Part 4

It has been pointed out by Judge Stallo, of Philadelphia, in his _Concepts of Physics_, that such a hypothesis as that of Dalton is no explanation; that a fact of nature, as, for example, the fact of simple and multiple proportions, is not _explained_ by being minified. Allowing the general truth of this statement, it is, nevertheless, undoubted that chemistry owes much to Dalton’s hypothesis—a lucky guess at first, it represents one of the fundamental truths of nature, although its form must be somewhat modified from that in which Dalton conceived it. Dalton’s work was first expounded by Thomas Thomson, professor at Glasgow, in his _System of Chemistry_, published in 1805; and subsequently in Dalton’s own _New System of Chemical Philosophy_, the three volumes of which were published in 1808, in 1810, and in 1827.

The determination of these “Constants of Nature” was at once followed out by many chemists, Thomson among the first. But chief among the chemists who have pursued this branch of work was Jacob Berzelius, a Swede, who devoted his long life (1779–1848) to the manufacture of compounds, and to the determination of their composition, or, as it is still termed, the determination of the “atomic weights”—more correctly, “equivalents”—of the elements of which they are composed. It is to him that we owe most of our analytical methods, for, prior to his time, there were few, if any, accurate analyses. Although Lavoisier had devised a method for the analysis of compounds of carbon, viz., by burning the organic compounds in an atmosphere of oxygen contained in a bell-jar over mercury, and measuring the volume of carbon dioxide produced, as well as that of the residual oxygen, Berzelius achieved the same results more accurately and more expeditiously by heating the substance, mixed with chlorate of potassium and sodium chloride, and then estimating the hydrogen as well as the carbon; this process was afterwards perfected by Liebig. Berzelius, however, was able to show that compounds of carbon, like those of other elements, were instances of combination in constant and in multiple proportions.

In 1815 two papers were published in the _Annals of Philosophy_ by Dr. Prout, which have had much influence on the progress of chemistry. They dealt with the figures which were being obtained by Thomson, Berzelius, and others, at that time supposed to represent the “atomic weights” of the elements. Prout’s hypothesis, based on only a few numbers, was that the atomic weights of all elements were multiples of that of hydrogen, taken as unity. There was much dispute regarding this assertion at the time, but as it was contradicted by Berzelius’s numbers, the balance of opinion was against it. But about the year 1840 Dumas discovered an error in the number (12.12) given by Berzelius as the atomic weight of carbon; and with his collaborator, Stas, undertook the redetermination of the atomic weights of the commoner elements—for example, carbon, oxygen, chlorine, and calcium. This line of research was subsequently pursued alone by Stas, whose name will always be remembered for the precision and accuracy of his experiments. At first Dumas and Stas inclined to the view that Prout’s hypothesis was a just one, but it was completely disproved by Stas’s subsequent work, as well as by that of numerous other observers. It is, nevertheless, curious that a much larger proportion of the atomic weights approximate to whole numbers than would be foretold by the doctrine of chances, and perhaps the last has not been heard of Prout’s hypothesis, although in its original crude form it is no longer worthy of credence.

