The Principles of Chemistry Volume I (of 2)

[1] Chemistry, like every other science, is at once a means and an end. It is a means of attaining certain practical results. Thus, by its assistance, the obtaining of matter in its various forms is facilitated; it shows new possibilities of availing ourselves of the forces of nature, indicates the methods of preparing many substances, points out their properties, &c. In this sense chemistry is closely connected with the work of the manufacturer and the artisan, its sphere is active, and is a means of promoting general welfare. Besides this honourable vocation, chemistry has another. With it, as with every other elaborated science, there are many lofty aspirations, the contemplation of which serves to inspire its workers and adherents. This contemplation comprises not only the principal data of the science, but also the generally-accepted deductions, and also hypotheses which refer to phenomena as yet but imperfectly known. In this latter sense scientific contemplation varies much with times and persons, it bears the stamp of creative power, and embraces the highest forms of scientific progress. In that pure enjoyment experienced on approaching to the ideal, in that eagerness to draw aside the veil from the hidden truth, and even in that discord which exists between the various workers, we ought to see the surest pledges of further scientific progress. Science thus advances, discovering new truths, and at the same time obtaining practical results. The edifice of science not only requires material, but also a plan, and necessitates the work of preparing the materials, putting them together, working out the plans and the symmetrical proportions of the various parts. To conceive, understand, and grasp the whole symmetry of the scientific edifice, including its unfinished portions, is equivalent to tasting that enjoyment only conveyed by the highest forms of beauty and truth. Without the material, the plan alone is but a castle in the air—a mere possibility; whilst the material without a plan is but useless matter. All depends on the concordance of the materials with the plan and execution, and the general harmony thereby attained. In the work of science, the artisan, architect, and creator are very often one and the same individual; but sometimes, as in other walks of life, there is a difference between them; sometimes the plan is preconceived, sometimes it follows the preparation and accumulation of the raw material. Free access to the edifice of science is not only allowed to those who devised the plan, worked out the detailed drawings, prepared the materials, or piled up the brickwork, but also to all those who are desirous of making a close acquaintance with the plan, and wish to avoid dwelling in the vaults or in the garrets where the useless lumber is stored.

Knowing how contented, free, and joyful is life in the realm of science, one fervently wishes that many would enter its portals. On this account many pages of this treatise are unwittingly stamped with the earnest desire that the habits of chemical contemplation which I have endeavoured to instil into the minds of my readers will incite them to the further study of science. Science will then flourish in them and by them, on a fuller acquaintance not only with that little which is enclosed within the narrow limits of my work, but with the further learning which they must imbibe in order to make themselves masters of our science and partakers in its further advancement.

Those who enlist in the cause of science have no reason to fear when they remember the urgent need for practical workers in the spheres of agriculture, arts, and manufacture. By summoning adherents to the work of theoretical chemistry, I am confident that I call them to a most useful labour, to the habit of dealing correctly with nature and its laws, and to the possibility of becoming truly practical men. In order to become actual chemists, it is necessary for beginners to be well and closely acquainted with three important branches of chemistry—analytical, organic, and theoretical. That part of chemistry which is dealt with in this treatise is only the groundwork of the edifice. For the learning and development of chemistry in its truest and fullest sense, beginners ought, in the first place, to turn their attention to the practical work of analytical chemistry; in the second place, to practical and theoretical acquaintance with some special chemical question, studying the original treatises of the investigators of the subject (at first, under the direction of experienced teachers), because in working out particular facts the faculty of judgment and of correct criticism becomes sharpened; in the third place, to a knowledge of current scientific questions through the special chemical journals and papers, and by intercourse with other chemists. The time has come to turn aside from visionary contemplation, from platonic aspirations, and from classical verbosity, and to enter the regions of actual labour for the common weal, to prove that the study of science is not only air excellent education for youth, but that it instils the virtues of industry and veracity, and creates solid national wealth, material and mental, which without it would be unattainable. Science, which deals with the infinite, is itself without bounds.

[2] I recommend those who are commencing the study of chemistry with my book to first read only what is printed in the large type, because in that part I have endeavoured to concentrate all the fundamental, indispensable knowledge required for that study. In the footnotes, printed in small type (which should be read only after the large text has been mastered), certain details are discussed; they are either further examples, or debatable questions on existing ideas which I thought useful to lay before those entering into the sphere of science, or certain historical and technical details which might be withdrawn from the fundamental portion of the book. Without intending to attain in my treatise to the completeness of a work of reference, I have still endeavoured to express the principal developments of science as they concern the chemical elements viewed in that aspect in which they appeared to me after long continued study of the subject and participation in the contemporary advance of knowledge.

I have also placed my personal views, suppositions, and arguments in the footnotes, which are chiefly designed for details and references. But I have endeavoured to avoid here, as in the text, not only all that I consider doubtful, but also those details which belong either to special branches of chemistry (for instance, to analytical, organic, physical, theoretical, physiological, agricultural, or technical chemistry), or to different branches of natural science which are more and more coming into closer and closer contact with chemistry. Chemistry, I am convinced, must occupy a place among the natural sciences side by side with mechanics; for mechanics treats of matter as a system of ponderable points having scarcely any individuality and only standing in a certain state of mobile equilibrium. For chemistry, matter is an entire world of life, with an infinite variety of individuality both in the elements and in their combinations. In studying the general uniformity from a mechanical point of view, I think that the highest point of knowledge of nature cannot be attained without taking into account the individuality of things in which chemistry is set to seek for general higher laws. Mechanics may be likened to the science of statesmanship, chemistry to the sciences of jurisprudence and sociology. The general universe could not be built up without the particular individual universe, and would be a dry abstract were it not enlivened by the real variety of the individual world. Mechanics forms the classical basis of natural philosophy, while chemistry, as a comparatively new and still young science, already strives to—and will, in the future introduce a new, living aspect into the philosophy of nature; all the more as chemistry alone is never at rest or anywhere dead—its vital action has universal sway, and inevitably determines the general aspect of the universe. Just as the microscope and telescope enlarge the scope of vision, and discover life in seeming immobility, so chemistry, in discovering and striving to discern the life of the invisible world of atoms and molecules and their ultimate limit of divisibility, will clearly introduce new and important problems into our conception of nature. And I think that its rôle, which is now considerable, will increase more and more in the future; that is, I think that in its further development it will occupy a place side by side with mechanics for the comprehension of the secrets of nature. But here we require some second Newton; and I have no doubt that he will soon appear.

[3] I was much helped in gathering data from the various chemical journals of the last five years by the abstracts made for me by Mr. Y. V. Kouriloff, to whom I tender my best thanks.

[4] The English translation was made by G. Kamensky, and edited by A. J. Greenaway; published by Longmans, Green & Co.

[5] The German translation was made by L. Jawein and A. Thillot; published by Ricker (St. Petersburg).

[6] The French translation has been commenced by E. Achkinasi and H. Carrion from the fifth edition, and is published by Tignol (Paris).

[7] The fifth edition was not only considerably enlarged, compared with the preceding, but also the foundations of the periodic system of the elements were placed far more firmly in it than in the former editions. The subject-matter was also divided into text and footnotes, which contained details unnecessary for a first acquaintance with chemistry. The fifth edition sold out sooner than I expected, so that instead of issuing supplements (containing the latest discoveries in chemistry), as I had proposed, I was obliged to publish the present entirely new edition of the work.

[8] This hypothesis is not only mentioned in different parts of this book, but is partly (from the aspect of the specific gravity of solutions) developed in my work, The Investigation of Solutions from their Specific Gravity, 1887.

[1] The investigation of a substance or a natural phenomenon consists (a) in determining the relation of the object under examination to that which is already known, either from previous researches, or from experiment, or from the knowledge of the common surroundings of life—that is, in determining and expressing the quality of the unknown by the aid of that which is known; (b) in measuring all that which can be subjected to measurement, and thereby denoting the quantitative relation of that under investigation to that already known and its relation to the categories of time, space, temperature, mass, &c.; (c) in determining the position held by the object under investigation in the system of known objects guided by both qualitative and quantitative data; (d) in determining, from the quantities which have been measured, the empirical (visible) dependence (function, or ‘law,’ as it is sometimes termed) of variable factors—for instance, the dependence of the composition of the substance on its properties, of temperature on time, of time on locality, &c.; (e) in framing hypotheses or propositions as to the actual cause and true nature of the relation between that studied (measured or observed) and that which is known or the categories of time, space, &c.; (f) in verifying the logical consequences of the hypotheses by experiment; and (g) in advancing a theory which shall account for the nature of the properties of that studied in its relations with things already known and with those conditions or categories among which it exists. It is certain that it is only possible to carry out these investigations when we have taken as a basis some incontestable fact which is self-evident to our understanding; as, for instance, number, time, space, motion, or mass. The determination of such primary or fundamental conceptions, although not excluded from the possibility of investigation, frequently does not subject itself to our present mode of scientific generalisation. Hence it follows that in the investigation of anything, there always remains something which is accepted without investigation, or admitted as a known factor. The axioms of geometry may be taken as an example. Thus in the science of biology it is necessary to admit the faculty of organisms for multiplying themselves, as a conception whose meaning is as yet unknown. In the study of chemistry, too, the notion of elements must be accepted almost without any further analysis. However, by first investigating that which is visible and subject to direct observation by the organs of the senses, we may hope that in the first place hypotheses will be arrived at, and afterwards theories of that which has now to be placed at the basis of our investigations. The minds of the ancients strove to seize at once the very fundamental categories of investigation, whilst all the successes of recent knowledge are based on the above-cited method of investigation without the determination of ‘the beginning of all beginnings.’ By following this inductive method, the exact sciences have already succeeded in becoming accurately acquainted with much of the invisible world, which directly is imperceptible to the organs of sense (for example, the molecular motion of all bodies, the composition of the heavenly luminaries, the paths of their motion, the necessity for the existence of substances which cannot be subjected to experiment, &c.), and have verified the knowledge thus obtained, and employed it for increasing the interests of humanity. It may therefore be safely said that the inductive method of investigation is a more perfect mode of acquiring knowledge than the deductive method alone (starting from a little of the unknown accepted as incontestable to arrive at the much which is visible and observable) by which the ancients strove to embrace the universe. By investigating the universe by an inductive method (endeavouring from the much which is observable to arrive at a little which may be verified and is indubitable) the new science refuses to recognise dogma as truth, but through reason, by a slow and laborious method of investigation, strives for and attains to true deductions.

[2] A substance or material is that which occupies space and has weight; that is, which presents a mass attracted by the earth and by other masses of material, and of which the objects of nature are composed, and by means of which the motions and phenomena of nature are accomplished. It is easy to discover by examining and investigating, by various methods, the objects met with in nature and in the arts, that some of them are homogeneous, whilst others are composed of a mixture of several homogeneous substances. This is most clearly apparent in solid substances. The metals used in the arts (for example, gold, iron, copper) must be homogeneous, otherwise they are brittle and unfit for many purposes. Homogeneous matter exhibits similar properties in all its parts. By breaking up a homogeneous substance we obtain parts which, although different in form, resemble each other in their properties. Glass, pure sugar, marble, &c., are examples of homogeneous substances. Examples of non-homogeneous substances are, however, much more frequent in nature and the arts. Thus the majority of the rocks are not homogeneous. In porphyries bright pieces of a mineral called ‘orthoclase’ are often seen interspersed amongst the dark mass of the rock. In ordinary red granite it is easy to distinguish large pieces of orthoclase mixed with dark semi-transparent quartz and flexible laminæ of mica. Similarly, plants and animals are non-homogeneous. Thus, leaves are composed of a skin, fibre, pulp, sap, and a green colouring matter. As an example of those non-homogeneous substances which are produced artificially, gunpowder may be cited, which is prepared by mixing together known proportions of sulphur, nitre, and charcoal. Many liquids, also, are not homogeneous, as may be observed by the aid of the microscope, when drops of blood are seen to consist of a colourless liquid in which red corpuscles, invisible to the naked eye owing to their small size, are floating about. It is these corpuscles which give blood its peculiar colour. Milk is also a transparent liquid, in which microscopical drops of fat are floating, which rise to the top when milk is left at rest, forming cream. It is possible to extract from every non-homogeneous substance those homogeneous substances of which it is made up. Thus orthoclase may he separated from porphyry by breaking it off. So also gold is extracted from auriferous sand by washing away the mixture of clay and sand. Chemistry deals only with the homogeneous substances met with in nature, or extracted from natural or artificial non-homogeneous substances. The various mixtures found in nature form the subjects of other natural sciences—as geognosy, botany, zoology, anatomy, &c.

[3] All those events which are accomplished by substances in time are termed ‘phenomena.’ Phenomena in themselves form the fundamental subject of the study of physics. Motion is the primary and most generally understood form of phenomenon, and therefore we endeavour to reason about other phenomena as clearly as when dealing with motion. For this reason mechanics, which treats of motion, forms the fundamental science of natural philosophy, and all other sciences endeavour to reduce the phenomena with which they are concerned to mechanical principles. Astronomy was the first to take to this path of reasoning, and succeeded in many cases in reducing astronomical to purely mechanical phenomena. Chemistry and physics, physiology and biology are proceeding in the same direction. One of the most important questions of all natural science, and one which has been handed down from the philosophers of classic times, is, whether the comprehension of all that is visible can be reduced to motion? Its participation in all, from the ‘fixed’ stars to the most minute parts of the coldest bodies (Dewar, in 1894 showed that many substances cooled to -180° fluoresce more strongly than at the ordinary temperature; i.e. that there is a motion in them which produces light) must now be recognised as undoubtable from direct experiment and observation, but it does not follow from this that by motion alone can all be explained. This follows, however, from the fact that we cannot apprehend motion otherwise than by recognising matter in a state of motion. If light and electricity be understood as particular forms of motion, then we must inevitably recognise the existence of a peculiar luminiferous (universal) ether as a material, transmitting this form of motion. And so, under the present state of knowledge, it is inevitably necessary to recognise the particular categories, motion and matter, and as chemistry is more closely concerned with the various forms of the latter, it should, together with mechanics or the study of motion, lie at the basis of natural science.

[4] The verb ‘to react’ means to act or change chemically.

[5] If a phenomenon proceeds at visible or measurable distances (as, for instance, magnetic attraction or gravity), it cannot be described as chemical, since these phenomena only take place at distances immeasurably small and undistinguishable to the eye or the microscope; that is to say, they are purely molecular.

[6] For this purpose a piece of iron may be made red hot in a forge, and then placed in contact with a lump of sulphur, when iron sulphide will be obtained as a molten liquid, the combination being accompanied by a visible increase in the glow of the iron. Or else iron filings are mixed with powdered sulphur in the proportion of 5 parts of iron to 3 parts of sulphur, and the mixture placed in a glass tube, which is then heated in one place. Combination does not commence without the aid of external heat, but when once started in any portion of the mixture it extends throughout the entire mass, because the portion first heated evolves sufficient heat in forming iron sulphide to raise the adjacent parts of the mixture to the temperature required for starting the reaction. The rise in temperature thus produced is so high as to soften the glass tube.

[7] Sulphur is slightly soluble in many thin oils; it is very soluble in carbon bisulphide and in some other liquids. Iron is insoluble in carbon bisulphide, and the sulphur therefore can be dissolved away from the iron.

[8] Decomposition of this kind is termed ‘dry distillation,’ because, as in distillation, the substance is heated and vapours are given off which, on cooling, condense into liquids. In general, decomposition, in absorbing heat, presents much in common to a physical change of state—such as, for example, that of a liquid into a gas. Deville likened complete decomposition to boiling, and compared partial decomposition, when a portion of a substance is not decomposed in the presence of its products of decomposition (or dissociation), to evaporation.

[9] A reaction of rearrangement may in certain cases take place with one substance only; that is to say, a substance may by itself change into a new isomeric form. Thus, for example, if hard yellow sulphur be heated to a temperature of 250° and then poured into cold water it gives, on cooling, a soft, brown variety. Ordinary phosphorus, which is transparent, poisonous, and phosphorescent in the dark (in the air), gives, after being heated at 270° (in an atmosphere incapable of supporting combustion, such as steam), an opaque, red, and non-poisonous isomeric variety, which is not phosphorescent. Cases of isomerism point out the possibility of an internal rearrangement in a substance, and are the result of an alteration in the grouping of the same elements, just as a certain number of balls may be grouped in figures and forms of different shapes.

[10] Thus the ancients knew how to convert the juice of grapes containing the saccharine principle (glucose) into wine or vinegar, how to extract metals from the ores which are found in the earth's crust, and how to prepare glass from earthy substances.

[11] The experiments conducted by Staas (described in detail in Chap. XXIV. on Silver) form some of the accurate researches, proving that the weight of matter is not altered in chemical reactions, because he accurately weighed (introducing all the necessary corrections) the reacting and resultant substances. Landolt (1893) carried on various reactions in inverted and sealed glass U-tubes, and on weighing the tubes before reaction (when the reacting solutions were separated in each of the branches of the tubes), and after (when the solutions had been well mixed together by shaking), found that either the weight remained perfectly constant or that the variation was so small (for instance, 0·2 milligram in a total weight of about a million milligrams) as to be ascribed to the inevitable errors of weighing.

[11 bis] The idea of the mass of matter was first shaped into an exact form by Galileo (died 1642), and more especially by Newton (born 1643, died 1727), in the glorious epoch of the development of the principles of inductive reasoning enunciated by Bacon and Descartes in their philosophical treatises. Shortly after the death of Newton, Lavoisier, whose fame in natural philosophy should rank with that of Galileo and Newton, was born on August 26, 1743. The death of Lavoisier occurred during the Reign of Terror of the French Revolution, when he, together with twenty-six other chief farmers of the revenue, was guillotined on May 8, 1794, at Paris; but his works and ideas have made him immortal.

[12] By covering iron with an enamel, or varnish, or with unrustable metals (such as nickel), or a coating of paraffin, or other similar substances, it is protected from the air and moisture, and so kept from rusting.

[13] Such an experiment may easily be made by taking the finest (unrusted) iron filings (ordinary filings must be first washed in ether, dried, and passed through a very fine sieve). The filings thus obtained are capable of burning directly in air (by oxidising or forming rust), especially when they hang (are attracted) on a magnet. A compact piece of iron does not burn in air, but spongy iron glows and smoulders like tinder. In making the experiment, a horse-shoe magnet is fixed, with the poles downwards, on one arm of a rather sensitive balance, and the iron filings are applied to the magnet (on a sheet of paper) so as to form a beard about the poles. The balance pan should be exactly under the filings on the magnet, in order that any which might fall from it should not alter the weight. The filings, having been weighed, are set light to by applying the flame of a candle; they easily take fire, and go on burning by themselves, forming rust. When the combustion is ended, it will be clear that the iron has increased in weight; from 5½ parts by weight of iron filings taken, there are obtained, by complete combustion, 7½ parts by weight of rust.

[14] For the purpose of experiment, it is most convenient to take copper carbonate, which may be prepared by the experimenter himself, by adding a solution of sodium carbonate to a solution of copper sulphate. The precipitate (deposit) so formed is collected on a filter, washed, and dried. The decomposition of copper carbonate into copper oxide is effected by so moderate a heat that it may be performed in a glass vessel heated by a lamp. For this purpose a thin glass tube, closed at one end, and called a ‘test tube,’ may be employed, or else a vessel called a ‘retort.’ The experiment is carried on, as described in example three on p. 11, by collecting the carbonic anhydride over water, as will be afterwards explained.

[15] Gas delivery tubes are usually made of glass tubing of various diameters and thicknesses. If of small diameter and thickness, a glass tube is easily bent by heating in a gas jet or the flame of a spirit lamp, and it may also be easily divided at a given point by making a deep scratch with a file and then breaking the tube at this point with a sharp jerk. These properties, together with their impermeability, transparency, hardness, and regularity of bore, render glass tubes most useful in experiments with gases. Naturally they might be replaced by straws, india-rubber, metallic, or other tubes, but these are more difficult to fix on to a vessel, and are not entirely impervious to gases. A glass gas delivery tube may be hermetically fixed into a vessel by fitting it into a perforated cork, which should be soft and free from flaws, and fixing the cork into the orifice of the vessel. To protect the cork from the action of gases it is sometimes previously soaked in paraffin, or it may be replaced by an india-rubber cork.

[16] Gases, like all other substances, may be weighed, but, owing to their extreme lightness and the difficulty of dealing with them in large masses, they can only be weighed by very sensitive balances; that is, in such as, with a considerable load, indicate a very small difference in weight—for example, a centigram or a milligram with a load of 1,000 grams. In order to weigh a gas, a glass globe furnished with a tight-fitting stop-cock is first of all exhausted of air by an air-pump (a Sprengel pump is the best). The stop-cock is then closed, and the exhausted globe weighed. If the gas to be weighed is then let into the globe, its weight can be determined from the increase in the weight of the globe. It is necessary, however, that the temperature and pressure of the air about the balance should remain constant for both weighings, as the weight of the globe in air will (according to the laws of hydrostatics) vary with its density. The volume of the air displaced, and its weight, must therefore be determined by observing the temperature, density, and moisture of the atmosphere during the time of experiment. This will be partly explained later, but may be studied more in detail by physics. Owing to the complexity of all these operations, the mass of a gas is usually determined from its volume and density, or from the weight of a known volume.

[17] The copper carbonate should be dried before weighing, as otherwise—besides copper oxide and carbonic anhydride—water will be obtained in the decomposition. Water forms a part of the composition of malachite, and has therefore to be taken into consideration. The water produced in the decomposition may be all collected by absorbing it in sulphuric acid or calcium chloride, as will be described further on. In order to dry a salt it must be heated at about 100° until its weight remains constant, or be placed under an air pump over sulphuric acid, as will also be presently described. As water is met with almost everywhere, and as it is absorbed by many substances, the possibility of its presence should never be lost sight of.

[18] As the decomposition of red oxide of mercury requires so high a temperature, near redness, as to soften ordinary glass, it is necessary for this experiment to take a retort (or test tube) made of hard glass, which is able to stand high temperatures without softening. For the same reason, the lamp used must give a strong heat and a large flame, capable of embracing the whole bottom of the retort, which should be as small as possible for the convenience of the experiment.

[19] The pneumatic trough may naturally be made of any material (china, earthenware, or metal, &c.), but usually a glass one, as shown in the drawing, is used, as it allows the progress of the experiment to be better observed. For this reason, as well as the ease with which they are kept clean, and from the fact also that glass is not acted on by many substances which affect other materials (for instance, metals), glass vessels of all kinds—such as retorts, test tubes, cylinders, beakers, flasks, globes, &c.—are preferred to any other for chemical experiments. Glass vessels may be heated without any danger if the following precautions be observed: 1st, they should be made of thin glass, as otherwise they are liable to crack from the bad heat-conducting power of glass; 2nd, they should be surrounded by a liquid or with sand (Fig. 2), or sand bath as it is called; or else should stand in a current of hot gases without touching the fuel from which they proceed, or in the flame of a smokeless lamp. A common candle or lamp forms a deposit of soot on a cold object placed in their flames. The soot interferes with the transmission of heat, and so a glass vessel when covered with soot often cracks. And for this reason spirit lamps, which burn with a smokeless flame, or gas burners of a peculiar construction, are used. In the Bunsen burner the gas is mixed with air, and burns with a non-luminous and smokeless flame. On the other hand, if an ordinary lamp (petroleum or benzine) does not smoke it may be used for heating a glass vessel without danger, provided the glass is placed well above the flame in the current of hot gases. In all cases, the heating should be begun very carefully by raising the temperature by degrees.

Fig. 2.—Apparatus for distilling under a diminished pressure liquids which decompose at their boiling points under the ordinary pressure. The apparatus in which the liquid is distilled is connected with a large globe from which the air is pumped out; the liquid is heated, and the receiver cooled.

[20] In order to avoid the necessity of holding the cylinder, its open end is widened (and also ground so that it may be closely covered with a ground-glass plate when necessary), and placed on a stand below the level of the water in the bath. This stand is called ‘the bridge.’ It has several circular openings cut through it, and the gas delivery tube is placed under one of these, and the cylinder for collecting the gas over it.

[21] Drying is necessary in order to remove any water which may be held in the salts (see Note 17, and Chapter I., Notes 13 and 14).

[22] The exact weights of the re-acting and resulting substances are determined with the greatest difficulty, not only from the possible inexactitude of the balance (every weighing is only correct within the limits of the sensitiveness of the balance) and weights used in weighing, not only from the difficulty in making corrections for the weight of air displaced by the vessels holding the substances weighed and by the weights themselves, but also from the hygroscopic nature of many substances (and vessels) causing absorption of moisture from the atmosphere, and from the difficulty in not losing any of the substance to be weighed in the several operations (filtering, evaporating, and drying, &c.) which have to be performed before arriving at a final result. All these circumstances have to be taken into consideration in exact researches, and their elimination requires very many special precautions which are impracticable in preliminary experiments.

[23] Besides which, in the majority of cases, the first explanation of most subjects which do not repeat themselves in everyday experience under various aspects, but always in one form, or only at intervals and infrequently, is usually wrong. Thus the daily evidence of the rising of the sun and stars evokes the erroneous idea that the heavens move and the earth stands still. This apparent truth is far from being the real truth, and, as a matter of fact, is contradictory to it. Similarly, an ordinary mind and everyday experience concludes that iron is incombustible, whereas it burns not only as filings, but even as wire, as we shall afterwards see. With the progress of knowledge very many primitive prejudices have been obliged to give way to true ideas which have been verified by experiment. In ordinary life we often reason at first sight with perfect truth, only because we are taught a right judgment by our daily experience. It is a necessary consequence of the nature of our minds to reach the attainment of truth through elementary and often erroneous reasoning and through experiment, and it would be very wrong to expect a knowledge of truth from a simple mental effort. Naturally, experiment itself cannot give truth, but it gives the means of destroying erroneous representations whilst confirming those which are true in all their consequences.

[24] It is true that Stahl was acquainted with a fact which directly disproved his hypothesis. It was already known (from the experiments of Geber, and more especially of Ray, in 1630) that metals increase in weight by oxidation, whilst, according to Stahl's hypothesis, they should decrease in weight, because phlogiston is separated by oxidation. Stahl speaks on this point as follows:—‘I am well aware that metals, in their transformation into earths, increase in weight. But not only does this fact not disprove my theory, but, on the contrary, confirms it, for phlogiston is lighter than air, and, in combining with substances, strives to lift them, and so decreases their weight; consequently, a substance which has lost phlogiston must be heavier.’ This argument, it will be seen, is founded on a misconception of the properties of gases, regarding them as having no weight and as not being attracted by the earth, or else on a confused idea of phlogiston itself, since it was first defined as imponderable. The conception of imponderable phlogiston tallies well with the habit and methods of the last century, when recourse was often had to imponderable fluids for explaining a large number of phenomena. Heat, light, magnetism, and electricity were explained as being peculiar imponderable fluids. In this sense the doctrine of Stahl corresponds entirely with the spirit of his age. If heat be now regarded as motion or energy, then phlogiston also should be considered in this light. In fact, in combustion, of coals for instance, heat and energy are evolved, and not combined in the coal, although the oxygen and coal do combine. Consequently, the doctrine of Stahl contains the essence of a true representation of the evolution of energy, but naturally this evolution is only a consequence of the combination occurring between the coal and oxygen. As regards the history of chemistry prior to Lavoisier, besides Stahl's work (to which reference has been made above), Priestley's Experiments and Observations on Different Kinds of Air, London, 1790, and also Scheele's Opuscula Chimica et Physica, Lips., 1788–89, 2 vols., must be recommended as the two leading works of the English and Scandinavian chemists showing the condition of chemical learning before the propagation of Lavoisier's views, and containing also many important observations which lie at the basis of the chemistry of our times. A most interesting memoir on the history of phlogiston is that of Rodwell, in the Philosophical Magazine, 1868, in which it is shown that the idea of phlogiston dates very far back, that Basil Valentine (1394–1415), in the Cursus Triumphalis Antimonii, Paracelsus (1493–1541), in his work, De Rerum Natura, Glauber (1604–1668), and especially John Joachim Becher (1625–1682), in his Physica Subterranea, all referred to phlogiston, but under different names.

[25] An Englishman, named Mayow, who lived a whole century before Lavoisier (in 1666), understood certain phenomena of oxidation in their true aspect, but was not able to develop his views with clearness, or support them by conclusive experiments; he cannot therefore be considered, like Lavoisier, as the founder of contemporary chemical learning. Science is a universal heritage, and therefore it is only just to give the highest honour in science, not to those who first enunciate a certain truth, but to those who are first able to convince others of its authenticity and establish it for the general welfare. But scientific discoveries are rarely made all at once; as a rule, the first teachers do not succeed in convincing others of the truth they have discovered; with time, however, a true herald comes forward, possessing every means for making the truth apparent to all, but it must not be forgotten that such are entirely indebted to the labours and mass of data accumulated by many others. Such was Lavoisier, and such are all the great founders of science. They are the enunciators of all past and present learning, and their names will always be revered by posterity.

[26] Many of the ancient philosophers assumed the existence of one elementary form of matter. This idea still appears in our times, in the constant efforts which are made to reduce the number of the elements; to prove, for instance, that bromine contains chlorine or that chlorine contains oxygen. Many methods, founded both on experiment and theory, have been tried to prove the compound nature of the elements. All labour in this direction has as yet been in vain, and the assurance that elementary matter is not so homogeneous (single) as the mind would desire in its first transport of rapid generalisation is strengthened from year to year. All our knowledge shows that iron and other elements remain, even at such a high temperature as there exists in the sun, as different substances, and are not converted into one common material. Admitting, even mentally, the possibility of one elementary form of matter, a method must be imagined by which it could give rise to the various elements, as also the modus operandi of their formation from one material. If it be said that this diversitude only takes place at low temperatures, as is observed with isomerides, then there would be reason to expect, if not the transition of the various elements into one particular and more stable form, at least the mutual transformation of some into others. But nothing of the kind has as yet been observed, and the alchemist's hope to manufacture (as Berthollet puts it) elements has no theoretical or practical foundation.

[27] The weakest point in the idea of elements is the negative character of the determinative signs given them by Lavoisier, and from that time ruling in chemistry. They do not decompose, they do not change into one another. But it must be remarked that elements form the limiting horizon of our knowledge of matter, and it is always difficult to determine a positive side on the borderland of what is known. Besides, there is no doubt (from the results of spectrum analysis) that the elements are distributed as far as the most distant stars, and that they support the highest attainable temperatures without decomposing.

[28] Possibly some of their compounds are compounds of other already-known elements. Pure and incontestably independent compounds of these substances are unknown, and some of them have not even been separated, but are only supposed to exist from the results of spectroscopic researches. There can be no mention of such contestable and doubtful elements in a short general handbook of chemistry.

[28 bis] Clark in America made an approximate calculation of the amount of the different elements contained in the earth's crust (to a depth of 15 kilometres), and found that the chief mass (over 50 per cent.) is composed of oxygen; then comes silicon, &c.; while the amount of hydrogen is less than 1 per cent., carbon scarcely 0·25 per cent., nitrogen even less than 0·03 per cent. The relative masses of such metals as Cu, Ni, Au is minute. Judging from the density (see Chapter VIII.) of the earth, a large proportion of its mass must be composed of iron.

[29] This word, first introduced, if I mistake not, into chemistry by Glauber, is based on the idea of the ancient philosophers that combination can only take place when the substances combining have something in common—a medium. As is generally the case, another idea evolved itself in antiquity, and has lived until now, side by side with the first, to which it is exactly contradictory; this considers union as dependent on contrast, on polar difference, on an effort to fill up a want.

[30] Especially conclusive are those cases of so-called metalepsis (Dumas, Laurent). Chlorine, in combining with hydrogen, forms a very stable substance called ‘hydrochloric acid,’ which is split up by the action of an electrical current into chlorine and hydrogen, the chlorine appearing at the positive and the hydrogen at the negative pole. Hence electro-chemists considered hydrogen to be an electro-positive and chlorine an electro-negative element, and that they are held together in virtue of their opposite electrical charges. It appears, however, from metalepsis, that chlorine can replace hydrogen (and, inversely, hydrogen can replace chlorine) in its compounds without in any way changing the grouping of the other elements, or altering their chief chemical properties. For instance, acetic acid in which hydrogen has been replaced by chlorine is still capable of forming salts. It must be observed, whilst considering this subject, that the explanation suggesting electricity as the origin of chemical phenomena is unsound, since it attempts to explain one class of phenomena whose nature is almost unknown by another class which is no better known. It is most instructive to remark that together with the electrical theory of chemical attraction there arose and survives a view which explains the galvanic current as being a transference of chemical action through the circuit—i.e., regards the origin of electricity as being a chemical one. It is evident that the connection is very intimate, although both phenomena are independent and represent different forms of molecular (atomic) motion, whose real nature is not yet understood. Nevertheless, the connection between the phenomena of both categories is not only in itself very instructive, but it extends the applicability of the general idea of the unity of the forces of nature, conviction of the truth of which has held so important a place in the science of the last ten years.

[31] I consider that in an elementary text-book of chemistry, like the present, it is only possible and advisable to mention, in reference to chemical mechanics, a few general ideas and some particular examples referring more especially to gases, whose mechanical theory must be regarded as the most complete. The molecular mechanics of liquids and solids is as yet in embryo, and contains much that is disputable; for this reason, chemical mechanics has made less progress in relation to these substances. It may not be superfluous here to remark, with respect to the conception of chemical affinity, that up to the present time gravity, electricity, and heat have all been applied to its elucidation. Efforts have also been made to introduce the luminiferous ether into theoretical chemistry, and should that connection between the phenomena of light and electricity which was established by Maxwell be worked out more in detail, doubtless these efforts to elucidate all or a great deal by the aid of luminiferous ether will again appear in theoretical chemistry. An independent chemical mechanics of the material particles of matter, and of their internal (atomic) changes, would, in my opinion, arise as the result of these efforts. Two hundred years ago Newton laid the foundation of a truly scientific theoretical mechanics of external visible motion, and on this foundation erected the edifice of celestial mechanics. One hundred years ago Lavoisier arrived at the first fundamental law of the internal mechanics of invisible particles of matter. This subject is far from having been developed into a harmonious whole, because it is much more difficult, and, although many details have been completely investigated, it does not possess any starting points. Newton only came after Copernicus and Kepler, who had discovered empirically the exterior simplicity of celestial phenomena. Lavoisier and Dalton may, in respect to the chemical mechanics of the molecular world, be compared to Copernicus and Kepler. But a Newton has not yet appeared in the molecular world; when he does, I think that he will find the fundamental laws of the mechanics of the invisible motions of matter more easily and more quickly in the chemical structure of matter than in physical phenomena (of electricity, heat, and light); for these latter are accomplished by particles of matter already arranged, whilst it is now clear that the problem of chemical mechanics mainly lies in the apprehension of those motions which are invisibly accomplished by the smallest atoms of matter.

[32] The theory of heat gave the idea of a store of internal motion or energy, and therefore with it, it became necessary to acknowledge chemical energy, but there is no foundation whatever for identifying heat energy with chemical energy. It may be supposed, but not positively affirmed, that heat motion is proper to molecules and chemical motion to atoms, but that as molecules are made up of atoms, the motion of the one passes to the other, and that for this reason heat strongly influences reaction and appears or disappears (is absorbed) in reactions. These relations, which are apparent and hardly subject to doubt on general lines, still present much that is doubtful in detail, because all forms of molecular and atomic motion are able to pass into each other.

[33] The reactions which take place (at the ordinary or at a high temperature) directly between substances may be clearly divided into exothermal, which are accompanied by an evolution of heat, and endothermal, which are accompanied by an absorption of heat. It is evident that the latter require a source of heat. They are determined either by the directly surrounding medium (as in the formation of carbon bisulphide from charcoal and sulphur, or in decompositions which take place at high temperatures), or else by a secondary reaction proceeding simultaneously, or by some other form of energy (light, electricity). So, for instance, hydrogen sulphide is decomposed by iodine in the presence of water at the expense of the heat which is evolved by the solution in water of the hydrogen iodide produced. This is the reason why this reaction, as exothermal, only takes place in the presence of water; otherwise it would be accompanied by a cooling effect. As in the combination of dissimilar substances, the bonds existing between the molecules and atoms of the homogeneous substances have to be broken asunder, whilst in reactions of rearrangement the formation of any one substance proceeds simultaneously with the formation of another, and, as in reactions, a series of physical and mechanical changes take place, it is impossible to separate the heat directly depending on a given reaction from the total sum of the observed heat effect. For this reason, thermochemical data are very complex, and cannot by themselves give the key to many chemical problems, as it was at first supposed they might. They ought to form a part of chemical mechanics, but alone they do not constitute it.

[34] As chemical reactions are effected by heating, so the heat absorbed by substances before decomposition or change of state, and called ‘specific heat,’ goes in many cases to the preparation, if it may be so expressed, of reaction, even when the limit of the temperature of reaction is not attained. The molecules of a substance A, which is not able to react on a substance B below a temperature t, by being heated from a somewhat lower temperature to t, undergoes that change which had to be arrived at for the formation of A B.

[35] It is possible to imagine that the cause of a great many of such reactions is, that substances taken in a separate state, for instance, charcoal, present a complex molecule composed of separate atoms of carbon which are fastened together (united, as is usually said) by a considerable affinity; for atoms of the same kind, just like atoms of different kinds, possess a mutual affinity. The affinity of chlorine for carbon, although unable to break this bond asunder, may be sufficient to form a stable compound with atoms of carbon, which are already separate. Such a view of the subject presents a hypothesis which, although dominant at the present time, is without sufficiently firm foundation. It is evident, however, that not only does chemical reaction itself consist of motions, but that in the compound formed (in the molecules) the elements (atoms) forming it are in harmonious stable motion (like the planets in the solar system), and this motion will affect the stability and capacity for reaction, and therefore the mechanical side of chemical action must be exceedingly complex. Just as there are solid, physically constant non-volatile substances like rock, gold, charcoal, &c., so are there stable and chemically constant bodies; while corresponding to physically volatile substances there are bodies like camphor, which are chemically unstable and variable.

[36] Contact phenomena are separately considered in detail in the work of Professor Konovaloff (1884). In my opinion, it must be held that the state of the internal motions of the atoms in molecules is modified at the points of contact of substances, and this state determines chemical reactions, and therefore, that reactions of combination, decomposition, and rearrangement are accomplished by contact. Professor Konovaloff showed that a number of substances, under certain conditions of their surfaces, act by contact; for instance, finely divided silica (from the hydrate) acts just like platinum, decomposing certain compound ethers. As reactions are only accomplished under close contact, it is probable that those modifications in the distribution of the atoms in molecules which come about by contact phenomena prepare the way for them. By this the rôle of contact phenomena is considerably extended. Such phenomena should explain the fact why a mixture of hydrogen and oxygen yields water (explodes) at different temperatures, according to the kind of heated substance which transmits this temperature. In chemical mechanics, phenomena of this kind have great importance, but as yet they have been but little studied. It must not be forgotten that contact is a necessary condition for every chemical reaction.

[1] In practice, the chemist has to continually deal with gases, and gases are often collected over water; in which case a certain amount of water passes into vapour, and this vapour mixes with the gases. It is therefore most important that he should be able to calculate the amount of water or of moisture in air and other gases. Let us imagine a cylinder standing in a mercury bath, and filled with a dry gas whose volume equals v, temperature t°, and pressure or tension h mm. (h millimetres of the column of mercury at 0°). We will introduce water into the cylinder in such a quantity that a small part remains in the liquid state, and consequently that the gas will be saturated with aqueous vapour; the volume of the gas will then increase (if a larger quantity of water be taken some of the gas will he dissolved in it, and the volume may therefore he diminished). We will further suppose that, after the addition of the water, the temperature remains constant; then since the volume increases, the mercury in the cylinder falls, and therefore the pressure as well as the volume is increased. In order to investigate the phenomenon we will artificially increase the pressure, and reduce the volume to the original volume v. Then the pressure or tension will be greater than h, namely h + f, which means that by the introduction of aqueous vapour the pressure of the gas is increased. The researches of Dalton, Gay-Lussac, and Regnault showed that this increase is equal to the maximum pressure which is proper to the aqueous vapour at the temperature at which the observation is made. The maximum pressure for all temperatures may be found in the tables made from observations on the pressure of aqueous vapour. The quantity f will be equal to this maximum pressure of aqueous vapour. This may be expressed thus: the maximum tension of aqueous vapour (and of all other vapours) saturating a space in a vacuum or in any gas is the same. This rule is known as Dalton's law. Thus we have a volume of dry gas v, under a pressure h, and a volume of moist gas, saturated with vapour, under a pressure h + f. The volume v of the dry gas under a pressure h + f occupies, from Boyle's law, a volume vh / h + f consequently the volume occupied by the aqueous vapour under the pressure h + f equals v - vh / h + f , or vf / h + f . Thus the volumes of the dry gas and of the moisture which occurs in it, at a pressure h + f, are in the ratio f : h. And, therefore, if the aqueous vapour saturates a space at a pressure n, the volumes of the dry air and of the moisture which is contained in it are in the ratio (n - f) : f, where f is the pressure of the vapour according to the tables of vapour tension. Thus, if a volume N of a gas saturated with moisture be measured at a pressure H, then the volume of the gas, when dry, will be equal to N H - f / H . In fact, the entire volume N must be to the volume of dry gas x as H is to H - f; therefore, N : x = H : H - f, from which x = N H - f / H . Under any other pressure—for instance, 760 mm.—The volume of dry gas will be xH / 760 , or H - f / 760 , and we thus obtain the following practical rule: If a volume of a gas saturated with aqueous vapour be measured at a pressure H mm., then the volume of dry gas contained in it will be obtained by finding the volume corresponding to the pressure H, less the pressure due to the aqueous vapour at the temperature observed. For example, 37·5 cubic centimetres of air saturated with aqueous vapour were measured at a temperature of 15·3°, and under a pressure of 747·3 mm. of mercury (at 0°). What will be the volume of dry gas at 0° and 760 mm.?

The pressure of aqueous vapour corresponding to 15·3° is equal to 12·9 mm., and therefore the volume of dry gas at 15·3° and 747·3 mm. is equal to 37·5 × 747·3 - 12·9 / 747·3 ; at 760 mm. it will be equal to 37·5 × 734·4 / 760 ; and at 0° the volume of dry gas will be 37·5 × 734·4 / 760 × 273 / 273 + 15·3 = 34·31 c.c.

From this rule may also be calculated what fraction of a volume of gas is occupied by moisture under the ordinary pressure at different temperatures; for instance, at 30° C. f = 31·5, consequently 100 volumes of a moist gas or air, at 760 mm., contain a volume of aqueous vapour 100 × 31·5 / 760 , or 4·110; it is also found that at 0° there is contained 0·61 p.c. by volume, at 10° 1·21 p.c., at 20° 2·29 p.c., and at 50° up to 12·11 p.c. From this it may be judged how great an error might be made in the measurement of gases by volume if the moisture were not taken into consideration. From this it is also evident how great are the variations in volume of the atmosphere when it loses or gains aqueous vapour, which again explains a number of atmospheric phenomena (winds, variation of pressure, rainfalls, storms, &c.)

If a gas is not saturated, then it is indispensable that the degree of moisture should be known in order to determine the volume of dry gas from the volume of moist gas. The preceding ratio gives the maximum quantity of water which can be held in a gas, and the degree of moisture shows what fraction of this maximum quantity occurs in a given case, when the vapour does not saturate the space occupied by the gas. Consequently, if the degree of moisture equals 50 p.c.—that is, half the maximum—then the volume of dry gas at 760 mm. is equal to the volume of dry gas at 760 mm. multiplied by h - 0·5f / 760 , or, in general, by h - rf / 760 where r is the degree of moisture. Thus, if it is required to measure the volume of a moist gas, it must either be thoroughly dried or quite saturated with moisture, or else the degree of moisture determined. The first and last methods are inconvenient, and therefore recourse is usually had to the second. For this purpose water is introduced into the cylinder holding the gas to be measured; it is left for a certain time so that the gas may become saturated, the precaution being taken that a portion of the water remains in a liquid state; then the volume of the moist gas is determined, from which that of the dry gas may be calculated. In order to find the weight of the aqueous vapour in a gas it is necessary to know the weight of a cubic measure at 0° and 760 mm. Knowing that one cubic centimetre of air in these circumstances weighs 0·001293 gram, and that the density of aqueous vapour is 0·62, we find that one cubic centimetre of aqueous vapour at 0° and 760 mm. weighs 0·0008 gram, and at a temperature t° and pressure h the weight of one cubic centimetre will be 0·0008 × h / 760 × 273 / 273 + t . We already know that v volumes of a gas at a temperature t° pressure h contain v × f / h volumes of aqueous vapour which saturate it, therefore the weight of the aqueous vapour held in v volumes of a gas will be

v x 0·0008 × f / 760 × 273 / 273 + t

Accordingly, the weight of water which is contained in one volume of a gas depends only on the temperature and not on the pressure. This also signifies that evaporation proceeds to the same extent in air as in a vacuum, or, in general terms (this is Dalton's law), vapours and gases diffuse into each other as if into a vacuum. In a given space, at a given temperature, a constant quantity of vapour enters, whatever be the pressure of the gas filling that space.

From this it is clear that if the weight of the vapour contained in a given volume of a gas be known, it is easy to determine the degree of moisture r = p / v × 0·0008 × 760 / t × 273 + t / 273 . On the is founded the very exact determination of the degree of moisture of air by the weight of water contained in a given volume. It is easy to calculate from the preceding formula the number of grams of water contained at any pressure in one cubic metre or million cubic centimetres of air saturated with vapour at various temperatures; for instance, at 30° f = 31·5, hence p = 29·84 grams.

The laws of Mariotte, Dalton, and Gay-Lussac, which are here applied to gases and vapours, are not entirely exact, but are approximately true. If they were quite exact, a mixture of several liquids, having a certain vapour pressure, would give vapours of a very high pressure, which is not the case. In fact the pressure of aqueous vapour is slightly less in a gas than in a vacuum, and the weight of aqueous vapour held in a gas is slightly less than it should be according to Dalton's law, as was shown by the experiments of Regnault and others. This means that the tension of the vapour is less in air than in a vacuum. The difference does not, however, exceed 5 per cent. of the total pressure of the vapours. This decrement in vapour tension which occurs in the intermixture of vapours and gases, although small, indicates that there is then already, so to speak, a beginning of chemical change. The essence of the matter is that in this case there occurs, as on contact (see preceding footnote), an alteration in the motions of the atoms in the molecules, and therefore also a change in the motion of the molecules themselves.

In the uniform intermixture of air and other gases with aqueous vapour, and in the capacity of water to pass into vapour and form a uniform mixture with air, we may perceive an instance of a physical phenomenon which is analogous to chemical phenomena, forming indeed a transition from one class of phenomena to the other. Between water and dry air there exists a kind of affinity which obliges the water to saturate the air. But such a homogeneous mixture is formed (almost) independently of the nature of the gas in which evaporation takes place; even in a vacuum the phenomenon occurs in exactly the same way as in a gas, and therefore it is not the property of the gas, nor its relation to water, but the property of the water itself, which compels it to evaporate, and therefore in this case chemical affinity is not yet operative—at least its action is not clearly pronounced. That it does, however, play a certain part is seen from the deviation from Dalton's law.

[2] In falling through the atmosphere, water dissolves the gases of the atmosphere, nitric acid, ammonia, organic compounds, salts of sodium, magnesium, and calcium, and mechanically washes out a mixture of dust and microbes which are suspended in the atmosphere. The amount of these and certain other constituents is very variable. Even in the beginning and end of the same rainfall a variation which is often very considerable may be remarked. Thus, for example, Bunsen found that rain collected at the beginning of a shower contained 3·7 grams of ammonia per cubic metre, whilst that collected at the end of the same shower contained only O·64 gram. The water of the entire shower contained an average of 1·47 gram of ammonia per cubic metre. In the course of a year rain supplies an acre of ground with as much as 5½ kilos of nitrogen in a combined form. Marchand found in one cubic metre of snow water 15·63, and in one cubic metre of rain water 10·07, grams of sodium sulphate. Angus Smith showed that after a thirty hours' fall at Manchester the rain still contained 34·3 grams of salts per cubic metre. A considerable amount of organic matter, namely 25 grams per cubic metre, has been found in rain water. The total amount of solid matter in rain water reaches 50 grams per cubic metre. Rain water generally contains very little carbonic acid, whilst river water contains a considerable quantity of it. In considering the nourishment of plants it is necessary to keep in view the substances which are carried into the soil by rain.

River water, which is accumulated from springs and sources fed by atmospheric water, contains from 50 to 1,600 parts by weight of salts in 1,000,000 parts. The amount of solid matter, per 1,000,000 parts by weight, contained in the chief rivers is as follows:—the Don 124, the Loire 135, the St. Lawrence 170, the Rhone 182, the Dnieper 187, the Danube from 117 to 234, the Rhine from 158 to 317, the Seine from 190 to 432, the Thames at London from 400 to 450, in its upper parts 387, and in its lower parts up to 1,617, the Nile 1,580, the Jordan 1,052. The Neva is characterised by the remarkably small amount of solid matter it contains. From the investigations of Prof. G. K. Trapp, a cubic metre of Neva water contains 32 grams of incombustible and 23 grams of organic matter, or altogether about 55 grams. This is one of the purest waters which is known in rivers. The large amount of impurities in river water, and especially of organic impurity produced by pollution with putrid matter, makes the water of many rivers unfit for use.

