THE
PRINCIPLES OF CHEMISTRY

By D. MENDELÉEFF
TRANSLATED FROM THE RUSSIAN (SIXTH EDITION) BY
GEORGE KAMENSKY, A.R.S.M.
OF THE IMPERIAL MINT, ST PETERSBURG: MEMBER OF THE RUSSIAN PHYSICO-CHEMICAL SOCIETY
EDITED BY
T. A. LAWSON, B.Sc. Ph.D.
EXAMINER IN COAL-TAR PRODUCTS TO THE CITY AND GUILDS OF LONDON INSTITUTE FELLOW OF THE INSTITUTE OF CHEMISTRY
IN TWO VOLUMES
VOLUME II.
LONGMANS, GREEN, AND CO
39 PATERNOSTER ROW, LONDON
NEW YORK AND BOMBAY
1897
All rights reserved

[Table III.]

The periodic dependence of the composition of the simplest compounds and properties of the simple bodies upon the atomic weights of the elements.

[A] From analogy there is reason for thinking that the atomic weight of selenium is really slightly less than 79·0.

Columns 1, 2, 3, and 4 give the molecular composition of the hydrogen and metallo-organic compounds, exhibiting the most characteristic forms assumed by the elements. The first column contains only those which correspond to the form RX₄, the second column those of the form RX₃, the third of the form RX₂, and the fourth of the form RX, so that the periodicity stands out clearly (see Column 16).

Column 5 contains the symbols of all the more or less well-known elements, placed according to the order of the magnitude of their atomic weights.

Column 6 contains the atomic weights of the elements according to the most trustworthy determinations. The names of the investigators are given in parenthesis. The atomic weight of oxygen, taken as 16, forms the basis upon which these atomic weights were calculated. Some of these have been recalculated by me on the basis of Stas's most trustworthy data (see Chapter [XXIV.] and the numbers given by Stas in the table, where they are taken according to van der Plaats and Thomsen's calculations).

Columns 7–14 contain the composition of the saline compounds of the elements, placed according to their forms, RX, RX₂ to RX₈ (in the 14^th column). If the element R has a metallic character like H, Li, Be, &c., then X represents Cl, NO₃, ½ SO₄, &c., haloid radicles, or (OH) if a perfect hydrate is formed (alkali, aqueous base), or ½ O, ½ S, &c. when an anhydrous oxide, sulphide, &c. is formed. For instance, NaCl, Mg(NO₃)₂, Al₂(SO₄)₃, correspond to NaX, MgX₂, and AlX₃; so also Na(OH), Mg(OH)₂, Al(OH)₃, Na₂O, MgO, Al₂O₃, &c. But if the element, like C or N, be of a metalloid or acid character, X must be regarded as (OH) in the formation of hydrates; (OM) in the formation of salts, where M is the equivalent of a metal, ½ O in the formation of an anhydride, and Cl in the formation of a chloranhydride; and in this case (i.e. in the acid compounds) Z is put in the place of X; for example, the formulæ COZ₂, NO₂Z, MNO₂Z, FeO₂Z₂, and IZ₃ correspond to CO(NaO)₂ = Na₂CO₃, COCl₂, CO₂, NO₂(NaO) = NaNO₃, NO₂Cl, NO₂(OH) = HNO₃; MnO₃(OK) = KMnO₄, ICl, &c.

The 15th column gives the compositions of the peroxides of the elements, taking them as anhydrous. An asterisk (*) is attached to those of which the composition has not been well established, and a dash (—) shows that for a given element no peroxides have yet been obtained. The peroxides contain more oxygen than the higher saline oxides of the same elements, are powerfully oxidising, and easily give peroxide of hydrogen. This latter circumstance necessitates their being referred to the type of peroxide of hydrogen, if bases and acids are referred to the type of water (see Chapter XV., Note [7] and [11 bis]).

The 16th column gives the composition of the lower hydrogen compounds like N₃H and Na₂H. They may often be regarded as alloys of hydrogen, which is frequently disengaged by them at a comparatively moderate temperature. They differ greatly in their nature from the hydrogen compounds given in columns 1–4 (see Note [12]).

Column 17 gives the specific gravity of the elements in a solid and a liquid state. An asterisk (*) is placed by those which can either only be assumed from analogy (for example, the sp. gr. of fluorine and hydrogen, which have not been obtained in a liquid state), or which vary very rapidly with a variation of temperature and pressure (like oxygen and nitrogen), or physical state (for instance, carbon in passing from the state of charcoal to graphite and diamond). But as the sp. gr. in general varies with the temperature, mechanical condition, &c., the figures given, although chosen from the most trustworthy sources, can only be regarded as approximate, and not as absolutely true. They clearly show a certain periodicity; for instance, the sp. gr. diminishes from Al on both sides (Al, Mg, Na, with decreasing atomic weight; and Al, Si, P, S, Cl, with increasing atomic weight, it also diminishes on both sides from Cu, Ru, and Os.)

The same remarks refer to the figures in the 18th column, which gives the so-called atomic volumes of the simple bodies, or the quotient of their atomic weight and specific gravity. For Na, K, Rb, and Cs the atomic volume is greatest among the neighbouring elements. For Ni, Pd, and Os it is least, and this indicates the periodicity of this property of the simple bodies.

The last (19th) column gives the melting points of the simple bodies. Here also a periodicity is seen, i.e. a maximum and minimum value between which there are intermediate values, as we see, for instance, in the series Cl, K, Ca, Sc, and Ti, or in the series Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Ge.

PRINCIPLES OF CHEMISTRY
CHAPTER XV
THE GROUPING OF THE ELEMENTS AND THE PERIODIC LAW

It is seen from the examples given in the preceding chapters that the sum of the data concerning the chemical transformations proper to the elements (for instance, with respect to the formation of acids, salts, and other compounds having definite properties) is insufficient for accurately determining the relationship of the elements, inasmuch as this may be many-sided. Thus, lithium and barium are in some respects analogous to sodium and potassium, and in others to magnesium and calcium. It is evident, therefore, that for a complete judgment it is necessary to have, not only qualitative, but also quantitative, exact and measurable, data. When a property can be measured it ceases to be vague, and becomes quantitative instead of merely qualitative.

Among these measurable properties of the elements, or of their corresponding compounds, are: (a) isomorphism, or the analogy of crystalline forms; and, connected with it, the power to form crystalline mixtures which are isomorphous; (b) the relation of the volumes of analogous compounds of the elements; (c) the composition of their saline compounds; and (d) the relation of the atomic weights of the elements. In this chapter we shall briefly consider these four aspects of the matter, which are exceedingly important for a natural and fruitful grouping of the elements, facilitating, not only a general acquaintance with them, but also their detailed study.

Historically the first, and an important and convincing, method for finding a relationship between the compounds of two different elements is by isomorphism. This conception was introduced into chemistry by Mitscherlich (in 1820), who demonstrated that the corresponding salts of arsenic acid, H₃AsO₄, and phosphoric acid, H₃PO₄, crystallise with an equal quantity of water, show an exceedingly close resemblance in crystalline form (as regards the angles of their faces and axes), and are able to crystallise together from solutions, forming crystals containing a mixture of the isomorphous compounds. Isomorphous substances are those which, with an equal number of atoms in their molecules, present an analogy in their chemical reactions, a close resemblance in their properties, and a similar or very nearly similar crystalline form: they often contain certain elements in common, from which it is to be concluded that the remaining elements (as in the preceding example of As and P) are analogous to each other. And inasmuch as crystalline forms are capable of exact measurement, the external form, or the relation of the molecules which causes their grouping into a crystalline form, is evidently as great a help in judging of the internal forces acting between the atoms as a comparison of reactions, vapour densities, and other like relations. We have already seen examples of this in the preceding pages.[1] It will be sufficient to call to mind that the compounds of the alkali metals with the halogens RX, in a crystalline form, all belong to the cubic system and crystallise in octahedra or cubes—for example, sodium chloride, potassium chloride, potassium iodide, rubidium chloride, &c. The nitrates of rubidium and cæsium appear in anhydrous crystals of the same form as potassium nitrate. The carbonates of the metals of the alkaline earths are isomorphous with calcium carbonate—that is, they either appear in forms like calc spar or in the rhombic system in crystals analogous to aragonite.[1 bis] Furthermore, sodium nitrate crystallises in rhombohedra, closely resembling the rhombohedra of calc spar (calcium carbonate), CaCO₃, whilst potassium nitrate appears in the same form as aragonite, CaCO₃, and the number of atoms in both kinds of salts is the same: they all contain one atom of a metal (K, Na, Ca), one atom of a non-metal (C, N), and three atoms of oxygen. The analogy of form evidently coincides with an analogy of atomic composition. But, as we have learnt from the previous description of these salts, there is not any close resemblance in their properties. It is evident that calcium carbonate approaches more nearly to magnesium carbonate than to sodium nitrate, although their crystalline forms are all equally alike. Isomorphous substances which are perfectly analogous to each other are not only characterised by a close resemblance of form (homeomorphism), but also by the faculty of entering into analogous reactions, which is not the case with RNO₃ and RCO₃. The most important and direct method of recognising perfect isomorphism—that is, the absolute analogy of two compounds—is given by that property of analogous compounds of separating from solutions in homogeneous crystals, containing the most varied proportions of the analogous substances which enter into their composition. These quantities do not seem to be in dependence on the molecular or atomic weights, and if they are governed by any laws they must be analogous to those which apply to indefinite chemical compounds.[2] This will be clear from the following examples. Potassium chloride and potassium nitrate are not isomorphous with each other, and are in an atomic sense composed in a different manner. If these salts be mixed in a solution and the solution be evaporated, independent crystals of the two salts will separate, each in that crystalline form which is proper to it. The crystals will not contain a mixture of the two salts. But if we mix the solutions of two isomorphous salts together, then, under certain circumstances, crystals will be obtained which contain both these substances. However, this cannot be taken as an absolute rule, for if we take a solution saturated at a high temperature with a mixture of potassium and sodium chlorides, then on evaporation sodium chloride only will separate, and on cooling only potassium chloride. The first will contain very little potassium chloride, and the latter very little sodium chloride.[3] But if we take, for example, a mixture of solutions of magnesium sulphate and zinc sulphate, they cannot be separated from each other by evaporating the mixture, notwithstanding the rather considerable difference in the solubility of these salts. Again, the isomorphous salts, magnesium carbonate, and calcium carbonate are found together—that is, in one crystal—in nature. The angle of the rhombohedron of these magnesia-lime spars is intermediate between the angles proper to the two spars individually (for calcium carbonate, the angle of the rhombohedron is 105° 8′; magnesium carbonate, 107° 30′; CaMg(CO₃)₂, 106° 10′). Certain of these isomorphous mixtures of calc and magnesia spars appear in well-formed crystals, and in this case there not unfrequently exists a simple molecular proportion of strictly definite chemical combination between the component salts—for instance, CaCO₃,MgCO₃—whilst in other cases, especially in the absence of distinct crystallisation (in dolomites), no such simple molecular proportion is observable: this is also the case in many artificially prepared isomorphous mixtures. The microscopical and crystallo-optical researches of Professor Inostrantzoff and others show that in many cases there is really a mechanical, although microscopically minute, juxtaposition in one whole of the heterogeneous crystals of calcium carbonate (double refracting) and of the compound CaMgC₂O₆. If we suppose the adjacent parts to be microscopically small (on the basis of the researches of Mallard, Weruboff, and others), we obtain an idea of isomorphous mixtures. A formula of the following kind is given to isomorphous mixtures: for instance, for spars, RCO₃, where R = Mg, Ca, and where it may be Fe,Mn …, &c. This means that the Ca is partially replaced by Mg or another metal. Alums form a common example of the separation of isomorphous mixtures from solutions. They are double sulphates (or seleniates) of alumina (or oxides isomorphous with it) and the alkalis, which crystallise in well-formed crystals. If aluminium sulphate be mixed with potassium sulphate, an alum separates, having the composition KAlS₂O₈,12H₂O. If sodium sulphate or ammonium sulphate, or rubidium (or thallium) sulphate be used, we obtain alums having the composition RAlS₂O₈,12H₂O. Not only do they all crystallise in the cubic system, but they also contain an equal atomic quantity of water of crystallisation (12H₂O). Besides which, if we mix solutions of the potassium and ammonium (NH₄AlS₂O₈,12H₂O) alums together, then the crystals which separate will contain various proportions of the alkalis taken, and separate crystals of the alums of one or the other kind will not be obtained, but each separate crystal will contain both potassium and ammonium. Nor is this all; if we take a crystal of a potassium alum and immerse it in a solution capable of yielding ammonia alum, the crystal of the potash alum will continue to grow and increase in size in this solution—that is, a layer of the ammonia or other alum will deposit itself upon the planes bounding the crystal of the potash alum. This is very distinctly seen if a colourless crystal of a common alum be immersed in a saturated violet solution of chrome alum, KCrS₂O₈,12H₂O, which then deposits itself in a violet layer over the colourless crystal of the alumina alum, as was observed even before Mitscherlich noticed it. If this crystal be then immersed in a solution of an alumina alum, a layer of this salt will form over the layer of chrome alum, so that one alum is able to incite the growth of the other. If the deposition proceed simultaneously, the resultant intermixture may be minute and inseparable, but its nature is understood from the preceding experiments; the attractive force of crystallisation of isomorphous substances is so nearly equal that the attractive power of an isomorphous substance induces a crystalline superstructure exactly the same as would be produced by the attractive force of like crystalline particles. From this it is evident that one isomorphous substance may induce the crystallisation[4] of another. Such a phenomenon explains, on the one hand, the aggregation of different isomorphous substances in one crystal, whilst, on the other hand, it serves as a most exact indication of the nearness both of the molecular composition of isomorphous substances and of those forces which are proper to the elements which distinguish the isomorphous substances. Thus, for example, ferrous sulphate or green vitriol crystallises in the monoclinic system and contains seven molecules of water, FeSO₄,7H₂O, whilst copper vitriol crystallises with five molecules of water in the triclinic system, CuSO₄,5H₂O; nevertheless, it may be easily proved that both salts are perfectly isomorphous; that they are able to appear in identically the same forms and with an equal molecular amount of water. For instance, Marignac, by evaporating a mixture of sulphuric acid and ferrous sulphate under the receiver of an air-pump, first obtained crystals of the hepta-hydrated salt, and then of the penta-hydrated salt FeSO₄,5H₂O, which were perfectly similar to the crystals of copper sulphate. Furthermore, Lecoq de Boisbaudran, by immersing crystals of FeSO₄,7H₂O in a supersaturated solution of copper sulphate, caused the latter to deposit in the same form as ferrous sulphate, in crystals of the monoclinic system, CuSO₄,7H₂O.

Hence it is evident that isomorphism—that is, the analogy of forms and the property of inducing crystallisation—may serve as a means for the discovery of analogies in molecular composition. We will take an example in order to render this clear. If, instead of aluminium sulphate, we add magnesium sulphate to potassium sulphate, then, on evaporating the solution, the double salt K₂MgS₂O₈,6H₂O (Chapter XIV., Note [28]) separates instead of an alum, and the ratio of the component parts (in alums one atom of potassium per 2SO₄, and here two atoms) and the amount of water of crystallisation (in alums 12, and here 6 equivalents per 2SO₄) are quite different; nor is this double salt in any way isomorphous with the alums, nor capable of forming an isomorphous crystalline mixture with them, nor does the one salt provoke the crystallisation of the other. From this we must conclude that although alumina and magnesia, or aluminium and magnesium, resemble each other, they are not isomorphous, and that although they give partially similar double salts, these salts are not analogous to each other. And this is expressed in their chemical formulæ by the fact that the number of atoms in alumina or aluminium oxide, Al₂O₃, is different from the number in magnesia, MgO. Aluminium is trivalent and magnesium bivalent. Thus, having obtained a double salt from a given metal, it is possible to judge of the analogy of the given metal with aluminium or with magnesium, or of the absence of such an analogy, from the composition and form of this salt. Thus zinc, for example, does not form alums, but forms a double salt with potassium sulphate, which has a composition exactly like that of the corresponding salt of magnesium. It is often possible to distinguish the bivalent metals analogous to magnesium or calcium from the trivalent metals, like aluminium, by such a method. Furthermore, the specific heat and vapour density serve as guides. There are also indirect proofs. Thus iron gives ferrous compounds, FeX₂, which are isomorphous with the compounds of magnesium, and ferric compounds, FeX₃, which are isomorphous with the compounds of aluminium; in this instance the relative composition is directly determined by analysis, because, for a given amount of iron, FeCl₂ only contains two-thirds of the amount of chlorine which occurs in FeCl₃, and the composition of the corresponding oxygen compounds, i.e. of ferrous oxide, FeO, and ferric oxide, Fe₂O₃, clearly indicates the analogy of the ferrous oxide with MgO and of the ferric oxide with Al₂O₃.

Thus in the building up of similar molecules in crystalline forms we see one of the numerous means for judging of the internal world of molecules and atoms, and one of the weapons for conquests in the invisible world of molecular mechanics which forms the main object of physico-chemical knowledge. This method[5] has more than once been employed for discovering the analogy of elements and of their compounds; and as crystals are measurable, and the capacity to form crystalline mixtures can be experimentally verified, this method is a numerical and measurable one, and in no sense arbitrary.

The regularity and simplicity expressed by the exact laws of crystalline form repeat themselves in the aggregation of the atoms to form molecules. Here, as there, there are but few forms which are essentially different, and their apparent diversity reduces itself to a few fundamental differences of type. There the molecules aggregate themselves into crystalline forms; here, the atoms aggregate themselves into molecular forms or into the types of compounds. In both cases the fundamental crystalline or molecular forms are liable to variations, conjunctions, and combinations. If we know that potassium gives compounds of the fundamental type KX, where X is a univalent element (which combines with one atom of hydrogen, and is, according to the law of substitution, able to replace it), then we know the composition of its compounds: K₂O, KHO, KCl, NH₂K, KNO₃, K₂SO₄, KHSO₄, K₂Mg(SO₄)₂,6H₂O, &c. All the possible derivative crystalline forms are not known. So also all the atomic combinations are not known for every element. Thus in the case of potassium, KCH₃, K₃P, K₂Pt, and other like compounds which exist for hydrogen or chlorine, are unknown.

Only a few fundamental types exist for the building up of atoms into molecules, and the majority of them are already known to us. If X stand for a univalent element, and R for an element combined with it, then eight atomic types may be observed:—

RX, RX₂, RX₃, RX₄, RX₅, RX₆, RX₇, RX₈.

Let X be chlorine or hydrogen. Then as examples of the first type we have: H₂, Cl₂, HCl, KCl, NaCl, &c. The compounds of oxygen or calcium may serve as examples of the type RX₂: OH₂, OCl₂, OHCl, CaO, Ca(OH)₂, CaCl₂, &c. For the third type RX₃ we know the representative NH₃ and the corresponding compounds N₂O₃, NO(OH), NO(OK), PCl₃, P₂O₃, PH₃, SbH₃, Sb₂O₃, B₂O₃, BCl₃, Al₂O₃, &c. The type RX₄ is known among the hydrogen compounds. Marsh gas, CH₄, and its corresponding saturated hydrocarbons, C_nH_2n+2, are the best representatives. Also CH₃Cl, CCl₄, SiCl₄, SnCl₄, SnO₂, CO₂, SiO₂, and a whole series of other compounds come under this class. The type RX₅ is also already familiar to us, but there are no purely hydrogen compounds among its representatives. Sal-ammoniac, NH₄Cl, and the corresponding NH₄(OH), NO₂(OH), ClO₂(OK), as well as PCl₅, POCl₃, &c., are representatives of this type. In the higher types also there are no hydrogen compounds, but in the type RX₆ there is the chlorine compound WCl₆. However, there are many oxygen compounds, and among them SO₃ is the best known representative. To this class also belong SO₂(OH)₂, SO₂Cl₂, SO₂(OH)Cl, CrO₃, &c., all of an acid character. Of the higher types there are in general only oxygen and acid representatives. The type RX₇ we know in perchloric acid, ClO₃(OH), and potassium permanganate, MnO₃(OK), is also a member. The type RX₈ in a free state is very rare; osmic anhydride, OsO₄, is the best known representative of it.[6]

The four lower types RX, RX₂, RX₃, and RX₄ are met with in compounds of the elements R with chlorine and oxygen, and also in their compounds with hydrogen, whilst the four higher types only appear for such acid compounds as are formed by chlorine, oxygen, and similar elements.

Among the oxygen compounds the saline oxides which are capable of forming salts either through the function of a base or through the function of an acid anhydride attract the greatest interest in every respect. Certain elements, like calcium and magnesium, only give one saline oxide—for example, MgO, corresponding with the type MgX₂. But the majority of the elements appear in several such forms. Thus copper gives CuX and CuX₂, or Cu₂O and CuO. If an element R gives a higher type RX_n, then there often also exist, as if by symmetry, lower types, RX_n-2, RX_n-4, and in general such types as differ from RX_n by an even number of X. Thus in the case of sulphur the types SX₂, SX₄, and SX₆ are known—for example SH₂, SO₂, and SO₃. The last type is the highest, SX₆. The types SX₅ and SX₃ do not exist. But even and uneven types sometimes appear for one and the same element. Thus the types RX and RX₂ are known for copper and mercury.

Among the saline oxides only the eight types enumerated below are known to exist. They determine the possible formulæ of the compounds of the elements, if it be taken into consideration that an element which gives a certain type of combination may also give lower types. For this reason the rare type of the suboxides or quaternary oxides R₄O (for instance, Ag₄O, Ag₂Cl) is not characteristic; it is always accompanied by one of the higher grades of oxidation, and the compounds of this type are distinguished by their great chemical instability, and split up into an element and the higher compound (for instance, Ag₄O = 2Ag + Ag₂O). Many elements, moreover, form transition oxides whose composition is intermediate, which are able, like N₂O₄, to split up into the lower and higher oxides. Thus iron gives magnetic oxide, Fe₃O₄, which is in all respects (by its reactions) a compound of the suboxide FeO with the oxide Fe₂O₃. The independent and more or less stable saline compounds correspond with the following eight types :—

R₂O; salts RX, hydroxides ROH. Generally basic like K₂O, Na₂O, Hg₂O, Ag₂O, Cu₂O; if there are acid oxides of this composition they are very rare, are only formed by distinctly acid elements, and even then have only feeble acid properties; for example, Cl₂O and N₂O.

R₂O₂ or RO; salts RX₂, hydroxides R(OH)₂. The most simple basic salts R₂OX₂ or R(OH)X; for instance, the chloride Zn₂OCl₂; also an almost exclusively basic type; but the basic properties are more feebly developed than in the preceding type. For example, CaO, MgO, BaO, PbO, FeO, MnO, &c.

R₂O₃; salts RX₃, hydroxides R(OH)₃, RO(OH), the most simple basic salts ROX, R(OH)X₃. The bases are feeble, like Al₂O₃, Fe₂O₃, Tl₂O₃, Sb₂O₃. The acid properties are also feebly developed; for instance, in B₂O₃; but with the non-metals the properties of acids are already clear; for instance, P₂O₃, P(OH)₃.

R₂O₄ or RO₂; salts RX₄ or ROX₂, hydroxides R(OH)₄, RO(OH)₂. Rarely bases (feeble), like ZrO₂, PtO₂; more often acid oxides; but the acid properties are in general feeble, as in CO₂, SO₂, SnO₂. Many intermediate oxides appear in this and the preceding and following types.

R₂O₅; salts principally of the types ROX₃, RO₂X, RO(OH)₃, RO₂(OH), rarely RX₅. The basic character (X, a halogen, simple or complex; for instance, NO₃, Cl, &c.) is feeble; the acid character predominates, as is seen in N₂O₅, P₂O₅, Cl₂O₅; then X = OH, OK, &c., for example NO₂(OK).

R₂O₆ or RO₃; salts and hydroxides generally of the type RO₂X₂, RO₂(OH)₂. Oxides of an acid character, as SO₃, CrO₃, MnO₃. Basic properties rare and feebly developed as in UO₃.

R₂O₇; salts of the form RO₃X, RO₃(OH), acid oxides; for instance, Cl₂O₇, Mn₂O₇. Basic properties as feebly developed as the acid properties in the oxides R₂O.

R₂O₈ or RO₄. A very rare type, and only known in OsO₄ and RuO₄.

It is evident from the circumstance that in all the higher types the acid hydroxides (for example, HClO₄, H₂SO₄, H₃PO₄) and salts with a single atom of one element contain, like the higher saline type RO₄, not more than four atoms of oxygen; that the formation of the saline oxides is governed by a certain common principle which is best looked for in the fundamental properties of oxygen, and in general of the most simple compounds. The hydrate of the oxide RO₂ is of the higher type RO₂2H₂O = RH₄O₄ = R(HO)₄. Such, for example, is the hydrate of silica and the salts (orthosilicates) corresponding with it, Si(MO)₄. The oxide R₂O₅, corresponds with the hydrate R₂O₅3H₂O = 2RH₃O₄ = 2RO(OH)₃. Such is orthophosphoric acid, PH₃O₃. The hydrate of the oxide RO₃ is RO₃H₂O = RH₂O₄ = RO₂(OH)₂—for instance, sulphuric acid. The hydrate corresponding to R₂O₇ is evidently RHO = RO₃(OH)—for example, perchloric acid. Here, besides containing O₄, it must further be remarked that the amount of hydrogen in the hydrate is equal to the amount of hydrogen in the hydrogen compound. Thus silicon gives SiH₄ and SiH₄O₄, phosphorus PH₃ and PH₃O₄, sulphur SH₂ and SH₂O₄, chlorine ClH and ClHO₄. This, if it does not explain, at least connects in a harmonious and general system the fact that the elements are capable of combining with a greater amount of oxygen, the less the amount of hydrogen which they are able to retain. In this the key to the comprehension of all further deductions must be looked for, and we will therefore formulate this rule in general terms. An element R gives a hydrogen compound RH_n, the hydrate of its higher oxide will be RH_nO₄, and therefore the higher oxide will contain 2RH_nO₄ - nH₂O = R₂O_{8 - n}. For example, chlorine gives ClH, hydrate ClHO₄, and the higher oxide Cl₂O₇. Carbon gives CH₄ and CO₂. So also, SiO₂ and SiH₄ are the higher compounds of silicon with hydrogen and oxygen, like CO₂ and CH₄. Here the amounts of oxygen and hydrogen are equivalent. Nitrogen combines with a large amount of oxygen, forming N₂O₅, but, on the other hand, with a small quantity of hydrogen in NH₃. The sum of the equivalents of hydrogen and oxygen, occurring in combination with an atom of nitrogen, is, as always in the higher types, equal to eight. It is the same with the other elements which combine with hydrogen and oxygen. Thus sulphur gives SO₃; consequently, six equivalents of oxygen fall to an atom of sulphur, and in SH₂ two equivalents of hydrogen. The sum is again equal to eight. The relation between Cl₂O₇ and ClH is the same. This shows that the property of elements of combining with such different elements as oxygen and hydrogen is subject to one common law, which is also formulated in the system of the elements presently to be described.[7]

In the preceding we see not only the regularity and simplicity which govern the formation and properties of the oxides and of all the compounds of the elements, but also a fresh and exact means for recognising the analogy of elements. Analogous elements give compounds of analogous types, both higher and lower. If CO₂ and SO₂ are two gases which closely resemble each other both in their physical and chemical properties, the reason of this must be looked for not in an analogy of sulphur and carbon, but in that identity of the type of combination, RX₄, which both oxides assume, and in that influence which a large mass of oxygen always exerts on the properties of its compounds. In fact, there is little resemblance between carbon and sulphur, as is seen not only from the fact that CO₂ is the higher form of oxidation, whilst SO₂ is able to further oxidise into SO₃, but also from the fact that all the other compounds—for example, SH₂ and CH₄, SCl₂ and CCl₄, &c.—are entirely unlike both in type and in chemical properties. This absence of analogy in carbon and sulphur is especially clearly seen in the fact that the highest saline oxides are of different composition, CO₂ for carbon, and SO₃ for sulphur. In Chapter [VIII.] we considered the limit to which carbon tends in its compounds, and in a similar manner there is for every element in its compounds a tendency to attain a certain highest limit RX_n. This view was particularly developed in the middle of the present century by Frankland in studying the metallo-organic compounds, i.e. those in which X is wholly or partially a hydrocarbon radicle; for instance, X = CH₃ or C₂H₅ &c. Thus, for example, antimony, Sb (Chapter [XIX.]) gives, with chlorine, compounds SbCl₃ and SbCl₅ and corresponding oxygen compounds Sb₂O₃ and Sb₂O₅, whilst under the action of CH₃I, C₂H₅I, or in general EI (where E is a hydrocarbon radicle of the paraffin series), upon antimony or its alloy with sodium there are formed SbE₃ (for example, Sb(CH₃)₃, boiling at about 81°), which, corresponding to the lower form of combination SbX₃, are able to combine further with EI, or Cl₂, or O, and to form compounds of the limiting type SbX₅; for example, SbE₄Cl corresponding to NH₄Cl with the substitution of nitrogen by antimony, and of hydrogen by the hydrocarbon radicle. The elements which are most chemically analogous are characterised by the fact of their giving compounds of similar form RX_n. The halogens which are analogous give both higher and lower compounds. So also do the metals of the alkalis and of the alkaline earths. And we saw that this analogy extends to the composition and properties of the nitrogen and hydrogen compounds of these metals, which is best seen in the salts. Many such groups of analogous elements have long been known. Thus there are analogues of oxygen, nitrogen, and carbon, and we shall meet with many such groups. But an acquaintance with them inevitably leads to the questions, what is the cause of analogy and what is the relation of one group to another? If these questions remain unanswered, it is easy to fall into error in the formation of the groups, because the notions of the degree of analogy will always be relative, and will not present any accuracy or distinctness Thus lithium is analogous in some respects to potassium and in others to magnesium; beryllium is analogous to both aluminium and magnesium. Thallium, as we shall afterwards see and as was observed on its discovery, has much kinship with lead and mercury, but some of its properties appertain to lithium and potassium. Naturally, where it is impossible to make measurements one is reluctantly obliged to limit oneself to approximate comparisons, founded on apparent signs which are not distinct and are wanting in exactitude. But in the elements there is one accurately measurable property, which is subject to no doubt—namely, that property which is expressed in their atomic weights. Its magnitude indicates the relative mass of the atom, or, if we avoid the conception of the atom, its magnitude shows the relation between the masses forming the chemical and independent individuals or elements. And according to the teaching of all exact data about the phenomena of nature, the mass of a substance is that property on which all its remaining properties must be dependent, because they are all determined by similar conditions or by those forces which act in the weight of a substance, and this is directly proportional to its mass. Therefore it is most natural to seek for a dependence between the properties and analogies of the elements on the one hand and their atomic weights on the other.

