Chapter C: E. Dutton, Critical observations on theories of the earth’s (6)

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.

For instance, if the system is heated above the fixed temperature, ice disappears and if the pressure is raised, vapor is condensed. If this same system of water alone contains but two phases, for instance, liquid and vapor, F = 1 + 2 − 2 = 1, or there is one degree of freedom. In such a system, one physical condition such as temperature can be varied independently, but only one, without destroying a phase. For instance, the temperature may be raised or lowered, but for every value of temperature there is a corresponding value for the vapor-pressure. One is a function of the other. If both values are varied independently, one phase will disappear, either vapor condensing entirely to water or the reverse. Finally if the system consists of one phase only, as water vapor, F = 2, or the system is divariant, which means that at any given temperature it is possible for vapor to exist at varying pressures.

The illustration which has been given relates to physical equilibrium, but the rule is applicable to cases involving chemical changes as well. In comparing the phase-rule with the law of mass action, it will be noticed that both have to do with equilibrium. The great advantage of the former is that it is entirely independent of the molecular condition of the substances in the different phases. For instance, it makes no difference so far as the application of the rule is concerned, whether a substance in solution is dissociated, undissociated or combined with the solvent. In any case, the solution constitutes one phase. On the other hand, the rule is purely qualitative, giving information only as to whether a given change in conditions is possible. The law of mass action is a quantitative expression so that when the value of the constant is once known, the change can be calculated which takes place in the entire system if the concentration of one substance is varied. The law, however, requires a knowledge of the molecular condition of the reacting substances, which may be uncertain or unknown, and chiefly on this account it has, like the phase-rule, often only a qualitative significance.

The phase rule has served as a most valuable means of classifying systems in equilibrium and as a guide in determining the possible conditions under which such systems can exist. As illustrations of its practical application, van’t Hoff used it as an underlying principle in his investigations on the conditions under which salt deposits have been formed in nature, and Rooseboom was able by its means to explain the very complicated relations existing in the alloys of iron and carbon which form the various grades of wrought iron, steel and cast iron.

_Thermochemistry._—This branch of chemistry has to do with heat evolved or absorbed in chemical reactions. It is important chiefly because in many cases it furnishes the only measure we have of the energy changes involved in reactions. To a great extent, it dates from the discovery by Hess in 1840 of a fundamental law which states that the heat evolved in a reaction is the same whether it takes place in one or in several stages. This law has made it possible to calculate the heat values of a large number of reactions which cannot be determined by direct experiment.

Thermochemistry has been developed by a comparatively few men who have contributed a surprisingly large number of results. Favre and Silbermann, beginning shortly after 1850, improved the apparatus for calorimetric determinations, which is called the calorimeter, and published many results. At about the same time Julius Thomsen, and in 1873 Berthelot, began their remarkable series of publications which continued until recently. Thomsen’s investigations were published in 1882 in =4= volumes. It is probably safe to say that the greater part of the data of thermochemistry was obtained by these two investigators. The bomb calorimeter, an apparatus for determining heat values by direct combustion, was developed by Berthelot. The recent work of Mixter at Yale, published in the Journal, and of Richards at Harvard should be mentioned particularly. Mixter’s work in this field began in 1901 (=12=, 347). Using an improved bomb calorimeter, he has developed a method of determining the heats of formation of oxides by combustion with sodium peroxide. By this same method as well as by direct combustion in oxygen, he has obtained results which appear to equal or excel in accuracy any which have ever been obtained in his field of work. Richards’s work has consisted largely of improvements in apparatus. He developed the so-called adiabatic calorimeter which practically eliminates one of the chief errors in thermal work caused by the heating or cooling effect of the surroundings. This modification is being generally adopted where extremely accurate work is required.

_Organic Chemistry._

One hundred years ago qualitative tests for a few organic compounds were known, the elements usually occurring in them were recognized, and some of them had been analyzed quantitatively, but organic chemistry was far less advanced than inorganic, and almost the whole of its enormous development has taken place during our period.

