A
HISTORY OF CHEMISTRY
FROM EARLIEST TIMES TO
THE PRESENT DAY
BEING ALSO
AN INTRODUCTION TO THE STUDY OF THE
SCIENCE
BY
ERNST VON MEYER, PH.D.
PROFESSOR OF CHEMISTRY IN THE TECHNICAL HIGH SCHOOL, DRESDEN
TRANSLATED WITH THE AUTHOR'S SANCTION
BY
GEORGE McGOWAN, PH.D.
SECOND ENGLISH EDITION, TRANSLATED FROM THE SECOND
GERMAN EDITION, WITH NUMEROUS ADDITIONS
AND ALTERATIONS
MACMILLAN AND CO., LIMITED
NEW YORK : THE MACMILLAN COMPANY
1898
The Right of Translation and Reproduction is Reserved
RICHARD CLAY AND SONS, LIMITED,
LONDON AND BUNG AY.
First Edition 1891.
Second Edition 1898.
PREFACE TO THE FIEST GERMAN EDITION
NEARLY five decades have passed by since Hermann Kopp's
classical Geschichte der Chemie 1 began to appear, and it is
now fifteen years since this was followed by the same
indefatigable author's Entwickelung der Chemie in der
neueren Zeit?-
The publication of these comprehensive works, in con-
junction with which Hofer's Histoire de la Chimie must be
named, and the further descriptions of the growth of
chemistry within particular periods given both by Kopp
himself and by other writers, might lead one to suppose that
there was no pressing need for further work in the same
direction at the present time.
This point can, the author thinks, be best discussed by
his making a few remarks here with respect to the aim and
plan of the present volume.
In this History of Chemistry the attempt has been made
to describe within short compass the development of
chemical knowledge, and especially of the general doctrines
of chemistry which have thus been gradually evolved, from
their earliest beginnings up to the present day. After a
1 "History of Chemistry."
2 " The Development of Chemistry in Recent Times."
85421
vi PREFACE TO THE FIRST GERMAN EDITION
general account of the main directions followed by chemistry
in the various ages, the growth of particular branches of the
science has been more or less minutely detailed.
In the general descriptions great emphasis has been laid
upon the genesis of particular ideas, and their expansion into
important dogmas or comprehensive theories. At the same
time, in order that a vivid picture of the various periods and
their distinguishing characteristics might be presented to
the reader, short accounts have been given of the works, and
in some cases of the lives, of the men who originated and
developed such views.
In the special sections, on the other hand, the attempt
has been made to collect together fundamental facts, which
have been sifted and relegated to their proper branch of the
science, and thus to offer as clear a description as possible of
the state of chemical knowledge at the time in question.
That neither in this nor in the history of the develop-
ment of theoretical views could completeness be thus
achieved, hardly requires to be stated. But the author has
at all events endeavoured to give a fair synopsis of the most
important theories and facts which constitute the foundation
of chemistry as we now know it.
The growth of chemical knowledge during recent times,
since Boyle, and especially since Lavoisier, naturally forms
the principal subject of the following chapters. The author
is fully aware of the many difficulties which have to be met
here, difficulties which increase in extent the nearer we
approach to the history of our own period. We stand too
close to the development of the theoretical views of these
latter days to feel certain of always preserving the unbiassed
PREFACE TO THE FIRST GERMAN EDITION vii
temperament which is essential to the true historian. But,
notwithstanding this, the author has ventured the attempt
to carry the record of the history of chemistry up to the
present day.
In this task he has done his best to preserve throughout
an objective attitude ; and he has further been guided by
the earnest desire to contribute effectively towards shedding
a clear light upon the opposing views held with respect
to the development and the importance of the chemical
doctrines of to-day. It has also been his duty as an
historian to endeavour to apply to the services rendered by
eminent investigators of quite recent years a calmer and
j uster criticism than has hitherto in many cases been meted
out to them.
ERNST VON MEYER.
LEIPZIG, 7th October, 1888.
TRANSLATOR'S PEEFACE TO THE FIRST
ENGLISH EDITION
THE author, in his preface to the original German edition,
discusses the question whether there is any necessity for
a new history of chemistry in his own language at the
present day. That there is full room for one in this country
will be admitted upon all hands. It is therefore hoped that
the appended history will prove not only useful to the student,
but also interesting to the general reader who is desirous of
gaining some idea of the development of chemical science.
The translator has done his best to reproduce clearly the
sense of the German original. And, since Professor von
Meyer has been so kind as to read over the first corrected
proofs, as well as to answer a great many queries, it is hoped
that this has been achieved.
A considerable number of small alterations and additions
have been made for this edition, most of them by the author,
but some by the translator with the author's concurrence.
While these may reasonably be supposed to have improved
the book, they have not altered its character in the slightest
degree. The translator has further added a number of
duplicate references to English journals (to such papers as
were published both in German and English), and also a few
new ones, for the greater convenience of English readers.
TRANSLATOR'S PREFACE
In conclusion, he would express his indebtedness to the
various gentlemen who have been kind enough to give him
the benefit of their criticism and advice upon different points,
with regard to which his own special knowledge was insuffi-
cient, and also to those others who have assisted him in the
matter of references, etc.
UNIVERSITY COLLEGE OF N. WALES, BANGOR,
March, 1891.
AUTHOR'S NOTE TO THE FIRST ENGLISH
EDITION
It was a great satisfaction to me that the translation of
this history was undertaken by my former pupil, Dr. McGowan,
and I desire to express here my appreciation of the manner
in which he has entered into the spirit of the work, and to
offer him my hearty thanks for all his trouble in the matter.
May the book find many friends among the English-
speaking peoples, and help to stimulate the interest of its
readers in the development of our science.
ERNST VON MEYER.
LEIPZIG, February, 1891.
TRANSLATOR'S PREFACE TO THE SECOND
ENGLISH EDITION
THE present edition is a translation of the second German
edition (published in 1895), with a number of further addi-
tions and alterations, most of these latter having been made
by the author, but a good many of them by myself, with his
approval ; and, as in the case of the previous edition, the
proof sheets had the benefit of the author's revision after my
own corrections were made.
In his preface to the second German edition Professor
von Meyer expresses his gratification at the success of
the English version, and then goes on to speak of the
additional sources of information on subjects of historical
chemistry which have during the last few years become
available for reference. Among these are the Berzelius-
Liebig and the Liebig-Wb'hler Letters, the Letters and
Journals of Scheele, Priestley's Letters, and the autobio-
graphical fragment which Liebig left behind him. In
addition, there are the recently published and valuable his-
torical researches of Berthelot on the chemistry of the early
Middle Ages, and the writings of Ladenburg, Schorlemmer,
Thorpe, Grimaux, and others on the development of chem-
istry within certain definite periods, or on the life and work
of particular chemists.
TRANSLATOR'S PREFACE
I may, perhaps, be permitted to add my word of appreci-
ation to what the author has said with regard to the friendly
reception of the first English edition both in this country
and in America, and to express the hope that the present
edition may be found at least equally acceptable.
GEORGE McGOWAN.
BALING, LONDON, W.
July, 1898.
TABLE OF CONTENTS
PAGE
LIST OF ABBREVIATIONS .... . xxiii
INTRODUCTION 1
p
CHAPTER I
FROM THE EARLIEST TIMES TO THE BIRTH OF ALCHEMY . . 5
Theoretical Views upon the Composition of Substances, and
especially upon the elements, 6. Aristotle's Elements, 7.
The Empirical Chemical Knowledge of the Ancients, 9.
Metallurgy of the Older nations— Gold, 11 ; Silver, Copper,
Iron, 13 ; Lead, Tin, etc., 14; Mercury, 15. The Manufacture
of Glass, 16. Pottery, 17. The Manufacture of Soap, 17. Dye-
ing, 17. The beginnings of Pharmacy, 18.
CHAPTER II
THE AGE OF ALCHEMY 21
General History of Alchemy 23
Origin and First Signs of Alchemistic Efforts, 23. The Alex-
andrian Academy, 27. The A Ichemy of the A rabians— Geber and
his Disciples, 28-30. Alchemy among the Western Nations, 30.
Albertus Magnus, Roger Bacon, 31. Arnaldus Villanovanus, 32.
Raymundus Lullus, 33. Basilius Valentinus, 36.
, Special History of Alchemy 37
Theories and Problems of the Alchemistic Period, 37. The
pseudo-Geber, 39-41. Views of Basilius Valentinus, etc., 41.
The Philosopher's Stone, 42.
Practical -Chemical Knowledge of the Alchemists, 45.
Technical Chemistry — Gold, 46. Silver, 46. Copper and
other metals, 47. Pottery, Glass, Dyeing, 47-48. Pharma-
ceutical Chemistry, 48.
CONTENTS
Knowledge of the Alchemists with regard to Chemical Com-
pounds, 49. Alkalies, 50, Acids, 51. Salts, 52. Preparations
of Antimony, etc. , 54. Organic Compounds, 56.
The Fortunes of Alchemy during the last Four Centuries, 58.
A Short Review of Alchemistic Efforts, 63.
CHAPTER III
PAGE
HISTORY OP THE IATRO-CHEMICAL PERIOD 65
General History of this Period . 67
Paracelsus and his school, 67. The latro-chemical Doctrines
of Paracelsus, 69. Turquet de Mayerne, 73. Libavius, 74.
Van Helmont and his Contemporaries, 75. The work of van
Helmont, 73. Sala and Sennert, 80. Sylvius and Tachenius,
80. Georgius Agricola, 80. Palissy, 85. Glauber, 86.
Special History of the latro-chemical Period .... 87
Technical Chemistry, 87. Metallurgy, 88. Pottery and
Glass Manufacture, 89. Dyeing, etc., 90.
Development of Pharmacy and of the Knowledge of Chemical
Preparations, 91. Inorganic Compounds, 91. Organic Com-
pounds, 96.
CHAPTER IV
HISTORY OF THE PERIOD OF THE PHLOGISTON THEORY, FROM
BOYLE TO LAVOISIER 100
INTRODUCTION 100
General History of the Phlogistic Period .... 103
Robert Boyle, 103. Mayow, 107. Lemery and Homberg, 107.
Kunkel and Becher, 109. Stahl and the Phlogiston Theory, 110.
Fr. Hoffmann and Boerhave, 113.
The development of Chemistry, and particularly of the
Phlogiston Theory, after StahVs Time, 115. Neumann, Eller,
Pott, Marggraf, 115-116. Geoffrey, Duhamel de Monceau,
Rouelle, Macquer, 117-119. Black, 119. Cavendish, 121.
Priestley, 122. Bergman and Scheele, 124-125.
Special History of the Phlogistic Period 128
Pneumatic Chemistry and its Relations to the Doctrine of
Phlogiston, 128. The Discovery of Oxygen and the Composition
of Air, 130.
Development of Theoretical Vieivs in the Phlogistic Period, 134,
Views regarding Elements and Chemical Compounds, 135.
CONTENTS
Views regarding Chemical Affinities and its Causes, 137.
Geoffrey's Tables of Affinities, 138.
Practical Chemical Knowledge, in the, Phlogistic Age, 140.
The Development of Analytical Chemistry, 141. Boyle, 141.
Fr. Hoffmann, Marggraf, Scheele, 142-143. Bergman, 143. The
beginnings of Gas Analysis, 145.
Technical Chemistry in the Phlogistic Age — Metallurgy, 146.
The Ceramic Industry, Dyeing, 147.
Technico-chemical Preparations — Acids and Alkalies, 147.
The Discovery of Elements, 149. Inorganic and Organic Com-
pounds, 150-151.
Pharmaceutical Chemistry, 154.
Concluding Remarks upon this Period, 155.
CHAPTER V
PAGE
HISTORY OF THE MOST RECENT PERIOD (FROM THE TIME OF
LAVOISIER UP TO NOW) 158
Introduction . . 158
General History of Chemistry during this Period . . 160
Lavoisier and the Antiphlogistic Chemistry, 160. Lavoisier's
Life and Work, 160 et seq. His Combustion Theory, 164-167.
Triumph of the Antiphlogistic Chemistry, 168. Beginnings of
a Rational Chemical Nomenclature, 170. Guyton de Morveau,
172. Berthollet, 173. Fourcroy, 174. Vauquelin, 176. %\
The State of Chemistry in Germany at the end of the 1\
Eighteenth Century, 177. Klaproth, 178. The State of Chemistry
in England, Scotland and Sweden, 180.
Development of the Doctrine of Chemical proportions, 181.
Richter, 182. His law of Neutralisation, 183. The Beginnings
of Stdchiometry, 185. Proust, 185. Hi scon test with Berthollet,
186. Recognition of Constant Combining Proportions, 187.
Dalton's Atomic Theory 188
Law of Multiple Proportions, 189-190. Dalton's Attempts to
determine the relative Atomic Weights of the Elements, 191.
His Atomic Weights and Chemical Symbols, 193-194.
Further Development of the Atomic Theory, 194. Thomas
Thomson, 194. Wollaston, 195. Humphry Davy, his Life and
most important Work, 195-199. Gay-Lussac, 199. His Law of
Volumes and Work generally, 200-201 . Front's Hypothesis and its
Effects, Wl.
Berzelius — A Survey of his Work 203
Biographical Notice, 204. His Influence upon the Develop-
CONTENTS
ment of Analytical and Organic Chemistry, 205-207. His
Experimental Researches, 205-207. Berzelius as a Teacher and
Writer, 207-209. His general Character, 209.
Development of the Atomic Theory by Berzelius, 210. His
Determinations of relative Atomic Weights, 211 et seq. His
Oxygen Law, 212.
Influence of Gay-Lussac's Law of Volumes upon the Atomic
Theory, 214. Avogadro's Hypothesis, 215. Application of the
Law of Volumes by Berzelius, 216. The Position of the Atomic
Theory in 1818, 217. Dulong and Petit's Law, 220. Influence
of the Doctrine of Isomorphism upon the Atomic Theory, 221.
Mitscherlich, 222.
The Atomic Weight System of Berzelius from 1821 to 1826, 223.
Dumas' Attempt to alter the Atomic Weights, 225. Failure of
this Attempt, 227. Faraday, 227. His Law of Definite
Electrolytic Action, 228.
The Electro- Chemical Theories of Davy and Berzelius, 229 et
seq. The Dualistic System of Berzelius, 233. His Chemical
Nomenclature and Notation, 234-237.
Manifestations against Dualism, 237. Discovery of the
Alkali Metals, 238. Recognition of the Elementary Nature of
Chlorine, 240. Theory of the Hydrogen A cids (Davy and Dulong),
241. Doctrine of the PolybasicA cids (Liebig), 243. Graham, 244.
Development of the Dualistic Doctrine in the Domain of
Organic Chemistry, 246. The Growth of Organic Chemistry
previous to 1811, 246. The Position of Berzelius with regard to
Organic Chemistry, 248. Development of Views respecting
Radicals, 249.
Isomerism and its Influence on the Development of Organic
Chemistry, 250. Observations of Liebig, Wohler, Faraday, and
Berzelius, 251. Clearer Definition of the terms Isomerism,
Polymerism, and Metamerism by Berzelius, 252.
The older Radical Theory, 253. The Etherin Theory,
(Dumas and Boullay), 253-254. Liebig and Wohler's Work upon
Benzoyl Compounds, 254. The Ethyl Theory of Berzelius and
Liebig, 256. Position of the Radical Theory in 1837, 258.
Definition of the term Radical, 260. Bunsen, 260. His Work
upon the Cacodyl Compounds, 261. The significance of the
Radical Theory, 261.
Liebig, Wohler, and Dumas — A Survey of their more import-
ant Work, 262. Justus Liebig, his Life and Work, 262. Liebig as
a Teacher, 265. His Literary Activity, 266. His experimental
Researches, 267. Friedrich Wohler, 270. Wohler as a Teacher
and Writer, 271. His services to Science, 272. Dumas, his Life
and Work, 272-275.
The Development of Unitary Views in Organic Chemistry, 275.
CONTENTS
Substitution Theories, 275. Dumas' Laws of Substitution, 276.
Laurent's Substitution or Nucleus Theory, 278. Criticism of the
same, 279. Dumas' Type Theory, 280. His Unitary System,
281. The Overthrow of Berzelius' Dualistic Doctrine, 282.
Berzelius' Fight against the Substitution Theory and his Defeat,
282 et seq.
Fusion of the older Theory of Types with the Radical Theory
by Laurent and Gerhardt, 286. Laurent and Gerhardt, a Sketch
of their Lives, 286. Gerhardt's Theory of Residues, 287. His
Law of Basicity, 289. Gerhardt' s first Classification of Organic
Compounds, 289. His Reform of the Atomic Weight System, 290.
The distinguishing between the terms Molecule, Atom, and Equival-
ent by Laurent and Gerhardt, 293. Work preparatory to the new
Type Theory— Wurtz and A. W. Hofmann, 295-298. Williamson's
Experiments on the Formation of Ethers, 298. His Opinions
with regard to the "Typical" View, 299. Gerhardt' s new
Theory of Types, 300. Work preparatory to this, 301. Deriva-
tion of Organic Compounds from Types, 303. Gerhardt's Views
upon Chemical Constitution, 304. Criticisms upon his Type
Theory, 306. Extension of the Type Theory by Kekule,
307. Kekule, 308. Mixed Types, 308. Marsh Gas as a Type,
309. Position of the Type Theory in 1858, 310.
Development of the Newer Radical Theory by Kolbe — A Survey
of Kolbe' s Life and Work, 311. The Re-animation of the Radical
Theory by him — Frankland's Co-operation, 313. Copulated or
Conjugate Compounds, 315. Setting aside of the Notion of
Copulation by Frankland, 316. Kolbe's Carbonic Acid Theory,
317. The Derivation of Organic Compounds from Inorganic, 317.
Kolbe's most important Experimental Researches, 319. His Atti-
tude towards the older and the newer Chemistry, 320. Kolbe's
real Types, 321.
PAGE
The founding of the Doctrine of the Saturation-Capacity
of the Elements by Frankland 322
Preparatory steps towards this Doctrine, 322. Frankland's
services here, 322 et seq. Assumption of a varying Saturation-
Capacity, 325. Discussions on the Subject by Odling, William-
son, and Wurtz, 326-327.
The Recognition of the Valency of Carbon, 327. Kekul6's
services here, 329. Kolbe and Frankland's share in the Matter,
329.
Development of Chemistry under the Influence of the
Doctrine of Valency during the last Thirty Years . . 331
Beginnings of the Structure Theory — Kekule and Couper, 332.
Establishment of the true Atomic Weights by Cannizzaro, 335.
b
xviii CONTENTS
Discussions regarding the Nature of " Structure " by Butlerow
and Erlenmeyer, 336.
Controversies respecting constant and varying Valency of the
Elements, 337. Views upon varying Valency held by Frankland,
Kolbe, etc., 337-338; by Erlenmeyer, Wurtz, and Naquet, 338.
Kekule's Theory of a Constant Valency, 338 ; Grounds for the
Assumption of a varying Valency, 340 et seq.
The further Development of the Structure Theory — The chief
Directions taken by Organic Chemistry during the last Thirty
Years, 342. Views upon the linking of Atoms, 343. Constitu-
tion of Organic Compounds according to the Structure Theory, 344.
Saturated and Unsaturated Compounds, 344. Kekule's Theory
of the Aromatic Compounds, 346. Modifications in this Theory
proposed by Ladenburg, Glaus, and Baeyer, 348-349. Constitu-
tion of pyridine, pyrrol, etc., 350-351. Victor Meyer's more pre-
cise Conception of the term Aromatic Compounds, 351. Applica-
tion of Structural -chemical Conceptions to the Investigation of Iso-
merism, 351. Position-isomerism, 353. Tautomerism or Desmo-
tropism, 354-355. Geometrical isomerism (Wislicenus), 356.
Allo-isomerism (Michael), 356. The supposed Spacial Arrangement
of atoms, 357 et seq. The Development of Important Methods for
investigating the Constitution of Organic Compounds, 361.
Synthetic Methods (Wohler, Kolbe, Frankland, Baeyer, Kekule,
Ladenburg, Fittig, W. H. Perkin sen., and others), 361.
Chemical Behaviour of Organic Compounds, 365.
The Main Currents in Inorganic and General Chemistry during
the last Thirty Years, 367. Application of the Structure Theory
to Inorganic Compounds, 368. Important Researches in In-
organic Chemistry, 369. The Periodic System of the Elements
(Newlands, L. Meyer, Mendelejeff), 370. Crookes' Hypothesis
of a Primary Material, 374. General Significance of Physico-
chemical Investigations, 375. Ostwald, 377. Van 't Hoff, 377.
CHAPTER VI
PAGE
SPECIAL HISTORY OF THE VARIOUS BRANCHES OF CHEMISTRY
FROM LAVOISIER TO THE PRESENT DAY . . . 379
Introduction 381
History of Analytical Chemistry 384
Qualitative Analysis of Inorganic Substances, 384. Use of
the Spectroscope for this purpose, 385. Quantitative Analysis of
Inorganic Substances, 386. Kaproth, Vauquelin, 386. Lavoisier,
Proust, Berzelius, 387. Dumas, Erdmann and Marchand,
Marignac, and Stas, 388. H. Rose, Wohler, Fresenius, 389.
CONTENTS
Docimacy, 390. Volumetric Analysis, 390. Its Development
by Gay-Lussac, Bunsen, Mohr, etc., 391. Development of
Methods of Gas Analysis, 392. The Analysis of Organic
Substances (Lavoisier, Gay-Lussac and Thenard, Berzelius,
Liebig), 393-397. Legal-chemical Analysis, 397. Technico-
chemical Methods, 398.
PAGE
The Progress in Pure Chemistry from Lavoisier to the
Present Time 400
Special History of Inorganic Chemistry 400
The Discovery of Elements, and the Determination of their
Atomic Weights, 401. Oxygen, Nitrogen and Hydrogen, 401-402.
The Halogens, 402. Selenium, Tellurium, etc., 403. Boron and
Carbon, 404. Allotropy, 405. The Metals of the Alkalies and
Alkaline Earths, 407-408. Beryllium, Cadmium, Thallium,
Aluminium, Indium, Gallium, 408-409. Metals of the Cerium
Group, 409. Nickel and Cobalt, 410. Chromium, Titanium,
Germanium, etc., 410-411. Vanadium and allied Elements, 412.
Metals of the Platinum Group, 413. Argon, Krypton, Metar-
gon, Neon and Helium, 414-417. Rayleigh, 414. Ramsay, 415.
Supposed new Elements, 417.
Inorganic Compounds, 418. Hydrogen Compounds of the
Halogens, 418. Oxygen Compounds of Hydrogen and of the
Halogens, 418. Sulphur, Selenium and Tellurium Compounds, J.
420. Compounds of Nitrogen, Phosphorus, etc., 421-424. Com-
pounds of Boron, Silicon, and Carbon, 424. Compounds of the
Alkali and Alkaline Earth Metals, 426. Compounds of the
Metals of the Iron Group, etc., 427. Compounds of Tin, Vana-
dium, etc., 429. Compounds of Gold, Platinum, etc., 430.
Special History of Organic Chemistry in the Nineteenth
Century 432
Hydrocarbons and their Derivatives, 433. The Alcohols and
Analogous Compounds, 437. Carboxylic Acids, 441. Acid Chlor-
ides, Anhydrides, and Amides, 444. Oxy- and Amido- Acids, 446.
Aldehydes, 448. Ketones and Ketonic Acids, 451. Carbohy-
drates and Glucosides, 454. Haloid Derivatives of the Hydro-
carbons, etc., 457. Nitro- and Nitroso-Compounds, 460.
Sulphur Compounds, 462. Organic Nitrogen Compounds
(Amines, etc.), 465. Phosphines, Arsines, Stibines, 469. Azo-
Compounds, 470. Diazo-Compounds, 470. Hydrazines, Cyano-
gen Compounds, 472-478. Pyridine and Quinoline Bases, 478.
Their Relation to Vegetable Alkaloids, 482. Pyrrol and Analo-
gous Compounds, 484. Organo-metallic Compounds, 486.
b 2
CONTENTS
History of Physical Chemistry in Recent Times . . . 488
Determination of Vapour Density and the Application of this,
490. Dissociation, 492. The Liquefaction of Gases, 492. The
Kinetic Theory of Gases, 493. Spectrum Analysis, 494. Atomic
Volumes of Solids and Liquids, 495. Laws regulating the Boiling
Temperature, 496. Specific Heat of Solid Bodies, 497. Optical
Behaviour of Solids and Liquids (Refraction, Circular Polarisa-
tion), 498. Diffusion, etc., 500. Theory of Solution ; Electrolytic
Dissociation, 501. The Electrolysis of liquid or of dissolved Sub-
stances, 503. Isomorphism, etc., 505. Thermo- Chemistry, 507.-
Julius Thomsen ; Berthelot, 508. Photo- Chemistry, 509.
Development of the Doctrine of Affinity since the Time of
Bergman, 512. Bergman's Doctrine of Affinity, 512. Berthollef s
Doctrine oj Affinity, 513. The Supplanting of Bertholletf s Opinions
by other Doctrines, 515. The Revival of Berthollef s Doctrines,
517. The latest Development of the Doctrine of Affinity, 519.
Sketch of the History of Mineralogical Chemistry during
the last Hundred Years . .522"
Its Earlier History, 522. The Chemical Mineral System of
Berzelius, 524. Other Mineral Systems, 525. The more recent
Development of Mineral Chemistry, 525-526. The Artificial
Production of Minerals — Beginnings of Geological Chemistry, 527.
Development of Agricultural and of Physiological Chemistry 530
Agricultural Chemistry and Vegetable Physiology, 531. The
Humus Theory, 531. Reform of Agricultural Chemistry by
Liebig, 532. Its further Development by Liebig and his School,
533. Nitrification and the Assimilation of free Nitrogen by
plants, 534-535.
The Development of Phy to -Chemistry, 536. Important
Phyto-Chemical Researches, 537-538.
The Development, of Zoo-Chemistry, 539. Researches upon
the Constituents of the Animal Body, 539. The Chemistry of
the Animal Secretions — Saliva, Gastric Juice, Bile, Blood, 541 ;
Milk, Urine, 542. Metabolism, 544.
Fermentation; Putrefaction, 546. Views regarding
Fermentation, 546 et seq. Organised and Unorganised Fer-
ments, 548. The Phenomena of Putrefaction, 548. The
Ptomaines, 549.
The Relation of Chemistry to Pathology and Therapeutics^
549. Bacteriology, 550. Antiseptics, Anaesthetics, and Anti-
pyretics, 550-551.
The Relation of Chemistry to Pharmacy, 552.
CONTENTS xxi
History of Technical Chemistry during the last Hundred
Years 554
Introduction, 554. Development of Technical Instruction,
556. Literature on Technical Chemistry, 556.
The Progress of Metallurgy , 557. Iron and Steel, 557. Nickel,
Silver, the Galvano-Plastic Process, Aluminium, 558-559.
Mineral Pigments, 560.
Development of the Great Chemical Industries, 561.
Sulphuric Acid, 561. The Soda Industry, 562-564. Hydro-
chloric Acid, Chlorine, and Bleaching Powder, 565-566.
Bromine and Iodine, 566. Nitric Acid, Gunpowder, 566-567.
Other Explosives, Matches, 568.
The Manufacture of Soap, etc., 569. Ultramarine, 570.
Glass, Earthenware, and Pottery, 570, 571. Mortar, Paper,
571, 572. Starch, Beet-Sugar, 572-574.
Fermentation Processes, 574. The Manufacture of Spirits,
575. The Quick Vinegar Process, 575.
The Aniline Colours and other similar Dyes, 576. Phthal-
e'ins, Azo-Dyes, 578. Alizarine, the Safranines, Indigo Blue,
579. Dyeing, 580. Tanning, 580.
Various Chemical Preparations, 581. Various Products
from Coal-tar ; Illuminants, 582. Heating Materials, 584.
The Growth of Chemical Instruction in the Nineteenth
Century, more especially in Germany .... 586
The State of Education in Science at the end of the
Eighteenth Century, 586. Experimental Lectures, 587. The
Development of Practical Instruction (Berzelius, Liebig), 587-
588. The Erection of Laboratories for General Instruction in
Germany, 588 et seq. Erdmann, 590. The State of Scientific
Education in France, Great Britain, etc., 591. Improvements
in the Construction of Chemical Laboratories, 593.
Chemical Literature, 594. Text-books, 594. Larger
Treatises and Encyclopedias, 595. Periodical Journals, 596.
Yearly Reports (Jahresberichte), 597. The Necessity for
Criticism in Chemical Literature, 598. The Study of Original
Memoirs, 598.
INDEX OF AUTHORS' NAMES . 601
INDEX OF SUBJECTS 613
ABBREVIATIONS OF THE NAMES OF MOST OF
THE JOURNALS TO WHICH REFERENCE
HAS BEEN MADE
Ann. Chem. . . Liebig's Annalen der Chemie und Pharmacie (begun
1832).
Ann. Chim. . . Annales de Chimie et de Physique (begun 1816 ; five
series).
Ami. de Chimie . The same journal from 1789 to 1815.
Ann. des Mines . Annales des Mines.
Ann. of Philosophy Annals of Philosophy (edited by Thomas Thomson,
1813-26). This journal was subsequently merged
in the Philosophical Magazine.
Ann. Phys. . . The new Series (Neue Folge) of Poggendorff's Annalen.
Archiv. Pharm. '. Archiv der Pharmacie (begun 1832).
Bayer. Akad. . . Sitzungsberichte der Bayerischen Akademie der Wiss-
enschaften.
Ber Berichte der Deutschen chemischen Gesellschaft (begun
1868).
Bull. Soc. Chim. . Bulletin de la Societe Chimique de Paris (begun 1864).
Chem. Centr. . . Chemisches Centralblatt (begun 1848).
Chem. News . . Chemical News (begun 1860).
Compt. Rend. . . Comptes Rendus des Seances de 1' Academic des Sciences
(begun 1835).
Crell's Ann. . . Chemische Annalen von L. v. Crell (1784-1805).
Dingl. Journ. . . Dingler's Polytechnisches Journal (begun 1820).
Gazz. Chim. Ital. . Gazzetta Chimica Italiana (begun 1871).
Gilb. Ann. . . . Annalen der Physik von Gilbert und Gr en (1798-1824).
/Bericht iiber die Entwickelung der Chemischen Indus- m
Hofmanrfs *r^e wahrend des letzten Jahrzehnts von Hofmann
Bericht etc. . (began 1875, but ceased after the publication of
\ two volumes).
Jahres. Berz. . . Jahresberichte iiber die Fortschritte der Chemie und
Mineralogie von Berzelius (1821-47).
Jahres. d. Chemie Jahresberichte iiber die Fortschritte der Chemie von
Liebig und anderen (begun 1847).
LIST OF ABBREVIATIONS
Journ. Chem. Ind. Journal of the Society of Chemical Industry (begun
1882).
Journ. Chem. Soc. Journal of the Chemical Society (Memoirs and Pro-
ceedings, vols. i.-iii., 1841-47 ; Journal begun 1848).
Journ. de Phys. . Journal de Physique (1778-94 ; 1798-1823).
Journ. pr. Chem. Journal fiir praktische Chemie (begun 1834 ; the new
series begun 1870).
Mon. Sclent. . . Moniteur Scientifique (edited by Quesneville, begun
1857).
Phil. Mag. . . Philosophical Magazine (begun 1798).
Phil. Trans. . . Philosophical Transactions of the Roya) Society (begun
1666).
Phil. Trans. E. . Philosophical Transactions of the Royal Society of
Edinburgh (begun 1788).
Pogg. Ann. . . Annalender Physikund Chemie von PoggendorfF (begun
1824 ; new series begun 1877).
Proc. JR. S. . . Proceedings of the Royal Society [begun 1800. Vols.
i. -iv. (1800-1843) are entitled "Abstracts of the
Papers printed in the Philosophical Transactions of
the Royal Society of London," and vols. v. , vi.
(1843-1854) " Abstracts of Papers communi-
to the Royal Society." The final form of title,
"Proceedings of the Royal Society of London,"
begins with vol. vii., published in 1856].
Proc. JR. S. E. . Proceedings of the Royal Society of Edinburgh (begun
1845).
Rec. Trav. Chim. . Recueil des Travaux Chimiques (begun 1882).
Schiveigg. Journ. Journal fiir Chemie und Physik von Schweigger
(1811-33).
Wagner's Jahresber. Jahresbericht iiber die Leistungen der chemischen
Technologic von Wagner (begun 1856).
Wiener Monatshefte Monatshefte fiir Chemie und verwandte Theile anderer
Wissenschaften (begun 1880).
Ztschr. anal. Chem. Zeitschrift fiir analytische Chemie von Fresenius (begun
1862).
Ztschr. Chem. . Zeitschrift fiir Chemie (1865-71); this was a continua-
tion of the Kritische Zeitschrift (begun 1858).
Ztschr. phys. Chem. Zeitschrift fiir physikalische Chemie, Stochiometrie,
und Verwandtschaftslehre (edited by Ostwald and
van 't Hoff ; begun 1887).
ERRATA.
Page 27, line 18, from top, for "Synesius" read "Synesios."
„ 357, ,, 2, from top, for " Lebel " read " Le Bel."
„ 386, , , 2, from top, for ' ' Kirchoff " read ' < Kirchhoff. "
,, 407, ,, 19, from top, for " Matth lessen " read "Mathiessen."
,, *46, ,, 17, from top, for " R. Hofmann " read " R. Hoffmann."
„ 481, ,, 5, from foot, for ' ' Huisberg " read " Hinsberg."
,, 499, ,, 5, from foot, for "Lebel" read " Le Bel."
,, 502, ,, 11, from foot, for "Eykman" read "Eykmann."
, , 505, , , 11, from foot, for ' ' Scherer ' ' read ' ' Scheerer. "
,, 537, ,, 7, from top, for "formic acid" read "formic aldehyde.
,, 543, ,, 11, from foot for "Scherer" read "Scheerer."
,, 558, ,, 7, from foot, for "Pattison" read "Pattinson."
„ 575, note 4, for " Schiizenbach " read " Schiitzenbach."
A HISTOKY OF CHEMISTEY
INTRODUCTION
CHEMISTRY has for the last two hundred years or so been
defined as the study of the composition of substances. Its
first task, therefore, lies in ascertaining the constituents of
which the material world surrounding us is composed, in
reducing these constituents to their elements, and in building
up new chemical compounds from the latter. Hand in hand
with these analytic and synthetic problems there goes the
further task of determining the laws which regulate the
chemical combination of matter.
The problems just indicated occupy, in the widest sense
of the word, the attention of chemists to-day. The prob-
lems of chemistry were, however, different in former times,
and it is precisely these differences in aim which characterise
the various epochs into which the history of the science may
therefore be divided.
The oldest nations with regard to which we possess
reliable information — the Egyptians, Phoenicians, Jews and
others — did indeed possess a certain disjointed knowledge of
chemical processes acquired accidentally; but these were
applied for their practical results alone, and not with the
object of deducing any comprehensive scientific explanation
from them. We meet with similar conditions among the
earliest cultured European nations, the Greeks and Romans,
who owed most of their knowledge of chemical facts to the
peoples just named. Nowhere do we find in antiquity the
endeavour to gain an insight into chemical processes by
2 A HISTORY OF CHEMISTRY INTRO.
means of definitely planned experiments. Although the
Ancients were wholly without such data, furnished by exact
research, as are nowadays held to be indispensable, this
did not prevent them from speculating as to the nature of
the- universe; indeed, those theoretical views upon the
nature of matter, on the " elements " of which the world
was composed, have given to the earliest age of chemistry
its own particular stamp. Some of these systems — especi-
ally Aristotle's system of the elements — continued to hold
sway for many centuries, and influenced more especially the
whole teaching of the Middle Ages.
From the above-mentioned doctrine of the nature of the
elements was developed the theory of the transmutation of
metals, or rather the fixed belief that one element can be
transformed into another. Even so far back as the beginning
of our own era, at first in Egypt, there began the striving to
transmute the base metals into the noble, to " create " gold
and silver.
The art by which this was to be achieved was termed
chemia (^/W<z), a name dating, so far as actual proof goes,
from the fourth century, but in reality probably from an
earlier period.1
There are many indications that this conception of the
aim of chemistry and of the problems which it had to solve
predominated for centuries following, e.g. it lies at the
root of the definition giverHby-Suidas, the author of an
encyclopedia, who lived in the eleventh century: "Chem-
istry, the artificial preparation of silver and gold ; " further,
" XPV(707rol/^a " was a very commonly used designation for
chemistry over a long period.
This task, the solution of which was the aim of the
1 This word is of Egyptian origin and is probably founded on the North
Egyptian word CMmi, the name for Egypt. It also means, however,
"black," and hence there is still some doubt whether the word x^M6*0 °f
that period denotes Egyptian art or, as Hoffmann in the article " Chemie,"
in the Dictionary of Chemistry edited by A. Ladenburg, endeavours to
prove, the employment of a black -coloured preparation valuable for al-
chemistical purposes. The mode of writing x^6'0* and ^ne derivation of
this word from xvP-&s> mav ^e regarded as incorrect.
INTRO. INTRODUCTION
so-called Alchemy,1 characterises the • alchemistic period, a
period extending from at least the fourth century of our era
to the first half of the sixteenth. It is impossible to state
with perfect exactitude the date at which alchemy took its
rise, its origin being lost in the mists of the past. The
labours of the alchemists, who strove by all imaginable
methods to attain to the philosopher's stone (by the aid of
which not only were the noble metals to be produced from
the base, but also the life of man to be prolonged), had the
effect of largely extending the area of the then existing
knowledge of chemical facts.
In the first half of the sixteenth century, almost contem-
poraneously with the Reformation, i.e. with the birth of a
new epoch in the world's history, chemistry began to develop
in a new direction, without, however, losing all at once its
alchemistic tendencies. Chemistry, which had already
proved itself a valuable helpmeet to medicine in the
preparation of active remedies, came to be looked upon as
the basis of the whole medical art. Health and illness were
reduced to chemical processes in the human body ; only by
means of chemical preparations could an unhealthy body be
restored to its normal condition ; in short, the absorption of
medicine in chemistry, the fusion of both together, was the
cry which emanated from Paracelsus. Van Helmont, de le
Boe Sylvius, Tachenius and others were the chief exponents
of this doctrine, which characterises the period of Medical or
latro-Chemistry. The fact that technical chemistry was
advanced at the same time, through the labours of indi-
viduals such as Georgius Agricola, was without influence on
the prevailing tendency of the science of that age.
From the middle of the seventeenth century on, the
iatro-chemical current gradually underwent substitution by
another. After that date chemistry strove hard to becpme a
self-supporting branch of natural science, quite independent
of every other. Indeed, the history of chemistry proper
begins with Robert Boyle, who taught, as its main object,
the acquisition of a knowledge of the composition of bodies.
The conception of this aim marks the date from which
1 This term with the Arabic prefix "al" became naturalised very early.
B 2
4 A HISTORY OF CHEMISTRY INTRO.
chemistry may be regarded as a science striving towards
an ideal goal along the paths of exact research, without
regard to practical results, and solely with the object of
arriving at the truth.
The most important problem, whose solution occupied all
the chemists of note at that day, was the question of the
chemical reasons underlying the phenomena of combustion.
Since Stahl's attempt to explain the latter, the hypothetical
fire stuff Phlogiston — which was supposed to escape during
every combustion — was regarded as the universal principle of
combustibility. This doctrine held sway over chemists at
the end of the seventeenth and during the greater part of
the eighteenth centuries to such an extent that we are
justified in characterising this period (after the death of iatro-
chemistry) as the period of the Phlogiston Theory.
The fall of the latter, and its replacement by the anti-
phlogistic system of Lavoisier, bring us to the commencement
of the chemical era in which we are still living. For, upon
the foundation laid by Lavoisier and his co-workers, and
firmly fixed by Dalton, Berzelius and others, the structure of
the new chemistry rises. The founding and developing of
the chemical atomic theory, and its extension to all parts of
chemical science, characterise this latest epoch, to which the
period of Lavoisier's reform of chemistry was a necessary
stepping-stone ; it is, therefore, to be designated as the
period of the Chemical Atomic Theory. An insight into
the conditions which it involved being only possible by
careful quantitative researches, the balance has been, since
the time of Lavoisier; the most valuable instrument of the
chemist. H. Kopp is, therefore, fully justified in naming
the epoch which begins with the French savant the period of
quantitative research. Of late years the first aim of chem-
istry, i.e. the exact determination of the composition of
substances, has been accompanied by the investigation of
the relations which exist between their physical properties
and chemical composition. But the light of the atomic
theory permeates the whole, so that one is forced to regard
it as the guiding star of modern chemistry.
CHAPTER I
FROM THE EARLIEST TIMES TO THE BIRTH OF
ALCHEMY
THE characteristics of this period, which have been already
referred to, justify one in designating it the period of crude
empiricism with regard to chemical facts. In sharp contrast
with the disinclination of the Ancients towards experiment,
through which alone the secrets of nature are to be un-
ravelled, stood their great love of speculation, by means of
which they did not hesitate to attempt an explanation of the
ultimate reasons of all things. Aristotle, to whom the natural
sciences owed the direction which they followed for a very
long time, pointed to deduction as the road which should
lead to the goal. Instead of drawing general conclusions
from accurately observed facts, the Ancients preferred to
advance from the general to the particular. The position of
all the natural sciences in far-back times, especially that of
chemistry, is sufficient to prove how the most mischievous
errors crept in and became firmly established in consequence
of following the purely deductive method.
The philosophical writings of the Ancients, especially those
of the Greeks and Romans, give us a tolerably distinct idea
of their theoretical views. Certain writings of Aristotle, and
also the " Trepl \l6wv " of his pupil Theophrastus, are of
especial value for the criticism of the empirical chemical
knowledge of these times. The works of Dioscorides on
Materia Medica and particular chapters of the Historia
Naturalis of the elder Pliny give us an exceptionally clear
insight into the knowledge of the Ancients. Dioscorides, who
6 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CH.
was born about the middle of the first century at Anazarbos,
enlarged his acquirements, already great, by experiences
collected on long journeys. His fame as a physician holds
good among the Turkish doctors to this day. The work of
Pliny above-mentioned contains exceedingly valuable records
of the state of scientific knowledge in his time ; it also ^hows,
however, that the author was by no means master of the
immense amount of material which he had collected l from
tradition, but which he had not really assimilated.
Theoretical Views upon the Composition of Substances, and
upon the Elements?
The question of the ultimate constituents of bodies, i.e., of
the elements which go to build up the world, occupied the
minds of the oldest nations. To give an exhaustive description
of their speculations on the point does not come within the
scope of this work ; what is wanted is rather to call special
attention to those views which have exercised a permanent
influence upon the chemical ideas of later times.
This applies in a particular degree to the doctrine of the
elements, which originated with Empedoclfis, although it
usually bears Aristotle's name; also, but to a much lesser
extent, to the ideas of the older Greek philosophers regarding
the original material of which the world, according to them,
was built up. Views like that of Thales^ (in the sixth cen-
tury B.C.), that water is the ground material, or those of
Anaximenes and Heraclitna (in the same century), who
ascribed to air and fire respectively the same role, have had
no influence upon the development of chemical knowledge.
1 Pliny the younger characterised the work of his uncle as " opus diffusum,
eruditum, nee minus varium, quam ipsa natura," and similar admiration
of it was expressed by other authors of the day. Our thanks are due to
E. O. von Lippmann, who has recently published a memoir entitled Die
chemischen Kenntnisse des Plinius ("Pliny's Knowledge of Chemistry"), in
which the whole subject is treated in lucid style (vide Mittheilungen aus dem
Osterlande, vol. v., p. 370).
2 Cf. Kopp, Geschichte der Chemie, vol. i. p. 29 ; vol. ii. p. 267 ; also
Hofer, Histoire de la Chimie, vol. i. p. 72.
THE ELEMENTS OF ARISTOTLE
Democritus (in the fifth century B.C.) also took a ground
material as the basis of his speculations, but subdivided this
further in that he imagined it to be made up of the smallest
possible particles, of atoms, which differed from one another
\in form and size, but not in the nature of their substance.
All tie changes in the world consisted, according to him, in
the separation and recombination of these atoms, which were
supposed to be in a state of continual motion. This doc-
trine, which at first sight appears to accord with our present
chemical atomic theory, but which in reality has nothing in
common with the latter, was further developed by Epicurus,
as may be well seen in the didactic poem of Lucretius, De
Rerum Natura.
The four so-called "elements" — air, water, earth and
fire — were regarded by that intellectually great philosopher,
Empedocles of Agrigent (about 440 B.C.), as the basis of the
world ; but neither he himself nor Aristotle, who adopted these
into his system of natural philosophy, looked upon them as
different kinds of matter, but as different properties carried
about by one original matter.1 Their chief qualities (the
primce qualitates of the later scholastics) he held to be those
apparent to the touch, viz., warm, cold, dry, and moist. Each
of the four so-called elements is characterised by the pos-
session of two of these properties, air being warm and moist,
water moist and cold, earth cold and dry, and fire dry and
warm. The differences in the material world were, therefore,
to be ascribed to the properties inherent in matter. From
the assumption that these latter can alter, there necessarily
follows the immediate conviction that substances can be
transformed, one into the other. It is easy to see how, when
based upon speculations of this nature, the belief in the
transformation of water into air should establish itself, for
both have the property of moistness in common, while cold,
the individual property of water, can be converted by the
addition of heat into the second chief property of air. And
it is not surprising that considerations of this kind on the
1 Cf. the ingenious exposition by Th. Gomperz in his work " Griechische
Denker," p. 183 (Leipzig, Veit and Co.).
8 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CH.
states of aggregation of matter should lead to the idea of
transforming one kind of matter into another. It was doubt-
less by the generalisation of such views that the belief in the
possibility of the transmutation of metals, which formed the
chief feature of the alchemistic period, grew to the extent
that it did.
Aristotle considered that his four elements were insufficient
in themselves to explain the phenomena of nature ; he there-
fore assumed a fifth one, termed ovcria, which he imagined
to possess an ethereal or immaterial nature and to permeate
the whole world. As the " quinta essentia " this played an
immense rdle among the followers of the Aristotelian doctrine
in the Middle Ages, and gave rise to endless confusion, from
the endeavours of many (who, unlike Aristotle, supposed it to
be material) to isolate it.
There seems to be a high degree of probability in the
assumption that Empedocles and Aristotle did not themselves
deduce their theory of the elements, but derived it from
other sources ; thus the oldest writings of India teach that
the world consists of the four elements mentioned above,1
together with ether,2 which last is most likely related to
Aristotle's overt a.
It is unnecessary to point out how widely the above views
of the Greek philosophers with regard to the elements de-
viate from the conceptions of modern chemistry.
With respect also to the meaning of the term " chemical
combination," one meets, even if only occasionally, with
opinions diametrically opposed to those obtaining at the
present day ; the formation of a substance by the interaction
of others was looked upon as the creation of a new matter,
and the destruction of the original substances from which it
was produced was assumed. Everywhere men were contented
with theoretical explanations, without attempting to prove
their correctness by actual experiment. This want shows
1 Instead of air, the element wind is given.
2 So teaches Buddha (as Dr. Pfungst has been good enough to inform
me) ; see the Anguttara Nikdja, vol. i. fol. c.e. Here consciousness is
named as the sixth element.
i EMPIRICAL CHEMICAL KNOWLEDGE OF THE ANCIENTS 9
itself very markedly in the manner in which the Ancients
regarded the numerous chemical facts which they had learned
by empirical methods, and mostly by accident.
The Empirical Chemical Knowledge of the Ancients.1
The Egyptians stand out prominently from among the
earlier civilised nations as having usefully applied their
knowledge of chemical processes, acquired by chance observa-
tions, to useful purposes ; the needs of everyday life and the
desire to make that life a comfortable one were the incentives.
Their country formed a kind of focus in which was con-
centrated the chemical knowledge of the time, if one may so
designate an acquaintance with technical processes. The
Egyptians already possessed at a very early date a large
experience in the production of metals and alloys, in dyeing,
in the manufacture of glass, and also in the making and
application of pharmaceutical and antiseptic preparations.
The chemical art proper, revered as " holy " (ayia re^vrj), was
jealously guarded by the priesthood as a treasure at once
precious and profitable. Only the elect might penetrate its
mysteries. That laboratories, in which chemical operations
of various kinds were carried out, actually formed adjuncts
to the temples, is clearly proven by the inscriptions found in
such chambers, e.g. at Dendera and Edfu.
There can scarcely be a doubt that the Phoanicians and
Jews obtained their knowledge of the manufacture of import-
ant technical products from the Egyptians. In like manner,
and to an even greater extent, was there a wealth of chemical
experience laid open to the Greeks, and afterwards to the
Romans, by reason of their close relations with the ancient
country Chemi (see p. 2, note 1). The writings of such
eminent Greek philosophers as Solon, Pythagoras, Demo-
critus and Plato, who succeeded in gaining the confidence of
the Egyptian priesthood, contributed in no small degree to
the spread of such practical knowledge.
1 Cf. Kopp, Gesch. d. Chemie, vols. iii. and iv. ; Hofer, Hist., vol. i. p.
106 et seq.
10 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CH.
But all the knowledge so gained was purely empirical ; long
ages were to pass before the various items of which it was com-
posed were brought together under a general scientific stand-
point. In this section of the book merely those portions of
applied chemistry which were known to the Ancients will be
treated of. That a people, so gifted as the Greeks were, should
have failed to understand how to group together the numerous
observations in those subjects which lay ready to their hand,
and to draw conclusions from them, can only be explained by
the whole tendency of their thought, and particularly by their
undervaluing the inductive method. Aristotle's opinion that
"industrial work tends to lower the standard of thought"
was certainly of influence here. In accordance with this
dictum the educated Greeks held aloof from the observation
and practice of technical chemical processes; a theoretical
explanation of the reactions involved in these lay outside
their circle of interests. To this want of sympathy is cer-
tainly to be ascribed the fact that the discovery of even the
most important chemical processes is but very seldom to be
connected with the names of distinct historical persons;
while, on the other hand, the old historians give detailed
records of those men who advanced untenable opinions on the
constitution of the world.
Before giving an account of the state of practical chemical
knowledge in early times, it may be remarked in passing
that much uncertainty often prevailed in consequence of
different products being called by one and the same name.
Substances were not distinguished according to their chemi-
cal behaviour, the investigation of which possessed no interest
for the Ancients, but were classified according to their out-
ward appearance and source, a confounding of similar or
identification of dissimilar substances thus frequently result-
ing. Two samples of one and the same compound — soda, for
instance — were looked upon as different, if the external
appearance seemed to indicate a dissimilarity. Much dis-
crimination has been found to be, and still is, requisite in
order to clear up the indistinct points in the records of the
old historians.
METALLURGY OF THE OLDER NATIONS 11
Metallurgy of the Old Nations}-
We find in the earliest records of the civilised nations (the
Egyptians, Jews, Indians, etc.) an acquaintance with the
working of different metals. By the younger of those nations
mythical personages were held to have taught this art, e.g.
Prometheus, Cadmus, etc., by the Greeks. If the translations
of the Hebrew words in the Old Testament signifying
" metals " are correct, then the Jews were acquainted with
six, viz. gold, silver, copper, iron, lead and tin ; this may be
considered certain as regards the first four, which either
occur native or are readily reduced from their ores. They
are recorded in the Old Testament in the order just given.
The name " metals " is derived, according to Pliny, from
the fact of their never occurring separately but in veins
together, /-ter' d\\a.2 Even at that early period glance, duc-
tility and hardness were held to be characteristics of a metal.
With regard to the origin of metals and ores in the interior
of the earth, the Ancients had formed the most extravagant
conceptions ; they believed, on the ground of Aristotle's
weighty testimony, that they were produced by the penetra-
tion of air into the vitals of the earth, and consequently
assumed that the amount of metal or ore increased as the
mine proceeded inwards.
The Greeks, and especially the Romans, were intimately
acquainted with many metallurgical processes ; Dioscorides,
Pliny and later historians give fairly exact data for the
obtaining and smelting of ores, but not the slightest attempt
is made to explain the chemical processes which this
involves.
The noble metals gold and silver, whose stability in the
1 The following works have been used for reference : — R. Andree, Die
Metalle bei denNatiirvdlkem(Veitund Co., Leipzig, 1884) ; Beck, Geschichte
des Eisens (Vieweg, Braunschweig, 1884 ; 2nd. ed. 1891) ; 0. Schrader,
Sprachvergleichung und Urgeschichte (Jena, 1883) ; and also various treatises
by K. B. Hofmann, to whom the author is greatly indebted for much
information on the subject.
2 Herodotus gives ^iraXKov as signifying a mine.
12 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CH.
fire had not escaped the Ancients, were those earliest known
(in prehistoric times), and were highly valued; the fact of
their occurring native, and the ease with which they can be
worked, afford a sufficient explanation of this.1 The exceed-
ing malleability of gold excitec^ the astonishment of the
older nations in a high degree^ and rendered possible
the gilding of objects by covering them with thin plates of
the metal. The later discovery of affixing a layer of gold by
means of the amalgamation process was known considerably
before the time of Pliny.
In the second century B.C. we meet with the first records 2
of a cupellation process, by which gold was freed from
admixtures; in fact, an operation similar to the so-called
lead process was then carried out, gold dust being melted
with lead and salt for a number of days. The purification of
gold by means of mercury was also well known in Pliny's
time.
Silver, which the enterprising Phoenicians are supposed to
have supplied to the other civilised nations from Armenia
and Spain, where rich silver ores occur, was, according
to the record of Strabo, i.e. at the begining of our era,
purified in a precisely similar manner to gold, viz. by
fusion with lead. The separation of silver from gold does
not appear to have been known before our era, at any rate
an extant record 3 states that Archimedes was not possessed
1 The gold mines of Nubia (the Egyptian name nub, i.e. gold, is perhaps
connected with the designation of that country) were worked very ex-
tensively by the Egyptians. According to the records of Agatharchides
and of Diodorus Siculus, in which pity is expressed for the slaves employed
in the work, the finely ground gold ore was washed out and the heavy residue
melted. In the time of Rameses II. the mines yielded gold to the value of
£125,000,000 sterling per annum. The gold-producing land of Ophir, from
which the Pho3nicians obtained the precious metal, is supposed to have
been in India, Midian (Arabia), or on the east coast of Africa. The same
energetic trading nation opened up for the Greeks the first gold mines on
the island of Thasos.
2 This record, which originated with Agatharchides, is to be found in
Diodorus.
3 Archimedes attempted to determine whether the crown of King Hiero
contained silver, and, if so, how much ; this problem he tried to solve by
taking the specific gravity, not by chemical means.
i METALLURGY OF THE OLD NATIONS 13
of the means to accomplish this. From indications which
Pliny gives, however, it appears that in his time a kind of
cementation process was practised, which probably consisted
in the treatment of silver containing gold with salt and
alum shale. Moreover, an amalgam of gold and silver was
regarded in ancient times as a particular individual metal,
being termed asem by the Egyptians, and rfXe/crpos by the
Greeks (amber being distinguished as TO r)\eK.rpov). From
this also it may be concluded that at that time no method
was known of separating the metals.
The data concerning copper (termed %d\/c6<;, aes 1), which
has been known from very primitive times (being first found
in the neolithic stone age), frequently refer to its alloys with
other metals, especially to bronze ; the latter, as is well known,
was very early used for making weapons, ornaments and
utensils. Copper, which was universally employed in pre-
historic times, was found native in many places (e.g. in Egypt),
or was readily smelted from malachite or similar copper ores.
All the civilised nations, which have been named, were
acquainted with bronze before they had learnt to prepare its
other constituent, metallic tin, no mention of which is made
in old Egyptian records. With regard to the smelting pro-
cesses by which the " aes " of the Ancients was obtained,
nothing certain is known.
Iron, the extraction and working of which was not dis-
covered till after that of copper and bronze, but which, never-
theless, goes back to very ancient times also,2 was prepared
in smelting furnaces ; the old authors do not, however, give
any particulars as to the actual process.3 The ores used are
1 The Roman aes has the same stem as the Sanscrit word ayas, signify-
ing ore ; the latter designation cuprum for copper is an abbreviation of aes
cyprium (so called because of its occurrence in Cyprus).
2 According to Lepsius, iron has been in use in Egypt for more than
5000 years, having served primarily for the manufacture of hard instru-
ments, while utensils of all kinds were made from bronze.
3 Old Roman smelting furnaces with their appurtenances have recently
been excavated near Eisenberg in the Pfalz. The form of apparatus used by
the Egyptians for the smelting of iron can be arrived at approximately from
inscriptions, etc. ; it is worthy of note that bellows of the same shape as
those of Ancient Egypt are in use in the interior of Africa at the present da}\
14 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CH.
supposed to have been brown iron ore and magnetite ; that
meteoric iron was first employed is an improbable and un-
proven assumption. The tempering of iron was early learnt
in Ancient Egypt; even in the time of Pliny the un-
desirable property of impure iron, which we now term
brittleness, was known, and its capability of assuming the
peculiarity of the magnet stone when brought into contact
with the latter, was also observed.
Lead * was likewise known from very early times, having
been prepared and turned to good account, by the Greeks
and Romans more especially. Little, however, is known
with regard to the smelting processes for it, Pliny's records
on the subject being indistinct ; but the smelting was
probably carried out on a refining hearth. On the other
hand we have many details as to the use of lead for making
water pipes, writing tablets, coins, etc. Soldering with lead
or with an alloy of lead and tin was also well known. Since
cooking utensils were often made of lead, symptoms of lead
poisoning occurred frequently ; but notwithstanding this, the
metal was prized as a medecine.
Recent discoveries in Egyptian tombs have brought to
light the fact that tin also was prepared fairly pure in olden
times, and that it found numerous applications. Among the
Romans lead and tin were distinguished from one another as
plumbum nigrum and plumbum candidum.2 The alloy of
the two together, i.e. solder, played, as already mentioned, an
important part in technical work. Still older and of even
greater significance was the use of bronze,3 which one meets
with among the most ancient civilised nations.
1 Cf. K. B. Hofmann's Das Blei bei den Volkern des Alterthums (Berlin,
1885).
2 The word stannum, which now denotes tin, appears in Pliny's time
to have signified an alloy of tin and lead. Whether the Kaffo-irepos
of the Iliad stood for tin is likewise highly problematical. It is equally
uncertain from whence the Phoenicians obtained this metal (or an alloy of
it) ; whether from India, with which they had commercial relations, or
from Britain and Iberia. The similiarity between the Sanscrit word Jcastira
and the Greek word KO.O O(T epos has been used as an argument in favour of
the former assumption (cf. A. v. Humboldt, Kosmos, ii. § 409).
3 K. B. Hofmann considers that the name bronze, with regard to the
i METALLURGY OF THE OLD NATIONS 15
Zinc,1 as an individual metal, was certainly not known to
the Ancients, but its alloys with copper (^aX/eo?, ope^aX/eo<?)
found the widest application.
Brass, the first description of which is given by Aristotle
as the " metal of the Mosynoeci " (from which the German
word Messing, signifying brass, is undoubtedly derived), was
for long regarded as copper which had been coloured yellow
by fusing it with an earth (cadmia) ; 2 it was only recognised
as an alloy at a much later date. The change in colour
produced in copper by certain additions to it played — in the
transmutation of metals — an important part in the alchemistic
age.
The first records as to mercury are to be found in
Theophrastus (about 300 B.C.), who gives its preparation
from cinnabar by means of copper and vinegar, and terms it
"liquid silver." Dioscorides describes the production of
mercury, which he at first termed vSpdpyvpos, from cinnabar
and iron, i.e. by a process of simple elective affinity, without,
however, making the slightest attempt to explain the process.
For the carrying out of this operation, an exceedingly im-
perfect distilling apparatus was used. Pliny makes mention
both of the purification of the metal, by squeezing it through
leather, and also of its poisonous nature. It did not escape
the Ancients that other metals, gold in especial, were altered
by mercury (cf. p. 12); indeed Vitruvius gives a minute
recipe for the recovery of gold in worn-out sewn draperies
by means of it.
An account will be given later on of several metallic com-
pounds known in ancient times.
origin of which there has been much dispute, is probably derived from the
word ftpovit'fiffio}', meaning an alloy, a word possibly borrowed from the
Persian. The view, held even so early as in Pliny's time, that "bronze"
was derived from (aes) Brundusinum, has been proved untenable.
1 Cf . K. B. Hofmann's paper in the Zeitschriftfur Berg- und Huttenwesen,
vol. xli. Nos. 46—51.
2 Even so early as 300 B.C., " cadmia" was famous as a medicine. The
word likewise means " tutty " (oxide of zinc), or also rich zinc ore. Accord-
ing to K. B. Hofmann, it is not improbable that galmei (cadmia, calamine)
is derived from cadmia ; i.e. those three terms appear to be synonymous.
16 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CH.
Beginnings of Technical Chemistry among the Ancients.
The Manufacture of Glass. — The art of making
vessels from glass originated in China and Egypt, and had
for a long time its chief habitat in Thebes ; from there it
spread to the Phoenicians and other Eastern nations, the
Greeks first acquiring it — so far as actual proof goes — in the
fifth century B.C. Pliny is the first to give a distinct
account of the preparation of glass by fusing sand and soda
together.1
The artificial colouring of glass by metallic oxides,
especially oxide of copper, was very early discovered. Many
of the remains which have been found in Ancient Egypt
indicate that the manufacture of glass must at that time
have attained to a high degree of perfection, methods for
producing enamels and artificial gems being then known.
Pliny states that beryl, opal, sapphire, amethyst, etc., could be
imitated, but that at the same time these imitations were
distinguishable from the real stones through being softer and
lighter.
The first preparation of glass presupposes in any case
an acquaintance with soda or potash ; the former of these
was found as a natural product on the shores of certain
lakes, e.g. in Macedonia and Egypt, while carbonate of
potash was obtained from a very early period by lixiviating
the ashes of plants, and also, according to Dioscorides, by
igniting tartar. These two salts 2 were frequently mistaken
for one another on account of their similar action. They
were largely used for the preparation of soap, and also
directly for washing clothes, cleansing the skin and the teeth
(just as the ash of tobacco, which is rich in carbonate of
potash, is often employed as a tooth-powder at the present
1 The discovery of glass in Egypt was undoubtedly accidental, soda
having been added as a flux to sand containing gold for the purpose of
extracting the latter.
2 The Hebrew neter probably denotes soda, while the Latin nitrum is
employed by Pliny for both alkaline salts. The designation alkali came
originally from the Arabs.
i MANUFACTURE OF POTTERY AND SOAP 17
day), and also as ingredients of medicines. Lastly, the
ashes of plants and saltpetre were much prized as effective
manures.
To the art of pottery must be ascribed an age at least
as great as that of the preparation of the nobler metals and
of glass. Even the old Egyptians understood how to coat
their originally simple earthen vessels with coloured enamel.
At a later date the ceramic industry prospered among the
Etruscans, and also in many towns of Southern Italy and
Asia Minor. Porcelain, which was discovered and employed
by the Chinese, remained entirely unknown to the older
civilised European nations.
The Manufacture of Soap. — Of no slight interest is
the fact that the saponification of fats by means of alkalies,
with the object of preparing soap — that is to say, a com-
plicated process of organic chemistry — , was already practised
in ancient times. Pliny's records on the subject make it
probable that in Germany and Gaul soap was prepared from
animal fat and the aqueous extract of ashes, the latter
being strengthened (rendered caustic) by the addition of
lime. Further, there was a distinction drawn between soft
and hard soaps, according as potash or soda (the latter being
obtained from the ashes of shore plants in Gaul) was used
in the preparation.1
Dyeing likewise belongs to the arts which the Egyptians,
Lydians, Phoenicians and Jews greatly developed. They
knew how to fix certain dyes on cloth by means of mordants,
alum 2 playing an important part here ; indeed the dyeing of
purple had attained to a high state of perfection among the
Phoenicians. Pliny mentions the application both of madder
dye and of litmus (the gatulian purple). Indigo blue seems
to have been more used at that time for painting than for
1 From K. B. Hofmann's researches it appears to be doubtful whether
the sapo of the Romans meant soap, and not rather a depilatory.
2 Under ffTvirrripia or alumen of the Ancients must be understood sub-
stances of astringent properties generally, although alum itself is what is
usually meant ; being prepared from alum shale, it contained green vitriol
as an impurity.
C
18 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CHAP,
dyeing, but with this exception mineral substances were
employed as paints. The principal of these in Pliny's time
were white lead, cinnabar, vermilion, smalt,1 verdigris, red
oxide of iron and soot. This last, mixed with gum, also
served as ink. Numerous recent researches 2 have proved
that sulphide of lead (galena) formed the basis of the much-
used old Egyptian cosmetic mesdem, — and not native sulphide
of antimony, as was at one time supposed. Mesdem was
also a highly prized medicine. The use of preparations of
antimony belongs to a later period. — The sulphides of
arsenic, realgar and orpiment, served both as pigments and as
medicines, although their poisonous action was known. In
short, the Ancients had access to a considerable number
of colouring chemical compounds, some of these being the
earliest chemical preparations to be manufactured on a large
scale.
As has been already indicated, the use of such arti-
ficially prepared products in medicine also extends to a
period very far back, even although, in referring to this,
one can only speak of the first beginnings of a pharma-
ceutical chemistry. But a connection between the chemical
art and pharmacy established itself very early indeed, e.g.
among the Egyptians, who were doubtless the first to employ
actual chemical preparations for medicinal purposes. Thus
verdigris, white lead, litharge, alum, soda and saltpetre
served for the making of salves and other medicaments,
while the preparation of lead plaister from litharge and oil
was much practised in the time of Dioscorides. Iron rust
was a very old medicine, its use being ascribed to ^Escula-
pius, while sulphur and copper vitriol containing iron (chal-
canthum) were valuable ingredients of the medical treasury
1 Davy found cobalt in certain antique glasses, and assumed from this
that smalt had been used in their manufacture. Accbrding to Fouque (Compt.
Rend., vol. cviii. p. 325) Egyptian glass contained only oxide of copper as the
colouring material ; but vitrifiable pigment containing cobalt has been again
found recently in small Egyptian statuary.
2 Collected and critically examined by K. B. Hofmann in his paper : —
Ueber Mesdem (Mittheilungen des Vereins der Arzte in Steiermark, 1894,
Nos. 1 and 2).
i ORGANIC SUBSTANCES KNOWN IN ANCIENT TIMES 19
before our era ; but the important preparations of antimony
and mercury can be proved to have first come into notice in
the alchemistic period.
Most of the officinal compounds just referred to were
also used for other purposes, as has already been mentioned
\ in a few cases. The combustion-product of sulphur, for
\instance, was employed for fumigation (vide Homer), for the
purification of clothes, the conservation of wine, and for
' destroying impure colours (Pliny), while copper vitriol and
alum were used in dyeing operations. — In closing this short
account of the knowledge possessed by the Ancients with
regard to chemical compounds, the following substances may
be mentioned, substances whose practical application dates
from a very early period. In ancient times lime was burnt,
and after being slaked, was used for preparing mortar, and
also, as already stated, for causticising soda (cf. p. 17). Of
Ithe acids, acetic acid 1 in the form of crude wine vinegar was
bhe earliest known, its presence being assumed in all acid
plant juices. The mineral acids, which are of such import-
ance in technical chemistry, were only discovered in the
succeeding epoch.
Other organic compounds known at the beginning of our
era, and doubtless even before then, were sugar (from the
sugar-cane), starch2 (from wheat), many fatty oils (from
seeds and fruits, the oil being extracted either by pressing
or by boiling with water), petroleum, and oil of turpentine,
which last was obtained by the distillation of pine resin in
very imperfect apparatus.3 Of the fatty oils, olive, almond
and castor oils, etc., were known and used for a variety of
purposes, the first-named — e.g. — for extracting perfumes from
1 The Ancients had the most extravagant ideas with regard to the
solvent power of vinegar upon mineral substances, as may be gathered from
the concordant statemants of Livy and Plutarch that Hannibal, in his pass-
age across the Alps, cleared the way of rocks by means of it. The story ••
which Pliny tells of Cleopatra may also be recalled here, — how she, in ful-
filment of her wager to consume a million sesterces at one meal, dissolved
costly pearls in vinegar and drank the solution.
2 &/j.v\ov, so called from its being prepared without millstones, and the
production of which is described by Dioscorides.
3 Prof. K. B. Hofmann kindly tells me that the earliest account of a
destillatio per decensum is to be found in Ae'tius (Aldine Ed., fol. 10).
c 2
20 FROM EARLIEST TIMES TO THE BIRTH OF ALCHEMY CHAP, i
flowers, leaves, etc. Ethereal oils were also known and
employed in large number. — The animal fats played an
important part in medicine, and Pliny's mention of sheeps-
wool grease, among other things, is noteworthy here, seeing
that it has recently been brought into use again in the form
of lanoline. — Pliny does not seem to have been acquainted
with cane sugar ; but one frequently comes across passages
in his writings referring to the occurrence and remarkable
actions of vegetable poisons (alkaloids).
Such compounds as spirits of wine, carbonic acid, etc.,
which are formed in many processes of fermentation, e.g. in
the making of wine, beer and bread, remained unknown to
the Ancients. It is true that they noticed in these cases
and also in others — natural emanations of gas, for instance —
the presence of a kind of air prejudicial to breathing and
even under certain circumstances fatal to life, but it did not
occur to them to recognise in this a gas different from
atmospheric air.
This lack of the gift of observation, this disinclination to
go to the root of any phenomenon, in fact, a certain in-
difference with regard to natural events, are characteristics
of the attitude of the Ancients towards nature. Instead of
experimenting with natural products, they infinitely preferred
to call speculation to their aid, so that the most superficial
observations gave rise to opinions which, when uttered by
high authorities, attained to the dignity of dogmas. How
otherwise than from an extreme lack of the desire of
observation can one explain Aristotle's assertion that a vessel
filled with ashes will contain as much water as one which is
empty ? A further instance of the credulity of that time is
given in the conviction expressed by Pliny, and universally
held, that air can be transformed into water, and vice versa,
that earth is produced from water, and that rock-crystal also
proceeds from the latter. The assumption that water can
be transformed into earth has often come up again at later
periods, having exercised the minds of people even in com-
paratively recent times ; as it subsequently assumed the
form of an important question of dispute, it will be referred
to in detail later on.
CHAPTER II
THE AGE OF ALCHEMY
IN the introduction to this book Egypt is spoken of as the
mother-land of Alchemy. The University of Alexandria was
especially instrumental in the propagation of the latter during
the first centuries of our era ; it was the carrier and inter-
mediary for the alchemistic doctrines, more particularly at
the time of the fall of the Western Roman Empire.
The attempts to convert the base metals into the noble
ones had their origin in superficial observations, which ap-
peared to give a strong support to the belief in this trans-
mutation. Among such accidental observations was that of
the deposition of copper upon iron utensils left in copper
mines from the waters which accumulated there. What
more natural than to conclude that a transmutation of iron
into copper had occurred ? For the production of gold or
silver from copper, the transformation of the latter into
yellow or white alloys by means of earthy substances such
as calamine or arsenic appeared to give warrant. Finally,
the fact that a residue of gold or silver remained behind
when an alloy with lead or an amalgam with mercury was
strongly heated, indicated the generation of those noble metals.
To these considerations of a practical nature, which
strengthened the conviction as to the transmutation of
metals, but which inferred a gross self-deception on the
part of the observer himself — to say nothing of their being
turned to good account by crafty knaves — there came to be
allied, in this epoch for the first time, the tendency to group
together chemical facts from common points of view.
22 THE AGE OF ALCHEMY CHAP.
It was precisely in the mode in which it was attempted
to explain the composition of the metals that there lay a
powerful and ever-active charm, leading to the belief in the
ennobling of the baser metals and to continually repeated
efforts to achieve this. The first beginnings in an experi-
mental direction, which we meet with early in the alchemistic
period, although very incomplete, indicate nevertheless a
distinct step in advance as compared with the deductive
method which had hitherto reigned supreme, and whose fruits
consisted, for the most part, in the setting up of mystic cos-
mogonies. The few observations which were made remained,
however, isolated — that is, were not grouped together in a
connected manner.
That the attempts to attain to a knowledge of the
processes of nature by the inductive method were but slight
at best in the alchemistic period, is explained by the
supremacy of the Aristotelian doctrine, which, amalgamated
with the Neo-Platonic philosophy, trammelled the minds of
men throughout almost the whole of the Middle Ages. Even
the Christian theology had to compromise with this system,
the product of the joint work being scholasticism, which
imprinted its stamp upon all the mental efforts of that
time and prevented their free development. The relation of
the alchemistic tendencies to the Aristotelian philosophy has
been already indicated (p. 7).
The limitation of this epoch between the first appearance
of alchemistic conceptions (in the fourth century) and the
bold attempt of Paracelsus to call in chemistry to the aid
of medicine (in the beginning of the sixteenth centurv) is
thus a natural one, since, during the whole of this time, one
and the same keynote runs through all the questions bearing
upon chemistry, viz. the idea of ennobling the metals.
People were so convinced of the practicability of this for many
centuries, that almost every one who devoted himself to
chemistry, and many others besides, strove hopefully towards
this long-desired goal. The early mixing up of astrological
and cabalistic nonsense with these alchemistic endeavours
marks very distinctly the degeneration of the latter.
ii ORIGIN AND FIRST SIGNS OF ALCHEMY 23
Alchemy by no means ceased to exist on the appearance
of the new iatro-chemical doctrines, but gradually receded
as chemistry became more of a science. True, its seductive
problems are often seen to throw a weird lightning flash on
the chemists' camp, and to exercise upon even the most
eminent of them an undoubted influence ; but upon the main
lines which chemistry has followed ever since the time of Boyle,
the phantasies of alchemy have had no appreciable effect.
Notwithstanding, however, that this influence was but slight,
a short account of the position of alchemy during the last
four centuries cannot properly be omitted, and will therefore
be added as an appendix to this section of the book.
GENERAL HISTORY OF ALCHEMY.1
Origin'2' and First Signs of Alchemistic Efforts.
The sources from which the belief in the practicability of
the transmutation of metals was nourished, and which in the
course of centuries gradually expanded into a broad stream
of the most mischievous errors, have their origin in the gray
mists of antiquity. No actual proof of these must be
looked for : we depend, with regard to them, upon mythical
and mystical traditions. The first historical sources, too,
are small in number and very obscure. But we find among
various nations distinct signs of alchemy having been pursued
as a secret science and having been held in honour.
When one recalls to mind that Ancient Egypt was a
1 Cf. Kopp, Gesch. d. Chemie, vol. i. p. 40, et seq. ; also his work, Die
Alchemie in dlterer und neuerer Zeit (Heidelberg, 1886).
2 Cf. particularly M. Berthelot's Les Origines de rAlchimie (Paris, 1885)
and his Introduction d I'jZtude de*la Chimie des Anciens et du Moyen-dge
(Paris, 1889) ; also H. W. Schaefer's admirable treatise : — Die Alchemie ;
ihr aegyptisch-griechischer Ursprung, efcc. (Fleusburg, 1887 ; School-
calendar). M. Berthelot has indeed rendered signal service by his publica-
tion and critical revision of old alchemistic works, such as the Leyden
papyrus, and Greek and Arabic MSS. Quite recently, in conjunction
with certain philologists, he has given to the world the Collection des Anciens
Alchimistes Grecs and La Chimie en Moyen-dge.
24 THE AGE OF ALCHEMY CHAP.
centre of the higher culture, and, especially, that it was a
country where the chemical art was practised, one feels no
surprise that the earliest reliable records of alchemy are to
be found there. / Egyptian sources, partly such as have been
preserved to us by the Leyden papyrus (about 300 A.D.), and
partly the writings of the Alexandrians from the third to the
seventh century A.D., constitute the most valuable aids at our
disposal for a historical proof of the origin of alchemy. The
influence of the doctrines and practical recipes contained in
these works upon the alchemy of the entire Middle Ages is
easily demonstrable.
The tradition according to which, among other know-
ledge, the art of ennobling metals had been brought from
heaven to earth by demons, was universally diffused in the
first centuries of our era ; Zosimos of Panopolis states that
the mystical book from which this art was to be learned was
termed, xfifiev and the art itself ^fieia. This myth doubt-
less sprang from one exactly similar which is to be found in
the apocryphal book of Enoch ; indeed indications of it
are to be met with even in Genesis. The later alchemists
were inclined to refer the origin of alchemy to the time
before the flood, thinking that a special sanctity would accrue
to their art from this great age. Moreover, they wrote down
various biblical characters as alchemists, on the authority
of certain passages in Holy Writ, for instance, Moses and his
sister Miriam, and the Evangelist John. When legends
such as these found credence in the Middle Ages, it is hardly
surprising that the records as to the origin of this art,
which remain to us from ancient times, should have upheld
their authority over a very long period.
The first personality with which the origin of alchemy
is associated is that of Hermes Trismegistos,1 " the three times
great," who was said to have been the author of books upon
the holy art ; he was, moreover, generally reverenced as the
discoverer of all the arts and sciences. The then popular
expressions " hermetic," " hermetic writings " and " hermetic
1 This designation is probably first found in Tertullian (end of the second
century of our era). Of. Schaefer, p. 4, &c.
ii ALCHEMY AMONG THE EGYPTIANS 25
art " l recalled this undoubtedly mythical personage even so
recently as in the present century. In Romish Egypt pillars
were erected in honour of this Hermes, upon which alchemistic
inscriptions were cut in hieroglyphics.
Who then was this Hermes ? One has to seek in him, as
ancient traditions indicate almost certainly, the personified
idea of strength, i.e. the old Egyptian godhead Thot (or
Theuth), which, when endowed with the serpent-staff as the
symbol of wisdom, was compared by the Greeks with their
Hermes, the latter designation being thus transferred to the
Egyptian god.2 Alchemy, as a holy and divine art, whose
special task consisted in tHe prej^afioli~ofTHe"metals, was
kept secret and fostered by the priesthood, the sons of kings
alone being permitted to penetrate its mysteries. The esti-
mation in which it was held rose in exact proportion with
the belief that Egypt owed to alchemy its riches.
When and in what way the influence of other nations
made itself felt upon the alchemy of the Egyptians, it is
difficult to determine. The Babylonish astrologers, without
doubt, undertook the fusion of astrology and magic; in
particular, the mutual relations between the sun and planets
and the metals, which were taken for granted for so many
centuries, were of old Babylonish origin. According to the
account of the Neo-Platonist Olympiodor (in the fifth century
A.D.), gold corresponds to the sun, silver to the moon, copper
to Venus, iron to Mars, tin to Mercury, and lead to Saturn.3
Certain passages in the works of Dioscorides, Pliny, and
the Gnostics enable us to conclude that the transmutation
of copper into silver and gold was regarded as an as-
certained fact during the first centuries of our era.4 The
1 The designation "spagiric art" (from (nrdw, to separate, and ayfipw,
to unite) occurs for the first time in the sixteenth century.
2 This identity is confirmed by the fact that, in the inscriptions on the
temple of Dakke on the Nile dedicated to Thot, the three names Thot,
Hermes and Mercurius occur, the first in hieroglyphics, the second in
Greek, and the third in Latin (cf. Schaefer, p. 7).
3 Even in Galen are to be found statements with regard to the influence '
of the planets upon the metals.
4 The Chinese also busied themselves with alchemy at that time, the
26 THE AGE OF ALCHEMY CHAP.
" duplication of the metals," which is to be found in the
writings of first-century authors, and which also plays a part
in the Leyden papyrus, likewise refers to the transmutation
of metals. The designation of this art as " Chemia " probably
appears for the first time in an astrological treatise of Julius
Firmicus (in the fourth century).
Berthelot has made a careful study of the Leyden papyrus
(found in Thebes in the third century A.D.), and has com-
pared it with later alchemistic writings. This has led him
to the conclusion that an intimate connection existed between
the industrial production of the noble metals, the dyeing of
fabrics, and the colouration of glass (whence the frequent
expressions : — Tingiren der Metalle ; Tincturen, etc.). The
alleged processes of transmutation, which were currently
believed for hundreds of years, consisted in artifices for de-
basing the noble metals, but at the same time imitating
their appearance as nearly as possible in less costly alloys.
It is quite likely that, as time went on, the idea took
possession of many kinds that the gold and silver were newly
created by some supernatural aid. It would thus seem as if
alchemy originated in the fraudulent practices of gold- workers.
The records of the study of alchemy go on increasing from
the 4th century, much information regarding it being found
in the writings of the Alexandrian savants of that time,
especially in those of Zosimos, Synesios and Olympiodor. In
addition to these, various pseudo-authors, especially pseudo-
Democritus, are cited here as witnesses to the spread of
alchemy ; the philological-historical critic is not yet, however,
in a position to fix the dates at which these works were written.
In the Middle Ages people did not hesitate to accept the
writings of the false Democritus, and also those of a pseudo-
Aristotle, as originating from the ancient philosophers
Democritus and Aristotle themselves. The later alchemists
also fathered counterfeit writings upon Thales, Heraclitus
and Plato, in order to make use of the great authority of
those names for their own ends.
transformation of tin into silver, and of the latter into gold, being held to
have been actually accomplished.
ii ALCHEMY AMONG THE EGYPTIANS 27
Zosimos of Panopolis, a voluminous author of the fifth
century, who was looked upon as one of the greatest authori-
ties among alchemists both of that date and of later times,
is said to have written twenty- eight books treating of alchemy,
of which, however, only small fragments remain. His mysti-
cal recipes are quite unintelligible, and yet he distinctly
speaks of the fixation of mercury, of a tincture l which changes
silver into gold, and also of a divine water (panacea). Refer-
ence is frequently made to the work of the pseudo-Democri-
tus, (frvarifca KOI fjuvo-Tifca. The graphic and mysterious
language of Zosimos appears to have exercised a permanent
influence upon the works of the later Alexandrians, and also,
subsequently, upon those of the alchemists of the Middle
Ages.
The end of the fourth century and the beginning of the
fifth constitute, without doubt, the period in which the study
of alchemy reached its zenith among the Alexandrians;
but the works of Synesius upon alchemy and magic, and
those of Olympiodor, who bore the surname of " TTO^T???,"
operator, do not yield much certain information with regard
to definite operations or to the knowledge of chemical facts.
How many works which would have been valuable for the
history of chemistry were lost through the destruction of the
Serapeum, which marked the completion of the overthrow of
Hellenic culture in Egypt, cannot at this distance of time
be estimated. That all acquaintance with chemical opera-
tions, and chemical knowledge and skill generally, were not
thereby quite exterminated was due to the relations which
were before that developed between the Alexandrians and
the Byzantine savants ; for, from the sixth century on, applied
chemistry, which may also be said to include alchemy, found
-a foothold at Byzantium. Even in Egypt itself the know-
ledge of chemistry was not completely extirpated by that
catastrophe, but continued to exist by fostering certain
branches of industry, which, without it, could never have
been developed. Lastly, the conviction that metals could
1 The term " mercurius philosophorum," which is often found in later
writings, was first used by Synesius.
28 THE AGE OF ALCHEMY CHAP
be transmuted had fixed its roots too deeply to allow of this
art, by which endless riches were to be attained, dying a
natural death.
The Alchemy of the Arabians.
The germs of chemical knowledge, which had lain hidden
in the brains of a few philosophers, attained to a marvellous
growth among the Arabians, who overran and conquered
Egypt in the seventh century ; it might have appeared much
more likely that they would crush the arts and sciences
rather than be the instruments of their resurrection. It was
certainly curious that this people, originally strangers to
science, should assume the care of it and cause it to flourish
in an undreamt-of degree, at a time when culture remained
at its lowest ebb in most European countries, and everything
had to give way to the pressure of the conditions produced
by the migration of the nations.1
The first appearance of the Arabians in Egypt, where they
destroyed much priceless literary treasure by fire, did not
seem to herald any such change of opinion. They very soon
learnt, however, to assimilate the elements of the education
of the conquered peoples,2 so that we find (especially after
the conquest of Spain, in the beginning of the eighth
century) many cities of learning springing up ; to these in
the following centuries the European nations — especially
France, Italy and Germany — sent crowds of earnest students,
1 Alex, von Humboldt gives expression to this point in the following
words : " The Arabians, an original Semitic stock, partially drove away the
barbarism which had overwhelmed Europe for two centuries, convulsed as
it had been by revolutions. They turned to the everlasting springs of
Greek philosophy, and thereby assisted not only in preserving the culture
of science, but in widening it and opening out new paths to the investigators
of nature."
2 Reference may just be made here to the important part played by the
Nestorians in engrafting the scientific spirit upon the Arabians, and in
enriching them with practical chemical knowledge. The latest researches
of Berthelot and others leave no doubt that the Arabians derived from the
Syrians much— if not indeed the greater part — of their knowledge of
chemistry.
ii ALCHEMY AMONG THE ARABIANS 29
who applied themselves, for the most part, to the study of
medicine, mathematics and optics. From the Arabian uni-
versities of Cordova and other Spanish cities, where alchemy
was also ardently studied, it made its way to the other
western nations, among which it attained to its full develop-
ment in the thirteenth century.
A renown quite unexampled, and an authority which con-
tinued all through the Middle Ages, were attained by the
physician and alchemist Dschafar, afterwards known to
western nations by the name of Geber. About his life (he
is supposed to have lived in the ninth and tenth centuries)
nothing is known. It is possible, too, that Geber himself
has been sometimes confused with his pupil Dschabir of
Tharsis.
There can indeed be no dispute that with the name Geber
was propagated the memory of a personality, with which the
chemical knowledge of the time was bound up. But Berthe-
lot's recent researches l have proved that the Latin writings
hitherto ascribed to Geber cannot have come from him. The
oldest of these — the celebrated Summa Perfectionis Magisterii
— was not written before the middle of the fourteenth cen-
tury ; and the De Investigations Veritatis and De Investiga-
tione Perfectionis Metallorum, formerly regarded as genuine,
belong to an even later date. In fact, the whole of what
were supposed to be Geber's writings are apocryphal.
The Arabic MSS. of the real Geber, which Berthelot's
investigations have now brought to light, prove that he did
not really profess the knowledge and the opinions with
which he has been credited. On the contrary, we find Geber
adhering closely to the Grseco-Alexandrian alchemists, and
bringing forward many mystical views, e.g., the belief in
the influence of the planets upon the metals. There is no
distinct indication in his writings of the theory of the metals
hitherto ascribed to him (see below). Geber can therefore
no longer be regarded as the author of the Latin treatises
with which, up to now, his name has been associated. These
1 See p. 23, Note 2. Of. also two papers by Berthelot in the Revue des
deux Mondes, Sept. 15th and Oct. 1st, 1893.
30 THE AGE OF ALCHEMY CHAP,
writings contain, in fact, the collected knowledge of the four
or five centuries after his time.
The disciples of Geber, famous Arabian physicians like
Maslema, Rhazes, Avicenna, Avenzoar, Abukases and Averr-
hoes, may possibly have exercised a retarding influence upon
the development of medical science and of pharmacy. And
it is extremely doubtful whether they advanced chemistry in
any material degree. It is worthy of note that Rhazes dis-
tinctly assumes the transmutation of metals, while Avicenna
disputes it.
Alchemy among the Christian Nations of the West during
the Middle Ages.
The doctrines of the Egypto-Greek and Arabian alchemists
gradually penetrated into France, Italy and Germany, certain
Byzantine savants — Michael Psellus among them — also con-
tributing to the spread of alchemistic ideas. Eastern in-
fluence is recognised distinctly for the first time in the
earliest appearance — of which there is clear proof — of an
alchemist in Germany at the court of Adalbert von Bremen
(about 1063), as recorded by Adam von Bremen ; a baptised
Jew named Paul gave out that he had learnt in Greece the
art of transmuting copper into gold, and he appears to have
imposed upon the above-named ecclesiastical prince. The
next certain records of alchemistic endeavours in Germany
date from the thirteenth century, at which period alchemy
was studied by men famous for their learning, and was conse-
quently developed in a high degree.
The transformation of the base metals into the noble by
means of the philosopher's stone formed at that date the
cardinal point towards which all chemical knowledge was
directed. Vinzenz of Beauvais1 (in the first half of the
thirteenth century) and, after him, men like Albertus
Magnus, Roger Bacon, Arnaldus Villanovanus and Ray-
mund Lully, whose chief works belong to the same century.
] Vincentius Bellovacensis.
ii ALCHEMY DURING THE MIDDLE AGES 31
regarded the transmutation of metals as an incontrovertible
fact. These maintained that the philosopher's stone did
exist, and was endowed with the most marvellous powers
(see below), their dogmas being based upon those of the
Aristotelians and of the Egypto-Greek alchemists. In ad-
dition to these, the most distinguished representatives of
chemistry, all of whom belonged to the priestly class, must
be mentioned the famous Thomas Aquinas ; the latter did not
indeed materially advance the knowledge of chemistry, but
he stood up at various times for the truth of the doctrine
of transmutation of metals.
The influence of the four men above-mentioned upon
the history of chemistry renders biographical notices of
them desirable; their views upon the alchemistic problem,
and also their very considerable practical knowledge, will be
treated of under special sections. Their writings have to be
criticised with some caution, since many of the alchemistic
treatises of later times were given out to the world under
their names.
Albertus Magnus, or, more properly, Albert von Bollstadt.
born at Lauingen on the Danube in 1193, taught philo-
sophy, grammar, alchemy, etc., publicly as a Dominican in
Hildesheim, Regensburg, Cologne and Paris, and became
Bishop of Regensburg in 1260. He retired, however, to
the cloister five years later, and died in the Dominican
convent of Cologne after having devoted himself for fifteen
years to scientific work. Albertus Magnus was held, both
by his contemporaries and still more during the later Middle
Ages, as a man of the greatest erudition and widest acquire-
ments, the degrees of which are given by Tritheim, an
author of the fifteenth century, in the following words :
Magnus in magia natural*, major in philosophia, maximus
in theologia. His noble character also earned for him the
highest respect. Of his numerous memoirs, the two — De
Alchymia and De Rebus Metallicis et Mineralibus are of
the most value for adjudging his position with regard to
alchemy.
Roger Bacon was born in Somersetshire in 1214, and
32 THE AGE OF ALCHEMY CHAP.
studied science, as well as theology, both at Oxford and
Paris. The veneration felt by posterity for his marvellous
and many-sided knowledge is shown by the title which it
conferred upon him of Doctor Mirabilis. Since he did not
hesitate to oppose in many points the orthodox beliefs of his
day, he was subjected to bitter persecution and penalties.
His death probably occurred in the year 1294.
His firm belief in the power of the philosopher's stone,
not only to transform a million times its own weight of
base metal into gold, but also, to prolong life, seems to
us incomprehensible when contrasted with the otherwise
enlightened views which he held and propagated. This
undisguised recognition of miracle-working, and this bias
towards the marvellous, are directly opposed by the fact
that Roger Bacon taught the working out of carefully
devised experiments as a special kind of research, by which
new data for the knowledge of nature should be acquired.
He is to be regarded as the intellectual originator of
experimental research, if the departure in this direction is
to be coupled with any one name — a direction which,
followed more and more as time went on, gave to the
science its own particular stamp, and ensured its steady
development. The most important works of Roger Bacon
are the following: — Opus Majus; Speculum Alchemice ; and
Breve Breviarium de Dono Dei. He did not apparently do
much towards the spread and development of practical
chemical knowledge.
In the life and work of the two notable alchemists,
Arnaldus Villanovanus and Raymundus Lullus, the alchem-
istic tendencies of their century are clearly reflected, although
much uncertainty exists as to many points, especially in the
life of the latter, and also with regard to the works ascribed
to Lully. Both of them at all events were held in high
esteem, not only during their lives, but also- in the centuries
following. Arnaldus Villanovanus, whose birthplace is un-
certain, practised as a physician in Barcelona in the second
half of the thirteenth century. His opinions, however,
causing great offence to the priests, he was obliged to
ii ARNALDUS VILLANOVANUS AND RAYMUNDUS LULLUS 33
flee from there, and after vainly endeavouring to escape
persecution in Paris and in various towns of Italy, he at
last found an asylum in Sicily with King Frederick II.
Summoned to Avignon by Pope Clement V., then seriously
ill, he lost his life by shipwreck on the way thither, about
the year 1313. He had special opinions of his own as to
the nature and efficacy of the philosopher's stone, and also
with regard to the noble metals obtained through its means.
Among his writings may be mentioned : Rosarius Philosoph-
orum ; DC Vinis ; and De Venenis.
A similarly restless life was foreordained for Raymund
Lully, a life which comprised in itself the greatest contradic-
tions and eccentricities. Shortly after his death the object of
a traditional glorification, Lully possessed among alchemists
the fame of having attained to the highest which it was in
the power of their art to achieve. The historical critic has
a difficult task in dealing with him ; for while, on the one
hand, many of the writings ascribed to him are obviously
counterfeit, there are, on the other, no sufficient data for
deciding as to which of the remainder are really genuine.
Thus there is very great uncertainty whether the alchemist
Raymund Lully is identical with the famous grammarian and
dialectician of the same name, who was called by his admirers
Doctor Ulumindtissimus ; for this view, which has been held
by many, is strongly opposed by the fact that criticisms of
alchemy are to be found in many of the works of the latter.
Most of the records which we possess of the life of Ray-
mund Lully agree in stating that he was descended from a
noble Spanish family, and was born in the year 1235.
After leading a dissipated life at the court of Aragon, he
abjured the pleasures of the world in his thirtieth year and
devoted himself to science. It was probably Bacon and
Villanovanus who initiated him into the secrets of alchemy.
When somewhat aged, he gave himself up to the conversion
of the heathen, undertaking several journeys to Africa for
this purpose ; his reception there, however, was more than
once of the worst, and he was at last stoned to death in
the year 1315. Tradition has it that he lived for several
D
34 THE AGE OF ALCHEMY CHAP.
years after that date in the unresting study of alchemy,
but there can be no doubt as to the untenability of this
report.
His alchemistic doctrines were very obscure; and still
more incomprehensible and hidden in deep mystic darkness
are his recipes for the ennobling of the metals. Certainly
none of the alchemists who preceded him have ascribed to
the philosopher's stone such powers as he did ; for he was
able to cry out presumptuously : " If the sea were of
mercury, I would change it into gold."1 And not only
gold, but also all precious stones, and that highest good —
health, — together with long life, were to be obtained through
its means. Of the writings which are attributed to him,
the Testamentum, Codicillus sen Vademecum, and Experimenta
are regarded as genuine.
The earliest of the Latin writings formerly ascribed to
Geber (e.g., the Summa, mentioned on p. 29) may possibly
have come into circulation soon after Lully's death. It is
worthy of note, and also important for fixing with more or
less accuracy the date at which they lived, that neither
Albertus Magnus nor Raymund Lully refer to these writ-
ings, which grew in repute from the close of the fourteenth
century onwards. The information which one finds in the
works of the pseudo-Geber is by no means inconsiderable.
Great progress is apparent in the recipes given for the
making of preparations ; in the use of apparatus such as
the water-bath, the ash-bath, and improved furnaces ; and in
the description of chemical operations like sublimation,
filtration, crystallisation, distillation, &c., &c. All this
leaves no doubt on the mind as to the high standard of
practical chemical knowledge which the pseudo-Geber
possessed. The important question of the constitution of
•the metals out of mercury and sulphur will be discussed
later on.
The history of alchemy in the fourteenth and first half
of the fifteenth centuries contains no single name which
will compare in eminence with those of the above-mentioned
1 Mare tingerem, si mercurius esset.
ii ALCHEMY IN THE UTH AND 15TH CENTURIES 35
philosophers, as the alchemists themselves preferred to be
called.
This must not be taken as meaning that the supposed
art of making gold had died out ; on the contrary, it bore
its strangest fruit during that period. If it be desired to
connect specific names with the study of alchemy at that
time, then the Frenchman Nicolas Flamel, Isaac Hollandus
the elder and the younger, Count Bernardo da Trevigo, and
Sir George Ripley may be mentioned as among those who
were supposed to be in possession of the wonder-working
philosopher's stone. These men did nothing, however, to
materially advance the knowledge of chemistry.
Alchemy was at this time fostered and protected at
many of the European courts, for nothing appeared to be
more simple than to recuperate embarrassed finances by
means of artificial gold. Many documents in the history
of that century bear record to the frequent disappoint-
ments which were certain to come about sooner or later, —
decrees against the practice of alchemy, threatenings of
those who contravened these with the severest punishments,
and accounts of discoveries of the most bare-faced imposi-
tions. Alchemy found especial protection at the court of
Henry VI. of England, in spite of the fact that the kings
preceding him had had to pay heavily for their leaning
towards the hermetic art, and that a stringent law against
it had been promulgated by Henry IV. The consequence of
the favour shown to it by these monarchs was the production
of large quantities of counterfeit gold which, in the form of
coinage, inundated neighbouring countries. Charles VII. of
France, who was then at war with England, was seduced by
an alchemist, Le Cor, into a similar experiment, and thereby
materially increased the debt of his country ; to the alche-
mistic gold which he set in circulation were added the
English " Rose nobles." Counterfeit coining, carried out on
such a large scale, was hardly calculated to raise the reputa-
tion in which alchemy was held.
Chemistry, not being enriched during that time by any
facts of importance, likewise suffered from this depreciation ;
D 2
36 THE AGE OF ALCHEMY CHAP.
it first received new life from the work of BasiLYalentine,
whose acquirements in practical chemistry even now excite
our wonder. This remarkable man was the real precursor
of the iatro-chemical period, even although he was unable
to free himself from the fetters of the alchemistic faith.
Of his life practically nothing is known ; from his writings
we learn his name and the time, approximately, in which he
lived, viz. the second half of the fifteenth century, and
also that he was a Benedictine monk of Southern Germany.
The most important of his works were published in the
beginning of the seventeenth century by a city chamberlain
Tolde in Frankenhausen, Thuringia ; whether foreign matter
has become mixed up with them cannot now be deter-
mined. So much is certain, that Basil Valentine was re-
garded as an oracle by alchemists so early as the end of
the fifteenth and beginning of the sixteenth centuries, and
was held in higher honour than Geber, higher even than
Raymund Lully, besides being admired by many who had
nothing to do with alchemy. His works were spread
abroad by means of copies, and excited the interest of
the Emperor Maximilian I. to such a degree that he
caused a searching inquiry to be made in the year 1515 as to
which Benedictine convent the famous author had dwelt in ;
but unfortunately his efforts in this direction were without
result, as were also all later ones.
An account will be given further on both of his theoretical
views and of his wide acquaintance with practical chemistry.
Among the writings which are presumably his, and which
are at the same time of the most importance, are the follow-
ing : — Triumphwagen des Antimonii (" Triumphal Car of
Antimony ") ; Von dem grossen Stein der Uralten Weisen (" On
the Great Stone of the Ancient Philosophers ") ; OJfenbarung
der verborgenen Handgriffe ("Revelation of the Hidden Key") ;
Letztes Testament (" Last Testament ") ; Schlussreden (" Con-
cluding Words ").
In the first-mentioned work we possess what for that
time was a marvellous description of an element -and its
compounds, the knowledge of these being due mainly to
ii ALCHEMISTIC THEORIES AND PROBLEMS 37
Basil Valentine himself. The language which he employs
is frequently obscured by mystical pictures and alchemistic
ideas; but, while he thus appears as a visionary on the
one hand, he excites on the other our highest admiration
from the fulness of his temperate and conscientious obser-
vations, as well as from the rational views he takes of
subjects which were then, for the most part, judged
erroneously. The rich experiences in practical chemistry
which he made his own cause him to stand out as the
most distinguished chemist of the whole alchemistic period.
His boldness, too, in proposing the use of chemical prepara-
tions for medicinal purposes led the way in a direction
which soon after his time became the prevailing one, viz.
the iatro-chemical, which dominated the succeeding age.
Notwithstanding all this, Basil Valentine was an out-and-out
alchemist, holding, as such, the most exaggerated ideas as to
the power of the philosopher's stone ; just as the tendency
towards alchemy and the firm belief in the possibility
of transmuting metals and of prolonging life continued
engrained in many of the iatro-chemists.
SPECIAL HISTORY OF ALCHEMY.
Theories and Problems of the Alchemistic Period.
The alchemistic ideas, with the transmutation of metals as
their leading principle, have been proved (as already men-
tioned) to have originated and to have been first systemati-
cally fostered in Egypt. The first attempt to explain this
assumed transmutation, by a theoretical conception of the
nature of metals, was made very early. From a similar
endeavour, i.e. from regarding transmutation — then looked
upon as an incontrovertible fact — as a consequence of the
constitution of the metals, there sprang the doctrine con-
tained in the works ascribed to Geber, which in its essentials
predominated during the alchemistic period. It was thus
always the metals which gave rise to the early chemical
theories.
38 THE AGE OF ALCHEMY CHAP.
If we penetrate to the kernel of the doctrines of the
Alexandrians through the veil of mysticism which envelops
it, we see that these philosophers were permeated with the
idea that the metals were alloys of varying composition.
From this it necessarily followed that the transformation
of one metal into another was possible, either through the
addition of new metallic substances or the expulsion of
some already present. Such transformations of similar sub-
stances into one another appear much less wonderful than
those of dissimilar ones like air, water and earth, which were
mutually convertible, according to the teaching of the
Platonists and Aristotelians. The means for bringing about
these changes in the metals, the substances which it was
necessary to add to them, and the operations which had to
be gone through, were either kept secret or obscured by
indistinct figurative language. The various colours of the
metals, and their alteration by melting them with others,
played a prominent part in alchemistic processes ; in impart-
ing thereby the colour of a noble metal to a base one, much
was supposed to have been attained. For the Alexandrians,
therefore, and also for the alchemists of the Middle Ages,
the colouring of metals was synonymous with their trans-
mutation. The chief operations were the so-called Xantkosis,
Leukosis and Melanosis, which were compared with the pro-
cesses followed in the dyeing of cloth. The old designation
of tinctures for the media by which this transformation was
brought about, gives expression to the idea that the latter
consisted in a dyeing operation.
As may be imagined, no trace can be found of any distinct
chemical conception, or of any knowledge of the actual opera-
tions which take place in these transmutations. At the root,
however, of these endeavours of the Alexandrian alchemists
to produce noble metals from base, lay speculations purely
philosophical, which strongly excited and strengthened the
belief in the transmutation of metals. These were partly
taken from the writings of Plato, especially from his Timceus,
which was highly esteemed by the Alexandrians, and partly
from the philosophy of Aristotle. Both of these Greeks held
« DOCTRINES OF THE PSEUDO-GEBER 39
the opinion that the (so-called) elements in general were
capable of transformation into one another,1 and an extension
of this idea led to the assumption that the same applied to the
metals. The observations of the supposed generation of noble
metals from base, which have been already discussed, were
looked upon as proofs of the correctness of this supposition.
In the writings hitherto attributed to Geber, but which,
according to Berthelot, are not of earlier date than the four-
teenth century, we find a specific chemical theory of the metals,
a, theory which, supported by the great authority of Geber's
name, found universal recognition in the later Middle Ages.
This theory looks upon classes of bodies from a chemical
point of view, and seeks to explain the difference between the
substances comprising these by assuming a peculiar chemical j
composition. The metals consist of sulphur and mercury, /
which are present in them in different proportions and in
different degrees of purity.2
The transmutation of metals consists, according to him, in
an arbitrary alteration of their composition ; the ennobling
of them, specially, in a purification and fixation of the mer-
cury. The idea of creating a metal anew, which we find
highly developed among Western alchemists, is not to be
found in the pseudo-Geber's writings. This, together with
the application of his theory, is proved by the following
sentences, which comprise in themselves his theoretical and
practical chemical programme : " To assert that one substance
can be produced from another which does not contain it, is
1 This idea comes out very clearly in the following passage from
Timceus : — " We believe from observation that water becomes stone and
earth by condensation, and wind and air by subdivision ; ignited air be-
comes fire, but this, when condensed and extinguished, again takes the
form of air, and the latter is then transformed into mist, which dissolves
into water. From this, lastly, are produced rocks and earth."
2 The pseudo-Geber sometimes added arsenic to the above-named con-
stituents of the metals as a third possible one, without however laying
emphasis upon this extension. Here and there, also, Aristotle's doctrine
of the four different states of matter appears to get mixed up with his views
upon the composition of the metals, the "four elements" being regarded
to some extent as subsidiary constituents, sulphur and mercury being the
princit)al ones.
40 THE AGE OF ALCHEMY CHAP.
folly. Since, however, all metals consist of sulphur and mer-
cury, we can add to them the constituent in which they are
deficient, or abstract the one which is present in excess. In
order to achieve this, make use of the art : calcination, subli-
mation, decantation, solution, distillation, coagulation (crys-
tallisation), and fixation. The active agents are the salts,
alums, vitriols, borax, the strongest vinegar and fire."
The varying origin of the works hitherto ascribed to Geber
explains why in many passages of these writings no distinc-
tion is drawn between the supposed two constituents of the
metals and natural sulphur and mercury, while we frequently
find him expressing, in others, the opinion that the former
are not identical with the latter. The mercury and sulphur
present in the metals were, in this second case, looked upon
as being of an abstract nature; thus mercury conferred
glance, malleability, fusibility, and what we consider metallic
properties generally, while sulphur, on account of its com-
bustibility, was regarded as being present because of the
alteration of many metals in the fire. The noble metals,
those which withstood the fire, therefore consisted of almost
pure mercury, which however could not be identical with the
ordinary substance of that name, since the latter was volatile ;
this property was ascribed to the fact of ordinary mercury
containing sulphur. By means of these and similar assump-
tions, contradictions between theory and facts were easily set
aside, the alchemists of later times especially distinguishing
themselves in this way.
For the solution of the possible problem of the transmuta-
tion of metals — possible, that is, in the sense of the above
theory, — so-called " medicines " are, according to the pseudo-
Geber, requisite, these being distinguished as possessing
different power and virtue. The medicines of the first order
do indeed produce changes in the base metals, but these
changes are not permanent. Those of the second order parti-
ally alter the properties of such metals into those of the
noble ones,1 but the transmutation proper is only effected by
1 The Particulars of the later alchemists appear to have corresponded
to medicines of the second order.
ii VIEWS OF THE LATER ALCHEMISTS 41
the medicine of the third order, which is variously designated
as the Philosopher's Stone, the Grand Elixir, or the Magistermm
(masterpiece).1 The accounts which the pseudo-Geber gives
of the preparation of the medicines of higher order are wholly
unintelligible ; it should, however, be emphasised that there
is a wide difference between these and the incredible ex-
aggerations of which other alchemists were guilty, when
speaking of the efficacy of such secret preparations.
One cannot but feel surprised that the alchemists of the
thirteenth and fourteenth centuries, possessing as they did a
fairly extensive knowledge of chemistry, should have re-
mained satisfied with such speculations as to the constitution
of the metals, without actually trying to isolate the sub-
stances that they assumed as being present in these and
other bodies. Instead of endeavouring to gain an insight
into their composition by experiment, they brought forward
fresh hypotheses to controvert obvious objections, e.g., that
the above-mentioned constituents (mercury, &c.) were not
identical with the substances commonly so named.
The above theory of the metals underwent an extension
by Basil Valentine, who assumed the presence in them of a
third constituent, viz. salt.2 By the term salt he did not
mean a definite chemical compound, such as common salt,
but rather the principle of solidification and power of with-
standing fire, just as sulphur determined the combustibility
or change in the fire and also the colour, and mercury the
metallic character and volatility. Basil Valentine generalised
his opinion in this way, that he assumed these three essential
principles in all substances, an assumption which Paracelsus
appropriated later on, and made the basis of his iatro-chemical
doctrine.
Their views upon the composition of the elementary bodies
being so very obscure and so utterly wrong, one sees how
impossible it was for the alchemists to explain chemical
1 At a later period the great elixir was distinguished from the small one,
which only transmuted the base metals into silver.
2 Isaac Hollandus had before this spoken of the saline principle of the
metals.
42 THE AGE OF ALCHEMY CHAP.
processes rightly, connected as these are with the formation
of compounds. Some very incomplete attempts were made
to give a theoretical explanation of isolated observations,
but these only led to gross errors creeping in ; the calcina-
tion of the metals, for instance, was supposed to depend
upon the escape of moisture or of some other constituent,
an idea which reappeared in another form in the later theory
of phlogiston. The above theory of the composition of
metals is sufficient evidence of the small amount of trouble
which was taken to find out the true chemical constituents
of bodies.
We may safely say that scientific chemistry only really
began with the fruitful endeavours to discover the real com-
position of substances. It is out of the question to speak of
this as applying to a time when it was considered as proved
that the formation of a chemical compound was identical
with the annihilation of its original components, a new
substance being created. This view was the almost sole
predominating one during the later alchemistic period,
although in the works of the pseudo-Geber we find some
indications o£ more correct opinions on the composition of
many chemical compounds (the recognition of mercury and
sulphur, for instance, as constituents of cinnabar).
Contemporaneously with the holding of such theories
based upon no facts whatever, the Western alchemists
strove in every imaginable way to obtain the philosopher's
stone, — mercurius philosophorum.1 Those of them who were
in happy possession of the means for transmuting metals,
attributed to it the most astounding powers. In order to
give some idea of the aberration of mind caused by the
alchemistic problem, a few of the extraordinary assertions of
well-known alchemists with regard to the preparation and
efficacy of the philosopher's stone may be mentioned here.
For its preparation (we are now speaking more particu-
larly of the thirteenth century onwards) a materia prima
was requisite, to obtain which was the hardest task of all.
The most incredible substances, natural products of every
1 Cf. the Engler lecture :— Der Stein der Weisen (Carlsruhe, 1889).
ii THE PHILOSOPHER'S STONE 43
kind, were taken as raw materials for the manufacture of
this preparation, and worked up in every conceivable way.
Those who laid claim to the possession of the philosopher's
stone took very good care to keep the secret of their materia
prima to themselves. They described all kinds of operations
with it 1 in the most enigmatical recipes, employing at the
same time mystical drawings, such as those of the dragon, the
red or green lion, the lily, the white swan, &c., and well knew
how to keep their imitators, of whom there were formerly shoals
(isolated cases being found even in this century), in a state
of continual tension. That this was possible is explained
by the immovable and almost universal belief in the trans-
mutation of metals, by means of the philosopher's stone,
during the Middle Ages.
To the latter the greatest miracles were ascribed ; thus,
Roger Bacon does not hesitate to say that it was able to
transform a million times its weight of base metal into gold
(millies millia et ultra). Others, e.g. Arnaldus Villanovanus,
were more modest in their estimate of its powers, stating
that it could convert into gold one hundred times its weight
of mercury. Others, again, surpassed even Bacon, as the
following passage from the Testamentum Novissimum, ascribed
to Lully, proves : " Take of this precious medicine a small
piece, as large as a bean. Throw it upon a thousand ounces
of mercury, and this will be changed into a red powder.
Put one ounce of the latter upon one thousand ounces of
mercury, which will thereby be transformed into a red
powder. Of this, again, an ounce thrown upon a thousand
ounces mercury, will convert it entirely into medicine.
Throw an ounce of this on a thousand ounces of fresh
mercury, and it will likewise turn into medicine. Of this
last medicine, throw once more an ounce upon a thousand
ounces of mercury, and this will be entirely changed into
gold, which is better than gold from the mines." One sees
clearly, from these and other fraudulent assertions, that the
simple standpoint which the Egypto-Greek alchemists
1 The process of fixation, a term which indicated the solidification of
mercury by the transmutation, was of special importance.
44 THE AGE OF ALCHEMY CHAP.
assumed with regard to the question of the transmutation
of metals, was departed from in the later Middle Ages.
In view of such excesses, which are an insult to the
human understanding, it causes no surprise to find attributed
to the philosopher's stone other results which are, if possible,
/ \even more incredible; being a universal medicine, health
and life were to be preserved and ensured by it. State-
ments as to the power of prolonging life possessed by the
elixir were also rife in the later Middle Ages, and it\was no
unusual assertion that adepts, the fortunate possessors of
the panacea, had been able to prolong their lives to 400 years
and more. The long lives of the patriarchs were explained
by the assumption that they were acquainted with this
universal medicine. In the time of the Arabian alchemists
healing properties were ascribed to gold prepared artificially
and brought into the potable form (aurum potabile), and
from this the belief in the medicinal power of the philoso-
pher's stone appears to have originated.
Alchemistic ideas produced their most absurd results
towards the end of the Middle Ages and in still more recent
times, the creation of living beings by means of the philo-
sopher's stone being not merely held as possible, but being
actually taught ; this marks the acme of the mental aber-
ration they induced.
The melancholy picture, which the condition 'of alchemy
presents to us at various periods, becomes still more sombre
and involved in deeper shadow from the fact that men
did not hesitate to affirm the Divine assistance and to claim
predestination, in order to explain the marvellous effects of
the philosopher's stone. Gross abuse was made in this way
of the name of the Deity, and also of prayers and' biblical
quotations, by the alchemists of the thirteenth century, and
still more by their successors. There is no need to go into
further details upon this point here, but it is necessary to
mention it in order that the methods by which the problems
of alchemy were treated at different periods may appear in
their proper light.
Upon the development of chemistry as a science, the
ii PRACTICAL-CHEMICAL KNOWLEDGE 45
alchemistic doctrines — especially the theories of the composi-
tion of metals — had only a slight and an indirect influence.
The excesses to which they gave rise have — as aberrations
of mind, enchaining a large portion of the educated — a
higher value for the history of civilisation than for that of
chemistry. The main significance of alchemy for the latter
lies in this, — that the endeavours to solve the problem of the
transmutation of metals were the cause of actual work
with materials of every kind ; and the result of this was
a not inconsiderable increase in the knowledge of applied
chemistry during the alchemistic age. The following section
will be devoted to an account of the latter.
Practical- Chemical Knowledge in the Alchemistic Period.1
When one considers upon what superficial observations
the conviction of the transmutability of metals was based,
and how readily wholly untenable theories upon the com-
position of bodies were brought forward and accepted, one
feels no surprise that comparatively little progress was
made, during the succeeding epochs, towards explaining the
numerous chemical processes already known to the Ancients.
The acquirements in chemistry during these centuries them-
selves likewise 'remained, for the most part, empirical; it
was but seldom that the composition of chemical compounds
was even in some degree correctly indicated. The fantastic
treatment of chemistry — a treatment wholly foreign to the
exact sciences — has been sufficiently detailed in the preceding
section. We must not omit to mention, however, that the
addition of new facts to those already known, and the gain
of experience in the fields of technical and pharmaceutical
chemistry and in the manufacture of chemical preparations,
were not inconsiderable.
1 Cf. Kopp, Gesch. d. Chemie, vols. iii. and iv. ; Hofer, Histoire, etc.,
vol. i. p. 317, et seq.; Gmelin, Gesch. d. Chemie.; and Berthelot, La Trans-
mission de la Science Antique du Moyen-dge.
46 THE AGE OF ALCHEMY CHAP.
Technical Chemistry. — Metallurgy, upon which the
infant powers of an early developed technique were expended,
shows, upon the whole, but little progress. Towards the end
of the alchemistic period certain other metals were indeed
added to those already known, viz., the semi-metal antimony,
together with bismuth and zinc ; but these can only lay claim
to a subordinate position in the circle of metallurgical processes
generally. From the eleventh century on, mining increased
among the Western nations, in Germany especially in the
Harz, Nassau and Schlesien. So far as our present in-
formation goes, only trifling alterations were made in the
preparation and purification of the metals.1
Gold was obtained and purified from other metals and
admixtures by the old method of cupellation (working with
lead), already accurately described by the pseudo-Geber. The
latter knew that the desired result was ensured and its pro-
gress hastened by the addition of saltpetre, and, further, that
copper and tin, but not silver, could be separated from gold
in this way. In the fifteenth century there was added to
this the process of purifying gold by fusing it with antimony
trisulphide ore (Spiessglanzerz), a method which is given in
detail by Basil Valentine. Alloys of gold were often fraudu-
lently prepared of set purpose.
The extraction of silver from its ores was accomplished,
as in Pliny's time, by fusion with lead, an operation
first termed, " Aussaigern" by Basil Valentine. The only
means of separating gold from silver which was known up
to a comparatively recent date, was the cementation -process
of the Ancients. The wet process with nitric acid appears
to have been first successful in the time of Albertus Magnus,
at least he is the earliest to indicate it ; an absolutely
1 The work entitled Schedula Diversarum Artium, which was written by
Theophilus Presbyter, a Benedictine of the eleventh century, gives a true
picture of the state of technical industry in his time, particularly of the
working up of metals, something being also said about their production
from the ores.— A tenth-century manuscript, Mappce Clavicula, edited by
Berthelot, contains an essay on the noble metals, and by its agreement
with recipes found in the Leyden papyrus, conclusively shows the close
connection with the Egypto-Greek alchemy.
METALLURGY 4T
certain acquaintance with the process is first to be found
in Agricola.
From the importance which was attached to the successful
working-up of gold and silver ores, one understands how the
closest attention was given from an early period to the definite
quantitative yield of the noble metals. Accurate balances
came into use, their employment in cupellation and cementa-
tion processes being made obligatory by law ; one thus meets
here with the first beginnings of a docimacy.
With regard to the metallurgy of iron, lead, tin and
copper in the alchemistic period, there are no particular
improvements to record. Basil Valentine (fifteenth century)
states that the last metal was also obtained by the wet
process as the so-called cement copper, by precipitating a
solution of copper vitriol with iron. The changes undergone
by these metals on being heated and on treatment with
chemical reagents, especially acids, were closely studied,
and thereby the knowledge of metallic preparations decidedly
enlarged. (See p. 52.)
Mercury, which played such an important part in the
theoretical views of the alchemists, was prepared on a large
scale for technical purposes by roasting quicksilver ores in
improved furnaces, especially after the opening up of the
rich Idrian mines in the fifteenth century. The prepara-
tion of the metal by distilling a mixture of sublimate and
caustic lime was well known to Basil Valentine. For its
purification he gives various processes, some of which had
been already described by the pseudo-Geber. Mercury was
much used, particularly for the extraction of gold and silver
(by the so-called amalgamation process) and for gilding.
Metallic zinc and bismuth, and also cobalt ore, are like-
wise mentioned by Basil Valentine, but the metals themselves
do not seem to have been employed technically; some
preparations of zinc, however, were. A special place among
chemical preparations is to be assigned to antimony and its
compounds, the knowledge of which is due to Basil Valentine
himself. (See p. 54.)
In pottery and glass manufacture, important improve-
48 THE AGE OF ALCHEMY CHAP.
ments in single points were made during the alchemistic
period ; but it is also noticeable here that the interest in
the chemical processes remains a purely external one, no
attempt being made to give a scientific explanation of the
facts empirically arrived at. The general use of glazes con-
taining lead and tin for earthenware vessels is worthy of
mention, as is also the burning of colours into glass (the
whole mass having formerly been coloured by the addition of
metallic oxides during fusion).
Dyeing remained stationary on the whole, so far as the
chemical media for fixing the colour on the fibre were con-
cerned ; alum was universally employed as a mordant, being
manufactured on a large scale in different places. The
introduction of the kermes dye (cochineal) into European
countries by the Arabians, that of orchilla, already known in
ancient Rome (from the East in the thirteenth century),
and, lastly, the gradual supplanting of the (blue) dye from
woad by indigo, are the most important technico-chemical
events in the domain of dyeing.
Condition of Pharmaceutical Chemistry.
Although the Arabians and the later Western savants
busied themselves with chemical operations, and thereby
arrived at preparations of the most various kinds, the pharma-
ceutical chemistry of that period only profited slightly by
this ; it was Basil Valentine who inaugurated a new era by
his bold attempts to apply chemical preparations to medicinal
purposes. The opening up of the intimate connection exist-
ing between chemistry and medicine, which led to the high
development of pharmacy, was reserved for the period of iatro-
chemistry. The Arabians prepared their medicines strictly
according to the recipes of Galen, Andromachus and others,
which were transmitted to them, according to Leo Africanus,
by the Nestorians.1 Apothecaries' shops, in which the
remedies were almost exclusively prepared from vegetable
1 For their influence upon the Arabians see note 2, p. 28.
ii KNOWLEDGE OF CHEMICAL COMPOUNDS 49
substances, sprang up at an early date. To the Arabians
belongs the credit of having improved and rendered the
process of distillation serviceable for this purpose : distilled
water, ethereal oils, and other products (especially spirit
of wine) obtained by distillation, to which the most wonder-
ful results were ascribed, soon came into general use.
These apothecaries' shops with their fittings then spread
into Spain, Southern Italy (into Salerno in the eleventh cen-
tury) and, somewhat later, into Germany. The recipes of
that time for the preparation of medicines, the imperfect
pharmacopeias,1 show that the doctrines and axioms of Galen
and the Arabian physicians remained the standards up to the
end of the fifteenth century. The position of the physician
with regard to the apothecary was early fixed by legal statute,
it being considered advisable to draw a sharp distinction be-
tween the man who had to prescribe the medicines and the
man who had to make them.
With respect to chemical preparations proper, a few new
ones were added to those already used in medicine, e.g. salt-
petre, mercury in the form of grey ointment, and — towards
the end of the fifteenth century, at the instigation of Basil
Valentine — various mercurial and antimonial preparations
(see p. 54). Almost all the physicians of that time took up,
however, an antagonistic position with regard to the last of
these, being of opinion that the undoubted poisonous properties
of antimony compounds were incompatible with their internal
use.
Knowledge of the Alchemists with regard to Chemical
Compounds.
It has already been mentioned that the knowledge of the
true composition of chemical compounds was but slightly
extended during this period ; we have therefore to deal here
with the state of empirical knowledge as affecting substances
prepared artificially, together with a few occurring naturally.
1 The first German pharmacopeia (Arzneibuch) was drawn up by Ortholph
von Baierland and appeared in 1477.
E
50 THE AGE OF ALCHEMY CHAP.
The tendency to group together observed facts under a
common point of view showed itself at an early date with
respect to salts, of which a large number were known. The
pseudo-Geber regarded solubility in water as a general charac-
teristic ; later on the generic name sal was made to include a
variety of substances, e.g. the vitriols, potash, soda, saltpetre,
alum, etc. Other chemical compounds of totally different
nature, viz. the alkalies and acids, were added to the class of
salts by many alchemistic writers, the term sal being thus
widely extended and distorted ; it was reserved for a later
century to fix it without any ambiguity. In addition to the
common designation sal for a number of heterogeneous bodies,
we find in the writings of that time the generic name spiritus
for the volatile acids, e.g. spiritvis salis for hydrochloric acid ;
also the name spiritus urince for volatile alkaline salt (car-
bonate of ammonia). The individual salts are distinguished
by the word which follows sal, for instance, sal petrce, sal
maris, etc. ; for alkalies, such as caustic potash, the expression
nitrum alcalisatum is frequently used. One seldom meets
in the alchemistic age with a strict distinction between
potash and soda, or between their carbonates, while, on the
other hand, preparations of carbonate of potash obtained in
different ways were regarded as dissimilar products.1
This acquaintance with the carbonates of soda and potash
was accompanied by a knowledge of the lyes obtained from
them by the addition of lime, the strongly alkaline and solvent
power of these lyes being largely made use of, e.g. in the pre-
paration of milk of sulphur. Tjhe name " alkali " is first met
with in the writings ascribed to Geber, while the designation
"caustic" had been already employed by Dioscorides for
burnt lime, and at a later period for lyes. The question of
the occurrence of alkalies in plants was frequently discussed
among the alchemists ; although it did not escape some of
them that different amounts of ash and of alkali were found
in different parts of a plant, only a few held the opinion
that the alkali was really present in the plant itself, most of
1 The salt from the ashes of plants was termed sal vegetabile, and that
from tartar, sal tartari.
if SULPHURIC, NITRIC, AND HYDROCHLORIC ACIDS 51
them believing that it was first produced during the inciner-
ation of the latter.
It was formerly taken for granted that the Arabians
possessed a very considerable knowledge of the acids, in com-
parison with that of the Ancients, who were totally unac-
quainted with the mineral acids. This assumption was based
upon the fact that in the treatise De Inventione Veritatis, at-
tributed to Geber, he explained the method of obtaining
nitric acid by distilling a mixture of saltpetre, copper vitriol,
and alum in certain proportions; it was designated aqua
dissolutiva or aqua fortis. We know now, however, that this
manuscript does not date further back than the fourteenth
century. The preparation of nitric acid from saltpetre and
sulphuric acid was known to alchemists of a later date ; and
we find Basil Valentine speaking of it as a process which had
been in operation for a long time.
Sulphuric acid was certainly obtained by the pseudo-Geber,
for he mentions as noteworthy that when alum is strongly
heated, a spirit distils over which possesses a high degree of
solvent power ; he does not, however, appear to have investi-
gated its properties more closely. The writings of Basil
Valentine show that the preparation of sulphuric acid by dis-
tilling a mixture of iron vitriol and pebbles, and also by setting
fire to sulphur after the addition of saltpetre to it, was known
not only to himself but also to his predecessors. An aqueous
solution of sulphurous acid, the combustion product proper
of sulphur, was frequently confounded with sulphuric acid.
Basil Valentine is the first to describe the preparation of
aqueous hydrochloric acid, which he terms spiritus salis, by
heating a mixture of common salt and green vitriol, and also
its behaviour towards many of the metals and their oxides.
He likewise knew that a mixture of this acid with aquafortis
was the so-called aqua rrgis, now termed aqua regia, which
the pseudo-Geber had already made use of, obtaining it by
the solution of salmiac in nitric acid.
Nitric acid and aqua regia l (so-called because it dissolved
1 Albertus Magnus terms them respectively aqua prima and aqua
stcunda.
E 2
52 THE AGE OF ALCHEMY CHAP.
gold, the king of metals) were highly prized by the alchemists
of the West. The observation that almost nothing was
able to withstand this aqua regia, even sulphur being "con-
sumed" by it, strengthened the conviction that in it they
possessed a liquid which very nearly approximated to the
long-sought-for "alkahest," the universal solvent. On the
same grounds oil of vitriol was greatly valued, many indeed
regarding it as the sulphur philosophorum, or, at least, as a
substance which would lead to the acquirement of the materia,
prima.
Among the salts which were already known in Pliny's
time, and whose properties were carefully investigated by
the alchemists, alum and some of the vitriols deserve special
mention, the former being obtained in various places from
alum shale. The pseudo-Geber tells us how to purify it by
recrystallisation from water, and terms it alumen de rocca
(from the name of its chief source, the town Roccha), a term
which long remained in vogue in France as alun de roche.
The fact that alum contained an alkaline salt was overlooked,
and its true composition remained unknown. Iron and
copper vitriols were lagely employed in different chemical
operations. The pseudo-Geber describes the preparation of
the pure products by crystallisation, and Basil Valentine the
production of iron vitriol by dissolving iron in sulphuric
acid, a method which indicated the composition of the salt,
although he did not explain this correctly.
The important salts, saltpetre, salmiac and carbonate of
ammonia, first became known and used for chemical purposes
in the alchemistic period. The author of the works ascribed
*^to Geber was well acquainted with potash saltpetre, as it
served him for the preparation of nitric acid ; and there is
every reason to suppose that it was used in even earlier
times for the production of fire-works and such like things,
after its property of deflagrating with red-hot carbon had
oeeu recognised. The oldest designations for it were sal
Vetrce and sal petrosum. Ray m und Lully also termed it sal
nitri, but distinguished between it and nitram, the fixed
alkali of the older writers; in the sixteenth century this
ii SALTS OF AMMONIA AND OF THE METALS 53
latter word was converted into natron, while the name nitrum
was given to potash saltpetre.
The same applies to the term salmiac, sal ammoniacum,
as to that of nitrum, in so far that both of them had originally
a different meaning from what they now possess ; for the sal
ammoniacum of the Ancients was without doubt rock-salt.
At the time when the pseudo-Geber's works were written,
on the other hand, this name, which is also metamorphosed
into sal armeniacum (Armenian salt), could only mean
salmiac. The sal armoniacum of Basil Valentine led to the
contraction salmiac. At first this salt appears to have been
partly prepared from dung, and partly to have been found
as a natural product of volcanic origin.
Carbonate of ammonia, well known to the alchemists of
the thirteenth century as volatile alkaline salt (spiritus urince)
was obtained by distilling putrefied urine. Basil Valentine
taught how to prepare it from salmiac and fixed (carbonated)
alkali, a method which led a long time afterwards to the
proper recognition of the composition of the salt. The
pharmaceutical use of these two ammonia compounds, just
named, probably belongs to a later date.
The knowledge of the metallic salts was very decidedly
increased during the alchemistic period. A special interest
attached to a solution of gold in aqua regia, since from this
aurum potabile the most wonderful medicinal effects were
expected. The pseudo-Geber was the first to become
acquainted with nitrate of silver in the crystalline state, and
to observe the precipitation of its solution by one of common
salt, a reaction which came to be applied as a test both for
silver and for salt. The alchemists were also aware of the \
beautiful precipitation of metallic silver from a solution of its J
nitrate by means of mercury or copper.
Compounds of mercury early attracted the interest of
those who carried out chemical operations. The pseudo-Geber
described the preparation of mercuric oxide by calcining the
metal, and that of sublimate (mercuric chloride) by heating
a mixture of mercury, common salt, alum and saltpetre ; he also
54 THE AGE OF ALCHEMY CHAP.
taught how to prepare various amalgams.1 Basil Valentine
was acquainted with basic mercuric sulphate, and also with
mercuric nitrate. Being an advocate of heroic treatment,
he recommended the medicinal use both of the latter and of
sublimate.
Preparations of zinc and bismuth (e.g. zinc vitriol) were
well known towards the end of the fifteenth century, but
detailed records are wanting both of their formation and
their properties. Antimony and its compounds, on the other
hand, were the object of unwearied labours on the part of
Basil Valentine, as his treatise Triumphwagen des Antimonii
(" Triumphal Car of Antimony ") sufficiently testifies. He
shows how to prepare antimony itself from the native
sulphide (which was termed antimonium or stibium and was
known to the Ancients), by fusing it with iron. In his
treatise, WiederJiolung des grossen Steins der Uralten Weisen
(" Recovery of the Great Stone of the Ancient Philosophers ")
he writes : " If one adds some iron to the fused Spiessglas,2
there is produced by a particular manipulation a curious
star, which the wise men before me called the signet star of
philosophy." Basil Valentine was well aware that antimony
did not possess the properties of a metal in full degree, and
so he regarded it as a variety of one, especially as a variety of
lead; he sometimes talks of it as the lead of antimony.
Even in his time antimony was employed for alloys, which
served for the manufacture of printer's type, mirrors and
bells. It did not escape him, either, that Spiessglas con-
tained sulphur, and he was also acquainted with amorphous
sulphide of antimony and sulphur auratum (a mixture of
Sb2S3 and Sb2S5). He gives distinct recipes for the prepara-
tion of antimony trichloride (butter of antimony), of powder
of algaroth (basic chloride of antimony), of antimony trioxide,
1 This word is first found in the writings of Thomas Aquinas. The part
played by amalgams in the transmutation of metals has been already
considered.
2 This designation of Basil Valentine's for native sulphide of antimony
became altered later on into Spiessglanz.
ii METALLIC OXIDES ; SULPHUR 55
and of potassic antimoniate, and there can hardly be a doubt
that he recommended and applied those preparations for
internal use. With regard to the composition of these, he
only appears to have had a tolerably clear idea of that of
the sulphide.
Arsenic, which is so closely allied chemically to antimony,
and with whose sulphides the Ancients were acquainted, was
first prepared by the Western alchemists in the thirteenth
century ; Basil Valentine regarded it as a " bastard metal "
analogous to antimony. Arsenious acid is first distinctly
spoken of by the pseudo-Geber, having been obtained by the
roasting of realgar ; it was known as white arsenic, in contra-
distinction to the red and yellow varieties (realgar and
orpiment). Its occurrence in the smoke from pyrites burners
was also noticed by the observant Basil Valentine. Mention
has already been made of the important part which was played
in alchemistic operations by the property which arsenic pos-
sessed of turning copper white;1 indeed, this contributed
materially to the belief in the possibility of the transmutation
of copper into silver.
In addition to the metallic oxides which have been
already spoken of (those of mercury, antimony, etc.), and the
early known oxide of copper and oxides of lead (PbO and
Pb3O4), oxide of zinc and peroxide of iron may be specially
mentioned. The former of these, which separated in woolly
flakes when zinc was burnt, and which was therefore termed
lana philosophica, appears to have been known to Dioscorides,
but it is in the alchemistic period that we first come across
an intimate acquaintance with it. The alchemists of the
Middle Ages were familiar with peroxide of iron in the
different forms, red and yellow ; the designation colcothar, for
the ignited oxide, is to be found for the first time in Basil
Valentine's writings.
The theoretical importance which, from early times, was
ascribed to sulphur as a constituent of the metals, and also of
other bodies, leads to the question — How was the actual know-
1 On account of this behaviour, the pseudo-Geber calls arsenic medicina
Venerem decdbans.
56 THE AGE OF ALCHEMY CHAP.
ledge of this element and of its compounds acquired ? The
property possessed by sulphur of dissolving in aqueous alkalies,
and of being thrown down from such a solution as sulphur milk
upon the addition of acids, is described by the pseudo-Geber
in his treatise De Inventions Yeritatis ; the disappearance of
sulphur, when acted upon by aqua regia, was likewise re-
garded as solution. Basil Valentine is the first to give
definite details regarding flowers of sulphur, and also re-
garding the taking up of the element by many oils, a
property upon which the preparation of sulphur balsam
depended.
Mention has already been made of various sulphur com-
pounds, the sulphides of mercury and antimony among others
which were the most valuable materials for the production
not only of sulphur itself, but also of other bodies. These
had already been grouped together as forming a particular
variety of compounds, under the name oimarcasitce (Albertus
Magnus), zinc blende, galena, and iron and copper pyrites
being included among them. The peculiarity, which these
substances had in common, of giving off a product of such
characteristic odour as sulphurous acid when roasted, may
not unlikely have formed the main reason for thus gathering
them into one group. It must not be forgotten, how-
ever, that the formation of several metallic sulphides from
their components had been observe^, (e.g. that of cinnabar
from quicksilver and sulphur), and this may be supposed
to have contributed materially to a knowledge of their
composition.
In spite of many unequivocal observations to the con-
trary, people still held to the assumption that the metals
and almost all other substances contained sulphur. Organic
bodies, too, had to conform to this hypothesis; their real
constituents remained hidden, no sharp general distinction
being drawn between them and inorganic compounds. The
meagre attempts made to explain the formation of organic
substances, e.g. in fermentation processes, only give evidence
of confused and untenable views. The organic preparations
which were known in the alchemistic age were but few in
ii SPIRIT OF WINE, VINEGAR, ETC. 57
number. Among them spirit of wine l takes a prominent
place, its manufacture being gradually simplified and im-
proved after more perfect apparatus had been introduced by
the Alexandrians. In accordance with its importance for
medicinal and alchemistic purposes, it was usually termed aqua
vitce, the name alcohol being first met with in Libavius (end
of the sixteenth century). The preparation of concentrated
spirit of wine — as an excellent solvent for many things — by
repeated distillation, and also by dehydration with fused
potashes, was already known to Raymund Lully. To test its
strength, Basil Valentine recommends that a portion be
burnt, in order to see whether any water remains behind or
not. The latter alchemist was also acquainted with various
chemical transformations of alcohol, although he did not
obtain the resulting compounds in a state of purity ; among
these were the production of common ether by the action of
sulphuric acid, and of nitric and hydrochloric ethers by the
action of nitric and hydrochloric acids respectively. By the
" sweetening " ( Versilssung) of alcohol is to be understood
our term etherification. That alcohol is only formed during
the various processes of fermentation, which yield wine, beer
and spirits, was not perceived even by the most acute ob-
servers of that time; its pre-existence in unfermented
materials was thus taken for granted.
Increasing attentio.. was likewise paid to the product of
the acetic fermentation. The alchemists of the later Middle
Ages taught how to concentrate vinegar by distillation, and
they also prepared various salts of acetic acid, e.g. basic
acetate and sugar of lead. Other organic acids, too, were
noticed in different plant juices, but they were mostly mis-
taken for acetic acid. The addition to the medical treasury
of various resins and oils, especially ethereal oils, which were
obtained from plants by distillation in improved apparatus,
1 Berthelot (Ann. Chim., (6), vol. xxiii., p. 433) has traced with great
care the history of the discovery of spirit of wine, and has found that the
preparation of alcohol by distilling wine was accurately known so far back
as the time of Marcus Graecus (eighth century, A.D.).
58 THE AGE OF ALCHEMY CHAP.
is no evidence of scientific progress; this really begins for
organic chemistry with the discovery of methods for arriving
at the composition of organic compounds.
The Fortunes of Alchemy during the last Four Centuries.
After the labours of Basil Valentine, and especially after
the beginning of the iatro-chemical period, alchemy gradu-
ally became separated from chemistry, which was raising
itself to the rank of a science. Although, therefore, a record
of the alchemistic aims or rather errors of the last few centuries
does not properly come within the scope of a short history
of chemistry, they cannot be passed over in complete silence ;
the justification for this lies in the relations in which the most
eminent chemists of the sixteenth and seventeenth centuries
stood with regard to alchemy. The support given by such
men to the latter undoubtedly accounts to a large extent
for the belief in the transmutation of metals as an incon-
trovertible fact being but seldom affected, and this, notwith-
standing the great increase in chemical knowledge. Another
effective means by which the life of alchemy was prolonged,
consisted in the favour with which it was regarded by many
princes; the seductive prospect of easily acquired treasure
often rendered the latter a prey to designing alchemists.
The actual decay of alchemy, for which the numberless
disappointments of honest workers and the exposure of
numerous frauds paved the way, may be dated from the first
half of the eighteenth century, when the conviction of the
practicability of transmuting metals began to die out among
most chemists. Even up to the present century, however,
we find able and educated men in the thralls of alchemistic
chimeras, and directly opposing the simplest rules of
reason.
A distinction must be drawn during the iatro-chemical
period between alchemists and chemists, inasmuch as the
latter aimed at the solution of a scientific problem, viz. the
ii ALCHEMY DURING THE LAST FOUR CENTURIES 59
knowledge of the relations between chemistry and medicine.
At the same time this distinction must not be taken as
meaning that the most eminent among the iatro-chemists
were not firmly convinced that the ennobling of metals was
a fact, indeed some of them maintained that they were in
possession of the most powerful alchemistic specifics ; it was
but seldom, however, that chemists were at the same time
practical alchemists.
Paracelsus, who was greatly given to romantic exaggera-
tions, claimed for himself the widest knowledge of alchemy.
Van Helmont, whose authority was especially weighty, went
so far as to describe in detail the transmutation of mercury
into gold and silver, as effected by himself with the aid
of a very small quantity of a gold- and silver-producing philo-
sopher's stone. The opinion -held by the highly esteemed
Libavius respecting alchemy and what it could effect is
equally significant of the judgment of that period upon the
subject ; he regarded the transmutation of metals as an
accomplished fact. Other influential physicians of the six-
teenth century, such as Agricola — famed as an observant and
accomplished metallurgist, — Sennert, and Angelus Sal a, were
more cautious in their assertions with respect to alchemy,
but they never seriously contended against the possibility
of transmutation. Tachenius alone, the last iatro-chemist
of note, took up a sceptical position with regard to the
alchemistic problem ; he considered the evidence adduced in
favour of the ennobling of metals as insufficient, notwith-
standing that his famous teacher Sylvius had given himself
up unreservedly to the belief in their transmutation.
The power of this belief was still so great at that time,
when the phlogistic period was just beginning and chemistry
was striving to develop itself independently, that it took
firm root in the minds of even the most discerning men,
with Boyle at their head. The latter was firmly convinced
of the possibility of transmuting individual metals into one
another, as were also many of his contemporaries and
successors, e.g. Glauber, Homberg, Kunkel, Stahl and Boer-
have, of whose earnest desire to arrive at the truth there
60 THE AGE OF ALCHEMY CHAP.
can be no doubt whatever. That the wished-for goal was
never reached in spite of the most unwearied efforts, did not
shake their belief in the correctness of the assumptions of
alchemy ; Stahl alone began to doubt these towards the
end of his life, and warned his brethren against alchemistic
frauds. The vitality of the belief in transmutation depended
chiefly on the theoretical opinions which these men held re-
garding the composition of metals ; the primal error of the
pseudo-Geber and his disciples was thus propagated for
centuries through the alchemistic age.
Boerhave was the last distinguished chemist to support
with his great authority some of the alchemistic views,
while he failed to criticise others of the fraudulent asser-
tions with sufficient sharpness. After his time no notable
exponent of chemistry — which had now attained to the
rank of a science — spoke in their favour; but all the
greater was the number of cheats and swindlers who culti-
vated the lucrative field of gold-making even during the
eighteenth century. The conviction of the impossibility of
transmutation, which was at that time establishing itself
among scientific chemists, made its way but slowly into
outer circles. Credulity, and the hope of obtaining riches
for nothing, were the means of leading many into very
doubtful paths even so late as the end of last century and
the beginning of this one.1 The final echoes of the alche-
mistic problem, which had for so long a period of time
held the cultured of every nation in a state of tension, and had
even blinded eminent scientific men, only appear to die
away during the last decades of our own century.
Seeing the marvellous results which alchemy produced,
it is but natural to inquire more closely into the supposed
evidence in favour of the ennobling of metals, and to ask
what kind of observations led to this being regarded as a
matter of fact. If most weight is to be laid upon the
1 For details on these points, especially for an account of the interesting
relations of the Rosicrucians to alchemy, and of secret alchemistic as-
sociations, etc., see H. Kopp's Die Alchemie in dlterer und neuerer Zeit, a
book which gives us a clear insight into the workings of the alchemists.
ii POWER OF THE PHILOSOPHER'S STONE 61
statements of men who had established their claim as
practised observers, then first place must be given to the
records of the great physician and chemist van Helmont
(towards the middle of the seventeenth century), respecting
transmutation as carried out by himself; these records
afford the most remarkable testimony to the power of alche-
mistic illusions. Van Helmont had received from an
unknown source a small specimen of the philosopher's stone,
and with this he states that he transformed several portions
of mercury into pure gold, giving the exact proportions
by weight ; one part of this preparation sufficed to trans-
mute 2000 parts of mercury.
Soon after the death of van Helmont, Helvetius, body-
physician to the Prince of Orange, published a detailed
account of the transmutation of lead into gold, by means of
a trifling quantity of a preparation which had come to him
from the hand of a stranger. It appeared impossible to
doubt the testimony of such men, who were held in high
esteem by all the scientific investigators of that time.
More palpable proof of the actual transmutation of metals
was held to be furnished by the coins or ornaments prepared
from alchemistic gold up to and in the eighteenth century.1
The evidence, which came for the most part too late, that
these consisted of worthless alloys (e.g. bronze gilt over),
was all too soon forgotten. The findings of courts of justice,
too, in favour of alchemistic operations, were looked upon as
proofs of transmutation having been actually accomplished.
As has been already mentioned, a large number of
German princes gave unremitting support to the efforts of
the alchemists, being induced to do so by the hope of large
gains. Many of them worked zealously at transmutation
themselves, among others John, Burgrave of Niirnberg, who
received the surname of " the Alchemist " ; the Emperor
Rudolph II., the most powerful protector of the makers of
gold; the Elector Augustus of Saxony, the Elector John
George of Brandenburg, etc. etc. The courts of these
princes were the field-grounds of adepts, who for long
1 Cf. H. Kopp's Alchemic, vol. i., p. 90, et seq.
62 THE AGE OF ALCHEMY CHAP.
succeeded, by means of clever experiments, in maintaining a
belief in their art among these Maecenases, until, as usually
happened, they were unmasked as cheats and generally
severely punished, after having been the cause of excessive
expenditure on the part of their patrons.
It is impossible to enter here into details of the
romantic lives of alchemists like Leonhard Thurneysser,
physician at the court of John George of Brandenburg,
Sendivogius, Caetano (on whom the title of Count was
bestowed), St. Germain, Cagliostro, etc. The two last named
lived at a time when chemistry was strong enough as a
science to protect itself against the frauds of alchemy. The
opposition to the latter which was raised in the course of
the preceding century by chemists of repute, e.g. Geoffroy
the elder (the earlier warnings of Erasmus of Rotterdam,
Athanasius Kircher and Palissy having had no effect), led
to its ultimate fall, which even the amalgamation of alche-
mistic aims with those of the secret societies (Rosicrucians,
Illuminates, etc.) was powerless to retard. The belief in
the possibility of the transmutation of metals received its
actual deathblow from the new chemistry which began with
Lavoisier.1 At the same time, however, (i.e. about the year
1790), the Hermetic Society endeavoured to foster and main-
tain the alchemistic illusion in Germany. It has only recently
come to light that the leaders of this undertaking were.
Kortum (the poet-author of the Jobsiade and a practising
physician in Bochum, Westphalia) and a Dr. Bahrens,
a clergyman. But Wiegleb, a chemist and pharmacist of
merit, combated those belated efforts with entire success.
The melancholy errors which arose from the introduction
of the mystical religious element into alchemy can but be
indicated here ; the assertion, frequently made by adepts,
1 Schmieder, who published a history of alchemy in 1832 (in Halle), did
not hesitate to accept the transmutation of metals as having been actually
accomplished by various adepts. He expresses himself with more caution
regarding the assumed efficacy of the philosopher's stone as a medicine and
a means of prolonging life. Even in quite recent times we find the study
of alchemy carried on, ostensibly with result, e.g., in Paris in 1844 (cf.
Baudrimont, Traite de Chimie, vol. i. ).
ii GENERAL EFFECT OF ALCHEMY ON CHEMISTRY 63
that the secret of making gold was revealed to them through
the grace of God, only excites feelings of repugnance.1
Other frauds, which were likewise the products of alchemistic
effort during the eighteenth century, to go no further back,
merely provoke satire ; among these may be mentioned the
endeavours to prepare from the air the so-called ' ' substance
of shooting stars " (the alga Nostoc commune, which is found
in wet ground, was so regarded), and the materia prima
from "air-salt."
The benefits which have accrued to chemistry during
the last four centuries from the mania for producing
gold from the base metals, can only be estimated as very
slight. It was but very seldom that a discovery of technical
importance, like that of the making of porcelain by Bottger,
sprang from alchemistic work. On the other hand, it did a
vast amount of harm during that period, for it crippled the
usefulness of many able men who would undoubtedly
have advanced science had they not been influenced by
chimeras of an exciting nature ; as it was, they were led
away into the most tortuous paths.
We are thus forced to the above unfavourable criticism
of the work of the alchemists on their problem of the
transmutation of metals, in spite of the striking and
seemingly incontestable evidence in favour of the latter ; in
spite, also, of a strong inclination at the present time to a
belief in the mutual convertibility of elements chemically
similar — a belief grounded upon speculations which do not
seem to be without foundation. But in no single case, as
yet, has there been any positive evidence brought forward in
support of this idea.
If, therefore, we review the work of the alchemists during
1 Had such misuse of the name of God and of the Bible been made in
the time of Luther, as was later the case, or had he been aware of it, his
opinion of alchemy would have been a much lower one ; as a matter of fact
he valued it because of its bearing upon religious feeling. In contradis-
tinction to this stands Melanchthon's criticism of alchemy, a criticism
which testifies to the sobriety of his judgment (he called it imposturam
qvandam sophisticam).
64 THE AGE OF ALCHEMY CHAP, n
the last fifteen centuries, we arrive at the conclusion that it
was based upon a series of falsely interpreted chemical
problems. The expectation of the easy acquirement of
boundless riches, the auri sacra fames to which it led, formed
the powerful stimulus to the useless and yet continually
renewed efforts of an unsatisfied mankind.
CHAPTER III
HISTORY OF THE IATRO-CHEMICAL PERIOD
INTRODUCTION. — Traditional belief, which dominated every
branch of science during the Middle Ages, exercised
its power not least in the domain of alchemy, for almost
every one engaged in chemical pursuits was deluded by
the idea that gold and other bodies could be artificially
prepared. In the course of the fifteenth century, however,
this yoke, which had hindered the development of free
inquiry, was in many quarters cast off. The sciences,
hitherto studied almost alone in the cloister, now found a
foothold in the universities of France, England, Germany
and other countries, which were then both increasing in
number and expanding rapidly ; the free interchange of
ideas among these seats of learning rendered a development
of the sciences possible, as it had never been before. That
the discovery and spread of the art of printing contributed
materially to this, hardly requires to be stated; for new
ideas, which were opposed to those prevalent up till then,
and which had hitherto been restricted to a narrow circle,
became quickly disseminated by its aid. Any one could
inform himself as to the range of any particular science by
means of the encyclopedias and special memoirs which were
being printed in increasing numbers. As a consequence of
this, the capacity for independent criticism spread, one of
the most effectual of remedies against the domination of
the scholastics being thereby created. A further aid to
controverting scholastic principles was found in the in-
F
THE IATRO-CHEMICAL PERIOD CHAP.
ductive method, then gradually forcing itself forward, by
means of which the experimental sciences were called into
life.
In addition to these impulses of a freer spirit, chemistry
received a powerful impetus from the increase in scientific
knowledge which resulted from the discovery of the New
World and of the ocean route to the East Indies. All these
events testified to the birth of a new era, which found
its most powerful expression in the works of the Reforma-
tion.
At that time chemistry strove to free itself from the
exclusive domination of the alchemistic idea. And even
although the latter was not totally supplanted, still another
aim came into prominence, an aim to which a scientific
character could not be denied ; the chemical knowledge of
that day was, however, so very imperfect that a solution of
this new problem was not to be expected. Chemistry was,
in fact, to be intimately conjoined with medicine ; each (so
many opined) was to help the other. The chemist was to
discover the medicines, prepare them carefully, and investi-
gate them chemically, while the physician was to examine
and explain their action ; or, better still, both things were to
be united in one person. The mutual interaction of chemistry
and medicine is the main idea which runs through the iatro-
chemical age, and which gives to the latter its own particular
stamp.
What benefit, then, accrued to both of them from this ?
The answer is, a mutual enrichment, which did almost more
for chemistry than for medicine : for the former was raised
to a higher level through being transferred from the hands
of laboratory workers, who were mostly uneducated, to those
of men belonging to a learned profession and possessing a
high degree of scientific culture. The iatro-chemical age
thus formed an important period of preparation for chemistry,
a period during which the latter so extended her province that
she was enabled in the middle of the seventeenth century to
stand forth as a young science by the side of her elder sister
physics. That period was for chemistry an apprenticeship in
in LIFE AND WORK OF PARACELSUS 67
the fullest sense of the word, during which she laboriously
acquired the capacity to see that the iatro-chemical doctrines
were untenable, and to apply herself to her true vocation.
GENERAL HISTORY OF THE IATRO-CHEMICAL PERIOD
AND PARTICULARLY OF ITS THEORETICAL VIEWS.1
The main currents of the iatro-chemical age emanated
from Paracelsus, van Helmont and de le Boe Sylvius, with
whose name must be coupled that of his most distinguished
pupil, Tachenius, their doctrines being spread by schools
of greater or lesser importance. Besides these there were
some men who worked independently, or who at least did
not entirely subordinate themselves to their authority, of
whom Libavius, Glauber and Sala may be mentioned. Other
men like Agricola, Palissy, etc., employed their energies in
a totally different direction, giving all their attention to
technical chemistry.
Paracelsus and his School.2 — Paracelsus was the man
who, in the first half of the sixteenth century, opened out
new paths for chemistry and medicine by joining them
together. To him is undoubtedly due the merit of freeing
chemistry from the restrictive fetters of alchemy, by a clear
definition of scientific aims. He taught that " the object
of chemistry is not to make gold but to prepare medicines."
True, chemical remedies had been employed now and again
before his time, Basil Valentine in particular having sug-
gested their use ; but Paracelsus differed from his predecessor
in the theoretical motives which led him to employ them.
1 Cf. Kopp, Geschichte der Chemie, vol. i. p. 84.
2 The recent researches upon Paracelsus — more especially Fr. Mook's
Theophrastus Paracelsus (Wurzburg, 1876) ; E. Schubert and K. Sudhoff's
Paracelsus- Forschungen (Frankfurt, 1887-9) ; and Aberle's Grabdenkmat,
Schddel und Abbildungen des Theophrastus Paracelsus, etc. (Salzburg, 1891)
("The Gravestone, Skull, and Portraits of Theopbrastus Paracelsus, etc.")
— have thrown much light upon the life and works of this truly eccentric
man. They materially enhance our appreciation of the real services which
he rendered.
F 2
68 THE IATRO-CHEMICAL PERIOD CHAP.
He regarded the healthy human body as a combination of
certain chemical matters ; when these underwent change
in any way, illnesses resulted, and the latter could therefore
only be cured by means of chemical medicines. The fore-
going sentence contains the quintessence of Paracelsus'
doctrine ; the principles of the old school of Galen were
quite incompatible with it, these having- — indeed — had
nothing to do with chemistry.
Paracelsus entered the lists with great boldness and with
a marvellous vigour, to combat the old doctrines long accepted
by all physicians. Although his exaggerations here are
distinctly to be condemned, still he effectually obviated by
his action the growing stagnation of medicine, and partly
carried through valuable innovations, partly incited others
to do so.