This is the fundamental idea which leads to arranging all the elements according to their atomic weights. A periodic repetition of properties is then immediately observed in the elements. We are already familiar with examples of this:—

The essence of the matter is seen in these groups. The halogens have smaller atomic weights than the alkali metals, and the latter than the metals of the alkaline earths. Therefore, if all the elements be arranged in the order of their atomic weights, a periodic repetition of properties is obtained. This is expressed by the law of periodicity, the properties of the elements, as well as the forms and properties of their compounds, are in periodic dependence or (expressing ourselves algebraically) form a periodic function of the atomic weights of the elements.[8] Table I. of the periodic system of the elements, which is placed at the very beginning of this book, is designed to illustrate this law. It is arranged in conformity with the eight types of oxides described in the preceding pages, and those elements which give the oxides, R₂O and consequently salts RX, form the 1st group; the elements giving R₂O₂ or RO as their highest grade of oxidation belong to the 2nd group; those giving R₂O₃ as their highest oxides form the 3rd group, and so on; whilst the elements of all the groups which are nearest in their atomic weights are arranged in series from 1 to 12. The even and uneven series of the same groups present the same forms and limits, but differ in their properties, and therefore two contiguous series, one even and the other uneven—for instance, the 4th and 5th—form a period. Hence the elements of the 4th, 6th, 8th, 10th, and 12th, or of the 3rd, 5th, 7th, 9th, and 11th, series form analogues, like the halogens, the alkali metals, &c. The conjunction of two series, one even and one contiguous uneven series, thus forms one large period. These periods, beginning with the alkali metals, end with the halogens. The elements of the first two series have the lowest atomic weights, and in consequence of this very circumstance, although they bear the general properties of a group, they still show many peculiar and independent properties.[9] Thus fluorine, as we know, differs in many points from the other halogens, and lithium from the other alkali metals, and so on. These lightest elements may be termed typical elements. They include—

H.

Li, Be, B, C, N, O, F.

Na, Mg....

In the annexed table all the remaining elements are arranged, not in groups and series, but according to periods. In order to understand the essence of the matter, it must be remembered that here the atomic weight gradually increases along a given line; for instance, in the line commencing with K = 39 and ending with Br = 80, the intermediate elements have intermediate atomic weights, as is clearly seen in [Table III.], where the elements stand in the order of their atomic weights.

The same degree of analogy that we know to exist between potassium, rubidium, and cæsium; or chlorine, bromine, and iodine; or calcium, strontium, and barium, also exists between the elements of the other vertical columns. Thus, for example, zinc, cadmium, and mercury, which are described in the following chapter, present a very close analogy with magnesium. For a true comprehension of the matter[10] it is very important to see that all the aspects of the distribution of the elements according to their atomic weights essentially express one and the same fundamental dependence—periodic properties.[11] The following points then must be remarked in it.

1. The composition of the higher oxygen compounds is determined by the groups: the first group gives R₂O, the second R₂O₂ or RO, the third R₂O₃, &c. There are eight types of oxides and therefore eight groups. Two groups give a period, and the same type of oxide is met with twice in a period. For example, in the period beginning with potassium, oxides of the composition RO are formed by calcium and zinc, and of the composition RO₃ by molybdenum and tellurium. The oxides of the even series, of the same type, have stronger basic properties than the oxides of the uneven series, and the latter as a rule are endowed with an acid character. Therefore the elements which exclusively give bases, like the alkali metals, will be found at the commencement of the period, whilst such purely acid elements as the halogens will be at the end of the period. The interval will be occupied by intermediate elements, whose character and properties we shall afterwards describe. It must be observed that the acid character is chiefly proper to the elements with small atomic weights in the uneven series, whilst the basic character is exhibited by the heavier elements in the even series. Hence elements which give acids chiefly predominate among the lightest (typical) elements, especially in the last groups; whilst the heaviest elements, even in the last groups (for instance, thallium, uranium) have a basic character. Thus the basic and acid characters of the higher oxides are determined (a) by the type of oxide, (b) by the even or uneven series, and (c) by the atomic weight.[11 bis] The groups are indicated by Roman numerals from I. to VIII.

2. The hydrogen compounds being volatile or gaseous substances which are prone to reaction—such as HCl, H₂O, H₃N, and H₄C[12]—are only formed by the elements of the uneven series and higher groups giving oxides of the forms R₂O_n, RO₃, R₂O₅, and RO₂.

3. If an element gives a hydrogen compound, RX_m, it forms an organo-metallic compound of the same composition, where X = C_nH_2n+1; that is, X is the radicle of a saturated hydrocarbon. The elements of the uneven series, which are incapable of giving hydrogen compounds, and give oxides of the forms RX, RX₂, R_X3, also give organo-metallic compounds of this form proper to the higher oxides. Thus zinc forms the oxide ZnO, salts ZnX₂ and zinc ethyl Zn(C₂H₅)₂. The elements of the even series do not seem to form organo-metallic compounds at all; at least all efforts for their preparation have as yet been fruitless—for instance, in the case of titanium, zirconium, or iron.

4. The atomic weights of elements belonging to contiguous periods differ approximately by 45; for example, K[12 bis]

5. According to the periodic system every element occupies a certain position, determined by the group (indicated in Roman numerals) and series (Arabic numerals) in which it occurs. These indicate the atomic weight, the analogues, properties, and type of the higher oxide, and of the hydrogen and other compounds—in a word, all the chief quantitative and qualitative features of an element, although there yet remain a whole series of further details and peculiarities whose cause should perhaps be looked for in small differences of the atomic weights. If in a certain group there occur elements, R₁, R₂, R₃, and if in that series which contains one of these elements, for instance R₂, an element Q₂ precedes it and an element T₂ succeeds it, then the properties of R₂ are determined by the properties of R₁, R₃, Q₂, and T₂. Thus, for instance, the atomic weight of R₂ = ¼(R₁ + R₃ + Q₂ + T₂). For example, selenium occurs in the same group as sulphur, S = 32, and tellurium, Te = 125, and, in the 7th series As = 75 stands before it and Br = 80 after it. Hence the atomic weight of selenium should be ¼(32 + 125 + 75 + 80) = 78, which is near to the truth. Other properties of selenium may also be determined in this manner. For example, arsenic forms H₃As, bromine gives HBr, and it is evident that selenium, which stands between them, should form H₂Se, with properties intermediate between those of H₃As and HBr. Even the physical properties of selenium and its compounds, not to speak of their composition, being determined by the group in which it occurs, may be foreseen with a close approach to reality from the properties of sulphur, tellurium, arsenic, and bromine. In this manner it is possible to foretell the properties of still unknown elements. For instance in the position IV, 5—that is, in the IVth group and 5th series—an element is still wanting. These unknown elements may be named after the preceding known element of the same group by adding to the first syllable the prefix eka-, which means one in Sanskrit. The element IV, 5, follows after IV, 3, and this latter position being occupied by silicon, we call the unknown element ekasilicon and its symbol Es. The following are the properties which this element should have on the basis of the known properties of silicon, tin, zinc, and arsenic. Its atomic weight is nearly 72, higher oxide EsO₂, lower oxide EsO, compounds of the general form EsX₄, and chemically unstable lower compounds of the form EsX₂. Es gives volatile organo-metallic compounds—for instance, Es(CH₃)₄, Es(CH₃)₃Cl, and Es(C₂H₅)₄, which boil at about 160°, &c.; also a volatile and liquid chloride, EsCl₄, boiling at about 90° and of specific gravity about 1·9. EsO₂ will be the anhydride of a feeble colloidal acid, metallic Es will be rather easily obtainable from the oxides and from K₂EsF₆ by reduction, EsS₂ will resemble SnS₂ and SiS₂, and will probably be soluble in ammonium sulphide; the specific gravity of Es will be about 5·5, EsO₂ will have a density of about 4·7, &c. Such a prediction of the properties of ekasilicon was made by me in 1871, on the basis of the properties of the elements analogous to it: IV, 3, = Si, IV, 7 = Sn, and also II, 5 = Zn and V, 5 = As. And now that this element has been discovered by C. Winkler, of Freiberg, it has been found that its actual properties entirely correspond with those which were foretold.[13] In this we see a most important confirmation of the truth of the periodic law. This element is now called germanium, Ge (see Chapter [XVIII].). It is not the only one that has been predicted by the periodic law.[14] We shall see in describing the elements of the third group that properties were foretold of an element ekaaluminium, III, 5, El = 68, and were afterwards verified when the metal termed ‘gallium’ was discovered by De Boisbaudran. So also the properties of scandium corresponded with those predicted for ekaboron, according to Nilson.[15]

6. As a true law of nature is one to which there are no exceptions, the periodic dependence of the properties on the atomic weights of the elements gives a new means for determining by the equivalent the atomic weight or atomicity of imperfectly investigated but known elements, for which no other means could as yet be applied for determining the true atomic weight. At the time (1869) when the periodic law was first proposed there were several such elements. It thus became possible to learn their true atomic weights, and these were verified by later researches. Among the elements thus concerned were indium, uranium, cerium, yttrium, and others.

7. The periodic variability of the properties of the elements in dependence on their masses presents a distinction from other kinds of periodic dependence (as, for example, the sines of angles vary periodically and successively with the growth of the angles, or the temperature of the atmosphere with the course of time), in that the weights of the atoms do not increase gradually, but by leaps; that is, according to Dalton's law of multiple proportions, there not only are not, but there cannot be, any transitive or intermediate elements between two neighbouring ones (for example, between K = 39 and Ca = 40, or Al = 27 and Si = 28, or C = 12 and N = 14, &c.) As in a molecule of a hydrogen compound there may be either one, as in HF, or two, as in H₂O, or three, as in NH₃, &c., atoms of hydrogen; but as there cannot be molecules containing 2½ atoms of hydrogen to one atom of another element, so there cannot be any element intermediate between N and O, with an atomic weight greater than 14 or less than 16, or between K and Ca. Hence the periodic dependence of the elements cannot be expressed by any algebraical continuous function in the same way that it is possible, for instance, to express the variation of the temperature during the course of a day or year.

8. The essence of the notions giving rise to the periodic law consists in a general physico-mechanical principle which recognises the correlation, transmutability, and equivalence of the forces of nature. Gravitation, attraction at small distances, and many other phenomena are in direct dependence on the mass of matter. It might therefore have been expected that chemical forces would also depend on mass. A dependence is in fact shown, the properties of elements and compounds being determined by the masses of the atoms of which they are formed. The weight of a molecule, or its mass, determines, as we have seen, (Chapter [VII.] and elsewhere) many of its properties independently of its composition. Thus carbonic oxide, CO, and nitrogen, N₂, are two gases having the same molecular weight, and many of their properties (density, liquefaction, specific heat, &c.) are similar or nearly similar. The differences dependent on the nature of a substance play another part, and form magnitudes of another order. But the properties of atoms are mainly determined by their mass or weight, and are in dependence upon it. Only in this case there is a peculiarity in the dependence of the properties on the mass, for this dependence is determined by a periodic law. As the mass increases the properties vary, at first successively and regularly, and then return to their original magnitude and recommence a fresh period of variation like the first. Nevertheless here as in other cases a small variation of the mass of the atom generally leads to a small variation of properties, and determines differences of a second order. The atomic weights of cobalt and nickel, of rhodium, ruthenium, and palladium, and of osmium, iridium, and platinum, are very close to each other, and their properties are also very much alike—the differences are not very perceptible. And if the properties of atoms are a function of their weight, many ideas which have more or less rooted themselves in chemistry must suffer change and be developed and worked out in the sense of this deduction. Although at first sight it appears that the chemical elements are perfectly independent and individual, instead of this idea of the nature of the elements, the notion of the dependence of their properties upon their mass must now be established; that is to say, the subjection of the individuality of the elements to a common higher principle which evinces itself in gravity and in all physico-chemical phenomena. Many chemical deductions then acquire a new sense and significance, and a regularity is observed where it would otherwise escape attention. This is more particularly apparent in the physical properties, to the consideration of which we shall afterwards turn, and we will now point out that Gustavson first (Chapter X., Note [28]) and subsequently Potilitzin (Chapter XI., Note [66]) demonstrated the direct dependence of the reactive power on the atomic weight and that fundamental property which is expressed in the forms of their compounds, whilst in a number of other cases the purely chemical relations of elements proved to be in connection with their periodic properties. As a case in point, it may be mentioned that Carnelley remarked a dependence of the decomposability of the hydrates on the position of the elements in the periodic system; whilst L. Meyer, Willgerodt, and others established a connection between the atomic weight or the position of the elements in the periodic system and their property of serving as media in the transference of the halogens to the hydrocarbons.[16] Bailey pointed out a periodicity in the stability (under the action of heat) of the oxides, namely: (a) in the even series (for instance, CrO₃, MoO₃, WO₃, and UO₃) the higher oxides of a given group decompose with greater ease the smaller the atomic weight, while in the uneven series (for example, CO₂, GeO₂, SnO₂, and PbO₂) the contrary is the case; and (b) the stability of the higher saline oxides in the even series (as in the fourth series from K₂O to Mn₂O₇) decreases in passing from the lower to the higher groups, while in the uneven series it increases from the Ist to the IVth group, and then falls from the IVth to the VIIth; for instance, in the series Ag₂O, CdO, In₂O₃, SnO₂, and then SnO₂, Sb₂O₅, TeO₃, I₂O₇. K. Winkler looked for and actually found (1890) a dependence between the reducibility of the metals by magnesium and their position in the periodic system of the elements. The greater the attention paid to this field the more often is a distinct connection found between the variation of purely chemical properties of analogous substances and the variation of the atomic weights of the constituent elements and their position in the periodic system. Besides, since the periodic system has become more firmly established, many facts have been gathered, showing that there are many similarities between Sn and Pb, B and Al, Cd and Hg, &c., which had not been previously observed, although foreseen in some cases, and a consequence of the periodic law. Keeping our attention in the same direction, we see that the most widely distributed elements in nature are those with small atomic weights, whilst in organisms the lightest elements exclusively predominate (hydrogen, carbon, nitrogen, oxygen), whose small mass facilitates those transformations which are proper to organisms. Poluta (of Kharkoff), C. C. Botkin, Blake, Brenton, and others even discovered a correlation between the physiological action of salts and other reagents on organisms and the positions occupied in the periodic system by the metals contained in them.[17]

As, from the necessity of the case, the physical properties must be in dependence on the composition of a substance, i.e. on the quality and quantity of the elements forming it, so for them also a dependence on the atomic weight of the component elements must be expected, and consequently also on their periodic distribution. We shall meet with repeated proofs of this in the further exposition of our treatise, and for the present will content ourselves with citing the discovery by Carnelley in 1879 of the dependence of the magnetic properties of the elements on the position occupied by them in the periodic system. Carnelley showed that all the elements of the even series (beginning with lithium, potassium, rubidium, cæsium) belong to the number of magnetic (paramagnetic) substances; for example, according to Faraday and others,[17 bis] C, N, O, K, Ti, Cr, Mn, Fe, Co, Ni, Ce, are magnetic; and the elements of the uneven series are diamagnetic, H, Na, Si, P, S, Cl, Cu, Zn, As, Se, Br, Ag, Cd, Sn, Sb, I, Au, Hg, Tl, Pb, Bi.

Carnelley also showed that the melting-point of elements varies periodically, as is seen by the figures in [Table III.] (nineteenth column),[18] where all the most trustworthy data are collected, and predominance is given to those having maximum and minimum values.[19]

There is no doubt that many other physical properties will, when further studied, also prove to be in periodic dependence on the atomic weights,[19 bis] but at present only a few are known with any completeness, and we will only refer to the one which is the most easily and frequently determined—namely, the specific gravity in a solid and liquid state, the more especially as its connection with the chemical properties and relations of substances is shown at every step. Thus, for instance, of all the metals those of the alkalis, and of all the non-metals the halogens, are the most energetic in their reactions, and they have the lowest specific gravity among the adjacent elements, as is seen in [Table III.], column 17. Such are sodium, potassium, rubidium, cæsium among the metals, and chlorine, bromine, and iodine among the non-metals; and as such less energetic metals as iridium, platinum, and gold (and even charcoal or the diamond) have the highest specific gravity among the elements near to them in atomic weight; therefore the degree of the condensation of matter evidently influences the course of the transformations proper to a substance, and furthermore this dependence on the atomic weight, although very complex, is of a clearly periodic character. In order to account for this to some extent, it may be imagined that the lightest elements are porous, and, like a sponge, are easily penetrated by other substances, whilst the heavier elements are more compressed, and give way with difficulty to the insertion of other elements. These relations are best understood when, instead of the specific gravities referring to a unit of volume,[20] the atomic volumes of the elements—that is, the quotient A/d of the atomic weight A by the specific gravity d—are taken for comparison. As, according to the entire sense of the atomic theory, the actual matter of a substance does not fill up its whole cubical contents, but is surrounded by a medium (ethereal, as is generally imagined), like the stars and planets which travel in the space of the heavens and fill it, with greater or less intervals, so the quotient A/d only expresses the mean volume corresponding to the sphere of the atoms, and therefore [3root]A/d is the mean distance between the centres of the atoms. For compounds whose molecules weigh M, the mean magnitude of the atomic volume is obtained by dividing the mean molecular volume M/d by the number of atoms n in the molecule.[21] The above relations may easily be expressed from this point of view by comparing the atomic volumes. Those comparatively light elements which easily and frequently enter into reaction have the greatest atomic volumes: sodium 23, potassium 45, rubidium 57, cæsium 71, and the halogens about 27; whilst with those elements which enter into reaction with difficulty, the mean atomic volume is small; for carbon in the form of a diamond it is less than 4, as charcoal about 6, for nickel and cobalt less than 7, for iridium and platinum about 9. The remaining elements having atomic weights and properties intermediate between those elements mentioned above have also intermediate atomic volumes. Therefore the specific gravities and specific volumes of solids and liquids stand in periodic dependence on the atomic weights, as is seen in [Table III.], where both A (the atomic weight) and d (the specific gravity), and A/d (specific volumes of the atoms) are given (column 18).

Thus we find that in the large periods beginning with lithium, sodium, potassium, rubidium, cæsium, and ending with fluorine, chlorine, bromine, iodine, the extreme members (energetic elements) have a small density and large volume, whilst the intermediate substances gradually increase in density and decrease in volume—that is, as the atomic weight increases the density rises and falls, again rises and falls, and so on. Furthermore, the energy decreases as the density rises, and the greatest density is proper to the atomically heaviest and least energetic elements; for example, Os, Ir, Pt, Au, U.

In order to explain the relation between the volumes of the elements and of their compounds, the densities (column S) and volumes (column M/s) of some of the higher saline oxides arranged in the same order as in the case of the elements are given on p. [36]. For convenience of comparison the volumes of the oxides are all calculated per two atoms of an element combined with oxygen. For example, the density of Al₂O₃ = 4·0, weight Al₂O₃ = 102, volume Al₂O₃ = 25·5. Whence, knowing the volume of aluminium to be 11, it is at once seen that in the formation of aluminium oxide, 22 volumes of it give 25·5 volumes of oxide. A distinct periodicity may also be observed with respect to the specific gravities and volumes of the higher saline oxides. Thus in each period, beginning with the alkali metals, the specific gravity of the oxides first rises, reaches a maximum, and then falls on passing to the acid oxides, and again becomes a minimum about the halogens. But it is especially important to call attention to the fact that the volume of the alkali oxides is less than that of the metal contained in them, which is also expressed in the last column, giving this difference for each atom of oxygen.[22] Thus 2 atoms of sodium, or 46 volumes, give 24 volumes of Na₂O, and about 37 volumes of 2NaHO—that is, the oxygen and hydrogen in distributing themselves in the medium of sodium have not only not increased the distance between its atoms, but have brought them nearer together, have drawn them together by the force of their great affinity, by reason, it may be presumed, of the small mutual attraction of the atoms of sodium. Such metals as aluminium and zinc, in combining with oxygen and forming oxides of feeble salt-forming capacity, hardly vary in volume, but the common metals and non-metals, and especially those forming acid oxides, always give an increased volume when oxidised—that is, the atoms are set further apart in order to make room for the oxygen. The oxygen in them does not compress the molecule as in the alkalis; it is therefore comparatively easily disengaged.

As the volumes of the chlorides, organo-metallic and all other corresponding compounds, also vary in a like periodic succession with a change of elements, it is evidently possible to indicate the properties of substances yet uninvestigated by experimental means, and even those of yet undiscovered elements. It was possible by following this method to foretell, on the basis of the periodic law, many of the properties of scandium, gallium, and germanium, which were verified with great accuracy after these metals had been discovered.[23] The periodic law, therefore, has not only embraced the mutual relations of the elements and expressed their analogy, but has also to a certain extent subjected to law the doctrine of the types of the compounds formed by the elements: it has enabled us to see a regularity in the variation of all chemical and physical properties of elements and compounds, and has rendered it possible to foretell the properties of elements and compounds yet uninvestigated by experimental means; thus it has prepared the ground for the building up of atomic and molecular mechanics.[24]

Footnotes:

[1] For instance the analogy of the sulphates of K, Rb, and Cs (Chapter XIII., Note [1]).

[1 bis] The crystalline forms of aragonite, strontianite, and witherite belong to the rhombic system; the angle of the prism of CaCO₃ is 116° 10′, of SrCO₃ 117° 19′, and of BaCO₃ 118° 30′. On the other hand the crystalline forms of calc spar, magnesite, and calamine, which resemble each other quite as closely, belong to the rhombohedral system, with the angle of the rhombohedra for CaCO₃ 105° 8′, MgCO₃ 107° 10′, and ZnCO₃ 107° 40′. From this comparison it is at once evident that zinc is more closely allied to magnesium than magnesium to calcium.

[2] Solutions furnish the commonest examples of indefinite chemical compounds. But the isomorphous mixtures which are so common among the crystalline compounds of silica forming the crust of the earth, as well as alloys, which are so important in the application of metals to the arts, are also instances of indefinite compounds. And if in Chapter [I.], and in many other portions of this work, it has been necessary to admit the presence of definite compounds (in a state of dissociation) in solutions, the same applies with even greater force to isomorphous mixtures and alloys. For this reason in many places in this work I refer to facts which compel us to recognise the existence of definite chemical compounds in all isomorphous mixtures and alloys. This view of mine (which dates from the sixties) upon isomorphous mixtures finds a particularly clear confirmation in B. Roozeboom's researches (1892) upon the solubility and crystallising capacity of mixtures of the chlorates of potassium and thallium, KClO₃ and TlClO₃. He showed that when a solution contains different amounts of these salts, it deposits crystals containing either an excess of the first salt, from 98 p.c. to 100 p.c., or an excess of the second salt, from 63·7 to 100 p.c.; that is, in the crystalline form, either the first salt saturates the second or the second the first, just as in the solution of ether in water (Chapter [I.]); moreover, the solubility of the mixtures containing 36·3 and 98 p.c. KClO₃ is similar, just as the vapour tension of a saturated solution of water in ether is equal to that of a saturated solution of ether in water (Chapter I., Note [47]). But just as there are solutions miscible in all proportions, so also certain isomorphous bodies can be present in crystals in all possible proportions of their component parts. Van 't Hoff calls such systems ‘solid solutions.’ These views were subsequently elaborated by Nernst (1892), and Witt (1891) applied them in explaining the phenomena observed in the coloration of tissues.

[3] The cause of the difference which is observed in different compounds of the same type, with respect to their property of forming isomorphous mixtures, must not be looked for in the difference of their volumetric composition, as many investigators, including Kopp, affirm. The molecular volumes (found by dividing the molecular weight by the density) of those isomorphous substances which do give intermixtures are not nearer to each other than the volumes of those which do not give mixtures; for example, for magnesium carbonate the combining weight is 84, density 3·06, and volume therefore 27; for calcium carbonate in the form of calc spar the volume is 37, and in the form of aragonite 33; for strontium carbonate 41, for barium carbonate 46; that is, the volume of these closely allied isomorphous substances increases with the combining weight. The same is observed if we compare sodium chloride (molecular volume = 27) with potassium chloride (volume = 37), or sodium sulphate (volume = 55) with potassium sulphate (volume = 66), or sodium nitrate 39 with potassium nitrate 48, although the latter are less capable of giving isomorphous mixtures than the former. It is evident that the cause of isomorphism cannot be explained by an approximation in molecular volumes. It is more likely that, given a similarity in form and composition, the faculty to give isomorphous mixtures is connected with the laws and degree of solubility.

[4] A phenomenon of a similar kind is shown for magnesium sulphate in Note [27] of the last chapter. In the same example we see what a complication the phenomena of dimorphism may introduce when the forms of analogous compounds are compared.

[5] The property of solids of occurring in regular crystalline forms—the occurrence of many substances in the earth's crust in these forms—and those geometrical and simple laws which govern the formation of crystals long ago attracted the attention of the naturalist to crystals. The crystalline form is, without doubt, the expression of the relation in which the atoms occur in the molecules, and in which the molecules occur in the mass, of a substance. Crystallisation is determined by the distribution of the molecules along the direction of greatest cohesion, and therefore those forces must take part in the crystalline distribution of matter which act between the molecules; and, as they depend on the forces binding the atoms together in the molecules, a very close connection must exist between the atomic composition and the distribution of the atoms in the molecule on the one hand, and the crystalline form of a substance on the other hand; and hence an insight into the composition may be arrived at from the crystalline form. Such is the elementary and a priori idea which lies at the base of all researches into the connection between composition and crystalline form. Haüy in 1811 established the following fundamental law, which has been worked out by later investigators: That the fundamental crystalline form for a given chemical compound is constant (only the combinations vary), and that with a change of composition the crystalline form also changes, naturally with the exception of such limiting forms as the cube, regular octahedron, &c., which may belong to various substances of the regular system. The fundamental form is determined by the angles of certain fundamental geometric forms (prisms, pyramids, rhombohedra), or the ratio of the crystalline axes, and is connected with the optical and many other properties of crystals. Since the establishment of this law the description of definite compounds in a solid state is accompanied by a description (measurement) of its crystals, which forms an invariable, definite, and measurable character. The most important epochs in the further history of this question were made by the following discoveries:—Klaproth, Vauquelin, and others showed that aragonite has the same composition as calc spar, whilst the former belongs to the rhombic and the latter to the hexagonal system. Haüy at first considered that the composition, and after that the arrangement, of the atoms in the molecules was different. This is dimorphism (see Chapter [XIV.], Note [46]). Beudant, Frankenheim, Laurent, and others found that the forms of the two nitres, KNO₃ and NaNO₃, exactly correspond with the forms of aragonite and calc spar; that they are able, moreover, to pass from one form into another; and that the difference of the forms is accompanied by a small alteration of the angles, for the angle of the prisms of potassium nitrate and aragonite is 119°, and of sodium nitrate and calc spar, 120°; and therefore dimorphism, or the crystallisation of one substance in different forms, does not necessarily imply a great difference in the distribution of the molecules, although some difference clearly exists. The researches of Mitscherlich (1822) on the dimorphism of sulphur confirmed this conclusion, although it cannot yet be affirmed that in dimorphism the arrangement of the atoms remains unaltered, and that only the molecules are distributed differently. Leblanc, Berthier, Wollaston, and others already knew that many substances of different composition appear in the same forms, and crystallise together in one crystal. Gay-Lussac (1816) showed that crystals of potash alum continue to grow in a solution of ammonia alum. Beudant (1817) explained this phenomenon as the assimilation of a foreign substance by a substance having a great force of crystallisation, which he illustrated by many natural and artificial examples. But Mitscherlich, and afterwards Berzelius and Henry Rose and others, showed that such an assimilation only exists with a similarity or approximate similarity of the forms of the individual substances and with a certain degree of chemical analogy. Thus was established the idea of isomorphism as an analogy of forms by reason of a resemblance of atomic composition, and by it was explained the variability of the composition of a number of minerals as isomorphous mixtures. Thus all the garnets are expressed by the general formula: (RO)₃M₂O₃(SiO₂)₃, where R = Ca, Mg, Fe, Mn, and M = Fe, Al, and where we may have either R and M separately, or their equivalent compounds, or their mixtures in all possible proportions.