Berzelius made a great advance in the subject by establishing the fact, which had been doubted previously, that the elements in organic compounds are combined in constant, definite proportions. In 1823 Liebig brought to light the exceedingly important fact of isomerism by showing that silver fulminate had the same percentage composition as silver cyanate, a compound of very different properties. Isomeric compounds with identical molecular weight as well as the same composition have since been found in very many cases, and they have played a most important part in determining the arrangements of atoms in molecules. They have been found to be very numerous in many cases. For instance, three pentanes with the formula C_{5}H_{12}are known, all that are possible according to theory, and in each case the structure of the molecule has been established. On theoretical grounds it has been calculated that 802 isomeric compounds with the formula C_{13}H_{28} are possible, while with more complex formulas the numbers of isomers may be very much greater.

A particularly interesting case of isomerism was observed by Wöhler in 1828, when he found that ammonium cyanate changes spontaneously into urea

(NH_{4}CNO → N_{2}H_{4}CO).

This was the first synthesis of an organic compound from inorganic material, and it overthrew the prevailing view that vital forces were essential in the formation of organic substances. A great many natural organic compounds have been made artificially since that time, and some of them, such as artificial alizarin, indigo, oil of wintergreen, and vanillin, have more or less fully replaced the natural products. The preparation of a vast number of compounds not known in nature, many of which are of practical importance as medicines, dyes, explosives, etc., has been another great achievement of organic chemistry.

The development of our present formulas for organic compounds, by means of which in many cases the relative positions of the atoms can be shown with the greatest confidence, has been gradual. Formulas based on the dualistic idea of Berzelius were used for some time, type-formulas, with the employment of compound radicals, came later, the substitution of atoms or groups of atoms for others in chemical reactions came to be recognized, but one of the most important steps was the recognition of the quadrivalence of carbon and the general application of valency to atoms by Kekulé about 1858. This led directly to the use of modern structural formulas which have been of the greatest value in the theoretical interpretation of organic reactions. It was Kekulé also who proposed the hexagonal ring-formula for benzene, C_{6}H_{6}, which led to exceedingly important theoretical and practical developments. The details of the formulas for many other rings and complex structures have been established since that time, and there is no doubt that the remarkable achievements in organic chemistry during the past sixty years have been much facilitated by the use of these formulas.

Many important researches in organic chemistry have been carried out in the United States, and the activity in this direction has greatly increased in recent years. In this connection the large amount of work of this kind accomplished in the Sheffield Laboratory, at present under the guidance of Professor T. B. Johnson, should be mentioned.

It has happened that comparatively few publications on organic chemistry have appeared in the Journal, but it may be stated that the preparation of chloroform and its physiological effects were described by Guthrie (=21=, 64, 1832). Unknown to him, it had been prepared by Souberain, a French chemist, the previous year, but the former was the first to describe its physiological action. Silliman gave a sample to Doctor Eli Ives of the Yale Medical School, who used it to relieve a case of asthma. This was the first use of chloroform in medical practice (=21=, 405, 1832). Guthrie also described in the Journal (=21=, 284, 1832) his new process for converting potato starch into glucose, a method which is essentially the same as that used to-day in converting cornstarch into glucose. Lawrence Smith (=43=, 301, 1842 _et seq._), Horsford (=3=, 369, 1847 _et seq._), Sterry Hunt (=7=, 399, 1849), Carey Lea (=26=, 379, 1858 _et seq._), Remsen (=5=, 179, 1873 _et seq._), and others have contributed articles on organic chemistry.

_Agricultural Chemistry._

Until near the middle of the nineteenth century, it was believed that plants, like animals, used organic matter for food, and depended chiefly upon the humus of the soil for their growth. This view was held even long after it was known that plant leaves absorb carbon dioxide and give off oxygen, and after the ashes of plants had been accurately analyzed.

This incorrect view was overthrown by the celebrated German chemist, Liebig, who made many investigations upon the subject, and, properly interpreting previous knowledge, published a book in 1840 upon the application of chemistry to agriculture and physiology in which he maintained that the nutritive materials of all green plants are inorganic substances, namely, carbon dioxide, water, ammonia (nitrates), sulphates, phosphates, silica, lime, magnesia, potash, iron, and sometimes common salt. He drew the vastly important conclusion that the effective fertilization of soils depends upon replenishing the inorganic substances that have been exhausted by the crops.

