A Comprehensive Treatise on Inorganic and Theoretical Chemistry: volume 15. Ni, Ru, Rh, Pd, Os, Ir

824 Pages·33.266 MB·English

by  Mellor J.W.

v/
A C O M P R E H E N S I VE TREATISE ON INORGANIC AND
T H E O R E T I C AL C H E M I S T RY
VOLUME XV
Ni, Ru, Rh, Pd, Os, Ir
BY THK SAME AUTHOR
ELEMENTARY INORGANIC CHEMISTRY.
With 129 Illustrations. 3s. 6d.
INTERMEDIATE INORGANIC CHEMISTRY.
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MODERN INORGANIC CHEMISTRY.
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HIGHER MATHEMATICS FOR STUDENTS OF
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With 189 Diagrams. 2 Js. net.
A COMPREHENSIVE TREATISE ON INOR
GANIC AND THEORETICAL CHEMISTRY.
£3 3-s\ net each volume.
Vol. I. H, O.
With 274 Diagrams.
Vol. II. F, Cl, Br, I, Li, Na, K, Rb, Cs.
W^ith 170 Diagrams.
Vol. III. Cu, Ag, Au, Ca, Sr, Ba.
With 158 Diagrams.
Vol. IV. Ra and Ac Families, Be, Mg, Zn, Cd,
.Hg.
With 232 Diagrams.
Vol. V. B, Al, Ga, In, Tl, Sc, Ce, and Rare
Earth Metals, C (Part I).
With 206 Diagrams.
Vol. VI. C (Part II), Si, Silicates.
With 221 Diagrams.
Vol. VII. Ti, Zr, Hf, Th, Ge, Sn, Pb, Inert Gases.
With 255 Diagrams.
Vol. VIIL N, P.
With I 56 Diagrams.
Vol. IX. As, Sb, Bi, V, Cb, Ta.
With 161 Diagrams.
Vol. X. S, Se.
W^ith 217 Diagrams.
Vol. XL Te, Cr, Mo, W.
With 221 Diagrams.
Vol. XII. U, Mn, Ma and Re, Fe (Part I).
With 320 Diagrams.
Vol. XIII. Fe (Part II).
With 381 Diagrams.
Vol. XIV. Fe (Part III), Co.
With 277, Diagrams.
Vol. XV. Ni, Ru, Rh, Pd, Os, Ir.
With 423 Diagrams.
Vol. XVI. Pt and General Index, Completing
the Series. In the press.
A COMPREHENSIVE T
ON
INORGANIC AND THEORETICAL
CHEMISTRY
BY
J. W. MELLOR, D.Sc, F.R.S.
VOLUME XV
WITH 423 DIAGRAMS
L O N G M A N S, G R E EN A ND C O.
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CONTKNTS
CHAPTER 1,XVIII
NICKKT,
§ 1. The History of Nickel (1) ; § 2. The Oeeurrenco of Nickel (3) ; § 3. The Extraction
of Nickel (15) ; §4. The Preparation of Nickel (33) ; § 5. Nickel as a Catalyst (47) ;
§ 6. The Physical Properties of Nickel (5O) ; § 7. Chemical Properties of Nickel (14O) ;
§ 8. The Atomic Weight and Valency of Nickel (175) ; § 9. Jntermeta.llic Compounds
and Alloys of Nickel (178); § IO. Nickel Suboxides and Nickel Monoxide (373);
§11. Nickelosic and Nickelic Oxides (391) ; § 12. The Higher Oxides of Nickel (398) ;
§ 13. Nickel Fluorides (402) ; § 14. Nickel Chlorides (4O0) ; § 15. Nickelous Bromide
(425); §16. Nickelous Iodide (43O); §17. Nickel Sulphides (434); § 1S. Nickel
Sulphates (453) ; § 19. Nickel Carbonates (4S3) ; § 2O. Nickel Nitrate (4S7) ; § 21. Nickel
Phosphates (494).
CHAPTKR LXIX
JtUTHENIlTM
§ 1. The Occurrence of Ruthenium (498); §2. The Extraction and Preparation of
Ruthenium (499) ; § 3. The Physical Properties of Ruthenium (503) ; § 4. The
Chemical Properties of Ruthenium (5OS) ; § 5. The Atomic Weight and Valency of
Ruthenium (511) ; § 6. The Ruthenium Oxides (513) ; § 7. The Ruthenium Halides
(522) ; § 8. Ruthenium Sulphides and Sulphate (54O) ; § 9. The Ruthenium Ammines
(543).
CHAPTER LXX
RHODIUM
§ 1. The Occurrence of Rhodium (545) ; § 2. The Extraction and Preparation of Rhodium
(546) ; § 3. The Physical Properties of Rhodium (553) ; § 4. The Chemical Properties
of Rhodium (501) ; § 5. The Atomic Weight and Valency of Rhodium (507) ; § 0.
