CHAPTER III. ESTABLISHMENT OF GENERAL PRINCIPLES OF CHEMICAL SCIENCE--PERIOD OF DALTON. John Dalton , 1766-1844. The progress of chemical knowledge became so rapid in the early years of the present century, that although I have in this chapter called the time immediately succeeding that of Lavoisier "the period of John Dalton," and although I shall attempt to describe the advances made by this philosopher without considering those of his contemporaries Davy and Berzelius, yet I must insist on the facts that this arrangement is made purely for the sake of convenience, and that many of the discoveries of Davy, Berzelius and others came in order of time before, or followed close upon the publication of Dalton's atomic theory. Nevertheless, as the work of these men belongs in its essence to the modern period, and as the promulgation of the atomic theory by Dalton John Dalton, the second of three children of Joseph and Deborah Dalton, was born at Eaglesfield, a village near Cockermouth, in Cumberland, on the 5th of September 1766. One of the first meeting-houses established by the Society of Friends is to be found in Eaglesfield. The Dalton family had been settled for several generations on a small copyhold estate in this village. The first of them to join the Friends was the grandfather of John Dalton; his descendants remained faithful adherents of this society. Dalton attended the village schools of Eaglesfield and the neighbourhood until he was eleven years old, by which time, in addition to learning reading, writing and arithmetic, he had "gone through a course of mensuration, surveying, navigation, etc." At the age of ten his taste for measurements and calculations began to be remarked by those around him; this taste was encouraged by Mr. Robinson, a relative of Dalton, who recognizing the indomitable perseverance of the boy appears to have taken some care about this time in directing his mathematical studies. At the early age of twelve Dalton affixed to the door of his father's house a large sheet of paper When he was fifteen years old Dalton removed to Kendal, where he continued for eleven or twelve years, at first as assistant-master, and then, along with his elder brother Jonathan, as principal of a boarding school for boys. It was announced by the brothers that in this school "youth will be carefully instructed in English, Latin, Greek and French; also writing, arithmetic, merchants' accounts and the mathematics." The school was not very successful. Both brothers were hard, inflexible, and ungainly in their habits, and neither was fitted to become a successful teacher of boys: of the two, John had the gentler disposition, and was preferred by the boys; "besides, his mind was so occupied by mathematics that their faults escaped his notice." During this time Dalton employed his leisure in learning Latin, Greek and French, and in pursuing his studies in mathematics and natural philosophy. He became a frequent contributor to the Gentlemen's Diary, a paper which received problems of various kinds—chiefly mathematical—and presented prizes for their successful solution. Besides setting and answering mathematical "Whether, to a generous mind, is the conferring or receiving an obligation, the greater pleasure?" "Is it possible for a person of sensibility and virtue, who has once felt the passion of love in the fullest extent that the human heart is capable of receiving it (being by death or some other circumstance for ever deprived of the object of its wishes), ever to feel an equal passion for any other object?" In his answer to the second of these queries, Dalton carefully framed two hypotheses, and as carefully drew conclusions from each. The question in the Diary was by "Mira;" if "Mira" were a "rapturous maiden" she would not derive much comfort from the cold and mathematical answer by "Mr. John Dalton of Kendal." At Kendal Dalton made the acquaintance of Mr. Gough, who was about eight years older than Dalton, and had been blind from the age of two. Mr. Gough, we are assured by Dalton, was "a perfect master of the Latin, Greek and French tongues;" he understood "well all the different branches of mathematics;" there was "no branch of natural philosophy but what he was well acquainted with;" he knew "by the touch, taste and smell, almost On the 24th of March 1787 Dalton made his first entry in a book which he entitled "Observations on the Weather, etc.;" the last entry in this book he made fifty-seven years later on the evening preceding his death. The importance of Dalton's meteorological observations, as leading him to the conception of the atomic theory, will be noticed as we proceed. In the year 1793 Dalton, who was now twenty-seven years of age, was invited to Manchester to become tutor in the mathematical and natural philosophy department of a college recently established by influential Dissenters in that town. Eighty pounds for the session of ten months was guaranteed him; and he was provided with "rooms and commons" in the college at a charge of £27 10s. per session. He held this appointment for six years, when he retired, and continuing to live in Manchester devoted himself to researches in natural philosophy, gaining a living by giving private lessons in mathematics and physical science at a charge of 2s. 6d. per hour, or 1s. 6d. each if more than two pupils attended at the same time. Dalton was elected a Fellow of the Literary On one occasion during Dalton's stay at Kendal, as he was about to make a visit to his native village, he bethought himself that the present of a pair of silken hose would be acceptable to his mother. He accordingly purchased a pair marked "newest fashion;" but his mother's remark, "Thou hast brought me a pair of grand hose, John; but what made thee fancy so light a colour? I can never show myself at meeting in them," rather disconcerted him, as to his eyes the hose were of the orthodox drab colour. His mother insisted that the stockings were "as red as a cherry." John's brother upheld the "drab" side of the dispute; so the neighbours were called in, and gave their decision that the hose were "varra fine