XXIV. COPPER, SILVER, AND GOLD

XXIV. COPPER, SILVER, AND GOLD

That degree of analogy and difference which exists between iron, cobalt, and nickel repeats itself in the corresponding triad ruthenium, rhodium, and palladium, and also in the heavy platinum metals, osmium, iridium, and platinum. These nine metals form Group VIII. of the elements in the periodic system, being the intermediate group between the even elements of the large periods and the uneven, among which we know zinc, cadmium, and mercury in Group II. Copper, silver, and gold complete[1] this transition, because their properties place them in proximity to nickel, palladium, and platinum on the one hand, and to zinc, cadmium, and mercury on the other. Just as Zn, Cd, and Hg; Fe, Ru, and Os; Co, Rh, and Ir; Ni, Pd, and Pt, resemble each other in many respects, so also do Cu, Ag, and Au. Thus, for example, the atomic weight of copper Cu = 63, and in all its properties it stands between Ni = 59 and Zn = 65. But as the transition from Group VIII. to Group II., where zinc is situated, cannot be otherwise than through Group I., so in copper there are certain properties of the elements of Group I. Thus it gives a suboxide, Cu_{2}O, and salts, CuX, like the elements of Group I., although at the same time it forms an oxide, CuO, and salts CuX_{2}, like nickel and zinc. In the state of the oxide, CuO, and the salts, CuX_{2}, copper is analogous to zinc, judging from the insolubility of the carbonates, phosphates, and similar salts, and by the isomorphism, and other characters.[2] In the cuprous salts there is undoubtedly a great resemblance to the silver salts--thus, for example, silver chloride, AgCl, is characterised by its insolubility and capacity of combining with ammonia, and in this respect cuprous chloride closely resembles it, for it is also insoluble in water, and combines with ammonia and dissolves in it, &c. Its composition is also RCl, the same as AgCl, NaCl, KCl, &c., and silver in many compounds resembles, and is even isomorphous with, sodium, so that this again justifies their being brought together. Silver chloride, cuprous chloride, and sodium chloride crystallise in the regular system. Besides which, the specific heats of copper and silver require that they should have the atomic weights ascribed to them. To the oxides Cu_{2}O and Ag_{2}O there are corresponding sulphides Ag_{2}S and Cu_{2}S. They both occur in nature in crystals of the rhombic system, and, what is most important, copper glance contains an isomorphous mixture of them both, and retains the form of copper glance with various proportions of copper and silver, and therefore has the composition R_{2}S where R = Cu, Ag.

[1] The perfectly unique position held by copper, silver, and gold in the periodic system of the elements, and the degree of affinity which is found between them, is all the more remarkable, as nature and practice have long isolated these metals from all others by having employed them--for example, for coinage--and determined their relative importance and value in conformity with the order (silver between copper and gold) of their atomic weights, &c.

[2] Cupric sulphate contains 5 molecules of water, CuSO_{4},5H_{2}O, and the isomorphous mixtures with ZnSO_{4},7H_{2}O contain either 5 or 7 equivalents, according to whether copper or zinc predominates (Vol. II. p. 6). If there be a large proportion of copper, and if the mixture contain 5H_{2}O, the form of the isomorphous mixture (triclinic) will be isomorphous with cupric sulphate, CuSO_{4},5H_{2}O, but if a large amount of zinc (or magnesium, iron, nickel, or cobalt) be present the form (rhombic or monoclinic) will be nearly the same as that of zinc sulphate, ZnSO_{4},7H_{2}O. Supersaturated solutions of each of these salts crystallise in that form and with that amount of water which is contained in a crystal of one or other of the salts brought in contact with the solution (Chapter XIV., Note 27).

Notwithstanding the resemblance in the atomic composition of the cuprous compounds, CuX, and silver compounds, AgX, with the compounds of the alkali metals KX, NaX, there is a considerable degree of difference between these two series of elements. This difference is clearly seen in the fact that the alkali metals belong to those elements which combine with extreme facility with oxygen, decompose water, and form the most alkaline bases; whilst silver and copper are oxidised with difficulty, form less energetic oxides, and do not decompose water, even at a rather high temperature. Moreover, they only displace hydrogen from very few acids. The difference between them is also seen in the dissimilarity of the properties of many of the corresponding compounds. Thus cuprous oxide, Cu_{2}O, and silver oxide, Ag_{2}O, are insoluble in water: the cuprous and silver carbonates, chlorides, and sulphates are also sparingly soluble in water. The oxides of silver and copper are also easily reduced to metal. This difference in properties is in intimate relation with that difference in the density of the metals which exists in this case. The alkali metals belong to the lightest, and copper and silver to the heaviest, and therefore the distance between the molecules in these metals is very dissimilar--it is greater for the former than the latter (tables in Chapter XV.). From the point of view of the periodic law, this difference between copper and silver and such elements of Group I. as potassium and rubidium, is clearly seen from the fact that copper and silver stand in the middle of those large periods (for example, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br) which start with the true metals of the alkalis--that is to say, the analogy and difference between potassium and copper are of the same nature as that between chromium and selenium, or vanadium and arsenic.

Copper is one of the few metals which have long been known in a metallic form. The Greeks and Romans imported copper chiefly from the island of Cyprus--whence its Latin name, cuprum. It was known to the ancients before iron, and was used, especially when alloyed with other metals, for arms and domestic utensils. That copper was known to the ancients will be understood from the fact that it occurs, although rarely, in a native state, and is easily extracted from its other natural compounds. Among the latter are the oxygen compounds of copper. When ignited with charcoal, they easily give up their oxygen to it, and yield metallic copper; hydrogen also easily takes up the oxygen from copper oxide when heated. Copper occurs in a native state, sometimes in association with other ores, in many parts of the Urals and in Sweden, and in considerable masses in America, especially in the neighbourhood of the great American lakes; and also in Chili, Japan, and China. The oxygen compounds of copper are also of somewhat common occurrence in certain localities; in this respect certain deposits of the Urals are especially famous. The geological period of the Urals (Permian) is characterised by a considerable distribution of copper ores. Copper is met with in the form of cuprous oxide, or suboxide of copper, Cu_{2}O, and is then known as red copper ore, because it forms red masses which not unfrequently are crystallised in the regular system. It is found much more rarely in the state of cupric oxide, CuO, and is then called black copper ore. The most common of the oxygenised compounds of copper are the basic carbonates corresponding with the oxides. That these compounds are undoubtedly of aqueous origin is apparent, not only from the fact that specimens are frequently found of a gradual transition from the metallic, sulphuretted, and oxidised copper into its various carbonates, but also from the presence of water in their composition, and from the laminar, reniform structure which many of them present. In this respect malachite is particularly well known; it is used as a green paint and also for ornaments, owing to the diversity of the shades of colour presented by the different layers of deposited malachite. The composition of malachite corresponds with the basic carbonate containing one molecule of cupric carbonate to one of hydroxide: CuCO_{3},CuH_{2}O_{2}. In this form the copper frequently occurs in admixture with various sedimentary rocks, forming large strata, which confirms the aqueous origin of these compounds. There are many such localities in the Perm and other Governments bounding the Urals. Blue carbonate of copper, or azurite, is also often met with in the same localities; it contains the same ingredients as malachite, but in a different proportion, its composition being CuH_{2}O_{2},2CuCO_{3}. Both these substances may be obtained artificially by the action of the alkali carbonates on solutions of cupric salts at various temperatures. These native carbonates are often used for the extraction of copper, all the more as they very readily give metallic copper, evolving water and carbonic anhydride when ignited, and leaving the easily-reducible cupric oxide. Copper is, however, still more often met with in the form of the sulphides. The sulphides of copper generally occur in chemical combination with the sulphides of iron.[3] These copper-sulphur compounds (copper pyrites CuFeS_{2}, variegated copper ore Cu_{3}FeS_{3}, &c.) generally occur in veins in a rock gangue.

[3] Iron pyrites, FeS_{2}, very often contain a small quantity of copper sulphide (see Chapter XXII., Note 2 bis), and on burning the iron pyrites for sulphurous anhydride the copper oxide remains in the residue, from which the copper is often extracted with profit. For this purpose the whole of the sulphur is not burnt off from the iron pyrites, but a portion is left behind in the ore, which is then slowly ignited (roasted) with access of air. Cupric sulphate is then formed, and is extracted by water; or what is better and more frequently done, the residue from the roasting of the pyrites is roasted with common salt, and the solution of cupric chloride obtained by lixiviating is precipitated with iron. A far greater amount of copper is obtained from other sulphuretted ores. Among these copper glance, Cu_{2}S, is more rarely met with. It has a metallic lustre, is grey, generally crystalline, and is obtained in admixture with organic matter; so that there is no doubt that its origin is due to the reducing action of the latter on solutions of cupric sulphate. Variegated copper ore, which crystallises in octahedra, not infrequently forms an admixture in copper glance; it has a metallic lustre, and is reddish-brown; it has a superficial play of colours, due to oxidation proceeding on its surface. Its composition is Cu_{3}FeS_{3}. But the most common and widely-distributed copper ore is copper pyrites, which crystallises in regular octahedra; it has a metallic lustre, a sp. gr. of 4·0, and yellow colour. Its composition is CuFeS_{2}. It must be remarked that the sulphurous ores of copper are oxidised in the presence of water containing oxygen in solution, and form cupric sulphate, blue vitriol, which is easily soluble in water. If this water contains calcium carbonate, gypsum and cupric carbonate are formed by double decomposition: CuSO_{4} + CaCO_{3} = CuCO_{3} + CaSO_{4}. Hence copper sulphide in the form of different ores must be considered as the primary product, and the many other copper ores as secondary products, formed by water. This is confirmed by the fact that at the present time the water extracted from many copper mines contains cupric sulphate in solution. From this liquid it is easy to extract cupric oxide by the action of organic matter and various impurities of water. Hence metallic copper is sometimes found in natural products of the modification of copper sulphide and is probably deposited by the action of organic matter present in the water.

The extraction of copper from its oxide ores does not present any difficulty, because the copper, when ignited with charcoal and melted, is reduced from the impurities which accompany it. This mode of smelting copper ores is carried on in cupola or cylindrical furnaces, fluxes forming a slag being added to the mixture of ore and charcoal. The smelted copper still contains sulphur, iron, and other metallic impurities, from which it is freed by fusion in reverberatory furnaces, with access of air to the surface of the molten metal, as the iron and sulphur are more easily oxidised than the copper. The iron then separates as oxides, which collect in the slag.[4]

[4] Copper ores rich in oxygen are very rare; the sulphur ores are of more common occurrence, but the extraction of the copper from them is much more difficult. The problem here not only consists in the removal of the sulphur, but also in the removal of the iron combined with the sulphur and copper. This is attained by a whole series of operations, after which there still sometimes remains the extraction of the metallic silver which generally accompanies the copper, although in but small quantity. These processes commence with the roasting--i.e. calcination--of the ore with access of air, by which means the sulphur is converted into sulphurous anhydride. It should here be remarked that iron sulphide is more easily oxidised than copper sulphide, and therefore the greater part of the iron in the residue from roasting is no longer in the form of sulphide but of oxide of iron. The roasted ore is mixed with charcoal, and siliceous fluxes, and smelted in a cupola furnace. The iron then passes into the slag, because its oxide gives an easily-fusible mass with the silica, whilst the copper, in the form of sulphide, fuses and collects under the slag. The greater part of the iron is removed from the mass by this smelting. The resultant coarse metal is again roasted in order to remove the greater part of the sulphur from the copper sulphide, and to convert the metal into oxide, after which the mass is again smelted. These processes are repeated several times, according to the richness of the ore. During these smeltings a portion of the copper is already obtained in a metallic form, because copper sulphide gives metallic copper with the oxide (CuS + 2CuO = 3Cu + SO_{2}). We will not here describe the furnaces used or the details of this process, but the above remarks include the explanation of those chemical processes which are accomplished in the various technical operations which are made use of in the process (for details see works on metallurgy).

Besides the smelting of copper there also exist methods for its extraction from solutions in the wet way, as it is called. Recourse is generally had to these methods for poor copper ores. The copper is brought into solution, from which it is separated by means of metallic iron or by other methods (by the action of an electric current). The sulphides are roasted in such a manner that the greater part of the copper is oxidised into cupric sulphate, whilst at the same time the corresponding iron salts are as far as possible decomposed. This process is based on the fact that the copper sulphides absorb oxygen when they are calcined in the presence of air, forming cupric sulphate. The roasted ore is treated with water, to which acid is sometimes added, and after lixiviation the resultant solution containing copper is treated either with metallic iron or with milk of lime, which precipitates cupric hydroxide from the solution. Copper oxide ores poor in metal may be treated with dilute acids in order to obtain the copper oxides in solution, from which the copper is then easily precipitated either by iron or as hydroxide by lime. According to Hunt and Douglas's method, the copper in the ore is converted by calcination into the cupric oxide, which is brought into solution by the action of a mixture of solutions of ferrous sulphate and sodium chloride; the oxide converts the ferrous chloride into ferric oxide, forming copper chlorides, according to the equation 3CuO + 2FeCl_{2} = CuCl_{2} + 2CuCl + Fe_{2}O_{3}. The cupric chloride is soluble in water, whilst the cuprous chloride is dissolved in the solution of sodium chloride, and therefore all the copper passes into solution, from which it is precipitated by iron.

The same American metallurgists give the following wet method for extracting the Ag and Au occurring in many copper ores, especially in sulphurous ores: (1) The Cu_{2}S is first converted into oxide by roasting in a calciner; (2) the CuO is extracted by the dilute sulphuric acid obtained in the fourth process, the Cu then passes into solution, while the Ag, Au and oxides of iron remain behind in the residue (from which the noble metals may be extracted); (3) a portion of the copper in solution is converted into CuCl_{2} (and CaSO_{4} precipitated) by means of the CaCl_{2} obtained in the fifth process; (4) the mixture of solutions of CuSO_{4} and CuCl_{2} is converted into the insoluble CuCl (salt of the suboxide) by the action of the SO_{2} obtained by roasting the ore (in the first operation), sulphuric acid is then formed in the solution, according to the equation: CuSO_{4} + CuCl_{2} + SO_{2} + 2H_{2}O = 2H_{2}SO_{4} + 2CuCl; (5) the precipitated CuCl is treated with lime and water, and gives CuCl_{2} in solution and CuO in the residue; and lastly (6) the Cu_{2}O is reduced to metallic Cu by carbon in a furnace. According to Crooke's method the impure copper regulus obtained by roasting and smelting the ore is broken up and immersed repeatedly in molten lead, which extracts the Ag and Au occurring in the regulus. The regulus is then heated in a reverberatory furnace to run off the lead, and is then smelted for Cu.

The copper brought into the market often contains small quantities of various impurities. Among these there are generally present iron, lead, silver, arsenic, and sometimes small quantities of oxides of copper. As copper, when mixed with a small amount of foreign substances, loses its tenacity to a certain degree, the manufacture of very thin sheet copper requires the use of Chili copper, which is distinguished for its great softness, and therefore when it is desired to have pure copper, it is best to take thin sheet copper, like that which is used in the manufacture of cartridges. But the purest copper is electrolytic copper--that is, that which is deposited from a solution by the action of an electric current.

If the copper contains silver, as is often the case, it is used in gold refineries for the precipitation of silver from its solutions in sulphuric acid. Iron and zinc reduce copper salts, but copper reduces mercury and silver salts. The precipitate contains not only the silver which was previously in solution, but also all that which was in the copper. The silver solutions in sulphuric acid are obtained in the separation of silver from gold by treating their alloys with sulphuric acid, which only dissolves the silver.

Copper is characterised by its red colour, which distinguishes it from all other metals. Pure copper is soft, and may be beaten out by a hammer at the ordinary temperature, and when hot may be rolled into very thin sheets. Extremely thin leaves of copper transmit a green light. The tenacity of copper is also considerable, and next to iron it is one of the most durable metals in this respect. Copper wire of 1 sq. millimetre in section only breaks under a weight of 45 kilograms. The specific gravity of copper is 8·8, unless it contains cavities due to the fact that molten copper absorbs oxygen from the air, which is disengaged on cooling, and therefore gives a porous mass whose density is much less. Rolled copper, and also that which is deposited by the electric current, has a comparatively high density. Copper melts at a bright red heat, about 1050°, although below the temperature at which many kinds of cast iron melt. At a high temperature it is converted into vapour, which communicates a green colour to the flame. Both native copper and that cooled from a molten state crystallise in regular octahedra. Copper is not oxidised in dry air at the ordinary temperature, but when calcined it becomes coated with a layer of oxide, and it does not burn even at the highest temperature. Copper, when calcined in air, forms either the red cuprous oxide or the black cupric oxide, according to the temperature and quantity of air supplied. In air at the ordinary temperature, copper--as everyone knows--becomes coated with a brown layer of oxides or a green coating of basic salts, due to the action of the damp air containing carbonic acid. If this action continue for a prolonged time, the copper is covered with a thick coating of basic carbonate, or the so-called verdigris (the ærugo nobilis of ancient statues). This is due to the fact that copper, although scarcely capable of oxidising by itself,[5] in the presence of water and acids--even very feeble acids, like carbonic acid--absorbs oxygen from the air and forms salts, which is a very characteristic property of it (and of lead).[6] Copper does not decompose water, and therefore does not disengage hydrogen from it either at the ordinary or at high temperatures. Nor does copper liberate hydrogen from the oxygen acids; these act on it in two ways: they either give up a portion of their oxygen, forming lower grades of oxidation, or else only react in the presence of air. Thus, when nitric acid acts on copper it evolves nitric oxide, the copper being oxidised at the expense of the nitric acid. In the same way copper converts sulphuric acid into the lower grade of oxidation--into sulphurous anhydride, SO_{2}. In these cases the copper is oxidised to copper oxide, which combines with the excess of acid taken, and therefore forms a cupric salt, CuX_{2}. Dilute nitric acid does not act on copper at the ordinary temperature, but when heated it reacts with great ease; dilute sulphuric acid does not act on copper except in presence of air.

[5] Schützenberger showed that when the basic carbonate of copper is decomposed by an electric current it gives, besides the ordinary copper, an allotropic form which grows on the negative platinum electrode, if its surface be smaller than that of the positive copper electrode, in the form of brittle crystalline growths of sp. gr. 8·1. It differs from ordinary copper by giving not nitric oxide but nitrous oxide when treated with nitric acid, and in being very easily oxidised in air, and coated with red shades of colour. It is possible that this is copper hydride, or copper which has occluded hydrogen. Spring (1892) observed that copper reduced from the oxide by hydrogen at the lowest possible temperature was pulverulent, while that reduced from CuCl_{2} at a somewhat high temperature appeared in bright crystals. The same difference occurs with many other metals, and is probably partly due to the volatility of the metallic chlorides.

[6] This is taken advantage of in practice; for instance, by pouring dilute acids over copper turnings on revolving tables in the preparation of copper salts, such as verdigris, or the basic acetate 2C_{4}H_{6}CuO_{4},CuH_{2}O_{2},5H_{2}O, which is so much used as an oil paint (i.e. with boiled oil). The capacity of copper for absorbing oxygen in the presence of acids is so great that it is possible by this means (by taking, for example, thin copper shavings moistened with sulphuric acid) to take up all the oxygen from a given volume of air, and this is even employed for the analysis of air.

The combination of copper with oxygen is not only aided by acids but also by alkalis, although cupric oxide does not appear to have an acid character. Alkalis do not act on copper except in the presence of air, when they produce cupric oxide, which does not appear to combine with such alkalis as caustic potash or soda. But the action of ammonia is particularly distinct (Chapter V., Note 2). In the action of a solution of ammonia not only is oxygen absorbed by the copper, but it also acts on the ammonia, and a definite quantity of ammonia is always acted on simultaneously with the passage of the copper into solution. The ammonia is then converted into nitrous acid, according to the reaction: NH_{3} + O_{3} = NHO_{2} + H_{2}O, and the nitrous acid thus formed passes into the state of ammonium nitrite, NH_{4}NO_{2}. In this manner three equivalents of oxygen are expended on the oxidation of the ammonia, and six equivalents of oxygen pass over to the copper, forming six atoms of cupric oxide. The latter does not remain in the state of oxide, but combines with the ammonia.

A strong solution of common salt does not act on copper, but a dilute solution of the salt corrodes copper, converting it into oxychloride--that is, in the presence of air. This action of salt water is evident in those cases where the bottoms of ships are coated with sheet copper. From what has been said above it will be evident that copper vessels should not be employed in the preparation of food, because this contains salts and acids which act on copper in the presence of air, and give copper salts, which are poisonous, and therefore the food prepared in untinned copper vessels may be poisonous. Hence tinned vessels are employed for this purpose--that is, copper vessels coated with a thin layer of tin, on which acid and saline solutions do not act.

Both the oxides of copper, Cu_{2}O and CuO, are unacted on by air, and, as already mentioned, they both occur in nature.[6 bis] However, in the majority of cases copper is obtained in the form of cupric oxide and its salts--and the copper compounds used industrially generally belong to this type. This is due to the fact that the cuprous compounds absorb oxygen from the air and pass into cupric compounds. The cupric compounds may serve as the source for the preparation of cuprous oxide, because many reducing agents are capable of deoxidising the oxide into the suboxide. Organic substances are most generally employed for this purpose, and especially saccharine substances, which are able, in the presence of alkalis, to undergo oxidation at the expense of the oxygen of the cupric oxide, and to give acids which combine with the alkali: 2CuO - O = Cu_{2}O. In this case the deoxidation of the copper may be carried further and metallic copper obtained, if only the reaction be aided by heat. Thus, for example, a fine powder of metallic copper may be obtained by heating an ammoniacal solution of cupric oxide with caustic potash and grape sugar. But if the reducing action of the saccharine substance proceed in the presence of a sufficient quantity of alkali in solution, and at not too high a temperature, cuprous oxide is obtained. To see this reaction clearly, it is not sufficient to take any cupric salt, because the alkali necessary for the reaction might precipitate cupric oxide--it is necessary to add previously some substance which will prevent this precipitation. Among such substances, tartaric acid, C_{4}H_{6}O_{6}, is one of the best. In the presence of a sufficient quantity of tartaric acid, any amount of alkali may be added to a solution of cupric salt without producing a precipitate, because a soluble double salt of cupric oxide and alkali is then formed. If glucose (for instance, honey or molasses) be added to such an alkaline tartaric solution, and the temperature be slightly raised, it first gives a yellow precipitate (this is cuprous hydroxide, CuHO), and then, on boiling, a red precipitate of (anhydrous) cuprous oxide. If such a mixture be left for a long time at the ordinary temperature, it deposits well-formed crystals of anhydrous cuprous oxide belonging to the regular system.[7]

[6 bis] Copper, besides the cuprous oxide, Cu_{2}O, and cupric oxide, CuO, gives two known higher forms of oxidation, but they have scarcely been investigated, and even their composition is not well known. Copper dioxide (CuO_{2}, or CuO_{2},H_{2}O, perhaps CuOH_{2}O_{2}) is obtained by the action of hydrogen peroxide on cupric hydroxide, when the green colour of the latter is changed to yellow. It is very unstable, and is decomposed even by boiling water, with the evolution of oxygen, whilst the action of acids gives cupric salts, oxygen being also disengaged. A still higher copper peroxide is formed by heating a mixture of caustic potash, nitre, and metallic copper to a red heat, and by dissolving cupric hydroxide in solutions of the hypochlorites of the alkali metals. A slight heating of the soluble salt formed is enough for it to be decomposed into oxygen and copper dioxide, which is precipitated. Judging from Frémy's researches, the composition of the copper-potassic compound should be K_{2}CuO_{4}. Perhaps this is a compound of the peroxides of potassium, K_{2}O_{2}, and of copper, CuO_{2}.

[7] Colourless solutions of cuprous salts may also be obtained by the action of sulphurous or phosphorous acid and similar lower grades of oxidation on the blue solutions of the cupric salts. This is very clearly and easily effected by means of sodium thiosulphate, Na_{2}S_{2}O_{3}, which is oxidised in the process. Cuprous oxide can not only be obtained by the deoxidation of cupric oxide, but also directly from metallic copper itself, because the latter, in oxidising at a red heat in air, first gives cuprous oxide. It is prepared in this manner on a large scale by heating sheet copper rolled into spirals in reverberatory furnaces. Care must be taken that the air is not in great excess, and that the coating of red cuprous oxide formed does not begin to pass into the black cupric oxide. If the oxidised spiral sheet is then unbent, the brittle cuprous oxide falls away from the soft metal. The suboxide obtained in this manner fuses with ease. It is necessary to prevent the access of air during the fusion, and if the mass contains cupric oxide it must be mixed with charcoal, which reduces the latter. Cuprous chloride, CuCl, corresponding with cuprous oxide (as sodium chloride corresponds with sodium oxide), when calcined with sodium carbonate, gives sodium chloride and cuprous oxide, carbonic anhydride being evolved, because it does not combine with the cuprous oxide under these conditions. The reaction can be expressed by the following equation: 2CuCl + Na_{2}CO_{3} = Cu_{2}O + 2NaCl + CO_{2}. The cupric oxide itself, when calcined with finely-divided copper, this copper powder may be obtained by many methods--for instance, by immersing zinc in a solution of a copper salt, or by igniting cupric oxide in hydrogen), gives the fusible cuprous oxide: Cu + CuO = Cu_{2}O. Both the native and artificial cuprous oxide have a sp. gr. of 5·6. It is insoluble in water, and is not acted on by (dry) air. When heated with acids the suboxide forms a solution of a cupric salt and metallic copper--for example, Cu_{2}O + H_{2}SO_{4} = Cu + CuSO_{4} + H_{2}O. However, strong hydrochloric acid does not separate metallic copper on dissolving cuprous oxide, which is due to the fact that the cuprous chloride formed is soluble in strong hydrochloric acid. Cuprous oxide also dissolves in a solution of ammonia, and in the absence of air gives a colourless solution, which turns blue in the air, absorbing oxygen, owing to the conversion of the cuprous oxide into cupric oxide. The blue solution thus formed may be again reconverted into a colourless cuprous solution by immersing a copper strip in it, because the metallic copper then deoxidises the cupric oxide in the solution into cuprous oxide. Cuprous oxide is characterised by the fact that it gives red glasses when fused with glass or with salts forming vitreous alloys. Glass tinted with cuprous oxide is used for ornaments. The access of air must be avoided during its preparation, because the colour then becomes green, owing to the formation of cupric oxide, which colours glass blue. This may even be taken advantage of in testing for copper under the blow-pipe by heating the copper compound with borax in the flame of a blow-pipe; a red glass is obtained in the reducing flame, and a blue glass in the oxidising flame, owing to the conversion of the cuprous into cupric oxide.

Étard (1882), by passing sulphurous anhydride into a solution of cupric acetate, obtained a white precipitate of cuprous sulphite, Cu_{2}SO_{3},H_{2}O, whilst he obtained the same salt, of a red colour, from the double salt of sodium and copper; but there are not any convincing proofs of isomerism in this case.

Cupric chloride, CuCl_{2}, when ignited, gives cuprous chloride, CuCl--i.e. the salt corresponding with suboxide of copper--and therefore cuprous chloride is always formed when copper enters into reaction with chlorine at a high temperature. Thus, for example, when copper is calcined with mercuric chloride, it forms cuprous chloride and vapours of mercury. The same substance is obtained on heating metallic copper in hydrochloric acid, hydrogen being disengaged; but this reaction only proceeds with finely-divided copper, as hydrochloric acid acts very feebly on compact masses of copper, and, in the presence of air, gives cupric chloride. The green solution of cupric chloride is decolorised by metallic copper, cuprous chloride being formed; but this reaction is only accomplished with ease when the solution is very concentrated and in the presence of an excess of hydrochloric acid to dissolve the cuprous chloride. The addition of water to the solution precipitates the cuprous chloride, because it is less soluble in dilute than in strong hydrochloric acid. Many reducing agents which are able to take up half the oxygen from cupric oxide are able, in the presence of hydrochloric acid, to form cuprous chloride. Stannous salts, sulphurous anhydride, alkali sulphites, phosphorous and hypophosphorous acids, and many similar reducing agents, act in this manner. The usual method of preparing cuprous chloride consists in passing sulphurous anhydride into a very strong solution of cupric chloride: 2CuCl_{2} + SO_{2} + 2H_{2}O = 2CuCl + 2HCl + H_{2}SO_{4}. Cuprous chloride forms colourless cubic crystals which are insoluble in water. It is easily fusible, and even volatile. Under the action of oxidising agents, it passes into the cupric salt, and it absorbs oxygen from moist air, forming cupric oxychloride, Cu_{2}Cl_{2}O. Aqueous ammonia easily dissolves cuprous chloride as well as cuprous oxide; the solution also turns blue on exposure to the air. Thus an ammoniacal solution of cuprous chloride serves as an excellent absorbent for oxygen; but this solution absorbs not only oxygen, but also certain other gases--for example, carbonic oxide and acetylene.[8]

[8] The solubility of cuprous chloride in ammonia is due to the formation of compounds between the ammonia and the chloride. In a warm solution the compound NH_{3},2CuCl is formed, and at the ordinary temperature CuCl,NH_{3}. This salt is soluble in hydrochloric acid, and then forms a corresponding double salt of cuprous chloride and ammonium chloride. By the action of a certain excess of ammonia on a hydrochloric acid solution of cuprous chloride, very well formed crystals, having the composition CuCl,NH_{3},H_{2}O, are obtained. Cuprous chloride is not only soluble in ammonia and hydrochloric acid, but it also dissolves in solutions of certain other salts--for example, in sodium chloride, potassium chloride, sodium thiosulphate, and certain others. All the solutions of cuprous chloride act in many cases as very powerful deoxidising substances; for example, it is easy, by means of these solutions, to precipitate gold from its solutions in a metallic form, according to the equation AuCl_{3} + 3CuCl = Au + 3CuCl_{2}.

Among the other compounds corresponding with cuprous oxide, cuprous iodide, CuI, is worthy of remark. It is a colourless substance which is insoluble in water and sparingly soluble in ammonia (like silver iodide), but capable of absorbing it, and in this respect it resembles cuprous chloride. It is remarkable from the fact that it is exceedingly easily formed from the corresponding cupric compound CuI_{2}. A solution of cupric iodide easily decomposes into iodine and cuprous iodide, even at the ordinary temperature, whilst cupric chloride only suffers a similar change on ignition. If a solution of a cupric salt be mixed with a solution of potassium iodide the cupric iodide formed immediately decomposes into free iodine and cuprous iodide, which separates out as a precipitate. In this case the cupric salt acts in an oxidising manner, like, for example, nitrous acid, ozone, and other substances which liberate iodine from iodides, but with this difference, that it only liberates half, whilst they set free the whole of the iodine from potassium iodide: 2KI + CuCl_{2} = 2KCl + CuI + I.

It must also be remarked that cuprous oxide, when treated with hydrofluoric acid, gives an insoluble cuprous fluoride, CuF. Cuprous cyanide is also insoluble in water, and is obtained by the addition of hydrocyanic acid to a solution of cupric chloride saturated with sulphurous anhydride. This cuprous cyanide, like silver cyanide, gives a double soluble salt with potassium cyanide. The double cyanide of copper and potassium is tolerably stable in the air, and enters into double decompositions with various other salts, like those double cyanides of iron with which we are already acquainted.

Copper hydride, CuH, also belongs to the number of the cuprous compounds. It was obtained by Würtz by mixing a hot (70°) solution of cupric sulphate with a solution of hypophosphorous acid, H_{3}PO_{2}. The addition of the reducing hypophosphorous acid must be stopped when a brown precipitate makes its appearance, and when gas begins to be evolved. The brown precipitate is the hydrated cuprous hydride. When gently heated it disengages hydrogen; it gives cuprous oxide when exposed to the air, burns in a stream of chlorine, and liberates hydrogen with hydrochloric acid: CuH + HCl = CuCl + H_{2}. Zinc, silver, mercury, lead, and many other heavy metals do not form such a compound with hydrogen, neither under these circumstances nor under the action of hydrogen at the moment of the decomposition of salts by a galvanic current. The greatest resemblance is seen between cuprous hydride and the hydrogen compounds of potassium, sodium, Pd, Ca, and Ba.

When copper is oxidised with a considerable quantity of oxygen at a high temperature, or at the ordinary temperature in the presence of acids, and also when it decomposes acids, converting them into lower grades of oxidation (for example, when submitted to the action of nitric and sulphuric acids), it forms cupric oxide, CuO, or, in the presence of acids, cupric salts. Copper rust, or that black mass which forms on the surface of copper when it is calcined, consists of cupric oxide. The coating of the oxidised copper is very easily separated from the metallic copper, because it is brittle and very easily peels off, when it is struck or immersed in water. Many copper salts (for instance, the nitrite and carbonate) leave oxide of copper[8 bis] in the form of friable black powder, after being ignited. If the ignition be carried further, Cu_{2}O may be formed from the CuO.[8 tri] Anhydrous cupric oxide is very easily dissolved in acids, forming cupric salts, CuX_{2}. They are analogous to the salts MgX_{2}, ZnX_{2}, NiX_{2}, FeX_{2}, in many respects. On adding potassium or ammonium hydroxide to a solution of a cupric salt, it forms a gelatinous blue precipitate of the hydrated oxide of copper, CuH_{2}O_{2}, insoluble in water. The resultant precipitate is redissolved by an excess of ammonia, and gives a very beautiful azure blue solution, of so intense a colour that the presence of small traces of cupric salts may be discovered by this means.[9] An excess of potassium or sodium hydroxide does not dissolve cupric hydroxide. A hot solution gives a black precipitate of the anhydrous oxide instead of the blue precipitate, and the precipitate of the hydroxide of copper becomes granular, and turns black when the solution is heated. This is due to the fact that the blue hydroxide is exceedingly unstable, and when slightly heated it loses the elements of water and gives the black anhydrous cupric oxide: CuH_{2}O_{2} = CuO + H_{2}O.

[8 bis] The oxide of copper obtained by igniting the nitrate is frequently used for organic analyses. It is hygroscopic and retains nitrogen (1·5 c.c. per gram) when the nitrate is heated in vacuo (Richards and Rogers, 1893).

[8 tri] Oxide of copper is also capable of dissociating when heated. Debray and Joannis showed that it then disengages oxygen, whose maximum tension is constant for a given temperature, providing that fusion does not take place (the CuO then dissolves in the molten Cu_{2}O); that this loss of oxygen is followed by the formation of suboxide, and that on cooling, the oxygen is again absorbed, forming CuO.

[9] Cupric oxide and many of its salts are able to give definite, although unstable, compounds with ammonia. This faculty already shows itself in the fact that cupric oxide, as well as the salts of copper, dissolves in aqueous ammonia, and also in the fact that salts of copper absorb ammonia gas. If ammonia be added to a solution of any cupric salt, it first forms a precipitate of cupric hydroxide, which then dissolves in an excess of ammonia. The solution thus formed, when evaporated or on the addition of alcohol, frequently deposits crystals of salts containing both the elements of the salt of copper taken and of ammonia. Several such compounds are generally formed. Thus cupric chloride, CuCl_{2}, according to Deherain, forms four compounds with ammonia--namely, with one, two, four, and six molecules of ammonia. Thus, for example, if ammonia gas be passed into a boiling saturated solution of cupric chloride, on cooling, small octahedral crystals of a blue colour separate out, containing CuCl_{2},2NH_{3},H_{2}O. At 150° this substance loses half the ammonia and all the water contained in it, leaving the compound CuCl_{2},NH_{3}. Nitrate of copper forms the compound Cu(NO_{3}){2},2NH{3}· This compound remains unchanged on evaporation. Dry cupric sulphate absorbs ammonia gas, and gives a compound containing five molecules of ammonia to one of sulphate (Vol. I., p. 257, and Chapter XXII., Note 35). If this compound is dissolved in aqueous ammonia, on evaporation it deposits a crystalline substance containing CuSO_{4},4NH_{3},H_{2}O. At 150° this substance loses the molecule of water and one-fourth of its ammonia. On ignition all these compounds part with the remaining ammonia in the form of an ammoniacal salt, so that the residue consists of cupric oxide. Both the hydrated and anhydrous cupric oxide are soluble in aqueous ammonia.

The solution obtained by the action of aqueous ammonia and air on copper turnings (Note 6) is remarkable for its faculty of dissolving cellulose, which is insoluble in water, dilute acids, and alkalis. Paper soaked in such a solution acquires the property of not rotting, of being difficultly combustible, and waterproof, &c. It has therefore been applied, especially in England, to many practical purposes--for example, to the construction of temporary buildings, for covering roofs, &c. The composition of the substance held in solution is Cu(HO){2},4NH{3}.

If dry ammonia gas be passed over cupric oxide heated to 265°, a portion of the oxide of copper remains unaltered, whilst the other portion gives copper nitride, the oxygen of the copper oxide combining with the hydrogen and forming water. The oxide of copper which remains unchanged is easily removed by washing the resultant product with aqueous ammonia. Copper nitride is very stable, and is insoluble; it has the composition Cu_{3}N (i.e. the copper is monatomic here as in Cu_{2}O), and is an amorphous green powder, which is decomposed when strongly ignited, and gives cuprous chloride and ammonium chloride when treated with hydrochloric acid. Like the other nitrides, copper nitride, Cu_{3}N, has scarcely been investigated. Granger (1892), by heating copper in the vapour of phosphorus, obtained hexagonal prisms of Cu_{5}P, which passed into Cu_{6}P (previously obtained by Abel) when heated in nitrogen. Arsenic is easily absorbed by copper, and its presence (like P), even in small quantities, has a great influence upon the properties of copper--for instance, pure copper wire 1 sq. mm. in section breaks under a load of 35 kilos, while the presence of O·22 p.c. of arsenic raises the breaking load to 42 kilos.

Cupric oxide fuses at a strong heat, and on cooling forms a heavy crystalline mass, which is black, opaque, and somewhat tenacious. It is a feebly energetic base, so that not only do the oxides of the metals of the alkalis and alkaline earths displace it from its compounds, but even such oxides as those of lead and silver precipitate it from solutions, which is partially due to these oxides being soluble, although but slightly so, in water. However, cupric oxide, and especially the hydroxide, easily combines with even the least energetic acids, and does not give any compounds with bases; but, on the other hand, it easily forms basic salts,[9 bis] and in this respect outstrips magnesium and recalls the oxides of lead or mercury. Hence the hydroxide of copper dissolves in solutions of neutral cupric salts. The cupric salts are generally blue or green, because cupric hydroxide itself is coloured. But some of the salts in the anhydrous state are colourless.[10]

[9 bis] As a comparatively feeble base, oxide of copper easily forms both basic and double salts. As an instance we may mention the double salts composed of the dichloride CuCl_{2},2H_{2}O and potassium chloride. The double salt CuK_{2}Cl_{4},2H_{2}O crystallises from solutions in blue plates, but when heated alone or with substances taking up water easily gives brown needles CuKCl_{3} and at the same time KCl, and this reaction is reversible at 92° as Meyerhoffer (1889) showed (i.e. above 92° the simpler double salt is formed and below 92° the more complex salt). With an excess of the copper salt, KCl gives another double salt, Cu_{2}KCl_{5},4H_{2}O, the transition temperature of which is 55°. The instances of equilibria which are encountered in such complex relations (see Chapter XIV., Note 25, astrakhanite, and Chapter XXII., Note 23) are embraced by the law of phases given by Gibbs (Transactions of the Connecticut Academy of Sciences, 1875-1878, in J. Willard Gibbs' memoir 'On the equilibrium of heterogeneous substances:' and in a clearer and more accessible form in H. W. Bakhuis Roozeboom's papers, Rec. trav. chim., Vol. VI., and in W. Meyerhoffer's memoir Die Phasenregel und ihre Anwendungen, 1893, to which sources we refer those desiring fuller information respecting this law). Gibbs calls 'bodies' substances (simple or compound) capable of forming homogeneous complexes (for instance, solutions or intercombinations) of a varied composition; a phase--a mechanically separable portion of such bodies or of their homogeneous complexes (for instance, a vapour, liquid or precipitated solid), perfect equilibrium--such a state of bodies and of their complexes as is characterised by a constant pressure at a constant temperature even under a change in the amount of one of the component parts (for instance, of a salt in a saturated solution), while an imperfect equilibrium is such a one for which such a change corresponds with a change of pressure (for instance, an unsaturated solution). The law of phases consists in the fact that: n bodies only give a perfect equilibrium when n + 1 phases participate in that equilibrium--for example, in the equilibrium of a salt in its saturated solution in water there are two bodies (the salt and water) and three phases, namely, the salt, solution, and vapour, which can be mechanically separated from each other, and to this equilibrium there corresponds a definite tension. At the same time, n bodies may occur in n + 2 phases, but only at one definite temperature and one pressure; a change of one of these may bring about another state (perfect or not--equilibrium stable or unstable). Thus water when liquid at the ordinary temperature offers two phases (liquid and vapour) and is in perfect equilibrium (as also is ice below 0°), but water, ice, and vapour (three phases and only one body) can only be in equilibrium at 0°, and at the ordinary pressure; with a change of t there will remain either only ice and vapour or only liquid water and vapour; whilst with a rise of pressure not only will the vapour pass into the liquid (there again only remain two phases) but also the temperature of the formation of ice will fall (by about 7° per 1000 atmospheres). The same laws of phases are applicable to the consideration of the formation of simple or double salts from saturated solutions and to a number of other purely chemical relations. Thus, for example, in the above-mentioned instance, when the bodies are KCl, CuCl_{2}, and H_{2}O, perfect equilibrium (which here has reference to the solubility) consisting of four phases, corresponds to the following seven cases, considering only the phases (above 0°) A = CuCl_{2},2KCl,2H_{2}O; B = CuCl_{2}KCl; C = CuCl_{2},2H_{2}O,KCl, solution and vapour: (1) A + B + solution + vapour; (2) A + C + solution + vapour; (3) A + KCl + solution + vapour; (4) A + B + C + vapour (it follows that B + KCl + solution gives A); (5) A + C + KCl + vapour; (6) B + C + solution + vapour; and (7) B + KCl + solution + vapour. Thus above 92° A gives B + KCl. The law of phases by bringing complex instances of chemical reaction under simple physical schemes, facilitates their study in detail and gives the means of seeking the simplest chemical relations dealing with solutions, dissociation, double decompositions and similar cases, and therefore deserves consideration, but a detailed exposition of this subject must be looked for in works on physical chemistry.

[10] The normal cupric nitrate, CuN_{2}O_{6},3H_{2}O, is obtained as a deliquescent salt of a blue colour (soluble in water and in alcohol) by dissolving copper or cupric oxide in nitric acid. It is so easily decomposed by the action of heat that it is impossible to drive off the water of crystallisation from it before it begins to decompose. During the ignition of the normal salt the cupric oxide formed enters into combination with the remaining undecomposed normal salt, and gives a basic salt, CuN_{2}O_{6},2CuH_{2}O_{2}. The same basic salt is obtained if a certain quantity of alkali or cupric hydroxide or carbonate be added to the solution of the normal salt, which is even decomposed when boiled with metallic copper, and forms the basic salt as a green powder, which easily decomposes under the action of heat and leaves a residue of cupric oxide. The basic salt, having the composition CuN_{2}O_{6},3CuH_{2}O_{2}, is nearly insoluble in water.

