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Title: History of Chemistry, Volume II (of 2) Author: Edward Thorpe Release Date: September 26, 2017 [EBook #55631] Language: English Character set encoding: UTF-8 *** START OF THIS PROJECT GUTENBERG EBOOK HISTORY OF CHEMISTRY, VOL 2 *** Produced by Sonya Schermann, Charlie Howard, and the Online Distributed Proofreading Team at http://www.pgdp.net (This file was produced from images generously made available by The Internet Archive) London A HISTORY OF THE SCIENCES Astronomy, by Prof. George Forbes, F.R.S. Chemistry, 2 volumes, by Sir Edward Thorpe, C.B., D Sc., F.R.S., etc. (Director of Government Laboratories) Old Testament Criticism, by Prof. Archibald Duff (Prof. of Hebrew and Old Testament Theology in the United College, Bradford) In Active Preparation— New Testament Criticism, by F. C. Conybeare, M.A. (Late Fellow and Prælector of Univ. Coll., Oxford) Geology, by H. B. Woodward, F.R.S., F.G.S. (Assistant Director of Geological Survey) Geography, by Dr. Scott Keltie, F.R.G.S., F.S.A. G. P. PUTNAM’S SONS New York Justus von Liebig A H I S T O R Y O F T H E S C I E N C E S HISTORY OF C H E M I S T RY BY SIR EDWARD THORPE C.B., LL.D., F.R.S. AUTHOR OF “ESSAYS IN HISTORICAL CHEMISTRY,” “HUMPHRY DAVY: POET AND PHILOSOPHER,” “JOSEPH PRIESTLEY,” ETC., ETC. TWO VOLUMES II. From 1850 to 1910 WITH ILLUSTRATIONS G. P. PUTNAM’S SONS NEW YORK AND LONDON The Knickerbocker Press 1910 Copyright, 1910 by G. P. PUTNAM’S SONS This series is published in London by The Rationalist Press Association, Limited The Knickerbocker Press, New York PUBLISHERS’ NOTE A History of the Sciences has been planned to present for the information of the general public a historic record of the great divisions of science. Each volume is the work of a writer who is accepted as an authority on his own subject-matter. The books are not to be considered as primers, but present thoroughly digested information on the relations borne by each great division of science to the changes in human ideas and to the intellectual development of mankind. The monographs explain how the principal scientific discoveries have been arrived at and the names of the workers to whom such discoveries are due. The books will comprise each about 200 pages. Each volume will contain from 12 to 16 illustrations, including portraits of the discoverers and explanatory views and diagrams. Each volume contains also a concise but comprehensive bibliography of the subject- matter. The following volumes will be issued during the course of the autumn of 1909. The History of Astronomy. By George Forbes, M.A., F.R.S., M. Inst. C.E.; author of The Transit of Venus, etc. The History of Chemistry: Vol. I. circa 2000 B.C. to 1850 A.D. Vol. II. 1850 A.D. to date. By Sir Edward Thorpe, C.B., LL.D., F.R.S., Director of the Government Laboratories, London; Professor- elect and Director of the Chemical Laboratories of the Imperial College of Science and Technology; author of A Dictionary of Applied Chemistry. To be followed by: The History of Geography. By Dr. John Scott Keltie, F.R.G.S., F.S.S., F.S.A., Hon. Mem. Geographical Societies of Paris, Berlin, Rome, Brussels, Amsterdam, Geneva, etc.; author of Report on Geographical Education, Applied Geography. The History of Geology. By Horace B. Woodward, F.R.S., F.G.S., Assistant Director of Geological Survey of England and Wales; author of The Geology of England and Wales, etc. The History of Anthropology. By A. C. Haddon, M.A., Sc.D., F.R.S., Lecturer in Ethnology, Cambridge and London; author of Study of Man, Magic and Fetishism, etc. The History of Old Testament Criticism. By Archibald Duff, Professor of Hebrew and Old Testament Theology in the United College, Bradford; author of Theology and Ethics of the Hebrews, Modern Old Testament Theology, etc. The History of New Testament Criticism. By F. C. Conybeare, M.A., late Fellow and Praelector of Univ. Coll., Oxford; Fellow of the British Academy; Doctor of Theology, honoris causa, of Giessen; Officer d’ Academie; author of Old Armenian Texts of Revelation, etc. Further volumes are in plan on the following subjects: Mathematics and Mechanics. Molecular Physics, Heat, Life, and Electricity. Human Physiology, Embryology, and Heredity. Acoustics, Harmonics, and the Physiology of Hearing, together with Optics Chromatics, and Physiology of Seeing. Psychology, Analytic, Comparative, and Experimental. Sociology and Economics. Ethics. Comparative Philology. Criticism, Historical Research, and Legends. Comparative Mythology and the Science of Religions. The Criticism of Ecclesiastical Institutions. Culture, Moral and Intellectual, as Reflected in Imaginative Literature and in the Fine Arts. Logic. Philosophy. Education. CONTENTS CHAPTER I PAGE State of Chemistry in the Middle of the Nineteenth Century 1 Introductory. Some Founders of Modern Chemistry: Liebig, Wöhler, Dumas. Rapid Extension of Organic Chemistry after 1850: Laurent and Gerhardt, Hofmann. Development of theory in Organic Chemistry. Other representative men of the middle period of the Nineteenth Century: Graham, Williamson, Bunsen. Modern Chemistry in relation to the Atomic Theory. CHAPTER II The Chemical Elements Discovered since 1850 26 Nomenclature and Classification of Elements. Numerical relationships. Modes of discovery. The Spectroscope. Cæsium, rubidium, thallium, indium, gallium, scandium, germanium. The rare earth elements. Industrial applications of rare elements. CHAPTER III The Inactive Elements: Radium and Radio-Activity 43 Argon, helium, krypton, neon, and xenon. Radium. Disintegration theory of Rutherford and Soddy. Actinium and polonium. The emanations. CHAPTER IV Atoms and Molecules: Atomic Weights and Equivalents 61 Hypothesis of Avogadro. Stanislao Cannizzaro. Determination of molecular weights. Applicability of law of Dulong and Petit. Relations of molecular weight to osmotic pressures. Determination of atomic weights. Hypothesis of Prout, Dumas, Stas, Lord Rayleigh, Leduc, Morley, Guye, Theodore Richards. Validity of law of conservation of mass: Landolt. CHAPTER V The Molecular Theory