But other facts, which render the correlation of form and composition still more complex, have accumulated side by side with a mass of data which may be accounted for by admitting the conceptions of isomorphism and dimorphism. Foremost among the former stand the phenomena of homeomorphism—that is, a nearness of forms with a difference of composition—and then the cases of polymorphism and hemimorphism—that is, a nearness of the fundamental forms or only of certain angles for substances which are near or analogous in their composition. Instances of homeomorphism are very numerous. Many of these, however, may be reduced to a resemblance of atomic composition, although they do not correspond to an isomorphism of the component elements; for example, CdS (greenockite) and AgI, CaCO₃ (aragonite) and KNO₃, CaCO₃ (calc spar) and NaNO₃, BaSO₄ (heavy spar), KMnO₄ (potassium permanganate), and KClO₄ (potassium perchlorate), Al₂O₃ (corundum) and FeTiO₃ (titanic iron ore), FeS₂ (marcasite, rhombic system) and FeSAs (arsenical pyrites), NiS and NiAs, &c. But besides these instances there are homeomorphous substances with an absolute dissimilarity of composition. Many such instances were pointed out by Dana. Cinnabar, HgS, and susannite, PbSO₄3PbCO₃ appear in very analogous crystalline forms; the acid potassium sulphate crystallises in the monoclinic system in crystals analogous to felspar, KAlSi₃O₈; glauberite, Na₂Ca(SO₄)₂, augite, RSiO₃ (R = Ca, Mg), sodium carbonate, Na₂CO₃,10H₂O, Glauber's salt, Na₂SO₄,10H₂O, and borax, Na₂BrO₇,10H₂O, not only belong to the same system (monoclinic), but exhibit an analogy of combinations and a nearness of corresponding angles. These and many other similar cases might appear to be perfectly arbitrary (especially as a nearness of angles and fundamental forms is a relative idea) were there not other cases where a resemblance of properties and a distinct relation in the variation of composition is connected with a resemblance of form. Thus, for example, alumina, Al₂O₃, and water, H₂O, are frequently found in many pyroxenes and amphiboles which only contain silica and magnesia (MgO, CaO, FeO, MnO). Scheerer and Hermann, and many others, endeavoured to explain such instances by polymetric isomorphism, stating that MgO may be replaced by 3H₂O (for example, olivine and serpentine), SiO₂ by Al₂O₃ (in the amphiboles, talcs), and so on. A certain number of the instances of this order are subject to doubt, because many of the natural minerals which served as the basis for the establishment of polymeric isomorphism in all probability no longer present their original composition, but one which has been altered under the influence of solutions which have come into contact with them; they therefore belong to the class of pseudomorphs, or false crystals. There is, however, no doubt of the existence of a whole series of natural and artificial homeomorphs, which differ from each other by atomic amounts of water, silica, and some other component parts. Thus, Thomsen (1874) showed a very striking instance. The metallic chlorides, RCl₂, often crystallise with water, and they do not then contain less than one molecule of water per atom of chlorine. The most familiar representative of the order RCl₂,2H₂O is BaCl₂,2H₂O, which crystallises in the rhombic system. Barium bromide, BaBr₂,2H₂O, and copper chloride, CuCl₂,2H₂O, have nearly the same forms: potassium iodate, KIO₄; potassium chlorate, KClO₄; potassium permanganate, KMnO₄; barium sulphate, BaSO₄; calcium sulphate, CaSO₄; sodium sulphate, Na₂SO₄; barium formate, BaC₂H₂O₄, and others have almost the same crystalline form (of the rhombic system). Parallel with this series is that of the metallic chlorides containing RCl₂,4H₂O, of the sulphates of the composition RSO₄,2H₂O, and the formates RC₂H₂O₄,2H₂O. These compounds belong to the monoclinic system, have a close resemblance of form, and differ from the first series by containing two more molecules of water. The addition of two more molecules of water in all the above series also gives forms of the monoclinic system closely resembling each other; for example, NiCl₂,6H₂O and MnSO₄,4H₂O. Hence we see that not only is RCl₂,2H₂O analogous in form to RSO₄ and RC₂H₂O₄, but that their compounds with 2H₂O and with 4H₂O also exhibit closely analogous forms. From these examples it is evident that the conditions which determine a given form may be repeated not only in the presence of an isomorphous exchange—that is, with an equal number of atoms in the molecule—but also in the presence of an unequal number when there are peculiar and as yet ungeneralised relations in composition. Thus ZnO and Al₂O₃ exhibit a close analogy of form. Both oxides belong to the rhombohedral system, and the angle between the pyramid and the terminal plane of the first is 118° 7′, and of the second 118° 49′. Alumina, Al₂O₃, is also analogous in form to SiO₂, and we shall see that these analogies of form are conjoined with a certain analogy in properties. It is not surprising, therefore, that in the complex molecule of a siliceous compound it is sometimes possible to replace SiO₂ by means of Al₂O₃, as Scheerer admits. The oxides Cu₂O, MgO, NiO, Fe₃O₄, CeO₂, crystallise in the regular system, although they are of very different atomic structure. Marignac demonstrated the perfect analogy of the forms of K₂ZrF₆ and CaCO₃, and the former is even dimorphous, like the calcium carbonate. The same salt is isomorphous with R₂NbOF₅ and R₂WO₂F₄, where R is an alkali metal. There is an equivalency between CaCO₃ and K₂ZrF₆, because K₂ is equivalent to Ca, C to Zr, and F₆ to O₃, and with the isomorphism of the other two salts we find besides an equal contents of the alkali metal—an equal number of atoms on the one hand and an analogy to the properties of K₂ZrF₆ on the other. The long-known isomorphism of the corresponding compounds of potassium and ammonium, KX and NH₄X, may be taken as the simplest example of the fact that an analogy of form shows itself with an analogy of chemical reaction even without an equality in atomic composition. Therefore the ultimate progress of the entire doctrine of the correlation of composition and crystalline forms will only be arrived at with the accumulation of a sufficient number of facts collected on a plan corresponding with the problems which here present themselves. The first steps have already been made. The researches of the Geneva savant, Marignac, on the crystalline form and composition of many of the double fluorides, and the work of Wyruboff on the ferricyanides and other compounds, are particularly important in this respect. It is already evident that, with a definite change of composition, certain angles remain constant, notwithstanding that others are subject to alteration. Such an instance of the relation of forms was observed by Laurent, and named by him hemimorphism (an anomalous term) when the analogy is limited to certain angles, and paramorphism when the forms in general approach each other, but belong to different systems. So, for example, the angle of the planes of a rhombohedron may be greater or less than 90°, and therefore such acute and obtuse rhombohedra may closely approximate to the cube. Hausmannite, Mn₃O₄, belongs to the tetragonal system, and the planes of its pyramid are inclined at an angle of about 118°, whilst magnetic iron ore, Fe₃O₄, which resembles hausmannite in many respects, appears in regular octahedra—that is, the pyramidal planes are inclined at an angle of 109° 28′. This is an example of paramorphism; the systems are different, the compositions are analogous, and there is a certain resemblance in form. Hemimorphism has been found in many instances of saline and other substitutions. Thus, Laurent demonstrated, and Hintze confirmed (1873), that naphthalene derivatives of analogous composition are hemimorphous. Nicklès (1849) showed that in ethylene sulphate the angle of the prism is 125° 26′, and in the nitrate of the same radicle 126° 95′. The angle of the prism of methylamine oxalate is 131° 20′, and of fluoride, which is very different in composition from the former, the angle is 132°. Groth (1870) endeavoured to indicate in general what kinds of change of form proceed with the substitution of hydrogen by various other elements and groups, and he observed a regularity which he termed morphotropy. The following examples show that morphotropy recalls the hemimorphism of Laurent. Benzene, C₆H₆, rhombic system, ratio of the axes 0·891 : 1 : 0·799. Phenol, C₆H₅(OH), and resorcinol, C₆H₄(OH)₂, also rhombic system, but the ratio of one axis is changed—thus, in resorcinol, 0·910 : 1 : 0·540; that is, a portion of the crystalline structure in one direction is the same, but in the other direction it is changed, whilst in the rhombic system dinitrophenol, C₆H₃(NO₂)₂(OH) = O·833 : 1 : 0·753; trinitrophenol (picric acid), C₆H₂(NO)₃(OH) = 0·937 : 1 : 0·974; and the potassium salt = 0·942 : 1 : 1·354. Here the ratio of the first axis is preserved—that is, certain angles remain constant, and the chemical proximity of the composition of these bodies is undoubted. Laurent compares hemimorphism with architectural style. Thus, Gothic cathedrals differ in many respects, but there is an analogy expressed both in the sum total of their common relations and in certain details—for example, in the windows. It is evident that we may expect many fruitful results for molecular mechanics (which forms a problem common to many provinces of natural science) from the further elaboration of the data concerning those variations which take place in crystalline form when the composition of a substance is subjected to a known change, and therefore I consider it useful to point out to the student of science seeking for matter for independent scientific research this vast field for work which is presented by the correlation of form and composition. The geometrical regularity and varied beauty of crystalline forms offer no small attraction to research of this kind.

[6] The still more complex combinations—which are so clearly expressed in the crystallo-hydrates, double salts, and similar compounds—although they may be regarded as independent, are, however, most easily understood with our present knowledge as aggregations of whole molecules to which there are no corresponding double compounds, containing one atom of an element R and many atoms of other elements RX_n. The above types embrace all cases of direct combinations of atoms, and the formula MgSO₄,7H₂O cannot, without violating known facts, be directly deduced from the types MgX_n or SX_n, whilst the formula MgSO₄ corresponds both with the type of the magnesium compounds MgX₂ and with the type of the sulphur compounds SO₂X₂, or in general SX₆, where X₂ is replaced by (OH)₂, with the substitution in this case of H₂ by the atom Mg, which always replaces H₂. However, it must be remarked that the sodium crystallo-hydrates often contain 10H₂O, the magnesium crystallo-hydrates 6 and 7H₂O, and that the type PtM₂X₆ is proper to the double salts of platinum, &c. With the further development of our knowledge concerning crystallo-hydrates, double salts, alloys, solutions, &c., in the chemical sense of feeble compounds (that is, such as are easily destroyed by feeble chemical influences) it will probably be possible to arrive at a perfect generalisation for them. For a long time these subjects were only studied by the way or by chance; our knowledge of them is accidental and destitute of system, and therefore it is impossible to expect as yet any generalisation as to their nature. The days of Gerhardt are not long past when only three types were recognised: RX, RX₂, and RX₃; the type RX₄ was afterwards added (by Cooper, Kekulé, Butleroff, and others), mainly for the purpose of generalising the data respecting the carbon compounds. And indeed many are still satisfied with these types, and derive the higher types from them; for instance, RX₅ from RX₃—as, for example, POCl₃ from PCl₃, considering the oxygen to be bound both to the chlorine (as in HClO) and to the phosphorus. But the time has now arrived when it is clearly seen that the forms RX, RX₂, RX₃, and RX₄ do not exhaust the whole variety of phenomena. The revolution became evident when Würtz showed that PCl₅ is not a compound of PCl₃ + Cl₂ (although it may decompose into them), but a whole molecule capable of passing into vapour, PCl₅ like PF₅ and SiF₄. The time for the recognition of types even higher than RX₈ is in my opinion in the future; that it will come, we can already see in the fact that oxalic acid, C₂H₂O₄, gives a crystallo-hydrate with 2H₂O; but it may be referred to the type CH₄, or rather to the type of ethane, C₂H₆, in which all the atoms of hydrogen are replaced by hydroxyl, C₂H₂O₄2H₂O = C₂(OH)₆ (see Chapter XXII., Note [35]).

[7] The hydrogen compounds, R₂H, in equivalency correspond with the type of the suboxides, R₄O. Palladium, sodium, and potassium give such hydrogen compounds, and it is worthy of remark that according to the periodic system these elements stand near to each other, and that in those groups where the hydrogen compounds R₂H appear, the quaternary oxides R₄O are also present.

Not wishing to complicate the explanation, I here only touch on the general features of the relation between the hydrates and oxides and of the oxides among themselves. Thus, for instance, the conception of the ortho-acids and of the normal acids will be considered in speaking of phosphoric and phosphorous acids.

As in the further explanation of the periodic law only those oxides which give salts will be considered, I think it will not be superfluous to mention here the following facts relative to the peroxides. Of the peroxides corresponding with hydrogen peroxide, the following are at present known: H₂O₂, Na₂O₂, S₂O₇ (as HSO₄?), K₂O₄, K₂O₂, CaO₂, TiO₃, Cr₂O₇, CuO₂(?), ZnO₂, Rb₂O₂, SrO₂, Ag₂O₂, CdO₂, CsO₂, Cs₂O₂, BaO₂, Mo₂O₇, SnO₃, W₂O₇, UO₄. It is probable that the number of peroxides will increase with further investigation. A periodicity is seen in those now known, for the elements (excepting Li) of the first group, which give R₂O, form peroxides, and then the elements of the sixth group seem also to be particularly inclined to form peroxides, R₂O₇; but at present it is too early, in my opinion, to enter upon a generalisation of this subject, not only because it is a new and but little studied matter (not investigated for all the elements), but also, and more especially, because in many instances only the hydrates are known—for instance, Mo₂H₂O₈—and they perhaps are only compounds of peroxide of hydrogen—for example, Mo₂H₂O₈ = 2MoO₃ + H₂O₂—since Prof. Schöne has shown that H₂O₂ and BaO₂ possess the property of combining together and with other oxides. Nevertheless, I have, in the general table expressing the periodic properties of the elements, endeavoured to sum up the data respecting all the known peroxide compounds whose characteristic property is seen in their capability to form peroxide of hydrogen under many circumstances.

[8] The periodic law and the periodic system of the elements appeared in the same form as here given in the first edition of this work, begun in 1868 and finished in 1871. In laying out the accumulated information respecting the elements, I had occasion to reflect on their mutual relations. At the beginning of 1869 I distributed among many chemists a pamphlet entitled ‘An Attempted System of the Elements, based on their Atomic Weights and Chemical Analogies,’ and at the March meeting of the Russian Chemical Society, 1869, I communicated a paper ‘On the Correlation of the Properties and Atomic Weights of the Elements.’ The substance of this paper is embraced in the following conclusions: (1) The elements, if arranged according to their atomic weights, exhibit an evident periodicity of properties. (2) Elements which are similar as regards their chemical properties have atomic weights which are either of nearly the same value (platinum, iridium, osmium) or which increase regularly (e.g. potassium, rubidium, cæsium). (3) The arrangement of the elements or of groups of elements in the order of their atomic weights corresponds with their so-called valencies. (4) The elements, which are the most widely distributed in nature, have small atomic weights, and all the elements of small atomic weight are characterised by sharply defined properties. They are therefore typical elements. (5) The magnitude of the atomic weight determines the character of an element. (6) The discovery of many yet unknown elements may be expected. For instance, elements analogous to aluminium and silicon, whose atomic weights would be between 65 and 75. (7) The atomic weight of an element may sometimes be corrected by aid of a knowledge of those of the adjacent elements. Thus the combining weight of tellurium must lie between 123 and 126, and cannot be 128. (8) Certain characteristic properties of the elements can be foretold from their atomic weights.

The entire periodic law is included in these lines. In the series of subsequent papers (1870–72, for example, in the Transactions of the Russian Chemical Society, of the Moscow Meeting of Naturalists, of the St. Petersburg Academy, and Liebig's Annalen) on the same subject we only find applications of the same principles, which were afterwards confirmed by the labours of Roscoe, Carnelley, Thorpe, and others in England; of Rammelsberg (cerium and uranium), L. Meyer (the specific volumes of the elements), Zimmermann (uranium), and more especially of C. Winkler (who discovered germanium, and showed its identity with ekasilicon), and others in Germany; of Lecoq de Boisbaudran in France (the discoverer of gallium = ekaaluminium); of Clève (the atomic weights of the cerium metals), Nilson (discoverer of scandium = ekaboron), and Nilson and Pettersson (determination of the vapour density of beryllium chloride) in Sweden; and of Brauner (who investigated cerium, and determined the combining weight of tellurium = 125) in Austria, and Piccini in Italy.

I consider it necessary to state that, in arranging the periodic system of the elements, I made use of the previous researches of Dumas, Gladstone, Pettenkofer, Kremers, and Lenssen on the atomic weights of related elements, but I was not acquainted with the works preceding mine of De Chancourtois (vis tellurique, or the spiral of the elements according to their properties and equivalents) in France, and of J. Newlands (Law of Octaves—for instance, H, F, Cl, Co, Br, Pd, I, Pt form the first octave, and O, S, Fe, Se, Rh, Te, Au, Th the last) in England, although certain germs of the periodic law are to be seen in these works. With regard to the work of Prof. Lothar Meyer respecting the periodic law (Notes [12] and [13]), it is evident, judging from the method of investigation, and from his statement (Liebig's Annalen, Supt. Band 7, 1870, 354), at the very commencement of which he cites my paper of 1869 above mentioned, that he accepted the periodic law in the form which I proposed.

In concluding this historical statement I consider it well to observe that no law of nature, however general, has been established all at once; its recognition is always preceded by many hints; the establishment of a law, however, does not take place when its significance is recognised, but only when it has been confirmed by experiment, which the man of science must consider as the only proof of the correctness of his conjectures and opinions. I therefore, for my part, look upon Roscoe, De Boisbaudran, Nilson, Winkler, Brauner, Carnelley, Thorpe, and others who verified the adaptability of the periodic law to chemical facts, as the true founders of the periodic law, the further development of which still awaits fresh workers.

[9] This resembles the fact, well known to those having an acquaintance with organic chemistry, that in a series of homologues (Chapter [VIII.]) the first members, in which there is the least carbon, although showing the general properties of the homologous series, still present certain distinct peculiarities.

[10] Besides arranging the elements (a) in a successive order according to their atomic weights, with indication of their analogies by showing some of the properties—for instance, their power of giving one or another form of combination—both of the elements and of their compounds (as is done in [Table III.] and in the table on p. [36]), (b) according to periods (as in Table I. at the commencement of volume I. after the preface), and (c) according to groups and series or small periods (as in the same tables), I am acquainted with the following methods of expressing the periodic relations of the elements: (1) By a curve drawn through points obtained in the following manner: The elements are arranged along the horizontal axis as abscissæ at distances from zero proportional to their atomic weights, whilst the values for all the elements of some property—for example, the specific volumes or the melting points, are expressed by the ordinates. This method, although graphic, has the theoretical disadvantage that it does not in any way indicate the existence of a limited and definite number of elements in each period. There is nothing, for instance, in this method of expressing the law of periodicity to show that between magnesium and aluminium there can be no other element with an atomic weight of, say, 25, atomic volume 13, and in general having properties intermediate between those of these two elements. The actual periodic law does not correspond with a continuous change of properties, with a continuous variation of atomic weight—in a word, it does not express an uninterrupted function—and as the law is purely chemical, starting from the conception of atoms and molecules which combine in multiple proportions, with intervals (not continuously), it above all depends on there being but few types of compounds, which are arithmetically simple, repeat themselves, and offer no uninterrupted transitions, so that each period can only contain a definite number of members. For this reason there can be no other elements between magnesium, which gives the chloride MgCl₂, and aluminium, which forms AlX₃; there is a break in the continuity, according to the law of multiple proportions. The periodic law ought not, therefore, to be expressed by geometrical figures in which continuity is always understood. Owing to these considerations I never have and never will express the periodic relations of the elements by any geometrical figures. (2) By a plane spiral. Radii are traced from a centre, proportional to the atomic weights; analogous elements lie along one radius, and the points of intersection are arranged in a spiral. This method, adopted by De Chancourtois, Baumgauer, E. Huth, and others, has many of the imperfections of the preceding, although it removes the indefiniteness as to the number of elements in a period. It is merely an attempt to reduce the complex relations to a simple graphic representation, since the equation to the spiral and the number of radii are not dependent upon anything. (3) By the lines of atomicity, either parallel, as in Reynolds's and the Rev. S. Haughton's method, or as in Crookes's method, arranged to the right and left of an axis, along which the magnitudes of the atomic weights are counted, and the position of the elements marked off, on the one side the members of the even series (paramagnetic, like oxygen, potassium, iron), and on the other side the members of the uneven series (diamagnetic, like sulphur, chlorine, zinc, and mercury). On joining up these points a periodic curve is obtained, compared by Crookes to the oscillations of a pendulum, and, according to Haughton, representing a cubical curve. This method would be very graphic did it not require, for instance, that sulphur should be considered as bivalent and manganese as univalent, although neither of these elements gives stable derivatives of these natures, and although the one is taken on the basis of the lowest possible compound SX₂, and the other of the highest, because manganese can be referred to the univalent elements only by the analogy of KMnO₄ to KClO₄. Furthermore, Reynolds and Crookes place hydrogen, iron, nickel, cobalt, and others outside the axis of atomicity, and consider uranium as bivalent without the least foundation. (4) Rantsheff endeavoured to classify the elements in their periodic relations by a system dependent on solid geometry. He communicated this mode of expression to the Russian Chemical Society, but his communication, which is apparently not void of interest, has not yet appeared in print. (5) By algebraic formulæ: for example, E. J. Mills (1886) endeavours to express all the atomic weights by the logarithmic function A = 15(n - 0·9375t), in which the variables n and t are whole numbers. For instance, for oxygen n=2, t=1; hence A = 15·94; for antimony n=9, t=0; whence A=120, and so on. n varies from 1 to 16 and t from 0 to 59. The analogues are hardly distinguishable by this method: thus for chlorine the magnitudes of n and t are 3 and 7; for bromine 6 and 6; for iodine 9 and 9; for potassium 3 and 14; for rubidium 6 and 18; for cæsium 9 and 20; but a certain regularity seems to be shown. (6) A more natural method of expressing the dependence of the properties of elements on their atomic weights is obtained by trigonometrical functions, because this dependence is periodic like the functions of trigonometrical lines, and therefore Ridberg in Sweden (Lund, 1885) and F. Flavitzky in Russia (Kazan, 1887) have adopted a similar method of expression, which must be considered as worthy of being worked out, although it does not express the absence of intermediate elements—for instance, between magnesium and aluminium, which is essentially the most important part of the matter. (7) The investigations of B. N. Tchitchérin (1888, Journal of the Russian Physical and Chemical Society) form the first effort in the latter direction. He carefully studied the alkali metals, and discovered the following simple relation between their atomic volumes: they can all be expressed by A(2 - 0·0428An), where A is the atomic weight and n = 1 for lithium and sodium, ⁴⁄₈ for potassium, ⅜ for rubidium, and ²⁄₈ for cæsium. If n always = 1, then the volume of the atom would become zero at A = 46⅔, and would reach its maximum when A = 23⅓, and the density increases with the growth of A. In order to explain the variation of n, and the relation of the atomic weights of the alkali metals to those of the other elements, as also the atomicity itself, Tchitchérin supposes all atoms to be built up of a primary matter; he considers the relation of the central to the peripheric mass, and, guided by mechanical principles, deduces many of the properties of the atoms from the reaction of the internal and peripheric parts of each atom. This endeavour offers many interesting points, but it admits the hypothesis of the building up of all the elements from one primary matter, and at the present time such an hypothesis has not the least support either in theory or in fact. Besides which the starting-point of the theory is the specific gravity of the metals at a definite temperature (it is not known how the above relation would appear at other temperatures), and the specific gravity varies even under mechanical influences. L. Hugo (1884) endeavoured to represent the atomic weights of Li, Na, K, Rb, and Cs by geometrical figures—for instance, Li = 7 represents a central atom = 1 and six atoms on the six terminals of an octahedron; Na, is obtained by applying two such atoms on each edge of an octahedron, and so on. It is evident that such methods can add nothing new to our data respecting the atomic weights of analogous elements.

[11] Many natural phenomena exhibit a dependence of a periodic character. Thus the phenomena of day and night and of the seasons of the year, and vibrations of all kinds, exhibit variations of a periodic character in dependence on time and space. But in ordinary periodic functions one variable varies continuously, whilst the other increases to a limit, then a period of decrease begins, and having in turn reached its limit a period of increase again begins. It is otherwise in the periodic function of the elements. Here the mass of the elements does not increase continuously, but abruptly, by steps, as from magnesium to aluminium. So also the valency or atomicity leaps directly from 1 to 2 to 3, &c., without intermediate quantities, and in my opinion it is these properties which are the most important, and it is their periodicity which forms the substance of the periodic law. It expresses the properties of the real elements, and not of what may be termed their manifestations visually known to us. The external properties of elements and compounds are in periodic dependence on the atomic weight of the elements only because these external properties are themselves the result of the properties of the real elements which unite to form the ‘free’ elements and the compounds. To explain and express the periodic law is to explain and express the cause of the law of multiple proportions, of the difference of the elements, and the variation of their atomicity, and at the same time to understand what mass and gravitation are. In my opinion this is still premature. But just as without knowing the cause of gravitation it is possible to make use of the law of gravity, so for the aims of chemistry it is possible to take advantage of the laws discovered by chemistry without being able to explain their causes. The above-mentioned peculiarity of the laws of chemistry respecting definite compounds and the atomic weights leads one to think that the time has not yet come for their full explanation, and I do not think that it will come before the explanation of such a primary law of nature as the law of gravity.

It will not be out of place here to turn our attention to the many-sided correlation existing between the undecomposable elements and the compound carbon radicles, which has long been remarked (Pettenkofer, Dumas, and others), and reconsidered in recent times by Carnelley (1886), and most originally in Pelopidas's work (1883) on the principles of the periodic system. Pelopidas compares the series containing eight hydrocarbon radicles, C_nH_2n+1, C_nH_2n &c., for instance, C₆H₁₃, C₆H₁₂, C₆H₁₁, C₆H₁₀, C₆H₉, C₆H₈, C₆H₇, and C₆H₆—with the series of the elements arranged in eight groups. The analogy is particularly clear owing to the property of C_nH_2n+1 to combine with X, thus reaching saturation, and of the following members with X₂, X₃ … X₈, and especially because these are followed by an aromatic radicle—for example, C₆H₅—in which, as is well known, many of the properties of the saturated radicle C₆H₁₃ are repeated, and in particular the power of forming a univalent radicle again appears. Pelopidas shows a confirmation of the parallel in the property of the above radicles of giving oxygen compounds corresponding with the groups in the periodic system. Thus the hydrocarbon radicles of the first group—for instance, C₆H₁₃ or C₆H₅—give oxides of the form R₂O and hydroxides RHO, like the metals of the alkalis; and in the third group they form oxides R₂O₃ and hydrates RO₂H. For example, in the series CH₃ the corresponding compounds of the third group will be the oxide (CH)₂O₃ or C₂H₂O₃—that is, formic anhydride and hydrate, CHO₂H, or formic acid. In the sixth group, with a composition of C₂, the oxide RO₃ will be C₂O₃, and hydrate C₂H₂O₄—that is, also a bibasic acid (oxalic) resembling sulphuric, among the inorganic acids. After applying his views to a number of organic compounds, Pelopidas dwells more particularly on the radicles corresponding with ammonium.

With respect to this remarkable parallelism, it must above all be observed that in the elements the atomic weight increases in passing to contiguous members of a higher valency, whilst here it decreases, which should indicate that the periodic variability of elements and compounds is subject to some higher law whose nature, and still more whose cause, cannot at present be determined. It is probably based on the fundamental principles of the internal mechanics of the atoms and molecules, and as the periodic law has only been generally recognised for a few years it is not surprising that any further progress towards its explanation can only be looked for in the development of facts touching on this subject.

[11 bis] True peroxides (see Note [7]), like H₂O₂, BaO₂, S₂O₇ (Chapter [XX.]), must not be confused with true saline oxides even if the latter contain much oxygen (for instance, N₂O₅, CrO₃, &c.) although one and the other easily oxidise. The difference between them is seen in their fundamental properties: the saline oxides correspond to water, while the peroxides correspond in their reactions and origin to peroxide of hydrogen. This is clearly seen in the difference between Na₂O and Na₂O₂ (Chapter [XII.]). Therefore the peroxides should also have their periodicity. An element R, giving a highest degree of oxidation, R₂O_n, may give both a lower degree of oxidation, R₂O_n-m (where m is evidently less than n), and peroxides, R₂O_n+1, R₂O_n+2, or even more oxygen. This class of oxides, to which attention has only recently been turned (Berthelot, Piccini, &c.), may perhaps on further study give the possibility of generalising the capability of the elements to give unstable complex higher forms of combination, such as double salts, and in my opinion should in the near future be the field of new and important discoveries. And in contemporary chemistry, salts, saline oxides, hydrogen compounds, and other combinations of the elements corresponding to them constitute an important and very complex problem for generalisation, which is satisfied by the periodic law in its present form, to which it has risen from its first state, in which it gave the means of foreseeing (see later on) the existence of unknown elements (Ga, Sc, and Ge), their properties, and many details respecting their compounds. Until those improvements in the periodic system which have been proposed by Prof. Flavitzky (of Kazan) and Prof. Harperath (of Cordoba, in the Argentine Republic), Ugo Alvisi (Italy), and others give similar practical results, I think it unnecessary to discuss them further.