The normal carbonate of copper, CuCO_{3}, occurs in nature, although extremely rarely. If solutions of cupric salts be mixed with solutions of alkali carbonates, then, as in the case of magnesium, carbonic anhydride is evolved and basic salts are formed, which vary in composition according to the temperature and conditions of the reaction. By mixing cold solutions, a voluminous blue precipitate is formed, containing an equivalent proportion of cupric hydroxide and carbonate (after standing or heating, its composition is the same as malachite, sp. gr. 3·51: 2CuSO_{4} + 2Na_{2}CO_{3} + H_{2}O = CuCO_{3},CuH_{2}O_{2} + 2Na_{2}SO_{4} + CO_{2}. If the resultant blue precipitate be heated in the liquid, it loses water and is transformed into a granular green mass of the composition Cu_{2}CO_{4}--i.e. into a compound of the normal salt with anhydrous cupric oxide. This salt of the oxide corresponds with orthocarbonic acid, C(OH){4} = CH{4}O_{4} where 4H is replaced by 2Cu. On further boiling this salt loses a portion of the carbonic acid, forming black cupric oxide, so unstable is the compound of copper with carbonic anhydride. Another basic salt which occurs in nature, 2CuCO_{3},CuH_{2}O_{2}, is known as azurite, or blue carbonate of copper; it also loses carbonic acid when boiled with water. On mixing a solution of cupric sulphate with sodium sesquicarbonate no precipitate is at first obtained, but after boiling a precipitate is formed having the composition of malachite. Debray obtained artificial azurite by heating cupric nitrate with chalk.

The commonest normal salt is blue vitriol--i.e. the normal cupric sulphate. It generally contains five molecules of water of crystallisation, CuSO_{4},5H_{2}O. It forms the product of the action of strong sulphuric acid on copper, sulphurous anhydride being evolved. The same salt is obtained in practice by carefully roasting sulphuretted ores of copper, and also by the action of water holding oxygen in solution on them: CuS + O_{4} = CuSO_{4}. This salt forms a by-product, obtained in gold refineries, when the silver is precipitated from the sulphuric acid solution by means of copper. It is also obtained by pouring dilute sulphuric acid over sheet copper in the presence of air, or by heating cupric oxide or carbonate in sulphuric acid. The crystals of this salt belong to the triclinic system, have a specific gravity of 2·19, are of a beautiful blue colour, and give a solution of the same colour. 100 parts of water at 0° dissolve 15, at 25° 23, and at 100° about 45 parts of cupric sulphate, CuSO_{4}.[10 bis] At 100° this salt loses a portion of its water of crystallisation, which it only parts with entirely at a high temperature (220°) and then gives a white powder of the anhydrous sulphate; and the latter, on further calcination, loses the elements of sulphuric anhydride, leaving cupric oxide, like all the cupric salts. The anhydrous (colourless) cupric sulphate is sometimes used for absorbing water; it turns blue in the process. It offers the advantage that it retains both hydrochloric acid and water, but not carbonic anhydride.[11] Cupric sulphate is used for steeping seed corn; this is said to prevent the growth of certain parasites on the plants. In the arts a considerable quantity of cupric sulphate is also used in the preparation of other copper salts--for instance, of certain pigments[11 bis]--and a particularly large quantity is used in the galvanoplastic process, which consists in the deposition of copper from a solution of cupric sulphate by the action of a galvanic current, when the metallic copper is deposited on the negative pole and takes the shape of the latter. The description of the processes of galvanoplastic art introduced by Jacobi in St. Petersburg forms a part of applied physics, and will not be touched on here, and we will only mention that, although first introduced for small articles, it is now used for such articles as type moulds (clichés), for maps, prints, &c., and also for large statues, and for the deposition of iron, zinc, nickel, gold, silver, &c. on other metals and materials. The beginning of the application of the galvanic current to the practical extraction of metals from solutions has also been established, especially since the dynamo-electric machines of Gramme, Siemens, and others have rendered it possible to cheaply convert the mechanical motion of the steam engine into an electric current. It is to be expected that the application of the electric current, which has long since given such important results in chemistry, will, in the near future, play an important part in technical processes, the example being shown by electric lighting.

[10 bis] Although sulphate of copper usually crystallises with 5H_{2}O, that is, differently to the sulphates of Mg, Fe, and Mn, it is nevertheless perfectly isomorphous with them, as is seen not only in the fact that it gives isomorphous mixtures with them, containing a similar amount of water of crystallisation, but also in the ease with which it forms, like all bases analogous to MgO, double salts, R_{2}Cu(SO_{4}){2},6H{2}O, where R = K, Rb, Cs, of the monoclinic system.

Salts of this kind, like CuCl_{2},2KCl,2H_{2}O,PtK_{2}Cy_{4}, &c., present a composition CuX_{2} if the representation of double salts given in Chapter XXIII., Note 11, be admitted, because they, like Cu(HO){2}, contain Cu(X{2}K){2}, where X{2} = SO_{4}, i.e. the residue of sulphuric acid, which combines with H_{2}, and is therefore able to replace the H_{2} by X_{2} or O. A detailed study of the crystalline forms of these salts, made by Tutton (1893) (see Chapter XIII., Note 1), showed: (1) that 22 investigated salts of the composition R_{2}M(SO_{4}),6H_{2}O, where R = K, Rb, Cs, and M = Mg, Zn, Cd, Mn, Fe, Co, Ni, Cu, present a complete crystallographic resemblance; (2) that in all respects the Rb salts present a transition between the K and Cs salts; (3) that the Cs salts form crystals most easily, and the K salts the most difficultly, and that for the K salts of Cd and Mn it was even impossible to obtain well-formed crystals; (4) that notwithstanding the closeness of their angles, the general appearance (habit) of the potassium compound differs very clearly from the Cs salts, while the Rb salts present a distinct transition in this respect; (5) that the angle of the inclination of one of the axes to the plane of the two other axes showed that in the K salts (angle from 75° to 75° 38´) the inclination is least, in the Cs salts (from 72° 52´ to 73° 50´) greatest, and in the Rb salts (from 73° 57´ to 74° 42´) intermediate between the two; the replacement of Mg ... Cu produces but a very small change in this angle; (6) that the other angles and the ratio of the axes of the crystals exhibit a similar variation; and (7) that thus the variation of the form is chiefly determined by the atomic weight of the alkaline metal. As an example we cite the magnitude of the inclination of the axes of R_{2}M(SO_{4}){2},6H{2}O.

R = K Rb Cs M = Mg 75° 12´ 74° 1´ 72° 54´ Zn 75° 12´ 74° 7´ 72° 59´ Cd -- 74° 7´ 72° 49´ Mn -- 73° 3´ 72° 53´ Fe 75° 28´ 74° 16´ 73° 8´ Co 75° 5´ 73° 59´ 72° 52´ Ni 75° 0´ 73° 57´ 72° 58´ Cu 75° 32´ 74° 42´ 73° 50´

This shows clearly (within the limits of possible error, which may be as much as 30´) the almost perfect identity of the independent crystalline forms notwithstanding the difference of the atomic weights of the diatomic elements, M = Mg, Cu.

[11] In addition to what has been said (Chapter I., Note 65, and Chapter XXII., Note 35) respecting the combination of CuSO_{4} with water and ammonia, we may add that Lachinoff (1893) showed that CuSO_{4},5H_{2}O loses 4-3/4H_{2}O at 180°, that CuSO_{4},5NH_{3} also loses 4-3/4NH_{3} at 320°, and that only 1/4H_{2}O and 1/4NH_{3} remain in combination with the CuSO_{4}. The last 1/4H_{2}O can only be driven off by heating to 200°, and the last 1/4NH_{3} by heating to 360°. Ammonia displaces water from CuSO_{4},5H_{2}O, but water cannot displace the ammonia from CuSO_{4},5NH_{3}. If hydrochloric acid gas be passed over CuSO_{4},5H_{2}O at the ordinary temperature, it first forms CuSO_{4},5H_{2}O,3HCl, and then CuSO_{4},2H_{2}O,2HCl. When air is passed over the latter compound it passes into CuSO_{4}H_{2}O with a small amount of HCl (about 1/8HCl). At 100° CuSO_{4},5H_{2}O in a stream of hydrochloric acid gas gives CuSO_{4},1/4H_{2}O,2HCl, and then CuSO_{4},1/4H_{2}O,HCl, whilst after prolonged heating CuSO_{4} remains, which rapidly passes into CuSO_{4},5H_{2}O when placed under a bell jar over water. Over sulphuric acid, however, CuSO_{4},5H_{2}O only parts with 3H_{2}O, and if CuSO_{4},2H_{2}O be placed over water it again forms CuSO_{4},5H_{2}O, and so on.

[11 bis] Commercial blue vitriol generally contains ferrous sulphate. The salt is purified by converting the ferrous salt into a ferric salt by heating the solution with chlorine or nitric acid. The solution is then evaporated to dryness, and the unchanged cupric sulphate extracted from the residue, which will contain the larger portion of the ferric oxide. The remainder will be separated if cupric hydroxide is added to the solution and boiled; the cupric oxide, CuO, then precipitates the ferric oxide, Fe_{2}O_{3}, just as it is itself precipitated by silver oxide. But the solution will contain a small proportion of a basic salt of copper, and therefore sulphuric acid must be added to the filtered solution, and the salt allowed to crystallise. Acid salts are not formed, and cupric sulphate itself has an acid reaction on litmus paper.

The alloys of copper with certain metals, and especially with zinc and tin, are easily formed by directly melting the metals together. They are easily cast into moulds, forged, and worked like copper, whilst they are much more durable in the air, and are therefore frequently used in the arts. Even the ancients used exclusively alloys of copper, and not pure copper, but its alloys with tin or different kinds of bronze (Chapter XVIII., Note 35). The alloys of copper with zinc are called brass or 'yellow metal.' Brass contains about 32 p.c. of zinc; generally, however, it does not contain more than 65 p.c. of copper. The remainder is composed of lead and tin, which usually occur, although in small quantities, in brass. Yellow metal contains about 40 p.c. of zinc.[12] The addition of zinc to copper changes the colour of the latter to a considerable degree; with a certain amount of zinc the colour of the copper becomes yellow, and with a still larger proportion of zinc an alloy is formed which has a greenish tint. In those alloys of zinc and copper which contain a larger amount of zinc than of copper, the yellow colour disappears and is replaced by a greyish colour. But when the amount of zinc is diminished to about 20 p.c., the alloy is red and hard, and is called 'tombac.' A contraction takes place in alloying copper with zinc, so that the volume of the alloy is less than that of either metal individually. The zinc volatilises on prolonged heating at a high temperature and the excess of metallic copper remains behind. When heated in the air, the zinc oxidises before the copper, so that all the zinc alloyed with copper may be removed from the copper by this means. An important property of brass containing about 30 p.c. of zinc is that it is soft and malleable in the cold, but becomes somewhat brittle when heated. We may also mention that ordinary copper coins contain, in order to render them hard, tin, zinc, and iron (Cu = 95 p.c.); that it is now customary to add a small amount of phosphorus to copper and bronze, for the same purpose; and also that copper is added to silver and gold in coining, &c. to render it hard; moreover, in Germany, Switzerland, and Belgium, and other countries, a silver-white alloy (melchior, German silver, &c.), for base coinage and other purposes, is prepared from brass and nickel (from 10 to 20 p.c. of nickel; 20 to 30 p.c. zinc: 50 to 70 p.c. copper), or directly from copper and nickel, or, more rarely, from an alloy containing silver, nickel, and copper.[12 bis]

[12] Among the alloys of copper resembling brass, delta metal, invented by A. Dick (London) is largely used (since 1883). It contains 55 p.c. Cu, and 41 p.c. Zn, the remaining 4 p.c. being composed of iron (as much as 3-1/2 p.c., which is first alloyed with zinc), or of cobalt, and manganese, and certain other metals. The sp. gr. of delta metal is 8·4. It melts at 950°, and then becomes so fluid that it fills up all the cavities in a mould and forms excellent castings. It has a tensile strength of 70 kilos per sq. mm. (gun metal about 20, phosphor bronze about 30). It is very soft, especially when heated to 600°, but after forging and rolling it becomes very hard; it is more difficultly acted upon by air and water than other kinds of brass, and preserves its golden yellow colour for any length of time, especially if well polished. It is used for making bearings, screw propellers, valves, and many other articles. In general the alloys of Cu and Zn containing about 2/3 p.c. by weight of copper were for a long time almost exclusively made in Sweden and England (Bristol, Birmingham). These alloys for the most part are cheaper, harder, and more fusible than copper alone, and form good castings. The alloys containing 45-80 p.c. Cu crystallise in cubes if slowly cooled (Bi also gives crystals). By washing the surface of brass with dilute sulphuric acid, Zn is removed and the article acquires the colour of copper. The alloys approaching Zn_{2}Cu_{3} in their composition exhibit the greatest resistance (under other equal conditions; of purity, forging, rolling, &c.) The addition of 3 p.c. Al, or 5 p.c. Sn, improves the quality of brass. Respecting aluminium bronze see Chapter XVII. p. 88.

[12 bis] Ball (also Kamensky), 1888, by investigating the electrical conductivity of the alloys of antimony and copper with lead, came to the conclusion that only two definite compounds of antimony and copper exist, whilst the other alloys are either alloys of these two together or with antimony or with copper. These compounds are Cu_{2}Sb and Cu_{4}Sb--one corresponds with the maximum, and the other with the minimum, electrical resistance. In general, the resistance offered to an electrical current forms one of the methods by which the composition of definite alloys (for example, Pb_{2}Zn_{7}) is often established, whilst the electromotive force of alloys affords (Laurie, 1888) a still more accurate method--for instance, several definite compounds were discovered by this method among the alloys of copper with zinc and tin; but we will not enter into any details of this subject, because we avoid all references to electricity, although the reader is recommended to make himself acquainted with this branch of science, which has many points in common with chemistry. The study of alloys regarded as solid solutions should, in my opinion, throw much light upon the question of solutions, which is still obscure in many aspects and in many branches of chemistry.

Copper, in its cuprous compounds, is so analogous to silver, that were there no cupric compounds, or if silver gave stable compounds of the higher oxide, AgO, the resemblance would be as close as that between chlorine and bromine or zinc and cadmium; but silver compounds corresponding to AgO are quite unknown. Although silver peroxide--which was regarded as AgO, but which Berthelot (1880) recognised as the sesquioxide Ag_{2}O_{3}--is known, still it does not form any true salts, and consequently cannot be placed along with cupric oxide. In distinction to copper, silver as a metal does not oxidise under the influence of heat; and its oxides, Ag_{2}O and Ag_{2}O_{3}, easily lose oxygen (see Note 8 tri). Silver does not oxidise in air at the ordinary pressure, and is therefore classed among the so-called noble metals. It has a white colour, which is much purer than that of any other known metal, especially when the metal is chemically pure. In the arts silver is always used alloyed, because chemically-pure silver is so soft that it wears exceedingly easily, whilst when fused with a small amount of copper, it becomes very hard, without losing its colour.[13]

[13] There are not many soft metals; lead, tin, copper, silver, iron, and gold are somewhat soft, and potassium and sodium very soft. The metals of the alkaline earths are sonorous and hard, and many other metals are even brittle, especially bismuth and antimony. But the very slight significance which these properties have in determining the fundamental chemical properties of substances (although, however, of immense importance in the practical applications of metals) is seen from the example shown by zinc, which is hard at the ordinary temperature, soft at 100°, and brittle at 200°.

As the value of silver depends exclusively on its purity, and as there is no possibility of telling the amount of impurities alloyed with it from its external appearance, it is customary in most countries to mark an article with the amount of pure silver it contains after an accurately-made analysis known as the assay of the silver. In France the assay of silver shows the amount of pure silver in 1,000 parts by weight; in Russia the amount of pure silver in 96 parts--that is, the assay shows the number of zolotniks (4·26 grams) of pure silver in one pound (410 grams) of alloyed silver. Russian silver is generally 84 assay--that is, contains 84 parts by weight of pure silver and 12 parts of copper and other metals. French money contains 90 p.c. (in the Russian system this will be 86·4 assay) by weight of silver [English coins and jewellery contain 92·5 p.c. of silver]; the silver rouble is of 83-1/3 assay--that is, it contains 86·8 p.c. of silver--and the smaller Russian silver coinage is of 48 assay, and therefore contains 50 p.c. of silver. Silver ornaments and articles are usually made in Russia of 84 and 72 assay. As the alloys of silver and copper, especially after being subjected to the action of heat, are not so white as pure silver, they generally undergo a process known as 'blanching' (or 'pickling') after being worked up. This consists in removing the copper from the surface of the article by subjecting it to a dark-red heat and then immersing it in dilute acid. During the calcination the copper on the surface is oxidised, whilst the silver remains unchanged; the dilute acid then dissolves the copper oxides formed, and pure silver is left on the surface. The surface is dull after this treatment, owing to the removal of a portion of the metal by the acid. After being polished the article acquires the desired lustre and colour, so as to be indistinguishable from a pure silver object. In order to test a silver article, a portion of its mass must be taken, not from the surface, but to a certain depth. The methods of assay used in practice are very varied. The commonest and most often used is that known as cupellation. It is based on the difference in the oxidisability of copper, lead, and silver. The cupel is a porous cup with thick sides, made by compressing bone ash. The porous mass of bone ash absorbs the fused oxides, especially the lead oxide, which is easily fusible, but it does not absorb the unoxidised metal. The latter collects into a globule under the action of a strong heat in the cupel, and on cooling solidifies into a button, which may then be weighed. Several cupels are placed in a muffle. A muffle is a semi-cylindrical clay vessel, shown in the accompanying drawing. The sides of the muffle are pierced with several orifices, which allow the access of air into it. The muffle is placed in a furnace, where it is strongly heated. Under the action of the air entering the muffle the copper of the silver alloy is oxidised, but as the oxide of copper is infusible, or, more strictly speaking, difficultly fusible, a certain quantity of lead is added to the alloy; the lead is also oxidised by the air at the high temperature of the muffle, and gives the very fusible lead oxide. The copper oxide then fuses with the lead oxide, and is absorbed by the cupel, whilst the silver remains as a bright white globule. If the weight of the alloy taken and of the silver left on the cupel be determined, it is possible to calculate the composition of the alloy. Thus the essence of cupellation consists in the separation of the oxidisable metals from silver, which does not oxidise under the action of heat. A more accurate method, based on the precipitation of silver from its solutions in the form of silver chloride, is described in detail in works on analytical chemistry.

Silver occurs in nature, both in a native state and in certain compounds. Native silver, however, is of rather rare occurrence. A far greater quantity of silver occurs in combination with sulphur, and especially in the form of silver sulphide, Ag_{2}S, with lead sulphide or copper sulphide, or the ores of various other metals. The largest amount of silver is extracted from the lead in which it occurs. If this lead be calcined in the presence of air, it oxidises, and the resultant lead oxide, PbO ('litharge' or 'silberglätte,' as it is called), melts into a mobile liquid, which is easily removed. The silver remains in an unoxidised metallic state.[14] This process is called cupellation.

[14] In America, whence the largest amount of silver is now obtained, ores are worked containing not more than 1/5 p.c. of silver, whilst at 1/2 p.c. its extraction is very profitable. Moreover, the extraction of silver from ores containing not more than 0·01 p.c. of this metal is sometimes profitable. The majority of the lead smelted from galena contains silver, which is extracted from it. Thus near Arras, in France, an ore is worked which contains about 65 parts of lead and 0·088 part of silver in 100 parts of ore, which corresponds with 136 parts of silver in 100,000 parts of lead. At Freiberg, in Saxony, the ore used (enriched by mechanical dressing) contains about 0·9 of silver, 160 of lead, and 2 of copper in 10,000 parts. In every case the lead is first extracted in the manner described in Chapter XVIII., and this lead will contain all the silver. Not unfrequently other ores of silver are mixed with lead ores, in order to obtain an argentiferous lead as the product. The extraction of small quantities of silver from lead is facilitated by the fact (Pattinson's process) that molten argentiferous lead in cooling first deposits crystals of pure lead, which fall to the bottom of the cooling vessel, whilst the proportion of silver in the unsolidified mass increases owing to the removal of the crystals of lead. The lead is enriched in this manner until it contains 1/400 part of silver, and is then subjected to cupellation on a larger scale. According to Park's process, zinc is added to the molten argentiferous lead, and the alloy of Pb and Zn, which first separates out on cooling, is collected. This alloy is found to contain all the silver previously contained in the lead. The addition of 0·5 p.c. of aluminium to the zinc (Rossler and Edelman) facilitates the extraction of the Ag from the resultant alloy besides preventing oxidation; for, after re-melting, nearly all the lead easily runs off (remains fluid), and leaves an alloy containing about 30 p.c. Ag and about 70 p.c. Zn. This alloy may be used as an anode in a solution of ZnCl_{2}, when the Zn is deposited on the cathode, leaving the silver with a small amount of Pb, &c. behind. The silver can be easily obtained pure by treating it with dilute acids and cupelling.

The ores of silver which contain a larger amount of it are: silver glance, Ag_{2}S (sp. gr. 7·2); argentiferous-copper glance, CuAgS; horn silver or chloride of silver, AgCl; argentiferous grey copper ore; polybasite, M_{9}RS_{6} (where M = Ag, Cu, and R = Sb, As), and argentiferous gold. The latter is the usual form in which gold is found in alluvial deposits and ores. The crystals of gold from the Berezoffsky mines in the Urals contain 90 to 95 of gold and 5 to 9 of silver, and the Altai gold contains 50 to 65 of gold and 36 to 38 of silver. The proportion of silver in native gold varies between these limits in other localities. Silver ores, which generally occur in veins, usually contain native silver and various sulphur compounds. The most famous mines in Europe are in Saxony (Freiberg), which has a yearly output of as much as 26 tons of silver, Hungary, and Bohemia (41 tons). In Russia, silver is extracted in the Altai and at Nerchinsk (17 tons). The richest silver mines known are in America, especially in Chili (as much as 70 tons), Mexico (200 tons), and more particularly in the Western States of North America. The richness of these mines may be judged from the fact that one mine in the State of Nevada (Comstock, near Washoe and the cities of Gold Hill and Virginia), which was discovered in 1859, gave an output of 400 tons in 1866. In place of cupellation, chlorination may also be employed for extracting silver from its ores. The method of chlorination consists in converting the silver in an ore into silver chloride. This is either done by a wet or by a dry method, roasting the ore with NaCl. When the silver chloride is formed, the extraction of the metal is also done by two methods. The first consists in the silver chloride being reduced to metal by means of iron in rotating barrels, with the subsequent addition of mercury which dissolves the silver, but does not act on the other metals. The mercury holding the silver in solution is distilled, when the silver remains behind. This method is called amalgamation. The other method is less frequently used, and consists in dissolving the silver chloride in sodium chloride or in sodium thiosulphate, and then precipitating the silver from the solution. The amalgamation is then carried on in rotating barrels containing the roasted ore mixed with water, iron, and mercury. The iron reduces the silver chloride by taking up the chlorine from it. The technical details of these processes are described in works on metallurgy. The extraction of AgCl by the wet method is carried on (Patera's process) by means of a solution of hyposulphite of sodium which dissolves AgCl (see Note 23), or by lixiviating with a 2 p.c. solution of a double hyposulphite of Na and Cu (obtained by adding CuSO_{4} to Na_{2}S_{2}O_{3}). The resultant solution of AgCl is first treated with soda to precipitate PbCO_{3}, and then with Na_{2}S, which precipitates the Ag and Au. The process should be carried on rapidly to prevent the precipitation of Cu_{2}S from the solution of CuSO_{4} and Na_{2}S_{2}O_{3}.

Commercial silver generally contains copper, and, more rarely, other metallic impurities also. Chemically pure silver is obtained either by cupellation or by subjecting ordinary silver to the following treatment. The silver is first dissolved in nitric acid, which converts it and the copper into nitrates, Cu(NO_{3}){2} and AgNO{3}; hydrochloric acid is then added to the resultant solution (green, owing to the presence of the cupric salt), which is considerably diluted with water in order to retain the lead chloride in solution if the silver contained lead. The copper and many other metals remain in solution, whilst the silver is precipitated as silver chloride. The precipitate is allowed to settle, and the liquid is decanted off; the precipitate is then washed and fused with sodium carbonate. A double decomposition then takes place, sodium chloride and silver carbonate being formed; but the latter decomposes into metallic silver, because the silver oxide is decomposed by heat: Ag_{2}CO_{3} = Ag_{2} + O + CO_{2}. The silver chloride may also be mixed with metallic zinc, sulphuric acid, and water, and left for some time, when the zinc removes the chlorine from the silver chloride and precipitates the silver as a powder. This finely-divided silver is called 'molecular silver.'[15]

[15] There is another practical method which is also suitable for separating the silver from the solutions obtained in photography, and consists in precipitating the silver by oxalic acid. In this case the amount of silver in the solution must be known, and 23 grams of oxalic acid dissolved in 400 grams of water must be added for every 60 grams of silver in solution in a litre of water. A precipitate of silver oxalate, Ag_{2}C_{2}O_{4}, is then obtained, which is insoluble in water but soluble in acids. Hence, if the liquid contain any free acid it must be previously freed from it by the addition of sodium carbonate. The resultant precipitate of silver oxalate is dried, mixed with an equal weight of dry sodium carbonate, and thrown into a gently-heated crucible. The separation of the silver then proceeds without an explosion, whilst the silver oxalate if heated alone decomposes with explosion.

According to Stas, the best method for obtaining silver from its solutions is by the reduction of silver chloride dissolved in ammonia by means of an ammoniacal solution of cuprous thiosulphate; the silver is then precipitated in a crystalline form. A solution of ammonium sulphite may be used instead of the cuprous salt.

Chemically-pure silver has an exceeding pure white colour, and a specific gravity of 10·5. Solid silver is lighter than the molten metal, and therefore a piece of silver floats on the latter. The fusing-point of silver is about 950° C., and at the high temperature attained by the combustion of detonating gas it volatilises.[16] By employing silver reduced from silver chloride by milk sugar and caustic potash, and distilling it, Stas obtained silver purer than that obtained by any other means; in fact, this was perfectly pure silver. The vapour of silver has a very beautiful green colour, which is seen when a silver wire is placed in an oxyhydrogen flame.[17]

[16] Silver is very malleable and ductile; it may be beaten into leaves 0·002 mm. in thickness. Silver wire may be made so fine that 1 gram is drawn into a wire 2-1/2 kilometres long. In this respect silver is second only to gold. A wire of 2 mm. diameter breaks under a strain of 20 kilograms.

[17] In melting, silver absorbs a considerable amount of oxygen, which is disengaged on solidifying. One volume of molten silver absorbs as much as 22 volumes of oxygen. In solidifying, the silver forms cavities like the craters of a volcano, and throws off metal, owing to the evolution of the gas; all these phenomena recall a volcano on a miniature scale (Dumas). Silver which contains a small quantity of copper or gold, &c., does not show this property of dissolving oxygen.

The absorption of oxygen by molten silver is, however, an oxidation, but it is at the same time a phenomenon of solution. One cubic centimetre of molten silver can dissolve twenty-two cubic centimetres of oxygen, which, even at 0°, only weighs 0·03 gram, whilst 1 cubic centimetre of silver weighs at least 10 grams, and therefore it is impossible to suppose that the absorption of the oxygen is attended by the formation of any definite compound (rich in oxygen) of silver and oxygen (about 45 atoms of silver to 1 of oxygen) in any other but a dissociated form, and this is the state in which substances in solution must be regarded (Chapter I.)

Le Chatelier showed that at 300° and 15 atmospheres pressure silver absorbs so much oxygen that it may be regarded as having formed the compound Ag_{4}O, or a mixture of Ag_{2} and Ag_{2}O. Moreover, silver oxide, Ag_{2}O, only decomposes at 300° under low pressures, whilst at pressures above 10 atmospheres there is no decomposition at 300° but only at 400°.

Stas showed that silver is oxidised by air in the presence of acids. V. d. Pfordten confirmed this, and showed that an acidified solution of potassium permanganate rapidly dissolves silver in the presence of air.

It has long been known (Wöhler) that when nitrate of silver, AgNO_{3}, reacts as an oxidising agent upon citrates and tartrates, it is able under certain conditions to give either a salt of suboxide of silver (see Note 19) or a red solution, or to give a precipitate of metallic silver reduced at the expense of the organic substances. In 1889 Carey Lea, in his researches on this class of reactions, showed that soluble silver is here formed, which he called allotropic silver. It may be obtained by taking 200 c.c. of a 10 per cent. solution of AgNO_{3} and quickly adding a mixture (neutralised with NaHO) of 200 c.c. of a 30 per cent. solution of FeSO_{4} and 200 c.c. of a 40 per cent. solution of sodium citrate. A lilac precipitate is obtained, which is collected on a filter (the precipitate becomes blue) and washed with a solution of NH_{4}NO_{3}. It then becomes soluble in pure water, forming a red perfectly transparent solution from which the dissolved silver is precipitated on the addition of many soluble foreign bodies. Some of the latter--for instance, NH_{4}NO_{3}, alkaline sulphates, nitrates, and citrates--give a precipitate which redissolves in pure water, whilst others--for instance, MgSO_{4}, FeSO_{4}, K_{2}Cr_{2}O_{7}, AgNO_{3}, Ba(NO_{3}){2} and many others--convert the precipitated silver into a new variety, which, although no longer soluble in water, regains its solubility in a solution of borax and is soluble in ammonia. Both the soluble and insoluble silver are rapidly converted into the ordinary grey-metallic variety by sulphuric acid, although nothing is given off in the reaction; the same change takes place on ignition, but in this case CO{2} is disengaged; the latter is formed from the organic substances which remain (to the amount of 3 per cent.) in the modified silver (they are not removed by soaking in alcohol or water). If the precipitated silver be slightly washed and laid in a smooth thin layer on paper or glass, it is seen that the soluble variety is red when moist and a fine blue colour when dry, whilst the insoluble variety has a blue reflex. Besides these, under special conditions[18] a golden yellow variety may be obtained, which gives a brilliant golden yellow coating on glass; but it is easily converted into the ordinary grey-metallic state by friction or trituration. There is no doubt[18 bis] that there is the same relation between ordinary silver which is perfectly insoluble in water and the varieties of silver obtained by Carey Lea[18 tri] as there is between quartz and soluble silica or between CuS and As_{2}S_{2} in their ordinary insoluble forms and in the state of the colloid solution of their hydrosols (see Chapter I., Note 57, and Chapter XVII., Note 25 bis). Here, however, an important step in advance has been made in this respect, that we are dealing with the solution of a simple body, and moreover of a metal--i.e. of a particularly characteristic state of matter. And as boron, gold, and certain other simple bodies have already been obtained in a soluble (colloid) form, and as numerous organic compounds (albuminous substances, gum, cellulose, starch, &c.) and inorganic substances are also known in this form, it might be said that the colloid state (of hydrogels and hydrosols) can be acquired, if not by every substance, at all events by substances of most varied chemical character under particular conditions of formation from solutions. And this being the case, we may hope that a further study of soluble colloid compounds, which apparently present various transitions towards emulsions, may throw a new light upon the complex question of solutions, which forms one of the problems of the present epoch of chemical science. Moreover, we may remark that Spring (1890) clearly proved the colloid state of soluble silver by means of dialysis as it did not pass through the membrane.

[18] When solutions of AgNO_{3}, FeSO_{4}, sodium citrate, and NaHO are mixed together in the manner described above, they throw down a precipitate of a beautiful lilac colour; when transferred to a filter paper the precipitate soon changes colour, and becomes dark blue. To obtain the substance as pure as possible it is washed with a 5-10 p.c. solution of ammonium nitrate; the liquid is decanted, and 150 c.c. of water poured over the precipitate. It then dissolves entirely in the water. A small quantity of a saturated solution of ammonium nitrate is added to the solution, and the silver in solution again separates out as a precipitate. These alternate solutions and precipitations are repeated seven or eight times, after which the precipitate is transferred to a filter and washed with 95 p.c. alcohol until the filtrate gives no residue on evaporation. An analysis of the substance so obtained showed that it contained from 97·18 p.c. to 97·31 p.c. of metallic silver. It remained to discover what the remaining 2-3 p.c. were composed of. Are they merely impurities, or is the substance some compound of silver with oxygen or hydrogen, or does it contain citric acid in combination which might account for its solubility? The first supposition is set aside by the fact that no gases are disengaged by the precipitate of silver, either under the action of gases or when heated. The second supposition is shown to be impossible by the fact that there is no definite relation between the silver and citric acid. A determination of the amount of silver in solution showed that the amount of citric acid varies greatly for one and the same amount of silver, and there is no simple ratio between them. Among other methods of preparing soluble silver given by Carey Lea, we may mention the method published by him in 1891. AgNO_{3} is added to a solution of dextrine in caustic soda or potash; at first a precipitate of brown oxide of silver is thrown down, but the brown colour then changes into a reddish chocolate, owing to the reduction of the silver by the dextrine, and the solution turns a deep red. A few drops of this solution turn water bright red, and give a perfectly transparent liquid. The dextrine solution is prepared by dissolving 40 grams of caustic soda and the same amount of ordinary brown dextrine in two litres of water. To this solution is gradually added 28 grams of AgNO_{3} dissolved in a small quantity of water.

The insoluble allotropic silver is obtained, as was mentioned above, from a solution of silver prepared in the manner described, by the addition of sulphate of copper, iron, barium, magnesium, &c. In one experiment Lea succeeded in obtaining the insoluble allotropic Ag in a crystalline form. The red solution, described above, after standing several weeks, deposits crystals spontaneously in the form of short black needles and thin prisms, the liquid becoming colourless. This insoluble variety, when rubbed upon paper, has the appearance of bright shining green flakes, which polarise light.

The gold variety is obtained in a different manner to the two other varieties. A solution is prepared containing 200 c.c. of a 10 p.c. solution of nitrate of silver, 200 c.c. of a 20 p.c. solution of Rochelle salt, and 800 c.c. of water. Just as in the previous case the reaction consisted in the reduction of the citrate of silver, so in this case it consists in the reduction of the tartrate, which here first forms a red, and then a black precipitate of allotropic Ag, which, when transferred to the filter, appears of a beautiful bronze colour. After washing and drying, this precipitate acquires the lustre and colour peculiar to polished gold, and this is especially remarked where the precipitate comes into contact with glass or china. An analysis of the golden variety gave a percentage composition of 98·750 to 98·749 Ag. Both the insoluble varieties (the blue and gold) have a different specific gravity from ordinary silver. Whilst that of fused silver is 10·50, and of finely-divided silver 10·62, the specific gravity of the blue insoluble variety is 9·58, and of the gold variety 8·51. The gold variety passes into ordinary Ag with great ease. This transition may even be remarked on the filter in those places which have accidentally not been moistened with water. A simple shock, and therefore friction of one particle upon another, is enough to convert the gold variety into normal white silver. Carey Lea sent samples of the gold variety for a long distance by rail packed in three tubes, in which the silver occupied about the quarter of their volume; in one tube only he filled up this space with cotton-wool. It was afterwards found that the shaking of the particles of Ag had completely converted it into ordinary white silver, and that only the tube containing the cotton-wool had preserved the golden variety intact.

The soluble variety of Ag also passes into the ordinary state with great ease, the heat of conversion being, as Prange showed in 1890, about +60 calories.

[18 bis] The opinion of the nature of soluble silver given below was first enunciated in the Journal of the Russian Chemical Society, February 1, 1890, Vol. XXII., Note 73. This view is, at the present time, generally accepted, and this silver is frequently known as the 'colloid' variety. I may add that Carey Lea observed the solution of ordinary molecular silver in ammonia without the access of air.

[18 tri] It is, however, noteworthy that ordinary metallic lead has long been considered soluble in water, that boron has been repeatedly obtained in a brown solution, and that observations upon the development of certain bacteria have shown that the latter die in water which has been for some time in contact with metals. This seems to indicate the passage of small quantities of metals into water (however, the formation of peroxide of hydrogen may be supposed to have some influence in these cases).

As regards the capacity of silver for chemical reactions, it is remarkable for its small capacity for combination with oxygen and for its considerable energy of combination with sulphur, iodine, and certain kindred non-metals. Silver does not oxidise at any temperature, and its oxide, Ag_{2}O, is decomposed by heat. It is also a very important fact that silver is not oxidised by oxygen either in the presence of alkalis, even at exceedingly high temperatures, or in the presence of acids--at least, of dilute acids--which properties render it a very important metal in chemical industry for the fusion of alkalis, and also for many purposes in everyday life; for instance, for making spoons, salt-cellars, &c. Ozone, however, oxidises it. Of all acids nitric acid has the greatest action on silver. The reaction is accompanied by the formation of oxides of nitrogen and silver nitrate, AgNO_{3}, which dissolves in water and does not, therefore, hinder the further action of the acid on the metal. The halogen acids, especially hydriodic acid, act on silver, hydrogen being evolved; but this action soon stops, owing to the halogen compounds of silver being insoluble in water and only very slightly soluble in acids; they therefore preserve the remaining mass of metal from the further action of the acid; in consequence of this the action of the halogen acids is only distinctly seen with finely-divided silver. Sulphuric acid acts on silver in the same manner that it does on copper, only it must be concentrated and at a higher temperature. Sulphurous anhydride, and not hydrogen, is then evolved, but there is no action at the ordinary temperature, even in the presence of air. Among the various salts, sodium chloride (in the presence of moisture, air, and carbonic acid) and potassium cyanide (in the presence of air) act on silver more decidedly than any others, converting it respectively into silver chloride and a double cyanide.

Although silver does not directly combine with oxygen, still three different grades of combination with oxygen may be obtained indirectly from the salts of silver. They are all, however, unstable, and decompose into oxygen and metallic silver when ignited. These three oxides of silver have the following composition: silver suboxide, Ag_{4}O,[19] corresponding with the (little investigated) suboxides of the alkali metals; silver oxide, Ag_{2}O, corresponding with the oxides of the alkali metals and the ordinary salts of silver, AgX; and silver peroxide, AgO,[19 bis] or, judging from Berthelot's researches, Ag_{2}O_{3}. Silver oxide is obtained as a brown precipitate (which when dried does not contain water) by adding potassium hydroxide to a solution of a silver salt--for example, of silver nitrate. The precipitate formed seems, however, to be an hydroxide, AgHO, i.e. AgNO_{3} + KHO = KNO_{3} + AgHO, and the formation of the anhydrous oxide, 2AgHO = Ag_{2}O + H_{2}O, may be compared with the formation of the anhydrous cupric oxide by the action of potassium hydroxide on hot cupric solutions. Silver hydroxide decomposes into water and silver oxide, even at low temperatures; at least, the hydroxide no longer exists at 60°, but forms the anhydrous oxide, Ag_{2}O.[19 tri] Silver oxide is almost insoluble in water; but, nevertheless, it is undoubtedly a rather powerful basic oxide, because it displaces the oxides of many metals from their soluble salts, and saturates such acids as nitric acid, forming with them neutral salts, which do not act on litmus paper.[20] Undoubtedly water dissolves a small quantity of silver oxide, which explains the possibility of its action on solutions of salts--for example, on solutions of cupric salts. Water in which silver oxide is shaken up has a distinctly alkaline reaction. The oxide is distinguished by its great instability when heated, so that it loses all its oxygen when slightly heated. Hydrogen reduces it at about 80°.[20 bis] The feebleness of the affinity of silver for oxygen is shown by the fact that silver oxide decomposes under the action of light, so that it must be kept in opaque vessels. The silver salts are colourless and decompose when heated, leaving metallic silver if the elements of the acid are volatile.[20 tri] They have a peculiar metallic taste, and are exceedingly poisonous; the majority of them are acted on by light, especially in the presence of organic substances, which are then oxidised. The alkaline carbonates give a white precipitate of silver carbonate, Ag_{2}CO_{3}, which is insoluble in water, but soluble in ammonia and ammonium carbonate. Aqueous ammonia, added to a solution of a normal silver salt, first acts like potassium hydroxide, but the precipitate dissolves in an excess of the reagent, like the precipitate of cupric hydroxide.[21] Silver oxalate and the halogen compounds of silver are insoluble in water; hydrochloric acid and soluble chlorides give, as already repeatedly observed, a white precipitate of silver chloride in solutions of silver salts. Potassium iodide gives a yellowish precipitate of silver iodide. Zinc separates all the silver in a metallic form from solutions of silver salts. Many other metals and reducing agents--for example, organic substances--also reduce silver from the solutions of its salts.

[19] Silver suboxide (Ag_{4}O) or argentous oxide is obtained from argentic citrate by heating it to 100° in a stream of hydrogen. Water and argentous citrate are then formed, and the latter, although but slightly soluble in water, gives a reddish-brown solution of colloid silver (Note 18), and when boiled this solution becomes colourless and deposits metallic silver, the argentic salt being again formed. Wöhler, who discovered this oxide, obtained it as a black precipitate by adding potassium hydroxide to the above solution of argentous citrate. With hydrochloric acid the suboxide gives a brown compound, Ag_{2}Cl. Since the discovery of soluble silver the above data cannot be regarded as perfectly trustworthy; it is probable that a mixture of Ag_{2} and Ag_{2}O was being dealt with, so that the actual existence of Ag_{4}O is now doubtful, but there can be no doubt as to the formation of a subchloride, Ag_{2}Cl (see Note 25), corresponding to the suboxide. The same compound is obtained by the action of light on the higher chloride. Other acids do not combine with silver suboxide, but convert it into an argentic salt and metallic silver. In this respect cuprous oxide presents a certain resemblance to these suboxides. But copper forms a suboxide of the composition Cu_{4}O, which is obtained by the action of an alkaline solution of stannous oxide on cupric hydroxide, and is decomposed by acids into cupric salts and metallic copper. The problems offered by the suboxides, as well as by the peroxides, cannot be considered as fully solved.

[19 bis] Silver peroxide, AgO or Ag_{2}O_{3}, is obtained by the decomposition of a dilute (10 p.c.) solution of silver nitrate by the action of a galvanic current (Ritter). On the positive pole, where oxygen is usually evolved in the decomposition of salts, brittle grey needles with a metallic lustre, which occasionally attain a somewhat considerable size, are then formed. They are insoluble in water, and decompose with the evolution of oxygen when they are dried and heated, especially up to 150°, and, like lead dioxide, barium peroxide, &c., their action is strongly oxidising. When treated with acids, oxygen is evolved and a salt of the oxide formed. Silver peroxide absorbs sulphurous anhydride and forms silver sulphate. Hydrochloric acid evolves chlorine; ammonia reduces the silver, and is itself oxidised, forming water and gaseous nitrogen. Analyses of the above-mentioned crystals show that they contain silver nitrate, peroxide, and water. According to Fisher, they have the composition 4AgO,AgNO_{3},H_{2}O, and, according to Berthelot, 4Ag_{2}O_{5},2AgNO_{3},H_{2}O.

[19 tri] According to Carey Lea, however, oxide of silver still retains water even at 100°, and only parts with it together with the oxygen. Oxide of silver is used for colouring glass yellow.

[20] The reaction of Pb(OH)_{2} upon AgHO in the presence of NaHO leads to the formation of a compound of both oxides, PbO_n_Ag_{2}O, from which the oxide of lead cannot be removed by alkalies (Wöhler, Leton). Wöhler, Welch, and others obtained crystalline double salts, R_{2}AgX_{3}, by the action of strong solutions of RX of the halogen salts of the alkaline metals upon AgX, where R = Cs, Rb, K.