His career was not calculated to raise him in the esteem
of his opponents, that is, of nearly all the physicians of the
time. Paracelsus (his full name was Philippus Aureolus
Paracelsus Theophrastus Bombastus) was born at Einsiedeln1
in Switzerland in 1493, and returned to his native country
about 1525 as a physician celebrated for his wonderful
oures, after an extremely unsettled life and the most roman-
tic wanderings in almost every country in Europe. The
chair of Medical Science (therapeutics) at Basle was conferred
upon him, and this position, together with his fame as a
doctor, he made use of to spread the iatro-chemical doctrine,
.and to fight against the old medical school with every
possible dialectic weapon. He discredited the hitherto
undisputed authority of Galen and Avicenna, and succeeded
by means of popular lectures given in German, as well as
by his rude originality, in gaining a large number of
adherents. A quarrel with the Basle Municipal Council
soon compelled him, however, to leave that town (in 1527),
and after moving about restlessly in Alsace, Bavaria, Austria
and Switzerland, he at last came to Salzburg in the Tyrol,
where he died in 1541 in wretched circumstances. The
1 The name Eremita (Hermit) which was given to him by many, recalled
that of his native town (the verb einsiedeln means " to live like a hermit ").
in THE SYSTEM AND VIEWS OF PARACELSUS 69
assertion that Paracelsus was done to death by the hirelings
of physicians who were his enemies, has been proved to be
unfounded (Cf. Aberle, loc. cit.).
There has at all times been much difference of opinion
in criticising this gifted man, whose life offered such a rude
contrast to his mental capacity. Rated too high and even
extolled by his disciples,1 and also by many who disapproved
of his doctrines, he was, on the other hand, disparaged by
his opponents and by chemists who criticised him as
historians. The good to which he incited by his reforming
labours seldom found the recognition it deserved, from its
being so much mixed up with charlatanism and coarseness,
while the overweening estimation in which he held himself
helped to make him ridiculous in the eyes of thoughtful
physicians.
At the root of his iatro-chemical doctrines, which he
imagined were based upon ample experience, lay the
idea already mentioned, — that the operations which go
on in the human body are chemical ones, and that the
state of health depends upon the composition of the organs
and the juices. With respect to the constituents of organic
bodies, Paracelsus adhered to Basil Valentine's assumption
that the latter were composed of mercury, sulphur and salt.
Indeed, in spite of many contradictions in the details of his
theoretical views, this hypothesis forms the foundation of
his whole system.2 When one of these elements predomi-
nates or when it falls below its normal amount, illnesses
ensue. This idea is expressed in the most fantastic manner
in the writings of this strange man, as the following sentences-
show : —
An increase of the sulphur gives rise to fever and the plague,
an increase of mercury to paralysis and depression, and an in-
crease of salt to diarrhoea and dropsy. By the elimination of
1 Cf. A. N. Scherer's memoir Theophrastus Paracelstus (St. Petersburg,
1821). Francis Bacon criticised him more reasonably, praising his endeav
ours to get at the truth through the light of experience.
2 Medicine rests, according to the confused statement of Paracelsus,
upon four pillars, of which chemistry forms one ; the three others are
philosophy, astronomy and virtue.
70 THE IATRO-CHEMICAL PERIOD CHAP.
the sulphur, gout results, and by distilling it from one organ
into another, delirium, and so on. — However unfounded such
opinions are, it is possible to find a certain sense in them ;
on the other hand, his utterances upon the relations of the
individual organs and the secretions of the human body to the
metals and planets, to both of which he ascribes a mystical
influence, are quite unintelligible. Not less incomprehensible
is his assumption of a connection between the plague and
shooting stars. He designates tartarus as the cause of
various illnesses, meaning by this expression precipitates from
juices which in the healthy state contain no solid particles.
The deposition of concretionary matter, which he may have
observed in the affected organs during many diseases (such
-as gout, stone in the kidneys and gall-stones), no doubt led
him to this partially sound conclusion. The comparison of
such secretions with known sediments, particularly with
tartar, led to the general designation tartarus ; the word
had possibly also a double meaning, recalling the severe pains
which people afflicted with these ailments had to endure.
While Paracelsus endeavoured in this semi-rational, if also
fantastic, manner to reduce pathological processes to
chemical causes, he assumed nevertheless for his iatro-
chemical doctrine the action of particular forces in certain
cases, which forces he, in his drastic manner, pictured to
himself as personified. Digestion, in especial, was regulated
by the action of Archeus, who — as a good genius — rendered
the nutriment consumed digestible, effected the separation
of indigestible matters, and provided generally for the
preservation of a proper equilibrium. Diseases in the
stomach were produced by Archeus becoming ill. In this
interpretation of such a specific chemical process as digestion,
Paracelsus was disloyal to his own principles. It fell to the
later iatro-chemists to clear their doctrinal system from
this incongruity.
Diseases were to be cured by medicines (arcana), the
preparation of which, as we have already seen, was —
according to Paracelsus — the aim of chemistry. Due
recognition must be given here to the fact that this
in SERVICES RENDERED BY PARACELSUS 71
axiom infused new life into the effete medical doctrines.
Paracelsus enriched medicine with a large number of
valuable preparations. The manner in which he applied
most of these must remain unknown to us ; but it is certain
that he effected numerous brilliant cures in cases of serious
illness. With regard to the preparations which he employed,
we know that he was the first to stamp copper vitriol, corrosive
sublimate, sugar of lead and various antimony compounds
as medicines, these metallic compounds having hitherto been
looked upon with dread, on account of their poisonous
properties. Further, he brought into use dilute sulphuric
acid, " sweetened oil of vitriol " (sweetened by spirit of wine,
and which was known at a later date as Haller's acid),
tinctures of iron and iron saffron ; and he also introduced
better methods for preparing and utilising various essences
and extracts. He appears to have attained great success by
the judicious prescription of laudanum.
That Paracelsus gave a tremendous impetus to the higher
development of the apothecary's calling by such generous
additions to the medical treasury goes without saying ; for
before his time apothecaries' shops were nothing more than
stores for roots, herbs, syrups and confections of every kind,
the preparation of the latter being carried out exclusively
in them. The making of new medicines presupposed an
acquaintance with chemical facts and processes ; pharmacists
had therefore to be continually striving to attain to this
knowledge, pharmacy, in the proper sense of the word,
taking its beginning here. The service which Paracelsus
rendered in instigating physicians and apothecaries to busy
themselves with chemistry was a great one, but Scherer goes
too far when he says that " pharmacy owes everything to
Paracelsus." l
The trenchant innovations which Paracelsus strove to
introduce gave rise to violent agitations among his contem-
poraries, agitations which were continually receiving new
food from his numerous memoirs, circulated in various
languages, and dating the most part from the time after
1 Loc. tit.
72 THE IATRO-CHEMICAL PERIOD CHAP.
his departure from Basle. These gave frequent opportunity
for vehement contradictions on the part of the old medical
school. So far as their composition goes, his writings stand
upon a very low level, faithfully reflecting as they do the
unsettled life and rude attitude of their author. Every
one of them shows an illimitable self-conceit, many indeed
being written in a manner quite unworthy of an educated
man. His chemical knowledge and his views with regard
to the origin of diseases are best seen in the following
works : — Arclidioxa ; De Tinctura Physicorum ; De Morbis ex
Tartaro Oriundis ; Paramirum ; Grosse Wundarznei.
The results of the labours of Paracelsus were not
long in manifesting themselves. His pupils, inspired by
the new doctrines, glorified him as the reformer of
medicine; while the adherents of the old school, on the
other hand, resisted desperately the innovations and attacks
which undermined their views. A violent contest ensued and
continued for a long time, until it was decided, if not in
favour of Paracelsus, at least in that of the more moderate
iatro-chemists. It does not lie within the scope of this
work to enter minutely into these controversies, sufficing
as it does to indicate here the significance of the new
medico-chemical views for the development of chemistry./
But we may mention that the Swiss physician Erastus
(whose German name was Lieber), who remained faithful
to the doctrines of Galen, was Paracelsus's chief opponent,
and was especially instrumental in exposing the mischievous
contradictions which were accumulated in his later writings.
The medical world was agitated during the sixteenth century
by polemical writings on both sides. Of the disciples of
Paracelsus, who, less gifted than their master, paraphrased
his ideas and imitated his less amiable peculiarities,
especially his charlatanism, but who fell short of him as
scientists, Leonhard Thurneysser1 (called zum Thurm) was
1 A good account of Thurneysser' s performances is to be found in
Mochsen's admirable work, Beitrage zur Geschichte der Wissenschaften in der
Mark Brandenburg, etc. (Berlin and Leipzig, 1783). Cf. also A. W. Hof-
mann's admirable lecture, Berliner Alchemisten und Chemiker (1882).
in TURQUET DE MAYERNE; LIBAVIUS; CROLL 73
the best known. The latter achieved nothing of any note
for chemistry, but his unsuccessful appearance as an
adept ensures for him a place in the history of alchemy
cf. (p. 62).
The acts of men of this calibre, who wrought immense
mischief by the reckless use of poisonous preparations,
render intelligible the attempts which were made to put a
stop to their excesses by legal statute. This is seen, for
instance, by the parliament of Paris prohibiting the
prescription of antimonial preparations, and by the sentence
of condemnation which the medical faculty of Paris hurled
against every attempted innovation in the healing art.
But there belonged also to the school of Paracelsus men of
scientific eminence who did not subscribe to all his doctrines,
but rather regarded them from a critical point of view, and who
endeavoured in a rational manner to extract the good which
they contained. The most prominent of these at the end of
the sixteenth and beginning of the seventeenth centuries were
Turquet de Mayerne and Libavius, Oswald Croll and Adrian
van Mynsicht. These were for some time contemporaries
of van Helmont, and formed the connecting link between
Paracelsus and that remarkable man. They greatly enriched
not only medicine but also chemistry.
Turquet de Mayerne was born at Geneva in 1573,
and became a noted physician in Paris. Holding, however,
as he did, that the antimonial preparations now in ill-
repute were necessary, and therefore prescribing them, he
found it impossible to keep on good terms with his professional
brethren in that city, and preferred to become body-physician
to the King of England, in which country he died in 1655.
His knowledge of chemistry was very highly developed for
that age, as a consequence of which he laboured earnestly
for the rational application of chemical remedies, without
falling into the exaggerations of Paracelsus on the one hand,
or rejecting all the medicines of the school of Galen on the
other.
The physicians Croll and van Mynsicht busied them-
selves in a similar manner and at about the same time.
74 THE IATRO-CHEMICAL PERIOD CHAP.
Having a good knowledge of chemistry, they brought into
vogue many of the medicaments of Paracelsus, together with
other new preparations; among the latter, Croll was the
first to recommend the use of sulphate of potash and of
volatile salt of amber (succinic acid), and van Mynsicht that
of tartar emetic.
Andreas Libavius (Libau) attracts our attention in a
high degree by the critical position which he took up with
regard to the gross errors of the school of Paracelsus, and
especially also by many new observations which,, he con-
tributed to chemistry. He was the first chemist of note in
Germany who stood up manfully against the excesses of
Paracelsus, and who vigorously combated the defects in
his doctrines, the obscurities in his writings, his phantasies
and sophisms, and the employment of "secret remedies."
Originally a physician, Libavius attained to a wide knowledge
of chemistry, which he helped to extend, although latterly he
devoted himself chiefly to historical and philological studies.
He died in 1616 as director of the gymnasium at Coburg,
having previously worked with great success as a physician and
at the same time as head of the " Latin School " at Kothenburg
on the Tauber from 1591 to 1607. Thanks to his medical
knowledge and to his thorough general education, Libavius
was able to appreciate better than his contemporaries the
influence which chemistry ought to exercise upon medicine ;
he took up a position midway between those of Paracelsus
and his opponents, the latter of whom wished nothing less
than to banish chemistry from medical science. Notwith-
standing his sound judgment, however, of which he gave
many proofs, he could not quite free himself from the
predilection of his time towards alchemy.
Libavius did chemistry a real service in writing his
text-book, which was published in 1595 under the title
Alchymia, and which contained all the most important facts
and theories germane to the subject at that date. His
other writings, in which he combated the weak points of
the Paracelsian school (as indicated above), and also
described new chemical observations, appeared in three
in VAN HELMONT'S LIFE AND WORK 75
volumes shortly before his death, under the title Opera
Omnia Medico-chymica. We shall still have frequent
occasion to refer to his practical chemical knowledge, which
was attested by the discovery of important facts.
It is worthy of note that Libavius made a vigorous
effort to establish chemical laboratories, in which scientific
work should be carried out. From the proposals which he
brought forward with this end in view, it is evident that he
was desirous to provide plenty of accommodation in these
laboratories, and to furnish them with fittings of the most
varied kind.1
Johann Baptist van Helmont and his Contemporaries.
A distinguished place and a detailed notice in the
history of the iatro-chemical period is due to van Helmont,
one of the most eminent and independent chemists of his
time. Endowed with rich acquirements and experiences in
medicine and chemistry, he surpassed those of his con-
temporaries who worked in the same field. His life was
for the most part that of a scholar working in quiet,
although his brilliant outward circumstances (he belonged
to a noble Brabantine family) were hardly in keeping with
this. Born in Brussels in the year 15*77, he applied him-
self at an unusually early age to the study of philosophy
and theology; but finding no satisfaction in these, he
renounced them to devote himself to medicine. At first
an adherent of the old school of the Galenites, he soon
recognised its deficiencies and turned to the doctrines of
Paracelsus, accepting them, however, only in part. With a
growing enthusiasm for his physician's calling, he fought
against the old medical system, and materially contributed
by his brilliant services in bringing about its fall. Without
van Helmont, iatro-chemistry would never have attained to
1 For an account of the life and work of Libavius, cf. Ottmann's lecture
in the Verhandlungen der Gesetlschaft Deutscher Naturforscher, etc., 1894,
vol. ii. p. 79.
76 THE IATRO-CHEMICAL PERIOD CHAP.
the height to which it was raised later on by Sylvius and
Tachenius. In addition, he enriched pure chemistry by a
very great number of valuable observations. So attached
did he become to his scientific pursuits that he declined
the tempting offers of princes, preferring to investigate the
secrets of nature in his laboratory at Brussels, in which city
he died in 1644.
In van Helmont wonderful contradictions were united.
In contrast with his gift of sharp and temperate observation,
there was an intense inclination towards the supernatural, —
possibly the result of his mystical and magical studies, to
which, as well as to theology, he had applied himself. Thus
this same man, who laid the foundation of the first know-
ledge of gases, and showed thereby a keenness of perception
unapproached before his time by any other observer, defended
the transmutation of the base metals into gold with the
utmost vigour (cf. p. 61) ; his belief in this was grounded so
firmly that illusions arose from it which are to us incompre-
hensible.
After this it is easy to understand that van Helmont
was not free from fantastic ideas of a less questionable
nature. His theoretical views upon the elements and his
iatro-chemical doctrines yield many proofs of this ; but, on
the other hand, much of his knowledge was so sound, and'
he was able to expound it so much better than any of his
predecessors, that the good service which he rendered far
outweighed the bad effect of any of his mistakes.
Van Helmont had his own opinion with regard to the
primary substances of which matter was composed ; he
neither accepted all the four Aristotelian elements1 nor
those which were assumed by Basil Valentine, but looked
upon water as the chief constituent of all matter. That it
was present in organic bodies he concluded from the fact of
invariably finding it as a product of their combustion. He
imagined that he contributed a strong proof of this by an
1 With respect to air, it is uncertain whether van Helmont looked upon
it as an element or not. He denied altogether that fire could be of a material
nature, which is evidence of his extraordinary clearness of perception.
in VAN HELMONT'S CHEMICAL KNOWLEDGE 77
experiment which showed that plants could be made to grow
luxuriantly in pure water alone, which, he believed, was
their only nutriment under the circumstances. That he was
thereby convinced of the transformation of water into earthy
matter is therefore quite intelligible.
Whilst van Helmont thus subscribed to the same error
that held possession of many minds both before and after his
time, he nevertheless recognised much more clearly than his
contemporaries the unchangeableness of matter in numerous
instances ; thus he contributed more than any one else
to do away with the belief that the copper thrown down from
a solution of copper vitriol by means of iron was newly
created. He further showed that the same substance con-
tinued to exist in many of its compounds, e.g., silver in its
salts, and silica in water glass, the latter yielding, on
decomposition with acids (according to his own memorable
observations), the same amount of silicic acid as was originally
used to prepare it. These were views and observations of
the greatest moment; for, in place of the former obscure
conceptions as to the formation of chemical compounds, he
substituted the doctrine that the original substance, even
after undergoing chemical changes, remains present in the
new products. He had therefore clearly grasped the
fundamental idea of the conservation of matter in particular
cases.
Van Helmont thus stands out as unique in those ideas,
which pointed out new paths to chemistry. The relations
between chemistry and medicine too, the latter of which he
also ardently fostered, led him to views which likewise
possess a partial originality, since he endeavoured to decide
theoretical questions by means of experiments with juices
and other secretions of the animal body. The reactions
which go on in the liquids of the body were in his opinion of
especial importance, for, according as the latter were acid or
neutral, they regulated its most important functions. Besides
the chemical nature of the juices, fermentation was, according
to him, the principal cause of the organic processes ; but he
expresses himself less clearly upon this point than upon the
78 THE IATRO-CHEMICAL PERIOD CHAP.
significance of the chemical reactions. Indeed, he could not
quite free himself from the idea of Archeus governing diges-
tion and the processes connected with it. On the other
hand, he stood on solid ground in his explanation of vital
processes, when he took into account the chemical nature of
the juices. He held that the acid of the gastric juice
brought about digestion, but this, if present in excess, gave
rise to discomfort and illnesses, which were the more serious
the more acid there was ; and the latter could not then, as
under normal conditions, be neutralised by the alkali of the
bile, which mixes with the gastric juce in the duodenum.
To cure any of the ailments produced in this way, van
Helmont declared that medicines of an alkaline nature
(alkaline salts) must be used ; while those of an opposite
kind, which arose from a deficiency of acid, were to be
treated by medicines of an acid nature. He also recom-
mended the latter in cases of gout, stone and similar diseases,
which likewise originated (in his opinion) from an insufficient
or irregular admixture of the juices. These views show a
distinct advance upon those of Paracelsus. For, while the
latter assumed the presence of arbitrary constituents — in-
capable of preparation — in organic matter, van Helmont
searched for the actual substances themselves, and compared
the interactions of the various juices which mingle with one
another with similar reactions of solutions outside the organs ;
a procedure which laid the first foundation, however insecure,
of chemical physiology.
Van Helmont proved himself an original investigator of
the first rank, who opened out new ground for chemical
science by his researches on gases — researches which con-
stitute him the real founder of pneumatic chemistry ; though
this indeed only attained to a considerable development a
century after his time, when the discoveries connected Avith
it brought about the great reform of the science. If we
consider that before van Helmont's time the most various
gases, such as hydrogen, carbonic acid and sulphurous acid,
were looked upon as not differing materially from ordinary
air, and that he was the first to characterise gaseous sub-
in VAN HELMONT'S INFLUENCE ON CHEMISTRY 79
stances as different, by investigating their properties, we
gain some idea of the immense services which he rendered.
He it was who gave to them the generic name of " gas," l
and he further distinguished them from vapours, in so far
that the latter were condensed to liquids upon cooling, while
the former were not.
Van Helmont specially examined carbonic acid, and
showed how it was produced from limestone or potashes
with acids, from burning coal, and in the fermentation of
wine and beer ; he also pointed out its presence in the
stomach, and its occurrence in mineral waters and in many
natural cavities in the earth. He usually termed it gas
sylvestre? To the want of suitable apparatus for collecting
gases are to be ascribed the imperfections in many of his
observations, and also the confounding of carbonic acid with
other gases which were non-supporters of combustion like
itself; nevertheless he described the two combustible gases
—hydrogen and marsh gas — as peculiar varieties of air.
His collected works were published in 1648 by his son
under the title, Ortus Medicince ml Opera et Opuscula Omnia.
Van Helmont's influence upon his contemporaries and
upon the development of the iatro-chemical doctrines must
be rated very high. By his introduction of chemical ideas
into medical science, the latter was advanced, because the
use of chemical medicines seemed natural from thence-
forth; moreover, in his Pharmacopolium ac Dispensatorium
Modernum, he published suitable prescriptions for the pre-
paration of medicines. The scientific spirit which he
endeavoured to introduce into the healing art tended to
its more healthy development, in contrast with the crude
empiricism of the Paracelsian school.
In a similar manner, if in lesser degree, various other
physicians of that time were also active. Well equipped
1 In choosing this designation, van Helmont had Chaos in his mind, —
possibly also the process of fermentation (the Dutch word for the verb " to
ferment" is gisteri).
2 By the designation sylvestre, he doubtless meant to indicate the im-
possibility of condensing the gas ; at least he says in one passage : Gas
sylvestre, sive inco'ercibile, quod in corpus cogi non potest visibile.
80 THE IATRO-CHEMICAL PERIOD CHAP.
with chemical knowledge, they pursued the practice of their
calling, and were enabled by their clearness of vision to re-
cognise and combat many evils, e.g. those which arose from
the use of secret remedies ; among them we must mention
Angelus Sala and Daniel Sennert. Sala, who practised as
body-physician at the Mecklenburg Court in the first half of
the seventeenth century, awakens our surprise by his able criti-
cisms both of the Paracelsian and of the old medical schools,
and also by his (for that time) wide knowledge of chemistry.
This knowledge, conjoined with his solid medical experience,
was of the utmost value not only to pharmacy but also to
pure chemistry; for he formed correct ideas with regard to
the composition and reactions of many chemical compounds,
such as had never been advanced before his time. Thus he
tells us that salmiac consists of hydrochloric acid and car-
bonate of ammonia (fluchtiges Laugensalz), and he also knew
that sulphuric acid was able to drive out nitric acid from its
salts, — and so on.
Sennert, who taught as professor at Wittenberg in the
first quarter of the seventeenth century, devoted his energies
chiefly to proving to the medical world the wonderful
efficacy of chemical remedies, when these were properly applied.
It is true that he was never able to disentangle himself
from many of the- erroneous conceptions of Paracelsus, for
instance, from the doctrine of the three primary elements ;
but he worked effectively against the serious abuses
which had crept into medicine through the influence of
the last-named, especially against the so-called universal
remedies.
^Sylvius and Tachenius. — F. de le Boe (Dubois)
Sylvius was born at Hanau in 1614, and, after a thorough
grounding in scientific and medical studies, practised with
great success as a physician, and later on, until his death in
1672, was famous as professor of medical science in Leyden.
In his knowledge of medicine he far surpassed most of his
contemporaries. He was aware of the difference between
arterial and venous blood, and ascribed the red colour of the
in SYLVIUS AND TACHENIUS 81
former to the air absorbed in breathing. Combustion and
respiration were in his view precisely similar phenomena.
He directed all his efforts, as instanced in this latter case,
to proving that the processes which go on in the human body
— whether they be normal or pathological — were purely
chemical ones. The spiritualistic element which was mingled
with the doctrines of Paracelsus and van Helmont was to
be entirely set aside. Digestion, for instance, which only
appeared possible to the two latter by the intervention of
a spirit (Archeus), was regarded by Sylvius as a chemical
process in which the saliva primarily, but also the gastric
and pancreatic juices and the bile, were the most important
acting agents. To the acid, alkaline, or neutral reactions of
the juices of the body he ascribed an equal, if not a higher,
significance than van Helmont himself, following the latter
in this as in similar questions. Sylvius had a predilection for
comparing chemical with physiological and pathological pro-
cesses, which frequently led him into error. Medicine as a
whole, he considered, ought simply to be applied chemistry.
That these one-sided endeavours were bound to miscarry,
considering the state of chemical knowledge at that time,
requires no demonstration. And it is equally easy to
understand why his chemical doctrines brought less benefit
to medicine than to chemistry, seeing that educated physicians,
if they wished to comprehend them, were compelled to go
minutely into the study of chemical questions. This applied
in a very special degree to the new remedies, the prepara-
tion and rational application of which presupposed a know-
ledge of chemistry. Sylvius, addicted as he was to the use
of heroic medicines, did not hesitate to prescribe lapis
infernalis (nitrate of silver), sublimate and zinc vitriol for
internal use; and he was particularly enthusiastic about
antimonial and mercurial preparations.
While there are but few discoveries in pure chemistry
by Sylvius himself to chronicle, his pupil Otto Tachenius
proved himself an independent investigator, to whom the
science is indebted both for extremely valuable observations
and for speculations deduced from these. Of his life we
G
82 THE IATRO-CHEMICAL PERIOD CHAP.
only know that he was born at Herford in Westphalia, and
that, after moving about from place to place as an apothecary's
assistant, he applied himself to the study of medicine in
Italy towards the middle of the seventeenth century, and
practised in Venice as a physician. Although he attached the
greatest weight to clear relations between chemistry and
medicine, he had no hesitation in working mischief with
secret remedies. Tachenius was the last iatro-chemist of
note who followed the doctrines of Sylvius with enthusiasm.
In addition to him may be mentioned here the famous
English physician Willis (pb. 1675), who likewise advocated
similar views.
Tachenius, among his other valuable observations, con-
tributed materially to elucidating that problem which Boyle
considered the most important of all, viz. a knowledge of
the composition of bodies. It was with him that the first
serviceable definition of the term " salt," as a compound of an
acid and an alkali, originated. His statements on the com-
position of various compounds show great acuteness, which is
also seen in the value he attached to certain reactions as
tests for different substances. While Tachenius thus laid the
foundations of qualitative analysis in a more systematic manner
than his predecessors, his attention was also directed to the
quantitative proportions in which substances react chemically
— a point to which hardly any attention had hitherto been
paid ; and this he exemplified with tolerable accuracy by noting
the increase in weight which took place when lead was
transformed into minium. His writings, and also those
of his master Sylvius, treat for the most part of subjects
of chiefly medical interest, but, as we have just seen, facts
and opinions of importance to chemistry are also recorded
in them.
If we wish to arrive at the main result which the iatro-
chemical doctrines produced upon the development of chem-
istry, we must particularly bear in mind the point already
touched upon, viz. that the study of chemistry by physicians
who had had a thorough education helped materially to shape
its course on scientific lines. Notwithstanding the numerous
in DEVELOPMENT OF CHEMISTRY 83
errors and fantastic conceptions in which the iatro-chemists
were involved, we come across many very striking views, —
views which exercised a marked influence upon the whole
tendency of the succeeding epoch. Of these we would
mention here: (1) the recognition of the more intimate
components of salts, and the clearer comprehension of what
was meant by the terms "chemical compound" and "chem-
ical affinity," by a knowledge of which the chief aim of
chemistry, i.e. the investigation of the true composition of
bodies, was effectively advanced; and (2) the recognition
of the analogy between the processes of combustion and the
calcination of the metals on the one hand, and respiration on
the other. These were doctrines of very great weight indeed.
The phlogistic hypothesis, too, which predominated during the
greater portion of the eighteenth century, was indicated by
many of the iatro-chemists ; i.e. many of the latter had ideas
upon combustion which approximated to those of the phlo-
gistonists. Lastly, van Helmont's work upon gases exercised
the greatest influence on the development of pneumatic
chemistry, from which the impulse to the great reform of our
science at the end of last century sprang.
It is thus evident that many of the aims of the phlo-
gistonists were intimately connected with the observations
and opinions proper of the iatro-chemists. And while the
medico-chemical opinions of the latter were rudely upset
after the middle of the seventeenth century, their facts and
theories appertaining to chemistry were the means of guiding
the latter into scientific paths.
Agricola, Palissy, and the other Promoters of Applied Chemistry
during the latro-chemical Age.1
Independently of the main iatro-chemical current, chem-
istry in its applications to industries was fostered by men
who possessed, for their time, sound chemical knowledge.
1 Cf. Kopp, Gesch. d. Chem., vol. i. pp. 104, 128; and Hofer, Histoire
de la Chimie, vol. ii. pp. 38, 67 e.t seq.
G 2
84 THE IATRO-CHEMICAL PERIOD CHAP.
The chief of these were Georgius Agricola, who directed his
attention specially to metallurgy; Bernard Palissy, who
developed the ceramic art; and Joahnn Rudolf Glauber, who,
without ceasing to be an iatro-chemist, devoted his powers
for the most part to technical chemistry. The following
paragraphs give a few details explanatory of the services
rendered to the science by the knowledge and experiences of
those men ; but what we are chiefly concerned with here is
their significance from a more general point of view.
Georgius Agricola l was born at Glauchau in 1494, and be-
came a noted physician ; he died while mayor of Chemnitz
in 1555. He was thus a contemporary of Paracelsus. Al-
though, like the latter, a medical man, he followed totally differ-
ent lines. Without troubling himself about the storms which
raged round medicine in his day, he devoted himself by choice
to the study of mineralogy and metallurgy, being impelled
thereto by the flourishing mining and smelting industry of
Saxony, while at the same time he continued to practise as
a doctor. His chemical knowledge and wide experiences are
detailed by him in his principal work : De Re Metallica, libri
XII, which remained for a long time the most important
text-book of mineralogy. Through this, as well as through
his other writings — of which De Natura Fossilium, libri Jf,
and De Ortu et Causis Subterraneorum were also of especial
mineralogical value, — there runs quite a different tone from
what we find in Paracelsus. They are characterised by a
clearness of expression, a temperate conception of the opera-
tions described, and a distinct description both of the
apparatus employed and the processes followed, — qualities
which stamp Agricola as a true investigator. It was through
his writings, especially through the first of those named
above, that the more important operations in the working
up of ores for their metals first became generally known ;
and he was likewise the first to explain intelligibly the
1 Cf. G. H. Jacobi's dissertation : — Der Mineralog Georgius Agricola
und sein Verhattniss zur Wissenschaft winer Zeit (Leipzig, 1889). ("The
Mineralogist, Georgius Agricola, and his relation to the Science of his
Time.")
in GEORGIUS AGRICOLA, PALISSY AND GLAUBER 85
manufacture of other products obtained by smelting, and
of various preparations of technical importance. His works
are indispensable to the history of metallurgy.
His quiet objective modes of thought and investigation
did not, however, prevent him in his more mature age from
attributing a certain degree of liklihood to the alchemistic
problem, to which he had devoted himself warmly in his
youth; at the same time he had no sympathy with the
wild exaggerations which even then prevailed.
Working on lines similar to those of Agricola, and at about
the same period, the Italian Biringuiccio of Siena busied
himself with the processes of metallurgy, as detailed in his
work Pirotechnia, which appeared in 1540. This too is
marked by the clearness and exactitude with which various
technical procedures are described. Biringuiccio held aloof
from the iatro-chemical questions and the alchemistic doc-
trines of his day.
Bernard Palissy became distinguished as an investigator,
and as a man who allowed himself to be guided solely by the
results of experiment, at a time before the inductive method
was commonly recognised as the means of attaining to the
truth. It was in the domain of ceramic art that his principal
work lay ; and, although frequently disappointed in the results
he obtained, his untiring efforts at improvment in it were
ultimately followed by success. The simple and clearly
written works of Palissy enable us to appreciate the labours
and struggles of this remarkable and steadfast man, who,
beginning as a common potter destitute of the higher educa-
tion, became the great authority on his subject.1 He took his
first lessons from the book of nature, as he himself tells us ; 2
putting observation and experiment in the foreground, he
combated every speculation which was not based upon these,
especially such doctrines as had merely the stamp of authority
to back them. There could hardly have been any man of his
1 Hofer, who was the first to recognise the services of Palissy as they
deserved, speaks of him as " un des plus grands hommes dont la France
puisse s'enorgueillir " (Histoire de la Chimie, vol. ii. p. 92).
2 " Je rial point eu d'autre livre, que le del et la terre, lequel est connu de
tons et est donnd cl tons de connoistre et lire ce beau livre."
86 THE IATRO-CHEMICAL PERIOD CHAP.
time more free from prejudice ; his clear understanding and
circumspect criticism enabled him to cast aside the doctrines
o f Paracelsus, and to make use of the weapons of ridicule
against the mistaken beliefs of alchemy. His life extended
over nearly the whole of the sixteenth century, and might be
said to consist of a series of vicissitudes. Along with Agricola
he maybe looked upon as the chief exponent of experimental
chemistry in his time. His acuteness was further evidenced
in the domains of mineralogy and agricultural chemistry, to
the founding of which branches of science he largely con-
tributed.
Johann Rudolf Glauber, who was born at Karlstadt in
Franken (Bavaria) in 1604, and who died in 1668 at
Amsterdam, fostered applied chemistry ardently, and enriched
it by valuable observations. It was in this direction that
he chiefly worked, his iatro-chemical labours holding but a
secondary place. His life was an extremely restless one,
which may not improbably account for the unsettled and
almost discontented tone which runs through many of his
writings. Without a classical education, and imbued with
the prejudices of his age, he has been well designated the
Paracelsus of the seventeenth century. He was, in fact,
addicted to fantastic and superstitious ideas, and therefore
also to the extravagances of alchemy ; on the other hand, he
possessed exceptional talents of observation and invention,
regarding which some details will be given in the next section
of this book. In theoretical points of chemistry, too, he gave
proof of his clear-sightedness, explaining, for example, many
of the effects of chemical affinity in the decomposition of salts
by acids or bases, — and so on. He was the first to explain a
case of what we call double decomposition, — the mutual
action of mecuric chloride and antimony trisulphide upon one
another. Mention must also be made here of his perspica-
city in questions of national economy, his writings upon which
are to be found mixed up with his chemical papers, especially
in the six-volume work Teiitschland's Wohlfarth (" The Weal
of Germany "). Time after time Glauber sought to demon-
strate that his country should work up and improve its own
in ADVANCES IN TECHNICAL CHEMISTRY 87
products, and not leave this for other nations to do ; instead
of buying at a dear rate manufactured articles whose raw
material was obtained from Germany, that country ought to
make and export them herself.
With Glauber and Tachenius the iatro-chemical period
closes. Both of them belonged in many of their chemical
ideas and also in point of time (during the last years of their
lives) to the succeeding era, between which and the previous
one it is impossible to draw an absolutely sharp line. Both
aided chemistry by observations of extreme value, and
materially advanced the experimental method, which became
from thenceforth the sure guiding star of chemical research.
EXTENSION OF PRACTICAL CHEMICAL KNOWLEDGE IN
THE IATRO-CHEMICAL AGE.1
As was to be expected from the whole tendency of this
period, during which chemistry became so intimately united
to medicine, the gain of knowledge lay chiefly in respect to
chemical preparations, which it was hoped to apply as medi-
cines. The efforts to discover new remedies had the result of
causing chemical compounds, whether novel or already known,
to be investigated more carefully and scientifically than had
ever been done before. The products of the animal body
were zealously studied, and a small beginning was made in
physiological chemistry by the examination of milk, blood,
saliva, etc., which in its turn increased the interest felt in
organic compounds. In technical chemistry less progress was
made than in chemistry which was related to medicine. An
advance in the knowledge of the composition of substances
and in the observation of reactions, i.e. in qualitative analysis,
first became noticeable towards the end of the iatro-chemical
period.
Technical Chemistry. — The most eminent exponents
in this direction, chief among whom were Agricola and Palissy,
1 Cf. Kopp, Gesch. d. Chemie, vol. ii. pp. Ill, 126 ; vols. iii. and iv.
passim.
88 THE IATRO-CHEMICAL PERIOD CHAP.
have been already referred to. In their works, as also in
the writings of Biringuiccio, Caesalpin and others which are
devoted to technical chemistry, special weight is laid on the
particular operations by which technical products are ob-
tained, these operations being minutely described.
In Metallurgy Agricola and Libavius were the first to
point out a method by means of which it was possible to
estimate approximately the amount of metal in an ore ;
the science of testing thus gradually developed itself from
such beginnings. The more scientific treatment of applied
chemistry is further shown by the fact that by-products
began to be used which had previously been neglected, e.g. the
sulphur which escaped during the partial roasting of pyrites
was condensed, the tutty from zinc ores was utilised for
brass, and so on.
A knowledge of the individual metals, and of the methods
by which they could be obtained and worked up, became
extended in the sixteenth century by Agricola and other
authors making into common property what had hitherto
been only known to the few ; e.g. the separation of gold from
silver by means of nitric acid, which was first carried out on
a large scale in Venice towards the end of the fifteenth
century, and the amalgamation process, first applied in
Mexico about the middle of the sixteenth century for ex-
tracting silver from its ores, but only introduced into Europe
towards the end of the eighteenth. It is in the sixteenth
century that we find the first reliable observations on the
production of ruby glass by means of gold. Salts of the
latter metal and also of silver were more carefully investi-
gated, with reference particularly to their medical applica-
tion ; and some of their characteristic reactions — by which it
became possible to distinguish them from other substances —
were also noticed.
With respect to copper and its precipitation from a
solution of copper vitriol by means of iron, we find even
chemists of discernment like Libavius holding fast to the
old idea that a transmutation had occurred ; but others, e.g.
van Helmont and Sala, recognised the pre-existence of the
in METALLURGY ; POTTERY AND GLASS MANUFACTURE 89
copper. The metallurgical operations necessary for obtaining
iron became generally known through Agricola's writings,1
thus the production of steel by the puddling process was
first described by him. Steel was at that time regarded as
a very pure iron. Of the other metals, a knowledge of zinc
and bismuth was gradually acquired, although there was
often uncertainty about them, and they were frequently con-
founded with antimony. Tin, lastly, was much used in the
sixteenth century for tinning iron. But the iatro-chemical
age interested itself less in the metals themselves than in
the salts prepared from them, since there was always the
chance of these proving useful in medicine. (See under
Preparations.)
Pottery and Glass Manufacture. — The ceramic in-
dustry in particular made considerable progress, thanks to
the untiring efforts of Palissy; his only guide was the ex-
perience gained from innumerable trials, but he succeeded
in affixing beautiful and durable enamels on earthenware
vessels, especially on those of Fayence pottery. His obser-
vations on this point, and also on the application of different
clays for ceramic purposes, and the burning-in of colours, are
given in his work L'Art de Terre, which at the same time aims
at showing the value of the experimental method as opposed
to theory alone. Porta was also busy in Italy about the
middle of the sixteenth century with work similar to Palissy 's.
The manufacture of glass did not lag behind that of
pottery. From the Venetian factories, whose sixteenth-
century productions still astonish and delight the con-
noisseur, the art of making glass of the most various colours
and of different degrees of refrangibility spread to other
countries. The work of the Florentine Antonio Neri, en-
titled De Arte Vitraria, which appeared in 1640, not
improbably contributed materially to spreading a knowledge
of special operations, his large experience on the subject
being detailed in this book. Great skill was also attained
1 The significance of Agricola's work in this field is clearly seen in the
account given by L. Beck in his Geschichte des Eisens, vol. ii. p. 22, etc.
90 THE ATRO-CHEMICAL PERIOD CHAP.
even at that date in the imitation of precious stones, as
Porta's recipes show. One of the most important discoveries
of the time was that of cobalt blue by Christoph Schurer, a
Saxon glass-blower, who obtained it on fusing the cobalteous
residue from the manufacture of bismuth with glass ; it soon
became a much-prized article of commerce, being known
under the names zaffre (from sapphire), and, later on, smalt.
Dyeing. — One of the results of the discovery of
America and of the ocean route to the East Indies was seen
in the increased importation of indigo and cochineal, which
gave a fresh impetus to the dyeing industry. Many im-
proved methods of fixing these and other colours upon cloth —
e.g. the use of a solution of tin, the judicious mordanting of
the stuffs with alum, iron solution, etc. — were found out in
the sixteenth century. The dyer of that time might consult
the first text-book on this subject, written by the Venetian
Rosetti, which appeared in 1540. Glauber, too, made numer-
ous observations on dyeing processes, and aided not a little
in advancing a knowledge of these.
A new industry sprang up towards the end of the
fifteenth century in the rapidly extending distillation of
brandy ; up to that time spirit of wine was looked upon as
a medicine only, but now it began to be more and more
used, sufficiently diluted, as a drink. The development
of this branch of trade resulted in great improvements in
distilling apparatus, which also came to be of service in
laboratories. The interest which this industry excited is
seen from the numerous works upon the art of the distiller
which appeared at that time.
The applications of chemistry were in fact extended in
the most various directions, among others to agriculture, if
only in a modest degree; thus we find the gifted Palissy
calling attention to the importance of soluble salts in man-
ures, and recommending the addition of mineral substances,
e.g. marl, to these. Here we have the earliest beginnings of
a rational chemistry of agriculture.
KNOWLEDGE OF INORGANIC COMPOUNDS 91
Development of Pharmacy and of the Knowledge of Chemical
Preparations.
Pharmaceutical chemistry is most distinctly a creation
of the iatro-chemical age, during which it was taught that
the chief aim of chemistry lay in the discovery of medicines
that could be prepared artificially. In accordance with this
dictum, not only were the preparations already known, but
also those others which had been newly discovered after
much seeking, tested for their action upon the organism.
The circle of chemical facts was thus greatly widened by
these iatro-chemical labours. The influence of the latter
upon chemistry was made further apparent by the fact of
the drug- shops in which artificial preparations were made,
becoming the nurseries of hard-working chemists, who, espe-
cially in the succeeding generation, played an important part
in the building up of the scientific system.
Inorganic Compounds. — The preparation of mineral
acids showed improvements, and their investigation was
marked by advances which, however, only became of prac-
tical value later on, when the acids began to be employed
technically. Glauber taught how to prepare hydrochloric
acid from rock-salt and oil of vitriol, and also fuming nitric
acid from saltpetre and white arsenic.
To Libavius belongs the merit of simplifying the mode
of preparing sulphuric acid, and of proving that the acid
obtained in various ways — from alum, vitriol (sulphate of
iron), or sulphur and nitric acid — was one and the same sub-
stance. The behaviour of the acids just named to metals,
salts and organic compounds led to a knowledge of a great
number of bodies which had been either unknown hitherto,
or at least had never been produced in this particular way :
and thus, from their modes of preparation, deductions as to
their composition often became possible. Among such sub-
stances were the chlorides formed by the action of hydrochloric
acid upon many of the metals, which up to then had been
92 THE IATRO-CHEMICAL PERIOD CHAP,
prepared by heating the latter with sublimate, and hence
the presence of mercury in the resulting products was as-
sumed. Glauber, to whom we owe a knowledge of many of
them, — e.g. zinc, stannic, arsenious and cuprous chlorides —
disproved this erroneous assumption ; he and his contempo-
raries regarded these salts as compounds of the metal and
hydrochloric acid.
Salts were destined to play a very great part in medi-
cine. Especial interest was taken in the alkaline salts, both
from a theoretical point of view — their composition being a
frequent theme of discussion — and also from a practical, on
account of their technical and officinal applications.
Potash saltpetre, which was prepared on a large scale
on account of its increasing use in the manufacture of gun-
powder,1 was also prized as a medicine when fused. The
observation made by the pseudo-Geber — so important for
a knowledge of its composition — that saltpetre results on
saturating potashes with nitric acid, was first made use of
technically in the iatro-chemical age. Sulphate and chloride
of potash, which were prepared by many different methods
and known under various names, were employed as medi-
cines,— the former by Paracelsus, and the latter by Sylvius
and Tachenius (as sal febrifugum Sylvii). Carbonate of
potash, too, prepared from tartar and the ashes of plants,
was another medicament. Even iatro-chemists of eminence
like Tachenius believed in a chemical difference between
various potashes, according to their modes of preparation, —
an error which Boyle was the first to correct; still more
frequently do we meet with a confounding of potash salts
with those of soda, e.g. their carbonates and chlorides.
Glauber's sulphate of soda, obtained from the residue left in
the manufacture of hydrochloric acid, and known under the
name of sal mirabile, was highly prized by physicians.
Whether borax, which was used in soldering during the
iatro-chemical period, was also employed as a medicine is
doubtful.
1 Agricola describes the preparation of saltpetre in his work De Re
Metallica.
in SALTS OF AMMONIA AND OF THE EARTHS 93
Salts of ammonia were largely used, both officinally and
technically, especially sal ammoniac, whose manufacture was
attempted in Europe so early as the seventeenth century ;
its artificial formation from volatile alkaline salt and
hydrochloric acid was known to the iatro-chemists of that
time (Sylvius, Tachenius, Glauber), but it was only at a
much later date that its true composition was indicated.
The near relation thus found to exist between carbonate of
ammonia and salmiac led conversely to the preparation of
the former from the latter by means of carbonate of potash ;
from the apparently different action of samples of volatile
alkaline salt of diverse origin (from blood, urea and salmiac),
it was supposed that they were different compounds, but
this error was recognised by Tachenius. Of other salts of
ammonia we may mention the sulphate, discovered by
Libavius, the nitrate, by Glauber, and the acetate ; the
last, known as spiritus Mindereri (from its discoverer, the
physician Raymund Minderer), was much valued as a medicine
But few of the salts of the earths were known, and
there was uncertainty as to their composition. Lime and
alum earth (alumina), for instance, were supposed to be
pretty much the same. Of their salts, alum — prepared by
adding putrefied urine to the crude alum lye (the aqueous
extract from roasted aluminous shale) — was much prized
for its technical value, and was manufactured in large
quantity ; the alum of that day was thus essentially ammonia
alum. Agricola himself characterised gypsum as a compound
of lime, while chloride and nitrate of calcium were known
in the seventeenth century, and possibly even before then.
Agricola and his contemporaries were also aware that silica
(i.e. pure sand) — which was for long reckoned as one of the
earths — fused with potashes to a glass which was soluble in
water, and the clear-sighted Tachenius saw in this behaviour
an indication of the acid nature of the substance.
The salts of the heavy and of the noble metals, and
various preparations of the semi-metals (arsenic, antimony and
bismuth) were of much importance for iatro-chemistry, and
therefore also for the development of the chemical know-
94 THE IATRO-CHEMICAL PERIOD
ledge of that time. Basil Valentine, as we have alreacty
seen, had worked up a large number of antimonial pre-
parations and had recommended them for internal use prior
to the appearance of Paracelsus and his school. And
although, in consequence of the abuses resulting from secret
medicines containing antimony, sharp edicts were issued
prohibiting their employment, preparations of antimony came
notwithstanding more and more into favour, this being greatly
due to the efforts of Sylvius. Metallic antimony itself was
prescribed in pills, which were called " the everlasting," since
it was believed that they acted merely by contact, and that
therefore, after passing through the body, they could be used
again and again.1
It was during this period that " Kermes " mineral,
sulphur auratum, and powder of algaroth2 were added to
the medical treasury; antimoniate of potash — prepared by
detonating antimony trisulphide with saltpetre — was also
much used as a medicine. To Glauber more than any one
else is due a clearer knowledge of the chemistry of this and
other antimony compounds.
There was still great obscurity with regard to white
arsenic and the metal prepared from it, and also with respect
to other arsenic compounds; among the latter we may
mention arseniate of potash, which was prepared by fusing
the trioxide with saltpetre, and for which Paracelsus appears to
have had a great predilection as a medicine (arsenicum fixum).
Glauber was the first to prepare chloride of arsenic (AsCl3).
Preparations of bismuth were less used for medicinal pur-
poses, although the similarity between bismuth and antimony,
which often led to confusing the one with the other, did not
escape the iatro-chemists. Basic nitrate of bismuth was much
prized as a cosmetic, while the oxide, according to Agricola,
was used as a paint.
1 Lemery in his Cours et Chimie (1675) remarks upon the use of these
pills as follows : ' ' LorsqiCon avale la pillule perpettielle, die, est entrainee par
sa pesanteur, et elle purge par bas ; on la lave et on la redonne comme devant,
et ainsi perpetiiellement."
2 So called after the Veronese physician Victor Algarotus, who praised
it as pulvis angelicus.
COMPOUNDS OF ZINC, MERCURY, ETC. 95
Of the compounds of zinc, the oxide, zinc vitriol (which
Agricola terms chalcanthum candidum), and the chloride
became better known ; the last of these was prepared by
Glauber by heating calamine strongly with hydrochloric
acid, and it therefore contained basic salt. From tin
Libavius obtained its tetrachloride, by distilling it with
sublimate ; assuming in this the presence of mercury, he
termed it spiritus argenti mm sublimati, but later on it was
commonly known as spiritus fumans Libavii. The solution
of this compound, obtained by treating tin with aqua regia,
began to be applied by Drebbel in many dyeing operations
about the year 1630.
The discovery and investigation of ferric and plumbic
chlorides, the latter of which was used instead of white lead
as a paint, is likewise due to Glauber. The methods of pre-
paring many metallic salts already known were also much
improved, as is seen, for instance, in the description given
by Agricola of the preparation of iron and copper vitriols.
The iatro-chemists devoted much attention to the
production and medical application of quicksilver compounds.
It was given to Paracelsus to overcome the prejudices of
many against mercurial medicines, although most of the
physicians of the old school would have nothing to do with
them. Paracelsus and his disciples had no hesitation in
making use of metallic mercury — finely divided in pills, —
sublimate, and the so-called turpeth mineral (i.e. basic mer-
curic carbonate or sulphate, both of which went under this
name). In this way a much better knowledge of various
mercury compounds was gradually arrived at, some of these
compounds being already known and some newly discovered.
Among the latter were calomel and white precipitate (from
sublimate and ammonia), both of which were prized as
medicines. It was during this period that chemists gradually
learnt that cinnabar consisted of mercury and sulphur, and
that mercury itself belonged to the true and not to the half-
metals.
Of the compounds of silver, lapis infernalis (the nitrate)
was found useful in medicine, principally through Sala's re-
96 THE IATRO-CHEMICAL PERIOD CHAP.
commendation, and the sulphate and chloride of silver were
also known. The production of the latter on precipitating
a solution of silver with hydrochloric acid or common salt
dissolved in water, was made use of analytically as a test both
for silver and for chlorides.
Indeed the beginnings of qualitative analysis in the wet
way are to be sought for in .the iatro-chemical age, in so far
that conclusions regarding the presence of one or another
constituent were drawn from the appearance and behaviour
of precipitates, and of salts which crystallised out from solu-
tion. Tachenius laid especial weight on distinguishing such
precipitates by their colours, and he was himself able to
detect several metals in solution together by means of certain
reagents, such as tincture of galls, the carbonates of potash
and ammonia, caustic potash, etc.
Organic compounds became known in rapidly aug-
menting numbers, in consequence of the increasing attention
paid to the products of vegetable and animal assimilation ;
the actual knowledge of such bodies continued, however, very
superficial and incomplete, since their composition remained
quite obscure. Of the acids, acetic acid became better
known, and several of its salts were used in medicine with
good effect. It did not escape Glauber that the distillate
from wood contained an acid which strikingly resembled
that of vinegar. The iatro -chemists taught how to prepare
concentrated acetic acid by the distillation of verdigris,
whence it was known as copper spirit or radical vinegar ; and
this latter substance Tachenius was inclined to regard as van
Helmont's alkahest. The two acetates, sugar of lead and the
basic acetate, were also examined more accurately by
Libavius, and employed as medicines.1
Salts of tartaric acid, of which tartar had been known
for a long time, came to be valued as medicines in the sixteenth
century ; the discovery of the free acid itself belongs to a
1 The liquid which distils over on heating sugar of lead and which we
now know to contain acetone, was investigated repeatedly ; from its desig-
nation of quintessence, a specially high value seems to have been put upon it.
in KNOWLEDGE OF ORGANIC COMPOUNDS 97
much later date. The designation tartarus, applied to tartar,
was likewise the generic name in the iatro-chemical age for
other very different salts, e.g. for the salts of potash, in so far
as they were prepared from tartar, and also for sediments
from solutions, especially those from animal secretions. The
part which tartarus played in the theoretical considerations
of iatro-chemistry has already been spoken of. The salts of
other vegetable acids were also frequently termed tartarus,
e.g. salt of sorrel, which appears to have been often confused
with tartar. Neutral tartrate of potash, known as tartarus
tartarisatus, from its preparation from tartar and salt of tartar
(K2C03), and the double tartrate of potash and soda, called
Seignette salt after the man who accidentally discovered it,
likewise became known to chemists.
A compound of even greater importance to the medical
treasury than the tartrates just mentioned was tartar emetic,
the preparation of which from oxide of antimony and tartar
was described by the Dutch physician Mynsicht, and after-
wards more accurately by Glauber.1 A tartar containing
iron (tartarus ckalybeatus) became known through Sala's
Tartarologia. Paracelsus also made use of the distillate from
tartar — which is now known to contain pyro-tartaric acid
besides other substances — as a medicine (spiritus tartari).
Succinic acid, the near relation of which to tartaric has
only become clear in our own time, is described by Libavius
and Croll under the name of Bernsteinsalz (flos succini), what
they referred to being the distillation product of amber ;
Lemery was the first to recognise its acid nature, about 1675.
The acid juice of the apple and other fruits was employed for
preparing various medicines (e.g. the tinctura martis pomata),
before any attempt was made to isolate the acid itself. Free
benzoic acid, however, obtained by subliming gum benzoin,
was discovered and minutely described by the French
physician Blaise de Vigenere (1522-96) towards the end
of the sixteenth century, while Turquet de Mayerne described
1 It may just be mentioned here that the taking of small quantities of
tartar emetic, prepared by allowing wine to stand in goblets made of anti-
mony, had been a common practice long .before this.
H
98 THE IATRO-CHEMICAL PERIOD CHAP.
the improved method of preparing it in the dry way, which
is still practised at the present time. The juice of gall
apples, which contains tannic acid, and the extract of oak
bark were used by many iatro-chemists from the time of
Paracelsus to test for iron in solutions, especially in mineral
waters ; but no one succeeded in isolating either tannic or
gallic acid itself.
Although the old observation — that the fats were altered
chemically by the alkalies and metallic oxides — did not
lead the iatro-chemists to a knowledge of the fatty acids,
it guided many of them, the acute Tachenius in particular,
to the correct assumption that " oil or fat contains a hidden
acid." It was only one hundred and sixty years later that
Chevreul's work upon fats laid the firm foundation for the
present views upon their chemical constitution.
Spirit of wine — the aqua mice of the alchemists — con-
tinued to grow in importance during the iatro-chemical age,
as it had done in the alchemistic. This applied to it not
merely from a theoretical point of view, as being a product
of various fermentation processes to which much attention
was paid, but also from a practical, since Paracelsus and his
disciples used it largely in the preparation of essences and
tinctures.1
To the German physician Valerius Cordus is due the
first exact knowledge of the ether produced from alcohol by
acting upon it with sulphuric acid, although his instructions
for preparing it were only published after his death, and the
ether then accepted in the Pharmacopeias as oleum mtrioli
dulce verum (about 1560). His work, however, became for-
gotten so soon, that we find even such an accomplished
chemist as Stahl unaware of it. A mixture of alcohol and
ether, which later on enjoyed a wide popularity under the
name of Hoffman's drops, had probably been employed by
Paracelsus as a medicament. The knowledge of compound
1 The name alcohol (cdcool) for spirit of wine, which has been in common
use since the time of Libavius, had formerly quite another meaning, having
been applied indifferently to antimony sulphide, vinegar and various other
compounds.
in KNOWLEDGE OF ORGANIC COMPOUNDS 99
ethers remained very fragmentary, scarcely any addition hav-
ing been made to it since the observations of Basil Valentine
(p. 57).
The work done upon other organic substances led to their
practical application in medicine and in daily life, and also
to improvements in the modes of preparing them, e.g. in the
extraction of sugar from the sugar-cane, the juice being
clarified by white of egg and lime; but scientific know-
ledge with regard to such bpdies remained at the lowest
level.
H 2
CHAPTER IV
HISTORY OF THE PERIOD OF THE PHLOGISTON
THEORY, FROM BOYLE TO LAVOISIER
Introduction. — The reasons for naming this period of about
one hundred and twenty years the period of the phlogiston
theory, or of phlogistic chemistry, have been already stated
shortly (p. 4). For the first portion of this era the designa-
tion is in truth not absolutely fitting, since Robert Boyle —
the man who above all others gave a new direction to
chemistry at the time — did not concur in the phlogistic views.
The development proper of the phlogiston theory really took
place after his death. Nevertheless the period from Boyle to
Lavoisier may be so named, because the most important
part of chemical research during that time had to do with
the phenomena of combustion and — what was recognised as
analogous — the calcination of the metals. All the eminent
chemists of that day directed their attention to this problem
both theoretically and experimentally. It formed, especially
towards the end of this period, the centre around which the
whole of chemistry circled ; it became a stumbling-block to the
adherents of the old doctrines, and led to a reform of the
science so fundamental and far-reaching that the chemistry
of to-day still lives under it.
The iatro-chemical theories strove after the impossible,
and therefore quickly succumbed; the marked one-sided-
ness apparent in them, the gratuitous explanations of
life-processes, and the total neglect of the anatomy and
morphology of the organs, made their decline inevitable.
An opportunity was thus given to chemistry to loosen and
CHAP, iv GENERAL CHARACTERISTICS OF THIS PERIOD 101
finally break the bands which medicine had wound around
her, and to take up an independent position of her own.
She still remained for a time under the protection of the
healing art, to which she was indeed an indispensable aid ;
but from the time of Boyle onwards, the great aim of
chemistry was recognised as being the discovery of new
chemical facts, for the sake of arriving at the truth alone.
The spirit of true investigation which penetrated the
natural sciences at the end of the sixteenth and beginning
of the seventeenth centuries also began to extend itself to
chemistry, the development of physics exerting an especially
powerful influence upon the younger sister-science. The in-
ductive method, too, acquired a continually growing and
a lasting influence as a guide, the nature of which was
indicated by Francis Bacon 1 substantially as follows : —
" The true kind of experience is not the mere groping of
a man in the dark, who feels at random to find his way,
instead of waiting for the dawn or striking a light. ... It
begins with an ordered — not chaotic — knowledge of facts,
deduces axioms from these, and from the axioms again designs
new experiments." Equipped with such axioms, chemistry
might enrol itself among the exact sciences.
The learned societies which came into existence in the
second half of the seventeenth and beginning of the eighteenth
centuries, and whose periodicals spread abroad the results of
chemical investigations, aided materially towards the healthy
development of the science. The incitement they gave to
researches, which could then be submitted to verification by
other workers, was also of great value. Finally, they promoted
the reciprocal action of chemistry and allied branches of
science upon each other, an action so fruitful in its results,
by bringing their respective exponents into closer connection.
1 Novum Organon, Aphorism 82, paragraph 3. Bacon in the above para-
graph gave expression to no new idea, but merely called special attention
to the value of experience, a point already recognised by his predecessors
Palissy, Leonardo da Vinci, Paracelsus and others. Liebig in a series of
essays has proved conclusively how unjustifiable it is to designate Bacon as
the originator of the inductive method, and how little he was permeated by
the spirit of true research (see Liebig's Reden und Abfiandlungen, 1874).
102 THE PHLOGISTIC PERIOD CHAP.
The Royal Society, which was formed about the middle
of the seventeenth century by the amalgamation of the two
smaller scientific societies of Oxford and London, and which
began to publish the Philosophical Transactions in 1665,
furnishes a good instance of what has just been said. The
Italian academies, especially the Academia del Cimento of
Florence (1657), devoted themselves mostly to physical and
mathematical studies. In Vienna the Academia Naturae
Ouriosorum was started in 1652, taking the name of Ccesarea
Leopoldina in honour of its patron Leopold I. The Acade'mie
Roy ale originated in Paris in 1666 out of friendly meetings
which were held at the house of the physicist Mersenne ;
the Mtmoires de VAcaddmie des Sciences began to appear in
1699. The Berlin Academy was founded in 1700 by
Frederick I., Leibniz being its first president; and during
the earlier half of the eighteenth century the northern
countries followed suit with similar learned societies, that of
St. Petersburg being started in 1725, that of Stockholm in
1739, and that of Copenhagen in 1743.
That an extraordinary interest was felt at this time in
scientific questions is readily seen from the literature of the
day, which reflects the excitement — sometimes feverish in
its intensity — raised by isolated discoveries, like that of phos-
phorus, or by disputed problems, such as the question of the
cause of combustion.
The modes in -which chemical questions were treated did
indeed approximate to the methods followed in recent times,
but in one respect there was a striking distinction between
them. The chemical investigation of the phlogistic period
took very little note (and then only incidentally) of the propor-
tions by weight in which substances entered into reaction ; it
turned its attention almost alone to the qualitative side of
the phenomena. The introduction and subsequent develop-
ment of the phlogistic doctrines were only possible because of
the utter neglect of quantitative relations. Even acute ob-
servers who noticed that metals increased in weight upon
calcination, and thus came into direct conflict with the
phlogistic view, evaded the only correct explanation of this, —
iv ROBERT BOYLE 103
and, with it, of the phenomena of combustion — by far-fetched
conceptions. This blinding of the understanding by an
erroneous theory, consequent upon the refusal to look into all
the conditions which might have helped to clear up the ques-
tion, is peculiar to the period of phlogistic chemistry.
In spite, however, of the fundamental error which ran
through it, the period was a highly fruitful one for chemistry ;
1 it forms the indispensable introduction to the most recent
\phase of development of the science. And although it was
itself fettered by many erroneous ideas, still the phlogistic
age contributed largely to the refutation of mischievous errors,
e.g. those belonging to the iatro-chemical doctrines and the
false beliefs of alchemy.
GENERAL HISTORY OF THE PHLOGISTIC PERIOD1
Robert Boyle and his Contemporaries.
Boyle has been rightly spoken of as the investigator who,
by his creative genius, pointed out the new path to the
period just then beginning; it would be even better to say
that with him this new path originated. The spirit of pure
investigation, free from the fetters of alchemistic and iatro-
chemical conceptions, animated this remarkable man, whom
chemistry has to thank for teaching her the real aims which
she should pursue. The leading ideas of his scientific pro-
gramme, which are laid down in the Preliminary Discourse
(in Shaw's edition of Boyle's works, three vols., 1725), deserve
to be quoted here : —
P. xxvi. " ' * ' I saw that several chyjnaists had, by a
laudable diligence, obtain'd various productions, and hit
upon many more phenomena, considerable in their kind,
than could well be expected from their narrow principles ;
but finding the generality of those addicted to chymistry,
to have had scarce any view, but to the preparation of
1 Cf. H. Kopp, Gesch. d. Chemie, vol. i. p. 146 et seq. ; Hofer, Hist, de la
Chimie, vol. ii. p. 146 et seq.
104 THE PHLOGISTIC PERIOD CHAP.
medicines, or to the improving of metals, I was tempted to
consider the art, not as a physician or an alchymist, but a
philosopher. And, with this view, I once drew up a scheme
for a chymical philosophy ; which I shou'd be glad that any
experiments or observations of mine might any way con-
tribute to complete."
P. xviii. ". . . And, truly, if men were willing to regard
the advancement of philosophy, more than their own reputa-
tions, it were easy to make them sensible, that one of the
most considerable services they could do the world is, to
set themselves diligently to make experiments, and collect
observations, without attempting to establish theories upon
them, before they have taken notice of all the phenomena
that are to be solved."
Experimental methods,1 taken in conjunction with the
careful observation of actual phenomena, form therefore,
according to Boyle, the only sure foundation for specula-
tions. To have made this the common property of chemistry,
which from thenceforth strove to work out its fundamental
principles by means of experiment, is the undying service
rendered by Boyle.
His life 2 was devoted to fostering the natural sciences,
especially chemistry. The seventh son and fourteenth child of
the Earl of Cork, he was born on the 25th of January, 1626.
After an exceptionally careful training at Eton, he became a
student at Geneva, and continued his studies in the quiet of
his estate of Stalbridge until 1654, when he settled at
Oxford, carrying on there a constant intercourse with other
eminent men of learning. While at Oxford, he belonged to
a society called The Invisible College, the stimulating effect of
which doubtless led to the formation of the Royal Society.
From 1668 he lived in London, where he continued to work
actively, as he had done at Oxford, for the Royal Society,
which had been founded in 1663 ; he became its president
1 Thus he says that from these alone can we look for progress in all
useful knowledge.
2 For a pleasant account of Boyle's life and works cf. Thorpe's Essays in
Historical Chemistry, p. 1 et seq.
iv BOYLE'S VIEWS UPON THE ELEMENTS 105
in 1680 and held that office until his death in 1691. His
noble and unpretentious character, with its accompanying
modesty, and his simple religious tone, called forth astonish-
ment and admiration both from his contemporaries and his
successors. Wh^^^-Ciontrast Jbetween this modesty and the
rude assumption of Paracelsus, or the self-appreciation of
van Helmont and many other savants of the iatro-chemieal
age!
The services whichr Boyle rendered in the development
of chemistry stretch over tlje most various provinces of the
sctencej Isolated observations of importanc^ by which he
enricne^— indeed, fundamentally extended— /applied chem-
istry, fche\ knowledge of chemical compounds >and their
analysis, the chemistry of gase^, and pharmacy; will be
treate^ of in, the special part of "this bo6k. We have at
present only to do with the general significance of his work
and of his theoretical views for chemistry.
The term " element," which before Boyle's time was
a very fluctuating and therefore uncertain one, received
through him a more positive meaning. In his work,
Chemista Scepticus (1661), he criticises the Aristotelian and
the alchemistic elements, which were still accepted by many
in the iatro-chemical age. He enunciated the axiom that
only what can be demonstrated to be the undecomposable
constituents of bodies are to be regarded as elements ; and
he considered it hazardous to advance opinions as to the
properties of the elements in general, without having first
obtained a firm foundation in their actual properties in-
dividually. With a far-seeing glance he looked forward to the
discovery of a much greater number of elements than was at
that time assumed, at the same time contending that many of
the substances then held to be elementary were not really so.
Hand in hand with this wholesome simplification of views
upon the elements, there went fruitful ideas upon the
union of the elements to compounds, and also upon affinity
as the cause of chemical combination, l^oyle was the first
to state with perfect clearness that a chemical compound
results from the combination of two constituents, and that
106 THE PHLOGISTIC PERIOD CHAP.
| it possesses properties totally different from those of either
of its constituents alone. This definite opinion enabled him
to draw a sharp distinction between mixtures and chemical
compounds.
In order to explain the formation or decomposition of
compounds, Boyle advanced a corpuscular theory^which
gave evidence of his acuteness and showed how far he
was ahead of his contemporaries. In his opinion all
substances consisted of minute particles, and chemical
combination took place when particles of different matter
which mutually attracted each other came together. If
another substance interacted with this new body, whose
particles possessed a greater affinity for those of one of the
components of the latter than these components had for
each other, then decomposition ensued. In such simple
manner did Boyle endeavour to explain the formation and
decomposition of chemical compounds.
No one before him had grasped so clearly and treated so
successfully the main problem of chemistry, — the investigation
of the composition of substances. In doing this he had the
solid ground of experience and experiment under his feet,
and could always bring forward evidence for the probability
of his views. His endeavours to get at the root of the
composition of bodies gave a refreshing impetus to analytical
chemistry, which indeed before his time could hardly be said
to exist ; and we are at the same time indebted to him for
/fixing the meaning of a " chemical reaction." Boyle appears
to have been the first to make use of the term analysis, in the
sense in which it has since been employed by chemists.
. Boyle likewise devoted much attention to the question of
the cause of combustion and other similar phenomena, and
although his attempts at explaining these were not very
successful, his remarkable experiments on the part played by
air in combustion helped materially to the later solution of
the problem. His work on air and gases led him in 1660
to the memorable discovery of the now well-known law that
x "the volume of a gas varies inversely with the pressure"
(Mariotte found this out independently seventeen years later).
iv BOYLE'S WRITINGS ; LEMERY AND HOMBERG 107
Boyle's writings, which were already widely read" in his
, are characterised by simplicity of style and
clearness of expression ; they offer an agreeable contrast to
the works of many of the other chemists of his time, who
sought to hide their deficiencies in clear thought and accurate
knowledge by metaphorical and mysterious language. In
addition to other papers published in the Philosophical
Transactions, the following works of his, which were brought
out both in English and Latin, are to be especially men-
tioned : — The Sceptical Chymist (Chemista Scepticus) first pub-
lished anonymously in 1661, and afterwards in numerous
editions with Boyle's name as author ; Tentamina qucedam
Physiologica (1661); and Experimenta et Consider utiones de
Coloribus (1663).
Among the contemporaries of Boyle who also advanced the
natural sciences, especially chemistry, and of whom Willis,
Hooke, Wren and Hawksbee must be mentioned here, there
was one in particular who, although a practising physician
himself, rendered good service to chemistry by his observa-
tions on combustion and calcination, viz. John Mayow
(born 1645). His assumption — that atmospheric air
contained a substance1 (also present in saltpetre) which
combined with metals when they were calcined, and which
sustained respiration and converted the venous blood into
arterial — was bound to result in the right interpretation of
the phenomena of combustion, when the observations which
had led to it were sufficiently extended. Mayow's early
death in 1679 was perhaps the reason why this did not
come about, the development of the new chemistry being
greatly retarded in consequence.
Lemery and Homberg. — The Academic Royale rfes
Sciences formed in France the centre of union for chemists
in that country, the chief exponents of the science in
Boyle's time, particularly during the last quarter of the
seventeenth century, being Wilhelm Homberg and Nicolas
Lemery. Both of them being good observers, their work
1 Mayow termed this substance spiritus igno-aereus or nitro-a&reus.
108 THE PHLOGISTIC PERIOD CHAP.
tended chiefly to the development of practical chemistry,
which was especially indebted to Homberg for many valuable
contributions. In the scientific explanation of technical
processes they come a long way after Boyle ; Homberg, in
particular, was still trammelled by alchemistic views, and
held fast to the idea that substances consisted of sulphur,
mercury and salt.
Lemery, born in 1645, hardly did any independent
work on the treatment of theoretical questions, but he well
knew how to sift and put together the facts already known.
This is shown in his Cours de CJiymie1 brought out in 1675,
which was for long held to be the best text-book of chemistry,
and was so widely used that the author himself lived to see
thirteen editions of it published.
In addition to this literary work Lemery was exceedingly
active as a teacher, the last thirty years of his life being
taken up in that way ; in his earlier years he was much
involved in religious polemics, and hence was unable to turn
his chemical knowledge to the best account during that
period.
Lemery designated chemistry a " demonstrative science,"
and therefore sought to elucidate chemical operations by suit-
able experiments. In theoretical questions, e.g. in his views
upon combustion and upon the composition of substances, he
was for the most part an adherent of Boyle.
While Lemery was chiefly exercised, then, about the
effective propagation of his science, Homberg — born in 1652
and permanently settled in Paris after a restless life and
multifarious study — found particularly good opportunity, as
body-physician and alchemist to the Duke of Orleans, of
making numerous and sometimes important observations
in practical chemistry. Some of his researches, e.g. that upon
the saturation of acids by bases, contained fruitful germs
1 Shortly before the publication of the Cours de Chymie, two other text-
books appeared in Paris, both entitled Traite de Chymie, by Lefevre (1660)
and Chr. Glaser (1663), under the latter of whom Lemery had begun his
studies. Glaser's book treats chiefly of pharmaceutical, and Lefevre's of
theoretical chemistry, which latter, however, was not much advanced by it.
iv KUNKEL AND BECHER 109
which became developed later on in the hands of other
workers. Most of the writings of these two men, both of
whom died in the same year (1715), were published in the
Memoirs of the French Academy.
Kunkel and Bee her. — The most eminent German
chemist in Boyle's time was Kunkel, in conjunction with
whom Becher must also be named. Closely connected with
the latter was Stahl, the originator of the phlogiston theory,
of which the germs are to be seen in the views of both of the
men first mentioned.
Johann Kunkel, born at Rendsburg in 1630, did excellent
service to practical chemistry as an able experimenter and
acute observer. Originally a pharmacist, he early showed the
leaning towards alchemy which was decisive and fateful as
regarded the whole course of his life ; he was too honest
not to see through many of the frauds of adepts, but at the
same time was so firmly convinced of the possibility of the
transmutation of metals that he gave his life-work to
solving the problem. Employed as an alchemist by various
princes (among whom were the Dukes of Lauenburg, the
Elector John George of Saxony, and the great Elector of
Brandenburg), whose desires he was unable to gratify, he led
a restless life which came to a close at Stockholm in 1702,
where, by the favour of Charles XL, he had found a more
honourable position than any previously allotted to him.
Kunkel's preconceived opinions caused his writings to be per-
meated by mischievous errors, and to contain work bearing
upon alchemy. What a contrast between him and Boyle !
While the latter was seeking to ascertain the real composition
of substances, and to get at their demonstrable constituents,
the former still held to the tenet that all metals contained
mercury. Nevertheless, as a promoter of experimental
chemistry, and therefore of practical chemical knowledge,
Kunkel deservedly holds a high place.
Johann Joachim Becher, who was born at Speyer in
1635 and died in London in 1682, worked almost contem-
poraneously with Kunkel, but more for the theoretical
110 THE PHLOGISTIC PERIOD CHAP.
explanation of already observed facts than for the practical
side of the subject ; in his unsettled life and his propensity
towards new projects, he resembled the latter. He worked
as an alchemist at various courts (in Mainz, Munich and
Vienna), but he was too honourable to deceive his patrons,
and too candid to allow of his remaining long in any one place.
His bold technical projects almost always came to nothing ;
they show only too clearly their author's deficiency in practical
chemical knowledge. In theoretical questions as to the com-
position of substances Becher attempted to revive the old ideas
of Basil Valentine and Paracelsus in another form. In place
of mercury, sulphur and salt, he set up three " earths," of
which all inorganic (" sub-terrestrial ") bodies should consist,
viz. the mercurial, the vitreous and the combustible (terra
pinguis). The nature of any material depended upon the
proportions in which these three fundamental earths were
contained in it. Of especial importance w:as Becher's
assumption that, when substances were burnt or metals
calcined, the terra pinguis escaped, and that in this escape
lay the explanation of combustion ; it was from this concep-
tion that Stahl's phlogiston theory originated. The opinions
of Becher upon the production of salts and acids from
these earths were also received with approbation by his
disciples.
These theoretical views are to be found in Becher's
first work, Physica Subterranea (1669), and in his last,
Theses Chymicce (1682). His doctrines acquired great
celebrity through Stahl, whose work belongs for the most
part to the eighteenth century, on which he conferred a
character of its own by his development of the phlogiston
theory.
Stahl and the Phlogiston Theory.
The theory of the phenomena of combustion and other
analogous processes, which were to be explained by the
assumption of the hypothetical phlogiston, was the point round
which chemists in general gravitated during the eighteenth
iv STAHL'S PHLOGISTON THEORY 111
century; until the appearance of Lavoisier the phlogiston
theory received the assent of most investigators.
Georg Ernst Stahl, born at Anspach in 1660, devoted
himself to the study of medicine, and acquired, first at Jena
and later on at Halle — to whose university he had been called
as professor of medicine and chemistry in 1693 — , the reputa-
tion of a distinguished physician and academic teacher.
Appointed physician to the king in 1716, he removed to
Berlin, where he laboured with success for the extension of
chemical knowledge until his death in 1734. He worked
at chemistry in the true scientific spirit ; himself guided by
the ardent desire to discover the truth, he was able to draw
around him pupils animated by a similar aim. The most
eminent among the Berlin chemists of the succeeding
generation studied under him.
Even in his own lifetime the doctrines which he taught,
togetherwith a number of valuable detached observations, were
widely disseminated by means of his writings, and especially by
his lectures, the latter of which were published by several of
his pupils.1 Stahl, however, exercised his greatest influence
both upon his contemporaries and upon the succeeding genera-
tion by his phlogiston theory, which eclipsed all his other
chemical work.
Stahl himself freely recognised the close connection
between his views upon combustion and calcination and the
original ones of Becher ; he went to work, however, quite
differently from the latter, although his doctrine was grounded
upon Becher's idea regarding the combustible constituent.
This assumption of a constituent common to combustible
bodies (a " fire material," a " sulphur," and so on) was indeed
of older date than that of Becher's terra pinguis, which Stahl
at once utilised, in order to build up his phlogiston theory
thereon. This rests upon the hypothesis that combustible
substances — among which the metals capable of calcination
1 Among Stahl's writings we may name the Zymotechnia Fundamentally,
etc. (1697); Specimen Becherianum, etc. (1702); and Zufallige Gedanken uber
den Streit von dem sogenannten Sulphure ("Occasional Thoughts on the
Dispute regarding the so-called Sulphur"), (1718). Of his pupils, Juncker
was especially active in propagating the views of his master.
112 THE PHLOGISTIC PERIOD CHAP.
were reckoned — contain phlogiston as a common constit-
uent, which escapes on combustion or calcination. Since,
as was then held, every phenomenon bearing upon this could
be readily explained by the aid of such an assumption, it
was considered unnecessary to prove the actual existence of
phlogiston itself directly. Stahl was able by means of it
to group uniformly together and to explain a large number
of chemical reactions. The more violently the combustion of
any substance went on — so he taught, — the richer it was in
phlogiston ; coal, which can be almost entirely consumed,
was therefore to be regarded as nearly pure phlogiston. In
order to reproduce the original substance, its combustion-
products had to be added to it again; in this manner the
metals were " revived " from their calces, which, accord-
ing to Stahl's notion, had resulted from the former through
the escape of the phlogiston. When a metallic calx was
heated along with coal, the phlogiston so abundantly con-
tained in the latter combined with it, the metal being thus
reproduced ; consequently a metallic calx was a constituent
of a metal. Upon a like sophism rested Stahl's assumption
that sulphur consisted of sulphuric acid and phlogiston. He
saw in the production of sulphur, on heating sulphuric acid
or a sulphate with coal (phlogiston), a synthesis of the
former, and therefore a proof that sulphur was a compound
body. Upon the further logical conclusion, — that the pro-
ducts of combustion of any substance must be lighter than
that substance itself, seeing that they are constituents of it,
no importance was placed. And no attention was paid to
the numerous observations which showed that this was not the
case? — that, indeed, a calcination of the metals was accom-
panied by an increase in weight. It was facts like those
just named which, after a prolonged struggle, brought about
the overthrow of the phlogiston theory.
To Stahl belongs the merit of grouping together the
phenomena of oxidation and reduction, as we now term
these, albeit by the aid of a false hypothesis. The addition'
of phlogiston is equivalent to reduction, and its withdrawal
or escape to oxidation. The analogy between respiration
iv HOFFMANN AND BOERHAVE 113
and the decomposition of animal matters on the one
hand, and combustion on the other, did not escape Stahl,
who likewise assigned the chief role in these processes to
phlogiston.
The value of his theory lay therefore in the interpretation
which it afforded of a variety of processes from one common
point of view. The simplicity of this explanation blinded
both himself and the generation which followed him to such
a degree that they left unnoticed all the glaring contradic-
tions between actual facts and the phlogistic doctrine.
Notwithstanding this, however, the latter was not an
obstacle to the development of chemistry, seeing that
chemists like Black, Cavendish, Marggraf, Scheele, Bergman
and Priestley, who so greatly extended the science by their
wide-reaching discoveries, were phlogistonists in the full
sense of the word.
Hoffmann and Boer have. — Before speaking of the
further destinies of the phlogiston theory, and, in connec-
tion with this, of the state of chemistry at that date, the
work of two of Stahl's contemporaries who contributed
materially to the advancement of the science must be
considered, viz. Friedrich Hoffmann and Hermann Boerhave.
Both of these men were eminent physicians and accomplished
chemists, but they were not exactly adherents of Stahl's
phlogiston doctrine, although they held similar views with
regard to combustion.
Hoffmann, born at Halle in 1660, i.e. in the same year
as Stahl, after acquiring a thorough knowledge of medicine,
mathematics and the natural sciences, practised first as a
physician and then became professor of the science of medicine
in Halle, where he ultimately died in 1742, after an inter-
regnum spent in Berlin. His most important work was done
in medicine and in pharmaceutical and analytical chemistry.
He combated with success the iatro-chemical doctrines of
Sylvius and Tachenius, which still held their ground with
many physicians, exposing their absurdities and showing
to what nonsensical deductions such exaggerations led.
I
114 THE PHLOGISTIC PERIOD CHAP.
Many of his investigations and discoveries in pharmaceuti-
cal and analytical chemistry will be touched upon in the
special history of this time. Hoffmann's views on com-
bustion were very similar to those of Stahl. With respect
to the calcination of the metals and the reduction of their
oxides, however, he expressed opinions which approximate
to those held at the present day, believing, as he did,
that metallic calces contained a sal acidum' in addition to a
metal, the former of which escaped when the calces were
reduced. This assumption did away with the similarity
between combustion and calcination ; these phenomena
became indeed rather opposed to one another thereby, and
with this the special use of the phlogiston theory vanished.
Hoffmann was a very voluminous author, and his collected
works, entitled Opera Omnia Pkysico-medica. show clearness
of style and precision of expression.
Hermann Boerhave, born in 1668 at Voorhout near
Leyden, was originally destined for the study of theology,
but devoted himself to medicine, gaining at the same time
an excellent knowledge of the natural sciences, and especi-
ally of chemistry. From the year 1709 onwards, he was able
to utilise his catholic education to advantage as professor of
medicine, botany and chemistry in Leyden, and attained to
the highest distinction; he died there in 1738.
Boerhave's place in the history of chemistry is due not
to any striking experimental researches, but to the excep-
tional acuteness which he showed in noting and collating
chemical phenomena from one common point of view. His
large text-book Elementa Chemiw (1732) x was intended to
contain all the most important work done in chemistry,
and for a long time it remained by far the best guide to
the study of the science. His estimate of the latter as
an absolutely independent science, subordinate to no other,
1 The admirable English editions of Boerhave's text-book were edited
with great care and success by Dr. Peter Shaw. As a writer in the
Saturday Review has pointed out, the third edition of Shaw's translation,
which appeared in 1753 in two quarto volumes, contains a mass of original
notes of great value and, especially, some detailed catalogues of early
Greek writings upon alchemy.
iv BOERHAVE'S PLACE IN CHEMICAL HISTORY 115
and whose aim should be the investigation and perception
of chemical facts, was at once a beneficial and an elevated
one. In accordance with this view we find him condemning
the abuses which the iatro-chemists had introduced into
chemistry. The work of the alchemists he did not criticise
sharply enough ; in his endeavours to test the assertions
which they made, he believed that he found here and there
some corroboration of them, and was thus probably not dis-
inclined to decide in favour of the adepts in cases where
experience had not as yet spoken her last word. On the other
hand, he refuted many statements, such as those which told
of the fixation of mercury and of the production of the latter
from lead salts, and thus contributed to clear up and rectify
alchemistic opinions and assertions.
Boerhave appears to have concurred in the phlogiston
theory in many points, at least he expressed no opinions
contrary to Stahl's fundamental views, although he did not
agree in regarding the calces of the metals as the earthy
elements of these latter. Like many other investigators,1
Boerhave studied the processes involved in calcination, and
to him is due the valuable experimental contradiction of the
view put forth by Boyle and others, — that, during calcina-
tion, a ponderable fire-stuff is taken up, and thus the increase
in weight of the metals explained.
The Development of Chemistry, and particularly of the
Phlogiston Theory, after Stahl's time.
The influence of Stahl's doctrine manifested itself more
immediately in Germany, where it received the almost
unqualified support of chemists, Berlin remaining the
centre point of this theory. Among the men who upheld
and sought to propagate it, Marggraf was the most eminent.
Kaspar Neumann (born 1683) and Johann Theodor Eller
(born 1689), contemporaries of Stahl, were also active
adherents of the doctrine in the capital city of Prussia.
Both of them, as professors at the medico-chirurgical institute,
I 2
116 THE PHLOGISTIC PERIOD CHAP.
were in a high degree active in maintaining and spreading a
knowledge of chemistry. Their own observations were,
however, of little importance ; those of Eller were chiefly
upon subjects of medical physiology, and are full of untenable
speculations. Stahl's disciple and pupil Johann Heinrich
Pott (born 1692) enriched chemistry by many valuable
observations, but he was unfortunate in his explanation of
these, regarding boracic acid, for instance, — a substance
which he had himself investigated carefully — as consist-
ing of copper vitriol and borax. The results which he
achieved were not at all commensurate with his untiring
perseverance, which he showed, among other ways, in his en-
deavours to prepare porcelain. Although an adherent of the
phlogistic doctrine, Pott did not bring forward anything
new in its favour ; with regard to the nature of phlogiston
itself, he could only express the opinion that it was " a variety
of sulphur."
Andreas Sigismund Marggraf1 (1709-1782) was the
last and most eminent adherent of phlogistic views in
Germany. Destined originally for an apothecary, he
acquired a knowledge and practical experience of chemistry,
pharmacy and metallurgy as assistant to Neumann at Berlin,
and by sedulous study at the high schools of Frankfurt on
the Oder, Strasburg and Halle, and finally at the Freiberg
School of Mines ; this knowledge, accompanied as it was by ex-
ceptional gifts of observation, put him in a position to carry
out researches of the greatest value. One has only to think,
of the observations made by him in his work on phosphoric
acid, — observations which, considering the highly defective
state of chemical analysis at that date, fill us with admira-
tion ; of the proof which he furnished of the difference be-
tween alum and the so-called bitter earth (magnesia), sub-
stances which had hitherto been generally confounded ; and,
above all, of his investigation of the juice of the red beet, in
which he discovered cane sugar (see special section of this
book). It was during this research that Marggraf introduced
1 For an account of his life and works see A. W. Hofmann's charming
Erinnerungen aus der Berliner Vergangenheit, p. 10 et seq.
iv THE FRENCH PHLOGISTONISTS 117
the microscope into chemistry, as a valuable aid in distin-
guishing between different substances.
With this great talent for observation he united the gift
of drawing what were generally sound conclusions from his
work. In one point, however, Marggraf, like all phlogis-
tonists, was not in a position to do this ; although he had
himself proved that phosphorus increases in weight by
conversion into phosphoric acid, he could not free himself
from the idea that phlogiston escaped during this process of
combustion. And he could never be brought to see that
this conception was an erroneous one, although the anti-
phlogistic doctrine was brought out several years before his
death. Marggraf 's papers are almost all contained in the
Memoirs of the Berlin Academy ; most of them were
published during his lifetime in two volumes, under the
title Chemische Schriften.
The French Phlogistonists. — The chief exponents of
chemistry in France during the eighteenth century until
the downfall of the phlogistic system were Geoffroy,
Duhamel, Rouelle and Macquer, who concurred essentially
in Stahl's views. They enriched the science not only by
important facts, but also now and again by useful working
theories.
Stephan Frangois Geoffroy (the elder, to distinguish him
from his less celebrated younger brother, Claude Joseph,
whose work was chiefly pharmaceutico-chemical) was born
in Paris in 1672, and helped for some time in his father's
drug shop; he gave himself up, however, to chemical and
medical studies, and laboured with great success as professor
of medicine in the Jardin des Plantes from the year 1712
until his death in 1731. Geoffroy made himself a name
throughout the scientific world by his researches upon
chemical affinity ; his Tables des Rapports (tables of affinity),
in which the results of his most important observations are
collected, exercised a great influence upon the doctrine of
affinity. His theoretical views were less happy, e.g. he looked
upon the iron found in the ashes of plants as having been
118 THE PHLOGISTIC PERIOD CHAP.
produced artificially during the process of ignition. In the
questions of combustion and calcination he approximated
very closely to Stahl's view ; the metals, for example, he re-
garded as composed of earths and a species of sulphur.
Geoffroy rendered a real service by the energy with which he
attacked alchemistic frauds, subjecting these as he did to
critical examination in the memoir Des Supercheries concernant
la Pierre Philosophale, presented to the French Academy.
Geoffroy 's treatises were published partly in the
Memoirs of the French Academy, and partly in the
Philosophical Transactions. His long-celebrated work, Trac-
tatus de Materia Medica, shows what a high value he placed
upon chemistry as a sister science and aid to medicine.
Duhamel de Monceau (born 1700, died 1*781), of the
school of Lemery and Geoffroy, spent his entire life in Paris,
where his versatility gained for him a high reputation.
His sterling work was not by any means in pure chemistry
alone, but also in physics, meteorology, physiology, botany,
and — particularly — in chemistry as applied to agriculture.
We must make especial mention here of the fact that he
furnished definite proof of the difference between potash and
soda, by preparing the latter pure ; he also showed that it
was the base of rock-salt, borax and Glauber's salt. The
first proposals to prepare soda artificially from rock-salt
came from him, a fact which shows his far-sightedness.
Whilst Duhamel worked purely as an academician,
Guillaume Frai^ois Rouelle (born 1703, died 1770) was
mainly occupied in teaching,1 in which he greatly excelled ;
some of his pupils, particularly Lavoisier and Proust, arrived at
1 The numerous records of Rouelle' s activity as a teacher, which have
come down to us, enable us to form a clear picture of the conditions of
chemical teaching in those days, and at the same time to appreciate the
remarkable personality of the man. The lectures on chemistry were de-
livered by two professors, one of them treating the theory of chemical pro-
cesses, whilst the other, in conjunction with him, showed and explained
how they were carried out practically. While the former (Bourdelin)
fatigued his audience by abstract reasonings, Rouelle inspired the students
of practical chemistry by the vivacity of his discourse, during which he
frequently became so excited as to throw off his periwig and some of his
articles of clothing (cf. Hofer, Hist, de la Chimie, vol. ii. p. 378).
iv THE BRITISH PHLOGISTONISTS— BLACK 119
the highest eminence. At the same time he was also busy as an
investigator, as many admirable observations and conclusions
drawn from these show. Rouelle fixed the meaning of the term
" salt " (in the Memoirs of the Academy for 1 745) from a far
more general point of view than van Helmont or Tachenius
had done. The composition of a substance alone was sufficient
to tell him whether it belonged to the class of salts or not.
Salts were produced by the combination of acids of every kind
with the most various bases ; and, in addition to neutral salts,
he drew a distinction between acid and basic ones. With views
so clear as these, Rouelle was far ahead of his contemporaries.
Among the latter was Pierre Josephe Macquer (born
1718, died 1784), who was likewise an active and successful
teacher at the Jardin des Plantes, and who also aided
effectively in the spread of chemical knowledge by means of
his text-books.1 His own individual work lay less in
theoretical than in applied chemistry, to which he made
valuable contributions (especially in the manufacture of
pottery and in dyeing).
From the beginning of his career to its end Macquer
was a phlogistonist, and did all that he could to reconcile
the continually augmenting discrepancies between theory
and facts ; he paid no heed to proportions by weight, for it
was only in this way that he could maintain the phlogistic
hypothesis. And even although it was proved to be
erroneous and untenable several years before his death, he
was still unable to renounce it.
TheEnglish, Scotch and Swedish Phlogistonists.—
Joseph Black, professor of chemistry in the Universities of
Glasgow and Edinburgh successively, who was born in 1728
and died in 1799, advanced chemistry in an exceptional
degree by his splendid experimental researches, which were
published in the Philosophical Transactions ; in especial by his,
for that time, masterly investigations on carbonic acid and
its compounds with the alkalies and alkaline earths, which
1 The principal of these were : Elements de Chymie Thevrique (1749) ;
Elements de Chymie Pratique (1751) ; and his Dictionnaire de Chymie (1778).
120 THE PHLOGISTIC PERIOD CHAP.
were planned and carried out with the utmost ingenuity. His
observations led to a clear knowledge of processes which
had formerly been explained quite wrongly, and they drew
the attention of investigators in a special manner towards
gases ; the work done with these had the effect of causing
chemistry to proceed on new lines, and was, in fact, the
necessary forerunner of the latest epoch of the science.
In addition to this Black threw open a new field to physics
by the discovery of latent heat in 1 7 6 2, in which his wonder-
ful gift of experimenting came to his aid.1
In order to appreciate his labours at their true value,
and to compare them with those of other chemists who
busied themselves with similar questions, we have only to
fix our attention on his researches upon the alkaline earths
and the alkalies. The carbonates of these were before
Black's time regarded as simple substances ; and it was
further assumed that when limestone was burnt fire-stuff
was taken up, and that this went over into potashes or soda
when these were causticised by means of lime. Black, on
the contrary, proved by his researches that when limestone
or Magnesia alba was calcined, something escaped which led
to a loss of weight and which was identical with van
Helmont's gas sylvestre. This gas — which he termed fixed
air, because of its being held bound by caustic alkalies,
lime, etc. — he proved to be also present in the mild
alkalies ; and these latter became caustic when deprived of
their carbonic acid by lime or magnesia. In this truly
classical research we meet with methods which bear the
impress of an entirely new departure. That Black devoted
great attention to the proportions by weight of the com-
pounds which entered into the reaction is seen in all his
investigations ; and it is thus easy to understand how he
gave up the phlogiston theory and concurred in the doctrine
of Lavoisier when the correct explanation of combustion
and similar processes became possible through the discovery
of oxygen.
1 The Swedish physicist, J. C. Wilcke, also discovered latent heat
about the same time and independently of Black.
iv CAVENDISH'S LIFE AND WORK 121
Black, by his fundamental labours, did away with many
errors, and thereby prepared the way for the definite know-
ledge of the true composition of important chemical com-
pounds. Notwithstanding this, the evident conclusions
which followed from his researches on causticity were un-
favourably criticised by many of the chemists of his time,
and indeed their correctness disputed ; it is strange to find
that even Lavoisier could not bring himself candidly to
recognise Black's services in this respect, and that he rather
ranged himself on the side of the latter 's antagonists, who
were in reality unable to weaken one of his arguments.
In his countryman, Henry Cavendish, Black had a most
distinguished co-worker, who, while investigating quite
independently of him, did so upon similar lines, and to the
great benefit of chemistry. Cavendish, born at Nice in 1731,
devoted himself very quietly but not the less efficiently to
the natural sciences, which he studied thoroughly, especially
to physics and chemistry ; he died in London in 18 10.1
There is but little to be said about his life, for his
unsociable and retiring nature led him to shun anything like
publicity, and indeed it was only with reluctance that he
was induced to publish the results of his remarkable work ;
for this reason many valuable observations of his remained
unknown for some decades. Although Cavendish inherited
a large patrimony, he adhered throughout to a severely
simple style of living.
His masterly researches — so important both from a
physical and from a chemical standpoint — upon hydrogen
(inflammable air), which he was the first to distinguish as a
peculiar gas differing from all others, and also those upon
carbonic acid, constitute him one of the founders of
pneumatic chemistry and one of the originators of the new
era. To him we owe the proof, of what value need not be
said, that water consists of hydrogen and oxygen ; further,
1 The details of Cavendish's life and a picture of his peculiar disposition
are to be found in Wilson's Life of the Honourable H. C. Cavendish (1848).
Compare also Thorpe's clever memoir in his Essays in Historical Chemistry,
p. 70 et seq.
122 THE PHLOGISTIC PERIOD CHAP.
the proofs that atmospheric air is a mixture of nitrogen and
oxygen in constant proportions, and that nitric acid can be
produced by the chemical combination of these two latter
gases in presence of water. All these were discoveries of
the greatest moment. In them Cavendish himself forged
the most powerful weapon for the overthrow of the phlogiston
theory, notwithstanding which we find him still faithful to
the latter. His opposition to the antiphlogistic doctrine,
which he himself helped to found by his own investigations,
can only be explained by the fact that he did not pay
enough attention to the proportions by weight in the pro-
cesses of combustion, but explained the latter in a way
which appeared to him sufficiently convincing, viz. by regard-
ing hydrogen as identical with phlogiston.
Besides this Cavendish showed an absolutely marvellous
exactitude in his researches upon gases, whose specific
gravities and volume-ratios in chemical reactions he estab-
lished. With what ingenuity he thought out and carried
through physical experiments is well exemplified in his work
on the specific heats of metals, and in his attempt — the first
one which was successful — to determine the specific gravity
of the earth. Another instance will be fresh in the memory
of most readers, viz. Cavendish's surmise, from the results of
his own experiments on the combination of oxygen and
nitrogen, that there was possibly still another gas present in
the air in small quantity (argon). When one considers this
wonderful versatility and remembers the thorough mathe-
matical training that Cavendish had gone through, one
can but wonder the more that he laid too little stress upon
proportions by weight in chemical reactions.
The most zealous champion for the phlogistic idea at
that time was Joseph Priestley, to whom the chemistry of
gases owes an extraordinarily large number of new observa-
tions and important discoveries. In Priestley were united
an eccentric mind, in which fantastic speculations found a
place, and a simple and child-like disposition. He combated
the antiphlogistic doctrines until his death (in 1804) as no
other man did, although his own researches often went to
iv JOSEPH PRIESTLEY 123
strengthen, even to lay the foundations of, the latter. In
contrast with the quiet existence of Black and Cavendish,
wholly devoted to science, a wandering life full of vicissitudes
and even of persecutions was destined for Priestley,1 doubt-
less for the most part because of his relations to the English
Church and his own intolerance. Theology was his own
special subject, and he was already a minister when he first
carne more closely into contact with scientific questions.
Born at Fieldheads near Leeds in 1733, and acquainted
with poverty in his early years, he afterwards earned a
modest living as a teacher of languages (he taught Latin,
Greek, French, Italian and Hebrew), and then as a minister
of the Gospel. His versatility was further shown by the
fact that he also occasionally gave lectures in logic, history,
law, anatomy, etc. The numerous philosophical and theo-
logical books which he wrote, some of them very com-
prehensive, are probably now altogether forgotten, although
Priestley himself considered these his best work. A per-
sonal acquaintance with Benjamin Franklin led him to make
scientific researches, an early result of which was his
History of Electricity. Later on, in the comparative leisure
of librarian to Lord Shelburne, he found time for chemical
investigations, his most important work being done at this
period (1772—9).
After some years spent as minister of a meeting-house
in Birmingham, Priestley was obliged to leave the latter
town for London in 1791, an attack on Burke's writings upon
the French Revolution having raised popular opinion against
him, and indeed resulted in open mob-riot. A few years
later he emigrated to America, and settled at Northum-
berland near Philadelphia, where he died in 1804. Although
there is much of dilettantism in the mode in which Priestley
treats scientific problems, he rivets our attention by the
charm of his intense originality and perspicacity.
Endowed with an unusual gift for experimenting and
1 Thorpe's admirable paper (Essays, p. 28) gives a graphic account of
Priestley's life and many-sided activity. Compare also Priestley's Scientific
Correspondence, edited by H. C. Bolton (Ne^ York, 1892).
124 THE PHLOGISTIC PERIOD CHAP.
observing, he was able to treat the most difficult problems of
pneumatic chemistry, although lacking a thorough scientific
education. He prepared and investigated a large number
of gases which, with the exception of carbonic acid and
hydrogen, were practically unknown before his time. Of
all his discoveries, that of oxygen (in 1774) was the most
important ; it will be treated of later on. It is true, as we now
know, that Scheele had indeed preceded Priestley in many of
these observations, but he had omitted to publish his results soon
enough. Priestley's beautiful researches on this gas did not,
however, lead him to the correct explanation of combustion ;
he remained, on the contrary, true to the doctrine of phlo-
giston. But his mistaken ideas respecting this and similar
processes did not prevent him drawing from his own ob-
servations sagacious conclusions with regard to the series of
recurrent changes which oxygen undergoes in animal and
vegetable metabolism, — a far more complicated process
than that of combustion, which, tied as he was by a false
hypothesis, he was unable to explain.
Contemporaneously with the three last-named British
chemists, two most distinguished investigators, Torbern Olof
Bergman and Karl Wilhelm Scheele, were labouring in
Sweden as upholders of the phlogistic theory, which their
brilliant discoveries and observations only served so deeply
to undermine, that its supersession was inevitable. Bergman
had acquired such a wide knowledge of the natural sciences
that he taught with eminent success as professor of physics,
mineralogy and chemistry at Upsala. Born in the year 1735,
he died at the early age of forty-nine, doubtless from the
effect of overwork upon a weak constitution. | His chief
services to chemistry, to which from 1767 he principally
devoted himself, were in the domain of analysis, which he
treated systematically and enriched by valuable methods.
He knew well how to make his chemical experiences useful
for the definition and classification of minerals, and thereby
laid the foundation of mineralogical chemistry and chemical
geology. The current views upon chemical affinity thus
gained through him precision and clearness; the scientific
TV BERGMAN AND SCHEELE 125
character of chemistry was materially raised by such observa-
tions, and a general survey of chemical processes rendered
much easier. His papers appeared originally in the Memoirs
of the Academies of Stockholm and Upsala; later on they
were collected together, and published in five volumes in
1779-1788, under the title Opuscula Physica et Chemica.
Karl Wilhelm Scheele will remain for all time one of the
most distinguished of chemists ; and his fame is not lessened
by the fact that he continued all his life through a zealous
supporter of the phlogistic doctrine. In spite of this fact, of
the unfavourable conditions under which he lived, and of the
short span of his life, he contributed to chemistry a wealth of
new observations — many of them discoveries of supreme
value — which furnished a rich mine for the experimental
work and theoretical discussions of future generations.
Much new light has been thrown on Scheele's life and
scientific work by A. E. Nordenskiold's recently published
book: Karl Wilhelm Scheele: Nachgelassene Brief e, und
Aufzeichnungen (" Karl Wilhelm Scheele : His Letters and
Journals ") (Stockholm, 1892). This materially supplements
the earlier biographies of Crell, Sjosten-Wilcke, etc., and
gives us more especially a clear account of the genesis and of
the dates of Scheele's magnificent discoveries, while at the
same time we learn what a number of his observations, of
great importance, have hitherto remained unknown.
Scheele, born on the 9th of December, 1742, at Stralsund,
the capital of Pomerania, which at that time belonged to
Sweden, began at fourteen years of age his apprenticeship in
Gothenburg with Apothecary Bauch, who soon recognised
and appreciated the boy's remarkable gifts. Restricted
almost entirely to a few antiquated text-books, together with
the fairly good chemical inventory of the apothecary's shop,
Scheele, by his unwearied experimenting, acquired such a
knowledge of the properties and reactions of many substances
that, by the time he went to Malmo (in 1765) he had,
although still only an apprentice, gained more experience
than the majority of the chemists of the time. At Malmo,
and also in the succeeding posts he held (Stockholm, 1768-
126 THE PHLOGISTIC PERIOD CHAP.
1770, and Upsala, 1770-1775), he increased his knowledge of
the most important branches of chemistry without, however,
becoming so well known at the time as he deserved. It was
only when, through Gahn's good offices, he came into close
relation with Bergman — a connection which began in a
misunderstanding and coolness, but which developed into a
friendship — that Scheele continued to gain steadily in repu-
tation. After taking over the pharmacy at Koping in 1775,
he was able to devote himself more closely to scientific work,
and with still more brilliant results. The records of his
researches followed one another rapidly in the Transactions
of the Stockholm Academy, into which he had been received
as Studiosus Pharmacies in 1775. In 1777 he published the
results of his investigation on air, oxygen, combustion and
respiration in a volume entitled Chemische Alhandlung von
der Luft und dem Feuer ("A Chemical Essay on Air and
Fire"). After his early death at barely forty-four years of
age — a death undoubtedly hastened by a too close devotion
to science — his collected works were published in two volumes
in German by Hermbstadt (Berlin, 1793), under the title :
Sammtliche Physische und Chemische Werke.
It is not merely as an investigator and discoverer, but as
a high-principled and unassuming man, that Scheele merits
our warmest admiration. His aim and object was the dis-
covery of the truth. The letters of the man reveal to us in
the pleasantest way his high scientific ideal, his genuinely
philosophic temper, and his simple mode of thought. " It is
the truth alone that we desire to know, and what joy there is in
discovering it /" With these words he himself characterises
his own efforts.
It is not proposed to enter minutely at this point
into his varied investigations ; a general account only
of his services to science will be given here, and the more
important parts of his work will be referred to in short detail
later on.
Endowed with a most wonderful gift of observation
Scheele was able to bring to a successful conclusion
researches carried on with but very limited means at com-
iv SCHEELE'S GREAT ACHIEVEMENTS 127
mand. A brilliant proof of this is given in his investigations
upon black oxide of manganese (De Magnesia Nigra), which
many competent workers before him had studied without
succeeding in making its nature clear. During this research
Scheele discovered in rapid succession four new substances
— chlorine, oxygen, manganese and baryta — of which the
two first especially were of the utmost importance for the
proper understanding of chemical processes.
The way in which he isolated and noted the characteristics
of oxygen and also, previous to this, of a long series of hitherto
unknown gases, prove him to have been a magnificent ex-
perimenter. And similarly we see him as an incomparable
observer in the discovery of analytical methods and in the
opening out of entirely new fields of inorganic chemistry (see
special section). Scheele was the first to note the fact that
there are various stages in the oxidation of such metals as
iron, copper and mercury, notwithstanding that he still
adhered to the phlogistic hypothesis in explaining the com-
position of those products. With this knowledge he was far
ahead of Lavoisier, Proust and others.
In a manner nothing short of marvellous Scheele brought
his inventive genius to bear upon organic chemistry, which
had till then been left almost untouched; working out in
every direction new methods for isolating the products of
vegetable and animal metabolism, he prepared a large
number of acids and other organic compounds hitherto
unknown. Scheele was a pioneer in nearly every branch
of chemistry, being unique in power of observation and in
the quick comprehension of facts, although, it is true, not
always happy in his interpretation of these, fettered as he
was by the phlogiston theory. Scheele's discoveries will be
referred to separately in the various sections of the Special
History of Chemistry.
In order to properly., appreciate the condition of the
phlogiston theory in the seventh and eighth decades of the
eighteenth century — that is, shortly before its downfall, — the
development up to that date of a special section of chem-
istry, viz. pneumatic, must be considered. The work done
128 THE PHLOGISTIC PERIOD CHAP.
with gases, and, more especially, the knowledge acquired of
their properties and behaviour, had led finally to the correct
interpretation of combustion. The special history of the
phlogistic period thus falls to be treated of now.
DEVELOPMENT OF PARTICULAR BRANCHES OF THEO-
RETICAL AND PRACTICAL CHEMISTRY IN THE
PHLOGISTIC PERIOD.
Pneumatic Chemistry and its Relations to the
Doctrine of Phlogiston. — The influence which the in-
vestigation of gases, especially of oxygen, exercised in shaping
chemistry is sufficiently well known. Oxygen forms to some
extent the centre-point of chemical research during the last
quarter of the eighteenth century, for the knowledge of the
part which it played in combustion and similar processes led
to the setting aside of a doctrine that had dominated all
theoretical views for a hundred years ; and, further, because
results of the greatest importance were conjoined with its
study, inasmuch as this contributed materially to the develop-
ment of the atomic theory.
The services of the men whose observations did most
towards building up the chemistry of gases have already
been mentioned generally; it will suffice here to treat in
more detail certain of these observations together with a few
others. Boyle's researches show a marked advance over
those of van Helmont in the mode in which he collected
gases and worked with them ; at the same time neither he
nor his contemporaries felt quite sure whether carbonic acid
and hydrogen, whose characteristic properties he knew,
differed materially from atmospheric air. This uncertainty
is also seen in the work of later investigators, e.g. Hales ; the
erroneous idea that gases were ordinary air with various
admixtures, had fixed itself firmly in the minds of chemists.
To Black is due the merit of proving the precise difference
between carbonic acid and air, by showing the " fixation " of
the former by caustic alkalies. Cavendish, who recognised
iv PNEUMATIC CHEMISTRY 129
in hydrogen a peculiar gas, likewise helped to do away with
the misconception. That Scheele had already discovered
numerous gases by the year 1770, and had proved them to be
individual substances, is clearly shown in his letters and
journals (cf. pp. 124 — 5). Finally, we would mention here the
remarkable supplemental researches of Bergman on carbonic
acid (17 7 4).
"The methods of collecting gases had improved consider-
ably since Hales — and, before him, the little-known Moitrel
d'^Ilement — had effected a separation of the generating
vessel from the receiver. Air was found to be a fluid capable
of measurement which possessed weight, and which, like all
other fluids, could be transferred from one vessel to another.
The apparatus which Black, Priestley, Scheele and others
used, and those which we employ at the present day,
gradually developed themselves from that of Hales. Priestley
was the first to describe the collection of gases over mercury,
and he succeeded by this device in discovering gaseous
ammonia, hydrochloric acid, silicon fluoride and sulphurous
acid, — all of which had been overlooked so long as water only
was used for this purpose. Scheele had anticipated Priestley
in the isolation of some of these, as well as of nitric oxide
and sulphuretted hydrogen (about 1770), but had not pub-
lished his observations.
The discovery of so many gaseous substances of such
different character greatly excited the chemical world. The
properties of each gas were carefully examined ; and, after
Mayow's researches, and especially after the more exact
determinations by Cavendish, the density was taken as the
criterion of one gas differing from another and from atmo-
spheric air. Due regard was also paid to the greater or
lesser absorption of gases by water, as a distinct test for
some of them ; Bergman, for instance, determined with fair
accuracy the solubility of carbonic acid in water. But the
true composition of gaseous bodies remained unknown during
this epoch, great uncertainty prevailing even about the
simplest of them until Lavoisier had pronounced his opinion
as to the elementary nature of oxygen and hydrogen. How
K
130 THE PHLOGISTIC PERIOD CHAP.
could this indeed be otherwise, so long as the presence of
phlogiston was assumed in most gases ? Hydrogen was
considered identical with phlogiston by many chemists soon
after the middle of the eighteenth century, Cavendish and
Kirwan setting the precedent for this ; others looked upon
coal as being rich in phlogiston, if not as the latter itself.
The most various and often confused opinions were expressed
regarding the composition of carbonic acid, carbonic oxide,
nitric oxide, sulphurous acid, sulphuretted hydrogen and
other gases, these opinions being made to fit in with the
views of the phlogistic doctrine prevalent at that time.
Of greater moment than these varying opinions upon
the constitution of the gases just named were the long
unsettled questions : " Is atmospheric air a simple or a com-
pound body, and — if the latter — what are its constituents
or ingredients ? " These questions were solved experimen-
tally by chemists belonging to the phlogistic era, more par-
ticularly by S'cheele and Priestley ; but it was left to Lavoisier
to interpret their observations correctly. We must now
speak of the most important of the facts then brought to
light, which bore upon the composition of the air.1
The first observation which aided in overthrowing the
old assumption of air being a simple substance, was the be-
haviour of an enclosed volume to a body burning and to
metals heated in it. Boyle was -forced by his researches
in this direction to the supposition that one ingredient of
the air was necessary to respiration and combustion, and
to the calcination of the metals ; but he was unable to
isolate this ingredient, as was also Mayow, who, with his
assumption of a spiritus ingo-aereus, which brought about
combustion (cf. p. 107), came pretty near to the right in-
terpretation. It was, however, only a hundred years later,
after oxygen and nitrogen had been prepared successfully,
that the question approached its solution. Nitrogen, which
various investigators had already worked at, was first isolated
by Scheele ; but Rutherford, who discovered it independently
in 1772, by the absorption of the carbonic acid produced by
1 Cf. Ramsay's recent volume, The Gases of the Atmosphere (Macmillan
.and Co., 1896).
iv DISCOVERY OF OXYGEN BY SCHEELE AND PRIESTLEY 131
combustion or respiration in an enclosed volume of air, pre-
ceded Scheele in publication. It followed from their observa-
tions that this gas, which was incapable of sustaining either
combustion or respiration, must be one of the ingredients of
the atmosphere. The other was isolated and examined by
Scheele and Priestley. The journals already alluded to make
it clear that as early as 1771 — 1773, i.e. during the years of
his sojourn at Upsala, Scheele prepared oxygen by heating
black oxide of manganese with sulphuric or arsenic acid, and
also from nitrates and from the oxides of mercury and silver,
and noted its characteristics clearly. Priestley, who likewise
observed the gas at about the same time, without, however,
recognising its peculiar nature,1 first isolated it for certain
on August 1st, 1774, by heating red oxide of mercury ; and,
as he published his results earlier than Scheele, he has
hitherto been regarded as the first discoverer of oxygen,
whereas we now know the converse to be the case. Both
observed that this gas was capable of supporting combustion
and respiration in an intensified degree. Priestley named it
" dephlogisticated air," and Scheele at first aer vitriolicus, later
" fire air " and also " life air."
The momentous discovery of oxygen enabled both of them
to recognise air as being a mixture of two kinds of gas ; 2
Priestley calls nitrogen " phlogisticated air," and Scheele
terms it " spent air." They both found substances which
absorbed the one constituent of the air (oxygen). Here, again,
Scheele showed the greater versatility, for while Priestley
employed for this purpose saltpetre gas (nitric oxide), Scheele
made use of phosphorus, hydrate of protoxide of iron, mix-
tures of iron and sulphur, and moist iron filings. They made
the further important observation that, upon burning a candle
in an enclosed volume of air, exactly as much " fixed air "
(carbon dioxide) was generated as oxygen had vanished.
Notwithstanding all this they did not get at the right
1 Hales and Bayen, too, had observed oxygen previous to this, but also
without recognising its peculiar nature.
2 Scheele, in his treatise Von Luft und Feuer(" On Air and Fire"), puts
as the heading to a series of his investigations this sentence : — " The air
must be made up of elastic fluids of two kinds."
K 2
132 THE PHLOGISTIC PERIOD CHAP.
explanation of combustion, respiration and calcination, whose
analogy to one another they clearly saw : so prejudiced were
they by the idea that phlogiston escaped during these pro-
cesses, that the path distinctly marked out by their own ob-
servations was left for another to tread. Lavoisier was
destined to do this, as he easily threw aside the trivial
phlogistic prepossessions that he cherished at the beginning
of his scientific career. The others, indeed, upheld a con-
tradictory explanation of combustion and analogous processes,
in order to remain loyal to the phlogistic doctrine. But that
it was Priestley and Scheele who, by their exhaustive re-
searches on oxygen and the part which it played in the pro-
cesses just mentioned, furnished the experimental material
for the correct understanding of these, and not Lavoisier, is
beyond all question.
After the discovery of oxygen and of its chief properties
the days of the phlogistic theory were numbered, although
many of the most eminent chemists still held to it in spite
of accumulating contrary evidence. The greatest difficulty
in the way of the old doctrine was the fact, already known
for a long time, that, in those cases where phlogiston was
supposed to escape, the products became heavier instead of
decreasing in weight. The exact researches on the calcina-
tion of the metals,1 had their results been studied without
any preconceived opinions, ought to have led to the correct
explanation, viz. that one ingredient of the air combines
with the metals to form calces; for not only was the increase
in weight observed, but also the disappearance of a portion
of the air. But instead of drawing from this the conclusion
that the phlogistic hypothesis was untenable, chemists en-
deavoured to make the observed facts fit in with the latter
by putting a strained interpretation on them. Even Boyle,
acute as he was, tried to help himself by the false assumption
1 The earliest of such investigations, which yielded extremely valuable
observations on the increase in weight of the metals and the part played by
the air in their calcination, were undertaken by Jean Rey, Hooke, Mayow
and Boyle in the seventeenth century. Rey and Mayow came very near to
explaining the results of their experiments correctly.
iv RESULTS OF THE DISCOVERY OF OXYGEN 133
that the increase in weight was due to a ponderable fire-stuff.1
It was sought to show by pure philosophy alone, without the
faintest shadow of proof, that air was essential to calcination
and similar processes, by assuming that it must be present
in order to take up the escaping phlogiston. This expedient,
first brought forward by Becher and Stahl, was made use of
again and again by later phlogistonists.
While these latter imagined that they had thus correctly
interpreted the part played by the air, they followed Stahl's
example in paying no heed to the observed alteration in
weight, either regarding this as accidental or making the
most unhappy attempts at explaining it. Thus we find
Juncker, a pupil of Stahl's, pointing out that the metallic
calces were denser than the metals, and therefore heavier, —
an utter confounding of the absolute weight with the specific
gravity, and also a wrong assertion, since Boyle had already
shown in certain instances that the calces were specifically
lighter than their corresponding metals. Equally unscientific
was the assumption that the phlogiston which escaped in
these processes possessed a negative weight, and that, there-
fore, the residual product must be the heavier ; even Guyton
de Morveau and Macquer fell into this gross error. True, the
most able chemists of the phlogistic period did not concur in
these untenable views, but maintained that it was the business
of physicists to investigate such points.2 As a matter of
fact, it remained for the physicist Lavoisier to give the right
explanation of this, and, with it, that of combustion and
similar processes.
1 Boerhave showed the weakness of such an assumption by proving that
the weight of certain metals, e.g. silver, remained the same, whether they
were at the ordinary temperature or at a red heat. He, therefore, ex-
pressed the opinion that an increase in weight on calcination depended upon
the addition of a "saline ingredient" (salziges Theilchen) from the air.
2 Some chemists there were who did not regard the above observations
on the increase in weight of metals when calcined as meaningless ; Tillet,
for example, who made a communication to the French Academy in 1762
upon the increase in weight of lead, calling special attention at the same
time to the fact that a fit explanation of this had still to be given.
134 THE PHLOGISTIC PERIOD CHAP.
Development of some particular Theoretical Views in the
Phlogistic Period.
It is necessary to make one's self acquainted with the
growth of the more important chemical ideas of this time,
in order to properly appreciate the advances which they
show upon those of the preceding periods, and also in order
to comprehend the connection existing between the theo-
retical views of the phlogistic era and of that new one which
begins with Lavoisier. We have to deal here with the
meanings attached to the terms " element " and " chemical
compound," and also with the ideas of the phlogistonists
upon chemical affinity.
Views regarding Elements and Chemical Com-
pounds.— The position which Boyle took up with respect to
the question of the elements has been already spoken of; he
it was who established the scientific term " element," in that
he regarded as elements those actual constituents of com-
pound bodies which were capable of isolation and which
could not themselves be broken up into simpler substances.
With the increase of means for deciding the question
whether any substance is in this sense an element or not,
the boundary line between elements and chemical compounds
became more and more altered in position, but at the same
time sharper. Boyle further cherished the idea that the
elements attainable by chemists were not the ultimate
constituents of matter.
Notwithstanding the clearness with which Boyle set
forth the conditions which an element, according to his
view, must fulfil, we find among his contemporaries and
their successors a tendency to go back to the alchemistic
elements, and even to the Aristotelian. Willis, Lefevre and
Lemery associated earth and water with the three elements
of Basil Valentine and Paracelsus ; Becher also adhered to
those three under other names, adding water to them ; and
even Stahl was unable to free himself from ideas of this kind.
iv VIEWS REGARDING ELEMENTS AND COMPOUNDS 135
The erroneous assumption of the phlogiston theory—
that the products of combustion and calcination, i.e. acids
and metallic oxides, were simple, and the original substances
compound — had the most serious consequences in keeping
back a knowledge of the true elements. While Boyle
appeared inclined to reckon the metals among the latter,
their compound nature was never questioned from the time
of Stahl until the fall of the phlogistic doctrine; and,
conversely, the metallic calces and compounds produced in
an analogous manner (e.g. sulphuric acid, phosphoric acid
and water) were regarded as elements. Sulphur and
phosphorus belonged of course to the compounds. Phlogiston
itself, the supposed existence of which was due to this in-
version of actual relations, was regarded, on the other hand,
as an element. Only after this purely hypothetical state
of matters had been set aside by the proof that instead of
the escape of phlogiston the absorption of oxygen must
be allowed, and instead of the assimilation of phlogiston the
withdrawal of oxygen, did Lavoisier bring light into the
prevailing confusion — a confusion which was being continu-
ally increased by the addition of contradictory facts.
With respect to the term " chemical compound," and the
formation of such, ideas were developed during this period
which contained much that was sound, and which indicated
an advance over previous ones ; this is, of course, apart from
the erroneous assumption that those bodies which were
afterwards recognised as being simple (many metals and
some non-metals) were compounds of their oxides with
phlogiston. By the clearness of his views Boyle contributed
materially to an insight into the nature of chemical com-
pounds, and to a recognition of their dissimilarity to simple
substances. Boyle, Mayow and especially Boerhave gave
utterance to the weighty tenet that the characteristic
properties of substances which combine together chemically
do indeed disappear after such combination, but that never-
theless the latter are not lost, but are still present in the
compound. At that time it was necessary to defend this
truth, which became more distinctly formulated later on in
136 THE PHLOGISTIC PERIOD CHAP.
the law of the Conservation of Matter, against the old
delusion that the formation of a compound was synonymous
with the creation of a new substance. How clearly the
investigators just named had grasped the meaning of the
term " chemical compound," is shown by the sharp distinction
which they drew between it and a mixture of its components.
Analytical chemistry, which was meantime gradually
developing, aided towards a better understanding of the com-
position of substances, for by its means certain constituents of
salts and of other compounds could be distinguished from one
another. So long, however, as analysis remained merely
qualitative, and no account was taken of the proportions
by weight in which substances combined, any considerable
development of the meaning of the term "chemical com-
pound " was impossible ; this was reserved for the succeeding
age.
The defective knowledge of the quantitative composition
of substances forced chemists back upon conclusions drawn
from analogy, when they wished to obtain a survey of the
compounds known. It was to the endeavour to explain
similar phenomena by the assumption of a common prin-
ciple that the phlogistic theory owed its origin. Acids,
salts and metallic calces were looked upon as being of
analogous composition, both because of their behaviour
and their modes of formation. The distinct recognition of
the fact that salts were produced by the combination of acids
with bases was one of the greatest achievements of the
phlogistic period. Before the term " salt " assumed such a
definite form, indistinct ideas on the subject were very
prevalent ; we have only to recall that even such a man as
Stahl used the word for acids and alkalies as well as for
salts proper. After Boerhave, Geoffroy and Duhamel
had succeeded in giving greater precision to the con-
ceptions regarding these classes of compounds, Rouelle was
able (in 1*745) to define salts once for all as the products
of the union of acids with bases, — and he further drew a
sharp distinction between neutral salts (sels neutres par/aits')
on the one hand, and basic and acid salts on the other.
iv VIEWS WITH REGARD TO CHEMICAL AFFINITY 137
The characteristics of salts which formerly obtained —
their solubility in water and their taste, — therefore fell to the
ground, seeing that Kouelle included the insoluble silver and
mercurous chlorides among them.
But while Rouelle's views regarding the alkaline salts
were perfectly sound, he could not throw off the old idea
that the vitriols and other metallic salts consisted of metal
and acid ; it fell to Bergman to show that this was erroneous,
by the proof that it is the metallic calces and not the metals
themselves which combine with acids to salts.1 What an
advance is shown by those definite conceptions on the com-
position of salts, as compared with the vague ideas that even
Stahl not long before had given utterance to, viz. that salts
were made up of an earth and water !
Views regarding Chemical Affinity and its Causes.
—The old assumption that those bodies have an affinity for
one another which have something in common, that affinity,
in fact, is conditioned by this, according to the axiom similia
similibm, held its ground in speculative minds even into the
eighteenth century. The word affinitas, which expresses this
idea, and which was already employed by Albertus Magnus,
presupposes therefore the similarity of substances which
interact with one another. Boerhave, on the contrary,
stoutly maintained that it is unlike substances which show
the greatest tendency to combine with each other ; and,
notwithstanding that the reason given for the combination
of bodies is exactly the opposite of what was originally
taught as such, viz. their dissimilarity, the name " chemical
affinity" or "affinity" for this force has been generally
retained.2
After the time of Glauber, and especially after that of
Boyle, much attention was paid to the processes in which
the forces of affinity manifest themselves. Cases of so-
1 The following passage from the pseudo-Geber's Testamentum shows
that even then people were on the way towards the true explanation of
this. The passage is : Ex metallisfiunt sales post ipsorum calcinationem.
2 These terms were temporarily replaced by others, e.g. rapport
(Geoffroy), attractio (Bergman).
138 THE PHLOGISTIC PERIOD CHAP.
called simple elective affinity (aUractio electiva simplex, a
term which originated with Bergman) were interpreted
correctly by both the chemists just named, and also by
Mayow; for instance, the expulsion of ammonia from
salmiac by fixed alkali, by the assumption that the attraction
of the latter for hydrochloric acid was greater than that of
this acid for the ammonia (fliicTitiges Laugensalz). Observa-
tions of this kind on the expulsion or precipitation of bases
or acids from salts, by substances endowed with stronger
powers of affinity, soon induced chemists to work out the
order in which analogous bodies were separated from their
compounds by others. The observations on the precipitation
of metals and on the expulsion of various acids from salts
by means of sulphuric and nitric acids, among others, may
have tended in an especial degree to make clear the different
strengths of affinity in analogous bodies. The collation of
the results of numerous investigations on the behaviour of
acids and bases to salts, and of metals to metallic salts,
yielded tables of affinity, Tables des rapports (first published
by Geoffroy in 1718 in the Memoirs of the Paris Academy),
in which similar substances were so arranged that their
affinity to the dissimilar ones placed outside the table
gradually decreased.
The following table will serve to elucidate Geoffrey's
principle : —
SULPHURIC ACID.
Fixed alkali
Volatile alkali
Absorptive earth
Iron
Copper
Silver.
FIXED ALKALI.
Sulphuric acid
Nitric acid
Hydrochloric acid
Vinegar
Sulphur.
These tables of affinity remained in use for a considerable
period, although it was apparent that they stood in need of
amendment, and were frequently modified and enlarged. Their
deficiencies became especially obvious when chemists began
to recognise more fully the influence of heat upon the
iv GEOFFROY'S TABLES OF AFFINITY 139
progress of chemical reactions, and observed that some, whose
course under ordinary conditions was perfectly well known,
proceeded in an exactly opposite direction at a higher
temperature ; Stahl, for instance, had noted this correctly in
the interaction of calomel and silver at a lower, and of
chloride of silver and mercury at a higher temperature.
Such reciprocal reactions led to the proposal to prepare
tables of affinity for medium and high temperatures, both
for wet and dry (i.e. fusion) reactions. Bergman made the
attempt in 1775 to work out this proposal of Baume's by
investigating the mutual behaviour of a very large number
of compounds, with the result that the doctrine of chemical
affinity was materially advanced, in so far as this was
possible by such empirical work.
The results of his extended researches were utilised by
Bergman for setting up a theory of affinity, which will be
most conveniently considered in conjunction with Berthollet's
doctrine of affinity (see the history of the doctrine of affinity
in recent times). But even prior to the efforts of both of
these men, the cause of this affinity was a subject of frequent
reflection and of far-reaching speculation. Boyle's lucid
conception — that the small particles (of which, in his view,
different bodies were made up) attract each other — has
been already mentioned. The greater or lesser degree of
this mutual attraction of heterogeneous substances depended
upon the form and position of each small particle. He did
not, however, specially work out this idea, which lay at the
root of his corpuscular theory, doubtless because he was so
sagacious as to see that he could not possibly arrive at any
knowledge with regard to the shape of atoms. Lemery, on
the other hand, gave a loose rein to his fancy upon this
question. According to him, the combination of two sub-
stances— e.g. of an acid with a base — depended upon one of
the small particles being sharp and the other porous ; by the
fitting of the points into the cavities, combination was
effected. He further attempted to explain the throwing
down of precipitates, the solution of metals in acids, etc., in
a similar manner.
140 THE PHLOGISTIC PERIOD CHAP.
The force which the mutual attraction of the particles
calls forth was regarded by many, e.g. by Buffon (who
occasionally took part in the discussion of theoretical
chemical questions), as identical with that of gravitation.
But Bergman, who was also inclined to this assumption,
justly pointed out that, since these particles act upon one
another at the smallest possible distances, this force must
be exerted differently from that of gravity ; and Newton, who
also turned his attention to the point, likewise assumed a
difference between affinity and gravitation.
It was, however, impossible that this subject which dealt
with the phenomena of affinity could develop greatly in the
phlogistic period, since the proportions by weight in chemical
processes were hardly thought of at all. But the purely
qualitative investigation of a large number of reactions, from
whose outcome conclusions were to be drawn regarding the
interaction of individual components, had the effect of matur-
ing much good fruit, so that the unresting efforts of chemists
to enlighten themselves upon such questions turned out by
no means useless.
This indeed applies generally to the attempts of that
age in questions of theoretical chemistry — attempts which
were on the whole unhappy. The chief gain was on the
practical side, in the rich material accumulated by observa-
tion, the complete application of which was reserved for the
new era.
The most important achievements in practical chemistry
during this period will be touched upon briefly in the
following section, in so far as they have not already been
described in the general part.
History of Practical Chemical Knowledge in the Phlogistic Age.
The question of the composition of substances — that
problem which had been recognised as fundamental from
the time of Boyle — could only be solved by the experimental
method ; it was analytical chemistry, which had developed
iv DEVELOPMENT OF ANALYTICAL CHEMISTRY 141
since that time, that was to lead to this knowledge. This
indispensable branch of the science proved itself especially
useful to applied chemistry, whose growth also falls to be
recorded here. The products of technical importance lead
us, lastly, to those chemical compounds, a knowledge of
which was of moment at that time, and therefore also to the
pharmaceutical preparations and to a description of the state
of pharmacy during the phlogistic period.
Development of Analytical Chemistry. — Although
the question of the composition of chemical compounds was
still in a rudimentary stage, and a solution of it in such
a sense as we understand that word to-day was not to
be expected, yet great attention was paid during the
phlogistic period to those reactions by which it was possible
to detect substances with certainty. Qualitative analysis,
of which we had only the small beginnings to record in the
iatro-chemical age, was developed by the labours of Boyle,
Hoffmann, Marggraf, and especially Scheele and Bergman, in
such a way that the observations of antiphlogistic chemistry
which bore upon it could be accepted as valuable contribu-
tions. When we take into account the then prevailing
neglect of the proportions by weight of reacting substances,
it causes us no surprise that methods of quantitative
analysis were but seldom applied ; and yet, in spite of this,
we meet with several notable advances in the analysis both
of solid and gaseous bodies.
The analytical investigation of substances in the wet
way was greatly advanced by Boyle, and this in a systematic
manner as compared with the more scattered, although
valuable, observations of Tachenius. Boyle it was who
introduced the word analysis for those chemical reactions by
which individual substances could be recognised in presence
of one another. For the carrying out of such reactions he
employed certain reagents, of which he possessed, for his
time, an extensive knowledge. It was with him that the
systematic employment of plant juices as indicates originated,
either in solution or fixed upon paper, for the recognition of
142 THE PHLOGISTIC PERIOD CHAP.
acids, bases and neutral substances, and for this purpose he
studied and made particular use of the colouring matters in
the juices of litmus, violets and corn-flowers. Besides these
general reagents, which served to distinguish important
classes of compounds, Boyle introduced many other character-
istic ones which allowed of the recognition of individual sub-
stances in the form of precipitates. For the detection of
sulphuric and hydrochloric acids, respectively, he used solu-
tions of calcium and silver salts, and vice versa. Ammonia he
recognised by the production of a cloud when it came in
contact with hydrochloric or nitric acid; copper salts by
the blue solution which they gave with excess of volatile
alkaline salt; solutions containing iron by the black
colouration they yielded with infusions of tanning stuffs1
(from gall apples, oak leaves, etc.). He was also sometimes
happy in the way in which he applied careful observations
on the precipitation of certain metals by others, as tests
for these.
The salt solutions found in nature, mineral springs in
particular, had before this time stimulated the iatro-chemists
to search out the substances which they contained. Some
advances in the analysis of mineral waters became noticeable
at the end of the seventeenth and in the eighteenth centuries,
and we find at the same time the chemists engaged on the
subject inspired with the wish to prepare those natural
products artificially ; but the knowledge requisite for doing
this, i.e. a knowledge of the true, and especially of the
quantitative, composition of these waters, was wanting even
at the end of last century. Hoffmann investigated a large
number of mineral waters, and proved the presence in them
of carbonic acid, iron, common salt, and salts of magnesia
and lime, showing at the same time how to test for these ;
he also pointed out the characteristics of alkaline and sulphur
waters. In addition to this, he demonstrated the incorrect-
ness of previous statements as to the presence of gold, silver
and arsenic in such waters, and explained the connection
1 The prescription for preparing black iron ink from gall apples and
iron vitriol is due to Boyle.
iv PROGRESS IN CHEMICAL ANALYSIS 143
between the. occurrence of such exceptional salts as alum and
copper vitriol and the nature of the soil at those places. He
frequently made use of crystalline form to distinguish different
salts.
The observations made by Marggraf materially enlarged
the acquaintance with reagents suitable for the detection of
substances, and also the knowledge of the composition of
many compounds. He used, for instance, a solution of
prussiate of potash to test for iron, and applied the different
colourations which the salts of potash and soda impart to a
flame for their detection — a point that had also been observed
independently by Scheele. The behaviour of many salts to
caustic potash enabled Marggraf to arrive at their composition :
thus he proved that gypsum consisted of lime and sulphuric
acid, and that this acid was also present in heavy spar. As
already mentioned, he made use of the microscope for getting
at the crystalline forms of different substances.
That Scheele owed his mastery in the discovery of new
substances to the gift of deducing their presence from
certain reactions, and that he, therefore, greatly extended
analytical chemistry by a multitude of observations, hardly
requires to be stated. But, although in his knowledge of
the chemical behaviour of bodies he was equalled by no one
of his contemporaries, he unfortunately did not apply this
knowledge systematically, as Bergman did, thereby laying the
firm foundation for the methodical use of reagents, and, with
it, of qualitative analysis. The reactions which the latter
made use of as tests for baryta, lime, copper, sulphuretted
hydrogen, and sulphuric, oxalic, arsenious and carbonic acids,
etc., are those in vogue at the present day. Bergman also
drew attention to the general application of the fixed
alkalies for precipitating solutions of metals and earths ; to
many other reagents, such as sublimate, sugar of lead, and
liver of sulphur; and also to modes for estimating pre-
cipitates and separating salts. The first methods, by which
it was possible to test minerals and especially ores completely,
were due to him, viz. their digestion with hydrochloric or
nitric acid, or their fusion with carbonate of potash. There
144 THE PHLOGISTIC PERIOD CHAP.
can be no doubt, however, that he was indebted to Scheele
for many observations; the latter, for instance, fused up
minerals with alkalies so early as 1*772-3, perceived the dif-
ference between soluble and insoluble silicic acid, and carried
through the separation of iron and manganese by means of
acetic acid.
Qualitative analysis in the dry way made considerable
advances in the eighteenth century by the increasing use of
the blowpipe, the value of which in the examination of ores
was recognised more especially in Sweden. Gahn and
Bergman, together with the mineralogist Cronstedt, were
chiefly instrumental in introducing it into chemistry ; l in their
tests they employed borax, soda, cobalt solution and other re-
agents, and also made use of the difference between the
inner and outer flames, though Scheele was manifestly the
first to recognise and explain correctly the reason of this dif-
ference. But it was through Berzelius that the blowpipe be-
came universally employed and felt to be an almost indis-
pensable aid in analysis.
Attempts not merely to test for substances qualitatively,
but also to determine their quantity, were few in number
up to the time of Lavoisier, and yet it is evident from many
statements made by Boyle, Homberg, Marggraf, Scheele,
Bergman and others, that they sometimes endeavoured to
take the proportions by weight into account. How otherwise
is it possible to explain Marggraf s accurate determination of
the weight of the precipitate obtained by dissolving a given
quantity of silver and precipitating the solution with common
salt ; or Black's estimation of the weight of the precipitate
obtained by adding carbonate of soda to a solution of sulphate
of magnesia which corresponded to a definite amount of
magnesia alba, in order to prove the constant proportion of
fixed air in the latter ? Mention must also be made here of
1 After investigating the point with great care, J. Landauer (Ber. xxvi,
p. 898) has brought forward proof to show that it was Cronstedt who really
rendered the chief service here, and not Anton Swab, as has recently been
contended. G. v. Engestrom was the author of the first manual on the use
of the blow-pipe ; this was published in 1770 as an appendix to a work on
mineralogy.
iv THE BEGINNINGS OF GAS ANALYSIS 145
the determination of the weights of metallic precipitates (i.e-
the metals themselves) by Bergman and others. Bergman
was probably the first to proceed on the principle that an
element should not be itself isolated and estimated according
to its own weight, but separated in the most convenient
form as an insoluble precipitate, e.g. lime earth as oxalate
of lime, and sulphuric acid as sulphate of baryta.
In pneumatic chemistry, too, the necessity became
strongly felt of being able to detect different gases in
presence of one another by means of reagents, and to
estimate their relative volumes quantitatively. For this
purpose special absorptives were used, by the action of
which the differences in the gases had first been noticed.
Thus caustic potash was found to be suitable for the absorp-
tion and measurement of carbonic acid, and saltpetre gas
(nitric oxide), hydrate of protoxide of iron, moist sulphuret
of iron, or phosphorus, for that of oxygen. Of course the
results of such quantitative analysis were very inexact.1 But
Cavendish succeeded in making an extremely accurate
determination of the oxygen in air by the method suggested
by Volta, viz. by exploding with hydrogen. Unlike previous
experimenters, he found the composition of the air constant,
the oxygen amounting on the average to 20*85 per cent. ;
the mean, as determined at the present day, is 20'9 per cent.
As the foregoing short account shows, a great deal of
preparatory work, which chiefly required perfecting in the
quantitative direction, stood ready to hand at the period
which began with Lavoisier. The most important features
and principles of chemical analysis were contained in these
preparatory researches, and only waited for development.
1 As the result of very imperfect methods, Priestley and Scheele found
that the proportion of oxygen in air varied between 18 and 25 per cent.
The term " eudiometry " (>i;5tos, fine (applied to weather), and /xerpou,
a measure] came into use then, because it was supposed that the purity of
the air was arrived at by the determination of its oxygen ; and it has
continued to be employed in gas analysis in spite of its inaptness.
146 THE PHLOGISTIC PERIOD CHAP.
The State of Technical Chemistry in the Phlogistic Period.
Many chemists of the time, among whom we may mention
Boyle, Kunkel, Marggraf, Macquer and Duhamel, frequently
directed their efforts to applying their scientific experience of
chemical processes to the advancement of particular branches
of industry. Technical chemistry thus made good progress
during this period. We come across the beginnings of great
chemical industries, and are able to perceive the development
of a knowledge of technically important chemical preparations,,
whose manufacture has increased during this century in an
undreamt-of degree.
The distinction between applied and pure chemistry was
luniversally recognised towards the middle of the eighteenth
century. Serviceable text-books, treating of particular
branches of technical chemistry, were not wanting, the
conjunction of theory and practice so necessary for the
i Ifare of the latter being thus cared for. Analysis was
also successfully brought into the service of chemistry,
especially in the working-up of ores. Even so early as 168(>
Charles XL of Sweden had recognised the value of such
investigations, and had caused a technical laboratory to be
built. Here, under Hiarne's superintendence, all sorts of
natural products (such as ores and other minerals, soils, etc.)
were examined, and researches were instituted, with the
object of rendering chemical products of practical use, and of
applying in daily life the various results obtained.
In metallurgy the several modes of procedure underwent
only slight changes, but, as a consequence of the clearer com-
prehension of chemical reactions, light was thrown upon
many processes which had hitherto been wrongly explained.
The results of the researches of Bergman, Gahn and Rinman
came to be used in the manufacture of iron and steel, the
difference between these being traced to its true reason only
at the end of the phlogistic period. Marggraf taught an
easier mode of preparing zinc from calami ne in closed chambers,
with exclusion of air as far as possible, and thus made this.
iv ADVANCES IN TECHNICAL CHEMISTRY 147
useful metal more available. The manufacture of brass was
materially improved by Duhamel de Monceau, and that of
cast-iron and steel by the versatile Reaumur. The produc-
tion and working-up of particular metals, e.g. the engraving,
tinning and gilding of iron, the silvering of copper, etc., were
developed in many ways by Boyle and Kunkel.
A highly productive field was opened up for the ceramic
industry by the accidental discovery of porcelain, the manu-
facture of which, although carried out on a large scale at
Meissen, remained a secret until it was successfully solved at
Sevres in 1769 by the carefully planned experiments of
Reaumur and other later chemists, notably Macquer. Im-
provements and novelties in the manufacture of glass were
introduced by Kunkel and Boyle, e.g. in the preparatior
of ruby glass and in glass painting. Dyeing was likewise
enriched by the experiences of various chemists. New
colours, chief among which was Prussian blue (discovered
quite accidentally by the dyer Diesbach in 1710), together
with paints, such as mosaic gold and Scheele's green, were
made available for industrial purposes. And chemists, among
whom Stahl, Hellot and Macquer must be particularly men-
tioned, endeavoured not only to prepare and apply colours by
practical recipes, but also to aid the manufacturer by specula-
tions upon the modes in which dyeing processes are brought
about. Dyes were divided by them into two classes, accord-
ing as they were capable of being fixed upon cloth with or
without mordants, and Bancroft (in 1794) distinguished
these as adjective and substantive dyes. Scheele was the first
to give a correct explanation of the formation of lead white, a
substance much prized as a white paint.
Those technically important preparations, of which an
intimate knowledge was first gained in the phlogistic age,
constituted a valuable introduction to the chemical industries
of to-day. At that time the tendency of chemists was to
inquire whether this or that substance was technically
useful, just as in the preceding period they had tested
chemical compounds for their application to medicine. The
manufacture of acids and alkalies, the chemical industry
L 2
148 THE PHLOGISTIC PERIOD CHAP.
which constitutes the basis of nearly all others, was last
century only in its infancy, although even then some of
these products began to be made in considerable quantities.
Thus Boyle tells us that nitric acid was manufactured from
saltpetre in special " distilleries " (Brennereien) to more
advantage than was the case before, by improved methods
worked out by Stahl and others. Rouelle was the first
to show how it could be concentrated by distilling it with
oil of vitriol. Sulphuric acid was first manufactured on the
large scale in England (by Ward of Richmond) about the
middle of the eighteenth century, by burning sulphur with
the addition of saltpetre. The perishable and at the same
time costly glass balloons in which the process was carried
out were soon replaced — at first in Birmingham — by leaden
chambers, which are still indispensable for this manufacture ;
the continuous working of these chambers is an achievement
of our own century. The preparation of fuming sulphuric
acid from "weathered" iron vitriol had been known long
before that of oil of vitriol itself, which last, moreover,
received its name because of its production from this salt.
The manufacture of the fuming acid, based upon the old
observations of the pseudo-Geber and Basil Valentine, was
first carried on at Nordhausen in the Harz (whence its name
of Nordhausen sulphuric acid, still in vogue), being removed
subsequently to Bohemia. The time for the technical ap-
plication of hydrochloric acid and the chlorine generated from
it was not yet come ; hydrofluoric acid, however, was used for
etching glass by Schwanhardt of Ntirnberg so far back as the
seventeenth century.
The alkalies and their carbonates were, as in ancient
times, obtained from the ashes of plants, carbonised tartar
and incrustations on the soil, to be used for the production
of soap, glass, etc. The discovery of the practical prepara-
tion of soda from common salt, which revolutionised in-
dustrial chemistry, was reserved for the beginning of the
present epoch ; but even so early as the first half of the
eighteenth century some remarkable observations were made
which showed that it was possible to convert salt first into
iv ELEMENTS DISCOVERED DURING THIS PERIOD 149
sodic sulphate, and then the latter into soda — reactions which,
as he himself tells us, were turned to use by Leblanc, the
gifted originator of the soda industry.1
Duhamel de Monceau, one of those who showed how to
transform common salt into soda, deserves praise for intro-
ducing suitable processes for the preparation of various
products of technical importance, — salmiac, starch, soap, etc.
We find, in fact, the clearer knowledge of chemical reactions
resulting in improvements in old processes generally, and
many new manufactures created or at least prepared for, e.g.
the now enormous beet sugar industry by Marggrafs dis-
covery.
Knowledge of other important Compounds during the
Phlogistic Period.
The increase in the knowledge of the elements and of
chemical compounds — which, although of no special technical
value then, were partly destined to become so — was quite
remarkable in the phlogistic period, so that it is worth while
to take a short survey of these here. To the elements
known at that time (although they were not regarded as
such) various new ones were added, of which we may
mention phosphorus, chlorine, manganese (isolated by Gahn
in 1774), cobalt (Brandt, 1742), nickel (Cronstedt, 1750), and
platinum (Watson, 1750). The discovery of these was usually
preceded by a thorough investigation of their compounds,
although chance sometimes came into play, e.g. in the
isolation of phosphorus. This last discovery excited chemists
in an unwonted degree and produced an extraordinary sensa-
tion among educated circles in Germany, England and
France, on account of the marvellous properties of the new
body. Brand, a Hamburg alchemist, succeeded in 1669 in
obtaining phosphorus by distilling the residue from evapor-
1 A notable observation made by Scheele about the year 1770 deserves
mention here, viz. , that soda can be prepared by treating a solution of salt
with oxide of lead, filtering, and passing carbonic acid through the filtrate.
This process was patented by Turner in 1787.
150 THE PHLOGISTIC PERIOD CHAP.
ated urine, and gave it the same name as the Bologna stone
or phosphor (which was sulphide of barium, prepared by
heating the sulphate with carbon), already known. The two
leading chemists of the day, Boyle and Kunkel, endeavoured
for years to discover the secret of its preparation, and
ultimately succeeded, contributing thereby at the same time
to a better knowledge of the element.
Of the chemical compounds prepared artificially, it was
the combustion- and calcination-products of the elements,
i.e. acids and metallic oxides, which awakened the most
interest, in accordance with the tendency of the age ; and
accompanying this, the salts formed from these bodies were
carefully studied. A good deal has already been said with
regard to the knowledge of these substances. Although the
views as to their composition were quite erroneous, the
correct interpretation which "came later was materially aided
by the accurate investigation of their behaviour.
Of acids as combustion products, phosphoric acid deserves
the first mention. It was discovered by Boyle, and its
nature elucidated by an admirable research of Marggraf s,
who showed how it was produced by burning phosphorus,
and also by treating the latter with nitric acid ; he likewise
explained its production from urine. Further, that the
amount of phosphorus present in the latter depended upon
the nutriment taken, was distinctly stated by him. Scheele
and Gahn were the first to prove the presence of phosphoric
acid in bones. It has already been mentioned that the
earliest accurate knowledge of the combustion-products of
sulphur, coal, and of gases containing oxygen generally,
belongs to the second half of the eighteenth century.
Cavendish proved the composition of nitric acid by its
synthesis from nitrogen and oxygen (in presence of water),
but the clear result of his researches was obscured by phlo-
gistic accessories. The discovery and accurate examination
of nitrous acid — " volatile nitric acid " — was due to Scheele
in 1768 ; his able treatise on the subject was only published
recently along with his letters (loc. cit., p. 9).
The many investigations which were made on the pro-
iv INORGANIC AND ORGANIC PREPARATIONS 151
ducts of calcination of the metals and semi-metals greatly
advanced the knowledge of these. We may mention here the
recognition by Scheele of white arsenic as the calx of the
metallic arsenic and the oxidation of the former to arsenic
acid in 1775, his discovery of molybdic and tungstic acids,
and the investigation of the behaviour of quicksilver calx
upon heating — so pregnant in its results.
The knowledge that a salt consisted of an acid and a
base facilitated the survey of many compounds widely
apart from one another. Marggraf, for instance, showed
that sulphate of potash had an analogous composition to
gypsum and heavy-spar, although it was so unlike these.
The definite distinction of alum earth from lime earth, of the
latter from magnesia 1 (Hoffmann and Black), and of potash
from soda (Duhamel, Scheele, and others) belonged, with
many other discoveries, to the phlogiston theory in its
prime, and was of great service to the succeeding period.
A large number of new salts became known, among others
salts of manganese and bismuth (including the basic nitrate
of bismuth, so much valued as a cosmetic), compounds of
cobalt, nickel, platinum, etc. And the qualitative composi-
tion of many salts, whose nature had hitherto been quite
misunderstood, was correctly explained, e.g. that of alum,
borax, calamine and other compounds.
Organic Preparations. — The knowledge of organic
compounds was likewise much advanced, especially by
Scheele, who devised methods for discovering and isolating
organic acids. While new fields were thus opened up at
the close of the phlogistic period, those organic substances
which were already known were also further investigated.
It is true that the real composition (even qualitative) of all
these carbon compounds remained unrecognised, and this
complete ignorance hid itself behind meaningless expressions
-and periphrases ; thus oil and water, or a combustible and
1 Silicic acid, which had for long been reckoned among the earths as
*' vitrifiable earth," was first characterised by Scheele as a fire-proof acid
in the year 1773 (Letters, p. 69).
152 --.-'„£**-; THE PHLOGISTIC PERIOD CHAP.
a mercurial principle, were assumed as the constituents of
alcohol. It was again Lavoisier who pointed out the right
path here, by proving that carbon, hydrogen and oxygen
were the constituents of this as of most other organic
substances, and by indicating modes for determining the
proportions by weight of the elements just named.
Spirit of wine and the ethers which could be obtained
from it, together with common ether itself, were the
subjects of frequent investigation, so that they came to
be prepared fairly pure. Spirit of wine especially was
employed in analysis for the separation of different salts,
and attempts were made to deduce the amount of alcohol
in aqueous solutions of it from its specific gravity; the
beginnings of alcoholometry are to be found with Reaumur
in 1733 and Brisson in 1768. With respect to its forma-
tion in spirituous fermentations opinions were very confused ;
many, indeed, disputed this formation, assuming its pre-exist-
ence in the wine must, etc.
Ether, which was termed spiritus vini vitriolatus or
cethereus, became known through the labours of Frobenius
(about 1730), Hoffmann, Pott, Baume and others, and was
used medicinally admixed with spirit of wine (Hoffmann's
drops). The erroneous idea that it contained sulphur
prevailed for a long time, until this was finally done away
with by the investigation of Valentin Rose the younger
(in 1800).1 The name "sulphur ether" arose from this.
At that time any pungent volatile liquid was termed an
ether.
Nitrous2 ether, muriatic ether, and acetous3 ether, so
named because of their respective origins, were likewise
carefully investigated, and were valued as officinal prepara-
tions. Scheele's acuteness of observation is well shown by
the fact that he recognised the necessity for having a
mineral acid present during the formation of ethers of weak
1 Prior to this date, Hoffmann and Macquer correctly assumed that
ether was formed from alcohol by the elimination of water.
3 Our present nitrous ether, admixed with a little nitric ether, aldehyde,
etc. 3 Ethyl acetate.
iv KNOWLEDGE OF ORGANIC ATMTT ^ 153
acids, such as acetic and benzoic, a point which had been
overlooked before his time.
The knowledge of the organic acids was materially ex-
tended during the phlogistic period, especially towards its
close. Acetic acid, which had been longest known of any,
was now prepared in the concentrated pure state as the glacial
acid, and its combustibility was observed by Lauraguais.
Kunkel, Boyle and others believed in the identity of the
acetic acids prepared by fermentation and by the distilla-
tion of wood, without, however, being able to adduce definite
proof of this ; the latter was furnished by Thenard in 1802.
The resemblance between formic acid, discovered by Wray
in 1760, and acetic acid was early noticed, and led to con-
founding the one with the other, until Marggraf definitely
proved their dissimilarity.
Scheele showed how to prepare a large number of acids
from plant juices, by first forming their lime or lead salts,
and then decomposing these with suitable mineral acids,
usually sulphuric. In this way he discovered tartaric acid,
which had hitherto been overlooked in spite of the fact that
tartar had been known for a long time ; also citric, malic and
oxalic acids, the last of which he prepared by acting upon
sugar with nitric acid, and which he recognised as being
identical with the acetosellic acid he had obtained from wood-
sorrel. By treating milk sugar with nitric acid he was led to
the discovery of mucic acid, and by investigating sour milk
to that of lactic acid, while he found uric acid in (bladder)
stones. For other acids, already known, he devised improved
methods of preparation, e.g. for gallic and benzoic. Lastly,
his discovery of prussic acid in 1782, by decomposing yellow
prussiate of potash with sulphuric acid, is worthy of note.
The masterly investigation of it which he made enabled him
to give its qualitative composition with accuracy ; one only
requires to translate his phlogistic language into modern
chemical terms.
The fatty oils and animal fats were frequent subjects of
investigation, without their composition and chemical be-
haviour, especially towards the alkalies, becoming any clearer ;
154 THE PHLOGISTIC PERIOD CHAP.
and this in spite of an important observation made by Scheele
in the discovery of glycerine, or Oelsiiss, as he termed it, by
acting upon a fatty oil with litharge. The importance of this
observation was only recognised at a much later date. Only
the rudiments of preparatory researches are to be seen in
the chemistry of the sugars and of other products of animal
and vegetable metabolism, such as the ethereal oils, albumens,
etc.
Condition of Pharmaceutical Chemistry.
The interests which chemistry and pharmacy had in
common resulted in their exercising a beneficial action upon
one another. A large number of famous investigators owed
to the practice of pharmacy their stimulus to the study of
purely chemical phenomena ; of these we may mention
Kunkel, the Lemerys (father and son), Geoffrey, Kouelle,
Neumann, Marggraff and Scheele. While they themselves
and others contributed a wealth of the most valuable obser-
vations, indeed of fundamental discoveries, to chemistry,
pharmacy was at the same time materially advanced, not only
by those discoveries, but also by special pharmaceutical re-
searches. The chief gain for pharmacy lay in its intimate
fusion with pure chemistry. On the other hand, the work
required in apothecaries' shops proved itself the best pre-
paratory training for future chemists. The scientific taste
was nourished by excellent text-books on pharmaceutical
chemistry, e.g. Baume's ttttrnents de Pharmacie Thdorigue et
Pratique (l762),Hagen's Lehrbuclider Apotliekerkunst (Hagen's
Text-Book of Pharmacy), and was firmly established by the
founding of pharmaceutical laboratories ; the growth of the
latter belongs, however, more to the present epoch.
