Part 31

No important practical application has been found for any of these earthy oxides, except that about one per cent of cerium oxide is mixed with thorium oxide in incandescent gas-mantles in order to obtain greatly increased luminosity.

_The Inactive Gases._—As long ago as 1785, Cavendish, that remarkable Englishman who first weighed the world and first discovered the composition of water, actually obtained a little argon in a pure condition by sparking atmospheric nitrogen with oxygen converting it into nitric acid (another discovery of his) and absorbing the excess of oxygen. The volume of this residual gas as estimated by him corresponds very closely to the volume of argon in the atmosphere, as now known.

It was more than a century later, in 1894, that Rayleigh and Ramsay discovered argon in the air. Lord Rayleigh had found that atmospheric nitrogen was about one-half per cent heavier than chemical nitrogen, a fact which led to the investigation. It was only necessary to repeat Cavendish’s experiment on a large scale, or to absorb oxygen with hot copper and nitrogen with hot magnesium, in order to obtain argon. The gas attracted much attention, both on account of having but a single atom in its molecule, and particularly because it failed to enter into chemical combination of any kind. This gas has been used of late for filling the bulbs of incandescent electric lamps in cases where a gas pressure without chemical action is desired.

In 1890 and 1891, Hillebrand published in the Journal (=40=, 384, 1890: =42=, 390, 1891) a series of analyses of the mineral uraninite and reported in some samples of the mineral as much as 2·5 per cent of an inactive gas. Hillebrand examined the gas spectroscopically but, just missing an important discovery, he detected only the spectrum lines of nitrogen. Ramsay, in searching for argon in some sort of natural combination, and doubtless remembering Hillebrand’s work, heated some cleveite, a variety of uraninite, and obtained, not argon, but a new gas. This gave a yellow spectrum-line corresponding to a line previously observed in the light of the sun’s corona and attributed to an element in the sun called helium. Helium, therefore, in 1895 had been found on the earth. This gas is a constant constituent of uranium minerals, as it is produced by the breaking down of radioactive elements. It has been found in very small quantity in the atmosphere, and is the most difficult of all known gases to liquefy, as its boiling point, as shown by Onnes in 1908, is only 4° above the absolute zero. It has not yet been solidified.

In 1898 Ramsay and Travers, by the use of ingenious methods of fractional distillation and absorption by charcoal, obtained three other much rarer inactive gases from the atmosphere which they called neon, krypton and xenon.

The inactive gases are all colorless, and as they form no chemical compounds they are characterized by their densities, which give their atomic weights, by their boiling points, and by their characteristic Geissler-tube spectra.

The gaseous radium emanation, or niton, belongs also to the inactive group, and it was also collected and studied by Ramsay who was compelled to work with only 0·0001 cc. of it, as the volume obtained by heating radium salts is very small. It is an evanescent element, disappearing within a few days on account of radioactive disintegration. Meanwhile it glows brilliantly when liquefied and cooled to the temperature of liquid air. It has an atomic weight of 222, four units below that of radium, and the difference is considered as due to the loss by radium of an atom of helium in passing into the emanation.

_The Radioactive Elements._—The discovery of radium in 1898 by Madame Curie, and the study of that and other radioactive elements has produced a profound effect upon chemical theory. It was found that the two elements of the highest atomic weights, uranium and thorium, are always spontaneously decomposing into other elements at a fixed rate of speed which can be controlled by no artificial means, and that the elements resulting from these decompositions likewise undergo spontaneous changes into still other elements at greatly varying rates of speed, forming in each case a remarkable series of temporary elements. These transformations are accompanied by the emission at enormous velocities of three kinds of rays, one variety of which has been shown to consist of helium atoms. The greater number of the elements formed in these transformations have not as yet been obtained in a pure condition, and they are known only in connection with their radioactivity, volatility, etc.; but radium and niton, two of these products, have been obtained in a pure condition, so that their atomic weights and their places in the periodic system have been fixed.

We owe much of our knowledge of the radioactive transformations to the researches of Rutherford and of Soddy, and of their co-workers, but one of the important products of the transformation of uranium, an element which he called ionium, was characterized by Boltwood of Yale (=25=, 365, 1908).

Radium and niton, apart from their radioactive properties, resemble barium and the inert gases of the atmosphere, respectively. The rates at which their progenitors produce them, and the rates at which they themselves decompose, bring about a state of equilibrium after a time. Therefore a given amount of uranium, which decomposes exceedingly slowly, can yield even after thousands of years only a very small proportional quantity of undecomposed radium, one-half of which disappears in about 2500 years, because the amount decomposed must eventually be equal to the amount produced. The first conclusive evidence that radium is a product of the decomposition of uranium was given by Boltwood in the Journal (=18=, 97, 1904). He found that all uranium minerals contain radium; and the amount of radium present is always proportional to the amount of uranium, which shows the genetic relation between the two.

