Heroes of Science Part 9

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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. a.n.a.lyses of the oxalates of potash, published about the same time by Wollaston, afforded another ill.u.s.tration 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 a.s.signed to the atomic weight of an element can be found.

Hydrogen was the element chosen as a standard by Dalton. He a.s.sumed 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 a.n.a.lyses 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 a.s.sumed that the atom, or smallest particle, of water is built up of one atom of hydrogen and one atom of oxygen. Let it be a.s.sumed 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 a.s.sumed 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 a.s.sumptions will equally satisfy the figures obtained by a.n.a.lyzing 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 a.s.sumptions 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 const.i.tute 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 a.n.a.lytical 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 a.s.sertion 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 a.s.suming 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; a.s.sume 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 ma.s.s of water vapour was conceived by Dalton as "like a ma.s.s of small shot." Each shot exhibited the characteristic chemical properties of water vapour; it differed from the large quant.i.ty of vapour only in ma.s.s; 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, pota.s.sium carbonate; I, of potash; and K, an atom of soda.

[Ill.u.s.tration: 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, a.s.sume 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 cla.s.s 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, it was perhaps better to apply the term "atom" to both alike.

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 of hydrogen combine with one volume of oxygen to form two volumes of water vapour; that one volume of nitrogen combines with three volumes of hydrogen to form two volumes of ammonia gas, and so on. Now, as elements combine atom with atom, the weights of these combining volumes of elements must represent the relative weights of the atoms of the same elements.

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 the gas. The gas might be heated, or cooled, or otherwise physically altered, but each of the little particles remained intact; the moment however that this gas was mixed with another on which it could chemically react, these little particles split into smaller parts, but as the smaller parts so produced could not exist in this state, they seized hold of the corresponding very small parts of the other gas, and thus a particle of a compound gas was produced.

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 composed of the atoms of that element, and all of these atoms are supposed to be alike. We cannot get hold of elementary atoms and examine them, but we have a large ma.s.s of evidence in favour of the view which regards the molecule of an element as composed of parts each weighing less than the molecule itself.

The student of physics or chemistry now believes that, were a very small quant.i.ty 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 s.p.a.ce 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 ma.s.ses, 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 ident.i.ty; an electric spark is pa.s.sed through the mixture, and almost instantaneously he sees each hydrogen molecule split into two parts, and each oxygen molecule split into two parts, and then he sees these parts of molecules, these atoms, combine, a pair of hydrogen atoms with an atom of oxygen, to form compound molecules of water.

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 quant.i.ty 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 a.s.sumptions. 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 numbers of molecules," it follows that the ratio of the densities of any two gases must also be the ratio of the weights of the molecules which const.i.tute these gases. Thus, a given volume of water vapour weighs nine times more than an equal volume of hydrogen; therefore the molecule of gaseous water is nine times heavier than the molecule of hydrogen. One has therefore only to adopt a standard of reference for molecular weights, and Avogadro's law gives the means of determining the number of times any gaseous molecule is heavier than that of the standard molecule.

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. a.s.sume 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 is that each hydrogen molecule and each chlorine molecule has split into two parts, and that each half-molecule (or atom) of hydrogen has combined with one half-molecule (or atom) of chlorine, to produce one compound molecule of hydrochloric acid.

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. a.n.a.lysis 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 a.n.a.lyze 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. .h.i.therto been found in the molecule of any compound of oxygen.

The whole of the work done since the publication of Dalton's "New System"

has emphasized the importance of that chemist's remark, that no safe conclusion can be drawn as to the value of the atomic weight of an element except from a consideration of many compounds of that with other elements.

Heroes of Science Part 9

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