Many additions were made during this period to the
medical treasury by pharmaceutical chemistry. Of the new
medicines which then came into vogue, and whose nature
was often involved in mystery until they ceased to be secret
remedies, the following important ones may be mentioned > —
Carbonate of ammonia, which was contained in the famous
iv PHARMACEUTICAL CHEMISTRY 155
" English drops " ; sulphate of potash, valued under Glaser's
designation of sal polychrestum, which was obtained by
detonating sulphur with saltpetre; sulphate of magnesia,
first prepared from the Epsom (spring) water by Grew in
1695, and termed sal anglicum, and, later on, bitter salt;
and magnesia alba, obtained from the mother liquors in the
preparation of saltpetre by means of carbonate of potash.
Among the preparations of antimony, the Kermes minerale,
whose composition was only arrived at correctly during the
present century, came into repute. Ferric chloride in
alcoholic solution was a favourite secret medicine in the
first half of the eighteenth century under the name of
" gold drops " or nerve tincture ; its nature, however, soon
became recognised. Hoffmann's drops and the compound
ethers were likewise used officinally. Goulard introduced
basic acetate of lead after the middle of the last century as
a remedy for external use, and it is called by his name to
this day.
Many observations were made with regard to substances
of special antiseptic action, Kunkel pointing to the mineral
acids for this. The antiseptic properties of iron vitriol and
alum were made use of in the impregnation of wood with
these salts, according to the proposal of the Swede, Faggot.
In 1782, Scheele recommended the conservation of vinegar
by boiling it in closed vessels ; he was thus the discoverer
of the sterilisation method, now of such supreme import-
ance.
Concluding Remarks. — The period of phlogistic chem-
istry must be looked upon as the indispensable forerunner of
the new era which began with Lavoisier. The erroneous
conception which underlay the important phenomena of com-
bustion and calcination, and which spread itself over many
other processes, most assuredly did not prevent the young
science of chemistry from developing in a healthy manner.
Without doubt it was the experimental method which con-
tributed most to this. Hand in hand with this development
we find an increasing improvement in the means for observ-
156 THE PHLOGISTIC PERIOD CHAP.
ing chemical processes and for establishing the properties of
substances. These advances were due partly to improved ap-
paratus (for instance, the apparatus required for collecting and
measuring gases), and partly to the use of physical methods
of research ; and here we may note the more frequent deter-
minations of the specific gravity of bodies in different states
of aggregation, and the use of the microscope. The time had
not yet arrived when the balance was to be employed with
such great advantage for the exact determination of propor-
tions by weight in chemical, reactions, although a number of
noteworthy beginnings of quantitative analysis are to be
found.
It is especially to be noted as characteristic of this period
that chemistry now became fully awake to her own proper
task, which was to investigate the composition of substances,
and to find out the constituents from which they could be
prepared. Analytical chemistry was to aid in solving this
problem ; but useful and important results were achieved by
the synthetic method also.
The independent scientific character of chemistry showed
itself in the forms which its relations to other sciences
assumed. The previous dependence upon medicine and
pharmacy ceased ; instead of being their servant, chemistry
became their helper and adviser. It also came into close
contact with physics, mineralogy and botany, which resulted
in mutual advantage to all of them, and made chemistry
the indispensable helpmeet of the others. We have only to
think of the services rendered to those 'sciences by chemists,
e.g. to physics by Boyle, and to physics and mineralogy by
Bergman. This coalition with the -various other sciences had
the effect of opening up new common ground both for these
individually and for chemistry. We find the first scientific
treatment of mineralogical and physical chemistry during the
phlogistic period, and the advances made in organic prepared
the ground for physiological chemistry.
Nothing is less justifiable, therefore, than to assert that
chemistry was at that time no science, and that it was
Lavoisier who created one out of what was, before his
iv CONCLUDING REMARKS 157
time, a science only in name. The record of the services of
Boyle, Stahl, Black, Bergman, Scheele, Cavendish, Priestley,
Marggraf and others, is sufficient to prove the error of such
an assumption.1 In spite of the false hypothesis which lay
at the root of the phlogiston theory, it was the latter itself,
together with the work which resulted from it, that formed
the necessary foundation for the correct standpoints and the
numerous researches of the succeeding period.
1 Cf. Dumas' s Lemons sur la Philosophic Chimique (1837), p. 137; and
also the sentence with which Wurtz began his Histoire des Doctrines
Chimiques (1868) : " La chimie est line science franchise ; elle fat constitute
par Lavoisier," etc. Volhard investigated this statement and so completely
overthrew it (Journ. pr. Chem., N. F., vol. ii. p. 1 et seq.), that recent at-
tempts to minimise the force of his criticism have not only missed their
mark, but are unjustified in their form and style (see especially Grimaux'
Lavoisier (1888), pp. 128 and 363). The sentence by Grimaux (p. 128) :
" Toute la science modernerfest que le developpement de Pceuvre de Lavoisier"
can only be regarded as an extravagant exaggeration, exceeding even that
of Wurtz, just quoted. The most eminent among the antiphlogistonists,
moreover, never thought of calling in question the scientific tendency of
the chemical views which they themselves combated.
CHAPTER V
HISTORY OF THE MOST RECENT PERIOD (FROM
THE TIME OF LAVOISIER UP TO NOW)
THE beginning of the latest period of chemistry, to which
the present generation of investigators still belongs, is rightly
associated with Lavoisier's reforms, which turned the chemi-
cal science of his day into new paths ; he demonstrated the
supreme importance of the proportions by weight in chemical
reactions, which were wrongly interpreted when these were
disregarded. This applied in an especial degree to the
processes of combustion and similar phenomena, which
Lavoisier was the first to explain correctly. Of course
this explanation only became possible after Scheele's and
Priestley's discovery of oxygen. If we desire, therefore, to
associate the commencement of the new era with any par-
ticular event, it must be with the latter important discovery,
which has been already described in the history of the pre-
ceding period.
Lavoisier's combustion theory, with oxygen as its centre-
point, now stepped into the place of the phlogistic doctrine,
which had attained to the dignity of a dogma ; the chemistry
dominated by the latter was thus changed info the so-
called antiphlogistic system. A complete transformation of
all the ideas respecting combustion and calcination, and
therefore respecting the composition of the most important
substances, took place, — truly a reform in the fullest sense
of the word. For, all the reactions in which the escape of
phlogiston had hitherto been assumed depended, as Lavoisier
taught, upon the taking up of oxygen ; and, conversely,
CHAP, v THE MODERN CHEMICAL PERIOD 159
those processes which had been explained by assuming the
absorption of phlogiston, depended upon the separation of
oxygen.
Lavoisier showed that substances like sulphuric and
phosphoric acids and the metallic calces, which according
to the phlogistic doctrine were looked upon as elements,
were really compounds : while those regarded as compounds,
e.g. the metals, sulphur and phosphorus, he assumed to be
elementary.
It will be appropriate here to enter shortly again into
the chief points of dispute in which the phlogistic doctrine
became involved at the time of the discovery of oxygen
(about 1775), and by which its fall was accelerated. The
facts to which the phlogiston theory was unable to accommo-
date itself were many in number. To chemists who regarded
hydrogen as phlogiston — a frequent assumption — the great
difficulty arose of proving whence the phlogiston came which
escaped during the calcination of the metals, and the combus-
tion of sulphur, phosphorus and coal in closed vessels. The
reduction of the metallic oxides by hydrogen did indeed
appear to allow of a perfect explanation from the phlogistic
standpoint, if one paid no heed to the simultaneous forma-
tion of water and the diminution in weight of the oxides.
But how could a reduction of the metallic calx take place
without the presence of phlogiston (hydrogen) ? This occurred
in the case of those calces which were converted into metal
when heated alone in closed vessels. For the production of
quicksilver from red oxide of mercury and of silver and gold
from their oxides by heat, the phlogistic doctrine was able to
offer no explanation. It was, indeed, those reactions which
led to the discovery of oxygen that brought about the col-
lapse of the theory, and rendered possible the establishment
of the antiphlogistic system. And a few years later the
keystone was added to the latter by the proof that water,
which had hitherto been looked upon as an element, was a
compound of oxygen and hydrogeu.
160 THE MODERN CHEMICAL PERIOD CHAP.
GENERAL HISTORY OF CHEMISTRY DURING THIS
PERIOD.
Lavoisier and the Antiphlogistic Chemistry {from 1775
to the end of the Eighteenth Century).
Lavoisier's great achievement consisted in abolishing old
prejudices, and in the masterly application of scientific prin-
ciples to the explanation of chemical processes. A wealth of
important facts was handed down to him by the phlogisto-
nists; he himself did not add much to this in the way of
new chemical observations, but he sifted and collated, from a
point of view hitherto unattained, that which was ready to
hand, giving at the same time the correct explanation of
many processes. We shall not be wrong if we place such
services to the credit of his highly-trained physical and
mathematical mind, which early freed itself from the bonds
of the phlogistic hypothesis. As a physicist Lavoisier was
bound to take into account alterations in weight, e.g. in the
calcination of metals ; the properties of the products obtained
interested him in a lesser degree. This explains why he
himself made no independent chemical discoveries ; but the
unique service which he rendered in being the first to give a
comprehensive and correct explanation of the observations of
others remains incontestable.
Lavoisier lived to see his work appreciated in the highest
degree; he saw the fruit of his labours, the antiphlogistic
system, come out victorious in the fight with the phlogistic,
and propagate itself beyond France. — Anton Laurent
/"Lavoisier was born on August 26th, 1743, a year after
Scheele, but how different were the outward circumstances
of the two ! While the latter was early thrown upon his
own resources, and was in the fullest sense of the word ap
self-educated man, Lavoisier, the son of a distinguished
barrister, had a splendid training given him, and enjoyed
special opportunities for acquiring a thorough knowledge of
mathematics and physics, which exercised a permanent
v LAVOISIER'S LIFE AND WORK 161 ,
influence upon the whole tendency of his thoughts and
methods of investigation. In botany, too, in mineralogy and
geology, meteorology and anatomy he was well versed. Of
his teachers, the mathematician La Caille, the botanist B. de
Jussieu, and the mineralogist Guettard may be mentioned,
while it was Rouelle who initiated him into chemistry.
Even whilst still very young, Lavoisier gained great repute
by his scientific investigations, so that we find him received
(as Associate) into the French Academy in 1768, the imme-
diate cause of this being a prize essay upon the most suitable
method of street-lighting for large towns.
His earliest chemical work1 — particularly the research
upon the supposed transformation of water into earth, the
results of which he published in 1770 — afford clear evidence
of his physical methods. In this he proved that the total
weight of the closed glass vessel plus that of the water which
had for a long time been boiling in it remained unaltered,
but that the weight of the earth produced was exactly
equivalent to the loss in weight of the vessel ; the logical
conclusion to be drawn from this was that the earth came
from the glass and not from the water. What this earth
was he did not investigate; on the other hand, Scheele
was led to the same conclusions as Lavoisier by examining
it qualitatively.
The latter here recognised and laid stress on the use of
the balance as a reliable guide in chemical work. Soon
after this he busied himself with investigating the reactions,
involved in the combustion of substances and in the calcina-
tion of the metals, making use here of some previous obser-
1 With regard to Lavoisier's writings, the reader is referred to the
(Euvres de Lavoisier (piibliees par les soins du Ministre de V Instruction
Publique), which were published in Paris in 1862 ; and to the analyses of
his most important papers, given by H. Kopp in his Chemie in der neueren
Zeit (1874), and by Hofer in his Histoire de la Chimie, vol. ii. p. 490 et seq.
In addition to these, Grimaux' book, Lavoisier, 1743 — 1794 (published in
1888), is a valuable authority on Lavoisier's life and work, even allowing
for the fact that the laudation of the famous chemist is overdone in it (cf.
note, p. 157). This circumstance, together with the criticism meted out to
opponents, and exaggerations of various kinds, seriously detracts from the
value of what is in itself a great historical treatise.
M
162 THE MODERN CHEMICAL PERIOD CHAP.
vations by others on the increase in weight during such
€alcination. With the aid of an exceedingly delicate balance
he sought, in the first instance, to estimate exactly the
alterations in weight which occurred during these processes,
and to get at the reason for this. The results of these
labours, materially amplified by Priestley's and Scheele's
observations on oxygen and its chemical behaviour, formed
the foundation of Lavoisier's theory of combustion.
His position had, in the meantime, become a brilliant one ;
as Farmer-general (he began in 1768 by being an assistant
— adjoint), and, shortly after, as chief director of the saltpetre
industry, of which the Government had a monopoly, he had
plenty of leisure to devote to his own investigations, and
to assist the State both by his advice and by the introduc-
tion of valuable improvements (e.g. in the manufacture of
potash saltpetre, gunpowder, etc.). His numerous reports
on technical questions are evidence of his industry, his
versatility, and his wide-reaching influence. For such kind
of work he had ample opportunity as member of various
Commissions, e.g. of the Socitte1 d' Agriculture, the Bureau
de Consultation, the Commissions des Poids et MSsures, and
so on.
Closely related to his work upon combustion were the
important researches which he carried out in conjunction
with Laplace upon the latent heat of ice and the specific
heats of various bodies. It was his clear physical conception
of the nature of heat, as opposed to that of many phlogisto-
nists (who were unable to get rid of the assumption of a
ponderable caloric), which enabled Lavoisier to interpret
correctly those chemical reactions in which heat was evolved, —
the phenomena of combustion in particular.
Notwithstanding the extraordinary services which La-
voisier rendered to science, and, through the latter, to his
country, by applying his knowledge and experience with
never-flagging zeal for her benefit, he did not escape the fate
which befell so many of his fellow-citizens. Impeached under
the Reign of Terror, he was condemned to death, and
executed together with twenty-eight other Fermiers-ge'ndraux,
v LAVOISIER'S LIFE AND WORK 163
on the 8th of May, 1794.1 Amongst all his numerous friends
and admirers, only a few, including Hauy and Borde, and
only one chemist, Loysel, had the courage to protest against
this, but without effect. His more influential colleagues,
like Guy ton de Morveau, Monge, and especially Fourcroy,2
who took part in politics, and who had assuredly been able
during his five months' imprisonment to do something for
his deliverance, did not dare to offer any opposition to this
terrible crime.
Lavoisier published most of his works in the Memoirs of
the French Academy, over sixty papers by him being con-
tained in its volumes for the years 1768-87 ; some others
are to be found in the Journal de Physique and in the
Annales de Clnwiie? His projected plan of publishing an
edition of his collected works was only carried out long
1 Much light has been thrown upon this sad event by documents pub-
lished by Ed. Grimaux, which relate to the death of Lavoisier. It has been
conjectured that Marat hastened the proceedings against him from a feeling
of petty revenge, because of Lavoisier having unfavourably criticised a
treatise of his, entitled Recherches Physiques sur le Feu, which appeared in
1780. For Marat, in his infamous Ami du Peuple, had repeatedly de-
nounced Lavoisier and had brought about the impeachment, although he
did not himself survive to see the arrest of Lavoisier and his colleagues. In
the sentence, which was passed after an imprisonment and inquiry extend-
ing over five months, it was stated that he was condemned to death " as
convicted of originating or participating in a plot against the French
nation, the aim of which was to aid the enemies of France ; especially in
that he had practised every kind of extortion upon the people, and had
caused tobacco to be admixed with water and pernicious substances, to the
detriment of the health of the citizens who used it." — Cf. Grimaux' work,
Lavoisier, 1743-94, d'apres sa Correspondance, ses Manuscripts, etc. (Paris,
1888).
2 Grimaux' publication, just cited, and also Berthelot's Notice Historique
sur Lavoisier (Mon. Scient., 1890, p. 125), reflect seriously upon the indif-
ference to Lavoisier's fate shown by Fourcroy, de Morveau and others.
3 The dates upon which Lavoisier's papers appeared are of importance
for their criticism ; we have especially to remember here that the yearly
volumes of the Memoires de PAcaddmie did not correspond with the dates
of their publication, but that they were usually brought out several years
afterwards (e.g. the Mdmoires for 1772 in 1776, and those for 1782 in 1785).
The effect of this disarrangement has been great confusion with regard to
the actual time at which this and the other treatise was written by Lavoisier,
because of subsequent alterations in the papers. But, so far as it has been
found possible to verify them, those dates are given here.
M 2
164 THE MODERN CHEMICAL PERIOD CHAP,
after his death (1862-1892). His Opuscules Physiques et
Chymiques, which appeared in 1774, contained his ideas
upon the nature of gases and his views upon the processes
of combustion. In his Traitd EUmentaire de Cliimie (pr£sent6
dans un ordre nouveau et d'apres les dfoouvertes modernes),
published in 1789, he gave a summary of the most important
facts of chemistry, and explained them according to the anti-
phlogistic theory, which thus received its first text-book ;
by means of translations of this book the new doctrine was
materially propagated.
The researches of Lavoisier which were of greatest moment
for the development of chemistry were those which contri-
buted to the founding of the antiphlogistic system, and
which led to the overthrow of the phlogistic ; those, namely,
which treated of the phenomena of combustion, calcination
and respiration. The chief work of his life consisted in his
recognising and explaining the part played by oxygen in
these processes, and in this lies his abiding service.
The previous observations of Rey, Mayow and others,
who had attributed the increase in weight of the metals
during their calcination to an absorption of air, contained
only the first germs of the correct explanation of these pro-
cesses. From the year 1772 Lavoisier busied himself with
investigations bearing upon this subject, the first results of
which he delivered in a sealed note to the French Academy
on November 1st of that year. This note stated that by the
combustion of sulphur and phosphorus, and by the calcina-
tion of the metals, the weight of these substances increased
from the absorption of a large amount of air ; and that, by
the reduction of litharge with coal in an enclosed space, a
considerable quantity of air — a thousandfold the volume of
the litharge — was generated. Lavoisier was at this time
in the same position as Mayow had been, that is, still quite
uncertain as to which portion of the air caused this increase
in weight, as to the air itself being a mixture of gases, and
especially as to the nature of the process which went on in
the reduction of the litharge ; he was inclined to regard the
generated gas (carbonic acid) as the fluid originally combined
v BEGINNINGS OF HIS COMBUSTION THEORY 165
with the lead. This uncertainty was brought about by his
paying too little heed to the qualitative side of the chemical
reactions.
By repeating these and similar researches, however,
Lavoisier soon arrived at a clearer perception of the matter,
and he especially recognised his error with regard to the re-
duction of the oxide of lead. In 1774 he gave further details
of these observations, in particular of the calcination of tin ;x
the investigation was in its main points a repetition of
Boyle's, but Lavoisier was able to draw more correct con-
clusions from it than Boyle had done. A sealed retort, in
which some tin had previously been placed, was weighed
both before and after being heated, and found equally heavy
each time, whence the conclusion was drawn that no fire-
stuff had been absorbed ; on the retort being opened after
cooling, air rushed in, and the whole apparatus showed an
increase in weight exactly equal to that which the tin had
undergone by calcination. Lavoisier concluded from this
that calcination depends upon the absorption of air, i.e. that
the latter is the cause of the increase in weight.
But although we find in these results the beginnings of
his combustion theory, there was still wanting the definite
knowledge as to which portion of the air combined with the
metals and the combustible substances. Oxygen was in the
meantime discovered independently by Scheele and Priestley,
and they recognised in it the constituent of the air which
was necessary for combustion ; but Lavoisier held the key to
the explanation of his researches as soon as he received news
of this discovery. How he turned this to advantage is shown
in a paper written in 1775,2 in which the role of oxygen for
the general explanation of the reactions in question is fully
appreciated ; it was this gas which combined with the metals,
sulphur, phosphorus, coal, and so on. The production of car-
bonic acid from saltpetre and coal led him to the conclusion
that oxygen must likewise be present in this salt — a point
that Mayow indeed recognised a hundred years before this,
1 (Eitvres de Lavoisier, vol. ii. p. 105.
2 Cf. (Euvres, vol. ii. p. 125.
166 THE MODERN CHEMICAL PERIOD CHAP.
only that the latter terms it spiritus nitro-aereus instead of
oxygen. Strangely enough, no reference is made by Lavoisier
to the influence which Priestley's discovery of oxygen (com-
municated to him by Priestley himself) exercised upon his
researches with oxide of mercury and upon his explanation
of previous experiments.1
Lavoisier in due course arrived at perfect clearness in his
explanations, for instance, with regard to the composition of
atmospheric air ; it was in 1776 that he observed that the
combustion-product of the diamond consisted of carbonic
acid alone, and in the following year he showed that, by
burning phosphorus in a closed vessel, one-fifth of the volume
of air in the latter was used up, and non-respirable air
remained behind. The results of these researches, together
with the observations made by Scheele and Priestley, of
which he had in the meantime obtained fuller knowledge,
and the investigations which he made in 1777 on the com-
bustion of organic substances, the products of which he
proved to be carbonic acid and water, enabled Lavoisier to
establish the main points of his Combustion or Oxidation
Theory as follows2 : —
1 The attitude which Lavoisier sometimes took up with respect to the
observations and discoveries of others awakens painful feelings ; it is
melancholy to see an investigator of such splendid gifts so unjust regarding
the services of others. Thus Lavoisier makes no mention in his first
chemical paper, on the composition of gypsum, of Marggraf's important
researches, although these were among the best known of any, while more
than their due recognition was awarded to the other chemists who had
worked at the same subject. In a similar manner he ignored, in the
account of his researches on the composition of water, those of Cavendish
which proved the same point (i.e. its composition), and of whose results he
had positive knowledge through Blagden's information. Black's splendid
investigations upon fixed air, from which Lavoisier without doubt received
the greatest assistance towards his conception of the fixation of gases, he
treated in a cold and depreciatory manner, whilst the most trivial objec-
tions raised against Black were examined with the utmost minuteness and
care. These are unfortunately blots upon Lavoisier's reputation, notwith-
standing the lustre with which it has become surrounded through the
idealistic historical writings of Dumas, Wurtz, Grimaux and others. Cf.
also Thorpe's Essays, p. 87, and especially p. 110 et seq., in which many of
the disputed points in question are cleared up.
2 (Euvres, vol. ii. p. 226, in the Memoire sur la Combustion en gdndral.
v LAVOISIER'S OXIDATION THEORY 167
(1) Substances burn only in pure air (air eminemment
pur).
(2) This air is consumed in the combustion, and the increase
in weight of the substance burnt is equivalent to the decrease in
weight of the air.
(3) The combustible body is, as a rule, converted into an
acid by its combination with the pure air, but the metals, on the
other hand, into metallic calces.
The last sentence contains an idea of great moment,
which Lavoisier developed later into his theory of the com-
position of acids, according to which these latter contain
oxygen as the oxygenating or acidifying principle (principe
oxygine ou acidiftant). To establish this assumption, he
both made investigations himself and referred to and utilised
those of others ; in this way he states that sulphuric acid
consists of sulphur and oxygen, phosphoric acid of phosphorus
and oxygen, and nitric acid of saltpetre gas (nitric oxide)
and oxygen. The true composition of the last acid was
first determined by Cavendish, through its synthesis from
nitrogen and oxygen in presence of water. Hydrochloric
acid being a powerful acid, likewise contained oxygen,
according to Lavoisier's assumption, and this applied in still
stronger degree to the chlorine produced by its oxidation.
Lavoisier further occupied himself with the question — What
kind of oxygen-compound does hydrogen yield? without,
however, arriving at the correct explanation of this inde-
pendently ; for he expected to find an acid as the product
of its combustion, and therefore looked for one. It is the un-
disputed merit of the phlogistonist Cavendish to have proved
that water alone is produced by the combustion of hydrogen.1
This fundamental observation first proved itself fruitful,
1 With regard to this point and also to Watt's share in recognising the
composition of water, cf . H. Kopp's detailed memoir : Ueber die Entdeclcung
der Zusammensetzung des Wassers (Braunschweig, 1875). See also Berthelot's
essay on Lavoisier (Mon. Sclent., 1890, p. 138), and Thorpe's Essays, p. 110.
Berthollet's testimony (Ibid., note, p. 139) leaves no doubt whatever that
even Lavoisier's own friends admitted without any reservation Cavendish's
priority in this discovery.
68 THE MODERN CHEMICAL PERIOD CHAP.
however, in the hands of Lavoisier, who was thus enabled
to give at once the real composition of water (out of hydro-
gen and oxygen), while at the same time estimating the
relative proportions of these approximately. He also
correctly interpreted the decomposition of water by red-hot
iron, and its formation from the reduction of metallic oxides
by means of hydrogen. The generation of the latter gas
on dissolving metals in acids was likewise satisfactorily
explained. It was precisely this reaction which had
strengthened the phlogistonists in their opinion that the
metals contained phlogiston, which, being identical with
hydrogen, escaped on dissolving these in acids. The com-
position of water having been arrived at, Lavoisier now saw
that the hydrogen came from the water, and that the oxygen
of the latter united with the metal to oxide, which then in
its turn combined with the acid.1
With the knowledge of this, which came in the year
1783, the last obstacles with which the antiphlogistic
system had to contend were overcome : the phlogistic theory
could maintain itself no longer, but collapsed. Up to this
date Lavoisier was almost alone in the fight against it,
having only received material aid from eminent physicists
and mathematicians, like Laplace, Monge, Cousin, etc. But
now chemists of standing began to apply his ideas, at first in.'
France (Berthollet 1785, de Morveau 1786, and the diplo-
matically cautious Fourcroy not until 1787), and very soon
in other countries also (Kirwan, e.g., in 1792). Lavoisier's
critical treatises, which were directed to showing the un-
tenability of the phlogistic theory, conjoined with his Trcdtt
de Chimie, gave the final blow to that doctrine.
The main features of Lavoisier's work, which was the
means of leading chemistry into new paths, have now been
described ; but some of his observations and speculations, e.g.
his researches on the composition of organic compounds, and
his comprehensive ideas regarding metabolism in the organic
world, will be treated of in the special history of this time.
The systematic application of quantitative methods of re-
1 Laplace and Meusnier took an active share in these investigations.
v TRIUMPH OF ANTIPHLOGISTIC CHEMISTRY 169
search, and the unbiased treatment of chemical processes
from a rather physical point of view, led him to interpret
correctly the most important phenomena of chemistry, the
explanation of which had been sought for in vain by several
generations of investigators, fettered as they were by the
phlogiston theory. The material which these latter had
collected together, especially the observations of Black,
Scheele, Priestley and Cavendish, were indispensable to
Lavoisier ; we have only to recollect that the discoveries of
most importance for his system — of oxygen, and of the true
composition of water — were not made by himself. But his
genius, far transcending that of any of his contemporaries,
enabled him to get at the root of phenomena which they
failed to comprehend. After recognising that phlogiston
had no existence, and that oxygen was the gas necessary
for combustion, calcination and respiration, he translated the
obscure and wholly erroneous reactions in which phlogiston
was assumed into simple antiphlogistic language.
Although the quantitative method of research was followed
and duly valued by individual chemists both before and
during the time of Lavoisier, e.g. by Boyle, Black, Marggraf,
Cavendish, Scheele, and especially Bergman, still none of these
investigators made use of the balance as an aid to chemical
work with such a definite aim and perfect conviction of its
significance as he. Lavoisier was penetrated by the truth
that no matter is lost during chemical reactions, and he
gave admirable expression to this conviction of the conserva-
tion of matter by indicating chemical reactions by equations,
writing down as equal the substances before their interaction
with each other and the products of this interaction.1 What
1 In his Trait^ de Chimie (1789) there is the following notable passage in
connection with his researches on fermentation : " Rien ne se cree, ni dans
les operations de I'art ni dans celles de la nature, et Von peut poser en principe
que, dans toute operation, il y a une egale quantite de matiere avant et apres
V operation y que la qualite el la quantite des principes est la meme, et qu'il
n'y a que des changements, des modifications. C 'est sur ce principe qu'est
fonde tout Part defaire des experiences en chimie. On est oblige de. sxpposer,
dans toutes, une veritable egalite" ou Equation entre les principes des corps
qiCon examine et ceiix qiion retire par I 'analyse."
170 THE MODERN CHEMICAL PERIOD CHAP.
many others accepted as being correct, without emphasising
it particularly, was for him a law upon which he based his
speculations and researches. The weight of a compound
body was equal' to the aggregate weights of its constituents.
Although this last sentence now sounds so simple and self-
evident, it had to be proved to those who regarded heat as
material ; for the evolution of heat which took place during
chemical combination was bound to be accompanied by a
decrease in weight, if a caloric was assumed. Lavoisier was
kept from falling into this grievous error by his conception
of the nature of heat. His mati&re de chaleur had no weight ;
this he concluded from experiments in which he burnt sub-
stances in closed vessels, proving thereby that no diminution
in weight occurred. Many of his expressions show that his
views upon its nature approximate to the ' Mechanical
Theory of Heat.1 The phlogistonists, on the other hand,
who saw in heat a ponderable substance, were bound to
suffer shipwreck with such a false basis to start from.
The antiphlogistic system, the outcome of the proper
interpretation of those processes which were designated com-
bustion, calcination, reduction, etc., meant, in fact, a complete
reform of chemistry. The more important of the changes
which the latter underwent have been already detailed, but
it will be convenient here to refer shortly to the most
striking alterations thus effected in the views regarding
elements and chemical compounds. Contemporaneously
with the definite formation of these opinions went the attempts
to introduce a scientific nomenclature, which likewise fall to
be treated of now.
Boyle's view with respect to the term " element " was
retained by Lavoisier ; the latter, therefore, regarded as
elements those substances which could not be decomposed
into simpler ones. But then what immense alterations he
made in details here ! The metals and the most important
non-metals were ranked among the elements; compound
bodies like the alkalies, ammonia and the earths were indeed
numbered among these also, but not without great doubt
1 Cf. (Euvres, vol. ii. p. 285.
v BEGINNINGS OF A RATIONAL NOMENCLATURE 171
being expressed as to their elementary nature. Oxygen,
also recognised as an element, became, on account of its part
in combustion and its capacity for combining with so many
other elements, the centre point of the antiphlogistic system,
which indeed owed its inception to the knowledge of the
behaviour of other elements towards oxygen. The im-
portance which Lavoisier attached to this gas is clearly shown
in his theory of acids, just mentioned, and in the statement
that the bases which combine with acids likewise contain
oxygen. The composition of a large number of com-
pounds— oxides, acids and salts — was thus now rightly
interpreted, the phlogistic hypothesis having regarded as
simple the substances belonging to the first two of these
classes.
The extent of Lavoisier's knowledge and that of his dis-
ciples, and especially their views with respect to elements
and compounds, is to be seen in the work entitled Mtthode de
Nomenclature Chimiqtw, which was published by the former
in 1787 in conjunction with Guy ton de Morveau, Berthollet
and Fourcroy. The three last were the first French chemists
of note to give up the phlogiston theory and to follow the
" new chemistry." To Guyton de Morveau belongs the credit
of making the first attempt towards a convenient chemical
nomenclature, and thereby of inciting to the publication of
the above book.
In this work all substances are divided into elements and
compounds. To the former belonged — in addition to light
and heat — oxygen, hydrogen and nitrogen ; these formed the
first class. The second group contained the acid-forming
elements, — sulphur, phosphorus and carbon, to which were
added the hypothetical radicals of hydrochloric, hydrofluoric
and boracic acids. The third class comprised the metals, the
fourth the earths, and the fifth the alkalies ; but Lavoisier
considered the elementary nature of the last of these as so
improbable that in his Traite' de Chimie (1789) he no longer
included them among the elements. For the nomenclature
of the latter, the old names of the metals and of some of the
non-metals (e.g. soufre, phosphore, etc.) were retained, while
172 THE MODERN CHEMICAL PERIOD CHAP.
Lavoisier's new names for others of the non-metallic elements
{e.g. oxygene, Jiydrogene, azote) were introduced.
Compounds were classified as binary and ternary, and these
designations were to a great extent retained later on, although
it was found necessary to extend their meaning as chemistry
developed. To the binary compounds belonged, in the first
instance, the acids, whose names were composed of two words,
one of which (acide) was common to all, the other being
special to each acid, e.g^ acide carbonique, sulphurique, azotique.
In the case of two acids of one and the same element, the
name of that one which contained the less oxygen ended in
eitx, e.g. acide sulpkureux. The second group of binary com-
pounds embraced the oxygen compounds of the metals, which,
as bases, were placed opposite the acids ; they were given the
generic name of oxydes, that of the particular metal in ques-
tion being added (e.g. oxyde de plomb, etc.) The sulphur es
(e.g. sulphuretted hydrogen and the metallic sulphides), phos-
phures and carbures likewise belonged to the class of com-
pounds of two elements, as did also the compounds of the
metals with one another.
The principal ternary compounds were the salts, produced
by the combination of bases with acids ; their generic name
was derived from the latter, with the addition in each case of
that of the metal, alkali, or earth in question (e.g. nitrate de
plomb, sulfate de baryte, etc.).
The advance which is shown by this classification of
chemical compounds is very great. In place of false assump-
tions and designations devoid of any system, we find a correct
idea of the qualitative composition of substances, and a
rational nomenclature corresponding to this. The develop-
ment of the latter, and the international form which was
given to it by Berzelius, will be treated of below.
Guyton de Morveau, Berthollet and Fourcroy.
These three investigators, who, along with Lavoisier, laid
the foundation of a scientific chemical nomenclature, exercised
a further influence on the development of chemical doctrines
v GUYTON DE MORVEAU : BERTHOLLET 173
by their other work, the most important of which falls to be
considered here. — Guyton de Morveau, born at Dijon in 1 737,
began life as a lawyer (avocat), but gave up this career in order
to devote himself wholly to chemistry. His first attempt at
a chemical nomenclature brought him into close contact
with the French Academy, and in particular with Lavoisier,
the outcome of which was the book cited above. Elected a
deputy in 1791, Guy ton de Morveau did his best to render
his chemical knowledge and its practical application of use
to his country; we have only to recall here his efforts to
employ the air-balloon for strategic purposes in the battle of
Fleurus, his activity in helping to found the ficole Polytech-
nique, in which he subsequently became a professor, and his
services as Director of the Mint, etc. The part which he
played in politics was less beneficial — it was, in fact,
pernicious ; for, although an influential member of the
National Assembly and of the Convention, he did nothing
which could tend to lessen the excesses of the Revolution.
He died in Paris in 1 8 1 6.
To the main service which he rendered, viz. that of having
been efficacious in introducing a rational system of nomencla-
ture for chemical compounds, in place of the unmeaning names
and confusing synonyms1 hitherto in use, he added the
further one of developing this system by experimental
researches in analytical and technical chemistry. He also
aided in spreading abroad a knowledge of the labours of
Bergman, Scheele and Black, by making good translations of
their works.
Claude Louis Berthollet, born at Talloire in Savoy in
1748, had his home in Paris from the year 1772, and
showed a wonderful activity in the most various branches
of chemistry, especially after the year 1780, when he was
1 Thus sulphate of potash had five different names, most of which were
unintelligible, viz. sal polychrestum Glaseri, tartars vitriolatus, vitriolum
potassce, sal de duobus, and arcanum duplicatum. A large number of the
names in common use at that time for gases, salts, acids and bases have
been grouped together by Nordenskiold in an appendix to Scheele's Letters
(p. 467).
174 THE MODERN CHEMICAL PERIOD CHAP.
elected to the French Academy. He found vent for his
great organising talents as a teacher in the Normal and
Polytechnic Schools (after 1794), in Napoleon's historical
expeditions to Italy and Egypt, in which he took part, and
in undertakings for the public benefit. He attained to the
highest honours both under the Empire and after the Re-
storation, and died at Argeuil, near Paris, in 1822. During
the last years of his life, regular meetings attended by
eminent savants were held at his house, their proceedings
being published in the Mdmoires de la Sotiete d' Argeuil
(1807-1817). At first a phlogistonist, Berthollet frankly
declared for Lavoisier's doctrine in 1785.
His experimental researches were especially valuable and
fruitful during this period, i.e. from 1785 until his death.
Mention may be made here of those upon ammonia, prussic
acid, sulphuretted hydrogen and chlorate of potash, and upon
the practical application of chlorine ; he worked out with
substantial correctness the composition of the three hydrogen
compounds just named. But his researches and speculations
upon chemical affinity were of more general and far-reaching
significance his Essai de Statigue Ckimique exercised at that
time and st exercises a most powerful influence ' upon this
question. The cardinal points of his doctrine of affinity will
be given in detail in conjunction with the results obtained
by Proust (whose work arose from Berthollet's), the latter of
which led to the knowledge of definite chemical proportions,
and therefore belong to the history of the development of
the Atomic Theory.
Anton Francois Fourcroy (born 1755, died 1809) under-
stood as a teacher how to inspire his pupils with enthusiasm,
and worked in this way with quite remarkable vigour for the
propagation of the antiphlogistic system, aiding the latter
also by his writings. The chemical articles which he wrote
(after 1797) for the Encydope'die Mtthodique contain pane-
gyrics upon the antiphlogistic chemistry which, in his excess
of patriotic zeal, and possibly not without an egotistical
arri&re pensee,, he termed cliimie frangaise. Fourcroy ex-
v ANTON FRANCOIS FOURCROY 175
pounded the antiphlogistic doctrine in larger works also,
among others in his Systeme des Connaissances Chimiques, and
his Philosophic Chimique, etc.
Born one of an impoverished family, he had to earn the
money required for his studies under the most pressing
circumstances. His work in medicine and natural history
led to the honour of his inclusion in the French Academy in
1 785, a year after he had succeeded Macquer as professor at
the Jardin des Plantes. Later (especially after the Reign of
Terror), when Fourcroy was on the Public Education
Committee, he found an opportunity of utilising the
experiences which he had gained as a teacher. Under
Buonaparte (then Consul) he became himself Minister of
Public Instruction, the education of the country being
reorganised for the most part according to his views, and
special regard paid to scientific studies. It was certainly due
indirectly to him that chemistry bore such wonderful fruit
in France during the succeeding decades. Lastly, he took
the leading part in founding the Polytechnic and Medical
Schools, the ficole Centrale, and the Natural History
Museum.
Fourcroy 's great merit lay in his activity as an organiser
and teacher. And although his experimental investigations
yielded no results of great general significance, they served
as preparatory work in many branches, e.g. in those of
physiological and pathological chemistry. His conjoint
researches with Vauquelin, in which the latter undoubtedly
had the principal share, were of special importance with
regard to organic compounds, which had been but little
worked with up to that time.
The results of most of these researches were published
in the Annales de Ghimie, which was founded at Lavoisier's
instigation by Fourcroy, Berthollet and Guyton de Morveau.
This journal, which started into life during the first year of
the Revolution (1789), lived through the storms of the period
and formed the point of union for French chemists ; it was
at the same time the organ of the new doctrine, as opposed
to the older Journal de Physique, in which the last adherents
176 THE MODERN CHEMICAL PERIOD CHAP.
of the phlogiston theory endeavoured to uphold the latter.
The Me'moires of the French Academy appeared in 1789 for
the last time ; the Academy itself ceased to exist four years
after that date, to be replaced in 1 7 9 5 by the Institwt National
out of which the present Academic Fran$aise originated in
1815, shortly after the Restoration.
After Lavoisier's death the chief representatives of
chemistry in France were the three men just named,
together with Vauquelin the younger. The latter had won
by his researches the right of being numbered among those
who gave effective aid in firmly establishing the antiphlogistic
system. Vauquelin, born at Hebertot in 1763, was first
brought into contact with chemistry as an apothecary's
apprentice; a fortunate destiny led him to Fourcroy's
laboratory, in which he found employment as assistant. He
soon became Fourcroy's collaborates, and attracted the
attention of chemists in general by his brilliant work. From
1793 onwards he filled various posts of distinction, and
laboured with success in many different directions, succeeding
Fourcroy as Professor of Chemistry to the Medical Faculty
after the death of the latter; he died in 1829. Vauquelin
did not content himself with merely teaching chemistry by
lectures, but gave systematic practical instruction in his
laboratory to young men who were desirous of it, and thus
trained many chemists who afterwards rose to fame.
Vauquelin's work, which is characterised by great care-
fulness and exactitude, extended over the most various
branches of chemistry. His investigations of minerals
promoted the development of mineralogical chemistry, and
led him to the discovery of new bodies, e.g. chromium and
beryllia. His splendid gifts of observation likewise showed
themselves in organic chemistry, in the discovery of quinic
acid, asparagine, camphoric acid and other substances. His
papers are to be found for the most part in the Annales de
Chimie, of which he was one of the editors after 1791, but
some of them are contained in the Annales des Mines and
other journals. An " Introduction to Chemical Analysis,"
which appeared in the Annales de Chimie in 1799, may be
v STATE OF CHEMISTRY IN GERMANY 177
mentioned here; a German translation of this led to its
becoming better known and appreciated than would other-
wise have been the case. In 1812 Vauquelin published his
Manuel de I'Essayeur.
Fourcroy's contemporary and Berthollet's celebrated
opponent, Josephe Louis Proust, belongs — in virtue of his
chief work, which helped materially to found the doctrine of
chemical proportions — to the succeeding period, under which
he will therefore be spoken of. Other French chemists, e.g.
Pelletier, Gengembre, Bayen, Parmentier, etc., who gave in
their adhesion to the doctrine of Lavoisier during the lifetime
of the latter, were also active in chemical research, but they
produced no work of general significance; some of the
observations made by them will be referred to in the special
history of the chemistry of the time.
The State of Chemistry in Germany at the End of the
Eighteenth Century.
German chemists proved themselves much less accessible
to the antiphlogistic doctrines than Lavoisier's own country-
men. The more eminent among them only began to slacken
in their warfare against the new views, and to accommodate
themselves to these, during the last decade of the eighteenth
century. Of those who lived during that period, and who
were active both as investigators and teachers, Klaproth
deserves the first mention. Richter likewise participated in
the working out of a most important question for general
chemistry, in that he was the originator of " stochiometry" ;
his investigations are to be looked upon as valuable prepara-
tory work for the chemical atomic theory, and they will be
referred to under this. None of the other German chemists
of that time produced work of general importance, although
they laboured with success in particular departments of the
science. Some of the most noteworthy of these efforts will
find their place in the special history of certain branches of
chemistry ; Buchholz, Trommsdorff, Wiegleb and Westrumb
N
178 THE MODERN CHEMICAL PERIOD CHAP.
may be named here as having enriched pharmaceutical and
technical chemistry by valuable observations. Hermbstadt
and Girtanner were among the German chemists who first
frankly recognised the antiphlogistic system, and they
effectively aided in propagating it in their own country by
means of their writings,
Martin Heinrich Klaproth, born at Wernigerode in 174B
(i.e. in the same year as Lavoisier), only began to teach
chemistry — at the Berlin School of Artillery — when some-
what advanced in life, as he continued true to his apothecary's
calling till 1787; but this did not prevent him from carrying
out in his earlier years investigations of the utmost value, at
first under the guidance of Valentin Rose, and later on,
independently. It was to these latter researches that he
owed his reception into the Berlin Academy. When the
University was founded in the Prussian capital, he — although
sixty-seven years of age — was elected its first Professor of
Chemistry in 1810, and in this post he continued until the
beginning of 1 8 1 7 — the year of his death.
Klaproth was distinguished by the care and thoroughness
with which he carried out all his work; the quantitative
method of research was materially developed and improved
by him, and he thereby helped on the recognition of the
cardinal principles advocated by Lavoisier. After Klaproth
had convinced himself of the correctness of the antiphlogistic
doctrine, by thoroughly testing the reactions which took
place in combustion and calcination, he became one of its
truest adherents; and his example led many other German
chemists in the same direction. Other scientists, too, who
were not precisely chemists, took a part in the contest to
which these theories gave rise ; thus we find Alexander von
Humboldt publicly declaring for Lavoisier's doctrine in
1793.
Klaproth's researches in analytical chemistry were rightly
looked upon at that time as patterns for the younger gene-
ration of chemists. Like Vauquelin's efforts, they aimed
at establishing the composition of minerals by means
of improved analytical methods, and thereby laying the
v KLAPROTH'S LIFE AND WORK 179
foundation for a chemical classification of these. His
observations were so exact as to result in the discovery of
various elements and earths — e.g. uranium, titanium, cerium
and zirconia — while, at the same time, he corrected and
amplified results which had been arrived at by others upon
many new substances — e.g. tellurium, chromium and beryllium.
We shall frequently have occasion to refer to Klaproth's
meritorious work in the history of analytical and mineralo-
gical chemistry. His conscientiousness further showed itself in
the way in which, contrary to the custom prevalent among
chemists at that day, he published the results of his analysis ;
instead of merely stating the conclusions presumably arrived
at from his experiments, he gave the actual figures of these,
and so made it possible to subject them to a minute criticism
or correction.
The above sketch of Klaproth's work may be fitly
concluded by quoting the following sentence of A. W.
Hofmann's1 : — " Endued with a modesty totally alien to
all presumption, recognising to their full extent the services
of others, and tender of his fellow-men's weaknesses but
unsparing in the criticism of his own work, Klaproth will
remain to us for all time the model of a true investigator
of science."
Klaproth's experimental researches were published in
various journals, e.g. in the "Memoirs" of the Berlin Academy
and in Crell's Chemische Annalen ; he himself collected these
scattered papers together into a five-volume work, entitled
Beitrage zur chemischen Kenntnis der Mineralkorper (1795-
1810), to which a sixth volume, Chemische Abhandlungen
gemischten Inhalts, was added in 1815. His literary
activity was further shown in the publication of the
Chemisches Worterbuch (1807-1810), and in the revision
of the works of others, e.g. B. Gren's Handbuch der Chemie
(1806).
That chemistry in general was carefully fostered in
Germany during the two last decades of the eighteenth
century is also proved by the fact that various journals were
1 Chemische Erinnerungen.
N 2
180 THE MODERN CHEMICAL PERIOD CHAP.
started during that period, whose main object was the
publication of papers on chemistry. Among these were L.
von Crell's Chemische Annalen — whose editor merits our
praise, — which were a continuation of the Chemischcs Journal,
begun in 1778 ; Scherer's Allgemeines Journal der Chemie,
which was incorporated with Crell's Annalen after 1803 ;
and the Annalen der Physik, founded by Gren and Gilbert in
1798, and which since 1825 have appeared as Poggendorffs
Annalen der Physik und Chemie.
The State of Chemistry in England, Scotland and Sweden
towards the End of the Eighteenth Century.
The most distinguished chemists in England and Sweden
at the time of Lavoisier's attack upon the phlogiston theory,
viz. Black, Cavendish, Priestley, Scheele and Bergman, were
avowed opponents of the new doctrine. Black alone among
them, after considerable hesitation, frankly recognised its
truth. Cavendish, whose own discoveries contributed in great
degree to the downfall of the phlogistic view, could not bring
himself fairly to renounce it. The others, whose brilliant
work had likewise forged the best weapons for its overthrow,
died without being convinced of its untenability. Other
English chemists, for instance Henry, Kirwan, and Hatchet,
also tried to hold fast by the phlogistic hypothesis so long as
it appeared possible to say anything in its favour. Kirwan
especially, who was one of those who believed phlogiston to
be identical with hydrogen, continued the fight against the
new doctrine till 1792, in which year he subscribed to it
himself. Its first adherent in England was Lubbock, who
concurred in Lavoisier's views so early as 1784. The four
chemists just named, being representatives of their science
at that day, merit this brief mention ; they advanced par-
ticular branches of chemistry by their work, but did not
influence its general tendency. Thus their countryman,
John Dalton, who soon after this made such a wonderful step
in advance, showed only the greater individuality in pointing
v WORK PREPARATORY TO DALTON'S ATOMIC THEORY 181
out the new path, by following which chemical research has
since made such enormous strides.
After the deaths of Bergman and Scheele, Sweden had at
the close of the eighteenth century no chemist who enriched
the science with facts of general importance, though Ekeberg
and Gahn worked energetically at analytical and mineralogical
chemistry. It was only at the dawn of this century that
Berzelius' star arose, the light from which was to illumine
nearly every branch of chemistry during its first four decades.
A period singularly rich in scientific facts for chemistry thus
began with him, while in his contemporaries, Davy and Gay-
Lussac, the science possessed two other workers of the highest
power. Dalton's Atomic Theory, founded as it was upon the
doctrine of chemical proportions, formed the basis of all their
efforts.
Development of the Doctrine of Chemical Proportions.
Dalton s Atomic Theory.
The idea of atoms as forming the ultimate constituents of
matter often arose of old in speculative minds, without, however,
an exact chemical atomic theory being evolved from it.
Boyle's corpuscular theory was and remained merely a product
of ingenious speculation, which ended in the assumption of a
primary material, and therefore bore no fruit. Only after
a series of proven facts had led to the presupposition of
atoms, and after this assumption had enabled those facts
to be satisfactorily explained, could there be any talk of
founding a chemical atomic theory. The merit of estab-
lishing this is without a shadow of doubt due to John Dalton.
But before it could be brought to completion, the meaning of
the term " chemical proportions," according to which simple
substances united to form compound ones, had to be firmly
fixed ; and an important part of this problem was worked out
by two chemists before Dalton, viz. Richter and Proust.
Richter, whose work was to all intents and purposes un-
known to Dalton at the time when he conceived his atomic
182 THE MODERN CHEMICAL PERIOD CHAP.
theory1, founded the doctrine of chemical proportions without,
perhaps, seeing its great importance himself, while Proust
proved that the ratio in which two elements combine
chemically with one another is constant, or, if there is more
than one compound of these elements, the ratio alters
by definite increments. If we but consider that the
atomistic hypothesis, from which the chemical atomic theory
sprang, originated with an observation by Dalton which
followed from Proust's demonstrations, and which was com-
prised within the law of multiple proportions, we see how
intimate was the connection between the latter and these
preparatory labours (cf. note 1, p. 189).
Jeremias Benjamin Richter, born at Hirschberg in
Schlesien in 1762, became a mining official (Bergsekretar)
at Breslau, and then chemist (Bergassessor and Arkanist2) in
the porcelain manufactory at Berlin, in which city he died
in 1807. His researches — from which the doctrine of pro-
portions by weight was mainly established, and which showed
that acids combined with bases to form salts — together with
the conclusions which he drew from them, were published
by him in his Anfangsgrunden der Stochiometrie oder Mess-
kunst Chemischer Elemente ("Rudiments of Stochiometry, or
the Art of Measuring Chemical Elements"), (1792-1794),
and in his work entitled, Ueber die neueren Gegenstande in
der Chemie (" Upon recent Discoveries in Chemistry "), which
was published in eleven parts at irregular intervals between
1792 and 1802; this latter was in great part a continua-
tion of the first-mentioned book.
Many chemists before him had busied themselves with
the same task — the determination of the amounts of acid
and base in salts ; in addition to Kunkel, Lemery, Stahl
and Homberg, special mention must be made here of Wenzel
(who was born at Dresden in 1740, and died while director
of the Freiberg foundries in 1793), who placed beyond a
1 Angus Smith, Memoir of John Dalton and History of the Atomic-
Theory, p. 214.
2 Arkanist, meaning literally " secret chemist," was the German title in
use at that time.
v JEREMIAS BENJAMIN RICHTER 183
doubt the fact that acids and bases combine in constant
proportions, grounding this conclusion upon the results of
numerous and, for the most part, thoroughly serviceable
analyses. Richter was in a position to deduce the important
" law of neutralisation " (Neutralitatsgesetz) from his own
researches upon the quantities of bases and acids which
combine to form neutral salts — researches carried out with
great circumspection. Translated from his writings, ob-
scured as these were by much phlogistic verbiage,1 into the
chemical language of to-day, this runs somewhat as follows :
" When equal amounts of one and the same acid are rendered
neutral by different amounts of two or more bases, the latter
are equivalent to one another, and vice versa." It follows
quite clearly from his statements that he regarded those
quantities of oxides which contain equal amounts of oxygen
as equivalent to one another, i.e. as requiring like quantities
of a given acid to neutralise them. Richter had come to the
right conclusion as to the capacity of iron and quicksilver
to unite with oxygen in two proportions, from the composi-
tion of the corresponding salts. With these weighty
observations he thus anticipated the precisely similar ones
of Proust. Scheele had previously attained to the same
knowledge (cf. p. 127).
Notwithstanding that Richter's work contained such far-
reaching discoveries, these remained almost unnoticed, their
value being manifestly not recognised. This was partly due
to the peculiar phlogistic language — obscure and clumsy
— in which he clothed the results of. his researches. A
curious speculation in which he indulged may also have
caused his whole work to be unfavourably criticised, —
his assumption, namely, that a definite arithmetical relation
existed between the combining weights of the bases and
acids.2 Judicious as he was in other points, he believed that
he had found a proof that the combining weights of the bases
1 Although he had ceased to be a phlogistonist, Richter still made fre-
quent use of phlogistic expressions, which often obscured his writings.
2 Even before his scientific career had begun, Richter was animated with
the conviction that " chemistry was a branch of applied mathematics."
184 THE MODERN CHEMICAL PERIOD CHAP.
and acids form approximately regular series, — the former
arithmetical, and the latter geometrical. The importance
which he assigned to his "law of progression," and his
continuous efforts to furnish proofs in support of it, mani-
festly prevented him from perceiving the significance and
range of his law of neutralisation; indeed, he held this
speculation as being the more important of the two.
The chemical world was to a certain extent made
acquainted with the truths lying dormant in Richter's papers
by G< E. Fischer, who put his countryman's observations
into intelligible language; he collected together in a clear
manner the scattered numerical values which Richter had
arrived at as representing the amounts of bases and acids
which combined with one another, and thus prepared the
first table of equivalent weights.1 Notwithstanding that
the attention of chemists was in this way drawn to Richter's
researches, it was a long time before they became thoroughly
known and estimated at their true value. It was thus that
facts proved by him were rediscovered by others much later,
e.g. the combination of bases which contain equal amounts of
oxygen with equal quantities of the same acid, by Gay-Lussac,
who was without doubt unacquainted with this portion of
Richter's work. As Kopp pertinently remarks in his Ent-
wickehong der Chemie in der neueren Zeit, S. 152 (" Development
of Chemistry in Recent Times," p. 152): "The history of
our science affords few examples of important and well-proven
facts being overlooked for so long a time and to such an
extent; and, further, when the appreciation of these facts
did finally come, of the merit of their discovery being
minimised so far as the discoverer himself was concerned,
and the credit given in great part to another."
It was only long after his death that Richter's services
were recognised to their full extent.2 Starting from the
1 This table was published by Fischer in his translation of Berthollet's
Recherches sur Us Lois de VAffinitd. The fact that the latter adopted
Fischer's grouping in his work, Essai de Statique Chimique, vol. i. p. 134,
made Richter's labours known in France also.
2 Cf. especially C. Lowig's memoir, Jeremias Benjamin Richter, der
v JOSEPHE LOUIS PROUST 185
observation that the neutrality is not disturbed by the
mutual decomposition of two neutral salts, he created the
doctrine of equivalents ; he was the originator of " Stb'chio-
metry," 1 — " the art of chemical measurement, which has to
deal with the laws according to which substances unite to
form chemical compounds."
Josephe Louis Proust. — The work of this investigator,
who, independently of Richter, also partially proved the
validity of the law of chemical proportions, fell later in point
of time than the most important of Richter's researches.
Born at Angers in 1755, Proust went through Rouelle's
course of study, and then applied his knowledge of pharmacy
and chemistry in the first instance as manager of the
apothecary's shop attached to the Salpetriere Hospital in
Paris, and later as a teacher in different Spanish universities.
It was in Madrid, where he settled after 1791, that he
carried out his most celebrated investigations. The war
deprived him both of his post and of his splendidly equipped
laboratory in 1808, and it was only towards the end of his
life that his necessities were relieved by a pension, while
he was at the same time received into the Paris Academy ;
he died at his native town of Angers in 1826.
His most important work was the result of a series of
questions which Berthollet had propounded. At the end of
the eighteenth century (i.e. from 1798 onwards), the latter's
Kccherches sur les Lois de VAffinitt, which he collected together
in 1803 in his Essai d'une Statique Chimique, created an
extraordinary sensation. Grounding his objections upon
Entdecker der chemischen Proportioned, (Breslau, 1874) [" Jeremias Benjamin
Richter, the Discoverer of Chemical Proportions " (Breslau, 1874)]. Ac-
cording to Fischer, Richter's work was particularly emphasised by Gehlen,
Schweigger and Berzelius. The discovery of the law of neutralisation was
ascribed by Berzelius to Wenzel, in consequence of a misunderstanding on
the part of the former ; and it was left to H. Hess of St. Petersburg to
point out this error, thirty-three years after Richter's death.
1 Richter himself says that he was unable to devise a better name for
this than the word " Stb'chiometrie, from ffroix^ov, signifying something
which cannot be further divided, and /leTpe^, which denotes the finding out
of relative proportions. "
186 THE MODERN CHEMICAL PERIOD CHAP.
speculations apparently well founded, this gifted writer dis-
puted the fact that constant proportion was the rule with
regard to the constituents of chemical compounds. His
ideas upon chemical affinity, by which the combination of
substances with one another is regulated, will be treated of
in detail in the special history of this part of our science.
Suffice it to say here that, starting from the axiom that
chemical processes are dependent upon the relative masses
of the reacting bodies, he arrived at the conclusion that, in
a chemical compound which results from the union of two
substances, so much the more of the one substance must
enter into it, the more of that substance there is available,
always supposing that no exceptional circumstances stand in
the way of this mass-action. Berthollet's great reputation
may have been the reason why none of the other leading
chemists of the day raised any objections, although they
certainly did not concur in this view. For, with respect
to many compounds, salts especially, the constancy of the
combining proportions of their constituents was a fact be-
yond all doubt to men like Richter, Wenzel, Klaproth,
Vauquelin and others.
Proust took up the cudgels against Berthollet, and, by
means of exact experiment, overthrew one by one the
theoretical conclusions of his opponent. This memorable
controversy, which, beginning in IT 9 9, was continued for
eight years, and which was conducted on both sides with
consummate ingenuity and supplemented by laborious in-
vestigations, ended in the conclusive proof of constant
combining proportions.
To what extent Dalton was influenced by Proust's labours
in his researches in a similar direction, it is hard to say ; but
they were certainly not without some effect upon him, the
dispute between Berthollet and Proust being followed with the
keenest interest in scientific circles.
So early as the year 1799 Proust had proved the con-
stant composition both of natural and of artificial carbonate
of copper,1 and had called special attention to the unvarying
1 Ann. de Chimie, vol. xxxii. p. 30.
v THE PROUST- BERTHOLLET CONTROVERSY 187
proportions by weight in true chemical compounds, as opposed
to the varying ones in mixtures. Still more important than
these were observations — to be supplemented later on by
himself and others — upon the two stages of oxidation
which tin shows,1 and upon the two compounds which
iron forms with sulphur;2 for he particularly emphasised
the point that not only were the proportions between
the metals and oxygen or sulphur constant in the in-
dividual compounds, but also that the combining pro-
portions increase by leaps, and not gradually, when two
elements unite to form more than one compound. Ber-
thollet thought that he had proved exactly the opposite in
his researches on the formation of oxides and salts3 (e.g.
the nitrates of mercury), viz. that metals can form oxides
with gradually increasing amounts of oxygen. But Proust 4
showed that his experiments were wrong, and that he had
deduced his conclusions from the analysis of mixtures and
not of definite compounds. The superiority of Proust in
experimental points was clearly manifested, since he proved
to Berthollet that many of the substances which the latter
regarded as oxides contained chemically-combined water;
it was Proust who first classed the hydrates among chemical
compounds. In fact, he succeeded by generalisation and by
firmly establishing his view — that combination between the
other elements and oxygen or sulphur only takes place in
one or, at most, in a few proportions — in completely routing
the weak arguments of his opponent, many of which were
advanced without any experimental proof to support them.5
Proust had repeatedly laid stress upon the validity of
combining proportions, without however trying to get clearly
at the reasons for this. How near he was to recognising
the law of multiple proportions, which Dalton deduced from
his own researches — researches similar to Proust's, and not
excelling these in exactitude ! One is led to the surmise
1 Journ. de Phys., vol. li. p. 174. 2 Ibid., vol. liv. p. 89.
3 Cf. Essai de Statique Chimique, vol. ii. p. 399 et seq.
4 Joum. de Phys., vol. lix. pp. 260, 321.
6 Ibid., vol. Ixiii. pp. 364, 438.
188 THE MODERN CHEMICAL PERIOD CHAP.
that if Proust had calculated the results of his experiments
on the composition of binary compounds otherwise than he
did, he would have discovered that law. The happy idea
occurred to Dalton of reckoning the amounts of one element,
which combined in different proportions with another, in
terms of a given chosen quantity of the latter ; the result of
this was that the multiple proportions became manifest, and
these he explained by the aid of the atomic hypothesis.
DALTON'S ATOMIC THEORY.
John Dalton,1 the eldest son of a poor weaver, was
born at Eaglesfield in Cumberland on September 6th, 1766,
and had to make his own living at an early age as an
elementary teacher. Endowed with a strong bent towards
mathematics and physics, he acquired a sound knowledge of
these subjects, and was thus enabled to carry out indepen-
dent investigations in them, and to take the post of mathe-
matical and physical master in a college at Manchester in
1793. It was there, in 1794, that he made the important
discovery of colour-blindness, which he noticed in the first
instance in himself; as a consequence of this the phenomenon
goes by the name of Daltonism to the present day. He soon
included chemistry also in his studies, the most important
problem of which he was destined to solve. In his modesty
Dalton had no thought of acquiring for himself a brilliant
position in life, and a wide sphere of action ; after 1 7 9 9, in
fact, he supported himself by taking private pupils. The
highest reward for his truly philosophic mind consisted in
the elucidation of the truth. He died at Manchester in
1844.
Dalton's earlier researches on the physical behaviour of
gases (their expansion by heat and absorption by liquids)
1 For Dalton's life and work, compare the Memoirs of the Life and
Scientific Researches of John Dalton, by W. C. Henry, M.D. (Cavendish
Society, London, 1854), and Lonsdale's Li fe of Dalton ; the latter author has
preserved to us a number of traits which were characteristic of Dalton's
simple and kindly nature.
JOHN D ALTON 189
were of great influence upon his later chemical labours. For
it was through them that he acquired the experimental
dexterity which stood him in such good stead when analysing
those gases, whose composition led him to the law of multiple
proportions.
The discovery of this law, and the conception of the atomic
theory which arose from it,1 date from about 1802-1803.
After that time Dalton applied himself to the task of building
up a firm foundation for these by amplifying his observa-
tions; he only published his discovery in 1808, when the
first volume of his New System of Chemical Philosophy appeared.
But the outlines of the atomic theory had, with Dalton's
concurrence, been made public by Thomas Thomson — an
enthusiastic admirer of Dalton — in his System of Chemistry
a year before this, so that the first influence of this great
scientific event upon the chemical world is to be dated from
then. The second volume of Dalton's above-mentioned
work, with material additions to the researches originally
published, appeared in 1810, and the third volume so late
as 18 27, by which time its contents were mostly out of date.
The first of Dalton's observations which formed the
starting point for the atomic theory consisted in the deter-
mination of the composition of oil-forming gas (ethylene),
1 Interesting details respecting the steps by which Dalton was led to
the formulation of his atomic theory have recently been given in H. Debus's
Die Genesis von Dalton's Atomtheorie, Parts I and II [Ztschr. phys.
Chem., xx, 3 (1896); xxiv, 2 (1897)], and Roscoe and Harden's A New
View of the Origin of Dalton's Atomic Theory, a Contribution to Chemical
History, etc. (MacmillanandCo., 1896). Cf. Also H. Debus's pamphlet : —
Ueber einige Fundamentalsdtze der Chemie, insbesondere das Dalton-
Avogadro'sche Gesetz (1894). According to these authors, Dalton arrived
at the atomic hypothesis deductively about the year 1801, and not from
the result of his researches on the composition of gases. The discovery of
the law of multiple proportions was thus not the cause of the atomic theory
being brought forward, but, on the contra'ry, succeeded the latter. — This
is a point which is obviously of the first importance in the history of
chemistry. But the author feels that before he can himself express a
definite opinion on the subject, a more minute re-examination of the whole
question is required than the time at his disposal permits, before the issue
of the present edition. In the meantime, therefore, the different views are
merely placed before the reader.
190 THE MODERN CHEMICAL PERIOD CHAP.
and light carburetted hydrogen (methane). From his ana-
lyses of these two gases he concluded that, for the same
quantity of carbon, twice as much hydrogen was contained
in the latter as in the former, i.e. that the proportions of
hydrogen were as 2:1. This regularity induced him to
investigate other compounds in the same direction; thus,
in the case of carbonic oxide and carbonic acid, he found
that, for the same amount of carbon, the ratios of oxygen
present in these were again respectively as 1 : 2. His
conviction that there must be a law underlying these so
simple relations hardly required any further strengthening
after he had met with similar simple numerical proportions
in the results of his analysis of nitrous oxide, nitric oxide,
nitrous acid and nitric acid (i.e. the anhydrides of the two
last).1 He had, therefore, proved that when different quan-
tities of one element combined chemically with one and
the same quantity of another, these amounts stood in a
simple relation to one another — a relation which could be
expressed by whole numbers. The law of multiple pro-
portions was thus discovered; it had, indeed, been deduced
from experiments which were of necessity not very exact, as
was to be expected from the state of chemical analysis at
that time.
Dalton, however, did not remain content with this
important result, but sought an explanation of the numerical
relations which he had discovered. This was afforded him
by the atomistic hypothesis, in the assumption, not new in
itself, that substances consist of ultimate particles not
further divisible — of atoms. This hypothesis gave a satis-
factory explanation of the facts comprised within the law of
multiple proportions, for one now only required to substitute
absolute numbers for the relative ones, i.e. to assume that in
carbonic oxide (for instance) one atom of carbon was com-
bined with one of oxygen, and in carbonic acid one atom of
carbon with two of oxygen, and so on. Upon the firm basis
of this assumption Dalton erected his Atomic Theory, the
1 Dalton was, however, wrong in his analysis of nitric acid, which he
made out to consist of nitrogen and oxygen in the proportions of 1 atom to 2.
v DALTON'S ATOMIC THEORY 191
essence of which is given in the two succeeding para-
graphs : —
(1) Every element is made up of homogeneous atoms
whose iveight is constant.
(2) Chemical compoimds are formed ~by the union of
the atoms of different elements in the simplest numerical
proportions.
His speculations upon the atoms themselves, which
Dalton assumed for the sake of simplicity to be spherical in
shape, and also the hypothesis that they do not come into
direct contact with one another but are separated by a heat
zone, have but a merely subordinate significance as compared
with the above two sentences ; they exercised no influence
on the development of the chemical atomic theory.
Dalton now sought to deduce the relative atomic weights
from the proportions by weight in which the elements unite
to form compounds, proceeding to this task, which consti-
tuted the main feature l of his New System, with wonderful
confidence. Since he had no certain means of arriving at
these numeric proportions of the combining atoms, assump-
tions had to be made, and these were of the simplest kind.
The following statements by Dalton refer solely to compounds
of two elements.
When only one compound of two elements A and B is
known, we must assume that it is made up of one atom of
the one and one atom of the other : A + B (binary compound,
or atom of the second order. Dalton spoke of an elementary
atom as .an atom of the first order).
If two compounds of two elements A and C are known,
their composition is expressed by the symbols A + C and
A -{-20 (ternary compound, or atom of the third order).
When the composition of three compounds of two
1 Dalton's own words are : — (to ascertain) the relative weights of the
ultimate particles, both of simple and compound bodies, the number of simple
elementary particles which constitute one compound particle, and the number
of less compound particles which enter into the formation of one more com-
pound particle.
192 THE MODERN CHEMICAL PERIOD CHAP.
elements A and D had to be decided, then, according to
Dalton, the following combinations were the probable ones :
A+ D, A + 2D, and 2.4 + Z>. Atoms of the fourth order
(e.g. A + 3E), etc., were also allowed by Dalton, although
he favoured the more simple proportions. Compounds whose
atomic numbers were as 2 : 3 or 2 : 5, he explained as result-
ing from two atoms of a higher order than the elementary
atom (e.g. nitrous acid from one atom of nitric oxide and
one of nitric acid).1
Dalton's statement that the atomic weight of a compound
is equal to the sum of the atomic weights of its constitu-
ent elements appears to us nowadays self-evident ; but we
must not forget that at that period, in spite of Lavoisier's
energetic protest, the false idea of heat being material had
by no means been discarded by all chemists, many of them
still believing that a loss of matter occurred when heat was
evolved from the combination of two elements.
Setting out then from the above premises, Dalton en-
deavoured to determine the relative atomic weights of the
elements as follows : — Starting with water, as the only com-
pound of hydrogen and oxygen (peroxide of hydrogen being
at that time unknown), he estimated the proportions in which
both of these were present, and then took hydrogen as the
unit to which oxygen and other elements were to be referred.
1 Dalton's precise words, as given in his New System, second edition,
vol. i. p. 213, are as follows : —
"If there are two bodies, A and B, which are disposed to combine, the
following is the order in which the combinations may take place, beginning
with the most simple, namely :
" 1 atom of A + 1 atom of B= 1 atom of C, binary,
" 1 atom of A + 2 atoms of B = l atom of D, ternary," etc.
Again, at p. 214 : —
" 1st, When only one combination of two bodies can be obtained, it must
be presumed to be a binary one, unless some cause appear to the contrary.
"2d, When two combinations are observed, they must be presumed to
be a binary and a ternary.
"3d, When three combinations are obtained, we may expect one to be
a binary and the other two ternary.
"4th, When four combinations are observed, we should expect one
binary, two ternary, and one quaternary, etc."
v DALTON'S ATOMIC WEIGHTS 193
The relative values of the latter, as deduced from the com-
position of their oxygen and hydrogen compounds, were
according to his view their atomic weights. In this
way he determined the relative atomic weight of nitrogen
from the composition of ammonia, which, as the only com-
pound of hydrogen and nitrogen, consisted of one atom of
each of those elements ; and that of carbon from the analyses
of carbonic oxide and carbonic acid, using in this case the
value he had obtained for oxygen in the analysis of water.
As the analytical methods which he employed were liable
to many sources of error, it was impossible that his results
could be accurate ; but the great merit . belongs to Dalton
of having propounded the principle of the determination
of the relative atomic weights, or, to speak more correctly,
of the combining weights of the elements. How far his
first " atomic- weight numbers," as published by Thomson in
1805, differ from the values current to-day, is seen from the
following table : —
" Relative Atomic Weights."
According to
Dalton.
Their current
Values.
Hydrogen ....
Oxygen ....
1
6-5
1
7-98
Nitrogen ....
5
4-66
Carbon ....
5-4
6
Dalton published a greatly extended and, to some extentr
improved table of " relative atomic weights " in the first
volume of his work (1808), in which 7 is the value given for
oxygen ; the numbers which he obtained are too low through-
out, and deviate from the true values by several units in the
case of the elements of higher atomic weight.1 His attempt
to apply the atomic hypothesis to organic compounds must
1 This table of atomic weights shows his endeavours to round off the
numerical values, from his perception of the insufficiency of the methods
employed, as is seen in the following instances ; the figures appended below
in brackets, after those of Dalton, give the correct combining weights :
sulphur 13 (16), iron 38 (56), zinc 56 (64'9), copper 56 (63'3), silver 100 (108),.
mercury 167 (200).
O
194 THE MODERN CHEMICAL PERIOD CHAP.
also be mentioned here, although it turned out unsuccessful,
the results of his organic analyses being far from exact.
Nor must we forget Dalton's efforts to build up a system
of notation which should illustrate atomic composition.
The atoms of the elements were represented by various
circular symbols, e.g. oxygen by an empty circle O,
hydrogen by 0, nitrogen by 0 , and sulphur by ®.
These signs, placed conveniently near to each other,
indicated the supposed constitution of chemical compounds ;
for water the symbol 0O was used, for ammonia 00,
for sulphuric acid 1 ^ y ^ , and so on.
CJ^pU
But the simpler and easily decipherable system of nota-
tion which Berzelius introduced some time after this, pre-
vented Dalton's from ever coming into general use.
Further Development of the Atomic Theory.
The reception which Dalton's atomic theory found
among chemists was almost wholly favourable, although
there were not wanting a few to depreciate the new doctrine,
and even to ascribe the merit of its origination to others.
In Great Britain it found from the beginning an enthusiastic
adherent in Thomas Thomson,2 who, however, rather did it
harm than good by his excess of zeal, a fatal tendency to
speculation sometimes causing him to quit the sure ground
of exact experiment. It was of particular importance, at the
1 Dalton did not know the compound S03, but supposed that this
formula gave the composition of sulphuric acid.
2 Thomas Thomson (born 1773, died 1852) exercised no slight influence
on the growth of theoretical chemical views, especially in England, both by
his experimental researches in chemistry, and by his text-books. That it
was he who first gave to the public the principles of Dalton's atomic theory
has been mentioned already. As a historian of chemistry he was also active,
his History of Chemistry appearing in 1830-31. Most of his papers were
published in the Annals of Philosophy, which he himself edited. As pro-
fessor in the University of Glasgow (1818-1841) he was eminently success-
ful, founding there the first chemical laboratory for general instruction in
Great Britain.
FURTHER DEVELOPMENT OF THE ATOMIC THEORY 195
time a theory so far-reaching was set up, that the facts on
which it rested (still few in number) should be amplified and
deepened by reliable observations.
The estimations made by Thomson of the relative atomic
weights of elements and compounds were still more defective
than Dalton's, and became influenced subsequently in an in-
excusable manner by Prout's erroneous hypothesis, — and
that, too, after Berzelius had begun his long series of classical
labours with the accurate determination of atomic weights.
On the other hand, Thomson's investigation of the potash
salts of oxalic acid helped to confirm the atomic doctrine,
since they showed that the quantities of potash which
reacted with a given amount of oxalic acid were to each
other as 1 : 2 : 4 by weight. An analogous observation was
made by Wollaston,1 who found that in the neutral and acid
carbonates of potash the proportions of carbonic acid rela-
tively to the same weight of potash were as 1:2. The
applicability of the law of multiple proportions was thus also
proved for salts.
The position which from that time (about 1808) the
most distinguished investigators of the day — Davy, Berzelius
and Gay-Lussac — took up with regard to Dalton's atomic
theory, renders an account of their most important work
and their general services appropriate at this point. The re-
searches of Gay-Lussac upon gases, and even more the un-
resting efforts of Berzelius to work out sure foundations for
the determination of the true atomic weights, had the deepest
influence on the development of the atomic doctrine, which
is now the basis of chemistry.
Davy and Gay-Lussac; their life and work. — Davy
was at first sceptical with regard to Dalton's rights as theorigin-
1 W. H. Wollaston was born in 1766 (the same year as Dalton), and died
in 1828. Originally a physician, he soon gave himself up to the study of
physics and chemistry, enriching the former especially by important ob-
servations. At the same time he became favourably known by his chemical
researches, particularly by his work on the platinum metals. Most of his
papers are to be found in the Philosophical Transactions, but a few of them
in the A nnals of Philosophy.
o 2
196 THE MODERN CHEMICAL PERIOD CHAP.
ator of the atomic theory, and indeed, in 1809, he claimed for
Higgins the priority for this doctrine, the latter having made
use of the atomic hypothesis to explain chemical facts so-
early as 1*789 (in his work, A Comparative View of the
Phlogistic and Antiphlogistic Theories). Higgins certainly
expressed opinions which, on a superficial glance, appeared
similar to those of Dalton, stating as he did that the smallest
particles combine in simple numerical proportions to form
chemical compounds. But these views were brought forward
without any internal organic connection, and, moreover, they
were not based upon experiment. It became clear to Davy
later on that Higgins had no claim to be regarded as the
originator of the atomic theory, and he then frankly recog-
nised Dalton's service.
Humphry Davy, born at Penzance in Cornwall in 1778,
was destined for a distinguished career, to be cut short by an
early death, his creative genius being impaired during the
last years of his life by prolonged illness. So early as 1813,
when only thirty-five of age, he had to leave off work and
seek renewed health on the Continent, in Italy for the most
part. From that time he travelled a good deal. After 1820
he lived and worked again in England, but left it in 1827, never
to return, for he died in 1829 at Geneva on his homeward
journey.
While only a surgeon's assistant, Davy acquired by his
own energy such a wide knowledge of chemistry and the
natural sciences, that at twenty years of age he was able to
take the post of chemist in the newly- founded Pneumatic
Institution at Bristol. The aim which this institution had
set before itself was to test the various artificially prepared
gases for their physiological and medical action. It was
here that Davy carried out his researches on nitrous oxide,
whose intoxicating and stupefying action he discovered, and
on the effect of other gases (admixed with nitrogen) on the
organism, e.g. hydrogen and carbonic acid ; in this way he
laid the foundation of his fame as a great experimenter.
So early as 1801 we find him assistant professor at the Royal
Institution of London (very soon to become professor), and
HUMPHRY DAVY 197
shortly afterwards a member of the Royal Society, whose
president he became in 1820.
His most memorable work, which effected a complete
transformation in many branches of chemistry, was accom-
plished during the first thirteen years of this century. We
need only mention here the isolation of the metals of the
alkalies and alkaline earths by the galvanic current, through
which a whole series of hitherto undecomposed substances
were recognised as compound. An almost still more im-
portant result of these observations was the discovery of
the elementary nature of chlorine, which up till then was
held to be a compound ; this opened out entirely new stand-
points, which led to a transformation of the views upon the
constitution of acids. When it was proved that there
were acids which did not contain oxygen, a material altera-
tion in Lavoisier's theory became for the first time necessary.
Discoveries of such range as this characterise the period in
which Davy developed his wonderful activity. His most
important experimental researches will be described partly in
the further course of the general history of this period, and
partly in the synopsis of the progress of particular branches
of chemistry.
Davy contributed greatly by his popular lectures, es-
pecially by those given for the Board of Agriculture, to
heighten the public interest in chemistry during the first
decade of this century. He it was, too, who showed in what
high degree chemistry could and should meet the require-
ments of technical industries and of daily life ; we have only
to think in this connection of the miner's safety lamp which he
constructed.
Davy's genius in grasping chemical relations was especially
apparent in his efforts to discover the connection between
electricity and chemical affinity, both of which he regarded
as resulting from a common cause. He was the first to set
up an electro-chemical theory grounded upon experiments,
which were devised and carried out in a masterly manner,
and in this way he opened out the province in which
198 THE MODERN CHEMICAL PERIOD CHAP,
Berzelius was to work with such effect in the decade
following.1
Wherever Davy, with his aptitude for experiment and
acuteness of mind, treated chemical problems, he achieved
great results. Within the narrower limits of special research
also, e.g. in his invesigations on ammonium amalgam, phosgene,
eu chlorine, iodine, solid phosphuretted hydrogen, and the
phenomena of combustion, the fruits of his labours were at
once perceptible ; his work always left a deep mark. After
the year 1801 Davy published his most important papers in
the Philosophical Transactions, but some are to be found in the
Annales de Chimie and in the Journal de Physique. Of his
few larger works,2 the Elements of Chemical Philosophy
(1810-12) became best known, especially as it was soon
translated into French and German. After his death all his
works were collected together and published by his brother
John Davy.
In addition to the interest which Davy's wonderful
services to science call forth, there is to be added the purely
human interest in his personality. The nobility and poetry
of his nature are shown both in the journals which he kept
during his extended journeyings in France, Germany and
Italy, in his letters, and his Memoirs.2' The inventions made
by him for the public good raise still higher our regard for
this remarkable investigator.
1 Davy's electro-chemical theory of affinity will be described along with
that of Berzelius in one of the succeeding paragraphs.
2 The judgment which Berzelius passed upon Davy's literary activity,
in a letter written to Wohler in 1831, is of much interest (cf. Ber., vol. xv.
p. 3166). The latter had been deploring that he was overwhelmed with
literary work, whereupon Berzelius replied as follows: "Had Davy been
forced to occupy himself as much with writing as you have to do now, I am
convinced that he would have advanced chemistry by a hundred years ; but
he remained only a ' brilliant fragment ' (ylanzendes Bruchstiick), because he
was not compelled from the beginning to initiate himself thoroughly into
every part of the science as into one organic whole."
3 Memoirs of the Life of Sir Humphry Davy, by J. Davy (London,
1839). — A delightful monograph on Davy, based for the most part on Dr.
John Davy's work, has recently been written by T. E. Thorpe (Century
Science Series, Cassell and Co., 1896).
DAVY ; GAY-LUSSAC
Davy's historico-critical attitude towards Dalton's atomic
doctrine has been already spoken of. But although he
subsequently gave the latter credit for originating this
theory, he continued sceptical with regard to Dalton's con-
clusions.1 He would not admit that Dalton's atomic weights
were really such ; in his view these were merely the proportion
numbers of the elements, for the determination of whose
atomic weights there was no sure basis to go upon.
Wollaston had before this given utterance to a similar
circumspect criticism of Dalton's bold speculations, having
published in 1808 his opinion that the numbers arrived at
by Dalton gave, not the atomic weights, but the chemical
equivalents of the elements. Gay-Lussac, too, whose labours
began at that time to exercise such a powerful influence
on the development of chemistry, rejected the assumption of
atomic weights, and merely allowed that the ratio (rapport)
of one element (e.g. hydrogen, nitrogen, or iodine) to another
(e.g. oxygen) was established by analytical and synthetical
determinations.
Gay-Lussac, whose critical attitude to Dalton's atomic
theory has just been touched upon, helped on the latter in
a quite exceptional degree by his wide-reaching discovery of
the so-called " Law of volumes " — more, indeed, than he was
willing to confess.
Josephe Louis Gay-Lussac, born in 1 7 7 8 at St. Leonard
in the old province of Limousin, after acting as Fourcroy's
demonstrator became in 1809 professor of chemistry at the
Ecole Polytechnique (at which he had been a pupil up to the
year 1800), and at the same time held the chair of physics
at the Sorbonne. In 1832 he resigned his chair at the
Sorbonne to fill that of general chemistry at the Jardin des
Plantes ; he died in 1850. After his initiation into science
by Berthollet, and while still very young, Gay-Lussac aroused
the marked attention of his contemporaries by his physical
investigations on the behaviour of gases — investigations
which touched more or less on the province of chemistry.
Brief mention may also be made here of his bold balloon
1 Cf. particularly his Elements of Chemical Philosophy.
200 THE MODERN CHEMICAL PERIOD CHAP.
-ascents in 1804, undertaken at first along with Biot and
afterwards alone. His researches made after 1805, upon
the laws deducible from the combining volumes of gases
which unite chemically with one another, had most incisive
results. What rich fruit this yielded for chemistry as a
whole, and not merely for the chemistry of gases, will be
shown later on. Gay-Lussac's name is further associated
with the discovery of the definite relation which exists
between the volume of a gas and its temperature ; it was
only after this law had been worked out, a law which
supplemented that of Boyle and Mariotte, that reliable
measurements of gases could be made.
In his work which bore upon special branches of chemistry
Oay-Lussac likewise proved himself a masterly investigator ;
to exactitude in observing, and acuteness in explaining his
observations, he added a wonderful lucidity in expounding
his researches and the conclusions at which he arrived. His
work on iodine and cyanogen and their compounds would
-alone suffice to ensure him a place among the most dis-
tinguished chemists. How stimulating and full of matter
were his papers ! The one upon cyanogen, especially, was
the basis on which the radical theory was afterwards
developed, for cyanogen was characterised by Gay-Lussac as
the first compound radical. Even his minor work bears the
-classical stamp ; of it we may mention here his researches
•on the compounds of sulphur, and on the various stages of
oxidation of nitrogen, and his conjoint work with Thenard1
upon the alkali metals. Together with Liebig he investigated
the fulminates. Hidden in many of these pieces of work
1 L. J. Thenard, born in 1777, a pupil of Vauquelin and Berthollet,
became professor at the JiJcole Polytechnique and in the College de France,
and worked energetically for the promotion of the study of natural sciences
in France. His name is indissolubly united with that of Gay-Lussac,
their conjoint work leading to a knowledge of many chemical processes,
and contributing to the improvement of important methods. Thenard's
Traitd de Chimie ^Jlementaire, a text-book which was most widely used,
thanks to the happy synoptical arrangement of its contents, was of great
merit ; the first French edition of it was published in 1813-16, and the first
German edition (translated from the fifth French by Fechner) in 1825-33.
Thenard died in 1857.
v <:AY-LUSSAC'S WORK; PROUT'S HYPOTHESIS 201
there lay germs which were to expand into important
discoveries ; for example, his observation on the action of
chlorine upon wax laid the foundation for subsequent
researches upon substitution reactions.
By his work on technical subjects, Gay-Lussac proved
that he understood how to bring his results in analytical
chemistry to bear upon these. He is to be regarded as the
originator of volumetric analysis; and the improved ana-
lytical methods which he thus introduced, and which have
since come intc general use, have helped materially to ad-
vance chemical industries. We shall meet with his work in
almost every important branch of chemical investigation, —
in analytical, technical, physical and pure chemistry.
Gay-Lussac published most of his experimental results
in the Annales de Chimie,1 but a few of them are to be
found in the Memoirs de la Socie'te' d'Ar$euil and in the
Comptes Rendus. Of his papers which appeared separately,
mention may be made here of a number upon methods of
investigating and testing commercial products, silver ores,
etc., which, as a member of various commissions, he worked
out; also of the Recherches Physiques et Chimiques (1811),
which he edited conjointly with Thenard.
Prout's Hypothesis and its Effects.
During the period in which Davy and Gay-Lussac were
carrying on their brilliant work, and before the star of
Berzelius had attained to its full lustre, a literary-chemical
event occurred which made a profound impression upon nearly
all the chemists of that day, viz. the advancement of Prout's
hypothesis. This was one of those factors which materially
depreciated the atomic doctrine in the eyes of many
eminent investigators. On account of its influence upon the
further development of the atomic theory, this hypothesis
must be discussed here, although it has happened but seldom
1 After the year 1816 this journal was edited by Arago and himself
under the title Annales de Chimie et de Physique.
202 THE MODERN CHEMICAL PERIOD CHAP.
that an idea from which important theoretical conceptions
sprang, originated in such a faulty manner as it did.
In the year 1 8 1 5 a paper1 appeared in which the relation
between the atomic weights of elements and the specific
gravities of their vapours was treated of ; in this paper, and
still more positively in a second,2 published in the following
year, the tenet was set up by their anonymous author that
the atomic weights of the elements — taking that of hydrogen
as unity — were expressible by whole numbers, i.e. that they
were multiples of the atomic weight of the lightest element.3
From this there followed the hypothesis proper of Prout
(who had, in the meantime, become known as the author of
the above two papers), — that hydrogen may be regarded as
the primary matter from which all other elements are formed
by various condensations.
This idea, so lightly thrown out. and which adapted itself
so usefully to the incomplete investigations of others,4
possessed both then and at various later periods a great
charm for many chemists. Even before these papers had
been published, Dalton's friend Thomson had alluded to
the fact that, according to his own experiments and those
of others, the atomic weights of several of the elements were
multiples of those of oxygen. He endeavoured, indeed, to
establish the same point several years after this, without
considering that the numbers which Berzelius had found
in the meantime differed widely from his own, which had
therefore become of very doubtful value. Thomson was
the victim of this preconceived opinion ; he went so far as
to see in Prout 's assumption a fundamental law of chemistry,
1 Annals of Philosophy, vol. vi. p. 321.
2 Ibid., vol. vii. p. 111.
3 The author altered the numerical values of the atomic weights in a
highly arbitrary manner, so that they should not merely be whole numbers,
but should also show regular differences among each other, as is seen from
the following examples : —
Calcium 20 Iron 28 Chlorine 36
Sodium 24 Zinc 32 Potassium 40.
4 Prout himself was a physician, and his own investigations were few
in number and anything but conclusive.
BERZELIUS 203
Although Berzelius and, later, Turner and others proved
the untenability of Prout's hypothesis, many chemists still
inclined towards it. In his text-book of 1827, L. Gmelin
gave the " mixture weights " (Mischungsgewichte) as far as
possible in whole numbers, which he was assuredly not
justified in doing after Berzelius' classical researches. Later
still, about the year 1840, Dumas and Stas, who had
determined the atomic weights of carbon, oxygen, chlorine
and calcium with great exactitude, and also Erdmann and
Marchand in their numerous investigations in a like direc-
tion, betrayed a strong inclination to this hypothesis, the
weakness of which was afterwards proved by Stas himself
and by Marignac. The predilection shown by many chemists
for this conception, which led to such far-reaching deduc-
tions, helped to discredit the whole atomic doctrine in the
minds of thoughtful investigators.
Like Davy and Gay-Lussac, who, it is true, did not
specially occupy themselves with the problem of determining
the atomic weights of the elements, Berzelius kept himself
entirely free from those prepossessions ; and, since even at
that time he devoted all his energies to the solution of ques-
tions allied to this, his opinions possessed the very greatest
value. Firm, and not led away by the alluring simplicity^of
Prout's hypothesis, he held fast to his aim, — the accurate,
purely experimental determination of the atomic weights,
and by his masterly work he firmly established the then
unsteady edifice of the atomic doctrine.
BERZELIUS— A SURVEY OF HIS WORK.
The life of this investigator, who developed and enriched
chemistry in its most important branches as hardly any
other man has done, was the quiet and uneventful one of a
student. He was guided in his work by the great and com-
prehensive aims, — to investigate carefully the composition of
chemical compounds, and to arrive at the laws according to
which they are formed.
204 THE MODERN CHEMICAL PERIOD CHAP.
Jakob Berzelius was born at the little town of Westerlosa
in Ostergotland, Sweden, where his father was a schoolmaster,
on the 2 9th of August, 1779. A love for chemistry appears
to have developed itself in him at a very early date, but his
desire to devote himself to its study at Upsala was only
attained (in 179 8) under many difficulties and disappoint-
ments. The lectures and instruction given by his teachers
Afzelius and Ekeberg were uninspired by the spirit after
which Berzelius strove. We therefore find him turning to
the study of medicine, without, however, losing sight of
chemistry as an important aid to the latter. His early work,
especially that which he carried out along with Hisinger
upon the action of the galvanic current on salts, made him
known in his own country, so that in 1802 he was appointed
assistant professor in medicine, botany and pharmacy at the
University of Stockholm, and, five years later, professor of
medicine and pharmacy. In 1815 he was called to the
chair of chemistry in the newly-founded Chirurgico-Medical
Institute there. His lectures, which were at first purely
theoretical, according to the established custom, he began to
enliven by judiciously chosen experiments ; while a very im-
perfectly equipped laboratory enabled him to carry through the
exact experiments which were to firmly establisththe doctrine
of chemical proportions. In those modest rooms were accom-
plished the famous researches, most of them by himself alone,
but some in conjunction with specially gifted pupils. The
names of those latter are sufficient in themselves to show
the wonderful results which he achieved by his teaching ;
among them we may mention here Heinrich and Gustav
Rose, Mitscherlich, Wohler, Chr. Gmelin, Magnus and
Mosander.
From the year 1818, when he was nominated permanent
secretary to the Stockholm Academy, of which he had been
a member since 1808, and still more after 1832, when
Mosander succeeded him in his chair, Berzelius devoted
himself to literary work with an effectiveness which has
hardly been equalled by any chemist either before or after
him. His energetic life came to a close on the 7th of
v BERZELIUS' MORE IMPORTANT WORK 205
August 1848. In 1818 he was ennobled by King Charles
XIV., and in 1835 made a baron by the same monarch.
To give a short and at the same time succinct account of
the great scientific achievements of Berzelius is no easy
task, for these did not merely touch upon the main points
of chemistry, but penetrated deeply into them, and gave
rise to weighty reforms. After occupying himself for the
first seven years of his independent scientific work with
researches in various branches of the science, especially
physiological chemistry, and proving himself thereby to be
an exceptional observer, his efforts rose — from 1807 — to a
higher level. For, from that date, his entire energy was
devoted to one great aim; the minute investigation of
chemical proportions and, with that, the development of the
atomic doctrine he looked upon as his life-task. At the time
when he began his work upon the combining proportions of
the elements, the atomic doctrine was unknown to him. His
first researches were inspired by J. B. Richter's papers and
then by Davy's discoveries, before he was aware of the
results of Dalton's labours which had led to. the atomic
theory. How Berzelius built up the doctrine of proportions
by improving analytical methods and by the clear-sighted
interpretation of his own researches and those of others,
and how he created solid foundations for the determination
of atomic weights, will be described in the following section.
But we must just mention here that he greatly enriched
analytical chemistry by the discovery of new methods. These
were, indeed, indispensable to him for the attainment of his
great aim, for it was only by means of the most accurate pos-
sible analyses that the constancy of combining proportions
could be definitely proved. This was, however, by no means
the only branch of chemistry which was indebted to him, for
analysis in his hands was made to open up other and larger
domains. His first attempt to work out the composition of
minerals on the basis of the atomic theory, i.e. with the aid
of 'the law of multiple proportions, was made so early as the
year 1812, and his establishment of a chemical mineral
system created an extraordinary interest.
206 THE MODERN CHEMICAL PERIOD CHAP.
Of still more far-reaching effect were his successful en-
deavours to show that organic compounds were likewise
subject to the law of multiple proportions. After materially
improving the methods of analysis of organic bodies, he was
able to demonstrate in 1814 that simple atomic relations
prevail among the constituents of organic acids and of their
salts. The atomic theory thus became the guiding star both
for Berzelius and for the whole science.
Berzelius assumed that atoms were electrically polarised,
-and looked upon this as the cause of the combination of
elements in definite proportions. His electro-chemical
theory, developed from this assumption, and his dualistic
system, which was the immediate result of this theory, will
be described in detail along with other similar attempts at
explaining the phenomena of affinity.
Experiment formed the basis of his speculations. By
connected observations on the chemical behaviour of simple
and compound bodies, he extended the most important
branches of his science in a marvellous degree.
, Of his numerous researches on inorganic substances, that
upon selenium is a classical model, worthy to rank alongside
of Gay-Lussac's upon iodine. We may also call to mind
here his remarkable investigations upon ferro-cyanogen com-
pounds, sulpho-salts and fluorine compounds, among many
others. All his experimental work shows the originality of
a master mind ; and although his inventive genius was not
so great as that of Davy, his strict methods of procedure
and conscientious observations led him to discoveries of the
first importance.
The work of Berzelius in organic chemistry is less imposing
than that which has just been sketched, but we have only
to recall his discovery of racemic acid, and his important
investigations on its isomerism with tartaric acid, to see that
here, too, he made a deep mark. As he was the first to
apply the principles of the atomic theory to organic sub-
stances, so he sought to introduce his electro-chemical and
dualistic views here also. These efforts of his to simplify
complex relations were not however in this instance per-
BERZELIUS AS A TEACHER AND WRITER i2«»7
manently successful, for, although his radical theory had
a fruitful influence for a time, it was unable to hold its
ground against the unitary conception. Much of his work in
mineralogical and physiological chemistry was fundamental
in its nature, and was even that of a pioneer, since it had as
its immediate result (especially in mineralogical chemistry)
the setting up of entirely new points of view and new aims.
The grand creative genius of Berzelius and the joy he had
in his work are not only apparent in his experimental
researches, but show themselves also in his activity as a
teacher, whether as manifested in personal intercourse with
his pupils or as finding expression in writing. In his little
laboratory there assembled young men from far and near,
most of them already well versed in chemical knowledge, to
learn from his experience and then to further propagate his
doctrines. From Germany especially, where at that time
there was hardly any provision for practical chemical work,
came aspiring students, who subsequently advocated the
principles of his school and extended its influence.
Berzelius' literary activity is most strikingly shown in his
Lehrluch der Chemie,1 of which five editions, each of them
completely revised, appeared. Along with the absolute
thoroughness which we also admire in his experimental work,
clearness of description is united in this book with precision
of expression. He did not merely confine himself to the
simple exposition of known facts, but criticised with absolute
impartiality the experiments from which these were deduced.
His text-book remained a model, unapproached by any other,
during succeeding decades. The many-sidedness of Berzelius
and his power of work were also strikingly shown in the
Jahresbericht uler die Fortschritte in der Physik und Chemie
(" Annual Report on the Progress of Physics and Chemistry "),
1 This book came out for the first time in 1808-1818 in three volumes
(Swedish) ; the second Swedish edition (four vols., 1825-31) was translated
into German by Wohler, while the subsequent editions were printed
in German only. The third (four vols., 1833-35) and the fourth (four vols.,
1835-41) were done into German by Wohler "from the Swedish MSS. of
the author," while the fifth "original edition" (five vols., 1843-48) was
written by Berzelius himself with Wohler's co-operation.
208 THE MODERN CHEMICAL PERIOD CHAP.
twenty-seven volumes in all, which were published by him
in Swedish from the year 1821 until his death ; these were
also brought out in German by Gmelin for the first three
years, and subsequently by Wohler (in Tubingen). He had
undertaken to report to the Stockholm Academy upon the
work published on those subjects, a task which he performed
with diligence and perspicacity. With regard to work which
came at all within his own province, he knew to perfection
how to fill the role of critic, although on some occasions he
was led by the characteristics of particular experimental re-
searches to express a judgment which betrays a certain prepos-
session. Notwithstanding this, however, his Jahresberichte are
and will remain indispensable sources of information for any
one who wishes to understand the currents and changes of
opinion in the chemistry of that time.
The experimental researches of Berzelius were as a rule
first published in Swedish in the Transactions of the Stockholm
Academy, but most of them were afterwards given out in
German, and a few in English and French (in Gilbert's,
Poggendorff's, and Lielig's Annalen. the Annales de Chimie,
Annals of Philosophy, etc.). They are characterised by the
same excellences as his text-book.
The above sketch of his main achievements is sufficient to
indicate the qualities which distinguished Berzelius as a
classical investigator. Thoroughness and perseverance in
everything which he undertook ; exactness in all his observa-
tions, and the capacity for arranging these distinctly and ex-
plaining them clearly ; inviolable adherence to the results of
experience (which was his guide before everything else), and
an equally firm adherence to results which, in his opinion, had
been correctly arrived at from a number of data ; these were
the characteristics which distinguished this great man.
The desire to retain whatever of good the science possessed
was developed in him in an exceptional degree ; indeed, in sus-
taining this conservative attitude he went so far as to see a
danger to the steady development of chemistry in every in-
novation which called in question views already proved and
found useful. Hence his fervent opposition to many new
v REVIEW OF BERZELIUS' WORK 209
hypotheses which he had in the end to recognise as correct
His great services in furthering chemistry were, however, not
lessened by this peculiarity, which had its real cause in a pro-
found sense of justice ; on the contrary, by a prudent adherence
to approved opinions, Berzelius often prevented the confusion
to which the views he combated might probably have given
rise, had they been accepted without reservation. Not that
he was averse to healthy reform. But against anything
violent — to his mind revolutionary — he fought with all his
energy he did not shun even hot polemics l when anything
that he regarded as sound was at stake.
His pupil Heinrich Rose gave a comprehensive review of
his general character in the " Memorial Speech of Berzelius, "2
— a speech of great beauty and with a pleasant warmth of tone
running through it. At the close of it (p. 5 9) Rose says :
" The irresistible captivation which Berzelius exercised over
those who enjoyed the privilege of a lengthened intercourse
with him was only partly due to the lofty genius, whose
sparks flashed from all his work, and only partly to the
clearness, the marvellous wealth of ideas, and the untiring
care and great industry that gave everything with which he
had to do the stamp of the highest perfection. It was also —
and every one who knew him intimately will agree with me
in this, — it was also those qualities which placed him so high
as a man : it was his devotion to others, the noble friendship
which he showed to all whom he deemed worthy of it, the
great unselfishness and conscientiousness, the perfect and just
recognition of the services of others, — in short, it was all those
qualities which spring from an upright and honourable
character. " 3
1 His controversies with Dumas, Laurent, Liebig and others have
often been harshly and unfairly criticised, in that a false light has been
thereby thrown upon his whole work. The younger generation of
chemists, in especial, quickly forgot after his death the debt which was due
to him for the imperishable services which he had rendered in the building
up of the science. Indeed, derision and cheap ridicule of the mistakes he
made are still to be found in recent works which treat of the development
of chemical theories.
2 Delivered at a public meeting of the Berlin Academy, 3rd July, 1851.
3 The recently published letters of Berzelius and Liebig to each other,
P
210 THE MODERN CHEMICAL PERIOD CHAP.
We may close this section with the following words,
in which the same chemist portrays in a few lines the
wonderful work of his master : " When a man who is endowed
with exceptional talents as an investigator enriches every
branch of his science Vith the most pregnant facts, distin-
guishes himself equally in empirical and speculative research,
and grasps the whole subject in a philosophic sprit ; when he
arranges each detail systematically and clearly, and gives the
whole to the world in a doctrinal system, critically sifted and
put in as perfect a form as possible ; lastly, when he proves
himself a noble example of a practical and theoretical teacher
to a circle of pupils eager for knowledge, — that man so fulfils
the highest demands of his science, that he will continue to
shine forth as a brilliant model for ages to come. "
The Firm Establishment of the Doctrine of Chemical Propor-
tions and the Development of the Atomic Theory by
Berzelius ; together .with the share taken in these Toy
Gay-Lussac, Dulong and Petit, and Mitscherlich.
It has been already stated in the preceding section that
Berzelius regarded the investigation of chemical proportions,
and of the laws which regulate these, as his life task. Com-
pounds of oxygen formed the starting-point for his researches
and for the deductions which he drew from them, this element
being indeed, after the time of Lavoisier, the centre round
which the whole of chemistry ranged itself. Even in the
first investigations, which he began to publish in 1810 in
Swedish, and in 1811 in German (in Gilbert's Annalen, vols.
xxxvii., xxxviii., and xl.), Berzelius furnished powerful proofs
which embrace the years 1831-1845, confirm in the most absolute manner
the above kindly critique. This book, edited by Liebig's grandson, J.
Carriere, and published by Lehmann (Munich and Leipzig) in 1893, will
be welcomed as one of the best contributions that has been made to the
history of chemistry of late years. It will assuredly help towards a truer
criticism not merely of Berzelius and Liebig themselves, but also of many
other eminent men, and at the same time assist towards a clearer view of
various important points.
v DEVELOPMENT OF THE ATOMIC THEORY 211
of the existence of chemical and, more particularly, of mul-
tiple proportions in the oxygen compounds of the elements. If
we consider that he carried out this great work and the sub-
sequent investigations connected with it (for which entirely
new methods had to be devised), almost altogether by himself,
we shall gain some idea of the wonder which such achieve-
ments created anong his contemporaries.1
A true scientist, Berzelius knew how to advance from
the particular to the general ; he first collated a number of
important facts which, taken together, rendered possible the
gradual but firm establishment of the atomic theory. Among
these were the proofs that the proportion of sulphur to metal
in the metallic sulphides was the same as that in the cor-
responding sulphates ; that the amounts of oxygen in the
equivalents of bases were likewise the same ; and that in
salts of every kind the ratios between the quantities of base,
acid and water were simple ones, — and so on.
In the years 1812 to 1816 Berzelius investigated the
1 Many passages in the works of Berzelius proved that he looked upon
the firm establishment of the doctrine of chemical proportions, and, in con-
nection with this, the determination of the atomic weights of the elements
and the constitution of chemical compounds, as his chief task. His own
words may be quoted here to show how he, impressed as he was with the
incompleteness of previous work on the subject, strove to improve upon it :
' ' I soon convinced myself by new experiments that Dalton's numbers were
wanting in that accuracy which was requisite for the practical application
of his theory. I now perceived that if the light which had arisen upon
the whole science was to be propagated, the atomic weights of as large a
number of elements as possible, and, above all, of the most commonly
occurring ones, must be determined with the greatest accuracy attainable ;
and, together with this, the proportions according to which compound
atoms (zusammengesetzte Atome) combine among each other, as, for instance,
in salts, with the analysis of which I had been occupied for some time.
Without work of this kind no day could follow the morning dawn. This
was, therefore, the most important point for chemical research at the time,
and I devoted myself to it with unresting energy. Several of the more
important atomic weights I subjected, after lengthened intervals, to a
closer scrutiny, making use of improved experimental methods. After
work extending over ten years, the results of which have been published
in the scientific journals, I was able in 1818 to publish a table which con-
tained the atomic weights, as calculated from my experiments, of about
2000 simple and compound substances." — Lehrbuch der Chemie, vol. iii. p.
1161, fifth edition.
p 2
212 THE MODERN CHEMICAL PERIOD CHAP.
stages of oxidation of most of the metals and metalloids then
known (to use his own term for the non-metals), and, by deter-
mining the composition of these oxides, confirmed the law
of multiple proportions. And, notwithstanding that he some-
times proceeded from erroneous premises, e.g. from the
assumption that chlorine and ammonia contained oxygen,
his grasp of the subject was so complete that he was able
to keep the main conclusions drawn from his experiments
free from error.
Of special significance for the sound development of the
atomic doctrine were his efforts (intimately connected with
the work just mentioned) to deduce the relative atomic
weights of the elements, and also of compounds, from
the composition of chemical compounds as determined by
analysis. He went about this with great circumspection,
showing wonderful tact in the selection of proper footholds
from which to approach the difficult task. Already in one
of his earlier papers 1 we meet with the first statement of
the " oxygen law," according to which the amount of oxygen
in the acid of a salt stands in a simple numerical proportion
to that in the base, — a statement which was the result of
experience, and which Berzelius followed in many atomic
weight determinations.
The propositions which Dalton had brought forward with
a view of arriving at the atomic numbers of the constituents
of chemical compounds were rightly designated by Berzelius
as arbitrary. Among them, for example, was the assumption
that the atomic proportion of two elements to one another,
when only one compound of these was known, must be 1 : 1.
Berzelius, too, set out from simple premises, and had to
exercise all his ingenuity in order to find further support
for such assumptions. One of these latter (advanced at the
beginning of his work on the subject) was — that 1 atom of
one element A. combines with 1, 2, 3, or 4 atoms of
another element B. The less simple combining proportions
2 A : 3J? or 2 A : SB were first allowed by Berzelius about
the year 1819, and without any reservation only in 1827.
1 Gilbert's Annalen, vol. xxxviii. p. 161.
v RELATIVE ATOMIC WEIGHTS 213
With such propositions as a basis, even when including
the definitely expressed " oxygen law " (which had been
worked out in the meanwhile), Berzelius would have been
hardly more successful in solving the question of the number
of elementary atoms in a compound than Dalton and his
immediate successors, had he not known how to appreciate
the value of Gay-Lussac's important discovery of the " law
of volumes " for clearing up the points in question. By
making use of this, the simplest combining proportions in
which different elements unite became all at once apparent,
and, by applying it further, Berzelius was able to bring his
experimental work to its first conclusion. His Versuch uber
die Theorie der chemischen Proportioned, und uber die ckemischen
Wirkungen der Elektrizitdt (" Essay upon the Theory of
Chemical Proportions and upon the Chemical Action of
Electricity ") appeared first in 1814 in Swedish, in 1 8 1 9 in
French, and in 1820 in German.1 In this memorable
work for the history of chemistry he developed his concep-
tion of the atomic doctrine, and his ideas upon the relations
between chemical affinity and electric polarity. His dualistic
views stood out clearly here, and at the same time he devised
a new language and nomenclature for his system. Of special
importance was the collection of the results of his arduous
investigations in tables of the atomic weights of elements
and compounds ; he was able to give original figures for
about 2000 substances. In order to become thoroughly
acquainted with the grounds which influenced Berzelius in
his choice of these values, we must take into account the
law of volumes above all other things, because, as has already
been mentioned, he not only drew important inferences
from it, but used it almost from the beginning of his
researches as the basis of his atomic weight system.
1 Edited by K. A. Blode.
214 THE MODERN CHEMICAL PERIOD CHAP.
Influence of the Law of Volumes upon the Atomic Theory.
Among the greatest of the services rendered by Gay-
Lussac was the research which he published towards the end
of 1808 in the Mtmoires de la Socie'te' d'Argeuil, vol. ii. p. 20*7 x.
Having three years previously, in conjunction with Alexander
von Humboldt, observed that exactly two volumes of
hydrogen unite with one volume of oxygen to form water,
he showed by comprehensive investigations that similar
simple volumetric relations exist between all gases which
combine chemically with one another, and further, that the
gaseous products formed also stand in a simple volumetric
relation to their components. He proved this, for example,
in the formation of two volumes of carbonic acid from two
of carbonic oxide and one of oxygen, and in the combination
of hydrogen and chlorine and of ammonia and hydrochloric
acid in equal volumes ; he likewise showed that two volumes
of ammonia were composed of three volumes of hydrogen
and one of nitrogen, and two volumes of (anhydrous) sul-
phuric acid of two volumes of sulphurous acid and one of
oxygen. Several of these proportions he was able to deduce
from the results of other workers, e.g. Dalton, Davy and
Vauquelin, who had determined the volumes with fair
accuracy in their experiments on gaseous compounds, with-
out, however, recognising the underlying law.
Having concluded from their similar behaviour with
regard to changes of pressure and temperature that all gases
possess a like molecular constitution, Gay-Lussac deduced
from his researches, just quoted, the following important
}aw . — The weights of equal volumes of both simple
and compound gases, and therefore their densities,
are proportional to their empirically found combin-
1 In his Classiker der Exakten Wissenschaften, W. Ostwald has put
within every one's reach these papers of Gay-Lussac and of A. von Hum-
boldt, as well as the fundamental researches of Dalton and Davy already
referred to. A like service as regards chemical classics has been rendered
to English-speaking chemists in the Alembic Club Reprints, edited by Dr.
Leonard Dobbin, and published by W. F. Clay, Edinburgh.
v GAY-LUSSAC'S LAW OF VOLUMES ; AVOGADRO 215
ing weights, or to rational multiples of the latter.
In this sentence the old idea — that certain definite
relations exist in nature between the weight and mass
(pondere et mensura) of compounds — first found distinct
expression.
Gay-Lussac was himself inclined to connect his law of
volumes with the atomic theory, — indeed, he recognised in it
a support for the latter. But he was unable to set aside
certain difficulties which, in spite of the simplicity of the
known volume-relations, came in the way, and he therefore
adhered to his empirical standpoint.
The assumption obviously so closely related to the above,
viz. that equal volumes of different gases contain equal
numbers of smallest particles, and that, in the case of the
simple gases, these are not undecomposable but consist of
several atoms, was made so early as 1811 by Avogadro.1
From such an assumption it followed that the masses of
these smallest particles, i.e. the molecular weights of the
gases, were proportional to the vapour densities. The par-
ticles were termed by him molecules inttgrantes, and their
constituents (i.e. our atoms), molecules e'le'mentaires. Not-
withstanding the fruitfulness of those conceptions, and the
ease with which by their aid the mutual relations between
the volumes of gases and the atoms could be explained,
they remained almost unnoticed. The reason for this may
to some extent have been that Avogadro generalised too
boldly, extended his hypothesis to non-volatile substances,
and brought forward no new facts in support of it.
But although the conclusions drawn from the law of
volumes by the scientist just named remained unheeded at
the time, the law itself bore rich fruit for the atomic
doctrine. Dalton himself showed a disinclination to agree
with the results of Gay-Lussac's researches, indeed, he doubted
1 Journ. de Phys., vol. Ixxiii. p. 58. (This paper forms No. 8 of
Ostwald's Classiker; cf. also No. 4 of the Alembic Club Reprints. ) Amadeo
Avogadro, born 1776, died while still professor of physics at Turin in 1856.
It is through the treatise just mentioned that his name will always remain
famous.
216 THE MODERN CHEMICAL PERIOD CHAP.
their correctness. Thomson and Davy too did not perceive
that the law of volumes had any special significance from
the atomic point of view, as, although they frequently made
use of the volume-relations of gases to arrive at their com-
position, at other times they interpreted these relations
wrongly; thus they assumed that a volume of hydrogen
contained only half as many atoms as an equal one of
oxygen.
Berzelius, however, recognised in the law of volumes a
welcome corroboration of the atomic theory, and allowed
himself to be guided by it in his views upon the number of
atoms in chemical compounds, and, consequently, upon the
numerical values of the atomic weights. His " volume
theory" (Volumtheorie) contained the attempt to combine
Gay-Lussac's law with the atomic theory. He set forth the
atomistic view, which he had himself put into shape under
the influence of the law of volumes, definitely and con-
clusively in two papers.1 He started with the assumption
that in the case of every simple substance, when it was
in the gaseous form, one volume corresponded with one
atom, and therefore made use of the designation "volume
atoms" (Volumatome) for those smallest particles. Where-
ever it was practicable, he endeavoured to measure the
volumes of the combining substances, and from these deduced
the atomic numbers. The analysis of the compound, in
which the volumes of the elementary constituents were
known, led him to the true determination of the atomic
weights of the latter. Thus, from the fact that water con-
sists of two volumes of hydrogen and one of oxygen, he
deduced the atomic composition of water which holds at the
present day, together with the relative atomic weights of
oxygen and hydrogen; and from the (volumetric) mode of
formation of carbonic oxide and carbonic acid he arrived at
the true composition of these compounds, and at the atomic
weight of carbon, etc.
But, however much Berzelius was convinced at that date
(1813) of the superiority of this conception over the "cor-
1 Ann. of Philos., vol. ii. pp. 359, 443 (1813).
v THE ATOMIC WEIGHTS OF BERZELIUS IN 1818 217
puscular theory," which took no account of volume-relations,
he did not fail to recognise the limits of application of his
volume theory. To extend to non- volatile bodies the con-
ceptions which he had gained from gases seemed to him
hazardous; in fact, his doubts as to the possibility of
regarding all elements and chemical compounds from the
standpoint of the volume theory grew rapidly, as is easily
seen in his Essay upon the Theory of Chemical Proportions,
etc. (cf. p. 230), which was published a few years after this-
But he had, at any rate, found in the law of volumes a
valuable aid towards the determination of the atomic com-
position of numerous substances, and the deduction from this
of the atomic weights of many of the elements.
A glance at the table of atomic weights which he pub-
lished in 1818 shows how reliable the values found by him
are, comparing favourably as they do with those of other
observers. A later table given out by him in 1827 contained
marked improvements on the former one. and brought his
atomic weights still nearer to those current at the present
day. But great uncertainty still prevailed with regard to the
proportional numbers of many of the atomic weights, as com-
pared with that of hydrogen or oxygen. Berzelius took oxygen
(as the most important element, the " pole of chemistry ")
for the basis of his other atomic weights, making that of
oxygen = 100. His ground for this preference1 was that
oxygen was capable of combining chemically with every other
element ; in fact, oxygen compounds were almost the only
ones made use of at that time for the derivation of the atomic
weights.
If we calculate his values upon that of hydrogen, which
is now the customary unit, we obtain numbers that can be
compared with those in use to-day. The following selection
of such atomic weights from the year 1818 will serve to
1 In his text-book (first edition, vol. iii. p. 99) he expresses himself as
follows : "To refer the other atomic weights to that of hydrogen offers
not only no advantages, but has, in fact, many inconveniences, seeing that
hydrogen is very light and is seldom a constituent of inorganic compounds.
Oxygen, on the other hand, unites all the advantages in itself. It is, so to
speak, the centre-point round which the whole of chemistry revolves."
218 THE MODERN CHEMICAL PERIOD CHAP.
corroborate what has just been said (the current values are
those in brackets) : —
Carbon 12'12 (12) Lead 416 (207) Sodium 93.5 (23)
Oxygen 16 (15'96) Mercury 406 (200) Potassium 157. 6 (39)
Sulphur 32-3 (32) Copper 129 (63'3) Silver 433 '7 (108).
Iron 109-1(56)
The question now forces itself upon us — What were the
grounds which led Berzelius to assume twice as high a value
for many metals (e.g. iron, lead, mercury, copper, chromium,
tin, etc.), and four times as high a value for potassium, sodium
and silver, as are now assigned to them ? The reason lay in
his presupposition of the simplest possible combining pro-
portions, for at that time such proportions as 2:3, 2:5,
3 : 4, etc., appeared to him too complex ; only one atom of
an element was, in his then view, present in (a molecule
of) a compound. The compounds formed by the oxidation
of iron, for example, in which the proportions of oxygen
were as 2:3, and which we now express by the formulse
FeO and Fe203, had for him the composition expressed by
the formulae Fe02 and FeO3, whence the atomic weight of
iron came out double what we now have it. An analogous
composition was attributed to other metallic oxides corre-
sponding to the protoxide and sesquioxide of iron, so that
the atomic weights of their metals were doubled. In like
manner Berzelius was led, by the assumption that the ratio
of oxygen in potassic peroxide and oxide was as 3 : 2, to the
erroneous conclusion that the latter contained one atom of
potassium combined with two of oxygen, and the peroxide
one of potassium combined with three of oxygen ; hence for
potassium and the analogous monovalent elements sodium,
lithium and silver, whose oxides have in reality the general
formula Me2O, atomic weights four times higher than the
true ones were deduced.
Thus, in spite of Berzelius' gigantic labours, many points
attaching to his system of atomic weights still remained un-
certain ; there were as yet too few reliable and comprehen-
sive data to allow of the true relations of the values found
to that of hydrogen or oxygen being firmly established.
v DULONG AND PETIT 219
Berzelius himself was convinced of the insufficiency of the
methods by which he had determined the atomic composi-
tion of compounds, and, from this, the atomic weights of the
elements. Apart from his somewhat arbitrary suppositions,
he had merely found in the physical behaviour of gases—
in the relation of their specific gravities to the combining
weights — a good basis upon which to work out the question
of the magnitudes of the relative atomic weights.
The year 1819 brought with it two important dis-
coveries in physical chemistry which helped to clear up the
above uncertainties; attention was called almost simul-
taneously by Dulong and Petit1 to the relations between
the atomic weights of the elements and their specific heats,
and by Mitscherlich to the connection between similarity of
crystalline form and analogous constitution. The latter
discovery and the doctrine of isomorphism which grew out
of it were largely made use of by Berzelius for determining
relative atomic weights; but to Dulong and Petit 's state-
ment he paid much less heed, as it still required extension
and corroboration. Both of these discoveries have exercised
such a profound influence on the development of the atomic
weight system that they must be discussed shortly here, in
so far as they refer to the latter (cf. section devoted to the
history of Physical Chemistry).
1 P. L. Dulong, who was born in 1785 at Rouen, and died in 1838 while
Director of the Polytechnic School at Paris, rendered imperishable service,
more especially by his physico-chemical investigations. But, apart from
these, his purely chemical labours — e.g. that upon chloride of nitrogen, in
discovering which compound he lost an eye and several fingers (in 1811),
that upon the oxygen compounds of phosphorus and nitrogen, and his
fruitful speculations upon the constitution of acids — ensure him an honour-
able place in the history of the natural sciences.
T. A. Petit was born in 1791, and died while Professor of Physics at
the Polytechnic School so early as 1820. To chemists he is known by his
conjoint work with Dulong on the atomic heats of the elements (see above),
his other researches being purely physical.
220 THE MODERN CHEMICAL PERIOD CHAP,
Dulong and Petit's Law.
From researches 1 carried out in part with substances not
quite pure, and in part by methods upon which not much
reliance could be placed, those two investigators drew the
important conclusion that the specific heats of a number of
the solid elements, the metals in particular, were nearly
inversely proportional to their atomic weights. But, how-
ever bold these deductions were, deductions which they
expressed in the sentence: "The atoms of simple sub-
stances have equal capacities for heat," or, "The
atomic heats of the elements are equal," their confi-
dence in them was on the whole justified by later and more
accurate experiments; at any rate most of the metallic
elements fulfilled the Dulong -Petit law approximately.
The exceptions to it, shown by many of the non-metals in a
greater or lesser diminution of the atomic heats, have only
in some measure been explained in recent years by the proof
that the specific heats of such elements vary greatly with the
temperature. In the case of simple chemical compounds, too,
a relation was soon found between their specific heats and
atomic weights (by Neumann, in 1831).
When once its validity had been proved, the significance
of the Dulong-Petit law for the determination of the relative
atomic weights of the elements became immediately apparent.
One had merely to determine the specific heat of an element
in order to arrive at its atomic weight from this, taken in
conjunction with the atomic heat (which was assumed to be
a constant), i.e. the product of the specific heat into the
atomic weight. Dulong and Petit at once went on to apply
their law to this problem, and came to the conclusion — a con-
clusion which was later recognised as correct — that the atomic
weights ascribed by Berzelius to several of the metals must
be halved.
There was, however, as yet no pressing reason why the
latter, on a dispassionate review of Dulong and Petit's
1 Ann. Chim. Phys., vol. x. p. 395 (1819).
v ISOMORPHISM AND THE ATOMIC THEORY 221
results, should at once agree to this demand. That those
results were of great importance for theoretical chemistry
he willingly admitted, but he maintained that they had not
yet been proved to be of such general application that a law
could be formulated from them. He especially opposed any
fundamental alterations of his own atomic weights, as he
held that, if this were done, improbable atomic proportions
would have to be assumed for the compounds of some of the
elements. This attitude towards the Dulong-Petit law was
only gradually abandoned by Berzelius, after further proofs
bearing on the point had been adduced.
Influence of the Doctrine of Isomorphism upon Atomic
Weight Determinations.
After the founding and development of crystallography
by Rome de 1'Isle and Hauy, various experimenters had
observed that substances of different chemical composition
crystallise together in one and the same crystalline form.
As instances of this may be mentioned Gay-Lussac's ob-
servation that crystals of potash alum grow in a solution
of ammonia alum, while still retaining their original crystal-
line form, and Beudant's, that copper vitriol is obtained
in the same form as iron vitriol when a small quantity of
the latter is added to a solution of the former, and so on.
But neither this observation nor the definite statement
by Fuchs upon the replacement of certain substances in
minerals by others [his doctrine of "vicariating con-
stituents" (Vikariierenden Bestandtheilen1)'] led to the re-
cognition of the relation between crystalline form and
chemical constitution.
This important discovery 2 was reserved for E. Mitscher-
1 This means substitution without any accompanying change of crystal-
line form ; thus, to give one or two examples, Fe" can replace Ca", and Al'"
can replace Fe'" or Cr'" in this way.
2 Berl. Akad. Abhandlungen der phys. Klasse, 1818-19, p. 426; also
Ann. Chim. Phys., vol. xiv. p. 172; xix. p. 350.
222 THE MODERN CHEMICAL PERIOD CHAP,
lich,1 who explained the occurrence of isomorphous crystals
in substances of different nature by proving that they
possessed a similar chemical composition. Thus he found,
on examining the salts of phosphoric and arsenic acids, that
only those of analogous composition and containing equal
amounts of water of crystallisation were isomorphous. His
subsequent investigations of selenates and sulphates, of the
isomorphism of magnesium, and zinc oxides, and of iron,
chromium and aluminium salts, confirmed the intimate
connection existing between crystalline form and chemical
composition. At first, after making those observations,
Mitscherlich was of opinion that isomorphism depended
chiefly on the number of the elementary particles (in the
molecule), but he soon convinced himself that the chemical
nature of these had also to do with it.
Berzelius, who regarded the discovery of isomorphism as
" the most important since the establishment of the doctrine
of chemical proportions," endeavoured to arrive at the
atomic weights of the elements by the aid of isomorphous
compounds. For, according to him, isomorphism meant
similarity in atomic constitution ; chemists only required to
know the composition of one compound in order to deduce
1 Eilhard Mitscherlich was born in 1794 in Oldenburg, and died in 1863
at Berlin, where he worked as Klaproth's successor in the University from
the year 1821 ; he enriched chemistry by beautiful discoveries, and especi-
ally advanced it very greatly in the physical direction. At the beginning
of his career he devoted himself to oriental and linguistic studies, only
taking up the natural sciences incidentally ; but, after circumstances had
compelled him to turn wholly to medicine and its allied subjects, his
intercourse with Berzelius, to whom he went in Stockholm in 1819, was
decisive as to his future course. His work will frequently be referred to
in the special section of this book ; but mention may be made here of
his important investigation of manganic and permanganic acids, his work
upon selenic acid, and that upon benzene and its derivatives. His success-
ful attempts to prepare minerals artificially and his varied studies in geo-
logical chemistry give further proof of the many-sidedness of the man, his
greatest achievement of all being the discovery of isomorphism, mentioned
above. His Lehrbuch der Chemie is marked by originality both of form
and contents. For an account of Mitscherlich's life and work, see Hofmann's
Chemische Erinnerungen, etc., p. 30, and the Erinnerung an Eilhard Mit-
scherlich (" Memorial of Eilhard Mitscherlich," by Alexander Mitscherlich,
Berlin, 1894).
v THE ATOMIC THEORY IN 1826 223
that of the remaining isomorphous ones from it. The
quantities of the isomorphous elements which replaced one
another, referred to a definite unit, — say oxygen or hydrogen
— were regarded by Berzelius as the relative atomic weights.
He made extensive use of this new aid to confirm the cor-
rectness of his atomic weight determinations.
The Atomic Weight System of Berzeliiis, 1821—1826.
At first, in 1821, Berzelius did not consider that any
change [in the atomic weights was called for, as the new
facts could be made to accord with his determinations and
deductions. But five years later he resolved, after minute
consideration, upon certain modifications, which chiefly con-
sisted in halving the atomic weights of many of the elements.
The grounds which weighed with him in this he set forth in
a conclusive manner.1 What mainly necessitated the abandon-
ment of his former assumptions was the composition of chromic
oxide and chromic acid. The amount of oxygen in the
latter (so he writes) was to that of the base as 3:1 in
neutral salts, whence the composition CrO3 followed for
chromic acid ; while in chromic oxide the proportion was as
Cr2 : 03. But, in order to concede this last, he had to give
to ferric and aluminic oxides (oxygen compounds iso-
morphous with and capable of replacing chromic oxide) the
analogous compositions F203 and A12O3, and to their metals,
as a consequence, only half as large atomic weights as he
had previously done. Iron protoxide received the simplified
formula FeO, and the oxides of magnesium, zinc, nickel,
cobalt, etc., which were isomorphous with it, were regarded
as similarly constituted. The necessary result of all this
was, as already stated, the halving of the atomic weights
hitherto in use, so that these now conformed to Dulong
and Petit's law. With the atomic weights of sodium,
potassium and silver, which Berzelius likewise halved, the
circumstances were peculiar. He had arrived at the con-
clusion, with respect to basic oxides, that the strong bases
1 Pogg. Ann., vol. vii. p. 397; vol. viii. pp. 1, 177.
224 THE MODERN CHEMICAL PERIOD CHAP.
(such as oxide of potassium) contained metal and oxygen in
the proportion 1:1, and therefore gave potassium, sodium
and silver double their proper atomic weights ; for, according
to our present ideas, two atoms of the metal are combined in
these bases with one of oxygen. The following list by him
of the atomic weights of some of the more important elements,
with hydrogen as the unit, shows the approximation of the
numbers to those in use to-day, and also the amendment l
which some of them had undergone during the years 1818-26
<cf. table, p. 218)—
Carbon . 12 "25 (12) Lead . 207 '4 (207)
Oxygen
16 (15-96)
Mercury
202-8 (200)
Sulphur
32-24 (32)
Copper
63-4 (63-3)
Nitrogen .
14-18 (14)
Iron
54-4 (56)
Chlorine
35-47 (35-4)
Sodium
46-6 (23)
Phosphorus
31-4 <31)
Potassium .
78-5 (39)
Arsenic
75-3 (75)
Silver
216-6 (108)
The figures in brackets indicate the current values.
In this table of the year 1826 we find for the first time
the atomic weights of nitrogen and chlorine as simple sub-
stances. Berzelius held longer than any other chemist to
his assumption that they contained oxygen; the grounds
which necessitated his giving up this hypothesis are entered
into further on.
If we review these efforts of Berzelius at determining
the atomic weights of the elements, we see that he was
mainly guided, in the case of non-volatile bodies, by the
composition of the oxygen compounds, i.e. by the deter-
mination of the proportion of element to oxygen, and
1 Berzelius, who had devoted his whole energies to perfecting analytical
methods and amending the atomic weight numbers, had afterwards to
suffer harsh criticism from others who, by reason of improvements in such
methods, attained to still more exact results ; this applied in an especial
degree to Dumas (cf. Ann. Chem., vol. xxxviii. p. 141 et seq.), who deter-
mined the equivalent of carbon "with every imaginable precaution," and
found its value to be 6. The difference between this number and that
which Berzelius had found, viz. 6 '12, caused Dumas to utter the most severe
reproaches against the great master of analysis (cf. Berzelius' mild reply,
Lehrb. d. Chem., vol. iii. p. 1165, and Liebig's admirable protest against
Dumas' procedure, Ann. Chem., vol. xxxviii. p. 214 et seq.}.
DUMAS AND THE ATOMIC WEIGHTS
then, secondly, by the doctrine of isomorphism, while to the
Dulong-Petit law he allowed only a slight influence. In
those cases where the elements or simple compounds of
the elements were known in the gaseous state, his volume
theory came in as a help towards deducing the desired values.
Berzelius still held fast to the idea that the amounts of the
elements contained in equal gaseous volumes were propor-
tioned to their atomic weights. But this assumption was
soon overthrown by the remarkable results of an investiga-
tion which exercised such a profound influence on the views
of many chemists that it must be described at this point.
Dumas' Attempt to alter the Atomic Weights.
In the year 1827 a young chemist, J. B. A. Dumas (cf.
p. 272 et seq.\ who had already made himself favourably
known by other work, published a research,1 the great merit
of which lay in the working-out of an admirable method for
the determination of vapour densities. By this method he
succeeded in estimating the specific gravity of the vapours
of several elements ; and the relation existing between these
comparable values was, according to Dumas (who took up
here the same standpoint as Berzelius in his volume theory),
that of the relative atomic weights. The elements which he
adduced were iodine and mercury, and to these he added
phosphorus and sulphur a little later.2 The result of this
was that he obtained different numerical values from those
assumed by Berzelius for the atomic weights of the above
elements, which had been held for a year past. Taking the
atomic weight of hydrogen as 1, and that of oxygen as 16
(Berzelius' numbers), the above vapour densities gave the
values 123 for iodine, 101 for mercury, 6 2 '8 for phosphorus,
and 96 for sulphur. Further, Mitscherlich determined the
vapour density of arsenic in 1833, and calculated from this
the atomic weight 150. True, these numbers bore a simple
1 Ann. Chim. Phys., vol. xxxiii. p. 337.
2 Ibid., vol. xlix. p. 210; vol. 1. p. 170.
226 THE MODERN CHEMICAL PERIOD CHAP.
relation to the atomic weights of Berzelius, that of the latter
for mercury (200) being double, those for phosphorus and
arsenic (31 and 75) half, and that for sulphur (32) one-third
as great as the values deduced by Dumas from his vapour-
density determine ' ;ons, and held by him to be the correct
ones. The result ( :. this alteration of the atomic weights by
the latter was great confusion. Wh'le Berzelius remained
true to his own numbers, holding n ^r uric oxide, for ex-
ample, to be composed of mercury and oxyg^r '^ atomic
proportions, Dumas assumed in it two atoms of ury to
one of oxygen, and gave it the composition ana formula
which Berzelius ascribed to mercurous oxide, viz. Hg2O.
Again, to phosphuretted hydrogen, in which Berzelius quite
rightly assumed the proportions of three atoms of hydrogen
to one of phosphorus, on account of its analogy to ammonia,
Dumas gave twice as many atoms of hydrogen, and therefore
the formula PH6.
In making the above alterations Dumas' procedure was
quite without method, and only served to complicate matters
further. He drew a theoretical distinction between smallest
physical and chemical particles, bearing Avogadro's specu-
lations in mind; but this attempt at separating molecule
from atom remained not only unfruitful, but resulted in con-
fusion. The manner in which Dumas spoke of half an atom
of oxygen, and of hydrochloric acid as composed of half atoms
of hydrogen and chlorine, must have been unintelligible at
that time,1 and was sharply criticised by Berzelius.
A comparison of the atomic weights of Berzelius and
Dumas with those of to-day shows us how fully justified
the former was in adhering to his own, which he had
arrived at after the most mature consideration ; Berzelius'
values have proved to be the right ones. In view of recent
experience, however, he became more cautious in the use of
his volume theory, and from henceforth only applied the
law — that the atomic weights of the elements are propor-
1 If Dumas had been fully acquainted with Avogadro's ideas, he would
have expressed himself more distinctly, and have cleared up the opposing
points which remained unsolved.
MICHAEL FARADAY 227
tional to the densities of their vapours — to the permanent
The mighty reform which Dumas aimed at in this
section of theoretical chemistry remained without result ;
and there is justification for the reproa^ brought against
him by many, and more especially by Jferzelius, of having
introduced obscurity ,\jnd disorder into1" the atomic weight
system of the latter. <: For the sake of an unproven hypo-
thesis ™ t.^ neglected the most striking chemical analogies
(e.g. th :etween ammonia and phosphuretted hydrogen),
and frequently confused things which were perfectly clear.
In consequence of the objections which he raised to Berzelius'
atomic weights of the elements, the distrust of these latter
by contemporary chemists grew in extent, so that we find
even the most distinguished investigators like Gay-Lussac
•and Liebig doubting whether it was possible to determine
the relative weights of the atoms with certainty. They
would have satisfied themselves with establishing the equi-
valents, and leaving the atomic weights quite out of account.
The opposition to the atomic weight system of Berzelius was
at its height towards the end of the third and beginning of
the fourth decade of the century. In Germany, especially,
L. Gmelin advocated the establishment of the simplest
" combining weights"; but the certainty of being able to
determine the true equivalents of the elements was not in
itself sufficient, although Faraday's discovery of the electro-
lytic law in 1834 appeared to guarantee a solid basis for
this (see second paragraph below).
Michael Faraday, who was born in London in 1794, was
endowed with such exceptional inclination for the study of
the natural sciences and such experimental aptitude that he
worked his way up from humble circumstances, although he
had received no systematic training previous to his con-
nection with Davy. Davy immediately recognised the
extraordinary talents of the youth, and got him to assist him
in his work. Faraday's most important discoveries belong
to the domain of physics (his investigations on induction
Q 2
228 THE MODERN CHEMICAL PERIOD CHAP.
currents, electro-magnetism and diamagnetism). His electro-
lytic law, which was' of such supreme importance for the electro-
chemical theory, is touched upon below. He made himself
known to the chemical world more particularly by his
beautiful investigations on the liquefaction of gases, by his
work on the hydrocarbons from oil-gas (when he proved the
isomerism of butylene with ethylene), and by that on the
chlorides of carbon. He was one of the earliest to promote
the study of physical chemistry, which owed to him its first
great advance since the investigations of Dulong and Petit
on specific heat, and those of Mitscherlich on isomorphism.
The results of most of his experimental work were published
in the Philosophical Transactions, but some in Poggendorff's
Annalen and other journals. During the greater part of
his life (he died in 1867) he worked at the Royal Institu-
tion, in which he became professor in 1828. In addition to.
his wonderful gifts as an investigator, Faraday possessed in
an exceptional degree the power of clear and pleasant ex-
position ; the memory of his " Lectures to Children " at the
Royal Institution still survives (see his delightful little book,
The Chemical History of a Candle). In private life the
simplicity and amiability of his character made him greatly
beloved.1
Faraday made the memorable observation (see above) that
the same galvanic current decomposed electrolytes, e.g. water,
hydrochloric acid and metallic chlorides, in such a manner
that equivalent amounts of hydrogen or metal were separated
at the negative pole, and the corresponding quantities of
oxygen or chlorine at the positive.2 He grouped those facts
together under the title of "The Law of definite Electrolytic
Action." In the determination of electro-chemical equiva-
lents he saw a sure auxiliary means for fixing chemical
atomic weights in doubtful cases. Berzelius, however, did
not recognise any necessity in this case either for departing
1 A pleasant account of his life is given by Thorpe in his Essays, p. 142
et seq. , as a critique upon Bence Jones's Life and Letters of Faraday.
2 Phil. Trans, for 1834, or Pogg. Ann., vol. xxxiii. p. 301.
v DAVY'S ELECTRO-CHEMICAL THEORY 229
from his own atomic weights, but — obviously because of a
misconception — disputed the correctness of the numbers
obtained by the electrolytic method.
The time for a clear grasp of the terms equivalent, atom
and molecide, and for drawing a sharp distinction between
these, was not yet come. Berzelius was therefore perfectly
justified in adhering to his relative atomic weights, the best
proof for which was to be furnished later., But, as already
remarked, he now only made use of his volume-theory in a
greatly modified degree, in consequence of the results obtained
by Dumas and Mitscherlich. With regard to vapours, he
foresaw (in 1835) the possibility of the relation between
volume and atomic weight being a variable one (he drew a
distinction between gases and vapours, and only strictly
applied the law of volumes to the latter).
How, in the course of the succeeding decades, Gmelin's
combining weights became gradually replaced by the atomic
weights now in use (most of which had been brought forward
by Berzelius), will be detailed later on. The reader's atten-
tion will be chiefly directed in the following sections to
Berzelius' energy in a speculative direction, as shown in the
setting up of his dualistic system ; this last was the fruit of
an electro-chemical theory which, along with Davy's, now
falls to be briefly considered.
The Electro-Chemical Theories of Davy and Berzdim.
The perception that a close relation existed between
electrical force and chemical reaction spread rapidly at ttie
beginning of. the century, after the decomposition of water
into its constituents by the galvanic current had been-
proved by Nicholson and Carlisle (in 1800), and that of salts
into their bases and acids by Berzelius and Hisinger (in 1803).
The first fruit of the many and varied observations on .the
action of the current on chemical compounds, and on the
accompanying electromotive force in chemical reactions, was
230 THE MODERN CHEMICAL PERIOD CHAP.
Davy's Electro-Chemical Theory,1 which he thought that he
had founded on a firm basis by his ingeniously devised
researches, begun in the year 1800. He took as his
starting-point the proved experimental fact that different
substances, capable of combining chemically with one
another, e.g. copper and sulphur, became oppositely electri-
fied upon contact when insulated. Heating intensified the
resulting difference of potential, until it vanished in
consequence of the chemical combination of the substances.
This latter, Davy then reasoned, is simultaneous with the
equalisation of the potentials. The greater the difference
between these before combination, the greater must be
the chemical affinity of the different substances for one
another. By the addition of electricity to the compounds >
their constituents receive the same electric polarities which
they possessed before combination ; the positive constituents
go to the negative pole, and the negative ones to the
positive.
Davy inclined to the assumption that electrical processes
and the phenomena of chemical affinity arose from a common
cause. His electro-chemical theory was characterised by the
axiom that the small particles of substances which have an
affinity for one another only become oppositely electrified
upon contact. But later researches, especially those of
Berzelius, led to the abandonment of this principle, while,
otherwise, many of Davy's original icjeas were retained.
Berzelius brought forward the main outlines of his
electro-chemical theory in 1812,2 after having already at
various times expressed his views upon the indissolubility of
chemical and electrical processes, upon combustion as an
electro-chemical phenomenon, and on the probability of the
small particles being polarised. But the theory as a whole,
with its far-reaching conclusions, was first published in his
Versuch uber die Theorie der Chemischen Proportionen, etc.,
1 Phil. Trans., 1807, p. 1 ; cf. also his Elements of Chemical Philosophy.
Die Electrochemischen Untersuchungem Davys, with Annotations, constitutes
No. 45 of W. Ostwald's Klassiker.
2 Schweigger's Journ., vol. vi. p. 119.
v BERZELIUS' ELECTRO-CHEMICAL THEORY 231
already mentioned at p. 213. In this we see clearly how he
deduced his theory from facts, and then how, from the
standpoint so obtained, he succeeded in penetrating and
dominating with it the whole domain of chemistry. His
doctrine, developed in this way from the electro-chemical
point of view, continued the prevailing one for the next
twenty years, until it had to yield to the pressure of facts
with which it could not be reconciled.
Berzelius started with the primary assumption that the
atoms of elements were in themselves electric ; electric
polarity, therefore, was an essential property of these
smallest particles, which further possessed at least two
poles, whose quantities of electricity were in most cases
different, so that either positive or negative electricity
predominated in the particle as a whole. Thus elements
were divided into positive and negative, according to which-
ever of these electricities prevailed ; and this last point was
easily solved by noting whether the element in question
was separated at the negative or positive pole of the gal-
vanic battery upon electrolysis.1 In like manner Berzelius
assumed a polarity for compounds as well as for elements,
although, in consequence of the neutralisation of the
opposite electricities by one another in the formation of
compounds, this polarity was thereby weakened. The
intensity of the polarity was, according to him, a measure of
the excess of one or the other kind of electricity. The
dissimilar polar intensity of the small particles was regarded
as the cause of their various affinities (der verschiedenen
Affinitatswirkungeri). And, as the forces of affinity were
found to be dependent on the temperature, so polarity was
also to be regarded as a function of heat.
Chemical combination of the elements or compounds
consisted, according to Berzelius, in the attraction of the
dissimilar poles of the small particles, and in the consequent
neutralisation of the different electricities. If positive
1 At first Berzelius designated the elements after the poles at which
they were separated, i.e. he called the metals negative, and the metalloids
positive.
232 THE MODERN CHEMICAL PERIOD CHAP.
electricity predominated in the original substance, then an
electro-positive compound resulted, and vice versa. If the
electricities neutralised one another, then an electrically
indifferent product was the result. Oxygen, as the most
electro-negative element, served Berzelius here (as it had
done in his atomic weight estimations) as the standard by
which to determine the kind of polarity of the^ various
elements. Those elements which yielded basic compounds
with oxygen, even although only their lowest oxides were
basic, were classed as electro-positive, and those whose
oxides were acids as electro-negative. Following this
principle he arranged the simple substances in a series, in
which oxygen as the first member was followed by the other
metalloids, while hydrogen formed the bridge between the
latter and the metals, the whole ending with sodium and
potassium. In referring to this, Berzelius frequently stated
that many elements which were positively polar with regard
to some were negatively polar with regard to others, e.g.
sulphur was positive to oxygen, but negative to the metals
and hydrogen, — and so on. Oxygen alone he held to%&
an absolutely negative element, because in no case did it
behave as a positive one with respect to any other.
By the aid of such conceptions, which formed the
substance of his electro-chemical theory, Berzelius was en-
abled to give a satisfactory interpretation of the facts which
were at that time considered of greatest moment. The electro-
lytic processes, i.e. the separation of the positive and negative
constituents of compounds at the negative and positive poles
respectively, were explained in a simple manner by the
assumption that the galvanic current reinvested the small
particles of compound bodies with their original polarity.
The many and various manifestations of affinity could in
this way be referred back to a common cause.
Proceeding from this one hypothesis, — that electric
polarity was a property of the atoms of substances, — Berzelius
was able to bring y light and order into the province of
inorganic chemistry, which was at that time (1819) almost
the only branch of the science to be considered. His
v THE DUALISTIC SYSTEM OF BERZELIUS 233
electro-chemical theory led him, in the first instance, to a
perfectly definite conception of the " constitution or rational
composition of chemical compounds," and then to a nomen-
clature and corresponding system of formulae developed
from this. His efforts in this direction were crowned with
the greatest success. Even at the present day we cannot
do without the chemical language which he introduced,
although, on the other hand, his dualistic views on the com-
position of chemical compounds have not survived so long.
He was, however, the first to draw a precise distinction
between the empirical and rational composition of chemical
compounds. The constitution of the latter was, according to
him, arrived at by investigating their proximate constituents
(such being, for instance, Cu2O, CuO, and (C2H5)2O in copper
salts, ethers, etc.), and this task he regarded as one of the
most important which falls to the lot of the chemist. He
himself devoted his whole energies to its solution, the
electro-chemical theory serving as a means whereby he
might attain to this great end.
The Dualistic System of Berzelius.
The necessary consequence of the electro-chemical view-
was the assumption that every compound body consisted of
two parts, which were electrically different; without such
difference a chemical compound could not be formed.
Further, the constitution of the latter was known when its
positive and negative constituents were demonstrated. It
was again compounds of oxygen, — acids, bases and salts, —
by means of which Berzelius developed this, his dualistic
doctrine. The elements which were combined with oxygen
were the positive constituents, e.g. the metals in oxides,
and the metalloids in acids. The electro-chemical antithesis
was illustrated by the following formulae : —
+- +-
FeO BaO
Iron Barium Sulphuric Carbonic
protoxide oxide acid acid.
234 THE MODERN CHEMICAL PERIOD CHAP.
The anhydrous bases are the positive constituents of salts,
and the acids — in which negative polarity predominates —
the negative ones, as is shown by the formulae —
+ - +
BaO-S03 ZNOC02.
Berzelius considered that the strongest proof of the correct-
ness of this theory lay in the electrolytic decomposition of
compounds, especially of salts, into the above-mentioned two
portions, which were separated at the poles of opposite
electricity to their own. He further sought to explain the
composition of double salts according to the dualistic
hypothesis, giving, for example, sulphate of potash as the
positive, and sulphate of alumina as the negative constituent
of alum.
In the year 1819, when Berzelius published a detailed
exposition of his electro-chemical theory, he was convinced
that all acids contained oxygen. In his view water played
in hydrated acids the part of a weak electro-positive con-
stituent, and in metallic hydroxides that of a weak electro-
negative one ; the hydrates of sulphuric acid and of cupric
oxide therefore received the formulae —
H2OS03 CuO-H20.
The binary conception, which had already been applied by
Lavoisier to acids and bases, and even by Rouelle to salts,
thus received the strongest support from the electro-chemical
theory, and was materially developed in consequence. It
will be shown in the next section how Berzelius was obliged
to give up Lavoisier's one-sided theory of the oxygen acids.
The efforts of Berzelius to introduce a rational and
generally applicable nomenclature go back to the year
181 1.1 His nomenclature is a continuation of that of
Lavoisier, de Morveau and Berthollet, which however he
greatly extended and amplified, his first efforts in this
direction having been published in the Versuch iller die
1 Journ. de Phys., vol. Ixxiii. p. 257.
v BERZELIUS' SYSTEM OF NOTATION 235
Theorie der Chemischen Proportioned, etc., already frequently
mentioned. The division of the elements into metalloids
and metals, according to their electro-chemical character;
that of the positive oxygen compounds into suboxides,
oxides and peroxides ; and the corresponding division of the
acids (which were designated according to their degree of
oxidation), have been found to be so convenient that only
very trifling alterations have had to be made in them.
In like manner he designated the chlorine compounds
corresponding to the oxides by adding different final
syllables or prefixes, e.g. sub-chloride (Chlorur), chloride, per-
chloride, etc. In the nomenclature of the oxygen salts the
name of the acid constituent preceded that of the basic, e.g.
sulphate of oxide of copper.
He also endeavoured to apply similar principles in
naming organic compounds, whose constitution had been
determined on his own lines. But the time had not yet
come when it was possible to devise a rational nomenclature
for these.
Berzelius next established a system of chemical notation,1
connected in the most intimate possible manner with his
chemical nomenclature, which had given expression in clear
language to the electro-chemical views on the composition
of substances ; this notation was to attain the same end in a
more concise manner. In doing this he rendered an immense
service, for it thus became possible, by the aid of simple
symbols, not merely to express the composition of chemical
compounds, but to picture even complicated reactions in an
easily intelligible manner. He gave to each element a symbol,
which was usually the first or the first two letters of its Latin
name, less often of the Greek one ; thus the symbol jET stands
for hydrogen (hydrogenium), S for sulphur (sulphur), 0 for
oxygen (oxygenium), C for carbon (carlo), Ag for silver
(argentum), Hg for mercury (hydrargyrum), and so on.
These symbols denote at the same time the atomic weights
of the elements in question, referred to a definite unit.
1 Cf. particularly the Versuch uber die Theorie der Chemischen Propor-
tionen, p. 116, et seq.
236 THE MODERN CHEMICAL PERIOD CHAP.
By placing the symbols alongside of one another, and
adding a figure to indicate the number l of atoms when the
latter amounted to more than one, the formulae of chemical
compounds was obtained : e.g. H20 for water, S02 for
sulphurous acid, C02 for carbonic acid, Na2OC02 for
carbonate of soda, etc.
What an advance upon Dalton's attempts towards the
same end, his figures only serving to illustrate the simplest
of compound substances ! Dalton's notation was soon for-
gotten, never having indeed met with general approval,
while that of Berzelius became indispensable to chemists,
and still remains so.
Berzelius attached a special meaning to the symbols
with a bar drawn across them, these being employed by him
to indicate that the elements in question were in the state
of double atoms, or, as he put it,2 that " they remain
c onnected together ; " 3 this applied, for example, to the
hydrogen in water, JtO, to the chlorine in anhydrous per-
chloric acid,-G107J and to the iron in the sesquioxide,:Fe03.
This mode of notation, which had exceedingly bad results,
arose from Berzelius taking oxygen as his unit, and using
it as the standard for the saturation-capacities of other ele-
ments.4 He was thus led to the assumption of the double
atom constituting a chemical unit, and the above symbols
with bars served him to give expression to this ; at a later
period, however, he gave up using them, and reverted to the
true atomic weights. There were nevertheless many chemists
who would not concur in this view, cherished by Berzelius
for a time, of the atoms of certain elements being only
present as pairs in compounds ; these chemists assumed
1 Berzelius at first denoted the number of oxygen atoms by dots, and
that of sulphur atoms by commas, e.g. calcium oxide, Ca ; iron bisulphide,
Fe ; this system remained longest in use among mineralogists.
2 Lehrb. d. Chemie, fifth edition, vol. i. p. 121.
3 " . . . dass sie zusammenhdngend bleiben. "
4 Berzelius designated oxygen as "the measure of the relative weight
according to which an element entered into combination " (dass Mass der
relativen Gewichtsmenge, nach ivelcher ein Grundstoff vorzugsweise Ver-
bindiingen eingeht).
v MANIFESTATIONS AGAINST DUALISM 237
simple instead of double atoms and, with this, equivalents
instead of atoms. Blomstrand, who has shown in his admi-
rable work, Die Chemie der Jetztzeit (" The Chemistry of the
Present Time "), the close connection which exists between
the views of Berzelius and those held to-day, describes the
results of the system of notation and of the views just men-
tioned in the following eloquent words : " This erroneous
conception was without doubt the almost sole reason why
Berzelius' atomic theory found so little acceptance ; it
acted like a restraining curb in preventing the free develop-
ment of the latter, and led little by little to a peculiar
confusion with regard to the fundamental principles of
chemistry, the distinction between atomic weight and
equivalent becoming by degrees nearly effaced, until at last
the volume-atomic weights and the whole atomic theory
of Berzelius were almost forgotten by the great majority of
the chemists of his school."
Like every innovation, the admirable system of notation
which Berzelius recommended met with most violent opposi-
tion from many chemists, especially in England. People
spoke of " abominable symbols " which were more calculated
to introduce confusion than clearness.
In 1820, then, the dualistic system, with the electro-
chemical theory for its basis, stood fully equipped, and was
soon utilised by the vast majority of chemists as a guide in
the confusion which resulted from the daily accumulation
of new facts. Berzelius further attempted to apply the
dualistic hypothesis in organic chemistry, which, from the
third decade of the century, was more and more attracting
the attention of chemists. How it came into collision here
with the unitary theory, and had finally to succumb to the
latter, will be described further on.
Manifestations against Dualism — Theory of the Hydrogen
and of the Poll/basic Acids.
The tenet which was set up by Lavoisier, and which
Berzelius defended with all his power, — that the character
238 THE MODERN CHEMICAL PERIOD CHAP.
of acids depends upon their containing oxygen, and that
consequently this element is an unfailing constituent of their
salts, — this theory of the oxygen acids was already greatly
shaken towards the end of the first decade of the present
century, and was abandoned by most chemists during the
second, as a knowledge of facts opposed to it increased.
Finally Berzelius, who remained longest true to the older
idea, convinced himself of the existence of acids free from
oxygen. The gradual transformation of chemistry which
resulted from the setting aside of this dogma (that all acids
contained oxygen) was a thorough one, for the unadaptable
dualistic system was thereby battled with, and its fall pre-
pared for.
In order to thoroughly understand this change of views,
it is necessary that a clear light should be thrown upon the
facts which brought it about. The discovery of the alkali
metals by Davy and the allied researches which he made
on the nature of chlorine must be regarded as the starting-
points from which the light of the new knowledge radiated.
Before Davy, who had recognised in the galvanic current
a powerful means for decomposing chemical compounds,
isolated potassium and sodium from the alkalies by its aid,1
the latter were regarded as undecomposable ; and this
even although, from the time of Lavoisier, it was con-
sidered probable that they were constituted analogously to
the metallic oxides, and were therefore oxygen compounds.
This view was also held at an even earlier date
by Scheele, as his recently published journals show.
The many fruitless experiments which Davy had made with
the alkalies in solution were finally crowned with success
when he exposed these substances, only slightly moistened,
to the action of a strong current. His correct assumption,
that the metals separated at the negative pole were true
elements, did not indeed find immediate acceptance ; in fact
he himself was temporarily in doubt as to whether they did
not contain hydrogen, especially after the presence of the
latter • element in the alkalies had been proved by Gay-
1 Phil Tram, for 1808, p. 1.
v DAVY'S DISCOVERY OF THE ALKALI METALS 239
Lussac and Thenard, both of whom from this point took an
active part, by their researches,1 in the solution of the
problems in question. The idea that the alkali metals
might be hydrogen compounds had crept in from an analogy
drawn between them and ammonia ; at that time the latter
was supposed to contain oxygen, which was withdrawn from
it in the formation of ammonium amalgam. The erroneous
conclusion that the above metals contained Jhydrogen, which
resulted from this false interpretation, was however put
right by Gay-Lussac and Thenard, who explained the point
correctly. (Cf. "below. It was mainly upon the three re-
actions specified towards the end of the next paragraph that
Gay-Lussac and Thenard relied here ; from these the
elementary nature of the alkali metals, as well as of chlorine,
followed.) Consequently, from the year 1811, potassium
and sodium were regarded as metals and therefore as
elements.