In the case of niton, which is produced by radium, and is called also the radium emanation, the rate of decay is rapid, so that if the gas is expelled from radium by heating, equilibrium is reached after a few days, with the accumulation of the largest possible amount of niton.

The conclusion has been reached by Rutherford and others that the final product besides helium, in the radioactive transformations, is lead, or at least an element or elements resembling lead to such a degree that no separation of them by chemical means is possible. Atomic weight determinations by Richards and others have shown that specimens of lead found in radioactive minerals give distinctly different atomic weights from that of ordinary lead. This fact has led to the view that possibly the atoms of the elements are not all of the same weight, but vary within certain limits—a view that is contrary to previous conclusions derived from the uniformity in atomic weights obtained with material from many different sources.

The results of the investigations upon radioactivity have led to modified views in regard to the stability of the elements in general. There has been little or no proof obtained that any artificial transmutation of the elements is possible, but the spontaneous transformation of the radioactive elements brings forward the possibility that other elements are changing imperceptibly, and that a state of evolution exists among them. All of the radioactive changes that we know proceed from higher to lower atomic weights, and we are entirely ignorant of the process by which uranium and thorium must have been produced originally.

Since radioactive changes have been found to be accompanied by the release of vast amounts of energy, compared with which the energy of chemical reactions is trivial, a new aspect in regard to the structure of atoms has arisen,—they must be complex in structure, the seats of enormous energy.

The determination of the amount of radium in the earth’s crust has indicated that the heat produced by it is amply sufficient to supply the loss of heat due to radiation, and this source of heat is regarded by many as the cause of volcanic action. The sun’s radiant heat also has been supposed to be supplied by radioactive action, so that the older views regarding the limitation of the age of the earth and the solar system on account of loss of heat have been considerably modified by our knowledge of radioactivity.

_Physical Chemistry._

The application of physical methods as aids to chemical science began in early times, and some of these, such as the determinations of gas and vapor densities, specific heats, and crystalline forms have been mentioned already in this article. Within recent times physical chemistry has greatly developed and a few of its important achievements will now be described.

_Molecular Weight Determinations._—Gas and vapor densities in connection with Avogadro’s principle, formed the only basis for molecular weight determinations until comparatively recent times. The early methods of Gay-Lussac and Dumas for vapor density were supplemented in 1868 by the method of Hofmann, whereby vapors were measured under diminished pressure over mercury. In 1878 Victor Meyer introduced a simpler method depending upon the displacement of air or other gas by the vapor in a heated tube. As refractory tubes, such as those of porcelain or even iridium, could be used in this method, molecular weights at extremely high temperatures were determined with interesting results. For instance, it was found that iodine vapor, which shows the molecule I_{2} at lower temperatures, gradually becomes monatomic with rise in temperature, that sulphur vapor dissociates from S_{8} to S_{2} under similar conditions, and that most of the metals, including silver, have monatomic vapors.

In 1883 and later it was pointed out by Raoult that the molecular weights of substances could be found from the freezing points of their solutions, but this method was complicated from the fact that salts, strong acids and strong bases behaved quite differently from other substances in this respect, and allowances had to be made for the types of substances used. The complication was afterwards explained by the ionization theory of Arrhenius. Better apparatus for this method was soon devised by Beckmann, who introduced also a method depending upon the boiling points of solutions, and these two methods are still the standard ones for determining molecular weights in solution. They are very extensively employed by organic chemists.

It has been found that the majority of substances when dissolved have the same molecular weight as in the gaseous condition, provided that they can be volatilized at comparable temperatures. For instance, sulphur in solution has the formula S_{8}, iodine is I_{2} and the metals are monatomic.

_Van’t Hoff’s Law and Arrhenius’s Theory of Ions._—Modern views on solutions date largely from 1886, when van’t Hoff called attention to the relations existing between the osmotic pressure exerted by dissolved substances and gas pressure.

Pfeffer, a botanist, was the first to measure osmotic pressure (1877). Basing his conclusions chiefly upon Pfeffer’s determinations, van’t Hoff formulated a new and highly important law, which may be stated as follows: The osmotic pressure exerted by a substance in solution is equal to the gas pressure that the substance would exert if it were a gas at the same temperature and the same volume. Further investigations have fully established the fact that molecules in dilute solution obey the simple laws of gases.