[20 bis] According to Müller, ferric oxide is reduced by hydrogen (see Chapter XXII., Note 5) at 295° (into what ?), cupric oxide at 140°, Ni_{2}O_{3} at 150°; nickelous oxide, NiO, is reduced to the suboxide, Ni_{2}O, at 195°, and to nickel at 270°; zinc oxide requires so high a temperature for its reduction that the glass tube in which Müller conducted the experiment did not stand the heat; antimony oxide requires a temperature of 215° for its reduction; yellow mercuric oxide is reduced at 130° and the red oxide at 230°; silver oxide at 85°, and platinum oxide even at the ordinary temperature.

[20 tri] A silica compound, Ag_{2}OSiO_{2} is obtained by fusing AgNO_{3} with silica; this salt is able to decompose with the evolution of oxygen, leaving Ag + SiO_{2}.

[21] If a solution of a silver salt be precipitated by sodium hydroxide, and aqueous ammonia is added drop by drop until the precipitate is completely dissolved, the liquid when evaporated deposits a violet mass of crystalline silver oxide. If moist silver oxide be left in a strong solution of ammonia it gives a black mass, which easily decomposes with a loud explosion, especially when struck. This black substance is called fulminating silver. Probably this is a compound like the other compounds of oxides with ammonia, and in exploding the oxygen of the silver oxide forms water with the hydrogen of the ammonia, which is naturally accompanied by the evolution of heat and formation of gaseous nitrogen, or, as Raschig states, fulminating silver contains NAg_{3} or one of the amides (for instance, NHAg_{2} = NH_{3} + Ag_{2}O - H_{2}O). Fulminating silver is also formed when potassium hydroxide is added to a solution of silver nitrate in ammonia. The dangerous explosions which are produced by this compound render it needful that great care be taken when salts of silver come into contact with ammonia and alkalis (see Chapter XVI., Note 26).

Silver nitrate, AgNO_{3}, is known by the name of lunar caustic (or lapis infernalis); it is obtained by dissolving metallic silver in nitric acid. If the silver be impure, the resultant solution will contain a mixture of the nitrates of copper and silver. If this mixture be evaporated to dryness and the residue carefully fused at an incipient red heat, all the cupric nitrate is decomposed, whilst the greater part of the silver nitrate remains unchanged. On treating the fused mass with water the latter is dissolved, whilst the cupric oxide remains insoluble. If a certain amount of silver oxide be added to the solution containing the nitrates of silver and copper, it displaces all the cupric oxide. In this case it is of course not necessary to take pure silver oxide, but only to pour off some of the solution and to add potassium hydroxide to one portion, and to mix the resultant precipitate of the hydroxides, Cu(OH)_{2} and AgOH, with the remaining portion.[22] By these methods all the copper can be easily removed and pure silver nitrate obtained (its solution is colourless, while the presence of Cu renders it blue), which may be ultimately purified by crystallisation. It crystallises in colourless transparent prismatic plates, which are not acted on by air. They are anhydrous. Its sp. gr. is 4·34; it dissolves in half its weight of water at the ordinary temperature.[22 bis] The pure salt is not acted on by light, but it easily acts in an oxidising manner on the majority of organic substances, which it generally blackens. This is due to the fact that the organic substance is oxidised by the silver nitrate, which is reduced to metallic silver; the latter is thus obtained in a finely-divided state, which causes the black stain. This peculiarity is taken advantage of for marking linen. Silver nitrate is for the same reason used for cauterising wounds and various growths on the body. Here again it acts by virtue of its oxidising capacity in destroying the organic matter, which it oxidises, as is seen from the separation of a coating of black metallic powdery silver from the part cauterised.[22 tri] From the description of the preparation of silver nitrate it will have been seen that this salt, which fuses at 218°, does not decompose at an incipient red heat; when cast into sticks it is usually employed for cauterising. On further heating, the fused salt undergoes decomposition, first forming silver nitrite and then metallic silver. With ammonia, silver nitrate forms, on evaporation of the solution, colourless crystals containing AgNO_{3},2HN_{3} (Marignac). In general the salts of silver, like cuprous, cupric, zinc, &c. salts, are able to give several compounds with ammonia; for example, silver nitrate in a dry state absorbs three molecules (Rose). The ammonia is generally easily expelled from these compounds by the action of heat.

[22] So that we here encounter the following phenomena: copper displaces silver from the solutions of its salts, and silver oxide displaces copper oxide from cupric salts. Guided by the conceptions enunciated in Chapter XV., we can account for this in the following manner: The atomic volume of silver = 10·3, and of copper = 7·2, of silver oxide = 32, and of copper oxide = 13. A greater contraction has taken place in the formation of cupric oxide, CuO, than in the formation of silver oxide, Ag_{2}O, since in the former (13 - 7 = 6) the volume after combination with the oxygen has increased by very little, whilst the volume of silver oxide is considerably greater than that of the metal it contains [32 - (2 × 10·3) = 11·4]. Hence silver oxide is less compact than cupric oxide, and is therefore less stable; but, on the other hand, there are greater intervals between the atoms in silver oxide than in cupric oxide, and therefore silver oxide is able to give more stable compounds than those of copper oxide. This is verified by the figures and data of their reactions. It is impossible to calculate for cupric nitrate, because this salt has not yet been obtained in an anhydrous state; but the sulphates of both oxides are known. The specific gravity of copper sulphate in an anhydrous state is 3·53, and of silver sulphate 5·36; the molecular volume of the former is 45, and of the latter 58. The group SO_{3} in the copper occupies, as it were, a volume 45 - 13 = 32, and in the silver salt a volume 58 - 32 = 26; hence a smaller contraction has taken place in the formation of the copper salt from the oxide than in the formation of the silver salt, and consequently the latter should be more stable than the former. Hence silver oxide is able to decompose the salt of copper oxide, whilst with respect to the metals both salts have been formed with an almost identical contraction, since 58 volumes of the silver salt contain 21 volumes of metal (difference = 37), and 45 volumes of the copper salt contain 7 volumes of copper (difference = 38). Besides which, it must be observed that copper oxide displaces iron oxide, just as silver oxide displaces copper oxide. Silver, copper, and iron, in the form of oxides, displace each other in the above order, but in the form of metals in a reverse order (iron, copper, silver). The cause of this order of the displacement of the oxides lies, amongst other things, in their composition. They have the composition Ag_{2}O, Cu_{2}O_{2}, Fe_{2}O_{3}; the oxide containing a less proportion of oxygen displaces that containing a larger proportion, because the basic character diminishes with the increase of contained oxygen.

Copper also displaces mercury from its salts. It may here be remarked that Spring (1888), on leaving a mixture of dry mercurous chloride and copper for two hours, observed a distinct reduction, which belongs to the category of those phenomena which demonstrate the existence of a mobility of parts (i.e. atoms and molecules) in solid substances.

[22 bis] The reaction of 1 part by weight of AgNO_{3} requires (according to Kremers) the following amounts of water: at 0°, 0·82 part, at 19°·5, 0·41 part, at 54°, 0·20 part, at 110°, 0·09 part, and, according to Tilden, at 125°, 0·0617 part, and at 133°, 0·0515 part.

[22 tri] It may be remarked that the black stain produced by the reduction of metallic silver disappears under the action of a solution of mercuric chloride or of potassium cyanide, because these salts act on finely-divided silver.

Nitrate of silver easily forms double salts like AgNO_{3}2NaNO_{3} and AgNO_{3}KNO_{3}. Silver nitrate under the action of water and a halogen gives nitric acid (see Vol. I. p. 280, formation of N_{2}O_{5}), a halogen salt of silver, and a silver salt of an oxygen acid of the halogen. Thus, for example, a solution of chlorine in water, when mixed with a solution of silver nitrate, gives silver chloride and chlorate. It is here evident that the reaction of the silver nitrate is identical with the reaction of the caustic alkalis, as the nitric acid is all set free and the silver oxide only reacts in exactly the same way in which aqueous potash acts on free chlorine. Hence the reaction may be expressed in the following manner: 6AgNO_{3} + 3Cl_{2} + 3H_{2}O = 5AgCl + AgClO_{3} + 6NHO_{3}.

Silver nitrate, like the nitrates of the alkalis, does not contain any water of crystallisation. Moreover the other salts of silver almost always separate out without any water of crystallisation. The silver salts are further characterised by the fact that they give neither basic nor acid salts, owing to which the formation of silver salts generally forms the means of determining the true composition of acids--thus, to any acid H_{n}X there corresponds a salt Ag_{n}X--for instance, Ag_{3}PO_{4} (Chapter XIX., Note 15).

Silver gives insoluble and exceedingly stable compounds with the halogens. They are obtained by double decomposition with great facility whenever a silver salt comes in contact with halogen salts. Solutions of nitrate, sulphate, and all other kindred salts of silver give a precipitate of silver chloride or iodide in solutions of chlorides and iodides and of the halogen acids, because the halogen salts of silver are insoluble both in water[23] and in other acids. Silver chloride, AgCl, is then obtained as a white flocculent precipitate, silver bromide forms a yellowish precipitate, and silver iodide has a very distinct yellow colour. These halogen compounds sometimes occur in nature; they are formed by a dry method--by the action of halogen compounds on silver compounds, especially under the influence of heat. Silver chloride easily fuses at 451° on cooling from a molten state; it forms a somewhat soft horn-like mass which can be cut with a knife and is known as horn silver. It volatilises at a higher temperature. Its ammoniacal solution, on the evaporation of the ammonia, deposits crystalline chloride of silver, in octahedra. Bromide and iodide of silver also appear in forms of the regular system, so that in this respect the halogen salts of silver resemble the halogen salts of the alkali metals.[24]

[23] Silver chloride is almost perfectly insoluble in water, but is somewhat soluble in water containing sodium chloride or hydrochloric acid, or other chlorides, and many salts, in solution. Thus at 100°, 100 parts of water saturated with sodium chloride dissolve 0·4 part of silver chloride. Bromide and iodide of silver are less soluble in this respect, as also in regard to other solvents. It should be remarked that silver chloride dissolves in solutions of ammonia, potassium cyanide, and of sodium thiosulphate, Na_{2}S_{2}O_{3}. Silver bromide is almost perfectly analogous to the chloride, but silver iodide is nearly insoluble in a solution of ammonia. Silver chloride even absorbs dry ammonia gas, forming very unstable ammoniacal compounds. When heated, these compounds (Vol. I. p. 250, Note 8) evolve the ammonia, as they also do under the action of all acids. Silver chloride enters into double decomposition with potassium cyanide, forming a soluble double cyanide, which we shall presently describe; it also forms a soluble double salt, NaAgS_{2}O_{3}, with sodium thiosulphate.

Silver chloride offers different modifications in the structure of its molecule, as is seen in the variations in the consistency of the precipitate, and in the differences in the action of light which partially decomposes AgCl (see Note 25). Stas and Carey Lea investigated this subject, which has a particular importance in photography, because silver bromide also gives photo-salts. There is still much to be discovered in this respect, since Abney showed that perfectly dry AgCl placed in a vacuum in the dark is not in the least acted upon when subsequently exposed to light.

[24] Silver bromide and iodide (which occur as the minerals bromite and iodite) resemble the chloride in many respects, but the degree of affinity of silver for iodine is greater than that for chlorine and bromine, although less heat is evolved (see Note 28 bis). Deville deduced this fact from a number of experiments. Thus silver chloride, when treated with hydriodic acid, evolves hydrochloric acid, and forms silver iodide. Finely-divided silver easily liberates hydrogen when treated with hydriodic acid; it produces the same decomposition with hydrochloric acid, but in a considerably less degree and only on the surface. The difference between silver chloride and iodide is especially remarkable, since the formation of the former is attended with a greater contraction than that of the latter. The volume of AgCl = 26; of chlorine 27, of silver 10, the sum = 37, hence a contraction has ensued; and in the formation of silver iodide an expansion takes place, for the volume of Ag is 10, of I 26, and of AgI 39 instead of 36 (density, AgCl, 5·59; AgI, 5·67). The atoms of chlorine have united with the atoms of silver without moving asunder, whilst the atoms of iodine must have moved apart in combining with the silver. It is otherwise with respect to the metal; the distance between its atoms in the metal = 2·2, in silver chloride = 3·0, and in silver iodide = 3·5; hence its atoms have moved asunder considerably in both cases. It is also very remarkable, as Fizeau observed, that the density of silver iodide increases with a rise of temperature--that is, a contraction takes place when it is heated and an expansion when it is cooled.

In order to explain the fact that in silver compounds the iodide is more stable than the chloride and oxide, Professor N. N. Beketoff, in his 'Researches on the Phenomena of Substitutions' (Kharkoff, 1865), proposed the following original hypothesis, which we will give in almost the words of the author:--In the case of aluminium, the oxide, Al_{2}O_{3}, is more stable than the chloride, Al_{2}Cl_{6}, and the iodide, Al_{2}I_{6}. In the oxide the amount of the metal is to the amount of the element combined with it as 54·8 (Al = 27·3) is to 48, or in the ratio 112 : 100; for the chloride the ratio is = 25 : 100; for the iodide it = 7 : 100. In the case of silver the oxide (ratio = 1350 : 100) is less stable than the chloride (ratio = 304 : 100), and the iodide (ratio of the weight of metal to the weight of the halogen = 85 : 100) is the most stable. From these and similar examples it follows that the most stable compounds are those in which the weights of the combined substances are equal. This may be partly explained by the attraction of similar molecules even after their having passed into combination with others. This attraction is proportional to the product of the acting masses. In silver oxide the attraction of Ag_{2} for Ag_{2} = 216 × 216 = 46,656, and the attraction of Ag_{2} for O = 216 × 16 = 3,456. The attraction of like molecules thus counteracts the attraction of the unlike molecules. The former naturally does not overcome the latter, otherwise there would be a disruption, but it nevertheless diminishes the stability. In the case of an equality or proximity of the magnitude of the combining masses, the attraction of the like parts will counteract the stability of the compound to the least extent--in other words, with an inequality of the combined masses, the molecules have an inclination to return to an elementary state, to decompose, which does not exist to such an extent where the combined masses are equal. There is, therefore, a tendency for large masses to combine with large, and for small masses to combine with small. Hence Ag_{2}O + 2KI gives K_{2}O + 2AgI. The influence of an equality of masses on the stability is seen particularly clearly in the effect of a rise of temperature. Argentic, mercuric, auric and other oxides composed of unequal masses, are somewhat readily decomposed by heat, whilst the oxides of the lighter metals (like water) are not so easily decomposed by heat. Silver chloride and iodide approach the condition of equality, and are not decomposed by heat. The most stable oxides under the action of heat are those of magnesium, calcium, silicon, and aluminium, since they also approach the condition of equality. For the same reason hydriodic acid decomposes with greater facility than hydrochloric acid. Chlorine does not act on magnesia or alumina, but it acts on lime and silver oxide, &c. This is partially explained by the fact that by considering heat as a mode of motion, and knowing that the atomic heats of the free elements are equal, it must be supposed that the amount of the motion of atoms (their vis viva) is equal, and as it is equal to the product of the mass (atomic weight) into the square of the velocity, it follows that the greater the combining weight the smaller will be the square of the velocity, and if the combining weights be nearly equal, then the velocities also will be nearly equal. Hence the greater the difference between the weights of the combined atoms the greater will be the difference between their velocities. The difference between the velocities will increase with the temperature, and therefore the temperature of decomposition will be the sooner attained the greater be the original difference--that is, the greater the difference of the weights of the combined substances. The nearer these weights are to each other, the more analogous the motion of the unlike atoms, and consequently, the more stable the resultant compound.

The instability of cupric chloride and nitric oxide, the absence of compounds of fluorine with oxygen, whilst there are compounds of oxygen with chlorine, the greater stability of the oxygen compounds of iodine than those of chlorine, the stability of boron nitride, and the instability of cyanogen, and a number of similar instances, where, judging from the above argument, one would expect (owing to the closeness of the atomic weights) a stability, show that Beketoff's addition to the mechanical theory of chemical phenomena is still far from sufficient for explaining the true relations of affinities. Nevertheless, in his mode of explaining the relative stabilities of compounds, we find an exceedingly interesting treatment of questions of primary importance. Without such efforts it would be impossible to generalise the complex data of experimental knowledge.

Fluoride of silver, AgF, is obtained by dissolving Ag_{2}O or Ag_{2}CO_{3} in hydrofluoric acid. It differs from the other halogen salts of silver in being soluble in water (1 part of salt in 0·55 of water). It crystallises from its solution in prisms, AgFH_{2}O (Marignac), or AgF_{2}H_{2}O (Pfaundler), which lose their water in vacuo. Güntz (1891), by electrolising a saturated solution of Ag_{2}F, obtained polyfluoride of silver, Ag_{2}F, which is decomposed by water into AgF + Ag. It is also formed by the action of a strong solution of AgF upon finely-divided (precipitated) silver.

Silver chloride may be decomposed, with the separation of silver oxide, by heating it with a solution of an alkali, and if an organic substance be added to the alkali the chloride can easily be reduced o metallic silver, the silver oxide being reduced in the oxidation of the organic substance. Iron, zinc, and many other metals reduce silver chloride in the presence of water. Cuprous and mercurous chlorides and many organic substances are also able to reduce the silver from chloride of silver. This shows the rather easy decomposability of the halogen compounds of silver. Silver iodide is much more stable in this respect than the chloride. The same is also observed with respect to the action of light upon moist AgCl. White silver chloride soon acquires a violet colour when exposed to the action of light, and especially under the direct action of the sun's rays. After being acted upon by light it is no longer entirely soluble in ammonia, but leaves metallic silver undissolved, from which it might be assumed that the action of light consisted in the decomposition of the silver chloride into chlorine and metallic silver and in fact the silver chloride becomes in time darker and darker. Silver bromide and iodide are much more slowly acted on by light, and, according to certain observations, when pure they are even quite unacted on; at least they do not change in weight,[24 bis] so that if they are acted on by light, the change they undergo must be one of a change in the structure of their parts and not of decomposition, as it is in silver chloride. The silver chloride under the action of light changes in weight, which indicates the formation of a volatile product, and the deposition of metallic silver on dissolving in ammonia shows the loss of chlorine. The change does actually occur under the action of light, but the decomposition does not go as far as into chlorine and silver, but only to the formation of a subchloride of silver, Ag_{2}Cl, which is of a brown colour and is easily decomposed into metallic silver and silver chloride, Ag_{2}Cl = AgCl + Ag. This change of the chemical composition and structure of the halogen salts of silver under the action of light forms the basis of photography, because the halogen compounds of silver, after having been exposed to light, give a precipitate of finely-divided silver, of a black colour, when treated with reducing agents.[25]

[24 bis] The changes brought about by the action of light necessitate distinguishing the photo-salts of silver.

[25] In photography these are called 'developers.' The most common developers are: solutions of ferrous sulphate, pyrogallol, ferrous oxalate, hydroxylamine, potassium sulphite, hydroquinone (the last acts particularly well and is very convenient to use), &c. The chemical processes of photography are of great practical and theoretical interest; but it would be impossible in this work to enter into this special branch of chemistry, which has as yet been very little worked out from a theoretical point of view. Nevertheless, we will pause to consider certain aspects of this subject which are of a purely chemical interest, and especially the facts concerning subchloride of silver, Ag_{2}Cl (see Note 19), and the photo-salts (Note 23). There is no doubt that under the action of light, AgCl becomes darker in colour, decreases in weight, and probably forms a mixture of AgCl, Ag_{2}Cl, and Ag. But the isolation of the subchloride has only been recently accomplished by Güntz by means of the Ag_{2}F, discovered by him (see Note 24). Many chemists (and among them Hodgkinson) assumed that an oxychloride of silver was formed by the decomposition of AgCl under the action of light. Carey Lea's (1889) and A. Richardson's (1891) experiments showed that the product formed does not, however, contain any oxygen at all, and the change in colour produced by the action of light upon AgCl is most probably due to the formation of Ag_{2}Cl. This substance was isolated by Güntz (1891) by passing HCl over crystals of Ag_{2}F. He also obtained Ag_{2}I in a similar manner by passing HI, and Ag_{2}S by passing H_{2}S over Ag_{2}F. Ag_{2}Cl is best prepared by the action of phosphorus trichloride upon Ag_{2}F. At the temperature of its formation Ag_{2}Cl has an easily changeable tint, with shades of violet red to violet black. Under the action of light a similar (isomeric) substance is obtained, which splits up into AgCl + Ag when heated. With potassium cyanide Ag_{2}Cl gives Ag + AgCN + KCl, whence it is possible to calculate the heat of formation of Ag_{2}Cl; it = 29·7, whilst the heat of formation of AgCl = 29·2--i.e. the reaction 2AgCl = Ag_{2}Cl + Cl corresponds to an absorption of 28·7 major calories. If we admit the formation of such a compound by the action of light, it is evident that the energy of the light is consumed in the above reaction. Carey Lea (1892) subjected AgCl, AgBr, and AgI to a pressure (of course in the dark) of 3,000 atmospheres, and to trituration with water in a mortar, and observed a change of colour indicating incipient decomposition, which is facilitated under the action of light by the molecular currents set up (Lermontoff, Egoroff). The change of colour of the halogen salts of silver under the action of light, and their faculty of subsequently giving a visible photographic image under the action of 'developers,' must now be regarded as connected with the decomposition of AgX, leading to the formation of Ag_{2}X, and the different tinted photo-salts must be considered as systems containing such Ag_{2}X's. Carey Lea obtained photo-salts of this kind not only by the action of light but also in many other ways, which we will enumerate to prove that they contain the products of an incomplete combination of Ag with the halogens, (for the salts Ag_{2}X must be regarded as such). The photo-salts have been obtained (1) by the imperfect chlorination of silver; (2) by the incomplete decomposition of Ag_{2}O or Ag_{2}CO_{3} by alternately heating and treating with a halogen acid; (3) by the action of nitric acid or Na_{2}S_{2}O_{3} upon Ag_{2}Cl; (4) by mixing a solution of AgNO_{3} with the hydrates of FeO, MnO and CrO, and precipitating by HCl; (5) by the action of HCl upon the product obtained by the reduction of citrate of silver in hydrogen (Note 19), and (6) by the action of milk sugar upon AgNO_{3} together with soda and afterwards acidulating with HCl. All these reactions should lead to the formation of products of imperfect combination with the halogens and give photo-salts of a similar diversity of colour to those produced by the action of developers upon the halogen salts of silver after exposure to light.

The insolubility of the halogen compounds of silver forms the basis of many methods used in practical chemistry. Thus by means of this reaction it is possible to obtain salts of other acids from a halogen salt of a given metal, for instance, RCl_{2} + 2AgNO_{3} = R(NO_{3}){2} + 2AgCl. The formation of the halogen compounds of silver is very frequently used in the investigation of organic substances; for example, if any product of metalepsis containing iodine or chlorine be heated with a silver salt or silver oxide, the silver combines with the halogen and gives a halogen salt, whilst the elements previously combined with the silver replace the halogen. For instance, ethylene dibromide, C{2}H_{4}Br_{2}, is transformed into ethylene diacetate, C_{2}H_{4}(C_{2}H_{3}O_{2}){2}, and silver bromide by heating it with silver acetate, 2C{2}H_{3}O_{2}Ag. The insolubility of the halogen compounds of silver is still more frequently taken advantage of in determining the amount of silver and halogen in a given solution. If it is required, for instance, to determine the quantity of chlorine present in the form of a metallic chloride in a given solution, a solution of silver nitrate is added to it so long as it gives a precipitate. On shaking or stirring the liquid, the silver chloride easily settles in the form of heavy flakes. It is possible in this way to precipitate the whole of the chlorine from a solution, without adding an excess of silver nitrate, since it can be easily seen whether the addition of a fresh quantity of silver nitrate produces a precipitate in the clear liquid. In this manner it is possible to add to a solution containing chlorine, as much silver as is required for its entire precipitation, and to calculate the amount of chlorine previously in solution from the amount of the solution of silver nitrate consumed, if the quantity of silver nitrate in this solution has been previously determined.[25 bis] The atomic proportions and preliminary experiments with a pure salt--for example, with sodium chloride--will give the amount of chlorine from the quantity of silver nitrate. Details of these methods will be found in works on analytical chemistry.[25 tri]

[25 bis] In order to determine when the reaction is at an end, a few drops of a solution of K_{2}CrO_{4} are added to the solution of the chloride. Before all the chlorine is precipitated as AgCl, the precipitate (after shaking) is white (since Ag_{2}CrO_{4} with 2RCl gives 2AgCl); but when all the chlorine is thrown down Ag_{2}CrO_{4} is formed, which colours the precipitate reddish-brown. In order to obtain accurate results the liquid should be neutral to litmus.

[25 tri] Silver cyanide, AgCN, is closely analogous to the haloid salts of silver. It is obtained, in similar manner to silver chloride, by the addition of potassium cyanide to silver nitrate. A white precipitate is then formed, which is almost insoluble in boiling water. It is also, like silver chloride, insoluble in dilute acids. However, it is dissolved when heated with nitric acid, and both hydriodic and hydrochloric acids act on it, converting it into silver chloride and iodide. Alkalis, however, do not act on silver cyanide, although they act on the other haloid salts of silver. Ammonia and solutions of the cyanides of the alkali metals dissolve silver cyanide, as they do the chloride. In the latter case double cyanides are formed--for example, KAgC_{2}N_{2}. This salt is obtained in a crystalline state on evaporating a solution of silver cyanide in potassium cyanide. It is much more stable than silver cyanide itself. It has a neutral reaction, does not change in the air, and does not smell of hydrocyanic acid. Many acids, in acting on a solution of this double salt, precipitate the insoluble silver cyanide. Metallic silver dissolves in a solution of potassium cyanide in the presence of air, with formation of the same double salt and potassium hydroxide, and when silver chloride dissolves in potassium cyanide it forms potassium chloride, besides the salt KAgC_{2}N_{2}. This double salt of silver is used in silver plating. For this purpose potassium cyanide is added to its solution, as otherwise silver cyanide, and not metallic silver, is deposited by the electric current. If two electrodes--one positive (silver) and the other negative (copper)--be immersed in such a solution, silver will be deposited upon the latter, and the silver of the positive electrode will be dissolved by the liquid, which will thus preserve the same amount of metal in solution as it originally contained. If instead of the negative electrode a copper object be taken, well cleaned from all dirt, the silver will be deposited in an even coating; this, indeed, forms the mode of silver plating by the wet method, which is most often used in practice. A solution of one part of silver nitrate in 30 to 50 parts of water, and mixed with a sufficient quantity of a solution of potassium cyanide to redissolve the precipitate of silver cyanide formed, gives a dull coating of silver, but if twice as much water be used the same mixture gives a bright coating.

Silver plating in the wet way has now replaced to a considerable extent the old process of dry silvering, because this process, which consists in dissolving silver in mercury and applying the amalgam to the surface of the objects, and then vaporising the mercury, offers the great disadvantage of the poisonous mercury fumes. Besides these, there is another method of silver plating, based on the direct displacement of silver from its salts by other metals--for example, by copper. The copper reduces the silver from its compounds, and the silver separated is deposited upon the copper. Thus a solution of silver chloride in sodium thiosulphate deposits a coating of silver upon a strip of copper immersed in it. It is best for this purpose to take pure silver sulphite. This is prepared by mixing a solution of silver nitrate with an excess of ammonia, and adding a saturated solution of sodium sulphite and then alcohol, which precipitates silver sulphite from the solution. The latter and its solutions are very easily decomposed by copper. Metallic iron produces the same decomposition, and iron and steel articles may be very readily silver-plated by means of the thiosulphate solution of silver chloride. Indeed, copper and similar metals may even be silver-plated by means of silver chloride; if the chloride of silver, with a small amount of acid, be rubbed upon the surface of the copper, the latter becomes covered with a coating of silver, which it has reduced.

Silver plating is not only applicable to metallic objects, but also to glass, china, &c. Glass is silvered for various purposes--for example, glass globes silvered internally are used for ornamentation, and have a mirrored surface. Common looking-glass silvered upon one side forms a mirror which is better than the ordinary mercury mirrors, owing to the truer colours of the image due to the whiteness of the silver. For optical instruments--for example, telescopes--concave mirrors are now made of silvered glass, which has first been ground and polished into the required form. The silvering of glass is based on the fact that silver which is reduced from certain solutions deposits itself uniformly in a perfectly homogeneous and continuous but very thin layer, forming a bright reflecting surface. Certain organic substances have the property of reducing silver in this form. The best known among these are certain aldehydes--for instance, ordinary acetaldehyde, C_{2}H_{4}O, which easily oxidises in the air and forms acetic acid, C_{2}H_{4}O_{2}. This oxidation also easily takes place at the expense of silver oxide, when a certain amount of ammonia is added to the mixture. The oxide of silver gives up its oxygen to the aldehyde, and the silver reduced from it is deposited in a metallic state in a uniform bright coating. The same action is produced by certain saccharine substances and certain organic acids, such as tartaric acid, &c.

Accurate experiments, and more especially the researches of Stas at Brussels, show the proportion in which silver reacts with metallic chlorides. These researches have led to the determination of the combining weights of silver, sodium, potassium, chlorine, bromine, iodine, and other elements, and are distinguished for their model exactitude, and we will therefore describe them in some detail. As sodium chloride is the chloride most generally used for the precipitation of silver, since it can most easily be obtained in a pure state, we will here cite the quantitative observations made by Stas for showing the co-relation between the quantities of chloride of sodium and silver which react together. In order to obtain perfectly pure sodium chloride, he took pure rock salt, containing only a small quantity of magnesium and calcium compounds and a small amount of potassium salts. This salt was dissolved in water, and the saturated solution evaporated by boiling. The sodium chloride separated out during the boiling, and the mother liquor containing the impurities was poured off. Alcohol of 65 p.c. strength and platinic chloride were added to the resultant salt, in order to precipitate all the potassium and a certain part of the sodium salts. The resultant alcoholic solution, containing the sodium and platinum chlorides, was then mixed with a solution of pure ammonium chloride in order to remove the platinic chloride. After this precipitation, the solution was evaporated in a platinum retort, and then separate portions of this purified sodium chloride were collected as they crystallised. The same salt was prepared from sodium sulphate, tartrate, nitrate, and from the platinochloride, in order to have sodium chloride prepared by different methods and from different sources, and in this manner ten samples of sodium chloride thus prepared were purified and investigated in their relation to silver. After being dried, weighed quantities of all ten samples of sodium chloride were dissolved in water and mixed with a solution in nitric acid of a weighed quantity of perfectly pure silver. A slightly greater quantity of silver was taken than would be required for the decomposition of the sodium chloride, and when, after pouring in all the silver solution, the silver chloride had settled, the amount of silver remaining in excess was determined by means of a solution of sodium chloride of known strength. This solution of sodium chloride was added so long as it formed a precipitate. In this manner Stas determined how many parts of sodium chloride correspond to 100 parts by weight of silver. The result of ten determinations was that for the entire precipitation of 100 parts of silver, from 54·2060 to 54·2093 parts of sodium chloride were required. The difference is so inconsiderable that it has no perceptible influence on the subsequent calculations. The mean of ten experiments was that 100 parts of silver react with 54·2078 parts of sodium chloride. In order to learn from this the relation between the chlorine and silver, it was necessary to determine the quantity of chlorine contained in 54·2078 parts of sodium chloride, or, what is the same thing, the quantity of chlorine which combines with 100 parts of silver. For this purpose Stas made a series of observations on the quantity of silver chloride obtained from 100 parts of silver. Four syntheses were made by him for this purpose. The first synthesis consisted in the formation of silver chloride by the action of chlorine on silver at a red heat. This experiment showed that 100 parts of silver give 132·841, 132·843 and 132·843 of silver chloride. The second method consisted in dissolving a given quantity of silver in nitric acid and precipitating it by means of gaseous hydrochloric acid passed over the surface of the liquid; the resultant mass was evaporated in the dark to drive off the nitric acid and excess of hydrochloric acid, and the remaining silver chloride was fused first in an atmosphere of hydrochloric acid gas and then in air. In this process the silver chloride was not washed, and therefore there could be no loss from solution. Two experiments made by this method showed that 100 parts of silver give 132·849 and 132·846 parts of silver chloride. A third series of determinations was also made by precipitating a solution of silver nitrate with a certain excess of gaseous hydrochloric acid. The amount of silver chloride obtained was altogether 132·848. Lastly, a fourth determination was made by precipitating dissolved silver with a solution of ammonium chloride, when it was found that a considerable amount of silver (0·3175) had passed into solution in the washing; for 100 parts of silver there was obtained altogether 132·8417 of silver chloride. Thus from the mean of seven determinations it appears that 100 parts of silver give 132·8445 parts of silver chloride--that is, that 32·8445 parts of chlorine are able to combine with 100 parts of silver and with that quantity of sodium which is contained in 54·2078 parts of sodium chloride. These observations show that 32·8445 parts of chlorine combine with 100 parts of silver and with 21·3633 parts of sodium. From these figures expressing the relation between the combining weights of chlorine, silver, and sodium, it would be possible to determine their atomic weights--that is, the combining quantity of these elements with respect to one part by weight of hydrogen or 16 parts of oxygen, if there existed a series of similarly accurate determinations for the reactions between hydrogen or oxygen and one of these elements--chlorine, sodium, or silver. If we determine the quantity of silver chloride which is obtained from silver chlorate, AgClO_{3}, we shall know the relation between the combining weights of silver chloride and oxygen, so that, taking the quantity of oxygen as a constant magnitude, we can learn from this reaction the combining weight of silver chloride, and from the preceding numbers the combining weights of chlorine and silver. For this purpose it was first necessary to obtain pure silver chlorate. This Stas did by acting on silver oxide or carbonate, suspended in water, with gaseous chlorine.[26]

[26] The phenomenon which then takes place is described by Stas as follows, in a manner which is perfect in its clearness and accuracy: if silver oxide or carbonate be suspended in water, and an excess of water saturated with chlorine be added, all the silver is converted into chloride, just as is the case with oxide or carbonate of mercury, and the water then contains, besides the excess of chlorine, only pure hypochlorous acid without the least trace of chloric or chlorous acid. If a stream of chlorine be passed into water containing an excess of silver oxide or silver carbonate while the liquid is continually agitated, the reaction is the same as the preceding; silver chloride and hypochlorous acid are formed. But this acid does not long remain in a free state: it gradually acts on the silver oxide and gives silver hypochlorite, i.e. AgClO. If, after some time, the current of chlorine be stopped but the shaking continued, the liquid loses its characteristic odour of hypochlorous acid, while preserving its energetic decolorising property, because the silver hypochlorite which is formed is easily soluble in water. In the presence of an excess of silver oxide this salt can be kept for several days without decomposition, but it is exceedingly unstable when no excess of silver oxide or carbonate is present. So long as the solution of silver hypochlorite is shaken up with the silver oxide, it preserves its transparency and bleaching property, but directly it is allowed to stand, and the silver oxide settles, it becomes rapidly cloudy and deposits large flakes of silver chloride, so that the black silver oxide which had settled becomes covered with the white precipitate. The liquid then loses its bleaching properties and contains silver chlorate, i.e. AgClO_{3}, in solution, which has a slightly alkaline reaction, owing to the presence of a small amount of dissolved oxide. In this manner the reactions which are consecutively accomplished may be expressed by the equations:

6Cl_{2} + 3Ag_{2}O + 3H_{2}O = 6AgCl + 6HClO; 6HClO + 3Ag_{2}O = 3H_{2}O + 6AgClO; 6AgClO = 4AgCl + 2AgClO_{3}.

Hence, Stas gives the following method for the preparation of silver chlorate: A slow current of chlorine is caused to act on oxide of silver, suspended in water which is kept in a state of continual agitation. The shaking is continued after the supply of chlorine has been stopped, in order that the free hypochlorous acid should pass into silver hypochlorite, and the resultant solution of the hypochlorite is drawn off from the sediment of the excess of silver oxide. This solution decomposes spontaneously into silver chloride and chlorate. The pure silver chlorate, AgClO_{3}, does not change under the action of light. The salt is prepared for further use by drying it in dry air at 150°. It is necessary during drying to prevent the access of any organic matter; this is done by filtering the air through cotton wool, and passing it over a layer of red-hot copper oxide.

The decomposition of the silver chlorate thus obtained was accomplished by the action of a solution of sulphurous anhydride on it. The salt was first fused by carefully heating it at 243°. The solution of sulphurous anhydride used was one saturated at 0°. Sulphurous anhydride in dilute solutions is oxidised at the expense of silver chlorate, even at low temperatures, with great ease if the liquid be continually shaken, sulphuric acid and silver chloride being formed: AgClO_{3} + 3SO_{2} + 3H_{2}O = AgCl + 3H_{2}SO_{4}. After decomposition, the resultant liquid was evaporated, and the residue of silver chloride weighed. Thus the process consisted in taking a known weight of silver chlorate, converting it into silver chloride, and determining the weight of the latter. The analysis conducted in this manner gave the following results, which, like the preceding, designate the weight in a vacuum calculated from the weights obtained in air: In the first experiment it appeared that 138·7890 grams of silver chlorate gave 103·9795 parts of silver chloride, and in the second experiment that 259·5287 grains of chlorate gave 194·44515 grams of silver chloride, and after fusion 194·4435 grams. The mean result of both experiments, converted into percentages, shows that 100 parts of silver chlorate contain 74·9205 of silver chloride and 25·0795 parts of oxygen. From this it is possible to calculate the combining weight of silver chloride, because in the decomposition of silver chlorate there are obtained three atoms of oxygen and one molecule of silver chloride: AgClO_{3} = AgCl + 3O. Taking the weight of an atom of oxygen to be 16, we find from the mean result that the equivalent weight of silver chloride is equal to 143·395. Thus if O = 16, AgCl = 143·395, and as the preceding experiments show that silver chloride contains 32·8445 parts of chlorine per 100 parts of silver, the weight of the atom of silver[26 bis] must be 107·94 and that of chlorine 35·45. The weight of the atom of sodium is determined from the fact that 21·3633 parts of sodium chloride combine with 32·8445 parts of chlorine; consequently Na = 23·05. This conclusion, arrived at by the analysis of silver chlorate, was verified by means of the analysis of potassium chlorate by decomposing it by heat and determining the weight of the potassium chloride formed, and also by effecting the same decomposition by igniting the chlorate in a stream of hydrochloric acid. The combining weight of potassium chloride was thus determined, and another series of determinations confirmed the relation between chlorine, potassium, and silver, in the same manner as the relation between sodium, chlorine, and silver was determined above. Consequently, the combining weights of sodium, chlorine, and potassium could be deduced by combining these data with the analysis of silver chlorate and the synthesis of silver chloride. The agreement between the results showed that the determinations made by the last method were perfectly correct, and did not depend in any considerable degree on the methods which were employed in the preceding determinations, as the combining weights of chlorine and silver obtained were the same as before. There was naturally a difference, but so small a one that it undoubtedly depended on the errors incidental to every process of weighing and experiment. The atomic weight of silver was also determined by Stas by means of the synthesis of silver sulphide and the analysis of silver sulphate. The combining weight obtained by this method was 107·920. The synthesis of silver iodide and the analysis of silver iodate gave the figure 107·928. The synthesis of silver bromide with the analysis of silver bromate gave the figure 107·921. The synthesis of silver chloride and the analysis of silver chlorate gave a mean result of 107·937. Hence there is no doubt that the combining weight of silver is at least as much as 107·9--greater than 107·90 and less than 107·95, and probably equal to the mean = 107·92. Stas determined the combining weights of many other elements in this manner, such as lithium, potassium, sodium, bromine, chlorine, iodine, and also nitrogen, for the determination of the amount of silver nitrate obtained from a given amount of silver gives directly the combining weight of nitrogen. Taking that of oxygen as 16, he obtained the following combining weights for these elements: nitrogen 14·04, silver 107·93, chlorine 35·46, bromine 79·95, iodine 126·85, lithium 7·02, sodium 23·04, potassium 39·15. These figures differ slightly from those which are usually employed in chemical investigations. They must be regarded as the result of the best observations, whilst the figures usually used in practical chemistry are only approximate--are, so to speak, round numbers for the atomic weights which differ so little from the exact figures (for instance, for Ag 108 instead of 107·92, for Na 23 instead of 23·04) that in ordinary determinations and calculations the difference falls within the limits of experimental error inseparable from such determinations.

[26 bis] The results given by Stas' determinations have recently been recalculated and certain corrections have been introduced. We give in the context the average results of van der Plaats and Thomsen's calculations, as well as in Table III. neglecting the doubtful thousandths.

The exhaustive investigations conducted by Stas on the atomic weights of the above-named elements have great significance in the solution of the problem as to whether the atomic weights of the elements can be expressed in whole numbers if the unit taken be the atomic weight of hydrogen. Prout, at the beginning of this century, stated that this was the case, and held that the atomic weights of the elements are multiples of the atomic weight of hydrogen. The subsequent determinations of Berzelius, Penny, Marchand, Marignac, Dumas, and more especially of Stas, proved this conclusion to be untenable; since a whole series of elements proved to have fractional atomic weights--for example, chlorine, about 35·5. On account of this, Marignac and Dumas stated that the atomic weights of the elements are expressed in relation to hydrogen, either by whole numbers or by numbers with simple fractions of the magnitudes 1/2 and 1/4. But Stas's researches refute this supposition also. Even between the combining weight of hydrogen and oxygen, there is not, so far as is yet known, that simple relation which is required by Prout's hypothesis,[27] i.e., taking O = 16, the atomic weight of hydrogen is equal not to 1 but to a greater number somewhere between 1·002 and 1·008 or mean 1·005. Such a conclusion arrived at by direct experiment cannot but be regarded as having greater weight than Prout's supposition (hypothesis) that the atomic weights of the elements are in multiple proportion to each other, which would give reason for surmising (but not asserting) a complexity of nature in the elements, and their common origin from a single primary material, and for expecting their mutual conversion into each other. All such ideas and hopes must now, thanks more especially to Stas, be placed in a region void of any experimental support whatever, and therefore not subject to the discipline of the positive data of science.

