Sir William Ramsay.

A system of inorganic chemistry online

. (page 1 of 67)
Online LibrarySir William RamsayA system of inorganic chemistry → online text (page 1 of 67)
Font size
QR-code for this ebook


A SYSTEM



OF



INORGANIC CHEMISTRY



BY



WILLIAM EAMSAY, PH.D., F.E.S.



PROFESSOR OF CHEMISTRY IN UNIVERSITY COLLEGE. LONDON.




LONDON
J. & A. CHURCHILL

11, NEW EUELINGTON STEEET
1891



f



7EKSIT7




PREFACE



FOR more than twenty years, the compounds of carbon have
been classified in a rational manner ; and the relations
between the different groups of compounds and between the
individual members of the same groups have been placed in
a clear light. It is, doubtless, owing to the brilliant origin-
ators of this method of classification Kekule, Hofmann,
Wurtz, Frankland, and others too numerous to mention, but
whose names occupy a prominent place in the history of our
science that the domain of organic chemistry has been so
systematically and successfully enlarged, and that it presents
an aspect of orderly arrangement which can scarcely be
surpassed.

This has unfortunately not been the fate of the chemistry
of the other elements. Nearly twenty-five years have
elapsed since the discovery by Newlands, Mendeleeff, and
Meyer of the periodic arrangement of the elements ; and, in
spite of the obvious guide to a similar classification which it
furnishes, no systematic text-book has been written in English
with the periodic arrangement of the elements as a basis.

The reasons for this neglect have probably been that the
ancient and arbitrary line of demarcation between the non-
metals and the metals has been adhered to ; that too great
importance (from the standpoint of pure chemistiy) has been
assigned to the distinction between acid hydroxides and
basic hydroxides (acids and bases), which has tended to
obscure the fact that they belong essentially to the same
class of compounds, viz., the hydroxides ; and that the
chemistry of text-books has almost always been influenced
by commercial considerations. The first of these reasons



vi PREFACE.

has often led, among other anomalies, to the separation of such
closely allied elements as boron and aluminium, antimony
and bismuth, silicon and tin ; the second reason has often led
to the ignoring of the double halides, except in a few special
instances, and to the neglect of compounds such as double
oxides of the sesquioxides of the iron group, in which these
oxides play an acidic part ; while, for the third reason, those
methods of preparing compounds which are of commercial
importance are usually given, while other methods, as im-
portant from a scientific point of view, are often ignored ; the
borides, nitrides, &c. r have been almost completely neglected
since the time of JBerzelius ; and the less easily obtained
elements and compounds have been dismissed with scant
notice because of their rarity ; whereas they should obviously
be considered as important as the commoner ones in any
treatise on scientific chemistry.

The methods of classification adopted in this book are, as
nearly as the difference of subject' will permit, those which
have led to the systematic arrangement of the carbon com-
pounds. After a short historical preface, the elements are
considered in their order; next their compounds with the
halogens, including the double halides ; the oxides, sulphides,
selenides, and tellurides follow next, double oxides, such as
sulphates, for example, being considered among the com-
pounds of the simple oxides with the oxides of other ele-
ments ; a few chapters are then occupied with the borides,
carbides, and silicides, and the nitrides, phosphides, arsen-
ides, and antimonides ; and in these the organo-metallic com-
pounds, the double compounds of ammonia, and the cyanides
are considered; while a short account is given of alloys and
amalgams. The chemistry of the rare earths, which must at
present be relegated to a suspense account, is treated along
with spectrum analysis in a special chapter ; and the
systematic portion of the book concludes with an account
of the periodic table.

The periodic arrangement has been departed from in two
instances : the elements chromium, iron, manganese, cobalt,
and nickel have been taken after those of the aluminium



PREFACE. Vll

group ; and the elements copper, silver, gold, and mercury
have been grouped together and considered after the other
elements. It appeared to me that the analogies of these
elements would have been obscured, had the periodic arrange-
ment been strictly adhered to.

' It has bee^n thought desirable, instead of treating of
processes of manufacture under the heading of the re-
spective elements or compounds, to defer a description of
them to the end of the book, and to group them under
special headings, those compounds beipg, considered together
which are generally manufactured under one roof. In
describing manufactures, chemical principles have been con-
sidered, rather than the apparatus by means of which the
manufactures are carried on. The student,, having acquired
the requisite acquaintance with facts, is now better able to
appreciate these principles.