The chief part of the soluble substances in river water consists of the calcium salts. 100 parts of the solid residues contain the following amounts of calcium carbonate—from the water of the Loire 53, from the Thames about 50, the Elbe 55, the Vistula 65, the Danube 65, the Rhine from 55 to 75, the Seine 75, the Rhone from 82 to 94. The Neva contains 40 parts of calcium carbonate per 100 parts of saline matter. The considerable amount of calcium carbonate which river water contains is very easily explained from the fact that water which contains carbonic acid in solution easily dissolves calcium carbonate, which occurs all over the earth. Besides calcium carbonate and sulphate, river water contains magnesium, silica, chlorine, sodium, potassium, aluminium, nitric acid, iron and manganese. The presence of salts of phosphoric acid has not yet been determined with exactitude for all rivers, but the presence of nitrates has been proved with certainty in almost all kinds of well-investigated river water. The quantity of calcium phosphate does not exceed 0·4 gram in the water of the Dnieper, and the Don does not contain more than 5 grams. The water of the Seine contains about 15 grams of nitrates, and that of the Rhone about 8 grams. The amount of ammonia is much less; thus in the water of the Rhine about 0·5 gram in June, and 0·2 gram in October; the water of the Seine contains the same amount. This is less than in rain water. Notwithstanding this insignificant quantity, the water of the Rhine alone, which is not so very large a river, carries 16,245 kilograms of ammonia into the ocean every day. The difference between the amount of ammonia in rain and river water depends on the fact that the soil through which the rain water passes is able to retain the ammonia. (Soil can also absorb many other substances, such as phosphoric acid, potassium salts, &c.)

The waters of springs, rivers, wells, and in general of those localities from which it is taken for drinking purposes, may be injurious to health if it contains much organic pollution, the more so as in such water the lower organisms (bacteria) may rapidly develop, and these organisms often serve as the carriers or causes of infectious diseases. For instance, certain pathogenic (disease-producing) bacteria are known to produce typhoid, the Siberian plague, and cholera. Thanks to the work of Pasteur, Metchnikoff, Koch, and many others, this province of research has made considerable progress. It is possible to investigate the number and properties of the germs in water. In bacteriological researches a gelatinous medium in which the germs can develop and multiply is prepared with gelatin and water, which has previously been heated several times, at intervals, to 100° (it is thus rendered sterile—that is to say, all the germs in it are killed). The water to be investigated is added to this prepared medium in a definite and small quantity (sometimes diluted with sterilised water to facilitate the calculation of the number of germs), it is protected from dust (which contains germs), and is left at rest until whole families of lower organisms are developed from each germ. These families (colonies) are visible to the naked eye (as spots), they may be counted, and by examining them under the microscope and observing the number of organisms they produce, their significance may be determined. The majority of bacteria are harmless, but there are decidedly pathogenic bacteria, whose presence is one of the causes of malady and of the spread of certain diseases. The number of bacteria in one cubic centimetre of water sometimes attains the immense figures of hundreds of thousands and millions. Certain well, spring, and river waters contain very few bacteria, and are free from disease-producing bacteria under ordinary circumstances. By boiling water, the bacteria in it are killed, but the organic matter necessary for their nourishment remains in the water. The best kinds of water for drinking purposes do not contain more than 300 bacteria in a cubic centimetre.

The amount of gases dissolved in river water is much more constant than that of its solid constituents. One litre, or 1,000 c.c., of water contains 40 to 55 c.c. of gas measured at normal temperature and pressure. In winter the amount of gas is greater than in summer or autumn. Assuming that a litre contains 50 c.c. of gases, it may be admitted that these consist, on an average, of 20 vols. of nitrogen, 20 vols of carbonic anhydride (proceeding in all likelihood from the soil and not from the atmosphere), and of 10 vols. of oxygen. If the total amount of gases be less, the constituent gases are still in about the same proportion; in many cases, however, carbonic anhydride predominates. The water of many deep and rapid rivers contains less carbonic anhydride, which shows their rapid formation from atmospheric water, and that they have not succeeded, during a long and slow course, in absorbing a greater quantity of carbonic anhydride. Thus, for instance, the water of the Rhine, near Strasburg, according to Deville, contains 8 c.c. of carbonic anhydride, 16 c.c. of nitrogen, and 7 c.c. of oxygen per litre. From the researches of Prof. M. R. Kapoustin and his pupils, it appears that in determining the quality of a water for drinking purposes, it is most important to investigate the composition of the dissolved gases, more especially oxygen.

[3] Spring water is formed from rain water percolating through the soil. Naturally a part of the rain water is evaporated directly from the surface of the earth and from the vegetation on it. It has been shown that out of 100 parts of water falling on the earth only 36 parts flow to the ocean; the remaining 64 are evaporated, or percolate far underground. After flowing underground along some impervious strata, water comes out at the surface in many places as springs, whose temperature is determined by the depth from which the water has flowed. Springs penetrating to a great depth may become considerably heated, and this is why hot mineral springs, with a temperature of up to 30° and higher, are often met with. When a spring water contains substances which endow it with a peculiar taste, and especially if these substances are such as are only found in minute quantities in river and other flowing waters, then the spring water is termed a mineral water. Many such waters are employed for medicinal purposes. Mineral waters are classed according to their composition into—(a) saline waters, which often contain a large amount of common salt; (b) alkaline waters, which contain sodium carbonate; (c) bitter waters, which contain magnesia; (d) chalybeate waters, which hold iron carbonate in solution; (e) aërated waters, which are rich in carbonic anhydride; (f) sulphuretted waters, which contain hydrogen sulphide. Sulphuretted waters may be recognised by their smell of rotten eggs, and by their giving a black precipitate with lead salts, and also by their tarnishing silver objects. Aërated waters, which contain an excess of carbonic anhydride, effervesce in the air, have a sharp taste, and redden litmus paper. Saline waters leave a large residue of soluble solid matter on evaporation, and have a salt taste. Chalybeate waters have an inky taste, and are coloured black by an infusion of galls; on being exposed to the air they usually give a brown precipitate. Generally, the character of mineral waters is mixed. In the table below the analyses are given of certain mineral springs which are valued for their medicinal properties. The quantity of the substances is expressed in millionths by weight.

I. Sergieffsky, a sulphur water, Gov. of Samara (temp. 8° C.), analysis by Clause. II. Geléznovodskya water source No. 10, near Patigorsk, Caucasus (temp. 22·5°), analysis by Fritzsche. III. Aleksandroffsky, alkaline-sulphur source, Patigorsk (temp. 46·5°), average of analyses by Herman, Zinin and Fritzsche. IV. Bougountouksky, alkaline source, No. 17, Essentoukah, Caucasus (temp. 21·6°), analysis by Fritzsche. V. Saline water, Staro-Russi, Gov. of Novgorod, analysis by Nelubin. VI. Water from artesian well at the factory of state papers, St. Petersburg, analysis by Struve. VII. Sprüdel, Carlsbad (temp. 83·7°), analysis by Berzelius. VIII. Kreuznach spring (Elisenquelle), Prussia (temp. 8·8°), analysis by Bauer. IX. Eau de Seltz, Nassau, analysis by Henry. X. Vichy water, France, analysis by Berthier and Puvy. XI. Paramo de Ruiz, New Granada, analysis by Levy; it is distinguished by the amount of free acids.

[4] Sea water contains more non-volatile saline constituents than the usual kinds of fresh water. This is explained by the fact that the waters flowing into the sea supply it with salts, and whilst a large quantity of vapour is given off from the surface of the sea, the salts remain behind. Even the specific gravity of sea water differs considerably from that of pure water. It is generally about 1·02, but in this and also in respect of the amount of salts contained, samples of sea water from different localities and from different depths offer rather remarkable variations. It will be sufficient to point out that one cubic metre of water from the undermentioned localities contains the following quantity in grams of solid constituents:—Gulf of Venice, 19,122; Leghorn Harbour 24,312; Mediterranean, near Cetta, 37,665; the Atlantic Ocean from 32,585 to 35,695,; the Pacific Ocean from 35,233 to 34,708. In closed seas which do not communicate, or are in very distant communication, with the ocean, the difference is often still greater. Thus the Caspian Sea contains 6,300 grams; the Black Sea and Baltic 17,700. Common salt forms the chief constituent of the saline matter of sea or ocean water; thus in one cubic metre of sea water there are 25,000–31,000 grams of common salt, 2,600–6,000 grams of magnesium chloride, 1,200–7,000 grams of magnesium sulphate, 1,500–6,000 grams of calcium sulphate, and 10–700 grams of potassium chloride. The small amount of organic matter and of the salts of phosphoric acid in sea water is very remarkable. Sea water (the composition of which is partially discussed in Chapter X.) contains, in addition to salts of common occurrence, a certain and sometimes minute amount of the most varied elements, even gold and silver, and as the mass of water of the oceans is so enormous these ‘traces’ of rare substances amount to large quantities, so that it may be hoped that in time methods will be found to extract even gold from sea water, which by means of the rivers forms a vast reservoir for the numerous products of the changes taking place on the earth's surface. The works of English, American, German, Russian, Swedish, and other navigators and observers prove that a study of the composition of sea water not only explains much in the history of the earth's life, but also gives the possibility (especially since the researches of C. O. Makaroff of the St. Petersburg Academy) of fixing one's position in the ocean in the absence of other means, for instance, in a fog, or in the dark.

[5] The taste of water is greatly dependent on the quantity of dissolved gases it contains. These gases are given off on boiling, and it is well known that, even when cooled, boiled water has, until it has absorbed gaseous substances from the atmosphere, quite a different taste from fresh water containing a considerable amount of gas. The dissolved gases, especially oxygen and carbonic anhydride, have an important influence on the health. The following instance is very instructive in this respect. The Grenelle artesian well at Paris, when first opened, supplied a water which had an injurious effect on men and animals. It appeared that this water did not contain oxygen, and was in general very poor in gases. As soon as it was made to fall in a cascade, by which it absorbed air, it proved quite fit for consumption. In long sea voyages fresh water is sometimes not taken at all, or only taken in a small quantity, because it spoils by keeping, and becomes putrid from the organic matter it contains undergoing decomposition. Fresh water may he obtained directly from sea-water by distillation. The distilled water no longer contains sea salts, and is therefore fit for consumption, but it is very tasteless and has the properties of boiled water. In order to render it palatable certain salts, which are usually held in fresh water, are added to it, and it is made to flow in thin streams exposed to the air in order that it may become saturated with the component parts of the atmosphere—that is, absorb gases.

[6] Hard water is such as contains much mineral matter, and especially a large proportion of calcium salts. Such water, owing to the amount of lime it contains, does not form a lather with soap, prevents vegetables boiled in it from softening properly, and forms a large amount of incrustation on vessels in which it is boiled. When of a high degree of hardness, it is injurious for drinking purposes, which is evident from the fact that in several large cities the death-rate has been found to decrease after introducing a soft water in the place of a hard water. Putrid water contains a considerable quantity of decomposing organic matter, chiefly vegetable, but in populated districts, especially in towns, chiefly animal remains. Such water acquires an unpleasant smell and taste, by which stagnant bog water and the water of certain wells in inhabited districts are particularly characterised. Water of this kind is especially injurious at a period of epidemic. It may be partially purified by being passed through charcoal, which retains the putrid and certain organic substances, and also certain mineral substances. Turbid water may be purified to a certain extent by the addition of alum, which aids, after standing some time, the formation of a sediment. Condy's fluid (potassium permanganate) is another means of purifying putrid water. A solution of this substance, even if very dilute, is of a red colour; on adding it to a putrid water, the permanganate oxidises and destroys the organic matter. When added to water in such a quantity as to impart to it an almost imperceptible rose colour it destroys much of the organic substances it contains. It is especially salutary to add a small quantity of Condy's fluid to impure water in times of epidemic.

The presence in water of one gram per litre, or 1,000 grams per cubic metre, of any substance whatsoever, renders it unfit and even injurious for consumption by animals, and this whether organic or mineral matter predominates. The presence of 1 p.c. of chlorides makes water quite salt, and produces thirst instead of assuaging it. The presence of magnesium salts is most unpleasant; they have a disagreeable bitter taste, and, in fact, impart to sea water its peculiar taste. A large amount of nitrates is only found in impure water, and is usually injurious, as they may indicate the presence of decomposing organic matter.

[7]

Fig. 4.—Distillation by means of a metallic still. The liquid in C is heated by the fire F. The vapours rise through the head A and pass by the tube T to the worm S placed in a vessel R, through which a current of cold water flows by means of the tubes D and P.

Distilled water may be prepared, or distillation in general carried on, either in a metal still with worm condenser (fig. 4) or on a small scale in the laboratory in a glass retort (fig. 5) heated by a lamp. Fig. 5 illustrates the main parts of the usual glass laboratory apparatus used for distillation. The steam issuing from the retort (on the right-hand side) passes through a glass tube surrounded by a larger tube, through which a stream of cold water passes, by which the steam is condensed, and runs into a receiver (on the left-hand side).

Fig. 5.—Distillation from a glass retort. The neck of the retort fits into the inner tube of the Liebig's condenser. The space between the inner and outer tube of the condenser is filled with cold water, which enters by the tube g and flows out at f.

[8] One of Lavoisier's first memoirs (1770) referred to this question. He investigated the formation of the earthy residue in the distillation of water in order to prove whether it was possible, as was affirmed, to convert water into earth, and he found that the residue was produced by the action of water on the sides of the vessel containing it, and not from the water itself. He proved this to be the case by direct weighing.

[9] Taking the generally-accepted specific gravity of water at its greatest density—i.e. at 4° as one—it has been shown by experiment that the specific gravity of water at different temperatures is as follows:

A comparison of all the data at present known shows that the variation of the specific gravity S_t with the temperature t (determined by the mercurial thermometer) maybe expressed (Mendeléeff 1891) by the formula

S_t = 1 - (t - 4)² / (94·1 + t) (703·51 - t) 1·9

If the temperature be determined by the hydrogen thermometer, whose indications between 0° and 100° are slightly lower than the mercurial (for example, about 0·1° C. at 20°), then a slightly smaller sp. gr. will be obtained for a given t. Thus Chappuis (1892) obtained 0·998233 for 20°. Water at 4° is taken as the basis for reducing measures of length to measures of weight and volume. The metric, decimal, system of measures of weights and volumes is generally employed in science. The starting point of this system is the metre (39·37 inches) divided into decimetres (= 0·1 metre), centimetres (= 0·01 metre), millimetres (= 0·001 metre), and micrometres (= one millionth of a metre). A cubic decimetre is called a litre, and is used for the measurement of volumes. The weight of a litre of water at 4° in a vacuum is called a kilogram. One thousandth part of a kilogram of water weighs one gram. It is divided into decigrams, centigrams, and milligrams (= 0·001 gram). An English pound equals 453·59 grams. The great advantage of this system is that it is a decimal one, and that it is universally adopted in science and in most international relations. All the measures cited in this work are metrical. The units most often used in science are:—Of length, the centimetre; of weight, the gram; of time, the second; of temperature, the degree Celsius or Centigrade. According to the most trustworthy determinations (Kupfer in Russia 1841, and Chaney in England 1892), the weight of a c. dcm. of water at 4° in vacuo is about 999·9 grms. For ordinary purposes the weight of a c. dcg. may be taken as equal to a kg. Hence the litre (determined by the weight of water it holds) is slightly greater than a cubic decimetre.

[10] As solid substances appear in independent, regular, crystalline forms which are dependent, judging from their cleavage or lamination (in virtue of which mica breaks, up into laminae, and Iceland spar, &c., into pieces bounded by faces inclined to each other at angles which are definite for each substance), on an inequality of attraction (cohesion, hardness) in different directions which intersect at definite angles the determination of crystalline form therefore affords one of the most important characteristics for identifying definite chemical compounds. The elements of crystallography which comprise a special science should therefore he familiar to all who desire to work in scientific chemistry. In this work we shall only have occasion to speak of a few crystalline forms, some of which are shown in figs. 6 to 12.

Fig. 6.—Example of the form belonging to the regular system. Combination of an octahedron and a cube. The former predominates. Alum, fluor spar, suboxide of copper, and others.		Fig. 7.—Rhombic Dodecahedron of the regular system. Garnet.
Fig. 8.—Hexagonal prism terminated by hexagonal pyramids. Quartz, &c.		Fig. 9.—Rhombohedron. Calc spar, &c.
Fig. 10.—Rhombic system. Desmine.	Fig. 11.—Triclinic pyramid.	Fig. 12.—Triclinic system. Albite, &c.

[11] Of all known liquids, water exhibits the greatest cohesion of particles. Indeed, it ascends to a greater height in capillary tubes than other liquids; for instance, two and a half times as high as alcohol, nearly three times as high as ether, and to a much greater height than oil of vitriol, &c. In a tube one mm. in diameter, water at 0° ascends 15·3 mm., measuring from the height of the liquid to two-thirds of the height of the meniscus, and at 100° it rises 12·5 mm. The cohesion varies very uniformly with the temperature; thus at 50° the height of the capillary column equals 13·9 mm.—that is, the mean between the columns at 0° and 100°. This uniformity is not destroyed even at temperatures near the freezing point, and hence it may be assumed that at high temperatures cohesion will vary as uniformly as at ordinary temperatures; that is, the difference between the columns at 0° and 100° being 2·8 mm., the height of the column at 500° should be 15·2 - (5 × 2·8) = 1·2 mm.; or, in other words, at these high temperatures the cohesion between the particles of water would he almost nil. Only certain solutions (sal ammoniac and lithium chloride), and these only with a great excess of water, rise higher than pure water in capillary tubes. The great cohesion of water doubtless determines many of both its physical and chemical properties.

The quantity of heat required to raise the temperature of one part by weight of water from 0° to 1°, i.e. by 1° C., is called the unit of heat or calorie; the specific heat of liquid water at 0° is taken as equal to unity. The variation of this specific heat with a rise in temperature is inconsiderable in comparison with the variation exhibited by the specific heats of other liquids. According to Ettinger, the specific heat of water at 20° = 1·016, at 50° = 1·039, and at 100° = 1·073. The specific heat of water is greater than that of any other known liquid; for example, the specific heat of alcohol at 0° is 0·55—i.e. the quantity of heat which raises 55 parts of water 1° raises 100 parts of alcohol 1°. The specific heat of oil of turpentine at 0° is 0·41, of ether 0·53, of acetic acid 0·5274, of mercury 0·033. Hence water is the best condenser or absorber of heat. This property of water has an important significance in practice and in nature. Water prevents rapid cooling or heating, and thus tempers cold and heat. The specific heats of ice and aqueous vapour are much less than that of water; namely, that of ice is 0·504, and of steam 0·48.

With an increase in pressure equal to one atmosphere, the compressibility of water (see Note 9) is 0·000047, of mercury 0·00000352, of ether 0·00012 at 0°, of alcohol at 13° 0·000095. The addition of various substances to water generally decreases both its compressibility and cohesion. The compressibility of other liquids increases with a rise of temperature, but for water it decreases up to 53° and then increases like other liquids.

The expansion of water by heat (Note 9) also exhibits many peculiarities which are not found in other liquids. The expansion of water at low temperatures is very small compared with other liquids; at 4° it is almost zero, and at 100° it is equal to 0·0008; below 4° it is negative—i.e. water on cooling then expands, and does not decrease in volume. In passing into a solid state, the specific gravity of water decreases; at 0° one c.c. of water weighs 0·999887 gram, and one c.c. of ice at the same temperature weighs only 0·9175 gram. The ice formed, however, contracts on cooling like the majority of other substances. Thus 100 volumes of ice are produced from 92 volumes of water—that is, water expands considerably on freezing, which fact determines a number of natural phenomena. The freezing point of water falls with an increase in pressure (0·007° per atmosphere), because in freezing water expands (Thomson), whilst with substances which contract in solidifying the melting point rises with an increase in pressure; thus, paraffin under one atmosphere melts at 46°, and under 100 atmospheres at 49°.

When liquid water passes into vapour, the cohesion of its particles must be destroyed, as the particles are removed to such a distance from each other that their mutual attraction no longer exhibits any influence. As the cohesion of aqueous particles varies at different temperatures, the quantity of heat which is expended in overcoming this cohesion—or the latent heat of evaporation—will for this reason alone be different at different temperatures. The quantity of heat which is consumed in the transformation of one part by weight of water, at different temperatures, into vapour was determined by Regnault with great accuracy. His researches showed that one part by weight of water at 0°, in passing into vapour having a temperature t°, consumes 606·5 + 0·305t units of heat, at 50° 621·7, at 100° 637·0, at 150° 652·2, and at 200° 667·5. But this quantity includes also the quantity of heat required for heating the water from 0° to t°—i.e. besides the latent heat of evaporation, also that heat which is used in heating the water in a liquid state to a temperature t°. On deducting this amount of heat, we obtain the latent heat of evaporation of water as 606·5 at 0°, 571 at 50°, 534 at 100°, 494 at 150°, and only 453 at 200°, which shows that the conversion of water at different temperatures into vapour at a constant temperature requires very different quantities of heat. This is chiefly dependent on the difference of the cohesion of water at different temperatures; the cohesion is greater at low than at high temperatures, and therefore at low temperatures a greater quantity of heat is required to overcome the cohesion. On comparing these quantities of heat, it will be observed that they decrease rather uniformly, namely their difference between 0° and 100° is 72, and between 100° and 200° is 81 units of heat. From this we may conclude that this variation will be approximately the same for high temperatures also, and therefore that no heat would be required for the conversion of water into vapour at a temperature of about 400°. At this temperature, water passes into vapour whatever be the pressure (see Chap. II. The absolute boiling point of water, according to Dewar, is 370°, the critical pressure 196 atmospheres). It must here be remarked that water, in presenting a greater cohesion, requires a larger quantity of heat for its conversion into vapour than other liquids. Thus alcohol consumes 208, ether 90, turpentine 70, units of heat in their conversion into vapour.

The whole amount of heat which is consumed in the conversion of water into vapour is not used in overcoming the cohesion—that is, in internal accomplished in the liquid. A part of this heat is employed in moving the aqueous particles; in fact, aqueous vapour at 100° occupies a volume 1,659 times greater than that of water (at the ordinary pressure), consequently a portion of the heat or work is employed in lifting the aqueous particles, in overcoming pressure, or in external work, which may be usefully employed, and which is so employed in steam engines. In order to determine this work, let us consider the variation of the maximum pressure or vapour tension of steam at different temperatures. The observations of Regnault in this respect, as on those preceding, deserve special attention from their comprehensiveness and accuracy. The pressure or tension of aqueous vapour at various temperatures is given in the adjoining table, and is expressed in millimetres of the barometric column reduced to 0°.

The table shows the boiling points of water at different pressures. Thus on the summit of Mont Blanc, where the average pressure is about 424 mm., water boils at 84·4°. In a rarefied atmosphere water boils even at the ordinary temperature, but in evaporating it absorbs heat from the neighbouring parts, and therefore it becomes cold and may even freeze if the pressure does not exceed 4·6 mm., and especially if the vapour be rapidly absorbed as it is formed. Oil of vitriol, which absorbs the aqueous vapour, is used for this purpose. Thus ice may be obtained artificially at the ordinary temperature with the aid of an air-pump. This table of the tension of aqueous vapour also shows the temperature of water contained in a closed boiler if the pressure of the steam formed be known. Thus at a pressure of five atmospheres (a pressure of five times the ordinary atmospheric pressure—i.e. 5 × 760 = 3,800 mm.) the temperature of the water would be 152°. The table also shows the pressure produced on a given surface by steam on issuing from a boiler. Thus steam having a temperature of 152° exerts a pressure of 517 kilos on a piston whose surface equals 100 sq. cm., for the pressure of one atmosphere on one sq. cm. equals 1,033 kilos, and steam at 152° has a pressure of five atmospheres. As a column of mercury 1 mm. high exerts a pressure of 1·35959 grams on a surface of 1 sq. cm., therefore the pressure of aqueous vapour at 0° corresponds with a pressure of 6·25 grams per square centimetre. The pressures for all temperatures may be calculated in a similar way, and it will be found that at 100° it is equal to 1,033·28 grams. This means that if a cylinder be taken whose sectional area equals 1 sq. cm., and if water be poured into it and it be closed by a piston weighing 1,033 grams, then on heating it in a vacuum to 100° no steam will be formed, because the steam cannot overcome the pressure of the piston; and if at 100° 534 units of heat be transmitted to each unit of weight of water, then the whole of the water will be converted into vapour having the same temperature; and so also for every other temperature. The question now arises, to what height does the piston rise under these circumstances? that is, in other words, What is the volume occupied by the steam under a known pressure? For this we must know the weight of a cubic centimetre of steam at various temperatures. It has been shown by experiment that the density of steam, which does not saturate a space, varies very inconsiderably at all possible pressures, and is nine times the density of hydrogen under similar conditions. Steam which saturates a space varies in density at different temperatures, but this difference is very small, and its average density with reference to air is 0·64. We will employ this number in our calculation, and will calculate what volume the steam occupies at 100°. One cubic centimetre of air at 0° and 760 mm. weighs 0·001293 gram, at 100° and under the same pressure it will weigh 0·001293 / 1·368 or about 0·000946 gram, and consequently one cubic centimetre of steam whose density is 0·64 will weigh 0·000605 gram at 100°, and therefore one gram of aqueous vapour will occupy a volume of about 1·653 c.c. Consequently, the piston in the cylinder of 1 sq. cm. sectional area, and in which the water occupied a height of 1 cm., will be raised 1,653 cm. on the conversion of this water into steam. This piston, as has been mentioned, weighs 1,033 grams, therefore the external work of the steam—that is, that work which the water does in its conversion into steam at 100°—is equal to lifting a piston weighing 1,033 grams to a height of 1,653 cm., or 17·07 kilogram-metres of work—i.e. is capable of lifting 17 kilograms 1 metre, or 1 kilogram 17 metres. One gram of water requires for its conversion into steam 534 gram units of heat or 0·534 kilogram unit of heat—i.e. the quantity of heat absorbed in the evaporation of one gram of water is equal to the quantity of heat which is capable of heating 1 kilogram of water 0·534°. Each unit of heat, as has been shown by accurate experiment, is capable of doing 424 kilogram-metres of work. Hence, in evaporating, one gram of water expends 424 × 0·534 = (almost) 227 kilogram-metres of work. The external work was found to be only 17 kilogram-metres, therefore 210 kilogram-metres are expended in overcoming the internal cohesion of the aqueous particles, and consequently about 92 p.c. of the total heat or work is consumed in overcoming the internal cohesion. The following figures are thus calculated approximately:—

The work necessary for overcoming the internal cohesion of water in its passage into vapour decreases with the rise in temperature—that is, corresponds with the decrease of cohesion; and, in fact, the variations which take place in this case are very similar to those which are observed in the heights to which water rises in capillary tubes at different temperatures. It is evident, therefore, that the amount of external—or, as it is termed, useful—work which water can supply by its evaporation is very small compared with the amount which it expends in its conversion into vapour.

In considering certain physico-mechanical properties of water, I had in view not only their importance for theory and practice, but also their purely chemical significance; for it is evident from the above considerations that even in a physical change of state the greatest part of the work done is employed in overcoming cohesion, and that an enormous amount of internal energy must be expended in overcoming chemical cohesion or affinity.

[12] When it is necessary to heat a considerable mass of liquid in different vessels, it would be very uneconomical to make use of metallic vessels and to construct a separate furnace for each; such cases are continually met with in practice. Steam from a boiler is introduced into the liquid, or, in general, into the vessel which it is required to heat. The steam, in condensing and passing into a liquid state, parts with its latent heat, and as this is very considerable a small quantity of steam will produce a considerable heating effect. If it be required, for instance, to heat 1,000 kilos of water from 20° to 50°, which requires approximately 30,000 units of heat, steam at 100° is passed into the water from a boiler. Each kilogram of water at 50° contains about 50 units of heat, and each kilogram of steam at 100° contains 637 units of heat; therefore, each kilogram of steam in cooling to 50° gives up 587 units of heat, and consequently 52 kilos of steam are capable of heating 1,000 kilos of water from 20° to 50°. Water is very often applied for heating in chemical practice. For this purpose metallic vessels or pans, called ‘water-baths,’ are made use of. They are closed by a cover formed of concentric rings lying on each other. The vessels—such as beakers, evaporating basins, retorts, &c.—containing liquids, are placed on these rings, and the water in the bath is heated. The steam given off heats the bottom of the vessels to be heated, and thus effects the evaporation or distillation.

[13]

Fig. 13.—Drying oven, composed of brazed copper. It is heated by a lamp. The object to be dried is placed on the gauze inside the oven. The thermometer indicates the temperature.

In order to dry any substance at about 100°—that is, at the boiling point of water (hygroscopic water passes off at this temperature)—an apparatus called a ‘drying-oven’ is employed. It consists of a double copper box; water is poured into the space between the internal and external boxes, and the oven is then heated over a stove or by any other means, or else steam from a boiler is passed between the walls of the two boxes. When the water boils, the temperature inside the inner box will be approximately 100° C. The substance to be dried is placed inside the oven, and the door is closed. Several holes are cut in the door to allow the free passage of air, which carries off the aqueous vapour by the chimney on the top of the oven. Often, however, desiccation is carried on in copper ovens heated directly over a lamp (fig. 13). In this case any desired temperature may be obtained, which is determined by a thermometer fixed in a special orifice. There are substances which only part with their water at a much higher temperature than 100°, and then such air baths are very useful. In order to determine directly the amount of water in a substance which does not part with anything except water at a red heat, the substance is placed in a bulb tube. By first weighing the tube empty and then with the substance to be dried in it, the weight of the substance taken may be found. The tube is then connected on one side with a gas-holder full of air, which, on opening a stop-cock, passes first through a flask containing sulphuric acid, and then into a vessel containing lumps of pumice stone moistened with sulphuric acid. In passing through these vessels the air is thoroughly dried, having given up all its moisture to the sulphuric acid. Thus dry air will pass into the bulb tube, and as hygroscopic water is entirely given up from a substance in dry air even at the ordinary temperature, and still more rapidly on heating, the moisture given up by the substance in the tube will be carried off by the air passing through it. This damp air then passes through a U-shaped tube full of pieces of pumice stone moistened with sulphuric acid, which absorbs all the moisture given off from the substance in the bulb tube. Thus all the water expelled from the substance will collect in the U tube, and so, if this be weighed before and after, the difference will show the quantity of water expelled from the substance. If only water (and not any gases) come over, the increase of the weight of the U tube will be equal to the decrease in the weight of the bulb tube.

[14] Instead of under a glass bell jar, drying over sulphuric acid is often carried on in a desiccator consisting of a shallow wide-mouthed glass vessel, closed by a well-fitting ground-glass cover. Sulphuric acid is poured over the bottom of the desiccator, and the substance to be dried is placed on a glass stand above the acid. A lateral glass tube with a stop-cock is often fused into the desiccator in order to connect it with an air pump, and so allow drying under a diminished pressure, when the moisture evaporates more rapidly. The fact that in the usual form of desiccator the desiccating substance (sulphuric acid) is placed beneath the substance to be dried has the disadvantage that the moist air being lighter than dry air distributes itself in the upper portion of the desiccator and not below. Hempel, in his desiccator (1891), avoids this by placing the absorbent above the substance to be dried. The process of desiccation can be further accelerated by cooling the upper portion of the desiccator, and so inducing ascending and descending currents of air within the apparatus.

[15] Chappuis, however, determined that in wetting 1 gram of charcoal with water 7 units of heat are evolved, and on pouring carbon bisulphide over 1 gram of charcoal as much as 24 units of heat are evolved. Alumina (1 gram), when moistened with water, evolves 2½ calories. This indicates that in respect to evolution of heat moistening already presents a transition towards exothermal combinations (those evolving heat in their formation).

[16] Strong acetic acid (C₂H₄O₂), whose specific gravity at 15° is 1·055, does not become lighter on the addition of water (a lighter substance, sp. gr. = 0·999), but heavier, so that a solution of 80 parts of acetic acid and 20 parts of water has a specific gravity of 1·074, and even a solution of equal parts of acetic acid and water (50 p.c.) has a sp. gr. of 1·065, which is still greater than that of acetic acid itself. This shows the high degree of contraction which takes place on solution. In fact, solutions—and, in general, liquids—on mixing with water, decrease in volume.

[16 bis] Graham, in the jelly formed by gelatine, and De Vries in gelatinous silica (Chapter XVIII.) most frequently employed coloured (tinted) substances, for instance, K₂Cr₂O₇, which showed the rate of diffusion with very great clearness. Prof. Oumoff employed the method described in Chapter X., Note 17, for this purpose.

[17] The researches of Graham, Fick, Nernst, and others showed that the quantity of a dissolved substance which is transmitted (rises) from one stratum of liquid to another in a vertical cylindrical vessel is not only proportional to the time and to the sectional area of the cylinder, but also to the amount and nature of the substance dissolved in a stratum of liquid, so that each substance has its corresponding co-efficient of diffusion. The cause of the diffusion of solutions must be considered as essentially the same as the cause of the diffusion of gases—that is, as dependent on motions which are proper to their molecules; but here most probably those purely chemical, although feebly-developed, forces, which incline the substances dissolved to the formation of definite compounds, also play their part.

[18]

Fig. 15.—Dialyser. Apparatus for the separation of substances which pass through a membrane from those which do not. Description in text.

The rate of diffusion—like the rate of transmission—through membranes, or dialysis (which plays an important part in the vital processes of organisms and also in technical processes), presents, according to Graham's researches, a sharply defined change in passing from such crystallisable substances as the majority of salts and acids to substances which are capable of giving jellies (gum, gelatin, &c.) The former diffuse into solutions and pass through membranes much more rapidly than the latter, and Graham therefore distinguishes between crystalloids, which diffuse rapidly, and colloids, which diffuse slowly. On breaking solid colloids into pieces, a total absence of cleavage is remarked. The fracture of such substances is like that of glue or glass. It is termed a ‘conchoidal’ fracture. Almost all the substances of which animal and vegetable bodies consist are colloids, and this is, at all events, partly the reason why animals and plants have such varied forms, which have no resemblance to the crystalline forms of the majority of mineral substances. The colloid solid substances in organisms—that is, in animals and plants—almost always contain water, and take most peculiar forms, of networks, of granules, of hairs, of mucous, shapeless masses, &c., which are quite different from the forms taken by crystalline substances. When colloids separate out from solutions, or from a molten state, they present a form which is similar to that of the liquid from which they were formed. Glass may he taken as the best example of this. Colloids are distinguishable from crystalloids, not only by the absence of crystalline form, but by many other properties which admit of clearly distinguishing both these classes of solids, as Graham showed. Nearly all colloids are capable of passing, under certain circumstances, from a soluble into an insoluble state. The best example is shown by white of eggs (albumin) in the raw and soluble form, and in the hard-boiled and insoluble form. The majority of colloids, on passing into an insoluble form in the presence of water, give substances having a gelatinous appearance, which is familiar to every one in starch, solidified glue, jelly, &c. Thus gelatin, or common carpenter's glue, when soaked in water, swells up into an insoluble jelly. If this jelly be heated, it melts, and is then soluble in water, but on cooling it again forms a jelly which is insoluble in water. One of the properties which distinguish colloids from crystalloids is that the former pass very slowly through a membrane, whilst the latter penetrate very rapidly. This may be shown by taking a cylinder, open at both ends, and by covering its lower end with a bladder or with vegetable parchment (unsized paper immersed for two or three minutes in a mixture of sulphuric acid and half its volume of water, and then washed), or any other membranous substance (all such substances are themselves colloids in an insoluble form). The membrane must be firmly tied to the cylinder, so as not to leave any opening. Such an apparatus is called a dialyser (fig. 15), and the process of separation of crystalloids from colloids by means of such a membrane is termed dialysis. An aqueous solution of a crystalloid or colloid, or a mixture of both, is poured into the dialyser, which is then placed in a vessel containing water, so that the bottom of the membrane is covered with water. Then, after a certain period of time, the crystalloid passes through the membrane, whilst the colloid, if it does pass through at all, does so at an incomparably slower rate. The crystalloid naturally passes through into the water until the solution attains the same strength on both sides of the membrane. By replacing the outside water with fresh water, a fresh quantity of the crystalloid may be separated from the dialyser. While a crystalloid is passing through the membrane, a colloid remains almost entirely in the dialyser, and therefore a mixed solution of these two kinds of substances may be separated from each other by a dialyser. The study of the properties of colloids, and of the phenomena of their passage through membranes, should elucidate much respecting the phenomena which are accomplished in organisms.

[19] The formation of solutions may be considered in two aspects, from a physical and from a chemical point of view, and it is more evident in solutions than in any other department of chemistry how closely these provinces of natural science are allied together. On the one hand solutions form a particular case of a physico-mechanical interpenetration of homogeneous substances, and a juxtaposition of the molecules of the substance dissolved and of the solvent, similar to the juxtaposition which is exhibited in homogeneous substances. From this point of view this diffusion of solutions is exactly similar to the diffusion of gases, with only this difference, that the nature and store of energy are different in gases from what they are in liquids, and that in liquids there is considerable friction, whilst in gases there is comparatively little. The penetration of a dissolved substance into water is likened to evaporation, and solution to the formation of vapour. This resemblance was clearly expressed even by Graham. In recent years the Dutch chemist, Van't Hoff, has developed this view of solutions in great detail, having shown (in a memoir in the Transactions of the Swedish Academy of Science, Part 21, No. 17, ‘Lois de l'équilibre chimique dans l'état dilué, gazeux ou dissous,’ 1886), that for dilute solutions the osmotic pressure follows the same laws of Boyle, Mariotte, Gay-Lussac, and Avogadro-Gerhardt as for gases. The osmotic pressure of a substance dissolved in water is determined by means of membranes which allow the passage of water, but not of a substance dissolved in it, through them. This property is found in animal protoplasmic membranes and in porous substances covered with an amorphous precipitate, such as is obtained by the action of copper sulphate on potassium ferrocyanide (Pfeffer, Traube). If, for instance, a one p.c. solution of sugar he placed in such a vessel, which is then closed and placed in water, the water passes through the walls of the vessel and increases the pressure by 50 mm. of the barometric column. If the pressure be artificially increased inside the vessel, then the water will be expelled through the walls. De Vries found a convenient means of determining isotonic solutions (those presenting a similar osmotic pressure) in the cells of plants. For this purpose a portion of the soft part of the leaves of the Tradescantis discolor, for instance, is cut away and moistened with the solution of a given salt and of a given strength. If the osmotic pressure of the solution taken be less than that of the sap contained in the cells they will change their form or shrink; if, on the other hand, the osmotic pressure be greater than that of the sap, then the cells will expand, as can easily be seen under the microscope. By altering the amount of the different salts in solution it is possible to find for each salt the strength of solution at which the cells begin to swell, and at which they will consequently have an equal osmotic pressure. As it increases in proportion to the amount of a substance dissolved per 100 parts of water, it is possible, knowing the osmotic pressure of a given substance—for instance, sugar at various degrees of concentration of solution—and knowing the composition of isotonic solutions compared with sugar, to determine the osmotic pressure of all the salts investigated. The osmotic pressure of dilute solutions determined in this manner directly or indirectly (from observations made by Pfeffer and De Vries) was shown to follow the same laws as those of the pressure of gases; for instance, by doubling or increasing the quantity of a salt (in a given volume) n times, the pressure is doubled or increases n times. So, for example, in a solution containing one part of sugar per 100 parts of water the osmotic pressure (according to Pfeffer) = 58·5 cm. of mercury, if 2 parts of sugar = 101·6, if 4 parts = 208·2 and so on, which proves that the ratio is true within the limits of experimental error. (2) Different substances for equal strengths of solutions, show very different osmotic pressures, just as gases for equal parts by weight in equal volumes show different tensions. (3) If, for a given dilute solution at 0°, the osmotic pressure equal p°, then at t° it will be greater and equal to p°(1 + 0·00367t), i.e. it increases with the temperature in exactly the same manner as the tension of gases increases. (4) If in dilute solutions of such substances as do not conduct an electric current (for instance, sugar, acetone, and many other organic bodies) the substances be taken in the ratio of their molecular weights (expressed by their formulæ, see Chapter VII.), then not only will the osmotic pressure be equal, but its magnitude will be determined by that tension which would be proper to the vapours of the given substances when they would be contained in the space occupied by the solution, just as the tension of the vapours of molecular quantities of the given substances will be equal, and determined by the laws of Gay-Lussac, Mariotte, and Avogadro-Gerhardt. Those formulæ (Chapter VII., Notes 23 and 24) by which the gaseous state of matter is determined, may also be applied in the present case. So, for example, the osmotic pressure p, in centimetres of mercury, of a one per cent. solution of sugar, may be calculated according to the formula for gases:

Mp = 6200s(273 + t),

where M is the molecular weight, s the weight in grams of a cubic centimetre of vapour, and t its temperature. For sugar M = 342 (because its molecular composition is C₁₂H₂₂O₁₁). The specific gravity of the solution of sugar is 1·003, hence the weight of sugar s contained in a 1 per cent. solution = 0·01003 gram. The observation was made at t = 14°. Hence, according to the formula, we find p = 52·2 centimetres. And experiments carried on at 14° gave 53·5 centimetres, which is very near to the above. (5) For the solutions of salts, acids, and similar substances, which conduct an electric current, the calculated pressure is usually (but not always in a definite or multiple number of times) less than the observed by i times, and this i for dilute solutions of MgSO₄ is nearly 1, for CO₂ = 1, for KCl, NaCl, KI, KNO₃ greater than 1, and approximates to 2, for BaCl₂, MgCl₂, K₂CO₃, and others between 2 and 3, for HCl, H₂SO₄, NaNO₃, CaN₂O₆, and others nearly 2 and so on. It should be remarked that the above deductions are only applicable (and with a certain degree of accuracy) to dilute solutions, and in this respect resemble the generalisations of Michel and Kraft (see Note 44). Nevertheless, the arithmetical relation found by Van't Hoff between the formation of vapours and the transition into dilute solutions forms an important scientific discovery, which should facilitate the explanation of the nature of solutions, while the osmotic pressure of solutions already forms a very important aspect of the study of solutions. In this respect it is necessary to mention that Prof. Konovaloff (1891, and subsequently others also) discovered the dependence (and it may be a sufficient explanation) of the osmotic pressure upon the differences of the tensions of aqueous vapours and aqueous solutions; this, however, already enters into a special province of physical chemistry (certain data are given in Note 49 and following), and to this physical side of the question also belongs one of the extreme consequences of the resemblance of osmotic pressure to gaseous pressure, which is that the concentration of a uniform solution varies in parts which are heated or cooled. Soret (1881) indeed observed that a solution of copper sulphate containing 17 parts of the salt at 20° only contained 14 parts after heating the upper portion of the tube to 80° for a long period of time. This aspect of solution, which is now being very carefully and fully worked out, may be called the physical side. Its other aspect is purely chemical, for solution does not take place between any two substances, but requires a special and particular attraction or affinity between them. A vapour or gas permeates any other vapour or gas, but a salt which dissolves in water may not be in the least soluble in alcohol, and is quite insoluble in mercury. In considering solutions as a manifestation of chemical force (and of chemical energy), it must be acknowledged that they are here developed to so feeble an extent that the definite compounds (that is, those formed according to the law of multiple proportions) formed between water and a soluble substance dissociate even at the ordinary temperature, forming a homogeneous system—that is, one in which both the compound and the products into which it decomposes (water and the aqueous compound) occur in a liquid state. The chief difficulty in the comprehension of solutions depends on the fact that the mechanical theory of the structure of liquids has not yet been so fully developed as the theory of gases, and solutions are liquids. The conception of solutions as liquid dissociated definite chemical compounds is based on the following considerations: (1) that there exist certain undoubtedly definite chemical crystallised compounds (such as H₂SO₄,H₂O; or NaCl,2H₂O; or CaCl₂,6H₂O; &c.) which melt on a certain rise of temperature, and then form true solutions; (2) that metallic alloys in a molten condition are real solutions, but on cooling they often give entirely distinct and definite crystallised compounds, which are recognised by the properties of alloys; (3) that between the solvent and the substance dissolved there are formed, in a number of cases, many undoubtedly definite compounds, such as compounds with water of crystallisation; (4) that the physical properties of solutions, and especially their specific gravities (a property which can be very accurately determined), vary with a change in composition, and in such a manner as would be required by the formation of one or more definite but dissociating compounds. Thus, for example, on adding water to fuming sulphuric acid its density is observed to decrease until it attains the definite composition H₂SO₄, or SO₃ + H₂O, when the specific gravity increases, although on further diluting with water it again falls. Moreover (Mendeléeff, The Investigation of Aqueous Solutions from their Specific Gravities, 1887), the increase in specific gravity (ds), varies in all well-known solutions with the proportion of the substance dissolved (dp), and this dependence can be expressed by a formula ( ds / dp = A + Bp) between the limits of definite compounds whose existence in solutions must be admitted, and this is in complete accordance with the dissociation hypothesis. Thus, for instance, from H₂SO₄ to H₂SO₄ + H₂O (both these substances exist as definite compounds in a free state), the fraction ds / dp = 0·0729 - 0·000749p (where p is the percentage amount of H₂SO₄). For alcohol C₂H₆O, whose aqueous solutions have been more accurately investigated than all others, the definite compound C₂H₆O + 3H₂O, and others must be acknowledged in its solutions.

The two aspects of solution above mentioned, and the hypotheses which have as yet been applied to the examination of solutions, although they have somewhat different starting points, will doubtless in time lead to a general theory of solutions, because the same common laws govern both physical and chemical phenomena, inasmuch as the properties and motions of molecules, which determine physical properties, depend on the motions and properties of atoms, which determine chemical reactions. For details of the questions dealing with theories of solution, recourse must now be had to special memoirs and to works on theoretical (physical) chemistry; for this subject forms one of special interest at the present epoch of the development of our science. In working out chiefly the chemical side of solutions, I consider it to be necessary to reconcile the two aspects of the question; this seems to me to be all the more possible, as the physical side is limited to dilute solutions only, whilst the chemical side deals mainly with strong solutions.

[20] A system of (chemically or physically) re-acting substances in different states of aggregation—for instance, some solid, others liquid or gaseous—is termed a heterogeneous system. Up to now it is only systems of this kind which can be subjected to detailed examination in the sense of the mechanical theory of matter. Solutions (i.e. unsaturated ones) form fluid homogeneous systems, which at the present time can only be investigated with difficulty.

In the case of limited solution of liquids in liquids, the difference between the solvent and the substance dissolved is clearly seen. The former (that is, the solvent) may be added in an unlimited quantity, and yet the solution obtained will always be uniform, whilst only a definite saturating proportion of the substance dissolved can be taken, We will take water and common (sulphuric) ether. On shaking the ether with the water, it will be remarked that a portion of it dissolves in the water. If the ether be taken in such a quantity that it saturates the water and a portion of it remains undissolved, then this remaining portion will act as a solvent, and water will diffuse through it and also form a saturated solution of water in the ether taken. Thus two saturated solutions will be obtained. One solution will contain ether dissolved in water, and the other solution will contain water dissolved in ether. These two solutions will arrange themselves in two layers, according to their density; the ethereal solution of water will be on the top. If the upper ethereal solution be poured off from the aqueous solution, any quantity of ether may be added to it; this shows that the dissolving substance is ether. If water be added to it, it is no longer dissolved in it; this shows that water saturates the ether—here water is the substance dissolved. If we act in the same manner with the lower layer, we shall find that water is the solvent and ether the substance dissolved. By taking different amounts of ether and water, the degree of solubility of ether in water, and of water in ether, may be easily determined. Water approximately dissolves ¹⁄₁₀ of its volume of ether, and ether dissolves a very small quantity of water. Let us now imagine that the liquid poured in dissolves a considerable amount of water, and that water dissolves a considerable amount of the liquid. Two layers could not be formed, because the saturated solutions would resemble each other, and therefore they would intermix in all proportions. This is, consequently, a case of a phenomenon where two liquids present considerable co-efficients of solubility in each other, but where it is impossible to say what these co-efficients are, because it is impossible to obtain a saturated solution.

[21]

Fig. 16.—Bunsen's absorptiometer. Apparatus for determining the solubility of gases in liquids.

The solubility, or co-efficient of solubility, of a substance is determined by various methods. Either a solution is expressly prepared with a clear excess of the soluble substance and saturated at a given temperature, and the quantity of water and of the substance dissolved in it determined by evaporation, desiccation, or other means; or else, as is done with gases, definite quantities of water and of the soluble substance are taken and the amount remaining undissolved is determined.