One of the most noteworthy of the discoveries of the century was made by Gay-Lussac (1778–1850) in the year 1808. In conjunction with Alexander von Humboldt, Gay-Lussac had rediscovered about three years before what had previously been established by Cavendish—namely, that, as nearly as possible, two volumes of hydrogen combine with one volume of oxygen to form water, the gases having been measured at the same temperature and pressure. Humboldt suggested to Gay-Lussac that it would be well to investigate whether similar simple relations exist between the volumes of other gaseous substances when they combine with each other. This turned out to be the case; it appeared that almost exactly two volumes of carbonic oxide unite with one volume of oxygen to form carbon dioxide; that equal volumes of chlorine and hydrogen unite to form hydrochloric acid gas; that two volumes of ammonia gas consist of three volumes of hydrogen in union with one volume of nitrogen, and so on. From such facts, Gay-Lussac was led to make the statement that: The weights of equal volumes of both simple and compound gases, and therefore their densities, are proportional to their empirically found combining weights, or to rational multiples of the latter. Gay-Lussac recognized this discovery of his to be a support for the atomic theory; but it did not accord with many of the then received atomic weights. The assumption that equal volumes of gases contain equal numbers of particles, or, as they were termed by him, _molécules intégrantes_, was made in 1811 by Avogadro, professor of physics at Turin (1776–1856). This theory, which has proved of the utmost importance to the sciences both of physics and of chemistry, had no doubt occurred to Gay-Lussac, and had been rejected by him for the following reasons: A certain volume of hydrogen, say one cubic inch, may be supposed to contain an equal number of particles (atoms) as an equal volume of chlorine. Now these two gases unite in equal volumes. The deduction appears so far quite legitimate that one atom of hydrogen has combined with one atom of chlorine. But the resulting gas occupies two cubic inches, and must therefore contain the same number of particles of hydrogen chloride, the compound of the two elements, as one cubic inch originally contained of hydrogen, or of chlorine. Thus we have two cubic inches containing, of uncombined gases, twice as many particles as is contained in that volume, after combination. Avogadro’s hypothesis solved the difficulty. By premising two different orders of particles, now termed _atoms_ and _molecules_, the solution was plain. According to him, each particle, or molecule, of hydrogen is a complex, and contains two atoms; the same is the case with chlorine. When these gases combine, or rather _react_, to form hydrogen chloride, the phenomenon is one of a change of partners; the molecule, the double atom, of hydrogen splits; the same is the case with the molecule of chlorine; and each liberated atom of hydrogen unites with a liberated atom of chlorine, forming a compound, hydrogen chloride, which equally consists of a molecule, or double atom. Thus two cubic inches of hydrogen chloride consist of a definite number of molecules, equal in number to those contained in a cubic inch of hydrogen, plus those contained in a cubic inch of chlorine. The case is precisely similar, if other compounds of gases be considered.

Berzelius was at first inclined to adopt this theory, and indeed went so far as to change many of his atomic weights to make them fit it. But later he somewhat withdrew from his position, for it appeared to him that it was hazardous to extend to liquids and solids a theory which could be held only of gases. Avogadro’s suggestion, therefore, rested in abeyance until the publication, in 1858, by Cannizzaro, now professor of chemistry in Rome, of an essay in which all the arguments in favor of the hypothesis were collected and stated in a masterly manner. It will be advisable to revert to this hypothesis at a later point, and to consider other guides for the determination of atomic weights.

In 1819, Dulong (1785–1838), director of the Ecole Polytechnique at Paris, and Petit (1791–1820), professor of physics there, made the discovery that equal amounts of heat are required to raise equally the temperature of solid and liquid elements, provided quantities are taken proportional to their atomic weights. Thus, to raise the temperature of 56 grammes of iron through one degree requires approximately the same amount of heat as is required to raise through one degree 32 grammes of sulphur, 63.5 grammes of copper, and so on; these numbers representing the atomic weights of the elements named. In other words, _equal numbers of atoms have equal capacity for heat_. The number of heat units, or calories (one calory is the amount of heat required to raise the temperature of 1 gramme of water through 1° C.), which is necessary to raise the atomic weight expressed in grammes of any solid or liquid element through 1° C. is approximately 6.2; it varies between 5.7 and 6.6 in actual part. This affords a means of determining the true value of the atomic weight of an element, as the following example will show: The analysis of the only compound of zinc and chlorine shows that it contains 47.49 per cent. of zinc and 52.16 per cent. of chlorine. Now one grain of hydrogen combines with 35.5 grains of chlorine to form 36.5 grains of hydrogen chloride; and, as already remarked, one volume of hydrogen and one volume of chlorine combine, forming two volumes of hydrogen chloride. Applying Avogadro’s hypothesis, one molecule of hydrogen and one molecule of chlorine react to yield two molecules of hydrogen chloride; and as each molecule is supposed to consist in this case of two atoms, hydrogen chloride consists of one atom of each of its constituent elements. The amount of that element, therefore, which combines with 35.5 grains of chlorine may give the numerical value of the atomic weight of the element, if the compound contains one atom of each element; in that case the formula of the above compound would be zinc, and the atomic weight of zinc, 32.7; but if the formula is ZuCl3, the atomic weight of zinc would be 32.7 × 2; if ZuCl3, 32.7 × 3, and so on. The specific heat of metallic zinc enables this question to be solved. For it has been found, experimentally, to be about 0.095; and 6.2 ÷ 0.095 = 65.2, a close approximation to 32.7 × 2 = 65.4. The conclusion is therefore drawn that zinc chloride is composed of one atom of zinc in combination with two atoms of chlorine, that the atomic weight of zinc is 65.4, and that the molecular weight of zinc chloride is 65.4 + (35.5 × 2) = 136.4. Inasmuch as the relative weight of a molecule of hydrogen is 2 (that of an atom being 1), zinc chloride in the gaseous state should be 136.4 ÷ 2 = 68.2 times that of hydrogen, measured at the same temperature and pressure. This has been found, experimentally, to be the case.