[12] The hydrides generalised by the periodic law are those to which metallo-organic compounds correspond, and they are themselves either volatile or gaseous. The hydrogen compounds like Na₂H, BaH, &c. are distinguished by other signs. They resemble alloys. They show (see end of last chapter) a systematic harmony, but they evidently should not be confused with true hydrides, any more than peroxides with saline oxides. Moreover, such hydrides have, like the peroxides, only recently been subjected to research, and have been but little studied. The best known of these compounds are given in the 16th column of [Table III.], and it will be seen that they already exhibit a periodicity of properties and composition.

[12 bis] The relation between the atomic weights, and especially the difference = 16, was observed in the sixth and seventh decades of this century by Dumas, Pettenkofer, L. Meyer, and others. Thus Lothar Meyer in 1864, following Dumas and others, grouped together the tetravalent elements carbon and silicon; the trivalent elements nitrogen, phosphorus, arsenic, antimony, and bismuth; the bivalent oxygen, sulphur, selenium, and tellurium; the univalent fluorine, chlorine, bromine, and iodine; the univalent metals lithium, sodium, potassium, rubidium, cæsium, and thallium, and the bivalent metals beryllium, magnesium, strontium and barium—observing that in the first the difference is, in general = 16, in the second about = 46, and the last about = 87–90. The first germs of the periodic law are visible in such observations as these. Since its establishment this subject has been most fully worked out by Ridberg (Note [10]), who observed a periodicity in the variation of the differences between the atomic weights of two contiguous elements, and its relation to their atomicity. A. Bazaroff (1887) investigated the same subject, taking, not the arithmetical differences of contiguous and analogous elements, but the ratio of their atomic weights; and he also observed that this ratio alternately rises and falls with the rise of the atomic weights. I will here remark that the relation of the eighth group to the others will be considered at the end of this work in Chapter [XXII.]

[13] The laws of nature admit of no exceptions, and in this they clearly differ from such rules and maxims as are found in grammar, and other inventions, methods, and relations of man's creation. The confirmation of a law is only possible by deducing consequences from it, such as could not possibly be foreseen without it, and by verifying those consequences by experiment and further proofs. Therefore, when I conceived the periodic law, I (1869–1871, Note [9]) deduced such logical consequences from it as could serve to show whether it were true or not. Among them was the prediction of the properties of undiscovered elements and the correction of the atomic weights of many, and at that time little known, elements. Thus uranium was considered as trivalent, U = 120; but as such it did not correspond with the periodic law. I therefore proposed to double its atomic weight—U = 240, and the researches of Roscoe, Zimmermann, and others justified this alteration (Chapter [XXI.]). It was the same with cerium (Chapter [XVIII.]) whose atomic weight it was necessary to change according to the periodic law. I therefore determined its specific heat, and the result I obtained was verified by the new determinations of Hillebrand. I then corrected certain formulæ of the cerium compounds, and the researches of Rammelsberg, Brauner, Clève, and others verified the proposed alteration. It was necessary to do one or the other—either to consider the periodic law as completely true, and as forming a new instrument in chemical research, or to refute it. Acknowledging the method of experiment to be the only true one, I myself verified what I could, and gave every one the possibility of proving or confirming the law, and did not think, like L. Meyer (Liebig's Annalen, Supt. Band 7, 1870, 364), when writing about the periodic law that ‘it would be rash to change the accepted atomic weights on the basis of so uncertain a starting-point.’ (‘Es würde voreilig sein, auf so unsichere Anhaltspunkte hin eine Aenderung der bisher angenommenen Atomgewichte vorzunehmen.’) In my opinion, the basis offered by the periodic law had to be verified or refuted, and experiment in every case verified it. The starting-point then became general. No law of nature can be established without such a method of testing it. Neither De Chancourtois, to whom the French ascribe the discovery of the periodic law, nor Newlands, who is put forward by the English, nor L. Meyer, who is now cited by many as its founder, ventured to foretell the properties of undiscovered elements, or to alter the ‘accepted atomic weights,’ or, in general, to regard the periodic law as a new, strictly established law of nature, as I did from the very beginning (1869).

[14] When in 1871 I wrote a paper on the application of the periodic law to the determination of the properties of hitherto undiscovered elements, I did not think I should live to see the verification of this consequence of the law, but such was to be the case. Three elements were described—ekaboron, ekaaluminium, and ekasilicon—and now, after the lapse of twenty years, I have had the great pleasure of seeing them discovered and named Gallium, Scandium, and Germanium, after those three countries where the rare minerals containing them are found, and where they were discovered. For my part I regard L. de Boisbaudran, Nilson, and Winkler, who discovered these elements, as the true corroborators of the periodic law. Without them it would not have been accepted to the extent it now is.

[15] Taking indium, which occurs together with zinc, as our example, we will show the principle of the method employed. The equivalent of indium to hydrogen in its oxide is 37·7—that is, if we suppose its composition to be like that of water; then In = 37·7, and the oxide of indium is In₂O. The atomic weight of indium was taken as double the equivalent—that is, indium was considered to be a bivalent element—and In = 2 × 37·7 = 75·4. If indium only formed an oxide, RO, it should be placed in group II. But in this case it appears that there would be no place for indium in the system of the elements, because the positions II., 5 = Zn = 65 and II., 6 = Sr = 87 were already occupied by known elements, and according to the periodic law an element with an atomic weight 75 could not be bivalent. As neither the vapour density nor the specific heat, nor even the isomorphism (the salts of indium crystallise with great difficulty) of the compounds of indium were known, there was no reason for considering it to be a bivalent metal, and therefore it might be regarded as trivalent, quadrivalent, &c. If it be trivalent, then In = 3 × 37·7 = 113, and the composition of the oxide is In₂O₃, and of its salts InX₃. In this case it at once falls into its place in the system, namely, in group III. and 7th series, between Cd = 112 and Sn = 118, as an analogue of aluminium or dvialuminium (dvi = 2 in Sanskrit). All the properties observed in indium correspond with this position; for example, the density, cadmium = 8·6, indium = 7·4, tin = 7·2; the basic properties of the oxides CdO, In₂O₃, SnO₂, successively vary, so that the properties of In₂O₃ are intermediate between those of CdO and SnO₂ or Cd₂O₂ and Sn₂O₄. That indium belongs to group III. has been confirmed by the determination of its specific heat, (0·057 according to Bunsen, and 0·055 according to me) and also by the fact that indium forms alums like aluminium, and therefore belongs to the same group.

The same kind of considerations necessitated taking the atomic weight of titanium as nearly 48, and not as 52, the figure derived from many analyses. And both these corrections, made on the basis of the law, have now been confirmed, for Thorpe found, by a series of careful experiments, the atomic weight of titanium to be that foreseen by the periodic law. Notwithstanding that previous analyses gave Os = 199·7, Ir = 198, and Pt = 187, the periodic law shows, as I remarked in 1871, that the atomic weights should rise from osmium to platinum and gold, and not fall. Many recent researches, and especially those of Seubert, have fully verified this statement, based on the law. Thus a true law of nature anticipates facts, foretells magnitudes, gives a hold on nature, and leads to improvements in the methods of research, &c.

[16] Meyer, Willgerodt, and others, guided by the fact that Gustavson and Friedel had remarked that metalepsis rapidly proceeds in the presence of aluminium, investigated the action of nearly all the elements in this respect. For example, they took benzene, added the metals to be experimented on to it, and passed chlorine through the liquid in diffused light. When, for instance, sodium, potassium, barium, &c. are taken, there is no action on the benzene; that is, hydrochloric acid is not disengaged; but if aluminium, gold, or, in general, any metal having this power of aiding chlorination (Halogen-überträger) is employed, then the action is clearly seen from the volumes of hydrochloric acid evolved (especially if the metallic chloride formed is soluble in benzene). Thus, in group I., and in general among the even and light elements, there are none capable of serving as agents of metalepsis; but aluminium, gallium, indium, antimony, tellurium, and iodine, which are contiguous members in the periodic system, are excellent transmitters (carriers) of the halogens.

[17] The periodic relations enumerated above appertain to the real elements, and not to the elements in the free state as we know them; and it is very important to note this, because the periodic law refers to the real elements, inasmuch as the atomic weight is proper to the real element, and not to the ‘free’ element, to which, as to a compound, a molecular weight is proper. Physical properties are chiefly determined by the properties of molecules, and only indirectly depend on the properties of the atoms forming the molecules. For this reason the periods, which are clearly and quite distinctly expressed—for instance, in the forms of combination—become to some extent involved (complicated) in the physical properties of their members. Thus, for instance, besides the maxima and minima corresponding with the periods and groups, new molecules appear; thus, as regards the melting-point of germanium, a local maximum appears, which was, however, foreseen by the periodic law when the properties of germanium (ekasilicon) were forecast.

[17 bis] The relation of certain elements (for instance, the analogues of Pt) among diamagnetic and paramagnetic bodies is sometimes doubtful (probably partly owing to the imperfect purity of the reagents under investigation). This subject has been studied in some detail by Bachmetieff in 1889.

[18] It is evident that many of the figures, especially those exceeding 1000°, have been determined with but little exactitude, and some, placed in [Table III.] with the sign (?), I have only given on the basis of rough and comparative determinations, calculated from the melting-points of silver and platinum, now established by many observers. In [Table III.], besides the large periods whose maxima correspond with carbon, silicon, titanium, ruthenium (?), and osmium (?), there are also small periods in the melting-points, and their maxima correspond with sulphur, arsenic, antimony. The minima correspond with the halogens and metals of the alkalis. A distinct periodicity is also seen in taking the coefficients of linear expansion (chiefly according to Fizeau); for instance, in the vertical series (according to the magnitude of the atomic weight), Fe, Co, Ni, Cu, the linear expansion in millionths of an inch = 12, 13, 17, and 29; for Rh, Pd, Ag, Cd, In, Sn, and Sb the coefficients are 8, 12, 19, 31, 46, 26, and 12, so that a maximum is reached at In. In the series Ir (7), Pt (5), Au (14), Hg (60), Tl (31), Pb (29), and Bi (14), the maximum is at Hg and the minimum at Pt. Raoul Pictet expressed this connection by the fact that he found the product α(t + 273)∛(A/d) to be nearly constant for all elements in the free state, and nearly equal to 0·045, and being the coefficient of linear expansion, t + 273, the melting-point calculated from the absolute zero (-273°), and ∛(A/d), the mean distance between the atoms, if A is the atomic weight and d the sp. gr. of an element. Although the above product is not strictly constant, nevertheless Pictet's rule gives an idea of the bond between magnitudes which ought to have a certain connection with each other. De Heen, Nadeschdin, and others also studied this dependence, but their deductions do not give a general and exact law.

[19] Carnelley found a similar dependence in comparing the melting-points of the metallic chlorides, many of which he re-determined for this purpose. The melting-points (and boiling-points, in brackets) of the following chlorides are known, and a certain regularity is seen to exist in them, although the number (and degree of accuracy) of the data is insufficient for a generalisation:—

We will also enumerate the following data given by Carnelley, which are interesting for comparison: HCl -112° (-102°); RbCl 710°, SrCl₂ 825°, CsCl 631°, BaCl₂ 860°, SbCl₃ 73° (223°), TeCl₂ 209° (327°), ICl 27°, HgCl₂ 276° (303°), FeCl₃ 306°, NbCl₅ 194° (240°), TaCl₃ 211° (242°), WCl₆ 190°. The melting-points of the bromides and iodides are higher or lower than those of the corresponding chlorides, according to the atomic weight of the element and number of atoms of the halogen, as is seen from the following examples:—1. KCl 734°, KBr 699°, KI 634°; 2. AgCl 454°, AgBr 427° AgI 527°; 3. PbCl₂ 498° (900°), PbBr₂ 499° (861°), PbI₂ 383° (906°); 4. SnCl₄ below -20° (114°), SnBr₂ 30° (201°), SnI₄ 146° (295°) (see Chapter II. Note [27], and Chapter XI. Note [47]^bis, &c.)

Laurie (1882) also observed a periodicity in the quantity of heat developed in the formation of the chlorides, bromides, and iodides (fig. [79]), as is seen from the following figures, where the heat developed is expressed in thousands of calories, and referred to a molecule of chlorine, Cl₂, so that the heat of formation of KCl is doubled, and that of SnCl₄ halved, &c.: Na 195 (Ag 59, Au 12), Mg 151 (Zn 97, Cd 93, Hg 63), Al 117, Si 79 (Sn 64), K 211 (Li 187), Ca 170 (Sr 185, Ba 194), whence it is seen that the greatest amount of heat is evolved by the metals of the alkalis, and that in each period it falls from them to the halogens, which evolve very little heat in combining together. Richardson, by comparing the heats of formation of the fluorides also came to the conclusion that they are in periodic dependence upon the atomic weights of the combined elements.

Fig. 79.—Laurie's diagram for expressing the periodic variation of the heat of formation of the chlorides. The abscissæ give the atomic weights from 0 to 210, and the ordinates the amounts of heat from 0 to 220 thousand calories evolved in the combination with Cl₂, (i.e. with 71 parts of chlorine). The apices of the curve correspond to Li, Na, K, Rb, Cs, and the lower extremities to F, Cl, Br, and I.

In this respect it may not be superfluous to remark (1) that Thomsen, whose results I have employed above, observed a correlation in the calorific equivalents of analogous elements, although he did not remark their periodic variation; (2) that the uniformity of many thermochemical deductions must gain considerably by the application of the periodic law, which evidently repeats itself in calorimetric data; and if these data frequently lead to true forecasts, this is due to the periodicity of the thermal as well as of many other properties, as Laurie remarked; and (3) that the heat of formation of the oxides is also subject to a periodic dependence which differs from that of the heat of formation of the chlorides, in that the greatest quantity corresponds with the bivalent metals of the alkaline earths (magnesium, calcium, strontium, barium), and not with the univalent metals of the alkalis, as is the case with chlorine, bromine, and iodine. This circumstance is probably connected with the fact that chlorine, bromine, and iodine are univalent elements, and oxygen bivalent (compare, for instance, Chapter XI., Note [13], Chapter XXII., Note [40], Chapter XXIV., Note [28]^bis, &c.)

Keyser (1892), in investigating the spectra of the alkali metals and metals of the alkaline earths, came to the conclusion that in this respect also there is a regularity of a periodic character in dependence upon the atomic weights. Probably a closer and systematic study of many of the properties of the elements and of complex and simple bodies formed by them will more and more frequently lead to similar conclusions, and to extending the range of application of the periodic law.

[19 bis] Probably, besides thermo-chemical data (Note [19]), the refractive index, cohesion, ductility, and similar properties of corresponding compounds or of the elements themselves will be found to exhibit a dependence of the magnitude of the atomic weight upon the periodic law.

[20] Having occupied myself since the fifties (my dissertation for the degree of M.A. concerned the specific volumes, and is printed in part in the Russian Mining Journal for 1856) with the problems concerning the relations between the specific gravities and volumes, and the chemical compositions of substances, I am inclined to think that the direct investigation of specific gravities gives essentially the same results as the investigation of specific volumes, only that the latter are more graphic. [Table III.] of the periodic properties of the elements clearly illustrates this. Thus, for those members whose volume is the greatest among the contiguous elements, the specific gravity is least—that is, the periodic variation of both properties is equally evident. In passing, for instance, from silver to iodine we have a successive decrease of specific gravity and successive increase of specific volume. The periodic alternation of the rise and fall of the specific gravity and specific volume of the free elements was communicated by me in August 1869 to the Moscow Meeting of Russian Naturalists. In the following year (1870) L. Meyer's paper appeared, which also dealt with the specific volume of the elements.

[21] In my opinion the mean volume of the atoms of compounds deserves more attention than has yet been paid to it. I may point out, for instance, that for feebly energetic oxides the mean volume of the atom is generally nearly 7; for example, the oxides SiO₂, Sc₂O₃, TiO₂, V₂O₅, as well as ZnO, Ga₂O₃, GeO₂, ZrO₂, In₂O₃, SnO₂, Sb₂O₅, &c., whilst the mean volume of the atom of the alkali and acid oxides is greater than 7. Thus we find in the magnitudes of the mean volumes of the atom in oxides and salts both a periodic variation and a connection with their energy of essentially the same character as occurs in the case of the free elements.

[22] The volume of oxygen (judging by the table on p. [36]) is evidently a variable quantity, forming a distinctly periodic function of the atomic weight and type of the oxide, and therefore the efforts which were formerly made to find the volume of the atom of oxygen in the volumes of its compounds may be considered to be futile. But since a distinct contraction takes place in the formation of oxides, and the volume of an oxide is frequently less than the volume in the free state of the element contained in it, it might be surmised that the volume of oxygen in a free state is about 15, and therefore the specific gravity of solid oxygen in a free state would be about O·9.

[23] As an example we will take indium oxide, In₂O₃. Its sp. gr. and sp. vol. should be the mean of those of cadmium oxide, Cd₂O₂, and stannic oxide, Sn₂O₄, as indium stands between cadmium and tin. Thus in the seventies it was already evident that the volume of indium oxide should be about 38, and its sp. gr. about 7·2, which was confirmed by the determinations of Nilson and Pettersson (7·179) made in 1880.

[24] As the distance between, and the volumes of, the molecules and atoms of solids and liquids certainly enter into the data for the solution of the problems of molecular mechanics, which as yet have only been worked out to any extent for the gaseous state, the study of the specific gravity of solids, and especially of liquids, has long had an extensive literature. With respect to solids, however, a great difficulty is met with, owing to the specific gravity varying not only with a change of isomeric state (for example, for silica in the form of quartz = 2·65, and in tridymite = 2·2) but also directly under mechanical pressure (for example, in a crystalline, cast, and forged metal), and even with the extent to which they are powdered, &c., which influences are imperceptible in liquids. Compare Chapter XIV., Note [55]^bis.

Without going into further details, we may add to what has been said above that the conception of specific volumes and atomic distances has formed the subject of a large number of researches, but as yet it is only possible to lay down a few generalisations given by Dumas, Kopp, and others, which are mentioned and amplified by me in my work cited in Note [20], and in my memoirs on this subject.

1. Analogous compounds and their isomorphs have frequently approximately the same molecular volumes.

2. Other compounds, analogous in their properties, exhibit molecular volumes which increase with the molecular weight.

3. When a contraction takes place in combination in a gaseous state, then contraction is in the majority of instances also to be observed in the solid or liquid state—that is, the sum of the volumes of the reacting substances is greater than the volume of the resultant substance or substances.

4. In decomposition the reverse takes place to that which occurs in combination.

5. In substitution (when the volumes in a state of vapour do not vary) a very small change of volume generally takes place—that is, the sum of the volumes of the reacting substances is almost equal to the sum of the resultant substances.

6. Hence it is impossible to judge the volume of the component substances from the volume of a compound, although it is possible to do so from the product of substitution.

7. The replacement of H₂ by sodium, Na₂, and by barium, Ba, as well as the replacement of SO₄ by Cl₂, scarcely changes the volume, but the volume increases with the replacement of Na by K, and decreases with the replacement of H₂, by Li₂ Cu, and Mg.

8. There is no need for comparing volumes in a solid and liquid state at the so-called corresponding temperatures—that is at temperatures at which vapour tension is equal in each case. The comparison of volumes at the ordinary temperature is sufficient for finding a regularity in the relations of volumes (this deduction was developed with particular detail by me in 1856).

9. Many investigators (Perseau, Schröder, Löwig, Playfair and Joule, Baudrimont, Einhardt) have sought in vain for a multiple proportion in the specific volumes of solids and liquids.

10. The truth of the above is seen very clearly in comparing the volumes of polymeric substances. The volumes of their molecules are equal in a state of vapour, but are very different in a solid and liquid state, as is seen from the close resemblance of the specific gravities of polymeric substances. But as a rule the more complex polymerides are denser than the simpler.

11. We know that the hydroxides of light metals have generally a smaller volume than the metals, whilst that of magnesium hydroxide is considerably greater, which is explained by the stability of the former and instability of the latter. In proof of this we may cite, besides the volumes of the true alkali metals, the volume of barium (36) which is greater than that of its stable hydroxide (sp. gr. 4·5, sp. vol. 30). The volumes of the salts of magnesium and calcium are greater than the volume of the metal, with the single exception of the fluoride of calcium. With the heavy metals the volume of the compound is always greater than the volume of the metal, and, moreover, for such compounds as silver iodide, AgI (d = 5·7), and mercuric iodide, HgI₂ (d = 6·2, and the volumes of the compounds 41 and 73), the volume of the compound is greater than the sum of the volumes of the component elements. Thus the sum of the volumes Ag + I = 36, and the volume of AgI = 41. This stands out with particular clearness on comparing the volumes K + I = 71 with the volume of KI, which is equal to 54, because its density = 3·06.

12. In such combinations, between solids and liquids, as solutions, alloys, isomorphous mixtures, and similar feeble chemical compounds, the sum of the reacting substances is always very nearly that of the resulting substance, but here the volume is either slightly larger or smaller than the original; speaking generally, the amount of contraction depends on the force of affinity acting between the combining substances. I may here observe that the present data respecting the specific volumes of solid and liquid bodies deserve a fresh and full elaboration to explain many contradictory statements which have accumulated on this subject.

CHAPTER XVI
ZINC, CADMIUM, AND MERCURY

These three metals give, like magnesium, oxides RO, which form feebly energetic bases, and like magnesium they are volatile. The volatility increases with the atomic weight. Magnesium can be distilled at a white heat, zinc at a temperature of about 930°, cadmium about 770°, and mercury about 351°. Their oxides, RO, are more easily reducible than magnesia, and mercuric oxide is the most easily reducible. The properties of their salts RX₂ are very similar to the properties of MgX₂. Their solubility, power of forming double and basic salts, and many other qualities are in many respects identical with those of MgX₂. The greater or less ease with which they are oxidised, the instability of their compounds, the density of the metals and their compounds, their scarcity in nature, and many other properties gradually change with the increase of atomic weight, as might be expected from the periodicity of the elements. Their principal characteristics, as contrasted with magnesium, find a general expression in the fact that zinc, cadmium, and mercury are heavy metals.

Zinc stands nearest to magnesium in atomic weight and in properties. Thus zinc sulphate, or white vitriol, easily crystallises with seven molecules of water, ZnSO₄,7H₂O. It is isomorphous with Epsom salts, and parts with difficulty with the last molecule of water; it forms double salts—for instance, ZnK₂(SO₄)₂,6H₂O—exactly as magnesium sulphate does.[1] Zinc oxide, ZnO, is a white powder, almost insoluble in water,[2] like magnesia, from which, however, it is distinguished by its solubility in solutions of sodium and potassium hydroxides.[3] Zinc chloride[4] is decomposed by water, combines with ammonium chloride, potassium chloride, &c., just like magnesium chloride, forms an oxychloride, and also combines with zinc oxide.[4 bis]

Zinc, like many heavy metals, is often found in nature in combination with sulphur, forming the so-called zinc blende,[5] ZnS. It sometimes occurs in large masses, often crystallised in cubes; it is frequently translucent, and has a metallic lustre, although this is not so clearly developed as in many other metallic sulphides with which we shall hereafter become acquainted. The ores of zinc also comprise the carbonate, calamine, and silicate, siliceous calamine.

Fig. 80.—Distillation of zinc in a crucible placed in a furnace. o c, tube along which the vapour passes and condenses.

Metallic zinc (spelter) is most frequently obtained from the ores containing the carbonate[6]—that is, from calamine, which is sometimes found in thick veins: for instance, in Poland, Galicia, in some places on the banks of the Rhine, and in considerable masses in Belgium and England. In Russia beds of zinc ore are met with in Poland and the Caucasus, but the output is small. In Sweden, as early as the fifteenth century, calamine was worked up into an alloy of zinc and copper (brass), and Paracelsus produced zinc from calamine; but the technical production of the metal itself, long ago practised in China, only commenced in Europe in 1807—in Belgium, when the Abbé Donnet discovered that zinc was volatile. From that time the production increased until it is now about 150 million kilograms in Germany alone.

The reduction of metallic zinc from its ores is based on the fact that zinc oxide[7] is easily reduced by charcoal at a red heat: ZnO + C = Zn + CO. The zinc thus obtained is in a finely divided state and impure, being mixed with other metals reduced with it, but the greater portion is converted into vapour, from which it easily passes into a liquid or solid state. The reduction and distillation are carried on in earthenware retorts, filled with a mixture of the divided ore and charcoal. The vapours of zinc and gases formed during the reaction escape by means of a pipe leading downwards, and are led to a chamber where the vapours are cooled. By this means they do not come into contact with the air, because the neck of the retort is filled with gaseous carbonic oxide, and therefore the zinc does not oxidise; otherwise its vapour would burn in the air.[7 bis] The vapours of zinc, entering into the cooling chamber, condense into white zinc powder or zinc dust. When the neck of the retort is heated the zinc is obtained in a liquid state, and is cast into plates, in which form it is generally sold.

Commercial zinc is generally impure, containing a mixture of lead, particles of carbon, iron, and other metals carried over with the vapours, although they are not volatile at a temperature approaching 1000°. If it be required to obtain pure zinc from the commercial article, it is subjected to a further distillation in a crucible with a pipe passing through the bottom, the vapours formed by the heated zinc only having exit through the pipe cemented into the bottom of the crucible. Passing through this pipe, the vapours condense to a liquid, which is collected in a receiver. Zinc thus purified is generally re-melted and cast into rods, and in this form is often used for physical and chemical researches where a pure article is required.[8]

Metallic zinc has a bluish-white colour; its lustre, compared with many other metals, is insignificant. When cast it exhibits a crystalline structure. Its specific gravity is about 7—that is, varies from 6·8 to 7·2, according to the degree of compression (by forging, rolling, &c.) to which it has been subjected. It is very ductile, considering its hardness. For this reason it chokes up files when being worked. Its malleability is considerable when pure, but in the ordinary impure condition in which it is sold, it is impossible to roll it at the ordinary temperature, as it easily breaks. At a temperature of 100°, however, it easily undergoes such operations, and can then be drawn into wire or rolled into sheets. If heated further it again becomes brittle, and at 200° may be even crushed into powder, so completely does it lose its molecular cohesion. It melts at 418°, and distils at 930°.

Zinc does not undergo any change in the atmosphere. Even in very damp air it only becomes slowly coated with a very thin white coating of oxide. For this reason it is available for all objects which are only in contact with air. Therefore sheet zinc may be used for roofing and many other purposes.[9] This great unchangeability of zinc in the air shows its slight energy with regard to oxygen compared with the metals already mentioned, which are capable of reducing zinc from solutions. But zinc plays this part with regard to the remaining metals—for example, it reduces salts of lead, copper, mercury, &c. Although zinc is an almost unoxidisable metal at the ordinary temperature, it burns in the air on being heated, particularly when in the form of shavings or in the condition of vapour. At the ordinary temperature zinc does not decompose water—at any rate, if the metal be in a dense mass. But even at a temperature of 100° zinc begins little by little to decompose water; it easily displaces the hydrogen of acids at the ordinary temperature, and of alkalis on being heated.

In this respect the action of zinc varies a great deal with the degree of its purity. Weak sulphuric acid (corresponding with the composition H₂SO₄,8H₂O) at the ordinary temperature does not act at all on chemically pure zinc, and even a stronger solution acts very slowly. If the temperature be raised, and particularly if the zinc be previously slightly heated, so as to cover the surface with a film of oxide, chemically pure zinc acts on sulphuric acid. Thus, for example, one cubic centimetre of zinc in sulphuric acid having a composition H₂SO₄,6H₂O at the ordinary temperature in two hours only dissolves to the extent of 0·018 gram, and at a temperature of 100° about 3·5 grams. If we compare this slow action with that rapid evolution of hydrogen which occurs in the case of commercial zinc, we see that the influence of those impurities in the zinc is very great. Every particle of charcoal or iron introduced into the mass of the zinc, and likewise the connection of the zinc with a piece of another electro-negative metal, assists such a dissolution. The slowness of the action of sulphuric acid on pure zinc (and likewise on amalgamated zinc) may also be explained by the fact that a layer of hydrogen[10] collects on the surface of the metal, preventing contact between the acid and the metal.[10 bis]

The action of zinc on acids, and the consequent formation of zinc salts, interferes with its application in many cases, particularly for the preservation of liquids either containing or capable of developing acid. For this reason zinc vessels ought not to be used for the preparation or preservation of food, as this often contains acids which form poisonous salts with the zinc. Even ordinary water, containing carbonic acid, slowly attacks zinc.

Finely divided zinc, or zinc dust, obtained in the distillation of the metal when the receiver is not heated up to the melting point, on account of its presenting a large surface of contact and containing foreign matter (particularly zinc oxide), has in the highest degree the property of decomposing acids, and even water, which it easily decomposes, particularly if slightly heated. On this account zinc dust is often used in laboratories and factories as a reducing agent. A similar influence of the finely divided state is also noticed in other metals—for instance, copper and silver—which again shows the close connection between chemical and physico-mechanical phenomena. We must first of all turn to this close connection for an explanation of the widely spread application of zinc in galvanic batteries, where the chemical (latent, potential) energy of the acting substances is transformed into (evident, kinetic) galvanic energy, and through this latter into heat, light, or mechanical work.