The solubility of a gas in water is determined by means of an apparatus called an absorptiometer (fig. 16). It consists of an iron stand f, on which an india-rubber ring rests. A wide glass tube is placed on this ring, and is pressed down on it by the ring h and the screws i i. The tube is thus firmly fixed on the stand. A cock r, communicating with a funnel r, passes into the lower part of the stand. Mercury can be poured into the wide tube through this funnel, which is therefore made of steel, as copper would be affected by the mercury. The upper ring h is furnished with a cover p, which can be firmly pressed down on to the wide tube, and hermetically closes it by means of an india-rubber ring. The tube r r can be raised at will, and so by pouring mercury into the funnel the height of the column of mercury, which produces pressure inside the apparatus, can be increased. The pressure can also be diminished at will, by letting mercury out through the cock r. A graduated tube e, containing the gas and liquid to be experimented on, is placed inside the wide tube. This tube is graduated in millimetres for determining the pressure, and it is calibrated for volume, so that the number of volumes occupied by the gas and liquid dissolving it can be easily calculated. This tube can also be easily removed from the apparatus. The lower portion of this tube when removed from the apparatus is shown to the right of the figure. It will be observed that its lower end is furnished with a male screw b, fitting in a nut a. The lower surface of the nut a is covered with india-rubber, so that on screwing up the tube its lower end presses upon the india-rubber, and thus hermetically closes the whole tube, for its upper end is fused up. The nut a is furnished with arms c c, and in the stand f there are corresponding spaces, so that when the screwed-up internal tube is fixed into stand f, the arms c c fix into these spaces cut in f. This enables the internal tube to be fixed on to the stand f. When the internal tube is fixed in the stand, the wide tube is put into its right position, and mercury and water are poured into the space between the two tubes, and communication is opened between the inside of the tube e and the mercury between the interior and exterior tubes. This is done by either revolving the interior tube e, or by a key turning the nut about the bottom part of f. The tube e is filled with gas and water as follows: the tube is removed from the apparatus, filled with mercury, and the gas to be experimented on is passed into it. The volume of the gas is measured, the temperature and pressure determined, and the volume it would occupy at 0° and 760 mm. calculated. A known volume of water is then introduced into the tube. The water must be previously boiled, so as to be quite freed from air in solution. The tube is then closed by screwing it down on to the india-rubber on the nut. It is then fixed on to the stand f, mercury and water are poured into the intervening space between it and the exterior tube, which is then screwed up and closed by the cover p, and the whole apparatus is left at rest for some time, so that the tube e, and the gas in it, may attain the same temperature as that of the surrounding water, which is marked by a thermometer k tied to the tube e. The interior tube is then again closed by turning it in the nut, the cover p again shut, and the whole apparatus is shaken in order that the gas in the tube e may entirely saturate the water. After several shakings, the tube e is again opened by turning it in the nut, and the apparatus is left at rest for a certain time; it is then closed and again shaken, and so on until the volume of gas does not diminish after a fresh shaking—that is, until saturation ensues. Observations are then made of the temperature, the height of the mercury in the interior tube, and the level of the water in it, and also of the level of the mercury and water in the exterior tube. All these data are necessary in order to calculate the pressure under which the solution of the gas takes place, and what volume of gas remains undissolved, and also the quantity of water which serves as the solvent. By varying the temperature of the surrounding water, the amount of gas dissolved at various temperatures may be determined. Bunsen, Carius, and many others determined the solution of various gases in water, alcohol, and certain other liquids, by means of this apparatus. If in a determination of this kind it is found that n cubic centimetres of water at a pressure h dissolve m cubic centimetres of a given gas, measured at 0° and 760 mm., when the temperature under which solution took place was t°, then it follows that at the temperature t the co-efficient of solubility of the gas in 1 volume of the liquid will be equal to m / n × 760 / h .

This formula is very clearly understood from the fact that the co-efficient of solubility of gases is that quantity measured at 0° and 760 mm., which is absorbed at a pressure of 760 mm. by one volume of a liquid. If n cubic centimetres of water absorb m cubic centimetres of a gas, then one cubic centimetre absorbs m / n . If m / n c.c. of a gas are absorbed under a pressure of h mm., then, according to the law of the variation of solubility of a gas with the pressure, there would he dissolved, under a pressure of 760 mm., a quantity varying in the same ratio to m/n as 760 : h. In determining the residual volume of gas its moisture (note 1) must be taken into consideration.

Below are given the number of grams of several substances saturating 100 grams of water—that is, their co-efficients of solubility by weight at three different temperatures:—

Sometimes a substance is so slightly soluble that it may be considered as insoluble. Many such substances are met with both in solids and liquids, and such a gas as oxygen, although it does dissolve, does so in so small a proportion by weight that it might be considered as zero did not the solubility of even so little oxygen play an important part in nature (as in the respiration of fishes) and were not an infinitesimal quantity of a gas by weight so easily measured by volume. The sign ∞, which stands on a line with sulphuric acid in the above table, indicates that it intermixes with water in all proportions. There are many such cases among liquids, and everybody knows, for instance, that spirit (absolute alcohol) can be mixed in any proportion with water.

[22] Just as the existence must he admitted of substances which are completely undecomposable (chemically) at the ordinary temperature—and of substances which are entirely non-volatile at such a temperature (as wood and gold), although capable of decomposing (wood) or volatilising (gold) at a higher temperature—so also the existence must be admitted of substances which are totally insoluble in water without some degree of change in their state. Although mercury is partially volatile at the ordinary temperature, there is no reason to think that it and other metals are soluble in water, alcohol, or other similar liquids. However, mercury forms solutions, as it dissolves other metals. On the other hand, there are many substances found in nature which are so very slightly soluble in water, that in ordinary practice they may be considered as insoluble (for example, barium sulphate). For the comprehension of that general plan according to which a change of state of substances (combined or dissolved, solid, liquid, or gaseous) takes place, it is very important to make a distinction at this boundary line (on approaching zero of decomposition, volatility, or solubility) between an insignificant amount and zero, but the present methods of research and the data at our disposal at the present time only just touch such questions (by studying the electrical conductivity of dilute solutions and the development of micro-organisms in them). It must be remarked, besides, that water in a number of cases does not dissolve a substance as such, but acts on it chemically and forms a soluble substance. Thus glass and many rocks, especially if taken as powder, are chemically changed by water, but are not directly soluble in it.

[23] Beilby (1883) experimented on paraffin, and found that one litre of solid paraffin at 21° weighed 874 grams, and when liquid, at its melting-point 38°, 783 grams, at 49°, 775 grams, and at 60°, 767 grams, from which the weight of a litre of liquefied paraffin would be 795·4 grams at 21° if it could remain liquid at that temperature. By dissolving solid paraffin in lubricating oil at 21° Beilby found that 795·6 grams occupy one cubic decimetre, from which he concluded that the solution contained liquefied paraffin.

[24] Gay-Lussac was the first to have recourse to such a graphic method of expressing solubility, and he considered, in accordance with the general opinion, that by joining up the summits of the ordinates in one harmonious curve it is possible to express the entire change of solubility with the temperature. Now, there are many reasons for doubting the accuracy of such an admission, for there are undoubtedly critical points in curves of solubility (for example, of sodium sulphate, as shown further on), and it may be that definite compounds of dissolved substances with water, in decomposing within known limits of temperature, give critical points more often than would be imagined; it may even be, indeed, that instead of a continuous curve, solubility should be expressed—if not always, then not unfrequently—by straight or broken lines. According to Ditte, the solubility of sodium nitrate, NaNO₃, is expressed by the following figures per 100 parts of water:—

In my opinion (1881) these data should be expressed with exactitude by a straight line, 67·5 + 0·87t, which entirely agrees with the results of experiment. According to this the figure expressing the solubility of salt at 0° exactly coincides with the composition of a definite chemical compound—NaNO₃,7H₂O. The experiments made by Ditte showed that all saturated solutions between 0° and -15·7° have such a composition, and that at the latter temperature the solution completely solidifies into one homogeneous whole. Between 0° and -15·7° the solution NaNO₃,7H₂O does not deposit either salt or ice. Thus the solubility of sodium nitrate is expressed by a broken straight line. In recent times (1888) Étard discovered a similar phenomenon in many of the sulphates. Brandes, in 1830, shows a diminution in solubility below 100° for manganese sulphate. The percentage by weight (i.e. per 100 parts of the solution, and not of water) of saturation for ferrous sulphate, FeSO₄, from -2° to +65° = 13·5 + 0·3784t—that is, the solubility of the salt increases. The solubility remains constant from 65° to 98° (according to Brandes the solubility then increases; this divergence of opinion requires proof), and from 98° to 150° it falls as = 104·35 - 0·6685t. Hence, at about +156° the solubility should = 0, and this has been confirmed by experiment. I observe, on my part, that Étard's formula gives 38·1 p.c. of salt at 65° and 38·8 p.c. at 92°, and this maximum amount of salt in the solution very nearly corresponds with the composition FeSO₄,14H₂O, which requires 37·6 p.c. From what has been said, it is evident that the data concerning solubility require a new method of investigation, which should have in view the entire scale of solubility—from the formation of completely solidified solutions (cryohydrates, which we shall speak of presently) to the separation of salts from their solutions, if this is accomplished at a higher temperature (for manganese and cadmium sulphates there is an entire separation, according to Étard), or to the formation of a constant solubility (for potassium sulphate the solubility, according to Étard, remains constant from 163° to 220° and equals 24·9 p.c.) (See Chapter XIV., note 50, solubility of CaCl₂.)

[25] The latent heat of fusion is determined at the temperature of fusion, whilst solution takes place at the ordinary temperature, and one must think that at this temperature the latent heat would be different, just as the latent heat of evaporation varies with the temperature (see Note 11). Besides which, in dissolving, disintegration of the particles of both the solvent and the substance dissolved takes place, a process which in its mechanical aspect resembles evaporation, and therefore must consume much heat. The heat emitted in the solution of a solid must therefore be considered (Personne) as composed of three factors—(1) positive, the effect of combination; (2) negative, the effect of transference into a liquid state; and (3) negative, the effect of disintegration. In the solution of a liquid by a liquid the second factor is removed; and therefore, if the heat evolved in combination is greater than that absorbed in disintegration a heating effect is observed, and in the reverse case a cooling effect; and, indeed, sulphuric acid, alcohol, and many liquids evolve heat in dissolving in each other. But the solution of chloroform in carbon bisulphide (Bussy and Binget), or of phenol (or aniline) in water (Alexéeff), produces cold. In the solution of a small quantity of water in acetic acid (Abasheff), or hydrocyanic acid (Bussy and Binget), or amyl alcohol (Alexéeff), cold is produced, whilst in the solution of these substances in an excess of water heat is evolved.

The relation existing between the solubility of solid bodies and the heat and temperature of fusion and solution has been studied by many investigators, and more recently (1893) by Schröder, who states that in the solution of a solid body in a solvent which does not act chemically upon it, a very simple process takes place, which differs but little from the intermixture of two gases which do not react chemically upon each other. The following relation between the heat of solution Q and the heat of fusion p may then be taken: P / T₀ = Q / T = constant, where T₀ and T are the absolute (from -273°) temperatures of fusion and saturation. Thus, for instance, in the case of naphthalene the calculated and observed magnitudes of the heat of solution differ but slightly from each other.

The fullest information concerning the solution of liquids in liquids has been gathered by W. T. Alexéeff (1883–1885); these data are, however, far from being sufficient to solve the mass of problems respecting this subject. He showed that two liquids which dissolve in each other, intermix together in all proportions at a certain temperature. Thus the solubility of phenol, C₆H₆O, in water, and the converse, is limited up to 70°, whilst above this temperature they intermix in all proportions. This is seen from the following figures, where p is the percentage amount of phenol and t the temperature at which the solution becomes turbid—that is, that at which it is saturated:—

It is exactly the same with the solution of benzene, aniline, and other substances in molten sulphur. Alexéeff discovered a similar complete intermixture for solutions of secondary butyl alcohol in water at about 107°; at lower temperatures the solubility is not only limited, but between 50° and 70° it is at its minimum, both for solutions of the alcohol in water and for water in the alcohol; and at a temperature of 5° both solutions exhibit a fresh change in their scale of solubility, so that a solution of the alcohol in water which is saturated between 5° and 40° will become turbid when heated to 60°. In the solution of liquids in liquids, Alexéeff observed a lowering in temperature (an absorption of heat) and an absence of change in specific heat (calculated for the mixture) much more frequently than had been done by previous observers. As regards his hypothesis (in the sense of a mechanical and not a chemical representation of solutions) that substances in solution preserve their physical states (as gases, liquids, or solids), it is very doubtful, for it would necessitate admitting the presence of ice in water or its vapour.

From what has been said above, it will be clear that even in so very simple a case as solution, it is impossible to calculate the heat emitted by chemical action alone, and that the chemical process cannot be separated from the physical and mechanical.

[26] The cooling effect produced in the solution of solids (and also in the expansion of gases and in evaporation) is applied to the production of low temperatures. Ammonium nitrate is very often used for this purpose; in dissolving in water it absorbs 77 units of heat per each part by weight. On evaporating the solution thus formed, the solid salt is re-obtained. The application of the various freezing mixtures is based on the same principle. Snow or broken ice frequently enters into the composition of these mixtures, advantage being taken of its latent heat of fusion in order to obtain the lowest possible temperature (without altering the pressure or employing heat, as in other methods of obtaining a low temperature). For laboratory work recourse is most often had to a mixture of three parts of snow and one part of common salt, which causes the temperature to fall from 0° to -21° C. Potassium thiocyanate, KCNS, mixed with water (¾ by weight of the salt) gives a still lower temperature. By mixing ten parts of crystallised calcium chloride, CaCl₂,6H₂O, with seven parts of snow, the temperature may even fall from 0° to -55°.

[27] The heat which is evolved in solution, or even in the dilution of solutions, is also sometimes made use of in practice. Thus caustic soda (NaHO), in dissolving or on the addition of water to a strong solution of it, evolves so much heat that it can replace fuel. In a steam boiler, which has been previously heated to the boiling point, another boiler is placed containing caustic soda, and the exhaust steam is made to pass through the latter; the formation of steam then goes on for a somewhat long period of time without any other heating. Norton makes use of this for smokeless street locomotives.

[28]

Fig. 17.—Curves expressing the contraction, quantity of heat, and rises of temperature produced by mixing sulphuric acid with water. Percentage of H₂SO₄ is given along the axis of abscissae.

The temperatures obtained by mixing monohydrated sulphuric acid, H₂SO₄, with different quantities of water, are shown on the lowest curve in fig. 17, the relative proportions of both substances being expressed in percentages by weight along the horizontal axis. The greatest rise of temperature is 149°. It corresponds with the greatest evolution of heat (given on the middle curve) corresponding with a definite volume (100 c.c.) of the solution produced. The top curve expresses the degree of contraction, which also corresponds with 100 volumes of the solution produced. The greatest contraction, as also the greatest rise of temperature, corresponds with the formation of a trihydrate, H₂SO₄,2H₂O (= 73·1 p.c. H₂SO₄), which very likely repeats itself in a similar form in other solutions, although all the phenomena (of contraction, evolution of heat, and rise of temperature) are very complex and are dependent on many circumstances. One would think, however, judging from the above examples, that all other influences are feebler in their action than chemical attraction, especially when it is so considerable as between sulphuric acid and water.

[29] If a volume of gas v be measured under a pressure of h mm. of mercury (at 0°) and at a temperature t° Centigrade, then, according to the combined laws of Boyle, Mariotte, and of Gay-Lussac, its volume at 0° and 760 mm. will equal the product of v into 760 divided by the product of h into 1 + at°, where a is the co-efficient of expansion of gases, which is equal to 0·00367. The weight of the gas will be equal to its volume at 0° and 760 mm. multiplied by its density referred to air and by the weight of one volume of air at 0° and 760 mm. The weight of one litre of air under these conditions being = 1·293 gram. If the density of the gas be given in relation to hydrogen this must be divided by 14·4 to bring it in relation to air. If the gas be measured when saturated with aqueous vapour, then it must be reduced to the volume and weight of the gas when dry, according to the rules given in Note 1. If the pressure be determined by a column of mercury having a temperature t, then by dividing the height of the column by 1 + 0·00018t the corresponding height at 0° is obtained. If the gas be enclosed in a tube in which a liquid stands above the level of the mercury, the height of the column of the liquid being = H and its density = D, then the gas will be under a pressure which is equal to the barometric pressure less HD / 13·59 , where 13·59 is the density of mercury. By these methods the quantity of a gas is determined, and its observed volume reduced to normal conditions or to parts by weight. The physical data concerning vapours and gases must be continually kept in sight in dealing with and measuring gases. The student must become perfectly familiar with the calculations relating to gases.

[30] According to Bunsen, Winkler, Timofeeff, and others, 100 vols. of water under a pressure of one atmosphere absorb the following volumes of gas (measured at 0° and 760 mm.):—

1, oxygen; 2, nitrogen; 3, hydrogen; 4, carbonic anhydride; 5, carbonic oxide; 6, nitrous oxide; 7, hydrogen sulphide; 8, sulphurous anhydride; 9, marsh gas; 10, ammonia; 11, nitric oxide. The decrease of solubility with a rise of temperature varies for different gases; it is greater, the greater the molecular weight of the gas. It is shown by calculation that this decrease varies (Winkler) as the cube root of the molecular weight of the gas. This is seen from the following table:

The decrease in the coefficient of absorption with the temperature must be connected with a change in the physical properties of the water. Winkler (1891) remarked a certain relation between the internal friction and the coefficient of absorption at various temperatures.

[31] These figures show that the co-efficient of solubility decreases with an increase of pressure, notwithstanding that the carbonic anhydride approaches a liquid state. As a matter of fact, liquefied carbonic anhydride does not intermix with water, and does not exhibit a rapid increase in solubility at its temperature of liquefaction. This indicates, in the first place, that solution does not consist in liquefaction, and in the second place that the solubility of a substance is determined by a peculiar attraction of water for the substance dissolving. Wroblewski even considered it possible to admit that a dissolved gas retains its properties as a gas. This he deduced from experiments, which showed that the rate of diffusion of gases in a solvent is, for gases of different densities, inversely proportional to the square roots of their densities, just as the velocities of gaseous molecules (see Note 34). Wroblewski showed the affinity of water, H₂O, for carbonic anhydride, CO₂, from the fact that on expanding moist compressed carbonic anhydride (compressed at 0° under a pressure of 10 atmospheres) he obtained (a fall in temperature takes place from the expansion) a very unstable definite crystalline compound, CO₂ + 8H₂O.

[32] As, according to the researches of Roscoe and his collaborators, ammonia exhibits a considerable deviation at low temperatures from the law of Henry and Dalton, whilst at 100° the deviation is small, it would appear that the dissociating influence of temperature affects all gaseous solutions; that is, at high temperatures, the solutions of all gases will follow the law, and at lower temperatures there will in all cases be a deviation from it.

[33] The ratio between the pressure and the amount of gas dissolved was discovered by Henry in 1805, and Dalton in 1807 pointed out the adaptability of this law to cases of gaseous mixtures, introducing the conception of partial pressures which is absolutely necessary for a right comprehension of Dalton's law. The conception of partial pressures essentially enters into that of the diffusion of vapours in gases (footnote 1); for the pressure of damp air is equal to the sum of the pressures of dry air and of the aqueous vapour in it, and it is admitted as a corollary to Dalton's law that evaporation in dry air takes place as in a vacuum. It is, however, necessary to remark that the volume of a mixture of two gases (or vapours) is only approximately equal to the sum of the volumes of its constituents (the same, naturally, also refers to their pressures)—that is to say, in mixing gases a change of volume occurs, which, although small, is quite apparent when carefully measured. For instance, in 1888 Brown showed that on mixing various volumes of sulphurous anhydride (SO₂) with carbonic anhydride (at equal pressures of 760 mm. and equal temperatures) a decrease of pressure of 3·9 millimetres of mercury was observed. The possibility of a chemical action in similar mixtures is evident from the fact that equal volumes of sulphurous and carbonic anhydrides at -19° form, according to Pictet's researches in 1888, a liquid which may be regarded as an unstable chemical compound, or a solution similar to that given when sulphurous anhydride and water combine to an unstable chemical whole.

[34] The origin of the kinetic theory of gases now generally accepted, according to which they are animated by a rapid progressive motion, is very ancient (Bernouilli and others in the last century had already developed a similar representation), but it was only generally accepted after the mechanical theory of heat had been established, and after the work of Krönig (1855), and especially after its mathematical side had been worked out by Clausius and Maxwell. The pressure, elasticity, diffusion, and internal friction of gases, the laws of Boyle, Mariotte, and of Gay-Lussac and Avogadro-Gerhardt are not only explained (deduced) by the kinetic theory of gases, but also expressed with perfect exactitude; thus, for example, the magnitude of the internal friction of different gases was foretold with exactitude by Maxwell, by applying the theory of probabilities to the impact of gaseous particles. The kinetic theory of gases must therefore be considered as one of the most brilliant acquisitions of the latter half of the present century. The velocity of the progressive motion of the particles of a gas, one cubic centimetre of which weighs d grams, is found, according to the theory, to be equal to the square root of the product of 3pDq divided by d, where p is the pressure under which d is determined expressed in centimetres of the mercury column, D the weight of a cubic centimetre of mercury in grams (D = 13·59, p = 76, consequently the normal pressure = 1,033 grams on a sq. cm.), and g the acceleration of gravity in centimetres (g = 980·5, at the sea level and long. 45° = 981·92 at St. Petersburg; in general it varies with the longitude and altitude of the locality). Therefore, at 0° the velocity of hydrogen is 1,843, and of oxygen 461, metres per second. This is the average velocity, and (according to Maxwell and others) it is probable that the velocities of individual particles are different; that is, they occur in, as it were, different conditions of temperature, which it is very important to take into consideration in investigating many phenomena proper to matter. It is evident from the above determination of the velocity of gases, that different gases at the same temperature and pressure have average velocities, which are inversely proportional to the square roots of their densities; this is also shown by direct experiment on the flow of gases through a fine orifice, or through a porous wall. This dissimilar velocity of flow for different gases is frequently taken advantage of in chemical researches (see Chap. II. and also Chap. VII.) in order to separate two gases having different densities and velocities. The difference of the velocity of flow of gases also determines the phenomenon cited in the following footnote for demonstrating the existence of an internal motion in gases.

If for a certain mass of a gas which fully and exactly follows the laws of Mariotte and Gay-Lussac the temperature t and the pressure p be changed simultaneously, then the entire change would be expressed by the equation pv = C(1 + at), or, what is the same, pv = RT, where T = t + 273 and C and R are constants which vary not only with the units taken but with the nature of the gas and its mass. But as there are discrepancies from both the fundamental laws of gases (which will be discussed in the following chapter), and as, on the one hand, a certain attraction between the gaseous molecules must be admitted, while on the other hand the molecules of gases themselves must occupy a portion of a space, hence for ordinary gases, within any considerable variation of pressure and temperature, recourse should be had to Van der Waal's formula—

(p + a / v² )(v - p) = R(1 + at)

where a is the true co-efficient of expansion of gases.

The formula of Van der Waals has an especially important significance in the case of the passage of a gas into a liquid state, because the fundamental properties of both gases and liquids are equally well expressed by it, although only in their general features.

The further development of the questions referring to the subjects here touched on, which are of especial interest for the theory of solutions, must be looked for in special memoirs and works on theoretical and physical chemistry. A small part of this subject will be partially considered in the footnotes of the following chapter.

[35] Although the actual motion of gaseous molecules, which is accepted by the kinetic theory of gases, cannot be seen, yet its existence may be rendered evident by taking advantage of the difference in the velocities undoubtedly belonging to different gases which are of different densities under equal pressures. The molecules of a light gas must move more rapidly than the molecules of a heavier gas in order to produce the same pressure. Let us take, therefore, two gases—hydrogen and air; the former is 14·4 times lighter than the latter, and hence the molecules of hydrogen must move almost four times more quickly than air (more exactly 3·8, according to the formula given in the preceding footnote). Consequently, if a porous cylinder containing air is introduced into an atmosphere of hydrogen, then in a given time the volume of hydrogen which succeeds in entering the cylinder will be greater than the volume of air leaving the cylinder, and therefore the pressure inside the cylinder will rise until the gaseous mixture (of air and hydrogen) attains an equal density both inside and outside the cylinder. If now the experiment be reversed and air surround the cylinder, and hydrogen be inside the cylinder, then more gas will leave the cylinder than enters it, and hence the pressure inside the cylinder will be diminished. In these considerations we have replaced the idea of the number of molecules by the idea of volumes. We shall learn subsequently that equal volumes of different gases contain an equal number of molecules (the law of Avogadro-Gerhardt), and therefore instead of speaking of the number of molecules we can speak of the number of volumes. If the cylinder be partially immersed in water the rise and fall of the pressure can be observed directly, and the experiment consequently rendered self-evident.

[36] Here two cases occur; either the atmosphere surrounding the solution may be limited, or it may be proportionally so vast as to be unlimited, like the earth's atmosphere. If a gaseous solution be brought into an atmosphere of another gas which is limited—for instance, as in a closed vessel—then a portion of the gas held in solution will be expelled, and thus pass over into the atmosphere surrounding the solution, and will produce its partial pressure. Let us imagine that water saturated with carbonic anhydride at 0° and under the ordinary pressure is brought into an atmosphere of a gas which is not absorbed by water; for instance, that 10 c.c. of an aqueous solution of carbonic anhydride is introduced into a vessel holding 10 c.c. of such a gas. The solution will contain 18 c.c. of carbonic anhydride. The expulsion of this gas proceeds until a state of equilibrium is arrived at. The liquid will then contain a certain amount of carbonic anhydride, which is retained under the partial pressure of that gas which has been expelled. Now, how much gas will remain in the liquid and how much will pass over into the surrounding atmosphere? In order to solve this problem, let us suppose that x cubic centimetres of carbonic anhydride are retained in the solution. It is evident that the amount of carbonic anhydride which passed over into the surrounding atmosphere will be 18 - x, and the total volume of gas will be 10 + 18 - x or 28 - x cubic centimetres. The partial pressure under which the carbonic anhydride is then dissolved will be (supposing that the common pressure remains constant the whole time) equal to 18 - x / 28 - x , hence there is not in solution 18 c.c. of carbonic anhydride (as would be the case were the partial pressure equal to the atmospheric pressure), but only 18 18 - x / 28 - x , which is equal to x, and we therefore obtain the equation 18 18 - x / 28 - x = x, hence x = 8·69. Again, where the atmosphere into which the gaseous solution is introduced is not only that of another gas but also unlimited, then the gas dissolved will, on passing over from the solution, diffuse into this atmosphere, and produce an infinitely small pressure in the unlimited atmosphere. Consequently, no gas can be retained in solution under this infinitely small pressure, and it will be entirely expelled from the solution. For this reason water saturated with a gas which is not contained in air, will be entirely deprived of the dissolved gas if left exposed to the air. Water also passes off from a solution into the atmosphere, and it is evident that there might be such a case as a constant proportion between the quantity of water vaporised and the quantity of a gas expelled from a solution, so that not the gas alone, but the entire gaseous solution, would pass off. A similar case is exhibited in solutions which are not decomposed by heat (such as those of hydrogen chloride and iodide), as will afterwards be considered.

[37] However, in those cases when the variation of the co-efficient of solubility with the temperature is not sufficiently great, and when a known quantity of aqueous vapour and of the gas passes off from a solution at the boiling point, an atmosphere may be obtained having the same composition as the liquid itself. In this case the amount of gas passing over into such an atmosphere will not be greater than that held by the liquid, and therefore such a gaseous solution will distil over unchanged. The solution will then represent, like a solution of hydriodic acid in water, a liquid which is not altered by distillation, while the pressure under which this distillation takes place remains constant. Thus in all its aspects solution presents gradations from the most feeble affinities to examples of intimate chemical combination. The amount of heat evolved in the solution of equal volumes of different gases is in distinct relation with these variations of stability and solubility of different gases. 22·3 litres of the following gases (at 760 mm. pressure) evolve the following number of (gram) units of heat in dissolving in a large mass of water; carbonic anhydride 5,600, sulphurous anhydride 7,700, ammonia 8,800, hydrochloric acid 17,400, and hydriodic acid 19,400. The two last-named gases, which are not expelled from their solution by boiling, evolve approximately twice as much heat as gases like ammonia, which are separated from their solutions by boiling, whilst gases which are only slightly soluble evolve very much less heat.

[38] Among the numerous researches concerning this subject, certain results obtained by Paul Bert are cited in Chapter III., and we will here point out that Prof. Sechenoff, in his researches on the absorption of gases by liquids, very fully investigated the phenomena of the solution of carbonic anhydride in solutions of various salts, and arrived at many important results, which showed that, on the one hand, in the solution of carbonic anhydride in solutions of salts on which it is capable of acting chemically (for example, sodium carbonate, borax, ordinary sodium phosphate), there is not only an increase of solubility, but also a distinct deviation from the law of Henry and Dalton; whilst, on the other hand, that solutions of salts which are not acted on by carbonic anhydride (for example, the chlorides, nitrates, and sulphates) absorb less of it, owing to the ‘competition’ of the salt already dissolved, and follow the law of Henry and Dalton, but at the same time show undoubted signs of a chemical action between the salt, water, and carbonic anhydride. Sulphuric acid (whose co-efficient of absorption is 92 vols. per 100), when diluted with water, absorbs less and less carbonic anhydride, until the hydrate H₂SO₄,H₂O (co-eff. of absorption then equals 66 vols.) is formed; then on further addition of water the solubility again rises until a solution of 100 p.c. of water is obtained.

[39] Kremers made this observation in the following simple form:—He took a narrow-necked flask, with a mark on the narrow part (like that on a litre flask which is used for accurately measuring liquids), poured water into it, and then inserted a funnel, having a fine tube which reached to the bottom of the flask. Through this funnel he carefully poured a solution of any salt, and (having removed the funnel) allowed the liquid to attain a definite temperature (in a water bath); he then filled the flask up to the mark with water. In this manner two layers of liquid were obtained, the heavy saline solution below and water above. The flask was then shaken in order to accelerate diffusion, and it was observed that the volume became less if the temperature remained constant. This can be proved by calculation, if the specific gravity of the solutions and water be known. Thus at 15° one c.c. of a 20 p.c. solution of common salt weighs 1·1500 gram, hence 100 grams occupy a volume of 86·96 c.c. As the sp. gr. of water at 15° = 0·99916, therefore 100 grams of water occupy a volume of 100·08 c.c. The sum of the volumes is 187·04 c.c. After mixing, 200 grams of a 10 p.c. solution are obtained. Its specific gravity is 1·0725 (at 15° and referred to water at its maximum density), hence the 200 grams will occupy a volume of 186·48 c.c. The contraction is consequently equal to 0·56 c.c.

[40] The contractions produced in the case of the solution of sulphuric acid in water are shown in the diagram Fig. 17 (page 77). Their maximum is 10·1 c.c. per 100 c.c. of the solution formed. A maximum contraction of 4·15 at 0°, 3·78 at 15°, and 3·50 at 30°, takes place in the solution of 46 parts by weight of anhydrous alcohol in 54 parts of water. This signifies that if, at 0°, 46 parts by weight of alcohol be taken per 54 parts by weight of water, then the sum of their separate volumes will he 104·15, and after mixing their total volume will be 100.

[41] This subject will be considered later in this work, and we shall then see that the contraction produced in reactions of combination (of solids or liquids) is very variable in its amount, and that there are, although rarely, reactions of combination in which contraction does not take place, or when an increase of volume is produced.

[42] The compressibility of solutions of common salt is less, according to Grassi, than that of water. At 18° the compression of water per million volumes = 48 vols. for a pressure of one atmosphere; for a 15 p.c. solution of common salt it is 32, and for a 24 p.c. solution 26 vols. Similar determinations were made by Brown (1887) for saturated solutions of sal ammoniac (38 vols.), alum (46 vols.), common salt (27 vols.), and sodium sulphate at +1°, when the compressibility of water = 47 per million volumes. This investigator also showed that substances which dissolve with an evolution of heat and with an increase in volume (as, for instance, sal ammoniac) are partially separated from their saturated solutions by an increase of pressure (this experiment was particularly conclusive in the case of sal ammoniac), whilst the solubility of substances which dissolve with an absorption of heat or diminution in volume increases, although very slightly, with an increase of pressure. Sorby observed the same phenomenon with common salt (1863).

[43] The most trustworthy data relating to the variation of the specific gravity of solutions with a change of their composition and temperature, are collected and discussed in my work cited in footnote 19. The practical (for the amount of a substance in solution is determined by the aid of the specific gravities of solutions, both in works and in laboratory practice) and the theoretical (for specific gravity can be more accurately observed than other properties, and because a variation in specific gravity governs the variation of many other properties) interest of this subject, besides the strict rules and laws to which it is liable, make one wish that this province of data concerning solutions may soon be enriched by further observations of as accurate a nature as possible. Their collection does not present any great difficulty, although requiring much time and attention. Pickering in London and Tourbaba in Kharkoff must be ranked first among those who have pursued problems of this nature during recent years.

[44] Inasmuch as the degree of change exhibited in many properties on the formation of solutions is not large, so, owing to the insufficient accuracy of observations, a proportionality between this change and a change of composition may, in a first rough approximation and especially within narrow limits of change of composition, easily be imagined in cases where it does not even exist. The conclusion of Michel and Kraft is particularly instructive in this respect; in 1854, on the basis of their incomplete researches, they supposed that the increment of the specific gravity of solutions was proportional to the increment of a salt in a given volume of a solution, which is only true for determinations of specific gravity which are exact to the second decimal place—an accuracy insufficient even for technical determinations. Accurate measurements do not confirm a proportionality either in this case or in many others where a ratio has been generally accepted; as, for example, for the rotatory power (with respect to the plane of polarisation) of solutions, and for their capillarity, &c. Nevertheless, such a method is not only still made use of, but even has its advantages when applied to solutions within a limited scope—as, for instance, very weak solutions, and for a first acquaintance with the phenomena accompanying solution, and also as a means for facilitating the application of mathematical analysis to the investigation of the phenomenon of solution. Judging by the results obtained in my researches on the specific gravity of solutions, I think that in many cases it would be nearer the truth to take the change of properties as proportional, not to the amount of a substance dissolved, but to the product of this quantity and the amount of water in which it is dissolved; the more so since many chemical relations vary in proportion to the reacting masses, and a similar ratio has been established for many phenomena of attraction studied by mechanics. This product is easily arrived at when the quantity of water in the solutions to be compared is constant, as is shown in investigating the fall of temperature in the formation of ice (see footnote 49, p. 91).

[45] All the different forms of chemical reaction may be said to take place in the process of solution. (1) Combinations between the solvent and the substance dissolved, which are more or less stable (more or less dissociated). This form of reaction is the most probable, and is that most often observed. (2) Reactions of substitution or of double decomposition between the molecules. Thus it may be supposed that in the solution of sal ammoniac, NH₄Cl, the action of water produces ammonia, NH₄HO, and hydrochloric acid, HCl, which are dissolved in the water and simultaneously attract each other. As these solutions and many others do indeed exhibit signs, which are sometimes indisputable, of similar double decompositions (thus solutions of sal-ammoniac yield a certain amount of ammonia), it is probable that this form of reaction is more often met with than is generally thought. (3) Reactions of isomerism or replacement are also probably met with in solution, all the more as here molecules of different kinds come into intimate contact, and it is very likely that the configuration of the atoms in the molecules under these influences is somewhat different from what it was in its original and isolated state. One is led to this supposition especially from observations made on solutions of substances which rotate the plane of polarisation (and observations of this kind are very sensitive with respect to the atomic structure of molecules), because they show, for example (according to Schneider, 1881), that strong solutions of malic acid rotate the plane of polarisation to the right, whilst its ammonium salts in all degrees of concentration rotate the plane of polarisation to the left. (4) Reactions of decomposition under the influences of solution are not only rational in themselves, but have in recent years been recognised by Arrhenius, Ostwald, and others, particularly on the basis of electrolytic determinations. If a portion of the molecules of a solution occur in a condition of decomposition, the other portion may occur in a yet more complex state of combination, just as the velocity of the motion of different gaseous molecules may be far from being the same (see Note 34, p. 81).

It is, therefore, very probable that the reactions taking place in solution vary both quantitatively and qualitatively with the mass of water in the solution, and the great difficulty in arriving at a definite conclusion as to the nature of the chemical relations which take place in the process of solution will be understood, and if besides this the existence of a physical process, like the sliding between and interpenetration of two homogeneous liquids, be also recognised in solution, then the complexity of the problem as to the actual nature of solutions, which is now to the fore, appears in its true light. However, the efforts which are now being applied to the solution of this problem are so numerous and of such varied aspect that they will afford future investigators a vast mass of material towards the construction of a complete theory of solution.

For my part, I am of opinion that the study of the physical properties of solutions (and especially of weak ones) which now obtains, cannot give any fundamental and complete solution of the problem whatever (although it should add much to both the provinces of physics and chemistry), but that, parallel with it, should be undertaken the study of the influence of temperature, and especially of low temperatures, the application to solutions of the mechanical theory of heat, and the comparative study of the chemical properties of solutions. The beginning of all this is already established, but it is impossible to consider in so short an exposition of chemistry the further efforts of this kind which have been made up to the present date.

[46] If solutions are regarded as being in a state of dissociation (see footnote 19, p. 64) it would be expected that they would contain free molecules of water, which form one of the products of the decomposition of those definite compounds whose formation is the cause of solution. In separating as ice or vapour, water makes, with a solution, a heterogeneous system (made up of substances in different physical states) similar, for instance, to the formation of a precipitate or volatile substance in reactions of double decomposition.

[47] If the substance dissolved is non-volatile (like salt or sugar), or only slightly volatile, then the whole of the tension of the vapour given off is due to the water, but if a solution of a volatile substance—for instance, a gas or a volatile liquid—evaporates, then only a portion of the pressure belongs to the water, and the whole pressure observed consists of the sum of the pressures of the vapours of the water and of the substance dissolved. The majority of researches bear on the first case, which will be spoken of presently, and the observations of D. P. Konovaloff (1881) refer to the second case. He showed that in the case of two volatile liquids, mutually soluble in each other, forming two layers of saturated solutions (for example, ether and water, Note 20, p. 67), both solutions have an equal vapour tension (in the case in point the tension of both is equal to 431 mm. of mercury at 19·8°). Further, he found that for solutions which are formed in all proportions, the tension is either greater (solutions of alcohol and water) or less (solutions of formic acid) than that which answers to the rectilinear change (proportional to the composition) from the tension of water to the tension of the substance dissolved; thus, the tension, for example, of a 70 p.c. solution of formic acid is less, at all temperatures, than the tension of water and of formic acid itself. In this case the tension of a solution is never equal to the sum of the tensions of the dissolving liquids, as Regnault already showed when he distinguished this case from that in which a mixture of liquids, which are insoluble in each other, evaporates. From this it is evident that a mutual action occurs in solution, which diminishes the vapour tensions proper to the individual substances, as would be expected on the supposition of the formation of compounds in solutions, because the elasticity then always diminishes.

[48] This amount is usually expressed by the weight of the substance dissolved per 100 parts by weight of water. Probably it would be better to express it by the quantity of the substance in a definite volume of the solution—for instance, in a litre—or by the ratios of the number of molecules of water and of the substance dissolved.

[49] The variation of the vapour tension of solutions has been investigated by many. The best known researches are those of Wüllner in Germany (1858–1860) and of Tamman in Russia (1887). The researches on the temperature of the formation of ice from various solutions are also very numerous; Blagden (1788), Rüdorff (1861), and De Coppet (1871) established the beginning, but this kind of investigation takes its chief interest from the work of Raoult, begun in 1882 on aqueous solutions, and afterwards continued for solutions in various other easily frozen liquids—for instance, benzene, C₆H₆ (melts at 4·96°), acetic acid, C₂H₄O₂ (16·75°), and others. An especially important interest is attached to these cryoscopic investigations of Raoult in France on the depression of the freezing point, because he took solutions of many well-known carbon-compounds and discovered a simple relation between the molecular weight of the substances and the temperature of crystallisation of the solvent, which enabled this kind of research to be applied to the investigation of the nature of substances. We shall meet with the application of this method later on (see also Chapter VII.), and at present will only cite the deduction arrived at from these results. The solution of one-hundredth part of that molecular gram weight which corresponds with the formula of a substance dissolved (for example, NaCl = 58·5, C₂H₆O = 46, &c.) in 100 parts of a solvent lowers the freezing point of its solution in water 0·185°, in benzene 0·49°, and in acetic acid O·39°, or twice as much as with water. And as in weak solutions the depression or fall of freezing point is proportional to the amount of the substance dissolved, it follows that the fall of freezing point for all other solutions may be calculated from this rule. So, for instance, the weight which corresponds with the formula of acetone, C₃H₆O is 58; a solution containing 2·42, 6·22, and 12·35 grams of acetone per 100 grams of water, forms ice (according to the determinations of Beckmann) at 0·770°, 1·930°, and 3·820°, and these figures show that with a solution containing 0·58 gram of acetone per 100 of water the fall of the temperature of the formation of ice will be 0·185°, 0·180°, and 0·179°. It must be remarked that the law of proportionality between the fall of temperature of the formation of ice, and the composition of a solution, is in general only approximate, and is only applicable to weak solutions (Pickering and others).

We will here remark that the theoretical interest of this subject was strengthened on the discovery of the connection existing between the fall of tension, the fall of the temperature of the formation of ice, of osmotic pressure (Van't Hoff, Note 19), and of the electrical conductivity of solutions, and we will therefore supplement what we have already said on the subject by some short remarks on the method of cryoscopic investigations, although the details of the subject form the subject of more special works on physical chemistry (such as Ostwald's Lehrbuch der allgemeinen Chemie, 1891–1894, 2 vols.)

In order to determine the temperature of the formation of ice (or of crystallisation of other solvents), a solution of known strength is prepared and poured into a cylindrical vessel surrounded by a second similar vessel, leaving a layer of air between the two, which, being a bad conductor, prevents any rapid change of temperature. The bulb of a sensitive and corrected thermometer is immersed in the solution, and also a bent platinum wire for stirring the solution; the whole is then cooled (by immersing the apparatus in a freezing mixture), and the temperature at which ice begins to separate observed. If the temperature at first falls slightly lower, it nevertheless becomes constant when ice begins to form. By then allowing the liquid to get just warm, and again observing the temperature of the formation of ice, an exact determination may be arrived at. It is still better to take a large mass of solution, and induce the formation of the first crystals by dropping a small lump of ice into the solution already partially over-cooled. This only imperceptibly changes the composition of the solution. The observation should be made at the point of formation of only a very small amount of crystals, as otherwise the composition of the solution will become altered from their separation. Every precaution must be taken to prevent the access of moisture to the interior of the apparatus, which might also alter the composition of the solution or properties of the solvent (for instance, when using acetic acid).

With respect to the depression of dilute solutions it is known—(1) That the depression increases in almost direct proportion to the amount of the substance in solution (always per 100 parts of water), for example, for KCl when the solution contains 1 part of salt (per 100 parts of water) the depression = 0·45°, when the solution contains 2 parts of salt = 0·90°, with 10 parts of salt = 4·4°. (2) The greater the molecular weight expressed by the formula (see Chapter VII.), and designated by M, the less, under other similar conditions, will be the depression d, and therefore if the concentration of a solution (the amount by weight of substance dissolved per 100 parts of water) be designated by p, then the fraction M d / p or the molecular depression for a given class of substances will be a constant quantity; for example, in the case of methyl alcohol in water 17·3, for acetone about 18·0, for sugar about 18·5. (3) In general the molecular depression for substances whose solutions do not conduct an electric current is about 18·5, while for acids, salts, and such like substances whose solutions do conduct electricity, it is i times greater; for instance, for HCl, KI, HNO₃, KHO, &c., about 36 (i is nearly 2), for borax about 66, and so on where i varies in the same manner as it does in the case of the osmotic pressure of solutions (Note 19). (4) Different solvents (water, acetic acid, benzene, &c.) have each their corresponding constants of molecular depression (which have a certain remote connection with their molecular weight); for example, for acetic acid the molecular depression is about 39 and not 19 (as it is for water), for benzene 49, for methyl alcohol about 17, &c. (5) If the molecular weight M of a substance be unknown, then in the case of non-conductors of electricity or for a given group, it may be found by determining the depression, d, for a given concentration, p; for example, in the case of peroxide of hydrogen, which is a non-conductor of electricity, the molecular weight, M, was found to be nearly 34, i.e. equal to H₂O₂.

Similar results have also been found for the fall in the vapour tension of solutions (Note 51), and for the rise of their boiling points (hence these data may also serve for determining the molecular weight of a substance in solution, as is shortly described in Chapter VII., Note 27 bis). And as these conclusions are also applicable in the case of osmotic pressure (Note 19), and a variation in the magnitude of i, in passing from solutions which do not conduct an electric current to those which do conduct electricity is everywhere remarked, so it was natural to here seek that causal connection which Arrhenius (1888), Ostwald, and others expected to find in the supposition that a portion of the substance of the electrolyte is already decomposed in the very act of solution, into its ions (for example, NaCl into Na and Cl), or into the atoms of those individual substances which make their appearance in electrolysis, and in this way to explain the fact that i is greater for those bodies which conduct an electric current. We will not consider here this supposition, known as the hypothesis of ‘electrolytic dissociation,’ not only because it wholly belongs to that special branch—physical chemistry, and gives scarcely any help towards explaining the chemical relations of solutions (particularly their passage into definite compounds, their reactions, and their very formation), but also because—(1) all the above data (for constant depression, osmotic pressure, &c.) only refer to dilute solutions, and are not applicable to strong solutions; whilst the chemical interest in strong solutions is not less than in dilute solutions, and the transition from the former into the latter is consecutive and inevitable; (2) because in all homogeneous bodies (although it may be insoluble and not an electrolyte) a portion of the atoms may he supposed (Clausius) to be passing from one particle to another (Chapter X., Note 28), and as it were dissociated, but there are no reasons for believing that such a phenomenon is proper to the solutions of electrolytes only; (3) because no essential mark of difference is observed between the solution of electrolytes and non-conductors, although it might be expected there would be according to Arrhenius' hypothesis; (4) because it is most reasonable to suppose the formation of new, more complex, but unstable and easily dissociated compounds in the act of solution, than a decomposition, even partial, of the substances taken; (5) because if Arrhenius' hypothesis be accepted it becomes necessary to admit the existence in solutions of free ions, like the atoms Cl or Na, without any apparent expenditure of the energy necessary for their disruption, and if in this case it can be explained why i then = 2, it is not at all clear why solutions of MgSO₄ give i = 1, although the solution does conduct an electric current; (6) because in dilute solutions, the approximative proportionality between the depression and concentration may be recognised, while admitting the formation of hydrates, with as much right as in admitting the solution of anhydrous substances, and if the formation of hydrates be recognised it is easier to admit that a portion of these hydrates is decomposed than to accept the breaking-up into ions; (7) because the best conductors of electricity are solutions like the sulphates in which it is necessary to recognise the formation of associated systems or hydrates; (8) because the cause of electro-conductivity can be sooner looked for in this affinity and this combination of the substance dissolved with the solvent, as is seen from the fact, that (D. P. Konovaloff) neither aniline nor acetic acid alone conduct an electric current, a solution of aniline in water conducts it badly (and here the affinity is very small), while a solution of aniline in acetic acid forms a good electrolyte, in which, without doubt, chemical forces are acting, bringing aniline, like ammonia, into combination with the acetic acid; which is evident from the researches made by Prof. Konovaloff upon mixtures (solutions) of aniline and other amines; and, lastly, (9) because I, together with many of the chemists of the present day, cannot regard the hypothesis of electrolytic dissociation in the form given to it up to now by Arrhenius and Ostwald, as answering to the sum total of the chemical data respecting solutions and dissociation in general. Thus, although I consider it superfluous to discuss further the evolution of the above theory of solutions, still I think that it would he most useful for students of chemistry to consider all the data referring to this subject, which can be found in the Zeitschrift für physikalische Chemie, 1888–1894.

[50] This fact, which was established by Gay-Lussac, Pierson, and v. Babo, is confirmed by the latest observations, and enables us to express not only the fall of tension (p - p′) itself, but its ratio to the tension of water ( p - p′ / p ). It is to be remarked that in the absence of any chemical action, the fall of pressure is either very small, or does not exist at all (note 33), and is not proportional to the quantity of the substance added. As a rule, the tension is then equal, according to the law of Dalton, to the sum of the tensions of the substances taken. Hence liquids which are insoluble in each other (for example, water and chloride of carbon) present a tension equal to the sum of their individual tensions, and therefore such a mixture boils at a lower temperature than the more volatile liquid (Magnus, Regnault).

[51] If, in the example of common salt, the fall of tension be divided by the tension of water, a figure is obtained which is nearly 105 times less than the magnitude of the fall of temperature of formation of ice. This correlation was theoretically deduced by Goldberg, on the basis of the application of the mechanical theory of heat, and is repeated by many investigated solutions.

[52] Fritzsche showed that solutions of certain colouring matters yield colourless ice, which clearly proves the passage of water only into a solid state, without any intermixture of the substance dissolved, although the possibility of the admixture in certain other cases cannot be denied.

[53] As the solubility of certain substances (for example, coniine, cerium sulphate, and others) decreases with a rise of temperature (between certain limits—see, for example, note 24), so these substances do not separate from their saturated solutions on cooling but on heating. Thus a solution of manganese sulphate, saturated at 70°, becomes cloudy on further heating. The point at which a substance separates from its solution with a change of temperature gives an easy means of determining the co-efficient of solubility, and this was taken advantage of by Prof. Alexéeff for determining the solubility of many substances. The phenomenon and method of observation are here essentially the same as in the determination of the temperature of formation of ice. If a solution of a substance which separates out on heating be taken (for example, the sulphate of calcium or manganese), then at a certain fall of temperature ice will separate out from it, and at a certain rise of temperature the salt will separate out. From this example, and from general considerations, it is clear that the separation of a substance dissolved from a solution should present a certain analogy to the separation of ice from a solution. In both cases, a heterogeneous system of a solid and a liquid is formed from a homogeneous (liquid) system.

[54] Those salts which separate out with water of crystallisation and give several crystallohydrates form supersaturated solutions with the greatest facility, and the phenomenon is much more common than was previously imagined. The first data were given in the last century by Loewitz, in St. Petersburg. Numerous researches have proved that supersaturated solutions do not differ from ordinary solutions in any of their essential properties. The variations in specific gravity, vapour tension, formation of ice, &c., take place according to the ordinary laws.