With the elucidation of the above points, the question
as to whether chlorine was really a compound substance,
and not rather a simple one, rapidly approached its solution.
According to the assumption of Berthollet and Lavoisier,
hydrochloric acid contained oxygen combined with a radical
muriatique, and the chlorine which was liberated by its
oxidation was looked upon as oxidised hydrochloric acid,
and was therefore named so (oxy -muriatic acid). At the
time when Davy2 and Gay-Lussac and Thenard3 began
their memorable investigations, hydrochloric acid gas was
generally held to contain chemically combined water. But
even with the most powerful reducing agents these chemists
were unable to prove the presence of oxygen either in per-
fectly dry hydrochloric acid or chlorine, and this of itself
made them incline to the belief that chlorine was an element
and hydrochloric acid its hydrogen compound. The idea,
however, of oxygen being a necessary constituent of all acids
had taken such firm root that numerous fresh investigations
1 Ann. de Chimie, vol. Ivi. p. 205 ; vol. Ixv. p. 325.
2 Phil. Trans, for 1810, p. 231.
3 Memoires de la Societed'Arwuil, vol. ii. p. 339.
240 THE MODERN CHEMICAL PERIOD CHAP.
were required before it could be got rid of. The most
important of the observations which led to this were the
following : — Hydrogen and chlorine unite to form anhydrous
hydrochloric acid, which is decomposed by sodium with the
liberation of half its volume of hydrogen and the formation
of sodium chloride, while the latter also results directly from
the combination of sodium and chlorine.
Upon the ground of those facts Davy was the first to
express the distinct opinion that chlorine was an element,
suggesting for it the name1 by which it has since been
known. At first Gay-Lussac and Thenard had misgivings
about agreeing to this, fearing to disturb the uniformity of
the chemical system. But, after the former had completed
his famous investigation upon iodine, both he and Thenard,
as well as other French chemists, were obliged to concur in
Davy's view. Iodine and fluorine now received a place
among the elements, next to their analogue chlorine.
Berzelius did not allow himself to be convinced all at
once of the necessity for this thorough innovation, which
entailed the abandonment of the theory of oxygen acids.
The unity of chemical theory went with him before every-
thing else ; he saw in the projected reform an overthrow of
the principles which had governed the older chemical system.
After having given eloquent expression to his ideas on the
subject in letters to Marcet, Gilbert, Thomson and others,
he collected together the arguments in favour of the older
view in a treatise 2 entitled : Versucli einer Vergleicliung
der d/teren und der neueren Meinungen uber die Natur der
oxydierten Salzaure, zur Beurtheilung des Vorzuges der einen
v&r der anderen (" An attempt to compare the Old and New
Opinions with regard to the Nature of the Oxidised Muri-
atic Acid, and to estimate the Advantages of the One over
the Other"). His standpoint is clearly set forth in the
following words : " I decline to give in my adhesion to the
new doctrine until it has been made perfectly consistent
and uniform with the new theoretical science which its
1 Phil. Trails, for 1811, p. 1.
2 Gilbert's Annahn, vol. 1. p. 356.
v THEORY OF THE HYDROGEN ACIDS 241
authors claim to have built upon the ruins of the chemical
theory that they have demolished. For I demand un-
compromisingly from any chemical theorem that it shall
agree with the rest of chemical theory and be capable of
incorporation in it ; if this be not the case, then I must
reject it, unless, indeed, the evidence in its favour is of such
an incontrovertible nature as to necessitate a revolution in
the chemical theory with which it is at variance."
In one point, however, Berzelius soon gave up the
opinion that every acid must contain oxygen, by recognising
sulphuretted and telluretted hydrogens as hydrogen acids ;
this latter nomenclature (hydracides) was first made use of by
Gay-Lussac. At that time Berzelius still held that oxygen
was present in chlorine, iodine and fluorine, even after Gay-
Lussac's famous research upon the salts of hydrocyanic acid
had proved that these last were free from it. It was only after
he had been able to make the results of his own investigations
on ferro-cyanogen and sulpho-cyanogen compounds agree
with the theory of non-oxygenated acids that he resolved to
include chlorine and iodine among the elements. About
the same time (1820) he gave up the idea that nitrogen
and ammonia contained oxygen ; but it was not until 1825
that he abandoned what remained of his old view, by
including fluorine with chlorine and iodine among the salt-
forming elements or halogens ; * he drew a sharp distinction
between the haloid salts, i.e. the salts produced by the
combination of the above elements with the metals, and the
amphid salts, or those containing oxygen.
Theory of the Hydrogen Acids.
Several years before Berzelius had given up the oxygen-
acid theory, Davy,2 and almost at the same moment Dulong,3
made the attempt to bridge over the gap between the
oxygen and hydrogen acids by a uniform interpretation of
1 Jahresber., vol. vi. p. 185 ; also in his Lehrb. d. Chemie.
2 Phil. Trans, for 1815, p. 203.
3 Schweigger's Journal, vol. xvii. p. 229.
R
242 THE MODERN CHEMICAL PERIOD CHAP.
their constitution. In these efforts we see the beginnings of
the hydrogen-acid theory, which was to become of such
great importance a few decades later on. From his observa-
tion that iodic anhydride was devoid of acid properties, but
acquired them after combination with water, Davy drew the
conclusion that hydrogen and not oxygen was the acidifying
principle in the latter compound ; hydrogen, in his opinion,
was an essential constituent of all acids. The assumption,,
that hydrated acids and salts contained water or metallic
oxides together with acid anhydrides, he held to be un-
proven and unnecessary. Dulong expressed himself in a
similar sense after an investigation of oxalic acid and its
salts; the former he regarded as a compound of hydrogen
with carbonic acid, while in the latter he assumed an
analogous combination of the metals with the elements of
carbonic acid. In these discussions a dualistic conception
of acids and salts was still apparent, hydrogen and the
metals being placed opposite salt-forming radicals ; but the
way was now opened for a unitary theory of acids and salts.
Berzelius' criticism of those attempts to explain the
constitution of important classes of compounds was un-
usually mild ; but at the same time he adhered to his
dualistic view, since he laid special weight upon the possi-
bility of preparing the immediate constituents (of the acids),
the radicals of the hydrogen-acid theory being but seldom
capable of isolation.
As his electro-chemical theory became better known, and
was received with approbation, the opposing views of Davy
and Dulong lost ground ; it was only in the thirties that
they reappeared, with fresh arguments to back them up,
after which they were gradually accepted. The following
observation by Daniell (in the year 1840) upon the electrolysis
of salts was brought forward as an argument in their favour :
" When galvanic currents are passed through different electro-
lytes, e.g. acidified water, fused chloride of lead, or a solution
of sulphate of potash, amounts of hydrogen, lead and
potash are set free at the negative pole, which stand to
one another in the ratios of their chemical equivalent-
v LIEBIG'S THEORY OF POLYBASIC ACIDS 243
numbers." This is in accordance with Faraday's " Electro-
lytic Law," excepting that in the case of the sulphate of
potash an equivalent of hydrogen is liberated in addition to
an equivalent of the base. The current therefore appears to
do double work here, in spite of the law just mentioned ;
for, if it be assumed that the immediate constituents of one
equivalent of the salt are potash and sulphuric acid, then
only one equivalent of potash — as the electro-positive
portion — should result, and not one of potash plus one of
hydrogen. But this apparent contradiction is done away
with by adopting the view of Davy and Dulong, i.e. by
assuming potassium as the positive, and the radical SO4
(oxy-sulpliion) as the negative constituent. The two
equivalents of potash and hydrogen are then seen to be
secondary products of the decomposition of one equivalent
of water by the potassium originally separated at the
negative pole. The conclusion drawn from this observation
on the constitution of salts was then of course extended to
that of acids, in which hydrogen was assumed as the one
constituent, and a radical — either containing oxygen, or
free from it — as the other.
The theory of the hydrogen-acids became still more
clearly denned after Liebig had brought forward his : —
Doctrine of the Polybasic, Acids.1
This we shall consider here, although it only dates from
1834, because of its close connection with the above views
of Davy and Dulong. Many chemists at that time, Gay-
Lussac and Gmelin in especial, inclined to the assumption
that the atoms of the various metallic oxides contained one
atom of oxygen to one atom of metal, and combined with
one atom of acid to form neutral salts ; Berzelius too, after
1826, was of opinion that this combining proportion was
the rule. But a view of such simplicity as this, according
to which almost every acid was regarded as monobasic, could
1 Ann. Chem., vol. xxvi. p. 113.
R 2
244 THE MODERN CHEMICAL PERIOD CHAP.
no longer hold its ground after Graham's 1 famous investi-
gation of the phosphoric acids.2 For this chemist showed
that ordinary, pyro-, and meta-phosphoric acids contained
different amounts of " basic water " to 1 atom of P2O5, viz.
3, 2 and 1 atoms of water, these latter being replaceable by
metallic oxides. The different saturation-capacities of those
acids were in this way demonstrated, being held to depend
upon the amounts of basic water which entered into their
constitution.
Liebig built upon the ground which Graham had
prepared, and with such success that, by the aid of his
own admirable and comprehensive researches upon a large
number of acids, he was able to firmly establish his theory
of polybasic acids. By his investigations on citric, tartaric,
cyanuric, comenic and meconic acids, he convinced most
chemists that these resembled phosphoric acid in basicity (i.e.
were polybasic). He distinctly and definitely resisted the
application to them of the arbitrary tenet that the atoms of
all acids are equivalent to one another, and he gave as the
criterion of a polybasic acid its capability of forming com-
pound salts with different metallic oxides (e.g. such a salt as
PO4 -j J^2 V Liebig was the first to distinguish between
mono-, di-, and tri-basic acids.
In order to express the facts, he still made use of the de-
finition of acids in the dualistic sense, according to which
1 Thomas Graham, born in Glasgow in 1805, became in 1830 Professor
of Chemistry at Anderson's College of that city, and then in 1837 at Uni-
versity College, London. In 1855 he resigned this post on being appointed
Master of the Mint ; he died in 1869. His admirable text-book, Elements
of Chemistry, was used not only in England, but was recast and translated
into German by J. Otto and H. Kolbe. Graham's originality was shown
by his valuable physico-chemical investigations on the diffusion of gases,
osmose, etc. , which opened out new paths in the science, while at the same
time he enriched general chemistry, especially inorganic, by his purely
chemical work. Thanks to the generosity of Graham's old friend, the late
James Young of Kelly, his collected researches have been published in one
large volume, entitled Chemical and Physical Researches (Edinburgh, 1876).
A full account of Graham's life, and of the great services which he rendered
to chemistry, is given by Thorpe in his Essays, p. 160, et seq.
2 Phil. Trans, for 1833, p. 253 ; or Ann. Chem., vol. xii. p. 1.
v LIEBIG'S THEORY OF POLYBASIC ACIDS 245
these were regarded as compounds of one atom of acid anhy-
dride with one, two or three atoms of water. But this he
felt to be unsatisfactory, since it did not permit acids and
salts to be regarded from a uniform standpoint. He pointed out
with great acuteness the contradictions which were involved
in the retention of this view, summing up his criticism as
follows : " In order to explain one and the same phenomenon
we make use of two different methods. We are obliged to
ascribe to water the most various properties, calling it basic
water, water of hydration and water of crystallisation, while
at the same time we see it enter into compounds in which
it assumes no one of these forms. And all because we have
chosen to draw a sharp line of demarcation between haloid
and oxygen salts — a line not observable in the compounds
themselves, seeing that in all their relations they show
similar properties."
Liebig was led to the theory of hydrogen acids from
grounds of probability, and still more from grounds of con-
venience. The sentences in which he enunciates this
doctrine explain his standpoint so clearly and tersely that
they must be quoted here.
" Acids are particular compounds of hydrogen, in which
the latter can be replaced by metals."
" Neutral salts are those compounds of the same class in
which the hydrogen is replaced by its equivalent in metal.
The substances which we at present term anhydrous acids
only become, for the most part, capable of forming salts with
metallic oxides after the addition of water, or they are com-
pounds which decompose these oxides at somewhat high
temperatures."1
Those sentences distinctly show us the influence which the
accumulating observations on the substitution of hydrogen
by other elements had exercised upon Liebig. This inclina-
tion of the latter to a unitary hypothesis was keenly felt
1 Liebig here formulates sulphates as S04 + Me. The decomposition of
the metallic oxides to which he refers is their reduction, thus —
246 THE MODERN CHEMICAL PERIOD CHAP.
by Berzelius,1 who to the end of his life described Liebig's
theory of the polybasic acids as one which " has led to the
confusion of ideas, and has stood in the way of a more per-
fect knowledge." But in thus criticising views of such great
importance, and which served in quite an exceptional degree
to clear up the uncertain notions with respect to the term
" equivalent," Berzelius stood almost alone.
Development of the Dualistic Doctrine in the domain of
Organic Chemistry — The Older Radical Theory.
During the second, and still more during the third decade
of our century, organic chemistry emerged from its modest
beginnings, to play an important part even so early as in the
forties. It was destined to be the medium for the develop-
ment of important views and of doctrines evolved from these,
thereby reacting beneficially upon its elder sister inorganic
chemistry. At first it continued on pretty much the same
lines as the latter, the dualistic hypothesis, which had kept
its place so well with inorganic, being applied to organic
compounds also. Here again Berzelius struck in as a
reformer with all his accustomed energy, and guided for a
time the fortunes of organic chemistry. A glance at the
earlier history of the latter will show us how imperfect was
the knowledge of this branch of our science before the second
decade of the nineteenth century.
The Growth of Organic Chemistry previous to 1811.
So early as at the close of the seventeenth century
mineral substances were classed apart from vegetable and
animal, the three being treated separately in text-books of
1 The letters between Berzelius and Liebig, already referred to, give in-
structive and at the same time interesting details upon this point, and upon
the genesis and critical examination of Liebig's view ; they also show us
how the estrangement with Berzelius came about (cf. especially pp. 154,
159 etseq., and 166).
v EARLIER DEVELOPMENT OF ORGANIC CHEMISTRY 247
chemistry, in that of Lemery, for instance ; this division was
in accordance with the classification of natural substances
according to the three " kingdoms of nature," which was
even then in vogue. It was from this empirical standpoint
that the chemistry of organic compounds developed itself,
after Lavoisier had proved qualitatively that the main
constituents of these were carbon, hydrogen, oxygen and
sometimes nitrogen, occasionally together with sulphur and
phosphorus. How he sought to utilise this quantitatively
also, by working out a method of organic analysis, will be
described under the history of analytical chemistry. He it
was at all events who laid the foundation for a thorough
knowledge of the subject; for, before scientific investiga-
tion in this branch could become possible, the composition
of organic compounds had to be established. Notwith-
standing that but very little was known at that time about
the chemical constitution of these, Lavoisier tried to form
an opinion on the subject in particular cases. A point
worthy of special mention was his view — a view which for
long exercised great influence — that the organic acids were
oxides of compound radicals, while he supposed that most of
the mineral acids contained oxygen united with an element ;
this had indeed a distinct resemblance to the conceptions of
the radical theory adopted at a later period.
While Lavoisier and other chemists after him remained
true to the old classification of substances, Bergman began
about the year 1780 to distinguish organic from inorganic
bodies. But, in spite of the simplicity which this proposal
had to recommend it, the line which remained drawn between
vegetable and animal substances was only gradually removed
as the knowledge increased that the same chemical com-
pounds occurred both in vegetables and animals, as proved,
e.g. in the case of several fats, formic acid, benzoic acid, etc.
Still it was generally felt to be necessary to strictly separate
organic from inorganic bodies, it being represented as an
infallible distinction that the former could not be prepared
directly from their elements. But even this barrier was
destined to fall before very long, and both classes of com-
248 THE MODERN CHEMICAL PERIOD CHAP.
pounds to be regarded henceforth from the same stand-
points.
The Position of Berzelius with regard to Organic Chemistry.
At the beginning of this century chemists of such
eminence as Dalton, de Saussure, Proust, and especially Gay-
Lussac and Thenard, exercised all their ingenuity in trying
to work out a reliable method for determining the quantita-
tive composition of organic compounds, but the results of
their experiments only partly approximated to the truth.
Before Berzelius (1811), no one had attempted to give a
definite answer to the question whether the composition of
organic substances was, like that of inorganic, subject to the
law of multiple proportions ; whether, therefore, the former
were to be looked upon as chemical compounds in the sense
of the atomic theory. He himself had so far elaborated a
method of analysing the salts of organic acids that he was
able to deduce with tolerable certainty from his results the
existence of simple chemical proportions between the ele-
mentary constituents of an acid and the oxygen of the base.1
This first successful attempt to bring organic compounds
under the atomic theory, in the same way as inorganic, was
followed in 1813 and 1814 by investigations 2 carried on
with improved processes, which strengthened his conviction
that the law of multiple proportions applied in the fullest
degree to organic compounds also. In determining these
atomic weights, he recommended, as a principle to be
followed wherever possible, that the substances in question
should be analysed in the form of their compounds with
inorganic bodies (e.g. acids as metallic salts).
But even although these researches — the first made in
this direction — led to the recognition of an analogy between
the two classes of substances, still Berzelius did not
immediately make up his mind to regard organic com-
pounds as constituted exactly like inorganic (i.e. with
1 Gilbert's Annalen, vol. xl. p. 247.
2 See especially Annals of Philosophy, vols. iv. and v.
v THE VIEWS OF BERZELIUS UPON ORGANIC CHEMISTRY 249
respect to the arrangement of their constituent elements).
On the contrary, he considered it necessary to draw a sharp
distinction between the latter as binary, and organic com-
pounds as ternary and quaternary; for these, as he stated
in 1813, contain more than two elements. As a con-
sequence of this, compounds like marsh gas, cyanogen and
the hypothetical oxalic anhydride were classified as inorganic,
an arrangement which was long retained (and still is, to
some extent) on grounds of convenience, Gmelin being
especially strong in his recommendation of it. But this
empirical separation of the two series of substances soon
proved to be quite inadequate, particularly after various oils
had been recognised as binary compounds of carbon and
hydrogen of complex composition.
Berzelius himself made the attempt, in his treatise1
referred to above, to bridge over the gap between inorganic
and organic bodies by assuming that the latter, like the
former, are constituted binarily, but contain compound radi-
cals in place of elements.
Gay-Lussac's beautiful researches on cyanogen had
without doubt a powerful effect in reviving this idea, which
had already been advanced by Lavoisier, for they proved the
important fact that cyanogen, as a compound radical, can
play the part of an element perfectly. This in its turn gave
rise to further efforts to search for similar atomic complexes
(Atomkomplexe) in other organic compounds. Gay-Lussac
himself expressed the opinion that alcohol consisted of ethyl-
ene and water, and, as its vapour density proved, of equal
volumes of these ; while he assumed carbon and water as the
immediate constituents of sugar. Hydrochloric ether was
regarded by Robiquet as a compound of ethylene with
hydrochloric acid, and anhydrous oxalic acid by Dobereiner
as one of carbonic acid with carbonic oxide.
These efforts to look upon compound radicals as the
immediate constituents of organic substances may be
regarded as the beginnings of the radical theory. The
1 Versuch uber die Theorie der chemischen Proportionen, etc. (Dresden,,
1820).
250 THE MODERN CHEMICAL PERIOD CHAP.
above attempts at a solution were, however, disapproved of
by Berzelius, who raised a warning voice and declared them
incompatible with the electro-chemical views. In accordance
with the latter, the electro-negative oxygen was placed op-
posite to a compound radical as the positive constituent of
a, compound, thus showing that at that date Berzelius did not
believe in radicals containing oxygen. At that time also
he conceded the variability (Veranderlichkeit durch Substi-
tution) of radicals, but went back from this later on, thereby
putting an obstacle in the way of the healthy development
of the radical theory.
The time for the completion of this doctrine was not yet
come; but the theorising upon tlie proximate constituents
of organic compounds was of much benefit, in that it gave a
stimulus to the study of the latter. To the first task of
determining their empirical composition was added the far
higher one of investigating their chemical constitution by
getting at the proximate constituents, as these were under-
stood by Berzelius. The discovery of the first case of
isomerism in the third decade of the century gave a power-
ful impetus to this, and caused the great importance of the
task to be better appreciated, and a more correct idea of it
to be formed. If we try to picture to ourselves the stand-
point of the chemists of that day, we see how such startling
observations of compounds having the same chemical com-
position, but differing totally in their properties, forced them
of necessity to the conclusion that the cause of this
phenomenon (termed isomerism) was to be sought for in a
dissimilarity of the proximate constituents of the compounds
in question. What a powerful and continually renewed
-charm was thereby given to the search for those different
radicals of organic compounds !
Isomerism and its Influence on the Development of
Organic Chemistry.
Up to about the year 1820 it was considered an axiom
in chemistry that substances of the same qualitative and
v THE FIRST OBSERVED CASE OF ISOMERISM 251
quantitative composition must possess the same properties.
Even then, it is true, cases were known which appeared to
contradict this natural assumption, viz. the different modi-
fications of chromic oxide and of silicic acid, and, in especial,
the proof given by Berzelius of the two varieties of tin
dioxide. But little weight, however, was placed upon these
observations; they were simply looked upon as exceptions
to the general rule, and considered merely as indicating
physical differences, as in cases of dimorphism, of which a
number were known.
So little were chemists prepared for the existence of
substances of the same composition, but of different chemical
and physical properties, that most of them considered the
first observed case of isomerism in organic chemistry as due
to an error. In 1823 Liebig had found, on comparing his
analysis of silver fulminate with that of silver cyanate, which
Wohler had investigated a year before, that the results of
the analyses of both salts were alike.1 Satisfied of the cor-
rectness of his own work, he thought that Wohler had probably
made some mistake, but became convinced that this was not
the case upon repeating the investigation himself. From
that date, accordingly, two compounds, which differed as
widely as possible from one another chemically, were recog-
nized as having the same composition.
While Berzelius attached full significance to the above
observation, he did not immediately give in his adhesion to it,2
but rather waited for further confirmation of the point ; Gay-
Lussac, on the other hand, felt no doubt whatever as to the
correctness of the discovery, and explained the differences in
the above salts by assuming a difference in the manner in
which their constituent elements were combined. After
Faraday's discovery,3 in 1825, of a hydrocarbon in oil gas
which had the same composition as ethylene, but which
1 Ann. Chim. Phys., vol. xxiv. p. 264.
2 At first Berzelius was of opinion that an error had probably been
made on one side or the other (cf. Jahresbericht, vol. iv. p. 110 ; vol. v. p.
85).
3 Annals of Philosophy, vol. xi. pp. 44 and 95.
252 THE MODERN CHEMICAL PERIOD CHAP.
showed a totally different behaviour, and after Wohler in
1828 had obtained urea from the transformation of the
similarly composed cyanate of ammonium, chemists became
more conversant with the existence of isomeric compounds.
Berzelius only accepted those facts after hesitation, but
ultimately convinced himself of their absolute correctness by
experiments of his own. He proved that racemic acid had
the same composition as tartaric,1 and thereupon proposed the
term isomeric for those substances which, with the same
chemical composition, possess different properties. The
general designation isomerism has since then been retained.
Berzelius soon saw himself necessitated to define more strictly
the meaning to be attached to this word; 2 he distinguished
between polymerism and metamerism, as special cases of
isomerism, in essentially the same manner as we still do to-
day.3 His power of generalising, even with but a scanty
number of facts to go upon, was shown here in a very high
degree.
The ideas of Berzelius with regard to the probable cause
of isomerism in organic compounds are clearly shown in many
of his utterances ; in his view isomeric compounds are those
in which the atoms of the elementary constituents have
grouped themselves differently into compound radicals.
" The isomerism of compounds in itself presupposes that the
positions of the atoms in them must be different." To
conclude from this sentence that Berzelius looked upon the
problem of elucidating the relative positions of the atoms
in space as one which was soluble, is certainly not justifiable;
what he no doubt had in his mind was the determining of
the mutual relations of atoms in their compounds, and,
especially, the establishment of the mode in which atoms are
combined to form the proximate constituents or compound
radicals of compounds. The accumulating observations of
1 Berzelius1 Jahresber., vol. xi. p 44 (1832).
2 Ibid., vol. xii. p. 63 (1833).
3 Berzelius regarded the different modifications of elements as a par-
ticular case of isomerism ; the designation allotropy, now employed for
this, only dates from 1841.
v DUMAS AND BOULLAY'S ETHERIN THEORY 253
cases of isomerism quickly brought the question of chemical
constitution in this sense to the stage at which an experi-
mental solution of it was deemed possible, and this was
attempted by grouping together a number of organic com-
pounds on the basis of the hypothesis of definite common
radicals. The outcome of this attempt was the Radical
Theory, in the shaping of which Berzelius and Liebig had
the greatest share. To distinguish it from the more recently
revived form of views of a similar character, it is known as
the older Radical Theory.
The older Eadical Theory.
Prior to 1830, as has been already stated, efforts were
not wanting to explain the constitution of particular com-
pounds by the assumption of compound radicals. The
chief incitement to those efforts lay in the proof that
cyanogen acted like an element in its numerous compounds,
besides being known in the free state itself. The observation
that alcohol is easily transformed into ether and ethylene
may have given rise to the supposition that ethylene was a
constituent of both of these.
This idea, which was held by Gay-Lussac, had new life
imparted to it for the time being by Dumas and Boullay's
attempt1 to generalise it by extending it to derivatives of
-alcohol and ether. The radical " etherin/' 2 C2H4, was assumed
by them to be present in what afterwards became known as
ethyl compounds, and was compared with an inorganic
compound, ammonia. Like the latter, etherin was regarded
as a base, capable of forming a hydrate with water, and
ethers (analogous to salts) with acids. The following
table will help to explain the endeavours to establish
an analogy between organic and inorganic compounds
1 Ann. Chim. Phys., vol. xxxvii. p. 15 (1838).
2 The radical C2H4 had, at Berzelius' suggestion, received the name
^Etherin.
254 THE MODERN CHEMICAL PERIOD CHAP.
(some of the latter not having been isolated, as a matter
of fact) :—
Etherin, C2H4 Ammonia, H3N
Alcohol, C2H4 + H2O
Ether, 2C2H4 + H2O
Hydrochloric ether, C2H4 + HC1 . . | Chloride ^ammonia,
Acetic ether, 2C2H4 + C8H6O3 + H2O .
This attempt, which is known under the name of the
etherin theory, was so far the precursor of the true radical
theory in that it had the comparison of organic with inorganic
substances in common with the latter. In criticising it
Berzelius was thoroughly justified in emphasising the point
that it was quite admissible to group the above compounds
in tabular form alongside of one another, while at the same
time he expressed the opinion that their presumed constitution
was highly doubtful.
But the real development of the existing idea that organic
compounds owe their characteristics to the radicals which
they contain, was mainly brought about by Liebig and
Wohler's memorable research, entitled Ueber das Eadikal
der Benzoesaure (" Upon the Radical of Benzoic Acid ").2 In
this they proved incontestably that in numerous transforma-
tions of oil of bitter almonds, and of chlorine and bromine
compounds prepared from it, a radical of the composition
C14H10O2,3 which they termed Benzoyl, remained unaltered.
They showed by convincing experiments that this radical
may be assumed as present in benzoic acid, benzoyl chloride
and bromide, benzamide, benzoic ether and benzoyl sulphide,
and that it comports itself in these compounds like an
element. This piece of work was not only of profound signi-
ficance for the radical theory, but it has also exercised a most
1 Dumas' atomic weights, taking H=l, were C = 6, and 0 = 16.
2 Ann. Chem., vol. iii. p. 249 (1832). The correspondence between
Liebig and Wohler (edited in 1888 by A. W. v. Hofmann and E. Wohler)
gives a welcome insight into the origin of this pioneering piece of work,
while at the same time it constitutes the best memorial of the close friend-
ship existing between the two men.
3 Berzelius' atomic weights were : H = l, C = 12, O = 16.
v BERZELIUS AND LIEBIG'S ALKYL THEORY 255
powerful influence on the development of organic chemistry
generally, the new methods given in it for the preparation of
particular compounds having proved applicable to whole classes
The authors laid greatest stress upon the proof of a "com-
pound element, benzoyl, in a series of organic compounds."
Berzelius was so convinced by these astonishingly clear
results of the correctness of their interpretation, that he
concurred enthusiastically in the assumption of the radical
benzoyl ; 1 the facts were so strongly in its favour that he
felt himself compelled to give up his axiom, — that oxygen
cannot be a constituent of a radical. But unfortunately
this was only for a short time, as he soon reverted to the
opinion that the existence of oxygenated radicals was abso-
lutely incompatible with his electro-chemical theory.
Most chemists of that day held that the radicals which
were proved to be present in several compounds were to-
be regarded as atomic groups capable of existing separately,
and that their isolation should therefore be striven after.
Although benzoyl itself had not been isolated, as little doubt
was felt with respect to its separate existence as with respect
to that of calcium or of nitric anhydride, neither of which
had yet been obtained. The natural result of Liebig and
Wohler's investigation was a strong incitement to chemists
to search for the atomic groups peculiar to different series
of compounds, whose modes of formation and behaviour
pointed to a probable connection between them.
The radical theory proper, in the establishment of which
Berzelius and Liebig took part during the ensuing years,,
arose out of such endeavours. A series of organic compounds,
closely related to alcohol, furnished the most suitable object
for such a view, these compounds being even at that date
among the most carefully investigated of organic substances.
In 1833 Berzelius2 emphasised the necessity of assuming a
1 In his letter to Liebig and Wohler (Ann. Chem., vol. iii. p. 282),
Berzelius proposed the name Proin or Orthrin (from irpa>ta,nd 6p6pos respec-
tively, meaning "morning blush "), because with this research a new day
had dawned for organic chemistry.
2 Jahresber., vol. xiii. p. 190 et seq. The Berzelius-Liebig Letters (pp.
55 et seq. and 67) give many details as to the origin of this view.
256 THE MODERN CHEMICAL PERIOD CHAP.
binary structure for all organic as for all inorganic compounds
renouncing at the same time the idea of oxygenated radicals.
Benzoyl he explained as being the oxide of the complex
C4H10, the peroxide of this being anhydrous benzoic acid.
Ether he regarded as the sub-oxide of ethyl, and he gave to
it the formula (C2H5)20 ; this last corresponded to the
inorganic bases, and was combined with acids in ethers
exactly as the metallic oxides were in salts. Alcohol, on the
other hand, which is so nearly related to ether, was looked
upon by him as the oxide of a radical C2H6, a view which
entirely effaced the connection between the two compounds.1
Liebig,2 noting this error, published in the following
year his opinion that alcohol, as well as ether and its deriva-
tives, were compounds of one and the same radical ethyl, to
which, however, he gave the formula C4H10 (in place of C2H5
by Berzelius). His view is apparent from the following
table :—
Ether, C4H10O Ethyl iodide, C4H10I2
A i i, i n TT r» TT rk f Nitrous ether (Saltpeterdther).
Alcohol, C4H10O.H20 . . . {C4Hioo>N2o3 V
Ethyl chloride, C4H10C12 . . . Benzoic ether, C4H10O.C14H10O3.
He accordingly designated ether as ethyl oxide, and
alcohol as hydrate of ethyl oxide, comparing the former with
potassic oxide, and the latter with potassic hydroxide. Not-
withstanding, however, his recognition of the fact that the
same radical is common to both, he fell into an error which
Berzelius had avoided, viz. he attributed to alcohol and the
corresponding compounds twice the atomic weight that they
really possess. But apart altogether from these mistakes .of
Liebig and Berzelius, the advantages of their ethyl theory
were at once apparent. A broad pathway was opened out
1 Berzelius conceived himself obliged to take this view of the atomic
composition of alcohol and ether on account of their vapour densities ; from
these he deduced the correct molecular formulae, without, however, being
able to arrive at the true constitution of alcohol, as he did at that of
ether.
2 Ann. Chem., vol. ix. p. 1, Ueber die Konstitutiondes Aethers und seiner
Verbindungen ("On the Constitution of Ether and its Compounds ").
v LIEBIG'S SHARE IN THE RADICAL THEORY 257
for the conception that organic compounds were constituted
analogously to inorganic. Ethyl played in a large number of
compounds the same part as potassium or ammonium l did in
others. Liebig finally extended this comparison to mercaptan
and ethyl sulphide, then just discovered. It was due in a high
degree to his eloquent advocacy of the assumption of " com-
pound elements" that the radical theory found such wide
recognition.2
The leading chemists of that day held firm to their
expressed opinions regarding radicals: — Dumas to the
assumption that etherin was the radical of alcohol, etc. ;
Berzelius to the view that alcohol and ether had different
constitutions, although he did not absolutely deny the
admissibility of the extended ethyl theory; while Liebig
remained true to the latter. He differed most from Berzelius
upon the question of oxygenated radicals, which were in his
opinion indispensable ; thus he had no doubt that carbonic
oxide was a constituent of carbonic and also of oxalic acid.
But in one point those chemists were all agreed, viz. that
compound radicals existed as distinct constituents in their
compounds.
Liebig by degrees took up another and broader view of the
nature of radicals than Berzelius, who inclined more and
more to the opinion that they were unalterable. In Liebig,
on the other hand, we get frequent glimpses of the idea that
the grouping of the elements to radicals must prove of
essential service to a better understanding of the modes of
decomposition and formation of compounds. This conception
appears to have forced itself upon him from the result of an
1 In the place of the assumption that ammonia itself is combined with
acids in its salts, the view — originally held by Ampere (in 1816) and which
had now the authority of Berzelius to back it — gradually spread, that in
those salts ammonium, NH4, acts analogously to the metals.
2 We must not omit to state here that Kane, independently of Berzelius
and Liebig, pointed out the analogy between a radical Athereum, i.e. ethyl,
which was to be assumed in ether, alcohol, etc., and the hypothetical
ammonium ; the paper, however, in which he expressed this view (which
was published in 1833 in The Dublin Journal of Medical and Chemical
Science, vol. ii. p. 348) remained quite unnoticed.
258 THE MODERN CHEMICAL PERIOD CHAP
investigation1 which Regnault2 had undertaken at his
suggestion. The latter had obtained a substance of the
composition C4H6C12, which he termed chloro-aldehyde,
by decomposing ethylene chloride with alcoholic potash.
Liebig 3 thereupon expressed his opinion that the radical C4H6
was a constituent of this chloride and of numerous other
compounds; this radical he named acetyl, and he placed
it parallel to the hypothetical amidogen (Amid), and its
hydrogen compounds, ethylene and ethyl, to ammonia and
ammonium, thus: —
C4H6, acetyl, corresponds toN2H4, amidogen
C4H8, ethylene, ,, ,,N2H6, ammonia
C4H10, ethyl, ,, ,,N2H8, ammonium.
Liebig laid especial weight upon finding an expression
for the constitution of aldehyde and acetic acid; these he
looked upon as the protoxide and hydrated oxide of the
acetyl radical, and he gave them the formulae C4H6O.H20
and C4H6O3.H2O. This conception paved the way for the
explanation of the conversion of alcohol into aldehyde and
acetic acid, while at the same time it raised up doubt as to
the rigid unchangeability of a radical.
The year 1837 may be looked upon as that in which
the older radical theory attained to its zenith and stood
out most securely, in spite of the many attacks which it had
to undergo. Liebig and Dumas, who were convinced of
the untenability of the etherin theory, joined together to
make a thorough investigation of organic compounds with
1 Ann. Chem., vol. xv. p. 60.
2 H. V. Regnault, who was born at Aix-la-Chapelle in 1810 and died at
Auteuil near Paris in 1878, was a pupil of Liebig. Up to 1840 he gave his
attention to organic chemistry, which he enriched by valuable work, but
after that devoted himself to physico-chemical researches which will ensure
him a distinguished place in the history of the science. His many-sided-
ness is shown in his admirable investigations on the respiration of animals,
undertaken conjointly with Reiset. By means of translations, his Cours
j&ttmentaire de Chimie (1847-49) became well known and appreciated in
other countries besides France.
3 Ann. Chem. vol. xxx. p. 229.
v THE RADICAL THEORY IN 1837 259
respect to the radical theory. In a paper1 given out jointly
in his own name and Liebig's, Dumas set forth his altered
opinions and described the problems to be solved. Organic
chemistry was regarded by both as the Chemistry of Com-
pound Radicals, and was denned accordingly.2 These radi-
cals were compared with the elements, e.g. ethyl, methyl
(whose existence in wood spirit was deduced from Dumas
and Peligot's memorable research), and amyl* with the
metals, acetyl with sulphur, and so on; and their com-
pounds with the corresponding compounds of the elements,
e.g. ethyl sulphide (C2H5)9S, with sulphide of potassium,
K2S, etc.4
The chemists of that day did not, however, remain
content with simply contrasting organic with inorganic com-
pounds as an aid to getting at their formulae; on the
contrary, they applied in the happiest manner to the investi-
gation of organic compounds the principles which they
knew to hold good in inorganic chemistry, faithful to the
axiom enunciated by Berzelius in 1817 : " The application
of what is known regarding the combination of the elements
in inorganic nature, to the critical examination of their com-
pounds in organic, is the key by which we may hope to
1 Comptes Rendm, vol. v. p. 567. That this union of the two investiga-
tors was of short duration is easily intelligible when one considers
the different modes of thought and dispositions of the two men. The
criticism with respect to Dumas, which we find in the correspondence be-
tween Berzelius and Liebig, shows such a separation to have been inevitable.
Gay-Lussac throws a clear light on the occurrence in a letter to Liebig
which begins with the words : — Maintenant, mon cher Liebig, je vous felicite
d'etre sorti de la galere ou vous dtiez entre. Je ne concevais pas votre
mariage. . . ., etc. (The Berzelius- Liebig Letters, p. 171).
2 Cf. Liebig's Handb. d. organ. Chemie, p. 1.
3 Cf. Cahours' investigation of fusel oil, Ann. Ghent., vol. xxx. p. 228.
4 The following quotation from the paper cited above (note 1) shows
the then standpoint of Dumas and Liebig : " Organic chemistry possesses
its own elements, which sometimes play the part of chlorine or oxygen,
sometimes that of a metal. Cyanogen, amidogen, benzoyl and the radicals
of ammonia, of the fats, and of alcohol and its derivatives, constitute the
true elements of organic nature, while the simplest constituents, such as
carbon, hydrogen, oxygen and nitrogen, only appear when the organic sub-
stance is destroyed."
s 2
260 THE MODERN CHEMICAL PERIOD CHAP.
arrive at true ideas with respect to the composition of
organic substances."
As the presence of such atomic complexes in organic
compounds came to be assumed with more confidence, the
term radical became more sharply defined. Liebig himself
enunciated in 1838 three characteristics by which a com-
pound radical was distinguished. In bringing forward his
view he made use of cyanogen as an instance, and spoke
as follows : 1 " We term cyanogen a radical because (1) it
is the unchanging constituent of a series of compounds ;
(2) because it is capable of replacement in these by simple
substances; and (3) because, in those cases where it is
combined with one element, this latter can be exchanged
for its equivalent of another element." At least two of the
conditions here adduced had to be fulfilled in order that
an atomic complex might be stamped as a radical. The
existence of these conditions, moreover, could only be
established by the most minute investigation of the chemical
behaviour of organic bodies. That is to say, the nature of
the radicals assumed in the latter could only be arrived
at from the study of their reaction- and decomposition-
products.
The radical theory gave such a powerful impulse to the
science that its influence, even when it fell into error,
cannot be too greatly prized. Chemists of the highest
eminence were attracted to the task of investigating the
constituents of compounds which were related to one
another. Among the most fruitful of those efforts were a
series of admirable researches upon the cacodyl compounds2
by Robert Bunsen, begun in the year 1839 (see below).
Robert Wilhelm Bunsen, born at Gottingen on March 31st,
1811, became assistant-professor at the University there,
then succeeded Wohler at Cassel, and was appointed pro-
fessor in the University of Marburg in 1838. His next
post (only occupied for a short time) was at Breslau, after
1 Ann. Chem., vol. xxv. p. 3.
2 Ann. Chem., vol. xxxi. p. 175 ; vol. xxxvii. p. 1. ; vol. xlii. p. 14 ; vol.
xlvi. p. 1.
v ROBERT WILHEL&L BUNSEN 261
which he was called (in 1851) to Heidelberg, of whose
University he remained a bright ornament until his resig-
nation in 1889. Chemistry is indebted to him for a
vast number of the most important researches in every
branch of the science ; his name will therefore be very often
referred to in the special history of its various sections.
Beginning with work in inorganic chemistry, he soon turned
his attention to the organic compounds of arsenic, by
investigating which he raised up a powerful support for the
radical theory. His work upon gases led him to devise new
methods, by sifting and combining which he created the
gas analysis of to-day. The discovery of spectrum analysis
by him and Kirchhoff — one of the grandest and most fruitful
of the last fifty years — is fresh in every one's recollection.
His labours in other branches of physical, analytical, in-
organic and mineralogical chemistry will be referred to in
the detailed description of these. Throughout he has shown
himself an investigator of the most marked originality and
a pioneer in the science; while his career as a teacher,
extending over more than half a century, has been singularly
successful in its results.
Bunsen's researches on the cacodyl compounds resulted
in the proof that the so-called alkarsin, the product of the
distillation of acetate of potash with arsenious acid, con-
tained the oxide of an arseniuretted radical As2C4H12
(H = l, C = 12, As = 75), this radical remaining unchanged
in a long series of reactions of that oxide, and being even
itself capable of isolation. This " compound element " con-
taining arsenic (an unusual constituent of organic bodies) was
thus shown to be a true radical.
The investigations of Gay-Lussac upon cyanogen, of
Liebig and Wohler upon benzoyl compounds, and of Bunsen
upon the compounds of cacodyl, have been justly termed the
three pillars of the radical theory. The assumption of
radicals gained so immensely in probability from the results
of these researches, that the hypothesis which lay at the
root of the theory might now be regarded as well established.
In any case the older radical theory formed an indispensable
262 THE MODERN CHEMICAL PERIOD CHAP
link in the chain of theoretical views, and marked an extra-
ordinary advance upon the previous unconnected opinions.
And even although this theory (as it then stood) exercised
no very permanent effect directly, being soon overthrown by
opposing currents, it showed itself in a high degree capable
of further development. For, shortly after the catastrophe
which came upon it, it was able to throw off a few restraining
fetters and to start again into fresh life.
Before proceeding to describe the development of the
hypotheses directed against the older radical theory, it will
be convenient to give a short account here of the lives and
chief labours of the three chemists who were mainly in-
strumental in changing the direction of organic chemistry
during the third and fourth decades of the nineteenth
century, and who furthermore exercised a powerful influence
upon our science up to a very much more recent date.
Liebig, Wohler and Dumas — A Survey of their more
important Work.
Liebig and Wohler, who were guided by similar scientific
aims, and were at the same time close personal friends, must
be spoken of together in the history of the science; the
portrait of the one is incomplete unless supplemented by the
characteristic features of the other. The fruit of their
common labour is among the richest in the whole of
chemistry. The selection of their letters, extending from 1829
to 1873, which was edited1 by the late A. W. v. Hofmann,
with E. Wohler 's co-operation, is a memorial to the steadfast
friendship that existed between the two men, and at the same
time a most important contribution to the history of
chemistry.
Justus Liebig,2 whose influence in shaping the radical
1 Published by Vieweg, Brunswick, 1888.
2 Cf. the Memoirs by H. Kolbe, Journ. pr. Chem. (2), vol. viii. p. 428 ;
by A. W. v. Hofmann, Ber. , vol. vi. p. 465 ; and especially the various
memorial papers (partly by A. W. v. Hofmann) on Liebig and Wohler, Ber. ,
xxiii. Ref. p. 785 et seq. These last include, in an appendix, a fragment
v LIEBIG, WOHLER, AND DUMAS 263
theory and upon organic chemistry in general has just been
touched upon, earned by his scientific work the right to be
regarded as one of the most distinguished investigators of
the century. Born at Darmstadt on 12th May 1803, his
early years did not seem to give any special promise of the
fiery spirit which he later developed, although it was
not long before he felt himself drawn towards chemistry
with irresistible power. He has himself given us a graphic
description, in the autobiographical sketch already mentioned,
of the way in which he gained a knowledge of chemical facts
and phenomena, having determined at an early age to make
chemistry a study, to the utter astonishment of his teachers
and fellow pupils. He relates in pleasant manner how
" that disposition developed in myself, which is found in
chemists more than in students of other sciences, viz.,
to think in phenomena " (in Erscheinungen zu denken.) It
was this capacity which caused " all that I saw, whether in-
tentionally or unintentionally, to remain fixed in my memory
with photographic accuracy."
He soon forsook the calling of apothecary, through
which alone it was possible at that time to gain a practical
knowledge of chemistry, in order to devote himself to
academic studies. Relying on himself alone, he continued
his early-begun investigations upon fulminate of silver, which
he hoped would give him a certain definite position in science.
But however independent the youth thus showed himself in
this direction, he was unable to resist the influence of the
natural philosophy (or, as it might be better expressed in
English, physio-philosophy) current at that day. At a later
period we find him speaking with bitterness of the two years
that he had lost by it, during which time he studied under
of an autobiography of Liebig's. Compare also the Letters between Liebig
and Wohler, and Liebig and Berzelius. In 1895, W. A. Shenstone wrote a
short Life of Liebig for the Century Science Series (Cassell and Co. ), which
gives in brief compass an excellent picture of the man and the chemist,
though — from want of space — too little is said of his purely scientific
work.
204 THE MODERN CHEMICAL PERIOD CHAP.
Schelling at Erlangen.1 But he rescued himself from this
by going in search of his science to where, at that time, it
nourished most brilliantly, — to Paris, where Gay-Lussac,
Thenard, Dulong, Chevreul, Vauquelin and others were hard
at work. With recommendations from Alexander von
Humboldt to Gay-Lussac and other influential chemists, he
recovered himself in those surroundings (as he has himself so
delightfully described), and soon became closely associated
with Gay-Lussac, the result of which was their important
investigation of the fulminates. This piece of work paved a
way for him ; in 1824 he was called as professor to Giessen,
where he remained for twenty-eight years, but where at first
he had to fight hard and continuously in order to maintain
his position, his youth being a source of offence to the older
professors.2 In 1852 he accepted a call to the University of
Munich, being led to this by the desire to throw off the
fatigues of laboratory teaching and to live all the more
ardently for research. His magnificent labours were brought
to a close there by death, on 18th April, 1873, but the genius
which inspired them, and which had acted with such powerful
effect upon his contemporaries, continued to influence man-
kind. How powerful an influence he exercised — as shown in
his greatness as a teacher, in the transformation of whole
branches of the science, and in the setting aside of firmly
rooted views which in his opinion were erroneous — we shall
now attempt shortly to describe.
1 In an essay entitled Ueber das Studium der Naturwissenschaften
(" On the Study of the Natural Sciences "), published in 1840, Liebig ex-
pressed himself as follows : "I myself spent a portion of my student days
at a university where the greatest philosopher and metaphysician of the
century charmed the thoughtful youth around him into admiration and
imitation ; who could at that time resist the contagion ? I too have lived
through this period — a period so rich in words and ideas and so poor in
true knowledge and genuine studies ; it cost me two precious years of my
life."
2 G. Weihrich, in his pamphlet, Beitrdge zur Geschichte des chemis-
chen Unterrichts an der Universitdt Giessen (1891), has given a full and
careful account of Liebig's academic work and of his relations to the Uni-
versity.
v LIEBIG'S LIFE AND WORK 265
As a teacher Liebig stands almost alone. Berzelius, the
great master, only drew around himself pupils who had
already a considerable knowledge of the subject, and worked
(directly) in a comparatively narrow circle. Liebig, on the
other hand, founded a real school of chemistry, by sparing no
pains in instructing his pupils individually from the com-
mencement of their course of study. He was the first to give
systematic teaching in chemistry, for up to that time there
was no laboratory in existence which was devoted solely to
that purpose. And he was also the first to recognise the
necessity for having chemical institutes which should further
not merely the science itself, but also the many other
branches dependent upon it. His laboratory in Giessen
served as a pattern upon which numerous others were in the
course of years modelled, at first slowly but afterwards in more
rapid succession. By the charm of his own personality Lie-
big stimulated his pupils and inspired them with enthusiasm,
especially when the solution of a scientific question came up.
Kolbe has described for us his unique character as a teacher
in the following striking sentences: — " Liebig was not a teacher
in the ordinary sense of the word. Scientifically productive
himself in an unusual degree, and rich in chemical ideas, he
imparted the latter to his more advanced pupils, to be put
by them to experimental proof; he thus brought his pupils
gradually to think for themselves, besides showing and
explaining to them the methods by which chemical problems
might be solved experimentally."
In addition to this Liebig gave a new form and meaning
to his experimental lectures, so that here also he set up a
standard. His pupils were legion ; many of them afterwards
spread abroad the doctrines of their master in universities,
polytechnic institutes, technical schools, etc. Out of a
long list of them which might be given here, the following
may be mentioned : — A. W. v. Hofmann, Strecker, Fresenius,
Will, H. Buff, Fehling, Henneberg, Schlossberger, Rochleder,
Schlieper, Scherer, Redtenbacher, v. Bibra, Varrentrapp,
Th. Poleck, Playfair, Muspratt, Stenhouse, Brodie, Gerhardt,
Williamson, Wurtz, Frankland and Volhard.
266 THE MODERN CHEMICAL PERIOD CHAP.
The mental vigour which was shown in the results of
Liebig's teaching is also seen in his literary activity, which
awakens a feeling of astonishment by its many-sidedness,
embracing as it does the most various branches of the
science. Throughout it all we see the capacity of the true
investigator to state points correctly and clearly, to grasp
the connection between different processes distinctly, and to
draw able and ingenious conclusions. These merits impart
to Liebig's writings a great and ever-renewed charm. His
numerous experimental researches, together with the joint
ones with Wohler, were mostly published in the Annalen*
which he began to give out in 1832. His extended
investigations in physiological chemistry, which were begun
in 1837, led him on to the grand achievement of setting forth
the applications of chemistry to agriculture, physiology and
pathology in three separate works.2 In these he combated
the current doctrines which were held with regard to the
nutrition of plants and animals, basing his arguments upon
exact experiments. Notwithstanding the great excitement
which those publications produced, Liebig found leisure to
write his Chemische Brief e ("Chemical Letters," 1844), by
which he proved that chemistry might be treated popularly,
and yet at the same time scientifically. It is almost
inconceivable how he still found time remaining to devote to
1 Till 1840 this journal was termed Annalen der Pharmacie, and after
that date (with Wohler as joint editor) Annalen der Chemie und Phar-
macie.
2 Die Chemie in ihrer Anwendung auf Agrilcultur und Physiologic, 1840
(" Chemistry in its Application to Agriculture and Physiology," 1840);
Die Thierchemie oder organische Chemie in ihrer Anwendung auf Physiologic
und Pathologie, 1842 (" Animal or Organic Chemistry in its Application to
Physiology and Pathology," 1842) ; Der chemische Prozess der Erndhrung
der Vegetabilien und die Naturgesetze des Feldbaues, 1862 (" The Chemical
Processes in the Nutrition of Vegetables, and the Natural Laws of
Tillage," 1862). In one of his letters to Berzelius (Letters, p. 210) Liebig
tells us how and why he was led to take up this last branch of applied
chemistry. An "insurmountable distaste and repugnance to this dispu-
tation in chemistry had taken hold of him ; he was tired out (auf die Spitze
gestellt) by the controversy about the substitution theory," etc. Whereupon
he developed in broad lines the programme of his agricultural chemical
work.
v LIEBIG'S LITERARY ACTIVITY 267
the ffandwdrterbuck der reinen und angewandten Chemie
(" Dictionary of Pure and Applied Chemistry "), founded by
Wohler, Poggendorff and himself, and, after the death of Ber-
zelius in 1848, to the Jahresbericht uber die Fortschritte der
Chemie. In addition to all these there are still to be men-
tioned his occasional papers,1 some of which exercised a
powerful effect ; this applied in an especial degree to the
two essays upon the state of chemistry in Austria and
Prussia. In these, as in other papers devoted to questions
of theoretical chemistry (e.g. in his writings directed against
the views of Dumas, and of Laurent and Gerhardt), is shown
the sparkling critical vein of this gifted man, who, from his
rectitude and love of truth, never palliated what he felt to
be erroneous or insincere. Occasionally Liebig may have
gone too far in his critical utterances upon particular men ;
but the mainspring of his decided attitude with respect to
them was always the boundless love of science and of truth,
and an inflexible sense of justice.
As an investigator Liebig shows all his individuality.
To organic chemistry he had devoted the full powers of his
mind from the very beginning, without however neglecting
any important part of inorganic. His very first work — that
upon the fulminates — led to valuable results ; for, through it
the isomerism of cyanic and fulminic acids became recognised,
a new field for investigation being thereby opened up.
Another result of this laborious research upon these easily
decomposable substances was the perfecting of organic
analysis, to which Liebig gave its present form. By means
of methods improved by himself, he established the com-
position of numerous organic compounds, especially of
various acids. His work upon these last led him to a distinct
conception of the term basicity ; from this he developed his
doctrine of polybasic acids (already touched upon), doing
more to clear up the points involved here than any other
chemist before him.
1 These were published by M. Carriere under the title JReden und
Abhandlungen (" Speeches and Essays"), by Justus von Liebig. (In 1845
he was made a baron by the Grand Duke of Hesse.)
268 THE MODERN CHEMICAL PERIOD CHAP,
His previous admirable researches upon compounds
closely related to alcohol and acetic acid, e.g. ethyl-sulphuric
acid, aldehyde, acetal, chloral, etc., rendered him specially
capable of developing the radical theory and infusing fresh
life into it. The work which he did upon sulphocyanogen
compounds and upon the decomposition products of am-
monium sulphocyanide showed him as a brilliant experi-
menter in all his many-sidedness.
But his most remarkable achievements were the re-
searches carried out conjointly with Wohler, which bring them
both before us in their full freshness and power, and which
will long continue to call forth the admiration of chemists.
Wohler's work upon cyanic acid and Liebig's upon the ful-
minates drew them together; their friendship is beautifully
shown by the investigations which they undertook in common,
during which each animated the other, while striving at the
same time to do his best himself.1 And how strikingly was
the one man the complement of the other ! Liebig — fiery,
restless, and always advancing, able to utilise his rich
experiences gained in the preparation and analysis of organic
compounds for overcoming the hardest difficulties. Wohler,
on the other hand, quiet, almost prosaic, but not less conscious
of his aim than Liebig himself, exercising patience in clearing
up obscure points to which too little attention had been
paid. The memorable research upon the radical of benzoic
acid has been already detailed. The investigations upon
amygdalin cleared up the difficult point as to how bitter
almond oil was formed, and those upon uric acid, published
in the same year (1837), enriched organic chemistry to an
undreamt-of extent with a wealth of the most remarkable
compounds, — compounds which have quite recently proved
objects of the greatest interest to chemists. We are indeed
not wrong in asserting that the organic chemistry of to-day
is grounded mainly upon the pioneering labours of Liebig,
and of Liebig and Wohler together.
1 Cf. the letters of both quoted in A. W. v. Hofmann's Memoir of
Wohler, Ber., vol. xv. p. 3127 etseq., and also the Correspondence already
frequently referred to.
v LIEBIG AS AN INVESTIGATOR 269
In addition to all this, inorganic chemistry was anything
but neglected by Liebig, who enriched it by valuable obser-
vations on the most various subjects ; we have only to recall
his work upon the compounds of alumina, antimony and
silicic acid, and many analytical methods which he worked
out, e.g. the separation of nickel from cobalt. The results
obtained by him in the laboratory were often of great
service for technical chemistry; for instance, the improved
preparation of cyanide of potash for the galvano-plastic
process, and the reduction of a solution of silver by aldehyde
for the production of mirrors.
Liebig's share in the development of organic chemistry,
especially with regard to the views which had come to be
accepted in it, became less marked towards the end of the
thirties, as from that time he gave all his energies to the
solution of a great question which had only an indirect
bearing upon chemistry. The nutrition of plants and
animals, the transformations of matter in animated nature
—these were the grand problems which he strove to solve
by experimental researches in an entirely new direction.
The influences which emanated from him, the setting right
of erroneous views, the ingenious interpretation of natural
processes investigated by himself and his pupils, and the
stimulus which invariably accompanied his labours and
the deductions drawn from them, — all these can but be
referred to here. The most important results of those
researches will be spoken of under the history of physio-
logical chemistry. Liebig's experiments on the nutrition
of animals led him to distinguish clearly between nutrient
substances among themselves, and between these and
other substances which, though not directly nutrient, bring
about metabolic changes in the organism.1 By getting
at the relative nutritive values of these materials he
was enabled to introduce improved systems of feeding,
and so to further the laws of health; we have only to
recall here his extract of meat and his "children's food."
1 "... Unterscheidung der Ndhrstqffe unter sich und von den Genust-
mitteln. "
270 THE MODERN CHEMICAL PERIOD CHAP.
He was thus in this respect a general benefactor of
mankind.
We may close this attempt at depicting within narrow
limits the scientific achievements of Liebig with the follow-
ing eloquent words of A. W. v. Hofmann : — " If we sum up
in our minds all that Liebig did for the good of mankind —
in industries, in agriculture, and in the laws of health, we
may confidently assert that no other man of learning, in his
course through the world, has ever left a more valuable
legacy behind him."
Friedrich Wohler,1 whose work blended so happily with
that of Liebig, also proved himself by his own individual
researches a master in his science. By far the greater
portion of his work lay in the domain of inorganic chemistry
which he furthered in a remarkable degree.
Wohler's life may be sketched in a few sentences. Born
in the village of Eschersheim, near Frankfort on the Main,
on July 31st, 1800, he received in the latter city a splendid
education at the hands of such eminent teachers as Karl
Bitter, Grotefend, and F. C. Schlosser. There, too, he first
made acquaintance with chemistry, to which he remained
faithful, thanks to the influence of L. Gmelin, notwith-
standing that he went through the medical curriculum at
Marburg and Heidelberg. It was Gmelin, too, who re-
commended the young doctor of medicine to Berzelius, the
latter receiving him with open arms. After barely a year's
stay in Stockholm, — a year, however, rich in experiences
and uneffaceable impressions, and of which he himself has
given us such a clear picture2 — Wohler returned to Germany
in the autumn of 1824, to become shortly afterwards a
teacher in the Technical School (Gewerbeschule) at Berlin.
In 1831 he had to leave the pleasant and stimulating
society of his friends there (among whom we may mention
Mitscherlich, the brothers Rose, PoggendorfF and Magnus)
to fill the post of professor in the newly-founded Higher
Technical School at Cassel ; while in 1836 he accepted a
1 Cf. A. W. v. Hofmann's Memoir of Wohler, Ber., vol. xv. p. 3127 et
seq., and Ber., vol. 23, Ref. p. 833. 2 Ber., vol. viii. p. 838 et seq.
v WOHLER'S SCIENTIFIC WORK 271
call to Gb'ttingen as successor to Stromeyer, where, till his
death on 23rd September 1882, he remained a bright
ornament of the Georgia- Augusta (the university of that
town).
Wohler's influence as a teacher, especially after his re^
moval to Gottingen, may be described as enormous. Like
his friend Liebig, he laid the greatest weight upon a thorough
grounding in the rudiments of chemistry. The advantages
which he had gained from his analytical work under Berzelius
he now imparted to his pupils. Out of a long list of these,
a few may be named who themselves subsequently continued
to teach in the spirit of their master: — Th. Scherer, H.
Kolbe, Henneberg, Knop, Stadeler, Geuther, Limpricht,
Fittig, Beilstein, Hiibner and Zoller.
Wb'hler was especially active in a literary sense during
the earlier portion of his life, as is shown by his co-operation
in the Dictionary of Chemistry, already mentioned, and his
translations of the Text-Book and Annual Reports (Jahres-
lerichte) of Berzelius. The first edition of his Grundriss der
anorganischen Chemie (" Outlines of Inorganic Chemistry ")
occupying about 150 pages, appeared in 1831, the Organic
following in 1840 ; both of these went through numerous
editions.1 His results in the investigation of minerals he
collected together in 1853 in the valuable work, Praktische
Ubungen in der chemischen Analyse (" Practical Exercises in
Chemical Analysis ").2 His experimental researches — most
of which he published in the Annalen der Chemie, but some
of the earlier ones in Poggendorff's and in Gilbert's Annalen
— embrace almost every branch of inorganic chemistry.
Some of them also led to the opening up of important
branches of organic, e.g. his splendid work upon cyanic acid
and its salts, the discovery of urea, and also the investi-
gations carried on along with Liebig. In all of them, as
1 From its sixth edition the Organic Chemistry has been admirably
edited by Rudolf Fittig ; the fourteenth and fifteenth (the last) editions of
the Inorganic were given out by H. Kopp.
2 The second edition appeared in 1861 under the title Die Miner alanalyse
in Beispielen ("The Analysis of Minerals, illustrated by Examples").
272 THE MODERN CHEMICAL PERIOD CHAP.
also in his later labours, his remarkable gifts as an observer
are apparent.
We cannot enter into details at this point either with
regard to his work in analytical chemistry, which he enriched
by admirable methods, or to that in inorganic. But a few
investigations in the latter branch must just be mentioned,
viz. those upon aluminium, boron, silicon and titanium,
and their remarkable compounds, by which the resemblance
between the two last-named elements and carbon was clearly
brought to light.
The papers in which Wohler describes the results of his
experiments are written in a clear, forcible and simple
manner, and attract our attention not merely by those
characteristics — now-a-days somewhat rare, — but above all by
the depth of their contents. That he had plenty of humour
at command is proved by his letters to Liebig, and by the
delicious satires l which he wrote when Dumas allowed him-
self to be carried too far by the deductions that he drew
from the doctrine of substitution. Wohler never rushed of
his own accord into discussions upon important questions of
theoretical chemistry, — a trait characteristic of his quiet
disposition, and one which distinguishes him from Liebig,
the born reformer, who looked upon this as a matter of duty.
As has been already said, the two investigators will
remain inseparable in the history of chemistry. Liebig
himself gives expression to this in one of his last letters to
Wohler, dated December 31st, 1871, in the following
beautiful terms : — " Even after we are dead and our bodies
long returned to dust, will the ties which united us in life
keep our memory green, as an instance — not very frequent —
of two men who wrought and strove in the same field
without envy or ill-feeling, but who continued in the closest
friendship throughout."
Jean Baptiste Andre Dumas,2 who was born at Alais in
1800, and died at Cannes in 1884, rendered to his science
1 Ann. Chem., vol. xxxiii. p. 309 (see alsobelow, p. 282) ; also the Liebig
Berzelius Letters, p. 211, note.
2 Cf. A. W. v. Hofmann's Memoir, Ber., vol. xvii. fief. p. 629 et seq.
v DUMAS : A SURVEY OF HIS WORK 273
extraordinary services, to which we shall frequently have
occasion to refer. Beginning life as apprentice to an
apothecary in his native town, he found this calling uncon-
genial, and set out on foot for Geneva in the autumn of
1816. Coming in contact there with such distinguished
men as Pictet, Decandolle, de la Rive and others, he was
stimulated to scientific researches which quickly attracted
the attention of the savants just named. He made him-
self known particularly by the active part which he took in
the physiologico-chemical investigations of Prevost. With
the versatility which distinguished him, he soon began to
take up problems in organic as well as in physical chemistry.
In 1823, acting on A. v. Humboldt's advice, Dumas betook
himself to Paris, finding there the most friendly reception
at the hands of the eminent chemists of that city. At
Paris he spent the rest of his life, filling various posts as a
teacher and also other offices; he lectured with striking
effect at the Athenceum, the ficole Centrale des Arts et Manu-
facticres, the Sorbonne, and the polytechnic and medical
schools.
No laboratory having been placed at his disposal, he
established one at his own expense in 1832. After the
year 1848 Dumas was frequently called into the public
service, being for a long time minister of state, besides having
to fill other offices, so that his work as a teacher was often
interrupted. The keen interest which he felt in public
affairs was shown in many cases by his active co-operation,
e.g. in furnishing Paris with a water supply and in devis-
ing means to remedy the diseases of the silkworm and
vine, etc. In 1 8 6 8 he was further nominated permanent
secretary of the Academy, of which he had long been a
member.
We have still to make mention of the more important
of Dumas' literary labours. The first of the larger works
by which he became known was his Traitd de Chimie apliqude
aux Arts (1828); in its treatment of the matter, and
especially its arrangement, this remained a model for many
subsequent text -books on technology. The whole in-
V
274 THE MODERN CHEMICAL PERIOD CHAP,
dividuality of the man comes out in his Lemons sur la
Philosophic Chimique (published in 1837 by Bineau from
Dumas' lectures), in which he treats the development of
chemical theories with great clearness and with a rare
charm of style ; this work, however, cannot be regarded as
a strictly historical one. The numerous panegyrics which
Dumas delivered are in their form, down to the minutest
detail, carefully elaborated works of art ; among them may
be mentioned those upon Pelouze, Balard, Regnault and
Faraday.
The Essai de Statique Chimique des ~Etres Organists, par
MM. Dumas et Boussingault (1841), became especially well
known ; in this the life of plants and animals and, more
particularly, the processes of metabolism, were treated from
the chemical point of view. The opinions expressed here
were in part instigated by the pioneering work of Liebig, whose
influence however was not sufficiently recognised by the
authors, so that he felt himself called upon to draw atten-
tion to his perfectly justifiable claims in very distinct
language.1 A debt of gratitude is due to Dumas for the
pious service which he rendered in editing the reissue of
Lavoisier's works.2
Most of the numerous experimental researches which
we owe to Dumas were published by him in the Annahs de
Chimie et de Physique, of which he was one of the editors
after 1840. In recalling his most important and productive
labours, emphasis must be laid upon the great service which
he rendered in working out various methods of general
1 Ann. Chem., vol. xli. p. 351. In this as well as in other instances
Dumas unfortunately did not show in a favourable light. The historian is
bound to notice such facts, since they cannot be erased from the scientific
character of so eminent an investigator. Liebig criticised these peculiarities
of Dumas with great severity (cf. Ann. Chem., vol. ix. pp. 47, 129 ; also
Kolbe's claim of priority, Journ. pr. Chem. (2), vol. xvi. p. 30 ; and the
Berzelius-Liebig Letters, pp. 6, 7, 11, 34, 43, 45, 171, 238, etc.). Such occur-
rences are, to quote Liebig, "black leaves in the book of chemical history, —
black, because they absorb the rays of light without thereby becoming
luminous themselves. " Dumas was unable to disprove or even to minimise
the heavy charges which Liebig brought against him,
2 Cf. p. 161, note.
BEGINNINGS OF UNITARISM IN ORGANIC CHEMISTRY 275
application. His mode of determining vapour densities
and that of estimating nitrogen have found universal
appreciation. His admirable investigations in organic
chemistry shed a brilliant light over wide branches of it,
and guided many chemists for a time as to the direction in
which they should work. Mention must be made too of
his conjoint researches with Peligot l upon wood spirit and
upon sethal(from spermaceti), — compounds whose analogy
to alcohol he proved ; and of his discovery and investigation
of trichloracetic acid, which crowned the edifice of the sub-
stitution theory. The general character of his work naturally
led Dumas to take an active share in the discussion of
problems in theoretical chemistry. His rather unhappy
participation in the question of the values of the atomic
weights has been already noticed. The determinations
which (partly in conjunction with Stas) he made of the
atomic weights of carbon, oxygen and other elements deserve
to be recorded as experimental work carried out with the
utmost care and circumspection.
Apart from the shadow thrown upon Dumas' achieve-
ments by some of the incidents in his scientific life, his
services will long continue to excite the highest admira-
tion as evidences of a powerful and comprehensive mind.
The immense influence which he exercised upon the form
assumed by organic chemistry, and, in particular, upon the
development of general views opposed to dualism, will be
detailed in the following section.
The Development of Unitary Views in Organic
Chemistry. — Substitution Theories.
At the time when Dumas brought forward his own as
well as previous observations upon the substitution of
hydrogen by chlorine and other elements as a basis for
1 E. M. Peligot, born in 1811, was for a long time Professor of Chemistry
at the Conservatoire desArts et Metiers, and distinguished himself by much
admirable work in inorganic, organic and technical chemistry (beet sugar
industry) ; he died in April 1890. Cf. Mon. Scient. 1890, p. 885.
T 2
276 THE MODERN CHEMICAL PERIOD CHAP.
theoretical statements, the electro-chemical doctrine of Ber-
zelius, and the radical theory which fitted in with it, were in
high repute. The idea (deduced as it was from numerous
facts) that electro-positive elements like hydrogen could
be replaced by electro-negative ones like chlorine, oxygen
and others, was bound to become a stumbling-block for the
dualistic hypothesis, which could no longer after this be main-
tained in its integrity. The various attempts to explain the
phenomena of substitution from general standpoints, which
now fall to be detailed, were at the same time the significant
utterances of a struggling unitarism against the binary view.
In connection with this, one has to recall to mind that,
according to the position of Berzelius' dualistic doctrine at
that time, the radicals were looked upon as unalterable
atomic complexes. The consequence of the electro-chemical
view was the assumption that negative elements like chlorine,
bromine and oxygen could not enter into the composition of a
radical. That the observations on the substitution of hydro-
gen atoms in organic compounds by those other elements
was in direct contradiction to this assumption, appears to
us now self-evident.
Dumas' Laws of Substitution.
Some isolated facts, which proved that a substitution of
this kind could go on among the elements, were already
known when Dumas turned his whole attention to the
subject. Thus Gay-Lussac had established the formation of
cyanogen chloride from hydrocyanic acid, Faraday that of
sesquichloride of carbon (C2C16) from ethylene chloride, and
Liebig and Wohler the conversion of bitter almond oil into
benzoyl chloride. It had not escaped these chemists that
when the above compounds were subjected to the action of
chlorine, an amount of hydrogen, equivalent to the chlorine
which entered into them, was separated ; indeed, the opinion
was expressed (by some, if not all, of them) that the one
element had replaced the other.
v DUMAS' LAWS OF SUBSTITUTION 277
In the year 18341 Dumas, a propos of an investigation
on the mutual action between chlorine and oil of turpentine,
but more especially of his work upon the production of
chloral from alcohol, condensed into two empirical rules the
facts with regard to substitution, for which he proposed the
designation metalepsy (i.e. exchange, /^eraX^i/rt?). These
were not intended to comprise a theory of substitution, as
his first utterances on the subject show, but only to give
expression to the facts. They were as follows: —
" When a compound containing hydrogen is exposed to
the dehydrogenising action of chlorine, bromine, or iodine, it
takes up an equal volume of chlorine, bromine, etc., for each
atom of hydrogen that it loses.
" If the compound contains water, it loses the hydrogen
of this without replacement."
The second of these rules was deduced from the trans-
formation of alcohol into chloral, and was thus intended to
explain the mode of formation of the latter, and at the same
time to support Dumas' view of the constitution of alcohol,
the latter being regarded by him as a compound of ethylene
and water.
Dumas soon extended his statement to one of great
significance, viz. that in chemical reactions generally an
exchange of equivalents of one element for equivalents of
others takes place. It was from this standpoint that he
regarded the oxidation of alcohol to acetic acid, and that of
bitter almond oil to benzoic acid, etc. etc., and he emphasised
the point that each atom of hydrogen was here replaced by
half an atom of oxygen. Those views, which gave evidence
of great clearness of vision, were however obscured by
certain additions which could not fail to create confusion
with regard to the constitution of the compounds in question;
thus, to give one instance only, formic acid was looked upon
as a " metaleptic product " of alcohol, although such a rela-
tion could not be proved in this case.
1 Of. Ann. Chim. Phys. (2), vol. Ivi. pp. 113, 140.
278 THE MODERN CHEMICAL PERIOD CHAP.
Laurent's Substitution or Nucleus Theory.
Dumas limited himself at that time (1835) to condensing
the known facts into the two above-mentioned laws. But
his countryman Laurent went further, in that he took into
consideration the nature of the compounds produced by sub-
stitution, and compared them with the original ones. He was
thus led to the proposition1 that the structure and chemical
character of organic compounds are not materially altered by
the entrance of chlorine and the separation of hydrogen.
This law, when taken in conjunction with the view that
chlorine assumes the role of the substituted hydrogen, is the
kernel of the Substitution Theory proper, of which Laurent
must be regarded as the author ; for Dumas denied at that
time the analogy between substitution derivatives and the
original compounds, and in reply to Berzelius, who attacked
him for this assumption, threw the responsibility for it upon
Laurent.2
The latter then strove to erect a system by developing
the above doctrine, the result of his efforts being the so-
called Nucleus Theory,3 which was published in the year
1836; a short account of this must be given here, even
although it never met with very hearty approval.4 According
to Laurent, organic compounds contained nuclei (radicaux),
and he distinguished between original nuclei (radicaux
fondamentaux), composed of carbon and hydrogen in simple
atomic proportions, and derived nuclei (radicaux derives),
which were produced from the first-named either through the
substitution of hydrogen by other elements or by the taking
up of additional atoms. He further stated that compound
1 Laurent frequently enunciated this(cf. Ann. Chim. Phys. (2), vol. Ix.
p. 223; vol. Ixi. p. 125 ; vol. Ixvi. p. 326).
2 Comptes Rendus, vol. vi. pp. 647, 695. Laurent stood up for his own
view (Ann. Chim. Phys. (2), vol. Ixvii. p. 303).
3 Cf. Ann. Chim. Phys. (2), vol. Ixi. p. 125.
4 L. Gmelin did, it is true, make use of the subdivision of organic com-
pounds, according to different nuclei, as a basis in his well-known text-
book, and helped in this way to spread Laurent's views.
v LAURENT'S NUCLEUS THEORY 279
radicals like amidogen or nitroxyl might substitute in place
of elements. This attempted classification of organic com-
pounds, under the name of the neucleus theory, shows a
distinct connection with the radical theory ; but the one-
sided view of the latter — that the radicals were unalterable
— has here disappeared. While this change in principle
marks an advance, the abandonment of the relation between
organic and inorganic compounds was undoubtedly a great
defect, since it involved the loss of a support indispensable
for a natural classification of organic substances.
It was not difficult for the chief exponents of the radical
doctrine to prove the insufficient basis of the nucleus theory,
the more so that Laurent laid himself open to criticism not
merely as a theoriser but also as an experimenter. His
work was severely handled by Liebig, who came to the
conclusion that Laurent's theory was unscientific and there-
fore pernicious. Berzelius likewise raised his voice ener-
getically against it, and indeed went so far as to say that he
considered a detailed criticism of it superfluous. But, as a
matter of fact, Laurent was too much depreciated from this
side ; for, however much we may dissent from many of his
untenable speculations, his effort to classify organic com-
pounds on uniform principles, and to show their connection
with one another, was not without merit. In addition to
this he had effectively aided in overthrowing the dogma of the
unchangeability of radicals. And, finally, we are indebted
to him for the proof that Dumas' empirical rules of substitu-
tion are by no means always applicable.
Before Laurent, in conjunction with Gerhardt, had again
brought forward his ideas in a more perfect form, Dumas1
entered the lists to do battle against the radical theory, and,
with this, against the dualistic idea in general. His beautiful
discovery of " chloracetic acid " afforded him the immediate
occasion for this, and he now gave in his adhesion to
Laurent's opinions, which formerly he would have nothing to
do with. The substituting atoms, e.g. the halogens, take up
the role of the expelled hydrogen atoms, and the resulting
1 Ann. Chim. Phys. (2), vol. Ixxiii. p. 73 et seq.
280 THE MODERN CHEMICAL PERIOD CHAP.
halogen compounds must therefore show an analogy to the
original ones, — this was for Dumas the clear result of his
work upon trichloracetic acid ; and he drew the same con-
clusion from the similar relations existing between aldehyde
and chloral. To put his ideas into a more permanent form,
he referred such related compounds to definite types, from
which they were derivable.
Dumas Type Theory (1839).
This effort, which reminds us strongly of Laurent's
nucleus theory (since in this case also whole series of com-
pounds were referred to fixed atomic complexes), bears in
the history of chemistry the name of the Older Type Theory,
to distinguish it from the newer one of Laurent and
Gerhardt. Dumas was led to establish his theory of types l
from the behaviour of trichloracetic acid, as observed by him-
self; he laid stress upon the fact that, in spite of the
entrance of six atoms of chlorine in place of six atoms of
hydrogen,2 the character of this derivative remained essentially
the same as that of acetic acid itself. Both compounds are
monobasic acids, and both yield products of analogous com-
position with alkalies. From all this he concluded that
" there are in organic chemistry certain types which remain
unchanged, even when their hydrogen is replaced by an
equal volume of chlorine, bromine, or iodine." Acetic and
trichloracetic acids, aldehyde and chloral, marsh gas and
chloroform, belong severally to the same chemical types.
According to Dumas, one such type embraced compounds
which contained the same number of equivalents combined
in a like manner, and whose properties were in the main
similar. We see here that the mutual relations of com-
pounds belonging to one chemical type are the same as
1 Ann. Chim., vol. xxxiii. pp. 179 and 259; cf. also M. Berthelot's recent
work, Introduction & Fjfaude de la Chimie des Anciens et du Moyen Age
(1889).
2 Dumas assigned to acetic acid the formula C4H8O4, and to (tri)chlor-
acetic acid that of C4H2C16O4.
v DUMAS' UNITARY SYSTEM 281
those which Laurent assumed between his original and derived
nuclei.
But the term " chemical type " did not satisfy Dumas ;
he allowed it to merge into that of " mechanical type," 1 this
latter comprising all compounds which might be supposed to
be formed from one another by substitution, even if they
differed totally in properties. Acting on this idea, Dumas
quite rightly classified alcohol and acetic acid under the same
mechanical type ; but, on the other hand, he brought together
compounds which had no sort of connection with one
another, e.g. formic acid and methyl ether. The ultimate
result was that an empty scheme of formulation carried
the day over what was really good in this doctrine — a
doctrine developed from Laurent's nucleus theory. The
endeavour to arrange organic compounds upon certain
types outweighed and pushed aside the higher problems
which Berzelius had sketched out for chemical science.
The idea of definite atomic complexes or radicals, which was
meant to pave the way for a knowledge of the chemical
constitution of compounds, was superseded by the setting up
of mechanical types, and thus the link intended to connect
organic with inorganic compounds was completely snapped.
This total abandonment of the principles put forward
by Berzelius, and found by him to be so serviceable,
could not fail to arouse his liveliest opposition. Dumas had
characterised Berzelius' electro-chemical doctrine as erroneous ;
the unitary conception was to step into the place of the
dualistic which the latter theory involved. Every chemical
compound forms a complete whole, and cannot therefore consist
of two parts. Its chemical character is dependent primarily
upon the arrangement and number of the atoms, and in a lesser
degree upon their chemical nature. These propositions of
Dumas stood in the sharpest opposition to the doctrine of
Berzelius; they proclaimed a one-sided unitarism, which
was therefore combated by Berzelius with every force at
his command.
1 Regnault had already (in 1838) spoken in a similar sense of molecular
types, which remain unchanged in chemical reactions.
282 THE MODERN CHEMICAL PERIOD CHAP.
The Overthrow of Berzelius' Ducdistic Doctrine.
Dumas did not scruple to say plainly that the dualistic
doctrine was harmful and retarded the development of
organic chemistry, and he made every effort to set it aside
and to supplant it by the unitary theory. His attack upon
Berzelius' doctrine (at that time held in high repute by
most chemists) was vigorously answered both by the latter
and by Liebig. Liebig x indeed admitted many points which
were disputed by Berzelius, e.g. the fact of substitution, but
he protested against Dumas' wide extension of this principle
(of substitution). The assertion of the latter that every
element of a compound might be replaced by another, and
yet the type be retained, was characterised by Liebig as
entirely unproven, and met with an ironical rejoinder.2
Berzelius, who saw his whole system based upon the electro-
chemical theory threatened, directed his criticism in the
Jahresberichten for 1838 and the next five years or so against
the theory of types. In opposition to Dumas' unitary view
he set up, as sharply as it was possible to do, the electro-
chemical and therefore dualistic theory as the fundamental
principle ; he adhered indeed essentially to his former stand-
point, according to which electro-negative elements could in
no case enter into the composition of radicals.
Berzelius sought to get over the difficulties which the
substitution of hydrogen by chlorine and other elements
involved, by arguing that compounds formed in this manner
must have a constitution different from that of the original
ones. But here he entered upon dangerous ground, and was
thereby led, prudent investigator as he was, into the most
utter contradictions of the principles which he had formerly
held to be inviolable.
Berzelius first expressed himself upon the composition
of acetic and trichloracetic acids. While the former (i.e. the
1 Ann. Chem., vol. xxxiii. p. 301.
2 Cf. Ann. Chem., vol. xxxiii. p. 308. The satirical letter given here
was composed by Wohler and published by Liebig.
v BERZELIUS' FIGHT AGAINST THE SUBSTITUTION THEORY 283
anhydrous acid) l was regarded by him as the oxide of the
radical acetyl, and given the formula C4P3 + O3, he looked
upon trichloracetic acid as a so-called "copulated compound"
or " conjugate compound " (gepaarte Verbindung"2) of quite
different constitution, viz. as a chloride of carbon copulated
with oxalic acid, of the formula Cg-Gig + CgOg.3 But he could
not at that time make up his mind to follow this to its
logical conclusion, and to ascribe to acetic acid an analogous
composition (i.e. to write it down as methyl copulated with
oxalic acid), manifestly from the apprehension that he would
in so doing surrender a principle of his electro-chemical
doctrine. He attempted similarly to explain the constitu-
tion of other chlorine organic derivatives, by assuming
copulse (Paarlinge) containing chlorine, with the result that
a different rational formula was assigned to the mother
substance from that given to its derivatives.
These unfortunate attempts to explain by the speculative
method the constitution of chemical compounds, that prob-
lem which, in his own opinion, was the most important in
the science, led Berzelius completely astray. In order to
carry through his doctrine of copulse, he had to assume
arbitrary radicals in organic compounds, without being able
to adduce the least evidence in favour of such assumptions.
Above all, he did not see what these really led to, for he
overlooked the fact that his chlorinated copulae could only
be formed by the substitution of the hydrogen atoms of the
radical by chlorine.
Melsens'4 important observation, made in the year 1842,
1 Berzelius formulated acetic acid as hydrate, C4j=t3-03 + j*0, i.e. as a
compound of the anhydride (at that time unknown) with water.
2 The idea that certain organic compounds are copulated or conjugated
(gepaart) was definitely expressed for the first time in one of the earliest
of Gerhardt's papers (Ann. Chim. Phys. (2), vol. Ixxii. p. 184). In this
paper he used the word copulation (accouplement) to signify the combination
of organic substances with inorganic. The one portion of such compounds
he termed the copula (copule), e.g. the organic substance which is copulated
with an inorganic acid.
3 For an explanation of these " crossed " symbols, see p. 236.
4 Ann. Chim. Phys. (3), vol. x. p. 223.
284 THE MODERN CHEMICAL PERIOD CHAP.
that chloracetic acid is reconverted into acetic by the action
of potassium amalgam, convinced Berzelius1 that his view of
the two acids having different constitutions was no longer
tenable. He therefore decided to regard acetic acid in the
same way as its chlorine derivative, i.e. as a copulated oxalic
acid with the copula C2Jt3, formulating the two compounds
thus —
C2F3 + C2O3. jtO . . . Acetic acid.
s.tO . . . Chloracetic acid.
But in doing this he made the important admission of the
substitution of hydrogen by chlorine in the copula. And
even although he did emphasise the point that the latter
exercised no particular effect upon the compound to which
it belonged, he none the less recognised hereby a funda-
mental principle of the doctrine of substitution.
But, notwithstanding this admission, Berzelius remained
to the end of his life an opponent of the theory of types, and
endeavoured to uphold the dualistic view by every means in
his power. He had to undergo the pain, however, of finding
his hitherto faithful adherents no longer able to follow him
in this, and indeed of hearing them dissent publicly from
his treatment of the question as to how the constitution of
organic compounds was to be explained. Liebig, who had
already before this taken the facts of substitution into
account,2 declared openly against Berzelius' far-fetched
attempts at explanation,3 the more so since the chlorine
and bromine derivatives of aniline had been investigated in
the Giessen laboratory by A. W. v. Hofmann, and had been
accepted as evidence that the chemical character of a com-
pound depends to a not inconsiderable extent upon the
arrangement of its atoms. Liebig therefore turned himself
to the unitary theory. The following words 4 show us the
1 Lehrb. d. Chemie (fifth edition), vol. i. p. 709.
2 Ann. Chem., vol. xxxi. p. 119 ; vol. xxxii. p. 72.
3 Ibid., vol. 1. p. 295 ("Berzelius und die Probabilitatstheorien"). The
correspondence between Berzelius and Liebig, which has been so often re-
ferred to already, shows us in a truly dramatic way the gradual estrange-
ment of the two men. 4 Ibid. , vol. 1. p. 297.
v OVERTHROW OF THE DUALISTIC DOCTRINE 285
attitude taken up by Liebig, and we may be sure by others
also, towards Berzelius at that time : " During the last
years (of his life) Berzelius ceased to take an experimental
share in the solution of the problems of the time, and turned
the whole force of his mind to theoretical speculations ; but
these, not being the result of his own observations or
supported by them, found no echo or approval in the
science."
This much is certain, that, by carrying his speculations
too far, Berzelius had not only shaken the edifice of his own
doctrine, but had also greatly injured the radical theory,
more particularly by heaping up one unproven hypothesis
upon another. His opponents went so far as to assert that
he had by his arbitrary assumptions "made a theory
regarding substances which had no existence " in organic
chemistry. It almost seemed as if his whole system was
doomed to fall. One result of all this was that many
chemists became visibly discouraged, and, holding all specu-
lation as dangerous, either applied themselves to the
empirical side of the science, or turned to other subjects.
And yet, in spite of the slight regard in which the radical
theory was held in many quarters, it soon became evident
that, for the investigation of chemical constitution, the
assumption of radicals, which had displaced the theory of
types, was indispensable. In the course of the forties a
fusion of the radical theory with the older doctrine of types
took place on the unitary side; from the joint work of
Laurent and Gerhardt there resulted the new theory of types.
Upon the other side, at the same time, the much-derided
copulse were brought back to fresh life by H. Kolbe ; with
Frankland's aid a clearer notion of the meaning of copulated
compounds was arrived at, and thus the way was smoothed
for the establishment of the new radical theory and the
doctrine of valency.
286 THE MODERN CHEMICAL PERIOD
Fusion of the older Theory of Types with the Radical Theory
by Laurent and Gerhardt.
Of the two investigators whose joint work effected a
transformation of the old into the new theory of types,
Laurent — as mentioned above — had been already active as
the originator of the substitution theory proper. Although
both of them were resolute opponents of the dualistic view,
they had, nevertheless, no objection to make use of the con-
ception of radicals, though to these latter they attached a
meaning of their own. Besides Laurent and Gerhardt other
chemists contributed materially to the establishment of the
new theory of types, both by the ideas to which they gave
expression and by the observations that they made. The
stimulus thus given by Wurtz, Hofmann and Williamson
thus falls to be recorded here also.
Laurent and Gerhardt exercised a strong mutual in-
fluence upon, and undoubtedly supplemented one another.
Gerhardt was endowed with the special gift of bringing
together isolated facts under one common point of view, and
of drawing general conclusions therefrom. Laurent too was
happy in perceiving the great importance involved in par-
ticular ideas, and he kept himself freer from prepossessions
upon many points than his colleague.
A few sentences may be added here with regard to the
lives of these two men. Auguste Laurent, born at La Folie
near Langres in 1807, was initiated into chemistry by
Dumas, thus acquiring a special knowledge of the organic
part of it, to which with a certain one-sidedness he sub-
sequently remained faithful. His work upon naphthalene
and carbolic acid, together with their derivatives, is evidence
of this. After filling various posts, the last of which was a
chemical professorship at Bordeaux, Laurent became Warden
of the Mint at Paris, where he remained in intimate con-
nection with Gerhardt until his early death in 1853.
Charles Gerhardt was born at Strasburg in 1816, and
began his scientific career well equipped with a wide general
v LAURENT AND GERHARDT 287
education ; he studied chemistry at various places in
Germany, finally under the stimulating guidance of Liebig,
to whom he, like so many others, was so greatly indebted.
After working for several years in Paris, he became Pro-
fessor of Chemistry at Montpellier from 1844 to 184 8, and
after another prolonged residence in the first-named city
(where he opened a school for chemistry, which however
was not commercially a success), was called in 1855 to fill
the chemical chair in the Faculty of Sciences at Strasburg,
where he died in the following year. His important services
in the development of organic chemistry, together with the
joint theoretical views of Laurent and himself, are detailed
below.
Gerhardt' s Theory of Residues.
At the time that Gerhardt brought out his first scientific
work, the fight between the radical and substitution theories
was at its height. The latter found pronounced expression
in Dumas' theory of types, and was opposed not merely to
the dualistic views upon which the older radical theory was
based, but to radicals in general. Gerhardt doubtless felt
the disadvantages which the abandonment of the proximate
constituents of organic compounds involved. Without for-
saking the strict unitary standpoint of Dumas, he attempted
to reintroduce the disdained radicals into chemistry under
another name and with an altered meaning, — he set up the
theory of residues (thdorie des rdsidus).1
According to him, residues are atomic complexes which
remain over from the interaction of two compounds, as the
result of the stronger affinity of particular elements for one
another, and which combine together because they are
incapable of existing separately. Thus Gerhardt explained
the formation of nitro-benzene from benzene and nitric acid,
and, generally, the production of those bodies which he termed
" copulated compounds " (gepaarte Verbindungen) in the fol-
lowing simple manner : — " When two substances react with
1 Ann. Chim. Phys. (2) vol. Ixxii. p. 184.
288 THE MODERN CHEMICAL PERIOD CHAP.
one another, an element (e.g. hydrogen) present in the one
combines with another element (oxygen) present in the other
to produce a stable compound (water), while the residues
unite together." The latter he did not look upon as being
actual atomic groups present in the compound in question,
but as imaginary quantities ; they were in his view absolutely
distinct from the compounds of the same composition which
were known in the free state, e.g. sulphurous acid (S02) or
nitrogen peroxide (NO2). Gerhardt gave expression to this
difference by assuming the residues as being present in the
" substitution-form." Further, the supposition of different
residues in one and the same compound, according either
to its mode of formation or decomposition, was also
brought forward by him at that time.1
If we examine this conception of Gerhardt's more closely,
we see that his views upon substitution are expressed in the
same breath with those upon radicals as variable atomic
complexes. He endeavoured, in fact, to explain the pro-
cesses of substitution by the aid of this idea, in teaching that
an eliminated element is replaced by an equivalent of another
element or residue of the reacting substance.
Dumas and Laurent too had already said the same thing
in a different way. But Gerhardt knew how to draw im-
portant conclusions from his theory with regard to the
chemical nature of " copulated compounds " ; it did not
escape him that the saturation-capacities of the latter with
respect to bases were quite different from those of the
original acids before these had been " copulated " with an
alcohol or a hydrocarbon. Thus nitro-benzene, an indifferent
substance, was produced from nitric acid and benzene, and
the monobasic ether-sulphuric acids from sulphuric acid and
the alcohols. Gerhardt concluded from these and similar
observations that " the basicity of a copulated compound is
1 It must be mentioned here that the founders of the radical theory,
Berzelius and Liebig, had expressed at one time (the former in 1834, and
the latter in 1838) perfectly similar views as to the possibility of assuming
different radicals in the same compound (cf. Berzelius' Jahresbericht, vol.
xiv. p. 348 ; Ann. Ohem., vol. xxvi. p. 176).
v GERHARDT'S CLASSIFICATION OF ORGANIC COMPOUNDS 289
equal to the sum of the basicities of the copulating sub-
stances minus 1." By means of this, his " Law of Basicity "
(Basizitdtsgesetz}^ he was able to determine the chemical
nature of acids about whose saturation-capacities doubt still
prevailed at that time. With absolute definiteness he
stated acetic acid to be monobasic, although it forms an acid
sodium salt, and the same with regard to hydrochloric and
nitric acids, because all these yield only neutral ethers ;
while sulphuric and oxalic acids were dibasic because, on
copulation with an alcohol, they yield in the first instance
monobasic ether-acids.
Gerhardt' s first Classification of Organic Compounds.
Even before Gerhardt had attained to such clearness in
this important question, he had directed his endeavours to
the classification of organic compounds. His first attempt
at this is contained in the Precis de Chimie Organigue
(1842). Here we find him strongly influenced by Dumas
and his type theory ; like the latter, he avoided the use of
any formulae which might appear to indicate the proximate
or rational composition of chemical compounds. These he
arranged in an ascending series according to their empirical
formulae, in such a manner that substances containing equal
amounts of carbon constituted one group. Inclined to
express himself in figurative language, he compared this
classification of organic compounds to a ladder, whose
lowest steps were formed of the substances of simplest, and
whose highest of those of most complex composition. And
since, from the oxidation of compounds rich in carbon,
others which contain fewer atoms of that element are
produced, he gave his arrangement the name of " combustion
ladder " (echelh de combustion).
There was nothing of an unconstrained and natural
classification here; on the contrary, the most diverse
1 Cf. Comptes Rendus, vol. xvii. p. 312 ; Comptes rendus des Travaux
Chimiques par Laurent et Gerhardt (1845), p. 161.
U
290 THE MODERN CHEMICAL PERIOD CHAP.
substances were collected into one class, provided only they
fulfilled the necessary condition of containing the same
number of carbon atoms. Not the slightest heed was paid
to their chemical nature ; acetic ether was placed alongside
of butyric acid, and ethyl-oxalic acid alongside of succinic,
solely for the reason given above. We note distinctly here
the influence of Laurent, who not long before had made a
mechanical classification of organic substances in a precisely
similar manner (this, however, had made no impression).
Indeed, it is hardly conceivable to imagine how the
older radical theory could have sustained a more severe blow
than it did by the undue exaggeration of Dumas' theory of
types. Gerhardt himself quickly felt this; his attempt at
classification, which found its final and most definite ex-
pression in the new theory of types, showed distinctly that
he had found a point of connection with the views of the
radical theory, and that he strove to amalgamate the latter
with the doctrine of substitution.
Before setting forth in detail these labours of Gerhardt,
the efforts which he made — partly in conjunction with
Laurent — to bring about uniformity of view with regard to
the atomic weights of elements and compounds must be
touched upon. The great and lasting service which those
two men rendered in clearly defining what is meant by the
term " molecule," and therewith reviving Avogadro's hypo-
thesis, especially deserves our fullest recognition.
Gerhardt's "Equivalents"
At the beginning of the forties the uncertainty as to
what atomic weights should be ascribed to the elements, and
what atomic (i.e. molecular) weights to chemical compounds,
had become one of great moment. The doubt which Gay-
Lussac, Davy and others had previously urged against the
assumption of definite atomic weights was again brought
forward by Gmelin and his school. The atomic weight system
of Berzelius, that work which he had accomplished after such
v GERHARDT'S EQUIVALENTS 291
immense labour, came very near to being given up, or at
least greatly altered. In place of his atomic weights, based
as they were upon solid foundations, " combining weights "
were to be introduced, i.e. those values which were expressed
by the simplest proportions of the substances entering into
combination. All speculations upon relative atomic values
were to be banished, and only the most sober possible
formulation of chemical compounds attempted. The imme-
diate result of this reaction was the halving of a large
number of the atomic weights which Berzelius had intro-
duced into the science. In place of the values assumed by
him for carbon, oxygen, sulphur and most of the metals,
other values only half as great were taken ; these equivalents
were: C = 6, O = 8, S = 16, Ca = 20, Mg=12, and so on.
Gerhardt began to oppose these equivalents in the year
1842, and was able to prove by cogent arguments that their
assumption was inadmissible.1 He showed, namely, that
the amounts of water, carbonic acid, carbonic oxide and
sulphuric acid, which were separated during the reactions
of organic compounds, were never expressible by what was
known as one equivalent, but by two or some multiple of
two. The smallest equivalent formulae for those com-
pounds, according to Gmelin's view, were H2O2, C204>
C2O2 and S2O4. But, argued Gerhardt, there must be
an error underlying this : " the symbols H2O2 and C2O4
either express one equivalent, or they express two." If we
assume the former of these, then the formulae of the in-
organic compounds must be doubled ; if the latter, then the
" organic formulae " must be halved. Gerhardt did away
with the contradiction which existed in the formulation of
organic and inorganic compounds by reinstating Berzelius'
atomic weights for the elements carbon, oxygen and sulphur,
which were the ones of greatest moment here ; i.e. taking
H = l, then 0 = 12,0 = 16, and S = 32.2 But he earned
1 Cf . Journ. pr. Chem. , vol. xxvii. p. 439 ; also his Precis de Chimie
Organique, vol. i. p. 49.
2 Cf. Journ. pr. Chem., vol. xxx. p. 1. It is very extraordinary that
Gerhardt should have made no reference here to the identity of the atomic
weights which he proposed with those of Berzelius.
u 2
292 THE MODERN CHEMICAL PERIOD CHAP.
this reform only half way ; for, while he gave the proper
values for the elements just named, he was led by special
considerations to assume values for most of the metals which
were only half as great as those proposed by Berzelius.
Unlike the latter, who began by assuming that most of the
metallic oxides had the composition indicated by the
general formula MeO, Gerhardt compared these oxides
with water, giving them therefore the formula Me9O. He
thus arrived at the correct atomic weights of the monovalent
metals, but at incorrect ones for the divalent : e.g. for calcium
the value 20 instead of 40, for lead that of 103*5 instead of
207, and so on.
Apart from this incompleteness there was an obscurity in
Gerhardt 's views with respect to atomic weights which could
not fail to produce confusion ; he both called the atomic
weights just mentioned equivalents, and at the same time
made use of this term for those amounts of chemical com-
pounds which corresponded to their molecular weights, i.e.
speaking generally, for quantities which are by no means
necessarily equivalent chemically. Thus the quantities of
hydrochloric, sulphuric and acetic acids represented by the
formulae HC1, H2SO4 and C2H402, were in his mind equi-
valent to one another. We must here emphasise the point
that Gerhardt attached another meaning to this word to
what we now do; equivalents of chemical compounds were
for him merely the comparable quantities of these.
Absolute clearness in the above points was only arrived
at through Laurent's assistance. The latter definitely grasped
the distinctions between molecular, atomic and equivalent
weights, the correct determination of whose values constitutes
the basis of our present views upon molecule and atom ; it
was he who brought Avogadro's hypothesis back to life again,
and prepared the way for its development, so vitally im-
portant for chemical science.
v MEANING OF MOLECULE, ATOM AND EQUIVALENT 293
The distinguishing between the terms Molecule, Atom, and
Equivalent by Laurent and Gerhardt.
Gerhardt's most memorable efforts had for their aim the
expression of the composition of all chemical compounds by
means of formulae based upon one common standard, i.e.
formulae comparable with one another. The formulae of
volatile compounds ought, according to him, invariably to
indicate those quantities which occupy two volumes when in
the gaseous state, taking the volume of one atom of hydrogen
as equal to 1. This sound principle has ever since been fully
recognised.
Acting upon this, he altered the four-volume formulae of
many organic compounds into tioo-volume ones by halving
them. The false conception, much current at that time,
according to which acetic acid (for example) received the
formula C4H8O4, alcohol that of C4H12O2, and ethylene that
of C4H8, had grown up as the result of the dualistic views
upon the composition of organic compounds, and also of the
use of several incorrect atomic weights.1 It was precisely
to organic compounds — most of them volatile without de-
composition— that Gerhardt's law could be most extensively
applied, the law, namely, that their formulae depend upon
the amounts by weight which are contained in equal
volumes.
Much of Gerhardt's indistinctness, e.g. that produced by
his using the word " equivalent " in a totally mistaken sense,
was put right by Laurent. The latter pointed out with
emphasis and clearness 2 that Gerhardt's equivalents were
not even comparable with those of compounds, let alone of
equal value with them ; he showed that Gerhardt's equi-
valents of the elements must be regarded as their atomic
weights, and the equivalents of compounds as their molecular
1 For deducing the atomic composition of organic acids, the silver salts
of the latter were chiefly made use of ; for acetate of silver Berzelius had
arrived at the formula C4H603.AgO (Ag = 216), from which the composition
of the acid, as given above, followed. Alcohol was regarded by Liebig as
the hydrate of ethyl ether, and consequently formulated as C4H100-H2O,
whence the composition C4H8 was ascribed to ethylene, and so on.
2 Ann. Chim. Phys. (3), vol. xviii. p. 266.
294 THE MODERN CHEMICAL PERIOD CHAP.
weights. Laurent's merit consisted in clearly grasping the
meanings to be attached to these terms.
Laurent understood the molecular weight of an element
or chemical compound as meaning that quantity which,
under like conditions, occupies the same volume as two
atoms of hydrogen ; the quantity represented by the latter
he looked upon as a molecule of hydrogen. For him, there-
fore, the molecular weights of chlorine, oxygen, nitrogen
and cyanogen were expressed by the formulae C1.2, O2, N2
and (CN)2, and the molecular weights of hydrochloric and
acetic acids by the formulae HC1 and C2H4O2, because the
quantities indicated by those symbols filled, when in the
state of vapour, the same space as two parts by weight of
hydrogen. The agreement between his ideas and those of
Avogadro is plainly evidenced here ; but to Laurent belongs
the further merit of developing these in a high degree. He
defined the molecule as " the smallest quantity which can be
employed in order to produce a compound." And he saw a
proof of the correctness of this view in the fact that the
atoms of chlorine, bromine, hydrogen, etc., always act
chemically in pairs.
The atom, according to Laurent, is the smallest quantity
of an element which can be present in a compound; for
atomic weights he adopted the values proposed by Gerhardt,
which agreed to a great extent with those of Berzelius.
Equivalents, lastly, signified for him the " equivalent
amounts of analogous substances " (die gleichwertliigen Mengen
analoger Korper). This last definition led logically to the
assumption that one and the same element has more than
one equivalent, if it reacts with others in varying combining
proportions.1
The joint work of Laurent and Gerhardt upon this
1 "The idea of an equivalent includes in itself the view of a similar
function ; we know that one and the same element can fill the role of two
or of several others, whence it must follow that different weights also
correspond to those different functions. On the other hand, we find
different weights of the same metal, e.g. iron, copper, mercury, etc., re-
placing the hydrogen of acids, and thus forming salts which contain the
same metal but possess different properties. These metals have therefore
various equivalents" (cf. Comptes rendusdes Travaux Chimiques par Laurent
et Gerhardt (1849), p. 1. et seq.).
v WORK PREPARATORY TO THE NEW TYPE THEORY 295
question — so excessively important for theoretical chemistry
—found very little acceptance amongst chemists; indeed,
many of them actively opposed such a conception as that of
variable equivalent values. The sound but not yet sufficiently
grounded views of Laurent upon the magnitude of the mole-
cules (i.e. molecular weights) of elements and compounds did
not, however, succeed in making their way at that time
—towards the end of the forties. Gmelin's combining weights
were still for the most part adhered to, and at the date of the
appearance of Gerhardt's Lehrfawh der Chemie (1853) were
in such general use that the author, against his better judg-
ment, used Gmelin's numbers for the chemical symbols in
his first three volumes, i.e. he employed equivalent formula?.1
Stronger proof than that given by Laurent and Gerhardt
had to be adduced in order to convince people that the
atomic and molecular weights which they employed were
the correct ones. It was the researches of Williamson,
published at the beginning of the fifties, which were especially
instrumental in leading to this. The true perception was
again arrived at here from experience collected in the field
of organic chemistry.
Influence of the Researches of Wurtz, Hofmann and William-
son upon the Development of the Theory of Types (1848-51).
The discovery by Wurtz 2 and Hofmann of organic deri-
vatives of ammonia was of great importance for the firm
1 Gerhardt gave his reasons for using this notation in the preface to his
book (vol. i. pp. 1, 2) as follows : " J*y ai memefait le sacrifice de ma nota-
tion, pour m'en tenir aux formules anciennes, afin de mieux ddmontrer par
Vexemple, combien Vusage de ces dernieres est irrational, et de laisser au
temps le soin de consacrer une reforme que les chimistes n'ont pas encore
ge'ne'ralment adopte'e."
2 C. A. Wurtz, who was born at Strassburg in 1817 and died at Paris
in 1884, was a pupil of Liebig, Balard and Dumas ; his life and works have
been described very fully by A. W. v. Hofmann (Ber., vol. xx.p.815 et seq. ),
and by Friedel (Notice sur la Vie et les Travaux de Wurtz). From the
year 1845 onwards, Wurtz filled the post of professor at various teaching
institutions in Paris (including the Ecole de Medicine and the Sorbonne), his
influence becoming very great as time went on. The lucidity and general
296 THE MODERN CHEMICAL PERIOD CHAP.
establishment of the views finally comprised in Gerhardt's
theory of types. In 1849 Wurtz observed the remarkable
decomposition of cyanic ether by means of caustic potash,
whereby he discovered methylamine and ethylamine, com-
pounds so closely resembling ammonia.1 Before this
Berzelius had already expressed the view that the organic
nitrogenous bases in general might be looked upon as sub-
stances which were copulated with ammonia. Liebig, on
the other hand, regarded these as amido-compounds analo-
gous to the ethers. Wurtz fluctuated between these two
opinions, besides also suggesting the possibility of the
organic bases being substitution products of ammonia, e.g.
of " methyliak " (our methylamine) being ammonia in which
one hydrogen atom was replaced by methyl. At first, how-
ever, he appears to have given the preference to the older
view of Berzelius, according to which ethylamine, for example,
was " ammonia copulated with etherin."
The " typical " view of these bases was first arrived at
through A. W. v. Hofmann's brilliant researches upon amine
bases; the production of these from ammonia and haloid
compounds of the alkyls furnished a splendid proof of the
correctness of the view that those compounds were formed
from ammonia by the exchange of one or more hydrogen
atoms for alcohol radicals.2 The constitution of the imide
and nitrite bases, like that of di- and tri-ethylamine, could
form of his lectures were such as to make it a pleasure to listen to them.
From 1866 to 1875 he was Dean of the Medical Faculty, and in this position
materially aided in raising the standard of instruction in practical chemistry
and physiology for medical students. Among his writings were the Lemons
de Philosophic Chimique (1864) and La Thdorie Atomique (1879), works which
treated of questions in theoretical chemistry and which found much accept-
ance because of their clearness and the charming style in which they were
written ; also his Traite Elementaire de Chimie Medicale (1864), and the
Dictionnaire de Chimie Pure et Appliquee (edited by him). His admirable
experimental researches, by which he acted as a pioneer in opening up
particular branches of organic chemistry, will be spoken of under the special
history of the subject. Most of his work was published in the Annales de
Ghimie et de Physique, of which he became one of the editors in 1852, and
in the Comptes Rendus.
1 Comptes Rendus, vol. xxviii. p. 223 et seq.
2 Ann. Chem., vol. Ixxiv. p. 174.
v AUGUST WILHELM VON HOFMANN 297
scarcely be explained in any other way than by their deriva-
tion from ammonia, through the substitution of hydrogen
atoms by alkyl radicals. Before continuing this subject, a
short account must be given here of Hermann's life and work.
August Wilhelm von Hofmann, born at Giessen on 8th
April 1818, after several years of philosophical and juris-
tical studies devoted himself to chemistry under the guidance
of Liebig, whose assistant he soon became. After filling
for a short time the post of assistant-professor (Privatdocent)
at Bonn, he accepted in 1845 a call (made at Prince Albert's
instigation) to the newly founded College of Chemistry in
London, which became a government institution in 1853;
in 1855 he was also made a non-resident Assayer of the
Mint (these appointments, which were held by eminent
chemists, otherwise unconnected with the Mint, were
abolished in 1870). He likewise taught at the School of
Mines. In 1864 he removed back again to Bonn, and in
1865 was called to Berlin, as successor to Mitscherlich,
where he continued to work with quite exceptional brilliancy
until his death on May 5th, 1892.
Hofmann's work as a teacher was in every respect
extraordinarily fruitful, the most striking proof of this being
shown by the large number of his pupils who have since
attained to eminence. His organising talent found scope in
the building and fitting up of two admirable laboratories for
general instruction at Bonn and Berlin. To success as a
teacher there was also added, in a marked degree in his case,
success as an author ; here he showed the power of represent-
ing facts, and chemical doctrines founded upon them, in a
delightfully clear and perspicuous manner. As an instance
of this we may mention his Einleitung in die moderne Chemie
(" Introduction to Modern Chemistry "). The Obituary
Memoirs (upon Liebig, Wohler, Dumas, Sella and Wurtz) by
him are characterised by the loving care with which he enters
into the life and works of the men whom he extols, besides
being written in a most fascinating style.
As an investigator in experimental chemistry Hofmann
meets us at every step ; organic chemistry, more especially
298 THE MODERN CHEMICAL PERIOD CHAP.
the field of nitrogen and phosphorus compounds, was
thoroughly studied by him, and in part exhausted. Finally,
reference must be made here to the wonderful influence
which he exerted upon the coal tar colour industry, an industry
which to a great extent arose out of his scientific studies.
Most of Hofmann's papers were published in the Annalen
der Chemie and in the Berichte of the German Chemical
Society (at Berlin), which was founded by him in 1868, and
of which he was for a long time President. In November,
1892, F. Tiemann delivered before the German Chemical
Society a sympathetic and appreciative address upon his
life and work (Ber., vol. xxv. p. 3377).
It was only after these important investigations by
Hofmann on the constitution of the organic ammonia bases
that Wurtz clearly perceived that this relationship to
ammonia was the only conclusive explanation of those com-
pounds. He (Wurtz) condensed the result of the above
researches into the words : " It was thus that the ammonia
type was created."
To this Williamson,1 by his distinguished researches,2
added the water type, thereby with Wurtz and Hofmann
providing the foundation for Gerhardt's theory of types. In
his experiments Williamson started with the idea of replac-
ing hydrogen in known alcohols by hydrocarbons, so as to
obtain homologues of the former. The action of ethyl iodide
upon potassium ethylate yielded him, however, ethyl ether,
and not the expected ethylated alcohol. This result induced
him to try whether, by the action of potassium ethylate
upon methyl iodide, a mixture of ethyl and methyl ethers or
only one homogeneous compound would be produced. The
latter was found to be the case ; methyl- ethyl oxide, a " mixed
1 A. W. Williamson, born in 1824, was a pupil of Liebig and afterwards
filled for a long time the chair of chemistry in University College, London,
retiring from this post in 1887. Especially in the years between 1850-60
did he enrich organic chemistry with valuable observations, which led to
deductions of general application. His work upon the formation and con-
stitution of ethers, more particularly, was of the first importance.
2 Cf. especially Ann. Chem., vol. Ixxvii. p. 37 ; vol. Ixxxi. p. 73. Or
Journ. Chem. Soc., vol. iv. pp. 106 and 229.
v WILLIAMSON'S RESEARCHES ON ETHERS 299
ether," was obtained, and with this the much-discussed and
at that time burning question of the molecular weights of
ether and ethyl alcohol, and also that of the atomic weight of
oxygen, were solved.1 Liebig's idea that alcohol was the
hydrate of ether had to be given up ; on the other hand,
Williamson's researches proved that the molecular formulae
of both compounds which had been assumed "by Berzelius
were the correct ones. The formation of ether by the
interaction of alcohol and sulphuric acid, a process which
had so greatly exercised the minds of the most eminent
chemists, was thus now made perfectly clear by Williamson.
Alcohol and ether he regarded as analogous to and built
up on the type of water, as his definitions and formulae
show : —
0, Water ; °25O> Alcoho1 J 0' Ether'
This view (a view of which Laurent and other chemists
had previously spoken favourably as being an admissible one)
Williamson then proceeded to extend to many other sub-
stances, organic and inorganic, endeavouring at the same
time to make its advantages evident. Thus he compared
the acids, ketones (of whose true composition he had
furnished beautiful experimental proof by a process similar
to that mentioned above), and other compounds with water,
i.e. he derived from water the compounds just named, by the
substitution of one or both atoms of hydrogen by compound
radicals or elements. The following examples will serve to
illustrate his " typical " theory : —
P FT O "FT "NTi
°2g3vO, Acetic acid ; gO, Potassic hydrate ; g 2O, Nitric acid ;
p R n Acetic anhydride K ^n „.., .
K
known) ;
Williamson expressed himself as follows with regard to
the applicability of the typical view : 2 " The method here
1 Chancel arrived in a similar manner at the same result, independently
of Williamson (cf. Comptes Rendus, vol. xxxi. p. 521).
2 Journ. Chem. Soc., vol. iv. p. 239.
300 THE MODERN CHEMICAL PERIOD CHAP,
employed of stating the rational constitution of bodies by
comparison with water, seems to me to be susceptible of
great extension; and I have no hesitation in saying that
its introduction will be of service in simplifying our ideas,
by establishing a uniform standard of comparison by which
bodies may be judged of."
His confidence in the possibility of extending the
" typical " idea came out still more strongly upon another
occasion,1 when he expressed the opinion that reference to
the one type of water sufficed for all inorganic and for the
best-known organic compounds ; only that in the case of
many substances, e.g. dibasic acids, the formula of water
must be taken doubled. The views expressed here are also
to be found for the most part in Gerhardt's theory of types.
The most important result of Williamson's researches con-
sisted, however, not in the one-sided typical mode of ex-
plaining the constitution of chemical compounds, but rather
in the determination of the true molecular values of organic
substances. The methods which he made use of in order to
attain this end very soon proved themselves exceptionally
productive ; they led Gerhardt to the discovery of the acid
anhydrides, and Wurtz to that of mixed hydrocarbon radicals,
the investigation of both of which has finally settled the
controversy as to the molecular formulae of whole series of
organic compounds.
Grerhardt's new Theory of Types.2
What has just been said is sufficient to show how effec-
tively the " typical " view of organic compounds was furthered
by the experimental researches of Wurtz, Hofmann and
Williamson. Numerous nitrogenous compounds were re-
ferred to the ammonia type, and a still larger number of
oxygenated ones to the water type. Gerhardt consummated
1 Journ. Chem. Soc., vol. iv., p. 350 (1851).
'J Cf. Ann. Chim. Phys. (3), vol. xxxvii. p. 331 ; also Traite de Chimie,
vol. iv. (1856).
v FIRST STEPS TOWARDS GERHARDT'S TYPE THEORY 301
his work by adding to these the hydrogen and hydro-
chloric acid types, and then he made the attempt to include
all organic compounds under those few forms.
The endeavour to compare organic with inorganic bodies,
which was already so strongly marked in the radical theory,
was again distinctly apparent here ; and here again it was
ethyl compounds which mainly gave rise to the setting up
of inorganic types as models for organic compounds. So
early as 1846 Laurent * had thrown out the suggestion which
was established in full detail by Williamson later on, — that
alcohol and ether might be looked upon as derivatives of
water, thus —
H2O, Water ; ^O, Alcohol ; |£o, Ether.2
The inorganic acids and oxides too might be viewed
(according to Laurent) as substitution-products of water.
These compounds, so various in their natures, were regarded
as built up after the same pattern.
In and after 1848 the American chemist Sterry Hunt
published several papers,3 in which he gave a wide extension
to the typical view by showing how large numbers of oxy-
genated compounds, inorganic as well as organic, might be
pictured as derived from water, and how hydrocarbons belong
to the hydrogen type. But his work, being unknown in
Europe, did not in any way quicken the growth of the similar
ideas then running through many other minds. On the
other hand, the above definite utterances of Williamson
upon the reference of many organic compounds to water (as
the form of compound of most general application) un-
doubtedly brought about a more rapid development of the
doctrine of types. Not merely oxygenated bodies, but also
non-oxygenated ones like amines, were without any hesita-
tion taken as derived from water. Although Williamson
thus lost his firm standing ground in consequence of the all
too great elasticity of his formulae, he gained, on the other
1 Ann. Chim. Phys. (3), vol. xviii. p. 266 et seq.
2 Of. also Berzelius' view with regard to Ether, p. 256.
3 Amer. Journ. of Science (2), vols. v., vi., vii. and viii.
302 THE MODERN CHEMICAL PERIOD CHAP.
hand, marked advantages from the extension of the type
idea. He referred many compounds to the double or triple
water type, and thereby introduced the notion of polyatomic
radicals into chemistry. Sulphuric acid, for example, he
referred to two molecules of water in which two atoms of
hydrogen are replaced by sulphuryl (SO2) —
O
2 Mol. water ; SO
•>O2 Sulphuric acid ;
H °
while phosphoric acid was derived in a like manner from
three molecules of water, and so on.
Stimulated especially to it by his own important dis-
covery of the anhydrides of monobasic organic acids,1
Gerhardt collected the accumulated mass of " typical " ideas
and condensed them into uniformity. Before everything
else he desired to classify the large number of organic
compounds in a synoptical manner, and for this the water,
ammonia, hydrogen and hydrochloric acid types were to serve
as models. In addition to this he made use of a principle
for the co-ordination of organic substances, which had indeed
been already applied by other chemists, but never in such a
general manner, viz., he arranged them in different series,
the members of each series belonging to the same type.
His first classification of organic compounds (cf. p. 289)
did not possess the advantages which such a grouping in
series offered. Since then Schiel 2 had established the con-
ception of homology by directing attention to the equal
differences in the composition of analogous bodies, more
particularly, of the alcohols, while Dumas had proved the
same thing for the acids. And the researches of Kopp had
further shown, with the utmost clearness, not only the
chemical but also the physical resemblance of homologous
compounds.
1 Ann. Chem., vol. Ixxxii. p. 128. Those bodies, whose existence had
been predicted by Williamson, were formerly supposed by Gerhardt to be
incapable of preparation.
2 Ann. Chem., vol. xliii. p. 107 (1842).
v DERIVATION OF ORGANIC COMPOUNDS FROM TYPES 303
Gerhardt now collated the results of those preparatory
labours with great ingenuity, and associated with the series
of homologous bodies, which differed in composition by the
increment (CH2)W, other series of isologous and heterologous
compounds. The former of these were, according to him,
chemically analogous substances which show another com-
position-difference from homologous ones, e.g. ethyl alcohol,
C2H6O, and phenol, C6H6O ; propionic acid, C3H6O2, and
benzoic acid, C7H602, — compounds which differ from one
another by the increment C4. Heterologous series contain
such substances as are chemically dissimilar, but show a
close connection with one another in their modes of forma-
tion. To such a series belong, for instance, ethyl alcohol,
C2H6O, and acetic acid, C2H402 ; amyl alcohol, C5H120, and
valeric acid, C6H10O2.
As already mentioned, Gerhardt looked upon the members
of such series as derivatives of one of his four types, resulting
from these by the partial or complete substitution of their
hydrogen atoms by residues. From the water type were
derived (as Williamson had already taught) most of the
organic compounds, including the alcohols, acids, simple
and compound ethers, acid anhydrides, ketones, aldehydes
and salts. Alongside of water the analogously constituted
sulphuretted hydrogen was placed as an auxiliary type, and
from it the sulphur compounds corresponding to the oxygen
compounds just mentioned were derived, e.g. the sulphides,
mercaptans, thio-acids, etc. The following examples will
serve to illustrate what has just been said : —
H90 H C,H,0 C9HR H
Water Methyl alcohol Acetic anhydride Acetic ether Aldehyde.
Under the ammonia type were classified the amines,
amides and imides, phosphines, arsines, etc., thus —
(C2H5)3P
Methylamine Acetamide Succinimide Triethyl-phosphine.
The hydrogen type included the hydrocarbons, together
304 THE MODERN CHEMICAL PERIOD CHAP.
with the organo-metals ; and the analogous hydrochloric
acid type the chlorides, iodides, cyanides, etc., thus —
H CH3 CH3 C2H5. H CH, C2H5
H H C2H5 Zn ' Cl Cl CN '
Gerhardt was quite justified in terming this classification
of organic compounds according to types a syst&me unitaire,
for all assumption of an opposite within the chemical com-
pounds themselves, or of a binary structure, was here entirely
eliminated. Each compound was looked upon as a complete
whole ; even in those cases where the dualistic conception
appeared to be indicated (especially in that of salts), deriva-
tives of water alone were seen.
The question now arises, — did Gerhardt himself believe
that he would get nearer to the solution of that problem,
which Berzelius had designated as being of supreme import-
ance to chemistry, by setting up those types and referring
organic compounds to them ? Did he consider that he had
thereby materially advanced the solution of the chemical
constitution of organic bodies ? The answer to this must be
in the negative, if we mean " constitution " in Berzelius' sense.
Gerhardt repeatedly expressed the opinion that it was
impossible to arrive at the true constitution of these com-
pounds, meaning by this the arrangement of their atoms
(V arrangement des atomes). In his view no strictly rational
formulae for organic compounds could be brought forward
which would satisfy this demand, since several formulae
showing different proximate constituents or residues might
be looked upon as equally correct, according to the modes of
formation or decomposition of the compounds. Grounds of
expediency alone must decide whether one formula was to
be preferred to another ; that formula which explained the
larger number of methods of formation and decomposition
of the particular compound in question was to be chosen.
This elastic view was brought prominently forward by Ger-
hardt at every opportunity, especially in the fourth volume
of his text-book, and he emphasised the point that the con-
stitution of compounds, according to the type theory, was not
v GERHARDT'S VIEWS UPON CHEMICAL CONSTITUTION 305
the same thing as their rational composition in Berzelius'
sense.
Formulae were for Gerhardt merely pictures of the
changes which chemical compounds underwent ; they simply
illustrated the modes of formation and decomposition of the
latter. Types, on their part, even when their composition
is exceedingly simple, " do not in any respect show how the
atoms are grouped, but only the analogies of their meta-
morphoses. The type is the unit with which are compared
all those compounds which show analogous decompositions,
or which are the products of analogous decompositions."
After this exposition of Gerhardt's system in its main
points, it will be intelligible why it has been spoken of as
resulting from the fusion of the type theory of Dumas with
the older radical theory. Gerhardt had made use of par-
ticular parts in both of these, and had recast them slightly
for incorporation into his syst&me unitaire. The idea that
organic compounds are constructed on certain models, to
which they can be referred, originated essentially in the
older type doctrine, but, although hidden, it was also
contained in the radical theory; in the latter, groups of
organic substances had been directly compared with
analogously constituted inorganic ones. Now it was of
fundamental importance for the success of the new type
theory that it borrowed from the radical theory the concep-
tion of atomic groups which behaved like simple substances ;
these groups could not, however, exist in the free state, as
had formerly been supposed, but could only act in place of
elements in compounds. This conception, coupled with that
of the alterability (by substitution) of these atomic com-
plexes, has proved to be absolutely correct, and at the same
time of the greatest value. The question of the proximate
composition of the above groups was left unanswered, and
indeed untouched, by Gerhardt, the key to its solution being
supplied from quite another quarter, i.e. by Kolbe and
Frankland.
While the older type theory of Dumas ascribed no
appreciable influence to the chemical nature of the con-
x
306 THE MODERN CHEMICAL PERIOD CHAP.
stituents of a compound upon the character of the latter,
Gerhardt showed his greater insight in this point also by
recognising certain principles of Berzelius' school, even
when he appeared mainly intent on opposing their spirit.
He pointed out that the elements or atomic groups, which
take the place of hydrogen in his types, determine according
to their electro-chemical nature the nature of the result-
•tcr
ing compounds. Thus he represented potash, rrO, as a
NO
basic, and nitric acid, TT2O, as an acid body, because the
hydrogen of the neutral water was replaced respectively in
these by an electro-positive and an electro-negative radical ;.
O TT
but alcohol, | 5Q, as an almost neutral compound, ethyl
M
being of pretty much the same nature as hydrogen itself.
This return to views, which had formerly been combated so
vigorously by that side, deserves to be especially noted.
The criticisms passed upon Gerhardt's type theory at
that time varied very much. Many chemists, especially
the younger ones, greeted it as an important conquest on
the part of research. But, as a matter of fact, the favourable
reception given to the typical view was due to grounds of a
practical nature ; men gave it as their opinion quite frankly,
that the chief advantage which the reference of organic
compounds to a few inorganic types brought with it, con-
sisted in its thereby simplifying the study of organic
chemistry. Liebig, who had criticised Gerhardt's earlier
efforts at classifying organic compounds most severely,1
acknowledged later on2 the " utility of the so-called type
theory"; but at the same time he laid stress upon the
point that it left the weighty question of the formation
of organic compounds untouched. Kolbe took up a more
drastic attitude than this; he designated the grouping of
organic compounds into the above four types a mere playing
with formulae. His own efforts he directed to replacing
1 Ann. Chem.,vol. Ivii. p. 93, Herr Gerhardt unddie organische Chemie.
2 Ann. Chem., vol. cxxi. p. 163.
v EXTENSION OF THE TYPE THEORY BY KEKULE 307
these purely formal types by real ones, which should stand
in a natural connection to the compounds derived from
them. Indeed, there was a serious danger that a door would
be opened for empty formulation. We have only to recall
that Odling and also Wurtz1 endeavoured to simplify
Gerhardt's types by referring those of water and ammonia
to the double and triple hydrogen ones. With this the
momentous question of the chemical constitution of organic
compounds was diverted appreciably from the direction
which had been given to it by the school of Berzelius and
Liebig. The term " constitution," already very elastic in
Gerhardt's theory, threatened to lose all meaning by formu-
lation so exaggerated.
Extension of the Type Theory ~by KekuU.
Gerhardt did not live to enjoy the cordial reception
which was given by many chemists to the opinions laid
down by him in the fourth volume of his text-book. His
type theory underwent a not inconsiderable extension the
year after his death (in 1857), by the assumption of the
so-called mixed types, which aimed at making clear the
relations of many organic compounds to two or more types.
The more general application of this by Kekule2 was
preceded by Williamson's idea that certain organic com-
pounds might be derived from multiplied or condensed types.
Just as chemical compounds proceeded from these through
the substitution of several hydrogen atoms by polybasic
radicals, so different types like water and ammonia, or water
and hydrogen, etc., were conjoined in order to derive from
them those substances which had previously been known
as copulated compounds (gepaarte Verbindungen), to distin-
guish them from others which were readily classified under
one type.3 Kekule recognised in the removal of this
1 Cf. Ann. Chim. Phys. (3), vol. xliv. p. 305.
2 Ann, Chem., vol. civ., p. 129.
3 The same idea which Kekule generalised later on had indeed occurred
to Gerhardt, in so far that he had referred the aminic acids (for example) to
the mixed ammonia- water type.
x 2
380 THE MODERN CHEMICAL PERIOD CHAP.
barrier the main advantage which was to be derived from
the assumption of mixed types, as is apparent from the
following extract : " The so-called copulated compounds
are not constituted differently from other chemical com-
pounds; they can in like manner with these be referred
to types in which hydrogen is replaced by radicals ; and, in
respect to formation and saturation-capacity, they follow
the same laws which hold good for all chemical com-
pounds."1
Before continuing the subject, a short account must be
given of the career and labours of the famous chemist just
named. — August Kekule, born at Darmstadt on 7th Sep-
tember, 1829, became assistant professor of chemistry at
Heidelberg in 1856, and then professor at Ghent from 1858
to 1 8 6 5 ; in the latter year he was called to the University
of Bonn,, where he continued to labour until his death on
the 13th of July, 1896. There could be no stronger
testimony of his profound and wide-reaching influence as a
teacher than in the large number of his pupils who have
attained to eminence in their science. By his Lehrluck der
organischen Ghemie (" Text-Book of Organic Chemistry,"
Erlangen, begun to be published in 1859), in which he
endeavoured to work out the typical view and subsequently
the structural doctrine to their logical conclusions, he
exercised an immense influence upon the chemists of his
time. More especially, by his happy conception of benzene
(the basis of the " aromatic" hydrocarbons) as a hexamethine,
he furnished the direction for one of the most important and
wide-spreading branches of chemical research ; and this still
holds with undiminished force at the present moment. His
researches on fulminate of mercury, unsaturated dibasic acids,
and the condensation of aldehyde (to name only a few) proved
him to be an admirable investigator. Mention may also be
made here of his share in the editing of a former journal, the
Kritische Zeitschrift fur Chemie, etc., and of the present
Annalen der Chemie, in the latter of which most of his
experimental work was published. A warm tribute to his
1 Ann. Chem., vol. civ. p. 139.
v SETTING UP OF MIXED TYPES 309
memory, from the pen of H. Landolt, is to be found in the
JBerichte, vol. xxix. p. 1971 ; and the KekuM memorial lecture
by F. R. Japp, delivered before the Chemical Society on
December 15th, 1897, is reprinted in the Journ. Ckem. Soc.
for February, 1898.
A few examples of formulae will serve to make the use
of the mixed types intelligible : —
Cso6 H
j| O, Benzene-sulphonic acid, referred to — ;
H
H2N
°2 O, Carbamic acid, referred to S£
H fy
H°
Almost simultaneously with the above extension of the
type theory, a suggestion was made by Kekule' which, thanks
to special circumstances, was destined to give this theory a
far more extended application. 2. propos of his researches
upon fulminate of mercury,1 he had expressed the opinion
that the methyl compounds and the numerous bodies derived
from them might be referred to the type of marsh gas, to
which he gave the equivalent formula C2H4. He illustrated
the connection of several compounds to the new type by the
following examples : —
C2H4 C2H3C1 C2HC13 C2H3CN C2C13(NO4)
Methyl hydride Methyl chloride Chloroform Aceto-nitrile Chloro-picrin.
Kekule's formulation' here is noteworthy, in that he
uses atomic weights which he had formerly regarded as
incorrect, i.e. H = l, C = 6, and 0 = 8. And a remark that
he makes strikes one as strange — viz. that the new type was
not to be taken in the sense of Gerhardt's unitary theory,
but in that of Dumas' types. From this one might infer
that marsh gas was not intended to be placed alongside of
Gerhardt's four types ; but, notwithstanding this, to give it
a place by itself does not seem to have been meant by
Kekule, since he adds, quite in the spirit of the newer type
1 Ann. Chem., vol. ci. p. 200.
310 THE MODERN CHEMICAL PERIOD CHAP'
theory, that what he mainly wishes to indicate by his
formulae are the relations in which the compounds enume-
rated stand to one another.
In the following year (1858), however, the meaning
which he attached to methane as the mother substance of
a large number of compounds became more clear. But a
detailed account of his views upon this must be reserved for
a later section of the book, when the transition of the type
theory into the structure theory will come to be discussed.
Before, however, this development of chemical hypotheses
could be consummated, much work had to be done in order
to get nearer to a knowledge of the chemical constitution of
organic compounds. The types themselves could not aid
in the solution of this problem without their own nature
being first elucidated. The key to the explanation of these
relations was forged by the labours and speculations of
Frankland and Kolbe. To these two investigators is
primarily due the more profound insight into the constitu-
tion of organic substances as opposed to the typical and
therefore superficial view (der typisch schematischen). Their
researches contributed more than any others to bring about
the change in direction taken by the type theory; they
were, in fact, the indispensable preliminary to that trans-
formation of theoretical opinions which completed itself
towards the end of the fifties. The correctness of this
statement will be seen from what follows in the succeeding
sections.
It is true that the typists place quite another estimate
upon the services of Frankland and Kolbe. The influence
exercised by these two men on the remodelling of the type
theory has not only been greatly minimised, but even the
exact contrary has been asserted, viz. that " typical " hypo-
theses influenced them.1
1 Such erroneous conceptions are always long of being dispelled. Thus,
in the description of "the theories of to-day" in Wurtz's Histoire des
Doctrines Chimiques, the influence of the above two scientists is very much
neglected. It seems hardly credible that Frankland, the real originator of
the doctrine of valency, should scarcely be mentioned in this publication.
The same applies to the general section of Kekule's Lehrbuch der organischen
KOLBE'S LIFE AND WORK 311
Development of the Newer Radical Theory by Kolbe —
A Survey of his Principal Work.
Before speaking of Kolbe's scientific labours, which pro-
duced a deep and lasting effect on the development of
theoretical chemistry, a short sketch of his life may be fitly
appended here.1
Hermann Kolbe, son of the Pastor of Elliehausen near
Gottingen, was born in 1818, and applied himself to the
study of chemistry under Wohler's stimulating guidance in
1838. The results of his first research were published in
1842, and for the next forty-two years he continued to
enrich his science with a long succession of the most
valuable experimental and theoretical work. His outward
life, if we except perhaps the first few years immediately
following his university curriculum, was that of a German
scientist. From 1842-47 he was assistant to Bunsen at
Marburg and then to Playfair in London, during which
time he occupied himself mainly with practical chemical
work; after this came the years of his literary apprentice-
ship (1847-51) in Brunswick, where he had gone at the
request of the well-known publishers, Fr. Vieweg and Son
to take up the editorship of the Dictionary of Chemistry
started by Liebig. This work not being of such a nature as
to satisfy him permanently, he willingly accepted in 1851 a
call to Marburg, where, as Bunsen's successor, he developed
exceptional powers as a teacher, especially in the years
following 1858. In 1865 he was called to the University
of Leipzig, and worked there with marked success until his
death on 25th November 1884.
Chemie ; there the debt due to Frankland is absolutely ignored, while the
share in the development of organic chemistry taken by Dumas, Gerhardt,
Laurent and Kekule himself is minutely detailed. At a later date (cf. Ber.
for 1880, p. 7) Wurtz unreservedly acknowledged Frankland's service by
stating that he was the first to put forward the idea of the saturation-
capacity of elementary atoms.
1 Cf. the memoirs which appeared shortly after Kolbe's death by E. v.
Meyer, Journ. pr. Chem. (2), vol. xxx. p. 417 ; Voit, Bayer. Acad., 1885 ;
and A. W. v. Hofmann, Ber., vol. xvii. p. 2809.
312 THE MODERN CHEMICAL PERIOD CHAP,
The great influence which Kolbe exercised upon chemical
science depended to an unusual degree upon his experimental
work, which will be discussed later on, but at the same
time also upon his eminence as a teacher, in which respect he
may be spoken of along with Liebig. His method of teaching
was very like that of the latter and had the best results ;.
the student of practical chemistry was taught to observe
and think for himself. Kolbe's gifts as a teacher were
greatly enhanced by his sound common-sense and organising
talent, which showed themselves in a marked degree in the
building and fitting up of the new Leipzig laboratory (in.
1868).
In addition to his work as a teacher, based as this was
upon oral instruction, Kolbe was also extremely active in a
literary sense. Apart from his numerous scientific papers,
valuable articles for the ffandworterbuch der Chemie (" Dic-
tionary of Chemistry"), and occasional pamphlets, he pub-
lished a large Lehrbuch der organischen Chemie (" Text-
Book of Organic Chemistry," Braunschweig, 1854-65), and
smaller text-books both of inorganic and organic chemistry
(1877-83). These books are distinguished by clearness in
arrangement, precision of expression, a delightful style, and
perspicacity and acuteness in discussion.
In his writings upon questions of theoretical chemistry>
published for the last fourteen years of his life in the
Journal fur praktische Chemie (of which he succeeded
Erdmann as editor in 1870), Kolbe gave play to a keen
criticism, which became intensified as time went on, upon
the defects and extravagances which he considered were
due to the direction taken by modern chemistry. If those
critiques were often strongly polemical and did not altogether
avoid the danger of introducing the personality of many a
brother chemist, still his only aim in them was the welfare
of his beloved science, which he believed to be in serious
danger. His efforts at exposing error were often wrongly
interpreted by many of his contemporaries, just as Liebig's
polemical writings were often perversely criticised.
KOLBE AND FRANKLAND'S PIONEERING WORK 31S
The Re-animation of the Radical Theory by Kolbe —
Frarikland's Co-operation.
At the time when Kolbe published the first of his more
important researches,1 the doctrine advocated by Berzelius,
that organic compounds contain definite radicals which act
similarly to elements in inorganic compounds, had been
driven into the background by the attack of unitarism.
Many chemists were of opinion that the partly arbitrary
supposition of hypothetical radicals could not advance the
science any further. The assumption of copulae (Paarlinge)
in the so-called copulated compounds satisfied very few. In
short, the old radical theory in its original form was held to
be no longer capable of existence. The preference given by
the school of Gmelin to the simplest views which were
possible is sufficient evidence of this sense of discouragement.
Facts alone were to decide ; any intelligent grouping of
these facts together was deemed useless.
Kolbe now united the conclusions deduced from his
first researches with the declining theory of Berzelius ; he
endued the latter with new life by casting aside whatever
of it was dead and replacing this by vigorous principles.
From his own and other investigations he came to the
conclusion that the unalterability of radicals, as taught by
Berzelius, could no longer be maintained, since the facts of
substitution had to be taken into account. He did, indeed,
adopt Berzelius' hypothesis of copulse, but attached another
meaning to these, since he allowed that they exercised a not
inconsiderable influence upon the compounds with which
they were copulated.2
If we desire to sum up the main results of his labours
just cited, and of his synthesis of trichloracetic acid, so
immediately connected with them, we may do so as follows :
Trichloro-methyl-hyposulphuric acid (our present trichloro-
methyl-sulphonic acid), discovered by him, and trichlor-
1 Ann. Chem., vol. xlv. p. 41 ; vol. liv. p. 145.
2 Cf. Ann. Chem., vol. liv. p. 156.
314 THE MODERN CHEMICAL PERIOD CHAP.
acetic acid, together with the compounds free from chlorine
obtained from these by reduction, were analogously consti-
tuted acids, copulated respectively with trichloro-methyl and
methyl, thus —
C2C13 + S2O6 + HO C2H3 + S2O5 + HO
C2C13 + C203+H0 C2H3 + C203 + HO
True, the mode in which these two radicals were
combined with the acids was not yet known, but the germ
of the correct explanation with regard to the constitution
of carboxylic and sulphonic acids, which was given by Kolbe
at a later date, was already present here.
This germ was soon to undergo further development by
investigations carried out at first by Kolbe alone, and
afterwards together with Frankland in London. From their
beautiful researches on the transformation of the alkyl
cyanides into fatty acids,1 they concluded with perfect
precision that methyl, ethyl, and similar radicals were
immediate constituents of acetic acid and its homologues.
Kolbe himself was led to the same conclusion by his
important work upon the electrolysis of salts of the fatty
acids ; 2 he saw in the methyl and butyl, separated at the
positive pole from acetic and valerianic acids respectively,
the proof of the correctness of this assumption. He believed,
indeed, that he had isolated the radicals themselves; and
even although he was wrong in so thinking (the hydro-
carbons obtained by him having double the molecular
weight that the radicals would possess), this affected but
little the question of the constitution of the carboxylic acids.
The chief goal of his endeavours, i.e. the discovery of the
true composition of the above and similar acids, was still kept
in view by him, notwithstanding this mistake.
The outcome of this work of his was that the view pre-
viously held with regard to these organic acids no longer
satisfied him. He did not, however, abandon this all at
once, but rather developed from it a theory which approxi-
1 Ann. Chem., vol. Ixv. p. 288.
2 Ibid., vol. Ixix. p. 258.
v KOLBE'S DOCTRINE OF CONJUGATE COMPOUNDS 315
mated to the truth, and which soon showed itself capable of
further improvement. Even so early as when writing the
articles upon Formulae and Copulated Compounds for his
Dictionary (in 1848), he expressed and gave reasons for the
view that the fatty acids were oxygen compounds of the
radicals hydrogen, methyl, ethyl, &c., combined with the double
carbon equivalent C2.1
Acetic acid contained as its immediate constituent an
atomic complex constituted similarly to that of the cacodyl
compounds. Cacodyl itself, which was here for the first
time interpreted as being arsenic copulated with two methyl
radicals, corresponded to the so-called acetyl of acetic acid,
i.e. C2H3C2 (not to be confounded with the radical acetyl of
to-day, which at that time was known as acetoxyl).
Even at this early date Kolbe expressed the significant
opinion that in the acetyl (C2H3C2) of acetic acid, " the last
C2 alone forms the connecting-link for the oxygen, the
methyl being in some sort only an appendage." This idea,
which recalls Berzelius' doctrine of copulse, was based
upon the point that it was unessential for the nature of
the acids whether hydrogen or methyl, ethyl, etc., was copu-
lated with the C2.
He entered into these important ideas in detail in a
treatise entitled, Ueber die chemische Konstitution und Natur
der organischen Eadikale (" Upon the Chemical Constitu-
tion and Nature of the Organic Radicals").2 Taking his
stand upon the basis of the older radical doctrine, he built
this up into a living theory by eliminating from it all those
principles which stood in contradiction to the facts. But at
the same time he did not remain stationary upon the point
of vantage he had thus gained.
Under the influence of the admirable researches of
1 Kolbe, like many others, made use at this time of Gmelin's equivalent
weights, in which H=l, C = 6, 0 = 8, S = 16, etc. His formulae were, not-
withstanding this, molecular formulas ; thus he gave carbonic acid, acetic
acid, alcohol, aldehyde and acetone the same atomic (i.e. molecular) weights
as we employ for these substances to-day.
2 Ann. Chem., vol. Ixxv. p. 211 ; vol. Ixxvi. p. 1.
316 THE MODERN CHEMICAL PERIOD CHAP.
Frankland l upon the alcohol radicals and the organo-metallic
compounds, which were begun at that time, Kolbe advanced
step by step. With regard to this period, he stated de-
finitely himself,2 that " the want of clearness in (my) con-
ception of the mode in which the so-called copulae were
combined, was a great weakness in the hypothesis of
copulated radicals. . . . It is Frankland's merit to have
been the first to throw light upon this, and therewith to
have thereby completely done away with the idea of copula-
tion, by recognising the fact that the various elements possess
definite saturation-capacities."
Kolbe readily embraced his friend's views, and copulse
thus received a totally different meaning from what they
had formerly done; henceforth they were to be regarded
as integral parts of organic compounds and not as mere
appendages.
This change in his opinions was not long of bearing
fruit. And here it was again the fatty acids whose
constitution he undertook to work out. In 1 8 5 5 3 he first
gave definite expression to the view that the acids, con-
sidered as anhydrous, were derivatives of carbonic acid ;
1 Sir Edward Frankland, born at Churchtown, near Lancaster, on
January 18th, 1825, studied chemistry at the Museum of Practical Geology
in London, then with Liebig and Bunsen, and also under Kolbe' s stimulus
in Germany. He afterwards filled successively the chairs of chemistry in
the Owens College,' Manchester (1851-7), St. Bartholomew's Hospital,
London (1857), Royal Institution (1863), Royal School of Mines (1865), and
Normal School of Science, South Kensington (1881). This last chair he
resigned in 1885, retiring then from professorial work. Frankland attracted
the attention of chemists even by his earliest work, which led him to the
discovery of the organo-metals, and also by his joint researches with Kolbe.
The chief share which he took in the development of our present views
upon the valency of the elements will be discussed in detail later on, while
his other memorable investigations in organic chemistry will often have to
be referred to under the special history of this branch. Frankland's papers
have mostly been published in the English journals and the Annalen der
Chemie ; in 1877 they were collected into one volume, entitled Researches
in Pure, Applied and Physical Chemistry. He is also the author of the
text-book, Lecture Notes for Chemical Students.
2 Cf. Das chem. Laboratorium der Universitcit Marburg, etc. (Braun-
schweig, 1865), p. 32.
3 Handwb'rterbuch der Chemie, vol. vi. p. 802.
v DERIVATION OF ORGANIC COMPOUNDS FROM INORGANIC 317
for instance, acetic was methyl-carbonic acid, i.e. C2O4, in
which one oxygen-equivalent was replaced by methyl, C2H3.
The hydrated acids he still regarded dualistically as com-
pounds of the anhydrides with water.
The assumption that those acids were substitution-
products of carbonic acid had developed itself from the
views held regarding the organo-metallic compounds. Just
as Frankland explained cacodylic acid as arsenic acid with
two methyls in the place of two equivalents of oxygen,
and stanno-ethyl oxide as the corresponding tin derivative,
so did Kolbe happily interpret the constitution of other
organic compounds. He soon advanced beyond the field
of the organic acids, and developed the idea, similar to
that mentioned above, that many organic substances are
to be regarded as derivatives of carbonic acid, and many
others as derivatives of sulphuric. How this idea expanded
into a perfect whole is seen from his writings in the years
185 7-5 8,1 and also from those portions of his text-book which
were written both at that time and shortly before it. These
theoretical considerations and, with them, the revived radical
theory" attained to their completed form in a treatise pub-
lished in 1859, entitled, Ueber den naturlichen Zusammen-
hang der organischen mit den unorganischen Verbindungen,
die wissenschaftliche Grundlage zu einer naturgemdssen Klassi-
fikation der organischen chemischen Korper ("Upon the
Natural Connection existing between Organic and Inor-
ganic Compounds, being the Scientific Basis of a Rational
Classification of Organic Chemical Substances ").2
The main outcome of Kolbe's speculations is given in
the following sentence : " Organic compounds are all de-
rivatives of inorganic, and result from the latter — in some
cases directly — by wonderfully simple substitution-processes."
This idea runs through the whole treatise, and is illustrated
1 Ann. Chem., vol. ci. p. 257 ; this paper is a joint one with Frankland,
i.e. Kolbe lays emphasis on the point that he is here giving utterance both
to his own and Frankland's views. Cf. also Kolbe's pamphlet (1858), Ueber
die chemische Konstitution organischer Verbindungen ("On the Chemical
Constitution of Organic Compounds ").
2 Ann. Chem., vol. cxiii. p. 293.
318 THE MODERN CHEMICAL PERIOD CHAP.
with the most convincing clearness by numerous examples
taken from the wide field of organic chemistry.
The alcohols, carboxylic acids, ketones and aldehydes
were derived, according to Kolbe, from carbonic acid,
(C2O2)O2, and its hydrate, C2O2.y ^, respectively. The
polybasic carboxylic acids proceeded in the same way from
two or three molecules of the hydrated carbonic acid, through
the entrance of polyatomic radicals, just as the monobasic
did from one molecule. Similar definite views were ex-
pressed by Kolbe with regard to other classes of organic
compounds, e.g. the phosphinic and arsenic acids, amines
and amides, and the organo-metals, which he derived in the
simplest manner from inorganic compounds. He laid the
utmost emphasis upon his formulae being the unambiguous
expression of precise opinions ; with Gerhardt's assumption
that various constitutional formulae might, with equal justice,
be set up for one and the same compound, he had absolutely
nothing in common.
Kolbe himself gave a striking proof in the treatise
above mentioned of the capacity for development of his
views respecting the constitution of organic compounds.
He comprised in his survey not merely those classes of
compounds which were known, but advanced beyond them
to others at that time unknown. From the relations so
clearly recognised by him as existing between the alcohols
and the carboxylic acids, he deduced the possibility of pre-
paring new varieties of alcohols ; he predicted the existence
both of secondary and of tertiary alcohols,1 and even went
so far as to indicate a probable method for preparing and
decomposing the first of these. No such brilliant deduc-
tive treatment of chemical questions had as yet been seen
in organic chemistry. And the discovery of those classes
of compounds which he had prognosticated had not to be
waited for long ; Friedel isolated secondary propyl alcohol
in 1862, and Butlerow tertiary butyl alcohol in 1864.
The comprehensive speculations of Kolbe upon the
1 Cf. Ann. Chem., vol. cxiii. p. 307.
v KOLBE'S EXPERIMENTAL RESEARCHES 319
constitution of organic compounds could not have attained to
the firm hold and the wide significance which they did, had
they not been conjoined throughout with admirable experi-
mental work. We shall frequently have occasion, in the
special history of organic chemistry, to refer to those labours,
through which the rational composition of important classes
of compounds was first arrived at with certainty. Thus it
was his researches upon lactic acid which showed ifc to be
oxy-propionic, and the corresponding alanin to be amido-
propionic acid. Glycollic acid and glycocoll were likewise
shown by Kolbe to belong to the same class, the one being
proved to be oxy-, and the other amido-acetic acid ; he also
recognised salicylic acid as oxybenzoic, and the so-called
benzamic acid (Benzaminsdure) as amido-benzoic. He was
thus in a position to clear up the constitution of compounds
upon whose investigation chemists of such eminence as
Kekule and Wurtz had laboured in vain. Numerous sub-
stances, the names (Trivialbezeichnungeri) given to which
showed how little was known with respect to their constitu-
tion, received from Kolbe their proper place among other
compounds. The conversion of malic and tartaric acids into
succinic, which was carried out by Schmitt1 at his suggestion,
revealed at one stroke the hitherto unknown relations exist-
ing between the two first of these acids and the last. By
his researches upon taurine, which he taught how to prepare
artificially, he proved how both it and the isethionic acid
produced from it were constituted analogously to alanin
and lactic acid. And the same clearness shed itself over
the rational composition of asparagine and aspartic acid,
which he was the first to interpret correctly.
The above are merely the results of work performed
within a short period of time, but they are amply sufficient
to prove what undying service he rendered in investigating
the chemical constitution of organic compounds. And no
1 Rudolf Schmitt, born in 1830, filled the chair of chemistry at the
Dresden Technische Hochschuleirom 1871 to 1893,having previously occupied
other chemical posts at Marburg, Cassel and Niirnberg. His admirable
experimental researches extend over many branches of organic chemistry,
but deal more especially with the aromatic compounds.
320 THE MODERN CHEMICAL PERIOD CHAP.
mention has been made here of a large number of other
researches carried out at his suggestion and with his co-
operation; among these were the work of Griess upon the
class of diazo-compounds, Oefele's discovery of the sulphines,
and Volhard's synthesis of sarcosine.
In order to round off in some degree this short record of
Kolbe's achievements, we ought further to recall several
investigations made in the years following, i.e. after 1863,
in which he was guided throughout by the aspiration to
gain the furthest possible insight into the constitution of
organic compounds. Among these we may refer to his proof
of malonic acid resulting from cyan-acetic, and being there-
fore carboxyl-acetic acid, the discovery of nitro-me thane,
the series of memorable researches upon salicylic and para-
oxybenzoic acids, and lastly, that upon isatoic acid, which
was cut short by his death.
Kolbe's Attitude towards the older and the newer Chemistry.
In all Kolbe's investigations, whether speculative or
experimental, we feel the salutary historic method by which
they are characberised. He built upon the edifice already
existing, and remained in his scientific efforts in continuity
with the chiefs of the classical school. He was always glad
to acknowledge that his success as a chemist was due
primarily to Berzelius, and, after him, " to the great exem-
plars Liebig, Wohler and Bunsen, who, to use a phrase of
Berzelius, were true workers in chemistry " (wahre Bearleiter
der Chemie gewesen sind).
The criticisms passed upon Kolbe by his contemporaries,
in so far as regarded his attitude to organic chemistry,
differed very greatly. The exponents of the earlier period
appreciated his services better than the disciples of the
type theory, — a theory which he himself did not value at its
true worth. A few remarks upon the relation between
Kolbe's views and those of the typists will be in place here.
As already stated, he spoke of the type theory as being un-
KOLBE'S REAL TYPES 321
scientific ; he saw in it not a real theory but merely a play
upon formulae. In spite of his definite utterances upon this
point, however, it has been frequently asserted that he took
Gerhardt's doctrine of types as his basis, and that therefore
his derivation of organic compounds from carbonic acid,
carbonic oxide, sulphuric acid, sulphurous acid, etc., coin-
cided with that from the three types of hydrogen, water
and ammonia. Kolbe did indeed connect organic with
inorganic compounds, but he repeatedly emphasised the
point l that these latter were real types, as opposed to the
formal ones of the type theorists. His most ardent wish
was to fathom the chemical constitution of organic com-
pounds ; but to merely classify the latter upon certain models
or to go so far as to force them into arbitrary types, was
in the highest degree distasteful to him. Kolbe attached
special weight to the relations actually existing between
organic and inorganic bodies, whence the emphasis laid in
the title of his treatise, spoken of above, upon the " natural
connection between these as forming a scientific basis for a
rational classification of organic substances." Hence, also,
his attempts, begun at an early date, to prepare organic com-
pounds artificially from simple inorganic ones, with the object
of thus gaining an insight into their chemical constitution.
We thus see Kolbe pursuing his own way, not led aside
by the criticisms of his contemporaries, but working with
wonderful effect, more particularly in advancing a knowledge
of the rational composition of organic compounds. The
older radical theory acquired through him new life, and the
radicals themselves received a more profound meaning.
While in the type theory the latter were looked upon as
residues whose nature could be no further investigated,
Kolbe devoted his whole energies to breaking up the
radicals into their immediate constituents. To give but a
few examples, — he showed cacodyl to be arsene-dimethyl,
acetyl to be a compound of methyl and carbonyl, and the
alkyls to be derivatives of methyl. These and other results
of his investigations, together with the rich fruits of Frank -
1 Cf. (e.g.) Journ. pr. Chem. (2), vol. xxviii. p. 440.
Y
322 THE MODERN CHEMICAL PERIOD CHAP.
land's labours, were undoubtedly of the first importance,
indeed indispensable, for the development of the new type
doctrine into the structure theory.
These two men, the workers of greatest originality in the
field of organic chemistry during the storm-and-stress period
of the fifties, thus contributed most materially by their
labours to the recognition of the fact th.at the peculiarity of
Gerhardt's types rested upon the different saturation-capa-
cities of the elements which they contained. The chief
merit of having worked as a pioneer in this direction belongs
to Frankland.