The physical aspects of chemistry have generally been
kept in the background, and introduced only when necessary
to explain modern theories. I hold that a student should
have a fair knowledge of a wide range of facts before he
proceeds to the study of physical chemistry, which, indeed,
is a science in itself. But short tables of the more important
physical properties of elements, and of the simpler com-
pounds, have been introduced for purposes of reference.

It may be asked if such a system is easily grasped by the
student, and if it is convenient for the teacher. To this
question I can reply that, having used it for four years, I am
perfectly satisfied with the results. For the student, memory
work is lightened ; for the teacher, the long tedious descrip-
tion of metals and their salts is avoided ; and I have found
that the student's interest is retained, owing to the fact that
all the " fire-works " are not displayed at the beginning of
the course, but are distributed pretty evenly throughout.

It need hardly be mentioned that the teacher is not
required to teach, nor the student to remember, all the facts
as they are here set forth. It is necessary to make a
judicious selection. But it is of advantage to have the list
fairly complete for purposes of reference. It should be stated



Vlll PREFACE.

that, in the case of compounds of questionable existence,
they have received the benefit of the doubt. It is at least
well that they should be known, in order that their existence
may be brought to the test of renewed experiment.

References to original memoirs have been given where
important theoretical points are involved; or where doubt
exists ; and an attempt has been made to guide the reading
of students. As a rule, references to recent papers are
given ; the older references may be found in one of the
chemical dictionaries.

WILLIAM RAMSAY.

UNIVEESITT COLLEGE, LONDON,
January, 1891.



CONTENTS.



PART I.

PAGE

CHAPTER I. Introductory and Historical 1

CHAPTER II. Historical 14

PART II.
THE ELEMENTS.

CHAPTER III. Group 1. Hydrogen, lithium, sodium, potassium,

rubidium, and caesium . . . . . . . . . . . . 25

Group 2. Beryllium, or glucinum, calcium, strontium, barium . . 31

Group 3. Magnesium, zinc, cadmium . . . . . . - . . 33

Group 4. Boron, scandium, (yttrium), lanthanum, (ytterbium) .. 35

Group 5. Aluminium, gallium, indium, thallium . . . . . . 37

CHAPTER IV. Group 6. Chromium, iron, manganese, cobalt, nickel .. 40

Group 7. Carbon, titanium, zirconium, cerium, thorium . . . . 43

GroupS. Silicon, germanium, tin, (terbium), lead. . .. .. 49

CHAPTER V. Group 9. Nitrogen, vanadium, niobium, (didymium),

tantalum . . . . . . . . . . . . . . . . 53

Group 10. Phosphorus, arsenic, antimony, (erbium), bismuth . . 56
Group 11. (Oxygen, chromium). Molybdenum, tungsten, uran-
ium .. 60

Group 12. Oxygen, sulphur, selenium, tellurium . . . . . . 61

Appendix. Air . . . . . . . . . . . . . . . . 70

CHAPTER YI. Group 13. Fluorine, chlorine, bromine, iodine . . . . 72

Groups 14 and 15. Ruthenium, rhodium, palladium, osmium.

iridium, platinum . . . . . . . . . . . . . . 77

Groupie. Copper, silver, gold, mercury "V .. .. .. 79

General remarks on the elements . . V^ V . . . . . . 83

PART III.
THE HALIDES.

CHAPTER VII. Compounds and mixtures ; nomenclature . . . . 88
The states of matter ; Boyle's law ; Gay-Lussac's law ; Avogadro's

law " 91

Methods of determining the densities of gases . . . . . . 97



X CONTENTS.