[55] Inasmuch as air, as has been shown by direct experiment, contains, although in very small quantities, minute crystals of salts, and among them sodium sulphate, air can bring about the crystallisation of a supersaturated solution of sodium sulphate in an open vessel, but it has no effect on saturated solutions of certain other salts; for example, lead acetate. According to the observations of De Boisbaudran, Gernez, and others, isomorphous salts (analogous in composition) are capable of inducing crystallisation. Thus, a supersaturated solution of nickel sulphate crystallises by contact with crystals of sulphates of other metals analogous to it, such as those of magnesium, cobalt, copper, and manganese. The crystallisation of a supersaturated solution, set up by the contact of a minute crystal, starts from it in rays with a definite velocity, and it is evident that the crystals as they form propagate the crystallisation in definite directions. This phenomenon recalls the evolution of organisms from germs. An attraction of similar molecules ensues, and they dispose themselves in definite similar forms.

[56] At the present time a view is very generally accepted, which regards supersaturated solutions as homogeneous systems, which pass into heterogeneous systems (composed of a liquid and a solid substance), in all respects exactly resembling the passage of water cooled below its freezing point into ice and water, or the passage of crystals of rhombic sulphur into monoclinic crystals, and of the monoclinic crystals into rhombic. Although many phenomena of supersaturation are thus clearly understood, yet the spontaneous formation of the unstable hepta-hydrated salt (with 7H₂O), in the place of the more stable deca-hydrated salt (with mol. 10H₂O), indicates a property of a saturated solution of sodium sulphate which obliges one to admit that it has a different structure from an ordinary solution. Stcherbacheff asserts, on the basis of his researches, that a solution of the deca-hydrated salt gives, on evaporation, without the aid of heat, the deca-hydrated salt, whilst after heating above 33° it forms a supersaturated solution and the hepta-hydrated salt. But in order that this view should be accepted, some facts must be discovered distinguishing solutions (which are, according to this view, isomeric) containing the hepta-hydrated salt from those containing the deca-hydrated salt, and all efforts in this direction (the study of the properties of the solutions) have given negative results. As some crystallohydrates of salts (alums, sugar of lead, calcium chloride) melt straightway (without separating out anything), whilst others (like Na₂SO₄,10H₂O) are broken up, then it may be that the latter are only in a state of equilibrium at a higher temperature than their melting point. It may here be observed that in melting crystals of the deca-hydrated salt, there is formed, besides the solid anhydrous salt, a saturated solution giving the hepta-hydrated salt, so that this passage from the deca-to the hepta-hydrated salt, and the reverse, takes place with the formation of the anhydrous (or, it may be, monohydrated) salt.

Moreover, supersaturation (Potilitzin, 1889) only takes place with those substances which are capable of giving several modifications or several crystallohydrates, i.e. supersaturated solutions separate out, besides the stable normal crystallohydrate, hydrates containing less water and also the anhydrous salt. This degree of saturation acts upon the substance dissolved in a like manner to heat. Sulphate of nickel in a solution at 15° to 20° separates out rhombic crystals with 7H₂O, at 30° to 40° cubical crystals, with 6H₂O, at 50° to 70° monoclinic crystals, also containing 6H₂O. Crystals of the same composition separate out from supersaturated solutions at one temperature (17° to 19°), but at different degrees of saturation, as was shown by Lecoq de Boisbaudran. The capacity to voluntarily separate out slightly hydrated or anhydrous salts by the introduction of a crystal into the solution is common to all supersaturated solutions. If a salt forms a supersaturated solution, then one would expect, according to this view, that it should exist in the form of several hydrates or in several modifications. Thus Potilitzin concluded that chlorate of strontium, which easily gives supersaturated solutions, should be capable of forming several hydrates, besides the anhydrous salt known; and he succeeded in discovering the existence of two hydrates, Sr(ClO₃)₂,3H₂O and apparently Sr(ClO₃)₂,8H₂O. Besides this, three modifications of the common anhydrous salt were obtained, differing from each other in their crystalline form. One modification separated out in the form of rhombic octahedra, another in oblique plates, and a third in long brittle prisms or plates. Further researches showed that salts which are not capable of forming supersaturated solutions such as the bromates of calcium, strontium, and barium, part with their water of hydration with difficulty (they crystallise with 1H₂O), and decompose very slowly in a vacuum or in dry air. In other words the tension of dissociation is very small in this class of hydrates. As the hydrates characterised by a small dissociation tension are incapable of giving supersaturated solutions, so conversely supersaturated solutions give hydrates whose tension of dissociation is great (Potilitzin, 1893).

[57] Emulsions, like milk, are composed of a solution of glutinous or similar substances, or of oily liquids suspended in a liquid in the form of drops, which are clearly visible under a microscope, and form an example of a mechanical formation which resembles solution. But the difference from solutions is here evident. There are, however, solutions which approach very near to emulsions in the facility with which the substance dissolved separates from them. It has long been known, for example, that a particular kind of Prussian blue, KFe₂(CN)₆, dissolves in pure water, but, on the addition of the smallest quantity of either of a number of salts, it coagulates and becomes quite insoluble. If copper sulphide (CuS), cadmium sulphide (CdS), arsenic sulphide (As₂S₅) (the experiments with these substances proceed with great ease, and the solution obtained is comparatively stable), and many other metallic sulphides, be obtained by a method of double decomposition (by precipitating salts of these metals by hydrogen sulphide), and be then carefully washed (by allowing the precipitate to settle, pouring off the liquid, and again adding sulphuretted hydrogen water), then, as was shown by Schulze, Spring, Prost, and others, the previously insoluble sulphides pass into transparent (for mercury, lead, and silver, reddish brown; for copper and iron, greenish brown; for cadmium and indium, yellow; and for zinc, colourless) solutions, which may be preserved (the weaker they are the longer they keep) and even boiled, but which, nevertheless, in time coagulate—that is, separate in an insoluble form, and then sometimes become crystalline and quite incapable of re-dissolving. Graham and others observed the power shown by colloids (see note 18) of forming similar hydrosols or solutions of gelatinous colloids, and, in describing alumina and silica, we shall again have occasion to speak of such solutions.

In the existing state of our knowledge concerning solution, such solutions may be looked on as a transition between emulsion and ordinary solutions, but no fundamental judgment can be formed about them until a study has been made of their relations to ordinary solutions (the solutions of even soluble colloids freeze immediately on cooling below 0°, and, according to Guthrie, do not form cryohydrates), and to supersaturated solutions, with which they have certain points in common.

[58] Offer (1880) concludes, from his researches on cryohydrates, that they are simple mixtures of ice and salts, having a constant melting point, just as there are alloys having a constant point of fusion, and solutions of liquids with a constant boiling point (see note 60). This does not, however, explain in what form a salt is contained, for instance, in the cryohydrate NaCl + 10H₂O. At temperatures above -10° common salt separates out in anhydrous crystals, and at temperatures near -10°, in combination with water of crystallisation, NaCl + 2H₂O, and, therefore, it is very improbable that at still lower temperatures it would separate without water. If the possibility of the solidified cryohydrate containing NaCl + 2H₂O and ice be admitted, then it is not clear why one of these substances does not melt before the other. If alcohol does not extract water from the solid mass, leaving the salt behind, this does not prove the presence of ice, because alcohol also takes up water from the crystals of many hydrated substances (for instance, from NaCl + 2H₂O) at about their melting-points. Besides which, a simple observation on the cryohydrate, NaCl + 10H₂O, shows that with the most careful cooling it does not on the addition of ice deposit ice, which would occur if ice were formed on solidification intermixed with the salt.

I may add with regard to cryohydrates that many of the solutions of acids solidify completely on prolonged cooling (for example, H₂SO₄,H₂O), and then form perfectly definite compounds. For the solutions of sulphuric acid (see Chapter X.) Pickering obtained, for instance, a hydrate, H₂SO₄,4H₂O at -25°. Hydrochloric, nitric, and other acids also give similar crystalline hydrates, melting at low temperatures and presenting many similarities with the cryohydrates.

[59] See note 24.

[60] For this reason (the want of entire constancy of the composition of constant boiling solutions with a change of pressure), the existence of definite hydrates formed by volatile substances—for instance, by hydrochloric acid and water—is frequently denied. It is generally argued as follows: If there did exist a constancy of composition, then it would be unaltered by a change of pressure. But the distillation of constant boiling hydrates is undoubtedly accompanied (judging by the vapour densities determined by Bineau), like the distillation of sal ammoniac, sulphuric acid, &c., by a complete decomposition of the original compound—that is, these substances do not exist in a state of vapour, but their products of decomposition (hydrochloric acid and water) are gases at the temperature of volatilisation, which dissolve in the volatilised and condensed liquids; but the solubility of gases in liquids depends on the pressure, and, therefore, the composition of constant boiling solutions may, and even ought to, vary with a change of pressure, and, further, the smaller the pressure and the lower the temperature of volatilisation, the more likely is a true compound to be obtained. According to the researches of Roscoe and Dittmar (1859), the constant boiling solution of hydrochloric acid proved to contain 18 p.c. of hydrochloric acid at a pressure of 3 atmospheres, 20 p.c. at 1 atmosphere, and 23 p.c. at ¹⁄₁₀ of an atmosphere. On passing air through the solution until its composition became constant (i.e. forcing the excess of aqueous vapour or of hydrochloric acid to pass away with the air), then acid was obtained containing about 20 p.c. at 100°, about 23 p.c. at 50°, and about 25 p.c. at 0°. From this it is seen that by decreasing the pressure and lowering the temperature of evaporation one arrives at the same limit, where the composition should be taken as HCl + 6H₂O, which requires 25·26 p.c. of hydrochloric acid. Fuming hydrochloric acid contains more than this.

In the case already considered, as in the case of formic acid in the researches of D. P. Konovaloff (note 47), the constant boiling solution corresponds with a minimum tension—that is, with a boiling point higher than that of either of the component elements. But there is another case of constant boiling solutions similar to the case of the solution of propyl alcohol, C₃H₈O, when a solution, undecomposed by distillation, boils at a lower point than that of the more volatile liquid. However, in this case also, if there be solution, the possibility of the formation of a definite compound in the form C₃H₈O + H₂O cannot be denied, and the tension of the solution is not equal to the sum of tensions of the components. There are possible cases of constant boiling mixtures even when there is no solution nor any loss of tension, and consequently no chemical action, since the amount of liquids that are volatilised is determined by the product of the vapour densities into their vapour tensions (Wanklyn), in consequence of which liquids whose boiling point is above 100°—for instance, turpentine and ethereal oils in general—when distilled with aqueous vapour, pass over at a temperature below 100°. Consequently, it is not in the constancy of composition and boiling point (temperature of decomposition) that evidence of a distinct chemical action is to be found in the above-described solutions of acids, but in the great loss of tension, which completely resembles the loss of tension observed, for instance, in the perfectly-definite combinations of substances with water of crystallisation (see later, note 65). Sulphuric acid, H₂SO₄, as we shall learn later, is also decomposed by distillation, like HCl + 6H₂O, and exhibits, moreover, all the signs of a definite chemical compound. The study of the variation of the specific gravities of solutions as dependent on their composition (see note 19) shows that phenomena of a similar kind, although of different dimensions, take place in the formation of both H₂SO₄ from H₂O and SO₃, and of HCl + 6H₂O (or of aqueous solutions analogous to it) from HCl and H₂O.

[61] The essence of the matter may he thus represented. A gaseous or easily volatile substance A forms with a certain quantity of water, nH₂O, a definite complex compound AnH₂O, which is stable up to a temperature t° higher than 100°. At this temperature it is decomposed into two substances, A + H₂O. Both boil below t° at the ordinary pressure, and therefore at t° they distil over and re-combine in the receiver. But if a part of the substance AnH₂O is decomposed or volatilised, a portion of the undecomposed liquid still remains in the vessel, which can partially dissolve one of the products of decomposition, and that in quantity varying with the pressure and temperature, and therefore the solution at a constant boiling point will have a slightly different composition at different pressures.

[62] For solutions of hydrochloric acid in water there are still greater differences in reactions. For instance, strong solutions decompose antimony sulphide (forming hydrogen sulphide, H₂S), and precipitate common salt from its solutions, whilst weak solutions do not act thus.

[63] Supersaturated solutions give an excellent proof in this respect. Thus a solution of copper sulphate generally crystallises in penta-hydrated crystals, CuSO₄ + 5H₂O, and its saturated solution gives such crystals if it be brought into contact with the minutest possible crystal of the same kind. But, according to the observations of Lecoq de Boisbaudran, if a crystal of ferrous sulphate (an isomorphous salt, see note 55), FeSO₄ + 7H₂O, be placed in a saturated solution of copper sulphate, then crystals of hepta-hydrated salt, CuSO₄ + 7H₂O, are obtained. It is evident that neither the penta- nor the hepta-hydrated salt is contained as such in the solution. The solution presents its own particular liquid form of equilibrium.

[64] Efflorescence, like every evaporation, proceeds from the surface. In the interior of crystals which have effloresced there is usually found a non-effloresced mass, so that the majority of effloresced crystals of washing soda show, in their fracture, a transparent nucleus coated by an effloresced, opaque, powdery mass. It is a remarkable circumstance in this respect that efflorescence proceeds in a completely regular and uniform manner, so that the angles and planes of similar crystallographic character effloresce simultaneously, and in this respect the crystalline form determines those parts of crystals where efflorescence starts, and the order in which it continues. In solutions evaporation also proceeds from the surface, and the first crystals which appear on its reaching the required degree of saturation are also formed at the surface. After falling to the bottom the crystals naturally continue to grow (see Chapter X.).

[65] According to Lescœur (1883), at 100° a concentrated solution of barium hydroxide, BaH₂O₂, on first depositing crystals (with + H₂O) has a tension of about 630 mm. (instead of 760 mm., the tension of water), which decreases (because the solution evaporates) to 45 mm., when all the water is expelled from the crystals, BaH₂O₂ + H₂O, which are formed, but they also lose water (dissociate, effloresce at 100°), leaving the hydroxide, BaH₂O₂, which is perfectly undecomposable at 100°—that is, does not part with water. At 73° (the tension of water is then 265 mm.) a solution, containing 33H₂O, on crystallising has a tension of 230 mm.; the crystals, BaH₂O₂ + 8H₂O, which separate out, have a tension of 160 mm.; on losing water they give BaH₂O₂ + H₂O. This substance does not decompose at 73°, and therefore its tension = 0. In those crystallohydrates which effloresce at the ordinary temperature, the tension of dissociation nearly approximates to that of the aqueous vapour, as Lescœur (1891) showed. To this category of compounds belong B₂O₃(3 + x)H₂O, C₂O₄H₂(2 + x)H₂O, BaO(9 + x)H₂O, and SrO(9 + x)H₂O. And a still greater tension is possessed by Na₂SO₄10H₂O, Na₂CO₃10H₂O, and MgSO₄(7 + x)H₂O. Müller-Erzbach (1884) determines the tension (with reference to liquid water) by placing tubes of the same length with water and the substances experimented with in a desiccator, the rate of loss of water giving the relative tension. Thus, at the ordinary temperature, crystals of sodium phosphate, Na₂HPO₄ + 12H₂O, present a tension of 0·7 compared with water, until they lose 5H₂O, then 0·4 until they lose 5H₂O more, and on losing the last equivalent of water the tension falls to 0·04 compared with water. It is clear that the different molecules of water are held by an unequal force. Out of the five molecules of water in copper sulphate the two first are comparatively easily separated even at the ordinary temperature (but only after several days in a desiccator, according to Latchinoff); the next two are more difficultly separated, and the last equivalent is retained even at 100°. This is another indication of the capacity of CuSO₄ to form three hydrates, CuSO₄5H₂O, CuSO₄3H₂O, and CuSO₄H₂O. The researches of Andreae on the tension of dissociation of hydrated sulphate of copper showed (1891) the existence of three provinces, characterised at a given temperature by a constant tension: (1) between 3–5, (2) between 1–3, and lastly (3) between 0–1 molecule of water, which again confirms the existence of three hydrates of the above composition for this salt.

[65 bis] Sodium acetate (C₂H₃O₂Na,3H₂O) melts at 58°, but re-solidifies only on contact with a crystal, otherwise it may remain liquid even at 0°, and may be used for obtaining a constant temperature. According to Jeannel, the latent heat of fusion is about 28 calories, and according to Pickering the heat of solution 35 calories. When melted this salt boils at 123°—that is, the tension of the vapour given off at that temperature equals the atmospheric pressure.

[66] Such a phenomenon frequently presents itself in purely chemical action. For instance, let a liquid substance A give, with another liquid substance B, under the conditions of an experiment, a mere minute quantity of a solid or gaseous substance C. This small quantity will separate out (pass away from the sphere of action, as Berthollet expressed it), and the remaining masses of A and B will again give C; consequently, under these conditions action will go on to the end. Such, it seems to me, is the action in solutions when they yield ice or vapour indicating the presence of water.

[67] Certain substances are capable of forming together only one compound, others several, and these of the most varied degrees of stability. The compounds of water are instances of this kind. In solutions the existence of several different definite compounds must be acknowledged, but many of these have not yet been obtained in a free state, and it may be that they cannot be obtained in any other but a liquid form—that is, dissolved; just as there are many undoubted definite compounds which only exist in one physical state. Among the hydrates such instances occur. The compound CO₂ + 8H₂O (see note 31), according to Wroblewski, only occurs in a solid form. Hydrates like H₂S + 12H₂O (De Forcrand and Villard), HBr + H₂O (Roozeboom), can only be accepted on the basis of a decrease of tension, but present themselves as very transient substances, incapable of existing in a stable free state. Even sulphuric acid, H₂SO₄, itself, which undoubtedly is a definite compound, fumes in a liquid form, giving off the anhydride, SO₃—that is, it exhibits a very unstable equilibrium. The crystallo-hydrates of chlorine, Cl₂ + 8H₂O, of hydrogen sulphide, H₂S + 12H₂O (it is formed at 0°, and is completely decomposed at +1°, as then 1 vol. of water only dissolves 4 vols. of hydrogen sulphide, while at 0·1° it dissolves about 100 vols.), and of many other gases, are instances of hydrates which are very unstable.

[68] Of such a kind are also other indefinite chemical compounds; for example, metallic alloys. These are solid substances or solidified solutions of metals. They also contain definite compounds, and may contain an excess of one of the metals. According to the experiments of Laurie (1888), the alloys of zinc with copper in respect to the electro-motive force in galvanic batteries behave just like zinc if the proportion of copper in the alloy does not exceed a certain percentage—that is, until a definite compound is attained—for in that case particles of free zinc are present; but if a copper surface be taken, and it be covered by only one-thousandth part of its area of zinc, then only the zinc will act in a galvanic battery.

[69] According to the above supposition, the condition of solutions in the sense of the kinetic hypothesis of matter (that is, on the supposition of an internal motion of molecules and atoms) may be represented in the following form:—In a homogeneous liquid—for instance, water—the molecules occur in a certain state of, although mobile, still stable, equilibrium. When a substance A dissolves in water, its molecules form with several molecules of water, systems AnH₂O, which are so unstable that when surrounded by molecules of water they decompose and re-form, so that A passes from one mass of molecules of water to another, and the molecules of water which were at this moment in harmonious motion with A in the form of the system AnH₂O, in the next instant may have already succeeded in getting free. The addition of water or of molecules of A may either only alter the number of free molecules, which in their turn enter into systems AnH₂O, or they may introduce conditions for the possibility of building up new systems AmH₂O, where m is either greater or less than n. If in the solution the relation of the molecules be the same as in the system AmH₂O, then the addition of fresh molecules of water or of A would be followed by the formation of new molecules AnH₂O. The relative quantity, stability, and composition of these systems or definite compounds will vary in one or another solution. I adopted this view of solutions (1887, Pickering subsequently put forward a similar view) after a most intimate study of the variation of their specific gravities, to which my book, cited in note 19, is devoted. Definite compounds, An₁H₂O and Am₁H₂O, existing in a free—for instance, solid—form, may in certain cases be held in solutions in a dissociated state (although but partially); they are similar in their structure to those definite substances which are formed in solutions, but it is not necessary to assume that such systems as Na₂SO₄ + 10H₂O, or Na₂SO₄ + 7H₂O, or Na₂SO₄, are contained in solutions. The comparatively more stable systems An₁H₂O which exist in a free state and change their physical state must present, although within certain limits of temperature, an entirely harmonious kind of motion of A with n₁H₂O; the property also and state of systems AnH₂O and AmH₂O, occurring in solutions, is that they are in a liquid form, although partially dissociated. Substances A₁, which give solutions, are distinguished by the fact that they can form such unstable systems AnH₂O, but besides them they can give other much more stable systems An₁H₂O. Thus ethylene, C₂H₄, in dissolving in water, probably forms a system C₂H₄nH₂O, which easily splits up into C₂H₄ and H₂O, but it also gives the system of alcohol, C₂H₄,H₂O or C₂H₆O, which is comparatively stable. Thus oxygen can dissolve in water, and it can combine with it, forming peroxide of hydrogen. Turpentine, C₁₀H₁₆, does not dissolve in water, but it combines with it as a comparatively stable hydrate. In other words, the chemical structure of hydrates, or of the definite compounds which are contained in solutions, is distinguished not only by its original peculiarities but also by a diversity of stability. A similar structure to hydrates must be acknowledged in crystallo-hydrates. On melting they give actual (real) solutions. As substances which give crystallo-hydrates, like salts, are capable of forming a number of diverse hydrates, and as the greater the number of molecules of water (n) they (AnH₂O) contain, the lower is the temperature of their formation, and as the more easily they decompose the more water they hold, therefore, in the first place, the isolation of hydrates holding much water existing in aqueous solutions may be soonest looked for at low temperatures (although, perhaps, in certain cases they cannot exist in the solid state); and, secondly, the stability also of such higher hydrates will be at a minimum under the ordinary circumstances of the occurrence of liquid water. Hence a further more detailed investigation of cryohydrates may help to the elucidation of the nature of solutions. But it may be foreseen that certain cryohydrates will, like metallic alloys, present solidified mixtures of ice with the salts themselves and their more stable hydrates, and others will be definite compounds.

[70] The above representation of solutions, &c., considering them as a particular state of definite compounds, excludes the independent existence of indefinite compounds; by this means that unity of chemical conception is obtained which cannot be arrived at by admitting the physico-mechanical conception of indefinite compounds. The gradual transition from typical solutions (as of gases in water, and of weak saline solutions) to sulphuric acid, and from it and its definite, but yet unstable and liquid, compounds, to clearly defined compounds, such as salts and their crystallo-hydrates, is so imperceptible, that in denying that solutions pertain to the number of definite but dissociating compounds, we risk denying the definiteness of the atomic composition of such substances as sulphuric acid or of molten crystallo-hydrates. I repeat, however, that for the present the theory of solutions cannot be considered as firmly established. The above opinion about them is nothing more than a hypothesis which endeavours to satisfy those comparatively limited data which we have for the present about solutions, and of those cases of their transition into definite compounds. By submitting solutions to the Daltonic conception of atomism, I hope that we may not only attain to a general harmonious chemical doctrine, but also that new motives for investigation and research will appear in the problem of solutions, which must either confirm the proposed theory or replace it by another fuller and truer one; and I for my part cannot consider this to be the case with any of the other present doctrines of solutions (note 49).

[71] In combining with water one part by weight of lime evolves 245 units of heat. A high temperature is obtained, because the specific heat of the resulting product is small. Sodium oxide, Na₂O, in reacting on water, H₂O, and forming caustic soda (sodium hydroxide), NaHO, evolves 552 units of heat for each part by weight of sodium oxide.

[72] The diagram given in note 28 shows the evolution of heat on the mixture of sulphuric acid, or monohydrate (H₂SO₄, i.e. SO₃ + H₂O), with different quantities of water per 100 vols. of the resultant solution. Every 98 grams of sulphuric acid (H₂SO₄) evolve, on the addition of 18 grams of water, 6,379 units of heat; with twice or three times the quantity of water 9,418 and 11,137 units of heat, and with an infinitely large quantity of water 17,860 units of heat, according to the determinations of Thomsen. He also showed that when H₂SO₄ is formed from SO₃ (= 80) and H₂O (= 18), 21,308 units of heat are evolved per 98 parts by weight of the resultant sulphuric acid.

[73] Thus, for different hydrates the stability with which they hold water is very dissimilar. Certain hydrates hold water very loosely, and in combining with it evolve little heat. From other hydrates the water cannot be separated by any degree of heat, even if they are formed from anhydrides (i.e. anhydrous substances) and water with little evolution of heat; for instance, acetic anhydride in combining with water evolves an inconsiderable amount of heat, but the water cannot then be expelled from it. If the hydrate (acetic acid) formed by this combination be strongly heated it either volatilises without change, or decomposes into new substances, but it does not again yield the original substances—i.e., the anhydride and water, at least in a liquid form. Here is an instance which gives the reason for calling the water entering into the composition of the hydrate, water of constitution. Such, for example, is the water entering into the so-called caustic soda or sodium hydroxide (see note 71). But there are hydrates which easily part with their water; yet this water cannot be considered as water of crystallisation, not only because sometimes such hydrates have no crystalline form, but also because, in perfectly analogous cases, very stable hydrates are formed, which are capable of particular kinds of chemical reactions, as we shall subsequently learn. Such, for example, is the unstable hydrated oxide of copper, which is not formed from water and oxide of copper, but which is obtained just like far more stable hydrates, for example, the hydrated oxide of barium BaH₂O₂ equal to BaO + H₂O, by the double decomposition of the solution of salts with alkalies. In a word, there is no distinct boundary either between the water of hydrates and of crystallisation, or between solution and hydration.

It must be observed that in separating from an aqueous solution, many substances, without having a crystalline form, hold water in the same unstable state as in crystals; only this water cannot be termed ‘water of crystallisation’ if the substance which separates out has no crystalline form. The hydrates of alumina and silica are examples of such unstable hydrates. If these substances are separated from an aqueous solution by a chemical process, then they always contain water. The formation of a new chemical compound containing water is here particularly evident, for alumina and silica in an anhydrous state have chemical properties differing from those they show when combined with water, and do not combine directly with it. The entire series of colloids on separating from water form similar compounds with it, which have the aspect of solid gelatinous substances. Water is held in a considerable quantity in solidified glue or boiled albumin. It cannot be expelled from them by pressure; hence, in this case there has ensued some kind of combination of the substance with water. This water, however, is easily separated on drying; but not the whole of it, a portion being retained, and this portion is considered to belong to the hydrate, although in this case it is very difficult, if not impossible, to obtain definite compounds. The absence of any distinct boundary lines between solutions, crystallo-hydrates, and ordinary hydrates above referred to, is very clearly seen in such examples.

[1] The first experiments of the synthesis and decomposition of water did not afford, however, an entirely convincing proof that water was composed of hydrogen and oxygen only. Davy, who investigated the decomposition of water by the galvanic current, thought for a long time that, besides the gases, an acid and alkali were also obtained. He was only convinced of the fact that water contains nothing but hydrogen and oxygen by a long series of researches, which showed him that the appearance of an acid and alkali in the decomposition of water proceeds from the presence of impurities (especially from the presence of ammonium nitrate) in water. A final comprehension of the composition of water is obtained from the accurate determination of the quantities of the component parts which enter into its composition. It will be seen from this how many data are necessary for proving the composition of water—that is, of the transformations of which it is capable. What has been said of water refers to all other compounds; the investigation of each one, the entire proof of its composition, can only be obtained by the accumulation of a large mass of data referring to it.

[2] This gas is collected in a voltameter.

[3] In order to observe this explosion without the slightest danger, it is best to proceed in the following manner. Some soapy water is prepared, so that it easily forms soap bubbles, and it is poured into an iron trough. In this water, the end of a gas-conducting tube is immersed. This tube is connected with any suitable apparatus, in which detonating gas is evolved. Soap bubbles, full of this gas, are then formed. If the apparatus in which the gas is produced be then removed (otherwise the explosion might travel into the interior of the apparatus), and a lighted taper be brought to the soap bubbles, a very sharp explosion takes place. The bubbles should be small to avoid any danger; ten, each about the size of a pea, suffice to give a sharp report, like a pistol shot.

[4] In order to fill the tube with water, it is turned up, so that the closed end points downwards and the open end upwards, and water acidified with sulphuric acid is poured into it.

[4 bis] Owing to the gradual but steady progress made during the last twenty-five years in the production of an electric current from the dynamo and its transmission over considerable distances, the electrolytic decomposition of many compound bodies has acquired great importance, and the use of the electric current is making its way into many chemical manufactures. Hence, Prof. D. A. Lachinoff's proposal to obtain hydrogen and oxygen (both of which have many applications) by means of electrolysis (either of a 10 to 15 per cent. solution of caustic soda or a 15 per cent. solution of sulphuric acid) may find a practical application, at all events in the future. In general, owing to their simplicity, electrolytic methods have a great future, but as yet, so long as the production of an electric current remains so costly, their application is limited. And for this reason, although certain of these methods are mentioned in this work, they are not specially considered, the more so since a profitable and proper use of the electric current for chemical purposes requires special electro-technical knowledge which beginners cannot he assumed to have, and therefore, an exposition of the principles of electrotechnology as applied, to the production of chemical transformations, although referred to in places, does not come within the scope of the present work.

[5] As water is formed by the combination of oxygen and hydrogen, with a considerable evolution of heat, and as it can also be decomposed, this reaction is a reversible one (see Introduction), and consequently at a high temperature the decomposition of water cannot be complete—it is limited by the opposite reaction. Strictly speaking, it is not known how much water is decomposed at a given temperature, although many efforts (Bunsen, and others) have been made in various directions to solve this question. Not knowing the coefficient of expansion, and the specific heat of gases at such high temperatures, renders all calculations (from observations of the pressure on explosion) doubtful.

[6] Grove, in 1847, observed that a platinum wire fused in the oxyhydrogen flame—that is, having acquired the temperature of the formation of water—and having formed a molten drop at its end which fell into water, evolved detonating gas—that is, decomposed water. It therefore follows that water already decomposes at the temperature of its formation. At that time, this formed a scientific paradox; this we shall unravel only with the development of the conceptions of dissociation, introduced into science by Henri Sainte-Claire Deville, in 1857. These conceptions form an important epoch in science, and their development is one of the problems of modern chemistry. The essence of the matter is that, at high temperatures, water exists but also decomposes, just as a volatile liquid, at a certain temperature, exists both as a liquid and as a vapour. Similarly as a volatile liquid saturates a space, attaining its maximum tension, so also the products of dissociation have their maximum tension, and once that is attained decomposition ceases, just as evaporation ceases. Under like conditions, if the vapour be allowed to escape (and therefore its partial pressure be diminished), evaporation recommences, so also if the products of decomposition be removed, decomposition again continues. These simple conceptions of dissociation introduce infinitely varied consequences into the mechanism of chemical reactions, and therefore we shall have occasion to return to them very often. We may add that Grove also concluded that water was decomposed at a white heat, from the fact that he obtained detonating gas by passing steam through a tube with a wire heated strongly by an electric current, and also by passing steam over molten oxide of lead, he obtained, on the one hand, litharge (= oxide of lead and oxygen), and on the other, metallic lead formed by the action of hydrogen.

[6 bis] Part of the oxygen will also penetrate through the pores of the tube; but, as was said before, a much smaller quantity than the hydrogen, and as the density of oxygen is sixteen times greater than that of hydrogen, the volume of oxygen which passes through the porous walls will be four times less than the volume of hydrogen (the quantities of gases passing through porous walls are inversely proportional to the square roots of their densities). The oxygen which separates out into the annular space will combine, at a certain fall of temperature, with the hydrogen; but as each volume of oxygen only requires two volumes of hydrogen, whilst at least four volumes of hydrogen will pass through the porous walls for every volume of oxygen that passes, therefore, part of the hydrogen will remain free, and can be collected from the annular space. A corresponding quantity of oxygen remaining from the decomposition of the water can be collected from the internal tube.

[7] In order to demonstrate the difference of the affinity of oxygen for different elements, it is enough to compare the amounts of heats which are evolved in their combination with 16 parts by weight of oxygen; in the case of sodium (when Na₂O is formed, or 46 parts of Na combine with 16 parts of oxygen, according to Beketoff) 100,000 calories (or units of heat), are evolved, for hydrogen (when water, H₂O, is formed) 69,000 calories, for iron (when the oxide FeO is formed) 69,000, and if the oxide Fe₂O₃ is formed, 64,000 calories, for zinc (ZnO is formed) 86,000 calories, for lead (when PbO is formed) 51,000 calories, for copper (when CuO is formed) 38,000 calories, and for mercury (HgO is formed) 31,000 calories.

These figures cannot correspond directly with the magnitude of the affinities, for the physical and mechanical side of the matter is very different in the different cases. Hydrogen is a gas, and, in combining with oxygen, gives a liquid; consequently it changes its physical state, and, in doing so, evolves heat. But zinc and copper are solids, and, in combining with oxygen, give solid oxides. The oxygen, previously a gas, now passes into a solid or liquid state, and, therefore, also must have given up its store of heat in forming oxides. As we shall afterwards see, the degree of contraction (and consequently of mechanical work) was different in the different cases, and therefore the figures expressing the heat of combination cannot directly depend on the affinities, on the loss of internal energy previously in the elements. Nevertheless, the figures above cited correspond, in a certain degree, with the order in which the elements stand in respect to their affinity for oxygen, as may be seen from the fact that the mercury oxide, which evolves the least heat (among the above examples), is the least stable is easily decomposed, giving up its oxygen; whilst sodium, the formation of whose oxide is accompanied by the greatest evolution of heat, is able to decompose all the other oxides, taking up their oxygen. In order to generalise the connection between affinity and the evolution and the absorption of heat, which is evident in its general features, and was firmly established by the researches of Favre and Silbermann (about 1840), and then of Thomsen (in Denmark) and Berthelot (in France), many investigators, especially the one last mentioned, established the law of maximum work. This states that only those chemical reactions take place of their own accord in which the greatest amount of chemical (latent, potential) energy is transformed into heat. But, in the first place, we are not able, judging from what has been said above, to distinguish that heat which corresponds with purely chemical action from the sum total of the heat observed in a reaction (in the calorimeter); in the second place, there are evidently endothermal reactions which proceed under the same circumstances as exothermal (carbon burns in the vapour of sulphur with absorption of heat, whilst in oxygen it evolves heat); and, in the third place, there are reversible reactions, which when taking place in one direction evolve heat, and when taking place in the opposite direction absorb it; and, therefore, the principle of maximum work in its elementary form is not supported by science. But the subject continues to be developed, and will probably lead to a general law, such as thermal chemistry does not at present possess.

[8] If a piece of metallic sodium be thrown into water, it floats on it (owing to its lightness), keeps in a state of continual motion (owing to the evolution of hydrogen on all sides), and immediately decomposes the water, evolving hydrogen, which can be lighted. This experiment may, however, lead to an explosion should the sodium stick to the walls of the vessel, and begin to act on the limited mass of water immediately adjacent to it (probably in this case NaHO forms with Na, Na₂O, which acts on the water, evolving much heat and rapidly forming steam), and the experiment should therefore be carried on with caution. The decomposition of water by sodium may he better demonstrated, and with greater safety, in the following manner. Into a glass cylinder filled with mercury, and immersed in a mercury bath, water is first introduced, which will, owing to its lightness, rise to the top, and then a piece of sodium wrapped in paper is introduced with forceps into the cylinder. The metal rises through the mercury to the surface of the water, on which it remains, and evolves hydrogen, which collects in the cylinder, and may be tested after the experiment has been completed. The safest method of making this experiment is, however, as follows. The sodium (cleaned from the naphtha in which it is kept) is either wrapped in fine copper gauze and held by forceps, or else held in forceps at the end of which a small copper cage is attached, and is then held under water. The evolution of hydrogen goes on quietly, and it may he collected in a bell jar and then lighted.

[9] This reaction is vigorously exothermal, i.e. it is accompanied by the evolution of heat. If a sufficient quantity of water be taken the whole of the sodium hydroxide, NaHO, formed is dissolved, and about 42,500 units of heat are evolved per 23 grams of sodium taken. As 40 grams of sodium hydroxide are produced, and they in dissolving, judging from direct experiment, evolve about 10,000 calories; therefore, without an excess of water, and without the formation of a solution, the reaction would evolve about 32,500 calories. We shall afterwards learn that hydrogen contains in its smallest isolable particles H₂ and not H, and therefore it follows that the reaction should be written thus—2Na + 2H₂O = H₂ + 2NaOH, and it then corresponds with an evolution of heat of +65,000 calories. And as N. N. Beketoff showed that Na₂O, or anhydrous oxide of sodium, forms the hydrate, or sodium hydroxide (caustic soda), 2NaHO, with water, evolving about 35,500 calories, therefore the reaction 2Na + H₂O = H₂ + Na₂O corresponds to 29,500 calories. This quantity of heat is less than that which is evolved in combining with water, in the formation of caustic soda, and therefore it is not to be wondered at that the hydrate, NaHO, is always formed and not the anhydrous substance Na₂O. That such a conclusion, which agrees with facts, is inevitable is also seen from the fact that, according to Beketoff, the anhydrous sodium oxide, Na₂O, acts directly on hydrogen, with separation of sodium, Na₂O + H = NaHO + Na. This reaction is accompanied by an evolution of heat equal to about 3,000 calories, because Na₂O + H₂O gives, as we saw, 35,500 calories and Na + H₂O evolves 32,500 calories. However, an opposite reaction also takes place—NaHO + Na = Na₂O + H (both with the aid of heat)—consequently, in this case heat is absorbed. In this we see an example of calorimetric calculations and the limited application of the law of maximum work for the general phenomena of reversible reactions, to which the case just considered belongs. But it must be remarked that all reversible reactions evolve or absorb but little heat, and the reason of the law of maximum work, not being universal must first of all be looked for in the fact that we have no means of separating the heat which corresponds with the purely chemical process from the sum total of the heat observed, and as the structure of a number of substances is altered by heat and also by contact, we can scarcely hope that the time approaches when such a distinction will be possible. A heated substance, in point of fact, has no longer the original energy of its atoms—that is, the act of heating not only alters the store of motion of the molecules but also of the atoms forming the molecules, in other words, it makes the beginning of or preparation for chemical change. From this it must be concluded that thermochemistry, or the study of the heat accompanying chemical transformations, cannot he identified with chemical mechanics. Thermo-chemical data form a part of it, but they alone cannot give it.

[10] The composition of water, as we saw above, was determined by passing steam over red-hot iron; the same method has been used for making hydrogen for filling balloons. An oxide having the composition Fe₃O₄ is formed in the reaction, so that it is expressed by the equation 3Fe + 4H₂O = Fe₃O₄ + 8H.

[11] The reaction between iron and water (note 10) is reversible. By heating the oxide in a current of hydrogen, water and iron are obtained. From this it follows, from the principle of chemical equilibria, that if iron and hydrogen be taken, and also oxygen, but in such a quantity that it is insufficient for combination with both substances, then it will divide itself between the two; part of it will combine with the iron and the other part with the hydrogen, but a portion of both will remain in an uncombined state.

Therefore, if iron and water be placed in a closed space, decomposition of the water will proceed on heating to the temperature at which the reaction 3Fe + 4H₂O = Fe₃O₄ + 8H commences; but it ceases, does not go on to the end, because the conditions for a reverse reaction are attained, and a state of equilibrium will ensue after the decomposition of a certain quantity of water. Here again (see note 9) the reversibility is connected with the small heat effect, and again both reactions (direct and reverse) proceed at a red heat. But if, in the above-described reaction, the hydrogen escapes as it is evolved, then its partial pressure does not increase with its formation, and therefore all the iron can he oxidised by the water. In this we see the elements of that influence of mass to which we shall have occasion to return later. With copper and lead there will be no decomposition, either at the ordinary or at a high temperature, because the affinity of these metals for oxygen is much less than that of hydrogen.

[12] In general, if reversible as well as non-reversible reactions can take place between substances acting on each other, then, judging by our present knowledge, the non-reversible reactions take place in the majority of cases, which obliges one to acknowledge the action, in this case, of comparatively strong affinities. The reaction, Zn + H₂SO₄ = H₂ + ZnSO₄, which takes place in solutions at the ordinary temperature, is scarcely reversible under these conditions, but at a certain high temperature it becomes reversible, because at this temperature zinc sulphate and sulphuric acid split up, and the action must take place between the water and zinc. From the preceding proposition results proceed which are in some cases verified by experiment. If the action of zinc or iron on a solution of sulphuric acid presents a non-reversible reaction, then we may by this means obtain hydrogen in a very compressed state, and compressed hydrogen will not act on solutions of sulphates of the above-named metals. This is verified in reality as far as was possible in the experiments to keep up the compression or pressure of the hydrogen. Those metals which do not evolve hydrogen with acids, on the contrary, should, at least at an increase of pressure, be displaced by hydrogen. And in fact Brunner showed that gaseous hydrogen displaces platinum and palladium from the aqueous solutions of their chlorine compounds, but not gold, and Beketoff succeeded in showing that silver and mercury, under a considerable pressure, are separated from the solutions of certain of their compounds by means of hydrogen. Reaction already commences under a pressure of six atmospheres, if a weak solution of silver sulphate be taken; with a stronger solution a much greater pressure is required, however, for the separation of the silver.

[13] For the same reason, many metals in acting on solutions of the alkalis displace hydrogen. Aluminium acts particularly clearly in this respect, because its oxide gives a soluble compound with alkalis. For the same reason tin, in acting on hydrochloric acid, evolves hydrogen, and silicon does the same with hydrofluoric acid. It is evident that in such cases the sum of all the affinities plays a part; for instance, taking the action of zinc on sulphuric acid, we have the affinity of zinc for oxygen (forming zinc oxide, ZnO), the affinity of its oxide for sulphuric anhydride, SO₃ (forming zinc sulphate, ZnSO₄), and the affinity of the resultant salt, ZnSO₄, for water. It is only the first-named affinity that acts in the reaction between water and the metal, if no account is taken of those forces (of a physico-mechanical character) which act between the molecules (for instance, the cohesion between the molecules of the oxide) and those forces (of a chemical character) which act between the atoms forming the molecule, for instance, between the atoms of hydrogen giving the molecule H₂ containing two atoms. I consider it necessary to remark, that the hypothesis of the affinity or endeavour of heterogeneous atoms to enter into a common system and in harmonious motion (i.e. to form a compound molecule) must inevitably be in accordance with the hypothesis of forces including homogeneous atoms to form complex molecules (for instance, H₂), and to build up the latter into solid or liquid substances, in which the existence of an attraction between the homogeneous particles must certainly be admitted. Therefore, those forces which bring about solution must also be taken into consideration. These are all forces of one and the same series, and in this may be seen the great difficulties surrounding the study of molecular mechanics and its province—chemical mechanics.

[14] It is acknowledged that zinc itself acts on water, even at the ordinary temperature, but that the action is confined to small masses and only proceeds at the surface. In reality, zinc, in the form of a very fine powder, or so-called ‘zinc dust,’ is capable of decomposing water with the formation of oxide (hydrated) and hydrogen. The oxide formed acts on sulphuric acid, water then dissolves the salt produced, and the action continues because one of the products of the action of water on zinc, zinc oxide, is removed from the surface. One might naturally imagine that the reaction does not proceed directly between the metal and water, but between the metal and the acid, but such a simple representation, which we shall cite afterwards, hides the mechanism of the reaction, and does not permit of its actual complexity being seen.

[15] According to Thomsen the reaction between zinc and a very weak solution of sulphuric acid evolves about 38,000 calories (zinc sulphate being formed) per 65 parts by weight of zinc; and 56 parts by weight of iron—which combine, like 65 parts by weight of zinc, with 16 parts by weight of oxygen—evolve about 25,000 calories (forming ferrous sulphate, FeSO₄). Paracelsus observed the action of metals on acids in the seventeenth century; but it was not until the eighteenth century that Lémery determined that the gas which is evolved in this action is a particular one which differs from air and is capable of burning. Even Boyle confused it with air. Cavendish determined the chief properties of the gas discovered by Paracelsus. At first it was called ‘inflammable air’; later, when it was recognised that in burning it gives water, it was called hydrogen, from the Greek words for water and generator.

[15 bis] If, when the sulphuric acid is poured over the zinc, the evolution of the hydrogen proceed too slowly, it may be greatly accelerated by adding a small quantity of a solution of CuSO₄ or PtCl₄ to the acid. The reason of this is explained in Chap. XVI., note 10 bis.

[16]

Fig. 21.—A very convenient apparatus for the preparation of gases obtained without heat. It may also replace an aspirator or gasometer.

As laboratory experiments with gases require a certain preliminary knowledge, we will describe certain practical methods for the collection and preparation of gases. When in laboratory practice an intermittent supply of hydrogen (or other gas which is evolved without the aid of heat) is required the apparatus represented in fig. 21 is the most convenient. It consists of two bottles, having orifices at the bottom, in which corks with tubes are placed, and these tubes are connected by an india-rubber tube (sometimes furnished with a spring clamp). Zinc is placed in one bottle, and dilute sulphuric acid in the other. The neck of the former is closed by a cork, which is fitted with a gas-conducting tube with a stopcock. If the two bottles are connected with each other and the stopcock be opened, the acid will flow to the zinc and evolve hydrogen. If the stopcock be closed, the hydrogen will force out the acid from the bottle containing the zinc, and the action will cease. Or the vessel containing the acid may be placed at a lower level than that containing the zinc, when all the liquid will flow into it, and in order to start the action the acid vessel may be placed on a higher level than the other, and the acid will flow to the zinc. It can also be employed for collecting gases (as an aspirator or gasometer).

Fig. 22.—Continuous aspirator. The tube d should be more than 32 feet long.

In laboratory practice, however, other forms of apparatus are generally employed for exhausting, collecting, and holding gases. We will here cite the most usual forms. An aspirator usually consists of a vessel furnished with a stopcock at the bottom. A stout cork, through which a glass tube passes, is fixed into the neck of this vessel. If the vessel be filled up with water to the cork and the bottom stopcock is opened, then the water will run out and draw gas in. For this purpose the glass tube is connected with the apparatus from which it is desired to pump out or exhaust the gas.

Fig. 23.—Gasholder.

The aspirator represented in fig. 22 may be recommended for its continuous action. It consists of a tube d which widens out at the top, the lower part being long and narrow. In the expanded upper portion c, two tubes are sealed; one, e, for drawing in the gas, whilst the other, b, is connected to the water supply w. The amount of water supplied through the tube b must be less than the amount which can be carried off by the tube d. Owing to this the water in the tube d will flow through it in cylinders alternating with cylinders of gas, which will be thus carried away. The gas which is drawn through may be collected from the end of the tube d, but this form of pump is usually employed where the air or gas aspirated is not to be collected. If the tube d is of considerable length, say 40 ft. or more, a very fair vacuum will be produced, the amount of which is shown by the gauge g; it is often used for filtering under reduced pressure, as shown in the figure. If water be replaced by mercury, and the length of the tube d be greater than 760 mm., the aspirator may be employed as an air-pump, and all the air may be exhausted from a limited space; for instance, by connecting g with a hollow sphere.

Gasholders are often used for collecting and holding gases. They are made of glass, copper, or tin plate. The usual form is shown in fig. 23. The lower vessel B is made hermetically tight—i.e., impervious to gases—and is filled with water. A funnel is attached to this vessel (on several supports). The vessel B communicates with the bottom of the funnel by a stopcock b and a tube a, reaching to the bottom of the vessel B. If water be poured into the funnel and the stopcocks a and b opened, the water will run through a, and the air escape from the vessel B by b. A glass tube f runs up the side of the vessel B, with which it communicates at the top and bottom, and shows the amount of water and gas the gasholder contains. In order to fill the gasholder with a gas, it is first filled with water, the cocks a, b and e are closed, the nut d unscrewed, and the end of the tube conducting the gas from the apparatus in which it is generated is passed into d. As the gas fills the gasholder, the water runs out at d. If the pressure of a gas be not greater than the atmospheric pressure and it be required to collect it in the gasholder, then the stopcock e is put into communication with the space containing the gas. Then, having opened the orifice d, the gasholder acts like an aspirator; the gas will pass through e, and the water run out at d. If the cocks be closed, the gas collected in the gasholder may be easily preserved and transported. If it be desired to transfer this gas into another vessel, then a gas-conducting tube is attached to e, the cock a opened, b and d closed, and the gas will then pass out at e, owing to its pressure in the apparatus being greater than the atmospheric pressure, due to the pressure of the water poured into the funnel. If it be required to fill a cylinder or flask with the gas, it is filled with water and inverted in the funnel, and the stopcocks b and a opened. Then water will run through a, and the gas will escape from the gasholder into the cylinder through b.

[17] When it is required to prepare hydrogen in large quantities for filling balloons, copper vessels or wooden casks lined with lead are employed; they are filled with scrap iron, over which dilute sulphuric acid is poured. The hydrogen generated from a number of casks is carried through lead pipes into special casks containing water (in order to cool the gas) and lime (in order to remove acid fumes). To avoid loss of gas all the joints are made hermetically tight with cement or tar. In order to fill his gigantic balloon (of 25,000 cubic metres capacity), Giffard, in 1878, constructed a complicated apparatus for giving a continuous supply of hydrogen, in which a mixture of sulphuric acid and water was continually run into vessels containing iron, and from which the solution of iron sulphate formed was continually drawn off. When coal gas, extracted from coal, is employed for filling balloons, it should be as light, or as rich in hydrogen, as possible. For this reason, only the last portions of the gas coming from the retorts are collected, and, besides this, it is then sometimes passed through red-hot vessels, in order to decompose the hydrocarbons as much as possible; charcoal is deposited in the red-hot vessels, and hydrogen remains as gas. Coal gas may be yet further enriched in hydrogen, and consequently rendered lighter, by passing it over an ignited mixture of charcoal and lime.

