156.
, Decomposition of, 15G.
, Distinction from antimony tri-
hydride, 156.
tri iodide, 177-181, 182.
, Am inornate, 179.
, Complex compounds of, 179-1 81.
, , with organic bases, 181.
, Hydrolysis, 179.
, Molecular weight, 179.
, Preparation, L77.
, Properties, 178-181.
trioxide, 142, 1 M, Hi;}, 178, 179, 181,
185-191, 198, 199, 204, 208.
^ Amphotcric properties, 188.
, Hydrated, 189-191.
- , Polymorphism, L85.
, Preparation, 185.
, Properties, 185-189.
, Reduction of, 183, 184, 187, 188.
, Use as catalyst, 188-189.
triselenidc, 204-20.1.
trisulphidc, 144, 170, 173, 179, 181, 182,
187, 188, 195-199.
, Complex unions formed from, 197.
, Preparation, 195.
., Properties, 196-199,
I Bismuth trisulphide, Solubility in aqueous
solutions of alkali sulphides, 197
tritelluride, 205.
trithionate, 204.
tungstates, 206.
uranates, 206.
, Valency, 154.
vapour, Absorption spectrum, 141.
, , Raie, ultima, 141.
, Fluorescence spectrum, 142.
, pressure, 13o.
, Volume change on melting, 133.
, Young's modulus, 132.
, Zeernan effect, 141.
Bismuthatcs, Alkali, 182, 193-194.
B ismuthi liydroxidiu //? , 191.
Bisrauthic acid, 192, 193.
Bismuthidcs, 149-1 o:). See also Alloy
systems.
Bismuthinite, 119, 120, 125, 195, 196.
, Seleniferous, 121.
Bismuthinitrites, 206-207.
Bismuthobromocyanides, 216.
Bismuthothiocyanates, 217.
Bisniuthothiocyanic acids, 216-217.
Bismuthyl bromate, 175.
bromide, 172, 173, 174.
chlorate, 169.
chloride, 167-169.
, Hydrated, 168.
, Preparation, 167.
, Properties, 168.
, Solubility in hydrochloric acid, 165.
cobaltmitrites, 207.
fluoride, 157, 158.
hydroxide, 175, 191.
iodide, 177, 179, 181.
nitrate, 146, 154.
nitrite, 206.
, Complex compounds of, 206.
Bisnmtite, 119, 122, 215.
Bismutoplagionite, 121.
Bismutosnmltite, 123.
Bismutosphacrite, 122, 215.
Bismutotantalite, 123.
Bolivian ite, 9.
Bolivite, 201.
Boulangerite, 7.
Bourn oiiite, 5.
Breithauptite, 13.
Britannia metal, 38.
Bromoantimonic acids, 46, 78.
, Salts of, 78.
Bromobismuthitcs, 174.
Brongniardite, 6.
CESIUM bismuth thiosulphate, 203.
Calcium stibiothiostilphate, 112.
Cervantite, 3, 9, 37, 91.
Chalcostibite, 4.
China ochre, 11.
Chiviatite, 121.
Cluoroantimonic acids, 36, 45, 71, 74-76.
, Salts of, 75.
Chlorobismuthites, 165-167.
Chlorobismuthous acid, 163-165.
246
AXTIMOXY AND BISMUTH.
Chlorobismuthous acid, Substituted am-
monium compounds of, 1G5.
Chondostibian, 10.
Cobalt antimonide, 64.
bismuth nitrate, 208.
Copper antimonide, 64.
antimonites, 90, 91.
bismuth, thiosulphate, 203.
Cordova ochre, 1 ] .
Coronguite, 12.
Corynite, 8.
Cosalite, 119, 121.
Cupric antimony oxyiodide, 83.
Cuprobisnmtite, 120.
Cuprous antimony iodocyanidc, 83.
Cylindrite, 8.
DAUBREITE, 167.
Derbylite, 12.
Diantimony dihydride, 48.
Diaphorite, 6.
/^-Dichloro-octachlorO'dibismuthites, 165.
Dimethoxybismuth, 177.
DragendorfFs reagent, 181.
Dyscrasite, 13.
ElCHBERGTTj:, 5, 121.
Emplectite, 120.
Epiboulangerite, 8.
Eulytite, 1~22, 217.
FALKINHAYNITE, 5.
Famatinitc, 8.
Flajolotitc, 13.
Flores antimonii, 84.
bismuti, 1.42, 185.
Flowers of bismuth, 142.
Franckeitc, 8.
Freezing point curves, Binary systems :
Antimony-sulphur, 97, 98.
Antimony trioxide-antimony trisulphide,
88, 109-110.
Antimony trisulphide-bismuth trisul-
phide, 199, 200.
Bismuth-bismuth trichloride, 158-159.
Bismuth-bromine, 171.
Bismuth-iodine, 175-176.
Bismuth-selenium, 195, 204.
Bismuth-sulphur, 194, 195.
Bismuth-tellurium, 194, 205.
Bismuth trioxide-lead monoxide, 188,
189.