Hermann and Stromeyer, in 1819, showed that cadmium is almost always found with zinc, and in many respects resembles it. When distilled the cadmium volatilises sooner, because it has a lower boiling point. Sometimes the zinc dust obtained by the first distillation of zinc contains as much as 5 per cent. of cadmium. When zinc blende, containing cadmium, is roasted, the zinc passes into the state of oxide, and the cadmium sulphide in the ore oxidises into cadmium sulphate, CdSO₄, which resists tolerably well the action of heat; therefore if roasted zinc blende be washed with water, a solution of cadmium sulphate will be obtained, from which it is very easy to prepare metallic cadmium. Hydrogen sulphide may be used for separating cadmium from its solutions; it gives a yellow precipitate of cadmium sulphide, CdS (according to the equation CdSO₄ + H₂S = H₂SO₄ + CdS),[11] which, on account of its characteristic colour, is used as a pigment.[11 bis] Cadmium sulphide, when strongly heated in air, leaves cadmium oxide, from which the metal may be obtained in precisely the same way as in the case of zinc.

Cadmium is a white metal, and when freshly cut is almost as white and lustrous as tin. It is so soft that it may be easily cut with a knife, and so malleable that it can be easily drawn into wire, rolled into sheets, &c. Its specific gravity is 8·67, melting point 320°, boiling point 770°; its vapours burn, forming a brown powder of the oxide.[12] Next to mercury it is the most volatile metal; hence Deville determined the density of its vapours compared with hydrogen, and found it to be equal to 57·1; therefore the molecule contains one atom whose weight = 112. V. Meyer found the like for zinc; the molecule of mercury also contains one atom.

Mercury resembles zinc and cadmium in many respects, but presents that distinction from them which is always noticed in all the heaviest metals (with regard to atomic weight and density) compared with the lighter ones—namely, that it oxidises with more difficulty, and its compounds are more easily decomposed.[12 bis] Besides compounds of the usual type RX₂, it also gives those of the lower type, RX, which are unknown for zinc and cadmium.[13] Mercury therefore gives salts of the composition HgX (mercurous salts) and HgX₂ (mercuric salts), the oxides having the formulæ Hg₂O and HgO respectively.

Mercury is found in nature almost exclusively in combination with sulphur (like zinc and cadmium, but is still rarer than them) in the form known as cinnabar, HgS (Chapter XX., Note [29]). It is far more rarely met with in the native or metallic condition, and this in all probability has been derived from cinnabar. Mercury ore is found only in a few places—namely, in Spain (in Almaden), in Idria, Japan, Peru, and California. About the year 1880 Minenkoff discovered a rich bed of cinnabar in the Bahmout district (near the station of Nikitovka), in the Government of Ekaterinoslav, so that now Russia even exports mercury to other countries. Cinnabar is now being worked in Daghestan in the Caucasus. Mercury ores are easily reduced to metallic mercury, because the combination between the metal and the sulphur is one of but little stability. Oxygen, iron, lime, and many other substances, when heated, easily destroy the combination. If iron is heated with cinnabar, iron sulphide is formed; if cinnabar is heated with lime, mercury and calcium sulphide and sulphate are formed, 4HgS + 4CaO = 4Hg + 3CaS + CaSO₄. On being heated in the air, or roasted, the sulphur burns, oxidises, forming sulphurous anhydride, and vapours of metallic mercury are formed. Mercury is more easily distilled than all other metals, its boiling point being about 351°, and therefore its separation from natural admixtures, decomposed by one of the above-mentioned methods, is effected at the expense of a comparatively small amount of heat. The mixture of mercury vapour, air, and products of combustion obtained is cooled in tubes (by water or air), and the mercury condenses as liquid metal.[14]

Mercury, as everybody knows, is a liquid metal at the ordinary temperature. In its lustre and whiteness it resembles silver.[15] At -39° mercury is transformed into a malleable crystalline metal; at 0° its specific gravity is 13·596, and in the solid state at -40° it is 14·39.[16] Mercury does not change in the air—that is to say, it does not oxidise at the ordinary temperature—but at a temperature approaching the boiling-point, as was stated in the Introduction, it oxidises, forming mercuric oxide. Both metallic mercury and its compounds in general produce salivation, trembling of the hands, and other unhealthy symptoms which are found in the workmen exposed to the influence of mercurial vapours or the dust of its compounds.

As many of the compounds of mercury decompose on being heated—for instance, the oxide or carbonate[17]—and as zinc, cadmium, copper, iron, and other metals separate mercury from its salts,[18] it is evident that mercury has less chemical energy than the metals already described, even than zinc and cadmium. Nitric acid, when acting on an excess of mercury at the ordinary temperature, gives mercurous nitrate, HgNO₃.[19] The same acid, under the influence of heat and when in excess (nitric oxide being liberated), forms mercuric nitrate, Hg(NO₃)₂. This,[20] both in its composition and properties, resembles the salts of zinc and cadmium. Dilute sulphuric acid does not act on mercury, but strong sulphuric acid dissolves it, with evolution of sulphurous anhydride (not hydrogen), and on being slightly heated with an excess of mercury it forms the sparingly soluble mercurous sulphate, Hg₂SO₄; but if mercury be strongly heated with an excess of the acid, the mercuric salt, HgSO₄,[21] is formed. Alkalis do not act on mercury, but the non-metals chlorine, bromine, sulphur, and phosphorus easily combine with it. They form, like the acids, two series of compounds, HgX and HgX₂. The oxygen compound of the first series is the suboxide of mercury, or mercurous oxide, Hg₂O, and of the second order the oxide HgO, mercuric oxide. The chlorine compound corresponding with the suboxide is HgCl (calomel), and with the oxide HgCl₂ (corrosive sublimate or mercuric chloride). In the compounds HgX, mercury resembles the metals of the first group, and more especially silver. In the mercuric compounds there is an evident resemblance to those of magnesium, cadmium, &c. Here the atom of mercury is bivalent, as in the type RX₂.[22] Every soluble mercurous compound (corresponding with the type of the suboxide of mercury), HgX, forms a white precipitate of calomel, HgCl, with hydrochloric acid or a metallic chloride, because HgCl is very slightly soluble in water, HgX + MCl = HgCl + MX. In soluble mercuric compounds, HgX₂, hydrochloric acid and metallic chlorides do not form a precipitate, because corrosive sublimate, HgCl₂, is soluble in water. Alkali hydroxides precipitate the yellow mercuric oxide from a solution of HgX₂, and the black mercurous oxide from HgX. Potassium iodide forms a dirty greenish precipitate, HgI, with mercurous salts, HgX, and a red precipitate, HgI₂, with the mercuric salts, HgX₂. These reactions distinguish the mercuric from the mercurous salts, which latter represent the transition from the mercuric salts to mercury itself, 2HgX = Hg + HgX₂. The salts, HgX, as well as HgX₂, are reduced by nascent hydrogen (e.g. from Zn + H₂SO₄), by such metals as zinc and copper, and also by many reducing agents—for example, hypophosphorous acid, the lowest grade of oxidation of phosphorus, by sulphurous anhydride, stannous chloride, &c. Under the action of these reagents the mercuric salts are first transformed into the mercurous salts, and the latter are then reduced to metallic mercury. This reaction is so delicate that it serves to detect the smallest quantity of mercury; for instance, in cases of poisoning, the mercury is detected by immersing a copper plate in the solution to be tested, the mercury being then deposited upon it (more readily on passing a galvanic current). The copper plate, on being rubbed, shows a silvery white colour; on being heated, it yields vapours of mercury, and then again assumes its original red colour (if it does not oxidise). The mercurous compounds, HgX, under the action of oxidising agents, even air, pass into mercuric compounds, especially in the presence of acids (otherwise a basic salt is produced), 2HgX + 2HX + O = 2HgX₂ + H₂O; but the mercuric compounds, when in contact with mercury, change more or less readily, and turn into mercurous compounds, HgX₂ + Hg = 2HgX. For this reason, in order to preserve solutions of mercurous salts, a little mercury is generally added to them.

The lowest oxygen compound of mercury—that is, mercurous oxide, Hg₂O—does not seem to exist, for the substance precipitated in the form of a black mass by the action of alkalis on a solution of mercurous salts gradually separates on keeping into the yellow mercuric oxide and metallic mercury, as does also a simple mechanical mixture of oxide, HgO, with mercury (Guibourt, Barfoed). The other compound of mercury with oxygen is already known to us as mercuric oxide, HgO, obtained in the form of a red crystalline substance by the oxidation of mercury in the air, and precipitated as a yellow powder by the action of sodium hydroxide on solutions of salts of the type HgX₂. In this case it is amorphous and more amenable to the action of various reagents (Chap. XI., Note [32]) than when it is in the crystalline state. Indeed, on trituration, the red oxide is changed into a powder of a yellow colour. It is very sparingly soluble in water, and forms an alkaline solution which precipitates magnesia from the solution of its salts.

Mercury combines directly with chlorine, and the first product of combination is calomel or mercurous chloride, Hg₂Cl₂. This is obtained, as above stated, in the form of a white precipitate by mixing solutions of mercurous salts with hydrochloric acid or with metallic chlorides. A precipitate of calomel is also obtained by reducing a boiling aqueous solution of corrosive sublimate, HgCl₂, with sulphurous anhydride. It is likewise produced by heating corrosive sublimate with mercury.[22 bis] Calomel may be distilled (although in so doing it decomposes and recombines on cooling from a state of vapour); its vapour density equals 118 compared with hydrogen (= 1) (see Note [23]). In the solid state its specific gravity is 7·0; it crystallises in rhombic prisms, is colourless, but has a yellowish tint, turns brown from the action of light, and when boiled with hydrochloric acid decomposes into mercury and corrosive sublimate. It is used as a strong purgative. Corrosive sublimate or mercuric chloride, HgCl₂, can be obtained from or converted into calomel by many methods.[23] An excess of chlorine (for instance, aqua regia) converts calomel and also mercury into corrosive sublimate. It owes its name corrosive sublimate to its volatility, and, in medicine up to the present day, it is termed Mercurius sublimatus seu corrosivus. The vapour density, compared with hydrogen (= 1) is 135; therefore its molecule contains HgCl₂. It forms colourless prismatic crystals of the rhombic system, boils at 307°, and is soluble in alcohol. It is usually prepared by subliming a mixture of mercuric sulphate with common salt, HgSO₄ + 2NaCl = Na₂SO₄ + HgCl₂. Corrosive sublimate combines with mercuric oxide, forming an oxychloride or basic salt,[23 bis] of the composition HgCl₂,2HgO (magnesium and zinc form similar compounds). This compound is obtained by mixing a solution of corrosive sublimate with mercuric oxide or with a solution of sodium bicarbonate. In general, with both mercurous and mercuric salts, there is a marked tendency to form basic salts.[24]

Mercury has a remarkable power of forming very unstable compounds with ammonia, in which the mercury replaces the hydrogen, and, if a mercuric compound be taken, its atom occupies the place of two atoms of the hydrogen in the ammonia. Thus Plantamour and Hirtzel showed that precipitated mercuric oxide dried at a gentle heat, when continuously heated (up to 100°-150°) in a stream of dry ammonia, leaves a brown powder of mercuric nitride, N₂Hg₃, according to the equation 3HgO + 2NH₃ = N₂Hg₃ + 3H₂O.[24 bis] This substance, which is attacked by water, acids, and alkalis (giving a white powder), is very explosive when struck or rubbed, evolving nitrogen, proving that the bond between the mercury and the nitrogen is very feeble.[25] By the action of liquefied ammonia on yellow mercuric oxide Weitz also obtained an explosive compound, dimercurammonium hydroxide, N₂Hg₄O, which corresponds with an ammonium oxide, (NH₄)₂O, in which the whole of the hydrogen is replaced by mercury. A solution of ammonia reacts with mercuric oxide, forming the hydroxide, NHg₂.OH, to which a whole series of salts, NHg₂X, correspond; these are generally insoluble in water and capable of decomposing with an explosion. But salts of the same type, but with one atom of mercury, NH₂HgX, are more frequently and more easily formed; they were principally studied by Kane, although known much earlier. Thus, if ammonia be added to a solution of corrosive sublimate (or, still better, in reverse order), a precipitate is obtained known as white precipitate (Mercurius præcipitatus albus) or mercurammonium chloride, NH₂HgCl, which may also be regarded not only as sal-ammoniac with the substitution of H₂ by mercury, but also as HgX₂, where one X represents Cl and the other X represents the ammonia radicle, HgCl₂ + 2NH₃ = NH₂.HgCl + NH₄Cl. When heated, mercurammonium chloride decomposes, yielding mercurous chloride; when heated with dry hydrochloric acid it forms ammonium chloride and mercuric chloride. Other simple and double salts of mercurammonium, NH₂HgX, are also known. Pici (1890) showed that all the compounds HgH₂NX may be regarded as compounds of the above-named Hg₂NX with NH₄X because their sum equals 2HgH₂X.[25 bis]

Mercury as a liquid metal is capable of dissolving other metals and forming metallic solutions. These are generally called ‘amalgams.’ The formation of these solutions is often accompanied by the development of a large amount of heat—for instance, when potassium and sodium are dissolved (Chapter XII., Note [39]); but sometimes heat is absorbed, as, for instance, when lead is dissolved. It is evident that phenomena of this kind are exceedingly similar to the phenomena accompanying the dissolution of salts and other substances in water, but here it is easy to demonstrate that which is far more difficult to observe in the case of salts: the solution of metals in mercury is accompanied by the formation of definite chemical compounds of the mercury with the metals dissolved. This is shown by the fact that when pressed (best of all in chamois leather) such solutions leave solid, definite compounds of mercury with metals. It is, however, very difficult to obtain them in a pure state, on account of the difficulty of separating the last traces of mercury, which is mechanically distributed between the crystals of the compounds. Nevertheless, in many cases such compounds have undoubtedly been obtained, and their existence is clearly shown by the evident crystalline structure and characteristic appearance of many amalgams. Thus, for instance, if about 2½ p.c. of sodium be dissolved in mercury, a hard, crystalline amalgam is obtained, very friable and little changeable in air. It contains the compound NaHg₅ (Chapter XII., Note [39]). Water decomposes it, with the evolution of hydrogen, but more slowly than other sodium amalgams, and this action of water only shows that the bond between the sodium and the mercury is weak, just like the connection between mercury and many other elements—for instance, nitrogen. Mercury directly and easily dissolves potassium, sodium, zinc, cadmium, tin, gold, bismuth, lead, &c., and from such solutions or alloys it is in most cases easy to extract definite compounds—thus, for instance, the compounds of mercury and silver have the compositions HgAg and Ag₂Hg₃. Objects made of copper when rubbed with mercury become covered with a white coating of that metal, which slowly forms an amalgam; silver acts in the same way, but more slowly, and platinum combines with mercury with still greater difficulty. This metal only readily forms an amalgam when in the form of a fine powder. If salts of platinum in solution are poured on to an amalgam of sodium, the latter element reduces the platinum, and the platinum separated is dissolved by the mercury. Almost all metals readily form amalgams if their solutions are decomposed by a galvanic current, where mercury forms the negative pole. In this way an amalgam may even be made with iron, although iron in a mass does not dissolve in mercury. Some amalgams are found in nature—for instance, silver amalgams. Amalgams are used in considerable quantities in the arts. Thus the solubility of silver in mercury is taken advantage of for extracting that metal from the ore by means of amalgamation, and for silvering by fire. The same is the case with gold. Tin amalgam, which is incapable of crystallising and is obtained by dissolving tin in mercury, composes the brilliant coating of ordinary looking-glasses, which is made to adhere to the surface of the polished glass by simply pressing by mechanical means sheets of tin foil bathed in mercury on to the cleansed surface of the glass.[26] (See ‘The Nature of Amalgams,’ by W. L. Dudley; Toronto, 1889.)

Footnotes:

[1] Zinc sulphate is often obtained as a by-product—for instance, in the action of galvanic batteries containing zinc and sulphuric acid. When the anhydrous salt is heated it forms zinc oxide, sulphurous anhydride, and oxygen. The solubility in 100 parts of water at O° = 43, 20° = 53, 40° = 63½, 60° = 74, 80° = 84½, 100° = 95 parts of anhydrous zinc sulphate—that is to say, it is closely expressed by the formula 43 + 0·52t.

An admixture of iron is often found in ordinary sulphate of zinc in the form of ferrous sulphate, FeSO₄, isomorphous with the zinc sulphate. In order to separate it, chlorine is passed through the solution of the impure salt (when the ferrous salt is converted into ferric), the solution is then boiled, and zinc oxide is afterwards added, which, after some time has elapsed, precipitates all the ferric oxide. Ferric oxide of the form R₂O₃ is displaced by zinc oxide of the form RO.

[2] Zinc oxide is obtained both by the combustion and oxidation of zinc, and by the ignition of some of its salts—for instance, those of carbonic and nitric acids; it is likewise precipitated by alkalis from a solution of ZnX₂ in the form of a gelatinous hydroxide. The oxide produced by roasting zinc blende (by burning in the air, when the sulphur is converted into sulphurous anhydride) contains various impurities. For purification, the oxide is mixed with water, and the sulphurous anhydride formed by roasting the blende is passed through it. Zinc bisulphite, ZnSO₃,H₂SO₃, then passes into solution. If a solution of this salt be evaporated, and the residue ignited, zinc oxide, free from many of its impurities, will remain. Zinc oxide is a light white powder, used as a paint instead of white lead; the basic salt, corresponding with magnesia alba, is used for the same purpose. V. Kouriloff (1890) by boiling the hydrate of the oxide with a 3 p.c. solution of peroxide of hydrogen obtained Zn₂H₂O₄ or the hydrate of the peroxide (= ZnO₂ZnH₂O₂ or a compound of 2ZnO with H₂O₂), which did not part with its oxygen at 100°, but only above 120°. Cadmium gives a similar compound of a yellow colour. Magnesium, although it does form such a compound, does so with great difficulty.

[3] For the solution of one part of the oxide 55,400 parts of water are required. Nevertheless, even in such a weak solution, zinc oxide (hydroxide, ZnH₂O₂) changes the colour of red litmus paper. Zinc oxide is obtained in the wet way by adding an alkali hydroxide to a solution of a zinc salt—for instance: ZnSO₄ + 2HKO = K₂SO₄ + ZnH₂O₂. The gelatinous precipitate of zinc hydroxide is soluble in an excess of alkali, which clearly distinguishes it from magnesia. This solubility of zinc hydroxide in alkalis is due to the power of zinc oxide to form a compound, although an unstable one, with alkalis—that is to say, points to the fact that zinc oxide already partly belongs to the intermediate oxides. The oxides of the metals above mentioned (except BeO) do not show this property. The property which metallic zinc itself has of dissolving in caustic alkali with the disengagement of hydrogen (the solution is facilitated by contact with platinum or iron) depends on the formation of such a compound of the oxides of zinc and the alkali metals. The solution of zinc hydroxide, ZnH₂O₂, in potash (in a strong solution), proceeds when these hydrates are taken in proportion to ZnH₂O₂ + KHO. If such a solution be evaporated to dryness, water extracts only caustic potash from the fused residue. When a solution of zinc hydroxide in strong alkali is mixed with a large mass of water, nearly all the oxide of zinc is precipitated; and, therefore, in weak solutions, a large quantity of the alkali is required to effect solution, which points to the decomposition of the zinc-alkali compounds by water. If strong alcohol be added to a solution of zinc oxide in sodium hydroxide, the crystallo-hydrate, 2Zn(OH)(ONa),7H₂O, separates.

[4] Zinc chloride, ZnCl₂, is generally employed in the arts in the form of a solution obtained by dissolving zinc in hydrochloric acid. This solution is used for soldering metals, impregnating wood, &c. The reason why it is thus employed may be understood from its properties. When evaporated it first parts with its water of crystallisation; on being further heated, however, it loses all traces of water, and forms an oily mass of anhydrous salt which solidifies on cooling. This substance melts at 250°, commences to volatilise at about 400°, and boils at 730°. The soldering of metals—that is, the introduction of an easily fusible metal between two contiguous metallic objects—is hindered by any film of oxide upon them; and, as heated metals easily oxidise, they are naturally difficult to solder. Zinc chloride is used to prevent the oxidation. It fuses on being heated, and, covering the metal with an oily coating, prevents contact with the air; but even if any oxide has formed, the free hydrochloric acid generally existing in the zinc chloride solution dissolves it, and in this way the metallic surface of the metals to be soldered is preserved fit for the adhesion of the liquid solder, which, on cooling, binds the objects together. Much zinc chloride is used also for steeping wood (telegraph-posts and railway-sleepers) in order to preserve it from decaying quickly; this preservative action is in all probability mainly due to the poisonous character of zinc salts (corrosive sublimate is still more poisonous, and a still better agent to preserve wood from decay), since decay is due to the action of lower organisms.

The specific gravity of solutions containing p per cent. of zinc chloride, ZnCl₂, is as follows:

The last line shows the change of specific gravity for 1° in ten-thousandth parts for temperatures near 15°. More accurate determinations of Cheltzoff, personally communicated by him, led him to conclude that solutions of zinc chloride follow the same laws as the solutions of sulphuric acid, which will be considered in Chapter [XX.]: (1) from H₂O to ZnCl₂,120H₂O s = S₀ + 92·85p + 0·1748p²; (2) from thence to ZnCl₂,40H₂O s = S₀ + 93·96p - 0·0126p²; (3) thence to ZnCl₂,25H₂O s = 11481·5 + 96·45(p - 15·89) + 0·4567(p - 15·89)²; (4) thence to ZnCl₂,10H₂O s = 12212·1 + 104·82(p - 23·21) + 0·7992(p - 23·21)²; (5) thence to p = 65 p.c. s = 14606·3 + 140·96(p - 43·05) + 1·4905(p - 43·05)², where s is the specific gravity of the solution at 15°, containing p p.c. of ZnCl₂ by weight, taking water at 4° = 10000, and where S₀ = 9991·6 (specific gravity of water at 15°). The compound of zinc chloride with hydrochloric acid has been mentioned in Vol. I. Chapter [X.]

Zinc chloride has a great affinity for water; it is not only soluble in it, but in alcohol, and on being dissolved in water becomes considerably heated, like magnesium and calcium chlorides. Zinc chloride is capable of taking up water, not only in a free state, but also in chemical combination with many substances. Thus, for instance, it is used in organic researches for removing the elements of water from many of the organic compounds.

[4 bis] When mixed with zinc oxide it forms, with remarkable ease, a very hard mass of zinc oxychloride, which is applied in the arts; for instance, in painting, to resist the action of water, or for cementing such objects as are destined to remain in water. Zinc oxychloride, ZnCl₂,3ZnO,2H₂O (= Zn₂OCl₂,2ZnH₂O₂), is also formed from a solution of zinc chloride by the action of a small quantity of ammonia on it after heating the precipitate obtained with the liquid for a considerable time; the admixture of ammonium salts with a mixture of a strong solution of zinc chloride with its oxide makes a similar mass, which does not solidify so rapidly, and is therefore more useful for some purposes. Moisture and cold do not change the hardened mass of oxychloride, and it also resists the action of many acids, and a temperature of 300°, which makes it a useful cement for many purposes. A solution of magnesium chloride with magnesium oxide forms a similar oxychloride. The mass solidifies best when there are equal quantities by weight of zinc in the chloride and oxide, and therefore when it has the composition Zn₂OCl₂ In preparing such a cement, naturally zinc oxide alone may be taken, and the requisite quantity of hydrochloric acid added to it. The capacity of ZnCl₂ to combine with water, ZnO, and HCl (and also with other metallic chlorides) indicates its property to combine with molecules of other substances, and therefore its compounds with NH₃, and especially a compound, ZnCl₂2NH₃, similar to sal-ammoniac, might be expected (i.e. 2NH₄Cl, in which H₂ is replaced by Zn). And indeed it has long been known that ZnCl₂ absorbs ammonia and gives solid substances capable of dissociating with the disengagement of NH₃. Among these compounds Isambert and V. Kouriloff (1894) obtained ZnCl₂6NH₃, ZnCl₂4NH₃, ZnCl₂2NH₃, and ZnCl₂NH₃. The dissociation tension of the two last-mentioned compounds at 218° is equal to 43·6 mm. and 6·7 mm. CdCl₂ also forms similar compounds with NH₃ (Kouriloff, 1894).

[5] This mineral has been given the name of ‘mock-ore,’ on account of its having the appearance (considerable density, 4·06, &c.) of ordinary metallic ores; it deceived the first miners, because it did not, like other ores, give metal when simply roasted in air and fused with charcoal. The white zinc oxide, formed by burning the vapours of zinc, was also called ’nihil album,’ or ‘white nothing,’ on account of its lightness.

[6] It may be here mentioned that by the word ore is meant a hard, heavy substance dug out of the earth, which is used in metallurgical works for obtaining the usual heavy metals long known and used. The natural compounds of sodium, or magnesium, are not called ores, because magnesium and sodium have not been long obtainable in quantity. The heavy metals, those which are easily reduced and do not easily oxidise, are exclusively those which are directly applied in manufactures. Ores either contain the metals themselves (for instance, ores of silver or bismuth), and the metals are then said to be in a native state, or else their sulphur compounds (blende, mock-ore, pyrites—as, for example, galena, PbS; zinc blende, ZnS; copper pyrites, CuFeS) or oxides (as the ores of iron), or salts (calamine, for instance). Zinc is incomparably rarer than magnesium, and is only well known because it is transformed from its ores into a metal which finds direct use in many branches of industry.

[7] Ores, when extracted from the earth by the miners, are often enriched by sorting, washing, and other mechanical operations. The sulphurous ores (and likewise others) are then generally roasted. Roasting an ore means heating it to redness in air. The sulphur then burns, and passes off in the form of sulphurous anhydride, SO₂, and the metal oxidises. The roasting is carried on in order to obtain an oxide instead of a sulphur compound, the oxide being reducible by charcoal. These methods, introduced ages ago, are met with in nearly all metallurgical works for practically all ores. For this reason the preparatory treatment of zinc blende furnishes zinc oxide: this is already contained in calamine.

[7 bis] with very impure ores, especially such as contain lead (PbS often accompanies zinc), the vapour of the reduced zinc is allowed to pass directly into the air. It burns and gives ZnO, which is used as a pigment.

[8] This zinc, although homogeneous, still contains certain impurities, to remove which it is necessary to prepare some salt of zinc in a pure state and transform it into carbonate, which latter is then distilled with charcoal; and, as thin sheets of zinc can only be obtained from very pure metal, they are frequently made use of in cases where pure zinc is required. In order to remove the arsenic from zinc, it was proposed to melt it and mix it with anhydrous magnesium chloride, by which means vapours of zinc chloride and arsenic chloride are formed. Perfectly pure zinc is made (V. Meyer and others) by decomposing, by means of the galvanic current, a solution of zinc sulphate to which an excess of ammonia has been added. The zinc used for Marsh's arsenic test (Chapter [XIX.]) is purified from As by fusing it with KNO₃ and then with ZnCl₂.

[9] Cornices and other architectural ornaments, remarkable for their lightness and beauty, are stamped out of sheet zinc. Zinc-roofing does not require painting, but it melts during a conflagration, and even burns at a strong heat. Many iron vessels, &c., are covered with zinc (‘galvanised’) in order to prevent them from rusting.

[10] Veeren (1891) proved this by simple experiments, finding that in vacuo the solution proceeds far more rapidly for both pure and commercial zinc, and still more rapidly in the presence of oxidising agents (which absorb the hydrogen) like CrO₃ and H₂O₂.

[10 bis] The addition of cupric sulphate, or, better still, a few drops of platinic chloride (the metals become reduced), to the sulphuric acid greatly accelerates the evolution of the hydrogen, because in this case, as with commercial zinc, galvanic couples are formed locally by the copper or platinum and the zinc, under the influence of which the zinc rapidly dissolves. The action of acids on metallic zinc of various degrees of purity has been the subject of many investigations, particularly important with reference to the application of zinc in galvanic batteries, whilst some investigations have direct significance for chemical mechanics, although from many points of view the matter is not clear. I consider it useful to mention certain of these investigations.

Calvert and Johnson made the following series of observations on the action of sulphuric acid of various degrees of concentration on 2 grams of pure zinc during two hours. In the cold the concentrated acid, H₂SO₄, does not act, H₂SO₄,2H₂O dissolves about 0·002 gram, but principally forms hydrogen sulphide, which is obtained also when the dilution reaches H₂SO₄,7H₂O, when 0·035 gram of zinc is dissolved. When largely diluted with water, pure hydrogen begins to be disengaged. H₂SO₄,2H₂O at 130° gives a mixture of hydrogen sulphide and sulphurous anhydride dissolving 0·156 gram of zinc.