It was pointed out by van’t Hoff that salts, strong acids and strong bases showed marked exceptions to his law in exerting much greater osmotic pressures than those calculated for them.

The next year in 1887, Arrhenius explained this abnormal behavior of salts, strong acids and strong bases by assuming that they dissociate spontaneously into ions when they dissolve, and that these more numerous particles act like molecules in producing osmotic pressure. He showed that these exceptional substances all conduct electricity in solution, while those conforming with van’t Hoff’s law do not, and according to his theory the ions become positively or negatively charged when they are formed, and these charged ions conduct the current. For example a molecule of sodium chloride was supposed to give the two ions Na^+ and Cl^-, thus exerting twice as much osmotic pressure as a single molecule.

Determinations of osmotic pressure or related values, such as depression of the freezing point and of electric conductivity, indicated that ionization could not be regarded as complete in any case except in exceedingly dilute solutions, and that the extent of ionization varied with different substances. The fact that osmotic pressures and electric conductivities gave closely agreeing results in regard to the extent of ionization in various cases, is the strongest evidence in support of the theory.

It was difficult at first for many chemists to believe that atoms, such as those of sodium and chlorine, and groups such as NH_{4} and SO_{4} could exist independently in solution, even though electrically charged. However, the theory rapidly gained ground and is now accepted by nearly every chemist as a satisfactory explanation of many facts.

During recent years, many investigations relating to osmotic pressure and ionization have been carried out in the United States, but only the work of Morse, A. A. Noyes, and the late H. C. Jones can be merely alluded to here. It should be mentioned that the eminent author of the ionic hypothesis gave the Silliman Memorial course of lectures at Yale in 1911 on Theories of Solution.

_Colloidal Solutions._—Graham, an English chemist, in 1861 was the first to make a distinction between substances forming true solutions, which he called crystalloids, and those of a gummy nature resembling glue, which in solution do not diffuse readily through parchment membranes, as crystalloids do, and which he called colloids. The separation of colloids by means of parchment was called dialysis, and this process has come into extensive use in preparing pure colloidal solutions. Slow diffusion is now regarded as characteristic of colloids rather than their gummy condition.

Colloidal solutions occupy an intermediate position between true solutions and suspensions, resembling one or the other according to the kind of colloid and the fineness of division. By preparing filters with pores of varying degrees of fineness, Bechold has been able to separate colloids from each other in accordance with the size of their particles. It has also been possible to prepare different solutions of a colloid varying gradually from one in which the particles were undoubtedly in suspension to one which had many of the properties of a true solution.

Beginning in 1889, Carey Lea described in the Journal (=37=, 476, 1889 _et seq._) a variety of methods for preparing colloidal solutions of the metals, consisting in general of treating solutions of metallic salts with mild reducing agents. His work on colloidal silver was particularly extensive and interesting. Solutions of this kind have recently yielded some extremely interesting results by means of the ultra-microscope, an apparatus devised by Zsigmondy and Siedentopf. A very intense beam of light is passed through the solution and observed at right angles with a powerful microscope. Under these conditions, particles much too small to be seen by other means, reveal their presence by reflected light. It has been possible in a very dilute solution of known strength to count the particles and thus to calculate their size. The smallest colloidal particles measured in this way were of gold and were shown to have approximately ten times the diameter, or 1000 times the volume, attributed to ordinary molecules. It is of interest that the particles appear in rapid motion corresponding to the well-known Brownian movement.

The chemistry of colloids has now assumed such importance that it may be considered as a separate branch of the science. It has its own technical journal and deals largely with the chemistry of organic products. All living matter is built up of colloids, and hæmoglobin, starch, proteins, rubber and milk are examples of colloidal substances or solutions. Among inorganic substances, many sulphides, silicic acid, and the amorphous hydroxides, like ferric hydroxide, frequently act as colloids.

_Law of Mass Action._—Berthollet about the beginning of the last century was the first chemist to study the effect of mass, or more correctly, the concentration of substances on chemical action. His views summarized by himself are as follows: “The chemical activity of a substance depends upon the force of its affinity and upon the mass which is present in a given volume.” The development of this idea, which is fundamentally correct, was greatly hindered by the fact that Berthollet drew the incorrect conclusion that the composition of chemical compounds depended upon the masses of the substances combining to produce them, a conclusion in direct contradiction to the law of definite proportions, and since this view was soon disproved by Proust and others, Berthollet’s law in its other applications received no immediate attention. Mitchell, however, pointed out in the Journal (=16=, 234, 1829) the importance of Berthollet’s work, and Heinrich Rose in 1842 again called attention to the effect of mass, mentioning as one illustration the effect of water and carbonic acid in decomposing the very stable natural silicates. Somewhat later several other chemists made important contributions to the question of the influence of concentration upon chemical action, but it was the Norwegians, Guldberg and Waage, who first formulated the law of mass action in 1867.