The Oxides of Rhodium (509) ; § 7. The Rhodium Halides (572) ; § 8. The
Rhodium Ammines (583) ; § 9. The Rhodium Sulphides (584) ; § 10. The Rhodium
Sulphates (586) ; § 11. The Carbonates, Nitrates, and Phosphates of Rhodium (589).
CHAPTER LXXI
PALLADIUM
§ 1. The Occurrence of Palladium (592) ; § 2. The Extraction and Preparation of Palladium
(594) ; § 3. The Physical Properties of Palladium (599) ; § 4. The Chemical Properties
of Palladium (616); §5. The Atomic Weight and Valency of Palladium (040) .
Vl CONTENTS
§ 6. Intermetallic Compounds and Alloys of Palladium (642) ; § 7. The Palladium
Oxides (654) ; § 8. Palladium Fluorides (658) ; § 9. Palladium Chlorides (660) ;
§10. Palladium Bromides (675) ; §11. Palladium Iodides (679) ; §12. The Palladium
Sulphides and Sulphates (681) ; § 13. Palladium Carbonates, Nitrates, and Phosphates
(684).
CHAPTER LXXII
OSMIUM
§ 1. The Occurrence of Osmium (686) ; § 2. The Extraction and Preparation of Osmium
(687) ; § 3. The Physical Properties of Osmium (691) ; § 4. The Chemical Properties
of Osmium (695) ; § 5. The Atomic Weight and Valency of Osmium (700) ; § 6. The
Osmium Oxides (702) ; § 7. The Osmium Fluorides (714) ; §8. The Osmium Chlorides
(716) ; § 9. The Osmium Bromides (722) ; § 10. Osmium Iodides (724) ; § 11. The
Osmium Sulphides and Sulphates (725) ; § 12. Some Nitrogen Compounds of Osmium
(727).
CHAPTER LXXIII
IRIDIUM
§ 1. The Occurrence of Iridium (730) ; § 2. The Extraction and Preparation of Iridium
(73J) ; § 3. The Physical Properties of Iridium (735) ; § 4. The Chemical Properties
of Iridium (743) ; § 5. The Atomic Weight and Valency of Iridium (749) ; § 6. The
Alloys and Intermetallic Compounds of Iridium (750) ; § 7. The Oxides of Iridium
(752*) ; § 8. The Iridium Fluorides (757) ; § 9. The Iridium Chlorides (757) ; § 10. The
Iridium Bromides (773) ; § 11. The Iridium Iodides (777) ; § 12. The Iridium
Ammines (779); §13. The Iridium Sulphides and Sulphates (781); §14. The
Carbonates, Nitrates, and Phosphates of Iridium (787).
INDEX 791
ABBRE VIATIONS
aq. = aqueous
atm. = atmospheric or atmosphere(s)
at. vol. = atomic volume(s)
at. wt. = atomic weight(s)
T° or 0K. = absolute degrees of temperature
b.p. = boiling point(s)
6° «= centigrade degrees of temperature
coeff. = coefficient
cone. — concentrated or concentration
dil. = dilute
eq. = equivalent(s)
f.p. = freezing point(s)
m.p. = melting point(s)
mol(s) /gram-molecule(s)
v ' = \gram-molecular
molfsl ^/moleculeCs)
mol (s). _ |
molecular
mol. ht. «= molecular heat(s)
mol. vol. = molecular volume(s)
mol. wt. = molecular weight(s)
press. = pressure(s)
sat. = saturated
soln. = solution (s)
sp. gr. = specific gravity (gravities)
sp. ht. = specific heat(s)
sp. vol. = specific volume(s)
temp. = temperature(s)
vap. = vapour
In the cross references the first number in clarendon typo is the number of the
volume ; the second number refers to the chapter ; and the succeeding number refers to the
44 §," section. Thus 5. 38, 24 refers to § 24, chapter 38, volume 5.
The oxides, hydrides, halides, sulphides, sulphates, carbonates, nitrates, and phosphates
are considered with the basic elements ; the other compounds are taken in connection with
the acidic element. Tho double or complex salts in connection with a given element include
those associated with elements previously discussed. The carbides, silicides, titanides,
phosphides, arsenides, etc., are considered in connection with carbon, silicon, titanium, etc.
The intermetallic compounds of a given element include those associated with elements
previously considered.