PAGE

CHAPTER VIII. Hydrogen fluoride, chloride, bromide, and iodide . . 104
Halides of lithium, sodium, potassium, rubidium, caesium, and

ammonium . . . . . . . . . . . . . . . . 115

CHAPTEE IX. Halides of beryllium, calcium, strontium, and barium .. 120

Halides of magnesium, zinc, and cadmium . . . . . . . . 123

Molecular formulae ; specific heats of elements . . . . . . 126

CHAPTEE X. Halides of boron, scandium, (yttrium), and lanthanum,

(ytterbium) 131

Halides of aluminium, gallium, indium, and thallium . . . . 133

Halides of chromium, iron, manganese, cobalt, and nickel. . . . 137

CHAPTEE XI. Halides of carbon, titanium, zirconium, cerium, and

thorium . . . . . . . . , . . . . . . . 144

Halides of silicon, germanium, tin, (terbium), and lead .. .. 148

CHAPTEE XII. Halides of nitrogen, vanadium, niobium, tantalum . . 157

Halides of phosphorus, arsenic, antimony, -(erbium), and bismuth. . 160

Halides of molybdenum, tungsten, and uranium . . . . . . 164

Halides of sulphur, selenium, and tellurium. . . . . . . . 166

CHAPTEE XIII. Compounds of the halogens with each other . . . . 169

Halides of ruthenium, rhodium, and palladium . . . . . . 170

Halides of osmium, iridium, and platinum . . . . . . 172

Halides of copper, silver, gold, and mercury. . . . . . . . 174

CHAPTEE XIY. Review of the halides ; their sources, preparation, and
properties ; their combinations and their reactions ; also their

molecular formulae . . 181



PART IV.

THE OXIDES, SULPHIDES, SELENIDES, AND
TELLURIDES.

CHAPTEE XV. Compounds of oxygen, sulphur, selenium, and tellurium

with hydrogen . . . . . . . . . , . . . . 191

Physical properties of water . . . . . . . . . . . . 199

Compounds of water with halides 203

CHAPTEE XVI. Classification of oxides . . . . 205

The dualistic theory . . 207

Constitutional and rational formulae . . . . . . . . . . 208

Oxides, sulphides, &c., of lithium, sodium, potassium, rubidium,

caesium, and ammonium .. .. .. .. .. ..211

Hydroxides and hydrosulphides . . . . . . '. . . . 214

CHAPTEE XVII. Oxides, sulphides, and selenides of beryllium, calcium,

strontium, and barium . . . . . . . . . . . . 218

Hydroxides and hydrosulphides . . . . . . . . . . 222

Oxides, sulphides, selenides, and tellurides of magnesium, zinc,

and cadmium 225



CONTENTS. Xi

PAGB

Hydroxides and hydrosulphides 229

Double oxides (zincates) ; oxyhalides . . .. .. .. ... 229

CHAPTER XVIII. Oxides and sulphides of boron, scandium, (yttrium),

lanthanum, (and ytterbium) . . 232

Double oxides (boracic acid and borates) . . . . . . . . 233

Oxyhalides 236

Oxides, sulphides, and selenides of aluminium, gallium, indium,

and thallium .. 237

Hydroxides and double oxides (aluminates, &c.) . . . . . . 239

Double sulphides and oxyhalides . . . . . . . . . . 242

CHAPTEB XIX. Monoxides, monosulphides, monoselenides, and mono-

tellurides of chromium, iron, manganese, cobalt, and nickel . . 243

Dihydroxides ; double sulphides 246

Sesquioxides, sesquisulphides, and sesquiselenides . . . . . . 248

Trihydroxides 251

Double oxides (spinels) .. .. ... .. .. .. .. 253

Double sulphides and oxyhalides . . . . . . . . . . 256

Dioxides and disulphides . . . . *. . . . . . . 258

Hydrated dioxides and double oxides (manganites) . . . . . . 260

Trioxides . . . . 261

Double oxides (chromates, ferrates, and manganates) . . . . 262

Perchromates and permanganates . . . . . . . . . . 266

Oxyhalides 268

CHAPTER XX. Monoxides and monosulphides of carbon, titanium,

zirconium, cerium, and thorium .. .. .. .. .. 270

Sesquioxides and sesquisulphides 273

Dioxides and disulphides . . . . . . . . . . . . 274

Compounds with water and with hydrogen sulphide . . . . 283

Carbonates, titanates, zirconates, thorates; carbon oxysulphide;

oxysulphocarbonates and sulphocarbonates . . . . . . 284

Oxyhalides .. .... .... .292

CHAPTER XXI. Monoxides, monosulphides, monoselenides, and mono-

tellurides of silicon, germanium, tin, and lead 294

Hydroxides ; compounds with oxides and with halides . . . . 297

Sesquioxides and sesquisulphides . . . . . . . . . . 299

Dioxides, disulphides, diseknides, and ditelluride 300

Compounds with water and oxides: silicates, stannates, and

plumbates . . . . . . . . . . . . . . . . 303

Sulphostannates .. .. 316

Oxyhalides 317

CHAPTER XXII. Oxides and sulphides of nitrogen, vanadium, niobium,

and tantalum 319

Compounds of pentoxides with water and oxides ; nitric, Tanadic,
niobic, and tantalic acids : nitrates, vanadates, niobates, and

tantalates 322

Oxyhalides 331



Xll CONTENTS.