The fundamental principles set forth by Liebig have been confirmed, and it has been found that the fertilizing constituents most commonly lacking in soils are nitrogen compounds, phosphates, and potassium salts, so that these have formed the important constituents of artificial fertilizers. Liebig himself found that humus is valuable in soils, because it absorbs and retains the soluble salts.

The foundation established by Liebig in regard to artificial fertilizers has led to an enormous application of these materials, much to the advantage of the world’s food supply.

It was Liebig’s belief, in accordance with the prevailing views, that decay and putrefaction as well as alcoholic and other fermentations were spontaneous processes, and when the eminent French chemist, Pasteur, in 1857, explained fermentation as directly caused by yeast, an epoch-making discovery which led to the explanation of decay and putrefaction by bacterial action and to the germ-theory of disease, the explanation was violently opposed by Liebig and other German chemists. Pasteur’s view prevailed, however, and since that time it has been found that various kinds of bacteria are responsible for the formation of ammonia from nitrogenous organic matter and also for the change of ammonia into the nitrates that are available as plant-food.

The long-debated question as to the availability of atmospheric nitrogen for plant-food was settled in 1886 by the discovery of Hellriegel that bacteria contained in nodules on the roots, especially of leguminous plants, are capable of bringing nitrogen into combination and furnishing it to the plants.

No more than an allusion can be made to agricultural experiment stations where soils, fertilizers, foods and other products are examined, and where other problems connected with agriculture are studied.

The late S. W. Johnson of Yale studied with Liebig and subsequently did much service for agricultural chemistry in this country, by his investigations, his teaching, and his writings. His book, “How Crops Grow,” published in 1868, gave an excellent account of the principles of agricultural chemistry. He did much to bring about the establishment of agricultural experiment stations in this country, and for a long time he was the director of the Connecticut Station.

In the Journal, as early as 1827, Amos Eaton (=12=, 370) published a simple method for the mechanical analysis of soils to determine their suitability for wheat-culture, and Hilgard, between 1872 and 1874, described an elaborate study of soil-analysis. J. P. Norton, a Yale professor, in 1847 (=3=, 322) published an investigation on the analysis of the oat, which was awarded a prize of fifty sovereigns by a Scotch agricultural society, while Johnson, Atwater, and others have contributed articles on the analysis of various farm products.

_Industrial Acids and Alkalies._

One hundred years ago sulphuric acid was manufactured on a comparatively very small scale in lead chambers. In 1818, an English manufacturer of the acid introduced the modern feature of using pyrites in the place of brimstone, while the Gay-Lussac tower in 1827 and the Glover tower in 1859 began to be applied as great improvements in the chamber process. Within about twenty years the contact process, employing platinized asbestos, has replaced the old chamber process to a large extent. It has the advantage of producing the concentrated acid, or the fuming acid, directly.

During our period the manufacture of sulphuric acid has increased enormously. Very large quantities of it have been used in connection with the Leblanc soda process in its rapid development. It came to be employed extensively for absorbing ammonia in the illuminating-gas industry, which was in its infancy one hundred years ago. New industries such as the manufacture of “superphosphates” as artificial fertilizers, the refining of petroleum, the manufacture of artificial dyestuffs and many other modern chemical products have greatly increased the demand for it, while its employment in the production of nitric and other acids, and for many other purposes not already mentioned, has been very great.

The manufacture of nitric acid has been greatly extended during our period on account of its employment for producing explosives, artificial dyestuffs, and for many other purposes. Chile saltpeter became available for making it about 1852. This acid has been manufactured recently from atmospheric nitrogen and oxygen by combining them by the aid of powerful electric discharges. This process has been used chiefly in Norway where water-power is abundant, as it requires a large expenditure of energy. A still more recent method for the production of nitric acid depends upon the oxidation of ammonia by air with the aid of a contact substance, such as platinized asbestos.