of Gases 79 Interdependence of the gaseous laws. Kinetic theory of gases: Bernoulli, Waterston, Clausius, Maxwell, Boltzmann, Schmidt, Graham. Gaseous diffusion. Van der Waals’s equation. Ratio of specific heats: Kundt and Warburg. Liquefaction of gases. Critical temperatures and pressures: Andrews, Pictet and Cailletet, Wroblewski, Olszewki, Dewar, Kammerlingh Onnes. Liquefaction of air on the large scale. Research at low temperatures. CHAPTER VI The Periodic Law 101 Prout, Thomson, Döbereiner, Newlands, De Chancourtois. Statement of the Periodic Law by Mendeléeff and Lothar Meyer. Its importance as a system of classification. CHAPTER VII Valency 112 Origin of conception of Valency: Williamson, Gerhardt, Frankland, Couper, Kekulé. Tetravalency of carbon and linkage of atoms. Rational and constitutional formulæ. Dynamical theories of valency. CHAPTER VIII The Chemistry of Aromatic Compounds 119 Peculiarities of aromatic compounds. Kekulé’s benzene theory. Its applications. The essential oils. Terpenes. Camphor. Synthesis of perfumes. Alkaloids. CHAPTER IX Stereo-Isomerism: Stereo-Chemistry 138 Opticity: Biot, Mitscherlich, Pasteur, Wislicenus, Van ’t Hoff, Le Bel. Asymmetry. Racemisation. Multirotation. Geometrical isomerism. Geometrical inversion. Stereo-isomerism among nitrogen, sulphur, selenium, tin, and silicon compounds. Tautomerism. Steric hindrance. v vi vii CHAPTER X Organic Synthesis: Condensation: Synthesis of Vital Products 152 Use of specific condensing reagents. Carbon suboxide. Artificial preparation of naturally occurring substances. Synthetic medicines. The ptomaines. Artificial alizarin. Indigo. The sugars and proteins: Emil Fischer. The doctrine of “vital force.” CHAPTER XI On the Development of Physical Chemistry Since 1850 171 Molecular volumes of liquids. Nature of solution. Van ’t Hoff’s application of the gas laws to phenomena of solution. Osmosis and osmotic pressure. Traube. Pfeffer. Semi-permeable membranes. Measurement of osmotic pressure. Arrhenius. Doctrine of ionisation. Its applicability to the explanation of chemical phenomena. Thermo-chemistry. Mass action. Nature of reversible reactions. Thermal and Electrolytic dissociation. Relation between chemical nature and opticity, magnetic rotation and viscosity. Theory of phases. Catalysis. Enzyme action. Relations between valency and volume. Photochemistry. Bibliography 187 Index 191 ILLUSTRATIONS PAGE Justus von Liebig Frontispiece Jean Baptiste André Dumas 9 Thomas Graham 13 From a painting by G. F. Watts, R.A., in the possession of the Royal Society Alexander William Williamson 15 Bunsen, Kirchhoff, and Roscoe 19 Sir William Ramsay 48 Marie Curie (née Sklodowska) 56 Stanislao Cannizzaro 65 Sir James Dewar 98 Dmitri Ivanowitsch Mendeléeff 110 August Kekulé von Stradonitz 126 Jacobus Henricus Van ’t Hoff 142 Emil Fischer 166 Svante August Arrhenius 180 HISTORY OF CHEMISTRY ix 1 I CHAPTER I State of Chemistry in the Middle of the Nineteenth Century n the preceding volume an attempt was made to outline the significant features in the development of chemistry, as an art and as a science, from the earliest times down to about the middle of the last century. Since that time chemistry has progressed at a rate and to an extent unparalleled at any period of its history. Not only have the number and variety of chemical products—inorganic and organic—been enormously increased, but the study of their modes of origin, properties, and relations has greatly extended our means of gaining an insight into the internal structure and constitution of bodies. This extraordinary development has carried the science beyond the limits of its own special field of inquiry, and has influenced every department of natural knowledge. Concurrently there has been a no less striking extension of its applications to the prosperity and material welfare of mankind. With the death of Davy the era of brilliant discovery in chemistry, wrote Edward Turner, appeared for the moment to have terminated. Although the number of workers in the science steadily increased, the output of chemical literature in England actually diminished for some years; and, as regards inorganic chemistry, few first-rate discoveries were made during the two decades prior to 1850. Chemists seemed to be of Turner’s opinion that the time had arrived for reviewing their stock of information, and for submitting the principal facts and fundamental doctrines to the severest scrutiny. Their activity was employed not so much in searching for new compounds or new elements as in examining those already discovered. The foundations of the atomic theory were being securely laid. The ratios in which the elements of known compounds are united were being more exactly ascertained. The efforts of workers, Graham excepted, seemed to be spent more on points of detail, on the filling-in of little gaps in the chemical structure, as it then existed, than in attempts at new developments. For a time—during the early ’thirties—chemists struggled with the claims of rival methods of notation, and it was only gradually that the system of Berzelius gained general acceptance. At none of the British universities was there anything in the nature of practical tuition in chemistry. Thomson, at Glasgow, occasionally permitted a student to work under him, but no systematic instruction was ever attempted. The first impulses came from Graham in 1837, when he took charge of the chemical teaching at the University of London, and when, in 1841, he assisted to create the Chemical Society of London. Four years later the Royal College of Chemistry in London was founded and placed under the direction of August Wilhelm Hofmann—one of the most distinguished pupils of Liebig. Under his inspiration the study of practical chemistry made extraordinary progress, and discovery succeeded discovery in rapid succession. In bringing Hofmann to England we had, in fact, imported something of the spirit and power of his master, Liebig. Among the pupils and co-workers of Hofmann were Warren de la Rue, Abel, Nicholson, Mansfield, Medlock, Crookes, Church, Griess, Martius, Sell, Divers, and