PAGE

Tetroxides or dioxides : tetrasulphide or disulphide . . . . 333

Compounds with oxides and sulphides ; hyporanadates and hypo-

sulphovanadates . . . . . . . . . . . . . . 335

Compounds with halides. Trioxides . . . . . . . . . . 336

Nitrites and vanadites . . . . . . . . . . . . . . 337

Compounds with halides .. .. .. .. .. ._;, 340

Nitric oxide ; yanadium monoxide . . . . . . . . . . 341

Nitrogen sulphide and selenide. Nitrosulphides . . . . . . 343

Nitrous oxide ; hyponitrites . . . . . . . . . . , . 343

CHAPTEE XXIII. Oxides, sulphides, selenides, and tellurides of phos-
phorus, arsenic, antimony, and bismuth. . . . . . it 346

Compounds of the pentoxides and pentasulphides ; orthophos-

phates, orthoarsenates, and orthoantimonates, &c. . . . . 352

Pyrophosphates, pyrarsenates, and pyrantimonates . . . . . . 363

Metaphosphates, metarsenates, and metantimonates . . . . 369

CHAPTER XXIY. Hypophosphoric acid . . 373

Compounds of trioxides and trisulphides ; phosphites, arsenites,

and antimonites ; their sulphur analogues . > . . . . 374

Hypophosphites . . . . . . . . . . . . . . . . 380

Compounds of oxides and sulphides with halides . . . . . . 332

CHAPTER XXV. Ozone (oxide of oxygen) . . . . . . . . . . 387

Oxides and sulphides of molybdenum, tungsten, and uranium , . 392
Hydroxides ; molybdates, tungstates, and uranates ; sulphur

analogues . . . . . . . . . . . . . . . . 396

Peruranates, persulphomolybdates . . . . . . . . . . 405

Compounds with halides . . . . . . . . . . . . 406

CHAPTER XXVI. Oxides of sulphur, selenium, and tellurium . . . . 409

Sulphuric, selenic, and telluric acids . . . . . . . . . , 414

Sulphates, selenates, and tellurates 419

Anhydrosulphuric acid and anhydrosulphates . . . . . . 432

CHAPTER XXVII. Sulphurous, selenious, and tellurous acids . . . . 435

Sulphites, selenites, and tellurites . . . . . . . . . , 436

Compounds of oxides with halides j sulphuryl chloride ; chloro-

sulphonic acid . . . . . . . . . . . . . . 440

Other acids of sulphur and selenium . . . . . . . . . . 443

Thiosulphates 444

Seleniosulphates 447

Hyposulphurous acid and hyposulphites 447

Dithionic acid and dithionates , . . . . . . . . . . . 448

Trithionic acid and trithionates . . . . . . . . . . 449

Seleniotrithionic acid ; tetrathionic acid . . . . . . . . 450

Pentathionic acid 451

Hexathionic acid. Constitution of the acids of sulphur and

selenium . . . . . . . . . . . . . . . . 452

Nitrososulphates 455

Compounds of sulphur, selenium, and tellurium with each other . . 455






'ERSITY

CONTENTS. o _ x



PAGB

CHAPTEE XXVIII. Oxides of chlorine, bromine, and iodine . . . . 459

Hypochlo rites, hypobromites, aiid hypoiodites . . . . . . 461

Chlorous acid and chlo rites .. .. .. ' "... 464

Chlorates, bromates, and iodates . . , . , 464

Perchlorates and periodates . . . . . . . . . . . 469

CHAPTER XXIX. Oxides, sulphides, and selenides of rhodium, ruthen-
ium, and palladium . . . . . . . . . . . . 476