Bismuth trisulphide-bismuth tritelluride,
199, 200.
Bismuth trisulphide-silvcr selenide, 199,
200.
GALENOBTSMUTTTE, 120.
Galicia ochre, 11.
Geocronite, 7.
Gold antimonitc, 90.
Goldiieldite, 5, 122.
Grey antimony ore, 97.
Grunlingite, 122.
Guanajuatite, 121, 204.
Guejarite, 4.
HARRIS process, 1 7.
Hauchccornite, 13, 123.
Heptachlorodibisrauthous acid, Salts of.
166.
Hexachlorobismutliites, 165.
Histrixite, 9, 121.
Horsfordite, 13.
Hyclrofluobismuthic acid, 157.
acid, 179.
-- , Salts of, 180-181.
JAMES ox m:, 6.
Joseito, 121.
KALLILTTE, 121.
Karelin itc, 201.
fvermes mineral, 110-111.
Kermcsite, 3, 8, 109-1 10.
Kilbrickcnite, 7.
Klaprotholile, 120.
Kobe! lite, 7, 121.
Ivocchlinitc, 123.
Kohl, 14.
LAMPROSTIBTAX, 12.
Langbanite, 10.
''Lcnkonin," 91.
Lewisite, 11.
Lillianite, 121.
Lithium antimoniodobromidc, 82.
''Liver of antimony,'' 106.
Livin^stonite, 5.
:s Luv extra," 91 .
MAGNESIUM bismuth nitrato, 208.
Macnctostibian, 12.
Manganese l)ismutli nitrate, 208.
Marsh's test, 115, 1 16.
Malaria perlaln Kc.rkr'nicjii, 93.
Matilditc, 120.
Manzeliitc, 1.1.
Melanostibian, 11.
Menechinitc, 7.
Merouric antimony iodocyanido, S3.
-- oxyiodide, 83.
M Mcnr-iiis r/it(i>., 15, 57.
Mercury bismuth nitrate, 208.
Meta.-antimonates, 96.
-antimomous acid, 89.
-- antimonites, 90.
-- bromoantirnonic acid, -46, 7.S.
-- , Salts of, 78.
-- chlomantimonatcs, 75.
-- chloroantimonio acid, 45, 74.
--- , Hydrolysis of, 74.
--- , Salts ol, 75.
-hypoantimonic acid, 46, 92.
-- " , Salts of, 93.
Miartryrite, 5.
Minerals, Antimony, 4-13.
, Bismuth, 119-125.
Mixitc, 123, 124.
Montanite, 122, 205.
SUBJECT INDEX.
XADORITE, 10.
Xagyagite, 9.
Nat'ive'bismuth, 110, 120, 131.
Xickel antimonicle, 64.
bismuth nitrate, 208.
OCHRE, China, 11.
-, Cordova, 11.
, Galicia, 11.
Ochrolite, 12.
Ores, Antimony, 3.
- , -, World's production of, 17.
, Bismuth, 110.
Orilio-antimonates, 90.
-antimonic acid, SO.
antim onions acid, 89.
chloroantimonates, 75.
-chloroantimonic acid, 74.
Oruetite, 122, 200.
Oxychloridcs of tervalent antimony, 66-69.
Panacea Antimonialis, 107.
Partziie, 9.
Pentachlorobismuthous acid, Salts of, 166.
Pewter, 38, 125.
Plagionite, 7.
Platynitc, 121.
Plumbostannite, 9.
Poly argy rite, 6.
Polybasite, 6.
Potassium antimonatc, 104.
antimoniodobromide, 82.
antimony oxysulphidc, 111.
antimonyl tartrate, 93.
bismuth thiosulphate, 203.
bismuthobromocyanide, 216.
meta-hypoantimonate, 93, 106.
pyro-antimonate, 97.
selenoantimonate, 113.
stibiothiosulphatc, 112.
thioantimonitc, 108.
thiobismuthitc, 188.
Powder of Algaroth, 15.
Pucherite, 123.
P'ulr/is (I'iKjelic'Us, 57.
Pyro-antimonious acid, 89.
Pyroargyrite, 5.
Pyro-chloroantimonates, 75.
-chloroantimonic acid, 74.
Pyi'ostilpnite, 5.
KATIITTE, 8.
Rezbanyitc, 119, 121.
Rhagite", 123, ]24.
Rivoiite, 1.0.
Romeite, 11, 91.
Rubidium bismuth thiosulphate, 203.
hypo-bromoantimonate, 78.
stibiothiosulphate, 112.
SAMSEYITE, 7.
Samsom'te, 6.
Schapbachite, 120.
Scliirmerite, 120.
Schlippe's salt, 107, 108-109.
Seleniferous bismuthinite, 121.
Selenium, Complex compounds of antimony
and, 113.
Selenoantimonates, 113.
Selenoantimonites, 113.
Senarmontite, 3, 9, 84, 85.
Silaonite, 121, 204.
Silberphylhnglanz, 9.