Perkin. Whilst at Giessen he had begun the study of the organic bases in coal-tar with a view more especially of establishing the identity of Fritzsche’s anilin with the benzidam of Zinin and the krystallin of Unverdorben. Hofmann continued to cultivate with unremitting zeal the field thus entered. With Muspratt he discovered paratoluidine and nitraniline; with Cahours allyl alcohol. His pupil Mansfield worked out, at the cost of his life, the methods for the technical extraction of benzene and toluene from coal-tar, and thereby made the coal-tar colour-industry possible. It was in attempting to synthesise quinine by the oxidation of aniline that Perkin, then an assistant at the college, obtained, in 1856, aniline purple, or mauve, as it came to be called by the French, the first of the so-called coal-tar colouring matters. In 1859 this was followed by the discovery of magenta, or fuchsine, by Verquin. For its manufacture Medlock, one of Hofmann’s pupils, in 1860 devised a process by which for a time it was almost exclusively made. Hofmann studied the products thus obtained, and showed that they were derivatives of a base he called rosaniline; and he demonstrated that the colouring matters were only produced through the concurrent presence of aniline and toluidine. He also proved that the base of the dye, known as aniline blue, was triphenylrosaniline. As the result of these inquiries he obtained the violet or purple colouring matters known by his name. Lastly, all his classical work on the amines, ammonium compounds, and the analogous phosphorus derivatives was done at the Royal College of Chemistry. Prior to the establishment by Liebig, in 1826, of the Giessen laboratory, the state of chemistry in Germany was not much, if at all, better than with us. The creation of the Giessen school initiated a movement which has culminated in the pre-eminent position which Germany now occupies in the chemical world. Students from every civilised country came to study and to work under its leader, and to carry away with them the influence of his example, the inspiration of his genius, and the stimulating power of his enthusiasm. Justus von Liebig, was born at Darmstadt on May 12, 1803, and after graduating at Erlangen, where he worked on the fulminates, he repaired to Paris and entered the laboratory of Gay Lussac, with whom he continued his inquiries. Returning to Germany, he was appointed Professor of Chemistry at Giessen in 1826, and began those remarkable series of scientific contributions upon which the superstructure of organic chemistry largely rests. He investigated the cyanates, cyanides, ferrocyanides, thiocyanates, and their derivatives. In conjunction with Wöhler he discovered the group of the benzoic compounds and created the radical theory. With Wöhler also he investigated uric acid and its derivatives. He discovered hippuric acid, fulminuric acid, chloral, chloroform, aldehyde, thialdine, benzil, and elucidated the constitution of the organic acids and the amides. He greatly improved the methods of organic analysis, and was thereby enabled to determine the empirical formulæ of a number of carbon compounds of which the composition was imperfectly known. He practically laid the foundations of modern agricultural chemistry, and to his teaching is due the establishment of an important branch of technology—the manufacture of chemical fertilisers. He worked on physiological chemistry, especially on the elaboration of fat, on the nature of blood, bile, and on the juice of flesh. He studied the processes of fermentation, and of the decay of organised matter. He was a most prolific writer. The Royal Society’s Catalogue of Scientific Papers enumerates no fewer than 317 contributions from his pen. He was the founder of the Annalen der Chemie, which is now associated with his name, and of the Jahresbericht; he published an Encyclopædia of Pure and Applied Chemistry and a Handbook of Organic Chemistry. His Familiar Letters on Chemistry was translated into every modern language, and exercised a powerful influence in developing popular appreciation of the value and utility of science. Liebig left Giessen in 1852 to become Professor of Chemistry at the University 2 3 4 5 6 of Munich and President of the Academy of Sciences. He died at Munich on April 18, 1874. With the name of Liebig that of Wöhler is indissolubly connected. Although the greater part of their work was not published in conjunction, what they did together exercised a profound influence on the development of chemical theory. Friedrich Wöhler was born at Eschersheim, near Frankfort, on July 31, 1800. After studying at Marburg, where he discovered, independently of Davy, cyanogen iodide, and worked on mercuric thiocyanate, he went to Heidelberg and investigated cyanic acid and its compounds, under the direction of Gmelin. In 1823 he worked with Berzelius at Stockholm, where he prepared some new tungsten compounds and practised mineral analysis. In 1825 he became a teacher of chemistry in the Berlin Trade School. Here he succeeded for the first time in preparing the metal aluminium and in effecting the synthesis of urea—one of the first organic compounds to be prepared from inorganic materials. Jointly with Liebig he worked upon mellitic and cyanic and cyanuric acids. In 1832 Wöhler, now appointed to the Polytechnic at Cassel, began with Liebig their memorable investigation on bitter-almond oil. In 1836 he was called to the Chair of Chemistry in the University of Göttingen, and with Liebig attacked the constitution of uric acid and its derivatives—the last great investigation the friends did in common. Wöhler subsequently devoted himself mainly to inorganic chemistry. He isolated crystalline boron, and prepared its nitrides, discovered the spontaneously inflammable silicon hydride, titanium nitride, and analysed great numbers of minerals and meteorites and compounds of the rarer metals. He made Göttingen famous as a school of chemistry. At the time of the one and twentieth year of his connection with the University it was found that upwards of 8000 students had listened