stuff, but uncommon scarlety." From this time Dalton made observations on the peculiarities of his own vision and that of others, and in his first paper read before the Literary and Philosophical Society in 1794, he described these peculiarities. He says, "Since the year 1790 the Dalton's work during the next six or eight years dealt chiefly with problems suggested by his meteorological observations; he published a volume on "Meteorological Observations and Essays," chiefly occupied with descriptions of the instruments employed, more especially of the thermometer and barometer, and an instrument for determining the dew-point of air. By this time he had established the existence of a connection of some kind between magnetism and the aurora, and had thus laid the foundations of a most important branch of meteorology. In 1799, in a note to a paper on rain and dew, he begins his work on aqueous vapour in the atmosphere by proving that water vapour exists as such in the air. This paper is quickly followed by another on the conducting power of water for heat. A very important paper was published in 1801, on the "Constitution of Mixed Gases, etc.," wherein Dalton asserted that the total pressure of a mixture of two gases on the walls of the containing vessel is equal to the sum of the pressures of each gas; in other words, that if one gas is removed the pressure now exerted by the remaining gas is exactly the same as was exerted by that gas in the original mixture. In a paper published much later (1826), when his views and experiments on this subject were matured, he writes: "It appears to me as completely demonstrated as any physical principle, that whenever two or more ... gases or vapours ... are put together, either into a limited or unlimited space, they will finally be arranged each as if it occupied the whole space, and the others were not present; the nature of the fluids and gravitation being the only efficacious agents." This conclusion was followed out and extended in a paper published in 1803, on the absorption of gases by water and other liquids, wherein he states that the amount of each gas mechanically dissolved by a liquid from a mixture of gases depends only on the quantity of that gas in the mixture, the other gases exerting no influence in this respect. Dalton now considered the variation in the In these papers on the "Constitution of Mixed Gases" Dalton also describes and illustrates a method whereby the actual amount of water vapour in a given bulk of atmospheric air may be found from a knowledge of the dew-point of that air, that is, the temperature at which the deposition of water in the liquid form begins. The introduction of this method for finding the humidity of air marks an important advance in the history of meteorology. In this series of papers published within the first three years of the present century Dalton evidently had before his mind's eye a picture of a gas as a quantity of matter built up of small but independent particles; he constantly speaks of pressures between the small particles of elastic It is very important to notice that Dalton makes use of this conception of small particles to explain purely physical experiments and operations. Although we know that during these years he was thinking much of "chemical combinations," yet we find that it was his observations on the weather which led him to the conception—a purely physical conception—of each chemically distinct gas as being built up of a vast number of small, equally heavy particles. A consideration of these papers by Dalton on the constitution of mixed gases shows us the method which he pursued in his investigations. "The progress of philosophical knowledge," he says, "is advanced by the discovery of new and important facts; but much more when these facts lead to the establishment of general laws." Dalton always strove to attain to general laws. The facts which he describes are frequently inaccurate; he was singularly deficient in manipulation, and he cannot claim a high place as a careful experimenter. He was however able to draw general conclusions of wide applicability. He seems sometimes to have stated a generalization in definite form before he had obtained any experimental verification of it. In the year 1802 Dalton conducted an examination of air from various localities, and concluded "This question I have duly considered, and though I am not yet able to satisfy myself completely, I am nearly persuaded that the circumstance depends upon the weight and number of the ultimate particles of the several gases, those whose particles are lightest and single being least absorbable, and the others more, accordingly as they increase in weight and complexity. An inquiry into the relative weights of the ultimate particles of bodies is a subject, as far as I know, entirely new. I have lately been prosecuting this inquiry with remarkable success. The principle cannot be entered upon in this paper; but I shall just subjoin the results, as far as they appear to be Here is the beginning of the atomic theory; and yet Dalton's strictly chemical experimental work lies in the future. The scope of the theory is defined in that sentence—"An inquiry into the relative weights of the ultimate particles of bodies." His paper on mixed gases is illustrated by a plate, In 1804 Dalton was invited to deliver a course of lectures in the Royal Institution of London, on heat, mixed gases and similar subjects. In these lectures he expounded his views on the constitution of gases, on absorption of gases by liquids, etc. These views drew much attention in this and other Fig. 2 Dalton's love of numerical calculations is noticeable in a trivial circumstance which he mentions in a letter from London to his brother. He tried to count the number of coaches which he met in going to the Friends' morning meeting: this he assures his brother he "effected with tolerable precision. The number was one hundred and four." During vacation time Dalton usually made a walking excursion in the Lake district. He was extremely This side of Dalton's nature was not often apparent. In him the