Bouchardat showed that if in a vessel made of glass or sulphur dilute sulphuric acid acting on a piece of zinc liberates one part of hydrogen, then the same acid with the same piece of zinc in the same time will liberate 4 parts of hydrogen if the vessel be made of tin—that is, zinc forms a galvanic couple with tin; in a leaden vessel 9 parts of hydrogen are set free, with a vessel of antimony or bismuth 13 parts, silver or platinum 38 parts, copper 50 parts, iron 43 parts. If a salt of platinum be added to the dilute sulphuric acid (1 part of acid and 12 parts of water), Millon determined that the rapidity of the action on the zinc is increased 149 times, and by the addition of copper sulphate is rendered 45 times greater than the action of pure sulphuric acid. The salts which are added are reduced to metals by the zinc, their contact serving to promote the reaction because they form local galvanic currents.

According to the observations of Cailletet, if, at the ordinary pressure, sulphuric acid with zinc liberates 100 parts of hydrogen, then with a pressure of 60 atmospheres 47 parts will be liberated and 1 part at a pressure of 120 atmospheres. With a reduced pressure under the receiver of an air-pump 168 parts are liberated. Helmholtz showed that a reduced pressure also exercises its influence on galvanic elements.

Debray, Löwel, and others showed that zinc liberates hydrogen and forms basic salts and zinc oxide with solutions of many salts—for instance, MCl_n, aluminium sulphate, and alum, Sodium and potassium carbonates scarcely act, because they form carbonates. The salts of ammonia act more strongly than the salts of potassium and sodium; the zinc remains bright. It is evident that this action is founded on the formation of double salts and basic salts.

The variation with concentration in the rate of the action of sulphuric acid on zinc (containing impurities) under otherwise uniform conditions is in evident connection with the electrical conductivity of the solution and its viscosity, although, when largely diluted, the action is almost proportional to the amount of acid in a known volume of the solution. Forging, casting the molten metal, and similar mechanical influences change the density and hardness of zinc, and also strongly influence its power of liberating hydrogen from acids. Kayander showed (1881) that when magnesium is submitted to the action of acids: (a) the action depends, not on the nature of the acid, but on its basicity; (b) the increase of the action is more rapid than the growth of the concentration; and (c) there is a decrease of action with the increase of the coefficient of internal friction and electrical conductivity.

Spring and Aubel (1887) measured the volume of hydrogen disengaged by an alloy of zinc and a small quantity of lead (0·6 p.c.), because the action of acids is then uniform. In order to deal with a known surface, spheres were taken (9·5 millimetres diameter) and cylinders (17 mm. dia.), the sides of which were covered with wax in order to limit the action to the end surfaces. During the commencement of the action of a definite quantity of acid the rapidity increases, attains a maximum, and then declines as the acid becomes exhausted. The results for 5, 10, and 15 per cent. of hydrochloric acid are given below. H denotes the number of cubic centimetres of hydrogen, D the time in seconds elapsing after the zinc spheres have been plunged into the acid. At 15° were obtained:

In consequence of the complex character of the phenomenon, the authors themselves do not consider their determinations as being conclusive, and only give them a relative significance; and in this connection it is remarkable that hydrobromic acid under similar conditions (with an equivalent strength) gives a greater (from 2 to 5 times) rapidity of action than hydrochloric acid, but sulphuric acid a far smaller velocity (nearly 25 times smaller). It is also remarkable that during the reaction the metal becomes much more heated than the acid.

It may be mentioned that zinc dust and zinc itself, when heated with hydrated lime and similar hydrates, disengages hydrogen: this method has even been proposed for obtaining hydrogen for filling war balloons.

[11] It may be here remarked that sulphate of zinc (especially in the presence of mineral acids) does not give a precipitate of sulphide of zinc, or is only slightly precipitated by sulphuretted hydrogen.

[11 bis] Sulphide of cadmium appears in two varieties of a similar chemical but different physical character: one is of a lemon colour, and the other bright red. Kloboukoff (1890) studied the physical properties of these varieties more closely. The sp. gr. of the former is 3·906, and of the latter 4·513. They belong to different crystallographic systems. The first variety may be converted into the second by friction or pressure, but the second cannot be converted into the first variety by these means.

[12] Amongst the compounds of cadmium very closely allied to the compounds of zinc, we must mention cadmium iodide, CdI₂, which is used in medicine and photography. This salt crystallises very well: it is prepared by the direct action of iodine, mixed with water, on metallic cadmium. One part of cadmium iodide at 20° requires for its solution 1·08 part of water. It may be remarked that cadmium chloride at the same temperature requires 0·71 part of water to dissolve it, so that the iodine compound of this metal is less soluble than the chloride, whilst the reverse relation holds in the case of the corresponding compounds of the alkali or alkaline earthy metals. Cadmium sulphate crystallises well, and has the composition 3CdSO₄,8H₂O, thus differing from zinc sulphate.

Cadmium oxide is soluble, although sparingly, in alkalis, but in the presence of tartaric and certain other acids the alkaline solution of cadmium oxide does not change when boiled, whilst a diluted solution in that case deposits cadmium oxide: this may also serve for separating zinc compounds from those of cadmium. Cadmium is precipitated from its salts by zinc, which fact may also be taken advantage of for separating cadmium; for this reason, in an alloy of zinc and cadmium, acids first of all extract the zinc. Cadmium is in all respects less energetic than zinc. Thus, for instance, it decomposes water with difficulty, and this only when strongly heated. It even acts but slowly on acids, but then displaces hydrogen from them. It is necessary here to call attention to the fact that for alkali and alkaline earthy metals (of the even series) the highest atomic weight determines the greatest energy; but cadmium (of the uneven series), whilst having a larger atomic weight than zinc, is less energetic. The salts of cadmium are colourless, like those of zinc. De Schulten obtained a crystalline oxychloride, Cd(OH)Cl by heating marble with a solution of cadmium chloride in a sealed tube at 200°.

[12 bis] According to its atomic weight, mercury follows gold in the periodic system, just as cadmium follows silver and zinc follows copper:—

Eventually we shall see the near relation of platinum, palladium, and nickel, and also of gold, silver, and copper, but we will now point out the parallelism between these three groups. The relation between the physical and also chemical properties is here strikingly similar. Nickel, palladium, and platinum are very difficult to fuse (far more so than iron, ruthenium, and osmium, which stand before them). Copper, silver, and gold melt far more easily in a strong heat than the three preceding metals, and zinc, cadmium, and mercury melt still more easily. Nickel, palladium, and platinum are very slightly volatile; copper, silver, and gold are more volatile; and zinc, cadmium, and mercury are among the most volatile metals. Zinc oxidises more easily than copper, and is reduced with more difficulty, and the same is true for mercury as compared with gold. These properties for cadmium and silver are intermediate in the respective groups. Relations of this kind clearly show the nature of the periodic law.

[13] Thus thallium, lead, and bismuth, following mercury according to their atomic weights, form, besides compounds of the highest types, TlX₃, PbX₄, and BiX₅, also the lower ones TlX, PbX₂, and BiX₃.

[14] During the condensation of the vapours of mercury in works, a part forms a black mass of finely-divided particles, which gives metallic mercury when worked up in centrifugal machines, or on pressure, or on re-distillation. In mercury we observe a tendency to easily split up into the finest drops, which are difficult to unite into a dense mass. It is sufficient to shake up mercury with nitric and sulphuric acids in order to produce such a mercury powder. The mercury separated (for instance, reduced by substances like sulphurous anhydride) from solutions, forms such a powder. According to the experiments of Nernst, this disintegrated mercury when entering into reactions develops more heat than the dense liquid metal—that is to say, the work of disintegration reappears in the form of heat. This example is instructive in considering thermochemical deductions.

[15] Mercury may sometimes be obtained in a perfectly pure state from works (in iron bottles holding about 35 kilos), but after being used in laboratories (for baths, calibration, &c.) it contains impurities. It may be purified mechanically in the following way: a paper filter with a fine hole (pricked with a needle) is placed in a glass funnel and mercury is poured into it, which slowly trickles through the hole, leaving the impurities upon the filter. Sometimes it is squeezed through chamois leather or through a block of wood (as in the well-known experiment with the air-pump). It may be purified from many metals by contact with dilute nitric acid, if small drops of mercury are allowed to pass through a long column of it (from the fine end of a funnel); or by shaking it up with sulphuric acid in air. Mercury may be purified by the action of an electric current, if it be covered with a solution of HgNO₃. But the complete purification of mercury for barometers and thermometers can only be attained by distillation, best in a vacuum (the vapour-tension of mercury is given in Chapter II., Note [27]). For this purpose Weinhold's apparatus is most often used. The principle of this apparatus is very ingenious, the distillation being effected in a Torricellian vacuum continuously supplied with fresh mercury, whilst the condensed mercury is continuously removed. This process of distillation requires very little attention, and gives about one kilo of pure mercury per hour.

[16] If the volume of liquid mercury at 0° be taken as 1000000, then, according to the determinations of Regnault (recalculated by me in 1875), at t it will be 1000000 + 180·1t + 0·02t².

[17] All salts of mercury, when mixed with sodium carbonate and heated, give mercurous or mercuric carbonates; these decompose on being heated, forming carbonic anhydride, oxygen, and vapours of mercury.

[18] Spring (1888) showed that, solid dry HgCl is gradually decomposed in contact with metallic copper. According to the determinations of Thomsen, the formation of a gram of mercurial compounds from their elements develops the following amounts of heat (in thousands of units): Hg₂ + O, 42; Hg + O, 31; Hg + S, 17; Hg + Cl, 41; Hg + Br, 34; Hg + I, 24; Hg + Cl₂, 63; Hg + Br₂, 51; Hg + I₂, 34; Hg + C₂N₂, 19. These numbers are less than the corresponding ones for potassium, sodium, calcium, barium, and for zinc and cadmium—for instance, Zn + O, 85; Zn + Cl₂, 97; Zn + Br₂, 76; Zn + I₂, 49; Cd + Cl₂, 93; Cd + Br₂, 75; Cd + I₂, 49.

[19] This salt easily forms the crystallo-hydrate HgNO₃,H₂O, corresponding with ortho-nitric acid, H₃NO₄ (the terms ortho-, pyro-, and meta-acids are explained in the chapter on Phosphorus), with the substitution of Hg for H. In an aqueous solution this salt can only be preserved in the presence of free mercury, otherwise it forms basic salts, which will be mentioned hereafter (Chapter VI., Note [59]).

[20] Mercuric nitrate, Hg(NO₃)₂,8H₂O, crystallises from a concentrated solution of mercury in an excess of boiling nitric acid. Water decomposes this salt; at the ordinary temperature crystals of a basic salt of the composition Hg(NO₃)₂,HgO,2H₂O are formed, and with an excess of water the insoluble yellow basic salt Hg(NO₃)₂,H₂O,2HgO. These three salts correspond with the type of ortho-nitric acid, (H₃NO₄)₂, in which mercury is substituted for 1, 2 and 3 times H₂. As all these salts still contain water, it is possible that they correspond with the tetrahydrate = N₂O₅ + 4H₂O = N₂O(OH)₈ if ortho-nitric acid = N₂O₅ + 3H₂O = 2NO(OH)₃.

[21] To obtain the mercuric salt a large excess of strong sulphuric acid must be taken and strongly heated. With a small quantity of water colourless crystals of HgSO₄,H₂O may be obtained. An excess of water, especially when heated, forms the basic salt (as in Note [20]), HgSO₄,2HgO, which corresponds with trihydrated sulphuric acid, SO₃ + 3H₂O = S(OH)₆, with the substitution of H₆ by 3Hg, which in mercuric salts is equivalent to H₆. Le Chatelier (1888) gives the following ratio between the amounts of equivalents per litre:

—that is, the relative amount of free acid decreases as the strength of the solution increases.

[22] The question of the molecular weight of calomel—that is, whether the mercury in the salts of the suboxide is monatomic or diatomic—long occupied the minds of chemists, although it is not of very great importance. It is only recently (1894) that this question can be considered as answered, thanks to the researches of V. Meyer and Harris, in favour of diatomicity—that is, that calomel is analogous to peroxide of hydrogen and contains Hg₂Cl₂ (like O₂H₂) in its molecule if corrosive sublimate contains HgCl₂ (like water OH₂). As a matter of fact, direct experiment gives the vapour density of calomel as about 118—that is, indicates that its molecule contains HgCl, whilst the molecule of the sublimate, judging also by the vapour density (nearly 136), contains HgCl₂; it might therefore be concluded that the mercury in the suboxide is not only monovalent (corresponding to H) but also monatomic, whilst in the oxide it is divalent and diatomic. Instances of a variable atomicity, as shown by the vapour density, are known in N₂O, NO, and NH₃, CO and CO₂, PCl₃ and PCl₅, and it might therefore be supposed that the present was a similar instance. But there are also instances of a variable equivalency which do not correspond to a variation of atomicity—for example, OH₂ (water) and OH (peroxide of hydrogen), CH₄ (methane), C₂H₅ (ethyl), and CH₂ (ethylene), &c. Here, according to the law of substitution, the residues of OH₂ and CH₄ combine together and give molecules; OHOH = O₂H₂ (peroxide of hydrogen) and CH₃CH₃ = C₂H₆ (ethane), &c. The same may be assumed also to be the relation of calomel to sublimate; the residue HgCl, which is combined with Cl in sublimate, corresponds to HgCl₂, and in calomel it may be supposed that this residue is combined with itself, forming the molecule Hg₂Cl₂. On this view of the composition of the molecule of calomel it would follow that in the state of vapour it breaks up into two molecules, HgCl₂ and Hg, when the vapour density would be about 118 (because that of sublimate is about 136 and that of mercury about 100), and that in cooling this mixture (like a mixture of HCl and NH₃) again gives Hg₂Cl₂. It was therefore necessary to prove that calomel is decomposed in the state of vapour. This was not effected for a long time, although Odling, as far back as the thirties, showed that gold becomes amalgamated (i.e. absorbs metallic mercury) in the vapour of calomel, but not in the vapour of sublimate. Recently, however, V. Meyer and Harris (1894) have shown that a greater amount of the vapour of mercury than of calomel passes (at about 465°) through a porous clay cell, containing calomel. This proves that the vapour of calomel contains a mixture of the vapours of Hg and HgCl₂, as would follow from the second hypothesis. Moreover, on introducing a heated piece of KHO into the vapour of calomel, Meyer observed the formation, not of suboxide (black), but of oxide of mercury (yellow). Therefore the molecular formula of calomel must be taken as Hg₂Cl₂ (and not HgCl).

[22 bis] Calomel (in Japanese ‘Keyfun’) has been prepared in Japan (and China) for many centuries, by heating mercury in clay crucibles with sea salt, which contains MgCl₂ and gives HCl. The vapour of the mercury reacts with this HCl and the oxygen of the air and forms calomel: 2Hg + 2HCl + O = Hg₂Cl₂ + H₂O. The calomel collects on the lid of the crucible in the form of a sublimate (Divers, 1894).

[23] HgCl₂ is partially converted into calomel even in the act of dissolving in ordinary water, especially under the action of light.

[23 bis] As feebly energetic bases (for instance, the oxides MgO, ZnO, PbO, CuO, Al₂O₃, Bi₂O₃, &c.), mercuric oxide (see Notes [20], [21]) and mercurous oxide easily give basic salts, which are usually directly formed by the action of water on the normal salt, according to the general equation (for mercuric compounds, RX₂):

or else are produced directly from the normal salt and the oxide or its hydroxide. Thus mercurous nitrate, when treated with water, forms basic salts of the composition 6(HgNO₃),Hg₂O,H₂O, 2(HgNO₃),Hg₂O,H₂O, and 3(HgNO₃),Hg₂O,H₂O, the first two of which crystallise well. Naturally it is possible either to refer similar salts to the type of hydrates—for instance, the second salt to the hydrate N₂O₅,4H₂O—or to view it as a compound, HgNO₃,HgHO, but our present knowledge of basic salts is not sufficiently complete to admit of generalisations. However, it is already possible to view the subject in the following aspects: (1) basic salts are principally formed from feeble bases; (2) certain metals (mentioned above) form them with particular ease, so that one of the causes of the formation of many basic salts must depend on the property of the metal itself; (3) those bases which readily form basic salts as a rule also readily form double salts; (4) in the formation of basic salts, as also everywhere in chemistry, where sufficient facts have accumulated, we clearly see the conditions of equally balanced heterogeneous systems, such as we saw, for instance, in the formation of double salts, crystallo-hydrates, &c.

The mercuric salts often form double salts (confirming the third thesis), and mercuric chloride easily combines with ammonia, forming Hg(NH₄)₂Cl₄, or in general HgCl₂nMCl. If a mixture of mercurous and potassium sulphates be dissolved in dilute sulphuric acid, the solution easily yields large colourless crystals of a double salt of the composition K₂SO₄,3HgSO₄,2H₂O. Boullay obtained crystalline compounds of mercuric chloride with hydrochloric acid, and mercuric iodide with hydriodic acid; and Thomsen describes the compound HgBr₂,HBr,4H₂O as a well-crystallised salt, melting at 13°, and having, in a molten state, a specific gravity 3·17 and a high index of refraction. Moreover, the capacity of salts for forming basic compounds has been considerably cleared up since the investigation (by Würtz, Lorenz, and others) of glycol, C₂H₄(OH)₂ (and of polyatomic alcohols resembling it), because the ethers C₂H₄X₂, corresponding with it, are capable of forming compounds containing C₂H₄X₂nC₂H₄O.

On the other hand, there is reason to think that the property of forming basic salts is connected with the polymerisation of bases, especially colloidal ones (see the chapter on Silica, Lead Salts, and Tungstic Acid).

[24] Mercuric iodide, HgI₂, is obtained first as a yellow, and then as a red, precipitate on mixing solutions of mercuric salts and potassium iodide, and is soluble in an excess of the latter (in consequence of the formation of the double salt, HgKI₃); of ammonium chloride (for a similar reason), &c. It crystallises at the ordinary temperature in square prisms of a red colour. On being heated, these change into yellow rhombic crystals, isomorphous with mercuric chloride. This yellow form of mercuric iodide is very unstable, and when cooled and triturated easily again assumes the more stable red form. When fused, a yellow liquid is obtained. Mercuric cyanide, Hg(CN)₂, forms one of the most stable metallic cyanides. It is obtained by dissolving mercuric oxide in prussic acid, and by boiling Prussian blue with water and mercuric oxide, ferric oxide being then obtained in the precipitate. Mercuric cyanide is a colourless crystalline substance, soluble in water, and distinguished by its great stability; sulphuric acid does not liberate prussic acid from it, and even caustic potash does not remove the cyanogen (a complex salt is probably produced), but the halogen acids disengage HCN. Like the chloride, it combines with mercuric oxide, forming the oxycyanide, Hg₂O(CN)₂, and it shows a very marked tendency to form double compounds—for example, K₂Hg(CN)₄. The alkali chlorides and iodides form similar compounds—for instance, the salt HgKI(CN)₂ crystallises very well, and is produced by directly mixing solutions of potassium iodide and mercuric cyanide.

Wells (1889) and Vare obtained and investigated many such double salts, and showed the possibility of the formation, not only of HgCl₂MCl and HgCl₂2MCl where M is a metal of the alkalis—for example, Cs—but also of HgCl₂3MCl,2(HgCl₂)MCl, and in general nHgX₂mMX, where X stands for various haloids.

[24 bis] See Chapter XIX., Note [6 bis]: Hg₃P₂. In studying the metallic nitrides it is necessary to keep the corresponding phosphides in mind.

[25] Hg₃N₂ is similar in composition to Mg₃N₂, &c. (Chapter [XIV.]) The readiness with which mercuric nitride explodes shows that the connection between the nitrogen and the mercury is very unstable, and explains the circumstance that the so-called mercury fulminate, or fulminating mercury, is an exceedingly explosive substance. This substance is prepared in large quantities for explosive mixtures; it enters into the composition of percussion caps, which explode when struck, and ignite gunpowder. Mercury fulminate was discovered by Howard, and from that time has been prepared in the following way: one part of mercury is dissolved in twelve parts of nitric acid, of sp. gr. 1·36, and when the whole of the mercury is dissolved, 5·5 parts of 90 p.c. alcohol are added, and the mass is shaken. A reaction then commences, accompanied by a rise in temperature due to the oxidation of the alcohol. As a matter of fact, many oxidation products are produced during the action of the nitric acid on the alcohol (glycolic acid, ethers, &c.) When the reaction becomes tolerably vigorous, the same quantity of alcohol is added as at the commencement, when a grey precipitate of the fulminate separates. This salt has the composition C₂Hg(NO₂)N. It explodes when struck or heated. The mercury in it may be replaced by other metals—for instance, copper or zinc, and also silver. The silver salt, C₂Ag₂(NO₂)N, is obtained in a precisely analogous manner, and is even more explosive. Under the action of alkali chlorides, only half the silver is replaced by the alkali metal, but if the whole of the silver be replaced by an alkali metal, then the salt decomposes. This is evidently because combinations of this kind proceed in virtue of the formation of substances in which mercury, and metals akin to it, are connected in an unstable way with nitrogen. Potassium and other light metals are incapable of entering into such connection and therefore, the substitution of potassium for mercury entails the splitting-up of the combination. Investigations of the fulminates were carried on by Gay-Lussac and Liebig, but only the investigations of L. N. Shishkoff fully cleared up the composition and relation of these substances to the other carbon compounds. Shishkoff showed that fulminates correspond with the nitro-acid, C₂H₂(NO₂)N. The explosiveness of the group depends partly on its containing at the same time NO₂ and carbon; we already know that all such nitrogen compounds are explosive. If we imagine that the NO₂ is replaced by hydrogen, we shall have a substance of the composition C₂H₃N. This is acetonitrile—that is, acetic acid + NH₃ - 2H₂O, or ethenyl nitrile, as shown in Chapter [VI.] The formation of an acetic compound by the action of nitric acid on alcohol is easily understood, because acetic acid is produced by the oxidation of alcohol, and the production of the elements of ammonia, indispensable for the formation of a nitrile, is accounted for by the fact that nitric acid under the action of reducing substances in many cases forms ammonia. Moreover a certain analogy has been found between fulminating acid and hydroxylamine, but details upon this subject must be looked for in works on organic chemistry. The explosiveness of fulminating mercury, the rapidity of its decomposition (gunpowder, and even guncotton, burn more slowly and explode less violently), and the force of its explosion, are such that a small quantity (loosely covered) will shatter massive objects.

The investigations of Abel on the communication of explosion from one substance to another are remarkable. If guncotton be ignited in an open space, it burns quietly; but if fulminating mercury be exploded by the side of it, the decomposition of the guncotton is effected instantaneously, and it then shatters the objects upon which it lies, so rapid is the decomposition. Abel explains this by supposing that the explosion of the fulminating salt brings the molecules of guncotton into a uniform or as it were harmonious state of vibration, which causes the rapid decomposition of the whole mass. This rapid decomposition of explosive substances defines the distinction between explosion and combustion. Besides this, Berthelot showed that from that form of powerful molecular concussion which takes place during the explosion of fulminating mercury, the state of strain and stability of equilibrium of substances which are endothermal, or capable of decomposing with the disengagement of heat—for instance, cyanogen, nitro compounds, nitrous oxide, &c.—is generally destroyed. Thorpe showed that carbon bisulphide, CS₂, also an endothermal substance, decomposes into sulphur and charcoal, when fulminating mercury is exploded in contact with it.

[25 bis] The capacity for replacing hydrogen in chloride of ammonium by metals also belongs to Zn and Cd. Kvasnik (1892), by the action of ammonia upon alcoholic solutions of CdCl₂ and ZnCl₂, obtained substances of the general formula M(NH₃Cl)₂, formed as it were from two molecules of sal-ammoniac by the substitution of two atoms of hydrogen by a diatomic metal. These substances appear as white, finely crystalline powders. Under the action of heat half the ammonia passes off, and a compound of the composition MClNH₃Cl is formed. The compounds of cadmium and zinc are distinguished from each other by the former being more volatile than the latter.

We may further remark that in the series Mg, Zn, Cd, and Hg the capacity to form double salts of diverse composition increases with the atomic weight. Thus, according to Wells and Walden's observations (1893), the ratio n : m for the type nMClmRCl₂ (M = K, Li, Na … R = Mg, Zn …) is for Mg 1 : 1, for Zn 3 : 1, 2 : 1, and 1 : 1; for Cd, besides this, salts are known with the ratio 4 : 1, and for Hg 3 : 1, 2 : 1, 1 : 1, 2 : 3, 1 : 2, and 1 : 5.

[26] I consider it appropriate here to call attention to the want of an element (ekacadmium) between cadmium and mercury in the periodic system (Chapter [XV.]) But as in the ninth series there is not a single known element, it may be that this series is entirely composed of elements incapable of existing under present conditions. However, until this is proved in one way or another, it may be concluded that the properties of ekacadmium will be between those of cadmium and mercury. It ought to have an atomic weight of about 155, to form an oxide EcO, a slightly stable oxide Ec₂O. Both ought to be feeble bases, easily forming double and basic salts. The volume of the oxide will be nearly 17·5, because the volume of cadmium oxide is about 16, and that of mercuric oxide 19. Therefore the density of the oxide will approach 171 ÷ 17·5 = 9·7. The metal ought to be easily fusible, oxidising when heated, of a grey colour, with a specific volume, about 14 (cadmium = 13, mercury = 15), and, therefore, its specific gravity (155 ÷ 14) will nearly = 11. Such a metal is unknown. But in 1879 Dahl, in Norway, discovered in the island of Oterö, not far from Kragerö, in a vein of Iceland spar in a nickel mine, traces of a new metal which he called norwegium, and which presented a certain resemblance to ekacadmium. Perfect purity of the metal was not attained, and therefore the properties ascribed to norwegium must be regarded as approximate, and likely to undergo considerable alteration on further study. A solution of the roasted mineral in acid was twice precipitated by sulphuretted hydrogen, and again ignited; the oxide obtained was easily reduced. When the metal was dissolved in hydrochloric acid largely diluted with water, and the solution boiled, the basic salt was precipitated, and thus freed from the copper which remained in the solution. The reduced metal had a density 9·44, and easily oxidised. If the composition NgO be assigned to the oxide, then Ng = 145·9. It fused at 254°; the hydroxide was soluble in alkalis and potassium carbonate. In any case, if norwegium is not a mixture of other metals, it belongs to the uneven series, because the heavy metals of the even series are not easily reducible. Brauner thinks that norwegium oxide is Ng₂O₃, the atom Ng = 219, and places it in Group VI., series 11, but then the feebly acid higher oxide, NgO₃, ought to be formed.

Amongst the metals accompanying zinc which have been named, but not authentically separated, must be included the actinium of Phipson (1881). He remarked that certain sorts of zinc give a white precipitate of zinc sulphide which blackens on exposure to light and then becomes white in the dark again. Its oxide, closely resembling in many ways cadmium oxide, is insoluble in alkalis, and it forms a white metallic sulphide, blackening on exposure to light. As no further mention has been made of it since 1882, its existence must be regarded as doubtful.

CHAPTER XVII
BORON, ALUMINIUM, AND THE ANALOGOUS METALS OF THE THIRD GROUP

If the elements of small atomic weight which we have hitherto discussed be placed in order, it will be clearly seen that, judging by the formulæ of their higher compounds, one element is wanting between beryllium and carbon. For lithium gives LiX, beryllium forms BeX₂, and then comes carbon giving CX₄. Evidently to complete the series we must look for an element forming RX₃, and having an atomic weight greater than 9 and less than 12. And boron is such a one; its atomic weight is 11, and its compounds are expressed by BX₃. Lithium and beryllium are metals; carbon has no metallic properties; boron appears in a free state in several forms which are intermediate between the metals and non-metals. Lithium gives an energetic caustic oxide, beryllium forms a very feeble base; hence one would expect to find that the oxide of boron, B₂O₃, has still more feeble basic properties and some acid properties, all the more as CO₂ and N₂O₅, which follow after B₂O₃ in their composition and in the periodic system, are acid oxides. And, indeed, the only known oxide of boron exhibits a feeble basic character, together with the properties of a feeble acid oxide. This is even seen from the fact that a solution of boron oxide reddens blue litmus and acts on turmeric paper as an alkali, and these reactions may be used for determining the presence of B₂O₃ in solutions. By themselves the alkali borates have an alkaline reaction, which clearly indicates the feeble acid character of boric acid. If they are mixed in solution with hydrochloric acid, boric acid is liberated, and if a piece of turmeric paper be immersed in this solution and then dried, the excess of hydrochloric acid volatilises, while the boric acid remains on the paper and communicates a brown coloration to it, just like alkalis.

Boron trioxide or boric anhydride enters into the composition of many minerals, in the majority of cases in small quantities as an isomorphous admixture, not replacing acids but bases, and most frequently alumina (Al₂O₃), for as a rule the amount of alumina decreases as that of the boric anhydride increases in them. This substitution is explained by the similarity between the atomic composition of the oxides of aluminium (alumina) and boron. The subdivision of oxides into basic and acid can in no way be sharply defined, and here we meet with the most conclusive proof of the fact, for the oxides of boron and aluminium belong to the number of intermediate oxides, closely approaching the limit separating the basic from the acid oxides. Their type (Chapter [XV.]) R₂O₃ is intermediate between those of the basic oxides R₂O and RO and those of the acid oxides R₂O₅ and RO₃. If we turn our attention to the chlorides, we remark that lithium chloride is soluble in water, is not volatile, and is not decomposed by water; the chlorides of beryllium and magnesium are more volatile, and although not entirely, still are decomposed by water; whilst the chlorides of boron and aluminium are still more volatile and are decomposed by water. Thus the position of boron and aluminium in the series of the other elements is clearly defined by their atomic weights, and shows us that we must not expect any new and distinct functions in these elements.