to his lectures or worked in his laboratory. He died on September 23, 1882. In France, Dumas exercised a no less powerful influence. If Liebig could reckon among his pupils Redtenbacher, Bromeis, Varrentrapp, Gregory, Playfair, Williamson, Gilbert, Brodie, Anderson, Gladstone, Hofmann, Will, and Fresenius; Dumas could point to Boullay, Piria, Stas, Melsens, Wurtz, and Leblanc—all of whom did yeoman service in developing the rapidly expanding branch of organic chemistry. Jean Baptiste André Dumas Jean Baptiste André Dumas was born on July 14, 1800, at Alais, where he was apprenticed to an apothecary. In his sixteenth year he went to Geneva and entered the pharmaceutical laboratory of Le Royer. Without, apparently, having received any systematic instruction in chemistry, he commenced the work of investigation. With Coindet he established the therapeutic value of iodine in the treatment of goître; with Prevost he attempted to isolate the active principle of digitalis, and studied the chemical changes in the development of the chick in the egg. In his twenty-fourth year Dumas went to Paris and became Répétiteur de Chimie at the École Polytechnique. He joined Audouin and Brongniart in founding the Annales des Sciences Naturelles, and began his great work on Chemistry Applied to the Arts, of which the first volume appeared in 1828. At about this time he devised his method of determining vapour densities, and published the results of a number of estimations made by means of it. With Boullay he began an inquiry on the compound ethers, out of which grew the etherin theory, which served as a stepping-stone to the theory of compound radicals— subsequently elaborated by Liebig and Wöhler. Dumas discovered the nature of oxamide and of ethyl oxamate, isolated methyl alcohol, and established the generic connection of groups of similarly constituted organic substances, or, in a word, the doctrine of homology. His work on the metaleptic action of chlorine upon organic substances eventually effected the overthrow of the electro- chemical theory of Berzelius and led to the theory of types, which, in the hands of Williamson, Laurent, Gerhardt, and Odling, was of great service in explaining the analogies and relationships of whole groups of organic compounds. He worked in every field of chemistry. He invented many analytical processes, established the gravimetric composition of water and of air, and revised the atomic weights of the greater number of the elements then known. Dumas exercised great influence in scientific and academic circles in France. He was an admirable speaker, and had rare literary gifts. On the creation of the Empire he was made a Senator, and was elected a member of the Municipal Council of Paris, of which he became president in 1859. He died on April 11, 1884. It was largely through the influence of these master-minds that chemistry took a new departure. Prior to their time organic chemistry hardly existed as a branch of science: organic products, as a rule, were interesting only to the pharmacist mainly by reason of their technical or medicinal importance. But by the middle of the nineteenth century the richness of this hitherto untilled field became manifest, and scores of workers hastened to sow and to reap in it. The most striking feature, indeed, of the history of chemistry during the past sixty years has been the extraordinary expansion of the organic section of the science. The chemical literature relating to the compounds of carbon now exceeds in volume that devoted to all the rest of the elements. In the middle of the nineteenth century chemists began to concern themselves with the systematisation of the results of the study of organic compounds, and something like a theory of organic chemistry gradually took shape. From this period we may date the attempts at expressing the internal nature, constitution, and relations of substances which, step by step, have culminated in our present representations of the structure and spatial arrangement of molecules. In 1850 the dualistic conceptions of Berzelius ceased to influence the doctrines of organic chemistry. The enunciation by Dumas of the principle of substitution, and its logical outcome in the nucleus theory and in the theory of types, had not only effected the overthrow of dualism, but was undermining the position of the radical theory of Liebig and Wöhler. The teaching of Gerhardt and Laurent had spread over Europe, and was influencing those younger chemists who, while renouncing dualism, were not wholly satisfied with a belief in compound radicals. Williamson’s discovery, in 1850, of the true nature of ether and of its relation to alcohol, and his subsequent preparation of mixed ethers, served not only to reconcile conflicting interpretations of the process of etherification, but also to reconcile the theory of types with that of radicals. Lastly, his method of representing the constitution of the ethers and their mode of origin gave a powerful stimulus to the use of type-formulæ in expressing the nature and relations of organic compounds. 7 8 10 11 12 13 Thomas Graham. From a painting by G. F. Watts, R.A., in the possession of the Royal Society. Other representative men of the middle period of the nineteenth century, in addition to Williamson, were Graham and Bunsen. The three men were investigators of very different type, and their work had little in common. But each was identified with discoveries of a fundamental character, constituting turning-points in the history of chemical progress, valuable either as regards their bearing on chemical doctrine or as regards their influence on operative chemistry. Thomas Graham was born in Glasgow on December 21, 1805, and, after studying under Thomas Thomson at the University of that city, attended the lectures of Hope and Leslie in Edinburgh. In 1830 he succeeded Ure as teacher of chemistry at Anderson’s College in Glasgow, and in 1837 was called to the Chair of Chemistry in the newly-founded University of London, in succession to Edward Turner. In 1854 he was made Master of the Mint. He died in London on September 16, 