The production of ammonia, which was very small a hundred years ago, has been vastly increased in connection with the development of the illuminating-gas industry and the employment of by-product coke ovens. This substance is very extensively used in refrigerating machines and also in a great many chemical operations, including the Solvay soda process. Ammonium salts are of great importance also as fertilizers in agriculture. The conversion of atmospheric nitrogen into ammonia on a commercial scale is a recent achievement. It has been accomplished by heating calcium carbide, an electric-furnace product made from lime and coke, with nitrogen gas, thus producing calcium cyanamide, and then treating this cyanamide with water under proper conditions. Another method devised by Haber consists in directly combining nitrogen and hydrogen gases under high pressure with the aid of a contact substance.

Leblanc’s method for obtaining sodium carbonate from sodium chloride by first converting the latter into the sulphate by means of sulphuric acid and then heating the sulphate with lime and coal in a furnace was invented as early as 1791, but it was not rapidly developed and did not gain a foothold in England until 1826 on account of a high duty on salt up to that time. Afterwards the process flourished greatly in connection with the sulphuric acid industry upon which it depended, and with the bleaching-powder industry which utilized the hydrochloric acid incidentally produced by it, and, of course, in connection with soap manufacture and many other industries in which the soda itself was employed.

About 1866 the Solvay process appeared as a rival to the Leblanc process. This depends upon the precipitation of sodium bicarbonate from salt solutions by means of carbon dioxide and ammonia, with the subsequent recovery of the ammonia. It has displaced the older process to a large extent, and it is carried on extensively in this country, for instance, at Syracuse, New York.

Other processes for soda depend upon the electrolysis of sodium chloride solutions. In this case caustic soda and chlorine are the direct products, and the chlorine thus produced and liquefied by pressure in steel cylinders, has become an important commercial article.

In earlier times wood-ashes were the source of potash and potassium salts. Wurtz in the Journal (=10=, 326, 1850) suggested the availability of New Jersey greensand as a source of potash and showed how this mineral could be decomposed, but it does not appear that this mineral has ever been utilized for the purpose. About 1861 the German potash-salt deposits began to be developed, and these have since become the chief source of this material. At present many efforts are being made to obtain potassium compounds from other sources, such as brines, cement-kiln dust, and feldspar and other minerals but thus far the results have not satisfied the demand.

_Conclusion._

This account of chemical progress has given only a limited view of small portions of the subject, because the amount of available material is so vast in comparison with the space allowed for its presentation. Since the Journal has published comparatively little organic chemistry, it was decided to make room for a better presentation of other things by giving only a brief discussion of this exceedingly active and important branch of the science. For similar reasons industrial and metallurgical chemistry, and other branches besides, in spite of their great growth and importance, have been neglected, except for some incidental references to them, and some account of a few of the more important industrial chemicals.

It appears that we have much reason to be proud of the advances in chemistry that have been made during the Journal’s period, and of the part that the Journal has taken in connection with them, and there seems to be no doubt that this progress has not diminished during more recent times.

The present tendency of chemical research is evidently towards a still greater development of organic chemistry, and an increased application of physics and mathematics to chemical theory and practice.

The very great improvements that have been made in chemical education, both in the number of students and the quality of instruction, during the period under discussion, and particularly in rather recent times, gives promise for excellent future progress.

_Note._

Footnote 153:

It appears that the most accurate experimental demonstration ever made
of this law was that of E. W. Morley, published in the Journal (=41=,
220, 276, 1891). He showed that 2·0002 volumes of hydrogen combine
with one volume of oxygen.

XI
A CENTURY’S PROGRESS IN PHYSICS

By LEIGH PAGE

_Dynamics._—At the beginning of the nineteenth century mechanics was the only major branch of physical science which had attained any considerable degree of development. Two centuries earlier, Galileo’s experiments on the rate of fall of iron balls dropped from the top of the Leaning Tower of Pisa, had marked the origin of dynamics. He had easily disproved the prevalent idea that even under conditions where air resistance is negligible heavy bodies would fall more rapidly than light ones, and further experiments had led him to conclude that the increase in velocity is proportional to the _time_ elapsed, and not to the _distance_ traversed, as he had at first supposed. Less than a century later Newton had formulated the laws of motion in the same words in which they are given to-day. These laws of motion, coupled with his discovery of the law of universal gravitation, had enabled him to correlate at once the planetary notions which had proved so puzzling to his predecessors. His success gave a tremendous stimulus to the development and extension of the fundamental dynamical principles that he had brought to light, which culminated in the work of the great French mathematicians, Lagrange and Laplace, a little over a hundred years ago.