The use of triangular diagrams for representing the properties of three-component
systems was suggested by G. G. Stokes (Proc. Roy. Soc, 49. 174, 1891). The method was
immediately taken up in many directions and it has proved of great value. With practice it
becomes as useful for representing the properties of ternary mixtures as squared paper is for
binary mixtures. The principle of triangular diagrams is based on the fact that in an equi
lateral triangle the sum of the perpendicular distances of any point from the three sides is
a constant. Given any three substances A, B and C, the composition of any possible
1
combination of these can be represented by a point in or on the triangle. The apices of the
vii
ABBREVIATIONS
VlU
trianale represent the single components A, B and C, the sides of the triangle represent binary
1
mixtures of A and B, B and C, or C and A ; and points within the triangle, ternary mixtures.
The compositions of the mixtures can be represented in percentages, or referred to unity, iu,
etc. In Fig. 1, pure A will be represented by a point at the apex marked A. If 1OO be the
Fia. J.
standard of reference, the point A represents 1OO per cent, of A and nothing else; mixtures
containing 8O per cent, of A are represented by a point on the line 88, 6O per cent, of A by a
point on the line 66, etc. Similarly with B and C—Figs. 3 and 2 respectively. Combine
Figs. 1, 2, and 3 into one diagram by superposition, and Fig. 4 results. Any point in this
*«S
/OO f&of C
of B
FiG. 4. Standard Reference. Triangle.
diagram, Fig. 4, thus represents u ternary mixture. For instance, the point M represents a
mixture containing 20 per cent, of A, 2O per cent, of B, and 60 per cent, of C.
CHAPTER 1,XVIII
NICKEL
§ 1. The History of Nickel
THE mineral kupfernickel described by U. Hiarne,1 in 1694, has the appearance
of a copper ore, but not the smallest particle of copper can be extracted from it.
According to F. X. M. Zippe, the word " nickel " appears to have been used amongst
the miners as a Schimpf name, that is, a disparaging or derogatory term derived
maybe from Nikolaus ; if so, then, as suggested by A. G. Charleton, the term
" kupfernickel " might be translated " Old NicJcs copper" and so J. Woodward
called it cuprum nicolai. We are told—vide cobalt—that the mediaeval Saxon miners
working the silver ores encountered minerals which had the appearance of good
silver ores, but, when smelted, emitted a disagreeable smell, and yielded no silver.
The miners concluded that these ores were bewitched by the Nixes and Cobolds
that dwelt underground. The objectionable minerals were thrown on to the
waste-heaps, and called contemptuously Nixes' ore and Cobolds" ore. Centuries
afterwards these minerals were found to be the arsenides of two new metals, and
the names of the metals, cobalt and nickel, arc thus derived from a mediaeval
superstition. The history was discussed by W. H. Baldwin.
The mineral has been previously discussed—9. 51, 10—as niccolite, its modern
cognomen. The idea that kupfernickel is a copper compound seems to have
prevailed at the end of the seventeenth and beginning of the eighteenth century,
for in 1726, J. H. Linck said that it is a cobalt ore mixed with copper; and
J. G. Wallerius, that it is a copper-red ore consisting of cobalt, iron, and arsenic.
Analogous views were held by J. A. Cramer, J. F. Henckel, and C von .Linnams
in the first half of the eighteenth century.
In 1751, A. F. Cronstedt 2 published in Stockholm a report of his examination
of some ores in the cobalt mines of Helsingland, Sweden. When the earth under
examination was weathered, it acquired a green crust, which furnished long crystals
of a green sulphate or vitriol. When the sulphate was calcined, it furnished a grey
calx, or colcothar, which when reduced yielded a yellowish, hard, brittle metal
with a white fracture. The metallic part of the vitriol furnished with borax a
brown glass. He therefore inferred that the earth contained in addition to iron
and cobalt a new semi-metal. When the soln. of the semi-metal in acid was treated
with a fixed alkali, it yielded a greenish-white precipitate free from copper.
A. F. Cronstedt then showed that the new semi-metal was the dominant base in
kupfernickel, and he accordingly retained the affix of reproach—nickel—for the
new semi-metal. He found that the kupfernickel of Freiberg contained arsenic,
sulphur, nickel, and iron ; and that the speies obtained in the preparation of smalt
contained a relatively large proportion of nickel. Nickel or nickel calx was found
to unite readily with sulphur, forming a yellow compound which when roasted
furnished nickel calx. Nickel forms a hard, white alloy with copper, which, unlike
nickel free from copper, forms in the borax bead a green glass, and a soln. of the
alloy in acid gives a precipitate of copper when treated with zinc or iron. These
facts were considered to demonstrate that nickel itself is free from copper.