[27] This hypothesis, for the establishment or refutation of which so many researches have been made, is exceedingly important, and fully deserves the attention which has been given to it. Indeed, if it appeared that the atomic weights of all the elements could be expressed in whole numbers with reference to hydrogen, or if they at least proved to be commensurable with one another, then it could be affirmed with confidence that the elements, with all their diversity, were formed of one material condensed or grouped in various manners into the stable, and, under known conditions, undecomposable groups which we call the atoms of the elements. At first it was supposed that all the elements were nothing else but condensed hydrogen, but when it appeared that the atomic weights of the elements could not be expressed in whole numbers in relation to hydrogen, it was still possible to imagine the existence of a certain material from which both hydrogen and all the other elements were formed. If it should transpire that four atoms of this material form an atom of hydrogen, then the atom of chlorine would present itself as consisting of 142 atoms of this substance, the weight of whose atom would be equal to 0·25. But in this case the atoms of all the elements should be expressed in whole numbers with respect to the weight of the atom of this original material. Let us suppose that the atomic weight of this material is equal to unity, then all the atomic weights should be expressible in whole numbers relatively to this unit. Thus the atom of one element, let us suppose, would weigh m, and of another n, but, as both m and n must be whole numbers, it follows that the atomic weights of all the elements would be commensurable. But it is sufficient to glance over the results obtained by Stas, and to be assured of their accuracy, especially for silver, in order to entirely destroy, or at least strongly undermine, this attractive hypothesis. We must therefore refuse our assent to the doctrine of the building up from a single substance of the elements known to us. This hypothesis is not supported either by any known transformation (for one element has never been converted into another element), or by the commensurability of the atomic weights of the elements. Although the hypothesis of the formation of all the elements from a single substance (for which Crookes has suggested the name protyle) is most attractive in its comprehensiveness, it can neither be denied nor accepted for want of sufficient data. Marignac endeavoured, however, to overcome Stas's conclusions as to the incommensurability of the atomic weights by supposing that in his, as in the determinations of all other observers, there were unperceived errors which were quite independent of the mode of observation--for example, silver nitrate might be supposed to be an unstable substance which changes, under the heatings, evaporations, and other processes to which it is subjected in the reactions for the determination of the combining weight of silver. It might be supposed, for instance, that silver nitrate contains some impurity which cannot be removed by any means; it might also be supposed that a portion of the elements of the nitric acid are disengaged in the evaporation of the solution of silver nitrate (owing to the decomposing action of water), and in its fusion, and that we have not to deal with normal silver nitrate, but with a slightly basic salt, or perhaps an excess of nitric acid which cannot be removed from the salt. In this case the observed combining weight will not refer to an actually definite chemical compound, but to some mixture for which there does not exist any perfectly exact combining relations. Marignac upholds this proposition by the fact that the conclusions of Stas and other observers respecting the combining weights determined with the greatest exactitude very nearly agree with the proposition of the commensurability of the atomic weights--for example, the combining weight of silver was shown to be equal to 107·93, so that it only differs by 0·08 from the whole number 108, which is generally accepted for silver. The combining weight of iodine proved to be equal to 126·85--that is, it differs from 127 by 0·15. The combining weights of sodium, nitrogen, bromine, chlorine, and lithium are still nearer to the whole or round numbers which are generally accepted. But Marignac's proposition will hardly bear criticism. Indeed if we express the combining weights of the elements determined by Stas in relation to hydrogen, the approximation of these weights to whole numbers disappears, because one part of hydrogen in reality does not combine with 16 parts of oxygen, but with 15·92 parts, and therefore we shall obtain, taking H = 1, not the above-cited figures, but for silver 107·38, for bromine 79·55, magnitudes which are still further removed from whole numbers. Besides which, if Marignac's proposition were true the combining weight of silver determined by one method--e.g. by the analysis of silver chlorate combined with the synthesis of silver chloride--would not agree well with the combining weight determined by another method--e.g. by means of the analysis of silver iodate and the synthesis of silver iodide. If in one case a basic salt could be obtained, in the other case an acid salt might be obtained. Then the analysis of the acid salt would give different results from that of the basic salt. Thus Marignac's arguments cannot serve as a support for the vindication of Prout's hypothesis.

In conclusion, I think it will not be out of place to cite the following passage from a paper I read before the Chemical Society of London in 1889 (Appendix II.), referring to the hypothesis of the complexity of the elements recognised in chemistry, owing to the fact that many have endeavoured to apply the periodic law to the justification of this idea 'dating from a remote antiquity, when it was found convenient to admit the existence of many gods but only one matter.'

'When we try to explain the origin of the idea of a unique primary matter, we easily trace that, in the absence of deductions from experiment, it derives its origin from the scientifically philosophical attempt at discovering some kind of unity in the immense diversity of individualities which we see around. In classical times such a tendency could only be satisfied by conceptions about the immaterial world. As to the material world, our ancestors were compelled to resort to some hypothesis, and they adopted the idea of unity in the formative material, because they were not able to evolve the conception of any other possible unity in order to connect the multifarious relations of matter. Responding to the same legitimate scientific tendency, natural science has discovered throughout the universe a unity of plan, a unity of forces, and a unity of matter; and the convincing conclusions of modern science compel every one to admit these kinds of unity. But while we admit unity in many things, we none the less must also explain the individuality and the apparent diversity which we cannot fail to trace everywhere. It was said of old "Give us a fulcrum and it will become easy to displace the earth." So also we must say, "Give us something that is individualised, and the apparent diversity will be easily understood." Otherwise, how could unity result in a multitude.

'After a long and painstaking research, natural science has discovered the individualities of the chemical elements, and therefore it is now capable, not only of analysing, but also of synthesising; it can understand and grasp generality and unity, as well as the individualised and multifarious. The general and universal, like time and space, like force and motion, vary uniformly. The uniform admit of interpolations, revealing every intermediate phase; but the multitudinous, the individualised--such as ourselves, or the chemical elements, or the members of a peculiar periodic function of the elements, or Dalton's multiple proportions--is characterised in another way. We see in it--side by side with a general connecting principle--leaps, breaks of continuity, points which escape from the analysis of the infinitely small--an absence of complete intermediate links. Chemistry has found an answer to the question as to the causes of multitudes, and while retaining the conception of many elements, all submitted to the discipline of a general law, it offers an escape from the Indian Nirvana--the absorption in the universal--replacing it by the individualised. However, the place for individuality is so limited by the all-grasping, all-powerful universal, that it is merely a point of support for the understanding of multitude in unity.'

Among the platinum metals ruthenium, rhodium, and palladium, by their atomic weights and properties, approach silver, just as iron and its analogues (cobalt and nickel) approach copper in all respects. Gold stands in exactly the same position in relation to the heavy platinum metals, osmium, iridium, and platinum, as copper and silver do to the two preceding series. The atomic weight of gold is nearly equal to their atomic weights;[28] it is dense like these metals. It also gives various grades of oxidation, which are feeble, both in a basic and an acid sense. Whilst near to osmium, iridium, and platinum, gold at the same time is able, like copper and silver, to form compounds which answer to the type RX--that is, oxides of the composition R_{2}O. Cuprous chloride, CuCl, silver chloride, AgCl, and aurous chloride, AuCl, are substances which are very much alike in their physical and chemical properties.[28 bis] They are insoluble in water, but dissolve in hydrochloric acid and ammonia, in potassium cyanide, sodium thiosulphate, &c. Just as copper forms a link between the iron metals and zinc, and as silver unites the light platinum metals with cadmium, so also gold presents a transition from the heavy platinum metals to mercury. Copper gives saline compounds of the types CuX and CuX_{2}, silver of the type AgX, whilst gold, besides compounds of the type AuX, very easily and most frequently forms those of the type AuCl_{3}. The compounds of this type frequently pass into those of the lower type, just as PtX_{4} passes into PtX_{2}, and the same is observable in the elements which, in their atomic weights, follow gold. Mercury gives HgX_{2} and HgX, thallium gives TlX_{3} and TlX, lead gives PbX_{4} and PbX_{2}. On the other hand, gold in a qualitative respect differs from silver and copper in the extreme ease with which all its compounds are reduced to metal by many means. This is not only accomplished by many reducing agents, but also by the action of heat. Thus its chlorides and oxides lose their chlorine and oxygen when heated, and, if the temperature be sufficiently high, these elements are entirely expelled and metallic gold alone remains. Its compounds, therefore, act as oxidising agents.[29]

[28] It might be expected from the periodic law and analogies with the series iron, cobalt, nickel, copper, zinc, that the atomic weights of the elements of the series osmium, iridium, platinum, gold, mercury, would rise in this order, and at the time of the establishment of the periodic law (1869), the determinations of Berzelius, Rose, and others gave the following values for the atomic weights: Os = 200, Ir = 197, Pt = 198, Au = 196, Hg = 200. The fulfilment of the expectations of the periodic law was given in the first place by the fresh determinations (Seubert, Dittmar, and Arthur) of the atomic weight of platinum, which proved to be nearly 196, if O = 16 (as Marignac, Brauner, and others propose); in the second place, by the fact that Seubert proved that the atomic weight of osmium is really less than that of platinum, and approximately Os = 191; and, in the third place, by the fact that after the researches of Krüss, Thorpe, and Laurie there was no doubt that the atomic weight of gold is greater than that of platinum--namely, nearly 197.

[28 bis] In Chapter XXII., Note 40, we gave the thermal data for certain of the compounds of copper of the type CuX_{2}; we will now cite certain data for the cuprous compounds of the type CuX, which present an analogy to the corresponding compounds AgX and AuX, some of which were investigated by Thomsen in his classical work, 'Thermochemische Untersuchungen' (Vol. iii., 1883). The data are given in the same manner as in the above-mentioned note:

R = Cu Ag Au R + Cl +33 +29 +6 R + Br +25 +23 0 R + I +16 +14 -6 R + O +41 + 6 -?

Thus we see in the first place that gold, which possesses a much smaller affinity than Ag, evolves far less heat than an equivalent amount of copper, giving the same compound, and in the second place that the combination of copper with one atom of oxygen disengages more heat than its combination with one atom of a halogen, whilst with silver the reverse is the case. This is connected with the fact that Cu_{2}O is more stable under the action of heat than Ag_{2}O.

[29] Heavy atoms and molecules, although they may present many points of analogy, are more easily isolated; thus C_{16}H_{32}, although, like C_{2}H_{4}, it combines with Br_{2}, and has a similar composition, yet reacts with much greater difficulty than C_{2}H_{4}, and in this it resembles gold; the heavy atoms and molecules are, so to say, inert, and already saturated by themselves. Gold in its higher grade of oxidation, Au_{2}O_{3}, presents feeble basic properties and weakly-developed acid properties, so that this oxide of gold, Au_{2}O_{3}, may be referred to the class of feeble acid oxides, like platinic oxide. This is not the case in the highest known oxides of copper and silver. But in the lower grade of oxidation, aurous oxide, Au_{2}O, gold, like silver and copper, presents basic properties, although they are not very pronounced. In this respect it stands very close in its properties, although not in its types of combination (AuX and AuX_{3}), to platinum (PtX_{2} and PtX_{4}) and its analogues.

As yet the general chemical characteristics of gold and its compounds have not been fully investigated. This is partly due to the fact that very few researches have been undertaken on the compounds of this metal, owing to its inaccessibility for working in large quantities. As the atomic weight of gold is high (Au = 197), the preparation of its compounds requires that it should be taken in large quantities, which forms an obstacle to its being fully studied. Hence the facts concerning the history of this metal are rarely distinguished by that exactitude with which many facts have been established concerning other elements more accessible, and long known in use.

In nature gold occurs in the primary and chiefly in quartzose rocks, and especially in quartz veins, as in the Urals (at Berezoffsk), in Australia, and in California. The native gold is extracted from these rocks by subjecting them to a mechanical treatment consisting of crushing and washing.[29 bis] Nature has already accomplished a similar disintegration of the hard rocky matter containing gold.[30] These disintegrated rocks, washed by rain and other water, have formed gold-bearing deposits, which are known as alluvial gold deposits. Gold-bearing soil is sometimes met with on the surface and sometimes under the upper soil, but more frequently along the banks of dried-up water-courses and running streams. The sand of many rivers contains, however, a very small amount of gold, which it is not profitable to work; for example, that of the Alpine rivers contains 5 parts of gold in 10,000,000 parts of sand. The richest gold deposits are those of Siberia, especially in the southern parts of the Government of Yeniseisk, the South Urals, Mexico, California, South Africa, and Australia, and then the comparatively poorer alluvial deposits of many countries (Hungary, the Alps, and Spain in Europe). The extraction of the gold from alluvial deposits is based on the principle of levigation; the earth is washed, while constantly agitated, by a stream of water, which carries away the lighter portion of the earth, and leaves the coarser particles of the rock and heavier particles of the gold, together with certain substances which accompany it, in the washing apparatus. The extraction of this washed gold only necessitates mechanical appliances,[31] and it is not therefore surprising that gold was known to savages and in the most remote period of history. It sometimes occurs in crystals belonging to the regular system, but in the majority of cases in nuggets or grains of greater or less magnitude. It always contains silver (from very small quantities up to 30 p.c., when it is called 'electrum') and certain other metals, among which lead and rhodium are sometimes found.

[29 bis] Sonstadt (1872) showed that sea water, besides silver, always contains gold. Munster (1892) showed that the water of the Norwegian fiords contains about 5 milligrams of gold per ton (or 5 milliardths)--i.e. a quantity deserving practical attention, and I think it may be already said that, considering the immeasurable amount of sea water, in time means will be discovered for profitably extracting gold from sea water by bringing it into contact with substances capable of depositing gold upon their surface. The first efforts might be made upon the extraction of salt from sea water, and as the total amount of sea water may be taken as about 2,000,000,000,000,000,000 tons, it follows that it contains about 10,000 million tons of gold. The yearly production of gold is about 200 tons for the whole world, of which about one quarter is extracted in Russia. It is supposed that gold is dissolved in sea water owing to the presence of iodides, which, under the action of animal organisms, yield free iodine. It is thought (as Professor Konovaloff mentions in his work upon 'The Industries of the United States,' 1894) that iodine facilitates the solution of the gold, and the organic matter its precipitation. These facts and considerations to a certain extent explain the distribution of gold in veins or rock fissures, chiefly filled with quartz, because there is sufficient reason for supposing that these rocks once formed the ocean bottom. R. Dentrie, and subsequently Wilkinson, showed that organic matter--for instance, cork--and pyrites are able to precipitate gold from its solutions in that metallic form and state in which it occurs in quartz veins, where (especially in the deeper parts of vein deposits) gold is frequently found on the surface of pyrites, chiefly arsenical pyrites. Kazantseff (in Ekaterinburg, 1891) even supposes, from the distribution of the gold in these pyrites, that it occurred in solution as a compound of sulphide of gold and sulphide of arsenic when it penetrated into the veins. It is from such considerations that the origin of vein and pyritic gold is, at the present time, attributed to the reaction of solutions of this metal, the remains of which are seen in the gold still present in sea water.

[30] However, in recent times, especially since about 1870, when chlorine (either as a solution of the gas or as bleaching powder) and bromine began to be applied to the extraction of finely-divided gold from poor ores (previously roasted in order to drive off arsenic and sulphur, and oxidise the iron), the extraction of gold from quartz and pyrites, by the wet method, increases from year to year, and begins to equal the amount extracted from alluvial deposits. Since the nineties the cyanide process (Chapter XIII., Note 13 bis) has taken an important place among the wet methods for extracting gold from its ores. It consists in pouring a dilute solution of cyanide of potassium (about 500 parts of water and 1 to 4 parts of cyanide of potassium per 1,000 parts of ore, the amount of cyanide depending upon the richness of the ore) and a mixture of it with NaCN, (see Chapter XIII., Note 12) over the crushed ore (which need not be roasted, whilst roasting is indispensable in the chlorination process, as otherwise the chlorine is used up in oxidising the sulphur, arsenic, &c.) The gold is dissolved very rapidly even from pyrites, where it generally occurs on the surface in such fine and adherent particles that it either cannot be mechanically washed away, or, more frequently is carried away by the stream of water, and cannot be caught by mechanical means or by the mercury used for catching the gold in the sluices. Chlorination had already given the possibility of extracting the finest particles of gold; but the cyanide process enables such pyrites to be treated as could be scarcely worked by other means. The treatment of the crushed ore by the KCN is carried on in simple wooden vats (coated with paraffin or tar) with the greatest possible rapidity (in order that the KCN solution should not have time to change) by a method of systematic lixiviation, and is completed in 10 to 12 hours. The resultant solution of gold, containing AuK(CN){2}, is decomposed either with freshly-made zinc filings (but when the gold settles on the Zn, the cyanide solution reacts upon the Zn with the evolution of H{2} and formation of ZnH_{2}O_{2}) or by sodium amalgam prepared at the moment of reaction by the action of an electric current upon a solution of NaHO poured into a vessel partially immersed in mercury (the NaCN is renewed continually by this means). The silver in the ore passes into solution, together with the gold, as in amalgamation.

[31] But the particles of gold are sometimes so small that a large amount is lost during the washing. It is then profitable to have recourse to the extraction by chlorine and KCN (Note 30).

In speaking of the extraction of gold the following remarks may not be out of place:

In California advantage is taken of water supplied from high altitudes in order to have a powerful head of water, with which the rocks are directly washed away, thus avoiding the greater portion of the mechanical labour required for the exploitation of these deposits.

The last residues of gold are sometimes extracted from sand by washing them with mercury, which dissolves the gold. The sand mixed with water is caused to come into contact with mercury during the washing. The mercury is then distilled.

Many sulphurous ores, even pyrites, contain a small amount of gold. Compounds of gold with bismuth, BiAu_{2}, tellurium, AuTe_{2} (calverite), &c., have been found, although rarely.

Among the minerals which accompany gold, and from which the presence of gold may be expected, we may mention white quartz, titanic and magnetic iron ores, and also the following, which are of rarer occurrence: zircon, topaz, garnet, and such like. The concentrated gold washings first undergo a mechanical treatment, and the impure gold obtained is treated for pure gold by various methods. If the gold contain a considerable amount of foreign metals, especially lead and copper, it is sometimes cupelled, like silver, so that the oxidisable metals may be absorbed by the cupel in the form of oxides, but in every case the gold is obtained together with silver, because the latter metal also is not oxidised. Sometimes the gold is extracted by means of mercury, that is, by amalgamation (and the mercury subsequently driven off by distillation), or by smelting it with lead (which is afterwards removed by oxidation) and processes like those employed for the extraction of silver, because gold, like silver, does not oxidise, is dissolved by lead and mercury, and is non-volatile. If copper or any other metal contain gold and it be employed as an anode, pure copper will be deposited upon the cathode, while all the gold will remain at the anode as a slime. This method often amply repays the whole cost of the process, since it gives, besides the gold, a pure electrolytic copper.

The separation of the silver from gold is generally carried on with great precision, as the presence of the silver in the gold does not increase its value for exchange, and it can be substituted by other less valuable metals, so that the extraction of the silver, as a precious metal, from its alloy with gold, is a profitable operation. This separation is conducted by different methods. Sometimes the argentiferous gold is melted in crucibles, together with a mixture of common salt and powdered bricks. The greater portion of the silver is thus converted into the chloride, which fuses and is absorbed by the slags, from which it may be extracted by the usual methods. The silver is also extracted from gold by treating it with boiling sulphuric acid, which does not act on the gold but dissolves the silver. But if the alloy does not contain a large proportion of silver it cannot be extracted by this method or at all events the separation will be imperfect, and therefore a fresh amount of silver is added (by fusion) to the gold, in such quantity that the alloy contains twice as much silver as gold. The silver which is added is preferably such as contains gold, which is very frequently the case. The alloy thus formed is poured in a thin stream into water, by which means it is obtained in a granulated form; it is then boiled with strong sulphuric acid, three parts of acid being used to one part of alloy. The sulphuric acid extracts all the silver without acting on the gold. It is best, however, to pour off the first portion of the acid, which has dissolved the silver, and then treat the residue of still imperfectly pure gold with a fresh quantity of sulphuric acid. The gold is thus obtained in the form of powder, which is washed with water until it is quite free from silver. The silver is precipitated from the solution by means of copper, so that cupric sulphate and metallic silver are obtained. This process is carried out in many countries, as in Russia, at the Government mints.

Gold is generally used alloyed with copper; since pure gold, like pure silver, is very soft, and therefore soon worn away. In assaying or determining the amount of pure gold in such an alloy it is usual to add silver to the gold in order to make up an alloy containing three parts of silver to one of gold (this is known as quartation because the alloy contains 1/4 of gold), and the resultant alloy is treated with nitric acid. If the silver be not in excess over the gold, it is not all dissolved by the nitric acid, and this is the reason for the quartation. The amount of pure gold (assay) is determined by weighing the gold which remains after this treatment. English gold (= 22 carats) coinage is composed of an alloy containing 91·66 p.c. of gold, but for many articles gold is frequently used containing a larger amount of foreign metals.

Pure gold may be obtained from gold alloys by dissolving in aqua regia, and then adding ferrous sulphate to the solution or heating it with a solution of oxalic acid. These deoxidising agents reduce the gold, but not the other metals. The chlorine combined with the gold then acts like free chlorine. The gold, thus reduced, is precipitated as an exceedingly fine brown powder.[31 bis] It is then washed with water, and fused with nitre or borax. Pure gold reflects a yellow light, and in the form of very thin sheets (gold leaf), into which it can be hammered and rolled,[31 tri] it transmits a bluish-green light. The specific gravity of gold is about 19·5, the sp. gr. of gold coin is about 17·1. It fuses at 1090°--at a higher temperature than silver--and can be drawn into exceedingly fine wires or hammered into thin sheets. With its softness and ductility, gold is distinguished for its tenacity, and a gold wire two millimetres thick breaks only under a load of 68 kilograms. Gold vaporises even at a furnace heat, and imparts a greenish colour to a flame passing over it in a furnace. Gold alloys with copper almost without changing its volume.[32] In its chemical aspect, gold presents, as is already seen from its general characteristics given above, an example of the so-called noble metals--i.e. it is incapable of being oxidised at any temperature, and its oxide is decomposed when calcined. Only chlorine and bromine combine directly with it at the ordinary temperature, but many other metals and non-metals combine with it at a red heat--for example, sulphur, phosphorus, and arsenic. Mercury dissolves it with great ease. It dissolves in potassium cyanide in the presence of air; a mixture of sulphuric acid with nitric acid dissolves it with the aid of heat, although in small quantity. It is also soluble in aqua regia and in selenic acid. Sulphuric, hydrochloric, nitric, and hydrofluoric acids and the caustic alkalis do not act on gold, but a mixture of hydrochloric acid with such oxidising agents as evolve chlorine naturally dissolves it like aqua regia.[32 bis]

[31 bis] Schottländer (1893) obtained gold in a soluble colloid form (the solution is violet) by the action of a mixture of solutions of cerium acetate and NaHO upon a solution of AuCl_{3}. The gold separates out from such a solution in exactly the same manner as Ag does from the solution of colloid silver mentioned above. There always remains a certain amount of a higher oxide of cerium, CeO_{2}, in the solution--i.e. the gold is reduced by converting the cerium into a higher grade of oxidation. Besides which Krüss and Hofmann showed that sulphide of gold precipitated by the action of H_{2}S upon a solution of AuKCy_{2} mixed with HCl easily passes into a colloid solution after being properly washed (like As_{2}S_{3}, CuS, &c., Chapter I., Note 57).

[31 tri] Gold-leaf is used for gilding wood (leather, cardboard, and suchlike, upon which it is glued by means of varnish, &c.), and is about 0·003 millimetre thick. It is obtained from thin sheets (weighing at first about 1/4 grm. to a square inch), rolled between gold rollers, by gradually hammering them (in packets of a number at once) between sheets of moist (but not wet) parchment, and then, after cutting them into four pieces, between a specially prepared membrane, which, when at the right degree of moisture, does not tear or stick together under the blows of the hammer.

[32] The formation of the alloys Cu + Zn, Cu + Sn, Cu + Bi, Cu + Sb, Pb + Sb, Ag + Pb, Ag + Sn, Au + Zn, Au + Sn, &c., is accompanied by a contraction (and evolution of heat). The formation of the alloys Fe + Sb, Fe + Pb, Cu + Pb, Pb + Sn, Pb + Sb, Zn + Sb, Ag + Cu, Au + Cu, Au + Pb, takes place with a certain increase in volume. With regard to the alloys of gold, it may be mentioned that gold is only slightly dissolved by mercury (about 0·06 p.c., Dudley, 1890); the remaining portion forms a granular alloy, whose composition has not been definitely determined. Aluminium (and silicon) also have the capacity of forming alloys with gold. The presence of a small amount of aluminium lowers the melting point of gold considerably (Roberts-Austen, 1892); thus the addition of 4 p.c. of aluminium lowers it by 14°·28, the addition of 10 p.c. Al by 41°·7. The latter alloy is white. The alloy AuAl_{2} has a characteristic purple colour, and its melting point is 32°·5 above that of gold, which shows it to be a definite compound of the two metals. The melting points of alloys richer in Al gradually fall to 660°--that is, below that of aluminium (665°).

Heycock and Neville (1892), in studying the triple alloys of Au, Cd, and Sn, observed a tendency in the gold to give compounds with Cd, and by sealing a mixture of Au and Cd in a tube, from which the air had been exhausted, and heating it, they obtained a grey crystalline brittle definite alloy AuCd.

[32 bis] Calderon (1892), at the request of some jewellers, investigated the cause of a peculiar alteration sometimes found on the surface of dead-gold articles, there appearing brownish and blackish spots, which widen and alter their form in course of time. He came to the conclusion that these spots are due to the appearance and development of peculiar micro-organisms (Aspergillus niger and Micrococcus cimbareus) on the gold, spores of which were found in abundance on the cotton-wool in which the gold articles had been kept.

As regards the compounds of gold, they belong, as was said above, to the types AuX_{3} and AuX. Auric chloride or gold trichloride, AuCl_{3}, which is formed when gold is dissolved in aqua regia, belongs to the former and higher of these types. The solution of this substance in water has a yellow colour, and it may be obtained pure by evaporating the solution in aqua regia to dryness, but not to the point of decomposition. If the evaporation proceed to the point of crystallisation, a compound of gold chloride and hydrochloric acid, AuHCl_{4}, is obtained, like the allied compounds of platinum; but it easily parts with the acid and leaves auric chloride, which fuses into a red-brown liquid, and then solidifies to a crystalline mass. If dry chlorine be passed over gold in powder it forms a mixture of aurous and auric chlorides, but the aurous chloride is also decomposed by water into gold and auric chloride. Auric chloride crystallises from its solutions as AuCl_{3},2H_{2}O, which easily loses water, and the dry chloride loses two-thirds of its chlorine at 185°, forming aurous chloride, whilst above 300° the latter chloride also loses its chlorine and leaves metallic gold. Auric chloride is the usual form in which gold occurs in solutions, and in which its salts are used in the arts and for chemical purposes. It is soluble in water, alcohol, and ether. Light has a reducing action on these solutions, and after a time metallic gold is deposited upon the sides of vessels containing the solution. Hydrogen when nascent, and even in a gaseous form, reduces gold from this solution to a metallic state. The reduction is more conveniently and usually effected by ferrous sulphate, and in general by the action of ferrous salts.[33]

[33] Stannous chloride as a reducing agent also acts on auric chloride, and gives a red precipitate known as purple of Cassius. This substance, which probably contains a mixture or compound of aurous oxide and tin oxide, is used as a red pigment for china and glass. Oxalic acid, on heating, reduces metallic gold from its salts, and this property may be taken advantage of for separating it from its solutions. The oxidation which then takes place in the presence of water may be expressed by the following equation: 2AuCl_{3} + 3C_{2}H_{2}O_{4} = 2Au + 6HCl + 6CO_{2}. Nearly all organic substances have a reducing action on gold, and solutions of gold leave a violet stain on the skin.

Auric chloride, like platinic chloride, is distinguished for its clearly-developed property of forming double salts. These double salts, as a rule, belong to the type AuMCl_{4}. The compound of auric chloride with hydrochloric acid mentioned above evidently belongs to the same type. The compounds 2KAuCl_{4},5H_{2}O, NaAuCl_{4},2H_{2}O, AuNH_{4}Cl_{4},H_{2}O, Mg(AuCl_{4}){2},2H{2}O, and the like are easily crystallised in well-formed crystals. Wells, Wheeler, and Penfield (1892) obtained RbAuCl_{4} (reddish yellow) and CsAuCl_{4} (golden yellow), and corresponding bromides (dark coloured). AuBr_{3} is extremely like the chloride. Auric cyanide is obtained easily in the form of a double salt of potassium, KAu(CN)_{4} by mixing saturated and hot solutions of potassium cyanide with auric chloride and then cooling.

If a solution of potassium hydroxide be added to a solution of auric chloride, a precipitate is first formed, which re-dissolves in an excess of the alkali. On being evaporated under the receiver of an air-pump, this solution yields yellow crystals, which present the same composition as the double salts AuMCl_{4}, with the substitution of the chlorine by oxygen--that is to say, potassium aurate, AuKO_{2}, is formed in crystals containing 3H_{2}O. The solution has a distinctly alkaline reaction. Auric oxide, Au_{2}O_{3}, separates when this alkaline solution is boiled with an excess of sulphuric acid. But it then still retains some alkali; however, it may be obtained in a pure state as a brown powder by dissolving in nitric acid and diluting with water. The brown powder decomposes below 250° into gold and oxygen. It is insoluble in water and in many acids, but it dissolves in alkalis, which shows the acid character of this oxide. An hydroxide, Au(OH)_{3} may be obtained as a brown powder by adding magnesium oxide to a solution of auric chloride and treating the resultant precipitate of magnesium aurate with nitric acid. This hydroxide loses water at 100°, and gives auric oxide.[34]

[34] If ammonia be added to a solution of auric chloride, it forms a yellow precipitate of the so-called fulminating gold, which contains gold, chlorine, hydrogen, nitrogen, and oxygen, but its formula is not known with certainty. It is probably a sort of ammonio-metallic compound, Au_{2}O_{3},4NH_{3}, or amide (like the mercury compound). This precipitate explodes at 140°, but when left in the presence of solutions containing ammonia it loses all its chlorine and becomes non-explosive. In this form the composition Au_{2}O_{3},2NH_{3},H_{2}O is ascribed to it, but this is uncertain. Auric sulphide, Au_{2}S_{3}, is obtained by the action of hydrogen sulphide on a solution of auric chloride, and also directly by fusing sulphur with gold. It has an acid character, and therefore dissolves in sodium and ammonium sulphides.

The starting-point of the compounds of the type AuX[35] is gold monochloride or aurous chloride, AuCl, which is formed, as mentioned above, by heating auric chloride at 185°. Aurous chloride forms a yellowish-white powder; this, when heated with water, is decomposed into metallic gold and auric chloride, which passes into solution: 3AuCl = AuCl_{3} + 2Au. This decomposition is accelerated by the action of light. Hence it is obvious that the compounds corresponding with aurous oxide are comparatively unstable. But this only refers to the simple compounds AuX; some of the complex compounds, on the contrary, form the most stable compounds of gold. Such, for example, is the cyanide of gold and potassium, AuK(CN){2}. It is formed, for instance, when finely-divided gold dissolves in the presence of air in a solution of potassium cyanide: 4KCN + 2Au + H{2}O + O = 2KAu(CN){2} + 2KHO (this reaction also proceeds with solid pieces of gold, although very slowly). The same compound is formed in solution when many compounds of gold are mixed with potassium cyanide, because if a higher compound of gold be taken, it is reduced by the potassium cyanide into aurous oxide, which dissolves in potassium cyanide and forms KAu(CN){2}. This substance is soluble in water, and gives a colourless solution, which can be kept for a long time, and is employed in electro-gilding--that is, for coating other metallic objects with a layer of gold, which is deposited if the object be connected with the negative pole of a battery and the positive pole consist of a gold plate. When an electric current is passed between them, the gold from the latter will dissolve, whilst a coating of gold from the solution will be deposited on the object.

[35] Many double salts of suboxide of gold belong to the type AuX--for instance, the cyanide corresponding to the type AuKX_{2}, like PtK_{2}X_{4}, with which we became acquainted in the last chapter. We will enumerate several of the representatives of this class of compounds. If auric chloride, AuCl_{3}, be mixed with a solution of sodium thiosulphate, the gold passes into a colourless solution, which deposits colourless crystals, containing a double thiosulphate of gold and sodium, which are easily soluble in water but are precipitated by alcohol. The composition of this salt is Na_{3}Au(S_{2}O_{3}){2},2H{2}O. If the sodium thiosulphate be represented as NaS_{2}O_{3}Na, the double salt in question will be AuNa(S_{2}O_{3}Na){2},2H{2}O, according to the type AuNaX_{2}. The solution of this colourless and easily crystallisable salt has a sweet taste, and the gold is not separated from it either by ferrous sulphate or oxalic acid. This salt, which is known as Fordos and Gelis's salt, is used in medicine and photography. In general, aurous oxide exhibits a distinct inclination to the formation of similar double salts, as we saw also with PtX_{2}--for example, it forms similar salts with sulphurous acid. Thus if a solution of sodium sulphite be gradually added to a solution of oxide of gold in sodium hydroxide, the precipitate at first formed re-dissolves to a colourless solution, which contains the double salt Na_{3}Au(SO_{3}){2} = AuNa(SO{3}Na)_{2}. The solution of this salt, when mixed with barium chloride, first forms a precipitate of barium sulphite, and then a red barium double salt which corresponds with the above sodium salt.

The oxygen compound of the type AuX, aurous oxide, Au_{2}O, is obtained as a greenish violet powder on mixing aurous chloride with potassium chloride in the cold. With hydrochloric acid this oxide gives gold and auric chloride, and when heated it easily splits up into oxygen and metallic gold.

APPENDIX I

AN ATTEMPT TO APPLY TO CHEMISTRY ONE OF THE PRINCIPLES OF NEWTON'S NATURAL PHILOSOPHY

BY PROFESSOR MENDELÉEFF

A LECTURE DELIVERED AT THE ROYAL INSTITUTION OF GREAT BRITAIN ON FRIDAY, MAY 31, 1889

Nature, inert to the eyes of the ancients, has been revealed to us as full of life and activity. The conviction that motion pervaded all things, which was first realised with respect to the stellar universe, has now extended to the unseen world of atoms. No sooner had the human understanding denied to the earth a fixed position and launched it along its path in space, than it was sought to fix immovably the sun and the stars. But astronomy has demonstrated that the sun moves with unswerving regularity through the star-set universe at the rate of about 50 kilometres per second. Among the so-called fixed stars are now discerned manifold changes and various orders of movement. Light, heat, electricity--like sound--have been proved to be modes of motion; to the realisation of this fact modern science is indebted for powers which have been used with such brilliant success, and which have been expounded so clearly at this lecture table by Faraday and by his successors. As, in the imagination of Dante, the invisible air became peopled with spiritual beings, so before the eyes of earnest investigators, and especially before those of Clerk Maxwell, the invisible mass of gases became peopled with particles: their rapid movements, their collisions, and impacts became so manifest that it seemed almost possible to count the impacts and determine many of the peculiarities or laws of their collisions. The fact of the existence of these invisible motions may at once be made apparent by demonstrating the difference in the rate of diffusion through porous bodies of the light and rapidly moving atoms of hydrogen and the heavier and more sluggish particles of air. Within the masses of liquid and of solid bodies we have been forced to acknowledge the existence of persistent though limited motion of their ultimate particles, for otherwise it would be impossible to explain, for example, the celebrated experiments of Graham on diffusion through liquid and colloidal substances. If there were, in our times, no belief in the molecular motion in solid bodies, could the famous Spring have hoped to attain any result by mixing carefully-dried powders of potash, saltpetre and sodium acetate, in order to produce, by pressure, a chemical reaction between these substances through the interchange of their metals, and have derived, for the conviction of the incredulous, a mixture of two hygroscopic though solid salts--sodium nitrate and potassium acetate?

In these invisible and apparently chaotic movements, reaching from the stars to the minutest atoms, there reigns, however, a harmonious order which is commonly mistaken for complete rest, but which is really a consequence of the conservation of that dynamic equilibrium which was first discerned by the genius of Newton, and which has been traced by his successors in the detailed analysis of the particular consequences of the great generalisation, namely, relative immovability in the midst of universal and active movement.

But the unseen world of chemical changes is closely analogous to the visible world of the heavenly bodies, since our atoms form distinct portions of an invisible world, as planets, satellites, and comets form distinct portions of the astronomer's universe; our atoms may therefore be compared to the solar systems, or to the systems of double or of single stars: for example, ammonia (NH_{3}) may be represented in the simplest manner by supposing the sun, nitrogen, surrounded by its planets of hydrogen; and common salt (NaCl) may be looked on as a double star formed of sodium and chlorine. Besides, now that the indestructibility of the elements has been acknowledged, chemical changes cannot otherwise be explained than as changes of motion, and the production by chemical reactions of galvanic currents, of light, of heat, of pressure, or of steam power, demonstrates visibly that the processes of chemical reaction are inevitably connected with enormous though unseen displacements, originating in the movements of atoms in molecules. Astronomers and natural philosophers, in studying the visible motions of the heavenly bodies and of matter on the earth, have understood and have estimated the value of this store of energy. But the chemist has had to pursue a contrary course. Observing in the physical and mechanical phenomena which accompany chemical reactions the quantity of energy manifested by the atoms and molecules, he is constrained to acknowledge that within the molecules there exist atoms in motion, endowed with an energy which, like matter itself, is neither being created nor capable of being destroyed. Therefore, in chemistry, we must seek dynamic equilibrium not only between the molecules, but also in their midst among their component atoms. Many conditions of such equilibrium have been determined, but much remains to be done, and it is not uncommon, even in these days, to find that some chemists forget that there is the possibility of motion in the interior of molecules, and therefore represent them as being in a condition of death-like inactivity.

Chemical combinations take place with so much ease and rapidity, possess so many special characteristics, and are so numerous, that their simplicity and order were for a long time hidden from investigators. Sympathy, relationship, all the caprices or all the fancifulness of human intercourse, seemed to have found complete analogies in chemical combinations, but with this difference, that the characteristics of the material substances--such as silver, for example, or of any other body--remain unchanged in every subdivision from the largest masses to the smallest particles, and consequently these characteristics must be properties of the particles. But the world of heavenly luminaries appeared equally fanciful at man's first acquaintance with it, so much so, that the astrologers imagined a connection between the individualities of men and the conjunctions of planets. Thanks to the genius of Lavoisier and of Dalton, man has been able, in the unseen world of chemical combinations, to recognise laws of the same simple order as those which Copernicus and Kepler proved to exist in the planetary universe. Man discovered, and continues every hour to discover, what remains unchanged in chemical evolution, and how changes take place in combinations of the unchangeable. He has learned to predict, not only what possible combinations may take place, but also the very existence of atoms of unknown elementary substances, and has besides succeeded in making innumerable practical applications of his knowledge to the great advantage of his race, and has accomplished this notwithstanding that notions of sympathy and affinity still preserve a strong vitality in science. At present we cannot apply Newton's principles to chemistry, because the soil is only being now prepared. The invisible world of chemical atoms is still waiting for the creator of chemical mechanics. For him our age is collecting a mass of materials, the inductions of well-digested facts, and many-sided inferences similar to those which existed for Astronomy and Mechanics in the days of Newton. It is well also to remember that Newton devoted much time to chemical experiments, and while considering questions of celestial mechanics, persistently kept in view the mutual action of those infinitely small worlds which are concerned in chemical evolutions. For this reason, and also to maintain the unity of laws, it seems to me that we must, in the first instance, seek to harmonise the various phases of contemporary chemical theories with the immortal principles of the Newtonian natural philosophy, and so hasten the advent of true chemical mechanics. Let the above considerations serve as my justification for the attempt which I propose to make to act as a champion of the universality of the Newtonian principles, which I believe are competent to embrace every phenomenon in the universe, from the rotation of the fixed stars to the interchanges of chemical atoms.

In the first place I consider it indispensable to bear in mind that, up to quite recent times, only a one-sided affinity has been recognised in chemical reactions. Thus, for example, from the circumstance that red-hot iron decomposes water with the evolution of hydrogen, it was concluded that oxygen had a greater affinity for iron than for hydrogen. But hydrogen, in presence of red-hot iron scale, appropriates its oxygen and forms water, whence an exactly opposite conclusion may be formed.

During the last ten years a gradual, scarcely perceptible, but most important change has taken place in the views, and consequently in the researches, of chemists. They have sought everywhere, and have always found, systems of conservation or dynamic equilibrium substantially similar to those which natural philosophers have long since discovered in the visible world, and in virtue of which the position of the heavenly bodies in the universe is determined. There where one-sided affinities only were at first detected, not only secondary or lateral ones have been found, but even those which are diametrically opposite; yet among these, dynamical equilibrium establishes itself not by excluding one or other of the forces, but regulating them all. So the chemist finds in the flame of the blast furnace, in the formation of every salt, and, with especial clearness, in double salts and in the crystallisation of solutions, not a fight ending in the victory of one side, as used to be supposed, but the conjunction of forces; the peace of dynamic equilibrium resulting from the action of many forces and affinities. Carbonaceous matters, for example, burn at the expense of the oxygen of the air, yielding a quantity of heat, and forming products of combustion, in which it was thought that the affinities of the oxygen with the combustible elements were satisfied. But it appeared that the heat of combustion was competent to decompose these products, to dissociate the oxygen from the combustible elements, and therefore to explain combustion fully it is necessary to take into account the equilibrium between opposite reactions, between those which evolve and those which absorb heat.

In the same way, in the case of the solution of common salt in water, it is necessary to take into account, on the one hand, the formation of compound particles generated by the combination of salt with water, and, on the other, the disintegration or scattering of the new particles formed, as well as of these originally contained. At present we find two currents of thought, apparently antagonistic to each other, dominating the study of solutions: according to the one, solution seems a mere act of building up or association; according to the other, it is only dissociation or disintegration. The truth lies, evidently, between these views; it lies, as I have endeavoured to prove by my investigations into aqueous solutions, in the dynamic equilibrium of particles tending to combine and also to fall asunder. The large majority of chemical reactions which appeared to act victoriously along one line have been proved capable of acting as victoriously even along an exactly opposite line. Elements which utterly decline to combine directly may often be formed into comparatively stable compounds by indirect means, as, for example, in the case of chlorine and carbon; and consequently the sympathies and antipathies which it was thought to transfer from human relations to those of atoms should be laid aside until the mechanism of chemical relations is explained. Let us remember, however, that chlorine, which does not form with carbon the chloride of carbon, is strongly absorbed, or, as it were, dissolved, by carbon, which leads us to suspect incipient chemical action even in an external and purely surface contact, and involuntarily gives rise to conceptions of that unity of the forces of nature which has been so energetically insisted on by Sir William Grove and formulated in his famous paradox. Grove noticed that platinum, when fused in the oxyhydrogen flame, during which operation water is formed, when allowed to drop into water decomposes the latter and produces the explosive oxyhydrogen mixture. The explanation of this paradox, as of many others which arose during the period of chemical renaissance, has led, in our time, to the promulgation by Henri Sainte-Claire Deville of the conception of dissociation and of equilibrium, and has recalled the teaching of Berthollet, which, notwithstanding its brilliant confirmation by Heinrich Rose and Dr. Gladstone, had not, up to that period, been included in received chemical views.

Chemical equilibrium in general, and dissociation in particular, are now being so fully worked out in detail, and supplied in such various ways, that I do not allude to them to develop, but only use them as examples by which to indicate the correctness of a tendency to regard chemical combinations from points of view differing from those expressed by the term hitherto appropriated to define chemical forces, namely, 'affinity.' Chemical equilibria, dissociation, the speed of chemical reactions, thermochemistry, spectroscopy, and, more than all, the determination of the influence of masses and the search for a connection between the properties and weights of atoms and molecules--in one word, the vast mass of the most important chemical researches of the present day--clearly indicate the near approach of the time when chemical doctrines will submit fully and completely to the doctrine which was first announced in the Principia of Newton.

In order that the application of these principles may bear fruit it is evidently insufficient to assume that statical equilibrium reigns alone in chemical systems or chemical molecules: it is necessary to grasp the conditions of possible states of dynamical equilibria, and to apply to them kinetic principles. Numerous considerations compel us to renounce the idea of statical equilibrium in molecules, and the recent yet strongly-supported appeals to dynamic principles constitute, in my opinion, the foundation of the modern teaching relating to atomicity, or the valency of the elements, which usually forms the basis of investigations into organic or carbon compounds.