Newton’s laws of motion, it must be remembered, apply only to a particle, or to those bodies which can be treated as particles in the problem under consideration. In his “Mécanique Analytique” Lagrange extended these principles so as to make it possible to treat the motion of a connected system by a method almost as simple as that contained in the second law of motion. Instead of three scalar equations for each of the innumerably large number of particles involved, he showed how to reduce the ordinary dynamical equations to a number equal to that of the degrees of freedom of the system. This is made possible by a combination of d’Alembert’s principle, which eliminates the forces due to the connections between the particles, and the principle of virtual work, which confines the number of equations to the number of possible independent displacements. The aim of Lagrange was to make dynamics into a branch of analysis, and his success may be inferred from the fact that not a single diagram or geometrical figure is to be found in his great work.

_Celestial Mechanics._—Almost simultaneously with the publication of the “Mécanique Analytique” appeared Laplace’s “Mécanique Celeste.” Laplace’s avowed aim was to offer a complete solution of the great dynamical problem involved in the solar system, taking into account, in addition to the effect of the sun’s gravitational field, those perturbations in the motion of each planet caused by the approach and recession of its neighbors. So successful was his analysis of planetary motions that his contemporaries believed that they were not far from a complete explanation of the world on mechanical principles. Laplace himself was undoubtedly convinced that nothing was needed beyond a knowledge of the masses, positions, and initial velocities of every material particle in the universe in order to completely predetermine all subsequent motion.

The greatest triumph of these dynamical methods was to come half a century later. The planet Uranus, discovered in 1781 by the elder Herschel, was at that time the farthest known planet from the sun. But the orbit of Uranus was subject to some puzzling variations. After sifting all the known causes of these disturbances, Leverrier in France and Adams in England independently reached the conclusion that another planet still more remote from the sun must be responsible, and computed its orbit. Leverrier communicated to Galle of Berlin the results of his calculations, and during the next few days the German astronomer discovered Neptune within one degree of its predicted position!

We shall mention but one other achievement of the methods of celestial mechanics. Those visitors of the skies, the comets, which become so prominent only to fade away and vanish perhaps forever, had interested astronomers from the earliest times. Soon after the discovery of the law of gravitation, Newton had worked out a method by which the elements of a comet’s orbit can be computed from observations of its position. It was found that the great majority of these bodies move in nearly parabolic paths and only a few in ellipses. Of the latter the most prominent is the brilliant comet first observed by Halley in 1681. It has reappeared regularly at intervals of seventy-six years; the last appearance in the spring of 1910 is no doubt well remembered by the reader. Kant had considered comets to be formed by condensing solar nebulæ, whereas Laplace had maintained that they originate in matter which is scattered throughout stellar space and has no connection with the solar system. A study of the distribution of inclinations of comet orbits by H. A. Newton (=16=, 165, 1878) of New Haven substantiated Laplace’s hypothesis, and led to the conclusion that the periodic comets have been captured by the attraction of those planets near to which they have passed. Of these comets a number have comparatively short periods, and are found to have orbits which are in general only slightly inclined to those of the planets, and are traversed in the same direction. Moreover, the fact that the orbit of each of these comets comes very close to that of Jupiter made it seem probable that they have been attached to the solar system by the attraction of this planet. Further confirmation of this hypothesis was furnished by H. A. Newton’s (=42=, 183 and 482, 1891) explanation of the small inclination of their orbits and the scarcity of retrograde motions among them.