THE FOUNDING OF THE DOCTRINE OF THE SATURATION-
CAPACITY OF THE ELEMENTS BY FRANKLAND.
In the foregoing section the influence exercised by
Frankland on the views developed by Kolbe with regard
to the constitution of organic compounds has been already
distinctly emphasised. It was Frankland who, in his
memorable paper, — On a New Series of Organic Compounds
containing Metals 1 — furnished the proof that the copulation
of radicals with elements (e.g. carbon, arsenic and sulphur),
as taught by Kolbe, depended upon a property inherent in the
elementary atoms of the compounds just named. The
notion of copulation was recognised by Frankland as being
one-sided, and the misconception which had crept in from
its use was done away with by him, — the idea, namely,
that the radicals present as so-called copulse in organic
substances exercised no appreciable influence upon those
compounds with which they were supposed to be copulated.
From his experiences gained from the organo-metallic
compounds, Frankland developed the doctrine of the valency
of the elements. If, freeing our minds from all prepossession,
we turn our glance backward, we recognise the germ of this
doctrine as being already present in the law of multiple
1 Phil. Trans., vol. cxlii. p. 417; Ann. Chem., vol. Ixxxv. p. 329. This
paper was read before the London Chemical Society in 1852.
v THE DOCTRINE OF SATURATION-CAPACITY 323
proportions, which stated that the elements show different,
but at the same time perfectly definite stages in their
combinations. Among the facts known at a very early
period was, for instance, that of one atom of phosphorus
combining with three and five atoms of chlorine to definite
compounds ; but the expression for this and other similar
observations, viz. that phosphorus and many other elements
were possessed of more than one valency, i.e. could manifest
varying saturation-capacities, had yet to be found. Further,
no one had any clear conception of a limit to the saturation-
capacities of elements, and, what was of the first importance,
a sharp distinction between the terms " atom " and " equiva-
lent " was still wanting. With regard to this latter point,
the experiences gained respecting the substitution of the
hydrogen of organic compounds by chlorine, oxygen, etc.,
and the deductions drawn from these had tended to elucidate
matters. So early as 1834 Dumas had pointed out that
1 atom of hydrogen was replaced by 1 atom of chlorine,
but only by J an atom of oxygen; those quantities were
therefore equivalent to 1 atom of hydrogen. The idea of
the " replaceable value " of certain metals also came more
distinctly into prominence through the doctrine of polybasic
acids, already spoken of; this was exemplified, for instance,
in Liebig's statement that 1 atom of antimony was equiva-
lent to 3 atoms of hydrogen, but one of potassium only to 1
atom of hydrogen. Notwithstanding this, however, a precise
expression for such facts as these had not yet been found.
In the course of the forties the conception of a chemical
equivalent as distinguished from an atom, a conception
which had been arrived at after so much labour, completely
died out ; the growing influence at that time of the Gmelin
school affords us eloquent testimony of this backward
step.
It is a remarkable fact that, for establishing the doctrine
of valency, it was not the simple compounds of inorganic
chemistry but the more complicated ones of organic that were
called into service. The relations which in the former
found clear expression, and were easily read in the law of
Y 2
324 THE MODERN CHEMICAL PERIOD CHAP.
multiple proportions, had to be first laboriously deciphered
here from organic compounds.
As stated already, it was the organo-metals from which
Frankland deduced the results which constitute the kernel
of our present theory of valency. He acted as pioneer in
this branch more than any other man, and distinguished
himself by his admirable investigations. Before him (more
particularly) Bunsen had accomplished his memorable work
on the cacodyl compounds, and cacodyl itself had been
designated by Kolbe as arsene-dimethyl. Relying upon his
own observations on the stanno-ethyl compounds, and on the
behaviour of the cacodyl derivatives and other bodies, Frank-
land proved with convincing clearness that the theory of
copulse was untenable. Frankland's train of reasoning was
somewhat as follows : — If we start with the latter theory, we
must assume that the power of the metals to combine with
oxygen is not altered by their being copulated with radicals.
But facts tell against such an assumption, as is seen at a
glance from the following examples: — Tin-ethyl (SnC4H5;
C = 6) ought, according to that theory, to unite with oxygen
in two proportions, but in reality it is only capable of taking
up one equivalent of this element, and not two, like tin itself.
Cacodyl, which is arsenic copulated with two methyls, does
indeed form two oxides, from which it might be argued that
the one with one equivalent of oxygen corresponded to
arsenic sub-oxide, and the other with three equivalents to
arsenious acid ; but this hypothesis affords no explanation
whatever of the fact that the latter compound is very
readily oxidisable, whereas its supposed analogue cacodylic
acid cannot be oxidised by any means.
These and similar contradictions were done away with by
Frankland in the simplest manner, by the assumption that
the so-called copulated compounds were derivatives of in-
organic bodies in which oxygen had been replaced by its
equivalent of hydrocarbon radicals. Stanno-ethyl oxide was
explained as tin dioxide, Sn02, in which one equivalent of
oxygen was replaced by ethyl, and cacodyl oxide as arsenious
acid, in which two equivalents of oxygen had been sub-
y THE SATURATION-CAPACITY OF THE ELEMENTS 325
stituted by two methyls. Frankland then proceeded to
extend this conception to other compounds in the most
felicitous manner, and — what was especially important —
thus brought the laws which are shown in the composition
of organic and inorganic substances into relation with the
fundamental properties of the elements which these contain.
He expressed his views upon this point in the following
sentences,1 which, from their great importance, have a claim to
a special place in a history of chemistry : " When the formulae
of inorganic chemical compounds are considered, even a super-
ficial observer is impressed with the general symmetry of their
construction. The compounds of nitrogen, phosphorus, anti-
mony, and arsenic, especially, exhibit the tendency of these
elements to form compounds containing 3 or 5 atoms of other
-elements ; and it is in these proportions that their affinities
are best satisfied : thus in the ternal group we have NO3
NH3, NI3, NS3, PO3, PH3, PC13, SbO3, SbH3, SbCl3, AsO3.
AsH3, AsCl3, etc. ; and in the five-atom group, N05, NH4O,
NH4I, P05, PH4I, etc. Without offering any hypothesis
regarding the cause of this symmetrical grouping of atoms,
it is sufficiently evident, from the examples just given, that such
a tendency or law prevails, and that, no matter what the
character of the uniting atoms may ~be, the combining power of
the attracting element, if I may be allowed the term, is
•ahoays satisfied ~by tine same number of these atoms"
In this way was established the doctrine that a varying,
but at the same time, within certain limits, definite satura-
tion-capacity appertains to the atoms of the elements. For
the ones which have just been named this was expressed
by the numbers 3 and 5; Frankland did not assume any
higher stage of saturation for them. By this treatise of
his, so rich in ideas and facts, he opened up a new field in
theoretical chemistry, which, assiduously cultivated as it has
been ever since, has served both as the centre- and the
starting-point for all chemical investigations. Under the
influence of the theory of valency all theoretical chemical
views thenceforth developed themselves, as will be clearly
Phil Trans., vol. cxlii. p. 417 ; Ann. Chem., vol. Ixxxv. p. 368.
326 THE MODERN CHEMICAL PERIOD CHAP,
seen from the following sections. The happy interpretation
of the constitution of the so-called copulated compounds was
the immediate cause of this great advance, in so far that
Frankland proved copulation to be a consequence of satura-
tion-capacity.
After the definite valency of particular elements had
bqen established by Frankland, it might have been imagined
that every chemist could have deduced for himself the
saturation-capacities of other elements from their behaviour.
Frankland's pioneering work did not, however/ produce fruit
with such rapidity. How slowly his views found acceptance
among chemists is proved by a paper of Odling's, published
in 1854, and entitled On the Constitution of Acids and Salts.1
The latter chemist still adhered firmly to the type theory.
He argued that salts and acids, especially those containing
oxygen, can be referred to the simple or multiple water type
in such a way that the hydrogen of the latter is partially
or completely substituted by elementary or compound
radicals of definite replaceable value. This latter term was
used by Odling to express what Frankland had done by
the word atomic. Iron and tin had, according to Odling,
two replaceable values, whose magnitudes he indicated by
the dashes which have since then been so largely employed,
thus : Fe" and Fe'", Sn' and Sn". Thus far he followed
Frankland's conception of the saturation-capacity of the
elements. For the polybasic acids he accepted Williamson's
views, in that he assumed in them oxygenated radicals of
definite replaceable value, which were introduced into the
type (H2O)n. Just as sulphuric acid was built up on the
double water type by the entrance of the diatomic radical
SO2, so he derived phosphoric and arsenic acids from the
triple water type (3H20) by introducing the atomic groups
(PO)'" and (AsO)'" ; while in the carbonates the radical CO,
with a replaceable value of 2, was assumed, and so on. But
mischievous obscurations now began to be mixed up with
this. As a result of his one-sided typical conception, Odling
did not hesitate to assume that the diatomic radical S02 acted
1 Journ. Chem. Soc., vol. vii. p. 1.
v VALENCY OF ELEMENTS AND RADICALS 327
as monatomic in dithionic acid,1 and the diatomic radical
CO as monatomic in oxalic acid ; and this last (for example)
he referred to the double water type, thus: (CO)'^p 1 20".
But, with all this, Odling deserves credit for being instru-
mental in causing a constant replaceable value to be ascribed
to particular elements, to hydrogen and oxygen in especial,
whereby the atomic weights of these two latter served as
standards for fixing the replaceable values of other elements
and compound radicals. Williamson afterwards helped most
materially to clear up the meaning of Odling's formulae, and
to bring about a more intelligent conception of the constitu-
tion of chemical compounds.2
- The utterances of Wurtz 3 and of Gerhardt 4 upon the
saturation-capacity of the nitrogen atom also showed that
Frankland's ideas acted but slowly ; for the last-named had
expressed himself on this point in almost exactly the same
sense three years previously. In many cases chemists were
content with merely the notion of compound radicals, with-
out investigating the influence of the contained elements
upon the saturation-capacities of . these complexes ; this
applied in an especial degree to the radicals composed
of carbon and hydrogen, with whose replaceable value (that
of the radicals) various eminent investigators occupied
themselves.
The Recognition of the Valency of Carbon.
A considerable time elapsed before any definite utter-
ance was made with regard to the valency of the carbon of
alcohol radicals — the organic element in the true sense of the
term. Instead of deducing this fundamental property from
its oxygen compounds, carbon monoxide and dioxide, a more
1 This he formulated :— (S02)'(S02)' \ 2Q
2 Cf. Journ. Chem. Soc., vol. vii. p. 137 ; or Ann.'Chem., vol. xci. p. 226.
3 Ann. Chim. Phys. (3), vol. xliii. p. 492 (1855). '
4 TraM de Chimie, vol. iv. pp. 595 and 602 (1856).
328 THE MODERN CHEMICAL PERIOD CHAP.
tedious method was adopted; it was the investigation of
carbon-containing radicals which led to the final solution
of the question. Among the researches which were of
effective service here, we must first mention that by Kay,1
made at Williamson's suggestion, upon "tribasic formic
ether " ; this compound, which resulted from chloroform
and sodium ethylate, was regarded as a derivative of three
atoms of ethyl alcohol, in which the three atoms of basic
hydrogen had been replaced by the "tribasic radical of
chloroform, CH." Ranking alongside of this important
piece of work came that of Berthelot upon glycerine.2
Aided materially by Wurtz's expositions, Berthelot charac-
terised this compound as a triatomic alcohol, since he
assumed in it a tribasic radical, C6H5 (C = 6), replacing three
atoms of hydrogen in the triple water type. To the alkyls
which took the place of three atoms of hydrogen, diatomic
ones were soon added, ethylene being so designated by
H. L. Buff.3 The brilliant discovery by Wurtz of the first
known diatomic alcohol, glycol,4 served as a corroboration of
this view.
Chemists were, it is true, upon the track of the cause
of the different replacing values of those radicals (CH)'",
(C6H5)'", and (C2HJ", for we find utterances by Gerhardt
and Wurtz to the effect that ethylene was dibasic, because
one atom of hydrogen had been withdrawn from the mono-
basic ethyl, and glyceryl tribasic, because it contained two
atoms of hydrogen less than the corresponding propyl. But
no one had attained to a complete explanation of these
radicals ; their saturation-capacities had never been distinctly
referred back to that of carbon.
In a paper entitled, Ueber die Konstitution und die
Metamorphosen der chemischen Verbindungcn und uber die
chemische Natwr des Kohlenstoffs (" On the Constitution and
Metamorphoses of Chemical Compounds, and on the Chemi-
1 Journ. Chem. Soc., vol. vii. p. 224.
2 Ann. Chim. Phys. (3), vol. xli. p. 319.
3 Ann. Chcm., vol. xcvi. p. 302.
4 Comptes Rendus, vol. xliii. p. 199.
v VALENCY OF CARBON 329
cal Nature of Carbon"),1 which was published in 1858,
Kekule drew the following nearly allied conclusion. He
applied to carbon what had already for a long time been
recognised with regard to other elements, — to nitrogen and
its chemical analogues in the first instance. The reasons
given by him for carbon being tetravalent are contained in
the following sentences : — " If we look at the simplest com-
pounds of this element, CH4, CH3C1, CC14, CHC13, COC12,
CO2, CS2 and CHN, we are struck by the fact that the
quantity of carbon which is considered by chemists as the
smallest amount capable of existence — the atom — always
binds four atoms of a monatomic or two of a diatomic
element, so that the sum of the chemical units of the ele-
ments combined with one atom of carbon is always equal to
four. We are thus led to the opinion that carbon is tetra-
tomic." This train of thought is almost the same as that
which led Frankland to deduce the tri- and penta-valence
of nitrogen, phosphorus, arsenic and antimony,2 the latter
chemist having also arrived at the saturation-capacities of
these elements from a study of their simplest compounds. It
follows from this that the above utterance of Kekule cannot
be regarded as a thoroughly original achievement, all the
more since the tetravalence of carbon had already been
recognised both by Kolbe and Frankland, and especially as
it formed the basis of the latter's statements upon the
constitution of organic compounds.3 In curious contrast
1 Couper, too, independently of Kekule, and shortly after the appearance
of the paper just cited, expressed the view that the atom of carbon was
tetravalent (cf. Comptes Rendus, vol. xlvi. p. 1157).
2 Cf. p 325.
3 Cf. Kolbe's publication entitled Zur Entwickelungsgeschichte der
theoretischen Chemie ("Contribution to the History of the Development of
Theoretical Chemistry"), Leipzig, 1881, p. 26 et seq., especially p. 33.
Others, too, have claimed for Kolbe the merit of being the first to perceive
the tetravalence of carbon, e.g, Blomstrand, who thus expresses himself in
his Chemie der Jetztzeit ("Chemistry of the Present Time"), p. 110 : "No
other chemist can lay the same claim as Kolbe to be regarded as the origin-
ator of the doctrine of the saturation -capacity of carbon. Alongside of him
must be placed Frankland, whose uninterrupted researches, conceived and
carried out with equal felicity, continually furnished new supports in aid of
the doctrine mentioned above, — a doctrine which comprises in itself every-
330 THE MODERN CHEMICAL PERIOD CHAP.
with the high value which most chemists have placed upon
this service of Kekule's is the depreciatory way in which
he talks of it himself.1
Kekule's service in this point must be sought for in the
fact that he endeavoured to get at the root of the problem
as to how two or more carbon atoms combine with one
another, and how their mutual affinities are satisfied. The
immediate result of these speculations was the doctrine of
the " linking of atoms " ( Verkettung der Atome) in chemical
compounds. Indirectly, Kolbe's and Frankland's views had
a most material share in developing this crowning edifice of
the structure theory.
thing that relates to saturation, and which has found in Kolbe's carbonic
acid theory by far its most important application." A. Glaus (Journ. pr.
Chem. (2), vol. iii. p. 267) has written in a similar sense. Kekule is there-
fore not justified in claiming for himself the merit "of having introduced
the idea of the atomicity of the elements into' chemistry " (" den Begrijf der
Atomigkeit der Elemente in die Chemie eingefiihrt zu haben "), (cf. Kekule,
Ztschr. Chem. for 1864, p. 689). This idea was without doubt primarily
due to Frankland, who expresses himself clearly and unequivocally on the
point hi his Experimental Researches (1877), p. 145, as follows : " This hypo-
thesis which was communicated to the Royal Society in the second of the
following papers" (cf. p. 325 of this book), "on 10th May 1-852, constitutes
the basis of what has since been called the doctrine of atomicity or equiva-
lence of elements ; and it was, so far as I am aware, the first announcement
of that doctrine."
1 Thus Kekule says, at the close of his above-mentioned treatise, p.
109 : "Lastly, I feel bound to emphasise the point that I myself attach but
a subordinate value to considerations of this kind. But since in chemistry,
when there is a total lack of exact scientific principles to go upon, we have
to content ourselves for the time being with conceptions of probability and
expediency, it appears appropriate that those views should be published,
because they seem to me to furnish a simple and tolerably general expression
precisely for the latest discoveries, and because therefore their application
may perhaps conduce to the finding out of new facts."
CHEMISTRY DURING THE LAST FORTY YEARS 331
DEVELOPMENT OF CHEMISTRY UNDER THE INFLUENCE
OF THE DOCTRINE OF VALENCY DURING THE LAST
FORTY YEARS.
The chemical atomic theory had been in existence for
nearly fifty years before the natural inference was drawn
with sufficient exactitude from it that each elementary atom
possesses a definite saturation-capacity, and that this is
expressible in some cases by a constant factor, but in most-
cases by a varying one/ In recognising this a great advance
was made, — an advance which showed itself particularly in the
fact that, after the establishment of the valency theory by
Frankland, people attained to a more definite conception of
the chemical constitution of inorganic, and more especially
of organic compounds. From thenceforth continuous efforts
were made to solve this problem, first recognised in its
fullest signification by JSerzelius, by the aid of the ideas
which Frankland had either himself expressed or had
induced in others. Chemists endeavoured, by breaking up
compound bodies (in part actually and in part on paper
only) and distributing the elementary atoms according
to their supposed saturation-capacities, to work out the
mutual relations of these ultimate constituents. In this
way there shone forth from valency a light which now
illumines the whole field of chemistry.
The theory of the linking of atoms was considered
by most chemists as the necessary result of the idea
that a saturation-capacity (with respect to other ele-
ments), expressible by figures, belonged to the atoms of each
individual element. With the development of this view, in
organic as well as in inorganic chemistry, many brains
have been busily engaged for the last forty years. The
idea of a definite saturation-capacity for each element has
formed a necessary aid in the solution of numerous important
points which have come up during this period, e.g. the
question of the nature of valency, the reasons for many cases
of isomerism hitherto unexplained, etc., and it still remains
an indispensable guide in all scientific chemical investigations.
332 THE MODERN CHEMICAL PERIOD CHAP.
Beginnings of the Structure Theory — KekuU and Couper.
The theory of types, according to which all organic
compounds were referred to a few simply constituted bodies,
had been rendered objectless by Frankland's conception of
that property of elements which we now term valency.
The types now presented themselves as hydrogen compounds
of mono-, di-, tri-, and tetra-valent elements. Had Frank-
land's ideas at once received the attention which they
merited, the detailed development of the theory of types,
as given by Gerhardt in the fourth volume of his text-book,
could have been entirely dispensed with.
Out of Frankland's idea of saturation-capacity there
grew the further notion that the elementary atoms could be
combined among themselves by one or more affinities,
according to their nature, and that a disappearance of
individual affinities took place as the result of this. This
idea was first advanced by Kekule, and shortly after by
Couper, in the treatises already referred to (in 1858).
These therefore contain the beginnings of the structure
theory.1
After having deduced the " tetratomicity " of carbon
from the composition of a number of simple compounds of
that element, Kekule expressed himself upon the constitu-
tion of compounds which contain more than one atom of
carbon as follows : 2 " In the case of substances containing
several carbon atoms we must assume that at least some of
the atoms (of the other elements present) are held bound by
the affinities of the carbon atoms, and that the latter are
themselves linked together, whereby a part of the affinity
of the one (carbon atom) is necessarily tied by an equally
large part of the affinity of the other."
"The simplest and therefore the most probable case of
1 The term "structure" (Struktur) was first introduced by Butlerow
(Ztschr. IChem. for 1861, p. 553); through it he quite unintentionally
awakened the erroneous idea that the actual spacial arrangement of the
atoms could be arrived at by the aid of the above hypothesis.
2 Ann. Chem., vol. cvi. p. 154.
v BEGINNINGS OF THE STRUCTURE THEORY 333
such a combination (Aneinanderlagerung) of two carbon
atoms is that in which one affinity of the one atom is tied
by one affinity of the other. Of the four affinity units of
each of the two carbon atoms, two are thus taken up in
keeping both atoms together ; six consequently remain over,
to be available for atoms of other elements."
Here, therefore, there was set up the hypothesis that the
carbon atoms join together,1 and lose in consequence a
portion of their affinities. Starting with the assumption
that more than two atoms of carbon can coalesce in the same
manner, Kekule generalised this particular case by establish-
ing the value 2n + 2 for the saturation-capacity of the
complex Cn. He did not, however, remain stationary at
this point, but represented further that "a more compact
combination of the carbon atoms" might be assumed in
other organic compounds, e.g. benzene and naphthalene. As
the " next most simple coalition of carbon atoms " he con-
ceived the case of the mutual interchange of two affinity-
units. The relations, too, of other polyvalent elements to
the carbon atoms were taken into account by him, and he
gave illustrations to show that these were bound either by
all their affinities or by a portion of them to the affinities
of the carbon.2 The main features of the doctrine of the
" Linking of Atoms " (Bindung der Atome) were contained in
those sentences of Kekule's.
Almost at the same time Couper,3 independently of Kekule,
arrived at similar views with respect to the mutual linking
of several carbon atoms. Being definitely of opinion that
Gerhardt's doctrine of types did not satisfy the claims required
by a theory, he made the attempt to get at the constitution
of chemical compounds by falling back upon the elementary
atoms. He laid stress upon the point that, in addition to the
affinity proper (Wahherwandtschaff), the degree of that
affinity (Gradveiwandtschaft) of the small particles came into
1 Sick aneinander lagern.
- Cf., for instance, Ann. Chem., vol. cvi. p. 155.
3 Comptes Rendm, vol. xlvi. p. 1157 ; Ann. Chim. Phys. (3) vol. liii.
p. 469.
334 THE MODERN CHEMICAL PERIOD CHAP.
play in the formation of chemical compounds. For the atom
of carbon the highest power of combination was expressible
by the number 4. In general he adopted Frankland's
doctrine of the varying saturation- capacities of the elements.
Couper further laid great emphasis upon the capacity of the
carbon atoms to unite with one another, and this in such a
manner that a part of their own individual power of com-
bination was thereby neutralised. This linking of the atoms,
he illustrated by bars drawn between the chemical symbols of
the combining particles ; he thus laid the foundation of the
so-called " structural formulae."1 The following examples will
serve to illustrate this : —
CH3 CH3 C0-OH
Alcohol : I ^ Acetic acid : I r? Oxalic acid.
n^2 nu2
0-OH °0-OH C0-OH
Both Kekule and Couper expressed with absolute de-
fmiteness the axiom that the " atomicity of the elements" was
to be made use of for arriving at the constitution of chemical
compounds. The idea of the term " atomicity " had without
any doubt been introduced by Frankland six years previous
to this. The further development of the above axiom and
its utilisation in the theory of the linking of atoms was
carried out mainly by Kekule, and in the succeeding years
also by Butlerow and Erlenmeyer.
Before an absolutely certain knowledge of the atomicity
or, better, the valency of the elements could be attained,
perfect clearness has to be arrived at with respect to the
magnitudes of the atomic weights ; and, more particularly,
the distinction between the atom and equivalent of polyvalent
elements had to be clearly grasped. That was, however, by
no means the case at this time. In writing the formulae of
chemical compounds, most chemists employed Gmelin's
equivalents from force of habit ; but, in making use of these,
1 Wurtz manifestly forgot Couper's paper in the Anncdes de Chimie et de
Physique,of which he (Wurtz) was one of the editors, for he took credit to
himself as being the first to make use of these linking-bars (see his Atomic
Theory, fourth English edition, p. 214, note).
v THE ATOMIC WEIGHTS : CANNIZZARO 335
the true chemical values of the atoms remained indistinct
and only became apparent after the conversion of the
equivalents into atomic weights. For instance, the functions
of the simple atoms C and S were ascribed to the double
equivalents C2 and S2 in the formulas employed by Kolbe,
while for hydrogen, chlorine, nitrogen and other elements,
the equivalents were identical with the atomic weights.1
And the disorder was increased by many chemists, Couper
among the number, giving to carbon its correct atomic weight
(12), while retaining the equivalent (8) for oxygen. It is
true that Gerhardt had already attempted to bring order into
the prevailing confusion, but his mode of procedure had not
been logical enough.2
Thanks to the efforts of the Italian chemist Cannizzaro, a
way was prepared in 1858 for the clearing up of this un-
satisfactory state of matters, although those efforts received
only tardy recognition. It was he who, by his criticism in a
paper entitled Sunto di un Corso de Filosofia Chimica
•(" Outlines of a Course of Chemical Philosophy "),3 threw
light upon the methods employed for arriving at the relative
atomic weights of the elements. He recognised, as especi-
ally reliable, the deduction of these values from the vapour
densities of chemical compounds, — a method now in uni-
versal use. And he further showed to what extent the
specific heats of the metals might be regarded as a trust-
worthy aid in the determination of their atomic weights,
1 The meaning of this is at once apparent if we take Kolbe's old formula
for acetic acid, C2H3. C202. OHO, and convert it into our present formula,
CH3. CO. OH, by changing the double atoms C2 and Oa into the single ones
C and 0.
2 Cf. p. 295.
3 Nuovo Cimento, vol. vii. p. 321. This paper was edited, with notes,
by the late Lothar Meyer for Ostwald's Classiker (German by Miolati) in 1891.
Stanislao Cannizzaro, born in 1826, first studied medicine, then chemistry
under Piria, and subsequently filled in succession the chairs of chemistry in
Genoa, Palermo, and (since 1871) in Rome. This last he still holds, while
he is at the same time a Senator and a member of the High Court of Public
Education (Mitglied des obersten Rathes des tiffentlichen Unterrichts). His
experimental researches, e.g. those on benzyl alcohol and on santonine and
allied compounds, are of a very high order.
336 THE MODERN CHEMICAL PERIOD CHAP.
wrong values for many of these having come to be accepted
as the result of Gerhardt's statements.
After the correct atomic weights of the elements had
been established in this way, it became possible to build up
the doctrine of the chemical values of the elements from a
more general point of view than before. First it was
applied to the compounds of carbon, whose constitution
became the subject of the most ardent investigation.
Kekule in his text-book (begun to be published in 1 8 5 9),
and Butlerow and Erlenmeyer in various papers and subse-
quently in text-books also, endeavoured to explain the
connection existing between the elementary atoms within
the molecules, by setting out with the conception that
a definite atomicity appertained to each element; carbon,
hydrogen, oxygen and nitrogen came primarily into question
here.
Butlerow was the first to express himself clearly upon
the principle which underlay these efforts, and, with this,
upon the nature of the Structure Theory (which received its
name from him).1 We must premise here that he took up
his position on the valency theory founded by Frankland,
according to which many of the elements possess a varying
saturation-capacity. Butlerow defined the structure of a
chemical compound as the " manner of the mutual linking of
the atoms in a molecule;" he -decisively rejected the idea
that it afforded any information as to the position of the
individual atoms in space. He advanced the opinion that
the chemical character of a compound depended first upon
the nature and quantity of its elementary constituents, and
then upon its chemical structure. The latter had, to his
mind, but one meaning ; he could not agree with Gerhardt
that several rational formulae might be proposed for one and
1 Ztschr. Chem. for 1861, p. 549 et seq. — Alexander Butlerow, who was
born in 1828 and died a few years ago, became professor of chemistry in the
University of Kasan in 1858, and in that of St. Petersburg in 1868. He
contributed materially to the development of organic chemistry by many
admirable experimental researches, and in a very special manner by his
Text-book of Organic Chemistry ; this latter, which appeared first in 1864
in Russian and in 1868 in German, has had a far-reaching influence.
v DISCUSSIONS ON THE NATURE OF VALENCY 337
the same chemical compound, one formula only appearing
possible to him.
The more that the former adherents of the type theory
came to feel the necessity for abandoning it, and, free from
the yoke of this doctrine, of basing all considerations with
respect to chemical constitution upon the " atomicity " of the
elements, the more definitely ought the views upon the
nature of this property of the elements to have shaped
themselves. — The conclusion, deduced from numerous ex-
periments, that the atoms of certain elements show a con-
stant combining value and the atoms of others a varying
one, came at that time into opposition with the opinion that
this capacity of the elements was invariable.
Controversies respecting constant and varying Valency of
the Elements.
Frankland, the originator of the doctrine of the satura-
tion-capacity of elementary atoms, held aloof from the lively
discussions to which it gave rise, more especially after the
year 1870. This in all probability accounts for his service in
developing such an important doctrine having been forgotten
by many chemists, and precisely by those who have taken
the most active share in the above discussions.1 About the
year 1860 Frankland's views regarding a saturation-capacity
peculiar to the elements, which, under certain circumstances,
might be a varying one, were accepted either tacitly or
expressly by most chemists of standing. Even so early as
1856 Gerhardt had stated in his text-book that nitrogen
was sometimes triatomic, sometimes pentatomic, — a view
which coincided exactly with that of Frankland. Wurtz,
Williamson and Couper also held this opinion, and not for
nitrogen and its analogues alone, but also as being
characteristic of many other elements ; that Kolbe likewise
agreed with Frankland on this point has been stated
already. In the assumption that a constant valency was
1 See Note ],p. 310.
z
338 THE MODERN CHEMICAL PERIOD CHAP.
characteristic of a few elements and a varying one character-
istic of many more, Kolbe merely saw another expression
for the law of multiple proportion ; this conception, as
corresponding with facts, he considered necessary, because
nothing was known of the real cause of valency.
This view, then, which had so many observations to sup-
port it, led to the conclusion that each element possessed a
maximum saturation-capacity; but that lower stages of satura-
tion might coexist along with this ; Kolbe had expressed him-
self in this sense so far back as the year 1 854.1 Towards the
beginning of the sixties, several chemists who took an active
part in developing the structure theory gave utterance to the
same opinion in a more definite manner. Erlenmeyer, in par-
ticular, maintained in various papers,2 and afterwards in his
Lehrbuck der organischen Chemie, that each element possesses a
maximum valency, or that each is furnished with a definite
number of Affinivalenten or affinity-points (Ajjinitdtspunkten),
only part of these, however, being in many cases combined
with the affinity-points of other elements. In ammonia,
for instance, only three of the five equivalents of the
nitrogen atom come into play, while in chloride of ammonium
all five are satisfied. Following this out, Erlenmeyer dis-
tinguished between saturated and unsaturated compounds.
Strickly speaking,, this is nothing else than Frankland's
view.
At about the same time a lively discussion with respect
to the atomicity of the elements went on between Wurtz
and Naquet3 on the one hand, and Kekule4 on the other.
The two former declared for the assumption of a varying
valency in the case of many of the elements, while Kekule,
on the other hand, expressed his opinion more definitely
than before that the " atomicity of the elements is a funda-
mental property of the atoms, quite as unalterable as their
atomic weights."
1 Cf. Lehrbuch der organischen Chemie, vol. i. p. 22.
2 Ztschr. Chem. for 1863, pp. 65, 97, and 609 ; for 1864, pp. 1, 72, and
628. 3 Ibid., p. 679.
4 Ibid., p. 689 ; Comptes Rendus, vol. Iviii. p. 510.
CRITICISM OF KEKULE'S THEORY
In order to confirm this theorem of absolute or constant
valency, and to reconcile it with conflicting facts, Kekule
was obliged to have recourse to hypotheses which laid them-
selves strongly open to criticism. A few examples may be
given here to illustrate his view of the valency of each
element being constant. According to him, nitrogen and its
chemical analogues acted only as trivalent, sulphur, like
oxygen, only as divalent, and chlorine, bromine and iodine
as monovalent. In order, therefore, to explain the consti-
tution of compounds, in which, upon the assumption of
a varying valency, the elements just named had a higher
saturation-value than he assigned to them, Kekule had to
presuppose a fundamental difference as existing between
compounds of one and the same element. To his first
hypothesis of absolutely constant valency he added the
further one, that those compounds, in which the elements
are present in their supposed normal values, are distinguished
from the others by a more compact structure ; the former he
termed atomic, and the latter molecular compounds. The
components of the latter, e.g. ammonia and hydrochloric acid
in salmiac, phosphorus trichloride and chlorine in phosphorus
pentachloride, were, according to his view, held together by
forces of another kind to those which acted in the atomic
compounds. In order to give expression to the looser con-
nection between the molecules of these substances, he placed
their components dualistically alongside of one another in
writing the formulae ; thus he gave PC13 . C12 as the formula
of phosphoric chloride, and H3N . H2S as that of ammonium
hydrosulphide. He would not admit a variation in the
saturation-values of nitrogen and phosphorus in compounds
like those just named.
Other chemists were thus justified in asking what his
grounds were for assuming such a distinction between the
forces by which chemical constitution was conditioned ; for,
in both kinds of compounds the same atomic laws held good.
Kekule regarded the breaking up of compounds into their
components at a somewhat high temperature as a criterion
of their being molecular compounds, while atomic compounds
z 2
340 THE MODERN CHEMICAL PERIOD CHAP.
were those which could be converted into the gaseous state
without decomposition. But this distinction between the
two categories could not be maintained in the face of known
facts ; it soon became evident that such an artificial partition
only served to introduce confusion and bring about contra-
dictions which were irreconcilable.
This theory of the constant valency of the elements could
not therefore long withstand the critical examination to
which it was subjected by Kolbe,1 and more especially by
Blomstrand,2 not to mention others. The known facts could
not by any possibility be brought into accordance with the
assumption of saturation-capacity being invariable, and this
helped more than anything else to cause the theory to be
abandoned by its most zealous adherents. How, for instance,
could the existence and behaviour of the organic ammonium
bases, the sulphones and sulphoxides, perchloric and periodic
acids, and many other compounds be explained by the aid
of the above hypothesis ? Other weighty arguments have
recently been brought forward which must be regarded as
incompatible with those urged shortly after the setting up
of Kekule's theory; to take compounds of one element
only, we may refer here to the discovery of the isomeric
triphenyl-phosphine oxides, in one of which the phosphorus
must be pentavalent, and also to the proof given of phos-
phorus pentafluoride existing in the gaseous state. Such
facts are not to be reconciled with the assumption of phos-
phorus being only trivalent.
1 Cf. Joum. pr. Chem. (2), vol. iv. p. 241.
2 In his work, Die Chemie der Jetztzeit, Blomstrand went carefully into
the doctrine of the saturation-capacity of the elements, and by his compre-
hensive treatment of the question materially lightened the labours of other
critics as to the share taken by different workers in its development. — C.
Wilhelm Blomstrand, born in 1826, filled the chair of chemistry in the
University of Lund in Sweden from 1854 until 1895 ; he died in 1897. His
eminent researches in various branches of mineralogical and also of organic
chemistry are distinguished by their thoroughness, and show the influence
of Berzelius, whose doctrines Blomstrand endeavoured, in his book men-
tioned above, to reconcile and bring into close connection with the more
recent views. From the electro-chemical basis, in especial, he was able to
throw light upon the valency question, and to gain for it new points of view.
v GROUNDS FOR ASSUMING A VARYING VALENCY 341
We may assert that in the course of the last thirty
years the majority of chemists have adopted the opinion
that the atoms of most of the elements possess a varying
saturation-capacity, varying according to the conditions.
The idea prescribed as essential at the time the theory of
an unchanging valency was set up, viz. that this was a
fundamental property of atoms, may be fully recognised
without our being thereby forced to the conclusion that the
valency of the elementary atoms must therefore be constant.
In connection with these weighty discussions upon the
nature of valency, reference may be made here to a problem
nearly related to it, which has given rise of recent years to
frequent debate, and also to important experimental work,
viz. — the question whether the individual affinity-units or
valencies of one element are alike or different. If we only
took into consideration some isolated facts, such as the dis-
similar functions of the two atoms of oxygen or sulphur in
carbonic acid and carbon disulphide respectively, we might be
inclined to favour the assumption of a difference in two
affinities of the carbon atom with respect to the other two.
But the numerous investigations which have been made by
Popoff, Schorlemmer, L. Henry, Rose and others, with the
object of deciding this point so far as regards carbon, have led
to the conclusion that its four affinities are alike.
The equality or inequality of the affinities of the
sulphur and nitrogen atoms is still undecided, notwith-
standing ^hat many facts bearing on the point have been
collected together. Among other researches we may men-
tion the work of Krtiger, which appeared to prove a
difference in the valencies of sulphur ; but, while his
results have been corroborated on one side, they have been
doubted on the other. The remarkable isomerism in the
derivatives of hydroxylamine, which has been worked out
by Lossen, seems quite compatible with the assumption of
the affinities of nitrogen being different; more recent
researches by Lessen, Beckmann, Behrend and Werner,
however, point to another solution of the question on
stereo-chemical lines.
342 THE MODERN CHEMICAL PERIOD CHAP.
The main directions which chemical investigation has
taken, since these discussions with regard to valency came
up, are characterised by the endeavour to gather from the
chemical behaviour of compounds an insight into their con-
stitution, by the aid of the assumption that the elements
have a definite saturation-capacity ; while at the same time
efforts are being made to arrive at the mutual relations
between the physical properties of compounds and their con-
stitution as determined by chemical means. To this problem,
which has only recently been assiduously attacked, although
it has been projected for a long time, an analogous one has
been added, viz. the elucidation of the connection which
obviously exists between the relative atomic weights of the
elements and their chemical and physical properties.
The further Development of the Structure Theory — The chief
Directions taken l>y Organic Chemistry during the last
thirty Years.
At a first glance it strikes one as strange that organic
chemistry in particular should have been made the field for
speculations as to the composition of chemical compounds,
speculations which had the valency theory as their basis.
The reason for this preference is undoubtedly to be sought
for in the peculiarity of that element which is never
wanting in the so-called organic compounds, carbon, even if
we allow for the fact that it was from compounds of carbon —
the organo-metallic ones — that the idea of the saturation-
capacity of elements developed itself.
From the tendency of the atoms of carbon to unite with
one another according to different degrees of affinity
(Gradvenvandtschaft), i.e. by the interchange of one, two,
or three affinities, the production of the variously com-
posed carbon compounds could be explained without
difficulty. The addition of elements like hydrogen, oxygen,
sulphur, nitrogen and chlorine to the complexes of carbon
atoms was rendered intelligible in a similar manner by
v VIEWS UPON THE LINKING OF ATOMS 343
assuming that the individual affinities of the elements named
were satisfied by a like number of affinities of carbon. The
combination of the carbon atoms among themselves or with
other elementary atoms, as illustrated in this way, was
termed " linking " ( Verkettung). From thenceforth the ad-
herents of the structure theory came to grasp more clearly
the problem of chemical investigation. They sought to
combine the atoms of the various elements in question
suitably with one another, according to their saturation-
capacities, directing their efforts mainly to investigating the
structure of the compounds of carbon, since inorganic sub-
stances, as being of much simpler composition, seemed to
offer few or even no difficulties to the application of the
above principle. The conceptions thus gained of the
structure of organic substances were then tested with more
or less minuteness by actual experiment, with the object of
seeing whether the modes of formation and decomposition of
the compounds in question, and their chemical behaviour
generally, agreed with the theoretical hypotheses.
The readiness with which many chemists took to the
construction of formulae which were meant to express the
mutual relations existing between the atoms of a compound,
i.e. the structure of the latter, may in some cases have given
rise to the belief that by the aid of such symbols an insight
into the actual arrangement of the atoms in space might be
obtained. Some investigators of eminence may have in-
cited to such daring hopes and expectations by indistinct
modes of expression and unhappily chosen comparisons and
illustrations. In the minds of younger chemists, especially,
it was easy for erroneous ideas regarding the problems of
chemistry to effect a lodgment. We may recall here that
Kekule spoke of the carbon atoms as sliding over and
adhering to one another,1 and of the other side of a molecule,
etc. ; that in his text-book he brought forward graphic
formula, in which the elementary atoms have different forms
according to their saturation-capacities ; and, further, that
1 " Von einem Zusammenschieben oder Aneinanderleimen der Kohlenstojf-
atome."
344 THE MODERN CHEMICAL PERIOD CHAP.
the smallest particles of an element have been pictured by
Naquet and Baeyer as furnished with small hooks, by which
they catch hold of one another. Metaphors such as these
tended, at any rate, to an over-estimation of the capabilities
of the structure theory.
The more prudent advocates of the latter, with Butlerow
at their head, dissented all along from the idea that such
formulae could furnish any picture of the arrangement of the
atoms in space. On the other side Kolbe, in particular, pro-
tested with all his critical acumen against such exaggerations,
as leading easily to error. He remained staunch to the point
of view which he had laid down in 1854,1 believing that no
clear conception could ever be arrived at as to how the atoms
of a compound were thus arranged.
Constitution of Organic Compounds according to the
Structure Theory.
Although the structure theory was unable to realise the
highly-pitched expectations which aimed at a knowledge of
the spacial arrangement of the atoms, it possessed none the
less great practical value. The development of organic
chemistry since the middle of the sixties shows in fact that,
through the aid of the structural hypothesis, the discovery
of new modes of formation and decomposition of compounds,
the recognition of the relations existing between various
classes of bodies, and, especially, the interpretation of the
constitution of numerous organic substances became possible.
Kekule's theory of the aromatic compounds (see below) forms
the most striking proof of this.
The working out of the constitution of the so-called
saturated compounds offered fewer difficulties than that
of the compounds poorer in hydrogen, — the unsaturated
ones. Kekule was the first to express the definite opinion
that in all fatty compounds the carbon atoms were united
to one another by an affinity of each, a point which might
1 Lehrb. d. organ. Chemie, vol. i. p. 13.
v CONSTITUTION OF UNSATURATED COMPOUNDS 345
have been deduced from Couper's and also from Kolbe's
rational formulae, had the equivalents used by them been
converted into the atomic symbols. The expositions given
by Kekule and also by Erlenmeyer, Butlerow, Glaus and
others in text-books of organic chemistry and occasional
papers, with regard to the constitution of such compounds
soon became the common property of nearly all chemists.
More difficult was the question — What was the function
of the carbon atoms in organic compounds poorer in
hydrogen ? With respect to the constitution of these,
Kolbe, Couper and Wurtz had already expressed the view
that in them — e.g. ethylene, acrylic acid, acetylene, etc. — one
or several atoms of carbon acted as divalent. Kekule*
hesitated at first between two opinions. He was, on the
one hand, inclined to assume a " more compact," i.e. a double
or treble, linking of particular pairs of carbon atoms in the
substances in question ; while, on the other, his experimental
researches upon unsaturated organic acids led him to prefer
the idea that the affinities of certain of their carbon atoms
were not completely saturated, and that these therefore
show gaps (Luckeri), by means of which the capability of
further combination which such compounds possess can be
explained. The latter of the two views coincided in the
main with the one mentioned above, in which divalent
carbon atoms were presupposed. Kekule, it is true, never
definitely admitted that he regarded the saturation-capacity
of carbon as a varying quantity. Of recent years preference
has been given to the conception of a double or treble
linking of the carbon atoms, although the other view does
not want for eminent adherents. Thus Fittig,1 from his
1 Rudolf Fittig, born 6th December, 1835, after working for several
years on the teaching staff of the University of Gottingen, became Professor
of Chemistry at Tubingen in 1869, and was called from thence to the Uni-
versity of Strasburg in 1876, where he still continues ; the beautiful
laboratory there was planned by him. His name will often be mentioned
in the special history of organic chemistry, which he has greatly enriched
by most admirable researches, more especially upon aromatic and un-
saturated compounds. Wohler's Grundriss der organischen Chemie (" Out-
346 THE MODERN CHEMICAL PERIOD CHAP.
work upon unsaturated acids, has expressed himself in favour
of the assumption of carbon being divalent in some of these
compounds.1 But the question of the constitution of such
compounds has not yet been conclusively answered ; for
numerous observations have been made which appear to
show that the complete solution of this problem by the aid
of structural-chemical hypotheses alone is impossible.
Theory of the Aromatic Compounds.
In Kekule's hands the structure theory scored by far
its greatest victory, in the deciphering of the constitution of
the so-called aromatic compounds.2 These were defined by
him as derivatives of benzene ; his first task therefore con-
sisted in elucidating the structure of this long-known hydro-
carbon, i.e. in explaining how the six carbon and the six
hydrogen atoms were combined together. Here Kekule
took up again his previously expressed idea of a more
compact linking of the carbon atoms, and discussed the
possible cases of how the six in benzene could be connected
together, setting out with the assumption that the carbon
acted as tetravalent and the hydrogen as monovalent. While
the compounds of the fatty series contained — in the language
then and now current — an open chain, Kekule assumed in
benzene a closed one, and pictured each of the six carbon
atoms present in the molecule as being united to two others.
The structural formula which followed from this was the
hexagon, since then so widely made use of, whose angles
were formed of carbon atoms linked alternately to each
other by one and two bonds, and also combined in every
case with one atom of hydrogen, thus —
lines of Organic Chemistry"), entirely recast by him and published under
the same title, has run through numerous editions ; he supplemented it in
1872 by the companion volume, Grundriss der anorganischen Chemie.
1 Cf. Ann. Chem., vol. clxxxviii. p. 95.
2 Bull. Soc. Chim. for 1865, p. 104; Ann. Chem., vol. cxxxvii. p. 129.
v KEKULE'S THEORY OF THE AROMATIC COMPOUNDS 347
H
C
HC CH
HC CH
Kekule and his pupils, together with many other chemists
who had busied themselves with the derivatives of benzene
after this view had been published, now directed their efforts
to comparing all the known and rapidly increasing observa-
tions bearing upon this class of bodies with the deductions
drawn from the above formula, and therewith to proving by
actual experiment the admissibility of the assumptions on
which the formula was based. An almost boundless number
of facts were thus collected together, which, taken as a whole,
were found to agree readily with Kekule's hypothesis. The
first inference to be drawn from it, viz. that the six hydrogen
atoms which were distributed similarly among the six carbon
ones were in every respect equal to one another, was con-
firmed by the observation, made over and over again, that
only one and the same product resulted from the replacement
of any one of the hydrogen atoms of benzene by a mono-
valent radical or element, and never a second isomeric
compound. When two or three atoms of hydrogen became
substituted, the case was otherwise. From his formula
Kekule deduced the number of isomers which were then to
be expected ; he stated his opinion that three isomeric com-
pounds, and not more, would result in both cases through
the replacement of two or three of the hydrogen atoms of
benzene by the same substituent. If two dissimilar radicals
took the place of two atoms of hydrogen, the number of
possible isomers was not increased; these did augment,
however, to a definite number when three hydrogen atoms
were replaced by two or three different substituents. The
truth of these and of other prognostications by Kekule has
• 348 THE MODERN CHEMICAL PERIOD CHAP.
since been verified in the most brilliant manner by a vast
number of observations.
This happy interpretation of the constitution of benzene
shed a great light over a hitherto neglected branch of the
science. Not merely the immediate derivatives of benzene,
but also substances much more distantly related to it, like
naphthalene and anthracene, and more recently phenanthrene,
fluorene and many other hydrocarbons, together with their
numberless and often important derivatives, had their
chemical constitution successfully investigated by the aid of
Kekule's hypothesis.
This hypothesis did not, however, completely satisfy
a number of chemists, who considered modifications in it
necessary. We need not enter here into the reasons which
led to such modifications, but may just mention Ladenburg's 1
prism formula and Claus's2 diagonal one (see appended figures),
which were brought forward by those investigators as explain-
ing more completely than Kekule's hexagon formula the
chemical behaviour of benzene.
1 JBer., vol. ii. p. 140 ; also his pamphlet, Theorie der aromatischen Ver-
bindungen. — Albert Ladenburg, born at Mannheim on July 2nd, 1842, has
been a notable contributor to organic chemistry by his excellent experi-
mental work. His chief researches have been upon the organic compounds
of silicon, the benzene derivatives, and more particularly the derivatives
of pyridine and piperidine. His Vortrdge uber die Entivickelungsgeschichte der
Chemie in den letzten 100 Jahren (1st edition, 1869, 2nd edition, 1887), is
well known as a genuine historical work. He is editor of the chemical
section of the EncyUopddie der Naturwissenschaften (published by Trewendt).
Since 1890 Ladenburg has held the chair of chemistry at Breslau, having
previously taught at Heidelberg and Kiel.
2 Theoretiache Betrachtungen und deren Anwendung zur Systematik der
organischen Chemie (1867), (" Theoretical Considerations and their Appli-
cation to the Systematising of Organic Chemistry "). Adolph Glaus, born
June 6th, 1840, studied under Kolbe and Wohler, and now holds the pro-
fessorship of chemistry at the University of Freiburg-im-Breisgau. His
experimental work has been mainly in organic chemistry, of which he has
systematically investigated various branches, — e.g. the derivatives of quino-
line, the fatty-aromatic ketones, etc. He has further from time to time
published papers giving his views on many important points of chemical
theory (cf. the Grundziige der modernen Theorie in der organischen Chemie,
Freiburg, 1871 ; and also the Journal fiir praktische Chemie since 1888).
CONSTITUTION OF THE AROMATIC COMPOUNDS 349
1IC CH
\/
CH
CH
HC/
\CH
HC-I-CH
\ X
HC/
SloH
H
Ladenburg's formula. Claus's formula.
The discussions upon this point still continue ; thus, the
results of recent admirable investigations on the hydro-
phthalic acids, etc., by A. von Baeyer l had, he considered,
given him grounds for disputing all the above hypotheses on
the constitution of benzene, while Glaus 2 maintained — and
not without cause — that Baeyer's view was identical with
his own. The latter has quite lately acknowledged 3 that
Claus's formula agrees best with known facts, including those
which cannot be made to harmonise with either Kekule's or
Ladenburg's hypothesis. The most recent discussions upon
the constitution of benzene, naphthalene, quinoline, etc., can
only be indicated here.4
But, notwithstanding all this, the fact must be fully
recognised that Kekule's conception, even although it by no
means affords a complete picture of the constitution of
benzene, has borne many and rich fruits. Through the
stimulus which was given by his theory of the aromatic
compounds, the work of numberless chemists with this class
of substances, work extending over a long period of time,
received a particular stamp of its own ; their chemical labours
have been carried out entirely under the influence of the
benzene theory.
The meaning of the term Aromatic Compmwids has of
1 Ann. Chem., vol. ccxlv. p. 103; vol. cell. p. 257; vol. cclviii. pp. 1
and 145.
2 Journ. pr. Chem. (2), vol. xxxvii. p. 455.
3 Ann. Chem., vol. cclxix. p. 177.
4 Cf. especially, in addition to the papers cited in note 3, p. 351, Ad.
Glaus, Journ. pr. Chem. (2), vol. xlviii. p. 576 ; vol. xlix. p. 505 ; W.
Marckwald, Ann. Chem., vol. cclxxiv. p. 331; Briihl, Journ. pr. Chem. (2),
vol. xlix. p. 201 ; E. Bamberger, Ann. Chem., vol. cclvii. p. 1 ; Collie,
Journ. Chem. Soc., vol. Ixxii. p. 1013.
350 THE MODERN CHEMICAL PERIOD CHAP.
late years undergone a wide extension since the near relation
of pyridine, quinoline and iso-quinoline and their derivatives
to benzene has come to be recognised. The ardour shown in
the investigation of these nitrogenous bodies, with their
endless derivatives, has gone on increasing in proportion with
the increasing surmise of a close connection existing between
them and the vegetable alkaloids, and with the actual proof
of this in some particular cases. . Kb'rner was the first to
propound the important idea that pyridine may be regarded
as benzene in which a methine (CH'") is replaced by the
trivalent nitrogen atom.1 The inferences drawn from this
with respect to the derivatives of pyridine, like those deduced
from the structure of benzene, have formed the subject of
numberless experimental researches and theoretical dis-
cussions which are still proceeding. Reference will be made
to some of the more important results of these investigations,
and of others upon the nitrogen compounds termed poly-
azines, in the special history of organic chemistry.
The efforts to gain a clear conception — in the widest sense
of the word — of the structure of benzene and its derivatives
have also been of use in the case of other classes of com-
pounds, especially for those analogous substances furfurane,
thiophene and pyrrol, which are now universally regarded
as being characterised by a closed five-membered ring
containing four carbon atoms together with an atom of
oxygen, an atom of sulphur, or the imido-group (NH)
respectively. Victor Meyer's 2 splendid and thorough re-
1 Dewar was the first to publish this view (Journ. Chem. Soc., vol. xxiv.
p. 145 ; or Ztsc.hr. Chem. for 1871, p. 117), Korner having however already
given utterance to it in his lectures.
2 Viktor Meyer, born 8th September, 1848, after filling the post of pro-
fessor of chemistry at Stuttgart and at Zurich, was called to the chief chem-
istry chair at Gottingen on Wohler's death in 1885, and removed from there
in 1889, to succeed Bunsen at Heidelberg ; he died suddenly on August 8th,
1897. His comprehensive researches upon nitro-compounds of the fatty
series, upon iso-nitroso compounds, and upon thiophene are among the
very first of our time, and have contributed largely to increase our know-
ledge of organic chemistry. The method devised by him for vapour-density
determinations has become a standard one, and has also been successfully
applied to the solution of important theoretical questions (e.g. to that of
v CHARACTERISTICS OF THE AROMATIC COMPOUNDS 351
searches on thiophene and its derivatives l have before all
others led conclusively to the recognition of the analogous
composition of the above substances, and also to a more pre-
cise conception of the term aromatic compounds. According
to Meyer,2 it is the chemical behaviour of a substance with
regard to nitric acid, sulphuric acid, bromine, and acid
chlorides (in the presence of chloride of aluminium) which
decides whether it has a claim to be ranked among those
compounds. He lays here the greatest weight upon facts,
whereas in previous determinations of the nature of this class
of substances the existence of a closed ring of six carbon
atoms was held to be a fundamental condition.
Those chemists 3 who have made a special study of the
constitution of benzene, naphthalene, quinoline, etc., are at
present inclined to think that the reciprocal linking of the
carbon atoms may vary with the metamorphoses of the com-
pounds in question, in such a way that the " central " bonds
change into the so-called double bonds, and vice versa', an
interchange of linkage is thus assumed. And although we
have as yet no knowledge of the actual nature of these modes
of linking, such speculations have a certain value, serving as
they may do to a better understanding of many curious facts.
Application of Structural-chemical Conceptions to the
Investigation of Isomerism.
Detailed reference % has already been made to the sig-
nificance which the investigation of the isomeric relations of
organic compounds has for the question of their chemical
the valency of aluminium). Among his most recent researches were those
on the iodo- and iodoso- compounds, and on the laws governing the esteri-
fi cation of aromatic acids. Lastly, Victor Meyer and Jacobsen's large
Lehrbuch der organischen Chemie is a work of very great value. A
short but appreciative memorial address on Victor Meyer by Liebermann
is to be found in the Berichte, vol. xxx, p. 2157.
1 Cf. his work, Die Thiophengruppt ("The Thiophene Group"), Braun-
schweig, 1888. 2 Ibid,} p 276.
3 Cf. especially Ad. Claus, Journ. pr. Chem. (2), vol. xlii. pp. 24, 260,
458 ; vol. xliii. p. 321.
352 THE MODERN CHEMICAL PERIOD CHAP.
constitution.1 Indeed, the efforts made during the last thirty
years to prepare as large a number of isomers as possible,
and to establish their structure, is a main feature of the mode
in which organic chemistry has been and still is being studied.
Before the derivatives of benzene had acquired that pre-
dominating interest for chemists which they afterwards came
to do, the constitution of metameric substances was held to
be sufficiently explained by a difference in the grouping of
the atoms of the radicals. We have only to recall here the
proof given of the rational composition of trimethylamine as
opposed to that of the isomeric propylamine; the reason
assigned for the metamerism of diethyl oxide and methyl-
propyl oxide ; and, lastly, to think of the secondary and
tertiary alcohols or acids, whose constitution was predicted
with perfect definiteness before they had been discovered
(i.e. of the metamerism of dimethyl-carbinol with ethyl-
carbinol, and that of trimethyl-carbinol with propyl-, iso-
propyl-, or methyl-ethyl-carbinol),2 &c.
To such satisfactorily explained cases of metamerism as
these, the investigation of the aromatic compounds now
added numerous others which, however, unlike the former,
could not be referred back to a different grouping of the
atoms in the radicals. Kekule therefore sought to explain
the similar composition of various benzene substitution pro-
ducts (e.g. of the three dibromo-benzenes, the three phenylene-
1 Cf. p. 250 et seq.
2 The rational formulae will serve to illustrate the above cases of meta-
merism —
CH3)
C3H7 ) x CH3 [ N C2H5 1 0 CH3
CH j
Propylamine Trimethylamine Diethyl oxide Methyl-propyl oxide
C(CH3)2(()H) CH2(C2H5) (OH)
Dimethyl-carbinol Ethyl-carbinol
CH3
pCaH7/^-rr» CC2H5(OH)
C(CH3)OH H2(0] H
Trimethyl-carbinol Propyl-carbinol Methyl-ethyl-carbinol
v EXPLANATION OF POSITION-ISOMERISM 353
dicarboxylic acids, &c.) from his conception of the struc-
ture of benzene, by assuming different relative positions
of the substituents to one another. Such compounds were
termed position-isomers. The question of the relative positions
occupied by the entering substituents, or, as it was also
called, the determination of the chemical position of the latter,
was ardently studied from different sides, after the problem
had been raised by Kekule. Among the investigations which
helped in a special degree towards the solution of this were
those of Baeyer upon the constitution of mesitylene and its
derivative isophthalic acid, those of Graebe upon naphthalene
and phthalic acid, and that of Ladenburg on terephthalic
acid. By the ingenious conclusions drawn from these and
many other researches, the structure of the so-called Ortho-,
Para-, and Meta-compounds was arrived at with considerable
certainty. Some errors, however, did creep in here, — for
instance, the wrong interpretation of the constitution of
quinone from theoretical considerations, a point which gave
rise to very great confusion before the mistake was finally
put right. Korner's researches x have been of immense
value for the determination of position; he introduced a
new method here.
The investigation of these metameric relations among
the derivatives of benzene materially lightened that of the
still more complicated phenomena among the pyridine and
quinoline bases which were referable to similar causes. The
metamerism of the pyridine-carboxylic acids and other
derivatives, which had been predicted on theoretical grounds
from conceptions as to the structure of pyridine, was
beautifully confirmed later on by the comprehensive re-
searches of Weidel, Skraup and others ; while considerations
of the same kind have proved equally fruitful in the investi-
gation of the derivatives of thiophene and pyrrol, and also
of indole and other aromatic compounds, such as the poly-
azines and poly-azoles.
But the certainty with which the constitution of meta-
meric substances was supposed to have been established left
1 Gazz. Chim. ItaL, vol. iv., p. 305.
A A
354 THE MODERN CHEMICAL PERIOD CHAP.
much to be desired in many cases. The symbols employed
to express the structure of such compounds were intended
to have but one definite meaning ; Gerhardt's view, that
several formulae might be used indifferently to picture the
reactions of the bodies in question, was entirely abandoned.
On the other hand, more organic compounds became known
whose constitution could be illustrated equally well by
two totally different formulae, according to their chemical
behaviour in different circumstances. Many of the reactions
of aceto-acetic ether, for instance, cause us to give to it the
constitution which is apparent in its name, but in others it
behaves like the ether of an oxy-crotonic acid; indeed
L. Claisen1 has just proved that its sodium compound is
derivable from the latter ether. Phloroglucin, which has
been for long, and justly, looked upon as trioxy -benzene,
may also be indicated, from some of its reactions, as a meta-
meric tricarbonyl compound.2
The constitution of these, as well as of certain other
compounds, e.g., isatin, oxindole, carbostyril, cyanamide, etc.,
is therefore capable of two explanations. Opinions are still
divided among chemists who have busied themselves with
this question as to which of the two possible structural
formulae is the correct one for such compounds. Baeyer
distinguishes between a stable (stabile) modification and an
unstable (Mile) one, the latter being termed the pseudo-form ;
for isatin, e.g., the formula containing hydroxyl is the stable
1 Ann. Chem., vol. ccxcvii. p. 92.
2 The tautomerism of the above compounds is seen from the following
formulae : —
CH2-CO-CH3 CH = C(OH)CH3
>-OC2H5 CO'OCoH5
CO-
C(OH) CO
A A
HC CH H2C CH2
(OH)C C(OH) OC CO
\ / V
CH OH2
v TAUTOMERISM OR DESMOTROPISM 355
modification, while pseudo-isatin is unknown in the free
(or unstable) state, only derivatives of it being capable of
existence.
C. Laar,1 who has discussed this question minutely, applies
the name tautomerism to these phenomena. A " change in
combination or position of hydrogen atoms " 2 is always in-
volved here, as is readily seen in what is doubtless the simplest
case of such a tautomerism — in hydrocyanic acid. The
chemical behaviour of this acid leads on the one hand to the
structural formula H — C=N, and on the other to that of
C = N — H (in which the carbon is divalent) ; in the former
case the hydrogen is linked with carbon, and in the latter
with nitrogen. Laar imagines oscillatory conditions within
the hydrocyanic acid molecule, which cause the hydrogen
atom to take up the one and the other position alternately ;.
he therefore presupposes the simultaneous existence of both
modifications. Since all cases of tautomerism depend upon
a change in the linking of the atoms of carbon, nitrogen and
oxygen with respect to hydrogen, Victor Meyer and Jacobsen
have proposed to replace the above indefinite term by the
better one of desmotropism.
During the last few years experimental and speculative
work have added largely to the number of known tautomeric
compounds. In a lecture entitled " Ueber Tautomerie"
delivered at Stuttgart last year (1897), W. Wislicenus gave
an excellent resumt of the most important investigations in
this field. Of special interest are those still rare cases in-
which the two tautomeric forms of a compound have
actually been observed, by W. Wislicenus himself and by
L. Claisen. Under these circumstances the former is justified
in concluding that tautomeric phenomena are reversable
intra-molecular changes which only lend themselves to ob-
servation in exceptional instances. According to F. Traube,3
" tautomerism is a particular kind of isomerism in which we
have to do with a state of equilibrium, excessively sensitive
1 Ber., vol. xviii. p. 648 ; vol. xix. p. 730.
2 Ein " Bindungs- oder Platzwechsel von Wasserstqffatomen."
3 Ber., vol. xxix. p. 1723.
A A 2
356 THE MODERN CHEMICAL PERIOD CHAP.
to outward conditions, of two isomers that change very
readily the one into the other."
Here then we have an instance of the constitution of one
and the same compound being expressible by two structural
formulae, either one of them apparently as correct as the
other. In another group of me tamers we find just the
opposite conditions, i.e., one and the same structural formula
applying to two totally different chemical compounds of the
same composition. J. Wislicenus 1 was the first to establish
such an identity in structure (Strulduridentaf) for two different
substances — the fermentation- and para-lactic acids.2 The
structure theory is therefore insufficient to explain such
cases of metamerism as this. Further instances of the same
kind are found in crotonic and iso-crotonic, fumaric and
maleic, and mesaconic and citraconic acids. Wislicenus
designated this species of metamerism geometrical isomerism,
and Michael, who has likewise occupied himself for a long
time with the study of this branch, allo-isomerism. These
phenomena are now grouped under the term Stereo-isomerism,
and the rapidly growing Stereo-chemistry now forms a distinct
branch of the science.
J. Wislicenus3 has attempted to explain phenomena of
1 Johannes Wislicenus, born at Klein-Eichstedt, near Querfurt in Thiir-
ingen, on 24th June, 1835, became in 1885 professor of chemistry and head
of the chief chemical laboratory in the University of Leipzig, after filling
from 1872-85 the corresponding post at Wtirzburg, before which he taught
at Ziirich. After the death of Strecker, whom he succeeded at Wiirzburg,
he re-edited the former's text-book of chemistry. His experimental re-
searches, most of which have been published in the Annalen der Chemie,
pertain almost exclusively to the domain of organic chemistry, in the special
history of which we shall frequently have occasion to refer to them. The
very important work which he did on the lactic acids impelled him even so
early as 1873 to the conclusion that the cause of the difference between two
of them must be sought for in the spacial relations of the atoms in the mole-
cule. His quite recent speculations upon geometrical isomers are referred
to above.
2 Ann. Chem., vol. clxvii. p. 343.
3 Cf. Die rdumliche Anordnung der Atome in organischen Molekiilen
(Leipzig, 1887), (" The Spacial Arrangement of the Atoms in Organic Mole-
cules ") ; also the Tageblatt der Naturforscherversammlung zu Wiesbaden,
1887 (" Journal of the Assembly of Scientists at Wiesbaden, 1887 ").
v VAN 'T HOFF AND LE BEL'S HYPOTHESIS 357
this kind by the aid of an hypothesis propounded by van
't Hoff and Lebel.1 According to this hypothesis, which was
designed with the object of explaining the optical activity of
isoraeric compounds, the centre of gravity of an atom of
carbon is supposed as in the middle of a tetrahedron, and
its four affinities as at the four corners. When two atoms
of carbon become linked together, with the subsequent
neutralisation of one affinity of each, then van 't Hoff and,
after him, Wislicenus assume that both are capable of
rotating in opposite directions about a common axis; and
the possibility of such rotation is supposed to cease with the
double or triple linking of the carbon atoms. Wislicenus
has made this hypothesis the basis of his discussions and his
later experimental researches. An important aid to this
conception is added in the supposition that, in the rotation
of systems with carbon atoms linked together by one affinity
of each, " specially directed forces, the affinity-energies,"
come into play, which regulate the spacial relations of the
atoms to one another. Wislicenus believes that in these
suppositions he possesses a means whereby " the establishing
of the spacial arrangement of atoms in particular cases may
be arrived at by experiment."
The theory which is based upon the presence of asym-
metric carbon atoms in chemical compounds is in point of
fact supported by many important observations. In the
first place it is to be noted that all optically active organic
compounds, whose constitution is established, contain one or
more asymmetric carbon atoms. The observations which
1 Cf. van 't HofFs pamphlet, Dix Annies dans Vhistoire d'une Theorie
(1887). Van 't Hoff first published his views on the subject in the small
volume, La Chimie dans VEspace, in 1875 (English edition by Marsh,
under the title Chemistry in Space, 1891 ; and German, by Herrmann, 1877
and 1894). Le Bel also brought out the same hypothesis, independently
of van 't Hoff, in the Bull. Soc. Chim. (2), vol. xxii. p. 337. Messrs. Long-
mans and Co. have just published (1898) a second revised and enlarged
English edition of van 't HoflPs The Arrangement of the Atoms in Space,
with a preface by Johannes Wislicenus, and an appendix entitled " Stereo-
Chemistry among Inorganic Substances," by Alfred Werner. The book is
translated and edited by Arnold Eiloart, who has made a special study of
this branch.
358 THE MODERN CHEMICAL PERIOD CHAP.
have been made upon racemic, malic, mandelic and lactic
acids, and upon a number of other substances, are in perfect
accord with the above theory. The plan of breaking up
inactive into active modifications, which was first followed
by Pasteur x with such striking success, has since been applied
in many other cases with equally good results. The theory has
proved especially fruitful during the last decade, as applied
by Emil Fischer2 in his brilliant researches on the sugars.
Further, A. von Baeyer's important work upon the hydro-
phthalic acids,3 whose isomerism is without doubt due to
differences in the spacial arrangement of the atoms, con-
stitutes a strong support for the theory of the asymmetric
carbon atom in " ring-shaped " structures.
The investigation of the isomerism of certain compounds,
in which the so-called " double linkage " of carbon is to be
found, has proved exceptionally fruitful. The work under-
taken by Johannes Wislicenus and his pupils 4 upon fumaric
and maleic, crotonic and iso-crotonic, angelic and tiglic acids,
and their halogen derivatives, with the object of getting at
the root of these phenomena, has led to surprising results,
which however do not harmonise with theory in many
respects. In fact the investigations of A. Michael 5 and
1 Louis Pasteur (born at Dole on December 27th, 1822, died at Paris on
September 28th, 1895) has proved a great pioneer in chemical as well as in
the biological sciences. It was indeed his systematic work upon optically
active compounds, especially the tartaric acids, which led him on to the
treatment of biological questions, — to the isolation and artificial culture of
pure ferments. His researches upon the alcoholic, lactic and acetic fermen-
tations constituted him a chief founder of the new zymo-chemistry and
bacteriology. The brewing industry is deeply indebted to him for the im-
provements which he brought about in it. Following on those researches
we have his great work on inoculation against splenic fever, dysentery and
hydrophobia. He belongs truly to the great benefactors of mankind.
2 Ber., vol. xxiii. p. 2114, vol. xxiv. p. 3997. See also the Special
History of Organic Chemistry.
3 Ann, Chem., vol. ccxlv. p. 103 ; vol. ccli. p. 257 ; vol. cclvi. p. 1 ;
vol. cclviii. pp. 1 and 145 ; vol. cclxvi. p. 169 ; vol. cclxix. p. 145.
4 Seethe pamphlet already quoted ; also Ann. Chem., vol. ccxlvi. p.
-53 ; vol. ccxlviii. pp. 1 and 281 ; vol. ccl. p. 224.
5 Cf. especially Journ. pr. Chem. (2), vol. xlvi. p. 400, besides preceding
numbers.
v GEOMETRIC-CHEMICAL ISOMERISM 359
others 1 have shown that contradictions occur in them which
throw doubt upon some of the theoretical hypotheses.
This idea of referring the cause of many cases of iso-
merism to the different geometrical arrangement of the
atoms has had a most stimulating effect, and has led to the
discovery of many hitherto overlooked relations existing
between isomeric substances. The work done upon the
dichlorides of tolane, the butylenes, the isomeric cinnamic
acids, erucic and brassidic acids, and upon the alkyl-succinic
acids deserve mention here.2 Of recent years there have
been numerous speculations advanced with the object of bring-
ing conflicting phenomena into accord with theory, e.g. Victor
Meyer and Kiecke's3 ideas upon the "constitution of the
carbon atom," and Bischoff's4 "dynamic hypothesis" of certain
cases of isomerism.
All this work is due to the circumstance, of which there
can no longer be any doubt, that geometric-chemical isomers
do really exist. During the last few years there have been
similar observations with regard to various nitrogen com-
pounds, and efforts have been made to trace these cases of iso-
merism back to spacial relations, — to the configuration of the
nitrogen atom. It is more especially in those compounds in
which we have a double linkage between the carbon and
nitrogen, i.e. =C:=N — , that such isomers have been noticed.
The theory of the stereo-isomerism of nitrogen compounds,
— a theory due to a great extent to Werner and Hantzsch,5
— is based upon the work of the late Victor Meyer and
Auwers, of Beckmann, and particularly of A. Hantzsch
himself on the oximes of aldehydes and ketones, together
1 Skraup, Wiener Moiiatshefte, etc, vol. xii. p. 119; Anschiitz, Ann.
Chem., vol. ccliv. p. 175.
2 Cf. Special History of Organic Chemistry.
3 Ber., vol. xxi. p. 951. 4 Ber., vol. xxiii. p. 1467.
5 Ber., vol. xxiii. pp. 1 and 1243. For the literature on the subject, see
Hantzsch's Grundriss der Stereochemie (Breslau, 1893). On p. 106 the vital
part of this theory is expressed as follows: — "In the language of the
valency theory, the geometrical isomerism of nitrogen compounds ....
depends upon the three valencies of the nitrogen atom not being in the
same plane in certain of these compounds."
360 THE MODERN CHEMICAL PERIOD CHAP.
with quite recent observations on the hydrazones and the
carbo-di-imides by Overton and others. There is no question
that a large number of important cases of isomerism have
been in a way explained by the assumption of spacial
differences in the relation of the nitrogen to the carbon
atom. But whether stereo-isomerism is to be assumed in as
many cases as Hantzsch is inclined to believe, is for the
present doubtful (compare the diazo-compounds in the
Special History of Organic Chemistry).
It is impossible to give a definite answer to the question
whether the spacial arrangement of the atoms within a mole-
cule actually corresponds with the configurations assumed
by the above-named scientists, for no proof can be furnished
of the correctness of these conceptions. The expectations
raised by them — of obtaining a deeper insight into the
mode in which the atoms are arranged in a compound — are
possibly pitched too high. Criticism has indeed begun —
as already indicated — to busy itself with the explanation
of geometrical isomerism in particular cases,1 but stereo-
chemical theories2 are not yet sufficiently advanced to give
us a clear view of the whole subject. The time has not yet
come for an objective historical account of stereo-chemistry,
in which theory and fact shall have their true values
assigned to them ; the subject is but in its infancy.
1 Ad. Glaus has been especially active in disputing the correctness of
the stereo-chemical view as applied to the isomeric oximes ; cf. Journ. pr.
Chem., vol. xliv. p. 312 ; vol. xlv. pp. 1, 556 ; vol. xlvi. p. 544.
2 Hantzsch's Grundriss der Stereochemie gives a good summary of the
work done in this branch of chemistry up to the year 1893. Compare also
Auwers' Die Entwickelung der Stereochemie (Heidelburg, 1890), and C. A.
Bischoff and P. Walden's Handbuch der Stereochemie (vol. i, 1894), which
goes minutely into the subject. In English there is Eiloart's book A
Guide to Stereo- Chemistry.
DEVELOPMENT OF SYNTHETIC METHODS 361
The Development of Important Methods for investigating
the Constitution of Organic Compounds.
The above-mentioned discussions upon isomers are suffi-
cient to show us how materially these have aided the
development of organic chemistry since the subject was
zealously taken in hand. Hardly any other group of
phenomena has furthered the solution of the question of
chemical constitution in a more lasting manner, for the
attempts to establish the constitution of isomeric bodies
have coincided with those whose aim was to fathom the cause
of isomerism. The methods followed during the last decade
for investigating the rational composition of organic com-
pounds have in great part developed themselves from others
previously in use. The paths which have led towards the
wished-for goals were smoothed by the indispensable
preparatory labours of Liebig, Wohler, Bunsen, Kolbe,
Frankland, Dumas, Williamson, Gerhardt, Hofmann, Wurtz
and others.
Synthetic Methods.
The mode of attaining to a knowledge of the constitu-
tion of organic compounds, which had been least worked
out of any, was their artificial preparation from others
of simpler composition. After Wohler had published his
memorable observation on the production of urea from its
elements, and had therewith furnished a complete synthesis
of it, years elapsed before any further successful work in
this direction fell to be recorded. Referring the reader to
the special history of organic chemistry, we need merely
recall here the important discoveries during the fifties by
Kolbe and Frankland, — the synthesis of acetic acid by the
former, and the building up of hydrocarbons from substances
of simpler composition by the latter.
The importance of synthetic research was from thence-
362 THE MODERN CHEMICAL PERIOD CHAP.
forth recognised in an increasing degree;1 indeed, it was
from artificial modes of preparation that the constitution of
many organic substances could first be deduced with cer-
tainty. Thus (to give only one or two instances) the rational
composition of acetic acid was arrived at from its production
from the methyl compounds — methyl cyanide and sodium-
methyl. The constitution of hydrocarbons was inferred
from their synthesis from halogen-alkyls with zinc or
sodium, and that of the ketones through their formation
from acid chlorides and zinc-alkyls. Light was thrown
upon the true composition of the oxy-acids by their
synthesis from aldehydes or ketones and hydrocyanic acid,
and also from phenates and carbonic acid. And to what a
wealth of synthetic reactions and discoveries of new com-
pounds have not the sodium derivatives of certain acid
ethers — e.g. aceto-acetic and malonic ethers — led !2
In every section of the wide field of organic chemistry,
great success has followed the application of synthetic
methods; and the worth of these latter is not to be
measured merely by the vast number of new compounds to
which they have given rise, but by their own intrinsic
value, which has shown itself in the knowledge thereby
gained of the chemical constitution of organic compounds.
The so-called condensation syntheses have proved themselves
of especial value in this direction. This term " condensa-
tion" has, since Baeyer's explanation on the subject, been
employed generally for those reactions in which several
similar or dissimilar molecules coalesce together, with
elimination of water, in such a manner that the carbon
atoms become linked to one another. A classical instance
of it (observed a long time ago by Kane, but first explained
by Baeyer, as above) is given in the transformation into
mesityl oxide — or into phorone — and then into mesitylene
1 In 1889 chemical literature was enriched by an admirable systematic
" Textbook of Syntheses " on a historical basis, in K'. Elb's Die Synthetischen
Darstellungsmethoden der Kohlenstoffverbindungen.
2 With reference to these and other syntheses, cf. the special history
of organic chemistry.
v "CONDENSATION" SYNTHESES 363
which acetone experiences under the influence of sulphuric
acid. Similar reactions go on in the case of other ketones
and of aldehydes — e.g. the condensation of acetic to crotonic
aldehyde (Kekule) — and that of a mixture of acetic and
benzoic aldehydes to cinnamic aldehyde. Through these
and other processes a bridge was thrown over the gap
between the saturated and unsaturated compounds, while
at the same time light was shed upon the constitution of the
latter. The reaction discovered by and called after W. H.
Perkin, sen., which depends on the condensation of aldehydes
with fatty acids, formed the basis of some notable researches
by Fittig, Claisen and others, while it likewise aided in
clearing up the rational composition of unsaturated acids.
A. von Baeyer,1 in conjunction with a large number of
his pupils (E. and O. Fischer, v. Pechmann, Konigs, Knorr,
E. Bamberger, Paal, etc.), has minutely investigated this
subject of condensation in the most admirable manner,
as have also Kekule", Fittig, Ladenburg, Victor Meyer,
Hantzsch, Claisen, W. H. Perkin, Graebe, Liebermann,
Collie, and, in fact, almost all chemists who have occupied
themselves with organic chemistry of recent years ; indeed,
this study seemed for a time to be the chief feature of
organic chemistry. The ardour for carrying out such
syntheses increased more especially after it was seen that
the chemical processes going on in plant organisms — i.e. the
formation of compounds rich in carbon from carbonic acid,
1 Adolf von Baeyer, born at Berlin on 30th November, 1835, became a
pupil of Bunsen and of Kekule, and applied himself under the stimulating
influence of the latter to organic chemistry, which he has enriched by a
wealth of admirable and important work. His untiring study of con-
densation reactions has led him to results of the highest value, which will
frequently be referred to in the special history of organic chemistry. From
his laboratory there has come forth much work of a fundamental nature ;
we need only recall here that of Graebe and Liebermann on alizarin, and
that of E. and 0. Fischer on rosaniline, etc. Since 1860, in which year
Baeyer became assistant professor in Berlin, he has continued energetic as
a teacher— first at the Berlin Technical College, then from 1872-75 in
Strasburg, and lastly, from 1875, in Munich, where, as head of the Uni-
versity laboratory, which was built after his own plans, he has found a
brilliant sphere of action.
364 THE MODERN CHEMICAL PERIOD CHAP,
water, and ammonia — were for the most part based upon
condensation. The history of organic chemistry can tell
of many results of efforts to imitate such natural processes,
or at least to prepare products which occur in the vegetable
kingdom (acids, colouring matters, alkaloids, carbohydrates,
etc.) from substances of simpler composition. The most
important of those vegetable acids which had long been
known were prepared synthetically, — oxalic acid from
carbonic, succinic acid from ethylene, malic and tartaric
acids from succinic, and citric acid from acetone (which,
like ethylene, could be built up from its elements) ;
further, benzoic acid from benzene, cinnamic acid from
benzaldehyde, and so on. By those observations, the list
of which might be extended by numerous others on the
artificial formation of acids occurring in the animal and
vegetable kingdoms (e.g. the syntheses of chelidonic, vulpic,
and uric acids), the chemical constitution of these sub-
stances was determined with greater precision than had
hitherto been possible.
Similarly from the synthesis of vegetable colouring
matters and other bodies — e.g. alizarin, purpurin, indigo
blue, cumarin and vanillin, — trustworthy conclusions have
been drawn with respect to their rational composition. The
important problem of preparing the sugars and vegetable
alkaloids artificially has been taken in hand with success, —
witness the beautiful researches of Emil Fischer1 upon car-
bohydrates, which have lately led to the artificial formation
of grape sugar, and the ingenious synthesis of conine by
Ladenburg.2
One may safely express the opinion that a clear idea of the
chemical constitution of these and other difficultly accessible
classes of compounds, whose proximate composition has as
yet been but imperfectly worked out, will only be arrived
at after they have been synthetised from simpler ones of known
structure. The history of the synthesis of organic com-
pounds has already proved the truth of this axiom in
numerous instances.
1 Cf. the special history of organic chemistry. 2 Ibid.
v CHEMICAL CONSTITUTION OF ORGANIC COMPOUNDS 365
The chemical behaviour of organic compounds is in every
case regarded as an aid of the first importance in working
out their constitution, and has been valued accordingly
ever since organic chemistry began to flourish. A short
sketch only can be given here of a few of the more important
methods which have been applied during these last decades,
with the object of getting at the chemical constitution of
organic compounds from their reactions, transformations and
decompositions.
The general principle of such methods consists, in contra-
distinction to that of the synthetic, in investigating the
products obtained by the chemical alteration of the com-
pounds in question, and in deducing the constitution of the
latter from these. In many cases of transformation the
chemist keeps his attention fixed upon particular elements
or atomic groups united to carbon, the carbon framework
itself undergoing no change ; in many others, on the
contrary, carbon is separated as carbonic acid, carbonic
oxide, or even in a more complex form. For those classes
of substances which are among the best investigated, special
reactions have been discovered which make it possible to
decide whether a hitherto unknown compound belongs to
this or that group. Of recent years great attention has
been paid to the refinement of such reactions. To mention
only one or two important steps in this direction: —
Phosphorus pentachloride, acetic anhydride and hydriodic
acid have been found of inestimable value for determining
whether an organic compound contains hydroxyl, and, if so,
what function that hydroxyl performs. Further, the trans-
formation of nitro- into amido-compounds by reduction,
and that of the latter into oxy-derivatives by oxidation,
the conversion of cyanides into carboxylic acids, of hydro-
carbons into acids, and of amido- into diazo-compounds, have
all become typical reactions, which, when rightly interpreted,
lead very quickly to the explanation of the constitution of
such bodies. Lastly, we may recall here the beautiful method
of V. Meyer and E. Fischer, by which the presence of the
carbonyl group in a compound can be proved by means of
366 THE MODERN CHEMICAL PERIOD CHAP
hydroxylamine or phenyl-hydrazine. All the above and
other similar reactions have for their aim the definite recog-
nition of the role of elementary atoms or compound radicals
in organic molecules, and with this the partial solution of
the constitution of these latter; in numberless instances
this aim has been accomplished.
The decompositions of organic substances into others
poorer in carbon, which may be made use of for deciding
the same point, are legion, and will just be touched upon
here, in order to illustrate the principle of the method.
This plan is the direct opposite of the synthetic; while by
the latter the constitution of an organic compound is deduced
from that of its components, the former leads to the same
conclusion through a study of the resulting decomposition -
products. To give only one or two examples : — Let us recall
the important inferences drawn by v. Baeyer from the decom-
position of derivatives of uric acid into simpler bodies ; the
constitution of those compounds thus deduced by him was
subsequently confirmed by direct synthesis. The researches by
Frankland, Geuther, Wislicenus and others on the modes of
decomposition of aceto-acetic ether must also be mentioned,
researches which, conjointly with other synthetic ones,
cleared up the constitution of the latter. Further, carbonic
acid, formic acid, etc., are very often eliminated from organic
compounds, whose decomposition-products thus furnish a
clue to their rational composition. The changes produced
by oxidation in the case of numerous substances, such as the
ketones, quinoline bases, naphthalene derivatives and unsatur-
ated compounds, furnish excellent proof of the invaluable aid
given by researches of this nature towards solving the
question of chemical constitution. For further details on
this point, the reader is referred to the special history of
organic chemistry.
By this co-operation, by the use of the various methods
which are now an integral part of organic chemistry, the
problem *of the rational composition of carbon compounds
has been brought distinctly nearer to its solution.
INORGANIC AND GENERAL CHEMISTRY 367
The Main Currents in Inorganic and General Chemistry
during the last Thirty-five Years.
The doctrine of the saturation-capacities of the elements,
which has proved of such extraordinary importance for the
development of organic chemistry, has not by any means
found the same rapid and general application in inorganic.
After Odling, so early as 1854, had applied Frankland's idea
of valency to the oxides of a large number of the elements,
remaining however at the same time enchained by the type
theory (cf. p. 325), gradual attempts were made by a number
of chemists, either in text-books or in their experi-
mental researches, to engraft on inorganic compounds the
ideas which had so quickly found acceptance with respect
to the linking of carbon atoms among themselves or with
other elements. The gain which arose from this was first
apparent in the systematising of these compounds, which
became classified into natural families according to the
valencies ascribed to the individual elements. Similarity in
saturation-capacity formed the common link which held the
different members of such groups together. Thus Frankland
had already recognised the analogy between nitrogen, phos-
phorus, arsenic and antimony, from the fact that they were
all capable of acting either as tri- or as pentavalent. Along-
side of carbon were ranged silicon, titanium and zirconium,
as being in the main tetravalent elements, whereas boron,
which had formerly been ranked along with carbon, was seen
to be trivalent, and was relegated to another group. These
and similar efforts to introduce clearness into the syste-
matising of the elements, by classifying them according to
their chemical values, soon led to the establishment of the
important Natural System of the Elements (cf. p. 370).
The problem of interpreting the constitution of inorganic
compounds similarly to that of organic, by getting at the
relations which exist between their component dements,
has not been treated with the same care as in the case of
the latter. For substances of simple composition the diffi-
368 THE MODERN CHEMICAL PERIOD CHAP.
culty of the point was usually under-estimated ; this showed
itself more particularly in the arbitrary attempts at ex-
plaining the constitution of inorganic compounds on the
supposition that the valencies of the elements were invariable.
Thus it was often overlooked that the chemical behaviour of
a substance was not in accordance with the structural formula
assigned to it. Sulphur chloride, for example, was given
S-C1
the formula, | , without any heed being paid to the fact
S-C1
that one of its atoms of sulphur behaved quite differently from
the other. And the constitution of phosphorus oxychloride
could only be illustrated by the adherents of constant
/0-C1
valency by the formula, P\~ Cl , a formula which in-
xci.
dicated an (unproven) difference between one chlorine atom
and the other two.
And how the ordinary rules were strained in order to
indicate the composition of more complex compounds !
According to Wurtz,1 the constitution of bodies rich in
oxygen could usually be explained by assuming the oxygen
atoms to be linked to one another; take, for example,
periodic anhydride, in which seven atoms of oxygen
were linked together in a chain, with the two supposed
monovalent iodine atoms at either end. This very one-
sided assumption of a constant valency of the elements
was however gradually superseded, a sounder view
taking the place of such artificial explanations. But trust-
worthy methods of arriving at the constitution of complex
compounds are scarcely yet developed in inorganic chemistry,
although in organic much has already been done in this
direction.
The researches of greatest value for inorganic chemistry
which have been made during the last few decades are those
upon particular elements, more especially upon such as had
hitherto been imperfectly or even not at all investigated.
1 Lemons de Philosophie Chimique, p. 157.
v RELATIONS BETWEEN THE ATOMIC WEIGHTS 369
Thus the work of Roscoe l on vanadium, of Marignac 2 on
niobium and tantalum, and of Zimmermann, Kruss, von der
Pfordten, Moissan and others on uranium, gold, titanium,
fluorine, etc., have enabled those elements to be put in their
proper place among the others ; this of course only became
possible after their chemical character had been thoroughly
examined. The same applies to the more recently dis-
covered elements — thallium, indium, gallium, scandium r
germanium, etc., which have likewise been investigated by
their discoverers in a masterly manner.
All these researches, which will be referred to again in
the special history of inorganic chemistry, have had the
same ends in view, viz. the establishment of the chemical
character, and, in particular, of the combining relations of
the element in question, and the most careful possible deter-
mination of its relative atomic weight. In addition to all
this, an increasing value has come to be laid upon the obser-
vation of its physical properties. Such investigations upon
individual elements became more systematised after it was
clearly seen that a close connection existed between their
chemical and physical properties on the one hand and
the magnitudes of their atomic weights on the other.
Of course, when it came to a question of proving this
intimate relation, the first thing was to determine the
1 Sir Henry E. Roscoe, born in 1833, was a pupil of Bunsen's. For
nearly thirty years he held the chair of chemistry at Owens College, Man-
chester, resigning in 1885. His work has been for the most part in in-
organic and physical chemistry, the Photochemical Researches by Bunsen
and Roscoe (London, 1858-1863) deserving mention here. He is also well
known as the joint author of Roscoe and Schlorlemmer's Treatise on
Chemistry, as well as of other smaller text-books on the science. His
Lessons in Elementary Chemistry has run through numerous editions, and
has been translated into a great many different languages.
2 J. C. Marignac, born at Geneva in 1817, retired several years ago>
from the professorial work to which he had devoted himself in his native
city since 1842, and died there on April 15th, 1894. With the exception
of some researches on the naphthalene derivatives, his most important
work has been in the determination of the atomic weights of numerous
elements, and in other subjects of inorganic chemistry. A detailed account
of his life and his services to the science has been given by E. Ador in th#
Archives des Sciences Physiques et Naturelhs, vol. xxxii, p. 5.
B B
370 THE MODERN CHEMICAL PERIOD CHAP.
relative atomic weights as accurately as it was possible
to do.
The efforts of many chemists had already for a long
time been directed to improving as far as practicable the
methods of determining atomic weights, before the importance
of this question for the systematising of the elements had
come to be recognised. The memorable labours of Berzelius
were followed during the forties by those of Turner, Dumas,
Marignac, Erdmann, Marchand and Pelouze, and were
crowned by the classical researches of Stas l upon the atomic
weights of oxygen, chlorine, bromine, iodine, nitrogen, sul-
phur, silver, etc. In Stas's case the extreme limit of
accuracy was reached which was possible with the means at
command. But this certainty with respect to the magnitudes
of the relative atomic weights only extended to some of the
elements, the values hitherto assigned to many (e.g. molyb-
denum, antimony, platinum, osmium, iridium, etc.) being
exceedingly inaccurate. Much has, however, been accom-
plished in this direction of late years.2
The Periodic System of the Elements.
Prout's hypothesis, according to which the atomic weights
of all the elements stand in a simple relation to that of
hydrogen, acted for a long period like a ferment, in that it
gave rise to continually renewed speculations upon the con-
nection which existed between the elements and their atomic
weights. The observed fact that chemically analogous ele-
1 Jean Servais Stas, born at Lowen in Belgium in 1813, died in 1891
at Brussels, where he had occupied the chair of chemistry in the Military
School for a number of decades. His unique services in the determination
of the atomic weights of the elements are universally recognised. The
various papers on this subject were published by him in a collected form
in the well-known work, Eecherches sur les Bapports rdciproques des Poids
Atomiques, and in the Nouvelles Recherches sur les Lois des Proportions
Chimiques, etc. Organic chemistry and forensic analysis are also indebted
to him for most important investigations (see Special History).
2 Cf. the Special History of Inorganic Chemistry.
v THE PERIODIC SYSTEM OF THE ELEMENTS 371
ments possessed either nearly equal atomic weights, or atomic
weights separated from one another by definite numerical
increments, afforded food for such theorising. For almost
seventy years attention has frequently been drawn, with
more or less emphasis and ability, to regularities of this
kind ; the discussions of the point by Dobereiner, L. Gmelin,
Pettenkofer, Dumas, Kremers, Odling and others may be
recalled here.1 But it is only of comparatively recent years
that a systematic classification has followed from those efforts
to discover a connection between the atomic weights and the
nature of the elements.
In the year 1864 Newlands2 in England and Lothar
Meyer3 in Germany — independently of one another —
arranged a number of the elements according to the
magnitudes of their atomic weights,4 and thereby observed
that while, at a superficial glance, the elements following
one another showed apparently no regularity in properties,
1 Cf. L. Meyer's Moderne Theorien (fifth German edition), p. 133.
2 Chem. News, vol. xxxii., pp. 21 and 192; also Newlands' pamphlet,
The Discovery of the Periodic Law (London, 1884). Mendelejeff, in his
Grundlagen der Chemie, p. 683, calls attention to the fact that, so early as
1862, some parts of the periodic law were enunciated by Chaucourtois.
3 Lothar Meyer, born 19th August, 1830, filled from 1876 until his death
on April 29th, 1895, the first chair of chemistry in the University of
Tiibingen, after having previously worked as an academic teacher in
Breslau, Neustadt-Eberswalde and Karlsruhe. His first experimental
researches dealt with questions of physiological chemistry ; but he after-
wards turned his attention more to theoretical and physico-chemical
problems. The outcome of this was his valuable work, Die Modemen
Theorien der Chemie (fifth edition, 1884), which has been translated into
English by Professors Bedson and Carleton Williams under the title,
Modern Theories of Chemistry ; compare also his Grundziige der theoret-
ischen Chemie (1890). The efforts mentioned above, which he made with
the object of firmly establishing the periodic system of the elements, led
him on to a careful review of all that had been written on their atomic
weights (cf. his and K. Seubert's meritorious work, Die Atomgewichte der
Elementeausden Originalzahlen neu berechnet, 1883) (" The Atomic Weights
of the Elements newly Recalculated from the Original Numbers"). A
detailed account of Lothar Meyer's life and work, from the pen of his
pupil Seubert, is to be found in the Berichte, vol. xxviii, Ref. p. 1109 ; and
another by Bedson in the Journal of the Chemical Society for 1896, p. 1403.
4 Cf. Moderne Theorien (first German edition, 1864).
B B 2
372 THE MODERN CHEMICAL PERIOD CHAP.
after the lapse of a certain period the chemical and physical
behaviour of the elements now succeeding each other strongly
recalled that of the previous group, in fact repeated it. The
elements which resembled one another were therefore united
into groups or natural families, and these in their turn
were distinguished from the periods, which comprised the
elements whose atomic weights lay between those of two suc-
cessive members of a natural family. This attempt to classify
the elements according to the magnitude of their atomic
weights, and to deduce from this an important connection
between the latter and the properties of the former, called
forth at first more astonishment than recognition. Indeed,
Newlands did not escape banter on the subject, being asked
whether he would not try, with a similar result, to classify
the elements according to the initial letters of their names.
After the year 1869 these very imperfect beginnings
were soon greatly extended and improved by Mendel ejeff1
and Lothar Meyer,2 quite independently of one another, the
atomic weights of various elements having in the mean-
time been determined with greater accuracy than before.
Mendelejeff made what was for that time the bold attempt
to classify all the elements according to the magnitudes of
their atomic weights, the correctness of some of which was
extremely doubtful. He was thus able to show that the
elements which belonged to a natural family, i.e. those
which were chemically similar, followed one another in
regular periods. In this way the elements were brought
together into a natural system, as it was termed, in which
1 Ztschr. Chem. for 1869, p. 405; and more fully, Ann. Chem., Supple-
ment, vol. viii., p. 133. — D. J. Mendelejeff, born at Tobolsk on February
7th, 1834, has devoted himself to researches on physical constants, e.g.
specific volumes, expansion of gases, etc. He is best known by his famous
treatise, Die Periodische Gesetzmassigkeit der chemischen Elemente, and
also by his very original text-book, Grundlagen der Chemie. Since 1866
he has held the chair of chemistry in the University of St. Petersburg,
having previously occupied that in the Technological Institute there.
2 Ann. Chem., Supplement, vol. vii., p. 354; and also in the recent
editions of his Moderne Theorien.
v CONSEQUENCES OF THE PERIODIC SYSTEM 373
however, there was much that was arbitrary because of the
inaccuracy of many of the atomic weights. But the funda-
mental idea developed by the above investigators, viz. that
the elements arrange themselves on the one hand into
periods, and on the other into natural families, and that
all their properties are periodic functions of their atomic
weights, has been strengthened and verified in every direc-
tion by many subsequent investigations. The latter applies
more especially to the chemical valency of the elements,
the electro-chemical character, the atomic volume, the
thermo-chemical behaviour and other physical properties,
all of which stand in periodic dependence to the magnitude
of the atomic weight.
These efforts, so invaluable for the systematising of the
elements, have led to many important deductions. Thus,
in virtue of the periodic system, definite values could be
assigned to the hitherto uncertain atomic weights of various
elements ; for each element claims a place of its own in this
system and an atomic weight corresponding with this place,
the magnitude of the latter being calculable within certain
limits. When, for example, only the equivalent of an
element was known, the atomic weight could be deduced
from its behaviour and from the position thus accruing to
it in the natural system, as was actually done, e.g., for
beryllium and indium. Further, a choice could be made
between different definite values for one and the same
element, and the more suitable one taken, to be afterwards
verified, of course, with the utmost care. In this way the
periodic system has been applied in the happiest manner to
correcting the atomic weights of molybdenum, antimony,
caesium, etc.
Other conclusions of a speculative nature have likewise
been drawn with the best results from this classification of
the elements into periods and natural families. The gaps
shown by the system at the time it was brought forward,
and in a lesser number to-day, were and are intended to
be filled up by new and hitherto undiscovered elements.
374 THE MODERN CHEMICAL PERIOD CHAP.
Mendelejeff sought to predict from the positions of such
blanks, not merely the existence of elements and their
approximate atomic weights, but also their properties and
chemical behaviour, together with that of some of the com-
pounds which they would form. His prognostigations have
been fulfilled in the most striking manner by the discovery
of gallium, scandium and germanium, and by the verification
of their behaviour as foreseen by him. On the other hand,
the position in the periodic table of the elements argon and
helium, recently discovered by Rayleigh and Ramsay, pre-
sents great difficulty, as these elements show no definite
chemical reactions. (Cf. the Special History of Inorganic
Chemistry.}
The perception of the fact that the physical and chemical
properties of all the elements show a periodic dependence
upon their atomic weights is therefore a result of this natu-
ral classification. But the discovery of the common cause
which underlies these peculiar relations, and its formulation
into a law, still remain tasks for the future. Some chemists
have thought to lift this veil already by assuming that all the
various elements, or at least those belonging to a natural
family, may be referred back to still simpler ones. We per-
ceive clearly here a reapproach to Prout's hypothesis, which
threatened to exercise such an unfavourable influence on the
rational development of the atomic doctrine, had not the
ablest chemists of the time raised a protest against its
admissibility. During the last few years Crookes has again
brought up this ticklish question, whether the so-called
elements are to be regarded as simple, and not rather as
compound.1 According to him, all the elements have re-
sulted by gradual condensation from a primary material
which he terms protyle, this view having been arrived at
from his observations on the phosphorescence spectra of the
1 Cf. Chem. News, vol. liv. ; also Crookes' Presidential Addresses to
the Chemical Society in 1888 and 1889, published in the Society's Journal
for those years. Compare, too, W. Preyer's Das genetische System der
chemischen Elemente (1893).
HERMANN KOPP 375
yttrium earths. The peculiar nature of these yttrium earths,
which consist of a variety of substances, has conduced greatly
to speculations of the kind.
But until the transformation of one element into another
has been incontestably proved by experiment, chemists can-
not give up the idea of indivisible elementary particles, i.e.
the present atomic theory.
The General Significance of Physico-chemical Investigations.
The relations thus discovered between the atomic weights
of the elements and their physical properties have materially
contributed to enlarge our knowledge of the boundary-land
between physics and chemistry. Many investigators had
previous to this followed the example of H. Kopp 1 (who
began his stimulating labours in the forties), in assiduously
tracing out the connection existing between the chemical
constitution of compounds and their physical behaviour.
1 Hermann Kopp, born 30th October, 1817, at Hanau (at which place his
father was an esteemed physician), after studying at Heidelberg, was
drawn through Liebig's attraction to Giessen, where he became assistant
professor of chemistry in 1841 and professor at a later date. At Giessen he
remained until his removal to the University of Heidelberg in 1864, where
he continued to work in full vigour until shortly before his death, which
took place on February 20th, 1892. His services as a historian of
chemistry have already been frequently referred to. All his historical
works [Geschichte der Chemie (" History of Chemistry "), 4 vols. 1843-47 ;
Die Entwickelung der Chemie in der neueren Zeit, 1873 ("The Development
of Chemistry in Recent Times"); Beitrdge zur Geschichte der Chemie
("Contributions to the History of Chemistry"); Die Alchemie in dlterer
und neuerer Zeit. (" Alchemy, Old and New ")] are distinguished by their
comprehensiveness and thoroughness. He possessed in a remarkable
degree the gift of sympathetically tracing out the development of im-
portant ideas and hypotheses. The stimulus produced by his physico-
chemical researches was a highly gratifying one (cf. the special history of
physical chemistry). In addition to all this, he took a share in the editing
of Liebig's Jahresbericht and of the Anncden der Chemie und Pharmacie,
besides writing his Lehrbuch der theoretischen Chemie (1863) for the Graham-
Otto series. Immediately after Kopp's death, A. W. von Hofmann de-
livered in his memory one of those biographical addresses, which none
could do so well as he. (See Ber., 1892, Ref. p. 505).
376 THE MODERN CHEMICAL PERIOD CHAP.
The advances made in this direction fall to be treated of in
the special history of physical chemistry. Here it need
merely be said that it has come to be more and more recog-
nised, especially within the last thirty or forty years, that
chemical investigation runs the danger of becoming one-sided
without a free use of physical aids. Chemists have perceived
the necessity for their science of physico-chemical methods.
Thus, what a wide application have not the latter found
in the estimation of the molecular weights of elements and
compounds ! The determination of vapour density has
proved its value for the attainment of this end in an infinite
number of cases, and has been applied to the solution of the
most important theoretical questions ; thus, of recent years
the saturation-capacities of numerous elements, e.g. tungsten,
vanadium, beryllium, thorium, germanium, aluminium, etc.,
have been established by the aid of this process. The con-
stant relations between the molecular weight of a substance
on the one hand and its point of solidification and the vapour
pressure of its solutions on the other, first definitely formu-
lated by Kaoult and de Coppet (independently), have rapidly
become the basis of easily-carried-out methods for the deter-
mination of molecular weights. In fact, the investigations
on the physical behaviour of solutions — e.g. their electric con-
ductivity, osmotic pressure, vapour pressure, etc. — have
during the last few years enlarged the boundaries of general
chemistry to an extent that was undreamt of.
We need only refer here to the deduction of the atomic
weights of elements from their specific heats, and of equiva-
lents from the electrolysis of salts, in order to emphasise the
significance of physical methods for establishing the most
important of chemical values. Of the wealth of work which
has been accomplished in the branches of spectrum analysis,
thermo-chemistry, electro-chemistry, upon the doctrine of
affinity ( VerwandtschaftsleJire), and in the investigation of
the connection between optical properties and chemical con-
stitution, an account will be given in the special section.
The position of chemistry to physics will there come out
more clearly than is possible at this point. Thanks to the
v OSTWALD AND VAN 'T HOFF 377
labours of Ostwald,1 van 't Hoff2 and others, the physical
conceptions of the transformation and conservation of
energy have now come into general application in chemistry
also, more especially in the explanation of affinity-pheno-
mena.
Similarly, the relation of chemistry to other branches of
science can only be properly represented by going into details.
This will show itself in the case of mineralogy, which is
1 Wilhelm Ostwald, born at Riga on September 2nd, 1853, taught first
in the University of Dorpat, then at the Riga Polytechnic from 1880 to
1887, and has since the latter year held the chair of Physical Chemistry in
the University of Leipzig. The amount of work which he has already done
in this branch of the science has been very great, the subject having been
immensely advanced both by his researches and his writings. Up to 1887
his papers were published in the Journal fur praktische Chemie, but since
that date in the Zeitschrift fur physikalische Chemie, which he himself
and van 't Hoff started, and continue to edit. Some papers have been
brought out in the Ber. der Konigl. Sachs Gesellschaft der Wissenschaften.
His large Lehrbuch der allgemeinen Chemie (2 vols.), of which two editions
have so far appeared, and also his Grundriss der allgemeinen Chemie, have
found universal acceptance. Part of the former has been translated into
English by M. M. P. Muir, while the English edition of the latter is by
James Walker. His Hand- und Hilfsbuch zur A usfuhrung physiko-chemischer
Messungen (1893), also translated into English by Walker, is of great
practical value. A smaller work, Die wissenschaftlichen Grundlagen der
Analytischen Chemie (1894), is also highly original— in fact, the only book
of its kind ; it too has been translated (by G. McGowan). Lastly, his large
work, Elektrochemie, ihre Geschichte und Lehre (1896), is thoroughly apposite
at the present time, and deserves special mention. In addition to these,
Ostwald's Klassiker der exakten Wissenschaften, being reprints of classical
scientific papers, have made these accessible to any reader of German (the
"Alembic " series is their analogue in this country).
2 J. H. van 't Hoff was born at Rotterdam on the 8th of August, 1852.
After studying at Delft, Leyden, Bonn, Paris and Utrecht, he became a
lecturer in the Veterinary College of the last-named city in 1876, and
Professor of Chemistry in the University of Amsterdam in 1878 ; in 1896
he was made an honorary professor of the University of Berlin. Van 't
Hoff has shown himself to be a man of singularly original mind, and his
work will be frequently referred to in the special sections of this book. In
addition to his numerous papers contributed to scientific journals and his
share in editing the Zeitschrift fur physikalische Chemie along with Ostwald,
he is the author of the following works :— La Chimie dans VEspace (1875) ;
Dix Anne'es dans VHistoire d'une Theorie (1887) ; Ansichten uber die
organische Chemie (1878-1881) (" Views upon Organic Chemistry ") ; Etudes
de Dynamique chimique (1884); and Lois de V fiquilibre chimique (1885).
378 THE MODERN CHEMICAL PERIOD CHAP, v
united to inorganic chemistry by a firm band. The con-
nection with physiology is proved by the fact that organic
chemistry is absolutely necessary to the latter. In fact, to
whatever quarter we turn in the extensive range of the
natural sciences, we find that chemistry is to most of them
an indispensable aid, and to the remaining ones useful
in a high degree. The history of the different branches of
natural science shows in the most distinct manner this con-
stantly recurring reciprocal action.
SPECIAL HISTORY OF THE VARIOUS BRANCHES
OF CHEMISTRY FROM LAVOISIER TO THE
PRESENT DAY
CHAPTER VI
SPECIAL HISTORY OF THE VARIOUS BRANCHES
OF CHEMISTRY FROM LAVOISIER TO THE
PRESENT DAY
Introduction. — In the general history of this period the
attempt has been made to set forth the more important
ideas and points of view which have led to the development
of particular doctrines, and at the same time to give a
description of the latter. In conjunction with these
objective discussions, short sketches have been appended of
the lives of those investigators who have exercised a
permanent effect upon the development of chemistry, and
more especially upon the systematising of it.
Up to the fourth or fifth decade of our century, the
leading chemists were able to cover in their work a very
large* part of the ground which was either occupied by
chemistry itself, or in which it was an indispensable aid ; we
have but to think of Berzelius and Liebig, and of their labours,
which were at the same time both pioneering and funda-
mental, in analytical and pure chemistry, physiology and
mineralogy. But during the later decades the tremendous
growth of the science has necessitated a large subdivision of
work, indeed an almost one-sided specialisation in research.
This may even give rise to the apprehension that, with
increasing specialisation, a danger is run of losing sight of
general guiding principles. Organic chemistry may serve as
an example of this subdivision of labour, particular branches
of it having been opened up which in themselves alone are
sufficient to absorb the full energies of large numbers of
382 HISTORY OF THE VARIOUS BRANCHES OF CHEMISTRY CHAP.
capable investigators ; take for instance the chemistry of the
aromatic compounds, and more especially that portion of it
comprising the pyridine and quinoline bases and similar
compounds richer in nitrogen. The new journals unmistak-
ably reflect this subdivision of labour. While formerly
Poggendorffs Annalen, Liebig's Annalen, the Journal fur
praktische Chemie, the Journal of the Chemical Society, &c.,
contained papers in every branch of the science, we now find
journals exclusively devoted to inorganic, physical, physio-
logical, agricultural, pharmaceutical and applied chemistry.
In the following special section of this book, which deals
with the different branches of chemistry in succession, such
facts and investigations are recorded as have contributed to
the true advancement of the various parts of our science.
The history of analytical chemistry is placed first in
order, since the latter is an indispensable aid to all chemical
research, and therefore to all the other branches of chemistry,
pure as well as applied. Following it comes the history of
pure chemistry, which divides itself into inorganic and
organic, although there is no natural partition between the
two. Next to pure chemistry stands physical, with whose
history that of the doctrine of affinity ( Verwandtschaftslehre)
is intimately bound up. It was the endeavour to discover
relations between chemical and physical properties which led
to the establishment of this important middle kingdom
between chemistry and physics.
That chemistry is necessary for the healthy growth of other
sciences is particularly shown in the history of mineralogical,
physiological and pathological chemistry, which are also
treated here according to their historical development. The
opening up and cultivation of the fields of mineralogy,
geology, and vegetable and animal physiology are indis-
solubly connected with the names of such distinguished
chemists as Lavoisier, Vauquelin, Klaproth, Berzelius and
Liebig.
Last in order comes the history of technical chemistry,
which illustrates in the most brilliant manner the influence
of chemical research upon the development of chemical
vi HISTORY OF THE VARIOUS BRANCHES OF CHEMISTRY 383
industry. To give a historical account of the penetration
of the scientific spirit and of chemical methods into this
branch, a branch hitherto worked empirically, is a task
which repays itself in a special degree.
As an appendix to the whole, an attempt has been made
to picture within short space the growth which chemical
instruction has undergone in the course of the present
century.
384 HISTORY OF ANALYTICAL CHEMISTRY CHAP.
HISTORY OF ANALYTICAL CHEMISTRY IN RECENT TIMES.
The main problem of chemistry, the investigation of the
true composition of compounds, necessarily carries along with
itself the constant endeavour to elaborate and perfect the
means employed for arriving at this end. Thus, since the
time of Lavoisier, analytical methods, which constitute the
tools for the solution of this problem, have been and are
being improved in a continuously increasing degree.
Qualitative Analysis of Inorganic Substances.
Even so early as during the phlogistic period, men like
Boyle, Hoffmann, Marggraf, and especially Scheele and
Bergman, had collected together a large number of valuable
observations, by means of which it was possible to test with
certainty for many inorganic compounds. In a knowledge
of the various reagents which served for this end Bergman
was the furthest advanced ; he it was who first attempted to
publish a system for the qualitative analysis of substances in
the wet way (cf. p. 143). From the analytical course of pro-
cedure which he proposed, and which had for its aim the
separation of different substances into particular groups by
converting them into insoluble compounds, the methods in
use at the present day have developed themselves. To the
perfecting of this (previous to the time of Berzelius, who also
worked with the greatest effect in this branch), Lampadius
and Gottling materially contributed ; the former published
in 1801 his Handbuchzw chemischen Analyse der Mineralien
(" Text-Book on the Chemical Analysis of Minerals "), and
the latter his Practische Anleitung zur prufenden und zer-
legenden CJiemie (" Practical Introduction to the Chemistry
of Testing and Decomposing"), — works in which the best
analytical methods of the time are given.
vi DEVELOPMENT OF QUALITATIVE ANALYSIS 385
The many and varied observations collected by Klaproth,
Vauquelin, Berzelius, Stromeyer and others in their analyses
of minerals further helped to strengthen the qualitative
method. The text-books of analytical chemistry by C. H.
Pfaff and Heinrich Rose enable us to judge of the rate of its
continuous development ; alongside of the latter of those
works, which became justly celebrated and ran through
numerous editions, must be placed the well-known and
highly prized Anleitung zur qualitativen chemischen Analyse
(" Introduction to Qualitative Chemical Analysis ") of R.
Fresenius, which covers the whole ground on the subject,
and is a marvel of thoroughness and accuracy. The pro-
cedure in qualitative analysis has undergone no material
alterations since Fresenius first published his book, and is
treated of in numerous works, most of which are intended to
instruct the beginner in its principles.1
Qualitative analysis in the dry way has been perfected
by the more general and improved use of the blowpipe,
which Berzelius2 and Hausmann were in a high degree
instrumental in introducing into chemistry and mineralogy.
This valuable little instrument has been employed with the
greatest success, more especially for the detection of the con-
stituents of minerals ; Bunsen's important flame-reactions 3
have, however, enabled it to be dispensed with in a number
of cases. Among the most noteworthy of dry reactions are
the spectroscopic, which, thanks to their extraordinary
delicacy and certainty, serve for the detection of the most
minute quantities of many metals, and have rendered pos-
sible the discovery of a number of new elements. Spectrum
analysis, through which we are able to deduce the nature of
a glowing substance by examining the light which it emits,
1 Out of the large number of such text-books, those of Beilstein,
Birnbaum, Classen, Drechsel, Geuther, Meclicus, Rammelsberg, Stadeler-
Kolbe,Will, Odling, Harcourt and Madan, Thorpe, Clowes, and Jones may
be mentioned.
2 His pamphlet, Ueber die Anwendung des Ltithrohrs ("On the
Application of the Blowpipe "), was first published in 1820; cf. also p. 144.
3 Ann. Chem., vol. cxxxviii. p. 257 ; also in a much extended form as
a separate pamphlet.
C C
386 HISTORY OF ANALYTICAL CHEMISTRY CHAP.
was founded by the masterly researches of Bunsen and
Kirch off;1 Talbot, Miller, Swan and others had before this
investigated the spectra of coloured flames, without however
applying their results with a definite aim to the analysis of
substances. The first proposal to utilise the different flame
colourations for distinguishing potash from soda salts was made
long ago by Marggraf2
Quantitative Analysis of Inorganic Substance*.
The accurate investigation of the behaviour of bases, acids
and salts towards different reagents, especially towards such
as yield with them either sparingly soluble or insoluble
precipitates, constituted the basis of the gravimetric estima-
tion of individual substances. Before the time of Lavoisier
few attempts had been made at quantitative analysis, but
the path which it was bound to follow had been already
clearly indicated by Bergman ; for he was the first to
enunciate the principle of converting the substance to be
analysed into a convenient form of known composition, and
then deducing from the weight of the compound thus pre-
cipitated or otherwise obtained that of the substance in
question. At that date chemists either already knew or
became acquainted with the precipitation of silver solutions
by hydrochloric acid, of solutions of lime salts by oxalic or
sulphuric acid, of lead salts by liver of sulphur or sulphuric
acid, and many similar reactions. It was Klaproth who
taught the ignition of precipitates before weighing them, in
those cases where they did not suffer decomposition through
this procedure, and he also co-operated largely with Vauquelin
in developing the quantitative analysis of minerals. The
observations of both of these chemists, especially of Klaproth
(who directed his efforts to ascertaining correctly the com-
position of those compounds into which the constituents of
the substances to be analysed were usually transformed),
1 Pof/g. Ann., vol. ex. p. 161.
2 Cf. p. 143. It has been already mentioned that Scheele made the same
observation.
vi DEVELOPMENT OF QUANTITATIVE ANALYSIS 387
attained to a fairly high degree of accuracy ; and this also
applies to the analyses of salts carried out by Wenzel at an
earlier date, although to these hardly any attention had been
paid. Richter's endeavours to establish the quantitative
composition of salts, and the success which followed them,
have been sufficiently described in the general history of this
period ; in spite of the fact that his analyses were not par-
ticularly accurate, he understood how to draw important
and correct deductions from them.
Lavoisier, who had from the outset of his scientific career
clearly grasped the importance of proportions by weight, and
with this of quantitative analysis, examined more par-
ticularly the composition of oxygen compounds, Thus he
established with tolerable correctness (for example) the
relation of carbon to oxygen in carbonic acid, but only
approximated to that of hydrogen to oxygen in water, and
was wide of the mark in the relation of phosphorus to oxygen
in phosphoric acid. He also sought to apply the values which
he had obtained for the composition of water and carbonic
acid to establishing the composition of organic substances.
Lavoisier, however, introduced no original methods for the
quantitative analysis of inorganic bodies and their separation
from one another.
Proust effected infinitely more in this branch, his
analytical work leading, as has already been stated, to a
clear grasp of the law of constant proportions, and of the
alteration by definite increments in combining proportions.
Quantitative analysis was also strengthened and extended by
the establishment of stochiometry (which found its perfect
support in Dalton's atomic theory), since a check upon the
results obtained was thereby rendered possible.
Endeavours were at that time mainly directed to the
determination of the relative atomic or, to speak more
correctly, combining weights. The splendid results obtained
by Berzelius from his pioneering labours in this direction
have already been detailed. He devised a large number of
new gravimetric methods of estimation, and tested those
already in use for the separation of substances, working out
c c 2
HISTORY OF ANALYTICAL CHEMISTRY CHAP.
better modes for attaining to this end. His researches on
the composition of chemical compounds embraced every
element which was at all well known. Berzelius, far more
than any other man, developed the principles by which
atomic weights could be established ; and the degree of
accuracy at which he arrived in his analyses is seen from
the tables of atomic weights published by him after the
year 1818 (cf. pp. 218 and 224).
The great task of determining the atomic weights — the
constants of the atomic theory — with the utmost possible
accuracy, has led ever since the time of Berzelius to the
development and improvement of gravimetric methods ; for,
what is required here is to establish by various procedures an
unalterable value for each element, a value which shall form
the basis for the composition of all the compounds of that
element. The efforts and speculations to round off these
numerical values in accordance with Prout's hypothesis were
replaced by exact quantitative determinations. Among the
latter the researches of Dumas, Erdmann and Marchand,
Marignac, and Stas deserve special mention.1
The systematic development of quantitative analysis was
thus mainly promoted by the investigation of mineral sub-
stances, since the chief requirement here was to find out
modes for separating their constituents from one another.
After the valuable preparatory labours of Bergman (with
whom, for instance, the fusion of silicates with alkaline
carbonates originated), and the researches of Klaproth,
Vauquelin and Proust, it was Berzelius who worked out
entirely new methods ; we need only recall here his plan of
decomposing silicates by hydrofluoric acid, and that of
separating metals from one another by means of chlorine.
He it was, too, who first employed far smaller quantities
of substances than the large amounts recommended by
Klaproth, who introduced the spirit-lamp which bears his
name, thus facilitating the ignition of precipitates, and who
taught how to incinerate the filter-paper and determine its
1 Cf. Lothar Meyer and K. Seubert, Die Atomgeivichte der Elemente
,(1883).
vi BERZELIUS, H. ROSE, WOHLER, FRESENIUS, ETC. 389
ash ; in fact, to speak generally, he was the first to make use
of a large number of practical contrivances and apparatus
for the carrying out of analyses. His greater analytical
researches, such as those upon platinum ores and on mineral
waters, show Berzelius as a master in devising good methods
of separation.
His pupils, more especially H. Rose1 and Fr. Wohler,
worked up the valuable experiences of their teacher, extended
them largely by wide-reaching observations of their own,
and made analytical methods public property by their
admirable books 2 on the analysis of minerals and chemical
bodies generally. R. Fresenius,3 until quite lately our chief
exponent of analytical chemistry, likewise perfected and
strengthened this branch of the science in all its various
parts by collating and sifting the methods formerly in use,
1 The brothers Heinrich and Gustav Rose belonged to a Berlin family
which produced distinguished chemists for several generations. Their
grandfather, Valentin Rose the elder, a pupil of Marggraf, and also their
father, Valentin Rose the younger, were energetic pharmacists and
chemists. Gustav Rose, who was born in 1798 and died in 1873 as Pro-
fessor of Mineralogy at Berlin, was only connected with chemistry in-
directly. But Heinrich Rose (born 1795, died 1864) was an ardent exponent
of the science, and enriched it by most important work, especially in
analytical and inorganic chemistry (see special history of these). He
reciprocated fully and truly the affection of his master Berzelius, as is
vividly shown in the beautiful memorial address which he gave of the
latter (cf. p. 209). In his two-volume Handbuch der analytischen Chemie,
H. Rose collected together in a masterly manner the best of the then
known methods in qualitive and quantitative analysis.
2 H. Rose, AiLsfdhrliches Handbuch der ancdytischen Chemie (" Detailed
Textbook of Analytical Chemistry") ; Fr. Wohler, Die Mineralanalyse in
Beispielen (" The Analysis of Minerals, illustrated by Examples ").
3 C. Remigius Fresenius, born at Frankfurt on the Maine in 1818, became
assistant to Liebig in Giessen in 1841, and assistant professor there in 1843 ;
in 1848 he opened his now universally known laboratory at Wiesbaden, which
has undergone a continuous extension, and been frequented by students
from all parts. His text-books of chemical analysis, of which the Qualitative
appeared for the first time in 1841, and the Quantitative in 1846, have had
an extraordinarily wide distribution, as their numerous editions in different
languages prove. Every one who has used them systematically cannot fail
to have been struck with their wonderful accuracy and at the same time
great breadth. Fresenius died suddenly, while still in active work, on June
llth, 1897.
390 HISTORY OF ANALYTICAL CHEMISTRY CHAP.
and, more especially, by working out many new ones. By
founding in 1862 the Zeitschrift fur analytische Chemie,
Fresenius supplied a centre-point for the analytical branch
of the science. It is impossible to enumerate here what
other workers (among whom Liebig, Thomson, Stromeyer,
Bunsen, Turner, Scheerer, Rammelsberg, Gibbs, Blomstrand,
R. Schneider, Pelouze, and Winkler may be named) have
done for the development of quantitative analysis.
We may, however, mention here that the galvanic
current has of late years been called in to the service of
analysis, the quantitative determination of many metals
being rendered possible by its aid. After Gibbs (in 186 5)
had worked out the electrolytic determination of copper,
and other chemists had subsequently busied themselves with
similar investigations, Alexander Classen1 rendered special
service in the development of the method. This branch of
chemical analysis is of the utmost use for metallurgy, in
which even already it forms an important part of docimacy.
The latter, originally confined to the determination of the
noble metals in the dry way, has expanded into an important
branch of analytical chemistry, particularly sine e C. Fr.
Plattner's comprehensive researches and the publication of
his classical book, Die Probierkunst mit dem Lothrohr Leip-
zig, 1835), ("Docimacy by Means of the Blowpipe").2
Volumetric Analysis.
Besides the analytical methods which have been touched
upon above,' volumetric ones have become developed within
the last seventy years or so; these are of great use, par-
ticularly in manufacturing chemistry and pharmacy, and
have therefore the widest application. Since in volumetric
1 Cf. his work, Handbuch der chemischen Analyse durch Electrolyse
("Text-Book of Chemical Analysis by means of Electrolysis"). In the
Berichte, vol. xxvii., p. 2060, there is a further paper by Classen, in which he
gives very useful data, regarding particular points in electrolytic determina-
tions.
2 Cf. Kerl's Metallische ProUerkunst ("Metallic Docimacy"), (1886);
Balling's Probierkunde ("Docimacy"), (1879), and his Fortschritte im Pro-
bierwesen ("Advances in Docimacy"), (1877).
vi VOLUMETRIC ANALYSIS 391
methods no weighing is required after the standard solutions
have once been made up, and the wished-for results are arrived
at simply by reading off the amounts of the solutions used,
much time is saved and at the same time sufficient accuracy
attained, the requirements of technical analysis (more
particularly) being thereby met.
Gay-Lussac must be regarded as the man who introduced
volumetric methods into the science, and rendered them
available for chemical industries; before him various in-
vestigators— of whom Descroizille and Vauquelin must be
specially mentioned — had attempted to apply such methods
empirically to comparative determinations of chemical
products.
Gay-Lussac worked out with the greatest care his
methods of chlwimetry (1824), of alkalimetry (1828), and of
the determination of chlorine and silver (1832).1 Notwith-
standing the excellent results which those volumetric pro-
cesses yielded, they received but slowly the recognition which
was their due. The application of permanganate of potash
to the estimation of iron by Margueritte in 1846, and, more
particularly, Bunsen's process with equivalent solutions of
iodine and sulphurous acid (by means of which a large
number of different substances can be accurately estimated
by one and the same reaction) are landmarks in the history
of " titrimetry," which soon after this began to rank alongside
of gravimetric analysis. One of the chief promoters of
volumetric methods was Friedrich Mohr, who both improved
old processes and introduced many new ones ; he rendered
great service by the publication of his Lehrbuch der chemischen
Titrirmethode ("Text -book of Volumetric Analysis").2
Among the many investigators who have enriched this
branch of the science we may name J. Volhard,3 who devised
an exact method (the determination of silver by means of
ammonium sulphocyanide) capable of numerous applications.
1 Cf. his Instruction sur Ufissai des Matieres par la Vote Humide (1833).
2 The latest edition of this is edited by A.Classen. Among other valu-
able books on volumetric analysis are those of Cl. Winkler, Medicus, and
Fleischer in Germany, and of Sutton in England.
3 Cf. Ann. Chem. vol. cxc. p. 1, et seq.
392 HISTORY OF ANALYTICAL CHEMISTRY CHAP.
In organic chemistry volumetric analysis has not been
able to take up anything like the same position that it has
in inorganic, the methods as yet introduced being wanting
in precision. Among the most noteworthy processes here
are Fehling's for the determination of grape sugar, Liebig's
for that of urea, the volumetric estimation of phenol by
means of bromine,1 etc.
Development of Methods of Gas Analysis.
The history of the volumetric analysis of liquids
naturally leads us on to a description of the efforts to
analyse gases qualitatively and quantitatively. It is worthy
of note here that the systematic qualitative analysis of these
was much later of being developed than their quantitative
determination. The first attempts in this direction were
made by Scheele, Priestley, Cavendish and Lavoisier, to be
followed by those of Dalton, Gay-Lussac, Henry, de Saussure
and others at the beginning of this century. But it has
been through Bunsen's fundamental researches2 that the
quantitative analysis of gases has been brought to such
perfection that those methods which depend upon the
absorption or combustion of the gas under investigation are
among the most exact of our science, having required but
trifling modifications since he first published them.
In addition to Bunsen's methods, others have been
worked out with a special view to technical gas analysis;
although the same as the former in their main principle,
these allow of determining the composition of the so-called
industrial gases by the aid of simple apparatus within a
short time, and with sufficient accuracy. Cl. Winkler and
1 Cf. Degener, Journ. pr. Chem. (2), vol. xvii. p. 390 ; Koppeschaar,
Ztschr. Ann. Chem. for 1876, p. 223.
- These researches of Bunsen's began about the year 1838, and were
Collected together under the title of Gasometrische Methoden (Brunswick,
1857 ; second edition, 1877) ; this most valuable work was translated into
English by Roscoe. Kolbe, in the HandworterbucJi (under the article
" Eudiometer "), had already brought the details of these methods before-
public notice so early as 1843.
vi DEVELOPMENT OF ORGANIC ANALYSIS 393
W. Hempel have rendered great service here by materially
simplifying the apparatus required and by generalising
methods.1 Among others who have done good work in gas
analysis of recent years may be mentioned Frankland,
Pettersson, Orsat, Coquillon and Bunte.
The qualitative analysis of gases has only quite recently
been developed scientifically, and here, too, Winkler has
laboured with success ; by the systematised use of absorptives
he has divided gases into different groups, thus proceeding
in the same manner as is done in the analysis of substances
in the wet way. The recent work by Ramsay and his col-
laborators in connection with the two new gases argon and
helium must also be referred to here. The improvements in
methods of gas analysis have drawn the attention of chemists
to gases in an increasing degree, and have proved of the
greatest benefit to theoretical as well as to practical chemistry.
The Analysis of Organic Substances.
The fact that animal and vegetable products, which
came to be comprised under the term " organic," always
contain carbon, usually hydrogen and oxygen, and frequently
also nitrogen, was — as already stated — a long time of being
recognised. Here again we have a brilliant proof of
Lavoisier's far-seeing glance, and of his power of drawing
general conclusions from detached observations. It had
indeed struck previous experimenters, e.g. van Helmont and
Boyle, that spirit of wine, wax, etc., form water when
burned, while Priestley perceived that carbonic acid was
produced at the same time; in fact Scheele stated in 1777
that both of these compounds were products of the com-
bustion of oils. After it had become clear to Lavoisier that
carbonic acid consisted of carbon and oxygen, and water of
1 Cf. Clemens Winkler, Anleitung zur chemischen Untersuchung der In-
dustriegase, Freiberg, 1876-77 (" Methods for the Chemical Examination of
Industrial Gases ") ; the same author's Lehrbuch der technischen Gasanalyse
second edition, 1892), ("Text-Book of Technical Gas Analysis") ; and W.
Hempel's Neue Methode zur Analyse der Gase (Brunswick, 1880), and Gas-
anaJytische Methoden(189Q).
394 HISTORY OF ANALYTICAL CHEMISTRY CHAP.
hydrogen and oxygen, he went on to deduce the composition
of organic substances. Thus, with the discovery of what
were the most important elements of organic compounds,
the first step in qualitative organic analysis was reached.
The principle of arriving at the constituents of organic
bodies by transforming them into compounds of known
composition has ever since been retained. In the same way
nitrogen, which Lavoisier himself recognised as being
peculiar to many organic substances,1 was detected by con-
version either into ammonia (Berthollet) or sodium cyanide
(Lassaigne), and phosphorus and sulphur by conversion into
phosphoric and sulphuric acids respectively.
While the elementary constituents of organic compounds
are thus easily arrived at, the detection of the compounds
.alongside of one another is a much harder task ; only small
beginnings have as yet been made at a systematic course
•of qualitative organic analysis, in the sense in which we
apply the term to inorganic.2 In many instances one
has to depend upon isolated characteristic reactions of
organic substances, e.g. in the investigation of colouring
matters, alkaloids, protein substances, carbohydrates, etc.
The quantitative analysis of organic compounds has
developed itself from the observation that carbonic acid and
water are products of their combustion ; the method, there-
fore, which served for the detection of the constituents
carbon and hydrogen was\applied in a perfected form to
their exact determination. Lavoisier was again the first
to point out the right path here ; he attempted to burn the
organic compound in question -completely, and to estimate
the resulting carbonic acid and water — the latter indirectly.
In order to be able to deduce the amounts of carbon and
hydrogen themselves, it was necessary to know the quanti-
tative composition both of carbonic acid and of water ; but,
since the values obtained by him for these were not very
1 How uncertain the tests for the elements of organic substances were
at the beginning of this century is shown by the fact that Proust believed
he had proved nitrogen to be an integral constituent of acetic acid.
- Cf. Barfoed's Qualitative Analyse organischer Ktirper ; also Allen's
Commercial Organic Analysis.
vi METHODS OF ORGANIC ANALYSIS 395
accurate,1 it was impossible that the results of his analysis
of an organic substance could turn out correct, and this all
the more from the method of the combustion being such as
to involve errors in itself.
Lavoisier's process for easily combustible substances was
to burn a weighed quantity in a known volume of oxygen,
contained in a receiver closed by mercury, and then to esti-
mate the resulting carbonic acid together with the residual
oxygen; from these data the amounts of carbon, hydrogen
and oxygen were calculated. For difficultly combustible
bodies, such as sugars and resins, Lavoisier (as we now learn
from his recently published journals) 2 used, instead of the
free gas, substances which yield up their oxygen upon being
heated, e.g. red oxide of mercury and red lead ; he thus
adopted the plan which later on became the standard one,
while at the same time he estimated the weight of the
carbonic acid produced by this oxidation by means of a
solution of caustic potash.
Had those researches become known at that time, organic
analysis would doubtless have undergone a more rapid
development than it actually did. The efforts of Dalton
(1803), Saussure (about 1800-1803), and Thenard (1807) to
arrive at the composition of organic compounds by exploding
their vapours with oxygen and analysing the resulting pro-
ducts would never have been made. Gay-Lussac and
Thenard3 endeavoured to solve this problem in a more
felicitous manner by the combustion of the organic substance
with chlorate of potash ; from the amounts of resulting
carbonic acid and residual oxygen they calculated the per-
centage of carbon, hydrogen and oxygen in the substance
under analysis, and attained in some instances at any rate to
1 The following are Lavoisier's figures for the composition of carbonic
acid and water (the correct values being given in brackets) : —
/-Carbon 28 percent. (27 '2)
Carbonic Acid . . . | Oxygen 72 „ (72'8)
Water- { Hydrogen 13' 1 „ (11-1)
I Oxygen 86 '9 „ (88 -9)
2 (Euvres de Lavoisier, vol. iii. p. 773.
3 Recherches Physico-chimiques, vol. ii. p. 265.
396 HISTORY OF ANALYTICAL CHEMISTRY CHAP,
serviceable results. Compared with this method, uncertain
as it was on account of the violence of the combustion, the
one followed by Berzelius showed a marked improvement ; l
for here the organic substance, mixed with chlorate of potash
and sodium chloride, was gradually decomposed, and then
not merely the resulting carbonic acid but also the water
determined directly — the latter by means of chloride of
calcium. A further advance was made by Gay-Lussac 2 in
1815, in the use of black oxide of copper as the oxidising
agent. But the rounding off of the whole procedure by the
introduction of a convenient bulb-shaped apparatus, and the
consequent simplification of the manipulation required, is due
to Liebig.3 Since his time elementary organic analysis has not
altered essentially, the modifications introduced having had
reference to the combustion furnaces (now heated by gas
instead of charcoal), and to the mode of carrying out the
combustion ; with respect to the latter, Koppfer's method 4
must be mentioned, a method by which the substance is
burnt in a current of oxygen, with the aid of platinum black.
Plans for the combustion of organic compounds in a stream
of oxygen had before this been proposed by Hess, Erdmann
and Marchand, Wohler, and others.
Quite recently W. Hempel5 has succeeded in carrying
out the combustion of organic compounds in oxygen under
pressure (i.e. in autoclaves), and has perfected the method so
much that it is now possible to make accurate determina-
tions, not merely of carbon and hydrogen, but also of
nitrogen and sulphur. Messinger 6 has also been successful
lately in estimating the carbon of organic compounds in the
wet way, by oxidation with permanganate of potash.
The exact determination of nitrogen in organic com-
pounds first became possible after Dumas 7 (in 1830) had
1 Annals of Philosophy, vol. iv. pp. 330, 401.
2 Schweigger' 's Journ., vol. xvi. p. 16 ; vol. xviii. p. 369.
3 Pogg. Ann., vol. xxi. p. 1 ; also his pamphlet, Anleituny zur Analyse
organischer Korper ("The Analysis of Organic Compounds").
4 Ber., vol. ix. p. 1377. 5 Ber., vol. xxx. p. 202.
6 Ber., vol. xxiii. p. 2756.
7 Ann. Chim. Phys., vol. xliv. pp. 133, 172; vol. xlvii. p. 196.
vi FORENSIC AND HYGIENIC CHEMISTRY 397
devised his admirable method. For many nitrogenous
organic substances the process worked out by Will and
Varrentrapp1 at a later date, in which the nitrogen is
estimated as ammonia, has proved itself thoroughly appli-
cable. In addition to these, the recent method of Kjeldahl2
must be mentioned, a method which is found to be of great
use, especially in agricultural-chemical analyses (for the
determination of protein). Since this method was devised,
it has been materially improved.
Only a bare reference can be made here to the numerous
methods for the determination of the halogens, sulphur, phos-
phorus and other elements ' which occur less often in organic
substances.3
Analytical methods have found the most extended appli-
cation in judicial cases, in questions of hygiene, and in all
the branches of technical chemistry; a short historical
account of them must therefore be given here. Forensic
chemistry, whose task consists in the absolutely certain
detection of poisons, could only reach its present stage of
development after analytical methods in general had been
placed upon a firm basis. Fresenius admirably depicted in
1844 the position and duties of a forensic chemist at that
date.4 The great progress which has since been made in
the precision with which poisons can be detected is dis-
tinctly seen by an examination of the various works on
legal-chemical analysis which have been published from time
to time.5 In addition to Fresenius — J. and R. Otto, Marsh,
Graham, Stas, Mohr, Husemann, Dragendorff and others
have rendered special service in working out good methods.
The Stas-Otto process for the detection of individual alkaloids
1 Ann. Chem., vol. xxxix. p. 257.
2 Ztsc.hr. anal. Chem., vol. xxii. p. 366 ; vol. xxiv. p. 199.
3 Cf. Fresenius' Quantitative Analysis.
4 Ann. Chem., vol. xlix. p. 275.
5 Reference may be made here to Otto's Anleitung zur Ausmittehmg der
Gifte(" Methods for the Detection of Poisons "), sixth edition, 1884 ; Christi-
son's Treatise on Poisons in relation to Medical Jurisprudence, Physiology,
and the Practice of Physic, which was first published in 1829 and which ran
through numerous editions ; and to Stevenson's new edition of Taylor
on Poisons.
398 HISTORY OF ANALYTICAL CHEMISTRY CHAP.
has proved of great importance for the development of this
branch ; since the discovery of the ptomaines,1 it has had to
undergo some modifications, as the resemblance between
many of the reactions of these products and those of the
vegetable alkaloids may easily give rise to most serious
mistakes, and in fact has already done so.
A special branch of chemical analysis is represented by
the methods of testing and investigating used in industrial
chemistry. Since these have for their aim the attainment
of a fair degree of accuracy within the shortest possible time,,
volumetric processes are the ones most frequently employed.
The rapidity with which acids and alkalies, chlorine, many
metals in their compounds, and other substances can be
determined quantitatively by volumetric methods, has
rendered it possible to exercise a continuous control over
manufacturing processes, — with what benefit need not be
said.
A glance into the most recent text-books of technico-
chemical methods 2 is sufficient to convince us of the high
degree of development to which these have been brought.
A large number of processes have in the course of time
been devised, more especially for the commercial analysis of
organic products ; we may recall here the estimation of sugar
by polarisation, the rapid determination of the heating power
of combustibles, the valuation of coal-tar dyes by test-coloura-
tions and by specific reactions, and the estimation of alcohol,
fat, albumen and starch, not to speak of numerous other
methods which have become standard ones in chemical tech-
nology.
For technical chemists, and in an equal degree for
medical officers of health, the development of the analysis
of articles of food and drink has been of the first importance ;
the pharmacist, too, frequently finds it needful to apply the
methods which have approved themselves in such cases. By
their aid the analyst is able to decide whether the products
1 Cf. the special history of physiological chemistry.
2 The works of Post (Brunswick, 1882), of Bockmann (Berlin, 1888), and
of Sutton may be mentioned here.
vi ANALYSIS OF FOODS AND DRINKS 399
are what they pretend to be, or, if they should be adulterated,
the nature of such adulteration. The reader has but to recall
to mind the quickly executed methods for analysing milk,
butter, meal, feeding-stuffs, wine, beer, coffee, etc., in order
to appreciate the true blessing of these applied analyses.
The gradual but continuous work of numerous investigators
has rendered possible the development, within a comparatively
short period of time, of the processes which have become
standard ones here. We cannot now refer in detail to the
services rendered by single individuals in this branch. Full
particulars are to be found in Konig's admirable work, Die
menschlichen Nahrungs- und Genussmittel (Berlin, 1883), a book
which furnishes a complete review of the subject, and at the
same time indicates clearly the share which different chemists
have taken in it. The Bibliothek fur Nahrungsmittel-
chemiker, edited by F. Ephraim, and published by Barth of
Leipzig, forms an excellent summary of works of this class ;
and in C. Fliigge's Lehrl)uch der hygienisclien Untersuchungs-
methoden ("Text-Book of Methods of Hygienic Research")
hygiene possesses a splendid guide for such investigations.
Among English books on the subject, A. Wynter Blyth's
Foods, their Composition and Analysis (4th Edition, 1896)
must also be mentioned.
As the importance of the analysis of foods and drinks
became by degrees better appreciated, the greater refinement
of analytical methods increased the need for laboratories in
which such investigations should be carried on continuously.
The long-cherished wish of many that the State1 should con-
trol these laboratories and their chemists has not yet been
realised. But the importance which is now attached to this
branch of analysis is shown in the increasing provision made
by universities and technical colleges for instruction in it.
Marked advances have also been made in this direction in
Great Britain of late years, thanks to a considerable extent
to the care and vigilance exercised by the Institute of
Chemistry.
1 The German Government is referred to here.
400 HISTORY OF INORGANIC CHEMISTRY CHAP.
THE PROGRESS IN PURE CHEMISTRY FROM LAVOISIER
TO THE PRESENT TIME
While only the main currents of chemistry have been
depicted in the general history of this period, we have now
in the following section to pick out, from the endless number
of experimental researches made, those which have materially
contributed to the extension of our chemical knowledge.
This rich material is divided between the two great branches
of inorganic and organic chemistry. If we glance back over
the labours of the last fifty years, we recognise that organic
chemistry has gone on preponderating more and more over
inorganic ; the former has outgrown the latter, — its elder
sister. But inorganic remains nevertheless the basis upon
which organic chemistry rests, although on the other hand
we must not forget that important fundamental principles
and doctrines (e.g. the doctrine of valency and the true
conception of chemical constitution) were first fruitfully
developed in the domain of organic chemistry.
SPECIAL HISTORY OF -INORGANIC CHEMISTRY
The great revolution in ideas with regard to the consti-
tution of many substances, which was brought about by
Lavoisier's system, has been described in detail in the
special part of this book. A large number of bodies, which
had formerly been looked upon as compound, belonged from
thenceforth to the elements ; while many, which had been
considered simple substances, were either proved to be com-
pounds, or were to be regarded as such from their analogy
to others. The clarifying process which Lavoisier had com-
menced went vigorously forward, thanks to the efforts of
Klaproth, Vauquelin, Proust, Davy, Berzelius, Gay-Lussac
and others. But we are still far from having attained to a
clear and definite knowledge of the nature of all the
vi THE DISCOVERY OF PARTICULAR ELEMENTS 401
-elements and their compounds, new elements being from
time to time added to the long series already known; and
the relations of those to the others have to be established
by an accurate study of their chemical behaviour. Emphasis
has already been laid upon the great effect which the so-
called periodic system has had on the classification of the
elements.
Historical Notes on the Discovery of Elements — The Deter-
mination of their Atomic Weights.
The knowledge of the elements was increased to a very
large extent soon after the death of Lavoisier (who had not
himself discovered any), and this exactly in proportion as
methods of chemical analysis became more perfect. While
Lavoisier was able to bring forward twenty-six elements in
his Traite1 de Chimie, the number of those whose existence
has been definitely established has now extended to at least
sixty-eight.
To the aid which was rendered by improved methods of
analysis, other means specially effective for the discovery
of new elements soon came to be added. Among these was
the application of the galvanic current to the decomposition
of chemical substances, the production of higher tempera-
tures, and the breaking up of haloid compounds by means of
the alkali metals; in spectrum analysis, lastly, chemistry
now possesses an invaluable instrument, which has already led
to the isolation of a number of most important elements.
After the establishment of the atomic theory, the original
task of acquiring a qualitative knowledge of a new element
and its compounds was supplemented by the further and
higher one of determining its relative atomic weight, and
explaining, on the basis of the atomic hypothesis, the con-
stitution of the compounds which it forms with other
elements.
For oxygen, which Lavoisier was the first to claim as a
simple substance, the elementary nature was always after-
wards maintained. Nitrogen, on the other hand, was
D D
402 HISTORY OF INORGANIC CHEMISTRY CHAP,
temporarily regarded by Davy (1808) and by Berzelius l
(1810) as a compound of an unknown element, nitricum
with oxygen, because only in this way could they find an
explanation of the basic properties of ammonia, in which
they likewise assumed the presence of oxygen. Davy was
the first of the two to give up this hypothesis in favour of
the simpler one of nitrogen being an element, Berzelius only
doing this in 1820. Pure nitrogen has just been subjected
to a searching process of diffusion by Ramsay and Travers,2
but the various fractions were found to have precisely the
same density, i.e. the gas showed perfect homogeneity.
Hydrogen, too, was for a short time looked upon by
Berzelius as being compound, i.e. as containing oxygen, and
the same applied to sulphur and phosphorus, in which the
presence of hydrogen and oxygen, besides that of other
unknown elements, was conjectured. That many dis*
tinguished chemists were inclined to regard chlorine as the
oxide of a hypothetical element has been already detailed,
as has also the profound influence which this view exercised
upon important sections of chemistry.3 Before this idea had
been abandoned by Berzelius, iodine — discovered by Courtois
in 1811 in the ashes of marine plants — was shown to be an
element analogous to chlorine, through the splendid re-
searches of Davy, and still more those of Gay-Lussac.4
Bromine, isolated by Balard5 in 1826 from the mother
liquor of sea-salt, and the investigation of which was materially
promoted by Lowig's6 labours in 1829, completed for a
1 Cf. Kopp, Gesch. der Chemie, vol. iii. p. 218.
2 Proc. E. S. for 1898. 3 Cf. p. 239.
4 Ann. de Chimie, vol. xci. p. 5 (1813).
5 Ann. Chim. Phys. (2), vol. xxxii. p. 337.
6 K. J. Lowig was born in 1803, and died at Breslau in 1890. After study-
ing under L. Gmelin and Mitscherlich, he taught at Zurich from 1833 to 1853,
in which year he became Professor of Chemistry at Breslau, continuing in
that post until 1889. Among his publications we may name : — Das Brom
und seine chemischen Verhdltnisse (1829), and his Lehrbuch der Chemie (1832 ;.
second edition, 1849), which latter was long in use as a text-book. His most
important experimental work is referred to in the special history of the sub-
ject, while a memorial notice by Landolt is to be found in the Berichte, vol.
xxiii. Ref. p. 905.
vi DETERMINATION OF ATOMIC WEIGHTS 403
long time the group of Berzelius' " halogen " elements.
Fluorine, the acid constituent of hydrofluoric acid, has only
quite recently been isolated for the first time by Moissan l
(in spite of a great many previous attempts 2), by the electro-
lysis of hydrofluoric acid under suitable conditions, and, as
was to be expected, has been found to be a substance of the
most violent chemical energy. Those researches of Moissan
upon fluorine are among the most noteworthy in inorganic
chemistry in modern times.
The atomic weights, those all-important constants, have
been determined with great accuracy for the non-metallic
elements already spoken of, and by various different methods
in each case. For oxygen, nitrogen, chlorine, bromine and
iodine, the classical researches of Marignac 3 and Stas 4 have
yielded the most reliable values ; for fluorine the determina-
tion by Christensen 5 may be regarded as the most exact.
Of late years the ratio between the atomic weights of
hydrogen and oxygen has been re-determined by a number
of different methods, with the result that a value has been
arrived at which is slightly different from that hitherto
accepted,6 viz., 1*0032: 16. It is hardly necessary to say
that the fixing of this constant deserves all the attention
which has been paid to it; among the recent minute ex-
perimental researches on the subject, those of Cooke and
Richards, Scott, Rayleigh, Morley, Keiser and Noyes may be
mentioned.
Tellurium (chemically analogous to sulphur, which had
been known for so long, but had first been characterised as
an element by Lavoisier) was discovered by Miiller von
Reichenstein in 1782, and investigated by Klaproth 7 in
1 Ibid. (6), vol. xii. p. 472 (1887) ; Comptes Rendus, vol. cut. p. 861 ; and
Ann. Chim. Phys. (6), vol. xxiv. p. 224.
2 Cf. Gore, Phil. Trans, for 1869, p. 173.
3 Cf. Ann. Chem., vol. xliv. p. 1 ; vol. lix. p. 284 ; vol. Ix. p. 180.
4 Untersuchungen ilber die Gesetze der chemischen Proportionen (Leipzig,
1887) (" Researches upon the Laws of Chemical Proportions ").
5 Journ. pr. Chem. (2), vol. xxxv. p. 541.
6 Cf. Ostwald, Lehrbuch der Allgemeinen Chemie, vol. i. p. 43 et seq.
(second edition). Ostwald holds that the atomic weights should be referred
to oxygen, taken as 16, instead of to hydrogen taken as 1.
7 CreWsAnn., vol. i. p. 91.
D D 2
404 HISTORY OF INORGANIC CHEMISTRY CHAP.
1798; an intimate knowledge of it was however first
arrived at through the investigations of Berzelius.1 Selenium
was discovered by Berzelius 2 in 1817, and, along with its
more important compounds, examined by him in the most
thorough manner. The atomic weights of the two last
elements have only recently been settled, after great fluc-
tuations, that of selenium3 being now taken as 79*07 and
that of tellurium4 as 125, previous determinations having,
for a long time caused the wrong value 127-128 to be
ascribed to the latter. This higher value was, no doubt, due
to the difficulty of freeing tellurium from other elements of
higher atomic weight. Since the work of Stas on the sub-
ject, the number 31*98 for sulphur has been accepted as
firmly established.
The discovery of the analogues of nitrogen, — phosphorus,
arsenic and antimony, to which bismuth may be added,
took place a long time ago ; but it is only of late years
that they, and more especially their compounds, have been
accurately investigated.5 For phosphorus, the correct atomic
weight arrived at by Berzelius was confirmed by Dumas
{who found the value 31*02); similarly his atomic weight
for arsenic (75) was corroborated by Pelouze and Dumas.
But on the other hand R. Schneider and Cooke have
proved, by their researches, that the value assumed by
Berzelius for antimony was much too high.
Boron was discovered simultaneously and independently
by Gay-Lussac6 and Davy,7 both of whom isolated it
from boracic acid, which already Lavoisier had regarded as
the oxide of an unknown element. Guided by a similar
view, Berzelius succeeded in 1 8 1 0 in discovering the element
1 Pogg. Ann., vol. xxxii. p. 28.
2 Schweigger's Journ. , vol. xxiii. pp. 309, 430.
3 Eckmann u. Petterson, Ber., vol. ix. p. 1210.
4 Brauner, Ber. , vol. xvi. p. 3055 ; Brauner has more recently found
a higher value than this, but he concludes from his experiments that, in
those cases where the value obtained is greater than 125, this is due to the
presence of some foreign substance (which has not yet been isolated) in the
tellurium (cf. Ztschr. Phys. Chem.,vol. iv. p. 344).
5 Cf . Thorpe and Tutton, Journ. Chem. Soc. , vol. Ivii. p. 545.
6 Recherches Phys. Chim.,vol. i. p. 276.
7 Phil. Trans, for 1809, p. 75.
vi ALLOTROPIC MODIFICATIONS OF ELEMENTS 405
combined with oxygen in silica, although he was only able
to prepare silicium pure for the first time in 1823 by the
action of potassium on potassium silico-fluoride ; 1 with this
he devised an important method for the isolation of various
elements.
The definite knowledge that diamond and graphite are
modifications of the element carbon belongs to the beginning
of the new period ; in addition to the researches of Lavoisier
in 1773 and those of Tennant in 1796, the proof furnished
by Mackenzie — that equal parts by weight of graphite,
charcoal and diamond yield equal amounts of carbonic acid
on combustion — was of special importance for the recog-
nition of the similar chemical nature of the three substances.
The phenomenon of allotropy, the term applied by
Berzelius to the existence of one and the same substance in
different modifications, has been observed with especial
frequency among the non-metals. The oldest example of
it was that offered by carbon, whose allotropic forms show
the greatest conceivable differences among each other;
experiments are still being made on these different modifica-
tions, more especially on the conversion of amorphous carbon
into diamond, — 2 a feat which has been accomplished by
Moissan. The most remarkable case of it, however, is
afforded by the conversion of ordinary oxygen into the
chemically active ozone, which was discovered by Schonbein,a
although van Marum had a long time previously (in 178 5)
called attention to the peculiar change produced in oxygen
by the electric spark. The beautiful investigations of
Schonbein, Marignac and de la Rive established the
substantial identity of ozone and oxygen, while those of
Andrews 4 and, more especially, of Soret 6 proved that the
1 Pogg. Ann., vol. i. p. 165.
2 Cf. Moissan, Comptes Rendus, vol. cxvi. p. 218.
3 Pogg. Ann. vol. 1. p. 616 (1840).
4 Phil. Trans, for 1856, p. 1 ; or Ann. Chem., vol. xcvii. p. 371. An-
drews and Tait, Phil. Trans, for 1861, p. 113 ; or Pogg. Ann., vol. cxii. p.
241.
5 Compt. Rend., vol. Ixiv. p. 904; or Ann. Chem., Suppl., vol. v. p.
148.
406 HISTORY OF INORGANIC CHEMISTRY CHAP.
molecule of ozone was made up of three atoms of oxygen.
Quite recently Shenstone has succeeded in obtaining a very
much larger yield of ozone from oxygen than was formerly
held to be possible. Reference must be made here, in passing,
to the remarkable observations of van 't Hoff and Jorissen,
Victor Meyer, Engler and others on the " rendering active "
(Activirung) of oxygen by other substances, such as the
phosphines, aldehydes, etc. It has been shown that the slowly
oxydised substance renders exactly the same amount of
oxygen active as it takes up itself.1
The allotropic modifications of sulphur were investigated
by Mitscherlich, and those of selenium by Berzelius and,
later, by Hittorff. The transformation of ordinary yellow
phosphorus into red was also observed by Berzelius, but
was first discovered with certainty by Schrotter 2 in 1845,
and its conversion into the metallic modification by HittorfF.