This law has been of enormous importance in chemical theory, since it explains a great many facts upon a mathematical basis. It applies particularly to equilibrium in reversible reactions, where it states that the product of the concentrations on the one side of a simple reversible equation bears a constant relation to the products of the concentrations on the other side, provided that the temperature remains constant. In cases of this kind where two gases or vapors react with two solids, the latter if always in excess may be regarded as constant in concentration, and the law takes on a simpler aspect in applying only to the concentrations of the gaseous substances. For example, in the reversible reaction

3Fe + 4H_{2}O ⇄ Fe_{3}O_{4} + 4H_{2},

which takes place at rather high temperatures, a definite mixture of steam and hydrogen at a definite temperature will cause the reaction to proceed with equal rapidity in both directions, thus maintaining a state of equilibrium, provided that both iron and the oxide are present in excess. If, however, the relative concentrations of the hydrogen and steam are changed, or even if the temperature is changed, the reaction will proceed faster in one direction than in the other until equilibrium is again attained.

The principle of mass action also explains why it is sometimes possible for a reversible reaction to become complete in either direction. For instance, in connection with the reaction that has just been considered, if steam is passed over heated iron and if hydrogen is passed over the heated oxide, the gaseous product in each case is gradually carried away, and the reaction continually proceeds faster in one direction than in the other until it is complete, according to the equations

3Fe + 4H_{2}O → 3Fe_{3}O_{4} + 4H_{2}, and

Fe_{3}O_{4} + 4H_{2} → 3Fe + 4H_{2}O.

Many other well-known and important facts, both chemical and physical, depend upon this law. It explains the circumstance that a vapor-pressure is not dependent upon the amount of the liquid that is present; it also explains the constant dissociation pressure of calcium carbonate at a given temperature, irrespective of the amounts of carbonate and oxide present; in connection with the ionic theory, it furnishes the reason for the variable solubility of salts due to the presence of electrolytes containing ions in common; and it elucidates Henry’s law which states that the solubilities of gases are proportional to their pressures.

Ostwald, more than any other chemist, has been instrumental in making general applications of this law, and he made particularly extensive use of it in connection with analytical chemistry in a book upon this subject which he published.

_The Phase Rule._—In 1876 Willard Gibbs of Yale published a paper in the Proceedings of the Connecticut Academy of Science on the “Equilibrium of Heterogeneous Substances,” and two years later he published an abstract of the article in the Journal (=16=, 441, 1878). He had discovered a new law of nature of momentous importance and wide application which is called the “Phase-Rule” and is expressed by a very simple formula.

The application of this great discovery to chemical theory was delayed for ten years, partly, perhaps, because it was not sufficiently brought to the attention of chemists, but largely it appears because it was not at first understood, since its presentation was entirely mathematical.

It was Rooseboom, a Dutch chemist, who first applied the phase-rule. It soon attracted profound attention, and the name of Willard Gibbs attained world-wide fame among chemists. When Nernst, who is perhaps the most eminent physical chemist of the present time, was delivering the Silliman Memorial Lectures at Yale a few years ago, he took occasion to place a wreath on the grave of Willard Gibbs in recognition of his achievements.

To understand the rule, it is necessary to define the three terms, introduced by Gibbs, _phase_, _degrees of freedom_ and _component_.

By the first term, is meant the parts of any system of substances which are mechanically separable. For instance, water in contact with its vapor has two phases, while a solution of salt and water is composed of but one. The degrees of freedom are the number of physical conditions, including pressure, temperature and concentration, which can be varied independently in a system without destroying a phase. The exact definition of a component is not so simple, but in general, the components of a system are the integral parts of which it is composed. Any system made up of the compound H_{2}O, for instance, whether as ice, water or vapor, contains but one component, while a solution of salt and water contains two. Letting P, F, and C stand for the three terms, the phase-rule is simply

F = C + 2 − P

that is, the number of degrees of freedom in a system in equilibrium equals the number of components, plus two, minus the number of phases. The rule can be easily understood by means of a simple illustration. In a system composed of ice, water and water vapor, there are three phases and one component and therefore

F = 1 + 2 − 3 = 0

Such a system has no degrees of freedom. This means that no physical condition, pressure or temperature can be varied without destroying a phase, so that such a system can only exist in equilibrium at one fixed temperature, with a fixed value for its vapor-pressure.