In 1833 occurred one of the greatest meteoric showers of history. Olmstead (=26=, 132, 1834) and Twining (=26=, 320, 1834) of New Haven noticed that these shooting stars traverse parallel paths, and were the first to suggest that they must be moving in swarms in a permanent orbit. From an examination of all accessible records, H. A. Newton (=37=, 377, 1864; =38=, 53, 1864) was able to show that meteoric showers are common in November, and of particular intensity at intervals of 33 or 34 years. He confidently predicted a great shower for Nov. 13th, 1866, which not only actually occurred but was followed by another a year later, showing that the meteoric swarm extended so far as to require two years to cross the earth’s orbit. H. A. Newton (=36=, 1, 1888) in America and Adams in England took up the study of meteoric orbits with great interest, and the former concluded that these orbits are in every sense similar to those of the periodic comets, implying that a swarm of meteors originates in the disintegration of a comet. In fact Schiaparelli actually identified the orbit of the Perseids, or August meteors, with Tuttle’s comet of 1862, and shortly after the orbit of the Leonids, or November meteors, was found to be the same as that of Tempel’s comet.

_Electromagnetism._—During the eighteenth century much interest had been manifested in the study of electrostatics and magnetism. Du Fay, Cavendish, Michell and Coulomb abroad and Franklin in America had subjected to experimental investigation many of the phenomena of one or both of these sciences, and in the early years of the nineteenth century Poisson developed to a remarkable extent the analytical consequences of the law of force which experiment had revealed. Both Laplace and he made much use of the function to which Green gave the name “potential” in 1828, and which is such a powerful aid in solving problems involving magnetism or electricity at rest.

Meantime electric currents had been brought under the hand of the experimenter by the discoveries of Galvani and Volta. Large numbers of cells were connected in series, and interest seemed to lie largely in producing brilliant sparks or fusing metals by means of a heavy current. Hare (=3=, 105, 1821) of the University of Pennsylvania constructed a battery consisting of two troughs of forty cells each, so arranged that the coppers and zincs can be lowered simultaneously into the acid and large currents obtained before polarization has a chance to interfere. This “deflagrator” was used to ignite charcoal in the circuit, or melt fine wires, and was for some time the most powerful arrangement of its kind. That “galvanism” is something quite different from static electricity was the opinion of many investigators; Hare considered the heat developed to be the distinguishing mark of the electric current. He says: “It is admitted that the action of the galvanic fluid is upon or between atoms; while mechanical electricity when uncoerced, acts only upon masses. This difference has not been explained unless by my hypothesis, in which caloric, of which the influence is only exerted between atoms, is supposed to be a principal agent in galvanism.”

Questioning minds were beginning to suspect that there must be some connection between electricity and magnetism. For lightning had been known to make magnets of steel knives and forks, and Franklin had magnetized a sewing needle by the discharge from a Leyden jar. Finally Oersted of Copenhagen undertook systematic investigation of the effect of electricity on the magnetic needle. His researches were without result until during the course of a series of lectures on “Electricity, Galvanism, and Magnetism” delivered during the winter of 1819–20 it occurred to him to investigate the action of an electric current on a magnetic needle. At first he placed the wire bearing the current at right angles to the needle, with, of course, no result; then it occurred to him to place it parallel. A deflection was observed, for to his surprise the needle insisted on turning until perpendicular to the wire.

Oersted’s discovery that an electric current exerts a couple on a magnetic needle was followed a few months later by Ampère’s demonstration before the French Academy that two currents flowing in the same direction attract each other, while two in opposite directions repel. The story goes that a critic attempted to belittle this discovery by remarking that as it was known that two currents act on one and the same magnet, it was obvious that they would act upon each other. Whereupon Arago arose to defend his friend. Drawing two keys out of his pocket he said, “Each of these keys attracts a magnet; do you believe that they therefore attract each other?”

A few years later Ampère showed how to express quantitatively the force between current elements, and indeed developed to a considerable degree the equivalence between a closed circuit carrying a current and a magnetic shell. So convincing was his analysis and so thorough his discussion of the subject, that Maxwell said of this memoir half a century later, “The whole, theory and experiment, seems as if it had leaped, full grown and full armed, from the brain of the ‘Newton of electricity.’ It is perfect in form and unassailable in accuracy; and it is summed up in a formula from which all the phenomena may be deduced, and which must always remain the cardinal formula of electrodynamics.”