L. Mond (London) proposes to manufacture hydrogen on a large scale from water gas (see infra, and Chapters VIII. and IX.), which contains a mixture of oxide of carbon (CO) and hydrogen, and is produced by the action of steam upon incandescent coke (C + H₂O = CO + H₂). He destroys the oxide of carbon by converting it into carbon and carbonic anhydride (2CO = C + CO₂), which is easily done by means of incandescent, finely-divided metallic nickel; the carbon then remains with the nickel, from which it may be removed by burning it in air, and the nickel can then be used over again (see Chapter IX., Note 24 bis). The CO₂ formed is removed from the hydrogen by passing it through milk of lime. This process should apparently give hydrogen on a large scale more economically than any of the methods hitherto proposed.

[18] Of the metals, only a very few combine with hydrogen (for example, sodium), and give substances which are easily decomposed. Of the non-metals, the halogens (fluorine, chlorine, bromine, and iodine) most easily form hydrogen compounds; of these the hydrogen compound of chlorine, and still more that of fluorine, is stable, whilst those of bromine and iodine are easily decomposed, especially the latter. The other non-metals—for instance, sulphur, carbon, and phosphorus—give hydrogen compounds of different composition and properties, but they are all less stable than water. The number of the carbon compounds of hydrogen is enormous, but there are very few among them which are not decomposed, with separation of the carbon and hydrogen, at a red heat.

[19] The reaction expressed by the equation CNaHO₂ + NaHO = CNa₂O₃ + H₂ may be effected in a glass vessel, like the decomposition of copper carbonate or mercury oxide (see Introduction); it is non-reversible, and takes place without the presence of water, and therefore Pictet (see later) made use of it to obtain hydrogen under great pressure.

[20] The reaction between charcoal and superheated steam is a double one—that is, there may be formed either carbonic oxide, CO (according to the equation H₂O + C = H₂ + CO), or carbonic anhydride CO₂ (according to the equation 2H₂O + C = 2H₂ + CO₂), and the resulting mixture is called water-gas; we shall speak of it in Chapter IX.

[21] Hydrogen obtained by the action of zinc or iron on sulphuric acid generally smells of hydrogen sulphide (like rotten eggs), which it contains in admixture. As a rule such hydrogen is not so pure as that obtained by the action of an electric current or of sodium on water. The impurity of the hydrogen depends on the impurities contained in the zinc, or iron, and sulphuric acid, and on secondary reactions which take place simultaneously with the main reaction. Impure hydrogen may be easily freed from the impurities it contains: some of them—namely, those having acid properties—are absorbed by caustic soda, and therefore may be removed by passing the hydrogen through a solution of this substance; another series of impurities is absorbed by a solution of mercuric chloride; and, lastly, a third series is absorbed by a solution of potassium permanganate. If absolutely pure hydrogen be required, it is sometimes obtained by the decomposition of water (previously boiled to expel all air, and mixed with pure sulphuric acid) by the galvanic current. Only the gas evolved at the negative electrode is collected. Or else, an apparatus like that which gives detonating gas is used, the positive electrode, however, being immersed under mercury containing zinc in solution. The oxygen which is evolved at this electrode then immediately, at the moment of its evolution, combines with the zinc, and this compound dissolves in the sulphuric acid and forms zinc sulphate, which remains in solution, and therefore the hydrogen generated will be quite free from oxygen.

[22] An inverted beaker is attached to one arm of the beam of a tolerably sensitive balance, and its weight counterpoised by weights in the pan attached to the other arm, If the beaker be then filled with hydrogen it rises, owing to the air being replaced by hydrogen. Thus, at the ordinary temperature of a room, a litre of air weighs about 1·2 gram, and on replacing the air by hydrogen a decrease in weight of about 1 gram per litre is obtained. Moist hydrogen is heavier than dry—for aqueous vapour is nine times heavier than hydrogen. In filling balloons it is usually calculated that (it being impossible to have perfectly dry hydrogen or to obtain it quite free from air) the lifting force due to the difference between the weights of equal volumes of hydrogen and air is equal to 1 kilogram (= 1,000 grams) per cubic metre (= 1,000 litres).

[23] The density of hydrogen in relation to the air has been repeatedly determined by accurate experiments. The first determination, made by Lavoisier, was not very exact; taking the density of air as unity, he obtained 0·0769 for that of hydrogen—that is, hydrogen as thirteen times lighter than air. More accurate determinations are due to Thomsen, who obtained the figure 0·0693; Berzelius and Dulong, who obtained 0·0688; and Dumas and Boussingault, who obtained 0·06945. Regnault, and more recently Le Duc (1892), took two spheres of considerable capacity, which contained equal volumes of air (thus avoiding the necessity of any correction for weighing them in air). Both spheres were attached to the scale pans of a balance. One was sealed up, and the other first weighed empty and then full of hydrogen. Thus, knowing the weight of the hydrogen filling the sphere, and the capacity of the sphere, it was easy to find the weight of a litre of hydrogen; and, knowing the weight of a litre of air at the same temperature and pressure, it was easy to calculate the density of hydrogen. Regnault, by these experiments, found the average density of hydrogen to be 0·06926 in relation to air; Le Duc, 0·06948 (with a possible error of ±0·00001), and this latter figure must now be looked upon as near to the truth.

In this work I shall always refer the densities of all gases to hydrogen, and not to air; I will therefore give, for the sake of clearness, the weight of a litre of dry pure hydrogen in grams at a temperature t° and under a pressure H (measured in millimetres of mercury at 0°, in lat. 45°). The weight of a litre of hydrogen

= 0·08986 × H / 760 × 1 / 1 + 0·00367t gram.

For aëronauts it is very useful to know, besides this, the weight of the air at different heights, and I therefore insert the adjoining table, constructed on the basis of Glaisher's data, for the temperature and moisture of the atmospheric strata in clear weather. All the figures are given in the metrical system—1,000 millimetres = 39·37 inches, 1,000 kilograms = 2204·3375 lbs., 1,000 cubic metres = 35,316·6 cubic feet. The starting temperature at the earth's surface is taken as = 15° C., its moisture 60 p.c., pressure 760 millimetres. The pressures are taken as indicated by an aneroid barometer, assumed to be corrected at the sea level and at lat. 45° C. If the height above the level of the sea equal z kilometres, then the weight of 1 cubic metre of air may be approximately taken as 1·222 - 0·12z + 0·00377z² kilogram.

Although the figures in this table are calculated with every possible care from average data, yet they can only be taken approximately, for in every separate case the conditions, both at the earth's surface and in the atmosphere, will differ from those here taken. In calculating the height to which a balloon can ascend, it is evident that the density of gas in relation to air must be known. This density for ordinary coal gas is from 0·6 to 0·35, and for hydrogen with its ordinary contents of moisture and air from 0·1 to 0·15.

Hence, for instance, it may be calculated that a balloon of 1,000 cubic metres capacity filled with pure hydrogen, and weighing (the envelope, tackle, people, and ballast) 727 kilograms, will only ascend to a height of about 4,250 metres.

[24] If a cracked flask be filled with hydrogen and its neck immersed under water or mercury, then the liquid will rise up into the flask, owing to the hydrogen passing through the cracks about 3·8 times quicker than the air is able to pass through these cracks into the flask. The same phenomenon may be better observed if, instead of a flask, a tube be employed, whose end is closed by a porous substance, such as graphite, unglazed earthenware, or a gypsum plate.

[25] According to Boyle and Mariotte's law, for a given gas at a constant temperature the volume decreases by as many times as the pressure increases; that is, this law requires that the product of the volume v and the pressure p for a given gas should be a constant quantity: pv = C, a constant quantity which does not vary with a change of pressure. This equation does very nearly and exactly express the observed relation between the volume and pressure, but only within comparatively small variations of pressure, density, and volume. If these variations be in any degree considerable, the quantity pv proves to be dependent on the pressure, and it either increases or diminishes with an increase of pressure. In the former case the compressibility is less than it should he according to Mariotte's law, in the latter case it is greater. We will call the first case a positive discrepancy (because then d(pv)/d(p) is greater than zero), and the second case a negative discrepancy (because then d(pv)/d(p) is less than zero). Determinations made by myself (in the seventies), M. L. Kirpicheff, and V. A. Hemilian showed that all known gases at low pressures—i.e. when considerably rarefied—present positive discrepancies. On the other hand, it appears from the researches of Cailletet, Natterer, and Amagat that all gases under great pressures (when the volume obtained is 500–1,000 times less than under the atmospheric pressure) also present positive discrepancies. Thus under a pressure of 2,700 atmospheres air is compressed, not 2,700 times, but only 800, and hydrogen 1,000 times. Hence the positive kind of discrepancy is, so to say, normal to gases. And this is easily intelligible. If a gas followed Mariotte's law, or if it were compressed to a greater extent than is shown by this law, then under great pressures it would attain a density greater than that of solid and liquid substances, which is in itself improbable and even impossible by reason of the fact that solid and liquid substances are themselves but little compressible. For instance, a cubic centimetre of oxygen at 0° and under the atmospheric pressure weighs about 0·0014 gram, and at a pressure of 3,000 atmospheres (this pressure is attained in guns) it would, if it followed Mariotte's law, weigh 4·2 grams—that is, would be about four times heavier than water—and at a pressure of 10,000 atmospheres it would be heavier than mercury. Besides this, positive discrepancies are probable because the molecules of a gas themselves must occupy a certain volume. Considering that Mariotte's law, strictly speaking, applies only to the intermolecular space, we can understand the necessity of positive discrepancies. If we designate the volume of the molecules of a gas by b (like van der Waals, see Chap. I., Note 34), then it must be expected that p(v - b) = C. Hence pv = C + bp, which expresses a positive discrepancy. Supposing that for hydrogen pv = 1,000, at a pressure of one metre of mercury, according to the results of Regnault's, Amagat's, and Natterer's experiments, we obtain b as approximately 0·7 to 0·9.

Thus the increase of pv with the increase of pressure must be considered as the normal law of the compressibility of gases. Hydrogen presents such a positive compressibility at all pressures, for it presents positive discrepancies from Mariotte's law, according to Regnault, at all pressures above the atmospheric pressure. Hence hydrogen is, so to say, a perfect gas. No other gas behaves so simply with a change of pressure. All other gases at pressures from 1 to 30 atmospheres present negative discrepancies—that is, they are then compressed to a greater degree than should follow from Mariotte's law, as was shown by the determinations of Regnault, which were verified when repeated by myself and Boguzsky. Thus, for example, on changing the pressure from 4 to 20 metres of mercury—that is, on increasing the pressure five times—the volume only decreased 4·93 times when hydrogen was taken, and 5·06 when air was taken.

The positive discrepancies from the law at low pressures are of particular interest, and, according to the above-mentioned determinations made by myself, Kirpicheff, and Hemilian, and verified (by two methods) by K. D. Kraevitch and Prof. Ramsay (London, 1894), they are proper to all gases (even to those which are easily compressed into a liquid state, such as carbonic and sulphurous anhydrides). These discrepancies approach the case of a very high rarefaction of gases, where a gas is near to a condition of maximum dispersion of its molecules, and perhaps presents a passage towards the substance termed ‘luminiferous ether’ which fills up interplanetary and interstellar space. If we suppose that gases are rarefiable to a definite limit only, having attained which they (like solids) do not alter in volume with a decrease of pressure, then on the one hand the passage of the atmosphere at its upper limits into a homogeneous ethereal medium becomes comprehensible, and on the other hand it would be expected that gases would, in a state of high rarefaction (i.e. when small masses of gases occupy large volumes, or when furthest removed from a liquid state), present positive discrepancies from Boyle and Mariotte's law. Our present acquaintance with this province of highly rarefied gases is very limited (because direct measurements are exceedingly difficult to make, and are hampered by possible errors of experiment, which may be considerable), and its further development promises to elucidate much in respect to natural phenomena. To the three states of matter (solid, liquid, and gaseous) it is evident a fourth must yet be added, the ethereal or ultra-gaseous (as Crookes proposed), understanding by this, matter in its highest possible state of rarefaction.

[26] The law of Gay-Lussac states that all gases in all conditions present one coefficient of expansion 0·00367; that is, when heated from 0° to 100° they expand like air; namely, a thousand volumes of a gas measured at 0° will occupy 1367 volumes at 100°. Regnault, about 1850, showed that Gay-Lussac's law is not entirely correct, and that different gases, and also one and the same gas at different pressures, have not quite the same coefficients of expansion. Thus the expansion of air between 0° and 100° is 0·367 under the ordinary pressure of one atmosphere, and at three atmospheres it is 0·371, the expansion of hydrogen is 0·366, and of carbonic anhydride 0·37. Regnault, however, did not directly determine the change of volume between 0° and 100°, but measured the variation of tension with the change of temperature; but since gases do not entirely follow Mariotte's law, the change of volume cannot be directly judged by the variation of tension. The investigations carried on by myself and Kayander, about 1870, showed the variation of volume on heating from 0° to 100° under a constant pressure. These investigations confirmed Regnault's conclusion that Gay-Lussac's law is not entirely correct, and further showed (1) that the expansion per volume from 0° to 100° under a pressure of one atmosphere, for air = 0·368, for hydrogen = 0·367, for carbonic anhydride = 0·373, for hydrogen bromide = 0·386, &c.; (2) that for gases which are more compressible than should follow from Mariotte's law the expansion by heat increases with the pressure—for example, for air at a pressure of three and a half atmospheres, it equals 0·371, for carbonic anhydride at one atmosphere it equals 0·373, at three atmospheres 0·389, and at eight atmospheres 0·413; (3) that for gases which are less compressible than should follow from Mariotte's law, the expansion by heat decreases with an increase of pressure—for example, for hydrogen at one atmosphere 0·367, at eight atmospheres 0·369, for air at a quarter of an atmosphere 0·370, at one atmosphere 0·368; and hydrogen like air (and all gases) is less compressed at low pressures than should follow from Mariotte's law (see Note 25). Hence, hydrogen, starting from zero to the highest pressures, exhibits a gradually, although only slightly, varying coefficient of expansion, whilst for air and other gases at the atmospheric and higher pressures, the coefficient of expansion increases with the increase of pressure, so long as their compressibility is greater than should follow from Mariotte's law. But when at considerable pressures, this kind of discrepancy passes into the normal (see Note 25), then the coefficient of expansion of all gases decreases with an increase of pressure, as is seen from the researches of Amagat. The difference between the two coefficients of expansion, for a constant pressure and for a constant volume, is explained by these relations. Thus, for example, for air at a pressure of one atmosphere the true coefficient of expansion (the volume varying at constant pressure) = 0·00368 (according to Mendeléeff and Kayander) and the variation of tension (at a constant volume, according to Regnault) = 0·00367.

[27] Permanent gases are those which cannot be liquefied by an increase of pressure alone. With a rise of temperature, all gases and vapours become permanent gases. As we shall afterwards learn, carbonic anhydride becomes a permanent gas at temperatures above 31°, and at lower temperatures it has a maximum tension, and may be liquefied by pressure alone.

The liquefaction of gases, accomplished by Faraday (see Ammonia, Chapter VI.) and others, in the first half of this century, showed that a number of substances are capable, like water, of taking all three physical states, and that there is no essential difference between vapours and gases, the only distinction being that the boiling points (or the temperature at which the tension = 760 mm.) of liquids lie above the ordinary temperature, and those of liquefied gases below, and consequently a gas is a superheated vapour, or vapour heated above the boiling point, or removed from saturation, rarefied, having a lower tension than that maximum which is proper to a given temperature and substance. We will here cite the maximum tensions of certain liquids and gases at various temperatures, because they may be taken advantage of for obtaining constant temperatures by changing the pressure at which boiling or the formation of saturated vapours takes place. (I may remark that the dependence between the tension of the saturated vapours of various substances and the temperature is very complex, and usually requires three or four independent constants, which vary with the nature of the substance, and are found from the dependence of the tension p on the temperature t given by experiment; but in 1892 K. D. Kraevitch showed that this dependence is determined by the properties of a substance, such as its density, specific heat, and latent heat of evaporation.) The temperatures (according to the air thermometer) are placed on the left, and the tension in millimetres of mercury (at 0°) on the right-hand side of the equations. Carbon bisulphide, CS₂, 0° = 127·9; 10° = 198·5; 20° = 298·1; 30° = 431·6; 40° = 617·5; 50° = 857·1. Chlorobenzene, C₆H₅Cl, 70° = 97·9; 80° = 141·8; 90° = 208·4; 100° = 292·8; 110° = 402·6; 120° = 542·8; 130° = 719·0. Aniline, C₆H₇N, 150° = 283·7; 160° = 387·0; 170° = 515·6; 180° = 677·2; 185° = 771·5. Methyl salicylate, C₈H₈O₃, 180° = 294·4; 190° = 330·9; 200° = 432·4; 210° = 557·5; 220° = 710·2; 224° = 779·9. Mercury, Hg, 300° = 246·8; 310° = 304·9; 320° = 373·7; 330° = 454·4; 340° = 548·6; 350° = 658·0; 359° = 770·9. Sulphur, S, 395° = 300; 423° = 500; 443° = 700; 452° = 800; 459° = 900. These figures (Ramsay and Young) show the possibility of obtaining constant temperatures in the vapours of boiling liquids by altering the pressure. We may add the following boiling points under a pressure of 760 mm. (according to the air thermometer by Collendar and Griffiths, 1891): aniline, 184° = 13; naphthalene, 217° = 94; benzophenone, 305° = 82; mercury, 356° = 76; triphenyl-methane, 356° = 44; sulphur, 444° = 53. And melting points: tin, 231° = 68; bismuth, 269° = 22; lead, 327° = 69; and zinc, 417° = 57. These data may be used for obtaining a constant temperature and for verifying thermometers. The same object may be attained by the melting points of certain salts, determined according to the air thermometer by V. Meyer and Riddle (1893): NaCl, 851°; NaBr, 727°; NaI, 650°; KCl, 760°; KBr, 715°; KI, 623°; K₂CO₃, 1045°; Na₂CO₃, 1098°; Na₂B₄O₇, 873°; Na₂SO₄, 843°; K₂SO₄, 1073°. The tension of liquefied gases is expressed in atmospheres. Sulphurous anhydride, SO₂, -30° = 0·4; -20° = 0·6; -10° = 1; 0° = 1·5; +10° = 2·3; 20° = 3·2; 30° = 5·3. Ammonia, NH₃, -40° = 0·7; -30° = 1·1; -20° = 1·8; -10° = 2·8; 0° = 4·2; +10° = 6·0; 20° = 8·4. Carbonic anhydride, CO₂, -115° = 0·033; -80° = 1; -70° = 2·1; -60° = 3·9; -50° = 6·8; -40° = 10; -20° = 23; 0° = 35; +10° = 46; 20° = 58. Nitrous oxide, N₂O, -125° = 0·033; -92° = 1; -80° = 1·9; -50° = 7·6; -20° = 23·1; 0° = 36·1; +20° = 55·3. Ethylene, C₂H₄, -140° = 0·033; -130° = 0·1; -103° = 1; -40° = 13; -1° = 42. Air, -191° = 1; -158° = 14; -140° = 39. Nitrogen, N₂, -203° = 0·085; -193° = 1; -160° = 14; -146° = 32. The methods of liquefying gases (by pressure and cold) will be described under ammonia, nitrous oxide, sulphurous anhydride, and in later footnotes. We will now turn our attention to the fact that the evaporation of volatile liquids, under various, and especially under low, pressures, gives an easy means for obtaining low temperatures. Thus liquefied carbonic anhydride, under the ordinary pressure, reduces the temperature to -80°, and when it evaporates in a rarefied atmosphere (under an air-pump) to 25 mm. (= 0·033 atmosphere) the temperature, judging by the above-cited figures, falls to -115° (Dewar). Even the evaporation of liquids of common occurrence, under low pressures easily attainable with an air-pump, may produce low temperatures, which may be again taken advantage of for obtaining still lower temperatures. Water boiling in a vacuum becomes cold, and under a pressure of less than 4·5 mm. it freezes, because its tension at 0° is 4·5 mm. A sufficiently low temperature may be obtained by forcing fine streams of air through common ether, or liquid carbon bisulphide, CS₂, or methyl chloride, CH₃Cl, and other similar volatile liquids. In the adjoining table are given, for certain gases, (1) the number of atmospheres necessary for their liquefaction at 15°, and (2) the boiling points of the resultant liquids under a pressure of 760 mm.

[28] Natterer's determinations (1851–1854), together with Amagat's results (1880–1888), show that the compressibility of hydrogen, under high pressures, may be expressed by the following figures:—

where p = the pressure in metres of mercury, v = the volume, if the volume taken under a pressure of 1 metre = 1, and s the weight of a litre of hydrogen at 20° in grams. If hydrogen followed Mariotte's law, then under a pressure of 2,500 metres, one litre would contain not 85, but 265 grams. It is evident from the above figures that the weight of a litre of the gas approaches a limit as the pressure increases, which is doubtless the density of the gas when liquefied, and therefore the weight of a litre of liquid hydrogen will probably be near 100 grams (density about 0·1, being less than that of all other liquids).

[29] Cagniard de Latour, on heating ether in a closed tube to about 190°, observed that at this temperature the liquid is transformed into vapour occupying the original volume—that is, having the same density as the liquid. The further investigations made by Drion and myself showed that every liquid has such an absolute boiling point, above which it cannot exist as a liquid and is transformed into a dense gas. In order to grasp the true signification of this absolute boiling temperature, it must be remembered that the liquid state is characterised by a cohesion of its particles which does not exist in vapours and gases. The cohesion of liquids is expressed in their capillary phenomena (the breaks in a column of liquid, drop formation, and rise in capillary tubes, &c.), and the product of the density of a liquid into the height to which it rises in a capillary tube (of a definite diameter) may serve as the measure of the magnitude of cohesion. Thus, in a tube of 1 mm. diameter, water at 15° rises (the height being corrected for the meniscus) 14·8 mm., and ether at t° to a height 5·35 - 0·028t° mm. The cohesion of a liquid is lessened by heating, and therefore the capillary heights are also diminished. It has been shown by experiment that this decrement is proportional to the temperature, and hence by the aid of capillary observations we are able to form an idea that at a certain rise of temperature the cohesion may become = 0. For ether, according to the above formula, this would occur at 191°. If the cohesion disappear from a liquid it becomes a gas, for cohesion is the only point of difference between these two states. A liquid in evaporating and overcoming the force of cohesion absorbs heat. Therefore, the absolute boiling point was defined by me (1861) as that temperature at which (a) a liquid cannot exist as a liquid, but forms a gas which cannot pass into a liquid state under any pressure whatever; (b) cohesion = 0; and (c) the latent heat of evaporation = 0.

This definition was but little known until Andrews (1869) explained the matter from another aspect. Starting from gases, he discovered that carbonic anhydride cannot be liquefied by any degree of compression at temperatures above 31°, whilst at lower temperatures it can be liquefied. He called this temperature the critical temperature. It is evident that it is the same as the absolute boiling point. We shall afterwards designate it by tc. At low temperatures a gas which is subjected to a pressure greater than its maximum tension (Note 27) is transformed into a liquid, which, in evaporating, gives a saturated vapour possessing this maximum tension; whilst at temperatures above tc the pressure to which the gas is subjected may increase indefinitely. However, under these conditions the volume of the gas does not change indefinitely but approaches a definite limit (see Note 28)—that is, it resembles in this respect a liquid or a solid which is altered but little in volume by pressure. The volume which a liquid or gas occupies at tc is termed the critical volume, and corresponds with the critical pressure, which we will designate by pc and express in atmospheres. It is evident from what has been said that the discrepancies from Mariotte and Boyle's law, the absolute boiling point, the density in liquid and compressed gaseous states, and the properties of liquids, must all he intimately connected together. We will consider these relations in one of the following notes. At present we will supplement the above observations by the values of tc and pc for certain liquids and gases which have been investigated in this respect—

Young and Guy (1891) showed that tc and pc clearly depend upon the composition and molecular weight.

[30] I came to this conclusion in 1870 (Ann. Phys. Chem. 141, 623).

[31]

Fig. 24.—General arrangement of the apparatus employed by Pictet for liquefying gases.

Pictet, in his researches, effected the direct liquefaction of many gases which up to that time had not been liquefied. He employed the apparatus used for the manufacture of ice on a large scale, employing the vaporisation of liquid sulphurous anhydride, which may be liquefied by pressure alone. This anhydride is a gas which is transformed into a liquid at the ordinary temperature under a pressure of several atmospheres (see Note 27), and boils at -10° at the ordinary atmospheric pressure. This liquid, like all others, boils at a lower temperature under a diminished pressure, and by continually pumping out the gas which comes off by means of a powerful air-pump its boiling point falls as low as -75°. Consequently, if on the one hand we force liquid sulphurous anhydride into a vessel, and on the other hand pump out the gas from the same vessel by powerful air-pumps, then the liquefied gas will boil in the vessel, and cause the temperature in it to fall to -75°. If a second vessel is placed inside this vessel, then another gas may be easily liquefied in it at the low temperature produced by the boiling liquid sulphurous anhydride. Pictet in this manner easily liquefied carbonic anhydride, CO₂ (at -60° under a pressure of from four to six atmospheres). This gas is more refractory to liquefaction than sulphurous anhydride, but for this reason it gives on evaporating a still lower temperature than can be attained by the evaporation of sulphurous anhydride. A temperature of -80° may be obtained by the evaporation of liquid carbonic anhydride at a pressure of 760 mm., and in an atmosphere rarefied by a powerful pump the temperature falls to -140°. By employing such low temperatures, it was possible, with the aid of pressure, to liquefy the majority of the other gases. It is evident that special pumps which are capable of rarefying gases are necessary to reduce the pressure in the chambers in which the sulphurous and carbonic anhydride boil; and that, in order to re-condense the resultant gases into liquids, special force pumps are required for pumping the liquid anhydrides into the refrigerating chamber. Thus, in Pictet's apparatus (fig. 24), the carbonic anhydride was liquefied by the aid of the pumps E F, which compressed the gas (at a pressure of 4–6 atmospheres) and forced it into the tube K, vigorously cooled by being surrounded by boiling liquid sulphurous anhydride, which was condensed in the tube C by the pump B, and rarefied by the pump A. The liquefied carbonic anhydride flowed down the tube K into the tube H, in which it was subjected to a low pressure by the pump E, and thus gave a very low temperature of about -140°. The pump E carried off the vapour of the carbonic anhydride, and conducted it to the pump F, by which it was again liquefied. The carbonic anhydride thus made an entire circuit—that is, it passed from a rarefied vapour of small tension and low temperature into a compressed and cooled gas, which was transformed into a liquid, which again vaporised and produced a low temperature.

Inside the wide inclined tube H, where the carbonic acid evaporated, was placed a second and narrow tube M containing hydrogen, which was generated in the vessel L from a mixture of sodium formate and caustic soda (CHO₂Na + NaHO = Na₂CO₃ + H₂). This mixture gives hydrogen on heating the vessel L. This vessel and the tube M were made of thick copper, and could withstand great pressures. They were, moreover, hermetically connected together and closed up. Thus the hydrogen which was evolved had no outlet, accumulated in a limited space, and its pressure increased in proportion to the amount of it evolved. This pressure was recorded on a metallic manometer R attached to the end of the tube M. As the hydrogen in this tube was submitted to a very low temperature and a powerful pressure, all the necessary conditions were present for its liquefaction. When the pressure in the tube H became steady—i.e. when the temperature had fallen to -140° and the manometer R indicated a pressure of 650 atmospheres in the tube M—then this pressure did not rise with a further evolution of hydrogen in the vessel L. This served as an indication that the tension of the vapour of the hydrogen had attained a maximum corresponding with -140°, and that consequently all the excess of the gas was condensed to a liquid. Pictet convinced himself of this by opening the cock N, when the liquid hydrogen rushed out from the orifice. But, on leaving a space where the pressure was equal to 650 atmospheres, and coming into contact with air under the ordinary pressure, the liquid or powerfully compressed hydrogen expanded, began to boil, absorbed still more heat, and became still colder. In doing so a portion of the liquid hydrogen, according to Pictet, passed into a solid state, and did not fall in drops into a vessel placed under the outlet N, but as pieces of solid matter, which struck against the sides of the vessel like shot and immediately vaporised. Thus, although it was impossible to see and keep the liquefied hydrogen, still it was clear that it passed not only into a liquid, but also into a solid state. Pictet in his experiments obtained other gases which had not previously been liquefied, especially oxygen and nitrogen, in a liquid and solid state. Pictet supposed that liquid and solid hydrogen has the properties of a metal, like iron.

[32]

Fig. 25.—Cailletet's apparatus for liquefying gases.

At the same time (1879) as Pictet was working on the liquefaction of gases in Switzerland, Cailletet, in Paris, was occupied on the same subject, and his results, although not so convincing as Pictet's, still showed that the majority of gases, previously unliquefied, were capable of passing into a liquid state. Cailletet subjected gases to a pressure of several hundred atmospheres in narrow thick-walled glass tubes (fig. 25); he then cooled the compressed gas as far as possible by surrounding it with a freezing mixture; a cock was then rapidly opened for the outlet of mercury from the tube containing the gas, which consequently rapidly and vigorously expanded. This rapid expansion of the gas would produce great cold, just as the rapid compression of a gas evolves heat and causes a rise in temperature. This cold was produced at the expense of the gas itself, for in rapidly expanding its particles were not able to absorb heat from the walls of the tube, and in cooling a portion of the expanding gas was transformed into liquid. This was seen from the formation of cloud-like drops like a fog which rendered the gas opaque. Thus Cailletet proved the possibility of the liquefaction of gases, but he did not isolate the liquids. The method of Cailletet allows the passage of gases into liquids being observed with greater facility and simplicity than Pictet's method, which requires a very complicated and expensive apparatus.

The methods of Pictet and Cailletet were afterwards improved by Olszewski, Wroblewski, Dewar, and others. In order to obtain a still lower temperature they employed, instead of carbonic acid gas, liquid ethylene or nitrogen and oxygen, whose evaporation at low pressures produces a much lower temperature (to -200°). They also improved on the methods of determining such low temperatures, but the methods were not essentially altered; they obtained nitrogen and oxygen in a liquid, and nitrogen even in a solid, state, but no one has yet succeeded in seeing hydrogen in a liquid form.

The most illustrative and instructive results (because they gave the possibility of maintaining a very low temperature and the liquefied gas, even air, for a length of time) were obtained in recent years by Prof. Dewar in the Royal Institution of London, which is glorified by the names of Davy, Faraday, and Tyndall. Dewar, with the aid of powerful pumps, obtained many kilograms of oxygen and air (the boiling point under the atmospheric pressure = -190°) in a liquid state and kept them in this state for a length of time by means of open glass vessels with double walls, having a vacuum between them, which prevented the rapid transference of heat, and so gave the possibility of maintaining very low temperatures inside the vessel for a long period of time. The liquefied oxygen or air can be poured from one vessel into another and used for any investigations. Thus in June 1894, Prof. Dewar showed that at the low temperature produced by liquid oxygen many substances become phosphorescent (become self-luminous; for instance, oxygen on passing into a vacuum) and fluoresce (emit light after being illuminated; for instance, paraffin, glue, &c.) much more powerfully than at the ordinary temperature; also that solids then greatly alter in their mechanical properties, &c. I had the opportunity (1894) at Prof. Dewar's of seeing many such experiments in which open vessels containing pounds of liquid oxygen were employed, and in following the progress made in researches conducted at low temperatures, it is my firm impression that the study of many phenomena at low temperatures should widen the horizon of natural science as much as the investigation of phenomena made at the highest temperatures attained in the voltaic arc.

[33] The investigations of S. Wroblewski in Cracow give reason to believe that Pictet could not have obtained liquid hydrogen in the interior of his apparatus, and that if he did obtain it, it could only have been at the moment of its outrush due to the fall in temperature following its sudden expansion. Pictet calculated that he obtained a temperature of -140°, but in reality it hardly fell below -120°, judging from the latest data for the vaporisation of carbonic anhydride under low pressure. The difference lies in the method of determining low temperatures. Judging from other properties of hydrogen (see Note 34), one would think that its absolute boiling point lies far below -120°, and even -140° (according to the calculation of Sarrau, on the basis of its compressibility, at -174°). But even at -200° (if the methods of determining such low temperatures be correct) hydrogen does not give a liquid even under a pressure of several hundred atmospheres. However, on expansion a fog is formed and a liquid state attained, but the liquid does not separate.

[34] After the idea of the absolute temperature of ebullition (tc, Note 29) had been worked out (about 1870), and its connection with the deviations from Mariotte's law had become evident, and especially after the liquefaction of permanent gases, general attention was turned to the development of the fundamental conceptions of the gaseous and liquid states of matter. Some investigators directed their energies to the further study of vapours (for instance, Ramsay and Young), gases (Amagat), and liquids (Zaencheffsky, Nadeschdin, and others), especially to liquids near tc and pc; others (Konovaloff and De Heen) endeavoured to discover the relation between liquids under ordinary conditions (removed from tc and pc) and gases, whilst a third class of investigators (van der Waals, Clausius, and others), starting from the generally-accepted principles of the mechanical theory of heat and the kinetic theory of gases, and assuming in gases the existence of those forces which certainly act in liquids, deduced the connection between the properties of one and the other. It would be out of place in an elementary handbook like the present to enunciate the whole mass of conclusions arrived at by this method, but it is well to give an idea of the results of van der Waals' considerations, for they explain the gradual uninterrupted passage from a liquid into a gaseous state in the simplest manner, and, although the deduction cannot be considered as complete and decisive (see Note 25), nevertheless it penetrates so deeply into the essence of the matter that its signification is not only reflected in a great number of physical investigations, but also in the province of chemistry, where instances of the passage of substances from a gaseous to a liquid state are so common, and where the very processes of dissociation, decomposition, and combination must be identified with a change of physical state of the participating substances, which has been elaborated by Gibbs, Lavenig, and others.

For a given quantity (weight, mass) of a definite substance, its state is expressed by three variables—volume v, pressure (elasticity, tension) p, and temperature t. Although the compressibility—[i.e., d(v)/d(p)]—of liquids is small, still it is clearly expressed, and varies not only with the nature of liquids but also with their pressure and temperature (at tc the compressibility of liquids is very considerable). Although gases, according to Mariotte's law, with small variations of pressure, are uniformly compressed, nevertheless the dependence of their volume v on t and p is very complex. This also applies to the coefficient of expansion [= d(v)/d(t), or d(p)/d(t)], which also varies with t and p, both for gases (see Note 26), and for liquids (at tc it is very considerable, and often exceeds that of gases, 0·00367). Hence, the equation of condition must include three variables, v, p, and t. For a so-called perfect (ideal) gas, or for inconsiderable variations of density, the elementary expression pv = Ra(1 + at), or pv = R(273 + t) should be accepted, where R is a constant varying with the mass and nature of a gas, as expressing this dependence, because it includes in itself the laws of Gay-Lussac and Mariotte, for at a constant pressure the volume varies proportionally to 1 + at, and when t is constant the product of tv is constant. In its simplest form the equation may be expressed thus:

pv = RT;

where T denotes what is termed the absolute temperature, or the ordinary temperature + 273—that is, T = t + 273.

Starting from the supposition of the existence of an attraction or internal pressure (expressed by a) proportional to the square of the density (or inversely proportional to the square of the volume), and of the existence of a real volume or diminished length of path (expressed by b) for each gaseous molecule, van der Waals gives for gases the following more complex equation of condition:—

(p + a / v² )(v - b) = 1 + 0·00367t;

if at 0° under a pressure p = 1 (for example, under the atmospheric pressure), the volume (for instance, a litre) of a gas or vapour he taken as 1, and therefore v and b be expressed by the same units as p and a. The deviations from both the laws of Mariotte and Gay-Lussac are expressed by the above equation. Thus, for hydrogen a must be taken as infinitely small, and b = 0·0009, judging by the data for 1,000 and 2,500 metres pressure (Note 28). For other permanent gases, for which (Note 28) I showed (about 1870) from Regnault's and Natterer's data, a decrement of pv, followed by an increment, which was confirmed (about 1880) by fresh determinations made by Amagat, this phenomena may be expressed in definite magnitudes of a and b (although van der Waals' formula is not applicable in the case of very small pressures) with sufficient accuracy for contemporary requirements. It is evident that van der Waals' formula can also express the difference of the coefficients of expansion of gases with a change of pressure, and according to the methods of determination (Note 26). Besides this, van der Waals' formula shows that at temperatures above 273( 8a / 27b -1) only one actual volume (gaseous) is possible, whilst at lower temperatures, by varying the pressure, three different volumes—liquid, gaseous, and partly liquid, partly saturated-vaporous—are possible. It is evident that the above temperature is the absolute boiling point—that is (tc) = 273( 8a / 27b - 1). It is found under the condition that all three possible volumes (the three roots of van der Waals' cubic equation) are then similar and equal (vc = 3b). The pressure in this case (pc) = a / 27b² . These ratios between the constants a and b and the conditions of critical state—i.e. (tc) and (pc)—give the possibility of determining the one magnitude from the other. Thus for ether (Note 29), (tc) = 193°, (tp) = 40, hence a = 0·0307, b = 0·00533, and (vc) = 0·016. That mass of ether which at a pressure of one atmosphere at 0° occupies one volume—for instance, a litre—occupies, according to the above-mentioned condition, this critical volume. And as the density of the vapour of ether compared with hydrogen = 37, and a litre of hydrogen at 0° and under the atmospheric pressure weighs 0·0896 gram, then a litre of ether vapour weighs 3·32 grams; therefore, in a critical state (at 193° and 40 atmospheres) 3·32 grams occupy 0·016 litre, or 16 c.c.; therefore 1 gram occupies a volume of about 5 c.c., and the weight of 1 c.c. of ether will then be 0·21. According to the investigations of Ramsay and Young (1887), the critical volume of ether was approximately such at about the absolute boiling point, but the compressibility of the liquid is so great that the slightest change of pressure or temperature has a considerable effect on the volume. But the investigations of the above savants gave another indirect demonstration of the truth of van der Waals' equation. They also found for ether that the isochords, or the lines of equal volumes (if both t and p vary), are generally straight lines. Thus the volume of 10 c.c. for 1 gram of ether corresponds with pressures (expressed in metres of mercury) equal to 0·135t - 3·3 (for example, at 180° the pressure = 21 metres, and at 280° it = 34·5 metres). The rectilinear form of the isochord (when v = a constant quantity) is a direct result of van der Waals' formula.

When, in 1883, I demonstrated that the specific gravity of liquids decreases in proportion to the rise of temperature [S_t = S₀ - Kt or S_t = S₀(1 - Kt)], or that the volumes increase in inverse proportion to the binomial 1 - Kt, that is, V_t = V₀(1-Kt)^-1, where K is the modulus of expansion, which varies with the nature of the liquid, then, in general, not only does a connection arise between gases and liquids with respect to a change of volume, but also it would appear possible, by applying van der Waals' formula, to judge, from the phenomena of the expansion of liquids, as to their transition into vapour, and to connect together all the principal properties of liquids, which up to this time had not been considered to be in direct dependence. Thus Thorpe and Rücker found that 2(tc) + 273 = 1/K, where K is the modulus of expansion in the above-mentioned formula. For example, the expansion of ether is expressed with sufficient accuracy from 0° to 100° by the equation S_t = 0·736/(1 - 0·00154t), or V_t = 1/(1 - 0·00154t), where 0·00154 is the modulus of expansion, and therefore (tc) = 188°, or by direct observation 193°. For silicon tetrachloride, SiCl₄, the modulus equals 0·00136, from whence (tc) = 231°, and by experiment 230°. On the other hand, D. P. Konovaloff, admitting that the external pressure p in liquids is insignificant when compared with the internal (a in van der Waals' formula), and that the work in the expansion of liquids is proportional to their temperature (as in gases), directly deduced, from van der Waals' formula, the above-mentioned formula for the expansion of liquids, V_t = 1/(1 - Kt), and also the magnitude of the latent heat of evaporation, cohesion, and compressibility under pressure. In this way van der Waals' formula embraces the gaseous, critical, and liquid states of substances, and shows the connection between them. On this account, although van der Waals' formula cannot be considered as perfectly general and accurate, yet it is not only very much more exact than pv = RT, but it is also more comprehensive, because it applies both to gases and liquids. Further research will naturally give a closer proximity to truth, and will show the connection between composition and the constants (a and b); but a great scientific progress is seen in this form of the equation of state.

Clausius (in 1880), taking into consideration the variability of a, in van der Waals' formula, with the temperature, gave the following equation of condition:—

(p + a / T(v + c)² )(v - b) = RT.

Sarrau applied this formula to Amagat's data for hydrogen, and found a = 0·0551, c = -0·00043, b = 0·00089, and therefore calculated its absolute boiling point as -174°, and (pc) = 99 atmospheres. But as similar calculations for oxygen (-105°), nitrogen (-124°), and marsh gas (-76°) gave tc higher than it really is, the absolute boiling point of hydrogen must lie below -174°.

[35] This and a number of similar cases clearly show how great are the internal chemical forces compared with physical and mechanical forces.

[36] The property of palladium of absorbing hydrogen, and of increasing in volume in so doing, may be easily demonstrated by taking a sheet of palladium varnished on one side, and using it as a cathode. The hydrogen which is evolved by the action of the current is retained by the unvarnished surface, as a consequence of which the sheet curls up. By attaching a pointer (for instance, a quill) to the end of the sheet this bending effect is rendered strikingly evident, and on reversing the current (when oxygen will be evolved and combine with the absorbed hydrogen, forming water) it may be shown that on losing the hydrogen the palladium regains its original form.

[37] Deville discovered that iron and platinum become pervious to hydrogen at a red heat. He speaks of this in the following terms:—‘The permeability of such homogeneous substances as platinum and iron is quite different from the passage of gases through such non-compact substances as clay and graphite. The permeability of metals depends on their expansion, brought about by heat, and proves that metals and alloys have a certain porosity.’ However, Graham proved that it is only hydrogen which is capable of passing through the above-named metals in this manner. Oxygen, nitrogen, ammonia, and many other gases, only pass through in extremely minute quantities. Graham showed that at a red heat about 500 c.c. of hydrogen pass per minute through a surface of one square metre of platinum 1·1 mm. thick, but that with other gases the amount transmitted is hardly perceptible. Indiarubber has the same capacity for allowing the transference of hydrogen through its substance (see Chapter III.), but at the ordinary temperature one square metre, 0·014 mm. thick, transmits only 127 c.c. of hydrogen per minute. In the experiment on the decomposition of water by heat in porous tubes, the clay tube may be exchanged for a platinum one with advantage. Graham showed that by placing a platinum tube containing hydrogen under these conditions, and surrounding it by a tube containing air, the transference of the hydrogen may be observed by the decrease of pressure in the platinum tube. In one hour almost all the hydrogen (97 p.c.) had passed from the tube, without being replaced by air. It is evident that the occlusion and passage of hydrogen through metals capable of occluding it are not only intimately connected together, but are dependent on the capacity of metals to form compounds of various degrees of stability with hydrogen—like salts with water.

[38] It appeared on further investigation that palladium gives a definite compound, Pd₂H (see further) with hydrogen; but what was most instructive was the investigation of sodium hydride, Na₂H, which clearly showed that the origin and properties of such compounds are in entire accordance with the conceptions of dissociation.

Since hydrogen is a gas which is difficult to condense, it is little soluble in water and other liquids. At 0° a hundred volumes of water dissolve 1·9 volume of hydrogen, and alcohol 6·9 volumes measured at 0° and 760 mm. Molten iron absorbs hydrogen, but in solidifying, it expels it. The solution of hydrogen by metals is to a certain degree based on its affinity for metals, and must be likened to the solution of metals in mercury and to the formation of alloys. In its chemical properties hydrogen, as we shall see later, has much of a metallic character. Pictet (see Note 31) even affirms that liquid hydrogen has metallic properties. The metallic properties of hydrogen are also evinced in the fact that it is a good conductor of heat, which is not the case with other gases (Magnus).

[39] If it be desired to obtain a perfectly colourless hydrogen flame, it must issue from a platinum nozzle, as the glass end of a gas-conducting tube imparts a yellow tint to the flame, owing to the presence of sodium in the glass.

[40] Let us imagine that a stream of hydrogen passes along a tube, and let us mentally divide this stream into several parts, consecutively passing out from the orifice of the tube. The first part is lighted—that is, brought to a state of incandescence, in which state it combines with the oxygen of the atmosphere. A considerable amount of heat is evolved in the combination. The heat evolved then, so to say, ignites the second part of hydrogen coming from the tube, and, therefore, when once ignited, the hydrogen continues to burn, if there be a continual supply of it, and if the atmosphere in which it burns be unlimited and contains oxygen.

[41] The combustibility of hydrogen may be shown by the direct decomposition of water by sodium. If a pellet of sodium be thrown into a vessel containing water, it floats on the water and evolves hydrogen, which may be lighted. The presence of sodium imparts a yellow tint to the flame. If potassium be taken, the hydrogen bursts into flame spontaneously, because sufficient heat is evolved in the reaction to ignite the hydrogen. The flame is coloured violet by the potassium. If sodium be thrown not on to water, but on to an acid, it will evolve more heat, and the hydrogen will then also burst into flame. These experiments must be carried on with caution, as, sometimes towards the end, a mass of sodium oxide (Note 8) is produced, and flies about; it is therefore best to cover the vessel in which the experiment is carried on.

[42] This property of spongy platinum is made use of in the so-called hydrogen cigar-lighter. It consists of a glass cylinder or beaker, inside which there is a small lead stand (which is not acted on by sulphuric acid), on which a piece of zinc is laid. This zinc is covered by a bell, which is open at the bottom and furnished with a cock at the top. Sulphuric acid is poured into the space between the bell and the sides of the outer glass cylinder, and will thus compress the gas in the bell. If the cock of the cylinder be opened the gas will escape by it, and will be replaced by the acid, which, coming into contact with the zinc, evolves hydrogen, and it will escape through the cock. If the cock be closed, then the hydrogen evolved will increase the pressure of the gas in the bell, and thus again force the acid into the space between the bell and the walls of the outer cylinder. Thus the action of the acid on the zinc may be stopped or started at will by opening or shutting the cock, and consequently a stream of hydrogen may be always turned on. Now, if a piece of spongy platinum be placed in this stream, the hydrogen will take light, because the spongy platinum becomes hot in condensing the hydrogen and inflames it. The considerable rise in temperature of the platinum depends, among other things, on the fact that the hydrogen condensed in its pores comes into contact with previously absorbed and condensed atmospheric oxygen, with which hydrogen combines with great facility in this form. In this manner the hydrogen cigar-lighter gives a stream of burning hydrogen when the cock is open. In order that it should work regularly it is necessary that the spongy platinum should be quite clean, and it is best enveloped in a thin sheet of platinum foil, which protects it from dust. In any case, after some time it will be necessary to clean the platinum, which may be easily done by boiling it in nitric acid, which does not dissolve the platinum, but clears it of all dirt. This imperfection has given rise to several other forms, in which an electric spark is made to pass before the orifice from which the hydrogen escapes. This is arranged in such a manner that the zinc of a galvanic element is immersed when the cock is turned, or a small coil giving a spark is put into circuit on turning the hydrogen on.

[43] Under conditions similar to those in which hydrogen combines with oxygen it is also capable of combining with chlorine. A mixture of hydrogen and chlorine explodes on the passage of an electric spark through it, or on contact with an incandescent substance, and also in the presence of spongy platinum; but, besides this, the action of light alone is enough to bring about the combination of hydrogen and chlorine. If a mixture of equal volumes of hydrogen and chlorine be exposed to the action of sunlight, complete combination rapidly ensues, accompanied by a report. Hydrogen does not combine directly with carbon, either at the ordinary temperature or by the action of heat and pressure. But if an electric current be passed through carbon electrodes at a short distance from each other (as in the electric light or voltaic arc), so as to form an electric arc in which the particles of carbon are carried from one pole to the other, then, in the intense heat to which the carbon is subjected in this case, it is capable of combining with hydrogen. A gas of peculiar smell called acetylene, C₂H₂, is thus formed from carbon and hydrogen.

[44] There is another explanation of the facility with which hydrogen reacts in a nascent state. We shall afterwards learn that the molecule of hydrogen contains two atoms, H₂, but there are elements the molecules of which only contain one atom—for instance, mercury. Therefore, every reaction of gaseous hydrogen must be accompanied by the disruption of that bond which exists between the atoms forming a molecule. At the moment of evolution, however, it is supposed that free atoms exist, and in this condition, according to the hypothesis, act energetically. This hypothesis is not based upon facts, and the idea that hydrogen is condensed at the moment of its evolution is more natural, and is in accordance with the fact (Note 12) that compressed hydrogen displaces palladium and silver (Brunner, Beketoff)—that is, acts as at the moment of its liberation.

[44 bis] There is a very intimate and evident relation between the phenomena which take place in the action of spongy platinum and the phenomena of the action in a nascent state. The combination of hydrogen with aldehyde may be taken as an example. Aldehyde is a volatile liquid with an aromatic smell, boiling at 21°, soluble in water, and absorbing oxygen from the atmosphere, and in this absorption forming acetic acid—the substance which is found in ordinary vinegar. If sodium amalgam be thrown into an aqueous solution of aldehyde, the greater part of the hydrogen evolved combines with the aldehyde, forming alcohol—a substance also soluble in water, which forms the principle of all spirituous liquors, boils at 78°, and contains the same amount of oxygen and carbon as aldehyde, but more hydrogen. The composition of aldehyde is C₂H₄O, that of alcohol C₂H₆O.