quiet, hard-working student generally appeared prominently marked; but on the half-holiday which he allowed himself on each Thursday afternoon, in order to enjoy the society of a few friends and to engage in his favourite amusement of a game at bowls, he laid aside something of the quietness, regularity and decorum which usually characterized him. "When it came to his turn to bowl he threw his whole soul into the game,... and it was not a little amusing to spectators to see him running after the ball across the green, stooping down as if talking to it, and waving his hands from one side to the other exactly as he wished the line of the ball to be, and manifesting the most intense interest in its coming near to the point at which he aimed." From the year 1803-4 Dalton becomes more and more a worker in chemistry. The establishment We have now arrived at the time when Dalton's inquiry into the "relative weights of the ultimate particles of bodies" was in his opinion sufficiently advanced for presentation to the scientific world; but I think we shall do better to postpone our consideration of this great inquiry until we have completed our review of the chief events in the life of Dalton, other than this the greatest event of all. Dalton did not look for rewards—he desired only the just fame of one who sought for natural truths; but after the publication of the "New System" rewards began to come to him. In 1817 he was elected a corresponding member of the French Academy of Sciences. In 1822, when his fame as a philosophical chemist was fully established, Dalton visited Paris. This visit gave him great pleasure. He was constantly in the society of the great men who then so nobly represented the dignity of natural science in France; Laplace, Cuvier, Biot, Arago, Gay-Lussac, Milne-Edwards and others were his friends. For some time after this visit he was more vivacious and communicative than usual, and we are told by one Dalton was elected a Fellow of the Royal Society in 1822, and four years later he became the first recipient of one of the Royal Medals, then founded by the King (George IV.). In 1830 he was elected one of the eight foreign Associates of the French Academy, an honour which is generally regarded as the highest that can be bestowed on any man of science. Dalton was one of the original members of the British Association for the Advancement of Science, and he attended most of the meetings from the first held in York in 1831 to that held in Manchester two years before his death. At the Oxford meeting of 1832 he was created D.C.L. by the University, and two years later the University of Edinburgh honoured herself by enrolling his name on the list of her doctors of law. About this time some of Dalton's scientific friends, who considered his work of great national importance, endeavoured to obtain a pension for him from the civil list. At the meeting of the British Association held at Cambridge in 1833, the president, Professor Sedgwick, was able to announce that "His Majesty, willing to manifest his attachment to science, and his regard for a character like that of Dr. Dalton, had graciously conferred on him, out of the funds of the civil list, a substantial mark of his royal favour." The "substantial mark of royal favour," the announcement of which Dalton received "with his customary quietness and simplicity of manner," consisted of a pension of £150 per annum, which was increased three years later to £300. The second part of Volume I. of his "New System" was published by Dalton in 1810, and the second volume of the same work in 1827. In 1844 a paper by him was read before the British Association, in which he announced some important discoveries with regard to the water in crystallizable He was seized with paralysis in 1837, but recovered to a great extent; a second attack in 1844 however completely prostrated him. On the 16th of July in that year he made the last entry in his book of "Observations on the Weather"—"Little rain;" next morning he became insensible and quietly passed away. It is as the founder of the chemical atomic theory that Dalton must ever be remembered by all students of physical and chemical science. To the Greek philosophers Leucippus and Democritus (flourished about 440-400 b.c.) we owe the conception that "The bodies which we see and handle, which we can set in motion or leave at rest, which we can break in pieces and destroy, are composed of smaller bodies, which we cannot see or handle, which are always in motion, and which can neither be stopped, nor broken in pieces, nor in any way destroyed or deprived of the least of their properties" (Clerk Maxwell). The heavier among these small indivisible bodies or atoms were regarded as always moving downwards. By collisions between these and the lighter ascending atoms lateral movements arose. By virtue of the natural law (as they said) that things of like weight and shape must come to the same place, the atoms of the various elements came together; thus larger masses of matter were formed; these again This doctrine was extended by Epicurus (340-270 B.C.), whose teaching is preserved for us in the poem of Lucretius (95-52 B.C.), "De Rerum Natura;" he ascribed to the atoms the power of deviating from a straight line in their descending motion. On this hypothesis Epicurus built a general theory to explain all material and spiritual phenomena. The ceaseless change and decay in everything around them was doubtless one of the causes which led men to this conception of atoms as indivisible, indestructible substances which could never wear out and could never be changed. But even here rest could not be found; the mind was obliged to regard these atoms as always in motion. The dance of the dust-motes in the sunbeam was to Lucretius the result of the more complex motion whereby the atoms which compose that dust are agitated. In his dream as told by Tennyson— "A void was made in Nature: all her bonds Cracked: and I saw the flaring atom-streams And torrents of her myriad universe, Ruining along the illimitable inane, Fly on to clash together again, and make Another and another