Shortly afterwards the dependence of a current on the conductivity of the wire used and the grouping of cells employed, was made clear by the work of Ohm. Many of his results were obtained independently by Joseph Henry (=19=, 400, 1831) of the Albany Academy, who described in 1831 a powerful electromagnet in which a great many coils of wire insulated with silk were wound around an iron core and connected in parallel with a single cell. He remarks in this paper that with long wires, as in the telegraph, many cells arranged in series should be used, whereas for several short wires connected in parallel a single cell with large plates is more efficient.

_Current Induction._—Impressed by the fact that electric charges have the power of inducing other charges on neighboring conductors without coming into contact with them, Faraday was engaged in investigating the possibility of an analogous phenomenon in the case of electric currents. His idea at first seems to have been that a current should induce another current in any closed conducting circuit which happens to be in its vicinity. Experiment readily showed the falsity of this conception, but a brief deflection of the galvanometer in the secondary circuit was noticed at the instant of making and breaking the current in the primary. Further experiments showed that thrusting a permanent steel magnet into a coil connected to a galvanometer caused the needle to deflect. In fact Faraday’s report to the Royal Society on November 24th, 1831, contains a complete account of all experimental methods available for inducing a current in a closed circuit.

While Faraday is entitled to credit for the discovery of current induction by virtue of the priority of his publication, it must not pass unnoticed that Henry obtained many of the same experimental results independently and some even earlier. Henry was at this time instructor in mathematics at the Albany Academy, and seven hours of teaching a day made it well nigh impossible to carry on original research except during the vacation month of August. As early as the summer of 1830 he had wound 30 feet of copper wire around the armature of a horseshoe electromagnet and connected it to a galvanometer. When the magnet was excited, a momentary deflection was observed. “I was, however, much surprised,” he says, “to see the needle suddenly deflected from a state of rest to about 20° to the east, or in a contrary direction, when the battery was withdrawn from the acid, and again deflected to the west when it was re-immersed.” In addition a deflection was obtained by detaching the armature from the magnet, or by bringing it again into contact. Had the results of these experiments been published promptly, America would have been entitled to credit for the most important discovery of the greatest of England’s many great experimenters. But Henry desired first to repeat his experiments on a larger scale, and while new magnets were being constructed, the news of Faraday’s discovery arrived. This occasioned hasty publication of the work already done in an appendix to volume =22=, 1832, of the Journal.

At almost the same time Henry made another important discovery and this time he was anticipated by no other investigator in making public his results. In the paper already referred to be describes the phenomenon known to-day as self-induction. “When a small battery is moderately excited by diluted acid and its poles, which must be terminated by cups of mercury, are connected by a copper wire not more than a foot in length, no spark is perceived when the connection is either formed or broken; but if a wire thirty or forty feet long be used, instead of the short wire, though no spark will be perceptible when the connection is made, yet when it is broken by drawing one end of the wire from its cup of mercury a vivid spark is produced.... The effect appears somewhat increased by coiling the wire into a helix; it seems to depend in some measure on the length and thickness of the wire; I can account for these phenomena only by supposing the long wire to become charged with electricity which by its reaction on itself projects a spark when the connection is broken.”

Soon after, Henry went to Princeton and there continued his experiments in electromagnetism. No difficulty was experienced in inducing currents of the third, fourth and fifth orders by using the first secondary as primary for yet another secondary circuit, and so on (=38=, 209, 1840). The directions of these currents of higher orders when the primary is made or broken proved puzzling at first, but were satisfactorily explained a year later (=41=, 117, 1841). In addition induced currents were obtained from a Leyden jar discharge. Faraday failed to find any screening effect of a conducting cylinder placed around the primary and inside the secondary. Henry examined the matter, and found that the screening effect exists only when the induced current is due to a make or break of the primary circuit, and not when it is caused by motion of the primary.