1869. Graham’s work was mainly devoted to that section of the science now known as physical chemistry. His contributions to pure chemistry are few in number. By far the most important is his discovery of metaphosphoric acid and its relations to the other modifications of phosphoric acid. Ortho- or ordinary phosphoric acid was known to Boyle; pyrophosphoric acid was discovered by Clark. Graham’s work is noteworthy as first definitely indicating the inherent property of the acids to combine with variable but definite amounts of basic substances by successive replacement of hydroxyl groups—the property we now term basicity, and was of fundamental importance in regard to its bearing on the constitution of acids and salts. Graham’s fame chiefly rests upon his discovery of the law of gaseous diffusion (1829–1831), upon his work on the diffusion of liquids, and upon his recognition of the condensed form of hydrogen he termed hydrogenium. Questions involving the conception of molecular mobility, indeed, constituted the main feature of his inquiries. We owe to him, among others, the terms crystalloid, colloid, dialysis, atmolysis, occlusion—all of which have taken a permanent place in the terminology of science. Alexander William Williamson. Alexander William Williamson was born at Wandsworth, London, on May 1, 1824. His father, a Scotchman and a fellow-clerk of James Mill (the father of John Stuart Mill) in the East India House, took an active share in the foundation, in 1826, of the University of London, subsequently known as University College. In 1840 the younger Williamson entered the University of Heidelberg with the intention of studying medicine; but, under the influence of Leopold Gmelin, he turned to chemistry. In 1844 he went to Giessen, to work under Liebig, and there made his first contributions to chemical science—viz., on the decomposition of oxides and salts by chlorine; on ozone; and on the blue compounds of cyanogen and iron. After graduating at Giessen he went, in 1846, to Paris, where he came under the influence of Comte, with whom he studied mathematics. In 1850, at Graham’s solicitation, he was appointed to the Chair of Practical Chemistry at University College, vacant by the death of Fownes. He at once embarked upon those researches which constitute his main contribution to science. In the attempt to build up the homologous series of the aliphatic alcohols from ordinary alcohol he succeeded in demonstrating the real nature of ether and its genetic relation to alcohol, and in explaining the process of etherification. The memoirs (1850–52) in which he embodied the facts had an immediate influence on the development of chemical theory. His explanation of the process of etherification familiarised chemists with the idea of the essentially dynamical nature of chemical change. He imported the conception of molecular mobility not only into the explanation of such metathetical reactions as the formation of the ethers, but into the interpretation of the phenomena of chemical change in general. In these papers, as also in one on the constitution of salts, published in 1851, he attempted to systematise the representation of the constitution and relations of oxidised substances—organic and inorganic —by showing how they may be regarded as built up upon the type of water considered as H O, H in which the hydrogen atoms are replaced, wholly or in part, by other chemically equivalent atoms. This idea was immediately adopted by Gerhardt, was further elaborated by Odling and Kekulé, and was eventually developed into a theory of chemistry. Williamson continued to direct the laboratory of University College until 1887, when he retired to the country. He died at Hindhead on May 6, 1904. Robert Wilhelm Bunsen was born at Göttingen on March 31, 1811, and after studying chemistry under Stromeyer, the discoverer of cadmium, went to Paris and worked with Gay Lussac. In 1836 he succeeded Wöhler as teacher of chemistry in the Polytechnic School of Cassel, and in 1842 became Professor of Chemistry in the University of Marburg. In 1852 he was called to Heidelberg, and occupied the Chair of Chemistry there until his retirement in 1889. He died at Heidelberg on August 16, 1899. Bunsen, Kirchhoff, and Roscoe. 16 17 18 Bunsen first distinguished himself by his classical work on the cacodyl compounds, obtained as the result of an inquiry into the nature of the so-called “fuming liquor of Cadet,” an evil-smelling, highly poisonous, inflammable liquid formed by heating arsenious oxide with an alkaline acetate. The investigation (1837–1845) is noteworthy, not only for the skill it exhibits in dealing with a difficult and highly dangerous manipulative problem, but also for the remarkable nature of its results and on account of their influence on contemporary chemical theory. The research, in the words of Berzelius, was the foundation-stone of the theory of compound radicals. The name cacodyl or kakodyl was suggested by Berzelius in allusion to the nauseous smell of the compounds of the new radical arsinedimethyl, As (CH3)2, as it was subsequently termed by Kolbe. Bunsen greatly improved the methods of gasometric analysis; these he applied, in conjunction with Playfair, to an examination of the gaseous products of the blast furnace in the manufacture of iron, and thereby demonstrated the enormous waste of energy occasioned by allowing the gases to escape unused into the air, as was then the universal practice. This inquiry effected a revolution in the manufacture of iron as important, indeed, as that due to the introduction of the hot blast. Bunsen devised methods for determining the solubility of gases in liquids, for ascertaining the specific gravity of gases, their rates of diffusion, and of combination or inflammation. In 1841 he invented the carbon-zinc battery, and applied it to the electrolytic production of metals, notably of magnesium, the properties of which he first accurately described. In 1844 he contrived the grease- spot photo-meter, which was long in general use for ascertaining the photometric value of illuminating gas. His methods of