Hydroxides 478

Sulphopalladites ; ruthenates and perruthenates . . . . . . 479

Oxides, sulphides, and selenides of osmium, iridium, and platinum. 480

Hydroxides .. .. 482

Osmites and platinates . . . . . . . . . . . . . . 483

Platinonitrites ; platinochlorosulphites ; platinicarbonyl com-
pounds ; dichloroplatiniphosphonic acid. . . . . . . . 485

Oxides, sulphides, selenides, and tellurides of copper, silver, gold,

and mercury . . . , . . . . . . . . . . 487

Hydroxides .. 491

Aurates. Double sulphides. Oxy- and sulpho-halides . . . . 492
Concluding remarks on the oxides, sulphides, &c. ; classification of

oxides 494

Constitutional formulae ; oxyhalides and double halides . . . . 495



PART V.
THE BOBIDES. THE CARBIDES AND SILICIDES.

CHAPTER XXX. The borides ; hydrogen boride . . 497

Magnesium, aluminium, manganese, silver, and iron borides . . 498

The carbides and silicides ; methane, or marsh-gas . . . . . . 498

Hydrogen silicide . . . . . . . . . . . . . . 500

Ethane ; silicoethane . . . . . . . . . . . . . . 501

Double compounds of ethyl and methyl ; " organo-metallic " com-
pounds . . . . . . . . . . . . . . ' . . 502

Ethylene.. .. ' .. .. .. < .. ;.'.'*' .. .. 507

Acetylene .. ' .. f WJR 508

Carbides and silicides of iron, &c. . . . . . . . . 510



PART VF.

THE NITRIDES, PHOSPHIDES, ARSENIDES, AND
ANTIMONIDES.

CHAPTER XXXI. Hydrogen nitrides, phosphides, arsenide, and anti-

monide ; ammonia, hydrazine, hydrazoic acid, &c. . . . . 512

Salts of phosphonium . . . . . . . . . . . . . 517

Hydroxylamine . . 523



XIV CONTENTS.

PAGE

Amido-compouads or amines . . . . . . . . . . 524

Salts of the amines 525

Chromamine salts . . . . . . . . . . . . . . 526

Cobaltamiiie salts . . . . . . ... . . . . . . 528

Methylamine, &c. ; the phosphines and arsines .. .. .. 532

Carbamide . . . . . . . . . . . . . . . . 532

Silicamines, titanamine, and zirconamine salts . . . . . . 533

Amides of phosphorus ; phosphamic acids . . . . . . . . 534

Sulphamines (sulphamic acids) . . . . . . . . . . 536

Amines of rhodium, ruthenium, and palladium . . . . . . 537

Osmamines, iridamines, and platinamines . . . . . . . . 539

Cupramines, argentamines, auramines, arid mercuramines . . . . 545

CHAPTER XXXII. The nitrides, phosphides, arsenides, and antimonides. 550

Cyanogen (carbon nitride) and its compounds .. .. .. 558

Ferrocyanides and ferricyanides, and analogous compounds . . 562

Platino- and platini-cyanides, and similar compounds . . . . 570

Constitution of cyanides . . . . . . . . . . . . 572



PART VII.

CHAPTEE XXXIII. Alloys. Hydrides 575

Alloys of lithium, sodium, potassium, &c. .. .. .. .. 577

calcium, barium, magnesium, zinc, &c. .. .. .. 578

aluminium, chromium, iron, &c. . . , . . . . . 581

tin and lead . . . . . . . . . . . . . . 585

antimony and bismuth . . . . . . . . . . 587

the palladium and platinum metals 588

copper, silver, gold, and mercury . . . . . . . . 589



PAET VIII.

CHAPTEE XXXIV. Spectrum analysis 591

Spectroscopy applied to the determination of atomic weights . . 598
The rare earths; the didymium group; the erbium group; the

yttrium group .. ..602

Solar and stellar spectra . . . . . . . . . . . . 606

CHAPTEE XXXV. The atomic and molecular weights of elements, and

the molecular weights of compounds . . . . . . . . 611

The specific heats of elements and compounds 617

The law of replacement. . . . . . . . . . . . . . 619

Isomorphism . . . . . . . . . . . . . . tt 620

The complexity of molecules .. .. .. .. .. ,. 621

The monatomic nature of mercury gas . . . . . . . . 624

CHAPTER XXXVI. The periodic arrangement of the elements . . . . 627

Numerical relations between atomic weights. . . . 629



CONTENTS. XV

PAGE

Relations between atomic weights and physical properties of

elements . . . . . . . 633

Comparison of the elements and their compounds 634

Prediction of undiscovered elements 639



PART IX.