[45] When, for instance, an acid and zinc are added to a salt of silver, the silver is reduced; but this may be explained as a reaction of the zinc, and not of the hydrogen at the moment of its formation. There are, however, examples to which this explanation is entirely inapplicable; thus, for instance, hydrogen, at the moment of its liberation easily takes up oxygen from its compounds with nitrogen if they be in solution, and converts the nitrogen into its hydrogen-compound. Here the nitrogen and hydrogen, so to speak, meet at the moment of their liberation, and in this state combine together.

It is evident from this that the elastic gaseous state of hydrogen fixes the limit of its energy: prevents it from entering into those combinations of which it is capable. In the nascent state we have hydrogen which is not in a gaseous state, and its action is then much more energetic. At the moment of evolution that heat, which would be latent in the gaseous hydrogen, is transmitted to its molecules, and consequently they are in a state of strain, and can hence act on many substances.

[46] Several numerical data and reflections bearing on this matter are enumerated in Notes 7, 9, and 11. It must be observed that the action of iron or zinc on water is reversible. But the reaction CuO + H₂ = Cu + H₂O is not reversible; the difference between the degrees of affinity is very great in this case, and, therefore, so far as is at present known, no hydrogen is liberated even in the presence of a large excess of water. It is to be further remarked, that under the conditions of the dissociation of water, copper is not oxidised by water, because the oxide of copper is reduced by free hydrogen. If a definite amount of a metal and acid be taken and their reaction be carried on in a closed space, then the evolution of hydrogen will cease, when its tension equals that at which compressed hydrogen displaces the metal. The result depends upon the nature of the metal and the strength of the solution of acid. Tammann and Nernst (1892) found that the metals stand in the following order in respect to this limiting tension of hydrogen:—Na, Mg, Zn, Al, Cd, Fe, Ni.

[47] This determination may be carried on in an apparatus like that mentioned in Note 13 of Chapter I.

[48] We will proceed to describe Dumas' method and results. For this determination pure and dry copper oxide is necessary. Dumas took a sufficient quantity of copper oxide for the formation of 50 grams of water in each determination. As the oxide of copper was weighed before and after the experiment, and as the amount of oxygen contained in water was determined by the difference between these weights, it was essential that no other substance besides the oxygen forming the water should be evolved from the oxide of copper during its ignition in hydrogen. It was necessary, also, that the hydrogen should be perfectly pure, and free not only from traces of moisture, but from any other impurities which might dissolve in the water or combine with the copper and form some other compound with it. The bulb containing the oxide of copper (fig. 26), which was heated to redness, should be quite free from air, as otherwise the oxygen in the air might, in combining with the hydrogen passing through the vessel, form water in addition to that formed by the oxygen of the oxide of copper. The water formed should be entirely absorbed in order to accurately determine its quantity. The hydrogen was evolved in the three-necked bottle. The sulphuric acid, for acting on the zinc, is poured through funnels into the middle neck. The hydrogen evolved in the Woulfe's bottle passes through U tubes, in which it is purified, to the bulb, where it comes into contact with the copper oxide, forms water, and reduces the oxide to metallic copper; the water formed is condensed in the second bulb, and any passing off is absorbed in the second set of U tubes. This is the general arrangement of the apparatus. The bulb with the copper oxide is weighed before and after the experiment. The loss in weight shows the quantity of oxygen which entered into the composition of the water formed, the weight of the latter being shown by the gain in weight of the absorbing apparatus. Knowing the amount of oxygen in the water formed, we also know the quantity of hydrogen contained in it, and consequently we determine the composition of water by weight. This is the essence of the determination. We will now turn to certain particulars. In one neck of the three-necked bottle a tube is placed dipping under mercury. This serves as a safety-valve to prevent the pressure inside the apparatus becoming too great from the rapid evolution of hydrogen. If the pressure rose to any considerable extent, the current of gases and vapours would be very rapid, and, as a consequence, the hydrogen would not be perfectly purified, or the water entirely absorbed in the tubes placed for this purpose. In the third neck of the Woulfe's bottle is a tube conducting the hydrogen to the purifying apparatus, consisting of eight U tubes, destined for the purification and testing of the hydrogen. The hydrogen, evolved by zinc and sulphuric acid, is purified by passing it first through a tube full of pieces of glass moistened with a solution of lead nitrate next through silver sulphate; the lead nitrate retains sulphurette hydrogen, and arseniuretted hydrogen is retained by the tube with silver sulphate. Caustic potash in the next U tube retains any acid which might come over. The two following tubes are filled with lumps of dry caustic potash in order to absorb any carbonic anhydride and moisture which the hydrogen might contain. The next two tubes, to remove the last traces of moisture, are filled with phosphoric anhydride, mixed with lumps of pumice-stone. They are immersed in a freezing mixture. The small U tube contains hygroscopic substances, and is weighed before the experiment: this is in order to know whether the hydrogen passing through still retains any moisture. If it does not, then the weight of this tube will not vary during the whole experiment, but if the hydrogen evolved still retains moisture, the tube will increase in weight. The copper oxide is placed in the bulb, which, previous to the experiment, is dried with the copper oxide for a long period of time. The air is then exhausted from it, in order to weigh the oxide of copper in a vacuum and to avoid the need of a correction for weighing in air. The bulb is made of infusible glass, that it may be able to withstand a lengthy (20 hours) exposure to a red heat without changing in form. The weighed bulb is only connected with the purifying apparatus after the hydrogen has passed through for a long time, and after experiment has shown that the hydrogen passing from the purifying apparatus is pure and does not contain any air. On passing from the condensing bulb the gas and vapour enter into an apparatus for absorbing the last traces of moisture. The first U tube contains pieces of ignited potash, the second and third tubes phosphoric anhydride or pumice-stone moistened with sulphuric acid. The last of the two is employed for determining whether all the moisture is absorbed, and is therefore weighed separately. The final tube only serves as a safety-tube for the whole apparatus, in order that the external moisture should not penetrate into it. The glass cylinder contains sulphuric acid, through which the excess of hydrogen passes; it enables the rate at which the hydrogen is evolved to be judged, and whether its amount should be decreased or increased.

Fig. 26.—Apparatus employed by Dumas for determining the composition of water. Described in text.

When the apparatus is fitted up it must be seen that all its parts are hermetically tight before commencing the experiment. When the previously weighed parts are connected together and the whole apparatus put into communication, then the bulb containing the copper oxide is heated with a spirit lamp (reduction does not take place without the aid of heat), and the reduction of the copper oxide then takes place, and water is formed. When nearly all the copper oxide is reduced the lamp is removed and the apparatus allowed to cool, the current of hydrogen being kept up all the time. When cool, the drawn-out end of the bulb is fused up, and the hydrogen remaining in it is exhausted, in order that the copper may be again weighed in a vacuum. The absorbing apparatus remains full of hydrogen, and would therefore present a less weight than if it were full of air, as it was before the experiment, and for this reason, having disconnected the copper oxide bulb, a current of dry air is passed through it until the gas passing from the glass cylinder is quite free from hydrogen. The condensing bulb and the two tubes next to it are then weighed, in order to determine the quantity of water formed. Dumas repeated this experiment many times. The average result was that water contains 1253·3 parts of hydrogen per 10,000 parts of oxygen. Making a correction for the amount of air contained in the sulphuric acid employed for producing the hydrogen, Dumas obtained the average figure 1251·5, between the extremes 1247·2 and 1256·2. This proves that per 1 part of hydrogen water contains 7·9904 parts of oxygen, with a possible error of not more than ¹⁄₂₅₀, or 0·03, in the amount of oxygen per 1 part of hydrogen.

Erdmann and Marchand, in eight determinations, found that per 10,000 parts of oxygen water contains an average of 1,252 parts of hydrogen, with a difference of from 1,258·5 to 1,248·7; hence per 1 part of hydrogen there would be 7·9952 of oxygen, with an error of at least 0·05.

Keiser (1888), in America by employing palladium hydride, and by introducing various fresh precautions for obtaining accurate results, found the composition of water to be 15·95 parts of oxygen per 2 of hydrogen.

Certain of the latest determinations of the composition of water, as also those made by Dumas, always give less than 8, and on the average 7·98, of oxygen per 1 part of hydrogen. However, not one of these figures is to be entirely depended on, and for ordinary accuracy it may be considered that O = 16 when H = 1.

[1] As regards the interior of the earth, it probably contains far less oxygen compounds than the surface, judging by the accumulated evidences of the earth's origin, of meteorites, of the earth's density, &c. (see Chapter VIII., Note 58, and Chapter XXII., Note 2).

[2] It is evident that the partial pressure (see Chapter I.) acts in respiration. The researches of Paul Bert showed this with particular clearness. Under a pressure of one-fifth of an atmosphere consisting of oxygen only, animals and human beings remain under the ordinary conditions of the partial pressure of oxygen, but organisms cannot support air rarefied to one-fifth, for then the partial pressure of the oxygen falls to one-twenty-fifth of an atmosphere. Even under a pressure of one-third of an atmosphere the regular life of human beings is impossible, by reason of the impossibility of respiration (because of the decrease of solubility of oxygen in the blood), owing to the small partial pressure of the oxygen, and not from any mechanical effect of the decrease of pressure. Paul Bert illustrated all this by many experiments, some of which he conducted on himself. This explains, among other things, the discomfort felt in the ascent of high mountains or in balloons when the height reached exceeds eight kilometres, and at pressures below 250 mm. (Chapter II., Note 23). It is evident that an artificial atmosphere has to be employed in the ascent to great heights, just as in submarine work. The cure by compressed and rarefied air which is practised in certain illnesses is based partly on the mechanical action of the change of pressure, and partly on the alteration in the partial pressure of the respired oxygen.

[3] At night, without the action of light, without the absorption of that energy which is required for the decomposition of carbonic anhydride into free oxygen and carbon (which is retained by the plants) they breathe like animals, absorbing oxygen and evolving carbonic anhydride. This process also goes on side by side with the reverse process in the daytime, but it is then far feebler than that which gives oxygen.

[4] The earth's surface is equal to about 510 million square kilometres, and the mass of the air (at a pressure of 760 mm.) on each kilometre of surface is about 10⅓ thousand millions of kilograms, or about 10⅓ million tons; therefore the whole weight of the atmosphere is about 5,100 million million (= 51 × 10¹⁴) tons. Consequently there are about 2 × 10¹⁵ tons of free oxygen in the earth's atmosphere. The innumerable series of processes which absorb a portion of this oxygen are compensated for by the plant processes. Assuming that 100 million tons of vegetable matter, containing 40 p.c. of carbon, formed from carbonic acid, are produced (and the same process proceeds in water) per year on the 100 million square kilometres of dry land (ten tons of roots, leaves, stems, &c., per hectare, or 1 / 100 of a square kilometre), we find that the plant life of the dry land gives about 100,000 tons of oxygen, which is an insignificant fraction of the entire mass of the oxygen of the air.

[5] The extraction of oxygen from water may be effected by two processes: either by the decomposition of water into its constituent parts by the action of a galvanic current (Chapter II.), or by means of the removal of the hydrogen from water. But, as we have seen and already know, hydrogen enters into direct combination with very few substances, and then only under special circumstances; whilst oxygen, as we shall soon learn, combines with nearly all substances. Only gaseous chlorine (and, especially, fluorine) is capable of decomposing water, taking up the hydrogen from it, without combining with the oxygen. Chlorine is soluble in water, and if an aqueous solution of chlorine, so-called chlorine water, be poured into a flask, and this flask be inverted in a basin containing the same chlorine water, then we shall have an apparatus by means of which oxygen may be extracted from water. At the ordinary temperature, and in the dark, chlorine does not act on water, or only acts very feebly; but under the action of direct sunlight chlorine decomposes water, with the evolution of oxygen. The chlorine then combines with the hydrogen, and gives hydrochloric acid, which dissolves in the water, and therefore free oxygen only will be separated from the liquid, and it will only contain a small quantity of chlorine in admixture, which can be easily removed by passing the gas through a solution of caustic potash.

[6]

Fig. 27.—Graham's apparatus for the decomposition of air by pumping it through india-rubber.

A difference in the physical properties of both gases cannot be here taken advantage of, because they are very similar in this respect. Thus the density of oxygen is 16 times and of nitrogen 14 times greater than the density of hydrogen, and therefore porous vessels cannot be here employed—the difference between the times of their passage through a porous surface would be too insignificant.

Graham, however, succeeded in enriching air in oxygen by passing it through india-rubber. This may be done in the following way:—A common india-rubber cushion, E (Fig. 27), is taken, and its orifice hermetically connected with an air-pump, or, better still, a mercury aspirator (the Sprengel pump is designated by the letters A, C, B). When the aspirator (Chapter II., Note 16) has pumped out the air, which will be seen by the mercury running out in an almost uninterrupted stream, and from its standing approximately at the barometric height, then it may be clearly observed that gas passes through the india-rubber. This is also seen from the fact that bubbles of gas continually pass along with the mercury. A minus pressure may be constantly maintained in the cushion by pouring mercury into the funnel A, and screwing up the pinchcock C, so that the stream flowing from it is small, and then a portion of the air passing through the india-rubber will be carried along with the mercury. This air may be collected in the cylinder, R. Its composition proves to be about 42 volumes of oxygen with 57 volumes of nitrogen, and one volume of carbonic anhydride, whilst ordinary air contains only 21 volumes of oxygen in 100 volumes. A square metre of india-rubber surface (of the usual thickness) passes about 45 c.c. of such air per hour. This experiment clearly shows that india-rubber is permeable to gases. This may, by the way, be observed in common toy balloons filled with coal-gas. They fall after a day or two, not because there are holes in them, but because air penetrates into, and the gas from, their interior, through the surface of the india-rubber of which they are made. The rate of the passage of gases through india-rubber does not, as Mitchell and Graham showed, depend on their densities, and consequently its permeability is not determined by orifices. It more resembles dialysis—that is, the penetration of liquids through colloid surfaces. Equal volumes of gases penetrate through india-rubber in periods of time which are related to each other as follows:—carbonic anhydride, 100; hydrogen, 247; oxygen, 532; marsh gas, 633; carbonic oxide, 1,220; nitrogen, 1,358. Hence nitrogen penetrates more slowly than oxygen, and carbonic anhydride more quickly than other gases. 2·556 volumes of oxygen and 13·585 volumes of carbonic anhydride penetrate in the same time as one volume of nitrogen. By multiplying these ratios by the amounts of these gases in air, we obtain figures which are in almost the same proportion as the volumes of the gases penetrating from air through india-rubber. If the process of dialysis be repeated on the air which has already passed through india-rubber, then a mixture containing 65 p.c. by volume of oxygen is obtained. It may be thought that the cause of this phenomenon is the absorption or occlusion (see Chap. II., Note 37) of gases by india-rubber and the evolution of the gas dissolved in a vacuum; and, indeed, india-rubber does absorb gases, especially carbonic anhydride. Graham called the above method of the decomposition of air atmolysis.

[7] The preparation of oxygen by this method, which is due to Boussingault, is conducted in a porcelain tube, which is placed in a stove heated by charcoal, so that its ends project beyond the stove. Barium oxide (which may be obtained by igniting barium nitrate, previously dried) is placed in the tube, one end of which is connected with a pair of bellows, or a gas-holder, for keeping up a current of air through it. The air is previously passed through a solution of caustic potash, to remove all traces of carbonic anhydride, and it is very carefully dried (for the hydrate BaH₂O₂ does not give the peroxide). At a dark-red heat (500–600°) the oxide of barium absorbs oxygen from the air, so that the gas leaving the tube consists almost entirely of nitrogen. When the absorption ceases, the air will pass through the tube unchanged, which may be recognised from the fact that it supports combustion. The barium oxide is converted into peroxide under these circumstances, and eleven parts of barium oxide absorb about one part of oxygen by weight. When the absorption ceases, one end of the tube is closed, a cork with a gas-conducting tube is fixed into the other end, and the heat of the stove is increased to a bright-red heat (800°). At this temperature the barium peroxide gives up all that oxygen which it acquired at a dark-red heat—i.e. about one part by weight of oxygen is evolved from twelve parts of barium peroxide. After the evolution of the oxygen there remains the barium oxide which was originally taken, so that air may be again passed over it, and thus the preparation of oxygen from one and the same quantity of barium oxide may be repeated many times. Oxygen has been produced one hundred times from one mass of oxide by this method; all the necessary precautions being taken, as regards the temperature of the mass and the removal of moisture and carbonic acid from the air. Unless these precautions be taken, the mass of oxide soon spoils.

As oxygen may become of considerable technical use, from its capacity for giving high temperatures and intense light in the combustion of substances, its preparation directly from air by practical methods forms a problem whose solution many investigators continue to work at up to the present day. The most practical methods are those of Tessié du Motay and Kassner. The first is based on the fact that a mixture of equal weights of manganese peroxide and caustic soda at an incipient red heat (about 350°) absorbs oxygen from air, with the separation of water, according to the equation MnO₂ + 2NaHO + O = Na₂MnO₄ + H₂O. If superheated steam, at a temperature of about 450°, be then passed through the mixture, the manganese peroxide and caustic soda originally taken are regenerated, and the oxygen held by them is evolved, according to the reverse equation Na₂MnO₄ + H₂O = MnO₂ + 2NaHO + O. This mode of preparing oxygen may be repeated for an infinite number of times. The oxygen in combining liberates water, and steam, acting on the resultant substance, evolves oxygen. Hence all that is required for the preparation of oxygen by this method is fuel and the alternate cutting off the supply of air and steam. In Kassner's process (1891) a mixture of oxide of lead and lime (PbO + 2CaO) is heated to redness in the presence of air, oxygen is then absorbed and calcium plumbate, Ca₂PbO₄, formed. The latter is of a chocolate colour, and on further heating evolves oxygen and gives the original mixture PbO + 2CaO—that is, the phenomenon is essentially the same as in Boussingault's process (with BaO), but according to Le Chatelier (1893) the dissociation tension of the oxygen evolved from Ca₂PbO₄ is less than with BaO₂ at equal temperatures; for instance, at 940°, 112 mm. of mercury for the first, and for the latter 210 mm. at 720°, and 670 mm. at 790°, while for Ca₂PbO₄ this tension is only reached at 1,080°. However, in Kassner's process the oxygen is absorbed more rapidly, and the influence of the presence of moisture and CO₂ in the air is not so marked, so that this process, like that of Tessié du Motay, deserves consideration.

[8] Even the decomposition of manganese peroxide is reversible, and it may be re-obtained from that suboxide (or its salts), which is formed in the evolution of oxygen (Chap. XI., Note 6). The compounds of chromic acid containing the trioxide CrO₃ in evolving oxygen give chromium oxide, Cr₂O₃, but they re-form the salt of chromic acid when heated to redness in air with an alkali.

[9] We shall afterwards see that it is only substances like barium peroxide (which give hydrogen peroxide) which should be counted as true peroxides, and that MnO₂, PbO₂, &c., should be distinguished from them (they do not give hydrogen peroxide with acids), and therefore it is best to call them dioxides.

[9 bis]Peroxide of barium also gives oxygen at the ordinary temperature in the presence of the solutions of many substances in a higher degree of oxidation. In this respect we may mention that Kassner (1890) proposes to obtain oxygen for laboratory purposes by mixing BaO₂ with FeK₃(CN)₆ (red prussiate of potash, Chapter XXII.): the reaction proceeds with the evolution of oxygen even on the addition of a very small quantity of water. In order to ensure a gradual evolution of gas the author proposes to introduce both substances into the reaction, little by little, instead of all at once, which may be done with the following arrangement (Gavaloffsky): finely powdered peroxide of barium is placed in an ordinary flask and sufficient water is added to fill the flask one-third full. The cork closing the flask has three holes; (1) for the gas-conducting tube; (2) for a rod to stir the BaO₂; and (3) for a glass rod terminating in a perforated glass vessel containing crystals of FeK₃(CN)₆. When it is desired to start the evolution of the oxygen, the vessel is lowered until it is immersed in the liquid in the flask, and the BaO₂ is stirred with the other rod. The reaction proceeds according to the equation, BaO₂ + 2FeK₃(CN)₆ = FeK₄(CN)₆ + FeK₂Ba(CN)₆ + O₂. The double salt, FeBa₂(CN)₆, crystallises out from the mother liquor. To understand the course of the reaction, it must be remembered BaO₂ is of a higher degree of oxidation, and that it parts with oxygen and gives the base BaO which enters into the complex salt FeK₂Ba(CN)₆ = Fe(CN)₂ + 2KCN + Ba(CN)₂, and this latter = BaO + 2HCN - H₂O. Moreover, FeK₃(CN)₆ contains the salt Fe₂(CN)₆ which also corresponds to the higher degree of oxidation of iron, Fe₂O₃, whilst after the reaction a salt is obtained which contains Fe(CN)₂, and corresponds to the lower degree of oxidation, FeO, so that (in the presence of water) oxygen is also set free on this side also, i.e. the reaction gives lower degrees of oxidation and oxygen.

[10] Scheele, in 1785, discovered the method of obtaining oxygen by treating manganese peroxide with sulphuric acid.

[11] All acids rich in oxygen, and especially those whose elements form lower oxides, evolve oxygen either directly at the ordinary temperature (for instance, ferric acid), or on heating (nitric, manganic, chromic, chloric, and others), or if basic lower oxides are formed from them, by heating with sulphuric acid. Thus the salts of chromic acid (for example, potassium dichromate, K₂Cr₂O₇) give oxygen with sulphuric acid; first potassium sulphate, K₂SO₄, is formed, and then the chromic acid set free gives a sulphuric acid salt of the lower oxide, Cr₂O₃.

[12] This reaction is not reversible, and is exothermal—that is, it does not absorb heat, but, on the contrary, evolves 9,713 calories per molecular weight KClO₃, equal to 122 parts of salt (according to the determination of Thomsen, who burnt hydrogen in a calorimeter either alone or with a definite quantity of potassium chlorate mixed with oxide of iron). It does not proceed at once, but first forms perchlorate, KClO₄ (see Chlorine and Potassium). It is to be remarked that potassium chloride melts at 766°, potassium chlorate at 359°, and potassium perchlorate at 610°. (Concerning the decomposition of KClO₃, see Chapter II., Note 47.)

[13] The peroxide does not evolve oxygen in this case. It may be replaced by many oxides—for instance, by oxide of iron. It is necessary to take the precaution that no combustible substances (such as bits of paper, splinters, sulphur, &c.) fall into the mixture, as they might cause an explosion.

[14] The decomposition of a mixture of fused and well-crushed potassium chlorate with powdered manganese peroxide proceeds at so low a temperature (the salt does not melt) that it may be effected in an ordinary glass flask. The apparatus is arranged in the same manner as in the decomposition of mercury oxide (Introduction), or as shown in the last drawing. As the reaction is exothermal, the decomposition of potassium chlorate with the formation of oxygen may probably be accomplished, under certain conditions (for example, under contact action), at very low temperatures. Substances mixed with the potassium chlorate probably act partially in this manner.

[15] Many other salts evolve oxygen by heat, like potassium chlorate, but they only part with it either at a very high temperature (for instance, common nitre) or else are unsuited for use on account of their cost (potassium manganate), or evolve impure oxygen at a high temperature (zinc sulphate at a red heat gives a mixture of sulphurous anhydride and oxygen), and are not therefore used in practice.

[16] Such is, at present, the only possible method of explaining the phenomenon of contact action. In many cases, such as the present one, it is supported by observations based on facts. Thus, for instance, it is known, as regards oxygen, that often two substances rich in oxygen retain it so long as they are separate, but directly they come into contact free oxygen is evolved from both of them. Thus, an aqueous solution of hydrogen peroxide (containing twice as much oxygen as water) acts in this manner on silver oxide (containing silver and oxygen). This reaction takes place at the ordinary temperature, and the oxygen is evolved from both compounds. To this class of phenomena may be also referred the fact that a mixture of barium peroxide and potassium manganate with water and sulphuric acid evolves oxygen at the ordinary temperature (Note 9). It would seem that the essence of phenomena of this kind is entirely and purely a property of contact; the distribution of the atoms is changed by contact, and if the equilibrium be unstable it is destroyed. This is more especially evident in the case of those substances which change exothermally—that is, for those reactions which are accompanied by an evolution of heat. The decomposition CaCl₂O₂ = CaCl₂ + O₂ belongs to this class (like the decomposition of potassium chlorate).

[17] Generally a solution of bleaching powder is alkaline (contains free lime), and therefore, a solution of cobalt chloride is added directly to it, by which means the oxide of cobalt required for the reaction is formed.

[18] It must be remarked that in all the reactions above mentioned the formation of oxygen may be prevented by the admixture of substances capable of combining with it—for example, charcoal, many carbon (organic) compounds, sulphur, phosphorus, and various lower oxidation products, &c. These substances absorb the oxygen evolved, combine with it, and a compound containing oxygen is formed. Thus, if a mixture of potassium chlorate and charcoal be heated, no oxygen is obtained, but an explosion takes place from the rapid formation of gases resulting from the combination of the oxygen of the potassium chlorate with the charcoal and the evolution of gaseous CO₂.

The oxygen obtained by any of the above-described methods is rarely pure. It generally contains aqueous vapour, carbonic anhydride, and very often small traces of chlorine. The oxygen may be freed from these impurities by passing it through a solution of caustic potash, and by drying it. If the potassium chlorate be dry and pure, it gives almost pure oxygen. However, if the oxygen be required for respiration in cases of sickness, it should be washed by passing it through a solution of caustic alkali and through water. The best way to obtain pure oxygen directly is to take potassium perchlorate (KClO₄), which can be well purified and then evolves pure oxygen on heating.

[19] With regard to the absolute boiling point, critical pressure, and the critical state in general, see Chapter II., Notes 29 and 34.

[20] Judging from what has been said in Note 34 of the last chapter, and also from the results of direct observation, it is evident that all substances in a critical state have a large coefficient of expansion, and are very compressible.

[21] As water consists of 1 volume of oxygen and 2 volumes of hydrogen, and contains 16 parts by weight of oxygen per 2 parts by weight of hydrogen, it therefore follows directly that oxygen is 16 times denser than hydrogen. Conversely, the composition of water by weight may be deduced from the densities of hydrogen and oxygen, and the volumetric composition of water. This method of mutual and reciprocal correction strengthens the practical data of the exact sciences, whose conclusions require the greatest possible exactitude and variety of corrections.

It must he observed that the specific heat of oxygen at constant pressure is 0·2175, consequently it is to the specific heat of hydrogen (3·409) as 1 is to 15·6. Hence, the specific heats are inversely proportional to the weights of equal volumes. This signifies that equal volumes of both gases have (nearly) equal specific heats—that is, they require an equal quantity of heat for raising their temperature by 1°. We shall afterwards consider the specific heat of different substances more fully in Chap. XIV.

Oxygen, like the majority of difficultly-liquefiable gases, is but slightly soluble in water and other liquids. The solubility is given in Note 30, Chap. I. From this it is evident that water standing in air must absorb—i.e. dissolve—oxygen. This oxygen serves for the respiration of fishes. Fishes cannot exist in boiled water, because it does not contain the oxygen necessary for their respiration (see Chap. I.)

[22] Certain substances (with which we shall afterwards become acquainted), however, ignite spontaneously in air; for example, impure phosphuretted hydrogen, silicon hydride, zinc ethyl, and pyrophorus (very finely divided iron, &c.)

[23] If so little heat is evolved that the adjacent parts are not heated to the temperature of combustion, then combustion will cease.

[24] The phosphorus must be dry; it is usually kept in water, as it oxidises in air. It should be cut under water, as otherwise the freshly-cut surface oxidises. It must be dried carefully and quickly by wrapping it in blotting-paper. If damp, it splutters on burning. A small piece should be taken, as otherwise the iron spoon will melt. In this and the other experiments on combustion, water should be poured over the bottom of the vessel containing the oxygen, to prevent it from cracking. The cork closing the vessel should not fit tightly, in order to allow for the expansion of the gas due to the heat of the combustion.

[25] An iron cup will melt with sodium in oxygen.

[26] In order to rapidly heat the lime crucible containing the sodium, it is heated in the flame of a blowpipe described in Chap. VIII.

[27] In order to burn a watch spring, a piece of tinder (or paper soaked in a solution of nitre, and dried) is attached to one end. The tinder is lighted, and the spring is then plunged into the oxygen. The burning tinder heats the end of the spring, the heated part burns, and in so doing heats the further portions of the spring, which then burns completely if sufficient oxygen be present.

[28] The sparks of rust are produced, owing to the fact that the volume of the oxide of iron is nearly twice that of the volume of the iron, and as the heat evolved is not sufficient to entirely melt the oxide or the iron, the particles must be torn off and fly about. Similar sparks are formed in the combustion of iron, in other cases also. We saw the combustion of iron filings in the Introduction. In the welding of iron small iron splinters fly off in all directions and burn in the air, as is seen from the fact that whilst flying through the air they remain red hot, and also because, on cooling, they are seen to be no longer iron, but a compound of it with oxygen. The same thing takes place when the hammer of a gun strikes against the flint. Small scales of steel are heated by the friction, and glow and burn in the air. The combustion of iron is still better seen by taking it as a very fine powder, such as is obtained by the decomposition of certain of its compounds—for instance, by heating Prussian blue, or by the reduction of its compounds with oxygen by hydrogen; when this fine powder is strewn in air, it burns by itself, even without being previously heated (it forms a pyrophorus). This obviously depends on the fact that the powder of iron presents a larger surface of contact with air than an equal weight in a compact form.

[29] The experiment may be conducted without the wires, if the hydrogen be lighted in the orifice of an inverted cylinder, and at the same time the cylinder be brought over the end of a gas-conducting tube connected with a gas-holder containing oxygen. Thomsen's method may be adopted for a lecture experiment. Two glass tubes, with platinum ends, are passed through orifices, about 1–1½ centimetre apart, in a cork. One tube is connected with a gas-holder containing oxygen, and the other with a gas-holder full of hydrogen. Having turned on the gases, the hydrogen is lighted, and a common lamp glass, tapering towards the top, is placed over the cork. The hydrogen continues to burn inside the lamp glass, at the expense of the oxygen. If the current of oxygen be then decreased little by little, a point is reached when, owing to the insufficient supply of oxygen, the flame of the hydrogen increases in size, disappears for several moments, and then reappears at the tube supplying the oxygen. If the flow of oxygen be again increased, the flame reappears at the hydrogen tube. Thus the flame may be made to appear at one or the other tube at will, only the increase or decrease of the current of gas must take place by degrees and not suddenly. Further, air may be taken instead of oxygen, and ordinary coal-gas instead of hydrogen, and it will then be shown how air burns in an atmosphere of coal-gas, and it can easily be proved that the lamp glass is full of a gas combustible in air, because it may be lighted at the top.

[29 bis] In fact, instead of a spark a fine wire may be taken, and an electric current passed through it to bring it to a state of incandescence; in this case there will be no sparks, but the gases will inflame if the wire be fine enough to become red hot by the passage of the current.

[30] Now, a great many other different forms of apparatus, sometimes designed for special purposes, are employed in the laboratory for the investigation of gases. Detailed descriptions of the methods of gas analysis, and of the apparatus employed, must be looked for in works on analytical and applied chemistry.

[31] They must be sealed into the tube in such a manner as to leave no aperture between them and the glass. In order to test this, the eudiometer is filled with mercury, and its open end inverted into mercury. If there be the smallest orifice at the wires, the external air will enter into the cylinder and the mercury will fall, although not rapidly if the orifice be very fine.

[32]The eudiometer is used for determining the composition of combustible gases. A detailed account of gas analysis would be out of place in this work (see Note 30), but, as an example, we will give a short description of the determination of the composition of water by the eudiometer.

Pure and dry oxygen is first introduced into the eudiometer. When the eudiometer and the gas in it acquire the temperature of the surrounding atmosphere—which is recognised by the fact of the meniscus of the mercury not altering its position during a long period of time—then the heights at which the mercury stands in the eudiometer and in the bath are observed. The difference (in millimetres) gives the height of the column of mercury in the eudiometer. It must be reduced to the height at which the mercury would stand at 0° and deducted from the atmospheric pressure, in order to find the pressure under which the oxygen is measured (see Chap. I. Note 29). The height of the mercury also shows the volume of the oxygen. The temperature of the surrounding atmosphere and the height of the barometric column must also be observed, in order to know the temperature of the oxygen and the atmospheric pressure. When the volume of the oxygen has been measured, pure and dry hydrogen is introduced into the eudiometer, and the volume of the gases in the eudiometer again measured. They are then exploded. This is done by a Leyden jar, whose outer coating is connected by a chain with one wire, so that a spark passes when the other wire, fused into the eudiometer, is touched by the terminal of the jar. Or else an electrophorus is used, or, better still, a Ruhmkorff's coil, which has the advantage of working equally well in damp or dry air, whilst a Leyden jar or electrical machine does not act in damp weather. Further, it is necessary to close the lower orifice of the eudiometer before the explosion (for this purpose the eudiometer, which is fixed in a stand, is firmly pressed down from above on to a piece of india-rubber placed at the bottom of the bath), as otherwise the mercury and gas would be thrown out of the apparatus by the explosion. It must also be remarked that to ensure complete combustion the proportion between the volumes of oxygen and hydrogen must not exceed twelve of hydrogen to one volume of oxygen, or fifteen volumes of oxygen to one volume of hydrogen, because no explosion will take place if one of the gases be in great excess. It is best to take a mixture of one volume of hydrogen with several volumes of oxygen. The combustion will then be complete. It is evident that water is formed, and that the volume (or tension) is diminished, so that on opening the end of the eudiometer the mercury will rise in it. But the tension of the aqueous vapour is now added to the tension of the gas remaining after the explosion. This must be taken into account (Chap. I. Note 1). If but little gas remain, the water which is formed will be sufficient for its saturation with aqueous vapour. This may be learnt from the fact that drops of water are visible on the sides of the eudiometer after the mercury has risen in it. If there be none, a certain quantity of water must be introduced into the eudiometer. Then the number of millimetres expressing the pressure of the vapour corresponding with the temperature of the experiment must be subtracted from the atmospheric pressure at which the remaining gas is measured, otherwise the result will be inaccurate (Chap. I. Note 1).

This is essentially the method of the determination of the composition of water which was made for the first time by Gay-Lussac and Humboldt with sufficient accuracy. Their determinations led them to the conclusion that water consists of two volumes of hydrogen (more exactly 2·003, Le Duc 1892), and one volume of oxygen. Every time they took a greater quantity of oxygen, the gas remaining after the explosion was oxygen. When they took an excess of hydrogen, the remaining gas was hydrogen; and when the oxygen and hydrogen were taken in exactly the above proportion, neither one nor the other remained. The composition of water was thus definitely confirmed.

[33] Concerning this application of the eudiometer, see the chapter on Nitrogen. It may be mentioned as illustrating the various uses of the eudiometer that Prof. Timeraseeff employed microscopically small eudiometers to analyse the bubbles of gas given off from the leaves of plants.

[34] Thus ¼ volume of carbonic oxide, an equal volume of marsh gas, two volumes of hydrogen chloride or of ammonia, and six volumes of nitrogen or twelve volumes of air added to one volume of detonating gas, prevent its explosion.

[35] If the compression be brought about slowly, so that the heat evolved succeeds in passing to the surrounding space, then the combination of the oxygen and hydrogen does not take place, even when the mixture is compressed by 150 times; for the gases are not heated. If paper soaked with a solution of platinum (in aqua regia) and sal ammoniac be burnt, then the ash obtained contains very finely-divided platinum, and in this form it is best fitted for igniting hydrogen and detonating gas. Platinum wire requires to be heated, but platinum in so finely divided a state as it occurs in this ash inflames hydrogen, even at -20°. Many other metals, such as palladium (175°), iridium, and gold, act with a slight rise of temperature, like platinum; but mercury, at its boiling point, does not inflame detonating gas, although the slow formation of water then begins at 305°. All data of this kind show that the explosion of detonating gas presents one of the many cases of contact phenomena. This conclusion is further confirmed by the researches of V. Meyer (1892). He showed that only a very slow formation of steam begins at 448°, and that it only proceeds more rapidly at 518°. The temperature of the explosion of detonating gas, according to the same author, varies according as to whether the explosion is produced in open vessels or in closed tubes. In the first case the temperature of explosion lies between 530°–606°, and in the second between 630°–730°. In general it may be remarked that the temperature of explosion of gaseous mixtures is always lower in closed vessels than when the detonating mixture flows freely through tubes. According to Freyer and V. Meyer, the following gases when mixed with the requisite amount of oxygen explode at the following temperatures:

The velocity of the transmission of explosion in gaseous mixtures is as characteristic a quantity for gaseous systems as the velocity of the transmission of sound. Berthelot showed that this velocity depends neither upon the pressure nor upon the size of the tubes in which the gaseous mixture is contained, nor upon the material out of which the tube is made. Dixon (1891) determined the magnitude of these velocities for various mixtures, and his results proved very near to those previously given by Berthelot. For comparison we give the velocities expressed in metres per second:

The addition of oxygen to detonating gas lowers the velocity of the transmission of explosion almost as much as the introduction of nitrogen. An excess of hydrogen on the contrary raises the velocity of transmission. It is remarked that the explosion of mixtures of oxygen with marsh gas, ethylene and cyanogen is transmitted more quickly if the oxygen be taken in such a proportion that the carbon should burn to oxide of carbon, i.e. the velocity of the explosion is less if the oxygen be taken in sufficient quantity to form carbonic anhydride. Observations upon liquid and solid explosives (Berthelot) show that in this case the velocity of transmission of explosion is dependent upon the material of the tube. Thus the explosion of liquid nitro-methyl ether in glass tubes travels at the rate (in dependence upon the diam., from 1 mm.–45 mm.) of from 1,890 to 2,482 metres, and in tubes of Britannia metal (3 mm. in diam) at the rate of 1,230 metres. The harder the tube the greater the velocity of transmission of explosion. The following are the velocities for certain bodies:

In conclusion we may add that Mallard and Le Chatelier (1882) observed that in the explosion of a mixture of 1 volume of detonating gas with n volumes of an inert gas, the pressure is approximately equal to 9·2 - 0·9n atmospheres.

[36] From the very commencement of the promulgation of the idea of dissociation, it might have been imagined that reversible reactions of combination (the formation of H₂ and O belongs to this number) commence at the same temperature as that at which dissociation begins. And in many cases this is so, but not always, as may be seen from the facts (1) that at 450–560°, when detonating gas explodes, the density of aqueous vapour not only does not vary (and it hardly varies at higher temperatures, probably because the amount of the products of dissociation is small), but there are not, as far as is yet known, any traces of dissociation; (2) that under the influence of contact the temperature at which combination takes place falls even to the ordinary temperature, when water and similar compounds naturally are not dissociated and, judging from the data communicated by D. P. Konovaloff (Introduction, Note 39) and others, it is impossible to escape the phenomena of contact; all vessels, whether of metal or glass, show the same influence as spongy platinum, although to a much less degree. The phenomena of contact, judging from a review of the data referring to it, must be especially sensitive in reactions which are powerfully exothermal, and the explosion of detonating gas is of this kind.

[37]

Fig. 33.—Favre and Silbermann's calorimeter for determining the heat evolved in combustion.

The amount of heat evolved in the combustion of a known weight (for instance, 1 gram) of a given substance is determined by the rise in temperature of water, to which the whole of the heat evolved in the combustion is transmitted. A calorimeter, for example that shown in fig. 33, is employed for this purpose. It consists of a thin (in order that it may absorb less heat), polished (that it should transmit a minimum of heat) metallic vessel, surrounded by down (c), or some other bad conductor of heat, and an outer metallic vessel. This is necessary in order that the least possible amount of heat should be lost from the vessels; nevertheless, there is always a certain loss, whose magnitude is determined by preliminary experiment (by taking warm water, and determining its fall in temperature after a definite period of time) as a correction for the results of observations. The water to which the heat of the burning substance is transmitted is poured into the vessel. The stirrer g allows of all the layers of water being brought to the same temperature, and the thermometer serves for the determination of the temperature of the water. The heat evolved passes, naturally, not to the water only, but to all the parts of the apparatus. The quantity of water corresponding to the whole amount of those objects (the vessels, tubes, &c.) to which the heat is transmitted is previously determined, and in this manner another most important correction is made in the calorimetric determinations. The combustion itself is carried on in the vessel a. The ignited substance is introduced through the tube at the top, which closes tightly. In fig. 33 the apparatus is arranged for the combustion of a gas, introduced by a tube. The oxygen required for the combustion is led into a by the tube e, and the products of combustion either remain in the vessel a (if liquid or solid), or escape by the tube f into an apparatus in which their quantity and properties can easily be determined. Thus the heat evolved in combustion passes to the walls of the vessel a, and to the gases which are formed in it, and these transmit it to the water of the calorimeter.

[38] This quantity of heat corresponds with the formation of liquid water at the ordinary temperature from detonating gas at the same temperature. If the water be as vapour the heat evolved = 58 major calories; if as ice = 70·4 major calories. A portion of this heat is due to the fact that 2 vols. of hydrogen and 1 vol. of oxygen give 2 vols. of aqueous vapour—that is to say, contraction ensues—and this evolves heat. This quantity of heat may be calculated, but it cannot be said how much is expended in the separation of the atoms of oxygen from each other, and, therefore, strictly speaking, we do not know the quantity of heat which is evolved in the reaction alone, although the number of units of heat evolved in the combustion of detonating gas is accurately known.

The construction of the calorimeter and even the method of determination vary considerably in different cases. Since the beginning of the nineties, a large number of determinations of the heat of combustion have been conducted in closed bombs containing compressed oxygen. The greatest number of calorimetric determinations were made by Berthelot and Thomsen. They are given in their works Essai de mécanique chimique fondée sur la thermochimie, by M. Berthelot, 1879 (2 vols.), and thermochemische Untersuchungen, by J. Thomsen, 1886 (4 vols.) The most important methods of recent thermochemistry, and all the trustworthy results of experiment, are given in Prof. P. F. Louginin's Description of the Different Modes of Determining the Heat of Combustion of Organic Compounds, Moscow, 1894. The student must refer to works on theoretical and physical chemistry for a description of the elements and methods of thermochemistry, into the details of which it is impossible to enter in this work. One of the originators of thermochemistry, Hess, was a member of the St. Petersburg Academy of Sciences. Since 1870 a large amount of research has been carried out in this province of chemistry, especially in France and Germany, after the investigations of the French Academician, Berthelot, and Professor Thomsen, of Copenhagen. Among Russians, Beketoff, Louginin, Cheltzoff, Chroustchoff, and others are known by their thermochemical researches. The present epoch of thermochemistry must be considered rather as a collective one, wherein the material of facts is amassed, and the first consequences arising from them are noticed. In my opinion two essential circumstances prevent the possibility of deducing any exact consequences, of importance to chemical mechanics, from the immense store of thermochemical data already collected: (1) The majority of the determinations are conducted in weak aqueous solutions, and, the heat of solution being known, are referred to the substances in solution; yet there is much (Chapter I.) which leads to the conclusion that in solution water does not play the simple part of a diluting medium, but of itself acts independently in a chemical sense on the substance dissolved. (2) Physical and mechanical changes (decrease of volume, diffusion, and others) invariably proceed side by side with chemical changes, and for the present it is impossible, in a number of cases, to distinguish the thermal effect of the one and the other kind of change. It is evident that the one kind of change (chemical) is essentially inseparable and incomprehensible without the other (mechanical and physical); and therefore it seems to me that thermochemical data will only acquire their true meaning when the connection between the phenomena of both kinds (on the one hand chemical and atomic, and on the other hand mechanical and molecular or between entire masses) is explained more clearly and fully than is at present the case. As there is no doubt that the simple mechanical contact, or the action of heat alone, on substances sometimes causes an evident and always a latent (incipient) chemical change—that is, a different distribution or motion of the atoms in the molecules—it follows that purely chemical phenomena are inseparable from physical and mechanical phenomena. A mechanical change may be imagined without a physical change, and a physical without a chemical change, but it is impossible to imagine a chemical change without a physical and mechanical one, for without the latter we should not be able to recognise the former, and it is by their means that we are enabled to do so.

[39] The flame, or locality where the combustion of gases and vapours takes place, is a complex phenomenon, ‘an entire factory,’ as Faraday says, and therefore we will consider flame in some detail in one of the following notes.

[40] If 34,500 units of heat are evolved in the combustion of 1 part of hydrogen, and this heat is transmitted to the resulting 9 parts by weight of aqueous vapour, then we find that, taking the specific heat of the latter as 0·475, each unit of heat raises the temperature of 1 part by weight of aqueous vapour 2°·1 and 9 parts by weight (2·1 ÷ 9) O°·23; hence the 34,500 units of heat raise its temperature 7,935°. If detonating gas is converted into water in a closed space, then the aqueous vapour formed cannot expand, and therefore, in calculating the temperature of combustion, the specific heat at a constant volume must be taken into consideration; for aqueous vapour it is 0·36. This figure gives a still higher temperature for the flame. In reality it is much lower, but the results given by different observers are very contradictory (from 1,700° to 2,400°), the discrepancies depending on the fact that flames of different sizes are cooled by radiation to a different degree, but mainly on the fact that the methods and apparatus (pyrometers) for the determination of high temperatures, although they enable relative changes of temperature to be judged, are of little use for determining their absolute magnitude. By taking the temperature of the flame of detonating gas as 2,000°, I give, I think, the average of the most trustworthy determinations and calculations based upon the determination of the variation of the specific heat of aqueous vapour and other gases (see Chapter XLI.)

[41] It is evident that not only hydrogen, but every other combustible gas, will give an explosive mixture with oxygen. For this reason coal-gas mixed with air explodes when the mixture is ignited. The pressure obtained in the explosions serves as the motive power of gas engines. In this case advantage is taken, not only of the pressure produced by the explosion, but also of that contraction which takes place after the explosion. On this is based the construction of several motors, of which Lenoir's was formerly, and Otto's is now, the best known. The explosion is usually produced by coal-gas and air, but of late the vapours of combustible liquids (kerosene, benzene) are also being employed in place of gas (Chapter IX.) In Lenoir's engine a mixture of coal-gas and air is ignited by means of sparks from a Ruhmkorff's coil, but in the most recent machines the gases are ignited by the direct action of a gas jet, or by contact with the hot walls of a side tube.

[41 bis] Let us consider as an example the combustion of sulphur in air and in oxygen. If 1 gram of sulphur burns in air or oxygen it evolves in either case 2250 units of heat—i.e. evolves sufficient heat for heating 2,250 grams of water 1° C. This heat is first of all transmitted to the sulphurous anhydride, SO₂, formed by the combination of sulphur with oxygen. In its combustion 1 gram of sulphur forms 2 grams of sulphurous anhydride—i.e. the sulphur combines with 1 gram of oxygen. In order that 1 gram of sulphur should have access to 1 gram of oxygen in air, it is necessary that 3·4 grams of nitrogen should simultaneously reach the sulphur, because air contains seventy-seven parts of nitrogen (by weight) per twenty-three parts of oxygen. Thus in the combustion of 1 gram of sulphur, the 2,250 units of heat are transmitted to 2 grams of sulphurous oxide and to at least 3·4 grams of nitrogen. As 0·155 unit of heat is required to raise 1 gram of sulphurous anhydride 1° C., therefore 2 grams require 0·31 unit. So also 3·4 grams of nitrogen require 3·4 × 0·244 or 0·83 unit of heat, and therefore in order to raise both gases 1° C. 0·31 + 0·83 or 1·14 unit of heat is required; but as the combustion of the sulphur evolves 2,250 units of heat, therefore the gases might be heated (if their specific heats remained constant) to 2250 / 1·14 or 1,974° C. That is, the maximum possible temperature of the flame of the sulphur burning in air will be 1,974° C. In the combustion of the sulphur in oxygen the heat evolved (2,250 units) can only pass to the 2 grams of sulphurous anhydride, and therefore the highest possible temperature of the flame of the sulphur in oxygen will be = 2250 / 0·31 or 7258°. In the same manner it may be calculated that the temperature of charcoal burning in air cannot exceed 2,700°, while in oxygen it may attain 10,100° C. For this reason the temperature in oxygen will always be higher than in air, although (judging from what has been said respecting detonating gas) neither one temperature nor the other will ever approximate to the theoretical amount.

[42] Faraday proved this by a very convincing experiment on a candle flame. If one arm of a bent glass tube be placed in a candle flame above the wick in the dark portion of the flame, then the products of the partial combustion of the stearin will pass up the tube, condense in the other arm, and collect in a flask placed under it (fig. 35) as heavy white fumes which burn when lighted. If the tube be raised into the upper luminous portion of the flame, then a dense black smoke which will not inflame accumulates in the flask. Lastly, if the tube be let down until it touches the wick, then little but stearic acid condenses in the flask.

[43] All transparent substances which transmit light with great ease (that is, which absorb but little light) are but little luminous when heated; so also substances which absorb but few heat rays, when heated transmit few rays of heat.

[44] There is, however, no doubt but that very heavy dense vapours or gases under pressure (according to the experiments of Frankland) are luminous when heated, because, as they become denser they approach a liquid or solid state. Thus detonating gas when exploded under pressure gives a brilliant light.

[45] If hydrogen gas be passed through a volatile liquid hydrocarbon—for instance, through benzene (the benzene may be poured directly into the vessel in which hydrogen is generated)—then its vapour burns with the hydrogen and gives a very bright flame, because the resultant particles of carbon (soot) become incandescent. Benzene, or platinum gauze, introduced into a hydrogen flame may be employed for illuminating purposes.