ascertaining the specific heats of solids and liquids were simple, ingenious, and accurate. In 1855–1863 he carried out, in conjunction with Roscoe, a long series of investigations on the chemical action of light. In 1859, in association with Kirchhoff, he devised the first methods of spectrum analysis, and explained the origin and significance of the Fraunhofer lines in the solar spectrum, thus laying the foundations of solar and stellar chemistry. The application of the spectroscope to analytical chemistry almost immediately resulted in his discovery of cæsium and rubidium. Bunsen worked on problems of chemical geology, and made a long series of analyses of volcanic products. With Schischkoff, he examined, in 1857, the products of fired gunpowder. He effected many improvements in analytical chemistry; devised the iodiometric method of volumetric analysis, and systematised the processes of water analysis. Lastly, he invented the gas-burner—a piece of apparatus with which his name is inseparably associated, and which has been of inestimable service to operative chemistry and in the arts. Bunsen was no theorist, and purely speculative questions had little or no interest for him. At the same time he was a great teacher, and made the chemical school of Heidelberg no less famous than the schools of Giessen and Göttingen. * * * * * The mass of material relating to the development of chemistry which has been accumulated during the past sixty years is so vast that it would be hopeless to attempt to survey it in detail within the limits of such a work as this. Nor, indeed, is this required in a history of this character. Those who desire information concerning the origin and sequence of the facts which collectively make up the superstructure of modern chemistry must be referred to the encyclopædias or larger treatises—or, preferably, to the numerous monographs, dealing with special sections, which the volume and complexity of the matter to be dealt with seem to render increasingly necessary. All we can do here is to attempt to show what has been the main outcome of this sixty years of incessant effort to elucidate the mysteries of chemical phenomena and to ascertain the nature of the conditions which control, modify, or determine them. All this effort is ultimately directed to the solution of the fundamental problem of the constitution of matter. The most significant result of this endeavour has been the elaboration and consolidation of the doctrine of chemical atoms, not necessarily of atoms in the limited Daltonian sense, but of atoms considered as associations of particles, or corpuscles—that is, of entities which may be divisible, but which, in the main, are not divided in the vast number of the transformations in which they are concerned. This modification of the original conception of Dalton has been thought by some to destroy the basis upon which his theory really rests. There is no necessity for such an assumption. So pronounced an atomist as Graham, as far back as 1863, in a suggestive paper entitled Speculative Ideas on the Constitution of Matter, enlarged the conception of the Daltonian atom in precisely the sense which recent experimental work appears to require. The present position, too, as it affects chemists, was equally well stated by Kekulé, in 1867, in the following terms: The question whether atoms exist or not has but little significance from a chemical point; its discussion belongs rather to metaphysics. In chemistry we have only to decide whether the assumption of atoms is an hypothesis adapted to the explanation of chemical phenomena. More especially have we to consider the question whether a further development of the atomic hypothesis promises to advance our knowledge of the mechanism of chemical phenomena. I have no hesitation in saying that, from a philosophical point of view, I do not believe in the actual existence of atoms, taking the word in its literal signification of indivisible particles of matter; I rather expect that we shall some day find for what we now call atoms a mathematico-mechanical explanation which will render an account of atomic weight, of atomicity, and of numerous other properties of the so-called atoms. As a chemist, however, I regard the assumption of atoms not only as advisable, but as absolutely necessary, in chemistry. I will even go further, and declare my belief that chemical atoms exist, provided the term be understood to denote those particles of matter which undergo no further division in chemical metamorphoses. Should the progress of science lead to a theory of the constitution of chemical atoms—important as such a knowledge might be for the general philosophy of matter—it would make but little alteration in chemistry itself. The chemical atoms will always remain the chemical unit; and for the specially chemical considerations we may always start from the constitution of atoms, and avail ourselves of the simplified expression thus obtained—that is to say, of the atomic hypothesis. We may, in fact, adopt the view of Dumas and of Faraday—that, whether matter be atomic or not, thus much is certain: that, granting it to be atomic, it would appear as it now does.1 1 The Study of Chemical Composition, by Ida Freund (Cambridge University Press), 1904. 