The discovery of " black " sulphur, and of two further modi-
fications of that element — one of which is soluble in water —
belong to the present time;3 as does also that of a new
form of phosphorus.4 The proof that boron and silicon,
already long known in the amorphous state, also exist
in the crystalline form, is due to Wohler. That allotropic
forms of metals can also exist has been shown by the
observations of Carey Lea, E. A. Schneider and others upon
silver ; 5 but there are still many points here which are
obscure. Nevertheless, it remains an undoubted fact that a
number of elements, especially among the non-metals, are
capable of existing in more than one form. Lastly, reference
may be made here to the discovery of allotropic modifications
of chemical compounds, e.g. mercuric sulphide and iodide,
arsenic trioxide, etc.
To the metals which were regarded as elements by La-
1 Cf. Ztschr. Phys. Chem., vol. xxiUp. 34 ; vol. xxiii. p. 668 ; Ber., vol.
xxx. p. 1669. 2 Pogg. Ann., vol. Ixxxi. p. 276.
3 Knapp, Journ. pr. Chem., vol. xliii. p. 305 ; Engel, Gompt. Rend., vol.
cxii. p. 866.
4 Vernon, Phil. Mag., vol. xxxii. p. 365.
6 Cf. E. v. Meyer, Journ. pr. Chem. (2) vol. Ivi, p. 241, for the literature
on the subject.
vi THE METALS OF THE ALKALIES 407
voisier many new ones were subsequently added, so a short
account of the isolation of these must be given here. The
memorable discovery of potassium and sodium, together
.with the conjoined discussion upon the nature of chlorine,
had such a deep influence on the development of important
chemical doctrines, that it has already been referred to in detail
in the general section of this book. The relative atomic
weights of these two alkali metals were determined by
Berzelius with fair accuracy, allowing for the fact that
he assumed their values to be four times greater than those
now assigned to them. Marignac, Dumas and Stas after-
wards arrived at much the same figures in their investiga-
tions already referred to.
Lithium was discovered by Arfvedson,1 a pupil of
Berzelius, in 1 8 1 7 ; he found it to be a constituent of
various minerals, e.g. petalite, and recognised its analogy to
potassium and sodium, but was unable to isolate the metal
itself. The latter was first properly investigated in 1855
by Bunsen and Matthiessen,2 who obtained it by electrolysis.
The red colouration which its salts impart to the spirit-of-
wine flame was noticed by C. G. Gmelin in 1818.
The discovery of rubidium and caesium 3 in lepidolite and
in the Dlirkheimer mineral water by Bunsen and Kirchhoff,
by the aid of spectrum analysis, was the first great gain
which accrued to chemistry from this new method. Since
the chemical reactions of the salts of these two alkali metals are
very similar to those of the salts of potassium, their presence
would undoubtedly have been overlooked but for the spec-
troscope. Indeed, several years before the discovery of caesium ,
the careful analyst Plattner4 had examined the mineral pollux,
which is rich in that element, and had been unable to explain
the deficiency in the results of his analyses, this being really
due to his taking the caesium sulphate present for a mixture of
the sulphates of potassium and sodium. The atomic weights
1 Schweigger's Journ., vol. xxii. p. 93.
2 Ann. Chem.> vol. xciv. p. 1U7.
3 Pogg. Ann., vol. ex. p. 167 ; vol. cxiii. p. 337 ; vol. cxviii. p. 94.
4 Ibid., vol. Ixix. p. 443.
408 HI&T-QRJ^^INORGANIC CHEMISTRY CHAP.
of caesium and rubidium were correctly estimated by Bunsen,
although too low a value was at first assigned to the former,,
in consequence of the supply of material at disposal being in-
sufficient. The atomic weight of lithium was definitely de-
termined by Stas as 7*01.
The metals barium, strontium, calcium and magnesium
were isolated by Davy from their amalgams, which Seebeck
had been the first to prepare ; but for a long time previous to
this baryta and lime had been regarded as the oxides of un-
known metals. Strontia had been discovered by Klaproth
and Hope, independently of one another, and had been char-
acterised as being similar to lime. Berzelius, Marignac and
Dumas determined the atomic weights of these four metals.
Magnesium, which has of late years increased in importance
for manufacturing purposes, has been found by Clemens
Winkler l to be an excellent reducing agent for metallic oxides.
His comprehensive researches were carried out with the ob-
ject of learning how the various metallic oxides comported
themselves to magnesium, and what capacity the reduced
metal showed for combining with hydrogen. Space will not
allow more than this brief reference to the valuable results
from the above piece of work, which has at the same time
added to our knowledge of many of the elements. Kamsay
also found magnesium to be the best agent for taking up the
nitrogen of the air in the preparation of argon.
Beryllium, whose oxide Vauquelin had discovered in 1 7 9 8
in the mineral beryl, was first obtained by Wohler 2 in 1828,
by acting upon its chloride with potassium. The atomic
weight gave rise to important discussions, since it remained
for a long time uncertain whether this amounted to twice or
three times its equivalent number. The point was only de-
cided by the recent researches of Nilson and Pettersson 3 on
the subject, which proved that beryllium, as a diatomic ele-
ment, possesses the atomic weight 91. Later work by Kriiss
and Moraht would make it appear, however, that this number
is still a little too high.
1 Ber., vol. xxiv. pp. 873, 1969. 2 Ibid., vol. xiii. p. 577.
3 Journ. pr. Chem. (2) vol. xxxiii. p. 15.
CADMIUM AND
Cadmium was first observed by Stromeyer in 1817, then
subsequently rediscovered by others, and recognised as being
similar to zinc in character ; its atomic weight has lately been
redetermined with great accuracy by Partridge. Thallium,
isolated by Crookes 1 in 1 8 6 1 from the selenious mud of the
sulphuric acid manufacture, owes its discovery to the character-
istic spectrum given by its salts. The chemical nature of
this metal, which approximates on the one hand to lead and on
the other to the metals of the alkalies, was mainly established
by Lamy, while Crookes determined its atomic weight.
Aluminium was isolated for the first time by Wohler 2 in
1827, by the action of potassium upon its chloride, and'
thus the conjecture which had long been entertained, that
alumina was the oxide of a metal, was confirmed. The
production of the metal on a large scale from its abundantly
occurring oxide, by means of the electric current, is a feat of
modern manufacture (see Special History). The elements in-
dium and gallium, which together with aluminium constitute
a family, were only discovered comparatively recently, the
first-named in 1863 by Reich and Richter,3 as a constituent
of the Freiberg zinc blende, and the second in 1875, also in
zinc ores, by Lecoq de Boisbaudran.4 Here again it was the
characteristic spectra of the two metals which led to their dis-
covery. Their atomic weights were determined by the dis-
coverers, and that of indium with especial accuracy also by
Cl. Winkler 5 and by Bunsen ; 6 while the atomic weight of
aluminium has been worked out with the utmost care by
Mallet.7
The isolation of the metals which constitute the cerium and
yttrium groups has presented unusual difficulties. Although
the discovery of yttria — impure, it is true, from admixture
with other earths — was accomplished by Gadolin nearly a
hundred years ago, and investigators of the first rank have
1 Chem. News, vol. iii. p. 193. 2 Pogg. Ann., vol. xi. p. 146.
3 Journ. pr. Chem., vol. Ixxxix. p. 444; vol. xc. p. 172; vol. xcii. p,
480.
4 Comptes Rendus, vol. Ixxxi. pp. 493, 1100.
5 Journ. pr. Chem., vol. cii. p. 282.
6 Pogg. Ann., vol. cxli. p. 28. 7 Phil. Trans, for 1880, p. 1003,
410 HISTORY OF INORGANIC CHEMISTRY CHAP.
busied themselves with the question, the chemistry of the
cerium metals is not even yet completely cleared up, and may
possibly remain unsolved for a considerable time to come.
After Klaproth and Berzelius had simultaneously prepared
cerium sesquioxide from cerite, and the latter had recognised
this as the oxide of a metal, Mosander discovered two new
oxides in crude yttria, the metals of which — lanthanum and
didymium — he isolated. A few years later (in 1 8 4 3) he added
to these two others, erbium and terbium, whose existence
and nature is not yet however definitely settled, in spite of
the admirable work which has been done on the subject.
This has given us a better knowledge of yttrium, while yttria,
which was formerly held to be a homogeneous substance, has
proved itself a mixture of the oxides of various metals, of
which, however, only one or two have as yet been isolated ;
witness the discovery of scandium by Nilson, and of ytterbium
by Marignac. The most recent additions to our knowledge of
the chemistry of this group of elements have been made by
Krtiss, Cl. Winkler, Bettendorf, Crookes, Brauner and others.
Cobalt and nickel, whose discovery belongs to a preceding
era (cf. p. 149), have lately been the subject of important
researches, more particularly because of the remarkable
compounds which they are capable of forming (see p. 428).
Winkler1 has proved that Kriiss' and Schmidt's view2 —
that another element, hitherto unknown, was present in
nickel and cobalt prepared in the ordinary way — is erroneous ;
and he has also given us most careful re-determinations of
their atomic weights.
The elements molybdenum, tungsten and uranium,
which belong to the same group as chromium, were dis-
covered like the latter itself in the first decades of the
modern period ; but their investigation is still being proceeded
with, thanks to the extraordinary diversity of the compounds
which they form with other elements (see below). Vau-
quelin discovered chromium in 1 7 9 7 as a constituent of red
lead spar, and he also contributed materially to a knowledge
of its compounds; Klaproth pointed out independently at
1 Ber., vol. xxii. p. 890. 2 Ser., vol. xxii. pp. 11 and 2026.
yi MOLYBDENUM, TUNGSTEN, URANIUM, ETC. 411
the same time that there was probably a new metal con-
tained in that mineral. The presence of molybdenum and
tungsten in their oxygen compounds was foreseen by Scheele
and Bergman, the former being isolated in 1783 by Hjelm,
and the latter by d'Elhujar. Uranium, lastly, or rather an
oxide of it which was looked upon as the element, was
detected by Klaproth in 1 7 9 8 as a principal constituent of
pitchblende ; Peligot l was the first to correct this error by
proving that the supposed element contained oxygen, and
also by preparing metallic uranium itself. The atomic
weights of chromium and uranium, as determined by Peligot,
have been corroborated by the recent estimations of Cl.
Zimmermann, Berlin, and especially Meineke. For molyb-
denum, a somewhat higher value than that obtained by
Berzelius has been arrived at from the work of Dumas,
Rammelsberg and others. The atomic weight found by
Schneider, Marchand and others for tungsten — viz. 183*5 —
has maintained its ground.
The elements which resemble tin in character — viz.
titanium, zirconium and thorium (to which germanium has
within the last few years been added) — belong practically to
the chemical history of this century ; for, although the oxides
of titanium and zirconium were discovered at the end of last
century, the isolation of the elements themselves was first
accomplished by Berzelius, by means of the method already
mentioned — viz. the decomposition of the double fluorides
with potassium. Berzelius2 also discovered thoria (ThO2)
and thorium in 1828; the atomic weight of this element
was, however, only definitely established at a much later period
by Nilson,3 the value then obtained by him being subse-
quently corroborated by the determination of the vapour
density of thorium chloride.4 Germanium, the youngest at
present of the metallic elements, was discovered some years
ago by Cl. Winkler,5 and led in his hands to some admirable
1 Ann. Chim. Phys. (3), vol. v. p. 5.
2 Pogg. Ann.y vol. xvi. p. 385. 8 Ber.t vol. xv. p. 2527.
4 Nilson u Kriiss, Ber., vol. xx. p. 1671.
Clemens Winkler, born in 1838, has held the Chair of Chemistry at
412 HISTORY OF INORGANIC CHEMISTRY CHAP.
experimental work,1 which threw the clearest light upon
its nature and that of its compounds. The impulse to look
for a new element was given him by the analysis of a
Freiberg silver ore, which invariably showed a deficit of about
7 per cent. This led to the surmise that some substance was
present for which the analytical methods in use were in-
adequate, just as in the case of caesium, already mentioned.
The atomic weight of germanium, as determined by Winkler,
agrees with the position which naturally falls to this element
in the periodic system.
Vanadium, tantalum and niobium — elements nearly
related to antimony and bismuth — have only become well
known through comparatively recent researches. Vanadium,
recognised as a constituent of certain lead ores by del Rio
so early as 1801, but more definitely by Sefstrom in 1830y
was isolated in the metallic state by Roscoe2 in 1867, who
proved that the substance hitherto taken for an element
really contained oxygen and nitrogen. The chemical relations
of this element and its compounds were admirably worked out
by him, and the atomic weight determined with certainty.
The investigations of Hatchett, Ekeberg, Wollaston and
Berzelius on the minerals columbite and tantalite, in the two
first decades of our century, had already pointed to the pre-
sence of the elements which afterwards received the names of
tantalum and niobium, although the elements themselves had
not been obtained. Nor did the work of H. Rose 3 lead either
to their isolation or to a correct knowledge of their compounds,
for in this case, too, niobium dioxide (Nb202) was regarded
as the element itself. It was the researches of Blomstrand 4
the School of Mines in Freiberg, Saxony, since 1873, having previous to-
that been engaged in practical mining work for fourteen years. Inorganic
and technical chemistry are indebted to him for some most admirable re-
searches, which have frequently included new methods, valuable either in
the laboratory or the manufactory. His most important papers are
referred to in the special history of analytical and of inorganic chemistry.
1 Journ. pr. Chem. (2), vol. xxxiv* p. 177 ; vol. xxxvi. p. 177.
2 Phil. Trans, for 1868, p. 1 ; or Ann. Chem., Suppl., vol. vi. p. 86.
3 Pogg. Ann., vol. xcix. p. 80; vol. civ. p. 432.
4 Journ. pr. Chem., vol. xcvii. p. 37.
vi THE PLATINUM GROUP OF METALS 413
and of Marignac * which first furnished definite standpoints
for a review of the chemical behaviour of the two elements
and their compounds, and for the fixing of their atomic
weights.
The metals of the platinum group, with the exception
of platinum itself,2 have all been discovered during this
century as constituents of platinum ores. Platinum was
only obtained perfectly pure after suitable methods had
been worked out for separating it from the accompany-
ing metals. Its employment for making certain kinds of
apparatus, so important for the development both of scien-
tific and of technical chemistry, also belongs to the present
period.
Palladium came in 1803 under its present name into
commerce, as a new metal, without its discoverer being
known; it was only at a later date that it was learnt
to have been isolated by Wollaston from platinum ore.3
The remarkable property which it possesses of combining
with hydrogen was first observed by Graham.4 The discovery
of palladium led Wollaston5 on to that of another of the
platinum metals, rhodium, which he thus named because of
the rose-red colour of its solutions. It was investigated
carefully by Berzelius,6 who made a minute study of the
platinum metals generally, and by C. E. Glaus;7 the
separation of rhodium from other metals is due primarily to
Bunsen,8 and to Deville and Debray. Tennant 9 was the first
to direct the attention of chemists to indium and osmium, as
two new metals which were contained in the residues left from
the solution of platinum ores ; while to Deville and Debray 10
we mainly owe the method of preparing both elements (the
heaviest substances as yet known) pure. Ruthenium, lastly,
1 Ann. Chim. Phys. (4), vol. viii. p. 5. 2 Cf. p. 149.
3 Phil. Trans, for 1804, p. 428. 4 Phil. Mag. (4), vol^ xxxii. p. 516.
5 Phil. Trans, for 1804, p. 419. 6 Pogg. Ann., vol. xiii. p. 437.
7 Beitrdge zur Chemie der Platinmetalle (Dorpat, 1854), (" Contributions
to the Chemistry of the Platinum Metals ").
8 Ann. Chem., vol. cxlvi. p. 265.
9 Phil. Trans, for 1804, p. 411.
10 Comptes Rendus, vol. Ixxxi. p. 839 ; vol. Ixxxii. p. 1076.
414 HISTORY OF INORGANIC CHEMISTRY CHAP,
was likewise discovered in platinum ores, as well as in
osmiridium, by Glaus,1 who has further given us most of our
knowledge of this element and its compounds, together with
its atomic weight. Debray 2 also investigated ruthenium and
its oxygen compounds comparatively recently.
Up to a short time ago the atomic weights of the
platinum metals had only in part been determined with the
requisite definiteness. For platinum itself the most reliable
value was supposed to be that obtained by Berzelius, viz,
1967, until Seubert3 showed (in 1880) that this figure was
too high by at least two units. The atomic weights of
palladium, rhodium and osmium were also determined by
Berzelius, but required further corroboration ; this applied
more especially to that of osmium. Of late years, however,
K. Seubert 4 has re-determined the atomic weights of iridium,;
osmium and rhodium, Keyser 5 that of palladium, and von
Joly 6 that of ruthenium, with the result that those important
constants have been brought into order in the above two
groups. At the same time the periodic system of the
elements has celebrated a new triumph, for it is only now
that the platinum and palladium metals accord with it, —
i.e. they now occupy the positions which they ought to do
according to theory.
Within the last four years the number of the elements
has been increased by two of peculiar interest — viz. argon,7
discovered in the air by Lord Rayleigh 8 and William
1 Ann. Chem., vol. Ivi. p. 257 ; vol. lix. p. 284.
2 Comptes Rendus, vol. cvi. pp. 100, 328.
3 Ann. Chem., vol. ccvii. p. 29; Ber., vol. xxi. p. 2179 ; also Dittmar
and Arthur, ibid., vol. xxi. Ref. p. 412.
4 Ber. , vol. xi. p. 1770; Ann. Chem., vol. cclxi. p. 257; vol. cclx. p.
314.
5 Amer. Chem. Journ., vol. xi. p. 398.
6 Compt. Rend., vol. cviii. p. 946.
7 Chem. News, vol. Ixx. p. 87 (1894) ; British Association Report for
1894 ; Phil. Trans, for 1895, vol. A. part 2, p. 187.
8 John William Strutt, third Lord Rayleigh, was born on November 12th,
1842. After a brilliant career at Cambridge, where he was senior wrangler
of his year and Smith's prizeman, he succeeded the late Clerk Maxwell as
professor of physics in the University of Cambridge (1879 — 1884). Since
1887 he has held the chair of Natural Philosophy in the Royal Institution.
vi ARGON AND HELIUM 415-
Ramsay,1 and helium discovered by Ramsay in the mineral
cleveite.2 Helium had already been found to exist in
the sun's chromosphere by Janssen3 so long ago as 1868,
i.e. he observed in the spectrum a new bright yellow
line which he designated D3. The spectrum was further
studied that year by Frankland and Lockyer, who also gave
to the new hypothetical element the name Helium.4 The
isolation of argon arose from and followed upon careful
determinations of the atomic weight of nitrogen by Lord
Rayleigh, who found that nitrogen obtained from air was
always specifically heavier by a distinct amount (about J
per cent.) than nitrogen prepared from chemical compounds.
The original paper in the Philosophical Transactions, already
quoted, will undoubtedly rank as a classic, the investigation
having been a particularly brilliant one. It is interesting to
recall that a hundred years ago, Cavendish, reasoning from the
results of his own experiments, had with marvellous acuteness
suggested the possibility of such a gas in the air, and had
surmised its approximate amount. Thanks to its incapacity
for combining with other elements, argon remains behind
after all the other gases in the air have been got rid of.
Although a physicist in the first instance, some of his work has been of the
highest importance for chemistry, notably that upon the density of nitrogen,
which led him and Ramsay on to the discovery of argon ; and, in a second-
ary degree, his determination of the ratio of the atomic weights of hydrogen
and oxygen.
1 William Ramsay, born at Glasgow on October 2nd, 1852, studied
chemistry under the late Professor Anderson at Glasgow University, and
then under Fittig at Tubingen. After acting for some years as chemical
assistant at the Andersonian College and afterwards at the University of
Glasgow, he was appointed in 1880 professor of chemistry in University-
College, Bristol, and also principal of that college in the following year.
In 1887 he succeeded Williamson in the chair of chemistry at University
College, London, which post he still holds. His earlier investigations
were in organic chemistry, but for the last twenty years or so they have
been mostly in physical and inorganic, both of which branches he has
greatly advanced by a wealth of work. In addition to his numerous pub-
lished papers, he is the author of the well-known and original text-book : —
A System of Inorganic Chemistry (J. and A. Churchill, 1891), besides
of smaller works, his last published volume being The Gases of the Atmos-
phere (Macmillan and Co., 1896).
2 Chem. News, vol. Ixxi. p. 151 ; Journ. Chem. Soc., vol. Ixvii. p. 1107,
3 Compt. Rend. vol. Ixvii. p. 838. 4 Lockyer, Proc., U.S., vol. xvii. p. 91.
416 HISTORY OF INORGANIC CHEMISTRY CHAP.
Helium, first obtained by heating cleveite with sulphuric
.acid, and since found in small quantity — often together
with argon — in a good many other minerals, as well as in the
gases from some mineral water springs, is equally indifferent.
Up to now, in spite of persistent effort, no compound of
-either argon or helium has been prepared. And further,
although most careful and laborious diffusion experiments
with both gases have been carried out,1 with the object of
seeing whether they were really elementary, the densities of
both have remained unaltered, i.e, it has been found im-
possible to subdivide them by diffusion into two or more
components. From the ratio of the specific heats at constant
volume and constant pressure, it follows that the molecule
.and atom are identical in both argon and helium, i.e, that the
.gases are monatomic.2
The above short survey of the discovery of elements
during the present chemical period is sufficient to allow of our
properly appreciating the extent of the achievements in this
branch of the science. Since chemists have had before
their eyes the task of assigning a definite place in the
periodic system to each element, the discovery of a new one
has possessed quite another charm, and also a far higher
significance than was formerly the case. What is now
aimed at is to determine the atomic weight of each with
such accuracy, and to examine its chemical behaviour with
such completeness, as to permit of its being classified in
1 Ramsay and Collie, Proc. R.S., vol. Ix. p. 206 (1896) ; Ramsay and
Travers, ibid. vol. Ixii. p. 316 (1897).
• < 2 Ramsay and Travers have just discovered another gas of characteristic
spectrum, which is present in the air in very small quantity, and to which
they have given the name krypton. It is monatomic and has a higher
density than argon (the discoverers expect that its atomic weight wfll be
found to be 81 or 82, in accordance with the periodic law). They found it
in the gas from the last 10 c.c. left on evaporating about a litre of liquid
air. — Further, by fractionating about 20 c.c. of crude liquid argon, they have
succeeded in subdividing the latter into the following three elementary
gases, each of which has a well-defined spectrum : — argon, metargon,
and neon. The atomic weights of argon and metargon will probably be
about 40, and that of neon about 20. Argon and metargon have been
proved to be monatomic, but neon has not yet been tested for this ; it will
no doubt be found monatomic like the others. (Proc. £.8. for 1898.)
vi DOUBTFUL ASSUMPTIONS OF NEW ELEMENTS 417
this system. In the case of none among the recently dis-
covered elements have those efforts been followed with such
signal success as in that of germanium. On the other hand,
as argon and helium cannot be properly fitted into the
periodic system, a suggestion has been made to set up a
separate group of" inactive elements " (Lecoq de Boisbaudran;
J. Thomsen.)1
We find in chemical literature many accounts of sup-
posed new elements, which afterwards turned out either to
have been prepared before, or to be mixtures of substances
partly already known and partly unknown. A passing
reference may be made here to the fantastic attempts of
Winterl 2 at the end of last and beginning of this century,
who imagined that he had decomposed several metals
into different elements. But even investigators of eminence
fell into errors which could only be explained by defects
in the analytical methods of their day ; thus Bergman
(in 1781) looked upon iron phosphide, prepared from
" cold-short " iron by means of hydrochloric acid, as a
new metal, to which he gave the name of siderum, and
Richter claimed impure nickel as an element, terming it
nickolanum. Even Berzelius thought that he had dis-
covered (in 1815) a hitherto unknown earth in some
Swedish minerals, but he corrected the error himself by
showing that the supposed new body was phosphate of
yttria. The history of the cerium metals, to which yttrium
belongs, and also of tantalum and niobium, shows more
especially a great many such errors, while even at the present
day a number of new elements are being brought forward
whose homogeneous nature is in the highest degree doubtful,
e.g. decipium, mosandrium, and philippium.3 Similarly, so
little is known yet ofmasrium* discovered in 1892, and of the
element still more recently obtained from bauxite, that
nothing can be said about them; and the same remark
applies to lucium and russium (Barriere ; Chrustschoff ).
1 Ber vol. xxix. Ref. p. 830.
2 Kopp, Gesch. d. Chemie, vol. ii. p. 282.
3 Comptes Rendus, vol. Ixxxvii. pp. 148, 559, 632, etc.
4 Mon. Scient. for 1892. p .514.
E E
418 HISTORY OF INORGANIC CHEMISTRY CHAP,
Extension of the Knowledge of Inorganic Compounds.
The general standpoints arrived at during the present
chemical period for the comprehension of inorganic chemical
compounds, more especially the opinions with regard to the
constitution of acids, bases, and salts, have been entered into
in detail in the first section of this book. It remains now
to give an account of the development of special knowledge
in this branch of the science. An exhaustive treatment of
the subject is of course impossible here ; only researches of
particular moment, which have materially aided in extending
the knowledge of chemistry, can be mentioned.
Hydrogen Compounds of the Halogens.
The remarkable behaviour of hydrogen with respect to
chlorine, — the readiness with which those two gases com-
bine, was first investigated by Davy and Gay-Lussac, and
afterwards made the subject of important physico-chemical
work by Roscoe and Bunsen.1 The researches of Davy and
Faraday 2 contributed greatly to a more intimate knowledge
of hydrochloric acid, showing among other things how to
condense the gas, while those of Roscoe and Dittmar3
established the chemical relations existing between
hydrochloric acid and water. Gay-Lussac and Balard
investigated hydriodic and hydrobromic acids, while the
fundamental researches of Gay-Lussac, Thenard and Berzelius
contributed a knowledge of hydrofluoric acid in aqueous
solution, and those of Gore 4 and Fremy 5 of this acid in the
gaseous state, these latter thus establishing its composition.
Nickles fell a victim to the frightful action of anhydrous
hydrofluoric acid in 1869. Ampere was the first to point out
the analogy between fluorine and chlorine.
Oxygen Compounds of Hydrogen and of the Halogens.
The investigations which led to a knowledge of the
composition of water have been already described ; the first
1 Poyg. Ann., vol. c. p. 43 ; or Phil. Trans, for 1857, p. 355 ; Ann. Chem.,
vol. xcvi. p. 357 ; cf . History of Physical Chemistry.
2 Phil. Trans, for 1823, p. 164. 3 Ann. Chem., vol. cxii. p. 337.
4 Phil. Trans, for 1869, p. 173. 5 Ann. Chim. Phys. (3), vol. xlvii. p. 5.
vi PEROXIDE OF HYDROGEN, ETC. 419
quantitative determination of its constituents, to which but
little exception could be taken, was made by Berzelius and
Dulong.1 The discovery of peroxide of hydrogen 2 by Thenard
in 1 8 1 8 showed that water was not the only oxide of that
element, while the chemical behaviour of this peroxide, which
was examined by Thenard, Schonbein, etc., and of recent
years by Scheme 3 and Traube,4 stamps it as one of the most
remarkable of inorganic compounds. It also appears to play
an important part in many of the processes of nature, and
the interest in it is heightened still further by the value
which it promises to have for technical chemistry. Wolf-
fenstein has lately succeeded in preparing pure hydrogen per-
oxide without difficulty by distilling it in vacuo.5
The various stages of oxidation of chlorine, iodine and
bromine have been the cause of much valuable work since
the beginning of our century, e.g. that of Gay-Lussac on
chloric acid, of Stadion on perchloric acid, of Davy and
Stadion on chlorine peroxide, of Millon6on chlorous acid,
and of Balard 7 on hypochlorous acid. The knowledge of
some of these compounds was much enlarged by Pebal's
latest researches,8 which established the nature of the so-
called euchlorine and of chlorine peroxide. The oxygen
compounds of iodine became known through the investi-
gations of Davy and Magnus ; periodic acid (discovered by
the latter)9 and iodic acid led later on to a knowledge of
several series of salts, from whose composition important
conclusions as to the saturation-capacity of iodine, and
therefore of the halogens generally, were drawn. Excepting
argon and helium, fluorine is the only element which does not
combine with oxygen.
1 Ann. Chim. Phys., vol. xv. p. 386 ; for later determinations of the
ratio H2 : 0, see p. 403. 2 Ann. Chim. Phys., vol. viii. p. 306 (1818).
3 Ann. Chem., vol. cxcii. p. 258 (Schone gives here a review of the
previous literature on the subject).
4 Cf. Ber. , vol. xx. p. 3345 ; vol. xxii. p. 1496 ; vol. xxvi. p. 1471.
5 Ber., vol. xxvii. p. 3307. 6 Ann. Chim. Phys. (3), vol. vii. p. 298.
7 Ibid., vol. Ivii. p. 225.
8 Ann. Chem., vol. clxxvii. p. 1 ; vol. ccxiii. p. 113.
9 Pogg. Ann., vol. xxviii. p. 514.
E E 2
420 HISTORY OF INORGANIC CHEMISTRY CHAP.
Sulphur, Selenium and Tellurium Compounds.
To the early known compounds of sulphur and oxygen,
sulphurous and sulphuric acids (the anhydride of the latter
having been discovered by Vogel and Dobereiner), others
came to be added, viz. " hyposulphurous acid " by Gay-
Lussac,1 and dithionic acid by Welter and Gay-Lussac (in
1819). The constitution of the first of these, which is really
thiosulphuric acid, was only made out at a much later date.2
The thio-acids containing more sulphur, and nearly related
to sulphuric acid, were discovered at the beginning of the
forties by Langlois, Forces and Gelis, and Wackenroder;
the question as to whether the pentathionic acid of the latter
really exists has. recently been vigorously discussed.3
To the above sulphur acids there has of late years been
added Schutzenberger's hyposulphurous acid (H2S02) the
chemical behaviour of which is of great interest.4 The two
well-known oxides of sulphur also received an addition in
R Weber's sesquioxide, S2O3.5 Lastly, mention may be
made here of per-sulphuric acid, whose existence Berthelot
showed to be probable, and for the anhydride of which he
assumed the formula S2O7 ; recent researches by Elbs and
others have solved its true composition, viz. HS04, which thus
corresponds with that of permanganic acid. Neither of these
compounds, however, (i.e. S2O7 and HS04) has yet been
obtained pure. The enormous impetus given to chemical
industries generally by the development of the sulphuric acid
manufacture must also be referred to. It is only within the
last few years that such simple derivatives of sulphuric
acid as the amide and imide have become known ; and
1 Ann. Chim., vol. Ixxxv. p. 199 ; sodium hyposulphite (thiosulphate)
was first prepared by Chaussier in 1799, and afterwards more carefully
examined by Vauquelin.
2 Cf. Schorlemmer, Journ. Chem. Soc. (2), vol. vii. p. 256.
3 Cf. Curtius u. Henkel, Journ. pr. Chem. (2), vol. xxxvii. p. 37 ; Debus,
Journ. Chem. Soc., vol. liii. p. 278 ; or Ann. Chem., vol. ccxliv. p. 76.
4 Comptes Rendus, vol. Ixix. p. 169.
5 Pogg. Ann., vol. clvi. p. 53.
vi COMPOUNDS OF NITROGEN, PHOSPHORUS, ETC. 421
the same thing applies to fluor-sulphuric acid and other
compounds.1
The compounds of selenium with hydrogen and oxygen
were investigated by Berzelius, and an account of them given
in his memorable treatise. After him there came Mitscherlich,
who discovered selenic acid, and therewith furnished a beauti-
ful confirmation of the analogy between selenium and sulphur
more especially from the isomorphism of the sulphates and
selenates. This chemical similarity has not however been
maintained in all respects, Michaelis 2 having recently shown
that the salts of selenious acid probably possess a constitution
different from that of sulphites.
The chlorine compounds of sulphur, selenium and tel-
lurium, the study of which has helped to characterise these
elements, have been examined at various times ; by his in-
vestigation of tellurium tetrachloride Michaens has lately
furnished an excellent proof of tellurium being tetratomic.
Even if we desired to mention only the more important
of the investigations which have aided in the discovery and
elucidation of the hydrogen, oxygen and halogen compounds
of nitrogen, phosphorus, arsenic and antimony, it would be
necessary to record a long series. Among them were the re-
searches of Davy, Berthollet and Henry, which made clear
the composition of ammonia, — so long looked upon as con-
taining oxygen. The discovery of phosphuretted hydrogen
(PH3) by Gengembre 3 in 1783, and the examination of it by
Pelletier (who was the first to prepare it pure), only became
fruitful after Davy's investigations ; the last-named eluci-
dated the composition of this gas, and pointed out its analogy
to ammonia, this being emphasised still more sharply by EL
Rose later on. Thenard 4 discovered liquid phosphuretted
hydrogen, and recognised in it the cause of the spontaneous in-
flammability of the not completely pure gaseous compound.
1 Cf. W. Traube, Ber., vol. xxvi. p. 607; Thorpe and Kirwan, Ztschr.
anorgan. Chem., vol. iii. p. 63; or Journ. Chem. Soc. vol. Ixi. p. 921.
2 Ann. Chem., vol. ccxli. p. 150. 3 CrelVs Ann., vol. i. p. 450.
4 Ann. Chim. Phys. (3), vol. xiv. p. 5. Compare also Gattermann and
Haussknecht, JSer., vol. xxiii. p. 1174.
422 HISTORY OF INORGANIC CHEMISTRY CHAP.
Arseniuretted and antimoniuretted hydrogens, which are
analogous to ammonia in composition, were first obtained in the
pure state by Soubeiran l and Pfaff.2 The former compound
cost Gehlen his life in 1815, from his not suspecting its ex-
treme poisonousness ; and the same fate has recently befallen
H. Schulze (of St. Jago). The great importance of the forma-
tion of arseniuretted hydrogen for the detection of minute
quantities of arsenic in judicial-chemical analyses (Marsh's
process) is well known.
The oxygen compounds of nitrogen played, as already
described, an important part in the history of the atomic theory,
even although the true composition of all these oxides was
not at that time made out. The number of the oxides of
nitrogen known in Dalton's time was supplemented by nitro-
gen peroxide, whose relation to the others was arrived at
through the researches of Berzelius, Gay-Lussac and Dulong ;
and by nitric anhydride, discovered by St. Claire Deville.
The various obscure points with respect to nitrous acid and
nitrogen peroxide have been for the most part explained by
the recent investigations of Hasenbach 3 Lunge,4 Ramsay 5
and others. The discovery of hyponitrous acid,6 the acid cor-
responding to nitrous oxide, enlarged still further the series of
the oxy-acids of nitrogen. W. Wislicenus and Paal, in-
dependently of one another, succeeded in preparing hypo-
nitrous acid by the interaction of hydroxylamine and nitrous
acid,7 and since then Hantzsch and Kaufmann have proved
that its molecular weight corresponds to the formula
N202H,8
Reference must also be made here to the important dis-
covery of hydroxylamine,9 which, from its value as a reagent,
1 Ann. Chim. Phys. (2), vol. xxiii. p. 307.
2 Pogg. Ann., vol. xl. p. 135.
3 Journ. pr. Chem. (2), vol. iv. p. 1.
4 Cf. Ber., vol. xviii. p. 1376 ; vol. xxi. p. 67.
5 Journ. Ghem^ Soc., vol. xlvii, pp. 187 and 672; vol. liii. p. 621 ; vol.
Ivii. p. 590 ; Phil. Mag., vol. xxiii. p. 129; vol. xxiv. p. 196.
6 Divers, Proc. R. S.t vol. xix. p. 425 ; Zorn, Ber., vol. x. p. 1306.
7 Ber., vol. xxvi. pp. 771 and 1026. 8 Ann. Chem., vol. ccxcii. p. 317.
9 Lessen, Ann. Chem., Suppl., vol. vi. p. 220.
vi HYDROXYLAMINE ; OXIDES OF PHOSPHORUS 423
has led to a knowledge of many remarkable compounds,
especially in organic chemistry. For a long time known only
in solution, it has now been obtained in the free state.1 Fremy's
acides sulfazotts have only of late years been recognised as
being really sulphoxyl-derivatives of ammonia and hydroxyl-
amine (e.g. HO.N. (SO2OH)2 and HO.NH.SO2OH).2 The
discovery of the more or less analogous amido-amine 3 (diamid-
ogen or hydrazine, H2N.NH2), filled up a long-felt gap. By
its interaction with other organic substances, a large series of
most important compounds has been prepared. From one such
derivative of hydrazine is obtained that remarkable compound
hydrazoic acid (or azo-imide), N3H, which, in spite of its ex-
cessively explosive nature, has been thoroughly investigated
by its discoverer, Curtius.4 W. Wislicenus,5 Noelting 6 and
others have devised further methods for preparing it.
Of the oxygen compounds of phosphorus, phosphorous and
phosphoric acids were known, although very imperfectly, in
Lavoisier's time ; the former was first prepared pure by
Davy, by treating phosphorus trichloride with water, but its
chemical constitution was only cleared up by later investiga-
tions. The recent admirable paper of Thorpe and Tutton 7
upon phosphorous oxide, P4O6, shows that the real properties
of this substance are very different from those formerly
attributed to it. The labours of Clarke, Gay-Lussac and
Stromeyer prepared the way for the recognition of the mutual
relations existing between ortho-, pyro-, and meta-phosphoric
acids, these being subsequently worked out by Graham ; 8 and
upon them Liebig established his far-reaching theory of poly-
basic acids.9 Hypophosphorous acid, whose salts were discovered
by Dulong in 1 8 1 6, has been the subject of important investi-
1 Lobry de Bruyn, Rec. Trav. Chem., vol. x. p. 101.
2 Cf. Raschig's admirable paper (which also gives a review of the
previous literature on the subject), Ann. Chem., vol. ccxli. p. 161.
3 Curtius u. Fay, Journ. pr. Chem. (2), vol. xxxix. p. 27.
4 Ber., vol. xxiii. p. 3023 ; vol. xxiv. p. 3341 ; Journ. pr. Chem. (2), vol.
xliii. p. 207.
5 Ber., vol. xxv. p. 2084. 5 Ber., vol. xxvi p. 86.
7 Journ. Chem. Soc., vol. IviL p. 545.
8 Phil. Trans, for 1833, vol. ii. p. 253. 9 Cf. p. 244.
424 HISTORY OF INORGANIC CHEMISTRY CHAP,
gations and discussions.1 Hypophosphoric acid,2 H4P2O6r
has also lately been added to the above oxygen compounds.
The discovery of the halogen compounds of nitrogen and
phosphorus has proved of particular interest, the latter
being largely employed for the preparation of many other sub-
stances, because of the readiness with which they enter into
reaction. Chloride of nitrogen was discovered by Dulong,&
who suffered serious injury in consequence of some of it ex-
ploding unexpectedly ; this dangerous substance, whose com-
position was hitherto uncertain, has of late been made the
subject of important investigations by Gattermann,4 who has
succeeded in preparing the pure chloride, NC13. The analogously
formed iodide of nitrogen was first prepared by Serullas,5
while Bunsen, Stahlschmidt and, quite recently, Raschig 6
have contributed towards a knowledge of its composition.
The chlorine compounds of phosphorus were prepared in the
first decade of our century, the trichloride by Gay-Lussac and
The'nard, and the pentachloride by Davy. The trifluoride of
phosphorus has only recently been prepared by Moissan ; the
pentafluoride, isolated by Thorpe,7 is of especial interest from
its not decomposing even at high temperatures, unlike the
other penta-haloid compounds of phosphorus. Wurtz dis-
covered phosphorus oxychloride, which is of great value as a
reagent in organic work, and H. Rose antimony pentachloride.
The oxybromide of phosphorus has been known for some
time, but it is only lately that Moissan has obtained the
oxyfluoride.
The halogen compounds of boron and silicon were mainly
investigated by Berzelius and, later, by Wohler and Deville,8
and they constituted the material from which those elements
themselves and others of their compounds were prepared ; the
1 Cf. Wurtz, Ann. Chem., vol. xliii. p. 318 ; vol. Ixviii. p. 41.
2 Salzer, Ann. Chem., vol. clxxxvii. p. 322 ; vol. cxciv. p. 28 ; vol. ccxL
p. 1 ; vol. ccxxxii. p. 114 ; Sanger, ibid., vol. ccxxxii. p. 1.
3 Schweigger's Journ., vol. viii. p. 302.
4 Ber., vol. xxi. p. 751.
5 Ann. Chim. Phys., vol. xlii. p. 200.
6 Ann. Chem., vol. ccxxx. p. 212.
7 Ann. Chem., vol. clxxxii. p. 201. 8 Ibid., vol. cv. p. 67 et seq-
vi COMPOUNDS OF BORON, SILICON AND CARBON 425
above researches, in fact, greatly extended the knowledge of
these substances generally. Among other points, the discovery
of boron nitride and silicon hydride may be mentioned here.1
To the careful investigation of volatile silicon compounds is
due the definite establishment of the atomic weight of
that element, and, with this, of the composition of silica, to
which another formula than the present was previously given.
In recent years there have been further important researches
on the halogen compounds of boron and silicon 2 by Moissan,.
Besson, and Sabatier.
Of the simple compounds of carbon, which from long
custom are assigned to inorganic chemistry, the greater
number were discovered and examined at the beginning of
this century. Details have already been given with respect
to carbonic acid and carbonic oxide. The study of the
phenomena of combustion, and particularly of the processes
which go on in the flame of burning carbon compounds, in
which the two gases just mentioned play a prominent part,
was first taken up by Davy, who advanced the subject
immensely by his beautiful researches. We must also refer
here to the more recent investigations of Frankland, Bloch-
mann, Heumann, Smithells, and Lewes, on the theory of
luminous flames. The luminous acetylene flame has again
within the last few years been the subject of much investiga-
tion and discussion among chemists, the object being to get
at the cause of the luminosity. The results have proved
that, in the main, Davy's old theory of luminous flames is
correct.
Carbon oxychloride or phosgene, which has proved of
exceptional value as a reagent in organic chemistry, was first
prepared by Davy in 1811, but carbon oxysulphide only com-
paratively recently by von Than.3 Carbon disulphide, on the
other hand, was obtained by Lampadius so early as 1796,
1 Wohler u. Buff, Ann. Chem., vol. cii. p. 120.
2 Compt. Rend., vols. cxii. and cxiii.
3 Ann. Chem., Suppl., vol. v. p. 236. The properties of the pure com-
pound were first established by Klason (Journ. pr. Chem. (2), vol. xxxv. p.
64).
426 HISTORY OF INORGANIC CHEMISTRY CHAP.
and more minutely investigated by Clement and Desormes
in 1802 ; it is now an important product of chemical manu-
facture. Its composition was arrived at correctly by
Vauquelin and Berzelius, after the most confused opinions
had previously been expressed with regard to its containing
hydrogen and nitrogen. The profound influence which the
classical researches of Gay-Lussac on cyanogen and its com-
pounds exercised upon the development of chemistry has
already been referred to.
Extension of the Knowledge of Metallic Compounds.
From the endless number of investigations which have
contributed towards a knowledge of the metallic compounds,
and, with this, of the metals themselves, the most important
must now be mentioned, if they have not already been
touched upon in the general section of this book.
The discoverers of the alkali metals also aided largely
in their investigation ; thus to Davy is due our knowledge
of the oxides of potassium and sodium, to Gay-Lussac
that of the corresponding peroxides, and to Bunsen that of
rubidium and caesium compounds. Sodium peroxide is
now manufactured in quantity. The enormous influence
which these researches on the compounds of the alkalies
exercised upon the development of chemical industries will
IDC detailed under the history of technical chemistry.
The peroxides of barium and calcium were discovered by
Gay-Lussac and Thenard. The knowledge of the nature
of chloride of lime was advanced by the researches of Balard,
who was the first to express the opinion — still held by
many — that this substance was a double compound of cal-
cium chloride and hypochlorite. Since that time numerous
further experiments have led many to regard it as an oxy-
chloride of calcium, which has given rise to a large amount
of discussion.1
The investigations which led to a knowledge of the com-
1 Cf. the work of Gopner, Wolters, Kraut, Lunge and others.
vi COMPOUNDS OF METALS OF THE IRON GROUP 427
pounds of beryllium and thallium have been cited above.1
New oxygen compounds of copper, in addition to the oxides
already known, were obtained by Rose 2 and Th^nard, while
Wb'hler discovered silver suboxide and peroxide; it must
however be mentioned here that the existence of the former
of these has been vigorously contested.3 The application of
silver salts for the fixation of light impressions (i.e. in
photography), so pregnant in its results, will be treated
under the history of physical chemistry. Those chemists
who shared in the discovery and investigation of aluminium,
indium and gallium, also contributed at the same time to
a knowledge of their compounds. With respect to the com-
pounds of alumina, pure chemistry has frequently been
called upon to elucidate difficult points pertaining to the
manufacture of ultramarine, porcelain, glass, &c.
The compounds of the metals which form the iron group
have been the object of a very large number of investigations,
among which we may mention those on the different stages of
oxidation of manganese by Liebig and Wohler,4 Mitscherlich 5
and, recently, Franke.6 The chlorine and fluorine compounds
of manganese were studied by Christensen. To the two
oxides of iron (FeO and Fe2O3), a knowledge of which we
owe to Proust and whose composition was established by
Berzelius, Fremy added ferric acid, which he also carefully
investigated; the existence of this acid was surmised by
Scheele. Light was thrown upon the nature of the
cyanogen compounds of iron by the beautiful researches of
Gay-Lussac, Berzelius, Gmelin (who discovered potassic ferri-
cyanide), and Liebig, out of which the present views held with
regard to these substances have developed themselves. The
1 Cf. pp. 408 and 409. 2 Pogg. Ann., vol. cxx. p. 1.
3 Wohler, Ann. Chem., vol. xxx. p. 1 ; Fiiedheim, Ber., vol. xxi. p.
316. On the other hand, von der Pfordten, who at first believed that he
had proved the existence of silver suboxide, has subsequently expressed
himself in favour of a " hydrate of silver," the most probable formula being
Ag4-H2O. (Ber., vol. xxi. p. 2288.)
4 Pogg. Ann., vol. xxi. p. 584.
5 Ibid., vol. xxv. p. 287.
6 Journ. pr. Chem. (2), vol. xxxvi. pp. 31, 166, 451.
428 HISTORY OF INORGANIC CHEMISTRY CHAP,
nitroprussides, so nearly allied to the ferrocyanides, were first
obtained by Playfair, but their constitution has yet to be
satisfactorily cleared up.
There are few more remarkable metallic compounds than
those recently discovered ones which carbon monoxide forms
with iron and nickel, when the gas is allowed to pass over
the hot and finely-divided metal.1 Nickel tetra-carbonyl^
Ni (CO)4, is especially interesting both from a physical
and chemical point of view, and it is to be hoped that by
means of it the question of the true atomic weight of nickel
will be ultimately solved. Whether, as Mond hopes, the
metallurgical production of nickel by the aid of this carbonyl
compound will be possible, remains to be proved.
The metallic carbides and several compounds of carbon
with other non-metallic elements are likewise very striking
substances. Although only discovered a short time ago, some
of them have already acquired great technical importance,
especially carbide of calcium, which is used at present for
the production of acetylene gas, and which will assuredly
play an even greater part in the future than it does now.
Silicon carbide or " carborundum " far surpasses corundum as
a polishing material for hard substances. Moissan's splendid
work on the carbides — of which a few were known previously,
but had only been superficially examined — has thrown much
light on these compounds.2
The chemistry of the cobalt salts was enriched by the
discovery of the remarkable and highly varied ammonio-
cobaltic compounds, which, observed by Genth for the first
time in 1851, were afterwards investigated by Fr. Rose,
Gibbs, Fremy, and especially Jorgensen.3 The last-named
investigator has brought the extraordinarily difficult question
of the chemical constitution of these bodies materially nearer
to its solution, by systematically examining the ammonia
1 Mond, Langer and Quincke, Journ. Chem. Soc., vol. Ivii. p. 749 ; Ber.,
vol. xxiv. p. 2248 ; Berthelot, Compt. Rend., vol. cxii. p. 1343.
2 Cf. Compt. Rend., vol. cxvii. p. 679 ; also vols. cxv. and cxvi. ; but
particularly his brochure, Le Four Electrique (Paris, 1897).
3 Cf . Journ. pr. Chem. (2), vol. xxiii. p. 227 ; vol. xxxi. pp. 49, 262 ; voL
xxxix. p. 1 ; vol. xli. p. 429.
vi COMPOUNDS OF MOLYBDENUM AND TUNGSTEN 429
compounds of those other metals analogous to cobalt in this
respect — chromium and rhodium.1
The. various combining relations which the different
members of the group of elements comprising molybdenum,
tungsten and uranium show towards other elements, have
only been fully understood of recent years. The admirable
work of Berzelius on molybdenum compounds has been
supplemented by that of Kriiss 2 on the sulphides, and of
Muthmann 3 on the oxides, as well as by the earlier investi-
gations of Blomstrand, Debray, Liechti and Kempe on the
halogen compounds of molybdenum. The chlorides of
tungsten were examined in detail by Roscoe, who thereby
advanced the knowledge of the saturation-capacity of this
element. The complicated salts of tungstic acid were first
studied by Margueritte, Scheibler, Marignac and v. Knorre,
but their ultimate constitution, as well as that of the
phospho-molybdic and phospho-tungstic acids, has still to
be unravelled. Tungsto- and molybdo-vanadic acids belong
to the " compound acids " which have recently been investi-
gated by Friedheim. The chemical nature of uranium and its
compounds has been worked out with most success by Cl.
Zimmermann4 whose able researches have largely supple-
mented the earlier ones of Peligot, Roscoe and others.
Of the compounds of tin and its chemical analogues,
the isomorphous double fluorides 5 aroused especial interest
from their proving the connection which exists between
silicon, titanium, zirconium and germanium. The peculiar
nature of titanium was elucidated in a striking manner
by the discovery of its nitrogen compounds,6 and more
recently by the preparation of its various sulphides.7
To Roscoe's admirable work8 is due most of our knowledge
1 Joum.pr. Chem. (2), vol. xxv. pp. 83, 321 ; vol. xxx. p. 1 ; vol. xxxiv.
p. 394.
2 Ann. Chem., vol. ccxxv. p. 1. 3 Ibid., vol. ccxxxviii. p. 109.
4 Ann. Chem., vol. ccxiii. p. 285 (contains a historical review) ; vol.
ccxxxii. p. 274 ; also Alibegoff, ibid., vol. ccxxxiii. p. 117.
5 Marignac, Ann. des Mines (5), vol. xv. p. 221.
6 Wb'hler, Ann. Chem. , vol. Ixxiii. p. 43. 7 Ann. Chem. , vol. ccxxxiv. p. 257.
8 Phil. Trans, for 1869, p. 679; or Ann. Chem., Suppl., vol. vii. p. 70.
430 HISTORY OF INORGANIC CHEMISTRY CHAP.
of vanadium, as he worked out correctly the different stages
of combination of this element with oxygen, chlorine, &c.,
and set right the former erroneous assumptions with regard
to the composition of these compounds. Gerland's investiga-
tions l on vanadyl salts and vanadic acids, and those of v. Hauer
on the salts of the latter, have also been of assistance here.
Similarly niobium and tantalum, whose chemical nature
had been completely misjudged, were given their proper
position among the other elements by the investigations
already cited, more particularly by the determination of the
true composition of the chlorides of both and of niobium
oxychloride,2 and by the examination of niobium fluoride and
hydride.3
Valuable work has also been done lately on the
compounds of gold, by Kriiss 4 more especially, which has
materially amplified the earlier researches of Proust,
Berzelius, Figuier, &c., and has served to establish the
chemical character and the atomic weight of this element.
The literature on platinum and its compounds is very
voluminous, and gives evidence of most excellent experimental
work. Reference may be made here to the discovery of the
peculiar reactions to which platinum can give rise in virtue
of its condensation of oxygen (the absorption of oxygen by
platinum and palladium has been proved to be true oxidation,
for the same amount of heat is given out by this absorption
as in the formation of the oxides PtO and PdO) 5 ; and to the
numerous investigations on the platinum-ammonium com-
pounds, the first of which were prepared by Magnus, and whose
peculiarities were studied by Gros, Reiset, Cleve, Thomsen and
Blomstrand/ The recently published work of Jorgensen:6
1 Ber., vol. ix. p. 874 ; vol. x. p. 2109 ; vol. xi. p. 98.
2 Deville and Troost, Gomptes JRendus, vol. Ix. p. 1221.
3 Kriiss and Nilson, Ber., vol. xx. p. 1676.
4 Cf. Kriiss, Ann Chem., vol. ccxxxvii. p. 274 (contains a historical
review) ; vol. ccxxxviii. pp. 30 and 241 ; Ber., vol. xxi. p. 126; Thorpe
and Laurie, Journ. Chem. Soc. , vol. li. pp. 565 and 866.
5 Mond, Ramsay and Shields, Phil. Trans., vol. clxxxvi. p. 657 ; vol.
cxc. p. 129.
6 Journ. <pr. Chem. (2), vol. xxxiii. p. 489.
vi PLATINUM COMPOUNDS, ETC. 431
Zur Constitution der Platinbasen (" On the Constitution of the
Platinum Bases "), marks an important step in the recognition
of the constitution of these bodies. The compounds which
carbon monoxide forms with chloride of platinum, discovered
by Schiitzenberger, have lately been carefully investigated by
Mylius and Forster and by Pullinger, who have thereby
contributed greatly to solving the problem of their
constitution.1
The researches which have assisted materially towards
a knowledge of the platinum metals have already been
mentioned under the history of the individual elements.
If we throw a glance over the wide field of inorganic
chemistry, with its seventy elements approximately and their
endless compounds, we cannot fail to recognise the fact that
the atomic theory has rendered the main service in their
classification. The endeavour, too, to establish periodic
relations between the properties of the elements and their
atomic weights has introduced order among the motley
array of the elements and their compounds. The question
of the constitution of the latter allows in most cases of a
simple and satisfactory answer ; as soon, however, as the
composition of inorganic compounds becomes complicated,
the usual aids to the solution of such points no longer suffice.
The consequence of this is that the rational composition
of a large number of compounds, whose empirical composition
has long been known, has not yet been cleared up; as
examples of such we may refer to the metallo-ammonia
compounds (e.g. those of cobalt and chromium), the poly-
silicic acids, the tungstic acids, and the host of compound
acids. Even the constitution of the carbonyl compounds of
nickel, iron, &c. is still uncertain.
1 Ber., vol. xxiv. pp. 2291, 2434 and 3751.
432 HISTORY OF ORGANIC CHEMISTRY CHAP.
SPECIAL HISTORY OF ORGANIC CHEMISTRY
IN THE NINETEENTH CENTURY.
The development of organic chemistry during the first few
years of this century has been already described under the
general history of the period (cf. p. 246) ; there, also, much of
the pioneering work accomplished in this branch of the subject
has been discussed, in so far, that is, as it had a determining
influence on the origin and growth of important theoretical
investigations. In this section the attempt will be made to
pick out from the superabundance of work done in organic
chemistry that which has proved of greatest significance,
and to arrange it according to its nature (not according to
its sequence in point of time) — more especially such in-
vestigations as have contributed to solving the question of
the chemical constitution of whole classes of bodies. The
general points of view by which individual experimenters
have been guided in those researches have already been
examined at various times in the first section of this book.
Before organic chemistry could be in a position to
develop itself independently, the following two conditions
had to be fulfilled : — In the first place, the determination of
the empirical composition of organic substances was necessary
(how this question was solved is described under the
history of analytical chemistry) ; l in the second, it had to be
proved that organic compounds were subject to the same
atomic laws as inorganic, and that they were not, as many
formerly assumed, to be classed as totally distinct from
the latter. To Berzelius, more than to any other man, is
due the removal of this dividing barrier between the two.
The most important methods, which have ever since
remained standard ones in organic chemistry, were created
by the fundamental researches of Gay-Lussac on cyanogen and
its compounds, of Liebig and Wohler on benzoyl and
1 Cf. p. 393.
vi THE HYDROCARBONS 433
uric acid, ef Bunsen on the compounds of cacodyl, of Dumas
and Peligot on wood-spirit, and by the investigations of
Kolbe, Frankland, A. W. Hofmann, Williamson, Gerhardt,
Wurtz, Kekul4 and others during -the fifties and sixties.
Many of these researches have already been referred to in
the general section, because of the influence which they
exercised on the development of views regarding the
chemical constitution of organic compounds ; but it will not
be altogether possible to avoid recurring to some of them in
this portion of the book.
The recognition of the totally different behaviour of the
so-called saturated, unsaturated, and aromatic substances
was of the first importance for the systematising of organic
compounds. A precise distinction between and definition of
the above three classes, more especially of the two latter, has
been gradually brought about in the course of the last few
decades, as the knowledge of them has been extended. In
the study of organic compounds, the investigation of
physical properties has of late years acquired very great
prominence ; and this is easily intelligible when it is stated
that such investigation has greatly advanced the solution of
the question of chemical constitution.
Hydrocarbons and their Derivatives.
The hydrocarbons, from which as the simplest organic
compounds all the others are derivable, have been, as befits
their " typical " importance, the object of numberless investi-
gations, which have led to the development of doctrines
of the utmost weight. We have only to think of the
determination of the composition of marsh gas and of ethylene,
which led to the recognition of multiple proportions, and
with this to the setting up of the atomic theory ; of the im-
portance of Faraday's researches on butylene for the
evolution of what became known as polymerism; of the
labours of Regnault and others on ethylene and its haloid
compounds, which afforded such rich food for the theories of
F F
434 HISTORY OF ORGANIC CHEMISTRY CHAP,
substitution ; and lastly, of the work of Kekule and his pupils
on benzene and its derivatives — investigations on which most
of the work in organic chemistry for the last thirty years has
been based.
Mitscherlich's researches on benzene (which he then
termed Benziri) sixty years ago, taught new methods of pre-
paring hydrocarbons ; the formation of this substance from
benzoic acid, in consequence of the separation of carbon
dioxide, became typical for a large number of similar
reactions, e.g. the production of cumene from cumic acid, of
methane from acetic acid, of chloroform from trichloracetic
acid, &c. Of great theoretical importance, too, was Kolbe's
mode of formation of hydrocarbons by the electrolysis of the
alkaline salts of the fatty acids, and also that of Frankland
by the action of zinc upon alkyl iodides ; the latter investi-
gations led to the discovery of the zinc alkyls, and opened up
this especially fruitful field in the synthesis of organic com-
pounds.1 The researches of Wurtz,2 which showed how the
combination of different alkyl radicals from hydrocarbons
might be effected by the action of sodium upon two alkyl
iodides, bore much fruit subsequently among the aromatic
compounds ; for, with this reaction as a model, the homologues
of benzene were prepared synthetically, while at the same
time the simple mode of formation allowed of their chemical
constitution being deduced.3
Another synthesis 4 of homologues of benzene, depending
upon the peculiar interaction of aluminic chloride with
mixtures of benzene and chlorine compounds (such as methyl
chloride), has also proved itself of general application, as well
as serviceable for the artificial production of other bodies, e.g.
ketones, acids, &c. Notwithstanding the care with which
these reactions have been studied, a conclusive explanation
of the mode of action of the aluminium chloride has still to
be given; this much, however, may be taken as proved —
that their cause is to be sought for in the formation of
1 Cf. p. 362. 2 Ann. Chim. Phys. (3), vol. xliv. p. 275.
:! Cf. Fittig, A nn. Chem., vol. cxxxi. p. 301.
4 Friedel and Crafts, Comptes fiendus, vols. Ixxxiv., Ixxxv., &c.
vi THE AROMATIC HYDROCARBONS 435
peculiar intermediate compounds of the chloride with
aromatic hydrocarbons (Gustavson).1
Berthelot's method 2 of forming hydrocarbons out of
different organic compounds by the action of hydriodic acid
upon them at rather high temperatures, must also be men-
tioned here, since it has led to important results in many
cases. And reference must be made to the method, so fre-
quently employed, of reducing oxygen compounds to
hydrocarbons by heating them with zinc dust.3 The work of
Berthelot on acetylene, of Butlerow and others on the buty-
lenes and amylenes, of Freund on trimethylene, of W. H.
Perkin, jun., on the derivatives of tri- and tetra-methylene, of
Liebermann on allylene, &c., has materially enlarged our
knowledge of the unsaturated hydrocarbons. The remark-
able processes of the isomerisation of such compounds have
recently been cleared up by the valuable researches of
Faworsky.4
Out of the extraordinarily large number of investigations
on aromatic hydrocarbons, whose constitution has given rise
to important discussions, there may be mentioned here (in
addition to the above) those of Fittig5 and Baeyer6 on
mesitylene, which was found to be " symmetrical " trimethyl-
benzene, and also those of Graebe 7 upon naphthalene, and of
Graebe and Liebermann 8 upon anthracene. Important con-
clusions were drawn from the two last with respect to the
chemical constitution of these already long-known hydro-
carbons, which from thenceforth were regarded as standing
in a simple relation to benzene.
Other coal-tar hydrocarbons of complex composition have
likewise been satisfactorily investigated ; thus phenanthrene,
the isomer of anthracene, has been shown by Fittig and
Ber., vol. xi. p. 2751.
Ann. Chim. Phys. (4), vol. xx. p. 392.
Baeyer, Ann. Chem., vol. cxl. p. 295.
Journ. pr. Chem. (2), vol. xxxvii. pp. 382, 417, 532.
Ztschr. Chem. for 1866, p. 518.
Ann. Chem., vol. cxl. p. 306.
Ann. Chem., vol. cxlix. p. 22.
Ibid., Suppl, vol. vii. p. 257.
F F 2
436 HISTORY OF ORGANIC CHEMISTRY CHAP.
Graebe l to be a diphenylene derivative of ethylene, fluorene
by Fittig2 to be diphenylene-methane, and chrysene by
Oraebe3 to be phenylene-naphthalene-ethylene. To Bam-
berger4 is due the elucidation of the chemical nature of
retene and pyrene. Lastly, the important researches of
Kraemer and Spilker 5 throw light on the question — how the
individual compounds occurring in coal-tar may be formed
during the distillation of the coal.
A wide field has been opened up within the last
ten years by the discovery of the hydrides of aromatic
hydrocarbons — compounds of remarkable character. It will
be sufficient to refer here to the comprehensive work of
Bamberger,6 Baeyer 7 and Markownikoff 8 on the subj ect. The
last-mentioned has proved that a long series of the constitu-
ents of petroleum, — the so-called naphthenes — belong to
this class of hydro-compounds. Again, many of the latter
show close relations to the terpenes, substances about which
until recently very little was known, but which have been made
more and more accessible by the admirable systematic work
of Wallach. 9 By means of definite reactions it has been
found possible to introduce order among the dire confusion
of these " ethereal oils "; and some quite recent researches of
A. von Baeyer10 have thrown much light upon the constitu-
tion of the terpenes.
We must further refer to the admirable work of E. and O.
Fischer, Zincke and others on the phenyl derivatives of
methane, more especially triphenyl-methane ; this last was
1 Ann. Chem., vol. clxvi. p. 361 ; vol. clxvii. p. 131.
2 Ibid., vol. cxciii. p. 134.
3 Ber., vol. xii. p. 1078.
4 Ann. Chem., vol. ccxxix.p. 102; Ber., vol. xx. p. 365.
5 Ber., vol. xxiii, pp. 78 and 3266.
6 Cf. especially Ber., vol. xxii. p. 767; vol. xxiv. p. 2463.
7 Ber., vol. xxv. p. 2122; vol. xxvi. pp. 229, 820.
8 Journ. pr. Chem. (2), vol. xlv. p. 561 ; vol. xlvi. p. 86 (this last gives
the literature on the subject).
9 Ann. Chem., vol. ccxxv., ccxxvii., ccxxx., ccxxxviii., ccxxxix., ccxli.,
•cclviii., cclxix., cclxxv. andcclxxvii. ; also his lecture on the Terpenes, Ber.,
vol. xxiv. p. 1525.
1 Ber., vol. xxvi. pp. 820, 2267, 2558 and 2861.
vi THE ALCOHOLS AND ETHERS 437
proved by E. and O. Fischer to be the mother-substance
of exceptionally valuable aniline dyes, whose constitution
was thus explained.
The continuous and increasing effort to express organic
compounds as derivatives of the hydrocarbons is further
shown by the nomenclature. With the object of systema-
tizing this on a uniform plan, an International Commission l
of chemists met a few years ago at Geneva. The system
adopted by this Commission makes the hydrocarbons the
basis of the nomenclature proposed. But whether all the
branches of organic chemistry are at present sufficiently
advanced to allow of a satisfactory solution of the question
is highly problematical.
The Alcohols and Analogous Compounds.
The close connection existing between the alcohols and
the hydrocarbons was clearly recognised when methyl alcohol
(the first member of a long series of compounds of this
nature) had been successfully prepared from methane, by
converting the latter into methyl chloride, and then trans-
forming this into the alcohol. Formerly regarded as the
hydrated oxides of hypothetical radicals, the alcohols were
after this characterised as hydroxyl derivatives of the
hydrocarbons. What an influence Williamson's researches
on the formation of ether and Kolbe's views on the con-
stitution of the alcohols had upon the development of the
opinions now held with regard to this point, has been
already described.
Among the most important of the investigations which
helped to establish our knowledge of the alcohols were those
of Dumas and Peligot2 on wood-spirit, whose analogy to
1 Compare the Rapport de la Sous- Commission nomme'e par le Congres
Chimique de 1889, &c. (Paris, 1892) ; the report by Pictet in the Archives
des Sciences Physiques et Naturelles, May 1892; Tiemann's report in the
Berichte, vol. xxvi. p. 1595 ; and Armstrong's report in Nature for 1892,
vol. xlvi. p. 56.
2 Ann. Chim. Phys., vol. Iviii. p. 5; vol. Ixi. p. 93.
438 HISTORY OF ORGANIC CHEMISTRY CHAP.
ethyl alcohol they clearly recognised. The true composition
of the latter was worked out by Saussure, who thus did
away with the fundamentally erroneous ideas regarding it
which had prevailed since the time of Lavoisier ; the latter
had indeed arrived at a correct knowledge of its constituents,
but not of the proportions in which these were present.
Equally important were the fact that aethal (C16H33OH), dis-
covered by Chevreul, was characterised as an analogue of
alcohol by Dumas and Peligot in spite of its unlikeness to the
latter, and the corresponding proof by Cahours l for the amyl
alcohol obtained from fusel oil, to which isobutyl alcohol2
was afterwards added. The discovery of the secondary and
tertiary alcohols, so memorable for the history of this class
of compounds, was, as already stated, prognosticated by
Kolbe. The series of the secondary carbinols was begun
with isopropyl alcohol, isolated by Friedel, and that of the
tertiary with Butlerow's trimethyl-carbinol. The modes of
formation of these substances (that of isopropyl alcohol
from acetone by the addition of hydrogen, and that of
trimethyl-carbinol from acetyl chloride and zinc methyl)
have since been extensively made use of for the preparation
of analogous compounds.
Carbinols of other series were investigated by Cannizzaro,
who discovered benzyl alcohol,3 the simplest carbinol of the
aromatic series, and by Cahours and Hofmann, who isolated
allyl alcohol ; 4 while an accurate acquaintance with various
new primary carbinols of the fatty series was arrived at by
the systematic researches of Lieben and Rossi.5 The
above-mentioned investigations were also of great importance
for the development of the views upon chemical constitution,
and more especially upon the isomerism of organic
compounds,
The knowledge of the polyatomic alcohols had its be-
ginning in the already-mentioned important researches of
1 Ann. Chim. Phys., vol. Ixx. p. 81 ; vol. Ixxv. p. 193.
2 Wurtz, Ann. Chem., vol. xciii. p. 107.
3 Ibid., vol. cxxiv. p. 324.
4 Ibid., vol. c. p. 356. 5 Cf. Ibid., vol. clviii. p. 137.
vi THE ALCOHOLS AND ETHERS 439
Berthelot on glycerine, as representing the triatomic
carbinols, and especially in those of Wurtz on the diatomic
glycols. In connection with these we would call attention
here to the notable discovery of the poly-ethylene alcohols,
and of ethylene oxide (distinguished by the readiness with
which it enters into reaction).
The discovery of the fact that certain sugars lare
polyatomic alcohols is of quite recent date ; mannite, for
instance, is a hexoxy-hexane and arabite, rhamnite and pentite
are pentoxy-hexanes. The " carbohydrates," being aldehydes
or ketones, are closely related to these.
The derivatives of the alcohols known as the simple
ethers, with common ethyl ether at their head, have
frequently been the subject of important investigations..
The discussions upon the constitution of ether and its mode
of formation — discussions which lasted for many years — were
brought to an end by the work of Williamson and Chancel,
which led to the discovery of mixed ethers.2
The knowledge of the compound ethers, frequently
now also called Esters, has been greatly extended within
the last sixty years. The recent observations of the late
Victor Meyer and his pupils on the formation of esters of
aromatic acids are of great interest here, the constitution of
these acids determining the path which the synthesis follows..
To the neutral ethers of the acids, the number of which has
gone on continuously increasing (but regarding which it is
impossible to mention here even the more important
researches), there have been added the so-called ether-acids,
whose chemical nature has been cleared up by the work of
Hennel, Serullas, Magnus and Regnault on ethyl-sulphuric
.and ethionic acids, of Pelouze on the ethyl-phosphoric
acids, of Mitscherlich on ethyl-oxalic acid, and other more
recent labours, e.g. that upon phenyl-ethyl-sulphuric acid by
Baumann, and upon ethyl-oxalic acid by Anschiitz.
Certain of the compounds prepared from ethyl alcohol
1 Comptes Rendus, vol. xlviii. p. 101 ; vol. xlix. p. 813.
2 Cf. p. 298.
3 Ber., vol. xxvii. pp. 1580, 3146; vol. xxviii. p. 2773.
440 HISTORY OF ORGANIC CHEMISTRY CHAP.
and other carbinols have played an important part in the
synthesis of organic substances, thanks to their capability of
reaction ; we have but to recall here the discovery of sodium
ethylate by Liebig, that of chloro-carbonic ether by Dumas,
and Debus' investigations of the products which result from
the oxidation of ethyl alcohol by nitric acid.
The first step towards a knowledge of those compounds
so nearly allied to the alcohols, which have received the
generic name of phenols, was Laurent's investigation of
carbolic acid and its derivatives.1 Gerhardt was the first to
point out the analogy between alcohol and phenol. Of
great importance for the development of this class of com-
pounds, and more especially for their technical production,
was that mode of formation of phenol itself which was first
observed by Kekule*2 and Wurtz,3 viz. by fusing benzene-
sulphonic acid with potash. This reaction soon led to the-
discovery of a large number of mono- and poly-atomic phenols ;
the naphthols and other oxy-derivatives of naphthalene, the di-
and trioxy-benzenes, etc. were isolated. The reactions of
these compounds turned out to be of remarkable interest
not merely from a technical, but also from a purely
scientific point of view; one need but refer to the
conversion of many phenols into quinones, and to the various
transformations of these latter by chlorine and bromine. The
comprehensive researches of Zincke 4 and his pupils on this
subject are worthy of special mention here ; the nature of
the peculiar decomposition-products of the phenols allowed
of conclusions being drawn as to the constitution of the
original compounds.
1 Ann. Chim. PJiys. (3), vol. iii. p. 195. Runge was the discoverer of
carbolic acid itself.
2 Lehrb. der. organ. Chemie, vol. iii. p. 13.
3 Ann. Chem., vol. cxliv. p. 121.
4 Ber., vol. xxi. p. 3540; vol. xxii. pp. 1024, 1467 ; vol. xxiii. pp. 230,,
1706, 2200, &c. ; Ann. Chem., vol. cclxi. p. 208.
vi EARLY WORK ON THE CARBOXYLIC ACIDS 44F
Carboxylic Acids.
A field of immense extent and fertility became open
to chemical research with the systematic investigation of
the acids contained in animal and vegetable fats, as well as
in other natural products. The important work on the fatty
acids, suggested in the first instance by Liebig, and which was-
accomplished by his pupils Varrentrapp, Rochleder, Bromeis,
Fehling, Redtenbacher and others, and that of Heintz1 upon
palmitic and stearic acids, not only materially supplemented '
the earlier investigations of Chevreul on the fats, but led
to the discovery of new and wider domains. Important
methods for the separation of the fatty acids resulted from
these labours. The common link which unites the com-
pounds of this class was only discovered when their chemical
constitution came to be understood. The successful efforts
of Kolbe, who was the first to recognise acetic as methyl-
carboxylic acid, and who established this view by direct
experiment, have been already described in the general
section. It has indeed been from acetic, as the most fully
investigated of all the carboxylic acids, that our present
ideas upon the constitution of the whole class of compounds
have developed themselves. The recognition of the correct
atomic composition of acetic acid by Berzelius in 1814, and
of its relation to alcohol by Dobereiner in 1821, was of
great importance for the solution of this problem.
After the constitution of the carboxylic acids had once
been grasped, it became possible for Kolbe to predict the
existence of other members of this class, as he had done in
the case of the alcohols, and thus existing blanks could be
filled up. Of special importance here was the discovery of
isobutyric acid,2 of the isomers of valeric acid — itself
already long known, and of other acids richer in carbon,
in the systematic investigation of which Lieben and
1 Ann. Chem., vol. Ixxxiv. p. 297; vol. Ixxxviii. p. 297; Journ. pr. Chem.
vol. Ixvi. p. 1.
2 Erlenmeyer, Ztschr. Chem. for 1865, p. 651.
442 HISTORY OF ORGANIC CHEMISTRY CHAP..
Rossi1 and Krafft, among others, have rendered great
service.
The knowledge of the polybasic saturated carboxylic
acids, whose chemical constitution was likewise only
thoroughly established by Kolbe's speculations, was greatly
advanced by the work of Berzelius, Fehling and others on
succinic acid (synthetised from ethylene cyanide by Maxwell
Simpson 2), by that of Arppe on adipic acid and homologous
compounds,3 and by the discovery and investigation of
malonic acid,4 &c. The ethers of this last acid have
served for the synthesis of homologues of malonic and other
polycarboxylic acids,5 thanks to the facility with which
they exchange hydrogen for sodium ; while from aceto-acetic
ether, which so closely resembles malonic, there have been
prepared numerous compounds belonging to this class, to
be afterwards systematically investigated. Drechsel's memor-
able synthesis of the simplest dibasic acid, oxalic, from
carbon dioxide and sodium,6 also deserves mention here.
The synthesis of the mono- and polybasic acids has proved
in most cases the best guide to their constitution.
The wide field of unsaturated carboxylic acids, some of
which (e.g. acrylic, angelic, fumaric and maleic) were dis-
covered at an early date, first became cultivated with
success after a clear idea of the constitution of these com-
pounds had been arrived at through Kekule's admirable
investigations7 on the two last-named and on the pyro-
citric acids, which explained the behaviour of these bodies
to nascent hydrogen ; and after Frankland and Duppa 8 had
made their beautiful syntheses, which resulted in the
1 Cf. Ann. Ghent. , vol. clix. p. 75; vol. clxv. p. 116.
2 Proc. JR. S., vol. x. p. 574 ; or Ann. Ghent., vol. cxviii. p. 373.
3 Ann. Chem., vol. cxv. p. 143; vol. cxx. p. 288.
4 Ibid., vol. cxxxi. p. 348.
5 Cf. Conrad, Bischoff, and Guthzeit, Ann. Chem., vol. cciv. p. 121 ;
vol. ccix. p. 211 ; vol. ccxiv. p. 31.
6 Ztschr. Chem. for 1868, p. 120.
i Ann. Chem., vol.cxxx. p. 21 ; vol. cxxxi. p. 81 ; Suppl., vol. i. p. 129 ;
vol. ii. p. 198.
8 Journ. Chem. Soc., vol. xviii. p. 133; or Ann. Chem., vol. cxxvi. p. 1.
iv UNSATURATED CARBOXYLIC ACIDS 443
conversion of oxalic ether into unsaturated carboxylic
acids. In fact this last investigation led Frankland to
express the view that acrylic acid and its homologues were
derivatives of acetic acid, and a simple explanation was
given of their transformation into the latter (by means of
potash). The more recent systematic researches of Fittig l
and his pupils on the unsaturated carboxylic acids have
contributed in great degree to round off and deepen our
knowledge of this class of compounds. The latest observa-
tions on the molecular transformations of the so-called a-/3-
unsaturated acids2 into the isomeric /9-y-acids, and vice
versa, calls for particular mention. Remarkable results, too,
have been obtained by A. Saytzeff and others on the
oxidation of such acids by permanganate of potash. The
discovery of tetrolic and propiolic acids 3 prepared the way
for an acquaintance with the carboxylic acids derived from
acetylene.
The discovery and careful investigation of peculiar
isomers among the unsaturated acids has been carried out
more particularly during the last ten years. The observa-
tions made on fumaric and maleic, crotonic and isocrotonic,
angelic and tiglic acids led to the successful attempt —
already spoken of on p. 356 — to explain the constitution of
these and similar isomers on stereo-chemical principles.
Facts bearing on this subject are gradually accumulating,
t.g. the discovery of the isomeric cinnamic acids by Lieber-
mann,4 the investigation of the relations existing between
erucic and brassidic 5 acids by Holt,6 Fileti and Saytzeff, &c ;
but we are not yet in possession of a theory which satisfac-
torily explains all the phenomena of this kind.
The class of the aromatic carboxylic acids, with benzoic
1 Ann. Chem., vol. clxxxviii. p. 87 ; vol. cxcv. p. 50 ; vol. cc. p. 21 ; vol.
ccvi. p. 1 ; vol. ccviii. p. 37.
2 Fittig, Ann. Chem., vol. cclxxxiii. pp. 47 and 269.
3 Geuther, Journ. pr. Chem. (2), vol. iii. p. 448 ; Bandrowski, Ber., vol.
xiii. p. 2340.
4 Ber., vol. xxiii. pp. 141, 512, 2510 ; vol. xxv. pp. 90, 950.
6 Ber., vol. xxiv. p. 4128; vol. xxv. p. 1961.
444 HISTORY OF ORGANIC CHEMISTRY CHAP,
acid at their head, has been the subject of innumerable and
fruitful researches. We have but to recall here the dis-
covery of the peculiar mode of formation of these com-
pounds from hydrocarbons by oxidation, as well as by the
direct introduction of the elements of carbonic acid by means-
of aluminic chloride;1 and the splendid investigations on
the di-, tri-, and poly-carboxylic acids of benzene,2 to the
last class of which the already long-known mellitic acid was
found to belong. The aromatic carboxylic acids of unsaturated
character, like cinnamic acid, etc., proved particularly easy
of examination after Perkin3 had worked out the reaction
now known by his name — a reaction which can be generally
applied to their formation. Lastly, the isolation of phenyl-
propiolic acid 4 and its derivatives has led to results of
importance.
The esters have in many cases proved serviceable for
obtaining other important derivatives of the carboxylic
acids; thus, by means of the reactions which have been
investigated by L. Claisen and W. Wislicenus, ketones
and ketonic acids, etc., have been prepared (see those
compounds).
The discovery of the chlorides, anhydrides and amides
of the carboxylic acids deserves particular mention herey
since these classes of compounds fill an important place in.
the history of organic chemistry. The first organic acid
chloride was benzoyl chloride, obtained by Liebig and
Wohler by the action of chlorine on oil of bitter almonds,
in their classical research already so frequently referred to.
The general method for the preparation of such compounds, i.e.,,
by acting upon organic acids with phosphorus pentachlorider
is due to Cahours ; 5 since then this reagent has been a
1 Friedel and Crafts, Comptes Rendus, vol. Ixxxvi. p. 1368.
2 Baeyer, Ann. Chem., Suppl., vol. vii. p. 1 ; vol. clxvi. p. 325; Fittigy
ibid., vol. cxlviii. p. 11 ; Graebe, ibid., vol. cxlix. p. 18, etc.
3 Journ. Chem. Soc., vol. xxi. p. 53 ; or Ann. Chem., vol. cxlvii. p. 229.
4 Glaser, Ann. Chem., vol. cliv. p. 140; Baeyer, JBer.,vol. xiii. p. 2258.
5 Ann. Chem.,vol Ix. p. 254. A. Cahours (1813-1891) filled the chairs of
chemistry at the Ecole Centrale and the Ecole Polytechnique of Paris, and
was at the same time Master of the Mint there. In addition to his
vi THE ACID CHLORIDES AND ANHYDRIDES 445
standard one in organic chemistry, and has proved its value
in the most varied circumstances, but more especially for
the replacement of oxygen or hydroxyl by chlorine. Phos-
phorus oxychloride was applied by Gerhardt,1 and phosphorus
trichloride by Bechamp2 for the same purpose; these are
however used but seldom in comparison with the penta-
chloride.
The great capability of reaction which the acid chlorides
possess had already been shown by Liebig and Wohler in
the case of benzoyl chloride, from which they prepared
the amide of benzoic acid with ammonia, the ether with
alcohol, and the sulphide with sulphide of lead, thus
introducing at the same time general modes of formation
for these classes of compounds. The acid chlorides after-
wards led Gerhardt3 on to the important discovery of the
acid anhydrides, which have likewise proved of great value
for the synthesis of organic compounds ; take, for instance,
acetic anhydride, so often used for obtaining other acetyl
compounds and condensation-products, and phthalic anhy-
dride, an extremely reactive substance. Brodie4 then
prepared from some of those anhydrides the peroxides of
the acid radicals, so remarkable in their behaviour, which
have since been ranked alongside of peroxide of hydrogen.
To the acid amides, a class which had been opened up by
Dumas' discovery of oxamide, Gerhardt added the anilides,
and thus gave the impulse to the sub-division of the former
into primary, secondary and tertiary amides. The discovery
of the aminic acids and the imides of polybasic acids must
Ldcons de Chimie generate fiUmentaire — a work greatly valued in France
— he published numerous researches which helped materially to advance
certain branches of organic chemistry; e.g., papers upon amyl alcohol,
cuminol, anisol, oil of winter green, the sulphines, arsines, stannines, and —
conjointly with A. W. Hofmann— upon allyl alcohol. But the claim put
forward by Etard in his obituary of Cahours (Bull. Soc. Chim. vol. vii. p. 1),
that the latter was the discoverer of sulphines, is mistaken ; the priority in
this belongs to von Oefele.
1 Ann. Chim. Phys. (3), vol. xxxvii. p. 285.
2 Comptes Rendus, vol. xl. p. 944.
8 Ann. Chem., vol. Ixxxii. p. 131 ; vol. Ixxxvii. p. 151.
4 Proc. R. S., vol. xii. p. 655 ; or Ann. Chem., vol. cxxix. p. 282.
446 HISTORY OF ORGANIC CHEMISTRY CHAP,
also be mentioned here, — compounds which are closely
related to the amides ; oxamic acid was isolated by Balard,
and succinimide by Fehling. And reference must be made,
too, to the connection between the acid nitriles and the
primary amides of the acids, the latter being converted into-
the former by the abstraction of the elements of water.
The investigation of certain derivatives of the carboxylic
acids has led to results of very great moment, in that
a thorough grasp has been gained of the relations existing
between them and two other great classes of compounds —
the oxy- and amido-aeids. The distinct idea which is now
associated with the terms " oxy-carboxylic acid " and " amido-
carboxylic acid" has developed itself from lactic acid and
alanin as oxy- and amido-propionic acids, and from those
other compounds already known for such a long time before
their constitution had been deciphered, — glycollic acid and
glycocoll. The work of Wurtz,1 and of R. Hofmann and
Kekule,2 among others, upon those substances, and especially
the decisive investigations of Kolbe, which furnished the key
to a thorough explanation of the facts, laid the foundation of
our present knowledge of these classes of compounds.3
Of great importance for the true recognition of the
relations of the substances just named to one another, and
to the carboxylic acids from which they are derived, was
the transformation of the amido- into oxy-acids by means
of nitrous acid (Piria, Strecker, etc.), andjihe conversion of
the latter into the corresponding carboxylic acids by means
of hydriodic acid. In this way the constitution of malic,
tartaric, aspartic, lactic, and many other acids was definitely
arrived at,4 so that the method may be considered as a
peculiarly valuable aid in elucidating the rational composition
of many organic compounds. Wislicenus5 has contributed
in a very marked degree to a knowledge of the various
1 Ann. Chim. Phys. (3), vol. lix. p. 171.
2 Ann. Chem., vol. cii. p. 11 ; vol. cv. p. 288. 3 Cf. p. 319.
4 Cf. Schmitt, Ann. Chem., vol. cxiv. p. 106 ; Kolbe, ibid., vol. cxxi. p,
232 ; Lautemann, ibid. , vol. cix. p. 268.
5 Ann. Chem., vol. cxxviii. p. 11 ; vol. clxvi. p. 3; vol. clxvii. p. 302.
vi THE OXY- AND AMIDO-ACIDS 447
lactic acids, his work on the subject having helped greatly
to extend the doctrine of isomerism. The idea of " physical
isomerism," which originated in the different behaviour
of substances of the same composition towards polarised
light, has since developed itself more and more, Pasteur's
memorable researches1 on Isevo- and dextro-tartaric acids,
and on the inactive racernic acid produced by their com-
bination, having previous to this thrown much light upon
the subject. It has been already explained how the theory
of the asymmetric carbon atom arose. The few isolated
observations which led to its establishment have since been
materially increased, and prediction has been verified by the
discovery, after patient search, of two lactic, mandelic and
malic acids, besides other compounds.
Once the constitution of many of the naturally occurring
oxy- and amido-acids became known, the synthetic prepara-
tion of such compounds was merely a question of time ;.
thus, lactic acid was prepared artificially from propionic acid
as well as from aldehyde,2 inactive tartaric acid from
dibromo-succinic,3 citric acid from acetone,4 hippuric acid
(first recognised as a definite compound by Liebig) from
glycocoll,5 and salicylic acid from phenol.
This last leads us to the aromatic oxy-acids, and to the
important method of their formation from phenates and
carbonic acid, discovered by Kolbe.6 A complete explanation
of this general reaction has only of late been given by
Schmitt,7 who has proved that the production of an isomer
(sodium phenyl-carbonate, C6H5O.O.CO2Na) precedes that
of the sodium salicylate. The observation that the phenates
behave very differently according to the nature of their
1 Ann. Chim. Phys. (3), vol. xxiv. p. 442; vol. xxviii. p. 56; vol. xxxviii.
p. 437.
2 Wislicenus, Ann. Chem., vol. cxxviii. p. 11.
3 Kekule, ibid., vol. cxvii, p. 124.
4 Grimaux and Adam, Comptes Rendus, vol. xc. p. 1252.
5 Dessaigne, Jahresber. d. Chem. for 1857, p. 367.
6 Cf. Ann. Chem., voL cxiii. p. 125 ; vol. cxv. p. 201 ; Journ. pr. Chern^
2), vol, x. p. 95.
7 Journ. pr. Chem. (2), vol. xxxi. p. 397.
448 HISTORY OF ORGANIC CHEMISTRY CHAP.
^alkali, — that, for instance, phenol-potassium and carbonic
.acid yield the isomeric para-oxy-benzoic acid instead of
salicylic, — deserves to be noted here as especially important.
Ost's discovery of the phenol-di- and tri-carboxylic acids,
which result from the same reaction at a higher temperature,
must also be recalled.
Of late years a special group has been formed of a
peculiar class of oxy-acids which readily change into the so-
called lactones or intra-molecular anhydrides, with separation
-of water. Fittig,2 in conjunction with his pupils, has investi-
gated this remarkable class of compounds systematically, and
.has largely contributed towards a knowledge of the relations
between the lactones and the corresponding acids, and also
of their constitution, which formerly received a different
interpretation; thus, the simplest member of the series,
butyro-lactone, was previously held to be the aldehyde of
succinic acid. The relation of many lactones to • unsaturated
acids is particularly interesting. Numerous lactonic acids have
also been examined, and found to be carboxylic derivatives
-of the lactones.
Aldehydes.
The knowledge of the aldehydes, so important from many
different points of view, has gone on steadily increasing ever
since bitter almond oil or benzoic aldehyde was first investi-
gated by Liebig and Wohler, and ordinary aldehyde also by
the former ; the latter compound, first obtained by Fourcroy
and Dobereiner, was carefully examined by Liebig. The
chemical constitution of the aldehydes and of the nearly allied
ketones was first definitely grasped and given expression to
by Kolbe. Both classes of compounds acquired special im-
portance after their capacity for combining with other organic
bodies became known; they were thenceforward largely
utilised for the synthesis of compounds richer in carbon.
1 Ibid. , (2), vol. xiv. p. 95.
2 Cf. Ann. Chem., vol. ccviii. p. 111. ; vol. ccxvi. p. 27; vol. ccxxvi.
p. 322 ; vol. ccxxvii. p. 1 ; vol. cclv. pp. 1, 257 ; vol. cclvi. p. 50 ; vol.
^clxviii. p. 1.
THE ALDEHYDES 449
Liebig 1 was the first to explain the relation of the aldehyde
of acetic acid to alcohol on the one hand, and to acetic
acid on the other, whereupon Berzelius pointed out clearly
the analogy existing between aldehyde and acetic acid
and bitter almond oil and benzoic acid respectively. The
mode of formation of the aldehydes, by oxidation of the
alcohols, has since then remained the general one. It was
only discovered at a much later date that members of this
class of compounds could be prepared from the salts of the
acids, by heating these with sodium formate.2 Still more
recent is the discovery of the method of preparing aromatic
aldehydes from phenols, chloroform and alkali (i.e. nascent
formic acid), a reaction which has led to the isolation of
some curious compounds.3 And quite lately Gattermann*
has made the remarkable observation that aldehydes are
formed by the union of a hydrocarbon with carbon monoxide
in presence of a mixture of hydrochloric acid, cuprous chloride
and chloride of aluminium. The aldehyde of formic acid, the
first member of its series, was prepared by A. W. Hofmann,6
the simplest representative of the di-aldehydes, glyoxal, having
already been obtained long before by Debus (1856) as one
of the products of the oxidation of alcohol. With regard to
aldehydes of complex composition, many of these were long
ago isolated from various ethereal oils, e.g. oil of cinnamon, oil of
cumin, etc., and recognised as analogues of ordinary aldehyde.
The agreeable odour which many aldehydes possess rendered
their artificial production desirable, and so in this way van-
illin, heliotropin and others were synthetised, and their con-
stitution established.
Ordinary aldehyde has been ever and anew the subject of
important investigations, more especially since Liebig and
Fehling observed its tendency to polymerise (into para- and
meta-aldehydes).6 Liebig's observation that benzoic aldehyde
1 Ann. Chem., vol. xiv. p. 133 ; vol. xxii. p. 273.
2 Piria, Ann. Chem., vol. c. p. 114 ; Limpricht, ibid., vol. ci. p. 291.
3 Reimer, Ber., vol. ix. p. 423; Tiemann, ibid., vol. ix. p. 824 ; vol. x.
p. 63.
4 Ber., vol. xxx. p. 1620. 5 Proc. 7?. £., vol. xvi. p. 156.
6 Ann. Chem., vol. xxv. p. 17 ; vol. xxvii. p. 319.
G G
450 HISTORY OF ORGANIC CHEMISTRY CHAP,
changed into the polymeric benzoin in presence of cyanide of
potassium must also be mentioned here ; it was the origin
of further work which led to the discovery of such interesting
compounds as benzile, benzilic acid, etc. And those researches
gained an increased interest through the discovery of aldol l (a
condensation product of aldehyde, of the same percentage
composition with it), and of its nearly allied compound, cro-
tonic aldehyde ; 2 the perception of the constitution of the
last-named substance was of importance in that it led to an
explanation of this " condensation," and therefore also of other
similar processes.
It was thus from aldehydes that a knowledge was gained
of the peculiar chemical reactions now known generally under
the above name of condensations. The aldehydes possess in a
superlative degree the capacity for combining with other com-
pounds of similar or dissimilar nature — e.g. acids, ketones,
amines, etc. — water being eliminated (cf. p. 363). They are
thus of exceptional value for the synthesis of organic com-
pounds. A. v. Baeyer was the first to point out that formic
aldehyde — the simplest member of the series — played a
prominent part in the building up of carbohydrates, acids,
and other compounds in plants.
The numerous investigations which have been made with
the object of explaining such reactions of aldehydes with
other compounds, under elimination of water, cannot be given
in detail here. Reference can only be made to those of W.
H. Perkin, sen., who showed how the condensation of aromatic
aldehydes with fatty acids might be effected, — a reaction
which, developed as it has been, still continues to yield rich
fruit ; 3 and to the researches of L. Claisen, who has systema-
tically examined the manifold condensation processes of which
the aldehydes and ketones are capable.4
While an extraordinary number of new and important
J Wurtz, Comptes Rendus, vol. Ixxiv. p. 1361.
2 Kekute, Ann. Chem., vol. clxii. pp. 92, 309.
3 Cf. Ann. Chem., vol. ccxvi. p. 115; vol. ccxxvii. p. 48, etc.
4 Cf. Ibid., vol. clxxx. p. 1 ; vol. ccxviii. p. 121 ; vol. ccxxiii. p. 137 ;
vol. ccxxxvii. p. 261 ; Ber., vol. xxi. p. 1135.
vi KETONES AND KETONIC ACIDS 451
compounds has been obtained in this way, the energies of many
workers have also been devoted for a long time to the pre-
paration of others resulting from the action of ammonia upon
the aldehydes (especially benzoic aldehyde), and, more recently,
to the compounds similarly obtained with hydroxylamine and
phenyl-hydrazine, i.e. the aldoximes and hydrazones.
The thio-aldehydes were first observed a long time ago, but
have only been investigated minutely of late years, more es-
pecially by Baumann ; remarkable cases of isomerism have
been discovered among them, to explain which recourse is
being had to stereo-chemistry. — Mention must also be made
of the discovery and gradual examination of the aldehyde-
alcohols, aldehyde-acids, oxy- and amido-aldehydes, and the
acetals, — these last being closely related to the aldehydes.
Like aldehyde itself, these various substances have proved
of much service for the synthesis of many important com-
pounds.
Ketones and Ketonic Acids.
The work done upon the ketones, compounds so closely
allied to the aldehydes, has also been most fruitful. The
simplest member of this class of bodies, acetone, had already
been known for a long time and had been the subject of fre-
quent investigation when Liebig l definitely established its
composition. Important points in the further history of the
ketones were (1) the discovery of their mode of formation
from acid chlorides and zinc alkyls,2 and (2) the preparation
of mixed ketones by distilling the lime salts of the two
carboxylic acids together.3 The formation of those peculiar
compounds, mesityl oxide, phorone and mesitylene, from
acetone was observed a long time ago, but it was only com-
pletely explained after similar processes depending upon the
condensation of aldehyde had been correctly interpreted.
1 Ann. Chem., vol. i. p. 223.
2 Freund, Ann. Chem., vol. cxviii. p. 1.
3 Williamson, Journ. Chem. Soc., vol. iv. p. 238 ; or Ann. Chem., voL
Ixxxi. p. 86.
G G 2
452 HISTORY OF ORGANIC CHEMISTRY CHAP.
The remarkable method, discovered by Friedel and Crafts, of
synthetising ketones from aromatic hydrocarbons and acid
chlorides in presence of chloride of aluminium,1 threw open
the wide field of fatty-aromatic ketones. The behaviour of
these last towards oxidising agents, especially permanganate
of potash, has been largely investigated and has led to very
curious results.2
The transformation of ketones into secondary carbinols
by the addition of hydrogen has been already spoken of.3
Equally worthy of notice was the conversion of acetone into
pinacone,4 a diatomic alcohol, and that of the latter into
pinacoline ; those reactions, extended to other — especially
to aromatic — ketones, have led to important results.5
The analogy of the ketones to the aldehydes is very clearly
shown by the fact that the former also react with hydroxyl-
amine and phenyl-hydrazine to produce oximes and hydra-
jzones, the investigation of which has likewise proved of great
value. (See below.)
Entirely new fields have been opened up by the investi-
gation of the di-ketones, to which acetyl- and benzoyl-
acetones, acetonyl-acetone, naphthoquinone, anthraquinone,
and, as recent researches have shown, benzoquinone and
similar compounds belong, — substances whose nature has
been elucidated by the labours of Graebe, Liebermann, Fittig,
Zincke, Claisen, Paal, Combes and others.
The beautiful condensation of esters with ketones, discov-
ered by Claisen,6 has made known to us the so-called
/3-diketones, these being totally distinct from the correspond-
ing a- and ^-compounds. The quinones are now regarded
with special interest, on account of a quinonic constitution
being assumed for many dyes. Indeed Armstrong, Nietzki
1 Ann. Chim. Phys. (6), vol. i. p. 449 ; or Ber., vol. xvii., Ref. p. 376.
2 Cf. Popoff, Ann. Chem., vol. clxi. p. 289; Glaus, Journ.pr. Chem. (2)
vol. xli. p. 396 ; and especially Wagner, ibid., vol. xliv. p. 257 (this last
gives the literature on the subject).
3 Cf. p. 438.
4 Fittig, Ann. Chem. vol. ex. p. 25 ; vol. cxiv. p. 54.
5 Cf. Zincke, £er., vols. x. and xi.
6 £er.,\ol. xxii. pp. 1009, 3273, etc.
vi THE KETONIC ACIDS 453
and others suppose that this actually determines the dye-
character of the compounds in question.
The acids known as croconic acid, carboxylic acid
(C10H4O10), etc., prepared from potassium carboxide, were
obtained a long time ago by Will and Lerch ; the beautiful
researches of Nietzki1 have shown that some of them are
related to benzoquinone, while others are derived from a
compound (not yet isolated) containing a ring-shaped mole-
cule of five carbon atoms. The obscurity hitherto surround-
ing the constitution of these remarkable bodies has thus
been dispersed. They are now known as poly-quinones.
The so-called ketonic acids, certain of which (e.g. pyro-
racemic) have been known for a long time, have of late years
awakened the interest of a large number of investigators,
and rightly so ; we have but to think of the splendid results,
more especially from the synthetic point of view, which
have been achieved with aceto-acetic ether,2 levulinic acid,s
acetone-dicarboxylic acid,4 benzoyl-carboxylic acid 5 (which
has become of importance through its relation to isatin), and
other similar compounds. These ketonic acids acquire a
still greater theoretical interest from the circumstance that
they show a double chemical behaviour, their constitution, as
judged from certain reactions, being that of hydroxyl com-
pounds, and as judged from certain others, that of carbonyl
ones.6 Thanks to the reaction discovered by Claisen and
W. Wislicenus, of which mention has already been frequently
made, the synthesis of the ketonic acids has been carried out
most thoroughly. These compounds have proved of the
greatest interest in many respects ; to mention only a few, —
take the production of oxalo-acetic and formyl-acetic esters 7
1 Ber., vol. xviii. pp. 499 and 1833 ; vol. xix. pp. 293 and 772.
2 Of. Wislicenus, Ann. Chem., vol. clxxxvi. p. 161 (contains a historical
review).
3 Conrad's investigations showed this to be j8-aceto-propionic acid (Ann.
Chem., vol. clxxxviii. p. 223).
4 v. Pechmann, Ber., vol. xvii. p. 2542; Ann. Chem., vol. cclxi. p.
151. 6 Claisen, Ber., vol. x. p, 430.
6 See General Section, p. 354.
7 Ber., vol. xx. pp. 2931, 3392. Claisen and v. Pechmann have lately
454 HISTORY OF ORGANIC CHEMISTRY CHAP.
and the remarkable transformations which these are capable
of undergoing, the synthesis of chelidonic acid 1 from oxalic
ether and acetone, and that of hydro-chelidonic acid and
others. And if, in addition to these points, we recollect that
a large number of interesting compounds like camphor,
menthone, dehydracetic acid, pyrone derivatives, etc., belong to
the family of ketones, we can form some idea of the extent of
the field, and of the variety of results to be obtained from it.
Camphor, especially, with its almost endless allied compounds
and derivatives, has for some years past been investigated
minutely and also with good results, but the views of different
experimenters as to its constitution are still far from
concordant. Among those who have done most here,
A. v. Baeyer Beckmann, Bredt, Bourcault, Friedel, Tiemann
and Wallach must be named.
Carbohydrates and Glucosidcs.
The sugar varieties, which are so widely distributed in
nature, and many of which have been known from an early
age, belong partly to the alcohols and partly to the aldehydes
and ketones. Just as the practical importance of many of
these bodies has increased in an extraordinary degree, so has
also their purely scientific interest augmented with an
advancing knowledge of the close relations which exist
between the sugar varieties and compounds whose constitu-
tion has been already worked out. Thus, many of the hexoses
have been transformed into mannite, which is now known to
be primary hexyl alcohol containing six hydroxyl groups in
place of five hydrogen atoms ; the rational composition of
saccharic, mucic and levulinic acids, which are more or less
intimately related to the sugars, has been arrived at ; and the
acid ethers of the latter have been obtained, &c. Such
observations as these give support to the assumption that
those carbohydrates which are comprised under the term
proved that this so-called formyl-acetic ester is really oxy-acrylic (Ber.,
vol. xxv. p. 1040). 1 jBer., vol. xxiv. p. 111.
vi THE CARBOHYDRATES 455
glucoses, or — better — hexoses, are to be regarded as derived
from hexatomic alcohols, from which two atoms of hydrogen
have been withdrawn in such a manner that they contain the
formyl of the aldehydes or the carbonyl of the ketones
{Baeyer, Fittig, V. Meyer).
The investigation of the individual sugars — of their
-chemical behaviour and the products of their decomposition-
has been participated in by a great number of chemists ;
-among those who have actively busied themselves with the
subject we may mention Brouchardat, Brown and Heron,
Kiliani, v. Lippmann, O'Sullivan, Salomon, Scheibler, Soxhlet,
Tollens 1 and, especially, Emil Fischer.2 Fischer's beautiful
investigations, published in the Berichte 3 during the last ten
years or so, have given us a deep insight into the constitution
of the sugars. They have not only corroborated the assump-
tion that the latter are partly aldehyde-alcohols (aldoses),
and partly ketone-alcohols (ketoses), but have also paved the
way for the stereo-chemical elucidation of the numberless
isomers which exist among them.
Phenyl-hydrazine (p. 365) has proved itsel£ of the greatest
value for characterising individual sugars ; and, by means of
the osazones produced by this interaction, the conversion of one
carbohydrate into another can be effected. The aldehydic or
ketonic nature of these compounds was established by this
reaction, by the formation of addition-compounds with hydro-
cyanic acid,4 and by other means. To crown all, various
1 Cf. Tollens' Handbuch der Kohlerihydrate ("Text-Book of the Carbo-
hydrates," second edition).
2 Emil Fischer, born on the 9th of October,}! 852, at Enskirchen in Rhenish
Prussia, was a pupil of A. von Baeyer. He has done an immense amount of
brilliant work in organic chemistry, much of which will be referred to in
the special section. After filling successively the chairs of Chemistry at
Erlangen and (after 1885) at Wurzburg, he was called in 1892 to Berlin as
successor to the late A. W. von Hofmann. His Anleitung zur Darstellung
organischer Prdparate has established itself as a laboratory manual,
8 Victor Meyer and Jacobsen's Lehrbuch der organischen Chemie, p. 876
et seq. , contains a very clear account of the chemistry of the sugars, besides
giving the literature on the subject. E. Fischer's lecture on the Sugar
Group (Ber., vol. xxiii. p. 2114) and his rdsumd of sugar syntheses (Ber.y
vol. xxvii. p. 3189) should also be read. 4 Kiliani ; E. Fischer.
456 HISTORY OF ORGANIC CHEMISTRY CHAR
sugars (partly new ones, partly sugars occurring in nature)
have been built up artificially from such simple compounds as
formic and glyceric aldehydes ; in this way E. Fischer has
succeeded in synthetising fruit and grape sugars.
That the systematic arrangement of the carbohydrates
has become infinitely clearer from these researches requires
no demonstration. The mono-saccharides are now dis-
tinguished from the poly-saccharides (cane sugar, starch, cel-
lulose, etc.), the former including not only the (6 -carbon)
glucoses or hexoses, but also compounds of similar chemical
character containing no more than 3, 4 and 5 atoms of
carbon in the molecule.
A great deal of work has also been done upon starch,,
dextrine, etc., among others by Brown and Heron,1 Brown
and Morris,2 and O'Sullivan. But, notwithstanding this, our
knowledge of the poly-saccharides, which are regarded as
ethereal anhydrides of the glucoses, is very imperfect indeed
in comparison with that of the mono-saccharides.
The glucosides,3 which stand in the most intimate rela-
tion to the glucoses, and whose occurrence in the vegetable
and animal kingdoms awakened the interest of chemists of
the highest eminence at a very early date, have been the sub-
jects of important work ever since the memorable investiga-
tion of Liebig and Wohler on amygdalin, and that of Piria on
salicin. Among other researches we would refer here to
those of Will 4 on myronic acid, of Tiemann and Haarmaiirt
on coniferin, of Will on sesculin, and lastly of Tiemann and de
1 Journ. Chem. Soc., vol. xxxv. p. 596; or Ann. Chem., vol. cxcix.
2 Journ. Chem. Soc. vol. Iv. p. 473.
3 Cf. the article Glycoside, by 0. Jacobsen, in Ladenburg's Handwo'rter-
buck der Chemie.
4 Heinrich Will (1812 — 1890), after working for some time with a phar-
macist, studied chemistry under L. Gmelin. Coming subsequently into
contact with Liebig, he became Docent at Giessen, succeeding to Liebig's
chair there when the latter was called to Munich, and soon making hia
mark as a teacher. Besides producing a great quantity of admirable
experimental work, mostly in organic chemistry, but partly in analytical,
the results of which were published in the Anncden der Chemie, his literary
labours were of very high value, notably his collaboration in editing Liebig's-
Jahresbericht and the Anncden.
vi ORGANIC HALOGEN COMPOUNDS 457
Laire on iridin, the glucoside of the Florentine iris root — re-
searches which resulted in the elucidation of the decomposi-
tion-products of the glucosides named, and which laid the
foundation for a knowledge of the constitution of these and
other compounds of the same class, so widely distributed in
nature. The expectation that those natural products will
ultimately be obtained artificially has been brought within
measurable distance by E. Fischer's recent discovery of a
simple method for preparing the glucosides of the alcohols.1
Haloid Derivatives of the Hydrocarbons and other
Compounds.
As an appendix to the results of the investigations referred
to above, investigations which have largely increased our know-
ledge of the hydrocarbons, alcohols, carboxylic acids, aldehydes
and ketones, some others must be mentioned here which
bear upon the haloid and other similar derivatives of those
compounds.
Hand in hand with the examination of the hydrocarbons
went that of their haloid- and nitre-derivatives, for in some
cases these were easily obtained from the hydrocarbons, while
in others they often served for the preparation of the latter.
The formation of chlorine and bromine compounds from
hydrocarbons was the subject of highly important discussions,
arising from the experiments upon substitution-reactions-
made and suggested by Dumas and Laurent, and for the ex-
planation of which special theories were advanced; take, for
example, the first investigations made in this direction —
those upon the action of chlorine on naphthalene, ethylene
and ethylene chloride.
Other views began to prevail when, with the setting up
of a new theory of the aromatic compounds, the difference
between the hydrogen atoms of the benzene molecule and
those belonging to the substituting radicals which had entered
it came to be recognised. This difference was markedly ap-
1 Ber., vol. xxvi. p. 2400; vol. xxvii. p. 1145.
458 HISTORY OF ORGANIC CHEMISTRY CHAP.
parent in the case of the halogens, and was clearly demon-
strated by the work of Kekule, Fittig, Beilstein and others.1
Further, the study of the remarkable isomeric relations, pre-
dicted on theoretical grounds by Kekule* for the derivatives
of benzene, led to the thorough examination of the haloid
substitution-products of the aromatic hydrocarbons.
After substitution by chlorine has been more or less in-
vestigated, attention was directed to the action of bromine
.and iodine upon organic compounds. And here it was soon
recognised that the presence of certain reagents such as
phosphorus, iodic acid and mercuric oxide had a wonderful
effect in facilitating the replacement of hydrogen by these
elements.
Closely connected with this were the researches on
the so-called "halogen carriers," which include a large
number of the elements — those, namely, whose compounds
with the halogens are capable of partially yielding up the
latter again ; this explains their action as halogen conveyers.
The above action has been examined more especially in the
case of the aromatic hydrocarbons; without entering into
details, we would refer here to the investigations2 on the
.subject carried out at L. Meyer's suggestion by Aronheim,
Page, Scheufelen, Schwalb and others, and to those of Will-
gerodt.3 The earliest observations on this point were made
by H. Mtiller in 1862, when he noticed how chlorine was
conveyed by iodine in the action of the former upon
benzene and its homologues.
Two classes of peculiar iodine-oxygen compounds have
.lately been added to the aromatic group by Willgerodt 4 and
Victor Meyer5 respectively. Corresponding in composition
with the nitroso- and nitro-compounds, they have been
1 Cf. Ann. Chem., vol. cxxxvi. p. 301 ; vol. cxxxvii. p. 192 ; vol. cxxxix.
p. 331.
2 Cf. Ann. Chem., vol. ccxxxi. p. 152 (contains a historical review).
3 Journ. pr. Chem. (2), vol. xxxiv. p. 264 ; cf. also Neumann, Ann. Chem.,
vol. ccxli. p. 33 ("Sulphuric Acid as a Carrier of Iodine").
4 Eer., vol. xxv. p. 3494; vol. xxvi. pp. 357, 1307, 1532.
5 Ber., vol. xxv. p. 2632 ; vol. xxvi. p. 1354 ; vol. xxvii. pp. 1592, 2326 ;
-vol. xxviii. p. 83.
vi ORGANIC HALOGEN COMPOUNDS 459
named accordingly (e.g. iodoso-benzene, C6H5IO, and iodo-
benzene, C6H5I02). The interesting iodonium bases must
also be included here.
Attempts, which have been to some extent followed with
success, have also been made to determine the laws govern-
ing the substitution of definite hydrogen atoms by halogens ;
in connection with this the recent systematic experiments of
Victor Meyer and his pupils deserve mention.1 An infinity
of work has been done in this direction with aromatic com-
pounds, the object being to determine the order in which
the hydrogen atoms of benzene and its homologues and of
their derivatives are thus replaced.
The numerous researches on the combination of halogens
with unsaturated hydrocarbons were of very great moment,
the first example of such an addition being afforded by
ethylene. It would be out of place here even to mention
only the more important investigations bearing upon reactions
of this nature; but it may be stated generally that our
present views with respect to the constitution of unsaturated
compounds have resulted in great degree from the behaviour
of such hydrocarbons to the halogens and halogen hydrides.
These addition-reactions have, besides, proved of unexpected
value in the explanation of cases of stereo-isomerism (cf. p.
358).
The modes of formation of haloid derivatives of the
hydrocarbons are typical, i.e. are also applicable to other
classes of compounds, e.g. acids, ketones, etc. And the same
holds good for the chemical behaviour of such compounds,
this having been in most cases first established for the haloid
derivatives. To mention only one or two of the researches
which have advanced our knowledge of the subject — take
the discovery and investigation of trichloracetic acid by
Dumas,2 that of chloral by Liebig and Dumas,3 and that of
monochlor-acetic and monochloro-propionic acids, from whose
chemical behaviour the constitution of the corresponding oxy-
1 Cf. V. Meyer and Fr. Miiller, Journ. pr. Chem. (2), vol. xlvi. p. 161.
2 Ann. Chem., vol. xxxii. p. 101.
3 Ibid., vol. i. p. 189; Ann. Chim. Phys.,vol. Ivi. p. 123.
460 HISTORY OF ORGANIC CHEMISTRY CHAP,
and amido-acids was established by Kolbe. It is impossible
to record here even the most important work of recent years
in this direction, but a passing reference must be made to
the production in theoretical quantity of aromatic halogen
derivatives from the corresponding diazo- or amido-com-
pounds.1
Mention must lastly be made of the important part
which the halogen compounds have played in organic
syntheses; take, for example, their interactions with sodio-
aceto-acetic ether, sodio-malonic ether, and the zinc alkyls,,
besides many other synthetic reactions.
Organic compounds of fluorine have repeatedly been the
object of research, notwithstanding which our knowledge of
them is still limited. Although six decades have passed
since methyl fluoride was described by Dumas and Peligot,,
it is only within the last few years that the systematic study
of these fluorine compounds has been taken in hand by
Moissan, Meslans and others.
Nitro- and Nitroso-compounds.
Mitscherlich's discovery and investigation of nitro-
benzene2 paved the way for a knowledge of the nitro-
compounds; the formation of this substance from benzene
and its relation to the latter were, however, only clearly
understood after the adoption of Dumas and Gerhardt's view
that nitro-benzene was a substitution-product of benzene.
Since then the group nitroxyl (NO2) has been ranked as a
substituent alongside of the halogens. There is scarcely any
reaction which has been more frequently applied among the
aromatic compounds than the action of nitric acid upon
them ; take, for instance, the discovery of mtro-naphthalene,
of di- and tri-nitrobenzenes, and of the nitro-derivatives
of benzoic acid, benzoic aldehyde, phenol, etc. Picric acid,
which was so much earlier known than nitro-benzene, was
first characterised as trinitro-phenol by Gerhardt. It may be
1 P. Griess and also 0. Sandmeyer, Ber.t vol. xvii. pp. 1633, 2651 ; vol.
xxiii. p. 1880. - Ann. Chem., vol. xii. p. 305.
vi NITRO- AND NITROSO-COMPOUNDS 461
taken for granted that nitro-derivatives of every aromatic
compound are known, or at any rate can be prepared.
Attention will be called later on to the history of some of the
classes of compounds proceeding from these nitro-derivatives,
e.g. the amines and azo-compounds, which have been destined
to play such a prominent part in industrial chemistry.
The first nitro-derivatives of saturated compounds date
from the year 1872, when Kolbe discovered nitro-methane l
and Victor Meyer nitro-ethane.2 The modes of formation of
these substances were particularly calculated to arouse the
reflection of chemists, since it was to have been expected
here that compounds of quite other constitution — ethers of
nitrous acid — would have been obtained instead. The
thorough investigation and explanation of the chemical
nature of nitro-ethane is due to V. Meyer. Those splendid
researches3 of his resulted further in the discovery (by
himself) of other remarkable compounds, which include the
nitrolic acids and nitrols. It must however be mentioned
that the constitution of the nitro-paraffins hitherto assumed,
viz. R(NO2), has of late been called in question more than
once, on the ground of the chemical behaviour of these
compounds.4
The nitrolic acids and nitrols have been proved to be
representatives of the two classes of isonitroso- and nitroso-
<jompounds, which have repeatedly, and more especially of
late years, awakened the interest of chemists. It was those
investigations of Victor Meyer and his pupils which estab-
lished the constitution of the isonitroso-compounds, and
showed how they were formed by the action of hydroxyl-
amine upon substances containing the radical carbonyl.
Thanks to this perfect reaction, so universally applicable,
many substances which were formerly numbered among the
nitroso-compounds have since been recognised as really
belonging to the class of their isomers. On the other hand,
1 Journ. pr. Chem. (2), vol. v. p. 427.
2 Ber., vol. v. pp. 399, 514.
3 Ann. Chem., vol. clxxi. p. 1 ; vol. clxxv. p. 88; vol. clxxx. p. 111.
4 Nef, Ann. Chem., vol. cclxxx. p. 263.
462 HISTORY OF ORGANIC CHEMISTRY CHAP,
the above reaction has proved itself a convenient means of
testing whether or not compounds contain the radical
carbonyl.1 From those simple researches there have thus
been drawn valuable conclusions with respect to the consti-
tution of whole classes of compounds, e.g. of the quinones.2
The compounds obtained by the action of hydroxylamine
on the aldehydes and ketones — the aldoximes and Jcetoximes
— have for a number of years back been much studied by
the late Victor Meyer, Beckmann, Behrend, Hantzsch, Auwers
and others, on account of the remarkable cases of isomerism
that they show. In fact, the investigation of isomeric
oximes and the peculiar chemical behaviour of these sub-
stances, form the basis of the stereo-chemistry of nitrogen
(cf. p. 359). Only a few chemists (Glaus, Minunni and Nef)
have brought forward arguments against this view, seeking
to explain these isomers on structural grounds.
Organic compounds containing the group phosphyl (POg)
were also prepared a few years ago;3 the constitution of
these is analogous to that of the nitro- and of the iodo-
compounds (p. 459 — 460).
Development of the Knowledge of Sulphur Compounds.
The examination of organic sulphur compounds has
proved of great value for the development of our views
upon the constitution of organic compounds generally, and
more especially upon the saturation-capacity of the sulphur
group of elements. Their investigation has led to the
abandonment of the one-sided opinion that sulphur, selenium
and tellurium can only act as divalent elements, by furnishing
proofs that they may also be tetra- or hexa-valent.
The earliest known of those compounds, which contain
sulphur combined in the same manner as the alcohols, carb-
1 In phenyl-hydrazine E. Fischer discovered an analogous and equally
serviceable reagent for carbonyl compounds, which has proved of the utmost
value in establishing the constitution of a very large number of substances
— the sugars, for instance (cf. p. 455). 2 Cf. p. 452.
3 Michaelis and Rothe, Ber., vol. xxv. p. 1747.
vi SULPHONIC ACIDS AND SULPHONES 46$
oxylic acids, ethers, etc., contain oxygen, was mercaptan, dis-
covered by Zeise ; its true constitution, as a hydrosulphide
corresponding to alcohol, was recognised by Liebig.1 To this-
there were soon added ethyl sulphide and its polysulphides,
whose analogy to the sulphides of the metals was obvious.
The similarly constituted selenium and tellurium compounds
were to a great extent worked out by Lowig 2 and Wohler.3
Of organic acids which contain sulphur in place of
oxygen, thiacetic acid,4 discovered by Kekule', was the first
known, although benzoyl sulphide had previous to this been
regarded as the " thio-anhydride " of such an acid. Since
then the number of these acids and their corresponding
aldehydes has been greatly extended (cf. p. 450). Thio-
glycollic acid (analogous to glycollic) and its analogues have
been investigated mainly by Klason.5
By the action of powerful reagents on many of the
compounds containing divalent sulphur, which have just
been spoken of, it has been found possible to prepare others
in which the sulphur present possesses a higher valency —
compounds which are comparable with sulphurous and
sulphuric acids, and which can be derived and in part
prepared from the latter. The earliest known of these
were the sulphonic acids and sulphones, whose first repre^
sentatives — phenyl-sulphonic acid and diphenyl-sulphone
(Sulphobenzid) — were obtained by Mitscherlich,6 by acting
upon benzene with sulphuric acid. These compounds, how-
ever, only came to be fully understood after Kolbe had
shown them to be derivatives of sulphuric acid and its
anhydride. Previous to this (in 1844) he had enlarged
the then existing knowledge of the sulphonic acids by hi&
work upon methyl-sulphonic acid and its chlorine derivatives.
The important discovery 7 of the transformation of hydrosul-
1 Ann. Chem., vol. xi. pp. 2, 11. 2 Pogg. Ann. vol. xxxvii. p. 552.,
3 -47171. Chem., vol. xxxv. p. Ill ; vol. Ixxxiv. p. 69.
4 Ibid., vol. xc. p. 311.
5 Cf. Ibid., vol. clxxxvii. p. 113.
6 Pogg. Ann., vol. xxix. p. 231 ; vol. xxxi. p. 628.
7 Lowig, Pogg. Ann., vol. xlvii. p. 153; Muspratt, Ann. Chem., vol,
Ixv. p. 251.
464 HISTORY OF ORGANIC CHEMISTRY CHAP.
phides, disulphides and sulphocyanides into sulphonic acids
furnished a general method for the preparation of the latter.
In a similar manner the conversion of the alkyl sulphides
into sulphones, which contain two atoms of oxygen more in
the molecule, was effected.1 Kolbe was again the first here
to point out definitely the analogy between sulphones and
ketones, and sulphonic and carboxylic acids. There have
been added lately to the di-ketones the di-sulphones and the
.sulphone-ketones (products intermediate between the two),
in whose investigation R. Otto 2 has done more than any
one else. The di- and tri-sulphonic acids, which correspond
to the poly-carboxylic, have been known for a long time,
Hofmann and Buckton 3 having been the first to investigate
them.
The mercaptals, sulphur analogues of the acetals, were
prepared by Baumann4 by the action of aldehydes upon
mercaptans ; and the mercaptols were got in the same way,
ketones being substituted for aldehydes. Among the di-
sulphones produced by the oxidation of the mercaptols is
the well-known soporific sulphonal.
Von Oefele's discovery of the sulphines 5 was particularly
pregnant in its results, because the existence of these com-
pounds stood in contradiction to the assumption that the
sulphur atom was invariably divalent. And the same
applies to the investigation of the sulph-oxides by Saytzeff,6
and to that of the sulphinic acids, whose formation and
chemical behaviour was cleared up by the work of Kalle,
Otto, Klason and others. Mention must also be made here
of the remarkable conversion of sulphinates into sulphones,7
and of sulphites into sulphonic acids 8 by means of alkyl
iodides, those reactions having led to conclusions respecting
1 Von Oefele, Ann. Chem., vol. cxxxii. p. 80.
2 Journ. pr. Chem. (2), vol. xxx. pp. 171, 321 ; vol. xxxvi. p. 401.
3 Ann. Chem., vol. c, p. 133.
4 Ann. Chem., vol. cclxxiv. p. 173; Ber., vol. xxvi. p. 2155.
5 Ann. Chem., vol. cxxvii. p. 370; vol. cxxxii. p. 82.
6 Ibid., vol. cxliv. p. 148.
7 Otto, Ber., vol. xiii. p. 1274.
8 Strecker, Ann. Chem., vol. cxlviii. p. 90.
vi ORGANIC AMMONIAS, ETC. 465
the constitution both of the sulphinic acids and the sulphites.
By the discovery and careful investigation of the thionyl-
amines, Michaelis has added another class to the list of
sulphur compounds. — Organic compounds of selenium and
tellurium corresponding to the above-mentioned sulphur
ones are as yet but sparingly known.
Organic Nitrogen Compounds,
An exceptionally wide field in organic chemistry was
opened up by the discovery of the nitrogenous bases corre-
sponding to ammonia. When their connection with the
latter was found out, the question of their chemical con-
stitution in general was solved, A. W. Hofmann's classical
researches1 on the substituted ammonias and ammonium
bases, whose salts result from the action of alkyl iodides upon
ammonia, deserve the first mention here, since they led to
the true perception of the constitution of these bodies, and
established a basis upon which they might be system atised.
His splendid work upon aniline and its numerous substitu-
tion-derivatives (e.g. cyan-aniline), begun in 1 843,2 and on the
addition products of this base, immensely enriched organic
chemistry. These investigations resulted in the discovery of
a wealth of new and striking facts, e.g. the observation of the
influence exerted by halogens entering the aniline molecule
upon the chemical character of the resulting compounds.3
Upon the basis of those labours, which prepared the way for
a knowledge of the aromatic bases, the aniline colour industry
has since developed itself in the most brilliant manner.
From a theoretical point of view, also, these researches on the
di- and tri-amines and on the corresponding ammonium bases
(obtained from ethylene bromide and ammonia) were of
special importance ; Hofmann, in fact, worked out and ex-
plained organic nitrogen compounds generally as no other
1 Ann. Chem., vol. Ixxiv. p. 117; vol. Ixxv. p. 356; cf . also p. 296 of
this book.
2 Ibid., vol. xlvii. p. 37, and numerous later papers.
3 Ibid., vol. liii. p. 1 ; cf. also p. 284 of this book.
H H
466 HISTORY OF ORGANIC CHEMISTRY CHAP,
man has done. His investigations on the formation of
substitution-products of ammonia contributed more than
anything else to the establishment of the " typical " theory
towards the end of the forties (cf. p. 295 et seq.).
The observation that the organic ammonias result from
the nitro-compounds by reduction1 was a point of special
significance in their history, this step having been first
effected by Zinin 2 in the conversion of nitro- into amido-
benzene. The above reaction has proved itself of the greatest
use as a general method, has served for the preparation of
di- and tri-amines, and has since been applied with success in
innumerable instances, besides having been extended to the
later discovered nitro-compounds of the fatty series. The
mode of formation of the primary amines from the cyanic
•ethers, discovered by Wurtz,3 must also be referred to here
as of historical importance, since the simplest organic
.ammonia, methylamine, was first prepared in this way.
From the vast number of observations on the chemical
behaviour of the classes of compounds in question, we can but
pick out a very few, such, namely, as have led to the elucida-
tion of their constitution and to the discovery of new and
important groups. To what an unlooked-for significance
the action of nitrous acid upon amines and similar bodies
(a reaction which had already been studied by Hofmann
.and others) attained in the hands of P. Griess, who demon-
strated the conditions under which diazo-compounds were
formed, and examined these with the utmost success ! To
the latter there were afterwards added the azo-compounds
.and hydrazines, classes which are of such importance as also
to merit a detailed description (see below). The transforma-
tion of aromatic amines into valuable dyes by oxidation,
observed by W. H. Perkin, sen., A. W. Hofmann, and others,
marked the commencement of a new era in chemical industry.
1 Bamberger and Wohl have found that the first product of a moderated
reduction (in neutral solution with zinc dust) is phenyl-hydroxylamine — a
compound of great reactive power (Ber. , vol. xxvii. pp. 1348, 1432).
2 Journ. pr. Chem., vol. xxvii. p. 149.
3 Ann. Chim. Phys. (3), vol. xxx. p. 443.
vi ORGANIC AMMONIAS, ETC. 467
Only a passing reference need be made here to the
-conversion of the organic ammonias into quinoline, acridine,
-quinoxaline and other basic substances by similar processes
of condensation, since these reactions will be considered
further on, especially in their connection with the pyridine
and quinoline bases, and the relations of the latter to the
.alkaloids.
Great advances have been made in the artificial produc-
tion of naturally-occurring nitrogenous substances, by suit-
able transformations of ammonia or amines. The important
work effected by Hofmann on the mustard oils brought out
clearly the relation existing between this class of compounds
and the amines, and furnished a firm basis for arriving at
their constitution.
Oil of mustard itself (allyl iso-thiocyanate), which is
obtained from the seeds of the black mustard, was prepared
from allylamine, and also by converting allyl iodide into the
thiocyanate, which changes on heating into the isomeric iso-
compound. Hofmann's investigation1 of the chemical be-
haviour of the mustard oils and their isomers the thiocyanates
left no doubt as to the constitution of these two classes.
After the base which was isolated from herring brine
had been recognised as identical with the artificially pre-
pared trimethylamine, further researches led to the synthesis
of the physiologically important compounds choline and
neurine from trimethylamine and ethylene-chlorhydrin,2 and
also to that of betaine, a substance found in the juice of
beet. And just as trimethylamine served for the formation
of the latter, so from methylamine and monochloro-acetic
acid sarcosine (found naturally in the juice of flesh) was
obtained ; further, by assimilating the elements of cyanamide,
sarcosine was converted into creatine. These reactions left
the constitution of the compounds perfectly plain.3 Refer-
ence must also be made here to the synthesis of many com-
1 Ber., vol. i. p. 176.
2 Wurtz, Ann. Chem., Suppl., vol. vi. pp. 116 and 197.
3 Volhard, Ann. Chem., voL cxxiii. p. 261 ; Jahresber. d. Chemie for
1868, p. 685.
H H 2
468 HISTORY OF ORGANIC CHEMISTRY CHAP,
pounds nearly related to urea, e.g. guanidine,1 and parabanic,
oxaluric and barbituric acids,2 which were known as deriva-
tives of uric acid long before they were prepared of set pur-
pose from urea. Uric acid itself was synthetised a few years
ago,3 after many unsuccessful attempts. Indeed urea and
guanidine — compounds of such great physiological impor-
tance— have proved themselves singularly suited for building
up complex " condensed " compounds, for instance, with the
ketonic esters and di-ketones. The constitution of the guana-
mines, substances obtained by the action of organic acids upon
guanidine, has lately been worked out by Bamberger,4 The
remarkable and highly nitrogenous compounds prepared from
amido-guanidine 5 must also be mentioned.
The study of the amides, which include urea and several
others of the compounds just mentioned, has gone on simul-
taneously with that of the amines. Here we can only refer
to the important conversion of these substances into cyanides
(by means of phosphorus pentoxide), and their re-formation
from the latter; and to the interesting behaviour of the
substituted amides with phosphorus pentachloride, a reaction
which has been studied more especially by Wallach,6 and
which has led to a knowledge of certain peculiar bases, the
oxalines. Hofmann 7 worked out the curious transformation
of amides into amines containing an atom of carbon less in
the molecule by subjecting them to the action of bromine in
alkaline solution. The corresponding thiamides, investigated
by Cahours, Hofmann, and many others, have on their part
been converted into other nitrogenous compounds, e.g. the
amidines,8 the study of which has likewise yielded many
1 Ann. Chem., vol. cxlvi. p. 259.
2 Ponomareff, Bull. Soc. Chim. , vol. xviii. p. 97 ; Grimaux, ibid., vol.
xxxi. p. 146.
3 Behrend and Roosen, Ann. Chem., vol. ccli. p. 235.
4 Nencki, Ber., vol. vii. p. 776 and 1584; Bamberger, Ber., vol. xxv.
p. 534.
6 Thiele, Ann. Chem., vol. cclxxiii. p. 133.
6 Ann. Chem., vol. clxxxiv. p. 1 ; vol. ccxiv. p. 193.
7 Ber., vol. xv. p. 765.
8 Wallach, Ann. Chem., vol. clxxxiv. pp. 5 and 91 ; Bernthsen, ibid.,
vol. clxxxiv. p. 321 ; vol. cxcii. p. 1.
vi PHOSPHINES AND PHOSPHONIUM BASES 469
useful results. The exhaustive researches by Pinner1 are
worthy of special notice here ; he has prepared the amidines
from the highly reactive imido-ethers, and has thoroughly
studied their chemical behaviour.
Through the discovery and investigation of the organic
compounds of phosphorus, antimony and arsenic, the con-
nection existing between those three elements themselves
and also their relation to nitrogen were proved in the clearest
manner, so that here, as well as in other cases, the study
of organic compounds has thrown a brilliant light upon
particular branches of inorganic chemistry. The phosphines
and phosphonium bases first became known through the
classical and comprehensive researches of A. W. Hofmann,2
and the corresponding compounds of the aromatic series
through those of Michaelis.3 The organic compounds of
phosphorus were thenceforth recognised as derivatives of the
well-known inorganic ones, — phosphuretted hydrogen (PH3)
and phosphonium iodide, and phosphorus tri- and penta-
chlorides. The study of the organic compounds of arsenic
and antimony, the former of which were admirably investi-
gated by Bunsen, and at a later date by Cahours, Baeyer and
Michaelis,4 and the latter by Lowig, Landolt, Michaelis5
and others, likewise led to the conclusion that those sub-
.stances were derivable from the inorganic compounds of
the elements. The influence exercised by some of these
researches upon the development of the doctrine of valency
has been already sufficiently referred to in the general
.section.
The field comprising the organic compounds of nitrogen
is by no means exhausted with the description of the classes
which have been shortly^ alluded to above. A number of
1 Compare his monograph, Die Imidodther und ihre Derivate ; or,
failing that, Ber., vol. xvi. p. 1654; vol. xvii. p. 2520 ; vol. xviii. p. 759.
2 Ber., vol. iv. p. 605 ; vol. v. p. 104 ; vol. vi. p. 306.
3 Cf. Ann. Chem., vol. clxxxviii. p. 275.
4 For the literature on the subject, cf. Ann. Chem., vol. cci. p. 184,
5 Cf. ibid., vol. ccxxxiii. p. 39 ; Ber., vol. xxvii. p. 244.
470 HISTORY OF ORGANIC CHEMISTRY CHAP.
others must be referred to here, with regard to the chemical
constitution of which much has also been accomplished;
many of these are now of great technical importance.
Of the azo-compounds, azo-benzene was the first to be
discovered (by Mitscherlich),1 while much later there came
azoxy-benzene by Zinin 2 and hydrazo-benzene by A. W.
Hofmann.3 The now universally accepted views held with
regard to these three kinds of azo-compounds are due to-
Erlenmeyer,4 and still more to Kekule,5 who assumed in azo-
benzene two doubly-linked nitrogen atoms, and in oxyazo- and
hydrazo-benzene two singly-linked ones. The ready produc-
tion of these and similar substances from diazo-compounds
has greatly tended to advance our knowledge of them. The
investigations of Griess, Kekule, Victor Meyer, H. Caro, Witt
and others, which showed how diazo- could be converted
into azo-compounds, have led to the establishment of a
flourishing industry — the manufacture of azo-dyes. The
doctrine of isomerism has also been enriched by a wealth of
observations arising out of these labours. The remarkable
molecular transformations of hydrazo-compounds into the
isomeric diamido-derivatives of diphenyl and its homologues,.
and of diazo-amido- into amido-azo-compounds, also fall to
be mentioned here. In this class it was the amido- and oxy-
derivatives of azo-benzene and its homologues which first
found employment as dyes. The view held by many, — that
the above substances are to be looked upon as derivatives of
quinone or quinone-imide respectively,6 is of importance for
understanding the connection between chemical constitution
and dye-character.
The diazo-compounds, so remarkable for their reaction-
capacity, were discovered by Griess 7 and investigated by him
1 Pogg. Ann., vol. xxxii. p. 324. 2 Ann. Chem., vol. Ixxxv. p. 328.
3 Jahresber. d. Ghemie for 1863, p. 424.
4 Ztschr. Chem. for 1863, p. 678.
5 Lehrb. d. Chem., vol. ii. p. 703.
6 Cf. Goldschmidt, Ber., vol. xxv. p. 1324.
7 Peter Griess (1829—1888), a pupil of Kolbe's, became assistant to A.
W. Hofmann in London, but relinquished that post after a short time, on
receiving in 1862 the appointment of chemist to Messrs. Allsopp and Sons>
vi DIAZO-COMPOUNDS ; GRIESS 471
in a long series of admirable researches, which disclosed
their most important characteristics. Griess showed how
they were formed by the action of nitrous acid on aromatic
amido-compounds, — a reaction which had previously been
studied under other conditions, and had not led then to the
discovery of those bodies. In a number of papers 1 dating
from the year 1859, which followed one another with great
rapidity, the above-named investigator made the chemical
world acquainted with the diazo-derivatives of phenol,
aniline and benzoic acid, and with their remarkable pro-
perties. The view accepted by most chemists with respect
to the constitution of these bodies, according to which two
atoms of nitrogen are linked together as in the azo-com-
pounds, originated with Kekule.2 Another view, in which
one of the nitrogen atoms is assumed to be pentavalent and
the other trivalent, was expressed by Blomstrand,3 who
brought forward arguments in its favour.
The existence of diazo-compounds in the fatty series has
only been proved comparatively recently by the exhaustive
researches of Curtius4 on diazo-acetic and diazo-succinic
ethers. The first of these, obtained by the action of nitrous
acid on amido-acetic ether, shows certain points of resem-
blance to the aromatic diazo-compounds, but also many differ-
ences ; its power of combining with other substances, nitrogen
being eliminated, is more strongly marked than in its aromatic
at their well-known brewery at Burton-on-Trent. Although continuing
there engaged in this branch of technical chemistry until his death, he at
the same time carried out a number of most valuable scientific researches.
His brilliant discovery and investigation of the diazo-compounds led him
on to the azo-dyes ; he was thus the father of this now enormous industry.
Griess's work generally was marked by great refinement of execution, as
well as great power of observation. A. W. von Hofmann has left us a full and
sympathetic account of his life, while E. Fischer and H. Caro have told of
his services to science (Ber., vol. xxiv. Ref. pp. 1007, 1058).
1 Ann. Chem. y vol. cxiii. p. 201 ; vol. cxvii. p. 1 ; vol. cxxi. p. 257 ; voL
cxxxvii. p. 39.
2 Ztschr. Chem. for 1866, p. 689.
3 In his Ohemie der Jetztzeit, p. 272; cf. also Ber., vol. viii. p. 51 ; and
Strecker, ibid., vol. v. p. 786.
4 Journ. pr. Chem. (2), vol. xxxviii. p. 401.
472 HISTORY OF ORGANIC CHEMISTRY CHAP.
congeners. Diazo-acetic ether is therefore of very great
value for the synthesis of other compounds. Diazo-methane
(the simplest of the diazo-compounds), discovered by v.
Pechmann,1 is also of the greatest interest,
Another class of bodies, the hydrazines, which stand in a
near relation to the diazo-compounds, was discovered in
1875 by E. Fischer2 and carefully investigated by him.3
Phenyl-hydrazine— the first of the series to be discovered —
has proved of the greatest value both as a specific reagent
and as an aid in the synthesis of complex compounds. Its
relation to diazo-compounds was definitely proved by Fischer,
through its formation from diazo-amido-benzene or diazo-
benzene chloride and its conversion into diazo-benzene imide.
The importance of phenyl-hydrazine and similar bases for
the preparation of hydrazones and osazones has already been
referred to ; they have also been of material aid to the theory
of stereo-isomerism.
The production of derivatives of pyrazolone and indole
(besides other condensed compounds) by the aid of phenyl-
hydrazine must be mentioned here. The latter substance is
also now used in large quantity for the manufacture of the
well-known febrifuge antipyrine. The simplest member of
this series— hydrazine itself — whose discovery is noticed in
the history of inorganic chemistry, likewise reacts with
the greatest readiness with aldehydes, ketones, and similar
substances, and hence has also proved of signal service in
extending the domain of nitrogen compounds (cf. the
papers by Curtius and his pupils on hydrazides and azides
of organic acids, Journ, pr. Chem. (2) vol. 1. and succeeding
volumes).
Within the last few years some remarkable reactions have
been carried out with diazo-compounds, which have led
either to hydrazones or to so-called formazyl derivatives ; the
reader is referred to the latest papers on the subject, which
1 Ber.t vol. xxviii. pp. 855 and 1624; cf. also Bamberger, ibid. p.
1682.
2 Ber., vol. viii. p. 589.
3 Ann. Chem., vol. cxc. p. 67 j vol. cxcix. p. 281 ; vol. ccxii. p. 316.
^i CYANOGEN AND HYDROCYANIC ACID 473
•explain these reactions.1 Von Pechmann's researches on the
oxidation of diazo-compounds and on their constitution are
also worthy of note.
After the discovery of the iso-diazo-compounds by Schraube
.and Bamberger, the constitution of the diazo-compounds
became a burning question. The addition of new facts has
greatly enlarged the chemistry of the subject. Blomstrand's
view (p. 471) has again come into favour; Hantzsch, on the
other hand, adheres strongly to the opinion that certain series
of isomeric diazo-compounds are stereo-isomeric ; while
Bamberger can find in the experimental results no proof for
Hantzsch's idea, but contends that a structural isomerism is
probable. This controversy has now gone on for some years
without any definite result being arrived at, although
Blomstrand, not long before his death, expressed himself in
favour of Bamberger's theory.2
Since Scheele's discovery of hydrocyanic acid, the
cyanogen compounds have been the subject of frequent
investigation by the most able chemists, so that the know-
ledge of them has been immensely increased. The develop-
ment of this branch of organic chemistry is in a great
degree due to the marked property possessed by most of
these compounds of changing into isomers, and also of com-
bining with other substances to yield new compounds.
The composition of prussic acid and of many of the
cyanides was worked out by Berthollet and Ittner, and
especially by Gay-Lussac in his classical researches, in
which he discovered cyanogen and recognised its analogy
to the halogens. He it was, too, who assumed in yellow
prussiate of potash (a substance already known for a long
time) the presence of the radical ferrocyanogen, while
Berzelius, adhering strictly to the dualistic theory, explained
it as being a double salt of iron protocyanide and cyanide of
1 V. Pechmann, Her., vol. xxv. p. 3175 ; Vol. xxvii. p. 219. Bamberger,
Ber.t vol. xxv. pp. 3201, 3539 ; vol. xxvi. p. 2978. W. Wislicenus, Ber.,
vol. xxv. p. 3459.
2 Cf. Ber., for the years 1894 — 1897 ; also Blomstrand, Journ. pr. Ghent.
2), vol. liii. p. 169 ; vol. liv. p. 305 ; vol. Iv. p. 481.
474 HISTORY OF ORGANIC CHEMISTRY CHAP,
potash. The discovery of potassium ferricyanide by L.
Gmelin in 1822, and that of the so-called nitro-prussides by
Playfair 1 extended the knowledge of cyanogen compounds of
complex composition, in which, at Graham's suggestion, the
radical tri-cyanogen was assumed.
Sulphocyanic acid, together with its salts, was discovered
by Porret, and subsequently investigated by Berzelius, who
established its composition; Liebig succeeded in isolating
cyanogen sulphide in 1829, and he also showed what
remarkable products were obtained from the decomposition of
ammonium sulphocyanide, viz. mellone, melame, melamine,
etc.2 Of recent years Reynolds, Volhard, Delitzsch and more
especially Klason,3 among others, have advanced our know-
ledge of this class of compounds.
Cyanic acid, whose chemical behaviour and relation to its-
own isomers gave rise to important discussions respecting the
constitution of all of them, was first isolated by Wohler,4
who was led during the investigation of its salts to his
memorable discovery of the artificial formation of urea.5
Cyanuric acid, obtained by Serullas from the solid cyanogen
chloride which he discovered, was recognised by Liebig and
Wohler as being of the same percentage composition as-
cyanic acid. The influence which this observation, taken in
conjunction with that of the isomerism of both of these
compounds with fulminic acid, had upon the doctrine of
isomeric substances, has already been discussed in the
general section of this book. The haloid compounds of
cyanogen have been known for a long time, cyanogen
chloride having been obtained by Berthollet, and the iodide
by Davy ; but cyanamide, which was destined to become of
so much importance for the synthesis of organic compounds,6
was first prepared in 1851 by Cloez and Cannizzaro.7
1 Phil. Trans, for 1849, vol. ii. p. 477. 2 Ann. Chem., vol. x. p. 11.
3 Cf. more particularly Journ. pr. Chem. (2), vol. xxxvi. p. 57 ; vol.
xxviii. p. 366. 4 Pogg. Ann., vol. xv. p. 619; vol. xx. p. 369.
5 Cf. p. 252.
6 Cf. Volhard's, Strecker's, and Drechsel's researches, more especially
Journ. pr. Chem. (2), vol. xi. p. 284.
7 Comptes Rendus, vol. xxxi. p. 62.
vi NITRILES AND CARBAMINES 475
Owing to the readiness with which they unite with other
substances, the cyanogen compounds as a whole have been
of great service for opening up new branches of the sciencer
and for advancing our knowledge of these ; take, for exampler
the formation of guanidine and its derivatives from cyana-
mide or cyanogen chloride and ammonia, and also the
formation of derivatives of the last-named compound.1 The
tendency shown by hydrocyanic acid to combine with alde-
hydes and ketones has already been mentioned ; this property
has rendered it possible to synthetise a large number of oxy-
carboxylic acids.
The compounds of cyanogen as well as of thiocyanogen
with organic radicals have, thanks to their diversity and
capacity for transformation, yielded an almost inexhaustible
material for investigation. The alkyl cyanides or nitriles,
with methyl cyanide at their head, were first prepared by
Dumas2 from the ammonium salts of the fatty acids, by
acting upon these with phosphoric anhydride; the amides
afterwards replaced the ammonium salts of the acids for this
purpose. The exceptionally important connection which
exists between the nitriles and the fatty acids was demon-
strated by Frankland and Kolbe 3 when they converted the
former into the latter by treatment with caustic potash.
Another passing reference may be made here to the general-
isation of this reaction, and the consequent production of an
immense number of carboxylic acids and their derivatives
from simpler compounds, even although it was spoken of
when those compounds themselves were being described.
The investigation of mandelic acid,4 resulting from oil of
bitter almonds and hydrocyanic acid in presence of hydro-
chloric, gave the first impetus to the study of the compounds
obtained under similar conditions from other aldehydes and
ketones. The simplest nitrile of the aromatic series, phenyl
1 Cf. Erlenmeyer, Ann. Chem., voL cxlvi. p. 253 ; A. W. Hofmann, ibid.r
vol. cxxxix. p. Ill ; Ber., vol. i. p. 145, etc.
2 Comptes Rendus, vol. xxv. pp. 383 and 442.
3 Ann. Chem., vol. Ixv. p. 269.
4 Liebig, Ann. Chem., vol. xviii. p. 319.
476 HISTORY OF ORGANIC CHEMISTRY CHAP.
cyanide or benzo-nitrile, was first observed by Fehling.1
Since then the number of these nitriles has been enormously
extended, all- those which correspond to the important
carboxylic acids being known. The amidoximes — derivatives
of the nitriles — which were discovered by Tiemann,2 are of
particular interest. The imido-ethers, which result from the
nitriles by the addition of one molecule of an alcohol, are
also worthy of note, because of the ease with which they
yield the amidines,3 compounds of great reactive power*
The cyanogen compounds corresponding to the halogen fatty
acids are also nearly related to the nitriles; the simplest
members of this series, viz., cyano-carbonic and cyan-acetic
acids, have led on to important transformation-products,
thanks to the ease with which they enter into reaction.
The isocyanides, isonitriles, or carbamines, which are
isomeric with the nitriles, were discovered simultaneously
by A. W. Hofmann 4 and Gautier,5 by different procedures,
their existence having previously been foreseen by Kolbe.
The perception of the cause of the isomerism existing between
these two classes of compounds marked an important
advance in theoretical chemistry. The conclusive explana-
tion of the similar isomerism between the alkyl thiocyanates
and the mustard oils, of which mustard oil proper (allyl
iso-thiocyanate) was the earliest known, is due to Hofmann ;
the latter succeeded both in preparing the iso-thiocyanates
.artificially, and in proving at the same time their chemical
constitution from their various decompositions.6 The dif-
ference in constitution between the thiocyanates arid the
mustard oils was especially seen in their transformations.
Hand in hand with the acquirement of the above knowledge
went the gradual establishment of the views upon the
-analogously constituted cyanic and isocyanic ethers; and
1 Ann. Chem., vol. xlix. p. 91.
2 Ber., vol. xvii. pp. 126, 1685, etc.
3 Cf. Pinner, JBer., vols. xvi. and xvii., and especially his monograph : —
J)ie Imidodther und ihre Derivate (Berlin, 1892).
4 Ann. Chem., vol. cxliv. p. 144 ; vol. cxlvi. p. 107.
5 Comptes Rendus, vol. Ixv. pp. 468 and 862.
6 Ber. , vol. i. pp. 26 and 169 ; vol. ii. pp. 116 and 452.
VI POLYMERIC CYANOGEN COMPOUNDS 477
here again Hofmann acted as the pioneer with his researches,
after the simplest compounds of this nature had been ob-
tained by Wurtz and Cloez. The ease with which the isocyanic
ethers and the corresponding mustard oils assimilate the
elements of ammonia and the amines led to the discovery of
the extensive class of the substituted ureas j1 the simplicity
of the reaction, upon which the formation of these substances
was based, allowed of the explanation of the numerous cases
of isomerism which occur here.
The question of the chemical constitution of the polymeric
cyanogen compounds presented far greater difficulties, the
number of these having increased to an extraordinary extent
after it was proved that cyanuric, fulminic and cyanic acids
had all the same percentage composition. It is only com-
paratively recently (i.e., since 1884) that a certain degree
of clearness has been arrived at with regard to the constitu-
tion of the cyanuric and isocyanuric compounds, and this has
been due more particularly to the admirable investigations
of A. W. Hofmann and of Klason, and also to those of Rathke,
Weddige, Bamberger and others, These researches have
proved that isocyanuric acid and isomelamine are not in
themselves capable of existence, although derivatives of both
are, The doctrine of stable and unstable modifications,
already referred to,2 was developed and strengthened mainly
from observations made upon these polymeric compounds.
The obscurity surrounding the compounds of this nature, as
well as those decomposition-products of ammonium sulpho-
cyanide known under the names of mellone, melame and
meleme, and the bases resulting from the nitriles by poly-
merisation (cyan-ethine, etc.), is now beginning to vanish,
and a knowledge of their constitution is being gradually
acquired. The recent work of Otto and Voigt, Weddige and
Krafft has introduced us to the true alkyl cyanurates, the
isomeric cyan-alkines (which are obtained directly from the
nitriles by the action of sodium or sodium ethylate)
possessing a totally different constitution. E. v. Meyer's
1 Cf. Wurtz, Ann. Chem., vol. Ixxx. p. 346; A. W. Hofmann, ibid.,
vol. xxxiii. p. 57. 2 Cf. p. 354 et seq.
478 HISTORY OF ORGANIC CHEMISTRY CHAP.
investigations l on this subject have proved that the cyan-
alkines are to be regarded as amido-miazines or amido-
pyrimidines ; the mode in which they are formed is an
instructive case of polymerisation, this being brought about
by the migration of hydrogen atoms. The formation of the
di-molecular nitriles,2 which from their behaviour are to be
•classified as imido-nitriles, depends upon a similar reaction,
but one which does not go so far.
The rational composition of fulminic acid and allied com-
pounds, e.g., fulminuric acid and other isomers, is now
becoming much better understood, thanks to the pioneering
researches of Liebig,3 and the investigations of Kekule,4
Schischkoff,5 and, more recently, of Steiner, Carstanjen,
JChrenberg,6 and especially Nef,7 the last-named chemist
assuming a divalent carbon atom ; the point, however, has
not yet been made absolutely clear.
Historical Notes on Pyridine and Quinoline.8
An extensive group of nitrogen compounds — the pyridine
and quinoline bases — has only been worked at with success
of quite recent years, although these substances were in part
discovered during the earliest decades of the century ; their
investigation has been carried on with the utmost zeal ever
since it came to be recognised that the vegetable alkaloids
were among their derivatives. The researches of Anderson 9
on the volatile bases of bone oil, those of Williams 10 on the
1 Journ. pr. Chem. (2), vol. xxxix. p. 262, besides preceding numbers.
2 E. v. Meyer, ibid., vol. xxxviii. p. 336 ; vol. xxxix. p. 188.
3 Ann. Chem., vol. xxvi. p. 146.
4 Ibid., vol. cv. p. 279. 5 Ibid., vol. ci. p. 213.
6 Journ. pr. Chem. (2), vol. xxv. p. 232 ; vol. xxx. p. 38.
7 Ann. Chem., vol. cclxxxvii. p. 265.
8 With regard to the sources of the following notes, cf. the pamphlets
of Metzger, Hesekiel and A. Pictet on these bases, and Calm-Buchka's
work, Die Chemie des Pyridins und seiner Derivate.
9 Phil. Trans. E., vol. xvi. p. 4, and vol. xx. (2), p. 247 ; Phil. Mag. (4),
vol. ii. p. 257 ; Ann. Chem., vols. lx., Ixx., Ixxv., Ixxx. and Ixxxiv.
10 Phil. Mag. (4), vol. viii. p. 24 ; Phil. Trans. 23., vol. xxi. (2), p. 315,
etc.
vi PYRIDINE AND QUINOLINE 479
similar bodies contained in coal tar, and Gerhardt's observa-
tion on the production of quinoline from quinine l were the
first beginnings in the cultivation of this field, which has
.since been worked with such wonderful success. The in-
vestigation of these substances received a special impetus
from the recognition of the similarity between the pyridine
bases and quinoline, and of the distinct analogy between
these substances and the aromatic compounds. The earliest
attempt to explain the constitution of pyridine and quinoline
was due to Korner,2 and it bore the richest fruit ; he assumed
these bodies to be benzene and naphthalene respectively, in
which a methine group (CH)'" was replaced by the trivalent
nitrogen atom. This hypothesis was applied to the facts
already known, to which a large number of new ones were
being continually added, with the result that they were with-
out difficulty made to accord with it. The theory of the
aromatic compounds, which had by this time become strongly
developed, gave those endeavours a more or less secure basis
to go upon, especially when it came to criticising and sifting
the rapidly augmenting number of isomers among the pyridine
and quinoline derivatives.
The connection of pyridine and quinoline with benzene
and naphthalene, assumed in the above hypothesis, was
clearly proved by a succession of beautiful researches. We
may refer here to the analogous behaviour with regard to ox-
idising agents shown by the alkylated pyridines and the
alkyl derivatives of benzene. The investigation of these
relations, more especially those of the isomeric methyl- and
ethyl-pyridines and the pyridine mono-carboxylic acids, we
owe to the admirable work of Weidel, Skraup, Ladenburg
and Wischnegradsky. Just as the admissibility of the hy-
pothesis respecting the constitution of benzene was arrived at
from the number of its substitution-products which could
actually be prepared, so in like manner a similar deduction
was drawn for pyridine, viz. that only the theoretically pos-
sible methyl-pyridines and pyridine-carboxylic acids were
capable of preparation, and no more.
1 Ann. Chem., vol. xlii. p. 310. 2 Cf. p. 350.
480 HISTORY OF ORGANIC CHEMISTRY CHAP,
Among the experimental researches which have furnished
further support for the above view must be mentioned those
of Konigs, Ladenburg and A. W, Hofmann, which distinctly
proved the connection between pyridine and piperidine (the-
latter containing six atoms of hydrogen more in the molecule
than the former). The analogy between this compound and
pyridine on the one hand, and hexahydro-benzene and
benzene on the other, thus became at once apparent.
Ladenburg found that sodium, acting on an alcoholic solu-
tion of the particular substance in question, was a most ex-
cellent reducing agent for pyridine bases, and since then it
has been used with good effect in numberless instances.