This teaching has led to brilliant explanations of very many chemical relations and to cases of isomerism, or the difference in the properties of substances having the same composition. It has been so fruitful in its many applications and in the foreshadowing of remote consequences, especially respecting carbon compounds, that it is impossible to deny its claims to be ranked as a great achievement of chemical science. Its practical application to the synthesis of many substances of the most complicated composition entering into the structure of organised bodies, and to the creation of an unlimited number of carbon compounds, among which the colours derived from coal tar stand prominently forward, surpass the synthetical powers of Nature itself. Yet this teaching, as applied to the structure of carbon compounds, is not on the face of it directly applicable to the investigation of other elements, because in examining the first it is possible to assume that the atoms of carbon have always a definite and equal number of affinities, whilst in the combinations of other elements this is evidently inadmissible. Thus, for example, an atom of carbon yields only one compound with four atoms of hydrogen and one with four atoms of chlorine in the molecule, whilst the atoms of chlorine and hydrogen unite only in the proportions of one to one. Simplicity is here evident, and forms a point of departure from which it is easy to move forward with firm and secure tread. Other elements are of a different nature. Phosphorus unites with three and with five atoms of chlorine, and consequently the simplicity and sharpness of the application of structural conceptions are lost. Sulphur unites only with two atoms of hydrogen, but with oxygen it enters into higher orders of combination. The periodic relationship which exists among all the properties of the elements--such, for example, as their ability to enter into various combinations--and their atomic weights, indicate that this variation in atomicity is subject to one perfectly exact and general law, and it is only carbon and its near analogues which constitute cases of permanently preserved atomicity. It is impossible to recognise as constant and fundamental properties of atoms, powers which, in substance, have proved to be variable. But by abandoning the idea of permanence, and of the constant saturation of affinities--that is to say, by acknowledging the possibility of free affinities--many retain a comprehension of the atomicity of the elements 'under given conditions;' and on this frail foundation they build up structures composed of chemical molecules, evidently only because the conception of manifold affinities gives, at once, a simple statical method of estimating the composition of the most complicated molecules.

I shall enter neither into details, nor into the various consequences following from these views, nor into the disputes which have sprung up respecting them (and relating especially to the number of isomerides possible on the assumption of free affinities), because the foundation or origin of theories of this nature suffers from the radical defect of being in opposition to dynamics. The molecule, as even Laurent expressed himself, is represented as an architectural structure, the style of which is determined by the fundamental arrangement of a few atoms, whilst the decorative details, which are capable of being varied by the same forces, are formed by the elements entering into the combination. It is on this account that the term 'structural' is so appropriate to the contemporary views of the above order, and that the 'structuralists' seek to justify the tetrahedric, plane, or prismatic disposition of the atoms of carbon in benzene. It is evident that the consideration relates to the statical position of atoms and molecules and not to their kinetic relations. The atoms of the structural type are like the lifeless pieces on a chess board: they are endowed but with the voices of living beings, and are not those living beings themselves; acting, indeed, according to laws, yet each possessed of a store of energy which, in the present state of our knowledge, must be taken into account.

In the days of Haüy, crystals were considered in the same statical and structural light, but modern crystallographers, having become more thoroughly acquainted with their physical properties and their actual formation, have abandoned the earlier views, and have made their doctrines dependent on dynamics.

The immediate object of this lecture is to show that, starting with Newton's third law of motion, it is possible to preserve to chemistry all the advantages arising from structural teaching, without being obliged to build up molecules in solid and motionless figures, or to ascribe to atoms definite limited valencies, directions of cohesion, or affinities. The wide extent of the subject obliges me to treat only a small portion of it, namely of substitutions, without specially considering combinations and decompositions, and even then limiting myself to the simplest examples, which, however, will throw open prospects embracing all the natural complexity of chemical relations. For this reason, if it should prove possible to form groups similar, for example, to H_{4} or CH_{6} as the remnants of molecules CH_{4} or C_{2}H_{7} we shall not pause to consider them, because, as far as we know, they fall asunder into two parts, H_{2} + H_{2} or CH_{4} + H_{2}, as soon as they are even temporarily formed, and are incapable of separate existence, and therefore can take no part in the elementary act of substitution. With respect to the simplest molecules which we shall select--that is to say, those of which the parts have no separate existence, and therefore cannot appear in substitutions--we shall consider them according to the periodic law, arranging them in direct dependence on the atomic weight of the elements.

Thus, for example, the molecules of the simplest hydrogen compounds--

HF H_{2}O H_{3}N H_{4}C hydrofluoric acid water ammonia methane

correspond with elements the atomic weights of which decrease consecutively

F = 19, O = 16, N = 14, C = 12.

Neither the arithmetical order (1, 2, 3, 4 atoms of hydrogen) nor the total information we possess respecting the elements will permit us to interpolate into this typical series one more additional element; and therefore we have here, for hydrogen compounds, a natural base on which are built up those simple chemical combinations which we take as typical. But even they are competent to unite with each other, as we see, for instance, in the property which hydrofluoric acid has of forming a hydrate--that is, of combining with water; and a similar attribute of ammonia, resulting in the formation of a caustic alkali, NH_{3},H_{2}O, or NH_{4}OH.

Having made these indispensable preliminary observations, I may now attack the problem itself and attempt to explain the so-called structure or rather construction, of molecules--that is to say, their constitution and transformations--without having recourse to the teaching of 'structuralists,' but on Newton's dynamical principles.

Of Newton's three laws of motion, only the third can be applied directly to chemical molecules when regarded as systems of atoms among which it must be supposed that there exist common influences or forces, and resulting compounded relative motions. Chemical reactions of every kind are undoubtedly accomplished by changes in these internal movements, respecting the nature of which nothing is known at present, but the existence of which the mass of evidence collected in modern times forces us to acknowledge as forming part of the common motion of the universe, and as a fact further established by the circumstance that chemical reactions are always characterised by changes of volume or the relations between the atoms or the molecules. Newton's third law, which is applicable to every system, declares that, 'action is also associated with reaction, and is equal to it.' The brevity of conciseness of this axiom was, however, qualified by Newton in a more expanded statement, 'the action of bodies one upon another are always equal, and in opposite directions.' This simple fact constitutes the point of departure for explaining dynamic equilibrium--that is to say, systems of conservancy. It is capable of satisfying even the dualists, and of explaining, without additional assumptions, the preservation of those chemical types which Dumas, Laurent, and Gerhardt created unit types, and those views of atomic combinations which the structuralists express by atomicity or the valency of the elements, and, in connection with them, the various numbers of affinities. In reality, if a system of atoms or a molecule be given, then in it, according to the third law of Newton, each portion of atoms acts on the remaining portion in the same manner, and with the same force as the second set of atoms acts on the first. We infer directly from this consideration that both sets of atoms, forming a molecule, are not only equivalent with regard to themselves, as they must be according to Dalton's law, but also that they may, if united, replace each other. Let there be a molecule containing atoms A B C, it is clear that, according to Newton's law, the action of A on B C must be equal to the action of B C on A, and if the first action is directed on B C, then the second must be directed on A, and consequently then, where A can exist in dynamic equilibrium, B C may take its place and act in a like manner. In the same way the action of C is equal to the action of A B. In one word every two sets of atoms forming a molecule are equivalent to each other, and may take each other's place in other molecules, or, having the power of balancing each other, the atoms or their complements are endowed with the power of replacing each other. Let us call this consequence of an evident axiom 'the principle of substitution,' and let us apply it to those typical forms of hydrogen compounds which we have already discussed, and which, on account of their simplicity, and regularity, have served as starting-points of chemical argument long before the appearance of the doctrine of structure.

In the type of hydrofluoric acid, HF, or in systems of double stars, are included a multitude of the simplest molecules. It will be sufficient for our purpose to recall a few: for example, the molecules of chlorine, Cl_{2}, and of hydrogen, H_{2}, and hydrochloric acid, HCl, which is familiar to all in aqueous solution as spirits of salt, and which has many points of resemblance with HF, HBr, HI. In these cases division into two parts can only be made in one way, and therefore the principle of substitution renders it probable that exchanges between the chlorine and the hydrogen can take place, if they are competent to unite with each other. There was a time when no chemist would even admit the idea of any such action; it was then thought that the power of combination indicated a polar difference of the molecules in combination, and this thought set aside all idea of the substitution of one component element by another.

Thanks to the observations and experiments of Dumas and Laurent fifty years ago, such fallacies were dispelled, and in this manner the principle of substitution was exhibited. Chlorine and bromine acting on many hydrogen compounds, occupy immediately the place of their hydrogen, and the displaced hydrogen, with another atom of chlorine or bromine, forms hydrochloric acid or bromide of hydrogen. This takes place in all typical hydrogen compounds. Thus chlorine acts on this principle on gaseous hydrogen--reaction, under the influence of light, resulting in the formation of hydrochloric acid. Chlorine acting on the alkalis, constituted similarly to water, and even on water itself--only, however, under the influence of light and only partially because of the instability of HClO--forms by this principle bleaching salts, which are the same as the alkalis, but with their hydrogen replaced by chlorine. In ammonia and in methane, chlorine can also replace the hydrogen. From ammonia is formed in this manner the so-called chloride of nitrogen, NCl_{3}, which decomposes very readily with violent explosion on account of the evolved gases, and falls asunder as chlorine and nitrogen. Out of marsh gas, or methane, CH_{4}, may be obtained consecutively, by this method, every possible substitution, of which chloroform, CHCl_{3}, is the best known, and carbon tetrachloride, CCl_{4}, the most instructive. But by virtue of the fact that chlorine and bromine act, in the manner shown, on the simplest typical hydrogen compounds, their action on the more complicated ones may be assumed to be the same. This can be easily demonstrated. The hydrogen of benzene, C_{6}H_{6}, reacts feebly under the influence of light on liquid bromine, but Gustavson has shown that the addition of the smallest quantity of metallic aluminium causes energetic action and the evolution of large volumes of hydrogen bromide.

If we pass on to the second typical hydrogen compound--that is to say, water--its molecule, HOH, may be split up in two ways: either into an atom of hydrogen and a semi-molecule of hydrogen peroxide, HO, or into oxygen, O, and two atoms of hydrogen, H; and therefore, according to the principle of substitution, it is evident that one atom of hydrogen can exchange with hydrogen oxide, HO, and two atoms of hydrogen, H, with one atom of oxygen, O.

Both these forms of substitution will constitute methods of oxidation--that is to say, of the entrance of oxygen into the compound--a reaction which is so common in nature as well as in the arts, taking place at the expense of the oxygen of the air or by the aid of various oxidising substances or bodies which part easily with their oxygen. There is no occasion to reckon up the unlimited number of cases of such oxidising reactions. It is sufficient to state that in the first of these oxygen is directly transferred, and the position, the chemical function, which hydrogen originally occupied, is, after the substitution, occupied by the hydroxyl. Thus ammonia, NH_{3}, yields hydroxylamine, NH_{2}(OH), a substance which retains many of the properties of ammonia.

Methane and a number of other hydrocarbons yield, by substitution of the hydrogen by its oxide, methyl alcohol, CH_{3}(OH), and other alcohols. The substitution of one atom of oxygen for two atoms of hydrogen is equally common with hydrogen compounds. By this means alcoholic liquids containing ethyl alcohol, or spirits of wine, C_{2}H_{5}(OH), are oxidised until they become vinegar, or acetic acid, C_{2}H_{3}O(OH). In the same way caustic ammonia, or the combination of ammonia with water, NH_{3},H_{2}O, or NH_{4}(OH), which contains a great deal of hydrogen, by oxidation exchanges four atoms of hydrogen for two atoms of oxygen, and becomes converted into nitric acid, NO_{2}(OH). This process of conversion of ammonium salts into saltpetre goes on in the fields every summer, and with especial rapidity in tropical countries. The method by which this is accomplished, though complex, though involving the agency of all-permeating micro-organisms, is, in substance, the same as that by which alcohol is converted into acetic acid, or glycol, C_{2}H_{4}(OH)_{2}, into oxalic acid, if we view the process of oxidation in the light of the Newtonian principles.

But while speaking of the application of the principle of substitution to water, we need not multiply instances, but must turn our attention to two special circumstances which are closely connected with the very mechanism of substitutions.

In the first place, the replacement of two atoms of hydrogen by one atom of oxygen may take place in two ways, because the hydrogen molecule is composed of two atoms, and therefore, under the influence of oxygen, the molecule forming water may separate before the oxygen has time to take its place. It is for this reason that we find, during the conversion of alcohol into acetic acid, that there is an interval during which is formed aldehyde, C_{2}H_{4}O, which, as its very name implies, is 'alcohol dehydrogenatum,' or alcohol deprived of hydrogen. Hence aldehyde combined with hydrogen yields alcohol; and united to oxygen, acetic acid.

For the same reason there should be, and there actually are, intermediate products between ammonia and nitric acid, NO_{2}(HO), containing either less hydrogen than ammonia, less oxygen than nitric acid, or less water than caustic ammonia. Accordingly we find, among the products of the deoxidation of nitric acid and the oxidation of ammonia, not only hydroxylamine, but also nitrous oxide, nitrous and nitric anhydrides. Thus, the production of nitrous acid results from the removal of two atoms of hydrogen from caustic ammonia and the substitution of the oxygen for the hydrogen, NO(OH); or by the substitution, in ammonia, of three atoms of hydrogen by hydroxyl, N(OH){3}, and by the removal of water: N(OH){3} - H_{2}O = NO(OH). The peculiarities and properties of nitrous acid--as, for instance, its action on ammonia and its conversion, by oxidation, into nitric acid--are thus clearly revealed.

On the other hand, in speaking of the principle of substitution as applied to water, it is necessary to observe that hydrogen and hydroxyl, H and OH, are not only competent to unite, but also to form combinations with themselves, and thus become H_{2} and H_{2}O_{2}; and such are hydrogen and the peroxide thereof. In general, if a molecule A B exists, then molecules A A and B B can exist also. A direct reaction of this kind does not, however, take place in water, therefore undoubtedly, at the moment of formation, hydrogen reacts on hydrogen peroxide, as we can show at once by experiment; and further because hydrogen peroxide, H_{2}O_{2}, exhibits a structure containing a molecule of hydrogen, H_{2}, and one of oxygen, O_{2}, either of which is capable of separate existence. The fact, however, may now be taken as thoroughly established, that, at the moment of combustion of hydrogen or of the hydrogen compounds, hydrogen peroxide is always formed, and not only so, but in all probability its formation invariably precedes the formation of water. This was to be expected as a consequence of the law of Avogadro and Gerhardt, which leads us to expect this sequence in the case of equal interactions of volumes of vapours and gases; and in hydrogen peroxide we actually have such equal volumes of the elementary gases.

The instability of hydrogen peroxide--that is to say, the ease with which it decomposes into water and oxygen, even at the mere contact of porous substances--accounts for the circumstance that it does not form a permanent product of combustion, and is not produced during the decomposition of water. I may mention this additional consideration that, with respect to hydrogen peroxide, we may look for its effecting still further substitutions of hydrogen by means of which we may expect to obtain still more highly oxidised water compounds, such as H_{2}O_{3} and H_{2}O_{4}. These Schönbein and Bunsen have long been seeking, and Berthelot is investigating them at present. It is probable, however, that the reaction will stop at the last compound, because we find that, in a number of cases, the addition of four atoms of oxygen seems to form a limit. Thus, OsO_{4}, KClO_{4}, KMnO_{4}, K_{2}SO_{4}, Na_{3}PO_{4}, and such like, represent the highest grades of oxidation.[1]

[1] Because more than four atoms of hydrogen never unite with one atom of the elements, and because the hydrogen compounds (e.g. HCl, H_{2}S, H_{3}P, H_{4}Si) always form their highest oxides with four atoms of oxygen, and as the highest forms of oxides (OsO_{4}, RuO_{4}) also contain four of oxygen, and eight groups of the periodic system, corresponding to the highest basic oxides R_{2}O, RO, R_{2}O_{3}, RO_{2}, R_{2}O_{5}, RO_{3}, R_{2}O_{7}, and RO_{4}, imply the above relationship, and because of the nearest analogues among the elements--such as Mg, Zn, Cd, and Hg; or Cr, Mo, W, and U; or Si, Ge, Sn, and Pt; or F, Cl, Br, and I, and so forth--not more than four are known, it seems to me that in these relationships there lies a deep interest and meaning with regard to chemical mechanics. But because, to my imagination, the idea of unity of design in Nature, either acting in complex celestial systems or among chemical molecules, is very attractive, especially because the atomic teaching at once acquires its true meaning, I will recall the following facts relating to the solar system. There are eight major planets, of which the four inner ones are not only separated from the four outer by asteroids, but differ from them in many respects, as, for example, in the smallness of their diameters and their greater density. Saturn with his ring has eight satellites, Jupiter and Uranus have each four. It is evident that in the solar systems also we meet with these higher numbers four and eight which appear in the combination of chemical molecules.

As for the last forty years, from the times of Berzelius, Dumas, Liebig, Gerhardt, Williamson, Frankland, Kolbe, Kekulé, and Butleroff, most theoretical generalisations have centred round organic or carbon compounds, we will, for the sake of brevity, leave out the discussion of ammonia derivatives, notwithstanding their simplicity with respect to the doctrine of substitutions; we will dwell more especially on its application to carbon compounds, starting from methane, CH_{4}, as the simplest of the hydrocarbons, containing in its molecule one atom of carbon. According to the principles enumerated we may derive from CH_{4} every combination of the form CH_{3}X, CH_{2}X_{2}, CHX_{3}, and CX_{4}, in which X is an element, or radicle, equivalent to hydrogen--that is to say, competent to take its place or to combine with it. Such are the chlorine substitutes already mentioned, such is wood-spirit, CH_{3}(OH), in which X is represented by the residue of water, and such are numerous other carbon derivatives. If we continue, with the aid of hydroxyl, further substitutions of the hydrogen of methane we shall obtain successively CH_{2}(OH){2}, CH(OH){3}, and C(OH){4}. But if, in proceeding thus, we bear in mind that CH{2}(OH){2} contains two hydroxyls in the same form as hydrogen peroxide, H{2}O_{2} or (OH){2}, contains them--and moreover not only in one molecule, but together, attached to one and the same atom of carbon--so here we must look for the same decomposition as that which we find in hydrogen peroxide, and accompanied also by the formation of water as an independently existing molecule; therefore CH{2}(OH){2} should yield, as it actually does, immediately water and the oxide of methylene, CH{2}O, which is methane with oxygen substituted for two atoms of hydrogen. Exactly in the same manner out of CH(OH){3} are formed water and formic acid, CHO(OH), and out of C(OH){4} is produced water and carbonic acid, or directly carbonic anhydride, CO_{2}, which will therefore be nothing else than methane with the double replacement of pairs of hydrogen by oxygen. As nothing leads to the supposition that the four atoms of hydrogen in methane differ one from the other, so it does not matter by what means we obtain any one of the combinations indicated--they will be identical; that is to say, there will be no case of actual isomerism, although there may easily be such cases of isomerism as have been distinguished by the term metamerism.

Formic acid, for example, has two atoms of hydrogen, one attached to the carbon left from the methane, and the other attached to the oxygen which has entered in the form of hydroxyl, and if one of them be replaced by some substance X it is evident that we shall obtain substances of the same composition, but of different construction, or of different orders of movement among the molecules, and therefore endowed with other properties and reactions. If X be methyl, CH_{4}--that is to say, a group capable of replacing hydrogen because it is actually contained with hydrogen in methane itself--then by substituting this group for the original hydrogen we obtain acetic acid, CCH_{3}O(OH), out of formic, and by substitution of the hydrogen in its oxide or hydroxyl we obtain methyl formate, CHO(OCH_{3}). These substances differ so much from each other physically and chemically that at first sight it is hardly possible to admit that they contain the same atoms in identically the same proportions. Acetic acid, for example, boils at a higher temperature than water, and has a higher specific gravity than it, whilst its metameride, methyl formate, is lighter than water, and boils at 30°--that is to say, it evaporates very easily.

Let us now turn to carbon compounds containing two atoms of carbon to the molecule, as in acetic acid, and proceed to evolve them from methane by the principle of substitution. This principle declares at once that methane can only be split up in the four following ways:--

1. Into a group CH_{3} equivalent with H. Let us call changes of this nature methylation.

2. Into a group CH_{2} and H_{2}. We will call this order of substitutions methylenation.

3. Into CH and H_{3}, which commutations we will call acetylenation.

4. Into C and H_{4}, which may be called carbonation.

It is evident that hydrocarbon compounds containing two atoms of carbon can only proceed from methane, CH_{4}, which contains four atoms of hydrogen by the first three methods of substitution; carbonation would yield free carbon if it could take place directly, and if the molecule of free carbon--which is in reality very complex, that is to say strongly polyatomic, as I have long since been proving by various means--could contain only C_{2} like the molecules O_{2}, H_{2}, N_{2}, and so on.

By methylation we should evidently obtain from marsh gas, ethane, CH_{3}CH_{3} = C_{2}H_{6}.

By methylenation--that is, by substituting group CH_{2} for H_{2}--methane forms ethylene, CH_{2}CH_{2} = C_{2}H_{4}.

By acetylenation--that is, by substituting three atoms of hydrogen, H_{3}, in methane--by the remnant CH, we get acetylene, CHCH = C_{2}H_{2}.

If we have applied the principles of Newton correctly, there should not be any other hydrocarbons containing two atoms of carbon in the molecule. All these combinations have long been known, and in each of them we can not only produce those substitutions of which an example has been given in the case of methane, but also all the phases of other substitutions, as we shall find from a few more instances, by the aid of which I trust that I shall be able to show the great complexity of those derivatives which, on the principle of substitution, can be obtained from each hydrocarbon. Let us content ourselves with the case of ethane, CH_{3}CH_{3}, and the substitution of the hydrogen by hydroxyl. The following are the possible changes:--

1. CH_{3}CH_{2}(OH): this is nothing more than spirit of wine, or ethyl alcohol, C_{2}H_{5}(OH) or C_{2}H_{6}O.

2. CH_{2}(OH)CH_{2}(OH): this is the glycol of Würtz, which has shed so much light on the history of alcohol. Its isomeride may be CH_{3}CH(OH){2}, but as we have seen in the case of CH(OH){2}, it decomposes, giving off water, and forming aldehyde, CH_{3}CHO, a substance capable of yielding alcohol by uniting with hydrogen, and of yielding acetic acid by uniting with oxygen.

If glycol, CH_{2}(OH)CH_{2}(OH), loses its water, it may be seen at once that it will not now yield aldehyde, CH_{3}CHO, but its isomeride, CH_{2}CH_{2}/O, the oxide of ethylene. I have here indicated in a special manner the oxygen which has taken the place of two atoms of the hydrogen of ethane taken from different atoms of the carbon.

3. CH_{3}C(OH){3} decomposed as CH(OH){3}, forming water and acetic acid, CH_{3}CO(OH). It is evident that this acid is nothing else than formic acid, CHO(OH), with its hydrogen replaced by methyl. Without examining further the vast number of possible derivatives, I will direct your attention to the circumstance that in dissolving acetic acid in water we obtain the maximum contraction and the greatest viscosity when to the molecule CH_{3}CO(OH) is added a molecule of water, which is the proportion which would form the hydrate CH_{3}C(OH)_{3}. It is probable that the doubling of the molecule of acetic acid at temperatures approaching its boiling-point has some connection with this power of uniting with one molecule of water.

4. CH_{2}(OH)C(OH){3} is evidently an alcoholic acid, and indeed this compound, after losing water, answers to glycolic acid, CH{2}(OH)CO(OH). Without investigating all the possible isomerides, we will note only that the hydrate CH(OH){2}CH(OH){2} has the same composition as CH_{2}(OH)C(OH)_{3}, and although corresponding to glycol, and being a symmetrical substance, it becomes, on parting with its water, the aldehyde of oxalic acid, or the glyoxal of Debus, CHOCHO.

5. CH(OH){2}C(OH{3}), from the tendency of all the preceding, corresponds with glyoxylic acid, an aldehyde acid, CHOCO(OH), because the group CO(OH), or carboxyl, enters into the compositions of organic acids, and the group CHO defines the aldehyde function.

6. C(OH){3}C(OH){3} through the loss of 2H_{2}O yields the bibasic oxalic acid CO(OH)CO(OH), which generally crystallises with 2H_{2}O, following thus the normal type of hydration characteristic of ethane.[2]

[2] One more isomeride, CH_{2}CH(OH), is possible--that is, secondary vinyl alcohol, which is related to ethylene, CH_{2}CH_{2}, but derived by the principle of substitution from CH_{4}. Other isomerides, of the composition C_{2}H_{4}O, such, for example, as CCH_{3}(OH), are impossible, because it would correspond with the hydrocarbon CHCH_{3} = C_{2}H_{4}, which is isomeric with ethylene, and it cannot be derived from methane. If such an isomeride existed it would be derived from CH_{2}, but such products are, up to the present, unknown. In such cases the insufficiency of the points of departure of the statical structural teaching is shown. It first admits constant atomicity and then rejects it, the facts serving to establish either one or the other view; and therefore it seems to me that we must come to the conclusion that the structural method of reasoning, having done a service to science, has outlived the age, and must be regenerated, as in their time was the teaching of the electro-chemists, the radicalists, and the adherents of the doctrine of types. As we cannot now lean on the views above stated, it is time to abandon the structural theory. They will all be united in chemical mechanics, and the principle of substitution must be looked on only as a preparation for the coming epoch in chemistry, where such cases as the isomerism of fumaric and maleic acids, when explained dynamically, as proposed by Le Bel and Van't Hoff, may yield points of departure.

Thus, by applying the principle of substitution, we can, in the simplest manner, derive not only every kind of hydrocarbon compound, such as the alcohols, the aldehyde-alcohols, aldehydes, alcohol-acids, and the acids, but also combinations analogous to hydrated crystals which usually are disregarded.

But even those unsaturated substances, of which ethylene, CH_{2}CH_{2}, and acetylene, CHCH, are types, may be evolved with equal simplicity. With respect to the phenomena of isomerism, there are many possibilities among the hydrocarbon compounds containing two atoms of carbon, and without going into details it will be sufficient to indicate that the following formulæ, though not identical, will be isomeric substantially among themselves:--CH_{3}CHX_{2} and CH_{2}XCH_{2}X, although both contain C_{2}H_{4}X_{2}; or CH_{2}CX_{2} and CHXCHX, although both contain C_{2}H_{2}X_{2}, if by X we indicate chlorine or generally an element capable of replacing one atom of hydrogen, or capable of uniting with it. To isomerism of this kind belongs the case of aldehyde and the oxide of ethylene, to which we have already referred, because both have the composition C_{2}H_{4}O.

What I have said appears to me sufficient to show that the principle of substitution adequately explains the composition, the isomerism, and all the diversity of combination of the hydrocarbons, and I shall limit the further development of these views to preparing a complete list of every possible hydrocarbon compound containing three atoms of carbon in the molecule. There are eight in all, of which only five are known at present.[3]

[3] Conceding variable atomicity, the structuralists must expect an incomparably larger number of isomerides, and they cannot now decline to acknowledge the change of atomicity, were it only for the examples HgCl and HgCl_{2}, CO and CO_{2}, PCl_{3} and PCl_{5}.

Among those possible for C_{3}H_{6} there should be two isomerides, propylene and trimethylene, and they are both already known. For C_{3}H_{4} there should be three isomerides: allylene and allene are known, but the third has not yet been discovered; and for C_{3}H_{2} there should be two isomerides, though neither of them is known as yet. Their composition and structure are easily deduced from ethane, ethylene, and acetylene, by methylation, by methylenation, by acetylenation and by carbonation.

1. C_{3}H_{8} = CH_{3}CH_{2}CH_{3} out of CH_{3}CH_{3} by methylation. This hydrocarbon is named propane.

2. C_{3}H_{6} = CH_{3}CHCH_{2} out of CH_{3}CH_{3} by methylenation. This substance is propylene.

3. C_{3}H_{6} = CH_{2}CH_{2}CH_{2} out of CH_{3}CH_{3} by methylenation. This substance is trimethylene.

4. C_{3}H_{4} = CH_{3}CCH out of CH_{3}CH_{3} by acetylenation or from CHCH by methylation. This hydrocarbon is named allylene.

5. C_{3}H_{4} = CHCH/CH_{2} out of CH_{3}CH_{3} by acetylenation, or from CH_{2}CH_{2} by methylenation, because CH_{2}CH/CH = CHCH/CH_{2}. This body is as yet unknown.

6. C_{3}H_{4} = CH_{2}CCH_{2} out of CH_{2}CH_{2} by methylenation. This hydrocarbon is named allene, or iso-allylene.

7. C_{3}H_{2} = CHCH/C out of CH_{3}CH_{3} by symmetrical carbonation, or out of CH_{2}CH_{2} by acetylenation. This compound is unknown.

8. C_{3}H_{2} = CC/CH_{2} out of CH_{3}CH_{3} by carbonation, or out of CHCH by methylenation. This compound is unknown.

If we bear in mind that for each hydrocarbon serving as a type in the above tables there are a number of corresponding derivatives, and that every compound obtained may, by further methylation, methylenation, acetylenation, and carbonation, produce new hydrocarbons, and these may be followed by a numerous suite of derivatives and an immense number of isomeric substances, it is possible to understand the limitless number of carbon compounds, although they all have the one substance, methane, for their origin. The number of substances is so enormous that it is no longer a question of enlarging the possibilities of discovery, but rather of finding some means of testing them analogous to the well-known two which for a long time have served as gauges for all carbon compounds.

I refer to the law of even numbers and to that of limits, the first enunciated by Gerhardt some forty years ago, with respect to hydrocarbons, namely, that their molecules always contain an even number of atoms of hydrogen. But by the method which I have used of deriving all the hydrocarbons from methane, CH_{4}, this law may be deduced as a direct consequence of the principle of substitutions. Accordingly, in methylation, CH_{3} takes the place of H, and therefore CH_{2} is added. In methylenation the number of atoms of hydrogen remains unchanged, and at each acetylenation it is reduced by two, and in carbonation by four, atoms--that is to say, an even number of atoms of hydrogen is always added or removed. And because the fundamental hydrocarbon, methane, CH_{4}, contains an even number of atoms of hydrogen, all its derivative hydrocarbons will also contain even numbers of hydrogen, and this constitutes the law of even numbers.

The principle of substitutions explains with equal simplicity the conception of the limiting compositions of hydrocarbons C_{n}H_{2_n_ + 2}, which I derived, in 1861,[4] in an empirical manner from accumulated materials available at that time, and on the basis of the limits to combinations worked out by Dr. Frankland for other elements.

[4] 'Essai d'une théorie sur les limites des combinaisons organiques,' par D. Mendeléeff, 2/11 août 1861, _Bulletin de l'Académie i. d. Sc. de St. Pétersbourg_, t. v

Of all the various substitutions the highest proportion of hydrogen is yielded by methylation, because in that operation alone does the quantity of hydrogen increase; hence, taking methane as a point of departure, if we imagine methylation effected (n - 1) times we obtain hydrocarbon compounds containing the highest quantities of hydrogen. It is evident that they will contain CH_{4} + (n - 1)CH_{2}, or C_{n}H_{2_n_} + {2}, because methylation leads to the addition of CH_{2} to the compound.

It will thus be seen that by the principle of substitution--that is to say, by the third law of Newton--we are able to deduce, in the simplest manner, not only the individual composition, the isomerism, and relations of substances, but also the general laws which govern their most complex combinations without having recourse either to statical constructions, to the definition of atomicities, to the exclusion of free affinities, or to the recognition of those single, double or treble bonds which are so indispensable to structuralists in the explanation of the composition and construction of hydrocarbon compounds. And yet, by the application of the dynamical principles of Newton, we can attain to that chief and fundamental object, the comprehension of isomerism in hydrocarbon compounds, and the forecasting of the existence of combinations as yet unknown, by which the edifice raised by structural teaching is strengthened and supported. Besides--and I count this for a circumstance of special importance--the process which I advocate will make no difference in those special cases which have been already so well worked out, such as, for example, the isomerism of the hydrocarbons and alcohols, even to the extent of not interfering with the nomenclature which has been adopted, and the structural system will retain all the glory of having worked up, in a thoroughly scientific manner, the store of information which Gerhardt had accumulated about the middle of the fifties, and the still higher glory of establishing the rational synthesis of organic substances. Nothing will be lost to the structural doctrine except its statical origin; and as soon as it will embrace the dynamic principles of Newton, and suffer itself to be guided by them, I believe that we shall attain for chemistry that unity of principle which is now wanting. Many an adept will be attracted to that brilliant and fascinating enterprise, the penetration into the unseen world of the kinetic relations of atoms, to the study of which the last twenty-five years have contributed so much labour and such high inventive faculties.

D'Alembert found in mechanics that if inertia be taken to represent force, dynamic equations may be applied to statical questions, which are thereby rendered more simple and more easily understood.

The structural doctrine in chemistry has unconsciously followed the same course, and therefore its terms are easily adopted; they may retain their present forms provided that a truly dynamical--that is to say, Newtonian--meaning be ascribed to them.

Before finishing my task and demonstrating the possibility of adapting structural doctrines to the dynamics of Newton, I consider it indispensable to touch on one question which naturally arises, and which I have heard discussed more than once. If bromine, the atom of which is eighty times heavier than that of hydrogen, takes the place of hydrogen, it would seem that the whole system of dynamic equilibrium must be destroyed.

Without entering into the minute analysis of this question, I think it will be sufficient to examine it by the light of two well-known phenomena, one of which will be found in the department of chemistry and the other in that of celestial mechanics, and both will serve to demonstrate the existence of that unity in the plan of creation which is a consequence of the Newtonian doctrines. Experiments demonstrate that when a heavy element is substituted for a light one in a chemical compound--for example, for magnesium, in the oxide of that metal, an atom of mercury, which is 8-1/3 times heavier--the chief chemical characteristics or properties are generally, though not always, preserved.

The substitution of silver for hydrogen, than which it is 108 times heavier, does not affect all the properties of the substance, though it does some. Therefore chemical substitutions of this kind--the substitution of light for heavy atoms--need not necessarily entail changes in the original equilibrium; and this point is still further elucidated by the consideration that the periodic law indicates the degree of influence of an increment of weight in the atom as affecting the possible equilibria, and also what degree of increase in the weight of the atoms reproduces some, though not all, of the properties of the substance.

This tendency to repetition--these periods--may be likened to those annual or diurnal periods with which we are so familiar on the earth. Days and years follow each other, but, as they do so, many things change; and in like manner chemical evolutions, changes in the masses of the elements, permit of much remaining undisturbed, though many properties undergo alteration. The system is maintained according to the laws of conservation in nature, but the motions are altered in consequence of the change of parts.

Next, let us take an astronomical case--such, for example, as the earth and the moon--and let us imagine that the mass of the latter is constantly increasing. The question is, what will then occur? The path of the moon in space is a wave-line similar to that which geometricians have named epicycloidal, or the locus of a point in a circle rolling round another circle. But in consequence of the influence of the moon it is evident that the path of the earth itself cannot be a geometric ellipse, even supposing the sun to be immovably fixed; it must be an epicycloidal curve, though not very far removed from the true ellipse--that is to say, it will be impressed with but faint undulations. It is only the common centre of gravity of the earth and the moon which describes a true ellipse round the sun. If the moon were to increase, the relative undulations of the earth's path would increase in amplitude, those of the moon would also change, and when the mass of the moon had increased to an equality with that of the earth, the path would consist of epicycloidal curves crossing each other, and having opposite phases. But a similar relation exists between the sun and the earth, because the former is also moving in space. We may apply these views to the world of atoms, and suppose that in their movements, when heavy ones take the place of those that are lighter, similar changes take place, provided that the system or the molecule is preserved throughout the change.

It seems probable that in the heavenly systems, during incalculable astronomical periods, changes have taken place and are still going on similar to those which pass rapidly before our eyes during the chemical reaction of molecules, and the progress of molecular mechanics may--we hope will--in course of time permit us to explain those changes in the stellar world which have more than once been noticed by astronomers, and which are now so carefully studied. A coming Newton will discover the laws of these changes. Those laws, when applied to chemistry, may exhibit peculiarities, but these will certainly be mere variations on the grand harmonious theme which reigns in nature. The discovery of the laws which produce this harmony in chemical evolution will only be possible, it seems to me, under the banner of Newtonian dynamics, which has so long waved over the domains of mechanics, astronomy, and physics. In calling chemists to take their stand under its peaceful and catholic shadow I imagine that I am aiding in establishing that scientific union which the managers of the Royal Institution wish to effect, who have shown their desire to do so by the flattering invitation which has given me--a Russian--the opportunity of laying before the countrymen of Newton an attempt to apply to chemistry one of his immortal principles.

APPENDIX II

THE PERIODIC LAW OF THE CHEMICAL ELEMENTS

BY PROFESSOR MENDELÉEFF

FARADAY LECTURE DELIVERED BEFORE THE FELLOWS OF THE CHEMICAL SOCIETY IN THE THEATRE OF THE ROYAL INSTITUTION, ON TUESDAY, JUNE 4, 1889

The high honour bestowed by the Chemical Society in inviting me to pay a tribute to the world-famed name of Faraday by delivering this lecture has induced me to take for its subject the Periodic Law of the Elements--this being a generalisation in chemistry which has of late attracted much attention.

While science is pursuing a steady onward movement, it is convenient from time to time to cast a glance back on the route already traversed, and especially to consider the new conceptions which aim at discovering the general meaning of the stock of facts accumulated from day to day in our laboratories. Owing to the possession of laboratories, modern science now bears a new character, quite unknown, not only to antiquity, but even to the preceding century. Bacon's and Descartes' idea of submitting the mechanism of science simultaneously to experiment and reasoning has been fully realised in the case of chemistry, it having become not only possible but always customary to experiment. Under the all-penetrating control of experiment, a new theory, even if crude, is quickly strengthened, provided it be founded on a sufficient basis; the asperities are removed, it is amended by degrees, and soon loses the phantom light of a shadowy form or of one founded on mere prejudice; it is able to lead to logical conclusions, and to submit to experimental proof. Willingly or not, in science we all must submit not to what seems to us attractive from one point of view or from another, but to what represents an agreement between theory and experiment; in other words, to demonstrated generalisation and to the approved experiment. Is it long since many refused to accept the generalisations involved in the law of Avogadro and Ampère, so widely extended by Gerhardt? We still may hear the voices of its opponents; they enjoy perfect freedom, but vainly will their voices rise so long as they do not use the language of demonstrated facts The striking observations with the spectroscope which have permitted us to analyse the chemical constitution of distant worlds, seemed, at first, applicable to the task of determining the nature of the atoms themselves; but the working out of the idea in the laboratory soon demonstrated that the characters of spectra are determined, not directly by the atoms, but by the molecules into which the atoms are packed; and so it became evident that more verified facts must be collected before it will be possible to formulate new generalisations capable of taking their place beside those ordinary ones based upon the conception of simple substances and atoms. But as the shade of the leaves and roots of living plants, together with the relics of a decayed vegetation, favour the growth of the seedling and serve to promote its luxurious development, in like manner sound generalisations--together with the relics of those which have proved to be untenable--promote scientific productivity, and ensure the luxurious growth of science under the influence of rays emanating from the centres of scientific energy. Such centres are scientific associations and societies. Before one of the oldest and most powerful of these I am about to take the liberty of passing in review the twenty years' life of a generalisation which is known under the name of the Periodic Law. It was in March 1869 that I ventured to lay before the then youthful Russian Chemical Society the ideas upon the same subject which I had expressed in my just written 'Principles of Chemistry.'

Without entering into details, I will give the conclusions I then arrived at in the very words I used:--

'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 (e.g. 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 to their so-called valencies as well as, to some extent, to their distinctive chemical properties--as is apparent, among other series, in that of lithium, beryllium, barium, carbon, nitrogen, oxygen, and iron.

'4. The elements which are the most widely diffused have small atomic weights.

'5. The magnitude of the atomic weight determines the character of the element, just as the magnitude of the molecule determines the character of a compound.

'6. We must expect the discovery of many yet unknown elements--for example, elements analogous to aluminium and silicon, whose atomic weight would be between 65 and 75.

'7. The atomic weight of an element may sometimes be amended by a knowledge of those of the contiguous elements. Thus, the atomic 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 aim of this communication will be fully attained if I succeed in drawing the attention of investigators to those relations which exist between the atomic weights of dissimilar elements, which, so far as I know, have hitherto been almost completely neglected. I believe that the solution of some of the most important problems of our science lies in researches of this kind.'

To-day, twenty years after the above conclusions were formulated, they may still be considered as expressing the essence of the now well-known periodic law.

Reverting to the epoch terminating with the sixties, it is proper to indicate three series of data without the knowledge of which the periodic law could not have been discovered, and which rendered its appearance natural and intelligible.

In the first place, it was at that time that the numerical value of atomic weights became definitely known. Ten years earlier such knowledge did not exist, as may be gathered from the fact that in 1860 chemists from all parts of the world met at Karlsruhe in order to come to some agreement, if not with respect to views relating to atoms, at any rate as regards their definite representation. Many of those present probably remember how vain were the hopes of coming to an understanding, and how much ground was gained at that Congress by the followers of the unitary theory so brilliantly represented by Cannizzaro. I vividly remember the impression produced by his speeches, which admitted of no compromise, and seemed to advocate truth itself, based on the conceptions of Avogadro, Gerhardt, and Regnault, which at that time were far from being generally recognised. And though no understanding could be arrived at, yet the objects of the meeting were attained, for the ideas of Cannizzaro proved, after a few years, to be the only ones which could stand criticism, and which represented an atom as--'the smallest portion of an element which enters into a molecule of its compound.' Only such real atomic weights--not conventional ones--could afford a basis for generalisation. It is sufficient, by way of example, to indicate the following cases in which the relation is seen at once and is perfectly clear:--

K = 39 Rb = 85 Cs = 133 Ca = 40 Sr = 87 Ba = 137

whereas with the equivalents then in use--

K = 39 Rb = 85 Cs = 133 Ca = 20 Sr = 43·5 Ba = 68·5

the consecutiveness of change in atomic weight, which with the true values is so evident, completely disappears.

Secondly, it had become evident during the period 1860-70, and even during the preceding decade, that the relations between the atomic weights of analogous elements were governed by some general and simple laws. Cooke, Cremers, Gladstone, Gmelin, Lenssen, Pettenkofer, and especially Dumas, had already established many facts bearing on that view. Thus Dumas compared the following groups of analogous elements with organic radicles:--

Diff. Diff. Diff. Diff. Mg = 12} P = 31} O = 8} }8 }44 }8 Li = 7 } Ca = 20} As= 75} S = 16} }16 }3 × 8 }44 }3 × 8 Na = 23} Sr = 44} Sb = 119} Se = 40} }16 }3 × 8 }2 × 44 }3 × 8 K = 39 } Ba = 68} Bi = 207} Te = 64}

and pointed out some really striking relationships, such as the following:--

F = 19. Cl = 35·5 = 19 + 16·5. Br = 80 = 19 + 2 × 16·5 + 28. I = 127 = 2 x 19 + 2 × 16·5 + 2 × 28.