Silver bismuth thiosulphate, 203.
Sodium antimonatc, 109.
antimoniodobromide, 82.
antimonites, 90.
bismuth thiosulphate, 203.
bisniuthate, 193.
bismuthide, 145.
bismuthipyrophosphate, 214.
hydrogen pyroantiinonate, 56.
meta-antimonite, 00.
, Trihydrate, 90.
potassium bismuthyl tartrate, 154.
pyro-antimonate, 90.
selenoantimonate, 112, 113.
thioantimonate, 107, 108-109.
thioantimonite, 90.
Spanish white, 209.
Stephanite, 6.
Stctefeldtite, 10.
St. ib la femrn a, 84 .
Stibianite, 10.
Stibiconite, 10, 92.
Stibine, 48-53. See also Antimony tri-
hy dridc.
Stibioferrite, 10.
Stibiotantalite, 13.
Stibiothiosulphates, J 12.
Stibium,, 14.
, Stibnite, 3, 14, 15, 36, 37, 97, 100, 101.
: Strontium bismuth thiosulphate, 203.
; stibiothiosulphate, 112.
: Stylotypite, 5.
; Sulphur auralum, 107.
' Sundlite, 6.
i Systems, Binary:
Antimony pentachloridc-antimony penta-
fluoridc, 56.
Antimony pentachloride-titanium tetra-
ehloride, 74.
Antimony trichloride-chlorine, 62.
Antimony trichloride- water, 67.
Bismuth-bismuth tribromide, 171.
Bismuth-bismuth trichloride, 158.
S y s t e m s , Tern ary :
Acid bismuth sulphate-sulphuric acid-
water, 201.
Antimony trichloride-hydrochloric acid-
water, 68.
Antimony trioxidc - hydrochloric acid-
water, 67.
Bismuth-sulphur-tellurium, 200.
Bismuth trioxide - hydrochloric acid-
water, 163, 164, 168".
Bismuth trioxide-nitrogen pentoxide-
water, 209-213.
Copper-antimony-sulphur, 103.
Xiekel-antimony-sulphur, 1 03.
See also Freezing point curves; Alloy
systems.
248
ANTIMONY AND BISMUTH.
TARTAR emetic, 15, 47.
Tazna, Mountain of, 119.
Taznite, 12.
Tetrachlorobismuthous acid, Salts of, 166.
Tetradymite, 119, 122, 205.
Tetrahedrite, 5.
Thallium bismuth thiosulphate, 203.
Thioantimonates, 3, 89, 106, 108-110.
Thioantimoiiie acid, 108.
Thioantimonites, 3, 83, 90, 104, 105-106,
109.
Thiobismuthites, ] 99-200.
Thorium C, 147, 155.
Thrombolite, 13, 91.
"Timonox," 91.
Tin antimonide, 64.
Topalite, 122.
/^-Trichloro-hexachloro-dibismuthites, 165.
Trimercuric antimony iodocyanide, 83.
Tripichyite, 12.
Type metal, 38, 44.
ULLMASNITE, 8.
Uranosphaerite, 123.
VALENTESTITE, 3, 9, 84, 85, 87.
Volgerite, 10.
Von Diestrite, 122.
Vrbaite, 8.
WALPCJKGITE, 123, 214.
Warreiiite, 7.
Webnerite, 6.
Wehrlite, 122.
Weibullite, 122.
Willy ami te, 13.
Witfichenite, 120.
Wolfachite, 8.
Wolfsbergite, 4.
ZINC antimoniodobromide, 82.
bismuth nitrate, 208.
Zinkenite, 7.
PATENT IFDEX.
BRITISH PATENTS.
189706
185.
j 332504
190.
250897
74.
348138
85.
298587
190,
215. ; 389619
83.
315811
17.
!
CANADIAN PATENTS.
252563
109.
| 324755
127.
FRENCH PATENTS.
605401
107.
706371
85.
640346
190.
i 720589
53.
665174
17.
! 725448
38, 43.
694283
16,
89, 188. ; 732320
84.
696448
85.
i
GERMAN PATENTS.
45222
54.
161776
111.
45224
54.
492686
107.
5038 J
54.
494454
127.
53618
54.
498921
128.
54219
68.
502198
127.
57615
54.
503806
128.
76168
54.
538286
190.
85626
54.
540983
147.
86668
54.
544933
128.
94124
107.
602697
53.
160110
110.
713277
1354806
1428041
1597018
1615226
1633754
1671203
1 753294
1778292
1780944
1786908
1801339
JAPANESE PATENT.
93504 185.
UNITED STATES PATENTS.
127.
185.
127.
16.
147.
107.
107.
64.
127.
16.
17.
127.
1809871
127.
1816620
127.
1 1821634
127.
1840028
127.
1844306
189.
l 1853534
127.
1853535
127.
1853536
127.
1870388
127.
1870470
127.
1873774
85.
1984480
83.
PRINTED IN GREAT BRITAIN' BY NEILL AND CO., LTD., EDINBURGH.
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