19 21 22 23 24 25 I The greater part of that which follows will be devoted, therefore, to an exposition of certain of the great advances in knowledge— many of them of primary importance—which have been made during the last fifty or sixty years and which have served to strengthen this extended conception of the atomic theory, and to establish its position as an article of the scientific faith of the twentieth century. CHAPTER II The Chemical Elements Discovered since 1850 n 1850 the number of substances generally recognised as chemical elements, in the sense in which that term was first employed by Boyle, was sixty-two. Two members—viz., the pelopium of Rose and the ilmenium of Hermann—were, however, subsequently shown to be identical with metals already known. At the present time (1910) the number of the chemical elements definitely recognised as such is eighty-two. In 1850, as now, they were broadly classified as metals and non-metals, although it was felt then, no less strongly than now, that no very clear line of demarcation was traceable between the two groups. Sixty years ago the elements usually styled non-metals were thirteen in number; to-day the number is nineteen—the increase being due to the inclusion of arsenic and the discovery of the so-called inactive elements, helium, argon, krypton, neon, and xenon. In 1850 there were forty-seven elements definitely classed as metals; in 1910 the number is sixty-three. At all periods in the history of chemistry as a science the general tendency has been to name substances, whenever possible, in accordance with the theoretical conceptions of the time, and hence it has happened that the same body at successive periods has had very dissimilar names. But in naming the substances we term elements, theoretical conceptions are not usually applicable. Oxygen, it is true, derives its name from such a conception; and, etymologically, the name connotes an error. Hydrogen, too, has no more right to be called the water former than oxygen. Davy, who invented the term chlorine, advocated that the chemical elements should be named from some distinguishing peculiarity, either of origin or of physical property. In the main this principle has been adopted especially in later years although there are numerous instances of names derived from pure arbitrary sources. It is largely for the reason that the names of the elements are, with rare exceptions, unconnected with theories that they have remained unchanged, whereas names of compounds, which are far more frequently dependent upon speculative ideas, have constantly been altered in order to comply with the prevailing hypotheses of the period. At the same time it is not always clear that the etymology of certain of the elements is well ascertained. It has been recently shown, for example that the commonly accepted origin of the word “antimony” from antimoine, based on the alleged experiences of mediæval ecclesiastics has no valid foundation. The word is, in reality, derived from the Arabic alhmoud: this became latinised to althimodium and eventually to antimonium. By the middle of the nineteenth century the system of symbolical notation suggested by Berzelius was everywhere current; and, stripped largely of its dualistic associations, this system still remains the most generally convenient method of expressing the composition, analogies, and numerical relations of substances. During the middle of the last century philosophic chemists, although subscribing, with hardly an exception, to the doctrine of definite combining proportions, were by no means agreed as to the sufficiency of Dalton’s explanation of the experimental laws of chemical combination; and the hypothesis of atoms in the Daltonian sense was not universally accepted. To some the atomic theory of Dalton, which assumed that the combining proportion was identical with the relative weight of the atom, was unnecessary as an explanation of the laws of combination. Or at most it was only one out of a variety of molecular conditions in which matter might exist. Consequently some chemists were in the habit of drawing a distinction between chemical atoms and physical atoms. The chemical atom was identical with the Daltonian atom but this was by no means the same as the physical atom of Democritus or Leucippus. The view in 1850, in fact, was not very dissimilar from that to which recent experimental inquiry has led. But it can hardly be said that the doubts were dependent upon valid experimental evidence; they arose rather from the erroneous interpretation of imperfectly ascertained facts—upon the supposed inconsistencies of the law of Gay Lussac with the hypotheses of Avogadro and Ampère. As soon as the facts were clearly perceived and the inconsistencies reconciled we heard less of the supposed distinction between the chemical and the physical atom. It is only within quite recent time, and as the result of entirely new lines of inquiry, that the distinction has been revived. In the early part of the last century attempts were made by Berzelius to classify the chemical elements according to their electro- chemical relations, and by Thomson according as they were “supporters” or “non-supporters of combustion.” It was soon perceived that Thomson’s system had no philosophical basis, and it quickly fell into disuse. After the discovery of isomorphism, an endeavour was made by Graham to arrange the simple bodies in accordance with their natural relations, and even before 1850 the various elements were grouped by him very much as now. This scheme of classification, somewhat modified by considerations of valency, and occasionally corrected by more accurate information concerning true analogies (as when vanadium was transferred by Roscoe to the nitrogen group), was in general use for practically a quarter of a century—in fact, until it was superseded by the gradual adoption of Mendeléeff’s arrangement based on periodicity. There can, however, be little doubt that this attempt by Graham at a natural classification paved the way along which Newlands and eventually Mendeléeff were led to devise our present rational system of grouping the chemical elements. The numerical relationships existing among the equivalents and atomic weights of the elements of certain of these groups, pointed 26 27 28 29 30 out by Dumas, Pettenkofer, Odling, Gladstone, and others, gave rise to much speculation. The values of the gradational differences, of course, depended upon whether equivalents or atomic weights were employed; but the immediate point is that, whichever basis was adopted, definite numerical relations were to be perceived. Thus, in the case of the group of the halogens, it was pointed out that the individual members are connected together as follows: Fluorine. Chlorine. Bromine. Iodine. 19 35.5 80 127 a a + d a + 2d + d´ 2a + 2d + 2d´ where a = 19; d = 16.5; d´ = 28. Thus, too, in the case of the nitrogen group: Nitrogen. Phosphorus. Arsenic. Antimony. Bismuth. 