A. Strecker, in his work 'Theorien und Experimente zur Bestimmung der Atomgewichte der Elemente' (Braunschweig, 1859), after summarising the data relating to the subject, and pointing out the remarkable series of equivalents--

Cr = 26·2 Mn = 27·6 Fe = 28 Ni = 29 Co = 30 Cu = 31·7 Zn = 32·5

remarks that: 'It is hardly probable that all the above-mentioned relations between the atomic weights (or equivalents) of chemically analogous elements are merely accidental. We must, however, leave to the future the discovery of the law of the relations which appears in these figures.'[1]

[1] 'Es ist wohl kaum anzunehmen, dass alle im Vorhergehenden hervorgehobenen Beziehungen zwischen den Atomgewichten (oder Aequivalenten) in chemischen Verhältnissen einander ähnliche Elemente bloss zufällig sind. Die Auffindung der in diesen Zahlen gesetzlichen Beziehungen müssen wir jedoch der Zukunft überlassen.'

In such attempts at arrangement and in such views are to be recognised the real forerunners of the periodic law; the ground was prepared for it between 1860 and 1870, and that it was not expressed in a determinate form before the end of the decade may, I suppose, be ascribed to the fact that only analogous elements had been compared. The idea of seeking for a relation between the atomic weights of all the elements was foreign to the ideas then current, so that neither the vis tellurique of De Chancourtois, nor the law of octaves of Newlands, could secure anybody's attention. And yet both De Chancourtois and Newlands like Dumas and Strecker, more than Lenssen and Pettenkofer, had made an approach to the periodic law and had discovered its germs. The solution of the problem advanced but slowly, because the facts, but not the law, stood foremost in all attempts; and the law could not awaken a general interest so long as elements, having no apparent connection with each other, were included in the same octave, as for example:--

1st octave of | | | | | | | | Newlands | H | F | Cl | Co & Ni | Br | Pd | I | Pt & Ir 7th Ditto | O | S | Fe | Se | Rh & Ru | Te | Au | Os or Th

Analogies of the above order seemed quite accidental, and the more so as the octave contained occasionally ten elements instead of eight, and when two such elements as Ba and V, Co and Ni, or Rh and Ru, occupied one place in the octave.[2] Nevertheless, the fruit was ripening, and I now see clearly that Strecker, De Chancourtois, and Newlands stood foremost in the way towards the discovery of the periodic law, and that they merely wanted the boldness necessary to place the whole question at such a height that its reflection on the facts could be clearly seen.

[2] To judge from J. A. R. Newlands's work, On the Discovery of the Periodic Law, London, 1884, p. 149; 'On the Law of Octaves' (from the Chemical News, 12, 83, August 18, 1865).

A third circumstance which revealed the periodicity of chemical elements was the accumulation, by the end of the sixties, of new information respecting the rare elements, disclosing their many-sided relations to the other elements and to each other. The researches of Marignac on niobium, and those of Roscoe on vanadium, were of special moment. The striking analogies between vanadium and phosphorus on the one hand, and between vanadium and chromium on the other, which became so apparent in the investigations connected with that element, naturally induced the comparison of V = 51 with Cr = 52, Nb = 94 with Mo = 96, and Ta = 192 with W = 194; while, on the other hand, P = 31 could be compared with S = 32, As = 75 with Se = 79, and Sb = 120 with Te = 125. From such approximations there remained but one step to the discovery of the law of periodicity.

The law of periodicity was thus a direct outcome of the stock of generalisations and established facts which had accumulated by the end of the decade 1860-1870; it is an embodiment of those data in a more or less systematic expression. Where, then, lies the secret of the special importance which has since been attached to the periodic law, and has raised it to the position of a generalisation which has already given to chemistry unexpected aid, and which promises to be far more fruitful in the future and to impress upon several branches of chemical research a peculiar and original stamp? The remaining part of my communication will be an attempt to answer this question.

In the first place we have the circumstance that, as soon as the law made its appearance, it demanded a revision of many facts which were considered by chemists as fully established by existing experience. I shall return, later on, briefly to this subject, but I wish now to remind you that the periodic law, by insisting on the necessity for a revision of supposed facts, exposed itself at once to destruction in its very origin. Its first requirements, however, have been almost entirely satisfied during the last 20 years; the supposed facts have yielded to the law, thus proving that the law itself was a legitimate induction from the verified facts. But our inductions from data have often to do with such details of a science so rich in facts, that only generalisations which cover a wide range of important phenomena can attract general attention. What were the regions touched on by the periodic law? This is what we shall now consider.

The most important point to notice is, that periodic functions, used for the purpose of expressing changes which are dependent on variations of time and space, have been long known. They are familiar to the mind when we have to deal with motion in closed cycles, or with any kind of deviation from a stable position, such as occurs in pendulum-oscillations. A like periodic function became evident in the case of the elements, depending on the mass of the atom. The primary conception of the masses of bodies, or of the masses of atoms, belongs to a category which the present state of science forbids us to discuss, because as yet we have no means of dissecting or analysing the conception. All that was known of functions dependent on masses derived its origin from Galileo and Newton, and indicated that such functions either decrease or increase with the increase of mass, like the attraction of celestial bodies. The numerical expression of the phenomena was always found to be proportional to the mass, and in no case was an increase of mass followed by a recurrence of properties such as is disclosed by the periodic law of the elements. This constituted such a novelty in the study of the phenomena of nature that, although it did not lift the veil which conceals the true conception of mass, it nevertheless indicated that the explanation of that conception must be searched for in the masses of the atoms; the more so, as all masses are nothing but aggregations, or additions, of chemical atoms which would be best described as chemical individuals. Let me remark, by the way, that though the Latin word 'individual' is merely a translation of the Greek word 'atom,' nevertheless history and custom have drawn a sharp distinction between the two words, and the present chemical conception of atoms is nearer to that defined by the Latin word than by the Greek, although this latter also has acquired a special meaning which was unknown to the classics. The periodic law has shown that our chemical individuals display a harmonic periodicity of properties dependent on their masses. Now natural science has long been accustomed to deal with periodicities observed in nature, to seize them with the vice of mathematical analysis, to submit them to the rasp of experiment. And these instruments of scientific thought would surely, long since, have mastered the problem connected with the chemical elements, were it not for a new feature which was brought to light by the periodic law, and which gave a peculiar and original character to the periodic function.

If we mark on an axis of abscissæ a series of lengths proportional to angles, and trace ordinates which are proportional to sines or other trigonometrical functions, we get periodic curves of a harmonic character. So it might seem, at first sight, that with the increase of atomic weights the function of the properties of the elements should also vary in the same harmonious way. But in this case there is no such continuous change as in the curves just referred to, because the periods do not contain the infinite number of points constituting a curve, but a finite number only of such points. An example will better illustrate this view. The atomic weights--

Ag = 108 Cd = 112 In = 113 Sn = 118 Sb = 120 Te = 125 I = 127

steadily increase, and their increase is accompanied by a modification of many properties which constitutes the essence of the periodic law. Thus, for example, the densities of the above elements decrease steadily, being respectively--

10·5 8·6 7·4 7·2 6·7 6·4 4·9

while their oxides contain an increasing quantity of oxygen--

Ag_{2}O Cd_{2}O_{2} In_{2}O_{3} Sn_{2}O_{4} Sb_{2}O_{5} Te_{2}O_{6} I_{2}O_{7}

But to connect by a curve the summits of the ordinates expressing any of these properties would involve the rejection of Dalton's law of multiple proportions. Not only are there no intermediate elements between silver, which gives AgCl, and cadmium, which gives CdCl_{2}, but, according to the very essence of the periodic law, there can be none; in fact a uniform curve would be inapplicable in such a case, as it would lead us to expect elements possessed of special properties at any point of the curve. The periods of the elements have thus a character very different from those which are so simply represented by geometers. They correspond to points, to numbers, to sudden changes of the masses, and not to a continuous evolution. In these sudden changes destitute of intermediate steps or positions, in the absence of elements intermediate between, say, silver and cadmium, or aluminium and silicon, we must recognise a problem to which no direct application of the analysis of the infinitely small can be made. Therefore, neither the trigonometrical functions proposed by Ridberg and Flavitzky, nor the pendulum-oscillations suggested by Crookes, nor the cubical curves of the Rev. Mr. Haughton, which have been proposed for expressing the periodic law, from the nature of the case, can represent the periods of the chemical elements. If geometrical analysis is to be applied to this subject, it will require to be modified in a special manner. It must find the means of representing in a special way, not only such long periods as that comprising

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br,

but short periods like the following:--

Na Mg Al Si P S Cl.

In the theory of numbers only do we find problems analogous to ours, and two attempts at expressing the atomic weights of the elements by algebraic formulæ seem to be deserving of attention, although neither of them can be considered as a complete theory, nor as promising finally to solve the problem of the periodic law. The attempt of E. J. Mills (1886) does not even aspire to attain this end. He considers that all atomic weights can be expressed by a logarithmic function,

15(n - 0·9375^t),

in which the variables n and t are whole numbers. Thus, for oxygen, n = 2, and t = 1, whence its atomic weight is = 15·94; in the case of chlorine, bromine, and iodine, n has respective values of 3, 6, and 9, whilst t = 7, 6, and 9; in the case of potassium, rubidium, and cæsium, n = 4, 6, and 9, and t = 14, 18, and 20.

Another attempt was made in 1888 by B. N. Tchitchérin. Its author places the problem of the periodic law in the first rank, but as yet he has investigated the alkali metals only. Tchitchérin first noticed the simple relations existing between the atomic volumes of all alkali metals; they can be expressed, according to his views, by the formula

A(2 - 0·00535A_n_),

where A is the atomic weight, and n is equal to 8 for lithium and sodium, to 4 for potassium, to 3 for rubidium, and to 2 for cæsium. If n remained equal to 8 during the increase of A, the volume would become zero at A = 46-2/3, and it would reach its maximum at A = 23-1/3. The close approximation of the number 46-2/3 to the differences between the atomic weights of analogous elements (such as Cs - Rb, I - Br, and so on); the close correspondence of the number 23-1/3 to the atomic weight of sodium; the fact of n being necessarily a whole number, and several other aspects of the question, induce Tchitchérin to believe that they afford a clue to the understanding of the nature of the elements; we must, however, await the full development of his theory before pronouncing judgment on it. What we can at present only be certain of is this: that attempts like the two above named must be repeated and multiplied, because the periodic law has clearly shown that the masses of the atoms increase abruptly, by steps, which are clearly connected in some way with Dalton's law of multiple proportions; and because the periodicity of the elements finds expression in the transition from RX to RX_{2}, RX_{3}, RX_{4}, and so on till RX_{8}, at which point, the energy of the combining forces being exhausted, the series begins anew from RX to RX_{2}, and so on.

While connecting by new bonds the theory of the chemical elements with Dalton's theory of multiple proportions, or atomic structure of bodies, the periodic law opened for natural philosophy a new and wide field for speculation. Kant said that there are in the world 'two things which never cease to call for the admiration and reverence of man: the moral law within ourselves, and the stellar sky above us.' But when we turn our thoughts towards the nature of the elements and the periodic law, we must add a third subject, namely, 'the nature of the elementary individuals which we discover everywhere around us.' Without them the stellar sky itself is inconceivable; and in the atoms we see at once their peculiar individualities, the infinite multiplicity of the individuals, and the submission of their seeming freedom to the general harmony of Nature.

Having thus indicated a new mystery of Nature, which does not yet yield to rational conception, the periodic law, together with the revelations of spectrum analysis, have contributed to again revive an old but remarkably long-lived hope--that of discovering, if not by experiment, at least by a mental effort, the primary matter--which had its genesis in the minds of the Grecian philosophers, and has been transmitted, together with many other ideas of the classic period, to the heirs of their civilisation. Having grown, during the times of the alchemists up to the period when experimental proof was required, the idea has rendered good service; it induced those careful observations and experiments which later on called into being the works of Scheele, Lavoisier, Priestley, and Cavendish. It then slumbered awhile, but was soon awakened by the attempts either to confirm or to refute the ideas of Prout as to the multiple proportion relationship of the atomic weights of all the elements. And once again the inductive or experimental method of studying Nature gained a direct advantage from the old Pythagorean idea: because atomic weights were determined with an accuracy formerly unknown. But again the idea could not stand the ordeal of experimental test, yet the prejudice remains and has not been uprooted, even by Stas; nay, it has gained a new vigour, for we see that all which is imperfectly worked out, new and unexplained, from the still scarcely studied rare metals to the hardly perceptible nebulæ, have been used to justify it. As soon as spectrum analysis appears as a new and powerful weapon of chemistry, the idea of a primary matter is immediately attached to it. From all sides we see attempts to constitute the imaginary substance helium[3] the so much longed for primary matter. No attention is paid to the circumstance that the helium line is only seen in the spectrum of the solar protuberances, so that its universality in Nature remains as problematic as the primary matter itself; nor to the fact that the helium line is wanting amongst the Fraunhofer lines of the solar spectrum, and thus does not answer to the brilliant fundamental conception which gives its real force to spectrum analysis.

[3] That is, a substance having a wave-length equal to 0·0005875 millimetre.

And finally, no notice is even taken of the indubitable fact that the brilliancies of the spectral lines of the simple substances vary under different temperatures and pressures; so that all probabilities are in favour of the helium line simply belonging to some long since known element placed under such conditions of temperature, pressure, and gravity as have not yet been realised in our experiments. Again, the idea that the excellent investigations of Lockyer of the spectrum of iron can be interpreted in favour of the compound nature of that element, evidently must have arisen from some misunderstanding. The spectrum of a compound certainly does not appear as a sum of the spectra of its components; and therefore the observations of Lockyer can be considered precisely as a proof that iron undergoes no other changes at the temperature of the sun than those which it experiences in the voltaic arc--provided the spectrum of iron is preserved. As to the shifting of some of the lines of the spectrum of iron while the other lines maintain their positions, it can be explained, as shown by M. Kleiber ('Journal of the Russian Chemical and Physical Society,' 1885, 147), by the relative motion of the various strata of the sun's atmosphere, and by Zöllner's laws of the relative brilliancies of different lines of the spectrum. Moreover, it ought not to be forgotten that if iron were really proved to consist of two or more unknown elements, we should simply have an increase in the number of our elements--not a reduction, and still less a reduction of all of them to one single primary matter.

Feeling that spectrum analysis will not yield a support to the Pythagorean conception, its modern promoters are so bent upon its being confirmed by the periodic law, that the illustrious Berthelot, in his work 'Les origines de l'Alchimie,' 1885, 313, has simply mixed up the fundamental idea of the law of periodicity with the ideas of Prout, the alchemists, and Democritus about primary matter.[4] But the periodic law, based as it is on the solid and wholesome ground of experimental research, has been evolved independently of any conception as to the nature of the elements; it does not in the least originate in the idea of a unique matter; and it has no historical connection with that relic of the torments of classical thought, and therefore it affords no more indication of the unity of matter or of the compound character of our elements, than the law of Avogadro, or the law of specific heats, or even the conclusions of spectrum analysis. None of the advocates of a unique matter have ever tried to explain the law from the standpoint of ideas taken from a remote antiquity when it was found convenient to admit the existence of many gods--and of a unique matter.

[4] He maintains (on p. 309) that the periodic law requires two new analogous elements, having atomic weights of 48 and 64, occupying positions between sulphur and selenium, although nothing of the kind results from any of the different readings of the law.

When we try to explain the origin of the idea of a unique primary matter, we easily trace that in the absence of inductions from experiment it derives its origin from the scientifically philosophical attempt at discovering some kind of unity in the immense diversity of individualities which we see around. In classical times such a tendency could only be satisfied by conceptions about the immaterial world. As to the material world, our ancestors were compelled to resort to some hypothesis, and they adopted the idea of unity in the formative material, because they were not able to evolve the conception of any other possible unity in order to connect the multifarious relations of matter. Responding to the same legitimate scientific tendency, natural science has discovered throughout the universe a unity of plan, a unity of forces, and a unity of matter, and the convincing conclusions of modern science compel every one to admit these kinds of unity. But while we admit unity in many things, we none the less must also explain the individuality and the apparent diversity which we cannot fail to trace everywhere. It has been said of old, 'Give us a fulcrum, and it will become easy to displace the earth.' So also we must say, 'Give us something that is individualised, and the apparent diversity will be easily understood.' Otherwise, how could unity result in a multitude?

After a long and painstaking research, natural science has discovered the individualities of the chemical elements, and therefore it is now capable not only of analysing, but also of synthesising; it can understand and grasp generality and unity, as well as the individualised and the multifarious. The general and universal, like time and space, like force and motion, vary uniformly; the uniform admit of interpolations, revealing every intermediate phase. But the multitudinous, the individualised--such as ourselves, or the chemical elements, or the members of a peculiar periodic function of the elements, or Dalton's multiple proportions--is characterised in another way: we see in it, side by side with a connecting general principle, leaps, breaks of continuity, points which escape from the analysis of the infinitely small--an absence of complete intermediate links. Chemistry has found an answer to the question as to the causes of multitudes; and while retaining the conception of many elements, all submitted to the discipline of a general law, it offers an escape from the Indian Nirvana--the absorption in the universal, replacing it by the individualised. However, the place for individuality is so limited by the all-grasping, all-powerful universal, that it is merely a point of support for the understanding of multitude in unity.

Having touched upon the metaphysical bases of the conception of a unique matter which is supposed to enter into the composition of all bodies. I think it necessary to dwell upon another theory, akin to the above conception--the theory of the compound character of the elements now admitted by some--and especially upon one particular circumstance which, being related to the periodic law, is considered to be an argument in favour of that hypothesis.

Dr. Pelopidas, in 1883, made a communication to the Russian Chemical and Physical Society on the periodicity of the hydrocarbon radicles, pointing out the remarkable parallelism which was to be noticed in the change of properties of hydrocarbon radicles and elements when classed in groups. Professor Carnelley, in 1886, developed a similar parallelism. The idea of M. Pelopidas will be easily understood if we consider the series of hydrocarbon radicles which contain, say, 6 atoms of carbon:--

I. II. III. IV. V. C_{6}H_{13} C_{6}H_{12} C_{6}H_{11} C_{6}H_{10} C_{6}H_{9} VI. VII. VIII. C_{6}H_{8} C_{6}H_{7} C_{6}H_{6}

The first of these radicles, like the elements of the 1st group, combines with Cl, OH, and so on, and gives the derivatives of hexyl alcohol, C_{6}H_{13}(OH); but, in proportion as the number of hydrogen atoms decreases, the capacity of the radicles of combining with, say, the halogens increases. C_{6}H_{12} already combines with 2 atoms of chlorine; C_{6}H_{11}, with 3 atoms, and so on. The last members of the series comprise the radicles of acids: thus C_{6}H_{8}, which belongs to the 6th group, gives, like sulphur, a bibasic acid, C_{6}H_{8}O_{2}(OH){2}, which is homologous with oxalic acid. The parallelism can be traced still further, because C{6}H_{5} appears as a monovalent radicle of benzene, and with it begins a new series of aromatic derivatives, so analogous to the derivatives of the aliphatic series. Let me also mention another example from among those which have been given by M. Pelopidas. Starting from the alkaline radicle of monomethylammonium, N(CH_{3})H_{3}, or NCH_{6}, which presents many analogies with the alkaline metals of the 1st group, he arrives, by successively diminishing the number of the atoms of hydrogen, at a 7th group which contains cyanogen, CN, which has long since been compared to the halogens of the 7th group.

The most important consequence which, in my opinion, can be drawn from the above comparison is that the periodic law, so apparent in the elements, has a wider application than might appear at first sight; it opens up a new vista of chemical evolutions. But, while admitting the fullest parallelism between the periodicity of the elements and that of the compound radicles, we must not forget that in the periods of the hydrocarbon radicles we have a decrease of mass as we pass from the representatives of the first group to the next, while in the periods of the elements the mass increases during the progression. It thus becomes evident that we cannot speak of an identity of periodicity in both cases, unless we put aside the ideas of mass and attraction, which are the real corner-stones of the whole of natural science, and even enter into those very conceptions of simple substances which came to light a full hundred years later than the immortal principles of Newton.[5]

[5] It is noteworthy that the year in which Lavoisier was born (1743)--the author of the idea of elements and of the indestructibility of matter--is later by exactly one century than the year in which the author of the theory of gravitation and mass was born (1643 N.S.). The affiliation of the ideas of Lavoisier and those of Newton is beyond doubt.

From the foregoing, as well as from the failures of so many attempts at finding in experiment and speculation a proof of the compound character of the elements and of the existence of primordial matter, it is evident, in my opinion, that this theory must be classed among mere utopias. But utopias can only be combated by freedom of opinion, by experiment, and by new utopias. In the republic of scientific theories freedom of opinions is guaranteed. It is precisely that freedom which permits me to criticise openly the widely-diffused idea as to the unity of matter in the elements. Experiments and attempts at confirming that idea have been so numerous that it really would be instructive to have them all collected together, if only to serve as a warning against the repetition of old failures. And now as to new utopias which may be helpful in the struggle against the old ones, I do not think it quite useless to mention a phantasy of one of my students who imagined that the weight of bodies does not depend upon their mass, but upon the character of the motion of their atoms. The atoms, according to this new utopian, may all be homogeneous or heterogeneous, we know not which; we know them in motion only, and that motion they maintain with the same persistence as the stellar bodies maintain theirs. The weights of atoms differ only in consequence of their various modes and quantity of motion; the heaviest atoms may be much simpler than the lighter ones: thus an atom of mercury may be simpler than an atom of hydrogen--the manner in which it moves causes it to be heavier. My interlocutor even suggested that the view which attributes the greater complexity to the lighter elements finds confirmation in the fact that the hydrocarbon radicles mentioned by Pelopidas, while becoming lighter as they lose hydrogen, change their properties periodically in the same manner as the elements change theirs, according as the atoms grow heavier.

The French proverb, La critique est facile, mais l'art est difficile, however, may well be reversed in the case of all such ideal views, as it is much easier to formulate than to criticise them. Arising from the virgin soil of newly-established facts, the knowledge relating to the elements, to their masses, and to the periodic changes of their properties has given a motive for the formation of utopian hypotheses, probably because they could not be foreseen by the aid of any of the various metaphysical systems, and exist, like the idea of gravitation, as an independent outcome of natural science, requiring the acknowledgment of general laws, when these have been established with the same degree of persistency as is indispensable for the acceptance of a thoroughly established fact. Two centuries have elapsed since the theory of gravitation was enunciated, and although we do not understand its cause, we still must regard gravitation as a fundamental conception of natural philosophy, a conception which has enabled us to perceive much more than the metaphysicians did or could with their seeming omniscience. A hundred years later the conception of the elements arose; it made chemistry what it now is; and yet we have advanced as little in our comprehension of simple substances since the times of Lavoisier and Dalton as we have in our understanding of gravitation. The periodic law of the elements is only twenty years old; it is not surprising, therefore, that, knowing nothing about the causes of gravitation and mass, or about the nature of the elements, we do not comprehend the rationale of the periodic law. It is only by collecting established laws--that is, by working at the acquirement of truth--that we can hope gradually to lift the veil which conceals from us the causes of the mysteries of Nature and to discover their mutual dependency. Like the telescope and the microscope, laws founded on the basis of experiment are the instruments and means of enlarging our mental horizon.

In the remaining part of my communication I shall endeavour to show, and as briefly as possible, in how far the periodic law contributes to enlarge our range of vision. Before the promulgation of this law the chemical elements were mere fragmentary, incidental facts in Nature; there was no special reason to expect the discovery of new elements, and the new ones which were discovered from time to time appeared to be possessed of quite novel properties. The law of periodicity first enabled us to perceive undiscovered elements at a distance which formerly was inaccessible to chemical vision; and long ere they were discovered new elements appeared before our eyes possessed of a number of well-defined properties. We now know three cases of elements whose existence and properties were foreseen by the instrumentality of the periodic law. I need but mention the brilliant discovery of gallium, which proved to correspond to eka-aluminium of the periodic law, by Lecoq de Boisbaudran; of scandium, corresponding to ekaboron, by Nilson; and of germanium, which proved to correspond in all respects to ekasilicon, by Winkler. When, in 1871, I described to the Russian Chemical Society the properties, clearly defined by the periodic law, which such elements ought to possess, I never hoped that I should live to mention their discovery to the Chemical Society of Great Britain as a confirmation of the exactitude and the generality of the periodic law. Now that I have had the happiness of doing so, I unhesitatingly say that, although greatly enlarging our vision, even now the periodic law needs further improvements in order that it may become a trustworthy instrument in further discoveries.[6]

[6] I foresee some more new elements, but not with the same certitude as before. I shall give one example, and yet I do not see it quite distinctly. In the series which contains Hg = 204, Pb = 206, and Bi = 208, we can imagine the existence (at the place VI-11) of an element analogous to tellurium, which we can describe as dvi-tellurium, Dt, having an atomic weight of 212, and the property of forming the oxide DtO_{3}. If this element really exists, it ought in the free state to be an easily fusible, crystalline, non-volatile metal of a grey colour, having a density of about 9·3, capable of giving a dioxide, DtO_{2}, equally endowed with feeble acid and basic properties. This dioxide must give on active oxidation an unstable higher oxide, DtO_{3}, which should resemble in its properties PbO_{2} and Bi_{2}O_{5}. Dvi-tellurium hydride, if it be found to exist, will be a less stable compound than even H_{2}Te. The compounds of dvi-tellurium will be easily reduced, and it will form characteristic definite alloys with other metals.

I will venture to allude to some other matters which chemistry has discerned by means of its new instrument, and which it could not have made out without a knowledge of the law of periodicity, and I will confine myself to simple substances and to oxides.

Before the periodic law was formulated the atomic weights of the elements were purely empirical numbers, so that the magnitude of the equivalent, and the atomicity, or the value in substitution possessed by an atom, could only be tested by critically examining the methods of determination, but never directly by considering the numerical values themselves; in short, we were compelled to move in the dark, to submit to the facts, instead of being masters of them. I need not recount the methods which permitted the periodic law at last to master the facts relating to atomic weights, and I would merely call to mind that it compelled us to modify the valencies of indium and cerium, and to assign to their compounds a different molecular composition. Determinations of the specific heats of these two metals fully confirmed the change. The trivalency of yttrium, which makes us now represent its oxide as Y_{2}O_{3} instead of as YO, was also foreseen (in 1870) by the periodic law, and it has now become so probable that Clève, and all other subsequent investigators of the rare metals, have not only adopted it, but have also applied it without any new demonstration to substances so imperfectly known as those of the cerite and gadolinite group, especially since Hillebrand determined the specific heats of lanthanum and didymium and confirmed the expectations suggested by the periodic law. But here, especially in the case of didymium, we meet with a series of difficulties long since foreseen through the periodic law, but only now becoming evident, and chiefly arising from the relative rarity and insufficient knowledge of the elements which usually accompany didymium.

Passing to the results obtained in the case of the rare elements beryllium, scandium, and thorium, it is found that these have many points of contact with the periodic law. Although Avdéeff long since proposed the magnesia formula to represent beryllium oxide, yet there was so much to be said in favour of the alumina formula, on account of the specific heat of the metals and the isomorphism of the two oxides, that it became generally adopted and seemed to be well established. The periodic law, however, as Brauner repeatedly insisted ('Berichte,' 1878, 872; 1881, 53), was against the formula Be_{2}O_{3}; it required the magnesia formula BeO--that is, an atomic weight of 9--because there was no place in the system for an element like beryllium having an atomic weight of 13·5. This divergence of opinion lasted for years, and I often heard that the question as to the atomic weight of beryllium threatened to disturb the generality of the periodic law, or, at any rate, to require some important modifications of it. Many forces were operating in the controversy regarding beryllium, evidently because a much more important question was at issue than merely that involved in the discussion of the atomic weight of a relatively rare element: and during the controversy the periodic law became better understood, and the mutual relations of the elements became more apparent than ever before. It is most remarkable that the victory of the periodic law was won by the researches of the very observers who previously had discovered a number of facts in support of the trivalency of beryllium. Applying the higher law of Avogadro, Nilson and Petterson have finally shown that the density of the vapour of the beryllium chloride, BeCl_{2}, obliges us to regard beryllium as bivalent in conformity with the periodic law.[7] I consider the confirmation of Avdéeff's and Brauner's view as important in the history of the periodic law as the discovery of scandium, which, in Nilson's hands, confirmed the existence of ekaboron.

[7] Let me mention another proof of the bivalency of beryllium which may have passed unnoticed, as it was only published in the Russian chemical literature. Having remarked (in 1884) that the density of such solutions of chlorides of metals, MCl_{n}, as contain 200 mols. of water (or a large and constant amount of water) regularly increases as the molecular weight of the dissolved salt increases, I proposed to one of our young chemists, M. Burdakoff, that he should investigate beryllium chloride. If its molecule be BeCl_{2} its weight must be = 80; and in such a case it must be heavier than the molecule of KCl = 74·5, and lighter than that of MgCl_{2}, = 93. On the contrary, if beryllium chloride is a trichloride, BeCl_{3} = 120, its molecule must be heavier than that of CaCl_{2} = 111, and lighter than that of MnCl_{2} = 126. Experiment has shown the correctness of the former formula, the solution BeCl_{2} + 200H_{2}O having (at 15°/4°) a density of 1·0138, this being a higher density than that of the solution KCl + 200H_{2}O (= 1·0121), and lower than that of MgCl_{2} + 200H_{2}O (= 1·0203). The bivalency of beryllium was thus confirmed in the case both of the dissolved and the vaporised chloride.

The circumstance that thorium proved to be quadrivalent, and Th = 232, in accordance with the views of Chydenius and the requirements of the periodic law, passed almost unnoticed, and was accepted without opposition, and yet both thorium and uranium are of great importance in the periodic system, as they are its last members, and have the highest atomic weights of all the elements.

The alteration of the atomic weight of uranium from U = 120 into U = 240 attracted more attention, the change having been made on account of the periodic law, and for no other reason. Now that Roscoe, Rammelsberg, Zimmermann, and several others have admitted the various claims of the periodic law in the case of uranium, its high atomic weight is received without objection, and it endows that element with a special interest.

While thus demonstrating the necessity for modifying the atomic weights of several insufficiently known elements, the periodic law enabled us also to detect errors in the determination of the atomic weights of several elements whose valencies and true position among other elements were already well known. Three such cases are especially noteworthy: those of tellurium, titanium and platinum. Berzelius had determined the atomic weight of tellurium to be 128, while the periodic law claimed for it an atomic weight below that of iodine, which had been fixed by Stas at 126·5, and which was certainly not higher than 127. Brauner then undertook the investigation, and he has shown that the true atomic weight of tellurium is lower than that of iodine, being near to 125. For titanium the extensive researches of Thorpe have confirmed the atomic weight of Ti = 48, indicated by the law, and already foreseen by Rose, but contradicted by the analyses of Pierre and several other chemists. An equally brilliant confirmation of the expectations based on the periodic law has been given in the case of the series osmium, iridium, platinum, and gold. At the time of the promulgation of the periodic law, the determinations of Berzelius, Rose, and many others gave the following figures:--

Os = 200; Ir = 197; Pt = 198; Au = 196.

The expectations of the periodic law[8] have been confirmed, first, by new determinations of the atomic weight of platinum (by Seubert, Dittmar, and M'Arthur, which proved to be near to 196 (taking O = 16, as proposed by Marignac, Brauner, and others); secondly, by Seubert having proved that the atomic weight of osmium is really lower than that of platinum, being near to 191; and thirdly, by the investigations of Krüss, Thorpe and Laurie, proving that the atomic weight of gold exceeds that of platinum, and approximates to 197. The atomic weights which were thus found to require correction were precisely those which the periodic law had indicated as affected with errors; and it has been proved, therefore, that the periodic law affords a means of testing experimental results. If we succeed in discovering the exact character of the periodic relationships between the increments in atomic weights of allied elements discussed by Ridberg in 1885, and again by Bazaroff in 1887, we may expect that our instrument will give us the means of still more closely controlling the experimental data relating to atomic weights.

[8] I pointed them out in the Liebig's Annalen, Supplement Band., viii. 1871, p. 211.

Let me next call to mind that, while disclosing the variation of chemical properties,[9] the periodic law, has also enabled us to systematically discuss many of the physical properties of elementary bodies, and to show that these properties are also subject to the law of periodicity. At the Moscow Congress of Russian Naturalists in August, 1869, I dwelt upon the relations which existed between density and the atomic weight of the elements. The following year Professor Lothar Meyer, in his well-known paper,[10] studied the same subject in more detail, and thus contributed to spread information about the periodic law. Later on, Carnelley, Laurie, L. Meyer, Roberts-Austen, and several others applied the periodic system to represent the order in the changes of the magnetic properties of the elements, their melting points, the heats of formation of their haloid compounds, and even of such mechanical properties as the coefficient of elasticity, the breaking stress, &c., &c. These deductions, which have received further support in the discovery of new elements endowed not only with chemical but even with physical properties, which were foreseen by the law of periodicity, are well known; so I need not dwell upon the subject, and may pass to the consideration of oxides.[11]

[9] Thus, in the typical small period of

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

we see at once the progression from the alkali metals to the acid non-metals, such as are the halogens.

[10] Liebig's Annalen, Supplement Band., vii. 1870.

[11] A distinct periodicity can also be discovered in the spectra of the elements. Thus the researches of Hartley, Ciamician, and others have disclosed, first, the homology of the spectra of analogous elements: secondly, that the alkali metals have simpler spectra than the metals of the following groups; and thirdly, that there is a certain likeness between the complicated spectra of manganese and iron on the one hand, and the no less complicated spectra of chlorine and bromine on the other hand, and their likeness corresponds to the degree of analogy between those elements which is indicated by the periodic law.

In indicating that the gradual increase of the power of elements of combining with oxygen is accompanied by a corresponding decrease in their power of combining with hydrogen, the periodic law has shown that there is a limit of oxidation, just as there is a well-known limit to the capacity of elements for combining with hydrogen. A single atom of an element combines with at most four atoms of either hydrogen or oxygen; and while CH_{4} and SiH_{4} represent the highest hydrides, so RuO_{4} and OsO_{4} are the highest oxides. We are thus led to recognise types of oxides, just as we have had to recognise types of hydrides.[12]

[12] Formerly it was supposed that, being a bivalent element, oxygen can enter into any grouping of the atoms, and there was no limit foreseen as to the extent to which it could further enter into combination. We could not explain why bivalent sulphur, which forms compounds such as

O O / \ / \ S | and S O, \ / \ / O O

could not also form oxides such as--

O--O O--O / \ / \ S | or S O, \ / \ / O--O O--O

while other elements, as, for instance, chlorine, form compounds such as--

Cl--O--O--O--O--K

The periodic law has demonstrated that the maximum extent to which different non-metals enter into combination with oxygen is determined by the extent to which they combine with hydrogen, and that the sum of the number of equivalents of both must be equal to 8. Thus chlorine, which combines with 1 atom or 1 equivalent of hydrogen, cannot fix more than 7 equivalents of oxygen, giving Cl_{2}O_{7}; while sulphur, which fixes 2 equivalents of hydrogen, cannot combine with more than 6 equivalents or 3 atoms of oxygen. It thus becomes evident that we cannot recognise as a fundamental property of the elements the atomic valencies deduced from their hydrides; and that we must modify, to a certain extent, the theory of atomicity if we desire to raise it to the dignity of a general principle capable of affording an insight into the constitution of all compound molecules. In other words, it is only to carbon, which is quadrivalent with regard both to oxygen and hydrogen, that we can apply the theory of constant valency and of bond, by means of which so many still endeavour to explain the structure of compound molecules. But I should go too far if I ventured to explain in detail the conclusions which can be drawn from the above considerations. Still, I think it necessary to dwell upon one particular fact which must be explained from the point of view of the periodic law in order to clear the way to its extension in that particular direction.

The higher oxides yielding salts the formation of which was foreseen by the periodic system--for instance, in the short series beginning with sodium--

Na_{2}O, MgO, Al_{2}O_{3}, SiO_{2}, P_{2}O_{5}, SO_{3}, Cl_{2}O_{7},

must be clearly distinguished from the higher degrees of oxidation which correspond to hydrogen peroxide and bear the true character of peroxides. Peroxides such as Na_{2}O_{2}, BaO_{2}, and the like have long been known. Similar peroxides have also recently become known in the case of chromium, sulphur, titanium, and many other elements, and I have sometimes heard it said that discoveries of this kind weaken the conclusions of the periodic law in so far as it concerns the oxides. I do not think so in the least, and I may remark, in the first place, that all these peroxides are endowed with certain properties obviously common to all of them, which distinguish them from the actual, higher, salt-forming oxides, especially their easy decomposition by means of simple contact agencies; their incapability of forming salts of the common type; and their capability of combining with other peroxides (like the faculty which hydrogen peroxide possesses of combining with barium peroxide, discovered by Schoene). Again, we remark that some groups are especially characterised by their capacity of generating peroxides. Such is, for instance, the case in the sixth group, where we find the well-known peroxides of sulphur, chromium, and uranium; so that further investigation of peroxides will probably establish a new periodic function, foreshadowing that molybdenum and tungsten will assume peroxide forms with comparative readiness. To appreciate the constitution of such peroxides, it is enough to notice that the peroxide form of sulphur (so-called persulphuric acid) stands in the same relation to sulphuric acid as hydrogen peroxide stands to water:--

H(OH), or H_{2}O, responds to (OH)(OH), or H_{2}O_{2},

and so also--

H(HSO_{4}), or H_{2}SO_{4}, responds to (HSO_{4})(HSO_{4}), or H_{2}S_{2}O_{8}.

Similar relations are seen everywhere, and they correspond to the principle of substitutions which I long since endeavoured to represent as one of the chemical generalisations called into life by the periodic law. So also sulphuric acid, if considered with reference to hydroxyl, and represented as follows:--

HO(SO_{2}OH),

has its corresponding compound in dithionic acid--

(SO_{2}OH)(SO_{2}OH), or H_{2}S_{2}O_{6}.

Therefore, also, phosphoric acid, HO(POH_{2}O_{2}), has, in the same sense, its corresponding compound in the subphosphoric acid of Saltzer:--

(POH_{2}O_{2})(POH_{2}O_{2}), or H_{4}P_{2}O_{6};

and we must suppose that the peroxide compound corresponding to phosphoric acid, if it be discovered, will have the following structure:--

(H_{2}PO_{4}){2} or H{4}P_{2}O_{8} = 2H_{2}O + 2PO_{3}.[13]

So far as is known at present, the highest form of peroxides is met with in the peroxide of uranium, UO_{4}, prepared by Fairley;[14] while OsO_{4} is the highest oxide giving salts. The line of argument which is inspired by the periodic law, so far from being weakened by the discovery of peroxides, is thus actually strengthened, and we must hope that a further exploration of the region under consideration will confirm the applicability to chemistry generally of the principles deduced from the periodic law.

[13] In this sense, oxalic acid, (COOH){2}, also corresponds to carbonic acid, OH(COOH), in the same way that dithionic acid corresponds to sulphuric acid, and subphosphoric acid to phosphoric; hence, if a peroxide corresponding to carbonic acid be obtained, it will have the structure of (HCO{3}){2}, or H{2}C_{2}O_{6} = H_{2}O + C_{2}O_{5}. So also lead must have a real peroxide, Pb_{2}O_{5}.

[14] The compounds of uranium prepared by Fairley seem to me especially instructive in understanding the peroxides. By the action of hydrogen peroxide on uranium oxide, UO_{3}, a peroxide of uranium, UO_{4},4H_{2}O, is obtained (U = 240) if the solution be acid; but if hydrogen peroxide act on uranium oxide in the presence of caustic soda, a crystalline deposit is obtained which has the composition Na_{4}UO_{8},4H_{2}O, and evidently is a combination of sodium peroxide, Na_{2}O_{2}, with uranium peroxide, UO_{4}. It is possible that the former peroxide, UO_{4},4H_{2}O, contains the elements of hydrogen peroxide and uranium peroxide, U_{2}O_{7}, or even U(OH){6},H{2}O_{2}, like the peroxide of tin recently discovered by Spring, which has the constitution Sn_{2}O_{5},H_{2}O_{2}.

Permit me now to conclude my rapid sketch of the oxygen compounds by the observation that the periodic law is especially brought into evidence in the case of the oxides which constitute the immense majority of bodies at our disposal on the surface of the earth.

The oxides are evidently subject to the law, both as regards their chemical and their physical properties, especially if we take into account the cases of polymerism which are so obvious when comparing CO_{2}, with Si_{n}O_{2_n_}. In order to prove this I give the densities s and the specific volumes v of the higher oxides of two short periods. To render comparison easier, the oxides are all represented as of the form R_{2}O_{n}. In the column headed [Delta] the differences are given between the volume of the oxygen compound and that of the parent element, divided by n--that is, by the number of atoms of oxygen in the compound:--[15]

s. v. [Delta] Na_{2}O 2·6 24 -22 Mg_{2}O_{2} 3·6 22 -3 Al_{2}O_{3} 4·0 26 +1·3 Si_{2}O_{4} 2·65 45 5·2 P_{2}O_{5} 2·39 59 6·2 S_{2}O_{6} 1·96 82 8·7 K_{2}O 2·7 35 -55 Sc_{2}O_{3} 3·86 35 0 Li_{2}O_{4} 4·2 38 +5 V_{2}O_{5} 3·49 52 6·7 Cr_{2}O_{6} 2·74 73 9·5

[15] [Delta] thus represents the average increase of volume for each atom of oxygen contained in the higher salt-forming oxide. The acid oxides give, as a rule, a higher value of [Delta], while in the case of the strongly alkaline oxides its value is usually negative.

I have nothing to add to these figures, except that like relations appear in other periods as well. The above relations were precisely those which made it possible for me to be certain that the relative density of ekasilicon oxide would be about 4·7; germanium oxide, actually obtained by Winkler, proved, in fact, to have the relative density 4·703.

The foregoing account is far from being an exhaustive one of all that has already been discovered by means of the periodic law telescope in the boundless realms of chemical evolution. Still less is it an exhaustive account of all that may yet be seen, but I trust that the little which I have said will account for the philosophical interest attached in chemistry to this law. Although but a recent scientific generalisation, it has already stood the test of laboratory verification, and appears as an instrument of thought which has not yet been compelled to undergo modification; but it needs not only new applications, but also improvements, further development, and plenty of fresh energy. All this will surely come, seeing that such an assembly of men of science as the Chemical Society of Great Britain has expressed the desire to have the history of the periodic law described in a lecture dedicated to the glorious name of Faraday.

APPENDIX III

ARGON, A NEW CONSTITUENT OF THE ATMOSPHERE

WRITTEN BY PROFESSOR MENDELÉEFF IN FEBRUARY 1895

The remarks made in Chapter V., Note 16 bis respecting the newly discovered constituent of the atmosphere are here supplemented by data (taken from the publications of the Royal Society of London) given by the discoverers Lord Rayleigh and Professor Ramsay in January 1895, together with observations made by Crookes and Olszewsky upon the same subject.

This gas, which was discovered by Rayleigh and Ramsay in atmospheric nitrogen, was named argon[1] by them, and upon the supposition of its being an element, they gave it the symbol A. But its true chemical nature is not yet fully known, for not only has no compound of it been yet obtained, but it has not even been brought into any reaction. From all that is known about it at the present time, we may conclude with the discoverers that argon belongs to those gases which are permanent constituents of the atmosphere, and that it is a new element. The latter statement, however, requires confirmation. We shall presently see, however, that the negative chemical character of argon (its incapacity to react with any substance), and the small amount of it present in the atmosphere (about 1-1/4 per cent. by volume in the nitrogen of air, and consequently about 1 per cent. by volume in air), as well as the recent date of its discovery (1894) and the difficulty of its preparation, are quite sufficient reasons for the incompleteness of the existing knowledge respecting this element. But since, so far as is yet known, we are dealing with a normal constituent of the atmosphere[1 bis], the existing data, notwithstanding their insufficiently definite nature, should find a place even in such an elementary work as the present, all the more as the names of Rayleigh, Ramsay, Crookes and Olszewsky, who have worked upon argon, are among the highest in our science, and their researches among the most difficult.[2] These researches, moreover, were directed straight to the goal, which was only partly reached owing to the unusual properties of argon itself.