Most chemists accepted A. F. Cronstedt's nickel as a new element, but, as
T. Bergman stated, some—e.g., B. G. Sage (1772), and A. G. Monnet (1775)—
VOL. xv. 1 B
2 INORGANIC AND THEORETICAL CHEMISTRY
" were led rather by vague conjecture and specious appearance than by satisfactory
experiment," and retained the old opinion that kupfernickel is a compound of
iron, copper, cobalt, and arsenic. They also considered cobalt and nickel to be
the same element. T. Bergman then examined the new element with the idea of
finding if the characteristics of A. F. Cronstedt's nickel were sufficient to establish
its right to recognition as an element sui generis. T. Bergman concluded that
whilst with the knowledge then available " it was not possible to obtain a perfect
and complete purification of nickel from all heterogeneous mixtures," sufficient
was known to establish the right of nickel to recognition as a metal with distinct
properties of its own which persist in all its combinations. He added :
Vague suspicions that nickel, cobalt, and manganese can be generated from iron
because of the difficulty involved in preparing the metals free from iron, must give way to
phenomena and properties which are constant, and the metals themselves must be regarded
as of an origin altogether distinct and peculiar to themselves. There is no doubt that
many well-known metals, acknowledged to bo distinct substances, would not endure more
severe trials than does nickel. . . . If the genesis of natural productions is to be established
by fanciful metamorphoses, the whole truth and certainty of natural philosophy must
soon be overturned. So long as plausible conjectures are substituted for opinions formed
on the sure basis of experiment, we shall always embrace the shadow for the substance.
N. Leblanc raised some objections to T. Bergman's conclusion that nickel is a
chemical individual .stti generis, but the work of J. B. Proust, J. B. Richter,
IJ. J. Thenard, and Jl. Tupputi removed all doubts, and since that time nickel has
occupied a place in the list of elements. The history of nickel has been discussed
by M. E. Weeks, L). F. Hehnemann, W. II. Baldwin, R. Kirwan, and F. KaprT.
The work of G. lvriiss and F. W. Schmidt led them to attribute the anomalous
positions of nickel and cobalt in the periodic table to the presence in ordinary
nickel and cobalt of an unknown, foreign element which was named gnomium, but
this opinion was not supported by the work of C. Winkler, IJ. Mond and co-workers,
P. Schutzenberger, and T. W. Richards and A. S. Cushman. A new element was
reported by B. O. von Vest to be present in nickel ore, and he proposed to call it
junonium or sirium, whilst IJ. W. Gilbert suggested vestaium or vesiium, but the
alleged element was shown by M. Faraday to be a mixture of nickel, iron, sulphur,
and arsenic. T. Dahll reported a new element—named nonvegiuni—in gersdorffite,
but the report has not been confirmed.
The analysis of the early Chinese alloy, jmefrfong, by G. von Engestrom, in 1776 ;
and the analyses of Bactrian coins, probably 200 B.C., by W. Flight, and
A. G. Oharleton, show that, at these remote periods, the ores employed for making
coinage metal contained some nickel—vide infra, the copper-nickel, and the copper-
nickel-zinc alloys. In 1777, J. C. F. Meyer noted that a Siberian meteorite when
treated with sulphuric acid gave a green soln. which became blue when treated
with ammonium chloride, but J. IJ. Proust, in 1799, is generally considered to
have been the first to demonstrate the presence of nickel in meteoritic iron—vide
infra, nickel-iron alloys.
REFEKENCES.
1 U. Hiarne, En kort Anledning till dtskillige Malmoch Bergarters, Stockholm, 21, 1694 ;
J. G. Wallerius, Mineralogia, Stockholm, 228, 1747 ; J. Woodward, Fossils of all kinds digested
into a Method suitable to their Mutual Relations, London, 1728 ; J. I>. Denso, Physikalische
Briefe, Stettin, 297, 1750; W. H. Baldwin, Joum. Chern. Education, 8. 1749, 1954, 1931;
C. von Linnaeus, Systema naturae., Lugduni Batavorura, 1735 ; J. F. Henckel, Pyritologia
oder Kiess-Historic, Leipzig, 1725 ; J. A. Cramer, Elementa artis docirrtastica;, Leyden, 1739 ;
J. H. Linck, Phil. Trans., 34. 102, 1727 ; Brevis commentellio de cobalto, Lipsise, 1726 ;
F. X. M. Zippe, Geschichte der Metalle, Wien, 256, 1857 ; A. G. Charleton, Joum. JSOC. Arts 42*
496, 1894 ; 43. 609, 1895.
8 J. B. Trommsdorff, Joum. Pharm., 16. 49, 1808 ; 17. 50, 1808; A. ~F. Cronstodt,
Mineralogie, Stockholm, 218, 1758 ; Svenska Akad. Handl., 12. 293, 1751 ; 15. 38, 1754 •
B. G. Sage, Elemens de minSralogie docimastique, Paris, 58, 1772 ; A. G. Monnet, Traite" de la
dissolution des mitauoc, Paris, 1775 ; T. Bergman, Ue niccolo, Stockholm, 1775 ; Opuscula
physica et chemica, Lipsise, 2. 231, 1788 ; J. B. Richter, CrelVs Ann., ii, 383, 1803 ; Gilbert's