14 31 75 119 207 a a + d a + d + d´ a + d + 2d´ a + d + 4d´ where a = 14; d = 17; d´ = 44. * * * * * On the basis of these and similar numerical relationships it was surmised that, just as the successive members of a group of homologous organic radicals are formed by increments of CH2, so the substances in the several groups of the elements may be produced by successive additions of some form of matter common to them all. This has its counterpart, somewhat modified, in the modern hypothesis of the disintegration of the elements. Dumas conceived the elements in any particular group to be built up by successive accretions of particular forms of matter; Rutherford and Soddy suppose them to be derived by the successive elimination of matter from some unstable parent substance. Since 1850 the existence of at least twenty-two new elements may be said to have been established. Of course, many more than this number have been announced, more or less tentatively; but subsequent investigation has either not confirmed their existence, or has definitely disproved it. The names, symbols, and atomic weights of the twenty-two, arranged in alphabetical order, are as follows: Argon A 39.9 Cæsium Cs 132.8 Dysprosium Dy 162.5 Europium Eu 152.0 Gadolinium Gd 157.3 Gallium Ga 69.9 Germanium Ge 72.5 Helium He 4.0 Indium In 114.8 Krypton Kr 83.0 Lutecium Lu 174.0 Neodymium Nd 144.3 Neon Ne 20.0 Praseodymium Pr 140.6 Radium Ra 226.4 Rubidium Rb 85.4 Samarium Sa 150.4 Scandium Sc 44.1 Thallium Tl 204.0 Thulium Tm 168.5 Xenon Xe 130.7 Ytterbium (Neoytterbium) }Yb 172.0 The additions have been due, to some extent, to the refinement of processes of analysis already in use, but more especially to the employment of new analytical methods; or, lastly, to the application of a generalisation concerning the mutual relations of the elements which has served to indicate not only the existence of new and specific members of families of elements already known, but to point out the probable mode of their occurrence.2 2 The substances which appear to be formed by the disintegration of uranium, radium, thorium—the 31 32 so-called radio-active elements—such as ionium, actinium, polonium, and the various emanations to which they give rise, are not here enumerated. They are dealt with in Chapter III. Although the existence of the element fluorine was surmised as far back as 1771, when Scheele first recognised that the product of the action of oil of vitriol upon fluor-spar contained a hitherto unknown substance, it was not until 1886 that this substance was definitely isolated by Moissan by the electrolysis of the acid potassium fluoride in solution in hydrogen fluoride. Cerium tetrafluoride, CeF4, and lead tetrafluoride, PbF4, when heated, were observed by Brauner to evolve a gas having a smell resembling that of hypochlorous acid, which was probably free fluorine. Certain violet-coloured varieties of fluor-spar, when powdered, emit a peculiar smell, which has been attributed to free fluorine. Gore observed that anhydrous hydrogen fluoride would not conduct electricity—a fact confirmed by Moissan. Moissan found, however, that on adding potassium fluoride to the liquid it readily suffered electrolysis with the liberation of free fluorine as a light greenish yellow gas with a pungent, irritating smell resembling that of hypochlorous acid. It has a vapour density corresponding with an atomic weight 19. By the application of cold and pressure it may be liquefied. At still lower temperatures it may be frozen to a white solid. Fluorine is characterised by an extraordinary chemical activity, and combines, even at ordinary temperatures, with a large number of substances. Sulphur, phosphorus, arsenic, antimony, boron, iodine, and silicon inflame or become incandescent in contact with it. It combines with hydrogen with explosive violence, even in the dark and at the lowest temperature. It unites also with the metals, occasionally with incandescence, and decomposes water with liberation of oxygen. The application, by Bunsen, of the spectroscope to chemical analysis almost immediately resulted in his discovery, in 1860, of cæsium, and, in 1861, of rubidium. Cæsium was first detected in the mineral water of Dürkheim in the Palatinate and in the mineral petalite, by the two blue lines it forms in the spectrum, whence its name from the Latin cæsius, used to designate the blue of the clear sky. Rubidium was found in a lepidolite by means of a number of lines in different parts of the spectrum not previously observed, two being especially remarkable in the outermost region of the visible red portion—whence the name of the element from the Latin rubidus, used to designate the darkest red colour. The new metals were found to have the closest analogies to potassium, with which they usually occur associated in nature. Rubidium is found in a number of lepidolites, leucite, spodumene, triphylite, mica, and orthoclase, and in the Stassfurt carnallite; in sea-water and in many mineral waters. It occurs also in the ashes of many plants such as those of beetroot, tobacco, tea, coffee, etc. It is doubtful if it is a normal constituent of plant food, attempts to introduce it in place of potash having failed. It is not improbable that these elements would have remained unknown except for spectrum analysis. At all events, one of them— cæsium—was missed in 1846 by Plattner, in the course of the analysis of the mineral pollucite, in which it occurs to the extent of one third of its weight. After the discovery of cæsium by Bunsen, this mineral was again analysed by Pisani, when it was found that the alkali which Plattner had mistaken for potassium was in reality cæsium. Cæsium is found to a very small extent in many mineral waters, in a variety of minerals, and in the ashes of plants. In 1861 Sir William Crookes made known the existence of a new element which he called thallium. He found it in a seleniferous deposit obtained from an oil of vitriol factory in the Harz. It was characterised by giving a bright green line in the spectroscope—whence its name from θαλλός, a green or budding...