Henry’s work was mainly descriptive; it remained for Faraday to develop a theory to account for the phenomena discovered and to prepare the way for quantitative formulation of the laws of current induction. This he did in his representation of a magnetic field by means of lines of force; a conception which he found afterwards to be equally valuable when applied to electrostatic problems. Every magnet and every current gives rise to these closed curves; in the case of a magnet they thread it from south pole to north, while a straight wire bearing a current is surrounded by concentric rings. The connection between lines of force and the induction of currents is contained in the rule that a current is induced in a closed circuit only when a change takes place in the number of lines of force passing through it. Furthermore the dependence of the current strength on the conductivity of the wire employed has led to recognition of the fact that it is the electromotive force and not the current itself which is conditioned by the change in magnetic flux.

Great interest was attached to the utilization of the newly discovered forces of electromagnetism. In 1831 Henry (=20=, 340, 1831) described a reciprocating engine depending on magnetic attraction and repulsion, and C. G. Page (=33=, 118, 1838; =49=, 131, 1845) devised many others. The latter’s most important work, however, was the invention of the Ruhmkorff coil. In 1836 (=31=, 137, 1837) he found the strongest shocks to be obtained, from a secondary coil of many windings forming a continuation of a primary of half the number of turns. His perfection of the self-acting circuit breaker (=35=, 252, 1839) widened the usefulness of the induction coil, and his substitution of a bundle of iron wires for a solid iron core (=34=, 163, 1838) greatly increased its efficiency.

_Conservation of Energy._—Perhaps the most important advance of the nineteenth century has been the establishment of the principle of conservation of energy. Despite the fact that the “principe de la conservation des force vives” had been recognized by the French mathematicians of the early part of the century, the application of this principle even to purely mechanical problems was contested by some scientists. Through the early numbers of the Journal runs a lively controversy as to whether there is not a loss of power involved in imparting momentum to the reciprocating parts of a steam engine only to check the motion later on in the stroke. Finally Isaac Doolittle (=14=, 60, 1828), of the Bennington Iron Works, ends the discussion by the pertinent remark: “If there be, as is contended by one of your correspondents, a loss of more than one third of the power, in transforming an alternating rectilinear movement into a continuous circular one by means of a crank, I should like to be informed what would be the effect if the proposition were reversed, as in the case of the common saw mill, and in many other instances in practical mechanics.”

A realization of the equivalence of heat and mechanical work did not come until the middle of the century, in spite of the conclusive experiments of the American Count Rumford and the English Davy before the year 1800. So firmly enthroned was the caloric theory, according to which heat is an indestructible fluid, that evidence against it was given scant consideration. In fact the success of the analytical method introduced by Fourier in 1822 for the solution of problems in conduction of heat only added to the difficulties of the adherents of the kinetic theory. But recognition of heat as a form of energy was on the way, and when it came it made its appearance almost simultaneously in half a dozen different places. Perhaps Robert Mayer of Heilbronn was the first to state explicitly the new principle. His paper “On the Forces of Inorganic Nature” was refused publication in Poggendorff’s Annalen, but fared better at the hands of another editor. During the next few years Joule determined the mechanical equivalent of heat experimentally by a number of different methods, some of which had already been devised by Carnot. Of those he used, the most familiar consists in churning up a measured mass of water by means of paddles actuated by falling weights and calculating the heat developed from the rise in temperature. However, the work of the young Manchester brewer received little attention from the members of the British Association before whom it was reported until Kelvin showed them its significance and attracted their interest to it. Meanwhile Helmholtz had completed a very thorough disquisition on the conservation of energy not only in dynamics and heat but in other departments of physics as well. His paper on “Die Erhaltung der Kraft” was frowned upon by the members of the Physical Society of Berlin before whom he read it, and received the same treatment as Mayer’s from the editor of Poggendorff’s Annalen. Helmholtz’s “Kraft,” like the “vis viva” of other writers, is the quantity which Young had already christened energy. Not many years elapsed, however, until the convictions of Mayer, Joule, Kelvin and Helmholtz became the most clearly recognized of all physical principles. As early as 1850 Jeremiah Day (=10=, 174, 1850), late president of Yale College, admitted the improbability of constructing a machine capable of perpetual motion, even though the “imponderable agents” of electricity, galvanism and magnetism be utilized.