[46] In flames the separate parts may be distinguished with more or less distinctness. That portion of the flame whither the combustible vapours or gases flow, is not luminous because its temperature is still too low for the process of combustion to take place in it. This is the space which in a candle surrounds the wick, or in a gas jet is immediately above the orifice from which the gas escapes. In a candle the combustible vapours and gases which are formed by the action of heat on the melted tallow or stearin rise in the wick, and are heated by the high temperature of the flame. By the action of the heat, the solid or liquid substance is here, as in other cases, decomposed, forming products of dry distillation. These products occur in the central portion of the flame of a candle. The air travels to it from the outside, and is not able to intermix at once with the vapours and gases in all parts of the flame equally; consequently, in the outer portion of the flame the amount of oxygen will be greater than in the interior portions. But, owing to diffusion, the oxygen, of course mixed with nitrogen, flowing towards the combustible substance, does finally penetrate to the interior of the flame (when the combustion takes place in ordinary air). The combustible vapours and gases combine with this oxygen, evolve a considerable amount of heat, and bring about that state of incandescence which is so necessary both for keeping up the combustion and also for the uses to which the flame is applied. Passing from the colder envelope of air through the interior of the flame, to the source of the combustible vapours (for instance, the wick), we evidently first traverse layers of higher and higher temperature, and then portions which are less and less hot, in which the combustion is less complete, owing to the limited supply of oxygen.

Fig. 36.—In the candle flame the portion C contains the vapours and products of decomposition; in the bright zone A the combustion has commenced, and particles of carbon are emitted; and in the pale zone B the combustion is completed.

Thus unburnt products of the decomposition of organic substances occur in the interior of the flame. But there is always free hydrogen in the interior of the flame, even when oxygen is introduced there, or when a mixture of hydrogen and oxygen burns, because the temperature evolved in the combustion of hydrogen or the carbon of organic matter is so high that the products of combustion are themselves partially decomposed—that is, dissociated—at this temperature. Hence, in a flame a portion of the hydrogen and of the oxygen which might combine with the combustible substances must always be present in a free state. If a hydrocarbon burns, and we imagine that a portion of the hydrogen is in a free state, then a portion of the carbon must also occur in the same form in the flame, because, other conditions being unchanged, carbon burns after hydrogen, and this is actually observed in the combustion of various hydrocarbons. Charcoal, or the soot of a common flame, arises from the dissociation of organic substances contained in the flame. The majority of hydrocarbons, especially those containing much carbon—for instance, naphthalene—burn, even in oxygen, with separation of soot. In that portion of the flame where the hydrogen burns the carbon remains unburnt, or at least partly so. It is this free carbon which causes the brilliancy of the flame. That the interior of the flame contains a mixture which is still capable of combustion may be proved by the following experiment: A portion of the gases may be withdrawn by an aspirator from the central portion of the flame of carbonic oxide, which is combustible in air. For this purpose Deville passed water through a metallic tube having a fine lateral orifice, which is placed in the flame. As the water flows along the tube portions of the gases of the flame enter, and, passing along the tube alternately with cylinders of water, are carried away into an apparatus where they can be investigated. It appears that all portions of the flame obtained by the combustion of a mixture of carbonic oxide and oxygen contain a portion of this mixture still unburnt. The researches of Deville and Bunsen showed that in the explosion of a mixture of hydrogen and of carbonic oxide with oxygen in a closed space, complete combustion does not ever take place immediately. If two volumes of hydrogen and one volume of oxygen be confined in a closed space, then on explosion the pressure does not attain that magnitude which it would were there immediate and complete combustion. It may be calculated that the pressure should attain twenty-six atmospheres. In reality, it does not exceed nine and a half atmospheres.

Hence the admixture of the products of combustion with an explosive mixture prevents the combustion of the remaining mass, although capable of burning. The admixture of carbonic anhydride prevents carbonic oxide from burning. The presence of any other foreign gas interferes in the same manner. This shows that every portion of a flame must contain combustible, burning, and already burnt substances—i.e. oxygen, carbon, carbonic oxide, hydrogen, hydrocarbons, carbonic anhydride, and water. Consequently, it is impossible to attain instantaneous complete combustion, and this is one of the reasons of the phenomenon of flame. A certain space is required, and the temperature must be unequal in different parts of it. In this space different quantities of the component parts are successively subjected to combustion, or are cooled under the influence of adjacent objects, and combustion only ends where the flame ends. If the combustion could be concentrated at one spot, then the temperature would be incomparably higher than it is under the actual circumstances.

The various regions of the flame have formed the frequent subject of experimental research, and the experiments conducted by Smithells and Ingle (1892) are particularly instructive; they show that the reducing (interior) and oxidising (exterior) portions of the flame of a burning gas may be divided by taking a Bunsen burner and surrounding the flame of the gas burnt in it, by another wider tube (without the access of air to the annular space or allowing only a small current of air to pass), when a gaseous mixture, containing oxide of carbon and capable of further combustion, will issue from this enveloping tube, so that a second flame, corresponding to the exterior (oxidising) portion of an ordinary flame, may be obtained above the enveloping tube. This division of the flame into two portions is particularly clear when cyanogen C₂N₂ is burnt, because the interior portion (where CO is chiefly formed according to the equation C₂N₂ + O₂ = 2CO + N₂, but a portion of the nitrogen is oxidised) is of a rose colour, while the exterior portion (where the CO burns into CO₂ at the expense of a fresh quantity of oxygen and of the oxides of nitrogen proceeding from the interior portions) is of a bluish-grey colour.

[47] Cotton waste (used in factories for cleaning machines from lubricating oil) soaked in oil and lying in heaps is self-combustible, being oxidised by the air.

[48] When it is desired to preserve a supply of vegetable and animal food, the access of the oxygen of the atmosphere (and also of the germs of organisms present in the air) is often prevented. With this object articles of food are often kept in hermetically closed vessels, from which the air has been withdrawn; vegetables are dried and soldered up while hot in tin boxes; sardines are immersed in oil, &c. The removal of water from substances is also sometimes resorted to with the same object (the drying of hay, corn, fruits), as also is saturation with substances which absorb oxygen (such as sulphurous anhydride), or which hinder the growth of organisms forming the first cause of putrefaction, as in processes of smoking, embalming, and in the keeping of fishes and other animal specimens in spirit, &c.

[49] It must be remarked that certain elements form oxides of all three kinds—i.e. indifferent, basic, and acid; for example, manganese forms manganous oxide, manganic oxide, peroxide of manganese, red oxide of manganese, and manganic anhydride, although some of them are not known in a free state but only in combination. The basic oxides contain less oxygen than the peroxides, and the peroxides less than the acid anhydrides. Thus they must be placed in the following general normal order with respect to the amount of oxygen entering into their composition—(1) basic oxides, suboxides, and oxides; (2) peroxides; (3) acid anhydrides. The majority of elements, however, do not give all three kinds of oxides, some giving only one degree of oxidation. It must further be remarked that there are oxides formed by the combination of acid anhydrides with basic oxides, or, in general, of oxides with oxides. For every oxide having a higher and a lower degree of oxidation, it might be said that the intermediate oxide was formed by the combination of the higher with the lower oxide. But this is not true in all cases—for instance, when the oxide under consideration forms a whole series of independent compounds—for oxides which are really formed by the combination of two other oxides do not give such independent compounds, but in many cases decompose into the higher and lower oxides.

[50] Blotting or unsized paper, soaked in a solution of litmus, is usually employed for detecting the presence of acids. This paper is cut into strips, and is called test paper; when dipped into acid it immediately turns red. This is a most sensitive reaction, and may be employed for testing for the smallest traces of acids. If 10,000 parts by weight of water be mixed with 1 part of sulphuric acid, the coloration is distinct, and it is even perceptible on the addition of ten times more water. Certain precautions must, however, be taken in the preparation of such very sensitive litmus paper. Litmus is sold in lumps. Take, say, 100 grams of it; powder it, and add it to cold pure water in a flask; shake and decant the water. Repeat this three times. This is done to wash away easily-soluble impurities, especially alkalis. Transfer the washed litmus (it is washed with absolute alcohol to remove the non-sensitive reddish colouring matter) to a flask, and pour in 600 c.c. of water, heat, and allow the hot infusion to remain for some hours in a warm place. Then filter, and divide the filtrate into two parts. Add a few drops of nitric acid to one portion, so that a faint red tinge is obtained, and then mix the two portions. Add spirit to the mixture, and keep it in a stoppered bottle (it soon spoils if left open to the air). This infusion may be employed directly; it reddens in the presence of acids, and turns blue in the presence of alkalis. If evaporated, a solid mass is obtained which is soluble in water, and may be kept unchanged for any length of time. The test paper may be prepared as follows:—Take a strong infusion of litmus, and soak blotting-paper with it; dry it, and cut it into strips, and use it as test-paper for acids. For the detection of alkalis, the paper must be soaked in a solution of litmus just reddened by a few drops of acid; if too much acid be taken, the paper will not be sensitive. Such acids as sulphuric acid colour litmus, and especially its infusion, a brick-red colour, whilst more feeble acids, such as carbonic, give a faint red-wine tinge. Test-paper of a yellow colour is also employed; it is dyed by an infusion of turmeric roots in spirit. In alkalis it turns brown, but regains its original hue in acids. Many blue and other vegetable colouring matters may be used for the detection of acids and alkalis; for example, infusions of cochineal, violets, log-wood, &c. Certain artificially prepared substances and dyes may also be employed. Thus rosolic acid, C₂₀H₁₆O₃ and phenolphthaleïn, C₂₀H₁₄O₄ (it is used in an alcoholic solution, and is not suitable for the detection of ammonia), are colourless in an acid, and red in an alkaline, solution. Cyanine is also colourless in the presence of acids, and gives a blue coloration with alkalis. Methyl-orange (yellow in an aqueous solution) is not altered by alkalis but becomes pink with acids (weak acids have no action), &c. These are very sensitive tests. Their behaviour in respect to various acids, alkalis, and salts sometimes give the means of distinguishing substances from each other.

[51] That water really is separated in the reaction of acid on alkaline hydrates, may be shown by taking some other intermediate hydrate—for example, alumina—instead of water. Thus, if a solution of alumina in sulphuric acid be taken, it will have, like the acid, an acid reaction, and will therefore colour litmus red. If, on the other hand, a solution of alumina in an alkali—say, potash—be taken, it will have an alkaline reaction, and will turn red litmus blue. On adding the alkaline to the acid solution until neither an alkaline nor an acid reaction is produced, a salt is formed, consisting of sulphuric anhydride and potassium oxide. In this, as in the reaction of hydrates, an intermediate oxide is separated out—namely, alumina. Its separation will be very evident in this case, as alumina is insoluble in water.

[52] The mutual interaction of hydrates, and their capacity of forming salts, may be taken advantage of for determining the character of those hydrates which are insoluble in water. Let us imagine that a given hydrate, whose chemical character is unknown, is insoluble in water. It is therefore impossible to test its reaction on litmus. It is then mixed with water, and an acid—for instance, sulphuric acid—is added to the mixture. If the hydrate taken be basic, reaction will take place, either directly or by the aid of heat, with the formation of a salt. In certain cases, the resultant salt is soluble in water, and this will at once show that combination has taken place between the insoluble basic hydrate and the acid, with the formation of a soluble saline substance. In those cases where the resultant salt is insoluble, still the water loses its acid reaction, and therefore it may he ascertained, by the addition of an acid, whether a given hydrate has a basic character, like the hydrates of oxide of copper, lead, &c. If the acid does not act on the given insoluble hydrate (at any temperature), then it has not a basic character, and it should be tested as to whether it has an acid character. This is done by taking an alkali, instead of the acid, and by observing whether the unknown hydrate then dissolves, or whether the alkaline reaction disappears. Thus it may he proved that hydrate of silica is acid, because it dissolves in alkalis and not in acids. If it be a case of an insoluble intermediate hydrate, then it will be observed to react on both the acid and alkali. Hydrate of alumina is an instance in question, which is soluble both in caustic potash and in sulphuric acid.

The degree of affinity or chemical energy proper to oxides and their hydrates is very dissimilar; some extreme members of the series possess it to a great extent. When acting on each other they evolve a large quantity of heat, and when acting on intermediate hydrates they also evolve heat to a considerable degree, as we saw in the combination of lime and sulphuric anhydride with water. When extreme oxides combine they form stable salts, which are decomposed with difficulty, and often show characteristic properties. The compounds of the intermediate oxides with each other, or even with basic and acid oxides, present a very different case. However much alumina we may dissolve in sulphuric acid, we cannot saturate the acid properties of the sulphuric acid, the resulting solution will always have an acid reaction. So also, whatever quantity of alumina is dissolved in an alkali, the resulting solution will always present an alkaline reaction.

[53] In order to give an idea of the quantity of heat evolved in the formation of salts I append a table of data for very dilute aqueous solutions of acids and alkalis, according to the determinations of Berthelot and Thomsen. The figures are given in major calories—that is, in thousands of units of heat. For example, 49 grams of sulphuric acid, H₂SO₄, taken in a dilute aqueous solution, when mixed with such an amount of a weak solution of caustic soda, NaHO, that a neutral salt is formed (when all the hydrogen of the acid is replaced by the sodium), evolves 15,800 units of heat.

These figures cannot be considered as the heat of neutralisation, because the water here plays an important part. Thus, for instance, sulphuric acid and caustic soda in dissolving in water evolve very much heat, and the resultant sodium sulphate very little; consequently, the amount of heat evolved in an anhydrous combination will be different from that evolved in a hydrated combination. Those acids which are not energetic in combining with the same quantity of alkalis required for the formation of normal salts of sulphuric or nitric acids always, however, give less heat. For instance, with caustic soda: carbonic acid gives 10·2, hydrocyanic, 2·9, hydrogen sulphide, 3·9 major calories. And as feeble bases (for example, Fe₂O₃) also evolve less heat than those which are more powerful, so a certain general correlation between thermochemical data and the degree of affinity shows itself here, as in other cases (see Chapter II., Note 7); this does not, however, give any reason for measuring the affinity which binds the elements of salts by the heat of their formation in dilute solutions. This is very clearly demonstrated by the fact that water is able to decompose many salts, and is separated in their formation.

[54] Carbonic anhydride evolves heat in dissolving in water. The solution easily dissociates and evolves carbonic anhydride, according to the law of Henry and Dalton (see Chapter I.) In dissolving in caustic soda, it either gives a normal salt, Na₂CO₃, which does not evolve carbonic anhydride, or an acid salt, NaHCO₃ which easily evolves carbonic anhydride when heated. The same gas, when dissolved in solutions of salts, acts in one or the other manner (see Chapter II., Note 38). Here it is seen what a successive series of relations exists between compounds of a different order, between substances of different degrees of stability. By making a distinction between the phenomena of solutions and chemical compounds, we overlook those natural transitions which in reality exist.

[55] This kind of decomposition may be easily observed by pouring a solution of sodium sulphate into a U-shaped tube and inserting electrodes in the two branches. If the solution be coloured with an infusion of litmus, it will easily be seen that it turns blue at the cathode, owing to the formation of sodium hydroxide, and red at the electro-positive pole, from the formation of sulphuric acid.

[56] In other cases the decomposition of salts by the electric current may be accompanied by much more complex results. Thus, when the metal of the salt is capable of a higher degree of oxidation, such a higher oxide may be formed at the positive pole by the oxygen which is evolved there. This takes place, for instance, in the decomposition of salts of silver and manganese by the galvanic current, peroxides of these metals being formed. Thus in the electrolysis of a solution of KCl, KClO₃ is formed, and of sulphuric acid (corresponding to SO₃) persulphuric acid, corresponding to S₂O₇. But all the phenomena as yet known may be expressed by the above law—that the current decomposes salts into metals, which appear at the negative pole, and into the remaining component parts, which appear at the positive pole.

[57] The above-enunciated generalisation of the conception of salts as compounds of the metals (simple, or compound like ammonium, NH₄), with the haloids (simple, like chlorine, or compound, like cyanogen, CN, or the radical of sulphuric acid, SO₄), capable of entering into double saline decomposition, which is in accordance with the general data respecting salts, was only formed little by little after a succession of most varied propositions as to the chemical structure of salts.

Salts belong to the class of substances which have been known since very early times, and have long been investigated in many directions. At first, however, no distinction was made between salts, acids, and bases. Glauber prepared many artificial salts during the latter half of the seventeenth century. Up to that time the majority of salts were obtained from natural sources, and that salt which we have referred to several times—namely, sodium sulphate—was named Glauber's salt after this chemist. Rouelle distinguished normal, acid, and basic salts, and showed their action on vegetable dyes, still he confounded many salts with acids (even now every acid salt ought to be regarded as an acid, because it contains hydrogen, which may be replaced by metals—that is, it is the hydrogen of an acid). Baumé disputed Rouelle's opinion concerning the subdivision of salts, contending that normal salts only are true salts, and that basic salts are simple mixtures of normal salts with bases and acid salts with acids, considering that washing alone could remove the base or acid from them. Rouelle, in the middle of the last century, however, rendered a great service to the study of salts and the diffusion of knowledge respecting this class of compounds in his attractive lectures. He, like the majority of the chemists of that period, did not employ the balance in his researches, but satisfied himself with purely qualitative data. The first quantitative researches on salts were carried on about this time by Wenzel, who was the director of the Freiburg mines, in Saxony. Wenzel studied the double decomposition of salts, and observed that in the double decomposition of neutral salts a neutral salt was always obtained. He proved, by a method of weighing, that this is due to the fact that the saturation of a given quantity of a base requires such relative quantities of different acids as are capable of saturating every other base. Having taken two neutral salts—for example, sodium sulphate and calcium nitrate—let us mix their solutions together. Double decomposition takes place, because calcium sulphate is formed, which is almost insoluble. However much we might add of each of the salts, the neutral reaction will still be preserved, consequently the neutral character of the salts is not destroyed by the interchange of metals; that is to say, that quantity of sulphuric acid which saturated the sodium is sufficient for the saturation of the calcium, and that amount of nitric acid which saturated the calcium is enough to saturate the sodium contained in combination with sulphuric acid in sodium sulphate. Wenzel was even convinced that matter does not disappear in nature, and on this principle he corrects, in his Doctrine of Affinity, the results of his experiments when he found that he obtained less than he had originally taken. Although Wenzel deduced the law of the double decomposition of salts quite correctly, he did not determine those quantities in which acids and bases act on each other. This was carried out at the end of the last century by Richter. He determined the quantities by weight of the bases which saturate acids and of the acids which saturate bases, and obtained comparatively correct results, although his conclusions were not correct, for he states that the quantity of a base saturating a given acid varies in arithmetical progression, and the quantity of an acid saturating a given base in geometrical progression. Richter studied the deposition of metals from their salts by other metals, and observed that the neutral reaction of the solution is not destroyed by this exchange. He also determined the quantities by weight of the metals replacing one another in salts. He showed that copper displaces silver from its salt, and that zinc displaces copper and a whole series of other metals. Those quantities of metals which were capable of replacing one another were termed equivalents.

Richter's teaching found no followers, because, although he fully believed in the discoveries of Lavoisier, yet he still held to the phlogistic reasonings which rendered his expositions very obscure. The works of the Swedish savant Berzelius freed the facts discovered by Wenzel and Richter from the obscurity of former conceptions, and led to their being explained in accordance with Lavoisier's views, and in the sense of the law of multiple proportions which had already been discovered by Dalton. On applying to salts those conclusions which Berzelius arrived at by a whole series of researches of remarkable accuracy, we arrive at the following law of equivalents—one part by weight of hydrogen in an acid is replaced by the corresponding equivalent weight of any metal; and, therefore, when metals replace each other their weights are in the same ratio as their equivalents. Thus, for instance, one part by weight of hydrogen is replaced by 23 parts of sodium, 39 parts of potassium, 12 parts of magnesium, 20 parts of calcium, 28 parts of iron, 108 parts of silver, 33 parts of zinc, &c.; and, therefore, if zinc replaces silver, then 33 parts of zinc will take the place of 108 parts of silver, or 33 parts of zinc will he substituted by 23 parts of sodium, &c.

The doctrine of equivalents would be precise and simple did every metal only give one oxide or one salt. It is rendered complicated from the fact that many metals form several oxides, and consequently offer different equivalents in their different degrees of oxidation. For example, there are oxides containing iron in which its equivalent is 28—this is in the salts formed by the suboxide; and there is another series of salts in which the equivalent of iron equals 18⅔—which contain less iron, and consequently more oxygen, and correspond with a higher degree of oxidation—ferric oxide. It is true that the former salts are easily formed by the direct action of metallic iron on acids, and the latter only by a further oxidation of the compound formed already; but this is not always so. In the case of copper, mercury, and tin, under different circumstances, salts are formed which correspond with different degrees of oxidation of these metals, and many metals have two equivalents in their different salts—that is, in salts corresponding with the different degrees of oxidation. Thus it is impossible to endow every metal with one definite equivalent weight. Hence the conception of equivalents, while playing an important part from an historical point of view, appears, with a fuller study of chemistry, to be but subordinate to a higher conception, with which we shall afterwards become acquainted.

The fate of the theoretical views of chemistry was for a long time bound up with the history of salts. The clearest representation of this subject dates back to Lavoisier, and was systematically developed by Berzelius. This representation is called the binary theory. All compounds, and especially salts, are represented as consisting of two parts. Salts are represented as compounds of a basic oxide (a base) and an acid (that is, an anhydride of an acid, then termed an acid), whilst hydrates are represented as compounds of anhydrous oxides with water. Such an expression was employed not only to denote the most usual method of formation of these substances (where it would be quite true), but also to express that internal distribution of the elements by which it was proposed to explain all the properties of these substances. Copper sulphate was supposed to contain two most intimate component parts—copper oxide and sulphuric anhydride. This is an hypothesis. It arose from the so-called electro-chemical hypothesis, which supposed the two component parts to be held in mutual union, because one component (the anhydride of the acid) has electro-negative properties, and the other (the base in salts) electro-positive. The two parts are attracted together, like substances having opposite electrical charges. But as the decomposition of salts in a state of fusion by an electric current always gives a metal, that representation of the constitution and decomposition of salts called the hydrogen theory of acids is nearer the truth than that which considers salts as made up of a base and an anhydride of an acid. But the hydrogen theory of acids is also a binary hypothesis, and does not contradict the electro-chemical hypothesis, but is rather a modification of it. The binary theory dates from Rouelle and Lavoisier, the electro-chemical aspect was zealously developed by Berzelius, and the hydrogen theory of acids is due to Davy and Liebig.

These hypothetical views simplified and generalised the study of a complicated subject, and served to support further arguments, but when salts were in question it was equally convenient to follow one or the other of these hypotheses. But these theories were brought to bear on all other substances, on all compound substances. Those holding the binary and electro-chemical hypotheses searched for two anti-polar component parts, and endeavoured to express the process of chemical reactions by electro-chemical and similar differences. If zinc replaces hydrogen, they concluded that it is more electro-positive than hydrogen, whilst they forgot that hydrogen may, under different circumstances, displace zinc—for instance, at a red heat. Chlorine and oxygen were considered as being of opposite polarity to hydrogen because they easily combine with it, nevertheless both are capable of replacing hydrogen, and, what is very characteristic, in the replacement of hydrogen by chlorine in carbon compounds not only does the chemical character often remain unaltered, but even the external form may remain unchanged, as Laurent and Dumas demonstrated. These considerations undermine the binary, and more especially the electro-chemical theory. An explanation of known reactions then began to be sought for not in the difference of the polarity of the different substances, but in the joint influences of all the elements on the properties of the compound formed. This is the reverse of the preceding hypothesis.

This reversal was not, however, limited to the destruction of the tottering foundations of the preceding theory; it proposed a new doctrine, and laid the foundation for the modern course of our science. This doctrine may be termed the unitary theory—that is, it strictly acknowledges the joint influences of the elements in a compound substance, denies the existence of separate and contrary components in them, regards copper sulphate, for instance, as a strictly definite compound of copper, sulphur, and oxygen; then seeks for compounds which are analogous in their properties, and, placing them side by side, endeavours to express the influence of each element in determining the united properties of its compound. In the majority of cases it arrives at conclusions similar to those which are obtained by the above-mentioned hypotheses, but in certain special cases the conclusions of the unitary theory are in entire opposition to those of the binary theory and its corollaries. Cases of this kind are most often met with in the consideration of compounds of a more complex nature than salts, especially organic compounds containing hydrogen. But it is not in this change from an artificial to a natural system, important as it is, that the chief service and strength of the unitary doctrine lies. By a simple review of the vast store of data regarding the reactions of typical substances, it succeeded from its first appearance in establishing a new and important law, it introduced a new conception into science—namely, the conception of molecules, with which we shall soon become acquainted. The deduction of the law and of the conception of molecules has been verified by facts in a number of cases, and was the cause of the majority of chemists of our times deserting the binary theory and accepting the unitary theory, which forms the basis of the present work. Laurent and Gerhardt must be considered as the founders of this doctrine.

[1] This conclusion, deduced by me as far back as 1878 (Moniteur Scientifique) by conceiving the molecules of ozone (see later) as more complex than those of oxygen, and ozone as containing a greater quantity of heat than oxygen, has been proved experimentally by the researches of Mailfert (1880), who showed that the passage of a silent discharge through a litre of oxygen at 0° may form up to 14 milligrams of ozone, and at -30° up to 60 milligrams; but best of all in the determinations of Chappuis and Hautefeuille (1880), who found that at a temperature of -25° a silent discharge converted 20 p.c. of oxygen into ozone, whilst at 20° it was impossible to obtain more than 12 p.c., and at 100° less than 2 p.c. of ozone was obtained.

[2] A series of electric sparks may be obtained by an ordinary electrical machine, the electrophorus machines of Holtz and Teploff, &c., Leyden jars, Ruhmkorff coils, or similar means, when the opposite electricities are able to accumulate at the terminals of conductors, and a discharge of sufficient electrical intensity passes through the non-conductors air or oxygen.

[3] A silent discharge is such a combination of opposite statical (potential) electricities as takes place (generally between large surfaces) regularly, without sparks, slowly, and quietly (as in the dispersion of electricity). The discharge is only luminous in the dark; there is no observable rise of temperature, and therefore a larger amount of ozone is formed. But, nevertheless, on continuing the passage of a silent discharge through ozone it is destroyed. For the action to be observable a large surface is necessary, and consequently a source of electricity at a high potential. For this reason the silent discharge is best produced by a Ruhmkorff coil, as the most convenient means of obtaining a considerable potential of statical electricity with the employment of the comparatively feeble current of a galvanic battery.

[4] v. Babo's apparatus was one of the first constructed for ozonising oxygen by means of a silent discharge (and it is still one of the best). It is composed of a number (twenty and more) of long, thin capillary glass tubes closed at one end. A platinum wire, extending along their whole length, is introduced into the other end of each tube, and this end is then fused up round the wire, the end of which protrudes outside the tube. The protruding ends of the wires are arranged alternately in two sides in such a manner that on one side there are ten closed ends and ten wires. A bunch of such tubes (forty should make a bunch of not more than 1 c.m. diameter) is placed in a glass tube, and the ends of the wires are connected with two conductors, and are fused to the ends of the surrounding tube. The discharge of a Ruhmkorff coil is passed through these ends of the wires, and the dry air or oxygen to be ozonised is passed through the tube. If oxygen be passed through, ozone is obtained in large quantities, and free from oxides of nitrogen, which are partially formed when air is acted on. At low temperatures ozone is formed in large quantities. As ozone acts on corks and india-rubber, the apparatus should be made entirely of glass. With a powerful Ruhmkorff coil and forty tubes the ozonation is so powerful that the gas when passed through a solution of iodide of potassium not only sets the iodine free, but even oxidises it to potassium iodate, so that in five minutes the gas-conducting tube is choked up with crystals of the insoluble iodate.

[5] In order to connect the ozoniser with any other apparatus it is impossible to make use of india-rubber, mercury, or cements, &c., because they are themselves acted on by, and act on, ozone. All connections must, as was first proposed by Brodie, be hermetically closed by sulphuric acid, which is not acted on by ozone. Thus, a cork is passed over the vertical end of a tube, over which a wide tube passes so that the end of the first tube protrudes above the cork; mercury is first poured over the cork (to prevent its being acted on by the sulphuric acid), and then sulphuric acid is poured over the mercury. The protruding end of the first tube is covered by the lower end of a third tube immersed in the sulphuric acid.

[6] The method above described is the only one which has been well investigated. The admixture of nitrogen, or even of hydrogen, and especially of silicon fluoride, appears to aid the formation and preservation of ozone. Amongst other methods for preparing ozone we may mention the following: 1. In the action of oxygen on phosphorus at the ordinary temperature a portion of the oxygen is converted into ozone. At the ordinary temperature a stick of phosphorus, partially immersed in water and partially in air in a large glass vessel, causes the air to acquire the odour of ozone. It must further be remarked that if the air be left for long in contact with the phosphorus, or without the presence of water, the ozone formed is destroyed by the phosphorus. 2. By the action of sulphuric acid on peroxide of barium. If the latter be covered with strong sulphuric acid (the acid, if diluted with only one-tenth of water, does not give ozone), then at a low temperature the oxygen evolved contains ozone, and in much greater quantities than in that ozone is obtained by the action of electric sparks or phosphorus. 3. Ozone may also be obtained by decomposing strong sulphuric acid by potassium manganate especially with the addition of barium peroxide.

[7] Ozone takes up the hydrogen from hydrochloric acid; chlorine is liberated, and can dissolve gold. Iodine is directly oxidised by ozone, but not by oxygen. Ammonia, NH₃, is oxidised by ozone into ammonium nitrite (and nitrate), 2NH₃ + O₃ = NH₄NO₂ + H₂O, and therefore a drop of ammonia, on falling into the gas, gives a thick cloud of the salts formed. Ozone converts lead oxide into peroxide, and suboxide of thallium (which is colourless) into oxide (which is brown), so that this reaction is made use of for detecting the presence of ozone. Lead sulphide, PbS (black), is converted into sulphate, PbSO₄ (colourless), by ozone. A neutral solution of manganese sulphate gives a precipitate of manganese peroxide, and an acid solution may be oxidised into permanganic acid, HMnO₄. With respect to the oxidising action of ozone on organic substances, it may be mentioned that with ether, C₄H₁₀O, ozone gives ethyl peroxide, which is capable of decomposing with explosion (according to Berthelot), and is decomposed by water into alcohol, 2C₂H₆O, and hydrogen peroxide, H₂O₂.

[8] This reaction is the one usually made use of for detecting the presence of ozone. In the majority of cases paper is soaked in solutions of potassium iodide and starch. Such ozonometrical or iodised starch-paper when damp turns blue in the presence of ozone, and the tint obtained varies considerably, according to the length of time it is exposed and to the amount of ozone present. The amount of ozone in a given gas may even to a certain degree he judged by the shade of colour acquired by the paper, if preliminary tests be made.

Test-paper for ozone is prepared in the following manner:—One gram of neutral potassium iodide is dissolved in 100 grams of distilled water; 10 grams of starch are then shaken up in the solution, and the mixture is boiled until the starch is converted into a jelly. This jelly is then smeared over blotting-paper and left to dry. It must always he remembered, however, that the colour of iodised starch-paper is changed not only by the action of ozone, but of many other oxidisers; for example, by the oxides of nitrogen (especially N₂O₃) and hydrogen peroxide. Houzeau proposed soaking common litmus-paper with a solution of potassium iodide, which in the presence of iodine would turn blue, owing to the formation of KHO. In order to determine if the blue colour is not produced by an alkali (ammonia) in the gas, a portion of the paper is not soaked in the potassium iodide, but moistened with water; this portion will then also turn blue if ammonia be present. A reagent for distinguishing ozone from hydrogen peroxide with certainty is not known, and therefore these substances in very small quantities (for instance, in the atmosphere) may easily he confounded. Until recent years the mistake has frequently been made of ascribing the alteration of iodised starch-paper in the air to the presence of ozone; at the present time there is reason to believe that it is most often due to the presence of nitrous acid (Ilosva, 1889).

[8 bis] Fluorine (Chap. XI.), acting upon water at the ordinary temperature, takes up the hydrogen, and evolves the oxygen in the form of ozone (Moissan, 1889), and therefore the reaction must be expressed thus:—3H₂O + 3F₂ = 6HF + O₃.

[9] Ozone is, so to say, an oxide of oxygen, just as water is an oxide of hydrogen. Just as aqueous vapour is composed of two volumes of hydrogen and one volume of oxygen, which on combining condense into two volumes of aqueous vapour, so also two volumes of oxygen are combined in ozone with one volume of oxygen to give two volumes of ozone. In the action of ozone on different substances it is only that additional portion of its molecule by which it differs from ordinary oxygen that combines with other bodies, and that is why, under these circumstances, the volume of the ozonised oxygen does not change. Starting with two volumes of ozone, one-third of its weight is parted with, and two volumes of oxygen remain.

The above observations of Soret on the capacity of turpentine for dissolving ozone, together with Schönbein's researches on the formation of ozone in the oxidation of turpentine and of similar volatile vegetable oils (entering into the composition of perfumes), also explain the action of this ethereal oil on a great many substances. It is known that turpentine oil, when mixed with many substances, promotes their oxidation. In this case it probably not only itself promotes the formation of ozone, but also dissolves ozone from the atmosphere, and thus acquires the property of oxidising many substances. It bleaches linen and cork, decolorises indigo, promotes the oxidation and hardening of boiled linseed oil, &c. These properties of turpentine oil are made use of in practice. Dirty linen and many stained materials are easily cleaned by turpentine, not only because it dissolves the grease, but also because it oxidises it. The admixture of turpentine with drying (boiled) oil, oil-colours, and lacs aids their rapid drying because it attracts ozone. Various oils occurring in plants, and entering into the composition of perfumes and certain scent extracts, also act as oxidisers. They act in the same manner as oil of turpentine and oil of cinnamon. This perhaps explains the refreshing influence they have in scents and other similar preparations, and also the salubrity of the air of pine forests. Water upon which a layer of turpentine oil has been poured acquires, when left standing in the light, the disinfecting and oxidising properties in general of ozonised turpentine (is this due to the formation of H₂O₂?).

[10] The densest, most complex, and heaviest particles of matter should, under equal conditions, evidently be less capable of passing into a state of gaseous motion, should sooner attain a liquid state, and have a greater cohesive force.

[11] The blue colour proper to ozone may be seen through a tube one metre long, filled with oxygen, containing 10 p.c. of ozone. The density of liquid ozone has not, so far as I am aware, been determined.

[12] All explosive bodies and mixtures (gunpowder, detonating gas, &c.) evolve heat in exploding—that is, the reactions which accompany explosions are exothermal. In this manner ozone in decomposing evolves latent heat, although generally heat is absorbed in decomposition. This shows the meaning and cause of explosion.

[13] In Paris it has been found that the further from the centre of the town the greater the amount of ozone in the air. The reason of this is evident: in a city there are many conditions for the destruction of ozone. This is why we distinguish country air as being fresh. In spring the air contains more ozone than in autumn; the air of fields more than the air of towns.

[13 bis] The question of the presence of ozone in the air has not yet been fully elucidated, as those reactions by which ozone is generally detected are also common to nitrous acid (and its ammonia salt). Ilosvay de Ilosva (1889), in order to exclude the influence of such bodies, passed air through a 40 per cent. solution of caustic soda, and then through a 20 per cent. solution of sulphuric acid (these solutions do not destroy ozone), and tested the air thus purified for the presence of ozone. As no ozone was then detected the author concludes that all the effects which were formerly ascribed to ozone should be referred to nitrous acid. But this conclusion requires more careful verification, since the researches of Prof. Schönbein on the presence of peroxide of hydrogen in the atmosphere.

[14] The oxidising action of ozone may be taken advantage of for technical purposes; for instance, for destroying colouring matters. It has even been employed for bleaching tissues and for the rapid preparation of vinegar, although these methods have not yet received wide application.

[15] Isomerism in elements is termed allotropism.

[16] A number of substances resemble ozone in one or other of these respects. Thus cyanogen, C₂N₂, nitrogen chloride, &c., decompose with an explosion and evolution of heat. Nitrous anhydride, N₂O₃, forms a blue liquid like ozone, and in a number of cases oxidises like ozone.

[17] It is evident that there is a want of words here for distinguishing oxygen, O, as an ultimate element, from oxygen, O₂, as a free element. The latter should be termed oxygen gas, did not custom and the length of the expression render it inconvenient.

[18] Schönbein states that the formation of hydrogen peroxide is to be remarked in every oxidation in water or in the presence of aqueous vapour. According to Struve, hydrogen peroxide is contained in snow and in rain-water, and its formation, together with ozone and ammonium nitrate, is even probable in the processes of respiration and combustion. A solution of tin in mercury, or liquid tin amalgam, when shaken up in water containing sulphuric acid, produces hydrogen peroxide, whilst iron under the same circumstances does not give rise to its formation. The presence of small quantities of hydrogen peroxide in these and similar cases is recognised by many reactions. Amongst them, its action on chromic acid in the presence of ether is very characteristic. Hydrogen peroxide converts the chromic acid into a higher oxide, Cr₂O₇, which is of a dark-blue colour and dissolves in ether. This ethereal solution is to a certain degree stable, and therefore the presence of hydrogen peroxide may be recognised by mixing the liquid to be tested with ether and adding several drops of a solution of chromic acid. On shaking the mixture the ether dissolves the higher oxide of chromium which is formed, and acquires a blue colour. The formation of hydrogen peroxide in the combustion and oxidation of substances containing or evolving hydrogen must be understood in the light of the conception, to be considered later, of molecules occupying equal volumes in a gaseous state. At the moment of its evolution a molecule H₂ combines with a molecule O₂, and gives H₂O₂. As this substance is unstable, a large proportion of it is decomposed, a small amount only remaining unchanged. If it is obtained, water is easily formed from it; this reaction evolves heat, and the reverse action is not very probable. Direct determinations show that the reaction H₂O₂ = H₂O + O evolves 22,000 heat units. From this it will be understood how easy is the decomposition of hydrogen peroxide, as well as the fact that a number of substances which are not directly oxidised by oxygen are oxidised by hydrogen peroxide and by ozone, which also evolves heat on decomposition. Such a representation of the origin of hydrogen peroxide has been developed by me since 1870. Recently (1890) Traube has pronounced a similar opinion, stating that Zn under the action of water and air gives, besides ZnH₂O₂, also H₂O₂.

[19] The formation of hydrogen peroxide from barium peroxide by a method of double decomposition is an instance of a number of indirect methods of preparation. A substance A does not combine with B, but A B is obtained from A C in its action on B D (see Introduction) when C D is formed. Water does not combine with oxygen, but as a hydrate of acids it acts on the compound of oxygen with barium oxide, because this oxide gives a salt with an acid anhydride; or, what is the same thing, hydrogen with oxygen does not directly form hydrogen peroxide, but when combined with a haloid (for example, chlorine), under the action of barium peroxide, BaO₂, it leads to the formation of a salt of barium and H₂O₂. It is to be remarked that the passage of barium oxide, BaO, into the peroxide, BaO₂, is accompanied by the evolution of 12,100 heat units per 16 parts of oxygen by weight combined, and the passage of H₂O into the peroxide H₂O₂ does not proceed directly, because it would be accompanied by the absorption of 22,000 units of heat by 16 parts by weight of oxygen combined. Barium peroxide, in acting on an acid, evidently evolves less heat than the oxide, and it is this difference of heat that is absorbed in the hydrogen peroxide. Its energy is obtained from that evolved in the formation of the salt of barium.

[20] Peroxides of lead and manganese, and other analogous peroxides (see Chap. III., Note 9), do not give hydrogen peroxide under these conditions, but yield chlorine with hydrochloric acid.

[21] The impure barium peroxide obtained in this manner may be easily purified. For this purpose it is dissolved in a dilute solution of nitric acid. A certain quantity of an insoluble residue always remains, from which the solution is separated by filtration. The solution will contain not only the compound of the barium peroxide, but also a compound of the barium oxide itself, a certain quantity of which always remains uncombined with oxygen. The acid compounds of the peroxide and oxide of barium are easily distinguishable by their stability. The peroxide gives an unstable compound, and the oxide a stable salt. By adding an aqueous solution of barium oxide to the resultant solution, the whole of the peroxide contained in the solution may be precipitated as a pure aqueous compound (Kouriloff, 1889, obtained the same result by adding an excess of BaO₂). The first portions of the precipitate will consist of impurities—for instance, oxide of iron. The barium peroxide then separates out, and is collected on a filter and washed; it forms a substance having a definite composition, BaO₂,8H₂O, and is very pure. Pure hydrogen peroxide should always be prepared from such purified barium peroxide.

[22] In the cold, strong sulphuric acid with barium peroxide gives ozone; when diluted with a certain amount of water it gives oxygen (see Note 6), and hydrogen peroxide is only obtained by the action of very weak sulphuric acid. Hydrochloric, hydrofluoric, carbonic, and hydrosilicofluoric acids, and others, when diluted with water also give hydrogen peroxide with barium peroxide. Professor Schöne, who very carefully investigated hydrogen peroxide, showed that it is formed by the action of many of the above-mentioned acids on barium peroxide. In preparing peroxide of hydrogen by means of sulphuric acid, the solution must be kept cold. A solution of maximum concentration may be obtained by successive treatments with sulphuric acid of increasing strength. In this manner a solution containing 2 to 3 grams of pure peroxide in 100 c.c. of water may be obtained (V. Kouriloff).

[23] With the majority of acids, that salt of barium which is formed remains in solution; thus, for instance, by employing hydrochloric acid, hydrogen peroxide and barium chloride remain in solution. Complicated processes would be required to obtain pure hydrogen peroxide from such a solution. It is much more convenient to take advantage of the action of carbonic anhydride on the pure hydrate of barium peroxide. For this purpose the hydrate is stirred up in water, and a rapid stream of carbonic anhydride is passed through the water. Barium carbonate, insoluble in water, is formed, and the hydrogen peroxide remains in solution, so that it may be separated from the carbonate by filtering only. On a large scale hydrofluosilicic acid is employed, its barium salt being also insoluble in water.

[23 bis] Hydrogen peroxide may be extracted from very dilute solutions by means of ether, which dissolves it, and when mixed with it the hydrogen peroxide may even be distilled. A solution of hydrogen peroxide in water may be strengthened by cooling it to a low temperature, when the water crystallises out—that is, is converted into ice—whilst the hydrogen peroxide remains in solution, as it only freezes at very low temperatures. It must be observed that hydrogen peroxide, in a strong solution in a pure state, is exceedingly unstable even at the ordinary temperature, and therefore it must be preserved in vessels always kept cold, as otherwise it evolves oxygen and forms water.

[24] Peroxide of sodium (Chap. XII., Note 49) is prepared by burning sodium in dry air.

[24 bis] Peroxide of hydrogen should apparently find an industrial application in the arts, for instance, (1) as a bleaching agent, it having the important advantage over chloride of lime, SO₂, &c., of not acting upon the material under treatment. It may be used for bleaching feathers, hair, silk, wool, wood, &c., it also removes stains of all kinds, such as wine, ink, and fruit stains; (2) it destroys bacteria like ozone without having any injurious effect upon the human body. It can also be used for washing all kinds of wounds, for purifying the air in the sick room, &c., and (3) as a preserving agent for potted meats, &c.

[25] As the result of careful research, certain of the catalytic or contact phenomena have been subjected to exact explanation, which shows the participation of a substance present in the process of a reaction, whilst, however, it does not alter the series of changes proceeding from mechanical actions only. Professor Schöne, of the Petroffsky Academy, has already explained a number of reactions of hydrogen peroxide which previously were not understood. Thus, for instance, he showed that with hydrogen peroxide, alkalis give peroxides of the alkaline metals, which combine with the remaining hydrogen peroxide, forming unstable compounds which are easily decomposed, and therefore alkalis evince a decomposing (catalytic) influence on solutions of hydrogen peroxide. Only acid solutions of hydrogen peroxide, and then only dilute ones, can be preserved well.

[26] Hydrogen peroxide, as a substance containing much oxygen (namely, 16 parts to one part by weight of hydrogen), exhibits many oxidising reactions. Thus, it oxidises arsenic, converts lime into calcium peroxide, the oxides of zinc and copper into peroxides; it parts with its oxygen to many sulphides, converting them into sulphates, &c. So, for example, it converts black lead sulphide, PbS, into white lead sulphate, PbSO₄, copper sulphide into copper sulphate, and so on. The restoration of old oil paintings by hydrogen peroxide is based on this action. Oil colours are usually admixed with white lead, and in many cases the colour of oil-paints becomes darker in process of time. This is partly due to the sulphuretted hydrogen contained in the air, which acts on white lead, forming lead sulphide, which is black. The intermixture of the black colour darkens the rest. In cleaning a picture with a solution of hydrogen peroxide, the black lead sulphide is converted into white sulphate, and the colours brighten owing to the disappearance of the black substance which previously darkened them. Hydrogen peroxide oxidises with particular energy substances containing hydrogen and capable of easily parting with it to oxidising substances. Thus it decomposes hydriodic acid, setting the iodine free and converting the hydrogen it contains into water; it also decomposes sulphuretted hydrogen in exactly the same manner, setting the sulphur free. Starch paste with potassium iodide is not, however, directly coloured by peroxide of hydrogen in the entire absence of free acids; but the addition of a small quantity of iron sulphate (green vitriol) or of lead acetate to the mixture is enough to entirely blacken the paste. This is a very sensitive reagent (test) for peroxide of hydrogen, like the test with chromic acid and ether (see Note 8).

[27] To explain the phenomenon, an hypothesis has been put forward by Brodie, Clausius, and Schönbein which supposes ordinary oxygen to be an electrically neutral substance, composed, so to speak, of two electrically opposite kinds of oxygen—positive and negative. It is supposed that hydrogen peroxide contains one kind of such polar oxygen, whilst in the oxides of the above-named metals the oxygen is of opposite polarity. It is supposed that in the oxides of the metals the oxygen is electro-negative, and in hydrogen peroxide electro-positive, and that on the mutual contact of these substances ordinary neutral oxygen is evolved as a consequence of the mutual attraction of the oxygens of opposite polarity. Brodie admits the polarity of oxygen in combination, but not in an uncombined state, whilst Schönbein supposes uncombined oxygen to be polar also, considering ozone as electro-negative oxygen. The supposition that the oxygen of ozone is different from that of hydrogen peroxide is contradicted by the fact that in acting on barium peroxide strong sulphuric acid forms ozone, and dilute acid forms hydrogen peroxide.

[27 bis] It should be mentioned that Schiloff (1893) on taking a 3 per cent. solution of H₂O₂, adding soda to it, and then extracting the peroxide of hydrogen from the mixture by shaking it with ether, obtained a 50 per cent. solution of H₂O₂, which, although perfectly free from other acids, gave a distinctly acid reaction with litmus. And here attention should first of all be turned to the fact that the peroxides of the metals correspond to H₂O₂, like salts to an acid, for instance, Na₂O₂ and BaO₂, &c. Furthermore, it must be remembered that O is an analogue of S (Chapters XV. and XX.), and sulphur gives H₂S, H₂SO₃, and H₂SO₄. And sulphurous acid, H₂SO₃, is unstable as a hydrate, and gives water and the anhydride SO₂. If the sulphur be replaced by oxygen, then instead of H₂SO₃ and SO₂, we have H₂OO₃ and OO₂. The latter is ozone, while the salt K₂O₄ (peroxide of potassium) corresponds to the hydrate H₂O₄ as to an acid. And between H₂O and H₂O₄ there may exist intermediate acid compounds, the first of which would be H₂O₂, in which, from analogy to the sulphur compounds, one would expect acid properties. Besides which we may mention that for sulphur, besides H₂S (which is a feeble acid), H₂S₂, H₂S₃, H₂S₅ are known. Thus in many respects H₂O₂ offers points of resemblance to acid compounds, and as regards its qualitative (reactive) analogies, it not only resembles Na₂O₂, BaO₂, &c., but also persulphuric acid HSO₄ (to which the anhydride S₂O₇ corresponds) and Cu₂O₇, &c., which will be subsequently described.

[28] Tamman and Carrara (1892) showed by determining the depression (fall of the temperature of the formation of ice, Chapters I. and VII.) that the molecule of peroxide of hydrogen contains H₂O₂, and not HO or H₃O₃.

[28 bis] The lower oxides of nitrogen and chlorine and the higher oxides of manganese are also formed with the absorption of heat, and therefore, like hydrogen peroxide, act in a powerfully oxidising manner, and are not formed by the same methods as the majority of other oxides. It is evident that, being endowed with a richer store of energy (acquired in combination or by absorption of heat), such substances, compared with others poorer in energy, will exhibit a greater diversity of cases of chemical action with other substances.

[29] If the point of support of a body lies in a vertical line below the centre of gravity, it is in unstable equilibrium. If the centre of gravity lies below the point of support; the state of equilibrium is very stable, and a vibration may take place about this position of stable equilibrium, as in a pendulum or balance, when finally the body assumes a position of stable equilibrium. But if, keeping to the same mechanical example, the body be supported not on a point, in the geometrical sense of the word, but on a small plane, then the state of unstable equilibrium may be preserved, unless destroyed by external influences. Thus a man stands upright supported on the plane, or several points of the surfaces of his feet, having the centre of gravity above the points of support. Vibration is then possible, but it is limited, otherwise on passing outside the limit of possible equilibrium another more stable position is attained about which vibration becomes more possible. A prism immersed in water may have several more or less stable positions of equilibrium. The same is also true with the atoms in molecules. Some molecules present a state of more stable equilibrium than others. Hence from this simple comparison it will be at once evident that the stability of molecules may vary considerably, that one and the same elements, taken in the same number, may give isomerides of different stability, and, lastly, that there may exist states of equilibria which are so unstable, so ephemeral, that they will only arise under particularly special conditions—such, for example, as certain hydrates mentioned in the first chapter (see Notes 57, 67, and others). And if in one case the instability of a given state of equilibrium is expressed by its instability with a change of temperature or physical state, then in other cases it is expressed by the facility with which it decomposes under the influence of contact or of the chemical influence of other substances.