We have but to think of the conversion of trimethylene
cyanide into piperidine and pentamethylene-diamine ; thi&
last compound, produced from the above-mentioned cyanide by
the addition of eight atoms of hydrogen in the molecule, was
proved to be identical with the ptomaine, cadaverine,
The different modes of formation of pyridine bases from
substances of simpler composition likewise assisted towards a
knowledge of their constitution, We may refer here to the
synthesis of one of the collidines from aldehyde-ammonia, as
well as from ethylidene chloride and ammonia : to that of a
chloro-pyridine from pyrrol-potassium and chloroform ; to
the researches of Hantzsch, which resulted in the artificial
production of lutidine ; and to the production of /3-methyl-
pyridine from glycerine (Stoehr).
The synthetic investigations of quinoline and its deriva^
tives have proved themselves extraordinarily fruitful ; they
have served more particularly to confirm the constitution as-
cribed to those compounds, this being also deducible from the
products of decomposition of the latter. Out of the great
amount of work done in this branch, only one or two re-
searches can be mentioned here, viz. those of Skraup, who
(doubtless stimulated by the previous investigations of
Konigs and Graebe) discovered the general method of pre-
paring quinoline and its derivatives, by the action of glycerine
on the aromatic amines ; Baeyer's beautiful investigations on
the formation of quinoline, oxy-quinoline, etc., by the con-
TI PYRIDINE AND QUINOLINE DERIVATIVES 481
densation of o-amido-phenyl compounds; the synthesis of
quinoline and its homologues from a mixture of o-amido-
benzaldehyde and other aldehydes by Friedlander ; and that
from aniline and aldehyde by v. Miller and Dobner. The
syntheses of homologues of quinoline and of quinoline-
carboxylic acids effected by C. Beyer and W. Pfitzinger are
also closely connected with the above modes of formation.
While these syntheses have made clear the constitution
of quinoline, other investigations have established its con-
nection with pyridine ; thus it was seen that the quinolinic
acid obtained by oxidising quinoline was a pyridine-dicar-
boxylic acid, the formation of which was in every respect
analogous to that of benzene-dicarboxylic acid from
naphthalene.
The minute study of the derivatives of quinoline has led
to a systematic investigation of the whole field, the researches
of Ad. Glaus l and his pupils on the halogen derivatives and
sulphonic acids of quinoline deserving special mention. In
this way other compounds of analogous constitution have been
isolated, e.g., the naphtho-quinolines and anthra-quinoline.
The discovery of iso-quinoline and its preparation from
derivatives of naphthalene (Gabriel, Bamberger, and Zincke)
also calls for notice.
The bases known as the di- and tri-azinesj which have been
investigated with much care during the last few years, stand
in the closest relation to pyridine and quinoline, just as these
do to benzene and naphthalene. In this connection the
work of Stoehr and of L. Wolff on pyrazine and piperazine
derivatives, and that of Pinner on pyrimidine must be
mentioned. The latest researches on cyanuric compounds
have shown these to be derivatives of triazine. Among the
highly nitrogenous compounds which proceed from quinoline,
the quinoxalines (Huisberg and others), which are analogous
to the pyrazines, and the quinazolines (Weddige, Paal, Wid-
mann and others), analogous to the pyrimidines, must be
named. — Specialization in organic chemistry has of late years
increased to such an extent that we have now detailed works
1 Journ. pr. Chem. from 1888 onwards.
I I
482 HISTORY OF ORGANIC CHEMISTRY CHAP.
dealing with branches of it that were either unknown or dis-
regarded only a short time ago.1
A still greater interest than that aroused by the discovery
of the compounds just named was awakened by the proof
(gradually arrived at from a long series of admirable
researches) of the intimate connection existing between
pyridine, quinoline and iso-quinoline and various vegetable
alkaloids, whose constitution was thereby explained. Wisch-
negradsky and then Konigs were the first to express the
opinion that the alkaloids were derivatives of pyridine or
quinoline. They grounded this view upon the conversion
of pyridine into piperidine, which is a decomposition-product
of the alkaloid piperine contained in pepper, and on the
retransformation of piperidine into pyridine ; to this was
added later on the precisely analogous conversion of conine
into conyrine, a propyl-pyridine.2 Quickly following the
recognition of this last important fact came the further one 3
that this alkaloid of hemlock was the dextro-rotatory
modification of a-propyl-piperidine.
Ladenburg's ingenious synthesis of conine 4 consisted in
the preparation of a-allyl-pyridine, the conversion of this (by
means of sodium) into a-propyl-piperidine, and the sub-
division of the latter optically inactive substance into its
active components.
The complete synthesis of other vegetable alkaloids is
without doubt merely a question of time ; some of them have
already been partially built up from their decomposition-
products, e.g., atropine from tropine and tropic acid (Laden-
burg), 5 and cocaine from ecgonine, benzoic acid and methyl
iodide (Merck).6 In the case of most of the alkaloids, —
nicotine, piperine, the alkaloids of opium, hydrastine, quinine,
strychnine, etc., the nature of their products of decomposition
1 Cf. 0. Kiihling's admirable Handbuch der stickstojfhaltigen Orthokon-
densationsprodukte (" Text-book of the Nitrogenous Ortho-condensation
Products." Berlin, 1893).
2 A. W. Hofmann, Ber.,vol. xvii. p. 825.
3 Cf. Ladenburg, Ann. Chem., vol. ccxlvii. p. 80 (1888).
4 Ber., vol. xxii. p. 1403.
3 Ann. Chem., vol. ccxvii. p. 74. 6 Ber., vol. xviii. p. 2952.
vi RELATION OF PYRIDINE, ETC., TO THE ALKALOIDS 483
affords a basis for conclusions with respect to their con-
stitution. The subject is too wide to be entered upon in
detail here. But it may just be stated that in most cases
the degradation-products show that a close connection exists
between the alkaloids and pyridine, quinoline, or iso-quinoline
as their nitrogenous nucleus.1 In addition to conine, the
constitution of the following important members of this class
has now been fairly well established: — nicotine (Pinner,
Blau) ; pitocarpine (Hardy and Calmels) ; cocaine (Einhorr^,
Merling) ; and papaverine (Goldschmidt).
The above very short summary of but a few of the many
investigations which have been carried out in this branch
is of itself sufficient to show how necessary is a knowledge
of the chemical nature and constitution of the pyridine and
quinoline bases for the proper understanding of the alkaloids,
and what a rich harvest may still be expected here.
Certain non-nitrogenous compounds also, which are
naturally related to the alkaloids, viz. meconic, comenic,
pyromeconic and chelidonic acids, whose constitution re-
mained quite obscure although the substances themselves
had long been known, have been shown, more particularly by
the recent researches 2 of Ost and of Lieben and Haitinger,
to be naturally connected with pyridine. Light was thrown
upon their constitution, as also upon that of the similarly
constituted compounds obtained from citric and malic acids,3
by the important observation that they are converted by
ammonia into oxypyridine-carboxylic acid. And Lieben
and Claisen's successful synthesis of chelidonic acid 4 has
finally solved the problem.
1 The literature on this branch of the science is already voluminous ;
the reader is specially referred to Pictet's admirable monograph : — Die
Pflanzenalkaloide, etc. (Berlin, 1891).
2 Journ. pr. Chem. (2), vol. xxvii. p. 257 ; vol. xxix. p. 57 ; Ber^ vol.
xvi. p. 1259.
3 A. W. Hofmann, Ber., vol. xvii. p. 2687 ; v. Pechmann, ibid., vol.
xvii. p. 936 ; vol. xix. p. 2694.
4 Wiener Mwwttshefte, vols. iv., v.,and vi. ; Ber., vol. xxiv. p. 111. ^
I I 2
484 HISTORY OF ORGANIC CHEMISTRY CHAP.
Pyrrol and Analogous Compounds.
Another group of compounds, of which pyrrol, furfurane
and thiophene are the representatives, has been the subject
of the most ardent investigation during recent years, with
the result that the constitution of these substances and also
that of many of their derivatives has been cleared up. The
analogy existing between those compounds gradually came
to be recognised ; they all contain the same nucleus, consist-
ing of four atoms of carbon and four of hydrogen, this being
combined in pyrrol with the imido-group (NH), in furfurane
with one atom of oxygen, and in thiophene with one atom of
sulphur. Their similarity to benzene became more apparent
the better they came to be known, and was shown in a
particularly striking manner in the investigation of thiophene
(discovered by Victor Meyer) and its derivatives. The work
which has been done upon this class of bodies is amongst
the most brilliant of our time.1
The artificial formation of thiophene from succinic acid
and phosphorus trisulphide, 2 that of pyrrol from succinimide
by means of zinc dust, and the conversion of pyrrol into
the compounds richer in hydrogen — pyrroline and pyrrolidine
(Ciamician) — are reactions of special importance, which helped
greatly to elucidate the constitution of these bodies. Pyrrol,
which was observed by Runge in coal tar and named by him,
and first isolated by Anderson, has with its rapidly-augmenting
host of derivatives been closely and comprehensively ex-
amined by Ciamician, Dennstedt, Paal and others of late
years, Schwanert 3 a long time ago having made the funda-
mental observation that pyrrol could be produced from
ammonium mucate.
The work done upon furfurane (which was discovered by
Limpricht 4) is to be taken in conjunction with that upon
pyromucic acid (first observed by Scheele, and recognised as
a distinct compound by Labillardiere) and its aldehyde fur-
furol (discovered by Dobereiner and examined by Stenhouse,
1 Cf. pp. 350—351. 2 Ber., vol. xviii p. 454.
3 Ann. Chem., vol. cxvi. p. 278. 4 Ibid., voL clxv. p. 281.
vi FURFURANE, PYRROL, AND INDOLE 485
Fownes and others). The analogy in behaviour of the
latter to benzoic aldehyde was proved more especially by
Baeyer and E. Fischer,1 and the close connection between
pyromucic and maleic acids by Hill.2 Paal's beautiful
investigations have shown that derivatives of furfurane,
thiophene and pyrrol are produced from 7-diketones and
7-diketonic acids,3 and have thus contributed in a marked
degree to solve the constitution of these compounds (i.e., of
pyrrol, etc.).
Among the aromatic compounds proper, to which the sub-
stances just named show a great similarity in chemical be-
haviour, indole (discovered by Baeyer) was recognised by
him as being an analogue of pyrrol, and was made the basis
of important researches which resulted in showing its relation
to the compounds of the indigo group, more particularly to
isatin, oxindole and dioxindole. Various derivatives of
indole have lately been prepared by a method discovered by
E. Fischer, — i.e, from the condensation of phenyl-hydrazine
with aldehydes and ketones.4 Cumarone, obtained by Fittig
and Ebert from cumarine, has been designated by Hantzsch 5
the " furfurane of the naphthalene series," and he has con-
firmed this view by some ingenious syntheses of its deriv-
atives. The analogy existing between the three compounds
furfurane, thiophene and pyrrol, and diphenylene oxide,
sulphide and imide (carbazole) respectively, was perceived
about the year 1885.
For some years past the attention of a large number of
investigators has been given to the study of compounds
which are related to pyrrol and its analogues as pyrazine and
pyrimidine are to pyridine, or quinazoline to quinoline
(cf. p. 481). Those remarkable compounds the azoles
(pyrazole, glyoxaline, triazole, etc.) are pyrrol derivatives of
this kind, which have been made known to us by the
researches of Marckwald, v. Pechmann, Bladin and others.
1 Ber., vol. x. p. 13.
2 Hid., vol. xiii. p. 734 ; Journ. Chem. Soc., vol. xl. p. 36.
a Cf. Paal's monograph on the subject (Wurzburg, 1890).
4 Ann. Chem., vol. ccxxxvi. p. 116.
5 Ber., vol. xix. p. 1290; also vol. xx.
486 HISTORY OF ORGANIC CHEMISTRY CHAP.
Pyrazolone, iso-pyrazolone and their derivatives have proved
of special interest in the hands of Knorr and his pupils,
Curtius and von Rothenburg, etc. The thiazoles and
oxazoles, derived from thiophene and furfurane respectively,
have been studied by Hantzsch, Claisen and others.
Organic-metallic Compounds.
After it had come to be seen that not only hydrogen,
oxygen, nitrogen, sulphur and the halogens could combine
directly with carbon, but also arsenic as well — a point which
Kolbe was the first to indicate in his interpretation of
cacodyl,1 — new fields in organic chemistry became opened up
in rapid succession. Frankland's discovery 2 of the action of
zinc on methyl and ethyl iodides, in which the metal breaks
up the iodide in order to combine with the alkyl radical, led
to a knowledge of the organo-metallic compounds. Thanks to
the readiness with which these enter into reaction, they have
been destined to aid in the development of organic chemistry
to an unlooked-for extent, more especially as regards syn-
thetic methods. With the aid of the zinc-alkyls many other
organo-metallic compounds were prepared and minutely in-
vestigated in due course, e.g. the ethyl compounds of tin,
mercury, lead, sodium, aluminium and other elements. 3
Among the last were those non-metals of which organic
compounds had not previously been known ; boric methide
and other similar substances were prepared by Frankland,4
and the important alkyl compounds of silicon by Friedel
and Krafts, the composition of these latter proving the
complete analogy between that element and carbon. To the
1 Cf. p. 324.
2 Journ. Chem. Soc., vol. ii. p. 263; ov Ann. Chem., vol. Ixxi. p. 171
(1849).
3 Cf. the papers of Buckton, Odling, Frankland, Cahours, Ladenburg,
etc. , in the Philosophical Transactions, Journal of the Chemical Society, and
Annalen der Chemie.
4 Proc. JR. 8., vol. xii. p. 123 ; or A nn. Chem., vol. cxxiv. p. 129. For
aromatic compounds of Boron, see Michaelis and others, Ber., vol. xxvii. p.
244.
vi ORGANO-METALLIC COMPOUNDS 487
organo-metallic compounds of the fatty series, various others
belonging to the aromatic have since been added, the first of
these having been mercury di-phenyl.1 Magnesium, bismuth
and thallium alkyls have also been prepared within the last
few years. The peculiar compounds of nickel, iron and
platinum with carbonic oxide, which find a place alongside
of the organo-metals, have already been spoken of under the
metals themselves.
The short description which has just been given of the
development of organic chemistry is sufficient, notwith-
standing its incompleteness, to allow of our recognising the
main currents which have prevailed, and which still do so, in
this branch of the science. The review of the numberless
organic substances, which have been investigated during the
last fifty or sixty years, is materially facilitated by the general
points of view which have become gradually established
from the classification of those compounds and from the
deduction of their chemical constitution. A prominent place in
this respect is to be given to the gradually growing perception
that organic compounds might be looked upon as derivatives
of inorganic, and to the increasing certainty with which
their constitution could be defined on the basis of the
saturation-capacities peculiar ^to the atoms of the various
elements.
1 R. Otto, Ann. Chem., vol. cliv. p. 93. Cf. more especially Michaelis'
work on the phosphenyl compounds, etc.
488 "•"HISTORY OF PHYSICAL CHEMISTRY CHAP.
HISTORY OF PHYSICAL CHEMISTRY IN RECENT TIMES1
The influence which certain branches of physics have ex-
ercised on the development of chemical doctrines cannot be
estimated too highly. It was through the introduction of
physical methods, more particularly through the application
of weighing, measuring and calculating to chemical problems,
that chemistry first became an exact science. The import-
ance of those methods, in so far as they have had a deter-
mining influence on the chemical tendency of the present
period, has already been entered into in the general section
of this book. From the time of Lavoisier onwards, it came
to be more and more clearly seen that an intimate connection
existed between the chemical and physical properties of sub-
stances. Definite relations were found to hold good both be-
tween the proportions by weight of substances which enter
into chemical combination and between the volumes of com-
bining gases (Avogadro, Gay-Lussac). Investigators sought
to determine the more important physical constants of com-
pounds in their various states of aggregation, e.g. the specific
gravity, specific heat, etc., as well as the changes in physical
properties which were brought about by chemical reactions,
and thus to arrive at general relations from which the
chemical constitution and physical behaviour of different sub-
stances could be elucidated. To the efforts at solving such
problems as these, physical chemistry owes its origin and
gradual development.
Although Lavoisier, in conjunction with certain eminent
physicists (Laplace, in particular), took up some of the above
1 With regard to the sources of information on which this and the follow-
ing sections are based, the reader is referred to W. Ostwald's admirable
Lehrbuch der allgemeinen Chemie, 1st. edition in two volumes, 1885 — 7 ;
2nd. completely revised edition, of which two volumes have so far been
published, 1890—1897 (cf. note 1, p. 377). W. Nernst's Theoretische Chemie
(1893), which has been translated into English by C. S. Palmer of Colorado,
is also a book of originality ; and this remark likewise applies to the earlier
work with the same title by Horstmann.
vi HISTORY OF PHYSICAL CHEMISTRY IN RECEmiES 489
problems, and Gay-Lussac at a later period established the
relations which exist between the volumes of different gases
and their chemical composition, while Dulong and Petit
pointed out the connection between the specific heat and
atomic weight of the elements, the boundary land between
physics and chemistry was first systematically explored by
Hermann Kopp ; with the investigations of the last-named
chemist on the relations between atomic weight and specific
gravity, on the laws which regulate the boiling temperatures
of liquids, and so on, the history of physical chemistry is in-
timately bound up. The attention paid to physico-chemical
questions has gone on steadily increasing during the last
three or four decades, and this applies in a special degree to
such as bear upon the relations between the thermo-chemical,
optical, and electro-chemical behaviour of substances and
their chemical constitution. All this work in physical
chemistry has found a rallying point in the Zeitschrift fur
physikalische Chemie, which was projected by Ostwald in 1 88 7,
and which has throughout been edited by himself and van 't
Hoff.
But there is another allied branch also, viz. that of
chemical affinity (Verwandtschafi), which has been greatly
benefited by the investigations just referred to. With the
aid of physico-chemical methods, and the calculations re-
quisite for these, a beginning is being made towards the
solution of the old problem respecting the cause and nature
of chemical affinity. It will therefore be appropriate to
speak of the history of the doctrine of affinity while describing
the development of physico-chemical researches. Through
both of these branches there runs the continuous endeavour
to make chemical reactions capable of mathematical treatment.
The behaviour of gases and vapours has been, almost more
than anything else, the subject of fruitful physico-chemical
investigations, doubtless because the physical properties of a
substance in the gaseous state are observable with fewer
complications than in any other, and hence definite relations
between these properties and the chemical constitution of
the compound are more readily apparent.
490 HISTORY OF PHYSICAL CHEMISTRY CHAP.
Determination of Vapour Density.
The laws of Boyle and Mariotte and of Gay-Lussac,
which expressed the connection between the volume of a gas
and its temperature and pressure, prepared the ground for a
knowledge of other relations. Gay-Lussac's law of volumes,
which has already been treated of,1 was the first result in
this branch which benefited chemistry in an exceptional
degree. The recognition of the intimate connection between
the specific gravity of a gas and its molecular weight we owe
to Avogadro,2 although it was a long time of taking root in
the science; this "law of Avogadro," which expresses the
above relation, still governs chemical research, and is an
indispensable aid in the determination of the molecular
weights of many chemical compounds.
The due appreciation of its value has led to continuous
endeavours towards simplifying and refining the methods for
determining the specific gravity of gases and vapours.
Dumas, as already mentioned, was the first to devise a
generally applicable method for vapour density determina-
tions,3 and by this he achieved great results. Another plan,
according to which the volume of vapour produced from a
given weight of substance is accurately estimated, was worked
out by Gay-Lussac and afterwards modified by Hofmann.4
And to the above methods there was added in 1878 that of
Victor Meyer,5 which depends upon the measurement of the
air (or any other indifferent gas) which is expelled from the
apparatus by the vapour resulting from a given weight of
the substance in question. The improvements which those
methods have undergone since their introduction cannot be
entered into here, but emphasis must be laid upon the point
that through their means the all-important knowledge of the
relative weights of the atoms and molecules of elements
and compounds has been immensely advanced.
The determination of the specific gravity of vapours has
proved in certain cases the most reliable means of decid-
1 Cf. p. 214. 2 Cf. pp. 215 and 294.
3 Ann. Chim. Phys., vol. xxxiii. p. 341.
4 Ber., vol. i. p. 198. 5 Ibid., vol. xi. pp. 1867 and 2253.
vi DETERMINATION OF VAPOUR DENSITY 491
ing between the values arrived at by different methods,
stochiometric or otherwise, and so getting at the correct
atomic weights of the elements. To give only some more
or less recent instances of this, we would refer to the de-
duction of the atomic weights of silicon, beryllium, thorium
and germanium from the vapour densities of their chlorides.
Starting with Avogadro's hypothesis — that the vapour density
is proportional to the molecular weight — chemists have been
able to deduce from the specific gravities of gasified elements
most striking conclusions with respect to the number of
atoms in their molecules at different temperatures. One
has but to think of the results of Dumas' and Mitscherlich's
investigations x on the vapour densities of sulphur, arsenic,
phosphorus and mercury, the molecules of which contain
different numbers of atoms, as was deduced at a later date
from the specific gravity of their vapours after the revivifica-
tion of Avogadro's law. The reader is further referred to the
important work of V. Meyer and of Nilson and Pettersson
on the vapour densities of compounds, more especially of such
as show a varying composition with changing temperature.
Aluminium chloride, for instance, has the simplest molecular
weight which is possible (that expressed by the formula
A1C13) at a temperature sufficiently high, but one double as
great (A12C16) at lower temperatures ; and the same applies
to stannous chloride (SnCl2 or Sn2Cl4), etc. The latest ef-
forts of workers in this field are being directed to the de-
composition of molecules into their elementary atoms, by
making use of exceedingly high temperatures (V. Meyer).
These few examples are sufficient to illustrate what has
just been said above. The significance which is attached
to the results of vapour density determinations is most
strikingly shown in the fact that such estimations are held
to be the most reliable means of getting at the valency of
an element, The amount of care, however, which is requisite
here, is proved by the different results obtained by different
experimenters, and is particularly apparent in the be-
haviour of aluminic chloride, from whose vapour density the
1 Cf. p. 225.
492 HISTORY OF PHYSICAL CHEMISTRY CHAP.
conclusion was drawn (and held to until quite recently) that
aluminium was tetravalent, although the whole behaviour of
the element pointed to its tri-valency ; this has now been
confirmed by the determination of the normal density of
vapour of the chloride.
Dissociation.
From the observations made upon what are known as
anomalous vapour densities, the cause of which has been
recognised in a gradually increasing decomposition of the
compound with rise of temperature, the doctrine of dissocia-
tion— so important for physical chemistry — has developed
itself ; the name " dissociation " was first made use of by
H. de St. Claire Deville to express decompositions of this
nature. He was the earliest (from the year 1857)1to
work systematically at this branch of the science, which has
also been made the subject of important investigations by
others since, e.g. Debray, Cahours, Wurtz, Horstmann, Isam-
bert and A. Naumann. Most of these experimenters did not
confine themselves to cases of so-called abnormal vapour
density alone, but studied generally the gradual increase in
decomposition of chemical compounds under an increasing
temperature. Of late years the assumption that every
electrolyte is dissociated in solution has come prominently
forward (see below).
The Liquefaction of Gases.
The investigation of the transition of gases and vapours
into the liquid and solid states has given rise to work of
exceeding importance. We have but to recall the com-
prehensive researches of Faraday 2 on the liquefaction of
gases which were at that date held to be uncondensable,
and especially the remarkable investigations of R. Pictet,3
Cailletet,4 Wroblevsky and Olzevsky,5 which proved that
1 Cf. Comptes Rendus, vol. xlv. p. 857.
2 Phil. Trans, for 1823, p. 160 ; and for 1845, p. 1.
3 Comptes Rendus, vol. Ixxxv. p. 1214 ; also in subsequent volumes of
the Archives des Sciences Naturelles.
4 Comptes Rendus, vol. Ixxxv. p. 1213 (1877).
5 Ann. Phys., N. F., vol. xx. p. 243, etc.
vi LIQUEFACTION OF GASES 493
there was no known gas that could withstand the combined
effect of sufficiently high pressure and low temperature. Nitro-
gen, oxygen, hydrogen and argon were thus all reduced by
these experimenters to the liquid, and nitrogen and argon to
the solid states, and their boiling temperatures determined,
— observations of very great moment. The recent work of
Linde and Hampson has greatly simplified the process for
the liquefaction of air, which will probably in the future
prove of importance from a technical point of view, e.g. may
cheapen the production of oxygen. Dewar has just suc-
ceeded in obtaining a measurable amount of liquid hydrogen
(about 50 c.c. at one time). Liquid hydrogen is clear and
colourless, it shows no absorption spectrum, and the meniscus
is as well defined as in the case of liquid air. The boiling
point, determined by Dewar with a platinum resistance
thermometer, is — 238°C., and the density of liquid hydrogen
at its boiling temperature is 0'07 approximately ; it is thus
by far the lightest liquid known. Hydrogen does not possess
in the liquid state the characters of a metal.1
Thirty years ago Andrews 2 had made a thorough study
of the conditions under which a gas can be liquefied, and
had established the important conceptions of " critical tem-
perature " and " critical pressure," Mendelejeff 3 having some
time before this made certain fundamental observations on
the subject.
Light was thrown upon the behaviour of gases to liquids
in the first decade of the century by the investigations of
Henry and Dalton, which established the fact that the
amount of absorption of a gas or of a mixture of gases by a
liquid is dependent upon the pressure, and this law was after-
wards confirmed by Bunsen's classical researches. 4
The Kinetic Theory of Gases.
The thorough investigation of gases, of their physical
behaviour in particular, led to the setting up of a theory by
1 Journ. Chem. Soc. for 1898, p. 528.
2 Pkil. Trans, for 1869, p. 575; or Pogg. Ann., Suppl., vol. v. p. 64
(1871).
3 Ann. Chem., vol. cxix. p. 11. 4 Ibid., vol. xciii. p. 1 (1855).
494 HISTORY OF PHYSICAL CHEMISTRY CHAP.
means of which the various phenomena exhibited by them—
specific heat, diffusion and friction — have been brought
together under one common standpoint and explained in a
satisfactory manner. The fundamental idea that a gas was
an assemblage of moving particles had previously been put
forward by D. Bernoulli in 1 7 3 8 and by Herapath, and Joule
had in 1851 made a great step in advance by calculating the
mean translational velocity of these particles. This idea, in
the hands of Kronig and more especially Clausius (in 1857),
gave birth to the modern kinetic theory of gases, which has
been so splendidly worked out by Clausius and Maxwell, and
since then perfected in detail by Boltzmann, O. E. Meyer,
van der Waals and many others. It may be regarded as
springing from the mechanical theory of heat.1
Spectrum Analysis.
The examination of the optical behaviour of glowing
gases and vapours has exercised a most profound influence
upon physical chemistry. Spectrum analysis has grown out
of some apparently insignificant and disconnected observa-
tions made by Marggraf, Scheele, Herschel and others upon
the light emitted by flames coloured by certain salts.
The spectra of such flames were investigated by various
physicists, among whom Talbot, Miller and Swan deserve
first mention ; but it was only after Kirchhoff2 (in 1860)
had made and proved the definite statement — that every
glowing vapour emits rays of the same degree of refrangi-
bility that it absorbs, — that spectrum analysis became de-
veloped by Bunsen and himself into one of the great branches
of our science. Its importance for analytical chemistry has
already been touched upon.
The application of the spectroscope to the determination
of the composition of the heavenly bodies, and with this the
firm establishment of stellar-physics, must be mentioned
1 For an account of the development of the above theory, see 0. E.
Meyer's work, Die Kinetische Theorie der Gase (Breslau, 1877) ; also Watson's
Kinetic Theory of Gases.
2 Pogg. Ann., vol. cix. p. 275.
vi SPECTRUM ANALYSIS : ATOMIC VOLUMES 495
here. With respect to general chemistry, the efforts to ar-
rive at harmonic relations between the lines of the spectrum
themselves, and at a connection between those lines and the
atomic weights of the elements which give rise to them, ap-
pear to be well founded, as is seen from the work of Maxwell,
Balmer, Stoney, Soret and Lecoq de Boisbaudran.1 A com-
plete theory of the spectral phenomena peculiar to gases re-
mains still a problem for the future, although much admir-
able preparatory work has been done on the subject.
Atomic Volumes of Solids and Liquids.
The endeavour to establish relations between the
physical properties of solid and liquid bodies and their
chemical composition has given rise to a large amount of
investigation, of which the most important must be men-
tioned here. H. Kopp was the first to work out in a
through manner the connection between the specific gravity
of elements and compounds and their atomic composition,
Dumas, Herapath, Karsten, Boullay and Ammermuller having
previously given some attention to the subject. After
establishing the atomic or specific volumes of these latter,
Kopp succeeded in discovering a number of relations, and,
more particularly, in working out the specific volumes of the
elementary atoms in compounds ; it thus became possible to
calculate the atomic volumes of complex compounds.2
The work done of recent years in this branch, among
which that of Thorpe, Lessen, Staedel and R. Schiff may be
mentioned, has for the most part been carried out upon the
principles laid down by Kopp ; it has resulted in bringing
out many new points of view, and has led to a number of
modifications in the values arrived at by him. The formerly
accepted opinion — that the atomic volumes of the elements
in their compounds are mostly invariable — has been greatly
shaken by this later work. Among the numerous researches
1 Cf. Ostwald's Lehrbuch, 2nd. edition, vol. i. p. 260 et seq.
2 Cf. Kopp's pioneering researches, Ann. Chem., vol. xli. p. 76 ; vol.
xcvi. pp. 153 and 303. The last piece of work which he carried out dealt
with the Molecular Volumes of Liquids (Ann. Chem., vol. ccl. p. 1).
496 HISTORY OF PHYSICAL CHEMISTRY CHAP,
(in addition to H. Kopp's) which have been made with the
object of discovering a connection between the volumes of
solid compounds and their atomic composition, those of
Schroeder are especially worthy of note. He assumes volume
units * of chemically analogous elements, and believes that
he has in this found the key to the solution of the above
problem (the doctrine of " Parallelosterism "). But here
again we are still far from a knowledge of any law governing
the atomic volumes of solid or liquid compounds, whereas, in
the case of gases, the simple relations existing between
specific gravity and composition were worked out a long
time ago.2
Laws regulating the Boiling Temperature?
Kopp was likewise the first, in his classical researches,4
to point out a connection between the boiling temperature
and the composition of compounds (more especially of organic
ones), in so far that he drew from his results the deduction
that approximately equal differences in boiling-point corre-
spond to equal differences in the composition of organic
substances. And even although this supposed regularity
turned out to be only applicable to certain compounds, and
could not be relied upon for other series, still Kopp's work
gave a powerful impetus to the search after actual relations
— expressible by figures — between boiling-point and chemi-
cal composition.
The question arose, — in what manner does the different
chemical constitution of isomeric and chemically analogous
compounds exercise an influence on their boiling tempera-
tures— to be subjected to examination by Kopp.5 Other
more recent and more extended investigations, e.g. those 6 of
1 These mnits he terms Steren. 2 Cf. pp. 214 and 490.
3 For the literature on this subject, cf . the article Siedepunkt in Fehling's
Handworterbuch by Nernst and Hesse.
4 Ann. Chem., vol. xli. pp. 86 and 169; vol. Iv. p. 166, etc.
6 Ann. Chem., vol. 1. p. 142 ; vol. xcvi. p. 1.
6 Cf. A. Naumann, Allgemeine und Physikalische Chemie(" General and
Physical Chemistry"), (1877), p. 553 et seq ; Ostwald, Lehrbuch der aMge-
meinen Chemie, 2nd. edition, vol. i., p. 330 et seq.
vi LAWS REGULATING BOILING TEMPERATURE 497
Linnemann, Schorlemmer, Zincke, Naumann and others, have
resulted in showing that there are a number of definite rela-
tions here also, without, however, having rendered it possible
to formulate a precise law setting forth the dependence of
boiling-point upon chemical constitution ; but it has been
clearly established that there is a distinct connection between
them. It is possible that a closer knowledge of the intimate
relation sought for may be arrived at rather from the
occasionally observed anomalies (e.g. the lowering of boiling
temperature with increasing molecular weight, as in the case
of the glycols and certain chlorine compounds, etc.) than from
regularities. The efforts to establish definite formulae for
the relationship of the vapour pressure of liquids to the
temperature have been followed with great success ; they have
resulted in the laws worked out by Duhring, Winkelmann,
and Ramsay and Young.
There have not been wanting zealous endeavours also to
discover regular relations between the temperatures at which
solid substances become liquid and their composition, but no
definite results have been arrived at in this way. Of more
importance, however, have been the researches made with the
object of determining melting-point and heat of solidification,
e.g. those of Pettersson and Nilson, and those on the
influence of pressure upon melting-point (James Thomson,
Bunsen). KrafFt and Weilandt1 have recently made some very
remarkable observations on the great reduction of the boiling-
point in a very high vacuum.
Specific Heat of Solid Bodies.
The work which has been done upon the specific heat of
elements and compounds is among the most important in
the whole field of physical chemistry, the dependence of this
property on the atomic composition having been definitely
established. We would recall here the Dulong-Petit law of
the approximate equality in the specific heats of solid
1 Ber., vol. xxix. p. 1316.
K K
498 HISTORY OF PHYSICAL CHEMISTRY CHAP,
elements, the significance of which for the development of the
atomic theory has already been detailed in the general
section ;x the extension of this law by Neumann ; and its en-
largement by Regnault's classical researches, as well as by
those of H. Kopp, Weber and others, which proved that the
specific heat varies with the temperature at which it is
determined. And even if the confidence felt in the applic-
ability of the Dulong-Petit law was shaken by the marked
deviation from it shown by certain elements, still its useful-
ness in a very large number of cases and the great value of
its principle remained ; as Berzelius had predicted, it formed
"the foundation of one of the most beautiful pages in
chemical theory." The investigation of the specific heat of
liquids has not led to conclusions of such a general nature
as have resulted in the case of solids.
Optical Behaviour of Solids and Liquids.
A long series of excellent experimental researches has
been induced by the endeavour to discover definite relations
between the optical behaviour of solid and liquid substances
and their chemical composition. The earlier labours of
Becquerel, Cahours and Deville, and the later ones of
Gladstone and Dale, Landolt, Briihl, Kanonikoff and others
have led to conclusions of importance respecting the con-
nection between the constitution of a substance and its
power of refracting a ray of light.2
The working out of the refraction-equivalents pertaining
to the individual elementary atoms within their compounds
has led to the discovery of stochiometric regularities with
respect to refraction. Of special interest is the proof that
the varying function or mode of combination of the elements,
carbon in particular, has a determining influence on the
molecular refraction. If the latter is accurately known,
1 Cf . p. 220.
2 For the literature on this subject, cf. Landolt and Bernstein's Physi-
Jcalische-Chemische Tabellen, p. 220 ; and Ostwald's Lehrbuch, 2nd. edition,
vol. i. p. 415 et seq.
vi CIRCULAR POLARIZATION 499
then conclusions may be drawn from the refractive power as
to the constitution. Deductions of this kind have been
applied more especially to solving the question of the consti-
tution of benzene. The great class of keto-compounds has
also been investigated optically, with the view of making
certain of the constitution.1
Only a passing reference can be made here to the
importance to crystallography of the observed relations
between light refraction and crystalline form, and to the
pioneering work of Brewster and Fresnelon the subject.
Another optical property of many substances, more especi-
ally organic, has greatly excited the interest of chemists
in quite recent years, viz. circular polarisation, which it has
been attempted, and with success, to connect closely with the
chemical constitution of the compounds in question. After
the first memorable investigations of Arago, Biot and
Seebeck had been made, the observation — that certain sub-
stances, whether in the solid or liquid state, are capable of
turning the plane of polarisation of light — was held to be
of importance for physics alone. It has only been since
Pasteur's beautiful researches2 on the optically active
tartaric acids, and the inactive racemic acid produced by
their combination, that relations between optical activity
and crystalline form have been discovered, and deductions
drawn from these as to chemical constitution.
The desire to gain light upon this point produced in
1 8 7 4 a theory, which was given out at the same time and
independently by Lebel 3 and van 't Hoff,4 and which is
based upon the hypothesis that the cause of this optical
activity is to be sought for in the presence of one or more
asymmetric carbon atoms, i.e. a carbon atom which is linked
to four other different atoms or radicals. Should this
1 Cf. particularly the latest investigations by Briihl, Journ. pr. Ghent.
(2), vols. xlix and 1 ; and the most recent volumes of the Berichte, especially
vol. xxix. p. 2902.
2 Comptes Rendus, vol. xxiii. p. 535 (1848) ; vol. xxix. p. 297 ; vol. xxxi.
p. 480.
3 Bull. Soc. Chim. (2), vol. xxii. p. 337.
4 Ibid. (2), vol. xxiii. p. 295.
K K 2
500 HISTORY OF PHYSICAL CHEMISTRY CHAP.
assumption become fully demonstrated (and it has this in its
favour, — that an asymmetric carbon atom has been found in
every optically active substance whose constitution has been
determined with the necessary accuracy), then it may with
confidence be stated that there is an intimate connection
between this physical property and chemical constitution.
We may again refer shortly here to van 't Hoif s spacial
conception of the distribution of the four valencies of the
carbon atom (represented as in the middle of a tetrahedron,
with its four affinities at the four corners), and to the
extension of this hypothesis by Wislicenus, who has ex-
plained by its means the constitution and formation of
geometrical isomers, e.g., fumaric and maleic acids, and the
crotonic acids, with their derivatives,1 and also the chemical
behaviour of these compounds. Such speculations have very
quickly proved themselves fruitful, in that they have led
to the perception of relations which had been hitherto
overlooked.
In addition to what has just been said with regard to circular
polarisation, mention must be made here of the work done
upon the rotation of the plane of polarisation by a magnet,
since stochiometric regularities, i.e., relations between mag-
netic polarisation and chemical constitution, have been
brought to light in this case also by the careful investigations
of W. H. Perkin sen.2
Diffusion, etc.
The properties of liquids which are comprised under
the designation " capillarity," together with the friction 3 and
diffusion of liquids and of solutions of solids in liquids,
have given rise to numerous and valuable researches.
Ramsay and Shields 4 have proved that by the measurement
1 Cf. p. 356.
2 Journ. pr. Chem. (2), vol. xxxi. p. 481 ; or Journ. Chem. Soc. vol.
xlv. , p. 421 ; also Journ. pr. Chem. vol. xxxii. p. 523.
3 Internal friction is treated historically in Ostwald's Lehrluch, 2nd.
edition., vol. i. p. 550, where one also finds an elegant method for its quan-
titative determination.
4 Journ. Chem. Soc. for 1894, p. 1089.
vi DIFFUSION ; THEORY OF SOLUTION 501
of the molecular surface energy of liquids, the latter can be
divided into two classes, viz., those of which the molecules
are as simple in the liquid as in the gaseous state (and this
applies to the generality of liquids), and those — such as
water and the alcohols — in which the molecules form com-
plices. This complexity of liquid molecules has been con-
firmed by Guye.1
Graham's memorable researches2 gave a powerful im-
pulse to the investigation of fluid friction and diffusion ;
here, too, relations have been found between these pheno-
mena and chemical composition. Mention must be made,
in conjunction with this, of his division of substances into
crystalloids and colloids, according to their behaviour on
diffusion. The reader is also referred to the work upon
osmose (so nearly connected with diffusion, and of such
great importance for physiology) by Jolly, C. Ludwig, Pfeffer
and Briicke. Pfeffer's observations on osmotic pressure
have proved of the first importance for the dissociation theory
of solution (see below).
Theory of Solution ; Electrolytic Dissociation?1
For about a dozen years past a number of eminent
investigators, who have devoted themselves to physical
chemistry, have been occupied with the question of solution ;
among those who have done most to extend this subject,
van 't Hoff, Arrhenius, Ostwald, Fr. Kohlrausch and Planck
must be named. The fundamental idea underlying this
work was that substances in highly dilute solution are in a
state which is comparable with that of gases. While this
idea was not a new one, van 't Hoff was the first to make the
following definite statement, and to bring forward strong
arguments in its support, viz. that the osmotic pressure of a
1 Ann. Chim. vol. xxxi. (6), p. 206.
2 Phil. Trans, for 1850, 1851, and 1861 ; or Ann. Chem., vols. Ixxvii.,
Ixxx., and cxxiii.
3 For the historical development of these speculations, see Ostwald's
Lehrbuch ; Nernst's Theoretische Chemie ; van't Hoff, Ber., vol. xxvii. p. 6 ;
Horstmann, Naturwissenchaftliche Rundschau for 1892, p. 465.
502 HISTORY OF PHYSICAL CHEMISTRY CHAP.
solution (e.g. a solution of sugar in water) is equal to the
pressure which the same quantity of dissolved substance
would exert if it were in the state of gas and filled the space
at present occupied by the solution.
Similar relations to those observed in the determination
of osmotic pressure had been found by various experimenters
(Blagden, Rudorff, de Coppet, and Raoult) when they estab-
lished the facts that the freezing point of a solution is
dependent on the concentration and the nature of the
dissolved substance, and that the lowering of the vapour
presure of a solution or the raising of its boiling point also
depends on the amount of substance dissolved.
Raoult was the first to point out the great significance of
these laws — laws which are theoretically deducible from
van 't HofFs axiom — for the determination of the molecular
weight of a dissolved compound.1 From those laws, therefore,
the deduction was immediately drawn that equi-molecular
solutions (i.e. solutions which contain, in equal volumes of the
solvent, quantities of different substances proportional to
their molecular weights) show the same osmotic pressure,
freezing point, vapour pressure and boiling point. And,
thanks to the facility with which freezing and boiling tem-
peratures can be determined, methods were quickly devised
by which the molecular weights of substances in solution
could in this way be arrived at. E. Beckmann has rendered
signal service in the practical elaboration and the scientific
testing of such methods, while Raoult, Auwers, Eykman and
others have striven to make this procedure for molecular
weight determination applicable as far as possible to every
case.
Of quite exceptional importance were the deductions
drawn when the osmotic pressure, freezing point and boiling
point of solutions of salts, acids and bases were viewed in the
light of the above-mentioned theory. The marked devia-
tions which were observed in this case found a simple explana-
tion in the assumption that these compounds un3erwent
dissociation when the solution became very dilute, — an
1 Ann. Chim. Phys. (6), vol. ii. p. 92.
vi ELECTROLYTIC DISSOCIATION ; ELECTROLYSIS 503
assumption which is in accordance with the numerous
observations on the electric conductivity of such -solutions.
Arrhenius was the first to attempt an explanation of this
behaviour of the dissolved electrolyte by assuming an
electrolytic dissociation, according to which every electrolyte
in aqueous solution undergoes dissociation into its ions, the
degree of dissociation depending on the dilution and on the
nature of the electrolyte itself. Although this hypothesis
has met with great opposition in many quarters, and although
it may seem at first sight to be far-fetched, there is no
denying its exceeding usefulness for the explanation of
numberless chemical processes ; it has proved itself of special
importance for electro-chemistry, analytical chemistry, and the
doctrine of affinity.1
Electrolysis of liquid or of dissolved Substances.
The importance of the first work which was done upon
this subject for the development of the electro-chemical
theory has already been shortly touched upon in the
general section.2 The connection, so early assumed between
electricity and chemical action, received the most brilliant
confirmation from Faraday's electrolytic law, according to
which equal amounts of electricity, when passed through
different electrolytes, set free equivalent quantities of
analogous substances at the two poles.3 This law was
vigorously contested by Berzelius, because it appeared to him
to imply that all the components of the substances decom-
posed by the current were held together in these by equal
affinities. Later experimental researches have corroborated
the validity of this law in its full extent, and permit of our
hoping for a definite solution of the important problem of
chemical equivalents, and, with this, of the true saturation-
1 Cf. Kiisser's very able paper in the Zeitschrift fur Elektrochemie, vol.
iv. p. 105, entitled Ueber lonenreaktionen und ihre Bedeutung fur die Elektro-
chemie ; Nernst's Die Elektrolytische Zersetzung wdssriger Ldsungen (Ber.,
vol. xxx. p. 1547); Dampier Whetham's "Solution and Electrolysis "(1895);
and Ostwald's recent work "The Scientific Foundations of Analytical
-Chemistry."
2 Cf . p. 229 et seq. 3 Cf> p> 228>
504 HISTORY OF PHYSICAL CHEMISTRY CHAP,
capacities of the elements ; the reader is here reminded of
Renault's investigations l on the various " electrolytic
equivalents " of one and the same element, according to the
nature of the compounds in which it is contained.
These and other observations, together with the above-
mentioned conceptions regarding the nature of solution, have
helped to make clearer the process of electrolysis itself, in so
far that they have shown the intimate mutual relations
existing between chemical and electrical energy. In the
light of this Faraday's law appears as the expression of the
fact that equal quantities of electricity require equivalent
amounts of ions in their passage through different electrolytes.
Electric conductivity and its relations both to physical pro-
perties and chemical composition have frequently been made
the subject of investigation, among others byG. Wiedemann,
Lenz, Long, and W. Ostwald. The recent work of the last-
named chemist, and of Walden and others of Ostwald's pupils,
more especially, has proved that a close connection exists
between the conductivity of acids and their affinity for bases.
Electro-chemistry has been advanced in an extraordinary
degree by the attempts to solve the problem of electrolytic
dissociation; and there can be no question that both
theoretical chemistry and electrical manufactures have been
and will continue to be greatly benefited by such researches.
Organic chemistry, too, has of recent years come into much
closer contact with electro-chemistry, as may be seen in the
important experimental work of Gattermann, Elbs and others,
and in the comprehensive reports of Lob, Neumann and
Elbs.2
It has been attempted, too, to connect magnetism with
chemical properties. The researches of Plticker, and especially
those of G. Weidemann,3 have, in fact, resulted in showing
that there are certain definite relations between the intensity-
of the magnetism of compounds and their chemical nature.
1 Ann. Chim. Phys. (4), vol. xi. p. 137.
2 Cf. Ztschr. fur Mektrochemie, vol. iv. p. 81.
3 Pogg. Ann., vol. cxxvii. p. 1 ; vol. cxxxv. p. 177.
vi ISOMORPHISM AND CHEMICAL CONSTITUTION 505-
Isomorphism, etc.
The investigation of the connection between the forms-
of solid bodies and their composition has been of great
importance for the development of chemical doctrines. The
growth of crystallography benefited mineralogy in the first
instance, but it also led to the discovery of isomorphismr
which — as already stated in the general section1 — exercised
great influence upon the atomic theory. The services
rendered here by E. Mitscherlich, to whom even his friend G.
Rose owed much, may again be recalled at this point.
Mitscherlich did away with the erroneous conceptions which
ascribed the crystalline form of a substance to the presence of
minute quantities of other bodies, and proved irrefutably the
connection existing between crystalline form and chemical
composition. The deduction drawn both by himself and by
Berzelius, viz. that in true cases of isomorphism of several
substances, the chemical constitution of all became known
as soon as that of any one of them was made out, because
similarity of crystalline form is " a mechanical consequence
of similarity in atomic constitution," — this deduction was
soon overthrown by observations of a contrary nature. It
was found that dissimilarly constituted substances might be
isomorphous, and analogously constituted ones heteromor-
phous ; Mitscherlich himself added to his brilliant discovery
of isomorphism that of dimorphism and polymorphism, while
Scherer pointed out cases of the so-called polymeric isomor-
phism, which proved that elementary atoms might be
replaced by atomic groups without change of crystalline
form.
These and other similar observations have resulted in the
view that isomorphism is only to be applied with great
caution as a means for determining chemical constitution,,
otherwise false conclusions are unavoidable. A passing
reference may be made here to the later researches of H.
Kopp upon the relations between isomorphism and atomic
volume, and to those of Schrauf, Pasteur and others upon the
1 Cf. p. 221.
.306 HISTORY OF PHYSICAL CHEMISTRY CHAP.
phenomena of isogonism. The problem — what changes of
crystalline form are produced through the substitution of
particular atoms by other atoms or radicals — has been
systematically attacked by P. Groth1 in the case of certain
groups of organic compounds ; the phenomenon of the partial
alteration of crystalline form, in consequence of such substi-
tution, he terms morphotropism. But much study is still
required for the investigation of this newly opened out branch
of the science. Among recent researches in this field, those
of Retgers, published in the Zeitschrift fur pJiysikalische
Chemie must be mentioned ; apart from his most admirable
work, he has critically examined that of other investigators
like Dufet, Bodlander and Wyrouboff.
The so-called allotropism of elements and compounds is
probably closely connected with polymorphism, i.e. with the
fact that the same chemical substance can exist in different
forms. A most important distinction between the two kinds
of phenomena consists, however, in this, — that we have in
the former case chemical as well as physical differences.
Reference has been already made, under the history of the
elements, to the discovery of certain of the more striking
" allotropic modifications" of these.2 But it may be men-
tioned at this point that material progress has recently been
attained in this branch through the investigation of the
physical constants of such allotropic bodies, e.g. their specific
heat, heat of combustion, atomic volume, etc.3
Speaking generally, chemists lean to the idea that the
same cause underlies both allotropism and polymerism, and
that therefore the former is to be explained by assuming that
different numbers of atoms (of one and the same element)
.are grouped together into dissimilar molecules ; as has been
stated already, the molecular weights of oxygen and ozone
have been established, and thus the difference between them
explained.
1 Pogg. Ann,, vol. cxli. p. 31.
2 Cf. pp. 405-406.
3 Cf. the work of Hittorff, Lemoine, and others.
EARLY WORK IN THERMO-CHEMISTRY 507
Thermo- Chemistry.
It is now a long time since the first attempts were made
to determine the amounts of heat liberated during and in
consequence of chemical reactions, with the object of there-
by arriving at a measure of the affinities active in those pro-
cesses. But the efforts of Laplace and Lavoisier, Davy^
Rumford and others in this direction remained incomplete,
their methods for the estimation of heat quantities being too
inexact.
Thermo-chemistry only became firmly established with
the exact measurement of the thermal changes accompanying
chemical reactions. Of the earlier investigations, those of
Favre and Silbermann on heat of combustion deserve special
mention, because the calorimeter was materially improved by
these chemists. Emphasis must also be laid here upon the
almost forgotten labours of G. H. Hess,1 who deduced from
his own observations the all-important principle of the Gon-
stanz der Warmesummen (i.e. that the heat evolved in the
formation of a given compound is always the same), and thus
taught in 1840 the application of the first law of the me-
chanical equivalent of heat to chemical reactions, before the
law itself had been brought forward.
From this principle Hess 2 established the point that the
.amount of heat evolved in any chemical reaction was always
the same, whether the reaction was consummated at once or
by degrees in separate instalments. This law, taken in con-
1 To Ostwald belongs the merit of having referred with emphasis, in his
Lehrbuch der allgemeinen Chemie, to the services of the St. Petersburg
chemist, Hess, as the founder of thermo-chemistry. On p. 12 of vol. ii. in
the 1st edition of his book (among other passages) Ostwald expresses himself
as follows : "In his fate we find a repetition of that which befel Richter,
the importance of whose work for stb'chiometry was for so long overlooked.
Hess himself (Journ. pr. Chem. , vol. xxiv. p. 420) assigned to the latter his
proper position by correcting the mistake of confounding Richter with
Wenzel, which was due to Berzelius. It is now again needful that the same
loving service should be rendered to him, who on his own part did justice
to an investigator wrongly criticised and too little esteemed in his own
day."
2 Pogg. Ann., vol. 1. p. 385 (1840).
508 HISTORY OF PHYSICAL CHEMISTRY CHAP,
junction with the principle at which Lavoisier and Laplace
had arrived fifty years before — viz. that the decomposition of
a compound into its constituents requires exactly the same
amount of heat as is evolved during its formation! from the
latter — constitutes the basis of thermo-chemistry.
Since the conception of heat as energy of motion found
perfect expression in the mechanical theory, and especially
since the development of the term energy, the above prin-
ciples appear as self-evident deductions from that theory.
The earliest application of the mechanical theory of heat to
thermo-chemical processes was made by Julius Thomsen,1 who
has devoted himself to investigating thermo-chemically the
more important chemical reactions, e.g., the formation of salts,
oxidation and reduction, and the combustion of organic com-
pounds. This branch of the science has been enriched by
him in an extraordinary degree, both by the working out of
new methods and by the systematic investigation of numer-
ous chemical processes. In addition to Thomsen, Berthelot 2
and especially (since 1 8 7 9) F. Stohmann 3 have contributed
1 Julius Thomsen, born at Copenhagen in 1826, where he continues to-
work as Professor at the University, has since 1852 applied himself with the
utmost ardour to building up and developing thermo-chemistry. The large
number of scattered papers, which contain the records of his comprehensive
researches, were some years ago collected together and published by him
in four volumes under the title Thermochemische Untersuchungen ( " Thermo-
chemical Researches").
2 M. P. E. Berthelot, born in Paris in 1827, became professor in the
College de France there, and recently held for short periods the posts of
Minister of Education and Foreign Minister ; he first made himself known
by the beautiful researches, already spoken of, entitled, Sur les Com-
binaisons de la Glycerine avec les Acides. He soon directed his attention
to the synthesis of organic compounds, which at that time had been but
little studied, and in his comprehensive work, Chimie Organique fondde sur
la Synthese (1860), gave a detailed account of the observations and discus-
sions in this branch of the science. Later on he turned with all his energy
to the experimental solution of thermo-chemical problems, which he col-
lected together in the two- volume book, Mdcanique Chimique fondde sur la
Thermochimie (1879) ; while last year (1897) he published a large work in
two volumes entitled Thermochimie. To him we also owe a number of
valuable historical works, dealing more particularly with the development
of alchemy and with the oldest chemical writings of the Middle Age (CL
p. 23, Note 2).
3 Cf. his papers, published in the Journ. pr. Chemie since 1879,
VI THERMO-CHEMISTRY 509
In conjunction with their pupils a large number of important
observations in thermo-chemistry, and have materially as-
sisted in the refinement of calorimetric methods.
The efforts of these investigators were mainly directed to
the discovery of relations between the thermo-chemical values
(which, calculated upon the molecular weights of the reacting
substances, were termed molecular heats) and the chemical
constitution of compounds. The heats of combustion, in
particular, furnished much food for speculations of this nature.
But although regularities of various kinds became apparent,
e.g. with respect to the heats of combustion and heats of
formation in homologous and other series, very great caution
requires to be exercised in forming deductions as to constitu-
tion from calorific values ; this has lately been clearly shown
by Bruhl,1 in a critique upon such attempts. A salutary
limit has thus been placed upon the too great extension and
over- valuation of the conclusions drawn from thermo-chemical
work, a temperate criticism (on the part of Lothar Meyer and
others) having previously done away with the erroneous view
that an absolute measure of affinity was furnished by the
heat evolved or absorbed in the formation or decomposition
of chemical compounds. In spite, however, of this failure,
thermo-chemical investigations will certainly prove to be in-
dispensable for the perfected doctrine of affinity of the future.
It should be added that the results of Stohmann's researches,
e.g. those on the heat of formation of the various hydrides of
benzene, promise to throw light upon the constitution of these
compounds.
Photo-chemistry.
This short account of the growth of physical chemistry
would be incomplete if nothing were said respecting the
Friedrich Stohmann, born in 1832, is Professor of Agricultural Chemistry
in the University of Leipzig, having previously filled a similar post at
Halle, while before that he was Director of the Agricultural Experimental
Station at Brunswick. He is well known by his numerous and fundamental
works, e.g. Handbuch der Zuckerfabrikation, Handbuch der Stdrkefabrika-
tion, etc. ; and by his editorship of the Encyklopedisches Handbuch der
technischen Chemie.
1 Journ. pr. Chemie (2), vol. xxxv. pp. 181, 209.
510 HISTORY OF PHYSICAL CHEMISTRY CHAP.
chemical action of light. The latter, a particular form of
radiant energy, gives rise to various chemical reactions, of
which the great process of assimilation in plants was the
earliest to attract the attention of chemists. The detailed
treatment of this process, first observed towards the end of
the last century, belongs to the recently developed science of
vegetable physiology.
The earliest superficial observations on the action of light
upon compounds of silver were made by Schultze so long ago
as at the beginning of the eighteenth century ; indeed, Boyle
had noticed the blackening of chloride of silver, but had as-
cribed it to the influence of the air. The fundamental ex-
periment which called photo-chemistry into life was made by
Scheele, who thus proved himself a pioneer in this as in
other branches of the science ; he studied the action of the
solar spectrum upon paper covered with silver chloride, and
established the point that the effect begins first and is
strongest in the violet portion. We must recall here too the
experiments of Ritter, who observed the action of the ultra-
violet rays ; and, especially, the epoch-making discoveries of
Daguerre and Talbot, who succeeded, after many attempts, in
permanently fixing light-pictures.1 This gave birth about
1839 to the art of photography, so enormously developed of
recent years.
1 The following notes may be added here upon the history of photo-
graphy (cf . Schiendl's Geschichte der Photographic, published by Hartleben,
Vienna) : Niepce had associated himself with Daguerre in his work, but
did not live to see the perfecting of the Daguerreotype process. Talbot
replaced Daguerre's silver plates by paper rendered sensitive to light.
Among the further advances made in photography may be mentioned the
production of negatives upon glass and the application of substances for
attaching the chloride of silver, e.g. albumen and collodion (Niepce de St.
Victor — the nephew of the Niepce mentioned above — and Legray, 1847) ;
the multiplication of photographic pictures through pressure by means of
the so-called photo-lithography, heliography, and the phototype method,
which in time became superseded by the splendid autotype process
(Meisenbach) and the heliotype one (Obernetter) ; and, lastly, the pre-
paration of plates particularly sensitive to light (bromo-gelatine, etc. ), or, to
speak generally, the introduction of the so-called dry-plate process. Much
interest has been aroused within the last few years by the discovery of
colour-photography by Lippmann and others, but the subject is as yet in
its infancy.
vi PHOTO-CHEMISTRY; ACTINOMETRY 511
The foundation of comparative photo-chemistry, which
is termed actinometry, was laid by the memorable researches
of Bunsen and Roscoe,1 Draper2 having previously made
important experiments in a similar direction. These in-
vestigators, along with others, e.g. B. H. W. Vogel, made
clear the laws to which the actinic rays are subject.
Especially remarkable were the results of the observations
on the absorption of chemically active rays, and upon photo-
chemical induction, a term employed by Bunsen and Roscoe
to designate the process by means of which the substance
sensitive to light was brought into such a condition that it
underwent decomposition proportional in amount to the
intensity of the light. In addition to the above, mention
must be made here of the remarkable researches of Tyndall
upon vapours and gases sensitive to light, in whose decom-
position the action of the light is shown ; thus /he proved
that the vapour of amyl nitrite (to give an instance) was
decomposed by the actinic rays.
The phenomena, whose investigation has just been dis-
cussed, come properly speaking under the doctrine of
affinity, whose task it is to show that chemical reactions, i.e.
the formation and decomposition of chemical compounds,
are the results of definite measurable forces. True, this
important branch of the science is still far from attaining to
such a goal ; but the development of the doctrine of affinity,3
a short sketch of which now falls to be given, shows that
much zealous work is being done with the view of solving
the difficult problems involved here.
1 Phil. Trans, for 1857, p. 355, and for 1863, p. 139 ; or Pogg. Ann.r
vol. c. p. 43 (1857) ; vol. cxvii. p. 531.
2 Phil. Mag. for 1843.
3 Compare the admirably clear rtsumd given by Ostwald in his Lehrbuch
der allgemeinen Chemie, 2nd edition, vol. ii. p. 1.
.312 HISTORY OF PHYSICAL CHEMISTRY CHAP.
Development of the Doctrine of Affinity since the
Time of Bergman.
In a previous section of this book an account has been
given of the earlier efforts to arrive at a knowledge of the
phenomena of affinity. Through most of the speculations
•upon this question, ever since the time of Boyle, there runs
the assumption that the so-called force of chemical affinity
is in the main identical with that of gravity ; only in that
the former is exerted within very small distances, whereby
the form of the material particles has to be taken into
account, are differences between the two forces apparent.
The attempts to estimate the affinity of substances for one
another remained at that time (i.e. previous to Berthollet)
very imperfect, because it was sought to determine qualita-
tirely the relative intensities of the affinities under arbitrary
conditions, without taking physical considerations into
account. This period, from about the time of Geoffrey
(1718) to that of Berthollet (18 00), is characterised by the
bringing out of " Tables of Affinity " ( Verwandtschaftstafeln).1
Bergman's doctrine of chemical affinity and his de-
terminations of the latter belong in part to this evolutionary
stage, although he paid more attention to the influence of
temperature upon the phenomena investigated by him than
his predecessors had done. The reaction proper against the
merely empirical conception of these latter is, however, to be
found in Berthollet, whose Essai de Statique Chimique was a
protest against the neglect of physical conditions during
chemical processes.
Bergmans Doctrine of Affinity.21
Although the work of this investigator belongs to the
phlogistic period, his doctrine of affinity can only be
conveniently treated of here, in order that it may be
compared or rather contrasted with that of Berthollet.
* Cf. p. 138.
2 Cf. Bergman's Opuscula phys. et chem., vol. iii. p. 291 (1783).
vi BERTHOLLET'S DOCTRINE OF AFFINITY 513
Bergman's conception of the phenomena of affinity, or perhaps
it would be more correct to say his method of designating
these phenomena, came into such general adoption that it is
to be found even now, at least portions of it are, in many
text-books.
The chief law of his doctrine states that the value of
the affinity between two substances which act chemically upon
one another is constant under similar conditions, and there-
fore that it is independent of the masses of those substances.
Bergman assumed the universal force of gravity as the cause
of affinity, this being, however, greatly modified by the form
and position of the small particles of the reacting bodies.
Partly from his own speculations with regard to affinity,
and partly from the incorrectly determined composition of
neutral salts, he drew erroneous conclusions with respect to
the magnitudes of the affinities of bases to acids, and vice
versa ; he thus set up the tenet that an acid has . the
strongest affinity for that base of which it saturates the
largest quantity, in order to form a neutral salt. Berthollet,
as will presently be shown, deduced precisely the opposite
from his own assumption, — that mass-action comes into
play in chemical processes. It is noteworthy that Bergman'
recognised the impossibility of carrying out absolute affinity-
determinations, and that he devoted his entire energies to
making relative ones (by decomposing one compound by
another), and then collating these in " affinity tables."
Berthollet 's Doctrine of Affinity.
Against Bergman's ideas, and especially against the
assumption that affinity is independent of the masses of the
interacting substances, Berthollet raised a lively opposition.
Setting out, like Bergman, with the hypothesis that affinity
is identical with gravity, he went on to emphasise the
undeniable conclusion that the forces of chemical affinity,
like those of general attraction, must be proportional to the
L L
514 HISTORY OF PHYSICAL CHEMISTRY CHAP.
masses of the acting substances. The further deductions
from this principle he worked out with masterly clearness in
his Essai de Statique Chimique.
These views of Berthollet did not at the time receive
the recognition which they merited, mainly, no doubt,
because their author came into collision with the established
facts of chemistry by carrying his deductions too far. His
fundamental law of the dependence of chemical action upon
the masses of the substances concerned in it led him to
regard the " chemical effect " of any body as the product of its
affinity and mass. From this he drew the further conclusion
that the formation and composition of a chemical compound
depended substantially upon the masses of the acting
constituents which went to produce it. According to this
view, any two substances must combine with one another in
constantly varying proportions ; with this deduction, how-
ever, Berthollet found himself in a serious dilemma.
But, if he went too far here, he so immensely advanced
the doctrine of affinity and followed up its true aims by a
more discreet application of his fundamental principle, that
the errors into which he fell may well be forgotten. He
pointed out with perfect clearness that it was impossible to
determine the absolute values of chemical affinities, seeing
that these were necessarily dependent to a great extent upon
the physical properties of the substances which were formed or
decomposed by the chemical reactions in question. Ac-
cording to him, such determining (and opposite) properties
were cohesion, i.e. the mutual attraction of the small particles
of any substance for one another, and elasticity, i.e. the
tendency of those particles to occupy the greatest possible
space. He saw in the greater or lesser insolubility of
substances a measure of cohesion, and in their volatility a
measure of elasticity, and by means of such conceptions
conclusively explained chemical changes in which the separa-
tion of a precipitate or the escape of a gas or vapour had a
•determining influence on the course of the reaction. In
fact, he stated distinctly that a complete rearrangement
vi BERTHOLLET'S DOCTRINES SUPPLANTED 515
( Umsetzung) of substances can only take place if cohesion or
elasticity comes into play, and never by the mere action of
affinity alone. He thus brought forward entirely new
points of view, which have borne much rich fruit.
The Supplanting of Berthollet 's Opinions by
other Doctrines.
The first good which resulted from Berthollet's concep-
tion consisted in the recognition of the uselessness of tables
of affinity, in so far as these were supposed to give the
relative affinities of different substances. The important
fundamental idea of his doctrine of affinity, viz. that the
chemical action of a body is proportional to its mass, and is
therefore to be expressed by the product of this into the
affinity (i.e. by a factor still to be determined), led Berthollet
to conclusions which were directly opposed to many known
facts, and to numerous other data worked out at that time
by Proust. The controversy between these two men, which
turned upon the question whether chemical compounds are
built up of elements in proportions which only alter in
amount by certain definite increments, or in proportions
which continually vary, has already been discussed in the
general section (cf. p. 185 et seq.).
In bringing forward his theory Berthollet either neglected
to pay sufficient heed to the stochiometric relations known
at that time, or else his knowledge of these was incomplete.
It is precisely to the circumstance that he carried his theory
of mass-action too far, and made it the starting-point for
the most far-reaching deductions, that we have to ascribe
the miscredit into which his principles — notwithstanding
their clearness — fell, in fact they were held to be totally
erroneous. It was thus that Bergman's doctrine, although
based upon wrong assumptions and therefore leading its
author to false conclusions, kept for so long a time the
upper hand, and this all the more readily since it could be
better made to accord with the atomic theory. The re-
L L 2
516 HISTORY OF PHYSICAL CHEMISTRY CHAP.
vival of Berthollet's principles was reserved for quite recent
times, after various isolated experimental researches had
furnished proof of their admissibility.
After Berthollet's temporary overthrow, the .rapidly
developing atomic theory formed the main subject of in-
terest for chemists ; and hand in hand with its development
went that of the electro-chemical doctrines, whose object it
was to show that the closest connection existed between
electricity and the force termed affinity.
The doctrine of affinity now sought to perfect itself
through the development of electro-chemistry ; Berzelius'
theory caused Berthollet's to be neglected. The successful
work which has since been accomplished, with the object
of getting at the actual relation between electrolysis and
affinity, enables us to perceive now that in those efforts the
investigators of that time were carried too far.
These endeavours could only result in showing the
qualitative differences in the affinities of different sub-
stances ; in fact, the electro-chemical theories reached
their culminating point in the proof of an analogy between
the electrical and chemical properties of substances. Fara-
day's electrolytic law, which threw light upon the quanti-
tative side of electrolytic processes, did not give any informa-
tion as to the relative magnitudes of the affinities of the
substances in question.
The fortunes of the most important of the electro-
chemical theories, that of Berzelius, have already been
described. Blomstrand's ingenious attempt l to bring it back
to life again has indeed shown how valuable it is for the
explanation both of chemical processes and of the constitu-
tion of compounds ; but it was unable at that time to aid
materially in penetrating the obscure domain of the phenom-
ena of affinity.
New prospects were opened out for the doctrine of
chemical affinity by the thorough investigation of thermo-
chemical processes, whose importance for physical chemistry
has already been referred to. But in this case also, as
1 Cf. his work, Die Chemie der Jetztzeit (1869).
vi REVIVAL OF BERTHOLLET'S DOCTRINES 517
in the application of electro-chemical conceptions to the
problems of affinity, the worth of thermo-chemical deter-
minations very soon became greatly over-estimated. Thus,
even Julius Thomsen, who was for a long period the most
eminent worker in this field, regarded the heat evolved
or absorbed in chemical reactions (more especially in the for-
mation and decomposition of compounds) as an absolute
measure of the affinity ; in his view the work of affinity was
transformed into measurable heat.
But although the inadequacy of thermo-chemistry for the
solution of the problems of affinity has now been made
manifest, its present and future significance must not be
depreciated. On the contrary, by the careful application of
thermo-dynamic principles to the interpretation of chemical
processes, great benefits have already accrued to the doctrine
of affinity.
The Revival of Berthollet's Doctrines.
The most powerful impulse to a further healthy develop-
ment was given to the doctrine of affinity by the revivifica-
tion of Berthollet's theory. This was accomplished in its
fullest extent by the publication in 1867 of the work of two
Scandinavian investigators, Guldburg and Waage.
Several years previous to this H. Rose had proved with
absolute clearness the mass-action of water in many reactions,
e.g. in the decomposition of alkaline sulphides and of
potassium bisulphate, and in the formation of basic salts.
The attention of such distinguished workers as Rose,
Malaguti, Gladstone and others had further been directed to
the study of the mutual decomposition of two salts, whether
those were soluble or one of them was insoluble. In fact,
attempts were made to work out in various ways the
relative affinities of particular substances, and thus to solve
a problem which Berthollet had sketched out theoretically.
The ideas of the latter received, lastly, valuable
experimental confirmation from the extremely important
researches of Berthelot and Pe'an de St. Gilles1 on the
1 Ann. Chim. Phys. (3), vols. Ixv. Ixvi. and Ixviii.
518 HISTORY OF PHYSICAL CHEMISTRY CHAP,
formation of compound ethers and ether-acids from an
alcohol and an acid. In subsequent theoretical discussions,
these and the more recent valuable experiments of Mensch-
kutkin1 (which furnished information with regard to the
chemical equilibrium existing between different substances
and to the time-rate of reaction) were applied with success to
proving and confirming the correctness of Berthollet's axioms.
The observations on chemical equilibrium in reciprocal
processes especially contributed to the general adoption of
those doctrines of Berthollet ; it was thought then (and still
is) that the values thus obtained offered the surest data for
arriving at the relative affinities of substances taking part in
a reaction. With regard to the ideas held respecting such
states of equilibrium, the opinion prevailed for a long time that
a statical equilibrium must be assumed. A reversal of this
was prepared for by the view originated and propounded by
Williamson2 in 1850, which was also worked out in-
dependently by Clausius several years afterwards, viz. that
the atoms of substances are in a state of continual motion, not
merely during chemical reactions but also when the sub-
stances are apparently at rest. A dynamical equilibrium
thus took the place of a statical, i.e. an equilibrium of the
opposing reactions. Pfaundler has of late ingeniously applied
such speculations to the explanation of the phenomena of
dissociation and of reciprocal reactions generally.
But although Williamson emphasised the point that his
speculations were in accord with Berthollet's principles, a
sufficiently secure and broad basis was still wanting, upon
which they could at that time be further developed. Such
a foundation for the building up of the doctrine of affinity
was furnished by the above-mentioned work of Guldberg and
Waage,3 who took Berthollet's axioms as their immediate
1 Cf. Ann. Chem., vol. cxcv. ; Journ. pr. Chemie (2), vols. xxv. xxvi.
and xxix.
2 In a paper read before the British Association at Edinburgh ; Ann.
Chem., vol. Ixxvii. p. 37,
8 Etudes sur Us Affinitds Chimiques (1867) ; this was published in German
in the Journ. pr. Chem. (2), vol. xix. p. 69.
vi THE GULDBERG-WAAGE THEORY 519
starting-point, reanimated these anew, and proved their
agreement with facts.
' Like Berthollet, the investigators just named stated the
chemical action of a substance as being proportional to its
active amount,1 the latter being given by the quantity con-
tained in unit of space. The intensity of the interaction of
two substances is expressed, according to them, by the pro-
duct of the active amounts ; but a coefficient 2 still remains to
be determined which shall express the dependence of the
reaction upon the nature of the substances taking part in it,
the temperature, and other factors. By the aid of such
hypotheses the relations existing between the amounts of
the reacting substances and their actions 3 can be deduced
mathematically. Important conclusions have also been drawn
from them with respect to time-rate of reaction and chemical
equilibrium, and these have been found to agree sufficiently
well with the results of actual experiment.
The latest Development of the Doctrine of Affinity.
Guldberg and Waage's theory, based as it was upon
Berthollet 's principles, has had an extraordinarily stimulating
effect. It has led in particular to the successful determina-
tion of the specific affinity-coefficients of different substances,
especially of bases and acids ; and these experimentally-
determined constants have been made use of to test the
correctness of the theory itself. Among the work done with
this aim in view, that of Ostwald 4 deserves special mention ;
he has determined by different methods, volumetric and
optical, the manner in which a base is distributed among
different acids present in excess, and has deduced from
this the specific affinity-coefficients of the latter. Julius
1 " .... seiner wirksamen Menge proportioned"
2 Such affinity-coefficients have hitherto only been determined in par-
ticular cases, and then only approximately.
3 Wirkungen.
4 Published in the Journ. pr. Chem. since the year 1877.
520 HISTORY OF PHYSICAL CHEMISTRY CHAP.
Thomsen 1 had previously attempted to solve the same
problem by thermo-chemical methods.
Ostwald 2 further sought, some years ago, to deduce the
affinity-coefficients of acids from reactions which go on with
a measurable velocity under the influence of those acids, e.g.
the decomposition of acetamide and of methyl acetate, and
the inversion of cane sugar ; in this case too, the results
obtained have shown a sufficiently near agreement with
calculation. The reader is referred, lastly, to the remarkable
relations — already spoken of — which have been discovered
by Arrhenius, and also by Ostwald, between the affinity-
coefficients and the capacity for (chemical) reaction of acids
and bases on the one hand, and their electrical conductivity
in dilute solution on the other. Ostwald's researches 3 have
thrown a surprisingly new light upon the chemical relations
— especially upon the constitution — of the compounds investi-
gated, showing as they do that the affinity-coefficients of
substances alter definitely according to the constitution of
the latter. At the same time it has turned out that the
position or function of the atoms has a determining influence
upon these coefficients, this important fact being most
apparent in the case of isomeric compounds, e.g. the oxy-
benzoic and chloro-propionic acids, etc.4 The general
conclusion to be drawn from these and other allied researches
is that the specific chemical actions of acids depend upon
their hydrogen ions and those of bases upon their
hydroxyl ions.
The limits, within which this short account of the de-
velopment of the doctrine of affinity is necessarily con-
fined, would be widely overstepped were the results of other
investigations — even taking only those of importance — to be
described. Merely a passing reference can be made to the
work of Wilhelmy, which has led to a better knowledge
1 Pogg. Ann., vol. cxxxviii. p. 575.
2 Cf. Journ. pr. Chem. for 1884 and 1885.
8 Cf. Journ. pr. Chem. (2), vol. xxxii. p. 300 ; and especially Ztschr.
phys. Chem., vol. iii. pp. 170, 241, and 369.
4 Cf . also Raoult's work bearing on affinity-coefficients, as developed by
Planck and others.
vi AIMS OF THE DOCTRINE OF AFFINITY 521
regarding time-rate of reaction, and to that of Menschutkin,
van 't Hoff, Horstmann and others, which has resulted in
making clear the conditions of chemical equilibrium in
various reactions.
The hypothesis that the small particles of substances are
in continual motion, not merely during chemical reactions,
but also when the whole system is in a state of equilibrium,
is now held to be indispensable for the new doctrine of
affinity. The clear comprehension of the various kinds of
energy, and especially of the relation of chemical energy to
the other forms, such as electric and thermic energies, etc.,
has resulted in greatly developing this branch of the science.1
The chief aim of the doctrine of affinity is to convert chemistry
into a branch of applied mechanics — an aim which Berthollet
and Laplace, notwithstanding the imperfection of the appli-
ances at command in their day, had the prescience to
designate as the highest possible.
1 Compare the able treatment of energetics in Ostwald's Lehrbuch der
allgemeinen Chemie, 2nd edition, vol. ii.
522 HISTORY OF MINERALOGICAL CHEMISTRY CHAP.
A SKETCH OF THE HISTORY OF MINERALOGICAL
CHEMISTRY DURING THE LAST HUNDRED YEARS. *
Mineralogy only attained to the rank of a science after it
had recognised the fact that chemistry was indispensable to
it for ascertaining the composition of minerals. It is true
that even in this century Mohs,2 who did so much for
minerals physics, almost denied that the chemical characters
of minerals had any signification ; but the system which he
set up was only temporarily adopted by a few scientists.
The benefits which accrued to mineralogy from the applica-
tion of chemical aids were so obvious that the latter could
never again be dispensed with. Mineralogy has been brought
to its present high position by the joint assiduous work
of mineralogists and chemists together. The beautiful aim
— of making clear the connection which exists between the
physical and chemical properties of individual minerals —
has firmly retained its place for the mineral chemist ever
since the labours of Berzelius, Mitscherlich, G. and H. Rose,
and others were consummated.
The first modest attempts to gain a knowledge of the
chemical composition of minerals were made in the seven-
teenth and first half of the eighteenth centuries, but these
did not extend beyond mere superficial observations of a
few qualitative reactions. In the second half of last century,
however, there was much important preparatory work done,
1 Cf. Kopp, Oeschichte der Chemie, vol. ii. p. 84 et seq. ; v. Kobell,
Geschichte der Mineralogie (1650-1860), more especially p. 303 et seq.
2 Mohs set up the axiom that a mineralogist had merely to consider
the natural-history properties of minerals, i.e. crystalline form, specific
gravity, hardness, and so on. If their chemical behaviour is taken inta
account, then, he expressly states, mineralogy oversteps its legitimate
bounds and entangles itself in difficulties. This renunciation of the most
important aid to mineralogical research is certainly characteristic.
Berzelius was fully justified in comparing such a mineralogist to a man who
objects to use a light in the dark, on the ground that he would thereby see
more than he actually requires to do.
vi THE EARLIER HISTORY OF THIS BRANCH 523
which helped materially to found the science of mineralogy.
Mineral chemistry had its distinguished exponents in
Bergman, and, a little later, in Klaproth and Vauquelin,
whose services in devising methods for the analysis of
inorganic substances have already been referred to.1 The
chemical investigation of minerals was carried on at that
time, upon the principles which they laid down, by numerous
other workers, among whom we may name Lampadius,
Bucholz, Wiegleb, Westrumb, Valentin Rose the younger,
Kirwan, Gadolin and Ekeberg.
The extraordinary benefit which accrued to mineralogy
from the introduction of the blowpipe by Cronstedt, and its
subsequent use by Gahn, Bergman, Rinman, and particularly
Berzelius, may again be emphasised at this point.2
Even before the gradual development of a mineral
chemistry, and also simultaneously with it, Rome" de 1'Isle,
Werner, Haliy and Bergman had recognised crystallography
as being essential to the study of mineralogy, and had
applied themselves to it. Haiiy, in particular, achieved
wonderful results in this branch ; he referred back the
various crystalline forms to a few primary ones, and took
account of chemical as well as of physical properties in
classifying minerals. That he carried his deductions too
far here is seen from his well-known axiom that difference
in crystalline form signifies also difference in chemical com-
position.
The endeavours made to classify minerals during that
period are for the most part characterised by the desire to
recognise their chemical as well as physical properties. If
this had only a subordinate signification in Cronstedt's,
Hauy's and especially Werner's systems, it was on the
other hand put prominently forward by Bergman3 as an
essential aid to the classification of minerals, so far as this
was possible with the then existing chemical knowledge.
But few of the mineralogists of that day, however, subscribed
to Bergman's principles, most of them giving in their
1 Cf. p. 384 et seq. 2 Cf. p. 385.
3 In his Sciagraphia Eegni Mineralis, etc. (1782).
524 HISTORY OF MINERALOGICAL CHEMISTRY CHAP.
adhesion to Werner's system, in which only a very modest
place was assigned to mineral chemistry.
A new life began for mineralogical chemistry when Ber-
zelius turned himself to its study. Basing his arguments upon
his own comprehensive labours, which had for their aim the
exact determination of the composition of minerals and
artificial inorganic compounds, he was enabled to show that
the doctrine of chemical proportions (and therefore the
atomic theory) was applicable in its fullest extent to minerals
also.1 He was the first to characterise these latter as
being in every respect "chemical compounds." At the
same time this gave him occasion to classify them simi-
larly to substances prepared artificially, and thus arose his
Chemical System,2 in which he gave definite expression to
the view that mineralogy should only form a part of, or an
appendage to, chemistry. The order of the minerals in his
system was determined by the position of their electro-positive
constituents in the so-called " tension series." Ten years
later 3 Berzelius altered his principle of classification, in so
far that he came to look upon the electro-negative con-
stituents as primarily determining this, and he arranged the
minerals accordingly. For his two main classes he took
non-oxidised and oxidised substances, and between these
he divided minerals with a marvellous perspicacity. All
previous attempts at classifying minerals according to
chemical principles were thrown into oblivion by Berzelius'
system.
The development of this system, whose main features
were subsequently reproduced in later classifications, was
influenced in the highest degree by an observation made by
N. Fuchs, viz. that certain substances can replace each other
in minerals, and still more by the extension of this doc-
trine through Mitscherlich's discovery of isomorphism.4 The
results of the analyses of minerals hitherto obtained were
henceforth regarded from entirely new points of view and
were in many cases simplified to an unexpected extent. A
1 Of. p. 205. 2 Schweigger's Journ., vols. xi. and xii. (1814),
3 Leonhard's Zeitschrift fur Mineralogie, vol. i. 4 Cf. p. 221.
vi LATER DEVELOPMENTS OF MINERAL CHEMISTRY 525
high, perhaps too high, significance was now attributed to
crystalline form in its connection with chemical composition.
This over-estimate quickly became manifest after Mitscherlich
discovered the first cases of dimorphism, — to be extended
later on to tri- and polymorphism. Haiiy's principle — that a
difference in crystalline form also means a difference in
chemical composition — was thereby overthrown; and, in spite
of the opposition of this distinguished investigator, the
doctrine of isomorphism took its place triumphantly in
mineralogy.
The various mineralogical systems which were brought
forward after that of Berzelius, i.e. after the year 1824,
are almost all characterised by the endeavour to classify
minerals according to their chemical composition, a greater
or lesser signification being at the same time attached to
their physical properties. In addition to G. Rose's classifi-
cation of mineral bodies, which rested upon a purely chemical
basis, the mixed systems of Beudant, C. F. Naumann,
and Hausmann may be named here as having become best
known.
The nomenclature of minerals has by no means kept
equal pace with their strictly scientific investigation. The
empirical principle still prevails here, this being apparent
from the way in which minerals are named after their
discoverers, or after localities in which they are found, or
according to their physical properties, etc., instead of the
name expressing or at least indicating their chemical com-
position.
Mineralogy owes its present flourishing condition to the
immense development of mineral chemistry. Berzelius and
his pupils, among whom Chr. Gmelin, E. Mitscherlich,
Wb'hler, H. and G. Rose, Svanberg and Mosander may be
mentioned, were the first to really open up the ground
which Bergman, Klaproth, Vauquelin and others had pre-
pared. It is impossible to give a detailed account here
of the wealth of new methods which have been devised for
the analysis of minerals, and for the separation of their
individual constituents. The almost inexhaustible field of
526 HISTORY OF MINERALOGICAL CHEMISTRY CHAP.
minerals has ever since then been investigated chemically
by numberless workers. To the problem which naturally
comes first, viz. the establishment of their empirical composi-
tion, the further and higher one was added of getting at
their chemical constitution. The silicates in particular, on
account of their extraordinary variety, have given rise to
continually renewed investigations.1
The limits of this short account of the development of
mineralogical chemistry do not permit of citing even a few
examples of the services rendered to this branch of the science
by such men as Stromeyer, Th. Scheerer, Rammelsberg,2
Bunsen and others. Among other chemists who have done
good work for mineralogical chemistry the following may be
named : — v. Bonsdorff, O. L. Erdmann, Marignac, Th. Thom-
son, Blomstrand, Deville, v. Hauer, Hermann, Th. Richter,
Sandberger, Smith and Brush, Streng, Cl. Winkler, P.
Jannasch, Th. Petersen ; to these many more names might
be added.
1 Efforts have not been wanting to apply specially to minerals the more
recent chemical views which have been arrived at with respect to the con-
stitution of organic compounds. Wurtz was the first to do this, by com-
paring the poly-ethylene alcohols (discovered by himself) with the poly-
silicic acids. That such attempts to explain the structure of the most
complex silicates have often overshot the mark, and have therefore re-
mained unfruitful, is due to the circumstance that the methods employed for
gaining an insight into the constitution of organic compounds cannot as a
rule be applied to inorganic.
2 C. Rammelsberg, born in Berlin in 1813, worked from the year 1840
partly at the Technical College (Gewerbeakademie) and partly at the Uni-
versity there, and was from 1874 until a few years ago head of the second
chemical laboratory of the latter ; he is since dead. His researches, which
greatly enriched inorganic and especially mineralogical chemistry, appeared
for the most part in Poggendorfs Annalen. He rendered very great service
by the publication of his Handbuch der Mineralchemie (second edition,
1875), and of his Krystallographisch-physikalische Chemie (1881-82).
vi ARTIFICIAL PRODUCTION OF MINERALS 527
The Artificial Production of Minerals * — Beginnings of
Geological Chemistry.
To the older analytical method, which was the one
naturally first followed in the investigation of minerals, the
synthetic method has in recent times been added, with the
result that mineralogical chemistry has been enriched by an
extraordinary number of new facts and has led to the de-
velopment of geological chemistry. The endeavour to imitate
and to explain the natural production of minerals, by pre-
paring them artificially under various conditions, has been
the cause of many memorable researches, of which a short
account must be given here.
After Berzelius had defined minerals as chemical com-
pounds whose composition was dependent upon the same
laws as that of compounds artificially produced, the problem
at once arose of preparing mineral substances from their
components. But several decades passed by, during which
mineral chemistry was developed by improved analytical
methods, before the synthesis of minerals was definitely
taken in hand with this conscious aim in view. Only
isolated observations on the artificial formation of such sub-
stances, e.g. of calc-spar and arragonite by G. Rose, and some
experiments made by Gay-Lussac, Berthier and Mitscherlich,
fall to be recorded during the first half of this century ; 2 the
brilliant development of this branch of mineralogical or
geological chemistry only began in 1851 with the memor-
able labours of Ebelmen, Durocher, Daubr^e and Se"narmont.
These investigators elaborated a series of methods which led
to the production of minerals under conditions similar in
part to those found in nature. It was justifiable to draw
careful deductions with respect to naturally occurring pro-
1 Cf. Die Kunstlich dargestellten Mineralien, etc. ("Artificially-prepared
Minerals"), by C. W. C. Fuchs (Haarlem, 1872); and the Synthese des
Mine'raux et des Roches, by Fouque and Michel Levy (Paris, 1882).
2 The earliest observation of this nature was doubtless that made by
James Hall upon the transformation of chalk into marble in 1801.
528 HISTORY OF MINERALOGICAL CHEMISTRY CHAP,
cesses from these methods of formation ; at any rate,
hypotheses which were brought forward to explain the
formation of minerals and rocks could be put to the test in
this way. Geology thus gained a firmer foothold, and found
in chemistry an indispensable helpmeet.1
Reference may be made here to Bunsen's beautiful in-
vestigations 2 upon the geological conditions of Iceland, and
especially upon the geysers, and to those on the formation of
volcanic rocks, all of which were productive of new views ;
and also to the labours of G. Bischof,3 who was indefatigable
in advancing chemical geology.
Among the distinguished array of investigators who made
further advances in this direction, and, in particular, who
discovered new modes of formation of minerals, H. St. Claire
Deville and Troost, Becquerel, Debray, Hautefeuille, Wohler,
Rammelsberg, R. Schneider, and especially Fouque* and
Michel Levy, stand out pre-eminent. Of recent years Friedel,.
Sarasin and Moissan have carried out important syntheses of
minerals.
The chief founders of the synthetic method in mineral-
ogical-geological investigations have been Frenchmen, and so
reference is with perfect justice made to a French school in
this branch, the five gentlemen last named being its principal
exponents of recent years.4
The modes of formation of minerals observed by them
1 Senarmont expressed himself in the following significant words with
regard to the necessity of chemistry for geology : " (Test a la chimie minera-
logique, que la gdologie doit I'utile contrdle experimental de ces conceptions
rationelles. Les mindraux cristallisds ont, en ejffet, une origine toute chimique,
et c'est I' 'experience chimique qui doit servir d'appui a la geologie, si elle veut
faire unpas de plus dans Pe'tude des roches, qui en sont composes."
2 Ann. Chem., vol. Ixii. p. 1 ; vol. Ixv. p. 70.
3 Cf. his Lehrbuch der chemischen Geologie.
4 Fouque" and Michel LeVy consider that the cause of this pre-eminence
in the above field is to be found in the " nature of the French national
character." The argument with which they support this assumption (see
p. 5 of the work, Synthese des Mindraux, etc. ) is so characteristic, that it
may find a place here : " Notre gdnie national rdpugne & Vidde d'accumuler
un trop grand nombre de fails scientifiques, sans les coordonner, et si cette
tendance nous entraine quelquefois cl des hypotheses hasarddes, elle a, d'autre
part, le mdrite, de nous induire aux experiences synthdtiques."
vi SYNTHESES OF MINERAL SUBSTANCES 529
vary greatly, the processes being partly wet and partly fusion
ones. To mention only one or two of the more important,
take the production of many natural minerals by the slow
mutual decomposition of two salts in solution, e.g. the form-
ation of quartz and calc-spar from gypsum and silicate of
potash in presence of carbonic acid ; the deposition of arti-
ficial minerals from solution (formation of gypsum) ; the pro-
duction of calc-spar or arragonite according to the conditions
prevailing ; the decomposition of various substances by water
under increased pressure (formation of quartz, wollastonite,
apophyllite, etc.); and, lastly, the production of numerous
minerals by processes requiring fusion and a white heat — pro-
cesses similar to those which go on in volcanoes (formation of
tridymite, olivine, and other silicates).
The synthesis of the numerous sulphides of copper, iron,
zinc and cadmium, partly in the dry and partly in the wet
way, also deserves mention, and this applies too to the arti-
ficial production of gems, e.g. of the ruby by Fre'my and of the
diamond, the latter having been obtained by Moissan in
minute crystals, by suitably cooling a carboniferous iron from
an excessively high temperature.
Since nature but seldom allows her workshops to be spied
into, the numerous experiments on the production of minerals,
made in imitation of natural processes, and which have been
carried to a successful issue, possess the highest significance
for the explanation of those processes. The repeated proofs
that one and the same mineral can be artificially prepared in
the most diverse ways, by wet as well as by fusion methods,
has rendered the former one-sided conception of geological
processes (i.e. the view that rock-masses have been produced
either in the wet way or by igneous action) almost impossible
now. The synthesis of minerals has riveted still more firmly
than before the already long-established link between
mineralogy and chemistry.
M M
530 HISTORY OF AGRICULTURAL CHEMISTRY CHAP.
DEVELOPMENT OF AGRICULTURAL AND OF
PHYSIOLOGICAL CHEMISTRY
The history of these branches of chemistry is primarily
associated with the work done by Liebig, of which a short
description has already been given in the General Section.
It is true that this gifted investigator had many predecessors,
who found out various isolated chemical facts of great import-
ance for vegetable and animal physiology ; but it was he who
first with far-seeing glance collected such facts together under
general points of view, and conjoined them with still more
important observations of his own. The ideas of a Palissy
upon the necessity of mineral substances for plant life ; l the
investigations which towards the end of the seventeenth
oentury led Malpighi and Mariotte to definite conclusions with
respect to the nutrition of plants through their leaves and
roots ; the bold and comprehensive speculations of Lavoisier 2
regarding metabolism in plants and animals, — his conviction
that the life processes are made up of a series of chemical
reactions ; lastly, the work of Fourcroy, Vauquelin, Proust,
Berzelius and Chevreul upon products of the animal body ;
— all these, together with other labours, served to prepare
the ground upon which Liebig afterwards raised the edifice
of chemistry in its relation to agriculture, physiology, and
pathology.
Those branches of chemistry are most closely interlaced
with organic, for one of their main problems consists in iso-
lating compounds of an organic nature and establishing the
composition of these. To this is added the further task of
elucidating the role which such substances fill in the organism.
Vegetable and animal physiology are especially indebted to
chemistry in questions of nutrition.
1 Cf. p. 90.
2 These are set forth in a paper written in 1792, but only published in
1860 (in vol. iv. of the (Euvres de Lavoisier}.
vi THE HUMUS THEORY 531
Agricultural Chemistry and Vegetable Physiology.1
The work done in physiological chemistry towards the
end of last century and the beginning of this by Priestley,
Ingen-Houss, Senebier and Th. de Saussure had led to many
important results with respect to the nutriment of plants.
One might now suppose that, from the analysis of the ashes
of plants, a distinct connection between the plants and the
soil would have been apparent. The decomposition of car-
bonic acid by the leaves, which was observed by those workers,
ought, one might further suppose, to have pointed to car-
bonic acid as the main source of the organic matter of plants.
In like manner the early made observation that salts of am-
monia were highly conducive to the growth of vegetables,2
might have found an explanation in the recognition of am-
monia as the source of their nitrogenous constituents.
These deductions, however, which now appear to us self-
evident, were not drawn, and it was sought to credit humus
as being the universal nutrient of plants, without paying any
heed to those older fundamental observations which have
just been mentioned. The processes of nutrition of plants
were thus entirely misunderstood, for, according to this
doctrine, they fed like animals upon organic matter.
This assumption, which dominated agricultural chemistry
for many decades, found its chief advocates in Germany and
France in Albrecht Thaer 3 and Mathieu de Dombasle re-
spectively. In their opinion inorganic salts, the importance
1 For the literature consulted on this subject (in addition to the books
and papers cited below), see the Geschichte der Botanik, by J. Sachs ; Lehr-
buch der Pflanzenphysiologie, by Pfeffer ; Lehrbuchder AgrihUturchemie, by
W. Knop ; Chimie et Physiologie appliquees a V Agriculture, etc., by L.
Grandeau ; Neues Handworterbuch der Chemie, vol. ij. pp. 119 and 1012 ;
and Ville's Artificial Manures etc. (English Edition by Crookes).
See also Storer's Agriculture, in some of its relations to Chemistry (2 vols.).
2 Nicolas Leblanc pointed out the importance of salts of ammonia in
this respect so long ago as at the end of last century.
3 Cf. his work, Grundsdtze der rationellen Landunrthschaft ("Principles
of Rational Husbandry"). Even Saussure, the originator of the doctrine
of plant nutrition, fell into the humus theory error.
M M 2
532 HISTORY OF AGRICULTURAL CHEMISTRY CHAP.
of which could not be absolutely denied, acted merely as
stimulants, and not as if they were essential to the growth
of the plant.1 Indeed, Thaer held that the formation (i.e.
creation) of earths in plants through their vital forces was
possible. In this assumption he followed the opinion of
Schrader, who so early as the year 1800 imagined that he
had proved by actual experiments the generation of the
ash-constituents of plants by the vital forces.2
Liebig put an abrupt end to this period of unscientific
attempts at explaining the process of plant nutrition by his
critical demolition of the humus doctrine. Taking his stand
upon a large number of investigations carried through by
himself and his pupils, in conjunction with earlier work done
by others, he brought out in 1840 his book, Die Chemie in
ihrer Anwendung auf Agrikultur und Pkysiologie5 ("Chemistry
in its Application to Agriculture and Physiology ") ; in this
he did battle with the arbitrary axioms of the humus theory,
and completely undermined the foundations of the latter,
hitherto looked upon as secure. The following sentences by
Liebig constitute the quintessence of his doctrine ; they
already contain the complete programme of the agricultural
chemistry which has been created since that time. " The nutri-
tive materials of all green plants are inorganic substances." . . .
" Plants live upon carbonic acid, ammonia (nitric acid), water,
phosphoric acid, sulphuric acid, silicic acid, lime, magnesia,
potash and iron ; many of them also require common salt."
..." Dung, the excrementa of the lower animals and of man,
does not act upon plant life through (the direct assimilation
of) its organic elements, but indirectly through the products
of its decomposition- and putrefaction-processes, i.e. by the
transformation of its carbon into carbonic acid, and of its
nitrogen into ammonia or nitric acid. Organic manure, which
1 Several writers have ascribed to Sprengel, who achieved so much for
botany, the merit of having proved the indispensability of the ash-
constituents for plants, but this is incorrect.
2 This erroneous view was first combated upon good grounds by Saussure,,
and then by Davy.
3 The incitement to this work came from the British Association for
the Advancement of Science.
vi LIEBIG'S GREAT SERVICES 533
consists of portions or debris of plants and animals, may be
replaced by the inorganic compounds into which it breaks
up in the ground." 1 From these axioms Liebig drew the
all-important conclusion that the soil must be replenished
with whatever constituents have been withdrawn from it
by the culture of plants, if its exhaustion is to be provided
against.
In the further development of this pregnant doctrine,
whose victory over the old system was soon complete, dis-
tinguished pupils of Liebig took part as well as himself.
Indeed nearly every agricultural chemist since that time has
come either directly or indirectly from Liebig's school.
Boussingault 2 strove independently after similar goals, and
the services which he rendered in earring out researches on
the nutrition of plants by new methods must be emphasised
here. The now world-famous field experiments of Lawes and
Gilbert at Woburn in Bedfordshire, begun more than half a
century ago, and which are being continued with unabated
vigour, will always hold a distinguished place in the history of
agricultural chemistry. And the service which the late
Georges Ville rendered to this branch of the science by his
work in France should also be borne in mind.
Definite researches were first made in order to explain
the chemical conditions existing in the soil, from which
plants are supplied with their purely mineral constituents.
These included the investigation of the processes involved in
the weathering of rocks, through which soil is produced.
Liebig, Boussingault, Deherain, Dietrich and others showed
by their investigations what were the parts played by the
1 Liebig himself carried out practical experiments in manuring, and
succeeded in changing a sandy piece of ground in the neighbourhood of
Giessen into a productive garden by the aid of mineral manures alone.
2 J. B. Boussingault, who was born in 1802 and who died in 1886, first
became known through his adventurous journeys in South America, where
he turned his catholic knowledge to brilliant account. After returning to
France he devoted himself more and more to agricultural-chemical
questions, which he treated partly in experimental researches, and partly
in his detailed works, ticonomie Rurale ; Agronomie ; Chimie Agricole et
Physiologic (1864).
534 HISTORY OF AGRICULTURAL CHEMISTRY CHAP.
active agents here, — water, carbonic acid and oxygen;
they also came to the conclusion that free nitrogen as such
was not directly assimilated by plants, but this view has
been overthrown by the work of Ville, Hellriegel and others
(Of. below). It is only after rocks have been "weathered" that
the inorganic substances necessary for the nutrition of plants
are brought into such a condition that they can be as-
similated by these. The valuable experimental work done
by E. Wolff, Henneberg, W. Knop, F. Stohmann, Zoller,
Lehmann and Nobbe, among others, upon the composition
of different soils must be mentioned here, and also the closely
allied experiments by them on the nutrition of plants in
sterile soils and in solutions of salts, — dry culture &&& water
culture. These methods have -served to solve the most im-
portant questions regarding plant nutrition.
These researches all went to prove that the same substances
as are found in the ashes of plants are the true nutrients of
the latter, and are absolutely indispensable to them. But
they did more than this, in showing the significance — indeed,
the determining influence — as regards nutrition, not merely
of the nature of the nutritive materials contained in the
soil, but also of the form in which these are present, and
of their action upon the other constituents.
The earliest series of experiments on the absorption by
different soils of the mineral constituents which serve as
food for plants was due to Liebig, while similar work by
Henneberg and Stohmann, Peters, Knop, Zoller, etc., must
also be recorded ; these observations were likewise of great
importance for the explanation of the action of manures.
A few words must be added here about nitrification in
soils and the assimilation of free nitrogen by plants, —
the most important discoveries in agricultural chemistry of
recent years. So long ago as 1849 the late Georges Ville, then
director of the Agricultural Experiment Station at Vincennes,
proved by actual experiment that certain plants could and
did assimilate free atmospheric nitrogen ; but at the time
his conclusions were strongly disputed, being directly opposed
to those of Boussingault and Liebig, and also to subsequent
vi NITRIFICATION ; ASSIMILATION OF NITROGEN 535
investigations by Lawes, Gilbert and Pugh in 1857. An
important experiment bearing on the point and extending
over many years was begun in 1 8 5 5 by Herr Schultz of
Lupitz in Altmark, Germany. He grew lupines on very
poor soil with the addition of non-nitrogeneous manures only,
and found that notwithstanding this, the soil became richer
in nitrogen year by year. The next step towards the solu-
tion of the question was the discovery in 1877 of the now
well-known process of nitrification in soils by MM. Schloesing
and Miintz, this nitrification being the work of definite
microbes, some of which have been isolated by Winogradsky,
Warington, and P. Frankland ; while the recent work of
Hellriegel and Wilfarth (in 1888), Frank, Schloesing, Ber-
thelot and others has proved that the direct assimilation of
atmospheric nitrogen by leguminous plants is brought about
by the agency of certain micro-organisms originally present
in the soil, which enter the root at a very early period of the
plant's growth. At the place where the micro-organism
enters, a disturbance is set up and a nodule or tubercle
formed, in which the micro-organism multiplies rapidly.
These nodules are highly nitrogenous substances, and through
their agency the plant is somehow enabled to assimilate the
free nitrogen of the air and to convert it into albuminous
compounds ; but how this is actually brought about has still
to be explained. Cultures of these specific bacteria are now
prepared on a manufacturing scale, under the name of
nitragins, for application to soils naturally deficient in them ;
but whether they will actually be of value on ordinary arable
land remains to be proved.1
Notwithstanding, however, that an immense number
of new facts have been brought to light through these
and other labours, the fundamental principles of Liebig's
doctrine have undergone no alteration since he first gave
them to the world in his pioneering work of 1840. He
clearly recognised in all its broad features how plants draw
their nutriment from the constituents of the air and the soil.
1 Cf. A. P. Aitken, Transactions of the Highland and Agricultural
Society for 1898, p. 299.
536 HISTORY OF AGRICULTURAL CHEMISTRY CHAP.
Upon this he based his doctrines of rational husbandry,
which have already borne the richest fruit, and in the
elaboration of which scientific and practical men are still
engaged.
Development of Phyto-Chemistry.
After the importance of various inorganic substances for
the life of plants had come to be recognised, the pressing
question arose for physiologico-chemical investigation — How
and in what phases is the formation of organic substances
from carbonic acid, ammonia and water consummated ?
The problem to be solved here consists in isolating the
chemical compounds present in the various organs of plants,
and in establishing their physiologico-chemical relations to
one another, — a magnificent task, and one which has already
occupied many able investigators.
The conversion of carbonic acid into organic com-
pounds under the influence of water and light, the process
of the assimilation of carbon, which was already correctly
apprehended in its main outlines by Saussure,1 has
naturally formed the subject of numerous investigations.
Thus recent researches by Lommel, Pfeffer, N. J. C. Muller,
Engelmann, and others have elucidated the nature of the
light rays which are active here. Much valuable work too
has been done upon chlorophyll, although the opinions of
men like Sachs, Pringsheim, etc., differ as to the part which
1 Cf. his Recherches Chimiques sur la Vegetation (1804). Previous to
this Ingen-Houss had observed the assimilation of carbonic acid and water
by the leaves of plants, but, being enchained by the phlogistic theory, had
not perceived that the oxygen thereby liberated came from this carbonic
acid. The above relation was first made clear by Senebier, and became a
certainty after Saussure's masterly researches, through which the balance
between the substances absorbed and eliminated was approximately ascer-
tained. Ingen-Houss, too, and Saussure still more definitely, recognised
that the converse of this assimilation process (i.e. a breathing in of oxygen
and giving out of carbonic acid) goes on in various parts of plants.
Saussure and, after him, Dutrochet and others further observed the evo-
lution of heat which accompanies respiration in plants, and thus established
a noteworthy analogy between the processes in the vegetable and animal
organisms.
vi PHYTO-CHEMICAL RESEARCHES 537
this substance plays in the assimilation of carbon. Specula-
tion has still, however, pretty free play in the answering of the
questions — What is the organic compound which is in the
first instance produced from the carbonic acid, and what are
the intermediate products in the formation of starch,
•cellulose, albumen, etc.?
A. v. Baeyer's view — that formic acid is produced in plants
by the reduction of carbon dioxide, and is then converted
into carbohydrates by numerous condensations, — has been
corroborated to some extent by the laboratory experiments
of O. Loew, Bockorny, E. Fischer and others. This assumption
is at any rate the simplest that could be brought forward to
explain the nutrient action of carbonic acid.
The multifarious substances produced by plants have been
the objects of ardent investigation, more especially since the
stimulus which was given to the subject by Liebig's work ;
the chemistry of plant life has been developed alongside
of that of animal life, particularly since the close of the
forties. Reference must be made here, in passing, to
Rochleder's researches in this field (so important from
the chemical point of view), upon caffeine, various glucosides,
tannic acids,1 and other vegetable products. The attention of
phyto-chemists has been directed in a special degree to the
nitrogenous compounds which are formed in plants, i.e. to the
albumens in the first instance, and then to the compounds
produced by the breaking up of these. After Mulder had
pointed out the similarity of the former to animal albumen,
they were investigated by Liebig and his pupils, and they
have formed the subject of excellent work by Ritthausen
during recent years. The hope that conclusions might be
arrived at with regard to the constitution of the albumens
from the nature of their decomposition-products, more
especially from the amido-acids like leucine, asparagine,
glutamic acid, etc., has not indeed been realised ; but, from
the point of view of vegetable physiology, the researches on
the nitrogenous compounds which are formed during the
1 Kraus's monograph : — Grundlinien zu einer Physiologic des Oerbestoffes
(1889) shows the importance of the tannic acids in vegetable physiology.
538 HISTORY OF AGRICULTURAL CHEMISTRY CHAP.
germination of seeds and other processes have furnished
much valuable preparatory work for the future development
of that branch of the science.1
There are, besides, many other vegetable products
containing nitrogen which have occupied the attention of
chemists as well as of physiologists, e.g. various glucosides
such as myronic acid and amygdalin, and, in particular, the
great class of the alkaloids, — compounds whose importance
for chemistry has already been discussed.
The carbohydrates in their signification for the life of
plants have likewise been much investigated, with regard
both to the conversion of some of them into others by
chemical means, and to their physiological modes of forma-
tion; but here again the necessary link is often wanting
between particular products. The reader is referred to
the pioneering investigations of Briicke, Nageli, Sachs and
others upon starch and the substances formed before it, e.g.
dextrose, and upon the connection which exists between
the formation of starch and the activity of chlorophyll ; to
the excellent work of Cross and Be van and others on cellu-
lose; to the numberless researches on the sugar varieties,
especially dextrose and cane sugar, the occurrence of the
latter in beetroot and its technical production from the same
having created a chemistry of its own ; and to the laborious
work which has been and still is being done with the object
of elucidating the chemical nature of the glucosides and
their peculiar behaviour to ferments. The most important
of the investigations upon vegetable fats, ethereal oils, and
various other (vegetable) compounds belong in the main to
organic chemistry proper, and have been referred to under
the history of this.
1 Cf. the investigations of E. Sehulze and others.
vi RESEARCHES IN PHYSIOLOGICAL CHEMISTRY 539
Development of Zoo-Chemistry }•
The physiological chemistry of the animal body, zoo-
chemistry, has made extraordinary progress since the early
investigations of Fourcroy and Vauquelin, Chevreul, Berzelius
and others were made. From the examination of the
chemical constituents of animal organs, secretions, etc., an
advance was made to the infinitely more difficult problem —
Under what conditions are those substances formed in the
organism, and what are their relations to one another?
From the chemical investigations which arose from this,
animal physiology was first constituted into the science as
we now know it. And this applies in a special degree to
the important question of nutrition, and, speaking generally,
to the modern views of the metabolic processes of the animal
body. Chemical investigation has thus been the means of
dispelling the obscurity in which so many erroneous views
grew and flourished.
Since the publication of the above-mentioned researches,
the most distinguished physiologists and chemists have co-
operated in the development of zoo-chemistry, in so far
as this has aimed at a knowledge of the substances of which
the animal body is composed. From the large number of
excellent investigations of this kind, only one or two can
be touched upon here. Reference must first be made to
the work of v. Bibra, Mulder, Fre'my and Heintz upon the
constituents of bones, through which the true composition of
these was established. Schmiedeberg's investigations, made
in 1891, have been the first to throw light upon the nature
of the substances present in bone cartilage.
The question as to the nature of the albumens has given
rise to many important researches, especially since Mulder
first proved the presence of compounds of this kind in plants,
and Liebig and his pupils strove to arrive at their composition ;
1 The numerous sources of physiologico-chemical investigations are to be
found in Hoppe-Seyler's Lehrbuch der physiologischen Chemie. Cf. also
Bunge's Lehrbuch der physiologischen und pathologischen Chemie. Only in
a few instances have direct references been given here.
540 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
but they have not as yet led to a knowledge of the true con-
stitution of these bodies. Among those who have worked
at this subject may be mentioned A. Schmidt, Graham,
Brucke, Johnson, Hoppe-Seyler, Kiihne, Hammarsten, Leh-
mann, Schiitzenberger, Nencki, Drechsel and Harnack. To
the physiologist the question of the behaviour of albumen
in the animal body (in particular, the changes which it
undergoes during digestion, etc.) is of more importance than
its rational composition. Some investigations will be
referred to later on, in which an answer to such physiological
questions is attempted.
The most important of the researches which led gradually
but ultimately to a true explanation of the composition of
fats have already been spoken of.1 The part played by fats
in metabolism has only been satisfactorily worked out of
recent years, and the same remark applies to the carbohy-
drates.2 The pathological occurrence of those substances has
also given much occupation to chemists, who, by furnishing
definite tests for sugar, albumen, etc., have in many cases
lightened, and even rendered possible, the diagnosis of a
disease by the physician.
As in all the other branches of chemistry, so too in
physiological and pathological, have special methods of a
zoo-chemical analysis gradually developed themselves and
become indispensable.
The investigations that have been made with the
object of elucidating the chemical processes which go on
in the animal organism, and with this the processes which
condition or accompany life, are almost innumerable. Our
present knowledge of the various animal fluids which take
part in such processes has only been attained by the most
arduous labours. To mention but one or two of these, refer-
ence may be made in the first instance to the more important
of the researches on the secretions which promote digestion.
The classical investigations of C. Ludwig, Brucke and Cl.
1 Cf. p. 441.
2 With regard to the chemical importance of the carbohydrates, see
p. 454 et seq.
vi GASTRIC JUICE, BILE, BLOOD, ETC. 541
Bernard proved that the secretions from the glands were to
be looked upon as resulting from essentially chemical pro-
cesses. The importance of the saliva for digestion was also
shown by its chemical investigation ; Leuchs, in 1831, dis-
covered the ferment ptycdin which saliva contains, and which
has the power of transforming starch into sugar, and the
chemistry of the saliva has since been materially advanced
by the later work of O. Nasse, C. Ludwig, Briicke, Herter
and others.
Many scientists of repute have occupied themselves with
the investigation of the gastric juice ; thus the work of C.
Schmidt, Bidder, Beaumont, Frerichs, Lehmann, v. Wittich
and others has resulted in establishing the composition of
this secretion, and also the peculiar nature of pepsin, the
ferment which it contains. The excessively important part
played by the latter in the digestion of the albumens, which
are thereby converted into peptones, has been mainly arrived
at through the labours of Lehmann, Hofmeister, Henninger,
and more recently Neumeister, Kuhne and Chittenden.
Our knowledge of the pancreatic fluid and of its power-
ful influence on the digestive process, which is due to the
presence in it of particular ferments, we owe to W. Kuhne,
Htimer and others.
The chemistry of the bile, lastly, which originated with
Strecker's memorable work1 on the bile-acids and their
decomposition-products, has been subsequently extended by
Stadeler, Frerichs, Gorup-Besanez, Maly, etc.
The present knowledge of the chemical composition of the
blood and of its various constituents (so difficult to separate
from one another), together with the chemical behaviour
of these, is the outcome of an infinite number of laborious
investigations ; and it is still very far from being complete.
Reference must be made here to the pioneering work of Al.
Schmidt upon the causes of the coagulation of blood ; to that
of C. Schmidt, Hoppe-Seyler, Htifner, Preyer and others on
haemoglobin and oxy-hsemoglobin, and the behaviour of these
to gases, and also to the successful application of the
1 Ann. CJiem., vols. Ixi. Ixv. Ixvii. and Ixx.
542 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
spectroscope here; further, to the memorable researches
which finally established the composition of the blood-gases
and especially the difference* existing between arterial and
venous blood in this respect. The services rendered by C.
Ludwig deserve to be particularly emphasised, the investiga-
tions which he carried out along with his pupils from the year
1858 far surpassing the earlier ones of Magnus and of L.
Meyer in accuracy.
The numerous researches, by means of which the quantita-
tive relations between the air inhaled and exhaled by animals
were exactly determined, have been of the utmost value for
a knowledge of the metabolic processes of the animal body.
We have only to recall here the experiments carried out on
a large scale by Pettenkofer and by Regnault and Reiset since
the year 1862, and the important observations by C. Ludwig,
and by Pettenkofer and Voit, on the effect of muscular exer-
tion upon the consumption of oxygen and the production of
carbonic acid.
The exceedingly numerous researches on the substances
which occur in blood serum, on the inorganic constituents of
blood, and on the pathological changes which the latter
undergoes, cannot be entered upon here.
Milk has been the subject of frequent investigation ever
since Chevreul, Lerch, Heintz and others established its
principal constituents. Much attention has been paid in
more recent work to the process of coagulation, to the changes
which milk undergoes in the organism, to the nature of the
albuminous compounds which it contains, and so on ; witness
the important researches on the subject by Soxhlet, Ham-
marsten, Hoppe-Seyler, and especially Lehmann.
Much excellent chemical and physiological work has been
done upon urine — the secretion of the kidneys. Take, for
instance, the observations on the artificial production of urea,
of such moment from a chemical point of view, and those
upon uric acid and its manifold transformation-products, the
synthesis of which has already been achieved.1 Then there
are, too, the important physiological and pathological investi-
1 Cf . The History of Organic Chemistry, pp. 467-468.
vi CHEMICAL COMPOSITION OF FLESH, ETC. 543
gations by Liebig, Voit, Bischoff, Fick and Wislicenus on the
separation of urea in its bearing upon metabolism ; the re-
searches on the formation of hippuric acid, by Wohler, Liebig,
Dessaignes and Meissner; on that of the phenol-sulphuric
acids by Baumann ; on the formation of sugar, albumen, gly-
curonic acid, cynurenic acid (an oxyquinoline-carboxylic acid)
and indole ; and on the separation of all of those substances
just named in the urine.
The explanation of the manner of origin of these and other
substances, which are partly found under normal conditions
and partly under pathological, has long been recognised as
constituting an important problem of physiological chemistry.
From the results of a large number of observations, a
systematic method of analysing urine has gradually been
developed,1 and this daily stands the practising physician in
good stead; for, from the occurrence or accumulation of
certain substances in the urine, the latter can recognise
particular diseases with greater precision than by any other
sign.
The work which has been done upon the chemical composi-
sition of flesh,2 a subject to which peculiar difficulties are
attached, can only be briefly referred to. Liebig's classical
researches on " the constituents of the fluids of flesh," 3 and
the nearly allied ones of his pupils Schlossberger, Scherer,
Strecker and Stadeler, prepared the way for later and even
more ambitious labours ; we would refer here to the observa-
tions of Helmholtz, Ranke, Briicke and others on the effect of
muscular action upon the chemical processes which go on in
muscle-substance, — observations to which the first incitement
may have been given by Liebig's ingenious and far-reaching
speculations. The important part which glycogen plays in
these, as well as in other processes (e.g. the processes of the
liver), was arrived at through the admirable work of Briicke,
Cl. Bernard, Klilz, v. Mering, Voit, etc.
1 Compare Neubauer and Vogel's book -.—Anleitung zur Analyse des
Harns.
2 Cf. (e.g.] Falk's book, Das Fleisch (1880).
3 Ann. Chem., vol. Ixii. p. 257.
544 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
From the rich material of facts relating to the chemical
composition and physiological importance of particular parts
of the animal organism, which have thus been accumulated,
the views regarding the metabolic processes of the animal
body have been developed, and indeed completed, in certain
of their details. The establishing of the laws which govern the
nutrition of animals was long ago felt to be of the first import-
ance. And here again Liebig gave the powerful impulse to
the first, even if incomplete, solution of this question from the
chemical standpoint.
The service which he rendered with regard to the develop-
ment of the doctrine of metabolism appears especially great
when one recalls to mind how erroneous were the opinions of
physiologists respecting the chemical processes going on in
the animal body, before he set forth his views on nutrition and
other physiological processes in his standard work, Die Thier-
ckemie oder die Organisclie Chemie in Hirer Anwendung auf
Physiologic und PatJiologie (1842), (" Animal Chemistry, or
Organic Chemistry in its Application to Physiology and
Pathology"). The most eminent physiologists of that time,
Tiedemann, Burdach and others, were by no means fully con-
vinced of the necessity of chemistry for their science ; to ex-
plain the processes in the organism they had recourse to " vital
forces," many of them indeed flatly refusing the aid of
chemistry. It was left to Liebig to form a truer estimate of
the problems of physiology and of the means to be used in
solving these ; the opinion which he expressed — that it must
adopt the methods of physics and chemistry — coming as this
did with the full weight of his authority, was quickly taken
to heart. And what a change came over physiology in con-
sequence !
The powerful influence exercised by Liebig on the de-
velopment of the doctrine of metabolism has already been
frequently referred to. But a short resume may be given
here of the main conclusions of his comprehensive work and
ingenious speculations. He endeavoured to establish the
various importance of different nutritives for the animal body,,
in so far that he defined the albumenoids as plastic compounds
vi METABOLISM 545
which served mainly for building up the tissues and as the
source of muscular power, and the fats and carbohydrates as
respiratory compounds, which went for the most part to pro-
duce the animal heat. It was he in fact who first drew sharp
distinctions between nutritive substances among themselves,
and between these and other substances which, while not
directly nutrient, bring about metabolic changes in the
organism.1 And he also successfully determined the relative
values of the former by direct experiment.
The potent effect of Liebig's ideas respecting nutrition
and metabolism showed itself during the succeeding years in
the splendid work which was done by Bidder and Schmidt,
Bischoff, Voit, Pettenkofer, Frerichs and others, as the result
of his stimulus. By the aid of improved methods and,
especially, by the use of larger respiration apparatus, Liebig's
views were subjected to a sharper scrutiny, and thus under-
went many corrections, more particularly with respect to the
role of albumen and to the formation of fat. But in all
essential points he was right. To the elucidation of the
functions and actions of particular nutritives in the animal
body, the classical researches 2 of Voit and Pettenkofer,
together with those of their pupils (among whom were Ranke,
Forster, Rubner, Falck, Fr. Hofmann and Renk) upon
nutrition, and therefore upon metabolism, have contributed
in an especial degree. An important deduction drawn from
these researches, viz. that fat is produced from albuminous
matter, has lately been disputed by Pfliiger 3 as having no
sufficient basis. This eminent physiologist is further of
opinion that it is not the carbohydrates and fats but the albu-
mens which are the sources of muscular power.
The aims of the above branch of physiological chemistry
are so intimately connected with those of hygiene that the
two overlap at this point. Hygiene may indeed be looked
upon as a branch of chemistry, having found in the latter
science the most powerful of all aids to her development.
1 Genussmittel.
2 Most of these were published in the Zeitschrift fur Biologic.
3 Pfluger's Archivfiir Physiologic, etc., vol. xli. p. 229.
N N
546 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
Reference has already been made in the history of analytical
chemistry1 to the continuous improvement in the methods of
analysis of foods and drinks, a point of such immense import-
ance to the community in general.
Fermentation ; Putrefaction?
The various processes by which ferments are set in
action, and by which their action is conditioned, have now
attained to such a supreme importance for hygiene and
for physiology as a whole, that a few words must be said
here with regard to the development of our knowledge of
the processes of fermentation and putrefaction during recent
years.
It is a long time since the vinous fermentation first
attracted the attention of chemists, but Lavoisier was the
earliest to recognize that the two main products re-
sulting from it — alcohol and carbonic acid — came from the
sugar present ; at the same time he attempted to work out
the quantitative relations between the latter and the two
former compounds. As to the reason for the breaking up of
sugar in the presence of yeast, no views were expressed at
that time which were at all tenable. Before it was known
that yeast consisted of living cells, Liebig's mechanical-
chemical theory of fermentation 3 gained many adherents.
This theory, which was propounded in the year 1839,
attempted to explain alcoholic fermentation and other
similar processes from one common point of view. Liebig
here regarded ferments in general as easily decomposable
bodies, from which the stimulus to the decomposition of
fermentable substances proceeded. This view recalls that
which Stahl and Willis had brought forward long before, for
they also assumed a transference of the motion of fermenting
1 Of. p. 398.
2 For the literature consulted here, see the articles "Fermente" and
"Garung" in the Handworterbuch der Chemie; A. Mayer, Lehrbuch der
Gahrungschemie ; and Schiitzenberger, Gdhrungserscheinungen.
3 Cf. Aim. Chem., vol. xxx. pp. 250 and 363.
vi RESEARCHES IN FERMENTATION ; PASTEUR 547
particles to a large number of others. Some investigators
had contented themselves with attributing to yeast a
" catalytic " action, but this simply meant the employment
of a word to cover their ignorance of the subject.
In 1 8 3 6, i.e. shortly before Liebig had brought out his
theory, Cagniard de Latour, Schwann, and Ktitzing made
simultaneously and independently of one another the impor-
tant discovery that yeast consists of low organisms which
are self-propagating. The subsequent comprehensive re-
searches of Pasteur l entirely confirmed the correctness of
these observations. From all this the vitalistic theory of
fermentation followed as a necessary consequence, although
its recognition was retarded by the force of Liebig's great
authority ; according to this theory the decomposition of the
sugar is dependent upon the vitality and consequent activity
of the yeast fungus.
Other processes of fermentation were now investigated
from the standpoint thus obtained, with the result that low
organisms were found to be the cause of the action in their
case also. We would refer here to the splendid researches
of Pasteur upon the acetic and lactic fermentations, of equal
importance physiologically and chemically ; to the discovery
of the particular fission fungi which gave rise to various
fermentations ; and to the work of Rees, de Bary, Brefeld,
A. Mayer, Fitz and others, the object of which was to
elucidate the conditions of the life and especially of the
nutrition of organised ferments (more particularly yeast and
its connection with fermentation), and also the products of
these latter.2 E. Chr. Hansen's wide-reaching investigations
in this branch have been of the utmost value, more especially
to the technical side of the brewing industry.3
1 Cf. his large works, fitudes sur la Btere,—sur le Vin,—surle Vinaigre.
2 C. Schmidt found succinic acid, and Pasteur glycerine, among the
products of the vinous fermentation. It is only of comparatively recent
years that sufficient attention has been paid to the various alcohols con-
tained in fusel oil, which are now recognised as products of secondary fer-
mentations.
3 Hansen, Untersuchungen aus der Praxis der Gdhrungsindiistrie
(Munich, 1890).
N N 2
548 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
Much vigorous discussion has ultimately led to agree-
ment upon the most important of the disputed points, with
regard to which the views of different workers were formerly
far apart. A twofold growth of the yeast cells is now estab-
lished, viz. (1) a growth in presence of oxygen, which is not
followed by fermentation, and (2) one in absence of oxygen,
through which fermentation is produced.1
The difference between organised and unorganised fer-
ments, the latter of which are termed enzymes, came to be
clearly recognised, this being mainly due to Pasteur's work.
The extraordinarily important functions of these unorganised
ferments in the animal and vegetable organisms has led
physiologists and chemists of the highest eminence to devote
their close attention to the subject, but as yet no satisfactory
theory of the action of such ferments has been brought forward;
in conjunction with this, reference must be made here to the
work of Nasse, Htifner, Traube, Hoppe-Seyler, Nencki, Al.
Schmidt and Wurtz. Quite recently Btichner 2 has isolated
an enzyme which is capable of inducing the alcoholic fer-
mentation in the absence of yeast cells.
The phenomena of putrefaction, which were placed by
Liebig in the same category with the processes of fermenta-
tion (both being brought about, in his view, by similar
mechanical-chemical causes), acquired a heightened physio-
logical interest after it was perceived that they were
connected with the presence of certain peculiar organisms.
Here again the researches of Pasteur and also of Nencki,
Hoppe-Seyler, etc., stand out pre-eminent. The chemical
examination of the products of putrefaction has led to
1 Liebig maintained an antagonistic attitude to the vitalistic theory of
fermentation ; he did not indeed contest the organised nature of yeast, but
would not acknowledge that the latter itself gave rise to fermentation
through its life processes. Instead of this he assumed in yeast the presence
of an albuminous ferment, which, on the death of the former, he imagined
to bring about the decomposition of the sugar into alcohol and carbonic
acid. Nageli's attempt to explain the phenomena of fermentation may be
looked upon as an effort to reconcile the vitalistic and mechanical theories
(cf. his Theorie der Gdhrung, 1879).
2 Ber., vol. xxxi. p. 568.
vi THE PHENOMENA OF PUTREFACTION ; PTOMAINES 549
remarkable results, which have also a high importance
for the chemist. Most interest has been centred in the
nitrogenous compounds which originate from the decomposi-
tion of animal albuminous substances by putrefaction ; thus
we would recall here the discovery of various amido-acids,
of indole and its homologues, and, particularly, of the so-
called ptomaines}- The formation of these powerful poisons,
which have also been called corpse alkaloids, because of their
likeness to the alkaloids from plants, is of the first im-
portance to the forensic chemist,2 seeing that cases have
occurred in which the ptomaines have been confounded with
the true alkaloids, on account of similarity in reaction. The
Italian toxicologist Selmi was the first to clearly recognise
the important role, from a forsenic point of view, of these
putrefaction bases, and he it was who gave them the generic
name by which they are now known, — the ptomaines.
In addition to Selmi — Otto, Husemann, Dragendorff,
Robert, Brieger and others have rendered good service in
extending our knowledge of these substances. Brieger, in
especial, and also Nencki, Stard, Gautier, Guareschi and
Mosso have succeeded in characterising certain ptomaines
chemically. The constitution of some of them has been
recently established, witness the beautiful syntheses of cada-
verine3 and of putrescine,4 which have been respectively
shown to be penta- and tetra-methylene diamines.
The Relation of Chemistry to Pathology and Therapeutics.
The phenomena of putrefaction possess the highest
interest for pathologists, because such processes lie at the
root of many diseases. An increasing knowledge of the
causes of these proceeses has thus resulted in the establish-
1 For a historical notice of these peculiar compounds, cf. Beckurts'
Ausmittelung giftiger alkaloide ("Detection of Poisonous Alkaloids"),
(Archiv Pharm. for 1886, p. 1041); also Armstrong, Journ. Chem. Ind.,
vol. vi. p. 482. 2 Cf. pp. 397-398. s Cf. p. 480.
4 Ber., vol. xx. p. 2216 ; vol. xxi. p. 2938.
550 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
ment of a close connection between chemistry and pathology,
the former having now become indispensable to the latter.
And this necessity for chemistry has shown itself not merely
in the investigation of the products of putrefaction ; through
its means the more delicate tests for the recognition and
distinction of disease-producing bacteria have been elaborated,
and it has thus been instrumental in helping to found the
new science of bacteriology. This subject cannot, however,
be entered into here.
Above all, it has been reserved for chemistry to direct
the attention of physicians to remedies for counteracting the
pathological processes induced by micro-organisms. Only a
passing reference can be made here to the wonderful results
which have been achieved in medicine and surgery, and also
on the large scale in the preservation of food and drink, by
the use of antiseptics. One is probably not wrong in
assuming that the old practices of smoking flesh and of
dipping wood into tar drew attention to the carbolic acid
which the latter contains, and the antiseptic action of which
has now found such world-wide application in Lister's
method of treating wounds. The discovery of the anti-
fermentation and anti-putrefaction powers of salicylic acid
by Kolbe originated in the idea that this compound
tended to break up into carbolic and carbonic acids in its
passage through the organism. The last decade has
introduced us to a large number of new antiseptics, which
are now used more or less in medical and hygienic practice ;
these are mostly substances which stand in a near chemical
relation to phenol, e.g., the homologous cresols and thymol,
the sulphonic and carloxylic acids of these, the iodo-deriva-
tives of phenol- and oxy-quinoline-sulphonic acids, etc. The
assumption made by various investigators — that axitifer-
ments and antiseptics act by precipitating or chemically
altering the readily decomposable albuminous substances
— explains the role of these in a sufficiently satisfactory
manner ; for, when those bodies are got rid of, the ferments
are deprived of their necessary nutriment.
The nearly allied question of the great benefit which
vi ANAESTHETICS, FEBRIFUGES, ETC. 551
chemistry has conferred upon medicine 1 by enlarging its
stock of remedies can only be touched upon very briefly, as
any detailed treatment of the subject here would overstep
the limits of this work. With the history of medicine in the
earlier ages the conditions were quite otherwise ; for, in the
iatro-chemical as well as in the phlogistic periods the latter
was in the main conjoined with the history of chemistry,
whereas now chemical investigation pursues totally distinct
aims.
To mention only one or two of the specially important services
which chemistry has rendered to medical science, take the
introduction of narcotics and anaesthetics — chloroform, ether,
nitrous oxide, chloral, bromide of potassium, sulphonal, etc.
A number of other chemical compounds have been proposed
as anaesthetics during the last few years, but none of them
have entered into serious competition with chloroform, ether
and nitrous oxide. And the same remark applies to the sub-
stances newly recommended as soporifics, e.g. urethane, para-
aldehyde, aceto-phenone, etc ; compared with sulphonal and
chloral, these have but little importance.
Reference must also be made to the success with which
naturally occurring sedatives and febrifuges have been re-
placed by others artificially prepared, e.g. quinine by antipy-
retic remedies like salicylic acid, acetanilide, antipyrine,
phenacetine, etc. It has already been shown 2 how, with the
acquisition of the knowledge that the alkaloids are derivatives
of pyridine or quinoline, a firmer foothold was gained for the
artificial formation of these natural products — an object which
has been striven after for so long.
1 H. Thorns' work :—Die Arzneimittel der organischen Ghemie gives an
excellent summary of the rapidly extending list of artificially prepared
medicines ; compare also Beckurts' reports on Pharmaceutical Chemistry
in the Jahrbuch der Chemie, vols. i — v.
2 Cf. pp. 482-483.
552 HISTORY OF PHYSIOLOGICAL CHEMISTRY CHAP.
The Eelation of Chemistry to Pharmacy.
With the rapid enlargement of the medical treasury,
the problems which confront the pharmacist have likewise
grown in a very high degree. If the latter is to do justice to
the demands which are made upon him, he must be equipped
with a catholic and thorough knowledge of chemistry. The
development of pharmaceutical chemistry in recent years is
for the most part concurrent with that of particular branches
of the pure and applied science. The discoveries of inorganic
and organic compounds which have proved of importance for
pharmacy have likewise been of great value for chemistry
itself.1
In the domain of analytical chemistry we see the assid-
uous and scientifically educated pharmacist striving after
similar aims with the chemist. The former ought to have a
thorough knowledge and be master of the approved analytical
methods which are required for the testing and examining of
officinal drugs as well as of food and drink, and should also
be prepared for legal cases where chemistry comes into play.2
Pharmaceutical chemistry is in fact connected in the
most intimate manner with pure chemistry, for both have the
same foundations. If we would convince ourselves of this, we
have but to look through the numerous recent text-books of
the former branch, to perceive that in contents and arrange-
ment they are much the same as those of the pure science.
So long ago as 1844 H. Kopp3 expressed himself pertinently
on the subject as follows : " Since the end of last century
pharmaceutical chemistry has deviated more and more from
the direction which it still followed during the earlier decades
of the latter, when it merely borrowed from the investigations
of scientific chemistry those results which had a bearing upon
the preparation of medicines. It became more and more
nearly allied to purely scientific chemistry ; pharmaceutical
1 Cf. The History of Pure Chemistry, p. 400 et seq.
2 Cf. pp. 397-399.
3 Geschichte der Chemie, vol. ii. p. 119.
vi RELATION OF CHEMISTRY TO PHARMACY 553
text-books, which formerly were mere collections of empirical
recipes, came to have a genuine scientific character, while the
journals originally brought out for pharmacy became import-
ant miscellanies for pure chemistry."
At the close of last century and beginning of this one the
relation of chemistry to pharmacy was, however, different
from what it is now. Then the latter was an Alma Mater
for the former, whereas now these positions are exactly re-
versed ; pharmacy enjoys to-day the fruits of a highly de-
veloped chemistry. In earlier times the study of pharmacy
was in truth the only road to that of pure chemistry, and
this is why the most eminent chemists from the end of last
century until well on in this one came from the pharma-
ceutical school. We have but to recall here the names of
Scheele, Rouelle, Klaproth, Vauquelin, Liebig, H. Rose and
many others.
The pharmaceutical institutes which began to spring into
life at the close of last century were of great value for the
education of chemists who wished at the same time to
become pharmacists, for in these any young man who was
anxious to learn received a course of systematic instruction.
The Trommsdorff Institute in Erfurt, founded in 1795, de-
serves special mention in this connection. And good text-
books of pharmacy were not wanting then either, e.g. Hagen's
ApothekerJcunst ("The Art of Pharmacy " 1 7 7 8), Gottling's
Handbuch der Pharmazie (1 80 0),Hermbstadt's,TrommsdorfFs,
Westrumb's, and Buchholz's text-books, etc. The Pharma-
ceutical Society of London dates from 1841.
A historical account of how pharmacy proper has de-
veloped along with chemistry during the present century is
unnecessary here, for the reasons already given.
554 HISTORY OF TECHNICAL CHEMISTRY CHAP,
HISTORY OF TECHNICAL CHEMISTRY DURING THE
LAST HUNDRED YEARS.1
The immense development of large chemical industries
and, in fact, of all the branches of chemical technology during
the present century is the natural consequence of the great
advances in chemical knowledge, and the rational application
of these to technical processes. The light of scientific re-
search has thus been shed upon the latter, and new branches
of industry have been grounded upon exact investigations^
The history of technical chemistry offers a continuous series V
of examples of this beneficial action of theory upon practice.
On the other hand, numerous questions have arisen in the
course of technical working which have given rise to investi-
gations of the highest value for pure chemistry.
The great advances which have been made in chemical
technology only became possible with the development of
analytical chemistry, which allowed of a olear insight into the
composition of the original, intermediate, and final products
of technical processes. Since the beginning of this century
methods of research have gradually become more perfect, ,
methods which more and more meet the requirements of the
technical chemist, and which have constituted andf still *
constitute the most important aids to the development of
chemical industry. Many of these methods have already
been referred to in the history of analytical cjjemistry,2 but
the reader may also be reminded at this point of their use
with respect to the wants of everyday life. The testing and
examination of articles of food and drink are now carried on
1 For the literature on the subject, see Wagner's Jahresberichte and hi&
Lehrbuchder Technologic ("Annual Reports" and " Text-Book of Tech-
nology") ; A. W. Hofmann's JBericht ilber die Entwickelung der Chemischen
Industrie (" Report on the Development of Chemical Industries," etc.,
1875-77) ; Karmarsch, Geschichte der Technologic, etc. ("History of Tech-
nology," etc. ) ; and the text-books referred to in the succeeding pages.
2 Cf. pp. 390, 392 and 398.
vi GROWTH OF CHEMICAL INDUSTRIES 555
in a very large number of laboratories, the methods employed
here having been elaborated from purely chemical investiga-
tions. This applies in a special degree to the analysis of
water, which is of such enormous importance alike from a
hygienic and an industrial point of view. We have only to
think how necessary it is to establish the chemical composi-
tion of a water before employing it for any manufacture ;
and the various processes of purification, too, to which it has
to be subjected, before it can be used for many purposes, are
based upon rational chemical researches and observations.
Another benefit which water analysis has conferred upon the
community at large consists in its having rendered possible
the artificial production of mineral waters, and thus called a
flourishing industry into life ; the great services rendered in
respect to this by F. A. Struve (1820) deserve to be recalled
here.
In the following pages mention will be chiefly made of
such work as has either led to the introduction of important
novelties into chemical technology or to the opening up of
new branches of the latter.
It is hardly possible to estimate the benefit to the national
well-being which has accrued, more especially in Germany,
England, France, Switzerland and Belgium, from the growth
of chemical industries. Take, for example, the coal-tar colour
manufacture in Germany, which has arisen upon foundations
of purely scientific work, and the alkali and sulphuric acid
manufactures in Great Britain. The former illustrates in the
most perfect manner the principle of the refinement of matter,
a troublesome and almost worthless waste product — tar — being
now worked up by chemical processes into a vast number of
valuable substances. And the same applies in greater or
less degree to the chief chemical industries of all the coun-
tries mentioned above ; in every case men are striving to
bring individual chemical processes to the highest state of
perfection by utilising all the waste products. The soda
industry of to-day offers a specially good instance of this, for
in it we find competing processes successfully carried on,
simply because they have called to their aid every means of
556 HISTORY OF TECHNICAL CHEMISTRY CHAP.
rational chemical investigation. There is indeed hardly any
branch of chemical manufacture of which the same may not
more or less be said.
Reference may also be made here to the development of
technical instruction,1 which has of course contributed im-
mensely to the advancement of chemical industries. Tech-
nical schools and colleges belong for the most part to the
present century. The earliest of those on the continent of
Europe were the ficole Polytechnigue of France, founded in
1794, and called at first the jfrcole Centrale des Travaux Publics,
the Vienna Polytechnic Institute (1815), and the Berlin Tech-
nical College (1821). The chemical laboratories of the above
and other similar institutions in Dresden, Darmstadt, Hanover,
Stuttgart, Munich, Zurich, etc. have continued to increase in
importance as aids to the furtherance of chemical manu-
factures. As every one knows, Great Britain is by no means
so well equipped with technical schools and colleges as many
of its neighbours on the Continent, but public opinion is now
becoming awakened on the subject, and the want is being
gradually supplied.
The literature on technical chemistry has sprung from
insignificant beginnings. Hermbstadt's works on Dyeing,
Bleaching, Distilling, etc., which were published in and after
the year 1820, deserve mention on account of their value at
that time. During the last fifty years immense strides
have been made in this respect, as is witnessed (e.g.) by the
excellent encyclopedias of Prechtl and Karmarsch, Muspratt-
Stohmann-Kerl, Bolley, Ure, Watts and Thorpe, and also by
the text-books upon chemical technology, among others those of
Dumas, Payen, Knapp, Wagner and Ost, in which the results
of theory and practice are given together. In addition to
these, the weekly and monthly journals, among which Dingier 's
Polytechnisches Journal, Wagner's Jahreslerichte (now edited
by F. Fischer) and the Journal of the, Society of Chemical
Industry may be named, supply us with information
upon the results of current chemico-technical investigation.
1 Cf. the excellent historical, critical and statistical work of Egon
Zoller : — Die Universitdten und technischen Hochschulen (Berlin, 1891).
vi METALLURGY OF IRON AND STEEL 557
By such means the closest connection between chemical
industry and the pure science is permanently maintained.
The Progress of Metallurgy.1
Although the production of iron and steel, as carried on
in the phlogistic period, gave rise to chemical work through
which the mutual relations of cast-iron, wrought-iron and
steel were in some measure explained, there still remained
a variety of problems in connection with these to be solved
at a later date. The improvement of analytical methods
rendered it possible to detect and estimate the various im-
purities in iron, — silicon, phosphorus, sulphur, arsenic, etc.,
— and at the same time to recognise their influence in
modifying the properties of the metal. The blast furnace
process was explained by the excellent investigations of
Gruner, Tunner, L. Binman, and others, the analyses of the
furnace gases by Bunsen 2 and Playfair 3 aiding in a special
degree towards the elucidation of the reactions which go on
in it. The determination of the composition of pig-iron — the
proof that a chemical compound of iron and carbon exists —
was also conducive to the establishment of a theory of the
blast furnace process. The Bessemer process for the pro-
duction of steel (1856) was the result of the clear perception
of the connection existing between iron and steel, while the
chemical investigation of the products which are formed
during its various stages greatly assisted its development.
The Thomas-Gilchrist process for dephosphorising iron,
introduced about the year 1878, has been a wonderful success.
Light was shed upon the theory of it by various analytical
researches, e.g. those of Finkener ; 4 while, on the other hand
scientific experiments by A. Frank, P. Wagner, and others
have led to the utilisation of the phosphoric acid which
1 Compare the works on metallurgy by B. Kerl, Stolzel, Balling and
others.
2 Cf. Pogg. Ann., vol. xlvi. p. 193.
3 Brit. Assoc. Reports for 1845, etc.
4 Cf. Wagner's Jahresber. for 1883, p. 136.
558 HISTORY OF TECHNICAL CHEMISTRY CHAP.
accumulates in the slag produced in the process — the Thomas
slag, — so that this latter has now become an artificial manure
of the first importance, being sold in a fine state of division
under the name of " basic slag." The ingenious application
of the spectroscope to the examination of the Bessemer flame,
whereby the end point of the reaction can be clearly distin-
guished,1 and the introduction of the Martin process must
also be referred to.
As another example of the utilisation of by-products, we
may take the successful working up into iron of iron pyrites
from which all the sulphur possible has been driven off.2 The
desire to waste no material of any value is also shown in the
process of manufacturing copper from pyrites whose sulphur
has been already utilised, — a process elaborated from chemical
researches.
The metallurgy of nickel has developed rapidly since
German silver began to be prepared upon a rational system,
and especially since its employment as an ingredient of
coins ; the German nickel coinage dates from 1873. Nickel
has, however, been long known to the Chinese, and used by
them for making a variety of articles. An alloy of nickel and
iron is now employed for armour-plating ships of war. A
passing reference may also be made to the remarkable at-
tempts to separate nickel from its ores in the form of the
volatile compound with carbon monoxide,3 and to regenerate
the monoxide from this.
Numerous improvements have been made in respect to
the production of silver, among others the Augustin and
Ziervogel extraction processes, and the Pattison and Parkes
processes for the desilverisation of lead ; while the metallurgy
of gold has also been facilitated by the introduction of good
methods for separating the latter from other metals, e.g. by
that of d'Arcet (1802), that of Plattner, and especially the
now well-known cyanide process. The most important addi-
tions to the technology of platinum were made by Deville and
1 Roscoe, Chem. Neius for 1871.
2 Gossage, Chem. Centr. for 1860, p. 783.
3 Mond, Mon. Sclent, for 1892, p. 785 ; or Nature of July 7th, 1892.
vi ELECTRO-METALLURGY 559
Debray after the year 1852, in the fusion of large quantities of
the metal and the introduction of methods which gave a
larger yield.
The galvano-plastic process, i.e. the precipitation upon one
metal of a thin layer of another one by means of electricity,
has proved itself of great importance. The original observa-
tion in this direction was made by de la Rive in 1836, and
this was followed by the publication in 1839 by Jacobi,and a
little later by Spencer, of the process from which the more
perfect electro-metallurgy of to-day has developed itself. The
share taken by the late Werner Siemens in this development
should not be forgotten.
Among the metals which have been isolated during the
present century, aluminium was first made available for
technical purposes by the assiduous and successful labours
of H. St. Claire Deville,1 while the Stassfurt mineral
carnallite has proved itself a convenient source from which
to prepare magnesium. The methods by which those metals
are actually produced have grown out of the work of their
discoverers.2
The application of electricity 3 for the extraction of metals
from their compounds, i.e. Electro-metallurgy, has made very
great progress during recent years, e.g. for the production
of copper, zinc, gold, and especially aluminium. Sodium,
which was before this used in such large quantity for the
manufacture both of aluminium and magnesium, is now con-
sequently of much less technical importance ; but as sodium
peroxide is coming into vogue for bleaching wool, silk and
feathers, there is probably a fresh field of usefulness in store
for this metal. The production of carbide of calcium,
already referred to, must also be mentioned in connection
with electro-metallurgical processes.
1 Comptes RenduSj vols. xxxviii. xxxix. and xl.
2 Cf. The History of Pure Chemistry.
3 Compare E. Ger land's report in the Chemiker Zeitung for 1893, No.
30 ; Cl. Winkler, ibid. 1892, No. 22 ; and especially Borcher's Elelctro-
metallurgie, 1891. See also a short paper by Thos. Ewan on The Industrial
Applications of Electro- Chemistry (Nature for June 2nd, 1898).
560 HISTORY OF TECHNICAL CHEMISTRY CHAP.
Numerous improvements have also been made in the
course of the century in the manufacture of alloys of every
kind. Thus, from zinc and copper there have been pre-
pared malleable brass, similor, etc., and from aluminium
and copper, aluminium bronze, besides a great many alloys
and amalgams of tin, including type metal ; this last used to
be made from antimony and lead only, but to these tin is
now added.
This century has also witnessed the production of all
sorts of metallic compounds, among which mineral pigments
take a prominent place. The most important improvement
in the manufacture of white lead was due to Thenard(lSOl),
Scheele having before this made some fundamental observations
on the subject (p. 147). Zinc white, which was made on an
experimental scale by Courtois so long ago as at the end of
last century, was first brought into general repute by Leclaire
in 1840, after which it came to be produced on the large
scale. The introduction of chrome colours, especially of chrome
green and chrome red, both of which are so highly valued for
enamelling, belongs to the present century. Schweinfurt
green, a double compound of cupric arsenite and acetate, was
discovered by Sattler in 1814; it was greatly in vogue for
a long time, but is now superseded by other colours on account
of its poisonous nature. The extended application of many
metallic salts, formerly prepared in small quantities only, to
new purposes (e.g. of nitrate of silver in photography, and of
the yellow and red prussiates of potash in dyeing) has led to
the rise of entirely new branches of manufacture. There are
now but few salts of any of the more plentifully occurring
metals which have not some use on the large scale ; for
instance, stannous and stannic chlorides and various salts of
aluminium, iron and manganese in dyeing, and compounds of
mercury, bismuth, antimony, zinc, etc., chiefly in pharmacy.
vi MANUFACTURE OF SULPHURIC ACID 561
Development of the Great Chemical Industries.
The great chemical industries are a product of our own time,
their growth having gone hand in hand with the growth of
pure chemistry. The manufactures of sulphuric acid and
soda, which may be looked upon as the basis of all the others,
and which are naturally followed by those of hydrochloric
acid, bleaching powder, chlorate of potash and other salts of
potassium, nitric acid, etc., only attained to their full vigour
after the various processes involved had been explained by
chemical investigation, and after the most favourable conditions
for those processes had been worked out. The introduction
of easy methods of analysis into technical industries has also
been of the utmost service to them.
Important practical improvements were made in the
manufacture of sulphuric acid1 so early as the beginning
of the present century, e.g. the amount of steam required
was regulated, and the process was made continuous (the
latter by Holker). The first attempt to explain this
remarkable chemical process of the formation of sulphuric
acid from sulphurous acid, air, water and nitrous gas
was made by Clement and Desormes,2 who recognised
the important part played by the nitric oxide. Later
researches by Peligot, and more especially by Cl. Winkler,3
R. Weber,4 Lunge, Schertel and others, have served to eluci-
date the reactions which go on between the above-mentioned
substances, and have therefore been of the utmost value in
respect to the manufacture of the acid ; they have led, for
example, to an exact knowledge of disturbing conditions,
which can therefore now be provided against. To Reich is
due the merit of having brought the technical process under
due control, by his analysis of the chamber gases ; and. ever
since Cl. Winkler called technical gas analysis into life, this
1 Cf. Lunge's Manufacture of Sulphuric Acid and Alkali.
2 Ann. de Chimie, vol. lix. p. 329.
3 Cf. Hofmann's Bericht, etc. , vol. i. p. 382.
4 Journ. pr. Ghem., vol. Ixxxv. p. 423 ; Pogg. Ann., vol. cxxvii.
p. 543.
O O
562 HISTORY OF TECHNICAL CHEMISTRY CHAP.
has been a regular part of the operation. How essential for
the manufacture the observations on the chemical behaviour
of nitrous acid to sulphurous and sulphuric have been, is
sufficiently evidenced by the introduction of the Gay-Lussac
and Glover towers to which they gave rise, and which have
made the process into one complete whole.
But if scientific chemistry has thus proved itself so neces-
sary for technical, the latter has likewise done much to
advance the former ; for many important discoveries, e.g.
those of selenium and thallium, have been rendered possible
by its aid, and researches of high value, such as those of
Lunge upon the various stages of the oxidation of nitrogen,
have arisen from technical questions.
The preparation of sulphuric anhydride from sulphur
dioxide and oxygen, which was formerly merely a lecture-
room experiment, has been converted into a technical process
through the admirable researches of Cl. Winkler,1 and thus
an important reagent has been made available for many
branches of chemical industry. Sulphurous acid, whose sole
technical application (practically speaking) for a long time
was in the manufacture of sulphuric acid, is now condensed
on the large scale and used for the bleaching of wool and
silk, and as a refrigerant, and it has also recently found an
extensive employment in the production of the so-called
sulphite-cellulose and in the precipitation of lime from sugar
juice. The utilisation of sulphurous acid for these purposes
is all the more striking when we remember that in the
roasting of sulphides it used often to be allowed to escape
into the air, to the great detriment both of human beings
and of vegetation.
The Soda Industry. — The transformation of common
salt, which occurs so abundantly in nature, forms the founda-
tion of this immense industry, whose history commences
with the beginning of the present chemical period. Nicolas
Leblanc 2 was the first to succeed in converting salt into soda,
1 Wagner's Jahresber. for 1879 and 1884.
2 This remarkable man, who was born at Issoudun (Indre) in 1742 (and
not, as usually stated, in 1753), derived no pecuniary benefit from his
vi THE SODA INDUSTRY 563
with sodic sulphate as an intermediate product, Malherbe
and De la Metherie having some time previously attempted
to utilise the latter substance in the same way, but without
material success. It was in 1791 that Leblanc commenced
the actual manufacture of soda, but political conditions and
other circumstances hindered its growth for a long time, the
chief difficulty being the high duty on salt. In the year 1823
Muspratt began the erection of his alkali works at Liverpool ;
his name deserves a foremost place in connection with the
development of the soda industry. The advantages which
have accrued to the manufacture of soda from chemical inves-
tigation are incalculable, but space will not allow of entering
minutely into them here. The simple analytical methods
which supplied the necessary information as to the composi-
tion of the raw, intermediate, and final products were and
are still of the first importance for the regulation of the tech-
nical process. The formation of soda from the sulphate, by
fusing the latter with coal and limestone, was ultimately so
far explained by exact chemical experiments l (after various
unsuccessful speculations on the subject by Dumas and others),
as to allow of a tenable theory of this fusion process being
brought forward.
Scientific researches have also given rise to numerous im-
portant improvements in the soda manufacture, e.g. to the
beautiful process of Hargreaves and Robinson (by which sul-
phate of soda is prepared directly without the previous pro-
duction of sulphuric acid), to the introduction of revolving
soda furnaces, and to many processes for utilising and
rendering harmless the unpleasant alkali waste. With re-
spect to the last, we would refer here to the work of Guckel-
berger, Mond, and Schaffner and Helbig, who succeeded in
making various laboratory reactions practicable on the large
scale. But the greatest advance of all in this direction is
great labours. He died in the utmost poverty in 1806, his death being due
to despair. A monument has recently been erected at his birthplace to
his memory.
1 Cf. Dubrunfaut in Wagner's Jahresber. for 1864, p. 177 ; Scheurer-
Kestner, ibid. 1864, p. 173 ; and, especially, Kolb, ibid. 1866, p. 136.
O O 2
564 HISTORY OF TECHNICAL CHEMISTRY CHAP.
the recent and exceedingly simple process of Chance,1 by
which nearly all the sulphur in alkali waste can be recovered
at a very cheap rate ; the result of this has been to enable
the Leblanc process to compete on more equal terms with the
younger ammonia-soda and electrolytic processes (see below).
Purely chemical observations have also led to what
was, until quite recently, unquestionably the most important
of all the innovations in the soda industry, viz. the conver-
sion of common salt into carbonate of soda, without the
intermediate formation of sulphate at all, by the ammonia-
soda process.2 Although the reaction upon which this
method is based is extremely simple, it took a very long time
before the most favourable conditions for it were established,
and before it was made into a practical success ; but this was
ultimately achieved by E. Solvay. The manufacture of
" ammonia soda " and of artificial manures has grown so
enormously of late years that the demand for salts of ammonia
has increased proportionately ; but this requirement has in its
turn been met by the introduction of improved apparatus for
the working up of gas liquor, and by the attempts to extract the
nitrogen of fuel in the form of ammonia,3 at the same time that
the heat from the fuel is itself being utilised. Here again the
mutual influence of one branch of manufacture upon another
is apparent, and also the benefits accruing to these from
scientific investigations.