[1] From the Greek [Greek: Argon]--inert.

[1 bis] In Note 16 bis, Chapter V., I mentioned that, judging from the specific gravity of argon, it might possibly be polymerised nitrogen, N_{3}, bearing the same relationship to nitrogen, N_{2}, that ozone, O_{3}, bears to ordinary oxygen. If this idea were confirmed, still one would not imagine that argon was formed from the atmospheric nitrogen by those reactions by which it was obtained by Rayleigh and Ramsay, but rather that it arises from the nitrogen of the atmosphere under natural conditions. Although this proposition is not quite destroyed by the more recent results, still it is contradicted by the fact that the ratio of the specific heats of argon was found to be 1·66, which, as far as is now known, could not be the case for a gas containing 3 atoms in its molecule, since such gases (see Chapter XIV., Note 7) give the ratio approximately 1·3 (for example, CO_{2}). In abstaining from further conclusions, for they must inevitably be purely conjectural, I consider it advisable to suggest that in conducting further researches upon argon it might be well to subject it to as high a temperature as possible. And the possibility of nitrogen polymerising is all the more admissible from the fact that the aggregation of its atoms in the molecule is not at all unlikely, and that polymerised nitrogen, judging from many examples, might be inert if the polymerisation were accompanied by the evolution of heat. In the following footnotes I frequently return to this hypothesis, not only because I have not yet met any facts definitely contradictory to it, but also because the chief properties of argon agree with it to a certain extent.

[2] The chief difficulty in investigating argon lies in the fact that its preparation requires the employment of a large quantity of air, which has to be treated with a number of different reagents, whose perfect purity (especially that of magnesium) will always be doubtful, and argon has not yet been transferred to a substance in which it could be easily purified. Perhaps the considerable solubility of argon in water (or in other suitable liquids, which have not apparently yet been tried) may give the means of doing so, and it may be possible, by collecting the air expelled from boiling water, to obtain a richer source of argon than ordinary air.

When it became known (Chapter V., Note 4 bis) that the nitrogen obtained from air (by removing the oxygen, moisture and CO_{2}, by various reagents) has a greater density than that obtained from the various (oxygen, hydrogen and metallic) compounds of nitrogen, it was a plausible explanation that the latter contained an admixture of hydrogen, or of some other light gas lowering the density of the mixture. But such an assumption is refuted not only by the fact that the nitrogen obtained from its various compounds (after purification) has always the same density (although the supposed impurities mixed with it should vary), but also by Rayleigh and Ramsay's experiment of artificially adding hydrogen to nitrogen, and then passing the mixture over red-hot oxide of copper, when it was found that the nitrogen regained its original density, i.e. that the whole of the hydrogen was removed by this treatment. Therefore the difference in the density of the two varieties of nitrogen had to be explained by the presence of a heavier gas in admixture with the nitrogen obtained from the atmosphere. This hypothesis was confirmed by the fact that Rayleigh and Ramsay having obtained purified nitrogen (by removing the O_{2}, CO_{2}, and H_{2}O), both from ordinary air and from air which had been previously subjected to atmolysis, that is which had been passed through porous tubes (of burnt clay, e.g. pipe-stem), surrounded by a rarefied space, and so deprived of its lighter constituents (chiefly nitrogen), found that the nitrogen from the air which had been subjected to atmolysis was heavier than that obtained from air which had not been so treated. This experiment showed that the nitrogen of air contains an admixture of a gas which, being heavier than nitrogen itself,[3] diffuses more slowly than nitrogen through the porous material. It remained, therefore, to separate this impurity from the nitrogen. To do this Rayleigh and Ramsay adopted two methods, converting the nitrogen into solid and liquid substances, either by absorbing the nitrogen by heated magnesium (Chapter V., Note 6, and Chapter XIV., Note 14), with the formation of nitride of magnesium, or else by converting it into nitric acid by the action of electric sparks or the presence of an excess of air and alkali, as in Cavendish's method.[3 bis] In both cases the nitrogen entered into reaction, while the heavier gas mixed with it remained inert, and was thus able to be isolated. That is, the argon could be separated by these means from the excess of atmospheric nitrogen accompanying it.[4] As an illustration we will describe how argon was obtained from the atmospheric nitrogen by means of magnesium.[5] To begin with, it was discovered that when atmospheric nitrogen was passed through a tube containing metallic magnesium heated to redness, its specific gravity rose to 14·88. As this showed that part of the gas was absorbed by the magnesium, a mercury gasometer filled with atmospheric nitrogen was taken, and the gas drawn over soda-lime, P_{2}O_{5}, heated magnesium[6] and then through tubes containing red-hot copper oxide, soda-lime and phosphoric anhydride to a second mercury gasometer. Every time the gas was repassed through the tubes, it decreased in volume and increased in density. After repeating this for ten days 1,500 c.c. of gas were reduced to 200 cc., and the density increased to 16·1 (if that of H_{2} = 1 and N_{2} = 14). Further treatment of the remainder brought the density up to 19·09. After adding a small quantity of oxygen and repassing the gas through the apparatus, the density rose to 20·0. To obtain argon by this process Ramsay and Rayleigh (employing a mercury air pump and mercury gasometers) once treated about 150 litres of atmospheric nitrogen. On another occasion they treated 7,925 c.c. of air by the oxidation method and obtained 65 c.c. of argon, which corresponds to 0·82 per cent. The density of the argon obtained by this means was nearly 19·7, while that obtained by the magnesium method varied between 19·09 and 20·38.

[3] It might also be supposed that this heavy gas is separated by the copper when the latter absorbs the oxygen of the air; but such a supposition is not only improbable in itself, but does not agree with the fact that nitrogen may be obtained from air by absorbing the oxygen by various other substances in solution (for instance, by the lower oxides of the metals, like FeO) besides red-hot copper, and that the nitrogen obtained is always just as heavy. Besides which, nitrogen is also set free from its oxides by copper, and the nitrogen thus obtained is lighter. Therefore it is not the copper which produces the heavy gas--i.e. argon.

[3 bis] It is worthy of note that Cavendish obtained a small residue of gas in converting nitrogen into nitric acid; but he paid no attention to it, although probably he had in his hands the very argon recently discovered.

[4] When in these experiments, instead of atmospheric nitrogen the gas obtained from its compound was taken, an inert residue of a heavy gas, having the properties of argon, was also remarked, but its amount was very small. Rayleigh and Ramsay ascribe the formation of this residue to the fact that the gas in these experiments was collected over water, and a portion of the dissolved argon in it might have passed into the nitrogen. As the authors of this supposition did not prove it by any special experiments, it forms a weak point in their classical research. If it be admitted that argon is N_{3}, the fact of its being obtained from the nitrogen of compounds might be explained by the polymerisation of a portion of the nitrogen in the act of reaction, although it is impossible to refute Rayleigh and Ramsay's hypothesis of its being evolved from the water employed in the manipulation of the gases. Three thousand volumes of nitrogen extracted from its compounds gave about three volumes of argon, while thirty volumes were yielded by the same amount of atmospheric nitrogen.

[5] The preparation of argon by the conversion of nitrogen into nitric acid is complicated by the necessity of adding a large proportion of oxygen and alkali, of passing an electric discharge through the mixture for a long period, and then removing the remaining oxygen. All this was repeatedly done by the authors, but this method is far more complex, both in practice and theory, than the preparation of argon by means of magnesium. From 100 volumes of air subjected to conversion into HNO_{3}, 0·76 volume of argon were obtained after absorbing the excess of oxygen.

[6] In these and the following experiments the magnesium was placed in an ordinary hard glass tube, and heated in a gas furnace to a temperature almost sufficient to soften the glass. The current of gas must be very slow (a tube containing a small quantity of sulphuric acid served as a meter), as otherwise the heat evolved in the formation of the Mg_{3}N_{2} (Chapter XIV., Note 14) will melt the tube.

Thus the first positive and very important fact respecting argon is that its specific gravity is nearly 20--that is, that it is 20 times heavier than hydrogen, while nitrogen is only 14 times and oxygen 16 times heavier than hydrogen. This explains the difference observed by Rayleigh between the densities of nitrogen obtained from its compounds and from the atmosphere (Chapter V., Note 4 bis). At 0° and 760 mm. a litre of the former gas weighs 1·2505 grm., while a litre of the latter weighs 1·2572, or taking H = 1, the density of the first = 13·916, and of the latter = 13·991. If the density of argon be taken as 20, it is contained in atmospheric nitrogen to the extent of about 1·23 per cent. by volume, whilst air contains about 0·97 per cent. by volume.

When argon had been isolated the question naturally arose, was it a new homogeneous substance having definite properties or was it a mixture of gases? The former may now be positively asserted, namely, that argon is a peculiar gas previously unknown to chemistry. Such a conviction is in the first place established by the fact that argon has a greater number of negative properties, a smaller capacity for reaction, than any other simple or compound body known. The most inert gas known is nitrogen, but argon far exceeds it in this respect. Thus nitrogen is absorbed at a red heat by many metals, with the formation of nitrides, while argon, as is seen in the mode of its preparation and by direct experiment, does not possess this property. Nitrogen, under the action of electric sparks, combines with hydrogen in the presence of acids and with oxygen in the presence of alkalis, while argon is unable to do so, as is seen from the method of separation from nitrogen. Rayleigh and Ramsay also proved that argon is unable to react with chlorine (dry or moist) either directly or under the action of an electric discharge, or with phosphorus or sulphur, at a red heat. Sodium, potassium, and tellurium may be distilled in an atmosphere of argon without change. Fused caustic soda, incandescent soda-lime, molten nitre, red-hot peroxide of sodium, and the polysulphides of calcium and sodium also do not react with argon. Platinum black does not absorb it, and spongy platinum is unable to excite its reaction with oxygen or chlorine. Aqua regia, bromine water, and a mixture of hydrochloric acid and KMnO_{4} were also without action upon argon. Besides which it is evident from the method of its preparation that it is not acted upon by red-hot oxide of copper. All these facts exclude any possibility of argon containing any already known body, and prove it to be the most inert of all the gases known. But besides these negative points, the independency of argon is confirmed by four observed positive properties possessed by it, which are:--

1. The spectrum of argon observed by Crookes under a low pressure (in Geissler-Plücker tubes) distinguishes it from other gases.[7] It was proved by this means that the argon obtained by means of magnesium is identical with that which remains after the conversion of the atmospheric nitrogen into nitric acid. Like nitrogen, argon presents two spectra produced at different potentials of the induced current, one being orange-red, the other steel-blue; the latter is obtained under a higher degree of rarefaction and with a battery of Leyden jars. Both the spectra of argon (in contradistinction to those of nitrogen) are distinguished by clearly defined lines.[8] The red (ordinary) spectrum of argon has two particularly brilliant and characteristic red lines (not far from the bright red line of lithium, on the opposite side to the orange band) having wave-lengths 705·64 and 696·56 (see Vol. I., p. 565). Between these bright lines there are in addition lines with wave lengths 603·8, 565·1, 561·0, 555·7, 518·58, 516·5, 450·95, 420·10, 415·95 and 394·85. Altogether 80 lines have been observed in this spectrum and 119 in the blue spectrum, of which 26 are common to both spectra.[9]

[7] The greatest brilliancy of the spectrum of argon is obtained at a tension of 3 mm., while for nitrogen it is about 75 mm. (Crookes). In Chapter V., Note 16 bis, it is said that the same blue line observed in the spectrum of argon is also observed in the spectrum of nitrogen. This is a mistake, since there is no coincidence between the blue lines of the argon and nitrogen spectra. However, we may add that for nitrogen the following moderately bright lines are known of wave-lengths 585, 574, 544, 516, 457, 442, 436, and 426, which are repeated in the spectra (red and blue) of argon, judging by Crookes' researches (1895); but it is naturally impossible to assert that there is perfect identity until some special comparative work has been done in this subject, which is very desirable, and more especially for the bluish-violet portion of the spectrum, more particularly between the lines 442-436, as these lines are distinguished by their brilliancy in both the argon and nitrogen spectra. The above-mentioned supposition of argon being polymerised nitrogen (N_{3}), formed from nitrogen (N_{2}), with the evolution of heat, might find some support should it be found after careful comparison that even a limited number of spectral lines coincided.

[8] At first the spectrum of argon exhibits the nitrogen lines, but after a certain time these lines disappear (under the influence of the platinum, and also of Al and Mg, but with the latter the spectrum of hydrogen appears) and leave a pure argon spectrum. It does not appear clear to me whether a polymerisation here takes place or a simple absorption. Perhaps the elucidation of this question would prove important in the history of argon. It would be desirable to know, for instance, whether the volume of argon changes when it is first subjected to the action of the electric discharge.

[9] Crookes supposes that argon contains a mixture of two gases, but as he gives no reasons for this, beyond certain peculiarities of a spectroscopic character, we will not consider this hypothesis further.

2. According to Rayleigh and Ramsay the solubility of argon in water is approximately 4 volumes in 100 volumes of water at 13°. Thus argon is nearly 2-1/2 times more soluble than nitrogen, and its solubility approaches that of oxygen. Direct experiment proves that nitrogen obtained from air from boiled water is heavier than that obtained straight from the atmosphere. This again is an indirect proof of the presence of argon in air.

3. The ratio k of the two specific heats (at a constant pressure and at a constant volume) of argon was determined by Rayleigh and Ramsay by the method of the velocity of sound (see Chapter XIV., Note 7 and Chapter VII., Note 26) and was found to be nearly 1·66, that is greater than for those gases whose molecules contain two atoms (for instance, CO, H_{2}, N_{2}, air, &c., for which k is nearly 1·4) or those whose molecules contain three atoms (for instance, CO_{2}, N_{2}O, &c., for which k is about 1·3), but closely approximate to the ratio of the specific heats of mercury vapour (Kundt and Warburg, k = 1·67). And as the molecule of mercury vapour contains one atom, so it may be said that argon is a simple gaseous body whose molecule contains one atom.[10] A compound body should give a smaller ratio. The experiments upon the liquefaction of argon, which we shall presently describe, speak against the supposition that argon is a mixture of two gases. The importance of the results in question makes one wish that the determinations of the ratio of the specific heats (and other physical properties) might be confirmed with all possible accuracy.[11] If we admit, as we are obliged to do for the present, that argon is a new element, its density shows that its atomic weight must be nearly 40, that is, near to that of K = 39 and Ca = 40, which does not correspond to the existing data respecting the periodicity of the properties of the elements in dependence upon their atomic weights, for there is no reason on the basis of existing data for admitting any intermediate elements between Cl = 35·5 and K = 39, and all the positions above potassium in the periodic system are occupied. This renders it very desirable that the velocity of sound in argon should be re-determined.[12]

[10] This portion of Rayleigh and Ramsay's researches deserves particular attention as, so far, no gaseous substance is known whose molecule contains but one atom. Were it not for the above determinations, it might be thought that argon, having a density 20, has a complex molecule, and may be a compound or polymerised body, for instance, N_{3} or NX_{n}, or in general X_{n}; but as the matter stands, it can only be said that either (1) argon is a new, peculiar, and quite unusual elementary substance, since there is no reason for assuming it to contain two simple gases, or (2) the magnitude, k (the ratio of the specific heats) does not only depend upon the number of atoms contained in the molecules, but also upon the store of internal energy (internal motion of the atoms in the molecule). Should the latter be admitted, it would follow that the molecules of very active gaseous elements would correspond to a smaller k than those of other gases having an equal number of atoms in their molecule. Such a gas is chlorine, for which k = 1·33 (Chapter XIV., Note 7). For gases having a small chemical energy, on the contrary, a larger magnitude would be expected for k. I think these questions might be partially settled by determining k for ozone (O_{3}) and sulphur (S_{6}) (at about 500°). In other words, I would suggest, though only provisionally, that the magnitude, k = 1·6, obtained for argon might prove to agree with the hypothesis that argon is N_{3}, formed from N_{2} with the evolution of heat or loss of energy. Here argon gives rise to questions of primary importance, and it is to be hoped that further research will throw some light upon them. In making these remarks, I only wish to clear the road for further progress in the study of argon, and of the questions depending on it. I may also remark that if argon is N_{3} formed with the evolution of heat, its conversion into nitrogen, N_{2}, and into nitride compounds (for instance, boron nitride or nitride of titanium) might only take place at a very high temperature.

[11] Without having the slightest reason for doubting the accuracy of Rayleigh and Ramsay's determinations, I think it necessary to say that as yet (February 1895) I am only acquainted with the short memoir of the above chemists in the 'Proceedings of the Royal Society,' which does not give any description of the methods employed and results obtained, while at the end (in the general conclusions) the authors themselves express some doubt as to the simple nature of argon. Moreover, it seems to me that (Note 10) there must be a dependence of k upon the chemical energy. Besides which, it is not clear what density of the gas Rayleigh and Ramsay took in determining k. (If argon be N_{3}, its density would be near to 21.) Hence I permit myself to express some doubt as to whether the molecule of argon contains but one atom.

[12] If it should be found that k for argon is less than 1·4, or that k is dependent upon the chemical energy, it would be possible to admit that the molecule of argon contains not one, but several atoms--for instance, either N_{3} (then the density would be 21, which is near to the observed density) or X_{6}, if X stand for an element with an atomic weight near to 6·7. No elements are known between H = 1 and Li = 7, but perhaps they may exist. The hypothesis A = 40 does not admit argon into the periodic system. If the molecule of argon be taken as A_{2}--i.e. the atomic weight as A = 20--argon apparently finds a place in Group VIII., between F = 19 and Na = 23; but such a position could only be justified by the consideration that elements of small atomic weight belong to the category of typical elements which offer many peculiarities in their properties, as is seen on comparing N with the other elements of Group V., or O with those of Group VI. Apart from this there appears to me to be little probability, in the light of the periodic law, in the position of an inert substance like argon in Group VIII., between such active elements as fluorine and sodium, as the representatives of this group by their atomic weights and also by their properties show distinct transitions from the elements of the last groups of the uneven series to the elements of the first groups of the even series--for instance,

Group VI. VII. VIII. I. II. Cr Mn Fe, Co, Ni Cu Zn

While if we place argon in a similar manner,

VI. VII. VIII. I. II. O = 16 F = 19 A = 20 Na = 23 Mg = 24

although from a numerical point of view there is a similar sequence to the above, still from a chemical and physical point of view the result is quite different, as there is no such resemblance between the properties of O, F and Na, Mg, as between Cr, Mn, and Cu, Zn. I repeat that only the typical character of the elements with small atomic weights can justify the atomic weight A = 20, and the placing of argon in Group VIII. amongst the typical elements; then N, O, F, A are a series of gases.

It appears to me simpler to assume that argon contains N_{3}, especially as argon is present in nitrogen and accompanies it, and, as a matter of fact, none of the observed properties of argon are contradictory to this hypothesis.

These observations were written by me in the beginning of February 1895, and on the 29th of that month I received a letter, dated February 25, from Professor Ramsay informing me that 'the periodic classification entirely corresponds to its (argon's) atomic weight, and that it even gives a fresh proof of the periodic law,' judging from the researches of my English friends. But in what these researches consisted, and how the above agreement between the atomic weight of argon and the periodic system was arrived at, is not referred to in the letter, and we remain in expectation of a first publication of the work of Lord Rayleigh and Professor Ramsey. [For more complete information see papers read before the Royal Society, January 31, 1895, February 13, March 10, and May 21, 1896, and a paper published in the Chemical Society's Transactions, 1895, p. 684. For abstracts of these and other papers on argon and helium, and correspondence, see 'Nature,' 1895 and 1896.

4. Argon was liquefied by Professor Olszewsky, who is well known for his classical researches upon liquefied gases. These researches have an especial interest since they show that argon exhibits a perfect constancy in its properties in the liquid and critical states, which almost[13] disposes of the supposition that it contains a mixture of two or more unknown gases. As the first experiments showed, argon remains a gas under a pressure of 100 atmospheres and at a temperature of -90°; this indicated that its critical temperature was probably below this temperature, as was indeed found to be the case when the temperature was lowered to -128°·6[14] by means of liquid ethylene. At this temperature argon easily liquefies to a colourless liquid under 38 atmospheres. The meniscus begins to disappear at between -119°·8 and -121°·6, mean -121° at a pressure of 50·6 atmospheres. The vapour tension of liquid argon at -128°·6, is 38·0 atmospheres, at -187° it is one atmosphere, and at -189°·6 it solidifies to a colourless substance like ice. The specific gravity of liquid argon at about -187° is nearly 1·5, which is far above that of other liquefied gases of very low absolute boiling point.

The discovery of argon is one of the most remarkable chemical acquisitions of recent times, and we trust that Lord Rayleigh and Professor Ramsay, who made this wonderful discovery, will further elucidate the true nature of argon, as this should widen the fundamental principles of chemistry, to which the chemists of Great Britain have from early times made such valuable contributions. It would be premature now to give any definite opinions upon so new a subject. Only one thing can be said; argon is so inert that its rôle in nature cannot be considerable, notwithstanding its presence in the atmosphere. But as the atmosphere itself plays such a vast part in the life of the surface of the earth, every addition to our knowledge of its composition must directly or indirectly react upon the sum total of our knowledge of nature.

[13] There only remains the very remote possibility that argon consists of a mixture of two gases having very nearly the same properties.

[14] The following data, given by Olszewsky, supplement the data given in Chapter II., Note 29, upon liquefied gases.

(tc) (pc) t _t__{1} s N_{2} -146° 35 -194°·4 -214° 0·885 CO -139°·5 35·5 -190° -207 ? A -121° 50·6 -187° -189°·6 1·5 O_{2} -118°·8 50·8 -182°·7 ? 1·124 NO -93°·5 71·2 -153°·6 -167° ? CH_{4} -81°·8 54·9 -164° -158°·8 0·415

where tc is the absolute (critical) boiling point, pc the pressure (critical) in atmospheres corresponding to it, t the boiling point (under a pressure of 760 mm.), t{1}_ the melting point, and s the specific gravity in a liquid state at t.

The above shows that argon in its properties in a liquid state stands near to oxygen (as it also does in its solubility), but that all the temperatures relating to it (tc, t, and t{1}) are higher than for nitrogen. This fully answers, not only to the higher density of argon, but also to the hypothesis that it contains N{3}. And as the boiling point of argon differs from that of nitrogen and oxygen by less than 10°, and its amount is small, it is easy to understand how Dewar (1894), who tried to separate it from liquid air and nitrogen by fractional distillation, was unable to do so. The first and last portions were identical, and nitrogen from air showed no difference in its liquefaction from that obtained from its compounds, or from that which had been passed through a tube containing incandescent magnesium. Still, it is not quite clear why both kinds of nitrogen, after being passed over the magnesium in Dewar's experiments, exhibited an almost similar alteration in their properties, independent of the appearance of a small quantity of hydrogen in them.

Concluding Remarks (March 31, 1895).--The 'Comptes rendus' of the Paris Academy of Sciences of March 18, 1895, contains a memoir by Berthelot upon the reaction of argon with the vapour of benzene under the action of a silent discharge. In his experiments, Berthelot succeeded in treating 83 per cent. of the argon taken for the purpose, and supplied to him by Ramsay (37 c.c. in all). The composition of the product could not be determined owing to the small amount obtained, but in its outward appearance it quite resembled the product formed under similar conditions by nitrogen. This observation of the famous French chemist to some extent supports the supposition that argon is a polymerised variety of nitrogen whose molecule contains N_{3}, while ordinary nitrogen contains N_{2}. Should this supposition be eventually verified, the interest in argon will not only not lessen, but become greater. For this, however, we must wait for further observations and detailed experimental data from Rayleigh and Ramsay.

The latest information obtained by me from London is that Professor Ramsay, by treating cleveite (containing PbO, UO_{3}, Y_{2}O_{3}, &c.) with sulphuric acid, obtained argon, and, judging by the spectrum, helium also. The accumulation of similar data may, after detailed and diversified research, considerably increase the stock of chemical knowledge which, constantly widening, cannot be exhaustively treated in these 'Principles of Chemistry,' although very probably furnishing fresh proof of the 'periodicity of the elements.'

* * * * *

INDEX OF AUTHORITIES

Abasheff, i. 75 Abel, ii. 56, 326, 410 Acheson, ii. 107 Adie, ii. 186 Alexéeff, i. 75, 94 Alluard, i. 458 Amagat, i. 132, 135, 140 Amat, ii. 171 Ammermüller, i. 504 Ampère, i. 309 Andréeff, i. 251 Andrews, i. 136, 203 Angeli, i. 266 Ansdell, i. 451 Arfvedson, i. 575 Arrhenius, i. 89, 92, 389 Aschoff, ii. 313 Askenasy, i. 508 Aubel, ii. 45 Aubin, i. 238 Avdéeff, i. 618; ii. 484 Avogadro, i. 309

Babo, v., i. 93, 200, 203 Bach, i. 394 Bachmetieff, ii. 31 Baeyer, v., i. 507 Bagouski, i. 384 Bailey, i. 449; ii. 29 Baker, i. 318, 403 Balard, i. 480, 494, 495, 505 Ball, ii. 414 Bannoff, i. 506 Barfoed, ii. 53 Baroni, i. 331 Barreswill, ii. 282 Baudrimont, ii. 35 Baumé, i. 193 Baumgauer, ii. 20 Baumhauer, i. 495 Bayer, ii. 76, 159 Bazaroff, i. 409; ii. 24, 68, 486 Becher, i. 17 Becker, i. 16 Beckmann, i. 91, 496; ii. 156 Becquerel, i. 228; ii. 97, 220 Beilby, i. 71 Beilstein, i. 373; ii. 188 Beketoff, i. 120, 122, 124, 146, 403, 459, 466, 534, 541, 574, 577; ii. 87, 102, 289, 429 Bender, i. 476 Benedict, ii. 65 Berglund, ii. 229 Bergman, i. 27, 435; ii. 100 Berlin, i. 95 Bernouilli, i. 81 Bernthsen, ii. 228 Bert, i. 86, 153 Bertheim, ii. 337 Berthelot, i. 171, 173, 189, 199, 229, 230, 258, 264, 266, 267, 272, 83, 289, 351, 372, 393, 394, 405, 415, 424, 438, 457, 463, 502, 506, 507, 518, 529, 537, 582; ii. 23, 57, 207, 209, 251, 253, 259, 345, 367 Berthier, ii. 8 Berthollet, i. 27, 31, 105, 433, 434, 459, 470, 502, 609 Berzelius, i. 131, 148, 194, 255, 379; ii. 8, 100, 102, 147, 148, 219, 281, 300, 485 Besson, i. 288; ii. 67, 70, 105, 179 Beudant, ii. 7, 8 Bineau, i. 100, 271, 452, 504; ii. 239 Binget, i. 75 Blaese, ii. 188 Blagden, i. 91, 428 Blake, ii. 30 Blitz, ii. 184 Blomstrand, ii. 299 Boerwald, ii. 279 Böttger, i. 595 Bogorodsky, i. 574 Boilleau, i. 415 Boisbaudran, L. de, i. 97, 102, 572, 600; ii. 6, 26, 90, 82, 284, 483 Bornemann, i. 509 Botkin, ii. 30 Bouchardat, ii. 45 Boullay, ii. 55 Bourdiakoff, i. 584, 617 Boussingault, i. 131, 157, 233, 235, 525, 615 Boyle, i. 124 Brand, ii. 150 Brandau, i. 481 Brandes, i. 72 Bravais, i. 233 Brauner, i. 490, 491; ii. 26, 59, 94, 96, 97, 134, 144, 194, 271, 483 Brewster, i. 569 Brigham, ii. 193 Brodie, i. 212, 351, 405; ii. 252 Brooke, ii. 357 Brown, i. 81, 88 Brugellmann, i. 616 Brunn, ii. 182, 189 Bruyn, i. 262 Brühl, i. 263, 337 Brunner, i. 124, 146, 263; ii. 230, 309, 534 Buchner, i. 615 Buckton, ii. 143 Buff, ii. 103 Bunge, i. 288 Bunsen, i. 43, 69, 78, 117, 180, 465, 568, 575, 576, 577; ii. 27, 289 Bussy, i. 75, 594, 619 Butleroff, i. 143 Bystrom, i. 585

Cagniard de Latour, i. 135, 345 Cahours, ii. 143, 173 Cailletet, i. 132, 138; ii. 45 Calderon, i. 596 Callender, i. 134 Calvert, i. 484; ii. 45 Cannizzaro, i. 584, 587 Carey-Lea, ii. 420, 424, 425, 432 Carius, i. 69, 481 Carnelley, i. 483, 515, 555; ii. 22, 29, 30, 31, 64, 143, 486 Carnot, ii. 294, 361 Caron, i. 595, 604, 610; ii. 336 Carrara, i. 213 Cass, ii. 85 Castner, i. 431, 535, 541 Cavazzi, ii. 160, 172, 182 Cavendish, i. 113, 125, 228; ii. 493 Chabrié, i. 229 Chappuis, i. 50, 199, 205, 264 Chapuy, i. 59 Cheltzoff, i. 393, 457, 582; ii. 41, 247 Cherikoff, ii. 102 Chertel, ii. 245 Chevillot, ii. 311 Chevreul, i. 530 Chigeffsky, ii. 62 Christomanos, i. 511 Chroustchoff, i. 353, 444; ii. 122 Chydenius, ii. 148, 485 Ciamician, i. 565, 573; ii. 486 Clark, i. 26 Classen, ii. 146 Clausius, i. 81, 93, 140, 142, 212, 309, 491 Clement, i. 494 Clève, ii. 26, 94, 97, 484 Cloez, i. 207, 246, 377 Clowes, i. 242 Collendar, i. 134 Comaille, i. 596 Comb, ii. 81 Connell, i. 508 Coppet, i. 91, 428, 601 Corenwinder, i. 501 Cornu, i. 565 Courtois, i. 494 Cracow, ii. 380 Crafts, i. 380 ; ii. 80, 83 Cremers, ii. 100 Croissier, i. 251 Crompton, i. 247 Crookes, i. 229, 617; ii. 20, 91, 96, 440, 491 Crum, ii. 79, 311 Cundall, i. 611 Curtius, i. 258, 265

Dahl, ii. 59 Dalton, i. 29, 78, 81, 109, 206, 271, 322 Dana, ii. 8 Davies, i. 484 Davy, i. 37, 114, 195, 255, 364, 460, 463, 484, 489, 494, 533, 541, 594, 604, 617 Deacon, i. 599 Debray, i. 609; ii. 45, 122, 291, 293, 384, 385 De Chancourtois, ii. 20, 26 De Forcrand, ii. 106, 211 De Haën, ii. 189 De Heen, i. 140 Delafontaine, ii. 97, 148, 198 De la Rive, i. 198; ii. 226 Del-Rio, ii. 197 De Saussure, i. 235, 240 De Schulten, ii. 48 Deville, St.-Claire, i. 4, 36, 118, 143, 179, 180, 227, 239, 280, 281, 301, 320, 392, 393, 399, 459, 467, 476, 477, 500, 534, 595, 608, 609; ii. 48, 80, 83, 85, 102, 147, 156, 198, 289, 309, 321, 352, 373, 374, 429 De Vries, i. 62, 64, 429 Dewar, i. 3, 5, 135, 139, 163, 297, 563, 565, 569, 585; ii. 176, 220 Dick, ii. 414 Dingwall, i. 486 Ditte, i. 72, 403, 430, 457, 509, 539, 618; ii. 64, 65, 85, 189, 249 Dittmar, i. 100, 452; ii. 240 Divers, i. 274, 294; ii. 54 Dixon, i. 171 Döbereiner, i. 145 Dokouchaeff, i. 344 Donny, i. 534 Dossios, i. 502 Draper, i. 465 Drawe, ii. 161 Drebbel, i. 294 Dulong, i. 131, 148, 437 Dumas, i. 28, 131, 148, 150, 233, 302, 320, 379, 471, 476, 584, 586, 604; ii. 22, 37, 62, 101, 156, 420 Dumont, ii. 197

Ebelmann, ii. 65 Eder, i. 566 Edron, ii. 95 Edwards, ii. 311 Egoreff, i. 569 Eissler, i. 553 Elbers, ii. 221 Emich, i. 286, 287 Emilianoff, ii. 126 Engel, i. 457; ii. 130, 132, 189, 206 Engelhardt, i. 530 Eötvös, i. 333 Erdmann, i. 150 Ernst, i. 399 Eroféeff, i. 352 Esson, ii. 314 Étard, i. 72, 516, 615; ii. 288, 335, 356 Ettinger, i. 53, 312

Famintzin, i. 611 Faraday, i. 134, 177, 296, 385, 463, 464 Favorsky, i. 373 Favre, i. 120, 172, 267, 582; ii. 83, 259, 284, 380 Fick, i. 62 Fisher, ii. 424 Fizeau, ii. 31, 429 Flavitzky, i. 21 Fleitmann, ii. 170 Foerster, ii. 375, 389 Forchhammer, ii. 311 Fordos, ii. 257 Fortmann, ii. 230, 366 Fourcroy, i. 114 Fowler, i. 449 Frank, ii. 88 Franke, ii. 311, 313 Frankel, ii. 294 Frankenheim, ii. 7 Frankland, i. 178, 357, 486; ii. 16, 143 Fraunhofer, i. 563 Frémy, i. 228, 489, 492; ii. 74, 131, 133, 142, 229, 290, 359 Freyer, i. 171, 488 Friedheim, ii. 197, 294 Friedel, i. 353, 472; ii. 80, 83, 103, 122 Friedrich, i. 49; ii. 144 Fritzsche, i. 94, 285, 600, 612; ii. 125, 218, 280, 341 Fromherz, ii. 313 Fürst, i. 484

Galileo, i. 7 Garni, i. 582 Garzarolli-Thurnlackh, i. 481 Gattermann, i. 596; ii. 102, 104 Gautier, i. 585 Gavaloffsky, i. 160 Gay-Lussac, i. 40, 61, 71, 93, 170, 302, 307, 406, 412, 460, 463, 464, 467, 500, 506, 508, 511, 515, 534, 539; ii. 8, 56, 256 Geber, i. 17 Gélis, ii. 257 Genth, ii. 359 Georgi, ii. 197 Georgiewics, ii. 64 Gerberts, i. 528 Gerhardt, i. 196, 309, 357, 388 Gerlach, i. 525 Gernez, i. 97; ii. 205 Geuther, i. 281, 283, 285; ii. 176 Gibbs, i. 140, 464; ii. 293, 410 Girault, i. 498 Gladstone, i. 337, 438, 573; ii. 213 Glatzel, ii. 213, 289, 309 Glauber, i. 17, 26, 193, 432 Glinka, i. 607 Goldberg, i. 93 Gooch, i. 484 Gore, i. 489, 492, 493 Graham, i. 62, 63, 98, 143, 155, 388, 429, 518, 601; ii. 77, 114, 131, 163, 170, 296, 307 Granger, ii. 157, 410 Grassi, i. 88 Green, ii. 310 Greshoff, i. 403 Griffiths, i. 135 Grimaldi, i. 537 Groth, ii. 10 Grouven, i. 615 Grove, i. 118, 119 Grünwald, i. 573 Grützner, ii. 296 Guckelberger, ii. 84 Guibourt, ii. 53 Guldberg, i. 439, 464 Güntz, i. 575; ii. 430 Gustavson, i. 443, 444, 472, 505, 547; ii. 29, 175 Guthrie, i. 99, 428, 601 Guy, i. 136

Habermann, ii. 210 Hagebach, i. 573 Hagen, i. 337 Haitinger, i. 593 Hammerl, i. 613 Hanisch, ii. 233 Hannay, i. 352; ii. 135 Harcourt, ii. 314 Hargreaves, i. 515 Harris, ii. 52 Hartley, i. 573; ii. 486 Hartog, ii. 268 Hasselberg, i. 566 Haüy, ii. 7 Haughton, ii. 20 Häussermann, i. 483 Hautefeuille, i. 199, 205, 264, 409, 414, 476, 477, 501, 538; ii. 102, 122, 379 Hayter, ii. 175 Hemilian, i. 132 Hempel, i. 59, 524 Henkoff, i. 530 Henneberg, ii. 170 Henning, ii. 3 Henry, i. 78, 81 Hérard, ii. 191 Hermann, ii. 8, 47, 197 Hermes, i. 529 Hertz, ii. 156 Hess, i. 178, 588 Heycock, i. 537; ii. 128, 448 Hillebrand, ii. 26, 93, 94, 484 Hintze, ii. 10 Hirtzel, ii. 55 Hittorf, ii. 155 Hodgkinson, ii. 432 Höglund, ii. 94 Hofmann, i. 302; ii. 146, 218, 447 Holtzmann, i. 505 Hoppé-Seyler, i. 611 Horstmann, i. 408 Houzeau, i. 202 Hughes, ii. 212 Hugo, ii. 21 Humboldt, i. 170 Humbly, i. 493; ii. 311 Hutchinson, i. 491 Huth, ii. 20 Huyghens, i. 569

Ikeda, ii. 152 Ilosva, i. 202 Inostrantzeff, i. 345; ii. 4 Isambert, i. 250, 257, 408; ii. 41 Ittner, i. 412

Janssen, i. 569 Jawein, ii. 170 Jay, i. 258 Jeannel, i. 104 Joannis, i. 251, 255, 405, 537, 559 Jörgensen, i. 498; ii. 359, 361, 376 Johnson, ii. 45 Jolly, i. 233 Joly, ii. 384, 385

Kamensky, ii. 414 Kammerer, i. 286, 462, 509; ii. 297 Kane, ii. 57 Kapoustin, i. 403 Karsten, i. 427, 428, 541, 599 Kassner, i. 158 Kayander, i. 133, 384; ii. 46 Keiser, i. 150 Kekulé, i. 358, 369, 507; ii. 294 Keyser, ii. 33 Khichinsky, i. 440 Kimmins, i. 510 Kirchhoff, i. 567 Kirmann, ii. 268 Kirpicheff, i. 132 Kjeldahl, i. 249; ii. 249 Klaproth, ii. 7, 145, 147, 301 Kleiber, i. 570 Klimenko, i. 465 Klobb, ii. 357 Klodt, i. 426 Knopp, ii. 338 Knox, i. 489 Kobb, ii. 125 Kobell, ii. 197 Koch, i. 44 Kohlrausch, i. 245, 525 Kolbe, i. 506 Kolotoff, i. 263 Konovaloff, i. 39, 65, 90, 93, 100, 140, 142, 172, 322; ii. 235, 268 Kopp, i. 586, 587, 612; ii. 3, 37 Koucheroff, i. 373 Kouriloff, i. 209, 247, 274; ii. 41 Kournakoff, i. 393; ii. 294, 365, 396 Kraevitch, i. 133, 134 Kraft, i. 65, 88, 537 Krafts, i. 393 Kreisler, i. 233 Kremers, i. 87, 443; ii. 244, 427 Kreider, i. 484 Krönig, i. 81 Krüger, ii. 282, 284 Krüss, ii. 355, 442, 447, 486 Kubierschky, ii. 213 Kühlmann, i. 608 Kuhnheim, i. 612 Kundt, i. 328, 589; ii. 496 Kvasnik, ii. 57 Kynaston, i. 522 Lachinoff, i. 116, 457; ii. 410 Ladenburg, ii, 103 Lamy, ii. 91 Landolt, i. 7, 337 Lang, i. 399 Langer, i. 226, 459, 462 Langlois, i. 570 ; ii. 257 Latchinoff (see Lachinoff), i. 103, 352 Laurent, i. 28, 196, 388, 471, 526; ii. 7, 9, 10, 117, 292 Laurie, i. 106; ii. 32, 442, 486 Lavenig, i. 140 Lavoisier, i. 7, 29, 49, 114, 131, 155, 379, 459 Leblanc, ii. 8 Le Chatelier, i. 158, 172, 350, 393, 399, 585, 588, 611; ii. 51, 65, 420 Le Duc, i. 131, 170 Lémery, i. 125 Lemoine, i. 501; ii. 155 Lerch, i. 405 Leroy, i. 285 Lesc[oe]ur, i. 103 Leton, ii. 425 Levy, ii. 102 Lewes, i. 371 Lewy, i. 232 Lidoff, ii. 209 Liebig, i. 195, 388, 495, 527; ii. 56 Linder, ii. 223 Liés-Bodart, i. 604, 612 Lisenko, i. 373 Liveing, i. 563, 569 Lockyer, i. 565, 569 Loew, ii. 376 Löwel, i. 525, 600; ii. 45, 284, 286 Loewig, i. 528; ii. 77 Loewitz, i. 96 Lossen, i. 262 Louget, i. 489 Louguinine, i. 360 Louise, ii. 81 Lovel, i. 515; ii. 338 Lubavin, i. 593 Lubbert, ii. 85, 170 Ludwig, i. 463 Luedeking, ii. 194 Luff, ii. 321 Lunge, ii. 244, 246 Lüpke, ii. 157 Lvoff, i. 358

Maack, i. 596 Mac Cobb, i. 612 Mac Laurin, i. 553 McLeod, ii. 180 Magnus, i. 93, 510 Mailfert, i. 199 Malaguti, i. 437; ii. 300 Mallard, i. 172, 393, 588; ii. 4 Mallet, i. 493 Maquenne, i. 349, 620, 621 Marchand, i. 150 Marchetti, ii. 288 Maresca, i. 534 Marguerite, ii. 292 Marignac, i. 198, 233, 428, 430, 453, 454, 518, 525, 600, 601; ii. 6, 9, 95, 101, 194, 197, 198, 199, 234, 239, 241, 244, 292, 293, 295, 357, 440, 486 Markleffsky, i. 273 Markovnikoff, i. 373 Maroffsky, ii. 138 Marshall, ii. 253, 365 Matigon, i. 258, 266 Maumené, i. 258 Maxwell, i. 81 Mayow, i. 17 Mendeléeff, i. 99, 132, 133, 136, 141, 275, 321, 357, 373, 377, 406, 426, 427, 428, 506, 587, 596; ii. 27, 33, 93, 94 Menschutkin, i. 171 Mente, ii. 270 Mermé, i. 462 Merz, i. 505 Meselan, i. 463 Metzner, ii. 189 Metchikoff, i. 44 Meusnier, i. 114 Meyer (Lothar), i. 226, 321, 403; ii. 21, 24, 26, 29, 33, 486 Meyer (Victor), i. 135, 171, 294, 303, 320, 427, 459, 462, 467, 488, 506, 508, 558; ii. 43, 48, 52, 80, 129, 184 Meyerhoffer, ii. 410 Miasnikoff, i. 372 Michaelis, ii. 175 Michel, i. 65, 88 Millon, i. 481, 484, 508 Mills, ii. 20 Mitchell, i. 156 Mitscherlich, i. 428, 527; ii. 1, 5, 8, 156, 184, 311, 313 Moissan, i. 202, 349, 353, 490, 564, 585, 621; ii. 66, 67, 70, 88, 100, 107, 147, 174, 196, 289, 295, 309, 311, 313, 321 Mond, i. 129, 400, 405; ii. 345, 367 Monge, i. 114 Monnier, i. 611 Montemartini, i. 279 Moraht, ii. 384 Moreau, ii. 298 Morel, i. 549 Mosander, ii. 97 Mühlhäuser, ii. 66, 107 Muir, ii. 193 Mulder, i. 515 Müller-Erzbach, i. 103 Müller, i. 427; ii. 425 Munster, ii. 443 Müntz, i. 238, 241, 420, 553 Muthmann, ii. 273 Mylius, ii. 375, 389