CHAPTEB XXXVII. Processes of manufacture 642

Combustion; fuels 642

CHAPTEB XXXVIII. Commercial preparation of the elements . . . . 651

Manufacture of sodium. . . . . . . . . . . . . 651

magnesium, zinc, and aluminium . . . . . . 652

iron and steel. . . . . . 653

nickel . . . . . . . . 658

tin and lead 659

antimony . . . . . . . . . . 660

'bismuth and copper . . . . 661

silver . . 662

gold 663

mercury . . 664

phosphorus 665

CHAPTER XXXIX. Utilisation of sulphur dioxide . . . . 667

Manufacture of sulphuric acid. . . . . 667

alkali 670

Preparation of sodium sulphate . . . 672

The Leblanc soda-process 673

Manufacture of caustic soda . . . . 675

Utilisation of tank-waste . . . . 676

Manufacture of chlorine . . . . 678

bleaching powder . . . . . 681

potassium chlorate . . . . 682

The ammonia- soda process . . . . 683



^S^A^f

PART I.






CHAPTER I.
INTRODUCTORY AND HISTORICAL.

THE first object of the Science of Chemistry is to ascertain the
composition of the various things which we see around us. Thus,
among familiar objects are air, water, rocks and stones, earth, the
baric, wood, and leaves of plants, the flesh, fat, and bones of animals,
and so on. Of what do these things consist ?

The second is to ask, Can such things be made artificially, and,
if so, by what methods ? Attempts to answer these questions
have led to the discovery of many different kinds of matter, some
of which have as yet resisted all efforts to split them up into still
simpler forms. Such ultimate kinds of matter are termed elements.
But other kinds of matter can often be produced when two or
more of the simpler forms or elements are brought together ; the
elements are then said to combine, and the new substances resulting
from their combination are called compounds.

The third object of the Science of Chemistry is the correct
classification of the elements and of their compounds ; those sub-
stances which are produced in a similar manner, or which act in a
similar manner when treated similarly, being placed in the same
class.

The fourth inquiry relates to the changes which different forms
of matter undergo when they unite with each other, or when they
split into simpler forms.

Fifthly, the conditions of change are themselves compared
with each other and classified ; and thus general laws are being
deduced, applicable to all such changes.

Lastly, the Science of Chemistry and the sister Science of
Physics join in speculations regarding the nature and structure of
matter, in the hope that it may ultimately be possible to account
for its various forms, the changes which they undergo, and the
relations existing between them.



2 INTRODUCTORY AND HISTORICAL.

To answer questions such as these, it is obvious that experi-
ments must be made. Each form of matter must be separately
exposed to different conditions ; heated, for example ; or placed
under the influence of an electric current; or brought together
with other kinds of matter ; before it is possible to know what it will
do. Now, the ancient philosophers did not perceive this necessity ;
nor indeed were they much concerned in making the inquiry.
Those nations which have left behind them a record of their
thoughts, the ancient inhabitants of India, Egypt, Greece, and
Rome, devoted their attention, if they aspired to be learned, to
oratory, to history, or to poetry. Their only scientific pursuits
were politics, ethics, and mathematics. Distinction was to be
gained in the forum, in the temple, or in the battlefield ; not in
wresting secrets from Nature. The practice of such of the arts as
were then known was in the hands of slaves and the lower classes
of the people, who were content to transmit their methods from
father to son, and whose achievements were unchronicled. The
citizens of the State, the wealthy and the leisured, despised these
low-class arts ; and, indeed, it was taught by Socrates and his fol-
lowers that it was foolish to abandon the study of those things
which more nearly concern man, for that of things external
to him. It was generally believed that by the exercise of pure
thought, without careful observation and experiment, a man
could know best the true nature of the objects external to him.
Thus Plato says in the 7th Book of the " Republic," " We shall
pursue Astronomy with the help of problems, just as we pursue
Geometry; but, if it is our design to become really acquainted with
Astronomy, we shall let the heavenly bodies alone." Elsewhere



Online LibrarySir William RamsayA system of inorganic chemistry → online text (page 1 of 67)