The production of " ammonia soda " has now attained to
such a height that the manufacture of " Leblanc soda "
has been greatly prejudiced. For many years back chemists
have been striving to solve the problem — how to obtain
hydrochloric acid or chlorine from the waste products of the
ammonia soda process ; should this be ultimately accomplished
on the practical scale, then it is hardly conceivable that the
Leblanc process can continue to exist. The numerous patents
referring to the processes carried out on the large scale by
1 Journ. Ghent. Ind., vol. vii. p. 162.
2 For the history of this, cf. Hofmann's Bericht, vol. i. p. 445.
3 Cf. Mond, Chemiker Zeitung for 1889, Nos. 81 and 82 : or Journ. Chem.
Ind., vol. viii. p. 505.
vi HYDROCHLORIC ACID ; BLEACHING POWDER 565
Weldon and Pechiney, Solvay and others show that no efforts
are being spared to overcome this difficulty.
Chemical labours have exercised a less profound influence
upon the manufacture of hydrochloric acid, which is neces-
sarily produced in such quantity in the Leblanc process,
although laboratory researches have led to important im-
provements with regard to its condensation by water, and
to its purification from admixed substances. It may be
mentioned here, as a curious point in chemical history, that
this acid, which is at present so cheap and which has at
times been almost worthless, was in Glauber's time the most
costly of the mineral acids.
The manufacture of chloride of lime, which uses up large
quantities of hydrochloric acid, has also derived great benefit
from chemical research, in fact it may be said to have arisen
from the latter. Berthollet's experiments upon the bleaching
action of chlorine and the chlorides (i.e. hypochlorites) of
the alkalies led to the manufacture of the bleach liquor
known under the name of Eau de Javelle. Chloride of lime
was first produced by Messrs. Tennant and Co. in Glasgow
in the year 1779. Weldon's beautiful process1 for the
recovery of the manganese dioxide, required in the pre-
paration of chlorine, from the otherwise worthless chlorine
waste — a process which has been in practical working since
1867 — grew out of exact laboratory experiments; at the
same time its development gave rise to a rich harvest of scien-
tific results. Deacon's method of producing chlorine'2 directly
from hydrochloric acid likewise originated in apparently
trivial observations ; a strictly scientific explanation of the
action of the copper salt on the mixture of hydrochloric acid
and air in this process has, however, still to be given.
The recent rapid development of electro-chemistry is
strikingly shown in the electrolytic production of chlorine,
caustic alkali, hypochlorites and chlorates from the chlorides
of the alkalies. This method has already entered into serious
1 Chem. News for September, 1870.
2 Journ. Chem. Soc. for 1872, p. 725.
566 HISTORY OF TECHNICAL CHEMISTRY CHAP.
competition with the older processes for obtaining these
substances.1
Bleaching powder itself has been the subject of numberless
investigations, made with the object of arriving at its consti-
tution. It may, in fact, be said that there is no other substance
of equally simple composition regarding the nature of which
so much doubt still prevails, notwithstanding all the efforts
which have been made to clear this up.2
The two other halogens, bromine and iodine, also became
in due course important from a technical point of view,
although their much lesser abundance in nature, and con-
sequent less extended practical application, cause them to be
produced in small quantities as compared with chlorine.
The manufacture of these is based upon the original work
of Gay-Lussac and Balard. Laboratory experiments have
also led to the production of iodine from mother liquors
which were formerly looked upon as valueless, e.g. those from
Chili saltpetre and from phosphorite after its treatment with
acid. To A. Frank 3 is due the merit of having made bromine
available for technical purposes, by preparing it from the
Stassfurt waste salts. Large quantities of both of these
halogens, especially bromine, (in combination with silver) are
now employed in photography.
Nitric acid also plays an important part in chemical in-
dustries, especially since the development of the manufacture
of explosives on a large scale. Potassium nitrate, which has
been known and valued for so .long, is still an indispensable
ingredient of black gunpowder. Since the introduction of
the nitrate of soda from the Chili deposits, nitric acid has
been prepared from it (instead of from the more expensive
nitrate of potash) by the old process of distillation with sul-
phuric acid, the latest step in advance here being the distilla-
tion of the nitric acid in a vacuum (Valentiner). At the
same time nitrate of soda is now largely converted into the
1 Cf. Oettel's Entwickelung der elektrochemischen Industrie (Stuttgart,
1896).
2 Cf. The History of Inorganic Chemistry, p. 426.
.3 Hofmanris Bericht, etc., vol. i. p. 127.
vi NITRIC ACID ; EXPLOSIVES 567
potash salt by double decomposition with chloride of potassium.
This process, so simple from a chemical point of view, could
however only be carried out on an extensive scale after the
rich deposits of potash salts at Stassfurt had been discovered ;
and it required careful chemical investigation to make those
salts available,1 for their composition had to be worked out,
and proper methods for separating them from one another
had to be devised. The large quantities of potassium chloride
which occur in the Stassfurt mines have led in certain instances
to the carrying out of the Leblanc process with it instead of
with common salt, and to the consequent production of car-
bonate of potash, or mineral potash, as it was called (H.
Griineberg, 1861). The extensive use of the Stassfurt potash
(and other) salts in the manufacture of artificial manures may
also be referred to here ; an immense new industry has thus
been developed concurrently with the increased produc-
tion of nitrate of soda, superphosphate of lime and salts of
ammonia.
A reference to the history of gunpowder, and of explosives
generally,2 must not be omitted here, and this all the more
because the discovery and use of the latter are connected in
the most intimate manner with the development of the
chemistry of the time. It is known that the Chinese and
Saracens made use long ago of mixtures similar to gunpowder
for fireworks, while in Europe it has been employed for the
propulsion of projectiles since the beginning of the fourteenth
century. But five hundred years passed before the chemical
reactions, which go on during the combustion of powder, were
in some degree understood. That its effect was due to the
production of gas was stated by van Helmont ; but it was only
through the exact experiments of Bunsen and SchischkofF3
upon the composition of powder gases and residues that the
foundation was laid for a theory of its combustion, this being
1 Cf. A. Frank, Hofmanris Bericht, etc., vol. i. p. 351 ; also Pfeiffer's
Kaliindiistrie ("The Potash Industry," 1887).
2 Cf. the lecture given by Lepsius before the Gesellschaft Deutscher
Naturforscher at Halle in 1891, entitled, Das alte und das neue Pidver,
p. 17. 3 Pogg. Ann., vol. cii. p. 53.
568 HISTORY OF TECHNICAL CHEMISTRY CHAP.
further developed by the later work of Linck, Karolyi, Abel
and Noble, Debus and others.
The explosives (with the exception of gunpowder), whose
preparation now forms such a great industry, have all been
made available for practical use by chemical investigations. The
epoch-making discovery of gun-cotton by Schonbein, Bottger,
and J. Otto (independently) in 1846 must be recalled here ;
its chemical nature and reaction upon ignition were cleared
up by the laborious work of Lenk, Karolyi, Heeren, Abel and
others. Nitro-glycerine had been known as a chemical pre-
paration, discovered by Sobrero, for fifteen years before it
began to find extended application in 1862, as the result of
Nobel's researches. The careful investigations of Abel, E.
Kopp and Champion upon its modes of formation and
chemical behaviour immensely facilitated both its own manu-
facture and that of its various preparations, — dynamite, etc.
Since 1888 an important forward step has been made here, in
that nitro-glycerine and gun-cotton — up to then only applicable
as explosives — were brought by the process of " gelatinis-
ing " into a condition in which they might be used with
safety in guns. The " smokeless powder," which is now so
much employed, but which varies widely in composition from
the various methods used in its preparation, is also to be
placed in the same category as the explosives just mentioned,
since it contains nitro-cellulose. Systematic chemical inves-
tigation has now rendered it possible to prepare this powder
with a definite ballistic value. Reference must also be made
again at this point to the famous researches of Liebig and other
chemists upon the fulminates, which rendered the manufacture
of fulminate of mercury and its use in the preparation of
fuses possible.
The whole match industry likewise owes its enormous
development to the increased knowledge of chemical pre-
parations and processes. What a contrast there is between
the " chemical tinder " of 1807 — i.e. matches containing a
mixture of chlorate of potash and sulphur, which were ignited
by dipping them into sulphuric acid — and our present friction
matches ! Those prepared with phosphorus were introduced
vi MATCHES; SOAP 569
in 1833 by Irinyi of Pesth, Homer of Vienna and Moldenhauer
of Darmstadt; they have since then undergone many im-
provements, the most important of these being subsequent to
the discovery of amorphous (non-poisonous) phosphorus, which
has been used since the year 1848, although for a long time
only in small quantity, either in the match itself or in the
material of the surface upon which the match is rubbed.
Phosphorus, which last century was still a chemical curiosity,
has been manufactured on the large scale for about fifty years.
Scheele's process for its preparation was improved upon by
Nicolas so far back as 1778, and has been materially modified
in recent years, e.g. by Fleck.
Hand in hand with the development of the soda industry
went the expansion of other branches of chemical manu-
facture, prominent among which was that of soap. In order
to appreciate the influence of chemical investigation upon
this, we have to recall to mind the pioneering labours of
Chevreul1 on the subject. The knowledge of the chemical
nature of fats to which they led was perfected by later work,
particularly by that of Heintz and of Berthelot, which finally
proved that the fats were neutral glycerine ethers of various
fatty acids.2 The manufacture of stearine candles and of
glycerine, which are important both as commercial and
household products, may be regarded as the fruits of the
labours just spoken of, in addition to which those of A. de Milly
(the originator of the stearine industry), Melsens, and Fremy
deserve special mention. Further valuable improvements
in these manufactures have been effected by chemical inves-
tigation within the last few years (cf. Deite's book upon the
manufacture of soap, the article on Soap in Thorpe's Dictionary,
by the late Alder Wright, Schadler's book on the technology
of Fats and Oils, and W. Lant Carpenter's volume on The
1 M. E. Chevreul, born in 1786, lived until 1889. He occupied in his
time a number of responsible posts in Paris, the last being that of Director
of the Dyeing Department and Professor of Chemistry as applied to dyeing
in the world-renouned Gobelins tapestry works. His classical Recherches
sur les corps gras aborigine animate gave rise to a great amount of work of
a physiologico-chemical nature upon dyes, adipocere and other substances.
2 Cf. p. 441.
570 HISTORY OF TECHNICAL CHEMISTRY CHAP.
Manufacture of Soaps and Candles, etc., 1895). From a
commercial point of view, the working out of methods for
determining the value of any oil or fat and for detecting
adulterations has been of the first importance (see Benedict's
admirable work, Analyse der Fette, Berlin, 1897 ; English
edition, revised and enlarged by Dr. J. Lewkowitsch, 1895).
Closely connected also with the soda industry stand the
manufactures of ultramarine and of glass. The former
substance, which is in a special degree a product of chemical
research, was discovered in 1828 by Chr. Gmelin, and
also at about the same time by Guimet. It has given rise
to a large amount of scientific investigation,1 which has led
to material improvements in the manufacture of the various
kinds of ultramarine, and has also explained particular
parts of the firing process, but from which no final opinion
has yet been formed as to the chemical nature of this
curious product. The two hypotheses still oppose one
another — viz. (1) that ultramarine is a definite chemical
compound, and (2) that it is a mixture similar to glass.
The recent work of F. Knapp 2 has, however, begun to
throw some light upon the cause of the colour of ultra-
marine.
Although the production of glass reached a high state of
development in olden times through pure empiricism, it too
has greatly benefited by chemical research. The manufacture
of glass with sulphate of soda and the -improvements in
flint and crystal glasses belong to the present century, while
progress has also been made in silvering (by Liebig), and in
glass painting, through the discovery of new mineral colours.
The investigations of Wohler, Knapp, Ebell, M. Muller and
others resulted in elucidating the chemical reasons for the
different colours of different glasses. Lastly, laboratory work
has greatly advanced the art of imitating the precious stones,
and, generally, of producing new varieties of glass. The
chemical reactions which go on during the formation of glass
1 The work of Leykauf, Biichner, R. Hoffmann, Knapp and
Guckelberger may be referred to here.
2 Journ. pr. Chem. (2), vol. xxxviii. p. 48.
vi EARTHENWARE AND POTTERY ; MORTAR 571
have given rise to much experimental -work,1 but the conclu-
sions drawn from this — as to whether glass is a true chemical
compound or not — have been very various. Chemical analysis
has of late years produced results not merely of scientific
interest, but of very great practical importance with regard
to the manufacture of glass.2
Water glass, which was known to Agricola, Glauber, etc.,
was made available for technical purposes by Fuchs in 1818,
and has since then been used for a great number of different
purposes — e.g. for impregnating wood, preparing cements,
protecting frescoes, etc.
Earthenware and Pottery. — Important practical im-
provements in this old field of industry are associated with the
names of Wedgwood, Littler, Sadler and others. C. Bischof,3
Richters,4 and, more recently, Seger5 have rendered good
service in their chemical investigations upon the nature of
fireclay, and on the connection between its composition and
its behaviour at high temperatures. The labours just cited
have also done much to improve the manufacture of pottery,
by enabling the proper mixtures of the ingredients to be
made. The ceramic art is further greatly indebted to
chemistry as regards glazing and the burning-in of colours.
The preparation and application of mortar, especially of
hydraulic cement, have likewise been greatly advanced by
purely chemical work, whereby a nearer approach has been
made to the solution of the much-discussed problem, — how
the hardening is to be explained from a chemical point of
view. Many investigations have been made with a view of
arriving at the explanation of this, the chief property of
cements, among others by Winkler, Feichtinger, Michaelis,6
1 Pelouze, Ann. Chim. Phys. (4), vol. x. p. 184 ; R. Weber, Wagner's
Jahresbericht for 1863, p. 391 ; Benrath, ibid., 1871, p. 398 ; also Benrath's
book, Die Glasfabrikation (" The Manufacture of Glass," 1875).
2 See the investigations of Schott, Mylius, R. WTeber, Forster, Gray
and Dobbie, and others.
3 Dingl. Journ., vols. clix. cxciv. cxcviii. and cc.
4 Ibid., vol. cxci. p. 150.
5 Ibid., vol. ccxxv ii. p. 70.
6 Cf. his pamphlet, Die hydraidischen Mortel, etc. (Leipzig, 1869).
572 HISTORY OF TECHNICAL CHEMISTRY CHAP.
F. Schott,1 Fr. Knapp 2 and Michel.3 The old view of the
hardening process, viz. that it consists entirely in the gradual
formation of a calcium silicate, had to be abandoned as in-
sufficient ; but a complete theory of it still remains to be given.
The advances made in the manufacture of paper can be
but partially touched upon here, the more especially since
they belong chiefly to the domain of mechanics. The
attempts to utilise raw vegetable products, particularly wood
and straw, for the production of paper, were first successfully
carried out in the year 1846. In caustic soda a reagent
was found by means of which cellulose could be prepared
from these materials ; while of late years a solution of calcium
sulphite in sulphurous acid has shown itself especially well
adapted for this purpose. The above process for the produc-
tion of sulphite cellulose resulted from the chemical investiga*
tions of Tilghman and especially Al. Mitscherlich. The
conversion of cellulose into cane-sugar or alcohol is another
problem which has been often attacked, and from many
different sides, but it still remains to be solved. Should
this ultimately be successfully carried out on the large scale,
a complete revolution would be effected in agriculture and
husbandry generally.4
The manufacture of starch and of the products obtained
from it has also derived great advantage from chemical
investigations. The transformation which starch undergoes
upon treatment with acids has only recently been cleared
up in some degree by the work of Marcker, Musculus,
O'Sullivan, Payen, Brown and Heron, Salomon, Allihn, etc.
The earliest observation on the production of starch-sugar
was made by Kirchhoff in 1811, and from this an important
branch of industry has now arisen ; dextrine, which has for
long been used as a substitute for natural gum, is obtained
as the intermediate product here.
1 Dingl. Journ., vol. ccii. p. 434; vol. ccix. p. 130.
2 Ibid., vol. ccii. p. 513.
3 Journ. pr. Chem. (2), vol. xxxiii. p. 548.
4 For details regarding cellulose and its applications, vide Cross, Bevan
and Beadle's excellent book on Cellulose, etc., (1895).
vi THE MANUFACTURE OF SUGAR 573
The beet-sugar industry has developed into something
enormous from experiments instituted by chemists on a
small scale.1 Marggrafs discovery, in 1747, that sugar was
present in the juice of beet, was not at that time capable of
being applied commercially. Achard, a pupil of Marggraf,
and, in a lesser degree, Hermbstadt, Lampadius and others,
again took up at the end of last century the problem of
obtaining sugar from beet on the large scale, and they did
succeed in devising a process which was carried out in
numerous factories during the years of the Napoleonic wars,
when the trade of the Continent was driven in upon itself.
But this process was unable to live long, being a very
imperfect one, and giving but a small yield of sugar. It
is from the year 1825 that the real rise of the beet-sugar
industry dates, various factors entering into its growth, not
the least of which was the practical application of chemical
knowledge. We have but to think, for example, of the
development of saccharimetric methods, whose aim was the
determination — either by chemical or by physical means — of
the percentage of sugar in beet juice ; of the improvements
in the refining process ; 2 of the recovery of the crystallisable
sugar in molasses, and so on. The filtration of the refined
juice through bone charcoal was first recommended by Figuier
in 1811, and then by Derosne in 1812, and has since become
an essential part of the process. The use of vacuum pans
for evaporating the syrup was introduced by Howard in 1813,
since which time many improvements have been made in
them. The extremely convenient diffusion process, for
obtaining the juice of the beet, was discovered by Roberts
(of Seelowitz, Mahren) in 1866, and soon came into general
use, at first in Austria. Osmosis, which was first applied on
the large scale by Dubrunfaut in 1863 for extracting the
crystallisable sugar from molasses, has been developed by
1 Cf. Stohmann's Zuckerfabrikation (1893); E. 0. v Lippmann's
Geschichte des Zuckers ; and the article on sugar in Thorpe's Dictionary of
Applied Chemistry by Newlands Brothers.
2 The decomposition of saccharate of lime by carbonic acid was intro-
duced by Barruel and Kuhlmann.
574 HISTORY OF TECHNICAL CHEMISTRY CHAP.
researches in physical chemistry, — another instance of the
practical utility of scientific investigation.
A passing reference may be made here to the good done
to this branch of industry by agricultural chemistry, in the
determination of the most favourable conditions for the
growth of beet, and the investigation of the composition of
the soils and manures employed, etc. Indeed, there is hardly
any other branch of technical chemistry so intimately con-
nected with agriculture as the beet-sugar manufacture. The
production of artificial manures has received a powerful im-
pulse from the immense quantity of beet now under cultiva-
tion. Lastly, pure chemistry itself has benefited in many
respects from the careful investigation of beet juice.1
The so-called saccharine, a compound containing sulphur
which is now manufactured from the toluene of coal-tar, and
which is used to a certain extent in lieu of sugar, offers an
example of the assiduity with which every branch of chemical
industry is being exploited with the object of imitating
natural products by artificial ones, and even of replacing
the former by other more active substances.
Fermentation Processes?
The development of the various manufactures involving
fermentation has been immensely advanced by chemical
investigation, while at the same time the nature of the pro-
cesses themselves has been brought into clear relief. In
place of the contact theory of Berzelius and Mitscherlich,
which was merely a re-statement of the facts in other words
and no explanation, we now have Pasteur's vital theory of
fermentation. To this also the "mechanical" theory of Liebig
had to give way, while Pasteur's opinion with respect to the
physiological functions of yeast became in its turn subsequently
1 E. 0. v. Lippmann, loc. cit.
- For the recent literature on the subject, see Hansen's Praxis der
Garungsindustrie ; Jorgensen's Mikroorqanismen der Gdhrung Industrie ;
Marcker's Spiritusindustrie ; and Thorpe's Dictionary.
vi FERMENTED LIQUORS ; ACETIC ACID 575
modified to a material extent through the researches of
others.1
The labours undertaken with the object of testing or
establishing theoretical views have also had a determining
influence upon the practical working of fermentation pro-
cesses, since the knowledge thus gained has rendered it
possible to subject these processes to a better control than
was formerly the case. Among the more important obser-
vations in this branch during the last few years is that of
Effront upon the favourable effect of a minute quantity of
hydrofluoric acid on the fermentation process.
The good which has been done by the application of
analysis to fermented liquors is evident at a glance, since any
defects in their mode of preparation thus become apparent.
A knowledge of the normal composition of wine and beer has
led to rational suggestions for the improvement of those
drinks. It would be out of place here to attempt even a bare
enumeration of the more important innovations in this branch,
many of which are due to Pasteur.2
The manufacture of spirits may be cited as one of the great
branches of industry which has been helped to its present
high state of development by chemical work. We have
also the enormous production of alcoholic preparations 3
from spirit itself, as well as from the first and last runnings of
the still ; the manufacture of ordinary and of compound
ethers, the latter of which are so largely used in perfumery
and for making artificial liqueurs ; and that of chloroform,
iodoform and chloral, whose importance in a medicinal sense
is sufficiently well known.
The knowledge that the formation of acetic acid from
alcohol depended upon the oxidation of the latter, formed the
basis of the Quick Vinegar Process* the development of which
1 Cf . The History of Physiological Chemistry, p. 546 et seq.
2 Cf. especially the works of Pasteur, Hansen and Jorgensen.
3 E.g. Ethyl iodide, bromide and nitrite ; propyl and isobutyl com-
pounds, etc.
4 This process was first carried out by Schiizenbach in Freiburg in 1823,
and then by Wagenmann in Berlin in 1824.
576 HISTORY OF TECHNICAL CHEMISTRY CHAP.
was the direct consequence of Dobereiner's work ; while, on
the other hand, the technical production of pyroligneous acid,
methyl alcohol, acetone, etc., arose from the chemical investi-
gation of the products of the distillation of wood.
The Aniline Colours and other similar Dyes.1
There is no industry which better illustrates the practical
good that accrues from scientific chemical researches than that
of coal-tar, the working up of this substance and perfecting of
the numerous methods involved in so doing having set in
motion and continued to permanently occupy the energies of a
large army of chemists. It was clearly proved here that pure
chemical work was the necessary preliminary to the develop-
ment of each and every branch of the whole coal-tar industry.
In no other section of technical chemistry have there been so
many discoveries made by systematic investigation as in that
of artificial dyes.
Out of the large number of important investigations by
which the industry has been advanced, only the most striking
can be mentioned here,2 — those which have had an undoubted
influence in shaping this branch of chemical manufacture.
This applies to A. W. Hofmann's classical researches upon
aniline and its derivatives, and upon rosaniline, the base of
fuchsine (magenta), and its derivatives; and also to the notable
work done by E. and O. Fischer upon para-rosaniline and
1 Cf. especially Nietzki's Chemie der Organischen Farbstoffe ("The
Chemistry of the Organic Colouring Matters," 1889) ; G. Schultz's Chemie
des Steinkohlentheers, etc. ("The Chemistry of Coal-Tar," etc., 1886-90).
R. Mohlau's Organische Farbstoffe welche in der Textilindustrie Verwendung
finden ("Organic Dyes used in the Textile Industry," 1890) ; and the very
valuable report on the Progress of the Colour Industry, etc., published
half-yearly by H. Erdmann in the journal, Chemische Industrie. The
utility of such a report may be gauged from the extraordinary amount of
literature continually appearing in this branch of the science.
2 For the references to special papers, see The History of Organic
Chemistry, the works cited in note 1, and Caro's lecture on the Develop-
ment of the Coal-Tar Colour Industry (Ber., vol. xxv. Ref. p. 955).
-vi THE COAL TAR COLOURS 577
rosaniline, which established the constitution of these com-
pounds. The deep significance for technical industry which
the investigations of Coupier and Rosenstiehl on the toluidines
possessed is sufficiently well-known, while important results
also accrued from these to the pure science. The beautiful
discovery of green dyes from oil of bitter almonds and benzo-
trichloride by 0. Fischer and Db'bner (working separately) in
1877 may likewise be recalled, as also the proof that these
substances were, like rosaniline and aurine, derivatives of
triphenyl-methane. It must not be forgotten that Mansfield's
work of fifty years ago laid the necessary foundation for the
development of the aniline industry,1 for it rendered possible
the production of benzene and its homologues from coal-tar
on the large scale, and also of nitro-benzene.
The first aniline dye which was produced upon a
technical scale was the violet prepared by Perkin in 1856,
by acting upon aniline with bichromate of potash and
sulphuric acid. A. W. Hofmann observed in 1858 the
formation of aniline red (magenta), which was shortly after-
wards manufactured by another method by Verguin of Lyons,
and introduced into commerce under the name of fuchsine.
This was quickly followed by Hofmann's discovery of aniline
blue, aniline violet and aniline green, which were further
proved by that chemist to be derivatives of fuchsine. The
discovery of methyl violet by Lauth in 1861 2 and that of
aniline black by Lightfoot in 1863 were of great practical
importance. While the constitution of this last compound is
still enveloped in mystery, that of the other aniline dyes is
now for the most part known, thanks especially to the investi-
gations of E. and O. Fischer, mentioned above. In addition
to this, new and important methods for the production of
rosaniline dyes have been discovered and developed, e.g.,
formic aldehyde and carbonyl chloride are now used for the
synthesis of magenta, methyl violet, and allied compounds.
1 Journ. Chem. Soc., vol. i. p. 244, vol. viii. p. 110. Mansfield fell a
victim to his work, dying of the severe burns which he received as the
result of an explosion.
2 This dye was not, however, prepared on the large scale until 1867.
P P
578 HISTORY OF TECHNICAL CHEMISTRY CHAP.
Chemical research has also borne rich fruit in respect to the
alizarine industry. This valuable dye was formerly prepared
entirely from the madder root, but is now, practically speaking,
obtained only from coal-tar, this revolution having been
brought about by Graebe and Liebermann's successful
synthesis (in 1869) of alizarine from anthracene, a constituent
of coal-tar. In fact, the madder plantations of Alsace, the
south of France and Algiers, which were in a flourishing con-
dition twenty-five or thirty years ago, have now almost ceased
to exist. In addition to this great practical triumph, the
purely scientific results, which consisted in the determination
of the chemical constitution of alizarine and similar com-
pounds, must also be borne in mind.
A. Baeyer's successful conversion of phthalic acid into
colouring matters (the phthaleins) was of practical import-
ance, since it led to Caro's discovery of the beautiful eosin
dyes, while it also proved itself fruitful from a purely
scientific point of view, as the elucidation of the constitution
of these phthaleins threw light upon other branches of the
subject.
From the memorable researches of P. Griess upon the
diazo-compounds, supplemented by those of Caro, Nietzki,
Witt and others, the manufacture of azo-dyes has arisen ; the
modes of formation and constitution of these were so clearly
made out by the above investigators that an endless series of
valuable colouring matters can now be produced by certain
typical reactions. The first azo-dye was brought into com-
merce under the name of aniline yellow so long ago as 1864,
without, however, its true constitution being known. It is
only since 1876 that the enormous development of this
industry dates ; quickly following upon one another came
chrysoidin, the tropseolines (most of which are yellow and
orange dyes), the Ponceaux and " Fast Red " of commerce
(red dyes distinguished by their purity), together with
Biebrich scarlet and crocein scarlet. The most important
discovery of recent years in this direction was that of the
" substantive cotton dyes," obtained from benzidine and
similar compounds by Botticher and others in 1884, as
vi INDIGO BLUE AND OTHER DYES 579
examples of which we may cite Congo red and chrysamine.
The fact that there are more than 150 azo-colours in the
market is sufficient evidence of the immense number of such
compounds.
The chemical investigation of methylene blue and the
safranines, new dyes of great value, has been of much import-
ance both practically and theoretically, the rational composition
of the former having been arrived at by Bernthsen, and that of
the latter by Nietzki and Witt. The great aim of so many
of the researches upon the organic colouring matters, viz.,
the elucidation of their relations to other compounds from
which they are readily derivable, has in the above cases been
attained ; methylene blue is derived from thio-diphenyl-
amine,and the safranines from phenazine. Similarly rosaniline,.
aurine and numerous allied substances have been proved to
be derivatives of triphenyl-methane ; the azo-dyes to be
derivatives of azo-benzene and azo-naphthalene ; and alizarine,
purpurine, etc., to be derivatives of anthraquinone. It is also
now known that the indophenols and indamines, the eurho-
dols and eurhodines, the rhodamines, etc., are derivatives of
definite chemical compounds not in themselves dyes, but
which become so by the entrance of certain atomic groups
into the molecule. Various attempts have lately been made
by Witt, Nietzki and Armstrong among others, to discover
definite relations between the chemical constitution of dyes
and their colouring properties, but these speculations have as
yet no claim to be looked upon as constituting a theory ; they
are more or less only a re-statement of facts.
The chemical investigation of indigo blue, the most
valuable of all blue dyes, has also been ardently prosecuted,
with a view of arriving at its constitution, which, however, is
not yet definitely settled. Most of our knowledge on the
subject is due to v. Baeyer. He succeeded several years ago
in preparing indigo artificially from simpler compounds con-
tained in coal-tar, but until quite recently no one was able to
convert any one of the known syntheses into a practical
commercial process. The new Heumann-Lederer method,
however, by which indigo blue is prepared from phenyl-amido-
p p 2
580 HISTORY OF TECHNICAL CHEMISTRY CHAP.
acetic acid, is carried out in a modified form by the well-
known Badische Aniline and Soda Manufactory, so that
" artificial " indigo is now in the market.
Dyeing and Tanning.
The processes by which colours are fixed upon vegetable or
animal fibres have been greatly improved since the chemical
nature of dyes came to be known, although there are some
cases in which a true explanation is still required of the mode
in which the fibres themselves and certain mordants act.
The earliest attempt, even if it was an imperfect one, to get
clear ideas upon this subject was made by Macquer in 1795.
The empiricism which prevailed for so long in the dyeing
industry has gradually been done away with, thanks to the
efforts of chemists to obtain a truer insight into the reac-
tions which dyeing involves. Attention must be called here
to the investigations of Knecht on the subject, according to
which the fixation of dyes by wool fibre is dependent on the
chemical nature of the latter.
With respect to the application of the more important dyes,
previous to the discovery of the coal-tar colours, it may be
mentioned that indigo was used in Europe from the first half
of last century, and madder red from the second half, while
picric acid came into vogue at the beginning of the present
one. The use of extract of campechy-wood (which is still
very considerable) dates from about the year 1840, and that
of the dye from the yellow berries of the Chinese plant,
Sophora japonica, from about 1848. Reference must also be
made to the improvements in the application of metallic
colours in dyeing, e.g., Prussian blue, chrome yellow, chrome
orange, etc.
Tanning, whose processes up to 1860 or so were almost
purely empirical, has been made susceptible of scientific
treatment through the investigations of Knapp, Eittner,
Bottinger and others. This subject ought to have a great
interest for chemists, seeing that, according to Knapp, it con-
vi CHEMICAL PREPARATIONS 581
stitutes a special case of dyeing, many analogies being apparent
between the two. The researches on the various tannic acids
have been of value from a theoretical point of view, both to
chemistry and to vegetable physiology. Among the important
practical innovations, for which this branch of manufacture
has to thank chemistry, the mineral tanning introduced by
Knapp, Heinzerling and others deserves notice. But there is
as yet no general theory of the various tanning processes.
Various Chemical Preparations.
An immense industry — that of so-called chemical prepar-
ations— has gradually been developed on scientific lines from
apparently insignificant beginnings, which had their origin in
the work of the apothecary; such ''preparations" belong
partly to inorganic, and partly to organic chemistry.1 As
instances of this we may take the great increase in the pro-
duction of silver salts, bromine and iodine for photographic
and other purposes, and the manufacture of numberless other
metallic salts, not to speak of newly introduced compounds
like the peroxides of hydrogen and sodium. The already
imposing list of inorganic preparations is being continually
added to. Here again it is scientific investigation which has
led to the use of such substances in manufactures generally.
The manufacture of organic preparations is still more
extensive. What a multiplicity of compounds, for instance,
is comprised under the term alcoholic preparations ! The
various alcohols themselves, their ethers and esters, chloro-
form, chloral, iodoform, aldehyde, etc., are now all essential to
chemical manufactures and to medicine; while among the
phenols, carbolic acid and the cresols, hydroquinone, pyro-
catechin, resorcin, pyrogallol and others, together with many
of their derivatives, have found extended application in
medicine, photography, and for disinfecting and other pur-
poses.
1 For the scientific importance of this branch of industry, and indeed
of technical chemistry generally, compare H. Wichelhaus's Wissenschaftliche
Bedeutung chemischer Arbeiten (1893).
582 HISTORY OF TECHNICAL CHEMISTRY CHAP.
The manufacture of organic acids, of which acetic acid has
already been referred to, also shows a continuous develop-
ment ; many of these compounds which occur in nature are
now prepared artificially on a large scale, the methods fol-
lowed being based upon scientific investigation. Thus, sali-
cylic acid is produced from carbolic (Kolbe and R Schmitt),
benzoic acid from toluene, phthalic acid from naphthalene,
cinnamic acid from benzoic aldehyde, and oxalic acid from
wood by treating the latter with alkali, etc. This last pro-
cess was discovered by Gay-Lussac in 1829, and its practical
application now constitutes an important industry.
The manufacture of aldehydes is likewise the result of
scientific work. Some of these, such as benzoic aldehyde, are
of importance for the colour industry, while others, like
vanillin and piperonal, are flavouring essences or scents. The
so-called ethereal oils belong to this last category ; and much
has been done by the researches of Wallach, Semmler,
Tiemann, Bertram and others to place their manufacture on a
sound basis. Systematic investigation has also brought about
great advances with regard to the vegetable alkaloids, as is evi-
dent in the strenuous endeavours to prepare artificial com-
pounds which shall have the same physiological actions as
quinine, morphine, atropine, etc.
Various other Products from Coal-tar ; Illuminants.
Coal-tar is the raw material from which many other
organic preparations are obtained, — it is, in fact, a rich mine
for numberless useful substances. Formerly a troublesome
waste material, it is now of at least equal value with the other
products from the distillation of coal. The manufacture of
ammonia and salts of ammonia from gas liquor is now a
thoroughly rational one, thanks to the careful chemical ex-
amination of the latter, and it forms a large and important
branch of industry. In consequence of the rapidly increasing
consumption of ammonia salts, more and more attention is
being paid to the problem of utilising the ammonia which
vi OTHER COAL-TAR PRODUCTS ; ILLUMINANTS 583
escapes into the air when coal is either converted into coke l
or is completely burnt. L. Mond 2 has lately set up an in-
geniously constructed apparatus on a large scale at North wich
in Cheshire, which serves not merely for heating purposes,
but at the same time allows of the condensation of the am-
monia produced. The manufacture of coal-gas has developed
in a more empirical manner, and has thus been less influenced
by recent chemical researches bearing upon the subject than
many other branches of industry ; but here, too, much good
has been done by the application of the methods of gas
analysis, and chemical experiments have also borne fruit in
the introduction of improved modes of purifying gas. It is
interesting to note here that acetylene, which is itself an
electro-technical product, appears destined to enter into
serious competition as an illuminant with the electric light.
The great influence which chemical investigations have
exercised upon the production of other illuminants has already
been touched upon, and is shown in the manufacture of stearic
acid from animal fats.3 Attempts have been made upon the
large scale to employ (the liquid) oleic acid, which occurs so
plentifully in nature, for the production of candles, by making
use of the well-known reaction with caustic potash, which
converts it into (solid) palmitic acid. The flourishing paraffin
manufacture 4 of Scotland and Germany, with its various
valuable by-products, also owes much to chemistry. ' But the
latter has still many problems to solve both in this field and
in that of the petroleum industry, as is evident from the
recent work of Markownikoff, Beilstein and Engler upon the
chemical nature of petroleum ; these researches are bringing
us nearer to a solution of the origin of this useful substance.
A short reference has already been made (p. 425) to the
theoretical points which bear upon illumination, and to the
causes of the luminosity or non-luminosity of different flames.5
1 Tar is now an important by-product in coking.
2 Journ. Chem. Ind. for 1889, p. 505. 3 Cf. p. 569.
4 Paraffin, which was discovered in wood-tar by Reichenbach in the
year 1830, is obtained practically from lignite or bituminous shale.
5 Cf. also Hans Bunte on "Recent Developments in Gas -Lighting," Her.,
vol. xxxi. p. 5.
584 HISTORY OF TECHNICAL CHEMISTRY CHAP.
Heating Materials.
That the knowledge gained through chemical analysis of
the composition of different kinds of fuel, of their products of
combustion, and of their chemical behaviour generally, is of
the first consequence, requires no demonstration. It is of
course impossible to refer here to the large number of im-
portant investigations in this field, but reference must be made
to the fundamental work of E. Richters and F. Muck ; l to the
improvements in the methods of analysis of furnace gases,2
which permit of conclusions being drawn with regard to the
course of any particular combustion ; and to the improvements
in heating apparatus which have been brought about by
chemical work, — the construction of generators and regener-
ators, whose history is inseparably connected with the names
of Aubertot, Thomas, Laurens and, above all others, Siemens.
" Water gas," prepared by passing steam over red-hot coal, is
now much used for heating and illuminating purposes, and it
will undoubtedly become even more employed in time ; this
is notably a case in which a great manufacture has arisen
from experiments on a very small scale.
Speculations regarding the origin of coal deposits, and the
metamorphoses which these undergo, have received much
support from the work which has been done upon the com-
position of coal and of the gases which are found enclosed in
it. And it is mainly to chemical research that we owe the
means of averting or at least diminishing the great dangers
to which coal miners are exposed from explosions of fire-damp,
— witness the Davy safety lamp. The subject is still being
assiduously worked at from time to time both by chemists
and by practical engineers. The zeal which the various
recent " Fire-Damp Commissions " of different countries
showed in their investigations is still fresh in the public
memory.
1 Cf. Muck, Grundzuge und Ziele der Steink&hlenchemie (" The Outlines
and Aims of the Chemistry of Coal," 2nd edition, 1891).
2 Cf. Winkler's Anleitung zur technischen Gasanalyse ("Methods of
Technical Gas Analysis") ; also p. 392 of this book.
vi VALUE OF CHEMICAL RESEARCH 585-
The above short sketch is sufficient to indicate how
enormous have been the benefits which laboratory research
has conferred upon every branch of technical chemistry, and
how the latter has been raised to a higher level by a con-
tinuous infusion of the scientific spirit. Nowhere can we find
a better illustration of Bacon's maxim : Scientia estpotentia.
586 CHEMICAL INSTRUCTION IN THE 19TH CENTURY CHAP.
THE GROWTH OF CHEMICAL INSTRUCTION IN THE NINE-
TEENTH CENTURY, MORE ESPECIALLY IN GERMANY, t
At the beginning of this century there was a marked want
of those facilities which, during the last few decades, have
been at the command of any one desirous of devoting himself
to the study of chemistry. At that time there were practi-
cally no laboratories for general instruction. In lectures upon
physics, mineralogy and anatomy, chemistry was relegated to
a very subordinate place. It is true that there were chairs of
chemistry in various universities and colleges, but the lectures
on this subject were usually conjoined with those upon one of
the others, just named, in such a manner that chemistry was
forced into the background. Chemical literature, lastly, was
still poor in works which either gave a review of the state of
the science at the time, or furnished regular reports of the
latest discoveries in it.
In France, where towards the end of the eighteenth
century it began to be perceived that instruction in natural
science must be fostered by every means at command, a start
was made far before any other countries in respect to the devel-
opment of chemical study. Up till then apothecaries' shops
were the only places where work in practical chemistry could
be carried on, and there merely after certain prescriptions and
not according to scientific methods. Yauquelin was the first
to organise a course of instruction in his small laboratory for
students anxious to learn, while after the first decade of the
century Gay-Lussac and Thenard also taught in their labor-
atories, which however were exceedingly cramped. Fourcroy
had already done an immense deal to raise the standard of
scientific instruction, and he contributed greatly by his bril-
1 In addition to the books referred to in the succeeding pages, compare
E. Zoller's book, mentioned on p. 556, and also Wallach's essay in Lexis'
Die deutschen Universitdten, vol. ii. p. 35 (1893).
vi DEVELOPMENT OF CHEMICAL INSTRUCTION 587
liant lectures l to ensure to chemistry a worthy position as a
course of study. But it was only after Liebig had taken up
the subject with his accustomed energy, that chemistry came
to be taught in the higher schools in essentially the same
manner as that to which we are now accustomed.2
The importance of lectures on chemistry, illustrated by
experiments, for the proper understanding of chemical re-
actions, was recognised a long time ago, more especially in
France.3 But during the early decades of the present
century this aid to study hardly existed in the higher
teaching institutions of Germany, and the so-called natural
philosophy of that day was such that it sorely handicapped
the development of exact scientific research. Chemistry, in
particular, was looked upon by the natural philosophers
as being no science at all, and was degraded by them into a
mere experimental art.
The efforts made by Davy, however, backed as these were
by an exceptional talent for devising and carrying out experi-
ments, and also by Gay-Lussac and Thenard's admirable
lectures, resulted from the beginning of this century in an
increasing demand for lectures with appropriate experimental
illustrations. Liebig has left to us a graphic description of
the effect which Gay-Lussac and Thenard's discourses had upon
himself, at that time a youth of eighteen. From this account
it is evident that these lectures gained an indescribable
charm from the " mathematical method, which transformed
each problem — wherever possible — into an equation," and by
a lucidity of expression which was " conjoined with a wonder-
ful experimental skill."
We know tha,t it was the lectures given by Marcet in
London which induced Berzelius in 1 8 1 2 to abandon the old
1 Compare Pariset's vivacious £loge de Fourcroy, cited in Hofer's
Histoire, vol. ii. p. 557.
2 Cf. below ; also 0. L. Erdmann's valuable and too little known pam-
phlet, Ueber das Studium der Chemie. Liebig willingly acknowledged the
great debt which he owed to Gay-Lussac, with whom he had worked as a
student (cf. Ber., vol. xxiii. Ref. p. 824).
3 Cf. The work of Rouelle, p. 118, note.
588 CHEMICAL INSTRUCTION IN THE 19TH CENTURY CHAP,
method of instruction and to make use of experiments in
introducing students to chemical science ; and the result of
this was conclusive. The subsequent good achieved by
Faraday, Liebig, Wohler, Bunsen, Wurtz, Kolbe and especially
A. W. Hofmann, through the new lecture experiments which
they devised, requires but to be mentioned. Those experi-
ments and many others have since taken a permanent place
in the teaching of chemistry.
Practical instruction in chemical laboratories, as com-
monly carried out at the present day, was developed by
Liebig. The gradual introduction into laboratories, through
his example, of teaching methods based upon a strictly
scientific foundation, created a wholesome reaction against
the still prevailing tendency of the natural philosophy 'of
the day, which was combated by Liebig all the more
energetically from his having himself suffered under its
pernicious influence.1 He first emphasised with all the force
at his command that the true centre-point of chemical study
lay not in lectures but in practical work. With what energy
and under what sacrifices he gave personal proof of this is
well known.2 True, Berzelius had already given instruction
in his laboratory to a limited number of pupils, mostly elder
ones, who in their turn propagated their master's doctrines,
but the real development of chemical teaching is due to
Liebig. He it was who laid down the order, now classical,
in which the various branches of the subject should succeed
one another, viz. (1) the systematic study of qualitative
and then of quantitative analysis,3 (2) exercises in the making
of preparations, and (3) attempts at independent research.
Liebig's laboratory was the centre from which, after
about the end of the twenties, the brightest light radiated.
He was the first to enunciate and apply the principle that
1 Cf. pp. 263-264.
2 Cf. the Memoir of him by Kolbe in the Journ. pr. Chem. (2), vol.
viii. p. 435 ; also Weihrich's essay (already quoted), p. 264, note 2.
3 The co-operation here of R. Fresenius, who was at one time assistant
to Liebig, and the stimulus given by him towards the creation of a system-
atic course of analytical work, will remain in lasting remembrance (cf. p.
389) ; the great service rendered by Will must also be emphasised.
vi m ERECTION OF GENERAL LABORATORIES 589
his pupils, be they students of pharmacy, technical chemistry,
mineralogy or physiology, should learn to treat chemical
questions practically. Thanks to the wonderful stimulus
which he was able to exert, there was founded in his modest
laboratory a school which left its stamp upon the chemistry
of the succeeding decades, and whose beneficial influence
is still felt all over the world at the present day. The
peculiarity of Liebig as a great teacher consisted, according
to Kolbe,1 in his " being able to stimulate his pupils to original
thought, and to inoculate them with the scientific spirit
while they were working out his own ideas."
The most eminent among the teachers of chemistry on the
Continent since the time of Liebig, of whom Wohler, Bunsen,
Erdmann, Kolbe, Kekule, Wurtz and A. W. Hofmann may be
named here, made the essential principles of his method of
teaching their own, while each added of course much that
was new, with the most beneficial results. The principles on
which chemistry is taught are the same both in the German
Universities and the Technical High Schools.
Numerous teaching laboratories were in due course
founded in the other German universities and colleges on
the model of the Giessen one, and about these a few notes
may fitly find a place here. How badly off Austria and
Prussia were in this respect, even so recently as the year
1840, was vividly depicted by Liebig in his two pamphlets
entitled Ueber den Zustand der Chemie in Qsterreich? — und
in Preussen 3 (" On the State of Chemistry in Austria, and in
Prussia "). Even in Berlin there were up to that time no
facilities for the study of practical chemistry. H. Rose and
Mitscherlich were hardly in a position to give regular
laboratory instruction, the space and means generally at
their disposal being very insufficient ; 4 and the same thing
applied to the other " high schools " of Prussia.
1 In his work, Das chemische Laboratorium der Universitdt Marburg,
etc., p. 26. In this the principles of Liebig's method of instruction are
described with exceptional clearness.
2 Ann. Chem., vol. xxv. p. 339. 3 Ibid., vol. xxxiv. pp. 97 and 355.
4 Cf . A. W. v. Hofmann' s Chemische Erinnerungen aus der Berliner Ver-
ffangenheit (1882V
590 CHEMICAL INSTRUCTION IN THE 19TH CENTURY CHAP.
In the meantime laboratories began to be established
elsewhere in Germany, e.g. at Gottingen, where Wohler set
up one in the course of the thirties, to be rebuilt and enlarged
in 1888; and at Marburg, where Bunsen began a regular
practical course in 1840. The chemical laboratory which
'Erdmann1 instituted at Leipzig in 1843 remained for a
long time the pattern of what a well-organised place of the
kind should be. It was only in the course of the fifties that
Heidelberg, Karlsruhe, Breslau, Greifswald and Konigsberg
followed suit with laboratories properly equipped for the
purposes in view.
A new era in the history of chemical institutions began
about the middle of the sixties, the famous laboratories at
Bonn and Berlin,2 both built according to A. W. Hofmann's
plans, being completed in 1867, while the equally well-
known Leipzig laboratory, designed by Kolbe, was finished
in 1868. The experience gained, both during the erection
of these and by their subsequent use, has been applied with
good results in the planning of later and even in some
respects finer institutes. Of the other new German labora-
tories, those of Aachen3 (18 70), Dresden (1875), Munich
(1877), the Berlin Technical College (1879), Kiel 1880),
Strassburg (1885), Gottingen (1888), Heidelberg (1892)
and Halle (1894), may be specially named. In Austria,
too, various excellent laboratories, have been built during the
last two decades, among which those of Graz and Vienna
stand out prominent.
1 Otto Linne Erdmann was born at Dresden in 1804, and died in 1867
while holding the post of Professor of Chemistry at Leipzig, where, since
1827, and especially after the organisation of the laboratory which he had
himself founded, he laboured with wonderful energy and with great suc-
cess. His rich experiences, and the views to which they gave rise, were
set forth in the weighty, if short, pamphlet entitled, Ueber das Studium
der Chemie (1861). That he was also active in a literary sense, his Lehr-
buch der Chemie and Orundriss der Waarenkunde (" Outlines of a Knowledge
of Technical Products "), etc., prove. In 1828 he started the Journal fur
technische und okonomische Chemie, which developed in 1834 into the
Journal fiir praktische Chemie. His numerous experimental researches
have helped to enrich mineral chemistry, the chemistry of the carbon com-
pounds, and also chemical technology.
2 Up to that date Berlin was without any large laboratory for general
instruction. 3 ^ ^ix la Chapelle.
vi TEACHING IN FRANCE AND GREAT BRITAIN 591
Among the many German University teachers who have
exercised a marked influence during the last forty years,
and who have not been already mentioned, von Baeyer
takes a foremost place, while in addition there are Glaus,
Erlenmeyer, E. Fischer, Fittig, Ladenburg, Lothar Meyer,
Victor Meyer, Strecker and Wislicenus.
The other countries of Europe have not kept pace with
Germany in the establishment of institutes for the teaching
of chemistry. There were, it is true, laboratories in France
at the beginning of the century in which such men as Gay-
Lussac, The"nard, Dulong, Chevreul and others carried out
their work, but the opportunities for general chemical
instruction were extremely few, the above institutes
receiving but trifling support from the State. And the
fees which a laboratory student had to pay were ex-
orbitant, being 1500 francs for an eight-months' course.
Even the efforts made to establish teaching laboratories
during the thirties by Dumas and Pelouze, and later on
by Wurtz, Gerhardt and others, were followed with but scant
success, because these chemists were thrown entirely on their
own resources.
Those conditions were only improved after Wurtz in
1869 presented his report x upon the German laboratories
to the French Minister of Education, in which he insisted
upon the necessity for establishing properly equipped
laboratories for practical instruction in chemistry. He
stated that at that date there was in France only one
chemical institute with the necessary means at command
— that of the ficole Normale Supfrieure, under the direction
of H. St. Claire Deville. E. Fremy, well known by his work
in inorganic and technical chemistry, had set up a
laboratory in 1864; and in the introduction to his
Encyclopedia of Chemistry he gives a detailed account of
the principles upon which chemistry was taught in it.
Fremy died in Paris in 1 8 9 4, at the age of eighty.
In Great Britain, too, it is only within the last twenty-five
or thirty years that the lack of roomy and well-equipped
1 Les halites Etudes pratiques dans les Universite's allemandes (1870).
592 CHEMICAL INSTRUCTION IN THE 19TH CENTURY CHAP.
laboratories has been remedied; and to this, especially of
late years, the recognition of the fact that the industries of
the country would be enormously benefited thereby has
greatly contributed. The first laboratory in Britain, small
though it was, in which a young man had the opportunity
of working practically at the subject, was that of Thomas
Thomson1 in Glasgow, established in 1 8 1 7. This was therefore
the first chemical laboratory for general instruction. After the
founding of the College of Chemistry 2 in London in 1845
(which quickly rose into a flourishing condition under the
leadership of A. W. Hofmann), the country became by
degrees well supplied with suitably equipped laboratories,
in which instruction substantially upon the lines of the
German school was given. In addition to the Universities
and a few of the older institutions for higher education in
London, etc., each of the University Colleges now scattered
over the country possesses its own chemical laboratory, and
the same thing applies in greater or less degree to the
colleges and schools for technical instruction which continue
to be founded with considerable rapidity. In fact, the mind
of the country is now becoming to some extent awakened to
the importance of the subject. Among the chemical labor-
atories, more or less recently erected, those at Manchester,
Leeds, Edinburgh, the City and Guilds Institute (South
Kensington, London), and Cambridge may be specially
named.
In Switzerland, Holland, Belgium, Italy, Russia, Scandi-
navia and America are now to be found numerous chemical
teaching institutes, arranged and fitted up in accordance with
the requirements of the age.
The increasing necessity for specialisation in chemistry,
1 Cf. p. 194.
2 The College of Chemistry was taken over by Government in 1853, and
was made a part of the Royal School of Mines, while at the same time
retaining a quasi-separate existence under its own name. In 1872 it was
moved from its old premises in Oxford Street to South Kensington. The
name College of Chemistry was finally merged into that of the Normal
School of Science and Royal School of Mines in 1881. In 1890 the N. S. S.
and R. S. M. were rechristened the Royal College of Science.
vi IMPROVEMENTS IN LABORATORY APPARATUS 593
and the consequent resulting division of labour, has made
itself evident in the establishment of laboratories for certain
definite purposes only. Thus we now find institutions
existing solely for researches in chemical physics, agri-
cultural chemistry, technological chemistry, physiological
chemistry, pharmaceutical chemistry and hygiene. What
a contrast between the present facilities for chemical study
and the opportunities of only a few decades back !
Among the more important improvements which have
been aimed at and achieved in the construction of labora-
tories during these last decades, are those which have
reference to arrangements for supplying plentiful ventilation
and good light. Then the means for carrying out chemical
operations have also been both greatly increased and im-
proved, e.g. coal and charcoal fires have been superseded
by gas, the Bunsen burner having played an important part
here. The apparatus, too, employed by chemists has under-
gone many refinements, as is readily seen in the delicate
balances and the appliances for filtering, distilling, heating
under ordinary and increased pressure, etc., which are now in
common use.1 The making of preparations is at present an
easy matter compared with what it used to be, this being in
part due to better methods of procedure ; by far the greater
number of these substances can now in fact be bought pure.
Chemists are thus freed from the difficulty which
1 The following points may be referred to with advantage here : — Water
suction pumps were introduced by Bunsen in 1868, and injector pumps a
little later by Arzberger, Zulkowsky, etc. , to be used for filtering and pro-
ducing a vacuum. Simple distillation was immensely facilitated by the
introduction of the Liebig condenser, while a reflux condenser appears to
have been first made use of by Kolbe and Frankland in 1847. Dittmar
and Anschiitz (independently of one another) were the first to distil under
diminished pressure. The water-bath, for which Berzelius devised a con-
venient form, has since been improved by arrangements, elaborated by
Fresenius, Bunsen, Kekule and others, for keeping the water in it at a
constant level. The use of gas regulators for the maintenance of a uniform
temperature may also be mentioned, and this again in conjunction with
Bunsen's name. Caoutchouc tubing appears to have been first brought
into general employment by Berzelius. And the first mention of the use of
sealed tubes for carrying out chemical reactions under pressure is to be
found in Wohler and Liebig's research on uric acid derivatives.
Q Q
594 CHEMICAL INSTRUCTION IN THE 19-TH CENTURY CHAP.
was ever present with them sixty or seventy years
ago, — of having laboriously to prepare even their most
simple reagents. Berzelius had to make his own yellow
prussiate of potash, the pure mineral acids, spirits of wine
for burning, etc. And how simple were the arrangements
generally in his laboratory ! l Many of the aids to practical
work which are now accepted as a matter of course had
in his day no existence.
Chemical Literature.
The manuals and text-books of chemistry and also the
journals have increased to a very large extent of late years,
thus greatly facilitating the study of the science. For a long
time Lavoisier's Traite" de Chimie remained the pattern of
what such a book should be, and upon it numerous others
were modelled, e.g. those of Girtanner, Gren, and Thomson.
Berzelius' large book on chemistry exercised an extraordinary
influence, especially after it had been translated into other
languages, and contributed in an exceptional degree to the
spread of chemical knowledge.
This great work, great both in its conception and in the
manner in which it was carried out, was afterwards taken in
many cases as the standard for the arrangement of chemical
matter in text-books which appeared later. Of these a few
may be mentioned here : — Thenard's TraiU de, Chimie $Umen-
taire ; Mitscherlich's^eAr&wcA der Chemie ; Liebig's Organische
Chemie ; Wohler's Grundriss der Chemie (" Outlines of
Chemistry "), from which sprang the well-known and widely-
read work of the same title by Fittig ; Regnault's Cours
Mtmentaire de Chimie, which formed the basis of Strecker's
Kurzes Lehrbuch der Chemie ; Graham's Elements of Chemistry,
from which arose Otto's large work, the organic portion of
which was written by Kolbe, while H. Kopp wrote the
general theoretical part (inorganic and organic), and
Buff and Zamminer the physico-chemical. Gerhardt's
1 Cf. Wohler's description, Ber., vol. xv. p. 3139.
vi TEXT-BOOKS AND DICTIONARIES OF CHEMISTRY 595
Traite de Chimie Organique (1853 to 1856), known as
the text-book of the type theory, greatly contributed
to the propagation of the latter, while Kekul^'s book,
which began to appear shortly after the last volume of
Gerhardt's Traitt had been published, served to develop the
" typical " view, and (in its second volume) strengthened his
own assumption as to the mode in which atoms are combined
with one another, i.e. the structure theory. It is unnecessary
to mention here even a few of the numerous text-books of
chemistry which have been written since then, for, belonging
as they do to the present era, they are already sufficiently
well known. A palpable want has recently been supplied
by the publication of W. Ostwald's, Nernst's and Horstmann's
admirable text-books of general theoretical and physical
chemistry, while Lothar Meyer's Moderne Theorien has
greatly helped to extend the interest felt in questions of
theoretical chemistry. Some of the best known text-books
on technical and physiological chemistry have been already
referred to.
There has likewise been no lack of chemical encyclo-
paedias since the great success of Liebig, in conjunction with
Wohler and Poggendorff, in the Handworterluch der reinen
und angewandten Chemie, which began to appear in 183*7.
Wurtz's Dictionnaire de Chimie pure et applique'e, Watts'
Dictionary of Chemistry, and Ladenburg's Handworterbuch
der Chemie have been written upon a similar plan. The
publication of Fremy's Encyclope'die de Chimie must also be
recalled.
Among the larger treatises of chemistry, which are
intermediate between the text- books proper and the
dictionaries, that of L. Gmelin justly excited the admiration
of his contemporaries by its consistent thoroughness. In
Beilstein's Handlmch der Organischen Chemie, already in
its third edition, the present huge mass of material
on the subject has been sifted and arranged in a masterly
manner. Dammer's Handbuch aims at doing for inorganic
chemistry what Beilstein's does for organic.
The periodical journals, whose number has gone on
Q Q 2
596 CHEMICAL INSTRUCTION IN THE 19TH CENTURY CHAP.
steadily increasing, have exercised the greatest influence
upon the enlargement and spread of chemical knowledge,
more especially since the beginning of this century. A
short account has already been given 1 of the condition of
this class of literature towards the end of last century. In
Germany, after the third decade of the present one, all the
more important chemical researches were for long published
either in Poggendorff s Annalen der Physik und Chemie or
in the Annalen der Chemie und Pharmazie, which was
at first edited by Liebig alone, but afterwards in con-
junction with Wohler. The latter journal, more particularly t
soon became the medium in which were discussed the experi-
mental and speculative chemical questions of the day. And
no one was better qualified to deal with those exhaustively
than Liebig himself.
In France the Annales de Chimie, founded in 1789
(the year of the Revolution) by Lavoisier, Fourcroy and
Berthollet, has always been appreciated and loyally supported.
Since 1816 it has appeared as the Annales de Chimie et
de Physique, its first editors under this" new title having been
Gay-Lussac and Arago, and it has all along contained the
records of pretty nearly all the more important French
chemical researches. The Comptes Rendus, which has been
published weekly by the Acade'mie Frangaise since the year
1835, includes among its numerous papers only comparatively
few and short accounts of chemical investigations.
In Great Britain, up to the year 1841, papers on chemical
subjects were published either in the Philosophical Transac-
tions, the Transactions of the Royal Society of Edinburgh,
etc., or in other more recent journals which have since been
superseded, such as Nicholson's Philosophical Journal, and
Thomson's (later Phillips') Annals of Philosophy. Since 1841 9
or at least since 1848, the Journal of the Chemical Society
has been the main organ of scientific chemistry in this country.
Apart from the original memoirs which it contains, this
1 Cf. pp. 175 and 179.
2 Until the year 1839 this journal bore the simpler title, Annalen der
Pharmazie.
vi CHEMICAL JOURNALS 597
journal has since 1871 greatly extended its usefulness by
giving copious abstracts of papers which have appeared in the
chemical journals of other countries.
And the other European countries have not been behind-
hand in the publication of chemical journals ; according to
the degree in which chemistry has found in them a
permanent home, so have journals of every shade and
variety sprung up. Most of these were and are still con-
nected with learned corporations — academies and chemical
societies — in Austria, Italy, Holland, Belgium, Switzerland.
Russia, Roumania and Scandinavia, and the same remark
-applies to the United States and Canada.
In Germany more particularly, which has now for long
been the chief centre for scientific chemical interests, thanks
to the favourable conditions for scientific instruction there,
.a number of new journals for the publication of papers
on purely chemical subjects have been added to those
older ones just mentioned. Among these are the Journal
fur Praktische Chemie, begun by Erdmann in 1834,
continued by Kolbe from 1870 to 1885, and since
the latter date edited by E. von Meyer; and, especially,
the Berichte der Deutschen Chemischen Gesellschaft, which
was brought into life with the founding of the German
Chemical Society at Berlin in 1 8 6 8, and in which one finds
a record of pretty nearly all that is being done in scientific
chemistry, either in the form of original papers or of abstracts l
from other journals. Mention must also be made here of
the Kritische Zeitschrift, known later on as the Zeitschrift
/ur Chemie, which was supported by such men as Kekule',
Erlenmeyer, Fittig and others, and the critical utterances
in which have often helped to throw light upon disputed
points in chemistry. The Chemische Centralblatt is also a
valuable journal of reference for every branch of the science.
Mention still remains to be made of the Jahresberichte
{" Yearly Reports ") on the progress of chemistry and allied
branches of science. The reports which were edited by
Berzelius (from 1821 to 1847) are unique, and are abso-
1 These abstracts are no longer printed in the Berichte, but in the
•Chemische Centralblatt.
598 CHEMICAL INSTRUCTION IN THE 19TH CENTURY CH. vi
lutely indispensable to any one who desires to make a de-
tailed study of the progress of chemistry during those
years. The continuation of them, which was undertaken by
Liebig in conjunction with other chemists, cannot be com-
pared with these earlier volumes, the new Jahresberichte
having been restricted into mere epitomes of reference with
regard to current chemical work. The Jahrbuch der Chemie,.
begun in 1891, and edited by R. Meyer in conjunction with
various collaborators, aims at giving a concise statement of
the more important advances in pure and applied chemistry.
The critic, whose use as a fermentive and corrective
agent will be denied by no one, seems, with but few
exceptions, either to have disappeared from the chemical
literature of recent years, or at all events to be at present
dormant. It is well to remember that the critical acumen
which was brought to bear upon the occasional errors of
chemical investigation by Berzelius and Liebig, and at a
later date by Kolbe, had a consolidating and not a disinte-
grating effect, even in those cases where the critic's argument
had a strongly polemical, and — to the subject of the attack
— a personal flavour.
The value of a minute study of good original papers has
time and again been insisted upon by the great teachers of
chemistry. The records of such experimental labours offer
to the student the best means of following out the author's
train of thought ; they thus strengthen the historical sense,
and at the same time strongly incite to criticism and to
emulation. They are therefore to be looked upon as among
the best literary aids to the study of chemistry. At the
same time they possess a high educational value from their
style and form alone. As Erdmann well says in his short
treatise, already cited, p. 60 : " By making use of such
sources of information the student learns at one and the same
time from a master of the science how and in what form
scientific results should be stated, how to distinguish between
what is and what is not essential, and how to condense the
subject-matter, while at the same time omitting from it
nothing of importance, so that no necessary element shall be
wanting for its critical examination."
INDEX OF AUTHOKS AND SUBJECTS
INDEX OF AUTHOKS' NAMES
The figures in thick type refer for the most part to those pages upon which
biographical notices occur, although they are also employed in some
cases for others on which points of special importance are recorded.
ABEL, 568
Abukases, 30
Achard, 573
Afzelius, 192
Agatharchides, 12
Agricola, 3, 47, 59, 83, 84, 88, 93,
95
Aitken, A. P., 535
Albertus Magnus, 30, 31, 34, 56,
137
Algarotus, 94
Allihn, 572
Ampere, 257, 418
Ammermiiller, 495
Anaximenes, 6
Anderson, 478, 484
Andrews, 405, 493
Anschiitz, 439, 593
Arago, 499, 596
d'Arcet, 558
Archimedes, 12
Arfvedson, 407
Aristotle, 2, 5, 6 et seq., 15, 20, 38
Armstrong, 452, 579
Arnaldus Villanovanus, 32, 43
Aronheim, 458
Arppe, 442
Arrhenius, 501, 503, 520
Arzberger, 593
Aubertot, 584
Augustin, 558,
Auwers, 462, 502
Avenzoar, 30
Averrhoes, 30
Avicenna, 30
Avogadro, 215, 290, 294, 490
BACON, Francis, 101, 585
Bacon, Roger, 30-31, 43
Baeyer, A. v., 349, 354, 358, 363,
366, 435, 436, 450, 454, 469, 480,
485, 537, 578, 579, 591
Bahrens, 62
Balard, 402, 418, 419, 426, 446, 566
Balling, 557
Balmer, 495
Bamberger, 363, 436, 466, 468, 472,
473, 477, 481
Bancroft, 147
de Bary, 547
Barriere, 417
Barruel, 573
Basilius Valentinus, 36, 37, 41, 46,
47, 48, 51, 52, 53etseq., 94
Baudrimont, 62
Baumann, 439, 451, 464, 543
Baume, 139, 154
Bayen, 131, 177
Beadle, 572
Beaumont, 451
Bechamp, 445
Becher, 109, 110, 134
Beckmann, E., 341, 359,454, 462,502
Beckurts, 551
Becquerel, 498, 528
Behrend, 341, 462
Beilstein, 458, 583, 595
Bence Jones, 228
Benedict, 570
Bergman, 124, 137, 138 et seq., 247,
384, 386, 417, 512, 523
Berlin, 411
Bernard, Claude, 541, 543
Bernoulli, 494
Bernthsen, 579
Berthelot, 23, 26, 28, 29, 39, 45, 46,
57, 153, 167, 168, 328, 420, 435,
508, 517, 569
602
INDEX OF AUTHORS' NAMES
Berthier, 527
Berthollet, 172, 173-174, 185 et seq.,
421, 473, 474, 513-519, 565, 596
Bertram, 582
Berzelius, 203-210, 210-213, 216
et seq., 223 et seq., 229-237, 240,
241 et seq., 248 etseq., 251-253,
255 et seq., 279, 281 et seq., 292,
313, 388 et seq., 396, 402, 404,
405, 408, 410, 411, 419, 421, 422,
424, 426, 429, 430, 441, 449, 474,
503, 516, 522, 523, 525, 587, 588,
593, 294, 597, 598
Besson, 425
Bettendorf, 410
Beudant, 221, 525
Bevan, 538, 572
Beyer, C., 481
v. Bibra, 539
Bidder, 541, 545
Biot, 499
Biringuiccio, 85
Bischof, C., 571
Bischof, G., 528
Bischoff, 543, 545
Bisehoff, C. A., 359
Black, 119-121, 128, 144, 180
Bladin, 485
Blagden, 166, 502
Blaise de Vigenere, 97
Blochmann, 425
Blomstrand, 237, 329, 340, 390, 412,
429, 430, 471, 473, 516, 526
Blyth, A. Wynter, 399
Bockorny, 537
Bodlander, 506
Boerhave, 60, 113, 114-115, 133,
135, 137
Bolley, 556
Boltzmann, 494
v. Bonsdorff, 526
Borcher, 559
Bottger, 63
Bottger, Rud., 568
Botticher, 578
Bottinger, 580
Boullay, 253, 495
Bourcault, 454
Bourdelin, 118
Boussingault, 274, 533, 535
Boyle, Robert, 3, 59, 92, 100,
103-107, 128, 133-136, 140 et seq.,
510
Brand, 149
Brandt, 149
Brauner, 410
Bredt, 454
Brefeld, 547
Brewster, 499
Brieger, 549
Brisson, 152
Brodie, 445
Bromeis, 441
Brown, 455, 572, 456
Brucke, 501, 538, 540, 543
Briihl, 349, 498, 499, 509
Brush, 526
Buchholz, 523, 553
Biichner, 548, 570
Buckton, 464
Buff, 328
Buffon, 140
Bunge, 539
Bunsen, 260-261,311, 385-386, 391,
392, 407, 413, 418, 424, 426, 433,
469, 493, 494, 497, 511, 526, 528,
557, 567, 589, 593
Bunte, 583
Butlerow, 332, 334, 336, 344, 435,
438
C^SALPIN, 88
Caetano, 62
Cagliostro, 62
Cagniard de la Tour, 547
Cahours, 259, 438, 444, 445, 468,
469, 492
Cailletet, 492
Calmels, 483
Cannizzaro, 335, 399, 438
Carlisle, 229
Caro, 470, 576, 578
Carpenter, 569
Carstanjen, 478
Cavendish, 121-122, 128-130, 145,
150, 169, 415
Champion, 568
Chance, 564
Chancel, 299, 439
Chaucourtois, 371
Chevreul, 438, 441, 530, 542, 569,
591
Chittenden, 541
Christensen, 403, 427
Christison, 397
Chrustschoff, 417
Ciamician, 484
Claisen, L., 355, 363, 444, 450, 452,
453, 483, 486
Clarke, 423
Classen, 390
Glaus, Ad., 345, 348, 349, 351, 360,
462, 481, 591
Claus, C. E., 413
Clausius, 494, 518
Clement, 426, 561
INDEX OF AUTHORS' NAMES
603
Cleve, 430
Cloez, 474, 477
Collie, 363, 349, 416
Combes, 452
Conrad, 453
Cooke, 403
de Coppet, 376, 502
Couper, 329, 333-334, 337, 345
Coupler, 577
Courtois, 402, 560
Cousin, 168
Crafts, 434, 452
Crell, 180
Croll, 74, 97
Cronstedt, 144, 149, 523
Crookes, 374, 409, 410
Cross, 538, 572
Curtius, 423, 471, 472, 486
DAGUEBBE, 510
Dale, 498
Dalton, 181, 188-195, 199, 493
Dammer, 595
Daniell, 242
Daubree, 527
Davy, Humphry, 195-199, 229 et
seq., 238, 239, 241 et seq., 290,
402, 404, 408, 418, 419, 421, 423,
424, 425, 426, 507, 584, 587
Davy, J., 198
Deacon, 565
Debray, 413, 429, 492, 528, 559
Debus, 189, 440, 449, 568
Deherain, 533
Deite, 569
Delitzsch, 474
Democritus, 7, 9
Dennstedt, 484
Derosne, 573
Descroizille, 391
Desormes, 426, 561
Dessaignes, 543
Deville, H. St. Claire, 413, 422, 424,
492, 498, 528, 559, 591
Dewar, 350, 493
Diesbach, 147
Dietrich, 533
Diodorus Siculus, 12
Dioscorides, 5, 11, 15, 16, 18, 50
Dittmar, 418, 593
Dobbie, 571
Dobereiner, 249, 371, 420, 441, 448,
484, 576
Dobner, 481, 577
Dombasle, 531
Dragendorff, 397, 549
Draper, 511
Drebbel, 95
Drechsel, 442, 540
Dschabir, 29
Dschafar or Geber, 29, 30
Dubrunfaut, 573
Dufet, 506
Duhamel de Monceau, 118, 136, 146,
147, 149
Diihring, 497
Dulong, 219, 220, 242, 419, 423, 424,
591
Dulong and Petit, 220, 497
Dumas, 224, 225-227, 253, 258,
272-275, 276-277, 280 et seq., 323,
370, 371, 396, 404, 407, 433, 437,
438, 460, 475, 490-491, 495, 556,
563, 591
Duppa, 442
Durocher, 527
Dutrochet, 536
EBELL, 570
Ebelmen, 527
Ebert, 485
Effront, 575
Ehrenberg, 478
Eiloart, 357
Einhorn, 483
Eittner, 580
Ekeberg, 181, 204, 412, 523
Elbs, 362, 504
d'Elhujar, 411
Eller, 115
Empedocles, 6, 8
Engelmann, 536
Engestrom, 144
Engler, 583, 406
Epicurus, 7
Erasmus of Rotterdam, 62
Erastus, 72
Erdmann, 203, 370, 388, 396, 526,
587, 589, 590, 597, 598
Erlenmever. 334, 336, 338, 470, 591,
, 597
Etard, 549
Ewan, 559
Eykmann, 502
FAGGOT, 155
Falck, 545
Faraday, 227-228, 251, 418, 433,
492, 503, 516
Favre, 507
Faworsky, 435
Fehling, 392, 441, 446, 449, 476,
496
Feichtinger, 571
Fick, 543
Figuier, 430, 573
604
INDEX OF AUTHORS' NAMES
Fileti, 443
Finkener, 501
Fischer, Emil, 358, 363, 364, 437,
455, 457, 462, 472, 485, 537, 576,
577, 591
Fischer, F., 556
Fischer, G. E., 184
Fischer, 0., 363, 437, 576, 577
Fittig, 345, 435, 443, 448, 452, 455,
458, 485, 591, 594, 597
Fitz, 547
Flamel, Nicolas, 35
Fleck, 569
Fliigge, 399
Fordos, 420
Forster, 545
Forster, 431, 571
Fouque, 528
Fourcroy, 163, 168, 171, 172, 174
et seq., 586, 596
Fownes, 485
Frank, A., 557, 566
Franke, 427
Frankland, E., 285, 310, 316 et seq.,
322 et seq., 329, 330, 331, 336, 361,
366, 367, 415, 425, 434, 442
Frankland, P. , 535
Fremy, 418, 423, 427, 529, 539, 569,
591, 595
Frerichs, 541, 545
Fresenius, R, 385, 389, 397, 588,
593, 529
Fresnel, 499
Freund, 435
Friedel, 434, 452, 454, 528
Friedheim, 429
Friedlander, 481
Frobenius, 152
Fuchs, 571 •
Fuchs, N., 524
GABRIEL, 481
Gadolin, 409, 523
Gahn, 144, 146, 149, 181, 523
Galen, 48
Gattermann, 424, 449
Gautier, 476, 549
Gay-Lussac, 195, 199-201, 210, 214
et seq., 239-241, 249, 290, 391,
395-396, 402, 404, 418-420, 422-
424, 426, 427, 473, 489, 490, 527,
562, 566, 582, 587
Geber (Dschafar), 29, 30
Gehlen, 422
Gelis, 420
Gengembre, 177, 421
Genth, 428
Geoffrey the elder, 62, 117, 138, 154
Geoffroy the younger, 117.
Gerhardt, 283, 286-295, 300-307,
327, 337, 440, 445, 460, 479, 591,
594
Gerland, 430, 559
Geuther, 366
Gibbs, 390, 428
Gilbert, 533, 535
Gilchrist, 557
Girtanner, 594
Gladstone, 498, 517
Glaser, 108, 155
Glauber, 86, 90, 92-97, 137
Glover, 562
Gmelin, C. G., 407
Gmelin, Chr., 192, 525
Gmelin, L., 227, 243, 278, 290, 295,
371, 474, 495
Goldschmidt, 483
Gomperz, 7
Gore, 418
Gorup-Besanez, 541
Gottling, 553
Goulard, 155
Graebe, 353, 363, 435, 452, 480, 578
Graham, 244, 413, 423, 501, 594
Gray, 571
Gren, 180, 594
Grew, 155
Griess, 320, 460, 466, 470-471, 578
Grimaux, 157, 161, 163, 166, 468
Gros, 430
Groth, 506
Griineberg, 567
Gruner, 557
Guareschi, 549
Guckelberger, 563, 570
Guimet, 570
Guldberg, 517 et seq.
Gustavson, 435
Guye, 501
Guyton de Morveau, 133, 163, 168,
171, 173, 175
HAARMANN, 456.
Hagen, 154, 553
Haitinger, 483
Hales, 128, 129, 131
Hall, 527
Hammarsten, 540, 542
Hampson, 493
Hansen, E. Chr., 547, 574, 575
Hantzsch, 359, 360, 363, 422, 462,
473, 480, 485, 486
Harden, 189
Hardy, 483
Hargreaves, 563
Harnack, 540
INDEX OF AUTHORS' NAMES
605
Hasenbach, 422
Hatchett, 180, 412
v. Hauer, 430, 526
Hausmann, 385, 525
Hautefeuille, 528
Hatty, 523, 525
Hawksbee, 107
Heeren, 568
Heintz, 441, 539, 542, 569
Heinzerling, 581
Helbig, 563
Hellot, 147
Hellriegel, 535
Helmholtz, v., 543
van Helmont, 59, 61, 75-79, 128
Helvetius, 61
Hempel, 393, 396
Henneberg, 534
Hennel, 439
Henninger, 541
Henry, 180, 341, 421, 493
Henry, W. C., 188
Heraclitus, 6
Herapath, 494, 495
Hermann, 526
Hermbstadt, 553, 556, 573
Hermes Trismegistos, 24, 25
Heron, 455, 456, 572
Herschel, 494
Herter, 541
Hess, 396
Hess, G. H., 507
Hesse, 496
Heumann, 425, 579
Hiarne, 146
Higgins, 196
Hill, 485
Hinsberg, 481
Hisinger, 204, 229
Hittorff, 406, 506
Hjelm, 411
van 't Hoff, 357, 377, 406, 489, 499-
502, 521
Hoffmann, Friedrich, 113, 142, 152
Hoffmann, R, 446, 570
Hofmann, A. W. von, 72, 179, 209,
284, 295, 296, 297 et seq., 439,
449, 465 et seq., 468, 469, 470,
476, 477, 480, 490, 576, 577, 589,
592
Hofmann, Frz., 545
Hofmann, K. B., 11, 14, 15, 17, 18,
19
Hofmeister, 541
Holt, 443
Homberg, 107-108, 144
Hooke, 107, 132
Hope, 408
Hoppe-Seyler, 539-542, 548
Horstmann, 488, 492, 501, 521, 595
Howard, 573
Hiifner, 541, 548
Humboldt, A. von, 214, 264, 273
Hunt, Sterry, 301
Husemann, 397, 549
INGEN-HOUSS, 531, 536
Irinyi, 569
Isaac Hollandus, 35, 41
Isambert, 492
Ittner, 473
JACOBI, 559
Jacobsen, 455
Jannasch, 526
Janssen, 415
Japp, 309
Jolly, 501
Joly, v., 414
Jorgensen, 428, 430, 574, 575
Jorissen, 406
Joule, 494
Julius Firmicus, 26
Juncker, 133
KALLE, 464
Kane, 257
Kanonikoff, 498
Karmarsch, 556
Karolyi, 568
Karsten, 495
Kaufmann. 422
Kay, 328
Keiser, 403
Kekule, 307, 308 et seq., 328-330,
332, 336, 338, 339, 344 et seq.,
347 et seq., 352, 353, 433, 440, 442,
446, 458, 463, 470, 471, 589, 593,
597
Kempe, 429
Kerl, 556, 557
Keyser, 414
Kiliani, 455
Kircher, 62
Kirchhoff, G. S. C., 572
Kirchhoff, Gust. , 386, 494
Kirwan, 130, 180, 523
Kjeldahl, 397
Klaproth, 178-179, 385, 386, 388,
403, 410, 411, 523
Klason, 463, 464, 474, 477
Knapp, 406, 556, 570, 572, 580, 581
Knecht, 580
Knop, W., 534
Knorr, 363, 486
v. Knorre, 429
606
INDEX OF AUTHORS' NAMES
Robert, 549
Kohlrausch, 501
Kolb, 563
Kolbe, 285, 306, 310, 311-322, 329,
330, 338, 345, 361, 437, 438, 441,
446, 447, 448, 461, 463, 475, 486,
582, 588, 589, 593, 594, 597, 598
Konig, 399
Kdnigs, 363, 480, 482
Kopp, E., 568
Kopp, H., 4, 375, 489, 495, 496,
498, 505, 594
Koppfer, 396
Korner, 350, 353, 479
Kortum, 62
Kraemer, 436
Krafft, 442, 477, 497
Kraus, 537
Kremers, 371
Kronig, 494
Kriiger, 341
Kriiss, 369, 408, 410, 411, 429, 430
Kuhling, 482
Kuhlmann, 573
Kiihne, 540, 541
Kiilz, 543
Kunkel, 109, 147, 153
Kiisser, 503
Kiitzing, 547
LAAR, 355
Labillardiere, 484
Ladenburg, 348, 349, 353, 363, 479,
480, 482, 591, 595
de Laire, 456
Lampadius, 425, 523, 573
Lamy, 409
Landauer, 144
Landolt, 469, 498
Langer, 428
Langlois, 420
Laplace, 168, 488, 508
Lassaigne, 394
Lauraguais, 153
Laurens, 584
Laurent, 278 et seq., 286-292, 293-
295, 301, 440, 457
Lauth, 577
Lavoisier, 4, 129, 158, 159, 160-172,
247, 386, 392-395, 401, 403, 405,
530, 546, 594, 596
Lawes, 533, 535
Lea, C., 406
Le Bel, 357, 499
Leblanc, 149, 531, 562
Leclaire, 560
Le Cor, 35
Lecoq de Boisbaudran, 409, 495
Lederer, 579
Lefevre, 108
Lehmann, 534, 540, 541, 542
Leibniz, 102
Lemery, 107-108, 134, 154
Lenk, 568
Lenz, 504
Lepsius, 567
Lerch, 453, 542
Leuchs, 541
LeVy, 528
Lewes, 425
Lewkowitsch, 570
Leykauf, 570
Libavius, 57, 59, 74, 88, 91, 93, 95,
97
Lieben, 438, 441, 483
Liebermann, 351, 363, 435, 443, 452,
578
Liebig, 243, 246, 251, 253, 254 et seq. ,
258-260, 262-270, 274, 284, 306,
396, 423, 427, 432, 440, 441, 444,
445, 447-449, 451, 456, 459, 463,
474, 478, 530, 532-533, 535, 536 et
seq., 543, 544, 546, 568, 570, 574,
587, 588 et seq., 594, 596, 598
Liechti, 429
Lightfoot, 577
Limpricht, 484
Linck, 568
Linde, 493
Linnemann, 497
v. Lippmann, 455, 573, 574-576
Lippmann, 510
Lister, 550
Littler, 571
Lob, 504
Lockyer, 415
Loew, 537
Lommel, 536
Long, 504
Lessen, 341, 495
Lowig, 402, 463, 469
Loysel, 163
Lubbock, 180
Lucretius, 7
Ludwig, C., 501, 540, 541, 542
Lunge, 422, 561
MACKENZIE, 405
Macquer, 117, 119, 146, 147, 580
Magnus, 270, 419, 430, 439, 542
Malaguti, 517
Malherbe, 563
Mallet, 409
Malpighi, 530
Maly, 541
Mansfield, 577
INDEX OF AUTHORS' NAMES
607
Marcet, 587
Marchand, 370, 388, 396, 411
Marcker, 572
Marckwald, 485
Marggraf, 115, 116-117, 143, 146,
150, 153, 157, 386, 573
Margueritte, 391, 429
Marignac, 369, 370, 388, 403, 405 et
seq., 410, 413, 429, 526
Mariotte, 106, 530
Markownikoff, 436, 583
Marsh, 357
Marsh, 422
Martin, 558
van Marum, 405
Maslema, 30
Mathiessen, 407
Maxwell, Clerk, 494
Mayer, A., 547
Mayow, 107, 129, 130, 135, 164, 165
McGowan, 377
Meineke, 411
Meissner, 543
Melsens, 283, 569
Mendelejen^Smtf seq., 493
Menschutkin/518, 521
Merck, 482
Mercurius, 25
v. Mering, 543
Merling, 483
Mersenne, 102
Meslans, 460
Meusnier, 168
Meyer, E. von, 406, 477, 597
Meyer, Lothar, 371, 372, 458, 591,
595
Meyer, O. E. , 494
Meyer, Richd., 598
Meyer, Victor, 350-351, 355, 359,
363, 406, 439, 455, 458, 459, 461,
462, 470, 484, 490, 491, 591
Michael, 356, 358
Michaelis, A., 421, 462, 465, 469,
486, 487
Michaelis, W., 571
Michel, 572
Miller, 386, 494
v. Miller, 481
Millon, 419
Milly, A. de, 569
Minderer, 93
Minunni, 462
Mitscherlich, AL, 572
Mitscherlich, E., 221-222, 225, 406,
421, 427, 434, 439, 460, 463, 505-
506, 522, 524, 525, 527, 589, 594
Mohlau, 576
Mohr, 391, 397
Mohs, 522
Moissan, 369, 403, 424, 425, 428,
460, 528,, 529
Moitrel d' Element, 129
Moldenhauer, 569
Mond, 428, 430, 563, 564, 583
Monge, 163, 168
Moraht, 408
Morley, 403
Morris, 456
Morveau. See Guyton de Morveau
Mosander, 204, 410, 525
Mosso, 549
Muck, 584
Mulder, 537, 539
Miiller, Fr., 459
Miiller, H., 458
Miiller, M., 570
Miiller, N. J. C., 536
Miiller v. Richenstein, 403
Miintz, 535
Musculus, 572
Muspratt, 556, 563
Muthmann, 429
Mylius, 431, 571
van Mynsicht, 73, 97
NAGELI, 538, 548
Naquet, 338, 344
Nasse, O., 541, 548
Naumann, A., 492, 497
Naumann, C. F., 525
Nef, 461, 462, 478
Nencki, 540, 548, 549
Neri, 89
Nernst, 488, 496, 503
Neubauer, 543
Neumann, F. C., 498, 504
Neumann, Kaspar, 115
Neumeister, 541
Newlands, 371
Newlands Brothers, 573
Newton, 140
Nicholson, 229, 596
Nickles, 418
Nicolas, 569
Niepce, 510
Niepce de St. Victor, 510
Nietzki, 452, 453, 578, 579
Nilson, 408, 410, 411, 491, 497
Nobbe, 534
Nobel, 568
Noble, 568
Noelting, 423
Nordenskiold, 125, 173
Noyes, 403
ODLING, 307, 326, 327, 371
v. Oefele, 320, 374, 445, 464
608
INDEX OF AUTHORS' NAMES
Oettel, 566
Olympiodor, 25, 26, 27
Olzevsky, 492
Ortholph von Baierland, 49
Ost, 448, 483, 556
Ostwald, 377, 488, 489, 501, 503, 504,
519, 520, 595
O'Sullivan, 455, 456, 572
Otto, J., 397, 568, 594
Otto, R., 464, 477, 487, 549
Overton, 360
PAAL, 363, 422, 452, 481, 484, 485
Page, 458
Palissy, 62, 83, 85-86, 89, 90, 530
Palmer, 488
Paracelsus, 3, 59, 67-72, 94
Pariset, 587
Parkes, 558
Parmentier, 177
Partridge, 409
Pasteur, 358, 447, 499, 505, 547, 548,
574, 575
Pattinson, 558
Payen, 556, 572
Pean de St. Gilles, 517
Pebal, 419
Pechiney, 565
v. Pechmann, 363, 453 472, 473, 485
Peligot, 275, 411, 429, 438, 460, 561
Pelletier, 177, 421
Pelouze, 370, 404, 439, 591
Perkin, W. H., jun., 435
Perkin, W. H., sen., 363, 444, 450,
466, 500, 577
Peters, 534
Petersen, 526
Petit, 210, 219, 220, 221
Pettenkofer, 371, 542, 545
Pettersson, 408, 491, 497
Pfaff, 385, 422
Pfaundler, 518
Pfeffer, 501, 536
Pfitzinger, 481
Pfliiger, 545
v. d. Pfordteii, 369, 427
Phillips, 569
Pictet, 483, 492
Pinner, 469, 476 481, 483
Piria, 446, 456
Planck, 501
Plato, 9, 38
Plattner, 390, 407, 558
Playfair, 311, 428, 474, 557
Pliny, 5, 6, 11-20
Pliicker, 504
Poggendorff, 596
Ponomareff, 468
Popoff, 341, 452
Porret, 474
Porta, 90
Pott, 116
Prechtl, 556
Preyer, 541
Priestley, 122-124, 130, 131 et seq.,,
162, 392, 531
Pringsheim, 536
Proust, 183, 185-188, 387, 388, 400,
430, 515
Prout, 201-203, 374
Psellus, Michael, 30
Pseudo-Aristotle, 26
Pseudo-Democritus, 26
Pseudo-Geber, 34, 39-40, 41, 42, 46,
47, 50-51, 52-56, 59
Pugh, 535
Pullinger, 431
Pythagoras, 9
QUINCKE, 428
RAMMELSBERG, 390, 411, 526, 528
Ramsay, 130, 374, 393, 402, 408,
415, 416, 422, 430, 497, 500
Ranke, 543, 545
Raoult, 376, 502
Raschig, 423, 424
Rathke, 477
Rayleigh, 374, 403, 414-415
Raymund Lully, 32, 33-34, 43, 52,
57
Reaumur, 147, 152
Redtenbachei?, 441
Rees, 547
Regnault, 258, 281, 433, 439, 542,
594
Reich, 409, 561
Reichenbach, 583
Reiset, 430, 542
Renault, 504
Renk, 545
Retgers, 506
Rey, 132
Reynolds, 474
Rhazes, 30
Richards, 403
Richter, J. B., 181-184, 185, 387.
417
Richter, Th., 409, 526
Richters, 571, 584
Riecke, 359
Rinman, 146, 523, 557
del Rio, 412
Ripley, 35
Ritter, 510
Ritthausen, 537
INDEX OF AUTHORS' NAMES
de la Rive, 405, 559
Roberts, 573
Robinson, 563
Robiquet, 249
Rochleder, 441, 537
Rome de 1'Isle, 221, 523
Romer, 569
Roscoe, 189, 369, 412, 418, 429, 511
Ruse, 341
Rose, Fr., 428
Rose, G., 389, 505, 522, 525, 527
Rose, H., 209, 385, 389, 412, 421,
424, 427, 517, 522, 525, 589
Rose, Valentin, the elder, 389
Rose, Valentin, the younger, 152,
389, 523
Rosenstiehl, 577
Rosetti, 90
Rossi, 438, 442
Rothe, 462
von Rothenburg, 486
Rouelle, 117, 118-119, 136, 137, 154,
161
Rubner, 545
Riidorff, 502
Rumford, 507
Runge, 484
Rutherford, 130
SACHS, 536, 538
Sabatier, 425
Sadler, 571
Sala, Angelus, 59, 80, 95
Salomon, 455, 572
Sandberger, 526
Sandmeyer, 460
Sarasin, 528
Sattler, 560
Saussure, Th. de, 392, 395, 531, 536
Saytzeff, 443, 464
Schadler, 569
Schaffner, 563
Scheele, 124, 125-127, 129, 130 et
seq., 143 etseq., 147, 149, 150-155,
162, 183, 238, 386, 392, 427, 494,
510, 560
Scheerer, 390, 505, 526, 543
Scheibler, 429, 455
Scherer, 180
Schertel, 561
Scheufelen, 458
Schiel, 302
Schiendl, 510
Schiff, R., 495
Schischkoff, 478, 567
Schloesing, 535
Schlossberger, 543
Schmidt, A., 540, 541, 548
Schmidt, C., 541, 545
Schmidt, F. W., 410
Schmiedeberg, 539
Schmieder, 62
Schmitt, K, 319, 447, 582
Schneider, E. A., 406
Schneider, R., 390, 404, 411
Schonbein, 405, 419, 568
Schone, 419
Schorlemmer, 341, 497
Schott, 571, 572
Schrader, 532
I Schraube, 473
Schrauf, 505
Schroeder, 496
Schrotter, 406
Schiirer, 90
Schiitzenberger, 420, 431, 540
Schiitzenbach, 575
Schultz, 535
Schulze, H., 422
Schulze, E., 538
Schultze, 510
Schwalb, 458
Schwanert, 484
Schwanhardt, 148
Schwann, 547
Scott, 403
Seebeck, 408, 499
Sefstrom, 412
Seger, 571
Seignette, 97
Selmi, 549
Semmler, 582
Senarmont, 527
Sendivogius, 62
Senebier, 531 536
Sennert, 59, 80
Serullas, 424, 439, 474
Seubert, 414
Shaw, 114
Shenstone, 263, 406
Shields, 430, 500
Siemens, W., 559, 584
Silbermann, 507
Simpson, Maxwell, 442
Skraup, 353, 479, 480
Smith, 526
Smithells, 425
Sobrero, 568
Solon, 9
Solvay, 565
Soret, 405, 495
Soubeiran, 422 .
Soxhlet, 455, 542
Spencer, 559
Spilker, 436
Sprengel, 532
R R
610
INDEX OF AUTHORS' NAMES
Stadion, 419
Stadeler, 541, 543
Staedel, 495
Stahl, 4, 59, 110-113, 133
Stahlschmidt, 424
Stas, 275, 370, 388, 397, 403, 404,
407
Steiner, 478
Stenhouse, 484
•Sterry Hunt, 301
Stevenson, 397
Stoehr, 480, 481
Stohmann, 508, 509, 534, 556, 573
Stolzel, 557
Stoney, 495
Storer, 531
Strecker, 466, 541, 543, 591, 594
Streng, 526
Stromeyer, 385, 390, 409, 423, 526
Struve, F. A., 555
Suidas, 2
Svanberg, 525
Swab, 144
Swan, 386, 494
Sylvius de le Boe, 59, 80-81, 82, 92,
93
Synesios, 26, 27
TACHENIUS, 59, 80, 81-82, 92, 93, 96
Talbot, 386, 510
Taylor, 397
Tennant, 405, 565
Tertullian, 24
Thaer, 531, 532
Thales, 6
v. Than, 425
Thenard, L. J., 200, 239, 395, 418,
419, 424, 426, 427, 587, 594
Thenard, P., 421
Theophilus Presbyter, 46
Theophrastus, 5, 15
Thorn, H., 551
Thomas, 557, 584.
Thomas and Gilchrist, 557
Thomas Aquinas, 31
Thomsen, J., 417, 430, 508, 517
Thomson, James, 497
Thomson, Th., 189, 194, 202, 390,
526, 592, 594
Thorpe, 104, 123, 167, 198, 228, 244,
423, 424, 430, 495
Thot, 25
Thurneysser, 62, 72
Tiemann, 454, 456, 476, 582
Tilghman, 572
Tillet, 133
Tollens, 455
Traube, F., 355
Traube, M., 419, 548
Travers, 402, 416
Trommsdorff, 177, 553
Troost, 528
Tunner, 557
Turner, 203, 390
Turquet de Mayerne, 73, 97
Tutton, 423
Tyndall, 511
VALENTINEB, 566
Valerius Cordus, 98
Varrentrapp, 397, 441
Vauquelin, 176-177, 385, 386, 391,
408, 410, 426, 523, 586.
Verguin, 577
Ville, 531, 533, 534, 535
Vinzenz of Beauvais, 30
Voigt, 477
Voit, 542, 545
Vogel, 543
Vogel, B. H. W., 420, 511
Volhard, 320, 391, 467, 474
Volta, 145
WAAGE, 517 et seq.
van der Waals, 494
Wackenroder, 420
Wagenmann, 575
Wagner, 452
Wagner, P., 557
Wagner, R., 556
Walden, 504
Walker, Jas., 377
Wallach, 436, 454, 468, 582, 586
Ward, 148
Warington, 535
Watson, 494
Watson, W., 149
Watt, 167
Watts, H., 595
Weber, 498
Weber, R., 420, 561, 571
Weddige, 477, 481
Wedgwood, 571
Weidel, 353, 479
Weihrich, 264, 588
Weilandt, 497
Weldon, 565
Welter, 420
Wenzel, 186, 387
Werner, A., 341, 359
Werner, A. G., 523, 524
Westrumb, 177, 523, 553
Whetham, 503
Wichelhaus, 581
Widmann, 481
Wiedemann, G., 504
INDEX OF AUTHORS' NAMES
611
Wiegleb, 62, 177, 523
Wilcke, 120
Wilfarth, 535
Wilhelmy, 520
Will, 397, 453, 456, 588
Willgerodt, 458
Williams, 478
Williamson, 295, 298 et seq., 326,
337, 439, 518
Willis, 107, 134
Winkelmann, 497
Winkler, 01., 392, 393, 408-410,
411-412, 526, 559, 561, 571
Winogradsky, 535
Winterl, 417
Wischnegradsky, 479, 482
Wislicenus, J., 356, 357, 358, 366,
446, 453, 500, 543, 591
Wislicenus, W., 355, 422, 423, 444,
453, 473
Witt, 470, 578, 579
v. Wittich, 541
Wohl, 466
Wohler, 252, 254, 262, 270-272, 389,
396, 406, 408, 424, 427, 432, 444,
456, 463, 474, 525, 528, 543, 570,
589, 594, 596
Wolff, E., 534
Wolff, L., 481
Wolffenstein, 419
Wollaston, 195 199, 412, 413
Wray, 153
Wren, 107
Wroblevsky, 492
Wurtz, 295-296, 298 et seq., 307,
310, 327, 328, 337, 368, 424, 434,
439, 440, 446, 450, 466, 467, 477,
492, 526, 548, 591, 595
Wyrouboff, 506
YOUNG, JAS., 244
Young, Sidney, 497
ZEISE, 463
Zamminer, 594
Ziervogel, 558
Zimmermann, Cl., 369, 411, 429
Zincke, 436, 439, 440, 452, 481, 497
Zinin, 466, 470
Zdller, 534, 556, 586
Zosimos of Panopolis, 24, 27
Zulkowsky, 593
R R 2
INDEX OF SUBJECTS
The figures in thick type refer to those pages upon which subjects are
treated in detail or points of special importance are recorded.
ABSORPTION of gases by water, 129
Academia Caesar ea Leopoldina, 102
del Cimento, 102
Acaddmie Franqaise, 176
Royale, 102
Academies and Learned Societies,
formation of, 101-102
Academies, Spanish, 28
Acetaldehyde, 449
Acetic acid, 19, 96, 153, 441, 575-
576
acid, constitution of, 282-283, 316,
et seq., 441
acid (glacial), 153
acid, synthesis of, 361
aldehyde, polymers of, 449
Aceto-acetic ether, 354, 442, 453
tautomerism of, 354
Acetone, 451
-dicarboxylic acid, 453
Acetyl, 315
theory (Liebig), 258
Acetylene, 435
as an illuminant, 583
Acid amides, 444, 468
anhydrides (Gerhardt), 300, 444,
445
chlorides, organic, 444, 445
nitriles, 314, 475
theory of (Lavoisier), 167
Acides, 172
Acids, 51, 91
constitution of (Berzelius), 233 et
seq.
constitution of (Davy), 241
constitution of (Liebig), 243-246
nomenclature of (Lavoisier), 172
organic, 153
Acids from plant juices (Scheele), 153
manufacture of organic, 582
always contain oxygen (Lavoisier),
167 et seq. ; contro version of this
view, 197, 238 et seq.
Acrylic acid, 442
Actinometry, 511
Adipic acid, 442
Adjective dyes, 147
Aer vitriolicus, 131
yEsculin, 456
^thal, 275, 438
jEthereum (Kane), 257
dZtherin, 253
theory, the, 253-254
Affinitas, 137
Affinity-coefficients, specific, 519 et
seq.
Affinity, degrees of, 334
determinations of, 512-521
doctrine of, 512-521
doctrine of (Bergman), 512-513
doctrine of (Berthollet), 174, 185,
513 et seq.
doctrine of, its latest development,
519
simple elective, 138
tables of (Geoffrey), 117, 138, 512
units of, 341
views as to its causes, 137-140
Affinity, chemical (Boyle), 105
chemical, views of the Phlogiston-
ists, 137 et seq.
doctrine of (Guldberg and Waage),
517, 519
Affinivalenten (Erlenmeyer), 338
Agricultural- chemical experiments
at Woburn, 533
614
INDEX OF SUBJECTS
Agricultural chemistry, 530 et seq.
Liebig's great services, 269, 530
et seq.
Air, composition of atmospheric, 122,
130-131, 145
Albumens, vegetable, 537
animal, 539
Alchemistic period, the, 21-64
Alchemistic speculations of the 13th
and 14th centuries, 41
Alchemists, practical-chemical
knowledge of the, 45 et seq.
Alchemy among the Arabians, 28 et
seq.
at the European courts, 35, 61, 62
books on, 23
decay of, 58 et seq.
during the last four centuries, 58-
64
general notes upon, 2-3
in Egypt, 23, 37
in the Christian countries of the
West, 30 et seq.
its relation to the Platonist philo-
sophy, 22
origin of, 21, 23 et seq.
position of chemists of repute in
the 16th and 17th centuries with
regard to it, 59 et seq.
problems of, 32 et seq.
relations of, to astrology, 25
special history of, 37 et seq.
theories of, 37 et seq.
Alcohol, 57, 98
constitution of (Berzelius), 256
meaning of the word, 98
preparations from, 575, 581
Alcoholometry, beginnings of, 152
Alcohols, 437, 440
constitution of (Kolbe), 318
polyatomic, 438
secondary and tertiary (Kolbe),
318
Aldehydes, 448-451
constitution of (Kolbe), 318
formation of, 449
Aldol, 450
Aldoses, 455
Aldoximes, 462
Alembic Club Reprints, 214
Alexandrian Academy, the, 21, 26,
37,38
Algaroth, powder of, 94
Alizarine, 578
Alkahest, 52, 96
Alkali, 50
Alkali metals, discovery of by Davy,
197, 238
Alkali metals (Gay Lussac and
Thenard), 200, 239
atomic weights of, 407
compounds of, 426
earlier views on their nature, 239
Alkali waste, 563-564
Alkalies, decomposition of, 238
Alkalimetry, 391
Alkaloids, derivatives of pyridine,
etc., 482-483
synthesis of, 482
tests for, 397-398
Alkarsin, 261
Alkyl cyanurates, 477
cyanides, 475
Alkyl-pyridines, 479
Alkyls, metallic, 487
Allo-isomerism (Michael), 356
Allotropy, 405, 406, 506
Alloys, 560
Allyl alcohol, 438
Allylamine, 467
Alum, 17, 52, 90, 93
earth, confounding of this with
lime, 93
Aluminium, 409, 559
bronze, 560
chloride, syntheses with, 434
Amalgamation processes for obtain-
ing silver, 47, 88
Amalgams, 560
Amides, 444-445
Amidines, 468, 476
Amido-acids, organic, 446
constitution of (Kolbe), 319
Amido-miazines, 478
-pyrimidines, 478
Amidoximes, 476
Amine bases ( Wurtz, Hofmann), 295
et seq.
Amines, 465 et seq.
Ammonia as a type, 296, 300
gas, discovery of, 129
manufacture of, 582-583
salts as medicines, 93
Ammonia soda, 564
Amygdalin, 268, 456
Amyl alcohol, 438
Anaesthetics, 551
Analysis, introduction of the word
by Boyle, 106, 141
Analysis, development of, 384 et seq.
legal-chemical, 397-398
of articles of food and drink, 398
of gases, 128, 145, 392
of inorganic substances, 384 et
seq.
of organic substances, 393 et seq.
INDEX OF SUBJECTS
615
Analysis, qualitative, 82, 96, 140
et seq., 384 et seq.
quantitative, 144, 178, 386, et seq.
technical, 398
volumetric, 390
Ancients, practical-chemical know-
ledge of the, 9 et seq.
Anhydrides of organic acids, 444
Aniline, 465, 576
black, 577
blue, 577
colours, 576 et seq.
green, 577
red, 576
violet, 577
yellow, 578
Annalen Chemische (Crell), 180
der Chemie undPharmazie (Liebig),
266, 596
der Physik, 180
der Physik und Chemie (Poggen-
dorff), 180, 596
Annales de Chimie, 175, 596
de Chimie et de Physique, 596
Anthracene, 435
Antimoniuretted hydrogen, 422
Antimony((BasilValentine),36, 47,54
compounds, organic, 469
pentachloride, 424
pills, 94
preparations, 37, 49, 54, 94
Antiphlogistic system, the, 158, 168
et seq.
in Germany, 177
in other countries, 180
Antipyrine, 472
Antiseptics, 155, 550
Apothecaries' shops, 49, 91
Apparatus for collecting gases, 129
of the alchemistic age, 34
Aquafortis, 51
regia, 51-52
vita, 57, 98
Arcana, 70
Arabian academies, 28
Arabians, chemistry among the, 28
et seq.
Arabite, 439
Archeiis, 70, 78
Argon, 122, 393, 414, 416, 419, 493
helium, and other monatomic
gases, their position in the Per-
iodic System, 374, 416-417
Aromatic compounds, meaning of
the term, 349-351
theory of (Kekule"), 346
(Ladenburg, Claus, and Baeyer),
348-349
Arsenic and its compounds, 55, 94,
404, 422
Arsenic acid, 151
Arsenious acid, 55, 151
Arseniuretted hydrogen, 422
Arsines, etc., 469
Ashes of plants as manure, 17
Asparagine, constitution of, 319
Assimilation in plants, 510, 534, 536
et seq.
Asymmetric carbon atom, 355
theory of (van 't Hoff and Le
Bel), SSGetseq., 447
Atom (Laurent), 294
Atomic compounds (Kekule"),
339-340
heat, 220, 497-498
hypothesis, the, 181, 188 -
theory, (Dalton's), 188, 194
theory, further development of,
194 et seq.
theory, further development of,
by Berzelius, 210 et seq.
preparatory work for (Richter),
181, (Proust), 185
volume, 495
weight determinations, 203, 388
weight (Laurent), 293-295
weight system of Berzelius and the
opposition to it, 205, 223-225,
227
weight tables (Berzelius), 218, 224
weight tables (Dalton), 193
weights (Berzelius), 211 et seq.,
217 et seq., 223 et seq.
weights, correction of, 373
weights, deduction of, by
Cannizzaro, 335
weights (Dumas), 225
weights, Dumas' opposition to
those of Berzelius, 225
weights (Erdmann and
Marchand), 370
weights (Gerhardt), 290 et seq.
weights, improvements in their
determination, 370, 387, 403
weights (Marignac), 370, 388, 403
weights of the metals, 406 et seq.
weights of the non-metals, 401
et seq.
weights, periodic arrangement of,
370 et seq.
weights, ratio of those of hydrogen
and oxygen, 403
weights, relative (Berzelius), 210
et seq., 218, 223
weights, relative (Dalton), 191
et seq.
616
INDEX OF SUBJECTS
Atomic weights, relative (Thomson),
195
weights (Stas), 370, 388, 403
weights, uncertainty as to them
generally, 227
weights, uncertainty as to those
of the metals, 218, 221
Atomicity of the elements, 334, 338
Atoms, conception of, 181
of various orders (Dalton), 191
spacial arrangement of, 252, 344,
356 et seq.
Atropine, 482
Aurum potabile, 44
Azo-compounds, 470
Azo-dyes, 470, 578
Azo-imide, 423
Azoles, 485
BACKWARD substitution, 283-284
Bacteriology, 550
Balance, importance of the
(Lavoisier), 161, 169
Barium, 408, 426
Bases, designation of, by Lavoisier,
172
Basic slag, 557-558
Basicity, law of (Gerhardt), 289
of acids, 243 et seq.
of acids, criterion of, 245
Beet sugar industry, 275, 573
Beetroot sugar, 116, 149, 573
Benzene, constitution of, as deduced
from molecular refraction, 499
constitution of (Baeyer), 349
constitution of (Glaus), 348
constitution of (Kekule), 346
constitution of (Ladenburg), 348
derivatives, isomerism of, 347,
351 et seq.
hexagon formula of, 347
Benzin, 434
Benzoic acid, 97, 256, 443, 582
Benzoic aldehyde, 448
Benzoyl-carboxylic acid, 453
Benzoyl the radical of benzoic acid,
254
Benzyl alcohol, 438
Berichte der Deutschen chemischen
Gesellschaft, 597
Berlin Academy, the, 102
blue, 147
Beryllia, 176
Beryllium, 408, 427
Berzelius-Liebig Letters, the, 209,
246, 259, 266, 272, 274, 284
Bessemer process, the, 557
Betaine, 467
Biblical characters as alchemists, 24
Bile, acids of the, 541
Bile, chemistry of the, 541
Bismuth, 47
preparations, 93, 94
Bitter almond oil, 254, 577
Bitter salt, 155
Black oxide of manganese (investiga-
tion of by Scheele), 127
Blast-furnace process, the, 557
Blood, chemistry of the, 541-542
gases, 542
Blowpipe, 144, 385, 390, 523
Boiling point of solutions, 502
Boiling point, laws regulating the,
496-497
Bonds, central, 351
double, 351
Bone charcoal for sugar refining, 573
Bones, constituents of, 539
Boracic acid, 116
Boron, 404, 424
methide, 486
Brandy, distillation of, 90
Brass, 15, 147
Bromine, 402, 566
Bronze, 13, 14
Bunsen burner, the, 593
Butylene, 433, 435
CACODYL compounds (Bunsen), 261
compounds, constitution of,
315-317
Cadaverine, 549, 480, 483
Cadmia, 15
Cadmium, 409
Csesium, 407
Caffeine, 537
Calcination of the metals, 132
Calcination of the metals (Lavoisier),
164 et seq.
Calcium, 408, 426
Calomel, 95
Calorimetry, 508-509
Campechy wood, extract of, 580
Capillarity, 500
Carbamines, 476
Carbides, metallic, 428
Carbinols, secondary and tertiary, 438
Carbohydrates, 454-456
their significance for plant life, 538
Carbolic acid, 550
Carbon, 405, 425
as a constituent of organic com-
pounds, 247
bisulphide, 425
compounds, saturated and unsatu-
rated, 344 et seq.
INDEX OF SUBJECTS
617
Carbon, determination of, 395-396
assimilation of, by plants, 536
et seq.
double linkage of, 358
oxysulphide, 425
Carbonate of ammonia, 53
Carbonic oxide, composition of
(Dalton), 190
acid, 79
acid, composition of, 387, 394
acid, composition of (Black),
119-120, 128
acid, composition of (Dalton),
190
Carborundum, 428
" Carboxylic acid," 453
Carboxylic acids, 441-448
acids, constitution of (Kolbe),
317-318
acids, saturated, 441 et seq.
acids, aromatic, 443-444
acids, unsaturated, 442
acids, chlorides, anhydrides and
amides of, 444 et seq.
Carbures, 172
Cavendish's researches on gases,
122
Cellulose, 572
Cement, 571
copper, 47
Ceramic art, the, 17, 147, 571
Cerium, 179
metals, the, 409-410
Chelidonic acid, 454, 483
Chemia, first use of the word, 26
Chemical compound, different from
a mixture, 136
art, the, 9
combination, according to the
ancients, 8
combination, according to the
Phlogistonists, 135
composition, distinction between
empirical and rational
(Berzelius), 233
compound, meaning of, 8, 41-42,
134 et seq.
compound, old ideas regarding, 8,
41
constitution of organic com-
pounds, methods for investiga-
ting this, 361 et seq.
equilibrium, statical and dynam-
ical, 518
equivalents (Lavoisier), 169
"tinder," 568
industries, the great, 561
journals, 382, 595 et seq.
Chemical nomenclature (Lavoisier),
171
nomenclature (Berzelius), 234
nomenclature of organic com-
pounds (recent), 437
notation (Dalton), 194
periods, the various, 1 et seq.
Chemistry, agricultural and physio-
logical, 90, 530 et seq.
analytical, in the modern period,
384399
analytical, 106, 124, 136, 141
analytical, its development by
Boyle, 106
antiphlogistic, 168 et seq.
applied, 83 et seq., 146 et seq., 554
et seq.
geological, 527 et seq.
in ancient Egypt, 9, 12, 13, 16
et seq., 23 et seq.
in olden times, 5-20
inorganic, 367 et seq. , 400-431
its meaning at different periods,
2 et^ seq.
meaning and origin of the word,
2, 23
mineralogical, 522-529
organic, 246 et seq., 432-487
pharmaceutical, 48 etseq., 91, 154,
552
physical, 488-521
pneumatic, founded by van
Helmont, 78
pneumatic, its further develop-
ment, 128 et seq., 145
tasks of, in the various ages, 1
technical, in recent times, 554-585
technical, in the iatro-chemical
age, 87
technical, in the phlogistic period,
146
the aims of, 1 et seq.
Chili saltpetre, 566
Chloral, 459, 551
Chloraldehyde, 258
Chloride of lime, 426, 565-566
Chlorimetry, 391
Chlorine, 148, 402
discovery of, 127
its action upon organic substances,
457 et seq.
recognised as an element, 197,
239-240
supposed composition of, 240
the name, 239
Chlorophyll, 536
Choline,, synthesis of, 467
Chrome colours, 560
618
INDEX OF SUBJECTS
Chromium, 410
discovery of, by Vauquelin, 176
Chrysamine, 579
Chrysene, 436
Chryso'idine, 578
Cinnabar, 95
Cinnamic acids, isomeric, 443
Circular polarisation, 499
polarisation, magnetic, 500
Citric acid, 153
Classification of organic compounds,
278-280, 289, 302
Coal gas, 583
Coal-tar colour industry, 576 et seq.
Coal-tar, products from, 582
Cobalt, 149, 410, 428
-ammonia compounds, 428
blue, 90
Cocaine, 483
Cohesion, 514
Coins of alchemistic gold, 61
Colcothar, 55
Collidines, 480
Colloids, 501
Colour photography, 510
Combining proportions, proof that
these are constant, 185 et seq.
weights (Gmelin), 227, 291,
295
Combustion according to Stahl,
110-113
according to Hoffmann, 114
according to Mayow, 107
correct explanation of, by
Lavoisier, 164 et seq.
-ladder (Gerhardt), 289
phenomena of, 425
theory of (Lavoisier), 158 et seq.,
166-167
Composition of substances according
to Becher, 109-110
Compounds, atomic, 339
classification of, at the beginning
of the Modern Period, 172
molecular, 339
Comptes Rendus, 596
Condensations, 450
meaning of, 362
of aldehydes, 452
Congo red, 579
Coniferin, 456
Conine, 482
synthesis of, 364
Conservation of matter (Lavoisier),
169
Constitution, chemical (Berzelius),
231, 252
chemical (Gerhardt), 304-307
Constitutional formulae (Kolbe),
318-319
Copper, 13, 47, 88, 560
oxide for organic analysis, 396
vitriol, 18
Copulee, 283, 284, 313 et seq.
Copulated or conjugated compounds,
283,288, 313e«6-eg., 324
Copulation, a consequence of satura-
tion capacity (Frankland), 325
meaning of, 283, 322 et seq.
Corpse alkaloids, 549
Corpuscular theory (Berzelius),
216-217
theory (Boyle), 106, 139
Cosmetic, old Egyptian, 18
Creatine, 467
Cresols, 550
Criticism, importance of (Kolbe),
598
Croconic acid, 453
Crotonic acids, 443
Crotonic aldehyde, 450
Crystalline form, its connection with
composition, 221-223
Crystallography, 523
Crystalloids, 501
Cultures, dry and water, 534
Cumarone, 485
Cyan-alkines, 477
Cyanic acid, 251, 474
Cyanamide, 474
Cyanogen, 200, 473
compounds of, 473-478
iron compounds of, 427-428
polymers of, 477
Cyanuric acid, 474
Daltonism, 188
Decipium, 417
Decomposition of molecules into
atoms, 491
Decomposition of organic com-
pounds.. 366
Deduction, significance of (Aris-
totle), 5, 10
Dephlogisticated air (oxygen), 131
Dephosphorisation of iron, 557
Desmotropism, 355
Destillatio per decensum, 19
Dextrine, 572
Diagonal formula of benzene, 349
Di-aldehydes, 449
Di-amines, 465
Diamond, artificial production of,
529
Di-azines, 481
Diazo-acetic ether, 471-472
INDEX OF SUBJECTS
619
Diazo-compouncls, 466, 470 et seq.
oxidation of, 472
Didymium, 410
Diffusion, 500
-process for sugar, 573
Digestion, 540
Di-ketones, 452
Dimorphism, 505
Dissociation, 492
electrolytic, 501 et seq.
Distillation, 19, 49, 57, 90, 593
Distilleries, 90
Di-sulphones, 464
Docimacy, beginnings of, 47
Docimacy of the noble metals, 88,
390
Double atoms (Berzelius), 236
Drinks, analysis of, 399
Dualism (Berzelius), 233, 243 et seq.
fight against, 237 et seq., 275
et seq
overthrow by Unitarism,282 et seq.
Duplication of the metals, 26
Dye character and chemical con-
stitution, supposed connection
between, 470
Dyeing, 17, 48, 90, 147, 580
Dyes, 147, 576
Dyes, distinction between adjective
and substantive, 147
synthesis of, 364
Dynamic hypothesis, the, 359
Dynamite, 568
EARTHENWARE, 17, 47-48, 85, 89,
571
Earths (Becher's), 110
Eau de Javelle, 565
Ecgonine, 482
tichelle de combustion (Gerhardt), 289
Effect, chemical, 514
Elasticity, 514
Electric conductivity, 503
Electro-chemistry, 504, 516, 565
-chemical equivalents (Faraday),
228
-chemical theory (Berzelius), 230
et seq., 516
-chemical theory (Davy), 229
-metallurgy, 559
Electrolysis, 228 et seq., 242, 503
Faraday's law of, 228, 503, 516
of salts of fatty acids, 314
Electrolytic determination of metals,
390
Electrolytic law (Faraday), 228
Element, meaning of the term
(Boyle), 105, 134
Element, meaning of (Lavoisier), 170
Elements, Aristotle's four, 7
classification of, 161
discovery of in recent times, 401
et seq.
discovery of in the phlogistic
period, 150 et seq.
discovery of supposed new, 417
natural families of, 372
of the alchemistic period, 37
et seq.
of the Phlogistonists, 134-135
old views regarding, 6 et seq.
Elixir, for transmuting metals, 41
Encyclopedias of chemistry, 595
Energy, 508 et seq., 521
Enzymes, 548
Eosin dyes, 578
Equilibrium, dynamical, 518
statical, 518
Equivalents, electro-chemical, 228,
503
of the elements (Gerhardt), 290
et seq.
of the elements (Gmelin), 290
of the elements (Laurent), 294
first table of (Richter-Fischer),
184
of the elements (Wollaston), 199
Equivalents instead of atomic
weights, 199, 227
Erbium, 410
Erucic acid, 443
Esters, 439
Ether as a fifth element, 8
-acids, 439
constitution of, 256
from alcohol, 98, 152
Ethereal oils, 20, 436
Etherin theory, the, 253-254
Ethers, compound, 439
mixed, 298, 439
simple, 439
varieties of, 152
(Williamson), 298
Ethionic acid, 439
Ethyl, 256
Ethyl ether, 439
ether, formation of (Williamson),
298
sulphide, 463
-sulphuric acid, 439
theory, the, 256
Ethylene, composition of (Dalton),
189-190
oxide, 439
Eurhodines, 579
Eurhodols, 579
620
INDEX OF SUBJECTS
Experimental lectures, 265, 586
et seq.
methods, development of, by
Boyle, 103-104
Explosives, 567-568
FATS, 19, 98, 153-154, 540
Fatty acid series, structure of com-
pounds of the, 344-346
Fatty acids, 441
acids, constitution of (Kolbe), 314
et seq.
Fatty oils, &c., 19
Fermentation, 79, 546 et seq.
former views regarding, 152
processes, 546 et seq. , 574
significance of (v. Helmont)) 77-78
theories, 546 et seq.
Ferments, organised and unorgan-
ised, 547-548
Ferric acid, 427
Ferricyanogen, 474
Ferrocyanogen, 473
Ferrocyanogen compounds (Berze-
lius), 206
Filter papers, incineration of, 388
Filtering appliances, 593
"Fire air" (oxygen), 131
" Fire-damp Commissions," 584
Fixation of carbonic acid by alkalies
(Black), 119-120, 128
of mercury, 27
" Fixed air" (Black), 120
Flame colourations (Marggraf,
Scheele), 143
reactions (Bunsen), 385
Flesh, chemistry of, 543
Fluorene, 436
Fluorine, 403
its analogy to chlorine, 418
compounds, 206, 418, 424
compounds, organic, 460
oxygen compounds of, 460
Foods, analysis of, 399
Formazyl compounds, 472
Formic acid, 153
aldehyde, 449, 450, 537
production of, in plants, 537
Formulae (Gerhardt's), 304-305
graphical (Kekule), 343
rational (Kolbe), 321
Formyl-acetic ester, 453
Four- volume formulae, 293
Freezing point of solutions, 502
Friction, fluid, 501
Fuchsine, 576
Fulminate of mercury (Kekule), 308
Fulminic acid, 478
Fulminic acid, isomerism with
cyanic acid, 251
Fulminuric acid, 478
Fumaric acid, 443
Furfurane, 350, 484
Furfurol, 484
Furnace gases, 557
GALL apples, juice of, 98
Gallium, 374, 409
Galmei, 15
Galvanic current used in analysis,
390
Galvano-plastic process, the, 559
Gas analysis, 392
analysis, beginnings of, 145
analysis, technical, 392
Gas regulators, 593
Gas sylvestre, 79
" Gas," the generic term, 79
Gases, absorption of, 493
critical pressure of, 493
critical temperature of, 493
discovery of many by Priestley
and Scheele, 123-124, 127, 128
et seq.
kinetic theory of, 493
liquefaction of, 492-493
their first collection over mercury,
129
the chemistry of gases in the
phlogistic period, 128 et seq.
van Helmont's researches on,
78-79
Gastric juice, 541
Geber's writings and doctrines, 29
Geometrical isomerism (J. Wisli-
cenus), 356 et seq.
Generators, 584
Germanium, 374, 411
German silver, 558
Glass, history and manufacture of,
16, 47-48, 89, 147, 570
Glauber's salt, 92
Glucoses, 454-455
constitution and synthesis of, 454
et seq.
Glucosides, 456
Glycerine, 154, 328, 438-439
Glyceryl, 328
Glycocoll, 319
Glycollic acid, 319
Glycogen, 543
Glycol, 328
Glycols, 439
Glyoxal, 449
Glyoxaline, 485
Gold, 11-12, 46-47, 88, 558
INDEX OF SUBJECTS
621
Gold, amalgamation of, 12
compounds of, 430
determination of its atomic weight.
430
separation from silver, 12, 88
Goulard's lotion, 155
Gradverwandtschaft, 333
Great chemical industries, the, 561
Groups of elements, 367, 370 et seq.
Guanidine, 468
Guanamines, 468
Gun-cotton, 568
Gunpowder, 567
Gypsum, 93
HALOGEN carriers, 458
derivatives of hydrocarbons, 457
et seq.
Halogens, the, 239-240, 402, 403
compounds of the, 239, 418, 424
hydrides of, 418
their action on the unsaturated
hydrocarbons, 459
Handworterbuch de Chemie, 267, 595
Heat, latent (Black), 120
latent (Lavoisier and Laplace),
162
nature of (Lavoisier), 162, 170
of combustion, 507 et seq.
of formation, constancy of (G. H.
Hess), 507
specific, its relation to atomic
weight (Dulong and Petit), 220
Heat-capacity of atoms, 220
Heating materials, 584
Helium, 393, 415, 416, 419
Hermetic Society, 62
Hermetic, 24-25
art, 24-25
Heterologous compounds, 303
Hexagon formula of benzene, 347
Hexoses, 454
Historia naturalis of Pliny, 5
History of chemistry, alchemistic
period, 21 -64
of chemistry, from Lavoisier till
now, 158-598
of chemistry, iatro - chemical
period, 65-99
of chemistry in early times, 5-20
of chemistry, phlogistic period,
100-157
Hoffmann's drops, 98
Homologous compounds, 303
Humus theory, the, 531 et seq.
Hydracides, 241
Hydrates of the metallic oxides,
discovery of, 187
Hydrazine, 423
Hydrazines, 472
Hydrazoic acid, i23
Hydrazones, 451, 455, 472
Hydrides of aromatic hydrocarbons,.
436
Hydrocarbons, 433-437
synthesis of, 361, 434
aromatic, 435
researches on, 433 et seq.
unsaturated, 433 et seq.
Hydrochloric acid, 51, 91
acid gas, 129
acid, manufacture of, 565
acid as a type, 302
Hydrocyanic acid, 153, 474
Hydrofluoric acid, 418
its first use for etching glass, 148
Hydrogen, 78, 121, 402
acids, 241 et seq.
a constituent of organic com-
pounds, 247
as a type, 302 et seq.
as the primary material (Prout),
202
as the unit in the determination
of atomic weights (Dal ton), 192
compounds of the halogens, 418
determination of, 395-396
properties of liquid (Dewar), 493
replacement of in organic com-
pounds, 458-459
Hydrogen acids, theory of the
(Davy; Dulong), 241 et seq..
245
Hydro-phthalic acids, 349, 358
Hydroxylamine, 422
as a specific reagent, 365-366,
451, 462
Hygiene, relations of, to chemistry,
397-399, 545-546
Hyponitrous acid, 422
IATRO-CHEMICAL doctrines of Para
celsus, 69 et seq.
doctrines of Sylvius, 81
doctrines of van Helmont, 76-78
period, the, 65-99
latro-chemistry, general notes upon
3
problems of, 66
latro-chemists, practical-chemical
knowledge of the, 87 et seq.
Illuminants, 583
Indamines, 579
Indigo blue (Baeyer), 579
blue, artificial production of, 579
Indium, 409
622
INDEX OF SUBJECTS
Indole, 485
derivatives of , 472
Indo-phenols, 579
Induction, photo-chemical, 511
Inductive methods, the gradual ap-
preciation of, 32, 65, 101
Industrial gases, 393
Industries, the great chemical, 561
Inflammable air, 121
Inorganic compounds, structure of,
343, 367 et seq.
Inorganic compounds, systematising
of, 367, 371, et seq.
Institut National, 176
Instruction, growth of chemical,
586-598
systematic chemical, 207, 265,
271, 312, 586 et seq.
technico-chemical, 556
chemical, in laboratories, 176, 194,
204, 207, 265, 588 et seq.
International Commission on chemi-
cal nomenclature of organic com-
pounds, 437
Iodine, 402, 566
recognised as an element, 240
Iodine (Gay-Lussac), 200
" lodo-benzene," 459
lodo- and iodoso-compounds, 351,
458-459
lodonium bases, 459
lodoso-benzene, 459
Ions, 503
Iridin, 457
Iridium, 413
Iron, 13-14, 47, 89, 147, 557-558
industry, the, 557
ores used in olden times, 13-14
Iron-carbonyl, 428, 487
Iron, chloride of, 95
compounds of, 427
Isatoic acid, 320
Iso-butyric acid, 441
Iso-cyanides, the, 476
Iso-cyanuric acid, 477
Iso-diazo-compounds, 473
Isogonism, 506
Isologous compounds, 303
Isomerisation of hydrocarbons, 435
Isomerism, 250-253
geometrical, 356 et seq., 500
of position, 352-353
physical, 447
in spite of identity in structure,
356
Isomers, 250-253
structural- chemical, interpreta-
tion of, 351 et seq.
Isomers among the unsaturated
acids, 443
Isomorphism (Mitscherlich), 221 et
seq., 505 et seq., 524
appreciation of its value by Ber-
zelius, 222-223
polymeric, 505
Iso-nitroso compounds, 461
Iso-propyl alcohol, 438
Iso-pyrazolone, 484
Jahrbuch der Chemie, 598
Jahresberichte der Chemie (Berzelius),
208, 597
der Chemie (Liebig), 267, 598
Journal, Allgemeines J. der Chemie,
180
de Physique, 175
fiir praktische Chemie, 312, 597
Journal of the Chemical Society, 596
of the Society of Chemical Indus-
try, 556
Journals, chemical, 595-598
Journals, old German chemical, 179
Juices, the animal, van Helmont's
views upon, 77-78
Kermes mineral, the, 94, 155
Ketones, 451-454
constitution of (Kolbe), 318
Ketones, fatty aromatic, 452
Ketonic acids, 451-454
Ketoses, 455
Ketoximes, 462
Krypton, 416
LABORATORIES, establishment of,
556, 586 et seq.
for students, 207, 265, 312, 586
et seq.
improvement of, 590
instruction in, 586 et seq.
recent, 590 et seq.
technical, 593
Laboratories, Egyptian, 9
Libavius' effort to establish
chemical laboratories three cen-
turies ago, 75
Laboratory fittings and apparatus,
593
Lactic acid, 153
acid, constitution of, 319
acids, the, 319, 446
Lactones, 448
Lactonic acids, 448
Lana philosophica, 55
Lanthanum, 410
Lapis infernalis, 95
INDEX OF SUBJECTS
623
Latent heat (Black), 120
Law of Boyle and Mariotte, 106
Lead, 14
acetates of, 57, 96
sugar of, 57, 96
Leblanc soda, 562 et seq.
Lecture experiments, 587
Lehrbuch der Chemie (Berzelius),
207
Levulinic acid, 453
Leyden papyrus, the, 23, 24, 26
Liebig- Wohler Letters, the, 254, 262,
263, 268, 272
Liebig's Autobiography, 263
" Life air" (oxygen), 131
Light, chemical action of, 509-511,
536
refraction of, 499
Lime used in ancient times, 19
Linkage, interchange of, 351, 355
Linking bars (Couper), 334
of atoms, 332 et seq., 343
Literature, the more recent chemi-
cal, 594 et seq.
technico-chemical, 556
Lithium, 407
Lucium, 417
Lutidine, 480
MADDER red, 578
Magenta, 576
Magisterium, 41
Magnesia alba, 155
Magnesium, 408, 559
Magnetism of chemical compounds,
504
Maleic acid, 443
Malic acid, 153
Malonic acid, 442
Manganese, 149
black oxide of (Scheele), 127
compounds, 427
Mannite, 439
Manuals of chemistry, 74, 108, 114,
119, 154, 266, 271, -273-274, 295,
312, 594 et seq.
Manures, artificial, 567, 574
Marcasitae, 56
Marsh gas, 79
gas as a type, 309
Martin process, the, 558
Masrium, 417
Mass-action, 513, 514, 517 et seq.
Matches, 568
Materia Medica (Dioscorides], 5
prima, 42, 63
Matiere de chaleur (Lavoisier), 170
Meconic acid, etc. , 483
Medicines of various orders for the
transmutation of metals, 40
of ancient times, 18 et seq.
of Paracelsus, 70-71
of the iatro-chemists, 73 et seq.
of the phlogistic period, 154-155
recent, 550-551
Melame, 474, 477
Melamine, 474
Meleme, 477
Mellitic acid, 444
Mellone, 474, 477
Melting points, 497
Mercaptals, 464
Mercaptans, 462-463
Mercaptols, 464
Mercurius philosophorum, 27, 30
et seq., 40 et seq.
Mercury, 15, 47
as a constituent of metals, 39
et seq.
salts of, 53, 95
Mesdem, the old Egyptian cosmetic,
18
Mesitylene, 353, 435
Metabolism, animal, 542, 545
vegetable, 530 et seq.
Metalepsy, 277
Metallic calces, 59, 164, 165, 112
chlorides, 91-92
compounds, recent work with,
426 et seq.
oxides, 55
salts in the alchemistic age, 52-53
Metallo-orgaiiic compounds, 322 et
seq., 486-487
Metallurgy, furtherance of, by
Agricola, 84, 88
in the alchemistic period, 46
in the phlogistic period, 146
of the ancients, 11
of recent times, 557-560
Metals, colouring of, 38
derivation and meaning of the
word, 11
duplication of, 26
ennobling of, 21, 25 et seq., 37
et seq.
increase in weight on calcination,
132, 164.
nature of (Boyle), 134
nature of (Stahl), 134
old chemical theory of the, 38
et seq.
oldest knowledge of the, 11 et
seq.
supposed composition of, in the
alchemistic age, 39, 41
624
INDEX OF SUBJECTS
Metals, transmutation of, 2, 8, 21 |
et seq., 37 et seq.
Metamerism, 252
Methane, composition of (Dalton),
190
Metargon, 416
Methods, analytical, 386 et seq.
technico-chemical, 398
synthetic, in organic
chemistry, 361 et seq.
Methyl violet, 577
Methylene blue, 579
Microscope, its application to chemi-
cal research (Marggraff), 117,
143
Milk, chemistry of, 542
Mineral potash, 567
Mineral system, the chemical (Ber-
zelius), 205
pigments, 560
pigments of ancient times, 18
tanning, 581
waters, artificial, 555
waters, analysis of, in the
Phlogistic period, 142
Mineralogical chemistry, 522-529
systems (Berzelius and others), 525
Minerals, analysis of, 176, 178, 205,
384 et seq., 389, 525
artificial production of, 527-529
classification of, 523 et seq.
classification of (Bergman), 124
Klaproth's researches on, 178
nomenclature of, 525
Mixture-weights of the elements (L.
Gmelin), 203
Modern chemical period, the (from
Lavoisier), 158-598
Molasses, crystallizable sugar from,
573
Molecular compounds (Kekule), 339
weight, determination of, by
vapour density, 376, 490
weight, determination of, in
solutions, 376, 502
heat, 509
weight (Laurent), 294
Molecule, definition of the term, by
Laurent, 294
Molecules, liquid, complexity of,
500-501
Molybdenum, 410, 429
Molybdic acid (Scheele), 151
Monochlor-acetic acid, 459
Mono-saccharides, 456
Mordants, 17, 47, 90, 147, 580
Morphotropism, 506
Mortar, 571
Mosaic gold, 147
Mosandrium, 417
Mucic acid, 153
Multiple types, 302
Muscular power, sources of, 545
Mustard oils, the, 467, 476
Myronic acid, 456
NAPHTHALENE, 435
Naphthenes, 436
Narcotics, 551
Natural Philosophy of the early
part of this century, 263
Neon, 416
Nestorians, the, 28
Neurine, synthesis of, 467
Neutralisation, law of (Richter), 183
Nickel, 149, 410, 558
Nickel-carbonyl, 428, 487
Nickolanum, 417
Nicotine, 483
Niobium (Marignac), 369, 410, 430
Nitragins, 535
Nitric acid, 51-52, 148, 566
acid, composition of, 122, 150
Nitric oxide, 130
Nitrification, 534
Nitriles, 475
dimolecular, 478
Nitro-benzene, 460
reduction of, 466
Nitro-ethane, 461
-glycerine, 568
-methane, 461
-prussides, 428
Nitro-compounds, organic, 460 et
seq.
Nitrogen chloride, 424
compounds, inorganic, 422 et seq.
compounds, organic, 465 et seq.
discovery of, 130
estimation of, 275, 396-397
diffusion of (Ramsay andTravers),
402
direct assimilation of, by plants,
535
density of, 415
group of elements, atomic weights
of, 404
group of elements, compounds of,
422 et seq.
oxides of, 422
iodide of, 424
Nitrolic acids, 461
Nitrols, 461
Nitroso-compounds, 461
Nitrous acid, 150
Nitrous oxide (Davy), K6
INDEX OF SUBJECTS
625
Nitrum, 16, 52
Nomenclature, chemical (Lavoisier,
etc.), 171-172
chemical (Berzelius), 234
Nordenskiold's Life and Journals of
Scheele, 125, 173
Notation, chemical (Dalton), 194
chemical (Berzelius), 235-237
Nuclei, original and derived
(Laurent), 278
Nucleus theory (Laurent), 278-280
Nutrients, 544-545
Nutrition of animals, 544 et seq.
of plants, 531 et seq., 536 et seq.
Oelsiiss, 154
Oils, ethereal, 20, 582
Oils (fatty) known in ancient times,
19
Optical activity, its connection with
chemical constitution, 357
Organic chemistry, development of,
up to 1811, 246 et seq.
special history of, 432-487
compounds, chemical behaviour of ,
365
compounds, constitution of, 317,
251 et seq. , 303 et seq. , 332 et seq. ,
344 et seq.
compounds, modes of decompos-
ing, 366
compounds, structure of, 336, 344
substances, qualitative composi-
tion of, 248, 393
substances, quantitative composi-
tion of, 248, 393 et seq.
Organic compounds, knowledge of,
in the phlogistic age. 151
classification of, 278-279, 289, 302
compounds, distinction from in-
organic, 246-247
Organo-metallic compounds (Frank-
land), 322 e* *eq., 486-487
Orthrin, 255
Osazones, 455, 472
Osmium, 414
Osmose, 501
Osmosis of sugar solutions, 573
Osmotic pressure, 501-502
Ostwald's Kla**ikert 214
Oxalic acid, 153, 582
acid, synthesis of (Drechsel). 442
Oxalines, 468
Oxalo-acetic ester, 453
Oxaluric acid, 468
Oxazoles, 486
Oxidation theory (Lavoisier), 166-
167
Oxy-acids, constitution of (Kolbe),
319
organic, 446
Oxydes, 172
Oxygen, absorption of, by palladium
and platinum, 430
" rendering active " of, 406
atomic weight of, 403
acids, theory of the, 167, 197,
237-238
law, the (Berzelius), 212
as the unit in atomic weight
determinations (Berzelius), 217
importance of, for the antiphlo-
gistic system, 171
importance of, for the atomic
theory, 210 et seq.
discovery of, 124, 127, 131 et seq.,
165
compounds of the metals, 426 et
seq.
compounds of nitrogen, phos-
phorus, etc., 422-423
compounds of the halogens, 418
compounds of sulphur, 420
• Oxy-muriatic acid, 239
Ozone, 405-406
PALLADIUM, 413
" Panacea" of the ancients, 27, 44
Paper manufacture, 572
Parabanic acid, 468
Paraffin industry, the, 583
" Parallelosterism," 496
Para-oxybenzoic acid, 448
Para-rosaniline, 576
Pathology, its relations to chemistry,
549 et seq.
Pattinson process, the, 558
Penta-methylene-diamine, 480
Pentite, 439
Pepsine, 541
Peptones, 541
Periodic system of the elements, 370
et seq.
Periods of the elements, 371-372
Periods, the various chemical, 1 et
seq.
the various chemical, their charac-
teristics, 1-4
Perkin's violet, 577
Peroxides of organic acid radicals,
445
Per-sulphuric acid, 420
Petroleum industry, the, 583
Pharmaceutical preparations of an-
cient times, 18
Pharmacy, development of, 71
S S
626
INDEX OF SUBJECTS
Pharmacy in the iatro-chemical age,
91 et seq.
its relations to chemistry, 552
Pharmacy, text books of, 553
instruction in, 553
Phenacetine, 551
Phenanthrene, 435
Phenols, 440
manufacture of, 581
Phenyl-hydrazine, 472
as a specific reagent, 365-366,
451, 455, 462
Phenyl-propiolic acid, 444
Philippium, 417
Philosopher's stone, the, 30 et seq.,
40 et seq.
Philosophical Transactions, the, 102,
596
Phlogistic period, general history of
the, 100-128
period, merits of the, 155-157
period, special history of the, 128-
155
period, the, 100-157
system, fall of the, 168
Phlogisticated air (nitrogen), 131
Phlogiston an element, 135
assumption of the hypothetical,
110 et seq.
its identification with hydrogen,
122, 130, 159
theory, beginnings of (Becher), 110
theory, development of (Stahl),
111 et seq.
theory, its development after
Stahl's time, 115 et seq.
theory, general notes on the, 4
theory, its value, 113
Phlogistonists, practical - chemical
knowledge of the, 140 et seq.
Phloroglucin, tautomerism of, 354
Phosgene, 425
Phosphines, etc., 469
Phosphonium bases, 469
Phosphoric acid, 117, 150
acids, basicity of, 244
Phosphorous oxide, 423
Phosphorus, 149, 404
manufacture of, 569
pentafluoride, 340
allotropic modifications of, 406
hydrides of, 421
oxygen compounds of, 423-424
Phosphyl compounds, 462
Photo-chemistry, 509-511
Photography, historical notes on,
510
Phthaleins, 578
Phthalic acid, 578
Physical chemistry, special history
of, 488-521
chemistry, its general significance,
375 et seq.
methods, application of, to chem-
istry, 156, 376
Physics, influence upon chemistry at
the beginning of the phlogistic
period, 101
Phyto-chemistry, 536 et seq.
Picric acid, 460, 580
Pigments of antiquity, the, 17-18
Piperidine, 408
Pitocarpine, 483
Planets, their relation to the metals,
25
Plant juices first used as indicators
by Boyle, 131
Plant-nutrients, 532 et seq.
Plastic compounds (nutritive), 544
Platinum, 149, 413, 558-559
bases, 430
chloride, compounds of with car-
bon monoxide, 431
compounds, 430
metals, the, 413-414
their atomic weights, 414
Poisons, methods for detecting, 397-
398
Polarity, electric, of atoms, 230-231
Poly-azines, 350, 353
Poly-azoles, 353
Polybasic acids, doctrine of the, 243
et seq.
Poly-carboxylic acids, 442
-sulphonic acids, 464
Polymerism, 252
Polymorphism, 505, 525
Poly-saccharides, 456
Porcelain, 17, 63, 147, 571
Position, determination of chemical,
352-353
Position-isomers, 353
Position of elements in the periodic
system, 373
Potash, distinction of, from soda,
92, 118
industry, the, 567
salts, deposits of, 567
salts as medicines, 92
Potashes, 16, 17
Potassium, 238, 407, 426
carboxide, acids from, 453
Potter's art, the, 17, 47, 89, 571
Pottery, 17, 47, 89, 571
Powder, smokeless, 568
Precious stones, artificial, 16, 570
INDEX OF SUBJECTS
627
Precious stones, old imitations of,
16
Precipitates, 96
Prediction of alcohols (Kolbe), 318
of new elements ( Mendel ejeff),
373-374
Preparations, chemical, their manu-
facture, 581-582
old chemical, 18
old medicinal, 18, 19
officinal, in the phlogistic age, 154
technico-chemical, in the phlo-
gistic age, 147
Pressure, critical, 493
Priestley's researches on gases,
123-124
Primary material, assumption of a,
374
Princes as patrons of alchemy, 61
Principe oxyyine, 167
Prism-formula of benzene, 348-349
Progression, law of (Richter), 183-
184
Prom, 255
Propiolic acid, 443
Proportion-numbers of the elements
(Davy), 199
Proportions, doctrine of chemical
(Richter), 182 et seq.
law of constant (Proust), 181,
185-188
law of multiple (Dalton), 189 et
seq.
law of multiple, further developed
by Berzelius, etc. , 210 et seq.
Protyle (Crookes), 374
Prout's hypothesis, 201 et seq., 370
Prussian blue, 147
Prussic acid, 153, 473
Pseudo-forms of compounds, 354
Ptomaines, 398, 549
Ptyalin, 541
Putrefaction, 548 et seq.
bases, 398, 549
Putrescine, 549
Pyra/ine, 485
Pyrazines, 481
Pyrazole, 483
Pyrazolone, 484
derivatives of, 472
Pyrene, 436
Pyridine, constitution of, 350, 479
bases, 478 et seq.
Pyrimidine, 481, 485
Pyrimidines, 481
Pyroligneous acid, 153
Pyromucic acid, 484
Pyrrol, 350, 484
Pyrrolidine, 484
Pyrroline, 484
QUALITATIVE tests for substances,
141-144
Quantitative researches, period of,
158 et seq.
Quick vinegar process, the, 575
Quinazoline, 485
Quinazolines, 481
Quinoline, 350, 480, 485
derivatives of, 481
Quinoline, synthesis of, 479 et seq.
Quinones, 452
Quinoxalines, 481
Quinta essentia, 8
Quintessence, 96
RACEMIC acid (discovery of), 206
acid, isomeric with tartaric, 252
Radical theory, first steps towards
the, 246, 249
theory, the newer, 313-320
the older, 253-262
theory, supersession of the older,
285
theory, fusion of the older radical
theory with the type theory by
Laurent and Gerhardt, 286
Radical vinegar, 96
Radicals, oxygenated, 255, 257
chemistry of compound, 259
compound, 247, 249
polyatomic, 302
the clearer definition of, 260
variability of, 257, 279
Reaction, time-rate of, 518-519
Reactions, specific, of organic com-
pounds, 365
Reagents, introduction into analysis,
141 et seq.
Reciprocal reactions, 518
Reform of chemistry by Lavoisier,
166, 170
Refraction-equivalents, 498
Regenerators, 584
Replaceable value of elements, 323,
326-327
Residues, theory of (Gerhardt), 287
Respiratory compounds (nutritive),
545
Retene, 436
Rhamnite, 439
Rhodamines, 579
Rhodium, 414
Rosaniline, 576
Royal Society, the, 102
Rubidium, 407, 426
628
INDEX OF SUBJECTS
Ruby, artificial production of, 529
glass, 89, 147
Russium, 417
Ruthenium, 413
SACCHARIDES, 456
Saccharimetry, 573
Saccharine, 574
Safety lamp, the Davy, 197, 584
Safranines, 579
Sal, 50
ammoniacum, 53
mirabile, 92
Salicin, 456
Salicylic acid, 319, 447, 550, 582
Saliva, chemistry of the, 541
Salmiac, 53, 93, 149
Sal nitri, 52
Salpetrce, 52
Sal polychrestum (Glaser's), 155
Salt as a constituent of the metals,
41
its meaning in the alchemistic
and iatro-chemical periods, 50,
82-83
Rouelle's definition of a, 119, 136
Salts, constitution of (Berzelius), 233
constitution of (Liebig), 245
nomenclature of (Lavoisier), 172
Saltpetre, 52, 92
as a manure, 17
Sarcosine, 467
Saturation-capacity, assumption of
a constant (Kekule), 338 et seq.
-capacity of the elements (Frank-
land), 322 et seq. , 325, 337
of carbon, 327 et seq.
Scandium, 369, 410
Scheele's Letters and Journals, 125
researches on gases, 129
Schweinfurt green, 560
Secretions, animal, 541
Seignette salt, 97
Selenium (Berzelius), 404
compounds, inorganic, 421
compounds, organic, 463
Sheep's-wool grease, 20
Siderum, 417
Silicates, fusion with alkaline car-
bonates (Bergman), 388
Silicon, 406
alkyl compounds of, 486
compounds of, 424
carbide, 428
Silver, 12, 46, 88, 558
mirrors (Liebig), 269
nitrate of, 53, 95, 560
allotropio modifications of, 406
Silver, oxides of, 427
extraction of, from ores, 558
Smalt, 90
Soap, 17, 148
manufacture, 569
Societies, learned, 101-102
Soda, 17, 18
artificial preparation of, 118, 148,
149, 569
industry, the, 562-564, 565
salts as medicines in the iatro-
chemical age, 92
Soda-waste, working up of, 563-
564
Sodium, 238, 407, 426, 559
Sodium peroxide, 426, 559
Soils from a chemical-agricultural
point of view, 531 et seq.
Solar spectrum, chemical action of
the, 510
Solder, 14
Solidification, Raoult's law of, 502
Solution, theory of, 376, 501 et seq.
Soporifics, 551
Spagiric art, the, 25
Special history of modern chemistry,
381 et seq.
Specific gravity of gases, 129
heat (Lavoisier ; Laplace), 162
heat of solids, 497
heats of the metals, relation to
their atomic weights (Dulong
and Petit), 220
volume, 495
Spectrum analysis, 385-386, 494
Spirit-lamp (Berzelius), 388
Spirit of wine, 49, 57, 98, 152
sweetening of, 57
Spirits, manufacture of, 575
Spiritus, 50
fumans Libavii, 95
igno-aereus (Mayow), 130
Mindereri, 93
salis, 50-51
tartari, 97
Starch, 19, 149, 456, 538, 572
sugar, 572
Stassfurt salts, 567
Statique Chimique (Berthollet), 174,
185, 514
Stearine candles, 569
Steel, 89, 146, 557
Steren, 496
Stereo-chemistry, 355 et seq.
of nitrogen, 359 et seq, 462
Stereo-isomerism, 355 et seq, 443,
459, 473
Stibines, &c., 469
INDEX OF SUBJECTS
629
Stochiometry, 387
founding of (Richter), 185
Strontium, 197, 408
Structural formulae (Couper), 334
Structure, chemical, 332, 336 et seq.
theory, beginnings of the, 332
et seq.
theory, development of the, 342
et seq.
Sublimate, 53
" Substantive cotton dyes," 578
dyes, 147
Substitution, first observations upon,
276
-form (Gerhardt), 288
laws of (Dumas), 276
theory (Laurent), 278
partial admission of, by Ber-
zelius, 284
Succinic acid, 97, 442
Sugar from beet juice, 116, 149, 573
estimation of, 392
refining of, 573
Sugar, known by the ancients, 19
from sugar cane, 99
Sugars, synthesis and constitution
of, 455-456
Sulphines, 464
Sulphinic acids, 465
Sulphite cellulose, 562, 572
Sulphone-ketones, 464
Sulphones, 464
Sulphonic acids, 463-464
Sulphonal, 464
Sulphoxides, 464
Sulphur, allotropic modifications of,
406
atomic weight of, 404
balsam, 56
as a constituent of the metals,
39, 55-56
Sulphur auratum, 94
Sulphur, compounds of, 420
compounds of the alchemistic
period, 55-56
compounds, organic, 460, 465
Sulphur > .'//'/•, 152
Sulphur, milk of, 56
Sulphur philosophorum, 52
Sulphur, recovery of, from alkali
waste, 563-564
Sulphures, 172
Sulphuretted hydrogen, discovery
of, 129
Sulphuric acid, 51, 91
acid, anhydrous, 562
acid, fuming, 148
acid, manufacture of, 148, 561
Sulphurous acid gas, 19, 129
acid, practical utilisation of, 562
Symbols, chemical (Berzelius), 235
(Dalton), 194
with bar across them (Berzelius),
236, 283
Synthesis by condensations, 362
of organic compounds, 361 et seq.
Syrians, culture among the, 28
System, chemical, of the minerals
(Berzelius), 524
natural, of the elements, 370
periodic, 370 et seq.
Systematization of inorganic
compounds, 367
of organic compounds, 433
Systeme unitaire (Gerhardt), 303-304
Tables des Rapports (Geoffrey), 117
Tables of affinity (Geoffrey), 117
Tannic acids, 537
Tanning, 580
Tantalum (Marignac), 369, 412-413,
430.
Tar, products from, 582
Tartar, 96-97
emetic, 73, 97
Tartaric acid, 153
acids (optically isomeric), 447
Tartarus, 70, 97 .
Taurine, constitution of, 319
Tautomerism, 354-355
Technical Schools and Colleges, 556
Tellurium, 403-404
compounds, inorganic, 420-421
compounds, organic, 462-463
Temperature, critical, 493
Tension-series of the elements (Ber-
zelius), 231-232
Terbium, 410
Terpenes, 436
Terra pinguis (Becher), 110
Tetrolic acid, 443
Text-books of chemistry. See
Manuals
Thallium, 409, 427
Therapeutics, relation of, to chemis-
try, 494-495
Thermo-chemistry, 507-509, 517
Thiacetic acid, 463
Thiamides, 468
Thiazoles, 486
Thio-aldehydes, 451
Thiocyanogen, 475
Thionylamines, 465
Thiophene, 350, 484
Thomas-Gilchrist process, the, 557
INDEX OF SUBJECTS
Thorium, 411
Thymol, 550
Tin, 14, 89
compounds of, 429
dioxides, isomeric, 251
perchloride of, 95
Tinctures, 38
Tincture for changing silver into
gold, 27
Tinder, chemical, 568
Titanium, 179, 411
Titrimetry, 201, 390
Toluidines, 577
Traite" fiUmentaire de Chimie (La-
vosier), 164
Tri- and Tetra-methylene deriva-
tives, 435
Tri-amines, 465
Tri-azines, 481
Triazole, 485 ,--" . • ' '
Tri-methylamine, 467
Trichloracetic acid, 275, -.280, 283,
459 . .
Trimethyl-carbinol, 438 <•'«!/*"''
Trimethylene, 435
Triphenyl- methane, 436
-phosphine oxides, isomeric, 340
Tropseolines, the, 578
Tungsten, 410, 429
Tungstic acid (Scheele), 151
Turpentine, oil of (known to the
ancients), 19
Turpeth mineral, 95
Tutty, 15
Two-volume formulae, 293
Type metal, 560
Type theory, the newer (Gerhardt),
300 et seq.
theory, the newer (Kekule), 307
et seq.
theory, the newer (Sterry Hunt),
301
the newer (Williamson), 298 et seq.
the newer, preparatory work for,
295 et seq.
theory, the older (Dumas), 280-
281
Types, chemical, 281
condensed, 302, 307
duplicated, 302, 307
(Gerhardtfs), 300 et seq.
mechanical, 281
mixed, 308-309
real, as opposed to formal, 307, 321
auxiliary, 303
ULTRAMARINE, 570
Unitarism, beginnings of, 237 et seq.
Unitarism, development of, 275, 281
et seq.
Universal medicine, 44
Universities, establishment of, 65
Unsaturated compounds, 345
Uranium, 179, 410, 429
Urea, estimation of, 392
synthesis of, 252, 361
Ureas, substituted, 477
Uric acid, 153, 268
derivatives of, 468
synthesis of, 468
Urine, 542
analysis of, 543
chemistry of the, 542-543
VALENCY of the elements. See
Saturation-capacity
tant or varying, 337-342
*ine of, its influence on the
••••( • &&&$pment of chemistry, 331
maximum, 338
, 326-328
oFcarbon, 327-330
definite, 331
varying, 325, 336
its application to inorganic com-
pounds, 367
Vanadium (Roscoe), 369, 412, 429
Vanillin, 449
Vapour density determination,
methods of, &c. (Dumas, Gay-
Lussac and Hofmann, Victor
Meyer), 225, 376, 490 et seq.
densities, abnormal, 492
pressure of liquids, 497
pressure of solutions, 502
Vegetable physiology, 530 et seq.
Versuch iiber die Theone der chemis-
chen Proportionen (Berzelius),
213, 235
Vitriols, 52
"Volume-atoms" (Berzelius), 216
Volume theory (Berzelius), 216,
229
Volumes, law of, extension by
Avogadro, 215
law of (Gay-Lussac), 200, 214 et
seq., 490
law of, its appreciation by Ber-
zelius, 216 et seq.
specific, 495
Volumetric analysis, 390
analysis, beginnings of, 201
Wahlverwandtschaft, 138, 333
Water as a type, 298 et seq.
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