Heroes of Science: Chemists

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 marks the beginning of this period, it seems better that we should have a clear conception of what was done by this chemist before proceeding to consider the advances made by his contemporaries and successors.

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 whereon he announced that he had opened a school for youth of both sexes; also that "paper, pens and ink" were sold within. The boy-teacher had little authority over his pupils, who challenged their master to fight in the graveyard, and broke the windows of the room into which they had been locked till their tasks should be learned.

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 problems in this journal, and also in the Ladies' Diary, Dalton sometimes ventured into the wider fields of mental phenomena. It seems strange to read that, even at the age of twenty-six, Dalton should occupy his leisure time composing answers to such queries as these:—

"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 every plant within twenty miles of Kendal." To the friendship of this remarkable man Dalton owed much; with his help he acquired a fair knowledge of the classical languages, and he it was who set Dalton the example of keeping a regular record of weather observations.

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 and Philosophical Society of Manchester in the year 1794; and from the time of his retiring from the tutorship of Manchester New College till the close of his life he spent a great part of his time in a room in the society's house in George Street, in studying and teaching. The fifty years thus spent are marked by few outward events. The history of Dalton's life from this time is the history of the development of his intellect, and the record of his scientific discoveries.

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 occasional study of botany obliged me to attend more to colour than before. With respect to colours that were white, yellow, or green, I readily assented to the appropriate term; blue, purple, pink and crimson appeared rather less distinguishable, being, according to my idea, all referable to blue. I have often seriously asked a person whether a flower was blue or pink, but was generally considered to be in jest." Dalton's colour-blindness was amusingly illustrated at a later time, when having been created D.C.L. by the University of Oxford he continued to wear the red robes of his degree for some days; and when his attention was drawn to the somewhat strange phenomenon, even in a university town, of an elderly gentleman in the dress of a Quaker perambulating the town day after day in a scarlet robe, he remarked that to him the gown appeared to be of the same colour as the green trees.

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 pressures of various gases caused by increasing or decreasing temperature, and then proceeded to discuss the relations which exist between the volumes of gases and the temperature at which these volumes are measured. He concluded that "all elastic fluids" under the same pressure expand equally by heat: and he adds the very important remark, "It seems, therefore, that general laws respecting the absolute quantity and the nature of heat are more likely to be derived from the study of elastic fluids than of other substances"—a remark the profound truth of which has been emphasized by each step in the advances made in our conception of the nature of heat since the time of Dalton.

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 fluids, of these particles as repelling each other, etc. In his "New System" he says, "A vessel full of any pure elastic fluid presents to the imagination a picture like one full of small shot."

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 that one hundred volumes of air are composed of twenty-one volumes of oxygen and seventy-nine volumes of nitrogen. This appears to have been his first piece of purely chemical work. But in the next year he again returns to physical phenomena. In the paper already referred to, on the absorption of gases by water and other liquids, published in this year, he had stated that "All gases that enter into water and other liquids by means of pressure, and are wholly disengaged again by the removal of that pressure, are mechanically mixed with the liquid, and not chemically combined with it." But if this be so, why, he asked, does not water mechanically dissolve the same bulk of every kind of gas? The answer which he gives to this question is found at the close of the paper; to the student of chemistry it is very important:—

"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 ascertained by my experiments." Then follows a "Table of the relative weights of the ultimate particles of gaseous and other bodies." The following numbers, among others, are given:—

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,[7] which shows how vividly Dalton at this time pictured to himself a quantity of gas as composed of many little particles, and how clearly he recognized the necessity of regarding all the particles of each elementary gas as alike, but as differing from those of every other elementary gas.

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 countries. "They are busy with them," he writes in 1804, "at London, Edinburgh, Paris and in various parts of Germany, some maintaining one side and some another. The truth will surely out at last."

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 fond of mountain scenery, but generally combined the pursuit of science with that of pleasure; he carried his meteorological instruments with him, determined the dew-point at various altitudes, and measured mountain heights by the aid of his barometer. Sometimes however he refused to have anything to do with science. A companion in one of these excursions says that he was "like a schoolboy enjoying a holiday, mocking the cuckoos, putting up and chasing the hares, stopping from time to time to point out some beautiful view, or loitering to chat with passing pedestrians."

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 of the atomic theory now engaged most of his time and attention. The results of his investigation of "the primary laws which seem to obtain in regard to heat and to chemical combinations" appeared in his "New System of Chemical Philosophy," Part I. of which, "On Heat, on the Constitution of Bodies and on Chemical Synthesis," was published in 1808.