Boron was originally known in the form of sodium borate, Na₂B₄O₇,10H₂O, or borax, or tincal, which was exported from Asia, where it is met with in solution in certain lakes of Thibet; it has also been discovered in California and Nevada, U.S.A.[1] Boric acid was afterwards found in sea-water and in certain mineral springs.[2] Its presence may be discovered by means of the green coloration which it communicates to the flame of alcohol, which is capable of dissolving free boric acid.[3] Many of the boron compounds employed in the arts are obtained from the impure boric acid which is extracted in Tuscany from the so-called suffioni. In these localities, which present the remains of volcanic action, steam mixed with nitrogen, hydrogen sulphide, small quantities of boric acid, ammonia, and other substances, issue from the earth.[3 bis] The boric acid partially volatilises with the steam, for if a solution of boric acid be boiled, the distillate will always contain a certain amount of this substance.[4]

If boric acid be introduced into an excess of a strong hot solution of sodium hydroxide, then, on slowly cooling, the salt NaBO₂,4H₂O crystallises out. This salt contains an equivalent of Na₂O to one equivalent B₂O₃. It might be termed a neutral salt did it not possess strongly alkaline reactions and easily split up into the alkali and the more stable borax or biborate of sodium mentioned above, which contains 2B₂O₃ to Na₂O.[5] This salt is prepared by the action of boric acid on a solution of sodium carbonate. Borax may be perfectly purified by crystallisation. If a saturated and hot solution of borax be mixed with strong hydrochloric acid, common salt and a normal crystalline hydrate of boric acid are formed. The composition of this hydrate is B(HO)₃, according to the form BX₃—that is, of the composition B₂O₃,3H₂O. This is the easiest method of obtaining pure boric acid. The water is easily expelled from this hydrate; it loses half at 100° and the remainder on further heating, and the remaining B₂O₃ or boric anhydride fuses at 580° (according to Carnelley), forming at first a ductile (easily drawn out into threads), tenacious mass and then a colourless liquid solidifying to a transparent glass, which absorbs moisture from the atmosphere and then becomes cloudy.[6] Only the alkaline salts of boric acid are soluble in water, but all borates are soluble in acids, owing to their easy decomposability and the solubility of boric acid itself. Although boric anhydride, B₂O₃, absorbs 3H₂O from damp air, still in the presence of water it always[7] combines with a less quantity of bases (borax only contains ¹⁄₆). However, fused boric anhydride forms a crystalline compound with magnesium of the same type as the hydrate (MgO)₃B₂O₃ (Ebelmann), and even with sodium it forms (Na₂O)₃B₂O₃ or Na₃BO₃ (Benedict). As a rule, the salts of boric acid contain less base, although they are all able to form saline compounds with bases when fused. Generally, vitreous fluxes are formed by this means,[8] which when fused recall ordinary aqueous solutions in many respects. Some of them crystallise on solidifying, and then they have, like salts, a definite composition. The property of boric anhydride of forming higher grades of combination with basic oxides when fused explains the power of fused borax to dissolve metallic oxides, and the experiments of Ebelmann on the preparation of artificial crystals of the precious stones by means of boric anhydride. Boric anhydride is, although with difficulty, volatile at a high temperature, and therefore if it dissolves an oxide, it may be partially driven off from such a solution by prolonged and powerful ignition; in which case the oxides previously in solution separate out in a crystalline form, and frequently in the same forms as those in which they occur in nature—for example, crystals of alumina, which by itself fuses with difficulty, have been obtained in this manner. It dissolves in molten boric anhydride, and separates out in natural rhombohedric crystals. In this way Ebelmann also obtained spinel—that is, a compound of magnesium and aluminium oxides which occurs in nature.[9]

Free boron was obtained (1809) by Davy, Gay-Lussac, and Thénard when they obtained the metals of the alkalis, for boric anhydride when fused with sodium gives up its oxygen to the sodium, and free boron is liberated as an amorphous powder like charcoal.[10] It is of a brown colour, specific gravity 2·45 (Moissan), and when dry does not alter in the air at the ordinary temperature; but it burns when ignited to 700°, and in so doing combines not only with the oxygen of the air, but also with the nitrogen. However, the combustion is never complete, because the boric anhydride formed on the surface covers the remaining mass of the boron, and so preserves it from the action of the oxygen. Acids, even sulphuric (forming SO₂) and phosphoric (forming phosphorus), easily oxidise amorphous boron, especially when heated, converting it into boric acid. Alkalis have the same action on it, only in this case hydrogen is evolved. Boron decomposes steam at a red heat, also with evolution of hydrogen.

Amorphous boron, like charcoal, dissolves in certain molten metals. The property of fused aluminium of dissolving boron in considerable quantity is very striking; on cooling such a solution, the boron partially combined with the aluminium separates out in a crystalline form, and its properties are then exceedingly remarkable. The crystalline boron may be obtained by heating (to 1,300°) the pulverulent boron with aluminium in a well-closed crucible, the access of air being prevented as far as possible. After cooling, crystals are observed on the surface of the aluminium, and may easily be separated by dissolving the latter in hydrochloric acid, which does not act on the crystals. The specific gravity of the crystals is 2·68; they are partially transparent, but are for the most part coloured dark brown; they contain about 4 p.c. of carbon and up to 7 p.c. of aluminium, so that they cannot be considered as pure boron. Nevertheless, the properties of this crystalline substance, which was obtained by Wöhler and Deville, are very remarkable. It most closely resembles the diamond in its properties—in fact, these crystals have the lustre and high refracting power proper to the diamond only, whilst their hardness competes with that of the diamond. Their powder polishes even the diamond, and like the diamond scratches the sapphire and corundum. Crystalline boron is much more stable with respect to chemical reagents than the amorphous variety, and as it resembles the diamond, so amorphous boron, on the other hand, distinctly recalls certain of the properties of charcoal; thus a certain resemblance exists between boron and carbon in a free state, which is further justified by the proximity of their positions in the periodic system.

Among the other compounds of boron, those with nitrogen and the halogens are the most remarkable. As already mentioned above, amorphous boron combines directly with nitrogen at a red heat. If it be heated in a glass tube in a stream of nitric oxide, perfect combustion takes place, 5B + 3NO = B₂O₃ + 3BN. If the residue be treated with nitric acid, the boric anhydride dissolves, whilst the boron nitride remains[11] as an extremely light white powder, which is sometimes partially crystalline and greasy to the touch, like talc. It is infusible and unchanged, even at the melting-point of nickel. In general, it is remarkable for its great stability with respect to chemical reagents. Nitric and hydrochloric acids, as well as alkaline solutions, and hydrogen and chlorine at a red heat, have no action on it. When fused with potash, it evolves ammonia, and when ignited in steam it also yields ammonia: 2BN + 3H₂O = B₂O₃ + 2NH₃.[12]

No less remarkable is the compound of boron with fluorine—boron fluoride, BF₃. It is produced in many instances when compounds of boron and of fluorine are brought together.[13] The most convenient method of preparing it is by heating a mixture of calcium fluoride with boric anhydride and sulphuric acid, 3CaF₂ + B₂O₃ + 3H₂SO₄ = 3CaSO₄ + 3H₂O + 2BF₃.[14] It is a colourless liquefiable gas (the liquid boils at -100°), which on coming into contact with damp air forms white fumes, owing to its combining with water. One volume of water dissolves as much as 1,050 volumes of this gas (Bazaroff), forming a liquid which disengages boron fluoride when heated, and distils over unaltered. Boron fluoride chars organic matter, owing to its taking up the water from it, and in this respect it acts like sulphuric acid. The behaviour of boron fluoride with water must be understood as a reversible reaction, since with water it yields hydrofluoric and boric acids, whilst they, acting on one another, re-form boron fluoride and water. A state of equilibrium is set up between these four substances (and between two reversible reactions) which is distinctly dependent on the mass of the water.[14 bis] When boron fluoride is in great excess, the equilibrated system, which is capable of distilling over (sp. gr. of the liquid 1·77), has a composition BF₃,2H₂O (or B₂O₃,H₂O,6HF). It has also its corresponding salts.[15] It is a caustic liquid, having the properties of a powerful acid; but it does not act on glass, which shows that there is no free hydrofluoric acid present. Under the action of water this system changes, with the formation of boric acid and hydroborofluoric acid (HBF₄) according to the equation 4BF₃H₄O₂ = 3HBF₄ + BH₃O₃ + 5H₂O.[16] This hydroborofluoric acid has its corresponding salts—for instance, KBF₄. On evaporating the aqueous solution this free acid decomposes, with the evolution of hydrofluoric acid, and a stable system is again obtained: 2HBF₄ + 5H₂O = B₂F₆H₁₀O₅ + 2HF. The resultant solution (containing 2BF₃,5H₂O, sp. gr. 1·58), which is identical with that formed by the evaporation of a solution of boric acid with hydrofluoric acid, again only contains a compound of boron fluoride with water. Probably there are various other possible and more or less stable states of equilibrium and definite compounds of boron fluoride, hydrofluoric acid, and water.

Nothing of this kind occurs with boron chloride, because hydrochloric acid does not act on boric acid. However, amorphous boron at 400° burns in chlorine, and at 410° forms boron chloride, BCl₃. The boron burns in the chlorine, forming a gas which, in a freezing mixture, condenses into a liquid boiling at 17°, and gives up its excess of chlorine, if there be any, to mercury. The specific gravity of this liquid is 1·42 at 6°. Boron chloride may also be directly obtained from boric anhydride by the simultaneous action of charcoal and chlorine at a high temperature: B₂O₃ + 3C + 3Cl₂ = 2BCl₃ + 3CO. It is also obtained by the action of phosphoric chloride on boric anhydride in a closed tube at 200° It is completely decomposed by water, like the chloranhydride of an acid, boric acid being formed; hence it fumes in the air: 2BCl₃ + 6H₂O = 2BH₃O₃ + 6HCl. Boron forms with bromine a similar compound, BBr₃, specific gravity at 6° = 2·64, boiling at 90°. The vapour densities of the fluoride, chloride, and bromide of boron show that they contain three atoms of the halogen in the molecule—that is, that boron is a trivalent element forming BX₃.[16 bis]

As in the first group lithium is followed by sodium, giving a more basic oxide, so in the second group beryllium is followed by magnesium, and so also in the third group there is, besides the lightest element, boron, whose basic character is scarcely defined, aluminium, Al = 27, whose oxide, alumina, has somewhat distinct basic properties, which, although not so powerful as in magnesium oxide, are more distinct than in boric anhydride. Among the elements of the third group, aluminium is the most widely distributed in nature; it will be sufficient to mention that it enters into the composition of clay to demonstrate the universal distribution of aluminium in the earth's crust.

Alumina is so named from its being the metal of alums (alumen).

Clay, which is so widely distributed and familiar to everybody, is the insoluble residue obtained after the action of water containing carbonic acid on many rocks, and especially on the felspars contained in some of them. Felspar is a compound containing potash or soda, alumina, and silica. The primary rocks, like granite, contain many similar compounds (see Chapter [XVIII.]: Felspars). Felspar is acted on by water containing carbonic acid, all the alkalis (potash and soda), and a portion of the silica passing into the water as substances which are soluble and carried away by it, whilst the alumina and silica left from the felspar remain on the spot where the solution has taken place. This is the original method of the formation of clay in its primary deposits among rocks along whose crevices the atmospheric water has permeated. Such primary deposits often contain a white pure clay, termed kaolin or porcelain clay. But such clay is a rarity, because the conditions for its formation are rarely met with. The water, whilst acting chemically on rocks, at the same time destroys them mechanically, and carries off the finely divided residues of disintegration with it. Clay is most easily subjected to this mechanical action of water, because it is composed of grains of exceedingly small size and void of any visible crystalline structure, which easily remain suspended in water. The cloudy water of running mountain streams generally contains particles of clay in suspension, owing to the above-described chemical and mechanical action of the water on the minerals contained in the mountain rocks. Together with these minute particles of clay the water carries away the coarser components on which it is not able to act—for example, splinters of rock, grains of mica, quartz, &c. They were originally held together by those minerals which form clay. When the water acts on these binding minerals, a sandy mass is formed which water bears away. The cloudy water in which the particles of clay and sand are held in suspension carries them to, and deposits them at, the estuaries of rivers, lakes, seas, and oceans. The coarser particles are first deposited and form sand and similar disintegrated rocky matter, whilst the clay, owing to its finely divided state, is carried on further, and is only deposited in the still parts of the rivers, lakes, &c. Such disintegrations of rocks and separations of clay from sand have been gradually going on during the millions of years of the earth's existence, and are now proceeding, and have been the cause of the formation of the immense deposits of sandstone and clay now forming a part of the earth's strata. Such beds of clay may have been transferred by currents and streams from one locality to another, so that we must distinguish between primary and secondary deposits of clay. In places these beds of clay have, owing to long exposure under water, and perhaps partially owing to the action of heat, undergone compression, and have formed the rocky masses known as clay slates and schists, which sometimes form entire mountains. Roofing slates belong to this class of rocks.

From what has been said above it will be evident that these deposits can never consist of a chemically pure and homogeneous substance, but will contain all kinds of extraneous insoluble finely divided matter, and especially sand—that is, fragments of rock, chiefly quartz (SiO₂). It is, however, possible to considerably purify clay from these impurities, owing to the fact that they are the result of mechanical disintegration, whilst the clay has been formed as a residue of the chemical alteration of rocky matter, and therefore its particles are incomparably more minute than the particles of sand and other rock fragments mixed with it. This difference in the size of the grains causes the clay to remain longer in suspension when shaken up in water than the coarser grains of sand. If clay be shaken up in water, and especially if it be previously boiled in it, and if after the first portion has settled the cloudy water be decanted, it will give a deposit of a very much purer clay than the original. This method is employed for purifying kaolin designed for the manufacture of the best kinds of china, earthenware, &c. A similar method is also employed in the investigation of earths for determining the composition of soils chiefly composed of a mixture of sand, clay, limestone, and mould. The limestone is soluble in dilute acids, but neither the clay nor sand passes into solution by this means, and therefore the limestone is easily separated in the investigation of soils. The clay is separated from the sand by a mechanical method similar to that described above, and termed levigation.[17]

By treating clay with strong sulphuric acid, which dissolves the alumina in it, and then (by means of an alkaline carbonate) dissolving the silica which was combined with the alumina in the clay (but not that occurring in the form of sand, &c., which is hardly dissolved by carbonate of soda solution at all even on boiling), we may form an idea of the proportion between the component parts of a clay; and by igniting it at a high temperature, we may determine the amount of water held in it. In the purer sorts of clay dried at 100° (sp. gr. of pure kaolin is about 2·5) this proportion is about 2SiO₂ : 2H₂O : Al₂O₃. In this case the conversion of felspar into kaolin is expressed by the equation:—

the compound K₂O,4SiO₂ passes into solution.

But as a rule clays contain from 45 to 60 p.c. of silica, from 20 to 30 p.c. of alumina, and about 12 p.c. of water; and it cannot be supposed that clays are always homogeneous, because they are an aggregation of residues (of silico-aluminous compounds) which are unacted on by water. Nevertheless, clays always contain a hydrous compound of alumina and silica, which is able to give up the alumina contained by it as a base to strong sulphuric acid, forming aluminium sulphate, which is soluble in water. After this treatment the silica remains, and is soluble in a solution of an alkaline carbonate.[18]

Clay is the source from which alumina, Al₂O₃, and the majority of the compounds of aluminium are prepared. Among these compounds the most important are the alums—that is, the double sulphates of potassium (and allied metals) and aluminium, AlK(SO₄)₂,12H₂O. When clay is treated with sulphuric acid diluted with a certain amount of water, aluminium sulphate, Al₂(SO₄)₃, is formed; and if potassium carbonate or sulphate be added to this solution, a double salt or alum is obtained in solution. The alums crystallise easily, and are prepared on a very large manufacturing scale owing to their being employed in the process of dyeing. Alums are soluble in water, and, on the addition of ammonia to their solutions, they give hydrous alumina, or aluminium hydroxide, as a white gelatinous precipitate, which is insoluble in water but easily soluble in acids, even when dilute, and in aqueous soda or potash. The solubility of alumina in acids indicates the basic character of the oxide, and its solubility in alkalis and its power of forming compounds with them shows the weakness of this basic character. However, the feeblest acids, even carbonic acid, take up the alkali from such a solution, and the alumina then separates out in a precipitate as the hydroxide. It must also be remembered as characteristic of the salt-forming properties of alumina that it does not combine with such feeble acids as carbonic, sulphurous, or hypochlorous, &c.—that is, its compounds with these acids are decomposed by water. It is also important to observe that the hydroxide is not soluble in aqueous ammonia.

Alumina, Al₂O₃—that is, the anhydrous aluminium oxide—is met with in nature, sometimes in a somewhat pure state, having crystallised in transparent crystals, which are often coloured by impurities (chromic, cobaltic, and ferric compounds). Such are the ruby and sapphire, the former red and the latter blue. They have a specific gravity 4·0, are distinguished by their very great hardness, which is second only to that of the diamond, and they represent the purest form of alumina. They are found in Ceylon and other islands of the Indian Archipelago, embedded in a rock matrix.[18 bis] Corundum is the same crystallised anhydrous alumina coloured brown by a trace of oxide of iron. A very much larger portion of this impurity occurs in emery, which is found in crystalline masses in Asia Minor and in Massachusetts, and owing to its extreme hardness is employed for polishing stones and metals. In this anhydrous and crystalline state the aluminium oxide is a substance which very powerfully resists the action of reagents, and is insoluble both in solutions of the alkalis and in strong acids. It is only capable of passing into solution after being fused with alkalis.[19] Alumina may be obtained in this form by artificial means if the hydroxide be ignited and then fused in the oxyhydrogen flame.[20] Alumina also occurs in nature in combination with water—as, for instance, in the rather rare minerals hydrargillite (sp. gr. 2·3), Al₂O₃,3H₂O = 2Al(HO)₃, and diaspore, Al₂O_3,H₂O = 2AlO(HO) (sp. gr. 3·4). A less pure hydrate, mixed with ferric oxide, sometimes occurs in masses (at Baux in the south of France) and is termed bauxite; it contains Al₂O₃,2H₂O = Al₂O(HO)₄ (sp. gr. 2·6). When bauxite is ignited with sodium carbonate, carbonic anhydride is liberated and the alumina then combines with the sodium oxide, forming a saline aluminate of the oxides of aluminium and sodium. This is taken advantage of in practice for the preparation of pure alumina compounds on a large scale, for bauxite is found in large masses (in the South of France, in Austria, and in Carolina in South America), and the resultant compound of alumina and sodium is soluble in water and does not contain ferric oxide. This solution when subjected to the action of carbonic anhydride gives a precipitate of aluminium hydroxide,[21] which with acids forms aluminium salts. If aqueous ammonia be added to a solution of aluminium sulphate a gelatinous precipitate is formed, which at first remains suspended in the liquid and then on settling forms a gelatinous mass, which itself indicates the colloidal property of aluminium hydroxide. The following points are characteristic of this colloidal state: (1) in an anhydrous state such a colloidal substance is insoluble in water, as alumina is; (2) in the hydrated state, it is gelatinous and insoluble in water; and (3) it is also capable of existing in solutions, from which it separates out in a non-crystalline state, forming a substance resembling glue. These different states of colloids were distinguished by Graham, who gave them the following very characteristic names. He called the gelatinous form of the hydrate hydrogel, i.e. a gelatinous hydrate, and the soluble form of the aqueous compound, hydrosol, from the Latin for a soluble hydrate. Alumina readily and frequently assumes these states. The gelatinous hydrate of alumina is its hydrogel. It is, as has been already mentioned, insoluble in water, and, like all similar hydrogels, shows not the faintest sign of crystallisation; it is apt to vary in many of its properties with the amount of water it contains, and loses its water on ignition, leaving a white powder of the anhydrous oxide. The hydrogel of alumina is soluble both in acids and alkalis. It may also be obtained by the evaporation of its solutions in such feebly energetic acids as volatile acetic acid. These properties are very frequently made use of in the arts, and especially in the processes of dyeing, because the hydrogel of alumina in precipitating attracts a number of colouring matters from their solutions, the precipitate being thus coloured by the dyes attracted.[22] The preparation of fixed dyes and the employment of aluminous compounds (mordants) in the processes of dyeing are founded on this fact.[23] When precipitated upon the fibres of tissues (calicoes, linens, &c.) the aluminium hydroxide renders them impermeable to water; this may be taken advantage of for the preparation of waterproof tissues.

The hydrosol of alumina—i.e. the soluble aluminium hydroxide—is more difficult to obtain.[24] In order to obtain this soluble variety of alumina, Graham took a solution of its hydrogel in hydrochloric acid—that is, a solution of aluminium chloride, which is able to dissolve a still further quantity of the hydrogel of alumina, forming a basic salt having probably one of the compositions Al(HO)Cl₂ or Al(HO)₂Cl. When such a solution, considerably diluted with water, is subjected to dialysis—that is, to diffusion through a membrane[25]—the hydrochloric acid diffuses through the membrane and leaves the alumina in the form of hydrosol. The resultant solution, even when only containing two or three per cent. of alumina, passes into the hydrogel state with such facility that it is sufficient to transfer it from one vessel to another which has not been previously washed with water, for the entire mass to solidify into a jelly. But a solution containing not more than one-half per cent. of alumina may even be boiled without coagulating; however, after the lapse of several days this solution will of its own accord yield the hydrogel of alumina.[25 bis]

With respect to alumina as a base, it is very important to observe that it is not only capable of combining with other bases[26] but that it does not give salts with feeble volatile acids (like carbonic and hypochlorous); it forms salts which are easily decomposed by water, especially when heated,[27] as well as double and basic salts,[28] so that it forms a clear example of a feeble base.[29] To these characteristics of alumina we must add that it not only gives compounds of the type AlX₃, but also the polymeric type Al₂X₆, even when X is a simple univalent haloid like chlorine. Deville and Troost showed (1857) that the vapour density of aluminium chloride (at about 400°) is 9·37 with respect to air—that is, nearly 135 with respect to hydrogen, and therefore the formula of its molecule is expressed by Al₂Cl₆, and not AlCl₃,[30] although in the case of boron, arsenic, and antimony, which give oxides R₂O₃ of the same composition as Al₂O₃, the chlorine compounds form non-polymeric molecules, BCl₃, AsCl₃, SbCl₃.[31] This duplication (polymerisation) of the form AlX₃ is connected with the facility with which the salts of aluminium combine with other salts to form double salts and with aluminium hydroxide itself to form basic salts.

Aluminium sulphate, Al₂(SO₄)₃, which is obtained by treating clay or the hydrates of alumina with sulphuric acid, crystallises in the cold with 27H₂O, or at the ordinary temperature in pearly crystals, which are greasy to the touch and contain 16H₂O.[32] Its solutions act like sulphuric acid—for instance, they evolve hydrogen with zinc, forming basic salts, which are sometimes met with in nature (aluminite, Al₂O₃,SO₃,9H₂O, alumiane, Al₂O₃,2SO₃, and others), and may be obtained by the decomposition of normal salts and by the direct solution of the hydroxide in normal salts: these exhibit a varying composition, (Al₂O₃)_n(SO₃)_m(H₂O)_q, where m/n is less than 3. Aluminium sulphate is now prepared (from the pure hydrate obtained from bauxite, Note [21]) in large quantities for dyeing purposes (instead of alums) as a mordant. With solutions of the alkali sulphates (potassium, sodium, ammonium, rubidium, and cæsium sulphates), the normal salt easily forms double salts, termed alums—for example, the ordinary crystalline alum contains KAl(SO₄)₂,12H₂O, or K₂SO₄,Al₂(SO₄)₃,24H₂O. In the ammonium alums (which leave a residue of alumina when ignited) the potassium is replaced by ammonium (NH₄). Alums are used in large quantities, because there is scarcely any other salt which crystallises so easily. In this respect the alums formed by potassium and ammonium are equally convenient to purify, because they present a considerable difference in their solubility at the ordinary and higher temperatures. If the crystallisation be conducted rapidly, the salt separates in minute crystals, but if it be slowly deposited, especially in large masses, as in factories, then crystals several centimetres long are sometimes obtained. At a higher temperature alums are very much more soluble, and crystallise with greater difficulty, and are therefore less easily freed from impurities; at 0° 100 parts of water dissolve 3 parts, at 30° 22 parts, at 70° 90 parts, and at 100° 357 parts of potassium alum.[33] The solubility of ammonium alum is slightly less. The specific gravity of potassium alum is 1·74, of ammonium alum 1·63, and of sodium alum 1·60. Alums easily part with their water of crystallisation; thus potash alum partially effloresces when exposed to the air, and loses 9 mol. H₂O under the receiver of an air-pump. At 100°, dry air passed over alums takes up nearly all their water. As we have already mentioned (Chapter [XV.]), the law of isomorphous substitutions exhibits itself more clearly in the alums than in any other salts, and all alums not only contain the same amount of water of crystallisation, MR(SO₄)₂,12H₂O (where M = K, NH₄, Na; R = Al, Fe, Cr), and appear in crystals whose planes are inclined at equal angles, but they also give every possible kind of isomorphous mixture. The aluminium in them is easily replaced by iron, chromium, indium and sometimes by other metals, whilst the potassium may be substituted by sodium, rubidium, ammonium, and thallium, and the sulphuric acid may be replaced by selenic and chromic acids.

Aluminium chloride, Al₂Cl₆, is obtained, like other similar chlorides, (for instance MgCl₂) either directly from chlorine and the metal, or by heating to redness an intimate mixture of the amorphous anhydrous oxide and charcoal in a stream of dry chlorine.[33 bis] The resultant sublimate is very volatile,[34] and forms a crystalline, easily fusible mass, which deliquesces in the air and easily dissolves in water, with the evolution of a large amount of heat.[34 bis] On evaporating this solution, hydrochloric acid and aluminium hydroxide are liberated. But if the solution be heated in a closed tube, with an excess of hydrochloric acid, then, on cooling, crystals of AlCl₃,6H₂O are obtained—that is, aluminium chloride both combines with water and is decomposed by it. And the faculty of the type AlX₃ for combining with other molecules is seen in the compounds of AlCl₃ with many other chlorine compounds. Thus, for example, a mixture of aluminium chloride with sulphur tetrachloride gives Al₂Cl₆,SCl₄, under the action of chlorine, whilst with phosphorus pentachloride it forms AlCl₃,PCl₅; it also combines with NOCl. Thus, the compounds AlCl₃,NOCl, AlCl₃,POCl₃, AlCl₃,3NH₃, AlCl₃,KCl, AlCl₃,NaCl are known.[35] The compound of aluminium and sodium chlorides, AlNaCl₄, is very fusible and much more stable in the air than aluminium chloride itself. It seems to be of the same type as the alums. This compound, AlNaCl₄, is employed in the extraction of metallic aluminium, as we shall presently proceed to describe. Aluminium bromide, which is obtained by the direct combination of metallic aluminium with bromine, closely resembles the chloride; it melts at 90°, volatilises at 270°, and its vapour density indicates the formula Al₂Br₆. Aluminium iodide is obtained by heating iodine with finely divided aluminium in a closed tube; it is so easily decomposed by oxygen that its vapour even explodes when mixed with it.[36]

Metallic Aluminium was first prepared by Wöhler in 1822 as a grey powder by the action of potassium on aluminium chloride. He afterwards (in 1845) obtained it as a white compact metal, unoxidisable in the air, and only slowly attacked by acids. Owing to the vast and wide occurrence of clay, many efforts have been made in investigating in detail the methods for the extraction of this metal. These efforts were brought to a successful issue (1854) by Sainte-Claire Deville, who is also renowned for his doctrine of dissociation. Experiments on a large scale have proved that metallic aluminium, although possessed of great lightness, strength, and durability, is not so generally suitable for technical purposes as was at first thought. Nitric and many other acids, indeed, do not act on it, but the alkalis, alkaline substances, and even salts—for instance, moist table salt—humidity, &c.,[36 bis] tarnish it, and hence objects made of aluminium suffer at the surfaces, alter, and cannot, as was hoped, replace the precious metals, from which it differs in its extreme lightness. But the alloys made with aluminium (especially with copper, for example aluminium bronze) are very valuable in their properties and applications.