The methods of determining the vapor densities, or relative weights of vapors, are three in number; the first method, due to Dumas (1827), consists in vaporizing the substance in question in a bulb of glass or of porcelain, at a known temperature, closing the bulb while still hot, and weighing it after it is cold. Knowing the capacity of the bulb, the weight of hydrogen necessary to fill it at the desired temperature can be calculated, and the density of the vapor thus arrived at. A second method was devised by Gay-Lussac and perfected by A. W. Hofmann (1868); and a third, preferable for its simplicity and ease of execution, is due to Victor Meyer (1881).

In 1858, as already remarked, Cannizzaro showed the connection between these known facts, and for the first time attention was called to the true atomic weights, which were, up to that time, confused with equivalents, or weights of elements required to replace one unit weight of hydrogen. These were generally regarded as atomic weights by Dalton and his contemporaries.

Some exceptions had been observed to the law of Dulong and Petit, viz., beryllium, or glucinium, an element occurring in emeralds; boron, of which borax is a compound; silicon, the component of quartz and flint, and carbon. It was found by Weber that at high temperatures the specific heats of these elements are higher, and the atomic heats approximate to the number of 6.2; but this behavior is not peculiar to these elements, for it appears that the specific heat of all elements increases with rise of temperature.

A certain number of exceptions have also been noticed to the law of Gay-Lussac, which may be formulated: the molecular weight of a compound in a gaseous state is twice its density referred to hydrogen. Thus equal volumes of ammonia and hydrogen chloride unite to form ammonium chloride. It was to be expected that the density should be half the molecular weight, thus:

NH3 + HCl = NH4Cl; and 53.5 ÷ 2 = 26.75 = density. (14+3) (1+35.5) 53.5

But the density actually found is only half that number, viz., 13.37; and for long this and similar cases were supposed to be exceptions to the law of Gay-Lussac, viz., that equal volumes of gases at the same pressure expand equally for equal rise of temperature. In other instances the gradual decrease in density with rise of temperature can be followed, as with chloral hydrate, the products of which are chloral and water.

It was recognized by St. Claire Deville (1857) that the decrease in density of such mixtures of gases was due, not to their being exceptions to Avogadro’s law, but to the gradual decomposition of the compound body with rise of temperature. To this gradual decomposition he gave the name _dissociation_. This conception has proved of the utmost importance to the science, as will be seen in the sequel. To take the above instance of ammonium chloride, its abnormal density is due to its dissociation into ammonia and hydrogen chloride; and the gas which is obtained on raising its temperature consists, not of gaseous ammonium chloride, but of a mixture of ammonia and hydrogen chloride, which, as is easily seen, occupy, when separate, twice the volume that would be occupied by the gaseous compound. Of recent years it has been shown by Brereton Baker that, if perfectly free from moisture, ammonium chloride gasifies as such, and that its density in the state of vapor is, in fact, 26.75.

The molecular complexity of gases has thus gradually become comprehended, and the truth of Avogadro’s law has gained acceptance. And as a means of picturing the behavior of gaseous molecules, the “Kinetic Theory of Gases” has been devised by Joule, Clausius, Maxwell, Thomson (Lord Kelvin), and others. On the assumption that the pressure of a gas on the walls of the vessel which contains it is due to the continued impacts of its molecules, and that the temperature of a gas is represented by the product of the mass of the molecules, or the square of their velocity, it has been possible to offer a mechanical explanation of Boyle’s law, that at constant temperature the volume of a gas diminishes in proportion as the pressure increases; of Gay-Lussac’s law, that all gases expand equally for equal rise of temperature, provided pressure is kept constant; the condition being that equal volumes of gases contain equal numbers of molecules. A striking support is lent to this chain of reasoning by the facts discovered by Thomas Graham (1805–1869), professor at University College, London, and subsequently master of the Royal Mint. Graham discovered that the rate of diffusion of gases into each other is inversely as the square roots of their densities. For instance, the density of hydrogen being taken as unity, that of oxygen is sixteen times as great; if a vessel containing hydrogen be made to communicate with one containing oxygen, the hydrogen will pass into the oxygen and mix with it; and, conversely, the oxygen will pass into the hydrogen vessel. This is due to the intrinsic motion of the molecule of each gas. And Graham found, experimentally, that for each volume of oxygen which enters the hydrogen vessel four volumes of hydrogen will enter the oxygen vessel. Now, 4 = √16; and as these masses are relatively 1 and 16, and their temperatures are equal, the square of their velocities are respectively 1 and 16.