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 who lived in the same house as he, "We frequently bantered him with having become half a Frenchman." Dalton especially valued the friendship of Clementine Cuvier, daughter of the great naturalist, with whom he became acquainted during his visit to Paris. All through life he greatly delighted in the society of cultivated women, and his warmest friendships were with gentlewomen. At one time, shortly after going to Manchester, he was much taken by a widow lady who combined great personal charms with considerable mental culture. "During my captivity," he writes to a friend, "which lasted about a week, I lost my appetite, and had other symptoms of bondage about me, as incoherent discourse, etc., but have now happily regained my freedom." The society of men who like himself were actively engaged in the investigation of natural science was also a source of much pleasure to Dalton. Such men used to visit him in Manchester, so that in the house of the Rev. Mr. Johns, in whose family he lived, "there were found from time to time some of the greatest philosophers in Europe."

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 salts, and thus brought a new class of facts within the range of the atomic theory.

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 coalesced, and so finally worlds came into existence.

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—

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 on the properties of those things which cannot be seen, but which yet exist. For two thousand years he has been trying to penetrate beneath the ever-changing appearances of Nature, and to find some surer resting-place whence he may survey these shifting pictures as they pass before his mental vision. The older atomists thought to find this resting-place, not in the atoms themselves, but in the wide spaces which they supposed to exist between the worlds:—

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 "elastic fluids" (i.e. gases) as consisting of vast numbers of atoms.

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 Berthollet and Proust regarding fixity of composition of compounds had nearly closed in favour of the latter chemist, who strongly upheld the affirmative side of the argument. But if Dalton's assumptions are correct, it is evident that when two elements form more than one compound, the quantity of element A in one of these must be a simple multiple of the quantity in the other of these compounds; because there must be a greater number of atoms of element A in the atom of one compound than in that of the other compound, and an elementary atom is assumed to be indivisible. Hence it follows that if one element be taken as a standard, it must be possible to affix to any other element a certain number which shall express the smallest quantity of that element which combines with one part by weight of the standard element; and this number shall also represent how many times the atom of the given element is heavier than the atom of the standard element, the weight of which has been taken to be one. If this element forms two compounds with the standard element, the amount of this element in the second compound must be expressed by a simple multiple of the number assigned to this element, because it is not possible, according to the fundamental assumptions of the theory, to form a compound by the combination of fractions of elementary atoms.

By pondering on the facts regarding chemical combinations which had been established by various workers previous to the year 1802, Dalton had apparently come to such conclusions as those now indicated.

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 hydrogen.[8]

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 Anchor, in the Strand. After dinner, these three chemists discussed the new theory for an hour and a half, Wollaston and Thomson trying to convince Davy of the truth of Dalton's theory; but "so far from being convinced, he went away, if possible, more prejudiced against it than ever."

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 said) as the atom of hydrogen weighs 1, the atom of oxygen must weigh 8. In drawing this conclusion it is assumed that the atom, or smallest particle, of water is built up of one atom of hydrogen and one atom of oxygen. Let it be assumed that the atom of water contains two atoms of hydrogen and one of oxygen, then the latter atom must weigh sixteen times as much as each atom of hydrogen; let it be assumed that three atoms of hydrogen combine with one atom of oxygen to form an atom of water, then the weight of the oxygen atom must be twenty-four times that of the hydrogen atom. Any one of these assumptions will equally satisfy the figures obtained by analyzing water (1: 8 = 2: 16 = 3: 24). Now, had we any method whereby we could determine how many times an atom of water is heavier than an atom of hydrogen we should be able to determine which of the foregoing assumptions is correct, and therefore to determine the atomic weight of oxygen. Hence, before the atomic weight of an element can be determined, there must be found some method for determining the atomic weights of compounds of that element. Unless this can be done the atomic theory is of little avail in chemistry.

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. In his "New System" he says that he wishes to show the importance of ascertaining "the relative weights of the ultimate particles both of simple and compound bodies, the number of simple elementary particles which constitute one compound particle, and the number of less compound particles which enter into the formation of one more compound particle."

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 and one atom of oxygen; and hence, from the data already given on page 130, it followed that the atomic weight of oxygen was 8. Two compounds of carbon and oxygen were known, each containing six parts by weight of carbon, in one case united with eight, and in the other case with sixteen parts by weight of oxygen. From Dalton's rules one of these was a binary, and the other a ternary compound; but as the atomic weight of oxygen had already been determined to be 8, that compound of carbon and oxygen containing eight of oxygen combined with six of carbon was decided to be binary, and that containing sixteen of oxygen (i.e. two atoms) to be ternary; and hence the atomic weight of carbon was determined to be 6.

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 "when only one combination of two bodies can be obtained, it must be presumed to be a binary one." Why may it not be ternary or quaternary? Why must the atom of water be built up of one atom of hydrogen combined with one atom of oxygen? Or, when two compounds are known containing the same pair of elements, why must one be binary and the other ternary?

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 atom of a compound can be determined, it is necessary that many combinations should be examined, not only of these elements with each other, but also of each of these with other elements; and he tells us that to gather together facts bearing on this general question of chemical synthesis was the object of his work from the time of the promulgation of the atomic theory.

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; D, of barium nitrate; E, of calcium chloride; F calcium nitrate; G, of calcium sulphate; H, potassium carbonate; I, of potash; and K, an atom of soda.