Naschold, i. 483 Nasini, i. 496; ii. 156 Natanson, i. 282, 409 Natterer, i. 132, 135, 141, 385 Naumann, i. 399, 408 Nernst, i. 62, 148; ii. 3, 50 Nensky, i. 245 Neville, i. 537; ii. 128, 448 Newlands, ii. 21, 26 Newth, i. 505 Newton, i. 7, 29 Nicklès, ii. 10 Nikolukin, i. 491; ii. 144 Nilson, i. 618; ii. 26, 37, 80, 83, 91, 94, 95, 271, 378, 483 Nordenskiöld, i. 241 Norton, i. 76; ii. 94 Nuricsán, ii. 264

Odling, ii. 52 Offer, i. 99 Ogier, i. 321, 509; ii. 159, 182 Olszewski, i. 139, 569; ii. 491, 497 Oppenheim, i. 506 Ordway, ii. 80 Osmond, ii. 326 Ossovetsky, ii. 137 Ostwald, i. 89, 92, 389, 441, 443 Oumoff, i. 62

Pallard, i. 491; ii. 83 Panfeloff, i. 603 Paracelsus, i. 17, 125, 129, 379 Parkinson, i. 596, Pashkoffsky, i. 595 Pasteur, i. 44, 241, 242 Paterno, i. 496; ii. 156 Pattison Muir, i. 436 Pebal, i. 315, 484 Péchard, ii. 282, 294, 296, 297 Pekatoros, i. 465 Peligot, ii. 299, 301 Pelopidas, ii. 22, 481 Pelouze, i. 463, 464, 480, 610; ii. 229 Penfield, i. 545; ii. 370 Perkin, i. 558; ii. 244 Perman, i. 537 Personne, i. 75, 506, 537 Petit, i. 584, 586 Petrieff, i. 440 Pettenkofer, ii. 22 Pettersson, i. 618, 619; ii. 37, 80, 83, 91, 197, 484 Pfaundler, i. 445; ii. 241, 430 Pfeiffer, i. 64 Pfordten, V. der, ii. 420 Phipson, i. 596; ii. 59 Piccini, ii. 23, 146, 197, 288, 298 Pici, ii. 57 Pickering, i. 88, 91, 99, 104, 106, 272, 333, 452, 517, 525, 529, 613; ii. 241, 245, 246, 247 Pictet, i. 81, 129, 137; ii. 31, 241 Picton, ii. 223 Pierre, i. 452, 495; ii. 226, 485 Pierson, i. 93 Pigeon, ii. 377 Pionchon, i. 585 Pistor, i. 399 Plantamour, ii. 5 Plaset, ii. 289 Plessy, ii. 257 Plücker, i. 572 Poggiale, i. 427 Poiseuille, i. 355 Poleck, ii. 296 Poluta, ii. 30 Popp, ii. 232 Potilitzin, i. 96, 97, 98, 445, 486, 499, 502, 509, 612; ii. 29, 357 Pott, ii. 100 Poulenc, ii. 174, 289 Prange, ii. 422 Prelinger, ii. 310 Priestley, i. 17, 154, 159, 297, 379, 402 Pringsheim, i. 465 Prost, i. 98, 486 Prout, i. 31; ii. 439 Puchot, i. 452 Pullinger, ii. 389

Quincke, i. 427, 495

Rammelsberg, i. 430, 510, 525; ii. 26, 161, 485 Ramsay, i. 133, 140, 141, 232, 247, 333, 495, 496, 581; ii. 128, 491 Rantsheff, ii. 20 Raoult, i. 91, 274, 330, 331, 332, 429 Rascher, ii. 85 Raschig, i. 263; ii. 229 Rathke, i. 399 Ray, i. 17 Rayleigh, i. 226, 232, 491 Rebs, ii. 213, 217 Recoura, i. 332; ii. 289 Regnault, i. 40, 53, 54, 90, 93, 131, 133, 297, 443, 495, 584, 587, 588; ii. 50, 208, 238 Reich, ii. 91 Reiset, i. 238 Remsen, ii. 335 Retgers, ii. 157, 158, 180 Reychler, ii. 65 Reynolds, i. 581 Richards, i. 526, 585; ii. 32, 432 Riche, i. 509; ii. 127, 292 Richter, i. 193, 194; ii. 91 Ridberg, ii. 21, 24, 486 Riddle, i. 135 Rideal, ii. 297 Roberts-Austen, ii. 486 Robinson, i. 515 Rodger, ii. 213, 263 Rodwell, i. 17 Roebuck, i. 294 Röggs, ii. 119 Rohrer, ii. 343 Roozeboom, i. 106, 452, 453, 464, 496, 506, 511, 599, 613; ii. 3, 226, 341, 410 Roscoe, i. 80, 100, 101, 379, 452, 463, 485, 486, 568, 572; ii. 26, 194, 196, 197, 297, 303, 485 Rose, i. 436, 437, 518, 525, 608, 612; ii. 8, 230, 235, 248, 281, 363, 428, 485 Rosenberg, ii. 351 Rossetti, i. 428 Rouart, Le, ii. 86 Rousseau, i. 354; ii. 337, 366, 378 Roux, ii. 81 Rudberg, ii. 136 Rücker, i. 142 Rüdorff, i. 91, 428, 598, 601 Rybalkin, i. 455

Sabanéeff, i. 371 Sabatier, i. 284; ii. 66 Saint Edmé, ii. 335 Saint Gilles, i. 431 Sakurai, i. 331 Salzer, ii. 161 Sarasin, ii. 122 Sarrau, i. 140, 142 Saunders, ii. 189 Scharples, i. 576 Scheele, i. 155, 161, 412, 459, 462, 608; ii. 100, 150, 291 Scheffer, i. 453 Scheibler, ii. 292, 296 Scherer, ii. 8 Schiaparelli, ii. 318 Schidloffsky, i. 238 Schiloff, i. 212 Schlamp, i. 332 Schiff, i. 430, 588; ii. 106, 267 Schloesing, i. 238, 239, 240, 553, 610 Schmidt, i. 539 Schneider, i. 89 Schöne, i. 208, 209, 211, 394, 617; ii. 15, 72, 219, 251, 488 Schönebein, i. 198, 202, 208, 212, 509; ii. 228, 463 Schottländer, ii. 447 Schröder, i. 75 Schroederer, ii. 366 Schrötter, ii. 153, 284 Schützenberger, i. 511, 579; ii. 102, 107, 228, 367, 389 Schuliachenko, i. 608 Schuller, ii. 180 Schultz, i. 518; ii. 273 Schulze, i. 98; ii. 215 Schuster, i. 572 Schwicker, ii. 227, 230 Scott, i. 405, 537, 558 Sechenoff, i. 80, 86 Seelheim, ii. 379 Sefström, ii. 197 Selivanoff, i. 476, 507, 508 Senderens, i. 284 Serullas, i. 485 Setterberg, i. 576 Seubert, ii. 27, 83, 343, 442 Sewitsch, i. 372 Shaffgotsch, i. 555 Shapleigh, ii. 95 Shenstone, i. 611 Shields, i. 333 Shishkoff, i. 276; ii. 56 Silberman, i. 120, 172; ii. 259 Sims, ii. 268 Skraup, ii. 346 Smith, i. 271 Smithson, ii. 100 Snyders, ii. 100 Sokoloff, ii. 85, 122 Solet, i. 509 Sonstadt, ii. 443 Sorby, i. 88 Soret, i. 66, 202, 203, 427 Spring, i. 38, 98, 434, 486; ii. 45, 50, 133, 223, 258, 288, 314, 423, 427 Stadion, i. 485 Stahl, i. 16 Stas, i. 7, 233, 379, 428, 498, 581; ii. 420, 434, 485 Staudenmaier, ii. 168 Stcherbakoff, i. 97, 428, 458, 601 Stohmann, i. 359, 360, 396 Stokes, i. 355 Stortenbeker, i. 511 Stromeyer, ii. 47 Struvé, i. 208, 612

Tait, i. 203 Tammann, i. 91, 148; ii. 170, 247 Tanatar, i. 511 Tchitchérin, ii. 21 Terreil, ii. 313 Than, i. 317 Thénard, i. 207, 229, 460, 464, 534, 539; ii. 251 Thillot, ii. 170 Thilorier, i. 385 Thomsen, i. 111, 120, 124, 131, 173, 189, 267, 359, 389, 396, 441, 453, 466, 472, 494, 502, 515, 529, 555, 582; ii. 9, 32, 50, 55, 105, 165, 208, 224, 264, 368, 370, 438, 442 Thorpe, i. 142, 285, 445, 493; ii. 27, 160, 173, 213, 259, 263, 268, 301, 313, 442, 486 Thoune, i. 294, 295 Tiemman, i. 213 Tilden, i. 516 Timeraséeff, i. 170 Timoféeff, i. 78 Tessié du Motay, i. 158 Tissandier, i. 78 Titherley, i. 539 Tivoli, ii. 183 Tomassi, ii. 339 Topsöe, i. 506 Tourbaba, i. 88; ii. 247 Trapp, i. 511 Traubé, i. 312, 611; ii. 270 Troost, i. 64, 274, 281, 320, 409, 414, 500, 538; ii. 80, 83, 102, 147, 156, 254, 379 Tscherbacheff, i. 577 Tutton, i. 543; ii. 160, 174, 412

Umoff, i. 429 Unverdorben, ii. 280 Urlaub, ii. 301

Valentine, i. 17 Van der Heyd, i. 599 Van der Plaats, i. 496; ii. 438 Van der Waals, i. 82, 140 Van Deventer, i. 599 Van Helmont, i. 379 Van Marum, i. 198 Van't Hoff, i. 64, 65, 331, 599; ii. 3 Vare, ii. 55 Vauquelin, i. 114, 619; ii. 7 Veeren, i. 612; ii. 45 Veley, i. 279 Verneuille, ii. 225 Vernon, ii. 151 Vèzes, ii. 391 Viard, ii. 285 Vignon, ii. 126, 131 Villard, i. 106, 296, 297 Villiers, ii. 259 Violette, i. 342, 345 Violle, i. 301 Vogt, i. 611 Volkovitch, ii. 201 Voskresensky, i. 345

Waage, i. 439 Wachter, i. 508 Wagner, i. 357 Wahl, ii. 310 Walden, ii. 57 Walker, ii. 143 Walmer, i. 573 Walter, ii. 256 Walters, ii. 234 Wanklyn, i. 100, 539 Warburg, i. 589; ii. 496 Warder, i. 450 Warren, ii. 102 Watson, i. 527; ii. 169 Watts, i. 526 Weber, i. 280, 583; ii. 83, 129, 131, 186, 230, 233, 234, 249 Weith, i. 502 Weitz, ii. 57 Welch, ii. 425 Weller, ii. 146 Wells, i. 477, 545; ii. 57, 370 Welsbach, ii. 96, 97 Weltzien, i. 204, 595 Wenzel, i. 193 Weruboff (see Wyruboff), ii. 4 Weselski, i. 507 Weyl, i. 255 Wheeler, i. 545 Wichelhaus, ii. 179 Wiedemann, i. 439, 588 Wilhelmj, ii. 315 Willgerodt, i. 508; ii. 29 Williamson, ii. 268 Wilm, ii. 376, 388 Winkler, i. 78, 79, 577, 594, 621; ii. 25, 30, 66, 97, 102, 124, 125, 147, 234, 246, 355, 483 Wischin, ii. 384 Wislicenus, i. 267, 294 Witt, ii. 3 Wöhler, i. 410, 619; ii. 85, 103, 107, 146, 285, 289, 420, 425 Wollaston, i. 8 Wreden, i. 507 Wright, ii. 321 Wroblewski, i. 79, 80, 106, 139, 387; ii. 226 Wülfing, ii. 119 Wülner, i. 91, 572 Würtz, i. 301, 476; ii. 171, 173, 213, 267 Wyruboff, ii. 4, 9

Young, i. 134, 136, 140, 141, 247, 495, 496

Zaboudsky, i. 354 Zaencheffsky, i. 140 Zimmermann, ii. 26, 303, 355, 485 Zinin, i. 276 Zörensen, i. 284 Zorn, i. 295

* * * * *

SUBJECT INDEX

Acid, acetic sp. gr. of solutions of, i. 59 -- arsenic, ii. 181 -- bismuthic, ii. 190 -- boric, ii. 64 -- carbamic, i. 408 -- chamber, i. 294 -- chloric, i. 482 -- chloroplatino-phosphorous, ii. 390 -- chlorosulphonic, ii. 268 -- chlorous, i. 481 -- chromic, i. 208; ii. 282 -- chromo-sulphuric, ii. 288 -- cyanic, i. 409 -- cyanuric, i. 409 -- dithionic, ii. 256 -- ferric, ii. 344 -- fluoboric, ii. 69 -- graphitic, i. 351 -- hydriodic, i. 501, 503, 505, 506 -- hydroborofluoric, ii. 69 -- hydrobromic, i. 80, 503, 505, 506 -- hydrochloric, i. 448, 451, 453 -- hydrocyanic, i. 406, 411 -- hydroferrocyanic, ii. 348 -- hydrofluoric, i. 49 -- hydrofluosilic, ii. 106 -- hydroplatinocyanic, ii. 386 -- hydrosulphurous, ii. 228 -- hydroruthenocyanic, ii. 388 -- hypochlorous, i. 479, 481 -- hyponitrous, i. 265, 294 -- hypophosphoric, ii. 161 -- hypophosphorous, ii. 172 -- iodic, i. 100, 508 -- isethionic, ii. 250 -- metantimonic, ii. 188 -- metaphosphoric, ii. 162, 169 -- metastannic, ii. 131 -- molybdic, ii. 292 -- nitric, i. 268, 272 -- Nordhausen, ii. 233 -- orthophosphoric, ii. 162 -- osmic, ii. 384 -- pentathionic, ii. 257 -- percarbonic, i. 394 -- perchloric, i. 484 -- periodic, i. 510 -- permanganic, ii. 313 -- permolybdic, ii. 297 -- pernitric, i. 264 -- persulphuric, ii. 251 -- pertungstic, ii. 297 -- phosphamic, ii. 179 -- phosphamolybdic, ii. 293 -- phosphorous, ii. 171 -- polysilicic, ii. 117 -- pyrophosphoric, ii. 169 -- pyrosulphuric, ii. 234 -- silenic, ii. 272 -- silicotungstic, ii. 295 -- stannic, ii. 130 -- sulphonic, ii. 249 -- sulphuric, i. 76, 77, 89, 111, 290, 294; ii. 235, 238, 241 -- telluric, ii. 272 -- tetrathionic, ii. 257 -- thiocarbonic, ii. 263 -- thiocyanic, ii. 263 -- thionic, ii. 255 -- thiosulphuric, ii. 230 -- trithionic, ii. 257 -- tungstic, ii. 292, 294 -- vanadic, ii. 196 Acids, i. 185 -- avidity of, i. 389, 442 -- basicity of, i. 387 -- complex, i. 197; ii. 293 -- fuming, i. 102 -- organic, i. 394, 396, 405 Acetylene, i. 372 Actinium, ii. 59 Affinity, chemical, i. 26, 389 Air, i. 131, 231, 233 Alchemy, i. 14 Alcohol, i. 53, 88 Alkali, metals, i. 558, 577 -- waste, ii. 204 Alkalis, i. 186 Allotropism, i. 207 Alloys, i. 537; ii. 128 Alumina, ii. 75 Aluminium, ii. 70, 85 -- bromide, ii. 84 -- bronze, ii. 88 -- carbide, ii. 88 -- chloride, ii. 80, 83 -- double chlorides, ii. 84 -- fluoride, ii. 83 -- hydroxide, ii. 75 -- iodide, ii. 85 -- nitrate, ii. 80 -- sulphate, ii. 82 Alums, ii. 5, 82, 343 Alunite, ii. 80 Amalgams, ii. 58 Amides, i. 258, 406 Amidogen, i. 258 -- hydrate, i. 258 Amines, i. 416 Ammonia, i. 229, 246 -- of crystallisation, i. 257 -- heat of solution of, i. 74 -- in air, i. 240 -- liquefaction of, i. 250 -- salts, i. 254 -- soda process, i. 524 -- solutions of, i. 80, 252 Ammonium, i. 254 -- amalgam, i. 255 -- bicarbonate, i. 527 -- carbamate, i. 407, 408 -- carbonate, i. 407 -- cobalt salts, ii. 359 -- dichromate, ii. 279 -- molybdate, ii. 292 -- nitrate, i. 273, 274 -- nitrite, i. 284 -- phosphates, ii. 167 -- sulphate, ii. 269 -- sulphide, ii. 218 Analogy of elements, i. 573, 578 Anthracite, i. 345 Antimoniuretted hydrogen, ii. 189 Antimony, ii. 186 -- chlorides, ii. 189 -- oxides, ii. 187, 188 -- sulphides, ii. 221 Aqua Regia, i. 467 Aqueous radicle, i. 213 Argon, i. 226, 232; App. III. Arsenic, ii. 179 -- anhydride, ii. 181 -- sulphides, ii. 221 -- tribromide, ii. 181 -- trichloride, ii. 180 -- trifluoride, ii. 181 Arsenious anhydride, ii. 184 -- oxychloride, ii. 180 Arsenites, ii. 185 Arseniuretted hydrogen, ii. 182 Astrakhanite, i. 59 Atmolysis, i. 156 Atomic theory, i. 216 -- volumes, ii. 33 -- weights, i. 21 Atoms and molecules, i. 322

Barium, i. 614, 617 -- chlorate, i. 483 -- chloride, i. 615 -- hydroxide, i. 616 -- metatungstate, ii. 295 -- nitrate, i. 615 -- oxide, i. 616 -- peroxide, i. 157, 160, 209, 617 -- sulphate, i. 614, 615 Bauxite, ii. 76 Benzalazine, i. 258 Berthollet's doctrine, i. 433 Beryllium, i. 618 -- atomic weight of, i. 325, 618 -- chloride, i. 584 -- oxide, i. 619 Binary theory, i. 195 Bismuth, ii. 189 -- nitrates, ii. 192 -- oxides, ii. 190, 191 Blast furnace, ii. 324 Bleaching, i. 469 -- powder, i. 162, 477 Boiling point, absolute, i. 130 Borates, ii. 63 Borax, ii. 61 Boric anhydride, ii. 64 Boron, ii. 60, 66 -- chloride, ii. 69 -- fluoride, ii. 67, 68 -- iodide, ii. 70 -- nitride, i. 227; ii. 67 -- oxide, ii. 60 -- specific heat of, i. 585 -- sulphide, ii. 62 Bromides, ii. 32 Bromine, i. 494 Bronze, ii. 127 Butyl alcohol, solubility of, i. 75

Cadmium, ii. 47 -- iodide, ii. 48 -- oxide, ii. 48 -- sulphide, ii. 47 Cæsium, i. 576 Calcium, i. 590, 604 -- carbonate, i. 592, 608, 609, 610 -- chloride, i. 237, 612 -- -- crystallohydrates of, i. 613 -- fluoride, i. 491 -- hypochlorite, i. 162 -- iodide, i. 604 -- peroxide, i. 607 -- phosphate, ii. 167 -- sulphate, i. 611 -- sulphide, ii. 220 Calomel, ii. 54 Carbamide, i. 409 Carbides, i. 349, 353 Carbon, i. 338 -- bisulphide, ii. 258 -- molecule of, i. 354 -- oxysulphide, ii. 264 -- tetrachloride, i. 473 Carbonic anhydride, i. 379 -- -- assimilation of by plants, i. 393 -- -- dissociation of, i. 392, 393, 399 -- -- in air, i. 238, 242 -- -- liquid, i. 385 -- -- solutions of, i. 80, 86 -- -- specific heat of, i. 393 Carbonic oxide, i. 396 -- -- and nickel, i. 405 Carborundum, ii. 107 Carboxyl, i. 395 Carnallite, i. 421, 544, 560 Catalytic phenomena, i. 211 Caustic potash, i. 550 -- soda, i. 529 Cements, ii. 122 Cerite metals, ii. 93 Cerium, ii. 93 Chamber crystals, i. 290; ii. 230 Charcoal, i. 343 Chemical change, rate of, ii. 314 -- transformations, i. 3 Chloranhydrides, i. 468; ii. 174, 175, 177 Chlorates, i. 482 Chlorides, i. 455, 466; ii. 31 Chlorine, i. 463 -- compounds, heat of formation of, i. 44 -- crystallohydrates of, i. 464 -- oxides, i. 479 -- preparation of, i. 460 -- solubility of, i. 463 Chloroform, i. 473 Chlorophosphamide, ii. 179 Chloryl compounds, i. 476 Chrome alum, ii. 283 Chromic acid, i. 208 -- anhydride, ii. 280 -- oxide, ii. 284, 285 Chromium, ii. 276, 289 -- chlorides, ii. 285 -- fluorides, ii. 280, 289 Chromyl chloride, ii. 281 Chryseone, ii. 108 Clay, ii. 70 Coal, i. 345 Cobalt, ii. 353 -- dioxide, ii. 366 -- fluoride, ii. 358 Cobaltamine salts, ii. 359 Cobaltic oxide, ii. 362 Cobalto-amine, ii. 359 Cobaltous hydroxide, ii. 358 Cohesion of liquids, i. 52 Coke, i. 345 Collodion cotton, i. 275 Colloids, i. 63; ii. 77, 423 Combination, chemical, i. 3 Combining weights, i. 21; ii. 439 Combustion, imperfect, i. 341 -- heat of, i. 172, 176, 399, 400 Compounds, definite and indefinite, i. 31 -- types of, ii. 10 Compressibility of solutions, i. 88 Conductivity, electro-molecular, i. 389 Contact reactions, i. 163, 290 Copper, ii. 400 -- carbonate, ii. 411 -- complex salts of, ii. 412 -- nitrate, ii. 411 -- nitride, ii. 409 -- sulphate, ii. 413 Corundum, ii. 75 Critical points, i. 141 Cryohydrates, i. 99 Cryoscopic investigations of solutions, i. 90, 332 Crystals, i. 51 Crystalline form, ii. 7 Crystallo-hydrates, i. 102 Crystalloids, i. 63 Cupellation, ii. 417 Cyanides, i. 406 Cyanogen, i. 406, 414 -- chloride, ii. 176

Decomposition, chemical, i. 4 Deliquescence, i. 104 Delta metal, ii. 414 Desiccator, i. 58 Detonating gas, i. 115, 170, 173 Depression of freezing point of solutions, i. 90, 92, 330 Dialysis, i. 63; ii. 114 Diamond, i. 350, 353 Didymium, ii. 93 Diffusion, rate of, i. 63 Dimorphism, i. 610, ii. 178 Disinfectants, i. 245 Disodium orthophosphate, ii. 166 Dissociation, i. 36, 282, 608 Distillation, dry, i. 4, 247, 342 Dust, atmospheric, i. 241

Efflorescence, i. 103 Ekacadmium, ii. 59 Ekasilicon, ii. 25 Electro-chemical theory, i. 195 Electric energy and thermal units, i. 582 Electrolysis, i. 116 Elements, i. 20 -- grouping of, ii. 1 -- typical, ii. 19 Emulsions, i. 98 Energy, chemical, i. 29 Equations, chemical, i. 278 Equivalents, law of, i. 194 Equivalent weights, i. 581 Ethane, i. 366 Ether, critical points of, i. 141 Ethylene, i. 370 Ethyl silicates, i. 104 Euchlorine, i. 484 Eudiometer, i. 169 Expansion, linear, of elements, ii. 31 Explosion, rate of transmission of, i. 171 Explosives, i. 275, 276

Felspar, ii. 122 Fermentation, i. 242 Ferric chloride, i. 558; ii. 340 -- hydrates, ii. 339 -- nitrate, ii. 340 -- orthophosphate, ii. 342 -- oxide, ii. 339 Ferrous chloride, ii. 335 -- sulphate, ii. 335 -- -- solubility of, i. 72 -- sulphide, ii. 210 Flame, i. 177, 179 Fluoborates, ii. 69 Fluorides, i. 491, 493 Fluorine, i. 203, 489 Fluorspar, i. 491 Formula, chemical, i. 151, 326 Freezing mixtures, i. 76 Fuel, calorific capacity of, i. 360 Furnace, electrical, i. 352 Fusco-cobaltic salts, ii. 360

Gadolinite metals, ii. 93 Gallium, ii. 88, 90 Gas, illuminating, i. 361 -- producers, i. 397 Gases, absorption of, i. 348 -- diffusion of, i. 83 -- expansion of, i. 133 -- liquefaction of, i. 134, 135, 137 -- measurement of, i. 78, 300 -- solution of, i. 68, 78, 86 -- theory of, i. 81, 83, 140 Germanium, ii. 26, 124 -- chloride, ii. 125 -- oxide, ii. 125 Glass, i. 123 -- soluble, ii. 110 Glauber's salt, i. 517 Glycols, ii. 117 Gold, ii. 442 -- alloys, i. 446, 447 -- chlorides, ii. 448, 450 -- colloid, ii. 447 -- cyanide, ii. 450 -- extraction of, ii. 444, 445 -- fulminating, ii. 450 -- oxides, ii. 448 -- refining, ii. 446 Graduators, i. 424 Graphite, i. 350, 351 Gros' salt, ii. 393 Guignet's green, ii. 285 Gunpowder, i. 557 Gypsum, i. 593, 611

Halogens, i. 445, 487, 499 Halogen compounds, heat of formation of, i. 494, 502; ii. 32 -- -- boiling-points of, i. 502 Hausmannite, ii. 10 Helium, i. 570; ii. 498 Hemimorphism, ii. 9 Homeomorphism, ii. 8 Homologous compounds, i. 358 Humus, i. 344 Hydrates, i. 109, 185 Hydrazine, i. 258 Hydrides, i. 621; ii. 23 Hydrocarbons, i. 355, 359 Hydrogen, i. 123, 129, 130, 142, 143, 146 -- pentasulphide, ii. 217 -- peroxide, i. 207, 312 Hydrosols, i. 98 Hydroxyl, i. 192, 213 Hydroxylamine, i. 262 Hypochlorites, i. 481 Hyponitrites, i. 294

Imides, i. 258 Indium, ii. 27, 37, 88, 97 Iodates, i. 509 Iodides, ii. 32 -- of nitrogen, i. 507 Iodine, i. 320, 321, 496, 497, 498 -- chlorides of, i. 511 Iodosobenzol, i. 508 Iridious oxide, ii. 382 Iridium, ii. 382 Iron, i. 585; ii. 317, 322 -- and carbonic oxide, ii. 345 -- cast, ii. 325 -- nitride, ii. 346 -- ores, ii. 319 -- sulphate, ii. 335 Isethionic acid, ii. 250 Isomorphism, i. 203, 368; ii. 1, 4, 8

Kaolin, ii. 70

Lakes, ii. 77 Lanthanum, ii. 93 Laughing gas, ii. 297 Law of Avogadro-Gerhardt, i. 309 -- -- Berthollet, i. 445 -- -- Boyle and Mariotte, i. 132 -- -- combining weights, i. 221 -- -- Dulong and Petit, i. 584 -- -- equivalents, i. 194 -- -- even numbers, i. 357 -- -- Gay Lussac, i. 133, 304, 307 -- -- Guldberg and Waage, i. 441 -- -- Henry and Dalton, i. 78 -- -- indestructibility of matter, i. 6 -- -- Kirchoff, i. 568 -- -- limits, i. 357 -- -- maximum work, i. 120 -- -- multiple proportions, i. 109, 214 -- -- partial pressures, i. 82 -- -- periodic, ii. 17 -- -- phases, ii. 410 -- -- reversed spectra, i. 568 -- -- specific heats, i. 584 -- -- substitution, i. 260, 365 -- -- volumes, i. 304 Lead, ii. 134 -- acetate, ii. 137 -- carbonate, ii. 140 -- chloride, ii. 139 -- chromate, ii. 136, 279 -- dioxide, ii. 142 -- nitrate, ii. 139 -- oxide, ii. 137 -- red, ii. 142 -- salts of, i. 491 -- tetrachloride, ii. 144 -- tetrafluoride, ii. 144 -- white, ii. 140 Leucone, ii. 107 Levigation, ii. 72 Light, chemical action of, i. 465 Lime, i. 605 Liquids, boiling points of, i. 135 Lithium, i. 574 -- carbonate, i. 575 Litharge, ii. 137 Litmus, i. 185 Lixiviation, methodical, i. 521 Luteocobaltic salts, ii. 359

Magnus' salt, ii. 392 Magnesia, i. 597 Magnesium, i. 590, 594 -- carbonate, i. 592, 602 -- chloride, i. 602 -- crystallohydrates of, i. 601 -- double salts of, i. 597 -- nitride, i. 595 -- silicide, ii. 102 -- sulphate, i. 600 Manganese, ii. 303 -- nitrides, ii. 310 -- oxides, ii. 306, 307, 308, 313 -- peroxide, i. 159; ii. 305 -- sulphate, ii. 307 Mass, influence of, i. 32, 436 Matches, ii. 154 Matter, primary, ii. 440 -- transmutability of, i. 14 Mercury, ii. 48 -- ammonia compounds, ii. 57 -- basic salts of, ii. 54 -- chlorides, ii. 52, 53, 54 -- compounds, heat of formation, ii. 50 -- cyanide, ii. 55 -- fulminating, ii. 56 -- iodide, ii. 55 -- nitrates, ii. 51 -- nitrides, ii. 56 -- oxides, ii. 53 -- sulphate, ii. 57 -- sulphides, ii. 221 Metalepsis, i. 28, 471 Metalloids, i. 23 Metals, i. 23 -- of alkaline earths, i. 64, 590, 591 -- of alkalis, i. 543 -- displacement of, ii. 427 Methane, i. 360 Moisture, determination of, in gases, i. 40 -- influence upon reaction, i. 403 Molecular volumes, ii. 37 -- weight and boiling point, i. 331 -- -- -- coefficient of refraction, i. 336 -- -- -- latent heat, i. 329 -- -- -- specific gravity of solutions, i. 335 -- -- -- surface tension, i. 334 Molecules, i. 319, 322 Molybdates, ii. 292 Molybdenum, ii. 290 -- anhydride, ii. 291 -- fluo-compounds, ii. 298 -- sulphides, ii. 297 Monophosphamide, ii. 178 Monosodium orthophosphate, ii. 167 Morphotropy, ii. 10

Naphtha, i. 373, 377 Nascent state, i. 33, 145, 146 Neodymium, ii. 97 Nickel, ii. 353 -- alloys, ii. 367 -- and carbonic oxide, ii. 367 -- fluoride, ii. 358 -- hydroxide, ii. 358 -- oxide, ii. 365 -- sulphate, i. 97; ii. 359 -- tetra-carboxyl, ii. 367 Niobium, i. 199; ii. 194, 198 Nitrates, i. 273 Nitres, i. 268, 555 Nitric anhydride, i. 280 -- oxide, i. 286 Nitrides, i. 227, 258, 620 Nitriles, i. 406 Nitrites, i. 284 Nitro-cellulose, i. 275 Nitro-compounds, i. 274 Nitrogen, i. 223, 225, 475 -- chloride, i. 476 -- iodide, i. 507 -- oxides of, i. 267, 280, 284, 294, 295 -- sulphide, ii. 270 Nitro-prussides, ii. 351 Nitroso-compounds, i. 288 Nitrosulphates, ii. 229 Nitrosyl chloride, ii. 176 Norwegium, ii. 59

Occlusion, i. 143 Olefiant gas, i. 370 Organo-metallic compounds, i. 356 Osmium, ii. 372, 382, 384 Osmotic pressure, i. 64 Osmuridium, ii. 383 Oxamide, i. 406 Oxidation, i. 16 Oxides, i. 183; ii. 36 Oxycobaltamine salts, ii. 359 Oxygen, i. 152, 157, 158, 163 -- compounds, heat of formation of, i. 120, 466 Ozone, i. 198, 229

Palladium, ii. 369 -- hydride, i. 143; ii. 380 Palladous chloride, ii. 379 -- iodide, ii. 379 Paracyanogen, i. 414 Paramorphism, ii. 9 Parasulphatammon, ii. 269 Peat, i. 344 Peligot's salt, ii. 281 Percentage composition, i. 326 Perchloric anhydride, ii. 282 Periodates, i. 510 Permanganic anhydride, ii. 313 Permolybdates, ii. 297 Peroxide, chloric, i. 484 Peroxides, i. 159; ii. 15, 23 Perstannic oxide, ii. 133 Persulphates, ii. 253 Petroleum, i. 373 Phenol, solubility of, i. 75 Phlogiston, i. 17 Phosgene gas, ii. 175 Phospham, ii. 178 Phosphides, ii. 157 Phosphine, ii. 158, 160 Phosphonium iodide, ii. 159 Phosphoric anhydride, ii. 161 Phosphorous anhydride, ii. 160 Phosphorus, ii. 149 -- ammonium compounds, ii. 178 -- chlorides, ii. 174 -- fluorides, ii. 173 -- iodides, i. 505, 506; ii. 172 -- oxychlorides, ii. 175 -- sulphides, ii. 213 -- sulphochloride, ii. 213 -- thermo-chemical data for, ii. 153 Phosphuretted hydrogen, ii. 158, 160 Photography, ii. 431 Photo-salts, ii. 432 Plants, chemical reactions in, i. 547 -- and nitrogen, i. 230 Platinic chloride, ii. 377 -- hydroxide, ii. 379 Platino-ammonium compounds, ii. 391 -- chlorides, i. 467; ii. 378 -- cyanides, ii. 386 -- nitrites, ii. 390 -- sulphites, ii. 390 Platinous chloride, ii. 379 Platinum, ii. 376 -- alloys, ii. 373 -- black, ii. 376 -- metals, ii. 369, 375 -- oxide, ii. 378 Poly-haloid salts, i. 545 Polymerism, i. 207, 367 Polysulphides, ii. 217 Potassium, i. 544, 558 -- aurate, ii. 449 -- bromide, i. 550 -- carbonate, i. 549 -- chlorate, i. 161, 482 -- chloride, i. 72, 543 -- chromate, ii. 280 -- cyanide, i. 412, 551 -- dichromate, ii. 278 -- ferricyanide, ii. 346 -- ferrocyanide, i. 346, 412 -- hydrosulphide, ii. 219 -- hydroxide, i. 548 -- iodide, i. 550 -- manganate, ii. 310 -- nitrate, i. 553 -- oxides, i. 559 -- permanganate, ii. 311 -- stannate, ii. 133 -- sulphate, i. 72, 549 -- sulphide, ii. 219 -- telluride, ii. 274 Praseocobaltic salts, ii. 361 Praseodidymium, ii. 97 Proteid substances, i. 224 Prout's hypothesis, ii. 439 Prussian blue, i. 419; ii. 349 Purpureocobaltic salts, ii. 361 Purpureotetramine salts, ii. 361 Pyrocollodion, i. 275 Pyronaphtha, i. 375 Pyrosulphuryl chloride, i. 321; ii. 235

Reactions, chemical, i. 3 -- -- conditions for, i. 34 -- -- contact, i. 39 -- -- endothermal, i. 30 -- -- exothermal, i. 30 -- -- limit of, i. 437 -- -- rate of, ii. 152 Recalescence, ii. 333 Reduction, i. 16 Refraction equivalent, i. 336 Regenerative furnaces, i. 398 Reiset's salts, ii. 394 Respiration, i. 152, 154, 387 Rhodium, ii. 381 Rock salt, i. 421 Roseocobaltic salts, ii. 360 Rosetetramine salts, ii. 361 Rubidium, i. 576 Ruthenium, ii. 372, 382, 384

Sal-ammoniac, i. 248, 318, 457 -- solubility of, i. 458 -- vapour density of, i. 317 Salts, i. 187, 419 -- acid, i. 193, 533 -- basic, i. 193, 533; ii. 54 -- double, i. 598 -- electrolysis of, i. 191 -- heat of formation, i. 189 -- melting points of, i. 135 -- pyro, i. 193 -- theory of, i. 193 Saponification, i. 530 Scandium, ii. 94 Selenium, ii. 273 -- chlorides, ii. 275 Selenious anhydride, ii. 271 Silica, i. 100; ii. 108 -- soluble, ii. 113 Silicates, i. 544; ii. 116 Silicon, ii. 99 -- chloride, ii. 103, 104 -- chloroform, ii. 103 -- bromide, ii. 104 -- fluoride, ii. 105 -- hydride, ii. 102, 103 -- iodide, ii. 105 -- iodoform, ii. 105 Silver, ii. 418 -- allotropic varieties of, ii. 421 -- bromide, ii. 429 -- chlorate, ii. 437 -- chloride, ii. 429 -- cyanide, ii. 433 -- fluoride, ii. 430 -- fulminating, ii. 426 -- hyponitrite, i. 294 -- iodide, ii. 429 -- nitrate, ii. 426 -- nitrite, i. 284 -- orthophosphate, ii. 164 -- oxides, ii. 424 -- peroxide, ii. 422 -- plating, ii. 434 -- soluble, ii. 420 -- subchloride, ii. 432 Slags, ii. 323 Smalt, ii. 354 Soaps, i. 531 Soda ash, i. 519 -- caustic, i. 527 -- manufacture of, i. 459 -- waste, i. 522 Soda lime, i. 237 Sodamide, i. 539 Sodium, i. 513, 533 -- alloys, i. 559 -- amalgams, i. 537 -- bicarbonate, i. 526 -- carbonate, i. 519, 525 -- -- crystallohydrates of, i. 108 -- -- manufacture of, i. 523 -- -- solutions of, i. 525 -- chloride, i. 419 -- -- double salts of, i. 430 -- -- solutions of, i. 88, 99, 429 -- hydride, i. 537 -- hydroxide, i. 528, 529 -- -- solutions of, i. 529 -- nitrate, i. 269 -- -- solutions of, i. 72 -- organo compounds of, i. 540 -- oxides, i. 540, 541 -- phosphates, ii. 166 -- platinate, ii. 378 -- pyrosulphate, i. 518 -- sesquicarbonate, i. 526 -- stannate, ii. 133 -- subchloride, i. 540 -- sulphate, i. 513 -- -- acid salt, i. 518 -- -- crystallohydrates of, i. 515 -- -- solutions of, i. 73, 515, 516 -- sulphite, ii. 226 -- thiosulphate, ii. 230 -- -- solutions of, i. 74 -- tungstate, ii. 294 Soils, i. 344; ii. 73 Solubility, coefficient of, i. 67, 71 Solutions, i. 330 -- aqueous, i. 59 -- boiling points of, i. 94, 100 -- crystallisation of, i. 427 -- colour of, i. 95 -- diffusion of, i. 61, 429 -- of double salts, i. 599 -- formation of ice from, i. 91, 428 -- heat of formation of, i. 74, 75, 76 -- of gases, i. 68 -- isotonic, i. 64 -- saturated, i. 65 -- specific gravity of, i. 429, 584 -- supersaturated, i. 96 -- theory of, i. 64, 89, 92, 97, 106, 215, 323, 608; ii. 3, 164 -- vapour tension of, i. 90, 92 -- volumes of, i. 87 -- Specific heat, i. 585, 586, 588 Spectra absorption, i. 566 Spectrum analysis, i. 560, 561 Stannic chloride, ii. 132 -- fluoride, ii. 132 -- oxide, ii. 130 -- sulphide, ii. 132 Stannous chloride, ii. 130 -- oxide, ii. 129 -- salts, ii. 129 Steam, vapour tension of, i. 54 Steel, ii. 327, 328, 330 Strontium, i. 615 -- chloride, i. 615 -- hydroxide, i. 615 -- nitrate, i. 615 -- oxide, i. 617 Substitution chemical, i. 5 Sulphamide, ii. 270 Sulphatammon, ii. 269 Sulphates, ii. 248 Sulphides, i. 98; ii. 213 Sulphonitrites, ii. 229 Sulphoxyl, ii. 250 Sulphur, ii. 200 -- chlorides of, ii. 264 Sulphuretted hydrogen, ii. 208 Sulphuric anhydride, ii. 232 -- peroxide, ii. 251 Sulphurous anhydride, ii. 224 Sulphuryl chloride, ii. 268 Superphosphates, ii. 168

Tantalum, ii. 194, 198 Tellurium, ii. 274 -- bromide, ii. 275 -- chlorides, ii. 275 Tellurous anhydride, ii. 271 Temperature, critical, i. 131 Test papers, i. 185 Thallium, ii. 88, 91 Thallic oxide, ii. 93 Thallous hydroxide, ii. 92 -- oxide, ii. 92 Thiocarbonates, ii. 262 Thionyl chloride, ii. 267 Thiophosgene, ii. 262 Thiophosphoryl fluoride, ii. 263 Theory, atomic, i. 216 -- unitary, i. 195 -- vortex, i. 217 Thermochemistry, i. 173 Thorium, ii. 148 Tin, ii. 125 -- alloys, ii. 127 Titanium, ii. 144 -- chloride, ii. 145 -- nitride, ii. 146 -- nitrocyanide, ii. 146 -- oxides, ii. 145 Tripoli, ii. 110 Trisodium orthophosphate, ii. 166 Tungstates, ii. 292 Tungsten, ii. 290 -- anhydride, ii. 291 -- nitride, ii. 297 -- sulphide, ii. 297 Turnbull's blue, ii. 350 Types of combination, ii. 10

Ultramarine, ii. 84 Uranium, ii. 30, 297 -- atomic weight of, ii. 26 -- dioxide, ii. 301 -- oxides, ii. 298 -- tetrachloride, ii. 301 Urano-alkali compounds, ii. 298 Uranyl, ii. 301 -- ammonium carbonate, ii. 300 -- nitrate, ii. 300 -- phosphate, ii. 300 Urea, i. 409

Valency of elements, i. 404, 418, 581 Van der Waal's formula, i. 82, 140 Vanadic anhydride, ii. 196 Vanadium, ii. 194 -- oxychloride, ii. 195 Vapour density, determination of, i. 301 Ventilation, i. 244 Viscosity, i. 355 Volumes, molecular, ii. 4 -- gases, i. 300

Water, i. 40 -- composition of, i. 114, 118, 148, 169, 305, 333 -- compressibility of, i. 53 -- of constitution, i. 109 -- of crystallisation, i. 95, 510 -- dissociation of, i. 118 -- expansion of, i. 53 -- gas, i. 129, 400, 401 -- hard, i. 47 -- hygroscopic, i. 56 -- mineral, i. 45 -- rain, i. 43 -- river, i. 43 -- sea, i. 46 -- specific heat of, i. 52 -- -- gravity of, i. 50 -- spring, i. 44 Wave lengths, i. 564 Wood, i. 339

Ytterbium, ii. 93 Yttrium, ii. 93

Zinc, ii. 39 -- ammonia-chlorides, ii. 41 -- chloride, ii. 40, 41 -- compounds, heat of formation of, ii. 51 -- oxide, ii. 39, 40 -- sulphate, ii. 39 Zirconium, ii. 146 -- chloride, ii. 147 -- hydroxide, ii. 147 -- oxide, ii. 147

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