frame of things For ever." The central quest of the physicist, from the days of Democritus to the present time, has been to explain the conception of "atom"—to develop more clearly the observed properties of the things which are seen and which may be handled as dependent "The lucid interspace of world and world Where never creeps a cloud, or moves a wind, Nor ever falls the least white star of snow, Nor ever lowest roll of thunder moans, Nor sound of human sorrow mounts to mar Their sacred everlasting calm." To the modern student of science the idea of absolute rest appears unthinkable; but in the most recent outcome of the atomic theory—in the vortex atoms of Helmholtz and Thomson—he thinks he perceives the very "foundation stones of the material universe." Newton conceived the atom as a "solid, massy, hard, impenetrable, movable particle." To the mind of D. Bernoulli the pressure exerted by a gas on the walls of a vessel enclosing it was due to the constant bombardment of the walls by the atoms of which the gas consisted. Atomic motion was the leading idea in the explanation of heat given by Rumford and Davy, and now universally accepted; and, as we have seen, Dalton was himself accustomed to regard all But in the year 1802 or so, Dalton thought that by the study of chemical combinations it would be possible to determine the relative weights of atoms. Assume that any elementary gas is composed of small, indivisible, equally heavy parts; assume that the weight of an atom of one element is different from that of the atom of any other element; and, lastly, assume that when elements combine the atom of the compound so produced is built up of the atoms of the various elements. Make these assumptions, and it follows that the relative weights of two or more elements which combine together must represent the relative weights of the atoms of these elements. We know that the fixity of composition of chemical compounds had been established before this time, largely by the labours of Black and Lavoisier. Fixity of composition had however been called in question by Berthollet, who held that elements combine together in very varying quantities; that, in fact, in place of there being two or three, or a few definite compounds of, say, iron and oxygen, there exists a graduated series of such bodies; and that the amount of iron which combines with oxygen depends chiefly on such physical conditions as the temperature, the pressure, etc., under which the chemical action occurs. But by the date of the publication of the first part of Dalton's "New System," the long dispute between By pondering on the facts regarding chemical combinations which had been established by various workers previous to the year 1802, Dalton had In his paper on the properties of the gases constituting the atmosphere, read to the Manchester Society on November 12, 1802, he stated that one hundred measures of common air would combine with thirty-six measures of "nitrous gas" in a narrow tube to produce an oxide of nitrogen, but with seventy-two measures of the same gas in a wide vessel to produce another oxide of nitrogen. These facts, he says, "clearly point out the theory of the process: the elements of oxygen may combine with a certain portion of nitrous gas, or with twice that portion, but with no intermediate quantity." In the concluding paragraph of his paper on absorption of gases by liquids, read on October 21, 1803, we found (see p. 116) that he had got so far in his inquiry into the "relative weights of the ultimate particles of bodies" as to give a table of twenty-one such weights. About this time Dalton made analyses of two gaseous compounds of carbon—olefiant gas and carburetted hydrogen or marsh-gas. He found that both are compounds of carbon and hydrogen; that in one 4.3 parts by weight of carbon are combined with one part by weight of hydrogen, and in the other the same amount (4.3) of carbon is combined with two parts by weight of This was a striking confirmation of his views regarding combination in multiple proportions, which views followed as a necessary deduction from the atomic hypothesis. From this time he continued to develop and extend this hypothesis, and in the year 1808 he published his "New System of Chemical Philosophy." The first detailed account of the atomic theory was however given to the chemical world the year before Dalton's book appeared. During a conversation with Dalton in the autumn of 1804 Dr. Thomas Thomson learned the fundamental points of the new theory, and in the third edition of his "System of Chemistry," published in 1807, he gave an account of Dalton's views regarding the composition of bodies. In the same year a paper by Thomson appeared in the Philosophical Transactions, wherein it was experimentally proved that oxalic acid combines with strontia to form two distinct compounds, one of which contains twice as much oxalic acid as the other, the amount of strontia being the same in both. Analyses of the oxalates of potash, published about the same time by Wollaston, afforded another illustration of the law of multiple proportions, and drew the attention of chemists to Dalton's theory. But the new theory was opposed by several very eminent chemists, notably by Sir Humphry Davy. In the autumn of 1807 Wollaston, Thomson and Davy were present at the dinner of the Royal Society Club, at the Crown and Soon after this Wollaston succeeded in convincing Mr. Davis Gilbert (afterwards President of the Royal Society) of the justness of the atomic theory, and he in turn so placed the facts and the reasoning before Davy, that from this time he became a supporter of the new theory. In order that the atomic theory should be fruitful of results, it was now necessary that the values of the atomic weights of many elements should be carefully determined. Let us consider what knowledge must be acquired before the value to be assigned to the atomic weight of an element can be found. Hydrogen was the element chosen as a standard by Dalton. He assumed that the atom of hydrogen weighs 1; the atomic weight of any other element is therefore a number which tells