The Deville method for the preparation of metallic aluminium is based on the decomposition of the above-mentioned compound of sodium and aluminium chlorides by metallic sodium. The compound is obtained by passing the vapour of aluminium chloride (evolved from a mixture of alumina, extracted from bauxite or cryolite, with charcoal ignited in a stream of chlorine) over red-hot salt, when the compound AlNaCl₄, is itself volatilised, and may in this manner be obtained pure. A mixture of this compound with salt and fluor spar, or with cryolite, is heated with a certain excess of sodium, cut into small lumps. On a large scale this operation is carried on in special furnaces with a small access of air and at a high temperature. The decomposition takes place chiefly according to the equation NaAlCl₄ + 3Na = 4NaCl + Al. Neither charcoal nor zinc will reduce the oxygen compounds of aluminium; even sodium and potassium do not act on alumina. Moreover, metallic aluminium, like magnesium, is able to reduce even the metals of the alkalis from their oxygen compounds. This is connected with the fact that the atom of oxygen evolves more heat in combining with Al (and Mg) than it does in combining with other metals; whilst on the other hand, chlorine (and the other halogens) evolve more heat in combining with the metals of the alkalis.[36 tri]

Since the close of the eighties the metallurgy of aluminium has taken a new direction, based upon the action of an electric current upon cryolite at a high temperature,[37] and the solution of oxide of aluminium (obtained from bauxite or in the form of corundum) in it; under these conditions metallic aluminium is reduced at the negative pole (cathode) in a sufficiently pure state, and if the cathode be copper, forms alloys with it. Such are Hall's and Cowle's (both in the United States) and the Neuhausen process (where the current is obtained from a dynamo worked by the Falls of the Rhine at Schaffhausen). As an example, we will describe (in the words of Prof. D. P. Konovaloff, who became acquainted with this process at the Chicago Exhibition), Hall's process as applied near Pittsburg, where it gives about 1,500 kilos of Al a day. An iron box (about 1 metre long and ½ metre wide), provided with a well rammed down charcoal lining, is charged with a mixture of cryolite and Al₂O₃ (from bauxite), over which salt is strewn, and a current of 5,000 ampères at 20 volts is passed through the mixture. The anode is composed of a carbon cylinder (about 9 cm. in diameter), while the charcoal lining forms the cathode. When the temperature inside the box is raised to a red heat by the current, the mixture fuses and the Al₂O₃ begins to decompose. The Al liberated collects at the bottom of the box, whilst the oxygen evolved burns the charcoal anode. When the decomposition is at an end, and the resistance of the mass increases, a fresh quantity of Al₂O₃ is added, and this is continued until the amount of impurities accumulated in the furnace and passing into the metal becomes too great.[37 bis]

Aluminium has a white colour resembling that of tin—that is, it is greyer than silver and has the feebly dull lustre of tin, but compared to tin and pure silver, aluminium is very hard. Its density is 2·67—that is, it is nearly four times lighter than silver and three times lighter than copper. It melts at an incipient red heat (600°), and in so doing is but slightly oxidised. At the ordinary temperature it does not alter in the air, and in a compact mass it burns with great difficulty at a white heat, but in thin sheets, into which it may be rolled, or as a very fine wire, it burns with a brilliant white light, since it forms an infusible and non-volatile oxide. Aluminium itself is non-volatile at a furnace heat. These properties render Al a very good reducing agent, and N. N. Beketoff showed that it reduces the oxides of the alkali metals (Chapter XIII., Note [42 bis]). Dilute sulphuric acid has scarcely any action on it, but the strong acid dissolves it, especially with the aid of heat. Nitric acid, dilute or strong, has no action whatever on it. On the other hand, hydrochloric acid dissolves aluminium with great ease, as do also solutions of caustic soda and potash. In the latter cases hydrogen is evolved.[38]

Aluminium forms alloys with different metals with great ease. Among them the copper alloy is of practical use. It is called aluminium bronze. This alloy is prepared by dissolving 11 p.c. by weight of metallic aluminium in molten copper at a white heat. The formation of the alloy is accompanied by the development of a considerable quantity of heat, so that it glows to a bright white heat. This alloy, which corresponds with the formula AlCu₃, presents an exceedingly homogeneous mass, especially if perfectly pure copper be taken. It is distinguished for its capacity to fill up the most minute impressions of the mould into which it may be cast, and by its extraordinary elasticity and toughness, so that objects cast from it may be hammered, drawn, &c., and at the same time it is fine-grained and exceedingly hard, takes an excellent polish, and, what is most important, its surface then remains almost unchangeable in the air, and has a colour and lustre which may be compared to that of gold alloys. Hence aluminium bronze is much used in the arts for making spoons, watches, vessels, forks, knives, and for ornaments, &c. No less important is the fact that the admixture of one-thousandth part of aluminium with steel renders its castings homogeneous (free from cavities) to an extent that could not be arrived at by other means, nor does the quality of the steel in any respect deteriorate by this admixture, but rather is it improved. In a pure state, aluminium is only employed for such objects as require the hardness of metals with comparative lightness, such as telescopes and various physical apparatus and small articles.

According to the periodic system of the elements, the analogues of magnesium are zinc, cadmium, and mercury in the second group. So also in the third group, to which aluminium belongs, we find its corresponding analogues gallium, indium, and thallium. They are all three so rarely and sparingly met with in nature that they could only be discovered by means of the spectroscope. This fact shows that they are partially volatile, as should be the case according to the property of their nearest neighbours, the very volatile zinc, cadmium and mercury. As with them, in gallium, indium, and thallium the density of the metal, decomposability of compounds, &c., rises with the atomic weight. But here we find a peculiarity which does not exist in the second group. In the latter, the fusibility increases with the atomic weight of magnesium, zinc, cadmium, and mercury; indeed, the heaviest metal—mercury—is a liquid. In the third group it is not so. In order to understand this it is sufficient to turn our attention to the elements of the further groups of the uneven series—for instance, to group V., containing phosphorus, arsenic, and antimony, or to group VI., with sulphur, selenium, and tellurium, and also to group VII., where chlorine, bromine and iodine are situated. In all these instances the fusibility decreases with a rise of atomic weight; the members of the higher series, the elements of a high atomic weight, fuse with greater difficulty than the lighter elements. The representatives of the uneven series of group III., aluminium, gallium, indium, thallium, forming, as they do, a transition, all show an intermediate behaviour. Here the most fusible of all is the medium metal gallium,[38 bis] which fuses at the heat of the hand; whilst indium, thallium, and aluminium fuse at much higher temperatures.

Zinc (group II.), which has an atomic weight 65, should be followed in group III. by an element with an atomic weight of about 69. It will be in the same group as Al and should consequently give R₂O₃, RCl₃, R₂(SO₄)₃, alums and similar compounds analogous to those of aluminium. Its oxide should be more easily reducible to metal than alumina, just as zinc oxide is more easily reduced than magnesia. The oxide R₂O₃ should, like alumina, have feeble but clearly expressed basic properties. The metal reduced from its compounds should have a greater atomic volume than zinc, because in the fifth series, proceeding from zinc to bromine, the volume increases. And as the volume of zinc = 9·2, and of arsenic = 18, that of our metal should be near to 12. This is also evident from the fact that the volume of aluminium = 11, and of indium = 14, and our metal is situated in group III., between aluminium and indium. If its volume = 11·5 and its atomic weight be about 69, then its density will be nearly 5·9. The fact that zinc is more volatile than magnesium gives reason for thinking that the metal in question will be more volatile than aluminium, and therefore for expecting its discovery by the aid of the spectroscope, &c.

These properties were indicated by me for the analogue of aluminium in 1871, and I named it (see Chapter [XV.]) eka-aluminium. In 1875, Lecoq de Boisbaudran, who had done much work in spectrum analysis, discovered a new metal in a zinc blende from the Pyrenees (Pierrefitte). He recognised its individuality and difference from zinc, cadmium, indium, and the other companions of zinc by means of the spectroscope; but he only obtained some fractions of a centigram of it in a free state. Consequently only a few of its reactions were determined, as, for instance, that barium carbonate precipitates the new oxide from its salts (alumina, as is known, is also precipitated). Lecoq de Boisbaudran named the newly discovered metal gallium. As one would expect the same properties for eka-aluminium as were observed in gallium, I pointed out this fact at the time in the Memoirs of the Paris Academy of Sciences. All the subsequent observations of Lecoq de Boisbaudran confirmed the identity between the properties of gallium and those indicated for eka-aluminium. Immediately after this the ammonium alum of gallium was obtained, but the most convincing proof of all was found in the fact that the density of gallium although first apparently different (4·7) from that indicated above, afterwards, when the metal was carefully purified from sodium (which was first used as a reducing agent), proved to be just that (5·9) which would have been looked for in the analogue of aluminium; and, what was very important, the equivalent (23·3) and atomic weight (69·8) determined by the specific heat (0·08) were shown by experiment to be such as would be expected. These facts confirmed the universality and applicability of the periodic system of the elements. It must be remarked that previous to it there was no means of either foretelling the properties or even the existence of undiscovered elements.[39]

Much more light has been thrown on that element of the aluminium group which follows after cadmium (its position in the periodic system is III., 7, that is, it is in group III. in the 7th series). This is indium, In, which also occurs in small quantities in certain zinc ores. It was discovered (1863) by Reich and Richter (and more fully investigated by Winkler) in the Freiberg zinc ores, and was named indium from the fact that it gives to the flame of a gas-burner a blue coloration, owing to the indigo blue spectral lines proper to it. The equivalent (see Chapter XV., Note [15]), specific heat, and other properties of the metal confirm the atomic weight In = 113.[40]

Inasmuch as we found among the analogues of magnesium in group II. a metal, mercury, heavier and more easily reduced than the rest, and giving two grades of oxidation, so we should expect to find a metal among the analogues of aluminium in group III. which would be heavy, easily reduced, and give two grades of oxidation, and would have an atomic weight greater than 200. Such is thallium. It forms compounds of a lower type, TlX, besides the higher unstable type TlX₃, just as mercury gives HgX₂ and HgX. In the form of the thallic oxide, Tl₂O₃, the base is but feebly energetic, as would be expected by analogy with the oxides Al₂O₃, Ga₂O₃, and In₂O₃, whilst in thallous oxide, Tl₂O, the basic properties are sharply defined, as might be expected according to the properties of the type R₂O (Chapter [XV.]). Thallium was discovered in 1861 by Crookes and by Lamy in certain pyrites. When pyrites are employed in the manufacture of sulphuric acid, they are burned, and give besides sulphurous anhydride the vapours of various substances which accompany the sulphur, and are volatile. Among these substances arsenic and selenium are found, and together with them, thallium. These substances accumulate in a more or less considerable quantity in the tubes through which the vapours formed in the combustion of the pyrites have to pass. When the methods of spectrum analysis were discovered (1860), a great number of substances were subjected to spectroscopic research, and it was observed that those sublimations which are obtained in the combustion of certain pyrites contained an element having a very sharply-defined and characteristic spectrum—namely, in the green portion of the spectra it gave a well-defined band (wave-length 535 millionth millimetres) which did not correspond with any then known element.[41]

Under the action of a galvanic current solutions of thallium salts deposit the metal in the form of a heavy powder. It is of a grey colour like tin, is soft like sodium, and has a metallic lustre. Its specific gravity is 11·8, it melts at 290°, and volatilises at a high temperature. When heated slightly above its melting point it forms an insoluble (in water) higher oxide, Tl₂O₃, as a dark-coloured powder, generally however accompanied by the lower oxide Tl₂O, which is also black but soluble in water and alcohol. This solution has a distinctly alkaline reaction. This thallous oxide, melts at 300°, and is easily obtained from the hydroxide TlHO by igniting it without access of air (in the presence of air the incandescent thallous oxide partly passes into thallic oxide). Thallous hydroxide, TlOH, crystallises with one molecule H₂O in yellow prisms which are very easily soluble in water. Metallic thallium may be used for its preparation, as the metal in the presence of water attracts oxygen from the air and forms the hydroxide. But metallic thallium does not decompose water, although it gives a hydroxide which is soluble in water.[41 bis] All the other data for the chemical and physical properties of thallium, of its two grades of oxidation and of their corresponding salts, are expressed by the position occupied by this metal in virtue of its atomic weight Tl = 204, between mercury Hg = 200, and lead Pb = 206.

Gallium, indium, and thallium belong to the uneven series, and there should be elements of the even series in group III. corresponding with calcium, strontium, and barium in group II. These elements should in their oxides R₂O₃ present basic characters of a more energetic kind than those shown by alumina, just as calcium, strontium, and barium give more energetic bases than magnesium, zinc, and cadmium. Such are yttrium and ytterbium, which occur in a rare Swedish mineral called gadolinite, and are therefore termed the gadolinite metals. To these belong also the metal lanthanum, which accompanies the two other metals cerium and didymium in the mineral cerite, and it therefore belongs to the cerite metals. All these metals and certain others accompanying them, give basic oxides R₂O₃. At first their formula was supposed to be RO, but the application of the periodic system required their being counted as elements of groups III. and IV., which was also confirmed by the determination of the specific heats of these metals,[42] and better still by the fact that Nilson and Clève, in their researches on the gadolinite metals (1879), discovered that they contain a peculiar and very rare element, scandium, which by the magnitude of its atomic weight, Sc = 44, and in all its properties, exactly corresponds with the metal (previously foretold on the basis of the periodic system) ekaboron, whose properties were determined by taking the cerite and gadolinite metals as forming oxides R₂O₃.[43]

The brevity of this work and the great rarity of the above-mentioned elements will give me the right to exclude their description, all the more as the principles of the periodic system enable many of their properties to be foreseen, and as their practical uses (cerium oxalate is used in medicine, and didymium oxide in the manufacture of glass, a mixture of the oxides of lanthanum and similar metals is employed for giving a bright light, as this mixture emits a brilliant white light when brought to incandescence) are very limited, by reason of their great rarity in nature, and the difficulty of separating them from one another.

Footnotes:

[1] Borax is either directly obtained from lakes (the American lakes give about 2,000 tons and the lakes of Thibet about 1,000 tons per annum), or by heating native calcium borate (see Note [2]) with sodium carbonate (about 4,000 tons per annum), or it is obtained (up to 2,000 tons) from the Tuscan impure boric acid and sodium carbonate (carbonic anhydride is evolved). Borax gives supersaturated solutions with comparative ease (Gernez), from which it crystallises, both at the ordinary and higher temperatures, in octahedra, containing Na₂B₄O₇,5H₂O. Its sp. gr. is 1·81. But if the crystallisation proceeds in open vessels, then at temperatures below 56°, the ordinary prismatic crystallo-hydrate B₄Na₂O₇,10H₂O is obtained. Its sp. gr. is 1·71, it effloresces in dry air at the ordinary temperature, and at 0° 100 parts of water dissolve about 8 parts of this crystallo-hydrate, at 50° 27 parts, and at 100° 201 parts. Borax fuses when heated, loses its water and gives an anhydrous salt which at a red heat fuses into a mobile liquid and solidifies into a transparent amorphous glass (sp. gr. 2·37), which before hardening acquires the pasty condition peculiar to common molten glass. Molten borax dissolves many oxides and on solidifying acquires characteristic tints with the different oxides; thus oxide of cobalt gives a dark blue glass, nickel a yellow, chromium a green, manganese an amethyst, uranium a bright yellow, &c. Owing to its fusibility and property of dissolving oxides, borax is employed in soldering and brazing metals. Borax frequently enters into the composition of strass and fusible glasses.

[2] We may mention the following among the minerals which contain boron: calcium borate, (CaO)₃(B₂O₃)(H₂O)₆, found and extracted in Asia Minor, near Brusa; boracite (stassfurtite), (MgO)₆(B₂O₃)₈,MgCl₂, at Stassfurt, in the regular system, large crystals and amorphous masses (specific gravity 2·95), used in the arts; ereméeffite (Damour), AlBO₃ or Al₂O₃B₂O₃, found in the Adulchalonsk mountains in colourless, transparent prisms (specific gravity 3·28) resembling apatite; datholite, (CaO)₂(SiO₂)₂B₂O₃,H₂O; and ulksite, or the boron-sodium carbonate from which a large quantity of borax is now extracted in America (Note [1]). As much as 10 p.c. of boric anhydride sometimes enters into the composition of tourmalin and axinite.

[3] This green coloration is best seen by taking an alcoholic solution of volatile ethyl borate, which is easily obtained by the action of boron chloride on alcohol.

[3 bis] P. Chigeffsky showed in 1884 (at Geneva) that in the evaporation of saline solutions many salts are carried off by the vapour—for instance, if a solution of potash containing about 17–20 grams of K₂CO₃ per litre be boiled, about 5 milligrams of salt are carried off for every litre of water evaporated. With Li₂CO₃ the amount of salt carried over is infinitesimal, and with Na₂CO₃ it is half that given by K₂CO₃. The volatilisation of B₂O₃ under these circumstances is incomparably greater—for instance, when a solution containing 14 grams of B₂O₃ per litre is boiled, every litre of water evaporated carries over about 350 milligrams of B₂O₃. When Chigeffsky passed steam through a tube containing B₂O₃ at 400°, it carried over so much of this substance that the flame of a Bunsen's burner into which the steam was led gave a distinct green coloration; but when, instead of steam, air was passed through the tube there was no coloration whatever. By placing a tube with a cold surface in steam containing B₂O₃, Chigeffsky obtained a crystalline deposit of the hydrate B(OH)₃ on the surface of the tube. Besides this, he found that the amount of B₂O₃ carried over by steam increases with the temperature, and that crystals of B(OH)₃ placed in an atmosphere of steam (although perfectly still) volatilise, which shows that this is not a matter of mechanical transfer, but is based on the capacity of B₂O₃ and B(OH)₃ to pass into a state of vapour in an atmosphere of steam.

[4] How it is that these vapours containing boric acid are formed in the interior of the earth is at present unknown. Dumas supposes that it depends on the presence of boron sulphide, B₂S₃ (others think boron nitride), at a certain depth in the earth. This substance may be artificially prepared by heating a mixture of boric acid and charcoal in a stream of carbon bisulphide vapour, and by the direct combination of boron and the vapour of sulphur at a white heat. The almost non-crystalline compound B₂S₃, sp. gr. 1·55, thus obtained is somewhat volatile, has an unpleasant smell, and is very easily decomposed by water, forming boric acid and hydrogen sulphide, B₂S₃ + 3H₂O = B₂O₃ + 3H₂S. It is supposed that a bed of boron sulphide lying at a certain depth below the surface of the earth comes into contact with sea water which has percolated through the upper strata, becomes very hot, and gives steam, hydrogen sulphide, and boric acid. This also explains the presence of ammonia in the vapours, because the sea water certainly passes through crevices containing a certain amount of animal matter, which is decomposed by the action of heat and evolves ammonia. There are several other hypotheses for explaining the presence of the vapours of boric acid, but owing to the want of other known localities the comparison of these hypotheses is at present hardly possible. The amount of boric anhydride in the vapours which escape from the Tuscan fumerolles and suffioni is very inconsiderable, less than one-tenth per cent., and therefore the direct extraction of the acid would be very uneconomical, hence the heat contained in the discharged vapours is made use of for evaporating the water. This is done in the following manner. Reservoirs are constructed over the crevices evolving the vapours, and the water of some neighbouring spring is passed into them. The vapours are caused to pass through these reservoirs, and in so doing they give up all their boric acid to the water and heat it, so that after about twenty-four hours it even boils; still this water only forms a very weak solution of boric acid. This solution is then passed into lower basins and again saturated by the vapours discharged from the earth, by which means a certain amount of the water is evaporated and a fresh quantity of boric acid absorbed; the same process is repeated in another reservoir, and so on until the water has collected a somewhat considerable amount of boric acid. The solution is drawn from the last reservoir A into settling vessels B D, and then into a series of vessels a, b, c. In these vessels, which are made of lead, the solution is also evaporated by the vapours escaping from the earth, and attains a density of 10° to 11° Baumé. It is allowed to settle in the vessel C, in which it cools and crystallises, yielding (not quite pure) crystalline boric acid. At temperatures above 100°, for instance, with superheated steam, boric acid volatilises with steam very easily.

Fig. 81.—Extraction of boric acid in Tuscany.

[5] Metals, like Na, K, Li, give salts of the type of borax, MBO₂ or MH₂BO₃. A solution of borax, Na₂B₄O₇, has an alkaline reaction, decomposes ammonia salts with the liberation of ammonia (Bolley), absorbs carbonic anhydride like an alkali, dissolves iodine like an alkali (Georgiewics), and seems to be decomposed by water. Thus Rose showed that strong solutions of borax give a precipitate of silver borate with silver nitrate, whilst dilute solutions precipitate silver oxide, like an alkali. Georgiewics even supposes (1888) boric anhydride to be entirely void of acid properties; for all acids, on acting on a mixture of solutions of potassium iodide and iodate, evolve iodine, but boric acid does not do this. With dilute solutions of sodium hydroxide Berthelot obtained a development of heat equal to 11½ thousand calories per equivalent of alkali (40 grams sodium hydroxide) when the ratio Na₂O : 2B₂O₃ (as in borax) was taken, and only 4 thousand calories when the ratio was Na₂O : B₂O₃, whence he concludes that water powerfully decomposes those sodium borates in which there is more alkali than in borax. Laurent (1849) obtained a sodium compound, Na₂O,4B₂O₃,10H₂O, containing twice as much boric anhydride as borax, by boiling a mixture of borax with an equivalent quantity of sal-ammoniac until the evolution of ammonia entirely ceased.

Hence it is evident that feeble acids are as prone to, and as easily, form acid salts (that is, salts containing much acid oxide) as feeble bases are to give basic salts. These relations become still clearer on an acquaintance with such feeble acids as silicic, molybdic, &c. This variety of the proportions in which bases are able to form salts recalls exactly the variety of the proportions in which water combines with crystallo-hydrates. But the want of sufficient data in the study of these relations does not yet permit of their being generalised under any common laws.

With respect to the feeble acid energy of boric anhydride I think it useful to add the following remarks. Carbonic anhydride is absorbed by a solution of borax, and displaces boric anhydride; but it is also displaced by it, not only on fusion, but also on solution, as the preparation of borax itself shows. Sulphuric anhydride is absorbed by boric acid, forming a compound B(HSO₄)₃, where HSO₄ is the radicle of sulphuric acid (D'Ally). With phosphoric acid, boric acid forms a stable compound, BPO₄, or B₂O₃P₂O₅, undecomposable by water, as Gustavson and others have shown. With respect to tartaric acid, boric anhydride is able to play the same part as antimonious oxide. Mannitol, glycerol, and similar polyhydric alcohols also seem able to form particularly characteristic compounds with boric anhydride. All these aspects of the subject require still further explanation by a method of fresh and detailed research.

[6] Ditte determined the sp. gr.:—

The last line gives the solubility, in grams, of boric acid, B(OH)₃, per 100 c.c. of water, also according to the determinations of Ditte.

[7] It is evident that, in the presence of basic oxides, water competes with them, which fact in all probability determines both the amount of water in the salts of boric acid as well as their decomposition by an excess of water. In confirmation of the above-mentioned competing action between water and bases, I think it useful to point out that the crystallo-hydrate of borax containing 5H₂O may be represented as B(HO)₃, or rather as B₂(OH)₆, with the substitution of one atom of hydrogen by sodium, since Na₂B₄O₇,5H₂O = 2B₂(OH)₅(ONa). The composition of the acid boric salts is very varied, as is seen from the fact that Reychler (1893) obtained (Cs₂O)3B₂O₃, (Rb₂O)2B₂O₃ (corresponding to borax) and (Li₂O)B₂O₃, and that Le Chatelier and Ditte obtained, for CaO, MgO, &c., (RO)B₂O₃, (RO)₂3B₂O₃, (RO)2B₂O₃, (RO)₂B₂O₃, and even (RO)₃B₂O₃.

[8] A glass can only be formed by those slightly volatile oxides which correspond with feeble acids, like silica, phosphoric and boric anhydrides, &c., which themselves give glassy masses, like quartz, glacial phosphoric acid, and boric anhydride. They are able, like aqueous solutions and like metallic alloys, to solidify either in an amorphous form or to yield (or even be wholly converted into) definite crystalline compounds. This view illustrates the position of solutions amongst the other chemical compounds, and allows all alloys to be regarded from the aspect of the common laws of chemical reactions. I have therefore frequently recurred to it in this work, and have since the year 1850 introduced it into various provinces of chemistry.

[9] If boric acid in its aqueous solutions proves to be exceedingly feeble, unenergetic, and easily displaced from its salts by other acids, yet in an anhydrous state, as anhydride, it exhibits the properties of an energetic acid oxide, and it displaces the anhydrides of other acids. This of course does not mean that the acid then acquires new chemical properties, but only depends on the fact that the anhydrides of the majority of acids are much more volatile than boric anhydride, and therefore the salts of many acids—even of sulphuric acid—are decomposed when fused with boric anhydride.

By itself boric acid is used in the arts in small quantity, chiefly for the preservation of meat and fish (which must be afterwards well washed in water) and of milk, and for soaking the wicks of stearin candles; the latter application is based on the fact that the wicks, which are made of cotton twist, contain an ash which is infusible by itself but which fuses when mixed with boric acid.

[10] Amorphous boron is prepared by mixing 100 parts of powdered boric anhydride with 50 parts of sodium in small lumps; this mixture is thrown into a powerfully heated cast-iron crucible, covered with a layer of ignited salt, and the crucible covered. Reaction proceeds rapidly; the mass is stirred with an iron rod, and poured directly into water containing hydrochloric acid. The action is naturally accompanied by the formation of sodium borate, which is dissolved, together with the salt, by the water, whilst the boron settles at the bottom of the vessel as an insoluble powder. It is washed in water, and dried at the ordinary temperature. Magnesium, and even charcoal and phosphorus, are also able to reduce boron from its oxide. Boron, in the form of an amorphous powder, very easily passes through filter-paper, remains suspended in water, and colours it brown, so that it appears to be soluble in water. Sulphur precipitated from solutions shows the same (colloidal) property. When borax is fused with magnesium powder, it gives a brown powder of a compound of boron and magnesium, Mg₂B (Winkler, 1890), but when a mixture of 1 part of magnesium and 3 parts of B₂O₃ is heated to redness (Moissan, 1892), it forms amorphous boron in the form of a chestnut-coloured powder, which, after being washed with water, hydrochloric and hydrofluoric acids, is fused again with B₂O₃ in an atmosphere of hydrogen in order to prevent the access of the nitrogen of the air, which is easily absorbed by incandescent amorphous boron.

Sabatier (1891) considers that a certain amount of gaseous hydride of boron is evolved in the action of hydrochloric acid upon the alloys of magnesium and boron, because the gas disengaged burns with a green flame. Still, the existence of hydride of boron cannot be regarded as certain.

Under the action of the heat of the electric furnace boron forms with carbon a carbide, BC, as Mühlhäuser and Moissan showed in 1893.

[11] At first boron nitride was obtained by heating boric acid with potassium cyanide or other cyanogen compounds. It may be more simply prepared by heating anhydrous borax with potassium ferrocyanide, or by heating borax with ammonium chloride. For this purpose one part of borax is intimately mixed with two parts of dry ammonium chloride, and the mixture heated in a platinum crucible. A porous mass is formed, which after crushing and treating with water and hydrochloric acid, leaves boron nitride. Boron fluoride, BF, is known, corresponding to BN; this body was obtained by Besson and Moissan (1891). The action of phosphorus upon iodide of boron, BI₃, forms PBI₂, and when heated to 500° in hydrogen it forms BP, which gives PH₃ with fused KHO.

[12] When fused with potassium carbonate it forms potassium cyanate, BN + K₂CO₃ = KBO₂ + KCNO. All this shows that boron nitride is a nitrile of boric acid, BO(OH) + NH₃ - 2H₂O = BN. The same is expressed by saying that boron nitride is a compound of the type of the boron compounds BX₃, with the substitution of X₃ by nitrogen, as the trivalent radicle of ammonia, NH₃.

[13] Boron fluoride is frequently evolved on heating certain compounds occurring in nature containing both boron and fluorine. If calcium fluoride is heated with boric anhydride, calcium borate and boron fluoride are formed, and the latter, as a gas, is volatilised: 2B₂O₃ + 3CaF₂ = 2BF₃ + Ca₃B₂O₆. The calcium borate, however, retains a certain amount of calcium fluoride.

[14] In order to avoid the formation of silicon fluoride the decomposition should not be carried on in glass vessels, which contain silica, but in lead or platinum vessels. Boron fluoride by itself does not corrode glass, but the hydrofluoric acid liberated in the reaction may bring a part of the silica into reaction. Boron fluoride should be collected over mercury, as water acts on it, as we shall see afterwards.

[14 bis] It appears to me that from this point of view it is possible to understand the apparently contradictory results of different investigators, especially those of Gay-Lussac (and Thénard), Davy, Berzelius, and Bazaroff. In the form in which the reaction of BF₃ on water is given here, it is evident that the act of solution in water is accompanied by complex but direct chemical transformations, and I think that this example should prove the justness of those observations upon the nature of solutions which are given in Chapter [I.]

[15] They are called fluoborates. They may be prepared directly from fluorides and borates. Such compounds of halogens with oxygen salts are known in nature (for instance, apatite and boracite), and may be artificially prepared. The composition of the fluoborates—for example, K₄BF₃O₂—may be expressed as that of a double salt, BO(OK),3KF. If an excess of water decomposes them (Bazaroff), this does not prove that they do not exist as such, for many double salts are decomposed by water.

[16] Fluoboric acid contains boron fluoride and water, hydrofluoboric acid, boron fluoride, and hydrofluoric acid. It is evident that on the one side the competition between water and hydrofluoric acid, and, on the other hand, their power to combine, are among the forces which act here. From the fact that hydroborofluoric acid, HBF₄, can only exist in an aqueous solution, it must be assumed that it forms a somewhat stable system only in the presence of 3H₂O.