[30] When, for example, any element forms several oxides, they are subject to the law of multiple proportions. For a given quantity of the non-metal or metal the quantities of oxygen in the different degrees of oxidation will stand as 1 : 2, or as 1 : 3, or as 2 : 3, or as 2 : 7, and so on. Thus, for instance, copper combines with oxygen in at least two proportions, forming the oxides found in nature, and called the suboxide and the oxide of copper, Cu₂O and CuO; the oxide contains twice as much oxygen as the suboxide. Lead also presents two degrees of oxidation, the oxide and peroxide, and in the latter there is twice as much oxygen as in the former, PbO and PbO₂. When a base and an acid are capable of forming several kinds of salts, normal, acid, basic, and anhydro-, it is found that they also clearly exemplify the law of multiple proportions. This was demonstrated by Wollaston soon after the discovery of the law in question. We saw in the first chapter that salts show different degrees of combination with water of crystallisation, and that they obey the law of multiple proportions. And, more than this, the indefinite chemical compounds existing as solutions may, as we saw in the same chapter, be brought under the law of multiple proportions by the hypothesis that solutions are unstable hydrates formed according to the law of multiple proportions, but occurring in a state of dissociation. By means of this hypothesis the law of multiple proportions becomes still more general, and all the aspects of chemical compounds are subject to it. The direction of the whole contemporary state of chemistry was determined by the discoveries of Lavoisier and Dalton. By endeavouring to prove that in solutions we have nothing else than the liquid products of the dissociation of definite hydrates, it is my aim to bring also this category of indefinite compounds under the general principle enunciated by Dalton; just as astronomers have discovered a proof and not a negation of the laws of Newton in perturbations.

[31] Leucippus, Democritus, and especially Lucretius, in the classical ages, represented matter as made up of atoms—that is, of parts incapable of further division. The geometrical impossibility of such an admission, as well as the conclusions which were deduced by the ancient atomists from their fundamental propositions, prevented other philosophers from following them, and the atomic doctrine, like very many others, lived, without being ratified by fact, in the imaginations of its followers. Between the present atomic theory and the doctrine of the above-named ancient philosophers there is naturally a remote historical connection, as between the doctrine of Pythagoras and Copernicus, but they are essentially different. For us the atom is indivisible, not in the geometrical abstract sense, but only in a physical and chemical sense. It would be better to call the atoms indivisible individuals. The Greek atom = the Latin individual, both according to the etymology and original sense of the words, but in course of time these two words have acquired a different meaning. The individual is mechanically and geometrically divisible, and only indivisible in a special sense. The earth, the sun, a man or a fly are individuals, although geometrically divisible. Thus the ‘atoms’ of contemporary science, indivisible in a chemical sense, form those units with which we are concerned in the investigation of the natural phenomena of matter, just as a man is an indivisible unit in the investigation of social relations, or as the stars, planets, and luminaries serve as units in astronomy. The formation of the vortex hypothesis, in which, as we shall afterwards see, atoms are entire whirls mechanically complex, although physico-chemically indivisible, clearly shows that the scientific men of our time in holding to the atomic theory have only borrowed the word and form of expression from the ancient philosophers, and not the essence of their atomic doctrine. It is erroneous to imagine that the contemporary conceptions of the atomists are nothing but the repetition of the metaphysical reasonings of the ancients. To show the true meaning of the atomism of the ancient philosophers, and the profound difference between their points of argument and those of contemporary men of science, I cite the following fundamental propositions of Democritus (B.C. 470–380) as the best expounder of the atomic doctrine of the ancients:—(1) Nothing can proceed from nothing, nothing that exists can disappear or be destroyed (and hence matter), and every change only consists of a combination or separation. (2) Nothing is accidental, there is a reason and necessity for everything. (3) All except atoms and vacua is reason and not existence. (4) The atoms, which are infinite in number and form, constitute the visible universe by their motion, impact, and consequent revolving motion. (5) The variety of objects depends only upon a difference in the number, form, and order of the atoms of which they are formed, and not upon a qualitative difference of their atoms, which only act upon each other by pressure and impact. (6) The spirit, like fire, consists of minute, spherical, smooth, and very mobile and all-penetrating atoms, whose motion forms the phenomenon of life. These Democritian, chiefly metaphysical, principles of atomism are so essentially different from the principles of the present atomic doctrine, which is exclusively applied to explaining the phenomena of the external world, that it may be useful to mention the essence of the atomic propositions of Boscovitch, a Slav who lived in the middle of the eighteenth century, and who is regarded as the founder of the modern atomic doctrines which, however, did not take hold upon the minds of scientific men, and were rarely applied prior to Dalton—i.e. until the beginning of the nineteenth century. The doctrine of Boscovitch was enunciated by him in 1758–1764 in his ‘Philosophiæ naturalis theoria reducta ad unicam legem virium in natura existentium.’ Boscovitch considers matter to be composed of atoms, and the atoms to be the points or centres of forces (just as the stars and planets may be considered as points of space), acting between bodies and their parts. These forces vary with the distance, so that beyond a certain very small distance all atoms, and hence also their aggregates, are attracted according to Newton's law, but at less distances, there alternate wave-like spheres of gradually decreasing attraction and increasing (as the distance decreases) repulsion, until at last at a minimum distance only the repellent action remains. Atoms, therefore, cannot merge into each other. Consequently, the atoms are held at a certain distance from each other, and therefore occupy space. Boscovitch compares the sphere of repulsion surrounding the atoms to the spheres of action of firing of a detachment of soldiers. According to his doctrine, atoms are indestructible, do not merge into each other, have mass, are everlasting and mobile under the action of the forces proper to them. Maxwell rightly calls this hypothesis the ‘extreme’ among those existing to explain matter, but many aspects of Boscovitch's doctrine repeat themselves in the views of our day, with this essential difference, that instead of a mathematical point furnished with the properties of mass, the atoms are endowed with a corporality, just as the stars and planets are corporal, although in certain aspects of their interaction they may be regarded as mathematical points. In my opinion, the atomism of our day must first of all be regarded merely as a convenient method for the investigation of ponderable matter. As a geometrician in reasoning about curves represents them as formed of a succession of right lines, because such a method enables him to analyse the subject under investigation, so the scientific man applies the atomic theory as a method of analysing the phenomena of nature. Naturally there are people now, as in ancient times, and as there always will be, who apply reality to imagination, and therefore there are to be found atomists of extreme views; but it is not in their spirit that we should acknowledge the great services rendered by the atomic doctrine to all science, which, while it has been essentially independently developed, is, if it be desired to reduce all ideas to the doctrines of the ancients, a union of the ancient dynamical and atomic doctrines.

[32] Dalton and many of his successors distinguished the atoms of elements and compounds, in which they clearly symbolised the difference of their opinion from the representations of the ancients. Now only the individuals of the elements, indivisible by physical and chemical forces, are termed atoms, and the individuals of compounds indivisible under physical changes are termed molecules; these are divisible into atoms by chemical forces.

[33] In the present condition of science, either the atomic or the dynamical hypothesis is inevitably obliged to admit the existence of an invisible and imperceptible motion in matter, without which it is impossible to understand either light or heat, or gaseous pressure, or any of the mechanical, physical, or chemical phenomena. The ancients saw vital motion in animals only, but to us the smallest particle of matter, endued with vis viva, or energy in some degree or other, is incomprehensible without self-existent motion. Thus motion has become a conception inseparably knit with the conception of matter, and this has prepared the ground for the revival of the dynamical hypothesis of the constitution of matter. In the atomic theory there has arisen that generalising idea by which the world of atoms is constructed, like the universe of heavenly bodies, with its suns, planets, and meteors, endued with everlasting force of motion, forming molecules as the heavenly bodies form systems, like the solar system, which molecules are only relatively indivisible in the same way as the planets of the solar system are inseparable, and stable and lasting as the solar system is lasting. Such a representation, without necessitating the absolute indivisibility of atoms, expresses all that science can require for an hypothetical representation of the constitution of matter. In closer proximity to the dynamical hypothesis of the constitution of matter is the oft-times revived vortex hypothesis. Descartes first endeavoured to raise it; Helmholtz and Thomson (Lord Kelvin) gave it a fuller and more modern form; many scientific men applied it to physics and chemistry. The idea of vortex rings serves as the starting point of this hypothesis; these are familiar to all as the rings of tobacco smoke, and may be artificially obtained by giving a sharp blow to the sides of a cardboard box having a circular orifice and filled with smoke. Phosphuretted hydrogen, as we shall see later on, when bubbling from water always gives very perfect vortex rings in a still atmosphere. In such rings it is easy to observe a constant circular motion about their axes, and to notice the stability the rings possess in their motion of translation. This unchangeable mass, endued with a rapid internal motion, is likened to the atom. In a medium deprived of friction, such a ring, as is shown by theoretical considerations of the subject from a mechanical point of view, would be perpetual and unchangeable. The rings are capable of grouping together, and in combining, without being absolutely indivisible, remain indivisible. The vortex hypothesis has been established in our times, but it has not been fully developed; its application to chemical phenomena is not clear, although not impossible; it does not satisfy a doubt in respect to the nature of the space existing between the rings (just as it is not clear what exists between atoms, and between the planets), neither does it tell us what is the nature of the moving substance of the ring, and therefore for the present it only presents the germ of an hypothetical conception of the constitution of matter; consequently, I consider that it would be superfluous to speak of it in greater detail. However, the thoughts of investigators are now (and naturally will be in the future), as they were in the time of Dalton, often turned to the question of the limitation of the mechanical division of matter, and the atomists have searched for an answer in the most diverse spheres of nature. I select one of the methods attempted, which does not in any way refer to chemistry, in order to show how closely all the provinces of natural science are bound together. Wollaston proposed the investigation of the atmosphere of the heavenly bodies as a means for confirming the existence of atoms. If the divisibility of matter be infinite, then air must extend throughout the entire space of the heavens as it extends all over the earth by its elasticity and diffusion. If the infinite divisibility of matter be admitted, it is impossible that any portion of the whole space of the universe can be entirely void of the component parts of our atmosphere. But if matter be divisible up to a certain limit only—namely, up to the atom—then there can exist a heavenly body void of an atmosphere; and if such a body be discovered, it would serve as an important factor for the acceptation of the validity of the atomic doctrine. The moon has long been considered as such a luminary and this circumstance, especially from its proximity to the earth, has been cited as the best proof of the validity of the atomic doctrine. This proof is apparently (Poisson) deprived of some of its force from the possibility of the transformation of the component parts of our atmosphere into a solid or liquid state at immense heights above the earth's surface, where the temperature is exceedingly low; but a series of researches (Pouillet) has shown that the temperature of the heavenly space is comparatively not so very low, and is attainable by experimental means, so that at the low existing pressure the liquefaction of the gases of the atmosphere cannot he expected even on the moon. Therefore the absence of an atmosphere about the moon, if it were not subject to doubt, would be counted as a forcible proof of the atomic theory. As a proof of the absence of a lunar atmosphere, it is cited that the moon, in its independent motion between the stars, when eclipsing a star—that is, when passing between the eye and the star—does not show any signs of refraction at its edge; the image of the star does not alter its position in the heavens on approaching the moon's surface, consequently there is no atmosphere on the moon's surface capable of refracting the rays of light. Such is the conclusion by which the absence of a lunar atmosphere is acknowledged. But this conclusion is most feeble, and there are even facts in exact contradiction to it, by which the existence of a lunar atmosphere may be proved. The entire surface of the moon is covered with a number of mountains, having in the majority of cases the conical form natural to volcanoes. The volcanic character of the lunar mountains was confirmed in October 1866, when a change was observed in the form of one of them (the crater Linnea). These mountains must be on the edge of the lunar disc. Seen in profile, they screen one another and interfere with observations on the surface of the moon, so that when looking at the edge of the lunar disc we are obliged to make our observations not on the moon's surface, but at the summits of the lunar mountains. These mountains are higher than those on our earth, and consequently at their summits the lunar atmosphere must he exceedingly rarefied even if it possess an observable density at the surface. Knowing the mass of the moon to be eighty-two times less than the mass of the earth, we are able to determine approximately that our atmosphere at the moon's surface would be about twenty-eight times lighter than it is on the earth, and consequently at the very surface of the moon the refraction of light by the lunar atmosphere must he very slight, and at the heights of the lunar mountains it must be imperceptible, and would be lost within the limits of experimental error. Therefore the absence of refraction of light at the edge of the moon's disc cannot yet be urged in favour of the absence of a lunar atmosphere. There is even a series of observations obliging us to admit the existence of this atmosphere. These researches are due to Sir John Herschel. This is what he writes: ‘It has often been remarked that during the eclipse of a star by the moon there occurs a peculiar optical illusion; it seems as if the star before disappearing passed over the edge of the moon and is seen through the lunar disc, sometimes for a rather long period of time. I myself have observed this phenomenon, and it has been witnessed by perfectly trustworthy observers. I ascribe it to optical illusion, but it must be admitted that the star might have been seen on the lunar disc through some deep ravine on the moon.’ Geniller, in Belgium (1856), following the opinion of Cassini, Eiler, and others, gave an explanation of this phenomenon: he considers it due to the refraction of light in the valleys of the lunar mountains which occur on the edge of the lunar disc. In fact, although these valleys do not probably present the form of straight ravines, yet it may sometimes happen that the light of a star is so refracted that its image might he seen, notwithstanding the absence of a direct path for the light-rays. He then goes on to remark that the density of the lunar atmosphere must be variable in different parts, owing to the very long nights on the moon. On the dark, or non-illuminated portion, owing to these long nights, which last thirteen of our days and nights, there must be excessive cold, and hence a denser atmosphere, while, on the contrary, on the illuminated portion the atmosphere must be much more rarefied. This variation in the temperature of the different parts of the moon's surface explains also the absence of clouds, notwithstanding the possible presence of air and aqueous vapour, on the visible portion of the moon. The presence of an atmosphere round the sun and planets, judging from astronomical observations, may be considered as fully proved. On Jupiter and Mars even bands of clouds may be distinguished. Thus the atomic doctrine, admitting a finite mechanical divisibility only, must he, as yet at least, only accepted as a means, similar to that means which a mathematician employs when he breaks up a continuous curvilinear line into a number of straight lines. There is a simplicity of representation in atoms, but there is no absolute necessity to have recourse to them. The conception of the individuality of the parts of matter exhibited in chemical elements only is necessary and trustworthy.

[1] See Note 15 bis.

[1 bis] The reason why there are no other nitrogenous substances within the earth's mass beyond those which have come there with the remains of organisms, and from the air with rain-water, must be looked for in two circumstances. In the first place, in the instability of many nitrogenous compounds, which are liable to break up with the formation of gaseous nitrogen; and in the second place in the fact that the salts of nitric acid, forming the product of the action of air on many nitrogenous and especially organic compounds, are very soluble in water, and on penetrating into the depths of the earth (with water) give up their oxygen. The result of the changes of the nitrogenous organic substances which fall into the earth is without doubt frequently, if not invariably, the formation of gaseous nitrogen. Thus the gas evolved from coal always contains much nitrogen (together with marsh gas, carbonic anhydride, and other gases).

[2] Copper (best as turnings, which present a large surface) absorbs oxygen, forming CuO, at the ordinary temperature in the presence of solutions of acids, or, better still, in the presence of a solution of ammonia, when it forms a bluish-violet solution of oxide of copper in ammonia. Nitrogen is very easily procured by this method. A flask filled with copper turnings is closed with a cork furnished with a funnel and stopcock. A solution of ammonia is poured into the funnel, and caused to drop slowly upon the copper. If at the same time a current of air be slowly passed through the flask (from a gasholder), then all the oxygen will be absorbed from it and the nitrogen will pass from the flask. It should be washed with water to retain any ammonia that may be carried off with it.

[3] The oxygen compounds of nitrogen (for example, N₂O, NO, NO₂) are decomposed at a red heat by themselves, and under the action of red-hot copper, iron, sodium, &c., they give up their oxygen to the metals, leaving the nitrogen free. According to Meyer and Langer (1885), nitrous oxide, N₂O, decomposes below 900°, although not completely.

[4] Chlorine and bromine (in excess), as well as bleaching powder (hypochlorites), take up the hydrogen from ammonia, NH₃, leaving nitrogen. Nitrogen is best procured from ammonia by the action of a solution of sodium hypobromite on solid sal-ammoniac.

[4 bis] Lord Rayleigh in 1894, when determining the weight of a volume of carefully purified nitrogen by weighing it in one and the same globe, found that the gas obtained from air, by the action of incandescent copper (or iron or by removing the oxygen by ferrous oxide) was always ¹⁄₂₀₀ heavier than the nitrogen obtained from its compounds, for instance, from the oxide or suboxide of nitrogen, decomposed by incandescent pulverulent iron or from the ammonia salt of nitrous acid. For the nitrogen procured from air, he obtained, at 0° and 760·4 mm. pressure, a weight = 2·310 grms., while for the nitrogen obtained from its compounds, 2·299 grms. This difference of about ¹⁄₂₀₀ could not be explained by the nitrogen not having been well purified, or by inaccuracy of experiment, and was the means for the remarkable discovery of the presence of a heavy gas in air, which will be mentioned in Note 16 bis.

[5] See Chapter II. Note 29.

[5 bis] See Note 11 bis.

[6] The combination of boron with nitrogen is accompanied by the evolution of sufficient heat to raise the mass to redness; titanium combines so easily with nitrogen that it is difficult to obtain it free from that element; magnesium easily absorbs nitrogen at a red heat. It is a remarkable and instructive fact that these compounds of nitrogen are very stable and non-volatile. Carbon (C = 12) with nitrogen gives cyanogen, C₂N₂, which is gaseous and very unstable, and whose molecule is not large, whilst boron (B = 11) forms a nitrogenous compound which is solid, non-volatile, and very stable. Its composition, BN, is similar to that of cyanogen, but its molecular weight, B_nN_n, is probably greater. Its composition, like that of N₂Mg₃, NNa₃, N₂Hg₃ and of many of the metallic nitrides, corresponds to ammonia with the substitution of all its hydrogen by a metal. In my opinion, a detailed study of the transformations of the nitrides now known, should lead to the discovery of many facts in the history of nitrogen.

[7] This reaction, so far as is known, does not proceed beyond a certain limit, probably because cyanogen, CN, itself breaks up into carbon and nitrogen.

[8] Frémy and Becquerel took dry air, and observed the formation of brown vapours of oxides of nitrogen on the passage of sparks.

[9] If a mixture of one volume of nitrogen and fourteen volumes of hydrogen be burnt, then water and a considerable quantity of nitric acid are formed. It may be partly due to this that a certain quantity of nitric acid is produced in the slow oxidation of nitrogenous substances in an excess of air. This is especially facilitated by the presence of an alkali with which the nitric acid formed can combine. If a galvanic current be passed through water containing the nitrogen and oxygen of the air in solution, then the hydrogen and oxygen set free combine with the nitrogen, forming ammonia and nitric acid.

When copper is oxidised at the expense of the air at the ordinary temperature in the presence of ammonia, oxygen is absorbed, not only for combination with the copper, but also for the formation of nitric acid.

The combination of nitrogen with oxygen, even, for example, by the action of electric sparks, is not accompanied by an explosion or rapid combination, as in the action of a spark on a mixture of oxygen and hydrogen. This is explained by the fact that heat is not evolved in the combination of nitrogen with oxygen, but is absorbed—an expenditure of energy is required, there is no evolution of energy. In fact, there will not be the transmission of heat from particle to particle which occurs in the explosion of detonating gas. Each spark will aid the formation of a certain quantity of the compound of oxygen and nitrogen, but will not excite the same in the neighbouring particles. In other words, the combination of hydrogen with oxygen is an exothermal reaction, and the combination of nitrogen with oxygen an endothermal reaction.

A condition particularly favourable for the oxidation of nitrogen is the explosion of detonating gas and air if the former be in excess. If a mixture of two volumes of detonating gas and one volume of air be exploded, then one-tenth of the air is converted into nitric acid, and consequently after the explosion has taken place there remain only nine-tenths of the volume of air originally taken. If a large proportion of air be taken—for instance, four volumes of air to two volumes of detonating gas—then the temperature of the explosion is lowered, the volume of air taken remains unchanged, and no nitric acid is formed. This gives a rule to be observed in making use of the eudiometer—namely that to weaken the force of the explosion not less than an equal volume of air should be added to the explosive mixture. On the other hand a large excess must not be taken as no explosion would then ensue (see Chapter III. Note 34). Probably in the future means will be found for obtaining compounds of nitrogen on a large industrial scale by the aid of electric discharges, and by making use of the inexhaustible mass of nitrogen in the atmosphere.

[10] In reality nitric oxide, NO, is first formed, but with oxygen and water it gives (brown fumes) nitrous anhydride, which, as we shall afterwards learn, in the presence of water and oxygen gives nitric acid.

[11] The nitric acid contained in the soil, river water (Chapter I., Note 2), wells, &c., proceeds (like carbonic anhydride) from the oxidation of organic compounds which have fallen into water, soil, &c.

[11 bis] Crookes employed a current of 15 ampères and 65 volts, and passed it through an induction coil with 330 vibrations per second, and obtained a flame between the poles placed at a distance of 46 mm. which after the appearance of the arc and flame could be increased to 200 mm. A platinum wire fused in the flame.

[12] This property of nitrogen, which under normal conditions is inactive, leads to the idea that under the influence of an electric discharge gaseous nitrogen changes in its properties; if not permanently like oxygen (electrolysed oxygen or ozone does not react on nitrogen, according to Berthelot), it may be temporarily at the moment of the action of the discharge, just as some substances under the action of heat are permanently affected (that is, when once changed remain so—for instance, white phosphorus passes into red, &c.), whilst others are only temporarily altered (the dissociation of S₆ into S₂ or of sal-ammoniac into ammonia and hydrochloric acid). Such a proposition is favoured by the fact that nitrogen gives two kinds of spectra, with which we shall afterwards become acquainted. It may be that the molecules N₂ then give less complex molecules, N containing one atom, or form a complex molecule N₃, like oxygen in passing into ozone. Probably under a silent discharge the molecules of oxygen, O₂, are partly decomposed and the individual atoms O combine with O₂, forming ozone, O₃.

[13] This reaction, discovered by Chabrié and investigated by Thénard, was only rightly understood when Deville applied the principles of dissociation to it.

[14] The action of nitrogen on acetylene (Berthelot) resembles this reaction. A mixture of these gases under the influence of a silent discharge gives hydrocyanic acid, C₂H₂ + N₂ = 2CNH. This reaction cannot proceed beyond a certain limit because it is reversible.

[15] Berthelot successfully employed electricity of even feeble potential in these experiments, which fact led him to think that in nature, where the action of electricity takes place very frequently, a part of the complex nitrogenous substances may proceed from the gaseous nitrogen of the air by this method.

As the nitrogenous substances of organisms play a very important part in them (organic life cannot exist without them), and as the nitrogenous substances introduced into the soil are capable of invigorating its crops (of course in the presence of the other nourishing principles required by plants), the question of the means of converting the atmospheric nitrogen into the nitrogenous compounds of the soil, or into assimilable nitrogen capable of being absorbed by plants and of forming complex (albuminous) substances in them, is one of great theoretical and practical interest. The artificial (technical) conversion of the atmospheric nitrogen into nitrogenous compounds, notwithstanding repeated attempts, cannot yet be considered as fulfilled in a practical remunerative manner although its possibility is already evident. Electricity will probably aid in solving this very important practical problem. When the theoretical side of the question is further advanced, then without doubt an advantageous means will be found for the manufacture of nitrogenous substances from the nitrogen of the air; and this is needed, before all, for the agriculturist, to whom nitrogenous fertilisers form an expensive item, and are more important than all other manures.

One thousand tons of farmyard manure do not generally contain more than four tons of nitrogen in the form of complex nitrogenous substances, and this amount of nitrogen is contained in twenty tons of ammonium sulphate, therefore the effect of a mass of farmyard manure in respect to the introduction of nitrogen may be produced by small quantities of artificial nitrogenous fertilisers (see Note 15 bis).

[15 bis] Although the numerous, and as far as possible accurate and varied researches made in the physiology of plants have proved that the higher forms of plants are not capable of directly absorbing the nitrogen of the atmosphere and converting it into complex albuminous substances, still it has been long and repeatedly observed that the amount of nitrogenous substances in the soil is increased by the cultivation of plants of the bean (leguminous) family such as pea, acacia, &c. A closer study of these plants has shown that this is connected with the formation of peculiar nodular swellings in their roots caused by the growth of peculiar micro-organisms (bacteria) which cohabit the soil with the roots, and are capable of absorbing nitrogen from the air, i.e. of converting it into assimilated nitrogen. This branch of plant physiology, which forms another proof of the important part played by micro-organisms in nature, cannot be discussed in this work, but it should be mentioned, since it is of great theoretical and practical interest, and, moreover, phenomena of this kind, which have recently been discovered, promise to explain, to some extent at least, certain of the complex problems concerning the development of life on the earth.

[16] Under the name of atmospheric air the chemist and physicist understand ordinary air containing nitrogen and oxygen only, notwithstanding that the other component parts of air have a very important influence on the living matter of the earth's surface. That air is so represented in science is based on the fact that only the two components above-named are met with in air in a constant quantity, whilst the others are variable. The solid impurities may be separated from air required for chemical or physical research by simple filtration through a long layer of cotton-wool placed in a tube. Organic impurities are removed by passing the air through a solution of potassium permanganate. The carbonic anhydride contained in air is absorbed by alkalis—best of all, soda-lime, which in a dry state in porous lumps absorbs it with exceeding rapidity and completeness. Aqueous vapour is removed by passing the air over calcium chloride, strong sulphuric acid, or phosphoric anhydride. Air thus purified is accepted as containing only nitrogen and oxygen, although in reality it still contains a certain quantity of hydrogen and hydrocarbons, from which it may be purified by passing over copper oxide heated to redness. The copper oxide then oxidises the hydrogen and hydrocarbons—it burns them, forming water and carbonic anhydride, which may be removed as above described. When it is said that in the determination of the density of gases the weight of air is taken as unity, it is understood to be such air, containing only nitrogen and oxygen.

[16 bis] Thanks to the remarkable discovery made in the summer of 1894 by Lord Rayleigh and Prof. Ramsay, the well-known component elements of air must now he supplemented by 1 p.c. (by volume) of a heavy gas (density about 19, H = 1), inactive like nitrogen, which was discovered in the researches made by Lord Rayleigh on the density of nitrogen as mentioned in note 4 bis. Up to the present time this gas has been always determined together with nitrogen, because it combines with neither the hydrogen in the eudiometer nor with the copper in the gravimetric method of determining the composition of air, and therefore has always remained with the nitrogen. It has been possible to separate it from nitrogen since magnesium absorbs nitrogen at a red heat, while this gas remains unabsorbed, and was found to have a density nearly one and a half time greater than that of nitrogen (is it not a polymer of nitrogen, N₃?). It is now known also that this gas gives a luminous spectrum, which contains the bright blue line observed in the spectrum of nitrogen. Owing to the fact that it is an exceedingly inert substance, even more so than nitrogen, it has been termed Argon. Further reference will be made to it in the Appendix.

[17] As a further proof of the fact that certain circumstances may change the composition of air, it will be enough to point out that the air contained in the cavities of glaciers contains only up to 10 p.c. of oxygen. This depends on the fact that at low temperatures oxygen is much more soluble in snow-water and snow than nitrogen. When shaken up with water the composition of air should change, because the water dissolves unequal quantities of oxygen and nitrogen. We have already seen (Chapter I.) that the air boiled off from water saturated at about 0° contains about thirty-five volumes of oxygen and sixty-five volumes of nitrogen, and we have considered the reason of this.

[18] The analysis of air by weight conducted by Dumas and Boussingault in Paris, which they repeated many times between April 27 and September 22, 1841, under various conditions of weather, showed that the amount by weight of oxygen only varies between 22·89 p.c. and 23·08 p.c., the average amount being 23·07 p.c. Brunner, at Bern in Switzerland, and Bravais, at Faulhorn in the Bernese Alps, at a height of two kilometres above the level of the sea, Marignac at Geneva, Lewy at Copenhagen, and Stas at Brussels, have analysed the air by the same methods, and found that its composition does not exceed the limits determined for Paris. The most recent determinations (with an accuracy of ±0·05 p.c.) confirm the conclusion that the composition of the atmosphere is constant.

As there are some grounds (which will be mentioned shortly) for considering that the composition of the air at great altitudes is slightly different from that at attainable heights—namely, that it is richer in the lighter nitrogen—several fragmentary observations made at Munich (Jolly, 1880) gave reason for thinking that in the upward currents (that is in the region of minimum barometric pressure or at the centres of meteorological cyclones) the air is richer in oxygen than in the descending currents of air (in the regions of anticyclones or of barometric maxima); but more carefully conducted observations showed this supposition to be incorrect. Improved methods for the analysis of air have shown that certain slight variations in its composition do actually occur, but in the first place they depend on incidental local influences (on the passage of the air over mountains and large surfaces of water, regions of forest and herbage, and the like), and in the second place are limited to quantities which are scarcely distinguishable from possible errors in the analyses. The researches made by Kreisler in Germany (1885) are particularly convincing.

The considerations which lead to the supposition that the atmosphere at great altitudes contains less oxygen than at the surface of the earth are based on the law of partial pressures (Chapter I.) According to this law, the equilibrium of the oxygen in the strata of the atmosphere is not dependent on the equilibrium of the nitrogen, and the variation in the densities of both gases with the height is determined by the pressure of each gas separately. Details of the calculations and considerations here involved are contained in my work On Barometric Levellings, 1876, p. 48.

On the basis of the law of partial pressure and of hypsometrical formulæ, expressing the laws of the variation of pressures at different altitudes, the conclusion may be deduced that at the upper strata of the atmosphere the proportion of the nitrogen with respect to the oxygen increases, but the increase will not exceed a fraction per cent., even at altitudes of four and a half to six miles, the greatest height within the reach of men either by climbing mountains or by means of balloons. This conclusion is confirmed by the analyses of air collected by Welch in England during his aëronautic ascents.

[19] The complete absorption of the oxygen may be attained by introducing moist phosphorus into a definite volume of air; the occurrence of this is recognised by the fact of the phosphorus becoming non-luminous in the dark. The amount of oxygen may be determined by measuring the volume of nitrogen remaining. This method however cannot give accurate results, owing to a portion of the air being dissolved in the water, to the combination of some of the nitrogen with oxygen and to the necessity of introducing and withdrawing the phosphorus, which cannot be accomplished without introducing bubbles of air.

[20] For rapid and approximate analyses (technical and hygienic), such a mixture is very suitable for determining the amount of oxygen in mixtures of gases from which the substances absorbed by alkalis have first been removed. According to certain observers, this mixture evolves a certain (small) quantity of carbonic oxide after absorbing oxygen.

[21] Details of eudiometrical analysis must, as was pointed out in Chap. III., Note 32, be looked for in works on analytical chemistry. The same remark applies to the other analytical methods mentioned in this work. They are only described for the purpose of showing the diversity of the methods of chemical research.

[22] Air free from carbonic anhydride indicates after explosion the presence of a small quantity of carbonic anhydride, as De Saussure remarked, and air free from moisture, after being passed over red-hot copper oxide, appears invariably to contain a small quantity of water, as Boussingault has observed. These observations lead to the assumption that air always contains a certain quantity of gaseous hydrocarbons, like marsh gas, which, as we shall afterwards learn, is evolved from the earth, marshes, &c. Its amount, however, does not exceed a few hundredths per cent.

[23] The analyses of air are accompanied by errors, and there are variations of composition attaining hundredths per cent.; the average normal composition of air is therefore only correct to the first decimal place.

[24] These figures express the mean composition of air from an average of the most accurate determinations; they are accurate within ±0·05 p.c.

[25] In Chapter III., Note 4, an approximate calculation is made for the determination of the balance of oxygen in the entire atmosphere; it may therefore he supposed that the composition of air will vary from time to time, the relation between vegetation and the oxygen absorbing processes changes; but as the atmosphere of the earth can hardly have a definite limit and we have already seen (Chapter IV., Note 33) that there are observations confirming this, it follows that our atmosphere should vary in its component parts with the entire heavenly space, and therefore it must he supposed that any variation in the composition by weight of the air can only take place exceedingly slowly, and in a manner imperceptible by experiment.

[26] The amount of moisture contained in the air is considered in greater detail in the study of physics and meteorology and the subject has been mentioned above, in Chapter I., Note 1, where the methods of absorbing moisture from gases were pointed out.

[27] Soda-lime is prepared in the following manner:—Unslaked lime is finely powdered and mixed with a slightly warmed and very strong solution of caustic soda. The mixing should be done in an iron dish, and the materials should be well stirred together until the lime begins to slake. When the mass becomes hot, it boils, swells up, and solidifies, forming a porous mass very rich in alkali and capable of rapidly absorbing carbonic anhydride. A lump of caustic soda or potash presents a much smaller surface for absorption and therefore acts much less rapidly. It is necessary to place an apparatus for absorbing water after the apparatus for absorbing the carbonic anhydride, because the alkali in absorbing the latter gives off water.

[28] It is evident that the calcium chloride employed for absorbing the water should be free from lime or other alkalis in order that it may not retain carbonic anhydride. Such calcium chloride may be prepared in the following manner: A perfectly neutral solution of calcium chloride is prepared from lime and hydrochloric acid; it is then carefully evaporated first on a water-bath and then on a sand-bath. When the solution attains a certain strength a scum is formed, which solidifies at the surface. This scum is collected, and will be found to be free from caustic alkalis. It is necessary in any case to test it before use, as otherwise a large error may be introduced into the results, owing to the presence of free alkali (lime). It is best to pass carbonic anhydride through the tube containing the calcium chloride for some time before the experiment, in order to saturate any free alkali that may remain from the decomposition of a portion of the calcium chloride by water, CaCl₂ + 2H₂O = CaOH₂O + 2HCl.

[29] Recourse is had to special methods when the determination only takes note of the carbonic anhydride of the air. For instance, it is absorbed by an alkali which does not contain carbonates (by a solution of baryta or caustic soda mixed with baryta), and then the carbonic anhydride is expelled by an excess of an acid, and its amount determined by the volume given off. A rapid method of determining CO₂ (for hygienic purposes) is given by the fall of tension produced by the introduction of an alkali (the air having been either brought to dryness or saturated with moisture). Dr. Schidloffsky's apparatus is based upon this principle. The question as to the amount of carbonic anhydride present in the air has been submitted to many voluminous and exact researches, especially those of Reiset, Schloesing, Müntz, and Aubin, who showed that the amount is not subject to such variations as at first announced on the basis of incomplete and insufficiently accurate determinations.

[30] It is a different case in enclosed spaces, in dwellings, cellars, wells, caves, and mines, where the renewal of air is impeded. Under these circumstances large quantities of carbonic anhydride may accumulate. In cities, where there are many conditions for the evolution of carbonic anhydride (respiration, decomposition, combustion), its amount is greater than in free air, yet even in still weather the difference does not often exceed one ten-thousandth (that is, rarely attains 4 instead of 2·9 vols. in 10000 vols. of air).

[31] In the sea as well as in fresh water, carbonic acid occurs in two forms, directly dissolved in the water, and combined with lime as calcium bicarbonate (hard waters sometimes contain very much carbonic acid in this form). The tension of the carbonic anhydride in the first form varies with the temperature, and its amount with the partial pressure, and that in the form of acid salts is under the same conditions, for direct experiments have shown a similar dependence in this case, although the quantitative relations are different in the two cases.

[32] In studying the phenomena of nature the conclusion is arrived at that the universally reigning state of mobile equilibrium forms the chief reason for that harmonious order which impresses all observers. It not unfrequently happens that we do not see the causes regulating the order and harmony; in the particular instance of carbonic anhydride, it is a striking circumstance that in the first instance a search was made for an harmonious and strict uniformity, and in incidental (insufficiently accurate and fragmentary) observations conditions were even found for concluding it to be absent. When, later, the rule of this uniformity was confirmed, then the causes regulating such order were also discovered. The researches of Schloesing were of this character. Deville's idea of the dissociation of the acid carbonates of sea-water is suggested in them. In many other cases also, a correct interpretation can only follow from a detailed investigation.

[33] The difference of the weight of a litre of dry air (free from carbonic anhydride) at 0° and 760 mm., at different longitudes and altitudes, depends on the fact that the force of gravity varies under these conditions, and with it the pressure of the barometrical column also varies. This is treated in detail in my works On the Elasticity of Gases and On Barometric Levellings, and ‘The Publications of the Weights and Measures Department’ (Journal of the Russian Physico-Chemical Society, 1894).

In reality the weight is not measured in absolute units of weight (in pressure—refer to works on mechanics and physics), but in relative units (grams, scale weights) whose mass is invariable, and therefore the variation of the weight of the weights itself with the change of gravity must not be here taken into account, for we are here dealing with weights proportional to masses, since with a change of locality the weight of the weights varies as the weight of a given volume of air does. In other words: the mass of a substance always remains constant, but the pressure produced by it varies with the acceleration of gravity: the gram, pound, and other units of weight are really units of mass.

[34] The tension of the aqueous vapour in the air is determined by hygrometers and other similar methods. It may also be determined by analysis (see Chapter I., Note 1).

[35] For rapid calculation the weight of a litre of air (in a room) in St. Petersburg, may under these conditions (H, t, and f) be obtained by the formula e = 1·20671 + 0·0016 [H₁ - 755 + 2·6(18° - t°)] where H₁ = H - 0·38f. In determining the weight of small and heavy objects (crucibles, &c. in analysis, and in determining the specific gravities of liquids, &c.) a correction may be introduced for the loss of weight in the air of the room, by taking the weight of a litre of air displaced as 1·2 gram, and consequently 0·0012 gram for every cubic centimetre. But if gases or, in general, large vessels are weighed, and the weighings require to be accurate, it is necessary to take into account all the data for the determination of the density of the air (t, H, and f), because sensitive balances can determine the possible variations of the weight of air, as in the case of a litre the weight of air varies in centigrams, even at a constant temperature, with variations of H and f. Some time ago (1859) I proposed the following method and applied it for this purpose. A large light and closed vessel is taken, and its volume and weight in a vacuum are accurately determined, and verified from time to time. On weighing it we obtain the weight in air of a given density, and by subtracting this weight from its absolute weight and dividing by its volume we obtain the density of the air.

[36] Schloesing studied the equilibrium of the ammonia of the atmosphere and of the rivers, seas, &c., and showed that the amount of the gas is interchangeable between them. The ratio between the amount of ammonia in a cubic metre of air and a litre of water at 0° = 0·004, at 10° = 0·010, at 25° = 0·040 to 1, and therefore in nature there is a state of equilibrium in the amount of ammonia in the atmosphere and waters.

[37] Whilst formed in the air these oxidising substances (N₂O₃, ozone and hydrogen peroxide) at the same time rapidly disappear from it by oxidising those substances which are capable of being oxidised. Owing to this instability their amounts vary considerably, and, as would be expected, they are met with to an appreciable amount in pure air, whilst their amount decreases to zero in the air of cities, and especially in dwellings where there is a maximum of substances capable of oxidisation and a minimum of conditions for the formation of such bodies. There is a causal connection between the amount of these substances present in the air and its purity—that is, the amount of foreign residues of organic origin liable to oxidation present in the air. Where there is much of such residues their amount must be small. When they are present the amount of organic substances must be small, as otherwise they would be destroyed. For this reason efforts have been made to apply ozone for purifying the air by evolving it by artificial means in the atmosphere; for instance, by passing a series of electrical sparks through the ventilating pipes conveying air into a building. Air thus ozonised destroys by oxidation—that is, brings about the combustion of—the organic residues present in the air, and thus will serve for purifying it. For these reasons the air of cities contains less ozone and such like oxidising agents than country air. This forms the distinguishing feature of country air. However, animal life cannot exist in air containing a comparatively large amount of ozone.

[38] Amongst them we may mention iodine and alcohol, C₂H₆O, which Müntz found to be always present in air, the soil, and water, although in minute traces only.

[39] A portion of the atmospheric dust is of cosmic origin; this is undoubtedly proved by the fact of its containing metallic iron as do meteorites. Nordenskiöld found iron in the dust covering snow, and Tissandier in every kind of air, although naturally in very small quantities.

[40] The idea of the spontaneous growth of organisms in a suitable medium, although still upheld by many, has since the work of Pasteur and his followers (and to a certain extent of his predecessors) been discarded, because it has been proved how, when, and whence (from the air, water, &c.) the germs appear; that fermentation as well as infectious diseases cannot take place without them; and chiefly because it has been shown that any change accompanied by the development of the organisms introduced may be brought about at will by the introduction of the germs into a suitable medium.

[41] In further confirmation of the fact that putrefaction and fermentation depend on germs carried in the air, we may cite the circumstance that poisonous substances destroying the life of organisms stop or hinder the appearance of the above processes. Air which has been heated to redness or passed through sulphuric acid no longer contains the germs of organisms, and loses the faculty of producing fermentation and putrefaction.

[42] Their presence in the air is naturally due to the diffusion of germs into the atmosphere, and owing to their microscopical dimensions, they, as it were, hang in the air in virtue of their large surfaces compared to their weight. In Paris the amount of dust suspended in the air equals from 6 (after rain) to 23 grams per 1,000 c.m. of air.

[43] We see similar cases everywhere. For example, the predominating mass of sand and clay in the soil takes hardly any chemical part in the economy of the soil in respect to the nourishment of plants. The plants by their roots search for substances which are diffused in comparatively small quantities in the soil. If a large quantity of these nourishing substances are removed, then the plants will not develop in the soil, just as animals die in oxygen.

[44] A man in breathing burns about 10 grams of carbon per hour—that is, he produces about 880 grams, or (as 1 cub.m. of carbonic anhydride weighs about 2,000 grams) about ⁵⁄₁₂ c.m. of carbonic anhydride. The air coming from the lungs contains 4 p.c. of carbonic anhydride by volume. The exhaled air acts as a direct poison, owing to this gas and to other impurities.

[45] For this reason candles, lamps, and gas change the composition of air almost in the same way as respiration. In the burning of 1 kilogram of stearin candles, 50 cubic metres of air are changed as by respiration—that is, 4 p.c. of carbonic anhydride will be formed in this volume of air. The respiration of animals and exhalations from their skins, and especially from the intestines and the excrements and the transformations taking place in them, contaminate the air to a still greater extent, because they introduce other volatile substances besides carbonic anhydride into the air. At the same time that carbonic anhydride is formed the amount of oxygen in the air decreases, and there is noticed the appearance of miasmata which occur in but small quantity, but which are noticeable in passing from fresh air into a confined space full of such adulterated air. The researches of Schmidt and Leblanc and others show that even with 20·6 p.c. of oxygen (instead of 20·9 p.c.), when the diminution is due to respiration, air becomes noticeably less fit for respiration, and that the heavy feeling experienced in such air increases with a lesser percentage of oxygen. It is difficult to remain for a few minutes in air containing 17·2 p.c. of oxygen. These observations were chiefly obtained by observations on the air of different mines, at different depths below the surface. The air of theatres and buildings full of people also proves to contain less oxygen; it was found on one occasion that at the end of a theatrical representation the air in the stalls contained 20·75 p.c. of oxygen, whilst the air at the upper part of the theatre contained only 20·36 p.c. The amount of carbonic anhydride in the air may be taken as a measure of its purity (Pettenkofer). When it reaches 1 p.c. it is very difficult for human beings to remain long in such air, and it is necessary to set up a vigorous ventilation for the removal of the adulterated air. In order to keep the air in dwellings in a uniformly good state, it is necessary to introduce at least 10 cubic metres of fresh air per hour per person. We saw that a man exhales about five-twelfths of a cubic metre of carbonic anhydride per day. Accurate observations have shown that air containing one-tenth p.c. of exhaled carbonic anhydride (and consequently also a corresponding amount of the other substances evolved together with it) is not felt to be oppressive; and therefore the five-twelfth cubic metres of carbonic anhydride should be diluted with 420 cubic metres of fresh air if it be desired to keep not more than one-tenth p.c. (by volume) of carbonic anhydride in the air. Hence a man requires 420 cubic metres of air per day, or 18 cubic metres per hour. With the introduction of only 10 cubic metres of fresh air per person, the amount of carbonic anhydride may reach one-fifth p.c., and the air will not then be of the requisite freshness.

[46] The ventilation of inhabited buildings is most necessary, and is even indispensable in hospitals, schools, and similar buildings. In winter it is carried on by the so-called calorifiers or stoves heating the air before it enters. The best kind of calorifiers in this respect are those in which the fresh cold air is led through a series of pipes heated by the hot gases coming from a stove. In ventilation, particularly during winter, care is taken that the incoming air shall be moist, because in winter the amount of moisture in the air is very small. Ventilation, besides introducing fresh air into a dwelling-place, must also withdraw the air already spoilt by respiration and other causes—that is, it is necessary to construct channels for the escape of the bad air, besides those for the introduction of fresh air. In ordinary dwelling-places, where not many people are congregated, the ventilation is conducted by natural means, in the heating by fires, through crevices, windows, and various orifices in walls, doors, and windows. In mines, factories, and workrooms ventilation is of the greatest importance.

Animal vitality may still continue for a period of several minutes in air containing up to 30 p.c. of carbonic anhydride, if the remaining 70 p.c. consist of ordinary air; but respiration ceases after a certain time, and death may even ensue. The flame of a candle is very easily extinguished in an atmosphere containing from 5 to 6 p.c. of carbonic anhydride, but animal vitality can be sustained in it for a somewhat long time, although the effect of such air is exceedingly painful even to the lower animals. There are mines in which a lighted candle easily goes out from the excess of carbonic anhydride, but in which the miners have to remain for a long time. The presence of 1 p.c. of carbonic oxide is deadly even to cold-blooded animals. The air in the galleries of a mine where blasting has taken place, is known to produce a state of insensibility resembling that produced by charcoal fumes. Deep wells and vaults not unfrequently contain similar substances, and their atmosphere often causes suffocation. The atmospheres of such places cannot be tested by lowering a lighted candle into it, as these poisonous gases would not extinguish the flame. This method only suffices to indicate the amount of carbonic anhydride. If a candle keeps alight, it signifies that there is less than 6 p.c. of this gas. In doubtful cases it is best to lower a dog or other animal into the air to be tested. If CO₂ be very carefully added to air, the flame of a candle is not extinguished (although it becomes very much smaller) even when the gas amounts to 12 p.c. of air. Researches made by F. Clowes (1894) show that the flames (in every case ¾ in. long) of different combustible substances are extinguished by the gradual addition of different percentages of nitrogen and carbonic acid to the air; the percentage sufficient to extinguish the flame being as follows (the percentage of oxygen is given in parenthesis):

The flames of all solid and liquid substances is extinguished by almost the same percentage of CO₂ or N₂, but the flames of different gases vary in this respect, and hydrogen continues to burn in mixtures which are far poorer in oxygen than those in which the flames of other combustible gases are extinguished; the flame of methane CH₄ is the most easily extinguished. The percentage of nitrogen may be greater than that of CO₂. This, together with the fact that, under the above circumstances, the flame of a gas before going out becomes fainter and increases in size, seems to indicate that the chief reason for the extinction of the flame is the fall in its temperature.

[47] Different so-called disinfectants purify the air, and prevent the injurious action of certain of its components by changing or destroying them. Disinfection is especially necessary in those places where a considerable amount of volatile substances are evolved into the air, and where organic substances are decomposed; for instance, in hospitals, closets, &c. The numerous disinfectants are of the most varied nature. They may be divided into oxidising, antiseptic, and absorbent substances. To the oxidising substances used for disinfection belong chlorine, and various substances evolving it, because chlorine in the presence of water oxidises the majority of organic substances, and this is why chlorine is used as a disinfectant for Siberian plagues. Further, to this class belong the permanganates of the alkalis and peroxide of hydrogen, as substances easily oxidising matters dissolved in water; these salts are not volatile like chlorine, and therefore act much more slowly, and in a much more limited sphere. Antiseptic substances are those which convert organic substances into such as are little prone to change, and prevent putrefaction and fermentation. They most probably kill the germs of organisms occurring in miasmata. The most important of these substances are creosote and phenol (carbolic acid), which occur in tar, and act in preserving smoked meat. Phenol is a substance little soluble in water, volatile, oily, and having the characteristic smell of smoked objects. Its action on animals in considerable quantities is injurious, but in small quantities, used in the form of a weak solution, it prevents the change of animal matter. The smell of privies, which depends on the change of excremental matter, may be easily removed by means of chlorine or phenol. Salicylic acid, thymol, common tar, and especially its solution in alkalis as proposed by Nensky, &c., are also substances having the same property. Absorbent substances are of no less importance, especially as preventatives, than the preceding two classes of disinfectants, inasmuch as they are innocuous. They are those substances which absorb the odoriferous gases and vapours emitted during putrefaction, which are chiefly ammonia, sulphuretted hydrogen, and other volatile compounds. To this class belong charcoal, certain salts of iron, gypsum, salts of magnesia, and similar substances, as well as peat, mould, and clay. Questions of disinfection and ventilation appertain to the most serious problems of common life and hygiene. These questions are so vast that we are here able only to give a short outline of their nature.