how many times the atom of that element is heavier than the atom of hydrogen. Thus, when Dalton said the atomic weight of oxygen is 8, he meant that the atom of oxygen is eight times heavier than that of hydrogen. How was this number obtained? Accurate analyses of water show that in this liquid one part by weight of hydrogen is combined with eight parts by weight of oxygen; but (it is I conceive it to be one of the signal merits of Dalton that he so clearly lays down rules, the best which could be devised at his time, for determining the atomic weights of compounds, or, what is the same thing, for determining the number of elementary atoms in one atom of any compound. Considering compounds of two elements, he divides these into binary, ternary, quaternary, etc., according as the compound atom contains two, three, four, etc., atoms of the elements. He then proceeds thus— "The following general rules may be adopted as guides in all our investigations respecting chemical synthesis:— "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. "2nd. When two combinations are observed, they must be presumed to be a binary and a ternary. "3rd. When three combinations are obtained, we may expect one to be binary and the other two ternary. "4th. When four combinations are observed, we should expect one binary, two ternary, and one quaternary," etc. Only one compound of hydrogen and oxygen was then known; hence it was presumed to be a binary compound, i.e. a compound the smallest particle of which consisted of one atom of hydrogen In the second part of the "New System" Dalton, guided by these rules, determined experimentally the atomic weights of a great many substances; but this was not the kind of work suited to Dalton's genius. His analytical determinations were generally inaccurate; nevertheless, he clearly showed how the values of the atomic weights of elements ought to be established, and he obtained results sufficiently accurate to confirm his general theory. To make accurate determinations of the relative weights of elementary atoms was one of the tasks reserved for the great Swedish chemist Berzelius (see pp. 162-170). When we examine Dalton's rules we must confess that they appear somewhat arbitrary. He does not give reasons for his assertion that Or, even assuming that this must be justified by facts, does it follow that Dalton's interpretation of the atomic structure of the two oxides of carbon is necessarily correct? These oxides contain 6 of carbon + 8 of oxygen, and 6 of carbon + 16 of oxygen, respectively. Take the second, 6: 16 = 3: 8; assume this to be a binary compound of one atom of oxygen (weighing 8) with one atom of carbon (weighing 3), then the other will be a ternary compound containing one atom of oxygen (8) and two atoms of carbon (6). Hence it appears that Dalton's rules were too arbitrary, and that they were insufficient to determine with certainty the atomic weights of some of the elements. Nevertheless, without some such rules as those of Dalton, no great advances could have been made in applying the atomic theory to the facts of chemical combination; and Dalton's rules were undoubtedly founded on wide considerations. In the appendix to Volume II. of his "New System" he expressly states that before the number of atoms of two elements present in the When we find that Dalton applied the term "atom" to the small particles of compound bodies, we at once see that by atom he could not always mean "that which cannot be cut;" he simply meant the smallest particle of a substance which exhibits the properties of that substance. A mass of water vapour was conceived by Dalton as "like a mass of small shot." Each shot exhibited the characteristic chemical properties of water vapour; it differed from the large quantity of vapour only in mass; but if one of these little pieces of shot were divided—as Dalton, of course, knew it could be divided—smaller pieces of matter would be produced. But these would no longer be water; they would be new kinds of matter. They are called oxygen and hydrogen. As aids towards gaining a clear conception of the "atom" of a compound as a definite building, Dalton made diagrammatic representations of the hypothetical structures of some of these atoms: the following plate is copied from the "New System:"—A represents an atom of alum; B, an atom of nitrate of alumina; C, of barium chloride; Fig. 3. But I think if we consider this application of the term "atom" to elements and compounds alike, we shall see objections to it. When an atom of a compound is divided the smaller particles so produced are each very different in chemical properties from the atom which has just been divided. We may, if we choose, assume that the atom of an element could in like manner be divided, and that the products of this division would be different from the elementary atoms; but such a division of an elementary atom has not as a matter of fact been yet accomplished, unless we class among elements substances such as potash and soda, which for many years were universally regarded as elements, and rightly so regarded because they had not been decomposed. In Dalton's nomenclature then, the term "atom" is applied alike to a small particle with definite properties known to be divisible into smaller particles, each with properties different from those of the undivided particle, and to a small particle which, so far as our knowledge goes, cannot be divided into any particle smaller than or different from itself. Nevertheless, if the atomic theory was to be victorious, it was necessary that it should be applied to elements and compounds alike. Until a clear conception should be obtained, and expressed in accurate language, of the differences in structure of the ultimate particles of compounds and of elements, These two difficulties—(1) the difficulty of attaching to the term "atom" a precise meaning applicable to elements and compounds alike, and (2) the difficulty of determining the number of elementary atoms in the atom of a given compound, and hence of determining the relative weights of elementary atoms themselves—were for many years