The question of the molecular complexity of gases being thus disposed of, it remains to be considered what are the relative complexity of liquid molecules. The answer is indicated by a study of the capillary phenomena of liquids, one method of measuring which is the height of their ascent in narrow or capillary tubes. We shall not enter here into detail as to the method and arguments necessary; suffice it to say that the Hungarian physicist Eötvös was the first to indicate the direction of research, and that Ramsay and Shields succeeded in proving that the complexity of the molecules of most liquids is not greater than that of the gases which they form on being vaporized; and also that certain liquids, _e.g._, water, the alcohols, and other liquids, are more or less “associated,” _i.e._, their molecules occur in couplices of two, three, four, or more, and as the temperature is raised the complexity of molecular structure diminishes.

As regards the molecular complexity of solids, nothing definite is known, and, moreover, there appears to be no method capable of revealing it.

While the researches of which a short account has now been given have led to knowledge regarding the nature of molecules, the structure of the molecule has excited interest since the early years of the century, and its investigation has led to important results. The fact of the decomposition of acidified water by an electric current, discovered by Nicholson and Carlisle, and of salts into “bases” and “acids” by Berzelius and Hisinger in 1803, led to the belief that a close connection exists between electric energy, or, as it was then termed, “electric force,” and the affinity which holds the constituents of chemical compounds in combination. In 1807 Davy propounded the theory that all compounds consist of two portions, one electro-positive and the other electro-negative. This idea was the result of experiments on the behavior of substances, such, for example, as copper and sulphur—if portions of these elements be insulated and then brought into contact they become oppositely electrified. The degree of electrification is intensified by rise of temperature until, when combination ensues, the electrification vanishes. Combination, therefore, according to Davy, is concurrent with the equalization of potentials. In 1812 Berzelius brought forward an electro-chemical theory which for the following twenty years was generally accepted. His primary assumption was that the atoms of elements, or, in certain cases, groups of atoms, are themselves electrified; that each atom, or group of atoms, possesses two poles, one positive, the other negative; that the electrification of one of these poles predominates over that of the other, so that the atom or group is itself, as a whole, electro-positive, or electro-negative; that combination ensued between such oppositely electrified bodies by the neutralization, partial or complete, of their electric charges; and, lastly, that the polarity of an element or group could be determined by noting whether the element or group separated at the positive or at the negative pole of the galvanic battery, or electrolysis. For Berzelius, oxygen was the most electro-negative and potassium the most electro-positive of the elements, the bridge between the “non-metals” and the “metals” being hydrogen, which, with nitrogen, forms a basic, or electro-positive, group, while with chlorine, etc., it forms electro-negative groups. The fact that an electric current splits compounds in solution into two portions led Berzelius to devise his “dualistic” system, which involved the assumption that all compounds consist of two portions, one electro-positive, the other electro-negative. Thus sulphate of magnesium and potassium was to be regarded as composed of electro-positive potassium sulphate in combination with electro-negative magnesium sulphate; the former in its turn consisted of electro-negative sulphur trioxide (SO3) in combination with electro-positive oxide of potassium (K2O); while each of these proximate constituents of potassium sulphate were themselves composed of the electro-negative oxygen in combination with electro-positive sulphur, or potassium. On contrasting sulphur with potassium, however, the former was considered more electro-negative than the latter; so that the group SO3 as a whole was electro-negative, while K2O was electro-positive. The symbols given above, which are still in universal use, were also devised by Berzelius for the purpose of illustrating and emphasizing his views. These views, however, met with little acceptance at the time in England.