stumbling-blocks in the path of the upholders of the Daltonian theory. The very great difficulty of clearly comprehending the full meaning of Dalton's proposed theory becomes apparent when we learn that within three years from the publication of Part I. of the "New System," facts were made known by the French chemist Gay-Lussac, and the true interpretation of these facts was announced by the Italian chemist Avogadro, which facts and interpretation were sufficient to clear away both the difficulties I have just mentioned; but that nevertheless it is only within the last ten or fifteen years that the true meaning of the facts established by Gay-Lussac and the interpretation given by Avogadro have been generally recognized. In 1809 Gay-Lussac, in a memoir on the combination of gaseous bodies, proved that gases combine chemically in simple proportions by volume, and that the volume of the product always bears a simple relation to the volumes of the combining gases. Thus, he showed that two volumes In 1811 Avogadro distinguished between the ultimate particles of compounds and elements. Let a gaseous element, A, combine with another gaseous element, B, to form a gaseous compound, C; then Avogadro supposed that the little particles of A and the little particles of B (Dalton's atoms) split up, each into two or more smaller particles, and that these smaller particles then combine together to form particles of the compound C. The smaller particles produced by splitting a Daltonian elementary atom were regarded by Avogadro as all identical in properties, but these very small particles could not exist uncombined either with each other or with very small particles of some other element. When the atom of a compound is decomposed, Avogadro pictured this atom as splitting into smaller particles of two or three or more different kinds, according as the compound had contained two or three or different elements. To Avogadro's mental vision an elementary gas appeared as built up of a great many little particles, each exhibiting in miniature all the properties of A compound gas was pictured by Avogadro as also built up of small particles, each exhibiting in miniature the properties of the gas, and each remaining undecomposed when the gas was subjected only to physical actions; but when the gas was chemically decomposed, each little particle split, but the very small parts thus produced, being each a particle of an elementary substance, continued to exist, and could be recognized by the known properties of that element. To the smallest particle of any substance (elementary or compound) which exhibits the properties of that substance, and which cannot be split into parts without destroying these properties, we now give the name of molecule. A molecule is itself a structure. It is built up of parts; each of these parts we now call an atom. The molecule of a compound is, of course, composed of the atoms of the elements which form that compound. The molecule may contain two or three or more unlike atoms. The molecule of an element is The student of physics or chemistry now believes that, were a very small quantity of a gas (say ammonia) or a drop of a liquid (say water) magnified to something like the size of the earth, he should see before him a vast heap of particles of ammonia or of water, each exhibiting all the properties by the possession of which he now distinguishes ammonia or water from all other kinds of matter. He believes that he should see these particles in motion, each moving rapidly from place to place, sometimes knocking against another, sometimes traversing a considerable space without coming into collision with any other. But the student tries to penetrate yet further into the nature of things. To the vision of the chemist these particles of almost inconceivable minuteness are themselves built up of smaller particles. As there is an architecture of masses, so is there an architecture of molecules. Hydrogen and oxygen are mixed; the chemist sees the molecules of each in their never-ceasing dance moving here and there among the molecules of the other, yet each molecule retaining its identity; an electric spark is passed through the mixture, and almost instantaneously he sees Avogadro's hypothesis gave the chemist a definition of "molecule;" it also gave him a definition of "atom." It is evident that, however many atoms of a given element there may be in this or in that compound molecule, no compound of this element can exist containing less than a single atom of the element in question; therefore an atom of an element is the smallest quantity of that element in the molecule of any compound thereof. And so we have come back to the original hypothesis of Dalton; but we have extended and modified that hypothesis—we have distinguished two orders of small particles, the molecule (of a compound or of an element) and the atom (of an element). The combination of two or more elements is now regarded as being preceded by the decomposition of the molecules of these elements into atoms. We have defined molecule and we have defined atom, but before we can determine the relative weights of elementary atoms we must have a means of determining the relative weights of compound molecules. The old difficulty still stares us in the face—how can we find the number of elementary atoms in the molecule of a given compound? The same naturalist who enriched chemical science by the discovery of the molecule as distinct from the atom, placed in the hands of chemists the instrument for determining the relative weights of molecules, and thus also the relative weights of atoms. The great generalization, usually known as Avogadro's law, runs thus: "Equal volumes of gases measured at the same temperature and under the same pressure contain equal numbers of molecules." Gay-Lussac had concluded that "equal volumes of gases contain equal numbers of atoms;" but this conclusion was rejected, and rightly rejected by Dalton, who however at the same time refused to admit that there is a simple relation between the combining volumes of elements. The generalization of Avogadro has however stood the test of experiment, and is now accepted as one of the fundamental "laws" of chemical science. Like the atomic theory itself, Avogadro's law is an outcome of physical work and of physical reasoning. Of late years the great naturalists, Clausius, Helmholtz, Joule, Rankine, Clerk Maxwell and Thomson have developed the physical theory of molecules, and have shown that Avogadro's law may be deduced as a necessary consequence from a few simple physical assumptions. This law has thus been raised, from being a purely empirical generalization, to the rank of a deduction from a wide, yet simple physical theory. Now, if "equal volumes of gases contain equal But consider the combination of a gaseous element with hydrogen; let us take the case of hydrogen and chlorine, which unite to form gaseous hydrochloric acid, and let us determine the volumes of the uniting elements and the volume of the product. Here is a statement of the results: one volume of hydrogen combines with one volume of chlorine to form two volumes of hydrochloric acid. Assume any number of molecules we please in the one volume of hydrogen—say ten—there must be, by Avogadro's law, also ten molecules in the one volume of chlorine; but inasmuch as the volume of hydrochloric acid produced is double that of either the hydrogen or the chlorine which combined to form it, it follows, by the same law, that twenty molecules of hydrochloric acid have been formed by the union of ten molecules of hydrogen with ten molecules of chlorine. The necessary conclusion Therefore we conclude that the hydrogen molecule is composed of two atoms, and that the chlorine molecule is also composed of two atoms; and as hydrogen is to be our standard element, we say that if the atom of hydrogen weighs one, the molecule of the same element weighs two. It is now easy to find the molecular weight of any gas; it is only necessary to find how many times heavier the given gas is than hydrogen, the weight of the latter being taken as 2. Thus, oxygen is sixteen times heavier than hydrogen, but 1: 16 = 2: 32, therefore the molecule of oxygen is thirty-two times heavier than the molecule of hydrogen. Ammonia is eight and a half times heavier than hydrogen, but 1: 8-1/2 = 2: 17, therefore the molecule of ammonia is seventeen times heavier than the molecule of hydrogen. This is what we more concisely express by saying "the molecular weight of oxygen is 32," or "the molecular weight of ammonia is 17," etc., etc. Now, we wish to determine the atomic weight of oxygen; that is, we wish to find how many times the oxygen atom is heavier than the atom of hydrogen. We make use of Avogadro's law and of the definition of "atom" which has been deduced from it (see p. 142). We know that eight parts by weight of oxygen combine with one part by weight of hydrogen to form water; but we do not know whether the molecule of water contains one atom of each element, or two atoms of hydrogen and one atom of oxygen, or some other combination of these atoms (see p. 131). But by vaporizing water and weighing the gas so produced, we find that water vapour is nine times heavier than hydrogen: now, 1: 9 = 2: 18, therefore the molecular weight of water gas is 18. Analysis tells us that eighteen parts by weight of water gas contain sixteen parts of oxygen and two parts of hydrogen; that is to say, we now know that in the molecule of water gas there are two atoms of hydrogen combined with sixteen parts by weight of oxygen. We now proceed to analyze and determine the molecular weights of as many gaseous compounds of oxygen as we can obtain. The outcome of all is that we have as yet failed to obtain any such compound in the molecule of which there are less than sixteen parts by weight of oxygen. In some of these molecules there are sixteen, in some thirty-two, in some forty-eight, in some sixty-four parts by weight of oxygen, but in none is there less than sixteen parts by weight of this element. Therefore we conclude that the atomic weight of oxygen is 16, because this is the smallest amount, referred to hydrogen taken as 1, which has hitherto been found in the molecule of any compound of oxygen. The whole of the work done since the publication We have thus got a clearer conception of "atom" than was generally possessed by chemists in the days of Dalton, and this we have gained by introducing the further conception of "molecule" as that of a quantity of matter different from, and yet similar to, the atom. The task now before us will for the most part consist in tracing the further development of the fundamental conception of Dalton, the conception, viz., of each chemical substance as built up of small parts possessing all the properties, other than the mass, of the whole; and—what we also owe to Dalton—the application of this conception to explain the facts of chemical combination. The circumstances of Dalton's early life obliged him to trust largely to his own efforts for acquiring knowledge; and his determination not to accept facts at second hand but to acquire them for himself, is very marked throughout the whole of his life. In the preface to the second part of the "New System" We should not expect such a man as this to make any great use of books; one of his friends tells us that he heard him declare on a public occasion that he could carry his library on his back, and yet had not read half of the books which comprised it. The love of investigation which characterized Dalton when young would naturally be increased by this course of intellectual life. How strong this desire to examine everything for himself became, is amusingly illustrated by a story told by his medical adviser, Dr. Ransome. Once when Dalton was suffering from catarrh Dr. Ransome had prescribed a James's powder, and finding his patient much better next day, he congratulated himself and Dalton on the good effects of the medicine. "I do not well see how that can be," said Dalton, "as I kept the powder until I could have an opportunity of analyzing it." As Dalton grew older he became more than ever disinclined to place much trust in the results obtained by other naturalists, even when these men were acknowledged to be superior to himself in manipulative and experimental skill. Thus, as we have already learned, he could not be brought to allow the truth of Gay-Lussac's experimentally established law regarding gaseous combinations; he preferred to attribute Gay-Lussac's results to That Dalton did not rank high as an experimenter is evident from the many mistakes in matters of fact which are to be found in the second part of his "New System." A marked example of his inaccuracy in purely experimental work is to be found in the supposed proof given by him that charcoal, after being heated to redness, does not absorb gases. He strongly heated a quantity of charcoal, pulverized it, and placed it in a Florence flask, which was connected by means of a stopcock with a bladder filled with carbonic acid: after a week he found that the flask and its contents had not sensibly increased in weight, and he concluded that no carbonic acid had been absorbed by the charcoal. But no trustworthy result could be obtained from an experiment in which the charcoal, having been deprived of air by heating, was again allowed to absorb air by being pulverized in an open vessel, and was then placed in a flask filled with air, communication between the carbonic acid and the external air being prevented merely by a piece of bladder, a material which is easily permeated by gases. Dalton used a method which can only lead to notable results in natural science when employed by a really great thinker; he acquired a few facts, and then thought out the meaning of these. That the law of multiple proportions is simply a generalization of facts, and may be stated apart from the atomic theory, is now generally admitted. But in Dalton's mind this law seems to have arisen rather as a deduction from the theory of atoms than to have been gained as a generalization from experiments. He certainly always stated this law in the language of the atomic theory. In one of his walking excursions he explained his theory to a friend, and after expounding his views regarding atomic combinations, he said that the examples which he had given showed the necessary existence of the principle of multiple proportions: "Thou knowest it must be so, for no man can split an atom." We have seen that carburetted hydrogen was one of the compounds on the results of the analysis of which he built his atomic theory; yet we find him saying of the constitution of this compound that "no correct notion seems to have been formed till the atomic theory was introduced and applied in the investigation." When Dalton was meditating on the laws of chemical combination, a French chemist, M. Proust, published analyses of metallic oxides, which proved that when a metal forms two oxides the amount of metal in each is a fixed quantity—that there is a sudden jump, as it were, from one oxide to another. We are sometimes told that from these experiments Proust would have recognized the law of multiple proportions had his analyses only been more accurate; but we know that Dalton's analyses were very inaccurate, and yet he not only recognized the law of multiple proportions, but propounded and established the atomic theory. Something more than a correct system of keeping books and balancing accounts is wanted in natural science. Dalton's experimental results would be the despair of a systematic analyst, but from these Dalton's genius evolved that splendid theory which has done so much to advance the exact investigation of natural phenomena. Probably no greater contrast could be found between methods of work, both leading to the establishment of scientific (that is, accurate and precise) results, than that which exists between the method of Dalton and the method pursued by Priestley. Priestley commenced his experiments with no particular aim in view; sometimes he wanted to amuse himself, sometimes he thought he might light upon a discovery of importance, sometimes his curiosity incited him to experiment. When he When we ask how it was that Dalton acquired his great power of penetrating beneath the surface of things and finding general laws, we must attribute this power in part to the training which he gave himself in physical science. It was from a consideration of physical facts that he gained the conception of ultimate particles of definite weight. His method was essentially dynamical; that is, he pictured a gas as a mass of little particles, each of which acted on and was acted on by, other particles. The particles were not thrown together anyhow; definite forces existed between them. Each elementary or compound gas was pictured as a system of little particles, and the properties of that gas were regarded as dependent on the nature and arrangement of these particles. Such a conception as this could only be gained by a careful and profound thinker versed in the methods of physical and mathematical science. Thus we see that although Dalton appeared to gain his great chemical results by a method which we are not generally inclined to regard as the method To me it appears that Dalton was pre-eminently distinguished by the possession of imagination. He formed clear mental images of the phenomena which he studied, and these images he was able to combine and modify so that there resulted a new image containing in itself all the essential parts of each separate picture which he had previously formed. From his intense devotion to the pursuit of science the development of Dalton's general character appears to have been somewhat dwarfed. Although he possessed imagination, it was the imagination of a naturalist rather than that of a man of broad culture. Perhaps it was a want of broad sympathies which made him trust so implicitly in his own work and so readily distrust the work of others, and which moreover led him astray in so many of his purely experimental investigations. Dalton began his chemical work about six years after the death of Lavoisier. Unlike that great philosopher he cared nothing for political life. The friends in whose family he spent the greater part of his life in Manchester were never able |